Low-Viscosity Route to High-Molecular-Weight Water-Soluble Polymers: Exploiting the Salt Sensitivity of Poly(N-acryloylmorpholine).

We report a new one-pot low-viscosity synthetic route to high molecular weight non-ionic water-soluble polymers based on polymerization-induced self-assembly (PISA). The RAFT aqueous dispersion polymerization of N-acryloylmorpholine (NAM) is conducted at 30 °C using a suitable redox initiator and a poly(2-hydroxyethyl acrylamide) (PHEAC) precursor in the presence of 0.60 M ammonium sulfate. This relatively low level of added electrolyte is sufficient to salt out the PNAM block, while steric stabilization is conferred by the relatively short salt-tolerant PHEAC block. A mean degree of polymerization (DP) of up to 6000 was targeted for the PNAM block, and high NAM conversions (>96%) were obtained in all cases. On dilution with deionized water, the as-synthesized sterically stabilized particles undergo dissociation to afford molecularly dissolved chains, as judged by dynamic light scattering and 1H NMR spectroscopy studies. DMF GPC analysis confirmed a high chain extension efficiency for the PHEAC precursor, but relatively broad molecular weight distributions were observed for the PHEAC-PNAM diblock copolymer chains (Mw/Mn > 1.9). This has been observed for many other PISA formulations when targeting high core-forming block DPs and is tentatively attributed to chain transfer to polymer, which is well known for polyacrylamide-based polymers. In fact, relatively high dispersities are actually desirable if such copolymers are to be used as viscosity modifiers because solution viscosity correlates closely with Mw. Static light scattering studies were also conducted, with a Zimm plot indicating an absolute Mw of approximately 2.5 × 106 g mol-1 when targeting a PNAM DP of 6000. Finally, it is emphasized that targeting such high DPs leads to a sulfur content for this latter formulation of just 23 ppm, which minimizes the cost, color, and malodor associated with the organosulfur RAFT agent.

Ligand-Directed Self-Assembly of Organic-Semiconductor/Quantum-Dot Blend Films Enables Efficient Triplet Exciton-Photon Conversion.

Blends comprising organic semiconductors and inorganic quantum dots (QDs) are relevant for many optoelectronic applications and devices. However, the individual components in organic-QD blends have a strong tendency to aggregate and phase-separate during film processing, compromising both their structural and electronic properties. Here, we demonstrate a QD surface engineering approach using electronically active, highly soluble semiconductor ligands that are matched to the organic semiconductor host material to achieve well-dispersed inorganic-organic blend films, as characterized by X-ray and neutron scattering, and electron microscopies. This approach preserves the electronic properties of the organic and QD phases and also creates an optimized interface between them. We exemplify this in two emerging applications, singlet-fission-based photon multiplication (SF-PM) and triplet-triplet annihilation-based photon upconversion (TTA-UC). Steady-state and time-resolved optical spectroscopy shows that triplet excitons can be transferred with near unity efficiently across the organic-inorganic interface, while the organic films maintain efficient SF (190% yield) in the organic phase. By changing the relative energy between organic and inorganic components, yellow upconverted emission is observed upon 790 nm NIR excitation. Overall, we provide a highly versatile approach to overcome longstanding challenges in the blending of organic semiconductors with QDs that have relevance for many optical and optoelectronic applications.

Using visual attention estimation on videos for automated prediction of autism spectrum disorder and symptom severity in preschool children.

Atypical visual attention in individuals with autism spectrum disorders (ASD) has been utilised as a unique diagnosis criterion in previous research. This paper presents a novel approach to the automatic and quantitative screening of ASD as well as symptom severity prediction in preschool children. We develop a novel computational pipeline that extracts learned features from a dynamic visual stimulus to classify ASD children and predict the level of ASD-related symptoms. Experimental results demonstrate promising performance that is superior to using handcrafted features and machine learning algorithms, in terms of evaluation metrics used in diagnostic tests. Using a leave-one-out cross-validation approach, we obtained an accuracy of 94.59%, a sensitivity of 100%, a specificity of 76.47% and an area under the receiver operating characteristic curve (AUC) of 96% for ASD classification. In addition, we obtained an accuracy of 94.74%, a sensitivity of 87.50%, a specificity of 100% and an AUC of 99% for ASD symptom severity prediction.

Synthesis and Characterization of Stimuli-Responsive Polymer Brushes in Nanofluidic Channels.

Nanochannels with controllable gating behavior are attractive features in a wide range of nanofluidic applications including viral detection, particle sorting, and flow regulation. Here, we use selective sidewall functionalization of nanochannels with a polyelectrolyte brush to investigate the channel gating response to variations in solution pH and ionic strength. The conformational and structural changes of the interfacial brush layer within the channels are interrogated by specular and off-specular neutron reflectometry. Simultaneous fits of the specular and off-specular signals, using a dynamical theory model and a fitting optimization protocol, enable detailed characterization of the brush conformations and corresponding channel geometry under different solution conditions. Our results indicate a collapsed brush state under basic pH, equivalent to an open gate, and an expanded brush state representing a partially closed gate upon decreasing the pH and salt concentration. These findings open new possibilities in noninvasive in situ characterization of tunable nanofluidics and lab-on-chip devices with advanced designs and improved functionality.

Space controlled environment agriculture offers pathways to improve the sustainability of controlled environmental agriculture on Earth.

Terrestrial controlled environment agriculture (CEA) will have an increasingly important role in food production. However, present CEA systems are energy- and resource-hungry and rarely profitable, requiring a step change in design and optimization. Here we argue that the unique nature of space controlled environment agriculture (SpaCEA), which needs to be both highly resource efficient and circular in design, presents an opportunity to develop intrinsically circular CEA systems. Life-cycle analysis tools should be used to optimize the provision and use of natural or electrical light, power, nutrients and infrastructure in CEA and/or SpaCEA systems, and to guide research and development into subsystems that bring strong environmental advantages. We suggest that SpaCEA public outreach can also be used to improve the perception of terrestrial CEA on Earth by using space as a gateway for exhibiting CEA food growing technologies. A substantial focus on SpaCEA development should be viewed as an efficient contribution to addressing major current CEA challenges.

Insights into the kinetics and self-assembly order of small-molecule organic semiconductor/quantum dot blends during blade coating.

Organic-inorganic nanocomposite films formed from blends of small-molecule organic semiconductors and colloidal quantum dots are attractive candidates for high efficiency, low-cost solar energy harvesting devices. Understanding and controlling the self-assembly of the resulting organic-inorganic nanocomposite films is crucial in optimising device performance, not only at a lab-scale but for large-scale, high-throughput printing and coating methods. Here, in situ grazing incidence X-ray scattering (GIXS) gives direct insights into how small-molecule organic semiconductors and colloidal quantum dots self-assemble during blade coating. Results show that for two blends separated only by a small difference in the structure of the small molecule forming the organic phase, crystallisation may proceed down two distinct routes. It either occurs spontaneously or is mediated by the formation of quantum dot aggregates. Irrespective of the initial crystallisation route, the small-molecule crystallisation acts to exclude the quantum dot inclusions from the growing crystalline matrix phase. These results provide important fundamental understanding of structure formation in nanocomposite films of organic small molecules and colloidal quantum dots prepared via solution processing routes. It highlights the fundamental difference to structural evolution which can be made by seemingly small changes in system composition. It provides routes for the structural design and optimisation of solution-processed nanocomposites that are compatible with the large-scale deposition manufacturing techniques that are crucial in driving their wider adoption in energy harvesting applications.

Mixed Small-Molecule Matrices Improve Nanoparticle Dispersibility in Organic Semiconductor-Nanoparticle Films.

Controlling the dispersibility of nanocrystalline inorganic quantum dots (QDs) within organic semiconductor (OSC):QD nanocomposite films is critical for a wide range of optoelectronic devices. This work demonstrates how small changes to the OSC host molecule can have a dramatic detrimental effect on QD dispersibility within the host organic semiconductor matrix as quantified by grazing incidence X-ray scattering. It is commonplace to modify QD surface chemistry to enhance QD dispersibility within an OSC host. Here, an alternative route toward optimizing QD dispersibilities is demonstrated, which dramatically improves QD dispersibilities through blending two different OSCs to form a fully mixed OSC matrix phase.

Solution and Solid-State Behavior of Amphiphilic ABA Triblock Copolymers of Poly(acrylic acid-stat-styrene)-block-poly(butyl acrylate)-block-poly(acrylic acid-stat-styrene).

A combination of statistical and triblock copolymer properties is explored to produce stable aqueous polymer dispersions suitable for the film formation. In order to perform an extensive structural characterization of the products in the dissolved, dispersed, and solid states, a wide range of symmetrical poly(acrylic acid-stat-styrene) x -block-poly(butyl acrylate) y -block-poly(acrylic acid-stat-styrene) x , poly(AA-st-St) x -b-PBA y -b-poly(AA-st-St) x , (x = 56, 108 and 140, y = 100-750; the AA:St molar ratio is 42:58) triblock copolymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) solution polymerization using a bifunctional symmetrical RAFT agent. It is demonstrated that the amphiphilic statistical outer blocks can provide sufficient stabilization to largely hydrophobic particles in aqueous dispersions. Such a molecular design provides an advantage over copolymers composed only of homoblocks, as a simple variation of the statistical block component ratio provides an efficient way to control the hydrophilicity of the stabilizer block, which ultimately affects the copolymer morphology in solutions and solid films. It was found by small-angle X-ray scattering (SAXS) that the copolymers behaved as dissolved chains in methylethylketone (MEK) but self-assembled in water into stable and well-defined spherical particles that increased in size with the length of the hydrophobic PBA block. These particles possessed an additional particulate surface structure formed by the statistical copolymer stabilizer block, which self-folded through the hydrophobic interactions between the styrene units. SAXS and atomic force microscopy showed that the copolymer films cast from the MEK solutions formed structures predicted by self-consistent field theory for symmetrical triblock copolymers, while the aqueous dispersions formed structural morphologies similar to a close-packed spheres, as would be expected for copolymer particles trapped kinetically due to the restricted movement of the blocks in the initial aqueous dispersion. A strong correlation between the structural morphology and mechanical properties of the films was observed. It was found that the properties of the solvent cast films were highly dependent on the ratios of the hard [poly(AA-st-St)] and soft (PBA) blocks, while the aqueous cast films did not show such a dependence. The continuous phase of hard blocks, always formed in the case of the aqueous cast films, produced films with a higher elastic modulus and a lower extension-to-break in a comparison with the solvent-cast films.

FoamPi: An open-source raspberry Pi based apparatus for monitoring polyurethane foam reactions.

Adiabatic temperature rise is an important method for determining isocyanate conversion in polyurethane foam reactions as well as many other exothermic chemical reactions. Adiabatic temperature rise can be used in conjunction with change in height and mass measurements to gain understanding into the blowing and gelling reactions that occur during polyurethane foaming as well as give important information on cell morphology. FoamPi is an open-source Raspberry Pi device for monitoring polyurethane foaming reactions. The device effectively monitors temperature rise, change in foam height as well as changes in the mass during the reaction. Three Python scripts are also presented. The first logs raw data during the reaction. The second corrects temperature data such that it can be used in adiabatic temperature rise reactions for calculating isocyanate conversion; additionally this script reduces noise in all the data and removes erroneous readings. The final script extracts important information from the corrected data such as maximum temperature change and maximum height change as well as the time to reach these points. Commercial examples of such equipment exist however the price (>£10000) of these equipment make these systems inaccessible for many research laboratories. The FoamPi build presented is inexpensive (£350) and test examples are shown here to indicate the reproducibility of results as well as precision of the FoamPi.

Hydrocarbon-Based Statistical Copolymers Outperform Block Copolymers for Stabilization of Ethanol-Water Foams.

Well-defined block copolymers have been widely used as emulsifiers, stabilizers, and dispersants in the chemical industry for at least 50 years. In contrast, nature employs amphiphilic proteins as polymeric surfactants whereby the spatial distribution of hydrophilic and hydrophobic amino acids within the polypeptide chains is optimized for surface activity. Herein, we report that polydisperse statistical copolymers prepared by conventional free-radical copolymerization can provide superior foaming performance compared to the analogous diblock copolymers. A series of predominantly (meth)acrylic comonomers are screened to identify optimal surface activity for foam stabilization of aqueous ethanol solutions. In particular, all-acrylic statistical copolymers comprising trimethylhexyl acrylate and poly(ethylene glycol) acrylate, P(TMHA-stat-PEGA), confer strong foamability and also lower the surface tension of a range of ethanol-water mixtures to a greater extent than the analogous block copolymers. For ethanol-rich hand sanitizer formulations, foam stabilization is normally achieved using environmentally persistent silicone-based copolymers or fluorinated surfactants. Herein, the best-performing fully hydrocarbon-based copolymer surfactants effectively stabilize ethanol-rich foams by a mechanism that resembles that of naturally-occurring proteins. This ability to reduce the surface tension of low-surface-energy liquids suggests a wide range of potential commercial applications.

Ultrafast exciton transport at early times in quantum dot solids.

Quantum dot (QD) solids are an emerging platform for developing a range of optoelectronic devices. Thus, understanding exciton dynamics is essential towards developing and optimizing QD devices. Here, using transient absorption microscopy, we reveal the initial exciton dynamics in QDs with femtosecond timescales. We observe high exciton diffusivity (~102 cm2 s-1) in lead chalcogenide QDs within the first few hundred femtoseconds after photoexcitation followed by a transition to a slower regime (~10-1-1 cm2 s-1). QD solids with larger interdot distances exhibit higher initial diffusivity and a delayed transition to the slower regime, while higher QD packing density and heterogeneity accelerate this transition. The fast transport regime occurs only in materials with exciton Bohr radii much larger than the QD sizes, suggesting the transport of delocalized excitons in this regime and a transition to slower transport governed by exciton localization. These findings suggest routes to control the optoelectronic properties of QD solids.

Toward polymer upcycling-adding value and tackling circularity.

Plastics have revolutionized modern life, but have created a global waste crisis driven by our reliance and demand for low-cost, disposable materials. New approaches are vital to address challenges related to plastics waste heterogeneity, along with the property reductions induced by mechanical recycling. Chemical recycling and upcycling of polymers may enable circularity through separation strategies, chemistries that promote closed-loop recycling inherent to macromolecular design, and transformative processes that shift the life-cycle landscape. Polymer upcycling schemes may enable lower-energy pathways and minimal environmental impacts compared with traditional mechanical and chemical recycling. The emergence of industrial adoption of recycling and upcycling approaches is encouraging, solidifying the critical role for these strategies in addressing the fate of plastics and driving advances in next-generation materials design.

Rational synthesis of novel biocompatible thermoresponsive block copolymer worm gels.

It is well known that reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA) enables the rational design of diblock copolymer worm gels. Moreover, such hydrogels can undergo degelation on cooling below ambient temperature as a result of a worm-to-sphere transition. However, only a subset of such block copolymer worms exhibit thermoresponsive behavior. For example, PMPC26-PHPMA280 worm gels prepared using a poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC26) precursor do not undergo degelation on cooling to 6 °C (see S. Sugihara et al., J. Am. Chem. Soc., 2011, 133, 15707-15713). Informed by our recent studies (N. J. Warren et al., Macromolecules, 2018, 51, 8357-8371), we decided to reduce the mean degrees of polymerization of both the PMPC steric stabilizer block and the structure-directing PHPMA block when targeting a pure worm morphology. This rational approach reduces the hydrophobic character of the PHPMA block and hence introduces the desired thermoresponsive character, as evidenced by the worm-to-sphere transition (and concomitant degelation) that occurs on cooling a PMPC15-PHPMA150 worm gel from 40 °C to 6 °C. Moreover, worms are reconstituted on returning to 40 °C and the original gel modulus is restored. This augurs well for potential biomedical applications, which will be examined in due course. Finally, small-angle X-ray scattering studies indicated a scaling law exponent of 0.67 (≈2/3) for the relationship between the worm core cross-sectional diameter and the PHPMA DP for a series of PHPMA-based worms prepared using a range of steric stabilizer blocks, which is consistent with the strong segregation regime for such systems.

Co-assembly and Structure of Sodium Dodecylsulfate and other n-Alkyl Sulfates in Glycerol: n-Alkyl Sulfate-Glycerol Crystal Phase.

HYPOTHESIS: Following the observation of a microfibrillar phase in sodium dodecylsulfate (SDS)-glycerol mixtures, it is hypothesized that this phase is a crystalline structure containing SDS and glycerol, where the interaction between sulfate and glycerol layers mediates the co-assembly, which also could be universal for similar systems formed by n-alkyl sulfate homologues. Experiment. n-alkyl sulfate glycerol solutions were studied using a combination of optical microscopy, small- and wide-angle X-ray scattering (SAXS/WAXS). Time-resolved SAXS was employed to determine the phase formation in SDS-glycerol-water mixtures. FINDINGS: The microfibrillar crystalline phase was reproduced in even-chained n-alkyl sulfates with a chain length between 12 and 18 carbon atoms, where the phase lamellar period increased uniformly with the alkyl chain length. Reconstruction of electron density profiles from the diffraction patterns allowed the lamellar structural motif of the phase, the glycerol location and stoichiometry to be determined. When SDS-glycerol-water mixtures with water concentration below 6 wt% are isothermally solidified at 20 °C, SDS-glycerol crystals and/or anhydrous SDS form, where the former is inhibited by the latter at higher water concentrations. The learnings from the SDS-glycerol phase formation allows new gels to be created, utilising the glycerol-sulfate motif generating microfibrils. This expands the knowledge of the applicable formulation space for SDS-water containing mixtures.

A facile method to control the phase behavior of hydroxypropyl cellulose.

We report a facile chemical method to convert the hydroxyl groups of hydroxypropyl cellulose (HPC) into carbamates. It was achieved by the reaction of HPC with N-methyl carbamoylimidazole, which is a safe and easy to handle replacement for the particularly hazardous reagent methyl isocyanate. Using a series of HPC with a range of molar substitution of hydroxypropyl groups, we synthesized HPC methylcarbamates showing lower critical solution temperature (LCST) in the range between 94 and 15 °C. A linear dependence of LCST versus methylcarbamate degree of substitution is observed. The lower the initial hydroxypropyl content of HPC, the greater the effect of methylcarbamate on the LCST. Surface tension study showed that methylcarbamate modification has an insignificant effect on the hydrophilic-hydrophobic balance of the macromolecules below LCST unless the molecular substitution of hydroxypropyl groups is so low (0.8) that the native cellulose OH groups can react with N-methyl carbamoylimidazole.

Computer vision in autism spectrum disorder research: a systematic review of published studies from 2009 to 2019.

The current state of computer vision methods applied to autism spectrum disorder (ASD) research has not been well established. Increasing evidence suggests that computer vision techniques have a strong impact on autism research. The primary objective of this systematic review is to examine how computer vision analysis has been useful in ASD diagnosis, therapy and autism research in general. A systematic review of publications indexed on PubMed, IEEE Xplore and ACM Digital Library was conducted from 2009 to 2019. Search terms included ['autis*' AND ('computer vision' OR 'behavio* imaging' OR 'behavio* analysis' OR 'affective computing')]. Results are reported according to PRISMA statement. A total of 94 studies are included in the analysis. Eligible papers are categorised based on the potential biological/behavioural markers quantified in each study. Then, different computer vision approaches that were employed in the included papers are described. Different publicly available datasets are also reviewed in order to rapidly familiarise researchers with datasets applicable to their field and to accelerate both new behavioural and technological work on autism research. Finally, future research directions are outlined. The findings in this review suggest that computer vision analysis is useful for the quantification of behavioural/biological markers which can further lead to a more objective analysis in autism research.

Controlling the structures of organic semiconductor-quantum dot nanocomposites through ligand shell chemistry.

Nanocrystal quantum dots (QD) functionalised with active organic ligands hold significant promise as solar energy conversion materials, capable of multiexcitonic processes that could improve the efficiencies of single-junction photovoltaic devices. Small-angle X-ray and neutron scattering (SAXS and SANS) were used to characterize the structure of lead sulphide QDs post ligand-exchange with model acene-carboxylic acid ligands (benzoic acid, hydrocinnamic acid and naphthoic acid). Results demonstrate that hydrocinnamic acid and naphthoic acid ligated QDs form monolayer ligand shells, whilst benzoic acid ligated QDs possess ligand shells thicker than a monolayer. Further, the formation of a range of nanocomposite materials through the self-assembly of such acene-ligated QDs with an organic small-molecule semiconductor [5,12-bis((triisopropylsilyl)ethynyl)tetracene (TIPS-Tc)] is investigated. These materials are representative of a wider set of functional solar energy materials; here the focus is on structural studies, and their optoelectronic function is not investigated. As TIPS-Tc concentrations are increased, approaching the solubility limit, SANS data show that QD fractal-like features form, with structures possibly consistent with a diffusion limited aggregation mechanism. These, it is likely, act as heterogeneous nucleation agents for TIPS-Tc crystallization, generating agglomerates containing both QDs and TIPS-Tc. Within the TIPS-Tc crystals there seem to be three distinct QD morphologies: (i) at the crystallite centre (fractal-like QD aggregates acting as nucleating agents), (ii) trapped within the growing crystallite (giving rise to QD features ordered as sticky hard spheres), and (iii) a population of aggregate QDs at the periphery of the crystalline interface that were expelled from the growing TIPS-Tc crystal. Exposure of the QD:TIPS-Tc crystals to DMF vapour, a solvent known to be able to strip ligands from QDs, alters the spacing between PbS-hydrocinnamic acid and PbS-naphthoic acid ligated QD aggregate features. In contrast, for PbS-benzoic acid ligated QDs, DMF vapour exposure promotes the formation of ordered QD colloidal crystal type phases. This work thus demonstrates how different QD ligand chemistries control the interactions between QDs and an organic small molecule, leading to widely differing self-assembly processes. It highlights the unique capabilities of multiscale X-ray and neutron scattering in characterising such composite materials.

Flow-induced crystallisation of polymers from aqueous solution.

Synthetic polymers are thoroughly embedded in the modern society and their consumption grows annually. Efficient routes to their production and processing have never been more important. In this respect, silk protein fibrillation is superior to conventional polymer processing, not only by achieving outstanding physical properties of materials, such as high tensile strength and toughness, but also improved process energy efficiency. Natural silk solidifies in response to flow of the liquid using conformation-dependent intermolecular interactions to desolvate (denature) protein chains. This mechanism is reproduced here by an aqueous poly(ethylene oxide) (PEO) solution, which solidifies at ambient conditions when subjected to flow. The transition requires that an energy threshold is exceeded by the flow conditions, which disrupts a protective hydration shell around polymer molecules, releasing them from a metastable state into the thermodynamically favoured crystalline state. This mechanism requires vastly lower energy inputs and demonstrates an alternative route for polymer processing.

Synthesis of High χ-Low N Diblock Copolymers by Polymerization-Induced Self-Assembly.

Polymerization-induced self-assembly (PISA) enables the scalable synthesis of functional block copolymer nanoparticles with various morphologies. Herein we exploit this versatile technique to produce so-called "high χ-low N" diblock copolymers that undergo nanoscale phase separation in the solid state to produce sub-10 nm surface features. By varying the degree of polymerization of the stabilizer and core-forming blocks, PISA provides rapid access to a wide range of diblock copolymers, and enables fundamental thermodynamic parameters to be determined. In addition, the pre-organization of copolymer chains within sterically-stabilized nanoparticles that occurs during PISA leads to enhanced phase separation relative to that achieved using solution-cast molecularly-dissolved copolymer chains.