Preparation and characterization of novel biocompatible cryogels of poly (vinyl alcohol) and egg-albumin and their water sorption study

Polyvinyl alcohol (PVA) and egg albumin are water-soluble, biocompatible and biodegradable polymers and have been widely employed in biomedical fields. In this paper, novel physically cross-linked hydrogels composed of poly (vinyl alcohol) and egg albumin were prepared by cyclic freezing/thawing processes of aqueous solutions containing PVA and egg albumin. The FTIR analysis of prepared cryogels indicated that egg albumin was successfully introduced into the formed hydrogel possibly via hydrogen bonds among hydroxyl groups, amide groups and amino groups present in PVA and egg albumin. The gels were also characterized thermally and morphologically by DSC and SEM-techniques, respectively. The prepared so called ‘cryogels’ were evaluated for their water uptake potential and influence of various factors such as chemical architecture of the spongy hydrogels, pH and temperature of the swelling bath were investigated on the degree of water sorption by the cryogels. The effect of salt solution and various simulated biological fluids on the swelling of cryogel was also studied. The in vitro biocompatibility of the prepared cryogel was also judged by methods such as protein (BSA) adsorption, blood clot formation and percentage hemolysis measurements.     

PVA基金属配合纳米纤维膜的制备及其性能研究

选用静电纺丝法制备的PVA纳米纤维毡为基体,与金属铜、铁离子发生配位反应,制备PVA基金属配合纳米纤维.采用原子吸收光谱分析仪研究了PVA纳米纤维膜吸附的金属离子含量,采用红外光谱(FT-IR)分析了PVA与金属离子的配合作用.同时研究了与金属离子配合对纳米纤维膜亲水性和力学性能的影响.实验结果表明,PVA纳米纤维与金...     

Designing of macroporous biocompatible cryogels of PVA–haemoglobin and their water sorption study

Macroporous polymeric materials are three-dimensional porous architectures having enormous utility in the areas of biomedical, biotechnological and separation sciences. Thus realizing the crucial role of macroporous polymeric materials in tissue engineering and allied fields the present paper discusses synthesis, characterization, and blood compatibility study of macroporous cryogels of PVA and haemoglobin. Biocompatible spongy and porous hydrogels of polyvinyl alcohol–haemoglobin have been synthesized by repeated freezing–thawing method and characterized by Infrared (FTIR), and ESEM techniques. The FTIR analysis of prepared cryogels indicated that haemoglobin was introduced into the cryogel possibly via hydrogen bonds formed amongst hydroxyl groups and amino groups present in PVA and haemoglobin, respectively. The ‘cryogels’ were evaluated for their water uptake potentials and influence of various factors such as chemical architecture of the spongy hydrogels, pH and temperature of the swelling bath were investigated on the degree of water sorption by the cryogels. The hydrogels were also swollen in salt solutions and various simulated biological fluids. The effect of drying temperature on its water sorption capacity was also studied. The biocompatibility of the prepared cryogels was judged by in vitro methods of blood-clot formation, percent haemolysis and protein (BSA) adsorption.     

氯化镁/甘油改性羧甲基淀粉/聚乙烯醇共混材料的结构与性能

为获得改性淀粉/聚乙烯醇(PVA)共混材料的结构与性能特征,以氯化镁/甘油为复配改性剂,采用溶液成膜方法制备了羧甲基淀粉(CMS)/PVA,研究了CMS/PVA复合膜的红外吸收特性、结晶性能、微观形貌、热性能、力学性能及生物降解性。研究结果表明,氯化镁和甘油可与CMS/PVA产生电子相互作用和氢键作用,阻碍CMS/PVA分子链的规整排列,提高羧甲基淀粉与PVA的相容性,降低CMS/PVA的结晶度和热稳定性。氯化镁/甘油复配改性剂对CMS/PVA的力学性能影响显著,可使CMS/PVA断裂伸长率和拉伸强度提高。氯化镁/甘油可促进CMS/PVA的降解,增加氯化镁/甘油复配改性剂中氯化镁的含量可提高复合膜的降解率。     

PVA/淀粉单层和多层复合材料的制备和性能研究

利用流延成形的方法制备PVA/淀粉单层和多层复合薄膜,并通过硅溶胶对其进行改性,对其力学性能和亲水性能进行研究,通过扫描电镜（SEM）、傅里叶红外（FT-IR）等对其进行表征。FT-IR结果表明,SiO₂与淀粉或PVA间发生脱水缩合,分子链间产生交联,SiO₂含量越多,交联程度越大。通过薄膜拉伸断口的SEM分析,在多层结构中,SiO₂颗粒能起到更好的增强增韧效果,多层结构比单层结构有着更高的抗拉强度和断裂延伸率。     

Fabrication and characterization of biodegradable composites based on microfibrillated cellulose and polyvinyl alcohol

Microfibrillated cellulose (MFC) based thin membrane-like fully biodegradable composites were produced by blending MFC suspension with polyvinyl alcohol (PVA). Desired MFC content in the composites could be easily obtained by varying the PVA solution concentration. Chemical crosslinking of PVA was carried out using glyoxal to increase the mechanical and thermal properties of the composites as well as to make the PVA partially water-insoluble. Examination of composite surfaces and fracture topographies indicated that the MFC fibrils were well bonded to PVA and uniformly distributed. Infrared spectroscopy showed that acetal linkages could be formed in the MFC–PVA composites by a glyoxal crosslinking reaction. Sol–gel and swelling results indicated that crosslinking reaction made PVA partially insoluble and reduced its swelling ability. The MFC–PVA composites had excellent tensile properties which were further enhanced by crosslinking. Thermogravimetric analysis (TGA) showed higher thermal stability for MFC–PVA composites compared to PVA. The crosslinked MFC–PVA composites showed even higher thermal stability. Differential scanning calorimetry (DSC) indicated that crosslinking increased the glass transition temperature and reduced melting temperature and crystallinity of PVA in MFC–PVA composites. Results also indicated that nano- and micro-fibrils in MFC inhibit the crystallization of PVA. These composites could be good candidates for replacing today’s traditional non-biodegradable plastics.     

Bacterial cellulose-based membrane-like biodegradable composites using cross-linked and noncross-linked polyvinyl alcohol

Bacterial cellulose (BC)-based membrane-like biodegradable composites were produced by immersing wet BC pellicles in polyvinyl alcohol (PVA) solution. The BC content in the BC–PVA composites can be adjusted by varying the concentration of PVA solution. Chemical cross-linking of PVA was carried out using glutaraldehyde to increase the mechanical properties of the composites as well as to make the PVA partially to highly water insoluble. Examination by scanning electron microscopy indicated that the PVA not only penetrated the BC network, but also filled the pores within the BC pellicle. Attenuated total reflectance-Fourier transform infrared spectroscopy showed that acetal linkages could be formed in the BC–PVA composites by a cross-linking reaction. Sol–gel results indicated that cross-linking reaction increasingly made PVA insoluble in water resulting in higher gel (cross-linked fraction) content in the PVA. Wide-angle X-ray diffraction results showed decreased crystallinity in cross-linked BC and PVA, as expected. It was also found that crystal size was smaller in PVA after cross-linking. The BC–PVA composites had excellent tensile properties and cross-linking increased these properties further. Thermogravimetric analysis showed higher thermal stability for BC–PVA composites compared to PVA. The cross-linked specimens, especially the highly cross-linked ones, showed even higher thermal stability. The methods developed in this study make it possible to control the PVA content in the composites as well as the cross-linking level of PVA. These composites could be good candidates for replacing traditional non-biodegradable plastics.     

Morphology and pore characteristics of bacterial cellulose/multiwalled carbon nanotube composite cryogels

Bacterial cellulose/multiwalled carbon nanotube (MWCNT) composite cryogels were prepared via sol-gel chemistry using epichlorohydrin as a crosslinker. Their morphology and pore characteristics were examined under various conditions. The bacterial cellulose/MWCNT composite cryogels had a macroporous structure that contained mesopores and micropores due to the MWCNTs that were homogeneously incorporated in the macroporous network structure.     

纤维素氨基甲酸酯的制备及再生膜的应用

以常用廉价溶剂N,N-二甲基乙酰胺(DMAc)为介质,以纤维素和尿素为原料,制备了纤维素氨基甲酸酯(CC),采用红外光谱、X射线衍射、扫描电镜等对产物的结构进行了表征,并对纤维素再生膜的截留性能进行了研究。结果表明,制备纤维素氨基甲酸酯的最佳反应条件为160℃,8 h;酯化前后,纤维素晶型没有发生明显的变化;制备的纤维素再生膜具有孔径很小的微孔,这些微孔能够使H_2O和Na_2SO_4在压力的作用下顺利通过,而对亚甲基蓝有良好的截留效果;因此,纤维素再生膜对含亚甲基蓝的废水具有良好的分离效果。     

微纳纤维素晶体/聚乙烯醇渗透汽化膜材料的研究

利用微纳纤维素晶体改性戊二醛交联的聚乙烯醇渗透汽化膜,考察了微纳纤维素晶体的添加对交联膜的影响,并对膜材料进行FT-IR和AFM检测。结果表明,添加0.5%的微纳纤维素晶体改性膜材料的渗透通量从423.14g.m2.h-1提高到751.61g.m2.h-1,分离因子基本不变;对膜材料进行FT-IR和AFM检测表明,微纳纤维素晶体与聚乙烯醇之间产生新的氢键缔合,改性膜材料表面规整、致密无孔。     

高结晶度氮化硼纳米片的制备及其与聚乙烯醇复合薄膜的性能

以具有特殊花瓣状形貌的硼酸镁纳米片为模板、前驱体和硼源, 以氨气为氮源合成了氮化硼纳米片(BNNSs), 通过 SEM、TEM、XRD、Raman和FT-IR等对其形貌和结构等进行了分析。结果表明: 合成的BNNSs为厚度仅约5 nm、横向尺寸150~300 nm、结晶度极高的单晶片层状h-BN, 多个BNNSs聚集形成了形貌与硼酸镁纳米片类似的形状。以所合成的BNNSs为填料, 制备了不同BNNSs添加量的BNNSs/聚乙烯醇(PVA)复合材料薄膜, 结果表明添加30% BNNSs的复合薄膜的弹性模量较纯PVA薄膜提高了约39.8%, 面内热扩散系数和热导率则分别最大提高了约7和8倍, 说明以此BNNSs做为填料能明显改善BNNSs/PVA复合薄膜的热学性能。     

Preparation and characterization of keratin-based biocomposite hydrogels prepared by electron beam irradiation

The biocompatible and highly porous keratin-based hydrogels were prepared using electron beam irradiation (EBI). The conditions for keratin-based hydrogel formation were investigated depending on several conditions, including the presence of poly(vinyl alcohol) (PVA), concentration of keratin solution, EBI dose, and poly(ethylene imine) (PEI) additives. The pure keratin (human hair and wool) aqueous solution was not gelled by EBI, while the aqueous keratin solutions blended with PVA were gelled at an EBI dose of more than 90 kGy. Furthermore, in the presence of PEI, the aqueous keratin solution blended with PVA could be gelled at a considerably lower EBI dose, even at 10 kGy. This finding suggests that the PEI additives significantly influence the rate of gelation and that PEIs function as an accelerator during gelation. The resulting keratin-based hydrogels were characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), gel fraction, degree of swelling, gel strength, and kinetics of swelling analyses.     

聚乙烯醇/纤维素纳米纤热塑性复合材料的制备及表征

将聚乙烯醇(PVA)、纤维素纳米纤(CNFs)通过熔融共混成功制备出高性能PVA/CNFs热塑性复合材料。采用扫描电镜、红外光谱、X射线衍射、差示扫描量热分析、热重分析对PVA/CNFs复合材料的微观形态及结构进行表征,对复合材料的物理力学性能进行测试。结果表明,选用适当的增塑剂与PVA、CNFs组合可实现PVA/CNFs共混体系的热塑成型;CNFs与PVA间的氢键作用有助于提高CNFs与PVA基体之间的相容性,从而优化PVA/CNFs复合材料的力学性能,拉伸强度从19.5 MPa增加到34.3 MPa,弹性模量从114.4 MPa增加到287.5 MPa。     

Evaluation of polyvinyl alcohols as mucoadhesive polymers for mucoadhesive buccal tablets prepared by direct compression

The purpose of the present work was to evaluate polyvinyl alcohols (PVAs) as a mucoadhesive polymer for mucoadhesive buccal tablets prepared by direct compression. Various polymerization degree and particle diameter PVAs were investigated for their usability. The tensile strength, in vitro adhesive force, and water absorption properties of the tablets were determined to compare the various PVAs. The highest values of the tensile strength and the in vitro adhesive force were observed for PVAs with a medium viscosity and small particle size. The optimal PVA was identified by a factorial design analysis. Mucoadhesive tablets containing the optimal PVA were compared with carboxyvinyl polymer and hydroxypropyl cellulose formulations. The optimal PVA gives a high adhesive force, has a low viscosity, and resulted in relatively rapid drug release. Formulations containing carboxyvinyl polymer had high tensile strengths but short disintegration times. Higher hydroxypropyl cellulose concentration formulations had good adhesion forces and very long disintegration times. We identified the optimal characteristics of PVA, and the usefulness of mucoadhesive buccal tablets containing this PVA was suggested from their formulation properties.     

复配增塑剂对聚乙烯醇薄膜性能的影响

以尿素/三乙醇胺为复配增塑剂,利用溶液共混法制备了改性PVA薄膜,通过FT-IR研究了尿素/三乙醇胺复配增塑剂与PVA间的相互作用,采用XRD,TGA,DSC表征了增塑改性PVA的结晶性能和热性能,同时分析了复配增塑剂的加入对PVA薄膜力学性能、透光性能、耐水性能的影响。实验结果表明,复配增塑剂的加入破坏了PVA分子中的氢键作用,降低了PVA的结晶度和熔点温度,热分解温度基本不变;随着复配增塑剂含量的增加,增塑改性后的PVA薄膜抗拉强度下降、断裂伸长率增加,透光性增加,溶胀率下降,溶失率增加。     

Comparative investigation of Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) in the determination of cotton fiber crystallinity

Despite considerable efforts in developing curve-fitting protocols to evaluate the crystallinity index (CI) from X-ray diffraction (XRD) measurements, in its present state XRD can only provide a qualitative or semi-quantitative assessment of the amounts of crystalline or amorphous fraction in a sample. The greatest barrier to establishing quantitative XRD is the lack of appropriate cellulose standards, which are needed to calibrate the XRD measurements. In practice, samples with known CI are very difficult to prepare or determine. In a previous study, we reported the development of a simple algorithm for determining fiber crystallinity information from Fourier transform infrared (FT-IR) spectroscopy. Hence, in this study we not only compared the fiber crystallinity information between FT-IR and XRD measurements, by developing a simple XRD algorithm in place of a time-consuming and subjective curve-fitting process, but we also suggested a direct way of determining cotton cellulose CI by calibrating XRD with the use of CI(IR) as references.     

以LiBr/C2H5OH/H2O为溶剂的PVA/SF共混体系的相容性

采用LiBr/C2H5OH混合溶剂制备丝素(SF)溶液,与聚乙烯醇(PVA)水溶液进行溶液共混后得到PVA/SF共混膜,采用扫描电镜,差示扫描量热分析,红外光谱,X射线衍射等方法对共混膜进行了形态和结构表征。研究表明,相对于将PVA水溶液与SF水溶液共混得到的共混体系,此方法制备的体系中两组分的相容性得到了一定程度的提高。在SF含量较小的情况下,共混体系中几乎观察不到两相结构的存在。证明在PVA/SF体系中,SF的溶剂选择及SF的含量影响两种组分的相容性。     

New cellulose-lignin hydrogels and their application in controlled release of polyphenols

Novel superabsorbant cellulose-lignin hydrogels (CL) were prepared by a new two-step procedure consisting in dissolving cellulose in an alkaline solution with further mixing with lignin, followed by the chemical crosslinking with epichlorohydrin. The crosslinking occurrence was verified by Fourier Transform Infrared spectroscopy (FT-IR). The effect of the structure features of cellulose-lignin hydrogels on their dehydration heat was evaluated by Differential Scanning Calorimetry (DSC). The Scanning Electron Microscopy (SEM) images reveal some morphological aspects of the hydrogels. The degree as well as the rate of swelling in a mixture of water:ethanol = 19:1 were estimated. The possible application of these hydrogels as controlled release systems was tested. Polyphenols known as having a wide range of biological effects were selected to be incorporated in such hydrogels by an optimal procedure. The extract of grapes seeds from the Chambourcin type was used as a source of polyphenols (PF). The amount of the incorporated polyphenols was estimated by UV-VIS measurements. Characterization of the hydrogels containing polyphenols was performed by FTIR spectroscopy. Some parameters were estimated based on the registered spectra, as H-bond energy (E_H), the asymmetric index (a/b) and the enthalpy of H-bond formation (ΔH). The modifications of the thermal behavior and morphology induced by the presence of the polyphenols in hydrogels were highlighted by DSC and SEM, respectively. The release of polyphenols from CL hydrogels depended on the lignin content from matrices, as assessed by spectral studies. Both loading with polyphenols and their release can be controlled by the composition of the hydrogels. The kinetic of polyphenols release was studied.     

Biodegradable amylose films reinforced by graphene oxide and polyvinyl alcohol

Graphene oxide/amylose (GO/amylose) composite films with different amounts of graphene oxide (GO), glycerol and polyvinyl alcohol (PVA) were prepared by a solution casting method. The structure, morphologies, and properties of the films were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermal gravimetric analysis, UV–vis spectroscopy and tensile tests. The results indicated good dispersion of the GO nanosheets in the GO/amylose composite films and consequently a significant improvement in their mechanical properties. The addition of GO increased the tensile strength of the GO/amylose films, significantly. When glycerol was used as a plasticizer, the elongation at break of the films increased. When PVA was also added to the composite films, the films were mechanically strong and flexible. The incorporation of GO also decreased the moisture absorbability and UV transmittance of the films. The stability of the GO/amylose films in acidic and alkaline solutions was also studied and the films had excellent stability in both acidic and alkaline aqueous mediums.     

多孔PVA/CNFs复合水凝胶的制备与性能

目的研究聚乙二醇(PEG)的加入对复合凝胶微观结构、溶胀性能和热稳定性的影响,扩大复合凝胶在包装领域的应用。方法以PEG为致孔剂,纳米纤维素(CNFs)为增强相,利用物理交联法制备出多孔聚乙烯醇/纳米纤维素复合水凝胶。结果 PEG作为致孔剂时可制得网络互穿结构的多孔水凝胶,复合凝胶的溶胀度可达到1000,相比于纯PVA水凝胶有极大的提高,同时加入CNFs的聚乙烯醇凝胶与纯的聚乙烯醇凝胶相比具有更好的热稳定性。结论这种有着高溶胀性和良好热稳定性的多孔复合凝胶可用于包装产品的保鲜与物流防护。