σ-Holes in Iodonium Ylides: Halogen-Bond Activation of Carboxylic Acids,Phenols and Thiophenols May Enable Their X−H Insertion Reactions

The first systematic evaluation of the electrostatic potential energy maps of iodonium ylides was conducted. We determined that they possess two σ-holes of differing electron deficiencies, with the more electropositive σ-hole located opposite the dative I−C bond to the β-dicarbonyl motif, and the lesser electropositive σ-hole located opposite the iodoarene C−I bond. We also conducted the first systematic evaluation of carboxylic acids, phenols and thiophenols in the O/S-alkylation reaction of iodonium ylides. While carboxylic acids and thiophenols were found to be generally viable, only phenols possessing electron-withdrawing substituents were effective. This high-yielding and highly chemoselective reaction is believed to involve halogen-bond activation of heteroatoms, and nicely complements existing diazo-based methods for alkylation of acidic functional groups.     

Thermal lensing, thermal management and transverse mode control in microchip VECSELs

Finite-element analysis is used to explore the practicalities and power-scaling potential of quasi-monolithic microchip vertical-external-cavity surface-emitting lasers: thermal lensing and its implications for transverse mode control are emphasised. A comparison is made between the use of sapphire and diamond heat spreaders. The experimental characterisation of an InGaAs/sapphire microchip VECSEL is presented as an exemplar system and the factors affecting slope efficiency, threshold and output power roll-over are examined. By comparing experimental measurements with the finite-element model, the key role of thermal lensing in transverse mode control is demonstrated. PACS 42.55.Xi; 42.55.Rz; 42.55.Px     

On the skew representations of the quantum affine algebra

An explicit realization of the skew representations of the quantum affine algebra U _q (gl _n ) is given. It is used to identify these representations in a simple way by calculating their highest weight, Drinfeld polynomials and the Gelfand-Tsetlin character (orq-character).     

The effects of a small transverse magnetic field upon acapacitively coupled RF discharge

A capacitively-coupled RF argon discharge at a pressure of 10 mTorr with a plate separation of 7.5 cm has been studied both experimentally and using a one-dimensional particle in cell simulation with Monte Carlo collisions. A magnetic field of 0 to 60 G is applied in the direction parallel to the capacitor plates. In the simulation it was found that as the magnetic field was increased such that the electron cyclotron orbit radius of the hot electrons became smaller than of the order of the discharge length, the electron heating in the bulk of the discharge increased. The dominant electron heating mechanism was observed to change from a stochastic sheath to a bulk ohmic electron heating mode, with a variation of field from a to 10 G. This was accompanied by a drop in the plasma density at small magnetic fields, which was also observed experimentally. At higher magnetic fields the plasma density was found to increase, A detailed discussion of the simulation results is presented drawing comparisons with the experimental results, with which there is good agreement, and a simple magnetohydrodynamic model for the bulk heating     

N-Oxide S–O chalcogen bonding in conjugated materials

Non-covalent bonding interactions, such as chalcogen bonding, can have a substantial effect on the electronic and physical properties of conjugated polymers and is largely dependent on the strength of interaction. Functional groups that are traditionally used to instill chalcogen bonding such as alkoxy or fluorine substituents can demand challenging synthetic effort, as well as have drastic effects on the electronics of a π-system. The incorporation of a N-oxide functionality into bithiazole-containing materials, a synthetically simple transformation, has been entirely overlooked until now. A systematic analysis of the effects of N-oxidation on the electronic and physical properties of bithiazole-containing materials has been undertaken. N-Oxidation has been found to affect the electronic band gap through increase of the HOMO and lowering of the LUMO. Furthermore, exceptionally strong intramolecular S–O chalcogen bonding interactions in the bithiazole core contribute to rigidification of the conjugated system. Computational analysis of this system has shown this N-oxide chalcogen bonding interaction to be significantly stronger than other chalcogen bonding interactions commonly exploited in conjugated materials.

N-Oxide incorporation into thiazole-containing conjugated materials can have substantial effects on both the electronic and physical properties. A notably strong non-covalent S–O interaction is observed between the N-oxide and neighbouring sulfur.     

Synthesis and characterization ofM 2(CCR)4(PMe3)4 dimetallapolyynes

The reaction betweenM ₂Cl₄(PMe₃)₄ (M = Mo, W) and four equivalents of LiCCR (R = Me,i-Pr,t-Bu, SiMe₃, Ph) in dimethoxyethane solution yields alkynyl-substituted, quadruply bonded complexes of the type M₂(CCR )₄(PMe₃)₄ in 10–90% yield. The electronic-absorption and¹H-,¹³ ₁₃C-, and³¹P-NMR spectroscopic data for these dimetallapolyyne complexes indicate that they are uncontaminated by chloride-containing impurities, and that they possess theD _2d geometry expected of compounds of the M₂X₄L₄ type. A single-crystal X-ray diffraction study of Mo₂(CCPr ⁱ )₄(PMe₃)₄ confirms this latter conclusion, and also reveals that the Mo₂ core of the complex is three-way disordered within the ordered quasi-cubic array of ligating atoms.     

Comparison of Ca2+ and Mg2+ binding to calmodulin. An enthalpy,entropy, and gibbs free energy analysis

A consistent set of G _B , H _B , and S _B parameters have been determined from ion specific electrode, calorimetric, and spectrophotometric studies for the binding of Ca²⁺ and Mg²⁺ to bovine calmodulin at pH=7.0 and an ionic strength I of 0.113M. A non-linear least squares analysis of calcium specific ion electrode data yields, on a molar basis, four calcium dissociation constants: 10^–7 for the first site, 10^–5 for the fourth site, and two constants between these values. Both calorimetric experiments and an indicator method provide evidence that Mg²⁺ binds to calmodulin, probably at the same sites as Ca²⁺, but with affinities about 100 times smaller: 4×10^–5 for the first site and 2×10^–3 for the fourth. Calorimetric titrations on Ca²⁺ binding to calmodulin in three buffers are consistent with 0.46 protons released upon binding at all four sites and yield an average H _B per site of 5.6 and 7.9 kJ-mol^–1 for Ca²⁺ and Mg²⁺, respectively. The entropy of the system increases by 524 and 361 J-K^–1-mol^–1 when Ca²⁺ and Mg²⁺, respectively, bind to four sites on calmodulin, i.e., the selectivity of calmodulin for Ca²⁺ is primarily derived from entropy effects. Further analysis based on elimination of the entropy term for the metal ions demonstrates that calmodulin bound to Ca²⁺ has a larger entropy than the unbound calmodulin; the opposite is true for calmodulin bound to Mg²⁺. These analyses are consistent with the hypothesis that Ca²⁺ forms tight complexes at all sites on calmodulin and that release of waters of hydration upon binding is the source of the increase of entropy in the system.