Structural interpretation of the 31P NMR chemical shifts in thiophosphate and phosphate: key effects due to spin-orbit and explicit solvent.

Structural interpretation of the 31P NMR shifts measured in O,O-diethyl thiophosphate (PT), 5,5-dimethyl-2-mercapto-1,3,2-dioxaphosphorinane 2-oxide (cPT), diethylphosphate (P) and 5,5-dimethyl-2-hydroxy-1,3,2-dioxaphosphinane 2-oxide (cP) was obtained by means of theoretical calculations including the effects of geometry, molecular dynamics, and solvent, relativistic effects and the effect of NMR reference. NMR calculations employed the B3LYP, BP86, BPW91, M06-2X, PBE0, MP2, and HF methods, the Iglo-n (n = II, III), cc-pVnZ (n = D, T, Q, 5), and pcS-n (n = 0, 1, 2, 3, 4) Gaussian-type basis sets and the Slater-type QZ4P atomic basis. Water solvent was described explicitly and/or implicitly. The effects due to molecular dynamics were calculated using molecular dynamics simulations with the GAFF force field and the TIP3P water molecules, and alternatively by means of the zero-point ro-vibrational averaging. Relativistic effects included the spin-orbit calculated within the two-component zero-order relativistic approximation and the effect with the four-component DFT method. Optimal geometries and large-amplitude dynamical motions within the "opened" PT and P molecules contrasted with notably different geometries and confined dynamical motions within the cPT and cP "closed" molecules. These structure-dynamical differences together with the different chemical structures of thiophosphate and phosphate due to a non-esterified sulphur or oxygen atom within the group considerably affected the magnitudes of 31P NMR shifts. The theoretical calculations enabled accurate and reliable structure-dynamical interpretation of the measured 31P NMR shifts. The effects due to explicit solvent and relativity turned out to be indispensable for obtaining accurate 31P NMR shifts particularly in the thiophosphates. Replacement of the non-esterified oxygen atom in the phosphate with sulphur makes NMR shielding of the phosphorus atom qualitatively different as compared to the NMR shielding of the phosphorus atom in phosphate, H3PO4 and PH3.

[Malignant melanoma of soft parts (clear cell sarcoma)--a rare case of multiorgan localization]. / Malígny melanóm mäkkých castí (svetlobunkový sarkóm)--raritný prípad viacorgánovej lokalizácie.

Malignant melanoma of soft parts (MMSP) is a rare tumor originally described by Enzinger in 1965 as clear cell sarcoma of tendons and aponeuroses because of its affinity to tenosynovial structures. Tumors are found predominantly at the extremities. First visceral case was described in 1993 in the duodenum. We describe the case of 64-years old man with malignant melanoma of soft parts in the stomach, in the pancreas, in the mesocolon, in the left thigh and in the left axilla. This patient was successfully treated surgically by the resection of the stomach, resection of the pancreatic head, extirpation of the tumor from mesocolon, from the left thigh and from the left axilla. In all these localisations the tumor was histologically and imunohistochemically proved to be MMSP (positivity: s-100 protein, vimentin, HMB-45 and negativity CK, EMA, desmin, actin). This multivisceral occurrence is extremely rare and according to the review of literature this is probably the first published case of MMSP in the stomach and in the pancreas.

[Hereditary nephropathy with signs of nephrotic syndrome]. / Hereditárna nefropatia s príznakmi nefrotického syndrómu.

The authors submit the description of two sisters with hereditary nephropathy, with symptoms of nephrotic syndrome. In the clinical picture dominated permanent anuria, rapid renal failure and death at the end of neonatal age. Histopathological findings classified the disease as infantile diffuse mesangial sclerosis. The third patient is a sporadic case of primary congenital nephrotic syndrome.

[Congenital nephrotic syndrome]. / Kongenitálny nefrotický syndróm.

Only one case of congenital nephrotic syndrome was recorded in a series of 2,500 bioptic examinations of the kidney performed over a period of 20 years. In necroptic material examined over the same period of time congenital nephrotic syndrome was recorded three times. At the first bioptic examination of the kidneys only minimal changes of glomeruli were diagnosed. Rebiopsy exhibited proliferation of mesangial cells, focal segmental glomerular sclerosis, cystically dilated tubules in the juxtamedular region of the cortex, and focal tubulointerstitial reactive changes, which in accordance with the clinical findings were assessed as congenital nephrotic syndrome of the Finnish type. Comparison of the findings observed at the first biopsy and at rebiopsy demonstrates the importance of proper collection of a representative sample for renal biopsy.

[Thin-needle aspiration cytology of the thyroid gland]. / Tenkojehlová aspiracní cytologie stítné zlázy.

A group of 187 fine needle aspiration cytology materials from thyroid gland was classified according to international cytology classification. The most important diagnostic criteria were presented for single lesions and correctness of cytologic evaluation compared with a complete bioptic finding.

[Cytologic diagnosis of stomach lesions]. / Cytologická diagnostika zaludecních lézí.

A group of 542 gastrofibroscopic cytological samples was compared with simultaneous gastrofibroscopic biopsy. The most important diagnostic criteria of single lesions derived from accepted cytological classification were discussed. Diagnostic value of cytology was advantageous.

[Thin-needle aspiration cytology of the mammary gland]. / Tenkojehlová aspiracní cytologie mlécné zlázy.

Fine-needle aspiration cytology of the Mammary gland proved advantageous and reliable in a group of 387 cases (not any false positivity, 0.7 per cent false negativity). The method is especially usable for prebioptic diagnosis enabling cytostatic therapy before operation on evident carcinomas and for mammary screening.