Poly(N‐isopropylacrylamide) gel‐based macroporous monolith for continuous‐flow recovery of palladium(II) ions

Macroporous monoliths, composed of thermoresponsive, tertiary‐aminated, and crosslinking monomers, were prepared for continuous‐flow separation of palladium(II) ions. N ‐Isopropylacrylamide was required to form the porous structure in the monoliths, indicating that the mechanism of porous structure formation involved polymerization‐induced phase separation of the poly(N ‐isopropylacrylamide) gel. Tertiary‐aminated monoliths showed adsorption selectivity for palladium(II) ions in hydrochloric media, compared with copper(II) ions. The maximum capacities of the monoliths with tertiary amine contents of 10, 20, 30, and 70 mol % for palladium(II) ions were 0.6, 1.1, 1.3, and 2.3 mmol/g, respectively. Darcy's permeabilities of water through the macroporous monolith were 10^?14 to 10^?13 m², and those were comparable to that through a commercially available membrane filter with a pore size of several micrometers. In the continuous‐flow process, the macroporous monolith with tertiary amine selectively adsorbed palladium(II) ions in the coexistence of copper(II) ions with 10 times higher concentration than the palladium(II) ions. The palladium(II) ions were eluted from the macroporous monolith, and the concentration of palladium(II) ions in the eluate was up to 45 times of that in the feed solution. The average enrichment factor and total recovery percentage of palladium(II) ions were 8.7 times and 95%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44385.     

Deposition of bone‐like apatite on modified silk fibroin films from simulated body fluid

Silk fibroin films with various calcium chloride contents were prepared by a cast film method and subsequent MeOH treatment. The conformational changes from α‐helix to β‐sheet structure were analyzed by Fourier transformed infrared attenuated total reflection spectroscopy measurements. The films obtained were soaked in 1.5‐times simulated body fluid (1.5 SBF) and the deposition of hydroxyapatite crystals were observed by scanning electron microscopy. The films with calcium chloride contents lower than 3 wt % relative to the silk fibroin were not mineralized under these conditions, while those with calcium chloride contents more than 5 wt % mineralized after 6 h. The X‐ray diffraction patterns and inductive coupled plasma spectroscopy analyses indicated that the hydroxyapatite crystals were grown by hydrolysis of octacalcium phosphate, as indicated by differences in diffraction intensities and changes in concentrations of calcium and phosphate ions in 1.5 SBF. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Self‐healing hydrogel of poly(vinyl alcohol)/graphite oxide with pH‐sensitive and enhanced thermal properties

Supramolecular hydrogel is a fascinating polymeric material composed of three‐dimensional noncovalent networks with many outstanding properties, especially reversible relevant performances. A self‐healing supramolecular hydrogel of poly(vinyl alcohol)/graphite oxide, with reversible pH responsiveness and good thermal stability, was prepared. The morphology, functional group changes, swelling performance, thermal stability, rheological performance, and self‐healing property of the PVA/GO hydrogel were investigated. A probable mechanism between the components and potential applications were also examined in our study. The experimental results show that the PVA/GO hydrogel was not only self‐healable without external stimulus or addition of any healing agents, but also pH sensitive and with good thermal stability. Green ingredients (PVA and GO) and a simple synthesis method (a freezing/thawing treatment) may pose little threat to the environment and also promote the production of such hydrogels. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46143.     

Influence of annealing treatment on the structure and properties of poly(4‐methyl‐1‐pentene)‐based films and membranes

The poly(4‐methyl‐1‐pentene) casting films were prepared by melt extrusion and annealed below the melting temperature. The effect of annealing conditions on the structure and properties of casting films and stretched membranes was discussed. In this work, a new peak around annealing temperature, as shown in melting curves, revealed the increase in thickness of lamellar structure. Annealing treatment led to improvements of amorphous thickness and crystal orientation. And the thickness of crystal phase correlated with the logarithm of annealing time. The increase in annealing temperature or time led to the improvements of the hard elasticity of samples. Additionally, the larger porosity of stretched membranes was observed as the annealing time and temperature increased. An optimum annealing condition to prepare microporous membranes was 30 min, 200 °C. This work also discussed the importance of annealing treatment in the preparation of microporous membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46491.     

Soluble‐eggshell‐membrane‐protein‐modified porous silk fibroin scaffolds with enhanced cell adhesion and proliferation properties

In this study, a porous silk fibroin (SF) scaffold was modified with soluble eggshell membrane protein (SEP) with the aim of improving the cell affinity properties of the scaffold for tissue regeneration. The pore size and porosity of the prepared scaffold were in the ranges 200–300 μm and 85–90%, respectively. The existence of SEP on the scaffold surface and the structural and thermal stability were confirmed by energy‐dispersive X‐ray spectroscopy, X‐ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. The cell culture study indicated a significant improvement in the cell adhesion and proliferation of mesenchymal stem cells (MSCs) on the SF scaffold modified with SEP. The cytocompatibility of the SEP‐conjugated SF scaffold was confirmed by a 3‐(4,5‐dimethyltriazol‐2‐y1)‐2,5‐diphenyl tetrazolium assay. Thus, this study demonstrated that the biomimic properties of the scaffold could be enhanced by surface modification with SEP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40138.     

Preparation of multi‐level honeycomb‐structured porous films by control of spraying atomized water droplets

Honeycomb‐structured porous films have been widely applied in various industrial areas such as chemical sensors, tissue engineering, and micro reactors. In this article, one novel self‐assembly approach is proposed to fabricate well‐ordered polyphenylene oxide honeycomb films by a facile control of spraying ultrasonic humidifier atomized water droplets. Proper spraying retention time is necessary for porous films formation with highly uniform pore size. The effect of atomized water droplets flux on the pore size and the regularity of the hexagonal arrays were experimentally investigated. The pore size became larger with increasing the solution concentration. Especially, honeycomb films with two‐level pores were fabricated by spraying atomized water droplets two times and the influence of interval time on the two‐level honeycomb films formation was investigated. Apart from analysis of structural characteristics, self‐assembly mechanism was also discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41163.     

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     

Biodegradation of Bombyx mori silk fibroin fibers and films

The in vitro biodegradation of Bombyx mori silk fibroin was studied by incubating fibers and films with proteolytic enzymes (collagenase type F, α‐chymotrypsin type I‐S, protease type XXI), for times ranging from 1 to 17 days. The changes in sample weight and degree of polymerization of silk fibers exposed to proteolytic attack were negligible. However, tensile properties were significantly affected, as shown by the drop of strength and elongation as a function of the degradation time. Upon incubation with proteolytic enzymes, silk films exhibited a noticeable decrease of sample weight and degree of polymerization, the extent of which depended on the type of enzyme, on the enzyme‐to‐substrate ratio, and on the degradation time. Protease was more aggressive than α‐chymotrypsin or collagenase. Film fragments resistant to enzymatic degradation were enriched in glycine and alanine. FT‐IR measurements showed that the degree of crystallinity of biodegraded films increased. Soluble degradation products of silk films consisted of a range of peptides widely differing in size, deriving from the amorphous sequences of the silk fibroin chains. Biodegraded fibers showed an increase of surface roughness, while films displayed surface cracks and cavities with internal voids separated by fiber‐like elements. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2383–2390, 2004     

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 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     

Study on porous silk fibroin materials. II. Preparation and characteristics of spongy porous silk fibroin materials

Porous silk fibroin materials, with average pore size 10 ∼ 300 μm, pore density 1 ∼ 2000/mm², and porosity 35 ∼ 70%, were prepared by freeze drying aqueous solution of silk fibroin obtained by dissolving silk fibroin in ternary solvent CaCl₂ · CH₃CH₂OH · H₂O. Pore size distribution of such materials mostly accorded with logarithmic normal distribution. It is possible to control the aforementioned structural parameters and the physical properties of moisture permeability, compressibility, strength, elongation, etc., by adjusting freezing temperature and concentration of silk fibroin solution. Above glass transition zone (−34 ∼ −20°C) of silk fibroin, the freezing temperature has more significant effect on the structure and properties of porous silk fibroin materials. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2192–2199, 2001     

Enhancement of the hydrophobicity of recycled polystyrene films using a spin coating unit

This article describes a technique for recycling polystyrene cups (PS_r) mixed with poly(butyl methacrylate) (PBMA) to produce PS_r/PBMA films and subsequently PS_r films by removing PBMA with a selective solvent (acetic acid), with the benefit of a reduction in environmental pollution generated by polystyrene waste. Removal of PBMA increases roughness, which generates a significant increase ( 34°) in the water contact angle, reaching its highest value at 128°. By increasing the hydrophobicity of surfaces, properties with important technical applications are acquired such as those used in antifouling paints, stain‐resistant surfaces, and surfaces that avoid the formation and accretion of ice on microelectronic devices. Roughness of PS_r/PBMA films is significantly affected by the concentration of both polymers and by the spin rate, reaching its highest value at 2% PS_r and 3% PBMA at 2000 . For optimal film deposition, a cheap spin coating unit was designed and built, with a price less than 4% of that of a commercially available spin coating unit. Lastly, it was found that the data obtained with our spin coating unit is described by the Meyerhofer model with accuracy of 88% ± 3%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45365.     

The cavitation development of poly(4-methyl-1-pentene) casting films studied by in situ small angle X-ray scattering

In this paper, the on-line small angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) characterization method was adopted to study the morphology evolution of poly(4-methyl-1-pentene) casting films during stretching. In this process, the lamellae structure was destroyed. And “bridge structure” was generated in the amorphous region. The scattering pattern changed obviously before and after cavities orientation. Stretching temperature and stretching speed mattered for the size of micropores. Low temperature helped generate more and larger voids. The faster stretching speed can improve the generation of cavities, enlarged cavitation number and helped its reorientation. These results provide the basic knowledge of how to produce poly(4-methyl-1-pentene) microporous membranes with high electrochemical performance.     

Microporous PDMAEMA‐based stimuli‐responsive hydrogel and its application in drug release

The microporous hydrogels (Pn‐Cm gels) composed of poly(dimethylaminoethyl methacrylate) and carboxymethylchitosan were synthesized in situ radical polymerization by using nano γ‐Fe₂O₃ particles as pore‐agent. The microporous structure formed through eliminating the Fe₂O₃ particles was designed to achieve a faster response rate and better drug loading effect. Comparing to the neat gels, Pn‐Cm gels exhibit deteriorative mechanical properties with the increased pores, while the gels still keep the elastic network structure which could bear some degree of tensile and compression deformation. Meantime, Pn‐Cm gels show similar temperature and pH double responsiveness with same isoelectric point shrink as that of neat gels, the swelling ability decreases slightly, and the deswelling rate increases with the increase of pores. Moreover, the 5‐fluorouracil was used as a target drug to explore the potential of this gel applied as drug‐release system. For Pn‐Cm gels, the more pores and carboxymethyl chitosan inside the gels are beneficial to the drug loading, all gels show a burst release of drug, being followed by a slow and sustained release with different rate. Comprehensively, the Pn‐Cm gels exhibit a better sustained release effect in the simulated stomach condition (pH = 2.1), the related release mechanism could be interpreted by the superposition of Fickian diffusion. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45326.     

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     

Elaboration of porosity for the alumina particle surfaces/ bimodal PP composite cast films under continuous stretching

Efforts have been focused on developing an interrelationship between machine direction orientation (MDO)/material variables and the porosity of Al₂O₃ particulate-filled orientable PP for various applications. Composite films were prepared by cast-extrusion followed by stretching up to 100% and 200% by the MDO machine. Cavitation could occur during film stretching when the adhesion between dispersed alumina and continuous polypropylene phase failed. Composite films with modified micro-particles and also nano ones could not generate any voids. On the other hand, composite specimens of unmodified micro-alumina particles generated micro-pores in the joint between dispersed particles and polymer during the hot stretching. Beta nucleation in these films, plays an important role in the generated ductility of the specimens. Cavitation effectiveness (no. of voids) or film permeability depended on the size and amount of alumina particles, in addition to the ratio and temperature of stretching. Cavitation particles with a size range of 0.7–3 μm, create cavities of about 3–7 μm. Generation of voids, by drawing environmentally friendly and antimicrobial active alumina particles, can be utilized in the fabrication of sustainable hygiene polypropylene films with desirable separation abilities for gases or small molecules. Furthermore, the polypropylene/alumina composite films have the potential for microwaveable packaging.     

Orientational behaviors of silk fibroin hydrogels

In this study, a novel shear‐induced silk fibroin (SF) hydrogel with three‐dimensional (3D) anisotropic and oriented gel skeleton/network morphology is presented. Amphipathic anionic and nontoxic sodium surfactin is blended with the SF to decrease its gelation time during the mechanical shearing process. The fibroin/surfactin blended solutions undergo a facial shearing process to accomplish a sol–gel transition within 1 hour. The dynamic sol–gel transition kinetic analysis, gel skeleton/network morphology, and mechanical property measurements are determined in order to visualize the fibroin/surfactin sol–gel transition during the shearing process and its resulting hydrogel. The results demonstrate that there is significant β‐sheet assembly from random coil conformations in the fibroin/surfactin blended system during the facile shearing process. The SF β‐sheets further transform into a fibrous large‐scale aggregation with orientational and parallel arrangements to the shearing direction. The shear‐induced fibroin/surfactin hydrogel exhibits notable anisotropic and oriented 3D skeleton/network morphology and a significant mechanical compressive strength in proportion to the shearing stress, compared with the control fibroin/surfactin hydrogel undergoing no shearing process. Due to its oriented gel skeleton/network structure and significantly enhanced mechanical properties, the shear‐induced fibroin/surfactin gel may be suitable as a biomaterial in 3D oriented tissue regeneration, including for nerves, the cultivation of bone cells, and the repair of defects in muscle and ligament tissues. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45050.     

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。     

Facile preparation for robust and freestanding silk fibroin films in a 1‐butyl‐3‐methyl imidazolium acetate ionic liquid system

Silk fibroin film (SFF) with excellent mechanical properties was prepared for the first time with Bombyx mori silk fibroin as the material and 1‐butyl‐3‐methyl imidazolium acetate ([Bmim]OAc) ionic liquid (IL) as the solvent. The aim was to understand whether the microstructure of SFF could be modified and whether the mechanical properties were improved when [Bmim]OAc IL was used as a solution. With this new system, the obtained SFF was easily peeled off of the substrate, and the silk fibroin proteins retained the α‐helix secondary structure (silk I). Further test results show that the tensile strength (126.8–129.7 MPa) and anti‐UV performance were stronger than the silk fibroin regenerated by traditional ways. Therefore, this study provided and identified a new method with [Bmim]OAc to obtain SFF with strong mechanical properties. This facile preparation and related SFF with excellent mechanical strength could have potential applications in biocompatible implants, synthetic coatings for artificial skin, and many other areas. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42822.     

Co‐extruded polymeric films for gas separation membranes

In recent years, gas separation has become an important step in many production process streams and part of final products. Through the use of melt co‐extrusion and subsequent orientation methods, gas separation membranes were produced entirely without the use of solvents, upon which current methods are highly dependent. Symmetric three layer membranes were produced using poly(ether‐block‐amide) (PEBA) copolymers, which serve as a selective material that exhibits a high CO₂ permeability relative to O₂. Thin layers of PEBA are supported by a polypropylene (PP) layer that is made porous through the use of two methods: (1) inorganic fillers or (2) crystal phase transformation. Two membrane systems, PEBA/(PP + CaCO₃) and PEBA/β‐PP, maintained a high CO₂/O₂ selectivity while exhibiting reduced permeability. Incorporation of an annealing step either before or after orientation improves the membrane gas flux by 50 to 100%. The improvement in gas flux was a result of either elimination of strain induced crystallinity, which increases the selective layer permeability, or improvement of the PP crystal structure, which may increase pore size in the porous support layer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39765.