Elucidation of structural restraints for phosphate residues with different hydrogen bonding and ionization states.

Solid state NMR spectroscopy and gauge including atomic orbital (GIAO) theoretical calculations were employed to establish structural restraints (ionization, hydrogen bonding, spatial arrangement) for O-phosphorylated l-threonine derivatives in different ionization states and hydrogen bonding strengths. These structural restraints are invaluable in molecular modeling and docking procedures for biological species containing phosphoryl groups. Both the experimental and the GIAO approach show that 31P delta ii chemical shift tensor parameters are very sensitive to the ionization state. The negative values found for the skew kappa are typical for -2 phosphates. The distinct span Omega values reflect the change of strength of hydrogen bonding. For species in the -1 ionization state, engaged in very strong hydrogen bonds, Omega is smaller than for a phosphate group involved in weak hydrogen bonding. For phosphates in the -2 ionization state, Omega is significantly smaller compared to -1 species, although the kappa for -1 samples never reaches negative values. For -1 phosphate residues, in the case when 1H one pulse and/or combined rotation and multiple pulse spectroscopy (CRAMPS) sequences fail and assignment of proton chemical shift is ambiguous, a combination of 1H-(13)C and 1H-(31)P 2D heteronuclear correlation (HETCOR) correlations is found to be an excellent tool for the elucidation of 1H isotropic chemical shifts. In addition, a 2D strategy using 1H-(1)H double quantum filter (DQF) correlations [a back-to-back (BABA) sequence in this work] is useful for analyzing the topology of hydrogen bonding. In the case of a multicenter phosphorus domain, 2D 31P-(31)P proton driven spin diffusion experiments give information about the spatial arrangement of the phosphate residues.

High-resolution solid-state NMR spectroscopy as a tool for investigation of enantioselective inclusion complexation.

In this paper, we showed the application of solid state-NMR (SS NMR) spectroscopy in structural studies of chiral compounds employing sample of (E)-1-diphenylphosphinoylpent-3-en-2-ol 1 as a model compound. Racemate of 1 was fully characterized by NMR techniques (both in liquid and solid phase) and X-ray crystallography. Theoretical calculations employing the GIAO approach were used to explain the influence of hydrogen bonding on 31P NMR shielding parameter in racemate. Enantioselective inclusion complexation (EIC) method with TADDOL as host molecule was applied to separate of enantiomers. The formation of host-guest complex and decomplexation procedure was monitored by means of the SS NMR. The liquid-state NMR, due to similarity of 13C and 31P spectral parameters was not able to distinguish racemate from enantiomer. In the solid phase, owing to distinction of hydrogen bonding and molecular packing in the crystal lattice, racemate and enantiomers were easy recognized by NMR spectroscopy.

Distance measurements in disodium ATP hydrates by means of 31P double quantum two-dimensional solid-state NMR spectroscopy.

POST-C7 measurements provide constraints allowing distinguishing crystal lattice organization and establishing intra and/or intermolecular distances between phosphorus atoms of triphosphate chains for different hydrates of disodium ATP salts. Double-quantum efficiency in function of excitation time obtained from series of two-dimensional spectra for POST-C7 experiments was used to set up of buildup curves and semi-quantitative measure of 31P-31P length.

Wilson's disease-cause of mortality in 164 patients during 1992-2003 observation period.

We studied the cause of death in a consecutive series of 164 patients with Wilson's disease (WD) diagnosed over an 11 year period. A total of 20 [12% (95% CI 10.3-16.0)] died during the observation period. The relative survival rate of all patients in our group was statistically smaller than in Polish population. The main cause of death was the diagnosis in advanced stage of disease, but in six patients presenting with mild signs, we observed the progression of the disease despite treatment. There was no difference in mortality rate in patients treated with d-penicillamine or zinc sulphate as initial therapy. The prognosis for survival in the majority of WD patients is favourable, provided that therapy is introduced early.

Effects of long-term treatment in Wilson's disease with D-penicillamine and zinc sulphate.

The results of treatment with D-penicillamine (D-P) or zinc sulphate (Zn) in 67 newly diagnosed cases of Wilson's disease have been compared. All patients (7 with hepatic, 1 with psychiatric and 59 with neurological or preclinical forms) were fully compliant. During 12 years of observation, 34 patients received d-P and 33 Zn as the primary treatment. Fifteen patients (44%) discontinued D-P, in 10 cases owing to side effects. Four (12%) patients discontinued Zn, in 2 cases because of side-effects. One patient who received Zn deteriorated during the first few months after the initiation of therapy. The effectiveness of long-term treatment with D-P and Zn was similar in those patients who were able to continue the initial therapy. Zn was tolerated better than D-P; we suggest, therefore, that it may be recommended as an initial therapy for patients in the preclinical stage of Wilson's disease or with neurological presentation of the disease. More observation is needed for patients with the hepatic and psychiatric forms of the disease.

Gamma delta + T cells in Wilson's disease.

Little is currently known about the role of gamma delta + T cells in disease pathogenesis. We have demonstrated elevated levels of gamma delta + T cells in the peripheral blood and cerebrospinal fluid of patients with Wilson's disease compared with other neurological diseases. The percentage of V delta 1 +/ gamma delta + T cells was between 20% and 50% in all patient groups; gamma delta + T cells in blood correlated with copper concentrations. The antigen reactivity of gamma delta + T cells and how the antigens relate to the gamma delta + T cells found in WD remains unknown. It remains unclear whether there is a direct reason for the elevated gamma delta + T cells population found in WD. Immunohistochemistry of frozen autopsy material from brain and liver of WD patients could allow exact localization of gamma delta + T cells and heat shock proteins in future studies.

[Evaluation of potassium iodide in Polish dietary salt]. / Ocena prawidlowosci jodowania krajowej soli spozywczej.

The consequences of iodine deficiency occurring still in Poland include serious health disorders in the population, such as psycho- somatic retardation, hypothyroidism, endemic goitre, even cretinism. Administration of iodized edible salt with daily diet is an effective method for prevention of iodine deficiency. The condition of success is the proper level of potassium iodide in this salt and adequate distribution of iodized salt in various regions of the country. Successful iodine prophylaxis should be based on iodination of edible salt in amounts of 30 +/- 10 mg of KJ/kg. The permission given in the period from February to May 1994 by the General Sanitary Inspector for the production and marketing of edible salt iodized in proportions of 30 +/- 10 mg KJ/kg opened the possibility of starting its production in salt mines. The purpose of the presently reported work was to assess, in cooperation with the Province Sanitary Epidemiological Stations, the adequacy of iodination of the Polish edible salt produced in the years 1994-1995. The study was carried out according to the Polish Standard "Salt (Sodium Chloride) /PN-80/C-84081.35. Potassium iodide determination by photo colorimetric method." In 1995 the number of edible salt samples analyzed was 2484, and this number included 2129 samples of iodized salt. Potassium iodide content agreeing with the above permission was found in 122 samples, that is in 57.4% of iodized salt samples. In 603 samples (28.3%) of iodized salt this content was below that given in the permissions. In 1994 this study was carried out taking 2172 samples of edible salt, including 1586 samples of iodized salt. The content of potassium iodide agreeing with the permissions (30 +/- 10 mg/kg) was found in 342 samples (28, 1%), but 272 (22.4%) samples of iodized salt produced by salt mines contained lower amounts of potassium iodide than the amount indicated in the permissions, but still within the limits set down in the Polish Standard (20 +/- 5 mg/kg). The obtained results (57.4%) indicate an improvement of the process of salt iodination as compared with the results obtained in 1992 and 1993 (38.3%) and 1994 (28.1%). However, varying amounts of potassium iodide differing from the accepted values were found in salt declared as iodized.

[Wilson disease with HCV infections]. / Wspólistnienie choroby Wilsona z zakazeniem wirusem C

In this paper we describe liver-related Wilson's disease in two sisters. The elder died of liver failure. Our patient, a 13-year old girl has hepatitis C coinfection. Gradual improvement was observed after Cuprenil, Zincteral and interferon (Intron A).

[Repeated radical operations in patients with a diagnosis of inoperable rectal cancer]. / Powtórne, radykalne operacje u chorych z rozpoznaniem nieoperacyjnych raków odbytnicy.

Three cases are presented of patients with rectal cancer, in whom the decision of radical operation was abandoned during surgical intervention. In these patients radical operation was done during repeated surgery.

[Determination of potassium iodide in Polish edible salt]. / Ocena zawartosci jodku potasowego w krajowej soli spozywczej.

The purpose of the study was to assess the correctness of salt iodination and its distribution in Poland. The subject of the study was salt for human consumption iodinated or not, according to Polish norm PN-88/C-84081/02 "Sól (chlorek sodowy). Requirements. Salt samples were taken from retail shops or stores in 36 provinces. The study was carried out in the years 1992-1993 according to PN-80/C-84081.35 "Sól (chlorek sodowy) standard. Potassium iodide was determined by photo-colorimetry. The total number of studied salt samples was 3418, including 2440 samples of iodinated salt. The per cent of samples with proper content of potassium iodide was from 30% to 50% depending on the producer. The study demonstrated that in most cases the process of salt iodination is done incorrectly.

[Content of nitrates in vegetables and potatoes 1987-1991]. / Zawartosc azotanów w warzywach i ziemniakach 1987-1991.

The purpose of the study was the assessment of nitrate content in vegetables and potatoes in relation to the acceptable levels of nitrates. The samples for the study were taken by workers of the Province Sanitary- Epidemiological Stations in 39-42 provinces, depending on the season of sampling. The samples were taken from retail shops. Nitrate content was determined by spectrophotometry after previous reduction in cadmium column. The study was conducted in the years 1987-1991. A total of 13,075 samples were analysed. The nitrate levels in excess of the acceptable values were found in 3.2 to 49.9% of the samples, depending on vegetable species. In the case of all vegetables and potatoes the value of the median of the nitrate content was never above the acceptable level. Permanent and systematic control of nitrate levels in vegetables and potatoes is mandatory.