Photoinduced charge transfer in helical polypeptides

Investigation of electron transfer in synthetic polypeptides provides an important probe of how charge entrainment is mediated in redox-active proteins, including photosynthetic reaction centers. Interest in this field has focused increasingly on experimental probes of photoinduced electron transfer kinetics and thermodynamics, and the influence of various features of polypeptide templates (e.g. the hydrogen bonding network, the permanent dipole moment for α-helices) that assemble redox groups for long range charge transfer. A review of the various approaches is presented here with attention to heliogenic peptides and the mediation of photoinduced charge entrainment.     

Role of solvation dynamics in excited state proton transfer of 1-naphthol in nanoscopic water clusters formed in a hydrophobic solvent

Excited state proton transfer (ESPT) in biologically relevant organic molecules in aqueous environments following photoexcitation is very crucial as the reorganization of polar solvents (solvation) in the locally excited (LE) state of the organic molecule plays an important role in the overall rate of the ESPT process. A clear evolution of the two photoinduced dynamics in a model ESPT probe 1-naphthol (NpOH) upon ultrafast photoexcitation is the motive of the present study. Herein, the detailed kinetics of the ESPT reaction of NpOH in water clusters formed in hydrophobic solvent are investigated. Distinct values of time constants associated with proton transfer and solvent relaxation have been achieved through picosecond-resolved fluorescence measurements. We have also used a model solvation probe Coumarin 500 (C500) to investigate the dynamics of solvation in the same environmental condition. The temperature dependent picosecond-resolved measurement of ESPT of NpOH and the dynamics of solvation from C500 identify the magnitude of intermolecular hydrogen bonding energy in the water cluster associated with the ultrafast ESPT process.     

Surface-assisted transient displacement charge technique. I. Photoinduced charge transfer in self-assembled monolayers

Surface-assisted photoinduced transient displacement charge (SPTDC) technique was developed in order to study light-induced charge transfer in surface-bound molecules and applied to investigation of self-assembled monolayers of 7-diethylaminocoumarin and 2,4-dinitrophenylamine. The dipole moment change measured by SPTDC correlates reasonably well with that measured in solution by standard PTDC technique and with semiempirical calculations. Shortening of the excited-state lifetime of surface-immobilized coumarin due to stimulated emission was observed in both fluorescence and dipole measurements. The dipole signal decline in low-polarity solvents indicates the importance of dipole-dipole interaction that causes reorientation of molecules upon photoexcitation.     

Effect of the excitation pulse frequency on the ultrafast photoinduced electron transfer dynamics

The dependence of the ultrafast photoinduced electron transfer dynamics in donor-acceptor complexes on the excitation pulse carrier frequency (spectral effect) has been investigated in the framework of a model involving three electronic state. The spectral effect has been shown to strongly depend on the angle theta between the reaction coordinate directions corresponding to optical and charge transfer transitions. Describing the solvent as a linear homogenous polar medium and accounting for Coulombic interaction of the transferred charge with the medium polarization fluctuations, the angle theta has been found out to be typically in the area 40 degrees -85 degrees. Exactly in this area of theta the spectral effect is predicted to be most pronounced.     

Ultrafast electron diffraction: oriented molecular structures in space and time.

The technique of ultrafast electron diffraction allows direct measurement of changes which occur in the molecular structures of isolated molecules upon excitation by femtosecond laser pulses. The vectorial nature of the molecule-radiation interaction also ensures that the orientation of the transient populations created by the laser excitation is not isotropic. Here, we examine the influence on electron diffraction measurements--on the femtosecond and picosecond timescales--of this induced initial anisotropy and subsequent inertial (collision-free) molecular reorientation, accounting for the geometry and dynamics of a laser-induced reaction (dissociation). The orientations of both the residual ground-state population and the excited- or product-state populations evolve in time, with different characteristic rotational dephasing and recurrence times due to differing moments of inertia. This purely orientational evolution imposes a corresponding evolution on the electron scattering pattern, which we show may be similar to evolution due to intrinsic structural changes in the molecule, and thus potentially subject to misinterpretation. The contribution of each internuclear separation is shown to depend on its orientation in the molecular frame relative to the transition dipole for the photoexcitation; thus not only bond lengths, but also bond angles leave a characteristic imprint on the diffraction. Of particular note is the fact that the influence of anisotropy persists at all times, producing distinct differences between the asymptotic "static" diffraction image and the predictions of isotropic diffraction theory.     

Preparation and functions of self‐assembled monolayers of helix peptides

Self‐assembled monolayers (SAMs) of helix peptides oriented vertically to a gold surface were prepared. Negative surface potentials of a few hundred millivolts were observed for the helix peptide SAMs when they were immobilized on gold through the N terminal of the peptides. However, positive surface potentials were generated in the helix peptide SAMs when the N terminal of the peptides was directed the opposite way. The large dipole moment of the helical peptide was thought to be the major factor for generation of the surface potential. The effect of the dipole moment on the electron transfer through the helix peptide SAMs was investigated. Photocurrent generation by photoexcitation of the N‐ethylcarbazolyl group of the peptide SAMs was accelerated by the dipole moment directed toward the gold substrate. Helical peptides were thus shown to be a suitable medium for electron transfer. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4826–4831, 2000     

Stark Absorption Spectroscopy of Peridinin and Allene-Modified Analogues

Stark absorption spectra of peridinin (Per) and five allene-modified analogues and their angular dependence as a function of an externally applied electric field were measured in methyl methacrylate polymer at 77K. In all cases, the energetically lowest absorption band has a significant change of static dipole moment upon photoexcitation (Δμ). In particular, Per has the largest value of |Δμ|. The angles between Δμ and the transition dipole moment of all the analogues were determined. It is suggested that the allene group in Per plays a key role as the electron donor in the charge transfer process following photoexcitation. The results of MNDO-PSDCI calculations support this idea.     

Effect of the π Bridge and Acceptor on Intramolecular Charge Transfer in Push–Pull Cationic Chromophores: An Ultrafast Spectroscopic and TD‐DFT Computational Study

Three (donor–π–acceptor)⁺ systems with a methyl pyridinium or quinolinium as the electron‐deficient group, a dimethyl amino as the electron‐donor group, and an ethylene or butadiene group as the spacer have been investigated in a joint spectroscopic and TD‐DFT computational study. A negative solvatochromism has been revealed in the absorption spectra, which implies a solution color change, and interpreted by considering the variation in the permanent dipole moment modulus and orientation upon photoexcitation. The fluorescence efficiency decreases upon increasing solvent polarity, in agreement with the excited‐state optimized geometries (planar in low‐polarity media and twisted in high‐polarity media). Femtosecond transient absorption has revealed the occurrence of a fast photoinduced intramolecular charge transfer (ICT) and the molecular factors that determine an efficient ICT. Considering the crucial role of the ICT in tuning the nonlinear optical (NLO) properties, these compounds can be considered promising NLO materials.     

On the role of hydrogen bonds in photoinduced electron-transfer dynamics between 9-fluorenone and amine solvents

Using ultrafast fluorescence upconversion and mid-infrared spectroscopy, we explore the role of hydrogen bonds in the photoinduced electron transfer (ET) between 9-fluorenone (FLU) and the solvents trimethylamine (TEA) and dimethylamine (DEA). FLU shows hydrogen-bond dynamics in the methanol solvent upon photoexcitation, and similar effects may be anticipated when using DEA, whereas no hydrogen bonds can occur in TEA. Photoexcitation of the electron-acceptor dye molecule FLU with a 400?nm pump pulse induces ultrafast ET from the amine solvents, which is followed by 100?fs IR probe pulses as well as fluorescence upconversion, monitoring the time evolution of marker bands of the FLU S(1) state and the FLU radical anion, and an overtone band of the amine solvent, marking the transient generation of the amine radical cation. A comparison of the experimentally determined forward charge-separation and backward charge-recombination rates for the FLU-TEA and FLU-DEA reaction systems with the driving-force dependencies calculated for the forward and backward ET rates reveals that additional degrees of freedom determine the ET reaction dynamics for the FLU-DEA system. We suggest that hydrogen bonding between the DEA molecules plays a key role in this behaviour.     

A comprehensive study of the solvent effects on the cycloaddition reaction of diethyl azodicarboxylate and ethyl vinyl ether: Efficient implementation of QM and TD‐DFT study

In this work, quantum chemistry calculations performed to study the kinetics and thermodynamic parameters of [2+2] cycloaddition reaction of diethyl azodicarboxylate and ethyl vinyl ether in eighty‐three solvents and gas phase. The solvent effect on the reaction path and electron density of the C2? N6 critical bond as the reaction coordinate at the TS was investigated. Calculated rate constants in various solvents showed that increase in the activation dipole moment accelerates the reaction. Based on the time‐dependent studies, using a conductor like polarizable continuum model solvation model, the solvent effects on the excitation energies of the reactants and transition states (TSs) and the corresponding chemical shifts were analyzed. Finally, some correlations between the rate constant and quantum reactivity indices such as electrophilicity index, chemical hardness, and electronic chemical potential were investigated. © 2014 Wiley Periodicals, Inc.     

Photophysical studies of 7-hydroxy-4-methyl-8-(4′-methylpiperazin-1′-yl) methylcoumarin: A new fluorescent chemosensor for zinc and nickel ions in water

The title compound, a new coumarin based fluorophore having a piperazine moiety as the photoinduced electron transfer (PET) switch was prepared and its photophysical properties studied in various solvents and under different pH. Solvatochromic shift in the fluorescence spectrum revealed an increase in the dipole moment in the lowest excited singlet state compared to that in the ground state. The compound also showed an interesting intramolecular photoinduced proton transfer phenomenon in the excited state under neutral pH. It was effectively utilized as a new Chelation-enhanced fluorescence (CHEF) based chemosensor for zinc and nickel ions in water.     

On the Role of Hydrogen Bonds in Photoinduced Electron‐Transfer Dynamics between 9‐Fluorenone and Amine Solvents

Using ultrafast fluorescence upconversion and mid‐infrared spectroscopy, we explore the role of hydrogen bonds in the photoinduced electron transfer (ET) between 9‐fluorenone (FLU) and the solvents trimethylamine (TEA) and dimethylamine (DEA). FLU shows hydrogen‐bond dynamics in the methanol solvent upon photoexcitation, and similar effects may be anticipated when using DEA, whereas no hydrogen bonds can occur in TEA. Photoexcitation of the electron‐acceptor dye molecule FLU with a 400 nm pump pulse induces ultrafast ET from the amine solvents, which is followed by 100 fs IR probe pulses as well as fluorescence upconversion, monitoring the time evolution of marker bands of the FLU S₁ state and the FLU radical anion, and an overtone band of the amine solvent, marking the transient generation of the amine radical cation. A comparison of the experimentally determined forward charge‐separation and backward charge‐recombination rates for the FLU‐TEA and FLU‐DEA reaction systems with the driving‐force dependencies calculated for the forward and backward ET rates reveals that additional degrees of freedom determine the ET reaction dynamics for the FLU‐DEA system. We suggest that hydrogen bonding between the DEA molecules plays a key role in this behaviour.     

Excited states of the high-frequency vibrational modes and kinetics of ultrafast photoinduced electron transfer

The effect of the carrier frequency of the exciting laser pulse on the kinetics of intramolecular photoinduced charge transfer in the multi-channel stochastic model is studied. It is shown that the population of different states of high-frequency intramolecular modes upon varying the frequency of the excitation pulse can considerably alter the rate constant of ultrafast charge transfer. It is found that a negative vibrational spectral effect is expected in the vicinity of a barrier-free area (the rate constant of photoinduced charge transfer decreases along with the carrier frequency of the excitation pulse), while a positive effect is predicted in areas of high and low exergonicity (an inverse dependence). It is concluded that the value of the spectral effect falls along with the time of vibrational relaxation. For ultrafast photo-induced charge transfer, however, it remains considerable up to relaxation times of 100 fs.     

Theoretical study of ultrafast heterogeneous electron transfer reactions at dye-semiconductor interfaces: coumarin 343 at titanium oxide

A theoretical study of photoinduced heterogeneous electron transfer in the dye-semiconductor system coumarin 343-TiO(2) is presented. The study is based on a generic model for heterogeneous electron transfer reactions, which takes into account the coupling of the electronic states to the nuclear degrees of freedom of coumarin 343 as well as to the surrounding solvent. The quantum dynamics of the electron injection process is simulated employing the recently proposed multilayer formulation of the multiconfiguration time-dependent Hartree method. The results reveal an ultrafast injection dynamics of the electron from the photoexcited donor state into the conduction band of the semiconductor. Furthermore, the mutual influence of electronic injection dynamics and nuclear motion is analyzed in some detail. The analysis shows that--depending on the time scale of nuclear motion--electronic vibrational coupling can result in electron transfer driven by coherent vibrational motion or vibrational motion induced by ultrafast electron transfer.     

The photokinetics of phenothiazine dyes with titanium trichloride in different solvents

The kinetic parameters of photoinduced electron transfer reaction of two phenothiazine dyes, methylene blue and methylene green with titanium trichloride, were determined in water and different aqueous-alcoholic solvents at different acidities by using a specially designed optical system. The rate of photoinduced electron transfer reaction was measured by determining the quantum yield of the reaction. The methylene green had a higher reactivity as compared to methylene blue with titanium trichloride. The graphical analysis showed that the reaction of dye with titanium trichloride follows pseudo–first-order kinetics. A reaction mechanism was proposed by considering the different excited states of dye and their possible interaction with the solvent and titanium trichloride. The different steps in the reaction mechanism were taken into consideration for deriving rate equations, which were used to determine the different rate constants in the reaction mechanism in different solvents.