Fibrillar gels via the self-assembly of poly(L-glutamate)-based statistical copolymers

作者: Charlotte D. Vacogne , Sarah M. Brosnan , Admir Masic , Helmut Schlaad

DOI: 10.1039/C5PY00491H

关键词:

摘要: Polypeptides having secondary structures often undergo self-assembly which can extend over multiple length scales. Poly(γ-benzyl-L-glutamate) (PBLG), for example, folds into α-helices and forms physical organogels, whereas poly(L-glutamic acid) (PLGA at acidic pH) or poly(L-glutamate) (PLG neutral/basic do not form hydrogels. We explored the gelation of modified PBLG investigated deprotection carboxylic acid moieties in such gels to yield unique This was accomplished through photo-crosslinking poly(γ-benzyl-L-glutamate-co-allylglycine) statistical copolymers toluene, tetrahydrofuran, 1,4-dioxane. Unlike most polymer-based chemical gels, our were prepared from dilute solutions (<20 g L−1, i.e., <2% w/v) low molar mass polymers. Despite concentrations masses, dioxane showed high mechanical stability little shrinkage; remarkably, they also exhibited a porous fibrillar network. Deprotection yielded pH responsive highly absorbent PLGA/PLG-based hydrogels (swelling ratio up 87), while preserving network structure, is an unprecedented feature context crosslinked PLGA gels. These outstanding properties are attractive biomedical materials.

参考文章(60)
Jianjun Cheng, Timothy J. Deming, Synthesis of polypeptides by ring-opening polymerization of α-amino acid N-carboxyanhydrides. Topics in Current Chemistry. ,vol. 310, pp. 1- 26 ,(2011) , 10.1007/128_2011_173
Sumana Chakrabarti, Wilmer G. Miller, Aggregation of poly(γ-benzyl-α,L-glutamate) Biopolymers. ,vol. 23, pp. 719- 734 ,(1984) , 10.1002/BIP.360230411
Anne Lardner, The effects of extracellular pH on immune function Journal of Leukocyte Biology. ,vol. 69, pp. 522- 530 ,(2001) , 10.1189/JLB.69.4.522
Ansgar Niehoff, Alexandre Mantion, Richard McAloney, Alexandra Huber, Jana Falkenhagen, Cynthia M. Goh, Andreas F. Thünemann, Mitchell A. Winnik, Henning Menzel, Elucidation of the structure of poly(γ-benzyl-l-glutamate) nanofibers and gel networks in a helicogenic solvent. Colloid and Polymer Science. ,vol. 291, pp. 1353- 1363 ,(2013) , 10.1007/S00396-012-2866-9
Yoshinobu Izumi, Hikaru Takezawa, Noriyuki Kikuta, Soichi Uemura, Akihiro Tsutsumi, Two-stage melting in dilute gels of poly(γ-benzyl L-glutamate) Macromolecules. ,vol. 31, pp. 430- 435 ,(1998) , 10.1021/MA9708609
Kai-Steffen Krannig, Helmut Schlaad, pH-Responsive Bioactive Glycopolypeptides with Enhanced Helicity and Solubility in Aqueous Solution Journal of the American Chemical Society. ,vol. 134, pp. 18542- 18545 ,(2012) , 10.1021/JA308772D
Timothy J. Deming, Polypeptide hydrogels via a unique assembly mechanism Soft Matter. ,vol. 1, pp. 28- 35 ,(2005) , 10.1039/B500307E
Sandeep S. Naik, Daniel A. Savin, Poly(Z-lysine)-Based Organogels: Effect of Interfacial Frustration on Gel Strength Macromolecules. ,vol. 42, pp. 7114- 7121 ,(2009) , 10.1021/MA9011126