Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate (in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.
The tetranuclear complexes [{(PiPr(3))(2)(CO)ClRu(mu-CH=CHpy)Ru Cl(CO)(PPh(3))(2)}(2)(mu-CH=CH-C(6)H(4)- CH=CH-1,4)] (3 a) and [{(PiPr(3))(2)(CO)ClRu(mu-CH=CHpy)RuCl(CO)(PPh(3))(2)}(2)(mu-CH=CH-C(6)H(4)-CH=CH-1,3)] (3b), which contain vinylpyridine ligands that connect peripheral Ru(PiPr(3))(2)(CO)Cl units to a central divinylphenylene-bridged diruthenium core, have been prepared and investigated. These complexes, in various oxidation states up to the tetracation level, have been characterized by standard electrochemical and spectroelectrochemical techniques, including IR, UV/Vis/NIR and ESR spectroscopy. A comparison with the results for the vinylpyridine-bridged dinuclear complex [PiPr(3))(2)(CO)ClRu(mu-CH=CHpy)RuCl(CO)(PPh(3))(2)(CH=CHPh)] (6) and the divinylphenylene-bridged complexes [{(EtOOCpy)(CO)Cl(PPh(3))(2)Ru}(2)(mu-CH=CH-C(6)H(4)-CH=CH-1,4)] (8a) and [{(EtOOCpy)(CO)Cl(PPh(3))(2)Ru}(2)(mu-CH=CH-C(6)H(4)-CH=CH-1,3)] (8b), which represent the outer sections (6) or the inner core (8a,b) of complexes 3a,b, and with the mononuclear complex [(EtOOCpy)(CO)(PPh(3))(2)RuCl(CH=CHPh)] (7) indicate that every accessible oxidation process is primarily centred on one of the vinyl ligands, with smaller contributions from the metal centres. The experimental results and quantum chemical calculations indicate charge- and spin-delocalization across the central divinylphenylenediruthenium part of 3a,b or the styrylruthenium unit of 6, but not beyond. The energy gap between the higher lying styryl- or divinylphenylenediruthenium-based and the lower occupied vinylpyridineruthenium-based orbitals increases in the order 6<3 b<3 a and thus follows the conjugation within the non-heteroatom-substituted aromatic vinyl ligand. 相似文献
Chloroselenates with Di- and Tetravalent Selenium: 77Se-NMR-Spectra, Syntheses, and Crystal Structures of (PPh4)2SeCl6 · 2 CH2Cl2, (NMe3Ph)2SeCl6, (K-18-crown-6)2SeCl6 · 2 CH3CN, PPh4Se2Cl9, (NEt4)2Se2Cl10, (PPh4)2Se3Cl8 · CH2Cl2, and (PPh4)2Se4Cl12 · CH2Cl2 The title compounds were obtained from reactions of selenium and selenium tetrachloride with PPh4Cl, NEt4Cl, NMe3PhCl, or (K-18-crown-6)Cl in dichloromethane or acetonitrile. (PPh4)2Se3Cl8 · CH2Cl2 was also formed from GeSe, PPh4Cl and chlorine in acetonitrile. The 77Se-NMR spectra of the solutions show the presence of dynamical equilibria which, depending on composition, mainly contain SeCl2, SeCl4, Se2Cl2, SeCl62–, Se2Cl62–, and/or Se2Cl102–. Solutions of AsCl3 and (PPh4)2Se4 in acetonitrile upon chlorination with Cl2 or PPh4AsCl6 yielded (PPh4)2Se2Cl6, while (PPh4)2As2Se4Cl12 was the product after chlorination with SOCl2. According to the X-ray crystal structure analyses the ions SeCl62–, Se2Cl9–, and Se2Cl102– have the known structures with octahedral coordination of the Se atoms. The structure of the Se3Cl82– ion corresponds to that of Se3Br82– consisting of three SeCl2 molecules associated via two Cl– ions. (PPh4)2Se4Cl12 · CH2Cl2 is isotypic with the corresponding bromoselenate and contains anions in which three SeCl2 molecules are attached to a SeCl62– ion; there is a peculiar Se–Se interaction. 相似文献
Driving under the influence of prescribed or illegal drugs increases the risk of having road accidents, just like driving
under the influence of alcohol. In forensic toxicology, an increasing number of blood samples must be analyzed for drugs.
Immunoassays tailored for a limited number of drugs (of abuse) are usually applied as prescreening tests at the roadside and/or
in the laboratory. However, many other common drugs, such as anesthetics, antidepressants, antiepileptics, antihistamines,
newer designer drugs, herbal drugs, neuroleptics (antipsychotics), opioids, or sedative-hypnotics, can also impair drivers.
Therefore, this paper reviews multianalyte single-stage and tandem gas or liquid chromatography–mass spectrometry (GC-MS or
LC-MS) procedures for the screening, identification, and validated quantification of such drugs in blood that have been reported
since 2003. Basic information about the biosample assayed, workup, chromatography, the mass spectral detection mode, and validation
data is summarized in tables. The pros and cons of the reviewed procedures are critically discussed, particularly with respect
to their probable usefulness in impaired driving toxicology.
Parts of this review were presented as a plenary lecture at T2007, the joint meeting of the International Council on Alcohol,
Drugs, and Traffic Safety (ICADTS) and The International Association of Forensic Toxicologists (TIAFT), Seattle (WA), August
26–30, 2007. 相似文献
Studies are described on the metabolism and the toxicological detection of the amphetamine-derived designer drug 2,4,5-trimethoxyamphetamine (TMA-2) in rat urine using gas chromatographic/mass spectrometric (GC/MS) techniques. The identified metabolites indicated that TMA-2 was metabolized by oxidative deamination to the corresponding ketone followed by reduction to the corresponding alcohol, O-demethylation followed by oxidative deamination, and finally O,O-bis-demethylation. All metabolites carrying hydroxy groups were found to be partly excreted in urine as glucuronides and/or sulfates. The authors' systematic toxicological analysis (STA) procedure using full-scan GC/MS after acid hydrolysis, liquid-liquid extraction, and microwave-assisted acetylation allowed the detection, in rat urine, of an intake of TMA-2 that corresponds to a common drug users' dose. Assuming similar metabolism, the described STA procedure in human urine should be suitable as proof of an intake of TMA-2. 相似文献