An efficient closed-shell singles and doubles coupled-cluster method

A reformulated set of equations for the closed-shell singles and doubles coupled-cluster (CCSD) method is presented. A computational cost of n_v⁴n₀²+7n_v³n₀³+1n_v²n₀⁴ for the n⁶ steps is obtained, where n_v is the number of virtual molecular orbitals included in the CCSD procedure, n₀ is the number of doubly occupied molecular orbitals and n=n₀+n_v. Test calculations for the cis and trans isomers of FNNF and planar and pyramidal CH₃⁻ are presented. Equilibrium structures determined with large Gaussian basis sets at the second-order Møller-Plesset (MP2) perturbation level of theory are reported and used for the other electron correlation methods. With the largest one-particle basis set (144 contracted Gaussian functions), the equilibrium geometries of cis- and trans-FNNF agree with experiment. Based on analyses of planar and pyramidal CH₃⁻ wavefunctions and the calculated inversion barrier, it is suggested that the molecular anion may not exist in a planar configuration but that autodetachment of an electron occurs before the transition state is reached. Comparisons of our new CCSD procedure demonstrate that coupled-cluster methods are not significantly more expensive than similar electron correlation techniques.     

Organic synthesis with sulphones—XVII: The anti-markownikoff halosulphonylation of olefins via an ionic pathway,and a new method of preparing benzenesulphonyl iodide

Iodine and bromine in the presence of sodium benzenesulphinate react with olefins in acetone solution to give halosulphones resulting from an apparent steric direction of attack at the intermediate halonium ion. A straightforward preparation of benzenesulphonyl iodide from benzenesulphonyl chloride and sodium iodide is also described.     

Adsorption of<Emphasis Type="Italic"> N</Emphasis>-dodecyl-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethyl-3-ammonio-1-propanesulfonate (DDAPS), a model zwitterionic surfactant,on the Au(111) electrode surface

Electrochemical measurements including cyclic voltammetry, differential capacity, and chronocoulometry have been used to characterize the adsorption behaviors of the zwitterionic surfactant N-dodecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (DDAPS) on the Au(111) electrode surface. The thermodynamics of the ideally polarized electrode have been employed to determine the Gibbs excess and the Gibbs energy of adsorption. The results show that the adsorption of DDAPS has a multistate character. The first two states are observed at potentials close to zero charge. At low bulk DDAPS concentrations, it corresponds to the formation of a film of nearly flat adsorbed molecules. At higher concentrations it is converted into a hemimicellar state. The second state is formed at negative potentials and charge densities close to 0 C cm^–2. It corresponds to a film of tilted molecules oriented with the hydrocarbon tail towards the metal and the polar head toward the solution.Dedicated to Professor Zbigniew Galus on the occasion of his 70^th birthday and in recognition of his many contributions to electrochemistry.     

Solid state separated-local-field NMR spectroscopy on half-integer quadrupolar nuclei: principles and applications to borane analysis

New multidimensional NMR methods correlating the quadrupolar and heteronuclear dipolar interactions affecting a half-integer quadrupolar spin in the solid state are introduced and exemplified. The methods extend separated-local-field magic-angle spinning (SLF MAS) NMR techniques that have been used successfully in spin-(1)/(2) spectroscopy to the study of S >/= (3)/(2) nuclei. In our implementation, these techniques avoid homonuclear proton decoupling requirements by relying on moderately fast MAS rates (6-15 kHz) and use rotor-synchronized constant-time pulse sequences to achieve nearly arbitrary amplifications of the apparent dipolar coupling strengths. The result is a suite of simple 2D NMR experiments, whose line shapes carry valuable information about the structure and dynamics of solids containing quadrupolar and proton nuclei. The potential of these sequences was exploited to gather new insight into the structure and dynamics of a variety of boron-containing samples. These experimental SLF schemes were also extended to 3D NMR experiments that incorporate multiple-quantum MAS, thus enabling the resolution needed to study multiple chemical sites in a solid and providing a useful tool for the assignment of inequivalent sites.     

The electronic structure of FeV-cofactor in vanadium-dependent nitrogenase

The electronic structure of the active-site metal cofactor (FeV-cofactor) of resting-state V-dependent nitrogenase has been an open question, with earlier studies indicating that it exhibits a broad S = 3/2 EPR signal (Kramers state) having g values of ∼4.3 and 3.8, along with suggestions that it contains metal-ions with valencies [1V³⁺, 3Fe³⁺, 4Fe²⁺]. In the present work, genetic, biochemical, and spectroscopic approaches were combined to reveal that the EPR signals previously assigned to FeV-cofactor do not correlate with active VFe-protein, and thus cannot arise from the resting-state of catalytically relevant FeV-cofactor. It, instead, appears resting-state FeV-cofactor is either diamagnetic, S = 0, or non-Kramers, integer-spin (S = 1, 2 etc.). When VFe-protein is freeze-trapped during high-flux turnover with its natural electron-donating partner Fe protein, conditions which populate reduced states of the FeV-cofactor, a new rhombic S = 1/2 EPR signal from such a reduced state is observed, with g = [2.18, 2.12, 2.09] and showing well-defined ⁵¹V (I = 7/2) hyperfine splitting, a_iso = 110 MHz. These findings indicate a different assignment for the electronic structure of the resting state of FeV-cofactor: S = 0 (or integer-spin non-Kramers state) with metal-ion valencies, [1V³⁺, 4Fe³⁺, 3Fe²⁺]. Our findings suggest that the V³⁺ does not change valency throughout the catalytic cycle.

Active site FeV-cofactor of the V-nitrogenase and the EPR spectrum of the reduced cofactor showing ⁵¹V-hyperfine coupling.     

A Novel Anti-Inflammatory d-Peptide Inhibits Disease Phenotype Progression in an ALS Mouse Model

Amyotrophic lateral sclerosis (ALS) is a progressive neurodegenerative disease characterised by selective neuronal death in the brain stem and spinal cord. The cause is unknown, but an increasing amount of evidence has firmly certified that neuroinflammation plays a key role in ALS pathogenesis. Neuroinflammation is a pathological hallmark of several neurodegenerative disorders and has been implicated as driver of disease progression. Here, we describe a treatment study demonstrating the therapeutic potential of a tandem version of the well-known all-d-peptide RD2 (RD2RD2) in a transgenic mouse model of ALS (SOD1*G93A). Mice were treated intraperitoneally for four weeks with RD2RD2 vs. placebo. SOD1*G93A mice were tested longitudinally during treatment in various behavioural and motor coordination tests. Brain and spinal cord samples were investigated immunohistochemically for gliosis and neurodegeneration. RD2RD2 treatment in SOD1*G93A mice resulted not only in a reduction of activated astrocytes and microglia in both the brain stem and lumbar spinal cord, but also in a rescue of neurons in the motor cortex. RD2RD2 treatment was able to slow progression of the disease phenotype, especially the motor deficits, to an extent that during the four weeks treatment duration, no significant progression was observed in any of the motor experiments. Based on the presented results, we conclude that RD2RD2 is a potential therapeutic candidate against ALS.     

Pd-catalysed cross coupling of terminal alkynes to diynes in the absence of a stoichiometric additive

An efficient, room temperature procedure for the cross-coupling of a range of terminal alkynes, using standard Sonogashira cross-coupling conditions (Pd/Cu) is presented. At higher reaction temperatures, head-to-tail or head-to-head dimerisation affords 1,3- and 1,4-disubstituted enynes, respectively as minor products.     

Dilatational rheology of beta-casein adsorbed layers at liquid-fluid interfaces

The rheological behavior of beta-casein adsorption layers formed at the air-water and tetradecane-water interfaces is studied in detail by means of pendant drop tensiometry. First, its adsorption behavior is briefly summarized at both interfaces, experimentally and also theoretically. Subsequently, the experimental dilatational results obtained for a wide range of frequencies are presented for both interfaces. An interesting dependence with the oscillation frequency is observed via the comparative analysis of the interfacial elasticity (storage part) and the interfacial viscosity (loss part) for the two interfaces. The analysis of the interfacial elasticities provides information on the conformational transitions undergone by the protein upon adsorption at both interfaces. The air-water interface shows a complex behavior in which two maxima merge into one as the frequency increases, whereas only a single maximum is found at the tetradecane interface within the range of frequencies studied. This is interpreted in terms of a decisive interaction between the oil and the protein molecules. Furthermore, the analysis of the interfacial viscosities provides information on the relaxation processes occurring at both interfaces. Similarly, substantial differences arise between the gaseous and liquid interfaces and various possible relaxation mechanisms are discussed. Finally, the experimental elasticities obtained for frequencies higher than 0.1 Hz are further analyzed on the basis of a thermodynamic model. Accordingly, the nature of the conformational transition given by the maximum at these frequencies is discussed in terms of different theoretical considerations. The formation of a protein bilayer at the interface or the limited compressibility of the protein in the adsorbed state are regarded as possible explanations of the maximum.