三苯胺-吡啶衍生物的三光子吸收及光限幅特性

合成了3个三苯胺-吡啶衍生物4-乙烯基吡啶-4'-(N,N-二苯胺基)苯(PPAB)、三[4-(4-吡啶乙烯基)苯]胺(TPPA)和4-(对-甲基-乙烯基吡啶碘盐)-4'-(N,N-二苯胺基)苯(PBPI),研究了它们的单光子荧光和三光子荧光性质.在1310nm飞秒激光激发下,化合物PPAB,PBPI and TPPA在二氯甲烷溶液中发出很强的三光子上转换荧光,荧光峰分别位于648,625,696nm.用飞秒Ti:Sapphire激光器非线性透过率法测得3个化合物在1310nm三光子吸收截面分别为1.91×10-79,3.46×10-79,3.64×10-79cm6·s2,它们具有很强的三光子吸收和光限幅效应.     

水助甲酰胺-H2O2氧化乙烯制环氧乙烷反应机理的理论研究

采用MP2方法研究了甲酰胺-H2O2氧化乙烯制取环氧乙烷的反应机理.优化得到了反应物、过渡态、中间体及产物的几何构型并计算了反应势垒.研究结果表明:没有水参与时,反应需要通过四元环过渡态完成,反应势垒很高,在常温下难以进行;有水参与时,在水分子的协助下,反应可以通过六元环过渡态完成,反应势垒较低,常温下反应容易进行.     

Discrimination of Ephedra plants with diffuse reflectance FT-NIRS and multivariate analysis

The secondary metabolites of different Ephedra plants are various. Therefore, the discrimination of different Ephedra plants is significant. An objective, easy-to-use, rapid and pollution-free approach is proposed for discriminating Ephedra plants of different species, habitats and picking times on the basis of diffuse reflectance Fourier transform near infrared spectroscopy (FT-NIRS) measurements and multivariate analysis. The Fourier transform near infrared diffuse reflectance spectra (NIRDRS) were acquired from 37 pulverized samples of Ephedra plants put in glass vials in the near infrared (NIR) region between 10 000 and 4000 cm⁻¹, averaging 64 scans per spectrum at a resolution of 4 cm⁻¹. After spectra processing and data pre-processing, spectral data were analyzed respectively with three multivariate analysis techniques: discriminant analysis (DA), self-organizing map (SOM) and back-propagation artificial neural network (BP-ANN). The proposed method could distinguish not only the Ephedra plants of three species and two habitats but also the plants picked at different times of day without special sample treatment and the use of chemical reagents. The performance indexes of the DA model were 84.2-91.9% and the prediction accuracies of both the SOM and the BP-ANN models reached 93.3-100.0%.     

Viable but nonculturable cells used in biosensor fabrication for long-term storage stability

In this paper, we first reported the viable but nonculturable (VBNC) cells used for fabricating biosensor. The organic-inorganic hybrid material composed of silica and the grafting copolymer of poly(vinyl alcohol) and 4-vinylpyridine (PVA-g-P(4-VP)) was used to immobilize microbial cells for biosensor fabrication. The VBNC cells were formed after the hybrid material dried, showing the cell walls were sacrificed. With the intracellular enzymes as core and the “sacrificed” cell walls as shell, the present VBNC cells maybe considered as a core/shell structure. The extracellular material worked as the scaffold for core/shell structure. The core/shell structure and the scaffold structure were demonstrated by single-cell level image analysis using confocal laser scanning microscopy (CLSM). The electrochemical method was adopted for further examining the enzyme activity of VBNC cells. The VBNC cells did not need nutrient treatment and other physicochemical factors for cell growth, which is a significant contribution for storing biosensor. A glucose-glutamic acid biosensor fabricated by the VBNC cells exhibited long-term storage stability for 100 days.     

High-performance affinity monolith chromatography for chiral separation and determination of enzyme kinetic constants

A new kind of immobilized human serum albumin (HSA) column was developed by using the sub-micron skeletal polymer monolith based on poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) [poly(GMA-EDMA)] as the support of high-performance affinity chromatography. Using the epoxide functional groups presented in GMA, the HSA immobilization procedure was performed by two different means. The affinity columns were successfully adopted for the chiral separation of d,l-amino acids (AAs). Then this method was shown to be applicable to the quantitative analysis of d-tryptophan, with a linear range between 12.0 μM and 979.0 μM, and a correlation coefficient above 0.99. Furthermore, it was used for the analysis of urine sample. This assay is demonstrated to be facile and relatively rapid. So it allows us to measure the enzyme catalytic activity in the incubation of d,l-AAs with d-AA oxidase and to study the kinetics of the enzyme reaction. It implied that the affinity monolithic columns can be a useful tool for studying DAAO enzyme reaction and investigating the potential enzyme mechanism requirement among chiral conversion.     

Diversification of a β-Lactam Pharmacophore via Allylic C-H Amination: Accelerating Effect of Lewis Acid Co-Catalyst

This report describes the use of Pd(II)/bis-sulfoxide 1 catalyzed intra- and intermolecular allylic C-H amination reactions to rapidly diversify structures containing a sensitive β-lactam core similar to that found in the monobactam antibiotic Aztreonam. Pharmacologically interesting oxazolidinone, oxazinanone, and linear amine motifs are rapidly installed with predictable and high selectivities under conditions that use limiting amounts of substrate. Additionally, we demonstrate for the first time that intramolecular C-H amination processes may be accelerated using catalytic amounts of a Lewis acid co-catalyst [Cr(III)(salen)Cl 2].     

Efficient synthesis of (Z)- and (E)-methyl 2-(methoxyimino)-2-phenylacetate

Direct oximation of 2-oxo-2-phenylacetate (3) gave the (Z)-methyl 2-(methoxyimino)-2-phenylacetate (1) in 71% yield, while the E oxime 2 was prepared from 3 in 65% yield via oxime isomerization of 2-(methoxyimino)-2-phenylacetic acid (5). Computational studies suggest that the isomerization of 5 is thermodynamically driven, while the direct oximation of ketoester 3 is kinetically controlled.     

Melting in two-dimensional Yukawa systems: a Brownian dynamics simulation

We studied the melting behavior of two-dimensional colloidal crystals with a Yukawa pair potential by Brownian dynamics simulations. The melting follows the Kosterlitz-Thouless-Halperin-Nelson-Young (KTHNY) scenario with two continuous phase transitions and a middle hexatic phase. The two phase-transition points were accurately identified from the divergence of the translational and orientational susceptibilities. Configurational temperatures were employed to monitor the equilibrium of the overdamped system and the strongest temperature fluctuation was observed in the hexatic phase. The inherent structure obtained by rapid quenching exhibits three different behaviors in the solid, hexatic, and liquid phases. The measured core energy of the free dislocations, E(c) = 7.81 ± 0.91 k(B)T, is larger than the critical value of 2.84 k(B)T, which consistently supports the KTHNY melting scenario.     

Assembly of a Novel Dumbbell‐type Dinuclear Copper(II) Complex: Synthesis,Structure and Properties

A new dumbbell‐type 4,4′‐bipy‐bridged dinuclear copper(II) complex, [Cu₂(4,4′‐bipy)L₂(H₂O)₂](ClO₄)₄ · 8CH₃OH · 10H₂O, where L = 1‐[bis(3‐aminopropyl)amino]‐2‐ propanol and bipy = bipyridine, has been synthesized and characterized, X‐ray crystallographic analysis shows that the [Cu₂(4,4′‐bipy)L₂(H₂O)₂]⁴⁺ cations and water molecules generate layer structures extending parallel to bc planes through hydrogen bonding interactions of O–H ··· O and C–H ··· O. The layers are also connected by hydrogen bonding interactions involving methanol, water, and perchlorate anions. These interactions lead to the formation of rectangular channels of 12.3 Å × 6.0 Å along the crystallographic c axis. Perchlorate anions fill in each channel in a sandwich‐like packing mode, they are joined with the adjacent layers by water heptamers. Magnetic susceptibility measurements show that the magnetic exchange interaction is weak although it has a regular π‐type electron transfer pathway. Furthermore, the electrochemical and thermogravimetric properties of the complex were also investigated.     

Novel efficient procedure for the conjugate addition of amines to electron deficient alkenes

The novel efficient procedure has been developed for the conjugate addition of amines to electron deficient alkenes using the novel SO₃H functionalized ionic liquid as catalyst. The results showed that the novel catalyst owned high activities for the reactions with excellent yields within several minutes. Various amines and electron deficient alkenes were successfully transformed to the corresponding products in the catalytic system. Operational simplicity, without need of any solvent, low cost of the catalyst used, room temperature, high yields, reusability, excellent chemoselectivity and wide applicability are the key features of this methodology.