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31.
Pd-catalyzed cross-coupling reactions of various arenediazonium salts with ArSi(OR)3 and KArBF3 have been achieved in good to excellent yields under simple aerobic conditions in water at room temperature. The functional group tolerance makes these transformations as attractive alternatives to the traditional cross-coupling approaches. Furthermore, the sequence can also be performed in a one-pot domino process, omitting the isolation of the intermediate arenediazonium salt. 相似文献
32.
A series of new ionic binuclear Pd(II) complexes supported by water‐soluble bis(α‐diimine) ligands were prepared and employed as catalysts for the palladium‐catalyzed Suzuki reaction in aqueous media. The binuclear nature of the complexes increased the reaction rate, while electronic and steric modification of the ligand frameworks had a remarkable influence upon the catalytic activity of the palladium complexes. The catalysts were shown to be homogeneous through mercury poisoning experiments and complexes could be recycled more than 10 times without loss of catalytic activity. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
33.
Dr. Paolo Destito Dr. Cristian Vidal Dr. Fernando López Prof. José L. Mascareñas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(15):4789-4816
During the last decade, there has been a tremendous interest for developing non-natural biocompatible transformations in biologically relevant media. Among the different encountered strategies, the use of transition metal complexes offers unique possibilities due to their high transformative power. However, translating the potential of metal catalysts to biological settings, including living cells or small-animal models such as mice or zebrafish, poses numerous challenges associated to their biocompatibility, and their stability and reactivity in crowded aqueous environments. Herein, we describe the most relevant advances in this direction, with a particular emphasis on the systems’ structure, their mode of action and the mechanistic bases of each transformation. Thus, the key challenges from an organometallic perspective might be more easily identified. 相似文献
34.
Homoallylic alcohols have been prepared in good yields by allylation of ketones with allyl bromide in the presence of stannous chloride dihydrate, zinc iodide, and ammonium chloride in water. 相似文献
35.
The undercooling of aqueous solutions of strontium nitrate a few mm3 in volume or microsized by dispersion within an emulsion is investigated. The experimental results are consistent with a succession of transformations in undercooled solutions of binaries. Following concentration, the undercoolings are from 14°C to 20°C for macrosamples or from 39°C to 60°C with emulsions. However it is observed that Sr(NO3)2 crystallizes into a metastable phase which can be preserved for a long time. The existence of this metastable crystalline phase has been evidenced by Differential Scanning Calorimetry and by an original evaporation method. The phase diagram, including the metastable phase, is presented. 相似文献
36.
Margarita Yu. Vozhdaeva Alfiya R. Kholova Igor A. Melnitskiy Ilya I. Beloliptsev Yulia S. Vozhdaeva Evgeniy A. Kantor Albert T. Lebedev 《Molecules (Basel, Switzerland)》2021,26(7)
The main drawback of drinking water chlorination involves the formation of quite hazardous disinfection by-products (DBPs), represented mainly by halogenated species. Based on the authors’ monitoring data since 2002, the prevalence of chlorine over bromine in the composition of volatile DBPs was shown for the drinking water in Ufa (Russia). However, the situation was completely reversed in the case of semi-volatile DBPs. The principal goal of the present study involved rationalization of the results of the long-term monitoring. Gas chromatography–mass spectrometry (GC-MS) was used for the qualitative and quantitative analysis of volatile DBPs. Identification of semi-volatile compounds was carried out with GC-MS, while gas chromatography with an atomic emission detector (GC-AED) was used for their quantification. A significant contribution of oxygen to the composition of semi-volatile compounds proves the decisive role of the dissolved organic matter oxidative destructive processes. Statistical analysis revealed notable linear correlations for trihalomethane and haloacetic acid formation vs. chlorine dose. On the contrary, halogenated semi-volatile products do not demonstrate any correlations with the water quality parameters or chlorine dose. Principal component analysis (PCA) placed them into separate groups. The results allow for proposing that formation of the organohalogenated species involved the fast penetration of bromine into the humic matter molecules and, further, their oxidative destruction by active chlorine. 相似文献
37.
To prepare cross‐linked silicone (silicone rubber) particles in an aqueous medium, we investigated two synthesis methods involving a miniemulsion system. The first method was based on cationic ring‐opening polymerization of cyclic siloxane, which is a common synthetic route for linear silicone oil and uses octamethylcyclotetrasiloxane (D4) as the monomer and dimeric D4 (bis‐D4) as the cross‐linker. Although this method produces silicone particles, the particles do not remain in the particulate state after drying because of low cross‐linking density. The polymerization mechanism of this method was also investigated, which proceeds under the ring‐opening reaction of D4 in monomer droplets and upon polycondensation of hydrolyzed D4, which occurs in the water phase (ie, outside the monomer droplets). This mechanism implied that introducing the cross‐linking structure into particles is difficult because of the low solubility of bis‐D4 in water. To overcome these difficulties, we demonstrated a second method of preparing silicone particles based on the thiol‐Michael addition reaction between thiol‐terminated silicone oil and triacrylate in miniemulsion systems. Transmission electron microscopy images indicated that the silicone particles obtained in the particulate state upon drying and the aggregates of these particles showed elasticity. 相似文献
38.
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 下载免费PDF全文
《Biomedical chromatography : BMC》2018,32(4)
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. 相似文献
39.
Silver nanoparticles supported on ionic‐tagged magnetic hydroxyapatite as a highly efficient and reusable nanocatalyst for hydrogenation of nitroarenes in water 下载免费PDF全文
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. 相似文献
40.