Taief Karrar Al, Nemec Stephanie, Middleton Isis A, Kilian Kristopher A, Thordarson Pall
School of Chemistry, University of New South Wales, Sydney, NSW, 2052, Australia.
The UNSW RNA Institute, University of New South Wales, Sydney, NSW, 2052, Australia.
Chemistry. 2025 May 14;31(27):e202404410. doi: 10.1002/chem.202404410. Epub 2025 Apr 21.
The amino acid sequence is crucial in controlling peptide-based hydrogel formation, whereby changing the position of a single amino acid can significantly alter the gel's properties. Herein, we report the gelation kinetics and cell viability of scrFmoc-GFFRDG (where we have scrambled the RGD-based gel hexapeptide; Fmoc-GFFRGD). The scrambled sequence showed improved gelation properties compared to the original Fmoc-GFFRGD sequence, with scrFmoc-GFFRDG forming a gel in under 10 min, significantly faster than the 2-h gelation time, and at a concentration eight times lower than the original Fmoc-GFFRGD sequence. We also examined the combination of the two gelators in a ratio of 1:1, final concentration of 0.4% (w/v). Interestingly, the stiffness of the hybrid hydrogel was ∼3 kPa, whereas individually, neither gelator at the same concentration exceeded 0.5 kPa. The cell-adhesion motif RGD improves the ability of the peptides to promote attachment of cells due to integrin recognition. However, when fibroblasts were cultured on the hydrogels, scrFmoc-GFFRDG yielded a higher level of α-SMA expression in cells than those cultured on Fmoc-GFFRGD, suggesting a microenvironment conducive to myofibroblast transitions. This study provides a new outlook on how a well-known scrambled peptide motif (RDG) can fine-tune hydrogel assembly and cell culture applications.
氨基酸序列对于控制基于肽的水凝胶形成至关重要,其中改变单个氨基酸的位置可显著改变凝胶的性质。在此,我们报告了scrFmoc-GFFRDG(我们对基于RGD的凝胶六肽进行了序列打乱;Fmoc-GFFRGD)的凝胶化动力学和细胞活力。与原始的Fmoc-GFFRGD序列相比,打乱后的序列显示出改善的凝胶化性质,scrFmoc-GFFRDG在不到10分钟内形成凝胶,明显快于2小时的凝胶化时间,且浓度比原始的Fmoc-GFFRGD序列低八倍。我们还以1:1的比例、最终浓度为0.4%(w/v)研究了两种凝胶剂的组合。有趣的是,混合水凝胶的硬度约为3 kPa,而单独使用时,相同浓度的两种凝胶剂都未超过0.5 kPa。细胞黏附基序RGD由于整合素识别而提高了肽促进细胞附着的能力。然而,当在水凝胶上培养成纤维细胞时,与在Fmoc-GFFRGD上培养的细胞相比,scrFmoc-GFFRDG在细胞中产生了更高水平的α-SMA表达,表明存在有利于肌成纤维细胞转变的微环境。这项研究为一个著名的打乱肽基序(RDG)如何微调水凝胶组装和细胞培养应用提供了新的视角。