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22 lines
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[
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"id": 1,
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"chunk": "# Supporting Information \n\nAntifogging/Antibacterial Coatings Constructed by",
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"category": " Results and discussion"
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"id": 2,
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"chunk": "# N-Hydroxyethylacrylamide and Quaternary",
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"category": " Introduction"
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"id": 3,
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"chunk": "# Ammonium-Containing Copolymers \n\nShan Bai, Xiaohui Li\\*, Yunhui Zhao, Lixia Ren, Xiaoyan Yuan\\* \n\nSchool of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300350, China \n\n\\* E-mail: lixiaohui@tju.edu.cn; yuanxy $@$ tju.edu.cn \n\nMaterials. Aminopropylisobutyl polyhedral oligomeric silsesquioxane (POSS- $\\mathrm{\\cdotNH}_{2}$ , $98\\%$ ) was purchased from Hybrid Plastics, USA and used without further purification. 2-(Dimethylamino)ethyl methacrylate (DMAEMA, $98.5\\%$ ) from J&K Scientific, China, N-(2-hydroxyethyl) acrylamide (HEAA, $98\\%$ ) from Energy Chemical and glycidyl methacrylate (GMA, $595\\%$ ) from TCI Chemical Industrial Development, China were filtered through an neutral alumina column before use. 2-Aminoethyl methacrylate hydrochloride (AEMA, $90\\%$ ) from Jiuding Chemical Technology, China, 1,3,5-triformylbenzene (TFB, $99\\%$ ) from Bide Pharmatech, China were used as received. (3-Aminopropyl)trimethoxysilane (APTES, $90\\%$ ), $^{2,2^{\\circ}}$ -azobisisobutyrobutyl acrylate (AIBN), 1-bromobutane $(>99\\%)$ , 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC, $98\\%$ ) and 4-dimethylaminopyridine (DMAP, $99\\%$ ) were purchased from Tianjin Heowns Biochemical Technology Co. Ltd., China. Triethylamine (TEA, ${\\tt>}99\\%$ ) and $^{4,4^{\\prime}}$ -azobis(4-cyanvaleric acid) (ACVA) were purchased from Tianjin Kemiou Chemical Reagent Co. Ltd., China, and ACVA was used after recrystallization in ethanol. 4-Cyanopentanoic acid dithiobenzoate (CPADB) was synthesized according to previous report.1 Mueller-Hinton broth (MHB) and nutrient agar were supplied by Beijing Aoboxing Biological Technology, China. Gram-positive bacteria Staphylococcus aureus (S. aureus, ATCC 6538) and gram-negative bacteria Escherichia coli (E. coli, ATCC 8739) were incubated in MHB at $37^{\\circ}\\mathrm{C}$ for $24\\mathrm{~h~}$ . LIVE/DEAD® BacLightTM bacterial viability kit (L13152) were purchased from ThermoFisher Scientific, USA. \n\nSynthesis of POSS-CPADB. CPADB ( $\\left(0.56\\mathrm{~g},2.0\\mathrm{~mmol}\\right)$ , EDC $(1.15\\mathrm{~g},\\:6.0\\mathrm{~mmol})$ and DMAP $(0.15\\mathrm{~g},\\ 1.2\\mathrm{~mmol})$ were dissolved in $20~\\mathrm{mL}$ DCM. After stirring and degassing with nitrogen for $30\\mathrm{min}$ , a solution of POSS- $\\mathrm{\\cdotNH}_{2}$ $(2.10\\ \\mathrm{g},2.4\\ \\mathrm{mmol})$ in 2 mL DCM was added to the mixture and continued to stir at room temperature under nitrogen atmosphere for $12\\mathrm{~h~}$ . Then, the mixture was concentrated and purified by column chromatography using petroleum ether/ethyl acetate $(4/1,\\nu/\\nu)$ as eluent to obtain POSS-CPADB. $^{1}\\mathrm{H}$ NMR spectrum ( $\\mathrm{CDCl}_{3}$ , δ ppm): $\\delta=4.43$ (6), $\\updelta=3.98$ (3), $\\delta=3.74$ (7), $\\delta=3.40$ (9), $\\delta=3.15$ (4, 8), $\\updelta=2.13\\ –1.90$ (2), $\\delta=1.77$ (11), $\\delta=$ 1.37 (10, 14), $\\delta=1.14–1.02$ (1), $\\updelta=0.99–0.83$ (12, 13, 15). \n\nSynthesis of Quaternary Ammonium Compounds. Quaternary ammonium compounds (QAC) was synthesized referring to literature procedure.2 DMAEMA $\\left(9.33\\mathrm{~g},0.06\\mathrm{~mol}\\right)$ and 1-bromobutane $(8.95\\mathrm{~g},0.065\\mathrm{~mol})$ ) were charged into a $100~\\mathrm{{mL}}$ volume flask. Then, $30~\\mathrm{mL}$ acetonitrile was added as solvent and the mixture was stirred at $50^{\\circ}\\mathrm{C}$ for $52\\mathrm{~h~}$ . The obtained monomer was purified by washing with diethyl ether five times and dried under vacuum at room temperature to afford a white power. $^{1}\\mathrm{H}$ NMR of QAC (CDCl3, δ ppm): $\\delta=6.15$ , 5.68 (1, 1’), 4.66 (3), 4.17 (4), 3.66(6), 3.53 (5), 1.94 (2), 1,76 (8), 1.42 (7), 0.99 (9). \n\nSynthesis of POSS-P(QAC-co-AEMA). POSS-P(QAC-co-AEMA) copolymer was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Typically, QAC ( $588.0~\\mathrm{mg}$ , 2 mmol), AEMA $\\cdot82.8~\\mathrm{mg},0.5~\\mathrm{mmol})$ , POSS-CPADB ( $11.4~\\mathrm{mg},$ , $0.01\\ \\mathrm{mmol}\\$ ) and AIBN $(0.4~\\mathrm{mg},0.0025~\\mathrm{mmol})$ dissolved in EtOH ( $\\mathrm{1~mL}$ ) were added into a 10 mL Schlenk flask. The flask was deoxygenated by three consecutive freeze-pump-thaw cycles before the polymerization was conducted at $70^{\\circ}\\mathrm{C}$ for $10\\mathrm{~h~}$ , and then quenched by rapid cooling immersion of the flask into iced water. The synthesized copolymer of POSS-P(QAC-co-AEMA) was precipitated into $n$ -hexane for five times and subsequently dialyzed for 3 days to lyophilize. \n\nSynthesis of P(HEAA-co-GMA). The copolymer of P(HEAA- $\\scriptstyle\\cdot c o$ -GMA) was synthesized by traditional free radical polymerization. Briefly, HEAA ( $516.0~\\mathrm{mg}$ , mmol) and GMA $(49.0~\\mathrm{mg},$ , mmol) were dissolved in mixed solvent of $\\mathrm{EtOH}/\\mathrm{H}_{2}\\mathrm{O}\\left(1/1,\\nu/\\nu\\right)$ , then $2.8~\\mathrm{mg}$ ACVA was added as the thermal initiator. After degassing by nitrogen for $30\\ \\mathrm{\\min}$ , the polymerization was performed at $65^{\\circ}\\mathrm{C}$ for $10\\mathrm{{h}}$ , and then the reaction mixture was precipitated in acetone. A certain volume of deionized water was added to the copolymer immediately after drying under vacuum at room temperature for storage of P(HEAA-co-GMA). \n\nCharacterizations of POSS-P(QAC-co-AEMA) and P(HEAA-co-GMA) Copolymers. Proton nuclear magnetic resonance ( $\\mathrm{^{1}H}$ NMR) spectroscopy (Bruker $400~\\mathrm{{MHz}}$ , Germany) was used to confirm the chemical structure of the prepared copolymers. Aqueous gel permeation chromatography (GPC) was conducted to measure the number-average molecular weight $(\\overline{{M}}_{n})$ of the synthesized copolymers, which was performed on a Viscotek’s GPC system using poly(ethylene glycol) as standards for calibration. The eluent was $0.5\\mathrm{~M~}$ acetic acid/0.5 M sodium acetate buffer solution $\\mathrm{(pH}\\ \\approx4.5\\$ with a flow rate of 1 mL/min. For synthesis POSS-P(QAC-co-AEMA), quaternary ammonium compound (QAC) was first prepared by quaternization of DMAEMA with 1-bromobutane to obtain $N.$ -(2-(methacryloyloxy)ethyl)- $.N,$ , $N.$ -dimethylbutan aminium bromide. Hydrophobic POSS was introduced owing to its enhanced stability and mechanical properties by taking POSS-CPADB as a RAFT agent for copolymerization of QAC and AEMA. As shown in Figure S1(a), the chemical shifts of double bond protons at 6.2-5.5 ppm disappeared and a broad peak of 2.13-1.86 ppm derived from methylene in the backbone chain could be observed, suggesting the copolymerization has been performed. All other chemical shifts were shown in the spectrum. It could be calculated from $^{1}\\mathrm{H}$ NMR spectrum that actual ratio of QAC and AEMA is 3:1 and the number-average molecular weight $(\\overline{{M}}_{n})$ of POSS-P(QAC-co-AEMA) copolymer obtained from GPC is $12.0\\times10^{4}$ . $\\mathrm{^{1}H}$ NMR and GPC results of P(HEAA- $.c o$ -GMA) copolymer were given in Figure S1(b). Compared with the spectra of HEAA and GMA, it could be seen from copolymer spectrum that each peak has corresponding proton attribution and the actual ratio of the two monomers is 15:1, which was consistent with the feeding ratio, indicating HEAA and GMA have similar competition rate in the process of copolymerization.3 The molecular weight of P(HEAA- $c o$ -GMA) is $9.94\\times10^{4}$ . \n\n \nFigure S1. (A) $^{1}\\mathrm{H}$ NMR spectra of POSS-CPADB, QAC, AEMA and copolymer POSS-P(QAC-co-AEMA), (B) $^{1}\\mathrm{H}$ NMR spectra of GMA, HEAA and copolymer P(HEAA-co-GMA), (C) GPC retention curves of the two synthesized copolymers. \n\nThickness of the Coatings. Scanning electron microscopy (Hitachi SU1510, Japan) was used to measure the thickness of the prepared coatings by observing the cross-sections after liquid nitrogen quenching. It was obtained from the SEM images showed in Figure S2 that the thickness of neat PPQA coating was $9.14{\\pm}0.39~\\upmu\\mathrm{m}$ , which was larger than that of neat PHG coating $(6.74{\\pm}0.17~\\upmu\\mathrm{m})$ . However, the three blending coatings, $\\mathrm{PPQA}_{2}/\\mathrm{PHG}_{1}$ , $\\mathrm{PPQA_{1}/P H G_{1}}$ , and $\\mathrm{PPQA_{1}/P H G_{2}}$ had similar thickness of $7.34{\\pm}0.36\\$ , $7.57{\\pm}0.59\\$ and $7.13{\\pm}0.22\\ \\upmu\\mathrm{m}$ , respectively. \n\n \nFigure S2. SEM images of the cross-sections for different coatings. \n\nAntifogging Properties of $\\mathbf{PQA_{1}}/\\mathbf{PHG_{1}}$ Coating. To investigate the effect of POSS on coating properties, the copolymer of P(QAC-co-AEMA) was also synthesized via RAFT polymerization. GPC result $(8.50\\times10^{4}$ ) indicated that it had similar molecular weight to POSS-P(QAC-co-AEMA). $\\mathrm{PQA_{1}/P H G_{1}}$ coating was also prepared by blending P(QAC-co-AEMA) with P(HEAA-co-GMA) at a ratio of $1/1$ . The antifogging performance of $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ blending coatings were evaluated and compared to explain the effect of POSS on antifogging performance. As shown in Figure S3(a), $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ coatings exhibited indistinguishable antifogging performance under both hot-vapor and cold-warm conditions. Furthermore, visible light transmittance of the two blending coatings was recorded immediately after removing them from $\\mathopen{}\\mathclose\\bgroup\\left.-20^{\\circ}\\mathrm{C}\\aftergroup\\egroup\\right.$ condition (Figure S3(b)). Compared with POSS-containing blending coating, $\\mathrm{PQA_{1}/P H G_{1}}$ coating showed a slightly increased transmittance only in lower wavelength range, probably ascribed to the absence of hydrophobic POSS. Therefore, it could be concluded that POSS had little effect on antifogging performances in the whole range of visible light wavelength. \n\n \nFigure S3. (a) Antifogging performance of $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ coatings. (B Transmittance of $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ coatings during cold-warm antifogging test. \n\nStability of the Coatings. The stability of the blending coatings was evaluated by firstly immersing the coatings into PBS buffer $\\mathrm{(pH~7.4)}$ at $37^{\\circ}\\mathrm{C}$ for $30~\\mathrm{min}$ , followed by testing their antifogging performance with hot-vapor method. As shown in Figure S4, though decreased transparency was observed for PPQA and PHG coating due to their original inferior antifogging ability, the three blending coatings of $\\mathrm{PPQA_{2}/P H G_{1}}$ , PPQA1/PHG1and $\\mathrm{PPQA_{1}/P H G_{2}}$ were still effective in preventing fog formation after immersion, suggesting their stability and long-last utilities to some extent. To investigate the effect of POSS on coating stability, $\\mathrm{PQA_{1}/P H G_{1}}$ coating were also treated with the same way. It could be seen that after $30~\\mathrm{min}$ of immersion, $\\mathrm{PQA_{1}/P H G_{1}}$ coating showed some dissolution on the edges, in contrast, all the prepared POSS-contained coatings kept the intact morphology, which demonstrated that the introduced POSS was favor of enhancement of coating stability. \n\n \nFigure S4. Hot-vapor antifogging performance of the prepared coatings after immersing them into PBS buffer for $30\\mathrm{min}$ . \n\nAntibacterial Properties of $\\mathbf{PQA_{1}}/\\mathbf{PHG_{1}}$ Coating. The minimal inhibitory concentrations (MIC) of P(QAC-co-AEMA) copolymer against $S.$ . aureus and $E$ . coli were tested and the compared results with that of POSS-P(QAC- $c o$ -AEMA) were shown in Figure S5(a). It could be seen that the MIC values of P(QAC-co-AEMA) were 128 and $256~\\upmu\\mathrm{g/mL}$ towards S. aureus and E. coli, respectively, being the same as that of POSS-P(QAC-co-AEMA) copolymer. Furthermore, the antibacterial properties of $\\mathrm{PQA_{1}/P H G_{1}}$ coating were also investigated via standard plate count method. As shown in Figure S5(b), the two coatings also exhibited comparable antibacterial activity against both bacteria strains. It was concluded that POSS had little effect on antibacterial property in this work. \n\n \nFigure S5. (a) Growth inhibition rates of POSS-P(QAC-co-AEMA) and P(QAC-co-AEMA) copolymers aqueous solution with a series of concentrations against S. aureus and $E$ . coli. (b) Growth inhibition rates of the $\\mathrm{PPQA_{1}/P H G_{1}}$ and $\\mathrm{PQA_{1}/P H G_{1}}$ blending coatings calculated by standard plate count methods. All data were obtained from at least three samples. \n\nRecycling Antibacterial Properties of the Coatings. In this work, the long-term and recycling antibacterial property of the blending coatings was investigated by first placing coating samples above the boiling water $90\\%$ RH, $70{\\sim}80^{\\circ}\\mathrm{C}\\$ for $30~\\mathrm{min}$ , followed by evaluating their antibacterial activity again via standard plate count method. As shown in Figure S6, all the prepared coatings maintained almost the same bacterial growth inhibition rates as before, which could indicate the long-term and recycling antibacterial property to some extent. \n\n \nFigure S6. Bacterial growth inhibition rates of the prepared coatings after exposing foggy condition $\\sim90\\%$ RH, $70{\\sim}80^{\\circ}\\mathrm{C}\\$ for $30\\mathrm{min}$ . \n\nCytotoxicity of the Coatings. The cytotoxicity of the coating against L929 has been detected by CCK-8 assay. As shown in Figure S7, the relative cell viabilities for all the prepared coatings were less than $60\\%$ . It was probably due to the quaternary ammonium compounds and the cell adhesion on the coating surfaces. In addition, 1,3,5-triformylbenzene, as an aldehyde compound, may also had effect on cytotoxicity. \n\nRelative cell viability $(\\%)=(O D_{\\mathrm{coating}}/O D_{\\mathrm{positive~control}}){\\times}100$ \n\n \nFigure S7. Relative cell viability against L929 on different coatings after $24\\mathrm{h}$ at $37^{\\circ}\\mathrm{C}$ . \n\nVideo S1. The video of the antifogging performance in vivo of bare glass. \n\nVideo S2. The video of the antifogging performance in vivo of $\\mathrm{PPQA_{1}/P H G_{2}}$ coating.",
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"category": " Materials and methods"
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"id": 4,
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"chunk": "# REFERENCES \n\n(1) Li, X. H.; Zhang, K. Q.; Zhao, Y. H.; Zhu, K. Y.; Yuan, X. Y. Formation of Icephobic Film from POSS-Containing Fluorosilicone Multi-Block Methacrylate Copolymers. Prog. Org. Coat. 2015, 89,150-159. (2) Wan, X.; Zhang, Y.; Deng, Y.; Zhang, Q.; Li, J.; Wang, K.; Li, J.; Tan, H.; Fu, Q. Effects of Interaction between a Polycation and a Nonionic Polymer on Their Cross-Assembly into Mixed Micelles. Soft Matter 2015, 11, 4197-4207. (3) Zhao, C.; Zheng, J. Synthesis and Characterization of Poly(N-hydroxyethylacrylamide) for Long-Term Antifouling Ability. Biomacromolecules 2011, 12, 4071-4079.",
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"category": " References"
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}
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