Molecular Characterization of Polymer Networks.

Polymer networks are complex systems consisting of molecular components. Whereas the properties of the individual components are typically well understood by most chemists, translating that chemical insight into polymer networks themselves is limited by the statistical and poorly defined nature of network structures. As a result, it is challenging, if not currently impossible, to extrapolate from the molecular behavior of components to the full range of performance and properties of the entire polymer network.

PolyDAT: A Generic Data Schema for Polymer Characterization.

Polymers are stochastic materials that represent distributions of different molecules. In general, to quantify the distribution, polymer researchers rely on a series of chemical characterizations that each reveal partial information on the distribution. However, in practice, the exact set of characterizations that are carried out, as well as how the characterization data are aggregated and reported, is largely nonstandard across the polymer community.

Copper Ligand and Anion Effects: Controlling the Kinetics of the Photoinitiated Copper(I) Catalyzed Azide-Alkyne Cycloaddition Polymerization.

The kinetics of photoinduced copper(I) catalyzed azide-alkyne cycloaddition (CuAAC) polymerizations were assessed as a function of copper(II) amine-based ligands. Copper(II) bromide ligated with 1,1,4,7,10,10-hexamethylenetetramine (HMTETA) exhibited the fastest kinetics in both Norrish type(I) and type(II) photoinitiating systems. A characteristic induction period is observed with these polymerizations and is manipulated by adding an external tertiary amine in Norrish Type(II) photoinitating systems or by changing the anion of the copper(II) salt.

Photoinitiated Copper(I) Catalyzed Azide-Alkyne Cycloaddition Reaction for Ion Conductive Networks.

The photoinitiated copper(I) catalyzed azide-alkyne cycloaddition (photo-CuAAC) is a 'click' reaction that enables spatially and temporally controlled polymerizations. The solvent-less photopolymerization of multi-functional azide and cationic alkyne monomers results in the rapid formation of a charged polymer network. Full conversion of these monomers is achieved within 30 minutes under mild, blue-light irradiation conditions (470 nm light at 30 mW/cm).

On-Resin Macrocyclization of Peptides Using Vinyl Sulfonamides as a Thiol-Michael "Click" Acceptor.

Macrocyclization of linear peptides imparts improved stability to enzymatic degradation and increases potency of function. Many successful macrocyclization of peptides both in solution and on-resin have been achieved but are limited in scope as they lack selectivity, require long reaction times, or necessitate heat. To overcome these drawbacks a robust and facile strategy was developed employing thiol-Michael click chemistry via an N-methyl vinyl sulfonamide.

Towards understanding the kinetic behaviour and limitations in photo-induced copper(i) catalyzed azide-alkyne cycloaddition (CuAAC) reactions.

The kinetic behaviour of the photo-induced copper(i) catalyzed azide-alkyne cycloaddition (CuAAC) reaction was studied in detail using real-time Fourier transform infrared (FTIR) spectroscopy on both a solvent-based monofunctional and a neat polymer network forming system. The results in the solvent-based system showed near first-order kinetics on copper and photoinitiator concentrations up to a threshold value in which the kinetics switch to zeroth-order. This kinetic shift shows that the photo-CuAAC reaction is not susceptible from side reactions such as copper disproportionation, copper(i) reduction, and radical termination at the early stages of the reaction.

Blue-light activated rapid polymerization for defect-free bulk Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) crosslinked networks.

A visible-light (470 nm wavelength) sensitive Type II photoinitiator system is developed for bulk Cu(i)-catalyzed azide-alkyne cycloaddition (CuAAC) reactions in crosslinked networks. The accelerated photopolymerization eliminates UV-mediated azide decomposition allowing for the formation of defect-free glassy networks which exhibit a narrow glass transition temperature.