Evaluation of gas chromatography-mass spectrometry in conjunction with chemometric resolution for identification of nitrogen compounds in crude oil

A chemometric resolution method is described for the identification of nitrogen compounds in crude oil. Prefractionation of crude oil into discrete chemical classes was performed by adsorption column chromatography using small quantities of neutral aluminum oxide and silicic acid. Subsequent high-resolution separation of individual components was achieved by using capillary column gas chromatography, and compound types were detected by mass spectrometer. In conjunction with a combined chemometric method, each principal chemical class was further resolved and separated, which made it possible to identify some nitrogen compounds in the investigated oils. To a certain extent, this method could relieve classical analysis of difficulty in identifying those species with poorly low contents or partially chromatographic overlaps, particularly in the cases where authentic standards were not available for addition into the unknown analytical systems to reveal what indeed existed in them.     

Preparation,structure, and some coordination properties of 2-chloro-3,3-diphenyl-3-thioxo-1-(2,4,6-tri-t-butylphenyl)-1,3-diphosphapropene

A sterically encumbered 3-thioxo-1,3-diphosphapropene, bearing a P=C-P=S skeleton, was prepared, characterised, and allowed to react with a carbonyltungsten(0) reagent and iodine affording the corresponding chelate tungsten(0) complex and charge-transfer complex with iodine, respectively, which were analysed by the X-ray crystallography.     

Discovery of a potent,selective protein tyrosine phosphatase 1B inhibitor using a linked-fragment strategy

Protein tyrosine phosphatase 1B (PTP1B) is an enzyme that downregulates the insulin receptor. Inhibition of PTP1B is expected to improve insulin action, and the design of small molecule PTP1B inhibitors to treat type II diabetes has received considerable attention. In this work, NMR-based screening identified a nonselective competitive inhibitor of PTP1B. A second site ligand was also identified by NMR-based screening and then linked to the catalytic site ligand by rational design. X-ray data confirmed that the inhibitor bound with the catalytic site in the native, "open" conformation. The final compound displayed excellent potency and good selectivity over many other phosphatases. The modular approach to drug design described in this work should be applicable for the design of potent and selective inhibitors of other therapeutically relevant protein tyrosine phosphatases.     

PNA for one-base differentiating protection of DNA from nuclease and its use for SNPs detection

By the combination of peptide nucleic acid (PNA) with single-stranded DNA specific nucleases, alteration of a single base to another in DNA has been detected with high accuracy. Only the DNAs in DNA/PNA duplexes involving a mismatch are efficiently hydrolyzed by these enzymes, whereas fully matching sequences are kept intact. This difference is visually scored by adding 3,3'-diethylthiadicarbocyanine, which changes its color from blue to purple upon binding to DNA/PNA duplexes. These findings are applied to the convenient and straightforward detection of single nucleotide polymorphisms (SNPs). When the target site in the sample DNA is completely complementary with the PNA, a notable amount of DNA/PNA duplex remains and thus the solution exhibits purple color. In the presence of even one mismatch between PNA and DNA, however, the DNA is completely digested by the enzyme and therefore the dye shows its intrinsic blue color. The SNPs in the apolipoprotein E gene of human DNA have been successfully genotyped by this method.     

Efficient Nazarov cyclizations of 2-alkoxy-1,4-pentadien-3-ones

Expeditious and high-yielding Nazarov cyclizations of 2-alkoxy-1,4-pentadien-3-ones are described. An example of a catalytic asymmetric Nazarov cyclization is presented. [reaction: see text]     

Surfactant driven flows overlying a hydrophobic epithelium: film rupture in the presence of slip

Both for tear films and along the airways within the lung, one has an extremely thin fluid layer overlying a biological substrate; in both cases surfactants either of natural origin, or artificially introduced, are important in driving fluid flows. There is evidence that slip can occur when hydrophilic liquids, similar to mucus or aqueous tear films, overlie hydrophobic epithelium. Utilizing results from recent experimental findings we examine the possible influence of slip upon tear film rupture, important in so-called dry eye, and upon surfactant-induced flows within the lung, used in surfactant replacement therapy.     

Formation of Monolayer Lipid Membranes in Water and Ethanol from Bolaamphiphiles

Three single-chain bolaamphiphiles containing two salicylidene units per molecule as the rigid segment were synthesized. Their aggregation behavior in water and ethanol has been studied. They can form monolayer membranes not only in water solution but also in pure ethanol. The presence of a relatively short methylene chain as a spacer at the center of the molecule has a dramatic influence on the morphology of the aggregates formed. Copyright 2001 Academic Press.     

Testing multivariate uniformity and its applications

Some new statistics are proposed to test the uniformity of random samples in the multidimensional unit cube These statistics are derived from number-theoretic or quasi-Monte Carlo methods for measuring the discrepancy of points in . Under the null hypothesis that the samples are independent and identically distributed with a uniform distribution in , we obtain some asymptotic properties of the new statistics. By Monte Carlo simulation, it is found that the finite-sample distributions of the new statistics are well approximated by the standard normal distribution, , or the chi-squared distribution, . A power study is performed, and possible applications of the new statistics to testing general multivariate goodness-of-fit problems are discussed.

     

Resonant spin excitation in an overdoped high temperature superconductor

An inelastic neutron scattering study of overdoped Bi(2)Sr(2)CaCu(2)O(8+delta) ( T(c) = 83 K) has revealed a resonant spin excitation in the superconducting state. The mode energy is E(res) = 38.0 meV, significantly lower than in optimally doped Bi(2)Sr(2)CaCu(2)O(8+delta) ( T(c) = 91 K, E(res) = 42.4 meV). This observation, which indicates a constant ratio E(res)/k(B)T(c) approximately 5.4, helps resolve a long-standing controversy about the origin of the resonant spin excitation in high temperature superconductors.