Electrochemical Treatment for Effectively Tuning Thermoelectric Properties of Free‐Standing Poly(3‐methylthiophene) Films

The degree of oxidation of conducting polymers has great influence on their thermoelectric properties. Free‐standing poly(3‐methylthiophene) (P3MeT) films were prepared by electrochemical polymerization in boron trifluoride diethyl etherate, and the fresh films were treated electrochemically with a solution of propylene carbonate/lithium perchlorate as mediator. The conductivity of the resultant P3MeT films depends on the doping level, which is controlled by a constant potential from ?0.5 to 1.4 V. The optimum electrical conductivity (78.9 S cm^?1 at 0.5 V) and a significant increase in the Seebeck coefficient (64.3 μV K^?1 at ?0.5 V) are important for achieving an optimum power factor at an optimal potential. The power factor of electrochemically treated P3MeT films reached its maximum value of 4.03 μW m^?1 K^?2 at 0.5 V. Moreover, after two months, it still exhibited a value of 3.75 μW m^?1 K^?2, and thus was more stable than pristine P3MeT due to exchange of doping ions in films under ambient conditions. This electrochemical treatment is a significant alternative method for optimizing the thermoelectric power factor of conducting polymer films.     

Folic acid-conjugated GdPO<Subscript>4</Subscript>:Tb<Superscript>3+</Superscript>@SiO<Subscript>2</Subscript> Nanoprobe for folate receptor-targeted optical and magnetic resonance bi-modal imaging

Both fluorescent and magnetic nanoprobes have great potential applications for diagnostics and therapy. In the present work, a folic acid-conjugated and silica-modified GdPO₄:Tb³⁺ (GdPO₄:Tb³⁺@SiO₂-FA) dual nanoprobe was strategically designed and synthesized for the targeted dual-modality optical and magnetic resonance (MR) imaging via a facile aqueous method. Their structural, optical, and magnetic properties were determined using transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR), ultraviolet-visible spectra (UV-Vis), photoluminescence (PL), and superconducting quantum interference device (SQUID). These results indicated that GdPO₄:Tb³⁺@SiO₂-FA were uniform monodisperse core-shell structured nanorods (NRs) with an average length of ~200 nm and an average width of ~25 nm. The paramagnetic property of the synthesized GdPO₄:Tb³⁺@SiO₂-FA NRs was confirmed with its linear hysteresis plot (M-H). In addition, the NRs displayed an obvious T₁-weighted effect and thus it could potentially serve as a T₁-positive contrast agent. The NRs emitted green lights due to the ⁵D₄ → ⁷F₅ transition of the Tb³⁺. The in vitro assays with NCI-H460 lung cancer cells and human embryonic kidney cell line 293T cells indicated that the GdPO₄:Tb³⁺@SiO₂-FA nanoprobe could specifically bind the cells bearing folate receptors (FR). The MTT assay of the NRs revealed that its cytotoxicity was very low. Further in vivo MRI experiments distinctively depict enhanced anatomical features in a xenograft tumor. These results suggest that the GdPO₄:Tb³⁺@SiO₂-FA NPs have excellent imaging and cell-targeting abilities for the folate receptor-targeted dual-modality optical and MR imaging and can be potentially used as the nanoprobe for bioimaging.     

Influence of grain size on luminescence properties of micro- and nanopowder Zn2V2O7 vanadate

Micro- and spongiform nanocrystalline Zn₂V₂O₇ compounds were synthesized by hydrothermal and solid-state reaction techniques, and their morphological features were investigated by scanning electron microscopy (SEM). The grain size ranges of the produced powders were 3–15, 0.5–2 μm, and 50–500 nm. The luminescence spectra of these compounds were measured under pulse cathode beam and photoexcitation (200–400 nm). The luminescence decay properties of Zn₂V₂O₇ were studied.It is found that the intensity, maximum position of luminescence spectra and luminescence decay time of Zn₂V₂O₇ samples depend considerably on the grain size of the synthesized powders. The processes of energy relaxation in Zn₂V₂O₇ and the observed size effect on the luminescence properties are also discussed.     

Synthesis and the effect of alkyl chain length on optoelectronic properties of diarylethene derivatives

Photochromic symmetrical diarylethene derivatives 1a-6a bearing different long alkyl chains at 2-position of thiophene rings have been synthesized and their structures have been determined by single-crystal X-ray diffraction analysis. The effect of alkyl chain length on their optoelectronic properties, such as photochromism in solution as well as in the crystalline phase and electrochemical performance was investigated in detail. These diarylethenes have showed good photochromic behavior both in solution and in the single crystalline phase. Introduction of the long alkyl chains at 2-position of bis(5-formyl-3-thienyl)perfluorocyclopentene increased the absorption coefficients of both open- and closed-ring isomers and induced bathochromic shifts of the maximal wavelength absorption of the closed-ring isomers. The long alkyl chains can also decrease the cyclization/cycloreversion quantum yields and the oxidation potentials. The cyclic voltammetry indicated that the band gap of these diarylethene derivatives was significantly affected by the alkyl chain length.     

三维各向同性谐振子的几何动量分布

尽管几何动量最初的引入是为了描述超面上的运动粒子的动量,却不需要限制在真实的曲面上.如果一个曲线坐标系包含了超面族和超面上的法向矢量作为一个坐标轴的单位矢量,几何动量可以定义在超面族上,并参与构造对易力学量完全集.在三维各向同性谐振子中,采用球坐标描述,存在等效球面,并在球面族上建立对易力学量完全集.因此,三维各向同性谐振子同时具有动量和几何动量分布.这两个动量的差,可以定义为径向动量,从而使得径向动量可以测量.那么,通过几何动量,可以显示出狄拉克引进的径向动量的物理意义,而不是一直认为的那样完全不具有观测意义.     

Investigation of electronic properties of alloyed double metal ring

The present work is a theoretical study of the electronic properties of alloyed double metal ring (ADMR) threaded by magnetic flux. The studied system is consisting of two rings connected parallel, with two different types of atomic sites. This work contains two parts. First is an analytical study of calculation of the energy spectrum, persistent current, Drude weight and low-field magnetic susceptibility of ADMR by the tight-binding method. Second is a computation study of electronic properties of the alloyed double metal ring by density functional theory (DFT). The latter part is considered as a complementary study of what was studied in the first part in order to determine the best materials which will be used to design alloyed double metal ring. Our results show that the on-site energies for both types of atoms, inter-ring coupling strength and hopping strengths play an interesting role in controlling the electronic properties.     

锂离子电池Sb基负极材料研究进展

Sb基材料作为一类合金机制的锂离子电池负极材料,因具有比容量高、安全性好等优点受到广泛关注。 然而,由于Sb基负极材料在充放电过程中的体积效应和本身导电性较差等问题导致的循环性能不理想,制约了其作为锂离子电池负极材料的商业化应用。 本文综述了近年来在锂离子电池Sb基各类负极材料方面的研究进展,重点介绍了它们的反应机理、合成方法及电化学性能,并对Sb基负极材料的发展方向进行了展望。     

Photochromism of new unsymmetrical diarylethenes with a quinoline moiety

Three unsymmetrical diarylethenes with a 6‐membered quinoline moiety were synthesized to investigate the effects of the substituents on their photochromism, and fluorescence, and the structure of one diarylethene was determined by single crystal X‐ray diffraction analysis. Quinoline was connected directly to the central perfluorocyclopentene ring as an aryl moiety and available to participate in photoisomerization reaction in solution, amorphous films, and crystalline phase. These diarylethenes exhibited good photochromism with excellent thermal stability and obvious fatigue resistance. The electron‐donating methoxy group could enhance the absorption maxima of closed‐ring isomers and the quantum yields of cyclization and cycloreversion, but the electron‐withdrawing trifluoromethyl had an opposite effect. In addition, they functioned as notable fluorescence switches in both solution and polymethylmethacrylate films, and the trifluoromethyl group and the methoxy group both increased the emission intensity. The results revealed that the quinoline moiety and substituents played a vital role in the process of photoisomerization reactions for these diarylethenes.     

基于成本效用分析的电能替代实证研究

近年来的雾霾让人们逐渐意识到环境保护的重要性,国网公司基于我国“多煤、少气、贫油”的国情,提出了以电代煤的电能替代方案。本文以在电力和煤炭的使用过程中可获得的热值作为效用,以使用过程中所需要的年费用作为成本,建立了电能替代的成本效用模型,计算出实现电力和煤炭相互替代的排污费临界值,并通过一个算例进行了实证分析。分析结果表明:电价、单位电力排污量、燃煤设备寿命对排污费临界值有正向影响;煤价、单位燃煤排污量、电力设备寿命对其有负向影响。最后,在分析的基础上给出了电能替代的政策建议。     

Photochromism of new unsymmetrical isomeric diarylethenes bearing a methoxyl group

Three new unsymmetrical isomeric diarylethenes having a methoxyl substituent at ortho‐, meta‐, and para‐position of the terminal benzene ring, namely 1‐(2,5‐dimethyl‐3‐thienyl)‐2‐[2‐methyl‐5‐(2‐methoxylphenyl)‐3‐thienyl]perfluorocyclopentene ( 1o ), 1‐(2,5‐dimethyl‐3‐thienyl)‐2‐[2‐methyl‐5‐(3‐methoxylphenyl)‐3‐thienyl]perfluorocyclopentene ( 2o ), and 1‐(2,5‐dimethyl‐3‐ thienyl)‐2‐[2‐methyl‐5‐(4‐methoxylphenyl)‐3‐thienyl]perfluorocyclopentene ( 3o ), have been synthesized. The substituent position effect of methoxyl group on their properties, including photochromism and fluorescence both in hexane solution and in PMMA film, and their electrochemical properties, were investigated in detail. These diarylethenes showed good photochromism both in solution and in PMMA film. For the same photochromic diarylethene backbone, the electron‐ donating methoxyl substituent can effectively depress the cyclization quantum yields and increase the cycloreversion quantum yields compared to those of diarylethenes bearing chlorine atoms reported previously. Diarylethenes 1o – 3o showed clear fluorescent switches by photoirradiation both in hexane and in PMMA film. In addition, cyclic voltammetry tests showed that the electron‐donating methoxyl group at different position on the terminal benzene ring had a significant effect on the electrochemical properties of these isomeric diarylethenes. Copyright © 2009 John Wiley & Sons, Ltd.