2‐Chloro‐4,5‐dihydroimidazole,Part X. Revisiting route to N‐heteroarylimidazolidin‐2‐ones

The ureidation reactions of 2‐ and 4‐picoline N‐oxides with 2‐chloro‐4,5‐dihydroimidazole are described. A mechanism of novel thioureidation reaction of 4‐picoline N‐oxide with 2‐(4,5‐dihydro‐1H‐imidazol‐2‐ylthioxy)‐4,5‐dihydro‐1H‐imidazole is proposed. Structural assignment is confirmed by ¹H and ¹³C nmr as well as by X‐ray crystallography.     

Determination of glutathione in spruce needles by liquid chromatography/tandem mass spectrometry

For the determination of glutathione (GSH) and its oxidized form (GSSG) in spruce needles their electrospray mass and MS/MS spectra were recorded with an ion trap mass spectrometer (ITMS, LCQ, Finnigan) and a triple stage quadrupole mass spectrometer (TSQ, Quattro II, Micromass). A study of the stability of GSH in aqueous solutions shows the presence of dimeric and trimeric forms of GSH, as well as GSSG, GSH-sulfonate and GSH-sulfinic acid. The same components were also found in extracts of spruce needles. We developed an assay which is suitable for monitoring low concentrations of GSH and similar compounds in plant tissues, employing the sensitivity and specificity of LC/MS/MS. Preliminary results on the mass spectrometric determination of GSH in spruce needles are given.     

Imidazole derivatives as the organic precursor of ZnO nano particle

N₁-Hydroxy-2,4,5-trisubstituted imidazoles were synthesized starting from 1,2-diketones. The crystal structure of 4,5-dimethyl-2-(3-nitrophenyl)-1H-imidazol-1-ol has been determined. An unusual intermolecular hydrogen bonding through the association of water molecule has been reported. These imidazole derivatives can be thought of as the organic precursor for the synthesis of zinc oxide nano particles.     

Ag and Cu loaded on TiO<Subscript>2</Subscript>/graphite as a catalyst for <Emphasis Type="Italic">Escherichia coli</Emphasis>-contaminated water disinfection

TiO₂ film was synthesized by means of the chemical bath deposition (CBD) method from TiCl₄ as a precursor and surfactant cetyl trimethyl ammonium bromide (CTAB) as a linking and assembling agent of the titanium hydroxide network on a graphite substrate. Ag and Cu were loaded on the TiO₂ film by means of electrodeposition at various applied currents. Photoelectrochemical testing on the composite of Ag-TiO₂/G and Cu-TiO₂/G was used to define the composite for Escherichia coli-contaminated water disinfection. Disinfection efficiency and the rate of disinfection of E. coli-contaminated water with Ag-TiO₂/G as a catalyst was higher than that observed for Cu-TiO₂/G in all disinfection methods including photocatalysis (PC), electrocatalysis (EC), and photoelectrocatalysis (PEC). The highest rate constant was achieved by the PEC method using Ag-TiO₂/G, k was 6.49 × 10⁻² CFU mL⁻¹ min⁻¹. Effective disinfection times of 24 h (EDT₂₄) and 48 h (EDT₄₈) were achieved in all methods except the EC method using Cu-TiO₂/G.     

Efficient kinetic bioresolution of 2-nitrocyclohexanol

The kinetic bioresolution of 2-nitrocyclohexanol 1 was investigated by screening a range of hydrolases both for enantioselective transesterification and for enantioselective hydrolysis of the corresponding acetate. By appropriate choice of biocatalyst and conditions, both enantiomers of cis and trans 2-nitrocyclohexanol 1 can be accessed in enantiopure form.     

A perturbed pK(a) at the binding site of the nicotinic acetylcholine receptor: implications for nicotine binding

A series of tethered quaternary ammonium derivatives of Tyr have been incorporated into the binding site of the nicotinic acetylcholine receptor (nAChR) using the in vivo nonsense suppression method, producing constitutively active (self-gating) receptors. We have incorporated primary, secondary, and tertiary amine tethered agonists to give receptors whose constitutive activity can be modulated by pH. Lowering the pH protonates the tethered amine, giving it a positive charge and allowing it to reversibly activate the receptor. Tertiary and secondary tethered amines, TyrO3T and TyrO3S, have been successfully incorporated at alpha149 in the nAChR. Constitutive currents at pH 5.5 are 6 times those at pH 9.0. The pKa of TyrO3T in the binding site appears to be 6 or lower, differing substantially from its pKa in solution ( approximately 9.3). This local pKa perturbation has substantial implications for pharmacological research on the nAChR: of the tertiary agonists considered, noracetylcholine experiences this pKa perturbation, while nicotine does not.     

Carbonates,thiocarbonates, and the corresponding monoalkyl derivatives: III. The 13C chemical shift tensors in potassium carbonate,bicarbonate and related monomethyl derivatives

The principal values of the 13C chemical shift tensors in potassium carbonate (K2CO3), trithiocarbonate (K2CS3), bicarbonate (KHCO3), methylcarbonate (KO2COCH3), S-methyl-monothiocarbonate (KO2CSCH3), O-methyl-monothiocarbonate (KOSCOCH3), S-methyl-dithiocarbonate (KOSCSCH3), and O-methyl-dithiocarbonate (KS2COCH3), were measured in solid-state nuclear magnetic resonance experiments. Chemical shift tensor calculations on the corresponding isolated anions were used to assign the chemical shift tensor orientations in the molecular frames of all anions. The correlation between experimental and calculated principal values improves significantly when the calculations are performed on isolated anions with proton-optimized X-ray geometries rather than on isolated anions with fully optimized geometries. Further considerable improvement in the correlation is achieved by utilizing the embedded ion method, which was recently developed to include electrostatic crystal potentials in chemical shift tensor calculations on ionic compounds. Similarities and differences in the chemical shift tensor orientations and principal values of the trigonal sp2 carbon atoms in the carbonate and thiocarbonate anions are compared with those known for condensed polyaromatic hydrocarbons.     

Time-dependent entropies associated with single mode radiation in a cavity

The time-dependent information theory entropy and generalized Gibbs entropy are evaluated for a continuous time Markov process (single mode radiation in a cavity).     

Measurement of traffic noise shielding provided by buildings

This paper presents a comparison between some current prediction methods for traffic noise shielding provided by buildings and the actual measured attenuations in typical residential areas. Generally, it was found that the method developed by the Department of Environment in the UK gives a reasonably accurate prediction of attenuation by shielding in fairly simple situations. In more complex situations, and particularly where a receiving position is close to a significant shielding structure, such as building, the attenuation obtained is underpredicted by the DOE method, thus the design facade levels for the rear of a building are overpredicted; however, in some other situations, the DOE method overpredicts the attenuation obtained. The attenuations measured for individual noise events under nominally identical conditions are shown to have large variations in attenuation.