pH、离子强度敏感性壳聚糖水凝胶的合成及其对辅酶A的控制释放

以壳聚糖(CS),L-天冬氨酸(ASP)和戊二醛(GA)为原料,合成了具有pH、离子强度敏感性的壳聚糖水凝胶CS-GA-ASP.研究了交联剂含量、pH、离子强度对水凝胶溶胀率的影响和水凝胶对辅酶A的控制释放.结果表明,水凝胶在酸性溶液中,溶胀率最大,在中性溶液中溶胀率最小;水凝胶在不同pH或不同离子强度的溶液中交替放置时,表现出良好的溶胀-退胀可逆性;在室温下,pH=3.7、6.8、9的缓冲溶液中,辅酶A的累积释放率分别为78%、92%和87%,且在pH=6.8的缓冲溶液中,辅酶A释放速率最快,在pH=3.7的缓冲溶液中时,辅酶A释放速率最慢.     

P(HEMA-co-MAA)纳米凝胶的制备与pH响应性

以甲基丙烯酸羟乙酯(HEMA)和甲基丙烯酸(MAA)为聚合单体,异辛烷为分散介质,Span80和Tween80为复配乳化剂,采用反相微乳液聚合法制得不同单体配比的聚(甲基丙烯酸羟乙酯-co-甲基丙烯酸)(P(HEMA-co-MAA))纳米凝胶。确定了产物的pKa值及实际单体物质的量比,对产物的形貌进行了表征并研究了产物的pH响应性.结果显示,MAA物质的量分数为20%的纳米凝胶的pKa值为5.83,在pH=3和pH=7时其数均粒径分别为48 nm和90 nm;当环境pH接近pKa值时,纳米凝胶分散液的浊度明显降低,溶胀率明显上升,表观黏度急剧增加,说明纳米凝胶具有良好的pH响应性。     

SA分子量及用量对SA/PNIPAAm semi-IPN水凝胶溶胀性能的影响

研究了海藻酸钠(SA)的分子量及用量对SA/聚(N-异丙基丙烯酰胺)半互穿网络(SA/PNIPAAm semi-IPN)水凝胶的平衡溶胀度、溶胀速率和消溶胀速率的影响。结果发现,水凝胶平衡溶胀度随着凝胶网络中SA组分分子量以及用量的增加而增大;在pH=1.0条件下,SA/PNIPAAm semi-IPN水凝胶的溶胀速率随着SA的分子量以及用量的增加而降低,在pH=7.4条件下,水凝胶的溶胀速率随着SA的分子量以及用量的增加而增大;SA用量较低时,分子量的大小对SA/PNIPAAm semi-IPN水凝胶的消溶胀速率有很大影响,随着SA用量的增加,分子量大小对水凝胶消溶胀速率的影响作用降低。     

羧甲基纤维素钠/聚(N-异丙基丙烯酰胺)半互穿网络水凝胶的制备及溶胀性能

制备了具有温度、pH双重敏感特性的羧甲基纤维素钠／聚（N-异丙基丙烯酰胺）的半互穿网络水凝胶（CMC／PNIPAAm semi—IPN）。研究了温度、pH对该凝胶溶胀度的影响。结果表明,在酸性（pH=1．0）和弱碱性（pH=7．4）条件下,semi—IPN凝胶溶胀度均随着温度的升高而下降,但在pH=1．0时,semi-IPN凝胶的溶胀度小于PNIPAAm凝胶的溶胀度;在pH-7．4时,结果正好相反。20℃时,该凝胶有良好的pH敏感性;而37℃时,敏感性不明显。同时对该凝胶的消溶胀动力学进行了研究,结果发现,试凝胶的消溶胀速率随着凝胶中CMC组分含量的增加而增大。     

pH敏感P(MAA-co-AM)水凝胶的制备及溶胀行为研究

以甲基丙烯酸(MAA)、丙烯酰胺(AM)为单体,N,N-亚甲基双丙烯酰胺作交联剂(BIS),过硫酸铵为引发剂(APS),用溶液聚合的方法合成水凝胶P(MAA-co-AM),研究了单体配比及干燥方式对水凝胶表面形貌以及对水、不同pH溶液及盐溶液的溶胀行为的影响。结果表明,P(MAA-co-AM)16凝胶(MAA/AM摩尔比为16∶100)冻干处理后具有均匀的大孔;与PAM和PMAA凝胶相比,P(MAA-co-AM)16凝胶的吸水溶胀速率快(1h溶胀平衡)、平衡溶胀比大(ESR=250)、pH体积响应变化大(pH为4.01、6.86、9.18时的ESR分别为20、60、141),吸盐率比PMAA有所提高。     

不同条件对PVA/CS复合水凝胶溶胀性能的影响

以聚乙烯醇(PVA)、壳聚糖(CS)为原料,戊二醛为交联剂,制备出PVA/CS复合水凝胶载体材料,改变PVA/CS的质量配比、交联剂含量、pH值和温度,考察了不同条件下对复合水凝胶溶胀性能的影响.结果表明,当PVA/CS质量比为3:1、交联剂体积分数为4%时所合成凝胶的溶胀性能较好;随着温度的升高,溶胀度不断减小;凝胶在酸性条件的溶胀性能远远优于碱性条件的溶胀性能.     

形状记忆型水凝胶的制备及其在药物控制释放中的应用

以戊二醛为交联剂,制备了pH敏感性明胶-果胶水凝胶(GT-PT)和明胶-辛基果胶水凝胶(GT-OPT),研究了交联剂用量、温度、pH值对凝胶溶胀性能的影响及溶胀-消溶胀性能。结果表明,当温度在30～60℃时,凝胶的溶胀率随温度的升高而增大;且具有明显的pH敏感性,碱性条件下的溶胀率大于酸性条件下的溶胀率;不同pH值条件下,明胶-果胶水凝胶具有"形状记忆"功能。包埋在水凝胶中的牛血清蛋白在pH=1.0时的释药率大于pH=7.8和pH=9.18时的释药率。此类水凝胶有望用于蛋白质的pH值及温度控制释放。     

pH敏感性壳聚糖/聚乙烯醇水凝胶的制备及其性能研究

制备了pH敏感性壳聚糖/聚乙烯醇(CS-PVA)水凝胶,研究了该水凝胶在室温下不同pH值介质中的溶胀比。发现在酸性溶液中,凝胶的溶胀比远大于在碱性溶液中的溶胀比,且其在不同pH值溶液中具有可逆溶胀-收缩行为,对药物氟哌酸具有缓释效果。     

抗冻pH敏感水凝胶聚α-甲基丙烯酸/丙烯酰胺的制备及性能研究

pH敏感水凝胶具有高含水、低摩擦、环境敏感等优良性能,在生物医药,环保等领域广为运用,但传统水凝胶因为低温易凝固限制了其应用范围。本实验以CaCl_2为增强剂,通过原位自由基聚合制备耐低温的水凝胶聚α-甲基丙烯酸/丙烯酰胺[P(AM/MAA)]。考察时间和pH对水凝胶P(AM/MAA)溶胀行为的影响,并重点探讨了低温对P(AM/MAA)凝固的影响。结果表明:添加了CaCl_2的P(AM/MAA)抗冻性能优越,pH敏感性能突出。     

温度/pH双重敏感性芦苇半纤维素基水凝胶的制备与表征

通过自由基聚合反应制备出以芦苇半纤维素为基材的温度/pH双重敏感性水凝胶材料。考察不同单体丙烯酸(AA)和N-异丙基丙烯酰胺(NIPAAm)摩尔比对其温度和pH的响应能力,探讨水凝胶的形成机制和消溶胀动力学行为。结果表明,四种不同单位摩尔比水凝胶均具有温度和pH双重敏感性,NIPAAm摩尔比含量高的水凝胶对温度响应更为敏感,而结构中的AA对水凝胶pH敏感行为起主要作用,消溶胀动力学符合准一级模型,消溶胀速率随NIPAAm摩尔比增加而加大。     

内盐凝胶的制备及对烟酰胺的控释

以甲基丙烯酸二甲基氨基乙酯(DMAE-MA)、衣康酸(IA)、亚甲基双丙基酰胺(BIS)和过硫酸钾(KPS)为原料在室温下制备内盐凝胶。研究了原料配方对凝胶形成的影响、内盐凝胶的吸水动力学及溶胀机制、凝胶的pH值敏感性以及对烟酰胺的负载与负载凝胶在不同pH值介质中的释放行为,并用红外光谱对凝胶结构进行了表征。结果表明,n(IA)/n(DMAEMA)>1后将降低单体的转化率,不利于凝胶的形成;内盐凝胶不具有高吸水性,其吸水溶胀机制符合Fickian扩散;在pH值为12的缓冲溶液中溶胀率比在pH值为3的缓冲溶液中高;凝胶对烟酰胺的负载率可以超过200%。在25℃下,烟酰胺在pH值为3的介质中释放比在pH值为12的介质中释放快。     

多重响应性P(AAEA-co-DMAA)水凝胶的合成及其性能研究

以具有多重响应性的新型单体4-乙酰基丙烯酰乙酸乙酯(AAEA)和N,N′-二甲基丙烯酰胺(DMAA)为原料,采用溶液自由基聚合法合成了具有多重响应性的水凝胶,研究了凝胶的溶胀行为以及在不同离子强度、温度、pH值条件下共聚水凝胶的响应性能。结果表明,随凝胶中AAEA含量的增加,凝胶的溶胀方式由Fick型转变为非Fick型;凝胶对外界离子强度、温度、pH值的变化产生响应,当NaCl浓度约为0.1mol/L时,凝胶的离子响应性出现较大的突变;随温度的升高,凝胶疏水性增大,85℃时凝胶的保水率只有60%;低pH值时,凝胶收缩,随pH值的增大,凝胶内P-AAEA部分解离加剧,静电斥力使凝胶溶胀。     

Preparation,properties, and drug release of thermo- and pH-sensitive poly((2-dimethylamino)ethyl methacrylate)/poly(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diethylacrylamide) semi-IPN hydrogels

In this paper, a series of semi-interpenetrating polymer network (semi-IPN) hydrogels based on poly((2-dimethylamino)ethyl methacrylate)/poly (N,N-diethylacrylamide) (PDMAEMA/PDEA) were synthesized by changing the initial PDMAEMA/DEA molar ratio at room temperature. The influence of this additive on the property of resulting PDEA hydrogels was investigated and characterized. The interior morphology by scanning electron microscopy (SEM) revealed that the semi-IPN hydrogels have interconnected porous network structures. The glass transition temperature (T _g) of the semi-IPN hydrogels was observed by differential scanning calorimetry (DSC). Equilibrium swelling ratio (ESR), swelling and deswelling dynamics of the hydrogels responding to temperature and pH were investigated in detail. Compared to PDEA, the semi-IPN hydrogels exhibited excellent mutative values in response to an alternation of the temperature and pH, and showed fast swelling and deswelling rates in response to temperature and pH change. The release behaviors of the model drug, aminophylline, were found dependent on hydrogel compositions and environmental temperature. These results suggest that the stimuli semi-IPN hydrogel have potential application as intelligent drug carriers.     

Thermo- and pH-sensitive behavior of hydrogels based on oligo (ethylene glycol) methacrylates and acrylic acid

Novel dual stimuli-responsive hydrogels were prepared by free-radical polymerization of 2-(2-methoxyethoxy) ethyl methacrylate (MEO₂MA) and oligo (ethylene glycol) methacrylate (OEGMA), as thermosensitive monomers, and acrylic acid (AAc), as a pH-sensitive monomer. Due to the thermosensitive monomers introduced in the macromolecular network, the synthesized materials possessed tunable thermal behavior. In addition, as well as by introducing in the polymerization feed pH-sensitive monomer AAc, the equilibrium swelling properties of the hydrogels can be tuned by three comonomers. Moreover, the de-swelling kinetics was studied by changing temperature and/or pH, and they could be well described with a first-order kinetics equation. Especially, the faster shrinking rates of hydrogels were observed when the simultaneous temperature and pH stimuli changed from pH 8/18 to pH 2/55 °C because of the cooperative thermo-/pH responses. The prepared dual temperature-/pH-sensitive PMOA hydrogels as a new material candidate may provide significant valuable information for various potential applications.     

壳聚糖/聚(N-异丙基丙烯酰胺)全互穿网络水凝胶的制备及性能

以壳聚糖(CS)和N-异丙基丙烯酰胺(NIPAAm)为原料,N,N'-亚甲基双丙烯酰胺(BIS)为交联剂,制备具有温度和pH值双敏感性的全互穿网络水凝胶(Full-IPN);利用红外光谱(FT-IR)对其分子结构进行表征,扫描电镜(SEM)观察其内部形貌,并通过DSC对其低临界溶解温度(LCST)进行表征,最后研究了不...     

快速响应的聚(N-异丙基丙烯酰胺)水凝胶的合成及性能

以羧甲基纤维素的水溶液为反应介质制备了快速响应的温度敏感性聚(N-异丙基丙烯酰胺)水凝胶。利用DSC对其相转变温度进行了表征,并测定了不同温度下达到平衡时水凝胶的溶胀比,研究了水凝胶的去溶胀动力学。结果表明,在聚合/交联过程中羧甲基纤维素的存在对PN IPA水凝胶的相转变温度几乎没有影响;与传统水凝胶相比,该水凝胶的溶胀性能有所提高,并且具有较快的响应速率。     

Preparation and characterization of hybrid pH-sensitive hydrogels of chitosan-co-acrylic acid for controlled release of verapamil

In the present work crosslinked hydrogels based on chitosan (CS) and acrylic acid (AA) were prepared by free radical polymerization with various feed compositions using N,N methylenebisacrylamide (MBA) as crosslinking agent. Benzoyl peroxide was used as catalyst. Fourier transform infrared spectra (FTIR) confirmed the formation of the crosslinked hydrogels. This hydrogel is formed due to electrostatic interaction between cationic groups in CS and anionic groups in AA. Prepared hydrogels were used for dynamic and equilibrium swelling studies. For swelling behavior, effect of pH, polymeric and monomeric compositions and degree of crosslinking were investigated. Swelling studies were performed in USP phosphate buffer solutions of varying pH 1.2, 5.5, 6.5 and 7.5. Results showed that swelling increased by increasing AA contents in structure of hydrogels in solutions of higher pH values. This is due to the presence of more carboxylic groups available for ionization. On the other hand by increasing the chitosan content swelling increased in a solution of acidic pH, but this swelling was not significant and it is due to ionization of amine groups present in the structure of hydrogel. Swelling decreased with increase in crosslinking ratio owing to tighter hydrogel structure. Porosity and sol-gel fraction were also measured. With increase in CS and AA contents porosity and gel fraction increased, whereas by increasing MBA content porosity decreased and gel fraction increased. Furthermore, diffusion coefficient (D) and the network parameters i.e., the average molecular weight between crosslinks (M_c), polymer volume fraction in swollen state (V_2s), number of repeating units between crosslinks (M_r) and crosslinking density (q) were calculated using Flory-Rehner theory. Selected samples were loaded with a model drug verapamil. Release of verapamil depends on the ratios of CS/AA, degree of crosslinking and pH of the medium. The release mechanisms were studied by fitting experimental data to model equations and calculating the corresponding parameters. The result showed that the kinetics of drug release from the hydrogels in both pH 1.2 and 7.5 buffer solutions was mainly non-Fickian diffusion.     

壳聚糖透明质酸复合水凝胶的制备及性能

用零长度的1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐(EDC·HCl)和N-羟基丁二酰亚胺(NHS)作为偶联剂和稳定剂制备了壳聚糖基透明质酸复合水凝胶,探讨了溶液pH值对该类水凝胶溶胀性的影响。溶液的pH在4.0时,该类水凝胶的溶胀率最低,升高和降低溶液的pH,该类水凝胶的溶胀率均升高,文中还对水凝胶的降解率进行了研究,实验发现,交联后的水凝胶具有一定的稳定性。包埋在此水凝胶中的牛血清蛋白(BSA)释放随载药介质pH值的变化而显著不同,pH 7.4条件下载药的水凝胶释药率大于pH 1.2条件下的释药率。因此,具有pH敏感性的壳聚糖透明质酸复合水凝胶在药物运输领域具有潜在的应用。     

聚丙烯酸类水凝胶的制备及其在碱性溶液中的pH敏感性

以（NH₄）₂S₂O₈和NaHSO₃为氧化-还原引发剂、N,N′-亚甲基双丙烯酰胺（MBA）为交联剂,采用自由基水溶液聚合方法,分别合成了聚丙烯酸（PAAc）、聚丙烯酰胺（PAAm）和系列丙烯酸（AAc）质量分数（fAAc）不同的聚（丙烯酸-co-丙烯酰胺）（P（AAc-co-AAm））水凝胶。进而分别对其在碱性缓冲溶液和NaOH溶液中的pH敏感行为进行了探讨。结果表明,PAAc和P（AAc-co-AAm）凝胶在2种溶液中均具有优良的pH响应行为,且在NaOH溶液中的溶胀比大于缓冲溶液中;而PAAm凝胶仅在NaOH溶液中具有pH敏感性。2种溶液中,随f（AAc）的增加,P（AAc-co-AAm）凝胶的平衡溶胀比（ESR）增大;但在缓冲溶液中,当f（AAc）≥20%时,P（AAc-co-AAm）凝胶的溶胀行为与PAAc相似,而当f（AAc）<20%时,其溶胀则同时表现出PAAc和PAAm凝胶的溶胀特性。溶胀机理分析表明,凝胶的溶胀主要受聚合物网络内静电排斥作用和离子屏蔽效应控制。     

Dynamical modeling and experimental evidence on the swelling/deswelling behaviors of pH sensitive hydrogels

A chemo-electro-mechanical fields coupling model was developed based on the Nernst-Planck equation, Donnan theory and elastic mechanics to investigate the swelling/deswelling dynamics of pH sensitive hydrogels. To test the model, chitosan hydrogels with pH sensitivity have been successfully prepared through a radiation crosslinking approach induced by Co-60 gamma ray. The deformation ratio of the hydrogels at radial direction is more than 100% when pH changes from 7 to 9. A finite element simulation was carried out to investigate the stress formation and diffusion inside the hydrogel in its deswelling process. Results showed that the data of simulation fit the experimental results well. Moreover, a stress-diffusion mechanism was proposed to explain the deswelling process.