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PubMed2004

Mixed-metal metallocryptands. Short metal-metal separations strengthened by a dipolar interaction.

The deep-red, air-stable mixed-metal metallocryptands, [AuPdTl(P2phen)3](PF6)2, 1.(PF6)2, and [AuPtTl(P2phen)3](PF6)2, 2.(PF6)2, are easily prepared in good yield (60-70%) by reacting 3 equiv of P2phen with 1 equiv of Au(THT)Cl, excess thallous acetate, and the appropriate amount of either Pd2(dba)3 for 1 or Pt(dba)2 for 2 in acetonitrile where P2phen is 2,9-bis(diphenylphosphino)-1,10-phenanthroline, THT is tetrahydrothiophene, and dba is dibenzylidineacetone. Compared to the more symmetrical bimetallic metallocryptands, these trimetallic species show shorter than expected Au(I)-Tl(I), Pt(0)-Tl(I), and Pd(0)-Tl(I) separations. The enhanced bonding interaction is attributed to the incorporation of the dissimilar capping metals introducing dipole moments that strengthen the dispersion forces responsible for maintaining the metallophilic interactions.

Journal Article↗
PubMed1976

Metal-metal bond lengths in complexes of transition metals.

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths.

Journal Article↗
PubMed2006

Silver enhancement of quantum dots resulting from (1) metabolism of toxic metals in animals and humans, (2) in vivo, in vitro and immersion created zinc-sulphur/zinc-selenium nanocrystals, (3) metal ions liberated from metal implants and particles.

Autometallographic (AMG) silver enhancement is a potent histochemical tool for tracing a variety of metal containing nanocrystals, e.g. pure gold and silver nanoclusters and quantum dots of silver, mercury, bismuth or zinc, with sulphur and/or selenium. These nanocrystals can be created in many different ways, e.g. (1) by manufacturing colloidal gold or silver particles, (2) by treating an organism in vivo with sulphide or selenide ions, (3) as the result of a metabolic decomposition of bismuth-, mercury- or silver-containing macromolecules in cell organelles, or (4) as the end product of histochemical processing of tissue sections. Such nano-sized AMG nanocrystals can then be silver-amplified several times of magnitude by being exposed to an AMG developer, i.e. a normal photographic developer enriched with silver ions. The present monograph attempts to provide a review of the autometallographic silver amplification techniques known today and their use in biology. After achieving a stronghold in histochemistry by Timm's introduction of the "silver-sulphide staining" in 1958, the AMG technique has evolved and expanded into several different areas of research, including immunocytochemistry, tracing of enzymes at LM and EM levels, blot staining, retrograde axonal tracing of zinc-enriched (ZEN) neurons, counterstaining of semithin sections, enhancement of histochemical reaction products, marking of phagocytotic cells, staining of myelin, tracing of gold ions released from gold implants, and visualization of capillaries. General technical comments, protocols for the current AMG methods and a summary of the most significant scientific results obtained by this wide variety of AMG histochemical approaches are included in the present article.

Animals↗
PubMed2000

A comparative joint simulator study of the wear of metal-on-metal and alternative material combinations in hip replacements.

While total hip replacement represents the major success story in orthopaedic surgery in the twentieth century, there is much interest in extending even further, early in the twenty first century, the life of implants. Osteolysis has been identified as a major factor limiting the life of prostheses, with indications that fine polyethylene wear debris, generated primarily at the interface between the femoral head and the acetabular cup, promotes the process. There is therefore considerable interest in the introduction of alternative wear resistant systems to limit the deleterious effects of wear. These alternatives include ceramic-on-ceramic and metal-on-metal configurations and the present paper is primarily concerned with the latter. Some six pairs of new metal-on-metal implants of 36 mm diameter and four pairs of existing metal-on-metal implants of 28 mm diameter were tested in a ten-station hip joint simulator in the presence of a 25 per cent bovine serum solution. The implants were tested in the anatomical position to 5 x 10(6) cycles. The new heads and cups were manufactured from CoCrMo alloy with careful attention being paid to sphericity and surface finish of both components. The wear performance of the new and existing metal-on-metal total hip replacements have been evaluated and compared. The overall wear rates have then been compared with previously reported wear rates for a zirconia-on-polyethylene prosthesis of 22 mm diameter tested on the same simulator. The comparison is taken further by recalling published penetration data for metal-on-polyethylene implants of 22 and 28 mm diameter and converting these to volumetric wear rates. It was found that the heads and cups in metal-on-metal joints wore by almost equal amounts and that the opposing surfaces converged to similar surface roughness as the testing time increased. Steady state wear rates were generally achieved after 1-2 x 10(6) cycles. The mean long-term wear rates for the metal-on-metal prostheses were very low, being 0.36 mm3/10(6) cycles and 0.45 mm3/10(6) cycles for the new implants of 36 mm diameter and established implants of 28 mm diameter respectively. These wear rates compare with 6.3 mm3/10(6) cycles for zirconia-on-ultra-high molecular weight polyethylene tested on the same simulator and representative clinical values for metal-on-polyethylene of 36 mm3/year for heads of 22 mm diameter and a reported range of 60-180 mm3/year for 28 mm heads. These values do not translate directly into numbers of particles, since the metallic debris from metal-on-metal joints is very fine. The number of metallic particles may exceed the number of polyethylene wear particles from an otherwise similar metal-on-polyethylene joint by a factor of 10(3). A detailed discussion of the size and morphology of wear debris and tissue reaction to various forms of debris is beyond the scope of this paper, but the biological response to polymeric, metallic and ceramic wear debris forms a major subject for further study. The present investigation nevertheless confirms the potential of carefully designed and manufactured metal-on-metal total replacement joints for the treatment of diseased and damaged hips.

Animals↗
PubMed2004

Using multiple metal-gill binding models and the toxic unit concept to help reconcile multiple-metal toxicity results.

Metal-gill binding models and biotic ligand models (BLMs) in general are designed to predict metal toxicity to aquatic organisms. These models calculate the amount of a metal-binding to a sensitive biological membrane, such as a fish gill, which equates with metal toxicity. Cation competition at the metal-binding site and anionic complexation in the water decrease metal-binding to the membrane, decreasing metal toxicity. These models have, to date, been developed for individual metals. To assess how these models handle multiple-metal interactions, metal-gill binding models for two to six metals were created and their behavior tested against the toxic unit (TU) concept assuming strict additivity. The multiple-metal models yield greater than strict additivity at low aqueous metal concentrations (Sigma < 1 TU), strict additivity at intermediate metal concentrations (Sigma = 1 TU), and less than strict additivity at high metal concentrations (Sigma > 1 TU), independent of the combination of metals. Deviations from strict additivity are due to the non-linear nature of the models, where greater than linear filling of binding sites occurs at low metal concentrations, and where strong competition for binding sites occurs at high metal concentrations, with a point of strict additivity between, where the metals sum to one toxic unit. Simulations with natural organic matter (NOM) show similar trends but are complex. Mathematical modeling of multiple-metal interactions may help in the interpretation of toxicity results from mixed-metal exposures to aquatic organisms.

Animals↗
PubMed1989

[Electric current around dental metals as a factor producing allergenic metal ions in the oral cavity].

Allergy to dental metal alloys has been reported to occasionally cause dermatitis, stomatitis, lichen planus and pustulosis palmaris et plantaris. According to Faraday's law of electrolysis, when electric current flows into an anode, cationic metal ions dissolve in parallel with the amount of the electric current. Therefore, when patients hypersensitive to metals have suffered from the above mentioned persistent dermatoses, measurement of voltages and electric currents around the dental alloys of the patient's oral cavities was deemed necessary, in order to investigate whether or not such dental metals have been supplied causative metal ions to the patients. For the investigation of electrochemical dissolution of metal ions; firstly, voltages and electric currents between the mucous membrane and standard dental alloy tips placed in the oral cavities of each 15 healthy volunteers and patients were measured. Secondly, the same study was performed with the mucous membrane and actually installed dental metals with 158 patients who showed positive reactions to dental metal series patch test allergens composed of 19 reagents. The results were as follows: 1) Voltages between the mucous membranes and standard metal plates placed in the oral cavities varied depending on the composition of the dental metal. 2) The above-mentioned voltages changed when various food were present in the oral cavity. 3) With the dental metals actually present in the metal-hypersensitive patient's oral cavities, the voltages between the adjacent mucous membrane and dental metals varied greatly, depending on the individual patient rather than on the types of metal. Certain alloys acted as cathodes with some patients, but as anodes with others. 4) Amalgam and silver alloys showed higher voltages and more electric current with the smaller ranges of variation than other kinds of alloys. Both of these alloys tended to act as anodes, therefore, the electrochemical dissolution of metal ions was expected to be higher than with other metals. 5) The voltages and electric currents were often higher between mucous membrane and metals than between metals. These findings indicate that the patient's own mucous membrane acts as cathode for the electrochemical dissolution rather than the dental metals. 6) Measuring the voltage and electric current in the patient's oral cavities is technically easy, and is considered to be valuable since the tendancy of electrochemical dissolution of metal ions from the dental metals is clearly demonstrated.

Adolescent↗
PubMed2005

An unusual lymphocytic perivascular infiltration in tissues around contemporary metal-on-metal joint replacements.

BACKGROUND: Metal-on-metal bearing surfaces have been reintroduced for use during total hip replacement. To assess tissue reactions to various types of articulations, we studied the histological appearance of periprosthetic tissues retrieved from around metal-on-metal and metal-on-polyethylene total hip replacements and compared these findings with the appearance of control tissues retrieved at the time of primary arthroplasty. METHODS: Periprosthetic tissues were obtained at the time of revision of twenty-five cobalt chromium-on-cobalt chromium, nine cobalt chromium-on-polyethylene, and ten titanium-on-polyethylene total hip arthroplasties. Control tissues were obtained from nine osteoarthritic hips at the time of primary total hip arthroplasty. Each tissue sample was processed for routine histological analysis, and sections were stained with hematoxylin and eosin. Quantitative stereological analysis was performed with use of light microscopy. RESULTS: Tissue samples obtained from hips with metal-on-metal implants displayed a pattern of well-demarcated tissue layers. A prominent feature, seen in seventeen of twenty-five tissue samples, was a pattern of perivascular infiltration of lymphocytes. In ten of the tissue samples obtained from hips with metal-on-metal prostheses, there was also an accumulation of plasma cells in association with macrophages that contained metallic wear-debris particles. The surfaces of tissues obtained from hips with metal-on-metal prostheses were more ulcerated than those obtained from hips with other types of implants, particularly in the region immediately superficial to areas of perivascular lymphocytic infiltration. The lymphocytic infiltration was more pronounced in samples obtained at the time of revision because of aseptic failure than in samples retrieved at the time of autopsy or during arthrotomy for reasons other than aseptic failure. Total-joint-replacement and surface-replacement designs of metal-on-metal prostheses were associated with similar results. Tissue samples obtained from hips with metal-on-polyethylene implants showed far less surface ulceration, much less distinction between tissue layers, no pattern of lymphocytic infiltration, and no plasma cells. The inflammation was predominantly histiocytic. Tissues retrieved from hips undergoing primary joint replacement showed dense scar tissue and minimal inflammation. CONCLUSIONS AND CLINICAL RELEVANCE: The pattern and type of inflammation seen in periprosthetic tissues obtained from hips with metal-on-metal and metal-on-polyethylene implants are very different. At the present time, we do not know the prevalence or clinical implications of these histologic findings, but we suggest that they may represent a novel mode of failure for some metal-on-metal joint replacements.

Biocompatible Materials↗
PubMed2005

Dynamics of metal subcellular distribution and its relationship with metal uptake in marine mussels.

We examined the dynamics of subcellular distribution of metals (Cd, Ag, and Zn) in the marine green mussel Perna viridis by partitioning the metals into the insoluble fraction (IF), heat-sensitive proteins (HSP), and metallothionein-like proteins (MTLP) during metal uptake and elimination. Variations in metal uptake and elimination then were correlated with the subcellular distributions of these metals. The IF and HSP were the first ligands to bind with the metals during the dissolved exposure, and more metals were found in the HSP when the metal influx rate was higher. However, to minimize toxicity, metals were redistributed from HSP to MTLP afterwards. The subcellular distribution of metals was dependent of the exposure route in the mussels. During dietary metal exposure, the metals attained equilibrium before they were assimilated and the metal assimilation efficiency was independent of the metal partitioning in different subcellular fractions. During the efflux, metals in the soluble fraction mediated depuration, whereas metals in the insoluble fraction acted as a final storage pool. Redistribution also may occur between the metal-sensitive and inactive pools without significant depuration as a secondary protective mechanism. We further demonstrated that the higher efflux rate of Ag and Cd was related to a higher partitioning in the MTLP and a lower partitioning in the IF. Our study shows that subcellular pools other than MTLP were involved in immediate metal handling in the bivalves. The wide dynamics of subcellular metal distribution suggests that the relevance of individual subcellular fractions is dependent on the exposure pathway.

Animals↗
PubMed2005

Structural determinants of metal selectivity in prokaryotic metal-responsive transcriptional regulators.

Metal ion homeostasis in prokaryotes is maintained by metal-responsive transcriptional regulatory proteins that regulate the transcription of genes encoding proteins responsible for metal detoxification, sequestration, efflux and uptake. These metalloregulatory, or metal sensor proteins, bind a wide range of specific metal ions directly; this in turn, allosterically regulates (enhances or decreases) operator/promoter binding affinity or promoter structure. Recent structural studies reveal five distinct families of metal sensor proteins. The MerR and ArsR/SmtB families regulate the expression of genes required for metal ion detoxification, efflux and sequestration; here, metal binding leads to activation (MerR) or derepression (ArsR/SmtB) of the resistance operon. In contrast, the DtxR, Fur, and NikR families regulate genes encoding proteins involved in metal ion uptake; in these cases, the metal ion functions as a co-repressor in turning off uptake genes under metal-replete conditions. Inspection of the structures of representative members from each metal sensor family reveals several common characteristics: (1) they function as homo-oligomers (either dimers or tetramers); (2) metal-binding ligands are found at subunit interfaces, with ligands derived from more than one protomer; this likely helps drive quaternary structural changes that mediate allosteric coupling between the metal and DNA binding sites; and (3) the primary determinant of metal ion selectivity within each protein family is dictated by the coordination geometry of the metal chelate, with trends consistent with expectations from fundamental inorganic chemistry. This review highlights recent efforts to elucidate the structure of metal sensing chelates and the molecular mechanisms of allosteric coupling in metal sensor proteins.

Allosteric Site↗
PubMed2004

Metal content of saliva of patients with and without metal restorations.

Many in vitro studies have confirmed the corrosion of dental alloys. However, in vivo corrosion studies, for example, recording of the release of metal ions into saliva, are scarce, and data on the repeatability of the metal content measurements of saliva are lacking. The present study examined the metal content of saliva of patients with and without metal restorations and assessed the repeatability of these data. The composition of each patient's oral cast alloys was analyzed using the energy-dispersive X-ray analysis of metal biopsy specimens and was compared to the metals found in saliva. Saliva analysis was performed using atomic absorption spectroscopy. Chemical analysis comprised the metals Ag, Au, Co, Cr, Cu, Fe, Ga, In, Ni, Pd, Pt, Sn, and Zn. The metals Ag, Cr, Cu, Fe, Ni, and Zn were found in saliva of patients without metal restorations, but these data showed statistically significant differences in the metal content between consecutively performed samples per patient. The metals Ag, Au, Cr, Cu, Fe, Ni, and Zn were identified in saliva of patients with metal restorations being higher in concentration than in control patients. In 77% of the cases at least one metal of the restoration was found in the patient's saliva. However, the metal content showed statistically significant differences between replicate samples of the same patient taken at different times. The metal content of saliva is affected among other things by intraoral metal restorations, but present data do not support the idea that it is a reliable indicator for the systemic exposure to metals released from dental alloys.

Chromium↗
PubMed2004

Density functional investigation of metal-metal interactions in mixed-valence d2d3 (Cr, Mo, W) and d3d4 (Mn, Tc, Re) face-shared [M2Cl9]2- systems.

The molecular and electronic structures of mixed-valence face-shared (Cr, Mo, W) d(2)d(3) and (Mn, Tc, Re) d(3)d(4) [M(2)Cl(9)](2-) dimers have been calculated by density functional methods in order to investigate metal-metal bonding in this series. The electronic structures of these systems have been analyzed using potential energy curves for the broken-symmetry and other spin states arising from the d(2)d(3) and d(3)d(4) coupling modes. In (d(2)d(3)) [Mo(2)Cl(9)](2-) and [W(2)Cl(9)](2-), the global minimum has been found to be a spin-doublet state characterized by delocalization of the metal-based electrons in a multiple metal-metal bond (with a formal bond order of 2.5). In contrast, weak coupling between the metal centers and electron localization are favored in (d(2)d(3)) [Cr(2)Cl(9)](2-), the global minimum for this species being a ferromagnetic S = 5/2 state with a relatively long Cr-Cr separation. The (d(3)d(4)) [Re(2)Cl(9)](2-) system also exhibits a global minimum corresponding to a metal-metal bonded spin-doublet state with a formal bond order of 2.5, reflecting the electron-hole equivalence between d(2)d(3) and d(3)d(4) configurations. Double minima behavior is predicted for (d(3)d(4)) [Tc(2)Cl(9)](2-) and [Mn(2)Cl(9)](2-) due to two energetically close low-lying states (these being S = 3/2 and S = 5/2 states for the former, and S = 5/2 and S = 7/2 states for the latter). A comparison of computational results for the d(2)d(2), d(2)d(3), and d(3)d(3) [W(2)Cl(9)](z-) series and the d(3)d(3), d(3)d(4), and d(4)d(4) [Re(2)Cl(9)](z-) series indicates that the observed trends in metal-metal distances can only be rationalized if changes in both the strength of sigma bonding and metal-metal bond order are taken into consideration. These two factors act conjointly in the W series but in opposition to one another in the Re series. In the case of the [Cr(2)Cl(9)](z-) and [Mn(2)Cl(9)](z-) dimers, the metal-metal bond lengths are significantly shorter for mixed-valence (d(2)d(3) or d(3)d(4)) than d(3)d(3) systems. This result is consistent with the fact that some degree of metal-metal bonding exists in the former (due to partial delocalization of a single sigma electron) but not in the latter (where all metal-based electrons are completely localized).

Journal Article↗
PubMed2000

Total hip arthroplasty with use of the Metasul metal-on-metal articulation. Four to seven-year results.

BACKGROUND: Total hip replacements with a metal-on-metal articulation were commonly used until the mid-1970s; most were then abandoned in favor of hip replacement with a metal-on-polyethylene articulation. The reason for this change was primarily early cup loosening, which was more prevalent with these metal-on-metal designs than it was with metal-on-polyethylene designs. In the late 1980s, a metal-on-metal design with improved clearance (adequate space between the femoral head and the acetabular articulation surface to allow fluid film lubrication and clearance of any debris from within this joint), metal hardness, and reproducible surfaces was introduced by Sulzer Orthopedics in Switzerland. Orthopaedic surgeons were interested in this Metasul articulation because the contribution of polyethylene wear particles to the failure of total hip replacements had become evident. This study was undertaken to review the clinical performance of this implant and to determine if early acetabular loosening or revision and wear and osteolysis were prevalent. METHODS: Between 1991 and 1994, seventy patients (seventy hips) had a total hip replacement with the Metasul metal-on-metal articulation and a cemented Weber cup. Nine patients died less than four years after the replacement; none of these deaths were related to the operation. Five patients were not available for radiographic evaluation, but they were contacted and it was known that the hip was not painful and had not been revised. Fifty-six patients (fifty-six hips) had complete clinical and radiographic data four to 6.8 years after the operation, and they made up the study group. The patients were evaluated with use of the Harris hip score, a patient-self-assessment form, and radiographs. RESULTS: At an average of 5.2 years (range, four to 6.8 years) after the operation, the average total Harris hip score for the fifty-three patients who did not have a revision was 89.6 points (range, 62 to 100 points). The average Harris pain score was 41.0 points (range, 30 to 44 points), and the average Harris limp score was 9.4 points (range, 5 to 11 points). One patient had revision of a loose cup, but there were no other loose acetabular components in the series. Two patients had revision of the acetabular component because of dislocation. No patient had a loose or revised femoral component. Therefore, the mechanical failure rate was one (2 percent) of fifty-six patients. Thirty-six of forty-seven patients who completed the patient-self-assessment form rated their result as excellent; seven, as very good; two, as good; one, as fair; and one, as poor. Wear could not be measured on radiographs because of the metal-on-metal articulation. No hip had radiographic evidence of acetabular osteolysis and two hips had calcar resorption, but there was no other radiographic evidence of focal osteolysis. CONCLUSIONS: Our four to seven-year experience with this articulation surface indicates that the clinical results are similar to those of total hip replacements with a metal-on-polyethylene articulation. We believe that the Metasul articulation may have a role in reducing the wear that occurs with total hip replacement. The Metasul articulation appears to be particularly indicated for more active patients. A historical comparison with the reports in the literature of which we are aware indicated that the hips in our study had a lower rate of acetabular revision and loosening than did those with previous metal-on-metal designs and that they had no more acetabular loosening or osteolysis than did those with metal-on-polyethylene articulations followed for an average of five years.

Adult↗
PubMed2006

Kinetics of metal binding by the toxic metal-sensing transcriptional repressor Staphylococcus aureus pI258 CadC.

The mechanisms by which metal ions are sensed in bacterial cells by metal-responsive transcriptional regulators (metal sensor proteins) may be strongly influenced by the kinetics of association and dissociation of specific metal ions with specific metalloregulatory targets. Staphylococcus aureus pI258-encoded CadC senses toxic metal pollutants such as Cd(II), Pb(II) and Bi(III) with very high thermodynamic affinities ( approximately 10(12)M(-1)) in forming either distorted tetrahedral (Cd/Bi) or trigonal (Pb) coordination complexes with cysteine thiolate ligands derived from the N-terminal domain (Cys7/11) and a pair of Cys in the alpha4 helix (Cys58/60). We show here that metal ion binding to this site (denoted the alpha3N or type 1 metal site) is characterized by two distinct kinetic phases, a fast bimolecular encounter phase and a slower intramolecular conformational transition. Metal association rates are fast ( approximately 10(5)-10(7)M(-1)s(-1)) and strongly dependent on the metal ion type in a manner that correlates with metal specificity in vivo. In contrast, the observed rate of the slower isomerization step is independent of the metal ion type (2.8+/-0.4s(-1)) but is reduced 6-fold upon substitution of Cys7, a key metal ligand that drives allosteric negative regulation of DNA binding. Chelator (EDTA)-mediated metal dissociation rates from the alpha3N site are extremely slow (10(-4)s(-1)). Where observable dissociation can be observed, a ternary CadC-metal ion-chelator complex is invoked, suggesting that metal-ligand exchange may be an important factor in metal sensing and resistance in the cell.

Bacterial Proteins↗
PubMed2004

Identification of Thlaspi caerulescens genes that may be involved in heavy metal hyperaccumulation and tolerance. Characterization of a novel heavy metal transporting ATPase.

Thlaspi caerulescens is a heavy metal hyperaccumulator plant species that is able to accumulate extremely high levels of zinc (Zn) and cadmium (Cd) in its shoots (30,000 microg g(-1) Zn and 10,000 microg g(-1) Cd), and has been the subject of intense research as a model plant to gain a better understanding of the mechanisms of heavy metal hyperaccumulation and tolerance and as a source of genes for developing plant species better suited for the phytoremediation of metal-contaminated soils. In this study, we report on the results of a yeast (Saccharomyces cerevisae) complementation screen aimed at identifying candidate heavy metal tolerance genes in T. caerulescens. A number of Thlaspi genes that conferred Cd tolerance to yeast were identified, including possible metal-binding ligands from the metallothionein gene family, and a P-type ATPase that is a member of the P1B subfamily of purported heavy metal-translocating ATPases. A detailed characterization of the Thlaspi heavy metal ATPase, TcHMA4, demonstrated that it mediates yeast metal tolerance via active efflux of a number of different heavy metals (Cd, Zn, lead [Pb], and copper [Cu]) out of the cell. However, in T. caerulescens, based on differences in tissue-specific and metal-responsive expression of this transporter compared with its homolog in Arabidopsis (Arabidopsis thaliana), we suggest that it may not be involved in metal tolerance. Instead, we hypothesize that it may play a role in xylem loading of metals and thus could be a key player in the hyperaccumulation phenotype expressed in T. caerulescens. Additionally, evidence is presented showing that the C terminus of the TcHMA4 protein, which contains numerous possible heavy metal-binding His and Cys repeats residues, participates in heavy metal binding. When partial peptides from this C-terminal domain were expressed in yeast, they conferred an extremely high level of Cd tolerance and Cd hyperaccumulation. The possibilities for enhancing the metal tolerance and phytoremediation potential of higher plants via expression of these metal-binding peptides are also discussed.

Adenosine Triphosphatases↗
PubMed1988

Correlation clusters in the accumulation of metals in human scalp hair: effects of age, community of residence, and abundances of metals in air and water supplies.

Scalp hair samples taken from 122 children and 27 adults from three native Indian villages in northern Alberta, Canada were analyzed for 32 metals, in an attempt to trace industrial pollution into the human population. One of the villages has been exposed since 1967 to increased levels of several metals due to its proximity to the world's first two oil sands petroleum extraction plants (Suncor and Syncrude), which release large amounts of metals into the environment. Metal-enriched particulates are emitted at a rate of 547-780 kg h-1 for Suncor, and 713-1067 kg h-1 for Syncrude. To test the hypothesis that hair content reflected accumulation of environmental metals, water and aerometric samples were collected and analyzed for their metal content. These analyses demonstrated that elevated levels of nine metals in hair from children in one of the control villages (Garden River) are (with the exception of Al) correlated with increased levels of metals in water and air. Moreover, increased levels of Cu, but lowest levels of all other metals were found in hair and environmental samples from one control village (Fort Chipewyan). Correlation matrices for metals in the hair samples revealed three sets of highly intercorrelated metals ('correlation clusters'): (i) Pb/Cd; (ii) Al/V/Fe; (iii) Ca/Mg/Sr/Ba. These groups of metals were significantly intercorrelated (r greater than 0.6, p less than 0.001) in the total population, and in both children and adults, or both males and females, as well as when the population was compared according to community of residence. The robustness of the clusters is particularly noteworthy in view of large differences in the proportions and absolute amounts of the various metals in hair from children in the three villages. Plots of metal levels in hair as a function of age of subject reveal a dramatic decrease in concentrations of Al, V, and Fe during the first years of life. The high levels of Al and V in hair from very young children may reveal a lower selectivity in metal absorption, and a higher risk of toxicity during a period of rapid growth when need for nutritionally essential metals is particularly high.

Adult↗
PubMed2005

Influence of metal exposure history on trace metal uptake and accumulation by marine invertebrates.

This paper reviews recent studies on the influence of trace metal exposure history on subsequent metal uptake in marine invertebrates, particularly bivalves and barnacles. Trace metal exposure may induce specific metal-binding ligands. Metallothionein-like proteins appear to play an important role in mediating metal uptake and hence accumulation, especially for Cd. Other ligands such as sulfide are important for Ag biokinetic changes in bivalves. The incorporation of trace metals into metal-rich granules appears to have little if any effect in modifying trace metal uptake. Furthermore, metals also interact strongly in their accumulation by marine animals. Generally, dissolved Hg uptake is reduced following exposure to other metals such as Ag, Cd, Cu, and Zn. Preexposure of marine mussels to Zn also causes concomitant changes in the uptake of other metals such as Cd sharing similar transport pathways. In general, barnacles are less responsive than mussels to trace metal exposure, presumably because of the dominance of detoxificatory pathways in which the accumulated metals are bound in granules (relatively biologically inactive pools). The tissue body burden and the detoxificatory fate of metals in animals seem to be more important in affecting metal accumulation than the nature of the exposure routes (aqueous vs. dietary) or of the exposure regimes. Trace metal accumulation may also be variable in different natural populations of bivalves as a result of different physicochemical environments and histories of exposure. We finally suggest a few areas for future research in this field.

Animals↗
PubMed1994

Structural studies of metal binding by inositol monophosphatase: evidence for two-metal ion catalysis.

The structure of inositol monophosphatase has been determined to 2.60 A resolution in complexes with Mn2+ and with Mn2+ and phosphate. In the Mn2+ complex, three metal cations and one Cl were bound in the active site on each of the two subunits of the enzyme. Ligands to the three metals include the side chains of Glu 70, Asp 90, Asp 93, and Asp 220, t he carbonyl group of Ile 92, several solvent molecules and the chloride, which is a ligand to each of the cations. When phosphate is soaked into these Mn2+ cocrystals, one of the three Mn2+ ions is expelled from the active site, leaving metal ions with octahedral and tetrahedral coordination geometry. In addition, the structure of apoinositol monophosphatase was determined to 2.5 A resolution. Residues 70-75, a two-turn helical segment which is involved in metal coordination, moves away from the metal binding site by 2-3 A in the absence of cations. Residues 30-40, which wrap around the metal binding site and interact with the metal indirectly through solvent molecules and protein ligands to the metal, become disordered in the absence of metal. In various metal complexes, segmental mobility is also observed in the residues which form the metal binding sites. The results of these studies of the interaction of inositol monophosphatase with cations suggest that the enzyme accomplishes phosphate ester hydrolysis using two metal ions, one with octahedral and one with tetrahedral coordination geometry. Broad metal-binding specificity appears to result from extensive flexibility in several of the protein segments which contribute metal ligands, from the presence of alternate metal ligands and from metal coordination spheres which include water molecules.

Apoenzymes↗
PubMed2005

The rationale for metal-on-metal total hip arthroplasty.

Metal-on-metal total hip arthroplasty has the longest clinical history of any of the currently used articular couples. Long-term followup of what are now considered suboptimal designs (eg, McKee Farrar, Ring, Sivash) has produced a wealth of knowledge regarding the safety and efficacy of this articular combination. Retrieval analysis of metal-on-metal total hip arthroplasty articular couples has shown wear between 1 and 5 microns per year after initial wear-in, in comparison with 100 to 200 microns per year associated with metal-on-polyethylene wear. The constituent metal ions released through wear of the metal-on-metal total hip arthroplasty are excreted primarily in the urine; serum levels have been 3 to 5 times higher in patients who have had metal-on-metal total hip arthroplasties than in control subjects. No adverse physiologic effects have been identified in the long-term followup of patients exposed to cobalt-chromium implants. The clinical results of metal-on-metal total hip arthroplasties equal or exceed those of conventional articular couples and rarely are associated with osteolysis compared with conventional couples. Additional advantages of the metal-on-metal combination are the ability to use larger-diameter femoral heads for enhanced stability and the absence of concern over possible fracture of the articular components. The long-term experiences with metal-on-metal total hip arthroplasty make this combination of implant material the conservative choice for success.

Arthroplasty, Replacement, Hip↗