Absorption measurements in dense cesium vapor using a UV–violet light-emitting diode

We present results of absorption measurements in a dense superheated cesium vapor generated in an all-sapphire cell using a UV–violet light-emitting diode as a continuum source. Due to the very effective thermal destruction of Cs₂ molecules, a number of diffuse and satellite bands appear around higher members of cesium principal series lines, which are not easily visible in saturated cesium vapor. From the temperature dependence of the diffuse features we can distinguish short-range singlet transitions from temperature-independent spectral features that stem either from a shallow lowest triplet state or from the long-range photo association spectra of triplet or singlet Cs₂ molecules. The limits of the present interpretation of the observed bands in the UV–violet spectral region are discussed. Received: 25 May 2000 / Revised version: 20 September 2000 / Published online: 13 December 2000     

硬脂酸单分子膜上电沉积Ag膜的研究

通过电沉积方法,以气/液界面上形成的硬脂酸单分子膜为模板诱导沉积金属银膜.考察了镀液pH值、单分子膜表面压及沉积电位对银膜形貌及结构的影响.实验发现,酸性镀液的气/液界面上形成的单分子膜不能诱导沉积银,而在中性和碱性镀液的气/液界面上可以诱导银膜的生长.当单分子膜处于液态或固态时,气/液界面有银膜形成;液态单分子膜上的银膜生长速度较快,且银膜的结构一致.随着电极电位的升高,银膜沉积的速度加快,呈环状向外生长的圆形银膜逐渐变得不规则.将不同实验条件下的银膜转移出来,采用扫描电镜(SEM)、透射电镜(TEM)对银膜的结构与形貌进行了表征.研究表明,银首先在单分子膜上异相成核,由八面体构型逐渐发展成星型,最终在气/液界面形成具有松枝状微观结构的光亮银膜.     

Hydrothermal synthesis of highly water-dispersible anatase nanocrystals from transparent aqueous sols of titanate colloids

Transparent colloidal aqueous solutions of anatase nanocrystals were hydrothermally synthesized from aqueous transparent sols with tetramethylammonium titanate colloids, the surfaces of which were modified with citric acid, by structural conversion of the titanate to anatase. This modification hindered coalescence of the titanate colloids during the hydrothermal synthesis. Although the amount of citric acid adsorbed on the colloids was reduced during hydrothermal treatment, a small amount of citric acid was adsorbed on the resulting anatase nanocrystals. Moreover, the use of the titanate colloids as a precursor was compared with the use of a citrato Ti complex, tetramethylammonium citratotitanate. The hydrothermal treatment of the transparent aqueous solutions of the Ti complex yielded opaque solutions with large anatase colloids, suggesting that the titanate colloids were useful for preparing transparent anatase colloidal solutions. Because the shape and size of resulting colloids may be dependent on the size and shape of starting colloids, the use of titanate colloids as a precursor may make it easy to control size and shape of anatase colloids.     

Highly thermostable and low birefringent norbornene‐styrene copolymers with advanced optical properties: A potential plastic substrate for flexible displays

This article reports the synthesis and characterization of an extremely high thermostable cyclic olefin copolymer with advanced optical properties resulting from the vinyl addition copolymerization of norbornene with styrene catalyzed by a substituted fluorenylamidodimethyltitanium catalyst [Me₂Si(3,6‐tBu₂Flu)(tBuN)]TiMe₂ activated with a [Ph₃C] [B(C₆F₅)₄]/Al(iBu)₃ cocatalyst using o‐dichlorobenzene as solvent. The prepared copolymer possesses a glass transition temperature as high as polyimide (T_g > 300 °C) and a high transmittance which is comparable with that of the conventional optical resins ([T] > 90%). The incorporation of polystyrene, which exhibits a negative birefringence into the vinyl‐added polynorbornene that possesses an intrinsic positive birefringence, effectively reduced the birefringent magnitude of the norbornene‐styrene copolymer due to a mutual compensation between these opposite‐sign birefringences. The absence of any functional and aromatic heterocyclic groups and the presence of highly hydrophobic saturated bicyclic rings in the copolymer main chains effectively prevented the diffusion of water/oxygen and thus enhanced the dimensional and optical stabilities of the material. Preliminary results on the characterization of the thermal stability, mechanical, and optical properties of the vinyl‐added norbornene‐styrene copolymers indicate that they satisfy all the rigorous requirements for a polymer to be applied as a flexible substrate for the manufacturing of the flexible displays. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Asymmetric Synthesis of Indoline from Achiral Phthalimide Involving Crystallization-Induced Deracemization

Asymmetric synthesis was performed by combining the photochemical reaction of an achiral substrate followed by crystallization-induced deracemization. The results indicated that a fused indoline produced by photochemical intramolecular δ-hydrogen abstraction and cyclization of N-(5-chloro-2-methylphenyl)phthalimide crystallized as a racemic conglomerate. Since this substrate has an aminal skeleton, racemization involving a ring-opening and ring-closing equilibrium process occurred under suitable conditions. Efficient racemization was observed in acetone containing a catalytic base, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Crystallization-induced dynamic deracemization by Viedma ripening from racemic indoline was performed with an excellent enantioselectivity of 99 % ee. Furthermore, one-pot asymmetric synthesis of the indoline was achieved by the photochemical reaction of achiral phthalimide followed by continuous attrition-enhanced deracemization converging to 99 % ee of enantiomeric crystals. This is the first example of asymmetric expression and amplification by photochemical hydrogen abstraction and crystallization-induced dynamic deracemization.     

Synthesis of cyclo‐olefin copolymer latexes and their carbon nanotube composite nanoparticles

An efficient and environmentally benign synthetic method for the production of the stabilized cyclo‐olefin copolymer latexes and their carbon nanotube composite nanoparticles has been developed using an emulsion ring opening metathesis copolymerization catalyzed by the 2nd generation Grubbs catalyst in aqueous solution. Homopolymerizations of norbornene (NB) and dicyclopentadiene (DCPD) in aqueous solution yield unstable polymer latexes in combination with a large amount of their flocculation fractions. Copolymerizations of NB or DCPD with a selected liquid cyclo‐olefin comonomer dramatically improve not only the colloidal stability of the copolymer latexes but also the thermal stability of the copolymer nanoparticles. The liquid cyclo‐olefin comonomer plays a double role as a liquefied agent for the solid NB and DCPD monomers before the emulsification treatment, and a reactive comonomer itself to control entirely the copolymerization system. The as‐prepared cyclo‐olefin copolymer latexes exhibit an exceptionally high compatibility with a well‐dispersed carbon nanotube (CNT) in aqueous solution due to strong π–π interactions between the graphitic surfaces of the CNT with the C‐C double bonds located on the cyclo‐olefin copolymer main chains. Accordingly, a binary blending of these two well‐dispersed colloidal systems in aqueous solution led to the fabrication, for the first time, of the highly electrical conductive cyclo‐olefin copolymer/CNT composite nanoparticles. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4584–4591     

A practical synthesis of a new series of isoflavanones

A practical six-step synthesis of 12 methylated and hydroxylated isoflavanones was accomplished starting from readily available m-xylene.A significant improvement of this procedure included application of the simple and commercially available reagents,avoidance of expensive reagents and catalysts,simple operations and excellent yields.     

Nonlinear growth in weighted networks with neighborhood preferential attachment

We propose a nonlinear growing model for weighted networks with two significant characteristics: (i) the new weights triggered by new edges at each time step grow nonlinearly with time; and (ii) a neighborhood local-world exists for local preferential attachment, which is defined as one selected node and its neighbors. Global strength-driven and local weight-driven preferential attachment mechanisms are involved in our model. We study the evolution process through both mathematical analysis and numerical simulation, and find that the model exhibits a wide-range power-law distribution for node degree, strength, and weight. In particular, a nonlinear degree–strength relationship is obtained. This nonlinearity implies that accelerating growth of new weights plays a nontrivial role compared with accelerating growth of edges. Because of the specific local-world model, a small-world property emerges, and a significant hierarchical organization, independent of the parameters, is observed.