文献类型：期刊文献

英文题名：Self-Assembly of Glycerol-Amphiphilic Janus Dendrimers Amplifies and Indicates Principles for the Selection of Stereochemistry by Biological Membranes

作者：Zhang, Dapeng[1,2];Xiao, Qi[1,3,4,5];Rahimzadeh, Mehrnoush[6,7];Liu, Matthew[1];Rodriguez-Emmenegger, Cesar[6,7,8,9];Miyazaki, Yusuke[10];Shinoda, Wataru[10];Percec, Virgil[1]

机构：[1]Univ Penn, Dept Chem, Roy & Diana Vagelos Labs, Philadelphia, PA 19104 USA;[2]East China Univ Sci & Technol, Sch Mat Sci & Engn, Lab Low Dimens Mat Chem, Shanghai 200237, Peoples R China;[3]Temple Univ, Inst Computat Mol Sci, Philadelphia, PA 19122 USA;[4]ET Healthcare Inc, 2455 Faber Pl, Palo Alto, CA 94303 USA;[5]Gator Bio, 2455 Faber Pl, Palo Alto, CA 94303 USA;[6]Leibniz Inst Interact Mat, DWI, D-52074 Aachen, Germany;[7]Rhein Westfal TH Aachen, Inst Tech & Macromol Chem, D-52074 Aachen, Germany;[8]Inst Bioengn Catalonia IBEC, Barcelona Inst Sci & Technol BIST, Carrer Baldiri Reixac,10,12, Barcelona 08028, Spain;[9]Inst Catalana Recerca Estudis Avancats ICREA, Passeig Lluis Co 23, Barcelona 08010, Spain;[10]Okayama Univ, Res Inst Interdisciplinary Sci, Okayama 7008530, Japan

年份：2023

卷号：145

期号：7

起止页码：4311

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20230713594698);WOS:【SCI-EXPANDED(收录号:WOS:000963805100001)】；

基金：This work was supported by the National Science Foundation grants DMR-1807127 (V.P.) and DMR-1720530 (to V.P.) , the P. Roy Vagelos Chair at the University of Pennsylvania (V.P.) , the Alexander von Humboldt Foundation (to V.P.) , the European Union?s Horizon H2020-NMBP-TR-IND-2018, EVPRO (Development of Extracellular Vesicles loaded hydrogel coatings with immunomodulatory activity for Promoted Regenerative Osseo integration of revision endo-prosthesis) grant 814495-2 (to C.R.-E.) , and JSPS KAKENHI grant no. JP21H01880 (to W.S.) . Calculations were performed at the facilities of the Research Center for Computational Science, Okazaki (project: 22-IMS-C108) and the Institute for Solid State Physics, and the University of Tokyo. We thank a reviewer for encouraging us to develop a molecular modelexplaining the self-assembly of onions from racemic amphiphilic JDs.

语种：英文

外文关键词：Biological membranes - Cytology - Enantiomers - Glycerol - Molecular dynamics - Phospholipids - Self assembly - Stereoselectivity

摘要：The principles for the selection of the stereo-chemistry of phospholipids of biological membranes remain unclear and continue to be debated. Therefore, any new experiments on this topic may help progress in this field. To address this question, three libraries of constitutional isomeric glycerol-amphiphilic Janus dendrimers (JDs) with nonsymmetric homochiral, racemic, and symmetric achiral branching points were synthesized by an orthogonal-modular-convergent methodology. These JDs amplify self-assembly, and therefore, monodisperse vesicles known as dendrimersomes (DSs) with predictable dimensions programmed by JD concentration were assembled by rapid injection of their ethanol solution into water. DSs of homochiral JD enantiomers, racemic, including mixtures of different enantiomers, and achiral exhibited similar DS size-concentration dependence. However, the number of bilayers of DSs assembled from homochiral, achiral, and racemic JDs determined by cryo-TEM were different. Statistical analysis of the number of bilayers and coarse-grained molecular dynamics simulations demonstrated that homochiral JDs formed predominantly unilamellar DSs. Symmetric achiral JDs assembled only unilamellar DSs while racemic JDs favored multilamellar DSs. Since cell membranes are unilamellar, these results indicate a new rationale for nonsymmetric homochiral vs racemic selection. Simultaneously, these experiments imply that the symmetric achiral lipids forming more stable membrane, probably had been the preferable assemblies of prebiotic cell membranes.