FTIR spectroscopic studies of the matrix photoionization and photolysis products of methylene halides

Matrix photoionization of methylene bromide produced absorptions at 1019, 897, and 788 cm^?1 identified previously as CBr₂⁺, CHBr₂⁺, and CHBr₂. High-resolution FTIR spectra revealed overlapping 1/2/1 triplets for natural bromine isotopes with individual linewidths near 0.2 cm^?1. New absorptions at 3121, 2897, and 1345 cm^?1 are assigned to the (CH₂Br⁺)Br cation complex which yields CHBr₂⁺ on photolysis. A substantially increased yield of the CHCl₂⁺ species made possible observation of the CH stretching mode at 3033 cm^?1 and the symmetric CCl₂ stretching mode at 845 cm^?1 along with the previously observed stronger 1291- and 1044-cm^?1 fundamentals. The high resolution and enhanced signal-to-noise capability of the FTIR are clearly demonstrated in this investigation.     

Further exploration of antimicrobial ketodihydronicotinic acid derivatives by multiple parallel syntheses

A synthetic reexamination of a series of ketodihydronicotinic acid class antibacterial agents was undertaken in an attempt to improve their therapeutic potential. A convenient new synthesis was developed involving hetero Diels-Alder chemistry producing 74 new analogs in a multiple parallel synthetic manner and these were examined in vitro for their antimicrobial potential. Several compounds demonstrated significant broad-spectrum activity against clinically derived bacterial strains but previously known 1-(2,4-difluorophenyl)-6-(4-dimethylaminophenyl)-4-pyridone-3-carboxylic acid (7) remained the most potent compound in this class. Cross-resistance with ciprofloxacin supported a commonality of mode of action. Permiabilization of Escherichia coli cells by polymyxin B significantly enhanced potency with these agents suggesting that poor cellular uptake was primarily responsible for the disappointing activity against bacteria that some of the analogs exhibited.     

PHOTOINACTIVATION OF CATALASE

Abstract— Inactivation of catalase with visible light (>400nm) has been studied in purified bovine liver catalase and in peroxisomal catalase in the mitochondrial fraction of rat liver. Light corresponding to that of maximal absorbance of the heme site (405 nm) was most effective in inactivation. Although photoinactivation is O₂ dependent, scavengers of OH radical, ¹O₂ and O⁻₂ did not protect against loss of activity in either system. Superoxide dismutase partially protected purified catalase added into the mitochondrial fraction system. However, complete protection of catalase was afforded by low concentrations of substrates such as formic acid or methanol which rapidly convert Compound I to Ferricatalase.     

An order-disorder transition in Sr2IrD5: Evidence for square pyramidal IrD5 units from powder neutron diffraction data

Neutron diffraction data have been collected on a powdered sample of Sr₂IrD₅ over a range of temperatures. The compound, which is cubic at room temperature, has been found to exhibit a gradual transformation to a tetragonal phase in the temperature range 200-140 K. As a result of the transition, deuterium atoms which randomly occupy sixfold positions in the cubic phase, become tetragonally ordered. A small fraction of the cubic phase remained untransformed at 4.2 K. Both the cubic and tetragonal structures are consistent with square pyramidal IrD₅ units with average Ir---D distances of 1.714 and 1.718 Å, respectively. Agreement factors, R₁, for the two structural analyses are 3.44 and 4.94%.     

A stereochemical test of a proposed structural feature of the nicotinic acetylcholine receptor

Understanding the gating mechanism of the nicotinic acetylcholine receptor (nAChR) and similar channels constitutes a significant challenge in chemical neurobiology. In the present work, we use a stereochemical probe to evaluate a proposed pin-into-hydrophobic socket mechanism for the alphaVal46 side chain of the nAChR. Utilizing nonsense suppression methodology we incorporated isoleucine (Ile), O-methyl threonine (Omt) and threonine (Thr) as well as their side chain epimers (the allo counterparts). Surprisingly, our results indicate that only the pro-S methyl group of the alphaVal46 side chain is sensitive to changes in hydrophobicity, consistent with the precise geometrical requirements of the pin-into-socket mechanism.     

Infrared spectra of methylidynes formed in reactions of re atoms with methane, methyl halides, methylene halides, and ethane: methylidyne C-H stretching absorptions, bond lengths, and s character

Rhenium carbyne complexes (HC identical with ReH 3, HC identical with ReH 2X, HC identical with ReHX 2, [X = F, Cl, and Br] and CH 3C identical with ReH 3) are produced by reactions of laser-ablated Re atoms with methane, methyl halides, methylene halides, and ethane via oxidative C-H(X) insertion and alpha-hydrogen migration in favor of the carbon-metal triple bond. The stabilities of the carbyne complexes relative to other possible products are predicted by DFT calculations. The diagnostic methylidyne C-H stretching absorptions of HC identical with ReH 3 and its mono- and dihalo derivatives are observed on the blue sides of the precursor C-H stretching bands, and the frequency decreases and the bond length increases in the order of H, F, Cl, and Br, following the decreasing s character in hybridization for the C-H bond. The dihalo methylidynes have higher C-H stretching frequencies and s characters than the monohalo species. The rhenium methylidynes have C s structures, and as a result the HC identical with ReH 3 and CH 3C identical with ReH 3 complexes have two equivalent shorter and one longer Re-H bonds, as compared to the tungsten methylidyne HC identical with WH 3 with three equivalent W-H bonds.     

Photodissociation dynamics of methyl nitrate at 193 nm: energy disposal in methoxy and nitrogen dioxide products

The photodissociation dynamics of methyl nitrate, CH(3)ONO(2), has been investigated at 193 nm by examining the products from the primary dissociation channel, namely CH(3)O and NO(2). The CH(3)O (X (2)E) photoproducts were probed by laser-induced fluorescence (LIF) on the A (2)A(1)-X (2)E transition under both nascent and jet-cooled conditions. The 3 and 3 bands originating from the vibrationless and C-O stretch (nu(3)) levels, respectively, were characterized to obtain the internal energy distribution of the CH(3)O products. Only a small fraction of the CH(3)O products (< or =10%) were produced with one quantum of C-O stretch excitation as determined from the relative intensities of the bands in combination with transition probabilities derived from dispersed fluorescence measurements and/or calculated Franck-Condon factors. The CH(3)O products also had minimal rotational excitation: those produced in the ground vibrational state had a rotational temperature of 238 +/- 7 K, corresponding to less than 1% of the available energy. Products with C-O stretch excitation were found to have a higher rotational temperature, but still a small fraction of the total energy. Combining the CH(3)O internal energy findings with previous photofragment translational energy measurements [X. Yang, P. Felder and J. R. Huber, J. Phys. Chem., 1993, 97, 10903] indicates that most of the available energy is deposited in the NO(2) fragment. This is verified through dispersed fluorescence measurements which show that the NO(2) fragment is produced electronically excited with internal energies extending to the NO + O dissociation limit. Ab initio calculations confirm that the dominant initial excitation is strongly localized on the NO(2) moiety. The calculations are also used to reveal the forces that give rise to internal excitation of the CH(3)O fragment upon electronic excitation.     

A combined experimental and theoretical study of uranium polyhydrides with new evidence for the large complex UH4(H2)6

Several monouranium and diuranium polyhydride molecules were investigated using quantum chemical methods. The infrared spectra of uranium and hydrogen reaction products in condensed neon and pure hydrogen were measured and compared with previous argon matrix frequencies. The calculated molecular structures and vibrational frequencies were used to identify the species present in the matrix. Major new absorptions were observed and compared with the previous argon matrix study. Spectroscopic evidence was obtained for the novel complex, UH4(H2)6, which has potential interest as a metal hydride with a large number of hydrogen atoms bound to uranium. Our calculations show that the series of complexes UH4(H2)1,2,4,6 are stable.     

Determination of steroid estrogens in wastewater by high performance liquid chromatography-tandem mass spectrometry

This paper discusses the requirement for, and presents an analytical procedure for, the determination of four steroid hormones and a conjugated steroid (estrone-3-sulfate) in wastewaters. The method utilizes LC/MS/MS following solid phase extraction and a two stage clean-up procedure, achieving limits of detection of 0.2 ng l(-1) for estriol, 17beta-estradiol and 17 alpha-ethinylestradiol, and 0.1 ng l(-1) for estrone and the conjugate. The approach demonstrates that using appropriate clean-up and deuterated internal standards, the impact of matrix effects on ionization can be overcome to reliably determine estrogens at environmentally relevant concentrations. The robustness of the method was demonstrated by achieving recoveries of >83% for all steroids in settled sewage and final effluent samples with relative standard deviations of 0.5-12%.