The synthesis of water soluble decalin-based thiols and S-nitrosothiols—model systems for studying the reactions of nitric oxide with protein thiols

Spivey, Alan C.; Colley, Jacqueline; Sprigens, Lindsey; Hancock, Susan M.; Cameron, David; Chigboh, Kordi; Veitch, Gemma E.; Frampton, Christopher S.; Adams, Harry

doi:10.1039/b503758a

Cited by 8 publications

(2 citation statements)

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“…The general instability of RSNOs has made them difficult to study. The most efficient synthetic approach to make more stable RSNO species has been focused on tertiary or aromatic derivatives bearing bulky groups in the 2 and 6 positions . Generally, these RSNOs are more stable than aliphatic secondary or primary RSNOs because of the increase in steric interactions associated with the dimerization of the thiyl radical that forms upon homolytic cleavage of the S–N bond .…”

Section: Introductionmentioning

confidence: 99%

Modulating Nitric Oxide Release byS-Nitrosothiol Photocleavage: Mechanism and Substituent Effects

et al. 2012

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The photochemistry and photophysics of a series of S-nitrosothiols (RSNOs) have been studied computationally. The photocleavage mechanism of the model compound CH(3)SNO to release CH(3)S· and ·NO was studied at the CASPT2 level resulting in a barrierless process when irradiating in the visible region (S(1)), in the near UV region (S(2)) and for photosensitized (T(1)) reaction. The absorption energy required to initiate photocleavage was calculated at the CASPT2 and B3P86 levels showing the possibility of the modulation of NO release by RSNO photoactivation as a function of the substituent R. Good correlations between the wavelengths of the lowest energy (1)(n,π*) and (1)(π,π*) transitions of aryl S-nitrosothiols and the corresponding Hammett constants of the substituents have been obtained.

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Section: Introductionmentioning

confidence: 99%

Modulating Nitric Oxide Release byS-Nitrosothiol Photocleavage: Mechanism and Substituent Effects

et al. 2012

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“…There is a paucity of structural data on RSNOs. The crystallographic results to date [5][6][7][8][9][10][11][12][13] reveal that RSNOs possess an elongated S-N bond (1.7-1.85 A ˚, Table 1 and Fig. 1) and can exist as cis (syn) and trans (anti) conformers.…”

Section: Introductionmentioning

confidence: 99%

Structure and stability of HSNO, the simplest S-nitrosothiol

Timerghazin

Peslherbe

English

2008

Phys. Chem. Chem. Phys.

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High-level ab initio calculations employing the CCSD and CCSD(T) coupled cluster methods with a series of systematically convergent correlation-consistent basis sets have been performed to obtain accurate molecular geometry and energetic properties of the simplest S-nitrosothiol (RSNO), HSNO. The properties of the S-N bond, which are central to the physiological role of RSNOs in the storage and transport of nitric oxide, are highlighted. Following corrections for quadruple excitations, core-valence correlation and relativistic effects, the CCSD(T) method extrapolated to the complete basis set (CBS) limit yielded values of 1.85 A and 29.2 kcal mol(-1) for the S-N bond length and the dissociation energy for homolysis of the S-N bond, respectively, in the energetically most stable trans-conformer of HSNO. The properties of the S-N bond strongly depend on the basis-set size and the inclusion of triple, and, to a lesser extent, quadruple excitations in the coupled cluster expansion. CCSD calculations systematically underestimate the S-N equilibrium distance and S-N bond dissociation energy by 0.05-0.07 A and 6-7 kcal mol(-1), respectively. The significant differences between the CCSD(T) and CCSD descriptions of HSNO, the high values of the coupled cluster T(1) (0.027) and D(1) (0.076) diagnostics, as well as the instability of the reference restricted Hartree-Fock (RHF) wavefunction indicate that the electronic structure of the SNO group possesses multireference character. Previous quantum-chemical data on RSNOs are reexamined based on the new insight into the SNO electronic structure obtained from the present high-level calculations on HSNO.

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