用二维FTIR研究纳米TiO2改性丝素蛋白聚集态结构转变

采用溶胶-凝胶方法制备纳米TiO₂复合丝素膜。UV和SEM测试结果表明,该丝素膜中纳米TiO₂均匀分散在丝素中,TiO₂粒径约为80 nm;同时采用一维红外光谱、二维红外相关光谱对纯丝素膜及复合丝素膜结构进行表征。结果表明,随着纳米TiO₂的生成,丝素蛋白中弱氢键缔合的N—H键以及自由的N—H键发生断裂及重组,生成了强氢键;丝素分子从无序状态转变为有序排列,同时无规线团构象及α螺旋构象向β折叠构象发生转变,最后促使丝素蛋白的结晶构象从Silk Ⅰ转变为Silk Ⅱ。     

Study on the properties of nano‐TiO2 particles modified silk fibroin porous films

Using the freeze‐drying method, Nano‐TiO₂/silk fibroin porous films were synthesized with different ratios of TiO₂ to silk fibroin solution. Through scanning electron microscopy (SEM), X‐ray diffraction (XRD), thermogravimetric analysis (TGA), tensile strain, and water‐solubility tests, the structures and properties of these porous films were characterized. The SEM results indicated that the pores of the nano‐TiO₂/silk fibroin porous films were uniformly distributed by the freeze‐drying method. The XRD analysis indicated that the formation of nano‐TiO₂ particles might induce a conformational transition of silk fibroin from the typical Silk I to the typical Silk II structure partly with an increase in the crystallinity of the porous films. Compared with the pure silk fibroin porous films, the mechanical properties of nano‐TiO₂/silk fibroin porous films were improved, and its heat transition temperature was also enhanced; however, the water‐solubility of this material was diminished. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structure and physical properties of silk fibroin/polyacrylamide blend films

This article deals with the characterization of blend films obtained by mixing silk fibroin (SF) and polyacrylamide (PAAm). The DSC curves of SF/PAAm blend films showed overlapping of the main thermal transitions characteristic of the individual polymers. The exothermic peak at 218°C, assigned to the β‐sheet crystallization of silk fibroin, slightly shifted to a lower temperature by blending. The weight‐retention properties (TG) of the blend films were intermediate between those of the two constituents. The TMA response was indicative of a higher thermal stability of the blend films, even at low PAAm content (≤25%), the final breaking occurring at about 300°C (100°C higher than pure SF film). The peak of dynamic loss modulus of silk fibroin at 193°C gradually shifted to lower temperature in the blend films, suggesting an enhancement of the molecular motion of the fibroin chains induced by the presence of PAAm. Changes in the NH stretching region of silk fibroin were detected by FTIR analysis of blend films. These are attributable to disturbance of the hydrogen bond pattern of silk fibroin and formation of new hydrogen bonds with PAAm. The values of strength and elongation at break of blend films slightly improved at 20–25% PAAm content. A sea–island structure was observed by examining the air surface of the blend films by scanning electron microscopy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1563–1571, 1999     

Rapid formation of flexible silk fibroin gel‐like films

Flexible silk fibroin gel‐like films with microporous morphology were prepared from B. mori silk fibroin fibers directly solubilized in formic acid/CaCl₂ solvent. These films were characterized by several analysis techniques to determine the structure and properties of films. The pore size of gel‐like films can be adjusted through SF concentration and Ca ions concentration. The controllable pore size in gel‐like films was grew from 3–5 μm to 100 μm under the increase of fibroin concentration from 1.0 wt % to 8.0 wt %. At the same time, the water content of silk fibroin gel‐like film decreased from 83.5 ± 3.4% to 68.2 ± 2.6%. With increasing Ca ions contents from 2.0 wt % to 10.0 wt % in dissolution process, the pore size and water content of silk fibroin gel‐like films grew larger, especially its water content values reached 86.2 ± 4.0% at 10.0 wt % Ca ions concentration. At wet condition, the gel‐like film with β‐sheet structure showed higher breaking stress (4.26 ± 0.31 MPa) and elongation (45.45 ± 15.79%) at 8.0 wt % concentration. With the preparation method, the membrane is hydrophilic and the pore size is adjustable, which contributes to high toughness and favorable cell growth environment, suggesting that these silk fibroin gel‐like films can be a potential candidate scaffold for biomedical applications, such as wound dressing, facial mask, contact lenses, etc. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41842.     

用二维FTIR研究纳米TiO2改性丝素蛋白聚集态结构转变

采用溶胶-凝胶方法制备纳米TiO₂复合丝素膜。UV和SEM测试结果表明,该丝素膜中纳米TiO₂均匀分散在丝素中,TiO₂粒径约为80 nm;同时采用一维红外光谱、二维红外相关光谱对纯丝素膜及复合丝素膜结构进行表征。结果表明,随着纳米TiO₂的生成,丝素蛋白中弱氢键缔合的N—H键以及自由的N—H键发生断裂及重组,生成了强氢键;丝素分子从无序状态转变为有序排列,同时无规线团构象及α螺旋构象向β折叠构象发生转变,最后促使丝素蛋白的结晶构象从Silk Ⅰ转变为Silk Ⅱ。     

Fabrication and characterization of silk fibroin/poly(ethylene glycol)/cellulose nanowhisker composite films

The flexible and transparent composite films were fabricated by a mixture of silk fibroin (SF), poly(ethylene glycol), and mulberry cellulose nanowhiskers (CNWs). The CNWs were uniformly dispersed in the matrix when its content was as high as 12 w/w%. The tensile properties of composite films generally depended on the nanowhisker content, but significantly improved when compared to the pure SF film. DMA analysis revealed that the alpha transition temperature increased gradually with the increase of nanowhisker content, probably due to the formation of interactions between the nanowhiskers and the SF molecular chains, leading to the mobility reduction of the amorphous SF. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Structure for electro‐spun silk fibroin nanofibers

Electro‐spinning was made using silk fibroin and it was found that silk fibroin nanofibers of partially oriented amorphous structure are producible using HFIP(1,1,1,3,3,3 hexafluoro‐2‐propanol) as a solvent for fibroin via the electro‐spinning setup equipped with parallel electrodes as a collector. Transformation from amorphous to silk I of a highly contracted beta‐turn form or amorphous to silk II of a regular array of antiparallel beta‐sheets occurred preferentially via the treatment with water vapor or ethanol, respectively. In addition the c‐axis of crystallites was oriented parallel to the fiber axis. When the electro‐spinning was made using a dish‐type collector filled with ethanol, a peculiar web texture was obtained. Such a web texture seems to be brought about by the shrinkage of fiber due to the crystallization of fibroin and/or surface tension of ethanol droplets formed between the fibers. In this spinning setup, the c‐axis of crystallites was also oriented parallel to the fiber axis. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Physical properties of silk fibroin/chitosan blend films

Silk fibroin/chitosan blend films were examined through IR spectroscopy to determine the conformational changes of silk fibroin. The effects of the fibroin/chitosan blend ratios (chitosan content) on the physical and mechanical properties were investigated to discover the feasibility of using these films as biomedical materials such as artificial skin and wound dressing. The mechanical properties of the blend films containing 10–40% chitosan were found to be excellent. The tensile strength, breaking elongation, and Young's modulus were affected by the chitosan contents of the blend films, which were also related to the density and degree of swelling. The coefficient of water vapor permeability of the blend films increased linearly with the chitosan content, and the values of 1000–2000 g m^?2 day^?1 were comparable to those of commercial wound dressings. Silk fibroin/chitosan blend films had good oxygen and water vapor permeabilities, making them useful as biomaterials. In particular, the blend film containing 40–50% chitosan showed very high oxygen permeability. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 928–934, 2001     

Production of silk sericin/silk fibroin blend nanofibers

Silk sericin (SS)/silk fibroin (SF) blend nanofibers have been produced by electrospinning in a binary SS/SF trifluoroacetic acid (TFA) solution system, which was prepared by mixing 20 wt.% SS TFA solution and 10 wt.% SF TFA solution to give different compositions. The diameters of the SS/SF nanofibers ranged from 33 to 837 nm, and they showed a round cross section. The surface of the SS/SF nanofibers was smooth, and the fibers possessed a bead-free structure. The average diameters of the SS/SF (75/25, 50/50, and 25/75) blend nanofibers were much thicker than that of SS and SF nanofibers. The SS/SF (100/0, 75/25, and 50/50) blend nanofibers were easily dissolved in water, while the SS/SF (25/75 and 0/100) blend nanofibers could not be completely dissolved in water. The SS/SF blend nanofibers could not be completely dissolved in methanol. The SS/SF blend nanofibers were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, and differential thermal analysis. FTIR showed that the SS/SF blend nanofibers possessed a random coil conformation and ß-sheet structure.     

从丝素水溶液中再生的丝纤维的结构与性能

通过使用表面皿直接拉伸、毛细管重力纺丝和人工拉伸3种不同的成丝方法,从高浓度再生丝素水溶液中制得了丝纤维。用偏光显微镜观察了丝纤维的取向,用拉曼光谱仪和Instron拉力仪表征了丝纤维的结构和力学性能。结果发现,经毛细管剪切流动后再拉伸有利于再生丝性能的提高,所得的丝有较好的取向和较多的β折叠结构,力学性能也相对较好。剪切在丝纤维的成形过程中起重要的作用。     

Compatibilization of acrylic polymer–silk fibroin blend fibers. I. Graft copolymerzation of acrylonitrile onto silk fibroin

To synthesize effective compatibilizers for the compatibilization of acrylic polymer–silk fibroin blend fibers, the homogeneous graft copolymerization of acrylonitrile onto silk fibroin, initiated by potassium persulfate–sodium bisulfite redox system in 60 wt % ZnCl₂ aqueous solution was investigated. The percentage graft, percentage efficiency, and molecular weight of the grafted polyacrylonitrile increase with the increase of the concentration of initiator, the concentration of acrylonitrile, and the temperature to optimum values, respectively, and then decrease. With the increase of reaction time, the percentage graft and percentage efficiency increase, whereas the molecular weight of the grafted polyacrylonitrile decreases. The influence of the reactionconditions on the molecular architecture of the graft copolymers is also discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1089–1097, 1998     

新型丝素复合膜的微结构表征及热稳定性

基于丝素的高分子复合材料可以广泛地应用于组织工程、生物医药和半导体材料等领域。通过物理-共混技术制备了一种新型生物高分子丝素/聚乳酸复合膜。利用扫描电镜、傅里叶红外光谱、拉曼光谱、X射线衍射和热分析技术对其形貌、结构和相态组分以及热稳定性进行了表征,探究了不同比例复合膜的微结构、相互作用机理和热稳定性。结果表明：随着丝素含量的增加,复合膜中的β-折叠含量增多,α-螺旋和无规卷曲含量减少,玻璃化转变温度提高;由于丝素与聚乳酸间的相互作用,提高了复合膜的热稳定性。     

Phase separation structure in poly(vinyl alcohol)/silk fibroin blend films

Blend films of a commercial poly(vinyl alcohol) (a-PVA) derived from vinyl acetate and silk fibroin (SF) obtained from degummed silk were prepared by mixing the aqueous solutions of both samples. A plain weave structure was recognized only in the blend films, whereas no structure was found for the superimposed films of both samples. The phase separation structure of the blend films was examined by microscopic observations elongation, tensile tests, and IR measurements. The microphase separation region increased with increase in the degree of polymerization of the PVA. In the IR spectra of the blend films with high PVA contents cast under certain conditions, the absorption peak attributed to the cross-β-form conformation of SF appeared strongly. Gelatin, a water-soluble and natural polymer, was also used for comparison with SF. The ternary phase diagram in an a-PVA/gelatin/H₂O system was obtained experimentally and the critical point was used to estimate the interaction parameter between PVA and gelatin molecules. The phase separation structure and the interaction between PVA and SF molecules were also discussed taking into consideration the results of the a-PVA/gelatin system. © 1998 SCI.     

Effect of heat treatment on the structural and conformational changes of regenerated Antheraea pernyi silk fibroin films

Regenerated Antheraea pernyi silk fibroin films prepared from calcium nitrate solution were treated with heat for crystallization. The structural and conformational changes caused by heat treatment were investigated with X-ray diffraction, infrared spectroscopy, and differential scanning calorimetry. The temperature and treatment time of heat greatly influenced the conformation of the regenerated films. The conformational change was caused by heat treatment over 230°C, and the transition was enhanced by increasing time and temperature. The contents of α-helix, β-sheet, and random-coil conformations were calculated and examined to investigate the effect of heat treatment on the conformational changes. The β-sheet structure could be transformed from a random-coil conformation on heat treatment, whereas the content of α-helix structure was nearly unchanged, regardless of heat-treatment conditions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2271–2276, 2001     

Preparation of semi‐interpenetrating polymer networks composed of silk fibroin and poly(ethylene glycol) macromer

Semi‐interpenetrating polymer networks (SIPNs) composed of silk fibroin (SF) and a poly(ethylene glycol) (PEG) diacrylate macromer were synthesized and characterized. The conformation of SF in SIPNs was changed from a random coil to a β‐sheet structure by formation of SIPNs with PEG, while the crystalline structures of SF and PEG in SIPNs was not changed. The decomposition temperature of SF in the SIPNs was inner‐shifted, an indication of SIPN formation between the SF and the PEG macromer. The tensile strength and elongation of the SIPNs were much higher than were those of SF itself or the SF/PEG blend and increased with an increase of the PEG content. The equilibrium water content of SF was remarkably increased by formation of SIPNs with PEG due to the hydrophilic property of PEG. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1848–1853, 2001     

离子液体对丝素蛋白溶解性能的影响

合成了一系列碱性离子液体,其中离子液体1-丁基-3-甲基咪唑乙酸盐([Bmim]AC)对丝素蛋白具有良好的溶解性能。考察了丝素蛋白在该离子液体中的溶解特性及在离子液体中的溶解温度和溶解时间,结果表明,在75℃下,溶解840 min,该离子液体对丝素蛋白的溶解能力达到15%(质量分数)。XRD和FTIR分析表明,再生丝素蛋白的构象以α-螺旋为主,丝素蛋白在溶解过程中没有发生衍生化。因此,[Bmim]AC离子液体是丝素蛋白的优良溶剂。     

Effect of moisture absorption on the thermal properties of Bombyx mori silk fibroin films

Films of regenerated Bombyx mori silk are strongly affected by absorbed moisture, a phenomenon studied here by differential scanning calorimetry (DSC). Exposure of previously dried films to environments of controlled relative humidity produces test samples of well-defined equilibrium moisture content. Ultimate moisture uptake is as high as 20–23% (by weight) at 75% relative humidity. The glass transition temperature, T_g, drops by 40°C at moisture uptakes as low as 2%, and T_g depressions as large as 140°C are observed at higher relative humidity. The moisture-induced decrease of T_g is completely reversible, as a film remoistened and then redried possesses an unchanged T_g. Trends in T_g with water uptake correspond reasonably well to predictions of a classical thermodynamic theory, indicating that the plasticization effect of moisture on the combined silk-water system can be satisfactorily explained from macroscopic properties of the constituents without any reference to specific interactions. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 401–410, 1997     

Study on porous silk fibroin materials. I. Fine structure of freeze dried silk fibroin

Silk fibroin solution was prepared by dissolving the silk fibroin in triad solvent CaCl₂ · CH₃CH₂OH · H₂O. In this article we tested and analyzed the state of frozen silk fibroin solution and fine structure of freeze dried porous silk fibroin materials. The results indicated that the glass transition temperature of frozen silk fibroin solution ranges from −34 to −20°C, and the initial melting temperature of ice in frozen solution is about −8.5°C. When porous silk fibroin materials are prepared by means of freeze drying, if freezing temperature is below −20°C, the structure of silk fibroin is mainly amorphous with a little silk II crystal structure, and if freezing temperature is above −20°C, quite a lot of silk I crystal structure forms. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2185–2191, 2001     

Acrylic polymer–silk fibroin blend fibers

Blends of acrylic polymer (containing acrylonitrile 91.7%, methyl acrylate 7%, and sodium methyl propenyl sulfonate 1.3% [wt %], denoted as PAC) with silk fibroin (SF) were studied in the form of drawn fibers with varied compositions. The strength, elongation, and specific work of rupture of the blend fibers decrease with increase of the SF content, whereas the modulus has a slight increase up to 20% (wt) SF and then decreases. With the addition of up to 30% (wt %) SF in the PAC matrix, the moisture absorption increases from 2.06 to 6.2% in comparison with the PAC. Scanning electron microscopy studies show that the blend fibers have a sheath–core structure, with SF mainly in the sheath and PAC in the core. FTIR, ATR, and X-ray diffraction results of the blend fibers are also presented. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:959–966, 1997     

丝素蛋白在离子液体中的溶解特性研究

文章以离子液体为溶剂,研究了丝素蛋白在离子液体中的溶解特性。首先研究了丝素蛋白在不同结构的离子液体1-烯丙基-3-甲基咪唑氯化物（[AMIM]C1）和1-丁基-3_-甲基咪唑氯化物（[BMIM]c1）中的溶解速率和溶解度。结果发现,相同条件下,丝素蛋白在[AMIM]cl中具有较快的溶解速率和较大的溶解度;随温度的升高,溶解速度加快,合适的温度为95～105℃;随着丝素蛋白浓度的增大,相同条件下丝素蛋白在离子液体中的溶解速度减慢。XRD结果表明,丝素蛋白的非晶相部分首先被溶解,晶相部分结构被破坏后与溶剂作用逐渐被溶解。采用粘度法测定了丝素蛋白分子质量随溶解时间和温度的变化,结果表明：随加热时间增加和温度升高,蛋白质分子质量减小。为保证丝素蛋白的稳定性和溶解速率,温度一般控制在100℃以下,溶解时间小于5h。