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.

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.

First Study of the

New astronomical observations point to a nucleosynthesis picture that goes beyond what was accepted until recently. The intermediate "i" process was proposed as a plausible scenario to explain some of the unusual abundance patterns observed in metal-poor stars. The most important nuclear physics properties entering i-process calculations are the neutron-capture cross sections and they are almost exclusively not known experimentally. Here we provide the first experimental constraints on the ^{139}Ba(n,γ)^{140}Ba reaction rate, which is the dominant source of uncertainty for the production of lanthanum, a key indicator of i-process conditions. This is an important step towards identifying the exact astrophysical site of stars carrying the i-process signature.

Proton Shell Gaps in N=28 Nuclei from the First Complete Spectroscopy Study with FRIB Decay Station Initiator.

The first complete measurement of the ß-decay strength distribution of _{17}^{45}Cl_{28} was performed at the Facility for Rare Isotope Beams (FRIB) with the FRIB Decay Station Initiator during the second FRIB experiment. The measurement involved the detection of neutrons and γ rays in two focal planes of the FRIB Decay Station Initiator in a single experiment for the first time. This enabled an analytical consistency in extracting the ß-decay strength distribution over the large range of excitation energies, including neutron unbound states. We observe a rapid increase in the ß-decay strength distribution above the neutron separation energy in _{18}^{45}Ar_{27}. This was interpreted to be caused by the transitioning of neutrons into protons excited across the Z=20 shell gap. The SDPF-MU interaction with reduced shell gap best reproduced the data. The measurement demonstrates a new approach that is sensitive to the proton shell gap in neutron rich nuclei according to SDPF-MU calculations.

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.

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.

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.

Mode of lysozyme protein adsorption at end-tethered polyethylene oxide brushes on gold surfaces determined by neutron reflectivity.

The mode of lysozyme protein adsorption at end-tethered thiol-terminated polyethylene oxide brushes grafted upon gold was determined in situ by neutron reflectivity using the INTER instrument at target station 2, ISIS, RAL, UK. It was found that the most probable position of protein adsorption at these weakly protein resistive brushes was at the gold-brush interface in the so-called primary protein position.

A new era in the treatment of multiple sclerosis.

Multiple sclerosis (MS) is an autoimmune disease of the central nervous system with a multifactorial aetiology and highly variable natural history. A growing understanding of the immunopathogenesis of the condition has led to an expanding array of therapies for this previously untreatable disease. While a cure for MS remains elusive, the potential to reduce inflammatory disease activity by preventing relapses and minimising disease progression is achievable. The importance of early treatment in minimising long-term disability is increasingly recognised. Most of the newer, more effective therapies are associated with risks and practical problems that necessitate an active management strategy and continuous vigilance. While the initiation of these therapies is likely to remain the responsibility of neurologists, other specialist physicians and general practitioners will be involved in the identification and management of adverse effects.

Randomized comparison trial of density and context of upper limb intensive group versus individualized occupational therapy for children with unilateral cerebral palsy.

AIM: To determine whether short-term intensive group-based therapy combining modified constraint-induced movement therapy and bimanual therapy (hybrid-CIMT) is more effective than an equal total dose of distributed individualized occupational therapy (standard care) on upper limb motor and individualized outcomes. METHOD: Fifty-three children with unilateral cerebral palsy (69% males; mean age 7y 10mo, SD 2y 4mo; Manual Ability Classification System level I, n=24; level II, n=23) were randomly allocated, and 44 received either hybrid-CIMT (n=25) or standard care (n=19). Standard care comprised six weekly occupational therapy sessions and a 12-week home programme. Outcomes were assessed at baseline, 13 weeks, and 26 weeks after treatment. RESULTS: Groups were equivalent at baseline. Standard care achieved greater gains on satisfaction with occupational performance after intervention (estimated mean difference -1.2, 95% CI -2.2 to -0.1; p=0.04) and Assisting Hand Assessment at 26 weeks (estimated mean difference 3.1, 95% CI 0.2-6.0; p=0.04). Both groups demonstrated significant improvements in dexterity of the impaired upper limb, and bimanual and occupational performance over time. The differences between groups were not clinically meaningful. INTERPRETATION: There were no differences between the two models of therapy delivery. Group-based intensive camps may not be readily available; however, individualized standard care augmented with a home programme may offer an effective alternative but needs to be provided at a sufficient dose.

Non-irradiated female survivors of childhood acute lymphoblastic leukaemia are at risk of long-term increases in weight and body mass index.

We report long-term, including final height, auxological data from our retrospective study of non-irradiated survivors of childhood acute lymphoblastic leukaemia (ALL). Body mass index (BMI) standard deviation score (SDS) increases in females, due to increased weight-SDS, persisted to final height, with probable adverse long-term health outcomes. In contrast, males demonstrated increased BMI-SDS in follow-up, due to reduced height-SDS, not increased weight-SDS, but such changes had resolved by final height. Childhood ALL survivors, particularly females, are therefore at potential increased risk of developing the metabolic syndrome during follow-up. We recommend that strategies to minimize weight gain should be implemented during ALL treatment.

Protein adsorption on well-characterized polyethylene oxide brushes on gold: dependence on molecular weight and grafting density.

The adsorption of lysozyme protein was measured ex situ on well-characterized gold surfaces coated by end-tethered polyethylene oxide brushes of various molecular weights and controlled grafting densities. The adsorbed amount of protein for different molecular weight brushes was found to collapse onto one master curve when plotted against brush coverage. We interpret this relationship in terms of a model involving site-blocking of the adsorption of proteins at the substrate and discuss the role of the physical attraction of PEO segments to gold. We account for our observation of a simple exponential relationship between protein adsorption and normalized brush coverage with a simple protein adsorption model. In contrast to other studies in similar systems, we do not observe protein adsorption on brushes at high grafting density, and we suggest that this discrepancy may be due to the solubility effects of salt upon the brushes, influencing their protein binding affinity, in the limit of high grafting density and high brush volume fraction.

Range verification in heavy-ion therapy using a hadron tumour marker.

Objective.A new method to estimate the range of an ion beam in a patient during heavy-ion therapy was investigated, which was previously verified for application in proton therapy.Approach.The method consists of placing a hadron tumour marker (HTM) close to the tumour. As the treatment beam impinges on the HTM, the marker undergoes nuclear reactions. When the HTM material is carefully chosen, the activation results in the emission of several delayed, characteristicγrays, whose intensities are correlated with the remaining range inside the patient. When not just one but two reaction channels are investigated, the ratio between these twoγray emissions can be measured, and the ratio is independent of any beam delivery uncertainties.Main results.A proof-of-principle experiment with an16O ion beam and Ag foils as HTM was successfully executed. The107Ag(16O,x)112Sb and the107Ag(16O,x)114Sb reaction channels were identified as suitable for the HTM technique. When only oneγ-ray emission is measured, the resulting range-uncertainty estimation is at the 0.5 mm scale. When both channels are considered, a theoretical limit on the range uncertainty of a clinical fiducal marker was found to be ±290µm.Significance.Range uncertainty of a heavy-ion beam limits the prescribed treatment plan for cancer patients, especially the direction of the ion beam in relation to any organ at risk. An easy to implement range-verification technique which can be utilized during clinical treatment would allow treatment plans to take full advantage of the sharp fall-off of the Bragg peak without the risk of depositing excessive dose into healthy tissue.

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.

Comparison Between Dimethyl Fumarate, Fingolimod, and Ocrelizumab After Natalizumab Cessation.

Importance: Natalizumab cessation is associated with a risk of rebound disease activity. It is important to identify the optimal switch disease-modifying therapy strategy after natalizumab to limit the risk of severe relapses. Objectives: To compare the effectiveness and persistence of dimethyl fumarate, fingolimod, and ocrelizumab among patients with relapsing-remitting multiple sclerosis (RRMS) who discontinued natalizumab. Design, Setting, and Participants: In this observational cohort study, patient data were collected from the MSBase registry between June 15, 2010, and July 6, 2021. The median follow-up was 2.7 years. This was a multicenter study that included patients with RRMS who had used natalizumab for 6 months or longer and then were switched to dimethyl fumarate, fingolimod, or ocrelizumab within 3 months after natalizumab discontinuation. Patients without baseline data were excluded from the analysis. Data were analyzed from May 24, 2022, to January 9, 2023. Exposures: Dimethyl fumarate, fingolimod, and ocrelizumab. Main Outcomes and Measures: Primary outcomes were annualized relapse rate (ARR) and time to first relapse. Secondary outcomes were confirmed disability accumulation, disability improvement, and subsequent treatment discontinuation, with the comparisons for the first 2 limited to fingolimod and ocrelizumab due to the small number of patients taking dimethyl fumarate. The associations were analyzed after balancing covariates using an inverse probability of treatment weighting method. Results: Among 66 840 patients with RRMS, 1744 had used natalizumab for 6 months or longer and were switched to dimethyl fumarate, fingolimod, or ocrelizumab within 3 months of natalizumab discontinuation. After excluding 358 patients without baseline data, a total of 1386 patients (mean [SD] age, 41.3 [10.6] years; 990 female [71%]) switched to dimethyl fumarate (138 [9.9%]), fingolimod (823 [59.4%]), or ocrelizumab (425 [30.7%]) after natalizumab. The ARR for each medication was as follows: ocrelizumab, 0.06 (95% CI, 0.04-0.08); fingolimod, 0.26 (95% CI, 0.12-0.48); and dimethyl fumarate, 0.27 (95% CI, 0.12-0.56). The ARR ratio of fingolimod to ocrelizumab was 4.33 (95% CI, 3.12-6.01) and of dimethyl fumarate to ocrelizumab was 4.50 (95% CI, 2.89-7.03). Compared with ocrelizumab, the hazard ratio (HR) of time to first relapse was 4.02 (95% CI, 2.83-5.70) for fingolimod and 3.70 (95% CI, 2.35-5.84) for dimethyl fumarate. The HR of treatment discontinuation was 2.57 (95% CI, 1.74-3.80) for fingolimod and 4.26 (95% CI, 2.65-6.84) for dimethyl fumarate. Fingolimod use was associated with a 49% higher risk for disability accumulation compared with ocrelizumab. There was no significant difference in disability improvement rates between fingolimod and ocrelizumab. Conclusion and Relevance: Study results show that among patients with RRMS who switched from natalizumab to dimethyl fumarate, fingolimod, or ocrelizumab, ocrelizumab use was associated with the lowest ARR and discontinuation rates, and the longest time to first relapse.

Baseline smoking status and the long-term risk of death or nonfatal vascular event in people with stroke: a 10-year survival analysis.

BACKGROUND AND PURPOSE: Smoking may exacerbate the risk of death or further vascular events in those with stroke, but data are limited. METHODS: 1589 cases of first-ever and recurrent stroke were recruited between 1996 and 1999 from a defined geographical region in North East Melbourne. Both hospital and nonhospital cases were included. Over a 10-year period, all deaths, recurrent stroke events, and acute myocardial infarctions that were reported at follow-up interviews were validated using medical records. Cox proportional hazards regression was used to assess the association between baseline smoking status (never, ex, and current) and outcome (death, acute myocardial infarction, or recurrent stroke). RESULTS: Patients who were current smokers (Hazard Ratio [HR], 1.30; 95% Confidence Interval [CI], 1.06-1.60; P=0.012) at the time of their stroke had poorer outcome when compared with those who had never smoked. Among those who survived the first 28 days of stroke, current smokers (HR, 1.42; 95% CI, 1.13-1.78; P<0.003) and ex-smokers (HR, 1.18; 95% CI, 1.01-1.39; P=0.039) at baseline had poorer outcome than those who had never smoked. Current smokers also had a greater risk of recurrent events than past smokers (HR, 1.23; 95% CI, 1.00-1.50; P=0.050). CONCLUSIONS: Patients who smoked at the time of their stroke or had smoked before their stroke had greater risk of death or recurrent vascular events when compared with patients who were never smokers. There are benefits of smoking cessation, with ex-smokers appearing to have a lesser risk of recurrent vascular events than current smokers.

Cortical excitability decreases in Lennox-Gastaut syndrome.

PURPOSE: We used transcranial magnetic stimulation (TMS) to investigate cortical excitability changes in Lennox-Gastaut syndrome (LGS), anticipating we would find a marked increase in excitability compared to other patients with refractory epilepsies. METHODS: Eighteen patients with LGS were studied. Motor threshold (MT), short intracortical inhibition (paired pulse TMS at 2 and 5 msec interstimulus intervals [ISIs]), intracortical facilitation (10 and 15 msec ISIs), and long intracortical inhibition (100-300 msec ISIs) were measured. Results were compared to those of 20 patients with chronic refractory idiopathic generalized epilepsy (IGE), 20 patients with chronic refractory focal epilepsy, and 20 healthy nonepilepsy controls. KEY FINDINGS: A significant decrease in cortical excitability was observed in LGS compared to the other two groups with refractory epilepsy as evidenced by increased MT and intracortical inhibition at both short (2, 5 msec ISIs), and long (100-300 msec ISIs) as well as decreased intracortical facilitation (10, 15 msec ISIs), (p < 0.01; effect sizes ranging from 0.3 to 1.8). Cortical excitability was also lower in LGS compared to nonepilepsy controls (increased MT and decreased intracortical facilitation; p < 0.05; effect sizes ranging from 0.5 to 0.9). SIGNIFICANCE: Interictal cortical excitability is decreased in LGS; a feature that distinguishes it from other refractory epilepsy syndromes. This decrease may be an important mechanism for the neurobehavioral comorbidities associated with LGS.

Competition between substrate-mediated π-π stacking and surface-mediated T(g) depression in ultrathin conjugated polymer films.

We report surface and interface effects in dynamics and chain conformation in the thin film of conjugated polymer PCDTBT. To probe dynamic anomalies, we measure the glass transition temperature (T(g)) of PCDTBT films as a function of thickness, and find that there is a significant depression in T(g) for films less than 100 nm thick; a result qualitatively similar to that observed in many other polymer film systems. However, for films less than 40 nm, the T(g) converges to a constant value of 20 K below its bulk value. Grazing incidence X-ray diffraction shows depth-dependent molecular organization that is associated with the unusual thickness-dependent dynamics.

Cortical excitability and neurology: insights into the pathophysiology.

Transcranial magnetic stimulation (TMS) is a technique developed to non-invasively investigate the integrity of human motor corticospinal tracts. Over the last three decades, the use of stimulation paradigms including single-pulse TMS, paired-pulse TMS, repetitive TMS, and integration with EEG and functional imaging have been developed to facilitate measurement of cortical excitability.Through the use of these protocols, TMS has evolved in-to an excellent tool for measuring cortical excitability.TMS has high sensitivity in detecting subtle changes in cortical excitability, and therefore it is also a good measure of disturbances associated with brain disorders. In this review, we appraise the current literature on cortical excitability studies using TMS in neurological disorders.We begin with a brief overview of current TMS measures and then show how these have added to our understand-ing of the underlying mechanisms of brain disorders.