The assessment of risk in relation to major hazards,with particular reference to nuclear reactors

The article concentrates mainly on the developing pattern of safety thinking and safety practices which have been brought about by, and in turn have influenced, the growth of modern industrial technology, particularly in the nuclear field.

The need to minimize the chance of accidents with serious consequences led to pursuit of safety by siting, by containment and by automatic built-in safety mechanisms; these are discussed.

Codes of practice and safety guidelines are becoming linked with more quantitative goals to achieve desired objectives in safety and reliability. This is particularly important in the assessment of major hazards.     

Exfoliation of a stack of platelets and intercalation of polymer chains: Effects of molecular weight,entanglement, and interaction with the polymer matrix

Exfoliation of a stack of sheets (a model for clay platelets) in a dynamic matrix of polymer chains is investigated by a computer simulation model. How the interplay between the thermodynamics (interaction-driven) and conformational (structural constraints) entropy affects the exfoliation of sheets is the subject of this study. A stack of four sheets with a small initial interlayer distance constitutes the layer on a discrete lattice. The layered platelets are immersed in a matrix represented by the mobile polymer chains which occupy a fraction (concentration) of the lattice sites. Both sheets and chains are modeled by the bond-fluctuation mechanism and execute their stochastic motion via Metropolis algorithm. An attractive and a repulsive interaction between the polymer matrix and platelets are considered. Exfoliation of the sheets is examined by varying the molecular weight of the polymer chains forming a dynamic network matrix with various degrees of entanglements. At low-molecular weight of the polymer, exfoliation is achieved with repulsive interaction and the exfoliation is suppressed with attractive matrix as sheets stick together via polymer mediated interaction introduced by intercalated polymer chains. Increasing the molecular weight of the polymer matrix suppresses the exfoliation of sheets primarily due to enhanced entanglement—at high-molecular weight (with the radius of gyration of polymer chains larger than the characteristic linear dimension of the platelets), the stacked (layered) morphology is arrested via entropic trapping and exfoliation ceases to occur. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2696–2710, 2008     

Multiple pathways for the oxygenation of a ruthenium(II) dithiocarbamate complex: S-oxygenation and S-extrusion

The reactions of Ru(bpy)(2)(N,N-dimethyldithiocarbamate)(+), 1, with O-atom-transfer reagents such as hydrogen peroxide, m-chloroperoxybenzoic acid, and oxone have been studied and several resulting derivatives isolated and structurally characterized. Both S-oxygenation and S-extrusion may occur depending upon reagent and conditions. Excess peroxygenation leads to a stable dioxygenate, Ru(bpy)(2)(N,N-dimethylthiocarbamatesulfinate-S,S)(+), 3. Stoichiometric oxygenation leads to mixtures of products from which two forms of monooxygenated species Ru(bpy)(2)(N,N-dimethylperoxydithiocarbamate-S,S), 2a, and Ru(bpy)(2)(N,N-dimethylperoxydithiocarbamate-O,S), 2b, and an S-extruded product, Ru(bpy)(2)(N,N-dimethylmonothiocarbamate)(+), 4, have been isolated as PF(6)(-) salts. The S,S-bound monooxygenate is unstable over time toward either O-atom-transfer reactions via disproportionation or reaction with phosphines or S-extrusion yielding complex 4 in which the thiocarbamate is bonded solely through the remaining S atom. All the complexes have been characterized by (1)H NMR, UV-vis, and mass spectroscopies, and all but the highly reactive 2a structurally determined by X-ray crystallography.     

Bonding in HNO-myoglobin as characterized by X-ray absorption and resonance raman spectroscopies

The EXAFS and resonance Raman spectra on the HNO-myoglobin adduct, 1, are consistent with the presence of HNO bound to a heme center. The three-dimensional structure about the heme center of 1 obtained from multiple-scattering (MS) analysis of the EXAFS of the heme protein yielded an Fe-N-O bond angle of 131 degrees and an Fe-N bond length of 1.82 A, which compare well with published values for model complexes containing RNO ligands. Resonance Raman spectra identified the nu(N=O) stretch at 1385 cm-1 (confirmed by 15N labeling), which corresponds well with those reported for small molecule HNO complexes. The wavelength of the nu(Fe-N) at 636 cm-1 of 1 is significantly higher than those of MbIINO and MbIIINO (554 and 595 cm-1, respectively). The XAFS, XANES, and resonance Raman data are all consistent with the structure deduced from the NMR experiments, providing more detail on the bonding between HNO and the metal center.     

Influence of Sulfur Metalation on the Accessibility of the Ni(II/I) Couple in [N,N'-Bis(2-mercaptoethyl)-1,5-diazacyclooctanato]nickel(II): Insight into the Redox Properties of [NiFe]-Hydrogenase

A redox model study of [NiFe] hydrogenase has examined a series of five polymetallics based on the metalation of the dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctane]Ni(II), Ni-1. Crystal structures of three polymetallics of the series have been reported earlier: [(Ni-1)(2)()Ni]Cl(2)(), [(Ni-1)(2)()FeCl(2)()](2)(), and [(Ni-1)(3)()(ZnCl)(2)()]Cl(2)(). Two are described here: [(Ni-1)(2)()Pd]Cl(2)().2H(2)()Ocrystallizes in the monoclinic system, space group P2(1)/c with cell constants a = 12.212(4) ?, b = 7.642(2) ?, c = 16.625(3) ?, beta = 107.69(2) degrees, V = 1443.230(0) ?(3), Z = 2, R = 0.051, and R(w) = 0.056. [(Ni-1)(2)()CoCl]PF(6)() crystallizes in the triclinic system, space group P&onemacr;, with cell constants a = 8.14(2) ?, b = 13.85(2) ?, c = 15.67(2) ?, alpha = 113.59(10) degrees, beta = 101.84(14) degrees, gamma = 94.0(2) degrees, V = 1561.620(0)?(3), Z = 2, R = 0.072, and R(w) = 0.077. In all Ni-1 serves as a bidentate metallothiolate ligand with a "hinge" angle in the range 105-118 degrees and Ni-M distances of 2.7- 3.7 ?. The most accessible redox event is shown by EPR and electrochemistry to reside in the N(2)S(2)Ni unit and is the Ni(II/I) couple. Charge neutralization of the thiolate sulfurs by metalation can (dependent on the interacting metal) stabilize the Ni(I) state as efficiently as methylation forming a thioether. The implication of these results for the heterometallic active site of [NiFe]-hydrogenase as structured from Desulfovibrio gigas (Volbeda, A., et al. Nature, 1995, 373, 580), the generality of the Ni(&mgr;-SR)(2)M hinge structure, and a possible explanation for the unusual redox potentials are discussed.