Strain distribution in WS2 monolayers detected through polarization-resolved second harmonic generation.

Two-dimensional (2D) graphene and graphene-related materials (GRMs) show great promise for future electronic devices. GRMs exhibit distinct properties under the influence of the substrate that serves as support through uneven compression/ elongation of GRMs surface atoms. Strain in GRM monolayers is the most common feature that alters the interatomic distances and band structure, providing a new degree of freedom that allows regulation of their electronic properties and introducing the field of straintronics. Having an all-optical and minimally invasive detection tool that rapidly probes strain in large areas of GRM monolayers, would be of great importance in the research and development of novel 2D devices. Here, we use Polarization-resolved Second Harmonic Generation (P-SHG) optical imaging to identify strain distribution, induced in a single layer of WS2 placed on a pre-patterned Si/SiO2 substrate with cylindrical wells. By fitting the P-SHG data pixel-by-pixel, we produce spatially resolved images of the crystal armchair direction. In regions where the WS2 monolayer conforms to the pattern topography, a distinct cross-shaped pattern is evident in the armchair image owing to strain. The presence of strain in these regions is independently confirmed using a combination of atomic force microscopy and Raman mapping.

Phosphate Glass Microspheres with Silver Nanoparticles for Whispering Gallery Mode Resonators.

Glass microspheres have gained significant attention over the years in the field of photonics due to their application in whispering gallery mode (WGM) microresonator platforms. However, the synthesis of glass spheres in the micro regime remains challenging, while it relies mostly on complicated synthetic methods or sol-gel chemistry. Herein, we demonstrate the controlled formation of phosphate glass microspheres by means of a simple, fast, low-temperature, post-glass melting thermal treatment of previously quenched glass. Moreover, we report on the simultaneous formation of silver nanoparticles (AgNPs) on the surface of glass spheres upon the same treatment. The formation of metal nanoparticles onto the glass spheres induces attractive optical and plasmonic properties, believed to be suitable for WGM resonator-based applications, as well as a wide range of optoelectronic, photonic, and sensing applications.

Nanoliposomes Permeability in a Microfluidic Drug Delivery Platform across a 3D Hydrogel.

Nanoliposomes are nano-sized vesicles that can be used as drug delivery carriers with the ability to encapsulate both hydrophobic and hydrophilic compounds. Moreover, their lipid compositions facilitate their internalization by cells. However, the interaction between nanoliposomes and the membrane barrier of the human body is not well-known. If cellular tests and animal testing offer a solution, their lack of physiological relevance and ethical concerns make them unsuitable to properly mimic human body complexity. Microfluidics, which allows the environment of the human body to be imitated in a controlled way, can fulfil this role. However, existing models are missing the presence of something that would mimic a basal membrane, often consisting of a simple cell layer on a polymer membrane. In this study, we investigated the diffusion of nanoliposomes in a microfluidic system and found the optimal parameters to maximize their diffusion. Then, we incorporated a custom made GelMA with a controlled degree of substitution and studied the passage of fluorescently labeled nanoliposomes through this barrier. Our results show that highly substituted GelMA was more porous than lower substitution GelMA. Overall, our work lays the foundation for the incorporation of a hydrogel mimicking a basal membrane on a drug delivery microfluidic platform.

Microglia-derived extracellular vesicles trigger age-related neurodegeneration upon DNA damage.

DNA damage and neurodegenerative disorders are intimately linked but the underlying mechanism remains elusive. Here, we show that persistent DNA lesions in tissue-resident macrophages carrying an XPF-ERCC1 DNA repair defect trigger neuroinflammation and neuronal cell death in mice. We find that microglia accumulate dsDNAs and chromatin fragments in the cytosol, which are sensed thereby stimulating a viral-like immune response in Er1Cx/- and naturally aged murine brain. Cytosolic DNAs are packaged into extracellular vesicles (EVs) that are released from microglia and discharge their dsDNA cargo into IFN-responsive neurons triggering cell death. To remove cytosolic dsDNAs and prevent inflammation, we developed targeting EVs to deliver recombinant DNase I to Er1Cx/- brain microglia in vivo. We show that EV-mediated elimination of cytosolic dsDNAs is sufficient to prevent neuroinflammation, reduce neuronal apoptosis, and delay the onset of neurodegenerative symptoms in Er1Cx/- mice. Together, our findings unveil a causal mechanism leading to neuroinflammation and provide a rationalized therapeutic strategy against age-related neurodegeneration.

Harnessing laser technology to create stable metal halide perovskite-rGO conjugates as promising electrodes for Zn-ion capacitors.

We report that the direct conjugation of metal halide perovskite nanocrystals on rGO sheets can provide high performance and stable electrodes for Zn-ion capacitors. It is the first time that metal halide nanocrystals have been used to enhance the energy storage of 2D materials in capacitors by introducing an additional pseudocapacitance mechanism. In particular, we present a simple, rapid and room temperature laser-induced method to anchor CsPbBr3 nanocrystals on rGO sheets without affecting the initial morphology and crystal structure of the two components. The flexible and high surface area of the rGO sheets enables the conjugation of individual metal halide perovskite nanocrystals, giving rise to new synergetic functionalities. As a result, the specific capacitance of the perovskite-rGO conjugated electrodes can be enhanced by 178- and 152-times compared to those of the plain rGO and perovskite electrodes respectively.

Influence of antireflection Si coatings on the damage threshold of fused silica upon irradiation with mid-IR femtosecond laser pulses.

Recent progress in the development of high-power mid-IR laser sources and the exciting laser driven physical phenomena associated with the irradiation of solids via ultrashort laser pulses in that spectral region are aimed to potentially create novel capabilities for material processing. In particular, the investigation of the underlying physical processes and the evaluation of the optical breakdown threshold (OBT) following irradiation of bulk dielectric materials with mid-IR femtosecond (fs) pulses have been recently presented. In this Letter, we will explore the conditions that generate sufficient carrier excitation levels which lead to damage upon irradiation of a dielectric material (SiO2) coated with antireflection (AR) semiconducting films (Si) of variable thickness with fs pulses. Simulation results demonstrate that the reflectivity and transmissivity of the Si/SiO2 are thickness dependent which can be employed to modulate the damage threshold of the substrate. The study is to provide innovative routes for selecting material sizes that can be used for antireflection coatings and applications in the mid-IR region.

Change of Conduction Mechanism in Polymer/Single Wall Carbon Nanotube Composites upon Introduction of Ionic Liquids and Their Investigation by Transient Absorption Spectroscopy: Implication for Thermoelectric Applications.

Polymer composites based on polycarbonate (PC) and polyether ether ketone (PEEK) filled with single-walled carbon nanotubes (SWCNTs, 0.5-2.0 wt %) were melt-mixed to investigate their suitability for thermoelectric applications. Both types of polymer composites exhibited positive Seebeck coefficients (S), indicative for p-type thermoelectric materials. As an additive to improve the thermoelectric performance, three different ionic liquids (ILs), specifically THTDPCl, BMIMPF6, and OMIMCl, were added with the aim to change the thermoelectric conduction type of the composites from p-type to n-type. It was found that in both composite types, among the three ILs employed, only the phosphonium-based IL THTDPCl was able to activate the p- to n-type switching. Moreover, it is revealed that for the thermoelectric parameters and performance, the SWCNT:lL ratio plays a role. In the selected systems, S-values between 61.3 µV/K (PEEK/0.75 wt % SWCNT) and -37.1 µV/K (PEEK/0.75 wt % SWCNT + 3 wt % THTDPCl) were reached. In order to shed light on the physical origins of the thermoelectric properties, the PC-based composites were studied using ultrafast laser time-resolved transient absorption spectroscopy (TAS). The TAS studies revealed that the introduction of ILs in the developed PC/CNT composites leads to the formation of biexcitons when compared to the IL-free composites. Moreover, no direct correlation between S and exciton lifetimes was found for the IL-containing composites. Instead, the exciton lifetime decreases while the conductivity seems to increase due to the availability of more free-charge carriers in the polymer matrix.

Microfluidic Systems for Neural Cell Studies.

Whereas the axons of the peripheral nervous system (PNS) spontaneously regenerate after an injury, the occurring regeneration is rarely successful because axons are usually directed by inappropriate cues. Therefore, finding successful ways to guide neurite outgrowth, in vitro, is essential for neurogenesis. Microfluidic systems reflect more appropriately the in vivo environment of cells in tissues such as the normal fluid flow within the body, consistent nutrient delivery, effective waste removal, and mechanical stimulation due to fluid shear forces. At the same time, it has been well reported that topography affects neuronal outgrowth, orientation, and differentiation. In this review, we demonstrate how topography and microfluidic flow affect neuronal behavior, either separately or in synergy, and highlight the efficacy of microfluidic systems in promoting neuronal outgrowth.

Upside-Down Preference in the Forskolin-Induced In Vitro Differentiation of 50B11 Sensory Neurons: A Morphological Investigation by Label-Free Non-Linear Microscopy.

In this study, we revealed a peculiar morphological feature of 50B11 nociceptive sensory neurons in in vitro culture related to the forskolin-induced differentiation of these cells growing upside-down on cover glass supports. Multi-photon non-linear microscopy was applied to monitor increased neurite arborization and elongation. Under live and unstained conditions, second harmonic generation (SHG) microscopy could monitor microtubule organization inside the cells while also correlating with the detection of cellular multi-photon autofluorescence, probably derived from mitochondria metabolites. Although the differentiated cells of each compartment did not differ significantly in tubulin or multi-photon autofluorescence contents, the upturned neurons were more elongated, presenting a higher length/width cellular ratio and longer neurites, indicative of differentiated cells. SHG originating from the axons' microtubules represented a proper tool to study neurons' inverted culture in live conditions without exogenous staining. This work represents the first instance of examining neuronal cell lines growing and differentiated in an upside-down orientation, allowing a possible improvement of 50B11 as a model in physiology studies of sensory neurons in peripheric nervous system disease (e.g., Fabry disease, Friedreich ataxia, Charcot-Marie-Tooth, porphyria, type 1 diabetes, Guillain-Barré syndrome in children) and analgesic drug screening.

Anisotropic 3D scaffolds for spinal cord guided repair: Current concepts.

A spinal cord injury (SCI) can be caused by unforeseen events such as a fall, a vehicle accident, a gunshot, or a malignant illness, which has a significant impact on the quality of life of the patient. Due to the limited regenerative potential of the central nervous system (CNS), SCI is one of the most daunting medical challenges of modern medicine. Great advances have been made in tissue engineering and regenerative medicine, which include the transition from two-dimensional (2D) to three-dimensional (3D) biomaterials. Combinatory treatments that use 3D scaffolds may significantly enhance the repair and regeneration of functional neural tissue. In an effort to mimic the chemical and physical properties of neural tissue, scientists are researching the development of the ideal scaffold made of synthetic and/or natural polymers. Moreover, in order to restore the architecture and function of neural networks, 3D scaffolds with anisotropic properties that replicate the native longitudinal orientation of spinal cord nerve fibres are being designed. In an effort to determine if scaffold anisotropy is a crucial property for neural tissue regeneration, this review focuses on the most current technological developments relevant to anisotropic scaffolds for SCI. Special consideration is given to the architectural characteristics of scaffolds containing axially oriented fibres, channels, and pores. By analysing neural cell behaviour in vitro and tissue integration and functional recovery in animal models of SCI, the therapeutic efficacy is evaluated for its successes and limitations.

Interfacing reduced graphene oxide with an adipose-derived extracellular matrix as a regulating milieu for neural tissue engineering.

Enthralling evidence of the potential of graphene-based materials for neural tissue engineering is motivating the development of scaffolds using various structures related to graphene such as graphene oxide (GO) or its reduced form. Here, we investigated a strategy based on reduced graphene oxide (rGO) combined with a decellularized extracellular matrix from adipose tissue (adECM), which is still unexplored for neural repair and regeneration. Scaffolds containing up to 50 wt% rGO relative to adECM were prepared by thermally induced phase separation assisted by carbodiimide (EDC) crosslinking. Using partially reduced GO enables fine-tuning of the structural interaction between rGO and adECM. As the concentration of rGO increased, non-covalent bonding gradually prevailed over EDC-induced covalent conjugation with the adECM. Edge-to-edge aggregation of rGO favours adECM to act as a biomolecular physical crosslinker to rGO, leading to the softening of the scaffolds. The unique biochemistry of adECM allows neural stem cells to adhere and grow. Importantly, high rGO concentrations directly control cell fate by inducing the differentiation of both NE-4C cells and embryonic neural progenitor cells into neurons. Furthermore, primary astrocyte fate is also modulated as increasing rGO boosts the expression of reactivity markers while unaltering the expression of scar-forming ones.

Laser-Structured Si and PLGA Inhibit the Neuro2a Differentiation in Mono- and Co-Culture with Glia.

BACKGROUND: The first step towards a successful neural tissue engineering therapy is the development of an appropriate scaffold and the in vitro study of the cellular response onto it. METHODS: Here, we fabricated nano- and micro- patterned Si surfaces via direct ultrafast laser irradiation, as well as their replicas in the biodegradable poly(lactide-co-glycolide), in order to use them as culture substrates for neuronal cells. The differentiation of neuro2a cells on the Si platforms and their replicas was studied both in a mono-culture and in a co-culture with glial cells (Schwann-SW10). RESULTS: It was found that the substrate's roughness inhibits the differentiation of the neuronal cells even in the presence of the differentiation medium, and the higher the roughness is, the more the differentiation gets limited. CONCLUSION: Our results highlight the importance of the substrate's topography for the controlled growth and differentiation of the neuronal cells and their further study via protein screening methods could shed light on the factors that lead to limited differentiation; thus, contributing to the long standing request for culture substrates that induce cells to differentiate.

Highly ordered laser imprinted plasmonic metasurfaces for polarization sensitive perfect absorption.

We present polarization-sensitive gap surface plasmon metasurfaces fabricated with direct material processing using pulsed laser light, an alternative and versatile approach. In particular we imprint laser induced periodic surface structures on nanometer-thick Ni films, which are back-plated by a grounded dielectric layer with TiO2 and ZnO deposition followed by Au evaporation. The procedure results in a metal-insulator-metal type plasmonic metasurface with a corrugated top layer consisting of highly-ordered, sinusoidal shaped, periodic, thin, metallic nanowires. The metasurface sustains sharp, resonant gap surface plasmons and provides various opportunities for polarization control in reflection, which is here switched by the size and infiltrating material of the insulating cavity. The polarization control is associated with the polarization sensitive perfect absorption and leads to high extinction ratios in the near-IR and mid-IR spectral areas. Corresponding Fourier-transform infrared spectroscopy measurements experimentally demonstrate that the fabrication approach produces metasurfaces with very well-defined, controllable, sharp resonances and polarization sensitive resonant absorption response which, depending on the insulating cavity size, impacts either the normal or the parallel to the nanowires polarization.

Influence of Heat Accumulation on Morphology Debris Deposition and Wetting of LIPSS on Steel upon High Repetition Rate Femtosecond Pulses Irradiation.

The fabrication of laser-induced periodic surface structures (LIPSS) over extended areas at high processing speeds requires the use of high repetition rate femtosecond lasers. It is known that industrially relevant materials such as steel experience heat accumulation when irradiated at repetition rates above some hundreds of kHz, and significant debris redeposition can take place. However, there are few studies on how the laser repetition rate influences both the debris deposition and the final LIPSS morphology. In this work, we present a study of fs laser-induced fabrication of low spatial frequency LIPSS (LSFL), with pulse repetition rates ranging from 10 kHz to 2 MHz on commercially available steel. The morphology of the laser-structured areas as well as the redeposited debris was characterized by scanning electron microscopy (SEM) and µ-Raman spectroscopy. To identify repetition rate ranges where heat accumulation is present during the irradiations, we developed a simple heat accumulation model that solves the heat equation in 1 dimension implementing a Forward differencing in Time and Central differencing in Space (FTCS) scheme. Contact angle measurements with water demonstrated the influence of heat accumulation and debris on the functional wetting behavior. The findings are directly relevant for the processing of metals using high repetition rate femtosecond lasers, enabling the identification of optimum conditions in terms of desired morphology, functionality, and throughput.

The role of mechanobiology on the Schwann cell response: A tissue engineering perspective.

Schwann cells (SCs), the glial cells of the peripheral nervous system (PNS), do not only form myelin sheaths thereby insulating the electrical signal propagated by the axons, but also play an essential role in the regeneration of injured axons. SCs are inextricably connected with their extracellular environment and the mechanical stimuli that are received determine their response during development, myelination and injuries. To this end, the mechanobiological response of SCs is being actively researched, as it can determine the suitability of fabricated scaffolds for tissue engineering and regenerative medicine applications. There is growing evidence that SCs are sensitive to changes in the mechanical properties of the surrounding environment (such as the type of material, its elasticity and stiffness), different topographical features provided by the environment, as well as shear stress. In this review, we explore how different mechanical stimuli affect SC behaviour and highlight the importance of exploring many different avenues when designing scaffolds for the repair of PNS injuries.

Laser-Induced Erasable and Re-Writable Waveguides within Silver Phosphate Glasses.

Femtosecond direct laser writing is a well-established and robust technique for the fabrication of photonic structures. Herein, we report on the fabrication of buried waveguides in AgPO3 silver metaphosphate glasses, as well as, on the erase and re-writing of those structures, by means of a single femtosecond laser source. Based on the fabrication procedure, the developed waveguides can be erased and readily re-inscribed upon further femtosecond irradiation under controlled conditions. Namely, for the initial waveguide writing the employed laser irradiation power was 2 J/cm2 with a scanning speed of 5 mm/s and a repetition rate of 200 kHz. Upon enhancing the power to 16 J/cm2 while keeping constant the scanning speed and reducing the repetition rate to 25 kHz, the so formed patterns were readily erased. Then, upon using a laser power of 2 J/cm2 with a scanning speed of 1 mm/s and a repetition rate of 200 kHz the waveguide patterns were re-written inside the glass. Scanning electron microscopy (SEM) images at the cross-section of the processed glasses, combined with spatial Raman analysis revealed that the developed write/erase/re-write cycle, does not cause any structural modification to the phosphate network, rendering the fabrication process feasible for reversible optoelectronic applications. Namely, it is proposed that this non-ablative phenomenon lies on the local relaxation of the glass network caused by the heat deposited upon pulsed laser irradiation. The resulted waveguide patterns Our findings pave the way towards new photonic applications involving infinite cycles of write/erase/re-write processes without the need of intermediate steps of typical thermal annealing treatments.

Fast and selective reduction of nitroarenes under visible light with an earth-abundant plasmonic photocatalyst.

Reduction of nitroaromatics to the corresponding amines is a key process in the fine and bulk chemicals industry to produce polymers, pharmaceuticals, agrochemicals and dyes. However, their effective and selective reduction requires high temperatures and pressurized hydrogen and involves noble metal-based catalysts. Here we report on an earth-abundant, plasmonic nano-photocatalyst, with an excellent reaction rate towards the selective hydrogenation of nitroaromatics. With solar light as the only energy input, the chalcopyrite catalyst operates through the combined action of hot holes and photothermal effects. Ultrafast laser transient absorption and light-induced electron paramagnetic resonance spectroscopies have unveiled the energy matching of the hot holes in the valence band of the catalyst with the frontier orbitals of the hydrogen and electron donor, via a transient coordination intermediate. Consequently, the reusable and sustainable copper-iron-sulfide (CuFeS2) catalyst delivers previously unattainable turnover frequencies, even in large-scale reactions, while the cost-normalized production rate stands an order of magnitude above the state of the art.

Fabrication of Biomimetic 2D Nanostructures through Irradiation of Stainless Steel Surfaces with Double Femtosecond Pulses.

Femtosecond laser induced changes on the topography of stainless steel with double pulses is investigated to reveal the role of parameters such as the fluence, the energy dose and the interpulse delay on the features of the produced patterns. Our results indicate that short pulse separation (Δτ = 5 ps) favors the formation of 2D Low Spatially Frequency Laser Induced Periodic Surface Structures (LSFL) while longer interpulse delays (Δτ = 20 ps) lead to 2D High Spatially Frequency LIPSS (HSFL). The detailed investigation is complemented with an analysis of the produced surface patterns and characterization of their wetting and cell-adhesion properties. A correlation between the surface roughness and the contact angle is presented which confirms that topographies of variable roughness and complexity exhibit different wetting properties. Furthermore, our analysis indicates that patterns with different spatial characteristics demonstrate variable cell adhesion response which suggests that the methodology can be used as a strategy towards the fabrication of tailored surfaces for the development of functional implants.

Laser-Induced Morphological and Structural Changes of Cesium Lead Bromide Nanocrystals.

Metal halide perovskite nanocrystals, an emerging class of materials for advanced photonic and optoelectronic applications, are mainly fabricated with colloidal chemistry routes. On the quest for new properties according to application needs, new perovskite systems of various morphologies and levels of doping and alloying have been developed, often also involving post-synthesis reactions. Recently, laser irradiation in liquids has been utilized as a fast method to synthesize or transform materials and interesting laser-induced transformations on nanocrystals were induced. These studies in general have been limited to small nanocrystals (~15 nm). In the case of halide perovskites, fragmentation or anion exchange have been observed in such laser-based processes, but no crystal structure transformations were actually observed or deliberately studied. Nanocrystals are more sensitive to light exposure compared to the corresponding bulk crystals. Additional factors, such as size, morphology, the presence of impurities, and others, can intricately affect the photon absorption and heat dissipation in nanocrystal suspensions during laser irradiation. All these factors can play an important role in the final morphologies and in the time required for these transformations to unfold. In the present work, we have employed a 513 nm femtosecond (fs) laser to induce different transformations in large nanocrystals, in which two phases coexist in the same particle (Cs4PbBr6/CsPbBr3 nanohexagons of ~100 nm), dispersed in dichlorobenzene. These transformations include: (i) the exfoliation of the primary nanohexagons and partial anion exchange; (ii) fragmentation in smaller nanocubes and partial anion exchange; (iii) side-by-side-oriented attachment, fusion, and formation of nanoplatelets and complete anion exchange; (iv) side-by-side attachment, fusion, and formation of nanosheets. Partial or complete Br-Cl anion exchange in the above transformations was triggered by the partial degradation of dichlorobenzene. In addition to the detailed analysis of the various nanocrystal morphologies observed in the various transformations, the structure-photoluminescence relationships for the different samples were analyzed and discussed.