An Analytical Method for Detecting Toxic Metal Cations Using Cyclotriveratrylene Derivative Capped Gold Nanoparticles

Cyclotriveratrylene-oxime (CTV-oxime) derivatives that terminate with a dithiolate linker were synthesized enabling the supramolecular scaffold to adhere to gold nanoparticles (AuNPs) with the bowl-shaped cavity of the CTV scaffold exposed for utilization in host–guest chemistry. Exposure of these CTV functionalized AuNPs to varying concentrations of di- and trivalent metal cations resulted in the formation of large CTV-AuNP polymeric clusters and an accompanying a shift in the plasmon resonance. These interactions between the CTV-AuNPs and the metal cations in solution provides proof-of-concept that supramolecular functionalized AuNPs can be used as a simple and straightforward, on-site detection system for toxic metal cations in solution. The order of binding affinity of the metals studied based on observed Kd values is Cu2+ \u3e Zn2+ \u3e Pb2+ \u3e Hg2+ \u3e Eu3+ \u3e Cd2+

Direct Patterning of a Cyclotriveratrylene Derivative for Directed Self-assembly of C60

A novel apex-modified cyclotriveratrylene (CTV) derivative with an attached thiolane-containing lipoic acid linker was directly patterned onto gold substrates via dip-pen nanolithography (DPN). The addition of a dithiolane-containing linker to the apex of CTV provides a molecule that can adhere to a gold surface with its bowl-shaped cavity directed away from the surface, thereby providing a surface-bound CTV host that can be used for the directed assembly of guest molecules. Subsequent exposure of these CTV microarrays to C60 in toluene resulted in the directed assembly of predesigned, spatially controlled, high-density microarrays of C60. The molecular recognition capabilities of this CTV template toward C60 provides proof-of-concept that supramolecular CTV scaffolds can be directly patterned onto surfaces providing a foundation for the development of organic electronic and optoelectronic materials

Apparent Alkyl Transfer and Phenazine Formation via an Aryne Intermediate

Treatment of chlorotriaryl derivatives 3a and 3d or fluorotriaryl derivatives 3b and 3e with potassium diisopropylamide afforded alkyl-shifted phenazine derivatives 5a/5b, rather than the expected 9-membered triazaorthocyclophane 2a. The phenazine derivatives were isolated in 78–98% yield depending on the halogen and alkyl group present. In the absence of the halogen (chloro or fluoro), the apparent alkyl shift proceeds more slowly and cannot proceed via the intermediacy of the aryne intermediate. Mechanistic possibilities include intramolecular nucleophilic attack on an aryne intermediate leading to a zwitterionic intermediate and alkyl transfer via a 5-endo-tet process, or via a Smiles rearrangement

Coping with shrinkage in Europe's cities and towns

An increasing number of cities and towns in Europe are facing population decline. In this article we focus on the challenges of this urban shrinkage process from a policy perspective. After a short review of the main causes and consequences of urban shrinkage in Europe, two common public policy responses are identified and evaluated: counteracting shrinkage and accepting shrinkage. Arguing that the latter is the most suitable approach, we recognise that coping with population decline is a complex urban governance process in which citizens inevitably have to play an important role. In shrinking environments, however, people are not always prepared to engage for their community. If policymakers want citizens to care for their community, they must enable them to do so. This may require a rethink of the specific tasks and roles of local government in Europe's shrinking cities and towns