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Publications (44)
A 1:1 binding stoichiometry of a host–guest complex need not consist of a single host and guest. Diarylviologens containing electron-donating substituents complexed with cucurbit[8]uril (CB[8]) in a 1:1 stoichiometry exhibit abnormally large binding enthalpies compared to typical enthalpy changes observed for 1:1 binary complexes. Here, several CB[...
Host-guest complexes exhibiting a 1:1 binding stoichiometry need not consist of a single host and guest. A series of oligopeptides, which were previously reported to have abnormally high binding enthalpies were investigated to deduce whether they exist as a 2:2 quaternary or a 1:1 binary complex with cucurbit[8]uril (CB[8]). Through a systematic st...
A modular strategy has been employed to develop a new class of fluorescent molecules, which generates discrete, dimeric stacked fluorophores upon complexation with multiple cucurbit[8]uril macrocycles. The multiple constraints result in a “static” complex (remaining as a single entity for more than 30 ms) and facilitate fluorophore coupling in the...
The challenge of quantitatively forming self‐assembled hetero‐dimers without other equilibrium by‐products is overcome through self‐sorting favored by the introduction of designed shape‐complementary moieties. Such a supramolecular strategy based on CB[8]‐directed dimerization is further applied to generate hetero‐chromophore dimers quantitatively,...
Controlling the spatial and temporal behavior of peptide segments is essential in the fabrication of functional peptide-based materials and nanostructures. To achieve a desired structure, complex sequence design is often required, coupled with the inclusion of unnatural amino acids or synthetic modifications. Herein, we investigate the structural p...
Peptide dimerization is ubiquitous in natural protein conjugates and artificial self-assemblies. A major challenge in artificial systems remains achieving quantitative peptide heterodimerization, critical for next-generation biomolecular purification and formulation of therapeutics. Here, we employ a synthetic host to simultaneously encapsulate an...
Supramolecular polymer networks are non-covalently crosslinked soft materials that exhibit unique mechanical features such as self-healing, high toughness and stretchability. Previous studies have focused on optimizing such properties using fast-dissociative crosslinks (that is, for an aqueous system, dissociation rate constant kd > 10 s−1). Herein...
In many natural and synthetic systems, quantifying the amount of water present within a material is crucial to understanding its mechanical properties. Furthermore, biological materials often rely on aqueous supramolecular...
Peptide dimerization plays an important role in both natural and artificial supramolecular systems. A major challenge to date is the quantitative heterodimerization of two peptides without formation of homodimers. Here, we employ a macrocyclic host to simultaneously encapsulate a canonical aromatic peptide and a non-canonical perfluorophenylalanine...
A correction to this paper has been published: https://doi.org/10.1007/s11242-021-01569-3
We introduce a new facile synthetic methodology for the preparation of alkyl pyridinium-containing acrylamide monomers. Inclusion complexes of these new monomers with CB[8] facilitate supramolecular crosslinking in a series of hydrogels formed through in situ polymerisation. The resulting hydrogels not only show greatly enhanced mechanical properti...
Wider use of timber has the potential to greatly reduce the embodied carbon of construction. Improved chemical treatment could help overcome some of the barriers to wider application of timber, by furthering the durability and/or mechanical properties of this natural material. Improving timber treatment by treating the whole volume of a piece of ti...
Co-polycondensation of the diimide-based diols N,N'-bis(2-hydroxyethyl)hexafluoroisopropylidene-diphthalimide, (HFDI), and N,N'-bis(2-hydroxy-ethyl)naphthalene-1,4,5,8-tetracarboxylic-diimide, (NDI), with aliphatic diacyl chlorides ClOC(CH2)
x
COCl (x = 5 to 8) affords linear copoly(ester-imide)s. Such copolymers interact with pyrene via supramole...
Machine learning is a valuable tool in the development of chemical technologies but its applications into supramolecular chemistry have been limited. Here, the utility of kernel-based support vector machine learning using density functional theory calculations as training data is evaluated when used to predict equilibrium binding coefficients of sm...
The challenge of quantitatively forming self‐assembled hetero‐dimers without other equilibrium by‐products is overcome through self‐sorting favored by the introduction of designed shape‐complementary moieties. Such a supramolecular strategy based on CB[8]‐directed dimerization is further applied to generate hetero‐chromophore dimers quantitatively,...
Phenyl-perfluorophenyl polar-π interactions have been revisited for the design and fabrication of functional supramolecular systems. The relatively weak associative interactions (ΔG ≈ -1.0 kcal/mol) have limited their use in aqueous self-assembly to date. Herein, we propose a strategy to strengthen phenyl-perfluorophenyl polar-π interactions by enc...
Co-polycondensation of the diimide-based diols N , N '-bis(2-hydroxyethyl)hexafluoro-isopropylidene-diphthalimide, (HFDI), and N , N '-bis(2-hydroxy-ethyl)naphthalene-1,4,5,8-tetracarboxylic-diimide, (NDI), with aliphatic diacyl chlorides ClOC(CH<sub>2</sub>) <sub>x</sub> COCl ( x = 5 to 8) affords linear copoly(ester-imide)s. Such copolymers inter...
Timber is the only widely used construction material we can grow. The wood from which it comes has evolved to provide structural support for the tree and to act as a conduit for fluid flow. These flow paths are crucial for engineers to exploit the full potential of timber, by allowing impregnation with liquids that modify the properties or resilien...
Polycondensation of the diimide-based diols N,N'-bis(2-hydroxyethyl)hexafluoro-isopropylidene-diphthalimide (HFDI), N,N'-bis(2-hydroxyethyl)pyromellitimide (PMDI), or N,N'-bis(2-hydroxyethyl)naphthalene-1,4,5,8-tetracarboxylic-diimide (NDI) with aliphatic diacyl chlorides ClOC(CH2)xCOCl (x = 1 to 8) affords linear poly(ester-imide)s. Homopolymers b...
Pseudo[2,3]rotaxanes have been successfully fabricated by the complexation of cucurbit[8]uril (CB[8]) macrocycles with extended viologen derivatives. Two design rules enable the incorporation of a third CB[8] onto a recently reported...
DFT, NMR, ITC, and cell confluence data are used to generate predictive algorithms of supramolecular binding to cucurbit[7]uril and experimentally validate these predictions.
DFT calculations are used as training data to predict equilibrium binding constants of small molecules to cucurbit[7]uril (CB[7]) with kernel-based support vector machine learning. This trained algorithm was then used to predict the binding of two promising small molecule drugs in the clinic against pediatric low grade glioma, TAK-580 and Selumetin...
Cucurbit[8]uril (CB[8]) mediated assembly of extended aryl viologens (EVs) into optically tunable dimers is reported for the first time. We show that the modular design and synthesis of a new class of π-conjugated viologen derivatives with rigid aromatic or heteroaromatic bridging units as well as electron donating molecular recognition motifs enab...
Stimuli-responsive hydrogels are attractive materials with many applications towards biomedicine, biology, construction, and manufacturing. Materials that can be cured or annealed rapidly at room temperature are of particular interest. In this work we develop a class of supramolecular coumarin-functionalised hydrogels formed via host-guest mediated...
For wood to be used to its full potential as an engineering material, it is necessary to quantify links between its cell geometry and the properties it exhibits at bulk scale. Doing so will make it possible to predict timber properties crucial to engineering, such as mechanical strength and stiffness, and the resistance to fluid flow, and to inform...
For wood to be used to its full potential as an engineering material, it is necessary to quantify links between its cell geometry and the properties it exhibits at bulk scale. Doing so will make it possible to predict timber properties crucial to engineering, such as mechanical strength and stiffness, and the resistance to fluid flow, and to inform...
The ability to mimic the activity of natural enzymes using supramolecular constructs (artificial enzymes) is a vibrant scientific research field. Herein, we demonstrate that cucurbit[7]uril (CB[7]) can catalyse Diels–Alder reactions for a number of substituted and unreactive N-allyl-2-furfurylamines under biomimetic conditions, without the need for...
Lumen impregnation, unlike most other wood modification methods, is typically assessed by the pore-filling ratio (PFR) (i.e. the fraction of luminal porosity filled) rather than by weight percentage gain (WPG). During lumen impregnation, the impregnants act on the voids in the wood rather than on the solid mass (e.g. cell walls), but the PFR cannot...
The ability to mimic the activity of natural enzymes using supramolecular constructs (artificial enzymes) represents a vibrant scientific research field. Herein, we demonstrate that cucurbit[7]uril (CB[7]) can catalyze Diels-Alder reactions for a number of substituted and unreactive N-allyl-2-furfurylamines under biomimetic conditions, without the...
The ability to mimic the activity of natural enzymes using supramolecular constructs (artificial enzymes) represents a vibrant scientific research field. Herein, we demonstrate that cucurbit[7]uril (CB[7]) can catalyze Diels-Alder reactions for a number of substituted and unreactive N-allyl-2-furfurylamines under biomimetic conditions, without the...
Lumen impregnation, unlike most other wood modification methods, is typically assessed by the pore-filling ratio (PFR) (i.e. the fraction of luminal porosity filled) rather than by weight percentage gain (WPG). During lumen impregnation, the impregnants act on the voids in the wood rather than on the solid mass (e.g. cell walls), but the PFR cannot...
Rigid gap nano-aggregates of Au nanoparticles formed using cucurbit[n]uril (CB[n]) molecules are used to investigate competitive binding of ethanol and methanol in an aqueous environment. We show it is possible to detect as little as 0.1% methanol in water and a ten times higher affinity to methanol over ethanol, making this a useful technology for...
We acknowledge financial support from the UK’s Engineering and Physical Sciences Research Council (grants EP/L027151/1, EP/K028510/1, EP/L015978/1, EP/N020669/1) and the European Research Council (grants LINASS 320503, MSCA-IF-2015-EF SPARCLEs 7020005 and MSCA-IF-2014-EF NANOSPHERE, 658360). RC acknowledges support from the Dr. Manmohan Singh schol...
Trees, and their derivative products, have been used by societies around the world for thousands of years. Contemporary construction of tall buildings from timber, in whole or in part, suggests a growing interest in the potential for building with wood at a scale not previously attainable. As wood is the only significant building material that is g...
A 1:1 binding stoichiometry of a host−guest complex need not consist of a single host and guest. Diarylviologens containing electron-donating substituents complexed with cucurbit[8]uril (CB[8]) in a 1:1 stoichiometry exhibit abnormally large binding enthalpies compared to typical enthalpy changes observed for 1:1 binary complexes. Here, several CB[...
2016 The AuthorsTrees, and their derivative products, have been used by societies around the world for thousands of years. Contemporary construction of tall buildings from timber, in whole or in part, suggests a growing interest in the potential for building with wood at a scale not previously attainable. As wood is the only significant building ma...
Correction for ‘Hybrid organic–inorganic supramolecular hydrogel reinforced with CePO 4 nanowires’ by Chenyan Liu et al. , Polym. Chem. , 2016, 7 , 6485–6489.
Trees, and their derivative products, have been used by societies around the world for thousands of years. Contemporary construction of tall buildings from timber, in whole or in part, suggests a growing interest in the potential for building with wood at a scale not previously attainable. As wood is the only significant building material that is g...
We report a method to enhance the stiffness in the rheological yield strain of cucurbit[8]uril (CB[8])-based hydrogels by introducing inorganic nanowires (NWs) into the supramolecular networks. The supramolecular hydrogel is comprised of methylviologen-functionalised poly(vinyl alcohol) (PVA-MV), hydroxyethyl cellulose with naphthyl moieties (HEC-N...
We report a method to enhance the stiffness in the rheological yield strain of cucurbit[8]uril (CB[8])-based hydrogels by introducing inorganic nanowires (NWs) into the supramolecular networks. The supramolecular hydrogel is comprised of methylviologen-functionalised poly(vinyl alcohol) (PVA-MV), hydroxyethyl cellulose with naphthyl moieties (HEC-N...
Rational control over cooperativity of multiple non-covalent interactions often plays an important role in the design and construction of supramolecular self-assemblies and materials, especially in precision supramolecular engineering. However, it still remains a challenge to control the cooperativity of multiple non-covalent interactions through t...
We demonstrate the preparation of surface-bound cucurbit[8]uril (CB[8]) catenanes on silica nanoparticles(NPs), where CB[8] was employed as a tethered supramolecular "handcuff" to selectively capture targetguest molecules. In this catenane, CB[8] was threaded onto a methyl viologen (MV2+) axle and immobilized onto silica NPs. The formation of CB[8]...
IntroductionConventional LbL MethodsUnconventional LbL Methods
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