Coupling of counterpropagating light waves in low-symmetry photorefractive crystals

Coupling of two counterpropagating coherent light waves in tin hypothiodiphosphate (Sn₂P₂S₆, SPS) is usually strongly inhibited because of severe space charge limitations. Analysis of two-beam coupling gain is performed for different orientations of the grating vector in this monoclinic crystal that takes into account the anisotropy of dielectric permittivity. Gain enhancements are predicted and demonstrated experimentally for several nontraditional orientations of counterpropagating waves.     

Micromechanical models of young's modulus of NR/organoclay nanocomposites

Small strain Young's moduli of natural rubber (NR)/organoclay nanocomposites were estimated using the Guth–Gold, Halpin–Tsai (HT), and Krieger–Dougherty (KD) models, and compared with experimental measurements of NR vulcanizates containing organo‐montmorillonite (OM) or organo‐sepiolite (OS). To account for the effect on modulus of the NR matrix of the vulcanization‐active modifier in the organoclay, a matrix modulus correction (MMC) term was derived from the vulcanization parameters of the nanocomposites. The KD model gave a better empirical fit with the experimental data than the Guth–Gold model, with both giving good agreement with particle shape factors estimated from transmission electron microscope (TEM) images. The HT model gave the best fit with experiment for both types of nanocomposite, and use of the MMC term meant that the empirical shape factor was sufficiently close to that estimated from TEM images that the model could potentially be used to accurately predict the Young's moduli of NR/OM and NR/OS nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1621–1627, 2011     

Doubly-occupied orbital MCSCF methods

A new computational method for a previously suggested Multi-Configuration SCF molecular wave function is developed and applied to some simple molecules. The method involves the use of a single Fock-like hamiltonian matrix for all the MCSCF orbitals and does not involve orthogonality constraints or coupling operators. Application to lithium hydride shows that this method is capable of recovering a large part of the correlation energy and compares very favourably with conventional lengthy CI methods.     

One-pot enol silane formation-Mukaiyama aldol reactions: Crossed aldehyde-aldehyde coupling,thioester substrates,and reactions in ester solvents

Trimethylsilyl trifluoromethanesulfonate (TMSOTf) and a trialkylamine base promote both in situ enol silane/silyl ketene acetal formation and Mukaiyama aldol addition reactions between a variety of reaction partners in a single reaction flask. Isolation of the required enol silane or silyl ketene acetal is not necessary. For example, crossed aldol reactions between α-disubstituted aldehydes and non-enolizable aldehydes yield β-hydroxy aldehydes in good yield. In a related reaction, the common laboratory solvent ethyl acetate functions as both an enolate precursor and a green reaction solvent. When thioesters are employed as enolate precursors, high yields for additions to non-enolizable aldehydes are routinely observed.     

Intra‐strain Variability in the Effects of Temperature on UV‐B Sensitivity of Cyanobacteria

Stratospheric ozone depletion is mostly marked over the Antarctic and to a lesser extent over the Arctic, though recent reports have revealed that this also occurs at lower latitudes. Continued depletion of ozone in the lower stratosphere allows more UVR to reach the Earth's surface. Furthermore, it is projected that surface water temperatures will increase by between 0.2 and 2.0°C by the year 2060 and this will directly or indirectly influence algal growth. The interactions between environmental factors are complicated by the existence of different strains (ecotypes) of the same species that may respond differently. To understand the interactive effects of temperature and UV‐B on two strains of Anabaena circinalis, we investigated the damaging effects of UV‐B on cell numbers and photosynthetic characteristics and also examined the effect of temperature on the capacity of cells to recover from such stress. Both strains of A. circinalis responded differently in terms of survival, photosynthetic characteristics and recovery with interactions between temperature and UV‐B. This could be due to the variations in strain‐specific photoreactive mechanisms. This needs to be explored further including more strains and species before definitive conclusions can be reached about effects of global change on cyanobacteria generally.     

Stereoinversion of Unactivated Alcohols by Tethered Sulfonamides

The direct, catalytic substitution of unactivated alcohols remains an undeveloped area of organic synthesis. Moreover, catalytic activation of this difficult electrophile with predictable stereo‐outcomes presents an even more formidable challenge. Described herein is a simple iron‐based catalyst system which provides the mild, direct conversion of secondary and tertiary alcohols to sulfonamides. Starting from enantioenriched alcohols, the intramolecular variant proceeds with stereoinversion to produce enantioenriched 2‐ and 2,2‐subsituted pyrrolidines and indolines, without prior derivatization of the alcohol or solvolytic conditions.