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41.
S. Nygren 《Journal of separation science》1979,2(6):319-323
The technique of programming the carrier gas flow rate in gas chromatography, especially in connection with the use of capillary columns shorter than 10 m can significantly accelerate GC analyses. Equations for calculation of the parameters of the exponential flow function and retention data are described. The effects of flow programming in a short capillary column are shown in a few chromatograms. Different programming rates are tested and compared with temperature programming. 相似文献
42.
A sensitive and convenient high-performance liquid chromatography-tandem mass spectrometry(HPLC-MS/MS) assay is described for the (5-HT(lB/lD)) receptor agonist sumatriptan in human plasma. Sumatriptan was recovered from plasma (81.8 +/- 6.8%) by liquid-liquid extraction. The mobile phase flow rate was 0.3 mL/min and consisted of methanol:water:formic acid (90:10:0.1, v/v/v). The analytical column (4.6 x 100 mm) was packed with Partisil C(8) (5 micro m). The standard curve was linear from 0.7 to 70.4 ng/mL (r(2) > 0.99). The lower limit of quantitation was 0.7 ng/mL. The assay was specific, accurate (percentage deviation from nominal concentrations were <15%), precise and reproducible (within- and between-day coefficients of variation <10.3%). Sumatriptan in plasma was stable over three freeze/thaw cycles and at room temperature for one day. The utility of the assay was demonstrated by following sumatriptan plasma concentrations in two healthy subjects for 8-12 h following a single 20 mg intranasal dose. 相似文献
43.
Summary A new equation is derived relating the retention index to the molecular polarizabilities, ionization potentials and permanent dipole moments of the stationary phase and the solute.Various implications of this equation to quantitative structure-retention relationships are discussed. 相似文献
44.
The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed. 相似文献
45.
A. V. Safronova L. N. Bochkarev N. E. Stolyarova I. K. Grigorieva I. P. Malysheva G. V. Basova G. K. Fukin E. V. Baranov Yu. A. Kurskii G. A. Abakumov 《Russian Chemical Bulletin》2006,55(2):218-221
New germanium-containing tungsten carbyne complexes Ph3GeC≡W(CH2R)3 (R = But or SiMe3) were synthesized by the reaction of the alkoxy derivative Ph3GeC≡W(OBut)3 with alkyllithium reagents RCH2Li. The new compounds were isolated in individual form as crystals in 95 and 90% yields, respectively, and were characterized
by elemental analysis, 1H and 13C NMR spectroscopy, and X-ray diffraction. X-ray diffraction study showed that the coordination environment of the W and Ge
atoms in the Ph3GeC≡ W(CH2But)3 and Ph3GeC≡W(CH2SiMe3)3 complexes can be described as a distorted tetrahedron.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 213—216, February, 2006. 相似文献
46.
Layzon A.L. da Silva Louis P. Sandjo Alechania Misturini Giovanni F. Caramori Maique W. Biavatti 《Journal of mass spectrometry : JMS》2019,54(11):915-932
Sesquiterpene lactones (SL) have been reported with various biological effects. Among the described SL skeletons, hirsutinolide and glaucolide have not been extensively studied by mass spectrometry (MS), especially how to distinguish them in organic matrices. Thus, this paper reports (1) a strategy of their differentiation based on MS behavior during the ionization and (2) a proposal of the fragmentation pattern for both SL‐subtypes. ESI(+)‐HRMS data of four isolated SL (hirsutinolides 1 and 3 ; glaucolides 2 and 4 ) were recorded by direct and UPLC water‐sample combined injections. These analyses revealed that hirsutinolides and glaucolides formed [M+Na]+ ion during the operation of the direct MS injection, and ([M+Na]+ and [M+H‐H2O]+) and [M+H]+ ions were respectively observed for hirsutinolides and glaucolides during the operation of combined UPLC water and sample MS injection. Computational simulations showed that the complex hirsutinolide ( 1 )‐Na+ formed with a lower preparation energy compared with the complex glaucolide ( 2 )‐Na+. However, despite their different behavior during the ionization process, ESI(+)‐HRMS/MS analyses of 1 ‐ 4 gave similar fragmentation patterns at m/z 277, 259, 241, and 231 that can be used as diagnostic ions for both skeletons. Moreover, the differentiation strategy based on the nature of the complex SL‐adducts and their MS/MS fragmentation pattern were successfully applied for the chemical characterization of the extract from Vernonanthura tweedieana using UPLC‐ESI‐HRMS/MS. Among the characterized metabolites, SL with hirsutinolide and glaucolide skeletons showed the aforementioned diagnostic fragments and an ionization behavior that was similar to those observed during the water‐sample combined injection. 相似文献
47.
Mechanisms for the initial stage of glyceraldehyde and glycine Maillard reaction under different pH conditions have been proposed, following usually the Hodge-scheme. Computations have been performed on the mechanisms at the standard state to test the possibility of the formation of different compounds, through evaluating the changes in Gibb's free energy during the reaction. Electronic energy changes during the reaction have also been evaluated. Glyceraldehyde+deprotonated glycine reaction has been found to be the most favorable for the formation of the Amadori rearrangement products in both gaseous and aqueous states. Due to the possibility of the production of both enol and keto forms of the Amadori rearrangement product, the rate of browning in glyceraldehyde+deprotonated glycine reaction is assumed to be faster than the others. Glyceraldehyde+unionized glycine reaction has been found to be more plausible for the formation of the keto form of the Amadori rearrangement products, particularly, in the gaseous phase. Glyceraldehyde+protonated glycine and glyceraldehyde+glycine zwitterion reactions are not favorable for the formation of the Amadori rearrangement products. Formation of hydroxyacetaldehyde from glyceralaldehyde, as one of the possible C2-fragmentation product, has been found to be favorable in the aqueous state. 相似文献
48.
Wilmer H. Perera Siddanagouda R. Shivanagoudra Jose L. Prez Da Mi Kim Yuxiang Sun Guddadarangavvanahally K. Jayaprakasha Bhimanagouda S. Patil 《Molecules (Basel, Switzerland)》2021,26(4)
Diabetes mellitus is a chronic disease and one of the fastest-growing health challenges of the last decades. Studies have shown that chronic low-grade inflammation and activation of the innate immune system are intimately involved in type 2 diabetes pathogenesis. Momordica charantia L. fruits are used in traditional medicine to manage diabetes. Herein, we report the purification of a new 23-O-β-d-allopyranosyl-5β,19-epoxycucurbitane-6,24-diene triterpene (charantoside XV, 6) along with 25ξ-isopropenylchole-5(6)-ene-3-O-β-d-glucopyranoside (1), karaviloside VI (2), karaviloside VIII (3), momordicoside L (4), momordicoside A (5) and kuguaglycoside C (7) from an Indian cultivar of Momordica charantia. At 50 µM compounds, 2–6 differentially affected the expression of pro-inflammatory markers IL-6, TNF-α, and iNOS, and mitochondrial marker COX-2. Compounds tested for the inhibition of α-amylase and α-glucosidase enzymes at 0.87 mM and 1.33 mM, respectively. Compounds showed similar α-amylase inhibitory activity than acarbose (0.13 mM) of control (68.0–76.6%). Karaviloside VIII (56.5%) was the most active compound in the α-glucosidase assay, followed by karaviloside VI (40.3%), while momordicoside L (23.7%), A (33.5%), and charantoside XV (23.9%) were the least active compounds. To better understand the mode of binding of cucurbitane-triterpenes to these enzymes, in silico docking of the isolated compounds was evaluated with α-amylase and α-glucosidase. 相似文献
49.
Srivastava SK Ojha AK Kiefer W Asthana BP 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):2832-2839
Raman spectra of propylamine (C3H7NH2) and its binary mixtures, C3H7NH2 + CH3OH with varying mole fractions of the reference system, C3H7NH2, C were recorded in two widely apart wavenumber regions, 3100-3600 cm(-1) and 1225-1325 cm(-1). In the former region, the two Raman bands at approximately 3305 and approximately 3326 cm(-1), obtained after the line shape analysis, which were assigned to symmetric nu(N-H) and anti-symmetric nu(N-H) stretching modes, respectively, show a downshift upon dilution. However, whereas the nu(N-H) anti-symmetric mode shows a shift of 18.6 cm(-1), the nu(N-H) symmetric mode shows a much smaller shift (5.7 cm(-1)) between neat liquid and high dilution, C = 0.1. This aspect has been explained using the optimized geometries calculated employing ab initio theory (MP2 level) for the neat C3H7NH2 and its different hydrogen-bonded complexes. The linewidth versus concentration plot for the nu(N-H) anti-symmetric stretching mode, however exhibits a distinct maxima at C = 0.4, which has been explained as a slight departure from the concentration fluctuation model. In the latter region, a symmetric peak is observed, which corresponds to nu(C-N) stretching mode, which shows an upshift upon dilution and an almost linear concentration dependence. This has also been explained in terms of the parameters obtained from the optimized geometries of the different hydrogen-bonded complexes. 相似文献
50.
The European strategy for dioxin monitoring of the food chain has defined high-resolution gas chromatography coupled to high-resolution mass spectrometry (HRGC/HRMS) method as the confirmatory method that can provide reliable and comparable results at sub-parts per trillion (ppt) level. This paper describes the first inter-laboratory study on dioxins, furans and dioxin-like PCBs by HRGC/HRMS method in animal feedingstuffs. Two different statistical approaches (ISO 5725 and Cofino’s statistics) were used for the statistical evaluation. For this particular study, the performances of the HRGC/HRMS method seem to be congener-independent in repeatability and reproducibility conditions over a concentration range covering more than four orders of magnitude. Results clearly show the effect of precision loss below 0.1 ppt level per congener in repeatability conditions and below 0.2 ppt level per congener in reproducibility conditions. LODs reported by the laboratories give median values of 0.02 ng/kg for most of the toxic congeners. Relative standard deviation between the laboratories’ mean values using upper-bound approach for TEQ calculation is 6.2%, more than twice the maximum level set at 0.75 ng TEQ/kg of product. 相似文献