Fabrication and performance of a three-dimensionally adjustable device for the amperometric detection of microchip capillary electrophoresis

A microchip CE-amperometric detection (AD) system has been fabricated by integrating a two-dimensionally adjustable CE microchip and an AD cell containing a one-dimensionally adjustable disk detection electrode in a Plexiglas holder. It facilitates the precise 3-D alignment between the channel outlet and the detection electrode without a complicated 3-D manipulator. The performance of this unique system was demonstrated by separating five aromatic amines (1,4-phenyldiamine, aniline, 2-methylaniline, 4-chloroaniline, and 1-naphthylamine) of environmental concern. Factors influencing their separation and detection processes were examined and optimized. The five analytes have been well separated within 140 s in a 74 cm long separation channel at a separation voltage of +2500 V using a 10 mM phosphate buffer (pH 3.5). Highly linear response is obtained for the five analytes over the range 20-200 microM with the detection limits ranging from 0.46 to 1.44 microM, respectively. The present system demonstrated long-term stability and reproducibility with RSDs of less than 5% for the peak current (n = 9). The new approach for the microchannel-electrode alignment should find a wide range of applications in CE, flowing injection analysis, and other microfluidic analysis systems.     

Et2NH2[Nd(S2CNEt2)4]的晶体结构和生成反应焓变

在干燥氮气气氛下,以无水乙醇为溶剂,制备了低水合氯化钕与二乙氨基荒酸二乙铵(D-DDC)配合物,确定其组成为Et2NH2[Nd(S2CNEt2)4].单晶结构分析表明,配合物中4个二乙氨基荒酸根各通过2个硫原子与钕离子成键形成八配位十二面体阴离子,并与二乙铵阳离子形成缔合型分子.晶体属单斜晶系,空间群P21/n,a=1.37517(14)nm,b=2.1146(2)nm,c=1.44641(15)nm,β=102.028(2)°,Z=4.用微量热法测定了298.15K下水合氯化钕和D-DDC在无水乙醇中的溶解焓及二乙氨基荒酸钕液相生成反应焓变分别为(-17.89±0.096),(50.280±0.151)和(-10.116±0.065)kJ/mol,求得固相生成反应焓变.     

Mass spectral fragmentation of (S,S)-2-substituted 4,4-diphenyl-3,1-oxazabicyclo[3.3.0]octanes: ring contraction of pyrrolidine and 1,3-oxazolidine in mass spectrometry

The mass spectral behaviour of (S,S)-2-substituted 4,4-diphenyl-3,1-oxazabicyclo[3.3.0]octanes has been studied with the aid of mass-analyzed ion kinetic energy spectrometry and accurate mass measurements under fast atom bombardment (FAB) and electron impact (EI) ionization conditions. Under FAB ionization, all compounds show a tendency to form protonated aldehyde or benzophenone ions and to form protonated 1-azabicyclo[3.1.0]hexane ions, which can further lose an ethylene or cyclopropane from the pyrrolidine ring to produce protonated 1-azabicyclo[1.1.0]butane ions and 3H-azirine ions, respectively. Under EI ionization, a similar fragmentation to that under FAB ionization was observed. The title compounds also show a tendency to yield oxirane ions and oxirenium ions by loss of pyrrolidine and pyrrolidine plus H. Ring contractions of 1,3-oxazolidine by loss of an aldehyde or ketone and of pyrrolidine by loss of an ethylene or cyclopropane were observed under both FAB and EI ionization conditions.     

A facile electrochemical synthesis of caffeic acid derivatives in the presence of acetylacetone or methyl acetoacetate in aqueous medium

The anodic oxidation of caffeic acid in the presence of acetylacetone or methyl acetoacetate in aqueous solution has been studied by cyclic voltammetry and controlled-potential electrolysis techniques. The result showed that caffeic acid was oxidized to the corresponding o-benzoquinone, which underwent further Michael-addition with acetylacetone or methyl acetoacetate to produce caffeic acid derivative 3,4-dihydroxy-6-(1-acetylacetone)-yl cinnamic acid 4a or 3,4-dihydroxy-6-(1-acetyl-methylacetate)-yl cinnamic acid 4b.     

Cellulose synthesis in maize: isolation and expression analysis of the cellulose synthase (CesA) gene family

Stalk lodging in maize results in significant yield losses. We have determined that cellulose per unit length of the stalk is the primary determinant of internodal strength. An increase in cellulose concentration in the wall might allow simultaneous improvements in stalk strength and harvest index. Cellulose formation in plants can be perturbed by mutations in the genes involved in cellulose synthesis, post-synthetic cellulose alteration or deposition, N-glycosylation, and some other genes with as yet unknown functions. We have isolated 12 members of the cellulose synthase (CesA) gene family from maize. The genes involved in primary wall formation appear to have duplicated relatively independently in dicots and monocots. The deduced amino acid sequences of three of the maize genes, ZmCesA10–12, cluster with the Arabidopsis CesA sequences that have been shown to be involved in secondary wall formation. Based on their expression patterns across multiple tissues, these three genes appear to be coordinately expressed. The remaining genes show overlapping expression to varying degrees with ZmCesA1, 7, and 8 forming one group, ZmCesA3 and 5 a second group, and ZmCesA2 and 6 exhibiting independent expression of any other gene. This suggests that the varying levels of coexpression may just be incidental except in the case of ZmCesA10–12, which may interact with each other to form a functional enzyme complex. Isolation of the expressed CesA genes from maize and their association with primary or secondary wall formation has made it possible to test their respective roles in cellulose synthesis through mutational genetics or transgenic approaches. This information would be useful in improving stalk strength.     

Study of Structures and Electronic Properties of Pdn–1Pb and Pdn （n≤8） Clusters

Geometric and electronic properties of Pdn–1Pb and Pdn (n≤8) clusters have been studied by using density functional theory with effective core potentials, focusing on the differences between mono- and bimetallic clusters. The average bond length of Pdn–1Pb (n≤8) bimetallic clusters is longer than that of pure palladium clusters except for n = 2 and 3. The most stable structure of Pdn–1Pb (n≤7) is the singlet where there is at least a Pd or Pb atom on its excited state. The energy gaps of Pd–Pb binary clusters are narrower than those of Pdn clusters, and then the chemical activity is strengthened when Pdn clusters are doped with Pb.     

关于超高分子量聚丙烯超拉伸膜的结构性能的研究——Ⅱ.形态结构变化对力学性能的影响

用X-射线衍射、动态力学测定等手段研究了不同拉伸倍数的超高分子量聚丙烯薄膜的力学性能的变化.以X-射线衍射法并基于串联力学模型的假设得到的各样品的表观晶区模量E_c~(app)约为34-38GPa.样品模量E_b随拉伸倍数增加而逐渐增大,其变化趋势与非晶区取向因子的变化相类似,说明非晶区取向是左右样品模量的重要因素.室温下,69倍拉伸样品的模量为27GPa,约为表观结晶模量的3/4,且其值在-150-160℃的温度范围内没有急剧变化,说明超拉伸明显改善了材料的力学性能及热稳定性.在各拉伸样品中,考虑伸直链结晶生成的可能性,利用并串联力学模型对伸直链结晶的体积分数做了估算,并对X-射线衍射法所得表观结晶模量进行了修正,认为室温下聚丙烯的真正晶区模量约为47GPa.     

Predictions of moiré excitons in twisted two-dimensional organic–inorganic halide perovskites

Recent breakthrough in synthesizing arbitrary vertical heterostructures of Ruddlesden–Popper (RP) perovskites opens doors to myriad quantum optoelectronic applications. However, it is not clear whether moiré excitons and flat bands can be formed in such heterostructures. Here, we predict from first principles that twisted homobilayers of RP perovskite, MA₂PbI₄, can host moiré excitons and yield flat energy bands. The moiré excitons exhibit unique and hybridized characteristics with electrons confined in a single layer of a striped distribution while holes localized in both layers. Nearly flat valence bands can be formed in the bilayers with relatively large twist angles, thanks to the presence of hydrogen bonds that strengthen the interlayer coupling. External pressures can further increase the interlayer coupling, yielding more localized moiré excitons and flatter valence bands. Finally, electrostatic gating is predicted to tune the degree of hybridization, energy, position and localization of moiré excitons in twisted MA₂PbI₄ bilayers.

Excitonic states in twisted MA₂PbI₄ bilayers were calculated by first-principles calculations.     

New perylene polyimides containing p‐n diblocks for sensitization in TiO2 solar cells

Three novel perylene polyimides (PPIs) containing p‐n diblock units were designed and synthesized for use in dye‐sensitized mesoporous TiO₂ solar cells. They all dissolve in m‐cresol and N‐methyl‐2‐pyrrolidone (NMP). Their visible light absorption, electrochemical and photoelectrochemical properties were systematically studied. The polyimides have band gap energies of 2.16, 2.19 and 2.25 eV deduced from ultraviolet–visible absorption spectra, and electron affinity (E_a) and ionization potential (IP) of ?3.93 and 6.10 eV for PPI1, ?3.94 and 6.13 eV for PPI2, ?3.93 and 6.59 eV for PPI3, respectively, deduced from cyclic voltammogram. Experimental data show that introduction of 4,4′‐bisaminetriphenylamine cannot only greatly enhance optic‐electro conversion efficiency, but also enhance the dissolubility which in favorable for making the devices. The relationship of structure and properties of PPI is discussed and the mechanism of photocurrent generation is explained. Copyright © 2004 John Wiley & Sons, Ltd.     

Diffusion-induced Spatio-temporal Oscillations in an Epidemic Model with Two Delays

We investigate a diffusive, stage-structured epidemic model with the maturation delay and freelymoving delay. Choosing delays and diffusive rates as bifurcation parameters, the only possible way to destabilize the endemic equilibrium is through Hopf bifurcation. The normal forms of Hopf bifurcations on the center manifold are calculated, and explicit formulae determining the criticality of bifurcations are derived. There are two different kinds of stable oscillations near the first bifurcation: ...