Poly(HEMA-co-AAm)水凝胶对氯霉素的缓释作用

采用本体共聚法制备poly(HEMA-co-AAm)（甲基丙烯酸羟乙酯与丙烯酰胺共聚物）水凝胶,采用恒温释放方法研究了poly(HEMA-co-AAm)水凝胶对氯霉素的缓释作用。结果表明,随水凝胶中AAm组分的含量增大,水凝胶对氯霉素的吸收量增大,氯霉素的释放速率也相应增大;随缓释介质的pH值下降,氯霉素的释放速率增大;在初始释放阶段,氯霉素的迁移速率随水凝胶中AAm组分的含量增大而增大,但随后并无明显影响。     

含硅水凝胶膜中Na+的渗透性

采用腔膜法测定Na 在γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH570)与甲基丙烯酸羟乙酯(HEMA)及N-乙烯基吡咯烷酮(NVP)共聚物水凝胶角膜接触镜材料中的渗透系数,研究了Na 渗透系数的影响因素。结果表明,Na 在水凝胶膜中的扩散过程为稳态扩散,其渗透系数随温度升高而显著增大,但温度超过60℃,Na 渗透系数的增大幅度显著下降;水凝胶膜中Na 的渗透系数随NVP及KH570质量分数增多而增大,但KH570的质量分数超过15%,Na 的渗透系数反而随KH570含量增多而减小,其原因在于Na 被聚合物中的微孔陷阱捕获而无法跳出。     

AM与HEMA共聚制备水凝胶接触镜材料及其溶胀性能

采用丙烯酰胺(AM)与甲基丙烯酸β-羟乙酯(HEMA)进行本体共聚制备水凝胶接触镜材料,研究了水凝胶的溶胀性能及其温度和pH值敏感性。结果表明,引发剂过氧化苯甲酰(BPO)用量为反应单体总质量的0.3%、反应温度80℃,产物溶胀之后为无色透明的玻璃状水凝胶;共聚物水凝胶具有较好的pH值敏感性,水凝胶在酸性溶液中溶胀,在碱性溶液中收缩:含有AM的水凝胶,其pH值敏感性较大:随AM的含量增大,共聚物水凝胶的溶胀速度和饱和含水量增大,随温度升高,水凝胶的饱和含水量下降,共聚物水凝胶中AM的含量对其温度敏感性无显著影响:SEM照片显示,AM与HEMA共聚物存在均匀的纤维状结构,并且共聚物中AM的含量越大,这种纤维状结构越大、越明显。     

丙烯酸β-羟丙酯/乙烯基吡咯烷酮共聚物及其水凝胶的合成和温敏行为的研究

用自由基共聚法合成了一系列 β-羟丙酯 (β-HPAT)和乙烯基吡咯烷酮 (NVP)的共聚物及其水凝胶。发现共聚物的水溶液有敏锐的温敏行为 ,最低汇溶温度 (LCST)随 NVP含量的增加而升高 ,随着反应单体总浓度的增加 ,相变敏锐性下降且 LCST也随之下降。通过考察水凝胶的溶胀率 (SR) ,发现共聚凝胶在适当的单体浓度、交联剂浓度和较宽的单体浓度配比范围内 ,有较灵敏的温敏行为     

含硅水凝胶角膜接触镜材料的脱水行为

采用重量法研究了γ–（甲基丙烯酰氧）丙基三甲氧基硅烷（KH570）与甲基丙烯酸–2–羟基乙酯（HEMA）及N–乙烯基吡咯烷酮（NVP）共聚物水凝胶角膜接触镜材料的脱水行为。结果表明,含硅水凝胶接触镜材料的脱水机理可采用两种极限情况下的幂律模型来描述,即脱水动力学级数n=0.5和n=1;当n=1时,水凝胶的失水率（Mt/M0c）与时间t成正比,为蒸发阶段;随后的脱水阶段中n=0.5,水凝胶的Mt/M0c与时间t1/2成正比,为扩散阶段;含硅水凝胶接触镜材料的脱水速率随单体NVP和 KH570含量增大而降低,随脱水温度的升高而提高,随盐离子浓度的增加而降低。     

P(AM/AMPS/NVP)降失水剂合成与耐温性能研究

采用自由基水溶液聚合法成功制备了丙烯酰胺(AM)/2-甲基-2-丙烯酰胺基丙磺酸(AMPS)/N-乙烯基吡咯烷酮(NVP)三元共聚耐温型降滤失剂,通过红外(FTIR)光谱和核磁C谱表征了共聚物的结构,通过元素分析考察了共聚物组成。热失重(TGA)表明,P(AM/AMPS/NVP)耐温性优于P(AM/AMPS)和P(AM),通过对三元共聚物的抗高温性和降失水性的研究,表明P(AM/AMPS/NVP)具有良好的耐温降滤失性能。     

三油酸甘油酯在共聚物水凝胶膜上的沉积作用

以N-乙烯吡咯烷酮、甲基丙烯酸羟乙酯以及甲基丙烯酸甲酯、甲基丙烯酸乙酯或者甲基丙烯酸丁酯为原料,采用本体共聚法制备共聚物水凝胶角膜接触镜材料,通过材料样品在三油酸甘油酯溶液中浸泡前后的浓度变化,计算沉积量,评价人眼泪液组分三油酸甘油酯在共聚物水凝胶角膜接触镜材料上的沉积作用。结果表明,三油酸甘油酯的沉积量随溶液浓度增大、沉积温度升高、沉积时间延长而增大;共聚物水凝胶材料中N-乙烯吡咯烷酮组分的含量越大,沉积量越大;而甲基丙烯酸甲酯、甲基丙烯酸乙酯或者甲基丙烯酸丁酯组分导致三油酸甘油酯的沉积量减小,以甲基丙烯酸甲酯最为明显。     

共聚物水凝胶接触镜材料与牛血清蛋白亲和性的影响因素

为了评价蛋白质在自行制备的共聚物水凝胶角膜接触镜材料上的沉积行为。将水凝胶膜样品置于牛血清蛋白(BSA)水溶液中,沉积一定时间后,采用染料染色结合分光光度法分析沉积前后牛血清蛋白浓度的变化,计算沉积量。实验发现,随沉积温度升高,牛血清蛋白的沉积量增大;沉积时间超过5天,仍然没有达到饱和沉积;牛血清蛋白的浓度越高,沉积量越大。共聚物水凝胶材料中,N-乙烯吡咯烷酮(NVP)组分的含量越大,沉积量越大;而甲基丙烯酸酯组分则导致牛血清蛋白的沉积量减小,以甲基丙烯酸甲酯(MMA)最为明显。     

水凝胶-水凝胶复合材料的制备与表征

将聚乙二醇400(PEG400)溶胀的交联N-乙烯吡咯烷酮(NVP)水凝胶微粒浸渍在含有引发剂过氧化苯甲酰(BPO)的甲基丙烯酸-2-羟基乙酯(HEMA)单体中并加热引发聚合反应,制备水凝胶-水凝胶复合材料,研究了产物的溶胀行为,并采用SEM、DSC对产物进行了表征。结果表明,水凝胶-水凝胶复合材料的饱和含水量随交联NVP水凝胶颗粒的含量及饱和含水量增大而增大,两种水凝胶之间的界面结构可分为包埋、部分互穿网络以及完全部分互穿网络等三种,其原因在于HEMA单体部分进入交联NVP水凝胶微粒并进行原位聚合的程度不同;处于分散相的水凝胶与处于连续相的水凝胶的吸水倍率不同,导致水凝胶-水凝胶复合材料吸水溶胀时不同相结构之间互相制约,处于分散相的水凝胶的大分子链不能充分伸展,非冻结水的熔融峰被自由水的熔融峰掩盖,表现为DSC谱图上非冻结水的熔融峰被自由水的熔融峰掩盖。     

聚乳酸-聚乙二醇热致复合水凝胶的制备及性能

将疏水性不同的共聚物混合制备可注射水凝胶。通过先核后臂法分别制备出线型聚乳酸-聚乙二醇(PLLAPEG)共聚物和星型聚乳酸-聚乙二醇单甲醚(PLLA-mPEG)共聚物,将两者水溶液进行混合,采用试管翻转法测定混合溶液热致相转变行为。结果表明:线型PLLA-PEG_(600)溶液相转变范围15—42℃,星型PLLA-mPEG750溶液相转变范围52—68℃,当星型PLLA-mPEG750溶液与线型PLLA-PEG_(600)溶液混合,形成了以疏水性较强的线型共聚物为核,疏水性较差的星型共聚物为壳的核壳结构复合物,其相转变温度介于2种共聚物相转变温度之间,可作为注射水凝胶。体外药物释放结果表明:复合水凝胶对所包载的盐酸乌拉地尔具有良好的缓释作用,动力学释放符合一级动力学方程。     

Kinetic degradation and controlled drug delivery system studies for sensitive hydrogels prepared by gamma irradiation

Ternary mixtures of N‐vinyl‐2‐pyrrolidone/itaconic acid and gelatin were irradiated by gamma rays at 30 kGy/s and at ambient temperature to prepared poly (NVP/IA and G) hydrogels. Poly (NVP/IA) hydrogels were prepared in different compositions (NVP/IA) mole ratio, (100/0), (98/1.5), (96.5/3.5), and (93/7.0) at 30 kGy. Then adding gelatin at different content (5, 10, 15, 20) mg to the best composition (NVP/IA/H₂O) (93/7)% for the characterization of network structure of these hydrogels, kinetic swelling drug release behavior and Scan Electron Microscope was studied. The equilibrium degree of swelling for P(NVP/IA) and P(NVP/IA/G) copolymer and the swelling‐degradation kinetics were also studies. According to dynamic swelling studies, both the diffusion exponent and the diffusion coefficient increase with increasing content of (IA), whereas, the addition of gelatin to (NVP/IA) composition by different content did not lead to any significant change in swelling percent. Also, the swelling behavior of copolymer hydrogels in response to pH value of the external media was studied, it is noted that the highest swelling values were at pH 4. The in vitro drug release behavior of these hydrogels was examined by quantification analysis with a UV/VIS spectrophotometers. Chlorpromazine hydrochloride was loaded into dried hydrogels to investigate the stimuli‐sensitive property at the specific pH and the drug release profile of these pH‐sensitive hydrogels in vitro. The release studies show that the highest value of release was at pH 4 which can be used for drug delivery system. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on Synthesis and Chloramphenicol Release of Poly（2-hydroxyethylmethacrylate-co-acrylamide） Hydrogels

In this article, poly（2-hydroxyethylmethacrylate-co-acrylamide） hydrogels were synthesized by bulk free-radical copolymerization of 2-hydroxyethylmethacrylate （HEMA） and acrylamide （AAm） for soft contact lens（SCL）-based ophthalmic drug delivery system. The copolymer was characterized with FT-IR and SEM, the swelling property of the hydrogels were studied by gravimetrical method, and chloramphenicol was used as a model drug to investigate drug release profile of the hydrogels. The results showed that poly（2-hydroxyethylmethacrylateco-acrylamide） hydrogels were transparent and useful SCL biomaterial, the water content increased as AAm content increase and pH decrease, and in the same way, hydrogel composition affected chloramphenicol release process too. Migration rate of chloramphenicol increased as the AAm content in the hydrogels increased in the first stage of diffusion process, whereas there was no significant difference thereafter.     

Synthesis,characterization, and application of PVP/PAM copolymer

The aim of this study was to synthesize copolymers from N‐vinyl‐2‐pyrrolidinone (NVP) and acrylamide (AM) at different molar ratios and investigate the influence of the different ratios on copolymers' properties. How copolymers affect the washing and stain‐repelling effects of carbon black, PET, Nylon, or cotton fabrics was also evaluated. Results show that as the AM content increased, the copolymers decomposed more slowly by heat, indicating better heat stability. In addition, copolymers were characterized as lowering surface tension and having excellent dispersing ability, low foaming properties, and excellent acid and alkaline resistance. The addition of copolymer can produce stain‐repelling effects against carbon black, PET, or Nylon‐colored fabrics. It was also determined that fabrics' stain‐repelling effects have no significant relationship to the NVP/AM molar ratio in copolymer synthesis. However, carbon black has better stain repellence as the AM monomer content increased. Two types of stain repellence gave better results when a higher concentration of copolymer was added. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 2006     

Radiation synthesis of interpenetrating polymer networks based on N‐vinyl pyrrolidone – acrylic acid copolymer and gelatin. I. Swelling,morphology, and thermal characterization for biomedical applications

Interpenetrating polymer networks (IPNs) based on N‐vinyl pyrrolidone (NVP) : gelatin (Ge), and a copolymer of NVP – acrylic acid (AA) : gelatin (Ge) were prepared using N‐N′methylenebisacrylamide (BIS) (0.5, 1% w/w) and glutaraldehyde (GLU) (0.5% v/v) as crosslinkers, respectively, by gamma irradiation technique. GLU was incorporated after irradiation to crosslink the gelatin chains, whereas BIS was placed in the respective solutions before irradiation. Several samples were prepared by varying the composition of gelatin to NVP or by changing the ratio of NVP : AA in preparing IPNs. The swelling behavior of the hydrogels was investigated as a function of variable doses, crosslinker (BIS) concentration, copolymer composition (NVP : AA ratio) or Ge : NVP ratio and pH of the immersion medium (3, 7.4, and 11). As expected, the swelling ratio increased with increasing acrylic acid content and decreased with increasing BIS content. No definite trend in the swelling behavior was observed as a function of dose. The interpenetration of the polymeric chains was established by morphological and thermal characterization. Scanning electron microscopy of IPNs showed a hybrid of coral and honeycomb structures as compared with the crosslinked polymers based on Ge and NVP (G_x and PVP_x). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1456–1463, 2007     

Photopolymerised thermo-responsive poly(N,N-diethylacrylamide)-based copolymer hydrogels for potential drug delivery applications

Novel thermo-sensitive N,N-diethylacrylamide (DEAAm) based copolymer hydrogels were prepared via UV-induced free radical bulk polymerisation. UV polymerisation was employed to avoid the use of potentially toxic solvents; solution polymerisation has been the most common means for the preparation of PDEAAm-based hydrogels in the literature to date. The resultant hydrogels were analysed using nuclear magnetic resonance, Fourier transform infrared spectroscopy and modulated differential scanning calorimetry. Parameters such as the crosslinking degree and the nature of the incorporated hydrophilic component, N-vinyl-2-pyrrolidone (NVP) or N,N-dimethylacrylamide (DMAAm) were found to impact hydrogel structure, mechanical properties and swelling kinetics. Pulsatile swelling studies indicated that the hydrogels had thermo-reversible properties which were greatly affected by test temperature, nature of hydrophilic monomer used and crosslinker content. Aminophylline was selected as a model solute for drug loading and release studies by thermal deswelling in HCl buffer (pH 1.4) and phosphate buffer media (pH 6.8). The observed lag time prior to significant drug release from the more crosslinked P(DEAAm-NVP) hydrogels could make them suitable for delayed specific release in the intestine and potential alternatives to layers or membranes in time-specific and site-specific swelling-controlled drug delivery systems.     

Swelling and drug‐release behavior of the poly(AA‐co‐N‐vinyl pyrrolidone)/chitosan interpenetrating polymer network hydrogels

A series of novel hydrogels were prepared from acrylic acid (AA), N‐vinyl pyrrolidone (NVP), and chitosan by photopolymerization. The swelling behavior, gel strength, and drug release behavior of the poly(AA/NVP) copolymeric hydrogels and corresponding interpenetrating polymer network hydrogels were investigated. Results showed that the swelling ratios for the present hydrogels decreased with an increase of NVP content in the gel, but the gel strength increased with an increase of NVP content in the gel. Results also showed that the drug‐release behavior for the gels is related to the ionicity of drug and the swelling ratio of the gel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2135–2142, 2004     

Gelation and degradation characteristics of in situ photo-crosslinked poly(l-lactide-co-ethylene oxide-co-fumarate) hydrogels

The objective of this work was to determine the gelation kinetics, extent of swelling, sol fraction, and degradation kinetics of photo-crosslinked poly(l-lactide-co-ethylene oxide-co-fumarate) (PLEOF) hydrogels, with N-vinyl-2-pyrrolidone (NVP) crosslinker, as a function of composition as well as the time and intensity of UV radiation. The gelation process was monitored by in situ rheometry. The crosslinking was shown to be facilitated by increasing NVP concentration up to a certain value above which the hydrogel shear modulus did not increase with additional amount of NVP. Increasing the hydrophobicity of PLEOF macromer resulted in a decrease in the hydrogel swelling ratio and increase in sol fraction which was due to a reduction in the apparent reactivity of the PLEOF fumarate units. The degradation characteristics of PLEOF hydrogels depended on the ratio of PLA to PEG with PLEOF 30/70 (30% lactide) having the highest degradation rate.     

Microspheres of copolymeric <Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone and 2-ethoxyethyl methacrylate for the controlled release of nifedipine

Free radical copolymerization of N-vinyl-2-pyrrolidone (NVP) with 2-ethoxyethyl methacrylate (EOEMA) was carried out with 2,2′-azobisisobutyronitrile (AIBN) initiator in 1,4-dioxane solvent at 60 °C. The resulting copolymers were characterized by FTIR, ¹H-NMR and ¹³C-NMR methods. Microspheres were prepared by varying the amount of NVP with respect to EOEMA. Nifedipine (NFD), a water-insoluble antihypertensive drug, was loaded into these microspheres by the oil in water emulsion technique followed by solvent evaporation. The effect of the proportion of NVP in the NVP/EOEMA copolymer on the controlled release of NFD from the microsphere matrix was investigated. Scanning electron micrographs (SEM) of the microspheres indicated spherical shapes in the size range 17–47 μm, even after loading with NFD. In vitro studies of the release of NFD from the NVP/EOEMA microspheres in pH 7.4 medium showed that the rate of NFD release was enhanced when the NVP content of the copolymer was high; the size of the microspheres also increased with increasing NVP content of the copolymer. Release data were analyzed using an empirical relation in order to elucidate the kinetics of the NFD release. This analysis indicated that a Fickian transport mode operates in this system.     

Radiation polymerization and controlled drug release of polymer hydrogels with NIPA and NVP

P(NIPA–NVP) and P(NIPA)/PVP interpenetrating polymer network hydrogels were synthesized by radiation polymerization in this article. Acetylsalicylic acid proved a model drug of salt resistance. Drug‐controlled release of these hydrogels containing acetylsalicylic acid was investigated. Influences of radiation dose, feed composition on the lower critical solution temperature (LCST), swelling behavior, salt dissolubility, and controlled release effect were discussed. The preferable preparation conditions for the titled aim were dose rate of 1 KGy/h, total dose of 30 KGy, feed monomer ratio of NIPA:NVP between 1:1 and 4:1, and total monomer concentration of 10%. As NVP content of the hydrogel increased, LCST rose, swelling ratios increased, salt resistance improved, and both swelling and deswelling rates slowed. Due to the ability of forming association complex, these hydrogels had the function of solubilization that made the drug release of difficult dissoluble medicine effective. These hydrogels had a higher drug release at physiological environment. The experimental results showed that these hydrogels were promising materials for causing solubilization and developing a long‐term controlled release system. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 724–729, 2003