An assessment of theoretical procedures for π-conjugation stabilisation energies in enones

We introduce a representative database of 22 α,β- to β,γ-enecarbonyl isomerisation energies (to be known as the EIE22 data-set). Accurate reaction energies are obtained at the complete basis-set limit CCSD(T) level by means of the high-level W1-F12 thermochemical protocol. The isomerisation reactions involve a migration of one double bond that breaks the conjugated π-system. The considered enecarbonyls involve a range of common functional groups (e.g., Me, NH₂, OMe, F, and CN). Apart from π-conjugation effects, the chemical environments are largely conserved on the two sides of the reactions and therefore the EIE22 data-set allows us to assess the performance of a variety of density functional theory (DFT) procedures for the calculation of π-conjugation stabilisation energies in enecarbonyls. We find that, with few exceptions (M05-2X, M06-2X, BMK, and BH&;HLYP), all the conventional DFT procedures attain root mean square deviations (RMSDs) between 5.0 and 11.7 kJ mol^?1. The range-separated and double-hybrid DFT procedures, on the other hand, show good performance with RMSDs below the ‘chemical accuracy’ threshold. We also examine the performance of composite and standard ab initio procedures. Of these, SCS-MP2 offers the best performance-to-computational cost ratio with an RMSD of 0.8 kJ mol^?1.     

On Transverse and Rotational Symmetries in Elastic Rods

The influences of transverse and rotational symmetries on the strain-energy functions of elastic rods are discussed. Complete function bases are presented and, for some constrained theories, these bases are also proven to be irreducible. The treatment of symmetry is based on a reformulation of a recent work by Luo and O’Reilly. It is also shown how this work relates to existing treatments by Antman and Healey for a particular constrained rod theory.     

1,4-Addition of aryl boronic acids to α,β-unsaturated ketones catalyzed by a CCC–NHC pincer rhodium complex

An air- and water-stable CCC–NHC pincer Rh complex catalyzed the 1,4-addition of aryl boronic acids to α,β-unsaturated ketones and aldehydes. This bench top method proceeds in eco-friendly solvents including methanol and water. The scope of boronic acids was expanded to include heterocyclic examples.     

The biological buffer bicarbonate/CO2 potentiates H2O2-mediated inactivation of protein tyrosine phosphatases

Hydrogen peroxide is a cell signaling agent that inactivates protein tyrosine phosphatases (PTPs) via oxidation of their catalytic cysteine residue. PTPs are inactivated rapidly during H(2)O(2)-mediated cellular signal transduction processes, but, paradoxically, hydrogen peroxide is a rather sluggish PTP inactivator in vitro. Here we present evidence that the biological buffer bicarbonate/CO(2) potentiates the ability of H(2)O(2) to inactivate PTPs. The results of biochemical experiments and high-resolution crystallographic analysis are consistent with a mechanism involving oxidation of the catalytic cysteine residue by peroxymonocarbonate generated via the reaction of H(2)O(2) with HCO(3)(-)/CO(2).     

Computational evaluation of mass filter acceptance and transmittance influenced by developing fields: An application of the plane method to investigate prefilter efficacy for rectangular wave operated mass filters

The acceptance of quadrupole mass filters is improved when the alternating current (AC) and direct current (DC) fields are developed separately. Physically, this is achieved when a short RF only quadrupole (prefilter) is situated directly ahead of the mass filter. The acceptance gained by a system operating with a prefilter can be observed as an increase in sensitivity over conventional operation. Frequency dynamic duty cycle based rectangular waveform driven (rectangular wave) mass filters, a recent development, currently do not operate with prefilters. Little is known about the influence of duty cycle changes on the acceptance of rectangular wave mass filters. The sensitivity gain seen by conventional systems operating with prefilters indicates that the sensitivity of duty cycle based rectangular wave systems should increase comparably. The objective of this work was to determine prefilter efficacy for nonspecific rectangular wave mass filter systems. In this work, the plane method of acceptance was used to model the change to the acceptance and transmittance of sine and rectangular waveform driven mass filters under different modes of field development. Both systems indicated a fourfold increase in sensitivity when the mass filtering DC or duty cycle was delayed.     

Centrality in Rees-Sushkevich varieties

Denote by RS _n the variety generated by all completely 0-simple semigroups over groups of exponent dividing n. Subvarieties of RS _n are called Rees-Sushkevich varieties and those that are generated by completely simple or completely 0-simple semigroups are said to be exact. For each positive integer m, define C _m RS _n to be the class of all semigroups S in RS _n with the property that if the product of m idempotents of S belongs to some subgroup of S, then the product belongs to the center of that subgroup. The classes C _m RS _n constitute varieties that are the main object of investigation in this article. It is shown that a sublattice of exact subvarieties of C ₂ RS _n is isomorphic to the direct product of a three-element chain with the lattice of central completely simple semigroup varieties over groups of exponent dividing n. In the main result, this isomorphism is extended to include those exact varieties for which the intersection of the core with any subgroup, if nonempty, is contained in the center of that subgroup. The equational property of the varieties C _m RS _n is also addressed. For any fixed n ≥ 2, it is shown that although the varieties C _m RS _n , where m = 1, 2, ... , are all finitely based, their complete intersection (denoted by C _∞ RS _n ) is non-finitely based. Further, the variety C _∞ RS _n contains a continuum of ultimately incomparable infinite sequences of finitely generated exact subvarieties that are alternately finitely based and non-finitely based. Received October 29, 2003; accepted in final form February 11, 2007.     

Modeling MEMS resonators with rod-like components accounting for anisotropy, temperature, and strain dependencies

Numerous systems can be described using masses and rods in transverse vibration. Motivated by the desire to model the effects of axial strain and temperature on systems of this type, we develop a procedure to determine the frequencies of transverse vibration of devices composed of rods and rigid masses as functions of these effects. Our models allow for the rods to be composed of anisotropic materials with material symmetry contained in the cubic system. The goal of the present paper is to demonstrate the modeling procedure using the example of a double-ended tuning fork (DETF). Following this, the results of a slightly more complicated model are compared with the experimental results found for a prototype MEMS DETF sensor composed of polycrystalline silicon.