Synergistic hierarchical silicone-modified polysaccharide hybrid as a soft scaffold to control cell adhesion and proliferation

In this study, a new type of polydimethylsiloxane-modified chitosan (PMSC) amphiphilic hydrogel was developed as a soft substrate to explore cellular responses for dermal reconstruction. The hydrogel wettability, mechanical stiffness and topography were controllable through manipulation of the degree of esterification (DE) between hydrophobic polydimethylsiloxane (PDMS) and hydrophilic N,O-(carboxymethyl)-chitosan (NOCC). Based on microphase separation, the incorporation of PDMS into NOCC increased the stiffness of the hybrid through the formation of self-assembled aggregates, which also provided anchor sites for cell adhesion. As the DE exceeded 0.39, the size of the PDMS-rich aggregates changed from nanoscale to microscale. Subsequently, the hierarchical architecture resulted in an increase in the tensile modulus of the hybrid gel up to fourfold, which simultaneously provided mechano-topographic guidance and allowed the cells to completely spread to form spindle shapes instead of forming a spherical morphology, as on NOCC (DE = 0). The results revealed that the incorporation of hydrophobic PDMS not only impeded acidic damage resulting from NOCC but also acted as an adhesion modification agent to facilitate long-term cell adhesion and proliferation on the soft substrate. As proved by the promotion on long-term type-I collagen production, the PMSC hybrid with self-assembled mechano-topography offers great promise as an advanced scaffold material for use in healing applications.     

Dual Thermo- and Photo-Responsive Micelles Based on Azobenzene-Containing Random Copolymer

Amphiphilic random copolymer poly(methacrylamido-azobenzene)-ran-poly(2-hydroxyethylacrylate) (PMAAAB-ran-PHEA) was synthesized via hydrolysis of poly(methacrylamido-azobenzene)-ran-poly[2-((2′-tetrahydropyranyl)oxy)ethylacrylate] (PMAAAB-ran-P(THP-HEA)), which was prepared by conventional radical polymerization. PMAAAB-ran-PHEA micelles were then prepared via dialysis method against water with DMF as solvent. The structure, morphology, size, and low critical solution temperature (LCST) of PMAAAB-ran-PHEA and its micelles were determined by ¹H-NMR, GPC, TEM, and DLS. The thermo- and photo-responsive behaviors of the resulting polymer micelles were investigated with Nile red as a fluorescence probe. The results showed that PMAAAB-ran-PHEA micelles were porous or bowl-shaped and its size was 135–150 nm, and its LCST was 55 °C when F_MAAAB of the random copolymer was 0.5351; the hydrophobicity of the micellar core was changed reversibly under the irradiation of UV light and visible light without release of Nile red or disruption of micelles; the size and solubilization capacity of the micelles were dependent on temperature, and Nile red would migrate for many times between the water phase and the micelles, and finally increasingly accumulated during the repeated heating and cooling processes.     

Graft copolymer emulsions of sodium alginate with hydroxyallsyl methacrylates for microencapsulation

A hybrid material with interesting capsule forming properties has been prepared by γ-initiated polymerization of hydroxyethyl methacrylate (HEMA) or other acrylic monomers in the presence of aqueous sodium alginate. For example, an aqueous solution of HEMA (1 wt%) and sodium alginate (1 wt%) was irradiated in a γ-source at a dose of 0.15 MR, to produce a stable emulsion which coalesced in the form of a homogeneous precipitate when added to 0.1 M CaCI₂. Polymerization of HEMA was presumed to be initiated by free radicals generated in the alginate by γ-irradiation. The emulsion consisted largely of polyHEMA homopolymer stabilized by an alginate-polyacrylate graft (or block) copolymer of highly branched and ill-defined character, which acts as surfactant to prevent coagulation of the emulsion. Erythrocytes were encapsulated in such an emulsion by extrusion of cell/copolymer emulsion mixture into HEPES buffered CaCI₂ (10 mM Ca). Cells appeared intact and functional after encapsulation. By SEM it appeared that the capsule wall consisted of microspheres of polyHEMA on the inner and outer surfaces held together by the alginate. Furthermore the capsule did not contain the internal meshwork, characteristic of calcium alginate homopolymer gels. Although much remains to be learned about these materials, the combination of the easy gelling characteristics of the alginate with the range of desirable properties (e.g. biocompatibility) afforded by the acrylic monomers may have a significant impact on the development of cell microencapsulation technology.     

含氧螺环侧基线型共聚物的光交联和应用

研究了乙烯基螺环原酯和马来酸酐共聚物的光交联反应 ,使用碘金翁盐作为阳离子光引发剂 ,在UV光作用下 ,通过乙烯基螺环原酯单元上的螺环开环聚合反应产生交联 ,产物的体积发生膨胀 ,膨胀率为 2 %左右。由于乙烯基螺环原酯单元生成的长侧链的作用 ,增进了高分子链的活动性 ,使得在固体膜中螺环开环反应转化率达到 80 %以上 ,同时光交联产物不产生脆性。进一步研究了光引发剂碘金翁盐 (PhI+Ph·R)X-的浓度和结构对乙烯基螺环原酯 /马来酸酐共聚物光交联反应的影响 ,发现螺环开环反应转化率随金翁盐浓度增大而增加 ,并于 2wt%出现最高点 ,而其取代基的碳链长度对交联速度的效果是C4>C8>C12 ,其对离子X-的影响则和它们的离子强度相关。应用乙烯基螺环原酯 /马来酸酐共聚物与改性环氧丙烯酸酯和季戊四醇三丙烯酸酯组成感光树脂 ,经曝光和碱水显影加工可获得清晰的图像。     

双亲性无规光敏共聚物的疏水基元对其 自组装胶束乳化性能的影响

设计合成了一系列具有不同化学组成的双亲性无规光敏共聚物,聚(7-对乙烯基苄氧基-4-甲基香豆素-r-丙烯酸)（P(VM-r-AA)）,通过选择性溶剂法自组装获得纳米胶束,并将纳米胶束用作大分子颗粒乳化剂,研究其在甲苯-水界面的稳定性能。研究表明：聚合物疏水基元含量的增加使自组装胶束结构由溶胀的微凝胶状向刚性颗粒状转变;同时,胶束初始乳化效率增加,但油水界面吸附稳定性显著下降。此外,通过对疏水基元PVM的摩尔分数为12%的胶束进行辐照交联,并研究其在不同pH下的乳化性能,结果表明：胶束表面溶胀的双亲性链段对其乳化性能产生了重要的影响。未交联的胶束保持着良好的乳化性能;而交联的胶束形变能力变差、刚性增强,在碱性条件下,彻底失去乳化能力。     

丙烯酸基蓖麻油氨基甲酸酯齐聚物的合成和表征

合成和表征了丙烯酸基蓖麻油氨基甲酸酯齐聚物(VTPU)。证明:2,4-甲苯二异氰酸酯(2,4-TDI)与丙烯酸羟乙酯(HEA)封端反应生成丙烯酸基单异氰酸酯(IPT)为二级反应。同样,ITP与蓖麻油(CAO)扩链反应亦为二级。通过对缩合反应速率常数和表观活化能的研究表明:VTPU的结构主要由2,4-TDI中对位和邻位二异氰酸基的活性差异所控制,而齐聚物表观粘度与二异氰酸酯的结构规整性有关。动态粘弹谱测试表明:当VTPU中硬链段含量为59%时,聚合物呈分相结构,抗张强度最高为18.2MPa,若增加至67%时,在100.7℃呈现单一转变峰,动态模量因而下降。     

P(4-VPPS-co-DMAPS)两性离子共聚物膜的制备及表征

首先,以4-乙烯基吡啶（4-VP）与甲基丙烯酸二甲氨乙酯（DMAEMA）为单体通过自由基共聚,得到聚（4-乙烯基吡啶-co-甲基丙烯酸二甲氨乙酯）共聚物（P（4-VP-co-DMAEMA））;然后,用1,3-丙磺酸内酯对P（4-VP-co-DMAEMA）侧链进行季铵化改性,得到不同离子化修饰程度的P（4-VP-co-DMAEMA）的两性离子共聚物（P（4-VPPS-co-DMAPS））。采用傅里叶转换红外光谱（FT-IR）、核磁共振氢谱（¹H-NMR）和凝胶渗透色谱（GPC）对P（4-VP-co-DMAEMA）和P（4-VPPS-co-DMAPS）的化学结构进行表征。用万能拉力试验机、差示扫描量热分析仪（DSC）、热重分析仪（TG）以及稀释涂布平板法对P（4-VP-co-DMAEMA）和P（4-VPPS-co-DMAPS）薄膜的力学性能、热学性能以及抗菌/防污性能进行了表征。探究了单体单元物质的量之比、季铵化修饰程度对P（4-VPPS-co-DMAPS）薄膜材料物理化学性能以及功能性的影响。结果表明：当两种单体单元的物质的量之比（n_4-VP/n_DMAEMA）为3/7,离子化修饰程度为20%时,得到的两性离子共聚物薄膜具有一定的热稳定性、韧性和强度,且兼具优异的抗菌/防污特性。     

EVA等离子体表面接枝丙烯酸的阻燃性能研究

以乙烯－醋酸乙烯共聚物通过等离子体接枝丙烯酸以达到阻燃的目的。接技后样品的点燃时间延长、极取氧指数提高、成炭量增加,说明接枝后的侧基（－ＣＯＯＨ,－ＣＯＯＮａ和－ＣＯＯＫ）在热降解过程中不仅知身参与成炭,而且强有力地促进了基体聚合物的成炭过程。     

两亲共聚物SMASS对水煤浆流变学性能的影响

合成了一系列接枝率不同的两亲性共聚物分散剂——对氨基苯磺酸接枝马来酸酐-苯乙烯共聚物(SMASS),并用氢核磁共振及红外光谱对其结构进行了表征。通过测量接触角,发现该分散剂能有效改善煤表面的亲水性;运用高级旋转流变仪研究了水煤浆自身浓度、分散剂及其用量对水煤浆流变性能及稳定性的影响。实验结果表明分散剂能有效降低水煤浆的表观黏度和屈服应力,大幅提高水煤浆的稳定性,并且发现接枝率为0.28的SMASS1效果最好。进一步对比了接枝率均为0.50左右的SMASS2(接枝率为0.49)和氨基萘磺酸接枝马来酸酐-苯乙烯共聚物SMANS2 (接枝率为0.50),及一种木质素类商用添加剂(AD)对水煤浆降黏增稳的影响,发现SMASS2的综合效果最好。由此证明,SMASS是一种新型有效且相对廉价的水煤浆分散剂,具有良好的工业应用前景。     

HEMA与HEA辐射共聚制备固定

应用低温辐射技术辐射诱导甲基丙烯酸β-羟乙酯(HEMA)和丙烯酸羟乙酯(HEA)共聚合制备了高分子载体,用增殖细胞技术固定氨氧化细菌。利用红外光谱(FT-IR)、X射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电子显微镜(SEM)以及接触角和含水率的测试对聚合物载体进行了性能表征。结果表明：经充分溶胀后的聚合物表面水接触角几乎为0,含水率为450%,润湿性能良好;聚合物表面具有极性官能团;聚合物的非晶结构有利于小分子尤其是水分子的渗透和扩散,多孔结构有利于微生物的生长和繁殖。以聚合物为载体固定化氨氧化细菌在处理含氨废水的过程中实现了短程硝化,在3种氨氮负荷（100、150、200 mg/L）条件下,氨氮去除率和亚硝化率可分别达到95%和90%以上。