Co-reporter:Alan A. Wiles, Xiaolu Zhang, Brian Fitzpatrick, De-Liang Long, Stuart A. Macgregor and Graeme Cooke
Dalton Transactions 2016 vol. 45(Issue 17) pp:7220-7225
Publication Date(Web):11 Apr 2016
DOI:10.1039/C6DT00875E
Chemical redox reactions have been exploited to transform unreactive vinylferrocene into a powerful dienophile for the Diels–Alder reaction and reactive substrate for thiol addition reactions upon conversion to its ferrocenium state. We have further investigated the ability of these reactions to facilitate redox-auxiliary-like reactivity by further hydrogenolyisis of the Diels–Alder adduct to the corresponding cyclopentane derivative.
Co-reporter:Alan A. Wiles, Brian Fitzpatrick, Niall A. McDonald, Mary Margaret Westwater, De-Liang Long, Bernd Ebenhoch, Vincent M. Rotello, Ifor D. W. Samuel and Graeme Cooke
RSC Advances 2016 vol. 6(Issue 10) pp:7999-8005
Publication Date(Web):19 Jan 2016
DOI:10.1039/C5RA22402K
The synthesis of acceptor-functionalised oligothiophene derivatives (t3, t6, t7, t8) is described, where the pteridine-2,4-dione acceptor units are arranged symmetrically in derivatives t6–t8. The symmetrical arrangement of acceptor units stems from the ability to selectively brominate the conjugated thiophene moiety of building block t3. Upon increasing the conjugation by going from t3 to t8, a significant increase in absorption toward the near-infrared region and a simultaneous narrowing of the HOMO/LUMO gap occurs, which may promote their future application as optoelectronic materials.
Co-reporter:Michele Cariello, Sungwoo Ahn, Kwang-Won Park, Suk-Kyu Chang, Jongin Hong and Graeme Cooke
RSC Advances 2016 vol. 6(Issue 11) pp:9132-9138
Publication Date(Web):22 Jan 2016
DOI:10.1039/C5RA21565J
In this article, we report the synthesis of new ferrocene incorporating dyes and their evaluation as sensitizers for dye-sensitized solar cells. We have shown that the sequential addition of alkyne units as π-spacers plays an important role in modulating their solution optical and redox properties. Likewise, the most extensively conjugated dye (Fc-D3) provided the highest power conversion efficiency (η) compared to the other less-conjugated dyes in the series. We have also demonstrated that the choice of electrolyte is important in determining η for this series of dyes.
Co-reporter:Bernd Ebenhoch, Nor B. A. Prasetya, Vincent M. Rotello, Graeme Cooke and Ifor D. W. Samuel
Journal of Materials Chemistry A 2015 vol. 3(Issue 14) pp:7345-7352
Publication Date(Web):05 Mar 2015
DOI:10.1039/C5TA00715A
We report the fabrication of solution-processed bulk heterojunction devices from subphthalocyanine (SubPc) units as the acceptor component and conventional polymeric donor materials such as MEH-PPV, P3HT and PTB7. The high solubility of the SubPc derivatives facilitated the formation of efficient donor/acceptor networks and provided power conversion efficiencies of 0.4% with MEH-PPV, 1.1% with P3HT and 3.5% with PTB7. A clear contribution of photon harvesting by the acceptor was identified from the external quantum efficiency spectra. Analysis of the current–voltage characteristics and photoluminescence quenching revealed trap-assisted and geminate recombination as a loss mechanism. Our results show that solution-processable SubPcs are a promising alternative to fullerenes for polymer solar cells.
Co-reporter:Stuart T. Caldwell, Catherine Maclean, Mathis Riehle, Alan Cooper, Margaret Nutley, Gouher Rabani, Brian Fitzpatrick, Vincent M. Rotello, Brian O. Smith, Belal Khaled, Patrice Woisel and Graeme Cooke
Organic & Biomolecular Chemistry 2014 vol. 12(Issue 3) pp:511-516
Publication Date(Web):27 Nov 2013
DOI:10.1039/C3OB41612G
In this article, we describe the synthesis of new biotin-functionalised naphthalene derivatives 3 and 4 and their complexation behaviour with avidin and neutravidin using a range of analytical techniques. We have shown using 2-(4′-hydroxyazobenzene)benzoic acid displacement and ITC experiments, that compounds 3 and 4 have the propensity to form reasonably high-affinity bioconjugates with avidin and neutravidin. We have also demonstrated using 1H NMR, UV-vis and fluorescence spectroscopy that the naphthalene moiety of 3 and 4 facilitates the formation of pseudorotaxane-like structures with 1 in water. We have then investigated the ability of avidin and neutravidin to modulate the complexation between 1 and 3 or 4. UV-vis and fluorescence spectroscopy has shown that in both cases the addition of the protein disrupts complexation between the naphthalene moieties of 3 and 4 with 1.
Co-reporter:Manal Al-Eid, SungHwan Lim, Kwang-Won Park, Brian Fitzpatrick, Chi-Hwan Han, Kyungwon Kwak, Jongin Hong, Graeme Cooke
Dyes and Pigments 2014 Volume 104() pp:197-203
Publication Date(Web):May 2014
DOI:10.1016/j.dyepig.2014.01.004
•Convenient synthesis of two dyes with acceptable power conversion efficiencies.•Increased conjugation important for higher power conversion efficiencies.•Low cost dyes have been prepared for more widespread photovoltaic applications.In this article, we report the facile synthesis of metal-free dyes 6 and 7, their solution-based optical and redox properties and their use as sensitizers in dye-sensitized solar cells (DSSCs). Our studies indicate that the addition of the second thiophene unit in dye 7, decreases the oxidation and reduction potential and consequently the band gap of the molecule compared to 6. Furthermore, increasing the length of the conjugated spacer also affects on the properties of the DSSCs, with dye 7 providing a higher power conversion efficiency compared to 6 (η = 4.49 versus 3.23%).Figure optionsDownload full-size imageDownload as PowerPoint slide
Co-reporter:Léna Sambe;Victor R. deLaRosa;Khaled Belal;Dr. François Stoffelbach;Dr. Joel Lyskawa;Dr. François Delattre;Marc Bria; Graeme Cooke; Richard Hoogenboom; Patrice Woisel
Angewandte Chemie 2014 Volume 126( Issue 20) pp:
Publication Date(Web):
DOI:10.1002/ange.201403560
Co-reporter:Léna Sambe;Victor R. deLaRosa;Khaled Belal;Dr. François Stoffelbach;Dr. Joel Lyskawa;Dr. François Delattre;Marc Bria; Graeme Cooke; Richard Hoogenboom; Patrice Woisel
Angewandte Chemie 2014 Volume 126( Issue 20) pp:5144-5148
Publication Date(Web):
DOI:10.1002/ange.201402108
Abstract
A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N-isopropylacrylamide) (PNIPAM) with side-chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat-p-phenylene) (CBPQT4+) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT4+ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.
Co-reporter:Léna Sambe;Victor R. deLaRosa;Khaled Belal;Dr. François Stoffelbach;Dr. Joel Lyskawa;Dr. François Delattre;Marc Bria; Graeme Cooke; Richard Hoogenboom; Patrice Woisel
Angewandte Chemie International Edition 2014 Volume 53( Issue 20) pp:
Publication Date(Web):
DOI:10.1002/anie.201403560
Co-reporter:Léna Sambe;Victor R. deLaRosa;Khaled Belal;Dr. François Stoffelbach;Dr. Joel Lyskawa;Dr. François Delattre;Marc Bria; Graeme Cooke; Richard Hoogenboom; Patrice Woisel
Angewandte Chemie International Edition 2014 Volume 53( Issue 20) pp:5044-5048
Publication Date(Web):
DOI:10.1002/anie.201402108
Abstract
A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N-isopropylacrylamide) (PNIPAM) with side-chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat-p-phenylene) (CBPQT4+) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT4+ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.
Co-reporter:Vikas Nandwana, Ifor Samuel, Graeme Cooke, and Vincent M. Rotello
Accounts of Chemical Research 2013 Volume 46(Issue 4) pp:1000
Publication Date(Web):November 19, 2012
DOI:10.1021/ar300132r
Flavins feature multiple attributes that explain their widespread occurrence in nature, including photostability, reversible electrochemistry, and especially the tunability of their optical, electronic, and redox properties by supramolecular interactions and modification of their chemical structure. Flavins are important redox cofactors for enzymatic catalysis and are central to a wide variety of processes, including biosynthesis, electron transport, photosynthesis, and DNA repair. The wide range of processes catalyzed by flavins makes them promising leads for synthetic catalysts. Their properties are also relevant to organic electronic and optoelectronic devices, where they have the potential to serve as photoactive electron carriers, a very uncommon property in current photovoltaic systems.In flavoenzymes, the flavin cofactor binds to the active site of the apoenzyme through noncovalent interactions. These interactions regulate cofactor recognition and tune the redox behavior of the flavin cofactor. In this Account, we describe the creation of host–guest systems based on small molecule, polymer, and nanoparticle scaffolds that explore the role of aromatic stacking on the redox properties of the flavin and provide insight into flavoenzyme function. We also describe the creation of synthetic flavin-based interlocked structures featuring aromatic stacking interactions, along with the use of aromatic stacking to direct self-assembly of flavin-based materials.The interplay between redox events and aromatic stacking interactions seen in these synthetic models is important for fundamental understanding of biological systems including the flavoenzymes. The precise control of aromatic interactions and binding of flavins not only underpins their biological activity but gives them the potential to be developed into novel organic optoelectronic materials based on tuned synthetic flavin–receptor assemblies. In a broader context, the redox properties of the flavin provide a very concise tool for looking at the role of electronics in aromatic stacking, an issue of general importance in biological and supramolecular chemistry.
Co-reporter:Catherine Elaine Maclean, Claire Louise Parkinson, Paul James Davis, Mark James Davis, Graeme Cooke
Tetrahedron Letters 2012 Volume 53(Issue 24) pp:2948-2950
Publication Date(Web):13 June 2012
DOI:10.1016/j.tetlet.2012.03.064
In this Letter we report a ferrocene-functionalised polydiacetylene liposome that has the propensity to respond colorimetrically and electrochemically upon binding to a cyclodextrin oligomer.
Co-reporter:Brian Fitzpatrick;Brian Creran;Vincent M. Rotello
Macromolecular Chemistry and Physics 2012 Volume 213( Issue 17) pp:1758-1767
Publication Date(Web):
DOI:10.1002/macp.201200225
Abstract
The synthesis of flavin-containing amphiphilic block copolymers using atom transfer radical polymerisation (ATRP) is described. In these systems, a flavin moiety is engineered into the ATRP initiator unit as an environmental probe and is subsequently used to produce three block copolymers featuring a hydrophobic methacrylate block and a DMAEM block. The dimethylamino unit of the latter is converted to a trimethylammonium unit to afford three amphiphilic block copolymers. Rheological measurements show that these materials form gels in dilute aqueous solution that can be disrupted upon irradiation with ultrasound. The disruption of the gel can be conveniently monitored by exploiting the solvatochromic nature of the S0–S2 absorption in the UV-vis spectrum in response to its changing environment.
Co-reporter:Brian Fitzpatrick;Brian Creran;Vincent M. Rotello
Macromolecular Chemistry and Physics 2012 Volume 213( Issue 17) pp:
Publication Date(Web):
DOI:10.1002/macp.201290052
Co-reporter:Jeremie Louisy, François Delattre, Joel Lyskawa, Aurélie Malfait, Catherine E. Maclean, Léna Sambe, Ning Zhu, Graeme Cooke and Patrice Woisel
Chemical Communications 2011 vol. 47(Issue 24) pp:6819-6821
Publication Date(Web):10 May 2011
DOI:10.1039/C1CC10571J
The addition of the surfactant SDS to an aqueous solution containing 1·2 results in the disassembly of the latter via the simultaneous incorporation of 1 into a micelle and the precipitation of 2 by an anion exchange reaction.
Co-reporter:Niall A. McDonald, Chandramouleeswaran Subramani, Stuart T. Caldwell, Nada Y. Zainalabdeen, Graeme Cooke, Vincent M. Rotello
Tetrahedron Letters 2011 Volume 52(Issue 17) pp:2107-2110
Publication Date(Web):27 April 2011
DOI:10.1016/j.tetlet.2010.11.004
In this Letter, we describe the formation of complexes between flavin and diamidopyridine functionalized porphyrin systems via hydrogen bonding and π-stacking interactions.
Co-reporter:Léna Sambe, François Stoffelbach, Joel Lyskawa, François Delattre, David Fournier, Laurent Bouteiller, Bernadette Charleux, Graeme Cooke, and Patrice Woisel
Macromolecules 2011 Volume 44(Issue 16) pp:6532-6538
Publication Date(Web):July 28, 2011
DOI:10.1021/ma2009854
The aqueous solution properties of amphiphilic tetrathiafulvalene (TTF) end-functionalized poly(N-isopropylacrylamide) (PNIPAM) derivative 1 have been studied. Fluorescence spectroscopy, dynamic light scattering (DLS) and differential scanning calorimetry (Nano-DSC) were used to monitor the temperature-induced micellization and showed that 1 underwent two successive phase transitions corresponding to unimer-to-micelle and lower critical solution temperature (LCST) transitions, respectively. We have investigated the complexation properties of the TTF unit toward cyclobis(paraquat-p-phenylene) (CBPQT4+) or the randomly methylated β-cyclodextrin (RAMEB) to manipulate the amphiphilicity of 1 and to control the unimer-to-micelle phase transition by forming pseudorotaxane-like architectures. For the RAMEB complex with 1, the addition of a competitive guest such as 1-adamantanol resulted in the restoration of amphiphilicity of polymer 1 and consequently the reformation of micelles.
Co-reporter:Kwang-Won Park, Luis A. Serrano, Sungwoo Ahn, Myung Hoon Baek, Alan A. Wiles, Graeme Cooke, Jongin Hong
Tetrahedron (23 February 2017) Volume 73(Issue 8) pp:1098-1104
Publication Date(Web):23 February 2017
DOI:10.1016/j.tet.2016.12.061
Co-reporter:Stuart T. Caldwell, Catherine Maclean, Mathis Riehle, Alan Cooper, Margaret Nutley, Gouher Rabani, Brian Fitzpatrick, Vincent M. Rotello, Brian O. Smith, Belal Khaled, Patrice Woisel and Graeme Cooke
Organic & Biomolecular Chemistry 2014 - vol. 12(Issue 3) pp:NaN516-516
Publication Date(Web):2013/11/27
DOI:10.1039/C3OB41612G
In this article, we describe the synthesis of new biotin-functionalised naphthalene derivatives 3 and 4 and their complexation behaviour with avidin and neutravidin using a range of analytical techniques. We have shown using 2-(4′-hydroxyazobenzene)benzoic acid displacement and ITC experiments, that compounds 3 and 4 have the propensity to form reasonably high-affinity bioconjugates with avidin and neutravidin. We have also demonstrated using 1H NMR, UV-vis and fluorescence spectroscopy that the naphthalene moiety of 3 and 4 facilitates the formation of pseudorotaxane-like structures with 1 in water. We have then investigated the ability of avidin and neutravidin to modulate the complexation between 1 and 3 or 4. UV-vis and fluorescence spectroscopy has shown that in both cases the addition of the protein disrupts complexation between the naphthalene moieties of 3 and 4 with 1.
Co-reporter:Bernd Ebenhoch, Nor B. A. Prasetya, Vincent M. Rotello, Graeme Cooke and Ifor D. W. Samuel
Journal of Materials Chemistry A 2015 - vol. 3(Issue 14) pp:NaN7352-7352
Publication Date(Web):2015/03/05
DOI:10.1039/C5TA00715A
We report the fabrication of solution-processed bulk heterojunction devices from subphthalocyanine (SubPc) units as the acceptor component and conventional polymeric donor materials such as MEH-PPV, P3HT and PTB7. The high solubility of the SubPc derivatives facilitated the formation of efficient donor/acceptor networks and provided power conversion efficiencies of 0.4% with MEH-PPV, 1.1% with P3HT and 3.5% with PTB7. A clear contribution of photon harvesting by the acceptor was identified from the external quantum efficiency spectra. Analysis of the current–voltage characteristics and photoluminescence quenching revealed trap-assisted and geminate recombination as a loss mechanism. Our results show that solution-processable SubPcs are a promising alternative to fullerenes for polymer solar cells.
Co-reporter:Jeremie Louisy, François Delattre, Joel Lyskawa, Aurélie Malfait, Catherine E. Maclean, Léna Sambe, Ning Zhu, Graeme Cooke and Patrice Woisel
Chemical Communications 2011 - vol. 47(Issue 24) pp:NaN6821-6821
Publication Date(Web):2011/05/10
DOI:10.1039/C1CC10571J
The addition of the surfactant SDS to an aqueous solution containing 1·2 results in the disassembly of the latter via the simultaneous incorporation of 1 into a micelle and the precipitation of 2 by an anion exchange reaction.
Co-reporter:S. M. Abdalhadi, A. Connell, X. Zhang, A. A. Wiles, M. L. Davies, P. J. Holliman and G. Cooke
Journal of Materials Chemistry A 2016 - vol. 4(Issue 40) pp:NaN15661-15661
Publication Date(Web):2016/09/23
DOI:10.1039/C6TA04483B
Precursors to three new 3,4-ethylenedioxythiophene (EDOT) incorportaing dyes have been synthesised via a one-pot C–H activation route using N,N-dimethylaniline as a donor group. We have extended this methodology to provide a convenient one-pot route to dye EDOT-Ph. The electrochemical and optical properties of the new dyes have been correlated with IV and EQE data for 1 cm2 dye-sensitized solar cell (DSSC) devices prepared using these dyes. The device data show that dye performance is strongly affected by the amount of chenodeoxycholic acid (CDCA) co-sorbent used. The best performance is for EDOT-Ph (η = 4.0%) at 10 mM CDCA compared to (η = 6.0% and η = 5.8%) for N719 and D205 control cells.
Co-reporter:Alan A. Wiles, Xiaolu Zhang, Brian Fitzpatrick, De-Liang Long, Stuart A. Macgregor and Graeme Cooke
Dalton Transactions 2016 - vol. 45(Issue 17) pp:NaN7225-7225
Publication Date(Web):2016/04/11
DOI:10.1039/C6DT00875E
Chemical redox reactions have been exploited to transform unreactive vinylferrocene into a powerful dienophile for the Diels–Alder reaction and reactive substrate for thiol addition reactions upon conversion to its ferrocenium state. We have further investigated the ability of these reactions to facilitate redox-auxiliary-like reactivity by further hydrogenolyisis of the Diels–Alder adduct to the corresponding cyclopentane derivative.