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Insight into multifunctional polyester fabrics finished by one-step eco-friendly strategy
Chemical Engineering Journal 358 (2019) 634–642
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Chemical Engineering Journal journal homepage: www.elsevier.com/locate/cej
Insight into multifunctional polyester fabrics finished by one-step ecofriendly strategy
T
Shiguo Chena, , Shaobo Zhanga, Massimiliano Galluzzia, Fan Lib, Xingcai Zhangc, , Xinghui Yangd, ⁎ Xiangyu Liua, Xiaohua Caia, Xingli Zhua, Bing Dua, Jianna Lie, Peng Huangb, ⁎
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a
Nanshan District Key Laboratory for Biopolymers and Safety Evaluation, Shenzhen Key Laboratory of Polymer Science and Technology, Guangdong Research Center for Interfacial Engineering of Functional Materials, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, China b Guangdong Key Laboratory for Biomedical Measurements and Ultrasound Imaging, School of Biomedical Engineering, Health Science Center, Shenzhen University, Shenzhen 518055, China c John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA d Guangzhou Fiber Product Testing and Research Institute, Guangzhou 511447, China e Shenzhen Key Laboratory of Translational Medicine of Tumor, Health Science Center, Shenzhen University, Shenzhen 518055, China
HIGHLIGHTS
excellent and durable antimicrobial and anti-mite polyester fabrics are fabricated. • The finished PET fabrics exhibit excellent hydrophilic and antistatic properties. • The antimicrobial PET fabrics exhibit no skin stimulation and toxicity. • Non-leaching improved cohesive force between the fibers leading to enhanced tear strength. • The • The finished PET fabrics maintain mechanical properties and vapor/air permeability. ARTICLE INFO
ABSTRACT
Keywords: Polyethylene terephthalate Eco-friendly finishing Photochemical reaction Multifunctional Long-lasting properties
Polyethylene terephthalate (PET) has been widely used in fabrics owing to its great mechanical properties, easy processability and quick drying. However, PET-based products always suffer from uncomfortable low sweat uptake and electrostatic charge buildup mainly due to its bad surface wettability. Moreover, porous fabrics may induce unfavorable mite and microorganism reproduction. Due to lack of reactive groups on the PET skeleton, it was very difficult to endow its surface hydrophilicity, antistatic properties, perdurable antimicrobial and anti-mite properties by conventional methods. In this work, we develop a one-step eco-friendly finishing strategy for PET fabrics through photochemical reaction using benzophenone group terminated quaternary ammonium salt (BP-QAS) as the finishing reagent. The asfinished PET fibers changed from incompact state to compact state due to the increased cohesive forces within individual fibers, resulting in improved tearing strength. The PET fabrics show significantly improved hydrophilicity, and antistatic properties. Furthermore, the as-finished PET fabrics exhibit excellent, durable broad-spectrum antimicrobial activities against gram-negative, gram-positive, drug-resistant bacteria and fungi. Moreover, our fabric shows long-lasting antimicrobial properties above AAA requirements after 50 laundering cycles. Usual PET fabrics generally have difficulty achieving AAA standards after 10 laundering cycles. In addition, our as-prepared fabrics showed excellent anti-mite activities against house dust mites based on disruption of the microbial and mite membrane due to oxidation stress, while no negative effects were observed for mouse and rabbit. The finished PET fabrics can be applied to multiple industries to prevent infectious diseases and improve public health, including but not limited to packaging, clothes, water treatment, and medical appliances.
1. Introduction The most commonly used polyester, polyethylene terephthalate
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(PET), has been broadly used in multiple industries especially textiles owing to its excellent strength, chemical resistance, processability, quick drying and dimensional stability [1,2]. However, surface
Corresponding authors. E-mail addresses: [email protected] (S. Chen), [email protected] (X. Zhang), [email protected] (P. Huang).
https://doi.org/10.1016/j.cej.2018.10.070 Received 22 August 2018; Received in revised form 1 October 2018; Accepted 8 October 2018 Available online 09 October 2018 1385-8947/ © 2018 Elsevier B.V. All rights reserved.
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hydrophilicity and water absorption of PET fabrics are poor, resulting in uncomfortably low sweat uptake, electrostatic-charge buildup and pilling [2,3]. Additionally, microorganisms can proliferate in porous PET fabrics due to the abundant adsorption of metabolic products from the skin s sweat/sebaceous glands [4–6], resulting in unfavorable odor, stains, and discoloration, the reduction of the textiles’ mechanical properties and cause cross-contamination [7]. Furthermore, 50% of the patients with asthma are sensitized to house dust mites, and the allergic reaction from exposure to mites is a leading cause of a severe worldwide health problem [8]. House dust mites exist widely in bed, pillow, and mattress fabrics where they can breed and colonize. Anti-mite fabrics are therefore urgently needed for the control of the disease and the protection of human health [9]. However, the anti-mite fabrics are barely studied and the anti-mite mechanisms are not yet clarified [10,11]. Therefore, the development of hydrophilic, antistatic, antimicrobial and anti-mite finishing methods for PET fabrics is highly desired and is the focus of this work. Many antimicrobials such as guanidinium [12,13], peptide [14–16], betaine [17–21], chitosan [22–24], nanofibrous membranes [25], nanoparticles [26–28], graphene [29,30] and cationic amino segments [6,31] have been developed to treat microbial and prevent infectious diseases transmission and infections. Among them, cationic quaternary ammonium salts (QAS) have attracted much attention in antimicrobial finishing of fabrics due to their excellent antimicrobial activities, lowcost and facile preparation process [32]. It is well known that QAS can interact with the cell membrane of bacteria [31] and create reactive oxygen species (ROS) that can cause cell death [33]. Additionally, hydrophilic and positively charged QAS could also endow PET fabrics with hydrophilic and antistatic properties to improve its wearing comfort. Despite considerable efforts and recent advances in the fabrication of enhanced hydrophilic and antimicrobial cotton fabrics, an effective finishing method to obtain hydrophilic and antimicrobial PET fabrics is still far from optimal owing to no reactive group in the PET molecular skeleton [34]. To enhance the perdurable hydrophilicity or antimicrobial activity of PET fabrics, reactive groups such as OH, COOH, and NH2 were introduced through alkaline hydrolysis [35,36], aminolysis [37–39], alcoholysis, plasma treatment [1], microwave irradiation [40], gamma-ray irradiation [41], or UV radiation [42], after then the hydrophilic and antimicrobial groups were bound to the PET molecular
backbone after surface grafting [39], layer-by-layer self-assembly [35,36], or atom transfer radical polymerization [37,43]. However, those strategies would cause a local deterioration of the PET molecular backbone, leading to significantly decrease in the mechanical properties and surface roughness of PET fabrics [43]. Additionally, their hydrophilicity and durable antimicrobial properties are still not satisfactory [37,43,44]. Therefore, it is of great importance to develop a new finishing technology to fabricate PET fabrics with excellent hydrophilicity, broad-spectrum antimicrobial and anti-mite properties as well as enhanced stability against long-term laundering without compromising its superiority. A novel benzophenone containing polyethylenimines has reported to be covalently bonded onto polymer surfaces using mild photo-crosslinking, imparting non-leaching thin antimicrobial coatings for fabrics [45]. However, the preparation process is relatively complicated, and the final yield is not satisfactory. Especially, no investigation of the perdurable antimicrobial activity, anti-mite activity and other wearability properties of the treated textiles had been reported. Herein, we developed a one-step eco-friendly photochemical finishing method to fabricate polyester fabrics with excellent hydrophilicity, antistatic property, perdurable antimicrobial, and anti-mite activities by using a benzophenone group terminated quaternary ammonium salt (BP-QAS, 1) as an antimicrobial and anti-mite finishing agent via mild UV light irradiation (λ = 365 nm, 1.71 mW/cm2) activated rapid photochemical hydrogen abstraction reaction [46]. Moreover, we found that the BPQAS finished PET fabrics (2) are significantly improved in properties (Scheme 1): (i) greatly enhanced hydrophilic and antistatic properties; (ii) broad-spectrum antimicrobial activities even including the killing of drug-resistant bacteria and fungi; (iii) excellent acaricidal activity; (iv) improved cohesive force between the fibers leading to the improved tear strength; (v) no skin irritation and no toxicity, which are significant improvements that have not been studied or shown in other studies. 2. Results The BP-QAS was synthesized by the bromination reaction of methyl group in 4-methylbenzophenone, followed by a nucleophilic substitution of 4-bromomethyl benzophenone with N,N-dimethyldodecylamine (Scheme S1). And the BP-QAS was bonded onto the surface of raw PET fabrics via the photochemical hydrogen abstraction reaction between
Scheme 1. Photochemical finishing of PET fabrics by using quaternary ammonium salt terminated with benzophenone group (BP-QAS) with an excellent hydrophilic property, antistatic property, durable broad-spectrum antimicrobial, and acaricidal activities. 635
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Fig. 1. Characterization. (a) SEM images of BP-QAS finished PET fabric (2) and raw PET fabric (3). (b) Breaking strength, (c) tear strength, (d) elongation at break, (e) water vapor permeability; and (f) air permeability.
BP-QAS and hydrocarbons of the PET skeleton (Scheme S2) [46] The grafting degree of QAS to PET fabrics was increased with the increment of BP-QAS concentration (Fig. S2a). The success of the finishing process was also confirmed by X-ray photoelectron spectroscopy (XPS) (Fig. S2b & c) and energy dispersive X-ray analysis (EDX) (Fig. S2d). The peak at 402.5 eV (N1s: positively charged nitrogen N+, Fig. S2b) and the peak at 67.6 eV (Br3d, Fig. S2c) of QAS can be seen only in 2. Meanwhile, Br peak was also observed in EDX of 2 (Fig. S2d). These results showed that BP-QAS was successfully bonded onto the surface of PET fabrics.
2.2. Hydrophilicity To determine the hydrophilicity of PET fabrics after been finished with 1, water contact angle (WCA) [43], capillary penetration [4], and atomic force microscopy (AFM) [48,49] were applied to systematically investigate the hydrophilicity of 2 compared with 3. The water wicking height of 2 quickly reached 52.8 mm within 0.5 h and finally reached 135 mm in 12 h. On the contrary, the water wicking height of 3 was only 20.5 mm and then almost kept constant (∼26 mm) in 0.5–3 h, and finally reached 38.2 mm in 12 h (Fig. 2a). These results show that 2 is more hydrophilic than 3. Therefore, BP-QAS finishing agent can enhance the hydrophilicity of the fabrics remarkably. The water droplets on the surface of 3 could not spread in 5 min due to the high WCA of 3 (about 91°). In comparison, the water droplets rapidly spread on the surface of 2 within 1 s, lowering the WCA of 2 to 0° (Fig. 2b), which is much lower than that of previous finished PET based on local chain deterioration [37,43]. An improved hydrophilicity of fabrics could usually enhance the interaction between the fibers, resulting in improved fiber cohesion. To verify above point, the fiber morphology and cohesive force analyses were carried out as shown in Fig. 2c &d. The fibers of 3 form a loose mesh, while the fibers of 2 form a tight structure. The increase of intermolecular force between fibers would increase the separation and breaking strength of PET fibers, resulting in the enhanced tear strength of 2. Adhesion force in a humid environment is a result of the capillary condensation of water on PET
2.1. Comprehensive performance evaluation In the field-emission scanning electron microscope (FE-SEM) images (Fig. 1a), the BP-QAS finished PET fabrics (2) displayed a smooth surface and the same cross-section as raw PET fabrics (3), indicating that the fibers were intact after treatment. This result is better than that obtained by previous grafting methods which increased surface roughness [1,38]. Compared to 3, the tear strength of 2 increased by 17.0% in the warp direction from 14.7 to 17.2 N, and by 21.6% in the weft direction from 9.7 to 11.8 N (Fig. 1b). The tensile strength (Fig. 1c), and elongation-at-break (Fig. 1d) of 2 were almost the same as 3. The water vapor/air transmission of 2 was barely changed as compared with 3 (Fig. 1e & f), i.e. 2 kept good air and water permeability. Therefore, our as-obtained fabrics can maintain good thermo-physiological comfort for the body [47]. 636
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Fig. 2. Multi-performance evaluation. (a) Capillary effect, (b) water contact angle, (c, d) surface topography, (e) adhesive force and (f) water absorption of finished PET fabric (2) and raw PET fabric (3). Error bars of (a, e, f) have been based on the maximum and minimum values of five parallel samples.
surface, A high adhesion is correlated with high hydrophilicity [48]. A quantitative analysis of adhesion force of 2 compared to 3 was further performed by AFM using a hydrophilic probe (silicon nitride) to evaluate its hydrophilicity, as shown in Fig. 2e. The adhesion force of 2 was more than three times that of 3 (Fig. 2e). Single force spectroscopy events (Fig. S3) and adhesion mapping (Fig. S4) are available in Supporting Information along with additional technical details about AFM adhesion experiments. Meanwhile, the water absorption measurements of 3 and 2 were carried out to evaluate the sweat transpiration of 2 that was related to the wearing comfort of PET fabrics. The water absorption of 2 rapidly reached 74.8% and 88.1% within 0.5 and 1 min, respectively. It reached a plateau in 1–9 min and finally reached 92.7% in 10 min. Conversely, the water absorption of 3 was only 51.7%, and it did not change within 10 min (Fig. 2f). Taken together, these results showed that BP-QAS dramatically increased the hydrophilicity, adhesion forces, and mechanical properties of PET fabrics.
water-based electrolyte solution (NaCl). Since 1 is a positively charged agent, 2 shows a positively charged surface compared with slightly negatively charged 3 (Fig. S5). Experimental data (available in Table S1) along with theoretical and technical details about electrostatic AFM in the liquid can be found in the Supporting Information. 2.4. Antimicrobial activity The viable cell count method [4] was applied to quantitatively study the antimicrobial ability of 2 and 3. Fig. 4a & b showed the antimicrobial activities of 3 and 2 against Escherichia coli (E. coli, ATCC25922), Acinetobacter baumanii (A. baumannii, ATCC11038), Staphylococcus aureus (S. aureus, ATCC6538), Pseudomonas aeruginosa (P. Aeruginosa, ATCC9027), Staphylococcus epidermidis (S. epidermidis, ATCC12228), Streptococcus pneumoniae (S. pneumoniae, ATCC19165), Methicillin resistant staphylococcus aureus (MRSA, ATCC33591) and Aspergillus niger (A.niger, ATCC16404), The antimicrobial rates of 2 reached more than 99.99% against all the gram-negative bacteria (E. coli, A. baumannii, P. Aeruginosa), gram-positive bacteria (S. aureus, S. epidermidis, S. pneumoniae), multidrug resistant bacteria (MRSA) and fungi (A. niger). The antimicrobial data indicated that 2 showed excellent antimicrobial abilities against all evaluated bacteria and fungi. The antimicrobial rates of 3 and 2 were also tested after 50 laundering cycles using the FZ/T 73023-2006 standard method [4]. As can be seen in Fig. 4c, the antimicrobial rates were 92.4% (gram-positive bacterium S. aureus), 79.4% (gram-negative bacterium E. coli), and 75.9% (Fungi C. albicans). All these antimicrobial results of 2 are much greater than those reference values of AAA class and 3(Fig. 4c). These results show that 2 maintained durable antimicrobial activities after 50 repeated laundering cycles. Meanwhile, the diameters of the inhibition zone (DIZs) on S. aureus, E. coli, and C. albicans [4,52] of the 1-time washing leached products of 2 were tested and the results were all 0 mm. These results show that there is no leaching of 1 from 2 (Fig. S6). These results also confirmed that 2 had excellent perdurable antimicrobial activity against multiple laundering. Therefore, 1 can be a well-immobilized antimicrobial agent for PET fabric.
2.3. Antistatic properties Usually, the improved hydrophilicity of PET fabric can endow the antistatic property of PET fabrics [1,50]. Charge density, electrostatic voltage and half-life of 2 compared with those of 3 are shown in Fig. 3. The charge density of 2 was 1 mC/m2, which is only 20% of that of 3 (Fig. 3a). Similarly, the electrostatic voltage decreased greatly from 597 V to 132 V (Fig. 3b), and the half-life of electrostatic voltage fell enormously from 163 s to 0.01 s after being finished with 1 (Fig. 3c). The half-life of the electrostatic voltage of 2 was only 0.06% of that of 3, and it is also much lower than that of previous hydrophilic modification of polyester fabric by synergetic effect of biological enzymolysis and non-ionic surfactant [51]. These results indicated that the antistatic property of 3 was greatly enhanced via 1 finishing approach. To further analyze the effect of the finishing functionalization of BPQAS, the surface charge densities of 2 and 3 fabrics were measured using AFM force spectroscopy focused on electrostatic interactions in a 637
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Fig. 3. Evaluation of antistatic property of PET fabrics. (a) Charge density; (b) Electrostatic voltage; (c) Half-life. Error bars have been based on the maximum and minimum values of five parallel samples.
The bactericidal kinetics of 2 were tested by the viable cell count method [4]. Compared to 3, 2 showed increased antimicrobial rates against both E. coli and S. aureus with the increment of contact time. In the first 30 mins, the antimicrobial rates of 2 against both tested bacteria went up by 99.8% (Fig. 3d & e). When the contact time is greater than 120 mins, no viable bacteria was detected. Therefore, 2 showed excellent antimicrobial activity.
previous protocols [53]. The mites were grown on the surfaces of 2 and 3, and then the acaricidal activities were then evaluated according to their acaricidal rates. Fig. 5b showed the acaricidal activities of 2 against house dust mites as compared with 3. The number of viable mites decreased sharply with contact time in 2. The acaricidal rates of 2 reached 96.5% and 99.9% after the house dust mites were co-cultured with 2 for 96 and 120 h, respectively. This implied that 2 had excellent acaricidal activity against house dust mites. In contrast, the anti-mite rate of 3 decreased very slowly with the contact time, reaching only 17.6% even after 120 h incubation time. The positively charged QAS can easily interact with the cell membrane of bacteria [31] and generate excessive reactive oxygen species (ROS). While the amount of ROS surpasses the organism’s detoxification and repairing abilities, it would lead to cell death [33]. However, the anti-mite mechanism of QAS has been barely studied. To investigate the potential anti-mite mechanism of BP-QAS finished PET fabrics, the effect of PET fabrics on nitric oxide (NO) and glutathione (GSH) were tested. The generation of ROS such as NO can induce apoptotic cascade
2.5. Anti-mite activity The anti-mite activity of 2 against house dust mites were evaluated according to the Chinese national standard method (GB/T 24253-2009) [53]. The anti-mite test results can be seen in Fig. 5. Anti-mite kinetics of 2 was investigated and compared with 3 by previous protocols [53]. The mite repellent rate of 2 was 99.9% after incubation for 24 h, and no viable mites were observed, which was much higher than that of 3 (about 17.6%) (Fig. 5a). Anti-mite kinetics of 2 was investigated compared with that of 3 by
Fig. 4. Evaluation of antimicrobial activities. (a) Antimicrobial activities of raw PET fabrics (3, A) and finished PET fabrics (2, B); (b) Antimicrobial rates of finished PET fabrics (2) compared to 3; (c) Durable antimicrobial activities of 3 and 2 after repeated laundering (50 times); (d) Antibacterial kinetic of 3 and 2 against (d) S. aureus (ATCC 6538) and (e) E. coli (ATCC 25922). 60 mg/mL of BP-QAS. Error bars of (d, e) have been based on the maximum and minimum values of three parallel samples. 638
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Fig. 5. Anti-mite activities assay. (a) Mite repellent rate of 2 and 3; A-with anti-mite effect, B-with strong anti-mite effect, C-with strong anti-mite effect. (b) The acaricidal kinetics of 2 and 3; (c) NO and (d) GSH level of mite treated by and 2 and 3; surface topographies of (e) control mite and (f) mites treated by 2.
histopathological abnormal was found in hematoxylin & eosin (H&E) stained images at any evaluated areas masked by 2 or 3 (Fig. 6b & c). The primary irritation index of 2 and 3 are all negligible (Table S2). The acute oral toxicity tests in mice were also carried out to further prove the safety and biocompatibility BP-QAS finished textiles. At all evaluated amounts, both death (Fig. 7a) and huge body weight lost (Fig. 7b) were not seen. Besides, among all studies, there is no obvious behavior difference for mices. Their explorative behaviors were as usual. Their hair glossiness and skin color and other appearances did not show any obvious change. They eat, drunk, and behaved like normal. After treatment with 2, major organs were gathered on day fourteen to do the histology tests. All stomach, kidney, liver, large intestine as well as small intestine tissues are tested and turned out to be normal. No obvious histopathological abnormality was found among all the H&E stained images in all tested doses (Fig. 7c).
thorough caspases [54]. As shown in Fig. 5c, the concentration of NO of untreated mites is only 5.3 µg/g tissue (control), however, the concentration of NO exposed to 2 at different contact times reached 21.54 µmol/g tissue (24 h), 36.9 µmol/g tissue (48 h) and 48.93 µmol/g tissue (72 h), respectively, which were four times (24 h), seven times (48 h) and nine times (72 h) as large as control mite, and they were also about three times as large as that of mites exposed to 3 at the same contact times (Fig. 5c). Excessive destructive ROS production can cause oxidative stress and lipid peroxidation, and subsequently bacteria death [55]. GSH is widely applied as a good oxidative stress indicator in cells. The GSH antioxidant system is foremost among the cellular protective mechanisms. GSH can help maintain the normal function of the immune system, and it has antioxidant effects and integrated detoxification. GSH level of mites exposed to 2 was lower than mites exposed to 3 after different time. Particularly, GSH level of mites exposed to 2 after 72 h decreased to 90.63 µmol/g tissue, which is only 23% of that of untreated mites and PET fabric treated mites (Fig. 5d). The result showed that there was a significant drop in the GSH level and subsequent loss of the protective effect of the peroxidase-GSH system of mites exposed to 2. At high dose, ROS and oxidative stress production could lead to toxicity [56]. The acaricidal mechanism of 2 may be ascribed to disruption of the mite membrane due to oxidation stress based on ROS such NO, and, subsequently, the killing of the mites. This destructive acaricidal mechanism triggered by excessive ROS was also confirmed by the morphological change in house dust mites caused by 2 using environmental scanning electron microscopy (ESEM) images, which revealed that the mites exposed to 3 maintained their integrity with no obvious morphological changes after 48 h (Fig. 5e). While the mite body exposed to 2 underwent a transformation from a full state to a shrunken state, and the skin of the back and abdomen roughened. The jaw became hollow, and four of the feet contracted toward the abdomen, and the bristles became disordered. The mites exposed to 2 lost their integrity, wrinkled outer membrane substantially and showed a destructive structure, indicating damage and death (Fig. 5f).
3. Discussion Mechanical properties are also very important for fabrics, especially for their long-lasting applications. In this work, mild UV light (λ = 365 nm) was utilized to finish PET fabrics with covalently bonded 1. Compared with oxidative damage of polymer and substrates exposed to higher energy UV [45], PET fibers maintained breaking strength and smooth surface topography of 2 because it did not damage the fiber structure of PET during the finishing process. Additionally, the finishing process induced by mild UV light is suitable for large-scale fabrication of PET fabrics. Utilizing photochemical hydrogen abstraction reaction, hydrophilic QAS group was introduced onto the PET surface with no obvious unwanted color change. The hydrophilicity and water absorption of PET fabrics were significantly improved, lending to excellent antistatic property and enhancing its comfort and wearability. In addition, the polar QAS group improved the intermolecular interaction of PET fibers, leading to high adhesion forces of PET fibers and preventing pilling. At the same time, increased cohesion force changed fibers from a loose to a tight state, resulting in a significant increase in tear strength. Therefore, the tear strength of 2 increased markedly, and there were no significant variations of elongation at break or tensile strength due to their retained fiber structures and the improved cohesive forces between the fibers. Meanwhile, Moisture and air transmission through fabrics are crucial for human comfort. The long alkyl chains-containing QAS was bound onto the surfaces of the PET textiles like ribbons fixed at only one end, and no dense coating film that would
2.6. Biocompatibility To test the safety and biocompatibility of textiles, 2 and 3 are exposed to the back of rabbit’s skin to test their irritation responses as illustrated in Fig. 6a. After contact for 24, 48, and 72 h, both erythema and edema are not found (Fig. 6a). Besides, no distinct 639
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Fig. 6. Rabbit skin irritation results according to ISO 10993. 10-2014 standard. (a) The images of rabbits’ back skin contacting with the sample (right) and negative control (left) at (I) 0 h, (II) 1 h, (III) 24 h, (IV) 48 h, and (V) 72 h. HE staining images of skin contacted with negative control (b) and sample (c). Scale bar represents 50 μm.
reduce their air and water permeability could be formed [32], so 2 showed no obvious decline of the air or water vapor permeability. Many antimicrobial PET fabrics with leaching antimicrobial agents were reported [34,57]. Generally, when antimicrobials are easy to be leached, these antimicrobial fabrics would reduce their antimicrobial performance, repeated laundering [58], and cause antimicrobial resistance due to sublethal concentrations of antimicrobials [59]. Additionally, leaching antimicrobials on textiles would kill the resident flora of nonpathogenic bacteria on the skin of the wearer, which are
important to the health of the skin as they can create an unfavorable environment for the growth of pathogenic bacteria [32]. Therefore, the synthesis of bound antimicrobial agents to replace their easy-leaching counterparts is critical. However, their durable antimicrobial finishing are challenging owing to the lack of reactive functional groups. To achieve perdurable antimicrobial activity, bound antimicrobial finishing methods have been developed for antimicrobial PET fabrics by damaging the PET backbone to produce reactive groups, followed by chemical modification. The above modified ways would increase the
Fig. 7. In vivo toxicity of sample. (a) Survival curves of mice after various treatments. The sample treated mice after oral administration showed 100% survival over 14 days. (b) Mice body weight gain percentages of mice after various treatments. The body weight of mice did not show significant change within 14 d. (c) HE staining images of major organs collected from different groups of mice on day 14. F: Female mice, M: Male mice. 640
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rough, and decline the mechanical properties of fabrics. Moreover, their durable antimicrobial properties and hydrophilicity was still not satisfied. Herein, we overcame the above challenges to fabricate PET fabrics with perdurable antimicrobial, anti-mite, antistatic, biocompatibility, and multi-laundering stability simultaneously by onestep eco-friendly strategy. The introduction of QAS to PET surface greatly improves its ability for strongly targeting to the oppositelycharged cell surface of bacteria to effectively kill the bacteria. The nonleaching property of 1 was further confirmed by the DIZ test results. It ensures durable antimicrobial and anti-mite activities of 2 after 50 laundering cycles. Since there is no 1 leached from 2, the drug resistance to 2 in microorganisms can be reduced [58], and skin irritations and toxicity can be inhibited [4,5]. Therefore, 1 is an excellent durable broad-spectrum antimicrobial and anti-mite finishing agent for fabrics. We attributed the antimicrobial mechanisms of 2 to the QASmicrobe binding [58] due to the attractive interaction between the positive charged cationic QAS on 2 and the oppositely charged microbe [60], followed by the ROS creation and microbe-killing. Anti-mite property is an important property that is less studied up to now. Here we demonstrated the excellent anti-mite property of our onestep eco-friendly finishing method for 2. The anti-mite property may have the same mechanism as antimicrobial property that may be related to destructive reactive oxygen species. Though the accurate antimite mechanism is not totally clear and new studies should be carried out in our future work, we paved a potential way for new anti-mite fabric studies. To sum up, BP-QAS is an excellent, durable broadspectrum antimicrobial and anti-mite finishing agent against gram-negative, gram-positive, and drug-resistant bacteria, fungi and house dust mites based on disruption of the microbial and mite membrane due to oxidation stress.
Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.cej.2018.10.070. References [1] J. Lv, Q. Zhou, T. Zhi, D. Gao, C. Wang, Environmentally friendly surface modification of polyethylene terephthalate (PET) fabric by low-temperature oxygen plasma and carboxymethyl chitosan, J. Clean Prod. 118 (2016) 187–196. [2] J.Y. Cho, C.J. Hong, H.M. Choi, Microwave-assisted glycolysis for PET with highly hydrophilic surface, Ind. Eng. Chem. Res. 52 (2013) 2309–2315. [3] J.Y. Cho, H.M. Choi, K.W. Oh, Rapid hydrophilic modification of poly(ethylene terephthalate) surface by using deep eutectic solvent and microwave irradiation, Text. Res. J. 86 (2016) 1318–1327. [4] S.G. Chen, L.J. Yuan, Q.Q. Li, J.N. Li, X.L. Zhu, Y.G. Jiang, O. Sha, X.H. Yang, J.H. Xin, J.X. Wang, F.J. Stadler, P. Huang, Durable antibacterial and nonfouling cotton textiles with enhanced comfort via zwitterionic sulfopropylbetaine coating, Small 12 (2016) 3516–3521. [5] S.B. Zhang, X.H. Yang, B. Tang, L.J. Yuan, K. Wang, X.Y. Liu, X.L. Zhu, J.N. Li, Z.C. Ge, S.G. Chen, New insights into synergistic antimicrobial and antifouling cotton fabrics via dually finished with quaternary ammonium salt and zwitterionic sulfobetaine, Chem. Eng. J. 336 (2018) 123–132. [6] M. Yu, Z. Wang, M. Lv, R. Hao, R. Zhao, L. Qi, S. Liu, C. Yu, B. Zhang, C. Fan, J. Li, Antisuperbug cotton fabric with excellent laundering durability, ACS Appl. Mater. Interfaces 8 (2016) 19866–19871. [7] Q. Yu, Z. Wu, H. Chen, Dual-function antibacterial surfaces for biomedical applications, Acta Biomater. 16 (2015) 1–13. [8] J. Virchow, V. Backer, P. Kuna, et al., Efficacy of a house dust mite sublingual allergen immunotherapy tablet in adults with allergic asthma: a randomized clinical trial, JAMA 315 (2016) 1715–1725. [9] V. Mahakittikun, J.J. Boitano, C. Komoltri, P. Ninsanit, T. Wangapai, Anti-mite covers: Potential criteria for materials used against dust mites, Text. Res. J. 79 (2009) 436–443. [10] J. Gabbay, J. Israel, Acaricidal fabric, US Patent 5,939,340,1999. [11] S. Rochat, C. Vidil, Use of zinc sulfide as an anti-mite agent, US Patent App. 10/500, 699, 2005. [12] W. Chin, G. Zhong, Q. Pu, C. Yang, W. Lou, P.F. De Sessions, B. Periaswamy, A. Lee, Z.C. Liang, X. Ding, S. Gao, C.W. Chu, S. Bianco, C. Bao, Y.W. Tong, W. Fan, M. Wu, J.L. Hedrick, Y.Y. Yang, A macromolecular approach to eradicate multidrug resistant bacterial infections while mitigating drug resistance onset, Nat. Commun. 9 (2018) 917. [13] P.A. Wender, W.C. Galliher, E.A. Goun, L.R. Jones, T.H. Pillow, The design of guanidinium-rich transporters and their internalization mechanisms, Adv. Drug Deliv. Rev. 60 (2008) 452–472. [14] R.E.W. Hancock, H.G. Sahl, Antimicrobial and host-defense peptides as new antiinfective therapeutic strategies, Nat. Biotechnol. 24 (2006) 1551–1557. [15] B.P. Mowery, S.E. Lee, D.A. Kissounko, R.F. Epand, R.M. Epand, B. Weisblum, S.S. Stahl, S.H. Gellman, Mimicry of antimicrobial host-defense peptides by random copolymers, J. Am. Chem. Soc. 129 (2007) 15474–15476. [16] M. Wenzel, A.I. Chiriac, A. Otto, D. Zweytick, C. May, C. Schumacher, R. Gust, H.B. Albada, M. Penkova, U. Krämer, R. Erdmann, N. Metzler-Nolte, S.K. Straus, E. Bremer, D. Becher, H. Brötz-Oesterhelt, H.-G. Sahl, J.E. Bandow, Small cationic antimicrobial peptides delocalize peripheral membrane proteins, PNAS 111 (2014) E1409–E1418. [17] L. Mi, S. Jiang, Integrated antimicrobial and nonfouling zwitterionic polymers, Angew. Chem. Int. Ed. 53 (2014) 1746–1754. [18] L. Zhang, Z. Cao, T. Bai, L. Carr, J.-R. Ella-Menye, C. Irvin, B.D. Ratner, S. Jiang, Zwitterionic hydrogels implanted in mice resist the foreign-body reaction, Nat. Biotechnol. 31 (2013) 553–556. [19] A.J. Keefe, S. Jiang, Poly(zwitterionic)protein conjugates offer increased stability without sacrificing binding affinity or bioactivity, Nat. Chem. 4 (2012) 60–64. [20] Z. Cao, L. Mi, J. Mendiola, E.-M. Jean-Rene, L. Zhang, H. Xue, S. Jiang, Reversibly switching the function of a surface between attacking and defending against bacteria, Angew. Chem. Int. Ed. 51 (2012) 2602–2605. [21] W. Wei, L. Yang, Z. Hui, C. Zhiqiang, Superdurable coating fabricated from a double-sided tape with long term “Zero” bacterial adhesion, Adv. Mater. 29 (2017) 1606506. [22] P. Li, Y.F. Poon, W. Li, H.Y. Zhu, S.H. Yeap, Y. Cao, X. Qi, C. Zhou, M. Lamrani, R.W. Beuerman, E.T. Kang, Y. Mu, C.M. Li, M.W. Chang, S.S.J. Leong, M.B. ChanPark, A polycationic antimicrobial and biocompatible hydrogel with microbe membrane suctioning ability, Nat. Mater. 10 (2011) 149–156. [23] Y.X. Chen, J.N. Li, Q.Q. Li, Y.Y. Shen, Z.C. Ge, W.W. Zhang, S.G. Chen, Enhanced water-solubility, antibacterial activity and biocompatibility upon introducing sulfobetaine and quaternary ammonium to chitosan, Carbohyd. Polym. 143 (2016) 246–253. [24] W.J. Zou, Y.X. Chen, X.C. Zhang, L.J. Na, S.L. Ming, G.Z. Fan, D. Bing, S.G. Chen, Cytocompatible chitosan based multi-network hydrogels with good antimicrobial, cell anti-adhesive and mechanical properties, Carbohyd. Polym. 202 (2018) 246–257. [25] Y. Si, Z. Zhang, W. Wu, Q. Fu, K. Huang, N. Nitin, B. Ding, G. Sun, Daylight-driven rechargeable antibacterial and antiviral nanofibrous membranes for bioprotective applications, Sci. Adv. 4 (2018) eaar5931. [26] A.P. Richter, J.S. Brown, B. Bharti, A. Wang, S. Gangwal, K. Houck, E.A. Cohen
4. Conclusion In view of the present disadvantage of durable functional finishing of polyester fibers, we develop a facile eco-friendly finishing technique for PET fabrics through photochemical reaction with BP-QAS. In this work, we explore a facile eco-friendly finishing technique for PET fabrics through photochemical reaction with benzophenone group terminated quaternary ammonium salt (BP-QAS). Compared to general finishing methods, antimicrobial, hydrophilic and positively charged small molecule compound was chemically bound onto the surfaces of the PET textiles like ribbons fixed at only one end without destruction of PET fiber structure, to impart long-lasting antimicrobial and antimite effects without damaging the mechanic performance, color, air permeability and water vapor permeability due to no dense coating film that would reduce their air and water permeability could be formed. The as-finished PET fibers changed from incompact state to compact state due to the increased cohesive forces within individual fibers, leading to significant better tear strength, hydrophilicity, hygroscopicity (absorption of sweat) and antistatic property. Moreover, the as-finished PET fabrics exhibit excellent, perdurable broad-spectrum antimicrobial and anti-mite activities against gram-negative, gram-positive, and drug-resistant bacteria, fungi and house dust mites based on disruption of the microbial and mite membrane due to oxidation stress. While no negative effects were observed for mouse and rabbit. The finished PET fabrics can be applied to multiple industries, including but not limited to packaging, clothes, water treatment, and medical appliances. Acknowledgements This work was supported by the National Natural Science Foundation of China (51773117, 51573097, 51573096), the Science and Technology Project of Guangdong Province (2015A010105033, 2014B09091041), the Collaborative Innovation and Technology Project for Shenzhen-Hong Kong Innovation Circle of Shenzhen city (SGLH20120926161415782). 641
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S. Chen et al.
[27] [28] [29] [30] [31] [32] [33] [34]
[35] [36] [37] [38] [39]
[40] [41] [42]
Hubal, V.N. Paunov, S.D. Stoyanov, O.D. Velev, An environmentally benign antimicrobial nanoparticle based on a silver-infused lignin core, Nat. Nanotechnol. 10 (2015) 817–823. S.G. Chen, Y.J. Guo, S.J. Chen, H.M. Yu, Z.C. Ge, X. Zhang, P.X. Zhang, J.N. Tang, Facile preparation and synergistic antibacterial effect of three-component Cu/TiO2/ CS nanoparticles, J. Mater. Chem. 22 (2012) 9092–9099. Q. Liu, J. Huang, J. Zhang, Y. Hong, Y. Wan, Q. Wang, M. Gong, Z. Wu, C.F. Guo, Thermal, waterproof, breathable, and antibacterial cloth with a nanoporous structure, ACS Appl. Mater. Interfaces 10 (2018) 2026–2032. X. Lu, X. Feng, J.R. Werber, C. Chu, I. Zucker, J.-H. Kim, C.O. Osuji, M. Elimelech, Enhanced antibacterial activity through the controlled alignment of graphene oxide nanosheets, PNAS 114 (2017) E9793–E9801. Y. Tu, M. Lv, P. Xiu, T. Huynh, M. Zhang, M. Castelli, Z. Liu, Q. Huang, C. Fan, H. Fang, R. Zhou, Destructive extraction of phospholipids from Escherichia coli membranes by graphene nanosheets, Nat. Nanotechnol. 8 (2013) 594. S. Chen, Q. Chen, Q. Li, J. An, P. Sun, J. Ma, H. Gao, Biodegradable synthetic antimicrobial with aggregation-induced emissive luminogens for temporal antibacterial activity and facile bacteria detection, Chem. Mater. 30 (2018) 1782–1790. J.W. Gu, L.J. Yuan, Z. Zhang, X.H. Yang, J.X. Luo, Z.F. Gui, S.G. Chen, Non-leaching bactericidal cotton fabrics with well-preserved physical properties, no skin irritation and no toxicity, Cellulose 25 (2018) 5415–5426. M.P. Brynildsen, J.A. Winkler, C.S. Spina, I.C. MacDonald, J.J. Collins, Potentiating antibacterial activity by predictably enhancing endogenous microbial ROS production, Nat. Biotechnol. 31 (2013) 160–165. Y.X. Chen, W. Lan, J.Y. Wang, R.R. Zhu, Z.W. Yang, D.L. Ding, G.M. Tang, K.R. Wang, Q. Su, E.Q. Xie, Highly flexible, transparent, conductive and antibacterial films made of spin-coated silver nanowires and a protective ZnO layer, Physica E 76 (2016) 88–94. L. Pérez-Álvarez, E. Lizundia, S. del Hoyo, A. Sagasti, L.R. Rubio, J.L. Vilas, Polysaccharide polyelectrolyte multilayer coating on poly(ethylene terephthalate), Polym. Int. 65 (2016) 915–920. D. Cheng, X. Lin, L. Fan, G. Cai, J. Wu, W. Yu, Preparation and characterization of polyelectrolyte/silver multilayer films on PET substrates and its antibacterial property, Polym. Compos. 36 (2015) 1161–1168. X. Jin, J. Yuan, J. Shen, Zwitterionic polymer brushes via dopamine-initiated ATRP from PET sheets for improving hemocompatible and antifouling properties, Colloid Surf B 145 (2016) 275–284. B. Lepoittevin, L. Costa, S. Pardoue, D. Dragoe, S. Mazerat, P. Roger, Hydrophilic PET surfaces by aminolysis and glycopolymer brushes chemistry, J. Polym. Sci. Polym. Chem. 54 (2016) 2689–2697. H. Poortavasoly, M. Montazer, T. Harifi, Aminolysis of polyethylene terephthalate surface along with in situ synthesis and stabilizing ZnO nanoparticles using triethanolamine optimized with response surface methodology, Mater. Sci. Eng. CMater. 58 (2016) 495–503. Y. Gao, R. Cranston, Recent advances in antimicrobial treatments of textiles, Text. Res. J. 78 (2008) 60–72. X. Ping, M. Wang, G. Xuewu, Surface modification of poly(ethylene terephthalate) (PET) film by gamma-ray induced grafting of poly(acrylic acid) and its application in antibacterial hybrid film, Radiat. Phys. Chem. 80 (2011) 567–572. V.H. Fragal, T.S.P. Cellet, G.M. Pereira, E.H. Fragal, M.A. Costa, C.V. Nakamura, T. Asefa, A.F. Rubira, R. Silva, Covalently-layers of PVA and PAA and in situ formed
[43]
[44] [45] [46] [47] [48] [49] [50] [51] [52] [53] [54] [55] [56] [57] [58] [59] [60]
642
Ag nanoparticles as versatile antimicrobial surfaces, Int. J. Biol. Macromol. 91 (2016) 329–337. S. del Hoyo-Gallego, L. Pérez-Álvarez, F. Gómez-Galván, E. Lizundia, I. Kuritka, V. Sedlarik, J.M. Laza, J.L. Vila-Vilela, Construction of antibacterial poly(ethylene terephthalate) films via layer by layer assembly of chitosan and hyaluronic acid, Carbohyd. Polym. 143 (2016) 35–43. W. Ali, P. Sultana, M. Joshi, S. Rajendran, A solvent induced crystallisation method to imbue bioactive ingredients of neem oil into the compact structure of poly (ethylene terephthalate) polyester, Mater. Sci. Eng. C-Mater. 64 (2016) 399–406. V.P. Dhende, S. Samanta, D.M. Jones, I.R. Hardin, J. Locklin, One-step photochemical synthesis of permanent, nonleaching, ultrathin antimicrobial coatings for textiles and plastics, ACS Appl. Mater. Interfaces 3 (2011) 2830–2837. D. Chen, C.-C. Chang, B. Cooper, A. Silvers, T. Emrick, R.C. Hayward, Photopatternable biodegradable aliphatic polyester with pendent benzophenone groups, Biomacromolecules 16 (2015) 3329–3335. Y. Liu, J.H. Xin, C.H. Choi, Cotton fabrics with single-faced superhydrophobicity, Langmuir 28 (2012) 17426–17434. D.I. Kim, J. Grobelny, N. Pradeep, R.F. Cook, Origin of adhesion in humid air, Langmuir 24 (2008) 1873–1877. H.J. Butt, B. Cappella, M. Kappl, Force measurements with the atomic force microscope: Technique, interpretation and applications, Surf. Sci. Rep. 59 (2005) 1–152. E.S. Abdel-Halim, F.A. Abdel-Mohdy, S.S. Al-Deyab, M.H. El-Newehy, Chitosan and monochlorotriazinyl-beta-cyclodextrin finishes improve antistatic properties of cotton/polyester blend and polyester fabrics, Carbohyd. Polym. 82 (2010) 202–208. A. Gao, H. Shen, H. Zhang, G. Feng, K. Xie, Hydrophilic modification of polyester fabric by synergetic effect of biological enzymolysis and non-ionic surfactant, and applications in cleaner production, J. Clean Prod. 164 (2017) 277–287. S.G. Chen, S.J. Chen, S. Jiang, M.L. Xiong, J.X. Luo, J.N. Tang, Z.C. Ge, Environmentally friendly antibacterial cotton textiles finished with siloxane sulfopropylbetaine, ACS Appl. Mater. Interfaces 3 (2011) 1154–1162. W. Wei, J. He, B. Yu, Y. Zou, F. Liu, X. Chen, J. Chen, Synthesis of microencapsulated benzyl benzoate with a CaCO3 shell and its application to the durable anti-mite finishing of nylon 6 fabric, RSC Adv. 6 (2016) 59624–59632. S. Arora, J. Jain, J.M. Rajwade, K.M. Paknikar, Cellular responses induced by silver nanoparticles: in vitro studies, Toxicol. Lett. 179 (2008) 93–100. S.G. Chen, Y.J. Guo, H.Q. Zhong, S.J. Chen, J.N. Li, Z.C. Ge, J.N. Tang, Synergistic antibacterial mechanism and coating application of copper/titanium dioxide nanoparticles, Chem. Eng. J. 256 (2014) 238–246. A. Nel, T. Xia, L. Mädler, N. Li, Toxic potential of materials at the nanolevel, Science 311 (2006) 622–627. M. Montazer, V. Allahyarzadeh, Electroless plating of silver nanoparticles/nanolayer on polyester fabric using AgNO3/NaOH and ammonia, Ind. Eng. Chem. Res. 52 (2013) 8436–8444. B. Simoncic, B. Tomsic, Structures of novel antimicrobial agents for textiles – a review, Text. Res. J. 80 (2010) 1721–1737. A. Harms, E. Maisonneuve, K. Gerdes, Mechanisms of bacterial persistence during stress and antibiotic exposure, Science 354 (2016) aaf4268. Y. Jin, H. Pei, W. Hu, Y. Zhu, H. Xu, C. Ma, J. Sun, H. Li, A promising application of chitosan quaternary ammonium salt to removal of Microcystis aeruginosa cells from drinking water, Sci. Total Environ. 583 (2017) 496–504.
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Insight into multifunctional polyester fabrics finished by one-step ecofriendly strategy
T
Shiguo Chena, , Shaobo Zhanga, Massimiliano Galluzzia, Fan Lib, Xingcai Zhangc, , Xinghui Yangd, ⁎ Xiangyu Liua, Xiaohua Caia, Xingli Zhua, Bing Dua, Jianna Lie, Peng Huangb, ⁎
⁎
a
Nanshan District Key Laboratory for Biopolymers and Safety Evaluation, Shenzhen Key Laboratory of Polymer Science and Technology, Guangdong Research Center for Interfacial Engineering of Functional Materials, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518055, China b Guangdong Key Laboratory for Biomedical Measurements and Ultrasound Imaging, School of Biomedical Engineering, Health Science Center, Shenzhen University, Shenzhen 518055, China c John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA 02138, USA d Guangzhou Fiber Product Testing and Research Institute, Guangzhou 511447, China e Shenzhen Key Laboratory of Translational Medicine of Tumor, Health Science Center, Shenzhen University, Shenzhen 518055, China
HIGHLIGHTS
excellent and durable antimicrobial and anti-mite polyester fabrics are fabricated. • The finished PET fabrics exhibit excellent hydrophilic and antistatic properties. • The antimicrobial PET fabrics exhibit no skin stimulation and toxicity. • Non-leaching improved cohesive force between the fibers leading to enhanced tear strength. • The • The finished PET fabrics maintain mechanical properties and vapor/air permeability. ARTICLE INFO
ABSTRACT
Keywords: Polyethylene terephthalate Eco-friendly finishing Photochemical reaction Multifunctional Long-lasting properties
Polyethylene terephthalate (PET) has been widely used in fabrics owing to its great mechanical properties, easy processability and quick drying. However, PET-based products always suffer from uncomfortable low sweat uptake and electrostatic charge buildup mainly due to its bad surface wettability. Moreover, porous fabrics may induce unfavorable mite and microorganism reproduction. Due to lack of reactive groups on the PET skeleton, it was very difficult to endow its surface hydrophilicity, antistatic properties, perdurable antimicrobial and anti-mite properties by conventional methods. In this work, we develop a one-step eco-friendly finishing strategy for PET fabrics through photochemical reaction using benzophenone group terminated quaternary ammonium salt (BP-QAS) as the finishing reagent. The asfinished PET fibers changed from incompact state to compact state due to the increased cohesive forces within individual fibers, resulting in improved tearing strength. The PET fabrics show significantly improved hydrophilicity, and antistatic properties. Furthermore, the as-finished PET fabrics exhibit excellent, durable broad-spectrum antimicrobial activities against gram-negative, gram-positive, drug-resistant bacteria and fungi. Moreover, our fabric shows long-lasting antimicrobial properties above AAA requirements after 50 laundering cycles. Usual PET fabrics generally have difficulty achieving AAA standards after 10 laundering cycles. In addition, our as-prepared fabrics showed excellent anti-mite activities against house dust mites based on disruption of the microbial and mite membrane due to oxidation stress, while no negative effects were observed for mouse and rabbit. The finished PET fabrics can be applied to multiple industries to prevent infectious diseases and improve public health, including but not limited to packaging, clothes, water treatment, and medical appliances.
1. Introduction The most commonly used polyester, polyethylene terephthalate
⁎
(PET), has been broadly used in multiple industries especially textiles owing to its excellent strength, chemical resistance, processability, quick drying and dimensional stability [1,2]. However, surface
Corresponding authors. E-mail addresses: [email protected] (S. Chen), [email protected] (X. Zhang), [email protected] (P. Huang).
https://doi.org/10.1016/j.cej.2018.10.070 Received 22 August 2018; Received in revised form 1 October 2018; Accepted 8 October 2018 Available online 09 October 2018 1385-8947/ © 2018 Elsevier B.V. All rights reserved.
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hydrophilicity and water absorption of PET fabrics are poor, resulting in uncomfortably low sweat uptake, electrostatic-charge buildup and pilling [2,3]. Additionally, microorganisms can proliferate in porous PET fabrics due to the abundant adsorption of metabolic products from the skin s sweat/sebaceous glands [4–6], resulting in unfavorable odor, stains, and discoloration, the reduction of the textiles’ mechanical properties and cause cross-contamination [7]. Furthermore, 50% of the patients with asthma are sensitized to house dust mites, and the allergic reaction from exposure to mites is a leading cause of a severe worldwide health problem [8]. House dust mites exist widely in bed, pillow, and mattress fabrics where they can breed and colonize. Anti-mite fabrics are therefore urgently needed for the control of the disease and the protection of human health [9]. However, the anti-mite fabrics are barely studied and the anti-mite mechanisms are not yet clarified [10,11]. Therefore, the development of hydrophilic, antistatic, antimicrobial and anti-mite finishing methods for PET fabrics is highly desired and is the focus of this work. Many antimicrobials such as guanidinium [12,13], peptide [14–16], betaine [17–21], chitosan [22–24], nanofibrous membranes [25], nanoparticles [26–28], graphene [29,30] and cationic amino segments [6,31] have been developed to treat microbial and prevent infectious diseases transmission and infections. Among them, cationic quaternary ammonium salts (QAS) have attracted much attention in antimicrobial finishing of fabrics due to their excellent antimicrobial activities, lowcost and facile preparation process [32]. It is well known that QAS can interact with the cell membrane of bacteria [31] and create reactive oxygen species (ROS) that can cause cell death [33]. Additionally, hydrophilic and positively charged QAS could also endow PET fabrics with hydrophilic and antistatic properties to improve its wearing comfort. Despite considerable efforts and recent advances in the fabrication of enhanced hydrophilic and antimicrobial cotton fabrics, an effective finishing method to obtain hydrophilic and antimicrobial PET fabrics is still far from optimal owing to no reactive group in the PET molecular skeleton [34]. To enhance the perdurable hydrophilicity or antimicrobial activity of PET fabrics, reactive groups such as OH, COOH, and NH2 were introduced through alkaline hydrolysis [35,36], aminolysis [37–39], alcoholysis, plasma treatment [1], microwave irradiation [40], gamma-ray irradiation [41], or UV radiation [42], after then the hydrophilic and antimicrobial groups were bound to the PET molecular
backbone after surface grafting [39], layer-by-layer self-assembly [35,36], or atom transfer radical polymerization [37,43]. However, those strategies would cause a local deterioration of the PET molecular backbone, leading to significantly decrease in the mechanical properties and surface roughness of PET fabrics [43]. Additionally, their hydrophilicity and durable antimicrobial properties are still not satisfactory [37,43,44]. Therefore, it is of great importance to develop a new finishing technology to fabricate PET fabrics with excellent hydrophilicity, broad-spectrum antimicrobial and anti-mite properties as well as enhanced stability against long-term laundering without compromising its superiority. A novel benzophenone containing polyethylenimines has reported to be covalently bonded onto polymer surfaces using mild photo-crosslinking, imparting non-leaching thin antimicrobial coatings for fabrics [45]. However, the preparation process is relatively complicated, and the final yield is not satisfactory. Especially, no investigation of the perdurable antimicrobial activity, anti-mite activity and other wearability properties of the treated textiles had been reported. Herein, we developed a one-step eco-friendly photochemical finishing method to fabricate polyester fabrics with excellent hydrophilicity, antistatic property, perdurable antimicrobial, and anti-mite activities by using a benzophenone group terminated quaternary ammonium salt (BP-QAS, 1) as an antimicrobial and anti-mite finishing agent via mild UV light irradiation (λ = 365 nm, 1.71 mW/cm2) activated rapid photochemical hydrogen abstraction reaction [46]. Moreover, we found that the BPQAS finished PET fabrics (2) are significantly improved in properties (Scheme 1): (i) greatly enhanced hydrophilic and antistatic properties; (ii) broad-spectrum antimicrobial activities even including the killing of drug-resistant bacteria and fungi; (iii) excellent acaricidal activity; (iv) improved cohesive force between the fibers leading to the improved tear strength; (v) no skin irritation and no toxicity, which are significant improvements that have not been studied or shown in other studies. 2. Results The BP-QAS was synthesized by the bromination reaction of methyl group in 4-methylbenzophenone, followed by a nucleophilic substitution of 4-bromomethyl benzophenone with N,N-dimethyldodecylamine (Scheme S1). And the BP-QAS was bonded onto the surface of raw PET fabrics via the photochemical hydrogen abstraction reaction between
Scheme 1. Photochemical finishing of PET fabrics by using quaternary ammonium salt terminated with benzophenone group (BP-QAS) with an excellent hydrophilic property, antistatic property, durable broad-spectrum antimicrobial, and acaricidal activities. 635
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Fig. 1. Characterization. (a) SEM images of BP-QAS finished PET fabric (2) and raw PET fabric (3). (b) Breaking strength, (c) tear strength, (d) elongation at break, (e) water vapor permeability; and (f) air permeability.
BP-QAS and hydrocarbons of the PET skeleton (Scheme S2) [46] The grafting degree of QAS to PET fabrics was increased with the increment of BP-QAS concentration (Fig. S2a). The success of the finishing process was also confirmed by X-ray photoelectron spectroscopy (XPS) (Fig. S2b & c) and energy dispersive X-ray analysis (EDX) (Fig. S2d). The peak at 402.5 eV (N1s: positively charged nitrogen N+, Fig. S2b) and the peak at 67.6 eV (Br3d, Fig. S2c) of QAS can be seen only in 2. Meanwhile, Br peak was also observed in EDX of 2 (Fig. S2d). These results showed that BP-QAS was successfully bonded onto the surface of PET fabrics.
2.2. Hydrophilicity To determine the hydrophilicity of PET fabrics after been finished with 1, water contact angle (WCA) [43], capillary penetration [4], and atomic force microscopy (AFM) [48,49] were applied to systematically investigate the hydrophilicity of 2 compared with 3. The water wicking height of 2 quickly reached 52.8 mm within 0.5 h and finally reached 135 mm in 12 h. On the contrary, the water wicking height of 3 was only 20.5 mm and then almost kept constant (∼26 mm) in 0.5–3 h, and finally reached 38.2 mm in 12 h (Fig. 2a). These results show that 2 is more hydrophilic than 3. Therefore, BP-QAS finishing agent can enhance the hydrophilicity of the fabrics remarkably. The water droplets on the surface of 3 could not spread in 5 min due to the high WCA of 3 (about 91°). In comparison, the water droplets rapidly spread on the surface of 2 within 1 s, lowering the WCA of 2 to 0° (Fig. 2b), which is much lower than that of previous finished PET based on local chain deterioration [37,43]. An improved hydrophilicity of fabrics could usually enhance the interaction between the fibers, resulting in improved fiber cohesion. To verify above point, the fiber morphology and cohesive force analyses were carried out as shown in Fig. 2c &d. The fibers of 3 form a loose mesh, while the fibers of 2 form a tight structure. The increase of intermolecular force between fibers would increase the separation and breaking strength of PET fibers, resulting in the enhanced tear strength of 2. Adhesion force in a humid environment is a result of the capillary condensation of water on PET
2.1. Comprehensive performance evaluation In the field-emission scanning electron microscope (FE-SEM) images (Fig. 1a), the BP-QAS finished PET fabrics (2) displayed a smooth surface and the same cross-section as raw PET fabrics (3), indicating that the fibers were intact after treatment. This result is better than that obtained by previous grafting methods which increased surface roughness [1,38]. Compared to 3, the tear strength of 2 increased by 17.0% in the warp direction from 14.7 to 17.2 N, and by 21.6% in the weft direction from 9.7 to 11.8 N (Fig. 1b). The tensile strength (Fig. 1c), and elongation-at-break (Fig. 1d) of 2 were almost the same as 3. The water vapor/air transmission of 2 was barely changed as compared with 3 (Fig. 1e & f), i.e. 2 kept good air and water permeability. Therefore, our as-obtained fabrics can maintain good thermo-physiological comfort for the body [47]. 636
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Fig. 2. Multi-performance evaluation. (a) Capillary effect, (b) water contact angle, (c, d) surface topography, (e) adhesive force and (f) water absorption of finished PET fabric (2) and raw PET fabric (3). Error bars of (a, e, f) have been based on the maximum and minimum values of five parallel samples.
surface, A high adhesion is correlated with high hydrophilicity [48]. A quantitative analysis of adhesion force of 2 compared to 3 was further performed by AFM using a hydrophilic probe (silicon nitride) to evaluate its hydrophilicity, as shown in Fig. 2e. The adhesion force of 2 was more than three times that of 3 (Fig. 2e). Single force spectroscopy events (Fig. S3) and adhesion mapping (Fig. S4) are available in Supporting Information along with additional technical details about AFM adhesion experiments. Meanwhile, the water absorption measurements of 3 and 2 were carried out to evaluate the sweat transpiration of 2 that was related to the wearing comfort of PET fabrics. The water absorption of 2 rapidly reached 74.8% and 88.1% within 0.5 and 1 min, respectively. It reached a plateau in 1–9 min and finally reached 92.7% in 10 min. Conversely, the water absorption of 3 was only 51.7%, and it did not change within 10 min (Fig. 2f). Taken together, these results showed that BP-QAS dramatically increased the hydrophilicity, adhesion forces, and mechanical properties of PET fabrics.
water-based electrolyte solution (NaCl). Since 1 is a positively charged agent, 2 shows a positively charged surface compared with slightly negatively charged 3 (Fig. S5). Experimental data (available in Table S1) along with theoretical and technical details about electrostatic AFM in the liquid can be found in the Supporting Information. 2.4. Antimicrobial activity The viable cell count method [4] was applied to quantitatively study the antimicrobial ability of 2 and 3. Fig. 4a & b showed the antimicrobial activities of 3 and 2 against Escherichia coli (E. coli, ATCC25922), Acinetobacter baumanii (A. baumannii, ATCC11038), Staphylococcus aureus (S. aureus, ATCC6538), Pseudomonas aeruginosa (P. Aeruginosa, ATCC9027), Staphylococcus epidermidis (S. epidermidis, ATCC12228), Streptococcus pneumoniae (S. pneumoniae, ATCC19165), Methicillin resistant staphylococcus aureus (MRSA, ATCC33591) and Aspergillus niger (A.niger, ATCC16404), The antimicrobial rates of 2 reached more than 99.99% against all the gram-negative bacteria (E. coli, A. baumannii, P. Aeruginosa), gram-positive bacteria (S. aureus, S. epidermidis, S. pneumoniae), multidrug resistant bacteria (MRSA) and fungi (A. niger). The antimicrobial data indicated that 2 showed excellent antimicrobial abilities against all evaluated bacteria and fungi. The antimicrobial rates of 3 and 2 were also tested after 50 laundering cycles using the FZ/T 73023-2006 standard method [4]. As can be seen in Fig. 4c, the antimicrobial rates were 92.4% (gram-positive bacterium S. aureus), 79.4% (gram-negative bacterium E. coli), and 75.9% (Fungi C. albicans). All these antimicrobial results of 2 are much greater than those reference values of AAA class and 3(Fig. 4c). These results show that 2 maintained durable antimicrobial activities after 50 repeated laundering cycles. Meanwhile, the diameters of the inhibition zone (DIZs) on S. aureus, E. coli, and C. albicans [4,52] of the 1-time washing leached products of 2 were tested and the results were all 0 mm. These results show that there is no leaching of 1 from 2 (Fig. S6). These results also confirmed that 2 had excellent perdurable antimicrobial activity against multiple laundering. Therefore, 1 can be a well-immobilized antimicrobial agent for PET fabric.
2.3. Antistatic properties Usually, the improved hydrophilicity of PET fabric can endow the antistatic property of PET fabrics [1,50]. Charge density, electrostatic voltage and half-life of 2 compared with those of 3 are shown in Fig. 3. The charge density of 2 was 1 mC/m2, which is only 20% of that of 3 (Fig. 3a). Similarly, the electrostatic voltage decreased greatly from 597 V to 132 V (Fig. 3b), and the half-life of electrostatic voltage fell enormously from 163 s to 0.01 s after being finished with 1 (Fig. 3c). The half-life of the electrostatic voltage of 2 was only 0.06% of that of 3, and it is also much lower than that of previous hydrophilic modification of polyester fabric by synergetic effect of biological enzymolysis and non-ionic surfactant [51]. These results indicated that the antistatic property of 3 was greatly enhanced via 1 finishing approach. To further analyze the effect of the finishing functionalization of BPQAS, the surface charge densities of 2 and 3 fabrics were measured using AFM force spectroscopy focused on electrostatic interactions in a 637
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Fig. 3. Evaluation of antistatic property of PET fabrics. (a) Charge density; (b) Electrostatic voltage; (c) Half-life. Error bars have been based on the maximum and minimum values of five parallel samples.
The bactericidal kinetics of 2 were tested by the viable cell count method [4]. Compared to 3, 2 showed increased antimicrobial rates against both E. coli and S. aureus with the increment of contact time. In the first 30 mins, the antimicrobial rates of 2 against both tested bacteria went up by 99.8% (Fig. 3d & e). When the contact time is greater than 120 mins, no viable bacteria was detected. Therefore, 2 showed excellent antimicrobial activity.
previous protocols [53]. The mites were grown on the surfaces of 2 and 3, and then the acaricidal activities were then evaluated according to their acaricidal rates. Fig. 5b showed the acaricidal activities of 2 against house dust mites as compared with 3. The number of viable mites decreased sharply with contact time in 2. The acaricidal rates of 2 reached 96.5% and 99.9% after the house dust mites were co-cultured with 2 for 96 and 120 h, respectively. This implied that 2 had excellent acaricidal activity against house dust mites. In contrast, the anti-mite rate of 3 decreased very slowly with the contact time, reaching only 17.6% even after 120 h incubation time. The positively charged QAS can easily interact with the cell membrane of bacteria [31] and generate excessive reactive oxygen species (ROS). While the amount of ROS surpasses the organism’s detoxification and repairing abilities, it would lead to cell death [33]. However, the anti-mite mechanism of QAS has been barely studied. To investigate the potential anti-mite mechanism of BP-QAS finished PET fabrics, the effect of PET fabrics on nitric oxide (NO) and glutathione (GSH) were tested. The generation of ROS such as NO can induce apoptotic cascade
2.5. Anti-mite activity The anti-mite activity of 2 against house dust mites were evaluated according to the Chinese national standard method (GB/T 24253-2009) [53]. The anti-mite test results can be seen in Fig. 5. Anti-mite kinetics of 2 was investigated and compared with 3 by previous protocols [53]. The mite repellent rate of 2 was 99.9% after incubation for 24 h, and no viable mites were observed, which was much higher than that of 3 (about 17.6%) (Fig. 5a). Anti-mite kinetics of 2 was investigated compared with that of 3 by
Fig. 4. Evaluation of antimicrobial activities. (a) Antimicrobial activities of raw PET fabrics (3, A) and finished PET fabrics (2, B); (b) Antimicrobial rates of finished PET fabrics (2) compared to 3; (c) Durable antimicrobial activities of 3 and 2 after repeated laundering (50 times); (d) Antibacterial kinetic of 3 and 2 against (d) S. aureus (ATCC 6538) and (e) E. coli (ATCC 25922). 60 mg/mL of BP-QAS. Error bars of (d, e) have been based on the maximum and minimum values of three parallel samples. 638
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Fig. 5. Anti-mite activities assay. (a) Mite repellent rate of 2 and 3; A-with anti-mite effect, B-with strong anti-mite effect, C-with strong anti-mite effect. (b) The acaricidal kinetics of 2 and 3; (c) NO and (d) GSH level of mite treated by and 2 and 3; surface topographies of (e) control mite and (f) mites treated by 2.
histopathological abnormal was found in hematoxylin & eosin (H&E) stained images at any evaluated areas masked by 2 or 3 (Fig. 6b & c). The primary irritation index of 2 and 3 are all negligible (Table S2). The acute oral toxicity tests in mice were also carried out to further prove the safety and biocompatibility BP-QAS finished textiles. At all evaluated amounts, both death (Fig. 7a) and huge body weight lost (Fig. 7b) were not seen. Besides, among all studies, there is no obvious behavior difference for mices. Their explorative behaviors were as usual. Their hair glossiness and skin color and other appearances did not show any obvious change. They eat, drunk, and behaved like normal. After treatment with 2, major organs were gathered on day fourteen to do the histology tests. All stomach, kidney, liver, large intestine as well as small intestine tissues are tested and turned out to be normal. No obvious histopathological abnormality was found among all the H&E stained images in all tested doses (Fig. 7c).
thorough caspases [54]. As shown in Fig. 5c, the concentration of NO of untreated mites is only 5.3 µg/g tissue (control), however, the concentration of NO exposed to 2 at different contact times reached 21.54 µmol/g tissue (24 h), 36.9 µmol/g tissue (48 h) and 48.93 µmol/g tissue (72 h), respectively, which were four times (24 h), seven times (48 h) and nine times (72 h) as large as control mite, and they were also about three times as large as that of mites exposed to 3 at the same contact times (Fig. 5c). Excessive destructive ROS production can cause oxidative stress and lipid peroxidation, and subsequently bacteria death [55]. GSH is widely applied as a good oxidative stress indicator in cells. The GSH antioxidant system is foremost among the cellular protective mechanisms. GSH can help maintain the normal function of the immune system, and it has antioxidant effects and integrated detoxification. GSH level of mites exposed to 2 was lower than mites exposed to 3 after different time. Particularly, GSH level of mites exposed to 2 after 72 h decreased to 90.63 µmol/g tissue, which is only 23% of that of untreated mites and PET fabric treated mites (Fig. 5d). The result showed that there was a significant drop in the GSH level and subsequent loss of the protective effect of the peroxidase-GSH system of mites exposed to 2. At high dose, ROS and oxidative stress production could lead to toxicity [56]. The acaricidal mechanism of 2 may be ascribed to disruption of the mite membrane due to oxidation stress based on ROS such NO, and, subsequently, the killing of the mites. This destructive acaricidal mechanism triggered by excessive ROS was also confirmed by the morphological change in house dust mites caused by 2 using environmental scanning electron microscopy (ESEM) images, which revealed that the mites exposed to 3 maintained their integrity with no obvious morphological changes after 48 h (Fig. 5e). While the mite body exposed to 2 underwent a transformation from a full state to a shrunken state, and the skin of the back and abdomen roughened. The jaw became hollow, and four of the feet contracted toward the abdomen, and the bristles became disordered. The mites exposed to 2 lost their integrity, wrinkled outer membrane substantially and showed a destructive structure, indicating damage and death (Fig. 5f).
3. Discussion Mechanical properties are also very important for fabrics, especially for their long-lasting applications. In this work, mild UV light (λ = 365 nm) was utilized to finish PET fabrics with covalently bonded 1. Compared with oxidative damage of polymer and substrates exposed to higher energy UV [45], PET fibers maintained breaking strength and smooth surface topography of 2 because it did not damage the fiber structure of PET during the finishing process. Additionally, the finishing process induced by mild UV light is suitable for large-scale fabrication of PET fabrics. Utilizing photochemical hydrogen abstraction reaction, hydrophilic QAS group was introduced onto the PET surface with no obvious unwanted color change. The hydrophilicity and water absorption of PET fabrics were significantly improved, lending to excellent antistatic property and enhancing its comfort and wearability. In addition, the polar QAS group improved the intermolecular interaction of PET fibers, leading to high adhesion forces of PET fibers and preventing pilling. At the same time, increased cohesion force changed fibers from a loose to a tight state, resulting in a significant increase in tear strength. Therefore, the tear strength of 2 increased markedly, and there were no significant variations of elongation at break or tensile strength due to their retained fiber structures and the improved cohesive forces between the fibers. Meanwhile, Moisture and air transmission through fabrics are crucial for human comfort. The long alkyl chains-containing QAS was bound onto the surfaces of the PET textiles like ribbons fixed at only one end, and no dense coating film that would
2.6. Biocompatibility To test the safety and biocompatibility of textiles, 2 and 3 are exposed to the back of rabbit’s skin to test their irritation responses as illustrated in Fig. 6a. After contact for 24, 48, and 72 h, both erythema and edema are not found (Fig. 6a). Besides, no distinct 639
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Fig. 6. Rabbit skin irritation results according to ISO 10993. 10-2014 standard. (a) The images of rabbits’ back skin contacting with the sample (right) and negative control (left) at (I) 0 h, (II) 1 h, (III) 24 h, (IV) 48 h, and (V) 72 h. HE staining images of skin contacted with negative control (b) and sample (c). Scale bar represents 50 μm.
reduce their air and water permeability could be formed [32], so 2 showed no obvious decline of the air or water vapor permeability. Many antimicrobial PET fabrics with leaching antimicrobial agents were reported [34,57]. Generally, when antimicrobials are easy to be leached, these antimicrobial fabrics would reduce their antimicrobial performance, repeated laundering [58], and cause antimicrobial resistance due to sublethal concentrations of antimicrobials [59]. Additionally, leaching antimicrobials on textiles would kill the resident flora of nonpathogenic bacteria on the skin of the wearer, which are
important to the health of the skin as they can create an unfavorable environment for the growth of pathogenic bacteria [32]. Therefore, the synthesis of bound antimicrobial agents to replace their easy-leaching counterparts is critical. However, their durable antimicrobial finishing are challenging owing to the lack of reactive functional groups. To achieve perdurable antimicrobial activity, bound antimicrobial finishing methods have been developed for antimicrobial PET fabrics by damaging the PET backbone to produce reactive groups, followed by chemical modification. The above modified ways would increase the
Fig. 7. In vivo toxicity of sample. (a) Survival curves of mice after various treatments. The sample treated mice after oral administration showed 100% survival over 14 days. (b) Mice body weight gain percentages of mice after various treatments. The body weight of mice did not show significant change within 14 d. (c) HE staining images of major organs collected from different groups of mice on day 14. F: Female mice, M: Male mice. 640
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rough, and decline the mechanical properties of fabrics. Moreover, their durable antimicrobial properties and hydrophilicity was still not satisfied. Herein, we overcame the above challenges to fabricate PET fabrics with perdurable antimicrobial, anti-mite, antistatic, biocompatibility, and multi-laundering stability simultaneously by onestep eco-friendly strategy. The introduction of QAS to PET surface greatly improves its ability for strongly targeting to the oppositelycharged cell surface of bacteria to effectively kill the bacteria. The nonleaching property of 1 was further confirmed by the DIZ test results. It ensures durable antimicrobial and anti-mite activities of 2 after 50 laundering cycles. Since there is no 1 leached from 2, the drug resistance to 2 in microorganisms can be reduced [58], and skin irritations and toxicity can be inhibited [4,5]. Therefore, 1 is an excellent durable broad-spectrum antimicrobial and anti-mite finishing agent for fabrics. We attributed the antimicrobial mechanisms of 2 to the QASmicrobe binding [58] due to the attractive interaction between the positive charged cationic QAS on 2 and the oppositely charged microbe [60], followed by the ROS creation and microbe-killing. Anti-mite property is an important property that is less studied up to now. Here we demonstrated the excellent anti-mite property of our onestep eco-friendly finishing method for 2. The anti-mite property may have the same mechanism as antimicrobial property that may be related to destructive reactive oxygen species. Though the accurate antimite mechanism is not totally clear and new studies should be carried out in our future work, we paved a potential way for new anti-mite fabric studies. To sum up, BP-QAS is an excellent, durable broadspectrum antimicrobial and anti-mite finishing agent against gram-negative, gram-positive, and drug-resistant bacteria, fungi and house dust mites based on disruption of the microbial and mite membrane due to oxidation stress.
Appendix A. Supplementary data Supplementary data to this article can be found online at https:// doi.org/10.1016/j.cej.2018.10.070. References [1] J. Lv, Q. Zhou, T. Zhi, D. Gao, C. Wang, Environmentally friendly surface modification of polyethylene terephthalate (PET) fabric by low-temperature oxygen plasma and carboxymethyl chitosan, J. Clean Prod. 118 (2016) 187–196. [2] J.Y. Cho, C.J. Hong, H.M. Choi, Microwave-assisted glycolysis for PET with highly hydrophilic surface, Ind. Eng. Chem. Res. 52 (2013) 2309–2315. [3] J.Y. Cho, H.M. Choi, K.W. Oh, Rapid hydrophilic modification of poly(ethylene terephthalate) surface by using deep eutectic solvent and microwave irradiation, Text. Res. J. 86 (2016) 1318–1327. [4] S.G. Chen, L.J. Yuan, Q.Q. Li, J.N. Li, X.L. Zhu, Y.G. Jiang, O. Sha, X.H. Yang, J.H. Xin, J.X. Wang, F.J. Stadler, P. Huang, Durable antibacterial and nonfouling cotton textiles with enhanced comfort via zwitterionic sulfopropylbetaine coating, Small 12 (2016) 3516–3521. [5] S.B. Zhang, X.H. Yang, B. Tang, L.J. Yuan, K. Wang, X.Y. Liu, X.L. Zhu, J.N. Li, Z.C. Ge, S.G. Chen, New insights into synergistic antimicrobial and antifouling cotton fabrics via dually finished with quaternary ammonium salt and zwitterionic sulfobetaine, Chem. Eng. J. 336 (2018) 123–132. [6] M. Yu, Z. Wang, M. Lv, R. Hao, R. Zhao, L. Qi, S. Liu, C. Yu, B. Zhang, C. Fan, J. Li, Antisuperbug cotton fabric with excellent laundering durability, ACS Appl. Mater. Interfaces 8 (2016) 19866–19871. [7] Q. Yu, Z. Wu, H. Chen, Dual-function antibacterial surfaces for biomedical applications, Acta Biomater. 16 (2015) 1–13. [8] J. Virchow, V. Backer, P. Kuna, et al., Efficacy of a house dust mite sublingual allergen immunotherapy tablet in adults with allergic asthma: a randomized clinical trial, JAMA 315 (2016) 1715–1725. [9] V. Mahakittikun, J.J. Boitano, C. Komoltri, P. Ninsanit, T. Wangapai, Anti-mite covers: Potential criteria for materials used against dust mites, Text. Res. J. 79 (2009) 436–443. [10] J. Gabbay, J. Israel, Acaricidal fabric, US Patent 5,939,340,1999. [11] S. Rochat, C. Vidil, Use of zinc sulfide as an anti-mite agent, US Patent App. 10/500, 699, 2005. [12] W. Chin, G. Zhong, Q. Pu, C. Yang, W. Lou, P.F. De Sessions, B. Periaswamy, A. Lee, Z.C. Liang, X. Ding, S. Gao, C.W. Chu, S. Bianco, C. Bao, Y.W. Tong, W. Fan, M. Wu, J.L. Hedrick, Y.Y. Yang, A macromolecular approach to eradicate multidrug resistant bacterial infections while mitigating drug resistance onset, Nat. Commun. 9 (2018) 917. [13] P.A. Wender, W.C. Galliher, E.A. Goun, L.R. Jones, T.H. Pillow, The design of guanidinium-rich transporters and their internalization mechanisms, Adv. Drug Deliv. Rev. 60 (2008) 452–472. [14] R.E.W. Hancock, H.G. Sahl, Antimicrobial and host-defense peptides as new antiinfective therapeutic strategies, Nat. Biotechnol. 24 (2006) 1551–1557. [15] B.P. Mowery, S.E. Lee, D.A. Kissounko, R.F. Epand, R.M. Epand, B. Weisblum, S.S. Stahl, S.H. Gellman, Mimicry of antimicrobial host-defense peptides by random copolymers, J. Am. Chem. Soc. 129 (2007) 15474–15476. [16] M. Wenzel, A.I. Chiriac, A. Otto, D. Zweytick, C. May, C. Schumacher, R. Gust, H.B. Albada, M. Penkova, U. Krämer, R. Erdmann, N. Metzler-Nolte, S.K. Straus, E. Bremer, D. Becher, H. Brötz-Oesterhelt, H.-G. Sahl, J.E. Bandow, Small cationic antimicrobial peptides delocalize peripheral membrane proteins, PNAS 111 (2014) E1409–E1418. [17] L. Mi, S. Jiang, Integrated antimicrobial and nonfouling zwitterionic polymers, Angew. Chem. Int. Ed. 53 (2014) 1746–1754. [18] L. Zhang, Z. Cao, T. Bai, L. Carr, J.-R. Ella-Menye, C. Irvin, B.D. Ratner, S. Jiang, Zwitterionic hydrogels implanted in mice resist the foreign-body reaction, Nat. Biotechnol. 31 (2013) 553–556. [19] A.J. Keefe, S. Jiang, Poly(zwitterionic)protein conjugates offer increased stability without sacrificing binding affinity or bioactivity, Nat. Chem. 4 (2012) 60–64. [20] Z. Cao, L. Mi, J. Mendiola, E.-M. Jean-Rene, L. Zhang, H. Xue, S. Jiang, Reversibly switching the function of a surface between attacking and defending against bacteria, Angew. Chem. Int. Ed. 51 (2012) 2602–2605. [21] W. Wei, L. Yang, Z. Hui, C. Zhiqiang, Superdurable coating fabricated from a double-sided tape with long term “Zero” bacterial adhesion, Adv. Mater. 29 (2017) 1606506. [22] P. Li, Y.F. Poon, W. Li, H.Y. Zhu, S.H. Yeap, Y. Cao, X. Qi, C. Zhou, M. Lamrani, R.W. Beuerman, E.T. Kang, Y. Mu, C.M. Li, M.W. Chang, S.S.J. Leong, M.B. ChanPark, A polycationic antimicrobial and biocompatible hydrogel with microbe membrane suctioning ability, Nat. Mater. 10 (2011) 149–156. [23] Y.X. Chen, J.N. Li, Q.Q. Li, Y.Y. Shen, Z.C. Ge, W.W. Zhang, S.G. Chen, Enhanced water-solubility, antibacterial activity and biocompatibility upon introducing sulfobetaine and quaternary ammonium to chitosan, Carbohyd. Polym. 143 (2016) 246–253. [24] W.J. Zou, Y.X. Chen, X.C. Zhang, L.J. Na, S.L. Ming, G.Z. Fan, D. Bing, S.G. Chen, Cytocompatible chitosan based multi-network hydrogels with good antimicrobial, cell anti-adhesive and mechanical properties, Carbohyd. Polym. 202 (2018) 246–257. [25] Y. Si, Z. Zhang, W. Wu, Q. Fu, K. Huang, N. Nitin, B. Ding, G. Sun, Daylight-driven rechargeable antibacterial and antiviral nanofibrous membranes for bioprotective applications, Sci. Adv. 4 (2018) eaar5931. [26] A.P. Richter, J.S. Brown, B. Bharti, A. Wang, S. Gangwal, K. Houck, E.A. Cohen
4. Conclusion In view of the present disadvantage of durable functional finishing of polyester fibers, we develop a facile eco-friendly finishing technique for PET fabrics through photochemical reaction with BP-QAS. In this work, we explore a facile eco-friendly finishing technique for PET fabrics through photochemical reaction with benzophenone group terminated quaternary ammonium salt (BP-QAS). Compared to general finishing methods, antimicrobial, hydrophilic and positively charged small molecule compound was chemically bound onto the surfaces of the PET textiles like ribbons fixed at only one end without destruction of PET fiber structure, to impart long-lasting antimicrobial and antimite effects without damaging the mechanic performance, color, air permeability and water vapor permeability due to no dense coating film that would reduce their air and water permeability could be formed. The as-finished PET fibers changed from incompact state to compact state due to the increased cohesive forces within individual fibers, leading to significant better tear strength, hydrophilicity, hygroscopicity (absorption of sweat) and antistatic property. Moreover, the as-finished PET fabrics exhibit excellent, perdurable broad-spectrum antimicrobial and anti-mite activities against gram-negative, gram-positive, and drug-resistant bacteria, fungi and house dust mites based on disruption of the microbial and mite membrane due to oxidation stress. While no negative effects were observed for mouse and rabbit. The finished PET fabrics can be applied to multiple industries, including but not limited to packaging, clothes, water treatment, and medical appliances. Acknowledgements This work was supported by the National Natural Science Foundation of China (51773117, 51573097, 51573096), the Science and Technology Project of Guangdong Province (2015A010105033, 2014B09091041), the Collaborative Innovation and Technology Project for Shenzhen-Hong Kong Innovation Circle of Shenzhen city (SGLH20120926161415782). 641
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[27] [28] [29] [30] [31] [32] [33] [34]
[35] [36] [37] [38] [39]
[40] [41] [42]
Hubal, V.N. Paunov, S.D. Stoyanov, O.D. Velev, An environmentally benign antimicrobial nanoparticle based on a silver-infused lignin core, Nat. Nanotechnol. 10 (2015) 817–823. S.G. Chen, Y.J. Guo, S.J. Chen, H.M. Yu, Z.C. Ge, X. Zhang, P.X. Zhang, J.N. Tang, Facile preparation and synergistic antibacterial effect of three-component Cu/TiO2/ CS nanoparticles, J. Mater. Chem. 22 (2012) 9092–9099. Q. Liu, J. Huang, J. Zhang, Y. Hong, Y. Wan, Q. Wang, M. Gong, Z. Wu, C.F. Guo, Thermal, waterproof, breathable, and antibacterial cloth with a nanoporous structure, ACS Appl. Mater. Interfaces 10 (2018) 2026–2032. X. Lu, X. Feng, J.R. Werber, C. Chu, I. Zucker, J.-H. Kim, C.O. Osuji, M. Elimelech, Enhanced antibacterial activity through the controlled alignment of graphene oxide nanosheets, PNAS 114 (2017) E9793–E9801. Y. Tu, M. Lv, P. Xiu, T. Huynh, M. Zhang, M. Castelli, Z. Liu, Q. Huang, C. Fan, H. Fang, R. Zhou, Destructive extraction of phospholipids from Escherichia coli membranes by graphene nanosheets, Nat. Nanotechnol. 8 (2013) 594. S. Chen, Q. Chen, Q. Li, J. An, P. Sun, J. Ma, H. Gao, Biodegradable synthetic antimicrobial with aggregation-induced emissive luminogens for temporal antibacterial activity and facile bacteria detection, Chem. Mater. 30 (2018) 1782–1790. J.W. Gu, L.J. Yuan, Z. Zhang, X.H. Yang, J.X. Luo, Z.F. Gui, S.G. Chen, Non-leaching bactericidal cotton fabrics with well-preserved physical properties, no skin irritation and no toxicity, Cellulose 25 (2018) 5415–5426. M.P. Brynildsen, J.A. Winkler, C.S. Spina, I.C. MacDonald, J.J. Collins, Potentiating antibacterial activity by predictably enhancing endogenous microbial ROS production, Nat. Biotechnol. 31 (2013) 160–165. Y.X. Chen, W. Lan, J.Y. Wang, R.R. Zhu, Z.W. Yang, D.L. Ding, G.M. Tang, K.R. Wang, Q. Su, E.Q. Xie, Highly flexible, transparent, conductive and antibacterial films made of spin-coated silver nanowires and a protective ZnO layer, Physica E 76 (2016) 88–94. L. Pérez-Álvarez, E. Lizundia, S. del Hoyo, A. Sagasti, L.R. Rubio, J.L. Vilas, Polysaccharide polyelectrolyte multilayer coating on poly(ethylene terephthalate), Polym. Int. 65 (2016) 915–920. D. Cheng, X. Lin, L. Fan, G. Cai, J. Wu, W. Yu, Preparation and characterization of polyelectrolyte/silver multilayer films on PET substrates and its antibacterial property, Polym. Compos. 36 (2015) 1161–1168. X. Jin, J. Yuan, J. Shen, Zwitterionic polymer brushes via dopamine-initiated ATRP from PET sheets for improving hemocompatible and antifouling properties, Colloid Surf B 145 (2016) 275–284. B. Lepoittevin, L. Costa, S. Pardoue, D. Dragoe, S. Mazerat, P. Roger, Hydrophilic PET surfaces by aminolysis and glycopolymer brushes chemistry, J. Polym. Sci. Polym. Chem. 54 (2016) 2689–2697. H. Poortavasoly, M. Montazer, T. Harifi, Aminolysis of polyethylene terephthalate surface along with in situ synthesis and stabilizing ZnO nanoparticles using triethanolamine optimized with response surface methodology, Mater. Sci. Eng. CMater. 58 (2016) 495–503. Y. Gao, R. Cranston, Recent advances in antimicrobial treatments of textiles, Text. Res. J. 78 (2008) 60–72. X. Ping, M. Wang, G. Xuewu, Surface modification of poly(ethylene terephthalate) (PET) film by gamma-ray induced grafting of poly(acrylic acid) and its application in antibacterial hybrid film, Radiat. Phys. Chem. 80 (2011) 567–572. V.H. Fragal, T.S.P. Cellet, G.M. Pereira, E.H. Fragal, M.A. Costa, C.V. Nakamura, T. Asefa, A.F. Rubira, R. Silva, Covalently-layers of PVA and PAA and in situ formed
[43]
[44] [45] [46] [47] [48] [49] [50] [51] [52] [53] [54] [55] [56] [57] [58] [59] [60]
642
Ag nanoparticles as versatile antimicrobial surfaces, Int. J. Biol. Macromol. 91 (2016) 329–337. S. del Hoyo-Gallego, L. Pérez-Álvarez, F. Gómez-Galván, E. Lizundia, I. Kuritka, V. Sedlarik, J.M. Laza, J.L. Vila-Vilela, Construction of antibacterial poly(ethylene terephthalate) films via layer by layer assembly of chitosan and hyaluronic acid, Carbohyd. Polym. 143 (2016) 35–43. W. Ali, P. Sultana, M. Joshi, S. Rajendran, A solvent induced crystallisation method to imbue bioactive ingredients of neem oil into the compact structure of poly (ethylene terephthalate) polyester, Mater. Sci. Eng. C-Mater. 64 (2016) 399–406. V.P. Dhende, S. Samanta, D.M. Jones, I.R. Hardin, J. Locklin, One-step photochemical synthesis of permanent, nonleaching, ultrathin antimicrobial coatings for textiles and plastics, ACS Appl. Mater. Interfaces 3 (2011) 2830–2837. D. Chen, C.-C. Chang, B. Cooper, A. Silvers, T. Emrick, R.C. Hayward, Photopatternable biodegradable aliphatic polyester with pendent benzophenone groups, Biomacromolecules 16 (2015) 3329–3335. Y. Liu, J.H. Xin, C.H. Choi, Cotton fabrics with single-faced superhydrophobicity, Langmuir 28 (2012) 17426–17434. D.I. Kim, J. Grobelny, N. Pradeep, R.F. Cook, Origin of adhesion in humid air, Langmuir 24 (2008) 1873–1877. H.J. Butt, B. Cappella, M. Kappl, Force measurements with the atomic force microscope: Technique, interpretation and applications, Surf. Sci. Rep. 59 (2005) 1–152. E.S. Abdel-Halim, F.A. Abdel-Mohdy, S.S. Al-Deyab, M.H. El-Newehy, Chitosan and monochlorotriazinyl-beta-cyclodextrin finishes improve antistatic properties of cotton/polyester blend and polyester fabrics, Carbohyd. Polym. 82 (2010) 202–208. A. Gao, H. Shen, H. Zhang, G. Feng, K. Xie, Hydrophilic modification of polyester fabric by synergetic effect of biological enzymolysis and non-ionic surfactant, and applications in cleaner production, J. Clean Prod. 164 (2017) 277–287. S.G. Chen, S.J. Chen, S. Jiang, M.L. Xiong, J.X. Luo, J.N. Tang, Z.C. Ge, Environmentally friendly antibacterial cotton textiles finished with siloxane sulfopropylbetaine, ACS Appl. Mater. Interfaces 3 (2011) 1154–1162. W. Wei, J. He, B. Yu, Y. Zou, F. Liu, X. Chen, J. Chen, Synthesis of microencapsulated benzyl benzoate with a CaCO3 shell and its application to the durable anti-mite finishing of nylon 6 fabric, RSC Adv. 6 (2016) 59624–59632. S. Arora, J. Jain, J.M. Rajwade, K.M. Paknikar, Cellular responses induced by silver nanoparticles: in vitro studies, Toxicol. Lett. 179 (2008) 93–100. S.G. Chen, Y.J. Guo, H.Q. Zhong, S.J. Chen, J.N. Li, Z.C. Ge, J.N. Tang, Synergistic antibacterial mechanism and coating application of copper/titanium dioxide nanoparticles, Chem. Eng. J. 256 (2014) 238–246. A. Nel, T. Xia, L. Mädler, N. Li, Toxic potential of materials at the nanolevel, Science 311 (2006) 622–627. M. Montazer, V. Allahyarzadeh, Electroless plating of silver nanoparticles/nanolayer on polyester fabric using AgNO3/NaOH and ammonia, Ind. Eng. Chem. Res. 52 (2013) 8436–8444. B. Simoncic, B. Tomsic, Structures of novel antimicrobial agents for textiles – a review, Text. Res. J. 80 (2010) 1721–1737. A. Harms, E. Maisonneuve, K. Gerdes, Mechanisms of bacterial persistence during stress and antibiotic exposure, Science 354 (2016) aaf4268. Y. Jin, H. Pei, W. Hu, Y. Zhu, H. Xu, C. Ma, J. Sun, H. Li, A promising application of chitosan quaternary ammonium salt to removal of Microcystis aeruginosa cells from drinking water, Sci. Total Environ. 583 (2017) 496–504.