Theoretical Studies on the First Hyperpolarizabilities of One-dimensional Donor-bridge-acceptor Chromophores and New Applications of BLA in Determining Molecular First Hyperpolarizabilities

We present a quantum-chemical analysis of the relationship between the bond length alteration （BLA） and the static first hyperpolarizability of a series of one-dimensional （1D） chromophores with donor-bridge-acceptor （D-B-A） structures. The calculated results show that the parameter BLA can be considered as an indicator to evaluate the molecular first hyper- polarizability. Along the direction of molecular ground-state dipole moments, the evolutions of BLA can be classified into three categories： the first is a non-monotonic line, which represents most chromophores; the second is monotonic increasing; and the third, contrarily, is monotonic decreasing. On the whole, the first hyperpolarizabilities of these studied chromophores are the monotonic functions of BLA along the direction of dipole moments. Therefore, the first hyperpolarizability of these 1D chromophores can be preliminarily evaluated in terms of the development of BLA without a rigorous computation. In other words, one can roughly estimate the relative magnitude of the first hyperpolarizability according to the optimized geometry.     

New developments in the field of reactive acrylic adhesives and sealing materials

The influence of oligomeric base on the properties of acrylic adhesives and sealants cured by radical mechanism is studied. New anaerobic materials on the basis of oligourethane(meth)acrylates (OUMs) are developed. It is shown that, by adjusting the OUM nature, it is possible to increase the heat and moisture stability of adhesive compositions. As a result of these works, UV-cured adhesive compositions, heat-cured adhesive for bonding untreated aluminum, and two-part adhesive compounds cured at both positive and negative temperatures are developed.     

Synthesis of unsymmetrical 1,2-bis(diorganochlorosilyl)ethanes

Unsymmetrical 1,2-bis(diorganylsilyl)ethanes were synthesized by two procedures. Hydrosilylation of chloro(vinyl)silanes were used to obtain compounds of the general formula ClMe₂SiCH₂CH₂SiRMeCl with different substituents (R = Et, Vin, Ph) on the silicon atom. Chlorodealkylation of 1,2-bis(trialkylsilyl)ethanes gave compounds of the general formula ClAlk₂SiCH₂CH₂SiAlk₂Cl (Alk = Me, Et, Pr). It is established that the latter reaction provides high yields only with Me-and Et-substituted compounds, whereas Pr-substituted products are formed in poor yields. The mechamism of this reaction based on quantum-chemical calculations is offered.     

Theoretical Studies on the Binding of Cd~（2＋） to Uracil and Its Thio-derivatives

The interaction of Cd2+ with uracil,2-thiouracil,4-thiouracil and 2,4-dithiouracil have been investigated by the density functional theory(DFT) calculations.For uracil and 2,4-dithiouracil,where the two basic sites are the same,Cd2+ attachment to the heteroatom at position 4 is preferred.However,for the systems where both types of basic centers,a carbonyl and a thiocarbonyl groups,are present,Cd2+ association with sulfur is favorable.The enhanced stability of these enolic and thiol forms comes from Cd2+ interaction with two basic sites simultaneously,which thereby triggers a significant aromatization of the ring.More significantly,the Cd2+ binding energy with uracil and its thio-derivatives is larger than the tautomerization barriers connecting the diketo-like forms with the corresponding enolic-like tautomers.Consequently,when associated with Cd2+,all tautomers are energetically accessible and should be observed in the gas phase.     

Effect of the diamagnetic dilution on the magnetic ordering and electrical conductivity in the Co3O2BO3: Ga ludwigite

Single crystals of cobalt ludwigite Co₃O₂BO₃ with diamagnetic substitution of Ga³⁺ ions for a part of the cobalt ions have been grown by the flux method. A detailed investigation of the crystal structure and magnetic properties of the compound has been carried out. A preferred character of the occupation of nonequivalent crystallographic positions by gallium has been revealed. It has been found that the effective magnetic moment and the magnetic ordering temperature are decreased compared to those in the original crystal of the Co₃O₂BO₃ ludwigite. It has been noted that the pronounced magnetic anisotropy observed in the crystallographic ab plane of the original material of the Co₃O₂BO₃ composition disappears in the presence of gallium.