Synthesis of Chemical Modified β-cyclodextrin and its Inclusion Behavior in Alcohol/Water Mixed Solvents

Abstract

The chemical modified β-cyclodextrin(CD), which bears a fluorophore group — N,N-dimethylamino-chalcone (DMAC), was synthesized. The self-inclusion behavior of this compound in aqueous solution and in alcohol/water mixed solvents was investigated in detail, and compared with the inclusion system of non-modified CD with free DMAC molecule. The results showed that a deep self-inclusion complex was formed for this compound in aqueous solution and had the ability to recognize different organic molecules by two fully different modes: “in-out” and “co-inclusion” mechanisms. The inclusion behavior of these systems in various ratio of alcohol/water mixture as solvents was investigated. The results indicated that the self-inclusion complex has a higher stability in alcohol/water mixed solvents than that in the case of non-modified CD. The chalcone group appended at β-CD enabled the host as a sensitive probe to study the inclusion behavior of CD.     

Synthesis and Crystal Structure of Blue Luminescent Cadmium(II) Coordination Networks with 4,4′-Bis(imidazol-1-ylmethyl)biphenyl from Different Solvent Systems

Two supramolecular complexes, [Cd(bimb)²Cl²] (1) and [Cd(bimb)(DMF)Cl²]·DMF (2) [bimb=4,4′-bis(imidazol-1-ylmethyl)biphenyl], were synthesized by reactions of CdCl²·2.5H²O with bimb ligand in ethanol and N,N′-dimethylformamide (DMF), respectively, and their structures were determined by X-ray crystallography. Complex 1 is an infinite 2D grid network bridged by bimb ligands, and the 2D sheets were further linked by C–H ?Cl hydrogen bonds to form a polycatenated 3D framework. Complex 2 has dicadmium(II) di-μ-chloride units which are connected by bimb bridging ligands to form an infinite non-interpenetrating 2D network. The results provide a nice example of the solvent system exerting a great effect on the construction of supramolecular frameworks.     

Short Communication: Crystal Structure of a Molecular Complex from Native β-Cyclodextrin and Copper(II) Chloride

Reaction of β-cyclodextrin (β-CD) with CuCl₂ in neutral aqueous solutions gave a stable molecular complex without any side-arm support. The X-ray crystallographic analysis clarified that the copper ion was located at the bottom of the primary-hydroxy side as a CuCl₂(H₂O)₂ form. Hydrogen bonds were found between the Cl and H₂O ligands and β-CD hydroxy and ether groups. The copper ion is axially coordinated with a hydroxy group of a neighboring β-CD molecule, giving a one-dimensional β-CD/CuCl₂ array.     

Tetralactam-modified gold electrodes for amperometric detection of acrylic acid

The presence of toxic acrylamide in a wide range of food products such as potato crisps, French fries or bread has been confirmed by Swedish scientists from Stockholm University. The neurotoxicity and possible carcinogenicity of this compound and its metabolites compel us to control them by quantitative and qualitative assays. Exposing acrylamide to pH extremes results in its hydrolysis to acrylic acid or its salt. In this work, we present the use of gold electrodes coated with self-assembled monolayers (SAMs) containing tetralactam molecules and its precursor as active elements for voltammetric detection of acrylic acid in water solution. The host molecules have been immobilised on the electrode surface by covalent Au–S bond or by embedment method into the thiol layer via hydrophobic and van der Waals interactions. Interactions with analytes were confirmed by Osteryoung square-wave voltammetry.     

Multifunctional triazolylferrocenyl Janus dendron: Nanoparticle stabilizer,smart drug carrier and supramolecular nanoreactor

Owing to their unique broken symmetry, amphiphilic Janus dendrimers and dendons provide fascinating properties for material, biological, pharmaceutical and biomedical applications. The integration of various organometallic moieties into these macromolecules will further offer the opportunity to form complex and intelligent architectures and materials. Here, we report a novel, simple and multifunctional Janus dendron containing redox‐reversible hydrophobic ferrocene (Fc) unit, complexing‐effective 1,2,3‐triazole ligand and biocompatible hydrophilic triethylene glycol termini. Silver and gold nanoparticles were firstly successfully prepared by using the Janus dendron as the reducing agent of Au(III) and Ag(I), and the stabilizer of the corresponding nanoparticles. The redox response of the Fc moiety was then employed to trigger the release of model drug, rhodamine B, encapsulated in supramolecular micelles formed by the self‐assembly of the Janus dendron. Finally, the precise and excellent metal‐complexing ability of the triazole group in this dendron was fully utilized to stabilize a water‐soluble Cu(I) catalyst, forming supramolecular nanoreactors for the catalysis of the copper(I)‐catalyzed azide alkyne cycloaddition click reaction in only water. The multifunctional characteristics of this dendron highlight the potential for organometallic Janus dendrimers and dendrons in the fields of functional materials and nanomedicines.     

Inter- and intramolecular non-covalent interactions in 1-methylimidazole-2-carbaldehyde complexes of copper,silver, and gold

Three new imidazole compounds, [CuBr₂(mimc)₂] (1), [Ag(mimc)₂][CF₃SO₃] (2), and [AuCl₃(mimc)] (3) (mimc = 1-methylimidazole-2-carbaldehyde), have been synthesized, structurally characterized, and further analyzed using the QTAIM analysis. The compounds exhibit self-assembled 3D networks arising from intermolecular non-covalent interactions such as metallophilic interactions, metal-π contacts, halogens–halogen interactions, and hydrogen bonds. These weak interactions have a strong impact on the coordination sphere of the metal atoms and on the packing of compounds 1, 2, and 3.