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"id": 1,
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"chunk": "# Supporting Information",
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"category": " References"
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"chunk": "# Amphiphilic Antifogging/Anti-icing Coatings Containing POSS-PDMAEMA- $b$ -PSBMA \n\nChuan Li, Xiaohui Li, Chao Tao, Lixia Ren, Yunhui Zhao, Shan Bai, and Xiaoyan Yuan\\* \n\nSchool of Materials Science and Engineering, and Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072, China \n\nE-mail: yuanxy $@$ tju.edu.cn; xyuan28 $@$ yahoo.com \n\nMaterials. Aminopropyllsobutyl POSS (apPOSS) was purchased from Hybrid Plastics, USA, and used as received. 2-(Dimethylamino) ethyl methacrylate (DMAEMA, $598.5\\%$ ), 2-bromoisobutyryl bromide (BIBB, $599\\%$ ) and ethyl-2-bromoisobutanoate (EBIB, $599\\%$ ) were supplied by Beijing Bailingwei Technology Co. Ltd., China. [2-(Methacryloyloxy) ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA, AR), 1,1,4,7,10,10-hexamethyl-triethylenetetramin (HMTETA, $597\\%$ ) , Igracure 2959 (AR), triethylamine (TEA, $599\\%$ ), 2,2,2-trifluoroethanol (AR) and ethyleneglycol dimethacrylate (EGDMA, $59\\%$ ) were obtained from Tianjin Xi'ensi Aupu Technology Co. Ltd., China. DMAEMA and EGDMA were passed through an alumina column to remove inhibitor. BIBB, EBIB, SBMA, HMTETA, TEA and Igracure 2959 were used without further purification. CuBr (AR) was bought from Tianjin Kermel Chemical Reagent Co. Ltd., China, and was dissolved in glacial acetic acid for $24\\mathrm{~h~}$ to remove $\\mathrm{CuBr}_{2}$ , and washed with methanol and glacial acetic acid for three times, and then dried under vacuum. All other reagents were supplied by Tianjin Yuanli Chemical Co. Ltd., China, and used as received without further purification. \n\nSynthesis of POSS-Br Initiator. POSS-Br as atom transfer radical polymerization (ATRP) initiator was prepared according to the reference.1 ApPOSS $(0.8745~\\mathrm{g},\\ 1\\ \\mathrm{mmol})$ and TEA 1 $\\mathrm{0.1518~g,}1.5\\mathrm{\\mmol}\\mathrm{}\\mathrm{},$ and THF $(20~\\mathrm{mL})$ ) were charged into a three-necked flask and degassed for at least three times. Degassed BiBB $\\mathrm{(0.2759~g,1.2~mmol}$ , dissolved in $10~\\mathrm{ml}$ THF) solution was slowly added into the flask at $0{}^{\\circ}\\mathrm{C}$ . The solution was magnetically stirred for $^{\\textrm{1h}}$ in an ice/water bath and then maintained at room temperature to react for another $12\\mathrm{~h~}$ . The precipitate was removed by filtration, and the filtrate was washed with a saturated aqueous solution of sodium bicarbonate and NaCl. Anhydrous sodium sulfate was added into the organic layer to eliminate residual moisture. Then, macroinitiator POSS-Br was obtained by removing solvent by a rotary evaporator and followed by vacuum drying (yield $75\\%$ ). \n\nSynthesis of POSS-PDMAEMA. POSS-PDMAEMA was synthesized by using POSS-Br as an ATRP macroinitiator. The mixture of POSS-Br $(0.1024\\ \\mathrm{g},0.1\\ \\mathrm{mmol})$ , DMAEMA $(1.8865\\ {\\mathrm{g}},$ 12 mmol), HMTETA $(0.0277~\\mathrm{g},\\ 0.12~\\mathrm{mmol})$ and THF $(2\\mathrm{~ml})$ ) was injected into the $10\\mathrm{mL}$ standard Schlenk flask. Highly pure nitrogen was filled the flask and then oxygen was removed by three freeze-pump-thaw cycles. Subsequently, CuBr $0.0144\\ \\mathrm{g},0.1\\ \\mathrm{mmol}$ ) was added quickly to the flask. Three freeze-pump-thaw cycles were carried out again to remove residual oxygen. The mixture was reacted at $50^{\\circ}\\mathrm{C}$ for 1.5, 2 and $2.5\\mathrm{h}$ , respectively, and terminated by dropping a few THF droplets into the flask. The solution was passed through a neutral alumina column to intercept ${\\mathrm{Cu}}^{2+}$ and concentrated in a rotary evaporator. Finally, POSS-PDMAEMA polymers with three different polymerization degrees, i.e., POSS-PDMAEMA $50$ , POSS-PDMAEMA70, and POSS-PDMAEMA90, were obtained by precipitating into cold $n$ -hexane and followed by drying in a vacuum oven for $24\\mathrm{h}$ . \n\nSynthesis of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\mathbf{b}$ -PSBMA. In order to obtain block copolymer POSS-PDMAEMA- $b$ -PSBMA, ATRP initiator POSS-Br was first synthesized, and followed by POSS-PDMAEMA-Br preparation from ATRP of DMAEMA. Using POSS-PDMAEMA-Br as the macroinitiator, three POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers with different polymerization degrees were synthesized via subsequent ATRP of SBMA. Typically, POSS-PDMAEMA-Br (0.01 mmol), SBMA (1 mmol) and HMTETA $(0.2\\mathrm{mmol})$ ) were dissolved in $6~\\mathrm{mL}$ mixed solvent of methanol-water $(1/1,\\mathbf{v}/\\mathbf{v})$ and were injected into the $25~\\mathrm{mL}$ standard Schlenk flask. The solution was degassed by three freeze-pump-thaw cycles under nitrogen atmosphere and then CuBr (0.1 mmol) was added quickly to the flask. Three freeze-pump-thaw cycles subsequently were carried out again to exclude remaining oxygen. The reaction mixture was stirred at $25~^{\\circ}\\mathrm{C}$ for $40\\mathrm{{h}}$ . POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA block copolymers were obtained by dialysis against deionized water for 3 days (MWCO 2000) and recovered by lyophilization. The POSS-PDMAEMA- $b$ -PSBMA block copolymers with different polymerization degrees and similar DMAEMA to PSBMA ratios, POSS- $\\mathrm{\\cdotD}_{50}–b–\\mathrm{S}_{7}$ , POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ , and POSS- $\\mathrm{\\cdotD}_{90}–b–\\ensuremath{\\mathrm{S}}_{13}$ were prepared. \n\nSynthesis of PDMAEMA- $\\mathbf{\\delta}_{\\mathbf{b}}$ -PSBMA. Similar to the synthesis of POSS-PDMAEMA- $\\cdot b$ - PSBMA, block copolymer PDMAEMA ${.50}$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA7 without POSS was synthesized by using ethyl-2-bromoisobutanoate as the initiator and followed by using PDMAEMA50-Br as the macroinitiator. PDMAE $\\mathrm{MA}_{50}$ -Br (0.01 mmol), SBMA (1 mmol) and HMTETA $(0.2\\mathrm{mmol})$ ) were dissolved in $6~\\mathrm{mL}$ mixed solvent of methanol-water $(1/1,\\mathbf{v}/\\mathbf{v})$ and were injected into the $25~\\mathrm{mL}$ standard Schlenk flask. The solution was degassed by three freeze-pump-thaw cycles under nitrogen atmosphere and then CuBr (0.1 mmol) was added quickly to the flask. Three freeze-pump-thaw cycles subsequently were carried out again to exclude remaining oxygen. The reaction mixture was stirred at $25~^{\\circ}\\mathrm{C}$ for $40\\mathrm{~h~}$ . The PDMAEMA $_{50}$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA7 block copolymer i.e., $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ , was obtained by dialysis against deionized water for 3 days (MWCO 2000) and recovered by lyophilization. \n\nCharacterizations of POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\pmb{b}$ -PSBMA. $\\mathrm{^{1}H\\ N M R}$ spectra were recorded on an INOVA ${500}~\\mathrm{MHz}$ spectrometer (USA) using $\\mathrm{CDCl}_{3}$ and $\\mathrm{D}_{2}\\mathrm{O}$ as solvents. $\\mathrm{^{1}H\\ N M R}$ spectra of apPOSS, POSS-Br, POSS-PDMAE $\\mathrm{\\uA_{70}}$ , POSS-PDMAEMA $70$ - $\\cdot b$ -PSBMA10 are shown in Figure S1. In comparison with the $\\mathrm{^1H}$ NMR spectrum of POSS- $\\cdot\\mathrm{NH}_{2}$ shown in Figure S1(a), there are representative δH (ppm) at 3.26 (f), 1.96 (h), 6.75 (g) in Figure S1(b), verifying that the initiator POSS-Br was successfully synthesized.2 For POSS-PDMAEMA70 (Figure S1(c)), the appearance of signals of DMAEMA δH (ppm) at 0.89-1.05 (a), 1.82-1.96 (b), 2.32 (d), 2.61 (e), 4.07 (f) and typical δH (ppm) at 0.60 (c) of POSS- $\\mathrm{\\cdotNH}_{2}$ could prove the structure of POSS-PDMAEMA70. Compared with POSS-PDMAEMA $70$ (Figure S1(c)), the chemical structure of POSS-PDMAEMA $70$ - $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA10 (Figure S1(d)) could be confirmed by the evident δH (ppm) at S-3 \n\n4.00 (a), 2.61 (b), 2.19 (c, j), 1.70-1.83 (d, l), 0.77-1.00 (e, p), 3.09 (f), 3.50 (g), 4.35 (h), 2.83 (i), \n3.66 (k).3 \n\n \nFigure S1. $\\mathrm{^{1}H\\ N M R}$ spectra of apPOSS (a), POSS-Br (b), POSS-PDMAEMA $^{70}$ in $\\mathrm{CDCl}_{3}$ (c), and POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ in ${\\bf D}_{2}\\mathrm{O}$ (d). \n\nFourier-transform infrared (FTIR) spectra of POSS-Br, POSS-PDMAEMA70, $\\mathrm{POSS-D}_{70^{-}}b.$ S10 were obtained on a Perkin-Elmer Spectrum 100 spectrometer (USA) using KBr pellet technique. As shown in Figure S2, the stretching vibration characteristic peak of Si-O-Si at $1112~\\mathrm{{cm}^{-1}}$ is apparent. The peak at $2954~\\mathrm{{cm}^{-1}}$ and $1323~\\mathrm{{cm}^{-1}}$ are attributed to the C-H stretching vibration and the C-H bending vibration, respectively. The signal at $695~\\mathrm{{cm}^{-1}}$ belongs to the C-Br stretching vibration.4,5 The data mentioned above further verify that POSS-Br was synthesized. In the FTIR spectra of POSS-PDMAEMA70, it is easily to find three C-H characteristic peaks at $2950~\\mathrm{cm}^{-1}$ , $2822~\\mathrm{{cm}^{-1}}$ and $2776~\\mathrm{{cm}^{-1}}$ . Meanwhile, the signals at $1723~\\mathrm{{cm}^{-1}}$ , $1457~\\mathrm{{cm}^{-1}}$ , $1270~\\mathrm{{cm}^{-1}}$ and 1112 $\\mathrm{cm}^{-1}$ belong to characteristic absorption bands of $\\scriptstyle\\mathbf{C=O}$ , C-N, $\\mathrm{CH}_{2}$ , and Si-O-Si respectively. All the date above mentioned demonstrates that POSS-PDMAEMA70 was prepared by ATRP. After copolymering with SBMA, we could find there was a new characteristic peak at $1039~\\mathrm{{cm}^{-1}}$ associated to the stretching vibration peak of $\\scriptstyle{\\mathsf{S}}=0$ , indicating the successful introduction of SBMA blocks. The peak appearance of C-O at $1149~\\mathrm{{cm}^{-1}}$ and the weaken strength of peak 1270 $\\mathrm{cm}^{-1}$ also proved the structure of POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ .6,7 \n\n \nFigure S2. FTIR of POSS-Br, POSS-PDMAEMA70 and POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ . \n\nThe molecular weight and polydispersity of the prepared copolymers PDMAEMA50, POSS-PDMAEMA with different polymerization degrees and $\\mathrm{D}_{50}–b–\\mathrm{S}_{7}$ were determined on a Waters 1515-2414 gel permeation chromatography (GPC, USA) with THF as the eluent and polystyrene as calibration. The polydispersity of the prepared polymers POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA were measured using a Viscotek’s GPC system with sodium acetate buffer $(0.5~\\mathrm{M}$ of NaAc and $0.5{\\mathrm{~M~}}$ of HAc, $\\mathrm{pH}=\\sim4.5)\\$ as the eluent at $30~^{\\circ}\\mathrm{C}$ at a flow rate of $1.0~\\mathrm{{mL}\\mathrm{{min}^{-1}}}$ . As shown in Figure S3, the unimodal GPC traces of POSS-PDMAEMA50, POSS-PDMAE $\\mathrm{\\uA_{70}}$ , POSS-PDMAEMA90, $\\mathrm{DMAEMA}_{50}$ , $\\mathrm{POSS-D}_{50^{-}}b{\\cdot}\\mathrm{S}_{7}$ , $\\mathrm{POSS-D}_{70}–b–\\mathrm{S}_{10}.$ , POSS- $\\mathrm{\\bfD}_{90}–b–\\mathrm{\\bfS}_{13}$ and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ represented narrow polydispersity with PDI values of 1.27, 1.26, 1.22, 1.08, 1.07, 1.08, 1.11, and 1.19, respectively, indicating that the controlled polymerization was achieved. Because the molecular weight of zwitterionic polymers was difficult to measure by GPC, so we employed $\\mathrm{^{1}H}$ NMR and GPC to determine the molecular weight of the copolymers in this work. The molecular weight of POSS-PDMAEMA and POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA copolymers were calculated through the $\\mathrm{^{1}H N M R}$ method, but the molecular weight of $\\mathbf{PDMAEMA}_{50}$ and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ were acquired by GPC due to its difficulty to adopt the $\\mathrm{^{1}H N M R}$ spectra by the integration of proton $\\mathrm{^{1}H N M R}$ feature signals. \n\n \nFigure S3. GPC curves of POSS-PDMAE $\\mathbf{MA}_{50}$ (a), POSS-PDMAE $\\mathbf{MA}_{70}$ (b), POSSPDMAEMA90 (c), $\\mathrm{DMAEMA_{50}}$ (d) and $\\mathrm{D}_{50^{-}}b{-}S_{7}$ (e) by using THF as the eluent, (A), and POSS- $\\mathbf{\\cdotD_{50}}–b\\mathbf{-S_{7}}$ (f), POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ (g) and POSS- $\\mathrm{\\cdotD}_{90^{-}}b{-}\\mathrm{S}_{13}$ (h) by using a sodium acetate buffer as the eluent (B). \n\nThermal gravimetric analysis (TGA) was implemented on a TA Q50 instrument (USA) under nitrogen atmosphere at a heating rate of $10~\\mathrm{{^{\\circ}C/m i n}}$ from 20 to $800~^{\\circ}\\mathrm{C}$ . The TGA tests of POSS-Br, POSS-PDMAEMA70, POSS-PDMAEMA $70$ - $b$ -PSBMA10 were carried out. As shown in Figures S4, the TGA curve of POSS-Br reveals that $T_{\\mathrm{d}}$ at $5\\%$ mass loss is about $223.9\\ ^{\\circ}\\mathrm{C}$ due to its excellent thermodynamic stability, probably resulting from the existence of Si-O-Si bonds. Pure PDMAEMA showed total decomposition at about $500~^{\\circ}\\mathrm{C}$ in the reference.8 In this work, the mass of $\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ decreased to about zero at the end of measurement. For POSS-PDMAE $\\mathbf{MA}_{70}$ and $\\mathrm{POSS-D}_{70}–b–\\ensuremath{\\mathrm{S}}_{10}$ , the mass loss reaches $95.2\\%$ at $500~^{\\circ}\\mathrm{C}$ , and whereafter the mass of polymers remains unchanged, demonstrating the existence of the POSS component in the copolymers. \n\n \nFigure S4. TGA curves of POSS-Br (a), POSS-PDMAEMA70 (b), POSS- $\\mathrm{\\cdotD}_{70^{-}}b{-}\\mathrm{S}_{10}$ (c), and $\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ (d). \n\nThermal remediation behavior and stability of the SIPN coatings. The sample C-POSS- $\\cdot\\mathrm{D}_{90}–b–\\mathrm{S}_{13}$ showed self-healing by vapor after scratched by a clean blade. The score disappeared completely after about 3 min as shown in Figure S5. \n\n \nFigure S5. Photographs of the C-POSS- $\\mathrm{.D}_{90}$ -b-S13 coating with a scratch (a), and the healable coating by vapor (b). \n\nFigure S6(a) shows the condition of the $\\mathrm{POSS-D}_{70^{-}}b{\\mathrm{-}}\\mathrm{S}_{10}$ coating before immersed in deionized water, suggesting that the coating was as transparent as bare glass. Figure S6(b) shows the condition of the POSS- $\\cdot\\mathrm{D}_{70^{-}}b{-}\\mathrm{S}_{10}$ coating during immersion in deionized water. An enough amount of deionized water was filled in the beaker, in which the coating sample was immersed. Figure S6(c) shows the condition of the $\\mathrm{POSS-D}_{70^{-}}b{\\mathrm{-}}\\mathrm{S}_{10}$ coating after immersion in deionized water for about $30~\\mathrm{min}$ . It can be seen that bare glass was obscure by water droplets, while the coating still kept its good transmittance. Thus, the coatings contain POSS-PDMAEMA- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -PSBMA show great stability for long-lasting utilities. \n\n \nFigure S6. Photographs of the C-POSS- $\\cdot\\mathrm{D}_{70}{-}b{-}\\mathrm{S}_{10}$ coating before (a), during (b) and after immersed in deionized water (c). \n\nATR-FTIR analysis of the SIPN coatings. Chemical surface characterization of the prepared SIPN coatings was analyzed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR, Perkin-Elmer Spectrum100, USA). Figure S7 shows ATR-FTIR spectra of the prepared coatings. The characteristic absorption peaks at $2822~\\mathrm{{cm}^{-1}}$ and $2776\\mathrm{cm}^{-1}$ are attributed to C-H vibration of the $\\J\\mathrm{-N}(\\mathrm{CH}_{3})_{2}$ group from PDMAEMA, while the peak at 2950 $\\mathrm{cm}^{-1}$ belongs to C-H stretching vibration from other groups. Meanwhile, the signals at $1723\\mathrm{cm}^{-1}$ , $1270~\\mathrm{{cm}^{-1}}$ and $1457~\\mathrm{{cm}^{-1}}$ belong to characteristic absorption bands of $\\scriptstyle\\mathbf{C=O}$ , C-N and $\\mathrm{CH}_{2}$ , respectively. Furthermore, the characteristic absorption peak at $1039~\\mathrm{{cm}^{-1}}$ is related to stretching vibration peak of $\\scriptstyle{\\mathsf{S}}=0$ in PSBMA. In addition, the absorbance of the O-H stretching bands of hydrogen bonding was detected at $3414~\\mathrm{{cm}^{-1}}$ . The wavenumber range $1204{\\cdot}1085\\ \\mathrm{cm}^{-1}$ in the curves of Figure S7(a,b,c) include the peaks of $\\mathbf{C}\\mathbf{-}\\mathbf{O}$ at $1149\\mathrm{cm}^{-1}$ and Si-O-Si at $1112\\mathrm{cm}^{-1}$ .4 And, curve Figure S7(d) shows the peak at $1149~\\mathrm{{cm}^{-1}}$ , which is attributed to characteristic absorption band of C-O.4 \n\n \nFigure S7. ATR-FTIR spectra of the SIPN coatings of C-POSS- $\\cdot\\mathrm{D}_{50^{-}}b{-}S_{7}$ (a), C-POSS-D70-b-S10 (b), C-POSS- $\\mathrm{\\bfD}_{90^{-}}b.\\mathrm{\\bfS}_{13}$ (c), and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ (d). \n\nTEM analysis of the SIPN Coatings. The SIPN coating morphologies were observed under a JEOL JEM100CXII transmission electron microscope (TEM, Japan) at $100\\mathrm{kV}$ . TEM samples were prepared by dropping a droplet of the dilute copolymer solutions ( $1\\mathrm{\\mt{\\%}}$ in trifluoroethanol) on a thin carbon-coated copper grid, and then UV-curing in a XL-1000 ultraviolet cross-linker apparatus (USA) for 30min. As seen from these images (Figure S8), the aggregated POSS clusters are in the size range of $10{\\sim}80~\\mathrm{nm}$ , and well dispersed. \n\n \nFigure S8. TEM images of the SIPN coatings of C-POSS-D $50$ -b-S7 (a), C-POSS-D $^{70}$ -b-S10 (b), C-POSS- $\\cdot\\mathrm{D}_{90}–b–\\mathrm{S}_{13}$ (c), and $\\mathrm{C}{\\cdot}\\mathrm{D}_{50}{\\cdot}b{\\cdot}\\mathrm{S}_{7}$ (d). \n\nDSC analysis of the SIPN Coatings. The SIPN coatings were analyzed by a TA Q2000 differential scanning calorimetry machine (DSC, USA). The samples containing a certain amount of deionized water were prepared by adding water into the SIPN coatings (about $4{\\sim}5~\\mathrm{mg}$ ) scraped from the glass slide, and keeping them in the aluminium pans for 10 days at room temperature. The heating rate had a negligible effect on the content of non-freezable bond water and bond water as shown in Table S1. \n\nTable S1. Water contents in different states in the samples analyzed by DSC at different heating rates \n\n\n<html><body><table><tr><td rowspan=\"2\">Sample</td><td rowspan=\"2\">Heating rate</td><td rowspan=\"2\">Wc (mg/mg)</td><td colspan=\"6\">Freezable water Wf (mg/mg)</td><td rowspan=\"2\">Non-freezable Bond bond water water Wb</td></tr><tr><td>Wf</td><td colspan=\"2\">Freezable bond water</td><td colspan=\"2\">Freezable free water</td></tr><tr><td></td><td>(C/min)</td><td></td><td>(mg/mg)</td><td>Wfb (mg/mg)</td><td>Tfbm (℃)</td><td>Wff (mg/mg)</td><td>Tffm (℃)</td><td>Wnfb (mg/mg)</td><td>(mg/mg)</td></tr><tr><td>C-POSS-D50-b-S7</td><td>5</td><td>1.21</td><td>0.76</td><td>0.13</td><td>-14.88</td><td>0.63</td><td>-1.56</td><td>0.45</td><td>0.58</td></tr><tr><td rowspan=\"4\">C-POSS-D7o-b-S10</td><td>10</td><td></td><td>0.76</td><td>0.14</td><td>-14.01</td><td>0.62</td><td>-1.30</td><td>0.45</td><td>0.59</td></tr><tr><td>15</td><td></td><td>0.76</td><td>0.14</td><td>-13.10</td><td>0.62</td><td>-1.07</td><td>0.45</td><td>0.59</td></tr><tr><td>5</td><td>1.20</td><td>0.77</td><td>0.11</td><td>-17.54</td><td>0.66</td><td>-2.06</td><td>0.43</td><td>0.54</td></tr><tr><td>10</td><td></td><td>0.77</td><td>0.16</td><td>-17.42</td><td>0.61</td><td>-1.91</td><td>0.43</td><td>0.59</td></tr><tr><td>C-POSS-D90-b-S13</td><td>15</td><td></td><td>0.77</td><td>0.15</td><td>-14.61</td><td>0.62</td><td>-1.73</td><td>0.43</td><td>0.58</td></tr><tr><td rowspan=\"4\"></td><td>5</td><td>1.22</td><td>0.77</td><td>0.14</td><td>-15.34</td><td>0.63</td><td>-1.96</td><td>0.45</td><td>0.59</td></tr><tr><td>10</td><td></td><td>0.77</td><td>0.14</td><td>-15.01</td><td>0.63</td><td>-1.50</td><td>0.45</td><td>0.59</td></tr><tr><td>15</td><td></td><td>0.77</td><td>0.15</td><td>-14.50</td><td>0.62</td><td>-1.11</td><td>0.45</td><td>0.60</td></tr><tr><td>5</td><td>1.24</td><td>0.72</td><td>0.11</td><td>-16.55</td><td>0.61</td><td>-2.41</td><td>0.52</td><td>0.63</td></tr><tr><td>C-D50-b-S7</td><td>10</td><td></td><td>0.72</td><td>0.09</td><td>-16.34</td><td>0.63</td><td>-2.13</td><td>0.52</td><td>0.61</td></tr><tr><td></td><td>15</td><td></td><td>0.72</td><td>0.12</td><td>-15.13</td><td>0.60</td><td>-1.87</td><td>0.52</td><td>0.64</td></tr></table></body></html>",
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"category": " Materials and methods"
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"chunk": "# References \n\n(1) Ma, L.; Geng, H. P.; Song, J. X.; Li, J. Z.; Chen, G. X.; Li, Q. F. Hierarchical Self-Assembly of Polyhedral Oligomeric Silsesquioxane End-Capped Stimuli-Responsive Polymer: From Single Micelle to Complex Micelle. J. Phys. Chem. B 2011, 115, 10586-10591. (2) Shao, Y.; Aizhao, P.; Ling, H. POSS End-Capped Diblock Copolymers: Synthesis, Micelle Self-Assembly and Properties. J. Colloid Interface Sci. 2014, 425, 5-11. (3) Zhang, M. M.; Shen, W.; Xiong, Q. Q.; Wang, H. W.; Zhou, Z. M.; Chen, W. J.; Zhang, Q. Q. Thermo-Responsiveness and Biocompatibility of Star-Shaped Poly[2-(dimethylamino) ethyl methacrylate]- $\\mathbf{\\nabla}\\cdot\\boldsymbol{b}$ -Poly(sulfobetaine methacrylate) Grafted on $\\upbeta$ -Cyclodextrin Core. Rsc Adv. 2015, 5, 28133-28140. (4) Li, Y. M.; Xu, B.; Bai, T.; Liu, W. G. Co-Delivery of Doxorubicin and Tumor-Suppressing p53 Gene Using a POSS-Based Star-Shaped Polymer for Cancer Therapy. Biomaterials 2015, 55, 12-23. (5) Liu, Y. H.; Yang, X. T.; Zhang, W. A.; Zheng, S. X. Star-Shaped Poly(ε-caprolactone) with Polyhedral Oligomeric Silsesquioxane Core. Polymer 2006,47, 6814-6825. (6) Chou, Y. N.; Chang, Y.; Wen, T. C. Applying Thermosettable Zwitterionic Copolymers as General Fouling-Resistant and Thermal-Tolerant Biomaterial Interfaces. ACS Appl. Mater. Interfaces 2015, 7, 10096-10107. (7) Dong, Z.; X, Mao, J.; Wang, D. P.; Yang M. Q.; Wang W. C.; Bo S. Q.; Ji X. L. Tunable Dual-Thermoresponsive Phase Behavior of Zwitterionic Polysulfobetaine Copolymers Containing Poly(N,N-dimethylaminoethylmethacrylate)-Grafted Silica Nanoparticles in Aqueous Solution. Macromol. Chem. Phys. 2014, 215, 111-120. (8) Zhang, P.; Yang, J. H.; Li, W. C.; Wang, W.; Liu, C. J.; Griffith, M.; Liu, W. G. Cationic Polymer Brush Grafted-Nanodiamond via Atom Transfer Radical Polymerization for Enhanced Gene Delivery and Bioimaging. J. Mater. Chem. 2011, 21, 7755-7764.",
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"category": " References"
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