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.

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.

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-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.

Prevalence of glucose intolerance in school age children. Population based cross-sectional study.

AIM: The aim of the study was to determine the prevalence of glucose intolerance among school children in south-eastern Poland. METHODS: Schools were randomly selected in the area and the entire school population was studied. We examined 1083 children (510 boys and 573 girls) in the mean age 14.49 years (age range: 7.9-19 years). Their weight and height were measured and body mass index (BMI) was calculated. Patients were classified as overweight or obese based on International Obesity Task Force (IOTF) criteria. We tested fasting glucose level in randomly selected children with normal weight (N=83) in all overweight and obese subjects (N=229). In children with fasting blood glucose level higher than 5.5 mmol/L (100 mg/dL) oral glucose tolerance test (OGTT) was performed. RESULTS: About 17.8% of children were overweight and 4.6% obese. Fasting hyperglycemia was found in 16.7% obese children. The calculated prevalence of fasting hyperglycemia for entire population was 6.7/1000. Impaired glucose tolerance (IGT) was found only in obese children. The prevalence of glucose intolerance in obese children was 7.1%, in contrast the calculated prevalence of glucose intolerance for the entire population was 3.0/1000 (95% confidence interval: 0-8.4/1000). CONCLUSION: Despite relatively high number of obese children, the prevalence of IGT among schoolchildren of south-eastern Poland remains low.

Iodine-induced hyperthyroidism--an epidemiological survey several years after institution of iodine prophylaxis in Poland.

In 1997, the obligatory model of iodine prophylaxis was introduced in Poland in order to correct the existing status of mild and/or moderate iodine deficiency. In order to monitor possible side-effects of increased iodine supply, studies on iodine-induced hyperthyroidism were initiated by establishing several regional registers of hyperthyroidism. In the present paper, the results of a two-year monitoring (2000-2001) have been summarized. There are no epidemiological data on hyperthyroidism prior to starting the iodine prophylaxis, but the obtained current data are comparable to observations in other countries, made after iodine supplementation. The incidence of iodine-induced hyperthyroidism did not exceed the acceptable level, thus confirming--together with previous observations on the effectiveness of iodine prophylaxis--the adequacy of applied dose of KI (30 microg/kg NaCl), used for salt iodization in Poland.

[Polish multicenter study on diabetes type I incidence in he age group 0-14 between 1998 and 1999]. / Wieloosrodkowe badania nad zapadalnoscia na cukrzyce typu 1 w grupie wiekowej 0-14 lat w Polsce w latach 1998-1999.

The increase in diabetes type 1 incidence observed in various centers in Poland and the need for a centralized study covering large population have resulted in the construction of a standardized registry of type 1 diabetes in 1998 within the Polish Multicenter Study in Diabetes Epidemiology. The aim of the study was to present the incidence rates of type 1 diabetes in the age group 0-14 in 7 distinct regions of Poland (Krakow, Wroclaw, Warsaw, Bialystok, Poznan, Rzeszow and Olsztyn centers) with over 30% of the Polish population at risk in 1998 and 1999. The data for the standardized registry were obtained prospectively from paediatric hospital wards and diabetes outpatient units. The incidence rates calculated in 1998 showed the highest value of 14.6 and 14.5/100,000 for Olsztyn and Warsaw, and the lowest (8.4/100,000) for Poznan center. In 1999 the highest value of 14.7/100,000 was noted in Krakow and the lowest (9.3/100,000) in Poznan center. The differences in diabetes type 1 incidence rates between age groups 0-4, 5-9 and 10-14 were found to be significant (p < 0.0005) and were also significant when incidence rates were compared between males and females in these age groups in the whole study area in 1998-1999 (p = 0.002 and p = 0.015 respectively).

[Polish multicenter study on type I diabetes incidence in the age group 15-29 between 1998 and 1999]. / Wieloosrodkowe badania nad zapadalnoscia na cukrzyce typu 1 w grupie wiekowej 15-29 lat w Polsce w latach 1998-1999.

The increase in diabetes type 1 incidence observed in various centers in Poland and the need for a centralized study covering a large population have resulted in the construction of a standardized registry of type 1 diabetes in 1998 within the Polish Multicenter Study in Diabetes Epidemiology. The aim of the study was to evaluate the incidence of type 1 diabetes in the age group 15-29 in 5 distinct regions of Poland (Krakow, Warsaw, Bialystok, Rzeszow and Olsztyn centers) with over 15% of the Polish population at risk in 1998 and 1999. The data for the standardized registry were obtained prospectively from hospital departments and diabetes outpatient units. The incidence rates calculated in 1998 showed the highest value of 11.2/100,000 for Krakow and its region, and the lowest (4.4/100,000) for Bialystok and its region. In 1999 the highest value of 12.3/100,000 was noted in Olsztyn and its region and the lowest (3.4/100,000) in Warsaw. There were significant differences in the incidence rates between the study centers were found. Incidence rates in the whole study area were significantly higher among males as compared with females in 1998 and 1999 (8.9/100,000 vs. 4.9/100,000; p = 0.0001), marked in the age groups 15-19 and 20-24 (p = 0.001 and p = 0.002 respectively). A significant increase in diabetes type 1 incidence (from 4.6/100,000 to 6.9/100,000) was found as compared with results of the "Three Cities Study" (1986-1988).

[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.

[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.

[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.

[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.

[Some aspects of epidemiology in insulin-dependent diabetes mellitus (IDDM) (I)]. / Niektóre kierunki badan w epidemiologii cukrzycy insulinozaleznej (IDDM) (I).

Epidemiological studies based on registries from many centers in the world revealed geographical variation of IDDM, with the highest incidence in Scandinavian countries. There is a gradient north to south in occurrence of IDDM, and differences in incidence between urban and rural populations. Poland is a country with a rather low incidence of IDDM, not exceeding 6/100,000 in the population 0-29 years of age until 1992. Generally a higher incidence of IDDM has been observed in Whites, there are differences between migrating populations ethnically homogenous. The highest incidence occurs in 10-14 age group, with male sex predominance.

[Some aspects of epidemiology in insulin-dependent diabetes mellitus (IDDM) (II)]. / Niektóre kierunki badan w epidemiologii cukrzycy insulinozaleznej (IDDM) (II).

Seasonality is a characteristic feature of IDDM incidence. The lowest incidence is observed in summer, whereas the highest in winter/autumn. The risk of IDDM increases in children with independently: breast feeding shorter then 3 months, feeding with cow's milk instead of breast feeding, early introducing of solid diet in babies, or high consumption of cow's milk in later years. Children with new onset IDDM have elevated levels of the antibodies against cow's milk proteins and beta-lactoglobulin. It has been proved that there is a connection with HLA DQalfaArg52 i DQbeta-Asp57 and polymorphic region of insulin gene, and the IDDM susceptibility.

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.

[Maternal age at the moment of birth and occurrence of insulin dependent diabetes mellitus (IDDM) in the child]. / Wiek matki w momencie urodzenia dziecka a wystepowanie u niego cukrzycy insulinozaleznej (IDDM).

The aim of the study was to determine whether advanced maternal age (over 35 years) on birth of a child had any influence on the incidence of IDDM in her offspring. The analysis has also taken into account the presence of other factors which may have some bearing on the incidence of the disease. They are the following: viral infections prior to the onset of IDDM, sequence of the affected child's birth in relation to other siblings, and family history of diabetes. The study included 243 persons who fell ill with IDDM at the age of 0-29 years in the period of January 1st 1980 to December 31st 1992 and the pair matched control group. They were all residents of the Rzeszów province at the onset of the disease. We have found that a positive family history of diabetes, viral infection especially epidemic parotitis, and parity are the factors which increase the incidence of IDDM. Advanced maternal age, over 35 years on child's birth, along with the above-mentioned factors, increase the incidence of IDDM.