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981.
Twelve 11C-labelled amines were prepared via 11C-carbonylation followed by reductive amination. The 11C-carbonylation was performed in the presence of tetrakis(triphenylphosphine)palladium using aryl iodides or aryl triflates, [11C]carbon monoxide and phenyl-/methylboronic acid. The [11C]ketones formed in this step were then transformed directly into amines by reductive amination using different amines in the presence of TiCl4 and NaBH3CN. The 11C-labelled amines were obtained with decay-corrected radiochemical yields in the range 2-78%. The radiochemical purity of the isolated products exceeded 98%. (13C)Benzhydryl-phenyl-amine was synthesised and analysed by NMR spectroscopy for confirmation of the labelling position. Specific radioactivity was determined for the same compound. The reference compounds were prepared by reductive amination of ketones using conventional reaction conditions and three of the compounds were novel. The presented approach is a new method for the synthesis of [11C]/(13C)amines. 相似文献
982.
We report on a theoretical study of the influence of the through-pore porosity on the main chromatographic performance parameters (reduced theoretical plate height, flow resistance, and separation impedance) of silica monoliths. To investigate this problem devoid of any structural uncertainties, computer-generated structural mimics of the pore geometry of silica monolithic columns have been studied. The band broadening in these synthetic monoliths was determined using a commercial Computational Fluid Dynamics (CFD) software package. Three widely differing external porosities (epsilon = 0.38, epsilon = 0.60, and epsilon = 0.86) are considered and are compared on the basis of an identical intra-skeleton diffusivity (Ds = 5 x 10(-10)m2/s), internal porosity (epsilon(int) = 0.5), and for the same phase retention factor (k' = 1.25). Since the data are obtained for perfectly ordered structures, the calculated plate heights and separation impedances constitute the ultimate performance ever to be expected from a monolithic column. It is found that, if silica monoliths could be made perfectly homogeneous, domain size-based reduced plate heights as small as h(min) approximately 0.8 (roughly independent of the porosity) and separation impedances as small as Emin approximately 130 (epsilon = 0.60) and Emin approximately 40 (epsilon = 0.86) should be achievable with pure water as the working fluid. The data also show that, although the domain size is a much better reduction basis than the skeleton size, the former is still not capable of bringing the van Deemter curves of different porosity columns into perfect agreement in the C term dominated velocity range. It is found that, in this range, large porosity monoliths can be expected to yield smaller domain size-based reduced plate heights than small porosity monoliths. 相似文献
983.
van den Pol E Petukhov AV Thies-Weesie DM Byelov DV Vroege GJ 《Journal of colloid and interface science》2010,352(2):354-358
The liquid crystalline phase behavior of sterically-stabilized goethite particles in toluene was studied using small-angle X-ray scattering. The results were compared with those from charged particles in water, with and without magnetic field: similarly rich phase behavior was found. Furthermore, the special magnetic properties were retained after coating the particles with amino-functionalized polyisobutylene chains. A remarkable difference between the aqueous and toluene samples is the latter's tendency to form gels. Smaller domains of the different liquid crystalline phases were observed and the columnar phase does not fully develop, furthermore a higher field is needed to align the full sample. 相似文献
984.
Assessment of commutability for candidate certified reference material ERM-BB130 “chloramphenicol in pork” 总被引:1,自引:0,他引:1
Reinhard Zeleny Håkan Emteborg Heinz Schimmel 《Analytical and bioanalytical chemistry》2010,398(3):1457-1465
Chloramphenicol (CAP), an effective antibiotic against many microorganisms, is meanwhile banned in the EU for treatment of
food-producing animals due to adverse health effects. The Institute for Reference Materials and Measurements (IRMM) is currently
developing a certified reference material (CRM) for CAP in pork, intended for validation and method performance verifications
of analytical methods. The material will be certified using liquid chromatography–tandem mass spectrometry (LC–MS/MS) and
gas chromatography–mass spectrometry (GC–MS) methods and has a target CAP level around the minimum required performance limit
(MRPL) of 0.3 μg/kg. To prove that the material can be applied as a quality control tool for screening methods, a commutability
study was conducted, involving five commercially available enzyme-linked immunosorbent assay kits and one biosensor assay
(BiaCore kit). Meat homogenates (cryo-milled wet tissue) with CAP concentrations around the MRPL and the candidate CRM (lyophilised
powder) were measured by LC–MS/MS and GC–MS as well as the six screening methods. Pairwise method comparisons of results obtained
for the two sample types showed that the CRM can successfully be applied as quality control (QC) sample to all six screening
methods. The study suggests that ERM-BB130 is sufficiently commutable with the investigated assays and that laboratories applying
one of the investigated kits therefore benefit from using ERM-BB130 to demonstrate the correctness of their results. However,
differences among the assays were observed, either in the abundance of bias between screening and confirmatory LC and GC methods,
the repeatability of test results, or goodness of fit between the methods. 相似文献
985.
Jaakko Laakia Alexey Adamov Matti Jussila Christian S. Pedersen Alexey A. Sysoev Tapio Kotiaho 《Journal of the American Society for Mass Spectrometry》2010,21(9):1565-1572
This study demonstrates how positive ion atmospheric pressure photoionization-ion mobility spectrometry-mass spectrometry
(APPI-IMS-MS) can be used to produce different ionic forms of an analy te and how these can be separated. When hexane:toluene
(9:1) is used as a solvent, 2,6-di-tert-butylpyridine (2,6-DtBPyr) and 2,6-di-tert-4-methylpyridine (2,6-DtB-4-MPyr) efficiently produce radical cations [M]+ and protonated [M + H]+ molecules, whereas, when the sample solvent is hexane, protonated molecules are mainly formed. Interestingly, radical cations
drift slower in the drift tube than the protonated molecules. It was observed that an oxygen adduct ion, [M + O2]+, which was clearly seen in the mass spectra for hexane:toluene (9:1) solutions, shares the same mobility with radical cations,
[M]+. Therefore, the observed mobility order is most likely explained by oxygen adduct formation, i.e., the radical cation forrning
a heavier adduct. For pyridine and 2-tert-butylpyridine, only protonated molecules could be efficiently formed in the conditions used. For 1- and 2-naphthol it was
observed that in hexane the protonated molecule typically had a higher intensity than the radical cation, whereas in hexane:toluene
(9:1) the radical cation [M]+ typically had a higher intensity than the protonated molecule [M + H]+. Interestingly, the latter drifts slower than the radical cation [M]+, which is the opposite of the drift pattern seen for 2,6-DtBPyr and 2,6-DtB-4-MPyr. 相似文献
986.
Patrik Ek Mårten Stjernström Åsa Emmer Johan Roeraade 《Rapid communications in mass spectrometry : RCM》2010,24(17):2561-2568
We describe a method for nanoelectrospray ionization mass spectrometry (nESI‐MS) of very small sample volumes. Nanoliter‐sized sample droplets were taken up by suction into a nanoelectrospray needle from a silicon microchip prior to ESI. To avoid a rapid evaporation of the small sample volumes, all manipulation steps were performed under a cover of fluorocarbon liquid. Sample volumes down to 1.5 nL were successfully analyzed, and an absolute limit of detection of 105 attomole of insulin (chain B, oxidized) was obtained. The open access to the sample droplets on the silicon chip provides the possibility to add reagents to the sample droplets and perform chemical reactions under an extended period of time. This was demonstrated in an example where we performed a tryptic digestion of cytochrome C in a nanoliter‐sized sample volume for 2.5 h, followed by monitoring the outcome of the reaction with nESI‐MS. The technology was also utilized for tandem mass spectrometry (MS/MS) sequencing analysis of a 2 nL solution of angiotensin I. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
987.
Gert H. Kristensen Morten M. Klausen Vagn A. Hansen Frants R. Lauritsen 《Rapid communications in mass spectrometry : RCM》2010,24(1):30-34
To study the long‐term dynamics of trihalomethanes (THMs) in a warm (31–33°C) public swimming pool, we built a robust membrane inlet mass spectrometer that could perform unsupervised, on‐site monitoring of the concentration of these compounds with off‐site, real‐time surveillance. The instrument was installed in a technical room below the pool and operated continuously for more than a year practically only interrupted for filament replacements every 6–8 weeks. One to two days after a filament replacement, the instrument stabilized and kept its calibration until shortly before the next filament burnout. The on‐line monitoring of THMs revealed a daily rhythm in the concentrations of chloroform and bromodichloromethane. They increased during the pool's closing hours and decreased during opening hours with the minimum concentration being approximately half of the maximum. Over the 1 year monitoring period, the variation in the maximum registered daily concentration was 30–100 µg/L for chloroform. The variation of bromodichloromethane was 5–10 µg/L, except during bursts of 1–2 days duration, where the concentration of bromodichloromethane could reach 100 µg/L. The burst in bromodichloromethane concentration was directly correlated with salt addition (sodium chloride) to the pool water for use in the pool's electrolytic in‐line chlorination system. A correlation between THM removal from the pool water and the operation of a strong water jet system was also found. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
988.
Sofia Målberg Dildare Basalp Anna Finne‐Wistrand Ann‐Christine Albertsson 《Journal of polymer science. Part A, Polymer chemistry》2010,48(5):1214-1219
The catalytic activities of Bi(III) acetate (Bi(OAc)3) and of creatinine towards the ring‐opening polymerization of L ‐lactide have been compared with those of a stannous (II) ethylhexanoate ((SnOct)2)‐based system and with those of a system catalyzed by enzymes. All four were suitable catalysts for the synthesis of high and moderate molecular weight poly(L ‐lactide)s and the differences in reactivity and efficiency have been studied. Linear and branched poly(L ‐lactide)s were synthesized using these bio‐safe initiators together with ethylene glycol, pentaerythritol, and myoinositol as coinitiators. The polymerizations were performed in bulk at 120 and 140 °C and different reactivities and molecular weights were achieved by adding different amounts of coinitiators. A molecular weight of 105,900 g/mol was achieved with 99% conversion in 5 h at 120 °C with a Bi(OAc)3‐based system. This system was comparable to Sn(Oct)2 at 140 °C. The reactivity of creatinine is lower than that of Bi(OAc)3 but higher compared with enzymes lipase PS (Pseudomonas fluorescens). A ratio of Sn(Oct)2Mo/Io 10,000:1 was needed to achieve a polymer with a reasonable low amount of tin residue in the precipitated polymer, and a system catalyzed by creatinine at 140 °C has a higher conversion rate than such a system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1214–1219, 2010 相似文献
989.
Francesco Aquilante Luca De Vico Nicolas Ferr Giovanni Ghigo Per‐ke Malmqvist Pavel Neogrdy Thomas Bondo Pedersen Michal Pitok Markus Reiher Bjrn O. Roos Luis Serrano‐Andrs Miroslav Urban Valera Veryazov Roland Lindh 《Journal of computational chemistry》2010,31(1):224-247
Some of the new unique features of the MOLCAS quantum chemistry package version 7 are presented in this report. In particular, the Cholesky decomposition method applied to some quantum chemical methods is described. This approach is used both in the context of a straight forward approximation of the two‐electron integrals and in the generation of so‐called auxiliary basis sets. The article describes how the method is implemented for most known wave functions models: self‐consistent field, density functional theory, 2nd order perturbation theory, complete‐active space self‐consistent field multiconfigurational reference 2nd order perturbation theory, and coupled‐cluster methods. The report further elaborates on the implementation of a restricted‐active space self‐consistent field reference function in conjunction with 2nd order perturbation theory. The average atomic natural orbital basis for relativistic calculations, covering the whole periodic table, are described and associated unique properties are demonstrated. Furthermore, the use of the arbitrary order Douglas‐Kroll‐Hess transformation for one‐component relativistic calculations and its implementation are discussed. This section especially focuses on the implementation of the so‐called picture‐change‐free atomic orbital property integrals. Moreover, the ElectroStatic Potential Fitted scheme, a version of a quantum mechanics/molecular mechanics hybrid method implemented in MOLCAS, is described and discussed. Finally, the report discusses the use of the MOLCAS package for advanced studies of photo chemical phenomena and the usefulness of the algorithms for constrained geometry optimization in MOLCAS in association with such studies. © 2009 Wiley Periodicals, Inc. J Comput Chem 2010 相似文献
990.