Durable antibacterial cotton fabrics with good performance enabled by quaternary ammonium salts

Durable antibacterial cotton fabrics with good performance enabled by quaternary ammonium salts | 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 Durable antibacterial cotton fabrics with good performance enabled by quaternary ammonium salts Qi Ding, Jiang-Long Liu, Yan-Yan Liu, Wen-Zhan He, Lin Zhang, and 1 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4034782/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 01 Jun, 2024 Read the published version in Cellulose → Version 1 posted 7 You are reading this latest preprint version Abstract For addressing the issue of limited durable antibacterial cotton fabric, this study developed and synthesized quaternary ammonium salt antimicrobial agents. The chemical structure was analyzed by FTIR and 1H NMR. The cotton fabric was subjected to surface modification techniques, such as pad-dry-cure, following the careful selection of appropriate quaternary ammonium salt. The chemical state and surface morphology were evaluated through XPS and SEM. Furthermore, the cotton fabric underwent comprehensive assessments, which included antibacterial testing, laundering cycle testing, evaluation of mechanical properties, and analysis of comfort performance. The results demonstrated that the treated cotton fabric achieved a high bacteriostatic and fungistatic rate of 99.99%, 87.5%, and 99.99% against S. aureus, E. coli, and C. albicans respectively even after 50 laundering cycles, while maintaining exceptional antibacterial effectiveness and laundering durability due to the formation of covalent bonds with the cotton fabric. The treated cotton fabric met AAA grade standards for antibacterial rate without causing any significant decline in mechanical properties. Furthermore, enhancements in hydrophilicity, softness, and wrinkle resistance were observed. Quaternary ammonium salt cotton fabric antibacterial laundering durability Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 1. Introduction Cotton fabric is highly favored by consumers due to its softness, hydrophilicity, comfort, skin-friendliness, and other characteristics, making it a popular choice in the textile industry. As cotton fabric comes into direct contact with the skin and absorbs sweat and other secretions from the human body (Chang and Wang 2023), it can provide breeding grounds and nutrients for bacteria. Therefore, antibacterial treatment of cotton fabric plays a crucial role in effectively preventing bacterial reproduction and reducing the risk of diseases caused by bacterial infections. For achieving antibacterial properties on natural fibers like cotton, various methods such as dipping method, padding method, and chemical grafting method have been extensively researched and applied (Gao et al. 2021). However, there are challenges associated with maintaining durable antibacterial efficacy of treated cotton fabric as well as issues related to color change after treatment that leads to significant deterioration in mechanical properties and poor hand experience. The primary goal moving forward is to attain durability, antibacterial efficacy, and enhanced hand. To accomplish this, the most efficacious strategy for augmenting both the endurance and antibacterial properties of cotton fabric entails covalently attaching the antimicrobial agent onto its surface. The ideal antibacterial agent should fulfill the following criteria: (1) exhibit a broad spectrum and high efficacy against bacteria; (2) not compromise the strength, moisture absorption, or other physical properties of cotton fabric; (3) demonstrate strong adhesion to cotton fabric while retaining durability and antibacterial activity after laundering cycles and exposure to sunlight; (4) possess low cost, simple processing requirements, and compatibility with other finishing agents (Liu et al. 2022). Among commonly employed antibacterial agents, natural alternatives offer abundant resources and good biocompatibility but suffer from limited antimicrobial activity, inadequate persistence, and complex extraction processes. Inorganic antimicrobials such as metal-ionic compounds are widely used; however, nanostructured antimicrobials with increased specific surface area for enhanced bacterial adsorption present drawbacks including toxicity, unstable performance, and susceptibility to discoloration. Photocatalytic antimicrobials suffer from the drawback of light dependence. Organic antibacterial agents exhibit a wide range of applications and possess strong bactericidal capabilities. In organic antimicrobials, the antimicrobial properties of halogenated amines are associated with their own structural characteristics. Upon contact with bacteria, N-X bonds exterminate them, transforming into N-H bonds and losing activity; subsequent halogenation restores the bactericidal properties by converting them back to N-X bonds. However, their limited hydrophilicity restricts their scope of application (Dong et al. 2017). Quaternary ammonium salts offer broad-spectrum antibacterial effects, simple production processes, rapid and efficient sterilization abilities, good hydrophilicity, and easy elution while minimizing secondary pollution (Wang et al. 2022). The positively charged N + in quaternary ammonium salts directly interacts with negatively charged cells through electrostatic adsorption (Gharibi et al. 2019; Makvandi et al. 2018). Either the long-chain alkyl group connected to N + penetrates the cell wall causing leakage of intracellular contents leading to cell death or the negative charge on the cell wall is attracted towards the side in contact with quaternary ammonium salts thereby reducing electronegativity on that side resulting in rupture of cell wall followed by leakage of intracellular contents leading to cell death. Gao et al. synthesized a nanocomposite material based on silicone quaternary ammonium salt for antibacterial finishing of cotton fabric. The resulting antibacterial rate of the fabric reached 90%, and even after 10 laundering cycles, the antibacterial rate against Escherichia coli and Staphylococcus aureus remained above 85%. Additionally, the finishing process improved the hydrophilicity, air permeability, and softness of the cotton fabric to some extent (Gao et al. 2019). Wang et al. optimized the antibacterial finishing process of cotton fabric using a novel BJK01 silicone quaternary ammonium salt antibacterial agent. After this treatment, the initial antibacterial rate of cotton fabric approached 100% without laundering, and it still maintained an antibacterial rate of 70% even after undergoing 50 laundering cycles while meeting AAA antimicrobial standards. However, it should be noted that quaternary ammonium salt finishing may lead to significant loss in durability, antimicrobial properties, strength as well as noticeable decline in whiteness, softness and wrinkle resistance. The objective of this experiment was to design and synthesize quaternary ammonium salt antibacterial agents with varying alkyl chain lengths, select an appropriate quaternary ammonium salt through antibacterial testing, and fabricate durable antibacterial cotton fabric using the pad-dry-cure method (Huang et al. 2022; Xu et al. 2018). The covalent cross-linking of the quaternary ammonium salt with the cotton fabric ensures minimal elution. Comprehensive analysis was conducted on the soft properties, wrinkle resistance, mechanical properties, and other wear characteristics of the cotton fabric. By achieving exceptional durability and antibacterial efficacy, we obtained a value-added multifunctional cotton fabric that exhibits excellent softness, wrinkle resistance, hydrophilicity, etc. (Shah et al. 2022). 2. Experimental Methods 2.1 Materials The cotton fabric (with a weight of 94 g/m 2 ) was obtained from Sunvim Co., Ltd. N-methyldiethanolamine was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Bromo-alkanes (bromo-n-octane, bromo-n-decane, bromo-dodecane, bromo-tetradecane, bromo-cetane) and 1,2,3,4-butane tetracarboxylic acid (BTCA) were sourced from Shanghai Maclin Biochemical Technology Co., Ltd. Anhydrous ethanol, ethyl acetate, Sodium hypophosphite monohydrate (SHP) and sodium hydroxide were procured from Sinopharm Chemical Reagent Co., Ltd. All chemical reagents used in this study were analytical purity. Staphylococcus aureus ( S. aureus, CMCC(B)44102), Escherichia coli ( E. coli, CMCC(B)26003), and Candida albicans ( C. albicans, ATCC10231) strains were obtained from Beijing Microbiological Culture Center. The commercial antibacterial agent AA used in this study was an industrial-grade product provided by Qingdao Rhine Textile Materials Co., Ltd. 2.2 Synthesis of quaternary ammonium salt antibacterial agents The N-methyldiethanolamine and bromo-alkanes with varying alkyl chain lengths were dissolved in anhydrous ethanol at 80 ℃ for reflux reaction for 24 h (Fan et al. 2015; Wynne et al. 2011). Then, the solvent was removed using a rotary evaporator, and the resulting white solid product underwent ethyl acetate washing followed by vacuum filtration. Finally, quaternary ammonium salt antibacterial agents with different alkyl chain lengths were obtained, named as QAS8, QAS10, QAS12, QAS14 and QAS16, respectively. Scheme 1. Synthesis of quaternary ammonium salt antimicrobial agents. 2.3 Preparation of durable antibacterial cotton fabric The cotton fabric was pretreated with 1% NaOH solution at 100 ℃ for 1 h, thoroughly washed, and subsequently dried at 60 ℃. The antibacterial finishing solutions were prepared by dissolving required quantity (1, 3, and 5 wt%) of quaternary ammonium salt in BTCA/SHP (1:0.5). The pH value of the finishing solutions was adjusted to 4 by adding hydrochloric acid or sodium hydroxide solution (Hong 2015; Wang et al. 2023a). The treated fabric was soaked twice and rolled twice (wet pick-up 100%). The fabric was pre-baked at 80 ℃ for 5 min, followed by baking at 160 ℃ for 3 min. After being thoroughly washed and dried at 80 ℃, durable antibacterial cotton fabric was obtained (Harifi and Montazer 2012). The treated cotton fabrics were designated as 1QCT, 3QCT and 5QCT, respectively. The untreated cotton fabric was referred to as CT. The cotton fabric processed by BTCA and SHP was named BC. Fig. 1. Schematic diagrams of the durable antibacterial cotton fabric treatment process. 2.4 Characterization Fourier Transform Infrared Spectroscopy (FTIR) measurements was conducted using a Nicolet iS 50 FTIR spectrometer (Thermo Fisher Scientific, USA), employing a resolution of 4 cm -1 and acquiring a signal through 32 scans. The 1 H Nuclear Magnetic Resonance spectra ( 1 H NMR) was acquired using a 400 MHz Bruker ANCE III HD spectrometer (Bruker, Germany), with CDCl 3 serving as the solvent. The minimum inhibitory concentration (MIC) of quaternary ammonium salts and AA against S. aureus and E. coli was determined by the broth microdilution method (Feng et al. 2017). In brief, the bacterial suspension (10 6 CFU/mL) was mixed with various concentrations of samples and then incubated in a sharking incubator at 37 ℃ for 24 h. As a control, MH broth was used instead of the sample solution. MIC is the lowest concentration of samples in the suspension that can inhibit the growth of a microorganism after overnight incubation. After 24 h of incubation, the minimum bactericidal concentration (MBC) and minimum fungal concentration (MFC) were determined by extracted mixed suspension and spotted on an agar plate incubated at 37 ℃ for another 24 h. The minimum concentration of samples that fully killed the bactericidal and funi on the agar plate was recorded as MBC and MFC, respectively. The dissolution/non-dissolution type of antibacterial cotton fabric was determined by the zone of inhibition (ZOI) test according to the Chinese GB/T 31713-2015. The X-ray photoelectron spectroscopy (XPS) analysis was performed using an Al K α excitation radiation on a Thermo Scientific K-Alpha instrument (Thermo Fisher Scientific, USA)(Chen et al. 2023). The surface morphology and elemental distribution of cotton fabric were examined using a scanning electron microscope equipped with an energy dispersive X-ray spectrometer (SEM-EDS, JSM-7800F, Nippon Electronics, Japan) under the following test conditions: gold spray treatment for 5 min and accelerating voltage of 15 kV. The antimicrobial activities of the cotton fabric were performed according to the GB/T 20944.3-2008 by a shake-flask method. Briefly, the clipped cotton samples were placed in the bacterial suspension and shaken for some time. After that, the diluted bacterial suspension was inoculated on agar plates and incubated at 37°C for 24 h. Finally, the survival rate of the microorganisms was calculated using the plate counting method, so that the antibacterial activity of the cotton fabric was determined by the colony forming units (CFU) on the agar plates. Each sample was repeated three times. According to AATCC 61-2013 No.1A, the laundering durability of cotton fabric was investigated using SW-20B standard laundering machine (Quanzhou Meibang Instrument CO. Ltd., China). The experimental procedure involved using a detergent with a mass fraction of 0.37% and subjecting the fabric at 40 ℃ for 45 min (1 laundering cycle is equivalent to 5 home or hand launderings). The cotton fabric underwent 5, 20 and 50 laundering cycles, respectively, denoted as 5 LC, 20 LC and 50 LC. After laundering test, the antibacterial activity of the washed cotton fabric was evaluated using an oscillation method, followed by quantification of antibacterial efficacy through live bacteria plate counting. According to GB/T 3923.1-2003, the tensile test was evaluated using the Instron5967 Universal Material Testing Machine (Instrang, USA). The test was conducted by preparing four warp and four weft samples measuring 50×200 mm , and taking the average value. The softness of cotton fabric was assessed using the ring method. This involved folding 160×40 mm fabric in half naturally, placing it horizontally, and measuring the height of the ring. In accordance with standard AATCC 66-2008, the fabric's Wrinkle Recovery Angle (WAR) was assessed using the M5010 Crease Recovery Tester (Mountain Spinning, China). For testing purposes, 15 ×40 mm fabric samples were prepared, consisting of three pieces in the warp direction and three pieces in the weft direction. The sum of average values from both directions represented the total crease recovery angle. The Theta Contact Angle Measuring Instrument (Biolin, Sweden) was employed to measure the contact angle of cotton fabric. According to the standard GB/T 17644-2008, the Datacolor 850 Color Matching System (Datacolor, China) was employed for assessing the whiteness of fabric. According to GB/T 5453-1997, the breathability of cotton fabric was assessed using a Breathability Analyzer (FX3300IV, TEXTEST, Switzerland). The hand (softness, deflection, slip), drape, crease recovery, and other indicators of cotton fabric were evaluated using the FES-3-10 instrument (NuCybertek, Mexico) in accordance with AATCC TM202. 3. Results And Discussion 3.1 Characterization of quaternary ammonium salt antibacterial agents The FTIR spectra of the synthesis of five quaternary ammonium salts were presented in Fig. 2 (a). The absorption peak at 3290 cm -1 was assigned to the stretching vibration of -OH group, which was indicative of the structure of quaternary ammonium salt. Additionally, the peaks at 2920 cm -1 and 2850 cm -1 belonged to the vibrations of -CH 3 and -CH 2 - groups, respectively. Furthermore, the N + -C stretching vibration peaks for QAS8, QAS10, QAS12, QAS14, and QAS16 were observed at 968, 962, 969, 975 and 965 cm -1 , respectively (Li et al. 2018; Shakil Hussain et al. 2019; Tang et al. 2016), which indicated that the reaction successfully happened between N-methyldiethanolamine and bromo-alkanes. To further verify the chemical structure of quaternary ammonium salts, the 1 H NMR spectra were employed and presented in Fig. 2 (b)-(f). The position labeled as H in the structural formula corresponded to the numbers indicated in the spectra. These synthesized quaternary ammonium salts exhibited similar structures, differing only in alkyl chain length, resulting in 1 H NMR spectra with variations observed in hydrogen atom counts at labeled 2 (1.23 ppm). Notably, an increase in alkyl chain length led to a corresponding increase in the number of hydrogen atoms at these positions (Zhang et al. 2018; Zhang et al. 2021). The successful synthesis of the quaternary ammonium salt was confirmed by FTIR and 1 H NMR spectroscopy. Fig. 2. FTIR spectra (a) and 1 H NMR spectra (b)-(f) of QAS8-QAS16. The MIC and MBC value of quaternary ammonium salts and AA were presented in Fig. 3. MIC, which referred to the minimum concentration of antibacterial agents that can inhibit microbial growth, was an important indicator for evaluating their efficacy (Bazina et al. 2019; Fanfoni et al. 2021). On the other hand, MBC represented the lowest concentration at which an antibacterial agent can completely kill bacteria. As shown in Fig. 3, the MIC value of QAS8 against S. aureus gradually decreased to 32 mg/L for QAS14 before stabilizing. Similarly, for E. coli , the MIC value decreased from 1024 mg/L (QAS8) to 16 mg/L (QAS16). The MBC value followed a similar trend with QAS8 showing a gradual decrease until reaching stability at 64 mg/L (QAS14), indicating that alkyl chain length affects its antibacterial activity by enhancing interaction with cell plasma membranes and promoting leakage of cellular components. Notably, QAS12 exhibited an MIC value of 128 mg/L and an MBC value of 256 mg/L against both S. aureus and E. coli while commercially available antimicrobial agent AA showed respective values of 32 mg/L (MIC) and 128 mg/L (MBC) against these strains. Considering their similarity to AA's MIC and MBC values, QAS12 and QAS14 were selected for further experiments on cotton fabric. Fig. 3. MIC and MBC values of quaternary ammonium salts and AA against E. coli and S. aureus . 3.2 Characterization of antibacterial cotton fabric ZOI results on cotton fabric were presented in Fig. 4. The agar plate of CT and BC exhibited a substantial presence of consecutive colonies of S. aureus , E. coli , and C. albicans . BTCA and SHP did not significantly influence the antibacterial properties of the base fabric. Additionally, QAS12 did not exhibit an obvious ZOI against E. coli and C. albicans ; however, it showed a clear ZOI against S. aureus which was absent in the treated cotton fabric sample. Quaternary ammonium salt-treated cotton fabric demonstrated excellent antibacterial effects. Compared to E. coli and C. albicans , the treated cotton fabric exhibited a wider bacterial inhibition zone with a width of 3 mm against S. aureus . Quaternary ammonium salts had some inhibitory effect on the growth of S. aureus , E. coli , and C. albicans . The isoelectric point (PI) of S. aureus is approximately 2-3, whereas the PI of E. coli ranges from 4 to 5, and that of C. albicans is around 6 (Uppu et al. 2023). Consequently, microorganisms exhibit a negative charge in near-neutral or weakly alkaline environments. As a result, S. aureus , with a higher number of negative charges, demonstrates enhanced affinity towards positively charged quaternary ammonium salts leading to augmented antibacterial efficacy against S. aureus . Compared to QAS12-treated cotton fabric, QAS14-treated ones demonstrated evident bactericidal activity against S. aureus , E. coli , and C. albicans with respective widths of ZOI measuring at 4.5, 1.5 and 2 mm, respectively, which suggested that QAS14 had stronger antimicrobial effected with enhanced dissolution. According to the GB/T 31713-2015 standard (Xu et al. 2021), ZOI with a width of less than 1 mm are classified as non-dissolution type, while those with a width of 1-5 mm are categorized as micro-dissolution type. ZOI ranging from 5-10 mm indicate moderate dissolution, and those exceeding 10 mm fall under high dissolution type. Non-soluble antibacterial agents possess active groups that can chemically bond with fabric, resulting in improved antibacterial properties and durability of cotton fabric. These agents did not penetrate bacteria but instead eliminate them by disrupting their structures, thereby preventing bacterial resistance without entering the human body and ensuring safety. Based on the analysis of MIC, MBC, and ZOI, QAS12 treated cotton fabric were selected for this study and referred to as QCT. Fig. 4. ZOI photographs of cotton fabric. To learn about the difference of functional group and chemical state of CT and QCT, FTIR spectra and XPS were utilized to examine. Fig. 5 (a) showed the FTIR spectra of QCT, and CT was used as control. In these results, the spectra of cotton fabric looked similar. But compared with CT, there are two novel characteristic peaks at 1730 cm -1 and 1580 cm -1 observed after treating with QAS12. These two peaks are attributed to the vibration of -COOH and N + group. Fig. 5 (b) showed the XPS full survey spectrum of QCT, in which C 1s and O 1s were severally identified (Li et al. 2020; Wang et al. 2023b). Besides, the N 1s high-resolution spectrum of (Fig. 5 (c)) showed a double band corresponding to C-N and N + , which had two strong peaks at 374.5 and 368.6 eV with a doublet splitting of about 6.0 eV, and two weak peaks at 399.7 eV and 402.2 eV. Through FTIR analysis of chemical structure and XPS analysis of surface elements on the cotton fabric, successful formation of ester bond covalent crosslinking between QAS12 and cotton fabric was confirmed. Fig. 5. FTIR spectra of CT and QCT (a), XPS full survey spectrum (b), and high-resolution spectra of N 1s (c). Fig. 6 (a) presented the SEM morphology of CT and QCT (Liu et al. 2013). From the results, a regular and even film is deposited on the surface of QCT compared with the smooth surface of CT. The above observations suggest that QAS12 is successfully loaded on the surface of cotton fabric. The EDS mapping showed the uniform distribution of N on QCT surface, certificating the adhesion of QAS12 treating on the surface of the cotton fabric (Lin et al. 2018). These observations, combined with SEM and EDS analyses, provided further evidence supporting the covalent cross-linking of QAS12 onto the cotton fabric surface. Fig. 6. SEM of CT and QCT (a) and EDS of QCT (b). 3.3 Performance analysis of durable antibacterial cotton fabric The antimicrobial activity of treated cotton fabric was further determined by the shaking flask method. In the test, the bacterial suspension was co-cultured with the cotton fabric under shaking for 24 h to ensure the cotton fabric full contact with the bacteria. After that, the suspension was diluted by a factor of ten to ten thousand times and then incubated on an agar plate for another 24 h. Fig. 7 (a) showed the digital photographs of the agar plate corresponding to CT, 1QCT, 3QCT, and 5QCT. It proved that all the agar plates corresponding to CT had some microbial growth of E. coli , S. aureus , and C. albicans , while those corresponding to 1QCT, 3QCT, and 5QCT showed fewer microbial colonies, indicating the antimicrobial activity of treated cotton fabric. Besides, the bacteriostasis rate of the treated cotton fabric was calculated by the plate-counting method to determine the antibacterial efficiency of the treated cotton fabric. As seen from Fig. 7 (b), excepted for the antibacterial rate of E. coli against the concentration of 1QCT which was found to be at a level of about only 98.5%, all other concentrations showed an antibacterial rate as high as 99.99%. Under conditions where inhibition rates for gram-positive bacteria, gram-negative bacteria and fungi were maintained at levels above or equal to 99.99%, we selected 3QCT for laundering test. Fig. 7 (c) showed that agar plates having microbial suspensions treated with 3QCT after 10 and 50 home laundering cycles still had no or very few microbial colonies (Jin et al. 2024). As can be seen from Fig. 7 (d), 3QCT showed high laundering durability and the antibacterial rates for S. aureus , E. coli , and C. albicans remained high at levels above or equal to 99.99%, 87.5% and 99.99%, respectively(Bukhari et al. 2023; Tian et al. 2014). This could be attributed to the fact that the outer membrane component of E. coli cells is composed of fat polysaccharide, and lipopolysaccharide exhibits significant toxicity, enabling it to resist the invasion of other materials such as antibacterials (Pei et al. 2023). Despite this, the antibacterial rate still met AAA standards, indicating that surface finishing with quaternary ammonium salts on cotton fabric can enhance its antibacterial durability. In summary, cotton fabric treated with different concentrations exhibited remarkable antibacterial properties against both gram-positive and gram-negative bacteria as well as fungi, while also demonstrating excellent wash resistance. This can be attributed to the chemical bonding between QAS12 and the cotton fabric surface, which prevents easy elution during washing processes and ensures good durability and antibacterial efficacy. Among various concentrations tested, 3% QAS12 finishing displayed exceptional antibacterial and washable properties; henceforth referred to as QCT for further investigation into other fabric characteristics. Fig. 7. Digital photos of agar plates having microbial suspensions with cotton fabric (a), bacteriostatic rates of cotton fabric of different concentrations (b), digital photos of agar plates having microbial suspensions with QCT after laundering cycles (c), and bacteriostatic rates of QCT versus the number of laundering cycles (d). The mechanical properties of cotton fabric were illustrated in Fig. 8 (a), which were crucial factors influencing the long-term durability of the fabric. These properties were evaluated based on the tensile strength and breaking elongation. As shown in Fig. 8 (a), compared to CT, QCT exhibited a decrease in weft tensile strength from 334 N to 294 N and a decrease in weft breaking elongation from 11% to 8%. Similarly, the warp tensile strength decreased from 685 N to 557 N while the warp breaking elongation remained unchanged at approximately 14%. These slight changes can be attributed to potential loss of strength caused by BTCA cross-linking with cellulose as well as acid degradation of cellulose. Additionally, high temperature baking can lead to degradation of macromolecular chains within the fibers. However, it is worth noting that these changes fall within an acceptable range, indicating that neither the finishing process nor finishing agent compromised the structural integrity of cotton fabric (Ke et al. 2020). The softness of cotton fabric was illustrated in Fig. 8 (b). A lower height indicated better softness. QCT exhibited a circle height that is 0.5 cm lower than CT (Xu et al. 2019), providing evidence for its superior softness and hand feel. This can be attributed to the irregular curly state formed by the alkyl chain in the molecular structure of quaternary ammonium salt, which contributes to the softness of the molecule. The flexible molecules adsorbed on the fiber surface act as lubricants, reducing both dynamic and static friction coefficients between fibers. Consequently, quaternary ammonium salt-treated cotton fabric demonstrates excellent durability, antibacterial properties, remarkable softness, and represents a multifunctional high-value-added textile (Li et al. 2023). The wrinkle resistance of cotton fabric was illustrated in Fig. 8 (c). A higher wrinkle recovery angle indicated better wrinkle resistance. Compared to CT, QCT exhibited an increased total crease recovery angle from 154° to 185°, indicating improved anti-wrinkle properties. The weak interaction force between molecules in the amorphous region of cellulose can be disrupted by water diffusion during washing, causing molecular chains in the amorphous region to easily slip under external forces. However, when a new position is reached, new hydrogen bonds or intermolecular van der Waals forces can form between cellulose molecular chains, providing fixation. Additionally, stretching the fabric alters the position of hydroxyl groups on cellulose molecules and separates original hydrogen bonds and intermolecular forces within fiber macromolecular chains in the amorphous region, leading to formation of new forces at these positions. By forming a cross-linked network structure with BTCA, cotton cellulose prevents easy slipping of molecular chains and thus enhances wrinkle resistance. Fig. 8. Tensile test (a), softness (b), and wrinkle Recovery Angle (c) of CT and QCT. The hydrophilicity and air permeability of cotton fabric directly impact the textile's comfort, while the whiteness significantly influences its aesthetic appeal. Evaluating the hydrophilicity, air permeability, and whiteness of cotton fabric allows for an assessment of both its comfort and beauty. The hydrophilicity of the cotton fabric was illustrated in Fig. 9 (a). It was characterized by the water contact angle (WCA) of the cotton fabric, which decreased from 44° to 27°, indicating a significant enhancement in hydrophilicity (Saha et al. 2021). A smaller contact angle corresponds to better hydrophilicity. This improvement can be attributed to the strong hydrophilic nature of the acyl oxygen group. The air permeability of QCT, which connected with the porosity of the cotton fabric and regarded as an essential factor in the breathability and heat exchange of the cotton fabric, was tested according to the Chinese GB/T 5453-1997 standard (Zhu et al. 2018). As shown in Fig. 9 (b), the air permeability of QCT only slightly decreased to 223 mm/s from 193 mm/s of CT. Thus, QAS12 had minimal impact on the breathability of the cotton fabric, it can be attributed to the pad-dry-cure process employed during cotton fabric treating, which leads to an increase in twisted and flat areas of the cotton fabric. Consequently, there is a decrease in porosity and air permeability. The whiteness of the cotton fabric was depicted in Fig. 9 (c) (Huang et al. 2019; Yeo and Lau 2021). Prior to finishing, the whiteness of the cotton fabric was measured at 88%, which remained almost unchanged at 87% post-finishing. Notably, no yellowing phenomenon was observed. In summary, the hydrophilicity of the treated cotton fabric improved while there was a slight decrease in air permeability; however, these changes were negligible compared to antibacterial textiles. This suggests that both the finishing process and quaternary ammonium salt antibacterial agent had minimal impact on the overall properties and usability of the finished cotton fabric. Hand assessment of the cotton fabric was performed on an apparatus to simulate the hand sensation when people touch a fabric. Some important parameters of the relative hand value, including softness, resilience, and smoothness scores of the fabric were recorded and presented in Fig. 9 (d). It can be observed that QCT had very few changes on the softness, resilience, and smoothness scores to 58, 26, 52 and 48 from 59, 24, and 52 of CT, respectively. It indicates that QCT have good tactile qualities involving a series of feel attributes and can present a feel near CT. Fig. 9. Hydrophilicity (a), air permeability (b), whiteness (c), and hand assessment (d) of CT and QCT. 4. Conclusion The quaternary ammonium salt antibacterial agents designed and synthesized in this experiment, together with the prepared durable antibacterial cotton fabric, demonstrated exceptional antimicrobial activity against gram-positive bacteria, gram-negative bacteria, and fungi. The concentration of the finishing agent was significantly lower than that of existing market antibacterial agents while maintaining excellent laundering durability. Even after undergoing 50 laundering cycles, the antibacterial rate of the cotton fabric still met the AAA antibacterial standard without any noticeable impact on its wearability or whiteness. Furthermore, hydrophilicity, softness, and wrinkle resistance were significantly improved. Although there was a slight decrease in mechanical properties and air permeability, it did not affect overall practical use. The quaternary ammonium salt antibacterial agents exhibited broad-spectrum bactericidal activity at a high rate. Additionally, the finishing method for cotton fabric proved to be simple, rapid, economical while resulting in durable and long-lasting antimicrobial effects due to chemical bonding between quaternary ammonium salt and cotton fibers. Declarations Ethical approval This article does not contain any studies with human participants or animals performed by any of the authors. Funding This work was financially supported by Young Elite Scientist Sponsorship Program by CAST (2022QNRC001) and Hubei Key Laboratory for New Textile Materials and Applications (FZXCL202203). Data availability Data will be made available on request. Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. References Bazina L et al. (2019) Discovery of novel quaternary ammonium compounds based on quinuclidine-3-ol as new potential antimicrobial candidates. Eur J Med Chem 163:626-635. Bukhari A et al. (2023) A novel formulation of triethyl orthoformate mediated durable, smart and antibacterial chitosan cross-linked cellulose fabrics. Int. J. Biol. Macromol 253:126813. 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Uppu D, Wang XG, Lee JC (2023) Contribution of Extracellular Membrane Vesicles To the Secretome of Staphylococcus aureus. Mbio 14.1: e03571-22. Wang G et al. (2022) A new class of quaternary ammonium compounds as potent and environmental friendly disinfectants. J Clean Prod 379:134632. Wang J, Fang K, Liu X, Zhang S, Qiao X, Liu D (2023a) A review on the status of formaldehyde-free anti-wrinkle cross-linking agents for cotton fabrics: Mechanisms and applications. Ind Crops Prod 200:116831. Wang Y, Zhang S, Zhu J, Li N, Yin Y (2023b) Fabrication of wood-inspired nanocellulose-based aerogels for efficient adsorption and filtration removal of Congo red. Ind Crops Prod 205: 117482. Wynne JH, Fulmer PA, McCluskey DM, Mackey NM, Buchanan JP (2011) Synthesis and Development of a Multifunctional Self-Decontaminating Polyurethane Coating. ACS Appl Mater Interfaces 3:2005-2011. Xu F, Zhong L, Xu Y, Zhang C, Zhang F, Zhang G (2019) Highly efficient flame-retardant and soft cotton fabric prepared by a novel reactive flame retardant. Cellulose 26:4225-4240. Xu J, Xie Z, Du F, Wang X (2021) One-step anti-superbug finishing of cotton textiles with dopamine-menthol. J Mater Sci Technol 69:79-88. Xu Q, Ke X, Shen L, Ge N, Zhang Y, Fu F, Liu X (2018) Surface modification by carboxymethy chitosan via pad-dry-cure method for binding Ag NPs onto cotton fabric. Int J Biol Macromol 111:796-803. Yeo WS, Lau WJ (2021) Predicting the whiteness index of cotton fabric with a least squares model. Cellulose 28:8841-8854. Zhang J, Tan W, Luan F, Yin X, Dong F, Li Q, Guo Z (2018) Synthesis of Quaternary Ammonium Salts of Chitosan Bearing Halogenated Acetate for Antifungal and Antibacterial Activities. Polymers 10(5), 530. Zhang X et al. (2021) Design and production of environmentally degradable quaternary ammonium salts. Green Chem 23:6548-6554. Zhu GC, Fang Y, Zhao LY, Wang JF, Chen WL (2018) Prediction of structural parameters and air permeability of cotton woven fabric. Text Res J 88:1650-1659. Scheme Scheme 1 is available in the Supplementary Files section. Additional Declarations No competing interests reported. Supplementary Files S1.jpg Scheme 1. Synthesis of quaternary ammonium salt antimicrobial agents. Cite Share Download PDF Status: Published Journal Publication published 01 Jun, 2024 Read the published version in Cellulose → Version 1 posted Editorial decision: Revision requested 23 Mar, 2024 Reviews received at journal 13 Mar, 2024 Reviewers agreed at journal 09 Mar, 2024 Reviewers invited by journal 09 Mar, 2024 Editor assigned by journal 09 Mar, 2024 Submission checks completed at journal 09 Mar, 2024 First submitted to journal 07 Mar, 2024 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. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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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-4034782","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":277802613,"identity":"d0dd8d04-8dc9-4e70-a665-01497c1afc9c","order_by":0,"name":"Qi Ding","email":"","orcid":"","institution":"Qingdao University","correspondingAuthor":false,"prefix":"","firstName":"Qi","middleName":"","lastName":"Ding","suffix":""},{"id":277802614,"identity":"0d18fcb3-f3dd-4d62-a23f-4cb2ce9e746f","order_by":1,"name":"Jiang-Long Liu","email":"","orcid":"","institution":"Qingdao University","correspondingAuthor":false,"prefix":"","firstName":"Jiang-Long","middleName":"","lastName":"Liu","suffix":""},{"id":277802615,"identity":"9a86cd4f-403a-4ce1-b161-516024f7a7bd","order_by":2,"name":"Yan-Yan Liu","email":"","orcid":"","institution":"Qingdao University","correspondingAuthor":false,"prefix":"","firstName":"Yan-Yan","middleName":"","lastName":"Liu","suffix":""},{"id":277802616,"identity":"eb483106-e8e5-484e-ab93-ccbaa2e1e6ab","order_by":3,"name":"Wen-Zhan He","email":"","orcid":"","institution":"Qingdao University","correspondingAuthor":false,"prefix":"","firstName":"Wen-Zhan","middleName":"","lastName":"He","suffix":""},{"id":277802617,"identity":"6a23995b-4111-43b9-9887-00930a84f713","order_by":4,"name":"Lin Zhang","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAAyElEQVRIiWNgGAWjYBACPmYGBgkGBgs5BoYEIJeNCC1sEC0SxiRoYYBoSWwgXgs778EbP/5IpPcdzzFg+FB2mIF/dgMhh/ElW/bwSOTOPPPGgHHGucMMEncOENLCYybBIyGRu+FGjgEzb9thBgOJBMJaJP8YSKQbgLT8JVaLNE+CRAJYCyORWoytZQ5IGM4886zgYM+5dB6JGwS08POfMbz55o+NPN/x5I0PfpRZy/HPIKAFAQ6AEQMPseohWkbBKBgFo2AUYAUAffE54dJu3KMAAAAASUVORK5CYII=","orcid":"","institution":"Qingdao University","correspondingAuthor":true,"prefix":"","firstName":"Lin","middleName":"","lastName":"Zhang","suffix":""},{"id":277802618,"identity":"e6cbe73c-9dfd-4a37-95fa-a6bd97f45419","order_by":5,"name":"Ying-Jun Xu","email":"","orcid":"","institution":"Qingdao University","correspondingAuthor":false,"prefix":"","firstName":"Ying-Jun","middleName":"","lastName":"Xu","suffix":""}],"badges":[],"createdAt":"2024-03-08 02:51:38","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4034782/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4034782/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s10570-024-05991-w","type":"published","date":"2024-06-01T14:07:43+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":52543854,"identity":"1549dd59-56ed-4b69-91f0-2fe16c60846b","added_by":"auto","created_at":"2024-03-12 18:10:24","extension":"jpg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":84377,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic diagrams of the durable antibacterial cotton fabric treatment process.\u003c/p\u003e","description":"","filename":"Picture2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/806a32535b574efc4de78716.jpg"},{"id":52543856,"identity":"78eeca06-6501-49fa-a3dc-3683abc6e7dd","added_by":"auto","created_at":"2024-03-12 18:10:24","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":128608,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra (a) and \u003csup\u003e1\u003c/sup\u003eH NMR spectra (b)-(f) of QAS8-QAS16.\u003c/p\u003e","description":"","filename":"Picture3.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/0af3eb93779c3f5fa5a7f76d.jpg"},{"id":52543860,"identity":"a48ccd44-a5d5-4dee-880f-2623d9e427aa","added_by":"auto","created_at":"2024-03-12 18:10:24","extension":"jpg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":261236,"visible":true,"origin":"","legend":"\u003cp\u003eMIC and MBC values of quaternary ammonium salts and AA against \u003cem\u003eE. coli \u003c/em\u003eand \u003cem\u003eS. aureus\u003c/em\u003e.\u003c/p\u003e","description":"","filename":"Picture4.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/92cbb44a0fb6f9ab7e05abdc.jpg"},{"id":52543862,"identity":"9c4343e2-30c0-4789-8f61-b0ce2f0f82ec","added_by":"auto","created_at":"2024-03-12 18:10:24","extension":"jpg","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":245288,"visible":true,"origin":"","legend":"\u003cp\u003eZOI photographs of cotton fabric.\u003c/p\u003e","description":"","filename":"Picture5.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/7dd3ef9cc4a9fc47f668107e.jpg"},{"id":52543857,"identity":"e409a8e7-6954-4409-b360-2ad9d7634bcf","added_by":"auto","created_at":"2024-03-12 18:10:24","extension":"jpg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":137662,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectra of CT and QCT (a), XPS full survey spectrum (b), and high-resolution spectra of N 1s (c).\u003c/p\u003e","description":"","filename":"Picture6.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/72911699fa3c3e2e26b60524.jpg"},{"id":52544787,"identity":"2a16598e-69ff-43d8-9559-b27a656645ae","added_by":"auto","created_at":"2024-03-12 18:18:24","extension":"jpg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":106458,"visible":true,"origin":"","legend":"\u003cp\u003eSEM of CT and QCT (a) and EDS of QCT (b).\u003c/p\u003e","description":"","filename":"Picture7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/804739b0f5ee92bb81d35a91.jpg"},{"id":52543853,"identity":"f1044a19-76f3-4073-b164-09ab22e75aa5","added_by":"auto","created_at":"2024-03-12 18:10:24","extension":"jpg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":308164,"visible":true,"origin":"","legend":"\u003cp\u003eDigital photos of agar plates having microbial suspensions with cotton fabric (a), bacteriostatic rates of cotton fabric of different concentrations (b), digital photos of agar plates having microbial suspensions with QCT after laundering cycles (c), and bacteriostatic rates of QCT versus the number of laundering cycles (d).\u003c/p\u003e","description":"","filename":"Picture8.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/f90b206177bc1bcf35f69ba4.jpg"},{"id":52543861,"identity":"061f8493-733f-457b-b491-0f38dd222673","added_by":"auto","created_at":"2024-03-12 18:10:24","extension":"jpg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":83180,"visible":true,"origin":"","legend":"\u003cp\u003eTensile test (a), softness (b), and wrinkle Recovery Angle(c) of CT and QCT.\u003c/p\u003e","description":"","filename":"Picture9.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/8320db3ced5477e41bc4d1d2.jpg"},{"id":52543859,"identity":"a10cd837-2f63-45c6-928d-3a904d791b3f","added_by":"auto","created_at":"2024-03-12 18:10:24","extension":"jpg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":195059,"visible":true,"origin":"","legend":"\u003cp\u003eHydrophilicity (a), air permeability (b), whiteness (c), and hand assessment (d) of CT and QCT.\u003c/p\u003e","description":"","filename":"Picture10.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/ca8308c68f7c76c4a9bdbc17.jpg"},{"id":60742336,"identity":"0fc8e71a-4e00-47f1-bdfb-fb5bc559bb73","added_by":"auto","created_at":"2024-07-20 14:07:48","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1919556,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/f68cc625-b2d8-4315-8525-6a2651d80de3.pdf"},{"id":52544786,"identity":"73b1e961-1cfc-4837-bcb6-f24246afee36","added_by":"auto","created_at":"2024-03-12 18:18:24","extension":"jpg","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":29833,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cstrong\u003eScheme 1.\u003c/strong\u003e Synthesis of quaternary ammonium salt antimicrobial agents.\u003c/p\u003e","description":"","filename":"S1.jpg","url":"https://assets-eu.researchsquare.com/files/rs-4034782/v1/67df477228c29b66092609d9.jpg"}],"financialInterests":"No competing interests reported.","formattedTitle":"Durable antibacterial cotton fabrics with good performance enabled by quaternary ammonium salts","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eCotton fabric is highly favored by consumers due to its softness, hydrophilicity, comfort, skin-friendliness, and other characteristics, making it a popular choice in the textile industry. As cotton fabric comes into direct contact with the skin and absorbs sweat and other secretions from the human body (Chang and Wang 2023), it can provide breeding grounds and nutrients for bacteria. Therefore, antibacterial treatment of cotton fabric plays a crucial role in effectively preventing bacterial reproduction and reducing the risk of diseases caused by bacterial infections. For achieving antibacterial properties on natural fibers like cotton, various methods such as dipping method, padding method, and chemical grafting method have been extensively researched and applied (Gao et al. 2021). However, there are challenges associated with maintaining durable antibacterial efficacy of treated cotton fabric as well as issues related to color change after treatment that leads to significant deterioration in mechanical properties and poor hand experience. The primary goal moving forward is to attain durability, antibacterial efficacy, and enhanced hand. To accomplish this, the most efficacious strategy for augmenting both the endurance and antibacterial properties of cotton fabric entails covalently attaching the antimicrobial agent onto its surface.\u003c/p\u003e\n\u003cp\u003eThe ideal antibacterial agent should fulfill the following criteria: (1) exhibit a broad spectrum and high efficacy against bacteria; (2) not compromise the strength, moisture absorption, or other physical properties of cotton fabric; (3) demonstrate strong adhesion to cotton fabric while retaining durability and antibacterial activity after\u0026nbsp;laundering cycles\u0026nbsp;and exposure to sunlight; (4) possess low cost, simple processing requirements, and compatibility with other finishing agents (Liu et al. 2022). Among commonly employed antibacterial agents, natural alternatives offer abundant resources and good biocompatibility but suffer from limited antimicrobial activity, inadequate persistence, and complex extraction processes. Inorganic antimicrobials such as metal-ionic compounds are widely used; however, nanostructured antimicrobials with increased specific surface area for enhanced bacterial adsorption present drawbacks including toxicity, unstable performance, and susceptibility to discoloration. Photocatalytic antimicrobials suffer from the drawback of light dependence. Organic antibacterial agents exhibit a wide range of applications and possess strong bactericidal capabilities. In organic antimicrobials, the antimicrobial properties of halogenated amines are associated with their own structural characteristics. Upon contact with bacteria, N-X bonds exterminate them, transforming into N-H bonds and losing activity; subsequent halogenation restores the bactericidal properties by converting them back to N-X bonds. However, their limited hydrophilicity restricts their scope of application (Dong et al. 2017). Quaternary ammonium salts offer broad-spectrum antibacterial effects, simple production processes, rapid and efficient sterilization abilities, good hydrophilicity, and easy elution while minimizing secondary pollution (Wang et al. 2022). The positively charged N\u003csup\u003e+\u003c/sup\u003e in quaternary ammonium salts directly interacts with negatively charged cells through electrostatic adsorption (Gharibi et al. 2019; Makvandi et al. 2018). Either the long-chain alkyl group connected to N\u003csup\u003e+\u003c/sup\u003e penetrates the cell wall causing leakage of intracellular contents leading to cell death or the negative charge on the cell wall is attracted towards the side in contact with quaternary ammonium salts thereby reducing electronegativity on that side resulting in rupture of cell wall followed by leakage of intracellular contents leading to cell death.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eGao et al. synthesized a nanocomposite material based on silicone quaternary ammonium salt for antibacterial finishing of cotton fabric. The resulting antibacterial rate of the fabric reached 90%, and even after 10\u0026nbsp;laundering cycles, the antibacterial rate against Escherichia coli and Staphylococcus aureus remained above 85%. Additionally, the finishing process improved the hydrophilicity, air permeability, and softness of the cotton fabric to some extent (Gao et al. 2019). Wang et al. optimized the antibacterial finishing process of cotton fabric using a novel BJK01 silicone quaternary ammonium salt antibacterial agent. After this treatment, the initial antibacterial rate of cotton fabric approached 100% without\u0026nbsp;laundering, and it still maintained an antibacterial rate of 70% even after undergoing 50\u0026nbsp;laundering cycles\u0026nbsp;while meeting AAA antimicrobial standards. However, it should be noted that quaternary ammonium salt finishing may lead to significant loss in durability, antimicrobial properties, strength as well as noticeable decline in whiteness, softness and wrinkle resistance.\u003c/p\u003e\n\u003cp\u003eThe objective of this experiment was to design and synthesize quaternary ammonium salt antibacterial agents with varying alkyl chain lengths, select an appropriate quaternary ammonium salt through antibacterial testing, and fabricate durable antibacterial cotton fabric using the pad-dry-cure method (Huang et al. 2022; Xu et al. 2018). The covalent cross-linking of the quaternary ammonium salt with the cotton fabric ensures minimal elution. Comprehensive analysis was conducted on the soft properties, wrinkle resistance, mechanical properties, and other wear characteristics of the cotton fabric. By achieving exceptional durability and antibacterial efficacy, we obtained a value-added multifunctional cotton fabric that exhibits excellent softness, wrinkle resistance, hydrophilicity, etc. (Shah et al. 2022).\u003c/p\u003e"},{"header":"2. Experimental Methods","content":"\u003cp\u003e\u003cem\u003e2.1 Materials\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eThe cotton fabric (with a weight of 94 g/m\u003csup\u003e2\u003c/sup\u003e) was obtained from Sunvim\u0026nbsp;Co., Ltd. N-methyldiethanolamine was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Bromo-alkanes (bromo-n-octane, bromo-n-decane, bromo-dodecane, bromo-tetradecane, bromo-cetane) and 1,2,3,4-butane tetracarboxylic acid (BTCA) were sourced from Shanghai Maclin Biochemical Technology Co., Ltd. Anhydrous ethanol, ethyl acetate, Sodium hypophosphite monohydrate (SHP) and sodium hydroxide were procured from Sinopharm Chemical Reagent Co., Ltd. All chemical reagents used in this study were analytical purity. Staphylococcus aureus (\u003cem\u003eS. aureus,\u003c/em\u003e CMCC(B)44102), Escherichia coli (\u003cem\u003eE. coli,\u003c/em\u003e CMCC(B)26003), and Candida albicans (\u003cem\u003eC. albicans,\u003c/em\u003e ATCC10231) strains were obtained from Beijing Microbiological Culture Center. The commercial antibacterial agent AA used in this study was an industrial-grade product provided by Qingdao Rhine Textile\u0026nbsp;Materials Co., Ltd.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e2.2 Synthesis of quaternary ammonium salt antibacterial agents\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eThe N-methyldiethanolamine and bromo-alkanes with varying alkyl chain lengths were dissolved in anhydrous ethanol at 80 ℃ for reflux reaction for 24 h (Fan et al. 2015; Wynne et al. 2011).\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThen, the solvent was removed using a rotary evaporator, and the resulting white solid product underwent ethyl acetate washing followed by vacuum filtration. Finally, quaternary ammonium salt antibacterial agents with different alkyl chain lengths were obtained, named as QAS8, QAS10, QAS12, QAS14 and QAS16, respectively.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eScheme 1.\u003c/strong\u003e Synthesis of quaternary ammonium salt antimicrobial agents.\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e2.3 Preparation of durable antibacterial cotton fabric\u0026nbsp;\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eThe cotton fabric was pretreated with 1% NaOH solution at 100 ℃ for 1 h, thoroughly washed, and subsequently dried at 60 ℃.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe antibacterial finishing solutions were prepared by dissolving required quantity (1, 3, and 5 wt%) of quaternary ammonium salt in BTCA/SHP (1:0.5). The pH value of the finishing solutions was adjusted to 4 by adding hydrochloric acid or sodium hydroxide solution (Hong 2015; Wang et al. 2023a). The treated fabric was soaked twice and rolled twice (wet pick-up 100%). The fabric was pre-baked at 80 ℃ for 5 min, followed by baking at 160 ℃ for 3 min. After being thoroughly washed and dried at 80 ℃, durable antibacterial cotton fabric was obtained (Harifi and Montazer 2012). The treated cotton fabrics were designated as 1QCT, 3QCT and 5QCT, respectively. The untreated cotton fabric was referred to as CT. The cotton fabric processed by BTCA and SHP was named BC.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 1.\u003c/strong\u003e Schematic diagrams of the durable antibacterial cotton fabric treatment process.\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e2.4 Characterization\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eFourier Transform Infrared Spectroscopy (FTIR) measurements was conducted using a Nicolet iS 50 FTIR spectrometer (Thermo Fisher Scientific, USA), employing a resolution of 4 cm\u003csup\u003e-1\u003c/sup\u003e and acquiring a signal through 32 scans.\u003c/p\u003e\n\u003cp\u003eThe \u003csup\u003e1\u003c/sup\u003eH Nuclear Magnetic Resonance spectra (\u003csup\u003e1\u003c/sup\u003eH NMR) was acquired using a 400 MHz Bruker ANCE III HD spectrometer (Bruker, Germany), with CDCl\u003csub\u003e3\u003c/sub\u003e serving as the solvent.\u003c/p\u003e\n\u003cp\u003eThe minimum inhibitory concentration (MIC) of\u0026nbsp;quaternary ammonium salts and AA\u0026nbsp;against \u003cem\u003eS. aureus\u003c/em\u003e and \u003cem\u003eE. coli\u0026nbsp;\u003c/em\u003ewas determined by the broth microdilution method (Feng et al. 2017). In brief, the bacterial suspension (10\u003csup\u003e6\u003c/sup\u003e CFU/mL) was mixed with various concentrations of samples and\u0026nbsp;then incubated in a sharking incubator at 37 ℃ for 24 h. As a control,\u0026nbsp;MH broth was used instead of the sample solution. MIC is the lowest concentration of\u0026nbsp;samples\u0026nbsp;in the suspension that can inhibit the growth of a microorganism after overnight incubation. After 24 h of incubation, the minimum bactericidal concentration (MBC) and minimum fungal concentration (MFC) were determined by extracted mixed suspension and spotted on an agar plate incubated at 37\u0026nbsp;℃\u0026nbsp;for another 24 h. The minimum concentration of\u0026nbsp;samples\u0026nbsp;that fully killed the bactericidal and funi on the agar plate was recorded as MBC and MFC, respectively.\u003c/p\u003e\n\u003cp\u003eThe dissolution/non-dissolution type of antibacterial cotton fabric was determined by the zone of inhibition (ZOI) test according to the Chinese GB/T 31713-2015.\u003c/p\u003e\n\u003cp\u003eThe X-ray photoelectron spectroscopy (XPS) analysis was performed using an Al K \u0026alpha; excitation radiation on a Thermo Scientific K-Alpha instrument (Thermo Fisher Scientific, USA)(Chen et al. 2023).\u003c/p\u003e\n\u003cp\u003eThe surface morphology and elemental distribution of cotton fabric were examined using a scanning electron microscope equipped with an energy dispersive X-ray spectrometer (SEM-EDS, JSM-7800F, Nippon Electronics, Japan) under the following test conditions: gold spray treatment for 5 min and accelerating voltage of 15 kV.\u003c/p\u003e\n\u003cp\u003eThe antimicrobial activities of the cotton fabric were performed according to the GB/T 20944.3-2008 by a shake-flask method. Briefly, the clipped cotton samples were placed in the bacterial suspension and shaken for some time. After that, the diluted bacterial suspension was inoculated on agar plates and incubated at 37\u0026deg;C for 24 h. Finally, the survival rate of the microorganisms was calculated using the plate counting method, so that the antibacterial activity of the cotton fabric was determined by the colony forming units (CFU) on the agar plates. Each sample was repeated three times.\u003c/p\u003e\n\u003cp\u003eAccording to AATCC 61-2013 No.1A, the\u0026nbsp;laundering durability\u0026nbsp;of cotton fabric was investigated using SW-20B standard\u0026nbsp;laundering\u0026nbsp;machine (Quanzhou Meibang Instrument CO. Ltd., China). The experimental procedure involved using a detergent with a mass fraction of 0.37% and subjecting the fabric at 40 ℃ for 45 min (1\u0026nbsp;laundering\u0026nbsp;cycle is equivalent to 5 home or hand\u0026nbsp;launderings). The cotton fabric underwent 5, 20 and 50 laundering cycles, respectively, denoted as 5 LC, 20 LC and 50 LC. After\u0026nbsp;laundering test, the antibacterial activity of the washed cotton fabric was evaluated using an oscillation method, followed by quantification of antibacterial efficacy through live bacteria plate counting.\u003c/p\u003e\n\u003cp\u003eAccording to GB/T 3923.1-2003, the tensile test was evaluated using the Instron5967 Universal Material Testing Machine (Instrang, USA). The test was conducted by preparing four warp and four weft samples measuring 50\u0026times;200 mm , and taking the average value.\u003c/p\u003e\n\u003cp\u003eThe softness of cotton fabric was assessed using the ring method. This involved folding 160\u0026times;40 mm fabric in half naturally, placing it horizontally, and measuring the height of the ring.\u003c/p\u003e\n\u003cp\u003eIn accordance with standard AATCC 66-2008, the fabric\u0026apos;s Wrinkle Recovery Angle (WAR) was assessed using the M5010 Crease Recovery Tester (Mountain Spinning, China). For testing purposes,\u0026nbsp;15\u0026nbsp;\u0026times;40 mm fabric samples were prepared, consisting of three pieces in the warp direction and three pieces in the weft direction. The sum of average values from both directions represented the total crease recovery angle.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe Theta Contact Angle Measuring Instrument (Biolin, Sweden) was employed to measure the contact angle of cotton fabric.\u003c/p\u003e\n\u003cp\u003eAccording to the standard GB/T 17644-2008, the Datacolor 850 Color Matching System (Datacolor, China) was employed for assessing the whiteness of fabric.\u003c/p\u003e\n\u003cp\u003eAccording to GB/T 5453-1997, the breathability of cotton fabric was assessed using a Breathability Analyzer (FX3300IV, TEXTEST, Switzerland).\u003c/p\u003e\n\u003cp\u003eThe hand (softness, deflection, slip), drape, crease recovery, and other indicators of cotton fabric were evaluated using the FES-3-10 instrument (NuCybertek, Mexico) in accordance with AATCC TM202.\u003c/p\u003e"},{"header":"3. Results And Discussion","content":"\u003cp\u003e\u003cem\u003e3.1 Characterization of quaternary ammonium salt antibacterial agents\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eThe FTIR spectra of the synthesis of five quaternary ammonium salts were presented in Fig. 2 (a). The absorption peak at 3290 cm\u003csup\u003e-1\u003c/sup\u003e was assigned to the stretching vibration of -OH group, which was indicative of the structure of quaternary ammonium salt. Additionally, the peaks at 2920 cm\u003csup\u003e-1\u0026nbsp;\u003c/sup\u003eand 2850 cm\u003csup\u003e-1\u003c/sup\u003e belonged to the vibrations of -CH\u003csub\u003e3\u003c/sub\u003e and -CH\u003csub\u003e2\u003c/sub\u003e- groups, respectively. Furthermore, the N\u003csup\u003e+\u003c/sup\u003e-C stretching vibration peaks for QAS8, QAS10, QAS12, QAS14, and QAS16 were observed at 968, 962, 969, 975 and 965 cm\u003csup\u003e-1\u003c/sup\u003e, respectively (Li et al. 2018; Shakil Hussain et al. 2019; Tang et al. 2016), which indicated that the reaction successfully happened between N-methyldiethanolamine and bromo-alkanes.\u003c/p\u003e\n\u003cp\u003eTo further verify the chemical structure of quaternary ammonium salts, the \u003csup\u003e1\u003c/sup\u003eH NMR spectra were employed and presented in Fig. 2 (b)-(f). The position labeled as H in the structural formula corresponded to the numbers indicated in the spectra. These synthesized quaternary ammonium salts exhibited similar structures, differing only in alkyl chain length, resulting in \u003csup\u003e1\u003c/sup\u003eH NMR spectra with variations observed in hydrogen atom counts at labeled 2 (1.23 ppm). Notably, an increase in alkyl chain length led to a corresponding increase in the number of hydrogen atoms at these positions (Zhang et al. 2018; Zhang et al. 2021).\u003c/p\u003e\n\u003cp\u003eThe successful synthesis of the quaternary ammonium salt was confirmed by FTIR and \u003csup\u003e1\u003c/sup\u003eH NMR spectroscopy.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 2.\u003c/strong\u003e FTIR spectra (a) and \u003csup\u003e1\u003c/sup\u003eH NMR spectra (b)-(f) of QAS8-QAS16.\u003c/p\u003e\n\u003cp\u003eThe MIC and MBC value of quaternary ammonium salts and AA were presented in Fig. 3. MIC, which referred to the minimum concentration of antibacterial agents that can inhibit microbial growth, was an important indicator for evaluating their efficacy (Bazina et al. 2019; Fanfoni et al. 2021). On the other hand, MBC represented the lowest concentration at which an antibacterial agent can completely kill bacteria. As shown in Fig. 3, the MIC value of QAS8 against \u003cem\u003eS. aureus\u003c/em\u003e gradually decreased to 32 mg/L for QAS14 before stabilizing. Similarly, for \u003cem\u003eE. coli\u003c/em\u003e, the MIC value decreased from 1024 mg/L (QAS8) to 16 mg/L (QAS16). The MBC value followed a similar trend with QAS8 showing a gradual decrease until reaching stability at 64 mg/L (QAS14), indicating that alkyl chain length affects its antibacterial activity by enhancing interaction with cell plasma membranes and promoting leakage of cellular components. Notably, QAS12 exhibited an MIC value of 128 mg/L and an MBC value of 256 mg/L against both \u003cem\u003eS. aureus\u003c/em\u003e and \u003cem\u003eE. coli\u003c/em\u003e while commercially available antimicrobial agent AA showed respective values of 32 mg/L (MIC) and 128 mg/L (MBC) against these strains. Considering their similarity to AA\u0026apos;s MIC and MBC values, QAS12 and QAS14 were selected for further experiments on cotton fabric.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 3.\u003c/strong\u003e MIC and MBC values of quaternary ammonium salts and AA against \u003cem\u003eE. coli\u003c/em\u003e\u003cem\u003e\u0026nbsp;\u003c/em\u003eand \u003cem\u003eS. aureus\u003c/em\u003e.\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.2 Characterization of antibacterial cotton fabric\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eZOI results on cotton fabric were presented in Fig. 4. The agar plate of CT and BC exhibited a substantial presence of consecutive colonies of \u003cem\u003eS. aureus\u003c/em\u003e,\u003cem\u003e\u0026nbsp;E. coli\u003c/em\u003e, and \u003cem\u003eC. albicans\u003c/em\u003e. BTCA and SHP did not significantly influence the antibacterial properties of the base fabric. Additionally, QAS12 did not exhibit an obvious ZOI against \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eC. albicans\u003c/em\u003e; however, it showed a clear ZOI against \u003cem\u003eS. aureus\u003c/em\u003e which was absent in the treated cotton fabric sample. Quaternary ammonium salt-treated cotton fabric demonstrated excellent antibacterial effects. Compared to \u003cem\u003eE. coli\u003c/em\u003e and \u003cem\u003eC. albicans\u003c/em\u003e, the treated cotton fabric exhibited a wider bacterial inhibition zone with a width of 3 mm against \u003cem\u003eS. aureus\u003c/em\u003e. Quaternary ammonium salts had some inhibitory effect on the growth of \u003cem\u003eS. aureus\u003c/em\u003e, \u003cem\u003eE. coli\u003c/em\u003e, and \u003cem\u003eC. albicans\u003c/em\u003e. The isoelectric point (PI) of \u003cem\u003eS. aureus\u003c/em\u003e is approximately 2-3, whereas the PI of \u003cem\u003eE. coli\u003c/em\u003e ranges from 4 to 5, and that of \u003cem\u003eC. albicans\u003c/em\u003e is around 6 (Uppu et al. 2023). Consequently, microorganisms exhibit a negative charge in near-neutral or weakly alkaline environments. \u0026nbsp;As a result, \u003cem\u003eS. aureus\u003c/em\u003e, with a higher number of negative charges, demonstrates enhanced affinity towards positively charged quaternary ammonium salts leading to augmented antibacterial efficacy against \u003cem\u003eS. aureus\u003c/em\u003e. Compared to QAS12-treated cotton fabric, QAS14-treated ones demonstrated evident bactericidal activity against \u003cem\u003eS. aureus\u003c/em\u003e, \u003cem\u003eE. coli\u003c/em\u003e, and \u003cem\u003eC. albicans\u003c/em\u003e with respective widths of ZOI measuring at 4.5, 1.5 and 2 mm, respectively, which suggested that QAS14 had stronger antimicrobial effected with enhanced dissolution. According to the GB/T 31713-2015 standard (Xu et al. 2021), ZOI with a width of less than 1 mm are classified as non-dissolution type, while those with a width of 1-5 mm are categorized as micro-dissolution type. ZOI ranging from 5-10 mm indicate moderate dissolution, and those exceeding 10 mm fall under high dissolution type. Non-soluble antibacterial agents possess active groups that can chemically bond with fabric, resulting in improved antibacterial properties and durability of cotton fabric. These agents did not penetrate bacteria but instead eliminate them by disrupting their structures, thereby preventing bacterial resistance without entering the human body and ensuring safety. Based on the analysis of MIC, MBC, and ZOI, QAS12 treated cotton fabric were selected for this study and referred to as QCT.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 4.\u003c/strong\u003e ZOI photographs of cotton fabric.\u003c/p\u003e\n\u003cp\u003eTo learn about the difference of functional group and chemical state\u0026nbsp;of CT and QCT, FTIR spectra and XPS were utilized to examine.\u0026nbsp;Fig. 5 (a)\u0026nbsp;showed the FTIR spectra of QCT, and CT was used as control. In these results, the spectra of cotton fabric looked similar. But compared with CT, there are two novel characteristic peaks at\u0026nbsp;1730 cm\u003csup\u003e-1\u003c/sup\u003e and 1580 cm\u003csup\u003e-1\u003c/sup\u003e observed after treating with QAS12. These two peaks are attributed to the vibration of -COOH and N\u003csup\u003e+\u003c/sup\u003e group.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eFig. 5 (b) showed the XPS full survey spectrum of QCT, in which C 1s and O 1s were severally identified (Li et al. 2020; Wang et al. 2023b). Besides, the N 1s high-resolution spectrum of (Fig. 5 (c)) showed a double band corresponding to C-N and N\u003csup\u003e+\u003c/sup\u003e, which had two strong peaks at 374.5 and 368.6 eV with a doublet splitting of about 6.0 eV, and two weak peaks at 399.7 eV and 402.2 eV. Through FTIR analysis of chemical structure and XPS analysis of surface elements on the cotton fabric, successful formation of ester bond covalent crosslinking between QAS12 and cotton fabric was confirmed.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 5.\u003c/strong\u003e FTIR spectra of CT and QCT (a), XPS full survey spectrum (b), and high-resolution spectra of N 1s (c).\u003c/p\u003e\n\u003cp\u003eFig. 6 (a) presented the SEM morphology of CT and QCT (Liu et al. 2013). From the results, a regular and even film is deposited on the surface of QCT compared with the smooth surface of CT. The above observations suggest that QAS12 is successfully loaded on the surface of cotton fabric.\u003c/p\u003e\n\u003cp\u003eThe EDS mapping showed the uniform distribution of N on QCT surface, certificating the adhesion of\u003cstrong\u003e\u0026nbsp;\u003c/strong\u003eQAS12 treating on the surface of the cotton fabric (Lin et al. 2018). These observations, combined with SEM and EDS analyses, provided further evidence supporting the covalent cross-linking of QAS12 onto the cotton fabric surface.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 6.\u003c/strong\u003e SEM of CT and QCT (a) and EDS of QCT (b).\u003c/p\u003e\n\u003cp\u003e\u003cem\u003e3.3 Performance analysis of durable antibacterial cotton fabric\u003c/em\u003e\u003c/p\u003e\n\u003cp\u003eThe antimicrobial activity of treated cotton fabric was further determined by the shaking flask method. In the test, the bacterial suspension was co-cultured with the cotton fabric under shaking for 24 h to ensure the cotton fabric full contact with the bacteria. After that, the suspension was diluted by a factor of ten to ten thousand times and then incubated on an agar plate for another 24 h. Fig. 7 (a) showed the digital photographs of the agar plate corresponding to CT, 1QCT, 3QCT, and 5QCT. It proved that all the agar plates corresponding to CT had some microbial growth of \u003cem\u003eE. coli\u003c/em\u003e, \u003cem\u003eS. aureus\u003c/em\u003e, and \u003cem\u003eC. albicans\u003c/em\u003e, while those corresponding to 1QCT, 3QCT, and 5QCT showed fewer microbial colonies, indicating the antimicrobial activity of treated cotton fabric. Besides, the bacteriostasis rate of the treated cotton fabric was calculated by the plate-counting method to determine the antibacterial efficiency of the treated cotton fabric. As seen from Fig. 7 (b), excepted for the antibacterial rate of \u003cem\u003eE. coli\u003c/em\u003e against the concentration of 1QCT which was found to be at a level of about only 98.5%, all other concentrations showed an antibacterial rate as high as 99.99%. Under conditions where inhibition rates for gram-positive bacteria, gram-negative bacteria and fungi were maintained at levels above or equal to 99.99%, we selected 3QCT for laundering test.\u003c/p\u003e\n\u003cp\u003eFig. 7 (c) showed that agar plates having microbial suspensions treated with 3QCT after 10 and 50 home laundering cycles still had no or very few microbial colonies (Jin et al. 2024). As can be seen from Fig. 7 (d), 3QCT showed high laundering durability and the antibacterial rates for \u003cem\u003eS. aureus\u003c/em\u003e, \u003cem\u003eE. coli\u003c/em\u003e, and \u003cem\u003eC. albicans\u003c/em\u003e remained high at levels above or equal to 99.99%, 87.5% and 99.99%, respectively(Bukhari et al. 2023; Tian et al. 2014). This could be attributed to the fact that the outer membrane component of \u003cem\u003eE. coli\u003c/em\u003e cells is composed of fat polysaccharide, and lipopolysaccharide exhibits significant toxicity, enabling it to resist the invasion of other materials such as antibacterials (Pei et al. 2023). Despite this, the antibacterial rate still met AAA standards, indicating that surface finishing with quaternary ammonium salts on cotton fabric can enhance its antibacterial durability. In summary, cotton fabric treated with different concentrations exhibited remarkable antibacterial properties against both gram-positive and gram-negative bacteria as well as fungi, while also demonstrating excellent wash resistance. This can be attributed to the chemical bonding between QAS12 and the cotton fabric surface, which prevents easy elution during washing processes and ensures good durability and antibacterial efficacy. Among various concentrations tested, 3% QAS12 finishing displayed exceptional antibacterial and washable properties; henceforth referred to as QCT for further investigation into other fabric characteristics.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 7.\u003c/strong\u003e Digital photos of agar plates having microbial suspensions with cotton fabric (a), bacteriostatic rates of cotton fabric of different concentrations (b), digital photos of agar plates having microbial suspensions with QCT after laundering cycles (c), and bacteriostatic rates of QCT versus the number of laundering cycles (d).\u003c/p\u003e\n\u003cp\u003eThe mechanical properties of cotton fabric were illustrated in Fig. 8 (a), which were crucial factors influencing the long-term durability of the fabric. These properties were evaluated based on the tensile strength and breaking elongation. As shown in Fig. 8 (a), compared to CT, QCT exhibited a decrease in weft tensile strength from 334 N to 294 N and a decrease in weft breaking elongation from 11% to 8%. Similarly, the warp tensile strength decreased from 685 N to 557 N while the warp breaking elongation remained unchanged at approximately 14%. These slight changes can be attributed to potential loss of strength caused by BTCA cross-linking with cellulose as well as acid degradation of cellulose. Additionally, high temperature baking can lead to degradation of macromolecular chains within the fibers. However, it is worth noting that these changes fall within an acceptable range, indicating that neither the finishing process nor finishing agent compromised the structural integrity of cotton fabric (Ke et al. 2020).\u003c/p\u003e\n\u003cp\u003eThe softness of cotton fabric was illustrated in Fig. 8 (b). A lower height indicated better softness. QCT exhibited a circle height that is 0.5 cm lower than CT (Xu et al. 2019), providing evidence for its superior softness and hand feel. This can be attributed to the irregular curly state formed by the alkyl chain in the molecular structure of quaternary ammonium salt, which contributes to the softness of the molecule. The flexible molecules adsorbed on the fiber surface act as lubricants, reducing both dynamic and static friction coefficients between fibers. Consequently, quaternary ammonium salt-treated cotton fabric demonstrates excellent durability, antibacterial properties, remarkable softness, and represents a multifunctional high-value-added textile (Li et al. 2023).\u003c/p\u003e\n\u003cp\u003eThe wrinkle resistance of cotton fabric was illustrated in Fig. 8 (c). A higher wrinkle recovery angle indicated better wrinkle resistance. Compared to CT, QCT exhibited an increased total crease recovery angle from 154\u0026deg; to 185\u0026deg;, indicating improved anti-wrinkle properties. The weak interaction force between molecules in the amorphous region of cellulose can be disrupted by water diffusion during washing, causing molecular chains in the amorphous region to easily slip under external forces. However, when a new position is reached, new hydrogen bonds or intermolecular van der Waals forces can form between cellulose molecular chains, providing fixation. Additionally, stretching the fabric alters the position of hydroxyl groups on cellulose molecules and separates original hydrogen bonds and intermolecular forces within fiber macromolecular chains in the amorphous region, leading to formation of new forces at these positions. By forming a cross-linked network structure with BTCA, cotton cellulose prevents easy slipping of molecular chains and thus enhances wrinkle resistance.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 8.\u003c/strong\u003e Tensile test (a), softness (b), and wrinkle Recovery Angle (c) of CT and QCT.\u003c/p\u003e\n\u003cp\u003eThe hydrophilicity and air permeability of cotton fabric directly impact the textile\u0026apos;s comfort, while the whiteness significantly influences its aesthetic appeal. Evaluating the hydrophilicity, air permeability, and whiteness of cotton fabric allows for an assessment of both its comfort and beauty.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003eThe hydrophilicity of the cotton fabric was illustrated in Fig. 9 (a). It was characterized by the water contact angle (WCA) of the cotton fabric, which decreased from 44\u0026deg; to 27\u0026deg;, indicating a significant enhancement in hydrophilicity (Saha et al. 2021). A smaller contact angle corresponds to better hydrophilicity. This improvement can be attributed to the strong hydrophilic nature of the acyl oxygen group.\u003c/p\u003e\n\u003cp\u003eThe air permeability of QCT, which connected with the porosity of the cotton fabric and regarded as an essential factor in the breathability and heat exchange of the cotton fabric, was tested according to the Chinese GB/T 5453-1997 standard\u0026nbsp;(Zhu et al. 2018).\u0026nbsp;As shown in Fig. 9 (b), the air permeability of QCT only slightly decreased to 223 mm/s from 193 mm/s of CT. Thus,\u0026nbsp;QAS12\u0026nbsp;had minimal impact on the breathability of the cotton fabric,\u0026nbsp;it can be attributed to the pad-dry-cure process employed during cotton fabric treating, which leads to an increase in twisted and flat areas of the cotton fabric. Consequently, there is a decrease in porosity and air permeability.\u003c/p\u003e\n\u003cp\u003eThe whiteness of the cotton fabric was depicted in Fig. 9 (c) (Huang et al. 2019; Yeo and Lau 2021). Prior to finishing, the whiteness of the cotton fabric was measured at 88%, which remained almost unchanged at 87% post-finishing. Notably, no yellowing phenomenon was observed. In summary, the hydrophilicity of the treated cotton fabric improved while there was a slight decrease in air permeability; however, these changes were negligible compared to antibacterial textiles. This suggests that both the finishing process and quaternary ammonium salt antibacterial agent had minimal impact on the overall properties and usability of the finished cotton fabric.\u003c/p\u003e\n\u003cp\u003eHand assessment of the cotton fabric was performed on an apparatus to simulate the hand sensation when people touch a fabric. Some important parameters of the relative hand value, including softness, resilience, and smoothness scores of the fabric were recorded and presented in Fig. 9 (d). It can be observed that QCT had very few changes on the softness, resilience, and smoothness scores to 58, 26, 52 and 48 from 59, 24, and 52 of CT, respectively. It indicates that QCT have good tactile qualities involving a series of feel attributes and can present a feel near CT.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFig. 9.\u003c/strong\u003e Hydrophilicity (a), air permeability (b), whiteness (c), and hand assessment (d) of CT and QCT.\u0026nbsp;\u003c/p\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eThe quaternary ammonium salt antibacterial agents designed and synthesized in this experiment, together with the prepared durable antibacterial cotton fabric, demonstrated exceptional antimicrobial activity against gram-positive bacteria, gram-negative bacteria, and fungi. The concentration of the finishing agent was significantly lower than that of existing market antibacterial agents while maintaining excellent laundering durability. Even after undergoing 50 laundering cycles, the antibacterial rate of the cotton fabric still met the AAA antibacterial standard without any noticeable impact on its wearability or whiteness. Furthermore, hydrophilicity, softness, and wrinkle resistance were significantly improved. Although there was a slight decrease in mechanical properties and air permeability, it did not affect overall practical use. The quaternary ammonium salt antibacterial agents exhibited broad-spectrum bactericidal activity at a high rate. Additionally, the finishing method for cotton fabric proved to be simple, rapid, economical while resulting in durable and long-lasting antimicrobial effects due to chemical bonding between quaternary ammonium salt and cotton fibers.\u0026nbsp;\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eEthical approval\u0026nbsp;\u003c/strong\u003eThis article does not contain any studies with human participants or animals performed by any of the authors.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u0026nbsp;\u003c/strong\u003eThis work was financially supported by Young Elite Scientist Sponsorship Program by CAST (2022QNRC001) and Hubei Key Laboratory for New Textile Materials and Applications (FZXCL202203).\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability\u0026nbsp;\u003c/strong\u003eData will be made available on request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of interests\u0026nbsp;\u003c/strong\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n\u003cli\u003eBazina L et al. 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Text Res J 88:1650-1659.\u003c/li\u003e\n\u003c/ol\u003e"},{"header":"Scheme ","content":"\u003cp\u003eScheme 1 is available in the Supplementary Files section.\u003c/p\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":"Quaternary ammonium salt, cotton fabric, antibacterial, laundering durability","lastPublishedDoi":"10.21203/rs.3.rs-4034782/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4034782/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"For addressing the issue of limited durable antibacterial cotton fabric, this study developed and synthesized quaternary ammonium salt antimicrobial agents. The chemical structure was analyzed by FTIR and 1H NMR. The cotton fabric was subjected to surface modification techniques, such as pad-dry-cure, following the careful selection of appropriate quaternary ammonium salt. The chemical state and surface morphology were evaluated through XPS and SEM. Furthermore, the cotton fabric underwent comprehensive assessments, which included antibacterial testing, laundering cycle testing, evaluation of mechanical properties, and analysis of comfort performance. The results demonstrated that the treated cotton fabric achieved a high bacteriostatic and fungistatic rate of 99.99%, 87.5%, and 99.99% against S. aureus, E. coli, and C. albicans respectively even after 50 laundering cycles, while maintaining exceptional antibacterial effectiveness and laundering durability due to the formation of covalent bonds with the cotton fabric. The treated cotton fabric met AAA grade standards for antibacterial rate without causing any significant decline in mechanical properties. Furthermore, enhancements in hydrophilicity, softness, and wrinkle resistance were observed.","manuscriptTitle":"Durable antibacterial cotton fabrics with good performance enabled by quaternary ammonium salts","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-03-12 18:10:18","doi":"10.21203/rs.3.rs-4034782/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-03-23T11:55:50+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-03-13T16:17:26+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"0f6e8eee-dd14-47b9-97b3-e9e3c915fba2","date":"2024-03-09T19:38:37+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-03-09T15:41:18+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-03-09T07:03:44+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-03-09T07:03:44+00:00","index":"","fulltext":""},{"type":"submitted","content":"Cellulose","date":"2024-03-08T02:41:42+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":"094e5122-0d06-418c-8211-3dc02a41cb8e","owner":[],"postedDate":"March 12th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-07-20T14:07:43+00:00","versionOfRecord":{"articleIdentity":"rs-4034782","link":"https://doi.org/10.1007/s10570-024-05991-w","journal":{"identity":"cellulose","isVorOnly":false,"title":"Cellulose"},"publishedOn":"2024-06-01 14:07:43","publishedOnDateReadable":"June 1st, 2024"},"versionCreatedAt":"2024-03-12 18:10:18","video":"","vorDoi":"10.1007/s10570-024-05991-w","vorDoiUrl":"https://doi.org/10.1007/s10570-024-05991-w","workflowStages":[]},"version":"v1","identity":"rs-4034782","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4034782","identity":"rs-4034782","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}