Imperial

One of the most significant challenges facing the healthcare community is the accurate and selective detection and quantification of trace levels of analyte. This can have enormous impact with numerous application, especially in the context of biosensing, where applications can range from early stage detection of disease to the identification of new markers amongst others. These challenges are compounded when the analysis of real samples or even complex mixtures are required. To address this need, single molecule or near single molecule methods are currently being heavily pursued which allows for the discrimination of events with low copy numbers by removing the “clouding” associated with ensemble averaging. Although strategies for detecting single molecules have existed for a number of years, efficient and cost-effective label-free methods without the need for chemical modification are lacking especially when considering smaller molecules directly in unprocessed clinical samples. As part of this proposal, I intend to address this limitation by developing new strategies in single molecule nanoscale sensing which will be both highly sensitive and selective for improved therapeutics and diagnostics applications.

The aim of the proposed project is to develop redox-active macrocycles for excellent electron and ion transporting materials. Such mixed ionic-electronic conductors are important for various state-of-the-art applications, for example organic battery electrodes, electrochemical transistors, electrochromic devices, and light-emitting electrochemical cells. So far, macrocycles are considerably underexplored regarding these applications; important aspects such as straightforward synthesis and self-assembly are usually not taken into account. The proposed project is going to change this by introducing new molecular design concepts; thereby, the project is expected to yield macrocycles with excellent electron and ion transport properties and to attract significant attention to macrocycles regarding the above mentioned applications. Cyanated paracyclophanetetraenes and related compounds with different aromatic units are selected as the target materials. Such fully unsaturated shape-persistent macrocycles often feature desirable properties, due to their strain and low conformational flexibility. Regarding the aim of electron transport, it is particularly useful that the macrocyclic structure facilitates intermolecular contacts and charge transport. Regarding the aim of ion transport, the potential self-assembly of shape-persistent macrocycles into tubular superstructures is encouraging as such structures can provide channels for the transport of ions. The specific objectives of the project are (i) the development and optimization of syntheses towards cyanated paracyclophanetetraenes using model compounds, (ii) the preparation of these cyanated macrocycles and related compounds with different aromatic units, and (iii) the investigation of their redox and self-assembly properties as well as the demonstration of their excellent electron and ion transport properties in devices such as transistors and batteries.

Observation and Modelling of Radiocarbon in Atmospheric Methane for Methane Source Identification Greenhouse gas emissions are the primary cause of global climate change, and methane (CH4) is the second most important contributor after carbon dioxide (CO2). Major sources of methane are both natural (wetlands) and anthropogenic (agriculture, landfills and fossil fuels). Current efforts to assess the anthropogenic CH4 influence on climate change and the effectiveness of mitigation policies for CH4 are limited by large uncertainties in estimates of total methane emissions and their attribution to various sources by accounting-based techniques. This project will pioneer and apply innovative techniques for atmospheric observation and modelling of radiocarbon in CH4 that will enable unique quantification of fossil fuel vs. biogenic CH4 sources at regional and global scales, thereby improving the estimation and attribution of CH4 emissions of different types. The proposed work will significantly advance the frontier of current research on atmospheric methane and the characterization of anthropogenic sources on policy-relevant scales, and it has the potential to influence climate policy and industrial practices over the next 10-20 years.