Lamellar Organo-Bridged Silicones

The acid-hydrolysis of an organo-bridged bisdiethoxysilylated molecular precursor bearing urea groups, (EtO)₂MeSi(CH₂)₃NHCONH(CH₂)₁₂NHCONH(CH₂)₃SiMe(OEt)₂, has been performed in pure aqueous medium. Scanning electron microscopy (SEM) analysis of the resulting insoluble solid revealed plate-like forms with a lamellar structure as determined by powder X-ray diffraction (PXRD) studies with a sharp peak at 28.5 Å. The solid state ²⁹Si MAS-NMR spectrum of this bridged siloxane hybrid is consistent with a moderately condensed material with complete preservation of the Si–C bonds throughout the hybrid network. In comparison, the classical sol–gel hydrolysis-condensation of the molecular precursor in ethanol with stoichiometric amount of water and fluoride anion as catalyst produced an amorphous featureless solid.     

A Novel Environmentally Benign Method for the Selective Oxidation of Alcohols to Aldehydes and Ketones

In the presence of [Ru(terpyridine)(2,6‐pyridinedicarboxylate)], aliphatic and benzylic alcohols are oxidized to the corresponding aldehydes or ketones with high selectivity by using hydrogen peroxide as the oxidant. There is no need for the addition of co‐catalysts or organic solvents. By applying an optimized reaction protocol, high catalyst productivity (turnover number>10 000) and activity (turnover frequency up to 14 800 h^?1) has been achieved.     

New intra-intermolecular criss-cross cycloaddition of unsymmetrical allenylazines with alkynes leading to three fused five-membered heterocycles

This report describes a new type of intra-intermolecular criss-cross cycloadditions. Thermal reactions of unsymmetrical allenylazines in the presence of alkynes led to three fused five-membered heterocycles in some cases. In the case of unsymmetrical substituted alkynes, a regioselectivity was observed. The molecular structures of all products are discussed. One X-ray crystal structure is also reported.     

氯化钙/水-醇溶液稀释热

电解质溶液稀释热是溶液的重要热性质之一．由它可计算不同浓度下电解质的溶解热、表现相对摩尔焓、溶液中反应热和化合物生成热等．在电解质溶液理论研究中，稀释热也是重要的基础数据．由稀释热可推算溶液中组分的活度系数、渗透系数、相对偏摩尔焓及表观摩尔热容等[1-3]．在化工生产中，稀释热是化工过程能量计算不可缺少的数据．电解质水溶液稀释热已有不少研究[2，4]．但电解质混合溶剂体系稀释热报导甚少．随着加盐精馏技术、海水淡化技术等研究的进展，急需这方面数据．本文作者已报告了CaCl2／C2H5OH－H2O体系[5]和CaCl2／n－C…     

生物质裂解产物的制备及HPLC检测其成分的虚拟仿真实验开发

In order to improve university laboratory teaching and practical education under the background of information technology, as well as overcome the difficulty for practical training, develop a virtual simulation experiment platform for rapid pyrolysis of natal materials and high-performance liquid chromatographic (HPLC) detection of its components. The experiment integrates the actual operation process of the plant to produce cleaved products by rapid pyrolysis of biomass with HPLC detection. The virtual experiment is divided into biomass sample pretreatment, rapid biomass pyrolysis, bio-oil extraction, and HPLC determination of complex components, making the biomass cleavage workshop "real" through simulation. This virtual simulation experiment fully integrates the utilization of biomass resources and basic chemistry courses (such as organic chemistry, instrumental analysis, chemical engineering principles, etc.), which are widely involved in agricultural and forestry majors with advantageous characteristics value.     

Trivalent atom contribution on solid-solid transformation of Ga13 polycation intercalated clay into sodalite investigated by X-ray absorption spectroscopy

Solid-solid transformation mechanism of Ga Keggin-type ion intercalated clay into sodalite has been clarified by X-ray diffraction (XRD), FT-IR spectroscopy, and X-rayabsorption spectroscopy (XAS). To follow the structural evolution precisely by XANES and EXAFS, the XAS active element containing polycation [Ga13O4(OH)24(H2O)12]7+ was intercalated into montmorillonite (MMT). FT-IR and XAS spectra confirm that the formation of sodalite framework is initiated by the delocalized rearrangement between silicate networks and collapsed interlayered Ga species, and is followed by the incorporation of Al in the octahedral sheet of clay (MMT). According to the XAS studies, it is found that the formation of Ga(Al)-O-Si species is strongly influenced by the trivalent cations, which are rapidly changed in the environment, followed by reaction with the silicate network of clay during the solid-solid transformation.     

Cure reaction and phase behavior of liquid crystalline epoxides-anhydride systems

A series of novel liquid crystalline epoxides with lateral substituents were cured with anhydrides and the cure kinetics was investigated by non-isothermal DSC technique. The results showed that the lengths of lateral substituents have great effect on the value of Ea. The curing reaction became less active, when the liquid crystalline epoxides have long lateral substituents and were controlled by diffusion at the late stage of cure. A nematic structure was observed by POM and XRD.     

Direct determination of estriol 3- and 16-glucuronides in pregnancy urine by column-switching liquid chromatography with electrospray tandem mass spectrometry

Using column-switching liquid chromatography/tandem mass spectrometry (LC-MS/MS), we developed an improved analytical method of urinary estriol glucuronides. This new method is derived predominantly from maternal and fetal precursors in pregnancy. We used in the following procedure: first, we filtered urine samples with a membrane filter. Next, we directly injected the 50 microL aliquot of urine samples onto a pre-column. Then, after activating the column-switching valve, we backflushed the loaded samples onto the C(18) analytical column. Urine samples can be assayed within 20 min without any sample preparation steps. We monitored separated estriol glucuronides by negative electrospray ionization (ESI) and selected-reaction monitoring (SRM). The calibration range of estriol-3-glucuronide (E3-3G) and estriol-16-glucuronide (E3-16G) was 0.1-20 microg/mL and the linearity of the method was 0.9984 for E3-3G and 0.9987 for E3-16G. The limits of detection at a signal-to-noise (S/N) ratio of 3 were 10 ng/mL (E3-3G) and 5 ng/mL (E3-16G). The analytical recovery was over 85% and, in general, inter-day and intra-day variability for precision and accuracy were less than 10%. When applied to a pregnancy urine sample to biomedical monitoring of the function of the maternal/fetal unit, the proposed method allowed rapid and sensitive screening for the detection of E3-3G and E3-16G.     

Construction and evaluation of nagR-nagAa::lux fusion strains in biosensing for salicylic acid derivatives

The NagR protein is a response regulatory protein found in the bacterium Ralstonia sp. U2 that is involved in sensing for salicylic acid and the subsequent induction of the operaon just upstream of its gene. The genes encoded for in this operon are involved in the degradation of salicylic acid. Escherichia coli strain RFM443 carrying a fusion of the Photorhabdus luminesscens luxCDABE operon with the nagR gene and upstream region of the nagAa gene was constructed and characterized with respect to its optimum temperature, its response time and kinetics, and its ability to deterctnumerous benzoic acid derivatives. Although capable of detecting 0.5 mM salicylic acid at any temperature between 28 and 40°C, this E. coli strain, labeled DNT5, showed its greatest relative activity at 30°C, i.e., the temperature at which the largest induction was seen. Furthermore, experiments done with numerous benzoic acid derivatives found the NagR protein to be responsive to only a few of the compounds tested, including salicylic acid and 3-methyl salicylic acid and 3-methyl saliyclic acid, and acetyl salicylic acid was the strongest inducer. The lower limits of detection for these compounds with E. coli strain DNT5 were also established, wit the native inducer, salicylic acid, giving the most sensitive response and detectable down to a concentration of about 2 μM. A second lux fusion plasmid was also constructed and transformed into an NahR background, Pseudomonas putida KCTC1768. Within this strain, NAGK-1768, the supplemental activity of the NahR protein on the nagAn promoter, was shown to extend both the range of chemicals detected and the sensitivity.