Catalytic Asymmetric Construction of Quaternary α‐Amino Acid Containing Pyrrolidines through 1,3‐Dipolar Cycloaddition of Azomethine Ylides to α‐Aminoacrylates

The first catalytic enantioselective 1,3‐dipolar cycloaddition of azomethine ylides to α‐aminoacrylate catalyzed by a AgOAc/ferrocenyl oxazolinylphosphine (FOXAP) system was developed, which exhibits excellent exo‐ and enantioselectivity (92–99 % ee). This process provides efficient access to useful 4‐aminopyrrolidine‐2,4‐dicarboxylic acid (APDC)‐like compounds containing a unique quaternary α‐amino acid unit.     

稀土-赤霉素配合物的合成与光谱表征

为了研究稀土与赤霉素的相互作用及其生物效应,在乙醇溶液中合成了两种新型稀土(Sm,Dy)-赤霉素(GA3)配合物,并对其进行了元素分析、质谱、紫外光谱、红外光谱、差热分析等表征。结果表明:配合物的组成为RE(GA3-)2Cl.6H2O(RE:Sm3+,Dy3+),镝-赤霉素配合物的热稳定性略高于钐-赤霉素配合物的。所得的两种配合物均易溶于二甲基甲酰胺、二甲基亚砜、甲醇、乙醇,不溶于水和丙酮中。     

Padé approximants for functions with branch points — strong asymptotics of Nuttall–Stahl polynomials

Let f be a germ of an analytic function at infinity that can be analytically continued along any path in the complex plane deprived of a finite set of points, \({f \in \mathcal{A}(\bar{\mathbb{C}} \setminus A)}\), \({\# A< \infty}\). J. Nuttall has put forward the important relation between the maximal domain of f where the function has a single-valued branch and the domain of convergence of the diagonal Padé approximants for f. The Padé approximants, which are rational functions and thus single-valued, approximate a holomorphic branch of f in the domain of their convergence. At the same time most of their poles tend to the boundary of the domain of convergence and the support of their limiting distribution models the system of cuts that makes the function f single-valued. Nuttall has conjectured (and proved for many important special cases) that this system of cuts has minimal logarithmic capacity among all other systems converting the function f to a single-valued branch. Thus the domain of convergence corresponds to the maximal (in the sense of minimal boundary) domain of single-valued holomorphy for the analytic function \({f\in\mathcal{A}(\bar{\mathbb{C}} \setminus A)}\). The complete proof of Nuttall’s conjecture (even in a more general setting where the set A has logarithmic capacity 0) was obtained by H. Stahl. In this work, we derive strong asymptotics for the denominators of the diagonal Padé approximants for this problem in a rather general setting. We assume that A is a finite set of branch points of f which have the algebro-logarithmic character and which are placed in a generic position. The last restriction means that we exclude from our consideration some degenerated “constellations” of the branch points.     

Edge Flips in Surface Meshes

Little theoretical work has been done on edge flips in surface meshes despite their popular usage in graphics and solid modeling to improve mesh equality. We propose the class of \((\varepsilon ,\alpha )\)-meshes of a surface that satisfy several properties: the vertex set is an \(\varepsilon \)-sample of the surface, the triangle angles are no smaller than a constant \(\alpha \), some triangle has a good normal, and the mesh is homeomorphic to the surface. We believe that many surface meshes encountered in practice are \((\varepsilon ,\alpha )\)-meshes or close to being one. We prove that flipping the appropriate edges can smooth a dense \((\varepsilon ,\alpha )\)-mesh by making the triangle normals better approximations of the surface normals and the dihedral angles closer to \(\pi \). Moreover, the edge flips can be performed in time linear in the number of vertices. This helps to explain the effectiveness of edge flips as observed in practice and in our experiments. A corollary of our techniques is that, in \(\mathbb {R}^2\), every triangulation with a constant lower bound on the angles can be flipped in linear time to the Delaunay triangulation.     

Modeling and analysis of a marine plankton system with nutrient recycling and diffusion

This article describes a nutrient‐phytoplankton‐zooplankton system with nutrient recycling in the presence of toxicity. We have studied the dynamical behavior of the system with delayed nutrient recycling in the first part of the article. Uniform persistent of the system is examined. In the second part of the article, we have incorporated diffusion of the plankton population to the system and dynamical behavior of the system is analyzed with instantaneous nutrient recycling. The condition of the diffusion driven instability is obtained. The conditions for the occurrence of Hopf and Turing bifurcation critical line in a spatial domain are derived. Variation of the system with small periodicity of diffusive coefficient has been studied. Stability condition of the plankton system subject to the periodic diffusion coefficient of the zooplankton is derived. It is observed that nutrient‐phytoplankton‐zooplankton interactions are very complex and situation specific. Moreover, we have obtained different exciting results, ranging from stable situation to cyclic oscillatory behavior may occur under different favorable conditions, which may give some insights for predictive management. © 2014 Wiley Periodicals, Inc. Complexity 21: 229–241, 2015     

Total synthesis of fuzinoside

The first total syntheses of fuzinoside (1b) were achieved from d-galactose through two strategies (BCA and ABC) in 11 (total yield: 5.0%) and 15 (total yield: 3.7%) steps, respectively. Comparison of NMR data of synthetic compound 1b and those of the fuzinoside isolated from the lateral roots of Aconitum carmicaelii suggests that the structure reported in the literature ^1 and 2 might not be accurate. The synthetic fuzinoside (1b) exhibited moderate cardiac activity in the isolated bullfrog heart assay.     

A sensitive immunosorbent bio-barcode assay based on real-time immuno-PCR for detecting 3,4,3',4'-tetrachlorobiphenyl

A functionalized gold-nanoparticle bio-barcode assay, based on real-time immuno-PCR (IPCR), was designed for the determination of 3,4,3',4'-tetrachlorobiphenyl (PCB77). 15 nm gold nanoparticles were synthesized, and modified with thiol-capped DNA and goat anti-rabbit IgG. The nanoparticle probes were used to replace antibody–DNA conjugate in the IPCR, and were fixed on the PCR tube wall via the immune reaction. Real-time PCR was performed to quantify the DNA signal directly. Under optimized conditions, the new method was used to detect PCB77 with a linearity range from 5 pg L^?1 to 10 ng L^?1, and the limit of detection (LOD) was 1.72 pg L^?1. Real samples of Larimichthys polyactis, collected from the East China Sea, were analyzed. Recovery was from 82 % to 112 %, and the coefficient of variation (CV) was acceptable. The results were compared with GC–ECD, revealing that the method would be acceptable for providing rapid, semi-quantitative, and reliable test results for making environmental decisions.

Rapid and simple electrochemical detection of morphine on graphene–palladium-hybrid-modified glassy carbon electrode

A hybrid of reduced graphene oxide–palladium (RGO–Pd) nano- to submicron-scale particles was simultaneously chemically prepared using microwave irradiation. The electrochemical investigation of the resulting hybrid was achieved using cyclic voltammetry and differential pulse voltammetry. RGO–Pd had a higher current response than unmodified RGO toward the oxidation of morphine. Several factors that can affect the electrochemical response were studied, including accumulation time and potential, Pd loading, scan rate, and pH of electrolyte. At the optimum conditions, the concentration of morphine was determined using differential pulse voltammetry in a linear range from 0.34 to 12 μmol L^?1 and from 14 to 100 μmol L^?1, with detection limits of 12.95 nmol L^?1 for the first range. The electrode had high sensitivity toward morphine oxidation in the presence of dopamine (DA) and of the interference compounds ascorbic acid (AA) and uric acid (UA). Electrochemical determination of morphine in a spiked urine sample was performed, and a low detection limit was obtained. Validation conditions including reproducibility, sensitivity, and recovery were evaluated successfully in the determination of morphine in diluted human urine.

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Simulation of oxidative stress of guanosine and 8-oxo-7,8-dihydroguanosine by electrochemically assisted injection–capillary electrophoresis–mass spectrometry

Oxidative stress plays a crucial role in DNA and RNA damage within biological cells. As a consequence, mutations of DNA can occur, leading to disorders like cancer and neurodegenerative and cardiovascular diseases. The oxidative attack of guanosine and 8-oxo-7,8-dihydroguanosine is simulated by electrochemistry coupled to capillary electrophoresis–mass spectrometry. The electrochemical conversion of the compound of interest is implemented in the injection protocol termed electrochemically assisted injection (EAI). In this way, oxidation products of guanosine can be generated electrochemically, separated by capillary electrophoresis, and detected by electrospray ionization time-of-flight mass spectrometry (EAI–CE–MS). A fully automated laboratory-made EAI cell with an integrated buffer reservoir and a compartment holding screen-printed electrodes is used for the injection. In this study, parameters like pH of the sample solution and the redox potential applied during the injection were investigated in terms of corresponding formation of well-known markers of DNA damage. The important product species, 8-oxo-7,8-dihydroguanosine, was investigated in a separate study to distinguish between primary and secondary oxidation products. A comparison of product species formed under alkaline, neutral, and acidic conditions is presented. To compare real biological systems with an analytical approach for simulation of oxidative stress, it is desirable to have a well-defined control over the redox potential and to use solutions, which are close to physiological conditions. In contrast to typical HPLC–MS protocols, the hyphenation of EAI, CE, and MS enables the generation and separation of species involved without the use of organic solvents. Thus, information of the electrochemical behavior of the nucleoside guanosine as well as the primary oxidation product 8-oxo-7,8-dihydroguanosine can be characterized under conditions close to the physiological situation. In addition, the migration behavior found in CE separations of product species can be used to identify compounds if several possible species have the same mass-to-charge values determined by MS detection.

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Ethylene (co-)polymerization by long-lifetime half-sandwich zirconium catalyst bearing a [SSO]-carborane ligand

Half-sandwich zirconium complex 3 containing tridentate carborane [S,S,O] ligand 2 [(HOC6H2R2-4,6)(CH2)SC(B10H10) C(Ph)2P=S, R=tBu] was synthesized by the reaction of CpZrCl3(Cp=η5-C5H5) with sodium salt of ligand 2. Zirconium complex 3 was characterized by elemental and NMR analyses. DFT calculations were also performed on complex 3 to analyze the stereochemistry. The results from DFT calculations indicate that structure S1, in which no sulfur atom bonds to the zirconium atom, exists at the lowest energy level. In the presence of methylaluminoxane(MAO), complex 3 exhibited good catalytic activities for ethylene polymerization and long life-time up to 10 h. Moreover, the complex 3/MAO system displayed excellent catalytic activities toword ethylene copolymerization with 1-hexene or polar olefins.