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排序方式: 共有347条查询结果,搜索用时 31 毫秒
21.
Chafia Bennaceur Carlos Afonso Sandra Alves Anne Bossée Jean-Claude Tabet 《Journal of the American Society for Mass Spectrometry》2013,24(8):1260-1270
Structural elucidation and distinction of isomeric neurotoxic agents remain a challenge. Tandem mass spectrometry can be used for this purpose in particular if a “diagnostic” product ion is observed. Different vibrational activation methods were investigated to enhance formation of diagnostic ions through consecutive processes from O,O-dialkyl alkylphosphonates. Resonant and non-resonant collisional activation and infrared multiphoton dissociation (IRMPD) were used with different mass spectrometers: a hybrid quadrupole Fourier transform ion cyclotron resonance (Qh-FTICR) and a hybrid linear ion trap-Orbitrap (LTQ/Orbitrap). Double resonance (DR) experiments, in ion cyclotron resonance (ICR) cell, were used for unambiguous determination of direct intermediate yielding diagnostic ions. From protonated n-propyl and isopropyl O-O-dialkyl-phosphonates, a diagnostic m/z 83 ion characterizes the isopropyl isomer. This ion is produced through consecutive dissociation processes. Conditions to favor its formation and observation using different activation methods were investigated. It was shown that with the LTQ, consecutive experimental steps of isolation/activation with modified trapping conditions limiting the low mass cut off (LMCO) effect were required, whereas with FT-ICR by CID and IRMPD the diagnostic ion detection was provided only by one activation step. Among the different investigated activation methods it was shown that by using low-pressure conditions or using non-resonant methods, efficient and fast differentiation of isomeric neurotoxic agents was obtained. This work constitutes a unique comparison of different activation modes for distinction of isomers showing the instrumental dependence characteristic of the consecutive processes. New insights in the dissociation pathways were obtained based on double-resonance IRMPD experiments using a FT-ICR instrument with limitation at low mass values.
? 相似文献
22.
Ana P. X. Mariano Ana L. C. C. Ramos Afonso H. de Oliveira Júnior Yesenia M. García Ana C. C. F. F. de Paula Mauro R. Silva Rodinei Augusti Raquel L. B. de Araújo Júlio O. F. Melo 《Molecules (Basel, Switzerland)》2022,27(3)
Eugenia klotzschiana O. Berg is a native species to the Cerrado biome with significant nutritional value. However, its volatile organic compounds (VOCs) chemical profile is not reported in the scientific literature. VOCs are low molecular weight chemical compounds capable of conferring aroma to fruit, constituting quality markers, and participating in the maintenance and preservation of fruit species. This work studied and determined the best conditions for extraction and analysis of VOCs from the pulp of Eugenia klotzschiana O. Berg fruit and identified and characterized its aroma. Headspace solid-phase microextraction (HS-SPME) was employed using different fiber sorbents: DVB/CAR/PDMS, PDMS/DVB, and PA. Gas chromatography and mass spectrometry (GC-MS) were employed to separate, detect, and identify VOCs. Variables of time and temperature of extraction and sample weight distinctly influenced the extraction of volatiles for each fiber. PDMS/DVB was the most efficient, followed by PA and CAR/PDMS/DVB. Thirty-eight compounds that comprise the aroma were identified among sesquiterpenes (56.4%) and monoterpenes (30.8%), such as α-fenchene, guaiol, globulol, α-muurolene, γ-himachalene, α-pinene, γ-elemene, and patchoulene. 相似文献
23.
Noncovalent complexes of DNA and Hoechst 33258 were investigated by ESI-FT/ICR MS in various activation modes (collision-induced dissociation (CID), sustained off-resonance irradiation collision-induced dissociation (SORI-CID), infrared multiphoton dissociation (IRMPD) and electron detachment dissociation (EDD)). The binding selectivity of Hoechst 33258 was confirmed by the comparative study of its noncovalent association with different DNA sequences. The CID spectra of [ds + HO - 5H](5-) obtained with a linear hexapole ion trap resulted in unzipping of the strands. This outcome is a clue to the drug-binding mode, shading light on the localization of the binding sites of Hoechst 33258 to the DNA sequence. The IRMPD and SORI-CID experiments mainly gave DNA backbone cleavages and internal fragment ions. From this result, information on the localization of the binding sites of Hoechst 33258 in the DNA sequence was obtained. No sodium cationization was observed on the DNA sequence ions although they were present on fragmentation of the duplex, indicating that the backbone cleavages were generated from the single strand associated with the Hoechst 33258 where the number of alkali cation is restricted. Under electron detachment (ED) conditions, multiple EDs were achieved for the [ds + HO - 5H](5-) ion without any significant dissociation. The presence of drug appears to enhance the stability of the multiply charged system. It was proposed that the studied noncovalent complex involved the formation of zwitterions and consequently strong salt-bridge interactions between DNA and drug. 相似文献
24.
V.I. Afonso D. Bazeia M.A. Gonzalez Len L. Losano J. Mateos Guilarte 《Nuclear Physics B》2009,810(3):427-459
This work deals with the construction of networks of topological defects in models described by a single complex scalar field. We take advantage of the deformation procedure recently used to describe kinklike defects in order to build networks of topological defects, which appear from complex field models with potentials that engender a finite number of isolated minima, both in the case where the minima present discrete symmetry, and in the non-symmetric case. We show that the presence of symmetry guide us to the construction of regular networks, while the non-symmetric case gives rise to irregular networks which spread throughout the complex field space. We also discuss bifurcation, a phenomenon that appear in the non-symmetric case, but is washed out by the deformation procedure used in the present work. 相似文献
25.
Cobalt compounds supported on 2-, 3-, and 4-aminopyridine-modified silica surfaces, named Sil2Co, Sil3Co, and Sil4Co, respectively, were used to catalyze the decomposition of hydrogen peroxide on ethanolic solutions at 293, 298, and 303 K. The calculated k values (x10(-4) s(-1)) for Sil2Co, Sil3Co, and Sil4Co are 0.65, 1.24, and 4.78 (293 K); 1.23, 1.87, and 6.33 (298 K); and 1.80, 2.80, and 10.30 (303 K), respectively. All obtained results evidence that such decomposition is a first-order reaction. Zinc-, nickel-, and copper-supported compounds were also tested, but exhibited a very low catalytic activity. By using the k values at 298 and 303 K, and employing the equation ln (k1/k2) = E(a)/R(1/T2-1/T1), the activation energy values for the considered reaction were Sil2Co = 57.20, Sil3Co = 60.60, and Sil4Co = 73.10 kJ mol(-1), respectively. The low values calculated for E(a) are in agreement with a free-radical mechanism. 相似文献
26.
27.
Dablemont C Proust A Thouvenot R Afonso C Fournier F Tabet JC 《Inorganic chemistry》2004,43(11):3514-3520
Reaction of [Bu(4)N](4)[H(3)PW(11)O(39)] with [Re(NPh)Cl(3)(PPh(3))(2)], in acetonitrile and in the presence of NEt(3), provided the first Keggin-type organoimido derivative [Bu(4)N](4)[PW(11)O(39)(ReNPh)] (Ph = C(6)H(5)) (1). The functionalization was clearly demonstrated by various techniques including (1)H and (14)N NMR, electrochemistry, and ESI mass spectrometry. Conditions for the formation of 1 are also discussed. 相似文献
28.
Ultrashort-laser-pulse-driven rewritable phase-change optical recording in Sb-based films 总被引:1,自引:0,他引:1
This paper reviews the work we have carried out over the last years on the development of ultrashort-laser-pulse-driven, rewritable,
phase-change optical memories. The materials we have tailored for this application are non-stoichiometric, Sb-rich amorphous
thin films, which can be crystallized upon irradiation with ultrashort laser pulses, showing a large optical contrast upon
transformation. This result makes them very promising for the development of rewritable phase-change optical memories under
ultrashort pulses, since the reversibility of the process has also been demonstrated. Adequate control of the heat-flow conditions
has allowed us to achieve a full transformation time faster than 400 ps for crystallization/amorphization using 30-ps pulses.
The crystallization threshold fluence has been found to decrease upon irradiation with pulses shorter than 800 fs, thus suggesting
the relevance of high-electronic-excitation-induced processes in the amorphous-to-crystalline phase transition. This has been
confirmed by the observation of an ultrafast, non-thermal phase transition occurring 200–300 fs after the arrival of the laser
pulse at the surface, for fluences above the crystallization threshold. The presence of this transient phase conditions the
final state induced therefore enabling the applicability of this material as a rewritable recording medium using femtosecond
pulses.
Received: 11 October 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002
RID="*"
ID="*"Corresponding author. Fax: +34-91/564-5557, E-mail: J.Solis@io.cfmac.csic.es 相似文献
29.
Schäfer T Rodrigues CM Afonso CA Crespo JG 《Chemical communications (Cambridge, England)》2001,(17):1622-1623
Non-porous membranes with the selective layer consisting of hydrophilic or hydrophobic polymers have been applied for the quantitative and selective recovery of solutes with different physico-chemical properties from a room-temperature ionic liquid, ([bmim][PF6]). 相似文献
30.
D. Munoz-Martin J.M. Fernandez-Navarro J. Siegel C.N. Afonso 《Applied Surface Science》2007,254(4):1111-1114
Lead-niobium-germanate planar waveguides have been produced by pulsed laser deposition. The composition of the waveguides is found to be relatively weakly dependent on the laser fluence, while their surface morphology is affected dramatically. Smooth surfaces are obtained for a narrow fluence range centered at 2.0 J/cm2, while particulates having typical diameters of <0.5 μm or droplets with typical diameters of <10 μm are observed at lower and higher fluences, respectively. The refractive index of the waveguides increases with fluence up to 2.1 at 2.0 J/cm2, which is close to the value of the bulk glass, and remains constant at higher fluences. Propagation losses show instead a minimum (≈6.5 dB/cm) at 2.0 J/cm2. The characteristics of the ablation process that leads to the ejection of solid particulates or molten droplets as well as the increase of the waveguides density on increasing the fluence are discussed to be responsible for the observed optical behavior. 相似文献