Potentiation of the cage effect in binary solvents detected by magnetic modulation of exciplex fluorescence

It was shown that selective solvation potentiates the cage effect in recombination of radical ion pairs formed in electron phototransport in binary solvents with components with strongly differing dielectric properties. This is manifested by a more pronounced (in comparison to single solvents) increase in the exciplex fluorescence in a magnetic field in solutions of pyrene with an excess of N,N-dimethylaniline. The magnitude of the magnetic effect, which is a function of the composition of the solvent, is equal to a maximum of 18% (B= 30 mT) for the benzene/dimethyl sulfoxide binary solvent with a 0.26 volume fraction of the latter. A simple model which explains the results obtained is proposed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2456–2463, November, 1991.     

Gas-phase electron diffraction studies of the icosahedral carbaboranes, ortho-, meta- and para-C2B10H12

The molecular structures of the three closo-carbaboranes, ortho-, meta- and para-C2B10H12, were experimentally determined using gas-phase electron diffraction (GED). All unique bond distances for ortho and meta carbaboranes were determined experimentally for the first time. For ortho-carbaborane (RG= 0.046), a model with C2v symmetry refined to give bond distances of 1.624(8) A for C-C, 1.093(8)A for C-H and 1.192(3)-1.196(3) A for B-H. For meta-carbaborane (RG= 0.040) a model with C2v symmetry refined to give a CC distance of 2.575(9) A. For para-carbaborane (RG= 0.062) a model with D5d symmetry refined to give a C-B bond distance of 1.698(3) A, B2-B3 of 1.785(1), B2-B7 of 1.774(4) and CC of 3.029(5)A. These GED structures are compared with geometries from other experimental diffraction methods (neutron, X-ray) and ab initio calculations.     

Zinc(II) and copper(II) complexes of edampda2−: octahedral,trigonal bipyramidal and in between [edampda2−=N,N′-bis-(pyridylmethyl)ethylenediamine-N,N′-diacetate]

ZnII and CuII complexes of the ligand edampda2– [N,N-bis(pyridylmethyl)-ethylenediamine-N,N-diacetate] have been studied in solution by 1H n.m.r. and e.p.r. spectroscopies, respectively. [ZnII(edampda)] exists in solution in a major octahedral isomer (ca. 83%) in which the two carboxylate donors and two pyridylmethyl donors remain stereochemically rigid up to 333K at pD=6.0. The major octahedral complex has equivalent glycinato and pyridyl donors as shown by equivalent AB quartets for each type of chelate. By contrast, the [ZnII(edta)]2– analogue complex is known to have processes which rapidly equilibrate the coordinated carboxylates leading to coalesced, broad singlets instead of AB quartets down to 273K (freezing point of the sample). The minor [ZnII(edampda)] species has one pendant pyridylmethyl arm. The complex does not increase in abundance up to 333K via dissociation of the major species, suggesting that it possesses a different five-coordinate geometry (approximate trigonal bipyramid). The [CuII(edampda)] complex exhibits an e.p.r. spectrum that is intermediate between rhombic or tetragonal CuII complexes (near D4h) and the reversed-e.p.r. type of trigonal bipyramidal CuII complexes (ca. D3h). The single g value of 2.079 for gg>2.03 identifies the [CuII(edampda)] complex as distorted toward trigonal bipyramidal whereas its [CuII(edtaH2)(H2O)] analogue is known to be distorted toward square pyramidal. A binuclear CuI complex of edampda2– is formed only as a transient, and it rapidly disproportionates into [CuII(edampda)] and Cu metal. A mononuclear [CuI(edampda)]– complex persists for up to 8 h, but is oxidized within 3 min by O2 to the CuII complex. [CuII(edampda)] oxidizes to CuIII with a highly irreversible wave on glassy-carbon at +1.09V compared to the [NiII/III(edampda)] wave at +1.32V.     

Synthesis, IR, UV/vis-, (1)H NMR and DFT study of chelatophore functionalized 1,3-benzoxazinone spiropyrans

Six novel functionalized spiropyran's derivatives of 2H-1,3-benzoxazinone series were synthesized by introducing the substituents with chelating ability into 2H-chromene part of the 8'-formyl-7'-hydroxy-3-methyl-4-oxo-3,4-dihydro-2H-1,3-benzoxazine-2-spiro-2'-[2H]-chromene (I) by condensation with 2-aminophenol, 2-amino-4-methylphenol, 2-amino-4-nitrophenol, 2-amino-1-methylbenzimidazole, 4-amino-4H-1,2,4-triazole, N-(4-aminophenyl)acetamide. (1)H NMR, UV/vis, IR spectroscopy combined with quantum-chemical calculations employing density functional theory (DFT) were used to study their structure. All substances, except 2-amino-4-nitrophenol derivative exist in solid state and in solution solely in closed spiroform, while the mentioned one undergoes partial spiropyran ring opening. In DMSO solution NMR spectra show ratio of 2:1 of closed and opened form, correspondingly.     

Modification of highly dispersed silica with zirconium acetylacetonate

The chemisorption of Zr(acac)₄ and the formation of nanoparticles of ZrO₂ on the surface of silica were studied by IR spectroscopy, thermogravimetry, thermal and X-ray phase analysis. The composition was established and the hydrolytic and thermal properties of ≡SiOZr(acac)₃ groups were investigated. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 44, No. 3, pp. 191–195, May/June, 2008.     

Resonant-Optical Detection of Nuclear Magnetization in the Si/CaF<Subscript>2</Subscript> Nanostructure

We have considered theoretically the characteristic features of optical detection of nuclear magnetization in the Si/CaF₂ structure under the conditions of EPR and NMR by measuring luminescence polarization. We show that application of EPR makes it possible to detect weak nuclear fields, but the time of spin relaxation of electrons imposes its constraint. The application of NMR is limited by nuclear fields of no less than 15–20 Gs. The possibility of using optical NMR for direct measurement of the nuclear field from changes in the luminescence polarization spectrum is shown. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 644–649, September–October, 2005.     

Flow Cytometry Analysis of <Emphasis Type="Italic">G</Emphasis><Subscript>0</Subscript>/<Emphasis Type="Italic">G</Emphasis><Subscript>1</Subscript> Diploid Cell Fraction in Ovarian Cancer Tissue

The proportion of diploid cells in the G₀/G₁ cell cycle phases was estimated by flow cytometry in 60 samples of stage III serous ovarian cancer tissue. The tumor tissue shows considerable heterogeneity with regard to the content of this tissue fraction, which ranged from 27 to 95% with a median of 73%. Statistically significant differences in the size of this fraction were identified by comparing tumor subgroups sensitive and resistant to first-line platinum-taxane chemotherapy. Predictive significance of the G₀/G₁ fraction was concluded and quantitative evaluation of this fraction is recommended for clinical use.     

Relation between crystal structure and electroluminescence in ZnS-Mn crystals

The electroluminescence of ZnS-Mn crystals annealed in zinc melt is investigated. When an external field of 10³-10⁴ V/cm is applied, continuous radiation is emitted over the whole volume of the spcimen. The volt-brightness characteristics are approximated by various functions and depend on the conditions of excitation. The results obtained are explained by the concentration of the electric field at barrier formed by partial dislocations at the place where they cut the hexagonal layers.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 33–37, September. 1985.     

Unusual structural and energetic features of homolytic bond dissociation: from tetrakis(disyl)diphosphine to tetrakis(di-tert-butylsilyl)hydrazine

Quantum chemical calculations of the structures and thermodynamics of homolytic dissociation of the central P-P and N-N bonds in tetrakis(disyl)diphosphine and tetrakis(di-tert-butylsilyl)hydrazine have been performed. The theory predicted negative standard enthalpies for homolytic bond dissociation in both cases, -71.0 and -108.4 kJ mol(-1) for the diphosphine and hydrazine, respectively, using the ONIOM (MP2/6-31+G*:B3LYP/3-21G*) level. The dissociation is accompanied by considerable structural changes in the radicals as compared to the corresponding fragments of the parent molecules, resulting in low dissociation enthalpies. The most pronounced changes in both radicals are the relaxation of bond angles in the substituents and a conformational change in the orientation of the substituent groups. In addition, the bis(di-tert-butylsilyl)aminyl radical displays a considerable increase in Si-N-Si angle and shortening of the Si-N bonds upon dissociation. These changes are not associated with any appreciable delocalisation of the lone electron, as the spin density is found from the B3LYP/3-21G* calculations to be largely concentrated on the nitrogen atom. It has been also shown that although the dissociation energies are low for both compounds, the intrinsic energies of the central bonds are still high, 140.6 kJ mol(-1) for the P-P bond in tetrakis(disyl)diphosphine and 490.6 kJ mol(-1) for the N-N bond in tetrakis(di-tert-butylsilyl)hydrazine, using the ONIOM method. The calculations predict that the dissociation of tetrakis(disyl)diphosphine would have negative free energy even without taking relaxation of the fragments into account, while the full potential of releasing about 306 kJ mol(-1) of energy stored in the ligands of tetrakis(di-tert-butylsilyl)hydrazine is only fully realised upon a considerable separation of the fragments.     

Preheating of a target by laser radiation through plasma and polymer aerogel

Processing of X-ray and optical streak-camera images after brightness amplification 5 proves unambiguously the existence of a preheating of the foil in two-layer targets (polymer aerogel plus Al foil). We observed this effect earlier at the accuracy limit of the experiment. Preheating may be explained by the initial transmission of laser radiation by an inhomogeneous plasma and aerogel remnants. The fraction of laser energy that passed through a microheterogeneous plasma to the foil or shell is small in comparison with the total energy in the pulse, but it comes to the target (foil or shell) at the initial period of the laser pulse and can be significantly affected by the dynamics of plasma and the efficiency of spherical cryogenic thermonuclear targets.