The structure of 3-iodobenzaldehyde (3IB) was characterized by FT-IR, Raman and single-crystal X-ray diffraction techniques. The conformational isomers, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of 3IB were examined using density functional theory (DFT) method, with the Becke-3-Lee-Yang-Parr (B3LYP) functional and the 6-311+G(3df,p) basis set for all atoms except for iodine. The LANL2DZ effective core basis set was used for iodine. Potential energy distribution (PED) analysis of normal modes was performed to identify characteristic frequencies. 3IB crystallizes in monoclinic space group P21/c with the O-trans form. There is a good agreement between the theoretically predicted structural parameters, and vibrational frequencies and those obtained experimentally. In order to understand halogen effect, 3-halogenobenzaldehyde [XC6H4CHO; X=F, Cl and Br] was also studied theoretically. The free energy difference between the isomers is small but the rotational barrier is about 8kcal/mol. An atypical behavior of fluorine affecting conformational preference is observed.
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 heterocyclic chalcone containing thiophene ring 1-(4-chlorophenyl)-3-(2-thienyl)prop-2-en-1-one, C13H9ClOS was synthesized and investigated using experimental techniques such as nuclear magnetic resonance (1H and 13C NMR), Fourier transform infrared spectroscopy (FTIR) at room temperature, differential scanning calorimeter (DSC) from room temperature to 500K and Raman scattering at the temperature range 10-413K in order to study its structure and vibrational properties as well as stability and possible phase transition. Density functional theory (DFT) calculations were performed to determine the vibrational spectrum viewing to improve the knowledge of the material properties. A reasonable agreement was observed between theoretical and experimental Raman spectrum taken at 10K since anharmonic effects of the molecular motion is reduced at low temperatures, leading to a more comprehensive assignment of the vibrational modes. Increasing the temperature up to 393K, was observed the typical phonon anharmonicity behavior associated to changes in the Raman line intensities, line-widths and red-shift, in special in the external mode region, whereas the internal modes region remains almost unchanged due its strong chemical bonds. Furthermore, C13H9ClOS goes to melting phase transition in the temperature range 393-403K and then sublimates in the temperature range 403-413K. This is denounced by the disappearance of the external modes and the absence of internal modes in the Raman spectra, in accordance with DSC curve. The enthalpy (ΔH) obtained from the integration of the endothermic peak in DSC curve centered at 397K is founded to be 121.5J/g.
The electronic absorption spectra of eight substituted acetic acids have been measured at room temperature in several solvents. The ground state dipole moments are evaluated experimentally for these molecules. These ground state values are used in conjunction with the spectral results to evaluate their first electronically excited state dipole moments. For all the molecules investigated here the dipole moments in the excited state are higher than their ground state values.
2-(4-Chlorophenyl)-2-oxoethyl 2-chlorobenzoate has been synthesized, its structural and vibrational properties have been reported using FT-IR and single-crystal X-ray diffraction (XRD) studies. The conformational analysis, optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of the synthesized compound (C15H10Cl2O3) have been examined by means of Becke-3-Lee-Yang-Parr (B3LYP) density functional theory (DFT) method together with 6-31++G(d,p) basis set. Furthermore, reliable conformational investigation and vibrational assignments have been made by the potential energy surface (PES) and potential energy distribution (PED) analyses, respectively. Calculations are performed with two possible conformations. The title compound crystallizes in orthorhombic space group Pbca with the unit cell dimensions a=12.312(5) Å, b=8.103(3) Å, c=27.565(11) Å, V=2750.0(19) Å(3). B3LYP method provides satisfactory evidence for the prediction of vibrational wavenumbers and structural parameters.
The structure of (E)-1-(4-Bromophenyl)-3-(napthalen-2-yl)prop-2-en-1-one (C19H13BrO) crystallized in the triclinic system of P-1 space group. The unit cell dimensions are: a=5.8944 (9)Å, b=7.8190 (12)Å, c=16.320 (2)Å, α=102.4364 (19)°, β=95.943 (2)°, γ=96.274 (2)° and Z=2. The physical properties of this compound was determined by the spectroscopic methods (FTIR and (1)H and (13)C NMR). Quantum chemical investigations have been employed to investigate the structural and spectral properties. The molecular structure, vibrational assignments, (1)H and (13)C NMR chemical shift values, non-linear optical (NLO) effect, HOMO-LUMO analysis and natural bonding orbital (NBO) analysis were calculated using HF and DFT/B3LYP methods with 6-311++G(d,p) basis set in the ground state. The results show that the theoretical calculation of the geometrical parameters, vibrational frequencies and chemical shifts are comparable with the experimental data. The crystal structure is influenced and stabilized by weak C-H⋯π interactions connecting the molecules into infinite supramolecular one dimensional ladder-like arrangement. Additionally, this compound is evaluated for their antibacterial activities against gram positive and gram negative strains using a micro dilution procedure and shows activities against a panel of microorganisms.
2-(4-Chlorophenyl)-2-oxoethyl 3-nitrobenzoate is synthesized by reacting 4-chlorophenacyl bromide with 3-nitrobenzoic 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.
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.
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.
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.
A new thiosemicarbazone derivative, N-(2-hydroxyphenyl)-2-[1-(pyridin-4-yl)ethylidene]hydrazinecarbothioamide (HPEH), has been synthesized, characterized, and further developed as a highly selective and sensitive colorimetric chemosensor for Hg2+ recognition in environmental water samples. Structural conformers of HPEH were successfully identified using a combination of the potential energy surface (PES) and time-dependent density functional theory (TD-DFT) methods. The synthesized HPEH was successfully characterized further and analyzed based on its harmonic vibrational frequencies, NMR spectra, and electronic transitions using the DFT approach. Sigma profiles were generated using the COSMO-RS approach to identify a compatible medium for HPEH to act as a chemosensor. The conditions for the highly sensitive and selective detection of Hg2+ by HPEH were successfully optimized using the statistical response surface methodology approach. The optimum sensing of HPEH occurred in an 8:2 v/v DMSO/pH 7.8 solution at a 20:60 μM HPEH/Hg2+ concentration and after a reaction time of 18 min, with statistically significant independent variables (p
The natural dyes anthocyanin and chlorophyll were extracted from Musa acuminata bracts and Alternanthera dentata leaves, respectively. The dyes were then applied as sensitizers in TiO2-based dye-sensitized solar cells (DSSCs). The ethanol extracts of the dyes had maximum absorbance. High dye yields were obtained under extraction temperatures of 70 to 80°C, and the optimal extraction temperature was approximately 80°C. Moreover, dye concentration sharply decreased under extraction temperatures that exceeded 80°C. High dye concentrations were obtained using acidic extraction solutions, particularly those with a pH value of 4. The DSSC fabricated with anthocyanin from M. acuminata bracts had a conversion efficiency of 0.31%, short-circuit current (Isc) of 0.9mA/cm2, open-circuit voltage (Voc) of 0.58V, and fill factor (FF) of 62.22%. The DSSC sensitized with chlorophyll from A. dentata leaves had a conversion efficiency of 0.13%, Isc of 0.4mA/cm-2,Voc of 0.54V, and FF of 67.5%. The DSSC sensitized with anthocyanin from M. acuminata bracts had a maximum incident photon-to-current conversion efficiency of 42%, which was higher than that of the DSSC sensitized with chlorophyll from A. dentata leaves (23%). Anthocyanin from M. acuminata bracts exhibited the best photosensitization effects.
A series of glass samples with chemical formula {[(TeO2)0.7(B2O3)0.3]0.7(ZnO)0.3}1-x(Dy2O3)xwhere x=0.01, 0.02, 0.03, 0.04 and 0.05M fraction were synthesized through conventional melt-quenching method. The most common way to fabricate a glass material is by fusion of two or more component oxides followed by their quenching. This technique is known as melt-quenching technique. Kaur et al. (2016) [1] highlighted that the melt-quenching method able to enhance the mechanical properties like hardness and flexural strength of the material. The nature of the glass systems is proven to be amorphous based on the XRD pattern. The FTIR spectra of the glass systems confirm the existence of five bands which are assigned for the BO4, BO3,TeO4and TeO3vibrational groups. The density of the glass systems is increased with the addition of Dy2O3while the molar volume is found to be inversely proportional to the density of the proposed glass. The optical properties of the glasses are determined through the absorption spectra obtained from the UV-VIS spectrophotometer. From the absorption spectra, the indirect and direct optical band gaps and the Urbach energy are found to be inversely proportional to each other. As the molar fraction of the Dy2O3increased, the optical band gaps are observed to increase as opposed to the Urbach energy. For this glass system, the values of refractive index, electronic polarizability, oxide ion polarizability and the optical basicity are found to decrease as the addition of the dysprosium oxide is increased. From the emission spectra, two intense blue and yellow emission bands are observed, which correspond to the4F9/2→6H15/2and4F9/2→6H13/2transitions of Dy3+ions respectively. The CIE chromaticity coordinates of the zinc borotellurite glass systems are found to be located in the white light region.
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.
To characterize the binding of a widely used herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D) to the major transporter in human circulation, human serum albumin (HSA), multi-spectroscopic approaches such as fluorescence, absorption and circular dichroism along with computational methods were employed. Analysis of the fluorescence and absorption spectroscopic data confirmed the 2,4-D-HSA complex formation. A static quenching mechanism was evident from the inverse temperature dependence of the KSV values. The complex was stabilized by a weak binding affinity (Ka = 5.08 × 103 M-1 at 298 K). Quantitative analysis of thermodynamic data revealed participation of hydrophobic and van der Waals interactions as well as hydrogen bonds in the binding process. Circular dichroism and three-dimensional fluorescence spectral results showed structural (secondary and tertiary) changes in HSA as well as microenvironmental perturbation around protein fluorophores (Trp and Tyr residues) upon 2,4-D binding. Addition of 2,4-D to HSA was found to improve protein's thermal stability. Competitive displacement results as well as computational analyses suggested preferred location of the 2,4-D binding site as Sudlow's site I (subdomain IIA) in HSA.
Inclusion complexes of R-ketoprofen and S-ketoprofen enantiomers with β-cyclodextrin (β-CD) in aqueous solution were studied using various spectroscopic techniques such as Raman, FTIR, UV and fluorescence. The different relative intensities and characteristic band shifts of the two enantiomers from Raman spectra suggests different interaction when complexed with β-CD. Raman experiments revealed a noticeable diminishing of the CC vibration and ring deformation, which indicate the embedding of ketoprofen inside the β-CD cavity. It's revealed that distinct differences between R- and S-ketoprofen in the presence of β-CD at neutral pH. The stoichiometry ratio and binding constant of the inclusion complexes were calculated using Benesi-Hildebrand plot. Both enantiomers showed stoichiometry ratio of 1:1 inclusion complex with β-CD. The binding constant of R-ketoprofen (4088 M-1) is higher than S-ketoprofen (2547 M-1). These values indicated that β-CD formed inclusion complexes more preferentially with R-ketoprofen than S-ketoprofen. Results demonstrated that β-CD can be used as a promising chiral selector for ketoprofen enantiomers.
Enhanced red and orange fluorescence emissions of Sm3+ Rare earth (RE) ions were observed in sodium‑zinc tellurite glasses embedded with silver and gold nanoparticles (NPs). The fine distribution of NPs in the glass matrix with an average diameter ~ 11.09 nm and ~3.86 nm for Ag and Au NPs respectively were confirmed by using transmission electron microscope (TEM). The embedding of Ag and Au NPs into the glass structure caused an increasing in the transition emission intensity of Sm3+ ions, which is ascribed to the progress of the presence of the localized surface Plasmon resonance (LSPR) indicating from the characteristic absorption peaks. The luminescence and absorption spectra have been discussed using a standard hypothesis Judd-Ofelt theory for a certain absorption transitions 6P3/2, 4I11/2, 6F11/2, 6F9/2, 6F7/2, 6F5/2, 6F3/2, 6H15/2, 6F1/2 and emission transitions 6H5/2, H7/2, 6H9/2 and H11/2 under 409 nm excitation of the Sm3+ ions. The decay life time curve exhibited a non-exponential behavior of the studied glass samples and the results were compared with the similar reported glasses. An efficient red and orange fluorescence emission illustrate that the Sm3+-doped sodium‑zinc tellurite embedded with Ag and Au NPs are potential materials for the laser illumination.
Fish epidermal mucus is an important reservoir of antipathogenic compounds which serves as the first line of the immune defence. Despite its significant role in the physiology and health of fish, detailed profiling of fish epidermal mucus has yet to be explored. Therefore, this study investigates a label-free colloidal surface-enhanced Raman spectroscopic (SERS) method for profiling grouper mucus. Gold nanoparticles were first synthesised using the standard citrate reduction and characterised using ultraviolet-visible spectroscopy, transmission electron microscopy and dynamic light scattering. The influence of acidified sodium sulphate (Na2SO4) at pH 3 as the aggregating agent on the enhancement of the SERS spectrum of different analyte samples including rhodamine 6G (R6G) dye, lysozyme solution and hybrid grouper (Epinephelus fuscoguttatus × Epinephelus lanceolatus) mucus was observed. Based on the results, an optimal Na2SO4 concentration of 1 M was recorded to achieve the highest enhancement of the SERS signal for R6G and grouper mucus, while the optimal concentration for lysozyme was 0.1 M. The results indicated a higher degree of aggregation induced by lysozyme than R6G and grouper mucus. A few overlapping peaks of the SERS spectra of lysozyme and grouper mucus made it possible to confirm the presence of lysozyme as potential biomarkers.
Wavelength selection is crucial to the success of near-infrared (NIR) spectroscopy analysis as it considerably improves the generalization of the multivariate model and reduces model complexity. This study proposes a new wavelength selection method, interval flower pollination algorithm (iFPA), for spectral variable selection in the partial least squares regression (PLSR) model. The proposed iFPA consists of three phases. First, the flower pollination algorithm is applied to search for informative spectral variables, followed by variable elimination. Subsequently, the iFPA performs a local search to determine the best continuous interval spectral variables. The interpretability of the selected variables is assessed on three public NIR datasets (corn, diesel and soil datasets). Performance comparison with other competing wavelength selection methods shows that the iFPA used in conjunction with the PLSR model gives better prediction performance, with the root mean square error of prediction values of 0.0096-0.0727, 0.0015-3.9717 and 1.3388-29.1144 are obtained for various responses in corn, diesel and soil datasets, respectively.
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.