Nature of π-Electronic Transitions in UV Spectra of Deoxyvasicinone and Its Derivatives

The principal types of electronic transitions in absorption spectra of deoxyvasicinone and its 6-amino- and 6-nitro-derivatives were determined by analyzing the electron-density distributions in excited states calculated using ZINDO/S.     

Chlorination of aromatic substrates catalyzed by the phthalocyanine complexes

The chlorination of benzene, toluene, and o-xylene with molecular chlorine in the presence of the phthalocyanine complexes of different structures was studied. The transformations of the catalysts during the reaction were investigated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1644–1647, August, 2008.     

γ-辐照对纯Y_2SiO_5和Eu~(3+)∶Y_2SiO_5晶体光谱性能的影响

研究了γ-辐照前后纯Y2SiO5和Eu3+掺杂的Y2SiO5晶体吸收光谱的变化,辐照后,未退火和氢气退火的纯Y2SiO5晶体在260~270 nm和320 nm波段产生了附加吸收峰,分别是由F心和O-心的吸收引起的;经过空气退火的纯YSO晶体中,由于消除了氧空位,因此辐照后没有出现色心吸收峰。在Eu3+∶Y2SiO5晶体中,不但有相同的F心和O-心吸收峰,而且还有Eu2+离子在300 nm和390 nm的吸收峰。随着辐照剂量的增加,色心附加吸收峰增强。空气退火能减少Eu3+∶Y2SiO5晶体中的色心,而氢气退火能增加色心。     

含氟碳菁染料聚集行为的研究

本文对五种不同结构的含氟碳菁染料的甲醇溶液及吸附在碘溴化银T 颗粒表面的聚集行为进行了研究 ,测定了照相性能 ,计算了增感倍率。Dye1 ,Dye2 ,Dye3在甲醇溶液中测得的单分子态吸收曲线 ,当取代基从C2 H5→CH3→无取代基时 ,最大吸收峰对应的波长向短波方向移动 ;乙基取代基的增感染料 (Dye1 )吸附在碘溴化银表面形成的J 聚集态峰值较高 ,对应的增感倍率也高。没有取代基的增感染料 (Dye3)不形成J 聚集 ,增感倍率低 ,有减感作用。Dye4与Dye5相比 ,Dye4具有尖而窄的J 聚集反射光谱 ,增感倍率高。结果表明 :不同结构的增感染料吸附在卤化银颗粒上形成的J 聚集态不同 ,吸收谱带窄的J 聚集态增感染料具有较高的增感倍率。     

Crystallographic report: Diiodo[tris(2‐pyridyl)amine]mercury(II), [(C5H4N)3N]HgI2

In mononuclear HgI₂[(C₅H₄N)₃N], mercury is tetrahedrally coordinated by two nitrogen atoms of a tris(2‐pyridyl)amine ligand and two iodides. The coordination moieties are connected by weak intermolecular Hg(II)···I interactions to give a one‐dimensional structure. Copyright © 2003 John Wiley & Sons, Ltd.     

1H and 13C NMR spectroscopic study of oxidation of D,L‐cystine and 3,3′‐dithiobis(propionic acid) with hydrogen peroxide in aqueous solution

The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D₂O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu²⁺ cations, but not Fe³⁺ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd.     

Radial and angular correlation in heliumlike ions

In the framework of nonrelativistic variational formalism a new type of basis set is proposed, to estimate separately the effect of radial and angular correlations on the ground‐state energy for helium isoelectronic sequence H^? to Ar¹⁶⁺. Effect of radial correlation is incorporated by using multiexponential functions arising from product basis sets suitably formed out of Slater‐type one‐particle orbitals. The angular correlation can be switched on by incorporating an expansion in terms of basis involving interparticle coordinates. With a set of six‐term Slater‐type one‐particle basis and five‐term interparticle expansion, the ground‐state energy of helium is estimated as ?2.9037236 (a.u.) compared with the multiterm variational estimates ?2.9037244 (a.u.) due to Pekeris and Thakkar and Smith and Drake. Matrix elements of different operators in the ground state have been calculated and found to be in good agreement with available accurate results. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003     

Transport properties of acetone aqueous solutions: molecular dynamics simulation and NMR studies

Two quantities η_rel and are applied to study the nonideal acetone–water association mixture. An all-atom acetone model and a TIP5P water model have been adopted for molecular dynamics simulation. We study the transport properties of the system comparing the 's of strong hydrogen bond and weak contact based on transport properties, MD simulations together with NMR experimental data and find good agreement of concentration dependence, which exhibits the cooperation effect.     

掺杂两种荧光染料的有机红光电致发光器件

制作了掺杂rubrene和4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl-9,enyl)-4H-pyran(DCJTB)两种荧光染料的红光有机电致发光器件。N,N’-diphenyl-N,N’-bis(1-naphthyl)-(1,1’-biphenyl)-4,4’-diamine(NPB)和掺杂的Tri-(8-hydroxyquinoline)aluminum(Alq3)分别作为空穴和电子传输层。我们发现掺rubrene和DCJTB的器件性能与只掺DCJTB的器件性能相比有所提高。器件性能的改善是因为掺入的rubrene能够促进从Alq3到DCJTB的能量转移。根据荧光衰减曲线,计算出从Alq3到DCJTB、从Alq3到rubrene以及从rubrene到DCJTB的能量转移速率分别为1.04×109,3.89×109,2.79×109s-1。可以看出能量通过rubrene从Alq3到DCJTB的转移速率是能量直接从Alq3到DCJTB的2.7倍。     

Stemmosides C and D, two novel unusual pregnane glycosides from Solenostemma argel: structural elucidation and configurational study by a combined NMR-quantum mechanical strategy

Stemmosides C and D, two novel pregnane glycosides characterized by an unusual C-17 side chain were isolated from the pericarps of Solenostemma argel. In addition, stemmoside D displays an uncommon 14β proton configuration, apparently being the first pregnane isolated from plants known to have a 15 keto, cis CD ring junction. Their structures have been established by ESIMS and NMR experiments. The relative configuration of the molecules was determined using a strategy based on the simulation of ¹H, ¹³C, and J coupling NMR parameters. DFT calculations of ¹H and ¹³C chemical shifts, and of the ¹H homonuclear spin–spin coupling constants were performed with the mPW1PW91 functional using the 6-31G(d,p) basis set on the fully optimized geometries of all the possible stereoisomers.