In: ChemBioChem, 2018, vol. 19, no. 9, p. 922–926
In nature, proteins serve as media for long‐distance electron transfer (ET) to carry out redox reactions in distant compartments. This ET occurs either by a single‐step superexchange or through a multi‐step charge hopping process, which uses side chains of amino acids as stepping stones. In this study we demonstrate that Phe can act as a relay amino acid for long‐distance electron...
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In: The Journal of Organic Chemistry, 2006, vol. 7, no. 14, p. 5312 -5319
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In: The Journal of Organic Chemistry, 2013, vol. 78, no. 7, p. 2908–2913
Parent cyclobutenedione 1 was photolyzed and ionized in an Ar matrix at 10K. The bisketene 2 that results in both cases (in the form of its radical cation after ionization) was characterized by its IR spectrum and by high-level quantum chemical calculations. Experiment and theory show that the neutral bisketene has only a single conformation where the two ketene moieties are nearly perpendicular,...
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In: The Journal of Organic Chemistry, 2009, vol. 74, no. 11, p. 4017–4023
The purpose of this paper is to convince practitioners of ¹H NMR spectroscopy to consider simple quantum chemical calculations as a viable option to aid them in the assignment of their spectra. To this end, it is demonstrated, on a test set of 80 conformationally stable molecules of various kinds carrying different functional groups, that, in contrast to what is claimed in the literature, large...
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In: The Journal of Physical Chemistry A, 2007, vol. 111, no. 9, p. 1667 -1676
The first few bands in the optical spectra of radical cations can often be interpreted in terms of A-type transitions that involve electron promotions from doubly occupied to the singly occupied molecular orbital (SOMO) and/or B-type transition which involve electron promotion from the SOMO to virtual molecular orbitals. We had previously demonstrated that, by making use of Koopmans' theorem, the...
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In: Journal of the American Chemical Society, 2013, vol. 135, no. 23, p. 8625–8631
Carbocations are crucial intermediates in many chemical reactions; hence, considerable effort has gone into investigating their structures and properties, for example, in superacids, in salts, or in the gas phase. However, studies of the vibrational structure of carbocations are not abundant, because their infrared spectra are difficult to obtain in superacids or salts (where furthermore the...
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In: Angewandte Chemie International Edition, 2006, vol. 45, no. 40, p. 6616 - 6619
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In: Journal of the American Chemical Society, 2006, vol. 128, no. 24, p. 7828 -7834
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In: The Journal of Physical Chemistry A, 2011, vol. 115, no. 26, p. 7700–7708
Extending our previous study on the title species (J. Phys. Chem. A2010, 114, 6787), we investigated the dimer cations that are formed on oxidation of the glucobrassin derivatives indole-3-carbinol (I3C) and diindolylmethane (DIM) and of parent indole (I). Radiolysis in ionic liquid and Ar matrices shows that, at sufficiently high concentrations and/or on...
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In: Organic & Biomolecular Chemistry, 2011, vol. 9, p. 3636-3657
The bond dissociation energies (BDEs) and radical stabilization energies (RSEs) which result from 166 reactions that lead to carbon-centered radicals of the type ˙CH₂X, ˙CHXY and ˙CXYZ, where X, Y and Z are any of the fourteen substituents H, F, Cl, NH₂, OH, SH, CH=CH₂, C≡CH, BH₂, CHO, COOH, CN, CH₃, and CF₃, were calculated using spin-restricted and -unrestricted variants of the...
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