A high-resolution MAS NMR study on the potential catalysts Mo/HBeta for olefin metathesis: The interaction of Mo species with HBeta zeolite

The interfacial interaction of Mo species with the HBeta zeolite was studied by multinuclear MAS NMR, XRD and N₂ adsorption. As proved by the quantitative ²⁷Al MAS NMR, this interaction is so strong as to dealuminate the framework of HBeta, and leads to a new peak appearing at −14 ppm, which indicates the formation of crystalline Al₂(MoO₄)₃. This can also be detected by XRD measurements when the Mo loading is as high as 9.0 wt.%. The corresponding quantitative ²⁹Si and ¹H MAS NMR spectra show that the amount of silanols and Brønsted acidic sites decrease obviously with increasing Mo loading. This also reveals an interaction between Mo species and HBeta support through an oxygen bridge resulting from condensation with the hydroxyls on the support. At higher Mo loadings, the interaction is so strong that it results in an extraction of aluminum from the zeolite framework, and subsequently appearance of Al₂(MoO₄)₃ and loss of Brønsted acidic sites. These can be correlated to the low catalytic activity of Mo/HBeta in metathesis of ethylene and 2-butylene to propylene.     

STRONG LAW OF LARGE NUMBERS AND ASYMPTOTIC EQUIPARTITION PROPERTY FOR NONSYMMETRIC MARKOV CHAIN FIELDS ON CAYLEY TREES

Some strong laws of large numbers for the frequcncies of occurrence of states and ordered couples of states for nonsymmetric Markov chain fields(NSMC)on Cayley trees are studied.In the proof,a new technique for the study of strong liinit theorems of Markov chains is extended to the case of Markov chain fields.The asymptotic equiparti- tion properties with almost everywhere(a.e.)convergence for NSMC on Cayley trees are obtained.     

DIRICHLET BOUNDARY VALUE PROBLEMS FOR SECOND-ORDER QUASI-LINEAR DIFFERENTIAL EQUATIONS WITH CHANGING SIGN NONLINEARITIES

This paper is concerned with the existence of positive solutions of two-point Dirichlet singular and nonsingular boundary problems for second-order quasi-linear differential equations with changing sign nonlinearities.     

Synthesis and Structural Characterization of Adduct [La(NO_3)_3·4H_2O]·2(BQEB)

Differentkindsofopenchaincrownethershavebeensynthesizedasthemodelcompoundsofionophoresandtheirinteractionswithsodium,potassiumandrareearthionshavealsobeenstudiedl'z.PanshowedCe(III)yieldedalf1complexwithl,8-bis(8'-quinolyloxy)-3,6-dioxaandtheCe(IIl)ioncoordinatedbothtoetheroxygenandquinolinenitrogenatoms3.TUmInleridentifiedtwolanthanidenitratecomplexeshavingastoichiometryof3:2(3RE:2L)'.InordertostUdythefunctionsofbothquinolineandbenzenering,introducedintothepolyetherchain,a1inearpolyether…     

Decisive Role of Symmetry in Structures of Three-Body Systems

A three-body system of identical particles is considered in order to demonstrate that the quantum-mechanical symmetry plays a decisive role in determining microscopic structures. Received March 14, 1994; revised July 29, 1994; accepted for publication October 19, 1994     

(4S)-4-羧基杂氮硅三环的合成

利用L-N,N-双(β-羟乙基)丝氨酸及L-N,N-双(β-羟乙基)苏氨酸与三乙氧基硅烷或氯烷基三乙氧基硅烷反应合成了具有手性的(4S)-4-羧基杂氮硅三环(1～5),并运用IR、~1HNMR、EI-MS等手段表征了结构。证据显示存在着贯穿笼状结构的N→Si配键。     

Chiral Cu(II) complex catalyzed enantioselective addition of phenylacetylene to N-aryl arylimines

Chiral tridentate N-tosylated aminoimine ligands were used in the Cu(II)-catalyzed enantioselective addition of phenylacetylene to N-aryl arylimines, affording products up to 92% ee.     

New catalytic effect of thiourea on the oxidative cyanation of N-aryltetrahydroisoquinolines

Thiourea itself has been introduced as a mild and efficient organocatalyst for the oxidative α -cyanation of N-aryltetrahydroisoquinolines (THIQs) with trimethylsilyl cyanide (TMSCN), giving the corresponding products in good to excellent yields. Experimental investigations demonstrated that thiourea acts as a radical initiator by abstracting hydroxyl radical (OH) from tert-butyl hydroperoxide (TBHP) directly instead of non-covalent hydrogen bondings (H-bondings) activation. The use of thiourea as a radical initiator offers a new avenue for innovative chemical transformations in organocatalyzed radical chemistry.     

A New Asterosaponin from the Starfish Culcita novaeguineae

A new asterosaponin named novaeguinoside A, along with a known saponin, asteronyl pentaglycoside sulfate, was isolated from the starfish Culcita novaeguineae. The new compound was identitied to be sodium 6α-O-{β-D-fucopyranosyl-(1→2)-β-D-fucopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-xylopyranosyl-(1→3)-[β-D-quinovopyranosyl}-5α-pregn-9(11)-en-20-one-3β-yl-sulfate by extensive spectral analysis and chemical evidence.     

Determination of Gossypol in Trace Level by Flow Injection Analysis with Chemiluminescence Detection

Gossypol, [1, 1′, 6, 6′, 7,7′-hexahydroxyl-5,5′-diisopropyl-3,3′-dimethyl-(2,2′-binaphtha- lene)-8,8′-dicarboxaldehyde] is a polyphenolic yellow compound naturally occurring in various parts of cotton plants1. The compound has been associated with