Nathaniel Bingham

Dr Nathaniel Bingham PhD, MChem, AMRSC


Teaching Fellow
PhD, MChem

Biography

My teaching

My publications

Publications

Nathaniel M. Bingham , Qamar un Nisa, Sophie H. L. Chua, Lea Fontugne, Matt P. Spick, Peter J. Roth (2020). Thioester-Functional Polyacrylamides: Rapid Selective Backbone Degradation Triggers Solubility Switch Based on Aqueous Lower Critical Solution Temperature/Upper Critical Solution Temperature
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Radical ring-opening polymerization is a clever strategy to incorporate cleavable linkages into otherwise nondegradable vinyl polymers. However, conventional systems suffer from slow copolymerization, harsh nonselective degradation conditions, and limited application potential because the degradation products (often oligomers or polymers themselves) have properties like those of the intact species. This work presents fast selective degradation accompanied by a drastic change in a key property, aqueous solubility. Thionolactone dibenzo[,]oxepane-5-thione was found to copolymerize radically with a range of primary, secondary, and tertiary neutral and zwitterionic acrylamides with rapid incorporation of degradable biphenyl thiocarboxylate repeat units. Intact copolymers displayed temperature-responsive (lower critical solution temperature or upper critical solution temperature-type) aqueous solubility behavior, tunable through the molar composition and (exploiting the non-azeotropic copolymerization behavior) comonomer sequence. Various conditions led to selective and complete degradation of the backbone thioesters through hydrolysis, aminolysis, transthioesterification (including under physiological conditions), and oxidative hydrolysis, which drastically increased aqueous solubility. Polymers containing as little as 8 mol % thioester repeat units underwent a temperature-independent insoluble–soluble transition upon degradation with cysteine or potassium persulfate. Insoluble polymers were used to block syringe filters, which allowed flow of degradant solutions only, relevant to lab-on-a-chip, sensing, and embolic biomedical applications.
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Matt P. Spick , Nathaniel M. Bingham, Yuman Li, Janella de Jesus, Catia Costa, Melanie J. Bailey, Peter J. Roth (2020). Fully Degradable Thioester-Functional Homo- and Alternating Copolymers Prepared through Thiocarbonyl Addition–Ring-Opening RAFT Radical Polymerization
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The radical ring-opening polymerization (RROP) of thionolactones provides access to thioester backbone-functional copolymers but has, to date, only been demonstrated on acrylic copolymers. Herein, the thionolactone dibenzo[,]oxepane-5-thione (DOT) was subjected to azobisisobutyronitrile (AIBN)-initiated free-radical homopolymerization, which produced a thioester-functional homopolymer with a glass-transition temperature of 95 °C and the ability to degrade exclusively into predetermined small molecules. However, the homopolymerization was impractically slow and precluded the introduction of functionality. Conversely, the reversible addition–fragmentation chain-transfer (RAFT)-mediated copolymerization of DOT with -methylmaleimide (MeMI), -phenylmaleimide (PhMI), and -2,3,4,5,6-pentafluorophenylmaleimide (PFPMI) rapidly produced well-defined copolymers with the tendency to form alternating sequences increasing in the order MeMI ≪ PhMI < PFPMI, with estimated reactivity ratios of DOT = 0.198 and PFPMI = 0.0078 for the latter system. Interestingly, defects in the alternating structure were more likely caused by (degradable) DOT–DOT sequences rather than (nondegradable) MI–MI sequences, which was confirmed through the paper spray mass spectrometric analysis of the products from aminolytic degradation. Upon the aminolysis of backbone thioesters, maleimide repeating units were ring-opened, forming bisamide structures. Conversely, copolymer degradation through a thiolate did not result in imide substitution but nucleophilic -fluoro substitution on PFPMI comonomer units, indicating the ability of DOT–MI copolymers to degrade under different conditions and to form differently functional products. The RROP of thionolactones has distinct advantages over the RROP of cyclic ketene acetals and is anticipated to find use in the development of well-defined degradable polymer materials.
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Nathaniel M. Bingham and Peter J. Roth (2018). Degradable vinyl copolymers through thiocarbonyl addition–ring-opening (TARO) polymerization
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The radical copolymerization of the thionolactone dibenzo[,]oxepane-5-thione with acrylates, acrylonitrile, and ,-dimethylacrylamide afforded copolymers containing a controllable amount of backbone thioesters which could be selectively cleaved. The process is compatible with RAFT polymerization and promising for the development of advanced degradable polymers.
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