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Exploring Versatile Sulfhydryl Chemistry in the Chain End of a Synthetic Polylactide

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Polymer Science Unit, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India
Cite this: Macromolecules 2012, 45, 21, 8561–8570
Publication Date (Web):October 29, 2012
https://doi.org/10.1021/ma302130f
Copyright © 2012 American Chemical Society

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    Abstract

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    Synthesis of an end-functionalized polylactide by ring-opening polymerization of lactide monomer using a functional initiator containing pyridyl disulfide group is reported. Molecular weight of the polymer determined by GPC matched very well with that determined by end-group analysis using the UV/vis method, suggesting survival of the end-group functionality during polymerization. DTT-induced reduction of the pyridyl disulfide group produced free sulfhydryl group quantitatively which was utilized for versatile chain-end modifications using various thiol-mediated high-yielding chemical transformations including thiol–ene, thiol–maleimide, and thiol–acrylate “click” reactions. This strategy was further extended to link two macromolecules by reaction of sulfhydryl-functionalized polylactide and acrylate-terminated poly(ethylene oxide) (PEO) which produced a block copolymer with an acid-labile β-thiopropionate linker between the two constituent blocks. This functional group could be cleaved under mild acidic condition to produce the individual parent polymers. Further as-synthesized pyridyl disulfide-terminated polylactide was treated with thiol-functionalized sugar moiety and n-type semiconducting naphthalene diimide (NDI) chromophore which also generated quantitative chain-end functionalization by thiol–disulfide exchange reaction. NDI-functionalized polylactide showed white light emission due to mixed emission from monomeric and excimer-type species. Further atomic force microscopic (AFM) studies revealed NDI-functionalized polymer formed uniform spherical aggregates upon drying of a drop-casted film on silicon surface possibly due to solvent-evaporation-induced defined organization of the polymer chain dictated by strong π-stacking interaction among the NDI chromophores.

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    Synthesis and characterization data of various small molecules containing thiol containing and thiol reactive functional groups and additional spectral data. This material is available free of charge via the Internet at http://pubs.acs.org.

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