Anion control of the formation of geometric isomers in a triple helical array

The amide-substituted unsymmetrical ligand L(1) upon coordination to Co(2+) forms the dinuclear triple helicate [Co(2)(L(1))(3)](4+) which exists as both possible C(1) and C(3) symmetric geometric isomers in solution, however, upon addition of nitrate ions, the formation of an anion binding cavity is favoured and hence the sole product is the C(3) symmetric isomer in which all three amide substituents are hydrogen bonded to the nitrate anion.     

Efficient synthesis of imidazoles from aldehydes and 1,2-diketones using microwave irradiation

[reaction: see text] A simple, high-yielding synthesis of 2,4,5-trisubstituted imidazoles from 1,2-diketones and aldehydes in the presence of NH(4)OAc is described. Under microwave irradiation, alkyl-, aryl-, and heteroaryl-substituted imidazoles are formed in yields ranging from 80 to 99%. Short syntheses of lepidiline B and trifenagrel illustrate the utility of this approach.     

Simple method for the assay of linezolid in Brain Heart Infusion broth by high-performance liquid chromatography

A simple HPLC method was developed and validated for quantification of linezolid in Brain Heart Infusion (BHI) broth. Eperezolid was employed as internal standard and the sample pre-treatment procedure was simple. Calibration standards ranged from 0.05 to 16 mg/L. Accuracy was within 7.8% and reproducibility (RSD) was less than 8.3%. Recovery was approximately 100% at all concentrations examined. Linezolid was stable in the autosampler insert for at least 24 h at ambient temperature and in BHI for 72 h at 37 degrees C. This assay is rapid and ideal for analysis of a large number of samples.     

Hierarchical self-assembly of noncovalent amphiphiles

Amphiphiles defined by noncovalent inclusion complexes between an alkylated beta-cyclodextrin and PEG-conjugated guests assemble into higher-ordered structures whose thermodynamic stability reflects that of the defining intermolecular interactions.     

Investigation of modified basal plane pyrolytic graphite electrodes: definitive evidence for the electrocatalytic properties of the ends of carbon nanotubes

The basis of the electrocatalytic nature of multi-wall carbon nanotubes is suggested to reside in electron transfer from the ends of nanotubes, which structurally resemble the behaviour of edge plane (as opposed to basal plane) graphite, and is demonstrated via the comparison of the electrochemical oxidation of epinephrine and the electrochemical reduction of ferricyanide at nanotube-modified electrodes using different types of graphite electrodes and with C(60)-modified electrodes.     

Measurement of internal magnetic field fluctuations in a reversed-field pinch by Faraday rotation

Magnetic field fluctuations (and the associated current perturbation) have been measured in the core of a high-temperature reversed-field pinch using a newly developed fast-polarimetry system. Radial magnetic field fluctuation levels of approximately 1% are measured in standard-reversed-field pinch discharges which increase to approximately 4% during the sawtooth crash (enhanced dynamo). The fluctuation level is reduced fourfold for high-confinement plasmas where the core-resonant tearing modes are suppressed.     

Amine-catalyzed coupling of aldehydes and ketenes derived from Fischer carbene complexes: formation of beta-lactones and enol ethers

Aldehydes react with ketenes generated from photolysis of Fischer chromium carbene complexes to generate either beta-lactones or enol ethers resulting from decarboxylation of beta-lactones. The reaction is catalyzed by tertiary amines and can occur with diastereoselectivity greater than 20:1 with DMAP as the catalyst.     

A simple clustering technique to improve QSAR model selection and predictivity: application to a receptor independent 4D-QSAR analysis of cyclic urea derived inhibitors of HIV-1 protease

A training set of 50 tetrahydropyrimidine-2-one based inhibitors of HIV-1 protease, for which the -log K(i) values were measured, was used to construct receptor independent 4D-QSAR models. A novel clustering technique was employed to facilitate and improve model selection as well as test set predictions. Following the manifold model theory, five unique models were chosen by the clustering algorithm (q(2) = 0.81-0.84). The models were used to map the atom type morphology of the inhibitor binding site of HIV-1 protease as well as to predict the potencies (-log K(i)) of 10 test set compounds. The rank-difference correlation coefficient was used to evaluate the quality of the test set predictions, which was improved from 0.39 to 0.68 when the clustering technique was applied. The set of five models, collectively, identify the important binding characteristics of the HIV protease receptor site. This study demonstrates that the selected simple clustering technique provides a discrete algorithm for model selection, as well as improving the quality of test set, or unknown, compound prediction as determined by the rank-difference correlation coefficient.     

Yttrium polyoxometalates. Synthesis and characterization of a carbonate-encapsulated sandwich-type complex

Reaction of A-alpha-PW(9)O(34)(9)(-) with YCl(3) in an aqueous Na(2)CO(3) solution produces a dianion-encapsulated A-type sandwich polyoxometalate, (YOH(2))(3)(CO(3))(A-alpha-PW(9)O(34))(2)(11)(-). The X-ray structure of this complex reveals that three Y(III) ions are sandwiched between two A-alpha-PW(9)O(34)(9)(-) moieties and that a carbonate dianion is encapsulated in the same plane as the three Y(III) atoms. The oxygen atoms of the CO(3)(2)(-) are sitting at the midpoints of the sides of the triangle formed by the three Y(III) ions. (31)P and (13)C NMR studies confirm that this complex is significantly more stable than the analogous A-type sandwich polyoxometalates containing divalent metals.