Mass spectral studies of some π-benzoylcyclopentadienylmanganese tricarbonyl derivatives

The loss of three CO groups from derivatives of π-C₆H₅COC₅H₄Mn(CO)₃ is a two-step mechanism in which the loss of two CO groups is followed by a third. Subsequent fragmentations generally involve rearrangement processes which often result in ring closure within the organic substrate. The central metal atoms plays an important part in such rearrangement processes and the positive charge can reside either on the metal or the ligand depending on the nature of the ligand. Fragmentation patterns are proposed for these systems.     

Structural and dynamical properties of methane clathrate hydrates

Equilibrium molecular dynamics (MD) simulations have been performed in both the NVT and NPT ensembles to study the structural and dynamical properties of fully occupied methane clathrate hydrates at 50, 125, and 200 K. Five atomistic potential models were used for water, ranging from fully flexible to rigid polarizable and nonpolarizable. A flexible and a rigid model were utilized for methane. The phonon densities of states were evaluated and the localized rattling modes for the methane molecules were found to couple to the acoustic phonons of the host lattice. The calculated methane density of states was found to be in reasonable agreement with available experimental data.     

The Copper Mediated Barbier Reactions of α,β-Unsaturated Ketones: Regioselective Conjugate and 1,2-Addition

The one-pot reaction of isophorone and other α, β,-unsaturated ketones with alkyl and aryl halides in the presence of magnesium and a copper salt (“Barbier” conditions) leads to the regiospecific formation of 1,4-addition products; the use of lithium leads to regioselective 1,2-addition.     

Towards the design of novel boron‐ and nitrogen‐substituted ammonia‐borane and bifunctional arene ruthenium catalysts for hydrogen storage

Electronic‐structure density functional theory calculations have been performed to construct the potential energy surface for H₂ release from ammonia‐borane, with a novel bifunctional cationic ruthenium catalyst based on the sterically bulky β‐diketiminato ligand (Schreiber et al., ACS Catal. 2012, 2, 2505). The focus is on identifying both a suitable substitution pattern for ammonia‐borane optimized for chemical hydrogen storage and allowing for low‐energy dehydrogenation. The interaction of ammonia‐borane, and related substituted ammonia‐boranes, with a bifunctional η⁶‐arene ruthenium catalyst and associated variants is investigated for dehydrogenation. Interestingly, in a number of cases, hydride‐proton transfer from the substituted ammonia‐borane to the catalyst undergoes a barrier‐less process in the gas phase, with rapid formation of hydrogenated catalyst in the gas phase. Amongst the catalysts considered, N,N‐difluoro ammonia‐borane and N‐phenyl ammonia‐borane systems resulted in negative activation energy barriers. However, these types of ammonia‐boranes are inherently thermodynamically unstable and undergo barrierless decay in the gas phase. Apart from N,N‐difluoro ammonia‐borane, the interaction between different types of catalyst and ammonia borane was modeled in the solvent phase, revealing free‐energy barriers slightly higher than those in the gas phase. Amongst the various potential candidate Ru‐complexes screened, few are found to differ in terms of efficiency for the dehydrogenation (rate‐limiting) step. To model dehydrogenation more accurately, a selection of explicit protic solvent molecules was considered, with the goal of lowering energy barriers for H‐H recombination. It was found that primary (1°), 2°, and 3° alcohols are the most suitable to enhance reaction rate. © 2014 Wiley Periodicals, Inc.     

Estimation of zeta potentials of titania nanoparticles by molecular simulation

Non-equilibrium molecular dynamics (NEMD) simulations have been performed for static electric fields for a range of positively charged spherical rutile-titania nanoparticles with radii of 1.5 to 2.9 nm for two different salt concentrations in water, in order to simulate electrophoresis directly. Using the observed limiting drag velocities, Helmholtz-Smoluchowski (HS) theory was used to estimate their ζ potentials. These estimates were compared to values from numerical solution of the non-linear Poisson-Boltzmann (PB) equation for representative configurations of the nanoparticles, in addition to idealised analytic and Debye-Hückel (DH) solutions about spherical particles of the same geometry and charge state, for the given salt concentrations. It was found that reasonable agreement was obtained between the various approaches, with the NEMD-HS results some 15%-15% smaller than the numerical PB results for more highly charged nanoparticles.     

Development of a trace gas stable isotope capture system in a mobile laboratory for temporal and spatial sampling of field and laboratory experiments

We describe the development of a novel mobile field laboratory, purposely designed for the automated capture and subsequent stable isotopic analyses of multiple gas samples. The multiple capture system is integrated into a mobile laboratory that is fully capable of measuring the concentration of carbon dioxide, methane and nitrous oxide trace gases in a flow-through system connected to a gas chromatograph fitted with both electron capture and flame ionisation detectors. The capture of gases is achieved by routing samples through a series of 135 mL gas flasks that are sealed by micro-solenoid valves triggered by a timing system. Trace gas light stable isotope ratio mass spectrometry can then be carried out on gas samples collected by the system (NERC (15)N Stable Isotope Facility). The excitingly unique potential of the system to the ecological research field is that it will allow the collection of cyclical data for three different trace gases both in real-time and in situ. We present data arising from the validation of this mobile system as well as a preliminary experimental assessment of this technique. This technique was used to measure delta(13)C in CO(2) and CH(4) in soil gases released from waterlogged cores and delta(13)C-CH(4) values were significantly depleted in wet cores compared with dry ones (p < 0.001).     

Global existence of time-dependent Yang-Mills-Higgs monopoles

We study the Cauchy problem for non-abelian Yang-Mills-Higgs theory in (3+1)-dimensional Minkowski spacetime. With suitable conditions on the background fields and a suitable choice of a Sobolev space for the subtracted gauge potentials and the Higgs field, we establish local existence. We then prove global existence by showing that an appropriate norm of the solutions cannot blow up in a finite time.     

Thin film pyrolytic carbon electrodes: A new class of carbon electrode for electroanalytical sensing applications

This communication describes the electrochemical properties of thin pyrolytic carbon (PyC) films created using a reliable, non-catalytic chemical vapour deposition (CVD) process. After deposition, the electron transfer characteristics of the films are optimised using a simple oxygen plasma treatment. The redox probes Ru(NH₃)₆^3+/2+, Fe(CN)₆^3?/4? and Fe^3+/2+ are employed to demonstrate that the resulting material is endowed with a large electrochemical surface area and outstanding electron transfer properties. Atomic force microscopy (AFM), Raman and X-ray photoelectron spectroscopy (XPS) are used to elucidate the morphology and chemical composition of the electrode surfaces. This material represents a new class of carbon electrode, and its large densities of edge-plane sites and oxygenated functionalities make it an ideal candidate for electrochemical sensor applications.     

Sequential monitoring of a Bernoulli sequence when the pre-change parameter is unknown

The task of monitoring for a change in the mean of a sequence of Bernoulli random variables has been widely studied. However most existing approaches make at least one of the following assumptions, which may be violated in many real-world situations: (1) the pre-change value of the Bernoulli parameter is known in advance, (2) computational efficiency is not paramount, and (3) enough observations occur between change points to allow asymptotic approximations to be used. We develop a novel change detection method based on Fisher’s exact test which does not make any of these assumptions. We show that our method can be implemented in a computationally efficient manner, and is hence suited to sequential monitoring where new observations are constantly being received over time. We assess our method’s performance empirically via using simulated data, and find that it is comparable to the optimal CUSUM scheme which assumes both pre- and post-change values of the parameter to be known.