Improved Strain Transfer Efficiency in Large-Area Two-Dimensional MoS2 Obtained by Gold-Assisted Exfoliation.

Strain engineering represents a pivotal approach to tailoring the optoelectronic properties of two-dimensional (2D) materials. However, typical bending experiments often encounter challenges, such as layer slippage and inefficient transfer of strain from the substrate to the 2D material, hindering the realization of their full potential. In our study, using molybdenum disulfide (MoS2) as a model 2D material, we have demonstrated that layers obtained through gold-assisted exfoliation on flexible polycarbonate substrates can achieve high-efficient strain transfer while also mitigating slippage effects, owing to the strong interfacial interaction established between MoS2 and gold. We employ differential reflectance and Raman spectroscopy for monitoring strain changes. We successfully applied uniaxial strains of up to 3% to trilayer MoS2, resulting in a notable energy shift of 168 meV. These values are comparable only to those obtained in encapsulated samples with organic polymers.

Urea-Comprising Single Core Diketopyrrolopyrrole Derivatives: Exploring the Synthesis, Self-Assembly and Charge Transport Properties.

Supramolecular electronics exploits the distinctive features stemming from noncovalent interactions, guiding the self-assembly of molecules to craft materials endowed with customized electronic functionalities. Hydrogen-bonded materials, characterized by their capacity to establish dynamic and stable networks, introduce an extra dimension to the development of supramolecular electronic systems. This study presents a comparative analysis of two remarkably small semiconductors utilizing diketopyrrolopyrrole functionalized with urea units as hydrogen-bonding motifs, strategically positioned at opposing ends of the conjugated core. We show how the subtle distinction in functionalization not only influences morphology and self-assembly dynamics via hydrogen-bonding and π-π stacking formation, but also holds significant consequences for ultimate charge transport properties. Our observations into the interplay of noncovalent interactions provide valuable insights and strategic pathways for the design of novel materials with enhanced electronic characteristics.

Acrylates Polymerization on Covalent Plasma-Assisted Functionalized Graphene: A Route to Synthesize Hybrid Functional Materials.

The modification of the surface properties of graphene with polymers provides a method for expanding its scope into new applications as a hybrid material. Unfortunately, the chemical inertness of graphene hinders the covalent functionalization required to build them up. Developing new strategies to enhance the graphene chemical activity for efficient and stable functionalization, while preserving its electronic properties, is a major challenge. We here devise a covalent functionalization method that is clean, reproducible, scalable, and technologically relevant for the synthesis of a large-scale, substrate-supported graphene-polymer hybrid material. In a first step, hydrogen-assisted plasma activation of p-aminophenol (p-AP) linker molecules produces their stable and covalent attachment to large-area graphene. Second, an in situ radical polymerization reaction of 2-hydroxyethyl acrylate (HEA) is carried out on the functionalized surface, leading to a graphene-polymer hybrid functional material. The functionalization with a hydrophilic and soft polymer modifies the hydrophobicity of graphene and might enhance its biocompatibility. We have characterized these hybrid materials by atomic force microscopy (AFM), X-Ray photoelectron spectroscopy (XPS) and Raman spectroscopy and studied their electrical response, confirming that the graphene/p-AP/PHEA architecture is anchored covalently by the sp3 hybridization and controlled polymerization reaction on graphene, retaining its suitable electronic properties. Among all the possibilities, we assess the proof of concept of this graphene-based hybrid platform as a humidity sensor. An enhanced sensitivity is obtained in comparison with pristine graphene and related materials. This functional nanoarchitecture and the two-step strategy open up future potential applications in sensors, biomaterials, or biotechnology fields.

High-Throughput Mechanical Exfoliation for Low-Cost Production of van der Waals Nanosheets.

A method is presented for scaling up the production of flakes of van der Waals materials via mechanical exfoliation. Using a roll-to-roll setup and an automatized, massive parallel exfoliation process, adhesive tapes with a high density of nanosheets of van der Waals materials are produced. The technique allows for obtaining a good trade-off between large lateral size and excellent area scalability, while also maintaining low cost. The potential of the method is demonstrated through the successful fabrication of field effect transistors and flexible photodetectors in large batches. This low-cost method to produce large area films out of mechanically exfoliated flakes is very general, and it can be applied to a variety of substrates and van der Waals materials and, moreover, it can be used to combine different van der Waals materials on top of each other. Therefore, it is believed that this production method opens an interesting avenue for fabrication of low-cost devices while maintaining a good scalability and performance.

Approaching the Intrinsic Properties of Moiré Structures Using Atomic Force Microscopy Ironing.

Stacking monolayers of transition metal dichalcogenides (TMDs) has led to the discovery of a plethora of new exotic phenomena, resulting from moiré pattern formation. Due to the atomic thickness and high surface-to-volume ratio of heterostructures, the interfaces play a crucial role. Fluctuations in the interlayer distance affect interlayer coupling and moiré effects. Therefore, to access the intrinsic properties of the TMD stack, it is essential to obtain a clean and uniform interface between the layers. Here, we show that this is achieved by ironing with the tip of an atomic force microscope. This post-stacking procedure dramatically improves the homogeneity of the interfaces, which is reflected in the optical response of the interlayer exciton. We demonstrate that ironing improves the layer coupling, enhancing moiré effects and reducing disorder. This is crucial for the investigation of TMD heterostructure physics, which currently suffers from low reproducibility.

Large Magnetoresistance of Isolated Domain Walls in La2/3 Sr1/3 MnO3 Nanowires.

Generation, manipulation, and sensing of magnetic domain walls are cornerstones in the design of efficient spintronic devices. Half-metals are amenable for this purpose as large low field magnetoresistance signals can be expected from spin accumulation at spin textures. Among half metals, La1- x Srx MnO3 (LSMO) manganites are considered as promising candidates for their robust half-metallic ground state, Curie temperature above room temperature (Tc = 360 K, for x = 1/3), and chemical stability. Yet domain wall magnetoresistance is poorly understood, with large discrepancies in the reported values and conflicting interpretation of experimental data due to the entanglement of various source of magnetoresistance, namely, spin accumulation, anisotropic magnetoresistance, and colossal magnetoresistance. In this work, the domain wall magnetoresistance is measured in LSMO cross-shape nanowires with single-domain walls nucleated across the current path. Magnetoresistance values above 10% are found to be originating at the spin accumulation caused by the mistracking effect of the spin texture of the domain wall by the conduction electrons. Fundamentally, this result shows the importance on non-adiabatic processes at spin textures despite the strong Hund coupling to the localized t2g electrons of the manganite. These large magnetoresistance values are high enough for encoding and reading magnetic bits in future oxide spintronic sensors.

Enhanced Field-Effect Control of Single-Layer WS2 Optical Features by hBN Full Encapsulation.

The field-effect control of the electrical and optical properties of two-dimensional (2D) van der Waals semiconductors (vdW) is one important aspect of this novel class of materials. Thanks to their reduced thickness and decreased screening, electric fields can easily penetrate in a 2D semiconductor and thus modulate their charge density and their properties. In literature, the field effect is routinely used to fabricate atomically thin field-effect transistors based on 2D semiconductors. Apart from the tuning of the electrical transport, it has been demonstrated that the field effect can also be used to modulate the excitonic optical emission of 2D transition metal dichalcogenides such as MoS2 or WSe2. In this paper, we present some recent experiments on the field-effect control of the optical and excitonic properties of the monolayer WS2. Using the deterministic transfer of van der Waals materials, we fabricate planar single-layer WS2 devices contacted by a gold electrode and partially sandwiched between two insulating hexagonal boron nitride (hBN) flakes. Thanks to the planar nature of the device, we can optically access both the hBN encapsulated and the unencapsulated WS2 regions and compare the field-effect control of the exciton population in the two cases. We find that the encapsulation strongly increases the range of tunability of the optical emission of WS2, allowing us to tune the photoluminescence emission from excitons-dominated to trions-dominated. We also discuss how the full encapsulation of WS2 with hBN helps reduce spurious hysteretic effects in the field-effect control of the optical properties, similar to what has been reported for 2D vdW field-effect transistors.

Improving the conductivity of graphite-based films by rapid laser annealing.

We present a method to anneal devices based on graphite films on paper and polycarbonate substrates. The devices are created using four different methods: spray-on films, graphite pencil-drawn films, liquid-phase exfoliated graphite films, and graphite powder abrasion-applied films. We characterize the optical properties of the films before and after laser annealing and report the two-terminal resistance of the devices for increased laser power density. We find the greatest improvement (16× reduction) in the resistance of spray-on film devices starting from 25.0 kΩ and reaching 1.6 kΩ at the highest annealing power densities. These improvements are attributed to local laser ablation of binders, stabilizers, and solvent residues left in the film after fabrication. This work highlights the utility of focused laser annealing for spray-on, drawn, printed, and abrasion fabricated films on substrates sensitive to heat/thermal treatments.

Combining Freestanding Ferroelectric Perovskite Oxides with Two-Dimensional Semiconductors for High Performance Transistors.

We demonstrate the fabrication of field-effect transistors based on single-layer MoS2 and a thin layer of BaTiO3 (BTO) dielectric, isolated from its parent epitaxial template substrate. Thin BTO provides an ultrahigh-κ gate dielectric effectively screening Coulomb scattering centers. These devices show mobilities substantially larger than those obtained with standard SiO2 dielectrics and comparable with values obtained with hexagonal boron nitride, a dielectric employed for fabrication of high-performance two-dimensional (2D) based devices. Moreover, the ferroelectric character of BTO induces a robust hysteresis of the current vs gate voltage characteristics, attributed to its polarization switching. This hysteresis is strongly suppressed when the device is warmed up above the tetragonal-to-cubic transition temperature of BTO that leads to a ferroelectric-to-paraelectric transition. This hysteretic behavior is attractive for applications in memory storage devices. Our results open the door to the integration of a large family of complex oxides exhibiting strongly correlated physics in 2D-based devices.

Is conventional brain MRI useful for the diagnosis of cluster headache in patients who meet ICHD-3 criteria? Experience in three hospitals in Spain.

OBJECTIVE: To assess the frequency of symptomatic structural lesions and the diagnostic yield of conventional brain MRI in cluster headache (CH). BACKGROUND: In contrast to migraine, brain MRI is recommended in patients with CH to exclude potential mimics. The prevalence of symptomatic CH is not known. METHODS: We retrospectively analysed in detail the brain MRIs of patients diagnosed as CH in 3 Neurology Services in Spain and reviewed their clinical history. Clinical diagnoses were reassessed based on the ICHD-3 criteria. RESULTS: We included 130 patients: 113 (86.9%) were male; mean age at diagnosis being 41.4 years (range 7-82). Forty-nine (37.7%) showed some abnormal MRI finding. Only in two cases potential symptomatic lesions were found: one trigeminal schwannoma and one craneopharyngioma, but both presented atypical features (facial hypoesthesia on examination and episodes of prolonged duration that had progressed to continuous refractory pain without specific pattern, respectively) and therefore did not fulfil the ICHD-3 CH criteria. The remaining abnormal MRI findings were: white matter lesions (24 patients; 18.4%), sinus inflammatory changes (13; 10.0%), small arachnoid cysts (5; 3.8%), empty sella turca (3; 2.3%), and other unspecific findings (8; 6.2%). All of them were not symptomatic based on neuroimaging characteristics, clinical course and response to treatment. CONCLUSIONS: Brain MRI in patients who meet ICHD-3 CH criteria, with no atypical clinical features, does not show any clinically-relevant findings, suggesting that these criteria are highly predictive of its primary origin and that systematic MRI is not useful for the diagnosis of typical CH.

Optical-Based Thickness Measurement of MoO3 Nanosheets.

Considering that two-dimensional (2D) molybdenum trioxide has acquired more attention in the last few years, it is relevant to speed up thickness identification of this material. We provide two fast and non-destructive methods to evaluate the thickness of MoO3 flakes on SiO2/Si substrates. First, by means of quantitative analysis of the apparent color of the flakes in optical microscopy images, one can make a first approximation of the thickness with an uncertainty of ±3 nm. The second method is based on the fit of optical contrast spectra, acquired with micro-reflectance measurements, to a Fresnel law-based model that provides an accurate measurement of the flake thickness with ±2 nm of uncertainty.

Processing and Study of Optical and Electrical Properties of (Mg, Al) Co-Doped ZnO Thin Films Prepared by RF Magnetron Sputtering for Photovoltaic Application.

In this study, high transparent thin films were prepared by radio frequency (RF) magnetron sputtering from a conventional solid state target based on ZnO:MgO:Al2O3 (10:2 wt %) material. The films were deposited on glass and silicon substrates at the different working pressures of 0.21, 0.61, 0.83 and 1 Pa, 300 °C and 250 W of power. X-ray diffraction patterns (XRD), atomic force microscopy (AFM), UV-vis absorption and Hall effect measurements were used to evaluate the structural, optical, morphological and electrical properties of thin films as a function of the working pressure. The optical properties of the films, such as the refractive index, the extinction coefficient and the band gap energy were systematically studied. The optical band gap of thin films was estimated from the calculated absorption coefficient. That parameter, ranged from 3.921 to 3.655 eV, was hardly influenced by the working pressure. On the other hand, the lowest resistivity of 8.8 × 10-2 Ω cm-1 was achieved by the sample deposited at the lowest working pressure of 0.21 Pa. This film exhibited the best optoelectronic properties. All these data revealed that the prepared thin layers would offer a good capability to be used in photovoltaic applications.

Graphene Oxide Microfibers Promote Regenerative Responses after Chronic Implantation in the Cervical Injured Spinal Cord.

Spinal cord injury (SCI) is characterized by the disruption of neuronal axons and the creation of an inhibitory environment for spinal tissue regeneration. For decades, researchers and clinicians have been devoting a great effort to develop novel therapeutic approaches which include the fabrication of biocompatible implants that could guide neural tissue repair in the lesion site in an attempt to recover the functionality of the nervous tissue. In this context, although fiberlike structures have been hypothesized to serve as a topographical guidance for axonal regrowth, work on the exploration of this type of materials is still limited for SCI. Aiming to develop such guidance platforms, we recently designed and explored in vitro reduced graphene oxide materials in the shape of microfibers (rGO-MFs). After preliminary studies to assess the feasibility of their implantation at the injured spinal cord in vivo, no evident signs of subacute local toxicity were noticed (10 days of implantation). In this work, we specifically examine for the first time the regenerative potential of these scaffolds, slightly modified in their fabrication for improved reproducibility, when chronically interfaced with a cervical spinal cord injury. After extensive characterization of their physicochemical properties and in vitro experiments with neural progenitor cells, their neural regenerative capacity in vivo is investigated in a rat experimental model of SCI after 4 months of implantation (chronic state). Behavioral tests involving the use of forelimbs are performed. Immunofluorescence studies evidence that rGO-MFs scaffolds foster the presence of neuronal structures along with blood vessels both within the epicenter and in the surroundings of the lesion area. Moreover, the inflammatory response does not worsen by the presence of this material. These findings outline the potential of rGO-MF-based scaffolds to promote regenerative features at the injured spinal cord such as axonal and vascular growth. Further studies including biological functionalization might improve their therapeutic potential by a synergistic effect of topographical and chemical cues, thus boosting neural repair after SCI.

New Concepts for Production of Scalable Single Layer Oxidized Regions by Local Anodic Oxidation of Graphene.

A deep comprehension of the local anodic oxidation process in 2D materials is achieved thanks to an extensive experimental and theoretical study of this phenomenon in graphene. This requires to arrange a novel instrumental device capable to generate separated regions of monolayer graphene oxide (GO) over graphene, with any desired size, from micrometers to unprecedented mm2 , in minutes, a milestone in GO monolayer production. GO regions are manufactured by overlapping lots of individual oxide spots of thousands µm2 area. The high reproducibility and circular size of the spots allows not only an exhaustive experimental characterization inside, but also establishing an original model for oxide expansion which, from classical first principles, overcomes the traditional paradigm of the water bridge, and is applicable to any 2D-material. This tool predicts the oxidation behavior with voltage and exposure time, as well as the expected electrical current along the process. The hitherto unreported transient current is measured during oxidation, gaining insight on its components, electrochemical and transport. Just combining electrical measurements and optical imaging estimating carrier mobility and degree of oxidation is possible. X-ray photoelectron spectroscopy reveals a graphene oxidation about 30%, somewhat lower to that obtained by Hummers' method.

Direct synthesis of graphene on silicon oxide by low temperature plasma enhanced chemical vapor deposition.

Direct graphene growth on silicon with a native oxide using plasma enhanced chemical vapour deposition at low temperatures [550 °C-650 °C] is demonstrated for the first time. It is shown that the fine-tuning of a two-step synthesis with gas mixtures C2H2/H2 yields monolayer and few layer graphene films with a controllable domain size from 50 nm to more than 300 nm and the sheet resistance ranging from 8 kΩ sq-1 to less than 1.8 kΩ sq-1. Differences are understood in terms of the interaction of the plasma species - chiefly atomic H - with the deposited graphene and the native oxide layer. The proposed low temperature direct synthesis on an insulating substrate does not require any transfer processes and improves the compatibility with the current industrial processes.

Clinical, genetic and neuropathological characterization of spinocerebellar ataxia type 37.

The autosomal dominant spinocerebellar ataxias (SCAs) consist of a highly heterogeneous group of rare movement disorders characterized by progressive cerebellar ataxia variably associated with ophthalmoplegia, pyramidal and extrapyramidal signs, dementia, pigmentary retinopathy, seizures, lower motor neuron signs, or peripheral neuropathy. Over 41 different SCA subtypes have been described evidencing the high clinical and genetic heterogeneity. We previously reported a novel spinocerebellar ataxia type subtype, SCA37, linked to an 11-Mb genomic region on 1p32, in a large Spanish ataxia pedigree characterized by ataxia and a pure cerebellar syndrome distinctively presenting with early-altered vertical eye movements. Here we demonstrate the segregation of an unstable intronic ATTTC pentanucleotide repeat mutation within the 1p32 5' non-coding regulatory region of the gene encoding the reelin adaptor protein DAB1, implicated in neuronal migration, as the causative genetic defect of the disease in four Spanish SCA37 families. We describe the clinical-genetic correlation and the first SCA37 neuropathological findings caused by dysregulation of cerebellar DAB1 expression. Post-mortem neuropathology of two patients with SCA37 revealed severe loss of Purkinje cells with abundant astrogliosis, empty baskets, occasional axonal spheroids, and hypertrophic fibres by phosphorylated neurofilament immunostaining in the cerebellar cortex. The remaining cerebellar Purkinje neurons showed loss of calbindin immunoreactivity, aberrant dendrite arborization, nuclear pathology including lobulation, irregularity, and hyperchromatism, and multiple ubiquitinated perisomatic granules immunostained for DAB1. A subpopulation of Purkinje cells was found ectopically mispositioned within the cerebellar cortex. No significant neuropathological alterations were identified in other brain regions in agreement with a pure cerebellar syndrome. Importantly, we found that the ATTTC repeat mutation dysregulated DAB1 expression and induced an RNA switch resulting in the upregulation of reelin-DAB1 and PI3K/AKT signalling in the SCA37 cerebellum. This study reveals the unstable ATTTC repeat mutation within the DAB1 gene as the underlying genetic cause and provides evidence of reelin-DAB1 signalling dysregulation in the spinocerebellar ataxia type 37.

In-Situ Scrutiny of the Relationship between Polymorphic Phases and Properties of Self-Assembled Monolayers of a Biphenyl Based Thiol.

Two polymorphic phases of ω-(4'-methylbiphenyl-4-yl) butane-1-thiol (BP4) molecules formed on Au(111) were investigated by multidimensional atomic force microscopy, combining conductivity measurements, electrostatic characterization, friction force mapping, and normal force spectroscopy. Based on the same molecular structure but differing in molecular order, packing density, and molecular tilt, the two phases serve as a test bench to establish the structure-property relationships in self-assembled monolayers (SAMs). From a detailed analysis of the charge transport and electrostatics, the contributions of geometrical and electronic effects to the tunneling are discussed.

Rare Neurodegenerative Diseases: Clinical and Genetic Update.

More than 600 human disorders afflict the nervous system. Of these, neurodegenerative diseases are usually characterised by onset in late adulthood, progressive clinical course, and neuronal loss with regional specificity in the central nervous system. They include Alzheimer's disease and other less frequent dementias, brain cancer, degenerative nerve diseases, encephalitis, epilepsy, genetic brain disorders, head and brain malformations, hydrocephalus, stroke, Parkinson's disease, multiple sclerosis, amyotrophic lateral sclerosis (ALS or Lou Gehrig's Disease), Huntington's disease, and Prion diseases, among others. Neurodegeneration usually affects, but is not limited to, the cerebral cortex, intracranial white matter, basal ganglia, thalamus, hypothalamus, brain stem, and cerebellum. Although the majority of neurodegenerative diseases are sporadic, Mendelian inheritance is well documented. Intriguingly, the clinical presentations and neuropathological findings in inherited neurodegenerative forms are often indistinguishable from those of sporadic cases, suggesting that converging genomic signatures and pathophysiologic mechanisms underlie both hereditary and sporadic neurodegenerative diseases. Unfortunately, effective therapies for these diseases are scarce to non-existent. In this chapter, we highlight the clinical and genetic features associated with the rare inherited forms of neurodegenerative diseases, including ataxias, multiple system atrophy, spastic paraplegias, Parkinson's disease, dementias, motor neuron diseases, and rare metabolic disorders.

Optical contrast and refractive index of natural van der Waals heterostructure nanosheets of franckeite.

We study mechanically exfoliated nanosheets of franckeite by quantitative optical microscopy. The analysis of transmission-mode and epi-illumination-mode optical microscopy images provides a rapid method to estimate the thickness of the exfoliated flakes at first glance. A quantitative analysis of the optical contrast spectra by means of micro-reflectance allows one to determine the refractive index of franckeite over a broad range of the visible spectrum through a fit of the acquired spectra to a model based on the Fresnel law.