Influence of configurational atomic order on the relative stability of bcc and close-packed structures in Cu-based alloys

We present a study of the influence of atomic order on the relative stability of the bcc and the 18R martensitic structures in a Cu2.96Al0.92Be0.12 crystal. Calorimetric measurements have shown that disorder increases the stability of the 18R phase, contrary to what happens in Cu-Zn-Al alloys for which it is the bcc phase that is stabilized by disordering the system. This different behavior has been explained in terms of a model recently reported. We have also proved that the entropy change at the martensitic transition is independent of the state of atomic order of the crystal, as predicted theoretically. Our results suggest that differences in the vibrational spectrum of the crystal due to different states of atomic order must be equal in the bcc and in the close-packed phases.

Lattice-dynamical study of the premartensitic state of the Cu-Al-Be alloys

Neutron-scattering techniques have been used to study the premartensitic state of a family of Cu-Al-Be alloys, which transform from the bcc phase to an 18R martensitic structure. We find that the phonon modes of the TA2[110] branch have very low energies with anomalous temperature dependence. A slight anomaly at q=2/3 was observed; this anomaly, however, does not change significantly with temperature. No elastic peaks, related to the martensite structure, were found in the premartensitic state of these alloys. The results are compared with measurements, performed under the same instrumental conditions, on two Cu-Al-Ni and a Cu-Zn-Al martensitic alloy.

Actividad sanguínea de superóxido dismutasa y glutatión peroxidasa en novillas a pastoreo

El objetivo de este estudio fue determinar el balance metabólico nutricional de Cu, Zn, Fe, Mn y Se, mediante la actividad sanguínea de SOD y GSH-Px y establecer la relación entre la concentración de Cu, Fe, Mn y Zn en el forraje y la actividad de SOD. Se tomaron 10 mL de sangre a 105 novillas seleccionadas en 15 rebaños lecheros de Caldas, Colombia (5º4' N y 75º3' O) y se tomaron muestras de forrajes para analizar Cu, Fe, Mn y Zn. El promedio de la actividad de SOD fue 1.390±1.299 U g-1 Hb, y estaba correlacionada con Cu, Mn y Fe en el forraje. La actividad promedio de GSH-Px fue 389±184 U g-1 Hb y fue observada una mayor frecuencia de valores deficitarios y bajo/marginales de 9%, habiendo sido más afectados los animales de zonas altas (>2.000 msnm). Bajo estas condiciones, estos resultados permiten señalar que la SOD es una enzima que puede emplearse como indicador del balance metabólico nutricional de Cu, Mn y Fe en bovinos a pastoreo, no está clara todavía su relación con Zn. La actividad de GSH-Px indica deficiencias en el balance metabólico nutricional de Se, en bovinos a pastoreo.

Uso de sílica e sílica-titânia organofuncionalizadas para a remoção de Cu(II) em aguardentes

Devido a necessidade da presença de cobre nos alambiques e as exigências cada vez mais acirradas com relação ao seu teor no destilado, é de interesse o desenvolvimento de metodologias para o controle deste metal nos destilados e/ou a sua remoção até níveis aceitáveis, em conformidade com as legislações nacional e internacional. Este trabalho investigou a potencialidade de dois sólidos: sílica modificada com trimetóxisili(propil)etilenodiamina (Si-Dia), e sílica-titânia, também modificada com trimetóxisili(propil)etilenodiamina (Si-Ti-Dia), como agentes removedores de íons Cu2+. Foram empregadas tanto soluções padrão de Cu2+, com teor alcoólico que simulavam aguardentes, como amostras reais de destilados. Os resultados indicam que um grama das matrizes Si-Dia e Si-Ti-Dia adsorvem 1,39 e 73,5mmol de Cu2+, respectivamente, a partir das soluções padrão, nas seguintes condições: tempo de contato 22h, pH 4,0; temperatura 25 ± 1,0°C e agitação constante. Para amostras reais, sob as mesmas condições de análises, o sólido Si-Dia reduziu as concentrações dos íons divalentes Cu, Zn e Fe em, respectivamente, 82, 83 e 64%, enquanto o Si-Ti-Dia, reduziu os mesmos íons em 88, 31 e 22%, respectivamente.

Síntesi, estructura i reactivitat de nous complexos de Cu, Ag i Ni contenint lligands triazamacrocíclics. Aplicacions en l'activació d'enllaços

· S'ha preparat i caracteritzat una família de complexos de Cu(III) contenint lligands triazamacrocíclics, estudiant-se les seves propietats estructurals, espectroscòpiques i redox. Aquesta àmplia família de complexos tenen un gran interès perquè permeten descriure les propietats dels complexos de Cu en un estat d'oxidació poc habitual i a més ens han permès mesurar de manera quantitativa l'efecte Meyerstein. · Una nova família de complexos de Cu(I) amb els lligands triazamacrocíclics es sintetitzada i caracteritzada per tècniques espectroscòpiques i estructurals, demostrant que aquests complexos presenten diferents estructures a l'estat sòlid i en dissolució. Així doncs, mentre que en dissolució es demostra per RMN que es tracta d'una espècie monomèrica, la determinació estructural per difracció de raigs X d'aquests complexos de Cu(I), ens confirma la formació d'espècies polimèriques. Per altra banda, s'ha estudiat la seva reactivitat; a) la seva implicació en la formació de lligands deuterats mitjançant l'intercanvi H/D en condicions suaus i b) la formació de complexos bisfenoxo a partir de la reactivitat entre els corresponents complexos de Cu(I) i oxigen molecular. De la mateixa manera, s'ha preparat el corresponent anàleg de Ag(I) en estat sòlid, obtenint la formació d'un polímer de Ag(I), el qual presenta a l'estat sòlid una estructura en forma de ziga-zaga, diferent a l'estructura del polímer de Cu(I), que és lineal. · S'ha determinat i proposat el mecanisme que té lloc en l'activació de l'enllaç C-H i posterior reacció de transferència per tal d'estabilitzar els productes finals mitjançant una reacció de desproporció. El seguiment de la reacció té lloc mitjançant tècniques espectroscòpiques com UV-vis. Dit seguiment, ens permet determinar les diferents influències electròniques sobre la reacció de formació dels complexos organometàl·lics de Cu(III). A més a més, el seguiment de la reacció a baixa temperatura ens permet determinar espectroscòpica i teòricament la formació d'un intermedi de Cu(II), i mitjançant la determinació dels paràmetres cinètics i termodinàmics es proposa un mecanisme de reacció. Posteriorment, s'ha assajat la reactivitat d'una sal de Cu(II) amb un lligand macrocíclic que conté un grup metil en el carboni orientat cap al centre del macrocicle, implicant la formació d'un intermedi agòstic. De la determinació estructural d'aquest intermedi de CuII i del lligand protonat, s'extreuen una sèrie de conclusions molt interessants, com són la demostració estructural de l'activació de l'enllaç C-C en la primera etapa de formació i de manera anàloga poder comparar-ho amb els sistemes macrocíclics HL2-HL6, demostrant la possible formació d'un intermedi agòstic, on es produeix l'activació de l'enllaç C-H. Aquesta similitud estaria d'acord amb els sistemes HL2-HL6, els quals espectroscòpica i teòricament s'havia detectat la presència d'un intermedi de característiques similars. Degut a l'acidesa d'aquest protó, i gràcies a la presència d'una base com és el propi lligand, aquest podia ésser extret donant lloc a la formació dels corresponents organometàl·lics de Cu(III). Dita estructura també representa un dels pocs exemples d'un organometàl·lic de CuII, un estat d'oxidació poc conegut dins d'aquest camp. · S'ha descrit la reactivitat dels nous complexos organometàl·lics de Cu(III), els quals sota medi pròtic i en condicions àcides o neutres són espècies totalment estables, però en condicions bàsiques o reductores aquestes espècies reaccionen donant lloc a la formació de noves espècies de tipus bisfenoxo, on el Cu es troba en estat d'oxidació +2. S'han caracteritzat mitjançant difracció de RX, on es s'observa l'entorn químic del Cu, la geometria del complex bisfenoxo i l'hidroxilació de l'anell aromàtic. · Finalment, s'ha descrit per primera vegada la síntesi i caracterització d'uns nous complexos organometàl·lics de Ni. Aquests són sintetitzats en base als càlculs teòrics realitzats sobre els nostres sistemes macrocíclics. Per aquests complexos hem investigat l'efecte del metall, canviant el coure per altres metalls de la primera sèrie de transició (Mn, Fe, Co, Ni, Cu, Zn) i de la segona sèrie de transició (Ru, Rh, Pd, Ag). Els resultats demostren que el Ni(II), és el metall que presenta una major capacitat de l'activació de l'enllaç C-H en aquests sistemes aromàtics. Aquests compostos s'oxiden lentament cap a complexos de Ni(III). Per altra banda, l'addició d'una sal de clor sobre una solució d'un complex de Ni(II) permet aïllar el corresponent complex de Ni(III), caracteritzat per ressonància de spin electrònic

Toxic effects of alcohol intake on prostate of rats

BACKGROUND. The present report was carried out to determine whether alcohol intake could induce prostate lesions.METHODS. We tested male rats for 300 days. Animals were divided into three groups: controls received only tap water as liquid diet; the chronic alcohol intake group received only ethanol solution in semivoluntary research; and the withdrawal group received the same treatment as chronic alcohol intake until 240 days, after which they reverted to drinking water.RESULTS. Chronic alcohol intake increased lipoperoxide concentrations and acid phosphatase activities. Cu-Zn superoxide dismutase (SOD) was decreased at 60 days, but approached controls values at 300 days following treatment. The serum increased alkaline phosphatase, and alanine transaminase activities reflected the chronic toxic effect of ethanol.CONCLUSIONS. Since SOD activity was unable to scavenge superoxide radical and lipoperoxide formation, we can conclude that superoxide is an important intermediate in prostate damage of chronic alcohol intake. (C) 1997 Wiley-Liss, Inc.

Differential/combined effect of water contamination with cadmium and nickel on tissues of rats

The contamination of water by metal compounds is a worldwide environmental problem. Concentrations of metals are widely related to biochemical values which are used in disease diagnosis due to environmental toxicity. The acute combined effects of cadmium and nickel on biochemical parameters were determined and compared with those of Cd2+ or Ni2+ alone in rats. Male adult rats were given drinking solutions of CdCl2 [Cd(II) cation, 100 mg/liter] or NiSO4 [Ni(II) cation, 100 mg/liter]. For the combined treatment, the animals (Ni+Cd) received both Ni(II)) cation (100 mg/liter) and Cd(II) cation (100 mg/liter). Nickel treatment induced increased alanine transaminase (ALT) activity and hepatotoxicity, but not renal injury. In contrast, cadmium exposure produced hepatic, renal and myocardial damage, characterized by increased creatinine, total and direct bilirubin concentrations and increased ALT and lactate dehydrogenase (LDH) activities. The combined effect Ni-Cd is less toxic than cadmium alone, suggesting antagonism between these toxicants. The toxicity of nickel and cadmium, alone and in combination, decreased Cu-Zn superoxide dismutase (SOD) activity and increased lipoperoxide formation. (C) 1998 Elsevier B.V. Ltd. All rights reserved.

Toxicity of chronic ethanol ingestion and superoxide radical formation on seminal vesicles of rats

The toxic effects of chronic ethanol ingestion were evaluated in male adult rats for 300 days. The animals were divided into three groups: the controls received only tap water as liquid diet; the chronic ethanol ingestion group received only ethanol solution (30%) in semivoluntary research; and the withdrawal group received the same treatment as chronic ethanol-treated rats until 240 days, after which they reverted to drinking water. Chronic ethanol ingestion induced increased lipoperoxide levels and acid phosphatase activities in seminal vesicles. Cu-Zn superoxide dismutase (SOD) decreased from its basal level 70.8 +/- 3.5 to 50.4 +/- 1.6 U/mg protein at 60 days of chronic ethanol ingestion. As changes in GSH-PX activity were observed in rats after chronic ethanol ingestion, while SOD activities were decreased in these animals, it is assumed that superoxide anion elicits lipoperoxide formation and induces cell damage before being converted to hydrogen peroxide by SOD. Ethanol withdrawal induced increased SOD activity and reduced seminar vesicle damage, indicating that the toxic effects were reversible, since increased SOD activity was adequate to scavenge superoxide radical formation. Superoxide radical is an important intermediate in the toxicity of chronic ethanol ingestion. Copyright (C) 1996 Elsevier B.V. Ltd

SUPEROXIDE RADICAL AND TOXICITY OF ENVIRONMENTAL NICKEL EXPOSURE

Three nickel compounds were tested for pancreatic, hepatic and osteogenic damage in rats by a single i.m. injection Ni++ (7 mg kg(-1)). The nickel induced biochemical alterations included significantly increased levels of serum alkaline phosphatase in rats with NiS (75%) and NiO (50%). Amylase and aspartate transaminase were also increased, and lipoperoxide was increased in rats with NiO (5.6-fold) and NiS (3.4-fold). No serum changes were observed with NiCl2. Daily injection of Cu-Zn superoxide dismutase (SOD) conjugated with polyethylene glycol prevented the serum level changes, indicating that superoxide radical is an important intermediate in toxicity of nickel insoluble compounds.

CLINICAL BIOCHEMICAL DETERMINATIONS IN THE MANGALARGA-PAULISTA HORSE - REFERENCE VALUES

Biochemical values are widely related with environmental agents, sex and age, and are used in disease diagnosis. Numerous reports have been published on the biochemical parameters of different breeds of horses. However, there is a paucity of information concerning Cu-Zn superoxide dismutase (SOD), ceruloplasmin, copper and zinc determinations in the serum. Blood samples from a total of 60 horses of the Mangalarga-Paulista breed, representing three age groups (0 to 4 months old, 6 to 18 months old and adult) were examined. Male horses have a higher mean value of SOD, ceruloplasmin and copper than do females. No significant sex-related difference was observed in serum zinc content of weaned and adult horses. SOD activity was significantly higher in adult animals. Since SOD has a protective effect against superoxide free radical toxicity and possesses anti-inflammatory activity, it is reasonable to assume that the increased activity of this enzyme may be due to an adaptation mechanism which protects the adult animal against oxygen toxicity.

A NEW CU-BASED SMA WITH EXTREMELY HIGH MARTENSITIC-TRANSFORMATION TEMPERATURES

A new series of high temperature copper based shape memory alloys has recently been patented. These alloys contain 8-20 wt% Al, 1-20 wt% Ag, 0-2 wt% of a minor element (preferably Co), balance copper. The martensitic start transformation temperatures of these alloys are above 200 degrees C and, in some cases, they have good high temperature stability and may be useful in commercial applications where higher operating temperatures than those obtained from Cu-Zn-Al and Cu-Al-Ni shape memory alloys are required.

Pancreas damage and intratracheal NiCl2 administration. Effects of nickel chloride.

Changes in activities of Cu-Zn superoxide dismutase (SOD- E.C.1.15.1.1.) and lactate dehydrogenase (LDH- E.C.1.1.1.27.) and levels of copper, total protein, triglycerides, phospholipids and total lipids were investigated in pancreas of rats after intratracheal administration of NiCl2 (8.4 mumol/kg). Nickel chloride induced increased SOD activity in pancreas and erythrocytes. This elevation was related to increased copper and decreased phospholipid content in pancreas of these animals. In conclusion, the ability of an animal to tolerate nickel chloride induced damage was governed by a delicate balance between the generation of cytotoxic agents and the various pancreas defense capabilities.

Protective effect of nickel chloride on superoxide damage: enhancement of CuZn superoxide dismutase affinity to the oxygen free radical.

The effect of nickel from soluble NiCl2 on Cu-Zn superoxide dismutase (SOD) activity, as well as on rate of nitro blue tetrazolium reduction, was studied in vitro since lipid peroxidation has been implicated in cell damage by nickel insoluble compounds, whose toxicity and carcinogenicity are well established. The physical and chemical nature of nickel compounds is one of the key determinations of its toxicity. Soluble nickel freely enter cells, but is just as readily excreted reducing the opportunity for production of lipid damage. Nickel from NiCl2 strongly activated SOD activity. In vitro addition of nickel chloride to a crude lung preparation altered the KM for SOD without changing the Vmax. Nickel chloride produced increased enzyme affinity to the substrate, because decreased (O2-) concentration that yields half-maximal velocity. The combination of nickel and SOD may contribute to stabilization of the particular conformation of SOD responsible for maximal catalytically activity.

Increased oxygen radical and high-dietary-carbohydrate pancreatic damage.

These data suggest that an improved understanding of the relationship between high dietary carbohydrate and the rate of lipid peroxidation may give some insight into possible treatment modalities for pancreatic damages and may shed light on molecular mechanisms underlying certain pathological processes. High dietary carbohydrate lesions are age related and induced alterations on ceruloplasmin, phospholipids, total proteins, copper and zinc serum levels. Significantly increased serum and pancreatic amylase, and lipoperoxide determinations were observed in 20 month old rats. Cu-Zn superoxide dismutase was decreased in these animals. Daily injection of Cu-Zn superoxide dismutase conjugated with polyethylene glycol (SOD-PEG) prevented the serum and pancreatic changes, indicating that superoxide radical is an important intermediate to high dietary carbohydrate lesion.

Long-term toxicity following acute administration of nickel

Nickel compounds have high potential risk for the health of populations and for this reason their toxic effects should be urgently established. To determine the effect of nickel monosulfide in the muscle at the injection site on pancreatic, hepatic, and osteogenic lesions and the potential therapeutic effect of Cu-Zn superoxide dismutase (SOD), male Wistar rats received single intramuscular injections of nickel monosulfide (NiS - 7 mg Ni2+/Kg). A group of these experimental rats were injected intraperitoneally, with a single weekly dose of SOD covalently linked to polyethylene glycol (SOD-PEG). Rats were sacrificed at 2, 4, 6, and 8 months after Ni2+ injection. Nickel monosulfide produced tumors at the injection site. The increased phospholipid, alanine transaminase (ALT), alkaline phosphatase (ALP), and amylase levels in serum, in absence of SOD-PEG, reflected the toxic effects on pancreatic, hepatic, and osteogenic tissues of rats. SOD activity was increased in serum of rats receiving SOD-PEG throughout the experiment, and no significant difference was observed in biochemical parameters of control and experimental rats in presence of SOD- PEG. Superoxide radical generated by Ni2+ is of primary importance in the development of tumors at the injection site. Superoxide anion (O2 -) is also an important toxic intermediate with respect to hepatic, pancreatic, and osteogenic injury, since SOD-PEG has a potential therapeutic effect.