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161.
162.
Andrea Amar Dr. Bernhard Blümich Prof. Dr. Federico Casanova Dr. 《Chemphyschem》2010,11(12):2630-2638
A new, fast magnetic resonance imaging (MRI) method is described and applied to map flow fields in systems with internal velocities rapidly varying along the streamlines. While conventional MRI techniques encode the velocity information in a preparatory period prior to the imaging acquisition module, our technique repeatedly refreshes the velocity encoding during a single‐shot imaging sequence. In this way, the maximum acceleration responsible for velocity variation of the molecules is increased by up to two orders of magnitude compared to standard procedures. Besides being compatible with high acceleration, this pulse sequence is suited to acquiring in a single scan the multiple velocity images required to construct a full velocity vector map. The power of this new methodology is demonstrated by following the internal dynamics of toluene droplets levitating in a counterflow of water during mass transfer of acetone from the water phase into the drop in the presence of surface‐active impurities. The dramatic reduction in measurement time allows visualization for the first time of the important impact of even small concentrations of acetone on accumulation of surfactants at the drop’s surface. 相似文献
163.
Bernhard Mayer‐Helm Ludwig Hofbauer Jutta Pani 《Journal of mass spectrometry : JMS》2010,45(7):715-721
The mass spectrometric behavior of four pairs of stereoisomers was investigated by liquid chromatography–electrospray ionization–mass spectrometry (LC–ESI–MS). The E‐ and Z‐isomers of the pesticides chlorfenvinphos, dimethomorph, mevinphos and phosphamidon—each with one double bond—were chosen for this study. The MS response of the individual isomers was investigated by infusing the isomers individually into the MS or after the separation of isomer mixtures via high‐performance liquid chromatography(HPLC). In the case of dimethomorph, the same MS response was found for the two isomers. In contrast to that, the individual isomers of chlorfenvinphos, mevinphos and phosphamidon showed different MS response both in the single ion monitoring (SIM) mode in single quadrupole MS and multiple reaction monitoring (MRM) mode in tandem MS. The MS response of the isomers partly depends on (1) the declustering potential of the precursor ion in the SIM mode, (2) the selected transition and (3) the collision energy in the MRM mode. Consequently, quantification by summation of the peak areas of the isomers is inaccurate due to over‐ or underestimating of one of the stereoisomers. Accurate quantitative results can only be achieved when the compound‐specific MS parameters are separately determined for each isomer. This can be done by using pure isomers or by the determination of the MS parameters after HPLC separation and the measurement of the actual isomer ratio with an independent technique. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
164.
Markus Langsdorf Alireza Ghassempour Andreas Römpp Bernhard Spengler 《Rapid communications in mass spectrometry : RCM》2010,24(19):2885-2899
A new tryptophyllin‐like peptide family was found in the skin secretion of the tree frog Hyla savignyi. Peptides were characterized by database‐independent sequencing strategies and specific ion fragmentation features were investigated. Skin secretions from specimens of Hyla savignyi were collected by mild electrical stimulation. Peptides were separated by reversed‐phase nano‐high‐performance liquid chromatography (nanoHPLC) and mass spectra were acquired online by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FTICR‐MS). Peptides were characterized by manual de novo sequencing and by composition‐based sequencing (CBS), appearing mostly as C‐terminal free acids and as their acid amide analogs. Amide peptides yielded lower intensities of y‐type ions after collision‐induced dissociation (CID) than their acid analogs. A mechanism of internal b‐ion formation (positive ion mode) and of CO2 elimination (negative ion mode) is proposed. We also exemplified phenomena such as the proline effect and formation of non‐direct sequence ions after sequence rearrangements. The occurrence of rearrangement products, of internal ions and of the proline effect made the CID spectra highly complex. CBS analysis nevertheless resulted in successful and highly reliable sequence analysis. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
165.
166.
Bis(tetraphenylphosphonium) hexachloridodiberyllate, (Ph4P)2[Be2Cl6], reacts with excess trimethylsilyl‐iso‐thiocyanate to give a mixture of colourless single crystals of (Ph4P)2[Be(NCS)4] ( 1 ) and (Ph4P)4[{Be2(NCS)4(μ‐NCS)2}{Be2(NCS)6(μ‐H2N2C2S2)}] ( 2 ), which can be separated by selection. Both complexes were characterized by X‐ray diffraction. Compound 1 can be prepared without by‐products by treatment of (Ph4P)2[BeCl4] with excess Me3SiNCS in dichloromethane solution. 1 : Space group I41/a, Z = 4, lattice dimensions at 100(2) K: a = b = 1091.2(1), c = 3937.1(3) pm, R1 = 0.0474. The [Be(NCS)4]2– ion of 1 forms tetragonally distorted tetrahedral anions with Be–N distances of 168.4(2) pm and weak intermolecular S ··· S contacts along [100] and [010]. 2 ·4CH2Cl2: Space group P , Z = 1, lattice dimensions at 100(2) K: a = 919.5(1), b = 1248.3(1), c = 2707.0(2) pm, α = 101.61(1) °, β = 95.08(1) °, γ = 94.52(1) °, R1 = 0.103. Compound 2 contains two different anionic complexes in the ratio 1:1. In {Be2(NCS)4(μ‐NCS)2}2–, the beryllium atoms are connected by (NCS)– bridging groups forming centrosymmetric eight‐membered Be2(NCS)2 rings with distances Be–N of 168(1) pm and Be–S of 235.2(9) pm. The second anion {Be2(NCS)6(μ‐H2N2C2S2)}2– consists of two {Be(NCS)3}– units, which are linked by the nitrogen atoms of the unique dimeric cyclo‐addition product of HNCS with Be–N distances of 179(1) pm. 相似文献
167.
Len Herald V. Lim Andreas B. Pribil Andreas E. Ellmerer Bernhard R. Randolf Bernd M. Rode 《Journal of computational chemistry》2010,31(6):1195-1200
Simulations using ab initio quantum mechanical charge field molecular dynamics (QMCF MD) and classical molecular dynamics using two‐body and three‐body potentials were performed to investigate the hydration of the Ca2+ ion at different temperatures. Results from the simulations demonstrate significant effects of temperature on solution dynamics and the corresponding composition and structure of hydrated Ca2+. Substantial increase in ligand exchange events was observed in going from 273.15 K to 368.15 K, resulting in a redistribution of coordination numbers to lower values. The effect of temperature is also visible in a red‐shift of the ion‐oxygen stretching frequencies, reflecting weakened ligand binding. Even the moderate increase from ambient to body temperature leads to significant changes in the properties of Ca2+ in aqueous environment. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 相似文献
168.
Morito H Eck B Dronskowski R Yamane H 《Dalton transactions (Cambridge, England : 2003)》2010,39(42):10197-10202
Ternary sodium borosilicide, Na(8)B(74.5)Si(17.5), was newly synthesized by heating a mixture of sodium, silicon and amorphous or crystalline boron at 1073-1273 K. The crystal structure of the black hexagonal prismatic single crystal obtained at 1273 K was analyzed. The X-ray diffraction reflections of the crystal were indexed with hexagonal cell parameters a = 10.2392(3) ? and c = 10.9215(4) ? (space group P6(3)/mmc, No. 194). The structural formula could be represented as Na(8)(B(12))(6)Si(16)[BSi](1.5)[B(2)](0.5). B(12) icosahedra form a three-dimensional framework having small triangular and large hexagonal channels along the c axis. Chains of [-Si-(Si-Si)(3)-Si-] surrounded by Na atoms are located in the large channels. Trigonal prism cages for Na atoms and for atom pairs of Si-B or B-B are alternately arrayed in the small channels. The ratio of Si-B and B-B pairs in the cage is around 3:1. 相似文献
169.
Literature published in the last decade concerning the use of mid-infrared spectrometry as a detection system in separation techniques employing a liquid mobile phase is reviewed. In addition to the continued use of isocratic liquid chromatographic (LC) techniques, advances in chemometric data evaluation techniques now allow the use of gradient techniques on a routine basis, thus significantly broadening the range of possible applications of LC-IR. The general trend towards miniaturized separation systems was also followed for mid-IR detection where two key developments are of special importance. Firstly, concerning on-line detection the advent of micro-fabricated flow-cells with inner volumes of only a few nL for transmission as well as attenuated total reflection measurements enabled on-line mid-IR detection in capillary LC and opened the path for the first successful realization of on-line mid-IR detection in capillary zone electrophoresis as well as micellar electrokinetic chromatography. Secondly, concerning off-line detection the use of micro-flow through dispensers now enables to concentrate eluting analytes on dried spots sized a few tens of micrometers, thus matching the dimensions for sensitive detection by mid-IR microscopy. Finally in an attempt to increase detection sensitivity of on-line mid-IR detection, mid-IR quantum cascade lasers have been used. Applications cover the field of food analysis, environmental analysis and the characterization of explosives among others. Best detection sensitivities for on-line and off-line detection have been achieved in miniaturized systems and are in the order of 50 ng and 2 ng on column, respectively. 相似文献
170.
By treatment of tris(azidomethyl)amine with dry hydrogen halide, azidochloromethane and azidobromomethane were prepared. The former product, which is more stable than the latter, was isolated as a colorless liquid. The desired azidohalomethanes are intermediates in the nucleophilic substitution of dihalomethanes to generate diazidomethane but could not be detected in this transformation. 相似文献