N,N-Dimethylbenzylamine, alkyl and aryl imines derived from benzaldehyde, and 2-phenyl-4,4-dimethyloxazoline all undergo cyclometallation with [IrCl 2 Cp*] 2 (Cp* = η-C 5 Me 5 ) when treated with NaOAc in dichloromethane at room temperature. The imines are also cyclometallated by [RhCl 2 Cp*] 2 under the same conditions whilst only N-alkyl imines are cyclometallated by [RuCl 2 (p-cymene)] 2 . The role of acetate in the cyclometallation is more than just as a base. X-Ray structures of cyclometallated complexes [MCl{C 6 H 4 -2-C(H)᎐ ᎐ NCH 2 CH 2 OMe-κC,N}(η-ring)](M = Ir, Rh ring = Cp*; M = Ru, ring = p-cymene), [MCl{C 6 H 4 -2-C(H)᎐ ᎐ NCH 2 CH 2 OMe-κC,N}Cp*](M = Ir, Rh), [RuCl(η 2 -O 2 CMe)(p-cymene)] and [IrCl 2 (NH 2 Ph)Cp*] are reported.

The hypoxic response in humans is regulated by the hypoxiainducible transcription factor system; inhibition of hypoxia-inducible factor (HIF) activity has potential for the treatment of cancer. Chetomin, a member of the epidithiodiketopiperazine (ETP) family of natural products, inhibits the interaction between HIF-␣ and the transcriptional coactivator p300. Structure-activity studies employing both natural and synthetic ETP derivatives reveal that only the structurally unique ETP core is required and sufficient to block the interaction of HIF-1␣ and p300. In support of both cell-based and animal work showing that the cytotoxic effect of ETPs is reduced by the addition of Zn 2؉ through an unknown mechanism, our mechanistic studies reveal that ETPs react with p300, causing zinc ion ejection. Cell studies with both natural and synthetic ETPs demonstrated a decrease in vascular endothelial growth factor and antiproliferative effects that were abrogated by zinc supplementation. The results have implications for the design of selective ETPs and for the interaction of ETPs with other zinc ion-binding protein targets involved in gene expression.

18The increasing prevalence of wound infections caused by antibiotic resistant bacteria is an urgent 19 challenge facing modern medicine. To address this issue the expedient use of antimicrobial metals 20 such as zinc, copper and silver were incorporated into an FDA-approved polymer (polycaprolactone -21 PCL) to produce filaments for 3D printing. These metals have broad-spectrum antimicrobial 22properties, and moreover, copper and zinc can enhance the wound healing process. 3D scanning 23 was used to construct 3D models of a nose and ear to provide the opportunity to customize shape 24 and size of a wound dressing to an individual patient. Hot melt extrusion was used to extrude pellets 25 obtained by vacuum-drying of solutions of PCL and the different metals in order to manufacture 26 metal-homogeneously-loaded filaments. Wound dressings with different shapes were produced with 27 the filaments containing different concentrations of metals. Release of the metals from the dressings 28 was determined by inductively coupled plasma atomic emission spectroscopy. All the different metal 29 dressings show fast release (up to 24 h) followed by slow release (up to 72 h). The antibacterial 30 efficacy of the wound dressings was tested using a thermal activity monitor system, revealing that 31 silver and copper wound dressings had the most potent bactericidal properties. This study shows 32 that 3D scanning and 3D printing, which are becoming simpler and more affordable, have the 33 potential to offer solutions to produce personalised wound dressings.

[reaction: see text]Reaction of indole amides 5 with tributylstannane gave spiroindolenines 9 which are readily converted into spiropyrrolidinyloxindoles. This tricyclic system is found in a number of interesting natural products.

Three-dimensional (3D) chemical models are a well-established learning tool used to enhance the understanding of chemical structures by converting two-dimensional paper or screen outputs into realistic three-dimensional objects. While commercial atom model kits are readily available, there is a surprising lack of large molecular and orbital models that could be used in large spaces. As part of a program investigating the utility of 3D printing in teaching, a modular size-adjustable molecular model and orbital kit was developed and produced using 3D printing and was used to enhance the teaching of stereochemistry, isomerism, hybridization, and orbitals.