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101.
M. Paleologou W. C. Purdy S. K. Misra S. Z. Korczak 《International journal of environmental analytical chemistry》2013,93(4):215-242
Abstract A novel reaction for the dechlorination of polychlorinated biphenyls (PCBs) as well as most other chlorinated aromatic and aliphatic compounds is evaluated and discussed in terms of its potential for analytical purposes. The active dechlorinating agent is prepared through the reaction of molten sodium or potassium with polyethylene glycols (MW >200), in the absence of oxygen, to form the corresponding alkali metal glycolate, a powerful nucleophilic agent. Special emphasis is given to the mechanistic aspects of the reaction and their importance in terms of achieving high and reproducible yields with analytical quantities of substrate, in short periods of time. The contribution of the techniques: ESR, NMR, IR, UV, MS, GC-ECD, LC-EC, CIDNP-NMR, conductimetry and chloride analysis (amperometric) in elucidating the reaction mechanism and providing valuable kinetic data is illustrated. This reaction can potentially be applied to the determination of PCBs in waste oils. 相似文献
102.
Kentaro Iwasaki Kazunori Umishita Shojun Hino Koichi Kikuchi Yohji Achiba 《Molecular Crystals and Liquid Crystals》2013,570(1):623-628
Abstract Ultraviolet photoelectron spectra of potassium dosed higher fullerenes are measured with a synchrotron radiation light source. Potassium dosing to higher fullerenes brings a new structure between the spectral onset of pristine fullerenes and the Fermi level. As the spectral edge of the new structure does not cross the Fermi level, potassium dosed higher fullerenes are not metallic but semiconductive. When the potassium is excessively dosed to the fullerenes, the lower binding energy structures above 5 eV become faint. In contrast to this phenomenon, four distinct structures appear between 5 and 14 eV. 相似文献
103.
Using a molecular dynamics simulation technique,we compared several commonly used ion-water models to describe the microscopic structures and dynamics in KSCN aqueous solutions.Results are compared with observations of femtosecond infrared vibrational-energy transfer and anisotropy measurements.The Jorgensen/TIP4P model is found to provide the best reproduction of clustering properties such as percentage of clustered ions,cluster-size distribution,concentration dependence of the water,and ion-rotation time constants. 相似文献
104.
Aleksandar Kremenovi Predrag Vuli 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(3):256-259
The X‐ray powder diffraction pattern that corresponds to the disordered state of kalsilite (potassium aluminium orthosilicate), KAlSiO4, is investigated. The directionality of (Al,Si)O4 tetrahedra within single six‐membered tetrahedral ring building units (S6R) could not be defined. With equal probability for the directionality of each tetrahedra within one S6R [free apex pointing up (U) or down (D)], an undefined sequence of U and D directionalities is needed to describe the S6R building units. The extinction conditions of disordered kalsilite are also different compared to ordered kalsilite within the space group P63. In disordered kalsilite, h0l and hhl reflections with l = 2n + 1 are systematically absent. 相似文献
105.
A variety of heterobiaryl compounds have been synthesized by the Suzuki‐Miyaura coupling reactions of heteroaryl halides with potassium aryltrifluoroborates. Pd (OAc)2 was found to be highly efficient for the Suzuki‐Miyaura coupling reactions of various heteroaryl halides with potassium aryltrifluoroborates in aqueous systems, delivering the corresponding heterobiaryl compounds in good to excellent yields. 相似文献
106.
Diana Gonzalez Joseph T. Golab Andrew J. Cigler James A. Kaduk 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(7):706-715
The crystal structures of a new polymorph of dipotassium hydrogen citrate, 2K+·HC6H5O72?, and potassium rubidium hydrogen citrate, K+·Rb+·HC6H5O72?, have been solved and refined using laboratory powder X‐ray diffraction and optimized using density functional techniques. In the new polymorph of the dipotassium salt, KO7 and KO8 coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis and [111]. The hydrophobic methylene groups face each other in the channels. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to the central ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to a different central carboxylate group. In the potassium rubidium salt, the K+ and Rb+ cations are disordered over two sites, in approximately 0.72:0.28 and 0.28:0.72 ratios. KO8 and RbO9 coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to an ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to the central carboxylate group. Density functional theory (DFT) calculations on the ordered cation structures suggest that interchange of K+ and Rb+ at the two cation sites changes the energy insignificantly. 相似文献
107.
Abstract In this study, the molecular weights of the polymer from vinyl benzoate has been reported for different dose rates and different temperatures. The mol.wt. remains around 4000. With increasing dose, the molecular weight increases to about 14,000. The degrees of polymerization and the kinetic chain lengths calculated from the experimentally determined G R values have been compared which show that the kinetic chain length is larger than the D ? Pn. From a plot of the (D ? Pn)?1 vs. R p , an intercept is obtained which is equal to 3.25 × 10?2 which is higher than obtained in conventional polymerization. By examining the effect of temperature on mol.wt., the dependence of R p on dose rate and the absence of induction period it has been concluded that chain transfer occurs to impurities that are generated during radiolysis. 相似文献
108.
Zheng Li Jin-Lan Yu Sheng-Yi Shi Wei Zhu 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5):1031-1037
A rapid method to N-acyl ureas from corresponding N-acyl thioureas is described. N-coumaroyl-N′-arylthioureas, which are easily prepared by the reaction of coumarin-3-carboxylic acid chloride with potassium thiocyanate and arylamines, can be expeditiously transformed into corresponding N-acyl ureas via r.t. grinding with wet silica supported potassium permanganate under solvent-free conditions in an excellent yield. 相似文献
109.
Yinghai Liu Jianping Zhang Rongyue Zhang Weiqi Zhou Shengxian Li 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1127-1132
In this article, the graft copolymerization of 4‐vinyl pyridine (4VP) onto nylon‐6 (PA6) using potassium diperiodacuprate (III) (DPC)–PA6 redox system as initiator is investigated in an alkaline medium. The structure and the properties of graft copolymer are confirmed by Fourier transfer infrared spectroscopy (IR), X‐ray diffraction and thermogravimetric analysis (TGA). The mechanism is proposed to explain the generation of radicals and the initiation. The effects of reaction variables, such as the initiator concentration, ratio of 4VP to PA6, pH, as well as reaction temperature and time are investigated. Graft copolymers with high grafting efficiency (>95%) were obtained, which indicated that the DPC–PA6 redox system was an efficient initiator for this graft copolymerization. The quaternized PA6‐g‐P4VP (QPAVP) is proven to be an excellent adsorbent to heavy metal ions. 相似文献
110.
Fernando R. Díaz Jorge L. Torres M. Angélica Del Valle Jorge H. Vélez J. Christian BernÈde Gastón A. East 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1101-1108
Poly(3,5‐dichloroaniline) was prepared by chemical oxidation in the presence of various sulfonic acids as doping agent, using potassium permanganate as oxidant. 1‐Naphtalene sulfonic acid, 2‐naphatalene sulphonic acid, 1,5‐naphtalene disulfonic acid, and p‐toluenesulfonic acid were the acids of choice. Infrared and UV‐Vis spectroscopy, utilized to characterize the polymers, revealed that the compounds exist in the emeraldine (conductive) oxidation state. The level of doping, conductivity, and morphology were determined as well. The presence of a sulfonic acid produces a morphological change, from granular to microtubule structures, which is responsible for the strong increase in the conductivity of the polymer. 相似文献