Features of emission and absorption of indotricarbocyanine dyes on extitation to higher electronic states

The manifestation of ion pairs in the absorption and emission of fluorescence by symmetric indotricarbocyanine dyes with the same cation and anions Br, I, and BF4 in ethanol, methylene chloride, and dichlorobenzene has been investigated. It is shown that the formation of ion pairs on passing to low-polarity solvents, along with the changes in the electronic absorption and emission spectra, manifests itself in the polarization and fluorescence excitation spectra. We were the first to establish that the presence of an equilibrium mixture of contact ion pairs and free ions in solutions has an effect on the position and probabilities of transitions not only for the first but also for higher excited singlet states of the molecules of polymethine dyes. The formation of ion pairs manifests itself more clearly when the spectral-luminescence properties of compounds in the shortwave spectral region are analyzed. It has been established that marked changes arise in the absorption, excitation, emission, and polarization fluorescence spectra, as well as in the lifetime and quantum yield of fluorescence in this spectral region when the solvent is changed

Spectral analysis of the structure of ultradispersed diamonds

The structure of ultradispersed diamonds (UDD) is studied by spectral methods. The presence of diamond crystal phase in the UDD is found based on x-ray analysis and Raman spectra. The Raman spectra also show sp2- and sp3-hybridized carbon. Analysis of IR absorption spectra suggests that the composition of functional groups present in the particles changes during the treatment

Generation of singlet oxygen by indotricarbocyanine dyes in low-polarity media

We present the results of a study of the spectral luminescence properties of three groups of indotricarbocyanine dyes, each of which is formed from compounds with the same cation and different anions. In high-polarity solvents, in the absorption and emission spectra of the dyes we see one type of center; in low-polarity solvents, due to the presence of different ionic forms of the dyes (free ions, contact ion pairs), we observe either one type or two types of centers. By analysis of the luminescence of molecular oxygen in the 1.27 µm spectral region, we determined the efficiency of photosensitization of 1O2 formation by dyes in deuterated solvents. We have shown that in low-polarity solvents, the yield for singlet oxygen generation is higher for indotricarbocyanine dyes which are found in the contact ion pair state and which also contain a heavy atom (I) in the anion. We have observed that an increase in the fraction of contact ion pairs in solution as the dye concentration increases or when an additional salt is introduced leads to an increase in the quantum yield for generation of singlet oxygen. In polar deuterated acetonitrile, the counterion has no effect on the efficiency of photosensitization of oxygen by the dyes

Fluorescence of the Polymethine Dye Tiks and Diagnostics af Cancert

It is shown that the fluorescence of the polymethine dye TIKS, whose absorption and fluorescence bands are located in the spectral region of transmission of biological tissues, can be recorded from a depth of up to 1.5 cm of an animal’s body. The intensity of the fluorescence recorded from the surface of the animal’s body in intravenous injection of the dye (1–2 mg/kg) is in direct proportion to its concentration in tumor nodes and muscles. In rapidly growing tumors, a high (up to 3.6) degree of contrast of the content of the dye is attained in tumor tissues as compared to the surrounding normal tissues. Over the course of 7 days after the injection, the dye is practically completely removed from both the tumor and normal muscular tissues. From the change in the fluorescence intensity in scanning the surface one can determine the regions of localization of tumor nodes against the background of the surrounding normal tissues and the presence of regions with a nonuniform distribution of the dye

Spectral-luminescent properties of cationic indotricarbocyanine dyes in cancerous cells and solutions

The spectral-luminescent properties of symmetrical indotricarbocyanine dyes with the same cation and different anions (Br−, BF4−) in cancerous HeLa cells, an isotonic solution of NaCl, and organic solvents have been investigated. It is shown that when these dyes are present in cells in nontoxic concentrations, they are in a monomeric state, they are localized in the region with a low dielectric permeability, bonded to biological macromolecules, and do not make contact with an aqueous medium. It has been established for the first time that the molecules of the polymeric dyes are present in cells predominantly in the form of contact ion pairs, and in a dye with the Br− anion the presence of free cations or solvately separated ionic pairs is revealed. It is shown that the shift of the ion equilibrium toward contact ion pairs for the dyes in the cells (as compared to the low-polarity organic solvents) can be due to the fairly high concentration of salts in the biosystem

Fluorescence of a photosensitizer based on an indotricarbocyanine dye in photochemotherapy

We present the results for studies of the spectral luminescence properties of a symmetric indotricarbocyanine dye (PD1) in HeLa tumor cells and animal tissues in vivo during a photochemotherapy session and after the end of the session. We have established that when the dye is exposed to light in tumor tissues, changes occur in the position and half-width of the dye fluorescence spectra, while in a culture of HeLa cells its spectral characteristics are constant. Based on analysis of the effect of overlap between the absorption spectra of endogenous biomolecules and the fluorescence spectra of the dye plus comparison of the experimental data with numerical modeling results, we have concluded that the observed changes in the fluorescence spectra of PD1 in vivo are due to a change in the ratio of the different forms of hemoglobin in the tumor tissue. We have shown that the spectral characteristics of PD1, fluorescing in the near IR range, correlate with the depth of tumor tissue necrosis achieved on exposure to light. We have established that tumor tissue necrosis occurs down to a depth of 2 cm in the case of all strains studied: S-45, SM-1, and W-256, where as a result of exposure to light, we observe an increase in the half-width and a short-wavelength shift of the fluorescence spectrum of the dye PD1, and also the intensity of its fluorescence does not recover

Spectral luminescence properties of indotricarbocyanine dye in biological tissues

We have established that the shape and position of the maximum in the fluorescence spectrum of an indotricarbocyanine dye in tumor and normal tissues in vivo change over time after intravenous injection of the dye. Based on analysis of the spectral properties of the dye in vivo and in blood plasma, the dependence of the properties on the time since injection has shown that in the living body, the environment of the dye molecule changes as the photosensitizer goes from the skin into the tissue. We have established that in tissues in vivo, the dye molecules are localized in a region with low dielectric constant of the medium. We have shown that the change in the ratio of the concentrations of the different forms of hemoglobin in the blood has an effect on the absorption and shape of the fluorescence spectrum of the dye in tissues in vivo

Influence of photon energy on the efficiency of photochemotherapy

It is found that when indotricarbocyanine dye in HeLa cells is exposed to photons with different energies the efficiency of cell damage is wavelength independent provided the photosensitizer absorbs the same number of photons per unit time. In vivo animal experiments with two strains of tumor show that when the wavelength of the irradiating light is increased (668, 740, and 780 nm) and the number of photons absorbed per unit time per unit volume of the tumors is held constant, the damage depth increases by a factor of 1.5 and 3, respectively. The observed changes are related both to differences in the in vivo tissue optical transmission with increasing wavelength and an increased local concentration of oxygen owing to photodissociation of oxy-hemoglobin

Spectral Properties of Single Crystals of Synthetic Diamond

The half-width of the spectrum of Raman scattering (RS) of the first order of a diamond single crystal grown in a nickel-free system containing nitrogen getters is identical to all growth sectors (1.69 ± 0.02 cm−1). The sectorial inhomogeneity is not reflected in the transmission spectra and birefringence of this crystal. The nitrogen concentration is 4⋅1017 cm−3. For different growth sectors of the diamond crystal grown in the Ni–Fe–C system, the half-width of the Raman line varies from 1.74 to 2.08 cm−1, differences in the transmission spectra and birefringence are observed, and photoluminescence is revealed. The concentration of nitrogen in the growth sectors {001} is 1.6⋅1019 cm−3, the content of nickel is estimated to be at a level of 1019 cm−3, and the content of nitrogen in the {111} sectors is 4⋅1019 cm−3

Optical properties of new indotricarbocyanine dye as a limiter of laser radiation power

We present results of experimental and theoretical studies of the optical characteristics of a new indotricarbocyanine dye that is capable of effectively limiting the power of laser radiation in the visible spectral range. The spectral-luminescent and energy characteristics of the dye molecules and their absorption spectra from the excited state with nanosecond resolution are investigated experimentally. Quantum-chemical methods are used to calculate electronic absorption spectra from the ground (S0 → Sn) and excited (S1 → Sn) states and to determine the nature of electronic states of the molecule and the rate constants of intramolecular photo-physical processes. The results of the theoretical research agree with experimental data. It is shown that the investigated dye has singlet-singlet absorption at 400–600 nm. Nonlinear absorption of the dye upon excitation by radiation of the second harmonic of a Nd:YAG laser is studied by z-scanning with an open diaphragm. The ratio of dye absorption cross sections from the excited and ground states at 532 nm is determined in the framework of a three-level model. The results are compared with those for previously studied compounds