Multifunctional bioactive glass scaffolds coated with layers of poly(d,l-lactide-co-glycolide) and poly(n-isopropylacrylamide-co-acrylic acid) microgels loaded with vancomycin

A new family of multifunctional scaffolds, incorporating selected biopolymer coatings on basic Bioglass® derived foams has been developed. The polymer coatings were investigated as carrier of vancomycin which is a suitable drug to impart antibiotic function to the scaffolds. It has been proved that coating with PLGA (poly(lactic-co-glycolic acid)) with dispersed vancomycin-loaded microgels provides a rapid delivery of drug to give antibacterial effects at the wound site and a further sustained release to aid mid to long-term healing. Furthermore, the microgels also improved the bioactivity of the scaffolds by acting as nucleation sites for the formation of HA crystals in simulated body fluid.     

非金属粉体化学镀银影响因素的研究

表面镀银的非金属粉体材料可作为导电填料用于多种领域,为探索不同助剂和pH值对镀层质量的影响及原因,以玻璃微球为材料,用几种不同高分子化合物(PEG,CMC和明胶等)做助剂,在不同的pH值(7.5,9.5,11.5和13.5)条件下进行反应,得到了镀层质量随反应时间的变化曲线(镀速曲线),并对镀银产品进行SEM分析.结果表明,PEG和乙醇均使镀层质量有所提高,其中PEG作用最明显,而CMC和明胶的加入则起反作用;镀银液pH值为13.5左右反应可得质量较好的镀层,并从机理方面对此进行了阐释;混合助剂在pH=13.5时以PEG和EtOH组合作助剂可得高质量的镀层.     

Biomimetic mineralization of partially bioresorbable glass fiber reinforced composite

The aim of this study was to investigate the biomimetic mineralization on the surface of a glass fiber reinforced composite with partially resorbable biopolymer matrix. The E-glass fibers were preimpregnated with a novel biopolymer of poly(hydroxyproline) amide, and further impregnated in the monomer system of bis-phenyl glycidyl dimethacrylate (Bis-GMA)—triethylene glycol dimethacrylate (TEGDMA), which formed interpenetrating polymer networks (IPN) with the preimpregnation polymer. After light-initiated polymerization of the monomer system, the rhombic test specimens (n = 6) were immersed in the simulated body fluid (SBF) with the bioactive glass for 24 h, and then the apatite nuclei were allowed to grow for 1, 3, 5 and 7 days in the SBF. The control test specimens (n = 3) were immersed in SBF without the bioactive glass. According to the scanning electron microscope (SEM), a mineral layer was formed on the surface of all the specimens, which were immersed with bioactive glass. The layer was thickened by the prolonged immersion time to a uniform layer. The Ca/P atomic ratio of the mineral varied between 1.30 and 1.54 as analyzed by the energy dispersive X-ray analysis (EDXA). The Fourier transform infrared spectroscopy (FT-IR) spectra gave signals for the mineral, which are characteristic of both bone-like apatite and orthocalciumphosphate. In conclusion, the mineral layer was formed on the surfaces of the specimens by biomimetic mineralization, the mineral being a mixture of bone-like apatite, orthocalciumphosphate and other calcium phosphates.     

PEG及其复合加工助剂对UHMWPE/PP共混物流变性能的影响

用高压毛细管流变仪研究了PEG、PEG与硅藻土和玻璃微珠的复合物对UHMWPE／PP(80／20)共混物加工流变性的影响,结果表明,少量PEG及其复合加工助荆均能显著降低UHMWPE／PP的熔体表现粘度,改善挤出物的外观质量。PEG与玻璃微珠对UHMWPE／PP熔体有协同降粘作用。     

控制聚合与沉淀协同作用改善高铁轨道板涂料用水玻璃性能

CaO可能对水玻璃酸碱度、Zeta电位产生影响,引起调控水玻璃中硅氧聚合体的聚合度和形成沉淀的协同作用,有望改善水玻璃的力学强度和耐水性。欲提高环保型高铁轨道板涂料用水玻璃的力学强度和耐水性,本实验拟采用CaO对水玻璃进行改性,并探索改性的相关机理。实验结果表明,CaO改性水玻璃力学强度提高77%,耐水性也明显提高。Zeta电位仪、pH计、X射线衍射仪、傅里叶红外光谱仪及固体核磁共振仪检测结果表明:添加CaO使水玻璃Zeta电位值、pH值均增大;在形成Ca²⁺的协同作用下,导致硅氧聚合体解聚、重组并限制聚合,主要以链状聚合体(Q²)存在。同时Ca²⁺与Q²结合形成耐水性较好、力学强度较高的CaO·xSiO₂·yH₂O(CSH)凝胶,而不是含大量Na⁺、耐水性差的硅氧聚合体。可以推断,CaO可产生控制聚合度和沉淀协同效应改善水玻璃性能,有望应用于高铁轨道板涂料用水玻璃。     

光刻法制备聚合物/液晶光栅

将明胶涂覆在表面经过取向处理的带有ITO电极的玻璃基板上，以紫外灯为光源，通过光掩模法，使明胶在光场的引发下发生光化学反应，样品显影刻蚀处理后呈栅状，将液晶注入光栅盒中，形成聚合物／液晶光栅。该光栅衍射效率可利用电场调控。采用He—Ne激光器对所制样品进行测试，结果表明，所制样品的栅结构较好。避免了液晶与聚合物相分离的不完全性和栅条边缘不整齐的现象。制得的光栅其第一衍射级次的开关比为87：1，显示了较好的开关能力。     

Intrinsic viscosity of polymers and biopolymers measured by microchip

Intrinsic viscosity provides insight to molecular structure and interactions in solution. A new microchip method is described for fast and accurate measurements of viscosity and intrinsic viscosity of polymer and biopolymer solutions. Polymer samples are diluted with solvent in the microfluidic chip by imposing pressure gradients across the channel network. The concentration and flow dilutions of the polymer sample are calculated from the fluorescent signals recorded over a range of dilutions. The viscosities at various polymer dilutions are evaluated using mass and momentum balances in the pressure-driven microchannel flow. The technique is particularly important to many chemical, biological, and medical applications where sample is available in very small quantities. The intrinsic viscosity experiments were performed for three classes of polymer solutions: (a) poly(ethylene glycol), polymers with linear hydrocarbon chains; (b) bovine serum albumin, biopolymer chains with hydrophobic and hydrophilic amino acids, and (c) DNA fragments, biological macromolecules with double-stranded polymeric chains. The measured values of intrinsic viscosity agree remarkably well with the available data obtained using different methods. The data exhibit power law behavior for molecular weight as described by the Mark-Houwink-Sakurada equation. Experiments were performed to understand the effect of solvent quality and salt concentration on molecular conformations and the intrinsic viscosity of the polymers. This method offers a new way to study the conformational changes in proteins and DNA solutions in various buffer conditions such as pH, ionic strength, and surfactants. The effects of shear rate in the microchannel and mixing time on the accuracy and limitation of the measurement method are discussed.     

Formulation and characterization of naked DNA and complexed DNA loaded polymer films

Sustained release of DNA from polymeric films is of considerable interest for enhanced and prolonged gene therapy. This report describes the detailed studies of the formulation of naked plasmid DNA (pDNA) and complexed DNA-incorporated polymer films and in vitro release of the DNA. The effect of hydrophilic polymers (PEG, HA) also studied to modulate the release of pDNA and complexed DNA (lipoplex) from slow biodegradable polymer (PCL) films. The polymer system consists of a biodegradable semi-crystalline polymer (PCL) blended with a hydrophilic polymer such as poly (ethylene glycol) (PEG) or hyaluronic acid (HA). For the release of pDNA (naked DNA), a burst effect was always seen, and the addition of HA and PEG did not suppress the burst release of pDNA from PCL films. For complexed pDNA (lipoplex), the release was slow, but it could be accelerated using additives such as PEG or HA. The transfection efficiency of the complexed DNA and the naked pDNA was determined in vitro using COS 7 cells to evaluate the bioactivity of the released DNA. Transfection was observed from released lipoplexes samples from PCL/HA film. Overall, this work suggested that these polymeric DNA delivery systems are promising for the local sustained release of DNA from implanted films.     

Molar mass profiling of synthetic polymers by free-solution capillary electrophoresis of DNA-polymer conjugates

The molar mass distribution of a polymer sample is a critical determinant of its material properties and is generally analyzed by gel permeation chromatography or more recently, by MALDI-TOF mass spectrometry. We describe here a novel method for the determination of the degree of polymerization of polydisperse, uncharged, water-soluble polymers (e.g., poly(ethylene glycol) (PEG)), based upon single-monomer resolution of DNA-polymer conjugates by free-solution capillary electrophoresis. This is accomplished by end-on covalent conjugation of a polydisperse, uncharged polymer sample (PEG) to a monodisperse, fluorescently labeled DNA oligomer, followed by electrophoretic analysis. The monodisperse, charged DNA "engine" confers to each conjugate an equal amount of electromotive force, while the varying contour lengths of the uncharged, polydisperse polymers engender different amounts of hydrodynamic drag. The balance of electromotive and hydrodynamic forces enables rapid, high-resolution separation of the DNA-polymer conjugates as a function of the size of the uncharged PEG tail. This provides a profile of the molar mass distribution of the original polymer sample that can be detected by laser-induced fluorescence through excitation of the dye-labeled DNA. We call this method free solution conjugate electrophoresis (FSCE). Theory-based analysis of the resulting electrophoresis data allows precise calculation of the degree of polymerization of the PEG portion of each conjugate molecule. Knowledge of the molecular mass of the uncharged polymer's repeat unit allows for direct calculation of the molar mass averages as well as sample polydispersity index. The results of these analyses are strikingly reminiscent of MALDI-TOF spectra taken of the same PEG samples. PEG samples of 3.4-, 5-, and 20-kDa nominal average molar mass were analyzed by FSCE and MALDI-TOF; the values of the molar mass averages, Mw and Mn, typically agree to within 5%. Measurements and molar mass calculations are performed without any internal standards or calibration. Moreover, when DNA-polymer conjugate analysis is performed in a chip-based electrophoresis system, separation is complete in less than 13 min. FSCE offers an alternative to MALDI-TOF for the characterization of uncharged, water-soluble polymers that can be uniquely conjugated to DNA.     

基底诱导聚合物相分离制备高度有序图形的研究

基底诱导聚合物相分离是一种制备高度有序图形化高分子薄膜的新技术。研究考察了PS/PVP共混物在图案化基底上的相分离图形化的影响因素。实验证明,聚合物薄膜的膜厚对图形的质量有着重要的影响。薄膜厚度过薄（小于100nm）反浸润现象导致薄膜不连续;薄膜很厚（大于300nm）时基底的诱导效应减弱。而在合适的膜厚情况下（约140nm）,基底图案对聚合物膜的表面形态有最好的诱导效果。另一个关键因素是基底图案的周期,当周期与聚合物本征颗粒的尺寸相近时图形化效果最好。     

Ternary semitransparent organic solar cells with a laminated top electrode

Abstract

Tinted and colour-neutral semitransparent organic photovoltaic elements are of interest for building-integrated applications in windows, on glass roofs or on facades. We demonstrate a semitransparent organic photovoltaic cell with a dry-laminated top electrode that achieves a uniform average visible transmittance of 51% and a power conversion efficiency of 3%. The photo-active material is based on a majority blend composed of a visibly absorbing donor polymer and a fullerene acceptor, to which a selective near-infrared absorbing cyanine dye is added as a minority component. Our results show that organic ternary blends are attractive for the fabrication of semitransparent solar cells in general, because a guest component with a complementary absorption can compensate for the inevitably reduced current generation capability of a high-performing binary blend when applied as a thin, semitransparent film.     

Flexural properties of glass fiber reinforced composite with multiphase biopolymer matrix

The aim of this study was to evaluate flexural properties of glass fiber-reinforced composites with a multiphase biopolymer matrix. Continuous unidirectional E-glass fibers were preimpregnated with a novel biopolymer of poly(hydroxyproline) amide and ester. The preimpregnated fibers were then further impregnated in a co-monomer system of Bis-GMA-TEGDMA, which formed semi-interpenetrating polymer networks (semi-IPN) with the preimpregnated polymer. After light initiated polymerization of the monomer system, rectangular shaped bar specimens (n = 4) were tested by the three-point bending test. The control material was a fiber-reinforced composite with a Bis-GMA-TEDGMA-matrix only. The mean flexural strength of poly(hydroxyproline) amide preimpregnated fiber composite was higher than that of the control (FS = 888 vs. 805 MPa). The poly(hydroxyproline) ester preimpregnated fibers resulted in lower strength (FS = 541 MPa). The results of this study suggest that preimpregnation of glass fibers with poly(hydroxyproline) amide and the use of such fibers in fiber-reinforced composites with IPN polymer matrices, can reach relatively high mechanical properties.     

Arrays of nanoscale lenses for subwavelength optical lithography

Poly(ethylene glycol) (PEG) polymer lens arrays are made by using dip-pen nanolithography to deposit nanoscale PEG features on hydrophobically modified quartz glass. The dimensions of the PEG lenses are controlled by tuning dwell time and polymer molecular weight. The PEG polymer lenses on the quartz substrate act as a phase-shift photomask for fabricating subwavelength scale features, ～ 100 nm in width. Depending upon UV irradiation time during the photolithography, the photoresist nanostructures can be transitioned from well-shaped (short time) to ring-shaped (long time) features. The technique can be used to pattern large areas through the use of cantilever arrays.     

Fabrication and characterization of PCL/gelatin composite nanofibrous scaffold for tissue engineering applications by electrospinning method

In the present study, composite nanofibrous tissue engineering-scaffold consisting of polycaprolactone and gelatin, was fabricated by electrospinning method, using a new cost-effective solvent mixture: chloroform/methanol for polycaprolactone (PCL) and acetic acid for gelatin. The morphology of the nanofibrous scaffold was investigated by using field emission scanning electron microscopy (FE-SEM) which clearly indicates that the morphology of nanofibers was influenced by the weight ratio of PCL to gelatin in the solution. Uniform fibers were produced only when the weight ratio of PCL/gelatin is sufficiently high (10:1). The scaffold was further characterized by Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric (TG) analysis, and X-ray diffraction (XRD). FT-IR and TG analysis indicated some interactions between PCL and gelatin molecules within the scaffold, while XRD results demonstrated crystalline nature of PCL/gelatin composite scaffold. Cytotoxicity effect of scaffold on L929 mouse fibroblast cells was evaluated by MTT assay and cell proliferation on the scaffold was confirmed by DNA quantification. Positive results of MTT assay and DNA quantification L929 mouse fibroblast cells indicated that the scaffold made from the combination of natural polymer (gelatin) and synthetic polymer (PCL) may serve as a good candidate for tissue engineering applications.     

Release of lysozyme from electrospun PVA/lysozyme-gelatin scaffolds

This article describes an electrospinning process in fabricating ultra fine fibers with core-shell structure. A biodegradable polymer, poly(vinyl alcohol) (PVA), was used as the shell; lysozyme was a kind of antioxidant; and gelatin were used as the core.Morphology and microstructure of the ultra fine fibers were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analysis. As a comparison, composite nanofiber PVA/lysozyme-gelatin blend was prepared by a normal electrospinning process. In vitro drug release behaviors of the nanofibrous membranes were determined in phosphatebuffered saline (PBS) solution. It was found that core-shell nanofibers PVA/lysozyme-gelatin obviously exhibit higher initial release rates compared to that of PVA/lysozymegelatin blend nanofibers. The current method may find wide application in controlled release of bioactive proteins and tissue engineering.     

Release of lysozyme from electrospun PVA/lysozyme-gelatin scaffolds

This article describes an electrospinning process in fabricating ultra fine fibers with core-shell structure. A biodegradable polymer, poly(vinyl alcohol) (PVA), was used as the shell; lysozyme was a kind of antioxidant; and gelatin were used as the core. Morphology and microstructure of the ultra fine fibers were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) analysis. As a comparison, composite nanofiber PVA/lysozyme-gelatin blend was prepared by a normal electrospinning process. In vitro drug release behaviors of the nanofibrous membranes were determined in phosphate-buffered saline (PBS) solution. It was found that core-shell nanofibers PVA/lysozyme-gelatin obviously exhibit higher initial release rates compared to that of PVA/lysozyme-gelatin blend nanofibers. The current method may find wide application in controlled release of bioactive proteins and tissue engineering.     

Properties and drug release profile of poly(N-isopropylacrylamide) microgels functionalized with maleic anhydride and alginate

This study highlights the advantages of functionalized poly(N-isopropylacrylamide) (PNIPAAm) microgels over pure PNIPAAm microgels in terms of polymer network properties and drug release profiles. PNIPAAm network was modified by addition of maleic anhydride (MA) as a comonomer and by formation of interpenetrating polymer network in the presence of alginate. The functionalized thermosensitive microgels in the size range from 20 to 80 μm and with better performance in comparison with pure PNIPAAm microgels were prepared by inverse suspension polymerization. The impact of MA and alginate on the PNIPAAm microgel structure was evaluated through analysis of microgel size, size distribution, volume phase transition temperature (VPTT), equilibrium swelling ratio as well as morphology of the system. It was shown that the controlled modification of PNIPAAm network could result in microgels of considerably improved swelling capacity with unchanged thermosensitivity and maintained open pore morphology. In addition, drug release behavior of microgels could be markedly altered. Release of procaine hydrochloride from the selected microgels was studied using Franz diffusion cell at temperatures below and above VPTT of the microgels. Temperature-controlled drug release pattern was dependent on the type of functionalization of PNIPAAm network. According to drug loading properties and drug release mechanism, PNIPAAm/MA copolymer microgels demonstrated the optimal performances.     

Separation of proteins from aqueous solution using cellulose acetate/poly (vinyl chloride) blend ultrafiltration membrane

Cellulose acetate (CA) membranes are widely used for ultrafiltration applications. CA and poly (vinyl chloride) (PVC) blend membranes are prepared by using polar solvent of N, N-dimethylformamide (DMF) by phase inversion method. Polyethylene glycol (PEG 600) is used as polymeric additive in the casting solution. The effect of polymer composition and additive concentration on surface morphology, porosity are studied. The morphology of prepared membranes is found to have asymmetric structure with dense skin layer and porous sub-layer. Applications of these membranes are carried out for rejection and permeation of macromolecular proteins such as trypsin, pepsin, egg albumin, bovine serum albumin. On increasing the concentration of PVC and PEG 600, protein rejection decreases whereas permeate flux increases.CA/PVC/PEG (70/30/10 wt%) blend membrane shows the highest permeation flux of 211.1 lm⁻² h⁻¹ for trypsin.     

添加致孔剂制备树脂基活性炭及电容性能研究

以碱性条件下合成的热固性酚醛树脂(PF)为原料,聚乙烯醇缩丁醛(PVB)和聚乙烯二醇(PEG)为致孔剂,采用聚合物共混炭化活化法制备双电层电容器用活性炭材料.通过热重(TG)分析探讨了PF,PF与PVB、PEG的共混物在炭化过程中的热解行为.考察了活化温度和活化时间对所得活性炭的收率、BET比表面积、孔径分布和比电容的影响,并进一步探讨了以这种活性炭材料作电极的双电层电容器的电容性能.结果表明,随着活化温度的升高,活化温度对活性炭收率的影响更为显著,所得活性炭的收率下降.聚合物PEG较PVB更适合作为成孔剂来控制活性炭的中孔孔径分布.酚醛树脂基活性炭电极比电容在850℃活化1 h为79.2F/g,而聚乙烯二醇/酚醛、聚乙烯醇缩丁醛/酚醛混合树脂基活性炭电极比电容则分别高达130.5和145.6F/g.     

Microfluidic Templating of Spatially Inhomogeneous Protein Microgels

3D scaffolds in the form of hydrogels and microgels have allowed for more native cell‐culture systems to be developed relative to flat substrates. Native biological tissues are, however, usually spatially inhomogeneous and anisotropic, but regulating the spatial density of hydrogels at the microscale to mimic this inhomogeneity has been challenging to achieve. Moreover, the development of biocompatible synthesis approaches for protein‐based microgels remains challenging, and typical gelation conditions include UV light, extreme pH, extreme temperature, or organic solvents, factors which can compromise the viability of cells. This study addresses these challenges by demonstrating an approach to fabricate protein microgels with controllable radial density through microfluidic mixing and physical and enzymatic crosslinking of gelatin precursor molecules. Microgels with a higher density in their cores and microgels with a higher density in their shells are demonstrated. The microgels have robust stability at 37 °C and different dissolution rates through enzymolysis, which can be further used for gradient scaffolds for 3D cell culture, enabling controlled degradability, and the release of biomolecules. The design principles of the microgels could also be exploited to generate other soft materials for applications ranging from novel protein‐only micro reactors to soft robots.