Spectral Region Research Articles

Enhanced data point importance: Layered significance of variables in multivariate calibration

BackgroundThe Enhanced Data Point Importance (EDPI) method, a systematic approach for evaluating the importance of data points in multivariate calibration, is introduced. Factor decomposition methods allow for the evaluation of the impact of variables on maintaining the structural pattern of data in the abstract space. Essential data points play a key role in these patterns and the method of Data Point Importance (DPI) aims to evaluate the essential data points in terms of their importance. All other points are rated by zero. In this contribution, DPI is extended to include inner points to evaluate the importance of these points in the absence of the essential points. The EDPI method employs convex peeling to sort data points systematically. ResultsEDPI method was applied to near-infrared and Raman spectroscopy data sets, including corn and alcohol mixtures and simulated data, to rank and select important variables. EDPI effectively identified variables that contributed to the preservation of the data structure and highlighted key spectral regions with different degrees of selectivity. In the alcohol dataset, EDPI revealed important physicochemical insights by focusing on specific regions where non-analytes spectra overlapped. It performed in a similar way to the Variable Importance in Projection (VIP) method, but with fewer variables selected. SignificanceThe experimental results obtained from calibrating near-infrared and Raman spectroscopic datasets using partial least squares highlight the effectiveness of the proposed EDPI strategy when contrasted with the conventional variable importance in projection (VIP) method for variable selection.

Applying Computational Spectroscopy Methods to Raman Spectra of Dicationic, Imidazolium-Based, Ionic Liquids.

Studying ionic liquids (ILs) through computational methods is one of the ways to accelerate progress in the design of novel and potentially green materials optimized for task-specific applications. Therefore, it is essential to develop simple and cost-effective computational procedures that are able to replicate and predict experimental data. Among these, spectroscopic measurements are of particular relevance since they are often implicated in structure-property relationships, especially in the infrared spectral region, where characteristic absorption and scattering processes due to molecular vibrations are ultimately influenced by the surrounding environment in the condensed phase. In this frame, we validate, vis-à-vis experimental data, an efficient theoretical method to compute the Raman spectra in the liquid phase of four especially synthesized dicationic ionic liquids and to assess the conformational cation/anion contributions to the experimental bands. The computational procedure is based on the assessment of the most probable conformations as evaluated by a computational protocol involving both molecular dynamics and ab initio methods.

Tailoring Ruthenium(II) and Rhenium(I) Complexes for Turn-On Luminescent Sensing of Antimony(III)

Antimony (Sb) is currently a widespread element with key roles in telecommunication, sustainable energy, and military industries, among others. Its significant toxicity determines the need to realize sensors for water, air, and soil and the industrial process monitoring of Sb species. Unfortunately, no antimony sensors exist so far, and just laboratory analysis methods are in use. We aimed to contribute to the development of optical sensors for the metalloid by tailoring, for the first time, luminescent Ru(II) and Re(I) polypyridyl complexes to probe and quantify the presence of Sb(III). The molecular design of the complexes includes the multifunctional Sb-binding 2-(2,2′-bithien-5-yl)-1H-imidazo[4,5-f]-1,10-phenanthroline (btip) ligand that ensures the molecular binding of Sb(III) in organic media. The Ru(II)-btip complex is additionally endowed with one 2,2′-bipyrazine (bpz) or two 1,4,5,8-tetraazaphenanthrene (tap) ligands, namely [Ru(bpz)(btip)2]2+ and [Ru(tap)2(btip)]2+, that boost the excited state oxidation potential of the probe, leading to an intramolecular photoinduced electron transfer from btip to the Ru(II) core. The latter is suppressed upon interaction with Sb(III), leading to an 11-fold increase in both the luminescence intensity and lifetime of [Ru(bpz)(btip)2]2+ in the presence of ca. 50 μmol L−1 of SbCl3 in organic medium. The fluorescence intensity of [Re(CO)3(H2O)(btip)]+ also increases upon interaction with Sb(III) but to a much lesser extent due to the intraligand π*→π nature of its emission compared to the Ru(II) ligand-to-metal excited state deactivation. However, the weak π*→d emission band in the red spectral region of the former is quenched by the semimetallic element. The sensing mechanisms of the Ru(II)- and Re(I)-btip probes that allow luminescence intensity (Ru, Re), ratiometric (Ru), and lifetime measurements (Ru) are compared and discussed in this initial solution sensing study.

Use of deperturbed and generalized second-order vibrational perturbation theories to study vibrational spectra intensity and the role of cubic force constant and total anharmonic matrix contributions to anharmonicity: [formula omitted]-thujone and S-camphor

Herein, we employ deperturbed second-order vibrational perturbation theory (DVPT2) and generalized VPT2 (GVPT2) methodologies to predict and analyze two distinct spectral regions in the infrared, VCD, and Raman spectra of α-thujone and S-camphor. The first spectral region spans from 3200 to 2900 cm−1, while the second region extends from 1800 to 500 cm−1. We aim to introduce and validate a program for the simultaneous analysis of vibrational spectra intensity in medium-sized molecules using GVPT2 and DVPT2. Furthermore, employing a graphical presentation (heat map) to illustrate the important contribution of cubic force constant and χ-matrix to anharmonicity.

CHARACTERISATION OF THE RESPONSE OF PRE-CLINICAL MODELS OF GLIOMA TO METABOLIC THERAPIES USING IN VIVO MAGNETIC RESONANCE SPECTROSCOPY

Abstract AIMS Magnetic resonance imaging (MRI) is routinely used to diagnose and monitor brain tumours. Magnetic resonance spectroscopy (MRS) allows us to record the metabolic profile of tumours in situ. This provides a non-invasive method to monitor the response of tumours to metabolic therapies. We aimed to characterise the response of pre-clinical models of glioma to metabolic therapies such as arginine deprivation and the ketogenic diet (KD) by MRS, to better understand what metabolic changes are occurring in the tumour. METHOD We performed orthotopic injection of three different cell lines, including the syngeneic models GL261 and CT2A, as well as a primary GBM cell line, into the striatum of C57BL/6 and athymic nude mice respectively. Mice were randomised to either arginine deprivation treatment using pegylated arginine deiminase (ADI), or KD, plus controls. In each animal, we collected single voxel MRS data using STEAM on both the tumour itself, and healthy brain. MRS data was exported in jMRUI format and analysed in R using the spant package, followed by PCA and OPLS-DA. RESULTS PCA showed that there is clear distinction between healthy and tumour spectra across all models. OPLS-DA indicated that the lipid and choline spectral regions were significantly associated with tumour, whereas the NAA and glutamine/glutamate regions were significantly associated with healthy brain. Integration of specific peaks associated with these metabolites confirmed these results. Subset analysis indicated distinct metabolic signatures between the syngeneic models and the primary GBM model. Furthermore, there is evidence to suggest that tumours in animals treated with arginine deprivation have a unique metabolic signature. CONCLUSION This data indicates that the tumour specific response to metabolic therapies can be measured by routine MRS screening. This would allow a non-invasive method by which clinicians could monitor the effectiveness of metabolic therapies in patients with gliomas.

Dressing AgNWs with MXenes Nanosheets: Transparent Printed Electrodes Combining High-Conductivity and Tunable Work Function for High-Performance Opto-Electronics.

High-work function transparent electrodes (HWFTEs) are key for establishing Schottky and Ohmic contacts with n-type and p-type semiconductors, respectively. However, the development of printable materials that combine high transmittance, low sheet resistance, and tunable work function remains an outstanding challenge. This work reports a high-performance HWFTE composed of Ag nanowires enveloped conformally by Ti3C2Tx nanosheets (TA), forming a shell-core network structure. The printed TA HWFTEs display an ultrahigh transmittance (>94%) from the deep-ultraviolet (DUV) to the entire visible spectral region, a low sheet resistance (<15 Ωsq-1), and a tunable work function ranging from 4.7 to 6.0eV. The introduction of additional oxygen terminations on the Ti3C2Tx surface generates positive dipoles, which not only increases the work function of the TA HWFTEs but also elevates the TA/Ga2O3 Schottky barrier, resulting in a high self-powered responsivity of 18mAW-1 in Ga2O3 diode DUV photodetectors, as demonstrated via experimental characterizations and theoretical calculations. Furthermore, the TA HWFTEs-based organic light-emitting transistors exhibit exceptional emission brightness of 5020cd m-2, being four-fold greater than that in Au electrodes-based devices. The innovative nano-structure design, work function tuning, and the revealed mechanisms of electrode-semiconductor contact physics constitute a substantial advancement in high-performance optoelectronic technology.

Study on UV-VIS characteristics of Aluminum Zinc Oxide nanoparticles through manganese substitution using Wemple-Di domenico method and diffuse reflectance spectroscopy

In this research Manganese-substitution impact on linear and nonlinear (NL) optical properties of Aluminum-doped ZnO (AlZnO) Nanoparticles (NPs) are investigated. Utilizing measured data of reflectance acquired from the DRS, the higher-order NL optical characteristics of the provided NPs are examined. The maximum quantity of NL susceptibility χ3 is measured to be around 3.945 × 10−10 esu at wavelength λ = 520 nm and 7.467 × 10−11 esu at wavelength λ = 530 nm for AlZnO and Manganese-substituted Aluminum-doped Zinc-Oxide (Mn-also) NPs, for particle sizes 14−67 nm and 11−54 nm, consecutively. Consequently, the synthesis method (sol–gel) which is used in this work concluded a decrease in particle size and different optical behavior especially in UV spectral regions during the substitution with Manganese in comparison with the AlZnO. This decrement assures that a decrease in the size of crystallite induces a decline in the χ3. The obtained optical parameters are red shifted with the Manganese substitution. Also, the NL absorption coefficient (β c(m/W)) is enhanced in the UV range. The maximum of the NL absorption coefficient (β c(m/W)), for AlZnO and Mn-AlZnO NPs, are determined (at λ = 250 nm) 2.24 × 10−18 (m/W) and 5.76 × 10−15 (m/W) respectively.

Laminar Flow Infrared Spectroelectrochemistry.

In this work, we advance lab-on-chip electrochemistry and spectroscopy by combining these capabilities onto a single platform, thereby achieving mid-infrared spectroelectrochemistry (SEC) for the first time. The key feature of this technique is the use of deterministic laminar flow patterns to precisely transport a reacted solution from upstream electrodes to a downstream spectral detection region. Laminar flow spectroelectrochemistry (LF-SEC) is therefore a completely new approach, which derives its distinction and advantage over traditional SEC by physically separating electrode and attenuated total reflection (ATR) elements. As such, these functional elements retain optimal properties, such as inert, highly conductive electrodes and a bare ATR element for sensitive Fourier transform infrared (FTIR) spectroscopy. By combining ATR-FTIR with a scanning aperture system, LF-SEC provides the additional advantage of spectroscopically monitoring reactions at individual electrodes. The LF-SEC system design is first optimized through a series of targeted experiments using a ferricyanide/ferrocyanide redox pair to validate electrochemical functionality, undertake spectroscopic calibration, optimize experimental parameters, and finally validate the quantitative relationship between FTIR results and the reaction rate under galvanostatic control. After optimization, we demonstrate the technique by monitoring the oxidation of the therapeutic compound ascorbic acid (vitamin C) in the presence of biomolecular interference from a molecule with an overlapping oxidation potential. We find that molecular availability causes the reaction to switch between reaction pathways, which we could finely monitor using LF-SEC. This work opens the door to future developments that take advantage of the microfluidic reactor setup, with benefits ranging from portability to high-throughput studies under precise reaction conditions.

Nanosized Eu3+-Doped NaY9Si6O26 Oxyapatite Phosphor: A Comprehensive Insight into Its Hydrothermal Synthesis and Structural, Morphological, Electronic, and Optical Properties.

Detailed analysis covered the optical and structural properties of Eu3+-doped NaY9Si6O26 oxyapatite phosphors, which were obtained via hydrothermal synthesis. X-ray diffraction patterns of NaY9Si6O26:xEu3+ (x = 0, 1, 5, 7, 10 mol% Eu3+) samples proved a single-phase hexagonal structure (P63/m (176) space group). Differential thermal analysis showed an exothermic peak at 995 °C attributed to the amorphous to crystalline transformation of NaY9Si6O26. Electron microscopy showed agglomerates composed of round-shaped nanoparticles ~53 nm in size. Room temperature photoluminescent emission spectra consisted of emission bands in the visible spectral region corresponding to 5D0 → 7FJ (J = 0, 1, 2, 3, 4) f-f transitions of Eu3+. Lifetime measurements showed that the Eu3+ concentration had no substantial effect on the rather long 5D0-level lifetime. The Eu3+ energy levels in the structure were determined using room-temperature excitation/emission spectra. Using the 7F1 manifold, the Nv-crystal field strength parameter was calculated to be 1442.65 cm-1. Structural, electronic, and optical properties were calculated to determine the band gap value, density of states, and index of refraction. The calculated direct band gap value was 4.665 eV (local density approximation) and 3.765 eV (general gradient approximation). Finally, the complete Judd-Ofelt analysis performed on all samples confirmed the experimental findings.

Original Blue Light-Emitting Diphenyl Sulfone Derivatives as Potential TADF Emitters for OLEDs

Organic light-emitting diodes (OLEDs) have emerged as one of the dominant technologies in displays due to their high emission efficiency and low power consumption. However, the development of blue color emitters has fallen behind that of red and green emitters, posing challenges in achieving optimal efficiency, stability, and accessibility. In this context, thermally activated delayed fluorescence (TADF) emitters hold promise as a potential solution for cost-effective, exceptionally efficient, and stable blue OLEDs due to their potential high efficiency and stability. TADF is a principle where certain organic materials can efficiently convert both singlet and triplet excitons, theoretically achieving up to 100% internal quantum efficiency. This research focused on diphenyl sulfone derivatives with carbazole groups as TADF compounds. Quantum chemical calculations and photoluminescence properties show the potential TADF properties of the molecules. New materials exhibit glass transition temperatures that would classify them as molecular glasses. Depending on the structure of the molecule, the photoluminescence emission is in the blue or green spectral region. Organic light-emitting diodes were fabricated from neat thin films of emitters by the wet casting method. The best performance in the deep blue emission region was achieved by a device with a turn-on voltage of 4 V and a maximum brightness of 178 cd/m2. In the blue-green emission region, the best performance was observed by an OLED with a turn-on voltage of 3.5 V, reaching a maximum brightness of 660 cd/m2.

Metabolomic Analysis of Histological Composition Variability of High-Grade Serous Ovarian Cancer Using 1H HR MAS NMR Spectroscopy.

In this work, the HR MAS NMR (high-resolution magic-angle spinning nuclear magnetic resonance) spectroscopy technique was combined with standard histological examinations to investigate the metabolic features of high-grade serous ovarian cancer (HGSOC) with a special focus on the relation between a metabolic profile and a cancer cell fraction. The studied group consisted of 44 patients with HGSOC and 18 patients with benign ovarian tumors. Normal ovarian tissue was also excised from 13 control patients. The metabolic profiles of 138 tissue specimens were acquired on a Bruker Avance III 400 MHz spectrometer. The NMR spectra of the HGSOC samples could be discriminated from those acquired from the non-transformed tissue and were shown to depend on tumor purity. The most important features that differentiate the samples with a high fraction of cancer cells from the samples containing mainly fibrotic stroma are the increased intensities in the spectral regions corresponding to phosphocholine/glycerophosphocholine, phosphoethanolamine/serine, threonine, uridine nucleotides and/or uridine diphosphate (UDP) nucleotide sugars. Higher levels of glutamine, glutamate, acetate, lysine, alanine, leucine and isoleucine were detected in the desmoplastic stroma within the HGSOC lesions compared to the stroma of benign tumors. The HR MAS NMR analysis of the metabolic composition of the epithelial and stromal compartments within HGSOC contributes to a better understanding of the disease's biology.

Near infrared diode-pumped lasing of femtosecond-laser-written Pr:LiLuF4 waveguide

In this Letter we report the near infrared operation of a femtosecond-laser-written diode-pumped Pr:LiLuF4 waveguide laser. By employing a circular depressed-cladding waveguide with propagation losses as low as 0.19dB/cm, we demonstrated lasing at 914 nm, with a maximum output power of 140mW and a slope efficiency of 24%. Moreover, we demonstrated the possibility of lasing in a waveguide device at 894 nm, 922 nm and 933 nm. To the authors knowledge, this is the first demonstration of a Pr-based waveguide laser operating in this spectral region.

Laser-induced fluorescence spectroscopic investigation of Echium amoenum decoction

Herbs containing medicinal ingredients with nutritional value have recently gained attention as an alternative to synthetic drugs. Aside from their pharmaceutical worthiness, a variety of naturally occurring chromophores with specific optical properties have made them valuable sources of natural pigments for many biophotonic applications. Echium Amoenum (EA) is one of the colorful flowers that has been used in traditional medicine for a long time. To our knowledge, although several studies have been carried out on the characterization of EA ingredients and their chemical activities, information on EA fluorescence is still lacking. Here, laser induced fluorescence (LIF) features of the decoction of EA petals were evaluated and found to be highly dependent on the excitation wavelength, EA concentration, and detection geometry. The abundance of pigments, the boundaries of their absorption/emission spectral regions, and the corresponding energy transfer ascertain the contribution of certain chromophores to the cumulative fluorescence activity. Upon deconvolution of the LIF spectra, it was revealed that the different emission bands of rosmarinic acid (corresponding to its dissociated forms) and the luminescent activity of luteolin and β-carotene mainly determine the quantum distribution of the fluorescence of EA. Angular measurement of LIF in a symmetric cylindrical arrangement revealed the presence of the inner filters mainly due to the reabsorption of LIF photons by anthocyanins (flavone, pelargonidin, delphinidin and cyanidin) and carotenoids. We hope that the obtained results will be useful in various fields of photochemistry and biophotonics.

Solution and Surface Solvation of Nitrate Anions with Iron(III) and Aluminum(III) in Aqueous Environments: A Raman and Vibrational Sum Frequency Generation Study.

Hydrated trivalent metal nitrate salts, Fe(NO3)3·9H2O and Al(NO3)3·9H2O, in both solid and aqueous phases are investigated. Raman and surface-selective vibrational sum frequency generation (SFG) spectroscopy, are used to shed light on ion-ion interactions and hydration in several spectral regions spanning low frequency (440-550 cm-1) to higher frequency modes of nitrate and water (720, 1050, 1250-1450, and 2800-3750 cm-1). These frequencies span the metal-water mode, nitrate in-plane deformation, nitrate symmetric and asymmetric modes, and the OH stretch of condensed phase water molecules. Comparison to NaNO3, and in some cases KNO3, is also shown, providing insight. Splitting and frequency shifts are observed and discussed for both the solid state and solution phase. The Lewis acidity of Fe3+ and Al3+ ions plays a significant role in the observed spectra, in particular for the nitrate asymmetric band splitting and frequency shift. The spectral response from water solvation for iron and aluminum nitrates is nonlinear as compared to linear for sodium nitrate, suggesting significantly different solvation environments that are limited by water hydration capacity at higher concentrations. Moreover, a non-hydrogen bonded OH, dangling OH, from hydrating water molecules is observed spectroscopically for Al and Fe nitrate solutions. Furthermore, aluminum nitrate perturbs the surface water structure more than iron nitrate despite aluminum being a weaker Lewis acid. The surface water structure is thus found to be unique for the Al(NO3)3 solutions as compared to both Fe(NO3)3 and NaNO3, such that surface solvation is more pronounced. This observation exemplifies the nature of the Fe(III) and Al(III) ions and their substantial influence on the surface water structure.

Electron Spin Dynamics of the Intersystem Crossing in Aminoanthraquinone Derivatives: The Spectral Telltale of Short Triplet Excited States.

We studied the excited state dynamics of two bis-amino substituted anthraquinone (AQ) derivatives, with absorption in the visible spectral region, which results from the attachment of a electron-donating group to the electron-deficient AQ chromophore. Femtosecond transient absorption spectra show that intersystem crossing (ISC) takes place in 190-320 ps, and nanosecond transient absorption spectra demonstrated an unusually short triplet state lifetime (2.06-5.43 μs) for the two AQ derivatives. Pulsed laser-excited time-resolved electron paramagnetic resonance (TREPR) spectra show an inversion of the electron spin polarization (ESP) phase pattern of the triplet state at a longer delay time after laser flash. Spectral simulations show faster decay of the Ty sublevel than the other two sublevels (τx = 15.0 μs, τy = 1.50 μs, τz = 15.0 μs); theoretical computation predicts initial overpopulation of the Ty sublevel, and rationalizes the short T1 state lifetime and the ESP inversion. Theoretical computations taking into account the electron-vibrational coupling, i.e., the Herzberg-Teller effect, successfully rationalize the TREPR experimental observations.

Improving Raman-Based Models for Real-Time Monitoring the CHO Cell Culture Process with Effective Variable Selection Strategies

Research has shown that Raman spectroscopy could be applied to monitor various components in mammalian cell culture in real time. In the process of application, it is necessary to ensure the performance of the Raman-based model. The variable selection strategy is an effective method that significantly influences the model performance and simplification. In this study, different variable selection strategies were evaluated, and the optimal variable selection strategy was determined for monitoring the CHO cell culture process. Firstly, a wide variety of spectral regions involving the Raman fingerprinting region and the C-H stretching region were investigated. Secondly, six different variable selection algorithms were meticulously assessed. Thirdly, the combination of different variable selection algorithms was used to improve model performance and simplify the model. Finally, the monitoring of cell culture processes was implemented. The findings underscored that commonly used spectral regions could improve the model performance but could not simplify the model well. Moving-window partial least square (MWPLS), genetic algorithm (GA), and random frog (RF) are more suitable for Raman modeling of the cell culture process, but they must be used after the spectral region selection. The combination of three variable selection algorithms (MWPLS-GA-RF) improved the model’s performance by 16–70% by selecting 30–60 variables, effectively simplifying the model. For glucose, lactate, viable cell density, and ammonium ion, real-time monitoring was performed well. This study will be helpful for researchers to select suitable variable selection strategies for building models for the real-time monitoring of cell culture.

Inline-delay Fourier transform imaging spectrometer for mid-IR ultrashort pulses

An inline-delay Fourier transform imaging spectrometer (iFTIS) is used to measure spatiospectral coupling in a mid-infrared (mid-IR) optical parametric amplifier (OPA). The method employs a compact inline delay line using a birefringent wedge pair and a microbolometer array as an imaging sensor, providing continuous spectral coverage from ∼0.4 to 4.5 µm in a single device. We find a spatial chirp that depends systematically on the OPA wavelength setting in the 3-4 µm range and also identify spatiospectral couplings beyond spatial chirp, highlighting the importance of advanced metrological techniques for this spectral region. Furthermore, we investigate the effect of depletion on the 2 µm pump beam and observe a complex spatiospectral reshaping. Our work opens the door to new applications of iFTIS to mid-IR laser science.

Enhanced SWIR Absorption in PMMA‐Coated TiN‐Based Metamaterial

AbstractAchieving highly efficient absorption in the short wavelength infrared (SWIR) spectral region is crucial for advancing numerous technologies. SWIR absorption enhances energy harvesting in solar cells, improves the sensitivity of infrared sensors, and enables precise control of thermal radiative properties in thermal emission devices. These advancements are essential for applications such as thermal imaging, night vision, and thermophotovoltaic systems. The study presents a simple, cost‐effective design of a polymer‐coated multilayer perfect absorber (MPA) metamaterial optimized for the SWIR spectral region. The proposed MPA structure is composed of four distinct layers: a top layer made of polymethyl methacrylate (PMMA) polymer, a second layer featuring arrays of circular titanium nitride (TiN) disks, a dielectric middle layer consisting of a pure zinc oxide (ZnO) film, and a bottom metallic layer formed by a thin film of TiN. The results demonstrate that the MPA achieves near‐perfect absorption, with a remarkable 99% efficiency centered at a wavelength of 1.3 µm. The absorption properties are further investigated with respect to various structural parameters to ensure better performance of the absorber. These absorbers hold great promise for applications in energy absorption, infrared sensing, thermal emission, and related fields.

ProTformer: Transformer-based model for superior prediction of protein content in lablab bean (Lablab purpureus L.) using Near-Infrared Reflectance spectroscopy

Lablab bean (Lablab purpureus L.), known for its higher protein content provides a promising alternative to reduce reliance on animal-based proteins and support sustainable agriculture. Nowadays, traditional methods for nutritional profiling have been outperformed by Convolutional Neural Networks (CNNs) integrated with Near-Infrared Reflectance Spectroscopy (NIRS). However, an advanced technique called Transformers, despite their potential, remains underexplored for prediction of key quality traits of crops. Thus, in the present study, we aimed to predict lablab bean protein content using a Transformer-based model (termed ProTformer) coupled with NIRS. The Dumas combustion method was used to determine protein content from 112 lablab bean genotypes. The performance of this model was compared with 1D CNN and Modified Partial Least Squares (MPLS)-based models. These models were evaluated using the Coefficient of Determination (RSQ), Residual Prediction Deviation (RPD), bias, and Corrected Standard Error of Prediction (SEP(C)). Our findings show that the Transformer-based model achieved the highest predictive accuracy (RSQ = 0.977, RPD = 13.92), surpassing the 1D CNN (RSQ = 0.956, RPD = 11.33) and MPLS (RSQ = 0.943, RPD = 10.53)- based models by 22.86% and 32.21% in RPD, respectively. The multi-head self-attention mechanism present in the Transformer-based model enables it to concurrently focus on different spectral regions, resulting in superior predictive performance. This study shows the potential of using Transformer-based models coupled with NIRS for nutritional profiling which could be effectively adapted for other crops for rapid screening of large germplasm available at global repositories.

IMPMH, direct tunable diode laser absorption spectroscopy for detection of water vapour under “Optically thick Condition”

Water vapour plays a crucial role in atmospheric processes. Hence, monitoring the altitude-related variations in water vapour properties is important to decipher atmospheric processes. Direct tunable diode laser absorption spectroscopy (dTDLAS) measures the concentration and temperature of gas molecules by scanning the rotation-vibration absorption lines using a high-spectral-resolution laser. In this study, we devised an integrated measurement and data processing method (integrative measurement and processing method for hygrometry, IMPMH) to enhance the in-situ airborne measurement capability of dTDLAS. We measured a wide range (240–18,000 ppm) of water vapour concentrations, aiming for atmospheric measurements in a highly water-saturated regime, called the “optically thick condition”. For recovering the full absorption spectra, the “integrative area” was defined and a difference factor D, which is the distance between two spectral regions with width corresponding to the half width of half maximum of the Voigt profile, was used to calculate the area. From the data, the low-bound concentration was measured to be 244 ppm. At D = 1.8, the transition concentration to the “optically thick condition” was measured to be 5,800 ppm. By increasing D from 1.8 to 2.8, the measurable upper-bound concentration increased to 17,993 ppm. IMPMH was applied to the measured data to estimate the final absorber density or water vapour concentration. The estimation was well-fitted with the measured detector signal with signal-to-noise ratio (SNR) of ∼ 300 of the residual spectrum, promising its applicability to in-situ airborne measurements. To validate IMPMH, the water vapour concentration range was divided into two regimes: (1) optically thick (5,800 < c < 18,000 ppm) and (2) optically thin (c < 5,800 ppm) conditions. Under the optically thick condition, IMPMH was validated by comparing the results between the short and long-path cells. In the optically thin condition, IMPMH was validated through comparison with the general dTDLAS method. Lastly, long-term stability of the dTDLAS system was validated by measuring 10 different concentrations (240–18,000 ppm) for 1000 s by characterising the precision and SNRs of the residual. The results demonstrate that IMPMH significantly enhances the in-situ airborne measurement capability of dTDLAS under both optically thick and thin conditions. Furthermore, requirements for the implementation of IMPMH in airborne measurement were investigated considering four aspects—sampling, low-pressure measurement, accuracy and precision, and multiplex detection. The results were examined with regard to atmospheric implications.