A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007     

Thermal Behavior of Urea-(D) Tartaric Acid and Urea-(DL) Tartaric Acid Crystals

The thermal behavior of two new non-linear optical (NLO) materials, urea-(D) tartaric acid (UDT) and urea-(DL) tartaric acid (UDLT) were studied by using DSC, TG and TMA. The results show that: 1) The two crystals have different melting points but similar decomposition temperatures due to the influences of intermolecular forces, which is attributed to the stereo effects of (D)-tartaric and (DL)-tartaric acid molecules; 2) There was only thermal expansion and no thermal contraction when the UDT and UDLT crystals were heated; 3) There was no phase transition within the measured temperature range; 4) The thermal expansion of the UDT and UDLT crystals shows a small anisotropy; 5) The specific heats of UDT and UDLT change linearly with temperature in the measured temperature range and the value for UDT is 1.321 J g-1 K-1 at 320 K while the specific heat of UDLT is 1.357 J g-1 K-1 at the same temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Catalytic Activity of Nickel Alloys in Anodic Oxidation of the Hypophosphite Ion as a Function of Their Composition

The rate of anodic oxidation of the hypophosphite ion on alloys Ni-P, Ni-B, and Ni-Mo-P is studied as a function of their composition and structure. The organic compounds that are customarily used to stabilize electrolytes of electroless nickel plating are shown to come useful when controlling composition of the Ni-P coatings at the expense of their different influence on the rates of partial processes of deposition of the alloy components. The formation of catalytic activity of such coatings is affected mostly by a structural factor. With alloys Ni-P, Ni-B, and Ni-Mo-P, whose composition was varied by altering the concentration of the source of the alloying component, dependence of catalytic activity of the surface on the composition is defined mainly by an electronic factor.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 972–980.Original Russian Text Copyright © 2005 by Sotskaya, Dolgikh, Ryabinina.     

Large second-order optical nonlinearities of s-triazine derivatives: View from micro molecules to macro crystals

Organic nonlinear optics (NLO) is also called mo-lecular nonlinear optics. In recent years organic mate-rials have been intensively studied because of their large NLO coefficients and structural diversities[1―3]. Second harmonic generation (SHG) is a bas…     

一种新型有机电致微腔结构的双模发射

采用结构Glass／DBR／ITO／NPB／NPB：Alq／Alq／Al制作了有机微腔电致发光器件。将空穴传输材料与发光材料以一定比例混合作为发光层，为了便于对比，在不改变有机层的膜厚的情况下同时制作了传统的异质结微腔器件，发现两种器件的发光光谱有很大不同，器件的复合效率与传统的异质结器件相比也得到了很大提高，这是因为将两种有机材料混合能消除界面势垒，提高器件的复合效率，从而提高了器件的发光性能，实现了微腔双模发射，且两个模式的半峰全宽分别为8nm和12nm。通过进一步优化器件结构可以实现微腔白光发射。     

Application of the stabilization method to interacting resonances

The stabilization method is applied to the case of interacting resonances in the photo-dissociation of van der Waals clusters composed by a rare gas atom bound to a dihalogen molecule. The study of an illustrative two-dimensional model consisting in a T-shaped NeI₂ molecule shows the adequacy of the method whenever the projection of the stabilization wave functions on the assumed prepared initial state is accounted for. The agreement of the fragmentation cross-sections with some previous results using the effective resolvent method and accurate close-coupling calculations is excellent. The method reveals its utility as a complementary tool since allows, through the analysis of the stabilization wave function in terms of zero-order levels, a precise characterization of the resonant states involved. Received 5 April 2002 / Received in final form 24 May 2002 Published online 19 July 2002     

Experimental investigation of the aquatic propulsion caused by localised flexural wave propagation in immersed wedges and plates

This paper describes the results of the experimental verification of the idea of wave-like aquatic propulsion of autonomous and man-inhabited vessels first published about 10 years ago by one of the present authors (V.V.K.). The idea is based on employing the unique type of localised flexural elastic waves propagating along edges of wedge-like structures immersed in water (wedge elastic waves). Such wedge-like structures supporting localised elastic waves can be attached like fish fins to a body of a small ship or a submarine and used for their propulsion. The proposed principle of employing localised flexural waves as a source of aquatic propulsion has been biologically inspired by the specific swimming mode used in nature by stingrays. To verify the idea experimentally, the first working prototype of a small catamaran using the above-mentioned wave-like propulsion via the attached rubber keel has been build and tested in Loughborough University. The tests have been carried out in two phases, in a water tank and then in open water. The test results have shown that the catamaran was propelled very efficiently and could achieve the speed of 36 cm/s, i.e., about one vehicle length per second, thus demonstrating that the idea of wave-like propulsion of small man-inhabited craft is viable. The reported proof of the viability of this idea may open new opportunities for marine craft propulsion, which can have far reaching implications.