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James A Holcombe

Publications and source records attributed to James A Holcombe.

4 recordsLinked to original sources

Detection of palladium by cold atom solution atomic absorption.

One of the largest obstacles in miniaturizing traditional atomic spectroscopic sources is the need for a thermal/electrical source for free atom production. A single article in the literature has demonstrated atomic absorption detection of Ag, Cu, and Pd in solution at room temperature for atoms in the gas phase, which may ultimately permit miniaturization. Unfortunately, several laboratories have found that reproducing the phenomenon has been difficult. Without a sound fundamental explanation of the processes leading to the signal, one must conclude that it can be done, but some unsuspected and unknown design/methodological nuances are responsible for only a single reported success. Gas phase atoms could exist at room temperature "in solution" if the atoms were trapped in very small bubbles. In the current study, submicrometer-sized bubbles were created in a flow-through cell during the mixing of an alcohol-water solution containing a reducing agent with water containing the analyte. A repeatable atomic absorption signal was produced. Replacement of ethanol with 1-propanol and use of a surfactant increased the signal. Limits of detection of approximately 100 ppb in Pd were achieved, and it is estimated that approximately 0.4% of the Pd initially added is contained within the bubbles as gaseous atoms. The paper discusses the fundamental processes needed to achieve a repeatable signal.

Journal Article↗

Poly(L-cysteine) as an electrochemically modifiable ligand for trace metal chelation.

The short-chain (n approximately equal to 50) homopolymer poly(L-cysteine) (PLC) has been previously studied for use as a novel metal chelator. PLC exhibits reversible oxidation-reduction chemistry involving the thiol groups of the cysteine (Cys) residues. Previously, chemical oxidation of the PLC immobilized on silica showed that metal binding capacity was minimal in the oxidized state. In this study, Cys and PLC are immobilized on a glassy carbon disk electrode (GCE) to study these redox processes and how they impact metal binding and release. Voltammetric and chronoamperometric methods were employed to demonstrate nearly monolayer coverage of both immobilized Cys monomer and immobilized PLC on GCE. The PLC-GCE exhibited a maximum metal binding capacity for Cd2+ of approximately 11 Cd2+ ions/chain. No detectable metal binding capacity was observed for oxidized PLC. The bound metals were capable of being efficiently released through disulfide bond formation and tertiary structure changes by means of repetitive oxidative pulses. The Cys-modified electrode exhibited a metal binding capacity for Cd2+ of approximately 1 Cd2+/Cys. Oxidized Cys did retain a significant capacity following oxidation, likely as a result of complexation with the terminal carboxylate site and unoxidized thiols. A glycine (Gly)-modified electrode was also evaluated as an amino acid control. Minimal Cd2+ binding was observed. Further metal binding studies were conducted using PLC-GCE with single metal solutions of Co2+, Cu2+, Ni2+, and Pb2+, as well as a multimetal solution composed of equal concentrations of all five target metals. The observed metal binding trend was as follows: Cu2+ > Cd2+ > Ni2+ > Pb2+ > Co2+. All metals were quantitatively released upon oxidation of PLC using the same anodic potential, 600 mV vs Ag/AgCl.

Cadmium↗

Optimizing the multielement analysis capabilities of an ICP quadrupole mass spectrometer using electrothermal vaporization sample introduction.

A mathematical solution and an experimental procedure are described for calculating the maximum number of transient signals, such as those obtained using ETV sample introduction into an ICPMS, that can be monitored by a scanning spectrometer, such as a quadrupole mass analyzer. The total number of masses that can be monitored per ETV firing is shown to be dependent on the values chosen for data collection (i.e., scan time and dwell time) and the necessary limits of detection required by the method. The theory shows the effect that statistical noise, peak shapes, and inconsistent peak appearance times have on the overall variance calculated for the sample concentration based on total counts or "peak area". Also included in the variance calculation is the contribution made by the autosampler as an example of one type of error that is not associated with the data collection parameters. The theory is validated by two experiments where 21 and 68 transient signals are monitored per ETV firing; and as predicted, a 10 ppb sample is accurately quantified with precision better than 9% in both cases.

Journal Article↗

Quantitative determination of single-bead metal content from a peptide combinatorial library.

An electrothermal vaporizer inductively coupled plasma mass spectrometer (ETV-ICPMS) was used to quantitatively screen metals bound to single polystyrene (TentaGel) beads with immobilized oligopeptides. Tests were performed using ETV-ICPMS to screen a series of identical beads as well as a series of combinatorial library beads exposed to a multimetal solution composed of Mg2+, Mn2+, Ni2+, Cu2+, Cd2+, Eu2+, and Pb2+. The residual metal content remaining bound to the beads after acid extractions was also analyzed by solid sampling of the entire bead using oxygen ashing in the ETV. Nine beads (80 mesh, 0.25 mmol g(-1) nominal capacity) containing covalently attached polyaspartic acid (PLAsp; n = 20) showed metal extract concentrations in the range of 4-130 ng mL(-1). After normalizing by bead volume, the precision of capacity measurements in a single bead (7-14%) was primarily dictated by analysis error and contributions from bead diameter measurement with negligible contributions, surprisingly, from variations in site density from bead to bead. A sample combinatorial library of the sequence GXXGXXGXXGXX (X = cysteine, aspartic acid, or glutamic acid and G = glycine) (60 mesh, 0.25 mmol g(-1) nominal capacity) was also used to demonstrate the utility of this method. Metal extract concentrations ranged from 1 to 1300 ng mL(-1) with significant concentration variation between beads, indicating the individual selectivity on each bead. For these larger beads, analysis precision (i.e., capacity precision) was further improved to 3-10% due to the overall increase in bead metal content. Through metal extract determinations, ETV-ICPMS was shown to be a viable nondestructive tool for full metal characterization of "hit" sequences belonging to a combinatorial library.

Binding Sites↗