CFA-15 - a perfluorinated metal-organic framework with linear 1-D CuII-chains containing accessible unsaturated, reactive metal centres.

The synthesis and crystal structure of the perfluorinated metal-organic framework CFA-15 (Coordination Framework Augsburg University-15), CuII3(tfpc)2(OH)2·DMF, as well as the crystal structure of its ligand (H2-tfpc = 3,5-bis(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) are described. The MOF crystallizes in the monoclinic crystal system within the chiral space group C2 (no. 5). It features a 3-D microporous framework with rhombic channels along the c-axis. The MOF is formed by 1-D chains of Cu(ii) ions expanding in the c-direction, bridged by OH- groups, DMF molecules and tfpc2- ligands. Two different Cu(ii) species are located within the structure, bridged in a {Cu1-Cu1-Cu2-Cu1-Cu1-Cu2} mode. By thermal treatment, it was possible to remove coordinated solvent molecules and generate free accessible, unsaturated and reactive metal centres. The structure of activated CFA-15 was refined via Rietveld method. DRIFT measurements, which were used to study adsorption of CO2 and NO in the MOF, showed a formation of a stable NO-CFA-15 complex. CFA-15 was further characterized by thermogravimetric analysis, variable temperature powder X-ray diffraction measurements, IR spectroscopy, as well as photoluminescence and gas sorption measurements. The isosteric heats of adsorption for CO, CO2, H2 and O2 were determined, and compared to DFT calculated sorption energies as well as to data reported in literature for similar materials.

Synthesis and characterization of a flexible metal organic framework generated from MnIII and the 4,4'-bipyrazolate-ligand.

The synthesis and crystal structure of a novel metal organic framework, constructed from MnIII, the 4,4'-bipyrazolate (BPZ) ligand and bridging hydroxyl groups is presented in this work. The network topology is identical to M-CFA-6 (M = Fe, Ga), but in the case of Mn-CFA-6, the structure crystallizes in the monoclinic crystal system due to the Jahn-Teller effect of the high spin d4 manganese(iii) centers. Thermal treatment of Mn-CFA-6 leads to decomposition of the framework above 150 °C. The porosity of Mn-CFA-6 was measured by carbon dioxide sorption, since solvent exchange and removal of the occluded solvent molecules leads to a compression of the pores. Electronic spectra of Mn-CFA-6 reveal two distinct absorption bands that are assigned to the two different manganese(iii) centers as revealed by the single crystal structure analysis. Furthermore, SQUID measurements exhibit ferromagnetic behaviour of Mn-CFA-6 below the magnetic ordering at 45 K and antiferromagnetic coupling above this temperature. Evaluation of the paramagnetic region by the Curie-Weiß formula reveals an effective moment of 4.8µB, which is very close to the spin-only value of MnIII centers.

CFA-14 - a perfluorinated metal-organic framework with linear 1-D CoII-chains showing temperature dependent spin-chain magnetic ordering.

The synthesis and crystal structure of the perfluorinated metal-organic framework (MOF) CFA-14 (Coordination Framework Augsburg University-14), CoII2(tfpb)(OH)2 (H2-tfpb = 1,4-bis(3,5-bis(trifluoromethyl)-1H-pyrazole-4-yl)benzene) are described. The cobalt-containing MOF crystallizes in the tetragonal crystal system within the space group I41/acd (no. 142) and the unit cell parameters are as follows: a = 20.3213(11) Å, c = 12.4045(8) Å, V = 5122.5(6) Å3. CFA-14 features a porous two-fold interpenetrated 3-D microporous structure constructed from 1-D chains of cobalt(ii) ions expanding in the c-direction, bridged by OH- groups and tfpb2- ligands. The structure exhibits quadratic channels running along the c-axis. CFA-14 is fully characterized by synchrotron single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR- and UV-Vis spectroscopy, photoluminescence and gas sorption measurements. Moreover, the magnetic properties of CFA-14 are examined via SQUID measurements.

CFA-13 - a bifunctional perfluorinated metal-organic framework featuring active Cu(i) and Cu(ii) sites.

The synthesis and crystal structure of the mixed-valent perfluorinated metal-organic framework (Me2NH2)[CFA-13] (Coordination Framework Augsburg University-13), (Me2NH2)[CuCu(tfpc)4] (H2-tfpc = 3,5-bis(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) is described. The copper-containing MOF crystallizes in the monoclinic crystal system within the space group P21/n (no. 14) and the unit cell parameters are as follows: a = 22.3887(19), b = 13.6888(8), c = 21.1804(13) Å, ß = 90.495(3)°, V = 6491.0(8) Å3. (Me2NH2)[CFA-13] features a porous 3-D structure constructed from two types of secondary building units (SBUs). Besides novel trinuclear [Cu(pz)4]- coordination units, the network also exhibits Cu(ii) paddle-wheel SBUs. (Me2NH2)[CFA-13] is fully characterized by single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence, gas sorption measurements and pulse chemisorption experiments. M[CFA-13] (M = K+, Cs+) frameworks were prepared by postsynthetic exchange of interchannel dimethylammonium cations. Moreover, it was shown that CO molecules can be selectively bound at Cu(i) sites of [Cu(pz)4]- units, whereas Cu(ii) paddle-wheel units bind selectively NH3 molecules.

Bistriazole-p-benzoquinone and its alkali salts: electrochemical behaviour in aqueous alkaline solutions.

Quinones are well known as redox-active compounds. In this work bistriazole-p-benzoquinone was prepared and its electrochemical behaviour in aqueous alkaline solutions was studied by cyclic voltammetry. Two successive one-electron reduction steps were observed - the first step was reversible and the second quasireversible. Based on the nature of the alkali cation, the potential of the cathodic peak minimum and the anodic peak maximum was shifted towards positive direction as follows Li+ > Na+ > K+. In order to know more about the chemical structure of the alkali salts, the lithium, sodium and potassium salts of bistriazole-p-benzoquinone were crystallized and their structure could be revealed by single crystal X-ray analysis. Additionally, the thermal stability of the compounds was investigated by thermogravimetric analysis and variable temperature X-ray powder diffraction analysis.

CFA-4 - a fluorinated metal-organic framework with exchangeable interchannel cations.

The syntheses and crystal structures of the fluorinated linker 1,4-bis(3,5-bis(trifluoromethyl)-1H-pyrazole-4-yl)benzene (H2-tfpb; 1) and the novel metal-organic framework family M[CFA-4] (Coordination Framework Augsburg University-4), M[Cu5(tfpb)3] (M = Cu(i), K, Cs, Ca(0.5)), are described. The ligand 1 is fully characterized by single crystal X-ray diffraction, photoluminescence-, NMR-, IR spectroscopy, and mass spectrometry. The copper(i)-containing MOF crystallizes in the hexagonal crystal system within the chiral space group P6322 (no. 182) and the unit cell parameters are as follows: a = 23.630(5) Å, c = 41.390(5) Å, V = 20 015(6) Å3. M[CFA-4] features a porous 3-D structure constructed from pentanuclear copper(i) secondary building units {Cu(pz)6}- (pz = pyrazolate). Cu(I)[CFA-4] is fully characterized by synchrotron single crystal X-ray diffraction, thermogravimetric analysis, variable temperature powder X-ray diffraction, IR spectroscopy, photoluminescence and gas sorption measurements. Moreover, thermal stability and gas sorption properties of K[CFA-4] and Cu(I)[CFA-4] are compared.

A structurally flexible triazolate-based metal-organic framework featuring coordinatively unsaturated copper(i) sites.

The novel metal-organic framework CFA-8 (Coordination Framework Augsburg University-8), [Cu2(tqpt)], containing the organic linker H2-tqpt {H2-tqpt = 6,6,14,14-tetramethyl-6,14-dihydroquinoxalino[2,3-b]phenazinebis-triazole}, has been synthesized. Reaction of H2-tqpt and anhydrous CuCl2 in N,N-dimethylacetamide (DMA) yields CFA-8 as orange crystals with lenticular shape. This framework shows a reversible breathing effect and is robust upon solvent removal. It has been characterized by single-crystal and powder X-ray diffraction, TGA, IR spectroscopy and gas sorption measurements. CO adsorption isotherms show that Cu(i) sites in this framework are able to bind carbon monoxide forming a weak complex which has been additionally characterized by IR spectroscopy and synchrotron powder X-ray diffraction measurements.

Incidence of IDDM in the province of Rzeszów, Poland, 0- to 29-year-old age-group, 1980-1992.

OBJECTIVE: To study the incidence of insulin-dependent diabetes mellitus (IDDM) in the province of Rzeszów, Poland, and to test for differences in incidence by age at diagnosis, time cluster, sex, urban-rural population, and season. RESEARCH DESIGN AND METHODS: A registry was established in 1990 to collect new IDDM cases among people 0-29 years of age, from 1980 to 1992. Data were collected according to the Diabetes Epidemiology Research International Group recommendations. RESULTS: The average age-standardized incidence of IDDM was 5.31/100,000 population (95% confidence interval [CI] 4.67-6.04) for those 0-29 years of age. Among males, it was 5.68/100,000 (CI 4.77-6.77), and among females it was 4.93/100,000 (CI 4.07-5.97). The incidence for children 0-14 years old was 5.11/100,000 (CI 4.27-6.11) and for those 15-29 years old, 5.55/100,000 (CI 4.60-6.68). The incidence of IDDM in autumn (September through November) was the highest (87 of 243 cases) and differed statistically from each of the other seasons. The incidence of IDDM among the urban and rural populations did not differ. There were also no differences between the sexes and the groups divided by 5-year age intervals. CONCLUSIONS: This study documents the low incidence rate and seasonal dependence of IDDM among people 0-29 years of age in the province of Rzeszów, Poland.

[Syndromes of thyroid hormone resistance]. / Zespoly opornosci na dzialanie hormonów tarczycy.

The authors have presented the contemporary knowledge concerning the syndromes of thyroid hormone resistance. There are three forms of this syndrome: Generalized Resistance of Thyroid Hormone, Pituitary Resistance to Thyroid Hormone and Peripheral Tissue Resistance to Thyroid Hormone. The illness appears in both family and sporadic forms. Etiology with the special concern to the molecular level is presented. The authors have also characterized the clinical picture, diagnostic methods and treatment of the syndrome.

[The syndrome of inappropriate TSH secretion of neoplastic origin (NIST)]. / Zespól nieprawidlowego wydzielania TSH o etiologii nowotworowej.

The authors present clinical features, diagnostic approach and treatment of inappropriate TSH secretion syndrome. To data above 80 cases of this syndrome have been described. The main clinical features are thyrotoxicosis and vascular goiter present in the patient with pituitary adenoma. High concentrations of free thyroid hormones coexist with elevated TSH serum level. In some cases hyperproduction of other anterior lobe pituitary hormones was found. The molar ratio alpha subunit to TSH exceeds 1.0. In the management of inappropriate TSH secretion syndrome hypophysectomy, irradiation and long-acting somatostatin analog octreotide are applied.

[Selected clinical characteristics of insulin dependent diabetes (IDDM) discovered in the years 1990-1992 in patients 0-29 years of age from the Rzeszów voivodship]. / Wybrane cechy kliniczne cukrzycy insulinozaleznej (IDDM) wykrytej w latach 1990-1992 u chorych w wieku 0-29 lat z województwa Rzeszowskiego.

The aim of the study was to analyse the clinical symptoms preceding the final diagnosis of IDDM, some features of the illness at the moment of the diagnosis and variants of treatment. We examined 54 patients, among them 28 males and 26 females. There were 23 and 31 persons between 0-14 and 15-29 years of age, respectively. The data were accumulated using questionnaires. We have shown that the newly diagnosed IDDM cases were characterised by typical clinical symptoms, early detection and 100% hospitalization. Most of the patients or their parents underwent the diabetic education during the patients first stay at hospital. Only monocomponent or human insulins were used in the case of patients between 0-14 years of age. Among the group 15-29 years of age in 13% of patients ordinary insulins (regular, NPH, Lente group) were administered as well. Intensive insulin therapy was used exclusively, but sporadically in the patients 15-29 years of age.

[Severe aplastic anemia as a complication of treatment with metizol]. / Ciezka niedokrwistosc aplastyczna jako powiklanie leczenia metizolem.

Aplastic anemia is the rare hematologic complication of the antithyroid medication. We present here the case of 39-years old female who was treated with Thiamazole due to Graves disease. This and the others cases cited in the literature indicate that antithyroid drugs-induced aplastic anemia is characterised by severe clinical status and profound marrow hypoplasia or aplasia but good prognosis with short term recovering.

[Abdominal actinomycosis imitating non-operable stage of cancer]. / Promienica brzuszna imitujaca nieoperacyjne stadium raka.

In a 44-year-old woman on the basis of short hospital medical observation and gynaecological consultations, malignancy of reproductive organs was preliminarily diagnosed. During the operation the gynaecological-surgical team confirmed the presence of generalized neoplastic process in the abdominal cavity. In the obtained surgical specimens actinomycosis was diagnosed by histological examination. Longterm antibiotic therapy caused an improvement of the patient's condition, increase of body weight, improvement of blood morphologic picture, regression of tumour-like changes in the liver. The case reminds the necessity of taking into account actinomycotic infection in the differential diagnosis of conditions suggesting a neoplastic process in the abdominal cavity.