新型氧离子导体La2Mo1.8Ga0.2O9陶瓷的合成及其电性能

通过高温固相合成法首次合成了La₂Mo_1.8Ga_0.2O₉陶瓷样品. 粉末XRD结果表明, 该样品为单一立方相La₂Mo₂O₉结构. 以陶瓷样品为固体电解质、多孔性铂为电极, 采用交流阻抗谱、气体浓差电池、氧泵等方法研究了样品在600～1000 ℃下各种气氛中的离子导电特性. 结果表明, 氧浓差电池电动势的实测值与理论值吻合得很好, 氧离子迁移数为1, 表明该陶瓷样品在该温度下氧气气氛中为一纯氧离子导体; 氧泵(氧的电化学透过)实验结果进一步证实了该样品在氧气气氛中为一纯氧离子导体; 在氧分压p(O₂)＝10^－5～10⁵ Pa的高氧分压气氛中, 电导率与氧分压变化基本无关, 表明在该氧分压范围内样品为纯离子导体, 这与氧浓差电池电动势测定结果相吻合; 在低氧分压为10^－5～10^－15 Pa范围内, 总电导率随氧分压降低而稍有升高, 表明在该氧分压范围样品为氧离子与电子的混合导体; 在600～1000 ℃下氧离子电导率＞10^－2 S•cm^－1, 显著高于母体La₂Mo₂O₉的氧离子电导率, 1000 ℃时的氧离子电导率为0.07 S•cm^－1.     

The exact bound in the Erdös-Ko-Rado theorem

This paper contains a proof of the following result: ifn≧(t+1)(k?t?1), then any family ofk-subsets of ann-set with the property that any two of the subsets meet in at leastt points contains at most \(\left( {\begin{array}{*{20}c} {n - t} \\ {k - t} \\ \end{array} } \right)\) subsets. (By a theorem of P. Frankl, this was known whent≧15.) The bound (t+1)(k-t-1) represents the best possible strengthening of the original 1961 theorem of Erdös, Ko, and Rado which reaches the same conclusion under the hypothesisn≧t+(k?t) \(\left( {\begin{array}{*{20}c} k \\ t \\ \end{array} } \right)^3 \) . Our proof is linear algebraic in nature; it may be considered as an application of Delsarte’s linear programming bound, but somewhat lengthy calculations are required to reach the stated result. (A. Schrijver has previously noticed the relevance of these methods.) Our exposition is self-contained.     

An improved method for assay of vitamin C in fish feed and tissues

Summary A method was devised to assay four forms of vitamin C: L-ascorbic acid (AA), dehydroascorbic acid (DHA), ascorbate-2-mono- and polyphosphate (AMP, APP), as well as ascorbate-2-monosulphate (AMS), in sample series of different fish tissues and feed. Direct and indirect detection were combined. Sample extractions were carried out with 0.2 mol L⁻¹ sodium acetate buffer (pH 4.8) and extracts were deproteinized after different chemical or enzymatic reactions, with perchloric acid. The DHA was reduced to AA with dithioerythritol (DTE). Ascorbate oxidase enzyme was used for the detection of background and an acidic phosphatase enzyme for the hydrolysis of different phosphate esters. Ascorbate-2-sulphate was detected directly with help of coinjection of the compound. Chromatographic analysis was carried out with a single column isocratic reverse phase method. The mobile phase was an aqueous buffer of 0.04 M sodium-acetate, 0.05 mM EDTA, 0.5 mM tetrabutylammonium dihydrogen phosphate (TBA) adjusted to pH 3.76 with 85% H₃PO₄ and with 24 mL methanol added to 1000 mL. C-18 columns were used with 0.6 mL min⁻¹ flow rate at 23°C. The vitamin C forms were detected by UV absorption at 250 nm. The determination limit was 1.0–5.0 μg g⁻¹ in AA equivalent. The standard deviations were between 1–6% and depended on the concentrations of vitamin C forms and tissues. Recoveries were between 90–96% in samples. Presented at: Balaton Symposium on High-Performance Separation Methods, Siófok, Hungary, September 3–5, 1997     

Synthesis of a model cyclic triblock terpolymer of styrene,isoprene, and methyl methacrylate

The synthesis of a model cyclic triblock terpolymer [cyclic(S‐b‐I‐b‐MMA] of styrene (S), isoprene (I), and methyl methacrylate (MMA) was achieved by the end‐to‐end intramolecular amidation reaction of the corresponding linear α,ω‐amino acid precursor [S‐b‐I‐b‐MMA] under high‐dilution conditions. The linear precursor was synthesized by the sequential anionic polymerization of S, I, and MMA with 2,2,5,5‐tetramethyl‐1‐(3‐lithiopropyl)‐1‐aza‐2,5‐disilacyclopentane as an initiator and amine generator and 4‐bromo‐1,1,1‐trimethoxybutane as a terminator and carboxylic acid generator. The separation of the unreacted linear polymer from the cyclic terpolymer was facilitated by the transformation of the unreacted species into high molecular weight polymers by the evaporation of the reaction solvent and the continuation of the reaction under high‐concentration conditions. The intermediate materials and the final cyclic terpolymer, characterized by size exclusion chromatography, vapor pressure osmometry, thin‐layer chromatography, IR and NMR spectroscopy, exhibited high molecular weight and compositional homogeneity. Dilute‐solution viscosity measurements were used as an additional proof of the cyclic structure. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1476–1483, 2002     

On a pair of functional equations of combinatorial interest

The equations of the title appear in the author's paper Chromatic Sums for Rooted Planar Triangulations, V: Special Equations. (Canadian Journal of Mathematics, 26 (1974), 893–907). They appear in that paper as Equations (24) and (25). They are simultaneous equations for two unknown functionsl andy ₂ of two variablesy ₁ andz. A parameter is involved. The main result is that for = 2 cos (2/n), wheren is a positive integer >1, the two equations can be reduced to a single equation (numbered (49)). Solutions of this are known forn <7. From such solutions we can expect to get information about the averaged chromatic polynomials of planar triangulations with a given number of triangles.The present work is basically an expository paper on the theory given in Chromatic Sums, V, but it includes some new results and many simplifications.     

On the singular graph and the Weyr characteristic of anM-matrix

LetA be anM-matrix in standard lower block triangular form, with diagonal blocksA _ii irreducible. LetS be the set of indices such that the diagonal blockA is singular. We define the singular graph ofA to be the setS with partial order defined by > if there exists a chain of non-zero blocksA _i, A_ij, , A_l.Let ₁ be the set of maximal elements ofS, and define thep-th level _p ,p = 2, 3, , inductively as the set of maximal elements ofS \( _{1 p-1}). Denote by _p the number of elements in _p . The Weyr characteristic (associated with 0) ofA is defined to be (A) = ( ₁, ₂,, _h ), where ₁ + + _p = dim KerA ^p ,p = 1, 2, , and _h > 0, _h+1 = 0.Using a special type of basis, called anS-basis, for the generalized eigenspaceE(A) of 0 ofA, we associate a matrixD withA. We show that(A) = ( ₁, , _h) if and only if certain submatricesD _p,p+1 ,p = 1, , h – 1, ofD have full column rank. This condition is also necessary and sufficient forE(A) to have a basis consisting of non-negative vectors, which is a Jordan basis for –A. We also consider a given finite partially ordered setS, and we find a necessary and sufficient condition that allM-matricesA with singular graphS have(A) = ( ₁, , _h). This condition is satisfied ifS is a rooted forest.The work of the second-named author was partly supported by the National Science Foundation, under grant MPS-08618 A02.     

Host–Guest Complexation of <Emphasis Type="Italic">β</Emphasis>-, <Emphasis Type="Italic">γ</Emphasis>-Cyclodextrin with Alkyl Trimethyl Ammonium Bromides in Aqueous Solution

As a continuation of our previous investigation, interactions between cyclodextrin (β-CD), γ-cyclodextrin (γ-CD) and alkyl trimethylammonium bromides in aqueous solutions have been studied with titration calorimetry and ¹H NMR at 298.15 K. The results are discussed in terms of the amphiphilic interaction of CD with surfactants and the iceberg structure formed by water molecules existing around the hydrophobic tail of surfactant molecules. The stoichiometry of the β-CD–surfactant system is 1:1 whereas that of the γ-CD–surfactant system is 1:2. The corresponding formation enthalpy (negative) of the complexes of the two systems decreases with an increase in the number of carbon atoms (n) in hydrophobic chain of surfactant molecule, C _n H_2n+1, whereas the entropy increases with the enlargement of n.     

Synthesis of 9-arylamino- and (Z)-9-arylimino-9H-pyrrolo[1,2-a]indoles by reactions of 2-(pyrrol-1-yl)benzaldehydes with aryl amines

Heating mixtures of 2-(pyrrol-1-yl)benzaldehydes and aryl amines under argon afforded 9-arylamino-9H-pyrrolo[1,2-a]indoles, via cyclization of the resulting 2-(pyrrol-1-yl)benzaldimine intermediates. Heating in the presence of oxygen afforded (Z)-9-arylimino-9H-pyrrolo[1,2-a]indoles, which were successfully hydrolyzed with hydrochloric acid to give pyrrolo[1,2-a]indol-9-ones.     

辅酶NAD(P)H模型分子的研究进展

辅酶NAD(P)H在生物体内起着重要的调节作用, 已引起了有机化学工作者极大的兴趣, 尤其是在还原反应的立体选择性上, 人们已经开展了大量的研究工作. 讨论了NAD(P)H模型分子进行立体专一性还原反应的影响因素, 并对NAD(P)H模型分子的研究工作做了总结.     

Spectrophotometric study of the complexation of iodine with 1,7-diaza-15-crown-5 in chloroform solution

The complex formation reaction between iodine and 1,7-diaza-15-crown-5 (DA15C5) has been studied spectrophotometrically in chloroform at 25°C. The resulting 1:2 (DA15C5:I₂) molecular complex was formulated as (DA15C5...;I⁺)I ₃ ^– . The spectrophotometric results, as well as the conductivity measurements, revealed that the gradual release of triiodide ion from its contact ion paired form in the molecular complex into the solution is the rate determining step of the reaction. The rate constant was calculated ask=(8.8±0.2)×10^–3 min^–1. The formation constant of the molecular complex was evaluated from the computer fitting of the absorbance-mole ratio data as logK _f=6.89±0.09.