负载金催化剂上CO氧化反应活性与金属氧化物载体中金属-氧结合能之间的关系

讨论了金属氧化物载体(MOx)对其负载纳米金催化剂(Au/MOx)上CO氧化反应的影响。采用典型的共沉淀法和沉积-沉淀法在完全相同的焙烧条件下制备了一系列MOx负载金催化剂,以CO氧化转化50%时的反应温度(T1/2)定量评价了MOx载体和Au/MOx催化剂的催化活性。进一步将MOx载体与相应Au/MOx催化剂的T1/2值之差对MOx载体的金属-氧结合能做曲线进行关联,发现二者呈明显的火山型关系。这一结果表明,采用具有适当金属-氧结合能(300–500 atom O)的MOx可大大提高沉积于其上的Au纳米颗粒的催化活性。     

Stereochemistry of the base-catalyzed methanolysis of 2-phenyl-tetrahydropyrrolo-1,3,2-oxazaphospholes

Diastereomerically pure bicyclic oxazaphospholes were prepared from L-prolinol and phenylphosphonic or thiophosphonic dichloride and their absolute configurations were determined based on the interpretation of NMR spectra. The base-catalyzed methanolysis of those compounds was found to proceed by exclusive PO bond cleavage with complete inversion of configuration.     

木根黄芩中-新黄酮的光谱特征

从木根黄芩(Scutellaria planipes Nakai et Kitag.)中分离得到一新黄酮类化合物. 该化合物被鉴定为5,7,3′,6′-tetrahydroxy-6,8,2′-trimethoxyflavone. 它有很强的抑制5-酯氧合酶活性. 由于该化合物的A环全部被取代，因此，应用一般的光谱技术很难准确归属各碳的化学位移. 我们应用¹³C-¹³C相关谱和酰化位移方法，明确归属了各碳的信号，并订正了文献中对部分信号的错误归属.     

Mizoroki-Heck type arylation of alkenes using aroyl chlorides under base-free conditions

The Mizoroki-Heck type arylation of alkenes with aroyl chlorides accompanied by decarbonylation efficiently proceeds in the presence of a palladium catalyst system, PdCl₂(PhCN)₂/(PhCH₂)Bu₃NCl, even without adding any base. The products can be isolated by a very simple procedure.     

Nylon 6 structure in solid state as studied by high-resolution 13C-NMR spectroscopy

High resolution ¹³C-NMR spectra of nylon 6 samples crystallized under various conditions and of a drawn sample were measured at room temperature by the cross polarization/magic angle spinning (CP/MAS) and pulse saturation transfer/magic angle spinning techniques. Additionally, ¹³C-NMR spectra of the drawn sample were measured at temperatures from 20 to 100°C by the CP/MAS technique and at 20 and 100°C by the low-power decoupling/magic angle spinning technique. The nylon 6 structure in the solid-state is discussed on the basis of these results. The solid-state ¹³C chemical shift data are used for reference in a study of conformation in solution.     

Addition of S-benzoyl phenylselenosulfide to olefins: selenothiocarboxylation

Heating of S-benzoyl phenylselenosulfide and olefins with AIBN afforded selenothiocarboxylated products generated by a free radical process with high regiospecificity but lack of stereoselectivity.     

High-resolution infrared spectrum of the ν2 and ν8 bands of CH2D2

A high-resolution infrared spectrum of methane-d₂ has been measured in the C-D stretching band region (2025–2435 cm^?1). Rotational structures of the ν₂ and ν₈ bands have been assigned by use of the ASSIGN-diagram method, and the c-type Coriolis interaction between ν₂ and ν₈ has been analyzed. The band origins, ν₂ = 2203.22 ± 0.01 cm^?1 and ν₈ = 2234.70 ± 0.01 cm^?1, the rotational constants and the centrifugal distortion constants for the two bands, and the Coriolis coupling constant, $\text{∥;ξ}{}_{28}{}^{\mathrm{c}}\text{∥; = 0.182 ± 0.015}\text{cm}{}^{\mathrm{?1}}$, have been determined.