Multifunctional cotton fabric with durable antibacterial, superhydrophobicity, and UV resistance based on Ag@TiO 2 Janus nanoparticles

Multifunctional cotton fabric with durable antibacterial, superhydrophobicity, and UV resistance based on Ag@TiO 2 Janus nanoparticles | 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 Multifunctional cotton fabric with durable antibacterial, superhydrophobicity, and UV resistance based on Ag@TiO 2 Janus nanoparticles Dangge Gao, Fangxing Wang, Bin Lyu, Jianzhong Ma, Zhouyang Zhao This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3191198/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 29 Jan, 2024 Read the published version in Cellulose → Version 1 posted 4 You are reading this latest preprint version Abstract The market demand for multifunctional cotton fabric is increasing. However, the key of developing cotton fabric with multiple functions is how to solve the problem of functional combination. In this study, silver@titanium dioxide Janus nanoparticles (Ag@TiO 2 Janus nanoparticles) were synthesized by Pickering emulsion polymerization and finished on the epoxy modified cotton fabric (Ag@TiO 2 Janus/E-cotton fabric). The Ag@TiO 2 Janus nanoparticles had asymmetric Janus structure, that one side being silane with hydrophilic amino group was covalently bonded with the epoxy group on the cotton fabric fibers and the other side being silane with hydrophobic long-chain alkane was faced the environment, which was to endow the cotton fabric durably superhydrophobic, UV resistance, and antibacterial. Characterization by SEM, XRD, EDS, EDS, FT-IR and TG verified the finishing of the cotton fabric with Ag@TiO 2 Janus nanoparticles. Ag@TiO 2 Janus/E-cotton fabric had a water contact angle of 160, after 50 wear cycles, the contact angle at the damaged part could still reach 152. Compared with raw cotton fabric, the antibacterial rate of Ag@TiO 2 Janus/E- cotton fabric to Escherichia coli (E. coli) and Streptococcus Urealyticus (S. aureus) is more than 95%. After 8 ultrasonic washing cycles, the antibacterial rate still maintained more than 80%. The UV protection performance of the finished cotton fabric was improved by 82.3%. Janus nanoparticles cotton fabric super-hydrophobic antibacterial durability UV resistance Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 1. Introduction cotton fabrics, one of the most common natural fiber textiles, are widely used in daily life by virtue of great softness [ 1 , 2 ] , low cost and air permeability [ 3 , 4 ] . With the improvement of the quality of life, endowing cotton fabric multiple functions has become the mainstream trend of high-quality development of the textile industry [ 5 – 7 ] . In particularly, under the current situation of frequent epidemic diseases, people's daily clothes and medical materials need to inhibit the growth and transmission of bacteria, reduce the adhesion between bacterial cells and materials surface and prevent the penetration of water droplets [ 8 ] . At the same time, people's daily clothes and medical materials should have anti-ultraviolet performance, mainly because the ozone layer is constantly destroyed, resulting in enhanced ultraviolet radiation, which is harmful to human skin health, such as skin aging, photosensitive rash and skin cancer [ 9 – 12 ] . Therefore, the design of multifunctional cotton fabric with antibacterial performance, super-hydrophobic performance and ultraviolet resistance is imperative. Titanium dioxide nanoparticles (TiO 2 NPs) have attracted much attention in fabricating functional cotton fabric due to its excellent ultraviolet resistance [ 13 ] , chemical stability [ 14 ] , antibacterial property [ 15 ] , photocatalytic property [ 16 ] , good biocompatibility and reasonable cost-effectiveness [ 17 ] . Although TiO 2 as functional finishing agent can endow the cotton fabric antibacterial ability via UV irradiation, the requirement of light irradiation conditions make the utilization rate of TiO 2 to the solar spectrum only about 3%, which limit the cotton fabric finished with TiO 2 for broad-spectrum antibacterial [ 18 ] . Luckily, many studies have been devoted to doping of TiO 2 with metal ions to enhance broad-spectrum antimicrobial property. The fermi energy level of noble metals are relatively low, electrons on the surface of TiO 2 are easily transferred to the surface of the noble metal to inhibit electron-hole recombination, thereby improving the light responsive range [ 19 , 20 ] . Furthermore, Ag nanoparticles (AgNPs) present a surface plasmon effect that induces electron transfer from metallic silver to TiO 2 resonance, resulting in charge separation actived by visible electromagnetic radiation [ 21 ] , which can enhance the photocatalytic and antimicrobial activities. For instance, Daniel J et al [ 22 ] . synthesized TiO 2 NPs coated by Ag (Ag/TiO 2 ) via sonochemistry, and the increase in silver dosage enable the optical bandgap of TiO 2 NPs to reduce from 3.2 eV to 2.6 eV, which improved broad-spectrum antimicrobial property of the cotton fabric. Janus nanoparticles refer to the non-centrosymmetric nanoparticles that integrate two different chemical compounds or functional into a structural system [ 23 ] . This flexible and controllable asymmetric structure can produce nanoparticles of different shapes and types such as amphiphilic Janus nanoparticles, anionic and cationic Janus nanoparticles, dumbbell Janus nanoparticles [ 24 ] . Among them, amphiphilic Janus nanoparticles are anisotropic nanomaterials with hydrophobic and hydrophilic properties, which can be used in cotton fabric functional finishing. Because amphiphilic Janus particles can not only provide low surface energy by hydrophobic side to endow the cotton fabric with superhydrophobic, but also improve the interaction force of nanoparticles and cotton fibers via hydrophilic side of the nanoparticles. Herein, we supposed amphiphilic Ag@TiO 2 Janus nanoparticles with one side comprising hydrophobic long-chain alkane, and the other side with hydrophilic amino group was covalently bonded with the epoxy group on the epoxy modified cotton fabric surface (Fig. 1 ). The aim was to endow the cotton fabric with the durable broad-spectrum antimicrobial, superhydrophobicity, and UV resistance properties. The finished cotton fabric were characterized in detail and their functional performance explored. 2. Experimental methods 2.1 Materials Titanium dioxide particles (100 nm in diameter) were supplied by Macklin (Shanghai, China). The paraffin wax with a melting point between 58°C and 60°C and Cyclohexane were supplied by Fuchen chemical reagents Co., LTD (Tianjin, China). The three kinds of silane coupling agents (3-aminopropyl) silane (KH550), n-octadecanetrichlorosilane (OTDS) and γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560) were supplied by Macklin (Shanghai, China). Cetyl Trimethyl Ammonium Bromide (CTAB), Sodium chloride (NaCl), Cyclohexane and Anhydrous ethanol were supplied by Tianli chemical reagents Co., LTD (Tianjin, China). Selected bacteria Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were saved by our laboratory and incubated at 37°C on a nutrient agar plate for 24 h before use. 2.2 Synthesis of Ag@TiO 2 microballoon sphere 2.2.1 Synthesis of Ag/C template Glucose was weighed and dissolved in deionized water, followed by addition of 0.10 mol/L AgNO 3 solution, mixed and stirred for 10 min, transferred into a 100 mL hydrothermal reaction kettle, reacted at 180 ℃ for 10 h, cooled to room temperature and then poured out; The produts were washed three times with ethyl alcohol by centrifugation and dried in an oven at 70 ℃ to obtain the Ag/C ball powder. 2.2.2 Synthesis of Ag@TiO 2 microballoon sphere 0.30 g Ag/C ball powder was ultrasonic dispersed in a certain amount of absolute ethanol for 5 min before transferred to a three-necked flask and added butyl titanate to react for 30 min at a mechanical stirring rate of 400 rpm/min; Then, a mixed solution of water, absolute ethanol and glacial acetic acid in a certain proportion was slowly dripped into the three-necked flask and reacted for 30 min. After 4 h of reaction, the products were washed three times with absolute ethanol and deionized water by centrifugation and dried in an oven to obtain dark brown powder, then which were calcined in muffle furnace for 3 h to obtain Ag@TiO 2 microspheres. 2.3 Synthesis of amphipathic Ag@TiO 2 Janus nanoparticles 2.3.1 Preparation of semi-coated paraffin colloid 10.00 g of paraffin wax was added into a three-necked flask and heated to melt at 75 ℃. 1.00 g of Ag@TiO 2 and 0.05 g of CTAB were dispersed in 90 mL of deionized water for ultrasonnic treatment for 10 min, then poured into the three-necked flask, stirred at high speed for an hour, and cooled to room temperature. With the decrease of temperature, paraffin wax solidified and turned into colloid. The wax colloid coated with Ag@TiO 2 was washed with deionized water and dried at 35 ℃ in vacuum. 2.3.2 Preparation of HO-Ag@TiO 2 -NH 2 particles A certain amount of paraffin colloidal particles and 1.00 g KH-550 were added into a beaker of 100 mL methanol aqueous solution and stirred magnetically at 37 ℃ for 10 h. Then the solid paraffin colloidal particles were rinsed with deionized water, and dried in vacuum oven at low temperature for 24 h. The dried modified paraffin colloid was dissolved in cyclohexane to dissolve the paraffin wax, then HO-Ag@TiO 2 -NH 2 released from the paraffin wax was washed with cyclohexane, ethanol and deionized water for three times by centrifugation. 2.3.3 Synthesis of Ag@TiO 2 Janus nanoparticles A certain amount of HO-Ag@TiO 2 -NH 2 particles were ultrasonicated in 50 mL of ethanol for 10 min, poured into a 100 mL three-necked flask, added with 3.00 g OTDS, and stirred at 65 ℃ in the dark for 12 h. The modified particles were centrifugally washed with ethanol and deionized water for three times by centrifugation. 2.4 Application experiment 2.4.1 Epoxy–functionalization of cotton fabric A certain amount of KH-560 and 100mL NaCl solution were added to the beaker, followed by addition of 0.10mol/L NaOH solution to adjust the pH of the solution to 10. The washed cotton fabric were added to the reaction system, and the temperature was adjusted to 60 ℃. It was taken out after reaction for 30 min under magnetic stirring, washed with deionized water and ethanol, and dried at 80 ℃ for preserevation. Finally, the epoxy modified cotton fabric (E-cotton fabric) were obtained. 2.4.2 The Ag@TiO 2 Janus nanoparticles graft on E-cotton fabric Janus nanoparticles were ultrasonically dispersed in 30 mL absolute ethyl alcohol, E-cotton fabric were soaked for 30 min, washed with absolute ethyl alcohol for 3 times, and dried at 80 ℃ for 30 min. 2.5 Characterization Scanning electron microscope (SEM) measurement (Hitachi S-4800) was used to observe the structural characteristics of Ag@TiO 2 microspheres and modified cotton fabric. In order to observe the asymmetric characteristics of Janus particles, the morphology of Janus particles were measured by transmission electron microscope (TEM) analyzer (Tecnai G2 F20 S-TWIN). The dynamic light scattering (DLS) measurement (Malvern Zetasizer NANO-ZS90) was used to measure the particles size distribution and average particles size (concentration diluted to 0.1 wt%). Infrared spectrum (FT-IR) measurement (Vertex70) was characterized the modification effect of KH550 and OTDS on Ag@TiO 2 nanoparticles and cotton fabric. Ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS; Agilent radius mark-2500). The particles of TiO 2 , HO-Ag@TiO 2 -NH 2 and Ag@TiO 2 Janus nanoparticles were analyzed by thermogravimetry (TG) analyzer (STA449F3-1053-M). The heating rate was 10 ℃/min and the temperature range was 40 ℃~ 800 ℃. The hydrophobic property of the fabric surface was estimated by measuring WCA using a contact angle 140 goniometer (DM-700, Kyowa). The microstructure of the sample and the dispersion state of Janus particles on the fibers of cotton fabric were observed and tested by Japanese S4800 scanning electron microscope, and the elements on the surface of the sample were analyzed by EDS. 2.6 Performance test of multifunctional cotton fabric 2.6.1 Hydrophobic durability test Dye water of different colors were prepared, and 0.50 µL drops were absorbed on the surface of cotton fabric by pipetting gun, and the existing state of drops on the surface of cotton fabric was observed. The cotton fabric were placed in a watch glasses filled with distilled water, and observed that the cotton fabric were kept at the liquid level. The modified cotton fabric were stirred in hot water at 80 ℃ for 3 h, followed by taking out and drying to measure the contact angle of the cotton fabric. The above steps were one cycle, and the hydrophobic durability was investigated through multiple cycles. In order to simulate the harsh corrosive environment, the modified cotton fabric were washed under different pH and solvent conditions or rubbed repeatedly to test its hydrophobic durability. 2.6.2 Antibacterial property test According to the standard QBT4341-2012, the antibacterial property of fabrics was tested by the bacteriostatic circle method. Modified culture medium, culture dish and phosphate (PBS) buffer were sterilized in autoclave, followed by pouring the cuiture medium into the culture dish under the ultra-clean workbench. E. coli and S. aureus were diluted with 20 mL PBS to obtain suspension. After the culture medium was cooled and solidified, 1.50 mL of suspension was removed from the culture medium and evenly coated with a coater. The circular fabric cut into 1 cm diameter (UV sterilized) was placed right in the middle of the culture medium, placed upside down in a constant temperature and humidity box, and cultured at 37 ℃. The growth of bacteria was observed after 24–48 h intervals. 2.6.3 Superhydrophobic stability test A small amount of chromium powder were put on the modified cotton fabric. Then the modified cotton fabric surface was washed with distilled water to observe the movement state of water droplets and chromium powder on the cotton fabric surface; The modified cotton fabric were contaminated with castor oil or rhodamine B dye to observed the degradation effect of the cotton fabric on the pollutants. 2.6.4 Laundry resistance test The laundry resistance of the modified cotton fabric were evaluated according to the test method of colony count (GB 4789.3–2016 and GB 4789.10–2016). The particle-treated cotton fabric were washed with an ultrasonic cleaner at an ultrasonic frequency of 40 kHz and an ultrasonic power of 180 W. Each washing cycle lasted for 30 min and the antibacterial rate of the modified cotton fabric treated in different washing cycles were detected. 3. Results and discussion 3.1 Synthesis of Ag@TiO 2 microspheres The morphologies of the Ag/C templates and Ag@TiO 2 microspheres were observed by SEM. The Ag/C templates were regular spheroids with uniform size and smooth surface without adhesion (Fig. 2 a). The Ag@TiO 2 microspheres were approximately 400 ~ 600 nm in diameter in the SEM image (as shown in Fig. 2 b). Compared with the surface of the original smooth Ag/C templates, the surface of the Ag@TiO 2 microspheres become rough, indicating that the templates surfaces were covered with TiO 2 layers, forming well-dispersed Ag@TiO 2 microspheres. The broken microspheres in Fig. 2 b could be seen to have shell structure. EDS result revealed the surface element distribution of Ag@TiO 2 microspheres as shown in Fig. 2 c. The distribution of Ti and O elements was very obvious. At the same time, a small amount of Ag element also appeared. This was mainly because in the calcination process of removing the template, with the disappearance of the carbon balls, the particles reduced into nano-Ag in the template remained in the TiO 2 shell. As the melting point of nano-silver was only 100 ℃, the Ag nano-core melted first during the calcination process at 450 ℃, and a small amount gradually seeped out of the TiO 2 shell and adhered to the hollow sphere TiO 2 shell, so Ag element also had a small distribution [ 25 ] . The XRD curves of nano-Ag, nano-TiO 2 and nano-Ag@TiO 2 microspheres were displayed in Fig. 2 d. The diffraction peaks of nano-Ag curves all appeared at 2θ = 38.2, 44.5 and 63.8, corresponding to (111), (200) and (220) crstallographic plane of silver respectively [ 26 ] . The obvious characteristic diffraction peaks in the nano-TiO 2 curve appeared around 2θ = 25.3, 38.1, 48.0, 53.8, 55.1 and 62.8, corresponding to (101), (004), (200), (105) and (211) crstallographic plane of anatase respectively [ 27 ] . In the curve of nano Ag@TiO 2 microspheres, besides the diffraction peak of anatase TiO 2 , the diffraction peak of nano silver appeared correspondingly, which indicated the silver was loaded on anatase TiO 2 . 3.2 Synthesis of Ag@TiO 2 Janus particles In order to prove the amphiphilicity of Ag@TiO 2 Janus nanoparticles, the Ag@TiO 2 microspheres were respectively modified by KH-550 (HO-Ag@TiO 2 -NH 2 ) and OTDS (C 18 -Ag@TiO 2 ) to endow the Ag@TiO 2 hydrophilicity and hydrophobicity. HO-Ag@TiO 2 -NH 2 , Ag@TiO 2 Janus nanoparticles and C 18 -Ag@TiO 2 were dispersed in the mixed system of methyl methacrylate and water respectively, and its dispersion states were compared, as shown in Fig. 3 a. The HO-Ag@TiO 2 -NH 2 microspheres with hydrophilic amino groups on the surface only dispersed in the lower water phase of the system, hydrophobic C 18 -Ag@TiO 2 microspheres with long-chain alkanes only dispersed in the upper oil phase of the system, and amphiphilic Ag@TiO 2 Janus nanoparticles stably existed in the oil-water interface. It indicated that Ag@TiO 2 Janus nanoparticles not only had both hydrophilic and hydrophobic segments, but also had stable amphiphilicity. In order to further explored the structural characteristics of Ag@TiO 2 Janus nanoparticles, silver labeling method was used to characterize (Fig. 3 b). As could be seen that the Ag@TiO 2 nanoparticles with a size of about 500 nm had a hollow structure, and the silver nanoparticles were clearly labeled on one side of the Ag@TiO 2 Janus nanoparticles. Therefore, the surface groups of the synthesized Ag@TiO 2 Janus nanoparticles were asymmetrically distributed, which further proved that the particles had Janus structural characteristics. The average particles size of unmodified Ag@TiO 2 , HO-Ag@TiO 2 -NH 2 and Ag@TiO 2 Janus particles were displayed in Fig. 3 c. The particles size of unmodified Ag@TiO 2 microspheres was 495 nm, that of HO-Ag@TiO 2 -NH 2 particles modified by silane coupling agent KH-550 was 515 nm, and that of Ag@TiO 2 Janus nanoparticles modified by amphiphilic modification was 627 nm. The average particles size of the three kinds of particles gradually increased with the increase of modification degree. In order to exist stably, the hydrophobic sides of amphiphilic Ag@TiO 2 Janus nanoparticles were as close as possible to reduce the contact area between hydrophobic sides and water, which caused the agglomeration state of the particles in the system to a greater extent and made the size of Ag@TiO 2 Janus nanoparticles increase. As shown in the Fig. 4 a, the unmodified Ag@TiO 2 , HO-Ag@TiO 2 -NH 2 and Ag@TiO 2 Janus particles were characterized by infrared spectroscopy. The FT-IR curves of unmodified Ag@TiO 2 microspheres had obvious O-H anti-symmetric stretching vibration absorption peaks and bending vibration absorption peaks at 3427 cm − 1 and 1630 cm − 1 , and the absorption peaks at 500–700 cm − 1 were characteristic absorption peaks of Ti-O and Ti-O-Ti of inorganic TiO 2 . As could be seen from the curve of HO-Ag@TiO 2 -NH 2 particles, the intensity of O-H absorption peak at 3427 cm − 1 was weaker than that of Ag@TiO 2 , which proved that silane coupling agent KH-550 had a condensation reaction with hydroxyl groups on the surface of Ag@TiO 2 , and the grafting of hydrophilic segments reduced the number of hydroxyl groups, thus affecting its absorption peak intensity. The peaks at 2908 cm − 1 and 2834 cm − 1 were the stretching vibration peaks of C-H in KH-550, and the wider peaks at 1030 cm − 1 and 661 cm − 1 were the stretching vibration peaks of C-N and the out-of-plane bending vibration peaks, respectively, and the stretching vibration peaks of Si-O in KH-550 at 1136 cm − 1 , thus indicating KH-550 was successfully grafted onto the surface of Ag@TiO 2 microspheres. Due to the OTDS had long -chain alkyl group, the stretching vibration peaks of C-H at 2908 cm − 1 and 2834 cm − 1 were stronger than those of HO-Ag@TiO 2 -NH 2 , and a strong bending vibration peak of C-H appears at 1470 cm − 1 . Therefore, the amphiphilic Ag@TiO 2 Janus nanoparticles were successfully prepared. According to the TG curve analysis of Ag@TiO 2 , HO-Ag@TiO 2 -NH 2 and Ag@TiO 2 Janus particles, the grafting amount of hydrophilic segment of KH-550 and hydrophobic segment of OTDS on the surface of Ag@TiO 2 microspheres were estimated, as shown in Fig. 4 b. The mass loss of unmodified Ag@TiO 2 microspheres was 2.47% in the temperature range of 25–800℃, which was mainly due to the adsorption of water, hydroxyl and oxidant on the surface of Ag@TiO 2 . It could be seen from the figure that the TG curve of HO-Ag@TiO 2 -NH 2 particles had three weight loss stages in the temperature range of 25–800 ℃, which was mainly caused by the volatilization of adsorbed water contained in the particles and the breakage of C-C bond on the hydrophilic segment grafted on the surface of Ag@TiO 2 . It indicated that KH-550 was grafted on the Ag@TiO 2 microspheres. TG curve of Ag@TiO 2 Janus nanoparticles also had three stages of thermal decomposition, which mainly caused by the free water and bound water in the particles were the main losses in the temperature range of 25–280 ℃, the breakage of C-C bonds on a large number of hydrophilic and hydrophobic segments grafted on the surface of Ag@TiO 2 in the temperature of 281–495 ℃ and the Si-O bond of KH-550 and ODTS grafted on Ag@TiO 2 was decomposed and lost weight in the temperature range of 496–800 ℃. Compared the mass loss of HO-Ag@TiO 2 -NH 2 and Ag@TiO 2 Janus nanoparticles in the second and third stages, the mass loss of Ag@TiO 2 Janus nanoparticles was greater than that of HO-Ag@TiO 2 -NH 2 , which indicated that a large number of hydrophobic segments were grafted on the surface of Ag@TiO 2 Janus nanoparticles. The amount of hydrophilic and hydrophobic segments grafted on Ag@TiO 2 Janus nanoparticles was estimated to be about 2.49% and 5.47%, respectively. 3.3 Preparation and characterization of multifunctional cotton fabric The SEM photograph of epoxy modified cotton fabric treated with Ag@TiO 2 Janus nanoparticles with different concentrations were shown in Fig. 5 . When the concentration of Ag@TiO 2 Janus nanoparticles was 1.5%, only a very small number of Ag@TiO 2 Janus nanoparticles were dispersed on the cotton fiber, so the contact angle of the Ag@TiO 2 Janus/E-cotton fabric was only 95, and the hydrophobic property was unsatisfactory. When the concentration was increased to 2.0%, the coating amount of Ag@TiO 2 Janus nanoparticles on the fiber surface increased, and the contact angle increased to 125. When the concentration was 2.5%, the contact angle reached the maximum of 160. As seen from Fig. 5 c that Ag@TiO 2 Janus nanoparticles not only wrapped tightly on the surface of the fiber, but also formed rugged dome-shaped clusters, and constructed multi-level rough structure, which could effectively improve the hydrophobicity of the fabric. Meanwhile, EDS analysis was performed on the cotton fabric modified by Ag @ TiO 2 Janus nanoparticles with the concentration of 2.5%. It could be seen from the figure that the Ti element was uniformly distributed, indicating that Ag@TiO 2 Janus nanoparticles were uniformly grafted onto the cotton fabric. Since the introduction amount of Ag in the Ag@TiO 2 microspheres was relatively small, the distribution of Ag element was relatively uniform but very small. As the silane coupling agents KH-550 and OTDS carried out amphiphilic modification on Ag@TiO 2 microspheres, the distribution of Si element appeared in the EDS spectrum of the Ag@TiO 2 Janus/E-cotton fabric. The distribution of C and N elements in the Ag@TiO 2 Janus/E-cotton fabric could also be seen in the figure, but the distribution of C element in the figure was more significant, which may be due to the large number of hydrophobic OTDS grafted onto Ag@TiO 2 microspheres. E-cotton fabric and Ag@TiO 2 Janus/E-cotton fabric were characterized by FT-IR, in order to detect the chemical bonding between Ag@TiO 2 Janus nanoparticles and epoxy groups on the surface of cotton fabric,as observed in Fig. 6 . The FT-IR curve of E-cotton fabric had a peak at 910 cm − 1 , which was the characteristic absorption peak of C-O-C from the epoxy group grafted on the surface of cotton fabric. From the curve of Ag@TiO 2 Janus/E-cotton fabric, it could be seen that the characteristic absorption peak intensity of C-O-C at 910 cm − 1 was obviously weaker than that of E-cotton fabric, which indicated that the amino groups on Ag@TiO 2 Janus nanoparticles reacted with epoxy groups on cotton fabric. 3.4 Application of multifunctional cotton fabric 3.4.1 Superhydrophobic durability In order to directly observe the hydrophobic effect of Ag@TiO 2 Janus/E-cotton fabric, the dyed water droplets were dropped on the cotton fabric, and the state of the dyed water droplets on the surface of cotton fabric was observed. As could be seen from Fig. 7 a, when the dyed water droped on the surface of unmodified raw cotton fabric, the water drops immediately collapsed, which was related to the presence of hydroxyl groups on the surface of the fibers and the capillary effect caused by the voids between fibers. Figure 7 b was a photo of water droplets placed on the surface of Ag@TiO 2 Janus/E-cotton fabric. The hydrophobic long-chain alkyl group on the one side of the Ag@TiO 2 Janus nanoparticles endowed the finished fabrics with the ability to repel liquids. The liquid droplets all maintain a spherical shape on the finished fabric and did not absorb into it. Figure 7 (c-d) shown the placing phenomenon of cotton fabric in aqueous solution before and after modification, in which 1 # was the original cotton fabric and 2 # was the cotton fabric modified by Ag@TiO 2 Janus nanoparticles. According to observe the placing state of the two cotton fabric in water, the hydrophobicity of the cotton fabric before and after modification could be detected. As shown in Fig. 7 c, when the cotton fabric were clamped on one side of the cotton fabric sample with tweezers and the other side was placed in water, the half of the unmodified raw cotton fabric easily immersed in water and dyed. Due to Ag@TiO 2 Janus/E-cotton fabric had good hydrophobic property, it was dyed without absorbing the aqueous solution. As shown in Fig. 7 d, when the original cotton fabric and Ag@TiO 2 Janus/E-cotton fabric were directly placed in the watch glasses of dyeing aqueous solution, the original cotton fabric would soon absorb water and sink, while the Ag@TiO 2 Janus/E-cotton fabric could still float above the liquid level after being placed, which indicated that the Ag@TiO 2 Janus/E-cotton fabric had good hydrophobic performance. Ag@TiO 2 Janus nanoparticles and epoxy-containing cotton fabric were bonded by stable chemical bonds, so the durability of Ag@TiO 2 Janus/E-cotton fabric was tested in various ways. For comparative study, the Ag@TiO 2 microspheres were hydrophobically modified by OTDS, so that only long-chain alkanes were grafted on their surfaces, and no amino groups that reacted with epoxy groups(C 18 -Ag@TiO 2 ). The particles were applied to cotton fabric finishing, and the obtained cotton fabric were named C 18 -Ag@TiO 2 /E-cotton fabric. The changing trend of water contact angle of Ag@TiO 2 Janus/E-cotton fabric and C 18 -Ag@TiO 2 /E-cotton fabric after long-time washing at 80 ℃ was investigated, as observed in Fig. 8 a. The two kinds of cotton fabric had the same original contact angle of 160. Compared with C 18 -Ag @ TiO 2 /E-cotton fabric, the contact angle of Ag@ TiO 2 /E-cotton fabric had a smaller change trend with time, which was the strong chemical bonding between the particles and the cotton fabric, so it could still maintain a good contact angle. Figure 8 b investigated the influence of friction cycles on the contact angle of fabrics. After friction cycles, both Ag@TiO 2 Janus/E-cotton fabric and C 18 -Ag@TiO 2 /E-cotton fabric were worn. Compared with the initial contact angle of 160 before friction loss, the contact angle of Ag@TiO 2 Janus/E-cotton fabric after friction treatment had a little decreasing trend in comparison to that of C 18 -Ag@TiO 2 /E-cotton fabric. From the photos in the figure, the water droplets in the damaged area of Ag@TiO 2 Janus/E-cotton fabric were still full, which indicated that Ag@TiO 2 Janus/E-cotton fabric still maintained the hydrophobic effect after abrasion. Figure 8 c presented the change of contact angle of Ag@TiO 2 Janus/E-cotton fabric under the condition of extreme pH solution and mechanical stirring. As seen that the contact angle of cotton fabric had almost unchangable with the stirring time, comparing with acidic or alkaline solution. On the one hand, the hydrophobic property of cotton fabric was provided by the covalent bond between the hydrophilic amino group of Ag@TiO 2 Janus nanoparticles and the epoxy group on the fiber, and the hydrophobic side was provided to the environment; On the other hand, the aggregation formed by self-assembly of Ag@TiO 2 Janus nanoparticles deposited on cotton fabric fibers to form a multi-level rough structure, which further improved the hydrophobic property of the fabrics. Therefore, when the hydrophobic cotton fabric were treated in an acid-base solution, the acid-base environment destroyed the non-covalent bonds between particle aggregates deposited on the surface of the cotton fabric, affected the assembly state of the particles, thus destroyed the multi-level rough structure on the cotton fabric, and finally weakened the hydrophobic property of the cotton fabric, resulted in the decrease of the contact angle. Figure 8 d was shown the influence of different solvent soaking treatments on the contact angle of Ag@TiO 2 Janus/E-cotton fabric. It could be seen from the figure that solvents such as absolute ethyl alcohol, cyclohexane, toluene, tetrahydrofuran and dimethylformamide had no obvious influence on the hydrophobic effect of cotton fabric. Especially, the contact angle of the modified cotton fabric treated with absolute ethanol slightly increased, which might be due to the rapid volatilization of ethanol, and the roughness induced by phase separation increased the contact angle of the treated fabrics by nearly 6. Ag@TiO 2 Janus/E-cotton fabric and C 18 -Ag@TiO 2 /E-cotton fabric were washed by ultrasonic, and the micro-morphology of cotton fabric before and after treatment was investigated. As shown in Fig. 9a 1 and Fig. 9b 1 , the fiber scanning photos of Ag@TiO 2 Janus/E-cotton fabric and C 18 -Ag@TiO 2 /E-cotton fabric before treatment were not much different, and the fiber surfaces of the two kinds of fabrics were densely coated with nanoparticles. Because the particles were grafted with hydrophobic segments, the initial water contact angles of the two kinds of cotton fabric were not much different, which were 160 and 161 respectively. From the photo of Ag@TiO 2 Janus/E-cotton fabric after ultrasonic water washing SEM in Fig. 9a 2 , there were still many particles that were evenly grafted on the surface of the fiber through chemical bonding. At this time, the contact angle was reduced to 152, but it still had excellent hydrophobic properties. After the C 18 -Ag@TiO 2 /E-cotton fabric were treated, due to the lack of chemical bonding between the particles and the cotton fabric, a large number of nanoparticles were fell off, and the water contact angle of the cotton fabric was decreased to 81, as displayed in Fig. 9b 2 . The EDS spectra of Ag@TiO 2 Janus/E-cotton fabric and C 18 -Ag@TiO 2 /E-cotton fabric after ultrasonic water washing were shown in Fig. 9a 3 and Fig. 9b 3 . There were elements of C, O, Ti, Ag and Si on the surface of cotton fiber after finishing with Ag@TiO 2 Janus and C 18 -Ag@TiO 2 nanoparticles, which indicated that the particles exist in cotton fabric. 3.4.2 Antibacterial durability In general, bacteria were easily attached to fabrics when it is worn for a long time, so the antibacterial performance of modified fabrics was important to assess. As shown in Fig. 10 , comparing the cotton fabric modified by different materials, it intdicated that Ag@TiO 2 Janus/ E-cotton fabric has excellent antibacterial properties against E. coli and S. aureus . According to the results in Fig. 10 (a 1 , a 2 , b 1 , b 2 ), no bacteriostatic rings appeared around the control cotton fabric, whether for E. coli or S. aureus. But the TiO 2 / E-cotton fabric was a slight inhibition zone around the TiO 2 nanoparticles treated cotton fabric for E. coli and S. aureus . This was mainly due to the fact that TiO 2 can generate electron/hole (e − / h + ) and further produces reactive oxygen species, such as .OH, O 2 − and H 2 O 2 , which can degrade bacterial proteins and lead to inhibition of biological growth. Comparing with TiO 2 / E-cotton fabric, Ag@TiO 2 nanoparticles treated cotton fabric presented obviously 3–4 mm inhibition zone for E. coli or S. aureus (Fig .10(a 3 ,b 3 )). It was mainly attribute to the induction of electron transfer from metallic silver to TiO 2 resonance after the addition of Ag, which lead to charge separation, inhibited electron-hole coincidence and promoted the generation of active oxygen, thus improving its antibacterial performance. Comparing with Ag@TiO 2 / E-cotton fabric, Ag@TiO 2 Janus nanoparticles finished cotton fabric showed excellent antibacterial performance against E. coli or S. aureus , which appeared 7–8 mm inhibition zone for E. coli or S. aureus (Fig .10(a 4 ,b 4 )). Due to the hydrophobic nature of the fiber surface after finishing with Ag@TiO 2 Janus particles ensure weaken the adhesion of bacteria to the substrate, thus achieving a synergistic antibacterial effect to endow with the Ag@TiO 2 Janus cotton fabric excellent antibacterial properties. The antibacterial durability of the cotton fabric finished with Ag@TiO 2 Janus nanoparticles against E. coli and S. aureus was shown in Fig. 11 . From the figure, the unwashed cotton fabric had excellent antibacterial effect, and the antibacterial rate reached over 99%. After 8 cycles of ultrasonic washing, the antibacterial rate of cotton fabric finished with Ag@TiO 2 Janus nanoparticles to E. coli and S. aureus still be kept above 85%, and the decrease was not significant compared with the antibacterial rate before washing. Ag@TiO 2 Janus/E-cotton fabric had excellent and lasting antibacterial properties to E. coli and S. aureus . The strong antibacterial activity was due to the excellent photocatalytic performance of Ag@TiO 2 Janus nanoparticles and the dual action of Ag + release. After 8 washing cycles, Ag@TiO 2 Janus/E-cotton fabric still showed high antibacterial activity against two kinds of bacteria, which indicated that the amino groups on Ag@TiO 2 Janus nanoparticles could form covalent bonds with epoxy groups on cotton fibers, which ensured that even under the strong washing action, the nanoparticles could still stably exist on the surface of cotton fibers, giving them long-term antibacterial activity. 3.4.3 Ultraviolet protection performance The transmission of E-cotton fabric and Ag@TiO 2 Janus/E-cotton fabric under ultraviolet irradiation was shown in Fig. 12 . It could be seen from the figure that, compared with E-cotton fabric, the lowest ultraviolet transmittance of Ag@TiO 2 Janus/E-cotton fabric in the ultraviolet band between 200 and 400 nm was reduced to about 20%, which indicated that the transmittance of cotton fabric treated with Ag@TiO 2 Janus nanoparticles in the ultraviolet region was significantly reduced. The results indicated that the application of Ag @ TiO 2 Janus nanoparticles to cotton fabric endowed the cotton fabric with anti-ultraviolet characteristics. 3.4.4 Wearability Test results of mechanical properties, softness, whiteness index and air permeability of raw cotton fabric, E-cotton fabric and Ag@TiO 2 Janus/E-cotton fabric were observed in Fig. 13 . Compared with the original cotton fabric, the tensile strength and elongation at break of E-cotton fabric and Ag@TiO 2 Janus/E-cotton fabric decreased slightly(Fig. 13 a). As could be seen from Fig. 13 b, compared with the original cotton fabric, the softness of the E-cotton fabric was almost unchanged, and the softness of the Ag@TiO 2 Janus/E-cotton fabric was obviously decreased, which was mainly due to the fact that the surface and voids of the fibers of the Ag@TiO 2 Janus/E-cotton fabric were grafted and filled with a large number of nanoparticles, and a certain rough structure was formed on the surface, which hindered the slippage between fibers, thus causing the softness of the cotton fabric. The whiteness index of cotton fabric finished with Ag@TiO 2 Janus nanoparticles had obviously decreased, which was due to the gray color of Ag@TiO 2 Janus nanoparticles, which had obvious influence on the whiteness index of Ag@TiO 2 Janus/E-cotton fabric, as displayed in Fig. 13 c. The air permeability of E-cotton fabric decreased slightly, which was due to a large number of organic segments of KH-560 grafted on cotton fibers, which hindered the gas from passing between cotton fibers, as demonstrated in Fig. 13 d. However, the air permeability of Ag@TiO 2 Janus/E-cotton fabric was basically unchanged, which might be due to the porous structure of TiO 2 shell of Ag@TiO 2 Janus nanoparticles, so the grafting of nanoparticles on cotton fabric did not affect the air permeability of the fabrics. 4.Conclusion For development of multifunctional durable cotton fabric, the two sides of Ag@TiO 2 microspheres respectively were carried aminosilane coupling agent and long-chain alkane to form an asymmetric Janus structure, and a multifunctional cotton fabric with durably superhydrophobic, antibacterial and UV resistance was prepared. FT-IR and TG characterization showed that the surface of Ag@TiO 2 microspheres was grafted with amino groups and long-chain alkanes, with the grafting amounts of 2.49% and 5.47% respectively. The stable state of Janus nanoparticles at the oil-water interface and TEM showed that the nanoparticles had typical amphiphilic Janus structure. Ag@TiO 2 Janus nanoparticles with different concentrations were used for cotton fabric finishing and modification. When the concentration of the Ag@TiO 2 Janus nanoparticles was 2.5%, the surface of cotton fibrics formed multi-level rough structure, and the contact angle of the fabric was 160. Ag@TiO 2 Janus nanoparticles were covalently grafted onto cotton fabric, and after high-temperature washing, abrasion and different chemical solvent treatments, it still maintained great hydrophobic durability. The antibacterial rate of Ag@TiO 2 Janus/E-cotton fabric to E. coli and S. aureus could be kept above 80% after 8 cycles of ultrasonic washing. In addition, the lowest ultraviolet transmittance of Ag@TiO 2 Janus/E-cotton fabric in the ultraviolet band of 200 ~ 400 nm could be reduced to about 20%. Declarations Acknowledgements The authors acknowledge the support for this study from the Key Project of Natural Science Basic Research Program of Shaanxi Province (Special Support, 2023JC-XJ-12). Authors contributions Dangge Gao conceived the concept, supervised the project and provided financial support and thoughts of manuscript. Fangxing Wang performed the experiment, prepared the samples and did the manuscript and analysis. Zhouyang Zhao performed the experiment and provided thought. Lyu Bin provided manuscript retouching and fund support. Jianzhong Ma provided the thought, manuscript retouching and fund. Funding This work was carried out with support from the Key Project of Natural Science Basic Research Program of Shaanxi Province (Special Support, 2023JC-XJ-12). Conflict of interest The authors declare no conflict of interest. Ethics approval All authors have understood and complied with the code of ethics, approved, and agreed to participate. Consent for publication All authors agreed to publish the paper. 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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Microporous and Mesoporous Materials, 314: 110856. https://doi.org/10.1016/j.micromeso.2020.110856 Gao S, Li H, Zheng L, et al (2021). Superhydrophobic and conductive polydimethylsiloxane/titanium dioxide@ reduced graphene oxide coated cotton fabric for human motion detection[J]. Cellulose, 28: 7373–7388. https://doi.org/10.1007/s10570-021-03951-2 Additional Declarations No competing interests reported. Supplementary Files Graphicformanuscript.docx Cite Share Download PDF Status: Published Journal Publication published 29 Jan, 2024 Read the published version in Cellulose → Version 1 posted Editorial decision: Major revision 24 Jul, 2023 Submission checks completed at journal 24 Jul, 2023 Editor assigned by journal 24 Jul, 2023 First submitted to journal 21 Jul, 2023 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. 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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-3191198","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":220986595,"identity":"e991009d-f8dd-4fe7-89d5-6aaa1d10535b","order_by":0,"name":"Dangge Gao","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA10lEQVRIiWNgGAWjYDCCA2DShoeNmfnAgQ8VxGtJk+Nnb0s8OOMM8VoOG0v2nDE+zNtChA6+42cPv/xSwZy44UbOhwO8DQzy/GIH8GuRPJOXZi1zhg2oJXfDAckdDIYzZyfg12JwIMfMWLKNB6LF8AxDgsFtQlrOvwFq+ScBctiDA4ltxGi5kWP88GODAcj7DAcOEqNF8sYbM2aGYwmgQDY42HBGgrBf+M7nGH/8UfMfFJWPP/+psJHnlyagBQjYpHkQHAmCykGA+eMPotSNglEwCkbBiAUAWf9Q0btxVYMAAAAASUVORK5CYII=","orcid":"","institution":"Shaanxi University of Science and Technology","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Dangge","middleName":"","lastName":"Gao","suffix":""},{"id":220986596,"identity":"f7fcdcf5-2401-40ee-beb8-54700f5af7b8","order_by":1,"name":"Fangxing Wang","email":"","orcid":"","institution":"Shaanxi University of Science and Technology","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Fangxing","middleName":"","lastName":"Wang","suffix":""},{"id":220986597,"identity":"a78ebe66-b248-403b-b450-78a8343c5aea","order_by":2,"name":"Bin Lyu","email":"","orcid":"","institution":"Shaanxi University of Science and Technology","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Bin","middleName":"","lastName":"Lyu","suffix":""},{"id":220986598,"identity":"2e7afe49-c8d9-4a8a-ac16-896d134e308f","order_by":3,"name":"Jianzhong Ma","email":"","orcid":"","institution":"Shaanxi University of Science and Technology","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Jianzhong","middleName":"","lastName":"Ma","suffix":""},{"id":220986599,"identity":"1d5f3cc4-4472-4b03-b91c-52df329a36f3","order_by":4,"name":"Zhouyang Zhao","email":"","orcid":"","institution":"Shaanxi University of Science and Technology","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Zhouyang","middleName":"","lastName":"Zhao","suffix":""}],"badges":[],"createdAt":"2023-07-21 08:59:25","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3191198/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3191198/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10570-023-05727-2","type":"published","date":"2024-01-29T15:00:48+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":40664516,"identity":"308b1fba-bfa6-4727-8abc-648a8fa47c72","added_by":"auto","created_at":"2023-07-27 14:20:49","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":276945,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic illustration of the synthesis of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus particles and finishing cotton fabric with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus particles\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/83597b1c148a4447e68b36b5.png"},{"id":40664523,"identity":"9084f99a-4413-4962-9453-7a1cda2da460","added_by":"auto","created_at":"2023-07-27 14:20:49","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":118012,"visible":true,"origin":"","legend":"\u003cp\u003eSEM images of\u003cstrong\u003e \u003c/strong\u003e(a) Ag/C templates and (b) Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres. EDS spectrum of (c) Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres. XRD curves of (d) nano Ag, nano TiO\u003csub\u003e2\u003c/sub\u003e and nano Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/8bf1f0c68275f49192077dba.png"},{"id":40664518,"identity":"02fc49bb-82cd-42c0-b152-18f65a24feca","added_by":"auto","created_at":"2023-07-27 14:20:49","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":240752,"visible":true,"origin":"","legend":"\u003cp\u003ea) dispersion state of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e((a)), Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus((b)) and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e((c)) at the interface between methyl methacrylate and deionized water , (b) TEM photos of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles labeled with silver and (c) Average particles size graph of unmodified Ag@TiO\u003csub\u003e2\u003c/sub\u003e, HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/d07c45264a86da0e7bca8cad.png"},{"id":40665618,"identity":"9e7e9432-bbca-4439-8f6f-a4a480d011a6","added_by":"auto","created_at":"2023-07-27 14:28:49","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":39002,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003e(\u003c/strong\u003ea) FT-IR spectra and (b) TG curves of Ag@TiO\u003csub\u003e2\u003c/sub\u003e, HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus 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14:36:49","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":12384,"visible":true,"origin":"","legend":"\u003cp\u003eFT-IR spectra of E-cotton fabric and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/9acb6d0dd1f6cbb6d691d236.png"},{"id":40664526,"identity":"c4420c7b-6084-4682-ad6c-71453af77a62","added_by":"auto","created_at":"2023-07-27 14:20:49","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":390202,"visible":true,"origin":"","legend":"\u003cp\u003ePlacement of dyed water droplets on raw cotton fabric (a) and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/750c8dd2d04921d29fe5c7e8.png"},{"id":40664520,"identity":"0ea73244-4b7d-4843-ac76-64444a6d2507","added_by":"auto","created_at":"2023-07-27 14:20:49","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":48984,"visible":true,"origin":"","legend":"\u003cp\u003eChanges of contact angles of Ag @ TiO\u003csub\u003e2 \u003c/sub\u003eJanus/e-cotton fabric and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric with (a) high temperature washing, (b) wear cycle, (c)pH value and (d) different organic solvent treatments\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/481a67da2aec28ceae1f73a4.png"},{"id":40665619,"identity":"87601d7c-a52f-4d72-b0e5-4ea8196fb690","added_by":"auto","created_at":"2023-07-27 14:28:49","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":258345,"visible":true,"origin":"","legend":"\u003cp\u003eSEM photos of Ag @ TiO\u003csub\u003e2\u003c/sub\u003e Janus/e-cotton fabric (a\u003csub\u003e1\u003c/sub\u003e-a\u003csub\u003e3\u003c/sub\u003e) and C\u003csub\u003e18\u003c/sub\u003e-Ag @ TiO\u003csub\u003e2\u003c/sub\u003e/e-cotton fabric (b\u003csub\u003e1\u003c/sub\u003e-b\u003csub\u003e3\u003c/sub\u003e) before and after ultrasonic treatment (a\u003csub\u003e1\u003c/sub\u003e, b\u003csub\u003e1\u003c/sub\u003e- before water washing; a\u003csub\u003e2\u003c/sub\u003e, b\u003csub\u003e2\u003c/sub\u003e- after water washing) and EDS spectra after water washing\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/f935a89db62580a70900ee1d.png"},{"id":40664528,"identity":"36c44bb2-6a8b-4b49-952e-d5295b557773","added_by":"auto","created_at":"2023-07-27 14:20:49","extension":"png","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":305851,"visible":true,"origin":"","legend":"\u003cp\u003eThe photograph of antibacterial effect of raw cotton fabric (a\u003csub\u003e1\u003c/sub\u003e, b\u003csub\u003e1\u003c/sub\u003e), TiO\u003csub\u003e2\u003c/sub\u003e/ E-cotton fabric (a\u003csub\u003e2\u003c/sub\u003e, b\u003csub\u003e2\u003c/sub\u003e), Ag@TiO\u003csub\u003e2\u003c/sub\u003e/ E-cotton fabric (a\u003csub\u003e3\u003c/sub\u003e,b\u003csub\u003e3\u003c/sub\u003e) and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/ E-cotton fabric (a\u003csub\u003e4\u003c/sub\u003e,b\u003csub\u003e4\u003c/sub\u003e) against \u003cem\u003eE.coli\u003c/em\u003e (a) and \u003cem\u003eS.aureus\u003c/em\u003e (b).\u003c/p\u003e","description":"","filename":"10.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/e1b3efe37f31f1bc9a04d0b3.png"},{"id":40665622,"identity":"7df19df9-5cec-44a9-a95a-c17e7315225a","added_by":"auto","created_at":"2023-07-27 14:28:49","extension":"png","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":9679,"visible":true,"origin":"","legend":"\u003cp\u003eantibacterial rate of Ag @ TiO\u003csub\u003e2\u003c/sub\u003e Janus/e-cotton fabric after ultrasonic water washing treatment\u003c/p\u003e","description":"","filename":"11.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/f886e89b5db96b37b18a982b.png"},{"id":40665623,"identity":"9c603ded-5efc-460b-95e8-279d09bad8a1","added_by":"auto","created_at":"2023-07-27 14:28:49","extension":"png","order_by":12,"title":"Figure 12","display":"","copyAsset":false,"role":"figure","size":14528,"visible":true,"origin":"","legend":"\u003cp\u003eUV protection performance of the E-cotton fabric and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric\u003c/p\u003e","description":"","filename":"12.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/e4dcf51f5ad53027b7b2e6d2.png"},{"id":40664524,"identity":"5ac6fc7d-a69e-44d3-bad9-5f723b0af729","added_by":"auto","created_at":"2023-07-27 14:20:49","extension":"png","order_by":13,"title":"Figure 13","display":"","copyAsset":false,"role":"figure","size":41910,"visible":true,"origin":"","legend":"\u003cp\u003ePhysical and mechanical strength (a), softness (b), whiteness (c) and air permeability (d) of the cotton fabric before and after modification\u003c/p\u003e","description":"","filename":"13.png","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/cde4b44c14133c8a9ddb7848.png"},{"id":50673806,"identity":"2dd4269f-d8c7-4ac8-8c65-c3337c8b68ab","added_by":"auto","created_at":"2024-02-05 15:06:25","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2443656,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/e3621e74-8a02-42a9-a4a7-f7b768c5ec94.pdf"},{"id":40666872,"identity":"55e705e9-7bf5-4718-a387-02a50f65ddba","added_by":"auto","created_at":"2023-07-27 14:36:49","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":2981141,"visible":true,"origin":"","legend":"","description":"","filename":"Graphicformanuscript.docx","url":"https://assets-eu.researchsquare.com/files/rs-3191198/v1/cca5a463370a33bd51c1c71d.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Multifunctional cotton fabric with durable antibacterial, superhydrophobicity, and UV resistance based on Ag@TiO 2 Janus nanoparticles","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003ecotton fabrics, one of the most common natural fiber textiles, are widely used in daily life by virtue of great softness\u003csup\u003e[\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]\u003c/sup\u003e, low cost and air permeability\u003csup\u003e[\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]\u003c/sup\u003e. With the improvement of the quality of life, endowing cotton fabric multiple functions has become the mainstream trend of high-quality development of the textile industry\u003csup\u003e[\u003cspan additionalcitationids=\"CR6\" citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]\u003c/sup\u003e. In particularly, under the current situation of frequent epidemic diseases, people's daily clothes and medical materials need to inhibit the growth and transmission of bacteria, reduce the adhesion between bacterial cells and materials surface and prevent the penetration of water droplets\u003csup\u003e[\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]\u003c/sup\u003e. At the same time, people's daily clothes and medical materials should have anti-ultraviolet performance, mainly because the ozone layer is constantly destroyed, resulting in enhanced ultraviolet radiation, which is harmful to human skin health, such as skin aging, photosensitive rash and skin cancer\u003csup\u003e[\u003cspan additionalcitationids=\"CR10 CR11\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]\u003c/sup\u003e. Therefore, the design of multifunctional cotton fabric with antibacterial performance, super-hydrophobic performance and ultraviolet resistance is imperative.\u003c/p\u003e \u003cp\u003eTitanium dioxide nanoparticles (TiO\u003csub\u003e2\u003c/sub\u003e NPs) have attracted much attention in fabricating functional cotton fabric due to its excellent ultraviolet resistance\u003csup\u003e[\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]\u003c/sup\u003e, chemical stability\u003csup\u003e[\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]\u003c/sup\u003e, antibacterial property\u003csup\u003e[\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]\u003c/sup\u003e, photocatalytic property\u003csup\u003e[\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]\u003c/sup\u003e, good biocompatibility and reasonable cost-effectiveness\u003csup\u003e[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]\u003c/sup\u003e. Although TiO\u003csub\u003e2\u003c/sub\u003e as functional finishing agent can endow the cotton fabric antibacterial ability via UV irradiation, the requirement of light irradiation conditions make the utilization rate of TiO\u003csub\u003e2\u003c/sub\u003e to the solar spectrum only about 3%, which limit the cotton fabric finished with TiO\u003csub\u003e2\u003c/sub\u003e for broad-spectrum antibacterial\u003csup\u003e[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]\u003c/sup\u003e. Luckily, many studies have been devoted to doping of TiO\u003csub\u003e2\u003c/sub\u003e with metal ions to enhance broad-spectrum antimicrobial property. The fermi energy level of noble metals are relatively low, electrons on the surface of TiO\u003csub\u003e2\u003c/sub\u003e are easily transferred to the surface of the noble metal to inhibit electron-hole recombination, thereby improving the light responsive range\u003csup\u003e[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]\u003c/sup\u003e. Furthermore, Ag nanoparticles (AgNPs) present a surface plasmon effect that induces electron transfer from metallic silver to TiO\u003csub\u003e2\u003c/sub\u003e resonance, resulting in charge separation actived by visible electromagnetic radiation\u003csup\u003e[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]\u003c/sup\u003e, which can enhance the photocatalytic and antimicrobial activities. For instance, Daniel J et al\u003csup\u003e[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]\u003c/sup\u003e. synthesized TiO\u003csub\u003e2\u003c/sub\u003e NPs coated by Ag (Ag/TiO\u003csub\u003e2\u003c/sub\u003e) via sonochemistry, and the increase in silver dosage enable the optical bandgap of TiO\u003csub\u003e2\u003c/sub\u003e NPs to reduce from 3.2 eV to 2.6 eV, which improved broad-spectrum antimicrobial property of the cotton fabric.\u003c/p\u003e \u003cp\u003eJanus nanoparticles refer to the non-centrosymmetric nanoparticles that integrate two different chemical compounds or functional into a structural system\u003csup\u003e[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]\u003c/sup\u003e. This flexible and controllable asymmetric structure can produce nanoparticles of different shapes and types such as amphiphilic Janus nanoparticles, anionic and cationic Janus nanoparticles, dumbbell Janus nanoparticles\u003csup\u003e[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]\u003c/sup\u003e. Among them, amphiphilic Janus nanoparticles are anisotropic nanomaterials with hydrophobic and hydrophilic properties, which can be used in cotton fabric functional finishing. Because amphiphilic Janus particles can not only provide low surface energy by hydrophobic side to endow the cotton fabric with superhydrophobic, but also improve the interaction force of nanoparticles and cotton fibers via hydrophilic side of the nanoparticles.\u003c/p\u003e \u003cp\u003eHerein, we supposed amphiphilic Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles with one side comprising hydrophobic long-chain alkane, and the other side with hydrophilic amino group was covalently bonded with the epoxy group on the epoxy modified cotton fabric surface (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e1\u003c/span\u003e). The aim was to endow the cotton fabric with the durable broad-spectrum antimicrobial, superhydrophobicity, and UV resistance properties. The finished cotton fabric were characterized in detail and their functional performance explored.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"2. Experimental methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Materials\u003c/h2\u003e \u003cp\u003eTitanium dioxide particles (100 nm in diameter) were supplied by Macklin (Shanghai, China). The paraffin wax with a melting point between 58\u0026deg;C and 60\u0026deg;C and Cyclohexane were supplied by Fuchen chemical reagents Co., LTD (Tianjin, China). The three kinds of silane coupling agents (3-aminopropyl) silane (KH550), n-octadecanetrichlorosilane (OTDS) and γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560) were supplied by Macklin (Shanghai, China). Cetyl Trimethyl Ammonium Bromide (CTAB), Sodium chloride (NaCl), Cyclohexane and Anhydrous ethanol were supplied by Tianli chemical reagents Co., LTD (Tianjin, China). Selected bacteria \u003cem\u003eEscherichia coli (E. coli)\u003c/em\u003e and \u003cem\u003eStaphylococcus aureus (S. aureus)\u003c/em\u003e were saved by our laboratory and incubated at 37\u0026deg;C on a nutrient agar plate for 24 h before use.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2 Synthesis of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microballoon sphere\u003c/h2\u003e \u003cdiv id=\"Sec5\" class=\"Section3\"\u003e \u003ch2\u003e2.2.1 Synthesis of Ag/C template\u003c/h2\u003e \u003cp\u003eGlucose was weighed and dissolved in deionized water, followed by addition of 0.10 mol/L AgNO\u003csub\u003e3\u003c/sub\u003e solution, mixed and stirred for 10 min, transferred into a 100 mL hydrothermal reaction kettle, reacted at 180 ℃ for 10 h, cooled to room temperature and then poured out; The produts were washed three times with ethyl alcohol by centrifugation and dried in an oven at 70 ℃ to obtain the Ag/C ball powder.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section3\"\u003e \u003ch2\u003e2.2.2 Synthesis of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microballoon sphere\u003c/h2\u003e \u003cp\u003e0.30 g Ag/C ball powder was ultrasonic dispersed in a certain amount of absolute ethanol for 5 min before transferred to a three-necked flask and added butyl titanate to react for 30 min at a mechanical stirring rate of 400 rpm/min; Then, a mixed solution of water, absolute ethanol and glacial acetic acid in a certain proportion was slowly dripped into the three-necked flask and reacted for 30 min. After 4 h of reaction, the products were washed three times with absolute ethanol and deionized water by centrifugation and dried in an oven to obtain dark brown powder, then which were calcined in muffle furnace for 3 h to obtain Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.3 Synthesis of amphipathic Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles\u003c/h2\u003e \u003cdiv id=\"Sec8\" class=\"Section3\"\u003e \u003ch2\u003e2.3.1 Preparation of semi-coated paraffin colloid\u003c/h2\u003e \u003cp\u003e10.00 g of paraffin wax was added into a three-necked flask and heated to melt at 75 ℃. 1.00 g of Ag@TiO\u003csub\u003e2\u003c/sub\u003e and 0.05 g of CTAB were dispersed in 90 mL of deionized water for ultrasonnic treatment for 10 min, then poured into the three-necked flask, stirred at high speed for an hour, and cooled to room temperature. With the decrease of temperature, paraffin wax solidified and turned into colloid. The wax colloid coated with Ag@TiO\u003csub\u003e2\u003c/sub\u003e was washed with deionized water and dried at 35 ℃ in vacuum.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section3\"\u003e \u003ch2\u003e2.3.2 Preparation of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e particles\u003c/h2\u003e \u003cp\u003eA certain amount of paraffin colloidal particles and 1.00 g KH-550 were added into a beaker of 100 mL methanol aqueous solution and stirred magnetically at 37 ℃ for 10 h. Then the solid paraffin colloidal particles were rinsed with deionized water, and dried in vacuum oven at low temperature for 24 h. The dried modified paraffin colloid was dissolved in cyclohexane to dissolve the paraffin wax, then HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e released from the paraffin wax was washed with cyclohexane, ethanol and deionized water for three times by centrifugation.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section3\"\u003e \u003ch2\u003e2.3.3 Synthesis of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles\u003c/h2\u003e \u003cp\u003eA certain amount of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e particles were ultrasonicated in 50 mL of ethanol for 10 min, poured into a 100 mL three-necked flask, added with 3.00 g OTDS, and stirred at 65 ℃ in the dark for 12 h. The modified particles were centrifugally washed with ethanol and deionized water for three times by centrifugation.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e2.4 Application experiment\u003c/h2\u003e \u003cdiv id=\"Sec12\" class=\"Section3\"\u003e \u003ch2\u003e2.4.1 Epoxy\u0026ndash;functionalization of cotton fabric\u003c/h2\u003e \u003cp\u003eA certain amount of KH-560 and 100mL NaCl solution were added to the beaker, followed by addition of 0.10mol/L NaOH solution to adjust the pH of the solution to 10. The washed cotton fabric were added to the reaction system, and the temperature was adjusted to 60 ℃. It was taken out after reaction for 30 min under magnetic stirring, washed with deionized water and ethanol, and dried at 80 ℃ for preserevation. Finally, the epoxy modified cotton fabric (E-cotton fabric) were obtained.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section3\"\u003e \u003ch2\u003e2.4.2 The Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles graft on E-cotton fabric\u003c/h2\u003e \u003cp\u003eJanus nanoparticles were ultrasonically dispersed in 30 mL absolute ethyl alcohol, E-cotton fabric were soaked for 30 min, washed with absolute ethyl alcohol for 3 times, and dried at 80 ℃ for 30 min.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e2.5 Characterization\u003c/h2\u003e \u003cp\u003eScanning electron microscope (SEM) measurement (Hitachi S-4800) was used to observe the structural characteristics of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres and modified cotton fabric. In order to observe the asymmetric characteristics of Janus particles, the morphology of Janus particles were measured by transmission electron microscope (TEM) analyzer (Tecnai G2 F20 S-TWIN). The dynamic light scattering (DLS) measurement (Malvern Zetasizer NANO-ZS90) was used to measure the particles size distribution and average particles size (concentration diluted to 0.1 wt%). Infrared spectrum (FT-IR) measurement (Vertex70) was characterized the modification effect of KH550 and OTDS on Ag@TiO\u003csub\u003e2\u003c/sub\u003e nanoparticles and cotton fabric. Ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS; Agilent radius mark-2500). The particles of TiO\u003csub\u003e2\u003c/sub\u003e, HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles were analyzed by thermogravimetry (TG) analyzer (STA449F3-1053-M). The heating rate was 10 ℃/min and the temperature range was 40 ℃~ 800 ℃. The hydrophobic property of the fabric surface was estimated by measuring WCA using a contact angle 140 goniometer (DM-700, Kyowa). The microstructure of the sample and the dispersion state of Janus particles on the fibers of cotton fabric were observed and tested by Japanese S4800 scanning electron microscope, and the elements on the surface of the sample were analyzed by EDS.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003e2.6 Performance test of multifunctional cotton fabric\u003c/h2\u003e \u003cdiv id=\"Sec16\" class=\"Section3\"\u003e \u003ch2\u003e2.6.1 Hydrophobic durability test\u003c/h2\u003e \u003cp\u003eDye water of different colors were prepared, and 0.50 \u0026micro;L drops were absorbed on the surface of cotton fabric by pipetting gun, and the existing state of drops on the surface of cotton fabric was observed. The cotton fabric were placed in a watch glasses filled with distilled water, and observed that the cotton fabric were kept at the liquid level. The modified cotton fabric were stirred in hot water at 80 ℃ for 3 h, followed by taking out and drying to measure the contact angle of the cotton fabric. The above steps were one cycle, and the hydrophobic durability was investigated through multiple cycles. In order to simulate the harsh corrosive environment, the modified cotton fabric were washed under different pH and solvent conditions or rubbed repeatedly to test its hydrophobic durability.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec17\" class=\"Section3\"\u003e \u003ch2\u003e2.6.2 Antibacterial property test\u003c/h2\u003e \u003cp\u003eAccording to the standard QBT4341-2012, the antibacterial property of fabrics was tested by the bacteriostatic circle method. Modified culture medium, culture dish and phosphate (PBS) buffer were sterilized in autoclave, followed by pouring the cuiture medium into the culture dish under the ultra-clean workbench. \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e were diluted with 20 mL PBS to obtain suspension. After the culture medium was cooled and solidified, 1.50 mL of suspension was removed from the culture medium and evenly coated with a coater. The circular fabric cut into 1 cm diameter (UV sterilized) was placed right in the middle of the culture medium, placed upside down in a constant temperature and humidity box, and cultured at 37 ℃. The growth of bacteria was observed after 24\u0026ndash;48 h intervals.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec18\" class=\"Section3\"\u003e \u003ch2\u003e2.6.3 Superhydrophobic stability test\u003c/h2\u003e \u003cp\u003eA small amount of chromium powder were put on the modified cotton fabric. Then the modified cotton fabric surface was washed with distilled water to observe the movement state of water droplets and chromium powder on the cotton fabric surface; The modified cotton fabric were contaminated with castor oil or rhodamine B dye to observed the degradation effect of the cotton fabric on the pollutants.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec19\" class=\"Section3\"\u003e \u003ch2\u003e2.6.4 Laundry resistance test\u003c/h2\u003e \u003cp\u003eThe laundry resistance of the modified cotton fabric were evaluated according to the test method of colony count (GB 4789.3\u0026ndash;2016 and GB 4789.10\u0026ndash;2016). The particle-treated cotton fabric were washed with an ultrasonic cleaner at an ultrasonic frequency of 40 kHz and an ultrasonic power of 180 W. Each washing cycle lasted for 30 min and the antibacterial rate of the modified cotton fabric treated in different washing cycles were detected.\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec21\" class=\"Section2\"\u003e \u003ch2\u003e3.1 Synthesis of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres\u003c/h2\u003e \u003cp\u003eThe morphologies of the Ag/C templates and Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres were observed by SEM. The Ag/C templates were regular spheroids with uniform size and smooth surface without adhesion (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003ea). The Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres were approximately 400\u0026thinsp;~\u0026thinsp;600 nm in diameter in the SEM image (as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003eb). Compared with the surface of the original smooth Ag/C templates, the surface of the Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres become rough, indicating that the templates surfaces were covered with TiO\u003csub\u003e2\u003c/sub\u003e layers, forming well-dispersed Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres. The broken microspheres in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003eb could be seen to have shell structure.\u003c/p\u003e \u003cp\u003eEDS result revealed the surface element distribution of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003ec. The distribution of Ti and O elements was very obvious. At the same time, a small amount of Ag element also appeared. This was mainly because in the calcination process of removing the template, with the disappearance of the carbon balls, the particles reduced into nano-Ag in the template remained in the TiO\u003csub\u003e2\u003c/sub\u003e shell. As the melting point of nano-silver was only 100 ℃, the Ag nano-core melted first during the calcination process at 450 ℃, and a small amount gradually seeped out of the TiO\u003csub\u003e2\u003c/sub\u003e shell and adhered to the hollow sphere TiO\u003csub\u003e2\u003c/sub\u003e shell, so Ag element also had a small distribution\u003csup\u003e[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]\u003c/sup\u003e.\u003c/p\u003e \u003cp\u003eThe XRD curves of nano-Ag, nano-TiO\u003csub\u003e2\u003c/sub\u003e and nano-Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres were displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003ed. The diffraction peaks of nano-Ag curves all appeared at 2θ\u0026thinsp;=\u0026thinsp;38.2, 44.5 and 63.8, corresponding to (111), (200) and (220) crstallographic plane of silver respectively\u003csup\u003e[\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]\u003c/sup\u003e. The obvious characteristic diffraction peaks in the nano-TiO\u003csub\u003e2\u003c/sub\u003e curve appeared around 2θ\u0026thinsp;=\u0026thinsp;25.3, 38.1, 48.0, 53.8, 55.1 and 62.8, corresponding to (101), (004), (200), (105) and (211) crstallographic plane of anatase respectively\u003csup\u003e[\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]\u003c/sup\u003e. In the curve of nano Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres, besides the diffraction peak of anatase TiO\u003csub\u003e2\u003c/sub\u003e, the diffraction peak of nano silver appeared correspondingly, which indicated the silver was loaded on anatase TiO\u003csub\u003e2\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec22\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Synthesis of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus particles\u003c/h2\u003e \u003cp\u003eIn order to prove the amphiphilicity of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles, the Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres were respectively modified by KH-550 (HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e) and OTDS (C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e) to endow the Ag@TiO\u003csub\u003e2\u003c/sub\u003e hydrophilicity and hydrophobicity. HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e, Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e were dispersed in the mixed system of methyl methacrylate and water respectively, and its dispersion states were compared, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e3\u003c/span\u003ea. The HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e microspheres with hydrophilic amino groups on the surface only dispersed in the lower water phase of the system, hydrophobic C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres with long-chain alkanes only dispersed in the upper oil phase of the system, and amphiphilic Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles stably existed in the oil-water interface. It indicated that Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles not only had both hydrophilic and hydrophobic segments, but also had stable amphiphilicity. In order to further explored the structural characteristics of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles, silver labeling method was used to characterize (Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). As could be seen that the Ag@TiO\u003csub\u003e2\u003c/sub\u003e nanoparticles with a size of about 500 nm had a hollow structure, and the silver nanoparticles were clearly labeled on one side of the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles. Therefore, the surface groups of the synthesized Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles were asymmetrically distributed, which further proved that the particles had Janus structural characteristics. The average particles size of unmodified Ag@TiO\u003csub\u003e2\u003c/sub\u003e, HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus particles were displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e3\u003c/span\u003ec. The particles size of unmodified Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres was 495 nm, that of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e particles modified by silane coupling agent KH-550 was 515 nm, and that of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles modified by amphiphilic modification was 627 nm. The average particles size of the three kinds of particles gradually increased with the increase of modification degree. In order to exist stably, the hydrophobic sides of amphiphilic Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles were as close as possible to reduce the contact area between hydrophobic sides and water, which caused the agglomeration state of the particles in the system to a greater extent and made the size of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles increase.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAs shown in the Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e4\u003c/span\u003ea, the unmodified Ag@TiO\u003csub\u003e2\u003c/sub\u003e, HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus particles were characterized by infrared spectroscopy. The FT-IR curves of unmodified Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres had obvious O-H anti-symmetric stretching vibration absorption peaks and bending vibration absorption peaks at 3427 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1630 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, and the absorption peaks at 500\u0026ndash;700 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were characteristic absorption peaks of Ti-O and Ti-O-Ti of inorganic TiO\u003csub\u003e2\u003c/sub\u003e. As could be seen from the curve of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e particles, the intensity of O-H absorption peak at 3427 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was weaker than that of Ag@TiO\u003csub\u003e2\u003c/sub\u003e, which proved that silane coupling agent KH-550 had a condensation reaction with hydroxyl groups on the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e, and the grafting of hydrophilic segments reduced the number of hydroxyl groups, thus affecting its absorption peak intensity. The peaks at 2908 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 2834 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were the stretching vibration peaks of C-H in KH-550, and the wider peaks at 1030 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 661 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were the stretching vibration peaks of C-N and the out-of-plane bending vibration peaks, respectively, and the stretching vibration peaks of Si-O in KH-550 at 1136 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, thus indicating KH-550 was successfully grafted onto the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres. Due to the OTDS had long -chain alkyl group, the stretching vibration peaks of C-H at 2908 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 2834 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were stronger than those of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e, and a strong bending vibration peak of C-H appears at 1470 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Therefore, the amphiphilic Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles were successfully prepared.\u003c/p\u003e \u003cp\u003eAccording to the TG curve analysis of Ag@TiO\u003csub\u003e2\u003c/sub\u003e, HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus particles, the grafting amount of hydrophilic segment of KH-550 and hydrophobic segment of OTDS on the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres were estimated, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e4\u003c/span\u003eb. The mass loss of unmodified Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres was 2.47% in the temperature range of 25\u0026ndash;800℃, which was mainly due to the adsorption of water, hydroxyl and oxidant on the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e. It could be seen from the figure that the TG curve of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e particles had three weight loss stages in the temperature range of 25\u0026ndash;800 ℃, which was mainly caused by the volatilization of adsorbed water contained in the particles and the breakage of C-C bond on the hydrophilic segment grafted on the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e. It indicated that KH-550 was grafted on the Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres. TG curve of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles also had three stages of thermal decomposition, which mainly caused by the free water and bound water in the particles were the main losses in the temperature range of 25\u0026ndash;280 ℃, the breakage of C-C bonds on a large number of hydrophilic and hydrophobic segments grafted on the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e in the temperature of 281\u0026ndash;495 ℃ and the Si-O bond of KH-550 and ODTS grafted on Ag@TiO\u003csub\u003e2\u003c/sub\u003e was decomposed and lost weight in the temperature range of 496\u0026ndash;800 ℃. Compared the mass loss of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles in the second and third stages, the mass loss of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles was greater than that of HO-Ag@TiO\u003csub\u003e2\u003c/sub\u003e-NH\u003csub\u003e2\u003c/sub\u003e, which indicated that a large number of hydrophobic segments were grafted on the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles. The amount of hydrophilic and hydrophobic segments grafted on Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles was estimated to be about 2.49% and 5.47%, respectively.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec23\" class=\"Section2\"\u003e \u003ch2\u003e3.3 Preparation and characterization of multifunctional cotton fabric\u003c/h2\u003e \u003cp\u003eThe SEM photograph of epoxy modified cotton fabric treated with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles with different concentrations were shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e5\u003c/span\u003e. When the concentration of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles was 1.5%, only a very small number of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles were dispersed on the cotton fiber, so the contact angle of the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric was only 95, and the hydrophobic property was unsatisfactory. When the concentration was increased to 2.0%, the coating amount of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles on the fiber surface increased, and the contact angle increased to 125. When the concentration was 2.5%, the contact angle reached the maximum of 160. As seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e5\u003c/span\u003ec that Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles not only wrapped tightly on the surface of the fiber, but also formed rugged dome-shaped clusters, and constructed multi-level rough structure, which could effectively improve the hydrophobicity of the fabric. Meanwhile, EDS analysis was performed on the cotton fabric modified by Ag @ TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles with the concentration of 2.5%. It could be seen from the figure that the Ti element was uniformly distributed, indicating that Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles were uniformly grafted onto the cotton fabric. Since the introduction amount of Ag in the Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres was relatively small, the distribution of Ag element was relatively uniform but very small. As the silane coupling agents KH-550 and OTDS carried out amphiphilic modification on Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres, the distribution of Si element appeared in the EDS spectrum of the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric. The distribution of C and N elements in the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric could also be seen in the figure, but the distribution of C element in the figure was more significant, which may be due to the large number of hydrophobic OTDS grafted onto Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eE-cotton fabric and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric were characterized by FT-IR, in order to detect the chemical bonding between Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles and epoxy groups on the surface of cotton fabric,as observed in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e6\u003c/span\u003e. The FT-IR curve of E-cotton fabric had a peak at 910 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, which was the characteristic absorption peak of C-O-C from the epoxy group grafted on the surface of cotton fabric. From the curve of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric, it could be seen that the characteristic absorption peak intensity of C-O-C at 910 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e was obviously weaker than that of E-cotton fabric, which indicated that the amino groups on Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles reacted with epoxy groups on cotton fabric.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec24\" class=\"Section2\"\u003e \u003ch2\u003e3.4 Application of multifunctional cotton fabric\u003c/h2\u003e \u003cdiv id=\"Sec25\" class=\"Section3\"\u003e \u003ch2\u003e3.4.1 Superhydrophobic durability\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn order to directly observe the hydrophobic effect of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric, the dyed water droplets were dropped on the cotton fabric, and the state of the dyed water droplets on the surface of cotton fabric was observed. As could be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e7\u003c/span\u003ea, when the dyed water droped on the surface of unmodified raw cotton fabric, the water drops immediately collapsed, which was related to the presence of hydroxyl groups on the surface of the fibers and the capillary effect caused by the voids between fibers. Figure\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e7\u003c/span\u003eb was a photo of water droplets placed on the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric. The hydrophobic long-chain alkyl group on the one side of the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles endowed the finished fabrics with the ability to repel liquids. The liquid droplets all maintain a spherical shape on the finished fabric and did not absorb into it. Figure\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e7\u003c/span\u003e(c-d) shown the placing phenomenon of cotton fabric in aqueous solution before and after modification, in which 1\u003csup\u003e#\u003c/sup\u003e was the original cotton fabric and 2\u003csup\u003e#\u003c/sup\u003e was the cotton fabric modified by Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles. According to observe the placing state of the two cotton fabric in water, the hydrophobicity of the cotton fabric before and after modification could be detected. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e7\u003c/span\u003ec, when the cotton fabric were clamped on one side of the cotton fabric sample with tweezers and the other side was placed in water, the half of the unmodified raw cotton fabric easily immersed in water and dyed. Due to Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric had good hydrophobic property, it was dyed without absorbing the aqueous solution. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e7\u003c/span\u003ed, when the original cotton fabric and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric were directly placed in the watch glasses of dyeing aqueous solution, the original cotton fabric would soon absorb water and sink, while the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric could still float above the liquid level after being placed, which indicated that the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric had good hydrophobic performance.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAg@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles and epoxy-containing cotton fabric were bonded by stable chemical bonds, so the durability of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric was tested in various ways. For comparative study, the Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres were hydrophobically modified by OTDS, so that only long-chain alkanes were grafted on their surfaces, and no amino groups that reacted with epoxy groups(C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e). The particles were applied to cotton fabric finishing, and the obtained cotton fabric were named C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric. The changing trend of water contact angle of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric after long-time washing at 80 ℃ was investigated, as observed in Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e8\u003c/span\u003ea. The two kinds of cotton fabric had the same original contact angle of 160. Compared with C\u003csub\u003e18\u003c/sub\u003e-Ag @ TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric, the contact angle of Ag@ TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric had a smaller change trend with time, which was the strong chemical bonding between the particles and the cotton fabric, so it could still maintain a good contact angle. Figure\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e8\u003c/span\u003eb investigated the influence of friction cycles on the contact angle of fabrics. After friction cycles, both Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric were worn. Compared with the initial contact angle of 160 before friction loss, the contact angle of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric after friction treatment had a little decreasing trend in comparison to that of C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric. From the photos in the figure, the water droplets in the damaged area of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric were still full, which indicated that Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric still maintained the hydrophobic effect after abrasion. Figure\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e8\u003c/span\u003ec presented the change of contact angle of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric under the condition of extreme pH solution and mechanical stirring. As seen that the contact angle of cotton fabric had almost unchangable with the stirring time, comparing with acidic or alkaline solution. On the one hand, the hydrophobic property of cotton fabric was provided by the covalent bond between the hydrophilic amino group of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles and the epoxy group on the fiber, and the hydrophobic side was provided to the environment; On the other hand, the aggregation formed by self-assembly of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles deposited on cotton fabric fibers to form a multi-level rough structure, which further improved the hydrophobic property of the fabrics. Therefore, when the hydrophobic cotton fabric were treated in an acid-base solution, the acid-base environment destroyed the non-covalent bonds between particle aggregates deposited on the surface of the cotton fabric, affected the assembly state of the particles, thus destroyed the multi-level rough structure on the cotton fabric, and finally weakened the hydrophobic property of the cotton fabric, resulted in the decrease of the contact angle. Figure\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e8\u003c/span\u003ed was shown the influence of different solvent soaking treatments on the contact angle of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric. It could be seen from the figure that solvents such as absolute ethyl alcohol, cyclohexane, toluene, tetrahydrofuran and dimethylformamide had no obvious influence on the hydrophobic effect of cotton fabric. Especially, the contact angle of the modified cotton fabric treated with absolute ethanol slightly increased, which might be due to the rapid volatilization of ethanol, and the roughness induced by phase separation increased the contact angle of the treated fabrics by nearly 6.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eAg@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric were washed by ultrasonic, and the micro-morphology of cotton fabric before and after treatment was investigated. As shown in Fig.\u0026nbsp;9a\u003csub\u003e1\u003c/sub\u003e and Fig.\u0026nbsp;9b\u003csub\u003e1\u003c/sub\u003e, the fiber scanning photos of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric before treatment were not much different, and the fiber surfaces of the two kinds of fabrics were densely coated with nanoparticles. Because the particles were grafted with hydrophobic segments, the initial water contact angles of the two kinds of cotton fabric were not much different, which were 160 and 161 respectively. From the photo of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric after ultrasonic water washing SEM in Fig.\u0026nbsp;9a\u003csub\u003e2\u003c/sub\u003e, there were still many particles that were evenly grafted on the surface of the fiber through chemical bonding. At this time, the contact angle was reduced to 152, but it still had excellent hydrophobic properties. After the C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric were treated, due to the lack of chemical bonding between the particles and the cotton fabric, a large number of nanoparticles were fell off, and the water contact angle of the cotton fabric was decreased to 81, as displayed in Fig.\u0026nbsp;9b\u003csub\u003e2\u003c/sub\u003e. The EDS spectra of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e/E-cotton fabric after ultrasonic water washing were shown in Fig.\u0026nbsp;9a\u003csub\u003e3\u003c/sub\u003e and Fig.\u0026nbsp;9b\u003csub\u003e3\u003c/sub\u003e. There were elements of C, O, Ti, Ag and Si on the surface of cotton fiber after finishing with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus and C\u003csub\u003e18\u003c/sub\u003e-Ag@TiO\u003csub\u003e2\u003c/sub\u003e nanoparticles, which indicated that the particles exist in cotton fabric.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec26\" class=\"Section3\"\u003e \u003ch2\u003e3.4.2 Antibacterial durability\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eIn general, bacteria were easily attached to fabrics when it is worn for a long time, so the antibacterial performance of modified fabrics was important to assess. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig14\" class=\"InternalRef\"\u003e10\u003c/span\u003e, comparing the cotton fabric modified by different materials, it intdicated that Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/ E-cotton fabric has excellent antibacterial properties against \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e. According to the results in Fig.\u0026nbsp;\u003cspan refid=\"Fig14\" class=\"InternalRef\"\u003e10\u003c/span\u003e(a\u003csub\u003e1\u003c/sub\u003e, a\u003csub\u003e2\u003c/sub\u003e, b\u003csub\u003e1\u003c/sub\u003e, b\u003csub\u003e2\u003c/sub\u003e), no bacteriostatic rings appeared around the control cotton fabric, whether for E. coli or S. aureus. But the TiO\u003csub\u003e2\u003c/sub\u003e/ E-cotton fabric was a slight inhibition zone around the TiO\u003csub\u003e2\u003c/sub\u003e nanoparticles treated cotton fabric for \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e. This was mainly due to the fact that TiO\u003csub\u003e2\u003c/sub\u003e can generate electron/hole (e\u003csup\u003e\u0026minus;\u003c/sup\u003e/ h\u003csup\u003e+\u003c/sup\u003e) and further produces reactive oxygen species, such as .OH, O\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e\u0026minus;\u003c/sup\u003e and H\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e, which can degrade bacterial proteins and lead to inhibition of biological growth. Comparing with TiO\u003csub\u003e2\u003c/sub\u003e/ E-cotton fabric, Ag@TiO\u003csub\u003e2\u003c/sub\u003e nanoparticles treated cotton fabric presented obviously 3\u0026ndash;4 mm inhibition zone for \u003cem\u003eE. coli\u003c/em\u003e or \u003cem\u003eS. aureus\u003c/em\u003e (Fig .10(a\u003csub\u003e3\u003c/sub\u003e,b\u003csub\u003e3\u003c/sub\u003e)). It was mainly attribute to the induction of electron transfer from metallic silver to TiO\u003csub\u003e2\u003c/sub\u003e resonance after the addition of Ag, which lead to charge separation, inhibited electron-hole coincidence and promoted the generation of active oxygen, thus improving its antibacterial performance. Comparing with Ag@TiO\u003csub\u003e2\u003c/sub\u003e/ E-cotton fabric, Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles finished cotton fabric showed excellent antibacterial performance against \u003cem\u003eE. coli\u003c/em\u003e or \u003cem\u003eS. aureus\u003c/em\u003e, which appeared 7\u0026ndash;8 mm inhibition zone for \u003cem\u003eE. coli\u003c/em\u003e or \u003cem\u003eS. aureus\u003c/em\u003e (Fig .10(a\u003csub\u003e4\u003c/sub\u003e,b\u003csub\u003e4\u003c/sub\u003e)). Due to the hydrophobic nature of the fiber surface after finishing with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus particles ensure weaken the adhesion of bacteria to the substrate, thus achieving a synergistic antibacterial effect to endow with the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus cotton fabric excellent antibacterial properties.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe antibacterial durability of the cotton fabric finished with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles against \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e was shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e11\u003c/span\u003e. From the figure, the unwashed cotton fabric had excellent antibacterial effect, and the antibacterial rate reached over 99%. After 8 cycles of ultrasonic washing, the antibacterial rate of cotton fabric finished with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles to \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e still be kept above 85%, and the decrease was not significant compared with the antibacterial rate before washing. Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric had excellent and lasting antibacterial properties to \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e. The strong antibacterial activity was due to the excellent photocatalytic performance of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles and the dual action of Ag\u003csup\u003e+\u003c/sup\u003e release. After 8 washing cycles, Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric still showed high antibacterial activity against two kinds of bacteria, which indicated that the amino groups on Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles could form covalent bonds with epoxy groups on cotton fibers, which ensured that even under the strong washing action, the nanoparticles could still stably exist on the surface of cotton fibers, giving them long-term antibacterial activity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec27\" class=\"Section3\"\u003e \u003ch2\u003e3.4.3 Ultraviolet protection performance\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe transmission of E-cotton fabric and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric under ultraviolet irradiation was shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig18\" class=\"InternalRef\"\u003e12\u003c/span\u003e. It could be seen from the figure that, compared with E-cotton fabric, the lowest ultraviolet transmittance of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric in the ultraviolet band between 200 and 400 nm was reduced to about 20%, which indicated that the transmittance of cotton fabric treated with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles in the ultraviolet region was significantly reduced. The results indicated that the application of Ag @ TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles to cotton fabric endowed the cotton fabric with anti-ultraviolet characteristics.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec28\" class=\"Section3\"\u003e \u003ch2\u003e3.4.4 Wearability\u003c/h2\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eTest results of mechanical properties, softness, whiteness index and air permeability of raw cotton fabric, E-cotton fabric and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric were observed in Fig.\u0026nbsp;\u003cspan refid=\"Fig20\" class=\"InternalRef\"\u003e13\u003c/span\u003e. Compared with the original cotton fabric, the tensile strength and elongation at break of E-cotton fabric and Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric decreased slightly(Fig.\u0026nbsp;\u003cspan refid=\"Fig20\" class=\"InternalRef\"\u003e13\u003c/span\u003ea). As could be seen from Fig.\u0026nbsp;\u003cspan refid=\"Fig20\" class=\"InternalRef\"\u003e13\u003c/span\u003eb, compared with the original cotton fabric, the softness of the E-cotton fabric was almost unchanged, and the softness of the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric was obviously decreased, which was mainly due to the fact that the surface and voids of the fibers of the Ag@TiO\u003csub\u003e2\u003c/sub\u003eJanus/E-cotton fabric were grafted and filled with a large number of nanoparticles, and a certain rough structure was formed on the surface, which hindered the slippage between fibers, thus causing the softness of the cotton fabric. The whiteness index of cotton fabric finished with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles had obviously decreased, which was due to the gray color of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles, which had obvious influence on the whiteness index of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric, as displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig20\" class=\"InternalRef\"\u003e13\u003c/span\u003ec. The air permeability of E-cotton fabric decreased slightly, which was due to a large number of organic segments of KH-560 grafted on cotton fibers, which hindered the gas from passing between cotton fibers, as demonstrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig20\" class=\"InternalRef\"\u003e13\u003c/span\u003ed. However, the air permeability of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric was basically unchanged, which might be due to the porous structure of TiO\u003csub\u003e2\u003c/sub\u003e shell of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles, so the grafting of nanoparticles on cotton fabric did not affect the air permeability of the fabrics.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003c/div\u003e"},{"header":"4.Conclusion","content":"\u003cp\u003eFor development of multifunctional durable cotton fabric, the two sides of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres respectively were carried aminosilane coupling agent and long-chain alkane to form an asymmetric Janus structure, and a multifunctional cotton fabric with durably superhydrophobic, antibacterial and UV resistance was prepared. FT-IR and TG characterization showed that the surface of Ag@TiO\u003csub\u003e2\u003c/sub\u003e microspheres was grafted with amino groups and long-chain alkanes, with the grafting amounts of 2.49% and 5.47% respectively. The stable state of Janus nanoparticles at the oil-water interface and TEM showed that the nanoparticles had typical amphiphilic Janus structure. Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles with different concentrations were used for cotton fabric finishing and modification. When the concentration of the Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles was 2.5%, the surface of cotton fibrics formed multi-level rough structure, and the contact angle of the fabric was 160. Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles were covalently grafted onto cotton fabric, and after high-temperature washing, abrasion and different chemical solvent treatments, it still maintained great hydrophobic durability. The antibacterial rate of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric to \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eS. aureus\u003c/em\u003e could be kept above 80% after 8 cycles of ultrasonic washing. In addition, the lowest ultraviolet transmittance of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric in the ultraviolet band of 200\u0026thinsp;~\u0026thinsp;400 nm could be reduced to about 20%.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors acknowledge the support for this study from the Key Project of Natural Science Basic Research Program of Shaanxi Province (Special Support, 2023JC-XJ-12).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthors contributions \u0026nbsp;\u003c/strong\u003eDangge Gao conceived the concept, supervised the project and provided financial support and thoughts of manuscript. Fangxing Wang performed the experiment, prepared the samples and did the manuscript and analysis. Zhouyang Zhao performed the experiment and provided thought. Lyu Bin provided manuscript retouching and fund support. Jianzhong Ma provided the thought, manuscript retouching and fund.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding \u0026nbsp;\u003c/strong\u003eThis work was carried out with support from the Key Project of Natural Science Basic Research Program of Shaanxi Province (Special Support, 2023JC-XJ-12).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest \u0026nbsp;\u003c/strong\u003eThe authors declare no conflict of interest.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics approval \u0026nbsp;\u003c/strong\u003eAll authors have understood and complied with the code of ethics, approved, and agreed to participate.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent for publication \u0026nbsp;\u003c/strong\u003eAll authors agreed to publish the paper.\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. The images or other third party material in this article are included in the article\u0026rsquo;s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article\u0026rsquo;s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eLi S, Lin X, Gong S, et al (2022). Waterborne polyurethane assembly multifunctional coating for hydrophobic and antibacterial fabrics[J]. 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Cellulose, 28: 7373\u0026ndash;7388.\u003c/span\u003e \u003cspan\u003e\u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10570-021-03951-2\u003c/span\u003e\u003cspan address=\"10.1007/s10570-021-03951-2\" 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":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Janus nanoparticles, cotton fabric, super-hydrophobic, antibacterial, durability, UV resistance","lastPublishedDoi":"10.21203/rs.3.rs-3191198/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3191198/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe market demand for multifunctional cotton fabric is increasing. However, the key of developing cotton fabric with multiple functions is how to solve the problem of functional combination. In this study, silver@titanium dioxide Janus nanoparticles (Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles) were synthesized by Pickering emulsion polymerization and finished on the epoxy modified cotton fabric (Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric). The Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles had asymmetric Janus structure, that one side being silane with hydrophilic amino group was covalently bonded with the epoxy group on the cotton fabric fibers and the other side being silane with hydrophobic long-chain alkane was faced the environment, which was to endow the cotton fabric durably superhydrophobic, UV resistance, and antibacterial. Characterization by SEM, XRD, EDS, EDS, FT-IR and TG verified the finishing of the cotton fabric with Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus nanoparticles. Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E-cotton fabric had a water contact angle of 160, after 50 wear cycles, the contact angle at the damaged part could still reach 152. Compared with raw cotton fabric, the antibacterial rate of Ag@TiO\u003csub\u003e2\u003c/sub\u003e Janus/E- cotton fabric to \u003cem\u003eEscherichia coli (E. coli)\u003c/em\u003e and \u003cem\u003eStreptococcus Urealyticus (S. aureus)\u003c/em\u003e is more than 95%. After 8 ultrasonic washing cycles, the antibacterial rate still maintained more than 80%. The UV protection performance of the finished cotton fabric was improved by 82.3%.\u003c/p\u003e","manuscriptTitle":"Multifunctional cotton fabric with durable antibacterial, superhydrophobicity, and UV resistance based on Ag@TiO 2 Janus nanoparticles","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-07-27 14:20:44","doi":"10.21203/rs.3.rs-3191198/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Major revision","date":"2023-07-25T00:05:03+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2023-07-24T06:39:36+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2023-07-24T06:39:36+00:00","index":"","fulltext":""},{"type":"submitted","content":"Cellulose","date":"2023-07-21T08:55:03+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"cellulose","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"cels","sideBox":"Learn more about [Cellulose](https://www.springer.com/journal/10570)","snPcode":"10570","submissionUrl":"https://submission.nature.com/new-submission/10570/3","title":"Cellulose","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"061a6362-07a2-408e-bab7-0df0586b6f6a","owner":[],"postedDate":"July 27th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-02-05T15:02:36+00:00","versionOfRecord":{"articleIdentity":"rs-3191198","link":"https://doi.org/10.1007/s10570-023-05727-2","journal":{"identity":"cellulose","isVorOnly":false,"title":"Cellulose"},"publishedOn":"2024-01-29 15:00:48","publishedOnDateReadable":"January 29th, 2024"},"versionCreatedAt":"2023-07-27 14:20:44","video":"","vorDoi":"10.1007/s10570-023-05727-2","vorDoiUrl":"https://doi.org/10.1007/s10570-023-05727-2","workflowStages":[]},"version":"v1","identity":"rs-3191198","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3191198","identity":"rs-3191198","version":["v1"]},"buildId":"FbvkV6FR0MCFSLy54lSbu","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}