Surface-Enhanced Raman Spectroscopy of Ammonium Nitrate Using Al Structures, Fabricated by Laser Processing of AlN Ceramic.

This work presents results on laser-induced surface structuring of AlN ceramic and its application in Surface-Enhanced Raman Spectroscopy (SERS). The laser processing is performed by nanosecond pulses in air and vacuum. Depending on the processing conditions, different surface morphology can be obtained. The ablation process is realized by ceramic decomposition as the formation of an aluminium layer is detected. The efficiency of the fabricated structures as active substrates in SERS is estimated by the ability of the detection of ammonium nitrate (NH4NO3). It is conducted for Raman spectrometer systems that operate at wavelengths of 514 and 785 nm where the most common commercial systems work. The obtained structures contribute to enhancement of the Raman signal at both wavelengths, as the efficiency is higher for excitation at 514 nm. The limit of detection (LOD) of ammonium nitrate is estimated to be below the maximum allowed value in drinking water. The analysis of the obtained results was based on the calculations of the near field enhancement at different conditions based on Finite Difference Time Domain simulation and the extinction spectra calculations based on Generalized Mie scattering theory. The structures considered in these simulations were taken from the SEM images of the real samples. The oxidation issue of the ablated surface was studied by X-ray photoelectron spectroscopy. The presented results indicated that laser structuring of AlN ceramics is a way for fabrication of Al structures with specific near-field properties that can be used for the detection of substances with high social impact.

Astrocytic uptake of posttranslationally modified amyloid-ß leads to endolysosomal system disruption and induction of pro-inflammatory signaling.

The disruption of astrocytic catabolic processes contributes to the impairment of amyloid-ß (Aß) clearance, neuroinflammatory signaling, and the loss of synaptic contacts in late-onset Alzheimer's disease (AD). While it is known that the posttranslational modifications of Aß have significant implications on biophysical properties of the peptides, their consequences for clearance impairment are not well understood. It was previously shown that N-terminally pyroglutamylated Aß3(pE)-42, a significant constituent of amyloid plaques, is efficiently taken up by astrocytes, leading to the release of pro-inflammatory cytokine tumor necrosis factor α and synapse loss. Here we report that Aß3(pE)-42, but not Aß1-42, gradually accumulates within the astrocytic endolysosomal system, disrupting this catabolic pathway and inducing the formation of heteromorphous vacuoles. This accumulation alters lysosomal kinetics, lysosome-dependent calcium signaling, and upregulates the lysosomal stress response. These changes correlate with the upregulation of glial fibrillary acidic protein (GFAP) and increased activity of nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB). Treatment with a lysosomal protease inhibitor, E-64, rescues GFAP upregulation, NF-κB activation, and synapse loss, indicating that abnormal lysosomal protease activity is upstream of pro-inflammatory signaling and related synapse loss. Collectively, our data suggest that Aß3(pE)-42-induced disruption of the astrocytic endolysosomal system leads to cytoplasmic leakage of lysosomal proteases, promoting pro-inflammatory signaling and synapse loss, hallmarks of AD-pathology.

Laser-Treated MXene as an Electrochemical Agent to Boost Properties of Semitransparent Photoelectrode Based on Titania Nanotubes.

In this study, Ti3C2Tx underwent laser treatment to reshape it, resulting in the formation of a TiO2/Ti3C2Tx heterojunction. The interaction with laser light induced the formation of spherical TiO2 composed of an anatase-rutile phase on the Ti3C2Tx surface. Such a heterostructure was loaded over a titania nanotube (TNT) layer, and the surface area was enhanced through immersion in a TiCl4 solution followed by thermal treatment. Consequently, the photon-to-electron conversion efficiency exhibits a 10-fold increase as compared to bare TNT. Moreover, for the sample produced with optimized conditions, five times higher photoactivity is observed in comparison to bare TNT. It was shown that under visible light irradiation the most photoactive heterojunction based on the tubular layer reveals a substantial drop in the charge transfer resistance of about 32% with respect to the dark condition. This can be attributed to the narrower band gaps of the modified material and improvement of the separation efficiency of the photogenerated electron-hole pairs. Overall results suggest that this investigation underscores TiO2/Ti3C2Tx as a promising noble-metal-free material that enhances both the electrochemical and photoelectrochemical performances of electrode materials based on TNT that can be further used in light-harvesting applications.

A liaison between chaperone-mediated autophagy and exocytotic lysosomes controls the dendritic metastable proteome.

The neuronal metastable proteome includes several aggregation-prone proteins related to neurodegeneration. The complex morphology of neurons with very thin processes and enhanced protein turnover therefore necessitates efficient local machinery to remove excessive protein. In recent work we revealed that chaperone-mediated autophagy (CMA) provides cargo for dendritic exocytic lysosomes, a mechanism that serves in the rapid removal of disease-relevant, supersaturated proteins such as TARDBP/TDP-43 (TAR DNA binding protein) and HTT (huntingtin). We found that lysosomal exocytosis requires docking of the lysosomal protein LAMP2B to the glutamatergic receptor scaffold DLG3/SAP102 and that it is regulated by GRIN/NMDA (N-methyl-D-aspartate)-receptor activity. Thus, the small caliber of dendritic processes might impose a need for local disposal of aggregation-prone proteins like TARDBP and HTT. Moreover, we observed that lysosomal exocytosis might serve in both protein removal and modulation of synaptic processes, and the latter might be an inevitable consequence of the necessity for local disposal of CMA clients in dendrites.

MicroRNA-92a-CPEB3 axis protects neurons against inflammatory neurodegeneration.

Neuroinflammation causes neuronal injury in multiple sclerosis (MS) and other neurological diseases. MicroRNAs (miRNAs) are important modulators of neuronal stress responses, but knowledge about their contribution to neuronal protection or damage during inflammation is limited. Here, we constructed a regulatory miRNA-mRNA network of inflamed motor neurons by leveraging cell type-specific miRNA and mRNA sequencing of mice undergoing experimental autoimmune encephalomyelitis (EAE). We found robust induction of miR-92a in inflamed spinal cord neurons and identified cytoplasmic polyadenylation element-binding protein 3 (Cpeb3) as a key target of miR-92a-mediated posttranscriptional silencing. We detected CPEB3 repression in inflamed neurons in murine EAE and human MS. Moreover, both miR-92a delivery and Cpeb3 deletion protected neuronal cultures against excitotoxicity. Supporting a detrimental effect of Cpeb3 in vivo, neuron-specific deletion in conditional Cpeb3 knockout animals led to reduced inflammation-induced clinical disability in EAE. Together, we identified a neuroprotective miR-92a-Cpeb3 axis in neuroinflammation that might serve as potential treatment target to limit inflammation-induced neuronal damage.

Chaperone-mediated autophagy in neuronal dendrites utilizes activity-dependent lysosomal exocytosis for protein disposal.

The complex morphology of neurons poses a challenge for proteostasis because the majority of lysosomal degradation machinery is present in the cell soma. In recent years, however, mature lysosomes were identified in dendrites, and a fraction of those appear to fuse with the plasma membrane and release their content to the extracellular space. Here, we report that dendritic lysosomes are heterogeneous in their composition and that only those containing lysosome-associated membrane protein (LAMP) 2A and 2B fuse with the membrane and exhibit activity-dependent motility. Exocytotic lysosomes dock in close proximity to GluN2B-containing N-methyl-D-aspartate-receptors (NMDAR) via an association of LAMP2B to the membrane-associated guanylate kinase family member SAP102/Dlg3. NMDAR-activation decreases lysosome motility and promotes membrane fusion. We find that chaperone-mediated autophagy is a supplier of content that is released to the extracellular space via lysosome exocytosis. This mechanism enables local disposal of aggregation-prone proteins like TDP-43 and huntingtin.

Scanning with Laser Beam over the TiO2 Nanotubes Covered with Thin Chromium Layers towards the Activation of the Material under the Visible Light.

This work presents pulsed UV laser treatment (355 nm, 2 Hz) of TiO2 nanotubes decorated with chromium oxides. The modification was performed in a system equipped with a beam homogenizer, and during the irradiation, the samples were mounted onto the moving motorized table. In such a system, both precisely selected areas and any large area of the sample can be modified. Photoelectrochemical tests revealed photoresponse of laser-treated samples up to 1.37- and 18-fold under the illumination with ultraviolet-visible and visible light, respectively, in comparison to bare titania. Optimal beam energy fluence regarding sample photoresponse has been established. Scanning electron microscopy images, X-ray diffraction patterns, along with Raman and X-ray photoelectron spectra, suggest that the enhanced photoresponse results from changes solely induced in the layer of chromium oxides. It is believed that the results of the present work will contribute to a wider interest in laser modification of semiconductors exhibiting improved photoelectrochemical activity.

Protein transport from pre- and postsynapse to the nucleus: Mechanisms and functional implications.

The extreme length of neuronal processes poses a challenge for synapse-to-nucleus communication. In response to this challenge several different mechanisms have evolved in neurons to couple synaptic activity to the regulation of gene expression. One of these mechanisms concerns the long-distance transport of proteins from pre- and postsynaptic sites to the nucleus. In this review we summarize current evidence on mechanisms of transport and consequences of nuclear import of these proteins for gene transcription. In addition, we discuss how information from pre- and postsynaptic sites might be relayed to the nucleus by this type of long-distance signaling. When applicable, we highlight how long-distance protein transport from synapse-to-nucleus can provide insight into the pathophysiology of disease or reveal new opportunities for therapeutic intervention.

The Impact of Side-Selective Laser Tailoring of Titania Nanotubes on Changes in Photoelectrocatalytic Activity.

Over the last few decades, titanium(IV) oxide-based materials have gained particular attention due to their stability, corrosion resistance, photocatalytic activity under UV light, and possibilities for modification. Among various structures, TiO2 nanotubes (NTs) grown on Ti foil or glass substrates and obtained through a simple anodization process are widely used as photocatalysts or photoanodes. During the anodization process, the geometry of the nanotubes (length, distribution, diameter, wall thickness, etc.) is easily controlled, though the obtained samples are amorphous. Heat treatment is required to transform the amorphous material into crystalline material. However, instead of time- and cost-consuming furnace treatment, fast and precise laser annealing is applied as a promising alternative. Nonetheless, laser treatment can result in geometry changes of TiO2 NTs, consequently altering, their electrochemical activity. Moreover, modification of the TiO2 NTs surfaces with transition metals and further laser treatment can result in materials with unique photoelectrochemical properties. In this regard, we gathered the latest achievements in the field of laser-treated titania for this review paper. We mainly focused on single structural and morphological changes resulting from pulsed laser annealing and their influence on the electrochemical properties of titania. Finally, the theoretical basis for and combination of laser- and metal-modifications and their impact on the resulting possibilities for electrochemical water splitting are also discussed.

Jacob-induced transcriptional inactivation of CREB promotes Aß-induced synapse loss in Alzheimer's disease.

Synaptic dysfunction caused by soluble ß-amyloid peptide (Aß) is a hallmark of early-stage Alzheimer's disease (AD), and is tightly linked to cognitive decline. By yet unknown mechanisms, Aß suppresses the transcriptional activity of cAMP-responsive element-binding protein (CREB), a master regulator of cell survival and plasticity-related gene expression. Here, we report that Aß elicits nucleocytoplasmic trafficking of Jacob, a protein that connects a NMDA-receptor-derived signalosome to CREB, in AD patient brains and mouse hippocampal neurons. Aß-regulated trafficking of Jacob induces transcriptional inactivation of CREB leading to impairment and loss of synapses in mouse models of AD. The small chemical compound Nitarsone selectively hinders the assembly of a Jacob/LIM-only 4 (LMO4)/ Protein phosphatase 1 (PP1) signalosome and thereby restores CREB transcriptional activity. Nitarsone prevents impairment of synaptic plasticity as well as cognitive decline in mouse models of AD. Collectively, the data suggest targeting Jacob protein-induced CREB shutoff as a therapeutic avenue against early synaptic dysfunction in AD.

The Anodization of Thin Titania Layers as a Facile Process towards Semitransparent and Ordered Electrode Material.

Photoanodes consisting of titania nanotubes (TNTs) grown on transparent conductive oxides (TCO) by anodic oxidation are being widely investigated as a low-cost alternative to silicon-based materials, e.g., in solar light-harvesting applications. Intending to enhance the optical properties of those photoanodes, the modification of the surface chemistry or control of the geometrical characteristics of developed TNTs has been explored. In this review, the recent advancement in light-harvesting properties of transparent anodic TNTs formed onto TCO is summarized. The physical deposition methods such as magnetron sputtering, pulsed laser deposition and electron beam evaporation are the most reported for the deposition of Ti film onto TCO, which are subsequently anodized. A concise description of methods utilized to improve the adhesion of the deposited film and achieve TNT layers without cracks and delamination after the anodization is outlined. Then, the different models describing the formation mechanism of anodic TNTs are discussed with particular focus on the impact of the deposited Ti film thickness on the adhesion of TNTs. Finally, the effects of the modifications of both the surface chemistry and morphological features of materials on their photocatalyst and photovoltaic performances are discussed. For each section, experimental results obtained by different research groups are evoked.

The needs of a synapse-How local organelles serve synaptic proteostasis.

Synaptic function crucially relies on the constant supply and removal of neuronal membranes. The morphological complexity of neurons poses a significant challenge for neuronal protein transport since the machineries for protein synthesis and degradation are mainly localized in the cell soma. In response to this unique challenge, local micro-secretory systems have evolved that are adapted to the requirements of neuronal membrane protein proteostasis. However, our knowledge of how neuronal proteins are synthesized, trafficked to membranes, and eventually replaced and degraded remains scarce. Here, we review recent insights into membrane trafficking at synaptic sites and into the contribution of local organelles and micro-secretory pathways to synaptic function. We describe the role of endoplasmic reticulum specializations in neurons, Golgi-related organelles, and protein complexes like retromer in the synthesis and trafficking of synaptic transmembrane proteins. We discuss the contribution of autophagy and of proteasome-mediated and endo-lysosomal degradation to presynaptic proteostasis and synaptic function, as well as nondegradative roles of autophagosomes and lysosomes in signaling and synapse remodeling. We conclude that the complexity of neuronal cyto-architecture necessitates long-distance protein transport that combines degradation with signaling functions.

Nanostructure of the laser-modified transition metal nanocomposites for water splitting.

Although hydrogen is considered by many to be the green fuel of the future, nowadays it is primarily produced through steam reforming, which is a process far from ecological. Therefore, emphasis is being put on the development of electrodes capable of the efficient production of hydrogen and oxygen from water. To make the green alternative possible, the solution should be cost-efficient and well processable, generating less waste which is a huge challenge. In this work, the laser-based modification technique of the titania nanotubes containing sputtered transition metal species (Fe, Co, Ni, and Cu) was employed. The characteristics of the electrodes are provided both for the hydrogen and oxygen evolution reactions, where the influence of the laser treatment has been found to have the opposite effect. The structural and chemical analysis of the substrate material provides insight into pathways towards more efficient, low-temperature water splitting. Laser-assisted integration of transition metal with the tubular nanostructure results in the match-like structure where the metal species are accumulated at the head. The electrochemical data indicates a significant decrease in material resistance that leads to an overpotential of only +0.69 V at 10 mA cm-2for nickel-modified material.

Neddylation-dependent protein degradation is a nexus between synaptic insulin resistance, neuroinflammation and Alzheimer's disease.

BACKGROUND: The metabolic syndrome is a consequence of modern lifestyle that causes synaptic insulin resistance and cognitive deficits and that in interaction with a high amyloid load is an important risk factor for Alzheimer's disease. It has been proposed that neuroinflammation might be an intervening variable, but the underlying mechanisms are currently unknown. METHODS: We utilized primary neurons to induce synaptic insulin resistance as well as a mouse model of high-risk aging that includes a high amyloid load, neuroinflammation, and diet-induced obesity to test hypotheses on underlying mechanisms. RESULTS: We found that neddylation and subsequent activation of cullin-RING ligase complexes induced synaptic insulin resistance through ubiquitylation and degradation of the insulin-receptor substrate IRS1 that organizes synaptic insulin signaling. Accordingly, inhibition of neddylation preserved synaptic insulin signaling and rescued memory deficits in mice with a high amyloid load, which were fed with a 'western diet'. CONCLUSIONS: Collectively, the data suggest that neddylation and degradation of the insulin-receptor substrate is a nodal point that links high amyloid load, neuroinflammation, and synaptic insulin resistance to cognitive decline and impaired synaptic plasticity in high-risk aging.

Simple synthesis route for fabrication of protective photo-crosslinked poly(zwitterionic) membranes for application in non-enzymatic glucose sensing.

This work focuses on the fabrication of non-enzymatic glucose sensing materials based on laser-formed Au nanoparticles embedded in Ti-textured substrates. Those materials possess good catalytic activity toward glucose oxidation in 0.1 × phosphate buffered saline as well as resistance to some interferants, such as ascorbic acid, urea, and glycine. The electrodes are further coated with three different polymers, that is, Nafion, photo-crosslinked poly(zwitterions) based on sulfobetaine methacrylate, and a hybrid membrane consisting of both polymers. Both the optimal integrity of the material and its catalytic activity toward glucose oxidation were maintained by the hybrid membranes with a large excess of poly(zwitterions) (mass ratio 20:1). The chemical structures of the as-formed membranes are confirmed by Fourier transform infrared spectroscopy. Due to the zwitterionic nature of the coating, the electrodes are resistant to biofouling and maintain electrochemical activity toward glucose for 4 days. Moreover, due to the synergistic effect of both Nafion and poly(zwitterions), the interference from the two compounds, namely, from acetylsalicylic acid and acetaminophen, was diminished. Besides the presence of polymer membranes, the electrode possesses a sensitivity of 36.8 µA cm-2  mM-1 in the linear range of 0.4-12 mM, while the limit of detection was estimated to be 23 µM. Finally, the electrodes are stable, and their response is not altered even by 1,000 bending cycles.

Jacob, a Synapto-Nuclear Protein Messenger Linking N-methyl-D-aspartate Receptor Activation to Nuclear Gene Expression.

Pyramidal neurons exhibit a complex dendritic tree that is decorated by a huge number of spine synapses receiving excitatory input. Synaptic signals not only act locally but are also conveyed to the nucleus of the postsynaptic neuron to regulate gene expression. This raises the question of how the spatio-temporal integration of synaptic inputs is accomplished at the genomic level and which molecular mechanisms are involved. Protein transport from synapse to nucleus has been shown in several studies and has the potential to encode synaptic signals at the site of origin and decode them in the nucleus. In this review, we summarize the knowledge about the properties of the synapto-nuclear messenger protein Jacob with special emphasis on a putative role in hippocampal neuronal plasticity. We will elaborate on the interactome of Jacob, the signals that control synapto-nuclear trafficking, the mechanisms of transport, and the potential nuclear function. In addition, we will address the organization of the Jacob/NSMF gene, its origin and we will summarize the evidence for the existence of splice isoforms and their expression pattern.

Influence of Annealing Atmospheres on Photoelectrochemical Activity of TiO2 Nanotubes Modified with AuCu Nanoparticles.

In this article, we studied the annealing process of AuCu layers deposited on TiO2 nanotubes (NTs) conducted in various atmospheres such as air, vacuum, argon, and hydrogen in order to obtain materials active in both visible and UV-vis ranges. The material fabrication route covers the electrochemical anodization of a Ti plate, followed by thin AuCu film magnetron sputtering and further thermal treatment. Scanning electron microscopy images confirmed the presence of spherical nanoparticles (NPs) formed on the external and internal walls of NTs. The optical and structural properties were characterized using UV-vis, X-ray diffraction, and X-ray photoelectron spectroscopies. It was proved that thermal processing under the argon atmosphere leads to the formation of a CuAuTi alloy in contrast to materials fabricated in air, vacuum, and hydrogen. The electrochemical measurements were carried out in NaOH using cyclic voltammetry, linear voltammetry, and chronoamperometry. The highest photoactivity was achieved for materials thermally treated in the argon atmosphere. In addition, the Mott-Schottky analysis was performed for bare TiO2 NTs and TiO2 NTs modified with gold copper NPs indicating a shift in the flatband potential. Overall, thermal processing resulted in changes in optical and structural properties as well as electrochemical and photoelectrochemical activities.

Enzyme Immobilization on Gold Nanoparticles for Electrochemical Glucose Biosensors.

More than 50 years have passed since Clark and Lyon developed the concept of glucose biosensors. Extensive research about biosensors has been carried out up to this day, and an exponential trend in this topic can be observed. The scope of this review is to present various enzyme immobilization methods on gold nanoparticles used for glucose sensing over the past five years. This work covers covalent bonding, adsorption, cross-linking, entrapment, and self-assembled monolayer methods. The experimental approach of each modification as well as further results are described. Designated values of sensitivity, the limit of detection, and linear range are used for the comparison of immobilization techniques.

Formation of the hollow nanopillar arrays through the laser-induced transformation of TiO2 nanotubes.

In the following article, we present a simple, two-step method of creating spaced, hollow nanopillars, from the titania nanotube arrays via pulsed laser-treatment. Due to the high ordering of the structure, the prepared material exhibits photonic properties, which has been shown to increase the overall photoefficiency. The optical and morphological changes in the titania nanotubes after pulsed laser-treatment with 532, 355, and 266 nm wavelengths in the 10-50 mJ/cm2 fluence range are studied. The investigation reveals, that by using appropriate wavelength and energy, the number of surface defects, geometrical features, or both can be tailored.

Anodic titania nanotubes decorated with gold nanoparticles produced by laser-induced dewetting of thin metallic films.

Herein, we combine titania layers with gold species in a laser-supported process and report a substantial change of properties of the resulting heterostructures depending on the major processing parameters. Electrodes were fabricated via an anodisation process complemented with calcination to ensure a crystalline phase, and followed by magnetron sputtering of metallic films. The obtained TiO2 nanotubes with deposited thin (5, 10 nm) Au films were treated with a UV laser (355 nm) to form Au nanoparticles on top of the nanotubes. It was proven that selected laser working parameters ensure not only the formation of Au nanoparticles, but also simultaneously provide preservation of the initial tubular architecture, while above-threshold laser fluences result in partial destruction (melting) of the top layer of the nanotubes. For almost all of the samples, the crystalline phase of the nanotubes observed in Raman spectra was maintained independently of the laser processing parameters. Enhanced photoresponse up to ca 6 mA/cm2 was demonstrated by photoelectrochemical measurements on samples obtained by laser annealing of the 10 nm Au coating on a titania support. Moreover, a Mott-Schottky analysis indicated the dramatically increased (two orders of magnitude) concentration of donor density in the case of a laser-treated Au-TiO2 heterojunction compared to reference electrodes.