The Interplay Between Spectrometer Development and Professional Spectroscopic Societies.

The post-World War II availability of commercial spectrometers spurred the development of professional spectroscopic societies: The Infrared and Raman Discussion Group in the UK, the Coblentz Society, and the Society for Applied Spectroscopy in the USA. There was a desire to ensure that customers understood the instrumentation and techniques, became part of a community, and had access to the latest subject matter knowledge. With the advent of low-cost routine instruments, and portable instruments in the field, professional societies have a distinct role to play in education and training, especially as libraries deaccession (withdraw) even comparatively recent books on practical spectroscopy.

LEGO Blocks as "Standard" Samples for Evaluation of Fluorescence Avoidance and Mitigation in Raman Spectroscopy.

Fluorescence interference in Raman spectroscopy is a well-known problem and is especially significant in portable instruments where the availability of a variety of exciting wavelengths is unlikely. Several fluorescence avoidance and mitigation schemes are described in the literature, and implemented by Raman spectrometer manufacturers, but there is no standard method for evaluating the accuracy and repeatability of these schemes. Some test samples shown in instrument descriptions, such as "dark rum" and "sesame seed oil" are not reproducible. Therefore, we propose a set of colored LEGO blocks as "standard" samples for this purpose; they have the attractive properties of being very low cost, rugged, non-toxic, easy to transport and store, and appear to be manufactured using a standard process. This paper shows the Raman spectra of a set of these blocks at different excitation wavelengths, acquired on laboratory instruments, along with their visible-near-infrared spectra. The goal is to qualitatively understand the origins of the observed fluorescence and lay the groundwork for exploring the effectiveness of methods currently implemented on handheld Raman instruments.

Field-portable detection of fentanyl and its analogs: A review.

The need to detect fentanyl and its analogs in the field is an important capability to help prevent unintentional exposure or overdose on these substances, which may result in death. Many portable methods historically used in the field by first responders and other field users to detect and identify other chemical substances, such as hazardous materials, have been applied to the detection and identification of these synthetic opioids. This paper describes field portable spectroscopic methods used for the detection and identification of fentanyl and its analogs. The methods described are automated colorimetric tests including lateral flow assays; vibrational spectroscopy (mid-infrared and Raman); gas chromatography-mass spectrometry; ion mobility spectrometry, and high-pressure mass spectrometry. In each case the background and key details of these technologies are outlined, followed by a discussion of the application of the technology in the field. Attention is paid to the analysis of complex mixtures and limits of detection, including the required spectral databases and algorithms used to interrogate these types of samples. There is also an emphasis on providing actionable information to the (likely) non-scientist operators of these instruments in the field.

Portable Spectroscopy.

Until very recently, handheld spectrometers were the domain of major analytical and security instrument companies, with turnkey analyzers using spectroscopic techniques from X-ray fluorescence (XRF) for elemental analysis (metals), to Raman, mid-infrared, and near-infrared (NIR) for molecular analysis (mostly organics). However, the past few years have seen rapid changes in this landscape with the introduction of handheld laser-induced breakdown spectroscopy (LIBS), smartphone spectroscopy focusing on medical diagnostics for low-resource areas, commercial engines that a variety of companies can build up into products, hyphenated or dual technology instruments, low-cost visible-shortwave NIR instruments selling directly to the public, and, most recently, portable hyperspectral imaging instruments. Successful handheld instruments are designed to give answers to non-scientist operators; therefore, their developers have put extensive resources into reliable identification algorithms, spectroscopic libraries or databases, and qualitative and quantitative calibrations. As spectroscopic instruments become smaller and lower cost, "engines" have emerged, leading to the possibility of being incorporated in consumer devices and smart appliances, part of the Internet of Things (IOT). This review outlines the technologies used in portable spectroscopy, discusses their applications, both qualitative and quantitative, and how instrument developers and vendors have approached giving actionable answers to non-scientists. It outlines concerns on crowdsourced data, especially for heterogeneous samples, and finally looks towards the future in areas like IOT, emerging technologies for instruments, and portable hyphenated and hyperspectral instruments.

Computational and ESR studies of electron attachment to decafluorocyclopentane, octafluorocyclobutane, and hexafluorocyclopropane: electron affinities of the molecules and the structures of their stable negative ions as determined from 13C and 19F hyperfine coupling constants.

High-resolution ESR spectra of the ground-state negative ions of hexafluorocyclopropane (c-C3F6*-), octafluorocyclobutane (c-C4F8*-), and decafluorocyclopentane (c-C5F10*-) are reported and their isotropic 19F hyperfine coupling constants (hfcc) of 198.6 +/- 0.4 G, 147.6 +/- 0.4 G, and 117.9 +/- 0.4 G, respectively, are in inverse ratio to the total number of fluorine atoms per anion. Together with the small value of 5.2 +/- 0.4 G determined for the isotropic 13C hfcc of c-C4F8*-, these results indicate that in each case the singly occupied molecular orbital (SOMO) is delocalized over the equivalent fluorines and possesses a nodal plane through the carbon atoms of a time-averaged D(nh) structure. A series of quantum chemical computations were carried out to further characterize these anions and their neutral counterparts. Both the B3LYP density functional and second-order Møller-Plesset perturbation theory (MP2) indicate that c-C3F6*- adopts a D(3h) geometry and a (2)A2'' ground electronic state, that c-C4F8*- adopts a D(4h) geometry and a (2)A2u ground electronic state, and that c-C5F10*- adopts a C(s) structure and a (2)A' electronic state. Moreover, the 19F hyperfine coupling constants computed with the MP2 method and a high quality triple-zeta basis set are within 1% of the experimental values. Also, the values computed for the 13C hfcc of c-C4F8*- are consistent with the experimental value of 5.2 G. Therefore, in keeping with the ESR results, these negative ions derived from first-row elements can be characterized as pi* species. In addition, the hypervalency of these perfluorocycloalkane radical anions has been clarified.