Formation of an Equilibrium Complex of Lactate Dehydrogenase with Chlorin e 6

Using spectrophotometric, spectral-luminescent, and polarization methods, we have detected the formation of strong equilibrium complexes of a key glycolytic enzyme — lactate dehydrogenase — with a promising photodynamic sensitizer — chlorin e ₆. It has been established that enzymes serve as the most sensitive targets destroying tumor cells subjected to photodynamic therapy.     

Spectral-luminescent properties of chlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript> and malate dehydrogenase complexes

Spectral confirmation of the formation of stable equilibrium complexes (association constant K _as = 210⁶ M^–1) of the Krebs cycle enzyme — malate dehydrogenase (MDH) — and one of the promising photodynamic sensitizers — chlorin e ₆ — have been obtained. It is shown that the incorporation of dye molecules into the protein globule of dimeric MDH (each subunit of which contains 4 tryptophan amino acid residues, each binding one molecule of chlorin e ₆) is accompanied by quenching of the tryptophan fluorescence of the enzyme. However, despite the overlapping of the fluorescence spectra of tryptophanyls of MDH and the absorption spectrum of chlorin e ₆, the fluorescence quenching observed is not caused by singlet-singlet inductive-resonant transfer of energy from the donor to the acceptor. The conclusion has been drawn that the reason for the absence of energy transfer from tryptophanyls to the dye is the more effective intertryptophan migration of energy to one of the most longwave amino acid residues, the quenching of the luminescence of which occurs due to the reversible photoinduced transfer of an electron to chlorin e ₆ (formation of a complex with charge transfer). The formation of a complex with charge transfer between chlorin e ₆ (when it is excited) and one of the amino acid residues of the enzyme that contact with the dye at its binding site on the protein molecule is also the most noncontradictory explanation of the observed (when bound with MDH) decrease in the quantum yield of fluorescence of chlorin e ₆ upon increase in the duration of its quenching. The question of the ability of MDH to act as one of the most sensitive targets responsible for the disturbance of mitochondrial functions and initiation of the apoptosis of tumor cells in the process of photodynamic therapy is discussed.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 749–758, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Spectral-Luminescent Studies of the “Photolon” Photosensitizer in Model Media and in Blood of Oncological Patients

Using the methods of steady-state absorption and fluorescence spectroscopy and flash-photolysis, the new photosensitizer Photolon (Stock Company Belmedpreparaty) and its basic chromophore part — the substance chlorin e ₆ — have been studied under model conditions. It has been shown that there are no considerable differences between the spectral-luminescent characteristics of Photolon and chlorin e ₆ at a concentration not exceeding 2.5·10^–5 M in ethanol, phosphate-saline buffer (pH 8.5), and isotonic solution. That is, the polyvinyl-pyrrolidone (PVP) entering into the composition of Photolon does not influence the chromophore characteristics being investigated. It has been found that an increase in the mass fraction of PVP in the buffer solution of chlorin e ₆ leads to an increase in the degree of polarization of chlorin e ₆ fluorescence and to a change in the spectral-luminescent and kinetic characteristics, pointing to the fact that the pigment is built into the hydrophobic portions of the polymer. Using the method of multiple scattering of light, it has been shown that both Photolon and chlorin e ₆ are present in the whole blood of donors and oncological patients mainly in the monomeric form; Photolon is quickly removed from the blood of patients (after 24 h, C 10^–3 mg/ml).     

Investigation of the intramembrane distribution of chlorin e6 derivatives by using fluorescence quenching

Belarusian State University, 4, F. Skorina Ave., Minsk, 220050, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 2, pp. 179–187, March–April, 1995     

Mechanism of complexing of chlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript> and tetra(<Emphasis Type="Italic">p</Emphasis>-carboxyphenyl)porphyrin with malate dehydrogenase

The mechanism of complexing of the tetrapyrrole-nature photodynamic sensitizers chlorin e₆ and tetra(p-carboxyphenyl)porphyrin (TCPP) with the Krebs-cycle enzyme malate dehydrogenase (MDG) has been investigated by spectral-luminescence methods. It is shown that each subunit entering into the composition of the MDG dimer molecule forms an equilibrium complex with one dye molecule. However, if the sites of bonding of TCPP on a protein molecule are independent, the MDG-chlorin e₆ complex has a negative cooperativity since after the dye is incorporated into the first subunit of the macromolecule, its penetration to the second subunit becomes difficult. This is explained by the fact that conformation transformations, arising as a result of the incorporation of chlorin into one of the MDG subunits, are transferred to the site of its bonding on other MDG subunits through the intersubunit contacts of the enzyme. It has been established that photosensitizers compete with the hydrophobic fluorescent probe 8-aniline-1-naphthalenesulfonate (ANS) (whose position in the MDG macromolecule was described in detail in the literature) for the sites of bonding on the protein molecule, which allows the conclusion that TCPP and chlorin e₆ are localized in the catalytic domain of MDG. In this case, the sites of bonding of these dyes and the sites of bonding of nicotinamide-adenine dinucleotide, occupying the MDG domain that bonds coenzymes, do not interact with each other.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 111–118, January–February, 2005.     

Bacteriochlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript> as a sensitizer for photodynamic therapy

A simple scheme of modification of the native pigment bacteriochlorophyll a, extracted from the biomass of phototropic bacteria, for the purpose of obtaining a water-soluble derivative — bacteriochlorin e ₆ — which is similar in molecular structure to the effective sensitizer chlorin e ₆ and, in addition, has an intense longwave absorption band in the near-infrared region of the spectrum where biological tissues weakly absorb light — has been developed. The ease of production of bacteriochlorin e ₆ in combination with its physicochemical and spectral properties allow it to be considered as a promising sensitizer for photodynamic therapy.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 745–748, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Electron dichroism effects in the relativistic (e, 2e) process for K-shell ionization of atoms

In this communication we present theoretical demonstration of electron dichroism in the relativistic (e, 2e) process for K-shell ionization of atoms in non-coplanar asymmetric geometry. The theoretical formalism has been developed in plane wave Born approximation and in this approximation the triple differential cross-section (TDCS) has been expressed as a product of kinematical factors and atomic structure functions. The longitudinal spin asymmetry in the relativistic (e, 2e) process on K-shell of atoms has been shown to depend on the interference between the transition charge and component of the transition current in the direction perpendicular to the scattering plane. Further, the longitudinal spin asymmetry has been shown to depend on incident electron energy, atomic number of the target, azimuthal angle of the ejected electron and scattered electron angle.     

Influence of the sample orientation in Sn<Subscript>2</Subscript>P<Subscript>2</Subscript>S<Subscript>6</Subscript> crystals on the hydrostatic piezoelectric coefficients

The influence of the sample orientation on the effective value of the hydrostatic piezoelectric coefficients d _h ⁽ⁱ⁾ of Sn₂P₂S₆ crystals has been studied. The hydrostatic piezoelectric coefficients d _h ⁽¹⁾ and d′ _h ⁽³⁾ , were measured, d _h ⁽¹⁾ =(244±3) pC/N and d′ _h ⁽³⁾ =(92±1) pC/N. The hydrostatic piezoelectric coefficient d _h ⁽³⁾ for orthogonal axis system was calculated to be d _h ⁽³⁾ =(87±2) pC/N. The, optimal orientation of the sample has been found as (Xy l)−20°-cut. Maximal value of the effective hydrostatic piezoelectric coefficient d _h ⁽¹⁾ equals 260 pC/N. Double rotated samples were also studied. The orientation of the samples insensitive to the pressure has been found. The theoretical mean value of hydrostatic piezoelectric coefficient (d _h ) _mean corresponding to randomly oriented Sn₂P₂S₆ grains in a poled composite has been calculated to be (d _h ) _mean =136 pC/N.     

Directional behavior of nuclear quadrupole resonance in YBa2Cu3O6

Powder samples of YBa₂Cu₃O₆ were magnetically aligned and the anisotropies in the systems were studied by means of Cu(1) nuclear quadrupole resonance (NQR) in the absence of external magnetic fields. Our room temperature measurements of the NQR lineshapes and the spin–lattice and spin–spin relaxation times as a function of the aligning magnetic field indicate that full microscopic alignment can be achieved by using a magnetic field of about 4.7 T, for which doublet line patterns arising from a hyperfine splitting were observed.     

三明治结构Tan(B3N3H6)n+1 团簇的磁性和量子输运性质

利用密度泛函理论和非平衡格林函数方法, 本文对小尺寸团簇Ta_n(B₃N₃H₆)_n+1 (n ≤ 4)的磁性和量子输运性质进行了系统的研究. 计算结果表明, 此类体系采用三明治结构作为其基态并且具有较高的稳定性. 体系的磁矩随团簇尺寸的增大而线性增大. 当把Ta_n(B₃N₃H₆)_n+1团簇耦合到Au电极上时, 形成的Au-Ta_n(B₃N₃H₆)_n+1-Au体系在有限偏压下展示出了较强的自旋过滤能力, 因而可以被看做是一类新型的低维自旋过滤器.     

57Fe Mössbauer spectroscopy studies of Sr2Fe1−x Cr x Mo1−x W x O6 double perovskite compounds

Polycrystalline double perovskites Sr₂Fe_1?x Cr _x Mo_1?x W _x O₆ with x = 0, 0.05, 0.10, 0.15, 0.20, and 0.30 have been prepared by sold state reactions. A continuous decrease of the tetragonal unit cell parameters α and c with increasing x values is observed. The highest Curie temperature T _C = 426 K is recorded for the x = 0.10 compound. ⁵⁷Fe Mössbauer spectroscopy measurements indicate a non-integral electronic configuration of ～3d^5.3 for the Fe ions at the ordered double perovskite structure for x ≤ 0.20, which reaches ～3d^5.4 for x = 0.30. Fe–Mo/W anti-site and anti-phase boundary defects are observed in all samples in equal concentrations of around 3% of the total number of Fe ions in their structure.     

Investigation of the Cr:LiSrAlF6 crystal by high-temperature Raman spectroscopy

In this paper, Cr-doped LiSrAlF₆ crystals are investigated using high-temperature Raman spectroscopy and the single-crystal Raman spectra of Cr:LiSrAlF₆ are analysed by factor group theory and comparison with other fluorides. The results indicate that Cr:LiSrAlF₆ is stable below its melting point; Raman peaks located at 561, 322 and 250 cm^-1 are assigned to the A_1g modes of AlF₆, SrF₆ and LiF₆ octachdra, respectively; with temperature increasing, Raman peaks associated with AlF₆ octahedra shift towards low frequencies, while LiF₆ and SrF₆ octahedra are temperature-insensitive; around the crystal melting point, three new Raman peaks occur, which are associated with the AlF₆ octahedral chain structure. Finally, the microstructural evolution of Cr:LiSrAlF₆ from room temperature to its melting point is discussed based on its Raman spectra.     

The effect of low intra-sublattice repulsion on phase diagram of YBa2Cu3O6+x : A Monte Carlo simulation study

We report the results of Monte Carlo simulation of the phase diagram and oxygen ordering in YBa₂Cu₃O_6+x for low intra-sublattice repulsion. At low temperatures, apart from tetragonal (T), orthorhombic (OI) and ‘double cell’ ortho II phases, there is evidence for two additional orthorhombic phases labelled here asOI andOIII. At high temperatures, there was no evidence for the decomposition of theOI phase into theT andOI phases. We find qualitative agreement with experimental observations and cluster-variation method results.     

The growth of a single crystal of Sr3CuIrO6 and its magnetic behavior compared to polycrystals

We have grown single crystals of the psuedo-one-dimensional compound Sr₃CuIrO₆, a K₄CdCl₆-derived monoclinic structure with Cu-Ir chains along the [101] direction. We present the ac and dc magnetization behavior of the single crystals in comparison with that of the polycrystalline form reported earlier. There is a distinct evidence for at least two magnetic transitions, at 5 K (T ₁) and 19 K (T ₂), with different relative magnitudes in the single and polycrystals. The low temperature magnetic relaxation behavior of both the forms is found to be widely different, exhibiting unexpected time dependence.     

Paracharge phenomenology: systematics of the new hadrons

A systematic semiquantitative account of all aspects of the strong and electromagnetic interactions of all the newly discovered hadronic states (theψ’s, theχ’s, etc.) is presented within the framework of the paracharge scheme. Extensions of ideas familiar from the SU₃ classification scheme to SU₄ are shown to provide an understanding of the new states seen in the decays ofψ (3.1) andψ′ (3.7), including their masses and gross decay characteristics. The decays ofψ (3.1) andψ′ (3.7) themselves are studied in some detail. Since these are of electromagnetic origin in the scheme, their electromagnetic mixing with the resonance at 4.15 GeV (theP-state of the scheme) is important. Once this is taken into account, the resulting picture is in excellent agreement with available data.     

Enhancement of the hydrophobicity of silk fabrics by SF6 plasma

Hydrophobic properties are of interest in fabric and textile manufacture. We have used radio-frequency inductively coupled SF₆plasma to modify the surface of Thai silk fabrics for the enhancement of the hydrophobic property. The water contact angle of fabrics increased from 0°up to 145°after SF₆ plasma treatment. The measured water absorption time was found to depend upon the treatment time and RF power, for SF₆ pressures lower than 0.05 Torr. At higher SF₆ pressures, all samples achieved absorption times in excess of 200 min, regardless of the treatment time and RF power. The morphology changes of fabrics after plasma treatment were characterized by scanning electron microscopy and atomic force microscopy. After plasma treatment, the RMS surface roughness of the fibres increased from about 10 to 30 nm. From X-ray photoelectron microscopy analysis, we found that the hydrophobicity of the fabrics is the highest when the fluorine/carbon ratio at the surface increases. A small decrease of the oxygen/carbon ratio was also observed on the fabrics that showed the longest absorption times.     

A facile method to synthesize nitrogen and fluorine co-doped TiO2 nanoparticles by pyrolysis of (NH4)2TiF6

The nitrogen and fluorine co-doped TiO₂ (N-F-TiO₂) nanoparticles of anatase crystalline structure were prepared by a facile method of (NH₄)₂TiF₆ pyrolysis, and characterized by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet visible (UV-Vis) spectroscopy etc. With the increase of calcination temperature, (NH₄)₂TiF₆ decomposed into TiOF₂ and NH₄TiOF₃ at first, and then formed anatase-type TiO₂ with thin sheet morphology. H₃BO₃ as oxygen source can promote the formation of anatase TiO₂, but decrease the F content in the N-F-TiO₂ materials due to the formation of volatile BF₃ during the precursor decomposition. The photocatalytic activity of the obtained N-F-TiO₂ samples was evaluated by the methylene blue degradation under visible light, and all the samples exhibited much higher photocatalytic activity than P25. Moreover, the merits and disadvantages of this proposed method to prepare doped TiO₂ are discussed.     

Effect of intervening structure between CuO2 sheets in heavily Fe-substituted high-Tc superconductor FeSr2YCu2O6+δ

Heavily Fe-substituted Ba₂YCu₃O_6+δ-type compound FeSr₂YCu₂O_6+δ exhibits superconductivity around 60 K, only when it is annealed in N₂ and subsequently in O₂. Cationic distribution in this compound is strongly dependent on ionic radius at the Y site, and its superconducting properties are affected by the cationic distribution. In contrast, although the compound with the substitution of fluorite-type unit for Y has cationic order, it does not exhibit superconductivity. We have analyzed the crystal structure of the compounds with the substitution of other lanthanoid elements for Y and with substitution of fluorite-type unit for Y.     

Fabrication of Ti ohmic contact to n-type 6H-SiC without high-temperature annealing

The effect of surface morphology of 6H-SiC substrate on the ohmic contact properties of Ti/6H-SiC structure is studied. The H-terminated surface on Si-face 6H-SiC is obtained by both dipping SiC into HF acid solution for 15 s and thermal heating SiC in hydrogen atmosphere at 1100 C for 10 min, while the H-terminated surface on C-face 6H-SiC could be obtained only by the latter method. Ti is deposited on Si-face and C-face SiC substrates with H-terminated surfaces and ohmic contact is obtained without high-temperature annealing.