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31.
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Alkyl dioxazaborolidines are air-stable and often crystalline organoboranes. A variety of Br?nsted acids activate allyl dioxazaborolidines to generate reactive allyl-transfer reagents in situ. These reagents add to aldehydes and ketones to generate the corresponding alcohols in good yields under mild conditions. The E- and Z-crotyl reagents react diastereoselectively with aldehydes and ketones to produce anti and syn adducts, respectively, a result consistent with a cyclic transition state (type I mechanism). 相似文献
33.
Robert Gruar Christopher James Tighe Lee M. Reilly Gopinathan Sankar Jawwad Arshad Darr 《Solid State Sciences》2010,12(9):1683-1686
Herein, we report the rapid single step hydrothermal synthesis of phase pure Bi2MoO6 (koechlinite) and Bi2Mo3O12, via a continuous hydrothermal flow synthesis (CHFS) reactor, which uses supercritical water of 375–450 °C at a pressure of 24.1 MPa as a crystallising medium. The product being obtained as highly crystalline nano-materials with high surface area. Simple variation in synthesis condition and appropriate solution stoichiometry were shown to be sufficient to select the phase of the product. The materials synthesised showed significant photcatalytic activity towards the decolourisation of methylene blue in comparison to a commercial gold standard photocatalyst. 相似文献
34.
Norman R. Reilly 《Semigroup Forum》2014,89(1):249-265
The author has shown previously how to associate a completely 0-simple semigroup with a connected bipartite graph containing labelled edges and how to describe the regular principal factors in the free objects in the Rees-Sushkevich varieties RS n generated by all completely 0-simple semigroups over groups from the Burnside variety G n of groups of exponent dividing a positive integer n by employing this graphical construction. Here we consider the analogous problem for varieties containing the variety B 2 , generated by the five element Brandt semigroup B 2, and contained in the variety NB 2 ∨G n where NB 2 is the variety generated by all left and right zero semigroups together with B 2. The interval [NB 2 ,NB 2 ∨G n ] is of particular interest as it is an important interval, consisting entirely of varieties generated by completely 0-simple semigroups, in the lattice of subvarieties of RS n . 相似文献
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Urocanic Acid (UCA) exists in mammalian skin primarily as the trans isomer and is photoisomerized to cis UCA upon UVB absorption. Our previous studies indicated that the photoisomerization of UCA is the initiating event in UBV-induced suppression of cell-mediated immunity (tUCA----cUCA----immune suppression). The purpose of this study was to verify the role of UCA in UV-induced immune suppression of contact hypersensitivity (CHS) in BALB/c mice. Since UCA is a metabolite of the amino acid L-histidine, we reasoned that increased dietary levels of histidine should raise skin tUCA levels. If skin tUCA is the UVB photoreceptor for immune suppression, this increase should enhance UV-induced suppression of CHS. HPLC analysis of skin from BALB/c mice given a histidine-rich diet (10%) showed that the total amount of UCA is significantly higher in these animals than in mice fed a normal diet. Further, levels of suppression of CHS of 3% and 49% in control fed mice, induced by 4.8 and 7.2 kJ/m2 UVB were significantly increased to 21% and 71% respectively in histidine-fed animals at these same UVB doses. These findings provide additional support for the UCA model for immune suppression, and provide the first evidence that UV-induced immune suppression can be enhanced by a dietary component, L-histidine. 相似文献
38.
Nonlinear kernel methods have been widely used to deal with nonlinear problems in latent variable methods. However, in the presence of structured noise, these methods have reduced efficacy. We have previously introduced constrained latent variable methods that make use of any available additional knowledge about the structured noise. These methods improve performance by introducing additional constraints into the algorithm. In this paper, we build upon our previous work and introduce hard‐constrained and soft‐constrained nonlinear partial least squares methods using nonlinear kernels. The addition of nonlinear kernels reduces the effects of structured noise in nonlinear spaces and improves the regression performance between the input and response variables. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
39.
Fernandez FM Hostetler D Powell K Kaur H Green MD Mildenhall DC Newton PN 《The Analyst》2011,136(15):3073-3082
Throughout history, poor quality medicines have been a persistent problem, with periodical crises in the supply of antimicrobials, such as fake cinchona bark in the 1600s and fake quinine in the 1800s. Regrettably, this problem seems to have grown in the last decade, especially afflicting unsuspecting patients and those seeking medicines via on-line pharmacies. Here we discuss some of the challenges related to the fight against poor quality drugs, and counterfeits in particular, with an emphasis on the analytical tools available, their relative performance, and the necessary workflows needed for distinguishing between genuine, substandard, degraded and counterfeit medicines. 相似文献
40.
Determination of the structure of heparin-derived oligosaccharides by 1H NMR is challenging because resonances for all but the anomeric protons cover less than 2 ppm. By taking advantage of increased
dispersion of resonances for the anomeric H1 protons at low pD and the superior resolution of band-selective, homonuclear-decoupled (BASHD) two-dimensional 1H NMR, the primary structure of the heparin-derived octasaccharide ∆UA(2S)-[(1 → 4)-GlcNS(6S)-(1 → 4)-IdoA(2S)-]3-(1 → 4)-GlcNS(6S) has been determined, where ∆UA(2S) is 2-O-sulfated ∆4,5-unsaturated uronic acid, GlcNS(6S) is 6-O-sulfated, N-sulfated β-d-glucosamine and IdoA(2S) is 2-O-sulfated α-l-iduronic acid. The spectrum was assigned, and the sites of N- and O-sulfation and the conformation of each uronic acid residue were established, with chemical shift data obtained from BASHD-TOCSY
spectra, while the sequence of the monosaccharide residues in the octasaccharide was determined from inter-residue NOEs in
BASHD-NOESY spectra. Acid dissociation constants were determined for each carboxylic acid group of the octasaccharide, as
well as for related tetra- and hexasaccharides, from chemical shift–pD titration curves. Chemical shift–pD titration curves
were obtained for each carboxylic acid group from sub-spectra taken from BASHD-TOCSY spectra that were measured as a function
of pD. The pK
As of the carboxylic acid groups of the ∆UA(2S) residues are less than those of the IdoA(2S) residues, and the pK
As of the carboxylic acid groups of the IdoA(2S) residues for a given oligosaccharide are similar in magnitude. Relative acidities
of the carboxylic acid groups of each oligosaccharide were calculated from chemical shift data by a pH-independent method. 相似文献