不可逆电活性药物米托蒽醌与脱氧核糖核酸的相互作用

研究了抗癌新药米托蒽醌(MXT)的电化学行为及与脱氧核糖核酸(DNA)的相互作用，推导了适用于研究不可逆电活性分子与DNA相互作用的电化学公式，运用该公式可以简便、快速地测定靶向分子与DNA的结合常数和结合位点数。实验发现，MXT与小牛胸腺DNA的结合以蒽醌母核的嵌插作用为主，同时，烃氨基侧链与骨架磷酸基团之间的静电吸引对母核起稳定作用，使化合物易于嵌入DNA的平面结构。MXT与DNA相互作用引起的峰电流的变化可以用于分析测定DNA。     

Cation recognition by new diester- and diamide-calix[4]arenediquinones and a diamide-benzo-15-crown-5-calix[4]arene

The synthesis, metal, ammonium and alkyl ammonium cation coordination chemistry and electrochemical recognition studies of new diester-and diamide-calix[4]arenediquinone receptors are described. In addition the synthesis and coordination properties of a novel diamide benzo-15-crown-5-calix[4]arene molecule is reported.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

PAMAM Dendrimers as Anchors for the Preparation of Electrocatalytically Active Ultrathin Metallic Films

This paper describes the formation of catalytically active thin films of Pt, Pt/Au, and Pt/Ru on gold substrates stabilized by amine‐terminated polyamidoamine (PAMAM) dendrimers. A monolayer of dendrimer is initially self‐assembled on the gold substrate, which serves as a template for the growth of catalytically active thin films. As dendrimers contain tens to hundreds of functional groups at the periphery, the aggregate strength of the multidentate interactions with the gold substrate leads to the formation of robust films. The films were found to exhibit high catalytic activity for the oxidation of small hydrocarbons such as methanol. Such films offer versatility and scope for the design of effective electrocatalysts, especially in the context of microfuel cells and “dendrichips”; hence, they could find applications in the fields of sensors, fuel cells, and waste‐water treatment.     

A mini-review on MXenes as versatile substrate for advanced sensors

MXenes have emerged as versatile 2D materials that are already gaining paramount attention in the areas of energy,catalyst,electromagnetic shielding,and sensors.The unique surface chemistry,graphene-like mo rphology,high hydrophilicity,metal-like conductivity with redox capability identifies MXenes,as an ideal material for surface-related applications.This short review summarizes the most recent reports that discuss the potential application of MXenes and their hybrids as a transducer material for advanced sensors.Based on the nature of transducing signals,the discussion is categorized into three sections,which include electrochemical(bio) sensors,gas sensors,and finally,electro-chemiluminescence fluorescent sensors.The review provides a concise summary of all the analytical merits obtained subsequent to the use of MXenes,followed by endeavors that have been made to accentuate the future perspective of MXenes in sensor devices.     

Homocoenzyme B12 and Bishomocoenzyme B12: Covalent Structural Mimics for Homolyzed,Enzyme‐Bound Coenzyme B12

Efficient electrochemical syntheses of “homocoenzyme B₁₂” ( 2 , Co_β‐(5′‐deoxy‐5′‐adenosyl‐methyl)‐cob(III )alamin) and “bishomocoenzyme B₁₂” ( 3 , Co_β‐[2‐(5′‐deoxy‐5′‐adenosyl)‐ethyl]‐cob(III )alamin) are reported here. These syntheses have provided crystalline samples of 2 and 3 in 94 and 77 % yield, respectively. In addition, in‐depth investigations of the structures of 2 and 3 in solution were carried out and a high‐resolution crystal structure of 2 was obtained. The two homologues of coenzyme B₁₂ ( 2 and 3 ) are suggested to function as covalent structural mimics of the hypothetical enzyme‐bound “activated” (that is, “stretched” or even homolytically cleaved) states of the B₁₂ cofactor. From crude molecular models, the crucial distances from the corrin‐bound cobalt center to the C5′ atom of the (homo)adenosine moieties in 2 and 3 were estimated to be about 3.0 and 4.4 Å, respectively. These values are roughly the same as those found in the two “activated” forms of coenzyme B₁₂ in the crystal structure of glutamate mutase. Indeed, in the crystal structure of 2 , the cobalt center was observed to be at a distance of 2.99 Å from the C5′ atom of the homoadenosine moiety and the latter was found to be present in the unusual syn conformation. In solution, the organometallic moieties of 2 and 3 were shown to be rather flexible and to be considerably more dynamic than the equivalent group in coenzyme B₁₂. The homoadenosine moiety of 2 was indicated to occur in both the syn and the anti conformations.     

Syntheses,structures and electrochemical properties of ruthenium(II/III) complexes with tetradentate Schiff base ligands

Three unsymmetrical tetradentate Schiff base ligands, H₂salipn, H₂salipn-Br₄ and H₂salipn-Cl₂, have been synthesized from the typical condensation reactions of treating 1,2-diaminopropane with salicylaldehyde, 3,5-dibromosalicylaldehyde and 5-chlorosalicylaldehyde, respectively. Treatment of [RuCl₂(PPh₃)₃] with one equivalent of H₂salipn or H₂salipn-Br₄ in the presence of triethylamine in tetrahydrofuran (THF) afforded the corresponding ruthenium(III) complexes [Ru^IIICl(PPh₃)(salipn)] (1) and [Ru^IIICl(PPh₃)(salipn-Br₄)] (2). Interaction of [RuHCl(CO)(PPh₃)₃] with one equivalent of H₂salipn-Cl₂ or H₂salipn-Br₄ under the same conditions led to isolation of ruthenium(II) complexes [Ru^II(CO)(PPh₃)(salalipn-Cl₂)] (3) and [Ru^II(CO)(PPh₃)(salalipn-Br₄)] (4), respectively, in which one of the imine bonds was nucleophilically attacked by hydride to result in the formation of a mixed imine-amine ligand. The molecular structures of 1?1.5CH₂Cl₂, 2, 3?0.5CH₂Cl₂ and 4 have been determined by single-crystal X-ray crystallography. The electrochemical properties of 1–4 were also investigated. Their cyclic voltammograms displayed quasi-reversible Ru(IV)/Ru(III) and Ru(III)/Ru(II) couples with E^o ranging from 0.67 to 1.05 V and 0.74 to 0.80 V vs. Ag/AgCl (0.1 M), respectively.     

Functional Polyoxometalate Thin Films via Electrostatic Layer-by-Layer Self-Assembly

Polyoxometalates (POMs) comprise a structurally diverse class of inorganic transition metal oxygen clusters which—owing to their unique electronic properties—hold promise for a host of technological applications such as electrochromic windows, sensors, or heterogeneous catalysts, prototypic examples of which will be briefly exemplified. The integration of POMs into functional architectures and devices, however, necessitates the development of general methods that allow positioning these clusters in well-defined supramolecular architectures, thin films, or mesophases. This short review highlights recent advances in the preparation of composite multilayers fabricated by electrostatic layer-by-layer self-assembly (ELSA) of POMs and a variety of water-soluble cationic species, including transition metal complexes, cationic surfactants, polycations and bipolar pyridine.     

Vanadium Doped Sol-Gel TiO2 Coatings

A study of the experimental conditions required to obtain vanadium doped sol-gel TiO2 coatings is presented. Tetraethyl orthotitanate was employed as the TiO2 source and VCl3, VOSO4 · H2O and VOSO4 dissolved H2SO4 where employed as vanadium sources.Dip coating has been used to produce coatings on silicon wafers, spectral carbon electrodes and titanium electrodes. Both supported and unsupported films have been studied by UV-Vis spectra, IR spectroscopy and X-ray diffraction (XRD). The measurements have been made on samples as prepared and treated thermally at temperatures between 100°C and 300°C. The thermal treatment temperatures have been established from DTA/TGA measurements.The vanadium doped sol-gel TiO2 coatings have been tested as sensors for redox potential measurements in electrochemical processes. The influence of both the thickness of films and the nature of substrate has been investigated.     

Chemically Sensitive Field‐Effect Transistors and Chemiresistors: New Materials and Device Structures

Electronic sensor technology remains of widespread and intense interest. There are compelling needs to detect chemical species ranging from small molecules dispersed in the gas phase to complex biopolymers in aqueous solution. This review describes some recent advances in three main areas: chemically sensitive resistors (chemiresistors, CRs) including inorganic and organic based devices, field effect transistors (FETs) with semiconducting layers and/or gates with chemical sensitivity, and sensors based on the differential conductivity of nanotubes and nanowires. Results reported in the last two to three years are emphasized, highlighting some current trends in the development of sensors for applications such as diagnostics, process monitoring, and security.