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101.
102.
Fei Z Zhao D Geldbach TJ Scopelliti R Dyson PJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(19):4886-4893
Imidazolium chlorides with one or two carboxylic acid substituent groups, 1-methyl-3-alkylcarboxylic acid imidazolium chloride, [Me[(CH2)nCOOH]im]Cl (n=1, 3), and 1,3-dialkylcarboxylic acid imidazolium chloride, [[(CH2)nCOOH]2im]Cl (n=1, 3), have been synthesized via their corresponding acid esters. Deprotonation of the carboxylic acid functionalized imidazolium chlorides with triethylamine affords the corresponding zwitterions [Me[(CH2)nCOO]im] (n=1, 3) and [[(CH2)nCOOH][(CH2)nCOO]im] (n=1, 3). Subsequent reaction of the zwitterions with strong acids gives the new imidazolium salts [Me[(CH2)nCOOH]im]X (n=1, 3; X=BF4, CF3SO3) and [[(CH2)nCOOH]2im]X (n=1, 3; X=BF4, CF3SO3), which exhibit melting points as low as -61 degrees C. The solid-state structures of two of the carboxylic acid functionalized imidazolium salts have been determined by single-crystal X-ray diffraction analysis. Extensive hydrogen bonding is present between the chloride and the imidazolium, with eight Cl.H interactions below 3 A. The pK(a) values of all the salts, determined by potentiometric titration, lie between 1.33 and 4.59 at 25 degrees C. 相似文献
103.
Schöbel H Leidlmair C Bartl P Aleem A Hager M Echt O Märk TD Scheier P 《Physical chemistry chemical physics : PCCP》2011,13(3):1092-1098
Helium nanodroplets are co-doped with C(60) and ammonia. Mass spectra obtained by electron ionization reveal cations containing ammonia clusters complexed with up to four C(60) units. The high mass resolution of Δm/m≈ 1/6000 makes it possible to separate the contributions of protonated, unprotonated and dehydrogenated ammonia. C(60) aggregates suppress the proton-transfer reaction which usually favors the appearance of protonated ammonia cluster ions. Unprotonated C(x)(NH(3))(n)(+) ions (x = 60, 120, 180) exceed the abundance of the corresponding protonated ions if n < 5; for larger values of n the abundances of C(60)(NH(3))(n)(+) and C(60)(NH)(n-1)NH(4)(+) become about equal. Dehydrogenated C(60)NH(2)(+) ions are relatively abundant; their formation is attributed to a transient doubly charged C(60)-ammonia complex which forms either by an Auger process or by Penning ionization following charge transfer between the primary He(+) ion and C(60). The abundance of C(x)NH(3)(+) and C(x)NH(4)(+) ions (x = 120 or 180) is one to two orders of magnitude weaker than the abundance of ions containing one or two additional ammonia molecules. However, a model involving evaporation of NH(3) or NH(4) from the presumably weakly bound C(x)NH(3)(+) and C(x)NH(4)(+) ions is at odds with the lack of enhancement in the abundance of C(120)(+) and C(180)(+). Mass spectra of C(60) dimers complexed with water complement a previous study of C(60)(H(2)O)(n)(+) recorded at much lower mass resolution. 相似文献
104.
Eugenio Aprea Franco Biasioli Silvia Carlin Tilmann D. Mrk Flavia Gasperi 《International journal of mass spectrometry》2008,275(1-3):117-121
The presence of benzene in food and in particular in soft drinks has been reported in several studies and should be considered in fundamental investigations about formation of this carcinogen compound as well as in quality control.Proton transfer reaction-mass spectrometry (PTR-MS) has been used here for rapid, direct quantification of benzene and to monitor its formation in model systems related to the use of benzoate, a common preservative, in presence of ascorbic acid: a widespread situation that yields benzene in, e.g., soft drinks and fruit juices.Firstly, we demonstrate here that PTR-MS allows a rapid determination of benzene that is in quantitative agreement with independent solid phase micro-extraction/gas chromatography (SPME/GC) analysis. Secondly, as a case study, the effect of different sugars (sucrose, fructose and glucose) on benzene formation is investigated indicating that they inhibit its formation and that this effect is enhanced for reducing sugars. The sugar-induced inhibition of benzene formation depends on several parameters (type and concentration of sugar, temperature, time) but can be more than 80% in situations that can be expected in the storage of commercial soft drinks. This is consistent with the reported observations of higher benzene concentrations in sugar-free soft drinks. 相似文献
105.
Fredrik Petersson Philipp Sulzer Chris A. Mayhew Peter Watts Alfons Jordan Lukas Märk Tilmann D. Märk 《Rapid communications in mass spectrometry : RCM》2009,23(23):3875-3880
This work demonstrates for the first time the potential of using recent developments in proton transfer reaction mass spectrometry for the rapid detection and identification of chemical warfare agents (CWAs) in real‐time. A high‐resolution (m/Δm up to 8000) and high‐sensitivity (~50 cps/ppbv) proton transfer reaction time‐of‐flight mass spectrometer (PTR‐TOF 8000 from Ionicon Analytik GmBH) has been successfully used to detect a number of CWA simulants at room temperature; namely dimethyl methylphosphonate, diethyl methylphosphonate, diisopropyl methylphosphonate, dipropylene glycol monomethyl ether and 2‐chloroethyl ethyl sulfide. Importantly, we demonstrate in this paper the potential to identify CWAs with a high level of confidence in complex chemical environments, where multiple threat agents and interferents could also be present in trace amounts, thereby reducing the risk of false positives. Instantaneous detection and identification of trace quantities of chemical threats using proton transfer reaction mass spectrometry could form the basis for a timely warning system capability with greater precision and accuracy than is currently provided by existing analytical technologies. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
106.
Zappa F Denifl S Mähr I Bacher A Echt O Märk TD Scheier P 《Journal of the American Chemical Society》2008,130(16):5573-5578
Attachment of free electrons to water clusters embedded in helium droplets leads to water-cluster anions (H2O)n(-) and (D2O)n(-) of size n > or = 2. Small water-cluster anions bind to up to 10 helium atoms, providing compelling evidence for the low temperature of these complexes, but the most abundant species are bare cluster anions. In contrast to previous experiments on bare water clusters, which showed very pronounced magic and anti-magic anion sizes below n = 12, the presently observed size distributions vary much more smoothly, and all sizes are easily observed. Noticeable differences are also observed in the stoichiometry of fragment anions formed upon dissociative electron attachment and the energy dependence of their yield. Spectroscopic characterization of these ultracold water-cluster anions promises to unravel the relevance of metastable configurations in experiments and the nature of the still controversial bonding sites for the excess electron in small water-cluster anions. 相似文献
107.
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109.
Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid‐Complex Tauto‐Conformers 下载免费PDF全文
Dr. Bernhard Schäfer Dr. Jean‐François Greisch Dr. Isabelle Faus Dr. Tilmann Bodenstein Dr. Ivan Šalitroš Dr. Olaf Fuhr Priv.‐Doz. Dr. Karin Fink Prof. Dr. Volker Schünemann Prof. Dr. Manfred M. Kappes Prof. Dr. Mario Ruben 《Angewandte Chemie (International ed. in English)》2016,55(36):10881-10885
The coordination of iron(II) ions by a homoditopic ligand L with two tridentate chelates leads to the tautomerism‐driven emergence of complexity, with isomeric tetramers and trimers as the coordination products. The structures of the two dominant [FeII4 L 4]8+ complexes were determined by X‐ray diffraction, and the distinctness of the products was confirmed by ion‐mobility mass spectrometry. Moreover, these two isomers display contrasting magnetic properties (FeII spin crossover vs. a blocked FeII high‐spin state). These results demonstrate how the coordination of a metal ion to a ligand that can undergo tautomerization can increase, at a higher hierarchical level, complexity, here expressed by the formation of isomeric molecular assemblies with distinct physical properties. Such results are of importance for improving our understanding of the emergence of complexity in chemistry and biology. 相似文献
110.
The synthesis of a novel imidazolium-tagged ruthenium complex, which represents a versatile precursor for aqueous and ionic liquid biphasic catalysis, is reported. Its utility is demonstrated in the highly enantioselective ionic liquid biphasic transfer hydrogenation of acetophenone and is compared to conventional (untagged) complexes. 相似文献