Molecular recognition between functionalized gold nanoparticles and healable, supramolecular polymer blends – a route to property enhancement

A new, healable, supramolecular nanocomposite material has been developed and evaluated. The material comprises a blend of three components: a pyrene-functionalized polyamide, a polydiimide and pyrene- functionalized gold nanoparticles (P-AuNPs). The polymeric components interact by forming well-defined p–p stacked complexes between p-electron rich pyrenyl residues and p-electron deficient polydiimide residues. Solution studies in the mixed solvent chloroform–hexafluoroisopropanol (6 : 1, v/v) show that mixing the three components (each of which is soluble in isolation), results in the precipitation of a supramolecular, polymer nanocomposite network. The precipitate thus formed can be re-dissolved on heating, with the thermoreversible dissolution/precipitation procedure repeatable over at least 5 cycles. Robust, self-supporting composite films containing up to 15 wt% P-AuNPs could be cast from 2,2,2- trichloroethanol. Addition of as little as 1.25 wt% P-AuNPs resulted in significantly enhanced mechanical properties compared to the supramolecular blend without nanoparticles. The nanocomposites showed a linear increase in both tensile moduli and ultimate tensile strength with increasing P-AuNP content. All compositions up to 10 wt% P-AuNPs exhibited essentially quantitative healing efficiencies. Control experiments on an analogous nanocomposite material containing dodecylamine-functionalized AuNPs (5 wt%) exhibited a tensile modulus approximately half that of the corresponding nanocomposite that incorporated 5 wt% pyrene functionalized-AuNPs, clearly demonstrating the importance of the designed interactions between the gold filler and the supramolecular polymer matrix

Fluoride degradable and thermally debondable polyurethane based adhesive

We report the one-pot, solvent free synthesis of a stimuli-responsive polyurethane (PU) adhesive. The hard domains within the supramolecular PU network contain a silyl protected phenol ‘degradable unit’ (DU). The DU undergoes rapid decomposition (<30 minutes) upon treatment with fluoride ions which causes depolymerisation of the linear PU adhesive. The mechanism of depolymerisation was investigated in solution using 1H NMR spectroscopy by following the degradation of the polymer in the presence of tetra-butylammonium fluoride (TBAF). In the absence of fluoride ions, the material behaves as a typical thermoplastic adhesive, and underwent four adhesion/separation cycles without loss of strength. The fluoride initiated depolymerisation of the PU adhesive in the solution state was verified by GPC analysis, showing reduction in Mn from 26.1 kg mol−1 for the pristine PU to 6.2 kg mol−1 for the degraded material. Degradation studies on solid samples of the PU which had been immersed in acetone/TBAF solution for 30 minutes exhibited a 91% reduction in their modulus of toughness (from 27 to 2 MJ m−3). Lap shear adhesion studies showed the fluoride responsive PU was an excellent material to join metallic, plastic, glass and wood surfaces. Pull adhesion tests confirmed that immersing the adhesive in TBAF/acetone solution resulted in a reduction in strength of up to 40% (from 160 N to 95 N at break) after drying

Effect of water-soluble polymers, polyethylene glycol and poly(vinylpyrrolidone),on the gelation of aqueous micellar solutions of Pluronic copolymer F127

The micellization of F127 (E98P67E98) in dilute aqueous solutions of polyethylene glycol (PEG6000 and PEG35000) and poly(vinylpyrrolidone) (PVP K30 and PVP K90) is studied. The average hydrodynamic radius (rh,app) obtained from the dynamic light scattering technique increased with increase in PEG concentration but decreased on addition of PVP, results which are consistent with interaction of the micelles with PEG and the formation of micelles clusters, but no such interaction occurs with PVP. Tube inversion was used to determine the onset of gelation. The critical concentration of F127 for gelation increased on addition of PEG and of PVP K30 but decreased on addition of PVP K90. Small-angle X-ray scattering (SAXS) was used to show that the 30 wt% F127 gel structure (fcc) was independent of polymer type and concentration, as was the d-spacing and so the micelle hard-sphere radius. The maximum elastic modulus (G0 max) of 30 wt% F127 decreased from its value for water alone as PEG was added, but was little changed by adding PVP. These results are consistent with the packed-micelles in the 30 wt% F127 gel being effectively isolated from the polymer solution on the microscale while, especially for the PEG, being mixed on the macroscale

Novel polyvinylpyrrolidones to improve delivery of poorly-water soluble drugs; from design to synthesis and evaluation

Polyvinylpyrrolidone is a widely used in tablet formulations with the linear form acting as a wetting agent and disintegrant whereas the cross-linked form is a super-disintegrant. We have previously reported that simply mixing the commercial cross-linked polymer with ibuprofen disrupted drug crystallinity with consequent improvements in drug dissolution behavior. In this study, we have designed and synthesized novel cross-linking agents containing a range of oligoether moieties which have then be polymerized with vinylpyrrolidone to generate a suite of novel excipients with enhanced hydrogen-bonding capabilities. The polymers have a porous surface and swell in most common solvents and in water; properties which suggest their value as disintegrants. The polymers were evaluated in simple physical mixtures with ibuprofen as a model poorly-water soluble drug. The results show that the novel PVPs induce the drug to become “X-ray amorphous”, which increased dissolution to a greater extent than that seen with commercial cross-linked PVP. The polymers stabilize the amorphous drug with no evidence for recrystallization seen after 20 weeks storage

Efficient access to conjugated 4,4′-bipyridinium oligomers using the Zincke reaction: Synthesis, spectroscopic and electrochemical properties

The cyclocondensation reaction between rigid, electron-rich aromatic diamines and 1,1′-bis(2,4-dinitrophenyl)-4,4′-bipyridinium (Zincke) salts has been harnessed to produce a series of conjugated oligomers containing up to twelve aromatic/heterocyclic residues. These oligomers exhibit discrete, multiple redox processes accompanied by dramatic changes in electronic absorption spectra

Conjugated, rod-like viologen oligomers: correlation of oligomer length with conductivity and photoconductivity

An iterative synthesis has been used to produce conjugated, monodisperse, viologen-based aromatic oligomers containing up to 12 aromatic/heterocyclic rings. The methoxy-substituted oligomers were soluble in common organic solvents and could be processed by spin coating. The conductivities of the resulting films (30 to 221 nm thick) increased by more than an order of magnitude as the oligomer length increased from unimer (1, 2.20×10-11 S cm-1) through dimer (2) to trimer (3, 6.87×10-10 S cm-1). The bandgaps of the materials were estimated from the absorption spectra of these thin films. The longest oligomer, 3, exhibited a noticeably narrower bandgap (2.3 eV) than the shorter oligomers (1 and 2 both 2.7 eV). Oligomer 3 also showed photoconductivity under irradiation across a wide range of wavelengths in the visible spectral region. In conjunction with DFT calculations of these systems our results suggest that structurally related viologen-type oligomers may find use in optoelectronic devices

Fluoride-responsive debond on demand adhesives: manipulating polymercrystallinity and hydrogen bonding to optimise adhesion strength at lowbonding temperatures

This paper reports the solvent-free synthesis of a series of sixfluoride responsive debond-on-demand poly-urethane (PU) adhesives that contain a silyl functionalised degradable unit (DU). To optimise the adhesionstrength and debonding nature of the adhesives, the chemical composition of the PUs was varied according tothe structure of the polyol or the diisocyanate component in the polymer mainchain.1H NMR spectroscopy wasused to study the depolymerisation behaviour in solution state. It showed thattetra-butylammoniumfluoride(TBAF) triggered the breakdown of the DU unit without fragmenting the polyol mainchain indiscriminately. Onexposure tofluoride ions, the PUs underwent depolymerisation with reductions in Mnranging from 64 to 90% asmeasured by GPC analysis. The morphology and thermal properties of the PUs were characterised by differentialscanning calorimetry (DSC), rheology and variable temperature (VT) SAXS/WAXS analysis. Each techniquedemonstrated the reversibility of the supramolecular polymer network under thermal stimuli. PUs containingpoly(butadiene) soft segments were amorphous with glass transition and viscoelastic transition temperaturesdependent on the nature of the soft segment and diisocyanate starting materials. The PU containing a polyestersoft segment exhibited a defined melting point at 49 °C. Mechanical stress-strain analysis of the series of PUsshowed each exhibited greater than 70% reduction in toughness after treatment with TBAF for 30 min as aconsequence of the chemo-responsive degradation of the polymer mainchain. The material featuring an ester-based polyol demonstrated excellent adhesion at bonding temperatures as low as 60 °C. Moreover, this materialcould be thermally rebonded if broken by force without loss in adhesion strength over three debond-rebondcycles. Lap shear adhesion tests showed a reduction in adhesive strength of approximately 40% (from 11.4 MPato 7.3 MPa) on exposure tofluoride ion

Synthesis and biological evaluation of benzodiazepines containing a pentafluorosulfanyl group

The widely used pentafluorosulfanyl group (SF5) was deployed as a bioisosteric replacement for a chloro-group in the benzodiazepine diazepam (Valium™). Reaction of 2-amino-5-pentafluorosulfanyl-benzophenone with chloroacetyl chloride followed by hexamethylenetetramine, in the presence of ammonia, led to 7-sulfurpentafluoro-5-phenyl-1H-benzo[1,4]diazepin-2(3H)-one (2c). The latter was able to undergo a Pd-catalysed ortho-arylation, demonstrating that these highly fluorinated benzodiazepines can be further modified to form more complicated scaffolds. The replacement of Cl by the SF5 group, led to a loss of potency for potentiating GABAA receptor activation, most likely because of a lost ligand interaction with His102 in the GABAA receptor α subunit. Dedicated to Professor Jonathan Williams, an inspirational and humble pioneer, a colleague and mentor in chemistry

Multivalency in healable supramolecular polymers: the effect of supramolecular cross-link density on the mechanical properties and healing of non- covalent polymer networks

Polymers with the ability to heal themselves could provide access to materials with extended lifetimes in a wide range of applications such as surface coatings, automotive components and aerospace composites. Here we describe the synthesis and characterisation of two novel, stimuli-responsive, supramolecular polymer blends based on p-electron-rich pyrenyl residues and p-electron-deficient, chain-folding aromatic diimides that interact through complementary p–p stacking interactions. Different degrees of supramolecular “cross-linking” were achieved by use of divalent or trivalent poly(ethylene glycol)-based polymers featuring pyrenyl end-groups, blended with a known diimide–ether copolymer. The mechanical properties of the resulting polymer blends revealed that higher degrees of supramolecular “cross-link density” yield materials with enhanced mechanical properties, such as increased tensile modulus, modulus of toughness, elasticity and yield point. After a number of break/heal cycles, these materials were found to retain the characteristics of the pristine polymer blend, and this new approach thus offers a simple route to mechanically robust yet healable materials

Solvent-free synthesis of core-functionalised naphthalene diimides by using a vibratory ball mill: Suzuki, Sonogashira and Buchwald–Hartwig reactions

Solvent-free synthesis by using a vibratory ball mill (VBM) offers the chance to access new chemical reactivity, whilst reducing solvent waste and minimising reaction times. Herein, we report the core functionalisation of N,N’-bis(2-ethylhexyl)-2,6-dibromo-1,4,5,8-naphthalenetetracarboxylic acid (Br2-NDI) by using Suzuki, Sonogashira and Buchwald–Hartwig coupling reactions. The products of these reactions are important building blocks in many areas of organic electronics including organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic cells (OPVCs). The reactions proceed in as little as 1 h, use commercially available palladium sources (frequently Pd(OAc)2) and are tolerant to air and atmospheric moisture. Furthermore, the real-world potential of this green VBM protocol is demonstrated by the double Suzuki coupling of a monobromo(NDI) residue to a bis(thiophene) pinacol ester. The resulting dimeric NDI species has been demonstrated to behave as an electron acceptor in functioning OPVCs