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151.
Raska CS Parker CE Huang C Han J Glish GL Pope M Borchers CH 《Journal of the American Society for Mass Spectrometry》2002,13(9):1034-1041
Both the matrix selected and the laser fluence play important roles in MALDI-quadrupole/time of flight (QqTOF) fragmentation processes. "Hot" matrices, such as alpha-cyano4-hydroxycinnamic acid (HCCA), can increase fragmentation in MS spectra. Higher laser fluence also increases fragmentation. Typical peptide fragment ions observed in the QqTOF are a, b, and y ion series, which resemble low-energy CID product ions. This fragmentation may occur in the high-pressure region before the first mass-analyzing quadrupole. Fragment ions can be selected by the first quadrupole (Q1), and further sequenced by conventional MS/MS. This allows pseudo-MS3 experiments to be performed. For peptides of higher molecular weight, pseudo-MS3 can extend the mass range beyond what is usually accessible for sequencing, by allowing one to sequence a fragment ion of lower molecular weight instead of the full-length peptide. Peptides that predominantly show a single product ion after MS/MS yield improved sequence information when this technique is applied. This method was applied to the analysis of an in vitro phosphorylated peptide, where the intact enzymatically-generated peptide showed poor dissociation via MS/MS. Sequencing a fragment ion from the phosphopeptide enabled the phosphorylation site to be unambiguously determined. 相似文献
152.
Yang M Wang GJ Wang SJ Li XT Xu YP Wang SP Xiang JD Pan SR Cao GX Ye WC 《Rapid communications in mass spectrometry : RCM》2005,19(12):1619-1623
23-Hydroxybetulinic acid is a newly isolated derivative of betulinic acid. The agent exhibits potential anti-tumor activity and functions in this regard via apoptosis. In support of pharmacokinetic and toxicological evaluations, a new assay based on liquid chromatography/mass spectrometry (LC/MS) was developed for the quantitative analysis of 23-hydroxybetulinic acid. Sample preparation consisted of extraction of the plasma by the addition of methylene chloride followed by centrifugation. Aliquots of the supernatant were analyzed using an isocratic reversed-phase high-performance liquid chromatography (HPLC) system coupled to a negative ion electrospray mass spectrometer. Molecules of 23-hydroxybetulinic acid and the internal standard limonin were detected using selected ion monitoring at m/z 471 and 469, respectively. The limit of detection of 23-hydroxybetulinic acid was 0.05 pg (0.11 fmol) injected on-column (10 pg/mL, 5 microL injection volume), and the limit of quantitation was 10 pg (21.19 fmol, 2 ng/mL, 5 muL injection volume). 23-Hydroxybetulinic acid was stable in plasma samples at -20 degrees C for at least 3 weeks. The intra-day and inter-day coefficients of variation of the assay were 3.0 and 4.8%, respectively. The utility of the assay was demonstrated by measuring 23-hydroxybetulinicacid in mouse plasma following intragastric administration (IG) in vivo. Pharmacokinetic parameters were calculated using the 3P97 pharmacokinetic software package. A two-compartment, first-order model was selected for pharmacokinetic modeling. The result showed that after IG of 200 mg/kg 23-hydroxybetulinic acid, the plasma concentrations reached peaks at 2 h with C(max) of 3.1 microg/mL. The 200 mg/kg 23-hydroxybetulinic acid suspension IG doses were found to have long elimination half-lives of 25.6 h and low bioavailability of 2.3%. No interference was noted due to endogenous substances. These analytical methods should be of value in future studies related to the development and characterization of 23-hydroxybetulinic acid. 相似文献
153.
Wang C Zhu G Li J Cai X Wei Y Zhang D Qiu S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(17):4975-4982
We demonstrate a novel strategy for the preparation of mesoporous silica-supported, highly dispersed, stable metal and bimetal nanoparticles with both size and site control. The supporting mesoporous silica, functionalized by polyaminoamine (PAMAM) dendrimers, is prepared by repeated Michael addition with methyl acrylates (MA) and amidation reaction with ethylenediamine (EDA), by using aminopropyl-functionalized mesoporous silica as the starting material. The encapsulation of metal nanoparticles within the dendrimer-propagated mesoporous silica is achieved by the chemical reduction of metal-salt-impregnated dendrimer-mesoporous silica by using aqueous hydrazine. The site control of the metal or bimetal nanoparticles is accomplished by the localization of inter- or intradendrimeric nanoparticles within the mesoporous silica tunnels. The size of the encapsulated nanoparticles is controlled by their confinement to the nanocavity of the dendrimer and the mesopore. For Cu and Pd, particles locate at the lining of mesoporous tunnels, and have diameters of less than 2.0 nm. For Pd/Pt, particles locate at the middle of mesoporous tunnels and have diameters in the range of 2.0-4.2 nm. The Pd and Pd/Pt nanoparticles are very stable in air, whereas the Cu nanoparticles are stable only in an inert atmosphere. 相似文献
154.
Qiutian Liu Chunxi Zhang Changneng Chen Hongping Zhu Yuheng Deng Jinhua Cai 《中国科学B辑(英文版)》1997,40(6):616-623
In a reaction system consisting of FeCl2, tetrathiometallate and cycloalkylthiolate, two Fe4S4 cubanelike cluster compounds were obtained with the following crystallographic data: (PhCH2NMe3)2 [ Fe4S4 (SC5H9)4] (I), monoclinic space groupP21/c,a = 1.632 7(4),b=1.122 9(3),c = 2. 802 5(10) nm, β= 94.63(2)°, Z=4, andR= 0.074; (Et4N)2[F4S4(SC6HlI)4] (II), tetragod space group
,a = l.167 05(9),b = 1.167 06(2),c = 2.063 26(5) nm,Z = 2, Dobs = 1. 28 g/cm3, andR = 0. 078. The participation of cycloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure. Meanwhile, the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed.
Project supported by the National Natural Science Foundation of China and the Climbing Program Foundation of China. 相似文献
155.
A racemic solution of (I) crystallizes as a conglomerate from which a crystal we selected was found to be (+)546-trans-[Co(3,2,3-tet)(NO2)2]Cl·3H2O (I), CoClO7N6C8H28. It crystallizes in the enantiomorphic space groupP2l2l2l, with lattice constantsa=18.501(15) å,b=14.433(2) å, andc=6.441(3) å;V=1720.07 å3 andd(calc. M.W.=414.73,Z=4)=1.601 g cm?3. A total of 2305 data were collected over the range of 4?≤2θ ≤55?; of these, 1724 (independent and withI > 3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ=11.920 cm?1), and the relative transmission coefficients ranged from 0.8258 to 0.9565. Refinement was carried out for both lattice enantiomorphs, and at this stage theR(F) andR w (F) residuals were, respectively, 0.0381 and 0.0479 for (+ + +) and 0.0448 and 0.0532 for (? ? ?). Thus, the former was selected as correct for our specimen, and the final cycle of refinement with the (+ + +) model converged toR(F) andR w (F) of 0.0315 and 0.0365. A racemic solution of (II) crystallizes as a conglomerate from which a crystal we selected was found to be (?)589-trans-[Co(3,2,3-tet)Cl2]NO3 (II), CoCl2O3N5C8H22. It crystallizes in the enantiomorphic space groujp,P2l with lattice constantsa=6.395(2) å,b=8.886(2) å,c=13.185(2) å, andΒ=99.24(2)?;V=739.59 å3 andd(calc. M.W.=366.14,Z=2)=1.646 g cm ?3. A total of 2912 data were collected over the range of 4?<2θ<64?; of these, 2147 (independent and withI≥3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ =15.424 cm?1), and the relative transmission coefficients ranged from 0.9632 to 0.9985. Refinement was carried out for both lattice enantiomorphs, and the finalR(F) andR w (F) residuals were, respectively, 0.0326 and 0.0328 for (+ + +) and 0.0347 and 0.0348 for (? ? ?). Thus, the (+ + +) was selected as correct for our specimen. A racemic solution of (III) crystallizes as a conglomerate from which a crystal we selected was found to be (+)589-trans-[Co(3,2,3-tet)(NO2)2]NO3 (III), CoO7N7C8H22. It crystallizes in the enantiomorphic space group,P2l with lattice constantsa=6.295(1) å, b=15.108(3) å,c=8.029(1) å, andΒ=100.28(2)?;V=751.35 å3 andd(calc. M.W.=387.24,Z=2)=1.712 g cm?3. A total of 2393 data were collected over the range of 4?≤2θ≤60?; of these, 1869 (independent and withI≥3σ(I)) were used in the structural analysis. Data were corrected for absorption (Μ=11.859 cm?1), and the relative transmission coefficients ranged from 0.8814 to 0.9976. Refinement was carried out for both lattice enantiomorphs and the finalR(F) andR w (F) residuals were, respectively, 0.0463 and 0.0482 for (+ + +) and 0.0441 and 0.0442 for (? ? ?). Thus, the latter was selected as correct for our specimen, and the final cycle of refinement with the (? ? ?) model converged toR(F) andR w (F) of 0.0436 and 0.0421. For all three compounds, the six-membered rings are chairs; the secondary nitrogens are chiral centers, and the five-membered rings are ordered and conformationally dissymmetric, as expected. Coincidentally, in (I), (II), and (III) the central rings are right-handed helices withδ(+50.0?),δ(+53.3?), andδ(+48.3?), respectively. Thus, the secondary nitrogens of all three cations are (R), rendering the cations chiral. The incidence of conglomerate crystallization intrans coordination compounds is rare, and those known are asymmetrically substituted (see Ref. 4 for the four known cases). Thus, the incidence of such crystallization mode in a new series of [trans- Co(amine ligands)X2]+ cations bearing symmetrical pairs oftrans ligands was an unexpected and welcomed event. In all three cases, the counteranions are bonded to the hydrogens of the terminal -NH2 moieties, thus forming an overall entity which resembles a macrocycle. In fact, parallels between the crystallization behavior of our compounds and that of macrocycles bearing related fragments is discussed. Finally, in the three compounds, homochiral cations are linked into infinite strings by hydrogen bonds between the axial ligands and amino hydrogens on adjacent cations of the string. In turn, strings are stitched together by the counteranions which form bonds with amino hydrogens on cations of adjacent strings. 相似文献
156.
The column-switching technique has been widely used to determine trace level ions in the presence of high concentration matrix.
A novel simplified column-switching method is proposed where bromate (as a model compound) was determined using this technique.
The switching time window was confirmed by the retention time of determined ions. This technique can completely carry out
the same function as the other column-switching technique do, but only one extra ten-way injection valve coupled to ion chromatograph
was used. By using column-switching technique, it is possible to determine 0.2 μg L−1 bromate in the presence of 100 mg L−1 chloride by direct injection of 2000 μL without any pretreatment and the relative standard deviation (RSD) of the peak height
for the eleven successive injections of 0.2 μg L−1 bromate solution is 23.1%. The detection limit for bromate is 0.09 μg L−1, which showed the method was very sensitive. The technique has been applied to the determination of bromate in drinking water,
and the spike recovery is in the range of 96–104%. 相似文献
157.
158.
用MNDO方法,全构型优化,研究了15个氮自由基4-RC6H4NH,和15个氧自由基4-RC6H4O(R=-H;-OCH3,-Cl,-F,-CN,-COCH3,-NO2,-CH3,-CF3,-SCH3,-C6H5,-Nh2,-BH2,-PH2,-SiH3)的稳定化能.结果表明:-NH2,-CH3,-OCH3,-F基团对自由基起稳定化作用,-CF3,-NO2;-CN,-COCH3,-BH2基团对自由基起去稳定化作用.苯基对氧自由基有较大的稳定化作用,而对氮自由基的稳定性影响较小.-SCH3,-PH2,-SiH3,-Cl基团表现弱的去稳定化作用.计算和实验结果基本相符. 相似文献
159.
Yajing Yin Ping Wu Yafen Lü Pan Du Yanmao Shi Chenxin Cai 《Journal of Solid State Electrochemistry》2007,11(3):390-397
A single-walled carbon nanotube (SWNT)-modified electrode was fabricated and characterized by SEM and ac impedance techniques.
The direct electrochemistry of cytochrome c (Cyt c), which was adsorbed on the surface of the SWNT, was studied by cyclic voltammetry. The results from cyclic voltammetry and
infrared spectroscopy indicated that Cyt c remained in its original structure and did not undergo structural change after its immobilization on the SWNT. Further results
demonstrated that the SWNT had promotional effects on the direct electron transfer of Cyt c and also indicated that the immobilized Cyt c retained its electrocatalytic activity to the reduction of H2O2. This modified electrode might be used in development of new biosensors and the biofuel cells. 相似文献
160.
Tao He Ying‐Fang Zou Cai‐Yuan Pan 《Journal of polymer science. Part A, Polymer chemistry》2002,40(20):3367-3378
Comb‐shaped graft copolymers with poly(methyl methacrylate) as a handle were synthesized by the macromonomer technique in two steps. First, polytetrahydrofuran acrylate (A‐PTHF), prepared by the living cationic ring‐opening polymerization of tetrahydrofuran, underwent homopolymerization with 1‐(ethoxycarbonyl)prop‐1‐yl dithiobenzoate as an initiator under 60Co γ irradiation at room temperature; Second, the handle of the comb‐shaped copolymers was prepared by the block copolymerization of methyl methacrylate with P(A‐PTHF) as a macroinitiator under 60Co γ irradiation. The two‐step polymerizations were proved to be controlled with the following evidence: the straight line of ln[M]0/[M] versus the polymerization time, the linear increase in the number‐average molecular weight with the conversion, and the relatively narrow molecular weight distribution. The structures of the P(A‐PTHF) and final comb‐shaped copolymers were characterized by 1H NMR spectroscopy and gel permeation chromatography. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3367–3378, 2002 相似文献