Copper(II) diamino acid complexes: quantum chemical computations regarding diastereomeric effects on the energy of complexation

[reaction: see text] Quantum chemical calculations were used to rationalize the observed enantiodifferentiation in the complexation of alpha-amino acids to chiral Cu(II) complexes. Apart from Cu(II)[bond]pi interactions and steric repulsions between the anchoring cholesteryl-Glu moiety and an aromatic amino acid R group, hydrogen bonding also plays a role. In fact, in the case of tryptophan, C[double bond]O...H[bond]N hydrogen bonding between the glutamate moiety and the tryptophan N[bond]H group compensates for the loss of intramolecular hydrogen-bonding and diminished Cu(II)[bond]pi interactions.     

Fabrication of hollow palladium spheres and their successful application to the recyclable heterogeneous catalyst for suzuki coupling reactions

Novel palladium hollow spheres were synthesized using silica spheres as a template, and they were successfully applied as recyclable heterogeneous catalysts for Suzuki cross coupling reactions.     

Synthesis of pyrimido[4,5-e][1,4]oxazepin-5-ones

Eighteen novel pyrimido[4,5-e][1,4]oxazepin-5-ones were prepared directly via the reaction of either ethyl 4-chloro-2-phenyl-5-pyrimidinecarboxylate (Ia) or ethyl 4-chloro-2-m-chlorophenyl-5-pyrimidinecarboxylate (Ib) with a variety of substituted 2-(alkylamino)ethanols. A typical example was the preparation of 8,9-dihydro-9-methyl-2-phenylpyrimido[4,5-e][1,4]-oxazepin-5(7H)-one (IIa) from the reaction of Ia with 2-(methylamino)ethanol. Hydrolytic cleavage of the lactone ring in IIa with sodium hydroxide solution, followed by acidification with hydrochloric acid afforded 4-[(2-hydroxyethyl)methylamino]-2-phenyl-5-pyrimidinecarboxylic acid (IV). Reactions of IIa with concentrated ammonium hydroxide or hydrazine also caused cleavage of the lactone ring, giving the corresponding amide (V) or hydrazide (VI), respectively. Structural assignments were supported by infrared and nuclear magnetic resonance spectra.     

贮氢材料电极循环寿命的定量预测定时放电半衰期法的应用

贮氢材料电极循环寿命的定量预测定时放电半衰期法的应用韩剑文，袁满雪，周作祥，赖城明（南开大学化学系天津３０００７１）关键词：贮氢电极，循环寿命，半衰期。前文￣［１］讨论了应用定终点电位放电半衰期法来预测贮氢材料电极循环寿命的问题。本文讨论如何采用定时...     

Qualitative features of the two-dimensional Raman spectrum in liquids

The theory presented earlier [J. Kim and T. Keyes, Phys. Rev. E 66, 051110 (2002)] is analyzed to determine the information available from the two-dimensional Raman spectrum R((5))(t(2),t(1)) in liquids. The known spectra are well represented by the sum of two products of ordinary time correlations predicted by the theory. The shape of R((5)) is related in general to the values of simple same-time averages and concepts amenable to physical intuition. Using standard models for the time correlations entering the theory, specific analytic expressions for the spectrum are obtained depending on two parameters and a time scale, and the behavior of the spectrum is mapped out in the parameter space.     

A Facile Construction of the Quadranoid Skeleton: Application to the Total Synthesis of (+/-)-Suberosenone

A tandem free radical cyclization-rearrangement sequence was designed and executed to produce tricyclo[4.3.2.0(1,5)]undecane 7 from cyclopentene 6A in a single operation. The total synthesis of suberosenone was accomplished from 7.     

Improving catalyst scope: use of multiple aniline substrates to optimize a palladium-catalyzed bisdiene cyclization

[reaction: see text] Combinatorial screening of five catalyst precursors and nine ligands with three substituted aniline trapping reagents uncovered a catalyst system that promotes efficient palladium-catalyzed cyclization-trapping with a series of substituted anilines of varying steric and electronic character. The results of the parallel optimization study illustrate the interdependency of the key reaction variables.     

Intramolecular Diels-Alder Reactions of Decatrienoates: Remote Stereocontrol and Conformational Activation(1)

The intramolecular Diels-Alder (IMDA) reactions of C(8)-substituted decatrienoates have been studied. The stereospecific formation of 11 via an endo-boat-9 transition state attests to the powerful directing influence of a C(8) substituent in the IMDA of decatrienoate. In addition, the contrasting observations that stereospecific 9 --> 11 occurs at room temperature while the nor-tert-butyl substrate (4a) requires 125 degrees C/5 h reaction conditions and produces a 60:40 mixture of diastereomers provide clear evidence that a bulky C(8) substituent is a powerful conformational activator of the IMDA.     

Correlating second harmonic optical responses of single Ag nanoparticles with morphology

Femtosecond laser excited second harmonic (SH) activity from single Ag nanoparticles is reported. A correlation of SH single-particle measurements with high-resolution imaging of particle morphology by TEM was achieved by creating position markers on an optical and electron transparent substrate (Si3N4 thin film, approximately 100 nm). We compared the SH activity of single Ag nanoparticles (nanospheres versus nanorods) and cluster structures (composed of two or multiple particles, e.g., dimers and trimers). The direct correlation of single-particle structures and SH activity, spectral and power dependence, strongly suggests one-photon resonant driven nonlinear oscillator response mechanism.     

Influence of extended π-conjugation units on carrier mobilities in conducting polymers

Carrier mobilities in thin films of copolymers with repeat units consisting of oligothiophenes bridged by Si atoms are measured over a range of doping levels, where the numbers of thienylenes in the repeat unit are 7, 8, 10, 12, and 14. The mobilities for these polymer films increased with the increase in doping level and the mobility enhancement followed an increasing order of the π-conjugation length. The magnitude of the mobility increase for the Si polymer comprising 14 thiophene units reached ca. 10⁴, implying that this π-conjugation length is almost sufficient to reproduce transport properties of polythiophenes.