THz, Raman, IR and DFT studies of noncentrosymmetric metal dicyanamide frameworks comprising benzyltrimethylammonium cations.

We report density functional theory (DFT) studies of vibrational modes for benzyltrimethylammonium cations (BeTriMe+) as well as THz, IR and Raman studies of [BeTriMe][M(dca)3(H2O)] (dca = N(CN)2-, dicyanamide; M = Mn2+, Co2+, Ni2+) and their anhydrous analogues. These studies show that the anhydrous BeTriMeMn and BeTriMeNi have the same or very similar structures and loss of water molecules leads to significant changes in the metal-dicyanamide frameworks. In particular, the number of dca modes decreases, suggesting increase of crystal symmetry, probablly related with decrease in the number of non-equivalent dca bridges from two to one. Although it is possible that dehydration leads to a replacement of the coordinate Mn-O (Ni-O) bonds by Mn-N (Ni-N) bonds, wherein N atoms come from the C≡N groups of previously non-bridged dca units, reversibility of the dehydration process indicates that such new bonds are either not formed or are very weak. The anhydrous Mn and Ni compounds undergo similar reversible phase transitions to lower symmetry phases. The driving force for these transitions is most likely ordering of dca linkers but this process is accompanied by weak distortion of the metal-dicyanamide frameworks. In the case of BeTriMeCo, the loss of water molecules also leads to significant changes in the cobalt-dicyanamide framework. However, the structure of this analogue is different from the structures of the Mn and Ni counterparts, the number of unique dca linkers is preserved and the dehydration process is irreversible, suggesting more drastic rearrangement of the metal-dicynamide framework.

Extensive pneumatisation of the sphenoid bone: anatomical investigation of the recesses of the sphenoid sinuses and their clinical importance.

BACKGROUND: There is a great variance between the extents of pneumatisation of the sphenoid sinuses that can reach beyond the body of the sphenoid bone. The purpose of this study was to find the prevalence of the recesses of the sphenoid sinuses in Polish adult population. MATERIALS AND METHODS: Two hundred ninety-six computed tomography (CT) scans of patients who did not present any pathology in the sphenoid sinuses were evaluated in this retrospective analysis. Spiral CT scanner (Siemens Somatom Sensation 16) was used to glean the medical images. Standard scan procedure was applied, with Siemens CARE Dose 4D option enabled. No contrast medium was administered. RESULTS: In the majority of the patients (93.92%), the pneumatisation of the sphenoid sinuses expanded beyond the body of the sphenoid bone; hence, there were recesses of the sinuses present. The most common variant was the presence of two recesses - 12.84% of cases. The prevalence of all the 17 recesses was only 0.34%. Amongst the uneven recesses present, the sphenoidal rostrum's recess (61.15% of the patients) and the inferior clinoid recess (56.42%) were the most common. Amongst the even recesses present, the lateral recess was prevalent in the majority (65.88%), whereas the posterior clinoid process' recess was the least common (9.8%). CONCLUSIONS: Presence of the recesses might facilitate access to the cranial fossae; hence, comprehensive evaluation of the sphenoid sinuses is of immense importance in order to avoid unnecessary drills through the hard bone, which could potentially damage the nearby neurovascular structures.

Protrusion of the carotid canal into the sphenoid sinuses: evaluation before endonasal endoscopic sinus surgery.

BACKGROUND: Many reports have previously indicated the vast number of anatomical variations of the sphenoid sinuses, e.g. presence of the recesses. Notwithstanding, there are a few crucial neurovascular structures directly neighbouring with the sinuses. The following research aimed to evaluate frequency prevalence of the carotid canal's protrusion into the sphenoid sinuses in adult population. MATERIALS AND METHODS: Computed tomography (CT) scans of the paranasal sinuses of 296 patients (147 females, 149 males) were analysed in this retrospective study. The patients did not present any pathology in the sinuses. Spiral CT scanner Siemens Somatom Sensation 16 was used in the standard procedure in the option Siemens CARE Dose 4D. RESULTS: Protrusion of the carotid canal was found in the majority of the patients - 55.74%, more frequently in males (65.1% of the patients) than in females (46.26% of the patients). The said variant - regardless of gender - was noted more often bilaterally (41.55% of the cases: 29.93% females, 53.02% males) than unilaterally (14.19% of the cases: 16.33% females, 12.08% males). In the unilateral type (regardless of gender), the protrusion was more common for the left sphenoid sinus - 10.81% of the patients (12.24% females, 9.4% males) than for the right - 3.38% of the patients (4.08% females, 2.68% males). CONCLUSIONS: Complicated structure of the paranasal sinuses, derived from the high prevalence of their anatomical variations, may perplex routine surgical interventions. Henceforth, referral for a CT scan is imperative in order to abate the risks associated with an invasive procedure in the said region.

Spectroscopic investigation and DFT modelling studies of Eu3+ complex with 1-(2,6-dihydroxyphenyl)ethanone.

Eu3+ complex with 1-(2,6-dihydroxyphenyl)ethanone in the solid state has been synthesized and characterized by elemental analysis, UV-visible, FT-IR and FT-Raman spectroscopies, powder X-ray diffraction, electron emission under femtosecond laser excitation. The stoichiometry and the formula of the studied complex have been proposed. Its physicochemical properties have been analyzed in terms of the structure and DFT calculations performed for the ligand. The luminescence and dynamics of the excited states depopulation have been studied using femtosecond laser excitation. Spectral and energetic transformation of femtosecond light impulses has been studied and possibility of the energy transfer between the ligand and the Eu3+ electron levels has been analyzed.

A large scale prospective clinical and psychometric validation of the EORTC colorectal (QLQ-CR29) module in Polish patients with colorectal cancer.

The purpose of our study was to assess if the Polish translation of the European Organisation for Research and Treatment of Cancer (EORTC) Colorectal Cancer (CRC)-Specific Quality of Life Questionnaire (QLQ-CR29) is an acceptable and psychometrically valid measure to collect quality of life (QoL) data in Polish patients with CRC for use in clinical trials and clinical practice. A total of 150 patients undergoing treatment for CRC were prospectively enrolled in the study. Psychometric assessment of the translated QLQ-CR29 structure, reliability, convergent and divergent validity, and clinical validity was subsequently performed. The Cronbach's alpha coefficient ranged from 0.70-0.89, indicating acceptable internal consistency. For test-retest reliability, the ICCs for each item ranged from 0.59-0.91, with exceptions for urinary incontinence and dysuria, indicating good to excellent reproducibility. In multi-trait scaling analyses, the criterion for item convergent and divergent validity was satisfied. The correlations between the EORTC QLQ-CR29 and QLQ-C30 scales were mostly low (r < .40), with a few items demonstrating higher correlations. The known group comparisons analyses demonstrated the ability of the questionnaire to distinguish between patients' differing age, stoma status, and treatment intent. The Polish translation of the QLQ-CR29 is a psychometrically reliable and valid tool. The results of this study are congruent with that of EORTC validation.

The hydrazo-bond in 4,4'-dimethyl-3,3'-dinitro-2,2'-hydrazobipyridine - crystal structure, conformation and vibrational characteristics.

The crystal and molecular structure of 4,4'-dimethyl-3,3'-dinitro-2,2'-hydrazobipyridine have been determined by X-ray diffraction and quantum chemical DFT analysis. The title compound crystallizes in P1¯ space group, with one-half molecule in the asymmetric unit. The molecular structure is stabilized by intramolecular NH···O hydrogen bonds. The molecules are linked by a combination of weak intermolecular CH⋯O interactions and also aromatic π-π stacking. The molecular structure of the studied compound has been determined using the DFT B3LYP/6-311G(2d,2p) approach and compared to that derived from X-ray studies. The IR and Raman wavenumbers have been calculated for the optimized geometry of a possible monomer structural model. The structural and vibrational properties of the intramolecular NH···O interaction are described.

Conformation of azo-bridge in 3,3'-dinitro-2,2'-azobipyridine and its 4,4'(or 5,5' or 6,6')-dimethyl-derivatives: vibrational studies and DFT quantum chemical calculations.

Syntheses of 3,3'-dinitro-2,2'-azobipyridine and 4,4' (or 5,5' or 6,6')-dimethyl-3,3'-dinitro-2,2'-azobipyridine have been described. Molecular structures of these compounds have been determined and compared, to the basic compound, azobipyridine, reported by us earlier. The conformation of the azo-bond and other structural data are discussed in terms of substitution place of methyl chromophore. Fourier transform IR and Raman spectra of these compounds have been measured and analysed. The 6-311G (2d,2p) basis set with the B3LYP functional have been used to discuss the space conformation and dynamics of the studied compounds.

The role of hydrogen bonds in the crystals of 2-amino-4-methyl-5-nitropyridinium trifluoroacetate monohydrate and 4-hydroxybenzenesulfonate - X-ray and spectroscopic studies.

Two new organic-organic salts, 2-amino-4-methyl-5-nitropyridinium trifluoroacetate monohydrate (AMNP-TFA), and 2-amino-4-methyl-5-nitropyridinium 4-hydroxybenzenesulfonate (AMNP-HBS), were obtained and characterized by means of FT-IR, FT-Raman and single crystal X-ray crystallography. In the former crystal, the cations, anions and water molecules are linked into layers by three types of hydrogen bonds, NPH⋯O, NAH⋯O and OH⋯O. These layers are connected by weaker CH⋯O hydrogen bonds. In the latter crystal, the cations and anions form one-dimensional structure through a number of hydrogen-bonding interactions involving the OH, NH(+) and NH2 groups as donors. In this case the NPH⋯O and NAH⋯O hydrogen bonds are formed. The combination of interactions between cations and anions results in the formation of columns. Additionally, there are π-π stacking interactions between the columns. The obtained X-ray structural data are related to the vibrational spectra of the studied crystals.

Structure, vibrational spectra and DFT characterization of the intra- and inter-molecular interactions in 2-hydroxy-5-methylpyridine-3-carboxylic acid--normal modes of the eight-membered HB ring.

Fourier transform IR and Raman spectra, XRD studies and DFT quantum chemical calculations have been used to characterize the structural and vibrational properties of 2-hydroxy-5-methylpyridine-3-carboxylic acid. In the unit-cell of this compound two molecules related by the inversion center interact via OH⋯N hydrogen bonds. The double hydrogen bridge system is spaced parallel to the (102) crystallographic plane forming eight-membered arrangement characteristic for pyridine derivatives. The six-membered ring is the second characteristic unit formed via the intramolecular OH⋯O hydrogen bond. The geometry optimization of the monomer and dimer have been performed applying the Gaussian03 program package. All calculations were performed in the B3LYP/6-31G(d,p) basis set using the XRD data as input parameters. The relation between the molecular and crystal structures has been discussed in terms of the hydrogen bonds formed in the unit cell. The vibrations of the dimer have been discussed in terms of the resonance inside the system built of five rings coupled via hydrogen bonds.

Comprehensive physicochemical studies of a new hybrid material: 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate.

A new organic-organic salt, 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate (AMNPO), and its deuterium analogue have been synthesized and characterized by means of FT-IR, FT-Raman, DSC and single crystal X-ray studies. The DSC measurements and temperature dependence of the IR and Raman spectra in the range 4-295 K show that it undergoes a reversible phase transition at ~240 K. At room temperature it crystallizes in noncentrosymmetric space group P21. The unit-cell is built of the 2-amino-4-methyl-3-nitropyridinium cations and oxalate monoanions which are connected via the N-H···O and O-H···O hydrogen bonds. The geometrical and hydrogen bond parameters are similar for non-deuterated (at 120 and 293 K) and deuterated compounds (at 90K). The phase transition is probably a consequence of order-disorder transition inside of hydrogen network. The 6-311G(2d,2p) basis set with B3LYP functional have been used to discuss the structure and vibrational spectra of the studied compound.

Intra- and inter-molecular hydrogen bonds, conformation and vibrational characteristics of hydrazo-group in 5-nitro-2-(2-phenylhydrazinyl)pyridine and its 3-, 4- or 6-methyl isomers.

Syntheses of 5-nitro-2-(2-phenylhydrazinyl)pyridine (5-nitro-2-phenylhydrazopyridine), 3-methyl-5-nitro-2-(2-phenylhydrazinyl)pyridine (3-methyl-5-nitro-2-phenylhydrazopyridine), 4-methyl-5-nitro-2-(2-phenylhydrazinyl)pyridine (4-methyl-5-nitro-2-phenylhydrazopyridine) and 6-methyl-5-nitro-2-(2-phenylhydrazinyl)pyridine (6-methyl-5-nitro-2-phenylhydrazopyridine) have been described. Their IR and Raman spectra have been measured and analyzed in terms of DFT quantum chemical calculations. The 6-311G(2d,2p) basis set with the B3LYP functional has been used to discuss the optimized structure and vibrational spectra. The vibrational characteristics of the hydrazo-bond have been reported with their relation to the inter- and intra-molecular hydrogen bonds formed in the studied systems. The role and influence of substitution position of the methyl chromophore on the structure and vibrational data have been discussed.

Heterozygous mis-sense mutations in Prkcb as a critical determinant of anti-polysaccharide antibody formation.

To identify rate-limiting steps in T cell-independent type 2 antibody production against polysaccharide antigens, we performed a genome-wide screen by immunizing several hundred pedigrees of C57BL/6 mice segregating N-ethyl-N-nitrosurea-induced mis-sense mutations. Two independent mutations, Tilcara and Untied, were isolated that semi-dominantly diminished antibody against polysaccharide but not protein antigens. Both mutations resulted from single-amino-acid substitutions within the kinase domain of protein kinase C-ß (PKCß). In Tilcara, a Ser552>Pro mutation occurred in helix G, in close proximity to a docking site for the inhibitory N-terminal pseudosubstrate domain of the enzyme, resulting in almost complete loss of active, autophosphorylated PKCßI, whereas the amount of alternatively spliced PKCßII protein was not markedly reduced. Circulating B cell subsets were normal and acute responses to B-cell receptor stimulation such as CD25 induction and initiation of DNA synthesis were only measurably diminished in Tilcara homozygotes, whereas the fraction of cells that had divided multiple times was decreased to an intermediate degree in heterozygotes. These results, coupled with evidence of numerous mis-sense PRKCB mutations in the human genome, identify Prkcb as a genetically sensitive step likely to contribute substantially to population variability in anti-polysaccharide antibody levels.

Vibrational spectra, crystal structure, DFT quantum chemical calculations and conformation of the hydrazo-bond in 6-methyl-3-nitro-2-(2-phenylhydrazinyl)pyridine.

The crystal and molecular structures of 6-methyl-3-nitro-2-(2-phenylhydrazinyl)pyridine (6-methyl-3-nitro-2-phenylhydrazopyridine) have been determined by X-ray diffraction and quantum chemical DFT analysis. The crystal is monoclinic, space group C2/c, with Z=8 formula units in the elementary unit cell of dimensions a=16.791(4), b=6.635(2), c=21.704(7)Å, ß=100.54(3)°. The molecule consists of two nearly planar pyridine subunits. A conformation of the linking hydrazo-bridge CNHNHC is bend and the dihedral angle between the planes of the phenyl and pyridine rings is 88.2(5)°. The hydrogen bonding of the type NH···N and possibly also CH···O favors a dimer formation in the crystal structure. The dimers are further linked by a NH···O hydrogen bond, so forming a layer parallel to the ab plane. The molecular structure of the studied compound has been determined using the DFT B3LYP/6-311G(2d,2p) approach and compared to that derived from X-ray studies. The IR and Raman wavenumbers have been calculated for the optimized geometry of a possible monomer structural model but the possibility of the dimer formation through the NH···N hydrogen bond has also been considered. The structural and vibrational properties of the intra-molecular NH···O interaction are described.

Molecular and crystal structures, vibrational studies and quantum chemical calculations of 3 and 5-nitroderivatives of 2-amino-4-methylpyridine.

The crystal structures of 2-amino-4-methyl-3-nitropyridine (I), 2-amino-4-methyl-3,5-dinitropyridine (II) and 2-amino-4-methyl-5-nitropyridine (III) have been determined. The compounds crystallize in the monoclinic P2(1)/n, triclinic P-1 and monoclinic C2/c space groups, respectively. These structures are stabilized by a combination of N-H···N and N-H···O hydrogen bonds and exhibit layered arrangement with a dimeric N-H···N motif in which the molecular units are related by inversion centre. The molecular structures of the studied compounds have been determined using the DFT B3LYP/6-311G(2d,2p) approach and compared to those derived from X-ray studies. The IR and Raman wavenumbers have been calculated from the optimized geometry of monomers and dimers formed in the unit cell and compared to the experimental values obtained from the spectra.

[Renal osteodystrophy in dialysis patients as estimated by three-point bone densitometry]. / Osteodystrofia nerkowa u chorych dializowanych w ocenie trzypunktowego pomiaru densytometrycznego.

The aim of a study was to estimate the renal osteodystrophy status using bone densitometry in relation to selected biochemical parameters of calcium-phosphate metabolism. The study population consisted of 123 patients with end-stage renal disease, including 24 patients treated with continuous ambulatory peritoneal dialysis (CAPD), aged between 22 and 73 years (mean 49.9 years), on dialysis program for mean period of 14.9 months and 99 patients on maintenance hemodialysis for mean period of 58.8 months, aged between 19 and 72 years (mean 46.6 years). Densitometric measurements using DEXA technique were performed in three different skeletal points: distal ends of both radial bones, lumbar spinal region and femoral neck. Concomitantly, serum concentrations of total and ionized calcium, phosphates and parathormone as well as alkaline phosphatase serum activity were measured. Among male patients treated with CAPD significantly higher BMD values in right forearm were found as compared to women treated with this method (0.769 vs. 0.616; p < 0.001). Higher values of BMD were also found in both forearms in whole CAPD population as compared to those on hemodialysis. However, there was no difference in densitometry results between CAPD and HD patients as well as between men and women within these groups, when measured in femoral neck and lumbar spinal region. Among hemodialysis patients higher levels of phosphates and PTH were found as compared to CAPD, doses of drugs used for treatment of osteodystrophy--calcium carbonate, aluminum hydroxide and active vitamin D were also higher in individuals on HD. In addition, in CAPD patients statistically significant, positive correlations were found between BMD value in lumbar spinal area as well as in femoral neck and amount of ingested calcium carbonate, between BMD in lumbar spinal area and aluminum hydroxide dose taken by patients and between BMD in both forearms and dose of active vitamin D. We failed to demonstrate any relationship between obtained densitometric results as well as biochemical markers of calcium-phosphate metabolism and quantitative parameters of dialysis adequacy in both treatment modes. Obtained results let us to conclude that renal osteodystrophy is less advanced in patients treated with peritoneal dialysis, however this may be related only to markedly shorter renal replacement therapy period in this group. Lack of significant abnormalities in densitometry measurements taken in lumbar spinal area and femoral neck, while they are present in forearms, may suggest that the latter point of skeleton may be most useful for identification of bone mass deficiency in dialyzed patients.

[Anticardiolipin antibodies in patients with Buerger's disease]. / Przeciwciala antykardiolipinowe w chorobie Buergera.

The aim of this study was to estimate the incidence of occurrence of anticardiolipin autoantibodies in patients with thromboangitis obliterans (TAO). Patients with Buerger's disease had statisticaverified significant higher frequency of anticardiolipin IgM antibodies than control group. This antibody may play a role in pathogenesis of TAO, although this results should be verified because of the small number of patients and diagnostic criteria.

Trichinella spiralis: induction of the basophilic transformation of muscle cells by synchronous newborn larvae. II. Electron microscopy study.

The present ultrastructure observations apply to the same experimental groups that were investigated in the first part of the study. The results of electron microscopy investigations correspond to those obtained using light microscopy methods. The ultrastructure data demonstrated that 1-h-old sNBL (group I) penetrated into the sarcoplasm of the muscle cells and transformed it basophilically, finally creating the "nurse cell-muscle larva complex." These larvae also caused transformation of the same muscle cells without being present in the sarcoplasm. The larvae of group II (9-h-old sNBL) preserved transformation potential as well, but it was less intensive. Not all NBL settled in the muscle cells; some of them remained in the intercellular spaces. Group II larvae present in the muscle cells underwent early degeneration and necrosis more often than did group I larvae; the inflammatory cell reactions in the vicinity of the larvae were more intensive. The basophilic transformation of muscle cells that did not contain larvae in their sarcoplasm was not intensive and often stopped at the level of cell nuclei. The larvae of group III (6-day-old sNBL) neither settled in the muscle cells nor transformed the cell sarcoplasm.

Trichinella spiralis: induction of the basophilic transformation of muscle cells by synchronous newborn larvae.

Newborn larvae (NBL) possess the "transformation potential" (TP) to induce the basophilic transformation of the muscle cell into the nurse cell and to create the nurse cell-muscle larva complex. For investigation as to whether TP is age-dependent, three groups of synchronous NBL (sNBL) were obtained at 1 h, 9 h, and 6 days of age, respectively, and were injected intramuscularly into mice. The TP was demonstrated to be high for both 1- and 9-h-old sNBL, but for 6-day-old sNBL, none was found. The earliest transformation of muscle cells was observed at 48 h postinfection (p.i.) in the first two groups of sNBL. Moreover, for 1-h-old sNBL the numbers of basophilically transformed muscle cells without larvae were 3-fold those of sNBL observed in histology sections. The results indicate that (1) due to the high TP observed in the 1-h-old sNBL group, NBL are born with TP; (2) the TP is lost by aging; and (3) the induction of the basophilic transformation of muscle cells is possible without direct contact between the muscle cell and NBL being required, as contact with released factor(s) alone may be enough.

[Biostimulating laser therapy as one method of treating bone and joint diseases]. / Laseroterapia biostymulacyjna jako jedna z metod leczenia schorzen ukladu kostno-stawowego.

An assessment of medium power semi-conductor laser treatment effectiveness was evaluated in 205 patients (132 females and 73 males) aged 57 to 75 (mean 62.5) years with pain syndrome in a course of hip, knee, shoulder, elbow, temporo-maxillaris and vertebral joints degenerative changes. Procedures were performed 3 times a week using punctual technique, sweeping and scanning. Total number of procedures ranged from 8 to 20 and radiation energy dose was 4 to 12 J/cm2. Favourable therapy effect was demonstrated as pain and oedema disappearance in about 40% of patients; insignificant therapeutic effect was achieved in 46.3% and lack of affect in 13.7% of individuals.

[Etiology and pathogenesis of urolithiasis]. / Etiologia i patogeneza kamicy ukladu moczowego.

For ages nephrolithiasis has been a widespread disease and clinical statistics prove that its morbidity index is still increasing, thus it becomes a social problem. Peak morbidity usually occurs at the age between 30 and 40, that is why many patients professionally active and creative have to leave their jobs for a long period. In contrast to earlier years, frequency of the disease occurrence in females is systematically increasing and nowadays it is only slightly lower from that in males. Etiology and pathogenesis of the disease is also not entirely explained. It is generally accepted that urinary stone formation is determined by multiple factors which affect first of all chemical composition and physical features of urine. Individual properties of the kidneys and urinary tract and infections especially with urease producing pathogens as well as environmental factors are also taken into account. The most favourable circumstances for nephrolithiasis occurrence is co-existence of all these factors.