Applied Spectroscopy

doi: 10.1177/00037028241292113pmid: 39425542

Hudgins, Michael Naylor; Knobbe, Todd K.; Hubbard, Julia; Steele, Andrew; Park, Justin G.; Schaller, Morgan F.

doi: 10.1177/00037028241275192pmid: 39238229

Carbonate minerals are globally distributed on the modern and ancient Earth and are abundant in terrestrial and marine depositional environments. Fluid inclusions hosted by calcite retain primary signatures of the source fluid geochemistry at the time of mineral formation (i.e., pCO2) and can be used to reconstruct paleoenvironments. Confocal laser Raman spectroscopy provides a quick, nondestructive approach to measuring the constituents of fluid inclusions in carbonates and is a reliable method for qualitatively determining composition in both the aqueous and gas phases. Here, we demonstrate a method for accurately quantifying bicarbonate and carbonate ion concentrations (down to 20 mM) and pH (7–11) from calcite fluid inclusions using confocal Raman spectroscopy. Instrument calibrations for carbonate (CO32–) and bicarbonate (HCO3–) concentrations and pH were performed using stock solutions. We show that the calcite host mineral does not affect the accurate quantification of carbonate solution concentrations and that these parameters can be used to estimate the pH and pCO2 of a solution entrapped within a fluid inclusion. We apply the technique to Icelandic spar calcite and find a [CO32–] = 0.11, [HCO3–] = 0.17, pH = 10.1, and CO2 parts per million = 2217. The presence of gaseous Raman bands for CO2, CH4, and H2S suggests that the mineral precipitated in a reducing environment.

Dias, Daniele T.; Rodrigues, Andressa O.; Pires, Pietra B.; Semianko, Betina C.; Fuziki, Maria E.K.; Lenzi, Giane G.; Sabino, Simone R.F.

doi: 10.1177/00037028241268158pmid: 39094004

The aim of this work was the development and morphological/chemical, spectroscopic, and structural characterization of titanium dioxide, niobium pentoxide, and titanium:niobium (Ti:Nb) oxides, as well as materials modified with ruthenium (Ru) with the purpose of providing improvement in photoactivation capacity with visible sunlight radiation. The new materials synthesized using the sol-gel methodology were characterized using the following techniques: scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), photoacoustic spectroscopy (PAS), and X-ray diffraction (XRD). The SEM–EDS analyses showed the high purity of the bases, and the modified samples showed the adsorption of ruthenium on the surface with the crystals’ formation and visible agglomerates for higher calcination temperature. The nondestructive characterization of PAS in the ultraviolet visible region suggested that increasing calcination temperature promoted changes in chemical structures and an apparent decrease in gap energy. The separation of superimposed absorption bands referring to charge transfers from the ligand to the metal and the nanodomains of the transition metals suggested the possible absorption centers present at the absorption threshold of the analyzed oxides. Through the XRD analysis, the formation of stable phases such as T-Nb16.8O42, o-Nb12O29, and rutile was observed at a lower temperature level, suggesting pore induction and an increase in surface area for the oxides studied, at a calcination temperature below that expected by the related literature. In addition, the synthesis with a higher temperature level altered the previously existing morphologies of the Ti:Nb, base and modified with Ru, forming the new mixed crystallographic phases Ti2Nb10O29 and TiNb2O7, respectively. As several semiconductor oxide applications aim to reduce costs with photoexcitation under visible light, the modified Ti:Ru oxide calcined at a temperature of 800 °C and synthesized according to the sol-gel methodology used in this work is suggested as the optimum preparation point. This study presented the formation of a stable crystallographic phase (rutile), a significant decrease in gap energy (2.01 eV), and a visible absorption threshold (620 nm).

Dorris, Austin L.; Umar, Abdul Rashid; Grieco, Christopher

doi: 10.1177/00037028241247072pmid: 38629126

In this work, we detail an ultrafast pump-probe transient absorption (TA) spectrometer capable of probing the near-infrared (NIR) spectral region from 900 to 2350 nm simultaneously. Two key advances were required to overcome previous spectral window limitations, which typically result from constrained supercontinuum ranges (e.g., 1700 nm) and/or InGaAs detector line rates, especially those with >1700 nm range. First, we generated a broadband NIR supercontinuum using the 1980 nm idler beam of an optical parametric amplifier and implement a unique spectral filtering scheme to balance the detected spectrum. Second, we used a prism-based spectrometer system equipped with high speed InGaAs cameras having ∼2500 nm sensitivity cutoffs. To the best knowledge of the authors, such an extended probe range was previously inaccessible because the combination of two optical geometries either using different supercontinuum crystal materials for generating the NIR and shortwave infrared (SWIR) regions, or using differing pump wavelengths, were required. Finally, we demonstrate the performance and capabilities of the ultrabroadband TA spectroscopy system by presenting data showing ultrafast charge photogeneration in a polymer : fullerene blend thin-film and comparing the results to the literature with a complete agreement.

Penkov, Nikita V.

doi: 10.1177/00037028241261097pmid: 38881287

This paper describes an approach based on the method of terahertz time-domain spectroscopy, which allows the analysis of dynamical hydration shells of proteins with a thickness of 1–2 nm. Using the example of bovine serum albumin in three conformations, it is shown that the hydration shells of the protein are characterized by increased binding of water molecules in the primary hydration layers, and in more distant areas of hydration, on the contrary, the water structure is somewhat destroyed. The fraction of free or weakly bound molecules, usually observed in the structure of liquid water in hydration shells, become more numerous but its average binding is greater than in undisturbed water. The energy distribution of hydrogen bonds in hydration shells is narrowed compared to undisturbed water. All these manifestations of hydration are most pronounced for the native conformation of the protein. Also, the hydration shells of the native protein are characterized by a smaller number of hydrogen bonds and a tendency to decrease their average energy compared to non-native conformations. The fact of a pronounced peculiarity of the hydration shells of the protein in the native conformation has been noted for different proteins before. However, the methodological approach used in this work for the first time allowed this peculiarity to be described by specific parameters of the intermolecular structure and dynamics of water.

Kelly, Evan M.; Egan, Miles J.; Colόn, Arelis; Angel, S. Michael; Sharma, Shiv K.

doi: 10.1177/00037028241257961pmid: 38853620

Raman spectroscopy allows for the unambiguous identification of materials through the inelastic scattering of light. This technique has a great many uses in various aspects of society from academic, scientific, and industry. This paper explores a specific type of Raman spectrometer called a spatial heterodyne Raman spectrometer (SHRSy), which is a variation of an interferometric spectrometer. It utilizes a Michelson interferometer and replaces the mirrors with gratings that transform it from a time-domain spectrometer to a spatial-domain spectrometer, allowing for the entirety of the spectrum to be captured at once. This study specifically tests a half-inch two-grating monolithic SHRS (½-in. 2g-mSHRS), which has a weight of <60 g and a size of 2.2 × 2.2 × 1.3 cm. To do this we excite a variety of organic liquids with a 532 nm neodymium-doped yttrium aluminum garnet (Nd:YAG) pulsed laser, using an excitation energy of 6.5 mJ/pulse and distance of 3 m in conjunction with an intensified charge-coupled device camera. This is the first time that the SHRS has been used for investigating polarized Raman spectra of liquids. We discuss and contrast the instrumental properties such as resolution, spectral range, étendue, and field of view with previously tested mSHRS to give context to the instrument's performance.

Anderson, Benjamin R.; Gese, Natalie; Eilers, Hergen

doi: 10.1177/00037028241267921pmid: 39094002

We characterize the subsurface thermal degradation of an inert analog of high-explosive molecular crystals (Eu:Y(acac)3(DPEPO)) (EYAD) embedded inside of a plastic bonded explosive simulant using feedback-assisted wavefront shaping-based fluorescence and Raman spectroscopies. This technique utilizes wavefront shaping to focus pump light inside a heterogeneous material onto a target particle, which significantly improves its spectroscopic signature. We find that embedding the EYAD crystals in the heterogeneous polymer results in improved thermal stability, relative to bare crystal measurements, with the crystal remaining fluorescent to >612 K inside of the heterogeneous material, while the bare crystal’s fluorescence is fully quenched by 500 K. We hypothesize that this improvement is due to the polymer restricting the effects of EYAD melting, which occurs at 400 K and is the primary mechanism for spectroscopic changes in the temperature range explored.

Bong, Cheolwoo; Im, Seong-kyun; Do, Hyungrok; Bak, Moon Soo

doi: 10.1177/00037028241268279pmid: 39091033

A new optical diagnostic method that predicts the global fuel–air equivalence ratio of a swirl combustor using absorption spectra from only three optical paths is proposed here. Under normal operation, the global equivalence ratio and total flow rate determine the temperature and concentration fields of the combustor, which subsequently determine the absorption spectra of any combustion species. Therefore, spectra, as the fingerprint for a produced combustion field, were employed to predict the global equivalence ratio, one of the key operational parameters, in this study. Specifically, absorption spectra of water vapor at wavenumbers around 7444.36, 7185.6, and 6805.6 cm–1 measured at three different downstream locations of the combustor were used to predict the global equivalence ratio. As it is difficult to find analytical relationships between the spectra and produced combustion fields, a predictive model was a data-driven acquisition. The absorption spectra as an input were first feature-extracted through stacked convolutional autoencoders and then a dense neural network was used for regression prediction between the feature scores and the global equivalence ratio. The model could predict the equivalence ratio with an absolute error of ±0.025 with a probability of 96%, and a gradient-weighted regression activation mapping analysis revealed that the model leverages not only the peak intensities but also the variations in the shape of absorption lines for its predictions.

Junjuri, Rajendhar; Gummadi, Arun Prakash; Gundawar, Manoj Kumar

doi: 10.1177/00037028241268348pmid: 39091035

We report the standoff/remote identification of post-consumer plastic waste by utilizing a low-cost and compact standoff laser-induced breakdown spectroscopy (ST-LIBS) detection system. A single plano-convex lens is used for collecting the optical emissions from the plasma at a standoff distance of 6.5 m. A compact non-gated Czerny–Turner charge-coupled device (CCD) spectrometer (CT-CCD) is utilized to analyze the optical response. The single lens and CT-CCD combination not only reduces the cost of the detection system by tenfold, but also decreases the collection system size and weight compared to heavy telescopic-based intensified CCD systems. All the samples investigated in this study were collected from a local recycling plant. All the measurements were performed with only a single laser shot which enables rapid identification while probing a large number of samples in real time. Furthermore, principal component analysis has shown excellent separation among the samples and an artificial neural network analysis has revealed that plastic waste can be identified within ∼10 ms only (testing time) with accuracies up to ∼99%. Finally, these results have the potential to build a compact and low-cost ST-LIBS detection system for the rapid identification of plastic waste for real-time waste management applications.

Sidorova, Mariia; Pavlov, Sergey G.; Böttger, Ute; Baqué, Mickael; Semenov, Alexei D.; Hübers, Heinz-Wilhelm

doi: 10.1177/00037028241267892pmid: 39091019

Raman spectroscopy is among the top analytical techniques for ultra-low-dense organic matter, crucial to the search for life and analysis of celestial body surfaces in space exploration missions. Achieving the ultimate sensitivity of in-situ Raman spectroscopy necessitates a breakthrough in detecting inelastically scattered light. Single-photon detectors (SPDs) operating in photon counting mode, which can differentiate between Raman and luminescence responses, are promising candidates for the challenging scientific requirements. Since large SPD arrays are not yet commercially available, a dispersive element can be adapted to a single-pixel detector. By exploiting chromatic dispersion in optical fibers and picosecond-pulsed excitation, we delay the arrivals of different spectral components onto a single-pixel SPD. This method also separates weak Raman signals from stronger luminescence through correlated time-domain measurements. We study the impact of fiber properties and the excitation wavelength of a pulsed laser on the spectral resolution of the fiber-dispersive Raman spectrometer (FDRS). Additionally, we demonstrate the FDRS’s potential for studying biomarkers and discuss its feasibility for analyzing inclusions in ice matrices.