Crystal structure, vibrational and optic properties of 2-N-methylamino-3-methylpyridine N-oxide - Its X-ray and spectroscopic studies as well as DFT quantum chemical calculations.

The crystal and molecular structure and physicochemical properties of 2-N-methylamino-3-methylpyridine N-oxide (MA3MPO) have been studied. MA3MPO was synthesized from 2-amino-3-methylpyridine by several steps to form colorless crystals suitable for crystallographic analysis. The data reveal that MA3MPO crystallizes in the monoclinic space group P21/n. The studied compound contains a nearly flat triply substituted pyridine skeleton whose structure is stabilized by an intramolecular N-H⋅⋅⋅O hydrogen bond. The N-oxide molecules are connected together by weak C-H⋯O hydrogen bonds, an acceptor of which is the oxygen atom from the N-oxide group. This leads to creation of two-dimensional network of hydrogen bonds. Its IR, Raman, UV-Vis and luminescence spectra have been measured and analyzed on the basis of DFT and NBO quantum chemical calculations in which the B3LYP/6-311++G(d,p) approach was applied. The distribution of the electron levels in the studied compound has been analyzed in terms of the possibility of its participation in the ligand-to-lanthanide ion energy transfer.

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.

Prophylactic cranial irradiation in small cell lung cancer: a single institution experience.

BACKGROUND: Prophylactic cranial irradiation (PCI) is used to prevent the development of brain metastases in small cell lung carcinoma. PCI confers an overall survival (OS) benefit in both limited and extensive stage disease. AIMS: We analyze the incidence of symptomatic brain metastases, progression-free survival (PFS) and OS in a cohort of patients who received PCI, in a 5-year period. METHODS: A retrospective review of all patients who had received PCI between 2006 and 2011 at the Whitfield Clinic was completed. Patient- and disease-related characteristics, the number of patients who developed brain metastases, PFS and OS data were collected. RESULTS: 24 patients were identified. 14 (58.3 %) patients were male, 10 (41.7 %) were female, with a mean age of 62.5 years (range 31-78). All patients were smokers. 12 (50 %) patients had limited stage small cell lung cancer (SCLC), 12 (50 %) had extensive stage disease. 2 (8.2 %) patients developed brain metastases post PCI (p = 0.478.) The median PFS for limited stage SCLC was 13 months (range 3-20) and 10 months (range 5-18) for extensive stage SCLC. Median OS was 15 months (range 4-29) in limited stage SCLC, and 11 months (range 5-29) in extensive stage SCLC. CONCLUSIONS: Our study demonstrated a low incidence of symptomatic brain metastases and favourable median PFS and OS in the patients that received PCI, when compared to published phase III data.

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.

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.

Polarized IR and Raman spectra and ab initio calculations for bis(guanidine) zirconium bis(nitrilotriacetate) hydrate single crystal [C(NH2)3]2[Zr[N(CH2COO)3]2](H2O)--the new laser Raman converter.

Fourier transform polarized IR and Raman spectra of bis(guanidine) zirconium bis(nitrilotriacetate) hydrate single crystal [C(NH(2))(3)](2)[Zr[N(CH(2)COO)(3)](2)](H(2)O) have been measured in the regions 30-4000 and 80-4000 cm(-1) and correlated with X-ray structural data. The factor group analysis has been applied in the discussion of the dichroic dependence of the vibrational modes. The assignment of the internal vibrations for the [Zr(nitrilotriacetate)2]2- complex ion has been based on the ab initio quantum chemical calculations. The usefulness of the studied crystal as Raman laser converter was analyzed basing on the comparison of the spontaneous and stimulated Raman spectra.

[The evaluation of the effectiveness of half-body irradiation as palliative treatment in patients with multiple bone metastases]. / Ocena skutecznosci napromieniania polowy ciala jako paliatywnej i przeciwbólowej radioterapii u chorych z mnogim rozsiewem nowotworowym w kosccu.

The results of simplified method of hemibody irradiation of 23 patients with multiple painful bone metastases are presented. In all cases without proven bone metastases in skull and distal part of limbs, these parts of the body were excluded from irradiated field. The study comprised 25 cases of hemibody irradiation. The degree of pain relief and performance status improvement was assessed one and two months after treatment, depending on clinical and histopathological diagnosis and type of bone metastases. The best symptomatic results were obtained in the cases of multiple myelomas (100% of pain relief), prostate cancers (the average degree of 78%) and lung cancers (88%). Considering histopathological diagnosis, the best answer was found in multiple myeloma and squamous cell cancer (88%). Taking into account type of metastases the best result was obtained in the cases of osteolytic metastases (65%). No difference between upper and lower hemibody irradiation was found. The statistically significant correlation between pain relief, performance status improvement and decrease of analgetics use was found. The obtained results suggest that presented simplified form of hemibody irradiation is an effective symptomatic treatment modality in the cases with multiple painful bone metastases, giving an increase of life quality without significant radiation morbidity.

[Prognostic factors in radiotherapy for hypopharyngeal cancer]. / Czynniki prognostyczne w radioterapii samodzielnej raka gardla dolnego.

This paper presents influence of selected prognostic factors on results of hypopharyngeal cancer radiotherapy used as only treatment in 97 patients irradiated in Centre of Oncology-Institute in Gliwice between 1980-1987. One-variant analysis showed statistically significant influence of gender, decrease of haemoglobin level during radiotherapy and higher T and N stages. Multivariant analysis demonstrated, that only locoregional status and treatment time has decisive importance on radiotherapy results. Thus, better results of treatment depend on lower T and N stages and correct radiotherapy time.

[[Radical radiotherapy in patients with laryngeal cancer in clinical material of Institute Oncology in Gliwice treated in year 1990-1996]. / Samodzielna radioterapia chorych na raka krtani w materiale klinicznym Instytutu Onkologii w Gliwicach w latach 1990-1996.

This paper presents influence of selected prognostic factors on results of laryngeal cancer radiotherapy used as the only treatment in 541 patients irradiated in Centre of Oncology-Institute in Gliwice between 1990-1996. The 3-year actuarial disease-free survival was 47.5% for supraglottic cancer and 67% for glottic cancer. Primary tumour localisation in glottis correlates with more favourable prognosis than that in supraglottic. For extralaryngeal involvement the most favourable prognosis was infiltration of cartilages and the worst one for the hypopharyngeal and oropharyngeal involvement. Pretreatment tracheostomy significantly correlates with the worst results.

[Head and neck lymph node metastases from unknown primary site]. / Przerzuty do wezlów chlonnych regionu glowy i szyi z nieznanego ogniska pierwotnego.

The aim of this paper was to evaluate the group of 50 patients with cervical nodes metastases from unknown primary site treated between 1980-1995 in Maria Sk_odowska-Curie Memorial Institute of Oncology in Gliwice. There were 42 males and 8 females ranging in age from 26 to 85 years (median 60). 24 patients underwent combined therapy (surgery with postoperative radiotherapy), 22 underwent radiotherapy. Only 4 patients were treated with surgery alone. 3-years DFS rates were 59% in group treated with combined method, and 10% in group treated only with radiation therapy (p = 0.003). After a median follow up of 39 months 10 primary tumors were discovered--8 in head and neck region, 2 in lower respiratory tracts. DFS rate in group with discovered primary tumors was 40%.

[Comparison of natural history of squamous cell carcinoma and nondifferentiated carcinoma localized in oro- and nasopharynx]. / Ocena porównawcza przebiegu klinicznego raka plaskonablonkowego i niezróznicowanego czesci ustnej i nosowej gardla.

Aim of this study is comparison of natural history between two subtypes of cancer: squamous and undifferentiated, which were localised in oro- and nasopharynx. Analysis has contained 175 patients with undifferentiatied and 510 patients with squamous cell cancers of oro- and nasopharynx, who were treated in Centre of Oncology--Institute branch Gliwice in 1980-1998. Presence of undiferentiated subtypes were bounded with shortening time of presence the symptoms of disease, most frequent exophytic type of infiltration than in squamous cancer with ulcerative--necrotic type of infiltration. Higher aggressiveness of undifferentiated cancer is based on higher frequency of distant and nodal metastases, metastases to contralateral nodes and higher percentage of conglomerates.