Photophysics and photochemistry of crystalline 5-fluorouracil

Fluorescence and photochemical processes in crystalline 5-fluorouracil (FU) were studied. It has been found by the spectral, luminescent, and ESR methods that upon photoirradiation of FU photoinduced electron and proton transfers occur, leading to the formation of three hydroxo tautomers and radical ion pairs, which are stabilized by the crystal matrix and luminesce with the emission wavelengths of 375, 415, 455 nm, and 530, 555 nm, respectively.     

Nitrogen-tellurium-containing heterocycles. 4. X-ray structure of 2-phenylbenzotellurazole

The crystal and molecular structure of 2-phenylbenzotellurazole is determined by x-ray methods. The heterocyclic fragment of the molecule is planar. The dihedral angle between planes of the heterocycle and the 2-phenyl substituent is 31.2. Somewhat shortened Te-N intermolecular ocntacts (3.43 å) are seen in the crystal. These do not substantially affect the physical properties of the compound.For Communication 3, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1690–1692, December, 1989.     

金属皂的晶体结构

钠、钾以外金属的高级脂肪酸盐通称金属皂。它们兼具金属盐和脂肪酸的特性,在工业上广泛用作为塑料助剂(热稳定剂、润滑剂等)、油漆催干剂、增稠剂、防水剂、脱模剂,爽滑剂等[1]。金属皂的许多特性随脂肪链长度和金属种类的不同而变化。稀土、碱土和锌、镉、铅等金属皂是重要的PVC热稳定剂和润滑剂[2,3]。前文[4,5]已报道了稀土金属皂结构的红外光谱和X 射线衍射谱,本文报道镁、钙、锶、钡、锌、镉、铅与棕榈酸、肉豆蔻酸、月桂酸、癸酸锌、辛酸形成金属皂结构的X 射线衍射谱。1　实验部分1 1　金属皂合成采用复分解法[1]合成,产物均…     

DNA base stacking involving adenine and 2-aminopurine

The potential energy surfaces of stacked structures consisting of adenine (A) and 2-aminopurine (2AP) have been investigated in the gas phase. Both face-to-back (the double-ring system of one base exactly on top of that of the other one) and face-to-face (one base flipped by 180°) A/A, 2AP/2AP and A/2AP stacks were considered. Minima and transition states were optimised at the counterpoise-corrected M06-2X/6-31+G(d) level of theory. For each type of stack, between five and nine minima were located, usually connected by low barriers of 1–2 kcal/mol. This shows the large conformational flexibility of these stacked base pairs. The double-ring system in A and 2AP affords multiple minima with similar twist angles, making the potential energy surface of stacks comprising of purine bases more complex than those of pyrimidine stacks. The locations of the stationary points on the potential energy surface differ for the three different systems; thus, the replacement of A by 2AP in a base stack changes its potential energy landscape.     

Structure and liquid crystalline properties of 2-hydroxyazobenzenes. X-ray diffraction, infra-red and DFT theoretical studies

The family of 2′-hydroxy-4′-alkyloxyazobenzenes containing in position 4 either CH₃ or Cl group with varying number of carbon atoms in alkyl group was analysed from the point of view of liquid crystalline properties and intramolecular OHN hydrogen bonding. The phase transition diagrams show that insertion of the OH group in 2′ position leads to a marked extention of mesophases as compared with parent azobenzenes and appearance in addition to nematic of the smectic SmA phase in the case of 4-chloro-derivatives. The role of chelate conjugating OHN hydrogen bonds in modification of mesophases is discussed based on DFT theoretical and X-ray as well as infrared studies. The importance of the molecule pairing is emphasized. Most important feature of mesophases and crystalline state of compounds under study is appearance of a continuous absorption down to 500 cm⁻¹ which is absent in solutions and Ar matrices.     

Vibrational spectroscopic and X-ray diffraction study of crystalline phases in the Li2O-SiO2 system

xLi₂O · (100 ? x)SiO₂ phases, where x = 20, 25, 33, 40, 50, 55, and 60 mol % (hereinafter, Li20, Li25, Li33, Li40, Li50, Li55, and Li60) were crystallized from melts, and their qualitative composition was determined by X-ray diffraction. The Li₆Si₂O₇ phase was established to precipitate during the crystallization of the melt containing 60 mol % Li₂O, thus enabling us to locate characteristic bands in the IR and Raman spectra of lithium pyrosilicate.     

Molecular structure of perfluoroolefin derivatives. 2. X-ray structural study of 3-p-cresoxyperfluoro-2-methylpent-2-ene

Conclusions Features of the molecular geometry of 3-p-cresoxyperfluoro-2-methylpent-2-ene are established by x-ray structural studies. Opposing steric and electronic effects of the bulky and electronegative R_F-substituents on the C atoms of the double bond in the perfluoroolefins are shown practically not to change the double bond length in comparison with ethylene.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1549–1552, July, 1989.     

In situ X-ray absorption fine structure studies of amorphous and crystalline polyoxovanadate cluster cathodes for lithium batteries

Amorphous and crystalline MetfV10 electrodes for lithium ion batteries were prepared by mixing MetfV10 with different binders: polyvinylidenefluoride (PVDF) or polytetrafluoroethylene (PTFE). The amorphous MetfV10 cathode demonstrates a higher specific capacity than the crystalline cathode. The reaction mechanism was studied using in situ X-ray absorption fine structure (XAFS) and impedance measurements. The X-ray absorption near-edge structure (XANES) results exhibited a 10-electron reduction per the formula of MetfV10 during discharge, resulting in a large capacity. Extended X-ray absorption fine structure (EXAFS) analyses suggested a slight expansion in the molecular size of MetfV10. The impedance measurements reveal that an increase of discharge capacities for the amorphous cathode is due to lower resistance than in the crystalline cathode. This study presents a rational selection of amorphous or crystalline cathode materials for high power and high energy density lithium batteries.     

Theoretical investigation of spectral properties and tautomerization mechanism of 2-aminopurine

In this work the spectral properties and tautomerization mechanism of 2-aminopurine are investigated using quantum chemical calculations. TD-DFT results lead to a conclusion that two tautomers of 2-aminopurine discussed in this work are fluorescent and present the pi-->pi* transition feature of vertical excitation and emission. It is predicted that the tautomerization of 2-aminopurine hardly occurs in a direct isomerization mechanism because of the high barrier. However, the explicit involvement of water molecules into the system reduces the barrier height considerably and hence makes the ground state reaction feasible. An explanation for the almost equal populations of the two tautomers in polar solvent is given through reaction mechanism analysis.     

Photophysics of representative ketocyanine dyes: dependence on molecular structure

Spectral properties of a new fluorescent ketocyanine dye have been discussed. The energy of maximum absorption/fluorescence of the dye exhibits bathochromic shift with increasing polarity of the medium. Both dipolarity-polarisability and hydrogen bond donation interaction contribute to solvation of the dye. Study of fluorescence parameters points to existence of different emitting states of the dye for aprotic and protic solvents. While the emitting state is the (1)(π, π*) state for aprotic solvents, fluorescence supposedly take place from a different emitting state involving H-bond formation in the excited state in protic solvents. Fluorescence parameters of the dye have been compared with those for a structurally similar symmetric ketocyanine dye. The faster decay of the dye relative to its symmetric counterpart has been explained as due to an increase of nonradiative decay.     

Photophysics and photostereomutation of Aryl methyl sulfoxides.

The effect of a methanesulfinyl group on the photophysics of several aromatic chromophores is reported. The spectroscopic singlet and triplet energies are affected only modestly, compared to that parent arenes, but the fluorescence yields fall by at least 1 order of magnitude. Fluorescence lifetimes are short. Fluorescence enhancements are observed on cooling the sulfoxides from room temperature to 77 K. High quantum yields of stereomutation are reduced as the temperature drops. There is not a consistent effect on triplet or phosphorescence yields. It is proposed that these results are consistent with a nonradiative pathway for deactivation of the singlet that results in stereomutation. A modest activation energy of a few kcal/mol is estimated for the photochemical racemization of 1-methanesulfinylpyrene.