ICP-MS

Gas chromatography and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC–TOFMS and GCxGC–TOFMS) were utilized to develop trace-level calibration curves in brewed green tea spiked with organochlorine and organophosphorus pesticide standards. A sensitive and robust calibration curve was developed from 10 to 500 parts per trillion (ppt), which allowed quantitative results to be determined for organochlorine–organophosphorus pesticides in brewed green tea. Exceptional limits of detection were achieved by GC–TOFMS and GCxGC–TOFMS at or below 10 ppt (solution concentration) for all but one of the pesticides. Stir bar sorption extraction (SBSE) was utilized to isolate the pesticide components from brewed green tea samples prior to analysis by GC–TOFMS and GCxGC–TOFMS. Different types of green tea were analyzed qualitatively by SBSE and GC–TOFMS with subsequent quantification for organochlorine–organophosphorus..

Beta-blockers are basic compounds that contain a secondary amino group in their structure. The amino substituents are typically an isopropyl group and a larger chain with a hydroxyl group in the beta position from the nitrogen atom (Table I). The simultaneous analysis of ?-blockers in biological samples is meaningful, and is made possible by the similarities in their structure. Gas chromatography (GC)–mass spectrometry (MS) has been the most used technique for their identification and quantification (4–6). However, most ?-blockers are nonvolatile and thus require derivatization via a cumbersome and time-consuming process before GC–MS analysis. In recent years, liquid chromatography (LC) coupled with mass spectrometric detection has evolved as the method of choice for drug analysis in the pharmaceutical, clinical, and forensic toxicology areas (4–8). In contrast to GC–MS, LC–MS-MS generally does not require derivatization and offers superior sensitivity. Moreover, due to the high specificity offered by LC–MS-MS, baseline chromatographic resolution often is not required, allowing for fast analysis in high-throughput environments.

The nanoLC LIT-TOF approach combines multiple capabilities that improve the ability to characterize complex protein mixtures significantly.

The usefulness of liquid chromatography–mass spectrometry–mass spectrometry (LC–MS-MS) methods for the unambiguous identification and quantification of pesticides in complex matrix samples is well known. Triple-quadrupole systems have proven to be useful for this task because of their high specificity in MS-MS mode and their low detection limits. However, working in MS-MS mode makes any MS system blind to other compounds of interest.

Because it is extremely rapid, biomarker discovery and identification using liquid chromatography–mass spectrometry (LC-MS), including both ion-trap and triple-quadrupole LC–MS, is well established. Fractionation of complex samples before LC–MS-MS analysis might be necessary to identify the proteins, greatly increasing the number of analyses required. In this case, there is ongoing debate regarding knowing whether the protein is identified correctly, knowing how much prior fractionation is needed to reduce complexity to the point where low-abundance proteins can be detected reliably, and balancing specificity with sensitivity.

Although not currently used in U.S. or European aquaculture, malachite green (MG) is still an effective and inexpensive fungicide that is used in other countries, particularly in Asia. During metabolism, MG reduces to leucomalachite green (LMG) (Figure 1), which has been shown to accumulate in fatty fish tissues. Trace levels of MG and LMG residues continue to be found in fish products. In a 2005 report, MG was found in 18 out of 27 live eel or eel products imported from China to Hong Kong local market and food outlets, resulting in a government recall and destruction of all remaining products (1).

The implementation of ICP-MS as a detection system for reversed-phase HPLC was proven to be a useful technique for the investigation of pharmaceutical molecules containing the heteroatoms sulfur, phosphorus, bromine, and chlorine, as well as organometallic compounds containing a transition metal such as cobalt.

Inductively coupled plasma (ICP) spectroscopy is an important optical emission technique, with strong applications in environmental testing and related areas. The basic principle of ICP involves the introduction of a liquid sample into an argon plasma torch, which provides the excitation energy required to stimulate atomic emission in the sample. The geometry of the torch with respect to the optical components provides one source of control over the analysis. The axial mode, with the optics directed toward the plasma jet, provides better detection levels, although the radial (side-on) mode generally is less problematic.

In this month's installment, columnist Ken Busch addresses the molecular applications of inductively coupled plasma linked with mass spectrometry (ICP-MS), and how those applications have developed.

Mass spectrometry has become a fundamental tool for compound identification or confirmation by virtue of its ability to obtain elemental composition determination (formula identification) by accurate mass measurements. The speed, sensitivity, and ease of interfacing the technique with gas chromatography and liquid chromatography make it the technique of choice for many applications. However, accurate mass measurements must be made with care, and sometimes they can require careful calibration procedures and validation methods. In addition to accurate mass measurements, the isotope abundance distribution also provides information unique to a given chemical formula. However, the mass spectral accuracy required for accurate isotope modeling has not been easy to obtain previously. More recent approaches (1–3) that calibrate the spectral line-shape show promise in obtaining the necessary level of spectral accuracy but still require careful calibration methods with the use of known standards. This article..

Today's ion traps use advanced scanning techniques such as automatic gain control, axial modulation, and triple resonance scanning, resulting in efficient control of both ionization and optimal storage of ions in the trap during analysis. These instruments provide excellent sensitivity and quantitative data, even in "dirty" samples.

Root diseases caused by soilborne plant pathogens are responsible for billions of dollars of losses annually in food, fiber, ornamental, and biofuel crops. The use of pesticides often is not an option to control plant diseases because of economic factors or potential adverse effects on the environment or human health. For this reason, many Americans are now buying pesticide-free organic foods. Organic agriculture has few options for controlling pests and thus must make full use of natural microbial biological control agents in soils that suppress diseases.

Mass spectrometry (MS) has advanced to analyze ever-larger biomolecules with the invention of soft ionization techniques like electrospray ionization (ESI). Although ESI has provided a method of generating ions of high mass, mass spectrometers generally suffer both lower sensitivity and lower resolution as the mass-to-charge ratio of an ion increases. To extend the mass range of ionized macromolecules beyond the limits of MS, macroion mobility spectrometry utilizes ion mobility sizing to characterize charge-reduced ESI-generated macroions from >5 kDa to beyond megadalton masses. One prominent application of macroion mobility spectrometry, highlighted here, is the high sensitivity analysis of intact proteins, antibodies, and conjugates in which molecular masses range from antibody light-chain fragments to high mass immunoglobulin multimers.

Drug discovery scientists are continually striving to improve productivity and efficiency in their workflows. From early discovery to clinical development, existing workflow bottlenecks represent an opportunity to develop solutions to speed the process and improve productivity. The key requirements for quantitative analysis are precision, accuracy, and linear dynamic range. With any quantitative instrument, the hope is that it will be applicable to a vast range of coumpounds, ruggest, and fast. New mass spectrometry (MS) technologies are being developed that meet these criteria and permit high throughput while enabling its application to areas in which speed limitations previously curtailed its practicality. In particular, in the area of ADME profiling, new MS platforms are becoming available that increase the throughput by at least 25-fold, by combining the speed of matrix-assisted laser desorption ionization (MALDI) with the specificity of triple-quadrupole MS. This is bound to greatly accelerate the ADME..

This article describes a fully automated online solid-phase extraction–liquid chromatography–tandem mass spectrometry (SPE–LC–MS-MS) setup using a mass spectrometer and an electrospray ionization probe for analyzing different groups of polar contaminants in natural waters. The goal was to develop an online SPE method for the quantification of sulfonamide antibiotics, including their acetyl metabolites, as well as for frequently used pesticides (triketones, phenylureas, chloracetanilides, phenoxyacetic acids, amides, and triazines) in ambient waters. The analytical methods were applied successfully for a field study in an agricultural region within the catchment area of Lake Greifensee near Zurich, Switzerland.

Multiline analysis, which consists of using several lines per element to detect positive or negative bias caused by spectral interferences, is an ideal way to use all the information emitted by the plasma and collected by a charge-coupled device detector. However, method development and validation become more complex. Dedicated software has been developed to overcome it, and analysis of geological samples will illustrate their benefit in achieving high reliability of results.

The multielement analysis of water is one of the major applications for inductively coupled plasma-optical emission spectroscopy (ICP-OES). This report describes the analysis of metals and trace elements in drinking water in terms of sensitivity, precision, and accuracy. Instrument parameters and line selection are described. Excellent recoveries were found for the standard reference material (SRM) NIST SRM 1640.

Two of the most significant areas of advancement in inductively coupled plasma-mass spectrometry (ICP-MS) with respect to clinical applications have been the evolution of the sample introduction system and the interface of liquid chromatography (LC). The complexity of the sample matrix creates challenges for a number of components involved with the introduction of ions into the mass spectrometer, including the nebulizer, spray chamber, torch, and interface cones. The development of LC-ICP-MS methods enables analysts to quantitate not only the total metal content but the form of the metal as well, a distinction that in many cases is crucial. Although the refinement of reaction and collision cell technology has been important for this application, much has been written elsewhere and it will not be addressed here.

Bottled water has become increasingly popular over the past several years for convenience and safety. In some areas where publicly supplied tap water is contaminated or contains bacteria, this assumption is valid. However, in areas with clean tap water, the presence of bottled water can be controversial because it might be less clean than the local tap. This article discusses the analysis of inorganic contaminants in bottled water, including regulated contaminants and bromate. Detection limit considerations and speed of analysis also are discussed.

One of the promises of array detector inductively coupled plasma (ICP) systems has been the ability to measure all elements in an unknown sample. Sometimes referred to as elemental fingerprinting, this capability can be extremely powerful for quality control (QC) and forensic applications. To take advantage of this capability, the ICP system employed must provide full wavelength coverage as well as the spectral data handling tools needed to do the "fingerprinting." This article will demonstrate some of the elemental fingerprinting capabilities of ICP.

The spectrometric techniques of inductively coupled plasma–optical emission spectrometry (ICP-OES) and inductively coupled plasma–mass spectrometry (ICP-MS) are compared for their applicability to regulatory water analyses, bearing in mind recent method approval changes. ICP-OES is found to be at its limit for confident detection of several elements for drinking water analysis, but is still suitable for many environmental water quality measurements. ICP-MS is the closest there is to a universally applicable technique for water analysis.

Assay sensitivity is the lowest concentration at which a targeted analyte can be measured and is often limited by chemical background or co-eluting interferences. FAIMS in combination with liquid chromatography (LC) and zero neutral loss tandem MS was used to remove chemical background and co-eluting interferences from the analysis of linoleic acid in cancer cell extracts. Concentration of endogenous linoleic acid was determined from back-calculation of standard calibration samples fortified with deuterium-labeled linoleic acid. No internal standard was used. LC–MS-MS analysis of the cancer cell extracts resulted in an increase in signal-to-noise ratio of 10-fold. The assay sensitivity was increased 10 times over the traditional LC–MS-MS experiment exclusively due to the new FAIMS technology.

More than 20 years passed after the introduction of Fourier transform–ion cyclotron resonance mass spectrometry (FT-MS) before advancements in electronics and computer technology enabled the development of practical, high-performance instruments. Modern analytical FT-MS instruments rely on sophisticated electronic circuitry and powerful computer software to achieve the dramatic resolving power and mass accuracy typical for the instrumentation. Here, the power of modern hybrid FT-MS instrumentation is discussed by demonstrating the capability of this instrumentation for selected applications such as the analysis of crude oil, intact protein, and fragile noncovalent complex samples.

Here we describe a new compact device for electron-capture dissociation (ECD) analysis of large peptides and posttranslational modifications of proteins, which can be difficult to analyze via conventional dissociation techniques such as collision-induced dissociation (CID). The new compact device realizes ECD in a radio frequency (RF) linear ion trap equipped with a small permanent magnet, which is significantly different than the large and maintenance-intensive superconducting magnet required for conventional ECD in Fourier-transform ion cyclotron resonance mass spectrometers. In addition to its compactness and ease of operation, an additional merit of an RF linear ion trap ECD is that its reaction speed is fast, comparable to CID, enabling data acquisition on the liquid-chromatography (LC) time scale. We interfaced the linear-trap ECD device to a time-of-flight mass spectrometer to obtain ECD spectra of phosphorylated peptides injected into a liquid chromatograph, infused glycopeptides, and intact small..

Metabolomics is a developing analytical approach that is growing rapidly in importance as a tool to improve diagnosis and treatment of disease, as well as to speed up the drug development process. Unlike genomics or proteomics, which only reveal part of what might be happening in a cell, metabolomic profiling can give an instantaneous snapshot of the entire physiology of that cell. This article describes the challenges associated with metabolomics research and new tools developed to overcome them.

The increased resolving power provided by comprehensive two-dimensional gas chromatography (GCxGC) extends the chromatographer's ability to rapidly detect and measure smaller components in complex mixtures beyond that which was possible previously, allowing for the identification of hazardous components in complex mixtures such as foodstuffs or emergency response samples. In target analysis, the increased numbers of peaks resulting from the sample matrix can be largely ignored during the review of data. However, when the nature of the analyte of interest is not entirely known, analysis of the samples might require screening through the entire peak table for compounds with specific chemical characteristics. For example, in the analysis of foodstuffs for pesticides (1,2), GCxGC coupled with a time-of-flight mass spectrometry (GCxGC–TOF-MS) can provide low detection limits for multiple analytes in these complex samples. Yet the question remains as to whether other toxic compounds, not included in the..

Reproducing analysis conditions is crucial to achieving consistent, accurate results in gas chromatography–mass spectrometry (GC–MS). Valid reproduction demands appropriate application of technique, solid method design, reliable and accurate equipment, and a dedicated team of well-practiced technicians and researchers. But even when all these conditions are met, users can be held back by the more subtle elements in GC–MS operations, such as cutting or changing a column, or setting up the same experiment on different equipment. Even getting the parameters of a test organized so that it can be reproduced elsewhere - in a laboratory across the hall, the country, or the world - can be daunting. Consistent GC–MS results depend upon retention-time reproducibility.