Electronically excited states of membrane fluorescent probe 4-dimethylaminochalcone. Results of quantum chemical calculations

Quantum-chemical calculations of ground and excited states for membrane fluorescent probe 4-dimethylaminochalcone (DMAC) in vacuum were performed. Optimized geometries and dipole moments for lowest-lying singlet and triplet states were obtained. The nature of these electronic transitions and the relaxation path in the excited states were determined; changes in geometry and charge distribution were assessed. It was shown that in vacuum the lowest existed level is of (n, π*) nature, and the closest to it is the level of (π, π*) nature; the energy gap between them is narrow. This led to an effective (1)(π, π*) →(1)(n, π*) relaxation. After photoexcitation the molecule undergoes significant transformations, including changes in bond orders, pyramidalization angle of the dimethylamino group, and planarity of the molecule. Its dipole moment rises from 5.5 Debye in the ground state to 17.1 Debye in the (1)(π, π*) state, and then falls to 2 Debye in the (1)(n, π*) state. The excited (1)(n, π*) state is a short living state; it has a high probability of intersystem crossing into the (3)(π, π*) triplet state. This relaxation path explains the low quantum yield of DMAC fluorescence in non-polar media. It is possible that (3)(π, π*) is responsible for observed DMAC phosphorescence.     

Spectral and photophysical properties of intramolecular charge transfer fluorescence probe: 4'-dimethylamino-2,5-dihydroxychalcone

The spectral and photophysical properties of a new intramolecular charge transfer (ICT) probe, namely 4′-dimethylamino-2,5-dihydroxychalcone (DMADHC) were studied in different solvents by using steady-state absorption and emission spectroscopy. Whereas the absorption spectrum undergoes minor change with increasing polarity of the solvents, the fluorescence spectrum experiences a distinct bathochromic shift in the band position and the fluorescence quantum yield increases reaching a maximum before decrease with increasing the solvent polarity. The magnitude of change in the dipole moment was calculated based on the Lippert–Mataga equation. These results give the evidence about the intramolecular charge transfer character in the emitting singlet state of this compound.     

Solvent effects on tamoxifen molecule interacting with a single-walled carbon nanotube: a theoretical NMR study

Quantum chemical calculations of the electronic structure of tamoxifen molecule interacting with an open end of a single-walled carbon nanotube (SWCNT) were carried out and the effects of solvents (water, methanol, DMSO, acetone) on the ¹H, ¹³C, ¹⁵N, and ¹⁷O NMR parameters were studied by the GIAO-HF/STO-3G, GIAO-HF/3-21G, and GIAO/B1LYP/3-21G methods using the GAUSSIAN-98 program. The largest σ_iso value was obtained for acetone, whereas the smallest one for water. The opposite trend was obtained for the shielding asymmetry η. According to calculations, atoms at interaction site bear negative charges. The O(43) and N(38) atoms produce negative charge because they have high electron affinities. The dipole moment of tamoxifen molecule in different solvents increases with increasing the dielectric constant of the solvent. The largest dipole moment value was obtained for water by the B1LYP/3-21G method.     

The electric dipole polarity of the ground and low-lying metastable excited states of NF.

NF (nitrogen monofluoride, fluoroimidogen) is isoelectronic with O2, and, like O2, it has a triplet configuration in the ground state, with two low-lying metastable singlet excited states. The dipole moment of the a 1Delta excited state was measured in 1973 to be 0.37 +/- 0.06 D; at the time its polarity was assumed to be normal (i.e., with the negative charge on the fluorine). However, high-level electronic structure calculations, which reproduce with high accuracy the known spectroscopic constants of the ground and excited states of NF, predict a dipole moment of -0.388 D for a 1Delta NF, indicating that, despite the electronegativities, this molecule carries a positive charge on fluorine. The other singlet state is predicted to have an even larger negative dipole moment; the ground-state triplet should have a very small positive moment. Singlet NF resembles in this respect CO and BF, from the N2 isoelectronic series, both of which also have negative dipole moments.     

Quantum theory of atoms in molecules charge-charge flux-dipole flux models for the infrared intensities of X(2)CY (X = H, F, Cl; Y = O, S) molecules

The molecular dipole moments, their derivatives, and the fundamental IR intensities of the X2CY (X = H, F, Cl; Y = O, S) molecules are determined from QTAIM atomic charges and dipoles and their fluxes at the MP2/6-311++G(3d,3p) level. Root-mean-square errors of +/-0.03 D and +/-1.4 km mol(-1) are found for the molecular dipole moments and fundamental IR intensities calculated using quantum theory of atoms in molecules (QTAIM) parameters when compared with those obtained directly from the MP2/6-311++G(3d,3p) calculations and +/-0.05 D and 51.2 km mol(-1) when compared with the experimental values. Charge (C), charge flux (CF), and dipole flux (DF) contributions are reported for all the normal vibrations of these molecules. A large negative correlation coefficient of -0.83 is calculated between the charge flux and dipole flux contributions and indicates that electronic charge transfer from one side of the molecule to the other during vibrations is accompanied by a relaxation effect with electron density polarization in the opposite direction. The characteristic substituent effect that has been observed for experimental infrared intensity parameters and core electron ionization energies has been applied to the CCFDF/QTAIM parameters of F2CO, Cl2CO, F2CS, and Cl2CS. The individual atomic charge, atomic charge flux, and atomic dipole flux contributions are seen to obey the characteristic substituent effect equation just as accurately as the total dipole moment derivative. The CH, CF, and CCl stretching normal modes of these molecules are shown to have characteristic sets of charge, charge flux, and dipole flux contributions.     

Dibenzo[a,c]phenazine: a polarity-insensitive hydrogen-bonding probe

A derivative of phenazine, dibenzo[a,c]phenazine (DBPZ), can be used as a very good hydrogen-bonding probe unlike its parent phenazine molecule. Steady-state absorption and fluorescence studies reveal that DBPZ is completely insensitive to polarity of the medium. However, DBPZ can form a hydrogen bond very efficiently in its first excited singlet state. The extent of this excited-state hydrogen-bond formation depends both on size and on hydrogen-bond donor ability of the solvents. Time-resolved fluorescence studies and theoretical calculations also suggest that this hydrogen-bond formation is much more favorable in the excited state as compared to the ground state. In the excited state, the electron density is pushed toward the nitrogen atoms from the benzene rings, thereby increasing the dipole moment of the DBPZ molecule. Although the dipole moment of DBPZ increases upon photoexcitation, like other polarity probes, the molecule remains fully insensitive to the polarity of the interacting solvent. This unusual behavior of DBPZ as compared to simple phenazine and other polarity probes is due to the structure of the molecule. Hydrogen atoms at the 1 and 8 positions of DBPZ are sterically interacting with a lone pair of electrons on the proximate nitrogen atoms and make both of the nitrogen atoms inaccessible to solvent molecules. For this reason, DBPZ cannot sense the polarity of the medium. However, DBPZ can only sense solvents, those that have hydrogen with some electropositive nature, that is, the hydrogen-bond donating solvents. Hydrogen being the smallest among all elements can only interact with the lone pair of electrons of nitrogen atoms. Thus, DBPZ can act as a sensor for the hydrogen-bond donating solvents irrespective of their dielectrics.     

The styrylpyridine dye for the silane sol-gel transition studies by time-dependent fluorescence

A trans-4-(p-N,N-dimethylaminostyryl)-N-vinylbenzylpyridinium chloride (vbDMASP) fluorescence probe was optimized in ground and excited state as a function of change in the microenvironment polarity, using the Amsol HyperChem program package. In the calculations, protic and aprotic solvents were used. On this basis a change in the molecule geometry after excitation, depending on the surrounding solvent, was determined. Absorption and steady-state fluorescence spectra of vbDMASP in the solvent of different polarity and in the model water-glycerol solutions were also recorded. On the basis of Stokes' shift change with the Onsager polarity scale a change in the dipole moment of the probe during transition from ground to excited state, in protic and aprotic solvents was determined. Since during the sol-gel transition of tetraethylorthosilane in the acidic environment both polarity and viscosity of the microenvironment change the vbDMASP probe was applied and fluorescence time-resolved measurements were done. On this basis the correlations between the results of time-resolved measurements for the multichromophoric probe applied in the gelation process and molecular optimization data are discussed.     

Study on the fluorescence properties of a new intramolecular charge transfer compound 1,5-diphenyl-3-(N-ethylcarbazole-3-yl)-2-pyrazoline

The fluorescence properties of a newly synthesized compound, 1,5-diphenyl-3-(N-ethylcarbazole-3-yl)-2-pyrazoline (DEP) have been studied. On excitation at 352 nm, the fluorescence spectrum exhibits a large red shift with an increase in the polarity of solvents. The intensity of the band is different in different solvents as well. The change in the dipole moment in various solvents at room temperature has been characterized by the absorption and steady state fluorescence techniques and calculated based on the Lippert-Mataga equation. DEP has an increase of dipole moment of 2.83 D units on excitation to the lowest singlet state. It is concluded that photo-induced charge transfer from N (1) to C (3) actually exists in the excited state of the pyrazoline moiety. Its fluorescence property is relative to viscosity and temperature of solvents. The phi(f) of DEP in neutral medium or basic medium is higher than acidic medium. In addition, when the concentration of DEP is higher than 10(-3) M, its fluorescence is quenched by the collision of each molecule. The red shift of the maximum emission of DEP attributes to the formation of aggregates and the conjugate system is strengthened.     

The styrylpyridine dye for the silane sol–gel transition studies by time-dependent fluorescence

A trans-4-(p-N,N-dimethylaminostyryl)-N-vinylbenzylpyridinium chloride (vbDMASP) fluorescence probe was optimized in ground and excited state as a function of change in the microenvironment polarity, using the Amsol HyperChem program package. In the calculations, protic and aprotic solvents were used. On this basis a change in the molecule geometry after excitation, depending on the surrounding solvent, was determined.Absorption and steady-state fluorescence spectra of vbDMASP in the solvent of different polarity and in the model water–glycerol solutions were also recorded. On the basis of Stokes’ shift change with the Onsager polarity scale a change in the dipole moment of the probe during transition from ground to excited state, in protic and aprotic solvents was determined.Since during the sol–gel transition of tetraethylorthosilane in the acidic environment both polarity and viscosity of the microenvironment change the vbDMASP probe was applied and fluorescence time-resolved measurements were done. On this basis the correlations between the results of time-resolved measurements for the multichromophoric probe applied in the gelation process and molecular optimization data are discussed.     

Energy of charged states in the acetanilide crystal: trapping of charge-transfer states at vacancies as a possible mechanism for optical damage

Calculations for the acetanilide crystal yield the effective polarizability (16.6 A(3)), local electric field tensor, effective dipole moment (5.41 D), and dipole-dipole energy (-12.8 kJ/mol). Fourier-transform techniques are used to calculate the polarization energy P for a single charge in the perfect crystal (-1.16 eV); the charge-dipole energy W(D) is zero if the crystal carries no bulk dipole moment. Polarization energies for charge-transfer (CT) pairs combine with the Coulomb energy E(C) to give the screened Coulomb energy E(scr); screening is nearly isotropic, with E(scr) approximately E(C)/2.7. For CT pairs W(D) reduces to a term deltaW(D) arising from the interaction of the charge on each ion with the change in dipole moment on the other ion relative to the neutral molecule. The dipole moments calculated by density-functional theory methods with the B3LYP functional at the 6-311++G(**) level are 3.62 D for the neutral molecule, changing to 7.13 D and 4.38 D for the anion and cation, relative to the center of mass. Because of the large change in the anion, deltaW(D) reaches -0.9 eV and modifies the sequence of CT energies markedly from that of E(scr), giving the lowest two CT pairs at -1.98 eV and -1.41 eV. The changes in P and W(D) near a vacancy are calculated; W(D) changes for the individual charges because the vacancy removes a dipole moment and modifies the crystal dielectric response, but deltaW(D) and E(C) do not change. A vacancy yields a positive change DeltaP that scatters a charge or CT pair, but the change DeltaW(D) can be negative and large enough to outweigh DeltaP, yielding traps with depths that can exceed 150 meV for single charges and for CT pairs. Divacancies yield traps with depths nearly equal to the sum of those produced by the separate vacancies and so they can exceed 300 meV. These results are consistent with a mechanism of optical damage in which vacancies trap optically generated CT pairs that recombine and release energy; this can disrupt the lattice around the vacancy, thereby favoring trapping and recombination of CT pairs generated by subsequent photon absorption, leading to further lattice disruption. Revisions to previous calculations on trapping of CT pairs in anthracene are reported.     

Solvatochromic study of 1,2-dihydroxyanthraquinone in neat and binary solvent mixtures

Preferential solvation of a solvatochromic probe has been studied in binary mixtures comprising of a non-protic and a protic solvent. The non-protic solvents employed are carbon tetrachloride (CCl(4)), acetonitrile (AcN) and N,N-dimethyl formamide (DMF) and the protic solvents are methanol (MeOH) and ethanol (EtOH). The probe molecule exhibits different spectroscopic characteristics depending upon the properties of the solubilizing media. The observed spectral features provide an indication of the microenvironment immediately surrounding the probe. Solvatochromic shifts of the ground and excited states of the probe were analysed by monitoring the charge transfer absorption band and the fluorescence emission spectra in terms of the solute-solvent and solvent-solvent interactions. Fluorescence emission spectra show the dual emission due to excited state proton transfer nature of the probe molecule. The effect of solvent and the excitation energy on dual emission are also studied. The observed magnitude of the Stokes shift in the above solvents has been used to deduce experimentally the dipole moment ratio of the probe molecule for the excited state to the ground state. The dipole moment of excited state is higher than the ground state.     

Quantum chemical simulation of the interaction of membrane fluorescent probe 4-dimethylaminochalcone with hydroxy groups of the environment

The quantum chemical simulation of the ground and electron-excited states of diverse complexes of fluorescent probe 4-dimethylaminochalcone (DMAC) and water in vacuo was performed by the HF/MP2 and RI-CC2 methods. Molecules of the DMAC probe and water can form five types of stable complexes. The geometries corresponding to the potential energy minimum and dipole moments for two lowest singlet and one lowest triplet states were calculated for each type of the complexes. The partial charges on the DMAC atoms and their changes due to the intramolecular charge transfer upon photoexcitation were determined. The coordination of the water molecule at the carbonyl group of DMAC is preferable in vacuo. The formation of hydrogen bonds between the carbonyl group of DMAC and water molecules decreases the energy of the excited state of the complex ¹(π, π*), due to which the fluorescence yield increases upon photoexcitation. The calculation results are confirmed by the experimental data on studying the fluorescence of the probe in binary mixtures of benzene and alcohols.     

Dual Solvatochromism of Neutral Red

Abstract— The effect of solvent polarity on the electronic absorption and fluorescence properties of neutral red (NR), a phenazine-based dye of biological importance has been investigated in several neat and mixed solvents. An unusual dual solvatochromic behavior has been observed that reveals the existence of two closely spaced electronic excited states in NR. In low-polarity solvents the fluorescence of the NR is mainly emitted from the localized excited state, whereas in high-polarity solvents the emission from the charge transfer state dominates. The dipole moments of the localized and charge transfer states of NR have been estimated from the solvatochromic shifts. The dipole moment of the localized excited state (4.8 D) is only slightly higher than that of the ground state (2.0 D), while that of the charge transfer state is drastically higher (17.5 D). Fluorescence quantum yields and the life-times of NR have been determined in different solvents and correlated with the solvatochromic shifts.     

Exploring the conformation,charge density distribution and the electrostatic properties of galanthamine molecule in the active site of AChE using DFT and AIM theory

Quantum chemical calculations and charge density analysis were carried out to understand the geometry, charge density distribution and the electrostatic properties of isolated galanthamine molecule (form I) and for the same lifted out from the active site (form II) of AChE. The optimized geometry of isolated galanthamine was obtained from a hybrid density functional theory (B3LYP/6‐311G**) calculation. A docking analysis on galanthamine with AChE was performed, and the lowest docked energy structure was selected from the active site of AChE for the further study. A single point energy quantum chemical calculation (B3LYP/6‐311G**) was carried out for the lowest energy structure, which was lifted from the galanthamine–AChE complex from molecular docking analysis. The structural comparison between (I) and (II) helps to understand the conformational modification of the galanthamine molecule in the active site. When the molecule present in the active site, the molecular geometry is seen to be significantly altered, specifically, large changes were observed in the outer core of the molecule while the inner core geometry is intact. The bond topological and electrostatic properties of (I) and (II) were calculated. The dipole moment of the galanthamine molecule also increases from 2.09 to 2.67 D in the process. A large negative electrostatic potential region is found at the vicinity of oxygen and nitrogen atoms of the molecule, which predominantly involve strong hydrophobic and electrostatic interactions with the amino acid residues TRP84, PHE330, GLY118, TYR70, and SER122 present in the active site of AChE. © 2013 Wiley Periodicals, Inc.     

QTAIM charge-charge flux-dipole flux models for the infrared fundamental intensities of the fluorochloromethanes

The molecular dipole moments, their derivatives, and the fundamental IR intensities of the fluoro-, chloro-, and fluorochloromethanes are determined from QTAIM atomic charges and dipoles and their fluxes at the MP2/6-311++G(3d,3p) level. Root-mean-square (rms) errors of 0.01 D and 5.6 km mol(-1) are found for the dipole moments and fundamental IR intensities calculated using QTAIM parameters when compared with those obtained directly from the MP2/6-311++(3d,3p) calculations and 0.04 D and 23.1 km mol(-1) when compared with the experimental values. Charge, charge flux, and dipole flux contributions are calculated for all the normal vibrations of these molecules. A large negative correlation coefficient of -0.92 is calculated between the charge flux and dipole flux contributions and indicates that electron transfer from one side of the molecule to the other during vibrations is accompanied by relaxation with electron density polarization in the opposite direction. The CF, CCl, and CH stretching normal modes of these molecules are shown to have characteristic sets of charge, charge flux, and dipole flux contributions. Although the FCF and ClCCl deformation normal modes can also be discriminated from one another based on the sizes and signs of these contributions, some HCH deformations have contributions that are similar to those for some of the ClCCl deformations.     

不同位置取代的三氰基乙烯基蒽的光谱行为的研究

本文设计合成了两个典型的共轭的电子给体与电子受体(D-A)化合物:2-三氰基乙烯基蒽(2-TCVA)与9-三氰基乙烯基蒽(9-TCVA),通过极性效应,温度效应对它们基态与激发态的光谱行为进行了表征。研究表明:这两个化合物均表现出显著的电荷转移(CT)吸收峰,分子受光激发后,9-TCVA只能在非极性溶剂中产生分子内电荷转移(ICT)态荧光,而2-TCVA在极性与非极性溶剂中都能从ICT态发光。另外,温度效应显示冻结态下,2-TCVA只发射ICT态荧光,而9-TCVA既发射类蒽(anthracene-like)荧光又发射ICT态荧光,造成这一现象的主要原因可能是2-TCVA与9-TCVA分子平面性上的差异而引起分子内电荷转移相互作用不同所致。文中还利用了Bilot-Kawski公式估算了化合物2-TCVA在激发态与基态时偶极矩的差值为18.8D。     

Morphology and optical properties of MgO thin films on Mo(0 0 1)

The photophysical properties of N-(1-naphthyl)-carbazole (1-NACZ), N-(2-naphthyl)-carbazole (2-NACZ), N-(1-naphthyl)-benzimidazole (1-NABI) and N-(2-naphthyl)-benzimidazole (2-NABI) were studied. The emission wavelengths of 1-NACZ and 2-NACZ were very sensitive to the polarity of solvents. The magnitude of change in the dipole moment was calculated based on the Lippert–Mataga equation. 1-NACZ and 2-NACZ had higher change in the dipole moment than that of 1-NABI and 2-NABI . The optical properties, including fluorescence quantum yield and fluorescence decay times, were determined in different polarity solvents. These gave the evidence about the intramolecular charge transfer character in the excited singlet state of 1-NACZ and 2-NACZ.     

Studies of Solvent Effects on Structure and Low Frequency Vibrational Spectra of 2,4-Dinitrotoluene

Solvent effects on 2,4-dinitrotoluene(2,4-DNT) molecule in different solvents(toluene,ethanol,and water) were studied via DFT PCM method at B3LYP/6-311+G(d,p) level. The influences of these solvents on the molecular structure,vibrational spectra,charge distribution,and dipole moment were studied as well. The results show that PCM computations are successful in describing the vibrational spectra of 2,4-DNT molecules in these solutions and the solvent effects on the low frequency vibrational spectra are weak.     

吩噻嗪给体受体衍生物激发态的电荷转移

A series of N-bonded donor-acceptor derivatives of phenothiazine containing phenyl （PHPZ）, anisyl （ANPZ）, pyridyl （PYPZ）, naphthyl （NAPZ）, acetylphenyl （APPZ）, and cyanophenyl （CPPZ） as an electron acceptor have been synthesized. Their photophysical properties were investigated in solvents of different polarities by absorption and emission techniques. These studies clearly revealed the existence of an intramolecular charge transfer （ICT） excited state in the latter four compounds. The solvent dependent Stokes shift values were analyzed by the modified Lippert-Mataga equation to obtain the excited state dipole moment values. The large excited state dipole moment suggests that the full （or nearly full） electron transfer take place in the A-D systems. In the system of A-D phenothiazine derivatives, the transition dipole moments Mflu were determined mainly by direct interactions between the solvent-equilibrated fluorescence ^1CT state and ground state because of their lack of significant change with increase of the solvent polarity. The electron structure and molecular conformation of phenothiazine derivatives will be significantly changed with the increase of the electron affinity of the N-10 substituent.     

Molecular structure,vibrational spectra,NBO analysis,first hyperpolarizability,and HOMO,LUMO studies of mesityl chloride by density functional methods

The FT-IR and FT-Raman vibrational spectra of mesityl chloride (2,4,6-trimethylbenzyl chloride) were recorded. The optimized geometry and wavenumbers in the ground state were calculated using density functional (B3LYP, and B3PW91) methods with standard 6-311G(d,p) basis set. The computed B3PW91/6-311G(d,p) results show the best agreement with the experimental values over the other methods. Natural bond orbital analysis of mesityl chloride is also carried out, which confirms the occurrence of strong intermolecular bonding, stability of the molecule arising from hyperconjugative interactions, and charge delocalization. The electric dipole moment (μ), polarizability (α), and first hyperpolarizability (β₀) which results also show that the mesityl chloride might have microscopic non-linear optical behavior with non-zero values. The calculated HOMO and LUMO energies show that charge transfer occur in the molecule. The results of the calculations were applied to simulated spectra of the title compound, which show excellent agreement with observed spectra.