Novel series of 2-(4,6-dimethoxy,1,3,5-triazin-2-yl) amino acid ester derivatives were synthesized using simple one pot method in methanol. The products were obtained in high yields and purities as observed from their spectral data, elemental analyses, GC-MS and X-ray crystallographic analysis. The B3LYP/6-311G(d,p) calculated molecular structures are well correlated with the geometrical parameters obtained from the X-ray analyses. The spectroscopic properties such as IR vibrational modes, NMR chemical shifts and UV-Vis electronic transitions were discussed both experimentally and theoretically. The IR vibrational frequencies showed good correlations with the experimental data (R(2)=0.9961-0.9995). The electronic spectra were assigned based on the TD-DFT results. Intense electronic transition band is calculated at 198.1nm (f=0.1389), 204.2nm (f=0.2053), 205.0 (f=0.1704) and 205.7 (0.2971) for compounds 6a-i, respectively. The molecular orbital energy levels contributed in the longest wavelength transition band were explained. For all compounds, the experimental wavelengths showed red shifts compared to the calculations due to the solvent effect. The NMR chemical shifts were calculated using GIAO method. The NBO analyses were performed to predict the stabilization energies due to the electron delocalization processes occur in the studied systems.
The [Co(Me(2)Salen)(PBu(3))(OH(2))]BF4 and [Co(Me(2)Salen)(PPh(3))(Solv)]BF(4), complexes were synthesized and characterized by FT-IR, UV-Vis, (1)H NMR spectroscopy and elemental analysis techniques. The coordination geometry of [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) was determined by X-ray crystallography. It has been found that the complex is containing [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) and [Co(Me(2)Salen)(PPh(3))(EtOH)]BF(4) hexacoordinate species in the solid state. Cobalt atom exhibits a distorted octahedral geometry and the Me(2)Salen ligand has the N2O2 coordinated environment in the equatorial plane. The [Co(Me(2)Salen)(PPh(3))(H(2)O)]BF(4) complex shows a dimeric structure via hydrogen bonding between the phenolate oxygen and hydrogens of coordinated H2O molecule. These complexes were incorporated into Montmorillonite-K10 nanoclay. The modified clays were identified by FT-IR, XRD, EDX, TGA/DTA, SEM and TEM techniques. According to the XRD results of the new nanohybrid materials, the Schiff base complexes are intercalated in the interlayer spaces of the clay. SEM and TEM micrographs show that the resulting hybrid nanomaterials have layer structures. Also, TGA/DTG results show that the intercalation reaction was taken place successfully.
The first example of non-symmetric isoflavone-based fast photo-switchable liquid crystals with different functional groups at the terminal position were synthesized and characterized. Polarizing optical microscopy study revealed that the compounds showed least ordered nematic phase. Optical photo switching study exhibited very fast photoisomerization effect in solution. The E-Z and Z-E conversion occurred around 3-5s and 40-700 s respectively. This is also the first example of para-substituted non-symmetric isoflavone liquid crystals exhibiting very fast photo switching property in solution. Argument based on non-symmetrical behaviour might be the reason for the observed behaviour.
The proliferation of pathogenic fungi in sugarcane crops poses a significant threat to agricultural productivity and economic sustainability. Early identification and management of sugarcane diseases are therefore crucial to mitigate the adverse impacts of these pathogens. In this study, visible and near-infrared spectroscopy (380-1400 nm) combined with a novel wavelength selection method, referred to as modified flower pollination algorithm (MFPA), was utilized for sugarcane disease recognition. The selected wavelengths were incorporated into machine learning models, including Naïve Bayes, random forest, and support vector machine (SVM). The developed simplified SVM model, which utilized the MFPA wavelength selection method yielded the best performances, achieving a precision value of 0.9753, a sensitivity value of 0.9259, a specificity value of 0.9524, and an accuracy of 0.9487. These results outperformed those obtained by other wavelength selection approaches, including the selectivity ratio, variable importance in projection, and the baseline method of the flower pollination algorithm.
Four dioxomolybdenum(VI) complexes were synthesized by reacting [MoO2(acac)2] with N-ethyl-2-(5-bromo-2-hydroxybenzylidene) hydrazinecarbothioamide (1), N-ethyl-2-(5-allyl-3-methoxy-2-hydroxybenzylidene) hydrazinecarbothioamide (2), N-methyl-2-(3-tert-butyl-2-hydroxybenzylidene) hydrazinecarbothioamide (3), and N-ethyl-2-(3-methyl-2-hydroxybenzylidene) hydrazinecarbothioamide (4). The molecular structures of 1, 2, and all the synthesized complexes were determined using single crystal X-ray crystallography. The binding properties of the ligand and complexes with calf thymus DNA (CT-DNA) were investigated via UV, fluorescence titrations, and viscosity measurement. Gel electrophoresis revealed that all the complexes cleave pBR 322 plasmid DNA. The cytotoxicity of the complexes were studied against the HCT 116 human colorectal cell line. All the complexes exhibited more pronounced activity than the standard reference drug 5-fluorouracil (IC50 7.3μM). These studies show that dioxomolybdenum(VI) complexes could be potentially useful in chemotherapy.
In the present work, the title chalcone, (2E)-3-(4-fluorophenyl)-1-(4-{[(1E)-(4-fluorophenyl) methylene]amino}phenyl)prop-2-en-1-one (abbreviated as FAMFC), was synthesized and structurally characterized by single-crystal X-ray diffraction. The compound is crystallized in the monoclinic system with non-centrosymmetric space group P21 and hence it satisfies the essential condition for materials to exhibit second-order nonlinear optical properties. The molecular structure was further confirmed by using FT-IR and 1H NMR spectroscopic techniques. The title crystal is transparent in the Vis-NIR region and has a direct band gap. The third-order nonlinear optical properties were investigated in solution (0.01M) by Z-scan technique using a continuous wave (CW) DPSS laser at the wavelength of 532nm. The title chalcone exhibited significant two-photon absorption (β=35.8×10-5cmW-1), negative nonlinear refraction (n2=-0.18×10-8cm2W-1) and optical limiting (OL threshold=2.73kJcm-2) under the CW regime. In support of the experimental results, a comprehensive theoretical study was carried out on the molecule of FAMFC using density functional theory (DFT). The optimized geometries and frontier molecular orbitals were calculated by employing B3LYP/6-31+G level of theory. The optimized molecular structure was confirmed computationally by IR vibrational and 1H NMR spectral analysis. The experimental UV-Vis-NIR spectrum was interpreted using computational chemistry under time-dependent DFT. The static and dynamic NLO properties such as dipole moments (μ), polarizability (α), and first hyperpolarizabilities (β) were computed by using finite field method. The obtained dynamic first hyperpolarizability β(-2ω;ω,ω) at input frequency ω=0.04282a.u. is predicted to be 161 times higher than urea standard. The electronic excitation energies and HOMO-LUMO band gap for FAMFC were also evaluated by DFT. The experimental and theoretical results are in good agreement, and the NLO study suggests that FAMFC molecule can be a potential candidate in the nonlinear optical applications.
The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 1-[5-(4-bromophenyl)-3-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol-1-yl]ethanone have been investigated experimentally and theoretically using Gaussian09 software package. The title compound was optimized using the HF/6-31G(d) (6D, 7F), B3LYP/6-31G (6D, 7F) and B3LYP/6-311++G(d,p) (5D, 7F) calculations. The B3LYP/6-311++G(d,p) (5D, 7F) results and in agreement with experimental infrared bands. The geometrical parameters are in agreement with XRD data. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis is used to determine the charge transfer within the molecule. Molecular electrostatic potential was also performed. From the MEP it is evident that the negative charge covers the C=O group and the positive region is over the rings. First hyperpolarizability is calculated in order to find its role in nonlinear optics. Molecular docking studies suggest that the compound might exhibit inhibitory activity against TPII and may act as anti-neoplastic agent.
2-(4-Chlorophenyl)-2-oxoethyl 3-methylbenzoate is synthesized by reacting 4-chlorophenacyl bromide with 2-methylbenzoic acid using a slight excess of potassium or sodium carbonate in DMF medium at room temperature. The structure of the compound was confirmed by IR and single-crystal X-ray diffraction studies. FT-IR spectrum of 2-(4-chlorophenyl)-2-oxoethyl-3-nitrobenzoate was recorded and analyzed. The crystal structure is also described. The vibrational wavenumbers were computed using HF and DFT methods and are assigned with the help of potential energy distribution method. The first hyperpolarizability and infrared intensities are also reported. The geometrical parameters of the title compound obtained from XRD studies are in agreement with the calculated (DFT) values. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using NBO analysis. The HOMO and LUMO analysis are used to determine the charge transfer within the molecule. MEP was performed by the DFT method.
Binding of a potent anticancer agent, ponatinib (PTB) to human serum albumin (HSA), main ligand transporter in blood plasma was analyzed with several spectral techniques such as fluorescence, absorption and circular dichroism along with molecular docking studies. Decrease in the KSV value with increasing temperature pointed towards PTB-induced quenching as the static quenching, thus affirming complexation between PTB and HSA. An intermediate binding affinity was found to stabilize the PTB-HSA complex, as suggested by the Ka value. Thermodynamic analysis of the binding phenomenon revealed participation of hydrophobic and van der Waals interactions along with hydrogen bonds, which was also supported by molecular docking analysis. Changes in both secondary and tertiary structures as well as in the microenvironment around Trp and Tyr residues of HSA were anticipated upon PTB binding to the protein, as manifested from circular dichroism and three-dimensional fluorescence spectra, respectively. Binding of PTB to HSA led to protein's thermal stabilization. Competitive ligand displacement experiments using different site markers such as warfarin, indomethacin and ketoprofen disclosed the binding site of PTB as Sudlow's site I in HSA, which was further confirmed by molecular docking analysis.
In the presence of hydroxyl and amine groups, chitosan is highly reactive; therefore, it could be used as a carrier in drug delivery. For this study, chitosan-Sm complexes with different concentrations of samarium from 2.5 to 25 wt.% have been successfully synthesized by the impregnation method. Chitosan combined with Sm3+ ions produced a drug carrier material with fluorescence properties; thus, it could also be used as an indicator of drug release with ibuprofen (IBU) as a model drug. We evaluated the spectroscopic and interaction properties of chitosan and Sm3+ ions, the interaction of chitosan-Sm matrices with IBU as a model drug, and the effect of Sm3+ ions addition on the chitosan ability to adsorb the drug. The result showed that the hypersensitive fluorescence intensity of chitosan-Sm (2.5 wt.%) is higher than the others, even though the adsorption efficiency of chitosan-Sm 2.5wt.% is lower (29.75%) than that of chitosan-Sm 25 wt.% (33.04%). Chitosan-Sm 25 wt.% showed the highest efficiency of adsorption of ibuprofen (33.04%). In the release process of ibuprofen from the chitosan-Sm-IBU matrix, the intensity of orange fluorescent properties in the hypersensitive peak of 4G5/2→6H7/2 transition at 590 nm was observed. Fluorescent intensity increased with the cumulative amount of IBU released; therefore, the release of IBU from the Sm-modified chitosan complex can be monitored by the changes in fluorescent intensity.
Complex dielectric permittivity measurements of propylene glycol (PG) in ethanol at various mole fractions were measured by using open-ended coaxial probe technique at different temperatures in the frequency range 0.02
A metal-free mesoporous carbon nitride (MCN) was investigated for the first time as an adsorbent for N-nitrosopyrrolidine (NPYR), which is one of the nitrosamine pollutants. Under the same condition, the adsorption capability of the MCN was found to be higher than that of the MCM-41. Since the adsorption isotherm was consistent with Langmuir and Freundlich model equations, it was suggested that the adsorption of NPYR molecules on the MCN occurred in the form of mono-molecular layer on the heterogeneous surface sites. It was proposed that MCN with suitable adsorption sites was beneficial for the adsorption of NPYR. The evidence on the interaction between the NPYR molecules and the MCN was supported by fluorescence spectroscopy. Two excitation wavelengths owing to the terminal N-C and N=C groups were used to monitor the interactions between the emission sites of the MCN and the NPYR molecules. It was confirmed that the intensity of the emission sites was quenched almost linearly with the concentration of NPYR. This result obviously suggested that the MCN would be applicable as a fluorescence sensor for detection of the NPYR molecules. From the Stern-Volmer plot, the quenching rate constant of terminal N-C groups was determined to be ca. two times higher than that of the N=C groups on MCN, suggesting that the terminal N-C groups on MCN would be the favoured sites interacted with the NPYR. Since initial concentration can be easily recovered, the interactions of NPYR on MCN were weak and might only involve electrostatic interactions.
Surface plasmon resonance (SPR) is a label-free optical spectroscopy that is widely used for biomolecular interaction analysis. In this work, SPR was used to characterize the binding properties of highly sensitive nanocrystalline cellulose-graphene oxide based nanocomposite (CTA-NCC/GO) towards nickel ion. The formation of CTA-NCC/GO nanocomposite has been confirmed by FT-IR. The SPR analysis result shows that the CTA-NCC/GO has high binding affinity towards Ni2+ from 0.01 until 0.1 ppm with binding affinity constant of 1.620 × 103 M-1. The sensitivity for the CTA-NCC/GO calculated was 1.509° ppm-1. The full width at half maximum (FWHM), data accuracy (DA), and signal-to-noise ratio (SNR) have also been determined using the obtained SPR curve. For the FWHM, the value was 2.25° at 0.01 until 0.08 ppm and decreases to 2.12° at 0.1 until 10 ppm. The DA for the SPR curves is the highest at 0.01 until 0.08 ppm and lowest at 0.1 until 10 ppm. The SNR curves mirrors the curves of SPR angle shift where the SNR increases with the Ni2+ concentrations. For the selectivity test, the CTA-NCC/GO has the abilities to differentiate Ni2+ in the mixture of metal ions.
The adsorption behavior of the amino acid, glycine (Gly), via the carboxyl, hydroxyl, and amino groups onto the surfaces of Al12N12 and Al16N16 fullerene-like cages were computationally evaluated by the combination of density functional theory (DFT) and molecular docking studies. It was found that Gly can chemically bond with the Al12N12 and Al16N16 fullerene-like cages as its amino group being more favorable to interact with the aluminum atoms of the adsorbents compared to carboxyl and hydroxyl groups. Oxygen and carbon doping were reported to reduce steric hindrance for Glycine interaction at Al site of Al12ON11/Gly and Al12CN11/Gly complexes. Interaction was further enhanced by oxygen doping due to its greater electron withdrawing effect. Herein, the Al12ON11/Gly complex where two carbonyl groups of Gly are bonded to the aluminum atoms of the Al12N12 fullerene-like cage is the most stable interaction configuration showing ∆adsH and ∆adsG values of -81.74 kcal/mol and -66.21 kcal/mol, respectively. Computational studies also revealed the frequency shifts that occurred due to the interaction process. Molecular docking analysis revealed that the Al12N12/Gly (-11.7 kcal/mol) and the Al12ON11/Gly (-9.2 kcal/mol) complexes have a good binding affinity with protein tumor necrosis factor alpha (TNF-α). TNF-α was implicated as a key cytokine in various diseases, and it has been a validated therapeutic target for the treatment of rheumatoid arthritis. These results suggest that the Al12N12/Gly complex in comparison with the Al16N16/Gly, Al12ON11/Gly, and the Al12CN11/Gly complexes could be efficient inhibitors of TNF-α.
This work describes a RP-HPLC method for the determination and interaction studies of cefpirome with ACE-inhibitors (captopril, enalapril and lisinopril) in various buffers. The separation and interaction of cefpirome with ACE-inhibitors was achieved on a Purospher Star, C18 (5 μm, 250×4.6 mm) column. Mobile phase consisted of methanol: water (80:20, v/v, pH 3.3); however, for the separation of lisinopril, it was modified to methanol-water (40:60, v/v, pH 3.3) and pumped at a flow rate of 1 mL min(-1). In all cases, UV detection was performed at 225 nm. Interactions were carried out in physiological pH i.e., pH 1 (simulated gastric juice), 4 (simulated full stomach), 7.4 (blood pH) and 9 (simulated GI), drug contents were analyzed by reverse phase high performance liquid chromatography. Method was found linear in the concentration range of 1.0-50.0 μg mL(-1) with correlation coefficient (r(2)) of 0.999. Precision (RSD%) was less than 2.0%, indicating good precision of the method and accuracy was 98.0-100.0%. Furthermore, cefpirome-ACE-inhibitors' complexes were also synthesized and results were elucidated on the basis of FT-IR, and (1)H NMR. The interaction results show that these interactions are pH dependent and for the co-administration of cefpirome and ACE-inhibitors, a proper interval should be given.
The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments of 3-(4-fluorophenyl)-5-phenyl-4,5-dihydro-1H-pyrazole-1-carbaldehyde have been investigated experimentally and theoretically. The title compound was optimized using at HF and DFT levels of calculations. The B3LYP/6-311++G(d,p) (5D,7F) results and in agreement with experimental infrared bands. The normal modes are assigned using potential energy distribution. The stability of the molecule arising from hyper-conjugative interaction and charge delocalization has been analyzed using natural bonding orbital analysis. The frontier molecular orbital analysis is used to determine the charge transfer within the molecule. From molecular electrostatic potential map, it is evident that the negative electrostatic potential regions are mainly localized over the carbonyl group and mono substituted phenyl ring and are possible sites for electrophilic attack and, positive regions are localized around all para substituted phenyl and pyrazole ring, indicating possible sites for nucleophilic attack. First hyperpolarizability is calculated in order to find its role in nonlinear optics. The geometrical parameters are in agreement with experimental data. From the molecular docking studies, it is evident that the fluorine atom attached to phenyl ring and the carbonyl group attached to pyrazole ring are crucial for binding and the results draw us to the conclusion that the compound might exhibit phosphodiesterase inhibitory activity.
FT-IR spectrum of (2E)-3-(3-nitrophenyl)-1-[4-piperidin-1-yl]prop-2-en-1-one was recorded and analyzed. The vibrational wavenumbers were computed using HF and DFT quantum chemical calculations. The data obtained from wavenumber calculations are used to assign IR bands. Potential energy distribution was done using GAR2PED software. The geometrical parameters of the title compound are in agreement with the XRD results. NBO analysis, HOMO-LUMO, first and second hyperpolarizability and molecular electrostatic potential results are also reported. The possible electrophile attacking sites of the title molecule is identified using MEP surface plot study. Molecular docking results predicted the anti-leishmanic activity for the compound.
In this study, the combination of novel valinomycin doped chitosan-graphene oxide (C-GO-V) thin film and surface plasmon resonance (SPR) system for potassium ion (K+) detection has been developed. The novel C-GO-V thin film was deposited on the gold surface using spin coating technique. The system was used to monitor SPR signal for K+ in solution with and without C-GO-V thin film. The K+ can be detected by measuring the SPR signal when C-GO-V thin film is exposed to K+ in solution. The sensor produces a linear response for K+ ion up to 100ppm with sensitivity and detection limit of 0.00948°ppm-1 and 0.001ppm, respectively. These results indicate that the C-GO-V film is high potential as a sensor element for K+ that has been proved by the SPR measurement.
Binding mechanisms of two selected pesticides, propazine (PRO) and quinoxyfen (QUI) with bovine serum albumin (BSA) was examined using fluorescence, absorption and molecular docking methods. Intrinsic fluorescence of BSA was quenched in the presence of both PRO and QUI. The quenching was ascertained to be conversely linked to temperature, which suggested the contribution of static quenching process in the PRO-BSA and QUI-BSA complex formations. This results were validated by the enhancement in absorption spectrum of BSA upon binding with PRO and QUI. Binding constant values (Kf = 9.55-0.60 × 10-3 M-1 for PRO-BSA system; Kf = 7.08-5.01 × 102 M-1 for QUI-BSA system) and number of binding site (n) values for the PRO-BSA and QUI-BSA systems at different temperatures affirmed a weak binding strength with a set of equivalent binding sites on BSA. Thermodynamic data obtained for both the PRO-BSA and QUI-BSA interactions predicted that the association process was spontaneous and non-covalent contacts such as hydrophobic interactions, van der Waals forces and hydrogen bonds participated in the binding reactions. This result was further supported by the molecular docking assessments. Three-dimensional spectral results revealed the microenvironmental alterations near tryptophan (Trp) and tyrosine (Tyr) residues in BSA by the addition of PRO and QUI. The docking analysis demonstrated the binding pattern for the PRO-BSA and QUI-BSA systems and disclosed the preferred binding site of both PRO and QUI as site I (subdomain IIA) of BSA.
The [Co(naphophen)(PPh3)(OH2)]ClO4 and [Co(naphophen)(PBu3)(OH2)]BF4 (where naphophen=bis(naphthaldehyde)1,2-phenylenediimine) complexes were synthesized and chracterized by FT-IR, UV-Vis, (1)H NMR, (13)C NMR spectroscopy and elemental analysis techniques. The coordination geometry of the synthesized complexes were determined by X-ray crystallography. Cobalt (III) complexes have six-coordinated pseudo-octahedral geometry in which the O(1), O(2), N(1) and N(2) atoms of the Schiff base forms the equatorial plane. These complexes showed a dimeric structure via hydrogen bonding between the phenolate oxygen and the hydrogens of the coordinated H2O molecule. The theoretical calculations were also performed to optimize the structure of the complexes in the gas phase to confirm the structures proposed by X-ray crystallography. In addition, UV-Visible and IR spectra of complexes were calculated and compared with the corresponding experimental spectra to complete the experimental structural identification. The synthesized complexes were incorporated onto the Montmorillonite-K10 nanoclay via simple ion-exchange reaction. The structure and morphology of the obtained nanohybrids were identified by FT-IR, XRD, TGA/DTA, SEM and TEM techniques. Based on the XRD results of the new nanohybrid materials, the Schiff base complexes were intercalated in the interlayer spaces of clay. SEM and TEM micrographs of the clay/complex shows that the resulting hybrid nanomaterials has layer structures.