Efficient synthesis of an aldehyde‐capped polythiophene containing fluorinated electron‐withdrawing groups

To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007     

Chemical synthesis and electric properties of the conducting copolymer of aniline and o‐aminophenol

A copolymer, poly(aniline‐co‐o‐aminophenol), was prepared chemically by using ammonium peroxydisulfate as an oxidant. The monomer concentration ratio of o‐aminophenol to aniline strongly influences the copolymerization rate and properties of the copolymer. The optimum composition of a mixture for the chemical copolymerization consisted of 0.3 M aniline, 0.021 M o‐aminophenol, 0.42 M ammonium peroxydisulfate, and 2 M H₂SO₄. The result of cyclic voltammograms in a potential region of ?0.20 to 0.80 V (vs.SCE) indicates that the electrochemical activity of the copolymer prepared under the optimum condition is similar to that of polyaniline in more acid solutions. However, the copolymer still holds the good electrochemical activity until pH 11.0. Therefore, the pH dependence of the electrochemical property of the copolymer is improved, compared with poly(aniline‐co‐o‐aminophenol) prepared electrochemically, and is much better than that of polyaniline. The spectra of IR and ¹H NMR confirm that o‐aminophenol units are included in the copolymer chain, which play a key role in extending the usable pH region of the copolymer. The visible spectra of the copolymers show that a high concentration ratio of o‐aminophenol to aniline in a mixture inhibits the chain growth. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5573–5582, 2007     

RANDOM EDGE can be exponential on abstract cubes

We prove that RANDOM EDGE, the simplex algorithm that always chooses a random improving edge to proceed on, can take a mildly exponential number of steps in the model of abstract objective functions (introduced by Williamson Hoke [Completely unimodal numberings of a simple polytope, Discrete Appl. Math. 20 (1988) 69-81.] and by Kalai [A simple way to tell a simple polytope from its graph, J. Combin. Theory Ser. A 49(2) (1988) 381-383.] under different names). We define an abstract objective function on the n-dimensional cube for which the algorithm, started at a random vertex, needs at least exp(const·n^1/3) steps with high probability. The best previous lower bound was quadratic. So in order for RANDOM EDGE to succeed in polynomial time, geometry must help.     

Structural and magnetic properties of RF sputtered FePt/Fe multilayers

Series of [FePt(4min)/Fe(t_Fe)]₁₀ multilayers have been prepared by RF magnetron sputtering and post-annealing in order to optimize their magnetic properties by structural designs. The structure, surface morphology, composition and magnetic properties of the deposited films have been characterized by X-ray diffractometer (XRD), Rutherford backscattering (RBS), scanning electron microscope (SEM), energy dispersive X-ray spectroscope (EDX) and vibrating sample magnetometer (VSM). It is found that after annealing at temperatures above 500 °C, FePt phase undergoes a phase transition from disordered FCC to ordered FCT structure, and becomes a hard magnetic phase. X-ray diffraction studies on the series of [FePt/Fe]_n multilayer with varying Fe layer thickness annealed at 500 and 600 °C show that lattice constants change with Fe layer thickness and annealing temperature. Both lattice constants a and c are smaller than those of standard ones, and lattice constant a decreases as Fe layer deposition time increases. Only a slight increase in grain size was observed as Fe layer decreased in samples annealed at 500 °C. However, the increase in grain size is large in samples annealed at 600 °C. The coercivities of [FePt/Fe]_n multilayers decrease with Fe layer deposition time, and the energy product (BH)_max reaches a maximum in the samples with Fe layer deposition time of 3 min. Comparison of magnetic properties with structure showed an almost linear relationship between the lattice constant a and the coercivities of the FePt phase.     

A matricial corona theorem II

We extend the ``matricial corona theorem' of M. Andersson to general algebras of functions which satisfy a corona theorem.

     

Observation of spontaneous pattern with six-fold symmetry in disk-shaped ZnO complex microstructures

Using a simple vapor phase transport technique, we have fabricated unique complex disk-shaped ZnO microstructures comprising a small disk coaxially grown on a large one and observed spatially perfect six-fold symmetric patterns. The observed results can be explained based on the spontaneous nanoindentation (NI) effect under the geometric constraints and the explanation can be extended to fathom the growth mechanism of other highly symmetrical ZnO nanostructures. Our results indicate that NI not only can elucidate the mechanical properties of surfaces and thin films but also is an effective approach to fabricate ordered nanostructures with high precision on the location of the building blocks. PACS 81.16.Rf; 81.07.-b; 81.05.Dz     

γ-LiAlO2晶体生长、改性和热学性质研究

采用快速提拉法生长出了透明、完整的γ-LiAlO2晶体,但是晶体的高熔点和易挥发性限制了γ-LiAlO2晶体质量.采用气相传输平衡法(vapor transport equilibration technique,VTE)工艺对晶体改性,半高宽(FWHM)值从116.9arcsec降至44.2arcsec,继续升高VTE处理温度至1300℃,FWHM值反而升高至55.2arcsec.快速提拉法生长出来晶体,[100]方向和[001]方向的热膨胀系数分别为17.2398×10-6/K,10.7664×10-6/K.经过三步VTE处理后[100]和[001]方向热膨胀系数降至16.6539×10-6/K和10.1784×10-6/K.     

Synthesis and characterization of highly fluorescent europium functionalized β-diketonate complexes

Several functionalized β-diketones and their europium complexes have been synthesized and characterized. The UV-Vis absorption, photoluminescent spectra, thermal and electrochemical properties of these complexes were investigated. The thermal analysis shows that the complexes have good thermal stability. By introducing the number of extended phenyl rings we succeeded in obtaining europium complexes with extremely high photoluminescent quantum yield (PLQY) in solution due to strong site isolation effect.     

The Matsumoto-Yor property and the structure of the Wishart distribution

This paper establishes a link between a generalized matrix Matsumoto-Yor (MY) property and the Wishart distribution. This link highlights certain conditional independence properties within blocks of the Wishart and leads to a new characterization of the Wishart distribution similar to the one recently obtained by Geiger and Heckerman but involving independences for only three pairs of block partitionings of the random matrix.In the process, we obtain two other main results. The first one is an extension of the MY independence property to random matrices of different dimensions. The second result is its converse. It extends previous characterizations of the matrix generalized inverse Gaussian and Wishart seen as a couple of distributions.We present two proofs for the generalized MY property. The first proof relies on a new version of Herz's identity for Bessel functions of matrix arguments. The second proof uses a representation of the MY property through the structure of the Wishart.