Synthesis and characterization of HC[C(Me)N(C(6)H(3)-2,6-i-Pr(2))](2)MX(2) (M = Al, X = Cl, I; M = Ga, In, X = Me, Cl, I): sterically encumbered beta-diketiminate group 13 metal derivatives

A series of group 13 metal complexes featuring the beta-diketiminate ligand [[(C(6)H(3)-2,6-i-Pr(2))NC(Me)](2)CH](-) (i.e., [Dipp(2)nacnac](-), Dipp = C(6)H(3)-2,6-i-Pr(2)) have been prepared and spectroscopically and structurally characterized. The chloride derivatives Dipp(2)nacnacMCl(2) (M = Al (3), Ga (5), In (8)) were isolated in good yield by the reaction of 1 equiv of Dipp(2)nacnacLi.Et(2)O (2) and the respective metal halides. The iodide derivatives Dipp(2)nacnacMI(2) (M = Al (4), Ga (6), In (9)), which are useful for reduction to afford M(I) species, were made by a variety of routes. Thus, 4 was obtained by treatment of the previously reported Dipp(2)nacnacAlMe(2) with I(2), whereas the gallium analogue 6 was obtained as a product of the reaction of "GaI" with Dipp(2)nacnacLi.Et(2)O, and 9 was obtained by direct reaction of InI(3) and the lithium salt. The methyl derivatives Dipp(2)nacnacMMe(2) (M = Ga (7), In (10)), which are analogous to the previously reported Dipp(2)nacnacAlMe(2), were synthesized by the reaction of GaMe(3) with Dipp(2)nacnacH (1) or by reaction of the indium chloride derivative 8 with 2 equiv of MeMgBr in diethyl ether. The compounds 3-10 exist as colorless, air- and moisture-sensitive crystalline solids. Their X-ray crystal structures feature nearly planar C(3)N(2) arrays in the Dipp(2)nacnac ligand backbone with short C-C and C-N distances that are consistent with a delocalized structure. However, there are large dihedral angles between the C(3)N(2) plane and the N(2)M metal coordination plane which have been attributed mainly to steric effects. The relatively short M-N distances are consistent with the coordination numbers of the metals and the normal/dative character of the nitrogen ligands. The compounds were also characterized by (1)H and (13)C NMR spectroscopy. (1)H NMR data for 7 revealed equivalent methyl groups whereas the spectrum of 10 displayed two In-Me signals which indicated that ring wagging was slow on the (1)H NMR time scale.     

Remarkable supramolecular catalysis of glycoside hydrolysis by a cyclodextrin cyanohydrin

(6AR,6DR)-6A,6D-di-C-cyano-beta-cyclodextrin (3) was synthesized and shown to catalyze hydrolysis of nitrophenyl glycosides with the reaction following Michaelis-Menten kinetics. At pH 7.4 and 25 degrees C, hydrolysis of 4-nitrophenyl-beta-glucopyranoside (2) was catalyzed with KM = 15 mM, kcat = 8.2 x 10-6 s-1, and kcat/kuncat = 1217. Catalysis was observed with concentration of 3 as low as 10 muM. Hydrolysis of the corresponding alpha-glucoside, alpha-galactoside, alpha-mannoside, and 2-nitrophenyl-beta-galactoside was also catalyzed by 3, with kcat/kuncat ranging from 283 to 2147. A series of analogues of 3 was prepared and investigated for catalysis of the hydrolysis of 2: (6AR,6DR)-6A,6D-di-C-propyl-beta-cyclodextrin (9) was not catalytic, while 6A,6D-di-C-cyano-6A,6D-dideoxy-beta-cyclodextrin (12) had a low catalytic activity (kcat/kuncat = 4). A kcat/kuncat = 48 was found for 6A,6D-dialdehydo-beta-cyclodextrin dihydrate (11). It was proposed that 3 acts by general acid catalysis on the bound substrate.     

Hoeffding's inequalities: A counterexample

A sequence : ₀ satisfiesHoeffding's inequality of order n if wheneverX ₁,...,X _n are independent nonnegative integer-valued elementary random variables and are independent identically distributed nonnegative integer-valued elementary random variables, the common distribution of which is the average of those ofX ₁,...,X _n. We show that for each integerm greater than 2 there exists a sequence satisfying Hoeffding's inequality of every order greater thanm but not that of orderm. This answers a question raised by Berg, Christensen, and Ressel.     

FCC Rolling Textures Reviewed in the Light of Quantitative Comparisons between Simulated and Experimental Textures

The crystallographic texture of metallic materials has a very strong effect on the properties of the materials. In the present article, we look at the rolling textures of fcc metals and alloys, where the classical problem is the existence of two different types of texture, the “copper-type texture” and the “brass-type texture.” The type of texture developed is determined by the stacking fault energy of the material, the rolling temperature and the strain rate of the rolling process. Recent texture simulations by the present authors provide the basis for a renewed discussion of the whole field of fcc rolling texture. We simulate the texture development with a model which allows us to vary the strength of the interaction between the grains and to vary the scheme for the calculation of the lattice rotation in the individual grains (type CL/MA or PR/PSA). For the deformation pattern we focus on {111}<110> slip without or with deformation twinning, but we also consider slip on other slip planes and slip by partial dislocations. We consistently make quantitative comparison of the simulation results and the experimental textures by means of a scalar correlation factor. We find that the development of the copper-type texture is best simulated with {111}<110> slip combined with type CL/PR lattice rotation and relatively strong interaction between the grains — but not with the full-constraint Taylor model and neither with the classical relaxed-constraint models. The development of the brass-type texture is best simulated with {111}<110> slip combined with PR/PSA lattice rotation and weak interaction between the grains. The possible volume effect of deformation twins on the formation of the brass-type texture is a controversial question which we discuss on the basis of our simulations as seen together with other investigations.     

Hybrid ZnO/polymer thin films prepared by RF magnetron sputtering

Zinc oxide/poly(acrylic acid) (ZnO/PAA) multilayered hybrid films with different layer thicknesses were prepared by radio frequency magnetron sputtering. Zinc peroxide was used as precursor materials for the preparation of ZnO layers, since the zinc peroxide decomposes to ZnO during the film deposition. The films have a high transmittance in the visible region and exhibit visible photoluminescence emission. The band gap energy of the films—determined by the Tauc relationship—decreases with increasing layer thickness (3.40–3.36 eV) due to the increasing crystalline size of the ZnO particles. The morphological investigations showed that a real layered hybrid film structure formed.     

23种挥发性有机化合物在3种吸附剂上漏出容量的测定评价

采用吸附热解吸－气相色谱－质谱法对23种挥发性有机化合物Chromosorb 106、Tenax TA、Tenax TG等3种吸附剂上漏出容量进行了测定。根据实验结果确定了不同的化合物应选择不同的吸附剂及相应的采样体积。结果表明,Chromosorb 106可较好地吸附低沸点的挥发性有机化合物,Tenax TA、Tenax TG均可用于沸点较高的挥发笥有机化合物吸附,这对测定大气中的有机化合物含量采样有一定的参考价值。     

MOCVD of Fe atoms on H/Si(111) surfaces using Fe-phthalocyanine

Single Fe atoms are deposited on hydrogen-passivated Si(111) surfaces by decomposition of FePc molecules. The metal-organic molecules are evaporated from powder in a heated crucible of an electron beam source. Scanning tunneling microscopy (STM) indicates the incorporation of the central Fe atom of the molecule into H/Si(111) in the near-surface region. This provides a possible precursor state for implantation deeper into the semiconductor substrate.