Powering smart materials by oscillatory chemical reactions
Lead Research Organisation:
Newcastle University
Department Name: Chemical Engineering & Advanced Material
Abstract
All plants and animals have the ability to adapt to the environment to some extent e.g. exhibit heliotropism (some flowers or leaves surfaces follow the direction of sunlight) or react to heat or pain. Following the same principle, instead of using materials designed to suit a range of conditions while not being optimal for any of them individually, we would prefer smart materials that have the ability to sense the conditions in their environment and adjust accordingly. The smart materials I am interested in are polymer gels that show a chemo-mechanical response, i.e. a change in the chemistry of the medium about the material results in a stepwise change in the volume that the material occupies by causing it to swell or collapse. This structural change may be used to force host molecules out of the gel structure (collapsing) or into the gel structure (swelling). One of the applications of the collapsing phenomenon is in drug delivery systems that would dispense drug molecules only under certain environmental conditions. On the other hand polymer gel swelling may be applied for the encapsulation of unwanted reaction inhibitors or pathogens in the media. Another application of smart polymer gels is as chemo-mechanical micro-valves where the valve (gel) is activated by a change in the medium. One example is a heat activated micro-valve. Upon heating the gel collapses and the valve opens while upon removing the heat the gel expands and the valve closes. This has direct application in the control of fluid flow and mixing in micro-size systems.An essential element in the application of smart materials is the stimulus that causes the occurrence of the change. The proposed research investigates the palladium-catalysed phenylacetylene oxidative carbonylation (PCPOC) reaction in methanol envisioning many applications of its versatile nature and importantly application as a stimulus. This is an extraordinary chemical system that exhibits pronounced oscillations in pH and reaction heat output when operated in a stirred batch reactor. As a chemical oscillator it falls into the field of nonlinear chemical dynamics that studies phenomena related to the temporally periodic or nearly periodic variation of the concentrations of one or more species in a reaction. The best known reaction of this type is the Belousov-Zhabotinsky reaction. The PCPOC reaction is an oscillating system of higher complexity and an exceptional example of oscillatory behaviour in reactions catalysed by metal complexes. There are a number of reasons why the PCPOC reaction is of such great importance: it provides a novel and not well understood pH oscillator; it represents the first example of complex molecules synthesised from relatively simple reagents proceeding in a catalytic system in an oscillatory mode; when operating this system in an oscillatory regime high levels of product selectivity may be achieved compared to operating in a non-oscillatory mode; besides oscillations in pH, synchronised oscillatory heat output is present; it exhibits two relevant stimuli, pH and temperature; it may have application in propelling nano devices by generating an oscillating force when coupled with a block of gel.This study is aimed at the cooperative interplay between experimental and theoretical investigation into the application of this carbonylation reaction as a stimulus. Predictive physico-chemical models of the PCPOC reaction will be developed and this system will be researched with pH sensitive polymers, temperature responsive polymers and materials sensitive to both (i.e. temperature and pH responsive polymeric composite membranes) as: (1) an environment containing the smart material; (2) an enclosed environment communicating with the environment containing the smart material and (3) an enclosed environment containing the smart material communicating with the targeted environment.
Organisations
People |
ORCID iD |
Katarina Novakovic (Principal Investigator) |
Publications
Donlon L
(2014)
Oscillatory carbonylation using alkyne-functionalised poly(ethylene glycol).
in Chemical communications (Cambridge, England)
Donlon L
(2014)
Oscillatory carbonylation of phenylacetylene in the absence of externally supplied oxidant
in Reaction Kinetics, Mechanisms and Catalysis
Donlon L.
(2014)
Oscillatory carbonylation using functional polymers
in Functional Polymeric Materials
Glenn Hurst (Author)
(2013)
Smart hydrogels for biomedical use with oscillatory reactions
Glenn Hurst (Author)
(2012)
Genipin-crosslinked chitosan-poly(vinyl pyrrolidone) hydrogel for coupling with pH oscillators
Hurst G
(2013)
A facile in situ morphological characterization of smart genipin-crosslinked chitosan-poly(vinyl pyrrolidone) hydrogels
in Journal of Materials Research
Hurst G.
(2012)
Characterisation of the structural properties of genipin crosslinked chitosan-poly(vinyl pryrrolidone) smart hydrogels
in Polymeric and Self-Assembled Hydrogels
Hurst G.
(2013)
Smart genipin-crosslinked chitosan-poly(vinyl pyrrolidone) as a self-oscillatory hydrogel
in ICMAT 2013
Hurst G.A.
(2014)
Prospective applications of pH responsive genipin crosslinked chitosan-polyvinylpyrrolidone hydrogels
in x International Symposium on Stimuli-Responsive Materials
Description | - Reproducible oscillatory behaviour in pH using polymer-bound substrates. This is first example of a polymer-bound substrate in an oscillatory system. Oscillatory chemical reactions are special cases of chemical reactions that have one or more species pulsing in their concentration (oscillating, going up and down in a certain rhythm) while others species are decreasing (reacting) or increasing (being produced). These reactions are considered very much life like and the area studying this type of reactions studies all kind of phenomena including animal coat patterns, such as those found on zebras, leopards, cheetahs and jaguars; riddles of rippled icicles; hexagon shaped rock formations; quorum sensing in bacteria; origins of life. - Reaction mechanism associated with experimentally recorded behaviour of polymeric oscillators, i.e. understanding of reaction kinetics governing the oscillatory process in this system. By understanding how this one works we can now attempt to design new systems. - In depth studies and understanding of small molecule oscillatory phenylacetylene carbonilation reaction both experimentally and in modelling studies. This system was crucial for expanding knowledge and is used as basis of the design of polymeric oscillator. - Synthesis and characterisation of low toxicity hydrogels responsive to pH as a stimuli. Key factor is usage of low toxicity crosslinking agent so that material is now biocompatible. These materials are of high importance as they are promising for in-vivo applications for drug delivery and tissue engineering. - In-vitro verification of hydrogels as scaffolds for mechanoresponsive cell growth. - In-vitro verification of hydrogels ability to carry and dispense medication indicating potential for drug delivery applications. |
Exploitation Route | I intend to pursue polymeric oscillators further via new grant application and aim to develop fully autonomous oscillatory materials e.g. materials we can use for chronopharmacoterapy, tissue engineering and ultimately to make artificial heart. Community working in the wider area of nonlinear dynamics in chemical systems shown interest for our polymeric oscillator discovery. Outcome of our research on stimuli responsive hydrogels will be pursued by both my research group and others for the likelihood of applications. |
Sectors | Education Healthcare Pharmaceuticals and Medical Biotechnology |
Description | Healthcare Technologies Impact Fellowship |
Amount | £466,121 (GBP) |
Funding ID | EP/N033655/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 12/2016 |
End | 05/2019 |
Description | New Directions for EPSRC Research Leaders |
Amount | £295,182 (GBP) |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | |
End | 12/2014 |
Description | School of Chemical Engineering and Advanced Materials Internal Scheme |
Amount | £19,536 (GBP) |
Organisation | Newcastle University |
Sector | Academic/University |
Country | United Kingdom |
Start | 05/2014 |
End | 08/2014 |
Description | School of Chemical Engineering and Advanced Materials, Internal Scheme |
Amount | £6,655 (GBP) |
Organisation | Newcastle University |
Sector | Academic/University |
Country | United Kingdom |
Start | 06/2013 |
End | 09/2013 |
Description | URO Visiting Professor/Fellows |
Amount | £3,800 (GBP) |
Organisation | Newcastle University |
Sector | Academic/University |
Country | United Kingdom |
Start |
Description | URO Visiting Professorship |
Amount | £4,000 (GBP) |
Organisation | Newcastle University |
Sector | Academic/University |
Country | United Kingdom |
Start | |
End | 05/2014 |
Description | EPSRC Early Career Fellowships Information Session |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | Yes |
Geographic Reach | Local |
Primary Audience | Other academic audiences (collaborators, peers etc.) |
Results and Impact | Since winning a Career Acceleration Fellowship I have taken part in numerous EPSRC Early Career Fellowships Information Session seeking to share my experience, encourage, motivate colleagues to pursue similar paths if they wish. Number of colleagues found information provided very useful. |
Year(s) Of Engagement Activity | 2009,2011,2012,2014 |
Description | Fellowship Event |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Other audiences |
Results and Impact | Sharing experience of winning and holding fellowships. Delivering talk followed by Q and A session. Audience were postdocs and junior academic staff. |
Year(s) Of Engagement Activity | 2019 |
Description | Invited talks |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Other academic audiences (collaborators, peers etc.) |
Results and Impact | Over the duration of the award in addition to talks at conferences I have been invited to deliver several seminars at UK Universities. This has enabled new collaborations and aided plans for future research directions. |
Year(s) Of Engagement Activity | 2009,2010,2011,2012,2013,2014 |
Description | National Science and Engineering Week 2014: Meet the Scientist event, Great North Museum (Hancock), 15th March 2014 |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | Yes |
Geographic Reach | National |
Primary Audience | Public/other audiences |
Results and Impact | I have spend one day in the museum explaining and demonstrating responsive materials to general public from nursery children to elderly. I was amassed how much interest they showed in my science and how many questions they had. I have benefited greatly from talking to general public and learning how to communicate my science at that level. |
Year(s) Of Engagement Activity | 2014 |
Description | Oscillatory system to deliver drugs, The Engineer |
Form Of Engagement Activity | A magazine, newsletter or online publication |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Media (as a channel to the public) |
Results and Impact | I have given and interview for The Engineer http://www.theengineer.co.uk/news/oscillatory-system-to-deliver-drugs/313205.article The interview attracted contacts from companies interested in soft materials for drug delivery. Also helped in getting invited to give seminars at Universities. |
Year(s) Of Engagement Activity | 2009 |
URL | http://www.theengineer.co.uk/news/oscillatory-system-to-deliver-drugs/313205.article |
Description | Research Staff Summer School |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | Yes |
Geographic Reach | Local |
Primary Audience | Other academic audiences (collaborators, peers etc.) |
Results and Impact | I was invited speaker at these events. The Summer School was aimed at research staff who are at the early stages of their research career at Newcastle, Durham and Sunderland Universities (e.g. within the first 2 years) and focused on key aspects for career advancement of the researcher role. Some attendees were motivated to apply for fellowships. |
Year(s) Of Engagement Activity | 2010,2011 |
URL | https://www.dur.ac.uk/training.course/graduate/?mode=details&schedule=3543 |
Description | Royal Academy of Engineering - North East Regional Event |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | Regional |
Primary Audience | Professional Practitioners |
Results and Impact | Event was aimed at raising awareness of the Royal Academy of Engineering, sharing information on how to become a Fellow of the Royal Academy of Engineering, learning which funding is available from the Royal Academy and learning about some research carried out with Academy funding. I was invited to give research talk. |
Year(s) Of Engagement Activity | 2019 |
Description | Women in Science -Newcastle University 28th March 2012 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | Yes |
Geographic Reach | National |
Primary Audience | Public/other audiences |
Results and Impact | Talk was very well received. Following this event I have been contacted by number of researchers who told me that I have inspired, encouraged and motivated them to pursue their careers further. I have been used as a School's case study in the Athena Swan application. |
Year(s) Of Engagement Activity | 2012 |
URL | http://www.ncl.ac.uk/diversity/about/networks/nu-women.php |