PubMed · 35035
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A M Klibanov. 1979. Enzyme stabilization by immobilization.. https://pubmed.ncbi.nlm.nih.gov/35035/
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Gas-phase protonation of pyridine with CH3NH3+, NH4+, t-C4H9+, H3O+ and CH5+ under thermal conditions was studied by variable-time neutralization-reionization mass spectrometry and ab initio calculations. N-Protonation was found to occur exclusively for CH3NH3+ through H3O+ and predominantly for CH5+. The calculated MP2/6-311G(2d,p) energies gave the proton affinities of N, C-2, C-3 and C-4 in pyridine as 924, 658, 686 and 637 kJ mol-1, respectively, which were in good agreement with previous experimental and theoretical results. Vertical neutralization of the N-protonated isomer (1H+) was accompanied by moderate Franck-Condon effects that deposited 20-21 kJ mol-1 in the 1H-pyridinium radicals (1H) formed. 1H was calculated by UMP2/6-311G(2d,p) and B3LYP/6-311G(2d,p) to be a bound species in its ground electronic state. A substantial fraction of stable 1H was detected in the spectra, which depended on the precursor ion internal energy. Deuterium labeling showed a specific loss of the N-bound hydrogen or deuterium in the radicals. The specificity increased with increasing internal energy in the radicals and decreasing contribution of ion dissociations following reionization. Variable-time measurements established specific loss of the N-bound deuterium also in dissociating low-energy 1D. Loss of hydrogen from 1H+ cations following reionization was highly endothermic and was accompanied by rearrangements that partially scrambled the ring hydrogens.
The earlier use of combined liquid chromatography/NMR spectrometry/mass spectrometry (LC/NMR/MS) involved the use of a particle beam interface. This paper describes further developments of this hyphenated technology, in particular the incorporation of an electrospray interface into the LC/NMR/MS system. This improved LC/NMR/MS system was designed for the support of a combinatorial library program. The power of this technique is demonstrated in the successful structural elucidation of each compound in a mixture of commercially available peptides.
Buckling transitions in superhelical DNA are sudden changes in shape that accompany a smooth variation in a key parameter, such as superhelical density. Here we explore the dependence of these transitions on the elastic constants for bending and twisting. A and C, important characteristics of DNA's bending and twisting persistence lengths. The large range we explore extends to other elastic materials with self-contact interactions, modeled here by a Debye-Hückel electrostatic potential. Our collective description of DNA shapes and energies over a wide range of p = A/C reveals a dramatic dependence of DNA shape and associated configurational transitions on p: transitions are sharp for large p but masked for small p. In particular, at small p, a nonplanar circular family emerges, in agreement with Jülicher's recent analytical predictions: a continuum of forms (and associated writhing numbers) is also observed. The relevance of these buckling transitions to DNA in solution is examined through studies of size dependence and thermal effects. Buckling transitions smooth considerably as size increases, and this can be explained in part by the lower curvature in larger plasmids. This trend suggests that buckling transitions should not be detectable for isolated (i.e., unbound) DNA plasmids of biological interest, except possibly for very large p. Buckling phenomena would nonetheless be relevant for small DNA loops, particularly for higher values of p, and might have a role in regulatory mechanisms: a small change in superhelical stress could lead to a large configurational change. Writhe distributions as a function of p, generated by Langevin dynamics simulations, reveal the importance of thermal fluctuations. Each distribution range (and multipeaked shape) can be interpreted by our buckling profiles. Significantly, the distributions for moderate to high superhelical densities are most sensitive to p, isolating different distribution patterns. If this effect could be captured experimentally for small plasmids by currently available imaging techniques, such results suggest a slightly different experimental procedure for estimating the torsional stiffness of supercoiled DNA than considered to date.