Influence of polymer molar mass and mixture stoichiometry on polyelectrolyte complexes of poly(l-arginine) and Poly(l-glutamic acid)

Influence of polymer molar mass and mixture stoichiometry on polyelectrolyte complexes of poly(l-arginine) and Poly(l-glutamic acid)
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聚合物摩尔质量和混合物化学计量对聚(L-精氨酸)和聚(L-谷氨酸)聚电解质复合物的影响

DOI:
10.1016/j.polymer.2022.125497
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发表时间:
2022
期刊:
影响因子:
4.6
通讯作者:
Castelletto V
Castelletto V
中科院分区:
化学2区
文献类型:
--
作者:
Castelletto V

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聚(L-精氨酸)(PARG)和聚(L-谷氨酸)(PLGA)均聚多肽通过精确的N-羧酸酐开环聚合方法定制合成,具有两个摩尔质量,匹配成对的阳离子和阴离子多肽(聚合度n = 100和n = 500)。用圆二色性(CD)和FTIR光谱,揭示了主要聚脯氨酸II(PPII)构象的存在下探测的同聚多肽的构象。小角X-射线散射(SAXS)显示浓度依赖性的峰和形状因子与highqscaling由于排除体积行为的蠕虫状链。然后,我们研究了在具有匹配摩尔质量的PARG和PLGA多肽对的混合物中的络合作用。用CD、SAXS和cryo-TEM研究了沉淀物、上清液和重悬沉淀物的结构。这些结果表明,与文献中先前的建议相反,沉淀物主要含有PPII样构象的多肽,并且仅存在最小的β-折叠含量(在某些测量的制备过程中干燥样品时其增强)。低温透射电镜和小角X射线衍射分析表明,沉淀物具有分形结构。我们对多肽复合物沉淀物结构的研究结果有助于理解蛋白质复合物的相分离和凝聚,并可能揭示蛋白质和肽类如Lewy和其他包涵体的细胞间体的形成。
Poly(l-arginine) (PARG) and poly(l-glutamic acid) (PLGA) homopolypeptides were custom synthesized by precisionN-carboxyanhydride ring-opening polymerization methods with two molar masses, matched for pairs of cationic and anionic polypeptides (degrees of polymerizationn= 100 andn= 500). The conformations of the homopolypeptides were probed using circular dichroism (CD) and FTIR spectroscopy which revealed the presence of mainly polyproline II (PPII) conformation. Small-angle X-ray scattering (SAXS) showed concentration-dependent polyelectrolyte peaks and form factor with highqscaling due to the excluded volume behaviour of the wormlike chains. We then examined polyelectrolyte complexation in mixtures of pairs of PARG and PLGA polypeptides with matched molar masses. Precipitation was generally observed and the structures of precipitates, supernatant and resuspended precipitates were investigated using CD, SAXS and cryo-TEM. These revealed that, contrary to prior suggestions in the literature, the precipitates contain mostly polypeptides in a PPII-like conformation, and there is only a minimal β-sheet content (which is enhanced upon drying the sample during preparation for certain measurements). The precipitates have a fractal-like structure as revealed by cryo-TEM and SAXS. Our findings on the structure of polypeptide complex precipitates contribute to the understanding of phase separation of polyelectrolyte complexes and coacervation and may shed light on the formation of inter-cellular bodies of proteins and peptides such as Lewy and other inclusion bodies.
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