Redox voltammetry of sub-parts per billion levels of Cu2+ at polyaspartate-modified gold electrodes

An electrochemical sensor for the detection of Cu2+ is reported which incorporates poly-l-aspartic acid (PLAsp) with 32–96 aspartate units as a selective ligand for the metal ion. PLAsp is covalently attached to a gold electrode modified with a monolayer of 3-mercaptopropionic acid using carbodiimide coupling via an N-hydroxysuccinimide (NHS) ester intermediate. The acid side groups and deprotonated peptide nitrogens on two aspartate moieties are thought to be primarily responsible for chelation of Cu2+, which remains bound when reduced to Cu+. A consequence of the multiple binding points that are available with a polypeptide is the low detection limit. The lowest concentration detected was 3 nM (0.2 ppb) achieved with Osteryoung square wave voltammetry. This detection limit compares favourably with that of ICP-OES and previously reported cysteine-modified electrodes. Analysis of tap and lake water samples using the PLAsp-modified electrode agreed well with ICP-OES analysis of the same samples.

Exploring the use of the tripeptide Gly–Gly–His as a selective recognition element for the fabrication of electrochemical copper sensors

The modification of electrodes with the tripeptide Gly–Gly–His for the detection of copper in water samples is described in detail. The tripeptide modified electrode was prepared by first self-assembling 3-mercaptopropionic acid (MPA) onto the gold electrode followed by covalent attachment of the tripeptide to the self-assembled monolayer using carbodiimide coupling. The electrodes were characterized using electrochemistry, a newly developed mass-spectrometry method and quantum mechanical calculations. The mass spectrometry confirmed the modification to proceed as expected with peptide bonds formed between the carboxylic acids of the MPA and the terminal amine of the peptide. Electrochemical measurements indicated that approximately half the MPA molecules in a SAM are modified with the peptide. The peptide modified electrodes exhibited high sensitivity to copper which is attributed to the stable 4N coordinate complex the peptide formed around the metal ion to give copper the preferred tetragonal coordination. The formation of a 4 coordinate complex was predicted using quantum mechanical calculation and confirmed using mass spectrometry. The adsorption of the copper to the peptide modified electrode was consistent with a Langmuir isotherm with a binding constant of (8.1 ± 0.4) 1010 M−1 at 25 °C.

Self-assembled monolayers into the 21st century : recent advances and applications

The modification of an interface on a molecular level with more than one molecular ‘building block' is essentially an example of the ‘bottom–up' fabrication principle of nanotechnology. The fabrication of such integrated molecular systems in electrochemistry has seen rapid progress in recent years via the development of sensing interfaces fabricated using self-assembled monolayers (SAMs). This review outlines recent advances and applications of self-assembled monolayers for modifying electrodes with an emphasis on the development of integrated molecular systems. First, some basic issues regarding fabricating integrated molecular systems, such as the role of the surface topography of the electrode and patterning surfaces, are discussed. Subsequently an overview of recent developments in pH, inorganic and bio sensing involving the use of SAMs is given. Finally emerging trends in using molecular building blocks in the fabrication of integrated molecular systems, such as nanotubes, dendrimers and nanoparticles, are reviewed.

Facile synthesis of graphene oxide hybrids bridged by copper ions for increased conductivity

In this article, we report a facile method for preparing graphene oxide (GO) hybrid materials consisting of copper ions (Cu2+) complexed with GO, where Cu2+ acted as bridges connecting GO sheets. The method of film formation is based on cross-linking GO using Cu2+ followed by filtration onto nanoporous supports. This binding can be rationalized due to the chemical interaction between the functional groups on GO and the metal ion. We observed that there was a decrease in charge transfer resistance through electrochemical study. It suggests that the presence of metal ions in GO films could introduce new energy levels along the electron transport pathway and open up possible conduction channels. We also found that the hybrid graphene film assembled with Cu2+ dramatically decreases resistance through flash light reduction.

Using a selective cadmium-binding peplipid to create responsive liquid crystalline nanomaterials.

A specific metal ion-responsive lipid liquid crystalline (LLC) dispersion system was fabricated, which can work in buffer solutions. The LLC matrix was prepared from phytantriol which spontaneously forms the reversed bicontinuous cubic phase in water, and a novel peptide-lipid conjugate (peplipid) consists of a myristate alkyl chain for anchoring into the phytantriol-based cubic bilayer and a peptide sequence for capturing a specific metal ion. The peplipid in its unbound state, when added into the phytantriol-based cubic system induces a positive effect on the bilayer curvature, resulting in the formation of the lamellar phase (vesicles) and the dispersion was transparent in appearance. Upon binding of the cadmium ion, the peplipid induces a negative effect on the lipid bilayer curvature and consequently leading to the formation of cubic phase and opaque appearance. In contrast, other metal ions, including buffering salts, could not sufficiently trigger the phase transition due to weak interaction with the peplipid. The high selectivity of metal ion interaction and triggered phase transition provide potential applications, such as in colloidal-mineral separation, triggered drug release and treatment of cadmium (II) pollution.

A biomimetic sensor for the detection of lead in water.

The monitoring of lead (II) ions (Pb(2+)) in water is essential for both human health and the environment. Herein, a simple yet innovative biosensor for Pb(2+) detection is presented. The sensor is developed by the self-assembly of gold nanoparticles (GNPs) core-satellite structure using naturally occurring tripeptide glutathione (GSH) as linker. The addition of Pb(2+) caused a red-to-blue color change and the localized surface plasmon resonance (LSPR) band was shifted to ca. 650nm. The limit of detection (LOD) is found to be 47.6nM (9.9ppb) by UV-vis spectroscopy with high selectivity against other heavy metals. This method offers a new strategy for heavy metal detection using functionalized GNPs.

Comparative analyses of cadmium and zinc uptake correlated with changes in natural resistance-associated macrophage protein (NRAMP) expression in Solanum nigrum L. and Brassica rapa

Environmental context Soils contaminated with metals can pose both environmental and human health risks. This study showed that a common crop vegetable grown in the presence of cadmium and zinc readily accumulated these metals, and thus could be a source of toxicity when eaten. The work highlights potential health risks from consuming crops grown on contaminated soils. Abstract Ingestion of plants grown in heavy metal contaminated soils can cause toxicity because of metal accumulation. We compared Cd and Zn levels in Brassica rapa, a widely grown crop vegetable, with that of the hyperaccumulator Solanum nigrum L. Solanum nigrum contained 4 times more Zn and 12 times more Cd than B. rapa, relative to dry mass. In S. nigrum Cd and Zn preferentially accumulated in the roots whereas in B. rapa Cd and Zn were concentrated more in the shoots than in the roots. The different distribution of Cd and Zn in B. rapa and S. nigrum suggests the presence of distinct metal uptake mechanisms. We correlated plant metal content with the expression of a conserved putative natural resistance-associated macrophage protein (NRAMP) metal transporter in both plants. Treatment of both plants with either Cd or Zn increased expression of the NRAMP, with expression levels being higher in the roots than in the shoots. These findings provide insights into the molecular mechanisms of heavy metal processing by S. nigrum L. and the crop vegetable B. rapa that could assist in application of these plants for phytoremediation. These investigations also highlight potential health risks associated with the consumption of crops grown on contaminated soils.

Capsular polypyrrole hollow nanofibers: an efficient recyclable adsorbent for hexavalent chromium removal

Capsular polypyrrole hollow nanofibers (PPy-HNFs) were fabricated via in situ polymerization of pyrrole on an organic-inorganic template, followed by acid etching. Their application in removing hexavalent chromium (Cr(vi)) from aqueous solution was then investigated. The morphologies of the capsular PPy-HNFs were studied by both scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which showed that the PPy-HNFs had a capsular structure in the walls of hollow nanofibers. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) data confirmed the adsorption of Cr on capsular PPy-HNFs. The adsorption capacity increased with reduced pH of the initial solution and the adsorption process can be described using the pseudo-second-order model. These capsular PPy-HNFs showed a high Cr(vi) adsorption capacity up to 839.3 mg g-1. This adsorption capacity was largely retained even after five adsorption/desorption cycles. Electrostatic attraction between Cr and PPy-HNFs was studied using a proposed adsorption mechanism. The capsular PPy-HNFs formed a flexible membrane, which allowed easy handling during application. This study has demonstrated the possibilities of using this capsular PPy-HNF membrane for heavy metal removal from aqueous solution.

Accumulation of six metals in the mangrove crab Ucides cordatus (Crustacea: Ucididae) and its food source, the red mangrove Rhizophora mangle (Angiosperma: Rhizophoraceae)

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

Acúmulo de metais pesados em cana-de-açúcar mediante a aplicação de lodo de esgoto e vinhaça

O uso de resíduos agroindustriais pode acumular metais pesados no solo e na planta. O objetivo deste trabalho foi avaliar os efeitos do lodo de esgoto e/ou vinhaça, aplicados no solo, disponibilizando Cd, Cr, Ni e Pb ao solo e quantificar as respectivas concentrações em plantas de cana-de-açúcar, após três aplicações anuais sucessivas. O experimento foi conduzido em condições de campo, com parcelas experimentais de cinco linhas espaçadas de 1,5 m e 10 m de comprimento. O delineamento experimental adotado foi o de blocos casualizados, com três repetições. Os tratamentos avaliados foram: 1. Lodo de esgoto com 100% de N; 2. Lodo de esgoto com 200% de N; 3. Vinhaça com 100% de K; 4. Vinhaça com 200% de K; 5. Lodo de esgoto+vinhaça com 100% de N e K; 6. Lodo de esgoto+vinhaça com 200% de N e K; 7. Testemunha (fertilização mineral). Os baixos teores de metais pesados (Cd, Cr, Ni e Pb) disponíveis no solo e nas partes das plantas de cana-de-açúcar indicam que o lodo de esgoto e a vinhaça, empregados nas doses mencionadas, não apresentaram, após três aplicações anuais sucessivas, potencial de contaminação do sistema solo-planta.

Lead distribution in organic matter of loamy oxisol treated with manure and its effect on microbial biomass

This paper reports a study regarding the distribution of lead in the organic matter fractions of a loamy oxisol treated with stable manure, and its effect on the soil microbial biomass. The experimental design was a completely randomized factorial with three replicates. Treatments were four lead (Pb) rates (0, 200, 400, and 600 mg kg(-1) soil), two levels of manure (0 and 30 Mg ha(-1)) and two sampling times (30 and 60 days after lead application). Total and soil lead soluble in Mehlich 1 extractant, and Ph in the different fractions of the organic matter (fulvic acid, humic acid, and residual) were evaluated along with the soil microbial biomass. Data showed that lead, applied as PbCl2, was concentrated in the residual fraction. The application of manure at the rate of 30 Mg ha(-1) did not affect lead distribution in the fractions until 60 days after incorporation. Lead extracted by Mehlich 1 increased as function of the quantity applied. Manure stimulated the growth of the soil microbial biomass which was reduced by the 200 mg kg(-1) doses of lead, with manure application, increasing, however, with larger rates. Mehlich 1 extracted only part of the lead present in the residual fraction.