Effects of ion-pairing on rate of electron transfer between immobilized gold nanoclusters and soluble redox probes

Hydrophilic gold nanoclusters were tethered onto gold electrodes modified with mixed 1-octane thiol/1,9-nonane dithiol monolayers. The heterogeneous electron transfer (ET) kinetics of soluble redox species in the supporting electrolyte were investigated at these electrodes by cyclic voltammetry (CV) in the presence and absence of the ion-pairing anions and . The redox species investigated, [Fe(CN)₆]^3−/4− and [Co(C₁₂H₈N₂)₃]^3+/2+ where oppositely charged. The results presented here reveal that the rate of ET for the negatively charged redox species decreases with decreasing ionic charging time constant of the electrolyte. The opposite trend is observed for the positively charged redox species.     

Direct calculation of the binding free energies of FKBP ligands

Direct calculations of the absolute free energies of binding for eight ligands to FKBP protein were performed using the Fujitsu BioServer massively parallel computer. Using the latest version of the general assisted model building with energy refinement (AMBER) force field for ligand model parameters and the Bennett acceptance ratio for computing free-energy differences, we obtained an excellent linear fit between the calculated and experimental binding free energies. The rms error from a linear fit is 0.4 kcal/mol for eight ligand complexes. In comparison with a previous study of the binding energies of these same eight ligand complexes, these results suggest that the use of improved model parameters can lead to more predictive binding estimates, and that these estimates can be obtained with significantly less computer time than previously thought. These findings make such direct methods more attractive for use in rational drug design.     

Facile one-pot synthesis of S-alkyl thiocarbamates

We report a novel one-pot two-step synthesis of a variety of S-alkyl thiocarbamates. This method offers a two-directional approach making use of trichloroacetyl chloride, requires no complex starting material, incorporates a variety of substituents, and proceeds in high yields.     

Analysis of oxytetracycline, tetracycline, and chlortetracycline in water using solid-phase extraction and liquid chromatography-tandem mass spectrometry

A method using liquid chromatography-tandem mass spectrometry has been developed for determination of trace levels of tetracycline antibiotics in ground water and confined animal feeding operation waste water. Oxytetracycline (OTC), tetracycline (TC), and chlortetracycline (CTC) were extracted from water samples using both polymeric and C18 extraction cartridges. The addition of a buffer containing potassium phosphate and citric acid improved tetracycline recoveries in lagoon water. Method detection limits determined in reagent water fortified with 1 microg l(-1) OTC, TC, and CTC were 0.21, 0.20, and 0.28 microg l(-1). Method detection limits in lagoon water samples fortified at 20 microg l(-1) for OTC, TC, and CTC were 3.6, 3.1, and 3.8 microg l(-1). Variability in recovery from laboratory fortified blanks ranged from 86 to 110% during routine analysis.     

Precision neutron interferometric measurement of the nd coherent neutron scattering length and consequences for models of three-nucleon forces

We have performed the first high precision measurement of the coherent neutron scattering length of deuterium in a pure sample using neutron interferometry. We find b(nd)=(6.665+/-0.004) fm in agreement with the world average of previous measurements using different techniques, b(nd)=(6.6730+/-0.0045) fm. We compare the new world average for the nd coherent scattering length b(nd)=(6.669+/-0.003) fm to calculations of the doublet and quartet scattering lengths from several modern nucleon-nucleon potential models with three-nucleon force (3NF) additions and show that almost all theories are in serious disagreement with experiment. This comparison is a more stringent test of the models than past comparisons with the less precisely determined doublet scattering length of (2)a(nd)=(0.65+/-0.04) fm.     

Search for second-generation leptoquark pairs in &pmacr;p collisions at radicals = 1.8 TeV

We have searched for second-generation leptoquark (LQ) pairs in the &mgr;&mgr;+jets channel using 94+/-5 pb(-1) of &pmacr;p collider data collected by the D0 experiment at the Fermilab Tevatron during 1993-1996. No evidence for a signal is observed. These results are combined with those from the &mgr;nu+jets and nunu+jets channels to obtain 95% confidence level (C.L.) upper limits on the LQ pair production cross section as a function of mass and beta, the branching fraction of a LQ decay into a charged lepton and a quark. Lower limits of 200(180) GeV/c(2) for beta = 1(1 / 2) are set at the 95% C.L. on the mass of scalar LQ. Mass limits are also set on vector leptoquarks as a function of beta.