Model for primary electron transfer and coupling of electronic states at reaction centers of purple bacteria

A detailed derivation is presented for relations making it possible to describe the effect of temperature on the halfwidth of the P960 and P870 absorption bands and also on the electron transfer (ET) rate at reaction centers (RCs) of the purple bacteria Rps. viridis and Rb. sphaeroides. Primary electron transfer is considered as a resonant nonradiative transition between P* and P⁺B _L ⁻ states (where P is a special pair, B_L is an additional bacteriochlorophyll in the L branch of the reaction center). It has been shown that the vibrational h_α mode with frequency 130–150 cm⁻¹ controls primary electron transfer. It has been found that the matrix element of the electronic transition between the states P* and P⁺B _L ⁻ is equal to 12.7 ± 0.9 and 12.0 ± 1.2 cm⁻¹ for Rps. viridis and Rb. sphaeroides respectively. The mechanism is discussed for electron transport from P* and B_L and then to bacteriopheophytin H_L. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 294–303, May–June, 2006.     

Sub-Structures Formed in the Excited State are Responsible for Tryptophan Residues Fluorescence in β-Lactoglobulin

Origin of tryptophan residues fluorescence in β-lactoglobulin is analyzed. Fluorescence lifetimes and spectra of β-lactoglobulin solution are measured at pH going from 2 to 12 and in 6 M guanidine. Tryptophan residues emit with three lifetimes at all conditions. Two lifetimes (0.4–0.5 ns and 2–4 ns) are in the same range of those measured for tryptophan free in solution. Lifetimes in the denatured states are lower than those measured in the native state. Pre-exponential values are modified with the protein structure. Data are identical to those already obtained for other proteins. Fluorescence lifetimes characterize internal states of the tryptophan residues (Tryptophan sub-structures) independently of the tryptophan environments, the third lifetime results from the interaction that is occurring between the Trp residues and its environment. Pre-exponential values characterize substructures populations. In conclusion, tryptophan mission occurs from substates generated in the excited state. This is in good agreement with the theory we described in recent works.     

Conformational and Functional Transitions in Class II α-mannosidase from <Emphasis Type="Italic">Aspergillus fischeri</Emphasis>

The conformational transitions in an oligomeric and high molecular weight class II α-mannosidase from Aspergillus fischeri were examined using fluorescence and CD spectroscopy under chemical, thermal and acid denaturing conditions. The enzyme lost the activity first and then the overall folded conformation and secondary structure. The midpoint values of GdnHCl mediated changes measured by inactivation; fluorescence and negative ellipticity were 0.48 M, 1.5 M and 1.9 M, respectively. The protein almost completely unfolded in 4.0 M GdnHCl but not at 90 °C. The inactivation and unfolding were irreversible. At pH 2.0, the protein exhibited molten-globule like intermediate with rearranged secondary and tertiary structures and exposed hydrophobic amino acids on the surface. This species showed increased accessibility of Trp to the quenchers and got denatured with GdnHCl in a different manner. The insoluble aggregates of a thermally denatured protein could be detected only in the presence of 0.25–0.75 M GdnHCl.     

Photophysical properties of mesonitrophenyl-substituted porphyrins and their dimers at 295 K

It is shown that at 295 K in meso-orthonitrophenyl-substituted octaethylporphyrins and their chemical dimers the steric interactions of the nitro-group and the volume substituents at β-positions of the pyrrole rings favor direct overlapping of molecular orbitals in a donor-acceptor pair. The efficient quenching of fluorescence of the nitroporphyrins in toluene is attributed to direct nonadiabatic electron transfer from the S₁-level of a porphyrin to the lower-lying state with charge transfer by the “through-space” mechanism. Quenching of the T₁-states is related with heat-stimulated transmission to the higher-lying states with charge transfer of the ion-radical pair as well as with enhancement of the probability of the nonradiative T₁→S₀-transition. To whom correspondence should be addressed. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 531–535, July–August, 1999.     

Conformational Flexibility of Cytokine-Like C-Module of Tyrosyl-tRNA Synthetase Monitored by Trp144 Intrinsic Fluorescence

The non-catalytic COOH-terminal module formed after proteolytic cleavage of full-length mammalian tyrosyl-tRNA synthetase displays dual function: tRNA binding ability and cytokine activity. With the aim to explore the intramolecular dynamics of C-module in solution we used fluorescence spectroscopy to study conformational changes of isolated protein. We used information from fluorescence spectra and computational model for characterization of a microenvironment of a single tryptophan residue (Trp144). Its fluorescence parameters and protection from quenching by Cs⁺ ions indicate the internal localization—buried into protein globule. The fluorescence quenching of Trp144 by acrylamide suggests rapid conformation dynamics of the C-module in nanosecond time scale. The temperature-induced conformational changes in the C-module were monitored by the fluorescence measurements of Trp144 emission and by red-edge excitation shift. An emission maximum shift up to ∼349 nm and significant decrease of the red-edge shift effect at 37–52 °C indicated a major conformational transition of Trp144 from buried native state into highly relaxing polar solvent environment.     

Ultrafast heat transfer on nanoscale in thin gold films

Heat transfer processes, induced by ultrashort laser pulses in thin gold films, were studied with a time resolution of 50 fs. It is demonstrated that in thin gold films heat is transmitted by means of electron–phonon and phonon–phonon interactions, and dissipated on nanoscale within 800 fs. Measurements show that the electron–phonon relaxation time varies versus the probe wavelength from 1.6 to 0.8 ps for λ=560–630 nm. The applied mathematical model is a result of transforming the two-temperature model to the hyperbolic heat equation, based on assumptions that the electron gas is heated up instantaneously and applying Cattaneo’s law to the phonon subsystem, agrees well with the experimental results. This model allows us to define time of electron–phonon scattering as the ratio of the heat penetration depth to the speed of sound in the bulk material that, in turn, provides an explanation of experimental results that show the dependence of the electron–phonon relaxation time on the wavelength.     

Microwave excited CO<Subscript>2</Subscript> laser with multiple units using orthogonal electric fields

The third order nonlinear optical properties of 4^′-methoxy chalcone and its derivatives have been investigated using a single-beam Z-scan technique with nanosecond laser pulses at 532 nm. The 4^′-methoxy chalcone and its derivatives are donor–acceptor–acceptor (D–A–A) and donor–acceptor–donor (D–A–D) type intramolecular charge transfer molecules. The nonlinear response in these molecules was found to increase with increase in (a) the electron acceptor strength in D–A–A type and (b) the donor strength of the substituted group in D–A–D type molecules. The χ⁽³⁾ value in these molecules is found to be of the order of 10^-13 esu. The observed increase in the third order nonlinearity in these molecules clearly indicates the electronic origin. The compounds exhibit good optical limiting at 532 nm. The best optical limiting behavior was observed with the molecule substituted by a strong electron donor. PACS 42.65.An; 42.70.Nq     

EPR Equilibration Measurement of the C–H Bond Enthalpy in the Methylene Groups of 1,3,5-Trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (Irganox)

On the basis of previous and current studies, it has been possible to evaluate and compare the bond dissociation energies of the phenol (O–H) bond and of the methylene and methyl (C–H) bonds in Irganox (trade name) by means of electron paramagnetic resonance records of galvinoxyl–irganoxyl hydrogen transfer reaction equilibria. The bond dissociation enthalpy of the C–H methylene and methyl bonds in Irganox was found to be 339.0 ± 3.0 kJ/mol, very close to the previously found value of 340.7 ± 3.0 kJ/mol for the O–H bond of some benzyl–phenolic antioxidant.     

An ionic liquid-type multiwall carbon nanotubes paste electrode for electrochemical investigation and determination of morphine

The direct electrochemistry of morphine on modified multiwall carbon nanotubes using carbon ionic liquid (i.e., 1-butyl-3-methylimidazolium hexafluoro phosphate, ([C4mim]–[PF6])) was studied. It was found that the electrode showed sensitive voltammetric response to morphine. The experimental results suggested that the modified electrode promoted electron transfer reaction for the oxidation of morphine. The electron transfer coefficient and charge transfer resistant (R _ct) of morphine at the modified electrode were calculated. Under the optimized conditions at pH 8.0, the peak current was linear to morphine concentrations over the concentration range of 0.45–450 μmol L⁻¹, using differential pulse voltammetry. The detection limit was 0.14 μmol L⁻¹. The proposed method was successfully applied to the determination of morphine in both ampoules and urine samples.     

Anisotropic momentum transfer in low-dimensional electron systems in a magnetic field

In low-dimensional systems with an asymmetric quantizing potential, an asymmetric electron energy spectrum ε(p)≠ε(−p), where p is the electron momentum, arises in the presence of a magnetic field. A consequence of such an energy spectrum is that momentum transfer to the electron system in mutually opposite directions in the presence of an external perturbation is different. Therefore, in the presence of a standing electromagnetic wave momentum is transferred from the wave to the electrons, which gives rise to a new type of electromotive force. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 8, 551–555 (25 October 1997)     

Surface Morphology of NiSi 2 /Si Films Obtained by the Method of Solid-Phase Deposition

Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy are used to study the formation of epitaxial layers of NiSi2 during Ni–Si deposition followed by annealing. It is shown that the formed NiSi2 film has an island structure when its thickness is h ≤ 150 Å and at h ≥ 200 Å the film is continuous. The band gap of the island and solid films is ~0.6 eV, while the values of the resistivity ρ differ by several orders of magnitude. It is found that the photoelectron spectrum of the NiSi2 film with h = 50 Å has peaks characteristic of both Si and NiSi2. The formation of the main peaks in the photoelectron spectrum of NiSi2 is explained by hybridization of the M1, M2, M3 states of Si with the М3, М4, М5 states of Ni.     

Conversion--electron gamma--ray coincidence spectroscopy of superdeformed 135Nd

Three mini-orange conversion–electron spectrometers and four Euroball Ge Cluster detectors have been used for γ–e^- coincidence spectroscopy of superdeformed ¹³⁵Nd. Transitions within the superdeformed band are shown to have the expected E2 multipolarity. The 766.5–keV transition which links the band to a positive-parity state has a conversion coefficient consistent with M1 multipolarity. Consequently, positive parity is deduced for the superdeformed band. No evidence for E0 transitions was found. Received: 22 December 1997 / Revised version: 19 January 1998     

Interpretation of the soret band of porphyrins based on the polarization spectrum of N-methyltetraphenylporphin fluorescence

Low-temperature (77 K) absorption, fluorescence, and fluorescence-excitation spectra and the fluorescence polarization spectrum for N-methyl-meso-tetraphenylporphin (N-methyl-TPP) are measured. Based on the polarization spectrum the absorption spectrum in the visible region (a “generic” porphyrin spectrum) is interpreted. In particular, it is shown that the fifth absorption band (the “Longo band”) that manifests itself in some porphyrins is a Q_y(0–2) band and does not belong to the individual electron transition. Emphasis is placed on the region of the Soret band. It is inferred that at least two allowed electron transitions (G →B_x and G→B_y) polarized mutually perpendicularly manifect themselves in this region. The interpretation of the Soret band of porphyrins [2] that attributes this band to one electron transition G→B_x is thereby rejected. This interpretation is confirmed by computer modeling of the polarization spectrum. Special features of the experimental polarization spectrum are explained by a more developed vibrational structure and, possibly, a larger half-width of the B_x band than the half-width of the B_y band. The contribution of the states of intramolecular charge transfer to the formation of the Soret band is discussed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 65–72, January–February, 1999.     

Luminescence of carbazolyl-containing polymers doped with iridium chelates

White light emission is shown to be obtainable at room temperature through the mixing of poly-N-vinylcarbazole (PVC) host fluorescence with fac-tris(2-phenylpyridyl)Ir(III) [Ir(ppy)₃] and bis[2-(2′-benzothienyl)pyridinato-N,C^3′](acetylacetonate)iridium (III) [Btp₂Ir(acac)] dopant phosphorescence whereas at very low temperature through the superposition of poly-N-epoxypropyl-3,6-dibromocarbazole (3,6-DBrPEPC) host and Btp₂Ir(acac) dopant phosphorescence emissions. The balance between basic colors is adjusted by the variation of triplet-emitter dopant concentrations. Spin-allowed singlet-singlet energy transfer from the host to iridium chelate dopants by the Forster mechanism is the dominant process in PVC. Spin-forbidden triplet-singlet transfer by the Forster mechanism from the host to the dopant occurs at low temperatures in 3,6-DBrPEPC due to strong spin-orbit coupling induced by the heavy bromine atoms. Spin-allowed transfer from the same host’s triplet excited state to the iridium chelate occurs via electron exchange at high temperatures. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 3, pp. 324–330, May–June, 2008.     

Localization and Environment of Tryptophans in Different Structural States of Concanavalin A

We have investigated the localization and environment of tryptophan residues in different quaternary and conformational states (tetrameric, dimeric, monomeric and unfolded) of metallized and demetallized concanavalin A (ConA) by selective chemical modification, fluorescence, and phosphorescence. ConA has four tryptophan residues (Trp 40, Trp 88, Trp 109 and Trp 182) per subunit. The pattern of oxidation by N-bromosuccinimide (NBS) shows that NBS modifies, in dimer, only Trp 182 which remains inaccessible in tetramer, two (Trp 88 along with Trp 182) in monomer, all four in unfolded form in presence of EDTA, and three (possibly Trp 40 along with Trp 88 and Trp 182) in unfolded form from native or remetallized ConA. Utilizing wavelength-selective fluorescence approach, we have observed a red edge excitation shift (REES) of 6–8 nm for tetramer and dimer. A more pronounced REES (11 nm) is observed for oxidized monomer compared to REES (3 nm) for unoxidized species. Acrylamide quenching shows the Stern-Volmer constant (K_SV) for dimer, monomer, unfolded ConA and unfolded apo-ConA being 3.8, 5.2, 12.8, 14.0 M⁻¹, respectively. Phosphorescence studies at 77 K give more structured spectra, with two (0,0) bands at 406.2 (weak) and 413.2 nm for tetramer. However, a single (0,0) band appears at 413.2 for dimer and 412.6 nm for monomer, while the (0,0) band of the oxidized monomer is red shifted to 414.4 nm. These results may provide important insight into subtlety of organization and environment of tryptophans in the context of folding and structural studies of oligomeric proteins including lectins.     

State selective electron capture in partially stripped ion-atom interaction at intermediate and high energies

Post form of “boundary corrected continuum intermediate state (BCIS)” approximation has been employed to study charge transfer cross-sections in collision of C^q+, N^q+ and O^q+ (q=1–5) with ground state atomic hydrogen in the energy range of 50–200 keV/amu. In this formalism we have adopted model potential for the interaction of the active electron with the projectile ion. Calculated results for total charge transfer cross-sections have significant improvement over other existing theoretical results in their comparison to the available experimental findings except for singly charge ions. Sub-shell distribution for total charge transfer cross-section has also been reported in graphical form. Predictions suggested by Olson in connection with the sub-shell distribution of total charge transfer cross-section has been reaffirmed. However, an oscillatory structure of charge state dependence of the total charge transfer cross-sections has not been found in the present investigation.     

Effect of the electron beam and ion flux parameters on the rate of plasma nitriding of an austenitic stainless steel

The method of nitriding of metals in an electron beam plasma is used to change the current density and energy of nitrogen ions by varying the electron beam parameters (5–20 A, 60–500 eV). An electron beam is generated by an electron source based on a self-heated hollow cathode discharge. Stainless steel 12Kh18N10T is saturated by nitrogen at 500°C for 1 h. The microhardness is measured on transverse polished sections to obtain the dependences of the nitrided layer thickness on the ion current density (1.6–6.2 mA/cm²), the ion energy (100–300 eV), and the nitrogen-argon mixture pressure (1–10 Pa). The layer thickness decreases by 4–5 μm when the ion energy increases by 100 V and increases from 19 to 33 μm when the ion current density increases. The pressure dependence of the layer thickness has a maximum. These results are in conflict with the conclusions of the theory of the limitation of the layer thickness by ion sputtering, and the effective diffusion coefficient significantly exceeds the well-known reported data.     

Selective Fluorimetric Recognition of Cesium Ion by 15-Crown-5-Anthracene

A selective fluorescent cesium optode on a chromoionophore consisting of anthracene covalently linked through an imine bond to a 15-crown-5 derivative has been reported. In the present system, 15-crown-5 derivative including anthracene was used a fluoroionophore. The fluorescence response mechanism is based on the photo-induced electron transfer (PET) from the lone pair of electrons of the nitrogen to the anthracene group and inhibition of PET system by cesium binding while increasing the fluorescence intensity. Emission intensity 15-crown-5 anthracene was measured at 500 nm with absorbance at 400 nm in CH₃CN–H₂O (1:1) media. The method shows a very good selectivity and sensitivity for cesium with respect to other cations such as K⁺, Na⁺ and Li⁺ with linear range and detection limit of 5.0 × 10⁻⁵ to 5.0 × 10⁻¹M and 3.0 × 10⁻⁶M respectively.     

Theory of the oscillatory dependence of the conductivity of two-component dielectric composites at room temperatures

It is predicted that at room temperatures a hopping mechanism of charge transfer plays a very important role and leads to temperature oscillations of the conductivity σ(T) of a dielectric composite. The dependence of the conductivity σ(ω) on the frequency of an alternating electric field is calculated. The relation obtained can be used to determine, first, the electron relaxation times and, second, and more importantly, the frequency of electron tunneling through the dielectric matrix from measurements of the conductivity in various frequency ranges. Zh. Tekh. Fiz. 69, 31–34 (March 1999)     

Investigation of excited-state proton transfer in 3-hydroxyflavone molecules

The dual fluorescence spectra of 3-hydroxyflavone molecules excited by electromagnetic radiation in the region of the S ₁ and S ₂ absorption bands in the temperature region of 20–80°C are studied using the dynamic quenching of the excited state. An analysis of the fluorescence parameters shows that heating the solution from room temperature to 60°C increases the proton transfer rate by a factor of 1.24 in the case of standard excitation into the main absorption band and even stronger (by a factor of 6.9) in the case of excitation into the second absorption band. The presence of a quencher reduces the yield of the two emission bands and noticeably increases the proton transfer rate, by a factor of 1.16 at room temperature and by a factor of 1.25 at 80°C. Upon excitation into the second singlet band, the transfer rate increases even more (especially at higher temperatures), by a factors of 1.24 and 3.5 for the same temperatures. The temperature dependences of the transfer rate constant allowed us to estimate the activation energies of the proton transfer reaction under different physical conditions and reach conclusions about the mechanism by which this reaction proceeds. It is found that the proton transfer activation energy decreases from 500 to 360 cm⁻¹ when measured in temperature ranges of 20–40 and 20–60°C. The introduction of a quencher with a concentration of 5 × 10⁻³ M increases the activation barrier to 534 and 471 cm⁻¹ in the same temperature ranges.