新型二硫纶·菲咯啉-5，6-二酮合铜(Ⅱ)配合物的磁性研究

报道了新合成的二氰基二硫纶·菲咯啉-5，6-二酮合铜(Ⅱ)配合物CuLL′(L=mnt^2-, 1,2-dicyano-1,2-ethylenedithiolate; L′=phen-5，6-dione, 1,10-phenanthroline-5,6-dione)的变温磁化率和电子顺磁共振波谱表征结果. 发现微晶粉体型的标题配合物CuLL′具有一定的顺磁性，形成四配位的近似于方形的结构. 探讨了这种配合物磁学特性与结构的关系.     

Synthesis under Micromave Irradition and Crystal Structure of 4''-Acetylbenzo-15 -crown-5thiosemicarbazone

The title compound is a bifunctional receptors including a thiourea group and a crown ether ring. Due to many possible potentials as a new class of reagents for membrane transports,ion-selective electrodes as well as reaction catalysts, the design and synthesis of bifunctional receptors for simultaneous binding of cations and anions is of ongoning interest in srprarnolecular chemistry1-5. In bifunctional receptors, the binding sites for anions and cations are covalently linked so as to exhibit allosteric or cooperative complexation where the binding affinity for anions(cations)is modified as a result of the cation(anion) complexation.Literature[6] reported that the ability of the thiourea group to bind anions is significantly enhanced when Na+ is bound to the crown moiety. To date, however only a few receptors of this class have been reported.6-8In this paper, we report an improved procedure under microwave irradiation that gives higher yields of title compound and needs fewer reaction times than traditional method.The structure of this compound was determined by IR ,element analysis and X-ray analysis.Scheme 1 The reaction equationThe crystal belongs to triclinic crystal system, P-1 space group, a=0.9547(0)nm, b=1.3637(3)nm,c=1.6029(3)nm, α =75.33(3) , β =83.62(3) , γ =70.99(3) ,Z=4,Dc=1.335g/cm3,F(000)=816,R1= 0.0557 ,wR2=0.1281. It is assembled into a three-dimensionalsupramolecule by intermolecular hydrogen bonds.     

One-pot Synthesis of 2, 5-Disubstituted Oxazoles Using Poly[styrene（iodosodiacetate）]

2,5-Disubstituted oxazoles were prepared conveniently by treatment of aromatic α-methyl ketones and nitriles with poly[styrene(iodosodiacetate)] in one-pot process.     

Isolation of 2-Chloro-5-methylpyridine from its Isomer 2-Chloro-3-methylpyridine by Formation of its Copper(II) Complex

2-Chloro-5-methylpyridine is an important intermediate for the preparation of biological active compounds, especially insecticides1, e.g. imidacloprid2, and is usually manufac- tured from 3-methylpyridine N-oxide. However, the manufacturing process also forms the by-products: 3-methylpyridine and its isomer 2-chloro-3-methylpyridine3. The pro- perties of the isomers are similar, it is difficult to separate by ordinary methods, such as distillation. Scheme 1 79.4%13.6%5.2%NClCH3NCH3ClNC…     

Thinking and Turing's test

The questions raised by A. M. Turing in his paper on thought and machines are discussed. Human thought is considered in turn as a concept of normal language usage, as a basic concept of psychology, and as the basis of intellectual activity. It is concluded that neither of these notions of thought identifies something specific that a human being can or cannot do. The imitation game proposed by Turing for deciding whether a machine can think is found to result from an arbitrary empoverishment of the channel of communication between the interrogator and the item under investigation. Turing's notions of thinking are shown to lead to logical difficulties. An alternative view of consciousness, that would place it beyond the reach of any finite test, is finally discussed.     

Effect of borohydride as reducing agent on the structures and electrochemical properties of Pt/C catalyst

In this paper, we found that boron deposited on the surface of support when sodium borohydride used as reducing agent during the preparation of Pt/C catalyst. The deposition of boron markedly reduces particle size of Pt, raises electrochemical active surface (EAS) area of catalyst and electrochemical activity for hydrogen evolution or oxygen reduction reaction (ORR) compared with which prepared using other reducing agents (hydrogen and formaldehyde).     

Influence of organic modifiers on morphology and crystallization of poly(ϵ‐caprolactone)/synthetic clay intercalated nanocomposites

ε‐caprolactone was polymerized in the presence of neat montmorillonite or organomontmorillonites to obtain a variety of poly(ε‐caprolactone) (PCL)‐based systems loaded with 10 wt % of the silicates. The materials were thoroughly investigated by different X‐ray scattering techniques to determine factors affecting structure of the systems. For one of the nanocomposites it was found that varying the temperature in the range corresponding to crystallization of PCL causes reversible changes in the interlayer distance of the organoclay. Extensive experimental and literature studies on this phenomenon provided clues indicating that this effect might be a result of two‐dimensional ordering of PCL chains inside the galleries of the silicate. Small angle X‐ray scattering and wide angle X‐ray scattering investigation of filaments oriented above melting point of PCL revealed that polymer lamellae were oriented perpendicularly to particles of unmodified silicate, while in PCL/organoclay systems they were found parallel to clay tactoids. Calorimetric and microscopic studies shown that clay particles are effective nucleating agents. In the nanocomposites, PCL crystallized 20‐fold faster than in the neat polymer. The crystallization rate in nanocomposites was also significantly higher than in microcomposite. Further research provided an insight how the presence of the filler affects crystalline fraction and spherulitic structure of the polymer matrix in the investigated systems. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2350–2367, 2007     

Photoelectron spectroscopic study of Li oxides on Li over-deposited V2O5 thin film surfaces

The Li oxides species formed on Li over-deposited V₂O₅ thin film surfaces have been studied by using X-ray and UV induced photoelectron spectroscopy (XPS and UPS). The photoelectron spectroscopic data show that the Li over-deposited V₂O₅ system itself is not stable. Further chemical decomposition reactions are taken place even under UHV conditions and lead to form Li₂O and Li₂O₂ compounds on the surface. The formation of Li₂O₂ causes to arise an emission line at about 11.3 eV in the valence band spectra.     

Association Behavior of 4-Acylpyrazolone Derivative and Tertiary Amine of High Molecular Weight in Antagonistic Synergistic Extraction of Palladium

To find an effective extraction and removal method for palladium(II), which is one of the main fission products from an acidic nuclear spent fuel solution, the extraction behavior of palladium(II) from a nitric acid medium by an acidic chelating extractant, 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5-one (HPMTP) and a tertiary amine of high molecular weight, tri-n-octylamine (TOA), has been studied by spectrophotometry. A noticeable antagonistic extraction effect was observed in the extraction system under the given conditions. To understand this phenomenon, a preliminary investigation was performed to explain the mechanism of this reaction. According to the theory of corresponding solutions (TCS), the association reaction between HPMTP and TOA is proposed in the organic phase. An associated species, HPMTP·TOA, formed through hydrogen bonding in a chloroform medium might be the main reason why an antagonistic extraction effect occurred. The association constant between HPMTP and TOA was calculated to be 2.86±0.05.     

Transition‐metal‐catalyzed reactions of 5‐methylene‐2‐oxazolidinone and 5‐methylene‐1,3‐thiazolidine‐2‐thione with isocyanates

5‐Methylene‐2‐oxazolidinone (1) and 5‐methylene‐1,3‐thiazolidine‐2‐thione (4) react with various isocyanates to give the corresponding urethanes 3 and 5 in high yields in the presence of palladium(0) or palladium(II) catalyst under mild reaction conditions. A mechanism is proposed. Copyright © 2003 John Wiley & Sons, Ltd.