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961.
Marotta E Paradisi C Cooks RG 《Journal of the American Society for Mass Spectrometry》2005,16(7):1081-1092
The ion chemistry of the title compounds, a nonafluorobutyl methyl ether and a hydrofluoropropane, is elucidated by a combination of studies using atmospheric pressure ionization mass spectrometry and triple quadrupole mass spectrometry. In the positive ion mode, the hydrofluoroether readily forms an [M - F]+ ion, attributable to hydronium ion induced dehydrofluorination, the product of which can be further hydrated to give a protonated hydrofluoroester. By contrast, the hydrofluoropropane does not react with the hydronium ion but rather gives hydrofluoroalkenylium cations via H atom and F atom abstraction by the dioxygen radical cation. In the negative ion mode, the fluorobutyl methyl ether undergoes dissociative electron capture with O2-*, O2-*(H2O), O3-*, and NO2- to generate the fluorobutoxy anion, which can dissociate by CF2[doublebond]O loss to give the perfluorocarbanion when the precursor ions are internally excited. The hydrofluoropropane reacts readily with common atmospheric anions to form molecular complexes with F-, O2-*, and O3-* and the strongly H-bonded species, O2-*(HF) and F-(HF). Interestingly, isomeric pentafluoropropanes form in the reaction with O2-*, either O2-*(HF) or F-(HF), depending on the specific pattern of the fluoro substitution. 相似文献
962.
Yang L Yang Z Cao W Chen L Xu J Zhang H 《The journal of physical chemistry. B》2005,109(23):11501-11504
The luminescence porous materials of CdTe or CdSe nanocrystals (NCs) were prepared by filling the corresponding NCs into the voids of colloidal crystal by co-deposition of polymer beads and NCs. After removing the beads with tetrahydrofuran (THF), the 3D-ordered porous materials of CdTe (or CdSe) NCs were obtained. The wavelength of maximum photoluminescence of the NCs porous material shows obvious red shift compared with their aqueous dispersion. Under the excitation of high-energy electron the porous materials of CdTe and CdSe NCs will emit photons that can be collected to form a cathode luminescence (CL) image. 相似文献
963.
Low-energy CAD product-ion spectra of various molecular species of phosphatidylserine (PS) in the forms of [M−H]− and [M−2H+Alk]− in the negative-ion mode, as well as in the forms of [M+H]+, [M+Alk]+, [M−H+2Alk]+, and [M−2H+3Alk]+ (where Alk=Li, Na) in the positive-ion mode contain rich fragment ions that are applicable for structural determination.
Following CAD, the [M−H]− ion of PS undergoes dissociation to eliminate the serine moiety (loss of C3H5NO2) to give a [M−H−87]− ion, which equals to the [M−H]− ion of a phoshatidic acid (PA) and give rise to a MS3-spectrum that is identical to the MS2-spectrum of PA. The major fragmentation process for the [M−2H+Alk]− ion of PS arises from primary loss of 87 to give rise to a [M−2H+Alk−87]− ion, followed by loss of fatty acid substituents as acids (RxCO2H, x=1,2) or as alkali salts (e. g., RxCO2Li, x=1,2). These fragmentations result in a greater abundance of [M−2H+Alk−87−R2CO2H]− than [M−2H+Alk−87−R1CO2H]− and a greater abundance of [M−2H+Alk−87−R2CO2Li]− than [M−2H+Alk−87−R1CO2Li]−; while further dissociation of the [M−2H+Alk−87−R2(or 1)CO2Li]− ions gives a preferential formation of the carboxylate anion at sn-1 (R1CO2−) over that at sn-2 (R2CO2−). Other major fragmentation process arises from differential loss of the fatty acid substituents as ketenes (loss of Rx′CH=CO, x=1,2). This results in a more prominent [M−2H+Alk−R2′CH=CO]− ion than [M−2H+Alk−R1′CH=CO]− ion. Ions informative for structural characterization of PS are of low abundance in the MS2-spectra of both the [M+H]+ and the [M+Alk]+ ions, but are abundant in the MS3-spectra. The MS2-spectrum of the [M+Alk]+ ion contains a unique ion corresponding to internal loss of a phosphate group probably via the fragmentation processes involving
rearrangement steps. The [M−H+2Alk]+ ion of PS yields a major [M−H+2Alk−87]+ ion, which is equivalent to an alkali adduct ion of a monoalkali salt of PA and gives rise to a greater abundance of [M−H+2Alk−87−R1CO2H]+ than [M−H+2Alk−87−R2CO2H]+. Similarly, the [M−2H+3Alk]+ ion of PS also yields a prominent [M−2H+3Alk−87]+ ion, which undergoes consecutive dissociation processes that involve differential losses of the two fatty acyl substituents.
Because all of the above tandem mass spectra contain several sets of ion pairs involving differential losses of the fatty
acid substituents as ketenes or as free fatty acids, the identities of the fatty acyl substituents and their positions on
the glycerol backbone can be easily assigned by the drastic differences in the abundances of the ions in each pair. 相似文献
964.
氯化钙/水-醇溶液稀释热 总被引:3,自引:0,他引:3
电解质溶液稀释热是溶液的重要热性质之一.由它可计算不同浓度下电解质的溶解热、表现相对摩尔焓、溶液中反应热和化合物生成热等.在电解质溶液理论研究中,稀释热也是重要的基础数据.由稀释热可推算溶液中组分的活度系数、渗透系数、相对偏摩尔焓及表观摩尔热容等[1-3].在化工生产中,稀释热是化工过程能量计算不可缺少的数据.电解质水溶液稀释热已有不少研究[2,4].但电解质混合溶剂体系稀释热报导甚少.随着加盐精馏技术、海水淡化技术等研究的进展,急需这方面数据.本文作者已报告了CaCl2/C2H5OH-H2O体系[5]和CaCl2/n-C… 相似文献
965.
Joeng-Shein Chen Harald Berndt Günther T?lg 《Fresenius' Journal of Analytical Chemistry》1992,344(12):526-534
Summary Various possibilities for the determination of trace impurities in high-purity iron by atomic spectrometry were investigated in detail. For Ba, Bi, Cd, Co, Cr, Cu, Mn, Ni, Pb, Ti and V, flame AAS, furnace AAS and ICP-OES were firstly evaluated in terms of their power of detection. Detection limits in the g/g-range could be achieved by direct determination. For determination in the ng/g-range a removal of iron by a solvent extraction technique prior to the instrumental measurement was required. The power of detection of direct determination, and of combined procedures were compared with regard to routine applicability and a minimization of systematic errors. 相似文献
966.
水溶性高聚物的研究进展 总被引:15,自引:4,他引:15
自八十年代初,水溶性高聚物再次成为高分子科学研究热点,评述了水溶性高聚物,特别是疏水缔合型改性水溶性高聚物的最新进展。 相似文献
967.
化学计量学定量分析模型的评价及应用 总被引:3,自引:0,他引:3
本文介绍了评价化学计量学校正技术所建立的定量分析模型定量分析效果的一种实用方法,根据定量分析模型对样品待测组分的计算值x与样品待测组分的标准值y建立简单回归模型:y=a+bx通过检验回归参数a=0,b=1的假设能否在一定概率水平上被接受,评价定量分析模型对样品待测组分的预测效果。 相似文献
968.
969.
Yu Liu Yong Chen Shi-Zhao Kang Li Li Chun-Hua Diao Heng-Yi Zhang 《Journal of inclusion phenomena and macrocyclic chemistry》2003,47(1-2):91-95
Two novel benzo-15-crown-5 tethered β-cyclodextrins 1 and 2have been synthesized by coupling substituted benzo-15-crown-5 with correspondingβ-cyclodextrin derivatives. Their inclusion complexation behavior withrepresentative guests, such as cyclohexanol, cyclohexane carboxylic acid, cyclohexaneacetic acid, sodium cyclohexane carboxylate, and potassium cyclohexane carboxylate,was investigated in aqueous solution by means of fluorescence spectrometry. As compared with parent β-cyclodextrin, benzo-15-crown-5 tethered β-cyclodextrins 1–2 display significantly enhanced molecular binding abilities and selectivities towards model substrates, especially towards substrates containing alkali-metal cations. These results indicate that, bearing two recognition sites in a single molecule, these supramolecular architectures can strongly enhance the molecular binding ability of parent β-cyclodextrin by the cooperative binding of the β-cyclodextrin cavity and the crown ether moiety. Possessing a shorter linker, crown ether-β-cyclodextrin 2 shows much higher binding affinity with guest molecules than crown ether-β-cyclodextrin 1, which may be attributed to the binding size and molecular multiple recognition behavior between host and guest. 相似文献
970.
A procedure for the simultaneous time-resolved fluoroimmunoassay for phenobarbital and phenytoin, based on the use of europium- and samarium-labeled haptens, has been investigated. These lanthanide ions are bound to the haptens by means of the anhydride of diethylenetriaminepentaacetic acid. The antibody is immobilized onto immunoplate in which samples are assayed in competitive immunoassay. After the immunoreactions and dissociation with a fluorescence enhancement solution, the fluorescence intensity is measured. The detection limits of the assay are, respectively, 20 ng/ml for phenobarbital and 50 ng/ml for phenytoin. Results obtained with the proposed methods correlate well (CV <10%). The inter-reactions between phenobarbital, phenytoin, and their antibodies are studied. 相似文献