


卷 122, 编号 2 (2017)
- 年: 2017
- 文章: 23
- URL: https://ogarev-online.ru/0030-400X/issue/view/10080
Spectroscopy of Atoms and Molecules
A comparative study of the processes of generation of singlet oxygen upon irradiation of aqueous preparations on the basis of chlorin e6 and coproporphyrin III
摘要
The photosensitizing ability of an agent based on chlorin e6 (Photoditazin), which is used for photodynamic diagnosis and therapy, is compared with that of a new preparation on the basis of coproporphyrin III in the environment of a phosphate buffer and a simulated biological environment (albumin solution). The efficiency of singlet-oxygen production was estimated by EPR spectroscopy and spectroscopy in the UV and visible ranges with the use of “chemical traps” of singlet oxygen. By irradiating drugs with LED emission centered at λmax = 520 nm, we determined the quantum yield of singlet-oxygen production in a buffer solution; the obtained values are 0.60 and 0.37 for chlorine and coproporphyrin, respectively. The steady-state concentration of singlet oxygen upon irradiation of solutions of the studied photosensitizers with concentrations of 12–43 μМ and the density of radiation power within the 6–96 W/cm2 region was found to be in the region of 1010–1011 molecules/cm3. It is shown that the introduction into the solution of egg albumin (0.1%) reduces the sensitizing properties of the two drugs by two to three times, while the efficiencies of the preparations with respect to singlet-oxygen production become almost identical (0.19 and 0.17).



Emission properties of apokamp discharge at atmospheric pressure in air, argon, and helium
摘要
Emission spectra of the plasma jet of apokamp discharge in air, helium, and argon are studied. Apokamp at atmospheric pressure is formed in the areas of strengthening of the electric field near the bends in the channel of the pulse-periodic discharge and is directed perpendicularly to the discharge channel. Apokamp consists of a bright narrow “appendage” connected with the discharge channel and with the diffuse jet emerging from the channel. It is shown that, in helium, the emission of the diffuse part of apokamp is dominated by N2 and N2+, while emission of the “appendage” display lines and bands of He, N2, N2+, O, and OH. In argon, emission spectra of the diffuse part of the plasma jets contain not only N2 and N2+, but also Ar lines. It is assumed that the surrounding air plays an important role in the formation of the diffuse part of apokamp in helium and argon.



Condensed-Matter Spectroscopy
Calculation of the optical spectra of the copper(I) complex with triphenylphosphine, iodine, and 3-pyridine-2-yl-5-phenyl-1H-1,2,4-triazole by the DFT method
摘要
The IR and UV spectra of the [CuIL(PPh3)] complex (PPh3 = triphenylphosphine, L = 3-pyridine- 2-yl-5-phenyl-1Н-1,2,4-triazole) have been analyzed in detail within the density functional theory (DFT) and its time-dependent version TD DFT. The standard functional B3LYP and sets of basis orbitals 6-311G(d,p) and Lanl2DZ are used for the atoms of the elements of periods I and II and for the iodine atom, respectively. The calculated IR spectra of the complex and free ligands coincide with the observed IR bands, due to which one can completely interpret all normal modes and confirm X-ray diffraction (XRD) data. Particular attention is paid to the structure of excited triplet (Т1) state in order to explain the role of copper and iodine ions in the formation of photo- and electroluminescence spectra. It is shown that the equilibrium Т1 state undergoes structural relaxation after the vertical excitation and significantly changes its electronic nature and the charge transfer structure.



A comparative study of singlet-oxygen generation by С60 and С70 fullerenes
摘要
The results of comparative investigations of singlet-oxygen generation by С60 and С70 fullerenes in tetrachloromethane solutions, aqueous suspensions, and solid-phase powders of fullerenes optically excited by cw diode arrays with different wavelengths and by pulsed xenon lamps with a band filter are presented. The measurements were performed by recording singlet-oxygen phosphorescence at the O2(1Δg)–O2(3Σg) transition (λ = 1270 nm).



On the possibility of determining anthracycline antibiotics in aqueous solutions using optical analytical system (biosensor)
摘要
We propose a version of the theory describing the circular dichroism spectra of cholesteric liquidcrystal dispersion particles of double-stranded DNA. The basis of the theory is the concept of absorption of electromagnetic waves by large molecular systems. The effect of physical parameters of dispersion particles on their circular dichroism is theoretically determined. It is experimentally demonstrated that circular dichroism can be used as a convenient tool for creating an optical analytical system for the determination of biologically active compounds that interact with DNA molecules.



Quantum electron plasma in one-dimensional metallic–dielectric photonic crystal
摘要
The interaction of the electromagnetic radiation with one-dimensional photonic crystal consisting of metal and transparent dielectric medium is studied numerically. Dielectric permeabilities of the electron plasma in the metal are considered both in the quantum Mermin and in the classical Drude–Lorentz approaches. It is shown that the reflection, transmission and absorption-frequency zones of electromagnetic radiation appear in the photonic crystal. In addition, the reflectance, transmittance and absorptance optical coefficients for such photonic crystal in the quantum approach differ from those coefficients in the Drude–Lorentz approach.



The effect of orientation and distance between donor and acceptor molecules on the efficiency of singlet–singlet energy transfer in Langmuir–Blodgett films
摘要
Singlet–singlet energy transfer between molecules of fluorescein and oxazine dyes in Langmuir–Blodgett films is studied experimentally. The dependence of the energy-transfer efficiency on the distance shows that the quenching of the donor fluorescence is the most efficient when the layers of the donor and acceptor molecules are in a direct contact. An increase in the distance between the donor and acceptor layers leads to a decrease in the energy-transfer efficiency. To establish the mutual orientation of the donor and acceptor molecules, quantum-chemical calculations of the energy transfer process in the donor–acceptor pair are carried out. The calculations show that the best correlation of the experimental and calculated values of the energy-transfer efficiency is observed when the interacting particles are shifted relative to each other by about ~0.12 nm in parallel planes. The presented approach can be used to estimate the relative orientation of interacting particles in multimolecular ensembles.



Temperature measurements using a projection to latent structures of fluorescence spectra of potassium–aluminum borate glasses with copper-containing molecular clusters
摘要
Luminescence spectra of a potassium–aluminum borate glass with copper-containing molecular clusters are presented in the temperature range of 295–624 K. Two methods of temperature measurement are compared with the aim of evaluating the possibility of their further application in optical temperature sensors: specifically, the classical method of measuring a temperature based on the spectral position of the fluorescence band peak and the measurement method based on projection to latent structures of fluorescence spectra in the visible range. It is shown that, concerning the accuracy of measuring a temperature, the fourdimensional space of latent structures is preferred for the case under consideration; it allows one to determine (using a training set of fluorescence spectra) a temperature with the relative error of no more than 1.2%.



Spectroscopic properties of polycrystals of supramolecular europium complexes with bathophenanthroline
摘要
Nanostructured supramolecular complex of europium(III) with bathophenanthroline (bphen), with detonation synthesis nanodiamonds (NDs) used as a structure-forming element, has been synthesized for the first time. The characteristics of the Eu(bphen)2(NO3)3 complex and the supramolecular complex with NDs, ND–Eu(bphen)2(NO3)2, are studied and compared using scanning electron microscopy (SEM), luminescence spectroscopy, IR spectroscopy, and electron-spin resonance (ESR) spectroscopy. The luminescence quantum yields of the complexes are estimated by the relative method using a β-diketonate complex of europium (III) with tris(thenoyltrifluoroacetone) and 1,10-phenanthroline (Eu(TTA)3phen) as a reference. It is found that the ND–Eu(bphen)2(NO3)2 supramolecular complex has a higher photoresistance than the complex without NDs and no worse thermal stability (up to a temperature of +150°C).



Photobleaching mechanisms of Radachlorin photosensitizer in aqueous solution
摘要
The time dependence of the fluorescence intensity of aqueous solutions of Radachlorin photosensitizer at different concentrations and the influence of the dissolved oxygen concentration on the fluorescence dynamics are analyzed. The experimental results are interpreted based on the numerical solution of the system of kinetic equations describing the photochemical processes that lead to the formation and degradation of singlet oxygen in solution. The influence of possible mechanisms of photosensitizer photobleaching is analyzed. It is shown that the main photobleaching mechanism under our experimental conditions is the chemical reaction between the photosensitizer in the triplet state and dissolved oxygen molecules. Two rate constants of electron-transfer chemical reactions, which are important for understanding the nature of the occurring photoprocesses, are determined.



Nonlinear and Quantum Optics
Purcell effect in one-dimensional photonic quasicrystals
摘要
The change in probability of spontaneous emission for emitter placed in one-dimensional photonic quasicrystal (optical Fibonacci lattice) was examined. When the dipole is placed in Fibonacci lattice two different scenarios can be expected: enhancing (if frequency and direction of the dipole emission correspond to optical eigenmode of structure, and position corresponds to maximum value of modes electric field profile) or suppression (in case of photonic band gap) of spontaneous emission rate. Fact that both effects are expressed in quasicrystals less than in the Bragg reflectors and in the microcavities was demonstrated.



Optical limiting in Pluronic F-127 hydrogel with nanocarbon inclusions
摘要
Characteristics of nonlinear optical limiting (limiting curves) of laser radiation in aqueous polymer systems with nanocarbon inclusions have been studied. Suspensions of nanotubes and soot stabilized by the amphiphilic polymer Pluronic F-127, the additives of which provide the system’s transition to a solid-like hydrogel aggregate state at room temperature, have been considered. The limiting materials after their optical breakdown by high-intensity radiation in the gel state have been regenerated using the thermoreversible hydrogel–isotropic solution phase transition. These systems are shown to be promising for self-healing optical materials.



Enhancement of high-order harmonics generated in laser-produced plasma using ionic resonances and nanoparticles
摘要
We review recently emerged methods of high-order harmonic enhancement in the extended laserproduced plasmas using ionic resonances and nanoparticles and show the difference of this approach with regard to previously used methods. Particularly, we analyze the harmonic generation in graphene and a few other clustered media using 800-nm-class lasers. We also discuss the application of parametric waves for frequency conversion towards the extreme ultraviolet range and show the resonance enhancement of harmonics in laser-produced zinc plasma using tunable mid-infrared pulses. The reviewed studies demonstrated the attractiveness of the joint application of the methods of harmonic enhancement using ionic resonances and nanoparticles.



Physical Optics
Generation of a longitudinal current upon interaction of a transverse electromagnetic wave with degenerate plasma
摘要
We consider degenerate plasma that is located in the field of a transverse electromagnetic wave. An electric current generated in the plasma by the electromagnetic field is sought. During classical description of the interaction of the electromagnetic wave with the plasma, the Vlasov kinetic equation is used, while, in quantum description, the quantum kinetic equation with the Wigner integral is applied. A nonlinear analysis has shown that that the electric current in the plasma has two nonzero components. One component of the electric current is directed along the vector potential of the electromagnetic field. The other nonzero component of the current is directed along the wave vector. In the present work, we analyze this component of the electric current. The case of collisionless plasma is examined.



Transient radiation in an anisotropic magnetodielectric plate in a waveguide
摘要
We have considered transient radiation of a charged particle in an anisotropic magnetodielectric plate placed into a regular waveguide. It is assumed that the charged particle passes through the plate moving at a constant velocity perpendicularly to the waveguide axis. Wave equations and analytical expressions for transverse electric (TE) and transverse magnetic (TM) fields in different regions of the waveguide have been obtained. Energies of transient radiation of the moving particle have been calculated. The properties of transient radiation and Vavilov–Cherenkov radiation have been analyzed for the case of a rectangular waveguide. Energies of transient radiation have been calculated for the case of a “thin” plate in the waveguide, when the wavelength in the plate is much greater than the length of the plate.



Analysis of the method of generalized separation of variables in the problem of light scattering by small axisymmetric particles
摘要
In the problem of light scattering by small axisymmetric particles, we have constructed the Rayleigh approximation in which the polarizability of particles is determined by the generalized separation of variables method (GSVM). In this case, electric-field strengths are gradients of scalar potentials, which are represented as expansions in term of eigenfunctions of the Laplace operator in the spherical coordinate system. By virtue of the fact that the separation of variables in the boundary conditions is incomplete, the initial problem is reduced to infinite systems of linear algebraic equations (ISLAEs) with respect to unknown expansion coefficients. We have examined the asymptotic behavior of ISLAE elements at large values of indices. It has been shown that the necessary condition of the solvability of the ISLAE coincides with the condition of correct application of the extended boundary conditions method (ЕВСМ). We have performed numerical calculations for Chebyshev particles with one maximum (also known as Pascal’s snails or limaçons of Pascal). The obtained numerical results for the asymptotics of ISLAE elements and for the matrix support theoretical inferences. We have shown that the scattering and absorption cross sections of examined particles can be calculated in a wide range of variation of parameters with an error of about 1–2% using the spheroidal model. This model is also applicable in the case in which the solvability condition of the ISLAE for nonconvex particles is violated; in this case, the SVM should be considered as an approximate method, which frequently ensures obtaining results with an error less than 0.1–0.5%.



Using the method of discrete dipoles to approximate solutions of the problems of light scattering and absorption by particles
摘要
A method of approximate calculation of the interaction inverse matrix in the method of discrete dipoles is proposed. The knowledge of this matrix makes it possible to determine the optical response of a system to the action of an electromagnetic wave with an arbitrary shape, which can be represented as a combination of vector spherical wave functions. The number of calculation operations of the matrix in the proposed method is considerably smaller than in the case of its direct calculation. In the case of a change in the refractive index of scattering particles, two methods of approximate calculation of the interaction inverse matrix are also proposed. This makes it possible to calculate the optical response of systems with new characteristics without direct solving equations of a system with a large dimension. The accuracy of the methods is numerically determined for particles with spherical and cubic shapes. It is shown that the methods are computationally efficient and can be used to calculate the values of polarization vectors inside particles and extinction and absorption cross sections of systems.



A theory of excitation of a planar semiconductor optical waveguide using a diffraction grating: Single-scattering approximation
摘要
The problem of excitation of a totally reflecting planar optical waveguide using a coupling diffraction grating in the form of a periodic relief of the waveguide-layer thickness is solved within the single-scattering approximation. The polariton mode in the presence of a quantum well near the waveguide is considered. Based on the developed concepts, the following experimental features of the dependence of the intensity of radiation conducted in the waveguide layer on the angle of incidence of the excitation beam on the coupling diffraction grating are interpreted: the dependence on the mode number, the interference effects in the presence of two coupling diffraction gratings, and the influence of the lower substrate boundary on the thermal behavior of the waveguide structure.



On the motion control of microparticles by means of an electromagnetic field increasing with time for spectroscopic applications
摘要
The possibility of controlling the motion of microparticles by means of external electromagnetic fields (nonresonance laser radiation, in particular) that induce potential wells for such particles, which are characterized by fixed spatial distribution but deepen over time to a certain level, are analyzed. It is assumed that the particles are located in high vacuum and are affected by nondissipative external forces. Slowing down of relatively fast particles when they pass through the discussed potential wells is shown. Such slowing down of particles is demonstrated using a nonresonance laser beam with intensity increasing over time as an example. Specific features of particle dynamics in the electromagnetic fields under consideration in the case of a one-dimensional rectangular potential well are studied in detail based on simple analytical relations derived from the fundamental equations of classical mechanics. The methods of particle cooling and localization demonstrated in the present work can substantially increase spectroscopy resolution of various microparticles, including, under certain conditions, atoms and molecules.



Polarization tomography of residual stress in monocrystals of YAG
摘要
An algorithm for determining the thermal stress in round cylindrical monocrystals by means of the integral photoelasticity method is analyzed. Transillumination in a cross section of a sample is assumed. The optical problem is solved within the framework of the paraxial approximation assuming weak birefringence. Reconstruction is based on the measurement of characteristic parameters of the polarized light propagated through the sample.



Mutual spatiotemporal coherence of optical fields in an amplitude-splitting interferometer
摘要
We have considered cross correlations of wave perturbations formed by optical fields at different points of space at the exit of an interferometer with the splitting of the amplitude of the initial wave field. Expressions for the longitudinal spatiotemporal cross-correlation function of perturbations on the optical axis of a Michelson interferometer have been obtained and analyzed. We have determined spatial and temporal intervals in which the wave fields excite mutually coherent perturbations in the exit channel of the interferometer in the free space and in the image space of the lens system. We have found that, in the free space, mutually correlated perturbations arise simultaneously in identical longitudinal intervals, whereas, in the image space, they arise at different times in spatial and temporal intervals varying along the optical axis of the lens. The influence of cross correlations of the wave fields on the interferometer signal has been analyzed.



Geometrical and Applied Optics
Measurement of the stress state of materials by reflection of polarization-modulated light
摘要
A method for measuring mechanical stresses of photoelastic materials from the difference between the reflection coefficients of orthogonally polarized light waves incident on the surface of the stressed medium is considered. Comparative results of measurements of the stress state of polymethylmethacrylate in the conventional transmission polarization optical scheme and by the proposed refraction method are presented. A case of normal light incidence is considered.



Holography
Holographic nanocomposite and a related diffraction element
摘要
Highly selective volume-diffraction gratings are recorded on a holographic acrylate nanocomposite. The holographic characteristics of the gratings are studied. It is shown that the diffraction efficiency of gratings can reach 50% and a 3D hologram is formed. The refractive index modulation is 0.048–0.065.


