Recent Developments in Ion Mobility Spectrometry

Abstract

The general principles and technical implementations of traditional time-of-flight ion mobility spectrometers and analyzers with field-dependent mobilities were reviewed in our last article in this journal. Recent advances in instrumentation and new applications since 2006 are highlighted in this review. In addition to traditional applications as military chemical-agent detectors, ion mobility techniques have become popular for different purposes. Though ion mobility spectrometry was solely used as vapor sensor in the past decades, further developments in ionization techniques (especially electrospray ionization) now permit its routine use for the analysis of liquid samples. The coupling of ion mobility spectrometry with selective sample preparation techniques such as molecular-imprinted polymers, coupling with chromatographic techniques, the use of dopants, and application of selective ionization sources has led to an expanded number of applications in industrial and environmental analysis with complex sample matrices due to an improved selectivity in comparison with traditional stand-alone spectrometers. Furthermore, new developments in hyphenated techniques, especially ion mobility–mass spectrometry couplings, has resulted in an increased number of new applications for the analysis of biomolecules and pharmaceutical samples and in clinical diagnostics.     

A comparison and evaluation of reduced-FOV methods for multi-slice 7 T human imaging

Eight different reduced field-of-view (FOV) MRI techniques suitable for high field human imaging were implemented, optimized, and evaluated at 7 T. These included selective Inner-Volume Imaging (IVI) based methods, and Outer-Volume Suppression (OVS) techniques, some of which were previously unexplored at ultra-high fields. Design considerations included use of selective composite excitation and adiabatic refocusing radio-frequency (RF) pulses to address B1 inhomogeneities, twice-refocused spin echo techniques, frequency-modulated pulses to sharply define suppressed regions, and pulse sequence designs to improve SNR in multi-slice scans. The different methods were quantitatively compared in phantoms and in vivo human brain images to provide measurements of relative signal to noise ratio (SNR), power deposition (specific absorption rate, SAR), suppression of signal, artifact strength and prevalence, and general image quality. Multi-slice signal losses in out-of-slice locations were simulated for IVI methods, and then measured experimentally across a range of slice numbers. Corrections for B1 nonuniformities demonstrated an improved SNR and a reduction in artifact power in the reduced-FOV, but produced an elevated SAR. Multi-slice sequences with reordering of pulses in traditional and twice-refocused IVI techniques demonstrated an improved SNR compared to conventional methods. The combined results provide a basis for use of reduced-FOV techniques for human imaging localized to a small FOV at 7 T.     

Dynamical fermions in lattice gauge theories: Metropolis and Langevin techniques in two dimensions

A variety of techniques for the inclusion of dynamical fermions in lattice gauge theory is examined. Three pseudo-fermionic techniques that have the characteristics desirable for an unquenched simulation of four-dimensional QCD are studied in detail. Langevin and Metropolis pseudo-fermionic techniques are implemented for a 64×64 lattice on the Distributed Array Processor and their relative merits examined both for free fermions and the lattice Schwinger model.     

Comparative study between interferometric and Z-scan techniques for thermal lensing characterization

This work presents an original, comparative study between two optical techniques for the analysis of thermal lensing induced by a low-power, cw laser beam focused onto a sample cell containing a weak absorbing medium. It deals with an interferometric technique and a Z-scan technique in real time. The interferometric method permits the determination of the spatial profile of the thermal lens. The development of the work puts in evidence the high sensitivity of both techniques for the detection and measurement of low absorption coefficients and refractive index changes in dye solutions at very low concentrations. Improvements in the sensitivity of both methods can make possible the measurement of very small phase shift distortions of the wavefront. One shows also the mutual complementary character of two techniques for the characterization and measurement of linear and nonlinear properties of materials.     

High-sensitivity transient spectroscopy using tunable diode lasers

Experimental techniques have been developed to monitor transient infrared absorptions using lead-salt tunable diode lasers. The techniques are easily implemented, yield sensitivities which are limited by detector noise at 10^–5 level of absorbance, and have a response time on the order of one microsecond. The transient absorption detection techniques are high frequency versions of the sweep integration technique pioneered by Jennings [Appl. Opt.19, 2695 (1980)]. TDL modulation rates of 100 kHz and 500 kHz allow for absorption sampling rates of 200 kHz and 1 MHz, respectively. In order to reproducibly achieve near-detector-noise-limited sensitivities for 100 kHz TDL modulation rates, an automated analog subtraction circuit has been developed which removes the effects of minor TDL power variations. At the 500 kHz modulation rate, digital filtering techniques are used to remove the effects of this power variation.     

Review of Fluorescence Suppression Techniques in Raman Spectroscopy

Abstract

Raman spectroscopy is an important and powerful technique for analyzing the chemical composition of biological or nonbiological samples in many fields. A serious challenge frequently encountered in Raman measurements arises from the existence of the concurrent fluorescence background. The fluorescence intensity is normally several orders of magnitude larger than the Raman scattering signal, especially in biological samples. Such fluorescence background must be suppressed in order to obtain accurate Raman spectra. Several different techniques have been explored for this purpose. These techniques could be generally grouped into time-domain, frequency-domain, wavelength-domain, and computational methods in addition to various Raman enhancement techniques and other unconventional methods. This review briefly describes the fundamental principles of each group of methods, reports the most recent advances, and makes comparison across those major categories of techniques in terms of cost and performance in a hope to guide interested readers to select proper methods for specific applications.     

X-ray and neutron studies of nanoscale atomic diffusion in thin films and multilayers

In the present work we review some X-ray and neutron based techniques capable of measuring diffusion lengths in thin films with an accuracy of a fraction of a nanometer. The techniques have been used for studying both self-diffusion of the constituent species in a thin film, as well as interdiffusion at the interfaces in multilayers. The high accuracy of the techniques in depth profiling of an element or a specific isotope makes very low diffusivities ∼10⁻²³ m²/s, amenable to measurements, and allows one to study the subtle effects of factors like internal stresses or structural relaxation on self-diffusion in compositionally homogeneous films. Depth selectivity of X-ray standing wave technique in multilayers makes it possible to distinguish between diffusion at the two types of the interfaces, namely A-on-B and B-on-A, in a single multilayer structure.     

Comparison of off-axis and in-line electron holography as quantitative dopant-profiling techniques

Many different dopant-profiling techniques are available for semiconductor device characterization. However, with length scales shrinking rapidly, only transmission electron microscopy (TEM) techniques promise to fulfil the spatial resolution required for the characterization of future device generations. Here, we use three advanced TEM techniques, off-axis electron holography, Fresnel imaging (in-line electron holography) and Foucault imaging, to examine a focused ion beam-prepared silicon p–n junction device. Experiments are carried out on electrically unbiased samples and with an electrical bias applied in situ in the TEM. Simulations are matched to experimental data to allow quantitative conclusions to be drawn about the underlying electrostatic potential distributions. The off-axis electron holography and Fresnel results are compared to assess whether the techniques are consistent, and whether they can be used to provide complementary information about dopant potentials in semiconductor devices.     

Empirical Frequentist Coverage of Deep Learning Uncertainty Quantification Procedures

Uncertainty quantification for complex deep learning models is increasingly important as these techniques see growing use in high-stakes, real-world settings. Currently, the quality of a model’s uncertainty is evaluated using point-prediction metrics, such as the negative log-likelihood (NLL), expected calibration error (ECE) or the Brier score on held-out data. Marginal coverage of prediction intervals or sets, a well-known concept in the statistical literature, is an intuitive alternative to these metrics but has yet to be systematically studied for many popular uncertainty quantification techniques for deep learning models. With marginal coverage and the complementary notion of the width of a prediction interval, downstream users of deployed machine learning models can better understand uncertainty quantification both on a global dataset level and on a per-sample basis. In this study, we provide the first large-scale evaluation of the empirical frequentist coverage properties of well-known uncertainty quantification techniques on a suite of regression and classification tasks. We find that, in general, some methods do achieve desirable coverage properties on in distribution samples, but that coverage is not maintained on out-of-distribution data. Our results demonstrate the failings of current uncertainty quantification techniques as dataset shift increases and reinforce coverage as an important metric in developing models for real-world applications.     

New space missions for mapping the Earth's gravity field

The knowledge of the gravity field of the Earth and of an associated reference surface of altitudes (the geoid) is necessary for geodesy, for improving theories of the physics of the planet interior and for modeling the ocean circulation in absolute. This knowledge comes from several observing techniques but, although it benefited from the artificial satellite approach, it remains incomplete and erroneous in places. Within a reasonable future, a substantial improvement can only come from new space techniques. Thanks to the intense lobbying by the concerned geoscientists, the coming decade will see the advent of three techniques already proposed in the seventies and to be implemented by different space agencies; these are the CHAMP, GRACE and GOCE missions.     

Optical Diagnosis for Thyroid and Parathyroid Tissues—A Review

Abstract

This article presents an overview of optical methodologies to aid the diagnosis and differentiation of thyroid and parathyroid tissues. In particular, we review the several techniques and associated methodologies that allow in vivo and ex vivo optical characterization of thyroid and parathyroid tissues. Emphasis is placed on the research potential of these techniques and whether intrinsic characteristics can provide useful contrast for the diagnosis of human thyroid and parathyroid malignant lesions.     

Sample Preparation for the Determination of Metals in Food Samples Using Spectroanalytical Methods—A Review

Abstract

The present article gives an overview of recent publications and modern techniques of sample preparation for food analysis employing atomic and inorganic mass spectrometric techniques, such as flame atomic absorption spectrometry, chemical vapor generation atomic absorption and atomic fluorescence spectrometry, graphite furnace atomic absorption spectrometry, inductively coupled plasma optical emission spectrometry, and inductively coupled plasma mass spectrometry. Among the most frequently applied sample preparation techniques for food analysis are dry ashing, usually with the addition of an ashing aid, and acid digestion, preferably with the assistance of microwave energy. Slurry preparation, particularly with the assistance of ultrasound, is increasingly used to reduce acid consumption and sample preparation time. Direct analysis of solid samples is gaining importance in the field of food analysis as it offers the highest sensitivity, avoids the use of acids and other aggressive reagents, makes possible the analysis of micro‐samples, and can be applied for fast screening analysis, e.g., of fresh meat.     

Paths Clustering and an Existence Result for Stochastic Vortex Systems

We prove, via a pathwise analysis, an existence result for stochastic differential equations with singular coefficients that govern stochastic vortex systems. The techniques are self-contained and rely on careful estimates on the displacements of particles, obtained by recursively identifying “vortex clusters“ whose mutual interactions can be controlled. This provides a non trivial extension of techniques of Marchioro and Pulvirenti⁽⁷⁾ for deterministic motion of vortices. AMS subject classification: 60H10, 60K35, 76B47     

Collective phenomena in heavy ion collisions

Collective flow from ultra-relativistic heavy ion collisions is an important hadronic observable sensitive to the early stages of system evolution. We have calculated flow components from a tilted, ellipsoidally expanding source. We also reviewed the recent experimental techniques used for calculation of the v _nFourier coefficients and pointed out a few possible problems connected to these techniques, which may lead to serious inaccuracy in the flow analysis.     

Defect structure studies using positron annihilation spectroscopy

The positron annihilation method is a new addition to the range of sensitive complementary nuclear techniques available for materials’ research. The preferential sensitivity of positrons towards micro-defect domains which are not assessable by other techniques makes it an attractive tool for many materials science problems. The present paper is intended as a brief introduction on the principle of measurements and its potential is exemplified with the help of results on some metallic and ceramic systems.     

Hurst exponent determination for digital speckle patterns in roughness control of metallic surfaces

In this paper, we present a study of metallic surface roughness using the Hurst exponent calculated from speckle pattern. A set of samples was prepared using polishing techniques and the roughness was directly measured by means of an optical profilometer. To study the H exponent, an experiment was performed by illuminating the samples using an expanded laser beam and the surface image was captured by a CCD camera. We applied techniques of the Hurst exponent calculation, traditionally calculated from surface profile, in the digitalized speckle patterns generated by the rough surfaces. We showed a clear dependence of the H exponent on roughness of the samples. We demonstrated that this tool is very sensitive to defects in the surfaces and can be used for roughness control.     

UHV-HREM and diffraction of surfaces

Characterization of the structure of surfaces is very important in order to develop a fundamental understanding of the electronic, mechanical and chemical properties of a material. While transmission electron microscopy imaging (TEM) and diffraction (TED) techniques are capable of providing surface structural information at the atomic level, such data would be suspect if obtained under conventional vacuum conditions (10^-6–10^-8 Torr). Ultrahigh vacuum (UHV) conditions are imperative during both preparation and observation of clean surfaces/interfaces. Conventional TEM techniques are very powerful for UHV-TEM investigations; however, the marriage of surface science and conventional TEM to yield an UHV-TEM is a complex task. These complexities and some of the results obtained using UHV-TEM and UHV-TED techniques for surfaces i.e. solid-vacuum interfaces will be illustrated.     

A study of 1.74 MHz atmospheric pressure dielectric barrier discharge for non-conventional treatments

The paper presents a study on the atmospheric pressure dielectric barrier discharge plasma, generated with Teflon covered electrodes in flowing helium at a driving frequency of 1.74 MHz. Besides generation techniques and running principle, an operating stability diagram is presented for the discharge. By means of optical emission techniques, characteristic temperatures were determined and the reactive species were identified. The applicability of generated discharge was tested by surface functionalization and bacterial inactivation. It was found that even for short treatment times the plasma is efficient for surface treatment and it can inactivate Escherichia coli with a D-time of 10 s.     

Optimum projection pattern generation for grey-level coded structured light illumination systems

Structured light illumination (SLI) systems are well-established optical inspection techniques for noncontact 3D surface measurements. A common technique is multi-frequency sinusoidal SLI that obtains the phase map at various fringe periods in order to estimate the absolute phase, and hence, the 3D surface information. Nevertheless, multi-frequency SLI systems employ multiple measurement planes (e.g. four phase shifted frames) to obtain the phase at a given fringe period. It is therefore an age old challenge to obtain the absolute surface information using fewer measurement frames. Grey level (GL) coding techniques have been developed as an attempt to reduce the number of planes needed, because a spatio-temporal GL sequence employing p discrete grey-levels and m frames has the potential to unwrap up to p^m fringes. Nevertheless, one major disadvantage of GL based SLI techniques is that there are often errors near the border of each stripe, because an ideal stepwise intensity change cannot be measured. If the step-change in intensity is a single discrete grey-level unit, this problem can usually be overcome by applying an appropriate threshold. However, severe errors occur if the intensity change at the border of the stripe exceeds several discrete grey-level units. In this work, an optimum GL based technique is presented that generates a series of projection patterns with a minimal gradient in the intensity. It is shown that when using this technique, the errors near the border of the stripes can be significantly reduced. This improvement is achieved with the choice generated patterns, and does not involve additional hardware or special post-processing techniques. The performance of that method is validated using both simulations and experiments. The reported technique is generic, works with an arbitrary number of frames, and can employ an arbitrary number of grey-levels.     

A Review on the Use of Near-Infrared Spectroscopy for Analyzing Feed Protein Materials

Abstract: Due to the strong link between feed and food, the quality and safety of feed protein materials are of public concern. Firstly, this article summarizes the recent advances in near-infrared reflectance spectroscopy (NIRS) techniques applied to the chemical content and traceability analyses of feed protein materials. The results show the potential of NIRS as an efficient first-line screening tool for monitoring the quality and safety of feed protein materials. Finally, future prospects and the need to increase the feasibility of industrial applications and improve the limit of detection of NIRS techniques for feed protein materials are discussed.