邻基参与与环化反应

本文总结了邻基参与的各类环化反应。     

Analysis of the monosaccharide components in Angelica polysaccharides by high performance liquid chromatography.

An analytical method of on-line high performance liquid chromatography (HLPC) was developed to simultaneously separate and identify the monosaccharide composition of three Angelica polysaccharide fractions (APF), named APF1, APF2 and APF3. In this method, APF were hydrolyzed into component monosaccharides and subsequently labeled with 1-phenyl-3-methyl-5-pyrazolone (PMP), and then the labeled monosaccharide derivatives were separated by a reverse-phase C18 column and monitored by UV absorbance at 250 nm. The results showed that nine monosaccharide derivatives have been well separated by HPLC under optimized conditions and the composition analysis of monosaccharides from APF samples could be achieved using acid hydrolysis and a set of monosaccharide standards. With this method, the within-day and day to day precisions of the composition determinations were 3.41-4.87% and 3.12-4.93% (RSD), respectively. The method was successfully applied to the determination of the component monosaccharides of Angelica polysaccharides.     

An efficient total synthesis of (+/-)-stemonamine

An efficient first approach to the Stemona alkaloid (+/-)-Stemonamine has been developed on the basis of a key TiCl4 promoted tandem Semipinacol rearrangement/Schmidt reaction and a Dieckmann condensation reaction.     

Existence of Solution for a Singular Elliptic Equation of Kirchhoff Type

We study both the existence and uniqueness of nonnegative solution to a singular elliptic problem of Kirchhoff type, whose model is:

$$\begin{aligned} {\left\{ \begin{array}{ll} -B\left( \dfrac{1}{2}\displaystyle \int _\Omega |\nabla u|^2\mathrm {d}x\right) \Delta u=\dfrac{h(x)}{u^\gamma }, &{}\quad x\in \Omega ,\\ u>0, &{}\quad x\in \Omega ,\\ u=0, &{}\quad x\in \partial \Omega , \end{array}\right. } \end{aligned}$$

where \(\Omega \subset \mathbb {R}^n(n\ge 1)\) is a smooth bounded domain, \(\gamma >1\), \(h\in L^1(\Omega )\) is positive (i.e., \(h(x)>0\) a.e. in \(\Omega \)), \(B : \mathbb {R}^+\rightarrow \mathbb {R}^+\) is a \(C^1\)-continuous function with positive lower bound. A necessary and sufficient condition will be given for the existence of weak solution of the general nonlocal singular elliptic with strong singularity. In addition, we prove that the solution is unique under some suitable conditions.

     

Antibody-functionalized magnetic nanoparticles for the detection of carcinoembryonic antigen using a flow-injection electrochemical device

A magnetocontrolled immunosensing strategy based on flow-injection electrochemical impedance spectroscopy (EIS) was developed for the determination of carcinoembryonic antigen (CEA) in human serum. The immunosensor was fabricated by immobilizing anti-CEA on epoxysilane-modified core–shell magnetic Fe₃O₄/SiO₂ nanoparticles. The detection principle is based on the difference between the resistances measured before and after the antigen–antibody interaction. The performance of the immunosensor and factors influencing this performance were also proposed. The resistance response depended linearly on the CEA concentration over the range 1.5–60 ng/ml, and the immunosensor gave a detection limit of 0.5 ng/ml (S/N = 3). Coefficients of variance (CVs) of <9.8% were obtained for the intra- and interassay precisions. The method was successfully applied to the analysis of CEA in human serum. The recoveries obtained by spiking CEA standards into normal serum were 87–113%. The performance of the immunosensor was compared with a commercially available CEA ELISA. Satisfactory results were obtained according to a paired t-test method (t value < t _critical at the 95% confidence level). Importantly, the proposed immobilization protocol could be further developed to immobilize other antigens or biocompounds. Figure This study introduced a magnetocontrolled electrochemical immunosensing strategy based on antibody-functionalized magnetic core–shell Fe₃O₄/SiO₂ nanoparticles for the determination of carcinoembryonic antigen in human serum     

Enantioselective α-hydroxylation of β-keto esters catalyzed by chiral S-timolol derivatives

A screen of aryloxy aminopropanol organocatalysts derived from the β-blocker inhibitor S-timolol determined the most active catalyst of asymmetric α-hydroxylation of β-keto esters. (R)-1-(tert-butylamino)-3-(3,4,5-trimethoxyphenoxy) propan-2-ol (3k) was the most effective derivative, enantioselectively catalyzing α-hydroxylation of β-keto esters using tert-butyl hydroperoxide as the oxidant in hexane to afford the corresponding products in excellent yield and with good enantioselectivity (up to 96% yield, 88% ee).     

Structural dependence of microwave dielectric properties of ixiolite structured ZnTiNb2O8 materials: crystal structure refinement and Raman spectra study

Structural and property relationships of ixiolite structured ZnTiNb(2)O(8) microwave dielectric materials were studied by structure refinement and Raman spectra analysis. The vibration modes which have Raman activities of the ixiolite structure were assigned for the first time. The bands with wavenumbers greater than 450 cm(-1) can be associated with several modes (A(g(2)), B(3g(1)), B(3g(2)), A(g(1)), B(1g(2)), A(g(3)), B(2g(2))) involving the stretching of the cation-O bonds. For wavenumbers between 250 and 450 cm(-1), the bands are due, principally, to the bending of O-cation-O (B(1g(1)), B(2g(1)), B(1g(3))). The origin of the bands with wavenumbers below 250 cm(-1) would be lattice vibrations (B(1g(4)), A(g(4)), B(3g(4)), B(2g(4))), mainly associated with cation ions. The correlation between bond strength and packing fraction, Raman shift, full width at half maximum (FWHM) of Raman spectra were discussed. With increase of bond strength, the oxygen octahedron became rigid, the Raman shift increased, and the damping behavior became weaker. With increase of Raman shift, the dielectric constant decreased. With increase of packing fraction and decrease of FWHM, the Q(f) (quality factor × resonance frequency) value increased. The τ(f) (temperature coefficient of resonance frequency) decreased with increase of bond strength. And there was no direct relationship between oxygen octahedron distortion and τ(f). The excellent microwave dielectric properties of ZnTiNb(2)O(8) in this work were: dielectric constant (ε) = 34.4, Q(f) = 56,900 GHz, τ(f) = -47.94 × 10(-6)/°C.     

咪唑类离子液体[C10mim][NTf2]萃取铈(IV)

以咪唑类离子液体1-癸基-3-甲基咪唑三氟磺酰亚胺盐[C10mim][NTf2]为萃取剂,研究了其对铈(Ⅳ)的萃取行为,分别考察了萃取时间、料液浓度、硝酸浓度、离子液体咪唑环上烷基链长、无机盐浓度和温度对萃取过程的影响。 热力学计算表明,萃取过程是自发的放热过程。 推测可能的萃取机理是阴离子交换机理。 对萃取液进行了反萃考察,在硫酸浓度为1.0 mol/L时,反萃率为85.1%。     

一种基于碳纳米管/高分子复合材料的流量控制致动器

利用超顺排碳纳米管/高分子复合材料设计和制造了一种半透明的流量控制致动器. 这种致动器能够像阀门一样工作,展示了一种新颖的不需要沉重的机械传动装置就可以实现流体流速控制的方法. 通过电功率（或电压）能够实现对流体流速的精确控制,或者截断流体. 透过半透明的致动器壁,能够清晰的观察到流量控制的过程. 这个致动器具有低驱动电压（<6 V）,良好的生物兼容性,良好的柔性和长的使用寿命（5000次循环以上）等优点,在仿生领域具有广阔的应用前景.     

Effects of annealing ambience on ZnO:N films grown by MOCVD and the p-type doping mechanism of ZnO:N films investigated by XANES

ZnO:N thin films were deposited on sapphire substrate by metal organic chemical vapor deposition with NH₃ as N-doping sources. The reproducible p-type ZnO:N film with hole concentration of ∼10¹⁷ cm⁻³ was successfully achieved by subsequent in situ thermal annealing in N₂O plasma protective ambient, while only weak p-type ZnO:N film with remarkably lower hole concentration of ∼10¹⁵ cm⁻³ was obtained by annealing in O₂ ambient. To understand the mechanism of the p-type doping behavior of ZnO:N film, X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption near-edge spectroscopy (XANES) measurements have been applied to investigate the local electronic structure and chemical states of nitrogen atoms in ZnO:N films.