Copper(II)–Ammonia Complexation Equilibria in Aqueous Solutions at Temperatures from 30 to 250°C by Visible Spectroscopy

The spectra of copper(II)–ammonia solutions in 2 mol-kg^–1 NH₄NO₃(aq) were recorded as a function of pH with a new UV–visible flow cell, capable of operating at conditions up to 325°C and 300 bars. Equilibrium constants for the formation of copper(II)–ammonia complexes Cu(NH₃)_n ²⁺, 1 n 4, from 30 to 150°C were determined by evolving factor analysis and nonlinear least-squares regression. Measurements at higher temperatures were limited by thermal decomposition of NH₄NO₃(aq). The formation constants of Cu(NH₃)_n ²⁺ decrease with temperature, consistent with extrapolations of literature data from measurements below 100°C. Measurements above 150°C were carried out in 0.5 mol-kg^–1 CF₃SO₃H (aq), at the very high ammonia concentrations required to avoid the precipitation of CuO(s). The spectra are consistent with Cu(NH₃)₄ ²⁺ as the predominant species, based on extrapolations of peak maxima and molar absorptivities from lower temperatures. Shifts in the spectra of Cu²⁺ and the Cu(NH₃)_n ²⁺ species to higher wavelength and increases in molar absorbance with increasing temperature are discussed in terms of the structure of the complexes.     

Silver nanoparticles supported on ionic‐tagged magnetic hydroxyapatite as a highly efficient and reusable nanocatalyst for hydrogenation of nitroarenes in water

A novel chemically modified magnetic hydroxyapatite (MHAp) was prepared and used as support and stabilizer for the synthesis of silver nanoparticles. First, 1,4‐diazabicyclo[2.2.2]octane (DABCO) was successfully grafted onto the surface of MHAp, and then silver nanoparticles were homogeneously loaded on mesoporous MHAp‐DABCO (ionic‐tagged MHAp) nanocomposite by in situ chemical reduction of silver nitrate using sodium borohydride. The structure and properties of the resulting MHAp‐DABCO‐Ag nanocomposite were confirmed using various techniques. The catalytic activity of ionic‐tagged MHAp‐Ag nanocatalyst was investigated for the hydrogenation reaction of nitroarenes in aqueous media. The results reveal that the Ag‐containing inorganic–organic nanocomposite is highly efficient for the reduction of a wide range of aromatic nitro compounds under green conditions. The superparamagnetic nature of the nanocatalyst leads to its being readily removed from solution via application of a magnetic field, and it can be easily stored and reused.     

A novel fast method for aqueous derivatization of THC,OH‐THC and THC‐COOH in human whole blood and urine samples for routine forensic analyses

A novel aqueous in situ derivatization procedure with propyl chloroformate (PCF) for the simultaneous, quantitative analysis of Δ⁹‐tetrahydrocannabinol (THC), 11‐hydroxy‐Δ⁹‐tetrahydrocannabinol (OH‐THC) and 11‐nor‐Δ⁹‐tetrahydrocannabinol‐carboxylic acid (THC‐COOH) in human blood and urine is proposed. Unlike current methods based on the silylating agent [N,O‐bis(trimethylsilyl)trifluoroacetamide] added in an anhydrous environment, this new proposed method allows the addition of the derivatizing agent (propyl chloroformate, PCF) directly to the deproteinized blood and recovery of the derivatives by liquid–liquid extraction. This novel method can be also used for hydrolyzed urine samples. It is faster than the traditional method involving a derivatization with trimethyloxonium tetrafluoroborate. The analytes are separated, detected and quantified by gas chromatography–mass spectrometry in selected ion monitoring mode (SIM). The method was validated in terms of selectivity, capacity of identification, limits of detection (LOD) and quantification (LOQ), carryover, linearity, intra‐assay precision, inter‐assay precision and accuracy. The LOD and LOQ in hydrolyzed urine were 0.5 and 1.3 ng/mL for THC and 1.2 and 2.6 ng/mL for THC‐COOH, respectively. In blood, the LOD and LOQ were 0.2 and 0.5 ng/mL for THC, 0.2 and 0.6 ng/mL for OH‐THC, and 0.9 and 2.4 ng/mL for THC‐COOH, respectively. This method was applied to 35 urine samples and 50 blood samples resulting to be equivalent to the previously used ones with the advantage of a simpler method and faster sample processing time. We believe that this method will be a more convenient option for the routine analysis of cannabinoids in toxicological and forensic laboratories.     

Mass‐spectrometry‐based lipidomics

Lipids, which have a core function in energy storage, signalling and biofilm structures, play important roles in a variety of cellular processes because of the great diversity of their structural and physiochemical properties. Lipidomics is the large‐scale profiling and quantification of biogenic lipid molecules, the comprehensive study of their pathways and the interpretation of their physiological significance based on analytical chemistry and statistical analysis. Lipidomics will not only provide insight into the physiological functions of lipid molecules but will also provide an approach to discovering important biomarkers for diagnosis or treatment of human diseases. Mass‐spectrometry‐based analytical techniques are currently the most widely used and most effective tools for lipid profiling and quantification. In this review, the field of mass‐spectrometry‐based lipidomics was discussed. Recent progress in all essential steps in lipidomics was carefully discussed in this review, including lipid extraction strategies, separation techniques and mass‐spectrometry‐based analytical and quantitative methods in lipidomics. We also focused on novel resolution strategies for difficult problems in determining C=C bond positions in lipidomics. Finally, new technologies that were developed in recent years including single‐cell lipidomics, flux‐based lipidomics and multiomics technologies were also reviewed.     

Cross‐coupling reactions using porous multipod Cu2O microcrystals as recoverable catalyst in aqueous media

Porous multipod Cu₂O microcrystals were found to be an efficient, highly recyclable and eco‐friendly catalyst for the cross‐coupling reactions of aryl halides and terminal alkynes with high yields in aqueous media. Noteworthy, the Cu₂O catalyst can be reused for several times without significant decrease in catalytic activity.     

溶剂萃取预处理对低阶煤大分子结构的影响

为了研究溶剂预处理对低阶煤的固有大分子结构的影响,本研究对锡林郭勒褐煤（XLL）和神府次烟煤（SFC）分别进行了四氢呋喃（THF）索氏抽提、二硫化碳/N-甲基-2-吡咯烷酮（CS₂/NMP）混合溶剂抽提及热溶处理,并对所得抽余煤进行了傅里叶红外漫反射光谱分析（DRIFT）、热重分析（TGA）、压汞法分析（MI）和溶胀度测定。结果表明,溶剂抽提导致煤大分子结构重排和再缔合。其中,THF索式抽提和CS₂/NMP混合溶剂抽提可以改变非共价键交联作用,特别是氢键作用分布,从而不同程度地松弛煤大分子结构。然而,高温溶剂热溶处理主要促进了煤大分子的共价键交联,尤其是对锡林郭勒褐煤（XLL）。所有抽取煤的溶胀都受Fickian扩散控制,且所有抽取煤的溶胀活化能都低于原煤。     

Copper‐Mediated Reversible Deactivation Radical Polymerization in Aqueous Media

Key advances within the past 10 years have transformed copper‐mediated radical polymerization from a technique which was not very tolerant of protic media into a range of closely related processes capable of controlling the polymerization of a wide range of monomers in pure water at ppm catalyst loadings. This approach has afforded water‐soluble macromolecules of desired molecular weight, architecture, and chemical functionality, with applications ranging from drug delivery to oil processing. In this Review we highlight and critically evaluate the synthetic methods that have been developed to control radical polymerization in water by using copper complexes as well as identify future areas of interest and challenges still to be overcome.     

磷酸氢二钾催化多组分一锅法反应合成1,4-二氢吡喃并[2,3-c]吡唑衍生物

绿色、简便、高效的催化四组分反应合成吡喃并[2,3-c]吡唑类杂环化合物是当今有机化学领域的研究热点。 本文发展了在水与聚乙二醇(PEG-200)的混合液中,廉价易得的磷酸氢二钾(K₂HPO₄·3H₂O)催化乙酰乙酸乙酯、水合肼、芳香醛和丙二腈的多组分“一锅法”反应,合成一系列1,4-二氢吡喃并[2,3-c]吡唑-5-腈衍生物,产率为88%~98%。 该方法避免了使用复杂昂贵的催化剂和繁琐的纯化过程。     

Mg-Al-CO3水分散液的稳定性及流变性

水滑石;水分散体系;层状结构;Mg-Al-CO3水分散液的稳定性及流变性     

微波辅助聚乙二醇-硫酸铵双水相体系萃取铂、钯及非等温动力学

微波辅助聚乙二醇-硫酸铵双水相体系萃取铂、钯及非等温动力学