Synthesis and spectroscopic properties of cobalt(III) complexes of some aroyl hydrazones: x-ray crystal structures of one cobalt(III) complex and two aroyl hydrazone ligands

Cobalt(III) complexes of diacetyl monooxime benzoyl hydrazone (dmoBH(2)) and diacetyl monooxime isonicotinoyl hydrazone (dmoInH(2)) have been synthesized and characterized by elemental analyses and spectroscopic methods. The X-ray crystal structures of the two hydrazone ligands, as well as that of the cobalt(III) complex [Co(III)(dmoInH)(2)]Cl center dot 2H(2)O, are also reported. It is found that in the cobalt(III) complexes the Co(III) ion is hexa-coordinated, the hydrazone ligands behaving as mono-anionic tridentate O,N,N donors. In the [Co(III)(dmoInH) (2)]Cl center dot 2H(2)O complex, the amide and the oxime hydrogens are deprotonated for both the ligands, while the isonicotine nitrogens are protonated. In the [Co(III)(d-moBH)(2)] Cl complex, only the amide nitrogens are deprotonated. It is shown that the additional hydrogen bonding capability of the isonicotine nitrogen results in different conformation and supramolecular structure for dmoInH(2), compared to dmoBH(2), in the solid state. Comparing the structure of the [CoIII(dmoInH)(2)]Cl center dot 2H(2)O with that of the Zn(II) complex of the same ligand, reported earlier, it is seen that the metal ion has a profound influence on the supramolecular structure, due to change in geometrical dispositions of the chelate rings.

The ecological impact of conquest and colonization on a medieval frontier landscape: combined palynological and geochemical analysis of lake sediments from Radzyń Chełminski, northern Poland

Slavic and German colonization of the southern Baltic between the 8th and 15th centuries A.D. is well-documented archaeologically and historically. Despite the large number of pollen profiles from Poland, few palaeoecological studies have examined the ecological impact of a process that was central to the expansion of European, Christian, societies. This study aims to redress this balance through multiproxy analysis of lake sediments from Radzyń Chełminski, Northern Poland, using pollen, element geochemistry (Inductively Coupled-Optical Emission Spectroscopy [ICP-OES]), organic content, and magnetic susceptibility. The close association between lake and medieval settlements presents the ideal opportunity to reconstruct past vegetation and land-use dynamics within a well-documented archaeological, historical, and cultural context. Three broad phases of increasing landscape impact are visible in the pollen and geochemical data dating from the 8th/9th, 10th/11th, and 13th centuries, reflecting successive phases of Slavic and German colonization. This involved the progressive clearance of oak-hornbeam dominated woodland and the development of an increasingly open agricultural landscape. Although the castles and towns of the Teutonic Order remain the most visible signs of medieval colonization, the palynological and geochemical data demonstrate that the major phase of woodland impact occurred during the preceding phase of Slavic expansion; Germans colonists were entering a landscape already significantly altered.

Efficient masking of corrosion and fission products such as Ni(II) and Pd(II) in the presence of the minor actinide Am(III) using hydrophilic anionic or cationic bis-triazines

Water soluble anionic and cationic bis-triazine ligands are able to suppress (mask) the extraction of corrosion and fission products such as Ni(II) and Pd(II) that are found in PUREX raffinates. Thus it is possible to separate these elements from the minor actinide Am(III). Although some masking agents have previously been developed that retard the extraction of Pd(II), this is the first time a masking agent has been developed for Ni(II).

Are sulfurous soil amendments (S0, Fe(II)SO4, Fe(III)SO4) an effective tool in the restoration of heathland and acidic grassland after four decades of rock phosphate Fertilization?

This paper deals with the complex issue of reversing long-term improvements of fertility in soils derived from heathlands and acidic grasslands using sulfur-based amendments. The experiment was conducted on a former heathland and acid grassland in the U.K. that was heavily fertilized and limed with rock phosphate, chalk, and marl. The experimental work had three aims. First, to determine whether sulfurous soil amendments are able to lower pH to a level suitable for heathland and acidic grassland re-creation (approximately 3 pH units). Second, to determine what effect the soil amendments have on the available pool of some basic cations and some potentially toxic acidic cations that may affect the plant community. Third, to determine whether the addition of Fe to the soil system would sequester PO4− ions that might be liberated from rock phosphate by the experimental treatments. The application of S0 and Fe(II)SO4− to the soil was able to reduce pH. However, only the highest S0 treatment (2,000 kg/ha S) lowered pH sufficiently for heathland restoration purposes but effectively so. Where pH was lowered, basic cations were lost from the exchangeable pool and replaced by acidic cations. Where Fe was added to the soil, there was no evidence of PO4− sequestration from soil test data (Olsen P), but sequestration was apparent because of lower foliar P in the grass sward. The ability of the forb Rumex acetosella to apparently detoxify Al3+, prevalent in acidified soils, appeared to give it a competitive advantage over other less tolerant species. We would anticipate further changes in plant community structure through time, driven by Al3+ toxicity, leading to the competitive exclusion of less tolerant species. This, we suggest, is a key abiotic driver in the restoration of biotic (acidic plant) communities.

Diruthenium(II, III) complexes of ibuprofen, aspirin, naproxen and indomethacin non-steroidal anti-inflammatory drugs: Synthesis, characterization and their effects on tumor-cell proliferation

[Ru-2(dNSAID)(4)Cl] and novel [Ru-2(dNSAID)(4)(H2O)(2)]PF6 complexes, where dNSAID = deprotonated carboxylate from the non-steroidal anti-inflammatory drugs (NSIDs), respectively: ibuprofen, Hibp (1) and aspirin, Hasp (2); naproxen, Hnpx (3) and indomethacin, Hind (4), have been prepared and characterized by optical spectroscopic methods. All of the compounds exhibit mixed valent Ru-2(II, III) cores where metal-metal bonds are stabilized by four drug-carboxylate bridging ligands in paddlewheel type structures. The diruthenium complexes and their parent NSAIDs showed no significant effects for Hep2 human larynx or T24/83 human bladder tumor. In contrast, the coordination of Ru-2(II,III) core led to synergistic effects that increased significantly the inhibition of C6 rat glioma proliferation in relation to the organic NSAIDs naproxen and ibuprofen, The possibility that the complexes Ru-2-ibp and Ru-2-npx may exert effects (anti-angiogenic and anti-matrix metalloprotease) that are similar to those exhibited by NAMI-A opens new horizons for in vivo C6 glioma model studies. (C) 2007 Elsevier Ltd. All rights reserved.

The value of a saved tree : The lifecycle of CO2-emissions associated with the combination of printing paper and electricity production of wood in the U.S. and Sweden

The pulp- and paper production is a very energy intensive industry sector. Both Sweden and the U.S. are major pulpandpaper producers. This report examines the energy and the CO2-emission connected with the pulp- and paperindustry for the two countries from a lifecycle perspective.New technologies make it possible to increase the electricity production in the integrated pulp- andpaper mill through black liquor gasification and a combined cycle (BLGCC). That way, the mill canproduce excess electricity, which can be sold and replace electricity produced in power plants. In thisprocess the by-products that are formed at the pulp-making process is used as fuel to produce electricity.In pulp- and paper mills today the technology for generating energy from the by-product in aTomlinson boiler is not as efficient as it could be compared to the BLGCC technology. Scenarios havebeen designed to investigate the results from using the BLGCC technique using a life cycle analysis.Two scenarios are being represented by a 1994 mill in the U.S. and a 1994 mill in Sweden.The scenariosare based on the average energy intensity of pulp- and paper mills as operating in 1994 in the U.S.and Sweden respectively. The two other scenarios are constituted by a »reference mill« in the U.S. andSweden using state-of-the-art technology. We investigate the impact of varying recycling rates and totalenergy use and CO2-emissions from the production of printing and writing paper. To economize withthe wood and that way save trees, we can use the trees that are replaced by recycling in a biomassgasification combined cycle (BIGCC) to produce electricity in a power station. This produces extra electricitywith a lower CO2 intensity than electricity generated by, for example, coal-fired power plants.The lifecycle analysis in this thesis also includes the use of waste treatment in the paper lifecycle. Both Sweden and theU.S. are countries that recycle paper. Still there is a lot of paper waste, this paper is a part of the countries municipalsolid waste (MSW). A lot of the MSW is landfilled, but parts of it are incinerated to extract electricity. The thesis hasdesigned special scenarios for the use of MSW in the lifecycle analysis.This report is studying and comparing two different countries and two different efficiencies on theBLGCC in four different scenarios. This gives a wide survey and points to essential parameters to specificallyreflect on, when making assumptions in a lifecycle analysis. The report shows that there arethree key parameters that have to be carefully considered when making a lifecycle analysis of wood inan energy and CO2-emission perspective in the pulp- and paper mill in the U.S. and in Sweden. First,there is the energy efficiency in the pulp- and paper mill, then the efficiency of the BLGCC and last theCO2 intensity of the electricity displaced by BIGCC or BLGCC generatedelectricity. It also show that with the current technology that we havetoday, it is possible to produce CO2 free paper with a waste paper amountup to 30%. The thesis discusses the system boundaries and the assumptions.Further and more detailed research, including amongst others thesystem boundaries and forestry, is recommended for more specificanswers.

Push or pull? : The relationship between quality of care and use of complementary and alternative medicine among patients with lung cancer in Sweden

Little is known about relationships between quality of care (QoC) and use of complementary and alternative medicine (CAM) among patients with lung cancer (LC). Purpose: This study examines CAM-use among patients with LC in Sweden, associations between QoC and CAM-use among these patients, and reported aspects of LC-care perceived as particularly positive and negative by patients, as well as suggestions for improving QoC. Methods: Survey data from 94 patient members of the Swedish LC patient organization about CAM-use and QoC as measured by the instrument “Quality from the patient’s perspective” were analyzed. Results: Fifty (53%) LC-patients used CAM, with 40 of the CAM-users reporting that CAM helped them. The most common CAMs used were dietary supplements and natural remedies, followed by prayer. Significantly more patients reported using prayer and meditation for cure than was the case for other types of CAM used. Less than half the CAM-users reported having spoken with staff from the biomedical health care system about their CAM-use. Patients provided numerous suggestions for improving LC-care in a variety of areas, aiming at a more effective and cohesive care trajectory. No differences in QoC were found between CAM-users and non-CAM-users, but differences in CAM-use i.e. type of CAM, reasons for using CAM, and CAM-provider consulted could be associated with different experiences of care. Conclusions: It is important to recognize that CAM-users are not a homogeneous group but might seek different types of CAMs and CAM-providers in different situations depending on experiences of care.

On administrative borders and accessibility to public services: : The case of hospitals in Sweden.

An administrative border might hinder the optimal allocation of a given set of resources by restricting the flow of goods, services, and people. In this paper we address the question: Do administrative borders lead to poor accessibility to public service such as hospitals? In answering the question, we have examined the case of Sweden and its regional borders. We have used detailed data on the Swedish road network, its hospitals, and its geo-coded population. We have assessed the population’s spatial accessibility to Swedish hospitals by computing the inhabitants’ distance to the nearest hospital. We have also elaborated several scenarios ranging from strongly confining regional borders to no confinements of borders and recomputed the accessibility. Our findings imply that administrative borders are only marginally worsening the accessibility.

Perceptions of Sustainability and Functional Aspects on Liquid Carton Board Packaging Materials versus Competing Materials for Juice Applications in Sweden

This research explores the downstream perceptions of liquid carton board versus competing materials in packaging applications for juice. The methodology used is focus groups. The context is sustainability and functional performance, and related potential implications for the beverage industry value chain. The purpose is to get a deeper insight and understanding of functionality in relation to juice beverage packaging. The results confirm that there is no optimal packaging for every juice product, but a multitude, depending on the distribution channel, retail outlet, customer preferences, and context of consumption. There are some general packaging preferences, but the main deciding criteria for purchase seem to be the product characteristics in terms of quality, taste, brand, price and shelf life. For marketing reasons, packaging has to be adopted to the product and its positioning, liquid carton board packaging seem to have some functional advantages in distribution and is considered as sustainable and functional among many consumers. Major drawbacks seem to be shape limitations, lack of transparency, and lack of a “premium look”. To improve packaging performance and avoid sub-optimization, actors in the beverage industry value chain need to be integrated in development processes.

Novel catalyst systems based on Ni(II), Ti(IV), and Cr(III) complexes for oligo-and polymerization of ethylene

The complex of Brookhart Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6- diisopropylphenyl)-acenaphthenediimine) has been characterized after impregnation on silica (S1) and MAO-modified silicas (4.0, 8.0 and 23.0 wts.% Al/SiO2 called S2, S3 and S4, respectively). The treatment of these heterogeneous systems with MAO produces some active catalysts for the polymerization of the ethylene. A high catalytic activity has been gotten while using the system supported 1/S3 (196 kg of PE/mol[Ni].h.atm; toluene, Al/Ni = 1000, 30ºC, 60 min and atmospheric pressure of ethylene). The effects of polymerization conditions have been tested with the catalyst supported in S2 and the best catalytic activity has been gotten with solvent hexane, MAO as cocatalyst, molar ratio Al/Ni of 1000 and to the temperature of 30°C (285 kg of PE/mol[Ni].h.atm). When the reaction has been driven according to the in situ methodology, the activity practically doubled and polymers showed some similar properties. Polymers products by the supported catalysts showed the absence of melting fusion, results similar to those gotten with the homogeneous systems by DSC analysis. But then, polymers gotten with the transplanted system present according to the GPC’s curves the polydispersity (MwD) varies between 1.7 and 7.0. A polyethylene blend (BPE/LPE) was prepared using the complex Ni(α-diimine)Cl2 (1) (α-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {TpMs*}TiCl3 (2) (TpMs* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesitylpyrazol-1-yl)) supported in situ on MAO-modified silica (4.0 wts. -% Al/SiO2, S2). Reactions of polymerization of ethylene have been executed in the toluene in two different temperatures (0 and 30°C), varying the molars fraction of nickel (xNi), and using MAO as external cocatalyst. To all temperatures, the activities show a linear variation tendency with xNi and indicate the absence of the effect synergic between the species of nickel and the titanium. The maximum of activity have been found at 0°C. The melting temperature for the blends of polyethylene produced at 0 °C decrease whereas xNi increases indicating a good compatibility between phases of the polyethylene gotten with the two catalysts. The melting temperature for the blends of polyethylene showed be depend on the order according to which catalysts have been supported on the MAO-modified silica. The initial immobilization of 1 on the support (2/1/S2) product of polymers with a melting temperature (Tm) lower to the one of the polymer gotten when the titanium has been supported inicially (1/2/S2). The observation of polyethylenes gotten with the two systems (2/1/S2 and 1/2/S2) by scanning electron microscopy (SEM) showed the spherical polymer formation showing that the spherical morphology of the support to been reproduced. Are described the synthesis, the characterization and the catalytic properties for the oligomerization of the ethylene of four organometallics compounds of CrIII with ligands ([bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]amine] chromium (III) chloride (3a), [bis[2-(3,5- dimethyl-l-pyrazolyl)ethyl]benzylamine] chromium (III) chloride (3b), [bis[2-(3,5-dimethyl-lpyrazolyl) ethyl]ether] chromiun(III)chloride (3c), [bis[2-(3-phenyl-lpyrazolyl) ethyl]ether]chromiun(III)chloride (3d)). In relation of the oligomerization, at exception made of the compounds 3a, all complex of the chromium showed be active after activation with MAO and the TOF gotten have one effect differentiated to those formed with CrCl3(thf)3. The coordination of a tridentate ligand on the metallic center doesn't provoke any considerable changes on the formation of the C4 and C6, but the amount of C8 are decrease and the C10 and C12+ have increased. The Polymers produced by the catalyst 3a to 3 and 20 bar of ethylene have, according to analyses by DSC, the temperatures of fusion of 133,8 and 136ºC respectively. It indicates that in the two cases the production of high density polyethylene. The molar mass, gotten by GPC, is 46647 g/mols with MwD = 2,4 (3 bar). The system 3c/MAO showed values of TOF, activity and selectivity to different α-olefins according to the pressure of ethylene uses. Himself that shown a big sensibility to the concentration of ethylene solubilized.

Biosorption of Cr(III) using in natura and chemically treated tropical peats

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dens invaginatus type III: report of a case and 10-year radiographic follow-up

Aim the purpose of this article is to report the 10-year follow-up of a right mandibular central incisor with 'dens invaginatus' that was root filled.Summary 'Dens invaginatus ' is a rare malformation of teeth, probably resulting from an infolding of the dental papilla during tooth development. It has alternatively been called 'dens in dente' and 'dilated composite odontome'. Radiographic examination may clearly demonstrate this feature, although no signs may be recognized clinically. If no entrance to the invagination can be detected and there are no signs of pulp pathosis, then no treatment is required other than fissure sealing of the invagination. In deep invaginations, it is likely that root-canal treatment may be required. Occasionally, when the tooth has an immature root, apexification is necessary. Root-canal treatment of a right mandibular central incisor with 'dens invaginatus ' is described along with 10-year follow-up.Key learning pointsBoth clinical and radiographic examinations are necessary to determine morphological features of teeth before root-canal treatment.Sensibility testing to determine the pulp condition is critical prior to treatment.

Thermal Behaviour Studies of Solid State Lanthanide (III) and Yttrium (III) Compounds of Cinnamylidenepyruvic Acid in an Atmosphere of Air

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dissociation of enzymatic and pharmacological properties of piratoxins-I and -III, two myotoxic phospholipases A(2) from Bothrops pirajai snake venom

Piratoxins (PrTX) I and III are phospholipases A(2) (PLA(2)s) or PLA(2) homologue myotoxins isolated from Bothrops pirajai snake venom, which also induce myonecrosis, bactericidal activity against Escherichia coli, disruption of artificial membranes, and edema. PrTX-III is a catalytically active hemolytic and anticoagulant Asp49 PLA(2), while PrTX-I is a Lys49 PLA, homologue, which is catalytically inactive on artificial substrates, but promotes blockade of neuromuscular transmission. Chemical modifications of His, Lys, Tyr, and Trp residues of PrTX-I and PrTX-III were performed, together with cleavage of the N-terminal octapeptide by CNBr and inhibition by heparin and EDTA. The lethality, bactericidal activity, myotoxicity, neuromuscular effect, edema inducing effect, catalytic and anticoagulant activities, and the liposome-disruptive activity of the modified toxins were evaluated. A complex pattern of functional differences between the modified and native toxins was observed. However, in general, chemical modifications that significantly affected the diverse pharmacological effects of the toxins did not influence catalytic or membrane disrupting activities. Analysis of structural changes by circular dichroism spectroscopy demonstrated significant changes in the secondary structure only in the case of N-terminal octapeptide cleavage. These data indicate that PrTX-I and PrTX-III possess regions other than the catalytic site, which determine their toxic and pharmacological activities. (C) 2001 Academic Press.