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.     

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。     

Ratio of Protein Fractions in Cereal Grains Cultivated in Uzbekistan

The glutelin fraction was used as the food value index of local corn. The base-soluble fraction was used as a test of the glassiness of local strains of rice grain. The content of gliadins and glutelins did not change over 24 h after wheat grain cultivated in Uzbekistan was moistened.     

Synthesis and properties of noncoplanar rigid‐rod aromatic polyhydrazides and poly(1,3,4‐oxadiazole)s containing phenyl or naphthyl substituents

Two new phenyl‐ and naphthyl‐substituted rigid‐rod aromatic dicarboxylic acid monomers, 2,2′‐diphenylbiphenyl‐4,4′‐dicarboxylic acid ( 4 ) and 2,2′‐di(1‐naphthyl)biphenyl‐4,4′‐dicarboxylic acid ( 5 ), were synthesized by the Suzuki coupling reaction of 2,2′‐diiodobiphenyl‐4,4′‐dicarboxylic acid dimethyl ester with benzeneboronic acid and naphthaleneboronic acid, respectively, followed by alkaline hydrolysis of the ester groups. Four new polyhydrazides were prepared from the dicarboxylic acids 4 and 5 with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. These polyhydrazides were amorphous and readily soluble in many organic solvents. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass transition temperatures in the range of 187–234 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(1,3,4‐oxadiazole)s exhibited T_g's in the range of 252–283 °C, 10% weight‐loss temperature in excess of 470 °C, and char yield at 800 °C in nitrogen higher than 54%. These organo‐soluble polyhydrazides and poly(1,3,4‐oxadiazole)s exhibited UV–Vis absorption maximum at 262–296 and 264–342 nm in NMP solution, and their photoluminescence spectra showed maximum bands around 414–445 and 404–453 nm, respectively, with quantum yield up to 38%. The electron‐transporting properties were examined by electrochemical methods. Cyclic voltammograms of the poly(1,3,4‐oxadiazole) films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited reversible reduction redox with E_onset at ?1.37 to ?1.57 V versus Ag/AgCl in dry N,N‐dimethylformamide solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6466–6483, 2006     

Effect of the pore surface modification of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes

We have investigated the effect of the surface state and surface treatment of the pores of an inorganic substrate on the plasma‐grafting behavior of pore‐filling‐type organic/inorganic composite membranes. Shirasu porous glass (SPG) was used as the inorganic substrate, and methyl acrylate was used as the grafting monomer. The grafting rate increased as the density of silanol on the SPG substrate increased. This result suggests that radicals are generated mainly at the silanol groups on the pore surface by plasma irradiation. The SPG substrates were treated with silane coupling agents used to control the mass of organic material bonded to the pore surface. The thickness of the grafted layer became thinner as the mass of organic material bonded to the pore surface of SPG increased. This decrease in the thickness of the grafted layer could be explained by the decrease in the penetration depth of vacuum ultraviolet rays contained in plasma having a wavelength of less than 160 nm that generated radicals in the pores of the substrate. The thickness of the grafted layer inside the SPG substrates could be controlled through the control of the mass of organic material bonded to the pore surface of the SPG substrate. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 846–856, 2006     

Chiral soluble polymers and microspheres for enantioselective crystallization

A series of chiral polymers based on poly(N‐acryl) amino acids was synthesized using a convergent synthetic approach. These chiral polymers have been used as chiral additives to induce enantioselective crystallization of racemic or conglomerate amino acids in solutions. These polymeric additives showed strong capabilities to enhance highly enantioselective resolution during the crystallization of amino acids. In addition, these polymers caused unusual modifications of amino acid crystal morphologies. Furthermore, spherical microparticles of those same chiral polymers were also shown active in similar chiral discriminations during amino acid crystallizations occurring on microparticle surfaces. Our study demonstrates the high potential of chiral polymers and microparticles to resolve amino acids throughout crystallization processes. High enantiomeric excesses in one targeted enantiomer of amino acids can also be maximized via time‐dependent kinetic control of crystallizations. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3009–3017, 2006     

Radiation induced decomposition of halogenated organic compounds in water

Decomposition by ionizing radiations of p-chlorophenol and tetrachloroethylene in synthetic water samples at about 2 mg Cl L⁻¹, has been studied on laboratory-scale experiments. Bicarbonate/carbonate and nitrate ions, at two concentration levels (20 and 200 mg HCO₃⁻¹ and 1 and 50 mg NO₃⁻L⁻) were added to synthetic samples in order to evaluate their influence on decomposition yield. At 5 kGy γ dose level, a quantitative degradation of p-chlorophenol is obtained whereas only qualitative consideration can be drawn on tetracholoroethylene. Comparative study with respect to degradation of p-cholophenol solutions (about 2 mg Cl L⁻¹) by γ-rays and electron beam irradiation treatment at 0.5 kGy dose level, are in progress; preliminary results indicate that irradiation with γ-rays seems to be more efficient in terms of removal efficiency respect to electron beams source.