Chiral separation of underivatized amino acids in supercritical fluid chromatography with chiral crown ether derived column

The supercritical fluid chromatographic separation of underivatized amino acids was explored using immobilized chiral crown ether column CROWNPAK CR-I (+) and mass spectrometric detection. The type of modifier, acidic additives, and the role of water were investigated. Enantioseparation was achieved for all 18 amino acids investigated with short retention times (less than 3 minutes) and average resolution of greater than 5.0. Analysis of enantiomerically pure standards demonstrated the D enantiomer eluted first for all amino acids using a CROWNPAK CR-I (+) column.     

Investigation of the chiral recognition ability of human carboxylesterase 1 using indomethacin esters

Human carboxylesterase 1 (hCES1) is an enzyme that plays an important role in hydrolysis of pharmaceuticals in the human liver. In this study, elucidation of the chiral recognition ability of hCES1 was attempted using indomethacin esters in which various chiral alcohols were introduced. Indomethacin was condensed with various chiral alcohols to synthesize indomethacin esters. The synthesized esters were hydrolyzed with a human liver microsome (HLM) solution and a human intestine microsome (HIM) solution. High hydrolytic rate and high stereoselectivity were confirmed in the hydrolysis reaction in the HLM solution but not in the HIM solution, and these indomethacin esters were thought to be hydrolyzed by hCES1. Next, these indomethacin esters were hydrolyzed in recombinant hCES1 solution and the hydrolysis rates of the esters were calculated. The stereoselectivity confirmed in HLM solution was also confirmed in the hCES1 solution. In the hydrolysis reaction of esters in which a phenyl group is bonded next to the ester, the V_max value of the (R) form was 10 times larger than that of the (S) form.     

Successful use of a novel lux® i-Amylose-1 chiral column for enantioseparation of “legal highs” by HPLC

Bath salts, fumigations, cleaners and air fresheners, behind these terms substances are hidden, which count as “Legal Highs”. These fancy names are used to pretend Legal Highs as harmless compounds, to circumvent legal regulations for marketing as well as to increase the sales. Besides classic illicit drugs of synthetic origin such as amphetamines, cocaine and MDMA, the trade of these compounds, also known as new psychoactive substances (NPS), is not uncommon today. In many countries, NPS are still not subject to drug control. Among them, there are stimulants such as new amphetamine derivatives or cathinones, which possess a chiral centre. Little is known about the fact that the two possible enantiomers may differ in their pharmacological effect. The aim of this study was to test a novel HPLC column for the enantioseparation of a set of 112 NPS coming from different chemical groups and collected by internet purchases during the years 2010–2018. The CSP, namely Lux® 5 μm i-Amylose-1, LC Column 250 x 4.6 mm, was run in normal phase mode under isocratic conditions, UV detection was performed at 245 nm and 230 nm, injection volume was 10 μl and flow rate was 1 ml/min. With a mobile phase consisting of n-hexane/isopropanol/diethylamine (90:10:0.1), herein, 79 NPS were resolved into their enantiomers successfully, for 37 of them baseline resolution was achieved. After increase of lipophily of the mobile phase to 99:1:0.1, another 27 compounds were baseline separated. It was found that all separated NPS are traded as racemic compounds.     

有机物料还田对双季稻田土壤有机碳及其活性组分的影响

有机物料还田是提升农田土壤有机碳、培肥土壤的重要措施。为探讨不同有机物料的还田效果,采用室外培养方法,研究了在等碳输入条件下,施用水稻秸秆、紫云英、生物有机肥、猪粪和水稻秸秆生物炭对洞庭湖双季稻区潮土有机碳和活性有机碳组分含量的影响。结果表明: 经过180 d的培养试验,与不施用有机物料相比,施用有机物料提高了土壤活性有机碳含量。生物有机肥、猪粪和水稻秸秆生物炭处理分别使土壤有机碳含量显著提升了26.1%、9.7%和30.7%,水稻秸秆和紫云英对土壤有机碳含量的提升效应在试验期间并不显著。水稻秸秆和紫云英还田更有利于土壤可溶性有机碳和微生物生物量碳的积累,猪粪更有利于土壤可溶性有机碳的积累,生物有机肥更有利于土壤微生物生物量碳和易氧化有机碳的积累,水稻秸秆生物炭则更有利于土壤微生物生物量碳和轻组有机碳的积累。与水稻秸秆还田相比,紫云英、生物有机肥、猪粪和水稻秸秆生物炭还田使土壤碳库管理指数分别提高了31.8%、111.6%、62.2%和50.7%。从土壤固碳和土壤碳库管理指数来看,生物有机肥、猪粪和水稻秸秆生物炭的还田效果优于水稻秸秆和紫云英还田。     

Stereocontrolled Reduction of Alpha-Methyl Beta-Ketoesters by Geotrichum Candidum

The conditions of the reduction of racemic ethyl 2-methyi-3-oxobutanoate by the mould Geotrichum candidum have been investigated in order to produce exclusively the corresponding (2S, 3S) anti hydroxyester. The alteration of the syn/anti hydroxyester ratio previously observed is the result of an interconversion equilibrium involving the oxoester. The syn ester formation is inhibited by ageing the biomass in water before use, or by effecting the reduction in the presence of sodium chloride. Optimized conditions are described allowing the production of the anti ester in high yield and high optical purity.     

Role of particle coating in controlling skin damage photoinduced by titania nanoparticles

TiO₂ nanoparticles hazard is associated to their photocatalytic activity causing release of DNA damaging ROS (Reactive Oxygen Species), lipid peroxidation and skin damage. Various coatings have been proposed to minimize photocatalysis, while keeping the potential to block UV radiations. Uncoated and variously coated commercial nano-titania have been classified on the basis of UVB-induced lipoperoxidation of linoleic acid. A selection of the most and the least protective specimens was then examined by ESR (Electron Spin Resonance) to evidence the presence of surface paramagnetic centres and the release of ROS in aqueous suspensions (spin trapping). Paramagnetic centres and ROS were correlated with the extent of lipid peroxidation. When tested on porcine skin (mimicking the human one), titania acted as on linoleic acid. The combined use of lipid peroxidation of simple fatty acids with ESR analysis is here proposed as a possible screening tool for the evaluation of the potential toxicity of nano-titania in sunscreen preparations.     

Flow cytometric estimation of ‘labile iron pool’ in human white blood cells reveals a positive association with ageing

A small part of cellular iron, usually called ‘labile iron pool’ (LIP), is not securely stored and has the potential to catalyse the formation of highly reactive oxygen species. The present work estimated LIP levels in human white cells by using the analytical power of flow cytometry. The method relies essentially on already established principles but has the added value of monitoring LIP in different subpopulations of human blood cells concurrently in a single sample. Examination of 41 apparently healthy individuals revealed a positive correlation between LIP levels and the age of the donors (r=0.656, 0.572 and 0.702 for granulocytes, lymphocytes and monocytes, respectively, p<0.0001), indicating that cells of older individuals are prone to oxidations in conditions of oxidative stress. It is suggested that LIP estimation may represent a valuable tool in examinations searching for links between iron and a variety of oxidative stress-related pathological conditions.     

Intense photon emission induced by fracture of γ–irradiated Dy‐, Tm‐, Sm‐ and Mn‐doped CaSO4 single crystals

When an γ‐irradiated Dy‐, Tm‐, Sm‐ or Mn‐doped CaSO₄ crystal is impulsively deformed, two peaks appear in the ML intensity versus time curve, whereby the first ML peak is found in the deformation region and the second in the post‐deformation region of the crystals. In this study, intensities I_m1 and I_m2 corresponding to first and second ML peaks, respectively, increased linearly with an impact velocity v₀ of the piston used to deform the crystals, and times t_m1 and t_m2 corresponding to the first and second ML peaks, respectively, decreased with impact velocity. Total ML intensity initially increased with impact velocity and then reached a saturation value for higher values of impact velocity. ML intensity increased with increasing γ‐doses and size of crystals. Results showed that the electric field produced as a result of charging of newly‐created surfaces caused tunneling of electrons to the valence band of the hole‐trapping centres. The free holes generated moved in the valence band and their subsequent recombination with electron trapping centres released energy, thereby resulting in excitation of luminescent centres. Copyright © 2012 John Wiley & Sons, Ltd.     

(+)-9-Benzyloxy-α-Dihydrotetrabenazine as an Important Intermediate for the VMAT2 Imaging Agents: Absolute Configuration and Chiral Recognition

This article reports, for the first time, on the absolute configuration of (+)-9-benzyloxy-α-dihydrotetrabenazine ( 8 ), as determined from the perspective of X-ray crystallography. Compound 8 was prepared by a six-step reaction using 3-benzyloxy-4-methoxybenzaldehyde ( 1 ) as a starting material. The X-ray crystal diffraction structure of two compounds, racemic 9-benzyloxy-tetrabenazine ( 5 ) and the diastereomeric salt of compound 8 , is also described for the first time in this article. The X-ray results and the chiral HPLC helped elucidate that compound 8 has an absolute configuration as 2R,3R,11bR. The crystal structure of racemic compound 5 contains two symmetry- independent molecules in the unit cell. Interestingly, while they are structural isomers, they are enantiomers, too, i.e., in solution, because they are not mirror images of each other in the crystal lattice. In order to elucidate the intermolecular interaction mechanism of the diastereomeric salt of compound 8 , its crystal packing was investigated with regard to the weak interactions, such as salt bridge, OH…O and CH…O hydrogen bonds, and intermolecular CH…π interaction. The results showed that the carbonyl-assisted salt bridges and the OH…O hydrogen bonds formed polar columns in the crystal structure of the diastereomeric salt of compound 8 , resembling butterflies with open wings as viewed along the c-axis. These polar columns were extended to three-dimensional network by intermolecular CH…O hydrogen bonds and intermolecular CH…π interactions. Chirality, 2013. © 2013 Wiley Periodicals, Inc.