Fmoc-Diphenylalanine Self-Assembly Mechanism Induces Apparent pKa Shifts

被引:397
作者
Tang, Claire [1 ,2 ]
Smith, Andrew M. [1 ,2 ]
Collins, Richard F. [2 ]
Ulijn, Rein V. [1 ,2 ,3 ]
Saiani, Alberto [1 ]
机构
[1] Univ Manchester, Sch Mat, Manchester M1 7HS, Lancs, England
[2] Univ Manchester, MIB, Manchester M1 7DN, Lancs, England
[3] Univ Strathclyde, WestCHEM, Glasgow G1 1XL, Lanark, Scotland
基金
英国工程与自然科学研究理事会;
关键词
SUPRAMOLECULAR HYDROGELS; REVERSED HYDROLYSIS; PEPTIDE; MINERALIZATION; BIOMATERIALS; NANOFIBERS; SCAFFOLDS; CELLS;
D O I
10.1021/la900653q
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report the effect of pH on the self-assembly process of Fmoc-diphenylalanine (Fmoc-FF) into fibrils consisting of antiparallel beta-sheets and show that it results in two apparent pK(a) shifts of similar to 6.4 and similar to 2.2 pH units above the theoretical pK(a) (3.5). Using Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), wide angle X-ray scattering (WAXS), and oscillatory rheology, these two transitions were shown to coincide with significant structural changes. An entangled network of flexible fibrils forming a weak hydrogel dominates at high pH. while nongelling flat rigid ribbons form at intermediate pH values. Overall. this study provides further understanding of the self-assembly mechanism of aromatic short peptide derivatives.
引用
收藏
页码:9447 / 9453
页数:7
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