蒙脱土纳米片增强的仿生结构强韧水凝胶薄膜

传统单网络水凝胶力学性能差,难以作为对力学强度和综合性能方面有高要求的硬脑膜修复材料使用。提高水凝胶的力学性能对于水凝胶的应用具有重要意义。本文通过蒸发诱导组装方法制备了聚乙烯醇/蒙脱土（PVA/MMT）水凝胶薄膜,该水凝胶薄膜具有优异的机械性能和抗疲劳性能。所制备的PVA/MMT水凝胶薄膜厚度为200 - 300 μm之间,断裂应力为9.5 ± 0.2 MPa、模量为9.0 ± 0.9 MPa、疲劳强度为1154.02 J?m-2,性能优于现有的生物聚合物水凝胶。加入蒙脱土（MMT）后,PVA/MMT水凝胶薄膜的机械性能得到提升。这得益于MMT在PVA/MMT水凝胶薄膜中形成有序的层状结构。PVA70/MMT30水凝胶薄膜借助戊二醛交联后,PVA和MMT之间形成C-O-C共价键,促使薄膜的机械性能进一步提高。     

聚乙烯醇和丙烯酸-β-羟乙酯水凝胶的摩擦学特性

合成水凝胶是由水溶性单体聚合得到的轻度交联的高分子柔顺链网络 .高分子交联网络与水之间的相互作用决定着水凝胶的物理化学性质[1,2 ] .水凝胶常应用于生物医学材料和生物传感器等方面 .如接触眼镜的材料就常用甲基丙烯酸 -β-羟乙酯和聚乙烯醇 (PVA)为主要成分的水凝胶 ,所以对其摩擦性质的研究会丰富对生物医用材料的认识 .关于水凝胶的摩擦性质的研究 ,除 Osada等[3] 研究了聚乙烯醇及一些天然水凝胶在几牛顿到几十牛顿的负载下的摩擦行为外 ,尚少报道 .PVA水凝胶的结晶度对其性能影响甚大 ,但他们没有涉及结晶度与 PVA水凝胶的摩…     

聚乙烯醇/壳聚糖复合水凝胶的物理化学性质

测定了聚乙烯醇(PVA)和壳聚糖(CS)复合水凝胶的平衡含水量、熔融焓、等温溶胀动力学和非等温失水动力学等性质,讨论了水凝胶的组成和制备参数对这些性质的影响.结果显示:PVA/CS复合水凝胶具有适宜于软骨修复替代材料的网络结构和平衡含水量.CS与PVA复合减弱了凝胶的结晶度,但却增强了水与凝胶支架的相互作用.尽管水凝胶力学拉伸强度有所降低,但却优化了凝胶的生物相容性和降解能力.PVA/CS复合水凝胶是一种潜在的软骨修复材料,作为一种理论研究的模型体系,它将促进热力学在复杂医用材料方面的应用.     

PVA水凝胶的弹性和溶胀特性研究

采用硼酸与聚乙烯醇化学交联方法制备了聚乙烯醇(PVA)水凝胶,通过对PVA水凝胶的弹性与溶胀性能的研究,优选出交联剂硼酸与聚乙烯醇的最佳配比量;探究温度对PVA水凝胶弹性的影响以及时间、矿化度、温度对PVA水凝胶溶胀特性的影响。结果表明,随硼酸用量的增加,PVA水凝胶的溶胀率与弹性模量值都表现出先增大后减小的特征,当硼酸:PVA=10%时,PVA水凝胶的弹性和溶胀特性均最佳;PVA水凝胶在水溶液中溶胀率随时间的增长逐渐增大,40h后基本达到溶胀平衡;随矿化度的增大而减少,耐矿化度强,在10%盐度水中还能膨胀1倍,适用于高矿化度油藏;耐温性强,随温度的增大变化不大,适用于油藏温度。     

冷冻/解冻制备的聚乙烯醇水凝胶的结构和流变性研究

研究了冷冻/解冻法制备的不同浓度(5wt%～25wt%)聚乙烯醇(PVA)水凝胶的结构和流变行为之间的关系.由XRD确定了凝胶中PVA的结晶度和晶粒尺寸.用应力流变仪研究了凝胶的流变行为,包括动态模量和蠕变等.在频率为1Hz和低应力的条件下,测量了凝胶的储能模量和损耗模量.在该试验条件下,PVA水凝胶的形变是完全可以回复的.低频率区和低应变区的储能模量随浓度增加而变大,但当浓度超过20wt%时,储能模量增加速率明显降低.由PVA水凝胶在1Hz时的储能模量和结晶度的数据,理论分析得到了形成PVA水凝胶的最低PVA浓度和最小结晶度.当PVA浓度低于15wt%时,储能模量主要由PVA的微晶控制,分子链间的氢键影响很小.通过低应变区储能模量的数值计算出了凝胶网孔尺寸的结构参数.同时对不同温度下PVA水凝胶的储能模量数据进行了标度分析.PVA水凝胶的蠕变行为显示,随浓度提高,凝胶的蠕变黏弹性由线性向非线性转变.     

肝素钠/聚乙烯醇复合水凝胶的制备与性能

通过循环冷冻-解冻法,制成了肝素钠/聚乙烯醇(HS/PVA)复合水凝胶材料。 探讨了不同质量分数肝素钠对复合水凝胶材料的可见光透过率、含水率、亲水性、力学性能以及肝素钠释放量的影响。 结果表明,复合水凝胶的可见光透过率为92%以上,溶胀平衡的含水率为72%~78%,亲水性较纯PVA水凝胶有所提升,拉伸强度和断裂伸长率都稍有下降。 细胞粘附实验结果表明,适量的肝素钠的释放可以达到减少细胞粘附的效果。 这种HS/PVA复合水凝胶材料有望用作人工角膜中心区材料。     

PVA-PAMPS-PAA三元互穿网络型水凝胶的合成及其性能研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)以及聚乙烯醇(PVA)为原料,制备了PVA-PAMPS-PAA三元互穿网络型(T-IPN)水凝胶.红外分析表明,PVA与PAA以及PAMPS之间形成了较强的氢键,使得PVA分子上的C—O伸缩震动吸收峰移向了低波数处.X射线衍射以及电镜分析表明,当PVA用量较低时,PVA能均匀的穿插于凝胶网络中,形成完善的互穿网络结构,当PVA用量过高时,部分的PVA结晶而使得凝胶出现相分离.研究了该三元互穿网络型水凝胶的溶胀性能,结果表明,该水凝胶的平衡溶胀比在200至340之间,并且随着AA以及AMPS用量的增加,凝胶的溶胀速率以及平衡溶胀比均升高.该三元互穿网络型水凝胶在酸性溶液中和在碱性溶液中表现出截然不同的消溶胀性能;并且随着溶液pH的升高,凝胶在pH=9.0附近出现体积突变,表现出pH敏感性.通过研究T-IPN水凝胶的抗压缩性能发现,利用线型高分子、柔性高分子网络以及刚性高分子网络制备的三元互穿网络型水凝胶能在高溶胀比下保持较高的强度.溶胀比为180的T-IPN水凝胶,其最大抗压缩强度可达12.1 MPa.进一步研究发现,凝胶的组成以及溶胀比均对凝胶的抗压缩强度和压缩应变均存在较大的影响.     

多孔PVA水凝胶的组成、形貌及泊松比等力学性能研究

制备了不同含量的纯聚乙烯醇(PVA)水凝胶和不同表面活性剂含量的多孔PVA水凝胶,采用数字散斑测量其泊松比,并使用电镜和显微镜观察其微观结构,探讨了纯PVA水凝胶与多孔PVA水凝胶组成、微观结构、泊松比、压缩模量和体积模量的变化及相互关系.研究发现,采用表面活性剂成孔,反复冷冻成型制备的闭孔结构水凝胶,其泊松比随应力应变增加而减小;随PVA含量增加而泊松比值减小;随表面活性剂含量增加,孔径变大,泊松比值减小.PVA水凝胶泊松比值与压缩模量和体积模量的比值成正比.     

聚乙烯醇/羧甲基壳聚糖共混水凝胶的辐射合成及性能

采用电子加速器辐照法制备了聚乙烯醇(PVA)/羧甲基壳聚糖(CMCH)共混水凝胶;研究了PVA与CMCH的配比、辐照剂量、温度以及pH值对PVA/CMCH共混水凝胶性能的影响.实验发现,PVA与CMCH在辐照剂量为40 kGy、配比为w(PVA)/w(CMCH)=5/1的条件下可得到强度较好的PVA/CMCH共混水凝胶,该水凝胶具有一定的温度和pH敏感性:在5~20℃时具有较高的溶胀率,温度在20℃以上溶胀率较低;水凝胶在pH<4.0和pH>6.0时溶胀率均较大,而当pH为4.0~6.0时溶胀率较小.     

PVA增强P(AAEA-co-AA)温度敏感性水凝胶的合成及其性能研究

以4-乙酰基丙烯酰乙酸乙酯(AAEA)、丙烯酸(AA)以及PVA为原料, 通过自由基溶液聚合法, 制备了PVA-P(AAEA-co-AA)半穿网络型(s-IPN)水凝胶. 红外分析表明, AAEA主要以烯醇式结构存在, 并且由于PAAEA, PAA以及PVA之间较强的氢键作用, 使得PAAEA以及PVA分子上的C-O伸缩振动吸收峰移向了低波数处. 电镜分析表明, PVA能贯穿于P(AAEA-co-AA)交联网络中, 从而有效阻碍凝胶的相分离|而XRD研究发现, 当PVA用量较少时, PVA能均匀的贯穿于凝胶网络中, 形成完善的互穿网络结构, 当PVA用量过高时, PVA不能有效地贯穿于聚合物交联网络中而出现结晶. 采用DSC对s-IPN水凝胶的体积相转变进行了研究, 结果表明, 该s-IPN水凝胶的体积相转变温度(VPTT)在54.0至57.8 ℃之间, 并且随着PVA用量的增加, 凝胶的VPTT逐渐升高. 研究了该s-IPN水凝胶的抗压缩性能, 结果表明, PVA与P(AAEA-co-AA)形成的半互穿网络结构能有效提高凝胶的抗压缩强度, 其最大抗压缩强度可达8.4 MPa. 对凝胶的温度敏感性研究发现, 当外界温度低于VPTT时, 凝胶能保持溶胀状态|而当温度高于VPTT时, 凝胶的平衡溶胀度迅速下降, 表现为温度敏感性.     

NMR characterization of styrene-divinylbenzene gel beads using freezing point depression of benzene

Freezing processes of benzene in the presence of styrene-divinylbenzene gel beads were investigated by proton nuclear magnetic resonance spectroscopy. Some portion of benzene in the pore did not freeze below its freezing point, which was detected until ?80°C. Temperature dependence of the amount of unfrozen benzene was discussed in relation to the pore size and the cross-linking density of gel beads. The small pore size and high crosslinking density increased the amount of unfrozen benzene, whereas the polymer matrix concentration showed little effect on the freezing processes. © 1995 John Wiley & Sons, Inc.     

Study of the self‐diffusion of poly(ethylene glycol)s in poly(vinyl alcohol) aqueous systems

We have measured the self‐diffusion coefficients of a series of oligo‐ and poly(ethylene glycol)s with molecular weights ranging from 150 to 10,000, in aqueous solutions and gels of poly(vinyl alcohol) (PVA), using the pulsed‐gradient spin‐echo NMR techniques. The PVA concentrations varied from 0 to 0.38 g/mL which ranged from dilute solutions to polymer gels. Effects of the diffusant size and polymer concentration on the self‐diffusion coefficients have been investigated. The temperature dependence of the self‐diffusion coefficients has also been studied for poly(ethylene glycol)s with molecular weights of 600 and 2,000. Several theoretical models based on different physical concepts are used to fit the experimental data. The suitability of these models in the interpretation of the self‐diffusion data is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2396–2403, 1999     

Physically crosslinked poly(vinyl alcohol)-hydroxyethyl starch blend hydrogel membranes: Synthesis and characterization for biomedical applications

Poly(vinyl alcohol), PVA is a polymer of great importance because of its many appealing characteristics specifically for various pharmaceutical and biomedical applications. Physically crosslinked hydrogel membranes composed of different amounts of hydroxyethyl starch (HES) in (PVA) and ampicillin were prepared by applying freeze–thawing method. This freezing–thawing cycle was repeated for three consecutive cycles. Physicochemical properties of PVA–HES membrane gel such as gel fraction, swelling, morphology, elongation, tensile strength, and protein adsorption were investigated. Introducing HES into freeze–thawed PVA structure affected crystal size distribution of PVA; and hence physicochemical properties and morphological structure have been affected. Increased HES concentration decreased the gel fraction %, maximum strength and break elongation. Indeed it resulted into a significant incrementing of the swelling ability, amount of protein adsorption, broader pore size, and pore distribution of membrane morphological structure. Furthermore, an increase in HES concentration resulted in better and still lower thermal stability compared to virgin PVA and freeze–thawed PVA. The maximum weight loss of PVA–HES hydrogel membranes ranged between 18% and 60% according to HES content, after two days of degradation in phosphate buffer saline (PBS), which indicates they are biodegradable. Thus, PVA–HES hydrogel membranes containing ampicillin could be a novel approach for biomedical application e.g. wound dressing purposes.     

Estimation of polyacrylamide gel pore size from Ferguson plots of normal and anomalously migrating DNA fragments. I. Gels containing 3% N,N'-methylenebisacrylamide

The mobilities of normal and anomalously migrating DNA fragments were determined in polyacrylamide gels of different acrylamide concentrations, polymerized with 3% N,N'-methylenebisacrylamide as the crosslinker. The DNA samples were a commercially available 123-bp ladder and two molecular weight ladders containing multiple copies of two 147-base pair (bp) restriction fragments, obtained from the MspI digestion of plasmid pBR322. One of the 147 bp fragments is known to migrate anomalously slowly in polyacrylamide gels. Ferguson plots were constructed for all multimer ladders, using both absolute mobilities and relative mobilities with respect to the smallest DNA molecule in each data set. If the retardation coefficients were calculated from the relative mobilities, and the rms radius of gyration was used as the measure of DNA size, the Ogston equations were obeyed and the gel fiber parameters could be calculated. The effective pore sizes of the gels were estimated from the gel concentration at which the mobility of a given DNA molecule was reduced to one-half its mobility at zero gel concentration. The estimated pore radii ranged from approximately 130 nm for 3.5% gels to approximately 70 nm for 10.5% gels. These values are much larger than the pore sizes previously determined for the polyacrylamide matrix.     

Multiple use of slab gels in sequencing apparatus for separation of polymerase chain reaction products

Attempting to assess whether a decrease of the electrophoresis temperature could prevent or reduce the extent of gel well deformations, and whether the utilization of native polyacrylamide gels (without urea) could speed up the separation of polymerase chain reaction (PCR)-amplified products with an automated 377 DNA sequencer, denatured PCR products were subjected to electrophoresis in 6% native gels under 45 degrees C. Results show that a decrease of the electrophoresis temperature from 51 degrees C (recommended by the User's Manual) to 45 degrees C substantially facilitates the preservation of gel wells, and that all PCR products tested migrate significantly faster in native than in denatured (with urea) gels of the same concentration. The combination of a 6% native gel and a lower (45 degrees C) electrophoresis temperature permits multiple uses of a given gel with consistent results, consequently reducing the electrophoresis time and reagent costs.     

Time-resolving analysis of cryotropic gelation of water/poly(vinyl alcohol) solutions via small-angle neutron scattering

The structural transformations occurring in initially homogeneous aqueous solutions of poly(vinyl alcohol) (PVA) through application of freezing (-13 degrees C) and thawing (20 degrees C) cycles is investigated by time resolving small-angle neutron scattering (SANS). These measurements indicate that formation of gels of complex hierarchical structure arises from occurrence of different elementary processes, involving different length and time scales. The fastest process that could be detected by our measurements during the first cryotropic treatment consists of the crystallization of the solvent. However, solvent crystallization is incomplete, and an unfrozen liquid microphase more concentrated in PVA than the initial solution is also formed. Crystallization of PVA takes place inside the unfrozen liquid microphase and is slowed down because of formation of a microgel fraction. Water crystallization takes place in the early 10 min of the treatment of the solution at subzero temperatures, and although below 0 degrees C the PVA solutions used for preparation of cryogels should be below the spinodal curve, occurrence of liquid-liquid phase separation could not be detected in our experiments. Upon thawing, ice crystals melt, and transparent gels are obtained that become opaque in approximately 200 min, due to a slow and progressive increase of the size of microheterogeneities (dilute and dense regions) imprinted during the fast freezing by the crystallization of water. During the permanence of these gels at room temperature (for hours), the presence of a high content of water (higher than 85% by mass) prevents further crystallization of PVA. Crystallization of PVA, in turn, is resumed by freezing the gels at subzero temperatures, after water crystallization and consequent formation of an unfrozen microphase. The kinetic parameters of PVA crystallization during the permanence of these gels at subzero temperatures are the same shown by PVA during the first freezing step of the solutions.     

Microporous,Thermosensitive Organic-Inorganic Hybrid Hydrogel Prepared by Freezing

Thermally triggered shrinking rates of poly(N-isopropyl-acrylamide) (PNIPA) -based organic-inorganic hydrogel could be accelerated by applying the ice templating method. Freezing and subsequent rehydration of gels is an effective way to prepare the porous polymer network that leads to rapid expelling of pore water. The shrinking coefficients obtained by fitting Fick's law to the data increased two orders of magnitude as compared with the conventional gel before freezing. The microstructure of gels generated during freezing gels had advantage to expel the pore water rapidly probably due to the PNIPA aggregation through the hydrophobic interaction.     

Microstructure of acid-induced caseinate gels containing sucrose: quantification from confocal microscopy and image analysis

We investigate the effect of sucrose on the microstructure of sodium caseinate gels induced by acidification. The average pore size and the fractal properties of two-dimensional slices of the gels are studied using confocal scanning laser microscopy and image analysis. The addition of sucrose promotes stronger and more fine-stranded gels while re-arrangements of the network tend to be prevented. Whereas the fractal dimension itself is not sensitive to changes in the gel microstructure upon addition of sucrose, the maximum cut-off distance, up to which fractal scaling behaviour applies, is substantially reduced, as is the average pore size. The overall microstructural changes seem to be consistent with previous rheological and light scattering studies of the same system.     

Microporous, fast response cellulose ether hydrogel prepared by freeze-drying

A simple and effective method of preparing fast-response gels is developed. The freeze-drying and subsequent rehydration of thermosensitive gels alters the microstructural properties of the gels in a way that leads to rapid shrinking rates. Microporous hydroxypropyl cellulose (HPC) gels were created by this method to investigate the influence of the process on the swelling and shrinking kinetics of the gels in response to temperature changes. Micropores of different size ranges were produced by freezing gels with different amounts of water at −20 °C. Water content was the key factor to control the microporosity and the shrinking rates of gels. After the freezing treatment, an effective diffusion coefficient for shrinking could be determined by fitting Fick's law to the data (5.2 × 10⁻⁴ cm²/s). This was an increase of two orders of magnitude over that of the untreated, non-porous gel (6.0 × 10⁻⁶ cm²/s). The magnitude of the shrinking coefficient indicates that the shrinking rate of the microporous gel is probably limited by the convective flow, as unsteady flow through porous media follows the same differential equation as Fick's law, but with much greater transport coefficients, as observed here. Physically, the shrinking rate may be determined by the level of interconnected-cells in a microporous structure present at the beginning of shrinking process because the convection through the interconnected-cells is estimated to be much slower than the polymer network diffusion rate of the struts of micropores (0.1–3.0 μm) as well as heat transfer.     

Hyaluronic acid‐poly(vinyl alcohol) composite cryo‐gel for biofunctional material application

Recently, applications of hyaluronic acid (HA) as a biomaterial were investigated. However, the weak structure of HA gel and the effects of using cross‐linker raised concerns during in vivo resolution. In this study, we investigated the method to solve these two problems using physical cross‐linking and compositing with poly(vinyl alcohol) (PVA). Various weight ratios of HA and PVA solutions were mixed, adjustment of pH to 1.8 using HCl then used to fabricate HA‐PVA cryo‐gel by freezing‐thawing. Young's modulus of the prepared gel rose with the increase of both HA and PVA concentrations or either one of them. We estimated that HA and PVA have exhibited these mechanical properties due to forming a double network. HA‐PVA gel showed kinetic friction force of approximately 10 times of PVA gel, while water contact angle and protein adsorption of HA‐PVA gels were remarkably decreased. The properties of the prepared gel suggest that it can be used for postoperative adhesion prevention applications.