Enantioselective henry reactions catalyzed by chiral N-metal complexes containing R(+)/S(−)-α-ethylphenyl amines

A series of novel N-metal complexes containing chiral α-ethylphenyl amines was synthesized and they catalyzed asymmetric Henry reactions affording products with high enantioselectivity.     

Synthesis,Structure, and Magnetic Properties of Three Novel Sandwich‐type Tungstobismuthates with Triethanolamine

Three novel sandwich‐type polyoxotungstates ( 1 – 3 ) were synthesized in good yield using an in‐situ conventional solution synthesis method by reaction in aqueous media below 80 °C. Compounds 1 – 3 represent the first structurally characterized β‐B‐BiW₉ sandwich‐type polyoxometalates with triethanolamine cations. All three compounds have the same building unit [(X(H₂O)₃)₂(X_0.5W_0.5O)₂(β‐B‐BiW₉O₃₃)₂)]^10– [X = Mn^II ( 1 ), Co^II ( 2 ), Ni^II ( 3 )]. The adjacent units of 1 or 2 are joined by Na⁺ cations in different ways to construct 1D chains or 2D sheets. A 3D supramolecular structure is further formed by hydrogen bond interactions among water molecules and protonated triethanolamine cations. Meanwhile only compound 3 shows a 0D structure. The compounds were characterized by elemental analysis, IR spectroscopy, TG analysis, and single‐crystal X‐ray diffraction. Magnetic measurements on a sample of 1 show the presence of paramagnetic interactions.     

Synthesis and calming activity of helicid derivatives containing the 3,4-dihydropyrimidin-2(<Emphasis Type="Italic">H</Emphasis>)-one and 3,4-dihydropyrimidine-2(<Emphasis Type="Italic">H</Emphasis>)-thione moiety

A series of novel helicid derivatives containing 3,4-dihydropyrimidin-2(1H)-one and 3,4-dihydropyrimidine2(1H)-thione moiety (3a–3f and 4a–4f) were synthesized starting from helicid. The structure of the new compounds were characterized by ¹H NMR, IR and HR-MS spectra. The sedative-hypnotic activities of the target compounds were evaluated using the test of spontaneous locomotor activity in mice. All of the derivatives produced moderate to high activities; in particular, compound 4a presented the most potent sedative-hypnotic effect in comparison to the other derivatives, and derivatives 3a, 3c, 3d, 3e and 3f also showed potent activities.     

Gene Cloning,Expression, and Characterization of a Family 51 α-<Emphasis Type="SmallCaps">l</Emphasis>-Arabinofuranosidase from <Emphasis Type="Italic">Streptomyces</Emphasis> sp. S9

An α-l-arabinofuranosidase gene, abf51S9, was cloned from Streptomyces sp. S9 and successfully expressed in Escherichia coli BL21 (DE3). The full-length gene consisted of 1,506 bp and encoded 501 amino acids with a calculated mass of 55.2 kDa. The deduced amino acid sequence was highly homologous with the α-l-arabinofuranosidases belonging to family 51 of the glycoside hydrolases. The recombinant protein was purified to electrophoretic homogeneity by Ni-NTA affinity chromatography and subsequently characterized. The optimal pH and temperature for the recombinant enzyme were 6.0 and 60∼65 °C, respectively. The enzyme showed a broad pH range of stability, retaining over 75% of the maximum activity at pH 5.0 to 11.0. The specific activity, K _m, and V _max with p-nitrophenyl-α-l-arabinofuranoside as substrate were 60.0 U mg⁻¹, 1.45 mM, and 221 μmol min⁻¹ mg⁻¹, respectively. Abf51S9 showed a mild but significant synergistic effect in combination with xylanase on the degradation of oat-spelt xylan and soluble wheat arabinoxylan substrates with a 1.19- and 1.21-fold increase in the amount of reducing sugar released, respectively. These favorable properties make Abf51S9 a good candidate in various industrial applications.     

Gene Cloning,Overexpression, and Characterization of the Nitrilase from <Emphasis Type="Italic">Rhodococcus rhodochrous</Emphasis> tg1-A6 in <Emphasis Type="Italic">E. coli</Emphasis>

A DNA fragment containing the entire coding sequence of nitrilase gene was amplified from Rhodococcus rhodochrous tg1-A6 with high nitrilase activity using PCR and sequenced. The open reading frame of the nitrilase gene contains 1,101 base pairs, which encodes a putative polypeptide of 366 amino acid residues. The nitrilase gene was cloned into an expression vector pET-28a and expressed in an Escherichia coli strain BL21(DE3). The enzymatic activity of nitrilase, which converts various nitriles to the corresponding carboxylic acids, was detected to reach 24.5 U/ml at 9 h in the recombinant bacteria.     

Syntheses,crystal structures,and magnetic and luminescent properties of a series of lanthanide coordination polymers with chelidamic acid ligand

A series of lanthanide(III) complexes with chelidamic acid ligand, [Ln(C₇H₂NO₅)·3H₂O]_n·nH₂O (Ln = La (1), Y (2), Sm (3), and Nd (4)), [Gd₂(C₇H₂NO₅)₃·4H₂O]_n·2nH₂O (5) and [Ce(C₇H₂NO₅)·1.5H₂O]_n (6), have been synthesized by hydrothermal method and structurally characterized by single-crystal X-ray diffraction. Complexes 1–4 are isostructural and possess 2D framework. Complex 5 contains two different Gd(III) ions linked through carboxylate group to form a 2D framework. Complex 6 exhibits a (4⁴) topology 2D network. The variable-temperature magnetic properties of 3 and 5 have been investigated. Furthermore, the photoluminescent properties of 1, 2, 3, and 5 at room temperature were also studied.     

Magnetic particle based electrochemical sensing platform for PCR amplicon detection

This work reports a novel electrochemical PCR detection platform using magnetic particles as a separation tool. A redox-active intercalator, anthraquinonemonosulfonic acid (AQMS), was firstly intercalated into biotin labeled PCR amplicons, and the resulting complex was then captured by streptavidin-coated magnetic particles (MPs) to form AQMS–DNA–MP conjugates. Subsequently, these conjugates were attracted to the bottom of the tube and separated from the solution by applying an external magnetic field, resulting in a significant reduction of the concentration of solution AQMS. The concentration changes of solution AQMS, which reflect the presence and quantity of PCR amplicons, were monitored by differential pulse voltammetry (DPV) on a chip electrode. PCR cycle number-dependent as well as the initial template DNA concentration-dependent performances were investigated. This electrochemistry based PCR detection platform is simple, convenient and inexpensive, and may have potential applications for practical sample monitoring.     

Simultaneous determination of uric acid and ascorbic acid at the film of chitosan incorporating cetylpyridine bromide modified glassy carbon electrode

A glassy carbon electrode (GCE) modified with the film composed of chitosan incorporating cetylpyridine bromide is constructed and used to determine uric acid (UA) and ascorbic acid (AA) by differential pulse voltammetry (DPV). This modified electrode shows efficient electrocatalytic activity and fairly selective separation for oxidation of AA and UA in mixture solution. UA is catalyzed by this modified electrode in phosphate buffer solution (pH 4.0) with a decrease of 80 mV, while AA is catalyzed with a decrease of 200 mV in overpotential compared to GCE, and the peak separation of oxidation between AA and UA is 260 mV, which is large enough to allow the determination of one in presence of the other. Under the optimum conditions, the anodic peak currents (I _pa) of DPV are proportional to the concentration of UA in the range of 2.0 × 10⁻⁶ to 6.0 × 10⁻⁴ M, with the detection limit of 5.0 × 10⁻⁷ M at a signal-to-noise ratio of 3 (S/N = 3) and to that of AA in the range of 4.0 × 10⁻⁶ to 1.0 × 10⁻³ M, with the detection limit of 8.0 × 10⁻⁷ M (S/N = 3).     

Docosyltrimethylammonium chloride modified glassy carbon electrode for simultaneous determination of dopamine and ascorbic acid

A glassy carbon electrode (GCE) modified with docosyltrimethylammonium chloride (DCTMACl) is used for simultaneous determination of dopamine (DA) and ascorbic acid (AA) using differential pulse voltammetry (DPV) technique in 0.10 mol·L^?1 phosphate buffer solution of pH 5.0. The cationic surfactant DCTMACl modified film has a positive charge. DA exists as the positively charged species, whereas AA is the negatively charged one in the solution. Thus, at DCTMACl film-modified GCE, the oxidation peak potential of AA shifts toward less negative potential and the peak current of AA increases a little, while the oxidation peak potential of DA shifts toward more positive potential and peak current decreases greatly in comparison with that on bare electrode. The two anodic peaks are separated around 200 mV. Under optimal conditions, the catalytic peak currents obtained from DPV increase linearly with concentrations of DA and AA in the ranges of 1.0?×?10^?5 to 1.0?×?10^?3?mol·L^?1. This electrode has good reproducibility, high stability in its voltammetric response, and low detection limit (micromolar) for both AA and DA. The modified electrode has been applied to the determination of DA and AA in injection.