Stable Anticancer Gold(III)–Porphyrin Complexes: Effects of Porphyrin Structure

In the design of physiologically stable anticancer gold(III) complexes, we have employed strongly chelating porphyrinato ligands to stabilize a gold(III) ion [Chem. Commun. 2003 , 1718; Coord. Chem. Rev. 2009 , 253, 1682]. In this work, a family of gold(III) tetraarylporphyrins with porphyrinato ligands containing different peripheral substituents on the meso‐aryl rings were prepared, and these complexes were used to study the structure–bioactivity relationship. The cytotoxic IC₅₀ values of [Au(Por)]⁺ (Por=porphyrinato ligand), which range from 0.033 to >100 μM , correlate with their lipophilicity and cellular uptake. Some of them induce apoptosis and display preferential cytotoxicity toward cancer cells than to normal noncancerous cells. A new gold(III)–porphyrin with saccharide conjugation [Au(4‐glucosyl‐TPP)]Cl ( 2 a ; H₂(4‐glucosyl‐TPP)=meso‐tetrakis(4‐β‐D ‐glucosylphenyl)porphyrin) exhibits significant cytostatic activity to cancer cells (IC₅₀=1.2–9.0 μM ) without causing cell death and is much less toxic to lung fibroblast cells (IC₅₀>100 μM ). The gold(III)–porphyrin complexes induce S‐phase cell‐cycle arrest of cancer cells as indicated by flow cytometric analysis, suggesting that the anticancer activity may be, in part, due to termination of DNA replication. The gold(III)–porphyrin complexes can bind to DNA in vitro with binding constants in the range of 4.9×10⁵ to 4.1×10⁶ dm³ mol^?1 as determined by absorption titration. Complexes 2 a and [Au(TMPyP)]Cl₅ ( 4 a ; [H₂TMPyP]⁴⁺=meso‐tetrakis(N‐methylpyridinium‐4‐yl)porphyrin) interact with DNA in a manner similar to the DNA intercalator ethidium bromide as revealed by gel mobility shift assays and viscosity measurements. Both of them also inhibited the topoisomerase I induced relaxation of supercoiled DNA. Complex 4 a , a gold(III) derivative of the known G‐quadruplex‐interactive porphyrin [H₂TMPyP]⁴⁺, can similarly inhibit the amplification of a DNA substrate containing G‐quadruplex structures in a polymerase chain reaction stop assay. In contrast to these reported complexes, complex 2 a and the parental gold(III)–porphyrin 1 a do not display a significant inhibitory effect (<10 %) on telomerase. Based on the results of protein expression analysis and computational docking experiments, the anti‐apoptotic bcl‐2 protein is a potential target for those gold(III)–porphyrin complexes with apoptosis‐inducing properties. Complex 2 a also displays prominent anti‐angiogenic properties in vitro. Taken together, the enhanced stabilization of the gold(III) ion and the ease of structural modification render porphyrins an attractive ligand system in the development of physiologically stable gold(III) complexes with anticancer and anti‐angiogenic activities.     

Bis(imino)pyridine palladium(II) complexes as efficient catalysts for the Suzuki–Miyaura reaction in water

Bis(imino)pyridine palladium(II) complexes 3 and 4 of type [PdCl(L)PF₆] are found to be efficient catalysts for Suzuki–Miyaura reactions of aryl halides and arylboronic acids. The reactions proceed smoothly to generate the corresponding biaryl compounds in moderate to excellent yields. The synthesis of various fluorinated biphenyl derivatives was successfully achieved by the complex 4 catalyzed the Suzuki–Miyaura reaction in the presence of surfactants bearing a long alkyl chain. Copyright © 2009 John Wiley & Sons, Ltd.     

Advanced form-finding for cable-strut structures

A numerical method is presented for form-finding of cable-strut structures. The topology and the types of members are the only information that is required in this form-finding process. Dummy members are used to transform the cable-strut structure with supports into self-stressed system without supports. The requirement on rank deficiencies of the force density and equilibrium matrices for the purpose of obtaining a non-degenerate d-dimensional self-stressed structure has been explicitly discussed. The spectral decomposition of the force density matrix and the singular value decomposition of the equilibrium matrix are performed iteratively to find the feasible sets of nodal coordinates and force densities which satisfy the minimum required rank deficiencies of the force density and equilibrium matrices, respectively. Based on numerical examples it is found that the proposed method is very efficient, robust and versatile in searching self-equilibrium configurations of cable-strut structures.     

An amperometric ethanol sensor based on foam nickel electrode

An amperometric sensor using foam nickel electrode as the working electrode for the measurement of ethanol in alkaline solution has been developed. Cyclic voltammetry and chronoamperometry are employed to analyze electrochemical behavior of the electrode. The results show that the oxidation of ethanol is more efficient on the foam nickel electrode than that on the nickel foil electrode. The sensor exhibits a good linear relationship between response current and ethanol concentration in the range of 4 to 1400 ppm with a detection limit of 0.8 ppm. The sensitivity and the response time of the sensor are 4.63 μA/ppm and 10 s respectively. Additionally, the sensor has 60 days shelf-life time at least.     

A general solution for static piezothermoelastic problems of crystal class 6mm solids

In this paper, a general solution for three-dimensional static piezothermoelastic problems of crystal class 6mm solids is presented. The general solution involves four piezoelastic potential functions and a piezothermoelastic potential function, of which four piezoelastic potential functions are governed by weighted harmonic differential equations. Compared with the general solution given by Ashida et al., in which seven potential functions are introduced, the general solution proposed in the present paper is more rigorously derived. Moreover, it has a simple form and is convenient for application. As an illustrative example, the problem of a pyroelectric half-space subjected to axisymmetric heating is studied. Numerical results of displacements stresses, electric potential and electric displacements are obtained for a cadmium selenide half-space. Thermally induced displacements and stress distribution are compared with those obtained for the same material without piezoelectric and pyroelectric effects. Project supported by the National Natural Science Foundation of China (19872060).     

Solvent Effects on Aza‐anionic Cycloaromatization of 2‐(2‐Substituted‐ethynyl)benzonitriles

The methanolysis of 2‐(2‐aryl ethynyl)benzonitriles is accelerated when the polar aprotic solvents are added, which could enhance the 6‐endo pathway and give isoquinolones, though the 5‐exo pathway is occupied mostly. The yields of products would also be in creased.     

Effect of metal ions in organic synthesis. Part XXXI. Synthesis of new 3-carbonyl- and 3-carboxy-1-heterocyclaminopyrroles by copper(II) chloride-catalyzed reaction of heterocyclic azoalkenes

The direct synthesis of a new class of unknown 1-heterocyclamino-3-carbonylpyrroles and 1-heterocyclamino-3-carboxypyrroles by copper(II) chloride-catalyzed reaction of heterocyclic conjugated azoalkene derivatives with β-diketones and β-ketoesters is reported.     

多亚甲基桥连双巴比妥的合成及鉴定

在ＰＴＣ条件下合成了多亚甲基桥连的双巴比妥类化合物１～３，并通过了元素分析，ＩＲ及＾１ＨＮＭＲ予以鉴定。     

Preparation of gradient copolymers via ATRP using a simultaneous reverse and normal initiation process. I. Spontaneous gradient

Spontaneous gradient copolymers were prepared in both bulk and miniemulsion systems via Atom Transfer Radical Polymerization (ATRP) utilizing a Simultaneous Reverse and Normal Initiation (SR & NI) process. Both instantaneous and cumulative compositions were used to characterize the gradient copolymers. The gradient copolymers were obtained with an array of gradient compositions ranging from a subtle to strong variation in monomer distribution along the polymer backbones, depending on the ratio of comonomers initially added to the copolymerization system. The compositions of the gradient copolymer produced in miniemulsion systems were similar to those generated in bulk. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3616–3622, 2005