Cronin Group
/*electrochemical systems*/

Cronin Group Research

Molecular Fundamentals
Inorganic Biology
Synthetic Systems
Hybrid Devices
Polyoxometalates and Self-Assembly
Molecular Metal Oxides
Complex Systems
Synthetic Biology
Artificial Life and Evolvability
3D Printing
Digital Synthesis
Chemical Robots
Solar Fuels
CMAC

Research Overview

Research in the Cronin Group is focussed on the potential of complex chemical systems derived from non biological building blocks to have a major impact on our fundamental understanding of the interplay of chemical systems and to revolutionise modern technologies. To this end the Cronin group works within four major research "areas" of Molecular Fundamentals, Inorganic Biology, Synthetic Systems and Hybrid Devices. The Cronin Group believes in a synergistic approach to research with research areas and projects reinforcing each other to enable fundamental advances to be made.

This research feeds into a number of major applications being investigated in the cronin group with the intention of realising the real-world benefits of the fundamental science being conducted. These applications range from developing materials for solar fuel devices to producing potential drug and drug delivery candidates.

Research Overview

Research in the Cronin Group is focussed on the potential of complex chemical systems derived from non biological building blocks to have a major impact on our fundamental understanding of the interplay of chemical systems and to revolutionise modern technologies. To this end the Cronin group works within four major research "areas" of Molecular Fundamentals, Inorganic Biology, Synthetic Systems and Hybrid Devices. The Cronin Group believes in a synergistic approach to research with research areas and projects reinforcing each other to enable fundamental advances to be made.

This research feeds into a number of major applications being investigated in the cronin group with the intention of realising the real-world benefits of the fundamental science being conducted. These applications range from developing materials for solar fuel devices to producing potential drug and drug delivery candidates.

Molecular Fundamentals

Understanding of the fundamental behaviour of nano-sized materials is crucial to the development of new technologies which benefit society. The knowledge we gain from our research in this area acts as the foundation for the ambitious and exciting chemistry taking place in the Cronin Group. The Cronin group has a long history of investigating the fundamentals of molecular metal oxide synthesis, with our focus on the development of materials which have an inherent functionality such as redox-activity, host-guest chemistries and magnetic capabilities. Learning to reliably design and incorporate these properties into molecular materials represents a real leap forward in the applications of metal oxide technologies.

Technologies based on solid-state metal oxides are worth over a trillion dollars per year, but there are significant costs attached to these technologies, such as the need for high temperature processing. Molecular level processing, on the other hand, promises technologies which offer significant advantages in terms of both easy control and low costs. This is not routinely possible as yet. Our fundamental work is to design and synthesise new molecular metal oxide clusters with controllable sizes and elemental compositions, which can be directly transferred and manipulated to assemble nanoscale doping dots with adjustable structures and tuneable physical properties after appropriate post-treatments.

Inorganic Biology

Our growing understanding of complex chemical systems has allowed a fundamental change in the way chemists both perceive and investigate the chemical world. We have already shown the potential of this approach in our work with template-directed cluster synthesis under flow, growth and control of metal oxide based microtubes and construction of membranous inorganic chemical cells iCHELLs.

In biological systems, arguably the ultimate example of chemical complexity, subtle control of a huge number of interlinked non-equilibrium processes is achieved by partitioning within semi-permeable membranes, which are fine-tuned in their ability to allow or deny the passage of different chemical species. We are increasingly drawn to the complex and highly evolved mechanisms found in nature, to help us to design and build molecular ensembles and aggregates of our own; that can effectively ‘build’ or ‘manage’ themselves without needing our constant intervention. Research under the Inorganic Biology theme aims to put together a toolbox of inorganic materials; molecular metal oxides, hybrid-functionalised polyoxometalates and coordination compounds, which allows us to construct pre-designed complex chemical systems that have emergent properties, i.e. properties pertaining to the overall system rather than just its components. It is often proposed that in order for a system to be considered as living, it requires, at a minimal level, some form of containment such as a membrane or cell-wall, and a means of sequestering material from its environment to facilitate growth and/or replication. Coupled to this, some form of information storage and ability pass that information from one entity to the next generation allows Darwinian evolution to take place. By combining our inorganic toolbox and knowledge of chemical complexity, we can start to address these points; metal oxide based membranes for containment, growth and division by osmotically driven morphogenesis and information storage in molecular metal oxides, and will eventually be able to synthesise an inorganic chemical cell capable life-like function.

Synthetic Systems

The Cronin group is developing revolutionary techniques in chemical synthetics which will alow the literal 'evolution' of materials to fulfil a desired function. Using a combination of fundamental insights into the interconnected nature of synthetic reaction networks with the use of purpose designed reaction hardware, our aim is initially the understanding and control of the self-assembly processes and finally the designing of molecular nanoparticles with the desired functionality which will stimulate an impact in modern technologies. In order to do this inorganic nano-sized molecules are being designed and built "to order" to conduct specific tasks at the nano-level. Our highest priority targets tasks involve energy applications (water splitting, storage devices, quantum computing, molecular electronics, catalysis and solar fuel devices).

Hybrid Devices

Polyoxometalates are highly versatile cluster building blocks that can self-organize in 1D, 2D and 3D frameworks. We have recently illustrated their potential for example in devices for memory storage, catalysts for water - splitting reactions or materials for microtubes fabrication.

Even though we have only scratched the surface of their potential and many great discoveries are to be made, these fantastic properties can surely be enhanced when “covalently” linked to organic molecules with selected properties. These hybrid organic - inorganic materials benefit from mixed organic - inorganic behaviors, and therefore cannot be treated as purely inorganic or purely organic. One of the main challenges and difficulties is the design and discovery of new synthetic ways compatible with the nature of both sub-components and to extend the number of POMs building blocks available for hybrid systems. The organic components can be based upon the same self-recognition motifs used in conventional supramolecular chemistry (eg. H-bonds, electrostatic interactions, pi-stacking, reversible covalent bonds…) and can rearrange upon external stimuli, on a surface, in solution, or in the solid state (eg. single crystal to single crystal transformation). A better understanding of the molecular interactions in these different states is gained via AFM, NMR, mass spectrometry, X-Ray analysis, DSC and result in materials with properties useful in medicine (drug delivery, cell recognition, anticancer agent, contrast agent for medical imaging) or in electronics (photoswitchable devices, surface water-splitting devices). The understanding and therefore the control over intermolecular interactions is the key for the design of more and more complex chemical systems that could potentially self-sustain in an oscillatory mode, and that could thereafter lead to an evolvable chemical system eg. a primitive form of life.

The term “self-assembly” is often used as an all-encompassing explanation to rationalize the formation of very large molecules and supramolecular aggregates, but unfortunately this term lacks specific mechanistic details specifically in the formation of supramolecular systems. These details could be very important in the ongoing efforts to understand, control, predict, and then design multifunctional inorganic materials by use of molecular synthons, which exhibit well-defined structure and linkable geometries. The Cronin group developed a dynamic synthetic procedure in a flow system that enabled real-time adjustment of the three input variables (pH, concentration of molybdate, and reducing agent) controlling the synthesis of complex self-assembled chemical systems such as the molybdenum blue (MB) compounds. This approach allowed us to probe the self-assembly of the MB nanoparticles, where by controlling the degree of reduction of the polyoxomolybdate clusters we managed to trap an elusive supramolecular intermediate species and shed light upon the formation mechanism of the MB family.

Molecular Metal Oxides (MMOs)

Traditional bulk metal oxides, such as titanium oxide and indium tin oxide, have a wide variety of uses in modern technologies such as catalysis and electronics. These materials however are reaching their limit of exploitation in modern technologies. Molecular Metal Oxides (MMO) represent a class of material whose potential has not yet begun to be realised. These nanoscale materials can have radically differing properties to their bulk analogues, which are affected not only by the chemical composition of the material, but also the structural morphology of the cluster material. The Cronin group developed over the years novel synthetic approaches allowing the generation of new building block libraries which can be used as transferable set of synthons for the manufacturing of large and potential functional architectures in a programmable fashion.

Network Flow Systems

Both traditional polyoxometalate-based synthetic approaches and fundamental self-assembly mechanisms are being under intensive reviewing because one-pot reactions mask a vast and complex range of intricate self-assembly processes. Therefore it is difficult to predict or control the assembly processes. In early 2010, flow systems were employed in POM chemistry for the first time. This approach unrevealed the mechanism of formation of giant polyoxomolybdates. Since this fundamental discovery, a new generation of PC-controlled configurable reactors has been designed for automating/accelerating the discovery of new complex inorganic architectures. Two advanced configurable reactors enable the synthesis of nano-scale complex inorganic architectures by controlling macroscopic variables only in a unique fashion based on chemical mixture programming and fast resolution on in-situ experimental variable monitoring. The development of such fully automated reactor systems revolutionize and open new areas in experiment design in research laboratories, due to the potential applications in accelerating discovery of inorganic clusters, organic reactons and materials.

Synthetic Biology

Synthetic Biology is essentially the development of engineered biological parts that we can manipulate in more controllable fashion. Using engineered automated experimental systems developed by the group, we are working towards automated screening and directed evolution of genetically engineered cells, such as E.coli and Synechocystis. In this context, 3D printing technology only provides custom-made reaction/culture chambers, but also enables us to monitor and manipulate biological cells in conjunction with integrated sensor (e.g. optical density sensor) and acuator devices (solenoid valves for fluidic control). As a long-term perspective, we will be able to further integrate with other analytica devices developed by the group, such as flow IR and flow NMR, and microfluidic assay systems, from which we will able to gain better understandings of complex biological processes inside cells.

Artificial Life and Evolvability

Microfluidics describes the study and development of systems which control small volumes of fluids (typically on the picolitre to nanolitre scale).

The Cronin Group has set up the facilities to enable microfabrication of Lab-on-a-Chip devices. Therefore, by using droplet-based microfluidic technology, we aim to access a large number of individual experiments per unit time with enhanced analytical performance. Manipulation of microdroplets with high precision enhances the realization of diverse operations within a device such as formation, fusion, fission, mixing, sorting and transport of droplets.

3D Printing

3D-printing has the potential to transform science and technology creating bespoke, low-cost appliances which have previously required dedicated facilities. An attractive but unexplored application is using the 3D-printer to initiate chemical reactions by printing the reagents directly into the 3D-reactionware matrix, putting reactionware design, construction and operation under digital control.

Using a low-cost 3D-printer and open-source design software, we produced reactionware for organic and inorganic synthesis, including printed-in catalysts, and other architectures with printed-in components for electrochemical and spectroscopic analysis. This allowed reactions to be monitored in situ so that different reactionware architectures could be screened for their efficacy for a given process, giving a digital feed-back mechanism for device optimisation. A reaction cascade is chosen for investigation and labware considered appropriate for this task is designed with the aid of suitable computer programs. This same suite of programs can then be used to execute the actual printing of the device(s) and to initiate the reactions, whilst other software monitors the reactions as they happen. The results at all stages along the way can be fed-back to allow optimisation of the printed labware for a particular outcome in subsequent device “generations”. As user input to this process is potentially minimal after the initial reaction cascade has been selected and the first iteration of devices designed, subsequent optimisation (or “evolution”) of the system towards a specific goal becomes a digitally-automated process. Taken together, this approach constitutes a cheap, automated and reconfigurable chemical discovery platform that makes techniques from chemical engineering accessible to typical synthetic laboratories.

Digital Synthesis / Microreagents

MICREAgents (Microscopic Chemically Reactive Electronic Agents) are electronic circuits on 3D microchips (“lablets”, of diameter = 100 µm) that self-assemble in pairs to enclose transient reaction compartments, using the electronics to control chemical access, surface coatings and reactions. Chemicals will be selectively concentrated, processed and released into the surrounding solution under local electronic control, in a similar way to which the genetic information in cells controls local chemical processes. The lablet devices will integrate transistors, supercapacitors, energy transducers, sensors and actuators, and this project represents a major international collaboration involving 10 different research groups. We are trying to provide power to these devices via POM-based supercapacitors, and working on creating the surface coatings on the lablets. The aim is that such smart MICREAgents could be poured into chemical mixtures to organize the chemistry from within. Ultimately, such micro-reactors, like cells in the bloodstream, will open up the possibility of controlling complex chemistry from the inside out.

Chemical Robots

A liquid handling robot designed to manipulate oil droplets in aqueous environments. Its aim is to explore oil and surfactant reaction space using a stochastic approach directed by a fitness function. It is equipped with multiple syringes and a camera which looks through the glass stage. Its movement on two axes can be controlled by the software in order to get a close-up picture anywhere in the experimental area for droplet tracking by image recognition.

A modified RepRap I3 which is equipped with controllable syringes to deliver other chemicals in addition to structural plastics in order to print chemistry directly into reactionware without human intervention in the print.

Solar Fuels

The Cronin Group is engaged in a multidisciplinary research project which aims to use an integrated approach to the sensing, binding, activation and transport of carbon dioxide in aqueous systems with the overall aim of producing a ‘solar fuel’ that could be used to replace fossil fuels.

Leading an international research initiative, ‘Glasgow Solar Fuels’, the Cronin group is using its expertise in developing nanoscale electronically switchable and redox active sensors, and binding molecules for small molecules such as carbon dioxide, to work towards their application in the development of solar harvesting systems for water splitting, carbon dioxide fixation, and developing this approach to the in-situ reduction of carbon dioxide to methanol. This research is in collaboration with, and builds on the world-leading team established at Glasgow by Neil Isaacs and Richard Cogdell in photosynthesis which has resulted in great advances in our understanding of the structure and function of the biological system, Photo-System 2 (PS2). By combining Inspiration from biological photoactive systems with the Cronin group’s background in the realisation of complex chemical systems and molecular devices, we hope to make a real impact to the future of energy production, waste management and reduction of pollution.

Centre for Innovative Manufacturing in Continuous Manufacturing and Crystallisation

This new national Centre brings together an initial team of 13 leading academics from across 7 UK institutions to work closely with our industry partners with a shared vision to accelerate the adoption of continuous manufacturing processes, systems and plants for the production of high-value chemical products to higher quality, at lower cost and more sustainably. By supporting a collaborative, multi-disciplinary programme the CMAC aims to: enable the change from batch to fully continuous manufacturing processes for high value chemical products, produce better chemical and pharmaceutical products (at lower cost) more sustainably through transformational change in how particles are manufactured and increase competitiveness of UK chemical manufacturers through reduced costs and higher value products.

Subgroup Leaders

Group Leader Prof. Lee Cronin
Molecular Fundamentals Dr. De-Liang Long
Inorganic Biology Dr. Geoff Cooper
Synthetic Systems Dr. Haralampos Miras
Hybrid Devices Dr. Marie Hutin

Collaborators

The Cronin group is involved in a wide range of collaborations both nationally and internationally with both academic and industrial researchers from all areas of the physical and biological sciences. Click below to expand.

UK Collaborators+

Dr Cameron Alexander, University of Nottingham
Dr. Euan Brechin, University of Edinburgh
Prof. Richard Cogdell, University of Glasgow
Dr. Graeme Cook, University of Glasgow
Prof. Ben G. Davis, University of Oxford
Prof. Yulong Ding, University of Leeds
Dr. Nikolaj Gadegaard, University of Glasgow
Dr. Justin Hargreaves, University of Glasgow
Dr. Malcolm Kadodwala, University of Glasgow
Prof. Natalio Krasnogor, University of Nottingham
Dr. Andrei N. Khlobystov, University of Nottingham
Prof. Alexei Lapkin, University of Warwick
Prof. Eric McInnes, University of Manchester
Prof. Paul McMillan, University College London
Dr. Mark Murrie, University of Glasgow
Prof. Miles Padgett, University of Glasgow
Prof. Chick Wilson, University of Bath
Prof. Richard Winpenny, University of Manchester
Dr. Huabing Yin, University of Glasgow

International Collaborators+

Prof. Alan Bond, Monash University, Australia
Prof. Edwin Constable, University of Basel, Switzerland
Prof. Dirk M. Guldi, University of Erlangen, Germany
Prof. Takashi Kato, University of Tokyo, Japan
Dr. Tia Keyes, Dublin City University, Ireland
Paul Kogerler, RWTH Aachen University, Germany
Prof. Tianbo Liu, Lehigh University, USA
Prof. Takayoshi Nakamura, RIES, Hokkaido University, Japan
Prof. Hiroyuki Nojiri, University of Tohoku, Japan
Prof. Hiroki Oshio, Tsukuba University, Japan
Prof: Bruno Pignataro, University of Palermo, Italy
Prof. Josep M. Poblet, University of Tarragona, Spain
Prof. Jurgen Schnack, University of Bielefeld, Germany
Prof. Sylvia Speller, University of Nijmegen, The Netherlands
Prof. Yu-Fei Song, Beijing University of Chemical Technology, China
Dr. Filip Teply, Institute of Organic Chemistry and Biochemistry AS CR, v.v.i., Czech Republic
Prof. Lin Xu, Northeast Normal University, China
Prof. Yingxi Elaine Zhu, University of Notre Dame, U.S.A.

Industrial Collaborators+

Research Projects