Gerardo Gamez

Atmospheric Pressure Chemical Ionization Source. 1. Ionization of Compounds in the Gas Phase

A novel chemical ionization source for organic mass spectrometry is introduced. This new source uses a glow discharge in the flowing afterglow mode for the generation of excited species and ions. The direct-current gas discharge is operated in helium at atmospheric pressure; typical operating voltages and currents are around 500 V and 25 mA, respectively. The species generated by this atmospheric pressure glow discharge are mixed with ambient air to generate reagent ions (mostly ionized water clusters and NO+), which are then used for the ionization of gaseous organic compounds. A wide variety of substances, both polar and nonpolar, can be ionized. The resulting mass spectra generally show the parent molecular ion (M+ or MH+) with little or no fragmentation. Proton transfer from ionized water clusters has been identified as the main ionization pathway. However, the presence of radical molecular ions (M+) for some compounds indicates that other ionization mechanisms are also involved. The analytical capabilities of this source were evaluated with a time-of-flight mass spectrometer, and preliminary characterization shows very good stability, linearity, and sensitivity. Limits of detection in the single to tens of femtomole range are reported for selected compounds.

Characterization of Cr(VI) binding and reduction to Cr(III) by the agricultural byproducts of Avena monida (oat) biomass.

Chromium contamination of the environment has become an important issue due to the potential health threat it poses. Conventional technologies to clean up heavy metal ions from contaminated waters have been utilized, but these technologies are not cost-effective. However, the use of agricultural waste byproducts for the removal of Cr(VI) from contaminated waters may be a new cost-effective alternative. Oat byproducts from the Juarez Valley in Mexico were studied for the ability to bind Cr(VI) under different temperature and time conditions. The metal binding ability of oat byproducts was calculated from experimental data collected at temperatures of 8, 26, and 54 degrees C, and time exposures of 1, 6, 24, 48, and 72 h at each temperature. These results showed that the binding of Cr(VI) to oat biomass increased as time and temperature increased. The bound chromium was recovered from the oat biomass by treatment with 0.2M HCl. Through the use of X-ray absorption spectroscopy, the reduction of Cr(VI) to Cr(III) was determined to occur by the oat byproducts. These results indicate that the use of agricultural waste byproducts could be a better alternative for the removal and subsequent reduction of Cr(VI) to Cr(III) from contaminated waters.

What Can We Learn from Ambient Ionization Techniques

Ambient mass spectrometry—mass spectrometric analysis with no or minimal effort for sample preparation—has experienced a very rapid development during the last 5 years, with many different methods now available for ionization. Here, we review its range of applications, the hurdles encountered for its quantitative use, and the proposed mechanisms for ion formation. Clearly, more effort needs to be put into investigation of matrix effects, into defining representative sampling of heterogeneous materials, and into understanding and controlling the underlying ionization mechanisms. Finally, we propose a concept to reduce the number of different acronyms describing very similar embodiments of ambient mass spectrometry.

Atmospheric Pressure Chemical Ionization Source. 2. Desorption−Ionization for the Direct Analysis of Solid Compounds

The flowing afterglow-atmospheric pressure glow discharge (APGD) ionization source described in part 1 of this study (in this issue) is applied to the direct analysis of condensed-phase samples. When either liquids or solids are exposed to the ionizing beam of the APGD, strong signals for the molecular ions of substances present on their surfaces can be detected without compromising the integrity of the solid sample structure or sample substrate. As was observed for gas-phase compounds in part 1 of this study, both polar and nonpolar substances can be ionized and detected by mass spectrometry. The parent molecular ion (or its protonated counterpart) is usually the main spectral feature, with little or no fragmentation in evidence. Preliminary quantitative results show that this approach offers very good sensitivity (detection limits in the picogram regime are reported for several test compounds in part 1 of this study) and linear response to the analyte concentration. Examples of the application of this strategy to the analysis of real-world samples, such as the direct analysis of pharmaceutical compounds or foods is provided. The ability of this source to perform spatially resolved analysis is also demonstrated. Preliminary studies of the mechanisms of the reactions involved are described.

Phytofiltration of hazardous cadmium, chromium, lead and zinc ions by biomass of Medicago sativa (Alfalfa)

Abstract Previous laboratory batch experiments of Medicago sativa (Alfalfa) indicated that the African shoots population had an appreciable ability to bind copper(II) and nickel(II) ions from aqueous solution. Batch laboratory pH profile, time dependency and capacity experiments were performed to determine the binding ability of the African shoots for cadmium(II), chromium(III), chromium(VI), lead(II), and zinc(II). Batch pH profile experiments for the mentioned ions indicated that the optimum pH for metal binding is approximately 5.0. Time dependency experiments for all the metals studied showed that metal binding to the African alfalfa shoots occurred within 5 min. Binding capacity experiments revealed the following amounts of metal ions bound per gram of biomass: 7.1 mg Cd(II), 7.7 mg Cr(III), 43 mg Pb(II), and 4.9 mg Zn(II). However, no binding occurred for chromium(VI). Nearly all of the metals studied were recoverable by treatment with 0.1 M HCl. Column experiments were performed to study the binding of Cd(II), Cr(III), Cr(VI), Pb(II) and Zn(II) to silica-immobilized African alfalfa shoots under flow conditions. These experiments showed that the silica immobilized African alfalfa shoots were effective for removing metal ions from solution, and over 90% of the bound Pb(II), Cu(II), Ni(II), and Zn(II), and over 70%Cd(II), were recovered after treatment with 10 bed volumes of 0.1 M HCl. The results from these studies will be useful for a novel phytofiltration technology to remove and recover heavy metal ions from aqueous solution.

Gold nanoparticles obtained by bio-precipitation from gold(III) solutions

The use of metal nanoparticles has shown to be very important in recent industrial applications. Currently gold nanoparticles are being produced by physical methods such as evaporation. Biological processes may be an alternative to physical methods for the production of gold nanoparticles. Alfalfa biomass has shown to be effective at passively binding and reducing gold from solutions containing gold(III) ions and resulting in the formation of gold(0) nanoparticles. High resolution microscopy has shown that five different types of gold particles are present after reaction with gold(III) ions with alfalfa biomass. These particles include: fcc tetrahedral, hexagonal platelet, icosahedral multiple twinned, decahedral multiple twinned, and irregular shaped particles. Further analysis on the frequency of distribution has shown that icosahedral and irregular particles are more frequently formed. In addition, the larger particles observed may be formed through the coalescence of smaller particles. Through modification of the chemical parameters, more uniform particle size distribution may be obtained by the alfalfa bio-reduction of gold(III) from solution.

Use of X-ray absorption spectroscopy and esterification to investigate Cr(III) and Ni(II) ligands in alfalfa biomass

Previously performed studies have shown that alfalfa shoot biomass can bind an appreciable amount of nickel(II) and chromium(III) ions from aqueous solution. Direct and indirect approaches were applied to study the possible mechanis ms involved in metal binding by the alfalfa biomass. The direct approach involves investigations of the metal-bound alfal fa shoot biomass by X-ray absorption spectroscopic analysis (XANES and EXAFS). Results from these studies suggest that ni ckel(II) and chromium(III) binding mostly occurs through coordination with oxygen ligands. Indirect approaches consist of chemical modification of carboxylate groups that have been shown to play an important role in metal binding to the alfal fa biomass. An appreciable decrease in metal binding resulted after acidic methanol esterification of the biomass, indica ting that carboxyl groups are entailed in the metal binding by the alfalfa biomass. In addition, base hydrolysis of the a lfalfa biomass increased the binding of these metals, which further indicates that carboxyl groups play an important role in the binding of these metal ions from solution. Therefore, by combining two different techniques, our results indicate that carboxylate groups are the major ligands responsible for the binding of nickel(II) and chromium(III) by alfalfa bio mass.

Spectroscopic and electrical studies of a solution-cathode glow discharge

A glow discharge using a solution as the cathode was investigated to add to the understanding of the operating mechanism and characteristics of such systems. The intensities and vertical distributions of emission from several analytes and background species were observed and compared with the vertical distribution of Fe excitation and OH rotational temperatures, as well as to electrical characteristics. The effects of the discharge gap size, the pH and conductivity of the solution, the applied current and the solution flow rate on these distributions were also studied. Detection limits for this system were found to be comparable to those of similar systems and mostly in range of tens of parts per billion.

A new, versatile, direct-current helium atmospheric-pressure glow discharge

A novel direct current glow discharge sustained in helium at atmospheric pressure has been developed. Current–voltage behavior and spectroscopic characteristics strongly suggest that the system operates in the glow regime, in spite of the high pressure. The diffuse and extremely stable discharge is typically operated within a voltage range of 300–900 volts (in the current-controlled mode) and at currents ranging over tens to hundreds of milliamps. Spatially resolved spectroscopic measurements of some selected species are presented. Rotational temperature profiles were calculated using the OH emission spectrum, yielding values in the positive column ranging from 1300 to 1600 K.

Real‐time, on‐line monitoring of organic chemical reactions using extractive electrospray ionization tandem mass spectrometry

Extractive electrospray ionization mass spectrometry (EESI-MS) for real-time monitoring of organic chemical reactions was demonstrated for a well-established pharmaceutical process reaction and a widely used acetylation reaction in the presence of a nucleophilic catalyst, 4-dimethylaminopyridine (4-DMAP). EESI-MS provides real-time information that allows us to determine the optimum time for terminating the reaction based on the relative intensities of the precursors and products. In addition, tandem mass spectrometric (MS/MS) analysis via EESI-MS permits on-line validation of proposed reaction intermediates. The simplicity and rapid response of EESI-MS make it a valuable technique for on-line characterization and full control of chemical and pharmaceutical reactions, resulting in maximized product yield and minimized environmental costs.