Synthesis and physicochemical characterization of end-linked poly(ethylene glycol)-co-peptide hydrogels formed by Michael-type addition
Synthesis and physicochemical characterization of end-linked poly(ethylene glycol)-co-peptide hydrogels formed by Michael-type addition
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DOI：
10.1021/bm025744e
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发表时间：
2003-05-01
影响因子：
6.2
通讯作者：
Hubbell, JA
中科院分区：
文献类型：
--
作者：
Lutolf, MP;Hubbell, JA
介绍了以多臂乙烯基磺酸端聚乙二醇大分子和α -omega半胱氨酸寡肽为共聚物，经michael型加成物逐步共聚合成新型杂化水凝胶的方法。通过原位流变学研究，交联动力学可以通过pH和靠近Cys的带电氨基酸残基的存在来控制，这可以调节巯基的pK(a)。这些末端连接的网络的特点是它们在水中的平衡膨胀，它们在膨胀状态下的粘弹性，以及它们的可溶性分数。结果表明，在交联过程中，结构和性能对制备状态（包括化学计量和前驱体浓度）非常敏感，而对pH值不太敏感。对于每个网络，弹性活性链的浓度(v)是利用Miller-Macosko理论从实验确定的溶胶组分中计算出来的，并与溶胀和流变学研究以及Flory经典网络模型计算得到的值进行比较。制备了具有不同大分子结构的水凝胶，其性质与大分子的功能和分子量有关。
The synthesis of novel hybrid hydrogels by stepwise copolymerization of multiarm vinyl sulfone-terminated poly(ethylene glycol) macromers and alpha-omega cysteine oligopeptides via Michael-type additions is described. Cross-linking kinetics, studied by in situ rheometry, can be controlled by pH and the presence of charged amino acid residues in close proximity to the Cys, which modulates the pK(a) of the thiol group. These end-linked networks were characterized by their equilibrium swelling in water, by their viscoelastic properties in the swollen state, and by their soluble fraction. It was demonstrated that structure and properties are very sensitive to the preparation state including stoichiometry and precursor concentration and less sensitive to the pH during cross-linking. For each network the concentration of elastically active chains (v) was calculated from experimentally determined sol fractions using Miller-Macosko theory and compared to values obtained from swelling and rheometry studies and by calculation from Flory's classical network models. Hydrogels were also prepared with varying macromer structures, and their properties were shown to respond to both macromer functionality and molecular weight.