Exploring the Impact of 1,8-Diioodoctane on the Photostability of Organic Photovoltaics.

Improving the photostability of the light-harvesting blend film in organic photovoltaics is crucial to achieving long-term operational lifetimes that are required for commercialization. However, understanding the degradation factors which drive instabilities is complex, with many variables such as film morphology, residual solvents, and acceptor or donor design all influencing how light and oxygen interact with the blend film. In this work, we show how blend films comprising a donor polymer (PBDB-T) and small molecule acceptor (PC71BM or ITIC) processed with solvent additive (DIO) yield very different film morphologies, device performance, and photostability. We show that DIO is retained approximately 10 times more effectively in ITIC based films compared to PC71BM. Unexpectedly, we see that while high volumes of DIO reduce photostability for encapsulated ITIC devices, when oxygen is introduced DIO can improve the lifetime of PBDB-T:ITIC based cells. Here, the addition of 3% DIO doubles the T 80 compared to ITIC based devices without DIO, suggesting that DIO-induced morphological changes interfere with or reduce photo-oxidative reactions.

The actin cytoskeleton plays multiple roles in structural colour formation in butterfly wing scales.

Vivid structural colours in butterflies are caused by photonic nanostructures scattering light. Structural colours evolved for numerous biological signalling functions and have important technological applications. Optically, such structures are well understood, however insight into their development in vivo remains scarce. We show that actin is intimately involved in structural colour formation in butterfly wing scales. Using comparisons between iridescent (structurally coloured) and non-iridescent scales in adult and developing H. sara, we show that iridescent scales have more densely packed actin bundles leading to an increased density of reflective ridges. Super-resolution microscopy across three distantly related butterfly species reveals that actin is repeatedly re-arranged during scale development and crucially when the optical nanostructures are forming. Furthermore, actin perturbation experiments at these later developmental stages resulted in near total loss of structural colour in H. sara. Overall, this shows that actin plays a vital and direct templating role during structural colour formation in butterfly scales, providing ridge patterning mechanisms that are likely universal across lepidoptera.

The Nanoscale Structure and Stability of Organic Photovoltaic Blends Processed with Solvent Additives.

Controlling the nanomorphology in bulk heterojunction photoactive blends is crucial for optimizing the performance and stability of organic photovoltaic (OPV) technologies. A promising approach is to alter the drying dynamics and consequently, the nanostructure of the blend film using solvent additives such as 1,8-diiodooctane (DIO). Although this approach is demonstrated extensively for OPV systems incorporating fullerene-based acceptors, it is unclear how solvent additive processing influences the morphology and stability of nonfullerene acceptor (NFA) systems. Here, small angle neutron scattering (SANS) is used to probe the nanomorphology of two model OPV systems processed with DIO: a fullerene-based system (PBDB-T:PC71BM) and an NFA-based system (PBDB-T:ITIC). To overcome the low intrinsic neutron scattering length density contrast in polymer:NFA blend films, the synthesis of a deuterated NFA analog (ITIC-d52) is reported. Using SANS, new insights into the nanoscale evolution of fullerene and NFA-based systems are provided by characterizing films immediately after fabrication, after thermal annealing, and after aging for 1 year. It is found that DIO processing influences fullerene and NFA-based systems differently with NFA-based systems characterized by more phase-separated domains. After long-term aging, SANS reveals both systems demonstrate some level of thermodynamic induced domain coarsening.

Tissue Equivalent Curved Organic X-ray Detectors Utilizing High Atomic Number Polythiophene Analogues.

Organic semiconductors are a promising material candidate for X-ray detection. However, the low atomic number (Z) of organic semiconductors leads to poor X-ray absorption thus restricting their performance. Herein, the authors propose a new strategy for achieving high-sensitivity performance for X-ray detectors based on organic semiconductors modified with high -Z heteroatoms. X-ray detectors are fabricated with p-type organic semiconductors containing selenium heteroatoms (poly(3-hexyl)selenophene (P3HSe)) in blends with an n-type fullerene derivative ([6,6]-Phenyl C71 butyric acid methyl ester (PC70 BM). When characterized under 70, 100, 150, and 220 kVp X-ray radiation, these heteroatom-containing detectors displayed a superior performance in terms of sensitivity up to 600 ± 11 nC Gy-1  cm-2 with respect to the bismuth oxide (Bi2 O3 ) nanoparticle (NP) sensitized organic detectors. Despite the lower Z of selenium compared to the NPs typically used, the authors identify a more efficient generation of electron-hole pairs, better charge transfer, and charge transport characteristics in heteroatom-incorporated detectors that result in this breakthrough detector performance. The authors also demonstrate flexible X-ray detectors that can be curved to a radius as low as 2 mm with low deviation in X-ray response under 100 repeated bending cycles while maintaining an industry-standard ultra-low dark current of 0.03 ± 0.01 pA mm-2 .

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.

Designing Effective Antimicrobial Nanostructured Surfaces: Highlighting the Lack of Consensus in the Literature.

Research into nanostructured materials, inspired by the topography of certain insect wings, has provided a potential pathway toward drug-free antibacterial surfaces, which may be vital in the ongoing battle against antimicrobial resistance. However, to produce viable antibacterial nanostructured surfaces, we must first understand the bactericidal mechanism of action and how to optimize them to kill the widest range of microorganisms. This review discusses the parameters of nanostructured surfaces that have been shown to influence their bactericidal efficiency and highlights the highly variable nature of many of the findings. A large-scale analysis of the literature is also presented, which further shows a lack of clarity in what is understood about the factors influencing bactericidal efficiency. The potential reasons for the ambiguity, including how the killing effect may be a result of multiple factors and issues with nonstandardized testing of the antibacterial properties of nanostructured surfaces, are then discussed. Finally, a standard method for testing of antimicrobial killing is proposed that will allow comparison between studies and enable a deeper understanding about nanostructured surfaces and how to optimize their bactericidal efficiency.

Exploring Nanoscale Structure in Perovskite Precursor Solutions Using Neutron and Light Scattering.

Tailoring the solution chemistry of metal halide perovskites requires a detailed understanding of precursor aggregation and coordination. In this work, we use various scattering techniques, including dynamic light scattering (DLS), small angle neutron scattering (SANS), and spin-echo SANS (SESANS) to probe the nanostructures from 1 nm to 10 µm within two different lead-halide perovskite solution inks (MAPbI3 and a triple-cation mixed-halide perovskite). We find that DLS can misrepresent the size distribution of the colloidal dispersion and use SANS/SESANS to confirm that these perovskite solutions are mostly comprised of 1-2 nm-sized particles. We further conclude that if there are larger colloids present, their concentration must be <0.005% of the total dispersion volume. With SANS, we apply a simple fitting model for two component microemulsions (Teubner-Strey), demonstrating this as a potential method to investigate the structure, chemical composition, and colloidal stability of perovskite solutions, and we here show that MAPbI3 solutions age more drastically than triple cation solutions.

The genetic basis of structural colour variation in mimetic Heliconius butterflies.

Structural colours, produced by the reflection of light from ultrastructures, have evolved multiple times in butterflies. Unlike pigmentary colours and patterns, little is known about the genetic basis of these colours. Reflective structures on wing-scale ridges are responsible for iridescent structural colour in many butterflies, including the Müllerian mimics Heliconius erato and Heliconius melpomene. Here, we quantify aspects of scale ultrastructure variation and colour in crosses between iridescent and non-iridescent subspecies of both of these species and perform quantitative trait locus (QTL) mapping. We show that iridescent structural colour has a complex genetic basis in both species, with offspring from crosses having a wide variation in blue colour (both hue and brightness) and scale structure measurements. We detect two different genomic regions in each species that explain modest amounts of this variation, with a sex-linked QTL in H. erato but not H. melpomene. We also find differences between species in the relationships between structure and colour, overall suggesting that these species have followed different evolutionary trajectories in their evolution of structural colour. We then identify genes within the QTL intervals that are differentially expressed between subspecies and/or wing regions, revealing likely candidates for genes controlling structural colour formation. This article is part of the theme issue 'Genetic basis of adaptation and speciation: from loci to causative mutations'.

Machine learning denoising of high-resolution X-ray nanotomography data.

High-resolution X-ray nanotomography is a quantitative tool for investigating specimens from a wide range of research areas. However, the quality of the reconstructed tomogram is often obscured by noise and therefore not suitable for automatic segmentation. Filtering methods are often required for a detailed quantitative analysis. However, most filters induce blurring in the reconstructed tomograms. Here, machine learning (ML) techniques offer a powerful alternative to conventional filtering methods. In this article, we verify that a self-supervised denoising ML technique can be used in a very efficient way for eliminating noise from nanotomography data. The technique presented is applied to high-resolution nanotomography data and compared to conventional filters, such as a median filter and a nonlocal means filter, optimized for tomographic data sets. The ML approach proves to be a very powerful tool that outperforms conventional filters by eliminating noise without blurring relevant structural features, thus enabling efficient quantitative analysis in different scientific fields.

Molecular Weight Tuning of Organic Semiconductors for Curved Organic-Inorganic Hybrid X-Ray Detectors.

Curved X-ray detectors have the potential to revolutionize diverse sectors due to benefits such as reduced image distortion and vignetting compared to their planar counterparts. While the use of inorganic semiconductors for curved detectors are restricted by their brittle nature, organic-inorganic hybrid semiconductors which incorporated bismuth oxide nanoparticles in an organic bulk heterojunction consisting of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl C71 butyric acid methyl ester (PC70 BM) are considered to be more promising in this regard. However, the influence of the P3HT molecular weight on the mechanical stability of curved, thick X-ray detectors remains less well understood. Herein, high P3HT molecular weights (>40 kDa) are identified to allow increased intermolecular bonding and chain entanglements, resulting in X-ray detectors that can be curved to a radius as low as 1.3 mm with low deviation in X-ray response under 100 repeated bending cycles while maintaining an industry-standard dark current of <1 pA mm-2 and a sensitivity of ≈ 0.17 µC Gy-1 cm-2 . This study identifies a crucial missing link in the development of curved detectors, namely the importance of the molecular weight of the polymer semiconductors used.

Graded Morphologies and the Performance of PffBT4T-2OD:PC71BM Devices Using Additive Choice.

The impact of several solvent processing additives (1-chloronaphthalene, methylnaphthalene, hexadecane, 1-phenyloctane, and p-anisaldehyde), 3% v/v in o-dichlorobenzene, on the performance and morphology of poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3‴-di(2-octyldodecyl)-2,2',5',22033,5″,2‴-quaterthiophen-5,5‴-diyl)] (PffBT4T-2OD):[6,6]-phenyl-C71-butyric acid methyl ester (PC71BM)-based polymer solar cells was investigated. Some additives were shown to enhance the power conversion efficiency (PCE) by ~6%, while others decreased the PCE by ~17-25% and a subset of the additives tested completely eliminated any power conversion efficiency and the operation as a photovoltaic device. Grazing-Incidence Wide Angle X-ray Scattering (GIWAXS) revealed a clear stepwise variation in the crystallinity of the systems when changing the additive between the two extreme situations of maximum PCE (1-chloronaphthalene) and null PCE (hexadecane). Small-Angle Neutron Scattering (SANS) revealed that the morphology of devices with PCE ~0% was composed of large domains with correlation lengths of ~30 nm, i.e., much larger than the typical exciton diffusion length (~12 nm) in organic semiconductors. The graded variations in crystallinity and in nano-domain size observed between the two extreme situations (1-chloronaphthalene and hexadecane) were responsible for the observed graded variations in device performance.

Cysteamine Decreases Low-Density Lipoprotein Oxidation, Causes Regression of Atherosclerosis, and Improves Liver and Muscle Function in Low-Density Lipoprotein Receptor-Deficient Mice.

Background We have shown previously that low-density lipoprotein (LDL) can be oxidized in the lysosomes of macrophages, that this oxidation can be inhibited by cysteamine, an antioxidant that accumulates in lysosomes, and that this drug decreases atherosclerosis in LDL receptor-deficient mice fed a high-fat diet. We have now performed a regression study with cysteamine, which is of more relevance to the treatment of human disease. Methods and Results LDL receptor-deficient mice were fed a high-fat diet to induce atherosclerotic lesions. They were then reared on chow diet and drinking water containing cysteamine or plain drinking water. Aortic atherosclerosis was assessed, and samples of liver and skeletal muscle were analyzed. There was no regression of atherosclerosis in the control mice, but cysteamine caused regression of between 32% and 56% compared with the control group, depending on the site of the lesions. Cysteamine substantially increased markers of lesion stability, decreased ceroid, and greatly decreased oxidized phospholipids in the lesions. The liver lipid levels and expression of cluster of differentiation 68, acetyl-coenzyme A acetyltransferase 2, cytochromes P450 (CYP)27, and proinflammatory cytokines and chemokines were decreased by cysteamine. Skeletal muscle function and oxidative fibers were increased by cysteamine. There were no changes in the plasma total cholesterol, LDL cholesterol, high-density lipoprotein cholesterol, or triacylglycerol concentrations attributable to cysteamine. Conclusions Inhibiting the lysosomal oxidation of LDL in atherosclerotic lesions by antioxidants targeted at lysosomes causes the regression of atherosclerosis and improves liver and muscle characteristics in mice and might be a promising novel therapy for atherosclerosis in patients.

X-Ray Ptychography with a Laboratory Source.

X-ray ptychography has revolutionized nanoscale phase contrast imaging at large-scale synchrotron sources in recent years. We present here the first successful demonstration of the technique in a small-scale laboratory setting. An experiment was conducted with a liquid metal-jet x-ray source and a single photon-counting detector with a high spectral resolution. The experiment used a spot size of 5 µm to produce a ptychographic phase image of a Siemens star test pattern with a submicron spatial resolution. The result and methodology presented show how high-resolution phase contrast imaging can now be performed at small-scale laboratory sources worldwide.

Control of Particle Size in the Self-Assembly of Amphiphilic Statistical Copolymers.

A range of amphiphilic statistical copolymers is synthesized where the hydrophilic component is either methacrylic acid (MAA) or 2-(dimethylamino)ethyl methacrylate (DMAEMA) and the hydrophobic component comprises methyl, ethyl, butyl, hexyl, or 2-ethylhexyl methacrylate, which provide a broad range of partition coefficients (log P). Small-angle X-ray scattering studies confirm that these amphiphilic copolymers self-assemble to form well-defined spherical nanoparticles in an aqueous solution, with more hydrophobic copolymers forming larger nanoparticles. Varying the nature of the alkyl substituent also influenced self-assembly with more hydrophobic comonomers producing larger nanoparticles at a given copolymer composition. A model based on particle surface charge density (PSC model) is used to describe the relationship between copolymer composition and nanoparticle size. This model assumes that the hydrophilic monomer is preferentially located at the particle surface and provides a good fit to all of the experimental data. More specifically, a linear relationship is observed between the surface area fraction covered by the hydrophilic comonomer required to achieve stabilization and the log P value for the hydrophobic comonomer. Contrast variation small-angle neutron scattering is used to study the internal structure of these nanoparticles. This technique indicates partial phase separation within the nanoparticles, with about half of the available hydrophilic comonomer repeat units being located at the surface and hydrophobic comonomer-rich cores. This information enables a refined PSC model to be developed, which indicates the same relationship between the surface area fraction of the hydrophilic comonomer and the log P of the hydrophobic comonomer repeat units for the anionic (MAA) and cationic (DMAEMA) comonomer systems. This study demonstrates how nanoparticle size can be readily controlled and predicted using relatively ill-defined statistical copolymers, making such systems a viable attractive alternative to diblock copolymer nanoparticles for a range of industrial applications.

Coordinated Ras and Rac Activity Shapes Macropinocytic Cups and Enables Phagocytosis of Geometrically Diverse Bacteria.

Engulfment of extracellular material by phagocytosis or macropinocytosis depends on the ability of cells to generate specialized cup-shaped protrusions. To effectively capture and internalize their targets, these cups are organized into a ring or ruffle of actin-driven protrusion encircling a non-protrusive interior domain. These functional domains depend on the combined activities of multiple Ras and Rho family small GTPases, but how their activities are integrated and differentially regulated over space and time is unknown. Here, we show that the amoeba Dictyostelium discoideum coordinates Ras and Rac activity using the multidomain protein RGBARG (RCC1, RhoGEF, BAR, and RasGAP-containing protein). We find RGBARG uses a tripartite mechanism of Ras, Rac, and phospholipid interactions to localize at the protruding edge and interface with the interior of both macropinocytic and phagocytic cups. There, we propose RGBARG shapes the protrusion by expanding Rac activation at the rim while suppressing expansion of the active Ras interior domain. Consequently, cells lacking RGBARG form enlarged, flat interior domains unable to generate large macropinosomes. During phagocytosis, we find that disruption of RGBARG causes a geometry-specific defect in engulfing rod-shaped bacteria and ellipsoidal beads. This demonstrates the importance of coordinating small GTPase activities during engulfment of more complex shapes and thus the full physiological range of microbes, and how this is achieved in a model professional phagocyte.

Rapid Scalable Processing of Tin Oxide Transport Layers for Perovskite Solar Cells.

The development of scalable deposition methods for perovskite solar cell materials is critical to enable the commercialization of this nascent technology. Herein, we investigate the use and processing of nanoparticle SnO2 films as electron transport layers in perovskite solar cells and develop deposition methods for ultrasonic spray coating and slot-die coating, leading to photovoltaic device efficiencies over 19%. The effects of postprocessing treatments (thermal annealing, UV ozone, and O2 plasma) are then probed using structural and spectroscopic techniques to characterize the nature of the np-SnO2/perovskite interface. We show that a brief "hot air flow" method can be used to replace extended thermal annealing, confirming that this approach is compatible with high-throughput processing. Our results highlight the importance of interface management to minimize nonradiative losses and provide a deeper understanding of the processing requirements for large-area deposition of nanoparticle metal oxides.

X-ray nano-tomography of complete scales from the ultra-white beetles Lepidiota stigma and Cyphochilus.

High resolution X-ray nano-tomography experiments are often limited to a few tens of micrometer size volumes due to detector size. It is possible, through the use of multiple overlapping tomography scans, to produce a large area scan which can encompass a sample in its entirety. Mounting and positioning regions to be scanned is highly challenging and normally requires focused ion beam approaches. In this work we have imaged intact beetle scale cells mounted on the tip of a needle using a micromanipulator stage. Here we show X-ray holotomography data for single ultra-white scales from the beetles Lepidiota stigma (L. stigma) and Cyphochilus which exhibit the most effective scattering of white light in the literature. The final thresholded matrices represent a scan area of 25 × 70 × 362.5 µm and 25 × 67.5 × 235µm while maintaining a pixel resolution of 25 nm. This tomographic approach allowed the internal structure of the scales to be captured completely intact and undistorted by the sectioning required for traditional microscopy techniques.

Millimeter-Scale Unipolar Transport in High Sensitivity Organic-Inorganic Semiconductor X-ray Detectors.

Hybrid inorganic-in-organic semiconductors are an attractive class of materials for optoelectronic applications. Traditionally, the thicknesses of organic semiconductors are kept below 1 µm due to poor charge transport in such systems. However, recent work suggests that charge carriers in such organic semiconductors can be transported over centimeter length scales opposing this view. In this work, a unipolar X-ray photoconductor based on a bulk heterojunction architecture, consisting of poly(3-hexylthiophene), a C70 derivative, and high atomic number bismuth oxide nanoparticles operating in the 0.1-1 mm thickness regime is demonstrated, having a high sensitivity of ∼160 µC mGy-1 cm-3. The high performance enabled by hole drift lengths approaching a millimeter facilitates a device architecture allowing a high fraction of the incident X-rays to be attenuated. An X-ray imager is demonstrated with sufficient resolution for security applications such as portable baggage screening at border crossings and public events and scalable medical applications.

Determination of the Thin-Film Structure of Zwitterion-Doped Poly(3,4-ethylenedioxythiophene):Poly(styrenesulfonate): A Neutron Reflectivity Study.

Doping poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is known to improve its conductivity; however, little is known about the thin-film structure of PEDOT:PSS when doped with an asymmetrically charged dopant. In this study, PEDOT:PSS was doped with different concentrations of the zwitterion 3-( N, N dimethylmyristylammonio)propanesulfonate (DYMAP), and its effect on the bulk structure of the films was characterized by neutron reflectivity. The results show that at a low doping concentration, the film separates into a quasi-bilayer structure with lower roughness (10%), increased thickness (18%), and lower electrical conductivity compared to the undoped sample. However, when the doping concentration increases, the film forms into a homogeneous layer and experiences an enhanced conductivity by more than an order of magnitude, a 20% smoother surface, and a 60% thickness increase relative to the pristine sample. Atomic force microscopy (AFM) and profilometry measurements confirmed these findings, and the AFM height and phase images showed the gradually increasing presence of DYMAP on the film surface as a function of the concentration. Neutron reflectivity also showed that the quasi-bilayer structure of the lowest concentration-doped PEDOT:PSS is separated by a graded rather than a well-defined interface. Our findings provide an understanding of the layer structure modification for doped PEDOT:PSS films which should prove important for device applications.

Phenotypic variation in Heliconius erato crosses shows that iridescent structural colour is sex-linked and controlled by multiple genes.

Bright, highly reflective iridescent colours can be seen across nature and are produced by the scattering of light from nanostructures. Heliconius butterflies have been widely studied for their diversity and mimicry of wing colour patterns. Despite iridescence evolving multiple times in this genus, little is known about the genetic basis of the colour and the development of the structures which produce it. Heliconius erato can be found across Central and South America, but only races found in western Ecuador and Colombia have developed blue iridescent colour. Here, we use crosses between iridescent and non-iridescent races of H. erato to study phenotypic variation in the resulting F2 generation. Using measurements of blue colour from photographs, we find that iridescent structural colour is a quantitative trait controlled by multiple genes, with strong evidence for loci on the Z sex chromosome. Iridescence is not linked to the Mendelian colour pattern locus that also segregates in these crosses (controlled by the gene cortex). Small-angle X-ray scattering data show that spacing between longitudinal ridges on the scales, which affects the intensity of the blue reflectance, also varies quantitatively in F2 crosses.