Mass Spectrometry,Review of the Basics: Ionization

Abstract: Mass spectrometry (MS) has become an integral tool in life sciences. The first step in MS analysis is ion formation (ionization). Many ionization methods currently exist; electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) are the most commonly used. ESI relies on the formation of charged droplets releasing ions from the surface (ion evaporation model) or via complete solvent evaporation (charge residual model). MALDI ionization, however, is facilitated via laser energy and the use of a matrix. Despite wide use, ESI cannot efficiently ionize nonpolar compounds. Atmospheric pressure chemical ionization (APCI) and atmospheric pressure photo ionization (APPI) are better suited for such tasks. APPI requires photon energy and a dopant, whereas APCI is similar to chemical ionization. In 2004, ambient MS was introduced in which ionization occurs at the sample in its native form. Desorption electrospray ionization (DESI) and direct analysis in real time (DART) are the most widely used methods. In this mini-review, we provide an overview of the main ionization methods and the mechanisms of ion formation. This article is educational and intended for students/researchers who are not very familiar with MS and would like to learn the basics; it is not for MS experts.     

Dry Ashing Preparation of (Quasi)solid Samples for the Determination of Inorganic Elements by Atomic/Mass Spectrometry

Abstract:

This work presents an overview of the development of dry ashing preparation techniques for solid and quasisolid sample analysis by atomic and inorganic mass spectrometry, including flame/graphite furnace atomic absorption spectrometry, chemical vapor generation atomic absorption/fluorescence spectrometry, and inductively coupled plasma–optical emission/mass spectrometry. This article also summarizes all of the dry ashing methods reported in the past 20 years. The dry ashing methods applied to sample preparation are classified as electrothermal ashing, microwave ashing, oxygen combustion, and other special ashing methods including laser, ultraviolet (UV)/ozone, and plasma. Moreover, the development of relevant devices is discussed in context.     

Inverse problems of magnetostatics and the design of double-focusing electron magnetic spectrometers

A method is proposed for the design of double-focusing electron magnetic spectrometers by using direct methods of solving inverse problems of magnetostatics. The conditions for double-focusing electron magnetic spectrometers in a system with two pairs of electromagnetic coils are determined for the first time in a third-order model, which appreciably improves the main optical characteristics of the device: the resolution and the luminosity. This system is used to design a real energy analyzer with a free toric chamber in the third-order model. Zh. Tekh. Fiz. 67, 66–69 (November 1997)     

Experimental determination of the dynamical properties of molecular crystals under pressure

Abstract

A main characteristic of molecular solids is the large difference between intra- and intermolecular interactions. This difference is reflected in the physical properties, especially in the dynamical properties and their pressure dependence. The three main techniques used to study the dynamical properties of crystals in diamond cells are reviewed, and each one is illustrated by an example which shows specific properties of molecular crystals.     

Determination of Heavy Metal Accumulation in Plant Samples by Spectrometric Techniques in Turkey

Abstract:

Heavy metals are significant and extremely persistent environmental pollutants and their toxicity is a problem of increasing significance for ecological, nutritional, and environmental reasons. Biomonitoring methods are gaining more importance because they allow for prediction, detection, and control of potential environmental hazards caused by heavy metal pollution. The objective of the present study was to collect and analyze research on heavy metal accumulation in plant samples using spectrometric detection techniques in Turkey published between 2003 and 2013. Five main criteria were predetermined to limit the study and better portray the studies on heavy metal accumulation using plant samples in Turkey. These criteria were as follows: studies aiming to determine heavy metal accumulation levels, studies sampling plant species growing at various localities in Turkey, studies using spectrometric detection techniques, studies published as journal articles, and studies undertaken between 2003 and 2013. Consequently, 47 studies that satisfied all criteria were considered and selected for this investigation. A content analysis method was used for the review and analysis of the selected studies. The results of the review analysis were grouped under three categories and the findings obtained in this scope were presented.     

Fluorimetric Determination of Morphine in Codeine

Abstract

Two easy to handle, sensitive and specific fluorimetric methods for the detection and determination of morphine in codeine are described. In method A the codeine sample investigated is treated with alkaline potassium ferricyanide, whereby morphine when present will produce the fluorescent dimer pseudomorphine. In method B, the codeine sample is thermally treated with gaseous ammonia on a chromatographic plate where morphine, if present, is converted to a highly fluorescent derivative. The limits of detection were 10 ng and 20 ng for methods A and B respectively.     

Chemical Vapor Generation with Slurry Sampling: A Review of Applications to Atomic and Mass Spectrometry

Abstract

A critical review of published analytical methods and techniques for chemical vapor generation (CVG) with slurry sample introduction for detection by atomic and mass spectrometry is presented. The nstrumentation used for the reaction as well as separation and transport of the species, influence of chemical and physical factors, and efficiency of the process are considered. A brief comparison of detection limits obtained with atomic absorption, emission, and fluorescence as well as mass spectrometry along with practical applications to analytical samples are summarized. The current state-of-the-art, including advantages and limitations of this approach, is discussed.     

Relaxation of a hard-sphere gas and criteria of validity of the calculations

The isotropic Boltzmann equation is solved using the Sonin moment system of equations. The main task here is the construction of a matrix describing the particle interaction. Such a matrix has been constructed analytically for various interaction cross sections in a number of papers [M. Barnsley and G. Turchetti, Lett. Nuovo Cimento 33, 347 (1982); G. Turchetti and M. Paolilli, Phys. Lett. A 90, 123 (1982); F. Schürrer and G. Kügerl, Phys. Fluids A 2, 609 (1990); A. Ya. énder and I. A. énder, Tech. Phys. 39, 997 (1994)]. Calculations of matrix elements arrived at by different methods for the hard-sphere model are compared. Some general properties of the matrix are found that can be used as criteria of the validity of the calculations. With the help of such criteria it is shown that the nonlinear matrix elements were calculated incorrectly by Schürrer and Kügerl (op. cit.). Zh. Tekh. Fiz. 68, 18–26 (May 1998)     

Preparation of Bone Samples in the Gliwice Radiocarbon Laboratory for AMS Radiocarbon Dating

Abstract

In the Gliwice Radiocarbon Laboratory, a system for preparation of samples for AMS dating has been built. At first it was used to produce graphite targets from plant macrofossils and sediments. In this study we extended its capabilities with the preparation of bones. We dealt with 3 methods; the first was the classical Longin method of collagen extraction, the second one included additional treatment of powdered bone in alkali solution, while in the third one carboxyl carbon was separated from amino acids obtained after hydrolysis of protein. The suitability of the methods was tested on 2 bone samples. Most of our samples gave ages >40kyr BP, suggesting good performance of the adapted methods, except for one sample prepared with simple Longin method. For routine preparation of bones we chose the Longin method with additional alkali treatment.     

Characterization of Greenhouse Soil Properties Using Mid-infrared Photoacoustic Spectroscopy

ABSTRACT

Evaluation of soil fertility is required for the sustainable production in greenhouses; however, routine agrochemical analytical methods are not practical since most of them are too time consuming and costly. In this study, Fourier transform midinfrared photoacoustic spectroscopy (FTIR-PAS) was applied as an alternative technique in the fast characterization of greenhouse soils. Nine source clays and 235 soil samples were obtained from different greenhouses in China, and their counterpart open-field soils were also sampled for comparison. The FTIR-PAS spectra of soil clays and soils were recorded with the wave-number range of 600–4000 cm^?1, and clear differences were observed among the spectra; soil organic matter (SOM) and soil clay played the main role in the spectral absorption. Partial least square regression (PLSR) models coupled to optimized spectral pretreatment were used to predict greenhouse soil properties, and FTIR-PAS spectra were closely related to SOM (R² = 0.94) and soil total nitrogen (R² = 0.90). For the other soil properties—such as pH, EC, water extractable P, K, Fe, and Cu—the calibration results were excellent or acceptable. These results suggested that FTIR-PAS could be used to determine most of greenhouse soil properties. Since the technique of FTIR-PAS is rapid and inexpensive, and it requires no sample pretreatment and little sample mass, it can be used in fast characterization of greenhouse soil and is a promising method for the management of greenhouse soil.     

New Experimental Data for the Validation of Radiative Heat Transfer

The numerical simulation of radiative heat transfer is now well established. Key ingredients in such a simulation model are calculated view factors that are used to describe the exchange of radiated energy between different surfaces. Several methods for the calculation of these geometrical factors are available, including Integration, Monte Carlo, and the Hemi-cube methods. Several analytical test cases are also available, such as the well-known “parallel plates” case, which allow modelers to validate their view factor routines. However, there is much less information available that combines both view factor information and heat transfer effects simultaneously.

This article describes the construction of a simple testing rig that allows experiments to be performed that combine view factor effects with measured heat transfer exchanged between surfaces only. The equipment has been used to consider simple cases, such as the parallel plates test case, and also cases where shadowing is important. The results of these experiments are presented as experimental benchmarking data for model users and developers.     

Vibrational Spectrometry Strategies for Quality Control of Procymidone in Pesticide Formulations

Abstract

Two vibrational spectrometry–based methodologies were developed for procymidone determination in wettable powdered pesticide formulations. The Fourier‐transform infrared (FTIR) procedure was based on the selective extraction of procymidone by chloroform and determination by peak area measurement between 1451 and 1441 cm^?1, using a baseline correction established between 1490 and 1410 cm^?1, and a precision of 0.4% and a limit of detection of 0.01% w/w procymidone for a sample mass of 25 mg were obtained. For FT‐Raman determination, the selected conditions were peak area measurement between 1005 and 995 cm^?1 Raman shift, with a baseline correction fixed between 1030 and 947 cm^?1, and a relative standard deviation of 1% and a limit of detection of 0.8% procymidone in the original sample were obtained. The sample frequency for FTIR determination was 30 hr^?1, lower than that for Raman with 40 hr^?1. FT‐Raman reduces to the minimum the reagent consumption and waste generation, also avoiding the sample handling and contact of the operator with the pesticide. It can be concluded that the proposed methods are appropriate for quality control in commercial pesticide formulations.     

Calculations of the EPR g-tensor using unrestricted two- and four-component relativistic approaches within the HF and DFT frameworks

ABSTRACT

Approaches and programs for calculations of the EPR g-tensor in the framework of the two- and four-component methods are still very rare. There are three main reasons for this: the wider community's unawareness of the importance of second- and higher order spin–orbit effects on the g-tensor, the methodological problems associated with performing such calculations and the lack of understanding of these problems. This paper reports on the implementation of a method for calculation of the g-tensor in the framework of the relativistic unrestricted two- and four-component Hartree–Fock and density functional theory approaches based on the Kramers pair formalism. This implementation allows us to analyse problems which arise when the g-tensor is calculated via Kramers pairs in the unrestricted framework.     

Advances in Electrothermal Atomization Atomic Absorption Spectrometry: Instrumentation,Methods, and Applications

Abstract

Electrothermal atomization (ETA) atomic absorption spectrometry (AAS) offers high sensitivity quantitative analysis of a wide variety of samples for metals. Following an introduction to this instrumental method, recent developments in instrumentation, methods of sample preparation, and significant applications are reviewed, illustrating significant developments. The focus of this review is on the practical application of ETA‐AAS for real sample analysis.     

Magnetic properties of an amorphous microconductor in the microwave range

The frequency dispersion of the magnetic permeability is taken into account in a calculation of the impedance of an amorphous microconductor. Possible methods of measuring the magnetic parameters are analyzed, and the main characteristics of an amorphous microconductor in the microwave range are described. Zh. Tekh. Fiz. 68, 136–137 (January 1998)     

Determination of Mycotoxins in Food: A Review of Bioanalytical to Analytical Methods

Abstract

This review highlights methods for the detection of the main mycotoxins: aflatoxins, fumonisins, ochratoxin, patulin, trichothecene, zearalenone, citrinin. Detection methods such as competitive or noncompetitive immunoassays, different biosensors, and the use of optoelectronics devices to miniaturize the equipment in a portable way, are described. The importance of spectroscopic techniques are underlined and the maxima permissible by various committees are indicated.     

Field camera versus phantom-based measurement of the gradient system transfer function (GSTF) with dwell time compensation

PurposeThe gradient system transfer function (GSTF) can be used to describe the dynamic gradient system and applied for trajectory correction in non-Cartesian MRI. This study compares the field camera and the phantom-based methods to measure the GSTF and implements a compensation for the difference in measurement dwell time.MethodsThe self-term GSTFs of a MR system were determined with two approaches: 1) using a dynamic field camera and 2) using a spherical phantom-based measurement with standard MR hardware. The phantom-based GSTF was convolved with a box function to compensate for the dwell time dependence of the measurement. The field camera and phantom-based GSTFs were used for trajectory prediction during retrospective image reconstruction of 3D wave-CAIPI phantom images.ResultsDifferences in the GSTF magnitude response were observed between the two measurement methods. For the wave-CAIPI sequence, this led to deviations in the GSTF predicted trajectories of 4% compared to measured trajectories, and residual distortions in the reconstructed phantom images generated with the phantom-based GSTF. Following dwell-time compensation, deviations in the GSTF magnitudes, GSTF-predicted trajectories, and resulting image artifacts were eliminated (< 0.5% deviation in trajectories).ConclusionWith dwell time compensation, both the field camera and the phantom-based GSTF self-terms show negligible deviations and lead to strong artifact reduction when they are used for trajectory correction in image reconstruction.     

Monte Carlo Calculations of XRF Intensities in Annular Arrangements of Radioactive Source,Sample, Cylindrical Collimator and Detector

ABSTRACT

A Monte Carlo (MC) computer program for the calculation of the distribution of characteristic X-ray intensities as a function of the counting geometry is described. The program evaluates the contribution to the intensities of a fluorescent line from each point of the source, sample and detector. The main considerations of the calculation are based on the critical nature of the internal geometry of the main analyzer components within an energy dispersive X-ray fluorescence (EDXRF) spectrometer. The K XRF intensities for the inner and outer radius of the annular-sample and collimator radius were measured. An optimum geometry can be obtained by varying the collimator radius and the detector-sample distance. The results of the calculations show that the intensity distribution of the radioisotope excited fluorescent radiation through annular sample area is strongly dependent on the collimator radius, with a maximum intensity effect with a smaller sample area and with decreasing collimator radius. An investigation of the XRF intensities in the annular sample surface as a function of collimator radius is discussed.     

Determination of Trace Elements in Vegetable Oils and Biodiesel by Atomic Spectrometric Techniques—A Review

Abstract

The determination of trace elements in edible oils and biodiesel using atomic spectrometric methods is reviewed. Problems related to sample pretreatment for appropriate sample introduction and calibration are addressed as well as the strategies to overcome them. Recent trends aimed at simplifying sample manipulation are presented. The applications and scope of atomic absorption spectrometry (AAS), flame optical emission spectrometry (F-OES), inductively coupled plasma–optical emission spectrometry (ICP-OES), and inductively coupled plasma–mass spectrometry (ICP-MS) techniques for the determination of trace metals in edible oils and biodiesel are discussed, as well as some current instrumental new developments.     

Automated measurement of fat infiltration in the hip abductors from Dixon magnetic resonance imaging

PurposeIntramuscular fat infiltration is a dynamic process, in response to exercise and muscle health, which can be quantified by estimating fat fraction (FF) from Dixon MRI. Healthy hip abductor muscles are a good indicator of a healthy hip and an active lifestyle as they have a fundamental role in walking. The automated measurement of the abductors' FF requires the challenging task of segmenting them. We aimed to design, develop and evaluate a multi-atlas based method for automated measurement of fat fraction in the main hip abductor muscles: gluteus maximus (GMAX), gluteus medius (GMED), gluteus minimus (GMIN) and tensor fasciae latae (TFL).MethodWe collected and manually segmented Dixon MR images of 10 healthy individuals and 7 patients who underwent MRI for hip problems. Twelve of them were selected to build an atlas library used to implement the automated multi-atlas segmentation method. We compared the FF in the hip abductor muscles for the automated and manual segmentations for both healthy and patients groups. Measures of average and spread were reported for FF for both methods. We used the root mean square error (RMSE) to quantify the method accuracy. A linear regression model was used to explain the relationship between FF for automated and manual segmentations.ResultsThe automated median (IQR) FF was 20.0(16.0–26.4) %, 14.3(10.9–16.5) %, 15.5(13.9–18.6) % and 16.2(13.5–25.6) % for GMAX, GMED, GMIN and TFL respectively, with a FF RMSE of 1.6%, 0.8%, 2.1%, 2.7%. A strong linear correlation (R² = 0.93, p < .001, m = 0.99) was found between the FF from automated and manual segmentations. The mean FF was higher in patients than in healthy subjects.ConclusionThe automated measurement of FF of hip abductor muscles from Dixon MRI had good agreement with FF measurements from manually segmented images. The method was accurate for both healthy and patients groups.