Australian Journal of Chemistry
Volume 64
Number 3 2011 RESEARCH FRONT: ICCC39 (39th International Conference on Coordination Chemistry): Bioinorganic Chemistry
Metals in biological systems was one of the major themes of the 39th International Conference on Coordination Chemistry (Adelaide, July 2010). This Research Front comprises papers from some of the leading participants in ICCC39 drawn from the 'bioinorganic' area.
Metallo-oxidases are a sub-family of multi-copper oxidase enzymes that catalyze oxidation of low-valent transition metal ions such as FeII, CuI, and MnII. They play important roles in nutrient metal uptake and homeostasis. This review discusses the molecular basis of the substrate specificities of these enzymes.
Metal coordination complexes are emerging as an important class of optical imaging probes. They may function not only as cellular stains but also as responsive probes, reporting changes in ionic composition. The critical factors in designing such probes are reviewed, and prospects considered for developing lanthanide(iii) probes capable of reporting changes in key bioactive anions.
The synthesis of four new bis(thiosemicarbazone) ligands with water-solubilizing aromatic sulfonate groups and their CuII complexes is presented. Two of the new ligands were radiolabelled with positron-emitting 64Cu with a view to assessing their potential as ligands that bind radioactive copper isotopes for application in diagnostic radiopharmaceuticals. The cellular uptake of the copper complexes was investigated in SH-SY5Y cells.
Treatment of A549 human lung carcinoma cells with a DNA metallointercalator complex containing a PtII-terpy (terpy = 2,2′:6′,2′′-terpyridine) unit linked to a functionalized closo-carborane cage results in the uptake of the complex within the cells (see figure), as determined by synchrotron X-ray fluorescence imaging.
The heterometallic complex [FeIIIZnII(BPBPMPV)(CH3COO)2](ClO4), prepared from the ligand 2-((bis(pyridin-2-ylmethyl)amino)methyl)-6-(((2-hydroxy-4-(4-vinylbenzyloxy)benzyl)(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol (H2BPBPMPV) possesses a pendant olefin substituent potentially suitable for copolymerization with appropriate monomers, is catalytically active towards an activated phosphate ester, and is a low-molecular-weight mimic of the purple acid phosphatase metalloenzymes.
The successful preparation of a novel azido group-containing ligand and its subsequent couplings to an alkyne-containing peptide nucleic acid (PNA) monomer and to a 17-mer alkyne-containing PNA oligomer using Click Chemistry is reported. Our attempts to complex Dpam-PNA with [NEt4]2[ReBr3(CO)3] and the [99mTc(CO)3(H2O)3]+ moiety are also discussed in detail.
Successful stabilization of triaminechloridoplatinum(ii) moieties by oxidation to PtIV has been demonstrated using a combination of electrochemistry and X-ray absorption near-edge spectroscopy analysis of the oxidation states in cancer cells.
A promising avenue of research in materials science is to follow the strategies used by nature to fabricate ornate hierarchical materials. This review outlines the biological synthesis of oxide nanomaterials achieved using fungal biosynthesis routes. A critical overview of the current status and future scope towards ‘green’ syntheses of oxide nanomaterials is also presented.
In this paper, we present recent work from our group focussed on the fabrication of nanopore and nanotube arrays of anodic aluminium oxide and nanotube titania using self-ordered electrochemistry and their applications in several key areas including template synthesis, molecular separation, optical sensing, and drug delivery.
The molecular behavior of fluorescently labelled generation 4 polyamidoamine (PAMAM) dendrimers (G4-FITC) in a cellular environment is investigated. G4-FTIC was found to buffer lysosomal pH and translocate into endosomes, lysosomes, mitochondria, and Golgi apparatus. The findings will facilitate the development of more effective PAMAM-mediated drug and gene delivery systems.
The synthesis and surface morphology of POSS-incorporated polymers such as 1NPONDI, 2NPONDI, and 3NPONDI was reported. The surface morphology and thermal properties of hybrids were affected by the POSS macromer. The hydrophilic/hydrophobic balance will be an important key to control the morphologies as well as final microstructures of the polymer matrix. The POSS molecule forms nano/micro level aggregations, giving evidence of the formation of microphase morphology and surface roughness. The study focussed on the dispersion, surface morphology, and the microstructure of POSS in TFNDI-NPONDI copolymer.
A highly efficient synthesis of p-carboethoxy-tristyryl and carboethoxy-terastyrenyl benzene derivatives through multiple Heck cross-coupling reaction is reported.
Neat liquid 3-alkoxy-2-bromothiophenes such as 2-bromo-EDOT have been shown to autopolymerize at room temperature and above, depending on their proton acidity and the nature and arrangement of substituents.
Quantum chemical calculations of the structure and stability of the MKr42+ series at the CCSD(T) theoretical level have been performed. The role of the interaction was investigated using the natural bond orbital (NBO), Laplacian, electron density deformation, electron localization function and reduced density gradient analysis. The results indicate that a covalent contribution occurs in the Kr-M2+ bonding.
Coordination spheres of ORTEP diagrams of [SmL2(NO3)(DMF)2]2 complex. Ligand L2 acts as a dibasic tetradentate, binding to SmIII through the phenolate oxygen atom, nitrogen atom of quinolinato unit, C=N group and –O–C=N– group. Dimerization of this monomeric unit occurs through the phenolate oxygen atoms leading to a central four-membered (SmO)2-ring.
The publication rate on RAFT polymerization continues to increase with the latest publication of a third update. Freely access the three reviews previously written by CSIRO scientists Moad, Rizzardo, and Thang on this subject in Australian Journal of Chemistry.