Interlayer bond formation in black phosphorus at high pressure

Black phosphorus was compressed at room temperature across the A17, A7 and simple-cubic phases up to 30 GPa, using a diamond anvil cell and He as pressure transmitting medium. Synchrotron X-ray diffraction showed the persistence of two previously unreported peaks related to the A7 structure in the pressure range of the simple-cubic phase. The Rietveld refinement of the data demonstrates the occurrence of a two-step mechanism for the A7 to simple-cubic phase transition, indicating the existence of an intermediate pseudo simple-cubic structure. From a chemical point of view this study represents a deep insight on the mechanism of interlayer bond formation during the transformation from the layered A7 to the non-layered simple-cubic phase of phosphorus, opening new perspectives for the design, synthesis and stabilization of phosphorene-based systems. As superconductivity is concerned, a new experimental evidence to explain the anomalous pressure behavior of Tc in phosphorus below 30 GPa is provided

Comparative chloroplast genomics: analyses including new sequences from the angiosperms Nuphar advena and Ranunculus macranthus

<p>Abstract</p> <p>Background</p> <p>The number of completely sequenced plastid genomes available is growing rapidly. This array of sequences presents new opportunities to perform comparative analyses. In comparative studies, it is often useful to compare across wide phylogenetic spans and, within angiosperms, to include representatives from basally diverging lineages such as the genomes reported here: <it>Nuphar advena </it>(from a basal-most lineage) and <it>Ranunculus macranthus </it>(a basal eudicot). We report these two new plastid genome sequences and make comparisons (within angiosperms, seed plants, or all photosynthetic lineages) to evaluate features such as the status of <it>ycf15 </it>and <it>ycf68 </it>as protein coding genes, the distribution of simple sequence repeats (SSRs) and longer dispersed repeats (SDR), and patterns of nucleotide composition.</p> <p>Results</p> <p>The <it>Nuphar </it>[GenBank:<ext-link ext-link-type="gen" ext-link-id="NC_008788">NC_008788</ext-link>] and <it>Ranunculus </it>[GenBank:<ext-link ext-link-type="gen" ext-link-id="NC_008796">NC_008796</ext-link>] plastid genomes share characteristics of gene content and organization with many other chloroplast genomes. Like other plastid genomes, these genomes are A+T-rich, except for rRNA and tRNA genes. Detailed comparisons of <it>Nuphar </it>with <it>Nymphaea</it>, another Nymphaeaceae, show that more than two-thirds of these genomes exhibit at least 95% sequence identity and that most SSRs are shared. In broader comparisons, SSRs vary among genomes in terms of abundance and length and most contain repeat motifs based on A and T nucleotides.</p> <p>Conclusion</p> <p>SSR and SDR abundance varies by genome and, for SSRs, is proportional to genome size. Long SDRs are rare in the genomes assessed. SSRs occur less frequently than predicted and, although the majority of the repeat motifs do include A and T nucleotides, the A+T bias in SSRs is less than that predicted from the underlying genomic nucleotide composition. In codon usage third positions show an A+T bias, however variation in codon usage does not correlate with differences in A+T-richness. Thus, although plastome nucleotide composition shows "A+T richness", an A+T bias is not apparent upon more in-depth analysis, at least in these aspects. The pattern of evolution in the sequences identified as <it>ycf15 </it>and <it>ycf68 </it>is not consistent with them being protein-coding genes. In fact, these regions show no evidence of sequence conservation beyond what is normal for non-coding regions of the IR.</p

Coordination polymerization of alkenylsilsesquioxanes and their copolymerization with olefins or styrene

Artykuł stanowi kontynuację przeglądu literatury dotyczącej koordynacyjnej polimeryzacji silseskwioksanów (POSS), zawierających zdolne do polimeryzacji wiązanie podwójne, oraz ich kopolimeryzacji głównie zolefinami, atakże ze styrenem. Zastosowanie katalizatorów metalocenowych aktywowanych metyloaluminoksanem (MAO) zapewnia efektywną (ko)polimeryzację silseskwioksanów zarówno zolefinami, jak istyrenem. Wprowadzenie do materiału polimerowego komonomeru POSS korzystnie wpływa na właściwości otrzymanych produktów, które cechują się większą odpornością termiczną oraz wytrzymałością mechaniczną niż ich odpowiedniki niezawierające POSS.The paper is acontinuation of literature review on the coordination polymerization of silsesquioxanes (POSS) containing apolymerizable double bond and their copolymerization with alkenes and styrene. In both these cases, an efficient (co)polymerization can be achieved by using metallocene catalysts activated with methylalumoxane (MAO). The incorporation of POSS comonomer to the polymeric material positively affects the properties of the obtained products. They show improved heat resistance and higher mechanical strength than their non-modified counterparts

Changes in the amount of reduced glutathione and activity of antioxidant enzymes in chosen mouse organs influenced by zymosan and melatonin administration

Reduced glutathione (GSH), superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSHPx) are vital components of the antioxidative barrier in animal cells. It is suggested more often now that the effectiveness of the protection of cells against the oxidative stress caused by the inflammation process depends on the amount of GSH and the activity of SOD, CAT and GSHPx. That is why the effect of zymosan A (40 mg/kg body mass) and the combined treatment with zymosan A (at the same dose) and melatonin (50 mg/kg body mass) on the amount of GSH in the blood and the amount of GSH and activity of SOD, CAT and GSHPx in the brain, liver and kidneys of male mice was estimated. Animals (n = 108) were decapitated after 3, 6 and 24 hours since the moment of the administration of only zymosan A, and combined zymosan A and after one hour melatonin. After the injection of zymosan A it was found that the amount of GSH is significantly lower after 3 and 6 hours in the blood and studied organs. The administration of zymosan A, followed by the administration of melatonin limited the decrease in the amount of this tripeptide in the same time. Simultaneously, the decrease in the amount of GSH in the studied organs was accompanied by a similar decrease in the activity of SOD, CAT and GSHPx after the injection of only zymosan A and a limited decrease in the activity after the administration of both zymosan A and melatonin. It is suggested that a decreased content of GSH and a decrease in the activity of the studied antioxidative enzymes is caused by the oxidative stress accompanying the inflammation process

Silsesquioxanes and their application in the synthesis of polymeric materials

Artykuł stanowi przegląd literatury dotyczącej syntezy oraz charakterystyki materiałów polimerowych zawierających silseskwioksany (POSS). Przedstawiono metody otrzymywania hybrydowych materiałów polimerowych zudziałem funkcjonalizowanych POSS na drodze click chemistry, polikondensacji, poliaddycji, metatezy zotwarciem pierścienia ipolimeryzacji rodnikowej zarówno konwencjonalnej, jak i kontrolowanej (ATRP).The paper is a literature review concerning the synthesis and characterization of polymeric materials containing silsesquioxanes (POSS). The methods of preparation of the functionalized POSS-containing hybrid polymeric materials using click chemistry, polycondensation, polyaddition, ring-opening metathesis and free-radical polymerization — both conventional and controlled (ATRP) — have been presented. Depending on the polyreaction mechanism, the type of monomer used and the structure of POSS cage, linear copolymers with silsesquioxane units in the main or side chains as well as star copolymers can be obtained. The incorporation of POSS into copolymer system results in increased glass transition and decomposition temperatures, better resistance to oxidation and improved mechanical properties when compared to the conventional polymeric systems

Effect of N-methyl-D-aspartic acid on activity of superoxide dismutase, catalase, glutathione peroxidase and reduced glutathione level in selected organs of the mouse

One of the major classes of ionotropic glutamate receptors is the class of N-methyl-D-aspartate receptors (NMDARs). Receptor activation recruits, via calcium signal transduction mechanisms which play important roles in oxidative metabolism, mitochondrial free radical production and occurrence of other mitochondrial factors which potentially contribute to excitotoxicity and neuronal death. In the present study, the effects of stimulation of NMDARs by applying N-methyl-D-aspartic acid (NMDA) in the brain, liver, kidneys and pancreas on change of the activity of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSHPx) and in the amount of reduced glutathione (GSH) in blood, brain, liver and kidneys has been investigated. Statistically significant decrease of the activity of SOD, CAT and GSHPx and in the amount of reduced glutathione (GSH) was found in the examined organs after administration of NMDA, an agonist of NMDA receptors, demonstrating that NMDA administration compromises the antioxidant status in the investigated organs of the mouse

Coordination (co)polymerization of olefins

Artykuł prezentuje podsumowanie wieloletnich prac w zakresie koordynacyjnej polimeryzacji olefin prowadzonych w Katedrze Technologii Chemicznej i Chemii Polimerów Wydziału Chemii Uniwersytetu Opolskiego. Począwszy od beznośnikowych i zakotwiczonych na oryginalnym nośniku chlorku magnezu z tetrahydrofuranem tytanowych i wanadowych katalizatorów Zieglera-Natty, zespół opolski włączył się w nurt światowych badań nad poszukiwaniem coraz to nowszych układów katalitycznych – bardziej aktywnych i produkujących poliolefiny o różnorodnych, pożądanych właściwościach. Dalsze badania polimeryzacji i kopolimeryzacji etylenu z wyższymi 1-olefinami prowadzono z zastosowaniem różnorodnych beznośnikowych i nośnikowych metalocenowych układów katalitycznych uzyskując z dużą wydajnością odpowiednie polimery i kopolimery. Polietylen o bardzo ciekawych właściwościach, np. niespotykanie wysokim stopniu krystaliczności, uzyskano w toku badań z użyciem cieczy jonowych jako swoistych nośników katalizatorów metalocenowych w dwufazowej polimeryzacji olefin. Obecnie trwają badania nad nową generacją układów katalitycznych, zwanych postmetalocenowymi, w skład których wchodzą kompleksy zawierające rozbudowane wielodonorowe ligandy, np. salenowe, salanowe, fenoksyiminowe i diamino-bis(fenolanowe). Wobec tych układów otrzymuje się homo- i kopolimery olefin o bardzo różnorodnych właściwościach: od ataktycznych produktów polimeryzacji 1-olefin o dużej masie molowej do polietylenu liniowego o bardzo dużej masie molowej typu UHMW czy polietylenu bimodalnego.The article is a summary of long-term research in field of coordination copolymerization of olefins carried out in the Division of Chemical Technology and Polymer Chemistry at the Faculty of Chemistry of the Opole University. Starting from titanium and vanadium Ziegler-Natta catalysts non-supported and anchored on original support of magnesium chloride with tetrahydrofuran, the Opole group joined the worldwide research trend on search for newer and newer catalytic systems – more active and producing polyolefins of various desired properties. Further studies of polymerization and copolymerization of ethylene with higher 1-olefins were conducted using various non-supported and supported metallocene catalytic systems producing respective polymers and copolymers with high yield. Polyethylene of very interesting properties, e.g. unusually high degree of crystallinity was produced in the course of research involving use of ionic liquids as specific support for metallocene catalysts in two phase polymerization of olefins. Currently, there are studies in progress on new generation of catalytic systems, called post-metallocene catalysts that include complexes bearing multidonor ligands, e.g. salen, salan, phenoxyimine and diaminobis(phenolate) ligands. Use of such systems enables production of olefin homo- and copolymers of wide variety of properties: from high molecular weight atactic products of 1-olefin polymerization to linear high molecular weight polyethylene of ultra of type UHMW and bimodal polyethylene

Correlations between somatic features, anteroposterior spinal curvatures and trunk muscle strength in schoolchildren

Background: Evaluation of body posture and strength of spinal muscles in children during their progressive ontogenesis is significant for the evaluation of their physical health condition and physical fitness. It is also a reference point in a process of control and medical care. Purpose: The aim if this study was to evaluate correlation between the selected features of somatic body structure, shape of anteroposterior spinal curves and force-velocity (FV) parameters of trunk muscles in school children. Participants and methods: The sample involved 104 children aged 10–11 years, 60 females (10.74 ± 0.7) and 44 males (10.50 ± 0.9). Body posture was assessed using the Moiré photogrammetry while trunk muscles (flexors and extensors) strength was measured isokinetically. Results: The results of the research revealed the existence of many average and strong correlations observed between the analysed somatic characteristics and forcevelocity (FV) parameters of trunk muscles. Correlation between the volume of the spinal curvatures in the sagittal plane and forcevelocity parameters of trunk extensors and flexors were average or weak for both groups of children. Conclusion: Somatic features indicated stronger correlation with trunk muscles' strength than with the size of the anteroposterior spinal curves

Synthesis of high-quality crystalline carbon nitride oxide by selectively driving the high-temperature instability of urea with pressure

One-step synthesis using only physical tools is an appealing “green” method for the realization of technological materials. High-pressure conditions are particularly suitable in the attainment of extended supramolecular networks and in combination with high-temperature are effective in selecting specific reaction pathways to increase product quality. Here we show how pressures below 3 GPa and temperatures on the order of 420 K are effective for the synthesis, from urea crystal phase IV, of 2D graphitic carbon nitride oxide with enhanced crystalline quality. Angle-dispersive X-ray diffraction and Fourier transform IR spectroscopy show that the reaction becomes less selective at higher pressure with the formation of melamine and ammonium carbamate as byproducts. An anomalous positive slope is shown by the P–T instability boundary, likely arising from unfavorable hydrogen bonding with respect to the topochemical path, making urea an interesting case study for gaining insight into the role of hydrogen bonding in solid-state reactivity