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991.
992.
Ultraviolet laser desorption/ionization mass spectrometry of single‐core and multi‐core polyaromatic hydrocarbons under variable conditions of collisional cooling: insights into the generation of molecular ions,fragments and oligomers 下载免费PDF全文
Francisco Gámez Ana R. Hortal Bruno Martínez‐Haya Jens Soltwisch Klaus Dreisewerd 《Journal of mass spectrometry : JMS》2014,49(11):1127-1138
The ultraviolet laser desorption/ionization of polyaromatic hydrocarbons (PAHs) has been investigated under different background pressures of an inert gas (up to 1.2 mbar of N2) in the ion source of a hybrid, orthogonal‐extracting time‐of‐flight mass spectrometer (oTOF‐MS). The study includes an ensemble of six model PAHs with isolated single polyaromatic cores and four ones with multiple cross‐linked aromatic and polyaromatic cores. In combination with a weak ion extraction field, the variation of the buffer gas pressure allowed to control the degree of collisional cooling of the desorbed PAHs and, thus, to modulate their decomposition into fragments. The dominant fragmentation channels observed are related to dehydrogenation of the PAHs, in most cases through the cleavage of even numbers of C―H bonds. Breakage of C―C bonds leading to the fragmentation of rings, side chains and core linkages is also observed, in particular, at low buffer gas pressures. The precise patterns of the combined fragmentation processes vary significantly between the PAHs. The highest abundances of molecular PAH ions and cleanest mass spectra were consistently obtained at the highest buffer gas pressure of 1.2 mbar. The effective quenching of the fragmentation pathways at this elevated pressure improves the sensitivity and data interpretation for analytical applications, although the fragmentation of side chains and of bonds between (poly)aromatic cores is not completely suppressed in all cases. Moreover, these results suggest that the detected fragments are generated through thermal equilibrium processes rather than as a result of rapid photolysis. This assumption is further corroborated by a laser desorption/ionization post‐source decay analysis using an axial time‐of‐flight MS. In line with these findings, covalent oligomers of the PAHs, which are presumably formed by association of two or more dehydrogenated fragments, are detected with higher abundances at the lower buffer gas pressures. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
993.
Dipl.‐Chem. Jens Willwacher Prof. Alois Fürstner 《Angewandte Chemie (International ed. in English)》2014,53(16):4217-4221
A concise synthesis of the putative structure assigned to the highly cytotoxic marine macrolide mandelalide A ( 1 ) is disclosed. Specifically, an iridium‐catalyzed two‐directional Krische allylation and a cobalt‐catalyzed carbonylative epoxide opening served as convenient entry points for the preparation of the major building blocks. The final stages feature the first implementation of terminal‐acetylene metathesis into natural product synthesis, which is remarkable as this class of substrates was beyond reach until very recently; key to success was the use of the highly selective molybdenum alkylidyne complex 42 as the catalyst. Although the constitution and stereochemistry of the synthetic samples are unambiguous, the spectra of 1 as well as of 11‐epi‐ 1 deviate from those of the natural product, which implies a subtle but deep‐seated error in the original structure assignment. 相似文献
994.
Probing Transient Conformational States of Proteins by Solid‐State R1ρ Relaxation‐Dispersion NMR Spectroscopy 下载免费PDF全文
Dr. Peixiang Ma Jens D. Haller Jérémy Zajakala Dr. Pavel Macek Dr. Astrid C. Sivertsen Prof. Dr. Dieter Willbold Dr. Jérôme Boisbouvier Dr. Paul Schanda 《Angewandte Chemie (International ed. in English)》2014,53(17):4312-4317
The function of proteins depends on their ability to sample a variety of states differing in structure and free energy. Deciphering how the various thermally accessible conformations are connected, and understanding their structures and relative energies is crucial in rationalizing protein function. Many biomolecular reactions take place within microseconds to milliseconds, and this timescale is therefore of central functional importance. Here we show that R1ρ relaxation dispersion experiments in magic‐angle‐spinning solid‐state NMR spectroscopy make it possible to investigate the thermodynamics and kinetics of such exchange process, and gain insight into structural features of short‐lived states. 相似文献
995.
Counterions Control Whether Self‐Assembly Leads to Formation of Stable and Well‐Defined Unilamellar Nanotubes or Nanoribbons and Nanorods 下载免费PDF全文
Dr. Dong Shi Christian Schwall George Sfintes Dr. Erling Thyrhaug Dr. Peter Hammershøj Dr. Marite Cárdenas Dr. Jens B. Simonsen Dr. Bo W. Laursen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(23):6853-6856
Self‐assembly of the amphiphilic π‐conjugated carbenium ion ATOTA‐1+ in aqueous solution selectively leads to discrete and highly stable nanotubes or nanoribbons and nanorods, depending on the nature of the counterion (Cl? vs. PF6?, respectively). The nanotubes formed by the Cl? salt illustrate an exceptional example of a structural well‐defined (29±2 nm in outer diameter) unilamellar tubular morphology featuring π‐conjugated functionality and high stability and flexibility, in aqueous solution. 相似文献
996.
Jens A. Iversen Rolf W. Berg Birgitte K. Ahring 《Analytical and bioanalytical chemistry》2014,406(20):4911-4919
Compared to traditional IR methods, Raman spectroscopy has the advantage of only minimal interference from water when measuring aqueous samples, which makes this method potentially useful for in situ monitoring of important industrial bioprocesses. This study demonstrates real-time monitoring of a Saccharomyces cerevisiae fermentation process using a Raman spectroscopy instrument equipped with a robust sapphire ball probe. A method was developed to correct the Raman signal for the attenuation caused by light scattering cell particulate, hence enabling quantification of reaction components and possibly measurement of yeast cell concentrations. Extinction of Raman intensities to more than 50 % during fermentation was normalized with approximated extinction expressions using Raman signal of water around 1,627 cm?1 as internal standard to correct for the effect of scattering. Complicated standard multi-variant chemometric techniques, such as PLS, were avoided in the quantification model, as an attempt to keep the monitoring method as simple as possible and still get satisfactory estimations. Instead, estimations were made with a two-step approach, where initial scattering correction of attenuated signals was followed by linear regression. In situ quantification measurements of the fermentation resulted in root mean square errors of prediction (RMSEP) of 2.357, 1.611, and 0.633 g/L for glucose, ethanol, and yeast concentrations, respectively. 相似文献
997.
Natalia Quinete Thomas Schettgen Jens Bertram Thomas Kraus 《Analytical and bioanalytical chemistry》2014,406(25):6151-6164
Polychlorinated biphenyls (PCBs) are among the most ubiquitous pollutants in the environment, and their metabolism leads to the formation of hydroxylated PCBs (OH-PCBs) and methyl sulfone PCBs (MeSO2-PCBs). These metabolites are generally more hydrophilic than the parent compound, and therefore are more easily eliminated from the body. However, some congeners have been shown to be strongly retained in human blood, binding to transthyretin with an affinity that is, in general, greater than that of the natural ligand thyroxin itself, which could result in toxicological effects, particularly on the thyroid system. Currently available analytical methods require, in general, extensive sample preparation, which includes a series of time-consuming and low-throughput liquid–liquid and back extractions, evaporations, several cleanup steps, and in some cases, derivatization prior to analysis by gas chromatography (GC) or liquid chromatography (LC) coupled with mass spectrometry (MS). Recent developments in the use of LC coupled with tandem MS (MS/MS) have brought some improvements in terms of sample preparation for the determination of PCB metabolites in blood, although there are still possibilities for continued development. The selected literature has evidenced few studies of LC–MS/MS-based methods, a lack of analytical standards, nonassessment of lower-chlorinated OH-PCBs, and scarce attention to MeSO2-PCBs in blood. This review aims to evaluate critically the currently available analytical methods for determination of OH-PCBs and MeSO2-PCBs in blood. 相似文献
998.
Efficient Access to Substituted Silafluorenes by Nickel‐Catalyzed Reactions of Biphenylenes with Et2SiH2 下载免费PDF全文
Jens Michael Breunig Puneet Gupta Dr. Animesh Das Dr. Samat Tussupbayev Dr. Martin Diefenbach Dr. Michael Bolte Prof. Dr. Matthias Wagner Prof. Dr. Max C. Holthausen Dr. Hans‐Wolfram Lerner 《化学:亚洲杂志》2014,9(11):3163-3173
The reaction of biphenylene ( 1 ) with Et2SiH2 in the presence of [Ni(PPhMe2)4] results in the formation of a mixture of 2‐diethylhydrosilylbiphenyl [ 2 (Et2HSi)] and 9,9,‐diethyl‐9‐silafluorene ( 3 ). Silafluorene 3 was isolated in 37.5 % and 2 (Et2HSi) in 36.9 % yield. The underlying reaction mechanism was elucidated by DFT calculations. 4‐Methyl‐9,9‐diethyl‐9‐silafluorene ( 7 ) was obtained selectively from the [Ni(PPhMe2)4]‐catalyzed reaction of Et2SiH2 and 1‐methylbiphenylene. By contrast, no selectivity could be found in the Ni‐catalyzed reaction between Et2SiH2 and the biphenylene derivative that bears tBu substituents in the 2‐ and 7‐positions. Therefore, two pairs of isomers of tBu‐substituted silafluorenes and of the related diethylhydrosilylbiphenyls were formed in this reaction. However, a subsequent dehydrogenation of the diethylhydrosilylbiphenyls with Wilkinson’s catalyst yielded a mixture of 2,7‐di‐tert‐butyl‐9,9‐diethyl‐9‐silafluorene ( 8 ) and 3,6‐di‐tert‐butyl‐9,9‐diethyl‐9‐silafluorene ( 9 ). Silafluorenes 8 and 9 were separated by column chromatography. 相似文献
999.
Jens E. T. Andersen 《Central European Journal of Chemistry》2014,12(2):194-205
A detailed method validation of graphite-furnace atomic absorption spectrometry (GFAAS) with Zeeman background correction was performed. The aim is to perform a detailed investigation of short-term precision as opposed to long-term precision. It was suggested that release of graphite flakes into the light path during measurement significantly influenced the performance of the method. It was found that significant deviations with respect to the certified values were frequent and an estimate of reliable uncertainties was obtained only after a high number of repetitions. Uncertainty of Interlaboratory testing was evaluated as a method to estimate uncertainties that are comparable to uncertainties that were obtained by Interlaboratory testing and to uncertainties predicted by the Horwitz curve. To a large extent, the uncertainty in measurement that was predicted by pooled calibrations corresponded to the uncertainties that were obtained from multiple determinations of unknowns. It was thus proposed that a large proportion of the difference in uncertainty in measurement between laboratories could be explained by properties of the different detectors. In order to support accuracy, it is suggested that a higher level of uncertainty should be accepted in analytical investigations. 相似文献
1000.