Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy最新文献

{"title":"A conjugated oligoelectrolyte for the recognition of uranyl ion in aqueous and soil samples via RGB method","authors":"","doi":"10.1016/j.saa.2024.125355","DOIUrl":"10.1016/j.saa.2024.125355","url":null,"abstract":"<div><div>The development of selective and practically applicable sensors for monitoring trace uranyl ions (UO₂²⁺) in an aqueous medium is the biggest challenge. This study presents the development of a conjugated oligoelectrolyte-based probe (COE) for the selective detection of UO₂²⁺ ions in water bodies. The COE is a water-soluble probe having an organic backbone with two ionic pendants at the terminal points. It changes its color to a dark yellow selectively in the presence of UO₂²⁺ ions. This visible change was integrated with a smartphone RGB color quantification method. The COE displayed an RGB chemo-dosimeter to selectively monitor UO₂²⁺ ions without interference from other metal ions. In the parallel experiment, COE displays a spectrofluorimetric emission signal at λ_ems. = 525 nm (with λ_exc. = 420 nm), which exhibits quenching of signal when interacted with UO₂²⁺ ions. The limit of detection (LOD) is found to be 3.07 × 10⁻² µM and 4.50 µM by spectrofluorimetric and RGB color value methods, respectively. ¹H NMR and XPS analysis investigated the mode of interaction, and it suggested that the quenching of the emission signal was due to the interaction between the electron-rich azomethine site of COE and UO₂²⁺ ion. The smartphone-based RGB color analysis makes COE a potential probe with reduced operation time and offers a fresh approach for the immediate, real-time detection of UO₂²⁺ ions in aqueous and soil samples.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142570817","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Using hyperspectral imaging to predict the occurrence of delayed graft function","authors":"","doi":"10.1016/j.saa.2024.125350","DOIUrl":"10.1016/j.saa.2024.125350","url":null,"abstract":"<div><div>Delayed Graft Function (DGF) is a prevalent complication in kidney transplantation (KT) that significantly affects allograft function and patient prognosis. Early and precise identification of DGF is crucial for improving post-transplant outcomes. In this study, we present KGnet, a predictive model leveraging hyperspectral imaging (HSI) to assess delayed graft function status. We analyzed 72 zero-hour biopsy samples from transplanted kidneys with confirmed pathological diagnoses, capturing spectral data across a wavelength range of 400 to 1000 nm. By examining spectral signatures related to tissue oxygenation, perfusion, and metabolic states, our approach enabled the detection of subtle biochemical changes indicative of DGF risk. The preprocessed spectral data were input into KGnet, achieving a prediction accuracy of 94 % for DGF occurrence, significantly outperforming existing predictive models. This study identifies key spectral signatures associated with DGF, allowing for precise risk prediction even before clinical symptoms emerge. Leveraging HSI for early detection introduces a novel pathway for individualized post-transplant management, offering substantial potential to enhance kidney transplantation outcomes and patient quality of life. These findings highlight significant clinical and research implications for the broader application of HSI in transplant medicine.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Graphene quantum dots as eco-friendly fluorescent probes for sensitive and selective determination of lumateperone in pharmaceutical preparation: Greenness and blueness assessment","authors":"","doi":"10.1016/j.saa.2024.125342","DOIUrl":"10.1016/j.saa.2024.125342","url":null,"abstract":"<div><div>This study investigates the potential of graphene quantum dots (GQDs) as fluorescent probes for the determination of the antipsychotic drug lumateperone. The spectral characteristics and sensing mechanism of the fluorescent probes were examined, revealing a static quenching mechanism as indicated by the Stern-Volmer analysis. Different factors affecting the quenching process, such as pH, concentration of QDs, and incubation time, were carefully tuned. The developed method was validated according to ICH guidelines, demonstrating excellent linearity in the range of 0.5–2.5 μg/mL, limits of detection and quantification of 0.1226 μg/mL and 0.3714 μg/mL, respectively, and high accuracy, precision, robustness and selectivity. Furthermore, the greenness and blueness of the proposed method were assessed using GAPI, AGREE, and BAGI tools, yielding an AGREE score of 0.78 and a BAGI score of 75 confirming its environmentally benign nature as well as analytical practicality. The method was successfully applied to determine lumateperone in a pharmaceutical formulation, highlighting its potential for routine quality control analysis. This study demonstrates the promising analytical capabilities of GQDs for the sensitive and selective detection of antipsychotic drug lumateperone, offering a simple, rapid, and green alternative to existing analytical techniques.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142561241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Manipulation of defect state emission in Zn chalcogenide quantum dots and their effects on chlorophyll spectral response","authors":"","doi":"10.1016/j.saa.2024.125348","DOIUrl":"10.1016/j.saa.2024.125348","url":null,"abstract":"<div><div>Water soluble Zn based quantum dots (QDs) are of interest due to their biocompatibility and less toxic features. They have been frequently used in studies related to biotechnology, especially in agriculture studies. However, to control the optical properties of Zn based QDs has still been a challenge. In this work, the defect state emission of ZnSe QDs was successfully controlled through two different routes; 1) By creating a sulfur rich outer region around the Se rich core 2) By changing the capping agent. Gradient alloyed ZnSeS QDs with Se rich core and S rich outer region were successfully synthesized with two different capping agents; N-Acetyl-L-Cysteine (NAC) and 3-Mercaptopropionic Acid (3-MPA). The contribution of emission originated from surface-defects almost disappeared in NAC capped ZnSeS QDs, with causing a significant increase in photoluminescence quantum yield. The interaction between Zn based QDs with chlorophyll molecules was also investigated. The absorption capacity of chlorophylls significantly enhanced upon interaction with 3-MPA capped ZnSeS QDs. Also, the spectral response of chlorophylls could be modulated through interaction with 3-MPA capped ZnSeS QDs, which could be manipulated by using ZnSeS QDs with different chemical composition. Our results indicated that ZnSeS QDs have potential to be used in agriculture, which could act as a modulator of light-harvesting capacity of chlorophylls. The ability to modulate chlorophyll spectral responses through QD interaction opens new possibilities for optimizing light utilization in photosynthetic organisms, thereby contributing to enhanced crop yields and more efficient use of light energy in natural and artificial ecosystems.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554214","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the potential of diosgenin as a promising antitumor agent through comprehensive spectroscopic characterization, solvent–solute interactions, topological properties, Hirshfeld surface, and molecular docking interactions with 2NZT and 2I1V proteins","authors":"","doi":"10.1016/j.saa.2024.125349","DOIUrl":"10.1016/j.saa.2024.125349","url":null,"abstract":"<div><div>This study characterizes the steroidal saponin diosgenin by theoretical and experimental spectroscopic techniques. Theoretical simulations were performed using the DFT/B3LYP/6-311++G(d,p) basis set to simulate spectroscopic, structural and other properties. Optimized geometries from simulations and experiments showed strong agreement, with R² value of 0.99846 for bond lengths and 0.88092 for bond angles. Vibrational spectra revealed distinctive peaks for the methyl, methylene, and methine groups in diosgenin. Solvent–solute interactions on the Frontier Molecular Orbitals (FMO), Molecular Electrostatic Potential (MEP) surfaces, and electronic spectra were analyzed, revealing insights into diosgenin’s behavior in different environments. The FMO energy gap shows that polar solvents like acetone, ethanol, and water have wider band gaps (6.22–6.23 eV) than non-polar solvents like benzene, chloroform, and toluene (6.17–6.20 eV), indicating stronger interactions with polar groups, enhanced stability, and reduced reactivity. NBO analysis shows substantial stabilization energy (14.71 kJ/mol) when electrons from oxygen’s (O₁) lone pair are donated to the anti-bonding orbital of O₂<img>C₁₅ through the transition of LP (2) → σ*. The carbon (C₁₅) situated between oxygen (O₁) and (O₂) exhibits increased electronegativity (−1.65605 e), confirming the electronegativity of the oxygen atoms. Hirshfeld surfaces shows that the crystal structure is mainly influenced by H…H (90.7 %) interaction. Topological analyses revealed molecular interactions and chemical bonding within diosgenin, highlighting its diverse chemical functionalities. Furthermore, molecular docking and ADME predictions underscores diosgenin’s potential biological activity against human hexokinase (−8.09 kcal/mol) and phosphofructokinase (−8.35 kcal/mol), suggesting its efficacy as an antitumor drug.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142570840","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Features of the defect structure of a lithium-gradient nonlinear optical single crystal LiNbO3 and their manifestation in the Raman spectra","authors":"","doi":"10.1016/j.saa.2024.125340","DOIUrl":"10.1016/j.saa.2024.125340","url":null,"abstract":"<div><div>LiNbO₃ crystal with a lithium composition gradient of Li/Nb = 0.8 wt%/cm (Li_0.97..1.01Nb_1.03..0.99O₃) were obtained. A monotonic change in the edge of the UV absorption edge is observed when scanning the surface of the gradient crystal along the growth direction. Raman spectra from different areas of studied crystal were analyzed in a wide frequency range, which includes the region of fundamental vibrations of the crystal lattice (100–900 cm⁻¹) and the region of overtone processes (900–3000 cm⁻¹). A compositionally homogeneous, congruent LiNbO₃ crystal was used as a comparison sample. It was found that in the spectra obtained from different parts of the gradient crystal, there is a significant scatter in the frequency values of the lines corresponding to the fundamental vibrations of the crystal lattice, but at the same time, the number of lines corresponding to the fundamental vibrations of the lattice for the gradient and compositionally homogeneous LiNbO₃ crystals is the same. Moreover, in the spectrum of a gradient crystal in the region of overtone processes of fundamental vibrations, significantly more lines (35 lines) are observed than in the spectrum of compositionally homogeneous crystals (15 lines). The data obtained show that the state of the defect structure of compositionally homogeneous crystals and gradient LiNbO₃ crystal is significantly different. The discovered differences between the defective structure of a gradient crystal and the defective structure of a compositionally homogeneous crystal may be the reason for compensation (damping) of distortions during nonlinear optical conversion of laser radiation by a gradient crystal due to the uneven temperature distribution along the length of the crystal. In compositionally homogeneous crystals, such temperature distortions significantly limit the efficiency of nonlinear optical conversion.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142578099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"How reliable is the evaluation of DNA binding constants? Insights and best practices based on an inter-laboratory fluorescence titration study","authors":"","doi":"10.1016/j.saa.2024.125354","DOIUrl":"10.1016/j.saa.2024.125354","url":null,"abstract":"<div><div>In all experimental sciences, the precision and reliability of quantitative measurements are paramount. This is particularly true when examining the interactions between small molecules and biomolecules/polyelectrolytes, such as DNAs/RNAs, and yet it is overlooked in most publications of thermodynamic binding parameters. This paper presents findings from COST Action 18202 “Network for Equilibria and Chemical Thermodynamics Advanced Research,” which assessed the consistency of data derived from the interactions of calf-thymus DNA (CT-DNA) with the fluorescent intercalator ethidium bromide (EB) through spectrofluorimetric titrations. We first discuss critical experimental aspects and propose a reference experimental protocol which can be used to calibrate procedures for the determination of nucleic acid binding equilibrium constants. We then fit the experimental points according to different procedures and analyse the results focusing on the statistical dispersion of the data, aiming at enlightening the strong and weak points of different fitting procedures. The implications of this work are significant, demonstrating how the statistical dispersion of experimental data can influence the interpretation of biochemical coordination mechanisms. Our study reveals that, despite rigorous protocol standardization, the determination of binding parameters remains sensitive to the choice of data fitting method, with deviations in the logarithmic stability constant (log<em>K</em>) values not falling below 5 % relative standard deviation (RSD), or ± 0.5 log<em>K</em> units for 95 % confidence. This variability evidences the critical need for standardized best practices in data treatment as well as experimental procedures. Although our study focuses on the EB/CT-DNA system through fluorescence titrations, the broader implications for other methodologies across various biochemical systems highlight the importance of this first-of-its-kind inter-laboratory comparison in advancing our understanding of biochemical coordination processes.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142578110","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Novel förster resonance energy transfer (FRET)-based ratiometric fluorescent probe for detection of cyanides by nucleophilic substitution of aromatic hydrogen (SNArH)","authors":"","doi":"10.1016/j.saa.2024.125339","DOIUrl":"10.1016/j.saa.2024.125339","url":null,"abstract":"<div><div>The development of novel fluorescent probes for real-time detection of cyanides (CN⁻) in environmental and biological systems has become a significant focus in chemical sensing. Particularly, ratiometric fluorescence sensing offers a unique method for precise and quantitative detection of cyanides, even under complex conditions. We report herein the design of a new ratiometric fluorescent probe for cyanides based on modulation of Förster resonance energy transfer (FRET) coupled with novel cyanide-induced nucleophilic substitution of aromatic hydrogen (SNArH). The target probe (<strong>R1</strong>) is developed by introducing coumarin fluorophores as FRET donors into a 3-nitro-naphthalimide acceptor, which is easily synthesized and exhibits a colorimetric change from colorless to faint yellow and a significant ratiometric fluorescence shift (Δλ = 114 nm) upon cyanide binding. A clear ratiometric signal at <em>I</em>₅₈₂/<em>I</em>₄₆₈ was obtained, with a limit of detection of 5.69 μM. The sensing mechanism was confirmed through ¹H NMR titration and LC-MS analysis. Additionally, <strong>R1</strong>-loaded strips were easily prepared, serving as a portable device for detecting CN⁻ with visible color changes. The probe <strong>R1</strong> has been successfully utilized for real-time monitoring of cyanide in food materials and water samples. Importantly, fluorescence bioimaging studies in HeLa cells were conducted, demonstrating the probe’s capability for ratiometric detection of exogenous CN⁻ in living systems.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Suppression of cross-interference in the absorption spectra of gas mixtures","authors":"","doi":"10.1016/j.saa.2024.125352","DOIUrl":"10.1016/j.saa.2024.125352","url":null,"abstract":"<div><div>In the quantitative analysis of mixed gases by tunable diode laser absorption spectroscopy, the overlapping of absorption spectra and mutual interference of multi-component gases can lead to problems of large measurement errors and low analysis accuracy. In this paper, an improved firefly algorithm is proposed and applied to the support vector machine regression model to solve this problem. The specific method includes introducing an adaptive step size to balance the local and global searches and using the gradient descent method to accelerate the parameter optimization process so as to improve the model’s generalization ability and prediction accuracy. The experimental results show that the maximum errors of the improved algorithm in the prediction of CH₄ and CO gas concentrations are no more than 0.0443 % and 2 ppm, with coefficients of determination, R², of 0.9994 and 0.99815. The promising results obtained by the system provide theoretical support for the realization of high-precision detection of multicomponent gases with a single source of light, and also demonstrate the high efficiency and feasibility of the method in practical detection.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142570844","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A comparative study and trace- level detection of volatile organic biomarkers using UV-IR-THz sources based high −Q helmholtz photoacoustic sensor","authors":"","doi":"10.1016/j.saa.2024.125332","DOIUrl":"10.1016/j.saa.2024.125332","url":null,"abstract":"<div><div>This paper reports the trace-level detection of volatile organic compounds (VOCs) like methanol, ethanol, and isopropanol, which are biomarkers for various diseases like diabetes, breast cancer, lung cancer, chronic pulmonary diseases, squamous cancer, cystic fibrosis, chronic liver diseases, chronic kidney diseases and so on. Here, the photoacoustic spectroscopy technique was used for the trace-level detection of these biomarkers using an indigenously designed tunable frequency (1.4 to 4 kHz range) Helmholtz photoacoustic (PA) cell. The study was carried out with UV (266 nm), Mid IR (5.4–7.3 µm) and THz (0.11 THz) range sources to explore and compare the PA signal generated by mentioned samples for different electronic vibrational and rotational level excitations. We achieved a low detection limit (LoD) of the order of 39.3 ppbV, 29.7 ppbV, and 11.6 ppbV for methanol, ethanol, and isopropanol, respectively using this non-invasive cost-effective, and fast technique. In addition, THz-based PA signal for these samples is reported for the first time.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142578111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}