Exploring physical and chemical properties in new multifunctional indium-, bismuth-, and zinc-based 1D and 2D coordination polymers.

Main group element coordination polymers (MGE-CPs) are important compounds for the development of multifunctional materials. However, there has been a shortage of studies regarding their structural, optical, catalytic, mechanical, and antibacterial properties. This work presents an exhaustive study of a set of crystalline MGE-CPs obtained from bismuth and indium metals and iminodiacetate, 1,2,4,5-benzenetetracarboxylate, and 2,2'-bipyridine as building blocks. An in-depth topological analysis of the networks was carried out. Additionally, nanoindentation studies were performed on two representative low-dimensional compounds in order to find the relationships between their structural features and their intrinsic mechanical properties (hardness and elasticity). The solid-state photoluminescence (SSPL) properties were also studied in terms of excitation, emission, lifetimes values, and CIE chromaticites. Moreover, the heterogeneous catalytic activities of the compounds were evaluated with the cyanosilylation reaction using a set of carbonylic substrates under solvent-free conditions. Finally, the inhibitory effect of the Bi-CPs on the growth of microorganisms such as Escherichia coli, Salmonella enterica serovar Typhimurium, and Pseudomonas aeruginosa, which are associated with relevant infectious diseases, is reported.

On the critical temperature discontinuity at the theoretical bcc-fcc phase transition in compressed selenium and tellurium superconductors.

Recent hydrides-driven advent in the high-pressure phonon-mediated superconductivity motivates research on chemical elements which compound with hydrogen. It is desired that such elements should allow chemical pre-compression of hydrogen to assure the induction of the superconducting phase with the high transition temperature (T C). Herein, we present detailed theoretical insight into the properties of the superconducting state induced under pressure (p) in two of such component elements, namely selenium (Se) and tellurium (Te) at [Formula: see text] GPa and [Formula: see text] GPa, respectively. The assumed external pressure conditions allow us to conduct our analysis just above previously theoretically predicted bcc-fcc structural phase transition of Se and Te, and identify the possible associated discontinuity effect of the critical temperature. In particular, our numerical analysis is conducted within Migdal-Eliashberg formalism, due to the confirmed electron-phonon pairing mechanism and relatively high electron-phonon coupling constant in the materials of interest. We predict that T C values in Se and Te equal 8.13 K and 5.96 K, respectively, and mark the highest critical temperature values for these elements within the postulated fcc phase. Additionally, we supplement these results by the estimated maximum values of the superconducting energy band gap and the effective mass of electrons. We predict that all these parameters can be used as a guidelines for experimental observation of the critical temperature discontinuity and the corresponding bcc-fcc phase transition in Se and Te superconductors. Moreover, we show that the thermodynamics of superconducting phase in both elements may exhibit deviations from the conventional estimates of the Bardeen-Cooper-Schrieffer theory, and suggest existence of the strong-coupling and retardation effects. Finally, we note that our results can be also instructive for future screening of chemical elements for applications in superconducting hydrides.

Cryogenic luminescent thermometers based on multinuclear Eu3+/Tb3+ mixed lanthanide polyoxometalates.

Here, the excellent thermal sensing capability of a multinuclear lanthanide polyoxometalate in the cryogenic region (<100 K) is presented for the first time. Up till now, no lanthanide polyoxometalates have been studied for their use as ratiometric luminescent thermometers. The investigated Tb3+ polyoxometalate cluster is doped with 1.6% (P1) and 8.4% (P2) of Eu3+ ions. When excited into the Mo-O charge transfer bands, at room temperature only the emission of the Eu3+ ions is observed suggesting a very efficient energy transfer between Mo-O→Tb3+→Eu3+. Only in the cryogenic region the emission of Tb3+ is also witnessed.

Multidoped Ln3+ gadolinium dioxycarbonates as tunable white light emitting phosphors.

Gadolinium dioxycarbonates co-doped with different visible emitting lanthanides were synthesized via a co-precipitation method using oxalic acid as a precipitating agent. Through XRD and DTA/TG investigations, the type-II hexagonal phase of the lanthanide dioxycarbonates was confirmed for all of the samples. The materials constitute of big agglomerates formed by submicrometrical particles. By varying the Ln3+ doping percentages and ratios and by changing the excitation wavelength the gadolinium dioxycarbonates activated with Sm3+, Eu3+, Tb3+, Dy3+ and Tm3+ showed tunable emission colors. Luminescence measurements were performed in order to determine: the luminescence behavior of the ions, the CIE coordinates, the CCT values and potential energy transfer. Interesting results were achieved upon exciting the samples at 351 nm and 365 nm demonstrating the possibility to obtain white emission in the dioxycarbonate matrix.

Cuticle hydrolysis in four medically important fly species by enzymes of the entomopathogenic fungus Conidiobolus coronatus.

Entomopathogenic fungi infect insects via penetration through the cuticle, which varies remarkably in chemical composition across species and life stages. Fungal infection involves the production of enzymes that hydrolyse cuticular proteins, chitin and lipids. Host specificity is associated with fungus-cuticle interactions related to substrate utilization and resistance to host-specific inhibitors. The soil fungus Conidiobolus coronatus (Constantin) (Entomophthorales: Ancylistaceae) shows virulence against susceptible species. The larvae and pupae of Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae), Calliphora vomitoria (Linnaeus), Lucilia sericata (Meigen) (Diptera: Calliphoridae) and Musca domestica (Linnaeus) (Diptera: Muscidae) are resistant, but adults exposed to C. coronatus quickly perish. Fungus was cultivated for 3 weeks in a minimal medium. Cell-free filtrate, for which activity of elastase, N-acetylglucosaminidase, chitobiosidase and lipase was determined, was used for in vitro hydrolysis of the cuticle from larvae, puparia and adults. Amounts of amino acids, N-glucosamine and fatty acids released were measured after 8 h of incubation. The effectiveness of fungal enzymes was correlated with concentrations of compounds detected in the cuticles of tested insects. Positive correlations suggest compounds used by the fungus as nutrients, whereas negative correlations may indicate compounds responsible for insect resistance. Adult deaths result from the ingestion of conidia or fungal excretions.

Increased proapoptotic activity of electron beam irradiated doxorubicin and epirubicin in multidrug-resistant human leukemic cells.

This study evaluated the effect of electron beam irradiation on the cytotoxic activity of anthracycline antibiotics such as doxorubicin (DOX), epirubicin (EPI), and dunorubicin (DAU) in human acute lymphoblastic leukemia cell line CCRF-CEM and its multidrug-resistant variant CCRF-VCR1000 cell line characterized by the overexpression of ABCB1 gene. Drugs were irradiated at doses of 10 and 25 kGy. Data from EPR studies proved that the highest concentration of free radicals was found in DOX and that the number of stable free radicals is always greater after irradiation. In in vitro studies, a higher cytotoxic activity of irradiated DOX and EPI in multidrug-resistant CCRF-VCR1000 cells was observed. This tendency was maintained during the storage at 4 °C for 90 days. Changes in CCRF-CEM cells' viability were not dependent on the irradiation status and its dose and were only drug-concentration dependent in all measurement time points. It was proved that increased potency of 25 kGy e-beam irradiated drugs results from their enhanced proapoptotic activity. Apoptotic cell death observed in CCRF-VCR1000 cells treated with irradiated drugs was caspase-8, -9, and -3 dependent and related to the increased Bax/Bcl-2 ratio. No significant differences in the effects of irradiated and non-irradiated drugs on p53 and NFκB transcription factor level and their translocation to the nucleus were noted. Increased activity of the irradiated drugs was not dependent on ABCB1 level.

Layered exfoliable crystalline materials based on Sm-, Eu- and Eu/Gd-2-phenylsuccinate frameworks. Crystal structure, topology and luminescence properties.

Three new layered metal-organic frameworks (MOFs) based on 2-phenylsuccinic acid (H2psa) and lanthanide ions with the formula [Ln2(C10H8O4)3(H2O)] (Ln = Eu, Sm and Eu-Gd) have been synthesized under solvothermal conditions and fully characterized by single-crystal X-ray diffraction, thermal and vibrational analyses. The compounds are isostructural featuring 2D frameworks that consist of infinite zigzag chains composed of [LnO8] and [LnO8(H2O)] edge-sharing polyhedra linked by psa ligands leading to layers further connected by weak π-π interactions in an edge orientation. Moreover, a topological study was carried out to obtain the simplified net for better comparison with structurally related compounds. The crystals were exfoliated into nanolayers after miniaturization by addition of sodium acetate as a capping agent in the reaction medium. Scanning electron microscopy was applied to characterize the miniaturized samples whereas the exfoliated hybrid nanosheets were studied by atomic force microscopy. The photoluminescence (PL) properties of the bulk compounds as well as the miniaturized and exfoliated materials were investigated and compared with other related ones. An exhaustive study of the Eu(iii)-based MOFs was performed on the basis of the obtained PL parameters (excitation and emission spectra, kr, knr, intrinsic quantum yields and lifetimes) to explore the underlying structure-property relationships.

Radiation sterilization of anthracycline antibiotics in solid state.

The impact of ionizing radiation generated by a beam of electrons of 25-400 kGy on the stability of such analogs of anthracycline antibiotics as daunorubicin (DAU), doxorubicin (DOX), and epidoxorubicin (EPI) was studied. Based on EPR results, it was established that unstable free radicals decay exponentially with the half-time of 4 days in DAU and DOX and 7 days in EPI after irradiation. Radiation-induced structural changes were analyzed with the use of spectrophotometric methods (UV-Vis and IR) and electron microscope imaging (SEM). A chromatographic method (HPLC-DAD) was applied to assess changes in the contents of the analogs in the presence of their impurities. The study showed that the structures of the analogs did not demonstrate any significant alterations at the end of the period necessary for the elimination of unstable free radicals. The separation of main substances and related substances (impurities and potential degradation products) allowed determining that no statistically significant changes in the content of particular active substances occurred and that their conversion due to the presence of free radicals resulting from exposure to an irradiation of 25 kGy (prescribed to ensure sterility) was not observed.

Transfer of IP3 through gap junctions is critical, but not sufficient, for the spread of apoptosis.

Decades of research have indicated that gap junction channels contribute to the propagation of apoptosis between neighboring cells. Inositol 1,4,5-trisphosphate (IP3) has been proposed as the responsible molecule conveying the apoptotic message, although conclusive results are still missing. We investigated the role of IP3 in a model of gap junction-mediated spreading of cytochrome C-induced apoptosis. We used targeted loading of high-molecular-weight agents interfering with the IP3 signaling cascade in the apoptosis trigger zone and cell death communication zone of C6-glioma cells heterologously expressing connexin (Cx)43 or Cx26. Blocking IP3 receptors or stimulating IP3 degradation both diminished the propagation of apoptosis. Apoptosis spread was also reduced in cells expressing mutant Cx26, which forms gap junctions with an impaired IP3 permeability. However, IP3 by itself was not able to induce cell death, but only potentiated cell death propagation when the apoptosis trigger was applied. We conclude that IP3 is a key necessary messenger for communicating apoptotic cell death via gap junctions, but needs to team up with other factors to become a fully pro-apoptotic messenger.

TLR-2 and TLR-9 are sensors of apoptosis in a mouse model of doxorubicin-induced acute inflammation.

Anthracycline antibiotics are inducers of an immunogenic form of apoptosis that has immunostimulatory properties because of the release of damage-associated molecular patterns. To study the mechanisms used by the innate immune system to sense this immunogenic form of cell death, we established an in vivo model of cell death induced by intraperitoneal injection of doxorubicin, a prototype of anthracyclines. The acute sterile inflammation in this model is characterized by rapid influx of neutrophils and increased levels of IL-6 and monocyte chemotactic protein-1. We demonstrate that acute inflammation induced by doxorubicin is associated with apoptosis of monocytes/macrophages and that it is specific for doxorubicin, an immunogenic chemotherapeutic. Further, the inflammatory response is significantly reduced in mice deficient in myeloid differentiation primary response gene 88 (MyD88), TLR-2 or TLR-9. Importantly, a TLR-9 antagonist reduces the recruitment of neutrophils induced by doxorubicin. By contrast, the acute inflammatory response is not affected in TRIF(Lps2) mutant mice and in TLR-3, TLR-4 and caspase-1 knockout mice, which shows that the inflammasome does not have a major role in doxorubicin-induced acute inflammation. Our findings provide important new insights into how the innate immune system senses immunogenic apoptotic cells and clearly demonstrate that the TLR-2/TLR-9-MyD88 signaling pathways have a central role in initiating the acute inflammatory response to this immunogenic form of apoptosis.

Influence of temperature on the life-cycle of Globodera spp.

The potato cyst nematodes (PCN) G. rostochiensis (Woll.) and G. pallida (Stone) are the most economically important pests of potato (Solanum tuberosum L.) in the UK and are widespread in ware potato growing regions in Europe. The new EU directive 2007/33/EC which came into effect July 1, 2010 aims to control their spread and limit further increases in populations. We are investigating the role of temperature in the life cycle of PCN to assess how this effects population multiplication in relation to managing PCN. Hatching and nematode development are stages in the life cycle that are affected by temperature and thus are important life stages that can be examined to determine the impact of temperature on the length of time required for one generation to be completed and the potential for final populations to increase on different potato genetic backgrounds. In some conditions a partial or complete second generation has also been observed within the growing season. Females have been observed on the surface of tubers and "pecking" skin damage can occur which may be a result of a second generation. We are investigating the influence of temperature on the potential for a second generation or the induction of diapause.

Karyotyping of the narrow-leafed lupin (Lupinus angustifolius L.) by using FISH, PRINS and computer measurements of chromosomes.

BAC (bacterial artificial chromosome) clones from the genomic BAC library of the narrow-leafed lupin (Lupinus angustifolius) were used for cytogenetic mapping of mitotic metaphase chromosomes of that species by the BAC-FISH technique. Location of the clones, together with cytogenetic markers localised earlier by FISH (fluorescence in situ hybridisation) and PRINS (primed in situ DNA labelling), was combined with computer-aided chromosome measurements, to construct the first idiogram of the narrow-leafed lupin. The chromosomes are meta- or submetacentric; the mean absolute chromosome lengths range from 1.9 microm to 3.8 microm, and mean relative lengths from 1.6% to 3.3%. Data concerning linkage of resistance to 2 fungal pathogens as well as assignment of the second linkage group to the appropriate chromosome are given for the first time.

Linear and nonlinear optical properties of azobenzene derivatives.

The results of computations of spectroscopic parameters of lowest-lying electronic excited states of azobenezene derivatives are presented. The analysis of experimentally recorded spectra was supported by quantum chemical calculations using density functional theory. The theoretically determined resonant (two-photon absorption probabilities) and non-resonant (first-order hyperpolarisability) nonlinear optical properties are also discussed, with an eye towards the performance of recently proposed long-range corrected (LRC) schemes (LC-BLYP and CAM-B3LYP functionals).

Anaemia is an independent predictor of poor outcome in patients with chronic heart failure.

BACKGROUND: Mild anaemia frequently occurs in patients with chronic heart failure (CHF), particularly in the advanced stages of the disease. The correction of anaemia with erythropoietin is a therapeutic possibility. The aim of this study was to assess prospectively the relationship between the prevalence of anaemia (haemoglobin level18 months in all survivors), and the end-point of the study was all-cause mortality. RESULTS: A total of 176 patients were enrolled (mean age: 63 years, New York Heart Association (NYHA) classification I/II/III/IV: 15/81/51/29; left ventricular ejection fraction (LVEF): 42%, ischaemic aetiology in 62%). In the whole population the mean haemoglobin level was 140+/-15 g/l. Anaemia was found in 18 (10%) patients, and was significantly more common in women than in men (18 vs. 7%, respectively, P=0.02) and in those with most severe CHF symptoms (frequency in NYHA I/II/III/IV: 0/9/10/21%, respectively; NYHA IV vs. I-III, P=0.03), but not related to the other clinical indices. Univariate analysis revealed NYHA class III-IV (hazard ratio 3.8, 95% CI: 1.6-8.9, P=0.003), low LVEF <35% (hazard ratio 2.3, 95% CI: 1.0-4.9, P=0.04) and anaemia (hazard ratio 2.9, 95% CI: 1.2-7.2, P=0.02) as predictors of 18-month mortality. In multivariate analysis, anaemia remained an independent predictor of death when adjusted for NYHA class and LVEF (hazard ratio: 2.6, 95% CI: 1.0-6.5, P=0.04). In anaemic patients, 18-month survival was 67% (95% CI: 45-89%) compared to 87% (81-92%) in patients with a normal haemoglobin level (P=0.016). CONCLUSIONS: Mild anaemia is a significant and independent predictor of poor outcome in unselected patients with CHF. Correction of low haemoglobin level may become an interesting therapeutic option for CHF patients.

Antibiotic sensitivity of bacteria isolated in 1998 and 1999 from patients with infections of upper airways residing in Western Pomerania.

Sensitivity to antibiotics of the most common pathogens isolated from the upper airways in north-west part of Poland shown significant regional variation. The rise in resistance to penicillin for Streptococcus pneumoniae (to 22%) and to macrolides for Streptococcus pyogenes, Streptococcus pneumoniae and Staphylococcus aureus was observed. No differences in sensitivity have been found between pathogens isolated from hospital and ambulatory patients.

Genetically modified tumour vaccines (GMTV) in melanoma clinical trials.

Since melanoma is a model immunogenic malignancy incurable in the disseminated phase of its natural course different immunotherapeutic approaches are tested in clinical trials. A number of tumour vaccines genetically modified (GMTV), with various immunostimulatory factors, are tested in phase I/II clinical trials. These factors include cytokines, tumour antigens (TA), costimulatory molecules or HLA antigens. We have designed a novel, mixed auto/allogeneic cellular melanoma vaccine modified with the IL-6 and the sIL-6R genes. Preclinical studies in a mouse model demonstrated that the IL-6/sIL-6R based vaccine is able to elicit efficient anti-tumour responses, mediated by CD8+ and NK cells, which resulted in inhibition of the tumour growth, metastases formation and prolonged survival of the animals treated. Irradiation of vaccine cells does not only lead to their sterilisation but also causes increased secretion of exogenous IL-6 and sIL-6R. Since January 1996 we have vaccinated more than one hundred metastatic melanoma patients. Promising clinical results (22% CR+PR, 32% SD) and the evidence of immune responses in the vaccinated patients have prompted us to design a phase III clinical trial which is to be open in 2000.

[Investigations on the prevalence of headache associated with mandibular dysfunction]. / Badania nad czestoscia wystepowania bólów glowy zwiazanych z dysfunkcja ukladu ruchowego narzadu zucia.

The role of mandibular dysfunction in the etiology of headache is still underestimated in the medical literature. For this reason an analysis of own questionnaire investigations published in the years 1983 to 1999 was done. These investigations were carried out in 3915 subjects aged 15-66. In order to determine the prevalence of headache associated with mandibular dysfunction in the analysis mandibular parafunctions and clicking in the temporomandibular joints (TMJs) were selected. The comparison of the prevalence of headache in groups with and without mandibular parafunctions and in groups with and without clicking in the TMJs has shown that the prevalence of headache was significantly higher in groups with mandibular parafunctions and with clicking in the TMJs than in groups without these disturbances. The difference in the prevalence of headache in the investigated groups has shown that headaches noted in the population can be associated with mandibular parafunctions in 18.2% and dependent on the age with clicking in the TMJs in 9.7% to 25%.