Carbendazim‐loaded electrospun poly(vinyl alcohol) fiber mats and release characteristics of carbendazim therefrom

Ultra‐fine poly(vinyl alcohol) (PVA) electrospun fiber mats containing carbendazim were successfully fabricated by electrospinning from the neat PVA solution containing carbendazim in various amounts based on the weight of PVA. The morphological appearance of both the neat and the carbendazim‐loaded electrospun PVA fibers were smooth and the incorporation of carbendazim in the neat PVA solution did not affect the morphology of the resulting fibers. The average diameters of the neat and the carbendazim‐loaded electrospun PVA fibers ranged between 155 and 160 nm. The chemical integrity of the as‐loaded carbendazim in the carbendazim‐loaded electrospun PVA fiber mats was intact as verified by the ¹H‐nuclear magnetic resonance spectroscopy. Thermal properties of the carbendazim‐loaded electrospun PVA fiber mats were analyzed by differential scanning calorimetry and thermogravimetric analysis. The release characteristics of the carbendazim‐loaded electrospun PVA mats were investigated by the total immersion method in distilled water at 30°C. The carbendazim‐loaded electrospun PVA mats exhibited greater amount of carbendazim released than the carbendazim‐loaded as‐cast films. Copyright © 2010 John Wiley & Sons, Ltd.     

Development of a silica monolith microbioreactor entrapping highly activated lipase and an experiment toward integration with chromatographic separation of chiral esters

Microbioreactors are effective for high-throughput production of expensive products from small amounts of substrates. Lipases are versatile enzymes for chiral syntheses, and are highly activated when immobilized in alkyl-substituted silicates by the sol-gel method. For practical application of sol-gel immobilized lipases to a flow system, a microbioreactor loaded with a macroporous silica monolith is well suited, because it can be easily integrated with a chromatographic separator for optical resolution. We attempted to develop a microbioreactor containing a silica monolith-immobilized lipase. A nonshrinkable silica monolith was first formed from a 4:1 mixture of methyltrimethoxysilane (MTMS) and tetramethoxysilane (TMOS). It was then coated with silica precipitates entrapping lipase, derived from a 4:1 mixture of n-butyltrimethoxysilane (BTMS) and TMOS. As a result, monolith treated with the BTMS-based silicate entrapping lipase exhibited approximately ten times higher activity than nontreated monolith-immobilized lipase derived from the MTMS-based silicate, in transesterification between glycidol and vinyl n-butyrate in isooctane. A commercially available chiral column was connected in series to the monolith microbioreactor, and a pulse of substrate solution was supplied at the inlet of the reactor. Successful resolution of the racemic ester produced was achieved in the chromatographic column.     

大豆分离蛋白/聚乙烯醇的电纺研究

对大豆分离蛋白(SPI)/聚乙烯醇(PVA)的电纺进行了研究, 讨论了溶液性质和甘油的加入对SPI/PVA电纺纤维形貌的影响, 并对SPI/PVA电纺膜进行了成分分析和力学性能表征. 结果表明, 加入甘油可以提高SPI/PVA的可电纺性, 同时使SPI/PVA电纺膜的拉伸强度从不含甘油的(5.17±0.62) MPa下降到含有甘油的(1.67±0.21) MPa, 而伸长率呈增加趋势.     

Preparation and characterization of stable chitosan nanofibrous membrane for lipase immobilization

Nanofibrous membrane with a fiber diameter of 80-150 nm was fabricated from mixed chitosan/poly(vinyl alcohol) (PVA) solution by an electrospinning process. Field emission scanning electron microscope and transmission electron microscope were used to characterize the morphology of the nanofibrous membrane. It was found that chitosan nanofibrous membrane with stabilized morphology could be prepared through removing most of PVA from the nascent one with 0.5 M NaOH aqueous solution. This treatment also resulted in an obvious decrease in fiber diameter. The stabilized chitosan nanofibrous membrane was explored as support for enzyme immobilization due to the characteristics of excellent biocompatibility, high surface/volume ratio, and large porosity. Lipase from Candida rugosa was immobilized on the nanofibrous membrane using glutaraldehyde (GA) as coupling reagent. The properties of the immobilized lipase were assayed and compared with the free one. Results showed that, the observed lipase loading on this nanofibrous membrane was up to 63.6 mg/g and the activity retention of the immobilized lipase was 49.8% under the optimum condition. The pH and thermal stabilities of lipase were improved after it was immobilized on the chitosan nanofibrous membrane. In addition, the experimental results of reusability and storage stability indicated that the residual activities of the immobilized lipase were 46% after 10 cycles and 56.2% after 30 days, which were obviously higher than that of the free one.     

Study on morphology of electrospun poly(vinyl alcohol) mats

Submicron poly(vinyl alcohol) (PVA) fiber mats were prepared by electrospinning of aqueous PVA solutions in 6-8% concentration. Fiber morphology was observed under a scanning electron microscope and effects of instrument parameters including electric voltage, tip-target distance, flow rate and solution parameters such as concentration on the morphology of electrospun PVA fibers were evaluated. Results showed that, when PVA with higher degree of hydrolysis (DH) of 98% was used, tip-target distance exhibited no significant effect on the fiber morphology, however the morphological structure can be slightly changed by changing the solution flow rate. At high voltages above 10 kV, electrospun PVA fibers exhibited a broad diameter distribution. With increasing solution concentration, the morphology was changed from beaded fiber to uniform fiber and the average fiber diameter could be increased from 87 ± 14 nm to 246 ± 50 nm. It was also found that additions of sodium chloride and ethanol had significant effects on the fiber diameter and the morphology of electrospun PVA fibers because of the different solution conductivity, surface tension and viscosity. When the DH value of PVA was increased from 80% to 99%, the morphology electrospun PVA fibers was changed from ribbon-like fibers to uniform fibers and then to beaded fibers. The addition of aspirin and bovine serum albumin also resulted in the appearance of beads.     

Stability of new optical pH sensing material based on cross-linked poly(vinyl alcohol) copolymer

Cross-linked poly(vinyl alcohol) (PVA)-silica gel copolymer has been employed as a optical pH sensor substrate for immobilisation of fluorescein. Cross-linking was carried out by the sol-gel process incorporating PVA in initial sol-gel solution of tetra-methoxysilane (TMOS) under acidic conditions. Three dimensional network formation could be achieved using compositions of PVA/TMOS=80-90/20-10 vol.% to result in crack-free films. The fluorescent sensor layers were prepared by dip-coating of gel solution onto glass slides. The dynamic fluorescence response towards different pH values was investigated in terms of the influence of sample ionic strength, membrane composition as well as age of sol-gel layers. Depending on the composition of the matrix pK_a values of 6.50, 6.68 and 7.06 were found 18 days after continues storage in buffer.     

Immobilized Laccase on Activated Poly(Vinyl Alcohol) Microspheres For Enzyme Thermistor Application

Poly(vinyl alcohol) (PVA) microspheres were prepared by inverse suspension crosslinked method, with glutaraldehyde as a crosslinking agent. PVA microspheres activated with aldehyde groups were employed for Trametes versicolor laccase immobilization. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy were used to characterize the activated PVA microspheres and PVA microspheres with immobilized laccase (Lac/PVA microspheres), which show that laccase was successfully immobilized on the PVA microspheres. The optimum pH and temperature coupling conditions for the immobilized laccase were determined to be 3.3 and 30 °C, respectively. Residual activity was also investigated by soaking the immobilized laccase in organic solvents at different concentrations, proving it chemically stable. Immobilized laccase exhibited good storage stability at 4 °C. The enzyme biosensor showed good performance in 2,2-azinobis(3-ethylthiazoline-6-sulfonate) and bisphenol A, with concentration ranges of 2 to 8 mM and 0.05 to 0.25 mM, respectively. Therefore, PVA microspheres may have high potential as support for enzyme thermistor applications.     

Immobilization of cellulase in nanofibrous PVA membranes by electrospinning

Electrospinning is a nanofiber-forming process by which either polymer solution or melt is charged to high voltages. With high specific surface area and porous structure, electrospun fibrous membranes are excellent candidates for immobilization of enzymes. In this paper, immobilization of cellulase in nanofibrous poly(vinyl alcohol) (PVA) membranes was studied by electrospinning. PVA and cellulase were dissolved together in an acetic acid buffer (pH 4.6) and electrospun into nanofibers with diameter of around 200 nm. The nanofibrous membranes were crosslinked by glutaraldehyde vapor and examined catalytic efficiency for biotransformations. The activity of immobilized cellulase in PVA nanofibers was over 65% of that of the free enzyme. Nanofibers were superior to casting films from the same solution for immobilization of cellulase. The activity of immobilized cellulase descended with ascending in enzyme loading efficiency and crosslinking time, which retained 36% its initial activity after six cycles of reuse.     

电纺聚乙烯醇超细纤维膜的性能研究

由电纺制备聚乙烯醇(PVA)超细纤维膜,以扫描电镜观察纤维的微观形貌,用X射线衍射研究超细纤维膜的结晶行为,并测定了PVA超细纤维膜的力学性能和吸水性.结果表明,PVA超细纤维的平均直径为(184±26)nm,超细纤维中PVA的结晶度和晶体有序程度较浇铸膜低.超细纤维膜的拉伸强度、模量和断裂伸长率均较浇铸膜差,吸水率在300%以上,高于浇铸膜.     

Measurement of size‐dependent glass transition temperature in electrospun polymer fibers using AFM nanomechanical testing

The glass transition temperature (T_g) of individual electrospun polymer polyvinyl alcohol fibers of varying diameter was measured using atomic force microscopy (AFM) based nanomechanical thermal analysis. Indentation and bending of individual electrospun fibers using AFM allowed the calculation of the elastic modulus of the polyvinyl alcohol (PVA) fibers across a range of different temperatures. The elastic modulus of electrospun PVA fibers was observed to decrease significantly when passing through T_g, which allowed accurate determination of T_g. The T_g of electrospun PVA fibers was shown to decrease for smaller fiber diameters especially for fiber diameters below 250 nm. This size‐dependent glass transition behavior of electrospun PVA fibers is indicated as being due to polymer chain confinement. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Calix[n]arene Carboxylic Acid Derivatives as Regulators of Enzymatic Reactions: Enhanced Enantioselectivity in Lipase-Catalyzed Hydrolysis of (R/S)-Naproxen Methyl Ester

Candida rugosa lipase was immobilized with a sol–gel encapsulation procedure in the presence and absence of a calix[n]arene carboxylic acid derivative grafted onto magnetic nanoparticles or in the presence of the calix[n]arene carboxylic acid derivative with Fe₃O₄ magnetic nanoparticles as an additive. Through the enantioselective hydrolysis of racemic naproxen methyl ester and the hydrolysis of p-nitrophenylpalmitate, the relative enzyme activity was evaluated and tested. These results show that the encapsulated lipase without supports has lower conversion and enantioselectivity compared to the Calix[n]COOH-based encapsulated lipase. It has also been observed that the Calix[4]COOH-based encapsulated lipase has excellent enantioselectivity (enantiomeric ratio (E)?>?400) as compared to encapsulated-free lipase enantioselectivity (E?=?137), and it also has an enantiomeric excess value of ~98 % for S-naproxen.     

Preparation of electrospun chitosan/poly(vinyl alcohol) membranes

Electrospinning of chitosan from its solutions in 2% aqueous acetic acid was studied by adding poly(vinyl alcohol) (PVA) as a “guest” polymer. Properties of the chitosan/PVA solutions including viscosity, conductivity, and surface tension were measured, and effects of the polymer concentration, chitosan/PVA mass ratio and processing parameters (applied voltage, flow rate, capillary-to-collector distance) on the electrospinnability of chitosan/PVA were investigated. Analyses of scanning electron micrographs and transmission electron micrographs suggested that the chitosan/PVA ultrafine fibers were often obtained along with beads, and chitosan was located in the elctrospun fibers as well as in the beads. Uniform chitosan/PVA fibers with an average diameter of 99 ± 21 nm could be prepared from a 7% chitosan/PVA solution in 40:60 mass ratio. Results of Fourier transform infrared spectroscopy and X-ray diffraction demonstrated that there were possible hydrogen bonds between chitosan and PVA molecules, which could weaken the strong interaction in chitosan itself and facilitate chitosan/PVA electrospinnability. The electrospun chitosan/PVA membranes showed higher water uptake and would have potential applications in wound dressings.     

Thermal,morphological, and mechanical properties of ethyl vanillin immobilized in polyvinyl alcohol by electrospinning process

In this study, polyvinyl alcohol (PVA) nanofibers with ethyl vanillin as an active compound were prepared using electrospinning technique. The final products of electrospinning process were in the form of nanofibers films. PVA/ethyl vanillin nanofibers, having fibers diameters in the range 100–1700 nm, were successfully electrospun from ethanol/water mixture of PVA and ethyl vanillin. The effects of immobilization process on ethyl vanillin thermal properties were investigated by differential scanning calorimetry (DSC). The results of DSC showed significant influence of immobilization process on thermal properties of ethyl vanillin. It was noticed that melting point of immobilized ethyl vanillin was lower (~55 °C) compared to free flavor (~77 °C). Our results showed that films based on PVA/ethyl vanillin nanofibers are mechanically stable.     

二氧化硅/聚乙烯醇杂化电纺纤维膜的制备与结构形态

用溶胶-凝胶(Sol-Gel)法制备了不同二氧化硅含量的PVA/SiO2杂化纺丝液,将其电纺成纤维膜.XRD结果表明,杂化电纺纤维膜的结晶度较纯PVA电纺纤维膜小;FTIR证实了PVA的羟基与正硅酸乙酯水解后的羟基发生了缩合反应,杂化电纺纤维膜是以网络结构形式相结合的;FESEM表明,PVA/SiO2质量比为4∶1时,纤维光滑,分散比较均匀.随着二氧化硅含量的增加,纤维直径变细,纺锤形珠节结构增多.加入金属盐NaCl和MgCl2后,纤维直径变细,圆形珠节增多.从理论上分析了纤维膜结构形态的形成机理.     

Novel antibacterial fibers of quaternized chitosan and poly(vinyl pyrrolidone) prepared by electrospinning

The preparation of continuous defect-free fibers from quaternized chitosan derivative (QCh) has been achieved by electrospinning of mixed aqueous solutions of QCh with poly(vinyl pyrrolidone) (PVP). The average fiber diameter significantly decreases from 2800 to 1500 nm on increasing the polyelectrolyte content. In order to impart to QCh/PVP electrospun fibers stability to water and water vapor, the fibers have been crosslinked by incorporation of photo-crosslinking additives into QCh/PVP spinning solutions and subsequent UV irradiation of the electrospun fibers. Photo-crosslinked QCh-containing electrospun mats show high antibacterial activity against the Gram-positive bacteria Staphylococcus aureus and Gram-negative bacteria Escherichia coli.     

Ability of poly(vinyl alcohol) fibers to initiate graft copolymerization

It was noted in a graft copolymerization reaction involving a system of poly(vinyl alcohol) fibers (PVA fibers), methyl methacrylate, and water that fibers oxidized with hydrogen peroxide or sodium hypochlorite or ferric ion-adsorbing fibers effectively initiate the reaction as in the case of cellulose fibers. The initiation reaction of the sample was markedly activated by the presence of a pretreatment with an oxidizing agent at a concentration on the order of 10^?9 mole/l., but the oxidized samples were sharply deactivated by such means as reduction and oximation. Since model initiators for the present system, such as iron(III) acetylacetonate-adsorbing PVA fibers or ferric ion-adsorbing fibres, with the co-existence of acetylacetone were observed to initiate graft copolymerization effectively, it is believed that carbonyl groups in modified PVA fibers could be a major factor for initiating copolymerization through interaction with metallic ions.     

Preparation of New Calix[4]arene-Immobilized Biopolymers for Enhancing Catalytic Properties of Candida rugosa Lipase by Sol–Gel Encapsulation

The article describes preparation of new calixarene biopolymers consisting of the immobilization of convenience calixarene derivative onto cellulose and chitosan biopolymers, and the encapsulation of these calixarene biopolymers with Candida rugosa lipase within a chemical inert sol–gel supported by polycondensation with tetraethoxysilane and octyltriethoxysilane. The catalytic properties of immobilized lipase were evaluated into model reactions employing the hydrolysis of p-nitrophenylpalmitate and the enantioselective hydrolysis of naproxen methyl esters from racemic prodrugs in aqueous buffer solution/isooctane reaction system. The resolution studies using sol–gel support have observed more improvement in the enantioselectivity of naproxen E?=?300 with Cel-Calix-E than with encapsulated lipase without calixarene-based materials. Furthermore, the encapsulated lipase (Cel-Calix-E) was still retained about 39 % of their conversion ratios after the fifth reuse in the enantioselective reaction.     

Study of the effect of poly(vinyl alcohol) concentration on the gelation point of poly(vinyl alcohol) poly(acrylic acid) semi‐IPN systems as determined by viscoelastic measurements

We report on the determination of the gelation point of semi‐interpenetrating polymer networks (semi‐IPNs) composed of poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAAc) formed by a sequential method. The evolution of the viscoelasticity during the gelation reaction of acrylic acid (AAc) in solutions of PVA has been monitored through the sol‐gel transition with dynamic mechanical experiments. The gelation time of the system increased with PVA concentration; however, the molecular structure of the gel, composed of swollen clusters, is rather independent of the presence of PVA. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1944–1949, 2005     

改性海藻酸钠聚集行为对电纺纳米纤维形貌的影响

以过硫酸钾(KPS)为引发剂, 采用双丙酮丙烯酰胺(DAA)对海藻酸钠(SA)进行改性, 制备了海藻酸钠-聚双丙酮丙烯酰胺两亲性共聚物(SA-PDAA). 将SA-PDAA与聚乙烯醇(PVA)复配, 并进行静电纺丝, 制得SA-PDAA/PVA电纺纳米纤维. 通过红外光谱、 差示扫描量热和荧光光谱表征了SA-PDAA的结构和性能, 通过黏度仪、 表面张力仪和电导率仪测试了SA-PDAA纺丝液的物理性能, 用扫描电子显微镜表征了SA-PDAA/PVA电纺纳米纤维的形貌, 考察了SA-PDAA/PVA电纺纳米纤维的释药性能. 结果表明, DAA接枝到SA分子链上, SA-PDAA的临界聚集浓度为0.072 g/L, SA-PDAA具有良好的两亲性, SA-PDAA/PVA电纺纳米纤维具有均一的形貌. 改性后的SA可以有效地减缓药物释放速度, 提高SA-PDAA/PVA电纺纳米纤维的缓释性能.     

The negative biodegradation of poly(vinyl alcohol) modified by aldehydes

Due to the wide application of PVA acetals, the biodegradation of PVA modified by formaldehyde, n-butyraldehyde, glyoxaldehyde and glutaraldehyde was conducted in an intensive biodegradation environment. Spectrophotometric analysis and weight loss were used to determine the biodegradation of PVA, and the changes of the mechanical properties of PVA acetals were also studied.An obvious decrease in biodegradation levels of all the modified samples was found, and a decrease in biodegradation level with increasing degree of acetals of PVA. The biodegradation of poly(vinyl formal) is better than poly(vinyl butyral) with the same degree of acetals whereas the biodegradation levels of poly(vinyl glyoxal) are lower than poly(vinyl glutaral) which has the same degree of crosslinking. The difference between the FT-IR of the samples before and after biodegradation indicated scission of residual PVA chain during the process.