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91.
92.
The kinetic-energy-dependent cross sections for the reactions of Co(n)+ (n = 2-16) with D2 are measured as a function of kinetic energy over a range of 0-8 eV in a guided ion-beam tandem mass spectrometer. The observed products are Co(n) D+ for all clusters and Co(n)D2+ for n = 4,5,9-16. Reactions for the formation of Co(n)D+ (n = 2-16) and Co9D2+ are observed to exhibit thresholds, whereas cross sections for the formation of Co(n)D2+ (n = 4,5,10-16) exhibit exothermic reaction behavior. The Co(n)+-D bond energies as a function of cluster size are derived from the threshold analysis of the kinetic-energy dependence of the endothermic reactions and are compared to previously determined metal-metal bond energies, D0(Co(n)+-Co). The bond energies of Co(n)+-D generally increase as the cluster size increases, and roughly parallel those for Co(n)+-Co for clusters n > or = 4. These trends are explained in terms of electronic and geometric structures for the Co(n)+ clusters. The bond energies of Co(n)+-D for larger clusters (n > or = 10) are found to be very close to the value for chemisorption of atomic hydrogen on bulk-phase cobalt. The rate constants for D2 chemisorption on the cationic clusters are compared with the results from previous work on cationic and neutral cobalt clusters. 相似文献
93.
在(298.15 ±0.01) K下用转动弹热量计测定了离子液体硫酸乙酯-1-甲基-3-乙基咪唑(EMIES)及合成它的原料1-甲基咪唑的恒容燃烧热,通过计算得到它们的标准燃烧焓 分别为(-2671±2) 和(-286.3±0.5) kJ·mol-1;标准生成焓 分别为(-3060±3) kJ·mol-1和(-2145±4) kJ·mol-1.结合文献上硫酸二乙酯的标准生成焓数据,得到了合成离子液体EMIES的反应热(-102.3±1.0) kJ·mol-1,与合成实验中观察到的强烈放热现象是一致的.根据离子液体EMIES的热容数据,计算了不同温度下EMIES的标准生成焓. 相似文献
94.
P. Song W. Guan C. Yao Z. M. Su Z. J. Wu J. D. Feng L. K. Yan 《Theoretical chemistry accounts》2007,117(3):407-415
Bond distances, dissociation energies, ionization potentials and electron affinities of 4d transition metal monoxides from
YO to CdO and their positive and negative ions were studied by use of density functional methods B3LYP, BLYP, B3PW91, BPW91,
B3P86, BP86, SVWN, MPW1PW91 and PBE1PBE. It was found that calculated properties are highly dependent on the functionals employed,
especially for dissociation energy. For most neutral species, pure density functionals BLYP, BPW91 and BP86 have good performance
in predicting dissociation energy than hybrid density functionals B3LYP, B3PW91 and B3P86. In addition, BLYP gives the largest
bond distance compared with other density functional methods, while SVWN gives shortest bond distance, largest dissociation
energy and electron affinity. For the ground state, the spin multiplicity of the charged species can be obtained by ± 1 of
their corresponding neutral species. 相似文献
95.
Guan F Uboh CE Soma LR Luo Y Li R Birks EK Teleis D Rudy JA Tsang DS 《Rapid communications in mass spectrometry : RCM》2002,16(17):1642-1651
Clenbuterol (CBL) is a potent beta(2)-adrenoceptor agonist used for the management of respiratory disorders in the horse. The detection and quantification of CBL can pose a problem due to its potency, the relatively low dose administered to the horse, its slow clearance and low plasma concentrations. Thus, a sensitive method for the quantification and confirmation of CBL in racehorses is required to study its distribution and elimination. A sensitive and fast method was developed for quantification and confirmation of the presence of CBL in equine plasma, urine and tissue samples. The method involved liquid-liquid extraction (LLE), separation by liquid chromatography (LC) on a short cyano column, and pseudo multiple reaction monitoring (pseudo-MRM) by electrospray ionization quadrupole time-of-flight tandem mass spectrometry (ESI-QTOF-MS/MS). At very low concentrations (picograms of CBL/mL), LLE produced better extraction efficiency and calibration curves than solid-phase extraction (SPE). The operating parameters for electrospray QTOF and yield of the product ion in MRM were optimized to enhance sensitivity for the detection and quantification of CBL. The quantification range of the method was 0.013-10 ng of CBL/mL plasma, 0.05-20 ng/0.1 mL of urine, and 0.025-10 ng/g tissue. The detection limit of the method was 13 pg/mL of plasma, 50 pg/0.1 mL of urine, and 25 pg/g of tissue. The method was successfully applied to the analysis of CBL in plasma, urine and various tissue samples, and in pharmacokinetic (PK) studies of CBL in the horse. CBL was quantified for 96 h in plasma and 288 h in urine post-administration of CLB (1.6 micro g/kg, 2 x daily x 7 days). This method is useful for the detection and quantification of very low concentrations of CBL in urine, plasma and tissue samples. 相似文献
96.
The complexes of poly(methacrylic acid-co-methyl methacrylate) network with poly(ethylene glycol) stabilized byhydrogen bonds were prepared. By introducing the poly(ethylene glycol), a large difference in storage modulus below andabove the glass transition temperature occurred and the complexes exhibited shape memory behaviors. The morphology ofcomplexes was studied by using DSC, WAXD, and DMA. The results indicate that the fixed phase of this kind of novelshape memory materials is the network, and the reversible phase is the amorphous state of PEG:PMAA complex phase. Theshape recoverability almost reaches 100%. This type of complexes can be regarded as a novel shape memory network. 相似文献
97.
离子交换树脂负载Ni—B无定形合金催化剂的制备与性能 总被引:2,自引:0,他引:2
制备了一种新型离子交换树脂负载的Ni-B无定形合金催化剂.用3种树脂作为催化剂载体,即弱酸型阳离子树脂D152,强酸型阳离子树脂D72及强碱型阴离子树脂D261.用XPS、TEM和ICP等技术对催化剂进行了表征.结果表明,催化剂上镍与带有功能基的载体树脂之间有着很强的相互作用,但其强度与所带的功能基有关.3种催化剂Ni2p3/2的XPS谱图上,NiB/D152催化剂的氧化态峰最小,而NiB/D261的氧化态峰最大.异丙醇脱氢反应活性实验证实了这一结果. 相似文献
98.
生物检材中乌头类生物碱的检验 总被引:2,自引:1,他引:2
用薄层 (TLC)、高效液相 光电二极管阵列检测器 (HPLC/DAD)、动物实验等方法对生物检材中乌头生物碱进行检验 ,并对这些方法进行比较。结果发现 ,TLC法为此类药物检验筛选的首选方法 ,最小检出量为 0 3μg。在进行HPLC检测时 ,以乌头生物碱的特征紫外吸收光谱和动物实验结果为重要的定性手段 ,其特征吸收波长为 (2 2 8± 2 )nm和 (2 75± 2 )nm。乌头生物碱在 2mg/L~ 5 0mg/L时其峰面积与质量浓度有很好的线性 ,相关系数为 0 9996。经实际案件证明 ,方法准确、灵敏 ,可用于生物检材中乌头类生物碱的检验。 相似文献
99.
100.
The Ru(II) organometallic antitumor complex [(eta(6)-biphenyl)RuCl(en)][PF(6)] (1) reacts slowly with the amino acid L-cysteine (L-CysH(2)) in aqueous solution at 310 K. Reactions were followed over periods of up to 48 h using HPLC, electronic absorption spectroscopy, LC-ESI-MS, and 1D or 2D (1)H and (15)N NMR spectroscopy. Reactions at a 1 mM/2 mM (Ru/L-CysH(2)) ratio were multiphasic in acidic solutions (pH 5.1) and appeared to involve aquation as the first step. Initially, 1:1 adducts involving substitution of Cl by S-bound or O-bound L-CysH(2), [(eta(6)-biphenyl)Ru(S-L-CysH)(en)](+) (4a) and [(eta(6)-biphenyl)Ru(O-L-CysH(2))(en)](2+) (4b) formed, followed by the cystine adduct [(eta(6)-biphenyl)Ru(O-Cys(2)H(2))(en)](2+) (3), and two dinuclear complexes from which half or all of the chelated ethylenediamine had been displaced, [(eta(6)-biphenyl)Ru(H(2)O)(microS,N-L-Cys)Ru(eta(6)-biphenyl)(en)](2+) (5) containing one bridging cysteine, and [(eta(6)-biphenyl)Ru(O,N-L-Cys-S)(S-L-Cys-N)Ru(eta(6)-biphenyl)(H(2)O)] (6) containing two bridging cysteines. The unusual cluster species [(biphenyl)Ru](8) (7a) was also detected by MS and was more prevalent in reactions at higher L-CysH(2) concentrations. Complex 5 was the dominant product at pH 2-5, but overall, only ca. 50% of 1 reacted with L-CysH(2) in these conditions. The reaction between 1 and L-CysH(2) was suppressed in 50 mM triethylammonium acetate solution at pH > 5 or in 100 mM NaCl. Only 27% of complex 1 reacted with L-methionine (L-MetH) at an initial pH of 5.7 after 48 h at 310 K and gave rise to only one adduct [(eta(6)-biphenyl)Ru(S-L-MetH)(en)](2+) (8). 相似文献