Direct aziridination of alkenes by a cationic (salen)ruthenium(VI) nitrido complex

[RuVI(N)(salchda)(CH3OH)]PF6 (1) (salchda = N,N'-bis(salicylidene)o-cyclohexyldiamine dianion) reacts readily with 2,3-dimethyl-2-butene at room temperature in the presence of pyridine or 1-methylimidazole to give initially [RuIV(Az1(-H))(salchda)(py)]PF6 (2, Az1 = 2,2,3,3-tetramethylaziridine), which is then slowly reduced to [RuIII(Az1)(salchda)(py)]PF6 (3). 1 also reacts with a variety of aryl-substituted alkenes such as styrene and trans-beta-methylstyrene in the presence of py or 1-MeIm to give the corresponding ruthenium(III) aziridine complexes. The structures of 3 and [RuIII(Az2)(salchda)(1-MeIm)]PF6 (4, Az2 = trans-2-methyl-3-phenylaziridine) have been determined by X-ray crystallography. The Ru-N(aziridine) distances (2.1049, 2.097 A) are consistent with a neutral aziridine ligand. The C-C and C-N distances in the aziridine ligands are all indicative of single bonds.     

Large-scale fabrication of wafer-size colloidal crystals, macroporous polymers and nanocomposites by spin-coating

This paper reports a simple spin-coating technique for rapidly fabricating three types of technologically important materials--colloidal crystal, macroporous polymer, and polymeric nanocomposite, each with high crystalline qualities and wafer-scale sizes. Dispersion of monodisperse silica colloids in triacrylate monomers is spin-coated onto a variety of substrates. Shear-induced ordering and subsequent polymerization lead to the formation of three-dimensionally (3D) ordered colloidal crystals trapped inside a polymer matrix. The thickness of as-synthesized colloidal crystal-polymer nanocomposite is highly uniform and can be controlled simply by changing the spin speed and time. Selective removal of the polymer matrix and silica spheres lead to the formation of large-area colloidal crystals and macroporous polymers, respectively. The wafer-scale process is compatible with standard semiconductor microfabrication, as multiple micrometer-sized patterns can be created simultaneously for potential device applications. Normal-incidence transmission spectra in the visible and near-infrared regions show distinct peaks due to Bragg diffraction from 3D ordered structures. The spin-coating process opens a new route to the fundamental studies of shear-induced crystallization, melting and relaxation.     

1,3‐dipolar cycloaddition reactions of nitrile oxides to prop‐1‐ene‐1,3‐sultone

The reaction of prop‐1‐ene‐1,3‐sultone 1 with a variety of nitrile oxides 3 afforded novel [3+2] cycloaddition products 4 in good yield. The cycloaddition reaction achieved excellent regioselectivity.     

CoCl_2·6H_2O or LaCl_3·7H_2O Catalyzed Biginelli Reaction. One-Pot Synthesis of 3,4-Dihydropyrimidin-2(1 H)-ones

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Electrochemical behavior and determination of epinephrine at a mercaptoacetic acid self-assembled gold electrode

The electrochemical behavior of epinephrine (EP) at a mercaptoacetic acid (MAA) self-assembled monolayer modified gold electrode was studied. The MAA/Au electrode is demonstrated to promote the electrochemical response of epinephrine by cyclic voltammetry. The possible reaction mechanism is also discussed. The diffusion coefficient D of EP is 6.85 × 10⁻⁶ cm² s⁻¹. In 0.1 mol L⁻¹ phosphate buffer (pH 7.20), a sensitive oxidation peak was observed at 0.177 V, and the peak current is proportional to the concentration of EP in the range of 1.0 × 10⁻⁵–2.0 × 10⁻⁴ mol L⁻¹ and 1.0 × 10⁻⁷–1.0 × 10⁻⁶ mol L⁻¹. The detection limit is 5 × 10⁻⁸ mol L⁻¹. The modified electrode is highly stable and can be applied to the determination of EP in practical injection samples. The method is simple, quick, sensitive and accurate.     

The Color Reaction of Mercury(II) with the New Reagent 2-Methylthiophenyldiazoaminoazobenzene and Its Application

A new and very sensitive and selective chromogenic reagent, 2-methylthiophenyldiazoaminoa-zobenzene (MTDAA), was synthesized and studied in detail for the determination of trace mercury(II) in water samples. The method is based on the color reaction between MTDAA and mercury(II). It was found that mercury(II) reacts with MTDAA in Na₂B₄O₇-NaOH buffer solution (pH = 10.0) to form 1 : 2 red complexes; these show maximum absorption at 520 nm. Beer’s law is obeyed in 0–15 µg of mercury(II) in 25 mL of solution. The apparent molar absorptivity of the complex is 1.33 × 10⁵ L/(mol cm); its limit of quantification, limit of detection, and relative standard deviation are 0.75 ng/mL, 0.27 ng/mL, and 1.0%, respectively, giving better sensitivity. The influence of the reaction variables and the effect of interfering ions are reported; most of the metal ions in water samples can be tolerated in considerable amounts. Only a few ions can interfere with the determination of trace mercury(II), but these can be eliminated by prior extraction. The proposed method is sensitive, simple, and rapid. It has been applied to the determination of trace mercury(II) in water samples with satisfactory results.__________From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 7, 2005, pp. 703–706.Original English Text Copyright © 2005 by Guo, Din, Tian, Liu, Chang, Meng.The text was submitted by the authors in English.     

The 7‐bromo derivative of 2‐amino‐2′‐deoxytubercidin fluorinated at the sugar moiety

The title compound, 2,4‐diamino‐5‐bromo‐7‐(2‐deoxy‐2‐fluoro‐β‐d ‐arabinofuranosyl)‐7H‐pyrrolo[2,3‐d]pyrimidine, C₁₁H₁₃BrFN₅O₃, shows two conformations of the exocyclic C4′—C5′ bond, with the torsion angle γ (O5′—C5′—C4′—C3′) being 170.1 (3)° for conformer 1 (occupancy 0.69) and 60.7 (7)° for conformer 2 (occupancy 0.31). The N‐glycosylic bond exhibits an anti conformation, with χ = −114.8 (4)°. The sugar pucker is N‐type (C3′‐endo; ³T₄), with P = 23.3 (4)° and τ_m = 36.5 (2)°. The compound forms a three‐dimensional network that is stabilized by several intermolecular hydrogen bonds (N—H...O, O—H...N and N—H...Br).     

Surmounting tumor resistance to metallodrugs by co-loading a metal complex and siRNA in nanoparticles

Copper complexes are promising anticancer agents widely studied to overcome tumor resistance to metal-based anticancer drugs. Nevertheless, copper complexes per se encounter drug resistance from time to time. Adenosine-5′-triphosphate (ATP)-responsive nanoparticles containing a copper complex CTND and B-cell lymphoma 2 (Bcl-2) small interfering RNA (siRNA) were constructed to cope with the resistance of cancer cells to the complex. CTND and siRNA can be released from the nanoparticles in cancer cells upon reacting with intracellular ATP. The resistance of B16F10 melanoma cells to CTND was terminated by silencing the cellular Bcl-2 gene via RNA interference, and the therapeutic efficacy was significantly enhanced. The nanoparticles triggered a cellular autophagy that amplified the apoptotic signals, thus revealing a novel mechanism for antagonizing the resistance of copper complexes. In view of the extensive association of Bcl-2 protein with cancer resistance to chemotherapeutics, this strategy may be universally applicable for overcoming the ubiquitous drug resistance to metallodrugs.

Bcl-2-related tumor resistance to anticancer drugs can be overcome by silencing the cellular Bcl-2 gene via RNA interference. The realization of the goal is exemplified by delivering Bcl-2 siRNA and a tumor-resistant Cu complex to cancer cells with an ATP-responsive nanocarrier.     

Direct injection of plasma to determine pseudoephedrine by high performance liquid chromatography with column switching

An HPLC method has been developed for the determination of pseudoephedrine in plasma using column switching. Preparation of the sample was simple in that only 1000 microL of water was added to 200 microL of plasma before injection. A 900 microL aliquot was injected onto the precolumn. Double distilled water was used to elute and remove proteins and polar components in the sample. The components retained on the precolumn were flushed forward onto the analytical column by the mobile phase (acetonitrile-0.2 mol/L ammonium sulphate, 10:90 v/v) with automated column switching. The limit of determination of pseudoephedrine in plasma was 12 ng/mL. The relative standard deviations of intra- and inter-assay for the determination of pseudoephedrine in plasma were 1.2-9.8% over the concentration range 1020-21.8 ng/mL. The mean recovery by on-line solid phase extraction was 94.76% (RSD = 1.1%).     

Unsymmetrical linear pentanuclear nickel string complexes: [Ni(5)(tpda)(4)(H(2)O)(BF(4))](BF(4))(2) and [Ni(5)(tpda)(4)(SO(3)CF(3))(2)](SO(3)CF(3))

The one-electron oxidized linear pentanuclear nickel complexes [Ni(5)(tpda)(4)(H(2)O)(BF(4))](BF(4))(2) (1) and [Ni(5)(tpda)(4)(SO(3)CF(3))(2)](SO(3)CF(3)) (2) have been synthesized by reacting the neutral compound [Ni(5)(tpda)(4)Cl(2)] with the corresponding silver salts. These compounds have been characterized by various spectroscopic techniques. Compound 1 crystallizes in the monoclinic space group P2(1)/n with a = 15.3022(1) A, b = 31.0705(3) A, c = 15.8109(2) A, beta = 92.2425(4) degrees, V = 7511.49(13) A(3), Z = 4, and compound 2 crystallizes in the monoclinic space group C2/c with a = 42.1894(7) A, b = 17.0770(3) A, c = 21.2117(4) A, beta = 102.5688(8) degrees, V = 14916.1(5) A(3), Z = 8. X-ray structural studies reveal an unsymmetrical Ni(5) unit for both compounds 1 and 2. Compounds 1 and 2 show stronger Ni-Ni interactions as compared to those of the neutral compounds.