Spectral and structural studies of dimethylphenyl betaine hydrate.

Hydrates of betaines can be divided into four groups depending on the interactions of their water molecules with the carboxylate group. Dimethylphenyl betaine crystallizes as monohydrate (1), in which water molecules mediate in hydrogen bonds between the carboxylate groups. The water molecules are H-bonded only to one oxygen atom of the dimethylphenyl betaine molecules and link them into a chain via two O(1W)-H⋯O hydrogen bonds of the lengths 2.779(2) and 2.846(2)Å. The structures of monomer (2) and dimer (4) hydrates in vacuum, and the structure of monomer (3) in an aqueous environment have been optimized by the B3LYP/6-311++G(d,p) approach and the geometrical results have been compared with the X-ray diffraction data of 1. The calculated IR frequencies for the optimized structure have been used for the assignments of FTIR bands, the broad absorption band in the range 3415-3230 cm(-1) has been assigned to the O(1w)-H⋯O hydrogen bonds. The correlations between the experimental (1)H and (13)C NMR chemical shifts (δexp) of 1 in D2O and the magnetic isotropic shielding constants (σcalc) calculated by the GIAO/B3LYP/6-311G++(d,p) approach, using the screening solvation model (COSMO), δexp =a+b σcalc, for optimized molecule 3 in water solution are linear and well reproduce the experimental chemical shifts.

Spectroscopic and structural investigation of 2,5-dicarboxy-1-methylpyridinium inner salt.

The structure of 2,5-dicarboxy-1-methylpyridinium inner salt (1), has been studied by X-ray diffraction, B3LYP/6-311G(d,p) calculations, FTIR, Raman and NMR spectroscopy. The molecules are linked by short intermolecular and asymmetric O-H⋯O hydrogen bonds of 2.486(2)Å between carboxyl and carboxylate groups of neighboring molecules into infinite chains. The hydrogen bonds in the molecules optimized by the B3LYP/6-311G(d,p) approach in trimer (2) and dimer (3) are slightly longer than in the crystal. The FTIR spectrum of the investigated inner salt is dominated by a broad and intense absorption in the 1500-800 cm(-1) region attributed to the ν(as)(OHO) and γ(OHO) vibrations of the strong hydrogen bond. In the Raman spectrum the broad absorption is absent. Linear correlations, δ(exp)=a+b σ(calc) between the experimental (1)H and (13)C NMR chemical shifts (δ(exp)) of the investigated inner salt in D2O and the calculated magnetic isotropic shielding constants (σ(calc)) for the optimized monomer (4a) solvated in water are reported. The pKa value for 1 of 2.31±0.02 was determined by the potentiometric titration.

Structure and conformation of 2,3-diethoxycarbonyl-1-methylpyridinium iodide studied by NMR, FTIR, Raman, X-ray diffraction and DFT methods.

Computational and spectroscopic properties of 2,3-diethoxycarbonyl-1-methylpyridinium iodide, 1, were studied. The crystal structure of 1 was analyzed by X-ray diffraction. Molecular geometry of title compound has been calculated using the density functional theory (DFT) at B3LYP/6-311G(d,p) level of theory and was compared with the experimental data. Iodide anion interacts electrostatically with the positively charged pyridinium nitrogen atom and via weak CH⋯I(-) hydrogen bonds. In crystals the N-methyl and ethoxycarbonyl groups are disordered in two orientations. The structures of 2 (in vacuum), 3 (in CHCl3) and 4 (in DMSO) optimized by the B3LYP/6-311G(d,p) approach are different than that in crystal 1. The experimental (13)C and (1)H chemical shifts (δexp) of the investigated ester in CDCl3 and DMSO-d6 correlate linearly with GIAO/B3LYP/6-311G(d,p) magnetic isotropic shielding constants calculated according to the screening solvation model (COSMO), δexp=a+b σcalc. The FTIR and Raman spectra of the solid compound are consisted with the X-ray structure.

[Alpha-L-fucosidase activity in patients with ductal cholelithiasis]. / Alfa-L-fukozydaza u chorych z przewodowymi postaciami kamicy zólciowej.

Alpha-L-fucosidase (ALF), AST, ALT and GGT activities were measured in blood serum of 36 patients with recurrent cholelithiasis (group I), 32 patients with ductal and/or bladder cholelithiasis (group II), 24 patients with focal changes in the liver (group III) and in 22 patients without disturbances of gastrointestinal tract (control group). A statistically significant increase in ALF activity was found in the patients with recurrent cholelithiasis as compared to the control group (p < 0.001), the patients of group II (p < 0.001) and the patients of group III (p < 0.05). The AST and ALT activities were higher both in group I and in group II than in the control group (p < 0.001 and p < 0.02 for group I and group II, respectively), whereas the mean GGT activity was significantly higher in all three patients groups as compared to the control group (p < 0.001 in all cases). On the basis of the observed differences in the activities of the enzymes studied it was postulated that the determination od ALF activity in blood serum of patients with cholelithiasis may provide the means for early diagnosis of the predisposition to recurrent stones.

[Analysis of changes in concentration of glycosylated hemoglobin and fructosamine during the first three weeks of treatment of children with newly diagnosed insulin-dependent diabetes]. / Analiza zmian stezenia hemoglobiny glikozylowanej i fruktozaminy w okresie trzech pierwszych tygodni leczenia dzieci ze swiezo rozpoznana cukrzyca insulinozalezna.

Blood serum fructosamine and blood glycosylated hemoglobin (HbA1) concentrations were determined in 47 children with newly diagnosed insulin-dependent diabetes during their first stay in the hospital. Three determinations at week's intervals were carried out in each patient. The mean values of concentration decrement after the first, second and third week of treatment were 0.47, 0.37 and 0.26 mmol/l, respectively, (median values 0.56, 0.33 and 0.17 mmol/l) for fructosamine concentration, and 1.8, 2.9 and 1.0% (median 1.5, 2.3 and 0.8%) for HbA1. No correlation was found between the weekly decrement values in fructosamine and HbA1 concentrations when all the values were taken into consideration, and only a slight positive correlation when the decrement after two weeks of treatment was considered (r = 0.57, p < 0.05). Very high rate of decrease in the concentration of glycosylated hemoglobin was noted in some children, reaching the values from 4 to even 8.6% per week.

[Epidemiologic studies after the disaster in Czernobyl in the population of children in the Krakow region]. / Badania epidemiologiczne po awarii w Czarnobylu w populacji dzieci w regionie krakowskim.

In 1989-1990 the epidemiologic studies about the impact of of Czarnobyl events on the health of children in Kraków and Nowy Sacz region were performed. The morphologic and functional changes of thyroid gland in children were estimated. Almost 90% of children in both districts received the iodine preparations for prophylactic reason. The mean time of intake was between 5-10 days following the Czarnobyl explosion. There were no relationship between the dose of iodine absorbed during prophylactic action and incidence of goiter. The prevalence of goiter amounted to 34.8-47.6% in boys and girls consecutively in Kraków district and 53.8-70.5% in Nowy Sacz. No hormonal changes in T3, T4 and TSH serum concentration were found in children with goiter and those without goiter. The complications after iodine intake were transient and seen only in a small number of children.

The relation between the results of determination of fructosamine and glycosylated proteins of blood serum.

Fructosamine concentration (measured by NBT reduction method) and the concentration of glycosylated proteins (measured by a direct UV spectrophotometry upon separation from nonglycosylated proteins by means of affinity chromatography, have been determined simultaneously in 52 samples of blood serum obtained from 42 children with diabetes mellitus and 10 children without metabolic disorders. A highly significant positive correlation (r = 0.96, p < 0.001) was found between the two parameters. It was concluded that fructosamine determination by NBT reduction test reflects the true concentration of glycosylated proteins of blood serum, provided that the proper correction factor derived from the equation of linear regression is used as shown in the following equation: Concentration of glycosylated proteins of blood serum in milligram = 2.78 x (fructosamine concentration in mmol/l + 1.26).

Free amino acids in basal and vagally stimulated gastric secretion.

The concentrations of the individual free amino acids were determined in one hour fraction of basal secretion and peak hydrogen ion secretion following stimulation with 2-deoxy-D-glucose (2-DG) (group I) or insulin (group II). Group I consisted of 9 patients with duodenal ulcer having hypersecretion of gastric acid as determined by histamine test; 7 patients with duodenal ulcer who underwent truncal vagotomy and had insulin test performed two weeks after the operation formed group II. The total concentration of free amino acids was similar in basal and in stimulated gastric juice in both groups. Also the concentrations of the individual amino acids did not change significantly after stimulation. There was, however, a significant increase following stimulation in the output of amino acids both in group I and in group II. This increase was parallel to that in the volume of gastric juice, which suggests that a definite amount of free amino acids is always present in the gastric juice, and that the secretion of these acids is not under vagal control.

[Monotherapy of epileptic children with monitoring of the serum levels of anticonvulsive drugs]. / Monoterapia u dzieci chorych na padaczke z wykorzystaniem monitorowania stezen leków przeciwpadaczkowych w surowicy krwi.

In 46 children with partial and primarily generalized seizures monotherapy was started with amizepine, luminal, mysodin or phenytoin. The treatment was monitored determining serum concentrations of the drugs. Monotherapy was effective in 74% of cases. In 89% of them the duration of treatment was one year, at least. In some children the values of amizepine, luminal and mysodin concentrations below the therapeutic level were effective. The evolution of electroencephalographic changes failed to correspond strictly to the clinical results of the treatment.

Sequential hydrolysis of three acyl ester bonds in triolein molecule by human gastric juice lipase.

Specificity of gastric juice lipase concerning the sequential hydrolysis of three acyl ester bonds of triolein molecule has been compared with that of pancreatic lipase. The rates of the individual hydrolytic steps were calculated by applying the method based on the amounts of chromatographically separated hydrolysis products present upon the incubation of tritium-labelled triolein with a lipolytic enzyme. It was found that in the case of gastric lipase the rates of all three steps of triolein hydrolysis are similar, whereas in the case of pancreatic lipase the last step proceeds at a much slower rate than the preceding ones.