Particle size distributions of silver nanoparticles at environmentally relevant conditions

Silver nanoparticles (Ag NPs) are becoming increasingly popular as antimicrobial agents in consumer goods with consequent risk to environmental health from discharges. Environmentally relevant fate and transport investigations are limited but essential to gain understanding towards bioavailability and toxicology. In this study, monodisperse 15 nm citrate-stabilised Ag NPs were synthesised, characterised and then fractionated by flow field-flow fractionation (FlFFF) at environmentally relevant conditions (pH 5 or 8, presence of natural organic macromolecules (NOM) and presence of sodium or calcium). At low ionic strength, Ag NPs particle size increased as pH increased from 5 to 8. However, changing the ionic strength from 10⁻³ to 10⁻² M Na increased instability of the Ag NPs, and loss of peak at pH 5 but in the presence of humic substance (HS), a reduction in NP size was seen, most likely due to a reduction in the diffuse layer. The presence of Ca²⁺ ions, at the higher ionic strengths caused complete loss of the solution Ag NPs with or without HS, most likely due to aggregation. At the lower Ca²⁺ ionic strength the Ag NPs were still unstable, but again, in the presence of HS the NPs were largely dispersed. The presence of HS improved stability of Ag NPs under these conditions by forming a surface coating resulting in both steric and charge stabilisation. This work implies that Ag NPs could have long residence times in aquatic systems in the presence of HS potentially resulting in increased bioavailability.     

Substituent electronic effects in chiral ligands for asymmetric catalysis

The majority of reports of ligand modification for catalysis have followed from systematic variation of the spatial demands of the catalyst. The focus of this review is to highlight selected major contributions to the area of substituent controlled electronic-tuning of some well known chiral ligands and the subsequent effect of these changes during asymmetric catalysis. The ligand types discussed include the salens, phosphites and phosphoramidites, ferrocene-containing ligands, oxazolines and axially chiral ligands. For each ligand type we attempt analyse the effect of systematic variation of electronics and note whether any improvements in catalyst activity and selectivity are obtained.     

Underpotential surface reduction of mesoporous CeO<Subscript>2</Subscript> nanoparticle films

The formation of variable-thickness CeO₂ nanoparticle mesoporous films from a colloidal nanoparticle solution (approximately 1–3-nm-diameter CeO₂) is demonstrated using a layer-by-layer deposition process with small organic binder molecules such as cyclohexanehexacarboxylate and phytate. Film growth is characterised by scanning and transmission electron microscopies, X-ray scattering and quartz crystal microbalance techniques. The surface electrochemistry of CeO₂ films before and after calcination at 500 °C in air is investigated. A well-defined Ce(IV/III) redox process confined to the oxide surface is observed. Beyond a threshold potential, a new phosphate phase, presumably CePO₄, is formed during electrochemical reduction of CeO₂ in aqueous phosphate buffer solution. The voltammetric signal is sensitive to (1) thermal pre-treatment, (2) film thickness, (3) phosphate concentration and (4) pH. The reversible ‘underpotential reduction’ of CeO₂ is demonstrated at potentials positive of the threshold. A transition occurs from the reversible ‘underpotential region’ in which no phosphate phase is formed to the irreversible ‘overpotential region’ in which the formation of the cerium(III) phosphate phase is observed. The experimental results are rationalised based on surface reactivity and nucleation effects.     

Applications of chiral C3-symmetric molecules

Throughout history symmetry and chirality have inspired artists and scientists alike. Given that rotational axes are the only elements of symmetry compatible with chirality, it is not surprising that C2- and C3-symmetrical molecules have attracted considerable attention. In recent years, the aesthetic appeal of C2-symmetrical molecules has been translated into many widely-used applications some of which are of commercial importance by its exploitation in the area of asymmetric catalysis. In contrast, exploitation of the arguably greater aesthetic appeal of C3-symmetric molecules is still in its infancy. This review, which surveys the applications of chiral C3-symmetrical molecules in the areas of asymmetric catalysis, molecular recognition and nanoarchitecture, has been designed with a view to identifying some of the most promising areas of application of these very beautiful molecules.     

Tracelessness Unmasked: A General Linker Nomenclature

Nowadays it is rare to find an issue of a major chemistry journal without at least one article on solid-phase synthesis. This is hardly surprising: the technique promises an end to arduous work-up procedures and the ability to facilitate the creation of vast libraries of compounds using combinatorial techniques. No longer is the technique only of interest to those involved in peptide synthesis: an enormous variety of product classes have now been prepared on and isolated from the solid phase. It is the "linker" which is the focus of this article. The linker's ultimate function is to release a product from the support into solution: it does this, without exception, with a chemical change to the product at the former linkage site. Some linkers, apparently, are "traceless". But what, in fact, is "tracelessness"? Twenty years ago, in a climate where cleavage of a linker resulted in formation of a polar carboxylic acid as the vestige of the support, the concept was attractive. Today the chemist is faced with a myriad of novel linkers which have the ability to release products bearing most major functionalities at the former linkage site and we will argue here that the term "traceless", although currently in widespread use, is meaningless. Instead, we propose a new categorization of linkers based on the functionality they release upon cleavage, and suggest a nomenclature to underpin this categorization. We anticipate that the article will also serve to highlight areas of linker technology in need of further research.     

High-density targeting of a viral multifunctional nanoplatform to a pathogenic, biofilm-forming bacterium

Nanomedicine directed at diagnosis and treatment of infections can benefit from innovations that have substantially increased the variety of available multifunctional nanoplatforms. Here, we targeted a spherical, icosahedral viral nanoplatform to a pathogenic, biofilm-forming bacterium, Staphylococcus aureus. Density of binding mediated through specific protein-ligand interactions exceeded the density expected for a planar, hexagonally close-packed array. A multifunctionalized viral protein cage was used to load imaging agents (fluorophore and MRI contrast agent) onto cells. The fluorescence-imaging capability allowed for direct observation of penetration of the nanoplatform into an S. aureus biofilm. These results demonstrate that multifunctional nanoplatforms based on protein cage architectures have significant potential as tools for both diagnosis and targeted treatment of recalcitrant bacterial infections.     

Heterogeneous thermal excitation and relaxation in supercooled liquids

We investigate a phenomenological model which rationalizes the effects of dielectric hole burning on the basis of heterogeneous dielectric and specific heat relaxation in supercooled liquids. The quantitative agreement between model predictions and dielectric hole-burning observations is lost if the assumption of correlated dielectric and thermal relaxation times is removed from the model. This suggests that dynamically distinct domains in real liquids are associated with a time constant which characterizes both the structural and thermal relaxation behaviors. The calculations demonstrate that the observed burn-induced modifications reflect the spectral selectivity and persistence time of the fictive temperatures within these domains, and that 100 or more cycles of the sinusoidal burn field can be required to saturate the heat accumulated in the slow degrees of freedom. It is also shown that the recovery of dielectric holes is entirely accounted for by the model, and that the persistence times do not provide direct insight into rate exchange processes. Additionally, the model predicts that the heating effects considered here are a significant source of nonlinear dielectric behavior, even in the absence of deliberate frequency selective hole burning.     

Aerobic oxidation reactions catalyzed by vanadium complexes of bis(phenolate) ligands

Vanadium(V) complexes of the tridentate bis(phenolate)pyridine ligand H(2)BPP (H(2)BPP = 2,6-(HOC(6)H(2)-2,4-(t)Bu(2))(2)NC(5)H(3)) and the bis(phenolate)amine ligand H(2)BPA (H(2)BPA = N,N-bis(2-hydroxy-4,5-dimethylbenzyl)propylamine) have been synthesized and characterized. The ability of the complexes to mediate the oxidative C-C bond cleavage of pinacol was tested. Reaction of the complex (BPP)V(V)(O)(O(i)Pr) (4) with pinacol afforded the monomeric vanadium(IV) product (BPP)V(IV)(O)(HO(i)Pr) (6) and acetone. Vanadium(IV) complex 6 was oxidized rapidly by air at room temperature in the presence of NEt(3), yielding the vanadium(V) cis-dioxo complex [(BPP)V(V)(O)(2)]HNEt(3). Complex (BPA)V(V)(O)(O(i)Pr) (5) reacted with pinacol at room temperature, to afford acetone and the vanadium(IV) dimer [(BPA)V(IV)(O)(HO(i)Pr)](2). Complexes 4 and 5 were evaluated as catalysts for the aerobic oxidation of 4-methoxybenzyl alcohol and arylglycerol β-aryl ether lignin model compounds. Although both 4 and 5 catalyzed the aerobic oxidation of 4-methoxybenzyl alcohol, complex 4 was found to be a more active and robust catalyst for oxidation of the lignin model compounds. The catalytic activities and selectivities of the bis(phenolate) complexes are compared to previously reported catalysts.     

C6-C8 bridged epothilones: consequences of installing a conformational lock at the edge of the macrocycle

A series of conformationally restrained epothilone analogues with a short bridge between the methyl groups at C6 and C8 was designed to mimic the binding pose assigned to our recently reported EpoA-microtubule binding model. A versatile synthetic route to these bridged epothilone analogues has been successfully devised and implemented. Biological evaluation of the compounds against A2780 human ovarian cancer and PC3 prostate cancer cell lines suggested that the introduction of a bridge between C6-C8 reduced potency by 25-1000 fold in comparison with natural epothilone D. Tubulin assembly measurements indicate these bridged epothilone analogues to be mildly active, but without significant microtubule stabilization capacity. Molecular mechanics and DFT energy evaluations suggest the mild activity of the bridged epo-analogues may be due to internal conformational strain.