A temperature-sensitive, reusable PTA-AgNO 3 -CS supramolecular polymer for 3D printing and strain sensing

A temperature-sensitive, reusable PTA-AgNO 3 -CS supramolecular polymer for 3D printing and strain sensing | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article A temperature-sensitive, reusable PTA-AgNO 3 -CS supramolecular polymer for 3D printing and strain sensing Shengqiang Liao, Miaomiao Jia, Juncheng Wang, Jiawen Liu, Xianzhi Kong, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8804107/v1 This work is licensed under a CC BY 4.0 License Status: Under Revision Version 1 posted 14 You are reading this latest preprint version Abstract Supramolecular polymers, formed through hydrogen bonds and dynamic metal coordination bonds, exhibit excellent reversibility and recyclability. In this study, dimethyl sulfoxide (DMSO) was used as a solvent to synthesize a PTA-AgNO 3 -CS (PAC) supramolecular polymer from thioctic acid (TA), silver nitrate (AgNO 3 ), and chitosan (CS). The non-covalent interactions in PAC enable self-healing and temperature sensitivity. This polymer demonstrates superior mechanical properties, freeze resistance, moisture retention, hemolysis resistance, blood clotting promotion, and antibacterial activity. Capable of 3D printing and repeated fabrication, PAC meets personalized tissue engineering scaffold requirements while reducing production costs. Doped with carbon nanotubes (CNTs), the polymer achieves enhanced conductivity, fatigue resistance, strain sensing sensitivity, and cyclic stability. Field tests using human motion monitoring have confirmed its effectiveness as a reliable strain sensor. Poly thioctic acid Supramolecular polymer Temperature sensitivity 3D printing Strain sensing Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 1. Introduction Supramolecular polymers are constructed through non-covalent interactions (including hydrogen bonds, metal coordination, π-π stacking, and host-guest interactions) between one or more molecular components. These reversible non-covalent bonds not only enable supramolecular polymers to undergo reversible structural, morphological, and performance switching when exposed to external stimuli, but also provide a flexible and robust platform for developing functional supramolecular materials and smart supramolecular devices[ 1 , 2 ]. Traditional polymers, primarily composed of covalent bonds, exhibit static structural stability and poor reversibility, making them difficult to dissociate through simple methods. In contrast, supramolecular polymers demonstrate distinct advantages such as self-healing properties, reusability, and intelligent responses to various biological stimuli. These characteristics significantly broaden the application scope of supramolecular polymers[ 3 , 4 ]. Supramolecular polymers, with their dynamic and reversible non-covalent crosslinking properties (such as hydrogen bonds, ionic bonds, and coordination bonds), provide customized structural designs, dynamic functional responses, and eco-friendly sustainable solutions for 3D printing[ 5 ]. These materials also exhibit critical properties including high tensile strength, self-healing capabilities, environmental stability, wide strain detection range, and high sensitivity, perfectly meeting the demands of strain sensors for mechanical adaptability, signal reliability, and long-term durability[ 6 , 7 ]. 3D printing technology, also known as additive manufacturing (AM), involves designing models using computer-aided design (CAD) software and printing three-dimensional structures through predefined programs in 3D printers[ 8 , 9 ]. The extrusion printing method works by pushing ink through a piston, which continuously flows in filament form from the nozzle and deposits onto the printing platform, completing the printed object. This printing method is fast and cost-effective[ 10 , 11 ]. Strain sensors will deform when stimulated by external forces, and then convert mechanical deformation into electrical signals, which have great application prospects in wearable devices[ 12 – 14 ], electronic skin[ 15 , 16 ], intelligent robots[ 17 , 18 ], medical care monitoring[ 19 , 20 ], etc. Supramolecular polymers, with their excellent flexibility, tensile strength, biocompatibility, and mechanical properties, are considered promising substrates for designing strain sensors[ 21 ]. To enhance their conductivity, conductive materials such as metals and carbon-based materials (carbon black, carbon nanotubes, graphene) can be incorporated. Among these, carbon nanotubes (CNTs) stand out in the strain sensor field due to their high electrical conductivity, exceptional flexibility, low density, and large aspect ratio[ 22 ]. Poly thioctic acid (PTA) is a class of high molecular weight polymers synthesized from natural small-molecule thioctic acid (TA) through ring-opening polymerization under light and heat stimulation[ 23 , 24 ]. The carboxyl groups in PTA can form hydrogen bonds with adjacent molecules, endowing the derived polymers with remarkable dynamic properties such as reprocess ability and self-repair capability. Moreover, the presence of carboxyl groups enables PTA to readily undergo modification reactions with various chemical units, making it possible to introduce multiple functional groups into TA-derived polymers[ 25 , 26 ]. Chitosan (CS), a natural polymer typically synthesized by removing acetyl groups from chitin through alkaline or enzymatic hydrolysis, ranks as the second most abundant biomolecule on Earth. Its backbone contains amino and hydroxyl groups, exhibiting exceptional properties including biodegradability, biocompatibility, non-toxicity, bioadhesion, and antibacterial activity[ 27 , 28 ]. Silver nitrate (AgNO 3 ) not only possesses the physical and chemical characteristics of silver but also forms metal coordination bonds, demonstrating broader antibacterial activity and superior biocompatibility[ 29 ]. Dimethyl sulfoxide (DMSO), often called the "universal solvent," serves as a cryoprotectant for bone marrow and blood cell cryopreservation due to its anti-inflammatory, analgesic, diuretic, and sedative effects[ 30 ]. This study utilizes DMSO as the primary solvent and TA, AgNO 3 , and CS as key raw materials to develop a PTA-AgNO 3 -CS (PAC) supramolecular polymer containing hydrogen bonds and dynamic metal coordination bonds. The non-covalent interactions in PAC enable self-healing properties, reprocessing ability, and temperature sensitivity. PAC also exhibits excellent mechanical strength, freeze resistance, and moisture retention. It demonstrates no significant hemolysis in red blood cells, promotes blood clotting, and shows remarkable antibacterial activity. For applications, PAC can be used for 3D printing and repeated printing, meeting the customized production needs of personalized tissue engineering scaffolds. Incorporating CNTs into PAC enhances its conductivity. The conductive PAC supramolecular polymer demonstrates outstanding fatigue resistance, strain sensing performance, sensitivity, and cyclic stability. Practical human motion monitoring has validated its effectiveness and reliability as a strain sensor. 2. Experimental section 2.1 Materials Thioctic acid (TA, 99%) and calcium chloride (CaCl 2 , 99%) were purchased from China Shanghai Aladdin Reagent Co., Ltd. Dimethyl sulfoxide (DMSO, 99%) was purchased from China Shanghai MacLin Biochemical Technology Co., Ltd. Silver nitrate (AgNO 3 , 99.8%) and acetic acid (HAC, 99%) were purchased from China Xilong Technology Co., Ltd. Chitosan (CS, deacetylation degree: 91%, viscosity: 100 mPa s) was purchased from Zhejiang Jinke Pharmaceutical Co., Ltd. Ethyl acetate (EAC, 99.5%) and sodium hydroxide (NaOH, 96%) were purchased from China Tianjin Kemiao Chemical Reagents Co., Ltd. Dry powder phosphate buffer (PBS) was purchased from China Beijing Lanjieke Technology Co., Ltd. Carbon nanotubes (CNTs, 95%, multilayer, diameter: 8–15 nm, inner diameter: 3-5nm, length: 10–50µm) were purchased from Jiangsu Xianfeng Nano Material Technology Co., Ltd. Sodium citrate anticoagulant sheep blood was purchased from China Shanghai Yuchun Biotechnology Co., Ltd. Escherichia coli and Staphylococcus aureus were purchased from China Guangdong Microbial Strain Preservation Center. 2.2 Synthesis of PAC supramolecular polymer The preparation process of PAC supramolecular polymer is shown in Fig. S1 . Step 1: Add 5 g of TA to DMSO and place it in a water bath at 70 ℃ for 20–40 min under stirring. Cool to room temperature to obtain the PTA solution. Step 2: Dissolve 0.017 g of AgNO 3 in 1 ml of DMSO by stirring until completely dissolved to prepare the AgNO 3 solution. Step 3: Disperse CS powder uniformly in 1.9 ml of H 2 O using magnetic stirring, then add glacial acetic acid and mix thoroughly to form the CS acetate aqueous solution. Step 4: Add the AgNO 3 solution to the PTA solution and stir magnetically for 15–30 min to achieve the PTA-NO 3 reaction mixture. Step 5: Drop the CS acetate aqueous solution into the PTA-NO 3 reaction mixture and stir vigorously until uniform. The resulting PAC supramolecular polymer printing ink is injected into a glass groove and left undisturbed for 8–12 hours to form the PAC supramolecular polymer. When the DMSO content was fixed at 22%, the CS-0%, CS-0.5%, CS-1.5%, and CS-2.5% PAC supramolecular polymers were prepared by adjusting the CS content. When the CS content was fixed at 0.5%, the DMSO-0%, DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers were obtained by modifying the DMSO content. Notably, the DMSO-0% PAC supramolecular polymer was replaced with a NaOH solution to dissolve TA. 2.3 3D printing of PAC supramolecular polymer 2.3.1 3D printing performance test of PAC supramolecular polymer M CS−0.5% , M CS−1.5% and M CS−2.5% printing inks were added to the barrel of an extrusion 3D printer to print long strips and grid printed parts. The effects of CS content on the printing performance of printing inks were discussed in three aspects: diameter deviation rate, area fidelity and high fidelity. The printing parameters are as follows: print nozzle 0.3 mm, extrusion pressure 20 mN, and printing speed 850 mm/min. Diameter deviation rate is calculated according to Eq. ( 1 ): $$\:\text{∆D}\text{=}\frac{\left(\text{D}\text{-}{\text{D}}_{\text{0}}\right)}{{\text{D}}_{\text{0}}}\text{×100%}$$ 1 Where: ∆D is the diameter deviation rate of the printing filament, D is the diameter of the actual printing filament (mm), and D 0 is the diameter of the printing needle (mm). Area fidelity is calculated according to Eq. ( 2 ): $$\:{\text{F}}_{\text{g}}\text{=}\frac{{\text{S}}_{\text{a}}}{{\text{S}}_{\text{t}}}\text{×100%}$$ 2 Where: F g is the area fidelity parameter of the grid, S a is the actual grid area (mm 2 ), S t is the theoretical grid area (mm 2 ). High fidelity is calculated according to Eq. ( 3 ): $$\:{\text{F}}_{\text{h}}\text{=}\frac{{\text{h}}_{\text{a}}}{{\text{h}}_{\text{t}}}\text{×100%}$$ 3 Where: F h is the high fidelity parameter, h a is the actual height (mm), h t is the theoretical height (mm). 2.3.2 Reprint of PAC supramolecular polymer The cured M CS-0.5% PAC supramolecular polymer scaffold was heated at 60 ℃ to transform the solidified PAC supramolecular polymer into a flowable sol. Using this sol as printing ink, we fabricated filaments and grid-shaped scaffolds. The study evaluated the reproducibility of the printing ink in three key aspects: diameter deviation rate, filament fidelity, and structural integrity. 2.4 Preparation of conductive supramolecular polymer with PTA-AgNO 3 -CS After adding CNTs to the PAC supramolecular polymer and ultrasonication for 40 min, the PAC supramolecular polymer was injected into the glass groove and left for 8–12 h to obtain the PAC conductive supramolecular polymer. The CS and DMSO contents were 0.5% and 22%, respectively. 2.5 Characterization 2.5.1 Infrared spectroscopy test The infrared spectrometer (Brook, Germany) was used to analyze the infrared spectrum of the freeze-dried powder of TA, PTA, PTA and AgNO 3 reactants, with a scanning range of 4000 ~ 500 cm − 1 and resolution of 4 cm − 1 . 2.5.2 Mechanical properties test The tensile test was conducted on a universal material mechanical testing machine (China Wanchen) equipped with a 100 N load cell. The PAC supramolecular polymer was formed into a dumbbell shape, with a total length of 35 mm, a measured length of 12 mm, a width of 2 mm, and a thickness of 1 mm, and axial tensile testing was performed at a loading speed of 100 mm/min. The compression test was conducted on a universal material testing machine equipped with a 100 N load cell. The PAC supramolecular polymer was formed into a cylindrical sample measuring 10 mm in height and 10 mm in diameter, which was compressed at a loading rate of 10 mm/min. The compressive strength (P) was calculated using Eq. (4): P = F / S (4) Where: P is the pressure (KPa), F is the applied pressure (N), and S is the cross-sectional area of the sample (m 2 ). 2.5.3 Adhesion performance The adhesion test was conducted on a universal material testing machine equipped with a 100 N load cell. The PAC supramolecular polymer was placed between two aluminum plates, maintaining a contact area of 20 mm×20 mm. After applying gentle pressure for 10 seconds and allowing it to rest for 60 seconds, shear tensile testing was performed immediately. The shear adhesion strength was calculated by dividing the maximum load by the contact area, with five repetitions per set. 2.5.4 Self-healing performance Two cylindrical PAC supramolecular polymers stained with methylene blue and rhodamine B were cut in two with a scalpel, then tightly bonded together, and left to repair by itself. The repair was observed after 6 hours. 2.5.5 Freeze resistance and moisture retention To evaluate DMSO's impact on PAC supramolecular polymer freeze resistance, two PAC supramolecular polymers (DMSO-0% and DMSO-22%) were placed in 25 ℃ and − 20 ℃ environments, respectively, for tensile bending testing. Differential Scanning Calorimetry (DSC) equipment (Nordirch, Germany) was employed to measure the PAC supramolecular polymer's freeze resistance under varying conditions: cooling from 40 ℃ to -60 ℃ at a rate of -10 ℃/min, holding at -30 ℃ for 5 minutes, followed by heating to 40 ℃ at 10 ℃/min. Thermal flow measurements were continuously monitored during both cooling and heating processes. In order to test the effect of DMSO on the water retention of the PAC supramolecular polymer, two kinds of PAC supramolecular polymers with DMSO-0% and DMSO-22% were stored in a room temperature container for 11 days, and the weight change of the two PAC supramolecular polymers was recorded every day. 2.5.6 In vitro blood compatibility. In vitro hemolysis experiments were conducted using sodium citrate-treated whole sheep blood to evaluate the hemolysis performance of the PAC supramolecular polymer. Weighing 1 ml of sheep blood and dispersing it in 10 ml of PBS buffer. The mixture was placed in a centrifuge and centrifuged at 2280 r/min three times. The lower layer of red blood cells after centrifugation was collected and diluted with PBS buffer at a ratio of 1:10 to obtain the red blood cell dilution. The red blood cell dilution and sample were placed in a clean test tube, and the color change of the solution within the test tube was observed. If the solution turned red, it indicated red blood cell rupture and hemolytic properties of the sample. Deionized water mixed with the red blood cell dilution served as the positive control, while PBS buffer mixed with the red blood cell dilution served as the negative control. All test tubes were incubated on a shaker maintained at 37 ℃ for 2 hours to ensure full contact between red blood cells and the sample. After incubation, the suspension in each test tube was transferred to a centrifuge (China Xiangyi) and centrifuged at 3230 r/min to effectively remove red blood cell fragments. Finally, the absorbance of the supernatant was precisely measured using a UV spectrophotometer (Shimadzu, Japan) at a wavelength of 540 nm. The hemolysis rate of the sample is calculated according to Eq. ( 5 ): $$\:\text{Hemolysis rate}\left(\text{%}\right)\text{=}\frac{{\text{OD}}_{\text{S}}\text{-}{\text{OD}}_{\text{n}}}{{\text{OD}}_{\text{P}}\text{-}{\text{OD}}_{\text{n}}}\text{×100%}$$ 5 Where: Hemolysis rate is the hemolysis rate of the sample, OD s is the absorbance of the sample, OD n is the absorbance of the negative control sample, OD p is the absorbance of the positive control sample. In vitro coagulation experiments were conducted using sodium citrate-treated whole sheep blood to evaluate the clotting performance of the PAC supramolecular polymer. The samples were placed in test tubes with a blank control group (without samples). 0.1 ml of recalcified blood was added and incubated in a 37 ℃ water bath for 0, 2, 4, 6, and 8 minutes. Deionized water was then added to terminate the clotting process. Blood supernatants were collected at each time point and absorbance measured at 540 nm. This measurement reflects hemoglobin (HA) release from free red blood cells. A higher relative hemoglobin retention rate (RHA) indicates slower clotting kinetics. The relative RHA is calculated according to Eq. ( 6 ): $$\:\text{RHA}\left(\text{%}\right)\text{=}\frac{{\text{HA}}_{\left(\text{t}\right)}}{{\text{HA}}_{\left(\text{0}\right)}}\text{×100%}$$ 6 Where: RHA is the retention rate relative to hemoglobin, HA (t) is the hemoglobin absorbance of the sample at the time of measurement, and HA (0) is the hemoglobin absorbance of the sample at the time of measurement without addition. 2.5.7 In vitro bacteriostatic test The antibacterial properties of Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus) were tested using the inhibition method. First, prepare nutrient agar medium by adding agar powder to distilled water, heating it in an oil bath at 100°C until boiling, then sterilizing it for 1 hour in a high-pressure steam sterilizer. Pour the liquid agar into petri dishes and sterilize under UV light for 30 minutes to obtain the final medium. Next, perform bacterial dilution: add 1 ml of physiological saline to test tubes containing bacterial cultures, scrape bacteria with a pipette, transfer to conical flasks with small beads (25 ml), then add 9 ml of saline to disperse the beads, creating a bacterial suspension. Dilute this suspension six times with 1 ml aliquots. Place 200 µl of diluted E.coli and S.aureus cultures on the nutrient agar medium in a laminar flow hood, spread evenly with a swab, and position UV-sterilized circular samples on the surface. Incubate at 37°C for 24 hours. The inhibition zone around the PAC supramolecular polymer reflects its antibacterial properties, and the radius of the inhibition area is measured using ImageJ software. 2.5.8 Conductivity test To test the conductivity of the PAC conductive supramolecular polymer, the conductive supramolecular polymer was sandwiched between two aluminum plates and connected to an LED indicator and a power supply with a wire. A certain voltage was applied and the LED indicator was observed. 2.5.9 Fatigue resistance test The fatigue resistance performance test was conducted on a universal material mechanical testing machine equipped with a 100 N load cell. The PAC conductive supramolecular polymer was formed into dumbbell-shaped specimens measuring 35 mm in total length, 12 mm in gauge length, 2 mm in width, and 1 mm in thickness. Continuous tensile cycles were performed at a constant speed of 100 mm/min, stretching the specimens to 10%, 20%, 30%, and 40% of their original lengths, respectively. 2.5.10 Strain sensing test. The strain sensing performance of conductive supramolecular polymer was tested using a mechanical testing machine and a source meter (Tektronix, USA). The PAC conductive supramolecular polymer was fabricated into a strip measuring 3 cm in length, 1 cm in width, and 2 mm in thickness. The strip was secured on the machine's fixture while connected to the Source Measure Unit's input terminal. By monitoring the resistance fluctuations through the Source Measure Unit, we recorded the PAC conductive supramolecular polymer's tensile strain sensing curve to obtain key parameters: sensitivity factor (GF), response time, and recovery time, which collectively reflect the material's sensitivity. GF represents the slope of the resistance-strain curve, response time indicates the duration from stress application to material deformation, and recovery time denotes the period required for the PAC conductive supramolecular polymer's resistance to return to its original state after strain unloading. A cyclic loading-unloading process was conducted with 40% strain applied to the PAC conductive supramolecular polymer, repeated 200 times. The resistance changes during this cyclic loading-unloading cycle were used to evaluate the PAC conductive supramolecular polymer's stability and durability. 2.5.11 Human detection The PAC conductive supramolecular polymer is made into a long strip of 3 cm long, 1 cm wide and 2 mm thick, which is attached to the finger joint, wrist, elbow and knee of the human body. The strip is connected to the input end of the Source Measure Unit, and the tensile strain sensing curve of the PAC conductive supramolecular polymer is recorded by the resistance fluctuation of the Source Measure Unit to complete the detection of human movement. 3. Results and discussion 3.1 Synthesis and structural characterization of PAC supramolecular polymer As shown in Fig. 1 a and Fig. S2 , TA is dissolved in DMSO and heated at 70 ℃ for 5 minutes. During this process, the disulfide bonds in TA break, allowing S radicals to interconnect and form new disulfide bonds, while carboxyl groups form hydrogen bonds, ultimately generating PTA. This reaction causes the 1690 cm − 1 peak of TA to split into two distinct peaks representing symmetric and asymmetric stretching vibrations of PTA's carboxyl groups. When AgNO 3 is added to PTA, a PTA-AgNO 3 solution is formed. The Ag + ions introduced into the polymer coordinate with carboxyl groups on PTA chains, causing shifts in the stretching peaks. Subsequently, CS solution is added and thoroughly mixed with the system. After cooling, the amino groups on the CS chains form hydrogen bonds with the carboxyl groups in PTA, while Ag + ions establish metal coordination bonds with both the amino and hydroxyl groups on the CS chains. These Ag + ions also link the PTA and CS chains, creating a dynamic network structure[ 31 – 33 ]. As shown in Fig. 1 b, the non-covalent interactions of the PAC supramolecular polymer. At elevated temperatures, hydrogen and metal coordination bonds break, then reform upon cooling. This temperature-sensitive behavior enables the supramolecular polymer to undergo thermal cycling decomposed at high temperatures and restored upon cooling-making PAC supramolecular polymer suitable for applications in 3D printing and self-healing materials[ 34 , 35 ]. 3.2 Mechanical properties of PAC supramolecular polymer As shown in Fig. 2 a, the tensile strength and modulus of the PAC supramolecular polymer first increase and then decrease with increasing CS content. The CS-0% PAC supramolecular polymer exhibits the lowest values at 0.24 MPa and 0.02 MPa, while the CS-0.5%, CS-1.5%, and CS-2.5% PAC supramolecular polymers show the highest values of 0.49 MPa and 0.05 MPa respectively. This is primarily because CS enhances the formation of coordination bonds with Ag + , creating a more compact network structure that boosts PAC supramolecular polymer strength. However, excessive CS content increases solution viscosity and weakens intermolecular interactions, thereby reducing tensile strength and modulus. The fracture elongation rate decreases from 2063% to 823% as CS content increases, likely due to significant changes in intermolecular interactions. The originally homogeneous structure breaks down, internal pore sizes expand, and molecular aggregation becomes disordered, ultimately resulting in non-uniform pore distribution. As shown in Fig. 2 b, the addition of DMSO significantly enhances the PAC supramolecular polymer's tensile strength, elongation at break, and tensile modulus. The DMSO-0% PAC supramolecular polymer exhibits the lowest values for these properties, while the DMSO-5% PAC supramolecular polymer shows the highest. The DMSO-22% PAC supramolecular polymer demonstrates the greatest elongation at break. This trend likely stems from DMSO's ability to improve the solubility and dispersion of components while forming hydrogen bonds with water molecules, creating strong intermolecular interactions. Conversely, reduced DMSO content increases solid content, decreases molecular spacing, and tightens the structure. These structural changes ultimately lead to increased tensile strength and modulus, while the elongation at break gradually decreases. As shown in Fig. 2 c and Fig. S3 , when the PAC supramolecular polymer's deformation reaches 70%, the compressive strength initially increases with rising CS content before decreasing. The CS-0% PAC supramolecular polymer exhibits the lowest compressive strength at 0.16 MPa, while the CS-0.5%, CS-1.5%, and CS-2.5% PAC supramolecular polymers show the highest strength at 0.27 MPa. This is primarily due to the CS molecules' rich content of amino and carboxyl groups, which form stronger coordination bonds with silver ions through complexation. These coordination bonds create a denser internal network structure within the PAC supramolecular polymer, enhancing inter-component connections and thus boosting compressive strength. However, excessive CS content may cause molecular chain entanglement and aggregation, disrupting the ordered network structure and weakening intermolecular interactions, ultimately leading to reduced compressive strength. As shown in Fig. 2 d and Fig. S4 , when the PAC supramolecular polymer deformation reaches 70%, the compressive strength initially increases with increasing DMSO solvent content before decreasing. The DMSO-0% PAC supramolecular polymer exhibits the lowest compressive strength at 0.05 MPa, while the DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers show maximum compressive strength of 0.35 MPa at 5% DMSO content. This phenomenon primarily stems from DMSO's ability as a polar organic solvent to form extensive hydrogen bond networks with water molecules. These hydrogen bonds enhance intermolecular forces, stabilizing the PAC supramolecular polymer's internal structure and thereby improving compressive strength. Additionally, appropriate DMSO concentration increases PAC supramolecular polymer viscosity, reducing molecular spacing and enhancing structural compactness, which further elevates compressive strength. 3.3 Adhesion, self-healing, frost resistance and moisture retention of PAC supramolecular polymer Figure 3 a shows physical photos of the PAC supramolecular polymer adhering to plastic, glass, rubber, and iron. The PAC supramolecular polymer demonstrates strong adhesion to these materials, primarily due to the carboxyl groups in TA and the abundant carboxyl and amino groups in CS. When contacting material surfaces, these functional groups interact with atoms or functional groups through various mechanisms. Figure 3 b presents the adhesion strength data of the PAC supramolecular polymer. As CS content increases, the adhesive strength rises, with CS-0% PAC supramolecular polymer showing the lowest adhesion (7.74 KPa). The CS-2.5% PAC supramolecular polymer achieves the highest strength at 67.74 KPa. This enhancement stems from CS molecules containing both amino and carboxyl groups, which form metal-coordinated bonds with aluminum sheets, thereby strengthening the interfacial bonding between the PAC supramolecular polymer and the metal substrate[ 36 , 37 ]. As the DMSO solvent content increases, the adhesive strength of the PAC supramolecular polymer first rises and then decreases. The DMSO-0% PAC supramolecular polymer exhibits the lowest tensile adhesion strength at 1.82 KPa, while the DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers show significant variations. Notably, the DMSO-12% PAC supramolecular polymer demonstrates the highest adhesion strength of 22.77 KPa. This is primarily attributed to DMSO's ability to enhance solubility and dispersion of components, which increases the number of functional groups interacting with aluminum plates, thereby boosting adhesion strength. However, excessive DMSO causes molecular chain extension, increasing contact opportunities between internal functional groups and aluminum plates. This expansion of cross-linking points ultimately reduces the interaction between functional groups and aluminum plates, leading to decreased adhesion strength. To investigate the self-healing properties of PAC supramolecular polymer, the PAC supramolecular polymer was stained with methylene blue and rhodamine B to create two cylindrical specimens in different colors. The specimens were cut with a scalpel, tightly bonded together, and left to self-repair under static conditions. As shown in Fig. S5 , the PTA-AgNO 3 -CS supramolecular polymer features a porous structure. When subjected to external forces, its pores deform (e.g., compress or collapse) to disperse stress and reduce crack propagation[ 38 ]. As shown in Fig. 3 c, after 12 hours, they were recombined, revealing fused edges without visible fracture marks under tensile stress. The self-healing mechanism stems from hydrogen bonds and dynamic metal-ligand coordination within the PAC supramolecular polymer. When subjected to external forces causing molecular breakage, altered intermolecular distances trigger hydrogen bonds to reorganize through thermal motion. Simultaneously, rapid adjustment and reconstruction of metal-ligand interactions enable seamless reconnection of fractured sections, achieving swift restoration to its original state[ 39 , 40 ]. Figure 3 d shows images of the PAC supramolecular polymer prepared with DMSO-0% and DMSO-22% at -25 ℃ and − 20 ℃ torsional states, respectively. The results demonstrate that the supramolecular polymer prepared using a H 2 O/DMSO binary solvent system maintains tensile bending performance at -20 ℃, whereas the PAC supramolecular polymer prepared with H 2 O solvent ruptures at -20 ℃. As shown in Fig. 3 e, the H 2 O-solvent-based PAC supramolecular polymer exhibits significant exothermic/endothermic peaks during cooling/heating processes from − 60 ℃ to 40 ℃, attributed to water crystallization/ice melting. In contrast, the DMSO-22% binary solvent system shows no significant thermal flow changes. This is due to hydrogen bonding interactions between DMSO and H 2 O, which tightly bind water molecules within the PAC supramolecular polymer network. This interaction significantly reduces free water content, preventing excessive ice crystal formation and growth at low temperatures. Consequently, the PAC supramolecular polymer maintains structural integrity through reduced ice-induced mechanical damage, preserving its network architecture and ensuring stable performance[ 41 ]. As shown in Fig. 3 f, the DMSO-22% PAC supramolecular polymer maintained its original morphology after 11 days of room-temperature storage, while the DMSO-0% PAC supramolecular polymer exhibited significant volume reduction. Fig. S6 reveals that the PAC supramolecular polymer experienced rapid dehydration at room temperature, with its water retention rate declining sharply. In contrast, the supramolecular polymer demonstrated excellent water-holding capacity, retaining 82% moisture content after 11 days. This stability is primarily attributed to the strong hydrogen bonds formed between DMSO and H 2 O. These hydrogen bonds effectively reduce water vapor pressure, which prevents water molecules from diffusing into the external environment. Consequently, the PAC supramolecular polymer's internal moisture content remains relatively stable, ensuring consistent physicochemical properties and enabling sustained functionality[ 42 ]. 3.4 In vitro blood compatibility and antibacterial properties of PAC supramolecular polymer. Figure 4 a shows the hemolytic performance of PAC supramolecular polymer. The H 2 O positive control demonstrates hemolysis, with the centrifuged supernatant appearing red and opaque. In contrast, the PBS negative control shows no hemolysis, yielding a clear supernatant after centrifugation. A hemolysis rate below 5% indicates excellent blood compatibility. When comparing the negative and positive controls, PAC supramolecular polymers containing 0-2.5% CS or 5–22% DMSO produced clear supernatants following blood culture centrifugation, demonstrating good blood compatibility. However, the DMSO-0% PAC supramolecular polymer showed opacity due to sodium hydroxide substitution for DMSO, indicating poor blood compatibility. As shown in Fig. 4 b, both 0-2.5% CS and 5–22% DMSO PAC supramolecular polymers exhibited hemolytic rates below 5%, showing no hemolysis[ 43 ]. Figure 4 c shows the coagulation performance of PAC supramolecular polymers. Compared with the blank control group, all other PAC supramolecular polymers (except CS-0% and DMSO-0%) began clotting within 2–4 minutes, while CS-0% took 6 minutes and DMSO-0% required 8 minutes[ 44 ]. Figure 4 d presents the relative hemoglobin levels (RHA) of PAC supramolecular polymer with varying CS and DMSO concentrations. The RHA values for CS-0.5%, CS-1.5%, CS-2.5%, DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers started decreasing at 4 minutes, whereas CS-0% and DMSO-0% maintained high RHA levels until 4 minutes. Notably, CS-0% PAC supramolecular polymer showed declining RHA from 6 minutes onward. These results demonstrate that CS significantly enhances PAC supramolecular polymer coagulation capacity, with CS-0.5%, CS-1.5%, CS-2.5%, DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers exhibiting excellent clotting performance. In contrast, DMSO-0% PAC supramolecular polymer, containing sodium hydroxide, caused blood damage and failed to coagulate effectively. Figure 5 a shows the inhibition zone images and diameters of PAC supramolecular polymer with varying CS concentrations on E.coli and S.aureus culture media. The results demonstrate that the PAC supramolecular polymer effectively inhibits both bacteria, indicating its antibacterial efficacy[ 45 ]. As shown in Fig. 5 b, the inhibition zones expand with increasing CS concentration. The 2.5% CS PAC supramolecular polymer exhibits the strongest inhibitory capacity against both pathogens, attributed to CS's potent antibacterial properties that enhance the PAC supramolecular polymer's antimicrobial performance. Figure 5 c shows the inhibition zone images and diameters of the PAC supramolecular polymer containing DMSO on E.coli and S.aureus culture media. The results demonstrate that the DMSO-containing PAC supramolecular polymer effectively inhibits both bacteria, indicating its antibacterial efficacy. As shown in Fig. 5 d, the DMSO-0% PAC supramolecular polymer exhibits the largest inhibition zone diameter due to sodium hydroxide's strong alkaline properties that inhibit bacterial growth. For the 5%, 12%, and 22% DMSO concentrations, the inhibition zones increase proportionally with DMSO content, confirming the PAC supramolecular polymer's bacteriostatic capability and showing that higher DMSO levels enhance its antimicrobial effectiveness. 3.5 Evaluation of 3D printing performance of PAC supramolecular polymer. By maintaining a fixed DMSO concentration of 22%, the CS content was adjusted to achieve CS-0.5%, CS-1.5%, and CS-2.5% as the PAC supramolecular polymer ink for printing. Then the 3D printing performance of supramolecular polymers was judged by diameter deviation rate, area fidelity and height fidelity[ 46 , 47 ]. As shown in Fig. 6 a and Fig. S7 , the M CS−0.5% exhibits the best fluidity, producing continuous and uniform extruded filaments. M CS−1.5% followed closely, while the M CS−2.5% printing ink resulted in PAC supramolecular polymer filaments with uneven thickness. A lower direct deviation rate indicates that the PAC supramolecular polymer filament diameter more closely matches the nozzle diameter, demonstrating superior printability and precision. As illustrated in Fig. 6 b, the M CS−0.5% printing ink demonstrated the smallest diameter deviation rate, exhibiting the best printability and filament precision. As shown in Fig. 6 c, the intersections between PAC supramolecular polymer filaments in single layer grids produced by M CS−0.5% , M CS−1.5%, and M CS−2.5% printing inks exhibit significant accumulation, which affects print quality. Notably, the M CS−0.5% ink demonstrates optimal accumulation patterns, printed product with higher precision. In contrast, the M CS−1.5% and M CS−2.5% inks result in noticeable accumulation at filament intersections. The area fidelity closely approximates 100%, indicating that the M CS−0.5% ink produces PAC supramolecular polymer grids with the closest theoretical area match. Figure 6 d further confirms this, showing the M CS−0.5% ink achieves the highest area fidelity with the most accurate alignment to the theoretical grid dimensions. As shown in Fig. 6 e, the morphology of the double layer grids printed with M CS−0.5% , M CS−1.5% , and M CS−2.5% inks demonstrates differences. The M CS−2.5% ink produced well-connected upper and lower layers with strong support from the base layer, showing minimal filament collapse. In contrast, both M CS−0.5% and M CS−1.5% ink resulted in grids with noticeable filament collapse and poor adhesion between layers, indicating weaker support from the base layer. The height fidelity closely approached 100%, with the M CS−2.5% ink printing the most structurally stable dual-layer grid as evidenced by Fig. 6 f. To evaluate the reproducibility of the printing ink, a heated solution of the cured M CS−0.5% PAC supramolecular polymer was used for secondary printing. Figure 6 g shows, The PAC supramolecular polymer filaments in the second print exhibit uniform thickness, with the single layer grid maintaining regular patterns. While the lower layer of the double layer grid demonstrates good adhesion to the upper layer, the lower layer shows inadequate support, resulting in filament discontinuities and accumulation. The reproducibility of the printing ink was assessed through three metrics: diameter deviation rate, area fidelity, and height fidelity. As shown in Fig. 6 h, compared to the initial print, the diameter deviation rate and area fidelity remained relatively stable, while the high fidelity showed a slight decrease. These findings collectively confirm that the PAC supramolecular polymer printing ink demonstrates reliable reproducibility. 3.6 Conductive properties and fatigue resistance of PAC conductive supramolecular polymer By gradually increasing the voltage, we observed the brightness changes of the LED indicator[ 48 ]. As shown in Fig. 7 a, when a 2V voltage was applied, the LED indicator emitted a faint light, indicating low current flow through the conductive supramolecular polymer and weak electrical signal transmission in the circuit. With the voltage being increased at a certain gradient, the LED's light became visibly brighter, demonstrating the continuous increase in current flow. This phenomenon primarily stems from the uniformly distributed carbon nanotubes (CNTs) within the PAC conductive supramolecular polymer system, which establish efficient conductive pathways. Even at lower voltages, these CNTs effectively transport electrons to power the LED, proving the PAC supramolecular polymer's excellent conductivity. Figure 7 b-e shows the 10-cycle loading-unloading curves of PAC conductive supramolecular polymer under 10%, 20%, 30%, and 40% tensile deformation. The results indicate that after the initial loading-unloading cycle, partial breakage of coordination bonds between silver ions and CS molecular chains occurred within the material. Additionally, stress-induced dissociation at the TA crosslinking point caused significant softening and weakening of its internal structure, leading to energy dissipation that prevented immediate recovery to the initial state. However, during subsequent nine cyclic loading tests at 10% and 20% deformation, the PAC conductive supramolecular polymer maintained consistent tensile strength and hysteresis loops compared to the initial state. This stability is attributed to the self-healing mechanism of the dynamic crosslinking network: broken silver-amino coordination bonds rapidly reformed through silver ion migration during unloading, while disulfide bonds between TA molecules underwent thiol-disulfide exchange reactions following stress release, enabling reconstruction of the three-dimensional network topology[ 49 ]. For PAC conductive supramolecular polymer at 30% and 40% deformation, the subsequent nine cyclic loading tests revealed differences in tensile strength and hysteresis loops compared to the first cycle. Although maintaining cyclic stability, mechanical properties exhibited gradual degradation. The results show that under the tensile deformation of 10%~20%, the material has excellent anti-fatigue performance and recovery performance, and can maintain relatively stable mechanical performance after multiple stress cycles. 3.7 Strain sensing of PAC conductive supramolecular polymer By connecting conductive supramolecular polymer to a universal testing machine, a real-time monitoring system for resistance changes was established. The conductive supramolecular polymer was subjected to tensile and cyclic tensile strain tests using the universal testing machine. The resistance variations during these processes were precisely measured with a universal meter, enabling determination of the PAC supramolecular polymer's strain sensing capability, strain sensitivity, and stability[ 50 , 51 ]. In the field of strain sensor material research, strain sensing performance serves as a key indicator for evaluating material suitability in this domain. For PAC supramolecular polymer materials, excellent strain sensing capability means they can accurately detect external stress changes and convert these variations into detectable electrical signals, which is crucial for achieving high-precision strain monitoring. As shown in Fig. 8 a, when subjected to 10%, 20%, 30%, and 40% deformation, the conductive supramolecular polymer underwent three repeated tensile cycles, maintaining consistent repeatability in resistance change rates. The results demonstrate that under identical strain conditions, this conductive supramolecular polymer consistently outputs stable resistance variation signals with reliable stability and repeatability. Moreover, significant differences in resistance change rates were observed across varying deformation levels, showing regular patterns as deformation increased progressively. This indicates that PAC conductive supramolecular polymer exhibits high sensitivity and reliable repeatability, with distinct response variations under different strain states. These characteristics enable effective differentiation of deformation levels, providing a solid performance foundation for applications in smart sensing and wearable devices. In the performance evaluation system of strain sensors, strain sensitivity serves as a key parameter for assessing material quality. This characteristic can be characterized by GF and response time, reflecting the practical applicability of conductive supramolecular polymer materials in strain sensor applications. The GF value represents the slope of the strain-resistance change rate curve, indicating the material's sensitivity to electrical resistance variations under strain. For instance, a higher GF value signifies more pronounced resistance changes under equivalent strain conditions, enabling easier detection and sensing. Figure 8 b shows the resistance variation of PAC conductive supramolecular polymer under 0–40% strain. Within the 10%-40% strain range, the strain rate of resistance change gradually increases with strain magnitude. Although the GF exhibits a slight downward trend with strain progression, the decrease remains relatively minor. Notably, GF maintains a high value even at 40% strain. These results conclusively demonstrate that PAC conductive supramolecular polymer retains sensitive resistance response capability under significant strain conditions, exhibiting excellent strain sensing performance. Figure 8 c illustrates the response time and recovery time of PAC conductive supramolecular polymer after being stretched to 10% strain, held for 1 second, and then released to return to its original 0% deformation state. As shown in the figure, the PAC conductive supramolecular polymer demonstrates a response time of 0.86 seconds and a recovery time of 0.83 seconds. Compared to similar commercial PAC supramolecular polymer materials, these values are notably lower. This rapid and precise reaction capability strongly reflects the excellent strain sensitivity of the PAC conductive supramolecular polymer. The strain sensing stability of PAC supramolecular polymer serves as a critical indicator for the durability and repeatability of PAC supramolecular polymer strain sensors, determining their long-term operational reliability under frequent stress. This performance directly impacts both sensor lifespan and the accuracy of monitoring data. Figure 8 d demonstrates the resistance change rate of PAC conductive supramolecular polymer during 200 tensile cycles at a constant 40% strain. The results show that as the number of cycles increased from 1 to 200, the PAC supramolecular polymer maintained stable fluctuations within a defined range. This consistent response highlights its exceptional stability, enabling reliable conversion of strain signals into stable resistance variations even under prolonged, repetitive strain applications. Furthermore, the consistent resistance changes across multiple cycles demonstrate outstanding reproducibility – applying identical 40% strain consistently yields nearly identical responses regardless of cycle count. These findings collectively confirm that PAC conductive supramolecular polymer exhibits superior long-term performance as a strain sensor. 3.8 Human detection performance of PAC conductive supramolecular polymer The PAC conductive supramolecular polymer was immobilized on human joints with frequent and representative movements such as fingers, wrists, elbows, and knees. These joints exhibit distinct motion patterns and ranges of motion, enabling comprehensive simulation of various daily activities. During human movement, the stretching and strain changes in joints and muscles drive the PAC supramolecular polymer. By connecting the PAC supramolecular polymer to a Source Measure Unit and observing resistance variations during motion[ 52 – 54 ], Fig. 9 demonstrates that as finger, wrist, knee, and elbow flexion occurs, the resistance change rate of the PAC conductive supramolecular polymer shows significant acceleration. The PAC supramolecular polymer exhibits rapid response speed, generating corresponding electrical signal changes almost instantaneously during joint movement, indicating its excellent real-time sensing capability. Furthermore, when performing repeated joint movements, the PAC supramolecular polymer consistently outputs stable and nearly identical resistance changes, demonstrating high stability and repeatability. Additionally, the resistance change rates across different joint motion ranges show clear variations, accurately reflecting each joint's movement status and amplitude, achieving precise motion perception. In summary, the PAC conductive supramolecular polymer demonstrates superior sensing performance and practical applicability for human joint motion monitoring. 4. Conclusion In summary, a PAC supramolecular polymer featuring hydrogen bonds and dynamic metal coordination bonds has been developed for 3D printing and strain sensing applications. The dynamic metal coordination bonds and hydrogen bonds endow the polymer with rapid self-healing capabilities and temperature-responsive behavior. This supramolecular polymer demonstrates excellent mechanical properties, blood compatibility, and significant inhibition of Escherichia coli and Staphylococcus aureus. In 3D printing applications, ink containing 0.5% CS exhibits optimal filament precision and single-layer grid area fidelity. The ink with 2.5% CS achieves the highest stability in double-layer grid structures, while the ink itself is reusable. These characteristics make the supramolecular polymer a promising candidate for biological scaffolds. For strain sensing applications, the addition of carbon nanotubes (CNTs) confers conductivity to the polymer. The conductive supramolecular polymer demonstrates superior fatigue resistance, strain sensing performance, sensitivity, and cyclic stability. Practical human motion monitoring has confirmed its effectiveness and reliability as a strain sensor. Declarations Supplementary Information: The online version contains supplementary material available at Acknowledgements: We are grateful for the financial support from the Natural Science Foundation of Heilongjiang Province of China (No. ZL2024E016), the Undergraduate Training Programs for Innovations by NEFU (No. 202510225580) and 2025 Provincial Higher Education Excellence Initiative: Funding for Joint Graduate Training Base Development through Industry-Education Integration. Authors contributions: S. L. and M. J. wrote the main manuscript text and prepared all figures. J. W. and J. L assisted in completing the photographs of samples in the manuscript. X. K., P. H. and J. D. discussed the results and proofread the manuscript. D. Z. conceptualized this review, supervised the writing process, edited and reviewed the manuscript. Data availability: The data that support the findings of this study are available from the corresponding author upon reasonable request. Funding : This work was supported by the Natural Science Foundation of Heilongjiang Province of China (No. ZL2024E016), the Undergraduate Training Programs for Innovations by NEFU (No. 202510225580) and 2025 Provincial Higher Education Excellence Initiative: Funding for Joint Graduate Training Base Development through Industry-Education Integration. Conflict of interest: The authors declare that they have no conflict of interest. Open Access: This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8804107","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":595183109,"identity":"7a616cdd-3649-4e8b-9efa-85049520f679","order_by":0,"name":"Shengqiang Liao","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Shengqiang","middleName":"","lastName":"Liao","suffix":""},{"id":595183116,"identity":"595f5a69-b548-4b5e-a512-bc169349ffa8","order_by":1,"name":"Miaomiao Jia","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Miaomiao","middleName":"","lastName":"Jia","suffix":""},{"id":595183121,"identity":"2c034da4-0751-44c8-9082-26f9c342f822","order_by":2,"name":"Juncheng Wang","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Juncheng","middleName":"","lastName":"Wang","suffix":""},{"id":595183123,"identity":"541a8d85-3e1f-4e98-ba32-fed6cfd63638","order_by":3,"name":"Jiawen Liu","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Jiawen","middleName":"","lastName":"Liu","suffix":""},{"id":595183124,"identity":"1b233685-3dcf-473e-b096-471105faa1e7","order_by":4,"name":"Xianzhi Kong","email":"","orcid":"","institution":"Heilongjiang Academy of Sciences","correspondingAuthor":false,"prefix":"","firstName":"Xianzhi","middleName":"","lastName":"Kong","suffix":""},{"id":595183125,"identity":"17326975-bd97-40da-9577-40916a65bba2","order_by":5,"name":"Pengfei Huo","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Pengfei","middleName":"","lastName":"Huo","suffix":""},{"id":595183126,"identity":"b99d4c3d-1390-45eb-bdf8-4697a20e477c","order_by":6,"name":"Jidong Dong","email":"","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":false,"prefix":"","firstName":"Jidong","middleName":"","lastName":"Dong","suffix":""},{"id":595183128,"identity":"4b4f989d-7a01-4bb7-8f84-67caa965c9c2","order_by":7,"name":"Dawei Zhang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA+ElEQVRIiWNgGAWjYDACCRDBBsTMzAcYGGxAvASitbABlaaRpIWBx4A4LfKzm589/FJml9jPzvPtwYeEwwz87DkGDD934NbCOOeYubHMueTEmc282w1nALVI9rwxYOw9g1sLs0SCmbRkG3PuhsO826R5fxxmMLiRY8DM2IZbC5tE+jeglvrc/Yd5nkn/AdpiT0gLj0SOmeTHtsO5G5h52KQZgFoMJAhokZDIKZNmOHe8fsZhNjPJnoR0HokzzwoO9uLRIj8jfZvkj7JqY/7+w88kfiRYy/G3J2988BOPFnAQ8CC7FEQcwK8BGNA/CKkYBaNgFIyCkQ0ARHFLxPqMIxcAAAAASUVORK5CYII=","orcid":"","institution":"Northeast Forestry University","correspondingAuthor":true,"prefix":"","firstName":"Dawei","middleName":"","lastName":"Zhang","suffix":""}],"badges":[],"createdAt":"2026-02-06 07:53:19","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8804107/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8804107/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":103299055,"identity":"2f5e2c32-e7bf-4116-b10f-7b9e63002efa","added_by":"auto","created_at":"2026-02-24 07:52:38","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":733854,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea\u003c/strong\u003e Synthesis, temperature-sensitive properties of PAC supramolecular polymer. \u003cstrong\u003eb\u003c/strong\u003e Non-covalent interactions of PAC supramolecular polymer.\u003c/p\u003e","description":"","filename":"image1.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/35a688237a22281590dd184c.png"},{"id":103505885,"identity":"60c19bc4-cca3-4c4c-8900-367773728ada","added_by":"auto","created_at":"2026-02-26 13:33:22","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":263276,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea\u003c/strong\u003eTensile strength, elongation at break, and tensile modulus of PAC supramolecular polymer with CS content. \u003cstrong\u003eb \u003c/strong\u003eTensile strength, elongation at break, and tensile modulus of PAC supramolecular polymer with DMSO content. \u003cstrong\u003ec\u003c/strong\u003e Compression stress-strain curve of PAC supramolecular polymer with CS content; \u003cstrong\u003ed \u003c/strong\u003eCompression stress-strain curve of PAC supramolecular polymer with DMSO content.\u003c/p\u003e","description":"","filename":"image2.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/6287a8ad536f5dc14d4dcd55.png"},{"id":103506984,"identity":"414f98b0-3505-4866-8440-f9fb8606b2ac","added_by":"auto","created_at":"2026-02-26 13:40:08","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":718177,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea \u003c/strong\u003ePhysical photos of PAC supramolecular polymer adhesion to various materials. \u003cstrong\u003eb\u003c/strong\u003e Adhesion strength of PAC supramolecular polymer under tensile loading mode. \u003cstrong\u003ec \u003c/strong\u003eSelf-healing process diagram of PAC supramolecular polymer. \u003cstrong\u003ed \u003c/strong\u003eTwisting photos of PAC supramolecular polymer with 0% DMSO and 22% DMSO at 25 ℃ and-20 ℃. \u003cstrong\u003ee\u003c/strong\u003e Thermal flow curves during cooling and heating processes. \u003cstrong\u003ef \u003c/strong\u003ePhysical photos of PAC supramolecular polymer with 0% DMSO and 22% DMSO were stored at room temperature for 11 days.\u003c/p\u003e","description":"","filename":"image3.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/47a0642cc458be0fb092ec2b.png"},{"id":103299064,"identity":"9cff58b6-96e7-4b8d-954a-188e1560596a","added_by":"auto","created_at":"2026-02-24 07:52:38","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":1293202,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea\u003c/strong\u003eHemolytic physical image of PAC supramolecular polymer. \u003cstrong\u003eb\u003c/strong\u003e Hemolysis rate of PAC supramolecular polymer. \u003cstrong\u003ec \u003c/strong\u003eCoagulation physical image of PAC supramolecular polymer. \u003cstrong\u003ed \u003c/strong\u003eRelative hemoglobin percentage of PAC supramolecular polymer.\u003c/p\u003e","description":"","filename":"image4.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/4b34ad743f00559f497565f1.png"},{"id":103506713,"identity":"c22a8483-607f-46f8-bd98-7efc54d4de5e","added_by":"auto","created_at":"2026-02-26 13:39:11","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":777744,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea\u003c/strong\u003eBacterial inhibition zones of PAC supramolecular polymer containing CS (E.coli and S.aureus). \u003cstrong\u003eb \u003c/strong\u003eDiameter of inhibition zones. \u003cstrong\u003ec \u003c/strong\u003eBacterial inhibition zones of PAC supramolecular polymer containing DMSO (E.coli and S.aureus).\u003cstrong\u003e d\u003c/strong\u003e Diameter of inhibition zones.\u003c/p\u003e","description":"","filename":"image5.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/ea53c7e1d659e283960f0542.png"},{"id":103299059,"identity":"125609a5-abd2-484b-b4bb-34d5a473ee4f","added_by":"auto","created_at":"2026-02-24 07:52:38","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":1592441,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea\u003c/strong\u003e Filament morphology of M\u003csub\u003eCS-0.5%\u003c/sub\u003e, M\u003csub\u003eCS-1.5%\u003c/sub\u003e, and M\u003csub\u003eCS-2.5%\u003c/sub\u003e. \u003cstrong\u003eb\u003c/strong\u003e Diameter deviation rates of M\u003csub\u003eCS-0.5%\u003c/sub\u003e, M\u003csub\u003eCS-1.5%\u003c/sub\u003e, and M\u003csub\u003eCS-2.5%\u003c/sub\u003e. \u003cstrong\u003ec\u003c/strong\u003e Single layer grid morphology of M\u003csub\u003eCS-0.5%\u003c/sub\u003e, M\u003csub\u003eCS-1.5%\u003c/sub\u003e, and M\u003csub\u003eCS-2.5%\u003c/sub\u003e. \u003cstrong\u003ed\u003c/strong\u003e Area fidelity of M\u003csub\u003eCS-0.5%\u003c/sub\u003e, M\u003csub\u003eCS-1.5%\u003c/sub\u003e, and M\u003csub\u003eCS-2.5%\u003c/sub\u003e.\u003cstrong\u003e e \u003c/strong\u003eDouble layer grid morphology of M\u003csub\u003eCS-0.5%\u003c/sub\u003e, M\u003csub\u003eCS-1.5%\u003c/sub\u003e, and M\u003csub\u003eCS-2.5%\u003c/sub\u003e. \u003cstrong\u003ef\u003c/strong\u003e High fidelity of M\u003csub\u003eCS-0.5%\u003c/sub\u003e, M\u003csub\u003eCS-1.5%\u003c/sub\u003e, and M\u003csub\u003eCS-2.5%\u003c/sub\u003e. \u003cstrong\u003eg\u003c/strong\u003e Filament morphology, single layer grid morphology and double layer grid morphology of secondary printing. \u003cstrong\u003eh\u003c/strong\u003e Diameter deviation rate, area fidelity and high fidelity of secondary printing.\u003c/p\u003e","description":"","filename":"image6.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/1872cca9a565f014a93867fd.png"},{"id":103299057,"identity":"976360aa-317d-4671-b888-d3c6bb244cf9","added_by":"auto","created_at":"2026-02-24 07:52:38","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":928863,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea\u003c/strong\u003eClosed circuit diagram of PAC conductive supramolecular polymer; Loading-unloading curves of PAC conductive supramolecular polymer at \u003cstrong\u003eb \u003c/strong\u003e10%, \u003cstrong\u003ec \u003c/strong\u003e20%, \u003cstrong\u003ed \u003c/strong\u003e30%, \u003cstrong\u003ee\u003c/strong\u003e40% tensile deformation.\u003c/p\u003e","description":"","filename":"image7.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/939bbf4b020a9140b277460a.png"},{"id":103505976,"identity":"5bf0fdc8-21a0-47dd-b498-6dfadf081d7b","added_by":"auto","created_at":"2026-02-26 13:33:42","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":223652,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003ea\u003c/strong\u003eResistance variation of PAC conductive supramolecular polymerduring tensile cycle at 10%, 20%, 30% and 40% deformation; \u003cstrong\u003eb\u003c/strong\u003e Rate of change in resistance for PAC conductive supramolecular polymeracross the 10%-40% strain range; \u003cstrong\u003ec \u003c/strong\u003eResponse time and recovery time of PAC conductive supramolecular polymer; \u003cstrong\u003ed\u003c/strong\u003eContinuous 200-tensile cycles under 40% strain on PAC conductive supramolecular polymer.\u003c/p\u003e","description":"","filename":"image8.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/ce48df2b4897983ec75994be.png"},{"id":103299062,"identity":"756f0389-78c6-4bff-a00a-f22e53d55b84","added_by":"auto","created_at":"2026-02-24 07:52:38","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":457445,"visible":true,"origin":"","legend":"\u003cp\u003eDetection of human joints by PAC conductive supramolecular polymer: \u003cstrong\u003ea \u003c/strong\u003efinger; \u003cstrong\u003eb\u003c/strong\u003e wrist; \u003cstrong\u003ec\u003c/strong\u003e knee; \u003cstrong\u003ed\u003c/strong\u003e elbow.\u003c/p\u003e","description":"","filename":"image9.png","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/3604a5c70091d08f5ec2b41b.png"},{"id":103509942,"identity":"1799aa1f-d626-4184-84dd-1c23983abc75","added_by":"auto","created_at":"2026-02-26 14:02:16","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":8540805,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/d772291c-c856-4cf4-84fe-70674f120c5c.pdf"},{"id":103506726,"identity":"873d3ddf-8adc-4e08-a4c1-1a84bfc4b295","added_by":"auto","created_at":"2026-02-26 13:39:14","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2222024,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryMaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/87e6f37c7070a87493afb0b0.docx"},{"id":103299061,"identity":"89eecc5f-7dd1-4eb4-8e1d-b9dc6b35abaa","added_by":"auto","created_at":"2026-02-24 07:52:38","extension":"jpeg","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":303684,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eGraphical abstract for online article\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"image10.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8804107/v1/1f3868dad6b8116538583c9b.jpeg"}],"financialInterests":"No competing interests reported.","formattedTitle":"A temperature-sensitive, reusable PTA-AgNO 3 -CS supramolecular polymer for 3D printing and strain sensing","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eSupramolecular polymers are constructed through non-covalent interactions (including hydrogen bonds, metal coordination, π-π stacking, and host-guest interactions) between one or more molecular components. These reversible non-covalent bonds not only enable supramolecular polymers to undergo reversible structural, morphological, and performance switching when exposed to external stimuli, but also provide a flexible and robust platform for developing functional supramolecular materials and smart supramolecular devices[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Traditional polymers, primarily composed of covalent bonds, exhibit static structural stability and poor reversibility, making them difficult to dissociate through simple methods. In contrast, supramolecular polymers demonstrate distinct advantages such as self-healing properties, reusability, and intelligent responses to various biological stimuli. These characteristics significantly broaden the application scope of supramolecular polymers[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eSupramolecular polymers, with their dynamic and reversible non-covalent crosslinking properties (such as hydrogen bonds, ionic bonds, and coordination bonds), provide customized structural designs, dynamic functional responses, and eco-friendly sustainable solutions for 3D printing[\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. These materials also exhibit critical properties including high tensile strength, self-healing capabilities, environmental stability, wide strain detection range, and high sensitivity, perfectly meeting the demands of strain sensors for mechanical adaptability, signal reliability, and long-term durability[\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. 3D printing technology, also known as additive manufacturing (AM), involves designing models using computer-aided design (CAD) software and printing three-dimensional structures through predefined programs in 3D printers[\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. The extrusion printing method works by pushing ink through a piston, which continuously flows in filament form from the nozzle and deposits onto the printing platform, completing the printed object. This printing method is fast and cost-effective[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. Strain sensors will deform when stimulated by external forces, and then convert mechanical deformation into electrical signals, which have great application prospects in wearable devices[\u003cspan additionalcitationids=\"CR13\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e], electronic skin[\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], intelligent robots[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e], medical care monitoring[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e], etc. Supramolecular polymers, with their excellent flexibility, tensile strength, biocompatibility, and mechanical properties, are considered promising substrates for designing strain sensors[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. To enhance their conductivity, conductive materials such as metals and carbon-based materials (carbon black, carbon nanotubes, graphene) can be incorporated. Among these, carbon nanotubes (CNTs) stand out in the strain sensor field due to their high electrical conductivity, exceptional flexibility, low density, and large aspect ratio[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e].\u003c/p\u003e \u003cp\u003ePoly thioctic acid (PTA) is a class of high molecular weight polymers synthesized from natural small-molecule thioctic acid (TA) through ring-opening polymerization under light and heat stimulation[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. The carboxyl groups in PTA can form hydrogen bonds with adjacent molecules, endowing the derived polymers with remarkable dynamic properties such as reprocess ability and self-repair capability. Moreover, the presence of carboxyl groups enables PTA to readily undergo modification reactions with various chemical units, making it possible to introduce multiple functional groups into TA-derived polymers[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. Chitosan (CS), a natural polymer typically synthesized by removing acetyl groups from chitin through alkaline or enzymatic hydrolysis, ranks as the second most abundant biomolecule on Earth. Its backbone contains amino and hydroxyl groups, exhibiting exceptional properties including biodegradability, biocompatibility, non-toxicity, bioadhesion, and antibacterial activity[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e, \u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. Silver nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e) not only possesses the physical and chemical characteristics of silver but also forms metal coordination bonds, demonstrating broader antibacterial activity and superior biocompatibility[\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. Dimethyl sulfoxide (DMSO), often called the \"universal solvent,\" serves as a cryoprotectant for bone marrow and blood cell cryopreservation due to its anti-inflammatory, analgesic, diuretic, and sedative effects[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThis study utilizes DMSO as the primary solvent and TA, AgNO\u003csub\u003e3\u003c/sub\u003e, and CS as key raw materials to develop a PTA-AgNO\u003csub\u003e3\u003c/sub\u003e-CS (PAC) supramolecular polymer containing hydrogen bonds and dynamic metal coordination bonds. The non-covalent interactions in PAC enable self-healing properties, reprocessing ability, and temperature sensitivity. PAC also exhibits excellent mechanical strength, freeze resistance, and moisture retention. It demonstrates no significant hemolysis in red blood cells, promotes blood clotting, and shows remarkable antibacterial activity. For applications, PAC can be used for 3D printing and repeated printing, meeting the customized production needs of personalized tissue engineering scaffolds. Incorporating CNTs into PAC enhances its conductivity. The conductive PAC supramolecular polymer demonstrates outstanding fatigue resistance, strain sensing performance, sensitivity, and cyclic stability. Practical human motion monitoring has validated its effectiveness and reliability as a strain sensor.\u003c/p\u003e"},{"header":"2. Experimental section","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n\u003ch2\u003e2.1 Materials\u003c/h2\u003e\n\u003cp\u003eThioctic acid (TA, 99%) and calcium chloride (CaCl\u003csub\u003e2\u003c/sub\u003e, 99%) were purchased from China Shanghai Aladdin Reagent Co., Ltd. Dimethyl sulfoxide (DMSO, 99%) was purchased from China Shanghai MacLin Biochemical Technology Co., Ltd. Silver nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e, 99.8%) and acetic acid (HAC, 99%) were purchased from China Xilong Technology Co., Ltd. Chitosan (CS, deacetylation degree: 91%, viscosity: 100 mPa s) was purchased from Zhejiang Jinke Pharmaceutical Co., Ltd. Ethyl acetate (EAC, 99.5%) and sodium hydroxide (NaOH, 96%) were purchased from China Tianjin Kemiao Chemical Reagents Co., Ltd. Dry powder phosphate buffer (PBS) was purchased from China Beijing Lanjieke Technology Co., Ltd. Carbon nanotubes (CNTs, 95%, multilayer, diameter: 8\u0026ndash;15 nm, inner diameter: 3-5nm, length: 10\u0026ndash;50\u0026micro;m) were purchased from Jiangsu Xianfeng Nano Material Technology Co., Ltd. Sodium citrate anticoagulant sheep blood was purchased from China Shanghai Yuchun Biotechnology Co., Ltd. Escherichia coli and Staphylococcus aureus were purchased from China Guangdong Microbial Strain Preservation Center.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\n\u003ch2\u003e2.2 Synthesis of PAC supramolecular polymer\u003c/h2\u003e\n\u003cp\u003eThe preparation process of PAC supramolecular polymer is shown in \u003cstrong\u003eFig. \u003cspan class=\"InternalRef\"\u003eS1\u003c/span\u003e\u003c/strong\u003e. Step 1: Add 5 g of TA to DMSO and place it in a water bath at 70 ℃ for 20\u0026ndash;40 min under stirring. Cool to room temperature to obtain the PTA solution. Step 2: Dissolve 0.017 g of AgNO\u003csub\u003e3\u003c/sub\u003e in 1 ml of DMSO by stirring until completely dissolved to prepare the AgNO\u003csub\u003e3\u003c/sub\u003e solution. Step 3: Disperse CS powder uniformly in 1.9 ml of H\u003csub\u003e2\u003c/sub\u003eO using magnetic stirring, then add glacial acetic acid and mix thoroughly to form the CS acetate aqueous solution. Step 4: Add the AgNO\u003csub\u003e3\u003c/sub\u003e solution to the PTA solution and stir magnetically for 15\u0026ndash;30 min to achieve the PTA-NO\u003csub\u003e3\u003c/sub\u003e reaction mixture. Step 5: Drop the CS acetate aqueous solution into the PTA-NO\u003csub\u003e3\u003c/sub\u003e reaction mixture and stir vigorously until uniform. The resulting PAC supramolecular polymer printing ink is injected into a glass groove and left undisturbed for 8\u0026ndash;12 hours to form the PAC supramolecular polymer. When the DMSO content was fixed at 22%, the CS-0%, CS-0.5%, CS-1.5%, and CS-2.5% PAC supramolecular polymers were prepared by adjusting the CS content. When the CS content was fixed at 0.5%, the DMSO-0%, DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers were obtained by modifying the DMSO content. Notably, the DMSO-0% PAC supramolecular polymer was replaced with a NaOH solution to dissolve TA.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\n\u003ch2\u003e2.3 3D printing of PAC supramolecular polymer\u003c/h2\u003e\n\u003cdiv id=\"Sec6\" class=\"Section3\"\u003e\n\u003ch2\u003e2.3.1 3D printing performance test of PAC supramolecular polymer\u003c/h2\u003e\n\u003cp\u003eM\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e, M\u003csub\u003eCS\u0026minus;1.5%\u003c/sub\u003e and M\u003csub\u003eCS\u0026minus;2.5%\u003c/sub\u003e printing inks were added to the barrel of an extrusion 3D printer to print long strips and grid printed parts. The effects of CS content on the printing performance of printing inks were discussed in three aspects: diameter deviation rate, area fidelity and high fidelity. The printing parameters are as follows: print nozzle 0.3 mm, extrusion pressure 20 mN, and printing speed 850 mm/min.\u003c/p\u003e\n\u003cp\u003eDiameter deviation rate is calculated according to Eq.\u0026nbsp;(\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e):\u003c/p\u003e\n\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\n\u003cdiv id=\"FileID_Equ1\" class=\"mathdisplay\"\u003e$$\\:\\text{∆D}\\text{=}\\frac{\\left(\\text{D}\\text{-}{\\text{D}}_{\\text{0}}\\right)}{{\\text{D}}_{\\text{0}}}\\text{\u0026times;100%}$$\u003c/div\u003e\n\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eWhere: \u003cem\u003e∆D\u003c/em\u003e is the diameter deviation rate of the printing filament, \u003cem\u003eD\u003c/em\u003e is the diameter of the actual printing filament (mm), and \u003cem\u003eD\u003c/em\u003e\u003csub\u003e\u003cem\u003e0\u003c/em\u003e\u003c/sub\u003e is the diameter of the printing needle (mm).\u003c/p\u003e\n\u003cp\u003eArea fidelity is calculated according to Eq.\u0026nbsp;(\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e):\u003c/p\u003e\n\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\n\u003cdiv id=\"FileID_Equ2\" class=\"mathdisplay\"\u003e$$\\:{\\text{F}}_{\\text{g}}\\text{=}\\frac{{\\text{S}}_{\\text{a}}}{{\\text{S}}_{\\text{t}}}\\text{\u0026times;100%}$$\u003c/div\u003e\n\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eWhere: \u003cem\u003eF\u003c/em\u003e\u003csub\u003e\u003cem\u003eg\u003c/em\u003e\u003c/sub\u003e is the area fidelity parameter of the grid, \u003cem\u003eS\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e is the actual grid area (mm\u003csup\u003e2\u003c/sup\u003e), \u003cem\u003eS\u003c/em\u003e\u003csub\u003e\u003cem\u003et\u003c/em\u003e\u003c/sub\u003e is the theoretical grid area (mm\u003csup\u003e2\u003c/sup\u003e).\u003c/p\u003e\n\u003cp\u003eHigh fidelity is calculated according to Eq.\u0026nbsp;(\u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e):\u003c/p\u003e\n\u003cdiv id=\"Equ3\" class=\"Equation\"\u003e\n\u003cdiv id=\"FileID_Equ3\" class=\"mathdisplay\"\u003e$$\\:{\\text{F}}_{\\text{h}}\\text{=}\\frac{{\\text{h}}_{\\text{a}}}{{\\text{h}}_{\\text{t}}}\\text{\u0026times;100%}$$\u003c/div\u003e\n\u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eWhere: \u003cem\u003eF\u003c/em\u003e\u003csub\u003e\u003cem\u003eh\u003c/em\u003e\u003c/sub\u003e is the high fidelity parameter, \u003cem\u003eh\u003c/em\u003e\u003csub\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sub\u003e is the actual height (mm), \u003cem\u003eh\u003c/em\u003e\u003csub\u003e\u003cem\u003et\u003c/em\u003e\u003c/sub\u003e is the theoretical height (mm).\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec7\" class=\"Section3\"\u003e\n\u003ch2\u003e2.3.2 Reprint of PAC supramolecular polymer\u003c/h2\u003e\n\u003cp\u003eThe cured M\u003csub\u003eCS-0.5%\u003c/sub\u003e PAC supramolecular polymer scaffold was heated at 60 ℃ to transform the solidified PAC supramolecular polymer into a flowable sol. Using this sol as printing ink, we fabricated filaments and grid-shaped scaffolds. The study evaluated the reproducibility of the printing ink in three key aspects: diameter deviation rate, filament fidelity, and structural integrity.\u003c/p\u003e\n\u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\n\u003ch2\u003e2.4 Preparation of conductive supramolecular polymer with PTA-AgNO\u003csub\u003e3\u003c/sub\u003e-CS\u003c/h2\u003e\n\u003cp\u003eAfter adding CNTs to the PAC supramolecular polymer and ultrasonication for 40 min, the PAC supramolecular polymer was injected into the glass groove and left for 8\u0026ndash;12 h to obtain the PAC conductive supramolecular polymer. The CS and DMSO contents were 0.5% and 22%, respectively.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e\n\u003ch2\u003e2.5 Characterization\u003c/h2\u003e\n\u003cdiv id=\"Sec10\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.1 Infrared spectroscopy test\u003c/h2\u003e\n\u003cp\u003eThe infrared spectrometer (Brook, Germany) was used to analyze the infrared spectrum of the freeze-dried powder of TA, PTA, PTA and AgNO\u003csub\u003e3\u003c/sub\u003e reactants, with a scanning range of 4000\u0026thinsp;~\u0026thinsp;500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and resolution of 4 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec11\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.2 Mechanical properties test\u003c/h2\u003e\n\u003cp\u003eThe tensile test was conducted on a universal material mechanical testing machine (China Wanchen) equipped with a 100 N load cell. The PAC supramolecular polymer was formed into a dumbbell shape, with a total length of 35 mm, a measured length of 12 mm, a width of 2 mm, and a thickness of 1 mm, and axial tensile testing was performed at a loading speed of 100 mm/min. The compression test was conducted on a universal material testing machine equipped with a 100 N load cell. The PAC supramolecular polymer was formed into a cylindrical sample measuring 10 mm in height and 10 mm in diameter, which was compressed at a loading rate of 10 mm/min. The compressive strength (P) was calculated using Eq.\u0026nbsp;(4):\u003c/p\u003e\n\u003cp\u003e\u003cem\u003eP\u003c/em\u003e\u0026thinsp;=\u0026thinsp;\u003cem\u003eF\u003c/em\u003e/\u003cem\u003eS\u003c/em\u003e (4)\u003c/p\u003e\n\u003cp\u003eWhere: \u003cem\u003eP\u003c/em\u003e is the pressure (KPa), \u003cem\u003eF\u003c/em\u003e is the applied pressure (N), and \u003cem\u003eS\u003c/em\u003e is the cross-sectional area of the sample (m\u003csup\u003e2\u003c/sup\u003e).\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec12\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.3 Adhesion performance\u003c/h2\u003e\n\u003cp\u003eThe adhesion test was conducted on a universal material testing machine equipped with a 100 N load cell. The PAC supramolecular polymer was placed between two aluminum plates, maintaining a contact area of 20 mm\u0026times;20 mm. After applying gentle pressure for 10 seconds and allowing it to rest for 60 seconds, shear tensile testing was performed immediately. The shear adhesion strength was calculated by dividing the maximum load by the contact area, with five repetitions per set.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec13\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.4 Self-healing performance\u003c/h2\u003e\n\u003cp\u003eTwo cylindrical PAC supramolecular polymers stained with methylene blue and rhodamine B were cut in two with a scalpel, then tightly bonded together, and left to repair by itself. The repair was observed after 6 hours.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec14\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.5 Freeze resistance and moisture retention\u003c/h2\u003e\n\u003cp\u003eTo evaluate DMSO's impact on PAC supramolecular polymer freeze resistance, two PAC supramolecular polymers (DMSO-0% and DMSO-22%) were placed in 25 ℃ and \u0026minus;\u0026thinsp;20 ℃ environments, respectively, for tensile bending testing. Differential Scanning Calorimetry (DSC) equipment (Nordirch, Germany) was employed to measure the PAC supramolecular polymer's freeze resistance under varying conditions: cooling from 40 ℃ to -60 ℃ at a rate of -10 ℃/min, holding at -30 ℃ for 5 minutes, followed by heating to 40 ℃ at 10 ℃/min. Thermal flow measurements were continuously monitored during both cooling and heating processes. In order to test the effect of DMSO on the water retention of the PAC supramolecular polymer, two kinds of PAC supramolecular polymers with DMSO-0% and DMSO-22% were stored in a room temperature container for 11 days, and the weight change of the two PAC supramolecular polymers was recorded every day.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec15\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.6 In vitro blood compatibility.\u003c/h2\u003e\n\u003cp\u003eIn vitro hemolysis experiments were conducted using sodium citrate-treated whole sheep blood to evaluate the hemolysis performance of the PAC supramolecular polymer. Weighing 1 ml of sheep blood and dispersing it in 10 ml of PBS buffer. The mixture was placed in a centrifuge and centrifuged at 2280 r/min three times. The lower layer of red blood cells after centrifugation was collected and diluted with PBS buffer at a ratio of 1:10 to obtain the red blood cell dilution. The red blood cell dilution and sample were placed in a clean test tube, and the color change of the solution within the test tube was observed. If the solution turned red, it indicated red blood cell rupture and hemolytic properties of the sample. Deionized water mixed with the red blood cell dilution served as the positive control, while PBS buffer mixed with the red blood cell dilution served as the negative control. All test tubes were incubated on a shaker maintained at 37 ℃ for 2 hours to ensure full contact between red blood cells and the sample. After incubation, the suspension in each test tube was transferred to a centrifuge (China Xiangyi) and centrifuged at 3230 r/min to effectively remove red blood cell fragments. Finally, the absorbance of the supernatant was precisely measured using a UV spectrophotometer (Shimadzu, Japan) at a wavelength of 540 nm. The hemolysis rate of the sample is calculated according to Eq.\u0026nbsp;(\u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e):\u003c/p\u003e\n\u003cdiv id=\"Equ4\" class=\"Equation\"\u003e\n\u003cdiv id=\"FileID_Equ4\" class=\"mathdisplay\"\u003e$$\\:\\text{Hemolysis rate}\\left(\\text{%}\\right)\\text{=}\\frac{{\\text{OD}}_{\\text{S}}\\text{-}{\\text{OD}}_{\\text{n}}}{{\\text{OD}}_{\\text{P}}\\text{-}{\\text{OD}}_{\\text{n}}}\\text{\u0026times;100%}$$\u003c/div\u003e\n\u003cdiv class=\"EquationNumber\"\u003e5\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eWhere: \u003cem\u003eHemolysis rate\u003c/em\u003e is the hemolysis rate of the sample, \u003cem\u003eOD\u003c/em\u003e\u003csub\u003e\u003cem\u003es\u003c/em\u003e\u003c/sub\u003e is the absorbance of the sample, \u003cem\u003eOD\u003c/em\u003e\u003csub\u003e\u003cem\u003en\u003c/em\u003e\u003c/sub\u003e is the absorbance of the negative control sample, \u003cem\u003eOD\u003c/em\u003e\u003csub\u003e\u003cem\u003ep\u003c/em\u003e\u003c/sub\u003e is the absorbance of the positive control sample.\u003c/p\u003e\n\u003cp\u003eIn vitro coagulation experiments were conducted using sodium citrate-treated whole sheep blood to evaluate the clotting performance of the PAC supramolecular polymer. The samples were placed in test tubes with a blank control group (without samples). 0.1 ml of recalcified blood was added and incubated in a 37 ℃ water bath for 0, 2, 4, 6, and 8 minutes. Deionized water was then added to terminate the clotting process. Blood supernatants were collected at each time point and absorbance measured at 540 nm. This measurement reflects hemoglobin (HA) release from free red blood cells. A higher relative hemoglobin retention rate (RHA) indicates slower clotting kinetics. The relative RHA is calculated according to Eq.\u0026nbsp;(\u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e):\u003c/p\u003e\n\u003cdiv id=\"Equ5\" class=\"Equation\"\u003e\n\u003cdiv id=\"FileID_Equ5\" class=\"mathdisplay\"\u003e$$\\:\\text{RHA}\\left(\\text{%}\\right)\\text{=}\\frac{{\\text{HA}}_{\\left(\\text{t}\\right)}}{{\\text{HA}}_{\\left(\\text{0}\\right)}}\\text{\u0026times;100%}$$\u003c/div\u003e\n\u003cdiv class=\"EquationNumber\"\u003e6\u003c/div\u003e\n\u003c/div\u003e\n\u003cp\u003eWhere: \u003cem\u003eRHA\u003c/em\u003e is the retention rate relative to hemoglobin, \u003cem\u003eHA\u003c/em\u003e\u003csub\u003e\u003cem\u003e(t)\u003c/em\u003e\u003c/sub\u003e is the hemoglobin absorbance of the sample at the time of measurement, and \u003cem\u003eHA\u003c/em\u003e\u003csub\u003e\u003cem\u003e(0)\u003c/em\u003e\u003c/sub\u003e is the hemoglobin absorbance of the sample at the time of measurement without addition.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec16\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.7 In vitro bacteriostatic test\u003c/h2\u003e\n\u003cp\u003eThe antibacterial properties of Escherichia coli (E.coli) and Staphylococcus aureus (S.aureus) were tested using the inhibition method. First, prepare nutrient agar medium by adding agar powder to distilled water, heating it in an oil bath at 100\u0026deg;C until boiling, then sterilizing it for 1 hour in a high-pressure steam sterilizer. Pour the liquid agar into petri dishes and sterilize under UV light for 30 minutes to obtain the final medium. Next, perform bacterial dilution: add 1 ml of physiological saline to test tubes containing bacterial cultures, scrape bacteria with a pipette, transfer to conical flasks with small beads (25 ml), then add 9 ml of saline to disperse the beads, creating a bacterial suspension. Dilute this suspension six times with 1 ml aliquots. Place 200 \u0026micro;l of diluted E.coli and S.aureus cultures on the nutrient agar medium in a laminar flow hood, spread evenly with a swab, and position UV-sterilized circular samples on the surface. Incubate at 37\u0026deg;C for 24 hours. The inhibition zone around the PAC supramolecular polymer reflects its antibacterial properties, and the radius of the inhibition area is measured using ImageJ software.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec17\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.8 Conductivity test\u003c/h2\u003e\n\u003cp\u003eTo test the conductivity of the PAC conductive supramolecular polymer, the conductive supramolecular polymer was sandwiched between two aluminum plates and connected to an LED indicator and a power supply with a wire. A certain voltage was applied and the LED indicator was observed.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec18\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.9 Fatigue resistance test\u003c/h2\u003e\n\u003cp\u003eThe fatigue resistance performance test was conducted on a universal material mechanical testing machine equipped with a 100 N load cell. The PAC conductive supramolecular polymer was formed into dumbbell-shaped specimens measuring 35 mm in total length, 12 mm in gauge length, 2 mm in width, and 1 mm in thickness. Continuous tensile cycles were performed at a constant speed of 100 mm/min, stretching the specimens to 10%, 20%, 30%, and 40% of their original lengths, respectively.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec19\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.10 Strain sensing test.\u003c/h2\u003e\n\u003cp\u003eThe strain sensing performance of conductive supramolecular polymer was tested using a mechanical testing machine and a source meter (Tektronix, USA). The PAC conductive supramolecular polymer was fabricated into a strip measuring 3 cm in length, 1 cm in width, and 2 mm in thickness. The strip was secured on the machine's fixture while connected to the Source Measure Unit's input terminal. By monitoring the resistance fluctuations through the Source Measure Unit, we recorded the PAC conductive supramolecular polymer's tensile strain sensing curve to obtain key parameters: sensitivity factor (GF), response time, and recovery time, which collectively reflect the material's sensitivity. GF represents the slope of the resistance-strain curve, response time indicates the duration from stress application to material deformation, and recovery time denotes the period required for the PAC conductive supramolecular polymer's resistance to return to its original state after strain unloading. A cyclic loading-unloading process was conducted with 40% strain applied to the PAC conductive supramolecular polymer, repeated 200 times. The resistance changes during this cyclic loading-unloading cycle were used to evaluate the PAC conductive supramolecular polymer's stability and durability.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec20\" class=\"Section3\"\u003e\n\u003ch2\u003e2.5.11 Human detection\u003c/h2\u003e\n\u003cp\u003eThe PAC conductive supramolecular polymer is made into a long strip of 3 cm long, 1 cm wide and 2 mm thick, which is attached to the finger joint, wrist, elbow and knee of the human body. The strip is connected to the input end of the Source Measure Unit, and the tensile strain sensing curve of the PAC conductive supramolecular polymer is recorded by the resistance fluctuation of the Source Measure Unit to complete the detection of human movement.\u003c/p\u003e\n\u003c/div\u003e\n\u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec22\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Synthesis and structural characterization of PAC supramolecular polymer\u003c/h2\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea and \u003cb\u003eFig. S2\u003c/b\u003e, TA is dissolved in DMSO and heated at 70 ℃ for 5 minutes. During this process, the disulfide bonds in TA break, allowing S radicals to interconnect and form new disulfide bonds, while carboxyl groups form hydrogen bonds, ultimately generating PTA. This reaction causes the 1690 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e peak of TA to split into two distinct peaks representing symmetric and asymmetric stretching vibrations of PTA's carboxyl groups. When AgNO\u003csub\u003e3\u003c/sub\u003e is added to PTA, a PTA-AgNO\u003csub\u003e3\u003c/sub\u003e solution is formed. The Ag\u003csup\u003e+\u003c/sup\u003e ions introduced into the polymer coordinate with carboxyl groups on PTA chains, causing shifts in the stretching peaks. Subsequently, CS solution is added and thoroughly mixed with the system. After cooling, the amino groups on the CS chains form hydrogen bonds with the carboxyl groups in PTA, while Ag\u003csup\u003e+\u003c/sup\u003e ions establish metal coordination bonds with both the amino and hydroxyl groups on the CS chains. These Ag\u003csup\u003e+\u003c/sup\u003e ions also link the PTA and CS chains, creating a dynamic network structure[\u003cspan additionalcitationids=\"CR32\" citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb, the non-covalent interactions of the PAC supramolecular polymer. At elevated temperatures, hydrogen and metal coordination bonds break, then reform upon cooling. This temperature-sensitive behavior enables the supramolecular polymer to undergo thermal cycling decomposed at high temperatures and restored upon cooling-making PAC supramolecular polymer suitable for applications in 3D printing and self-healing materials[\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e, \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec23\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Mechanical properties of PAC supramolecular polymer\u003c/h2\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea, the tensile strength and modulus of the PAC supramolecular polymer first increase and then decrease with increasing CS content. The CS-0% PAC supramolecular polymer exhibits the lowest values at 0.24 MPa and 0.02 MPa, while the CS-0.5%, CS-1.5%, and CS-2.5% PAC supramolecular polymers show the highest values of 0.49 MPa and 0.05 MPa respectively. This is primarily because CS enhances the formation of coordination bonds with Ag\u003csup\u003e+\u003c/sup\u003e, creating a more compact network structure that boosts PAC supramolecular polymer strength. However, excessive CS content increases solution viscosity and weakens intermolecular interactions, thereby reducing tensile strength and modulus. The fracture elongation rate decreases from 2063% to 823% as CS content increases, likely due to significant changes in intermolecular interactions. The originally homogeneous structure breaks down, internal pore sizes expand, and molecular aggregation becomes disordered, ultimately resulting in non-uniform pore distribution. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb, the addition of DMSO significantly enhances the PAC supramolecular polymer's tensile strength, elongation at break, and tensile modulus. The DMSO-0% PAC supramolecular polymer exhibits the lowest values for these properties, while the DMSO-5% PAC supramolecular polymer shows the highest. The DMSO-22% PAC supramolecular polymer demonstrates the greatest elongation at break. This trend likely stems from DMSO's ability to improve the solubility and dispersion of components while forming hydrogen bonds with water molecules, creating strong intermolecular interactions. Conversely, reduced DMSO content increases solid content, decreases molecular spacing, and tightens the structure. These structural changes ultimately lead to increased tensile strength and modulus, while the elongation at break gradually decreases.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec and \u003cb\u003eFig. S3\u003c/b\u003e, when the PAC supramolecular polymer's deformation reaches 70%, the compressive strength initially increases with rising CS content before decreasing. The CS-0% PAC supramolecular polymer exhibits the lowest compressive strength at 0.16 MPa, while the CS-0.5%, CS-1.5%, and CS-2.5% PAC supramolecular polymers show the highest strength at 0.27 MPa. This is primarily due to the CS molecules' rich content of amino and carboxyl groups, which form stronger coordination bonds with silver ions through complexation. These coordination bonds create a denser internal network structure within the PAC supramolecular polymer, enhancing inter-component connections and thus boosting compressive strength. However, excessive CS content may cause molecular chain entanglement and aggregation, disrupting the ordered network structure and weakening intermolecular interactions, ultimately leading to reduced compressive strength. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ed and \u003cb\u003eFig. S4\u003c/b\u003e, when the PAC supramolecular polymer deformation reaches 70%, the compressive strength initially increases with increasing DMSO solvent content before decreasing. The DMSO-0% PAC supramolecular polymer exhibits the lowest compressive strength at 0.05 MPa, while the DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers show maximum compressive strength of 0.35 MPa at 5% DMSO content. This phenomenon primarily stems from DMSO's ability as a polar organic solvent to form extensive hydrogen bond networks with water molecules. These hydrogen bonds enhance intermolecular forces, stabilizing the PAC supramolecular polymer's internal structure and thereby improving compressive strength. Additionally, appropriate DMSO concentration increases PAC supramolecular polymer viscosity, reducing molecular spacing and enhancing structural compactness, which further elevates compressive strength.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec24\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Adhesion, self-healing, frost resistance and moisture retention of PAC supramolecular polymer\u003c/h2\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea shows physical photos of the PAC supramolecular polymer adhering to plastic, glass, rubber, and iron. The PAC supramolecular polymer demonstrates strong adhesion to these materials, primarily due to the carboxyl groups in TA and the abundant carboxyl and amino groups in CS. When contacting material surfaces, these functional groups interact with atoms or functional groups through various mechanisms. Figure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb presents the adhesion strength data of the PAC supramolecular polymer. As CS content increases, the adhesive strength rises, with CS-0% PAC supramolecular polymer showing the lowest adhesion (7.74 KPa). The CS-2.5% PAC supramolecular polymer achieves the highest strength at 67.74 KPa. This enhancement stems from CS molecules containing both amino and carboxyl groups, which form metal-coordinated bonds with aluminum sheets, thereby strengthening the interfacial bonding between the PAC supramolecular polymer and the metal substrate[\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e, \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. As the DMSO solvent content increases, the adhesive strength of the PAC supramolecular polymer first rises and then decreases. The DMSO-0% PAC supramolecular polymer exhibits the lowest tensile adhesion strength at 1.82 KPa, while the DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers show significant variations. Notably, the DMSO-12% PAC supramolecular polymer demonstrates the highest adhesion strength of 22.77 KPa. This is primarily attributed to DMSO's ability to enhance solubility and dispersion of components, which increases the number of functional groups interacting with aluminum plates, thereby boosting adhesion strength. However, excessive DMSO causes molecular chain extension, increasing contact opportunities between internal functional groups and aluminum plates. This expansion of cross-linking points ultimately reduces the interaction between functional groups and aluminum plates, leading to decreased adhesion strength.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTo investigate the self-healing properties of PAC supramolecular polymer, the PAC supramolecular polymer was stained with methylene blue and rhodamine B to create two cylindrical specimens in different colors. The specimens were cut with a scalpel, tightly bonded together, and left to self-repair under static conditions. As shown in \u003cb\u003eFig. S5\u003c/b\u003e, the PTA-AgNO\u003csub\u003e3\u003c/sub\u003e-CS supramolecular polymer features a porous structure. When subjected to external forces, its pores deform (e.g., compress or collapse) to disperse stress and reduce crack propagation[\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec, after 12 hours, they were recombined, revealing fused edges without visible fracture marks under tensile stress. The self-healing mechanism stems from hydrogen bonds and dynamic metal-ligand coordination within the PAC supramolecular polymer. When subjected to external forces causing molecular breakage, altered intermolecular distances trigger hydrogen bonds to reorganize through thermal motion. Simultaneously, rapid adjustment and reconstruction of metal-ligand interactions enable seamless reconnection of fractured sections, achieving swift restoration to its original state[\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e, \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ed shows images of the PAC supramolecular polymer prepared with DMSO-0% and DMSO-22% at -25 ℃ and \u0026minus;\u0026thinsp;20 ℃ torsional states, respectively. The results demonstrate that the supramolecular polymer prepared using a H\u003csub\u003e2\u003c/sub\u003eO/DMSO binary solvent system maintains tensile bending performance at -20 ℃, whereas the PAC supramolecular polymer prepared with H\u003csub\u003e2\u003c/sub\u003eO solvent ruptures at -20 ℃. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ee, the H\u003csub\u003e2\u003c/sub\u003eO-solvent-based PAC supramolecular polymer exhibits significant exothermic/endothermic peaks during cooling/heating processes from \u0026minus;\u0026thinsp;60 ℃ to 40 ℃, attributed to water crystallization/ice melting. In contrast, the DMSO-22% binary solvent system shows no significant thermal flow changes. This is due to hydrogen bonding interactions between DMSO and H\u003csub\u003e2\u003c/sub\u003eO, which tightly bind water molecules within the PAC supramolecular polymer network. This interaction significantly reduces free water content, preventing excessive ice crystal formation and growth at low temperatures. Consequently, the PAC supramolecular polymer maintains structural integrity through reduced ice-induced mechanical damage, preserving its network architecture and ensuring stable performance[\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ef, the DMSO-22% PAC supramolecular polymer maintained its original morphology after 11 days of room-temperature storage, while the DMSO-0% PAC supramolecular polymer exhibited significant volume reduction. \u003cb\u003eFig. S6\u003c/b\u003e reveals that the PAC supramolecular polymer experienced rapid dehydration at room temperature, with its water retention rate declining sharply. In contrast, the supramolecular polymer demonstrated excellent water-holding capacity, retaining 82% moisture content after 11 days. This stability is primarily attributed to the strong hydrogen bonds formed between DMSO and H\u003csub\u003e2\u003c/sub\u003eO. These hydrogen bonds effectively reduce water vapor pressure, which prevents water molecules from diffusing into the external environment. Consequently, the PAC supramolecular polymer's internal moisture content remains relatively stable, ensuring consistent physicochemical properties and enabling sustained functionality[\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec25\" class=\"Section2\"\u003e \u003ch2\u003e3.4 In vitro blood compatibility and antibacterial properties of PAC supramolecular polymer.\u003c/h2\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea shows the hemolytic performance of PAC supramolecular polymer. The H\u003csub\u003e2\u003c/sub\u003eO positive control demonstrates hemolysis, with the centrifuged supernatant appearing red and opaque. In contrast, the PBS negative control shows no hemolysis, yielding a clear supernatant after centrifugation. A hemolysis rate below 5% indicates excellent blood compatibility. When comparing the negative and positive controls, PAC supramolecular polymers containing 0-2.5% CS or 5\u0026ndash;22% DMSO produced clear supernatants following blood culture centrifugation, demonstrating good blood compatibility. However, the DMSO-0% PAC supramolecular polymer showed opacity due to sodium hydroxide substitution for DMSO, indicating poor blood compatibility. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb, both 0-2.5% CS and 5\u0026ndash;22% DMSO PAC supramolecular polymers exhibited hemolytic rates below 5%, showing no hemolysis[\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ec shows the coagulation performance of PAC supramolecular polymers. Compared with the blank control group, all other PAC supramolecular polymers (except CS-0% and DMSO-0%) began clotting within 2\u0026ndash;4 minutes, while CS-0% took 6 minutes and DMSO-0% required 8 minutes[\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ed presents the relative hemoglobin levels (RHA) of PAC supramolecular polymer with varying CS and DMSO concentrations. The RHA values for CS-0.5%, CS-1.5%, CS-2.5%, DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers started decreasing at 4 minutes, whereas CS-0% and DMSO-0% maintained high RHA levels until 4 minutes. Notably, CS-0% PAC supramolecular polymer showed declining RHA from 6 minutes onward. These results demonstrate that CS significantly enhances PAC supramolecular polymer coagulation capacity, with CS-0.5%, CS-1.5%, CS-2.5%, DMSO-5%, DMSO-12%, and DMSO-22% PAC supramolecular polymers exhibiting excellent clotting performance. In contrast, DMSO-0% PAC supramolecular polymer, containing sodium hydroxide, caused blood damage and failed to coagulate effectively.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea shows the inhibition zone images and diameters of PAC supramolecular polymer with varying CS concentrations on E.coli and S.aureus culture media. The results demonstrate that the PAC supramolecular polymer effectively inhibits both bacteria, indicating its antibacterial efficacy[\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb, the inhibition zones expand with increasing CS concentration. The 2.5% CS PAC supramolecular polymer exhibits the strongest inhibitory capacity against both pathogens, attributed to CS's potent antibacterial properties that enhance the PAC supramolecular polymer's antimicrobial performance.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ec shows the inhibition zone images and diameters of the PAC supramolecular polymer containing DMSO on E.coli and S.aureus culture media. The results demonstrate that the DMSO-containing PAC supramolecular polymer effectively inhibits both bacteria, indicating its antibacterial efficacy. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed, the DMSO-0% PAC supramolecular polymer exhibits the largest inhibition zone diameter due to sodium hydroxide's strong alkaline properties that inhibit bacterial growth. For the 5%, 12%, and 22% DMSO concentrations, the inhibition zones increase proportionally with DMSO content, confirming the PAC supramolecular polymer's bacteriostatic capability and showing that higher DMSO levels enhance its antimicrobial effectiveness.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec26\" class=\"Section2\"\u003e \u003ch2\u003e3.5 Evaluation of 3D printing performance of PAC supramolecular polymer.\u003c/h2\u003e \u003cp\u003eBy maintaining a fixed DMSO concentration of 22%, the CS content was adjusted to achieve CS-0.5%, CS-1.5%, and CS-2.5% as the PAC supramolecular polymer ink for printing. Then the 3D printing performance of supramolecular polymers was judged by diameter deviation rate, area fidelity and height fidelity[\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e, \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea and \u003cb\u003eFig. S7\u003c/b\u003e, the M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e exhibits the best fluidity, producing continuous and uniform extruded filaments. M\u003csub\u003eCS\u0026minus;1.5%\u003c/sub\u003e followed closely, while the M\u003csub\u003eCS\u0026minus;2.5%\u003c/sub\u003e printing ink resulted in PAC supramolecular polymer filaments with uneven thickness. A lower direct deviation rate indicates that the PAC supramolecular polymer filament diameter more closely matches the nozzle diameter, demonstrating superior printability and precision. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb, the M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e printing ink demonstrated the smallest diameter deviation rate, exhibiting the best printability and filament precision.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ec, the intersections between PAC supramolecular polymer filaments in single layer grids produced by M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e, M\u003csub\u003eCS\u0026minus;1.5%,\u003c/sub\u003e and M\u003csub\u003eCS\u0026minus;2.5%\u003c/sub\u003e printing inks exhibit significant accumulation, which affects print quality. Notably, the M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e ink demonstrates optimal accumulation patterns, printed product with higher precision. In contrast, the M\u003csub\u003eCS\u0026minus;1.5%\u003c/sub\u003e and M\u003csub\u003eCS\u0026minus;2.5%\u003c/sub\u003e inks result in noticeable accumulation at filament intersections. The area fidelity closely approximates 100%, indicating that the M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e ink produces PAC supramolecular polymer grids with the closest theoretical area match. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed further confirms this, showing the M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e ink achieves the highest area fidelity with the most accurate alignment to the theoretical grid dimensions.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ee, the morphology of the double layer grids printed with M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e, M\u003csub\u003eCS\u0026minus;1.5%\u003c/sub\u003e, and M\u003csub\u003eCS\u0026minus;2.5%\u003c/sub\u003e inks demonstrates differences. The M\u003csub\u003eCS\u0026minus;2.5%\u003c/sub\u003e ink produced well-connected upper and lower layers with strong support from the base layer, showing minimal filament collapse. In contrast, both M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e and M\u003csub\u003eCS\u0026minus;1.5%\u003c/sub\u003e ink resulted in grids with noticeable filament collapse and poor adhesion between layers, indicating weaker support from the base layer. The height fidelity closely approached 100%, with the M\u003csub\u003eCS\u0026minus;2.5%\u003c/sub\u003e ink printing the most structurally stable dual-layer grid as evidenced by Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ef.\u003c/p\u003e \u003cp\u003eTo evaluate the reproducibility of the printing ink, a heated solution of the cured M\u003csub\u003eCS\u0026minus;0.5%\u003c/sub\u003e PAC supramolecular polymer was used for secondary printing. Figure\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eg shows, The PAC supramolecular polymer filaments in the second print exhibit uniform thickness, with the single layer grid maintaining regular patterns. While the lower layer of the double layer grid demonstrates good adhesion to the upper layer, the lower layer shows inadequate support, resulting in filament discontinuities and accumulation. The reproducibility of the printing ink was assessed through three metrics: diameter deviation rate, area fidelity, and height fidelity. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eh, compared to the initial print, the diameter deviation rate and area fidelity remained relatively stable, while the high fidelity showed a slight decrease. These findings collectively confirm that the PAC supramolecular polymer printing ink demonstrates reliable reproducibility.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec27\" class=\"Section2\"\u003e \u003ch2\u003e3.6 Conductive properties and fatigue resistance of PAC conductive supramolecular polymer\u003c/h2\u003e \u003cp\u003eBy gradually increasing the voltage, we observed the brightness changes of the LED indicator[\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, when a 2V voltage was applied, the LED indicator emitted a faint light, indicating low current flow through the conductive supramolecular polymer and weak electrical signal transmission in the circuit. With the voltage being increased at a certain gradient, the LED's light became visibly brighter, demonstrating the continuous increase in current flow. This phenomenon primarily stems from the uniformly distributed carbon nanotubes (CNTs) within the PAC conductive supramolecular polymer system, which establish efficient conductive pathways. Even at lower voltages, these CNTs effectively transport electrons to power the LED, proving the PAC supramolecular polymer's excellent conductivity.\u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003eb-e shows the 10-cycle loading-unloading curves of PAC conductive supramolecular polymer under 10%, 20%, 30%, and 40% tensile deformation. The results indicate that after the initial loading-unloading cycle, partial breakage of coordination bonds between silver ions and CS molecular chains occurred within the material. Additionally, stress-induced dissociation at the TA crosslinking point caused significant softening and weakening of its internal structure, leading to energy dissipation that prevented immediate recovery to the initial state. However, during subsequent nine cyclic loading tests at 10% and 20% deformation, the PAC conductive supramolecular polymer maintained consistent tensile strength and hysteresis loops compared to the initial state. This stability is attributed to the self-healing mechanism of the dynamic crosslinking network: broken silver-amino coordination bonds rapidly reformed through silver ion migration during unloading, while disulfide bonds between TA molecules underwent thiol-disulfide exchange reactions following stress release, enabling reconstruction of the three-dimensional network topology[\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e]. For PAC conductive supramolecular polymer at 30% and 40% deformation, the subsequent nine cyclic loading tests revealed differences in tensile strength and hysteresis loops compared to the first cycle. Although maintaining cyclic stability, mechanical properties exhibited gradual degradation. The results show that under the tensile deformation of 10%~20%, the material has excellent anti-fatigue performance and recovery performance, and can maintain relatively stable mechanical performance after multiple stress cycles.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec28\" class=\"Section2\"\u003e \u003ch2\u003e3.7 Strain sensing of PAC conductive supramolecular polymer\u003c/h2\u003e \u003cp\u003eBy connecting conductive supramolecular polymer to a universal testing machine, a real-time monitoring system for resistance changes was established. The conductive supramolecular polymer was subjected to tensile and cyclic tensile strain tests using the universal testing machine. The resistance variations during these processes were precisely measured with a universal meter, enabling determination of the PAC supramolecular polymer's strain sensing capability, strain sensitivity, and stability[\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e, \u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIn the field of strain sensor material research, strain sensing performance serves as a key indicator for evaluating material suitability in this domain. For PAC supramolecular polymer materials, excellent strain sensing capability means they can accurately detect external stress changes and convert these variations into detectable electrical signals, which is crucial for achieving high-precision strain monitoring. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ea, when subjected to 10%, 20%, 30%, and 40% deformation, the conductive supramolecular polymer underwent three repeated tensile cycles, maintaining consistent repeatability in resistance change rates. The results demonstrate that under identical strain conditions, this conductive supramolecular polymer consistently outputs stable resistance variation signals with reliable stability and repeatability. Moreover, significant differences in resistance change rates were observed across varying deformation levels, showing regular patterns as deformation increased progressively. This indicates that PAC conductive supramolecular polymer exhibits high sensitivity and reliable repeatability, with distinct response variations under different strain states. These characteristics enable effective differentiation of deformation levels, providing a solid performance foundation for applications in smart sensing and wearable devices.\u003c/p\u003e \u003cp\u003eIn the performance evaluation system of strain sensors, strain sensitivity serves as a key parameter for assessing material quality. This characteristic can be characterized by GF and response time, reflecting the practical applicability of conductive supramolecular polymer materials in strain sensor applications. The GF value represents the slope of the strain-resistance change rate curve, indicating the material's sensitivity to electrical resistance variations under strain. For instance, a higher GF value signifies more pronounced resistance changes under equivalent strain conditions, enabling easier detection and sensing. Figure\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003eb shows the resistance variation of PAC conductive supramolecular polymer under 0\u0026ndash;40% strain. Within the 10%-40% strain range, the strain rate of resistance change gradually increases with strain magnitude. Although the GF exhibits a slight downward trend with strain progression, the decrease remains relatively minor. Notably, GF maintains a high value even at 40% strain. These results conclusively demonstrate that PAC conductive supramolecular polymer retains sensitive resistance response capability under significant strain conditions, exhibiting excellent strain sensing performance. Figure\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ec illustrates the response time and recovery time of PAC conductive supramolecular polymer after being stretched to 10% strain, held for 1 second, and then released to return to its original 0% deformation state. As shown in the figure, the PAC conductive supramolecular polymer demonstrates a response time of 0.86 seconds and a recovery time of 0.83 seconds. Compared to similar commercial PAC supramolecular polymer materials, these values are notably lower. This rapid and precise reaction capability strongly reflects the excellent strain sensitivity of the PAC conductive supramolecular polymer.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe strain sensing stability of PAC supramolecular polymer serves as a critical indicator for the durability and repeatability of PAC supramolecular polymer strain sensors, determining their long-term operational reliability under frequent stress. This performance directly impacts both sensor lifespan and the accuracy of monitoring data. Figure\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003ed demonstrates the resistance change rate of PAC conductive supramolecular polymer during 200 tensile cycles at a constant 40% strain. The results show that as the number of cycles increased from 1 to 200, the PAC supramolecular polymer maintained stable fluctuations within a defined range. This consistent response highlights its exceptional stability, enabling reliable conversion of strain signals into stable resistance variations even under prolonged, repetitive strain applications. Furthermore, the consistent resistance changes across multiple cycles demonstrate outstanding reproducibility \u0026ndash; applying identical 40% strain consistently yields nearly identical responses regardless of cycle count. These findings collectively confirm that PAC conductive supramolecular polymer exhibits superior long-term performance as a strain sensor.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec29\" class=\"Section2\"\u003e \u003ch2\u003e3.8 Human detection performance of PAC conductive supramolecular polymer\u003c/h2\u003e \u003cp\u003eThe PAC conductive supramolecular polymer was immobilized on human joints with frequent and representative movements such as fingers, wrists, elbows, and knees. These joints exhibit distinct motion patterns and ranges of motion, enabling comprehensive simulation of various daily activities. During human movement, the stretching and strain changes in joints and muscles drive the PAC supramolecular polymer. By connecting the PAC supramolecular polymer to a Source Measure Unit and observing resistance variations during motion[\u003cspan additionalcitationids=\"CR53\" citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e], Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e demonstrates that as finger, wrist, knee, and elbow flexion occurs, the resistance change rate of the PAC conductive supramolecular polymer shows significant acceleration. The PAC supramolecular polymer exhibits rapid response speed, generating corresponding electrical signal changes almost instantaneously during joint movement, indicating its excellent real-time sensing capability. Furthermore, when performing repeated joint movements, the PAC supramolecular polymer consistently outputs stable and nearly identical resistance changes, demonstrating high stability and repeatability. Additionally, the resistance change rates across different joint motion ranges show clear variations, accurately reflecting each joint's movement status and amplitude, achieving precise motion perception. In summary, the PAC conductive supramolecular polymer demonstrates superior sensing performance and practical applicability for human joint motion monitoring.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eIn summary, a PAC supramolecular polymer featuring hydrogen bonds and dynamic metal coordination bonds has been developed for 3D printing and strain sensing applications. The dynamic metal coordination bonds and hydrogen bonds endow the polymer with rapid self-healing capabilities and temperature-responsive behavior. This supramolecular polymer demonstrates excellent mechanical properties, blood compatibility, and significant inhibition of Escherichia coli and Staphylococcus aureus. In 3D printing applications, ink containing 0.5% CS exhibits optimal filament precision and single-layer grid area fidelity. The ink with 2.5% CS achieves the highest stability in double-layer grid structures, while the ink itself is reusable. These characteristics make the supramolecular polymer a promising candidate for biological scaffolds. For strain sensing applications, the addition of carbon nanotubes (CNTs) confers conductivity to the polymer. The conductive supramolecular polymer demonstrates superior fatigue resistance, strain sensing performance, sensitivity, and cyclic stability. Practical human motion monitoring has confirmed its effectiveness and reliability as a strain sensor.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eSupplementary Information:\u0026nbsp;\u003c/strong\u003eThe online version contains supplementary material available at\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgements:\u003c/strong\u003e We are grateful for the financial support from the Natural Science Foundation of Heilongjiang Province of China (No. ZL2024E016), the Undergraduate Training Programs for Innovations by NEFU (No. 202510225580) and 2025 Provincial Higher Education Excellence Initiative: Funding for Joint Graduate Training Base Development through Industry-Education Integration.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors contributions:\u003c/strong\u003e S. L. and M. J. wrote the main manuscript text and prepared all figures. J. W. and J. L assisted in completing the photographs of samples in the manuscript. X. K., P. H. and J. D. discussed the results and proofread the manuscript. D. Z. conceptualized this review, supervised the writing process, edited and reviewed the manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability:\u0026nbsp;\u003c/strong\u003eThe data that support the findings of this study are available from the corresponding author upon reasonable request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003cstrong\u003e:\u0026nbsp;\u003c/strong\u003eThis work was supported by the Natural Science Foundation of Heilongjiang Province of China (No. ZL2024E016), the Undergraduate Training Programs for Innovations by NEFU (No. 202510225580) and 2025 Provincial Higher Education Excellence Initiative: Funding for Joint Graduate Training Base Development through Industry-Education Integration.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest:\u0026nbsp;\u003c/strong\u003eThe authors declare that they have no conflict of interest.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eOpen Access:\u0026nbsp;\u003c/strong\u003eThis article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. 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Adv Compos Hybrid Mater 8:323. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s42114-025-01395-x\u003c/span\u003e\u003cspan address=\"10.1007/s42114-025-01395-x\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Poly thioctic acid, Supramolecular polymer, Temperature sensitivity, 3D printing, Strain sensing","lastPublishedDoi":"10.21203/rs.3.rs-8804107/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8804107/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eSupramolecular polymers, formed through hydrogen bonds and dynamic metal coordination bonds, exhibit excellent reversibility and recyclability. In this study, dimethyl sulfoxide (DMSO) was used as a solvent to synthesize a PTA-AgNO\u003csub\u003e3\u003c/sub\u003e-CS (PAC) supramolecular polymer from thioctic acid (TA), silver nitrate (AgNO\u003csub\u003e3\u003c/sub\u003e), and chitosan (CS). The non-covalent interactions in PAC enable self-healing and temperature sensitivity. This polymer demonstrates superior mechanical properties, freeze resistance, moisture retention, hemolysis resistance, blood clotting promotion, and antibacterial activity. Capable of 3D printing and repeated fabrication, PAC meets personalized tissue engineering scaffold requirements while reducing production costs. Doped with carbon nanotubes (CNTs), the polymer achieves enhanced conductivity, fatigue resistance, strain sensing sensitivity, and cyclic stability. Field tests using human motion monitoring have confirmed its effectiveness as a reliable strain sensor.\u003c/p\u003e","manuscriptTitle":"A temperature-sensitive, reusable PTA-AgNO 3 -CS supramolecular polymer for 3D printing and strain sensing","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-02-24 07:52:30","doi":"10.21203/rs.3.rs-8804107/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-03-09T02:09:31+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-03-08T16:15:02+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-03-04T09:40:55+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-03-02T10:50:55+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"214212919281108367982131067022698715985","date":"2026-02-26T03:59:43+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"103020939886505731164525752004092828243","date":"2026-02-25T11:01:10+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"283342368307050625757842934308067584237","date":"2026-02-22T16:40:33+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"110725975515263259132693370031146186550","date":"2026-02-21T12:24:38+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"105844306046582677048881674670180232556","date":"2026-02-20T16:21:55+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"215220801062843492006944498222505898717","date":"2026-02-20T13:31:35+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-02-20T02:50:45+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2026-02-13T14:41:48+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2026-02-06T12:47:20+00:00","index":"","fulltext":""},{"type":"submitted","content":"Advanced Composites and Hybrid Materials","date":"2026-02-06T07:25:13+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"advanced-composites-and-hybrid-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"achm","sideBox":"Learn more about [Advanced Composites and Hybrid Materials](https://link.springer.com/journal/42114)","snPcode":"42114","submissionUrl":"https://submission.nature.com/new-submission/42114/3","title":"Advanced Composites and Hybrid Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"b31a63d2-36dc-4701-949f-acc4f7cf4e34","owner":[],"postedDate":"February 24th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"in-revision","subjectAreas":[],"tags":[],"updatedAt":"2026-05-16T14:10:06+00:00","versionOfRecord":[],"versionCreatedAt":"2026-02-24 07:52:30","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8804107","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8804107","identity":"rs-8804107","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}