Characterization of the weak SS bonds in the OSSSO and O2SSSO2 molecules.

The weak S1-S3 bonds in the OSSSO trans-disulfoxide and the corresponding sulfone, O(2)SSSO(2), are readdressed at the B3LYP/6-31+G(d) level using both the atoms-in-molecules (AIM) and the electron localization function (ELF) approaches. The S1-S3 bonds are clearly characterized as fractional (i.e.

Antibiotic therapy of hospitalized patients with community-acquired pneumonia: an international perspective from the CAPO Cohort Study.

The American Thoracic Society and the Infectious Diseases Society of America have developed evidence-based guidelines for the therapy of hospitalized patients with community-acquired pneumonia (CAP). In an attempt to evaluate if the care provided to hospitalized patients with CAP is in compliance with the care recommended by national guidelines, an international network of investigators has been collecting data from 40 hospitals in 13 countries. The care provided in the following areas of antibiotic therapy was analyzed: empiric antibiotic therapy, timing of initial antibiotic therapy, and switch from intravenous to oral antibiotic therapy.

A theoretical study of 31P NMR chemical shielding models for concentrated phosphoric acid solution.

Calculations on the hydrates, dimer, and trimer of phosphoric acid were carried out in an effort to obtain a viable model of the phosphorus NMR chemical shielding in 85% phosphoric acid solution. The theoretical approaches used the gauge-including-atomic-orbital (GIAO) 6-311+G(nd,p) basis set at both scaled density functional theory (sB3LYP) and estimated infinite order Møller-Plesset (EMPI) approaches and with the aug-cc-pvtz basis in the sB3LYP approach. Shieldings and hydrogen bonding stabilization energies are similar in the three approaches and indicate that the faster sB3LYP/6-311+G(nd,p) approach can be used with larger systems.

33S NMR spectra of sulfonium salts: calculated and experimental.

33S NMR chemical shifts were calculated by the scaled DFT and EMPI approaches for the fluoride, chloride and bromide of trimethylsulfonium ion (1) and S-methyltetrahydrothiophenium ion (2), in addition to the free cations. Experimental values were obtained for the iodides of 1 (delta +48, CS2 = 0 ppm) and 2 (delta +95), and were found to agree with the calculated values well within the standard deviation of 35 ppm (3.5% of the shielding range) established in earlier work for a great variety of sulfur compounds.

Bonding and 33S NMR chemical shielding in the thiophosphoryl group.

B3LYP and MP2 calculations at the 6-311 + G(nd,p) level (with n = 2 for second-row elements and n = 1 otherwise) were carried out using the atoms-in-molecules (AIM) approach to characterize the thiophosphoryl bond. A series of R(3)PS molecules were studied and compared with the corresponding R(3)PO systems. As with the phosphoryl bond, one cannot distinguish the thiophosphoryl bond from a standard P=S double bond by comparing bond distances.

Nature of bonding in the sulfuryl group.

The SO sulfuryl bond in a number of representative sulfoxides and sulfones has been studied at the B3LYP/6-311+G(d,p) level in the atoms-in-molecules (AIM) approach involving the AIM delocalization index and the Cioslowski-Mixon localized orbitals and associated covalent bond order. The sulfur-oxygen covalent bond is strongly polarized toward oxygen and the oxygen lone pairs provide significant backbonding to create short and strong SO bonds, similar in nature to those found in the analogous phosphoryl (PO) bond. Although the sulfoxides in general have larger delocalization indices than the sulfones, there is no correlation between these quantities and the bond dissociation energies.

Ligand Influences on Copper Cyanide Solid-State Architecture: Flattened and Fused "Slinky", Corrugated Sheet, and Ribbon Motifs in the Copper-Cyanide-Triazolate-Organoamine Family.

A series of novel composite inorganic-organic materials from the copper-cyanide-triazolate-organoamine system have been isolated and structurally characterized. An unusual interpenetrating layered structure type composed of fused and flattened "slinkies", [Cu(6)(CN)(5)(trz)] (1) (trz = triazolate, C(2)N(3)H(2)(-)), a complex corrugated layer structure, [Cu(5)(CN)(3)(trz)(2)(bpy)] (2), and a series of increasingly intricate one-dimensional ribbons, [Cu(3)(CN)(2)(trz)(bpy)], [Cu(3)(CN)(2)(trz)(phen)], and [Cu(4)(CN)(3)(trz)(phen)] (3-5), have been isolated from hydrothermal media. All trz ligands are deprotonated and participate in &mgr;(3)-bridging of Cu sites.

Methamphetamine toxicity is attenuated in mice that overexpress human manganese superoxide dismutase.

We have investigated methamphetamine (MA) toxicity in transgenic mice that overexpress the human form of mitochondrial manganese superoxide dismutase (MnSOD). Our results reveal a significant reduction in the long-term depletion of striatal dopamine and protein oxidation following repeated administration of MA in transgenic vs. non-transgenic littermates.

A spin label study of the urinary bladder luminal membrane.

Spin label experiments have been carried out on the urinary bladder luminal membrane of the bovine transitional epithelium employing the 5-, 7-, 12-, and 16-doxyl substituted stearic acid methyl esters, and compared for reference to similarly labeled bovine erythrocytes. The bladder membranes are significantly different from the bovine red blood cell membranes and show a lower order and polarity near the membrane surface. This fact and the general similarity of results for the bladder and isolated plaque membranes suggests that the highly organized proteins of the bladder membrane may act as a coat on the lipid bilayer and, while intrinsic in nature, do not significantly perturb the hydrophobic core of the lipid bilayer.

On the use of the spin labeling technique in the study of erythrocyte membranes.

ESR spectra and scanning electron micrographs of human erythrocytes spin labeled with the conventional stearic acid nitroxide substituted at the 5-position have been obtained over a range of label-to-lipid ratios. While morphological changes as previously reported (Bieri, V. G.

Electron spin resonance studies of erythrocytes from patients with myotonic muscular dystrophy.

Electron magnetic resonance experiments have demonstrated that spin-labeled myotonic erythrocyte membranes have spectra that are recognizably different from those of normal erythrocytes. The spin label incorporated in the erythrocyte membranes of patients having myotonic muscular dystrophy is apparently located in a less polar and somewhat more fluid region than the label in a normal membrane. Although the mechanisms of molecular interaction and their relationship to enzymatic differences is unclear, the results lend confirmation to the suggestion that myotonic muscular dystrophy may be a disease resulting from a basic membrane abnormality.