Three fluorinated Mo-Cu-thiolate isomers,[Ph4Ph[S2MoS2Cu(n-SPhF)], [n-SPhF = 2-fluorothiophenol (la)], 3-fluorothiophenol (lb), and 4-fluorothiophenol (1c)] were synthesized and spectroscopically characterized. The F-19-NMR signal of the fluorine atom in the.benzene has different chemical shift for each isomer, which is highly influenced by the local environment that can be manipulated by different solvents and solutes. The fluorine-19 chemical shift is an advantageous NMR structural probe in alternative to H-1-NMR [B.K. Maiti, T. Aviles, M. Matzapetakis, I. Moura, S.R. Pauleta, JJ.G. Moura, Eur. J. Inorg. Chem. (2012) 4159.], that can be used to provide local information on the pocket of the metal cluster in the Orange Protein (ORP). (C) 2014 Elsevier B.V. All rights reserved.

N2OR has been found to have two structural forms of its tetranuclear copper active site, the 4CuS Cu(Z)* form and the 4Cu2S Cu(Z) form. EPR, resonance Raman, and MCD spectroscopies have been used to determine the redox states of these sites under different reductant conditions, showing that the Cu(Z)* site accesses the 1-hole and fully reduced redox states, while the Cu(Z) site accesses the 2-hole and 1-hole redox states. Single-turnover reactions of N2OR for Cu(Z) and Cu(Z)* poised in these redox states and steady-state turnover assays with different proportions of Cu(Z) and Cu(Z)* show that only fully reduced Cu(Z)* is catalytically competent in rapid turnover with N2O.

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In this paper we address a solution for detecting and tolerating one of the most typical concurrency bugs: atomicity violations. More specifically, we address High-Level Atomicity Violations (HLAV). High-level atomicity violations result from the misspecification of the scope of an atomic block, by splitting it in two or more atomic blocks which may be interleaved with other atomic blocks. Figure 1 shows an example of this type of atomicity violation. The intuitive idea behind HLAV is that if two shared data items (e.g., memory locations) were both accessed inside an atomic block, they are interrelated and probably the programmer intention is that there shall be no interleavings between these two accesses. Therefore, if (in the same program) this two addresses are accessed separately in different atomic blocks, an unfortunate interleaving may cause an atomicity violation.

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