QM/MM studies of Ni-Fe hydrogenases: the effect of enzyme environment on the structure and energies of the inactive and active states

The catalytically active (Ni-SI and Ni-R) and inactive states (Ni-A and Ni-B) of Ni-Fe hydrogenases have been studied using density functional theory (DFT) methods. Both isolated clusters and clusters embedded in the enzyme have been used to model the Ni-A, Ni-B, Ni-SI and Ni-R states. The BP86 and B3LYP functionals were employed, and hybrid quantum mechanical (QM)/molecular mechanical (MM) methods were used for the embedded calculations. The QM/MM studies, rather than the isolated cluster calculations, were generally found to give structures which correlated better with X-ray data. The structure of the unready state (Ni-A), was correctly predicted by the QM/MM, but not by the isolated cluster calculation. Comparison with the observed crystal structure favoured the catalytically active state, Ni-SI, to be the protonated (Ni-SI(II)), rather than the unprotonated state (Ni-SI(I)). In the QM/MM studies, the binding of H(2) to Ni-SI(II) is preferred at the Ni (Ni-R(Ni)), rather than at the Fe centre (Ni-R(Fe)), in agreement with xenon binding studies, and in contrast to isolated cluster studies. These calculations cannot say with certainty which functional should be favoured, nor the preferred spin state of the catalytically active species. However, the lack of any predicted structure in which H(2) binds to the Fe centre, does favour a low spin state for Ni-SI(II), and the use of the BP86 functional. This is in agreement with recent high level ab initio calculations of a model of the Ni-SI(I) state.     

The dynamics of water exchange in gadolinium DOTA complexes studied by transition path sampling and potential of mean force methods

The mechanism of water exchange at the Gd centre of the two isomers of [Gd(iii)DOTA](-) (gadolinate(1-), [1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetato(4-)-N1,N4,N7,N10,O1,O4,O7,O10]) has been explored using transition path sampling and potential of mean force methods to sample those regions of phase space inaccessible to standard molecular dynamics simulation. We find that there are definite differences in the details of the solvent rearrangement accompanying the exchange of the capping water molecule for the two isomers. We conclude that these solvent effects, rather than any differences in the binding energy of the capping water, are central in determining the exchange rate. We find that the potential of mean force studies yield absolute and relative rates of water exchange for the two isomers that are in good agreement with experiment.     

Uniform Boundedness by Averaging

We consider a system of functional difierential equations with infinite delay and derive conditions on Liapunov functionals to ensure that solutions are uniformly bounded and uniformly ultimately bounded. The analysis is based on the method of finding a bound on the average values of unknown solutions and Jensen's inequality. Comparisons between our theorems and those existing in the literature are also given.     

Virtual Teams: What are their Characteristics, and Impact on Team Performance?

To date, efforts to understand virtual teaming have been largely anecdotal and atheoretical. Therefore, drawing from the extant research in the groups domain, we attempt to ground the definition of a virtual team in well-established group-level constructs, and design a simulation study to investigate the impact of different virtual team characteristics on team performance. Essentially, we argue that the virtual team is defined by three key characteristics—the virtual team context, the virtual team composition, and the virtual team structure. Using the VDT computational discrete event simulation model as our experimental platform, we simulated different virtual team models, and examined their impact on various team performance dimensions. We found that virtual team characteristics have different effects on different aspects of team performance. The virtual context team had a lower rework volume but higher coordination volume and longer project duration than the virtual composition team. Interestingly, we also found that the virtual structure team performed better than the software development team baseline model in all aspects of team performance. Based on these results, we proposed strategies to improve performance in different types of virtual team. Specifically, we propose (1) increasing the ease of communication and availability of routines in the virtual context team; (2) clarifying role expectations and fostering a team culture in the virtual composition team; and (3) implementing a lateral structure in the virtual team. Our results also suggest that firms should consider situational demands, specifically tolerance for errors and coordination volume, when considering the design of virtual teams.     

(1E,3E,5E)‐1,2,3,4,5,6‐Hexa­fluoro‐1,6‐di­phenyl­hexatriene

The title triene, C₁₈H₁₀F₆, was prepared via the Pd⁰ coupling reaction of (E)‐(1,2‐di­fluoro‐1,2‐ethenediyl)­bis­(tri­butyl­stan­nane) with (Z)‐β‐iodo‐α,β‐di­fluoro­styrene in N,N′‐dimethylformamide/tetrahydrofuran. The crystal structure shows the product to be the 1E,3E,5E isomer. Due to steric interactions between F atoms, the double bonds are not coplanar. The planes defined by the two terminal double bonds are almost perpendicular.     

Preparation of α,α-difluoromethylene functionalized sulfones

Sulfination of bromodifluoroacetate or acetamide 1 with sodium dithionite gives the corresponding sulfinates 2a , and 2b , respectively, which upon cuprous bromidc catalyzed allylation afford the allylsulfonyl-difluoroacetate and acetamides. Phenyl- or alkylsulfonyldifluoroacetates and acetamides can be readily prepared from reaction of 1 with thiolates, followed by oxidation with hydrogen peroxide.     

Exact mass measurements using a 7 tesla fourier transform ion cyclotron resonance mass spectrometer in a good laboratory practices-regulated environment

Fourier transform ion cyclotron resonance mass spectrometry has been found to produce reliable exact mass measurements using two different internal calibration methods. For these measurements, electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) were utilized both individually and in tandem. For internal calibration with a co-dissolved polyethylene glycol standard, measurements of 41 compounds resulted in an average absolute mass determination error of 0.7 ppm, with a standard deviation of 0.9 ppm. For comparison, internal calibration was effected through the simultaneous use of ESI and MALDI, with the former being used for the introduction of analyte ions and the latter for formation of polymethylmethacrylate calibrant ions. This technique led to mass measurements with an average absolute error of 0.8 ppm and a standard deviation of 1.0 ppm. In addition, exact mass measurements of tandem mass spectrometry fragment ions were made for 35 compounds using external calibration with a single internal mass standard. The observed average absolute error was 0.7 ppm with a standard deviation of 1.0 ppm.