title: Poly(sophorolipid) structural variation: effects on biomaterial physical and biological properties.
abstract: Diacetylated lactonic sophorolipids (polyLSL[6'Ac,6″Ac]), a biosurfactant, can be efficiently polymerized by ring-opening metathesis polymerization (ROMP). In this paper, enzyme-mediated chemical transformations are developed to regioselectively modify LSL[6'Ac,6″Ac] at sophorose primary hydroxyl positions (6' and 6″). The resulting modified LSLs were polymerized to expand polyLSL structural diversity, that is, polyLSL[6'OH,6″Ac], polyLSL[6'OH,6″OH], polyLSL[6'Bu,6″Ac], polyLSL[6'N3,6″Ac], and polyLSL[6'MA,6″Ac]. Controlled placement of azide and methacrylate at sophorolipid moieties enables the use of "click" reactions to introduce bioactive groups. Thermal analyses of polyLSLs showed that the acylation pattern at sugar moieties has a remarkable effect on chain stiffness and crystallinity. Films of polyLSL[6'Ac,6″Ac], polyLSL[6'OH,6″Ac], and polyLSL[6'Bu,6″Ac] exhibited nonbrittle behaviors with compressive elastic moduli ranging from ∼1.5 to ∼4.9 MPa. PolyLSLs were cytocompatible with human mesenchymal stem cells (h-MSCs), and examination of material-induced osteogenic cell lineage progression uncovered a dependence on polyLSL substitution at sophorose 6'-sites. This research reveals opportunities to regulate polyLSL physical properties and cell response behaviors by variation in substituents at polyLSL sophorolipid moieties.
authors.affiliation: Department of Chemistry and Biology, §Department of Biomedical Engineering, and ∥Center for Biotechnology and Interdisciplinary Studies, Rensselaer Polytechnic Institute (RPI) , 110 8th Street, Troy, New York 12180, United States.
authors.forename: Yifeng
authors.initials: Y
authors.lastname: Peng
authors.forename: Dany J
authors.initials: DJ
authors.lastname: Munoz-Pinto
authors.forename: Mingtao
authors.initials: M
authors.lastname: Chen
authors.forename: John
authors.initials: J
authors.lastname: Decatur
authors.forename: Mariah
authors.initials: M
authors.lastname: Hahn
authors.forename: Richard A
authors.initials: RA
authors.lastname: Gross
mesh_terms: D001672:Biocompatible Materials / Q000737:chemistry* / Q000494:pharmacology; D001688:Biological Products / Q000737:chemistry* / Q000494:pharmacology; D002175:Candida; D002448:Cell Adhesion / Q000187:drug effects / Q000502:physiology; D002478:Cells, Cultured; D006017:Glycolipids / Q000737:chemistry* / Q000494:pharmacology; D006801:Humans; D059630:Mesenchymal Stem Cells / Q000187:drug effects / Q000502:physiology*; D011108:Polymers / Q000737:chemistry* / Q000494:pharmacology
chemical_list: D001672:Biocompatible Materials; D001688:Biological Products; D006017:Glycolipids; D011108:Polymers