Recent comparability of oceanographic nutrients data: results of a 2003 intercomparison exercise using reference materials.

An intercomparison exercise was conducted using the recently developed Reference Material for Nutrients in Seawater (RMNS). Discrepancies of reported values among laboratories were greater than the homogeneity of RMNS samples and the reported analytical precision of nutrients. The variability of in-house standards of the participating laboratories might be the most likely source of interlaboratory discrepancies. Therefore, the use of common reference materials, i.e. certified RM, is essential to establish and improve the comparability of nutrient data of the world's oceans.     

Photochemical Smiles rearrangement and Meisenheimer complex formation catalyzed by hydroxide ion via electron hole transfer catalysis

[reactions: see text] Photochemical para-to-nitro Smiles rearrangement and para-to-nitro Meisenheimer complex formation occurs for nitrophenoxyethylamines with high concentrations of hydroxide ion in aqueous solution. Both photoreactions show first-order dependence on hydroxide ion concentration, but the mechanism involving hydroxide ion does not involve acid-base catalysis. The reactions take place from the triplet excited states of the nitrophenyl ethers. Analysis of quantum yields and kinetics is consistent with an electron hole transfer catalysis mechanism.     

Stereospecific polymerization of benzyl vinyl ether by BF3·OEt2

Polymerization of benzyl vinyl ether was carried out by BF₃·OEt₂, and the effects of polymerization conditions on the stereoregularity of the polymer were studied by NMR analysis. The polymerization at ?78°C in toluene gave a highly isotactic polymer. The isotacticity of the polymer was independent of the catalyst concentration but increased with a decrease in the initial monomer concentration and decreased slightly on raising the reaction temperature. When the polymerizations were carried out in toluene—nitroethane mixtures, a gradual decrease in the isotacticity and a rapid decrease in the molecular weight of the polymer were observed with increasing nitroethane in the solvent. The molecular weight of the polymer was almost constant, regardless of the catalyst concentration, and increased with increasing initial monomer concentration and decreasing polymerization temperature. When the polymerization was performed in toluene at ?78°C with a small amount of water or benzyl alcohol, a linear relationship was found between the reciprocal DP of the polymer and water or benzylalcohol concentration. The mechanisms of the initiation reaction and the stereoregulation in the polymerization were also discussed.     

Studies on the conformational aspects of inulin oligomers.

The conformational studies of inulin oligomers from G-F2 to G-F9, which isolated from Platycodon grandiflorum, suggested a plausible conformational change between G-F7 and G-F8 from the trends in their chemical shift patterns and molecular rotation; the oligomers higher than G-F8 would form some secondary conformations more rigid than shorter oligomers. On the other hand, spin-lattice relaxation (T1) studies of the protons proposed through-space interactions of 2- and 4-H's of glucose moiety in G-F5, presumably with some atom(s) of the terminal fructose moiety. This would reflect that the inulin molecule adopts a 5/1 helix.     

The measurement of serum human parathyroid hormone (h-PTH53-84) and effect of exercise on calcium metabolism

This study was focussed our attention on the measurement within the upper physiological level of human serum parathyroid hormone (PTH), using kits of human PTH 53-84. This assay kit was able to detect serum PTH in sera with subtle changes of serum calcium concentrations before and after short term exercise. These serum PTH levels before and after exercise seemed to be changed within the upper physiological levels of PTH. Thus, this study suggested that the assay kit was likely to become a useful tool of the measurement of the physiological level of serum PTH in humans.     

Charge Transfer Salts of BO with Paramagnetic Isothiocyanato Complex Anions: (BO)[M(isoq)2(NCS)4]; M=Cr or Fe, isoq=isoquinoline and BO=Bis(ethylenedioxo)tetrathiafulvalene

The preparation, X-ray structures and magnetic properties of two isostructural new charge transfer salts: (BO)[M(isoq)₂(NCS)₄]; M=Cr^III(1), Fe^III(2) and isoq=isoquinoline are reported. Their structure consists of alternate organic and inorganic layers, each layer being formed by mixed columns of BO radical cations and paramagnetic metal complex anions. There are short intermolecular contacts between donor and anion (S2_anion· · ·S4_BO<3.5 Å) and between adjacent BO molecules (O· · · O1<3.2 Å). The two compounds are insulators. ESR measurements show single signal without separating the donor and anion spins. The magnetic measurements obey the Curie-Weiss law and revealed dominant antiferromagnetic interactions between anion spin and donor spin, but long-range magnetic ordering did not occur down to 2 K. This is directly related to structural reasons which were deduced from a comparison of the title compounds with other 1:1 salts containing same anion complexes and different donors.     

Water solvent and local anesthetics: A computational study

There are various experimental studies regarding the toxicity and the time of action of local anesthetics, which contain general insights about their pharmacological and physicochemical properties. Although a detailed microscopic analysis of the local anesthetics would contribute to understanding these properties, there are relatively few theoretical studies about these molecules. In this article, we present the results from calculations performed for three local anesthetics: tetracaine, procaine, and lidocaine, both in their charged and uncharged forms, in aqueous environment. We have used the density functional theory and molecular dynamics simulations to study the structural characteristics of these compounds. The radial distribution function g(r) was used to examine the structure of water molecules surrounding different regions of the local anesthetics. We demonstrated the nonhomogeneous character of the anesthetics with respect to their affinity to water solvent molecules as well as the modifications in their affinity to water caused by changes in their charge state. We also observed that the biological potency of the anesthetics is more related to the behavior of specific groups within the molecule, which are responsible for the interaction with the lipid phase of membranes, rather than the general properties of the molecule as a whole. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Kinetics and stability of CH4-CO2 mixed gas hydrates during formation and long-term storage.

The formation of CH4-CO2 mixed gas hydrates was observed by measuring the change of vapor-phase composition using gas chromatography and Raman spectroscopy. Preferential consumption of carbon dioxide molecules was found during hydrate formation, which agreed well with thermodynamic calculations. Both Raman spectroscopic analysis and the thermodynamic calculation indicated that the kinetics of this mixed gas hydrate system was controlled by the competition of both molecules to be enclathrated into the hydrate cages. However, the methane molecules were preferentially crystallized in the early stages of hydrate formation when the initial methane concentration was much less than that of carbon dioxide. According to the Roman spectra, pure methane hydrates first formed under this condition. This unique phenomenon suggested that methane molecules play important roles in the hydrate formation process. These mixed gas hydrates were stored at atmospheric pressure and 190 K for over two months to examine the stability of the encaged gases. During storage, CO2 was preferentially released. According to our thermodynamic analysis, this CO2 release was due to the instability of CO2 in the hydrate structure under the storage conditions.     

Carbazole-Dendronized Luminescent Radicals

A series of carbazole-dendronized tris(2,4,6-trichlorophenyl)methyl (TTM) radicals have been synthesized. The photophysical properties of dendronized radicals up to the fourth generation were compared systematically to understand how structure–property relationships evolve with generation. The photoluminescence quantum yield (PLQY) was found to increase with the increasing generation, and the fourth generation (G4TTM) in cyclohexane solution showed a PLQY as high as 63 % at a wavelength of 627 nm (in the deep-red region) from the doublet state. The dendron modification strategy also showed a blue-shift of the emission on increasing the generation number, and the photostability was also increased compared to the bare TTM radical.     

Investigation of the Benzene–Naphthalene and Naphthalene–Naphthalene Potential Energy Surfaces: DFT/CCSD(T) Correction Scheme

The potential energy surfaces of the naphthalene dimer and benzene–naphthalene complexes are investigated using the recently developed DFT/CCSD(T) correction scheme [J. Chem. Phys. 2008 , 128, 114 102]. One and three minima are located on the PES of the benzene–naphthalene and the naphthalene dimer complexes, respectively, all of which are of the parallel‐displaced type. The stabilities of benzene–naphthalene and the naphthalene dimer are ?4.2 and ?6.2 kcal mol^?1, respectively. Unlike the benzene dimer, where the T‐shaped complex is the global minimum, the lowest‐energy T‐shaped structure is about 0.2 and 1.6 kcal mol^?1 above the global minimum on the benzene–naphthalene and the naphthalene dimer potential energy surfaces, respectively.