FT-Raman Spectra Research Articles

Novel Mo: CoFe2O4 nanoparticles combustion synthesis for opto-magneto-electrochemical applications: A systematic analysis

In current work, various concentrations (0.0 wt%, 0.10 wt%, 0.25 wt%, 0.50 %,0.75 wt%, and 1 wt%) of Molybdenum (Mo) - doped cobalt ferrite (CFO) nanoparticles (Mo:CFO NPs) were synthesized using the flash combustion approach. The structural analysis of the prepared Mo:CFO was examined by the XRD patterns, and the obtained crystallite size 48.64, 46.72, 22.81, 21.05, 18.03, and 19.31 nm for 0.0 wt%, 0.10 wt%, 0.25 wt%, 0.50 wt%, 0.75 wt%, and 1 wt% Mo:CFO NPs, respectively. The presence of stoichiometry and homogeneity of the prepared Mo:CFO NPs was confirmed by the EDX analysis. The five phonon modes of the prepared Mo:CFO NPs were recorded by FT-Raman spectra, and the phonon modes were observed around 220, 312, 479, 624, and 685 cm−1 that corresponded o T2g(2), Eg, T2g(1), A1g(2), and A1g(1) symmetries, respectively. The grain sizes of the pure CFO and Mo:CFO NPs were evaluated using the images of scanning electron microscopy (SEM) and obtained in the range of 39–61 nm, respectively. The presence of valence states Co (2p), Fe (2p), O (1 s), and Mo (3d) in the prepared 1 wt% Mo:CFO NPs were examined XPS spectra. The particle sizes ~26.4 nm and ~ 16.7 nm were obtained for pure CFO and 1 wt% Mo:CFO NPs using lognormal function fitting. The emission peaks at 445 ± 3, 521 ± 3, and 620 ± 2 nm in the PL spectra were observed by PL spectroscopy. The decrease in saturation magnetization Ms. (70.80–66.54 emu/g) and reduced remanent magnetization Mr. (24.22–18.64 emu/g) of prepared Mo: CFO NPs was observed in the MH analysis by SQUID analysis. The electrochemical study of Mo: CFO NPs (0.0 %, 0.25 %, 0.50 %, and 1.0 %) was done in a three-electrode assembly cell. The capacitance of values 650.0 Fg−1, 800.0 Fg-1, and 810.0 Fg−1 for pure CFO, 0.25 % Mo: CFO, and 0.50 % Mo: CFO were recorded in electrochemical analysis. The highest capacitance of 840.0 Fg−1 was observed for the electrode with 1.0 % Mo: CFO NPs. It was analyzed that the increase in CFO electrodes enhances their performance, and therefore, it can be utilized for multifunctional devices.

Exploring the impact of opioids on serum chemistry: Insights from FT-Raman spectroscopy and biochemical analysis

Opioids are drugs whose use has increased dramatically over the last two decades. Opioids are a family of drugs that includes the illegal drug heroin, synthetic opioids such as fentanyl, and painkillers that are legally available on prescription. Unfortunately, too long use of these drugs can lead to addiction, which might cause disturbed physiological and mental effects. Regular opioid usage might cause common mental disorders such as depression, anxiety, and panic disorder. However, there is still no rapid detection method to describe the chemical changes caused by the Opioid use disorder. For this reason, this study used conventional FT-Raman spectroscopic techniques with multivariate analysis to detect chemical changes in serum following opiate administration. In the FT-Raman spectrum collected from opioid-addicted patients, significant shifts of peaks at 892 cm−1, 966 cm−1, 1286 cm−1, 1459 cm−1 and 2940 cm−1 were visible in comparison with the spectrum of serum collected from the control group. Furthermore, changes in the ratio of amides and lipids were observed in the non-control group, suggesting that opioids could cause structural changes in the compounds. Synchronous spectra show auto peaks at 2914 cm−1, 3415 cm−1 while asynchronous negative cross area between 1005 cm−1 and 1800 cm−1 and around 3000 cm−1 indicate higher presence of polysaccharides and amides in comparison with other compounds in serum collected from non-control group. Finally, the PCA model, utilizing three components that explain 94.89 % of the data variation within the 300–3700 cm⁻¹ range, demonstrates excellent performance. The ensemble classification method achieves accuracies of 97.96 % and 95.00 % on the training and test datasets, respectively. Furthermore, the method achieves AUC-ROC scores of 1.00 and 0.99 for the training and test sets, effectively distinguishing between control and opioid-addicted individuals.

Detection of serum alterations in polysubstance use patients by FT-Raman spectroscopy

Substance use disorders pose significant health risks and treatment challenges due to the diverse interactions between substances and their impact on physical and mental health. The chemical effects of multiple substance use on bodily fluids are not yet fully understood. Therefore, this study aimed to investigate the chemical changes induced by a combination of substances compared to a control group. Analysis of FT-Raman spectra revealed structural alterations in the amide III, I, and C = O functional groups of lipids in subjects treated with opioids, alcohol and cannabis (polysubstance group). These changes were evident in the form of peak shifts compared to the control group. Additionally, an imbalance in the amide-lipid ratio was observed, indicating perturbations in serum protein and lipid levels. Furthermore, a 2D plot of two-track two-dimensional correlation spectra (2T2D-COS) demonstrated a shift towards dominance of lipid vibrations in the polysubstance use groups, contrasting with the predominance of the amide fraction in the control group. This observation suggests distinct molecular changes induced by multiple substance use, potentially contributing to the pathophysiology of substance use disorders. Principal Component Analysis (PCA) was utilized to visualize the data structure and identify outliers. Subsequently, Partial Least Squares Discriminant Analysis (PLS-DA) was employed to classify the polysubstance use and control groups. The PLS-DA model demonstrated high classification accuracy, achieving 100.00 % in the training dataset and 94.74 % in the test dataset. Furthermore, receiver operating characteristic (ROC) analysis yielded perfect AUC values of 1.00 for both the training and test sets, underscoring the robustness of the classification model.This study highlights the quantitative and qualitative changes in serum protein and lipid levels induced by polysubstance use groups, as evidenced by FT-Raman spectroscopy. The findings underscore the importance of understanding the chemical effects of polysubstance use on bodily fluids for improved diagnosis and treatment of substance use disorders. Moreover, the successful classification of spectral data using machine learning techniques emphasizes the potential of these approaches in clinical applications for substance abuse monitoring and management.

A comprehensive analysis of the spectroscopic and drug-like properties of dimethyl 5-hydroxybenzene-1,3-dicarboxylate: insights from DFT and MD simulations

ABSTRACT An in-depth investigation was undertaken to explore the ground-state molecular and electronic structure of Dimethyl 5-hydroxybenzene-1,3-dicarboxylate (D5HD). The potential energy scan of D5HD at various dihedral angles identified the lowest energy conformer, which was re-optimised at the higher basis set. The recorded FT-Raman and FT-IR spectra were compared with corresponding theoretical spectra, demonstrating a high degree of coherence. A comprehensive Natural Bond Orbital analysis was done for D5HD to gain insights for the overall electronic distribution within the molecule. Additionally, nonlinear optical (NLO) properties along with various DFT-based descriptors were calculated. Molecular docking studies against human acetylcholinesterase enzyme (PDB 2JF0), D5HD displayed good binding affinity. The study revealed that hydrogen bonded as well as van der Waals interactions exist between D5HD and different residues in the binding cavity of the target protein. The 100 ns MD simulation confirms the conformational stability of protein (2JF0)–ligand (D5HD) complex. The binding energy and residue decomposition analysis performed using MM-GBSA approach showed positive results with binding energy of −17.76 kcal/mol. Furthermore, D5HD effectively passed all pharmacokinetic filters, establishing its potential as a promising candidate in the quest for novel acetylcholinesterase inhibitors. Highlights Systematic exploration of the structure and spectroscopic properties of D5HD. Molecular docking between D5HD and acetylcholinesterase (PDB 2JF0) reveals the establishment of hydrogen bonds and Van der Waals interactions. D5HD successfully complies with all relevant pharmacokinetic filters. MD simulation analysis on 2JF0–D5HD complex confirms the conformational stability. Energy and residue decomposition based on MMGBSA approach.

Investigating the Formation of Different (NH4)2[M(H2O)5(NH3CH2CH2COO)]2[V10O28]·nH2O (M = CoII, NiII, ZnII, n = 4; M = CdII, MnII, n = 2) Crystallohydrates

Three hybrid compounds based on decavanadates, i.e., (NH4)2[Co(H2O)5(β-HAla)]2[V10O28]·4H2O (1), (NH4)2[Ni(H2O)5(β-HAla)]2[V10O28]·4H2O (2), and (NH4)2[Cd(H2O)5(β-HAla)]2[V10O28]·2H2O (3), (where β-Hala = zwitterionic form of β-alanine) were prepared by reactions in mildly acidic conditions (pH ~ 4) at room temperature. These compounds crystallise in two structure types, both crystallising in monoclinic P21/n space group but with dissimilar cell packing, i.e., as tetrahydrates (1 and 2) and as a dihydrate (3). An influence of crystal radii and spin state of the central atom in [M(H2O)5(β-HAla)]2+ complex cations on the crystal packing leading to the formation of different crystallohydrate forms was investigated together with previously prepared (NH4)2[Zn(H2O)5(β-HAla)]2[V10O28]·4H2O (4) and (NH4)2[Mn(H2O)5(β-HAla)]2[V10O28]·2H2O (5) and spin states of [M(H2O)5(β-HAla)]2+ (M = Co2+, Ni2+, and Mn2+) cations in solution were confirmed by 1H-NMR paramagnetic effects. FT-IR and FT-Raman spectra for 1–5 are in agreement with the X-ray structure analysis results.

Structural reactions, green chemistry solvents, topology surface, electronic and biological studies of 4-(dihydroxymethyl) pyridine-2-carbonitrile – Anti-tuberculosis activity

Spectroscopic properties of 4-(dihydroxymethyl) pyridine-2-carbonitrile have been theoretically scrutinized using DFT technique utilizing B3LYP approach along with 6–311G++(d,p) basis set. Electronic-stability, electronic transitions, and distribution of charge within the molecule were analyzed using FMO and NBO analyses, which involve π*(C13–C14) to π*(C10–C15) transition, with a maximum stabilization energy of 212.33 kcal/mol, which ascertain the molecule's stability. Vibrational assignments for FT-IR and FT-Raman spectrum have been conducted using PED for identifying functional groups. Topological analyses such as ELF, LOL, and RDG provided a comprehensive understanding of the distribution of charged particles across each element within molecule, enabling the identification of electrophilic and nucleophilic sites. DMPC adheres to Lipinski's rule of five, indicating suitability for oral administration similar to other drugs. Investigations using molecular docking were performed to analyze the biological asset of the compound. Protein 6UCR demonstrated superior binding potency with a minimum binding-energy reaching −8.5 kcal/mol, revealing its potential treatment for tuberculosis.

Investigation of the molecular structure of CHBP, biological activities and SARS-CoV-2 protein binding interaction by molecular and biomolecular spectroscopy approaches

The objective of this investigation is to learn more about the structural, electrical, spectroscopic, and physiochemical characteristics of biologically active cyano-4′-hydroxybiphenyl (CHBP). The title molecule’s optimized conformational analysis was computed using the DFT/B3LYP/6–311++G (d, p) level of theory. The observed wavenumbers were compared with theoretical FT-IR and FT-Raman spectra. 1H and 13C NMR experimental spectra in CDCl3 solution (solvent phase) were recorded and the chemical shift was calculated. NBO analysis was used to examine the transfer of charge as well as the intermolecular and intramolecular bonding of orbitals. The TD-DFT (time-dependent DFT) approach was used to estimate theoretical values for both the gas and solvent (ethanol) in the corresponding transitional research, which was conducted using UV–Vis’s spectra. Energy gap (Eg = 0.26764 eV) implies that the strong potential for charge transfer, and the stability of the CHBP compound. CHBP compound’s has bioactive nature, its drug-likeness and biological properties were evaluated. The predicted topological polar surface area of 44.02 \\AA2 for the molecule falls within the permissible range of < 140 \\AA2. Based on the docking results, the most stable docking score value is −6.84 kcal/mol. In that interaction, MET 165 affects both phenyl rings in a pi-sulphur fashion and a single bond hydrogen with protein moieties GLN 192. This suggests that the pi-alkyl in PRO 168 is a hydroxyl substitutional ring. Our findings demonstrate the CHBP compound is a good inhibitor against the SAR COVID-19 viral protein.

Vibrational assignments of monohydrate dimer of violuric acid by using FT-IR, FT-Raman and UV spectra and DFT calculations in different media

Experimental FT-IR, FT-Raman and UV spectra have been combined with hybrid B3LYP/6–311++G** calculations and the scaled quantum mechanical force field (SQMFF) methodology to study structural and vibrational properties of monohydrated dimer (MD) of violuric acid in gas and aqueous media. Complete vibrational assignments and its scaled force constants are reported together with the corresponding to anhydrous and monohydrate monomer. From four anhydrous C1, C2, C3, C4 monomers, C4 is the most stable in both media. In solution, the initial structure of C2 change to the tautomeric species most stable C4. The MD reveals a higher solvation energy while natural bond orbital (NBO) and atoms in molecules (AIM) calculations support the higher stability of this species due to the six H bonds interactions and to its higher expansion of volume in solution. The MD is the most reactive species, as revealed by the lowest gap value and by high global electrophilicity and most negative global nucleophilicity indexes. Very good concordances are observed among the predicted IR, Raman, 13C NMR and UV spectra and the corresponding experimental ones. Comparisons of predicted 13C NMR and electronic spectra with the experimental one show that those three species of violuric acid could be present in aqueous solution. Similar f(νC=O) and f(νC-O) force constants for the three species are justified by the important delocalization of electrons evidenced in anhydrous and monohydrate species by NBO calculations.

Simultaneous purification and oxidation of the as-synthesized MWCNTs with KMnO4 using phase transfer catalyst at three different pH medium by the hydrothermal method

Improving and streamlining current oxidation techniques for experimental is the main goal of the research described in the present article. By applying the pressure created while on the hydrothermal process to an autoclave walled with Teflon, simplifying the procedure was accomplished. By comparing the degrees of functionalization attained with the dispersibility in the substantially pure and functionalized multi-walled carbon nanotubes (MWCNTs) final product, the beneficial effect of the procedure was evaluated. In order to achieve this, the study looked at and investigated how as-synthesized MWCNTs from Fe-Mo/MgO catalyst were simultaneously purified and oxidized using the chemical vapor deposition (CVD) method. Aliquot-336 was used as phase transfer catalyst (PTC) by hydrothermal method under three different pH conditions. Following functionalization, nanotubes of carbon might easily combine with various chemical reagents to generate homogeneous dispersions or even well-aligned structures because of the functional groups linked to their surfaces. In this case, a chemical called reagent potassium permanganate (KMnO4) is necessary in order to target particular π-bonds while entirely destroying the nanotubes' graphene structures. The techniques have been explained in terms of mechanism, and the Fourier transform-infrared (FT-IR) spectroscopy has confirmed the functionalizations of the CNTs. These approaches were further explored through FT-Raman spectrum analysis, thermal assessments, energy dispersive X-ray spectroscopy (EDX), TEM (transmission electron microscopy) along with the help of EDX, and visible-near IR absorption and UV–visible absorption spectroscopy (ABS) procedures.

Effect of intermolecular interactions and pharmacokinetic profile of antidiabetic agent (E)-N,N‑diethyl-2-(5(3‑hydroxy-4-methoxybenzylidene)-2,4-dioxothiazolidin-3-yl) acetamide

Diabetes is a prevalent disease in South India, posing a severe threat to public health. To tackle this issue, researchers are focusing on developing multi-targeted ligands, and one promising candidate is (E)-N,N‑diethyl-2-(5(3‑hydroxy-4-methoxybenzylidene)-2,4-dioxothiazolidin-3-yl)acetamide (DMDA). Geometry optimization of DMDA was carried out using density functional theory with 6–311+G(d, p) basis set to develop a theoretical model close to the previously synthesized and reported DMDA. Natural Bond Orbital analysis was conducted to scrutinize the phenomena of charge delocalization and electronic exchange interactions governing both intermolecular and intramolecular associations. Moreover, the vibrational characteristics of the molecule were elucidated through FT-IR and FT-Raman spectra. Lowest Unoccupied Molecular Orbital and Highest Occupied Molecular Orbital have also been explored to enhance understanding of the molecule's electronic structure and reactivity. Hirshfeld surface analysis was utilized to investigate the interactions between molecules within the crystalline lattice. Absorption, distribution, metabolism, excretion, and toxicity (ADMET) analysis elucidates the potential pharmacokinetic profile of DMDA. Molecular docking was performed to predict the binding site responsible for various interactions with the targeted protein. By combining these techniques, a comprehensive molecular description of DMDA has been generated.There are three prominent intramolecular interactions within the ambit of van der Waals radii, leading to stability of the molecule. The presence of a broad and shallow band with a significant red shift provides evidence for the strong intermolecular OH hydrogen bonding. DMDA complies with Lipinski's Rule of Five, highlighting its favorable characteristics for pharmaceutical efficacy. The negative binding energies determined by docking studies ascertain the potential sites of ligand-protein interaction leading to inhibition of α-amylase and α-glucosidase enzyme.

Identification of cholesterol in different media by using the FT-IR, FT-Raman and UV–visible spectra combined with DFT calculations

In this investigation, the experimental FT-IR and FT-Raman spectra of cholesterol in the solid phase and in ethanol solution have been combined with the B3LYP/6–311++G** calculations and the scaled quantum mechanical force field (SQMFF) methodology, normal internal coordinates and transferable scaling factors to obtain the complete vibrational assignments of 216 vibration modes expected. Hence, complete vibrational assignments for that steroid of greatest biological importance are reported for first time in gas phase and ethanol solution together with its scaled force constants. Changes in the positions of some bands and in force constants values are observed in the different media due to the predicted intra-molecular interactions between CH3/CH3, CH3/CH2 and CH2/CH2 groups by atoms in molecules (AIM) calculations. The 1H- and 13C NMR chemical shifts of normal and deuterated cholesterol in aqueous solution confirm that the H atom of OH group is involved in the formation of H bonds in solution. Studies of experimental electronic spectra of cholesterol in different concentrations of ethanol revealed that the positions of peaks maxima increase conform increase the solution concentration. The natural bond orbital (NBO) analyses reveal that the polar OH group and the four fused rings play important roles in the stability and properties of cholesterol than the large hydrophobic moiety. Frontier orbitals predicted low reactivity of cholesterol in ethanol probably due to its high ω value in this medium.

Interactions of gliadins with flavonoids and their glycosides studied with application of FT-Raman spectroscopy

FT-Raman spectroscopy was applied to study interactions between wheat gliadins and three flavonoids and their glycosides. Complexes gliadins-flavonoids/glycosides were extracted from the model wheat dough. As flavonoids were used quercetin, naringenin, hesperetin and their glycosides rutin, naringin, hesperidin in the amount of 0.05%, 0.1% and 0.2%. The analysis of the FT-Raman spectra showed that the tested compounds caused changes in the secondary and tertiary structure of gliadins. In the case of gliadins, these changes concerned mainly α-helices. Quercetin induced a different type of structural changes compared to naringenin and hesperetin, which was probably due to the presence of a double bond on the C ring and an additional OH group on the B ring in the structure of this molecule. On the other hand, the interactions of glycosides with gliadins were affected by the place of attachment of the sugar part in the structure of the glycoside. Flavonoids/glycosides significantly increased the content of disulfide bridges in the g-g-g conformation. Changes in the amino acid microenvironment (tyrosine and tryptophan) indicate the formation of a more ordered structure in gliadins.

Synthesis, crystal structure, Hirshfeld surface analysis, spectral characterisation, non-covalent interactions and anti-microbial investigation on morpholinium adipate: a combined experimental and DFT approach

MPAA was synthesised and evaluated using spectroscopic methods and quantum chemical computations in the proposed investigation. Extensive quantum chemical computations were employed to analyse FT-IR, FT-Raman and NMR spectra of molecule morpholinium adipate (MPAA). The results of a single crystal X-ray diffraction (SCXRD) experiment were compared with estimated structural characteristics. In conjunction with the scaled force constants, a comprehensive vibrational assignment is provided for the 96 anticipated vibration modes of MPAA. Charge transport inside the molecule is exposed by the band gap energy of 5.959 eV, which is the consequence of the predicted Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) values of −6.991 and −1.031 eV, respectively. The inter- and intramolecular H-bonding contacts in the molecule were studied using natural bond orbital analysis to learn more about the biological active site. The eventual charge transfer inside the molecule is supported by frontier molecular orbital analysis and natural bond orbital analysis. The anti-bonding of H15–O24 atoms and the lone pair N14 had the greatest stabilising energy at 16.52 kcal/mol. Using Hirshfeld surface analysis methods, intermolecular connections and crystal packing of MPAA are investigated. The fukui and electrostatic potential plot analyses can provide information about the molecule’s electrophilic and nucleophilic locations. Antimicrobial tests have been performed to see how well the chemical worked against various bacterial and fungal strains. Docking of 8OEO (Aspergillus Niger), 7C2O (Candida parapsilosis), 2O6I (Enterococcus faecalis) and 1DZO (Pseudomonas aeruginosa) proteins has been done, and lowest binding energy −4.57 kcal/mol has been achieved for 7C2O protein.

Synthesis, structural examination, molecular interaction analysis, invitro and insilico anticancer activity investigation of a new curcumin derivative: 1- (4 – chlorobenzoyl) - 3, 5 - bis ((E) - 4 - methoxybenzylidene) piperidin - 4 – one

The title material, C28H24ClNO4, was synthesized using the Claisen-Schmidt condensation reaction and Schotten-Baumann reaction methods and crystallized. Geometrical parameters were determined for the grown crystal using the Single Crystal X-Ray Diffraction (SCXRD) technique. The title compound has been characterized and anzalyzed for its optical properties via1H1 and 13C NMR, FT-Raman, and FT-IR, UV and PL spectra. The melting point and thermal stability have been investigated using TG/DTA thermograms.Hirshfeld surfaces were developed in order to observe and quantify short contacts, CH…π and π...π stacking interactions. To determine how various interactions influence the overall Hirshfeld surface, 2D fingerprint plots were created, and it was discovered that the H…H contact's contribution was the most significant. Cytotoxic effect on HEK293 cell lines was performed and found to be highly toxic. To determine the compound's efficacy as an anticancer agent, a research was conducted using MCF-7 cell lines. Molecular docking simulation revealed that the title material (ligand) fits well at the active site of the target protein with PDB ID: 1M17. Pharmacokinetic, and ADMET properties revealed that the compound is exceedingly orally active, and after further biological and pharmaceutical investigations, the compound can be recommended as a drug candidate.

Synthesis, NMR, FT-IR, FT-Raman spectra and thermal studies of Choline bis(trifluoromethylsulfonyl)imide ionic liquid combined with DFT calculations

In an environmentally friendly manner, the reaction of choline chloride ([CHOL+][(Cl−]) with lithium bis(trifluoromethanesulfonyl)imide ([Li+][(CF3SO2)2N−]) in water leads to the formation of the ionic liquid(IL)choline bis(trifluoromethanesulfonyl)imide ([CHOL+][(CF3SO2)2N−]).The ionic liquid IL have been characterized by using1H, 13C and, 19F-NMR, FT-IR and FT-Raman spectroscopies. The experimental spectra have been combined with B3LYP/6–311++G** calculations to obtain complete assignments of vibrational spectra of IL and its cation by using the scaled mechanical quantum force field (SQMFF) methodology and the Molvib program. Here, we reported the 102 vibration modes of IL and the 36 of cation together with the scaled force constants for both species. The predicted structure shows the formation of the S-O···H interaction in agreement with experiments. Very good correlations evidence the comparisons among the experimental and theoretical NMR, FT-IR and FT-Raman spectra. The existence of the strong S-O···H interaction and other weak H bonds interactions are supported by NBO and AIM calculations. The analyses of gap values suggest a higher reactivity of IL in gas phase and a higher stability in aqueous solution. The comparison of this IL with [C8DABCO+][(CF3SO2)2N−] reveal that the [C8DABCO+] cation increases the reactivity of latter IL in solution. Besides a detailed characterization of its thermal (TGA/DSC) is presented. Investigation of the thermal properties demonstrated that the investigated IL can be classified as an ionic liquid, as the melting temperature is near room temperature. A glass transition and a cold crystallization were revealed at -75 and -26 °C.

FT-IR, FT-raman and UV spectra and ab initio HF and DFT study of conformational analysis, molecular structure and properties of ortho- meta– and para–chlorophenylboronic acid isomers

In this study, the FT-IR, FT-Raman, and UV–Vis spectroscopic properties of three monosubstituted phenylboronic acid derivatives: ortho-chlorophenylboronic acid (o-ClPhBA), meta-chlorophenylboronic acid (m-ClPhBA) and para-chlorophenylboronic acid (p-ClPhBA) molecules are investigated both experimentally and theoretically using Density Functional Theory (B3LYP) and Hartree Fock (HF). In order to find the stable possible conformations of the compounds, the conformational analysis was carried out by running potential energy surface (PES) scan by means of rotation of two structural parameters, the dihedral angles indicated as φ2 (C6–B–O1–H1A) and φ3 (C6–B–O2–H2A), varying from −180° to 180° with an increment of 10° using B3LYP/6-31G level of theory. Also, to determinate the most stable conformer for all the molecules, potential energy curve (PEC) the stable possible conformations on PES scan were investigated as a function of φ1 (C1-C6–B–O1) dihedral angle from 0° up to 180° with an increment of 10° using B3LYP/6–311++G(d,p) and HF/6–311++G(d,p) level of theory. For all the studied compounds, two conformational structures (conformer anti-anti, syn-syn) that did not have imaginary frequency values outside the equilibrium state (conformer anti-syn) were detected theoretically at the both methods.Due to their conformational flexibility, the relative stabilities of the anti-syn, anti-anti, and syn-syn conformers of o-ClPhBA, m-ClPhBA, and p-ClPhBA are 0.0, 4.66, and 6.76 kcal/mol, respectively, at the B3LYP/6–311++G(d,p) level of theory. For the HF/6–311++G(d,p) level of theory, the relative stabilities are 0.00, 4.54, and 6.11 kcal/mol for o-ClPhBA; 0.00, 3.98, and 1.51 kcal/mol for m-ClPhBA; and 0.00, 4.10, and 1.44 kcal/mol for p-ClPhBA, respectively. Some of the determined stable conformations of these molecules are different in symmetry groups. It was observed that the increase in the symmetry was effective in the of molecular properties, especially for vibrational frequencies. The structural parameter, dipole moments (μ), vibrational frequencies, polarizability (α), hyperpolarizability (β), the highest occupied molecular orbital (HOMO), and the lowest unoccupied molecular orbital (LUMO) of the stable conformers were calculated by using Ab initio HF/6–311++G(d,p) and DFT/B3LYP/6–311++G(d,p) level of theory. The assignments of fundamental vibrational modes of the studied molecule were performed based on total energy distribution (TED) analysis.

Growth, DFT, spectroscopic analysis, third-order NLO properties and optical limiting behavior of Bis(p-aminobenzoic acid-N) dichloro cadmium (II) (BPANDC) crystal

A new organic nonlinear optical crystal, Bis(p-aminobenzoic acid-N) dichloro cadmium (II) (BPANDC) has been grown by Slow Evaporation Solution Technique (SEST). The experiments were carried out to study the structural, optical, DFT and nonlinear optical properties of the grown crystals. The BPANDC crystal belongs to triclinic system with space group Pī with lattice parameters a = 6.359(4)Å, b = 7.509(11)Å, c = 17.263(7)Å, α= 94.50(2)˚, β=104.56(2)˚, γ=96.79(4)˚, and volume V = 787.20Å3. Using the TD-DFT method, the electronic absorption spectra of BPANDC was calculated in gas phase. The calculated FT-IR, FT-Raman spectrum, Molecular geometrical analysis, TD-DFT, HOMO–LUMO energy gap and Molecular electrostatic potential surface of BPANDC were calculated by DFT/ LANL2DZ basis set. The Z-scan analysis evidenced that the BPANDC exhibits sequential two-photon absorption induced reverse saturable absorption.

FT-Raman spectra in combination with machine learning and multivariate analyses as a diagnostic tool in brain tumors

Brain tumors are one of the most dangerous, because the position of these are in the organ that governs all life processes. Moreover, a lot of brain tumor types were observed, but only one main diagnostic method was used – histopathology, for which preparation of sample was long. Consequently, a new, quicker diagnostic method is needed. In this paper, FT-Raman spectra of brain tissues were analyzed by Principal Component Analysis (PCA), Hierarchical Cluster Analysis (HCA), four different machine learning (ML) algorithms to show possibility of differentiating between glioblastoma G4 and meningiomas, as well as two different types of meningiomas (atypical and angiomatous). Obtained results showed that in meningiomas additional peak around 1503 cm−1 and higher level of amides was noticed in comparison with glioblastoma G4. In the case of meningiomas differentiation, in angiomatous meningiomas tissues lower level of lipids and polysaccharides were visible than in atypical meningiomas. Moreover, PCA analyses showed higher distinction between glioblastoma G4 and meningiomas in the FT-Raman range between 800 cm−1 and 1800 cm−1 and between two types of meningiomas in the range between 2700 cm−1 and 3000 cm−1. Decision trees showed, that the most important peaks to differentiate glioblastoma and meningiomas were at 1151 cm−1 and 2836 cm−1 while for angiomatous and atypical meningiomas – 1514 cm−1 and 2875 cm−1. Furthermore, the accuracy of obtained results for glioblastoma G4 and meningiomas was 88 %, while for meningiomas – 92 %. Consequently, obtained data showed possibility of using FT-Raman spectroscopy in diagnosis of different types of brain tumors.

Spectroscopic characterization, quantum chemical and molecular docking investigations on methyl indole-3-carboxylate: A potent cervical cancer drug

Bioactive indole derivatives had great importance in recent years due to their numerous biological and pharmaceutical applications. In the present work, the vibrational, electronic, physicochemical, and inhibitory properties of the Methyl Indole-3-Carboxylate (MIC) molecule were predicted and analyzed. Initially, the molecular structure of the title molecule was optimized and its structural parameters were calculated, which were highly correlated with the previous reports. The simulated infrared and Raman spectra of the molecule were in good agreement with the FT-IR and FT-Raman spectra that were observed via the experiment. The observed UV–Visible spectrum validates the MIC molecule's π→π* electronic transition, which was also well matched with the simulated UV–Visible spectrum. The investigation of frontier molecular orbitals highlights intramolecular charge transfer across the molecule, establishing the bioactivity of the MIC molecule. The electron transport from the methyl group hydrogen atom H22 to the oxygen atom O11 is confirmed by Mulliken atomic charge distribution analysis and molecular electrostatic potential surface analysis. The calculated Fukui functions values validated the FMOs and Mulliken atomic charge distribution results. The natural bond orbital study further confirms the MIC molecule's intramolecular charge transfer and bioactivity. Molecular docking investigation results that the MIC molecule hinders the function of an enzyme known as Mitogen-activated protein kinase 14, which has been linked to cervical cancer. As a result, the present study provides the possibility towards the development of innovative to treat cervical cancer.

Crystal growth and vibrational spectroscopic studies on the novel NLO active 2-amino-4-methylpyridinium fluoroborate single crystal by experimental and computational technique

A semi-organic non-linear optical (NLO) single crystal of 2-amino-4-methylpyridinum fluoroborate(2AFB) to be synthesized and characterized via single crystal X-ray diffraction technique (SXRD), UV–Vis, FTIR and FT-Raman spectra. The quantum chemical calculations were carried out using density functional method (DFT) with B3LYP/6–31+G(D) basis set. The intermolecular interaction and stability of the title molecule have been obtained by NBO analysis. The molecular electrostatic potential and frontier molecular orbital analysis give a visual representation of charge distribution of the title molecule. The N-H…F interaction within 2AFB molecule was investigated via AIM and RDG analysis. The optical quality and energy band gap of 2AFB single crystal were found out using UV–visible spectral analysis. The emission spectra of the grown 2AFB single crystal has been examined by fluorescence spectral analysis. 2D fingerprint plot confirms the H…F and H…H interactions that exhibit the most significant contribution in crystal packing. The outcome of SXRD, UV-visible, HOMO-LUMO, NLO and Z-scan values were compared with earlier reported compounds and amongst which the analysed compound 2AFB shows good NLO activity. The NLO activity of the title molecule was confirmed theoretically and experimentally by DFT method and Z-scan technique.