Spectroscopy Journal

This paper presents a systematic absorption and circular dichroism spectroscopy study of short single strands of DNA, from 2 to 20 bases. They are composed of a sequence-specific nucleobase composition, either adenine (A), thymine (T), or AT repeats. The absorption spectra hypochromism and the circular dichroism one show butterfly-shaped spectra. Data analysis conducted on the spectra of these oligomers provides evidence for the formation of excitons and their delocalization length along the strand of DNA in relation to how many bases are involved in the excitonic coupling. In particular, the extent of this coupling is limited to adjacent nucleobases in the case of pure adenine strands but spans multiple nucleobases in the case of pure thymine strands. Predictably, AT repeats show a mixed behavior between the two. Full article

Mössbauer spectroscopy can be advantageous for studying catalysts. In particular, its use in in situ studies can provide unique access to structural features. However, special attention must be paid to the interpretation of data, since in most studies, the samples are not perfectly homogeneous. Balance and compromise should be found between the refinement of evaluations by extracting and interpreting data from spectra, while also considering the presence of possible inhomogeneities in samples. In this review, examples of studies on two types of catalysts are presented, from which, despite possible inhomogeneities, clear statements can be derived. The first example pertains to selected iron-containing microporous zeolites (with ⁵⁷Fe Mössbauer spectroscopy), from which unique information is collected on the coordination of iron ions. The second example is related to studies on supported PtSn alloy particles (with ¹¹⁹Sn probe nuclei), from which reversible modifications of the tin component due to interactions with the reaction partners are revealed. Full article

In this review, we demonstrate that the carotenoids–retinoids–cytochromes c triangle is an important cancer factor controlling most aspects of the development, proliferation, and progression of cancer. Cancer is a multidimensional disease that needs a balance between the enzymes controlling the amount of carotenoids, the production of retinoids (particularly retinoic acid), and the concentration of cytochromes (particularly cytochrome c). The proper balance between these enzymes will help in overcoming the bottleneck in cancer therapeutics using drugs. First, we discuss the impact of carotenoids on cancer. In the next section, we show how carotenoid cleavage products, including retinal, retinol, and retinoic acid, induce positive and negative effects on cancer development. Then, we discuss the impact of cytochrome c on cancer. We have demonstrated that an alteration in the cellular redox status of cytochrome c is a crucial factor in cancer, influencing numerous aspects of malignant progression. The results obtained by Raman imaging showed significant differences between normal and cancerous human cells. First, a significant redox imbalance in the hem group of cytochrome c with the upregulation of the reduced form of hem is observed. Cancer tissue has a higher concentration of reduced cytochrome c than normal tissue. Secondly, both breast and brain tumors exhibit enhanced de novo lipogenesis in comparison to normal cells. Third, this research illustrates the essential function of the extracellular matrix in oxidative phosphorylation and apoptosis pathways. Full article

Fourier transform infrared (FTIR) spectroscopy, coupled with machine learning (ML) analysis can be used for disease monitoring with high speed and accuracy, including the classification of mosquito samples by species, age and malaria detection. However, current FTIR instruments use low-brightness thermal light sources to generate infrared light, which limits their ability to measure complex biological samples, especially where high spatial resolution is necessary, such as for specific mosquito tissues. Moreover, these systems lack portability, which is essential for field applications. To overcome these issues, spectrometers using quantum cascade lasers (QCLs) have become an attractive alternative for building fast, and portable systems due to their high electrical-to-optical efficiency, small size, and potential for low-cost. Here, we present a QCL-based spectrometer prototype designed for large scale, low-cost, environmental field-based disease surveillance. Full article

Optical spectroscopic methods such as Raman spectroscopy offer several advantages for the analysis of water-soluble polymers (WSPs). There is often no need for complex sample preparation, and measurements are usually rapid, mostly non-destructive and no harmful chemicals are required. In this work, we investigated WSPs and their interaction with bacteria using Raman spectroscopic methods. We analyzed four different WSPs, each with three different molar masses, in solid form using Raman microscopy, and in aqueous solutions using another Raman system designed for measurements in cuvettes, to train predictive models for concentration determination. Thus, we were able to show both the high potential of these approaches, especially for fast and easy investigations both qualitatively and quantitatively, as well as their limitations. Furthermore, we chose one of the molar masses of each tested polymer to carry out extensive Raman spectroscopic investigations with Escherichia coli and Enterococcus faecium, and revealed that bacterial cells exposed to polymers exhibited distinguishable spectral characteristics compared to those not in contact with polymers. Using Raman microscopy combined with partial least squares discriminant analysis (PLS-DA), we effectively distinguished between these groups. Further chemometric analysis indicated potential polymer-induced modifications to the bacterial cell membranes. While this differentiation may partly reflect polymer interactions at the membrane level, it could also correspond to shifts in bacterial growth phases. Together, these findings suggest a complex interplay between polymer exposure and bacterial physiological states. Full article

Significance: We describe a novel, specimen-free diagnostic platform that can immediately detect both a metabolite (glucose) or an infection (COVID-19) by non-invasively using Raman spectroscopy and machine learning. Aim: Current diagnostic testing for infections and glucose monitoring requires specimens, disease-specific reagents and processing, and it increases environmental waste. We propose a new hardware–software paradigm by designing and constructing a finger-scanning hardware device to acquire Raman spectroscopy readouts which, by varying the machine learning algorithm to interpret the data, allows for diverse diagnoses. Approach: A total of 455 patients were enrolled prospectively in the COVID-19 study; 148 tested positive and 307 tested negative through nasal PCR testing conducted concurrently with testing using our viral detector. The tests were performed on both outpatients (N = 382) and inpatients (N = 73) at Holy Name Medical Center in Teaneck, NJ, between June 2021 and August 2022. Patients’ fingers were scanned using an 830 nm Raman System and then, using machine learning, processed to provide an immediate result. In a separate study between April 2023 and August 2023, measurements using the same device and scanning a finger were used to detect blood glucose levels. Using a Dexcom sensor and an Accu-Chek device as references, a cross-validation-based regression of 205 observations of blood glucose was performed with a machine learning algorithm. Results: In a five-fold cross-validation analysis (including asymptomatic patients), a machine learning classifier using the Raman spectra as input achieved a specificity for COVID-19 of 0.837 at a sensitivity of 0.80 and an area under receiver operating curve (AUROC) of 0.896. However, when the data were split by time, with training data consisting of observations before 1 July 2022 and test data consisting of observations after it, the model achieved an AUROC of 0.67, with 0.863 sensitivity at a specificity of 0.517. This decrease in AUROC may be due to substantial domain shift as the virus evolves. A similar five-fold cross-validation analysis of Raman glucose detection produces an area under precision–recall curve (AUPR) of 0.58. Conclusions: The combination of Raman spectroscopy, AI/ML, and our patient interface admitting only a patient’s finger and using no specimen offers unprecedented flexibility in introducing new diagnostic tests or adapting existing ones. As the ML algorithm can be iteratively re-trained with new data and the software deployed to field devices remotely, it promises to be a valuable tool for detecting rapidly emerging infectious outbreaks and disease-specific biomarkers, such as glucose. Full article

Dehydration is known to affect the rate of electron transfer backreaction from the light-induced charge separation state P⁺Q_A⁻ to the neutral ground state PQ_A in photosynthetic bacterial Reaction Centers. On the other hand, a 20 s continuous illumination period has been demonstrated to induce (at 297 K) formation of one or more light-adapted states at different levels of dehydration; these light-adapted states are believed to be related to peculiar response(s) from the protein. In this work, we applied time-resolved rapid-scan FTIR difference spectroscopy to investigate the protein response under dehydrated conditions (RH = 11%) at 281 K both after a flash and under prolonged continuous illumination. Time-resolved FTIR difference spectra recorded after a laser flash show a protein recovery almost synchronous to the electron transfer backreaction P⁺Q_A⁻ → PQ_A. Time-resolved FTIR difference spectra recorded after 20.5 s of continuous illumination (RH = 11%, T = 281 K) surprisingly show almost the same kinetics of electron transfer back reaction compared to spectra recorded after a laser flash. This means that the mechanism of formation of a light-adapted stabilized state is less effective compared to the same hydration level at 297 K and to the RH = 76% hydration level (both at 281 K and 297 K). Time-resolved FTIR difference spectra after continuous illumination also suggest that the 1666 cm⁻¹ protein backbone band decays faster than marker bands for the electron transfer back reaction P⁺Q_A⁻ → PQ_A. Finally, FTIR double-difference spectra (FTIR difference spectrum recorded after 18.4 s illumination minus flash-induced FTIR difference spectrum) suggest that at RH = 11%, a light-adapted state different from the one observed at RH = 76% is formed. A possible interpretation is that at RH = 11%, the protein response is modified by the fact that only protons can move easily, differently from water molecules, as instead observed for RH = 76%. This probably makes the formation of a real light-adapted P⁺Q_A⁻ stabilized state at RH = 11% unfeasible. Full article

The change in the geometry of 1,3-dicyanobenzene upon electronic excitation to the lowest excited singlet state has been elucidated by simultaneous Franck–Condon (FC) fits of the fluorescence emission spectra originating from the vibrationless origin and from four vibronic bands. The geometry changes obtained from the FC fits were compared to the results of ab initio calculations at the SCS-CC2/cc-pVTZ level of theory. We found close agreement between the spectral determination and the theoretical prediction of the geometry changes upon excitation. The aromatic ring opens upon excitation, resulting in a symmetrically distorted structure in the excited state. Full article

Rare-earth doped transparent glass-ceramic waveguides are playing a very crucial role in integrated optics. We fabricated ZnO-HfO₂ hybrid nanocrystals embedded with 70 SiO₂–(30-x) HfO₂–x ZnO (x = 0, 2, 5 and 7 mol %) ternary transparent glass-ceramic waveguides doped with 1 mol % Eu-ions. The formation and size of the nanocrystals evolved with an increase in ZnO concentration in the glass-ceramic waveguides. In this context, key factors of such nanocrystals embedded active glass-ceramic waveguides were optical losses and transparency. A lab-built m-line experimental set-up was used for the characterization of the waveguides. On the other hand, optical gain measurements of the Eu-doped hybrid nanocrystals embedded glass-ceramic waveguides were performed using the variable stripe length method. The optical amplification of the waveguides was investigated on the red emission line (⁵D₀ → ⁷F₂) of Eu-ions pumped by a 532 nm laser in a stripe-like geometry generated by a cylindrical lens. Here, we report, the optical gain in rare-earth activated glass-ceramic waveguides with nanocrystals of varying sizes formed in the waveguides with increasing ZnO concentration. Full article

In this paper, methods for the determination of clopidogrel bisulphate and metamizole sodium in rinse waters from industrial equipment, using multiwavelength UV spectrometry and the calculation of areas under curves, are proposed. Spectra were recorded in an aqueous medium without preliminary pH adjustment. A numerical integration of the spectra was performed in the wavelength range of 210 to 290 nm for clopidogrel bisulphate, and 220 to 320 nm for metamizole sodium. The methods enable the determination of clopidogrel bisulphate and metamizole sodium in solution in the concentration range of 1–100 mg/L, do not require lengthy sample preparation and complex analytical equipment, and are suitable for the routine determination of these drugs in rinse waters from industrial equipment. Full article

Bulk 2D electronic–vibrational (2D-EV) and 2D vibrational–electronic spectroscopies (2D-VE) were previously developed to correlate the electronic and vibrational degrees of freedom simultaneously, which allow for the study of couplings between electronic and vibrational transitions in photo-chemical systems. Such bulk-dominated methods have been used to extensively study molecular systems, providing unique information such as coherence sensitivity, molecular configurations, enhanced resolution, and correlated states and their dynamics. However, the analogy of interfacial 2D spectroscopy has fallen behind. Our recent work presented interface-specific 2D-EV spectroscopy (i2D-EV). In this work, we develop interface-specific two-dimensional vibrational–electronic spectroscopy (i2D-VE). The fourth-order spectroscopy is based on a Mach–Zehnder IR interferometer that accurately controls the time delay of an IR pump pulse pair for vibrational transitions, followed by broadband interface second-harmonic generation to probe electronic transitions. We demonstrate step-by-step how a fourth-order i2D-VE spectrum of AP3 molecules at the air/water interface was collected and analyzed. The line shape and signatures of i2D-VE peaks reveal solvent correlations and the spectral nature of vibronic couplings. Together, i2D-VE and i2D-EV spectroscopy provide coupling of different behaviors of the vibrational ground state or excited states with electronic states of molecules at interfaces and surfaces. The methodology presented here could also probe dynamic couplings of electronic and vibrational motions at interfaces and surfaces, extending the usefulness of the rich data that are obtained. Full article

Local heating was performed on a thermoplastic polymer film by contact with the tip of a soldering iron heated above the glass-transition temperature. The locally heated area was measured using microscopic Raman scattering spectroscopy, and the spatial distribution of the crystallinity was obtained from the low-frequency peak. The crystallinity distribution can be evaluated using the microscale spatial resolution. The temperature distribution around the locally heated area was calculated by applying the heat conduction equation, and good correspondence was obtained with the obtained crystallinity. Full article

Industrial agriculture, while necessary to meet current food production needs, can have damaging effects on the environment and local water supply. For monitoring purposes, Raman spectra of common fertilizers in solution are measured and presented. Raman spectra of the fertilizer species combined with data from Inductively Coupled Plasma Emission Spectrometry (ICP-AES) is used to construct an empirical model of contaminant concentration. This work expands upon the authors’ prior work in Raman Spectroscopy of Common Fertilizers in Bulk and in Aqueous Solution, which was presented during the virtual sessions at OSA Optical Sensors and Sensing Congress in 2021 (AIS, FTS, HISE, SENSORS, ES). Full article

In order to improve the security of information encryption, this paper proposes a novel method based on laser-induced breakdown spectroscopy (LIBS) technology in conjunction with a commercial general-purpose inkjet printer. A “sandwich” model, comprising three layers of a black ink block, a blue ink layer containing encrypted information, and another black ink block in order to render the information layer undetectable by other conventional optical imagers, was proposed. Because of the lower resolution requirements and better error tolerance of the Quick Response (QR) code, it was used as encryption information carrier. The “sandwich” structure was printed onto original paper using a commercial inkjet printer. The spatial distribution of the “LIBS secret key” on the paper was analyzed by LIBS spectra at different locations. After baseline removal, normalization, and spectral superposition, the contrast of decrypted images is enhanced to extract hidden information effectively. This method has the advantages of high security, low cost, and simple fabrication. It provides a new method with a potential application prospect for LIBS in the field of information encryption. Full article

Metastasis in oncological diseases remains one of the main reasons for negative prognosis regarding treatment. Any new data on the biophysical and biochemical characteristics of circulating metastatic cells will help to develop a concept for antimetastatic therapy. In this study, we found a number of differences in the spectroscopic and morphological features of circulating metastatic cells. FT-IR and Raman spectra cultivated by adhesive and de-adhesive methods (with the latter used as a model for metastatic cells) have shown spectroscopic features, namely in FT-IR spectra in the region of CH stretching vibrations, which are associated with structural rearrangements in the cell membrane, as well as changes in the intensity and position of the PO₂⁻ group vibration bands correlated with proliferative activity. The spectral features in the regions of OH stretching and Amide I vibrations as well as other spectral markers of the metastatic cells grown under different cultivation conditions were derived. Raman spectra showed a redistribution of the amino acid Tyr/Trp (tryptophan to tyrosine) ratio and in Tyr doublet intensity in the region of 500–900 cm⁻¹, as well as varying glycogen levels in different cells. The spectroscopic markers are in accordance with biochemical data. CARS and confocal optical microscopy were applied to determine the state of the cells and the F-actin expression level, which turned out to be higher for adhesive cells in comparison with de-adhesive cells. The shape and the morphological properties of the cells differ drastically. The correlation of vibrational markers with biochemical data and the cytofluorometric method was discussed. Full article

Multicomponent gas mixture diffusion in a microscale confined flow in the transition gas regime at Knudsen numbers (Kn) above 0.1 has potential engineering applications in gas-phase microfluidics. Although the calculation of the diffusion coefficient accounts for the influence of the concentration of other species in a multicomponent gas mixture, the higher rate of gas-wall collision at 0.1 < Kn ≤ 10 introduces additional complications not predicted by conventional calculation methods. Thus, simultaneous measurement of diffusion coefficients for multiple gas species ensures accurate estimation of the diffusion coefficient of a particular species that includes the effect of interactions with other species and wall surface conditions in a multicomponent gas mixture at Kn > 0.1. However, most experimental methods for measuring the diffusion coefficient are not species-specific and therefore cannot directly differentiate between the species diffusing in a gas mixture. Thus, this paper demonstrates a new experiment methodology consisting of a two-bulb diffusion configuration accompanied by a tunable diode laser absorption spectroscopy detection technique for species-specific, in-situ, simultaneous measurement of the effective diffusion coefficient for a CO₂-N₂O gas mixture in the transition gas regime. The experimental results are compared against direct simulation Monte Carlo calculations and the Bosanquet approximation showing a deviation that has not been reported in the literature before. Full article

2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a molecule widely employed as a very effective p-dopant of semi-conducting polymers, such as poly(3-hexylthiophene-2,5-diyl) (P3HT). The CN stretching transitions of F4TCNQ are exceptionally sensitive to the charge state of the molecule, thus allowing the doping diagnosis via IR spectroscopy. Less pronounced frequency shifts can reveal characteristics of the intermolecular environment. We present a systematic study based on Density Functional Theory (DFT) calculations and on experiments aimed at exploring how different factors, such as the charge state and the environment, modify the vibrational spectra of F4TCNQ. While several effects on the vibrational frequencies are well known and have been thoroughly investigated in the past, this study focuses on the infrared intensities of the CN stretching modes and reveals that they are strongly affected both by the charge state of the molecule and by the surrounding medium: it is then mandatory to consider such remarkable intensity modulation for any quantitative diagnosis based on spectroscopic measurements, e.g., concerning the number of F4TCNQ molecules involved in the formation of charge transfer complexes. Full article

Spectroscopic techniques have emerged as crucial tools in the field of malaria research, offering immense potential for improved diagnosis and enhanced understanding of the disease. This review article pays tribute to the pioneering contributions of Professor Henry Mantsch in the realm of clinical biospectroscopy, by comprehensively exploring the diverse applications of spectroscopic methods in malaria research. From the identification of reliable biomarkers to the development of innovative diagnostic approaches, spectroscopic techniques spanning the ultraviolet to far-infrared regions have played a pivotal role in advancing our knowledge of malaria. This review will highlight the multifaceted ways in which spectroscopy has contributed to the field, with a particular emphasis on its impact on diagnostic advancements and drug research. By leveraging the minimally invasive and highly accurate nature of spectroscopic techniques, researchers have made significant strides in improving the detection and monitoring of malaria parasites. These advancements hold the promise of enhancing patient outcomes and aiding in the global efforts towards the eradication of this devastating disease. Full article

Fluorinated organic compounds have demonstrated remarkable utility in medicinal chemistry due to their enhanced metabolic stability and potent therapeutic efficacy. Several examples exist of fluorinated non-steroidal anti-inflammatory drugs (NSAIDs), including diflunisal, flurbiprofen, and trifluoromethylated pyrazoles celecoxib and mavacoxib. These trifluoromethylated pyrazoles, which are most commonly constructed through the cyclocondensation of a trifluorinated 1,3-dicarbonyl and an aryl hydrazine, are also found in numerous other drug candidates. Here, we interrogate the effects of solvents and the presence of Brønsted or Lewis acid catalysts on catalyzing this process. We highlight the utility of benchtop ¹⁹F NMR spectroscopy in enabling the real-time quantification of reaction progress and the identification of fluorinated species present in crude reaction mixtures without the need for cost-prohibitive deuterated solvents. Ultimately, we find that the reaction solvent has the greatest impact on the rate and product yield, and also found that the relationship between the keto-enol equilibrium of the dicarbonyl starting material pyrazole formation rate is highly solvent-dependent. More broadly, we describe the optimization of the yield and kinetics of trifluoromethylpyrazole formation in the synthesis of celecoxib and mavacoxib, which is made possible through high-throughput reaction screening on benchtop NMR. Full article