Structurally colored semitransparent perovskite solar cells using one-step deposition of self-ordering microgel particles.

Semitransparent perovskite solar cells (STPSCs) have excellent potential for widespread application as building integrated photovoltaics. Widespread application of STPSCs could result in decreased CO2 footprints for buildings. Unfortunately, STPSCs tend to have poor aesthetic qualities (being usually red-brown in color) and low stability. Building on our previous work, here we use new poly(N-isopropylacrylamide) microgels (PNP MGs) to provide highly ordered non-close packed arrays within perovskite films that reflect some of the incident light to provide structural color to STPSCs. (MGs are swellable crosslinked polymer colloid particles.) We introduce PNP MGs into two different perovskites and achieve a wide gamut of reflected color and iridescence from the perovskite films. Devices containing the MGs have average visible transparency (AVT) values of greater than 25%. The best PCE for a MG-containing STPSC is 10.60% compared to 9.14% for the MG-free control. The MGs not only introduce structural color to the STPSCs but increase the PCE and stability. Equations are provided that enable the reflected color to be predicted from the formulation used to deposit the films. Our work shows that the self-ordering tendency of PNP MGs gives a viable new method for introducing structural color into STPSCs. Because our one-step method for introducing structural color into STPSCs is general, does not introduce any additional processing steps and is scalable whilst also improving device stability, this study may bring deployment of STPSCs closer.

Injectable Colloidal Hydrogels of N-Vinylformamide Microgels Dispersed in Covalently Interlinked pH-Responsive Methacrylic Acid-Based Microgels.

Injectable hydrogels offer great potential to augment damaged or degenerated soft tissues. A key criterion for such gels is that their modulus is as close as possible to that of the target tissue. The majority of synthetic hydrogels have used low molecular weight polymer chains which may cause problems if they diffuse away from the injection site and/or increase the local osmotic pressure. We previously introduced a different approach of injecting preformed ultra-high molecular weight pH-responsive microgels (MGs) that interlink to form hydrogels. MGs are crosslinked polymer colloid particles that swell when the pH approaches the particle pKa. These colloidal hydrogels are termed doubly crosslinked microgels (DX MGs). The gel moduli of previous DX MGs were much greater than that reported for human nucleus pulposus (NP) tissue of the spinal intervertebral disk. Here, we replace some of the pH-responsive poly(ethyl acrylate-co-methacrylic acid) (PEA-MAA) MGs with hydrophilic non-ionic MGs based on poly(N-vinylformamide) (NVF). We investigate the morphology and mechanical properties of these new injectable composite DX MGs and show that the mechanical properties can be tuned by systematically varying the NVF MG content. Using this approach, the gel moduli close to that for NP tissue are achieved. These injectable new pH-responsive gels exhibit low cytotoxicity. Our work provides a potential new system for minimally invasive intervertebral disk augmentation.

Highly Stretchable Conductive Covalent Coacervate Gels for Electronic Skin.

Highly stretchable electrically conductive hydrogels have been extensively researched in recent years, especially for applications in strain and pressure sensing, electronic skin, and implantable bioelectronic devices. Herein, we present a new cross-linked complex coacervate approach to prepare conductive hydrogels that are both highly stretchable and compressive. The gels involve a complex coacervate between carboxylated nanogels and branched poly(ethylene imine), whereby the latter is covalently cross-linked by poly(ethylene glycol) diglycidyl ether (PEGDGE). Inclusion of graphene nanoplatelets (Gnp) provides electrical conductivity as well as tensile and compressive strain-sensing capability to the hydrogels. We demonstrate that judicious selection of the molecular weight of the PEGDGE cross-linker enables the mechanical properties of these hydrogels to be tuned. Indeed, the gels prepared with a PEGDGE molecular weight of 6000 g/mol defy the general rule that toughness decreases as strength increases. The conductive hydrogels achieve a compressive strength of 25 MPa and a stretchability of up to 1500%. These new gels are both adhesive and conformal. They provide a self-healable electronic circuit, respond rapidly to human motion, and can act as strain-dependent sensors while exhibiting low cytotoxicity. Our new approach to conductive gel preparation is efficient, involves only preformed components, and is scalable.

Comparing pH-responsive nanogel swelling in dispersion and inside a polyacrylamide gel using photoluminescence spectroscopy and small-angle neutron scattering.

Nanosized probes that report their changes in dimensions within networks in response to environmental stimuli are potentially important for applications such as drug delivery, load-supporting hydrogels and soft robotics. Recently, we developed a fluorescent pH-responsive nanogel (NG) that used Förster-resonance energy transfer (FRET) to report changes in the probe separation and NG swelling within hydrogels using photoluminescence (PL) spectroscopy. However, FRET cannot measure nanoparticle dimensions and is subject to artefacts. Here, we report the use of small-angle neutron scattering (SANS) to study both the NGs in dispersion and in polyacrylamide (PAAm) gels as a function of pH. We compare the PL and SANS data for both systems and as a function of pH. The SANS data for the dispersed NGs indicate that they have a core-shell structure with a swollen mesh size of ∼1.0 nm. We hypothesized that the NGs inside the PAAm gel would show the same general changes in scattering as the pH is increased, as observed for the dispersed NGs, and this is confirmed by the data. In summary, the data confirm that PL is a suitable (accessible) method for reporting internal environmental changes within gels using NG probes.

Improving the Efficiency, Stability, and Adhesion of Perovskite Solar Cells Using Nanogel Additive Engineering.

Additive engineering has been applied widely to improve the efficiency and/or stability of perovskite solar cells (PSCs). Most additives used to date are difficult to locate within PSCs as they are small molecules or linear polymers. In this work, we introduce, for the first time, carboxylic acid-functionalized nanogels (NGs) as additives for PSCs. NGs are swellable sub-100 nm gel particles. The NGs consist of poly(2-(2-methoxyethoxy) ethyl methacrylate)-co-methacrylic acid-co-ethylenegylcol dimethacrylate (PMEO2MA-MAA-EGD) particles prepared by a scalable synthesis, which have a diameter of 40 nm. They are visualized in the perovskite films using SEM and are located at the grain boundaries. X-ray photoelectron and FTIR spectroscopy reveal that the NGs coordinate with Pb2+ via the -COOH groups. Including the NGs within the PSCs increased the grain size, decreased nonradiative recombination, and increased the power conversion efficiency (PCE) to 20.20%. The NGs also greatly increase perovskite stability to ambient storage, elevated temperature, and humidity. The best system maintained more than 80% of its original PCE after 180 days of storage under ambient conditions. Tensile cross-cut tape adhesion tests are used to assess perovskite film mechanical integrity. The NGs increased both the adhesion of the perovskite to the substrate and the mechanical stability. This study demonstrates that NGs are an attractive alternative to molecularly dispersed additives for providing performance benefits to PSCs. Our study indicates that the NGs act as a passivator, stabilizer, cross-linker, and adhesion promoter.

Site-Directed Differentiation of Human Adipose-Derived Mesenchymal Stem Cells to Nucleus Pulposus Cells Using an Injectable Hydroxyl-Functional Diblock Copolymer Worm Gel.

Adipose-derived mesenchymal stem cells (ASCs) have been identified for their promising therapeutic potential to regenerate and repopulate the degenerate intervertebral disk (IVD), which is a major cause of lower back pain. The optimal cell delivery system remains elusive but encapsulation of cells within scaffolds is likely to offer a decisive advantage over the delivery of cells in solution by ensuring successful retention within the tissue. Herein, we evaluate the use of a fully synthetic, thermoresponsive poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate) (PGMA-PHPMA) diblock copolymer worm gel that mimics the structure of hydrophilic glycosaminoglycans. The objective was to use this gel to direct differentiation of human ASCs toward a nucleus pulposus (NP) phenotype, with or without the addition of discogenic growth factors TGFß or GDF6. Accordingly, human ASCs were incorporated into a cold, free-flowing aqueous dispersion of the diblock copolymer, gelation induced by warming to 37 °C and cell culture was conducted for 14 days with or without such growth factors to assess the expression of characteristic NP markers compared to those produced when using collagen gels. In principle, the shear-thinning nature of the biocompatible worm gel enables encapsulated human ASCs to be injected into the IVD using a 21G needle. Moreover, we find significantly higher gene expression levels of ACAN, SOX-9, KRT8, and KR18 for ASCs encapsulated within worm gels compared to collagen scaffolds, regardless of the growth factors employed. In summary, such wholly synthetic worm gels offer considerable potential as an injectable cell delivery scaffold for the treatment of degenerate disk disease by promoting the transition of ASCs toward an NP-phenotype.

Bioinspired scaffolds that sequester lead ions in physically damaged high efficiency perovskite solar cells.

Hydroxyapatite nanoparticles (HAP NPs) are blended with TiO2 NPs to prepare mixed mesoporous scaffolds which are used to prepare high efficiency perovskite solar cells (PSCs) with a best power conversion efficiency (PCE) of 20.98%. HAP not only increases the PCE but also limits the concentration of Pb released in water from intentionally broken PSCs by ion sequestration thereby potentially offering a promising in-device fail-safe system.

Including fluorescent nanoparticle probes within injectable gels for remote strain measurements and discrimination between compression and tension.

The ability to remotely and non-invasively monitor and measure the strain within injectable gels used to augment soft tissue is highly desirable. Such information could enable real-time monitoring of gel performance and bespoke gel design. We report progress towards this goal using two fluorescent particle probe systems included within two different injectable gels. The two injectable gels have been previously studied in the contexts of intervertebral disc repair and stretchable gels for cartilage repair. The two fluorophore particle probes are blue or near-infrared (NIR) emitting and are present at very low concentrations. The normalised photoluminescence (PL) intensity from the blue emitting probe is shown to equal the compressive deformation ratio of the gels. Furthermore, the normalised ratio of the PL intensities for the blue and NIR probes varies linearly with deformation ratio over a wide range (from 0.2 to 3.0) with a seamless transition from compression to tension. Hence, PL can discriminate between compression and tension. The new approach established here should apply to other gels and enable remote detection of whether a gel is being compressed or stretched as well as the extent. This study may provide an important step towards remotely and minimally invasively measuring the strain experienced by load-supporting gels in vivo.

Using Soft Polymer Template Engineering of Mesoporous TiO2 Scaffolds to Increase Perovskite Grain Size and Solar Cell Efficiency.

The mesoporous (meso)-TiO2 layer is a key component of high-efficiency perovskite solar cells (PSCs). Herein, pore size controllable meso-TiO2 layers are prepared using spin coating of commercial TiO2 nanoparticle (NP) paste with added soft polymer templates (SPT) followed by removal of the SPT at 500 °C. The SPTs consist of swollen crosslinked polymer colloids (microgels, MGs) or a commercial linear polymer (denoted as LIN). The MGs and LIN were comprised of the same polymer, which was poly(N-isopropylacrylamide) (PNIPAm). Large (L-MG) and small (S-MG) MG SPTs were employed to study the effect of the template size. The SPT approach enabled pore size engineering in one deposition step. The SPT/TiO2 nanoparticle films had pore sizes > 100 nm, whereas the average pore size was 37 nm for the control meso-TiO2 scaffold. The largest pore sizes were obtained using L-MG. SPT engineering increased the perovskite grain size in the same order as the SPT sizes: LIN < S-MG < L-MG and these grain sizes were larger than those obtained using the control. The power conversion efficiencies (PCEs) of the SPT/TiO2 devices were ∼20% higher than that for the control meso-TiO2 device and the PCE of the champion S-MG device was 18.8%. The PCE improvement is due to the increased grain size and more effective light harvesting of the SPT devices. The increased grain size was also responsible for the improved stability of the SPT/TiO2 devices. The SPT method used here is simple, scalable, and versatile and should also apply to other PSCs.

Highly swelling pH-responsive microgels for dual mode near infra-red fluorescence reporting and imaging.

Near infra-red (NIR) fluorescence is a desirable property for probe particles because such deeply penetrating light enables remote reporting of the local environment in complex surroundings and imaging. Here, two NIR non-radiative energy transfer (NRET) fluorophores (Cy5 and Cy5.5) are coupled to preformed pH-responsive poly(ethylacrylate-methacrylic acid-divinylbenzene) microgel particles (PEA-MAA-5/5.5 MGs) to obtain new NIR fluorescent probes that are cytocompatible and swell strongly. NIR ratiometric photoluminescence (PL) intensity analysis enables reporting of pH-triggered PEA-MAA-5/5.5 MG particle swelling ratios over a very wide range (from 1-90). The dispersions have greatly improved colloidal stability compared to a reference temperature-responsive NIR MG based on poly(N-isopropylacrylamide) (PNP-5/5.5). We also show that the wavelength of maximum PL intensity (λ max) is a second PL parameter that enables remote reporting of swelling for both PEA-MAA-5/5.5 and PNP-5/5.5 MGs. After internalization the PEA-MAA-5/5.5 MGs are successfully imaged in stem cells using NIR light. They are also imaged after subcutaneous injection into model tissue using NIR light. The new NIR PEA-MAA-5/5.5 MGs have excellent potential for reporting their swelling states (and any changes) within physiological settings as well as very high ionic strength environments (e.g., waste water).

Self-curing super-stretchable polymer/microgel complex coacervate gels without covalent bond formation.

Elastic physical gels are highly desirable because they can be conveniently prepared and readily shaped. Unfortunately, many elastic physical gels prepared in water require in situ free-radical polymerization during the gel formation stage. In contrast, complex coacervate gels are physical gels that can be prepared by simply mixing two pre-formed oppositely-charged polyelectrolytes. However, as far as we are aware, highly elastic complex coacervate gels have not yet been reported. Herein, we combine polyanionic microgel particles with a well-known commercially-available cationic polyelectrolyte to prepare polymer/microgel complex coacervate (PMCC) physical gels. This new family of gels requires annealing at only 37 °C and behaves like a covalent gel but does not form covalent bonds. Thermal reconfiguration of the dynamic ionic bonds transforms the shapeable pre-gel into a highly elastic gel that is super-stretchable, adhesive, self-healing, highly swellable and can be further toughened using Ca2+ as an ionic crosslinker. Our PMCC gels have excellent potential for applications as engineering gels and structural biomaterials, as well as for wound healing and water purification.

Core-Shell-Shell Nanoparticles for NIR Fluorescence Imaging and NRET Swelling Reporting of Injectable or Implantable Gels.

Injectable gels that support load are desirable for restoring the mechanical properties of degenerated load-bearing tissue. As these gels become increasingly sophisticated, the need to remotely image them and monitor their swelling increases. However, imaging such gels and monitoring their swelling using noninvasive means is challenging. Here, we use a very low concentration of near-infrared (NIR) core-shell-shell (CSS) reporter nanoparticles to both image and monitor swelling changes of two load-supporting gels. The load-supporting injectable gel consisted of covalently interlinked pH-responsive microgel (MG) particles. The latter gel was not cytotoxic and is termed a doubly cross-linked microgel (DX MG). Inclusion of a complementary fluorescent dye enabled ratiometric monitoring of gel swelling changes in response to pH via nonradiative resonance energy transfer (NRET). In addition, changes in the CSS nanoparticle emission intensity provided a NIR-only method that could also be used to monitor gel swelling. The gel was able to be imaged using NIR light, after being subcutaneously injected into a tissue model. To demonstrate versatility of our approach, CSS and the dye were included within a model implantable gel (poly(acrylamide/acrylic acid)) and fluorescent detection of swelling investigated. Because the concentrations of the reporting species were too low to affect the mechanical properties, our approach to remote gel imaging and swelling monitoring has good potential for application in injectable gels and implants.

Using green emitting pH-responsive nanogels to report environmental changes within hydrogels: a nanoprobe for versatile sensing.

Remotely reporting the local environment within hydrogels using inexpensive laboratory techniques has excellent potential to improve our understanding of the nanometer-scale changes that cause macroscopic swelling or deswelling. Whilst photoluminescence (PL) spectroscopy is a popular method for such studies this approach commonly requires bespoke and time-consuming synthesis to attach fluorophores which may leave toxic residues. A promising and more versatile alternative is to use a pre-formed nanogel probe that contains a donor/acceptor pair and then "dope" that into the gel during gel assembly. Here, we introduce green-emitting methacrylic acid-based nanogel probe particles and use them to report the local environment within four different gels as well as stem cells. As the swelling of the nanogel probe changes within the gels the non-radiative energy transfer efficiency is strongly altered. This efficiency change is sensitively reported using the PL ratiometric intensity from the donor and acceptor. We demonstrate that our new nanoprobes can reversibly report gel swelling changes due to five different environmental stimuli. The latter are divalent cations, gel degradation, pH changes, temperature changes and tensile strain. In the latter case, the nanoprobe rendered a nanocomposite gel mechanochromic. The results not only provide new structural insights for hierarchical natural and synthetic gels, but also demonstrate that our new green-fluorescing nanoprobes provide a viable alternative to custom fluorophore labelling for reporting the internal gel environment and its changes.

Highly compressive and stretchable poly(ethylene glycol) based hydrogels synthesised using pH-responsive nanogels without free-radical chemistry.

Poly(ethylene glycol) (PEG) based hydrogels are amongst the most studied synthetic hydrogels. However, reports on PEG-based hydrogels with high mechanical strength are limited. Herein, a class of novel, well-defined PEG-based nanocomposite hydrogels with tunable mechanical strength are synthesised via ring-opening reactions of diglycidyl ethers with carboxylate ions. The pH responsive crosslinked polyacid nanogels (NG) in the dispersed phase act as high functionality crosslinkers which covalently bond to the poly(ethylene glycol) diglycidyl ethers (PEGDGE) as the continuous matrix. A series of NG-x-PEG-y-z gels are prepared where x, y and z are concentrations of NGs, PEGDGE and the PEGDGE molecular weight, respectively. The hydrogel compositions and nano-structural homogeneity of the NGs have strong impact on the enhancement of mechanical properties which enables property tuning. Based on this design, a highly compressive PEG-based nanocomposite hydrogel (NG-13-PEG-20-6000) exhibits a compressive stress of 24.2 MPa, compressive fracture strain greater than 98% and a fracture energy density as high as 1.88 MJ m-3. The tensile fracture strain is 230%. This is amongst one of the most compressive PEG-based hydrogels reported to-date. Our chemically crosslinked gels are resilient and show highly recoverable dissipative energy. The cytotoxicity test shows that human nucleus pulposus (NP) cells remained viable after 8 days of culture time. The overall results highlight their potential for applications as replacements for intervertebral discs or articular cartilages.

Do the properties of gels constructed by interlinking triply-responsive microgels follow from those of the building blocks?

Microgels (MGs) are swellable crosslinked polymer colloids. They can also be used as the only building block to construct nanostructured hydrogels which are denoted as doubly crosslinked microgels (DX MGs). Here, new triply responsive DX MGs comprised of interlinked MGs of oligo(ethylene glycol)methacrylate (OEGMA), 2-(2-methoxyethoxy)ethyl methacrylate (MEO2MA), methacrylic acid (MAA) and a o-nitrobenzyl-based UV photocleavable crosslinker are investigated. The MGs swelled or collapsed in response to temperature and pH changes. These behaviours were rationalised with a generic model using Monte Carlo simulations. The MGs also degraded when UV irradiated due to photocleavage of nPh. DX MGs were assembled from the MGs to give injectable gels that were not cytotoxic to nucleus pulposus cells. Comparison of the responsive properties of the DX MGs and MGs showed that the temperature and pH responses of the former were mostly governed by the latter. However, two key differences were found. Firstly, whilst increasing the crosslinker mol% in the MG building blocks (x) did not change MG particle swelling, the compression modulus (E) and swelling of the DX MG gels were strongly affected by x. The E value for the gels was tuneable using x which is a potentially useful new observation for DX MGs. Secondly, UV irradiation of the DX MGs enhanced gel mechanical photostability in contrast to the behaviour of the MGs. We find that the properties of the DX MGs do not simply follow those of the parent MGs and propose mechanisms to account for the differences. The new family of multi-responsive DX MGs presented in this study have potential application for soft tissue repair as injectable gels or as gel implants which report sterilisation.

Using microgels to control the morphology and optoelectronic properties of hybrid organic-inorganic perovskite films.

Microgels (MGs) are crosslinked polymer colloid particles that swell in a good solvent. Although MGs have been studied for over 80 years their ability to control the morphology and optoelectronic properties of composite films containing photoactive materials is in its infancy. Solution processable hybrid organic-inorganic perovskites such as CH3NH3PbI3-zClz have attracted enormous fundamental and applied interest because of their outstanding optoelectronic properties. There is considerable interest in establishing methods to control perovskite film morphology, for example, using micropatterning. Here, hydrophilic poly(N-vinylformamide)-based MGs were dispersed in perovskite precursor solution which was then spin coated to deposit CH3NH3PbI3-zClz/MG films for the first time. Remarkably, the CH3NH3PbI3-zClz/MG composites formed disordered inverse opal (DIO) films. The CH3NH3PbI3-zClz/MG composition ranges which gave DIO films are identified using a phase diagram. The pore wall thickness is shown to be controlled by the volume fraction of MGs used and a simple model is presented to explain this behaviour. The MGs not only caused CH3NH3PbI3-zClz to be more efficiently deposited but also increased light absorption and photoluminescence intensity. Demonstration solar cells constructed containing the DIO CH3NH3PbI3-zClz/MG films had an average conversion efficiency of 6.58 ± 0.81%. A mechanism for DIO film formation is discussed. The principles established in this study wherein MGs control the morphology and properties of CH3NH3PbI3-zClz/MG films should also apply to other perovskite/MG composites.

Plasmonic and colloidal stability behaviours of Au-acrylic core-shell nanoparticles with thin pH-responsive shells.

The localised surface plasmon resonance (LSPR) of Au nanoparticles (NPs) as well as its interaction with nearby entities provides a wealth of fundamental and practical information at the nanometre scale. A number of studies have investigated core-shell NPs with Au cores and polymer shells that are temperature-responsive. However, there are very few studies of pH-responsive Au-polymer NP shells. Precipitation polymerisation is a scalable method and here we establish such a method to synthesise pH-responsive Au-poly(methyl methacrylate) copolymer core-shell NPs without the need for pre-functionalisation. The comonomers used were methacrylic acid (MAA) or 2-carboxyethyl acrylate (CEA) and the shells were crosslinked with ethylene glycol dimethacrylate. A series of five core-shell systems with collapsed shell thicknesses less than 30 nm are studied. The shell-thicknesses for the CEA-based core-shell NPs are relatively thin (≤5 nm) compared to related Au-polymer core-shell NPs prepared using precipitation polymerisation. The LSPR properties of the core-shell NPs were dependent on the shell thickness and were successfully simulated using finite difference time domain (FDTD) calculations. Two systems are considered further as exemplars. The MAA-based core-shell system with the thickest shell exhibited enhanced colloidal stability to added electrolyte. The CEA-based core-shell dispersion with the thinnest shells displayed reversible pH-triggered aggregation and was cytocompatible for HeLa cells. Proof-of-concept data are presented that demonstrate intracellular pH reporting.

Core-shell-shell cytocompatible polymer dot-based particles with near-infrared emission and enhanced dispersion stability.

Polymer dots (PDs) are promising fluorescent probes for biomaterials applications. Here, novel cytocompatible composite PD particles have been synthesised with a core-shell-shell morphology. The particles show near-infrared emission, improved fluorescent brightness and enhanced colloidal stability compared to pure PDs. The particles also show non-radiative resonance energy transfer (NRET) with a model dye.

Surface structure, optoelectronic properties and charge transport in ZnO nanocrystal/MDMO-PPV multilayer films.

Blends of semiconducting nanocrystals and conjugated polymers continue to attract major research interest because of their potential applications in optoelectronic devices, such as solar cells, photodetectors and light-emitting diodes. In this study we investigate the surface structure, morphological and optoelectronic properties of multilayer films constructed from ZnO nanocrystals (NCs) and poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV). The effects of layer number and ZnO concentration (CZnO) used on the multilayer film properties are investigated. An optimised solvent blend enabled well-controlled layers to be sequentially spin coated and the construction of multilayer films containing six ZnO NC (Z) and MDMO-PPV (M) layers (denoted as (ZM)6). Contact angle data showed a strong dependence on CZnO and indicated distinct differences in the coverage of MDMO-PPV by the ZnO NCs. UV-visible spectroscopy showed that the MDMO-PPV absorption increased linearly with the number of layers in the films and demonstrates highly tuneable light absorption. Photoluminescence spectra showed reversible quenching as well as a surprising red-shift of the MDMO-PPV emission peak. Solar cells were constructed to probe vertical photo-generated charge transport. The measurements showed that (ZM)6 devices prepared using CZnO = 14.0 mg mL-1 had a remarkably high open circuit voltage of ∼800 mV. The device power conversion efficiency was similar to that of a control bilayer device prepared using a much thicker MDMO-PPV layer. The results of this study provide insight into the structure-optoelectronic property relationships of new semiconducting multilayer films which should also apply to other semiconducting NC/polymer combinations.

Highly deformable hydrogels constructed by pH-triggered polyacid nanoparticle disassembly in aqueous dispersions.

Most hydrogels are prepared using small-molecule monomers but unfortunately this approach may not be feasible for certain biomaterial applications. Consequently, alternative gel construction strategies have been established, which include using covalent inter-linking of preformed gel particles, or microgels (MGs). For example, covalently interlinking pH-responsive MGs can produce hydrogels comprising doubly crosslinked microgels (DX MGs). We hypothesised that the deformability of such DX MGs was limited by the presence of intra-MG crosslinking. Thus, in this study we designed new nanoparticle (NP)-based gels based on pH-swellable NPs that are not internally crosslinked. Two polyacid NPs were synthesised containing methacrylic acid (MAA) and either ethyl acrylate (EA) or methyl methacrylate (MMA). The PMAA-EA and PMAA-MMA NPs were subsequently vinyl-functionalised using glycidyl methacrylate (GMA) prior to gel formation via free-radical crosslinking. The NPs mostly disassembled on raising the solution pH but some self-crosslinking was nevertheless evident. The gels constructed from the EA- and MMA-based NPs had greater breaking strains than a control DX MG. The effect of varying the solution pH during curing on the morphology and mechanical properties of gels prepared using PMAA-MMA-GMA NPs was studied and both remarkable deformability and excellent recovery were observed. The gels were strongly pH-responsive and had tensile breaking strains of up to 420% with a compressive strain-at-break of more than 93%. An optimised formulation produced the most deformable and stretchable gel yet constructed using NPs or MGs as the only building block.