Importance of structural tightening, as opposed to partially bound States, in the determination of chemical shift changes at noncovalently bonded interfaces

Two models (A and B) have been proposed to account for decreased downfield chemical shifts of a proton bound by noncovalent interactions at a ligand/antibiotic interface as the number of ligand/antibiotic interactions is decreased. In model A, the proton involved in the noncovalent bond suffers a smaller downfield shift because the bond is, with a relatively large probability, broken, and not because it is longer. In model B, the proton involved in the noncovalent bond suffers a smaller downfield shift because the bond is longer, and not because it is, with a relatively large probability, broken. We show that model A cannot account for the chemical shift changes. Model B accounts for the process of positively cooperative binding, in which noncovalent bonds are reduced in length and thereby increase the stability of the organized state.     

Direct measurement of Criegee intermediate (CH2OO) reactions with acetone, acetaldehyde, and hexafluoroacetone

Criegee biradicals, i.e., carbonyl oxides, are critical intermediates in ozonolysis and have been implicated in autoignition chemistry and other hydrocarbon oxidation systems, but until recently the direct measurement of their gas-phase kinetics has not been feasible. Indirect determinations of Criegee intermediate kinetics often rely on the introduction of a scavenger molecule into an ozonolysis system and analysis of the effects of the scavenger on yields of products associated with Criegee intermediate reactions. Carbonyl species, in particular hexafluoroacetone (CF(3)COCF(3)), have often been used as scavengers. In this work, the reactions of the simplest Criegee intermediate, CH(2)OO (formaldehyde oxide), with three carbonyl species have been measured by laser photolysis/tunable synchrotron photoionization mass spectrometry. Diiodomethane photolysis produces CH(2)I radicals, which react with O(2) to yield CH(2)OO + I. The formaldehyde oxide is reacted with a large excess of a carbonyl reactant and both the disappearance of CH(2)OO and the formation of reaction products are monitored. The rate coefficient for CH(2)OO + hexafluoroacetone is k(1) = (3.0 ± 0.3) × 10(-11) cm(3) molecule(-1) s(-1), supporting the use of hexafluoroacetone as a Criegee-intermediate scavenger. The reactions with acetaldehyde, k(2) = (9.5 ± 0.7) × 10(-13) cm(3) molecule(-1) s(-1), and with acetone, k(3) = (2.3 ± 0.3) × 10(-13) cm(3) molecule(-1) s(-1), are substantially slower. Secondary ozonides and products of ozonide isomerization are observed from the reactions of CH(2)OO with acetone and hexafluoroacetone. Their photoionization spectra are interpreted with the aid of quantum-chemical and Franck-Condon-factor calculations. No secondary ozonide was observable in the reaction of CH(2)OO with acetaldehyde, but acetic acid was identified as a product under the conditions used (4 Torr and 293 K).     

Liquid chromatographic analysis of vitamin B6 in reconstituted infant formula: collaborative study

A liquid chromatographic (LC) method was validated for the determination of total vitamin B6 in infant formula. Total vitamin B6 was quantified by converting the phosphorylated and free vitamers into pyridoxine. Pyridoxine was determined by ion pair reversed-phase LC with fluorescence detection. The method was subjected to an AOAC collaborative study involving a factory-manufactured, milk- and soy-based infant formula. Each was spiked at 3 concentrations in the range of 0-1 microg/g and sent as blind duplicate to participant laboratories. Nine laboratories returned valid data which were statistically analyzed for outliers and precision parameters. The repeatability relative standard deviation (RSD(r)) ranges were 2.0-4.0 and 3.5-5.9% for fortified milk- and soy-based formulas, respectively. The reproducibility relative standard deviation (RSD(R)) ranges were 8.2-8.4 and 6.7-11.2% for fortified milk- and soy-based formulas, respectively. HORRAT values ranged from 0.42 to 0.53, indicating that the precision of the method is acceptable. The mean RSD(r):RSD(R) values were 0.60 and 0.55 for milk- and soy-based formulas, respectively. As expected, RSDs for the unfortified samples were higher, but their HORRAT values (0.81 and 2.06) helped define a realistic limit of quantitation as 0.05 microg/g. Recovery data were quantitative and varied between 81.4 and 98.0% (mean = 89.8%) for each of 6 spiked materials.     

Binding of an inhibitor of the p53/MDM2 interaction to MDM2

The mode of action of the secondary metabolite chlorofusin, which antagonises the interaction between p53 and MDM2, involves direct binding to the N-terminal domain of MDM2.     

昆虫信息素研究III: 拟蚜虫警戒素的研究

合成了一系列碳数为十五和十四的倍半萜类蚜虫警戒素,并进行了生物活性测定,从中筛选有效化合物.     

Sequential anaerobic-aerobic biodegradation of PCBs in soil slurry microcosms

Applied Biochemistry and Biotechnology - Many industrial locations have identified the need for treatment of polychlorinated biphenyl (PCB) wastes and remediation of PCB-contaminated sites....     

Dimensional scaling and renormalization

Chief features of dimensional scaling methods are exemplified by briefly reviewing prototypical applications and recent developments. The pseudoclassical large-D limit usually can be evaluated exactly regardless of the magnitude, nature, and number of strong, nonseparable dynamical interactions. Often, this limit can be accurately linked to D = 3 by perturbation or interpolation methods. This is because the dimension dependence of many-body effects tends to be smooth and mild when calibrated by appropriate one- or few-body problems. A simple renormalization procedure applied to atoms with up N ∼ 100 electrons yields a major part of the correlation energy. From Hartree-Fock input, a renormalized nuclear charge is determined which renders the dimensionally scaled energy at D → ∞ a good approximation to that for D = 3 with the actual Z. Prospects are discussed for other means to exploit dimensional scaling, including an analogous renormalization procedure for molecules. © 1996 John Wiley & Sons, Inc.     

Some variations on Kac's formula for Brownian motion

We show that under suitable conditions $$\begin{gathered} E_x f\left\{ {a + \int_0^t \beta \left[ {b + \int_0^s {\alpha \left( {X_r } \right)dr, c + s, X_s } } \right]ds, b + \int_0^t {\alpha \left( {X_s } \right)ds, c + t, X_t } } \right\} \hfill \\ = e^{tG} f\left[ {a, b, c, x} \right] \hfill \\ \end{gathered} $$ whereX _t is a Brownian motion andG is the generator of a (C ₀) contraction semigroupe ^tG.