Post covid seizure.

Introduction: Coronaviruses have been suspected to be associated with neurological manifestations in patients with respiratory tract infections. Corona Virus disease (COVID-19) develop seizures as a consequence of hypoxia, metabolic derangements, organ failure, or even cerebral damage that may happen in people with COVID-19. There is scarce data about the development of seizures after recovery from acute COVID-19 illness, especially in those who have had a mild disease. Case: A thirty three year old male patient with recent history of mild COVID-19 disease, with no known comorbidities, no history of substance abuse, presented with history of transient loss of consciousness. On examination had no lateralising signs, tongue bite was present. Inflammatory markers were found to be raised. MRI brain showed no significant abnormality. EEG done showed bilateral intermittent slowing. Conclusion: Post COVID-19 infection, the post-infectious inflammatory response can give rise to many neurological complication, seizure being one among them, as noted in our patient.

Chemical passivation of 2D transition metal dichalcogenides: strategies, mechanisms, and prospects for optoelectronic applications.

The interest in obtaining high-quality monolayer transition metal dichalcogenides (TMDs) for optoelectronic device applications has been growing dramatically. However, the prevalence of defects and unwanted doping in these materials remain challenges, as they both limit optical properties and device performance. Surface chemical treatments of monolayer TMDs have been effective in improving their photoluminescence yield and charge transport properties. In this scenario, a systematic understanding of the underlying mechanism of chemical treatments will lead to a rational design of passivation strategies in future research, ultimately taking a step toward practical optoelectronic applications. We will therefore describe in this mini-review the strategies, progress, mechanisms, and prospects of chemical treatments to passivate and improve the optoelectronic properties of TMDs.

Decoupling excitons from high-frequency vibrations in organic molecules.

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon-carbon stretch modes (1,000-1,600 cm-1) has been thought to be unavoidable1,2. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton-vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680-800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm-1, frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

Correlating activities and defects in (photo)electrocatalysts using in-situ multi-modal microscopic imaging.

Photo(electro)catalysts use sunlight to drive chemical reactions such as water splitting. A major factor limiting photocatalyst development is physicochemical heterogeneity which leads to spatially dependent reactivity. To link structure and function in such systems, simultaneous probing of the electrochemical environment at microscopic length scales and a broad range of timescales (ns to s) is required. Here, we address this challenge by developing and applying in-situ (optical) microscopies to map and correlate local electrochemical activity, with hole lifetimes, oxygen vacancy concentrations and photoelectrode crystal structure. Using this multi-modal approach, we study prototypical hematite (α-Fe2O3) photoelectrodes. We demonstrate that regions of α-Fe2O3, adjacent to microstructural cracks have a better photoelectrochemical response and reduced back electron recombination due to an optimal oxygen vacancy concentration, with the film thickness and extended light exposure also influencing local activity. Our work highlights the importance of microscopic mapping to understand activity, in even seemingly homogeneous photoelectrodes.

Suppression of Dexter transfer by covalent encapsulation for efficient matrix-free narrowband deep blue hyperfluorescent OLEDs.

Hyperfluorescence shows great promise for the next generation of commercially feasible blue organic light-emitting diodes, for which eliminating the Dexter transfer to terminal emitter triplet states is key to efficiency and stability. Current devices rely on high-gap matrices to prevent Dexter transfer, which unfortunately leads to overly complex devices from a fabrication standpoint. Here we introduce a molecular design where ultranarrowband blue emitters are covalently encapsulated by insulating alkylene straps. Organic light-emitting diodes with simple emissive layers consisting of pristine thermally activated delayed fluorescence hosts doped with encapsulated terminal emitters exhibit negligible external quantum efficiency drops compared with non-doped devices, enabling a maximum external quantum efficiency of 21.5%. To explain the high efficiency in the absence of high-gap matrices, we turn to transient absorption spectroscopy. It is directly observed that Dexter transfer from a pristine thermally activated delayed fluorescence sensitizer host can be substantially reduced by an encapsulated terminal emitter, opening the door to highly efficient 'matrix-free' blue hyperfluorescence.

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.

Tofacitinib in Patients Hospitalized With Moderate and Severe COVID-19: Not Just Another Kinase Inhibitor.

Background There has been an intense search for pharmacological agents that can complement corticosteroid therapy in the treatment of severe coronavirus disease 2019 (COVID-19). The Janus kinase inhibitor tofacitinib has shown promise in this regard. This study aimed to determine the impact of adding tofacitinib to standard care on the mortality and total duration of hospital stay in severe COVID-19. Methodology This retrospective study compared the mortality and total duration of hospital stay among patients admitted with severe COVID-19 to a designated COVID-19 hospital in south India who had received tofacitinib in addition to standard care versus standard care alone. Medical case records of severe COVID-19 patients were retrieved and screened for inclusion. Categorical variables such as mortality were expressed as proportions and compared using the chi-square test, while continuous variables such as total duration of hospital stay were compared via the independent t-test. The odds ratio (OR) was calculated for the mortality difference between the two groups. P-values ≤0.05 were considered significant. Results Following the initial screening of 250 medical records, 186 patients were included in the final analysis, of whom 103 had received tofacitinib and 83 had received standard care. There was no significant difference in mortality between the two groups (OR = 1.58 (95% confidence interval = 0.71 to 3.51); p = 0.26). The total duration of hospital stay was significantly longer among those in the tofacitinib group (17.14 ± 8.85 days vs. 14.04 ± 5.48 days; p = 0.01). Conclusions Tofacitinib did not improve the clinical outcomes when used to supplement corticosteroids in the treatment of severe COVID-19.

Direct Imaging of Carrier Funneling in a Dielectric Engineered 2D Semiconductor.

In atomically thin transition-metal dichalcogenides (TMDCs), the environmental sensitivity of the strong Coulomb interaction offers promising approaches to create spatially varying potential landscapes in the same continuous material by tuning its dielectric environment. Thus, allowing for control of transport. However, a scalable and CMOS-compatible method for achieving this is required to harness these effects in practical applications. In addition, because of their ultrashort lifetime, observing the spatiotemporal dynamics of carriers in monolayer TMDCs, on the relevant time scale, is challenging. Here, we pattern and deposit a thin film of hafnium oxide (HfO2) via atomic layer deposition (ALD) on top of a monolayer of WSe2. This allows for the engineering of the dielectric environment of the monolayer and design of heterostructures with nanoscale spatial resolution via a highly scalable postsynthesis methodology. We then directly image the transport of photoexcitations in the monolayer with 50 fs time resolution and few-nanometer spatial precision, using a pump probe microscopy technique. We observe the unidirectional funneling of charge carriers, from the unpatterned to the patterned areas, over more than 50 nm in the first 20 ps with velocities of over 2 × 103 m/s at room temperature. These results demonstrate the possibilities offered by dielectric engineering via ALD patterning, allowing for arbitrary spatial patterns that define the potential landscape and allow for control of the transport of excitations in atomically thin materials. This work also shows the power of the transient absorption methodology to image the motion of photoexcited states in complex potential landscapes on ultrafast time scales.

Fast Near-Infrared Photodetectors Based on Nontoxic and Solution-Processable AgBiS2.

Solution-processable near-infrared (NIR) photodetectors are urgently needed for a wide range of next-generation electronics, including sensors, optical communications and bioimaging. However, it is rare to find photodetectors with >300 kHz cut-off frequencies, especially in the NIR region, and many of the emerging inorganic materials explored are comprised of toxic elements, such as lead. Herein, solution-processed AgBiS2 photodetectors with high cut-off frequencies under both white light (>1 MHz) and NIR (approaching 500 kHz) illumination are developed. These high cut-off frequencies are due to the short transit distances of charge-carriers in the ultrathin photoactive layer of AgBiS2 photodetectors, which arise from the strong light absorption of this material, such that film thicknesses well below 120 nm are sufficient to absorb >65% of NIR to visible light. It is also revealed that ion migration plays a critical role in the photo-response speed of these devices, and its detrimental effects can be mitigated by finely tuning the thickness of the photoactive layer, which is important for achieving low dark current densities as well. These outstanding characteristics enable the realization of air-stable, real-time heartbeat sensors based on NIR AgBiS2 photodetectors, which strongly motivates their future integration in high-throughput systems.

Synthesis and intramolecular singlet fission properties of ortho-phenylene linked oligomers of diphenylhexatriene.

In molecular dimers that undergo intramolecular singlet fission (iSF), efficient iSF is typically accompanied by triplet pair annihilation at rates which prohibit effective triplet harvesting. Collisional triplet pair separation and intramolecular separation by hopping to additional sites in extended oligomers are both strategies that have been reported to be effective for acene based iSF materials in the literature. Herein, a family of highly soluble diphenylhexatriene (DPH) oligomers were synthesized and investigated using transient absorption spectroscopy to determine whether these approaches can be applied to the non-acene singlet fission chromophore, DPH. While iSF proceeds rapidly for all three new materials, neither concentration nor oligomer size result in significantly enhanced triplet pair lifetime relative to the dilute dimer case. These null results indicate the fallibility of the collisional separation and oligomerisation strategies.

Transient reactive phlebitis and intravenous ciprofloxacin: Is there an association?

Transient reactive phlebitis (TRP) is a rare adverse event seen with intravenous infusion of medications. It is characterised by the appearance of erythematous cord-like lesions along the superficial veins proximal to the site of infusion. It is rarely seen with drugs such as morphine, rocuronium, eptifibatide, propofol and vancomycin. The exact pathogenesis is not clear; however, certain proposed mechanisms are due to the direct activation of C-nociceptors, activation of the kallikrein-kinin system with bradykinin release, local mediator release or histamine release. Here, we report a case of TRP due to ciprofloxacin infusion.

Tailoring Interlayer Charge Transfer Dynamics in 2D Perovskites with Electroactive Spacer Molecules.

The family of hybrid organic-inorganic lead-halide perovskites are the subject of intense interest for optoelectronic applications, from light-emitting diodes to photovoltaics to X-ray detectors. Due to the inert nature of most organic molecules, the inorganic sublattice generally dominates the electronic structure and therefore the optoelectronic properties of perovskites. Here, we use optically and electronically active carbazole-based Cz-Ci molecules, where Ci indicates an alkylammonium chain and i indicates the number of CH2 units in the chain, varying from 3 to 5, as cations in the two-dimensional (2D) perovskite structure. By investigating the photophysics and charge transport characteristics of (Cz-Ci)2PbI4, we demonstrate a tunable electronic coupling between the inorganic lead-halide and organic layers. The strongest interlayer electronic coupling was found for (Cz-C3)2PbI4, where photothermal deflection spectroscopy results remarkably reveal an organic-inorganic charge transfer state. Ultrafast transient absorption spectroscopy measurements demonstrate ultrafast hole transfer from the photoexcited lead-halide layer to the Cz-Ci molecules, the efficiency of which increases by varying the chain length from i = 5 to i = 3. The charge transfer results in long-lived carriers (10-100 ns) and quenched emission, in stark contrast to the fast (sub-ns) and efficient radiative decay of bound excitons in the more conventional 2D perovskite (PEA)2PbI4, in which phenylethylammonium (PEA) acts as an inert spacer. Electrical charge transport measurements further support enhanced interlayer coupling, showing increased out-of-plane carrier mobility from i = 5 to i = 3. This study paves the way for the rational design of 2D perovskites with combined inorganic-organic electronic properties through the wide range of functionalities available in the world of organics.

Spatially Resolved Optical Efficiency Measurements of Luminescent Solar Concentrators.

Luminescent solar concentrators (LSCs) are able to concentrate both direct and diffuse solar radiation, and this ability has led to great interest in using them to improve solar energy capture when coupled to traditional photovoltaics (PV). In principle, a large-area LSC could concentrate light onto a much smaller area of PV, thus reducing costs or enabling new architectures. However, LSCs suffer from various optical losses which are hard to quantify using simple measurements of power conversion efficiency. Here, we show that spatially resolved photoluminescence quantum efficiency measurements on large-area LSCs can be used to resolve various loss processes such as out-coupling, self-absorption via emitters, and self-absorption from the LSC matrix. Further, these measurements allow for the extrapolation of device performance to arbitrarily large LSCs. Our results provide insight into the optimization of optical properties and guide the design of future LSCs for improved solar energy capture.

Production of Magnetic Arsenic-Phosphorus Alloy Nanoribbons with Small Band Gaps and High Hole Conductivities.

Quasi-1D nanoribbons provide a unique route to diversifying the properties of their parent 2D nanomaterial, introducing lateral quantum confinement and an abundance of edge sites. Here, a new family of nanomaterials is opened with the creation of arsenic-phosphorus alloy nanoribbons (AsPNRs). By ionically etching the layered crystal black arsenic-phosphorus using lithium electride followed by dissolution in amidic solvents, solutions of AsPNRs are formed. The ribbons are typically few-layered, several micrometers long with widths tens of nanometers across, and both highly flexible and crystalline. The AsPNRs are highly electrically conducting above 130 K due to their small band gap (ca. 0.035 eV), paramagnetic in nature, and have high hole mobilities, as measured with the first generation of AsP devices, directly highlighting their properties and utility in electronic devices such as near-infrared detectors, quantum computing, and charge carrier layers in solar cells.

The relationship between ionic-electronic coupling and transport in organic mixed conductors.

Organic mixed ionic-electronic conductors (OMIECs) directly convert between ionic and electronic charge through electrochemical (de)doping, enabling a wide range of applications in bioelectronics, neuromorphic computing, and energy storage and conversion. While both ionic and electronic transport are individually well characterized, their combined transport has been difficult to describe self-consistently. We use in situ measurements of electrochemical (de)doping of an archetypal OMIEC to inform a quasi-field drift-diffusion model, which accurately captures experimentally measured ion transport across a range of potentials. We find that the chemical potential of holes, which is modulated by changes in doping level, represents a major driving force for mixed charge transport. Using numerical simulations at device-relevant time scales and potentials, we find that the competition between hole drift and diffusion leads to diffuse space charge regions despite high charge densities. This effect is unique to mixed conducting systems where mobile ionic charges can compensate the accumulation or depletion of electronic charge, thereby screening electrostatic driving forces.

Hole-limited electrochemical doping in conjugated polymers.

Simultaneous transport and coupling of ionic and electronic charges is fundamental to electrochemical devices used in energy storage and conversion, neuromorphic computing and bioelectronics. While the mixed conductors enabling these technologies are widely used, the dynamic relationship between ionic and electronic transport is generally poorly understood, hindering the rational design of new materials. In semiconducting electrodes, electrochemical doping is assumed to be limited by motion of ions due to their large mass compared to electrons and/or holes. Here, we show that this basic assumption does not hold for conjugated polymer electrodes. Using operando optical microscopy, we reveal that electrochemical doping speeds in a state-of-the-art polythiophene can be limited by poor hole transport at low doping levels, leading to substantially slower switching speeds than expected. We show that the timescale of hole-limited doping can be controlled by the degree of microstructural heterogeneity, enabling the design of conjugated polymers with improved electrochemical performance.

Resonant Energy Transfer-Mediated Efficient Hole Transfer in the Ternary Blend Organic Solar Cells.

The ternary blend approach accomplished improved spectral coverage and enhanced the power conversion efficiency (PCE) of organic solar cells (OSCs). However, the role of the third component in improving the photovoltaic parameters needs critical analysis. Here, we introduced a wide band gap n-type twisted perylene diimide (TPDI) into the PM6:Y6 blend as a third component that improves spectral coverage and morphology, resulting in an overall increase in the efficiency of the OSCs. TPDI acts as an antenna for efficient energy- and charge-transfer processes. A systematic study compared charge- and energy-transfer dynamics and the orientational dependence nanomorphology of ternary blends with those of their binary counterparts. Femtosecond transient absorption measurements reveal enhanced hole-transfer efficiency in finely tuned ternary mixtures. This study provides a rational approach to identifying a third component to improve light management and morphology. These parameters enhance the energy and charge-transfer processes, improving the PCE of OSCs.

Room-Temperature Photoluminescence Mediated by Sulfur Vacancies in 2D Molybdenum Disulfide.

Atomic defects in monolayer transition metal dichalcogenides (TMDs) such as chalcogen vacancies significantly affect their properties. In this work, we provide a reproducible and facile strategy to rationally induce chalcogen vacancies in monolayer MoS2 by annealing at 600 °C in an argon/hydrogen (95%/5%) atmosphere. Synchrotron X-ray photoelectron spectroscopy shows that a Mo 3d5/2 core peak at 230.1 eV emerges in the annealed MoS2 associated with nonstoichiometric MoSx (0 < x < 2), and Raman spectroscopy shows an enhancement of the ∼380 cm-1 peak that is attributed to sulfur vacancies. At sulfur vacancy densities of ∼1.8 × 1014 cm-2, we observe a defect peak at ∼1.72 eV (referred to as LXD) at room temperature in the photoluminescence (PL) spectrum. The LXD peak is attributed to excitons trapped at defect-induced in-gap states and is typically observed only at low temperatures (≤77 K). Time-resolved PL measurements reveal that the lifetime of defect-mediated LXD emission is longer than that of band edge excitons, both at room and low temperatures (∼2.44 ns at 8 K). The LXD peak can be suppressed by annealing the defective MoS2 in sulfur vapor, which indicates that it is possible to passivate the vacancies. Our results provide insights into how excitonic and defect-mediated PL emissions in MoS2 are influenced by sulfur vacancies at room and low temperatures.

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.

Local symmetry breaking drives picosecond spin domain formation in polycrystalline halide perovskite films.

Photoinduced spin-charge interconversion in semiconductors with spin-orbit coupling could provide a route to optically addressable spintronics without the use of external magnetic fields. However, in structurally disordered polycrystalline semiconductors, which are being widely explored for device applications, the presence and role of spin-associated charge currents remains unclear. Here, using femtosecond circular-polarization-resolved pump-probe microscopy on polycrystalline halide perovskite thin films, we observe the photoinduced ultrafast formation of spin domains on the micrometre scale formed through lateral spin currents. Micrometre-scale variations in the intensity of optical second-harmonic generation and vertical piezoresponse suggest that the spin-domain formation is driven by the presence of strong local inversion symmetry breaking via structural disorder. We propose that this leads to spatially varying Rashba-like spin textures that drive spin-momentum-locked currents, leading to local spin accumulation. Ultrafast spin-domain formation in polycrystalline halide perovskite films provides an optically addressable platform for nanoscale spin-device physics.