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At least 1,153 records · Page 64

Protein Labeling via a Specific Lysine-Isopeptide Bond Using the Pilin Polymerizing Sortase from Corynebacterium diphtheriae

Proteins that are site-specifically modified with peptides and chemicals can be used as novel therapeutics, imaging tools, diagnostic reagents and materials. However, there are few enzyme-catalyzed methods currently available to selectively conjugate peptides to internal sites within proteins. Here we show that a pilus-specific sortase enzyme from Corynebacterium diphtheriae ((Cd)SrtA) can be used to attach a peptide to a protein via a specific lysine-isopeptide bond. Using rational mutagenesis we created (Cd)SrtA(3M), a highly activated cysteine transpeptidase that catalyzes in vitro isopeptide bond formation. (Cd)SrtA(3M) mediates bioconjugation to a specific lysine residue within a fused domain derived from the corynebacterial SpaA protein. Peptide modification yields greater than >95% can be achieved. We demonstrate that (Cd)SrtA(3M) can be used in concert with the Staphylococcus aureus SrtA enzyme, enabling dual, orthogonal protein labeling via lysine-isopeptide and backbone-peptide bonds.

McConnell, Scott A.↗

SMART transfer method to directly compare the mechanical response of water-supported and free-standing ultrathin polymeric films

Abstract Intrinsic mechanical properties of sub-100 nm thin films are markedly difficult to obtain, yet an ever-growing necessity for emerging fields such as soft organic electronics. To complicate matters, the interfacial contribution plays a major role in such thin films and is often unexplored despite supporting substrates being a main component in current metrologies. Here we present the shear motion assisted robust transfer technique for fabricating free-standing sub-100 nm films and measuring their inherent structural–mechanical properties. We compare these results to water-supported measurements, exploring two phenomena: 1) The influence of confinement on mechanics and 2) the role of water on the mechanical properties of hydrophobic films. Upon confinement, polystyrene films exhibit increased strain at failure, and reduced yield stress, while modulus is reduced only for the thinnest 19 nm film. Water measurements demonstrate subtle differences in mechanics which we elucidate using quartz crystal microbalance and neutron reflectometry.

36 MATERIALS SCIENCE↗

Age-aware constitutive materials model for a 3D printed polymeric foam

Abstract Traditional open or closed-cell stochastic elastomeric foams have wide-ranging applications in numerous industries: from thermal insulation, shock absorbing/gap-filling support cushions, packaging, to light-weight structural and positional components. Recent developments in 3D printing technologies by direct ink-write have opened the possibility of replacing stochastic foam parts by more controlled printed micro-structures with superior stress-distribution and longer functional life. For successful deployment as mechanical support or structural components, it is crucial to characterize the response of such printed materials to long-term external loads in terms of stress-strain behavior evolution and in terms of irreversible structural and load-bearing capacity changes over time. To this end, here we report a thermal-age-aware constitutive model for a 3D printed close-packed foam structure under compression. The model is based on the Ogden hyperfoam strain-energy functional within the framework of Tobolsky two-network scheme. It accurately describes experimentally measured stress-strain response, compression set, and load retention for various aging times and temperatures. Through the technique of time-temperature-superposition the model enables the prediction of long-term changes along with the quantification of uncertainty stemming from sample-to-sample variation and measurement noise. All aging parameters appear to possess the same Arrhenius activation barrier, which suggests a single dominant aging mechanism at the molecular/network level.

36 MATERIALS SCIENCE↗

Simultaneous cross-linking and p-doping of a polymeric semiconductor film by immersion into a phosphomolybdic acid solution for use in organic solar cells

Poly[ N -9'-heptadecanyl-2,7-carbazole- alt -5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PCDTBT) is shown to be simultaneously cross-linked and p-doped when immersed into a phosphomolybdic acid solution, yielding conductive films with low solubility that can withstand the solution processing of subsequent photoactive layers. Furthermore, such a modified PCDTBT film serves to improve hole collection and limit carrier recombination in organic solar cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid room temperature solubilization and depolymerization of polymeric lignin at high loadings

The relatively poor solubility of lignin in most pretreatment solvents remains one of the biggest challegnes in lignin valorization to improve overall biorefinery economics. In this work, rapid room temperature solubilization of lignin at high solid loadings (>30 wt%) can be easily achieved in a single step using ethylene glycol (EG). The solubilized lignin can be rapidly and quantitively recovered with the addtion of ethanol. The computational and nuclear magnetic resonance (NMR) spectroscopic studies confirm that strong hydrogen bond interactions between EG and the free hydroxyl groups present in lignin contribute to the lignin dissolution. In addition, hydrogen peroxide mediated depolymerization of dissolved lignin at low temperature (80 oC) was tested and the effect of EG molecules on depolymerization of ligin was also theoritically studied. The findings of this work provide mechanistic insights of hydrogen bond interactions in high lignin solubilization and valorization.

Environmental Molecular Sciences Laboratory↗

Microporous polymeric composite membranes with advanced film properties: pore intercalation yields excellent CO 2 separation performance

Polymers of intrinsic microporosity (PIMs) are revolutionary gas separation materials because of their ultra-high permeability, but suffer from low gas pair selectivity (for example CO 2 /N 2 ) and poor durability due to brittleness. In this paper, we present a simple solution to these problems by blending PIM-1 with compatible polymer blend composed of PIM-1 and an ether side chain polyphosphazene (MEEP80), which possesses better mechanical flexibility and higher CO 2 /N 2 selectivity than the native PIM-1 while maintaining high CO 2 permeability. Under mixed gas test conditions, a blend of 25 wt% MEEP80 in PIM-1 has a CO 2 permeability of 2440 barrer and a CO 2 /N 2 selectivity of 39 under mixed gas testing conditions, putting it among the best known polymers for CO 2 /N 2 separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, characterization, and polymerization of capped paddlewheel porous cages

Although paddlewheel-based structures are common among permanently porous metal–organic materials, suitable strategies for the isolation of metal node-terminated, capped paddlewheel-based cage structures remain limited. We explored the use of chelating dicarboxylate ligand derivates (esp) for the isolation of trimesate-linked cages, Mo 12 (btc) 4 (esp) 6 , that are structural analogs of the small octahedral pore of HKUST-1. The porosity of these novel cages is appreciably higher than that of previously reported structures of this type. We also demonstrate that pillaring the isolated cage with DABCO generated an amorphous polymer that featured exceptional thermal stability and enhanced porosity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗