Intramolecular interaction effects and the structure of N2OS and N2O2: An Ab initio study

An ab initio study of O?N? N?S with full geometry optimization has been carried out to corroborate the presence of an interaction between the terminal atoms in this type of structure, which, in O?N? N?O, apparently stabilizes the cis conformer. Using the unscaled 4–31G basis set with a full set of d functions on the sulfur, there is a potential minimun at the trans but not the cis geometry. A gauche conformer with a torsional angle of 77.2° is the most stable. With N₂O₂ this basis set gives potential minima at both the cis and trans geometries, but the trans conformer is slightly more stable, contrary to experiment and the results of (7,3) basis-set calculations reported in the literature in which Gaussian lobe functions were employed. Using a (9,5) basis set there is no longer a potential minimum at the cis geometry, and a gauche structure is more stable than the cis conformer as in the case of N₂OS with the less-extended basis set. Force constants (harmonic and anharmonic), compliance constants, relaxed force constants, and interaction-displacement coordinates for both molecules are compared for key structural elements.     

Development of an HPLC-NMR method for the determination of PAHs in soil samples - a comparison with conventional methods

A hyphenated HPLC-(1)H NMR method for the identification and quantification of PAHs in soil samples has been developed and applied to a PAH reference sample provided by the Federal Institute for Materials Research and Testing (BAM, Berlin, Germany). The results were compared with those obtained by HPLC-DAD, HPLC-F, and GC-MS analyses of the same sample.     

Synthetic studies on ecteinascidin-743: constructing a versatile pentacyclic intermediate for the synthesis of ecteinascidins and saframycins

[reaction: see text] The asymmetric synthesis of a highly functionalized pentacyclic tetrahydroisoquinoline relevant to the ecteinascidin, saframycin, safracin, and renieramycin family of antitumor alkaloids is described.     

Investigation of the self-assembly of hydrophobic self-complementary ionic tetrapeptides

The self-aggregation of two short ionic tetrapeptides (RWDW and RVDV, where R = arginine, V = valine, W = tryptophan, D = aspartic acid) was studied by different experimental techniques such as, atomic force microscopy (AFM), light scattering (LS), isothermal titration calorimetry (ITC) and viscosimetry. AFM was used to investigate the morphology of the aggregates; the AFM images showed the presence of fibrillar aggregates whose number and length increased with increasing oligopeptides concentration. On the other hand, the collected experimental calorimetric and physical chemical results consistently indicated a critical aggregation concentration (cac) around 0.5 and 2.0 mM for RWDW and RVDV respectively.     

New class of β-aminoalcohol ligands derived from isosorbide and isomannide: application in hydrogen transfer reduction of prochiral ketones

Starting from isosorbide and isomannide, two by-products from the starch industry, a family of chiral functionalized β-aminoalcohols presenting a THF ring has been synthesized as potential ligands for hydrogen transfer reduction of prochiral ketones. Under optimal conditions, more than 70% ee with an excellent conversion were obtained for the HTR of the acetophenone.     

Pharmacological interactions of essential oil constituents on the viability of micro-organisms

Complex interactions between numerous components of essential oils often contribute to the pharmacological effect and therapeutic outcome. To further elucidate these interactions, several essential oil constituents (EOCs) were combined in different ratios and their inhibitory effects on the growth of bacteria and yeast determined using the minimum inhibitory concentration (MIC) microplate assay. When combined and tested against Candida albicans, (+)-beta-pinene interacted antagonistically with (-)-menthone (sigmaFIC(T) = 9.80), but synergistically with 1,8-cineole (sigmaFIC(T) = 0.35). Against Escherichia coli, the combination of E- and Z-(+/-)-nerolidol and geranyl acetate displayed an additive interaction (sigmaFIC(T) = 1.04); while a variable interaction was observed between E- and Z-(+/-)-nerolidol and eugenol with antagonism and synergy being observed at different ratios of each EOC. The combination of either carvacrol or eugenol with an antimicrobial agent (ciprofloxacin or amphotericin B) resulted in synergistic interactions against all microorganisms tested. These favourable results further support the use of essential oil constituents as adjuvants in the development of a new generation of phytopharmaceuticals that can be used in combination with synthetic drugs against drug-resistant microorganisms.     

Ethanol/water solutions as certified reference materials for breath alcohol analyzer calibration

The Federal Institute for Materials Research and Testing (BAM), Germany, has issued a series of large volume ethanol in water certified reference materials (CRMs), primarily developed for the calibration of evidential breath alcohol analyzers in Germany. The certified parameter is the ethanol mass concentration at 20 °C. When used in a wet bath simulator, the solutions deliver gas samples that meet the requirements set by the Organization of Legal Metrology for calibration of breathalyzers. The materials were prepared gravimetrically by spiking of ethanol into water in single 5 L units. A complete uncertainty budget for the preparation process has been established. The purity of the commercial ethanol stock solution was identified to be the main source of uncertainty. For stability and homogeneity measurements and for the verification of the gravimetric mass concentration of the CRMs, a robust high-precision gas chromatography, with flame-ionization detection method for ethanol determination in aqueous samples was developed and validated. The good performance of this method has been demonstrated in several international comparisons organized by the Consultative Committee for Amount of Substance—Metrology in Chemistry at the International Bureau of Weights and Measures.     

Teacher preparation for a problem-solving curriculum in Singapore

Problem solving is at the heart of the Singapore Mathematics curriculum. However, it remains a challenge for teachers to realise this curricular goal in practice. Here, we review the efforts of Singapore mathematics teacher educators in incorporating problem-solving (teaching) competency in teacher education and PD programmes. We discuss conceptual and practical issues, actions taken and changes made in building teachers?? capacity to enact a problem-solving curriculum in a school-based design experiment project. In the project, teachers learnt problem solving, observed and then carried out lessons, using the ??Mathematics Practical????akin to the science practical??as key to instruction and assessment.     

Thermal conductivity of the PbGeO<Subscript>3</Subscript> and PbGe<Subscript>3</Subscript>O<Subscript>7</Subscript> glasses

This paper reports on a study of the thermal conductivity of the PbGeO₃ and PbGe₃O₇ glasses.