Quantitative determination of glutathione in single human erythrocytes by capillary zone electrophoresis with electrochemical detection

Glutathione (GSH) in single human erythrocytes is determined by capillary zone electrophoresis with end-column amperometric detection at a gold/mercury amalgam microelectrode. A capillary of 10 microm inner diameter is suitable for determination of GSH in an individual erythrocyte with a good signal-to-noise ratio. The limit of detection is 1 x 10(-7) mol/L or 26 amol and the linear dynamic range is 2 x 10(-7) to 2 X 10(-5) mol/L for the capillary. In this method, the calibration line is obtained with a capillary adsorbed before a certain amount of hemoglobin can be used for the quantification of GSH in the external standardization. The whole cell injection and the lack of necessity of a derivatization reaction lead to more accurate and precise results, which are closer to the macroscopic values of glutathione in human red blood cell (i.e., hemolysate) than those determined by indirect laser-induced fluorescence detection.     

Supramolecular framework adducts constructed of hexamethylenetetramine,aquated alkali metal cationic clusters,and hexacyanoferrates(II/III)

The reaction of alkali metal hexacyanoferrate(II/III) with (CH₂)₆N₄ (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK₂[Fe¹¹¹(CN)₆]·2HMT·4H₂O, H₂K₂[Fe¹¹(CN)₆]·2HMT·4H₂O, and HNa₂[Fe¹¹¹(CN)₆]· 2HMT·5H₂O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)₆]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate.     

Fragmentation of N-linked glycans with a matrix-assisted laser desorption/ionization ion trap time-of-flight mass spectrometer

N-Linked glycans were ionized from several matrices with a Shimadzu-Biotech AXIMA-QIT matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometer. [M+Na]+ ions were produced from all matrices and were accompanied by varying amounts of in-source fragmentation products. The least fragmentation was produced by 2,5-dihydroxybenzoic acid and the most by alpha-cyano-4-hydroxycinnamic acid and 6-aza-2-thiothymine. Sialic acid loss was extensive but could be prevented by formation of methyl esters. Fragmentation produced typical low-energy-type spectra dominated by ions formed by glycosidic cleavages. MS(n) spectra (n = 3 and 4) were used to probe the pathways leading to the major diagnostic ions. Thus, for example, an ion that was formed by loss of the core GlcNAc residues and the 3-antenna was confirmed as being formed by a B/Y rather than a C/Z mechanism. The proposed structures of several cross-ring cleavage ions were confirmed and it was shown that MS3 spectra could be obtained from as little as 10 fmol of glycan.     

Chemical studies on the anobiidae: Sex pheromone of the drugstore beetle, stegobium paniceum (L.) (coleoptera)

Chemical an spectroscopic evidence is presented to show that 2,3-dihydro-2,3,5-trimethyl-6-(1-methyl-2-oxobutyl)-4H-pyran-4-one (10) is the sex pheromone produced by the female drugstore beetle, Stegobium paniceum L.     

Matrix-dependent instability of selenium(IV) stored in teflon containers

Solutions of selenium(IV) standards with different acid matrices were stored in containers constructed of boosilicate glass, conventional polyethylene, and fluorinated ethylenepropylene (teflon FEP). After 50 days of storage in FEP, there were highly significant losses of Se(IV) from standards in either 5% HCl/5% H₂SO₄, or 5% H₂SO₄. Increasing the hydrochloric acid concentration, e.g., 15% HCl/5% H₂SO₄, greatly reduced this loss. Addition of selenium-75 (selenate-free) indicated that the losses did not result from physical adsorption onto container surfaces. It is shown that the losses were caused by oxidation of Se(IV) to Se(VI).     

The spectrophotometric determination of zirconium with disodium 3-hydroxy-4-[(6-methyl-2-pyridyl)azo]-2,7-naphthalenedisulfonate N-oxide

Summary The application of the reagent for the spectrophotometric determination of traces of zirconium is described. The effects due to acid concentration, reagent concentration, time and diverse ions are reported. Beer's law is obeyed and the molar absorbance coefficient at 577 nm is 3.2×10⁴.

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Die spektrophotometrische Bestimmung von Zirkonium mit Natrium-3-hydroxy-4-[(6-methyl-2-pyridyl) azo]-2,7-naphthalindisulfonat-N-oxid

Zusammenfassung Die Anwendung des genannten Reagens auf die spektrophotometrische Bestimmung von Zirkoniumspuren wurde beschrieben. Der Einfluß der Säurekonzentration, der Reagenskonzentration, der Zeit und verschiedener Fremdionen wurde untersucht. Das Beersche Gesetz wird befolgt; der molare Extinktionskoeffizient bei 577 nm beträgt 3,2 · 10⁴.

     

Investigations on the behaviour of acidic, basic and neutral compounds in capillary electrochromatography on a mixed-mode stationary phase

This work describes the separation of acidic, basic and neutral organic compounds as well as inorganic anions in a single run by capillary electrochromatography employing a stationary phase which exhibits both strong anion-exchange and reversed-phase chromatographic characteristics. The positive surface charge of this stationary phase provided a substantial anodic electroosmotic flow. The analytes were separated by a mixed-mode mechanism which comprised chromatographic interactions (hydrophobic interactions, ion-exchange) as well as electrophoretic migration. The influence of ion-exchange and hydrophobic interactions on the retention/migration of the analytes could be manipulated by varying the concentration of a competing ion and/or the amount of organic modifier present in the background electrolyte. Additionally the effects of pH changes on both the chromatographic interactions as well as the electrophoretic migration of the analytes were investigated.     

Development of a new reaction system for the synthesis of highly optically active alpha,gamma-substituted gamma-butyrolactones

A highly useful method for the synthesis of optically active alpha,gamma-substituted gamma-butyrolactones has been developed. The SmI(2)-induced reductive coupling of chiral 2-alkyl acrylates derived from isosorbide with ketones in the presence of (1S)-(-)-2,10-camphorsultam as a proton source give the chiral alpha,gamma-substituted gamma-butyrolactones in good yields and high enantiomeric purities (up to >99% ee for trans and 75% ee for cis). The reaction system has been investigated with various ketones, and it is demonstrated that this system is very effective for trans-alpha,gamma-substituted gamma-butyrolactones. Both the chiral auxiliary and the hindered proton source in this system are necessary for the observed excellent ee values of the products. The absolute configuration of the trans products is assigned on the basis of the X-ray crystal structure.     

Mass spectrometry of nitroazoles: 2—the mass spectra of methyl substituted nitroimidazoles

The mass spectra of six isomers of methylnitroimidazoles are reported and discussed. All compounds exhibit strong molecular ions, along with the characteristic fragmentations of aromatic nitro compounds. In some cases ortho effects—losses of OH^., H₂O, CHO^., CH₂O—are observed, due to interactions of adjacent substituents.     

Reduction of 4-arylidene-1,3-(2H,4H)isoquinolinediones

Catalytic hydrogenation of some 4-arylidene-1,3-(2H,4H)isoquinolinediones (1) afforded the corresponding 4-arylmethyl-1,3-(2H,4H)isoquinolinediones (2) , but reduction of 1 by sodium borohydride gave 4-arylmethyl-1(2H)isoquinolones (isocarbostyrils, 3). Compounds of type 1 studied had aryl substituents phenyl, 3,4-dimethoxyphenyl, 3,4-methyleneoxyphenyl and 2-furyl. In one example of sodium borohydride reduction of an N-methylisoquinolinedione derivative (1) the heterocylic ring was opened, and 2-(1-hydroxymethyl-2-phenylethenyl)-N-methylbenzamide (4) was obtained from 4-benzylidene-2-methyl-1,3-(2H,4H)isoquinolinedione.