Regiospecific Carboxylation of Certain Methoxylated 2-Tetralones

As a part of an ongoing synthetic program, certain aromatic ringmethoxylated tetralins, bearing synthetically useful functional groups at positions 2 and 3, were required. The literature¹ revealed that treatment of 6-methoxy-2-tetralone with NaH and dimethyl carbonate gave exclusive carbomethoylation at position 1. However, treatment of 2-tetralone and of 5-methoxy-2-tetralone with magnesium methoxy carbonate (“MMC”) followed by esterification with diazomethane was reported² go give the 3-carbomethoxy product (la, lb) exclusively, although in low (12 and 26%, respectively) yield. The use of MMC in regiospecific carboxylation of certain acylic ketones has also been reported³.     

The relaxation of HCN(011) by V-T,R and V-V energy transfer

Tuned output from an optical parametric oscillator has been used to excite HCN directly to its (011) level. By careful use of a “cold-gas filter”, it has proved possible to distinguish between the time-resolved fluorescence from HCN(011) and that from HCN(001) formed during collisional relaxation. Rate constants for relaxation from both levels have been obtained for the partners: (i) He, Ne, Ar and Kr, and (ii) HCN, CO₂, N₂O, OCS, CS₂, C₂H₂ and C₂D₂. With the rare gases, HCN(011) is relaxed to (001) by V-T,R energy transfer, with rate constants (cm³ molecule^?1 s^?1) at 298 ± 4 K of: k_He⁰¹¹ = (7.9 ± 1.05) × 10^?13; k_Ne⁰¹¹ = (1.56 ± 0.12) × 10^?13; k_Ar⁰¹¹ = (1.20 ± 0.17) × 10^?13; k_Kr⁰¹¹ = (6.7 ± 0.65) × 10^?14. The molecular collision partners also transfer HCN(011) to (001). The rates are much greater and clearly near-resonant V-V energy exchange is important. The results are compared to first-order Sharma-Brau theory, with fair agreement where near-resonant channels exist.     

On the solution a of second order singularly-perturbed boundary value problem by the Sinc-Galerkin method

Sinc methods are now recognized as an efficient numerical method for problems whose solutions may have singularities, or infinite domains, or boundary layers. This work deals with the Sinc-Galerkin method for solving second order singularly perturbed boundary value problems. The method is then tested on linear and nonlinear examples and a comparison with spline method and finite element scheme is made. It is shown that the Sinc-Galerkin method yields better results.     

Nanometer-scale wetting of the silicon surface by its equilibrium oxide

Despite the extremely broad technical applications of the Si/SiO2 structure, the equilibrium wetting properties of silicon oxide on silicon are poorly understood. Here, we produce new results in which a solid-state buffer method is used to systematically titrate oxygen activity about the Si/SiO2 coexistence value. The equilibrium morphology at the Si(001) surface over >8 decades of PO2 about coexistence is revealed to be a uniform sub-stoichiometric SiOx film of sub-nanometer thickness, coexisting with secondary island structures which coarsen with annealing time. A new thermodynamic method using chemical potential to stabilize and control surficial oxides in nanoscale devices is suggested.     

Dipole-bound CH3CN- ions: temperature dependence of ion production rates and lifetimes

The formation of long-lived (tau less, similar10 mus) dipole-bound CH(3)CN(-) ions through electron transfer in K(14p)CH(3)CN collisions is investigated as a function of target temperature. The rate for their formation is observed to decrease steadily with increasing target temperature. The results are consistent with earlier suggestions that only target molecules in the ground vibrational state and low-lying rotational states can form long-lived dipole-bound anions. For CH(3)CN, the data indicate that creation of long-lived ions requires that the target molecules be in states with rotational quantum numbers j less, similar20. The measurements further demonstrate that the lifetime of the longest-lived (tau greater, similar50 mus) ions is limited by blackbody-radiation-induced photodetachment.     

Addition of difluorocarbene to 3',4'-unsaturated nucleosides: synthesis of 2'-deoxy analogues with a 2-oxabicyclo[3.1.0]hexane framework

Treatment of protected 2'-deoxy-3',4'-unsaturated nucleosides derived from adenosine and uridine with difluorocarbene [generated from bis(trifluoromethyl)mercury and sodium iodide] gave fused-ring 2,2-difluorocyclopropane compounds. Stereoselective alpha-face addition to the dihydrofuran ring resulted from hindrance by the protected beta-anomeric nucleobases. A protected uracil compound was converted smoothly into the cytosine derivative via a 4-(1,2,4-triazol-1-yl) intermediate. Removal of the protecting groups gave new difluorocyclopropane-fused nucleoside analogues. The solid-state conformation of the nearly planar furanosyl ring in the uracil compound had a shallow 2E pucker, and a more pronounced 1E conformation was present in the furanosyl ring of the cytosine derivative.     

Synthesis, characterization, and antimicrobial activity of silver carbene complexes derived from 4,5,6,7-tetrachlorobenzimidazole against antibiotic resistant bacteria

Silver N-heterocyclic carbene complexes have been shown to have great potential as antimicrobial agents, affecting a wide spectrum of both Gram-positive and Gram-negative bacteria. A new series of three silver carbene complexes (SCCs) based on 4,5,6,7-tetrachlorobenzimidazole has been synthesized, characterized, and tested against a panel of clinical strains of bacteria. The imidazolium salts and their precursors were characterized by elemental analysis, mass spectrometry, (1)H and (13)C NMR spectroscopy, and single crystal X-ray diffraction. The silver carbene complexes, SCC32, SCC33, and SCC34 were characterized by elemental analysis, (1)H and (13)C NMR spectroscopy, and single crystal X-ray diffraction. These complexes proved highly efficacious with minimum inhibitory concentrations (MICs) ranging from 0.25 to 6 μg mL(-1). Overall, the complexes were effective against highly resistant bacteria strains, such as methicillin-resistant Staphylococcus aureus (MRSA), weaponizable bacteria, such as Yersinia pestis, and pathogens found within the lungs of cystic fibrosis patients, such as Pseudomonas aeruginosa, Alcaligenes xylosoxidans, and Burkholderia gladioli. SCC33 and SCC34 also showed clinically relevant activity against a silver-resistant strain of Escherichia coli based on MIC testing.     

An epidemiology model suggested by yellow fever

In this work, we construct and analyze a nonlinear reaction–diffusion epidemiology model consisting of two integral‐differential equations and an ordinary differential equation, which is suggested by various insect borne diseases, for example, Yellow Fever. We begin by defining a nonlinear auxiliary problem and establishing the existence and uniqueness of its solution via a priori estimates and a fixed point argument, from which we prove the existence and uniqueness of the classical solution to the analytic problem. Next, we develop a finite‐difference method to approximate our model and perform some numerical experiments. We conclude with a brief discussion of some subsequent extensions. Copyright © 2011 John Wiley & Sons, Ltd.     

Subdivision rules and virtual endomorphisms

Suppose f : S ² → S ² is a postcritically finite branched covering without periodic branch points. If f is the subdivision map of a finite subdivision rule with mesh going to zero combinatorially, then the virtual endomorphism on the orbifold fundamental group associated to f is contracting. This is a first step in a program to clarify the relationships among various notions of expansion for noninvertible dynamical systems with branching behavior.