New insights on river water chemistry by using non-centred simplicial principal component analysis: a case study

The use of perturbation and power transformation operations permits the investigation of linear processes in the simplex as in a vectorial space. When the investigated geochemical processes can be constrained by the use of well-known starting point, the eigenvectors of the covariance matrix of a non-centred principalcomponent analysis allow to model compositional changes compared with a reference point.The results obtained for the chemistry of water collected in River Arno (central-northern Italy) have open new perspectives for considering relative changes of the analysed variables and to hypothesise the relative effect of different acting physical-chemical processes, thus posing the basis for a quantitative modelling

Heavy metal accumulation by intestinal helminths of vertebrates

The relevancy of parasites as potential indicators of environmental quality has been increasing over the last years, mostly due to the variety of ways in which they respond to anthropogenic pollution. The use of fish parasites as bioindicators of heavy metal pollution in aquatic ecosystems has been widely studied. However, little information concerning terrestrial habitats is presently available. In fact, in the last two decades several studies have been performed worldwide in different habitats and/or conditions (theoretically both in polluted and unpolluted terrestrialecosystems, but mainly in aquatic ecosystems) in order to investigate heavy metal pollution using parasitological models. Different groups of vertebrates (mainly fish, mammals and birds) and several parasitological models have been tested involving acanthocephalans mostly, but also cestodes and nematodes. It is not the aim of this chapter to do a complete revision of the availabledata concerning this subject. Instead, we emphasize some general aspects and compile a mini-review of the work performed in this field by our research group. The results obtained until now allow confirming several parasitic models as promising bioindicator systems to evaluate environmental cadmium and mainly lead pollution in terrestrial non-urban habitats, as it was already demonstrated for aquatic ecosystems. The present knowledge also allows confirming that parasites can reveal environmental impact. Environmental parasitology is an interdisciplinary field, which needs simultaneous expertise from toxicology, environmental chemistry and parasitology. Furthermore, environmental parasitology should be taken into account in order to increase the efficiency of environmental monitoring programs.

Heavy metal accumulation by intestinal helminths of vertebrates

The relevancy of parasites as potential indicators of environmental quality has been increasing over the last years, mostly due to the variety of ways in which they respond to anthropogenic pollution. The use of fish parasites as bioindicators of heavy metal pollution in aquatic ecosystems has been widely studied. However, little information concerning terrestrial habitats is presently available. In fact, in the last two decades several studies have been performed worldwide in different habitats and/or conditions (theoretically both in polluted and unpolluted terrestrialecosystems, but mainly in aquatic ecosystems) in order to investigate heavy metal pollution using parasitological models. Different groups of vertebrates (mainly fish, mammals and birds) and several parasitological models have been tested involving acanthocephalans mostly, but also cestodes and nematodes. It is not the aim of this chapter to do a complete revision of the availabledata concerning this subject. Instead, we emphasize some general aspects and compile a mini-review of the work performed in this field by our research group. The results obtained until now allow confirming several parasitic models as promising bioindicator systems to evaluate environmental cadmium and mainly lead pollution in terrestrial non-urban habitats, as it was already demonstrated for aquatic ecosystems. The present knowledge also allows confirming that parasites can reveal environmental impact. Environmental parasitology is an interdisciplinary field, which needs simultaneous expertise from toxicology, environmental chemistry and parasitology. Furthermore, environmental parasitology should be taken into account in order to increase the efficiency of environmental monitoring programs.

Effects of cobalt-chromium everolimus eluting stents or bare metal stent on fatal and non-fatal cardiovascular events: patient level meta-analysis

Objectives: To examine the safety and effectiveness of cobalt-chromium everolimus eluting stents compared with bare metal stents. Design: Individual patient data meta-analysis of randomised controlled trials. Cox proportional regression models stratified by trial, containing random effects, were used to assess the impact of stent type on outcomes. Hazard ratios with 95% confidence interval for outcomes were reported. Data sources and study selection: Medline, Embase, the Cochrane Central Register of Controlled Trials. Randomised controlled trials that compared cobalt-chromium everolimus eluting stents with bare metal stents were selected. The principal investigators whose trials met the inclusion criteria provided data for individual patients. Primary outcomes: The primary outcome was cardiac mortality. Secondary endpoints were myocardial infarction, definite stent thrombosis, definite or probable stent thrombosis, target vessel revascularisation, and all cause death. Results: The search yielded five randomised controlled trials, comprising 4896 participants. Compared with patients receiving bare metal stents, participants receiving cobalt-chromium everolimus eluting stents had a significant reduction of cardiac mortality (hazard ratio 0.67, 95% confidence interval 0.49 to 0.91; P=0.01), myocardial infarction (0.71, 0.55 to 0.92; P=0.01), definite stent thrombosis (0.41, 0.22 to 0.76; P=0.005), definite or probable stent thrombosis (0.48, 0.31 to 0.73; P<0.001), and target vessel revascularisation (0.29, 0.20 to 0.41; P<0.001) at a median follow-up of 720 days. There was no significant difference in all cause death between groups (0.83, 0.65 to 1.06; P=0.14). Findings remained unchanged at multivariable regression after adjustment for the acuity of clinical syndrome (for instance, acute coronary syndrome v stable coronary artery disease), diabetes mellitus, female sex, use of glycoprotein IIb/IIIa inhibitors, and up to one year v longer duration treatment with dual antiplatelets. Conclusions: This meta-analysis offers evidence that compared with bare metal stents the use of cobalt-chromium everolimus eluting stents improves global cardiovascular outcomes including cardiac survival, myocardial infarction, and overall stent thrombosis.

Effects of cobalt-chromium everolimus eluting stents or bare metal stent on fatal and non-fatal cardiovascular events: patient level meta-analysis

Objectives: To examine the safety and effectiveness of cobalt-chromium everolimus eluting stents compared with bare metal stents. Design: Individual patient data meta-analysis of randomised controlled trials. Cox proportional regression models stratified by trial, containing random effects, were used to assess the impact of stent type on outcomes. Hazard ratios with 95% confidence interval for outcomes were reported. Data sources and study selection: Medline, Embase, the Cochrane Central Register of Controlled Trials. Randomised controlled trials that compared cobalt-chromium everolimus eluting stents with bare metal stents were selected. The principal investigators whose trials met the inclusion criteria provided data for individual patients. Primary outcomes: The primary outcome was cardiac mortality. Secondary endpoints were myocardial infarction, definite stent thrombosis, definite or probable stent thrombosis, target vessel revascularisation, and all cause death. Results: The search yielded five randomised controlled trials, comprising 4896 participants. Compared with patients receiving bare metal stents, participants receiving cobalt-chromium everolimus eluting stents had a significant reduction of cardiac mortality (hazard ratio 0.67, 95% confidence interval 0.49 to 0.91; P=0.01), myocardial infarction (0.71, 0.55 to 0.92; P=0.01), definite stent thrombosis (0.41, 0.22 to 0.76; P=0.005), definite or probable stent thrombosis (0.48, 0.31 to 0.73; P<0.001), and target vessel revascularisation (0.29, 0.20 to 0.41; P<0.001) at a median follow-up of 720 days. There was no significant difference in all cause death between groups (0.83, 0.65 to 1.06; P=0.14). Findings remained unchanged at multivariable regression after adjustment for the acuity of clinical syndrome (for instance, acute coronary syndrome v stable coronary artery disease), diabetes mellitus, female sex, use of glycoprotein IIb/IIIa inhibitors, and up to one year v longer duration treatment with dual antiplatelets. Conclusions: This meta-analysis offers evidence that compared with bare metal stents the use of cobalt-chromium everolimus eluting stents improves global cardiovascular outcomes including cardiac survival, myocardial infarction, and overall stent thrombosis.

Link between microstructure and properties in new metallurgical concepts for very low loss non-oriented electrical steel

The influence of chemistry and soaking temperature (maximal temperature of the continuous annealing) on the final properties of non-oriented electrical steels has been studied. With this objective two different studies have been performed. First the Mn, Ni and Cr content of a low loss electrical steel composition has been modified. An intermediate content and a high content of each element has been added in order to study the influence of this components on the magnetic looses, grain size and texture. Secondly the influence of the soaking temperature on magnetic properties, grain size and oxidation in four grades of non-oriented electrical steels (Steel A, B, C and D) was studied.

Collective spin excitations of alkali-metal clusters

The response function of alkali-metal clusters, modeled as jellium spheres, to dipole (L=1) and quadrupole (L=2) spin-dependent fields is obtained within the time-dependent local-spin-density approximation of density-functional theory. We predict the existence of low-energy spin modes of surface type, which are identified from the strength function. Their collectivity and evolution with size are discussed.

Shaping mechanisms of metal specificity in a family of metazoan Metallothioneins: evolutionary differentiation of Mollusc MTs.

Background: The degree of metal binding specificity in metalloproteins such as metallothioneins (MTs) can be crucial for their functional accuracy. Unlike most other animal species, pulmonate molluscs possess homometallic MT isoforms loaded with Cu+ or Cd2+. They have, so far, been obtained as native metal-MT complexes from snail tissues, where they are involved in the metabolism of the metal ion species bound to the respective isoform. However, it has not as yet been discerned if their specific metal occupation is the result of a rigid control of metal availability, or isoform expression programming in the hosting tissues or of structural differences of the respective peptides determining the coordinative options for the different metal ions. In this study, the Roman snail (Helix pomatia) Cu-loaded and Cd-loaded isoforms (HpCuMT and HpCdMT) were used as model molecules in order t o elucidate the biochemical and evolutionary mechanisms permitting pulmonate MTs to achieve specificity for their cognate metal ion. Results: HpCuMT and HpCdMT were recombinantly synthesized in the presence of Cd2+, Zn2+ or Cu2+ and corresponding metal complexes analysed by electrospray mass spectrometry and circular dichroism (CD) and ultra violet-visible (UV-Vis) spectrophotometry. Both MT isoforms were only able to form unique, homometallic and stable complexes (Cd6-HpCdMT and Cu12-HpCuMT) with their cognate metal ions. Yeast complementation assays demonstrated that the two isoforms assumed metal-specific functions, in agreement with their binding preferences, in heterologous eukaryotic environments. In the snail organism, the functional metal specificity of HpCdMT and HpCuMT was contributed by metal-specific transcription programming and cell-specific expression. Sequence elucidation and phylogenetic analysis of MT isoforms from a number of snail species revealed that they possess an unspecific and two metal-specific MT isoforms, whose metal specificity was achieved exclusively by evolutionary modulation of non-cysteine amino acid positions. Conclusion: The Roman snail HpCdMT and HpCuMT isoforms can thus be regarded as prototypes of isoform families that evolved genuine metal-specificity within pulmonate molluscs. Diversification into these isoforms may have been initiated by gene duplication, followed by speciation and selection towards opposite needs for protecting copper-dominated metabolic pathways from nonessential cadmium. The mechanisms enabling these proteins to be metal-specific could also be relevant for other metalloproteins.

Spontaneous mirror symmetry breaking in the limited enantioselective autocatalysis model: abyssal hydrotermal vents as scenario for the emergence of chirality in prebiotic chemistry

The emergence of chirality in enantioselective autocatalysis for compounds unable to transform according to the Frank-like reaction network is discussed with respect to the controversial limited enantioselectivity (LES) model composed of coupled enantioselective and non-enantioselective autocatalyses. The LES model cannot lead to spontaneous mirror symmetry breaking (SMSB) either in closed systems with a homogeneous temperature distribution or in closed systems with a stationary non-uniform temperature distribution. However, simulations of chemical kinetics in a two-compartment model demonstrate that SMSB may occur if both autocatalytic reactions are spatially separated at different temperatures in different compartments but coupled under the action of a continuous internal flow. In such conditions, the system can evolve, for certain reaction and system parameters, toward a chiral stationary state; that is, the system is able to reach a bifurcation point leading to SMSB. Numerical simulations in which reasonable chemical parameters have been used suggest that an ade- quate scenario for such a SMSB would be that of abyssal hydrothermal vents, by virtue of the typical temper- ature gradients found there and the role of inorganic solids mediating chemical reactions in an enzyme-like role. Key Words: Homochirality Prebiotic chemistry.

Structures of ethylenediaminetetraacetato (3-) metal complexes. I complexes with Co, Mg and Cd metals

(I): Hexaaquacobalt(II) aqua[ethylenediaminetetraacetato(3-)]cobaltate(II) dihydrate, [Co(H2O)6][Co(C10H13N2O8)(H2O)]2.2H2O (Ibis): Hexaaquamagnesium(II) aqua[ethylenediaminetetraacetato(3-)]magnesiate(II) dihydrate, [Mg(H2O)6][Mg(C10H13N2O8)(H2O)]2.2H2O (II):Tetraaquabis{aqua[ethylenediaminetetraacetato(3-)]cadmium(II)-O-O'}Cadmium(II) tetrahydrate

Structures of ethylenediaminetetraacetato (3-) metal complexes. I complexes with Co, Mg and Cd metals

(I): Hexaaquacobalt(II) aqua[ethylenediaminetetraacetato(3-)]cobaltate(II) dihydrate, [Co(H2O)6][Co(C10H13N2O8)(H2O)]2.2H2O (Ibis): Hexaaquamagnesium(II) aqua[ethylenediaminetetraacetato(3-)]magnesiate(II) dihydrate, [Mg(H2O)6][Mg(C10H13N2O8)(H2O)]2.2H2O (II):Tetraaquabis{aqua[ethylenediaminetetraacetato(3-)]cadmium(II)-O-O'}Cadmium(II) tetrahydrate

Structures of ethylenediaminetetraacetato (3-) metal complexes. I complexes with Co, Mg and Cd metals

(I): Hexaaquacobalt(II) aqua[ethylenediaminetetraacetato(3-)]cobaltate(II) dihydrate, [Co(H2O)6][Co(C10H13N2O8)(H2O)]2.2H2O (Ibis): Hexaaquamagnesium(II) aqua[ethylenediaminetetraacetato(3-)]magnesiate(II) dihydrate, [Mg(H2O)6][Mg(C10H13N2O8)(H2O)]2.2H2O (II):Tetraaquabis{aqua[ethylenediaminetetraacetato(3-)]cadmium(II)-O-O'}Cadmium(II) tetrahydrate

Metal dealing at the origin of the Chordata phylum: The metallothionein system and metal overload response in Amphioxus.

Non-vertebrate chordates, specifically amphioxus, are considered of the utmost interest for gaining insight into the evolutionary trends, i.e. differentiation and specialization, of gene/protein systems. In this work, MTs (metallothioneins), the most important metal binding proteins, are characterized for the first time in the cephalochordate subphylum at both gene and protein level, together with the main features defining the amphioxus response to cadmium and copper overload. Two MT genes (BfMT1 and BfMT2) have been identified in a contiguous region of the genome, as well as several ARE (antioxidant response element) and MRE (metal response element) located upstream the transcribed region. Their corresponding cDNAs exhibit identical sequence in the two lancelet species (B. floridae and B. lanceolatum), BfMT2 cDNA resulting from an alternative splicing event. BfMT1 is a polyvalent metal binding peptide that coordinates any of the studied metal ions (Zn, Cd or Cu) rendering complexes stable enough to last in physiological environments, which is fully concordant with the constitutive expression of its gene, and therefore, with a metal homeostasis housekeeping role. On the contrary, BfMT2 exhibits a clear ability to coordinate Cd(II) ions, while it is absolutely unable to fold into stable Cu (I) complexes, even as mixed species. This identifies it as an essential detoxification agent, which is consequently only induced in emergency situations. The cephalochordate MTs are not directly related to vertebrate MTs, neither by gene structure, protein similarity nor metal-binding behavior of the encoded peptides. The closest relative is the echinoderm MT, which confirm proposed phylogenetic relationships between these two groups. The current findings support the existence in most organisms of two types of MTs as for their metal binding preferences, devoted to different biological functions: multivalent MTs for housekeeping roles, and specialized MTs that evolve either as Cd-thioneins or Cu-thioneins, according to the ecophysiological needs of each kind of organisms.

Effective Electrodiffusion equation for non uniform nanochannels

We derive a one dimensional formulation of the Planck-Nernst-Poisson equation to describe the dynamics of of a symmetric binary electrolyte in channels whose section is of nanometric section and varies along the axial direction. The approach is in the spirit of the Fick-Jacobs di fusion equation and leads to a system of coupled equations for the partial densities which depends on the charge sitting at the walls in a non trivial fashion. We consider two kinds of non uniformities, those due to the spatial variation of charge distribution and those due to the shape variation of the pore and report one and three-dimensional solutions of the electrokinetic equations.