rashmi mishra | Oklahoma State University (original) (raw)
Papers by rashmi mishra
The European Physical Journal Applied Physics, 2017
In this paper the rate of electron emission from an illuminated hot metallic plate has been evalu... more In this paper the rate of electron emission from an illuminated hot metallic plate has been evaluated on the basis of the free electron theory of metals and Fowler's theory of photoelectric electron emission. The modification of the electron energy distribution (or enhancement of electron temperature) in the plate by energetic electrons (which get their normal energy enhanced on the surface by incident photons of frequency below threshold and are not emitted) has been taken into account. The thermionic current as modified by the electron temperature so enhanced by irradiation has been evaluated. The results may be applicable to thermionic convertors, as proposed to be operated by Schwede et al. [J.
Journal of Molecular Structure, 2017
Isoformononetin, a methoxylated isoflavone present in medicinal plants, has non-estrogenic bone f... more Isoformononetin, a methoxylated isoflavone present in medicinal plants, has non-estrogenic bone forming effect via differential mitogen-activated protein kinase (MAPK) signaling. Spectroscopic (FT-Raman, FT-IR, UV-vis and NMR spectra) and quantum chemical calculations using density functional theory (DFT) and 6-311++G(d,p) as a large basis set have been employed to study the structural and electronic properties of isoformononetin. A detailed conformational analysis is performed to determine the stability among conformers and the various possibilities of intramolecular hydrogen bonding formation. Molecular docking studies with different protein kinases were performed on isoformononetin and previously studied isoflavonoid, formononetin in order to understand their inhibitory nature and the effect of functional groups on osteogenic or osteoporosis associated proteins. It is found that the oxygen atoms of methoxy, hydroxyl groups attached to phenyl rings R1, R3 and carbonyl group attached to pyran ring R2, play a major role in binding with the protein kinases that is responsible for the osteoporosis; however, no hydrophobic interactions are observed between rings of ligand and protein. The electronic properties such as HOMO and LUMO energies were determined by timedependent TD-DFT which predict that conformer II is a little bit more stable and chemically low reactive than conformer I of isoformononetin. To estimate the structure-activity relationship, the molecular electrostatic potential (MEP) surface map, and reactivity descriptors are calculated from the optimized geometry of the molecule. From these results, it is also found that isoformononetin is kinetically more stable, less toxic, weak electrophile and chemically less reactive than formononetin. The atoms in molecules and natural bond orbital analysis are applied for the detailed analysis of intra and intermolecular hydrogen bonding interactions.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy, Jan 5, 2017
Research in the field of medicinal plants including Piper species like long pepper (Piper longum ... more Research in the field of medicinal plants including Piper species like long pepper (Piper longum L.- Piperaceae) is increasing all over the world due to its use in traditional and Ayurvedic medicine. Piplartine (piperlongumine, 5,6-dihydro-1-[(2E)-1-oxo-3-(3,4,5-trimethoxyphenyl)-2-propenyl]-2(1H)-pyridinone), a biologically active alkaloid/amide was isolated from the phytochemical investigations of Piper species, as long pepper. This alkaloid has cytotoxic, anti-fungal, anti-diabetic, anti-platelet aggregation, anti-tumoral, anxiolytic, anti-depressant, anti-leishmanial, and genotoxic activities, but, its anticancer property is the most promising and has been widely explored. The main purpose of the work is to present a solid state characterization of PPTN using thermal analysis and vibrational spectroscopy. Quantum mechanical calculations based on the density functional theory was also applied to investigate the molecular conformation and vibrational spectrum, which was compared w...
Journal of Molecular Structure, 2015
ABSTRACT Formononetin [7-hydroxy-3(4-methoxyphenyl)chromone or 4′-methoxy daidzein] is a soy isof... more ABSTRACT Formononetin [7-hydroxy-3(4-methoxyphenyl)chromone or 4′-methoxy daidzein] is a soy isoflavonoid that is found abundantly in traditional Chinese medicine Astragalus mongholicus (Bunge) and Trifolium pretense L. (red clover), and in an Indian medicinal plant, Butea (B.) monosperma. Crude extract of B. monosperma is used for rapid healing of fracture in Indian traditional medicine. In this study, a combined theoretical and experimental approach is used to study the properties of formononetin. The optimized geometry was calculated by B3LYP method using 6-311++G(d,p) as a large basis set. The FT-Raman and FT-IR spectra were recorded in the solid phase, and interpreted in terms of potential energy distribution (PED) analysis. Density functional theory (DFT) is applied to explore the nonlinear optical properties of the molecule. Good consistency is found between the calculated results and observed data for the electronic absorption, IR and Raman spectra. The solvent effects have been calculated using time-dependent density functional theory in combination with the integral equation formalism polarized continuum model, and the results are in good agreement with observed measurements. The double well potential energy curve of the molecule about the respective bonds, have been plotted, as obtained from DFT/6-31G basis set. The computational results diagnose the most stable conformer of formononetin. The HOMO–LUMO energy gap of possible conformers has been calculated for comparing their chemical activity. Chemical reactivity has been measured by reactivity descriptors and molecular electrostatic potential surface (MEP). The 1H and 13C NMR chemical shifts of the molecule were calculated by the Gauge including atomic orbital (GIAO) method. Furthermore, the role of CHO intramolecular hydrogen bond in the stability of molecule is investigated on the basis of the results of topological properties of AIM theory and NBO analysis. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013
Clopidogrel hydrogen sulfate (+)-(S)-(2-chlorophenyl)-6,7-dihydrothieno[3,2-c]pyridine-5(4H)-acet... more Clopidogrel hydrogen sulfate (+)-(S)-(2-chlorophenyl)-6,7-dihydrothieno[3,2-c]pyridine-5(4H)-acetate sulfate (1:1), is a selective adenosine diphosphate (ADP) receptor antagonist often used in the treatment of coronary artery, peripheral vascular and cerebrovascular diseases. In the present communication, a comparative study of two polymorphic forms (forms 1 and 2) of clopidogrel hydrogen sulfate (CLP) has been reported. There is difference in conformation and intermolecular hydrogen bonding pattern of two forms. These differences are nicely reflected in the vibrational spectra. The molecular structure, fundamental vibrational frequencies and intensity of the vibrational bands of CLP form 1 are interpreted with the aid of structure optimizations and normal mode analysis based on ab initio HF and DFT method employing 6-311++G(d,p) basis. Polymorphism in CLP have been studied using various characterization tools like FT-Raman, FT-IR spectroscopy and DSC in combination with the quantum chemical calculations. UV-vis spectroscopic studies along with HOMO-LUMO analysis of both polymorphs were performed. The solvent effect calculated by TD-DFT/IEF-PCM/6-31G model results complements with the experimental findings. Stability of the molecule arising from hyper conjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013
The global problem of advancing bacterial resistance to newer drugs has led to renewed interest i... more The global problem of advancing bacterial resistance to newer drugs has led to renewed interest in the use of Chloramphenicol Palmitate (C27H42Cl2N2O6) [Palmitic acid alpha ester with D-threo-(-),2-dichloro-N-(beta-hydroxy-alpha-(hydroxymethyl)-p-nitrophenethyl)acetamide also known as Detereopal]. The characterization of the three polymorphic forms of Chloramphenicol Palmitate (CPP) was done spectroscopically by employing FT-IR and FT-Raman techniques. The equilibrium geometry, various bonding features, and harmonic wavenumbers have been investigated for most stable form A with the help of DFT calculations and a good correlation was found between experimental data and theoretical values. Electronic properties have been analyzed employing TD-DFT for both gaseous and solvent phase. The theoretical calculation of thermodynamical properties along with NBO analysis has also been performed to have a deep insight into the molecule for further applications.
Molecular Simulation, 2013
ABSTRACT Imatinib, a phenylaminopyrimidine compound is a therapeutic drug for treatment of chroni... more ABSTRACT Imatinib, a phenylaminopyrimidine compound is a therapeutic drug for treatment of chronic myelogeneous leukaemia and gastrointestinal stromal tumours. It is well known that imatinib mesylate (ImM) exists in two polymorphic forms alpha and beta. In this work, a computational study on molecular properties of ImM polymorphs is presented using density functional theory, B3LYP functional and 6-311G(d,p) as basis set. Natural bond orbital analysis is carried out to investigate the various conjugative and hyperconjugative interactions within the molecule and their second-order stabilisation energy (E-(2)). The local nucleophilic reactivity descriptors such as Fukui functions (f(k)(-)), local softness (s(k)(-)) and electrophilicity indices (omega(-)(k)) analyses are carried out to determine the reactive sites within the molecule. To determine strength and nature of intra-and intermolecular interactions, topological parameters as electron density (ED) (rho(BCP)), Laplacian of ED (del(2) rho(BCP)) and total electron energy density (H-BCP) at bond critical points have been analysed by 'quantum theory of atoms in molecules' in detail. The computed first hyperpolarisability (beta(0)) for both forms of ImM molecule (10.927 and 10.354 x 10(-30) esu) suggests that the investigated molecule is an attractive object in future for non-linear optical properties. Molecular electrostatic potential surface of ImM has been mapped to predict the inhibitory activity and binding affinity with a panel of protein tyrosine kinases.
Journal of Structural Chemistry, 2011
A systematic study on the structural characteristics of the 2-pyranone ring containing molecules ... more A systematic study on the structural characteristics of the 2-pyranone ring containing molecules with bromine, nitrile, and amide substituents at the C-3 position in the ring is conducted in the electronic ground (S 0) state by DFT calculations using the B3LYP/6-311++G** method. The geometrical structure of the bromine substituted compound, which shows potent hepatoprotective activity, is studied both in the ground (S 0) and first excited singlet (S 1) states using RHF/6-311++G** and CIS/6-311++G** methods respectively. The molecules are found to exist in two isomeric forms gauche and trans that have the enthalpy difference of less than 3.32 kcal/mol; the latter is the preferred orientation in the gaseous phase. The S 1 state is a 1 (S,S*) state that arises S-electron transfer from the region of a double bond in the pyranone ring to the region of the internuclear bond connecting the 2-pyranone and benzene rings. A complete vibrational analysis is conducted for the 3-bromo-6-(4-Chlorophenyl)-4-thiomethyl-2H-pyran-2-one molecule based on the experimental infrared spectra in the 50-4000 cm-1 region and DFT/6-311++G** computations of vibrational frequencies for the gauche and trans isomeric forms. Spectral assignments based on the potential energy distribution along the internal coordinates confirm the non-planar structure of the molecule. K e y w o r d s: 2-pyranone, molecular conformation, infrared spectra, DFT. Ground state (S 0) Molecule 1 Molecule 2 Molecule 3 gauche trans gauche trans gauche trans
Physics of Plasmas, 2015
By utilizing the recent concept [G. Delzanno et al., Phys. Plasmas 12, 062102 (2005) and G. Delza... more By utilizing the recent concept [G. Delzanno et al., Phys. Plasmas 12, 062102 (2005) and G. Delzanno and X. Tang, Phys. Rev. Lett. 113, 035002 (2014)] that the radial potential, experienced by an electron in the vicinity of a positively charged spherical particle depends on the transverse momentum of the electron, we have evaluated the rate of thermionic and photoelectron emission from a positively charged spherical particle and the corresponding average electron energy in a plasma, with Debye Screening. The effect of screening is manifested in the magnitude of a maximum in the radial potential energy versus r curve and is characterized by a parameter b which depends solely on ðr 0 =kÞ. Simple expressions for the change in the rates of emission and corresponding electron energy due to inclusion of the mechanism (mentioned above) in the analysis have been derived. The results of numerical computations have been presented and discussed. Simple expressions for the rates of electron emission from positively charged particles and corresponding average electron energy are necessary in the study of kinetics of complex plasmas. This work suffers from the limitation that the Debye length and even the nature of screening is not apriori known. In general, the evaluation of the nature of shielding and the shielding length requires a self consistent computation, similar to that carried out by Delzanno and Tang [Phys. Rev. Lett. 113, 035002 (2014)] in their work on thermionic emission in vacuum.
Poonam Tandon (2014) A comparative computational study on molecular structure, NBO analysis, mult... more Poonam Tandon (2014) A comparative computational study on molecular structure, NBO analysis, multiple interactions, chemical reactivity and first hyperpolarisability of imatinib mesylate polymorphs using DFT and QTAIM approach, Molecular Simulation, Imatinib, a phenylaminopyrimidine compound is a therapeutic drug for treatment of chronic myelogeneous leukaemia and gastrointestinal stromal tumours. It is well known that imatinib mesylate (ImM) exists in two polymorphic forms a and b. In this work, a computational study on molecular properties of ImM polymorphs is presented using density functional theory, B3LYP functional and 6-311G(d,p) as basis set. Natural bond orbital analysis is carried out to investigate the various conjugative and hyperconjugative interactions within the molecule and their second-order stabilisation energy (E (2)). The local nucleophilic reactivity descriptors such as Fukui functions (f 2 k), local softness (s 2 k) and electrophilicity indices (v 2 k) analyses are carried out to determine the reactive sites within the molecule. To determine strength and nature of intra-and intermolecular interactions, topological parameters as electron density (ED) (r BCP), Laplacian of ED (f 2 r BCP) and total electron energy density (H BCP) at bond critical points have been analysed by 'quantum theory of atoms in molecules' in detail. The computed first hyperpolarisability (b 0) for both forms of ImM molecule (10.927 and 10.354 £ 10 230 esu) suggests that the investigated molecule is an attractive object in future for non-linear optical properties. Molecular electrostatic potential surface of ImM has been mapped to predict the inhibitory activity and binding affinity with a panel of protein tyrosine kinases.
Research in the field of medicinal plants including Piper species like long pepper (Piper longum ... more Research in the field of medicinal plants including Piper species like long pepper (Piper longum L.-Piperaceae) is increasing all over the world due to its use in traditional and Ayurvedic medicine. Piplartine (piperlongumine, 5,6-dihydro-1-[(2E)-1-oxo-3-(3,4,5-trimethoxyphenyl)-2-propenyl]-2(1H)-pyridinone), a biologically active al-kaloid/amide was isolated from the phytochemical investigations of Piper species, as long pepper. This alkaloid has cytotoxic, anti-fungal, anti-diabetic, anti-platelet aggregation, anti-tumoral, anxiolytic, anti-depressant, anti-leishmanial, and genotoxic activities, but, its anticancer property is the most promising and has been widely explored. The main purpose of the work is to present a solid state characterization of PPTN using thermal analysis and vibrational spectroscopy. Quantum mechanical calculations based on the density functional theory was also applied to investigate the molecular conformation and vibrational spectrum, which was compared with experimental results obtained by Raman scattering, far (terahertz) and mid-infrared adsorption spectroscopy. NBO analysis has been performed which predict that most intensive interactions in PPTN are the hyperconjugative interactions between n(1) N6 and π*(O1\ \C7) having delocalization energy of 50.53 kcal/mol, Topological parameters have been analyzed using 'AIM' analysis which governs the three bond critical points (BCPs), one di-hydrogen, and four ring critical points (RCPs). MEP surface has been plotted which forecast that the most negative region is associated with the electronegative oxygen atoms (sites for nucleophilic activity). Theoretically , to confirm that the title compound has anti-cancer, anti-diabetic and anti-platelet aggregation activities, it was analyzed by molecular docking interactions with the corresponding target receptors. The obtained values of H-bonding parameters and binding affinity prove that its anti-cancer activity is the more prominent than the other properties.
![Research paper thumbnail of Molecular structure, spectral investigation (1H NMR, 13C NMR, UV–Visible, FT-IR, FT-Raman), NBO, intramolecular hydrogen bonding, chemical reactivity and first hyperpolarizability analysis of formononetin [7-hydroxy-3(4-methoxyphenyl)chromone]: A quantum chemical study](https://attachments.academia-assets.com/61429793/thumbnails/1.jpg)
](Molecular structure, spectral investigation (1 H NMR, 13 C NMR, UV-Visible, FT-IR, FT-Raman), NBO... more Molecular structure, spectral investigation (1 H NMR, 13 C NMR, UV-Visible, FT-IR, FT-Raman), NBO, intramolecular hydrogen bonding, chemical reactivity and first hyperpolarizability analysis of formononetin [7-hydroxy-3(4-methoxyphenyl)chromone]: A quantum chemical study
Isoformononetin, a methoxylated isoflavone present in medicinal plants, has non-estrogenic bone f... more Isoformononetin, a methoxylated isoflavone present in medicinal plants, has non-estrogenic bone forming effect via differential mitogen-activated protein kinase (MAPK) signaling. Spectroscopic (FT-Raman, FT-IR, UVevis and NMR spectra) and quantum chemical calculations using density functional theory (DFT) and 6-311þþG(d,p) as a large basis set have been employed to study the structural and electronic properties of isoformononetin. A detailed conformational analysis is performed to determine the stability among conformers and the various possibilities of intramolecular hydrogen bonding formation. Molecular docking studies with different protein kinases were performed on isoformononetin and previously studied isoflavonoid, formononetin in order to understand their inhibitory nature and the effect of functional groups on osteogenic or osteoporosis associated proteins. It is found that the oxygen atoms of methoxy, hydroxyl groups attached to phenyl rings R1, R3 and carbonyl group attached to pyran ring R2, play a major role in binding with the protein kinases that is responsible for the osteoporosis; however, no hydrophobic interactions are observed between rings of ligand and protein. The electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT which predict that conformer II is a little bit more stable and chemically low reactive than conformer I of isoformononetin. To estimate the structure-activity relationship, the molecular electrostatic potential (MEP) surface map, and reactivity descriptors are calculated from the optimized geometry of the molecule. From these results, it is also found that isoformononetin is kinetically more stable, less toxic, weak electrophile and chemically less reactive than formononetin. The atoms in molecules and natural bond orbital analysis are applied for the detailed analysis of intra and intermolecular hydrogen bonding interactions.
In this paper the rate of electron emission from an illuminated hot metallic plate has been evalu... more In this paper the rate of electron emission from an illuminated hot metallic plate has been evaluated on the basis of the free electron theory of metals and Fowler's theory of photoelectric electron emission. The modification of the electron energy distribution (or enhancement of electron temperature) in the plate by energetic electrons (which get their normal energy enhanced on the surface by incident photons of frequency below threshold and are not emitted) has been taken into account. The thermionic current as modified by the electron temperature so enhanced by irradiation has been evaluated. The results may be applicable to thermionic convertors, as proposed to be operated by Schwede et al. [J.
On the basis of a dynamic analysis the effectiveness of dust suspension for the reduction and enh... more On the basis of a dynamic analysis the effectiveness of dust suspension for the reduction and enhancement of electron density in the E-layer of the ionosphere has been investigated in this paper. The analysis is based on the modelling of the E-layer as the Chapman α layer (validated earlier); the electron/ion production function, arrived at by Chapman and effective electron temperature-dependent electron-ion recombination coefficients in agreement with observations have been used. The balance of the charge on the particles and the number/ energy balance of the constituents have been taken into account. The following is the physics of the change in electron density in the ionosphere by the suspension of dust. First, the dust provides a source (emission) and sink (accretion) of electrons. Second, the dust emits photoelectrons with energies much higher than those of ambient electrons, which enhances the electron temperature, leading to a reduced electron-ion recombination coefficient, and thus to a higher electron density. An interplay of these processes and the natural processes of electron production/annihilation determines the electron density and temperature in the dust suspension in the ionosphere. The numerical results, corresponding to suspension of dust of silicate (high work function) and Cs coated bronze (low work function) in the E-layer at 105 km are presented and discussed.
This article summarises the main features of polymorphism, stressing on its physical aspects, cla... more This article summarises the main features of polymorphism, stressing on its physical aspects, classification, types, characterization and applications. We have also discussed the importance of this phenomenon in pharmaceutical compounds and why is it necessary to study polymorphism.
In the present manuscript a brief discussion about the new generation of plastic or polymer also ... more In the present manuscript a brief discussion about the new generation of plastic or polymer also called materials of 21 st century, which could be conductive once it undergoes a structural modification process called doping has been presented. Also how theoretical methods utilizing quantum chemical calculations can be employed to study various properties of these new generation polymers and what informations can be drawn from them about their structural and electronic properties has been discussed.
In this paper, we consider the nonlinearity in the propagation of electromagnetic (e.m.) waves in... more In this paper, we consider the nonlinearity in the propagation of electromagnetic (e.m.) waves in a
plasma caused by the electron temperature dependence of the coefficient of recombination of
electrons with ions; specifically, the ionospheric E layer has been investigated. The enhancement in
electron temperature by an intense electromagnetic wave causes reduction of the electron-ion
recombination coefficient and thereby enhancement of electron density, the electron collision frequency
also gets enhanced. The equations for number and energy balance of electrons and the
wave equation have been used to predict the dependence of electron density/collision frequency
and the nonlinear refractive index and absorption coefficient on aE20
(proportional to wave irradiance).
The dependence of the propagation parameters on aE20
has been used to investigate the nonlinear
electromagnetic wave propagation in the ionosphere. The study concludes that the electron
temperature dependence of the recombination coefficient should be considered in all analyses of
nonlinear plasma-e.m. wave interaction.
The European Physical Journal Applied Physics, 2017
In this paper the rate of electron emission from an illuminated hot metallic plate has been evalu... more In this paper the rate of electron emission from an illuminated hot metallic plate has been evaluated on the basis of the free electron theory of metals and Fowler's theory of photoelectric electron emission. The modification of the electron energy distribution (or enhancement of electron temperature) in the plate by energetic electrons (which get their normal energy enhanced on the surface by incident photons of frequency below threshold and are not emitted) has been taken into account. The thermionic current as modified by the electron temperature so enhanced by irradiation has been evaluated. The results may be applicable to thermionic convertors, as proposed to be operated by Schwede et al. [J.
Journal of Molecular Structure, 2017
Isoformononetin, a methoxylated isoflavone present in medicinal plants, has non-estrogenic bone f... more Isoformononetin, a methoxylated isoflavone present in medicinal plants, has non-estrogenic bone forming effect via differential mitogen-activated protein kinase (MAPK) signaling. Spectroscopic (FT-Raman, FT-IR, UV-vis and NMR spectra) and quantum chemical calculations using density functional theory (DFT) and 6-311++G(d,p) as a large basis set have been employed to study the structural and electronic properties of isoformononetin. A detailed conformational analysis is performed to determine the stability among conformers and the various possibilities of intramolecular hydrogen bonding formation. Molecular docking studies with different protein kinases were performed on isoformononetin and previously studied isoflavonoid, formononetin in order to understand their inhibitory nature and the effect of functional groups on osteogenic or osteoporosis associated proteins. It is found that the oxygen atoms of methoxy, hydroxyl groups attached to phenyl rings R1, R3 and carbonyl group attached to pyran ring R2, play a major role in binding with the protein kinases that is responsible for the osteoporosis; however, no hydrophobic interactions are observed between rings of ligand and protein. The electronic properties such as HOMO and LUMO energies were determined by timedependent TD-DFT which predict that conformer II is a little bit more stable and chemically low reactive than conformer I of isoformononetin. To estimate the structure-activity relationship, the molecular electrostatic potential (MEP) surface map, and reactivity descriptors are calculated from the optimized geometry of the molecule. From these results, it is also found that isoformononetin is kinetically more stable, less toxic, weak electrophile and chemically less reactive than formononetin. The atoms in molecules and natural bond orbital analysis are applied for the detailed analysis of intra and intermolecular hydrogen bonding interactions.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy, Jan 5, 2017
Research in the field of medicinal plants including Piper species like long pepper (Piper longum ... more Research in the field of medicinal plants including Piper species like long pepper (Piper longum L.- Piperaceae) is increasing all over the world due to its use in traditional and Ayurvedic medicine. Piplartine (piperlongumine, 5,6-dihydro-1-[(2E)-1-oxo-3-(3,4,5-trimethoxyphenyl)-2-propenyl]-2(1H)-pyridinone), a biologically active alkaloid/amide was isolated from the phytochemical investigations of Piper species, as long pepper. This alkaloid has cytotoxic, anti-fungal, anti-diabetic, anti-platelet aggregation, anti-tumoral, anxiolytic, anti-depressant, anti-leishmanial, and genotoxic activities, but, its anticancer property is the most promising and has been widely explored. The main purpose of the work is to present a solid state characterization of PPTN using thermal analysis and vibrational spectroscopy. Quantum mechanical calculations based on the density functional theory was also applied to investigate the molecular conformation and vibrational spectrum, which was compared w...
Journal of Molecular Structure, 2015
ABSTRACT Formononetin [7-hydroxy-3(4-methoxyphenyl)chromone or 4′-methoxy daidzein] is a soy isof... more ABSTRACT Formononetin [7-hydroxy-3(4-methoxyphenyl)chromone or 4′-methoxy daidzein] is a soy isoflavonoid that is found abundantly in traditional Chinese medicine Astragalus mongholicus (Bunge) and Trifolium pretense L. (red clover), and in an Indian medicinal plant, Butea (B.) monosperma. Crude extract of B. monosperma is used for rapid healing of fracture in Indian traditional medicine. In this study, a combined theoretical and experimental approach is used to study the properties of formononetin. The optimized geometry was calculated by B3LYP method using 6-311++G(d,p) as a large basis set. The FT-Raman and FT-IR spectra were recorded in the solid phase, and interpreted in terms of potential energy distribution (PED) analysis. Density functional theory (DFT) is applied to explore the nonlinear optical properties of the molecule. Good consistency is found between the calculated results and observed data for the electronic absorption, IR and Raman spectra. The solvent effects have been calculated using time-dependent density functional theory in combination with the integral equation formalism polarized continuum model, and the results are in good agreement with observed measurements. The double well potential energy curve of the molecule about the respective bonds, have been plotted, as obtained from DFT/6-31G basis set. The computational results diagnose the most stable conformer of formononetin. The HOMO–LUMO energy gap of possible conformers has been calculated for comparing their chemical activity. Chemical reactivity has been measured by reactivity descriptors and molecular electrostatic potential surface (MEP). The 1H and 13C NMR chemical shifts of the molecule were calculated by the Gauge including atomic orbital (GIAO) method. Furthermore, the role of CHO intramolecular hydrogen bond in the stability of molecule is investigated on the basis of the results of topological properties of AIM theory and NBO analysis. The calculated first hyperpolarizability shows that the molecule is an attractive molecule for future applications in non-linear optics.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013
Clopidogrel hydrogen sulfate (+)-(S)-(2-chlorophenyl)-6,7-dihydrothieno[3,2-c]pyridine-5(4H)-acet... more Clopidogrel hydrogen sulfate (+)-(S)-(2-chlorophenyl)-6,7-dihydrothieno[3,2-c]pyridine-5(4H)-acetate sulfate (1:1), is a selective adenosine diphosphate (ADP) receptor antagonist often used in the treatment of coronary artery, peripheral vascular and cerebrovascular diseases. In the present communication, a comparative study of two polymorphic forms (forms 1 and 2) of clopidogrel hydrogen sulfate (CLP) has been reported. There is difference in conformation and intermolecular hydrogen bonding pattern of two forms. These differences are nicely reflected in the vibrational spectra. The molecular structure, fundamental vibrational frequencies and intensity of the vibrational bands of CLP form 1 are interpreted with the aid of structure optimizations and normal mode analysis based on ab initio HF and DFT method employing 6-311++G(d,p) basis. Polymorphism in CLP have been studied using various characterization tools like FT-Raman, FT-IR spectroscopy and DSC in combination with the quantum chemical calculations. UV-vis spectroscopic studies along with HOMO-LUMO analysis of both polymorphs were performed. The solvent effect calculated by TD-DFT/IEF-PCM/6-31G model results complements with the experimental findings. Stability of the molecule arising from hyper conjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013
The global problem of advancing bacterial resistance to newer drugs has led to renewed interest i... more The global problem of advancing bacterial resistance to newer drugs has led to renewed interest in the use of Chloramphenicol Palmitate (C27H42Cl2N2O6) [Palmitic acid alpha ester with D-threo-(-),2-dichloro-N-(beta-hydroxy-alpha-(hydroxymethyl)-p-nitrophenethyl)acetamide also known as Detereopal]. The characterization of the three polymorphic forms of Chloramphenicol Palmitate (CPP) was done spectroscopically by employing FT-IR and FT-Raman techniques. The equilibrium geometry, various bonding features, and harmonic wavenumbers have been investigated for most stable form A with the help of DFT calculations and a good correlation was found between experimental data and theoretical values. Electronic properties have been analyzed employing TD-DFT for both gaseous and solvent phase. The theoretical calculation of thermodynamical properties along with NBO analysis has also been performed to have a deep insight into the molecule for further applications.
Molecular Simulation, 2013
ABSTRACT Imatinib, a phenylaminopyrimidine compound is a therapeutic drug for treatment of chroni... more ABSTRACT Imatinib, a phenylaminopyrimidine compound is a therapeutic drug for treatment of chronic myelogeneous leukaemia and gastrointestinal stromal tumours. It is well known that imatinib mesylate (ImM) exists in two polymorphic forms alpha and beta. In this work, a computational study on molecular properties of ImM polymorphs is presented using density functional theory, B3LYP functional and 6-311G(d,p) as basis set. Natural bond orbital analysis is carried out to investigate the various conjugative and hyperconjugative interactions within the molecule and their second-order stabilisation energy (E-(2)). The local nucleophilic reactivity descriptors such as Fukui functions (f(k)(-)), local softness (s(k)(-)) and electrophilicity indices (omega(-)(k)) analyses are carried out to determine the reactive sites within the molecule. To determine strength and nature of intra-and intermolecular interactions, topological parameters as electron density (ED) (rho(BCP)), Laplacian of ED (del(2) rho(BCP)) and total electron energy density (H-BCP) at bond critical points have been analysed by 'quantum theory of atoms in molecules' in detail. The computed first hyperpolarisability (beta(0)) for both forms of ImM molecule (10.927 and 10.354 x 10(-30) esu) suggests that the investigated molecule is an attractive object in future for non-linear optical properties. Molecular electrostatic potential surface of ImM has been mapped to predict the inhibitory activity and binding affinity with a panel of protein tyrosine kinases.
Journal of Structural Chemistry, 2011
A systematic study on the structural characteristics of the 2-pyranone ring containing molecules ... more A systematic study on the structural characteristics of the 2-pyranone ring containing molecules with bromine, nitrile, and amide substituents at the C-3 position in the ring is conducted in the electronic ground (S 0) state by DFT calculations using the B3LYP/6-311++G** method. The geometrical structure of the bromine substituted compound, which shows potent hepatoprotective activity, is studied both in the ground (S 0) and first excited singlet (S 1) states using RHF/6-311++G** and CIS/6-311++G** methods respectively. The molecules are found to exist in two isomeric forms gauche and trans that have the enthalpy difference of less than 3.32 kcal/mol; the latter is the preferred orientation in the gaseous phase. The S 1 state is a 1 (S,S*) state that arises S-electron transfer from the region of a double bond in the pyranone ring to the region of the internuclear bond connecting the 2-pyranone and benzene rings. A complete vibrational analysis is conducted for the 3-bromo-6-(4-Chlorophenyl)-4-thiomethyl-2H-pyran-2-one molecule based on the experimental infrared spectra in the 50-4000 cm-1 region and DFT/6-311++G** computations of vibrational frequencies for the gauche and trans isomeric forms. Spectral assignments based on the potential energy distribution along the internal coordinates confirm the non-planar structure of the molecule. K e y w o r d s: 2-pyranone, molecular conformation, infrared spectra, DFT. Ground state (S 0) Molecule 1 Molecule 2 Molecule 3 gauche trans gauche trans gauche trans
Physics of Plasmas, 2015
By utilizing the recent concept [G. Delzanno et al., Phys. Plasmas 12, 062102 (2005) and G. Delza... more By utilizing the recent concept [G. Delzanno et al., Phys. Plasmas 12, 062102 (2005) and G. Delzanno and X. Tang, Phys. Rev. Lett. 113, 035002 (2014)] that the radial potential, experienced by an electron in the vicinity of a positively charged spherical particle depends on the transverse momentum of the electron, we have evaluated the rate of thermionic and photoelectron emission from a positively charged spherical particle and the corresponding average electron energy in a plasma, with Debye Screening. The effect of screening is manifested in the magnitude of a maximum in the radial potential energy versus r curve and is characterized by a parameter b which depends solely on ðr 0 =kÞ. Simple expressions for the change in the rates of emission and corresponding electron energy due to inclusion of the mechanism (mentioned above) in the analysis have been derived. The results of numerical computations have been presented and discussed. Simple expressions for the rates of electron emission from positively charged particles and corresponding average electron energy are necessary in the study of kinetics of complex plasmas. This work suffers from the limitation that the Debye length and even the nature of screening is not apriori known. In general, the evaluation of the nature of shielding and the shielding length requires a self consistent computation, similar to that carried out by Delzanno and Tang [Phys. Rev. Lett. 113, 035002 (2014)] in their work on thermionic emission in vacuum.
Poonam Tandon (2014) A comparative computational study on molecular structure, NBO analysis, mult... more Poonam Tandon (2014) A comparative computational study on molecular structure, NBO analysis, multiple interactions, chemical reactivity and first hyperpolarisability of imatinib mesylate polymorphs using DFT and QTAIM approach, Molecular Simulation, Imatinib, a phenylaminopyrimidine compound is a therapeutic drug for treatment of chronic myelogeneous leukaemia and gastrointestinal stromal tumours. It is well known that imatinib mesylate (ImM) exists in two polymorphic forms a and b. In this work, a computational study on molecular properties of ImM polymorphs is presented using density functional theory, B3LYP functional and 6-311G(d,p) as basis set. Natural bond orbital analysis is carried out to investigate the various conjugative and hyperconjugative interactions within the molecule and their second-order stabilisation energy (E (2)). The local nucleophilic reactivity descriptors such as Fukui functions (f 2 k), local softness (s 2 k) and electrophilicity indices (v 2 k) analyses are carried out to determine the reactive sites within the molecule. To determine strength and nature of intra-and intermolecular interactions, topological parameters as electron density (ED) (r BCP), Laplacian of ED (f 2 r BCP) and total electron energy density (H BCP) at bond critical points have been analysed by 'quantum theory of atoms in molecules' in detail. The computed first hyperpolarisability (b 0) for both forms of ImM molecule (10.927 and 10.354 £ 10 230 esu) suggests that the investigated molecule is an attractive object in future for non-linear optical properties. Molecular electrostatic potential surface of ImM has been mapped to predict the inhibitory activity and binding affinity with a panel of protein tyrosine kinases.
Research in the field of medicinal plants including Piper species like long pepper (Piper longum ... more Research in the field of medicinal plants including Piper species like long pepper (Piper longum L.-Piperaceae) is increasing all over the world due to its use in traditional and Ayurvedic medicine. Piplartine (piperlongumine, 5,6-dihydro-1-[(2E)-1-oxo-3-(3,4,5-trimethoxyphenyl)-2-propenyl]-2(1H)-pyridinone), a biologically active al-kaloid/amide was isolated from the phytochemical investigations of Piper species, as long pepper. This alkaloid has cytotoxic, anti-fungal, anti-diabetic, anti-platelet aggregation, anti-tumoral, anxiolytic, anti-depressant, anti-leishmanial, and genotoxic activities, but, its anticancer property is the most promising and has been widely explored. The main purpose of the work is to present a solid state characterization of PPTN using thermal analysis and vibrational spectroscopy. Quantum mechanical calculations based on the density functional theory was also applied to investigate the molecular conformation and vibrational spectrum, which was compared with experimental results obtained by Raman scattering, far (terahertz) and mid-infrared adsorption spectroscopy. NBO analysis has been performed which predict that most intensive interactions in PPTN are the hyperconjugative interactions between n(1) N6 and π*(O1\ \C7) having delocalization energy of 50.53 kcal/mol, Topological parameters have been analyzed using 'AIM' analysis which governs the three bond critical points (BCPs), one di-hydrogen, and four ring critical points (RCPs). MEP surface has been plotted which forecast that the most negative region is associated with the electronegative oxygen atoms (sites for nucleophilic activity). Theoretically , to confirm that the title compound has anti-cancer, anti-diabetic and anti-platelet aggregation activities, it was analyzed by molecular docking interactions with the corresponding target receptors. The obtained values of H-bonding parameters and binding affinity prove that its anti-cancer activity is the more prominent than the other properties.
Molecular structure, spectral investigation (1 H NMR, 13 C NMR, UV-Visible, FT-IR, FT-Raman), NBO... more Molecular structure, spectral investigation (1 H NMR, 13 C NMR, UV-Visible, FT-IR, FT-Raman), NBO, intramolecular hydrogen bonding, chemical reactivity and first hyperpolarizability analysis of formononetin [7-hydroxy-3(4-methoxyphenyl)chromone]: A quantum chemical study
Isoformononetin, a methoxylated isoflavone present in medicinal plants, has non-estrogenic bone f... more Isoformononetin, a methoxylated isoflavone present in medicinal plants, has non-estrogenic bone forming effect via differential mitogen-activated protein kinase (MAPK) signaling. Spectroscopic (FT-Raman, FT-IR, UVevis and NMR spectra) and quantum chemical calculations using density functional theory (DFT) and 6-311þþG(d,p) as a large basis set have been employed to study the structural and electronic properties of isoformononetin. A detailed conformational analysis is performed to determine the stability among conformers and the various possibilities of intramolecular hydrogen bonding formation. Molecular docking studies with different protein kinases were performed on isoformononetin and previously studied isoflavonoid, formononetin in order to understand their inhibitory nature and the effect of functional groups on osteogenic or osteoporosis associated proteins. It is found that the oxygen atoms of methoxy, hydroxyl groups attached to phenyl rings R1, R3 and carbonyl group attached to pyran ring R2, play a major role in binding with the protein kinases that is responsible for the osteoporosis; however, no hydrophobic interactions are observed between rings of ligand and protein. The electronic properties such as HOMO and LUMO energies were determined by time-dependent TD-DFT which predict that conformer II is a little bit more stable and chemically low reactive than conformer I of isoformononetin. To estimate the structure-activity relationship, the molecular electrostatic potential (MEP) surface map, and reactivity descriptors are calculated from the optimized geometry of the molecule. From these results, it is also found that isoformononetin is kinetically more stable, less toxic, weak electrophile and chemically less reactive than formononetin. The atoms in molecules and natural bond orbital analysis are applied for the detailed analysis of intra and intermolecular hydrogen bonding interactions.
In this paper the rate of electron emission from an illuminated hot metallic plate has been evalu... more In this paper the rate of electron emission from an illuminated hot metallic plate has been evaluated on the basis of the free electron theory of metals and Fowler's theory of photoelectric electron emission. The modification of the electron energy distribution (or enhancement of electron temperature) in the plate by energetic electrons (which get their normal energy enhanced on the surface by incident photons of frequency below threshold and are not emitted) has been taken into account. The thermionic current as modified by the electron temperature so enhanced by irradiation has been evaluated. The results may be applicable to thermionic convertors, as proposed to be operated by Schwede et al. [J.
On the basis of a dynamic analysis the effectiveness of dust suspension for the reduction and enh... more On the basis of a dynamic analysis the effectiveness of dust suspension for the reduction and enhancement of electron density in the E-layer of the ionosphere has been investigated in this paper. The analysis is based on the modelling of the E-layer as the Chapman α layer (validated earlier); the electron/ion production function, arrived at by Chapman and effective electron temperature-dependent electron-ion recombination coefficients in agreement with observations have been used. The balance of the charge on the particles and the number/ energy balance of the constituents have been taken into account. The following is the physics of the change in electron density in the ionosphere by the suspension of dust. First, the dust provides a source (emission) and sink (accretion) of electrons. Second, the dust emits photoelectrons with energies much higher than those of ambient electrons, which enhances the electron temperature, leading to a reduced electron-ion recombination coefficient, and thus to a higher electron density. An interplay of these processes and the natural processes of electron production/annihilation determines the electron density and temperature in the dust suspension in the ionosphere. The numerical results, corresponding to suspension of dust of silicate (high work function) and Cs coated bronze (low work function) in the E-layer at 105 km are presented and discussed.
This article summarises the main features of polymorphism, stressing on its physical aspects, cla... more This article summarises the main features of polymorphism, stressing on its physical aspects, classification, types, characterization and applications. We have also discussed the importance of this phenomenon in pharmaceutical compounds and why is it necessary to study polymorphism.
In the present manuscript a brief discussion about the new generation of plastic or polymer also ... more In the present manuscript a brief discussion about the new generation of plastic or polymer also called materials of 21 st century, which could be conductive once it undergoes a structural modification process called doping has been presented. Also how theoretical methods utilizing quantum chemical calculations can be employed to study various properties of these new generation polymers and what informations can be drawn from them about their structural and electronic properties has been discussed.
In this paper, we consider the nonlinearity in the propagation of electromagnetic (e.m.) waves in... more In this paper, we consider the nonlinearity in the propagation of electromagnetic (e.m.) waves in a
plasma caused by the electron temperature dependence of the coefficient of recombination of
electrons with ions; specifically, the ionospheric E layer has been investigated. The enhancement in
electron temperature by an intense electromagnetic wave causes reduction of the electron-ion
recombination coefficient and thereby enhancement of electron density, the electron collision frequency
also gets enhanced. The equations for number and energy balance of electrons and the
wave equation have been used to predict the dependence of electron density/collision frequency
and the nonlinear refractive index and absorption coefficient on aE20
(proportional to wave irradiance).
The dependence of the propagation parameters on aE20
has been used to investigate the nonlinear
electromagnetic wave propagation in the ionosphere. The study concludes that the electron
temperature dependence of the recombination coefficient should be considered in all analyses of
nonlinear plasma-e.m. wave interaction.