Vibrational Spectroscopic Techniques Research Articles

Analyzing TVB-N in snakehead by Bayesian-optimized 1D-CNN using molecular vibrational spectroscopic techniques: Near-infrared and Raman spectroscopy

Total volatile basic nitrogen (TVB-N) is one of the key indicators for assessing fish freshness. This research employed near-infrared (NIR) and Raman spectroscopy methods to detect the TVB-N content in snakehead fillets. We extracted feature variables associated with TVB-N from NIR and Raman spectroscopy using Variable Crossover Point Arithmetic - Improved Reduced-Input Vector (VCPA-IRIV). Using these features, we established partial least squares (PLS) and One-dimensional Convolutional Neural Network (1D-CNN) models. Subsequently, data fusion strategies were employed to predict the TVB-N content. Notably, feature-level fusion in conjunction with Bayesian-optimized 1D-CNN, reached the best results, as evidenced by calibration and predictive correlation coefficients of 0.9677 and 0.9676 for TVB-N. These findings underscore the effectiveness of both NIR and Raman spectroscopy in evaluating fish freshness. The fusion of these two vibrational spectroscopy techniques enables a more rapid, efficient and comprehensive quantification of fish freshness.

Vibrational Spectroscopy Can Be Vulnerable to Adversarial Attacks.

Nondestructive detection methods based on vibrational spectroscopy have been widely used in many critical applications in a variety of fields such as the chemical industry, pharmacy, national defense, security, and so on. As these methods/applications rely on machine learning models for data analysis, studying the threats associated with adversarial examples in vibrational spectroscopy and defenses against them is of great importance. In this paper, we propose a novel adversarial method to attack vibrational spectroscopy, named SynPat, where synthetic peaks produced by a physical model are placed at key locations to form adversarial perturbations. Our new attack generates perturbations that successfully deceive machine learning models for Raman and infrared spectrum analysis while they blend much better into the spectra and hence are unnoticeable to human operators, unlike the existing state-of-the-art adversarial attacking methods, e.g., images and audio. We verified the superiority of the proposed SynPat by an imperceptibility test conducted by human experts and of defense experiments by an AI detector. To the best of our knowledge, this is a first thorough study on the robustness of vibrational spectroscopic techniques against adversarial samples and defense mechanisms. Our extensive experiments show that machine learning models for vibrational spectroscopy, including conventional and deep models for Raman or infrared classification and regression, are all vulnerable to adversarial perturbations and thus may pose serious security threats to our society.

Predicting Boar Sperm Survival during Liquid Storage Using Vibrational Spectroscopic Techniques.

Artificial insemination (AI) plays a critical role in livestock reproduction, with semen quality being essential. In swine, AI primarily uses cool-stored semen adhering to industry standards assessed through routine analysis, yet fertility inconsistencies highlight the need for enhanced semen evaluation. Over 10-day storage at 17 °C, boar semen samples were analyzed for motility, morphology, sperm membrane integrity, apoptosis, and oxidative stress indicators. Additionally, machine learning tools were employed to explore the potential of Raman and near-infrared (NIR) spectroscopy in enhancing semen sample evaluation. Sperm motility and morphology gradually decreased during storage, with distinct groups categorized as "Good" or "Poor" survival semen according to motility on Day 7 of storage. Initially similar on Day 0 of semen collection, "Poor" samples revealed significantly lower total motility (21.69 ± 4.64% vs. 80.19 ± 1.42%), progressive motility (4.74 ± 1.71% vs. 39.73 ± 2.57%), and normal morphology (66.43 ± 2.60% vs. 87.91 ± 1.92%) than their "Good" counterparts by Day 7, using a computer-assisted sperm analyzer. Furthermore, "Poor" samples had higher levels of apoptotic cells, membrane damage, and intracellular reactive oxygen species on Day 0. Conversely, "Good" samples maintained higher total antioxidant capacity. Raman spectroscopy outperformed NIR, providing distinctive spectral profiles aligned with semen biochemical changes and enabling the prediction of semen survival during storage. Overall, the spectral profiles coupled with machine learning tools might assist in enhancing semen evaluation and prognosis.

2D Material-Based Surface-Enhanced Raman Spectroscopy Platforms (Either Alone or in Nanocomposite Form)-From a Chemical Enhancement Perspective.

Surface-enhanced Raman spectroscopy (SERS) is a vibrational spectroscopic technique with molecular fingerprinting capability and high sensitivity, even down to the single-molecule level. As it is 50 years since the observation of the phenomenon, it has now become an important task to discuss the challenges in this field and determine the areas of development. Electromagnetic enhancement has a mature theoretical explanation, while a chemical mechanism which involves more complex interactions has been difficult to elucidate until recently. This article focuses on the 2D material-based platforms where chemical enhancement (CE) is a significant contributor to SERS. In the context of a diverse range (transition metal dichalcogenides, MXenes, etc.) and categories (insulating, semiconducting, semimetallic, and metallic) of 2D materials, the review aims to realize the influence of various factors on SERS response such as substrates (layer thickness, structural phase, etc.), analytes (energy levels, molecular orientation, etc.), excitation wavelengths, molecular resonances, charge-transfer transitions, dipole interactions, etc. Some examples of special treatments or approaches have been outlined for overcoming well-known limitations of SERS and include how CE benefits from the defect-induced physicochemical changes to 2D materials mostly via the charge-transport ability or surface interaction efficiency. The review may help readers understand different phenomena involved in CE and broaden the substrate-designing approaches based on a diverse set of 2D materials.

Expanding the scope of resonance Raman spectroscopy in hydrogenase research: New observable states and reporter vibrations

Oxygen-tolerant [NiFe] hydrogenases are valuable blueprints for the activation and evolution of molecular hydrogen under application-relevant conditions. Vibrational spectroscopic techniques play a key role in the investigation of these metalloenzymes. For instance, resonance Raman spectroscopy has been introduced as a site-selective approach for probing metal-ligand coordinates of the [NiFe] active site and FeS clusters. Despite its success, this approach is still challenged by a limited number of detectable active-site states – due to missing resonance enhancement or intrinsic light sensitivity – and difficulties in their assignment. Utilizing two oxygen-tolerant [NiFe] hydrogenases as model systems, we illustrate how these challenges can be met by extending excitation and detection wavelength regimes in resonance Raman spectroscopic studies. Specifically, we observe that this technique does not only probe low-frequency metal-ligand vibrations but also high-frequency intra-ligand modes of the diatomic CO/CN− ligands at the active site of [NiFe] hydrogenases. These reporter vibrations are routinely probed by infrared absorption spectroscopy, so that direct comparison of spectra from both techniques allows an unambiguous assignment of states detected by resonance Raman spectroscopy. Moreover, we find that a previously undetected state featuring a bridging hydroxo ligand between Ni and Fe can be probed using higher excitation wavelengths, as photoconversion occurring at lower wavelengths is avoided. In summary, this study expands the applicability of resonance Raman spectroscopy to hydrogenases and other complex metalloenzymes by introducing new strategies for probing and assigning redox-structural states of the active site.

Radiobiological Applications of Vibrational Spectroscopy: A Review of Analyses of Ionising Radiation Effects in Biology and Medicine

Vibrational spectroscopic techniques, such as Fourier transform infrared (FTIR) absorption and Raman spectroscopy (RS), offer unique and detailed biochemical fingerprints by detecting specific molecular vibrations within samples. These techniques provide profound insights into the molecular alterations induced by ionising radiation, which are both complex and multifaceted. This paper reviews the application of rapid and label-free vibrational spectroscopic methods for assessing biological radiation responses. These assessments span from early compartmentalised models such as DNA, lipid membranes, and vesicles to comprehensive evaluations in various living biological models, including tissues, cells, and organisms of diverse origins. The review also discusses future perspectives, highlighting how the field is overcoming methodological limitations. RS and FTIR have demonstrated significant potential in detecting radiation-induced biomolecular alternations, which may facilitate the identification of radiation exposure spectral biomarkers/profiles.

ZnO nanostructures grown from spent batteries: Ambient catalytic aspects and novel mechanistic insights

The present work includes a facile and economic microwave assisted hydrothermal synthesis of Zinc Oxide (ZnO), Diethylene Triamine Pentaacetic Acid (DTPA) stabilized Zinc Oxide (ZD) and DTPA stabilized Silver doped Zinc Oxide (ZAD) nanostructures using Zn from spent alkaline batteries. The synthesised nanostructures were well characterised using electronic, vibrational and X-Ray spectroscopic techniques as well as thermal and microscopic techniques revealing the successful stabilisation of DTPA in ZD and doping of Ag in ZAD. The Fourier Transform Infrared Spectroscopy (FTIR) spectra showed peaks characteristic to the presence of ZnO in the fingerprint region and those to the presence of DTPA. The X-Ray Diffraction Spectroscopy (XRD) pattern of ZnO, ZD and ZAD indicated the hexagonal wurtzite structure of ZnO and face centred cubic metallic Ag in ZAD. The Transmission Electron Microscopy (TEM) images revealed rod shaped morphology for ZnO and spherical morphologies for ZD and ZAD. The nanostructures proved to be efficient catalysts to achieve 100 % degradation of Malachite Green, Crystal Violet and Reactive Blue-21 and their binary mixtures under ambient conditions in presence of Hydrogen peroxide (H2O2). ZAD exhibited relatively rapid degradation with rate constants 0.754 min−1, 0.187 min−1 and 0.0150 min−1 for MG, CV, and RB-21 respectively as well as 99 % reduction in Chemical Oxygen Demand (COD) value of the dye solutions. Scavenging studies and Electron Paramagnetic Resonance (EPR) studies using different spin trapping agents revealed the involvement of singlet oxygen species, hydroxyl radicals (OH.) and superoxide radicals (O2.-) in the degradation process. This work aligns with Sustainable Development Goals 6, 12 and 13.

The application of vibrational spectroscopy in forensic analysis of biological evidence.

Vibrational spectroscopy is a powerful analytical domain, within which Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy stand as exemplars, offering high chemical specificity and sensitivity. These methodologies have been instrumental in the characterization of chemical compounds for an extensive period. They are particularly adept at the identification and analysis of minute sample quantities. Both FTIR and Raman spectroscopy are proficient in elucidating small liquid samples and detecting nuanced molecular alterations. The application of chemometrics further augments their analytical prowess. Currently, these techniques are in the research phase within forensic medicine and have yet to be broadly implemented in examination and identification processes. Nonetheless, studies have indicated that a combined classification model utilizing FTIR and Raman spectroscopy yields exceptional results for the identification of biological fluid-related information and the determination of causes of death. The objective of this review is to delineate the current research trajectory and potential applications of these two vibrational spectroscopic techniques in the detection of body fluids and the ascertainment of causes of death within the context of forensic medicine.

Investigation of titanium(IV)-oxo complexes stabilized with α-hydroxy carboxylate ligands: structural analysis and DFT studies.

This paper explores the findings on the structures and physicochemical properties of titanium-oxo complexes (TOCs) stabilized by 9-hydroxy-9-fluorenecarboxylate ligands. Two complexes, with the overall formulas [Ti4O(OiPr)10(O3C14H8)2] (1) and [Ti6O4(OiPr)2(O3C14H8)4(O2CEt)6] (2), have been synthesized. The structures of the isolated crystals (1 and 2) were determined using single-crystal X-ray diffraction. Molecular structure analysis of the crystals also employed vibrational spectroscopic techniques (IR and Raman), UV-Vis diffuse reflectance spectroscopy (UV-Vis-DRS), and powder X-ray diffraction (XRD). Density functional theory (DFT) was utilized to elucidate the electronic structures of these complexes. Furthermore, the theoretical charge distribution in 1 and 2 and their reactivity were calculated. The results of these investigations suggest that the reactivity of 2 is significantly greater than that of 1.

Interpretable support vector machine for authentication of omega-3 fish oil supplements using Raman spectroscopy

The use of machine learning algorithms to develop automated analytical methods and smart sensors has drastically increased in recent years. Although these algorithms often provide great performances, the poor interpretability is one of their main limitations. In this work, we present an efficient method to authenticate certified omega-3 fish oil supplements which relies on a vibrational spectroscopic technique (Raman spectroscopy) and a chemically interpretable machine learning algorithm (interval support vector machine, iSVM). The Raman spectra were collected from 248 certified and 520 non-certified omega-3 fish oil samples in a non-destructive fashion. Key differences in the chemical composition of certified and non-certified supplements were unveiled by correlating the iSVM discriminant capability with Raman bands in the corresponding spectral intervals. Proper figures of merit (e.g., accuracy and F1 score) were estimated and critically discussed, and an additional external validation was performed with independent samples to assess the model's robustness and generalization capability. In addition to the excellent chemical interpretability, which revealed the great importance of Raman bands of unsaturated fats to authenticate samples, the proposed Raman-iSVM method showed to be accurate (96 and 92% for internal and external validation sets, respectively), rapid, portable, and computationally cost-effective. Therefore, we believe this method can readily be implemented for in-situ quality monitoring of omega-3 fish oil supplements and other food products.

Screening the capability of vibrational spectroscopic techniques for simultaneous quantification of vitamins B1, B6, and B12 in a powder blend

The rising possibilities of vibrational spectroscopy coupled with multivariate modeling, enables many applications of these well-established analytical techniques, easy-to-use for rapid and non-destructive analysis. Owing to the lack of need for hazardous solvents or reagents in sample preparation, FTIR, NIR and Raman spectroscopy belong to the group of environmentally friendly techniques, known as “green analytical techniques”. Such characteristics re-introduce them into the pharmaceutical industry, especially as part of process-analytical-technology (PAT) tools for both qualitative and quantitative analysis.This research aimed to assess the potential of ATR-FTIR, NIR and Raman as a PAT for the quantification of Vitamins B1 (thiamine), B6 (pyridoxine) and B12 (cyanocobalamin) in a powder blend, using a partial least square (PLS) regression model, as well as to monitor the powder blend homogeneity.Results from each of the vibrational spectroscopy techniques were compared with those obtained by HPLC, which served as the reference analytical technique for quantifying the active substances in complex matrices using multivariate analysis. The developed PLS models were evaluated for their ability to quantify each of the active substances in the powder blend. The ATR-FTIR, NIR and Raman spectrum segments, revealed by the Variable Importance for Projection (VIP) plot for each model, respectively, were linked to the band assignment of each active ingredient.The statistical indicators of the models (interpretation rate (R2X and R2Y), predictive ability (Q2 and RMSEP) and accuracy (RMSEE)) demonstrated their suitability for in-process estimation of vitamin B1, B6 and B12 contents in powder blends. Estimating B12 content proved more challenging, likely due to sampling issues related to its low content in the powder blend. Nevertheless, the observed variability in the models aligns with the variability in results obtained by HPLC, indicating the lack of blend homogeneity. Therefore, the quantification models could be considered for a further upgrade as PAT for monitoring the powder blend homogeneity during the manufacturing of vitamin blends.

Molecular symmetry change of perfluoro-n-alkanes in ‘Phase I’ monitored by infrared spectroscopy

Phase diagram of polytetrafluoroethylene (PTFE) comprises four regions. Phases II and IV are characterized by twisted perfluoroalkyl (Rf) chains having different twisting rate of 13/6 and 15/7, respectively, while Phase III is characterized by a planer trans-zigzag molecular skeleton like a normal alkyl chain. These are confirmed by X-ray and electron diffraction and have already been established. Unlike these, Phase I is left an unresolved matter. This phase is complicated indeed and is not symbolized by a single molecular structure. At an ambient pressure, Phase I is the temperature region above 30 ºC (303 K), and the helical molecular structure is supposed to be gradually untwisted with an elevating temperature. This untwisting image is roughly suggested by the diffraction, neutron scattering, and thermal expansion techniques, but the conventional approaches have all experimental limitations because the untwisting accompanies disorder (or defect) in the twist along the chain. To explore the transition between two different helical structures of the Rf chain having disordered structures, vibrational spectroscopic techniques are expected to be an alternative approach. For infrared spectroscopy, for example, the twisting rate of the molecule is simply recognized as a degree of molecular symmetry. Here, we show that the band progression peaks of the CF2 symmetric stretching vibration mode are quite sensitive and useful for pursuing the molecular symmetry change in Phase I for both peak intensity and position using perfluoro-n-alkanes having different chain length covering both even and odd number of the CF2 groups.Graphical abstract

N···C═O n → π* Interaction: Gas-Phase Electronic and Vibrational Spectroscopy Combined with Quantum Chemistry Calculations.

Herein, we have used gas-phase electronic and vibrational spectroscopic techniques for the first time to study the N···C═O n → π* interaction in ethyl 2-(2-(dimethylamino) phenyl) acetate (NMe2-Ph-EA). We have measured the electronic spectra of NMe2-Ph-EA in the mass channels of its two distinct fragments of m/z = 15 and 192 using a resonant two-photon ionization technique as there was extensive photofragmentation of NMe2-Ph-EA. Identical electronic spectra obtained in the mass channels of both fragments confirm the dissociation of NMe2-Ph-EA in the ionic state, and hence, the electronic spectrum of the fragment represents that of NMe2-Ph-EA only. UV-UV hole-burning spectroscopy proved the presence of a single conformer of NMe2-Ph-EA in the experiment. Detailed quantum chemistry calculations reveal the existence of a N···C═O n → π* interaction in all six low-energy conformers of NMe2-Ph-EA. A comparison of the IR spectrum of NMe2-Ph-EA acquired from the gas-phase experiment with those obtained from theoretical calculations indicates that the experimentally observed conformer has a N···C═O n → π* interaction. The present finding might be further valuable in drug design and their recognition based on the N···C═O n → π* interaction.

Rovibrational analysis of AlCO3, OAlO2, and HOAlO2 for possible atmospheric detection.

The lack of observational data for the AlO molecule in the mesosphere/lower thermosphere may be due to ablated aluminum reacting quickly to form other species. Previously proposed reaction pathways show that aluminum could be ablated in the atmosphere from meteoritic activity, but there currently exist very limited spectroscopic data on the intermediates in these reactions, limiting the possible detection of said molecules. As such, rovibrational spectroscopic data are computed herein using quartic force field methodology at four different levels of theory for the neutral intermediates AlCO3, OAlO2, and HOAlO2. Each molecule exhibits multiple vibrational modes with large vibrational transition intensities. For instance, the C-O stretch (ν1) in AlCO3 has a harmonic intensity of 536 km mol-1, the Al-O stretch (ν2) in OAlO2 has an intensity of 678 km mol-1, and the out-of-plane torsion (ν9) in HOAlO2 has an intensity of 158 km mol-1. All three molecules have exceptionally large dipole moments of 6.27, 4.21, and 5.04D, respectively. These properties indicate that all three molecules are good candidates for potential atmospheric observation utilizing vibrational and/or rotational spectroscopic techniques.

Conformational and environmental effects on the electronic and vibrational properties of dyes for solar cell devices.

The main challenge for solar cell devices is harvesting photons beyond the visible by reaching the red-edge (650-780nm). Dye-sensitized solar cell (DSSC) devices combine the optical absorption and the charge separation processes by the association of a sensitizer as a light-absorbing material (dye molecules, whose absorption can be tuned and designed) with a wide band gap nanostructured semiconductor. Conformational and environmental effects (i.e., solvent, pH) can drastically influence the photophysical properties of molecular dyes. This study proposes a combined experimental and computational approach for the comprehensive investigation of the electronic and vibrational properties of a unique class of organic dye compounds belonging to the family of red-absorbing dyes, known as squaraines. Our focus lies on elucidating the intricate interplay between the molecular structure, vibrational dynamics, and optical properties of squaraines using state-of-the-art density functional theory calculations and spectroscopic techniques. Through systematic vibrational and optical analyses, we show that (i) the main absorption peak in the visible range is influenced by the conformational and protonation equilibria, (ii) the solvent polarity tunes the position of the UV-vis absorption, and (iii) the vibrational spectroscopy techniques (infrared and Raman) can be used as informative tools to distinguish between different conformations and protonation states. This comprehensive understanding offers valuable insights into the design and optimization of squaraine-based DSSCs for enhanced solar energy conversion efficiency.

Crossroads of vibrational (infrared and Raman) spectroscopy and X-ray powder diffraction in identification and characterization of some minerals – advantages and limitations. A review

Many analytical methods have been successfully employed for the study of minerals, in particular, vibrational infrared (FTIR) and Raman spectroscopies and X-ray powder diffraction (XRPD). The advantages of the vibrational spectroscopic techniques for identifying and characterizing minerals include: rapid and versatile use; qualitative and quantitative chemical signatures; distinctive chemical fingerprint of a material; indirect determination of the crystal features (polymorphism, isomorphism, coordination, degree of deformation of structural polyhedra); small sample quantity (area less than 1 μm2 for Raman); wide coverage of 4,000 – 50 cm−1 region in a single scan; in situ and direct measurements without sample preparation; nondestructive use; etc. On the other hand, XRPD is a destructive technique that, depending on the method used and the density of the material, requires from a few micrograms up to around 5 grams of sample quantity for analysis. In spite of that, it is a rapid and powerful technique used in mineral studies with relatively straightforward interpretation of the results. During the last decade, portable X-ray powder diffractometers for the nondestructive analysis of art and archeological materials have been developed along with the portable and hand-held vibrational spectroscopy instrument. Here, some advantages and limitations in the process of the complementary use of FTIR and Raman vibrational spectroscopy and XRPD for identification and characterization of minerals are outlined.

Rapid quantification models for assessing melamine adulteration in sport nutrition supplements via benchtop and portable NIRS instruments

Sport nutrition supplements (SNS) are vulnerable to adulteration with melamine, artificially augmenting their protein content as determined by conventional assay methodologies. Vibrational spectroscopy techniques are suitable for the detection of adulteration because they allow rapid analysis, require minimal sample preparation, and can perform numerous analyses in a short time. The aim of this study was to develop rapid quantification models for the determination of melamine adulteration in a variety of SNS matrices using NIRS (near-infrared spectroscopy) in combination with multivariate data processing. Moreover, a comparison of benchtop and portable NIR instruments was carried out. Employing a stepwise approach involving OPLS-DA and PLS analysis, matrix discrimination and prediction ability were investigated. The benchtop instrument effectively discriminated among matrices (R2Y = 0.964, Q2 = 0.933), while the portable device, although showing a slightly altered pattern, maintained favorable discrimination capability (R2Y = 0.966, Q2 = 0.931). The quantitative PLS models for each SNS matrix exhibited comparable statistical indicators for both instruments with reasonable errors for melamine content estimation and prediction (RMSEE: 0.3–2.4 %, RMSEP: 0.98–2.99 %). Higher estimation and prediction errors were observed for protein-containing samples in both acquisition modes, probably due to the tendency of protein agglomeration and adhesion to different surfaces, which affects the homogeneity of the powder. Despite data loss due to the narrower spectral range and lower resolution of the portable instrument, all models were found to be suitable for predicting melamine content in sport nutrition supplements.

Study of biphasic calcium phosphate (BCP) ceramics of tilapia fish bones by age

Biphasic calcium phosphate (BCP), consisting of bioceramics such as HAp + β-TCP and Ca10(PO4)6(OH)2 + Ca3(PO4)2, is a popular choice for optimizing performance due to its superior biological reabsorption and osseointegration. In this study, BCP was produced by calcining the bones of tilapia fish (Oreochromis niloticus) reared in net cages and slaughtered at an age ranging from 15 to 420 days. The bones were cleaned and dried, calcined at 900 °C for 8 h, and then subjected to high-energy grinding for 3 h to produce BCP powders. After the calcination process, the crystalline phase’s hydroxyapatite (HAp) and/or beta-tricalcium phosphate (β-TCP) were present in the composition of the bioceramic. The age-dependent variation in phase composition was confirmed by complementary vibrational spectroscopy techniques, revealing characteristic peaks and bands of the bioceramic. This variation was marked by an increase in HAp phase and a decrease in β-TCP phase. Thermogravimetric Analysis (TGA) and Differential Thermal Analysis (DTA) from 25 to 1400 °C showed the characteristic mass losses of the material, with a greater loss observed for younger fish, indicating the complete removal of organic components at temperatures above 600 °C. Comparison of the results obtained by X-Ray Diffraction (XRD) and Rietveld refinement with Raman spectroscopy showed excellent agreement. These results showed that with temperature and environment control and adequate fish feeding, it is possible to achieve the desired amounts of each phase by choosing the ideal age of the fish. This bioceramic enables precise measurement of HAp and β-TCP concentrations and Ca/P molar ratio, suitable for medical orthopedics and dentistry.

Vibrational Analysis and Concentration Dependent SERS Study of Cefoperazone

Cefoperazone is a broad-spectrum antibiotic that is extremely efficient in the treatment of respiratory, abdominal, or genital infections. Vibrational spectroscopic techniques, FT-IR, Raman, and SERS, along with DFT calculations, were involved in investigating the normal modes of vibration and adsorption behavior of this antibiotic. Using both the experimental and theoretical data, the bands in the Raman and IR spectra were assigned to the normal vibrational modes. The SERS spectra were successively obtained by using silver and gold colloidal nanoparticles as a substrate. Their analysis revealed that the molecule is chemisorbed on the nanostructured surface through the as-denoted nitrogen ring. Changes observed in the SERS spectra recorded at different cefoperazone concentrations, i.e., modifications in the relative intensity of specific bands suggest the reorientation of adsorbed molecules towards the metal surface.

Spectroscopic and computational studies of the biomolecular complex of chemotherapy drug, lomustine and a nucleotide base adenine

Cancer is still the leading cause of death in both developing and economically developed countries. There is still a need to create new drugs with higher efficacy despite substantial research on the biological pathways of cancer, target identification, and development of therapeutic interventions. Lomustine is an anticancer medication, while Adenine is a purine derivative with great potential for use as a cancer therapy. The present study is carried out to understand the geometrical and quantum chemical parameters of the Adenine + Lomustine as a potential anti-cancer agent by means of the density functional theory method and vibrational spectroscopic techniques. Natural bond orbital analysis, powder X-ray diffraction and quantum theory of atom in molecule analysis are used for investigating the intermolecular hydrogen bond formed in the biomolecular complex. The oral bioavailability and pharmacological activity of the Adenine + Lomustine complex is estimated by drug likeness and bioactivity score prediction. Docking of the biomolecular complex is also carried out against the chosen receptors.