Vibrational Spectroscopic Study Research Articles

Photooxidation of Nonanoic Acid by Molecular and Complex Environmental Photosensitizers.

Photochemical aging and photooxidation of atmospheric particles play a crucial role in both the chemical and physical processes occurring in the troposphere. In particular, the presence of organic chromophores within atmospheric aerosols can trigger photosensitized oxidation that drives the atmospheric processes in these interfaces. However, the light-induced oxidation of the surface of atmospheric aerosols, especially those enriched with organic components, remains poorly understood. Herein, we present a gravimetric and vibrational spectroscopy study aimed to investigate the photosensitized oxidation of nonanoic acid (NA), a model system of fatty acids within organic aerosols, in the presence of complex organic photosensitizers and molecular proxies. Specifically, this study shows a comparative analysis of the photosensitized reactions of thin films containing nonanoic acid and four different organic photosensitizers, namely marine dissolved organic matter (m-DOM) and humic acids (HA) as environmental photosensitizers, and 4-imidazolecarboxaldehyde (4IC) and 4-benzoylbenzoic acid (4BBA) as molecular proxies. All reactions show predominant photooxidation of nonanoic acid, with important differences in the rate and yield of product formation depending on the photosensitizer. Limited changes were observed in the organic photosensitizer itself. Results show that, among the photosensitizers examined, 4BBA is the most effective in photooxidizing nonanoic acid. Overall, this work underscores the role of chromophores in the photooxidation of organic thin films and the relevance of such reactions on the surface of aerosols in the marine environment.

Role of Intermolecular Interactions in Deep Eutectic Solvents for CO2 Capture: Vibrational Spectroscopy and Quantum Chemical Studies.

Recent research and reviews on CO2 capture methods, along with advancements in industry, have highlighted high costs and energy-intensive nature as the primary limitations of conventional direct air capture and storage (DACS) methods. In response to these challenges, deep eutectic solvents (DESs) have emerged as promising absorbents due to their scalability, selectivity, and lower environmental impact compared to other absorbents. However, the molecular origins of their enhanced thermal stability and selectivity for DAC applications have not been explored before. Therefore, the current study focuses on a comprehensive investigation into the molecular interactions within an alkaline DES composed of potassium hydroxide (KOH) and ethylene glycol (EG). Combining Fourier transform infrared (FT-IR) and quantum chemical calculations, the study reports structural changes and intermolecular interactions induced in EG upon addition of KOH and its implications on CO2 capture. Experimental and computational spectroscopic studies confirm the presence of noncovalent interactions (hydrogen bonds) within both EG and the KOH-EG system and point to the aggregation of ions at higher KOH concentrations. Additionally, molecular electrostatic potential (MESP) surface analysis, natural bond orbital (NBO) analysis, quantum theory of atoms-in-molecules (QTAIM) analysis, and reduced density gradient-noncovalent interaction (RDG-NCI) plot analysis elucidate changes in polarizability, charge distribution, hydrogen bond types, noncovalent interactions, and interaction strengths, respectively. Evaluation of explicit and hybrid models assesses their effectiveness in representing intermolecular interactions. This research enhances our understanding of molecular interactions in the KOH-EG system, which are essential for both the absorption and desorption of CO2. The study also aids in predicting and selecting DES components, optimizing their ratios with salts, and fine-tuning the properties of similar solvents and salts for enhanced CO2 capture efficiency.

Synthesis, vibrational, thermal, topological, electronic, electrochemical stability and DFT studies of new DABCO based ionic liquids

The design of new ILs with different anions could provide interesting physico-chemical properties and for these reasons, the knowledge about the synthesis, the thermal, vibrational, topological, electronic, electrochemical properties and interaction between the selected cation-anion in these ILs are important subjects. Therefore, the understanding about these properties of these compounds is an important subject of study. In this work, we studied three ionic liquids based on the 1-decyl-1,4-diazabicyclo[2.2.2]octane, DABCO-cation, where the corresponding anions were [Br]-, [PF6]-, and [N(SO₂CF₃)₂]-. The syntheses of these bicyclic DABCO ionic liquids are based on an alkylation reaction of 1,4-diazabicyclo[2.2.2] octane and 1-bromodecanefollowed by anion exchange. The obtained ILs are characterized by 1H, 13C, 19F and 31P-NMR spectroscopy. Vibrational spectroscopy studies are conducted by infrared (FTIR/ATR) and Raman spectroscopy in the wavenumber range 600–4000 cm-1 and 45–3500 cm-1, respectively. Furthermore, the thermal stabilities were investigated using the thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) methods. Results indicate that the thermal stability follow the order [C10DABCO][Br]<[C10DABCO][PF6]<[C10DABCO][N(SO₂CF₃)₂]. Additionally, the structural parameters, electrostatic potential (ESP) maps, interaction energies, non-covalent interaction (NCI), atoms in molecule (AIM) analysis, natural bond orbital (NBO), frontier molecular orbital (FMO) analysis and Electrochemical window (ECW) are studied and analyzed by means of DFT calculations at the M06–2X-GD3/AUG–cc–pVDZ level of theory.

Reactions of Aluminum Oxide Cluster Cations with Ethane: A Mass-Spectrometric and Vibrational Spectroscopy Study.

The pathways for the reactions of aluminum oxide cluster ions with ethane have been measured. For selected ions (Al2O+, Al3O2+, Al3O4+, Al4O7+) the structure of the collisionally-stabilized reaction intermediates were explored by measuring the photodissociation vibrational spectra from 2600 cm-1 to 3100 cm-1. Density functional theory was used to calculate features of the potential energy surfaces for the reactions and the vibrational spectra of intermediates. Generally, more than one isomer contributes to the observed spectrum. The oxygen-deficient clusters Al2O+ and Al3O2+ have large C-H activation barriers, so only the entrance channel complexes in which intact C2H6 binds to aluminum are observed. This interaction leads to a substantial (~200 cm-1) red shift of the C-H symmetric stretch in ethane, indicating significant weakening of the proximal C-H bonds. In Al3O4+, the complex formed by interactions with three C2H6 is investigated and, in addition to entrance channel complexes, the C-H activation intermediate Al3O4H+(C2H5)(C2H6)2 is observed. For oxygen-rich Al4O7+, the C2H6 is favored to bind at an aluminum site far from the reactive superoxide group, reducing the reactivity. As expected, oxygen-rich species and open-shell cluster ions have smaller barriers for C-H bond activation, except for Al3O4+ which is predicted and observed to be reactive.

Electrodeposited manganese carbonate as an electrocatalyst for hydrogen evolution reaction in acidic medium

The electrolysis of water is the key method for hydrogen production but the high overpotential necessitates electrocatalysts. Traditionally, Pt is used, but it is scarce and costly. Herein, MnCO3 is unveiled as an electrocatalyst for the production of hydrogen. MnCO3 is electrodeposited onto pencil graphite by chronoamperometric method and confirmed by XRD and vibrational spectroscopic studies. MnCO3 electrodeposited for 15 min at 2 V demonstrates a good HER activity (overpotential of 123 mV to reach 10 mA cm−2) in 0.5 M H2SO4 with a Tafel slope of 79 mV dec−1. In addition, MnCO3 exhibited good stability during continuous operation (over 3000 cycles and 14 h). Though MnCO3 requires higher overpotential than the benchmark catalyst (Pt/C) to reach 10 mA cm−2, it outperforms Pt/C at higher current density (≥75 mA cm−2) demonstrating that MnCO3 could be used as an electrocatalyst to produce H2 at a high rate from acidic medium.

Electronic and vibrational spectroscopic study complemented with the computational evaluation of hydroxychloroquine mixed with silver nanoparticles

Synthesized silver nanoparticles via laser liquid ablation were characterized using XRD, TEM, EDS, UV–Vis, and Raman spectroscopy. The AgNPs were then conjugated with HCQ at different concentrations. The study aimed to explore the effectiveness of HCQ against malaria and autoimmune diseases as well as how conjugating AgNPs with HCQ would broaden its activity against various infections and diseases, owing to the antimicrobial activity of AgNPs. The electronic and vibrational study of HCQ and its mixture showed a successful conjugation of the two, which would increase the potent of HCQ against SARS Coronavirus (SARS-COV-2) infection. Steady-state absorption measurements revealed a broadband peak at around 337.4 nm (3.68 eV), corresponding to a π to π* transition in the quinoline ring of the HCQ molecule. In addition, the AgNPs Localized Surface Plasmon Resonance (LSPR) band centred around 408 nm exhibited an intensity decrease with an increase in the concentration of HCQ. The experimental Raman spectra exhibited bands similar to the density function theory (DFT) calculated spectra centred at 392 cm−1, 768 cm−1, 1392 cm−1, 2928 cm−1, 3224 cm−1, 3656 cm−1, and 3808 cm−1. TEM, EDS, and XRD analysis confirmed the formation of 8.75 nm AgNPs. Understanding the electronic and vibrational spectroscopic properties of the interaction between HCQ and AgNPs, as deduced from the spectroscopic results supported by DFT, can significantly benefit researchers in the pharmaceutical industry. Researchers could apply this knowledge to overcome drug resistance, repurpose existing drugs, and reduce the side effects of conventional clinically approved drugs.

Neutron Vibrational Spectroscopic Study of the Acetylene: Ammonia (1:1) Cocrystal Relevant to Titan, Saturn's Moon.

The surface of Titan, Saturn's icy moon, is believed to be composed of various molecular minerals with a great diversity in structure and composition. Under the surface conditions, 93 K and 1.45 atm, most small molecules solidify and form minerals, including acetylene and ammonia. These two compounds can not only form single-component solids but also a 1:1 binary cocrystal that exhibits intriguing rotor phase behavior. This cocrystal is a putative mineral on Titan and other planetary bodies such as comets. In addition, the structure of the cocrystal is relevant to fundamental science as it can help better understand the emergence of rotor phases. Here, we present a detailed vibrational neutron spectroscopic study supported by a neutron powder diffraction study on the cocrystal and the single-phase solids. The experimentally observed spectral bands were assigned based on theoretical calculations. The established spectra-properties correlations for the cocrystal corroborate the observed properties. To the best of our knowledge, this study presents the first example of the application of neutron vibrational spectroscopy in studying Titan-relevant organic minerals.

Activation Energy of Ion Desorption at Ionic Liquid/Pt Electrode Interfaces: A Sum-Frequency Generation Vibrational Spectroscopic Study.

Electrolyte/electrode interfaces of room-temperature ionic liquids (RTILs) exhibit hysteretic responses to different applied potentials owing to the differences in the ion adsorption/desorption processes; the ion desorption requires excess potential, which reflects the activation energy of ion desorption. Thus far, the contributions of the ion adsorption energy and the activation barrier for ion desorption toward the ion-dependent excess potential have not been quantified. Herein, we report on our infrared-visible sum-frequency generation vibrational spectroscopy study of the hysteretic responses of the anion adsorption/desorption at Pt electrode interfaces using neat, binary, and diluted RTILs composed of 1-butyl-3-methylimidazolium cations ([C4mim]+) and bis(trifluoromethanesulfonyl)amide ([TFSA]-) and trifluoromethanesulfonate ([OTf]-) anions. Experimental results are compared to the theoretical calculations for the electric double layer model. The hysteretic response of the RTIL/Pt interface derives predominantly from the activation energy of anion desorption, which causes the negative excess potential required for anion desorption. A comparison of the anion adsorption/desorption behaviors of neat RTILs with those of binary and diluted RTILs reveals that the large activation energy of anion desorption at the neat RTIL/Pt interface originates largely from the activation barrier for restructuring ionic layering in the diffuse layer.

Rietveld refined structural, elastic, XPS, and dielectric evaluations of Zn-doped Cd–Mg spinel ferrites for high-frequency applications

Sol-gel auto ignition route was utilized to synthesize a series of Zn-doped Cd–Mg spinel ferrites with composition Cd0.5-xMg0.5ZnxFe2O4 (x = 0.0, 0.1, 0.2, and 0.3). All of the prepared nanomaterials that were annealed for 4 h at 900 °C had a cubic structure and were spinel, according to X-ray diffraction studies. The lattice constant decreased as the Zn concentration increased. This is because of the substituent's lower radii. The W–H plot, Size strain plot, and Sherrer Formula were used to calculate the crystallite size, which was in the range of a nanometer. Vibrational spectroscopy studies have also shown that M − O bonds are present in every processed sample and that a spinel cubic structure has formed. Additionally, the cationic distribution and cubic spinel structure were validated by Rietveld refinement of the XRD data. The analysis using X-ray photoelectron spectroscopy (XPS) has confirmed the presence of all metal ions in their respective electronic states. The dielectric characteristics in the 1 MHz-6 GHz range of frequencies were ascertained using an impedance analyzer. Jonscher's power law validated the conduction mechanism in the synthesized ferrite samples. The relaxation time constant calculated from impedance Cole-Cole plots shows that the conduction in all the synthesized nanomaterials was due to the grains rather than the grain boundaries. The minimum reflection loss of −36.54 dB was achieved for Zn-doped Cd–Mg ferrites at x = 0.3. The prepared Zn-doped Cd–Mg spinel ferrites would be an excellent material for high-frequency microwave absorption applications.

Correlating Structure with Spectroscopy in Ascorbate Peroxidase Compound II.

Structural and spectroscopic investigations of compound II in ascorbate peroxidase (APX) have yielded conflicting conclusions regarding the protonation state of the crucial Fe(IV) intermediate. Neutron diffraction and crystallographic data support an iron(IV)-hydroxo formulation, whereas Mössbauer, X-ray absorption (XAS), and nuclear resonance vibrational spectroscopy (NRVS) studies appear consistent with an iron(IV)-oxo species. Here we examine APX with spectroscopy-oriented QM/MM calculations and extensive exploration of the conformational space for both possible formulations of compound II. We establish that irrespective of variations in the orientation of a vicinal arginine residue and potential reorganization of proximal water molecules and hydrogen bonding, the Fe-O distances for the oxo and hydroxo forms consistently fall within distinct, narrow, and nonoverlapping ranges. The accuracy of geometric parameters is validated by coupled-cluster calculations with the domain-based local pair natural orbital approach, DLPNO-CCSD(T). QM/MM calculations of spectroscopic properties are conducted for all structural variants, encompassing Mössbauer, optical, X-ray absorption, and X-ray emission spectroscopies and NRVS. All spectroscopic observations can be assigned uniquely to an Fe(IV)═O form. A terminal hydroxy group cannot be reconciled with the spectroscopic data. Under no conditions can the Fe(IV)═O distance be sufficiently elongated to approach the crystallographically reported Fe-O distance. The latter is consistent only with a hydroxo species, either Fe(IV) or Fe(III). Our findings strongly support the Fe(IV)═O formulation of APX-II and highlight unresolved discrepancies in the nature of samples used across different experimental studies.

Phase transitions of choline dihydrogen phosphate: A vibrational spectroscopy and periodic DFT study.

Choline dihydrogen phosphate, [Chol][H2PO4], is a proton-conducting ionic plastic crystal exhibiting a complicated sequence of phase transitions. Here, we address the argument in the literature around the thermal properties of [Chol][H2PO4] using Raman and infrared microspectroscopy. The known structure of the low-temperature crystal, which contains the anti-conformer of [Chol]+ and hydrogen-bonded dimers of anions, was used to do periodic density functional theory calculations of the vibrational frequencies. Raman spectra indicate that the solid-solid transition at 20 °C is linked to a conformational change to the gauche [Chol] conformer with a concurrent local rearrangement of the anions. The distinct bands of lattice modes in the low-frequency range of the Raman spectra vanish at the 20 °C transition. Given the ease with which metastable crystals can be produced, Raman mappings demonstrate that a sample of [Chol][H2PO4] at ambient temperature can contain a combination of anti- and gauche conformers. Heating to 120 °C causes continuous changes in the local environment of anions rather than melting as suggested by a recent calorimetric investigation of [Chol][H2PO4]. The monotonic change in vibrational spectra is consistent with earlier observations of a very small entropy of fusion and no abrupt jump in the temperature dependence of ionic conductivity along the phase transitions of [Chol][H2PO4].

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.

Time-resolved vibrational spectroscopic study of molecular nanoaggregate photocatalysts.

The controlled aggregation of organic chromophores into supramolecular structures offers a way to control and tune photocatalytic activity. However, the underlying mechanisms of charge transfer and accumulation are still unclear. Time-resolved vibrational spectroscopy is a powerful structural probe for studying photogenerated intermediates. Here, we employ time-resolved infrared (TRIR) spectroscopy to study CNP (2,6-bis(4-cyanophenyl)-4-(9-phenyl-9H-carbazol-3-yl)pyridine-3,5-dicarbonitrile) and its supramolecular aggregates. We show that excitation of the charge transfer (CT) band of semi-crystalline nanofibers (CNP-f) gives rise to long-lived delocalised polarons, which form within the instrument response timescale. By contrast the CNP nanospheres (CNP-s) give rise to a shorter lived polaron that appears to have a greater degree of localization. CNP-f and CNP-s are known to show markedly different levels of photocatalytic activity for hydrogen and hydrogen peroxide formation which are rationalised owing to these differences in photodynamics immediately following photon absorption.

Theoretical Study of the Two-Dimensional Vibrational Sum Frequency Generation Spectroscopy of the Air-Water Interface at Varying Temperature and Its Connections to the Interfacial Structure and Dynamics.

We performed a theoretical study of the temperature variation of two-dimensional vibrational sum frequency generation (2D-VSFG) spectra of the OH stretch modes at air-water interfaces in the mid-IR region. The calculations are performed at four different temperatures from 250 to 325 K by using a combination of techniques involving response function formalism of nonlinear spectroscopy, electronic structure calculations, and molecular dynamics simulations. Also, the calculations are performed for isotopically dilute solutions so that the intra- and intermolecular coupling between the vibrational modes of interest can be ignored. We have established the connections of temperature variation of various frequency- and time-dependent features of the calculated spectra to the changes in the underlying structure and dynamics of the interfaces. The results reveal that interfacial water is dynamically more heterogeneous than bulk water, with three dominant dynamical processes exhibiting their corresponding time-dependent features in the 2D-VSFG spectrum. These are the spectral diffusion of hydrogen-bonded OH groups at the interface, conversion of an initially hydrogen-bonded OH group to a dangling OH which is a stable state for surface water, unlike the bulk water, and the third one, which involves the conversion of an initially free or dangling OH group to its hydrogen-bonded state at the interface. The temporal appearance of the cross peaks corresponding to interconversion of the hydrogen-bonded state to the dangling state or vice versa of an interfacial OH group is found to take place at a slower rate than the dynamics of spectral diffusion of hydrogen-bonded molecules at the interface, which, in turn, is slower than the corresponding spectral diffusion of bulk water molecules. The temperature variation of these dynamic processes can be linked to the decay of appropriate hydrogen-bond and non-hydrogen-bond time correlation functions of interfacial water molecules for the different air-water systems studied in this work.

Mössbauer and Nuclear Resonance Vibrational Spectroscopy Studies of Iron Species Involved in N-N Bond Cleavage.

Diketiminate-supported iron complexes are capable of cleaving the strong triple bond of N2 to give a tetra-iron complex with two nitrides (Rodriguez et al., Science, 2011, 334, 780-783). The mechanism of this reaction has been difficult to determine, but a transient green species was observed during the reaction that corresponds to a potential intermediate. Here, we describe studies aiming to identify the characteristics of this intermediate, using a range of spectroscopic techniques, including Mössbauer spectroscopy, electronic absorption spectroscopy, Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy, and nuclear resonance vibrational spectroscopy (NRVS) complemented by density functional theory (DFT) calculations. We successfully elucidated the nature of the starting iron(II) species and the bis(nitride) species in THF solution, and in each case, THF breaks up the multiiron species. Various observations on the green intermediate species indicate that it has one N2 per two Fe atoms, has THF associated with it, and has NRVS features indicative of bridging N2. Computational models with a formally diiron(0)-N2 core are most consistent with the accumulated data, and on this basis, a mechanism for N2 splitting is suggested. This work shows the power of combining NRVS, Mössbauer, NMR, and vibrational spectroscopies with computations for revealing the nature of transient iron species during N2 cleavage.

Luminescent rhenium(I) complex with cyanopentafluorophosphate ligand: Synthesis, characterization, and photophysics

A tricarbonyl Re(I) phenanthroline complex (1) with anionic cyanopentafluorophosphate [NCPF5]– ligand has been synthesized and characterized. Although the structure of the complex has also been determined by X-ray crystallography, the identity of the [NCPF5]– needs to be confirmed by the vibrational spectroscopic study. The cyanopentafluorophosphate Re(I) phenanthroline complex 1 also exhibits phosphorescence derived from a 3MLCT excited state. Importantly, as the MLCT absorption and emission energies of 1 are comparable to those of the structurally related complexes with the strongest π-accepting anionic isocyanoborate ligands, it reveals the exceptionally strong π-accepting ability of [NCPF5]–. This result suggests that [NCPF5]– is a promising alternative to isocyanoborate ligands for designing phosphorescent materials, catalysts and photocatalysts.

Experimental and computational study on the spectroscopic approach, chemical reactivity, hyperpolarizabilities and in-silico ligand-protein docking of 5-Chloro-2,4,6-trifluoropyrimidine

The 5-Chloro-2,4,6-trifluoropyrimidine (5CTFP) was chosen for extensive investigation of its theoretical and experimental vibrational assignments, structural discussion, and spectroscopic studies of Fourier-transform infrared (FT-IR), Fourier transform-Raman (FT-Raman), Ultraviolet–visible (UV–vis), and Nuclear magnetic resonance (NMR) by Hartree-Fock (HF) functional with 6-311+G(2d,p) basis set. The spectrum of detailed vibrational interpretation was to be provided by the MOLVIB software. Bonding orbitals participate in all stages of NBO analysis as donors and acceptors, which stabilises molecules through intermolecular charge transfer. Molecular docking research was used to foreseen the binding interactions of 5CTFP derivative with the estrogen receptor 3WZD. Auto-dock software was used to conduct receptor-ligand docking investigation. According to the molecular docking results, the highest mean negative binding affinity (−5.639 kcal/mol) was exhibited by the current chemical. Based on five-point rule of Lipinski, drug similarity was determined, and the ADMET variables were also predicted.

Extracorporeal membrane oxygenation and effects on tendon tissue: A vibrational spectroscopy study.

Extracorporeal membrane oxygenation (ECMO) is an invasive medical technique used to provide life support in persons with insufficient cardiac and respiratory functionalities, or to preserve, postmortem, and organ function addressing organ/tissue transplant. Although a lot of information is available about organs in their entirety, the safety and effectiveness of allogeneic tissues collected from ECMO donors have not been fully elucidated. In this preliminary study, samples of tibial and peroneal human tendons were analyzed along their length with Raman microspectroscopy and attenuated total reflection-Fourier transform infrared micro-imaging. Both techniques evidenced a different chemical composition in the terminal with respect to the central part of the tendon. Thus, a differentiated analysis was performed depending on the specific position with respect to the bone or the muscle junctions. Spectroscopic analyses showed significant differences in the characteristics of the extracellular matrix between tendons from ECMO and non-ECMO donors, suggesting changes in the amino acid (proline and hydroxyproline) content and protein structure.

FTIR vibrational and 13C NMR spectroscopic study of the effect on ionic transport behavior of NaClO4 in N,N-dimethylacetamide and its binary mixtures with 2-aminoethanol

FTIR vibrational and 13C NMR spectroscopic study of the effect on ionic transport behavior of NaClO4 in N,N-dimethylacetamide and its binary mixtures with 2-aminoethanol

Synthesis, spectral characterizations, vibrational spectroscopy, DFT-computations, antibacterial, antioxidant, and molecular docking studies of the novel (Z)-2-(5-((10-hexyl-10H-phenothiazin-3-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl) acetic acid

The Synthesized novel compound of (Z)-2-(5-((10-hexyl-10H-phenothiazin-3-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl) acetic acid (PTZTZ) was charecterized by nuclear magnetic resonance (1H, 13C), FTIR, UV–Visible, (Total Ion Current) Chromatogram, and ESI full mass spectrum analyses. The determination of DFT analyses of the PTZTZ optimized structure, geometric parameters, UV–Visible Spectroscopy, and FTIR, and their experimental measurement was compared with the resultant estimated results. The frontier molecular orbitals (FMOs), Mulliken's population analysis, and molecular electrostatic potential (MEP) of the title molecule were revealed by theoretical calculations using Gaussian 09 and the fundamental set B3LYP/6-311++G (d,p) level. According to Pharmacological Screening, the title compound showed strong bactericidal activity with a maximum zone of inhibition of (19.8 ± 0.5 mm) at 2.5 g/mL against Proteus mirabilis (MTCC 1771) and scavenging activity analysis of DPPH scavenging trait ranging from (38.8 ± 0.6% to 88.6 ± 4.0%), (H2O2) Hydrogen peroxide exhibited maximal scavenging property of 74.10.2% (p < 0.05), ABTS reducing potential exhibited maximum trait ranging from (39.1 ± 1.2% to 77.8 ± 6.4%), and Ferric reducing antioxidant power (FRAP) exhibited maximum Ferric reducing antioxidant power (FRAP) potential trait ranging from (16.0 ± 0.6% to 43.6 ± 0.5%). Using Discovery Studio 4.0 and ADMET (Absorption, Distribution, Metabolism, Excretion, and Toxicity) profile analysis tools, in-silico molecular docking studies revealed the active pocket of the 1HD2 protein to evaluate the evaluation of genotoxicology. Using molecular docking, the compound PTZTZ displayed a greater binding interaction energy of -240.3 (Kcal/mol) against the target protein. The greatest results of this research show that phenothiazine derivatives have superior activity and extremely low binding energy toward the active pocket of protein. In DFT investigations, the title compound demonstrated a minimal energy band gap.