Synthesis of peptides based onβ-(N1-uracilyl)-α-alanine

The synthesis of peptides which include a DL--(N₁-uracilyl)--alanine (DL-willardiine) residue as an N-terminal or C-terminal group was investigated, dipeptides of DL-willardiine with glycine and L-tyrosine were obtained, and DL-willardiyl-DL-willardiine was synthesized; the latter is the simplest representative of the family of monotonic homopeptides which contain, as a repeating side substituent, a natural nucleic base capable of participation in intermolecular interactions of the complementary type.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 404–408, March, 1971.     

Influence of ethanol oxidation rate on the lactate/pyruvate ratio and phosphorylation state of the liver in fed rats.

The effect of the ethanol oxidation rate on the interaction between the phosphorylation state (the [ATP]/[ADP] X [HPO4]2- ratio) and the redox state (the free [NAD+]/[NADH] ratio) of the liver cytosol was studied in intact fed rats. The rate of ethanol oxidation was inhibited to different degrees with pyrazole. The ethanol oxidation rate had no influence on the liver lactate level but correlated significantly with the pyruvate level. Accordingly, a significant correlation was also found between the ethanol oxidation rate and the lactate/pyruvate ratio. The rate of ethanol oxidation correlated significantly with the liver 3-phosphoglycerate level. No change in the glyceraldehyde-3-phosphate level was found. No correlation was found between the ethanol oxidation rate and the glyceraldehyde-3-phosphate/3-phosphoglycerate redox couple. Ethanol administration slightly increased the liver ATP level, but the simultaneous administration of pyrazole eliminated this effect. Other adenine nucleotides and HPO4 2- were not changed. The changes in the rate of ethanol oxidation had no effect on the phosphorylation state in the fed liver. It is assumed that in the fed liver the phosphorylation state is so well stabilized that the redox level has no influence.     

Synthesis of polycyclic structures by the Diels-Alder reaction of inner-outer-ring 1,3-bis(trimethylsilyloxy)dienes

A Diels-Alder reaction of novel inner-outer-ring 1,3-silyloxydienes 5-8 with a variety of dienophiles to afford highly functionalized polycyclic structures is reported. The inner-outer-ring 1,3-silyloxydienes 5-8 containing five- to seven-membered carbocyclic and heterocyclic rings were prepared in a single reaction vessel from 2-acetylcyclocarbonyls in quantitative yields. The Diels-Alder reaction with 1,4-benzoquinone (BQ), dimethyl acetylenedicarboxylate (DMAD), and methyl vinyl ketone (MVK) proceeded smoothly at room temperature, affording functionalized polycyclic naphthols, phenols, and enones with high regioselectivity and good yields (39-75%). Moreover, dienes 5-8 also reacted in a hetero-Diels-Alder reaction with benzaldehyde (BA) and N-benzylideneaniline (NBA) in the presence of catalytic amounts of ZnCl2, affording substituted polycyclic pyranones and pyridinones in good yields (40-93%). Overall, our synthetic strategy provides straightforward access to an interesting set of polycyclic structures useful for natural and nonnatural product synthesis.     

Determination of lithium in human serum by electrothermal atomic absorption spectrometry

An efficient method was developed for the determination of nanogram levels of lithium in biological samples. Serum samples from human subjects from southeastern Spain, treated or not treated with lithium carbonate, were analyzed by electrothermal atomic absorption spectrometry. The samples were previously treated with a matrix modifier consisting of 0.1% Triton X-100 and injected through a graphite tube with L'vov platform. The Li concentrations measured by the procedure described for the 3 certified reference samples used were not significantly different (p > 0.05) than certified levels. Sample recoveries and variability during several days, with coefficients of variation from 4.00 to 14.8%, demonstrated the reliability and accuracy of this technique. Mean Li concentration determined in the serum of individuals with psychiatric disorders treated with Li (n = 117, 5.077 +/- 1.795 microg Li/mL) was significantly higher (p < 0.001) than that in individuals not treated with Li (n = 24, 1.902 +/- 2.054 ng Li/mL).     

Use of diode-array detectors for the simultaneous spectrophotometric determination of calcium and magnesium by flow injection

A method for the simultaneous flow injection spectrophotometric determination of calcium and magnesium with Arsenazo III based on the use of diode-array detector and merging zones is described. The method is applicable to the resolution of mixtures in which the chromogenic reagent has a high absorbance and its spectrum strongly overlaps those of its complexes. In resolving the mixtures, the excess reagent is considered as another component. Quantitation is based on the normal absorbance and first-derivative absorbance spectra. The method is applied to 0.2–1.5 μg ml^?1 Ca and 0.1–1.0 μg ml^?1 Mg. The analysis rate is 50 h^?1.     

Synthesis and properties of esters and amido esters of 1-(2-thienyl)-2,2,2-trichloroethylphosphorous acid

Conclusions The esterification of amido- and ester-amidophosphites with 1-(2-thienyl)-2,2,2-trichloroethanol gave the l-(2-thienyl)-2,2,2-trichloroethyl dialkyl- and 1-(2-thienyl)-2,2,2-trichloroethyl alkylamidophosphites, which easily add sulfur or are oxidized to the corresponding thiophosphates and phosphates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 182–187, January, 1981.     

Determination of four nitroimidazole residues in poultry meat by liquid chromatography-mass spectrometry

A multi-residue liquid chromatography-mass spectrometry (LC-MS) assay method is described for the determination of four nitroimidazoles in poultry muscle. The extraction procedure is based on liquid-liquid extraction with ethyl acetate followed by an evaporation step. A deuterated internal standard is used. The LC separation was made on a C18 bonded silica column with an aqueous formic acid (0.2%) solution-methanol-acetonitrile (81:13:6) mobile phase. Following electrospray ionization, the protonated molecular ion [M+H]+ is obtained for each compound. Monitoring several ions for each nitroimidazole provides the specificity required for confirmatory assay. Validation of the method was performed to estimate linearity, intra-day and inter-day repeatability, accuracy and detection limit. The present method is capable of identifying nitroimidazole residues in muscle at levels below 5 microg/kg.     

Rapid and sensitive liquid chromatographic determination of carbamazepine suitable for use in monitoring multiple-drug anticonvulsant therapy.

A rapid, sensitive and selective method for the determination of carbamazepine and its major metabolite in plasma has been developed. Other commonly used anticonvulsants can be determined in the same procedure without interference. After extraction with dichloromethane, the components are separated by high-pressure liquid chromatography without further clean-up or concentration on a column packed with small-particle silica gel. The mean recovery from plasma is 98.6% with a relative standard deviation of 1.6%. The detection limit for carbamazepine is approximately 2 ng/ml, requiring 1 ml of plasma.     

Reaction of mercury(II) and xylenol orange-I Effect of the buffering media

The influence of the buffering medium on the reaction of Hg(II) with Xylenol Orange has been studied. Amine-type compounds are complexed by Hg(II)/Xylenol Orange with a sharp hyperchromic effect on the reagent itself, at 590 nm, but complex formation of Hg(II)/Xylenol Orange in non-amine-type buffer, such as citric acid-phosphate, gives a hypochromic effect on Xylenol Orange at 580 nm. Hg(II) is determined at pH 7.5 in two ranges of concentration, 2-9 ppm in citrate buffer, measured at 580 nm ( = 2.50 x 10(4)), and 6-11 ppm in hexamine buffer, at 590 nm ( = 4.18 x 10(4)).     

Crystal structure and magnetic structure of TbOOH

The monoclinic modification of terbium oxide hydroxide, TbOOH, was prepared using hydrothermal technique. The crystal structure was investigated by three-dimensional single-crystal X-ray analysis and was refined to a conventional R-value of 8.1%. The space group is $\text{P2}{}_1\text{m}$, No. 11, with a = 6.04 Å, b = 3.69 Å, c = 4.33 Å, and β = 109.0°. The terbium atom is seven coordinated with oxygen atoms, and the structure is not hydrogen bonded.The compound is antiferromagnetic with a Néel temperature of 10°K. Neutron diffraction powder patterns were measured at 300°K and 4.2°K. The magnetic super lattice reflections were indexed on the basis of a monoclinic unit cell with the dimensions a_M = 2a, b_M = b, c_M = c, and β_M = β, where a, b, c, and β are the dimensions of the chemical unit cell. The structure contains two independent magnetic atoms. A nonclinear antiferromagnetic arrangement of the spins describes the magnetic structure. The spin at one atom has an angle of 43° with the ac plane and the projection of the spin on the ac plane has an angle of 59° with the a axis. The spin on the other atom has an angle of ?43° with the ac plane, the projection having the same angle of 59° with the a axis.