Laser-induced breakdown spectroscopy for detection of explosives residues: a review of recent advances, challenges, and future prospects

In this review we discuss the application of laser-induced breakdown spectroscopy (LIBS) to the problem of detection of residues of explosives. Research in this area presented in open literature is reviewed. Both laboratory and field-tested standoff LIBS instruments have been used to detect explosive materials. Recent advances in instrumentation and data analysis techniques are discussed, including the use of double-pulse LIBS to reduce air entrainment in the analytical plasma and the application of advanced chemometric techniques such as partial least-squares discriminant analysis to discriminate between residues of explosives and non-explosives on various surfaces. A number of challenges associated with detection of explosives residues using LIBS have been identified, along with their possible solutions. Several groups have investigated methods for improving the sensitivity and selectivity of LIBS for detection of explosives, including the use of femtosecond-pulse lasers, supplemental enhancement of the laser-induced plasma emission, and complementary orthogonal techniques. Despite the associated challenges, researchers have demonstrated the tremendous potential of LIBS for real-time detection of explosives residues at standoff distances. Figure This review discusses the application of laser-induced breakdown spectroscopy (LIBS) to the problem of explosive residue detection. LIBS offers the capability for real-time, standoff detection of trace amounts of residue explosives on various surfaces     

Micro‐thermal analysis of polymers: current capabilities and future prospects

The current state of development of micro‐thermal analysis (micro‐TA) and related techniques are briefly reviewed. Results for a PET/epoxy resin composite and a bilayer polymer film are given as illustrations. Details are given of a new interface that enables the micro‐TA unit to be placed inside a conventional FTIR spectrometer to carry out photothermal IR microscopy. New results are presented for a micro‐pyrolysis‐mass spectroscopy technique. The limitations of the current instrumentation are discussed in terms of the overriding problem being one of spatial resolution. Images obtained using pulsed force mode AFM with a high‐resolution heated tip indicate the scope for future development of this technique. The possibility of even higher spatial resolution with other forms of probe are discussed along with the potential for imaging micro‐pyrolysis time of flight mass spectroscopy and even tomography. It is concluded that these methods offer excellent prospects for characterising a wide range of polymer systems.     

Application of multivariate data-analysis techniques to biomedical diagnostics based on mid-infrared spectroscopy

The objective of this contribution is to review the application of advanced multivariate data-analysis techniques in the field of mid-infrared (MIR) spectroscopic biomedical diagnosis. MIR spectroscopy is a powerful chemical analysis tool for detecting biomedically relevant constituents such as DNA/RNA, proteins, carbohydrates, lipids, etc., and even diseases or disease progression that may induce changes in the chemical composition or structure of biological systems including cells, tissues, and bio-fluids. However, MIR spectra of multiple constituents are usually characterized by strongly overlapping spectral features reflecting the complexity of biological samples. Consequently, MIR spectra of biological samples are frequently difficult to interpret by simple data-analysis techniques. Hence, with increasing complexity of the sample matrix more sophisticated mathematical and statistical data analysis routines are required for deconvoluting spectroscopic data and for providing useful results from information-rich spectroscopic signals. A large body of work relates to the combination of multivariate data-analysis techniques with MIR spectroscopy, and has been applied by a variety of research groups to biomedically relevant areas such as cancer detection and analysis, artery diseases, biomarkers, and other pathologies. The reported results indeed reveal a promising perspective for more widespread application of multivariate data analysis in assisting MIR spectroscopy as a screening or diagnostic tool in biomedical research and clinical studies. While the authors do not mean to ignore any relevant contributions to biomedical analysis across the entire electromagnetic spectrum, they confine the discussion in this contribution to the mid-infrared spectral range as a potentially very useful, yet underutilized frequency region. Selected representative examples without claiming completeness will demonstrate a range of biomedical diagnostic applications with particular emphasis on the advantageous interaction between multivariate data analysis and MIR spectroscopy.     

Infrared detection in flow analysis - developments and trends (review)

Flow analysis offers an inexpensive and versatile means for the automation of analytical procedures and hence it has been incorporated in many different techniques. However, the use of infrared detection in flow analysis systems is not common. Whereas Fourier transform infrared (FTIR) spectroscopic detection has been routinely used in gas chromatography (GC), its use for liquid chromatography, and now for flow analysis, flow injection analysis, or sequential injection analysis, is not frequent. The most prominent reasons are probably: (i) the strong absorption of most of the common solvents, specially water, (ii) the relative poor sensibility compared to UV–vis, fluorescence, etc. (iii) FTIR is normally not even considered a valuable detection technique, (iv) problems arising from obtaining adequate information from transient IR signals from the injected samples, and (v) only a few analytical chemist uses routinely the FTIR technique. This practice neglects that IR spectroscopy offers some unique features that now, using modern FTIR instrumentation, can be exploited in an advantageous manner. It is important to realize that each sample (analyte/matrix) represents a special and unique analytical problem; which defines the mode of operation and implementation of the IR technique. Flow analysis–IR techniques – as well as all techniques – has a number of shortcomings to solve these problems. In this article, most of these strategies such as the use of: baseline correction, derivative spectroscopy, stopped flow systems, reverse flow systems, multiparametric calibrations, etc., will be discussed. Additionally, recent developments in on-line gas phase generation–FTIR and hydride generation–FTIR spectrometry, as well as the principles of the HPLC–FTIR and capillary electrophoresis–FTIR hyphenation are also discussed. This review aims to provide an account of the state of the art, of these relatively new techniques. Its beginning, developments, applications and new trends, basically in the MID–IR, and by using transmission cells.     

Diffuse reflectance Fourier transform IR spectroscopy

Fourier transform infrared (FTIR) spectroscopy has greatly enhanced the utility and range of applications of infrared (IR) spectroscopy in chemistry. Until the development of routine FTIR instrumentation, applications of IR were essentially limited to direct transmission measurements. Newer sampling methods in FTIR spectroscopy can be successful with less than 1% throughput of the infrared radiation and yet yield a spectrum with acceptable signal-to-noise ratio. The decreasing cost of FTIR spectrometers has made a number of such sampling techniques accessible for routine applications without compromises in performance. This article will describe one of these, diffuse reflectance.     

Liquid scintillation counting for determination of radionuclides in environmental and nuclear application

Liquid scintillation counting (LSC) is a major technique not only for measurement of pure beta emitting radionuclides, but also radionuclides decay by electron capture and alpha emission. Although it is a conventional radiometric technique, but still a competitive techniques for the measurement of many radionuclides. This paper summaries the major development of this measurement technique in instrumentation, methodology and applications in the past decades. The progresses in the instrumentation and methodology mainly focus on the commercialization of triple-to-double coincidence ratio based LSC techniques and its application in the determination of different radionuclides. An overall review and discussion on the LSC based analytical methods for the determination of major radionuclides in environmental researches, decommissioning of nuclear faculties and nuclear application are presented, in both measurement techniques and sample preparation using radiochemical separation. Meanwhile the problems and challenges in the development and application of the LSC are also discussed.     

Electrospray mass spectrometry: a tool for elemental speciation

Recent progress in the development of electrospray mass spectrometry (ESMS) as a tool for elemental speciation is reviewed. Reports wherein ESMS is used to qualitatively determine the presence of metal ions (inorganic, organometallic and complexed) and non-metallic inorganic species have grown exponentially over the last decade. In addition to elemental speciation, impact in other areas such as gas-phase chemistry, inorganic–organometallic chemistry and biological mass spectrometry has been prolific. The review is structured to cover each of the areas listed above, and also includes a brief introduction, discussion of the electrospray process, discussion of instrumentation and other relevant application areas. An overview of the types of species/complexes studied is given in each section along with a brief discussion of the application objectives and analytical aspects. Analytical considerations for the development of ESMS as a tool for elemental speciation are also raised, including, application, quantitation, sensitivity, limitations and future directions. The impact of speciation strategies involving stand-alone ESMS, ESMS coupled with on-line separation techniques and the inclusion of ESMS in dual (multiple) technique strategies are presented. High backgrounds due to chemical noise and signal suppression (matrix effects) appear to be two important factors limiting sensitive detection of most analytes. The use of sample pre-treatment, pre-concentration or separation techniques is necessary to alleviate these problems. Although ESMS currently suffers from a number of limitations, continued instrumentation and methods development will improve its capability and diversify the impact of ESMS as a tool for elemental speciation.     

Analyses of representative biomarkers of exposure and effect by chromatographic, mass spectrometric, and nuclear magnetic resonance techniques: method development and application in life sciences

Biomarkers are essential tools in monitoring studies, which include environmental monitoring, biological monitoring, biological effect monitoring, and health surveillance, as well as drug development processes. Their discovery, validation, and analysis require highly sensitive and selective analytical technologies. In this regard, gas and liquid chromatography, mass spectrometry, and nuclear magnetic resonance spectroscopy have facilitated great achievements in all these areas. In addition and closely related to biomarkers, the ongoing developments in these techniques promise a better understanding of the nature and mechanisms of toxic effects originating from various chemical, biological, or physical sources. This Review compiles studies performed on selected biomarkers with respect to both method development and application. Section 1 summarizes the concept of biomarkers; their application in various industrial/occupational, agricultural, drug developmental, and medical/clinical platforms. This section also focuses on biotransformation studies in close relation to biomarker discovery and validation, and on major techniques utilized in this area. In Section 2, biotransformation of volatile anesthetics in humans with a focus on mercapturic acid derivatives as potential biomarkers of effect is reviewed. The use of GC-ECD, GC/MS, and 19F-NMR in these studies is described. Section 3 focuses on the analysis of aldehydic lipid peroxidation degradation products by GC-ECD in mammalian cells in which oxidative stress induced chemically, and in humans after various challenges; anesthetic exposure, ischemia-reperfusion, and controlled endurance exercise. In Section 4, method development for protein and DNA oxidation products by LC-tandem MS and its application in mammalian cells and in humans are summarized. Possibilities, limitations, and future perspectives are discussed in Section 5.     

FTIR and GC as complementary tools for analysis of corrosive gases

The gas metrology laboratory of the National Metrology Institute of South Africa has developed methodology for the gravimetric preparation of corrosive gas mixtures such as nitric oxide (NO) in nitrogen, as well as sulphur dioxide (SO₂) in nitrogen or synthetic air. Fourier transform infrared (FTIR) spectroscopy has been used to analyse for trace and ultra trace levels of infrared active gaseous species, such as NO, nitrogen dioxide and SO₂ that are difficult to analyse by other means. These corrosive gas mixtures are also analysed using gas chromatography with pulsed helium ionisation detection to complement the work done using FTIR with infrared active impurities. A comparison between the techniques of FTIR, gas chromatography and non-dispersive infrared spectroscopy for corrosive gas analysis is also presented.     

Polarization modulation Fourier transform infrared spectroscopy

Polarization modulation Fourier transform infrared spectroscopy can be measured by either double modulation FTIR or interferometric modulation FTIR techniques. The principles of both techniques are presented with examples of representative measurements. The relative advantages and disadvantages of each method are compared.     

Proteins in action monitored by time-resolved FTIR spectroscopy.

In the post genome era proteins coming into the focus of life sciences. X-ray structure analysis and NMR spectroscopy are established methods to determine the geometry of proteins. In order to determine the molecular reaction mechanism of proteins, time-resolved FTIR (trFTIR) difference spectroscopy emerges as a valuable tool. In this Minireview we describe the trFTIR difference spectroscopy and show its application on the light-driven proton pump bacteriorhodopsin (bR), the photosynthetic reaction center and the GTPase Ras, which is crucial in signal transduction. The main principles of the technique are presented, including a summary of triggering techniques, scan modes and analysis.     

Raman piezo-spectroscopic analysis of natural and synthetic biomaterials

Raman piezo-spectroscopy of bone, teeth, and artificial joints is reviewed with emphasis placed on confocal microprobe techniques. Characteristic spectra are presented and quantitative assessments of their phase structure and stress dependence are shown. Vibrational spectroscopy is used here to study the microscopic stress response of cortical bone to external stress (with or without internal damages), to define microscopic stresses across the dentine–enamel junction under increasing external compressive load, and to characterize interactions between prosthetic implants and biological environment. Confocal spectroscopy allows acquisition of spatially resolved spectra and stress imaging with high spatial resolution.     

Total internal reflection Raman spectroscopy

Total internal reflection (TIR) Raman spectroscopy is an experimentally straightforward, surface-sensitive technique for obtaining chemically specific spectroscopic information from a region within approximately 100-200 nm of a surface. While TIR Raman spectroscopy has long been overshadowed by surface-enhanced Raman scattering, with modern instrumentation TIR Raman spectra can be acquired from sub-nm thick films in only a few seconds. In this review, we describe the physical basis of TIR Raman spectroscopy and illustrate the performance of the technique in the diverse fields of surfactant adsorption, liquid crystals, lubrication, polymer films and biological interfaces, including both macroscopic structures such as the surfaces of leaves, and microscopic structures such as lipid bilayers. Progress, and challenges, in using TIR Raman to obtain depth profiles with sub-diffraction resolution are described.     

蛋白质结构的FT-IR研究进展

随着蛋白质使用领域的增加,迫切需要知道它在不同环境中的结构特征及生物活性。目前,测定蛋白质结构的方法很多,包括X射线衍射技术、圆二色光谱(CD)、质谱、FT-IR等。FT-IR(傅立叶变换光谱)法不仅能够测定不同环境中的蛋白质结构及生物活性,而且能够测定其二级结构的相对含量。本文简要综述FT-IR技术用于蛋白质结构的研究进展。     

Thermochemical and physical properties of printed circuit board laminates and other polymers used in the electronics industry

Theories behind four thermal analysis techniques are reviewed, and relevant case studies are used to illustrate the application of these techniques to measure; various parameters relevant to printed circuit board laminates and engineering polymers.Thermogravimetric analysis (TGA) is used to determine the filler content of polymers and composites and when combined with Fourier transform infrared (FTIR) spectroscopy can be used for the chemical analysis of evolved gases.Differential scanning calorimetry (DSC) is used to measure the melting point of polymers and the degree of cure of prepregs, laminates and adhesives.Thermomechanical analysis (TMA) is used to measure the coefficient of thermal expansion (CTE) and the glass transition temperature (Tg) of laminates, and dynamic mechanical analysis (DMA) is used to measure the storage modulus, loss; modulus and Tan δ of polymers.     

Compositional dynamics of a commercial wine fermentation using two-dimensional FTIR correlation analysis

We have demonstrated that compositional changes occurring during a commercial red wine fermentation can be effectively monitored using FTIR spectroscopy and modelled with the aid of two-dimensional correlation techniques. This study represents a novel application of two-dimensional spectroscopy and showed that the reaction rates for the conversion of fructose and glucose to alcohol were different, with the latter being more rapid. The use of a simple three-component model serves to aid interpretation of the data and the results obtained confirm the value of two-dimensional FTIR correlation spectroscopy as a chemometric tool which has considerable potential for process monitoring.     

Cathodoluminescence Microscopy and Spectroscopy of Opto-Electronic Materials

Cathodoluminescence (CL) microscopy and spectroscopy are enabling techniques for the microcharacterisation of technologically important materials. Recent advances in SEM instrumentation have considerably expanded the microanalytical capabilities of the CL technique. In this paper, following a brief overview of the principles and practice of CL microscopy and spectroscopy, a number of examples are presented that demonstrate the utility of the technique for the microcharacterisation of advanced opto-electronic materials.     

Analysis of a coloured Dutch map from the eighteenth century: the need for a multi-analytical spectroscopic approach using portable instrumentation

A Dutch map from the eighteenth century was multi-analytically analysed making use of energy dispersive X-ray fluorescence (EDXRF), Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), Raman and scanning electron microscopy coupled to energy dispersive spectrometry (SEM-EDS). The cellulosic support was characterised and its state of conservation was evaluated. Besides, paramagnetic impurities were detected together with copper metallic chips. The colours present in some areas of the map were also analysed. Vermilion, carbon black and organic pigments were found. Surprisingly, in the green areas, the rare presence of the mineral moolooite (copper oxalate) was detected. A possible biological attack is discussed in order to explain the presence of such compound. Almost all of the techniques used in the analysis were portable, non-destructive and non-invasive, which is very desirable when analysing objects belonging to Cultural Heritage. The need for a multi-analytical approach using portable instrumentation is also discussed.