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Abstract The Q‐speciation and the role of modifier dynamics on network relaxation in the supercooled mixed‐alkali–alkaline‐earth (MAAE) Na–Ba metaphosphate liquids are investigated using a combination of³¹P nuclear magnetic resonance (NMR) spectroscopy, calorimetric, electrical conductivity, and rheological measurements. Progressive replacement of Na with Ba in these glasses is shown to result in an increasing disproportionation of Q²species via the reaction: 2Q² = Q¹+ Q³. Unlike mixed‐alkali liquids, the Na–Ba metaphosphate liquids display a monotonic variation in isothermal electrical conductivity, glass transition temperature, calorimetric and kinetic fragility, and isothermal viscosity. It is hypothesized that this monotonic variation arises from the lack of elastic facilitation of network relaxation via coupled hopping of Na–Ba pairs as these modifier cations are prohibited from mixing randomly due to the differences between their size, mass, charge, and mobility. Isobaric heat capacity measurements provide supporting evidence in favor of a such a nonrandom mixing between the modifier cations in Na–Ba metaphosphate glasses and liquids. 

The effects of atomic mass in terms of its zero-point vibrational energy, on molar volume, glass transition temperature Tg, and viscosity are studied in glassy and supercooled B2O3 liquids using boron isotope substitutions. The molar volume decreases and Tg and isothermal viscosity increase on the substitution of lighter 10B isotopes with the heavier 11B isotopes. These effects are argued to be a manifestation of the higher zero-point vibrational energy of the lighter isotope, which along with the anharmonicity of the potential well, results in a longer equilibrium inter-atomic distance and larger mean-square displacement with respect to that for the heavier isotope. The isotope effect on viscosity is increasingly enhanced as the temperature approaches Tg, which is shown to be consistent with the prediction of the elastic models of viscous flow and shear relaxation. 

The incorporation of the nonstandard amino acid para-nitro-L-phenylalanine (pN-Phe) within proteins has been used for diverse applications, including the termination of immune self-tolerance. However, the requirement for the provision of chemically synthesized pN-Phe to cells limits the contexts where this technology can be harnessed. Here we report the construction of a live bacterial producer of synthetic nitrated proteins by coupling metabolic engineering and genetic code expansion. We achieved the biosynthesis of pN-Phe in Escherichia coli by creating a pathway that features a previously uncharacterized nonheme diiron N-monooxygenase, which resulted in pN-Phe titers of 820 ± 130 µM after optimization. After we identified an orthogonal translation system that exhibited selectivity toward pN-Phe rather than a precursor metabolite, we constructed a single strain that incorporated biosynthesized pN-Phe within a specific site of a reporter protein. Overall, our study has created a foundational technology platform for distributed and autonomous production of nitrated proteins.