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.     

离子键交联的聚两性电解质凝胶在不同pH和不同电解质溶液中溶胀行为研究

以丙烯酸(AA)和甲基丙烯酸二乙氨基乙酯(DEAM)形成的离子复合物与丙烯酰胺(AAm)共聚,合成了一种新型的离子键交联的聚两性电解质凝胶(PADA).由于分子之间的氢键作用,PADA凝胶并不是在A/C(负正离子单体摩尔比)为1,而是在A/C为1.55处有最大消溶胀.与共价键交联的聚两性电解质凝胶相比,PADA凝胶的溶胀行为具有更强的pH敏感性.PADA凝胶在不同pH缓冲溶液中的溶胀行为表明,在pH 3~4之间消溶胀程度最大.在偏离该pH区域时凝胶均发生溶胀.但凝胶的溶胀程度在pH<3的酸性溶液中随A/C的增加而降低;而在pH>4的偏碱性溶液中随其增加而增加.在不同价数的离子溶液中,离子浓度对于PADA凝胶的平衡溶胀有着不同的影响.对于一价的NaCl溶液,PADA凝胶有典型的反聚电解质效应.但对于高价的CaCl2和柠檬酸三钠溶液,只在较低的浓度下,才表现出反聚电解质效应.而在较高盐浓度时,随盐浓度的增加其溶胀比反而降低.这可能与高价离子形成的离子键交联有关.与pH对PADA凝胶溶胀程度的影响相似,在CaCl2溶液中,PADA凝胶的溶胀程度随A/C的增加而降低;而在柠檬酸三钠溶液中则刚好相反.这种独特的溶胀行为似乎与高价离子电荷的正负性有关.     

pH响应性阳离子型微凝胶的制备及性质研究

以甲基丙烯酸-(N,N-二甲氨基)乙酯(DMAEMA)和丙烯酸乙酯(EA)为共聚单体, 二甲基丙烯酸乙二醇酯(EGDMA)为交联剂, 采用半连续乳液聚合法, 制备了具有pH响应性的阳离子型微凝胶, 并研究不同聚合条件对所合成的微凝胶性质的影响. 利用透射电子显微镜(TEM)、激光粒度分析仪和流变仪对微凝胶进行一系列表征. 研究了介质pH值对微凝胶的形态、平均粒径、zeta电位、溶液浊度(透光率)的影响, 以及NaCl盐溶液对微凝胶分散体系稳定性的影响. 结果表明, 这类阳离子型微凝胶体系具有良好的pH响应性, 在pH＝7左右发生相转变. 此外, 研究表明不同浓度NaCl溶液对微凝胶的稳定性有一定影响, 临界絮凝浓度约为1.3 mol&#8226;L－1.     

离子键交联聚两性电解质凝胶在电场作用下的溶蚀现象

以丙烯酸(AA)和甲基丙烯酸二乙氨基乙酯(DEAM)形成的离子复合物和丙烯酰胺(AAm)为单体,采用自由基聚合制备了一系列新型的离子键交联聚两性电解质凝胶(PADA凝胶).非接触直流电场的实验表明,该离子键交联的PADA凝胶在电场下发生溶蚀现象,该现象鲜见文献报道.PADA凝胶的溶蚀速率与电场强度、溶液浓度、pH值、酸碱基团摩尔比、溶液离子价态等诸多因素有关,如溶蚀随电压的升高而增大,随盐溶液浓度的加大而增大.其溶蚀动力学研究表明PADA凝胶的溶蚀度随时间线性的增加,即溶蚀速率在整个实验时间内基本保持恒定.     

可自去除模板法制备环境响应性PNIPAM空心微球

本文采用可自去除模板法制备了单分散的聚（N-异丙基丙烯酰胺） （PNIPAM）空心微球, 用透射电子显微镜（TEM）研究了不同工艺条件对微球尺寸和形貌的影响机制. 结果表明, 酸性单体甲基丙烯酸（MAA）的加入量决定了PNIPAM微球空腔的形成速度; 而MAA及表面活性剂十二烷基硫酸钠（SDS）的加入量对空心微球的粒径及空腔大小亦有明显影响. 具体地讲, 当MAA的浓度从1.06 mmol/L增加到4.24 mmol/L时, 空心微球的平均粒径从250 nm左右增加到约450 nm, 内部空腔尺寸从40 nm增加到270 nm; 而当SDS的浓度从0增加到0.62 mmol/L时, 空心微球的平均粒径及内部空腔尺寸分别从450和270 nm降低到320和130 nm. 紫外分光光度计和动态光散射的检测结果显示, 所得PNIPAM空心微球具有受pH控制的温度敏感性.     

两性聚电解质溶液的分子热力学模型和分子动力学模拟

从带电硬球混合物出发采用化学缔合理论建立了聚电解质和两性聚电解质溶液的分子热力学模型.用考虑溶剂的粘滞力和热浴随机力作用的分子动力学(MD)方法模拟了聚电解质和两性聚电解质溶液的渗透系数.对模型预测结果和MD模拟结果进行了比较,表明基于化学缔合理论的分子热力学模型可以用于聚电解质溶液和两性聚电解质溶液热力学性质的预测,对于均聚电解质溶液效果令人满意,对由直径不同的离子构成的聚电解质溶液,模型的预测效果变差,有待进一步改进.该模型对两性聚电解质溶液渗透系数的预测效果比对聚电解质溶液的预测效果更好.     

离子凝胶反应法制备壳聚糖/N,O-羧甲基壳聚糖微球

以一氯乙酸与壳聚糖反应形成N,O-羧甲基壳聚糖两性聚电解质,分光光度法测定其等电点IEP=2．86。以此两性聚电解质与壳聚糖可以在一定条件下形成微球,光学显微镜和电子显微镜测试表明,控制两种聚电解质配比可以制备不同粒径大小的微球,而超声功率对微球粒径的影响较小。红外光谱测试表明微球中N,O-羧甲基壳聚糖羧基以羧酸根形式存在,分光光度与电导法联合测定表明两种聚电解质以离子凝胶作用形成微球,其最佳制备条件为IEP（CM-CHITOSAN）〈pH〈pKa（CS）,在此较宽的pH值范围内微球可稳定存在。     

接枝型聚两性电解质CS-g-PLGA的合成及溶液性质

合成了以壳聚糖(CS)为主链、 聚(L-谷氨酸)(PLGA)为侧链的接枝型聚两性电解质CS-g-PLGA(CGA), 表征了其结构与组成, 探讨了pH值、 离子强度和离子种类等对CGA水溶液性质的影响. 研究发现, 随着溶液离子强度的增大, CGA的等电点(IEP)移向高pH值; 离子水化半径越大, 对CGA分子中相反电荷的屏蔽作用越弱, 对IEP的影响越小; CGA中氨基和羧基相对含量越接近, 对溶液离子强度的变化越敏感. 此外, CGA具有显著的pH响应性, 在酸性及碱性溶液中分别形成结构相反的聚集体. 在CS主链氨基含量相近的条件下, 聚集体的稳定性随PLGA链长的增加而提高. 酸性溶液中聚集体粒径取决于CS主链的电荷数; 碱性溶液中PLGA侧链越长则平均粒径越大.     

微波辐射无皂乳液聚合制备聚氰基丙烯酸正丁酯微球

在微波辐射的"非致热效应"作用下,采用不含乳化剂的无皂乳液聚合,制备了聚氰基丙烯酸正丁酯(PBCA)微球。通过透射电子显微镜观察了微球的形态结构,利用激光光散射粒度测定仪测定了微球的粒径大小及其分布,探讨了柠檬酸浓度、氰基丙烯酸正丁酯(BCA)用量、微波辐射功率等对微球粒径的影响。研究结果表明,与常规无皂乳液聚合相比较,微波作用下的无皂乳液聚合反应时间缩短,得到的PBCA微球粒径更小,分散性更好。柠檬酸浓度增加,PBCA微球粒径逐渐增大;单体浓度增加,或微波功率增加,PBCA微球的粒径先减小后增大。当柠檬酸质量分数为0.005%、BCA体积分数为1.0%、微波功率为600W时,所制得的微球粒径最小,为200nm左右。     

氯盐溶液中甲烷水合物高压分解条件及影响因素

向水合物储层注入盐类溶液是水合物常规开采技术之一,所以必须掌握储层压力条件下盐类溶液中水合物分解条件及其影响因素.本文研究了NaCl、MgCl2、CaCl2氯盐溶液中甲烷水合物分解条件,结果表明NaCl(2.0、1.0、0.5 mol·L-1)、MgCl2 (1.0、0.5 mol·L-1)和CaCl2 (1.0、0.5 mol·L-1)溶液中甲烷水合物的分解温度比纯水中分别降低了(4.8、2.4、1.0 K (NaCl))、(5.3、1.5 K (MgCl2))和(4.3、1.8 K (CaCl2)).以van der Waals 和Platteeuw 热力学模型为基础,结合电解质溶液中水的活度方程(Pitzer-Mayorga 方程),给出了氯盐溶液中水合物分解条件热力学模型,进而比较了模型计算值与实验值,结果显示两者非常吻合.分析表明,氯盐溶液中离子静电作用产生的水分子溶剂化效应和盐析效应降低了水的活度而导致水合物分解温度降低.     

盐溶液调控海藻酸钙微球中的自由羧酸根及其对阿霉素的装载和释放行为研究

采用膜乳化-凝胶化法制备了粒径窄分布的海藻酸钙微球.用不同浓度的氯化钠溶液处理微球来调控微球中的自由羧酸根的含量.用原子吸收光谱和红外光谱表征了微球中钙、钠离子以及化学基团的变化,证明盐处理后海藻酸钙微球内发生了钠离子置换钙离子的过程,海藻酸中的羧酸根由螯合态转变为自由态.用盐处理后的微球吸附带正电荷的小分子抗癌药物阿霉素的能力大大提高,其中用浓度1.8%的氯化钠溶液处理后的微球载药量达到1310μg/mg,是未处理微球的10倍.负载药物的微球具有pH敏感的释放行为,在pH5.5的PBS溶液中的释放速率和释放量显著大于在pH 7.4的PBS溶液中.     

Acrolein polymerization: Monodisperse,homo, and hybrido microspheres,synthesis, mechanism,and reactions

Monodisperse polyacrolien (PA) microspheres were obtained by a single step process via two mechanisms: (a) aqueous polymerization of acrolein under alkaline conditions and (b) aqueous radical polymerization of acrolein by irradiation with a cobalt source. The diameter of the former microspheres can be varied from 0.04 up to 8 μm. The monodispersity of the system is also discussed. The diameter of the latter microspheres can be varied up to 0.2 μm. Hybrido PA microspheres were formed by grafting PA microspheres of average diameter of 0.1 μm obtained by irradiation onto the surface of PA microspheres produced by the alkaline mechanism. The aldehyde content of the microspheres prepared by irradiation is much higher than those of the microspheres formed under alkaline conditions. The aldehyde groups were used for the covalent binding of ligands containing primary amino groups, such as proteins and drugs, in a single step under physiological pH.     

Graft copolymers having hydrophobic backbone and hydrophilic branches. X. Preparation and properties of water-dispersible polyanionic microspheres having poly(methacrylic acid) branches on their surfaces

The free radical copolymerization of poly(t-butyl methacrylate) (PBMA) macromonomer with styrene in ethanol give monodispersed microspheres with 0.8-1.6 μm diameter. The resulting microspheres were treated with HCl solution to convert into anionic microspheres having poly(methacrylic acid) chains. ESCA analysis of the microsphere surface suggested that PBMA chains were favorably located on the surface of the microspheres. The particle size of the microspheres decreased with increasing molecular weight and concentration of the macromonomer. Water dispersibilities of the microspheres were evaluated by measuring the relative turbidity of the suspension of microspheres as a function of pH. The results show that they were strongly dependent on pH. © 1995 John Wiley & Sons, Inc.     

Characterization and chemistry of polyaldehyde microspheres

The chemical composition of polyacrolein (PA) microspheres of various types as well as polyglutaraldehyde (PGL) microspheres was elucidated. Nephelometric measurements were used for studying the stability properties of the polyaldehyde microspheres in different pH and salt concentrations. The stability of the aldehyde groups themselves at various pH and temperature was also determined. The polyaldehyde microspheres covalently bind amino ligands, e.g., proteins, antibodies, enzymes, and drugs in a single step. The effect of temperature and the influence of thiol compounds on the reaction between the polyaldehyde microspheres and amino ligands was examined. The reaction of the polyaldehyde microspheres with sodium hydrogen sulfite is also described.     

导电聚间甲基苯胺空心微球的制备及表征

在无任何掺杂酸的条件下,以过硫酸铵(APS)既为氧化剂、又为掺杂剂,采用无模板(template-free)自组装的方法制备了导电聚间甲基苯胺(PMT)空心微球.该空心微球的平均直径约为2μm,壳的厚度约为140nm.研究表明PMT空心微球是以球状的间甲苯胺胶束为软模板(soft-template)经过自组装过程而形成的.借助FTIR、UV-Vis和XRD等结构表征证实自组装的空心微球为导电态的聚间甲基苯胺.     

Investigation of salt properties with electro-acoustic measurements and their effect on dynamic binding capacity in hydrophobic interaction chromatography

The pH dependence in hydrophobic interaction chromatography (HIC) is usually discussed exclusively in terms of protein dependence and there are no clear defined trends. Many of the deviations from an ideal solution are caused solely by the high salt concentration, as protein concentration is usually negligible. So pH dependency in hydrophobic interaction chromatography could also be the result of pH dependent changes of ion properties from the salt solution. The possibility that pH dependent ion hydration or ion association in highly concentrated salt solutions may influence the dynamic protein binding capacity onto HIC resins was investigated. In buffer solutions commonly used in HIC e.g. sodium chloride, ammonium sulphate and sodium citrate pH dependent maxima in the electro-acoustic signals were found. These maxima are related to an increase of the ion sizes by hydration or ion association. At low ionic strength the maxima are in the range between 4.5 and 6 and they increased in concentrated electrolyte solutions to values between 6 and 8. The range of these maxima is in the same region as dynamic protein binding capacity maxima often observed in HIC. For a qualitative interpretation of this phenomenon of increased protein stabilization by volume exclusion effect extended scaling theory can be used. This theory predicts a maximum of protein stabilization if the ratio of salt ion diameter to water is 1.8. According to the hypothesis raised here, if the pH dependent ratio of salt ion diameter to water approaches this value the transport of the protein in the pore system is less restricted and an increase in binding capacity can be produced.     

One-pot synthesis and characterization of crosslinked polyphosphazene dopamine microspheres for controlled drug delivery applications

Inorganic–organic hybrid and highly cross-linked poly(cyclotriphosphazene-co-dopamine) microspheres (PCTD) were successfully synthesized by a one-step precipitation polymerization technique. In the polymerization reaction, dopamine (a neurotransmitter), hexachlorocyclotriphosphazene (HCCP, N₃P₃Cl₆) and triethylamine (TEA) were used as a monomer, a crosslinker molecule and an acid acceptor, respectively. The characterization of PCTD microspheres was performed by SEM-EDX, FTIR, XRD, TGA and DLS. The particle size of microspheres were determined as 1.042?µm. The usability of synthesized novel polyphosphazene microspheres for controlled drug release was investigated using acriflavine as a model drug. Acriflavine has antimicrobial and anticancer properties. As drug release medium pH:7.4 (PBS) and pH: 5.0 buffer solutions were used. They were the pH of blood and the approximate pH of the environment in which the cancerous cells are located, respectively. PCTD microspheres have 19.5?mgg^?1 drug storage capacity and 29% (pH: 5.0) and 47% (pH: 7.4) of the acriflavine was released from PCTD microspheres at 37?°C during 7?days.     

用无乳化剂乳液聚合法制备聚丙烯醛微球

本文应用无乳化剂乳液聚合法合成了粒度均一、具有活泼醛基的聚丙烯醛微球,并对丙烯醛聚合动力学和影响微球直径,活泼醛基含量的因素进行了研究。用合成的微球同不同的氨基酸和午血清白蛋白反应,结果表明:该微球在生理pH条件下同含有伯氨基的化合物具有较高的结合容量。因此,在无乳化剂存在下,采用乳液聚合法制备聚丙烯醛微球是一种合成具有干净表面的聚丙烯醛微球的新方法。     

Core–Shell Hollow Microspheres of Magnetic Iron Oxide@Amorphous Calcium Phosphate: Synthesis Using Adenosine 5′‐Triphosphate and Application in pH‐Responsive Drug Delivery

Drug nanocarriers with magnetic targeting and pH‐responsive drug‐release behavior are promising for applications in controlled drug delivery. Magnetic iron oxides show excellent magnetism, but their application in drug delivery is limited by low drug‐loading capacity and poor control over drug release. Herein, core–shell hollow microspheres of magnetic iron oxide@amorphous calcium phosphate (MIO@ACP) were prepared and investigated as magnetic, pH‐responsive drug nanocarriers. Hollow microspheres of magnetic iron oxide (HMIOs) were prepared by etching solid MIO microspheres in hydrochloric acid/ethanol solution. After loading a drug into the HMIOs, the drug‐loaded HMIOs were coated with a protective layer of ACP by using adenosine 5′‐triphosphate (ATP) disodium salt (Na₂ATP) as stabilizer, and drug‐loaded core–shell hollow microspheres of MIO@ACP (HMIOs/drug/ACP) were obtained. The as‐prepared HMIOs/drug/ACP drug‐delivery system exhibits superparamagnetism and pH‐responsive drug‐release behavior. In a medium with pH 7.4, drug release was slow, but it was significantly accelerated at pH 4.5 due to dissolution of the ACP shell. Docetaxel‐loaded core–shell hollow microspheres of MIO@ACP exhibited high anticancer activity.     

Characteristics of pH-sensitive hydrogel microsphere of poly(acrylamide-<Emphasis Type="Italic">co</Emphasis>-methacrylic acid) with sharp pH–volume transition

The forming process and characteristics of monodispersed hydrogel microspheres of poly(acrylamide–methacrylic acid) with sharp pH–volume transition were studied. pH-/ion-sensitive and thermosensitive behaviors of microspheres sampled at various stage of polymerization were evaluated by using the dynamic light scattering. It was observed that the sharpness of pH–volume transition increased with the increase in monomer conversion. Both thermo- and ion-sensitive behaviors were affected by pH. At pH 4.3, the hydrodynamic diameter of microspheres monotonically and slightly decreased with the increase in temperature, whereas at pH 3.5 and 3.8, the curves of thermo–volume transition were similar to those of pH–volume transition with a maximum temperature at 25 and 20 °C, respectively. Increasing the [CaCl₂] was to decrease the hydrodynamic diameters of microspheres, irrespective of pH. However, a region at lower [NaCl] was found, where the diameter increased with the increase in [NaCl]. Moreover, the range of diameter increasing extended to higher [NaCl] as pH increased.