Spectroscopy System Research Articles

Are We There Yet? Is There Such a Thing as an Expert Calibration System for Vibrational Spectroscopy?

The development of an expert calibration system (ECS) for spectroscopic-based process analytical chemistry would be a significant advancement aimed at automating the creation of high-quality calibration models for standard zero-order and first-order calibrations as well as multidimensional imaging applications. The concept of ECS would seek to reduce the reliance on users’ extensive knowledge of chemometrics all the while leveraging their domain knowledge and understanding of specific sample physical and chemical properties. By providing automated tools and guidance, an ECS would aim to streamline the calibration process, improve calibration transfer, enhance operator efficiency, and improve the overall consistency and reliability of analytical results produced using advanced chemometrics and machine earning techniques. In this article, we resurrect the discussion from nearly three decades ago.

Orbits and Dynamical Masses for Six Binary Systems in the Hyades Cluster

We report long-baseline interferometric observations with the CHARA Array that resolve six previously known double-lined spectroscopic binary systems in the Hyades cluster, with orbital periods ranging from 3 to 358 days: HD 27483, HD 283882, HD 26874, HD 27149, HD 30676, and HD 28545. We combine those observations with new and existing radial-velocity measurements, to infer the dynamical masses for the components as well as the orbital parallaxes. For most stars, the masses are determined to be better than 1%. Our work significantly increases the number of systems with mass determinations in the cluster. We find that, while current models of stellar evolution for the age and metallicity of the Hyades are able to reproduce the overall shape of the empirical mass–luminosity relation, they overestimate the V-band fluxes by about 0.1 mag between 0.5 and 1.4 M ⊙. The disagreement is smaller in H, and near zero in K, and depends somewhat on the model. We also make use of the TESS light curves to estimate rotation periods for our targets, and detect numerous flares in one of them (HD 283882), estimating an average flaring rate of 0.44 events per day.

Visible core spectroscopy at Wendelstein 7-X.

This paper presents an overview of recent hardware extensions and data analysis developments to the Wendelstein 7-X visible core spectroscopy systems. These include upgrades to prepare the in-vessel components for long-pulse operation, nine additional spectrometers, a new line of sight array for passive spectroscopy, and a coherence imaging charge exchange spectroscopy diagnostic. Progress in data analysis includes ion temperatures and densities from multiple impurity species, a statistical comparison with x-ray crystal spectrometer measurements, neutral density measurements from thermal passive Balmer-alpha emission, and a Bayesian analysis of active hydrogen emission, which is able to infer electron density and main ion temperature profiles.

Design of a multichannel vacuum ultraviolet spectroscopy system for SPARC.

The design of a vacuum ultraviolet spectroscopy system has been performed to monitor and provide feedback for impurity control in SPARC. The spectrometer, covering a wavelength range of 10-2000Å through a flat-field configuration with diffraction gratings, incorporates five survey lines of sight. This allows for comprehensive impurity analysis across the core and four divertor regions (inner/outer and upper/lower). Its compact modular design facilitates vertical stacking of each spectrometer unit, significantly reducing space in the tokamak hall, where a dedicated radiation shielding bunker will be built. Safety features include a secondary helium enclosure to mitigate tritium permeation risks during deuterium-tritium (D-T) operations and shielding within the beamlines for enhanced radiation protection. The silicon carbide mirror design for divertor observation ensures its survivability in the in-vessel environment of SPARC, validated by thermal and electromagnetic analysis. Signal modeling and data acquisition testing results show that an exposure time of a few milliseconds is appropriate considering photon flux reaching the detector, demonstrating the system's capability for discharge control that includes disruption avoidance.

Miniaturized spectroscopy system based on a semiconductor nanofilm

Abstract Spectroscopy plays a pivotal role in various applications for industrial and commercial analysis. Conventional spectroscopy instruments include various discrete optical components like light sources, monochromators and detectors. These components are mechanically intricate and require space for the mechanisms that adjust and calibrate them, which increases the instrument’s footprint and make them less adjustable for portable applications. This drawback initiated the increase in the demand for miniatured spectral detection systems. Here, we present a low-cost ultra-compact miniaturized spectral detection system, which integrates both linear variable light sources, sample chambers and detectors within a centimetre-scale chip. The linear variable light generation across wavelengths ranging from 480 nm to 600 nm is achieved by stimulating different regions of the ZnCdSeS bandgap-graded semiconductor nanofilm with ultraviolet light. We demonstrate the capability of the system with precise identification of liquids. Our device overcomes the typical miniaturization limits imposed by discrete optical components, and long light paths in conventional spectroscopy instruments and opens up numerous potential applications across various fields due to its portability, ease of use, and lower cost.

Determination of soluble solids content in loquat using near-infrared spectroscopy coupled with broad learning system and hybrid wavelength selection strategy

Soluble solids content (SSC) serves as a crucial metric in assessing loquat quality. To achieve fast, non-destructive, and accurate detection of SSC, the combination of near-infrared (NIR) spectroscopy and broad learning system (BLS) model was developed in this study. Meanwhile, the influence of six spectral preprocessing methods and six wavelength selection algorithms on SSC prediction was explored, and the performance of the BLS model was compared with the widely used partial least squares regression (PLSR) and least squares support vector machine (LS-SVM) models. The results showed that Savitzky-Golay smoothing combined with standard normal transformation (SG-SNV) offered the optimal pretreatment, and the hybrid method, namely interval variable iterative space shrinking analysis and successive projections algorithm (iVISSA-SPA), emerged as the most effective wavelength selection method. The BLS model outperformed both PLSR and LS-SVM models. Specifically, the BLS model based on the iVISSA-SPA method achieved the optimal SSC prediction results, with RP2 = 0.8646, RMSEP = 0.5104, and RPD = 2.7481. Therefore, NIR spectroscopy coupled with the BLS model and hybrid wavelength selection strategy could rapidly, non-destructively and accurately detect the SSC of loquat, providing a viable alternative for SSC prediction in fruit.

Design of an Optimized Terahertz Time-Domain Spectroscopy System Pumped by a 30 W Yb:KGW Source at a 100 kHz Repetition Rate with 245 fs Pulse Duration

Ytterbium laser sources are state-of-the-art systems that are increasingly replacing Ti:Sapphire lasers in most applications requiring high repetition rate pulse trains. However, extending these laser sources to THz Time-Domain Spectroscopy (THz-TDS) poses several challenges not encountered in conventional, lower-power systems. These challenges include pump rejection, thermal lensing in nonlinear media, and pulse durations exceeding 100 fs, which consequently limit the detection bandwidth in TDS applications. In this article, we describe our design of a THz-TDS beamline that seeks to address these issues. We report on the effectiveness of temperature controlling the Gallium Phosphide (GaP) used to generate the THz radiation and its impact on increasing the generation efficiency and aiding pump rejection while avoiding thermal distortions of the residual pump laser beam. We detail our approach to pump rejection, which can be implemented with off-the-shelf products and minimal customization. Finally, we describe our solution based on a commercial optical parametric amplifier to obtain a temporally compressed probe pulse of 55 fs duration. Our study will prove useful to the increasing number of laboratories seeking to move from the high-energy, low-power THz time-domain spectroscopy systems based on Ti:Sapphire lasers, to medium-energy, high-power systems driven by Yb-doped lasers.

Reliability of brain metrics derived from a Time-Domain Functional Near-Infrared Spectroscopy System

With the growing interest in establishing brain-based biomarkers for precision medicine, there is a need for noninvasive, scalable neuroimaging devices that yield valid and reliable metrics. Kernel’s second-generation Flow2 Time-Domain Functional Near-Infrared Spectroscopy (TD-fNIRS) system meets the requirements of noninvasive and scalable neuroimaging, and uses a validated modality to measure brain function. In this work, we investigate the test-retest reliability (TRR) of a set of metrics derived from the Flow2 recordings. We adopted a repeated-measures design with 49 healthy participants, and quantified TRR over multiple time points and different headsets—in different experimental conditions including a resting state, a sensory, and a cognitive task. Results demonstrated high reliability in resting state features including hemoglobin concentrations, head tissue light attenuation, amplitude of low frequency fluctuations, and functional connectivity. Additionally, passive auditory and Go/No-Go inhibitory control tasks each exhibited similar activation patterns across days. Notably, areas with the highest reliability were in auditory regions during the auditory task, and right prefrontal regions during the Go/No-Go task, consistent with prior literature. This study underscores the reliability of Flow2-derived metrics, supporting its potential to actualize the vision of using brain-based biomarkers for diagnosis, treatment selection and treatment monitoring of neuropsychiatric and neurocognitive disorders.

Label-free detection of inclusion body formation in E. coli with application of terahertz

Extensive production of recombinant protein is essential for use in various fields. Bacterial cells, especially the Escherichia coli (E. coli) expression system, are widely used for the production of recombinant proteins due to their advantages in time and cost. However, the formation of inclusion bodies (IBs) caused by the production of recombinant protein is a significant issue. Therefore, a precise tool for the detection of IBs is in high demand. In this study, we demonstrated a label-free and rapid sensing platform for the detection of IBs formation in E. coli using terahertz-time domain spectroscopy (THz-TDS) system and terahertz metamaterials. The detection was based on the local polarity difference between E. coli samples with induced (positive) and non-induced (negative) protein overexpression. The formation of IBs in positive samples resulted in a decrease in local polarity compared to negative samples. This local polarity difference, strongly related to intermolecular interactions, influenced THz absorption as the THz regime involves weak intermolecular vibrational modes. Experimental results showed that the THz transmittance (ΔT) and resonance frequency shift (Δf) were significantly different between positive and negative samples, confirming the effectiveness of our method. Specifically, positive samples exhibited a ΔT value of 26.57% and a Δf value of 0.12 THz, while negative samples showed a ΔT value of 31.83% and a Δf value of 0.14 THz. These results highlight the capability of our platform to detect IBs rapidly and accurately.

The Time Course of Changes in Prefrontal Cortex Activity During Walking in People With Parkinson’s Disease

Background Walking abnormalities in people with Parkinson’s disease (PD) are characterized by a shift in locomotor control from healthy automaticity to compensatory, executive control, mainly located in the prefrontal cortex (PFC). Although PFC activity during walking increases in people with PD, the time course of PFC activity during walking and its relationship to clinical or gait characteristics is unknown. Objective To identify the time course of PFC activity during walking in people with PD. To investigate whether clinical or gait variables would explain the PFC activity changes. Methods Thirty-eight people with PD tested OFF medication wore a portable, functional near-infrared spectroscopy (fNIRS) system to record relative PFC activity while walking. Wearable inertial sensors recorded spatiotemporal gait characteristics. Based on the PFC activity (fNIRS) in the late phase of the walking task (final 40 seconds), compared to the early phase (initial 40 seconds), participants were separated into 2 groups: reduced or sustained PFC activity. Results People with PD who reduced PFC activity during walking had less impaired gait (eg, faster gait speed) than those who had a sustained increase in PFC activity (P < .05). Cognitive set-shifting ability explained 18% of the PFC activation in the group with a sustained increase in PFC activity (P = .033). Conclusions The time course of reduction in PFC activity corresponds to less impaired gait performance in people with PD, while a sustained increase in PFC activity is related to worse cognitive flexibility. Reduction in PFC activity while walking may indicate a less impaired, automatic control of walking.

Fiberoptic Laser-Induced Breakdown Spectroscopy System for in situ Measurement in a Hazardous Environment

We report the development of a novel fiberoptic laser-induced breakdown spectroscopy (FOLIBS) system for material characterization applications. The system utilizes a 1000-µm optical fiber to transport the laser beam to remote locations for elemental analysis via laser-induced breakdown spectroscopy. Air-fiber interface damage, internal damage, and air breakdown issues during laser-fiber coupling are identified and corresponding solutions are presented. For evaluating the physical properties of the plasma generated by the FOLIBS system, spectroscopic characterization is carried out using a titanium sample. The spectral features collected from a natural uranium sample are also presented. Hence, this rapid, remote, and flexible measurement technique is promising for in situ measurements in hazardous environments in nuclear energy, nuclear safeguards, and nonproliferation applications.

High-Throughput Raman Spectroscopy by Horizontally Shifted Collection Fibers.

Optical fiber probe-based Raman spectroscopy systems are widely used for in situ measurements ranging from material characterization to biomedical applications. However, small Raman cross sections necessitate the use of high-power lasers or long exposure times that limit Raman's larger application to multiple research fields. This limitation can be overcome by collecting more Raman photons through additional collection fibers with taller detectors. This system configuration requires replacement of the detector and modification of the spectrograph to incorporate larger optical components, making it a costly and cumbersome option. In probe-based Raman systems, a typical detector image shows stacked collection fibers on the vertical axis and Raman spectra on the horizontal axis. While the vertical pixels are fully packed with multiple collection fibers, horizontal pixels have broad silent regions due to the narrow bandwidth of Raman peaks, potentially wasting valuable detector pixels. Here, we propose a new approach utilizing horizontally shifted collection fibers rather than vertically stacked ones. We designed and fabricated a novel collection fiber bundle that has horizontally shifted optical fibers in two vertical lines at the spectrograph entrance. This custom-made fiber bundle was incorporated into the imaging spectrograph to provide multiple horizontally shifted spectra on the detector. Through deconvolution, the original spectra can be recovered with an improved detection limit from greater photon collection. We demonstrate an enhanced limit of detection on various bioanalytes, such as glucose, urea, and lactate. Further, we applied the probe to measure tissue Raman spectra and successfully decomposed them into basis spectra, demonstrating the potential application of high-throughput in vivo tissue diagnosis. Our approach provides a simple, cost-effective, and universal method to increase the throughput without modifying existing Raman spectrometers.

Investigating cortical hypoxia in multiple sclerosis via time-domain near-infrared spectroscopy.

Hypoperfusion and tissue hypoxia have been implicated as contributory mechanisms in the neuropathology of multiple sclerosis (MS). Our objective has been to study cortical oxygenation in vivo in patients with MS and age-matched controls. A custom, multiwavelength time-domain near-infrared spectroscopy system was developed for assessing tissue hypoxia from the prefrontal cortex. A cross-sectional case-control study was undertaken assessing patients with secondary progressive MS (SPMS) and age-matched controls. Co-registered magnetic resonance imaging was used to verify the location from which near-infrared spectroscopy data were obtained through Monte Carlo simulations of photon propagation. Additional clinical assessments of MS disease severity were carried out by trained neurologists. Linear mixed effect models were used to compare cortical oxygenation between cases and controls, and against measures of MS severity. Thirty-three patients with secondary progressive MS (median expanded disability status scale 6 [IQR: 5-6.5]; median age 53.0 [IQR: 49-58]) and 20 age-matched controls were recruited. Modeling of photon propagation confirmed spectroscopy data were obtained from the prefrontal cortex. Patients with SPMS had significantly lower cortical hemoglobin oxygenation compared with controls (-6.0% [95% CI: -10.0 to -1.9], P = 0.004). There were no significant associations between cortical oxygenation and MS severity. Using an advanced, multiwavelength time-domain near-infrared spectroscopy system, we demonstrate that patients with SPMS have lower cortical oxygenation compared with controls.

Multimodal analysis of cortical activation in young male adults with internet gaming disorder: A resting state EEG-fNIRS study

BackgroundInternet gaming disorder (IGD) has become increasingly prevalent worldwide and is recognized as a significant public health concern because of its negative consequences on individuals mental and physical health, social relationships, academic performance and overall well-being. While research on IGD has gained significant momentum in the past decade, the neural substrates underlying this disorder remains unclear. This study aims to investigate resting-state cortical activation in male subjects with IGD using a concurrent functional near infrared spectroscopy (fNIRS) and electroencephalography (EEG) hybrid system. MethodsTwenty-two male individuals with IGD (18–23 years old) and twenty-two male healthy, age-matched healthy controls were included in the study. Mean oxygenation of the prefrontal cortex (PFC) and whole head neural activity were measured using fNIRS and EEG respectively, during eyes-open and eyes-closed conditions at the resting state. EEG signals were decomposed into distinct frequency sub-bands with wavelet transform, followed by the analysis of the power spectral density within each band. Mean oxygenation of PFC is measured using a multichannel fNIRS system. ResultsResults revealed that the individuals with IGD had significantly higher beta power in the frontal region compared to the control group. Individuals with IGD showed significantly increased PFC oxygenation compared to healthy controls. Additionally, both frontal beta power and PFC oxygenation were significantly correlated with IGD severity. However, there were no significant correlations observed between oxygenation and beta powers. ConclusionThis study is the first to examine resting-state cortical activation using multimodal EEG-fNIRS system in young adults with IGD. Moreover, it provides an important contribution to the understanding of the underlying neural mechanisms of IGD and offer new insights for the diagnosis and intervention of the disorder using multimodal EEG-fNIRS system. Further studies should aim to replicate the findings of this study using a larger and more culturally diverse sample to support the neurophysiological basis of IGD.

Dual-Task Effect on Center of Pressure Oscillations and Prefrontal Cortex Activation Between Young and Older Adults

ABSTRACT Purpose: This study aimed to investigate the dual-task effect on conventional center of pressure (CoP) outcomes, CoP oscillations, and prefrontal cortex (PFC) activation between young and older adults. Methods: Fourteen healthy older adults (age: 66.25 ± 3.43 years) and another fourteen gender-matched young adults (age: 19.80 ± 0.75 years) participated in this study. Participants completed single-task and dual-task standing trials in a fixed order. The displacement of CoP and PFC activation were recorded using a Force plate and a functional near-infrared spectroscopy system, respectively. Two-way MANOVAs were used to examine the group and task effects. Additionally, the Pearson correlation analyses were used to investigate the relationship between CoP oscillations and PFC activation. Results: Our results showed a worse balance performance, greater CoP oscillations of 0–0.1 (11.03 ± 8.24 vs. 23.20 ± 12.54 cm2) and 0.1–0.5 (13.62 ± 9.30 vs. 30.00 ± 23.12 cm2) Hz in the medial-lateral direction and higher right (dorsomedial: −0.0003 ± 0.021 vs. 0.021 ± 0.021 & ventrolateral: 0.0087 ± 0.047 vs. 0.025 ± 0.045 mol/ml) and left (dorsomedial: 0.0033 ± 0.024 vs. 0.020 ± 0.025 & ventrolateral: 0.0060 ± 0.037 vs. 0.034 ± 0.037 mol/ml) PFC activation in response to a secondary cognitive task in older adults (p < .05). Older adults also showed significant positive correlations between CoP oscillations in the anterior-posterior direction and PFC activation under the single-task standing. Conclusion: These results suggest that older adults presented a loss of postural automaticity contributing to cognitive dysfunction. Moreover, heightened CoP oscillations at 0–0.5 Hz in response to a secondary cognitive task could provide evidence of a loss of automaticity, which might be associated with a greater reliance on the sensory inputs.

Design of water vapor spectroscopy system for Raman Lidar based on sampled fiber Bragg grating

Design of water vapor spectroscopy system for Raman Lidar based on sampled fiber Bragg grating

Basic research for identification and classification of organophosphorus pesticides in water based on ultraviolet-visible spectroscopy information.

In this study, the goal was to develop a method for detecting and classifying organophosphorus pesticides (OPPs) in bodies of water. Sixty-five samples with different concentrations were prepared for each of the organophosphorus pesticides, namely chlorpyrifos, acephate, parathion-methyl, trichlorphon, dichlorvos, profenofos, malathion, dimethoate, fenthion, and phoxim, respectively. Firstly, the spectral data of all the samples was obtained using a UV-visible spectrometer. Secondly, five preprocessing methods, six manifold learning methods, and five machine learning algorithms were utilized to build detection models for identifying OPPs in water bodies. The findings indicate that the accuracy of machine learning models trained on data preprocessed using convolutional smoothing + first-order derivatives (SG + FD) outperforms that of models trained on data preprocessed using other methods. The backpropagation neural network (BPNN) model exhibited the highest accuracy rate at 99.95%, followed by the support vector machine (SVM) and convolutional neural network (CNN) models, both at 99.92%. The extreme learning machine (ELM) and K-nearest neighbors (KNN) models demonstrated accuracy rates of 99.84% and 99.81%, respectively. Following the application of a manifold learning algorithm to the full-wavelength data set for the purpose of dimensionality reduction, the data was then visualized in the first three dimensions. The results demonstrate that the t-distributed domain embedding (t-SNE) algorithm is superior, exhibiting dense clustering of similar clusters and clear classification of dissimilar ones. SG + FD-t-SNE-SVM ranks highest among the feature extraction models in terms of performance. The feature extraction dimension was set to 4, and the average classification accuracy was 99.98%, which slightly improved the prediction performance over the full-wavelength model. As shown in this study, the ultraviolet-visible (UV-visible) spectroscopy system combined with the t-SNE and SVM algorithms can effectively identify and classify OPPs in waterbodies.

Label-Free Assessment of Neuronal Activity Using Raman Micro-Spectroscopy.

Given the pivotal role of neuronal populations in various biological processes, assessing their collective output is crucial for understanding the nervous system's complex functions. Building on our prior development of a spiral scanning mechanism for the rapid acquisition of Raman spectra from single cells and incorporating machine learning for label-free evaluation of cell states, we investigated whether the Paint Raman Express Spectroscopy System (PRESS) can assess neuronal activities. We tested this hypothesis by examining the chemical responses of glutamatergic neurons as individual neurons and autonomic neuron ganglia as neuronal populations derived from human-induced pluripotent stem cells. The PRESS successfully acquired Raman spectra from both individual neurons and ganglia within a few seconds, achieving a signal-to-noise ratio sufficient for detailed analysis. To evaluate the ligand responsiveness of the induced neurons and ganglia, the Raman spectra were subjected to principal component and partial least squares discriminant analyses. The PRESS detected neuronal activity in response to glutamate and nicotine, which were absent in the absence of calcium. Additionally, the PRESS induced dose-dependent neuronal activity changes. These findings underscore the capability of the PRESS to assess individual neuronal activity and elucidate neuronal population dynamics and pharmacological responses, heralding new opportunities for drug discovery and regenerative medicine advancement.

Terahertz Spectra of Mannitol and Erythritol: A Joint Experimental and Computational Study.

Sugar substitutes, which generally refer to a class of food additives, mostly have vibration frequencies within the terahertz (THz) band. Therefore, THz technology can be used to analyze their molecular properties. To understand the characteristics of sugar substitutes, this study selected mannitol and erythritol as representatives. Firstly, PXRD and Raman techniques were used to determine the crystal structure and purity of mannitol and erythritol. Then, the THz time-domain spectroscopy (THz-TDS) system was employed to measure the spectral properties of the two sugar substitutes. Additionally, density functional theory (DFT) was utilized to simulate the crystal configurations of mannitol and erythritol. The experimental results showed good agreement with the simulation results. Finally, microfluidic chip technology was used to measure the THz spectroscopic properties of the two sugar substitutes in solution. A comparison was made between their solid state and aqueous solution state, revealing a strong correlation between the THz spectra of the two sugar substitutes in both states. Additionally, it was found that the THz spectrum of a substance in solution is related to its concentration. This study provides a reference for the analysis of sugar substitutes.

Charge exchange recombination spectroscopy on the alkali beam of Wendelstein 7-X.

Measurements of ion temperature profiles are required to assess the energy and particle transport processes in the Wendelstein 7-X stellarator. This device is equipped with a diagnostic alkali beam, which can be utilized to determine local impurity temperatures and densities by Charge Exchange Recombination Spectroscopy (CXRS). It could provide such profiles in the edge plasma, where other diagnostics are less efficient. With this contribution, first results of CXRS measurements on the sodium beam from the scientific operation phase OP2.1 are presented. The spectroscopic system was in commissioning phase lacking some of the final optical components. Thus, the aim of the diagnostics during this campaign was to explore the measurement capabilities. Based on the processed spectra, the prospects of C5+ and C6+ ion temperature and concentration measurements are discussed. The results indicate that with the final optical setup under installation, the diagnostics could provide ion temperature profiles in the edge with 3mm radial resolution and at least 1s temporal resolution.