Representational similarity scores of digits in the sensorimotor cortex are associated with behavioral performance.

Previous studies aimed to unravel a digit-specific somatotopy in the primary sensorimotor (SM1) cortex. However, it remains unknown whether digit somatotopy is associated with motor preparation and/or motor execution during different types of tasks. We adopted multivariate representational similarity analysis to explore digit activation patterns in response to a finger tapping task (FTT). Sixteen healthy young adults underwent magnetic resonance imaging, and additionally performed an out-of-scanner choice reaction time task (CRTT) to assess digit selection performance. During both the FTT and CRTT, force data of all digits were acquired using force transducers. This allowed us to assess execution-related interference (i.e., digit enslavement; obtained from FTT & CRTT), as well as planning-related interference (i.e., digit selection deficit; obtained from CRTT) and determine their correlation with digit representational similarity scores of SM1. Findings revealed that digit enslavement during FTT was associated with contralateral SM1 representational similarity scores. During the CRTT, digit enslavement of both hands was also associated with representational similarity scores of the contralateral SM1. In addition, right hand digit selection performance was associated with representational similarity scores of left S1. In conclusion, we demonstrate a cortical origin of digit enslavement, and uniquely reveal that digit selection is associated with digit representations in primary somatosensory cortex (S1). Significance statement In current systems neuroscience, it is of critical importance to understand the relationship between brain function and behavioral outcome. With the present work, we contribute significantly to this understanding by uniquely assessing how digit representations in the sensorimotor cortex are associated with planning- and execution-related digit interference during a continuous finger tapping and a choice reaction time task. We observe that digit enslavement (i.e., execution-related interference) finds its origin in contralateral digit representations of SM1, and that deficits in digit selection (i.e., planning-related interference) in the right hand during a choice reaction time task are associated with more overlapping digit representations in left S1. This knowledge sheds new light on the functional contribution of the sensorimotor cortex to everyday motor skills.

Can Ferroelectricity Improve Organic Solar Cells?

Blends of semiconducting (SC) and ferroelectric (FE) polymers have been proposed for applications in resistive memories and organic photovoltaics (OPV). For OPV, the rationale is that the local electric field associated with the dipoles in a blend could aid exciton dissociation, thus improving power conversion efficiency. However, FE polymers either require solvents or processing steps that are incompatible with those required for SC polymers. To overcome this limitation, SC (poly(3-hexylthiophene)) and FE (poly(vinylidene fluoride-trifluoroethylene)) components are incorporated into a block copolymer and thus a path to a facile fabrication of smooth thin films from suitably chosen solvents is achieved. In this work, the photophysical properties and device performance of organic solar cells containing the aforementioned block copolymer consisting of poly(vinylidene fluoride-trifluoroethylene): P(VDF-TrFE), poly(3-hexylthiophene): P3HT and the electron acceptor phenyl-C61 -butyric acid methyl ester: [60]PCBM are explored. A decrease in photovoltaic performance is observed in blends of the copolymer with P3HT:[60]PCBM, which is attributed to a less favorable nanomorphology upon addition of the copolymer. The role of lithium fluoride (the cathode modification layer) is also clarified in devices containing the copolymer, and it is demonstrated that ferroelectric compensation prevents the ferroelectricity of the copolymer from improving photovoltaic performance in SC-FE blends.

Impact of Everolimus and Low-Dose Cyclosporin on Cytomegalovirus Replication and Disease in Pediatric Renal Transplantation.

In order to investigate the hypothesis that the mammalian target of rapamycin inhibitor everolimus (EVR) shows anticytomegalovirus (CMV) activity in pediatric patients, we analyzed the impact of EVR-based immunosuppressive therapy on CMV replication and disease in a large cohort (n = 301) of pediatric kidney allograft recipients. The EVR cohort (n = 59), who also received low-dose cyclosporin, was compared with a control cohort (n = 242), who was administered standard-dose cyclosporin or tacrolimus and an antimetabolite, mostly mycophenolate mofetil (91.7%). Multivariate analysis revealed an 83% lower risk of CMV replication in the EVR cohort than in the control cohort (p = 0.005). In CMV high-risk (donor+/recipient-) patients (n = 88), the EVR-based regimen was associated with a significantly lower rate of CMV disease (0% vs. 14.3%, p = 0.046) than the standard regimen. In patients who had received chemoprophylaxis with (val-)ganciclovir (n = 63), the CMV-free survival rates at 1 year and 3 years posttransplant (100%) were significantly (p = 0.015) higher in the EVR cohort (n = 15) than in the control cohort (n = 48; 1 year, 75.0%; 3 years, 63.3%). Our data suggest that in pediatric patients at high risk of CMV, an EVR-based immunosuppressive regimen is associated with a lower risk of CMV disease than a standard-dose calcineurin inhibitor-based regimen.

Can ferroelectric polarization explain the high performance of hybrid halide perovskite solar cells?

The power conversion efficiency of photovoltaic cells based on the use of hybrid halide perovskites, CH3NH3PbX3 (X = Cl, Br, I), now exceeds 20%. Recently, it was suggested that this high performance originates from the presence of ferroelectricity in the perovskite, which is hypothesized to lower charge recombination in the device. Here, we investigate and quantify the influence of mesoscale ferroelectric polarization on the device performance of perovskite solar cells. We implement a 3D drift diffusion model to describe the solar cell operation. To account for the mesoscale ferroelectricity, we incorporate domains defined by polarization strength, P, in 3D space, forming different polarization landscapes or microstructures. Study of microstructures with highly-ordered polarized domains shows that charge transport and recombination in the solar cell depends significantly on the polarization landscape viz. the orientation of domain boundaries and the size of domains. In the case of the microstructure with random correlated polarization, a realistic scenario, we find indication of the existence of channels for efficient charge transport in the device which leads to lowering of charge recombination, as evidenced by the high fill factor (FF). However, the high open-circuit voltage (VOC), which is typical of high performance perovskite solar cells, is unlikely to be explained by the presence of ferroelectric polarization in the perovskite.

Controlling the assembly of CdS nanorods via solvent and acidity.

We report control over the phase behavior of CdS nanorods via the solvent and acidity. CdS nanorods were synthesized using alkane phosphonic acid ligands, which were replaced after synthesis by a series of aromatic ligands. Change of ligand enabled us to cast films from different solvents. By replacing toluene with ethanol or water the rod-rod interactions dominate over rod-substrate interactions, thereby favoring simple hexagonal ordering (2D). When dispersed in water, a net electrostatic charge on the nanorods could be induced by deprotonating the ligands at high pH. This net charge favors 2D nematic ordering over homeotropic ordering of the nanorods on a substrate. A calculation of the van der Waals and electrostatic interactions is presented that explains the observed influence of solvent and pH.

Describing the light intensity dependence of polymer:fullerene solar cells using an adapted Shockley diode model.

Solar cells are generally optimised for operation under AM1.5 100 mW cm(-2) conditions. This is also typically done for polymer solar cells. However, one of the entry markets for this emerging technology is portable electronics. For this market, the spectral shape and intensity of typical illumination conditions deviate considerably from the standard test conditions (AM1.5, 100 mW cm(-2), at 25 °C). The performance of polymer solar cells is strongly dependent on the intensity and spectral shape of the light source. For this reason the cells should be optimised for the specific application. Here a theoretical model is presented that describes the light intensity dependence of P3HT:[C60]PCBM solar cells. It is based on the Shockley diode equation, combined with a metal-insulator-metal model. In this way the observed light intensity dependence of P3HT:[C60]PCBM solar cells can be described using a 1-diode model, allowing fast optimization of polymer solar cells and module design.

Close-Space Sublimation as a Scalable Method for Perovskite Solar Cells.

Vacuum techniques for perovskite photovoltaics (PV) are promising for their scalability but are rarely studied with techniques readily adaptable for industry. In this work, we study the use of close-space sublimation (CSS) for making perovskite solar cells, a technique that has seen widespread use in industry, including in PV, and benefits from high material-transfer and low working pressures. A pressed pellet of formamidinium iodide (FAI) can be used multiple times as an organic source, without needing replacement. Using CSS at a rough vacuum (10 mbar), efficient cesium formamidinium lead iodide perovskite based solar cells are obtained reaching a maximum photoconversion efficiency (PCE) of 18.7%. They maintain their performance for >650 h when thermally stressed at 85 °C in a nitrogen environment. To explain the initial rise in PCE upon heating, we used drift-diffusion simulations and identified a reduction in bulk trap density as the primary factor.

Sequential vs myeloablative vs reduced intensity conditioning for patients with myelodysplastic syndromes with an excess of blasts at time of allogeneic haematopoietic cell transplantation: a retrospective study by the chronic malignancies working party of the EBMT.

The optimal conditioning for patients with higher risk MDS receiving potentially curative allogeneic haematopoietic stem cell transplant(allo-HCT) remains to be defined. This is particularly the case for patients with excess of blasts at time of allo-HCT. Sequential (Seq) conditioning, whereby chemotherapy is followed rapidly by transplant conditioning, offers an opportunity to decrease disease burden, potentially improving outcomes allo-HCT outcomes. Herein we present the only analysis comparing Seq to myeloablative (MAC) and reduced intensity conditioning (RIC) specifically focussed on MDS patients with excess of blasts at allo-HCT. 303 patients were identified in the EBMT registry, receiving RIC (n = 158), Seq (n = 105), and MAC (n = 40). Median follow-up was 67.2 months and median age at allo-HCT was 59.5 years (IQR 53.5-65.6). For the entire cohort, 3 y overall survival (OS) was 50% (95% CI 45-56%) and relapse free survival (RFS) 45% (95% CI 40-51%). No significant differences in OS (log-rank p = 0.13) and RFS (log-rank p = 0.18) were observed between conditioning protocols. On multivariable analysis, lower performance status, worse IPSS-R cytogenetics, sibling donor (compared to 8/8 MUD) and ≥20% blasts at allo-HCT were associated with worse outcomes. In conclusion, the Seq protocol did little to influence the outcome in this high-risk group of patients, with outcomes mostly determined by baseline disease risk and patient characteristics such as performance status.

Vacuum-Deposited Cesium Tin Iodide Thin Films with Tunable Thermoelectric Properties.

Most current thermoelectric materials have important drawbacks, such as toxicity, scarceness, and peak operating temperatures above 300 °C. Herein, we report the thermoelectric properties of different crystalline phases of Sn-based perovskite thin films. The 2D phase, Cs2SnI4, is obtained through vacuum thermal deposition and easily converted into the black ß phase of CsSnI3 (B-ß CsSnI3) by annealing at 150 °C. B-ß CsSnI3 is a p-type semiconductor with a figure of merit (ZT) ranging from 0.021 to 0.033 for temperatures below 100 °C, which makes it a promising candidate to power small electronic devices such as wearable sensors which may be interconnected in the so-called Internet of Things. The B-ß phase is stable in nitrogen, whereas it spontaneously oxidizes to Cs2SnI6 upon exposure to air. Cs2SnI6 shows a negative Seebeck coefficient and an ultralow thermal conductivity. However, the ZT values are 1 order of magnitude lower than for B-ß CsSnI3 due to a considerably lower electrical conductivity.

A method for identifying the cause of inefficient salt-doping in organic semiconductors.

Doping to enhance the electrical conductivity of organic semiconductors is not without its challenges: The efficacy of this process depends on many factors and it is not always clear how to remedy poor doping. In the case of doping with salts, one of the possible causes of poor doping is a limited yield of integer charge transfer resulting in the presence of both cations and anions in the film. The charge of such ions can severely limit the electrical conductivity, but their presence is not easily determined. Here we introduce a set of simple conductivity measurements to determine whether poor doping in the case where the dopant is a salt is due to limited integer charge transfer. By tracking how the conductivity changes over time when applying a bias voltage for an extended amount of time we can pinpoint whether unwanted ions are present in the film. Firstly, we introduce the principle of this approach by performing numerical simulations that include the movement of ions. We show that the conductivity can increase or decrease depending on the type of ions present in the film. Next, we show that the movement of these dopant ions causes a build-up of space-charge, which makes the current-voltage characteristic non-linear. Next, we illustrate how this approach may be used in practice by doping a fullerene derivative with a series of organic salts. We thus provide a tool to make the optimization of doping more rational.

Backbone-driven host-dopant miscibility modulates molecular doping in NDI conjugated polymers.

Molecular doping is the key to enabling organic electronic devices, however, the design strategies to maximize doping efficiency demands further clarity and comprehension. Previous reports focus on the effect of the side chains, but the role of the backbone is still not well understood. In this study, we synthesize a series of NDI-based copolymers with bithiophene, vinylene, and acetylenic moieties (P1G, P2G, and P3G, respectively), all containing branched triethylene glycol side chains. Using computational and experimental methods, we explore the impact of the conjugated backbone using three key parameters for doping in organic semiconductors: energy levels, microstructure, and miscibility. Our experimental results show that P1G undergoes the most efficient n-type doping owed primarily to its higher dipole moment, and better host-dopant miscibility with N-DMBI. In contrast, P2G and P3G possess more planar backbones than P1G, but the lack of long-range order, and poor host-dopant miscibility limit their doping efficiency. Our data suggest that backbone planarity alone is not enough to maximize the electrical conductivity (σ) of n-type doped organic semiconductors, and that backbone polarity also plays an important role in enhancing σ via host-dopant miscibility. Finally, the thermoelectric properties of doped P1G exhibit a power factor of 0.077 µW m-1 K-2, and ultra-low in-plane thermal conductivity of 0.13 W m-1K-1 at 5 mol% of N-DMBI, which is among the lowest thermal conductivity values reported for n-type doped conjugated polymers.

Scaling theory for percolative charge transport in disordered molecular semiconductors.

We present a scaling theory for charge transport in disordered molecular semiconductors that extends percolation theory by including bonds with conductances close to the percolating one in the random-resistor network representing charge hopping. A general and compact expression is given for the charge mobility for Miller-Abrahams and Marcus hopping on different lattices with Gaussian energy disorder, with parameters determined from numerically exact results. The charge-concentration dependence is universal. The model-specific temperature dependence can be used to distinguish between the hopping models.

Validity of the Einstein relation in disordered organic semiconductors.

It is controversial whether energetic disorder in semiconductors is already sufficient to violate the classical Einstein relation, even in the case of thermal equilibrium. We demonstrate that the Einstein relation is violated only under nonequilibrium conditions due to deeply trapped carriers, as in diffusion-driven current measurements on organic single-carrier diodes. Removal of these deeply trapped carriers by recombination unambiguously proves the validity of the Einstein relation in disordered semiconductors in thermal (quasi)equilibrium.

Trap-assisted recombination in disordered organic semiconductors.

The trap-assisted recombination of electrons and holes in organic semiconductors is investigated. The extracted capture coefficients of the trap-assisted recombination process are thermally activated with an identical activation energy as measured for the hole mobility µ(p). We demonstrate that the rate limiting step for this mechanism is the diffusion of free holes towards trapped electrons in their mutual Coulomb field, with the capture coefficient given by (q/ε)µ(p). As a result, both the bimolecular and trap-assisted recombination processes in organic semiconductors are governed by the charge carrier mobilities, allowing predictive modeling of organic light-emitting diodes.

Revealing Charge Carrier Mobility and Defect Densities in Metal Halide Perovskites via Space-Charge-Limited Current Measurements.

Space-charge-limited current (SCLC) measurements have been widely used to study the charge carrier mobility and trap density in semiconductors. However, their applicability to metal halide perovskites is not straightforward, due to the mixed ionic and electronic nature of these materials. Here, we discuss the pitfalls of SCLC for perovskite semiconductors, and especially the effect of mobile ions. We show, using drift-diffusion (DD) simulations, that the ions strongly affect the measurement and that the usual analysis and interpretation of SCLC need to be refined. We highlight that the trap density and mobility cannot be directly quantified using classical methods. We discuss the advantages of pulsed SCLC for obtaining reliable data with minimal influence of the ionic motion. We then show that fitting the pulsed SCLC with DD modeling is a reliable method for extracting mobility, trap, and ion densities simultaneously. As a proof of concept, we obtain a trap density of 1.3 × 1013 cm-3, an ion density of 1.1 × 1013 cm-3, and a mobility of 13 cm2 V-1 s-1 for a MAPbBr3 single crystal.

Controlling n-Type Molecular Doping via Regiochemistry and Polarity of Pendant Groups on Low Band Gap Donor-Acceptor Copolymers.

We demonstrate the impact of the type and position of pendant groups on the n-doping of low-band gap donor-acceptor (D-A) copolymers. Polar glycol ether groups simultaneously increase the electron affinities of D-A copolymers and improve the host/dopant miscibility compared to nonpolar alkyl groups, improving the doping efficiency by a factor of over 40. The bulk mobility of the doped films increases with the fraction of polar groups, leading to a best conductivity of 0.08 S cm-1 and power factor (PF) of 0.24 µW m-1 K-2 in the doped copolymer with the polar pendant groups on both the D and A moieties. We used spatially resolved absorption spectroscopy to relate commensurate morphological changes to the dispersion of dopants and to the relative local doping efficiency, demonstrating a direct relationship between the morphology of the polymer phase, the solvation of the molecular dopant, and the electrical properties of doped films. Our work offers fundamental new insights into the influence of the physical properties of pendant chains on the molecular doping process, which should be generalizable to any molecularly doped polymer films.

Molecular Doping Directed by a Neutral Radical.

Molecular doping makes possible tunable electronic properties of organic semiconductors, yet a lack of control of the doping process narrows its scope for advancing organic electronics. Here, we demonstrate that the molecular doping process can be improved by introducing a neutral radical molecule, namely nitroxyl radical (2,2,6,6-teramethylpiperidin-i-yl) oxyl (TEMPO). Fullerene derivatives are used as the host and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazoles (DMBI-H) as the n-type dopant. TEMPO can abstract a hydrogen atom from DMBI-H and transform the latter into a much stronger reducing agent DMBI•, which efficiently dopes the fullerene derivative to yield an electrical conductivity of 4.4 S cm-1. However, without TEMPO, the fullerene derivative is only weakly doped likely by a hydride transfer following by an inefficient electron transfer. This work unambiguously identifies the doping pathway in fullerene derivative/DMBI-H systems in the presence of TEMPO as the transfer of a hydrogen atom accompanied by electron transfer. In the absence of TEMPO, the doping process inevitably leads to the formation of less symmetrical hydrogenated fullerene derivative anions or radicals, which adversely affect the molecular packing. By adding TEMPO we can exclude the formation of such species and, thus, improve charge transport. In addition, a lower temperature is sufficient to meet an efficient doping process in the presence of TEMPO. Thereby, we provide an extra control of the doping process, enabling enhanced thermoelectric performance at a low processing temperature.

Trends in allogeneic haematopoietic cell transplantation for myelofibrosis in Europe between 1995 and 2018: a CMWP of EBMT retrospective analysis.

We performed a retrospective assessment of patient- and transplant-specific characteristics and outcomes for 4142 patients undergoing allogeneic haematopoietic cell transplant for myelofibrosis between 1995 and 2018 across 278 centres. Activity increased steadily across the four analysed eras (<2006, 2006-2010, 2011-2014 and 2015-2018). Median recipient age increased over time between the earliest and most recent cohort (49.4 years (range, 20.1-68) versus 59.3 years (range, 18.1-78.1). Increasing number of patients with a Karnofsky performance status <90 underwent transplant over time. Increased utilisation of matched unrelated donors was apparent (<2006, 22.5% versus 2015-18, 45.2%; p < 0.001). Decreased use of myeloablative conditioning, increased use of busulphan-based platforms and anti-thymocyte globulin was evident. Of note, rates of acute (a)GVHD grade II-IV by day +100 decreased over time (p = 0.027) as did rates of chronic (c) GVHD, predominantly extensive cGVHD (<2006, 36% (31-41%) versus 2015-18, 23% (21-25%); p = 0.001). Overall, significant factors associated with worse overall survival and non-relapse mortality (NRM) remained older age, use of donors other than matched sibling, recipient CMV seropositivity and a lower Karnofsky performance status (<90). Multivariable analysis demonstrated improvements in overall survival and reductions in relapse risk over time with stable NRM rates despite increasing numbers of older, less fit patients and use of unrelated donors.

Amphipathic Side Chain of a Conjugated Polymer Optimizes Dopant Location toward Efficient N-Type Organic Thermoelectrics.

There is no molecular strategy for selectively increasing the Seebeck coefficient without reducing the electrical conductivity for organic thermoelectrics. Here, it is reported that the use of amphipathic side chains in an n-type donor-acceptor copolymer can selectively increase the Seebeck coefficient and thus increase the power factor by a factor of ≈5. The amphipathic side chain contains an alkyl chain segment as a spacer between the polymer backbone and an ethylene glycol type chain segment. The use of this alkyl spacer does not only reduce the energetic disorder in the conjugated polymer film but can also properly control the dopant sites away from the backbone, which minimizes the adverse influence of counterions. As confirmed by kinetic Monte Carlo simulations with the host-dopant distance as the only variable, a reduced Coulombic interaction resulting from a larger host-dopant distance contributes to a higher Seebeck coefficient for a given electrical conductivity. Finally, an optimized power factor of 18 µW m-1 K-2 is achieved in the doped polymer film. This work provides a facile molecular strategy for selectively improving the Seebeck coefficient and opens up a new route for optimizing the dopant location toward realizing better n-type polymeric thermoelectrics.

The effect of three-dimensional morphology on the efficiency of hybrid polymer solar cells.

The efficiency of polymer solar cells critically depends on the intimacy of mixing of the donor and acceptor semiconductors used in these devices to create charges and on the presence of unhindered percolation pathways in the individual components to transport holes and electrons. The visualization of these bulk heterojunction morphologies in three dimensions has been challenging and has hampered progress in this area. Here, we spatially resolve the morphology of 2%-efficient hybrid solar cells consisting of poly(3-hexylthiophene) as the donor and ZnO as the acceptor in the nanometre range by electron tomography. The morphology is statistically analysed for spherical contact distance and percolation pathways. Together with solving the three-dimensional exciton-diffusion equation, a consistent and quantitative correlation between solar-cell performance, photophysical data and the three-dimensional morphology has been obtained for devices with different layer thicknesses that enables differentiating between generation and transport as limiting factors to performance.