Search

Dimer and trimer analogues of Spiro-OMeTAD are porous hole transport materials with improved conductivity compared to the parent material and give higher power conversion efficiencies in perovskite solar cells.

JMS acknowledges the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001 for PhD funding. LKJ acknowledges support from the Marie Skłodowska-Curie Individual Fellowship (European Commission) (MCIF: no. 745776) and funding from UKRI-FLF through MR/T022094/1. GC thanks the EPSRC (EP/E036244/1) for funding. BODIPY-based materials are well known for their outstanding chemical and photo-stability as well as their ease of synthesis and tunability of their frontier molecular orbitals. These are attractive features for hole transporting materials (HTMs) for perovskite solar cells (PSCs) that could help improve device stability and cost. In this paper, we report the straightforward synthesis of a new BODIPY small molecule, PTZ-PTZ-BDP , functionalised with phenothiazine moieties in both the meso and α positions giving rise to a Y-shaped structure. As estimated by DFT calculations, and confirmed by electrochemical and ambient photoemission spectroscopy studies, PTZ-PTZ-BDP presents appropriate energy levels suitable for its use as a HTM in PSCs. Electrochemical measurements also reveal several redox processes with excellent reversibility. Systematic evaluation of its performance as HTM in n–i–p PSC with and without dopants was conducted and the device parameters compared with commonly used HTMs of spiro-OMeTAD and PTAA. The CH3NH3PbI3 based PSCs incorporating simple solution processed PTZ-PTZ-BDP as HTM demonstrated a champion power conversion efficiency of 14.6%, matched in performance and shelf-life stability to complex and expensive state-of-the-art HTMs, showing that BODIPY based HTMs are a promising direction for perovskite solar cells. Publisher PDF

GC acknowledges the EPSRC for funding (EP/E036244/1). JMS acknowledges the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001 for PhD funding. JMS also acknowledges Dr Nor Basid Adiwibawa Prasetya for helpful advice. Dr L. K. Jagadamma acknowledges support from a Marie Skłodowska-Curie Individual Fellowship (European Commission) (MCIF: No. 745776). Thiophene-based semiconductors are amongst the most successful materials in organic electronics. In this contribution, we present the synthesis and characterisation of two thiophene-based macrocycles as well as their evaluation in organic-electronic devices. McT-1 is composed of ten thiophene moieties, whereas in McT-2, four additional electron-deficient benzothiadiazole moieties are incorporated to form a donor–acceptor (D–A) π-system. Red-shifted and broadened absorption spectra as well as more positive redox potentials are observed in McT-2, whereas McT-1 displays a sharper absorption band with a higher extinction coefficient. Macrocycle McT-1 shows emission in the yellow region whereas McT-2 displays emission in the red wavelength region. DFT calculations predict the macrocycles to comprise of mainly the E,E isomers with a near-planar structure, which is further supported by the single crystal X-ray structure for McT-1. Their charge transporting properties are determined by fabricating thin-film OFETs. The photovoltaic properties of McT-1 and McT-2 are also investigated by fabricating bulk heterojunction (BHJ) devices and their potential as photodetectors has been evaluated. Publisher PDF

Organic-based electrodes for Li- and Na-ion batteries present attractive alternatives to commonly applied inorganic counterparts which can often carry with them supply-chain risks, safety concerns with thermal runaway, and adverse environmental impact. The ability to chemically direct the structure of organic electrodes through control over functional groups is of particular importance, as this provides a route to fine-tune electrochemical performance parameters. Here, we report two benzo-dipteridine derivatives, BF-Me2 and BF-H2, as high-capacity electrodes for use in Li- and Na-ion batteries. These moieties permit binding of multiple Li-ions per molecule while simultaneously ensuring low solubility in the supporting electrolyte, often a precluding issue with organic electrodes. Both display excellent electrochemical stability, with discharge capacities of 142 and 182 mAh g–1 after 100 cycles at a C/10 rate and Coulombic efficiencies of 96% and ∼ 100% demonstrated for BF-Me2 and BF-H2, respectively. The application of a Na-ion cell has also been demonstrated, showing discharge capacities of 88.8 and 137 mAh g–1 after 100 cycles at a C/2 rate for BF-Me2 and BF-H2, respectively. This work provides an encouraging precedent for these and related structures to provide versatile, high-energy density, and long cycle-life electrochemical energy storage materials.

International audience; Chiral biological and pharmaceutical molecules are analyzed with phenomena that monitor their very weak differential interaction with circularly polarized light. This inherent weakness results in detection levels for chiral molecules that are inferior, by at least six orders of magnitude, to the single molecule level achieved by state-of-the-art chirally insensitive spectroscopic measurements. Here, we show a phenomenon based on chiral quantum metamaterials (CQMs) that overcomes these intrinsic limits. Specifically, the emission from a quantum emitter, a semiconductor quantum dot (QD), selectively placed in a chiral nanocavity is strongly perturbed when individual biomolecules (here, antibodies) are introduced into the cavity. The effect is extremely sensitive, with six molecules per nanocavity being easily detected. The phenomenon is attributed to the CQM being responsive to significant local changes in the optical density of states caused by the introduction of the biomolecule into the cavity. These local changes in the metamaterial electromagnetic environment, and hence the biomolecules, are invisible to “classical” light-scattering-based measurements. Given the extremely large effects reported, our work presages next generation technologies for rapid hypersensitive measurements with applications in nanometrology and biodetection.

With the increased application of batteries in powering electric vehicles as well as potential contributions to utility-scale storage, there remains a need to identify and develop efficient and sustainable active materials for use in lithium (Li)- and sodium (Na)-ion batteries. Organic cathode materials provide a desirable alternative to inorganic counterparts, which often come with harmful environmental impact and supply chain uncertainties. Organic materials afford a sustainable route to active electrodes that also enable fine-tuning of electrochemical potentials through structural design. Here, we report a bis-anthraquinone-functionalized s-indacene-1,3,5,7(2H,6H)-tetraone (BAQIT) synthesized using a facile and inexpensive route as a high-capacity cathode material for use in Li- and Na-ion batteries. BAQIT provides multiple binding sites for Li- and Na-ions, while maintaining low solubility in commercial organic electrolytes. Electrochemical Li-ion cells demonstrate excellent stability with discharge capacities above 190 mAh g-1 after 300 cycles at a 0.1C rate. The material also displayed excellent high-rate performance with a reversible capacity of 142 mAh g-1 achieved at a 10C rate. This material affords high power capabilities superior to current state-of-the-art organic cathode materials, with values reaching 5.09 kW kg-1. The Na-ion performance was also evaluated, exhibiting reversible capacities of 130 mAh g-1 after 90 cycles at a 0.1C rate. This work offers a structural design to encourage versatile, high-power, and long cycle-life electrochemical energy-storage materials.

Traditionally, metal free DSSCs are fabricated from sensitizers designed using a donor–pi–acceptor (D–π–A) architecture. More recently, non-conventional dyes without strong donor units have emerged and have provided competitive power conversion efficiencies (PCEs) with respect to their (D–π–A)-based counterparts. Here, we report the synthesis and DSSC fabrication of oligothiophene molecules featuring two anchoring groups that do not possess strong donor moieties and are able to adopt V- and U-shape conformations. PCEs of 3.70% were obtained with the smaller 5-thiophene dyes (5T2A, 5T2A-E) possessing higher PCEs than their larger 8-thiophene counterparts containing diacetylene units (8T4A, 8T4A-E). Comparison to the DSSC properties of the analogous linear dye 5T, indicates that the architecture and structure of this series of dyes are likely responsible for their lower performance.

Controlling the swelling properties of hydrogels is of primary importance for many applications ranging from actuators and valves to tissue engineering and drug delivery. Herein, we report the use of cyclobis(paraquat-p-phenylene) (CBPQT4+,4X–) as a versatile host to fine-tune the swelling behavior of 1,5-dialkyloxynaphthalene guest containing poly(N,N-dimethylacrylamide) hydrogels (NaphtGelz) through supramolecular host–guest complexation. While the equilibrium swelling of NaphtGelz in water decreases with increasing amount of hydrophobic naphthalene groups, the opposite behavior is observed with superabsorbing behavior (up to 180 times their initial dry mass) upon immersion in aqueous solutions containing the macrocyclic CBPQT4+,4X– due to formation of tetracationic host–guest complexes. In this case, the swelling amplitude could be conveniently programmed either by variation of the naphthalene content of the hydrogels or by controlling the stoichiometry of the host–guest binding events. Furthermore, by modifying the nature of the counterions (X = Cl–, Br–, and I–) of the tetracationic CBPQT4+ macrocyclic host, the swelling of the hydrogels could be tuned in line with Pearson’s absolute hardness scale of X–. The swelling behavior of these supramolecular hydrogels could be successfully described by a theoretical model, taking into account the hydrophobic association of the naphthalene groups and their screening by host–guest complexation. Finally, addition of sodium dodecyl sulfate as a surfactant to the supramolecularly swollen hydrogels led to a large decrease in hydrogel size due to dissociation of the host–guest complexes and the formation of CBPQT4+,4DS– within the hydrogel.

We are grateful to EPSRC for financial support (grants EP/L012294/1 and EP/E036244/1). JMDS thanks CAPES for funding. NML thanks the Iraqi government for funding. Theresearch data supporting this publication can be accessed at DOI: http://dx.doi.org/10.5525/gla.researchdata.666 The study of small donor molecules as the active component of organic solar cells continues to attract considerable attention due to the range of advantages these molecules have over their polymeric counterparts. Here we report the synthesis and solar cell fabrication of three BODIPY small molecule donors. Two of the dyes feature triphenylamine and phenothiazine as donor units attached to the meso and α-positions of the BODIPY core (TPA-PTZ-DBP and PTZ-TPA-BDP). Additionally, we have synthesised a push–pull derivative featuring phenothiazine moieties in the α-positions and a nitrobenzene in the meso-position (N-TPA-BDP) in order to investigate what effect this type of functionalisation has on the photovoltaic properties compared to the other dyes. The optoelectronic properties were investigated and the dyes showed broad absorption in the near-infrared with high extinction coefficients. Electrochemical measurements indicated good reversibility for the dyes redox processes. In contrast with the all-donor functionalised systems, N-TPA-BDP demonstrated extensive HOMO–LUMO overlap by DFT. The dyes were investigated as donor molecules in bulk heterojunction solar cells along with PC71BM, and under optimal donor to acceptor ratio PTZ-TPA-BDP showed the highest PCE of 1.62%. N-PTZ-BDP:PC71BM was the only blend to further improve upon thermal annealing reaching the highest conversion efficiency among the dyes of 1.71%. A morphology comprised of finely mixed donor and acceptor components is observed for BHJ blends of each of the three donors at their optimum fullerene content. Upon thermal annealing, these morphological features remain mostly the same for PTZ-TPA-BDP:PC71BM and TPA-PTZ-DBP:PC71BM blends whereas for N-PTZ-BDP:PC71BM the domains show a larger size. These dyes show that phenothiazine functionalisation of BODIPY is useful for solar cells because it gives strong and broad absorption extending to the near infra-red and materials with reversible redox properties – both of which are desirable for organic solar cells. Publisher PDF

Organic hole-transporting materials (HTM) have shown excellent ability in achieving high efficiency\ud perovskite solar cells. However, their high cost significantly limits their applications in scaling-up\ud perovskite solar cells. Here, we report an efficient, low-cost HTM, called TAT-tBuSty, comprising a\ud central triazatruxene moiety with 3 terminal tert-butoxy styrene groups and 3 hexyl side chains on the\ud indole nitrogen. For the first time, we use an inexpensive liquid precursor to attach the donor ligand to\ud the molecule. This enables purification of the HTM using a silica plug and recrystallization without the\ud need for complicated column chromatography, which is typically required to purify solid-precursorprepared\ud HTMs. We estimate that the cost for the purified TAT-tBuSty is $69.90 g�1, which is 35%\ud cheaper than the widely-used 2,207,70-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,90-spirobifluorene\ud (spiro-OMeTAD; ca. $112.05 g�1). Using this low-cost TAT-tBuSty as the HTM in a caesium-formamidinium\ud mixed-cation perovskite solar cell, we have successfully achieved a champion power conversion efficiency\ud (PCE) of 20.3% (19.4% stabilized efficiency), which is comparable to the efficiency of devices using the\ud reference spiro-OMeTAD HTM. Our work is crucial for up-scaling of next-generation high-performance\ud metal-halide perovskite solar cells.

The development of organic down-converting materials continues to attract attention in hybrid LED technology by obviating the need for non-sustainable rare-earth elements. In this work, a benzodiimidazole-based system (TPA-BDI) has been employed as a down-converting layer in a hybrid organic-inorganic LED device. A commercially available poly(urethane)-based resin is used as the encapsulating material, providing a dilute layer of TPA-BDI that is deposited on top of the GaN-based LED. Crucially, the solution-state emissive performance is generally maintained when encapsulated at low concentrations within this resin. A maximum luminous efficacy of 87 lm W -1 was demonstrated using a 1.0 mg ml -1 concentration of TPA-BDI in the resin. The suitability of using organic down-converters to produce green light from hybrid devices was demonstrated by the excellent repeatability of the device characteristics across a series of encapsulated LEDs.

We acknowledge support from EPSRC (grant number EP/L012294/1) and the European Research Council (grant number 321305). I. D. W. S. also acknowledges a Royal Society Wolfson Research Merit Award. Additives play an important role in modifying the morphology and phase separation of donor and acceptor molecules in bulk heterojunction (BHJ) solar cells. Here, we report triptycene (TPC) as a small-molecule additive for supramolecular control of phase separation and concomitant improvement of the power conversion efficiency (PCE) of PTB7 donor and fullerene acceptor-based BHJ polymer solar cells. An overall 60% improvement in PCE is observed for both PTB7:PC61BM and PTB7:PC71BM blends. The improved photovoltaic (PV) performance can be attributed to three factors: (a) TPC-induced supramolecular interactions with donor:acceptor components in the blends to realize a nanoscale phase-separated morphology; (b) an increase in the charge transfer state energy that lowers the driving force for electron transfer from donor to acceptor molecules; and (c) an increase in the charge carrier mobility. An improvement in efficiency using TPC as a supramolecular additive has also been demonstrated for other BHJ blends such as PBDB-T:PC71BM and P3HT:PCBM, implying the wide applicability of this new additive molecule. A comparison of the photostability of TPC as an additive for PTB7:PCBM solar cells to that of the widely used 1,8-diiodooctane additive shows ∼30% higher retention of PV performance for the TPC-added solar cells after 34 h of AM 1.5G illumination. The results obtained suggest that the approach of using additives that can promote supramolecular interactions to modify the length scale of phase separation between donor and acceptor is very promising and can lead to the development of highly efficient and stable organic photovoltaics. Postprint Postprint

The structural order of biopolymers, such as proteins, at interfaces defines the physical and chemical interactions of biological systems with their surroundings and is hence a critical parameter in a range of biological problems. Known spectroscopic methods for routine rapid monitoring of structural order in biolayers are generally only applied to model single-component systems that possess a spectral fingerprint which is highly sensitive to orientation. This spectroscopic behavior is not a generic property and may require the addition of a label. Importantly, such techniques cannot readily be applied to real multicomponent biolayers, have ill-defined or unknown compositions, and have complex spectroscopic signatures with many overlapping bands. Here, we demonstrate the sensitivity of plasmonic fields with enhanced chirality, a property referred to as superchirality, to global orientational order within both simple model and "real" complex protein layers. The sensitivity to structural order is derived from the capability of superchiral fields to detect the anisotropic nature of electric dipole-magnetic dipole response of the layer; this is validated by numerical simulations. As a model study, the evolution of orientational order with increasing surface density in layers of the antibody immunoglobulin G was monitored. As an exemplar of greater complexity, superchiral fields are demonstrated, without knowledge of exact composition, to be able to monitor how qualitative changes in composition alter the structural order of protein layers formed from blood serum, thereby establishing the efficacy of the phenomenon as a tool for studying complex biological interfaces.

The structure adopted by biomaterials, such as proteins, at interfaces is a crucial parameter in a range of important biological problems. It is a critical property in defining the functionality of cell/bacterial membranes and biofilms (i.e., in antibiotic-resistant infections) and the exploitation of immobilized enzymes in biocatalysis. The intrinsically small quantities of materials at interfaces precludes the application of conventional spectroscopic phenomena routinely used for (bio)structural analysis due to a lack of sensitivity. We show that the interaction of proteins with superchiral fields induces asymmetric changes in retardation phase effects of excited bright and dark modes of a chiral plasmonic nanostructure. Phase retardations are obtained by a simple procedure, which involves fitting the line shape of resonances in the reflectance spectra. These interference effects provide fingerprints that are an incisive probe of the structure of interfacial biomolecules. Using these fingerprints, layers composed of structurally related proteins with differing geometries can be discriminated. Thus, we demonstrate a powerful tool for the bioanalytical toolbox.

The authors thank the European Research Council for financial support (EXCITON Grant 321305). We studied crystallinity and exciton harvesting in bulk heterojunctions of a semiconducting polymer PffBT4T-2OD and electron acceptor PC71BM which are used to make highly efficient organic solar cells. Grazing incidence wide-angle X-ray scattering (GIWAXS) shows that the size of crystalline domains of PffBT4T-2OD increases to ~18 nm in photovoltaic blends upon thermal annealing at 100 °C for 5 minutes. These domains are larger than the typical exciton diffusion lengths in conjugated polymers. Time-resolved fluorescence measurements show that exciton diffusion length in PffBT4T-2OD increases from ~14 to ~24 nm upon thermal annealing, which enables efficient charge generation in blends with large domains. Solar cells prepared using thermally annealed blends show higher photocurrent, open circuit voltage and fill factor compared to as spin-coated blends which indicates reduced recombination losses. Our results demonstrate the advantages of large crystalline domains in organic photovoltaics, providing exciton diffusion is sufficient. Postprint

Coplanar metal-free organic dyes featuring a furylethynyl spacer with different donor residues (MeO-, MeS-, and Me2N-) have been synthesized. Density functional theory (DFT) calculations predicted that the Me2N- residue would facilitate more effective charge transfer from donor to acceptor than the MeO- and MeS- residues. In agreement with DFT calculations, the dye-sensitized solar cells (DSSCs) fabricated with the Me2N- functionalized dye exhibited the best power conversion efficiency (&eta, ), 2.88%. Furthermore, the effect of the furan spacer on the photophysical properties and DSSC parameters are discussed in comparison to a previously reported thiophene counterpart.

The ever-increasing demand for renewable energy has led to the intensification of research focused upon harnessing the abundant energy from sunlight. Solution processed organic solar cells fabricated using conjugated polymer donor materials dominated the early development of organic photovoltaics (OPV). More recently, organic solar cells fabricated using small molecule donors have become increasingly attractive due to the advantages these systems have over their polymeric counterparts. These include reproducible synthesis and the ability to more accurately develop structure-activity relationships. Here, we report the synthesis of thiophene based small molecule donors that have been used to investigate the influence of alkyne π-spacers on the optical, electronic and photovoltaic properties of solution-processable bulk-heterojunction (BHJ) organic OPV cells. Additionally, we compare the addition of 3,4-ethylenedioxythiophene (EDOT) units in place of the end-thiophene of these derivatives. We found that the compounds featuring alkyne moieties displayed poor charge transfer and blue-shifted UV–vis spectra, whereas the incorporation of the EDOT units increased charge transfer for the non-alkyne derivative resulting in red-shifted absorbance. DFT calculations predicted higher charge separation/mobility and lower charge generation for the compounds without alkyne units. Indeed, greater Jsc values and higher PCEs were found for the compounds lacking alkyne spacers. EDOT containing compounds showed poor performance which is likely due to an unfavourable morphology and higher HOMO level, leading to lower Voc. Hence, the simplest 5T-1 molecule showed the highest performance of 3.24%, which is c.a. 1.6x that of the alkyne-containing 5TA-1 and c.a. 2.9x that of the EDOT-containing derivative. This study demonstrates that alkyne spacers can be detrimental to orbital interactions, charge transfer and OPV performance, and that the EDOT unit can be added to provide greater charge transfer due to its auxiliary donating ability. However, careful design is required to ensure higher Voc values and a favourable morphology in thiophene-based solution-processable OPVs.

Three ‘D-π-A-π-A’ based dyes have been synthesized featuring MeO-, MeS- and Me2N- as donor residues and benzothiadiazole and cyanoacrylic acid residues as acceptor units. UV–vis spectroscopy, solution electrochemistry and DFT modelling indicated that the Me2N- residue has the most significant effect on optical and redox properties of a photosensitizer. DSSCs with the Me2N- functionalized dye gave the highest power conversion efficiency of the series (η = 5.61%), presumably due to the better donor ability of this unit, which promotes more effective intramolecular charge transfer (ICT) characteristics.

We thank the European Research Council (ERC) for financial support (EXCITON grant 321305). Data supporting this study is available at https://doi.org/10.17630/0e75f92d-6f8a-41be-ad45-ac6d1d890ee2. The singlet exciton diffusion length was measured in a small molecule electron donor material DR3TBDTT using fluorescence quenching at a planar interface with a cross-linked fullerene derivative. The one-dimensional exciton diffusion length was increased from ~16 to ~24 nm by annealing the film in carbon disulfide solvent vapor. Planar heterojunction solar cells were fabricated using bilayers of these materials and it was found that solvent vapor annealing increased the short circuit current density by 46%. This can be explained by improved exciton harvesting in the annealed bilayer. Postprint

The authors are grateful for funding from EPSRC under grant codes EP/L012294/1, EP/L012170/1 and EP/L015110/1. Sondos Abdullah J Almahmoud acknowledges the Ministry of Higher education in Saudi Arabia for the funding and support. Organic photovoltaic devices fabricated from small molecular donors continue to receive significant interest due to their desirable properties such as convenient synthesis, purification and batch-to-batch reproducibility. In this study, we have synthesized two small molecules based on an alternating A-D-A structure, utilizing a central EDOT donor moiety and either 2-ethylhexyl cyanoacetate ( SAM-80 ) or N-(2-ethylhexyl)cyanoacetamide ( SAM-72 ) units as acceptor termini. The small molecules were incorporated into bulk heterojunction solar cells with PC71BM . Our investigations have shown that the side chains utilized for SAM-80 only allow for solution processing using volatile solvents, such as chloroform, which limits the reproducibility of device fabrication. However, SAM-72 displays better solubility and devices fabricated using a SAM-72:PC71BM active layer reached average power conversion efficiencies of 1.9%, with fill factors reaching 60%. Post-processing methods such as thermal and solvent vapor annealing were found to significantly increase the stability of devices, but were not able to improve overall device performance. Publisher PDF

Dye-sensitized solar cells (DSSCs) continue to attract interest due to their lower cost production compared to silicon based solar cells and their improving power conversion efficiencies. Porphyrin-based sensitizers have become an important sub-class due to their strong absorption characteristics in the visible region, convenient modulation of properties through synthetic manipulation and class-leading power conversion efficiencies. In this article, we report the synthesis and characterization of two porphyrin-based dyes and their application as sensitizers in DSSCs. A thiophene and a furan moiety have been incorporated into the push–pull architecture as a π-bridge, allowing the systematic investigation of how these moieties influence the physical properties of the dyes and the performance of their resulting DSSCs. A significant difference in PCEs has been observed, with the furan containing dye (PorF, PCE = 4.5%) being more efficient than the thiophene-based analogue (PorT, PCE = 3.6%) in conjunction with the iodide/triiodide redox electrolyte.

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.

Four different oligoethylene glycol acrylates (OEGA), namely hydroxypropylacrylate (HPA), methoxy diethylene glycol acrylate (mDEGA), methoxy triethylene glycol acrylate (mTEGA) and 2-hydroxyethylacrylate (HEA) were homopolymerized via RAFT polymerization employing a naphthalene functionalized chain transfer agent resulting in thermoresponsive naphthalene-functionalized POEGAs with different hydrophilicities. Supramolecular inclusion complexes of these POEGAs with electron-deficient cyclophane cyclobis(paraquat-p-phenylene) tetrachloride (CBPQT4+) in water were studied. The association constants (Ka) were determined to study the effect that polymer hydrophilicity has on the Ka and results indicated that the nature of the polymer did not significantly influence the complexation strength and the association is mostly enthalpy driven. The impact of temperature on the host–guest complexes was also investigated. A continuous partial thermally induced dissociation of complexes was observed upon raising the temperature with a more distinct decrease in complexation around the cloud point temperature (TCP) of the POEGA employed, indicating the importance of the polymer phase transition for tuning the recognition properties of dialkoxynaphthalene end-decorated poly(oligoethylene glycol acrylate)s in water.

International audience; This communication describes the synthesis of a triple acid-functionalized RAFT agent and its use to prepare well-defined 3-arm star polymers of N,N-dimethylacrylamide (DMAc). A simple esterification reaction allowed the convenient integration of three electron-rich naphthalene recognition units on the RAFT agent platform and subsequently the elaboration of a naphthalene end-decorated telechelic 3-arm star PDMAc. This functionalized star polymer was further exploited to build a hydrogel with a complementary homoditopic host unit featuring tetracationic macrocycle cyclobis(paraquat-p-phenylene) units.

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.

Development of low-cost disposable plasmonic substrates is vital for the applicability of plasmonic sensing. Such devices can be made using injection-molded templates to create plasmonic films. The elements of these plasmonic films are hybrid nanostructures composed of inverse and solid structures. Tuning the modal coupling between the two allows optimization of the optical properties for nanophotonic applications.

International audience; We report a multi-stimuli responsive polymeric sensor consisting of a pseudorotaxane-like architecture fabricated from a 1,5-diaminonaphthalene end-functionalized poly(N-isopropyl)acrylamide (Napht-N-PNIPAM) and cyclobis(paraquat-p-phenylene) (CBPQT4+, 4Cl−). The coloured nature of the poly-pseudorotaxane provides a sensor for temperature and pH in water with an associated visible readout. To create this dual responsive polymeric sensor, a new chain transfer agent (Napht-N-CTA) incorporating a pH-responsive 1,5-diaminonaphthalene unit was synthesized and used for the polymerization of N-isopropylacrylamide via Reversible Addition-Fragmentation Chain Transfer (RAFT). The ability of Napht-N-PNIPAM to form a pseudorotaxane architecture with CBPQT4+, 4Cl− in aqueous media was studied by means of UV–Vis, NMR (1H, 2D-ROESY, DOSY) and ITC experiments. Interestingly, the pseudorotaxane architecture can be reversibly dissociated upon either heating the sample above its cloud point or protonating the nitrogen atoms of the 1,5-diaminonaphthalene-based guest unit by adjusting the pH to around 1. In both cases a dramatic colour change occurs from intense blue-green to colourless.

Optical spectroscopic methods do not routinely provide information on higher order hierarchical structure (tertiary/quaternary) of biological macromolecules and assemblies. This necessitates the use of time-consuming and material intensive techniques, such as protein crystallography, NMR, and electron microscopy. Here we demonstrate a spectroscopic phenomenon, superchiral polarimetry, which can rapidly characterize ligand-induced changes in protein higher order (tertiary/quaternary) structure at the picogram level, which is undetectable using conventional CD spectroscopy. This is achieved by utilizing the enhanced sensitivity of superchiral evanescent fields to mesoscale chiral structure.

GC and IDWS thank the EPSRC for funding (Grant EP/I00243X). NBAP thanks Directorate General of Higher Education (DGHE) of Republic Indonesia for PhD Scholarship Grant (948/E4.4/K/2013). IDWS also acknowledges a Royal Society Wolfson Research Merit Award. 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. Publisher PDF

Singlet exciton diffusion was studied in the efficient organic photovoltaic electron donor material DTS(FBTTh2)2. Three complementary time-resolved fluorescence measurements were performed: quenching in planar heterojunctions with an electron acceptor, exciton–exciton annihilation, and fluorescence depolarization. The average exciton diffusivity increases upon annealing from 1.6 × 10–3 to 3.6 × 10–3 cm2 s–1, resulting in an enhancement of the mean two-dimensional exciton diffusion length (LD = (4Dτ)1/2) from 15 to 27 nm. About 30% of the excitons get trapped very quickly in as-cast films. The high exciton diffusion coefficient of the material leads to it being able to harvest excitons efficiently from large donor domains in bulk heterojunctions.

This paper reports the synthesis of a series of new half-squaraine dyes (Hf-SQ) based around a common chromophoric unit consisting of linked indoline and squaric acid moieties. Carboxylate groups have been incorporated onto this core structure at four different points to study the influence of the anchoring group position on dye-sensitized solar cell (DSC) device performance. Dyes have been linked to TiO2 directly through the squaric acid moiety, through a modified squaric acid unit where a vinyl dicyano group has replaced one carbonyl, via an alkyl carboxylate attached to the indole N or through a carboxylate attached to the 4 position of a benzyl indole. Contact angle measurements have been studied to investigate the hydrophobic/hydrophilic properties of the dyes and the results have been compared to N719 and Z907. Full characterization data of all the dyes and synthetic intermediates are reported including single-crystal X-ray structural analysis for dye precursors; the indole (2a) and the half-squarylium esters (3a) and (6b), as well as the dyes (4c), (8) and (12). Dye colours range from yellow to red/brown in solution (lambda(max) range from 430 to 476 nm) with 3 ranging from 38 000 to 133 100 M-1 cm(-1). The performance of the dyes in DSCs shows the highest efficiency yet reported for a Hf-SQ dye (eta = 5.0%) for 1 cm(2) devices with a spectral response ranging from 400 to 700 nm depending on the dye substituents. Co-sensitization of half-squarylium dye (7b) with squaraine dye (SQ2) resulted in a broader spectral response and an improved device efficiency (eta = 6.1%). Density functional theory (DFT) calculations and cyclic voltammetry have been used to study the influence of linker position on dye HOMO-LUMO levels and the data has been correlated with I-V and EQE data.

Full employment has come to be regarded as dangerous and outdated. Graeme Cooke and Tony Dolphin reject this assertion and argue instead that full employment is the most plausible strategy for raising living standards and adequately funding our public services.

We have demonstrated controlled assembly between CdSe quantum dots (QDs) and a fullerene (C60) derivative via complementary three-point hydrogen bonding interactions. The recognition-mediated assembly facilitated an interpenetrated network morphology and hence efficient charge transfer from QD to C60.

International audience; Supramolecular polymer networks have been designed on the basis of a π-electron donor/acceptor complex: naphthalene (N)/cyclobis(paraquat-p-phenylene) (CBPQT4+ = B). For this purpose, a copolymer of N,N-dimethylacrylamide P(DMA-N1), lightly decorated with 1 mol% of naphthalene pendant groups, has been studied in semi-dilute un-entangled solution in the presence of di-CBPQT4+ (BB) crosslinker type molecules. While calorimetric experiments demonstrate the quantitative binding between N and B groups up to 60 °C, the introduction of BB crosslinkers into the polymer solution gives rise to gel formation above the overlap concentration. From a comprehensive investigation of viscoelastic properties, performed at different concentrations, host/guest stoichiometric ratios and temperatures, the supramolecular hydrogels are shown to follow a Maxwellian behavior with a strong correlation of the plateau modulus and the relaxation time with the effective amount of interchain cross-linkers and their dissociation dynamics, respectively. The calculation of the dissociation rate constant of the supramolecular complex, by extrapolation of the relaxation time of the network back to the beginning of the gel regime, is discussed in the framework of theoretical and experimental works on associating polymers.

International audience; Most polymeric thermoresponsive hydrogels contract upon heating beyond the lower critical solution temper-ature (LCST) of the polymers used. Herein, we report a supramolecular hydrogel system that shows the opposite temperature dependence. When the non-thermosesponsive hydrogel NaphtGel, containing dialkoxynaphthalene guest molecules,becomes complexed with the tetra cationic macro-cyclic host CBPQT4+, swelling occurred as a result of host–guest complex formation leading to charge repulsion between the host units,aswell as an osmotic contribution of chloride counter-ions embedded in the network. The immersion of NaphtGel in a solution of poly(N-isopropylacrylamide) with tetrathiafulvalene (TTF) end groups complexed with CBPQT4+ induced positive thermoresponsive behaviour. The LCST-induced dethreading of the polymer-based pseudoro-taxane upon heating led to transfer of the CBPQT4+ host and a concomitant swelling of NaphtGel. Subsequent cooling led to reformation of the TTF-based host–guest complexes in solution and contraction of the hydrogel.

The refractive index sensitivity of plasmonic fields has been exploited for over 20 years in analytical technologies. While this sensitivity can be used to achieve attomole detection levels, they are in essence binary measurements that sense the presence/absence of a predetermined analyte. Using plasmonic fields, not to sense effective refractive indices but to provide more "granular" information about the structural characteristics of a medium, provides a more information rich output, which affords opportunities to create new powerful and flexible sensing technologies not limited by the need to synthesize chemical recognition elements. Here we report a new plasmonic phenomenon that is sensitive to the biomacromolecular structure without relying on measuring effective refractive indices. Chiral biomaterials mediate the hybridization of electric and magnetic modes of a chiral solid-inverse plasmonic structure, resulting in a measurable change in both reflectivity and chiroptical properties. The phenomenon originates from the electric-dipole-magnetic-dipole response of the biomaterial and is hence sensitive to biomacromolecular secondary structure providing unique fingerprints of α-helical, β-sheet, and disordered motifs. The phenomenon can be observed for subchiral plasmonic fields (i.e., fields with a lower chiral asymmetry than circularly polarized light) hence lifting constraints to engineer structures that produce fields with enhanced chirality, thus providing greater flexibility in nanostructure design. To demonstrate the efficacy of the phenomenon, we have detected and characterized picogram quantities of simple model helical biopolymers and more complex real proteins.

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.

In 2008, we changed the gastrointestinal pathology laboratories in a gastrointestinal pathophysiology course to a more interactive format using modified team-based learning techniques and multimedia presentations. The results were remarkably positive and can be used as a model for pathology laboratory improvement in any organ system. Over a two-year period, engaging and interactive pathology laboratories were designed. The initial restructuring of the laboratories included new case material, Digital Atlas of Video Education Project videos, animations and overlays. Subsequent changes included USMLE board-style quizzes at the beginning of each laboratory, with individual readiness assessment testing and group readiness assessment testing, incorporation of a clinician as a co-teacher and role playing for the student groups. Student responses for pathology laboratory contribution to learning improved significantly compared to baseline. Increased voluntary attendance at pathology laboratories was observed. Spontaneous student comments noted the positive impact of the laboratories on their learning. Pathology laboratory innovations, including modified team-based learning techniques with individual and group self-assessment quizzes, multimedia presentations, and paired teaching by a pathologist and clinical gastroenterologist led to improvement in student perceptions of pathology laboratory contributions to their learning and better pathology faculty evaluations. These changes can be universally applied to other pathology laboratories to improve student satisfaction.

It is 20 years since the last edition of Marxism Today hit the newsstands. To mark that anniversary, this special edition of PPR is dedicated to reflecting on that unique magazine's contribution to Britain politics in the 1980s – and its lessons for politicians and intellectuals today.

In this Letter, we describe the formation of complexes between flavin and diamidopyridine functionalized porphyrin systems via hydrogen bonding and π-stacking interactions.

Guest Editors Graeme Cooke, Ivana Evans and Peter Skabara introduce this themed collection on functional organic materials for optoelectronic applications, in celebration of Professor Martin Bryce’s contributions to this field.

Complementary diaminopyridine–flavin dyads that provide liquid crystalline systems have been synthesised. The mesophases possess well-defined molecular architectures, thermal stability and wide ranges. Furthermore, chiral centres have been introduced to explore the role chirality plays on the end morphology. The introduction of stereo-centres into these systems offers effective control over mesophase morphology and generates well-defined columnar liquid crystals.

1,5-Di(hetero)arylated-pyridin-2(1H)-one derivatives have been readily obtained in good yields starting from 2-fluoro-5-pyridylboronic acid. The sequence comprises three steps: (i) palladium-catalysed Suzuki-Miyaura reaction; (ii) base-catalysed hydrolysis; (iii) copper-catalysed C–N coupling. X-ray crystal structures are reported for selected pyridin-2(1H)-one derivatives. These compounds are of interest as new scaffolds for drug discovery.