Metal and metalloid containing natural products and a brief overview of their applications in biology, biotechnology and biomedicine

Bioinorganic natural product chemistry is a relatively unexplored but rapidly developing field with enormous potential for applications in biology, biotechnology (especially in regards to nanomaterial development, synthesis and environmental cleanup) and biomedicine. In this review the occurrence of metals and metalloids in natural products and their synthetic derivatives are reviewed. A broad overview of the area is provided followed by a discussion on the more common metals and metalloids found in natural sources, and an overview of the requirements for future research. Special attention is given to metal hyperaccumulating plants and their use in chemical synthesis and bioremediation, as well as the potential uses of metals and metalloids as therapeutic agents. The potential future applications and development in the field are also discussed.

Electrochemical and spectroscopic investigation of redox processes for labile metal dithiocarbamate complexes

Although metal dithiocarbamate complexes have been studied extensively, there is in sate cases a distinct lack of data concerning redox properties and the products thereof. This is particularly true for complexes of the late transition and main group metals which are important in agriculture, industry, and chemical analysis. Hence, using electrochemical techniques, the redox behaviour of dithiocarbamate complexes of zinc, cadmium, mercury, lead, and tellurium has been examined. The products of oxidation and reduction have also been characterized by spectroscopic techniques (NMR, EPR, UV, and IR), mass spectrometry, conductivity, and Where possible, crystallographic study of an isolated compound. The species studied were without exception labile with the result that electrochemistry at mercury electrodes was influenced by the great stability of the mercury dithiocarbamate (Hg(RR’dtc) 2) complexes. Investigation of the latter showed that oxidative processes in the presence of mercury led to a new class of expounds: polymeric mercury dithiocarbamato cations. Oily one of these could be isolated as a solid, with the formula [Hg5(RR’dtc) 8](C104)2 For R=R’=ethyl the crystal structure was determined. For other metal dithiocarbamates the electrochemical behaviour at mercury electrodes in many ways paralleled that of the mercury analogues. Thus oxidative processes involved oxidation of electrode mercury to form mixed metal cationic species. Polarographic reduction led to the metal amalgam, usually via formation of mercury dithiocarbamate. Electrochemical studies at inert electrode materials such as platinum yielded distinctly different responses, with both oxidation and reduction being more difficult. Oxidation products at platinum electrodes gave identical polarographic responses to those firm mercury electrodes due to rapid interaction of the former with electrode mercury. The results are in sharp contrast to much of the previous work on transition metal dithiocarbamates for which electrochemical redox processes are often metal based arid not explicated by interaction with the electrode material.

Electrochemical metal ion sensors. Exploiting amino acids and peptides as recognition elements

Amino acids and peptides are known to bind metal ions, in some cases very strongly. There are only a few examples of exploiting this binding in sensors. The review covers the current literature on the interaction of peptides and metals and the electrochemistry of bound metal ions. Peptides may be covalently attached to surfaces. Of particular interest is the attachment to gold via sulfur linkages. Sulfur-containing peptides (eg cysteine) may be adsorbed directly, while any amino group can be covalently attached to a carboxylic acid-terminated thiol. Once at a surface, the possibility for using the attached peptide as a sensor for metal ions becomes realised. Results from the authors’ laboratory and elsewhere have shown the potential for selective monitoring of metal ions at ppt levels. Examples of the use of poly-aspartic acid and the copper binding peptide Gly-Gly-His for detecting copper ions are given.

Two-dimensional correlation localized surface plasmon resonance spectroscopy for analysis of the interaction between metal nanoparticles and bovine serum albumin

Time-resolved extinction spectra assisted with two-dimensional correlation spectroscopy (2DCOS) analysis and principal component analysis (PCA) were employed to investigate the interaction between bovine serum albumin (BSA) and metal nanoparticles (NPs). A series of localized surface plasmon resonance (LSPR) spectra of metal NPs were measured just after a small amount of BSA was added into metal colloids. Through 2DCOS analysis, remarkable changes in the intensities of the LSPR were observed. The interaction process was totally divided into three periods according to the PCA. Transmission electron microscopy, dynamic light scattering, and ζ-potential measurements were also employed to characterize the interaction between BSA and metal NPs. The addition of BSA brings silver NPs to aggregate through the electrostatic interaction between them, but it has less effect on gold NPs. In a gold and silver mixed system, gold NPs can affect the interaction of silver NPs and BSA, leading it to weaken. The combination of 2DCOS analysis and LSPR spectroscopy is powerful for exploring the LSPR spectra of the metal NP involved systems. This combined technique holds great potential in LSPR sensing through analysis of slight, slim spectral changes of metal colloids

Metals in the environment as risk factors for infectious diseases: gaps and opportunities

Many parts of the world in which common infectious diseases are endemic also have the highest prevalence of trace metal deficiencies or rising rates of trace metal pollution. Infectious diseases can increase human susceptibility to adverse effects of metal exposure (at suboptimal or toxic levels), and metal excess or deficiency can increase the incidence or severity of infectious diseases. The co-clustering of major infectious diseases with trace metal deficiency or toxicity has created a complex web of interactions with serious but poorly understood health repercussions, yet has been largely overlooked in animal and human studies. This book focuses on the distribution, trafficking, fate, and effects of trace metals in biological systems. Its goal is to enhance our understanding of the relationships between homeostatic mechanisms of trace metals and the pathogenesis of infectious diseases. Drawing on expertise from a range of fields, the book offers a comprehensive review of current knowledge on vertebrate metal-withholding mechanisms and the strategies employed by different microbes to avoid starvation (or poisoning). Chapters summarize current, state-of-the-art techniques for investigating pathogen-metal interactions and highlight open question to guide future research. The book makes clear that improving knowledge in this area will be instrumental to the development of novel therapeutic measures against infectious diseases. ContributorsM. Leigh Ackland, Vahid Fa Andisi, Angele L. Arrieta, Michael A. Bachman, J. Sabine Becker, Robert E. Black, Julia Bornhorst, Sascha Brunke, Joseph A. Caruso, Jennifer S. Cavet, Anson C. K. Chan, Christopher H. Contag, Heran Darwin, George V. Dedoussis, Rodney R. Dietert, Victor J. DiRita, Carol A. Fierke, Tamara Garcia-Barrera, David P. Giedroc, Peter-Leon Hagedoorn, James A. Imlay, Marek J. Kobylarz, Joseph Lemire, Wenwen Liu, Slade A. Loutet, Wolfgang Maret, Andreas Matusch, Trevor F. Moraes, Michael E. P. Murphy, Maribel Navarro, Jerome O. Nriagu, Ana-Maria Oros-Peusquens, Elisabeth G. Pacyna, Jozef M. Pacyna, Robert D. Perry, John M. Pettifor, Stephanie Pfaffen, Dieter Rehder, Lothar Rink, Anthony B. Schryvers, Ellen K. Silbergeld, Eric P. Skaar, Miguel C. P. Soares, Kyrre Sundseth, Dennis J. Thiele, Richard B. Thompson, Meghan M. Verstraete, Gonzalo Visbal, Fudi Wang, Mian Wang, Thomas J. Webster, Jeffrey N. Weiser, Günter Weiss, Inga Wessels, Bin Ye, Judith T. Zelikoff, Lihong Zhang

Seawater temperature effect on metal accumulation and toxicity in the subantarctic Macquarie Island isopod, Exosphaeroma gigas

Very little is currently known of subantarctic nearshore invertebrates' sensitivity to environmental metals and the role of temperature in this relationship. This study investigated Cu and Zn toxicity in the common subantarctic intertidal isopod, Exosphaeroma gigas, and the influence of temperature on Cu toxicity and bioaccumulation kinetics. Adult E. gigas are insensitive to Cu and Zn at concentrations of 3200 and 7400μg/L respectively in non-renewal tests at 5.5°C (ambient subtidal temperature) over 14days. Under renewed exposures over the same temperature and time period the LC50 for copper was 2204μg/L. A 10-fold increase in Cu body burden occurred relative to zinc, indicating E. gigas has different strategies for regulating the two metals. Copper toxicity and time to mortality both increased with elevated temperature. However, temperature did not significantly affect Cu uptake rate and efflux rate constants derived from biodynamic modelling at lower Cu concentrations. These results may be attributable to E. gigas being an intertidal species with physiological mechanisms adapted to fluctuating environmental conditions. Cu concentrations required to elicit a toxicity response indicates that E. gigas would not be directly threatened by current levels of Cu or Zn present in Macquarie Island intertidal habitats, with the associated elevated temperature fluctuations. This study provides evidence that the sensitivity of this subantarctic intertidal species to metal contaminants is not as high as expected, and which has significance for the derivation of relevant guidelines specific to this distinct subpolar region of the world.

Cadmium, copper, mercury, and zinc concentrations in tissues of the King Crab (Pseudocarcinus gigas) from southeast Australian waters

The concentrations of cadmium, copper, mercury, and zinc were determined in muscle (body, claw, and leg), hepatopancreas, and gill tissues of Pseudocarcinus gigas, an exceptionally large, long-lived, and deep-dwelling crab species. The accumulation patterns observed are discussed in terms of both intra- and interspecies variations, with particular attention to the possible consequences of the extreme size and depth range of P. gigas. Metal concentrations did not depend significantly on sex of the crab. Significant differences between tissues were detected for all metals, and the distribution of metal between the tissues was different for each metal. Significant correlations were found between metal concentrations in the various tissues and crab size, and these are discussed and rationalised. The concentrations of mercury and zinc in muscle tissue increased with crab size and were high compared to other crab species. The concentrations of cadmium and copper present in edible tissues were not especially high compared to other crab species, but the concentration of cadmium in the hepatopancreas is of dietary concern.

Observations of metal concentrations in tilapia (Oreochromis mossambicus)in reservoirs of South Sri Lanka

Samples of the muscle and liver of tilapia (Oreochromis mossambicus) obtained from the five reservoirs in four catchments in southern Sri Lanka in 1998 were analyzed for 16 elements: As, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn by inductively coupled plasma emission spectrophotometry, and Hg by atomic absorption spectrophotometry. The concentrations of Cr, Ni, and Pb were below the detection limits of the instrumental techniques employed in all samples. The elements As, Ca, Co, Cu, Fe, Hg, K, Mg, Mn, Na, Sr, and Zn were detected in the muscle and liver tissue, with Cd detected in some liver samples. There were no statistically significant differences between the individual concentrations of any of the metals and the site from which the tilapia were collected (P>0.05). Furthermore, no statistically significant correlations were found between total length of fish and metal concentration. No elements were found at concentrations of toxicological concern. However, a principal component analysis suggests that the populations of tilapia in the reservoirs may be exposed to different regimes of metals, possibly associated with different catchment land-use patterns.

Reduction of metal leaching in brown coal fly ash using geopolymers

Current regulations classify fly ash as a prescribed waste and prohibit its disposal in regular landfill. Treatment of the fly ash can reduce the leach rate of metals, and allow it to be disposed in less prescribed landfill. A geopolymer matrix was investigated as a potential stabilisation method for brown coal fly ash. Precipitator fly ash was obtained from electrostatic precipitators and leached fly ash was collected from ash disposal ponds, and leaching tests were conducted on both types of geopolymer stabilised fly ashes. The ratio of fly ash to geopolymer was varied to determine the effects of different compositions on leaching rates.

Using inorganic polymer to reduce leach rates of metals from brown coal fly ash

The burning of brown coal for electricity generation produces thousands of tonnes of fly ash each year. Treatment of the fly ash can reduce leach rates of metals and allow it to be disposed in less prescribed landfill. A geopolymer matrix was investigated as a potential stabilisation method for fly ash obtained from electrostatic precipitators and ash disposal ponds. The ratio of fly ash and geopolymer was varied to determine the effects of different compositions on leaching rates. The major element leachate concentrations obtained from pond ash were lower than that of precipitator fly ash. Conversely, precipitator ash-geopolymers were better for trace heavy metal stabilisation. Effective reduction of elemental concentrations in the leachate has been achieved, particularly for calcium, arsenic, selenium, strontium and barium. Scanning electron microscopy revealed the distribution of metals originated from fly ash and from added geopolymer material. It also showed that some elements are leached from ash particles to the geopolymer phase and others remained as undissolved particles. Qualitative analysis showed that fly ash particles interacted with the geopolymers phase through surface reactions.

Using geopolymer to minimise metals leaching from brown coal fly ash

Fly ash is generated from combustion of brown coal in power stations. The majority of fly ash is removed by electrostatic precipitators (ESP) and finally disposed into the landfill as prescribed wastes. A method was studied to add clay materials to the brown coal fly ash in order to form the so-called geopolymer network, which is effective at stopping the metal contents from leaching, and have minimum impact to the environment. The experiments were conducted parallel on leached fly ash and dry precipitator fly ash. The ratios of fly ash and added clay materials were varied to determine the effects of different compositions on leaching rates. Both X-ray diffraction analysis and scanning electron microscopy images showed that as the percentage of fly ash was increased, the formation of geopolymer is reduced. Eighteen metals and heavy metals were targeted during the leaching tests and the leachate samples were analysed using ICP-AES and ICP-MS. It was found that the reduction of metal leaching was achieved by adding up to 60% of fly ash to form the geopolymer like structure. Significant reductions were observed for calcium, strontium and barium. Leached fly ash achieved better stabilisation than dry precipitator fly ash for major elements. It's hard to quantify its effects on trace metals leaching due to their ultra low concentration in the fly ash. The samples spiked with trace metals of lead, zinc, mercury and barium showed remarkable reduction in leaching.

Degradation of the strength of porous titanium after alkali and heat treatment

Porous titanium with a porosity of 75% was fabricated by space-holder sintering through powder metallurgy. The effect of the alkali and heat treatment on the strength of the porous titanium was investigated. Results indicated that the alkali and heat treatment led to a significant decrease in the strength of the porous titanium, whichwas causedby the degradation due to corrosion of the struts of the porous titanium with a layer of the reaction products, grain pullout and micro-cracks.

Sulfur and heavy metals in biological tissue

The correlation between sulfur, metallothionein and heavy metals was investigated in biological samples from the aquatic environment. Samples of orange roughie, shark, goldfish and king crab were analysed for metals and sulfur. Results indicated that there was insufficient evidence to suggest any relationship between sulfur and total metals, but there was sufficient evidence to suggest a significant relationship existed between mercury and total sulfur in the biological tissues examined.

Biomimetic porous titanium scaffolds for orthopaedic and dental applications

The development of artificial organs and implants for replacement of injured and diseased hard tissues such as bones, teeth and joints is highly desired in orthopedic surgery. Orthopedic prostheses have shown an enormous success in restoring the function and offering high quality of life to millions of individuals each year. Therefore, it is pertinent for an engineer to set out new approaches to restore the normal function of impaired hard tissues.

Over the last few decades, a large number of metals and applied materials have been developed with significant improvement in various properties in a wide range of medical applications. However, the traditional metallic bone implants are dense and often suffer from the problems of adverse reaction, biomechanical mismatch and lack of adequate space for new bone tissue to grow into the implant. Scientific advancements have been made to fabricate porous scaffolds that mimic the architecture and mechanical properties of natural bone. The porous structure provides necessary framework for the bone cells to grow into the pores and integrate with host tissue, known as osteointegration. The appropriate mechanical properties, in particular, the low elastic modulus mimicking that of bone may minimize or eliminate the stress-shielding problem. Another important approach is to develop biocompatible and corrosion resistant metallic materials to diminish or avoid adverse body reaction. Although numerous types of materials can be involved in this fast developing field, some of them are more widely used in medical applications. Amongst them, titanium and some of its alloys provide many advantages such as excellent biocompatibility, high strength-to-weight ratio, lower elastic modulus, and superior corrosion resistance, required for dental and orthopedic implants. Alloying elements, i.e. Zr, Nb, Ta, Sn, Mo and Si, would lead to superior improvement in properties of titanium for biomedical applications.

New processes have recently been developed to synthesize biomimetic porous titanium scaffolds for bone replacement through powder metallurgy. In particular, the space holder sintering method is capable of adjusting the pore shape, the porosity, and the pore size distribution, notably within the range of 200 to 500 m as required for osteoconductive applications. The present chapter provides a review on the characteristics of porous metal scaffolds used as bone replacement as well as fabrication processes of porous titanium (Ti) scaffolds through a space holder sintering method. Finally, surface modification of the resultant porous Ti scaffolds through a biomimetic chemical technique is reviewed, in order to ensure that the surfaces of the scaffolds fulfill the requirements for biomedical applications.

Wear mechanisms in forming of HSS and AHSS

Code : C/64/09