A Novel pH-Sensitive MRI Contrast Agent

A tetrasubstituted derivative of 1,4,7,10-tetraazacyclododecane with amide coordinating groups and extended noncoordinating phosphonate groups forms a complex with gadolinium(III) (shown in the picture) which contains one slowly exchanging inner-sphere water molecule (tau(M)=21 μs). The 20-MHz water proton relaxivity of the complex was found to be highly pH dependent. Protonation of the noncoordinating phosphonate groups appears to catalyze prototropic exchange of the bound water protons, thereby providing a mechanism for enhanced water contrast below pH 7.     

Triorganosilyl Ethers of Benzaldehyde,m-Methoxybenzaldehyde and Anisoles

Synthesis of six new triorganosiloxybenzaldehydes, two m-methoxy-(triorganosiloxy)benzaldehydes, and seven methoxy(triorganosiloxy)benzenes are reported. From comparison of the stability of these compounds in the atmosphere, it is concluded that formyl group shows unfavorable influence and methoxy group shows favorable influence on the stability of these compounds. The oposite influences of these two groups on phenoxysilane linkage seems to connect with the oposite directiones of inductive effect of formyl group and resonance effect of methoxy group on the benzene ring.     

The Substituent Effects of tert-Butyl Radical Addition to 2-Substituted Allyl Chlorides

The relative rates for the addition reactions of tert-butyl radical to 2-substituted ally chlorides I have een determined. The correlation of log k/k₀, vs. σ_m gives a ρ mvalue of 3.59 with correlation coefficient of 0.930. When the substituent CH₂Cl is excluded, correlation coefficient raises to 0.990 and ρ value becomes 3.39. The large p value and the deviation of relative rate of substituent CH₂C1 are discussed.     

Cu(I) catalyst in DMF: an efficient catalytic system for the synthesis of furans from 2-(1-alkynyl)-2-alken-1-ones

The cyclization of 2-(1-alkynyl)-2-alken-1-ones 1 proceeded very smoothly in the presence of alcohols 2 with a catalytic amount of Cu(I)Br in DMF at 80 degrees C, leading to the formation of highly substituted furans 3. The catalytic system reported herein is easy to handle, compared to the previously known system wherein the reaction between 1 and 2 needed to use moisture sensitive gold(III) chloride.     

深圳市1408例儿童发中钙,铁,镁含量调查与分析

用火焰原子吸收法检测了深圳市１４０８例１３岁以下儿童发中钙，铁，镁的元素含量，并探讨了元素含量与年龄，性别的关系，结果显示，性别差异有显著意义，钙，镁含量随年龄增长有相似变化。     

The Photochemistry of Diazomethane the Reactions of Methylene with Toluene and P-Xylene in Liquid Phase (I)

The photochemistry of diazomethane in toluene and p-xylene solutions was investigated. The reactions of methylene with toluene gave eight products. In the diazomethane p-xylene solution, p-ethyltoluene, 1,2,4-trimethylbenzene, 1,4-dimethylcyclohepatriene-1,3,5 and three unidentified compounds were found as products of the reaction of methylene with p-xylene. The relative rates of addition and insertion reaction of methylene with toluene and p-xylene have been calculated.     

Enantioselective Addition of Iodine Azide to α,β-Unsaturated Carboxylic Acid Derivatives

The addition of iodine azide to chiral conjugated N-enoyl-sultam or α,β-unsaturated N-acyloxazolidinones generated two asymmetric centers at C(α) and C(β) with high π-face differentiation and regioselectivity. The diastereomerically pure product was easily obtained by crystallization with purity up to 94% de. The structure of 2a was determined by X-ray diffraction analysis which also indicated that B and 4 are reactive conformations.     

The RS-.HSR Hydrogen Bond: acidities of alpha,omega-dithiols and electron affinities of their monoradicals

Gas-phase acidities (deltaGo(acid)) have been measured for 1,2-ethanedithiol, 1,3-propanedithiol, and 1,4-butanedithiol, using a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Adiabatic electron affinities (EAs) of the thiolate monoradicals of these compounds were assigned from electron photodetachment spectra of their corresponding thiolate monoanions, acquired using a cw-ICR. The dithiols exhibit enhanced acidities (up to 8.7 kcal/mol in deltaGo(acid)) and greater EAs (up to 6.7 kcal/mol) than analogous monothiol species. These differences are attributed to an intramolecular RS-.HSR hydrogen bond in the thiolate anion. Considerations of the RO-.HOR hydrogen bond in monoanions of alpha,omega-diols and in the [CH(3)O-.HOCH(3)] complex anion suggest that the RS-.HSR hydrogen bond provides up to 9 kcal/mol extra stabilization.     

Chemische Vitamin D<Subscript>3</Subscript>-Bestimmung in Lebertran

The different aspects of Vitamin D₃ determination and the data reported in the literature are discussed. The spectrophotometric determination of Vitamin D₃ in cod-liver oil is carried out after the alkaline saponification, extraction of unsaponified parts, precipitation of accompanying sterols and the column- and thin-layer chromatographic purification and separation of vitamin D₃ on 40 cm plates from other vitamins. The dyestuff α-naphtholbenzein is suited well as standard substance for the better location and identification of vitamin D₃ zone on the thin-layer plate. The results obtained from the chemical method were checked through the simultaneous biological determination.     

Theoretical study of the effect of frit quality on chromatography using computational fluid dynamics

Summary Frits at both ends of a chromatographic column, especially for a preparative column, have significant influence on the flow distribution within the column and thus the column efficiency. However, frits have received little attention from chromatographers in the past. Here a theoretical study was conducted with the aid of CFD software FLUENT to investigate the effect of frits on the performance of homogeneous and heterogeneous chromatographic columns. A dimensionless number,FQ, was applied to characterize frit quality. This study visualized how frit quality affects the flow distribution and the concentration band, the shape of eluted pulse at the colum exit and column efficiency. Simulation results show that the development length of the flow distribution is related toFQ but has nothing to do with the packing heterogeneity. The curvature of the concentration band in a column depends onFQ and packing quality. This study shows column efficiency can be improved significantly by increasingFQ and/or frit permeability.