壳聚糖/聚乙烯醇/三聚磷酸钠三元复合微球的制备及其表征

由壳聚糖(CS)、聚乙烯醇(PVA)和三聚磷酸钠(TPP)制备了壳聚糖/聚乙烯醇/三聚磷酸钠三元复合微球,探讨了体系中壳聚糖含量对复合微球的影响,以及离子种类及浓度和pH值对复合微球溶胀度的影响。采用XRD、FTIR和SEM等测试技术对微球的组分、结构和形貌进行了表征。结果表明,CS和PVA具有良好的相容性,随着CS含量的增加,PVA的结晶性逐渐降低,复合微球的粒径约为400～950μm,表面较为粗糙;随着CS添加量的增加,凝胶平衡溶胀度先增大再减小,CS/PVA/TPP复合微球在pH值为3～8的溶胀度最大,且在同一种溶液中,随着离子浓度的增加,其溶胀度明显降低;复合微球具有溶胀-收缩可逆性,显示CS/PVA/TPP复合微球是pH/离子敏感型凝胶,可为药物缓释系统提供实验和理论依据。     

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.     

壳聚糖-聚丙烯酸复合水凝胶的药物控制释放行为

以壳聚糖(Cs)和丙烯酸(AA)为原料,利用自由基聚合法制备了具有孔洞结构的复合水凝胶Cs-PAA,并研究了AA的量、交联剂的量、聚合温度和AA的中和度对水凝胶溶胀度的影响以及复合水凝胶对烟酸的控制释放。 结果表明,Cs-PAA复合水凝胶具有良好的pH值、离子强度敏感性,且溶胀度最高达1228 g/g,其在pH=686的缓冲溶液中的烟酸累积释放率明显大于其在pH=1.80的缓冲溶液,因此Cs-PAA水凝胶可作为肠口服药物的载体。     

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.     

N-(2-磺酸基苯甲基)壳聚糖的合成、表征及其水凝胶的pH敏感性

通过两步反应合成了水溶性的N-(2-磺酸基苯甲基)壳聚糖(SBCS), 用IR, 1H NMR和UV-Vis谱对产物的结构进行了表征. 用胶体滴定法测定了N上2-磺酸基苯甲基的取代度. 以戊二醛为交联剂制备了N-(2-磺酸基苯甲基)壳聚糖水凝胶(SBCSG), 考察了凝胶在不同pH值缓冲溶液中的溶胀行为. 实验结果表明, SBCSG溶胀度随着凝胶交联度的增大而减小. 在碱性介质中SBCSG的溶胀度显著增大, 而在酸性介质中溶胀度显著减小, 在pH= 5.0缓冲液中的溶胀度达到最小值. SBCSG在碱性介质中的溶胀度随着侧链N上2-磺酸基苯甲基取代度增大而增大. 在pH=7.4的人工肠液和pH=1.0的人工胃液中SBCSG的溶胀-收缩具有可逆性, 显示出良好的pH敏感性. 有望作为pH敏感口服结肠定位给药系统药物载体.     

壳聚糖水凝胶微球的制备与溶胀性能

采用三聚磷酸钠(TPP)和六偏磷酸钠(SHMP)为复合交联剂,制备了离子交联网络结构的壳聚糖水凝胶微球。分析讨论了交联剂质量配比、pH以及离子强度等对壳聚糖微球溶胀性能的影响。结果表明:使用复合交联剂制备的微球的溶胀度比单独使用TPP或SHMP的分别低62.4%和41.3%,交联效率得到明显提高;当m(TPP)∶m(SHMP)=3∶5,交联剂pH=5时,制备的微球交联程度最好,结构最密实;在pH=1.2的缓冲溶液中,溶胀度可达到357%,而且凝胶没有任何破碎。微球具有较好的离子强度和pH敏感性,在酸性介质中有较高的溶胀度。     

PVA/P(AA-AM)水凝胶的制备及药物控制释放性能研究

以聚乙烯醇(PVA)、丙烯酸(AA)和丙烯酰胺(AM)为单体,过硫酸铵(APS)为引发剂、N,N'-亚甲基双丙烯酰胺(MBA)为交联剂,通过化学引发聚合制备互穿水凝胶PVA/P(AA-AM);用红外光谱(IR)、热重分析(TG)、差示扫描量热法(DSC)及扫描电镜(SEM)等测试方法对其进行了表征,并对其溶胀性能、p H敏感性以及离子强度对溶胀性能的影响进行了研究;并考察了该凝胶分别在p H=6.86和p H=1.80介质中对药物异烟肼和烟酸的控制释放行为。结果表明,PVA/P(AA-AM)水凝胶具有良好的p H、离子强度敏感性,在两种介质中异烟肼的累积释放率均高于烟酸,但异烟肼在p H=1.80的介质中的释放速度和累积释放率均高于其在p H=6.86的介质,烟酸则结果恰好相反。所以这种水凝胶有望用作靶向药物释放的载体。     

羧甲基壳聚糖水凝胶制备及其在药物控释中的应用

以戊二醛为交联剂制备了一系列羧甲基壳聚糖pH敏感水凝胶 .研究了合成条件对羧甲基壳聚糖水凝胶溶胀性能的影响 .实验结果表明羧甲基壳聚糖的脱乙酰度、交联剂用量对水凝胶溶胀率的影响较大 .pH=3 0时 ,水凝胶收缩 ,而pH =1 0 ,5 0 ,7 4 ,9 0时 ,水凝胶溶胀 ,且在碱性条件下水凝胶的溶胀率远大于酸性条件下的溶胀率 .包埋在此水凝胶中的水杨酸释放随载药介质的pH值和水凝胶半径大小的变化而显著不同 ,pH =1 0条件下载药的水凝胶的释药率大于pH =7 4 ,12 0条件下的释药率 ,且水凝胶的半径越大 ,释药速度和释药率也越大     

温度和pH双敏性PVME/CMCS水凝胶辐射交联制备及其性能

以聚甲基乙烯基醚(PVME)和羧甲基壳聚糖(CMCS)为原料, 采用电子束辐照交联方法制备聚甲基乙烯基醚/羧甲基壳聚糖(PVME/CMCS)水凝胶, 研究了温度、pH值、CMCS含量等对PVME/CMCS水凝胶溶胀度的影响, 同时以5-氟尿嘧啶(5-Fu)作模型药物, 初步探讨了凝胶药物释放性能. 结果表明, 辐射剂量在20—40 kGy时, 凝胶分数随辐射剂量的增加而快速增加, 辐射40 kGy以后趋于平衡. 在相同辐射剂量下, 随着体系中CMCS含量的增加, 凝胶分数反而减少. 该水凝胶具有一定的温度和pH敏感性, 其低临界溶解温度(LCST)在35 ℃左右, 并且在相同时间内和25及37 ℃下的溶胀反复可逆, 表现出较快的响应性. pH<3.0和pH>5.0时, 溶胀度较大; pH值为3.0~5.0时, 凝胶网络由于静电力收缩, 溶胀度较小. CMCS含量的增加和辐射剂量的减小均可提高凝胶载药量. 药物释放时间可通过改变体系中CMCS的含量和辐射剂量来调节.     

壳聚糖-丝心蛋白合金膜的研究(Ⅱ)──半互穿聚合物网络型膜对pH和离子的敏感性

研究了壳聚糖-丝心蛋白半互穿聚合物网络型膜对pH值和离子的敏感性,发现该膜在pH<3.3时溶胀度剧烈增加;在pH=2时,是否出现溶胀极大值与膜组分的含量及交联剂的含量有关;膜在不同pH值溶液中可交替溶胀和收缩,且这种溶胀-收缩行为重复可逆。同时,该膜在不同离子溶液中的溶胀度亦不同;在相同离子强度的溶液中,此膜在3价离子中的溶胀度最大。     

Effects of PVA,agar contents,and irradiation doses on properties of PVA/ws-chitosan/glycerol hydrogels made by γ-irradiation followed by freeze-thawing

Poly(vinyl alcohol) (PVA)/water soluble chitosan (ws-chitosan)/glycerol hydrogels were prepared by γ-irradiation and γ-irradiation followed by freeze-thawing, respectively. The effects of irradiation dose and the contents of PVA and agar on the swelling, rheological, and thermal properties of these hydrogels were investigated. The swelling capacity decreases while the mechanical strength increases with increasing PVA or agar content. Increasing the irradiation dose leads to an increase in chemical crosslinking density but a decrease in physical crosslinking density. Hydrogels made by irradiation followed by freeze-thawing own smaller swelling capacity but larger mechanical strength than those made by pure irradiation. The storage modulus of the former hydrogels decreases above 50 °C and above 70 °C it comes to the same value as that prepared by irradiation. The ordered association of PVA is influenced by both chemical and physical crosslinkings and by the presence of ws-chitosan and glycerol. These hydrogels are high sensitive to pH and ionic strength, indicating that they may be useful in stimuli-responsive drug release system.     

苯乙烯/马来酸酐共聚物智能水凝胶的制备与性能

合成了苯乙烯/马来酸酐共聚物接枝聚乙二醇400(PEG400)水凝胶.研究了环境pH、温度、离子强度对该凝胶溶涨性能的影响,并对凝胶的动态溶涨行为进行了分析.结果显示该水凝胶对环境pH、温度、离子强度等变化均作出体积相转变响应,表现出了智能高分子凝胶的特性.     

P(AA-DAC)两性聚电解质水凝胶的合成及性质

以丙烯酸(AA)和丙烯酰氧乙基三甲基氯化铵(DAC)为单体, 采用水溶液聚合法制备了P(AA-DAC)聚电解质水凝胶. 采用红外光谱和核磁共振等方法对其结构进行了表征. 研究了不同组成比的聚电解质水凝胶在去离子水、不同pH值溶液以及不同离子强度盐溶液中的溶胀行为. 研究结果表明, 摩尔比为1∶1的聚电解质水凝胶表现出典型的两性聚电解质凝胶的溶胀行为. 离子强度对其溶胀行为有着显著影响, 在溶液离子强度较高时, 凝胶网络的溶胀主要受溶剂向凝胶内部扩散所控制, 满足Fick型扩散规律n≤0.5, 随着溶液离子强度的增加, 凝胶网络平衡含水量增加, 扩散系数增大.     

Network structure and swelling behavior of poly(acrylamide/crotonic acid) hydrogels in aqueous salt solutions

Hydrogels with various ionic group contents were prepared from acrylamide and crotonic acid (CrA) monomers with 0–12.9 mol % CrA in aqueous solutions by radiation‐induced polymerization and gelation with γ rays from a ⁶⁰Co source. The volume swelling ratio of the poly(acrylamide/crotonic acid) hydrogels was investigated as a function of the pH and ionic strength of the swelling medium and the type of counterion in the swelling medium. The volume swelling ratio increased with an increase in pH and a decrease in the ionic strength. The volume swelling ratio of these hydrogels was evaluated with an equation, based on the Flory–Huggins thermodynamic theory, the James–Guth phantom network theory, and the Donnan theory of swelling of weakly charged ionic gels, that was modified here for the determination of the molecular weight between crosslinks (M_c) and the polymer–solvent interaction parameter (χ). The modified equation described very well the swelling behavior of the charged polymeric network. The same equation also provided the simultaneous measurement of these parameters for the systems investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1656–1664, 2003     

Preparation and characterization of hyaluronate-hydroxyethyl acrylate blend hydrogel for controlled release device

Hyaluronate-hydroxyethyl acrylate blend hydrogels were investigated as matrices for controlled release devices. Glycidyl methacrylate (GMA) derivatized HA (GMA-HA) was synthesized by coupling of GMA to HA in the presence of a suitable catalyst. These hydrogels were prepared by a free radical copolymerization of GMA-HA and hydroxyethyl acrylate. The water content of these hydrogels at equilibrium swelling in water (Ww) was 0.978+/-0.0073 (n=18); however, these hydrogel was mechanically tough and could be used as disk shape. The hydrogels swelling were found to depend on ionic strength and pH. The dried hydrogels quickly regained their original condition in water, and they swelled to more than 90% of its initial water contents after 30 min. This swelling-deswelling behavior was reproducible. The release of chlorpromazine HCl as a model cationic drug from the gels was suppressed significantly in water. The release increased with increasing the ionic strength and decreasing pH of bulk solutions.     

含甲基丙烯酸-N,N-二甲氨基乙酯水凝胶的紫外辐射合成及其性质研究

紫外光辐照 ,H2 O2 为光引发剂 ,N ,N′ 亚甲基双丙烯酰胺为交联剂合成了含甲基丙烯酸 N ,N 二甲氨基乙酯的水凝胶 .研究了水溶液中单体、光敏引发剂、交联剂浓度及光照时间对生成的水凝胶的凝胶含量和溶胀性能的影响 ,给出了最佳合成条件 .用该聚合法合成的聚甲基丙烯酸 N ,N 二甲氨基乙酯水凝胶不仅具有较好的透明性和适当的弹性 ,而且在 40℃和 pH =3时有明显的温度及 pH敏感性 .但离子强度对凝胶溶胀性能没有明显影响     

聚丙烯酰胺/聚异丙基丙烯酰胺互穿网络水凝胶的制备与性能

采用分步法用电子加速器辐射合成了聚丙烯酰胺(PAAm)/聚异丙基丙烯酰胺(PNIPAAm)互穿网络水凝胶,并考察了温度、pH值、离子强度对其溶胀性能的影响.研究表明:互穿水凝胶具有温度敏感性,且其体积相变与互穿网络中PAAm和PNIPAAm含量有关,随着网络中PAAm含量的增加水凝胶的体积相变趋于平缓,可以通过改变PAAm和PNIPAAm的组成比来控制水凝胶的体积相变行为.此外,互穿水凝胶还具有pH敏感性和一定的抗盐性.     

Radiation synthesis and uranyl‐ion adsorption of poly(2‐hydroxyethyl methacrylate/maleic acid) hydrogels

A new kind of copolymeric hydrogel adsorbent containing hydrophilic groups that both provides swelling in water and chelates with uranyl ions was synthesized, and its adsorptive ability for recovering uranium from aqueous media was investigated. The uranyl adsorption capacities of poly(2‐hydroxyethyl methacrylate/maleic acid) hydrogels were determined with a polarographic technique to be 3.2–4.8 (mg UO/g dry gel) from a 15‐ppm uranyl nitrate solution at pH, 6 depending on the molar content of maleic acid in the hydrogel. Adsorption studies showed that other stimuli, the temperature, and the ionic strength of the solution also have important roles in the uranyl‐ion adsorption capacity of these hydrogels. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 277–283, 2001     

The effect of external stimuli on the Bovine Serum Albumin adsorption capacity of poly(acrylamide/maleic acid) hydrogels prepared by gamma rays

The effects of external stimuli such as pH of the buffer solution, ionic strength, temperature and the amount of poly-electrolyte monomer in the hydrogel system on the Bovine Serum Albumin (BSA) adsorption capacity of poly(acrylamide/maleic acid) [P(AAm/MA)] hydrogels were investigated. Poly-electrolyte P(AAm/MA) hydrogels with varying compositions were prepared by irradiating acrylamide/maleic acid/water mixtures with γ rays at ambient temperature. Langmuir type adsorption isotherms were observed for all prepared hydrogels. Increase of ionic strength of the buffer solution from 0.01 to 0.1 mol dm⁻³ decreased the adsorption capacity of hydrogels and zero adsorption was observed in the presence of 0.1 mol dm⁻³ Na⁺ and Ca²⁺ ion in the adsorption medium. The adsorption capacity of hydrogels was found to increase from 0 to 120 mg BSA/g dry gel, by changing external stimuli and hydrogel composition.     

Swelling behaviors, tensile properties and thermodynamic studies of water sorption of 2-hydroxyethyl methacrylate/epoxy methacrylate copolymeric hydrogels

A series of copolymeric hydrogels based on 2-hydroxyethyl methacrylate (HEMA) and epoxy methacrylate (EMA) were synthesized by bulk polymerization. Swelling behaviors and tensile properties of hydrogels were studied. Dynamic swelling behaviors of copolymeric hydrogels indicate that the swelling process of these polymers follows Fickian behavior. The equilibrium water content (EWC) decreased and volume fraction of polymer in hydrogel (?₂) increased with EMA content increasing due to its hydrophobicity. The increase of ionic strength of swelling medium or temperature results in a decrease in EWC and an increase in values of ?₂. Young’s modulus and tensile strength of hydrogels, as well as effective crosslink density (v_e), increased as EMA content increased or ionic strength of swelling medium increased, attributing to increasing interaction between hydrophobic groups and polymer-polymer interaction with an increase in EMA content or in ionic strength. The polymer-solvent interaction parameter χ reflecting thermodynamic interaction was also studied. As EMA content, ionic strength of swelling medium or temperature increased, the values of χ increased. The values of χ and its two components χ_H and χ_S varied with increasing T. The negative values and trend of the enthalpy and entropy of dilution derived from values of χ_S and χ_H, could be explained on the basis of structuring of water through improved hydrogen bonding and hydrophobic interaction.