A Study of N-Butyl-(all-trans-retinylidene)amine and Its Protonated Species by 1H- and 13C-NMR. Spectroscopy

The Schiff base of all-trans-retinal was investigated in organic solution by ¹H- and ¹³C-NMR. at high field. Complete assignment of the ¹H-NMR. peaks of N-butyl-(all-trans-retinylidene)amine ( 2 ) and the N-butyl-(all-trans-retinylidene)-ammonium ion ( 3 ) was achieved by INDOR (internuclear double resonance). The vicinal proton coupling constants of the polyene chain show that the π-bond orders remain unchanged in N-butyl-(all-trans-retinylidene)amine relative to all-trans-retinal ( 1 ), but change towards larger π-delocalization in the N-butyl-(all-trans-retinylidene)ammonium ion. At ?-61° only one isomer of N-butyl-(all-trans-retinylidene)ammonium was observed. This was shown to be trans at the imine linkage and independent of the solvent. The trifluoroacetic acid counter-ion can approach the positive charge of the N-atom in the weakly polar solvent dichloromethane but not in the leveling solvent methanol. In dichloromethane the nature of the 1:1 complex is a H-bonded (O^?…H-N⁺) ion-pair whose rate of breaking and forming is rapid at RT. Strong stabilization of the ion-pair resulted from homo-conjugation with a second molecule of trifluoroacetic acid. Excess of acid efficiently diminished the isomerization rate at the C,N-bond.     

Novel and unusual triterpene from Black Cohosh. Determination of structure of 9,10-seco-9,19-cyclolanostane xyloside (cimipodocarpaside) by NMR, IR and Raman spectroscopy and DFT calculations

A new triterpene xyloside, designated cimipodocarpaside was isolated from a Black Cohosh (Actea racemosa L.) extract and its structure was elucidated by means of 1H, 13C NMR, IR and Raman spectroscopy supported by B3LYP/6-31G** calculations. The vibrational spectra were interpreted using the PED analysis of 273 fundamentals. Its structure comprises four condensed rings A-D which are 6, 7, 6, and 5-membered, respectively. An oxiirane ring is located in the side chain and a xylose moiety is attached to the A-ring. Comparison of the experimental 13C NMR data with the theoretical chemical shifts of 24S- and 24R-cimipodocarpaside isomers revealed that the isolated compound has the 24S-configuration. Combined spectroscopic and computational studies enabled the determination of the structure of cimipodocarpaside as (24S)-3β-hydroxy-24,25-oxiirane-16,23-dione-9,10-seco-9,19-cyclolanost-7(8),9(11),10(19)-trien-3-O-β-D-xylopyranoside. Triterpenes with 7-membered ring were thus far isolated from only Actea podocarpa DC. plants. This is the first report on the isolation of such a compound from Black Cohosh.     

亚烷基卡宾及取代亚烷基卡宾与环硫乙烷反应的量子化学研究

用量子化学的密度泛函理论(DFT)在6-311G(d, p)水平上对亚烷基卡宾及取代亚烷基卡宾与环硫乙烷的硫转移反应机理进行了系统的研究. 用IRC对过渡态进行了确认. 并用组态混合模型讨论了反应势垒(ΔE^≠)与XYC＝C的单-三态能量差ΔE_ST之间的关系. 结果表明, 取代基的电负性是控制反应的主要因素, 取代基的电负性越大, 取代基越多, π电子给予体越多, 单-三态能量差ΔE_ST就越小, 该反应的活化能就越小, 反应越容易发生. 同时还讨论了该反应中环硫乙烷的C—S键的解离过程. 并与标题化合物和环氧乙烷的氧转移反应进行了比较.     

Determination of Inorganic Sb(V) and Methylantimony Species by HPLC with Hydride Generation-Atomic Fluorescence Spectrometric Detection

 An on-line method for the separation and analysis of Sb(V) and Me₃Sb in the presence of Sb(III) in liquid samples is described. Inorganic and organic antimony species were separated using anion-exchange high-performance liquid chromatography (HPLC) coupled with hydride generation-atomic fluorescence detection (HG-AFS). Optimum conditions for the separation of antimony species by HPLC and the hydride generation conditions for the determination by HG-AFS were established. Matrix interference of the chromatographic determination was studied in relation to MgSO₄ and NaCl. The method developed was applied to the separation and determination of antimony species in spiked and natural water samples. The suitability of the method for analysis in microbial growth media and physiological studies involving methylantimony species is discussed. Received December 11, 2000. Revision April 26, 2001.     

A New Nonsymmetric As(OH)3 Species. Comparison with the Known C3 Species and Thermochemistry at the HF,DFT(B3LYP), MP2, MP4, and CCSD(T) Levels of Theory.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.     

HPLC/DAD,Antibacterial and Antioxidant Activities of Plectranthus Species (Lamiaceae) Combined with the Chemometric Calculations

The increase in antibiotic resistance and the emergence of new bacterial infections have intensified the research for natural products from plants with associated therapy. This study aimed to verify the antibacterial and antioxidant activity of crude extracts of the genus Plectranthus species, being the first report on the modulation of aminoglycosides antibiotic activity by Plectranthus amboinicus extracts. The chemical composition was obtained by chemical prospecting and High-Performance Liquid Chromatography with diode arrangement detector (HPLC/DAD). The antibacterial activities of the extracts alone or in association with aminoglycosides were analyzed using the microdilution test. The antioxidant activity was evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging. The phytochemical prospection allowed the flavonoids, saponins, tannins and triterpenoids to be identified. Quercetin, rutin, gallic acid, chlorogenic acid, caffeic acid, catechin, kaempferol, glycosylated kaempferol, quercitrin, and isoquercitrin were identified and quantified. The principal component analysis (PCA) observed the influence of flavonoids and phenolic acids from Plectranthus species on studied activities. Phytochemical tests with the extracts indicated, especially, the presence of flavonoids, confirmed by quantitative analysis by HPLC. The results revealed antibacterial activities, and synergistic effects combined with aminoglycosides, as well as antioxidant potential, especially for P. ornatus species, with IC₅₀ of 32.21 µg/mL. Multivariate analyzes show that the inclusion of data from the antioxidant and antibacterial activity suggests that the antioxidant effect of these species presents a significant contribution to the synergistic effect of phytoconstituents, especially based on the flavonoid contents. The results of this study suggest the antibacterial activity of Plectranthus extracts, as well as their potential in modifying the resistance of the analyzed aminoglycosides.     

Separation and Direct Chemical Determination of Nitrosamines by High Performance Liquid Chromatography (HPLC)

Abstract

Volatile and non-volatile nitrosamines are determined at subparts per million levels in a continuous, inexpensive, low-temperature procedure when samples are compatible with the aqueous-alcoholic solvents. Individual nitrosamines are resolved by gradient elution on appropriate HPLC columns, converted to nitrite ion by ultra-violet light, combined with modified Griess reagent and the red-colored product measured at 540 nanometers. Inorganic nitrite may be determined and two, organic compounds are known to interfere. The detection level for N-nitrosodimethyl amine is 0.1 parts per million.     

Synthesis and Characterization of Variable-valent Imidorhenium Species. A Family of Imidorhenium(VI) Amide Complexes and their Imidorhenium(V) Imine Precursors Related by Oxygen Atom Transfer

The synthesis of imidorhenium(V) [Re(NAr)Cl₃(L)] complexes is reported. Their reaction with dilute HNO₃ furnishes [Re(NAr)Cl₃(L′)] species incorporating monoionized iminoamide ligands (the ligands are abbreviated as L and L′ respectively). The iminoamide complexes exhibit sextet EPR spectra in CH₂Cl₂ solution at room temperature. They are electroactive in MeCN solution and to display two quasi reversible responses near 0.2 and 1.6 V which can be attributed to Re^V→Re^VI and Re^VI → Re^VII oxidations respectively. One of the [Re(NAr)Cl₃(L)] complexes has been structurally characterized. The trans influence of the amide nitrogen considerably lengthens the Re–N bond lying trans to the imido group. The triply bonded ReN–C moiety is linear.     

人血红蛋白及其三硝基甲苯加合物的高效液相色谱分离

介绍了采用反相大孔径Ｃ４柱分离血红蛋白（Ｈｂ）的新的高效液相色谱（ＨＰＬＣ）条件,流动相采用乙腈－水－三氟乙酸,在梯度洗脱方式下,对Ｈｂ中的血色素（ｈｅｍｅ）、α－和β－链以及未解离的球蛋白进行了分离,速度快且洗脱完全,并用于三硝基甲苯（ＴＮＴ）－Ｈｂ加合物的分离。结果在体外实验发现了ＴＮＴ－Ｈｂ加合物的形成,其水平为２０４ｐｍｏｌ／ｍｇＨｂ。     

一种新的分离三硝基甲苯及其代谢产物的高效液相色谱方法

An HPLC method is described for separation of TNT and its main reduction metabolites. Two columns(LC-C(18) and LC-CN)are connected in series and operated isocratically at 1.0mL/min with water-methanol-tetrahydrofuran(60+ 35+ 5 ). The baseline separation of 4-amino-2,6-dinitrotoluene(4A) and 2-amino-4,6-dinitrotoluene(2A) ,which are main metabolites of TNT,is obtained(Rs=2.1).     

Identification of Epilobium Species and Willow-herbs (Onagraceae) by HPLC Analysis of Flavonoids as Chemotaxonomic Markers

The aim of this work was to compare macro- and micromorphological characteristics and flavonoid composition of some Epilobium species and commercial willow-herbs for their authentication and quality control. In order to determine the flavonoid composition of extracts, the flavonol-glycosides were also hydrolised quantitatively to their aglycones. Before and after hydrolysis flavonoid fingerprints were studied by high-performance liquid chromatography using two different gradient mobile phase systems. Flavonoid composition was found to be suitable for the authentication of Epilobium species and commercial willow-herbs as an alternative to the current phytochemical study and time-consuming microscopic procedures [1]. The combined HPLC analysis of free flavonoid-aglycones and glycosides, developed in our laboratory can be used for the quality control of willow-herb samples and various commercial preparations.     

Study of chiral recognition mechanism of O,O-diethyl (p-methylbenzenesulfonamindo)-aryl(alkyl)-methylphosphonates by HPLC with a series of CSPs

Five chiral stationary phases (CSPs) were used to separate the enantiomers of a series of O,O-diethyl (p-methyl-benzenesulfonamindo)- aryl(alkyl)-methylphosphonates. A chiral recognition mechanism was presented to explain the resolution of these compounds. Results show that CSP with strong π-acceptor 3,5-dinitrobenzoyl group and high steric hindrance has the best resolution ability in chiral separation of O,O-diethyi (p-methyl-benzenesulfonamindo)- aryl(alkyl)-methylphosphonates. When a CSP has just a strong π-acceptor 3,5-dinitrobenzoyl or high steric hindrance it does not have good chiral resolution ability. The chiral recognition is more difficult when the CSP has more than one asymmetric center.     

Pierre Duhem: Mixture and Chemical Combination and Related Essays. Edited and translated, with an Introduction, by Paul Needham

The following is an essay review of Paul Needham's translation of Pierre Duhem's Lemixte et la combinaison chimique and a numberof other essays. In this review we describe theintent and general features of Le mixte and try to place it in the larger context of Duhem'sprogram for energetics. The long essay (Essay3) opposing Marcellin Berthelot'sthermochemistry is singled out for detailedcommentary, since it gives Duhem's reasons forendorsing Josiah Willard Gibbs's chemicalstatics. We argue that a chemical mechanics ofa Gibbsian sort, defended in Le mixte and otheressays in this volume, was the inspiration for,and basis of, Duhem's energetics. Needham'swelcome translations help an English-languageaudience to better understand the basiccontours of Duhem's important, if ultimatelymisguided, project. We conclude with somecomments on the difficulties in translatingDuhem and on the quality of the translationsNeedham has provided. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study on the Chromatographic Fingerprinting of Schisandra chinensis (Turcz.) Baill. by LC Coupled with Principal Component Analysis

Schisandra chinensis (Turcz.) Baill. is a rich source of lignans with diverse biological activities. Quantitative analysis and chromatographic fingerprinting of the fruitlets of the plant by liquid chromatography (LC) were performed in order to characterize and evaluate the region-related variation. Using the optimized LC method, satisfactory linearity and repeatability were obtained for all the test standards. This method was subsequently applied for the identification and quantitation of six lignans in fruitlets of Schisandra chinensis by comparing the retention time with that of authentic standards available. Principal component analysis (PCA) was also employed to assess the similarity and dissimilarity of the fingerprint profiles from different origins encompassing eleven areas from China and two samples from Japan. The work suggested that the fruitlets of Schisandra chinensis from Japan exhibited great difference with those from China as evidenced by the clear separation in the PCA scores plot as well as quantitative analysis e.g., schisandrin and deoxyschisandrin are 5.50 μg mg^?1 $ (\overline{X} ) $ and 0.90 μg mg^?1 $ (\overline{X} ) $ in the materials from China and 3.40 μg mg^?1 $ (\overline{X} ) $ and 1.90 μg mg^?1 $ (\overline{X} ) $ in the materials from Japan, respectively. Such a reliable method potentially provides an effective and convenient method for quality control of herbal medicine from different regions.