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101.
Ali Mohammad Akbar Mirza Aminul Huq Keng See Tho Wai Butcher Raymond J. 《Transition Metal Chemistry》2003,28(2):241-245
Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H2dapsme) which reacts with K2MCl4 (M = PdII, PtII) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me2CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H2dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K2PdCl4 in an EtOH–H2O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination. 相似文献
102.
链酚胺型配体锌(Ⅱ)配合物模拟碳酸酐酶研究 总被引:1,自引:2,他引:1
合成了酚胺型链状配体,N,N'-二(2-羟基苄基)丙二胺(H~2L)及其Zn(Ⅱ)配合物(ZnL),通过元素分析、IR和^1HNRM等手段进行了表征。采用pH电位滴定法,在25℃±0.1℃,I=0.1mol·dm^-^3(KNO~3)条件下,测定了配体的质子化常数以及配体与金属离子Zn(Ⅱ)配位反应平衡常数。讨论了配体与金属离子Zn(Ⅱ)的配位情况,得到了配位酚羟基的解离常数。运用分光光度法,在25℃±0.1℃,I=0.1mol·dm^-^3(KNO~3)条件下,在pH=5.5~9.0(50mmol·dm^-^3缓冲溶液)范围内,研究了配合物作为碳酸酐酶模拟物催化对-硝基苯酚乙酸酯(NA)水解动力学,得到了NA酯水解的配合物催化速率常数k~N~P。实验结果表明,ZnHL^+的配位酚羟基的解离常数pK~a为6.83;催化速率常数k~N~P与pH之间不存在Sigmoidal型曲线关系,而是在pH值中性附近有最大值,ZnHL^+对NA酯水解有很好的催化效果,并且采取双重催化机理,是碳酸酐酶很好的模拟物。 相似文献
103.
The mechanism of sorption of ions by polyurethanes has been investigated through detailed studies of the extraction of cobalt(II) thiocyanate and the salts of several organic acids. Polyether-based polyurethanes. particularly those containing poly(ethylene oxide), were found to be distinctly superior to polyesters in the sorption of salts and performed much better than might be expected by analogy with monomeric liquid solvents. The results were judged to be inconsistent with several possible mechanisms, including adsorption, solvent extraction, weak or strong base anion-exchange, and complexation of metal anions by the polymer. A new proposal, termed the cation chelation mechanism (CCM), was advanced to account for the observations. In this view, a number of cations (including those of the alkali metals, alkaline earth metals, some transition metals, NH(+)(4), RNH(+)(3) and perhaps H(3)O(+)) may be multiply complexed (chelated) by portions of the polymer, thus facilitating the sorption of accompanying anions. As predicted by the mechanism, moderately strong and selective complexation of several cations was observed to occur with the following order of selectivity: Li(+) < Na(+) < Cs(+) < Rb(+) < K(+) approximately NH(+)(4) < Ag(+) approximately Tl(+) < Ba(2+) < Hg(2+) < Pb(2+). Such behaviour parallels that known for many crown and non-cyclic polyethers and is therefore identified with the polyether portions of the polymer, which are thought to adopt helical conformations surrounding the complexed cations. The cation-chelation mechanism may be widely applicable to the sorption of ions of several types by polyether-based polyurethanes, particularly when large, hydrophobic anions (such as anionic metal complexes) are accompanied by an excess of chelatable cations. 相似文献
104.
C. M. Wai M. E. Dysart M. Blander R. R. Heinrich M. C. Oselka 《Journal of Radioanalytical and Nuclear Chemistry》1988,124(1):21-32
A lanthanum fluoride precipitation method for the separation of18F produced from the18O(p,n)18F reaction in alkali halide salts is described. This radiochemical separation method minimizes interferences from other positron emitters produced by proton bombardment and makes the accurate determination of ppm-level18O in complex alkali halide systems feasible. The interference from the19F(p,d)18F reaction is eliminated by keeping the proton energy less than 8.2 MeV. Applications of this technique to studies of dissolved oxide species in molten alkali halide salts are discussed. 相似文献
105.
Xu J Jiao P Deng D Zhang Q Tsang CW Chan AS 《Rapid communications in mass spectrometry : RCM》2002,16(12):1174-1179
The mass spectrometric fragmentation behaviour of five pairs of (R,R)- and (S,S)-4,5-bis(benzoxazol-2-yl)-2,2-dimethyl-1,3-dioxolane derivatives, one pair of (R,R)- and (S,S)-4,5-bis(benzothiazol-2-yl)-2,2-dimethyl-1,3-dioxolanes, and three pairs of (R,R)- and (S,S)-N,N'-bis(2-hydroxyaryl)-2,2-dimethyl-1,3-dioxolane-4,5-dicarbamides, all important compounds for asymmetric catalysis (P. Jiao et al., Tetrahedron Asymmetry 2001; 12: 3081), has been studied with the aid of mass-analyzed ion kinetic energy spectrometry and accurate mass measurements under electron impact ionization conditions. The spectral observations have been rationalized in terms of fragment ion structures and fragmentation mechanisms that will provide an aid to spectral interpretation for new compounds of this type. 相似文献
106.
Preconcentration of phosphate as molybdoantimonylphosphoric acid on polyurethane foam has been combined with X-ray fluorescence measurement of antimony for the indirect determination of phosphate. The extraction is optimum between pH 1 and 3.6 and no interference is observed from silicate. The precision is 5% RSD at the 0.25-mug ml level and the detection limit is 20 ng ml for 100 ml of sample solution. 相似文献
107.
Promotion of Ionic Liquid to Dimethyl Carbonate Synthesis from Methanol and Carbcn Dioxide 总被引:2,自引:0,他引:2
Promotion of ionic liquid, 1-ethyl-3-methylimidazolium bromide (emimBr), to the synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide in the presence of potassium carbonate and less amount of methyl iodide under mild conditions was investigated. The results showed that the high selectivity and raised yield of DMC was achieved due to the addition of emimBr in the reaction system. And effect of several reaction conditions such as temperature, pressure and amount of emimBr was discussed. 相似文献
108.
When trypsin reacts with Herring sperm DNA (hsDNA), Salmon sperm DNA (sDNA), and Calf thymus DNA (ctDNA) to form a complex,
the resonance Rayleigh scattering (RRS) was remarkably enhanced and new RRS spectra appear. These new spectra have similar
characteristics of RRS spectra. The maximum RRS peaks are at 307 nm (hsDNA, sDNA) and 290 nm (ctDNA), and other peaks are
at 350 nm. The scattering intensity is proportional to the concentration of DNA or trypsin; so this intereaction can be used
to determine trypsin using DNA or DNA using trypsin. In the determination of DNA using trypsin, the linear ranges for hsDNA,
sDNA, and ctDNA are 0–2.3, 0–2.5, and 0–1.9 μg·mL−1, and the detection limits are 0.4, 0.7, and 1.1 ng·mL−1, respectively. In the determination of trypsin using hsDNA, the linear range is 0–30.0 μg·mL−1, and the detection limit is 39.0 ng·mL−1. In this paper, the intereaction conditions were optimized. The affecting factors, chemical properties of the complex, and
the composition ratio of trypsin with DNA were investigated. Using trypsin as RRS probe, a sensitive method for the determination
of trace amounts of DNA was developed.
Translated from Chemical Journal of Chinese Universities, 2006, 27(3) (in Chinese) 相似文献
109.
Ching Hsuan Lin Zheng Rong Jiang Chun Shan Wang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(22):4084-4097
A 2,6‐dimethyl phenol–dipentene adduct was synthesized from dipentene (DP) and 2,6‐dimethyl phenol, and then a 2,6‐dimethyl phenol–DP epoxy was synthesized from the reaction of the resultant 2,6‐dimethyl phenol–DP adduct and epichlorohydrin. The proposed structures were confirmed by Fourier transform infrared, elemental analysis, mass spectra, NMR spectra, and epoxy equivalent weight titration. The synthesized 2,6‐dimethyl phenol–DP adduct was cured with 4,4‐diamino diphenyl methane, phenol novolac, 4,4‐diamino diphenyl sulfone, and 4,4‐diamino diphenyl ether. The thermal properties of the cured epoxy resins were studied with differential scanning calorimetry, dynamic mechanical analysis, dielectric analysis, and thermogravimetric analysis. These data were compared with those for the bisphenol A epoxy system. The cured 2,6‐dimethyl phenol–DP epoxy exhibited a lower dielectric constant (ca. 3.1), a lower dissipation factor (ca. 0.065), a lower modulus, lower thermal stability (5% degradation temperature = 366–424 °C), and lower moisture absorption (1.21–2.18%) than the bisphenol A system but a higher glass‐transition temperature (ca. 173–222 °C) than that of bisphenol A system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4084–4097, 2002 相似文献
110.