Department of Chemistry, National University of Singapore, Block S8, Level 5, Science Drive 3, Singapore 117543.
Langmuir. 2009 Aug 4;25(15):8763-73. doi: 10.1021/la9002127.
This study examines the structural properties of binary and tertiary mixtures made of the cold-setting biopolymers agarose and gelatin and a lipid phase with solid or liquid-like viscoelasticity. The working protocol included the techniques of small-deformation dynamic oscillation on shear, modulated differential scanning calorimetry and scanning electron microscopy, and theoretical modeling that adapted ideas of relating the morphology to the elastic modulus of synthetic polyblends and block polymers. The experimental setting was designed to encourage extensive phase separation in the binary gel of agarose and gelatin whose mechanical properties were rationalized on the basis of a bicontinuous blending law. The presence of two continuous phases allowed the slower-gelling component (gelatin) to exhibit favorable relative affinity for the solvent with increasing concentrations of the protein in the system. This is an unexpected outcome that contradicts the central finding of a single value of the p factor observed in the distribution of solvent between the continuous matrix and discontinuous inclusions of deswelled binary gels reported earlier in the literature. The incorporation of a lipid phase of effectively zero elastic modulus or in excess of 10(8) Pa in the composite aqueous gel weakens or reinforces the matrix accordingly. The elastic moduli and morphology of the tertiary blend were related to changing the relative phase volumes of components using analytical expressions of isotropically dispersed soft or rigid filler particles in a polymeric matrix.
本研究考察了由冷固生物聚合物琼脂糖和明胶以及具有固态或液态粘弹性的脂质相组成的二元和三元混合物的结构性质。工作方案包括在剪切下进行小变形动态振荡、调制差示扫描量热法和扫描电子显微镜的技术,以及理论建模,该建模采用了将形态与合成聚共混物和嵌段聚合物的弹性模量相关联的思路。实验设置旨在鼓励琼脂糖和明胶二元凝胶中广泛的相分离,其力学性能基于双连续共混定律进行了合理化。两个连续相的存在使得凝固速度较慢的成分(明胶)在系统中蛋白质浓度增加时对溶剂表现出有利的相对亲和力。这是一个出乎意料的结果,与文献中早先报道的二元凝胶中连续基质和溶胀的不连续夹杂物之间溶剂分布中观察到 p 因子单一值的中心发现相矛盾。在复合水凝胶中加入有效弹性模量为零或超过 10(8) Pa 的脂质相,会相应地削弱或增强基质。使用各向同性分散的软或硬填充颗粒在聚合物基质中的分析表达式,将三元共混物的弹性模量和形态与改变各组分的相对相体积相关联。