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941.
Xia Y Wu J McLuckey SA Londry FA Hager JW 《Journal of the American Society for Mass Spectrometry》2005,16(1):71-81
Ion/ion proton transfer reactions involving mutual storage of both ion polarities in a linear ion trap (LIT) that comprises part of a hybrid triple quadrupole/linear ion trap mass spectrometer have been effected. Mutual ion storage in the x- and y-dimensions arises from the normal operation of the oscillating quadrupole field of the quadrupole array, while storage in the z-dimension is enabled by applying unbalanced radio-frequency amplitudes to opposing sets of rods of the array. Efficient trapping (>90%) is achieved for thermalized ions over periods of several seconds. Reactions were demonstrated for multiply charged protein/peptide cations formed by electrospray with anions derived from glow discharge ionization of perfluoro(methyldecalin) (PMD) introduced from the side of the LIT rod array. Doubly and singly charged protein ions are readily formed via ion/ion reactions. The parameters that affect ion/ion reactions are discussed, including the degree of RF unbalance on the LIT rods, vacuum pressure, nature of the buffer gas, reaction time, anion abundance, and the low mass cutoff for ion/ion reaction. The present system has a demonstrated upper mass-to-charge ratio limit of at least 33,000. The system also has high flexibility with respect to defining MS(n) experiments involving both collision-induced dissociation (CID) and ion/ion reactions. Experiments are demonstrated involving beam-type CID in the pressurized collision quadrupole (Q2) followed by ion/ion reactions involving the product ions in the LIT. Ion parking experiments are also demonstrated using the mutual storage ion/ion reaction mode in the LIT, with a parking efficiency over 60%. 相似文献
942.
Many aspects of the behavior of surfactants have not been well understood due to the coupling of many different mechanisms.
Computer simulation is, therefore, attractive in the sense that it can explore the effect of different mechanisms separately.
In this paper, the shapes, structures and sizes of sodium dodecylbenzenesulfonate (SDBS) micelles under different concentrations
in an oil/water mixture were studied via molecular dynamics (MD) simulations using a simplified atomistic model which basically
maintains the hydrophile and lipophile properties of the surfactant molecules. Above the critical micellar concentration (cmc),
surfactant molecules aggregate spontaneously to form a wide variety of assemblies, from spherical to rodlike, wormlike and
bilayer micelles. Changes in their ratios of the principle moments of inertia (g1/g3, g2/g3) indicated the transition of micelle shapes at different concentrations. The aggregation number of micelle is found to have
a power-law dependence on surfactant concentration. 相似文献
943.
Zinc(II) and mercury(II) complexes were prepared by reacting isatin-3-thiosemicarbazone (ISTSCH) with zinc(II) acetate or mercury(II) bromide. The complexes were characterized by IR, Raman, diffuse reflectance, 1H and 13C NMR spectra and elemental analysis. Tetrahedral structures for Zn(ISTSC)2 and Hg(ISTSCH)Br2 are suggested. 相似文献
944.
Rakesh?Kumar?MahajanEmail author Jyoti?Chawla Mandeep?Singh?BakshiEmail author 《Colloid and polymer science》2004,282(10):1165-1168
Cloud point (CP) measurements of Tween 20 and Tween 80 were carried out in the presence of various glycol oligomers and triblock polymers (TBP). The cloud points of both Tween 20 and 80 decrease in the presence of both types of additives. Among the glycol oligomeric additives, ethylene glycol monobutyl ether was found to reduce the CP maximum. An increase in the repeating units of polymeric glycol additives leads to a decrease in CP. Reduction in the CP in the presence of TBP depends upon the increase in hydrophobic/hydrophilic ratio among the polypropylene to polyethylene units. 相似文献
945.
Paints and coatings are frequently encountered as types of materials that are submitted to forensic science laboratories as a result of trace evidence transfers. The aim of this study was to develop a method to complement the commonly used techniques in a forensic laboratory in order to better characterize these samples for forensic purposes. A laser ablation method has been used to simultaneously sample several layers directly prior to introduction into an inductively coupled plasma-mass spectrometer for the detection and quantification of the trace metals present in the layer(s). Time-resolved analysis plots displaying the elemental response and quantification of selected metals are compared to associate/discriminate paint samples. Matrix-matched standards were successfully incorporated into the analysis scheme for quantification of lead in the solid paint samples. Preparation of new matrix-matched standards for quantification of additional elements developed for this study are also presented. A sample set of eighteen (18) survey automotive paint samples have been analyzed with the developed method in order to determine the utility of LA-ICP-MS for trace element analysis of paints. 相似文献
946.
Beşli S Coles SJ Davies DB Eaton RJ Hursthouse MB Kiliç A Shaw RA Yenilmez Ciftçi G Yeşilot S 《Journal of the American Chemical Society》2003,125(16):4943-4950
A problem has arisen in using chiral shift reagents (CSR) and chiral solvating agents (CSA) to determine meso and racemic forms of diastereoisomers in which the stereogenic centers of the molecules are separated by achiral spacers. It is found that NMR signals of both meso and racemic forms of diastereoisomers may exhibit doubling on addition of CSR/CSA, which means that unequivocal assignments cannot be made without characterizing the effects for separate meso and racemic forms; this is particularly important for additions of CSR/CSA at relatively low concentrations, which always result in the splitting of some NMR signals of diastereoisomers. The phenomenon is demonstrated in the (31)P NMR spectra of meso and racemic forms of three spermine-bridged gem-disubstituted cyclotriphosphazatrienes, 1a-c, and compared with analogous achiral molecules, the per-substituted spermine-bridged cyclotriphosphazatrienes 2a-d. As expected, only one set of (31)P NMR signals was observed for the achiral compounds 2a-d, even on addition of CSA. Two sets of (31)P NMR ABX multiplets corresponding to meso and racemic diastereoisomers were observed for compounds 1a-c; on addition of CSA, the signals of at least one of the multiplets for each compound separated into more than the expected groups of three lines with an intensity distribution of 2:1:1. To understand this phenomenon, the meso and racemic forms of 1a and 1b and the meso form of 1c have been separated and characterized by X-ray crystallography. On addition of CSA to the racemic forms of 1a and 1b, the (31)P NMR spectrum shows the expected doubling of signals, but, unexpectedly, the same is observed for each of the meso forms of 1a-c. Analogous results using both CSA and CSR have been obtained for the meso and racemic forms of the diastereoisomeric piperazine-bridged macrocyclic-phosphazene compound, 3, whereas no effect was observed for the two meso forms of the doubly bridged macrocyclic-phosphazene compound 4. The phenomenon of doubling of the (31)P NMR signals of the meso form of singly bridged cyclotriphosphazatrienes, 1a-c and 3, is explained by consideration of the equilibrium in solution of independent complexation of a chiral ligand with molecules that have two chiral cyclophosphazene moieties separated by an achiral spacer group. The results show that the stereogenicity of such diastereoisomeric molecules in solution cannot be characterized unequivocally by NMR measurements on addition of either CSR or CSA. 相似文献
947.
Barrett B Borek-Dohalský V Fejt P Vaingátová S Huclová J Nemec B Jelínek I 《Analytical and bioanalytical chemistry》2005,383(2):210-217
A validated, highly sensitive, and selective HPLC method with MS–MS detection has been developed for quantitative determination
of azithromycin (AZI) in human Na2EDTA plasma. Roxithromycin (ROX) was used as internal standard. Human plasma containing AZI and internal standard was ultrafiltered
through Centrifree Micropartition devices and the concentration of AZI was determined by isocratic HPLC–MS–MS. Multiple reaction
monitoring mode (MRM) was used for MS–MS detection. The calibration plot was linear in the concentration range 2.55–551.43 ng mL−1. Inter-day and Intra-day precision and accuracy of the proposed method were characterized by R.S.D and percentage deviation,
respectively; both were less than 8%. Limit of quantification was 2.55 ng mL−1. The proposed method was used to determine the pharmacokinetic profile of AZI (250-mg tablets). 相似文献
948.
A quantitative analysis method for penicillins including ampicillin (AmP), benzyl penicillin (BP), oxacillin (OA) and amoxycillin (AmO) is proposed that makes use of the totally internally reflected resonance light scattering (TIR-RLS) signal from the penicillin at the H2O/CCl4 interface in the presence of cetyltrimethylammonium bromide (CTMAB), and enables the pharmacokinetics of penicillin taken orally and excreted through urine to be monitored. Penicillin is coadsorbed with CTMAB at the H2O/CCl4 interface in neutral solution, resulting in the formation of ion associates that display greatly enhanced TIR-RLS signals (maximum at 368–372 nm). This enhanced TIR-RLS intensity was found to be proportional to the penicillin concentration over the range 0.2×10–6 to 2.2×10–6 mol L–1, with limits of determination (3) of 5.0×10–8 to 7.0×10–8 mol L–1. Pharmacokinetics studies performed using the present method show that the excretion of orally-taken ampicillin through urine has a half-time of 1.05 h and an excremental quantum over 8 h of 49.3%, respectively. 相似文献
949.
Klaus Burger Gabor Radics Lothar Hennig Christoph B?ttcher Jan Spengler Fernando Albericio 《Monatshefte für Chemie / Chemical Monthly》2005,5(3):763-776
Starting from L-malic, L-citramalic, and rac. thiomalic acids routes to L-homoisoserine, 2-methyl-L-homoisoserine and rac. homoisocysteine have been developed. The new orthogonally protected and carboxy-activated building blocks are GABA as well as -hydroxy and -mercapto acid derivatives, suitable for the construction of peptide and depsipeptide surrogates. 相似文献
950.
M. Tešić M. Ratković V. Dondur R. Jankov 《Journal of Radioanalytical and Nuclear Chemistry》1992,158(1):183-191
The reaction of isotope exchange between [3-(iodophenyl)methyl]guanidine, mIBG, and [131]-iodide in relatively concentrated solutions, in the presence of different ammonium salts, in a closed system, over the temperature range from 130 to 150°C, has been investigated. The reaction occurs either with (NH4)2SO4 or CH3COOH, which indicates that the reaction goes through some intermediate stages. Kinetic studies show the influence of the additives. The activation energies for the reaction with (NH4)2SO4/H2O, (NH4)2SO4/CH3COOH and CH3COOH are 121.1, 115.1 and 84.5 kJ·mol–1, respectively. 相似文献