Surface Composition Research Articles

Parasitoid attachment ability and the host surface wettability

Climbing animals such as geckos and arthropods developed astonishing adhesive mechanisms which are fundamental for their survival and represent valuable models for biomimetic purposes. A firm adhesion to the host surface, in order to successfully lay eggs is necessary for the reproduction of most parasitoid insects. In the present study, we performed a comparative investigation on the attachment ability of four parasitoid species (the egg parasitoid Anastatus bifasciatus (Eupelmidae), the aphid parasitoid Aphidius ervi (Braconidae), the fly pupal ectoparasitoid Muscidifurax raptorellus (Pteromalidae) and the pupal parasitoid of Drosophila Trichopria drosophilae (Diapriidae)) with hosts characterized by a surface having different wettability properties. The friction force measurements were performed on smooth artificial (glass) surfaces showing different contact angles of water. We found that attachment systems of parasitoid insects are tuned to match the wettability of the host surface. Sexual dimorphism in the attachment ability of some tested species has been also observed. The obtained results are probably related to different microstructure and chemical composition of the host surfaces and to different chemical composition of the parasitoid adhesive fluid. The data here presented can be interpreted as an adaptation, especially in the female, to the physicochemical properties of the host surface and contribute to shed light on the coevolutionary processes of parasitoid insects and their hosts.

Changes in the enamel surface in patients with polymorphism of the <i>VDR</i> gene under the action of remineralizing composition and vitamin D

BACKGROUND: The leading role in the pathogenetic mechanism of caries development is the imbalance between the de and remineralization of hard tooth tissues. The combination of VDR alleles affects calcium-phosphate metabolism. In 65% of the human population, the structure of the VDR gene has a genetic polymorphism. AIM: To study the effect of vitamin D and a remineralizing paste on the enamel surface structure in patients with genetic polymorphism of VDR gene receptors. MATERIALS AND METHODS: In 18 individuals with a polymorphism index of the VDR A/A gene, a laboratory indicator of 25 (OH) vitamin D in the blood of 18.20±1.84 ng/ml, according to orthodontic indications, the retinated third molars in the lower jaw were removed. Then, the samples were lowered into three flasks of six pieces with 100 ml of artificial saliva. Containers with teeth were divided into groups: group 1, with a solution of artificial saliva only; group 2, an additional 1,000 IU of an aqueous solution of vitamin D; and group 3, tooth enamel was treated for 2 minutes with an electric toothbrush with a paste containing a remineralizing composition, immersed in artificial saliva with cholecalciferol 1,000 IU. The flasks were in the thermostat at a temperature of 37.4 C per day. In all samples, electron microscopy of the enamel contact surface at the level of the crown equator was performed using a Tescan Mira 3 LMU microscope (TESCAN, Czech Republic) with an Oxford X-MAX 5 energy dispersive X-ray detector (Oxford Instruments, United Kingdom) with analysis of local mineral composition. RESULTS: In group 1, with electron microscopy of enamel, areas of increased mineralization alternated with areas of reduced density. The coefficient of the molar ratio Ca/P was 1.32±0.13, indicating the destruction of hydroxyapatites. In group 2 the intercrystalline pore space was filled with calcium and phosphate ions. In group 3, the enamel surface acquired a smooth homogeneous relief. An increase in the weight percentage of trace elements was observed, and the Ca/P ratio was 2.20±0.02, which indicated a phase of remineralization. CONCLUSION: Patients with VDR gene polymorphism have a vitamin D deficiency in the blood serum. The trace element composition of the enamel surface is characterized by a phase of demineralization. Treatment with remineralizing paste and addition of cholecalciferol solution to artificial saliva changes the structure of hydroxyapatite and increases the caries-resistant properties of enamel.

Improved Compatibility of α-NaMnO2 Cathodes at the Interface with Safer and more Reliable Electrolytes.

The behaviour and compatibility of monoclinic sodium manganite, α-NaMnO2, cathodes at the interface with electrolytes based on the 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMIFSI) and N-trimethyl-N-butylammonium bis(fluorosulfonyl)imide (N1114FSI) ionic liquids is presented and discussed. The Na+ insertion process was analysed through cyclic voltammetry tests combined with impedance spectroscopy measurements and the cell performance was tested by charge-discharge cycles. XPS and FIB-SEM measurements allowed analysis of the surface composition and the morphology of post-mortem cathodes. Overall, the α-NaMnO2 cathode showed high reversibility in N1114FSI-based electrolyte, delivering 60 % of the initial capacity after 1200 cycles in conjunction with a Coulombic efficiency above 99%. To our knowledge, these very promising results are the best result obtained till now for monolithic α-NaMnO2 cathodes, are ascribable to the formation of a stable passive layer onto the electrode surface, as confirmed by spectroscopic analysis.

Fabrication of a coral-like barium titanate nano-piezoelectric coating and its effect on promoting osteogenic differentiation of rat bone marrow mesenchymal stem cells in vitro

Objective: To investigate the biocompatibility of coral-like barium titanate nano-piezoelectric coatings and the influence of ultrasound-excited piezoelectric effect on the early osteogenic differentiation. Methods: The barium titanate nano-piezoelectric coating (the coating group) was prepared on the surface of titanium metal by anodic oxidation, hydrothermal reaction and high-temperature annealing, and polished titanium specimens were used as control group. The surface morphology, composition, and crystal phase and hydrophilicity of the two groups of titanium specimens were characterized using scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and contact angle meter. The piezoelectric properties of the materials were characterized by piezoresponse force microscopy. Rat bone marrow mesenchymal stem cells (BMSC) were cultured and identified and seeded the surface of titanium specimens in two groups. The cells seeded on blank culture plates were used as blank group. After low intensity pulsed ultrasound intervention, cell proliferation and live/dead staining were detected to evaluate cytocompatibility of the coatings. Alkaline phosphatase (ALP) activity of each group was detected by ALP staining kit, and the expression of osteogenesis-related genes [integrin, bone morphogenetic protein 2 (BMP-2), Runt-related transcription factor 2 (RUNX2)] was detected by real-time fluorescent quantitative PCR (RT-qPCR) to evaluate the effect of the coating on promoting the early osteogenic differentiation of BMSC. Results: The surface of titanium specimens in the coating group showed a uniform coral-like morphology, and the diameter of the coral tentacles was 70-100 nm. The main component was tetragonal barium titanate. The surface hydrophilicity of the coating group (water contact angle 10.12°± 0.93°) was significantly better than that of the control group (water contact angle 78.32°±0.71°) (F= 10 165.91, P<0.001). The coating has a stable piezoelectric property with a piezoelectric constant of about 5 pC/N. Cell experiments showed that, with or without ultrasound, the cell proliferation activity of the coating group was significantly lower than that of the blank group and the control group on the third day (P<0.05). On the fifth day, with or without ultrasound, there was no significant difference in cell proliferation activity between the three groups (P>0.05). After 7 days of culture, the ALP activity of the coating group was significantly higher than that of the blank group and the control group (P<0.05). The results of RT-qPCR showed that the mRNA expression of integrin and BMP-2 in the coating group with ultrasound was significantly higher than that in the other groups with ultrasound, and was higher than that of the coating group without ultrasound (P<0.05). The expression of integrin mRNA in the control group with ultrasound was significantly higher than that in the control group without ultrasound (P<0.05). The expression of RUNX2 mRNA in the coating group with ultrasound was significantly higher than that in the coating group without ultrasound (P<0.05). Conclusions: The coral-like barium titanate nano-piezoelectric coating exhibits favorable biocompatibility and stable piezoelectric property, and facilitates the early osteogenic differentiation of BMSC under the excitation of low-intensity pulsed ultrasound.

In-situ synchrotron x-ray photoelectron spectroscopy study of medium-temperature baking of niobium for SRF application

In order to determine optimal parameters of vacuum thermal processing of superconducting radiofrequency niobium cavities exhaustive information on the initial chemical state of niobium and its modification upon a vacuum heat treatment is required. In the present work the chemical composition of the niobium surface upon ultra-high vacuum baking at 200 ∘C–400 ∘C similar to ‘medium-temperature baking’ and ‘furnace baking’ of cavities is explored in-situ by synchrotron x-ray photoelectron spectroscopy (XPS). Our findings imply that below the critical thickness of the Nb2O5 layer ( ≈1nm ) niobium starts to interact actively with surface impurities, such as carbon and phosphorus. By studying the kinetics of the native oxide reduction, the activation energy and the rate-constant relation have been determined and used for the calculation of the oxygen-concentration depth profiles. It has been established that the controlled diffusion of oxygen is realized at temperatures 200 ∘C–300 ∘C, and the native-oxide layer represents an oxygen source, while at 400 ∘C the pentoxide is completely reduced and the doping level is determined by an ambient oxygen partial pressure. Fluorine (F to Nb atomic ratio is 0.2) after the buffered chemical polishing was found to be incorporated into the surface layer probed by XPS ( ≈4.6nm ), and its concentration increased during the low-temperature baking (F/Nb = 0.35 at 230 ∘C) and depleted at higher temperatures (F/Nb = 0.11 at 400 ∘C). Thus, the influence of fluorine on the performance of mid-T baked, nitrogen-doped and particularly mild-baked (120 ∘C/48 h) cavities must be considered. The possible role of fluorine in the educed Nb+5→Nb+4 reaction under the impact of an x-ray beam at room temperature and during the thermal treatment is also discussed. The range of temperature and duration parameters of the thermal treatment at which the niobium surface would not be contaminated with impurities is determined.

Electro-osmotic Flow Generation via a Sticky Ion Action.

Selective transport of ions through nanometer-sized pores is fundamental to cell biology and central to many technological processes such as water desalination and electrical energy storage. Conventional methods for generating ion selectivity include placement of fixed electrical charges at the inner surface of a nanopore through either point mutations in a protein pore or chemical treatment of a solid-state nanopore surface, with each nanopore type requiring a custom approach. Here, we describe a general method for transforming a nanoscale pore into a highly selective, anion-conducting channel capable of generating a giant electro-osmotic effect. Our molecular dynamics simulations and reverse potential measurements show that exposure of a biological nanopore to high concentrations of guanidinium chloride renders the nanopore surface positively charged due to transient binding of guanidinium cations to the protein surface. A comparison of four biological nanopores reveals the relationship between ion selectivity, nanopore shape, composition of the nanopore surface, and electro-osmotic flow. Guanidinium ions are also found to produce anion selectivity and a giant electro-osmotic flow in solid-state nanopores via the same mechanism. Our sticky-ion approach to generate electro-osmotic flow can have numerous applications in controlling molecular transport at the nanoscale and for detection, identification, and sequencing of individual proteins.

Role of the Microstructure in the Li-Storage Performance of Spinel-Structured High-Entropy (Mn,Fe,Co,Ni,Zn) Oxide Nanofibers

High-entropy oxides with spinel structure (SHEOs) are promising anode materials for next-generation lithium-ion batteries (LIBs). In this work, electrospun (Mn,Fe,Co,Ni,Zn) SHEO nanofibers produced under different conditions are evaluated as anode materials in LIBs and thoroughly characterised by a combination of analytical techniques. The variation of metal load (19.23 or 38.46 wt% relative to the polymer) in the precursor solution and of calcination conditions (700 °C/0.5 h, or 700 °C/2 h followed by 900 °C/2 h) affects the morphology, microstructure, crystalline phase, and surface composition of the pristine SHEO nanofibers and the resulting electrochemical performance, whereas mechanism of Li+ storage does not substantially change. Causes of long-term (≥650 cycles) capacity fading are elucidated via ex situ synchrotron X-ray absorption spectroscopy. The results evidence that the larger amounts of Fe, Co, and Ni cations irreversibly reduced to the metallic form during cycling are responsible for faster capacity fading in nanofibers calcined under milder conditions. The microstructure of the active material plays a key role. Nanofibers composed by larger and better-crystallized grains, where a stable solid/electrolyte interphase forms, exhibit superior long-term stability (453 mAh g−1 after 550 cycles at 0.5 A g−1) and rate-capability (210 mAh g−1 at 2 A g−1).

Assessment of the Influence of Fabric Structure on Their Electro-Conductive Properties.

Electro-conductive fabrics are key materials for designing and developing wearable smart textiles. The properties of textile materials depend on the production method, the technique which leads to high conductivity, and the structure. The aim of the research work was to determine the factors affecting the electrical conductivity of woven fabrics and elucidate the mechanism of electric current conduction through this complex, aperiodic textile material. The chemical composition of the material surface was identified using scanning electron microscopy energy dispersion X-ray spectroscopy. The van der Pauw method was employed for multidirectional resistance measurements. The coefficient was determined for the assessment of the electrical anisotropy of woven fabrics. X-ray micro-computed tomography was used for 3D woven structure geometry analysis. The anisotropy coefficient enabled the classification of electro-conductive fabrics in terms of isotropic or anisotropic materials. It was found that the increase in weft density results in an increase in sample anisotropy. The rise in thread width can lead to smaller electrical in-plane anisotropy. The threads are unevenly distributed in woven fabric, and their widths are not constant, which is reflected in the anisotropy coefficient values depending on the electrode arrangement. The smaller the fabric area covered by four electrodes, the fewer factors leading to structure aperiodicity.

Development and characterization of AZ91/AlN magnesium matrix composites via friction stir processing

Magnesium AZ91/AlN-based surface composites have been synthesized using the friction stir processing (FSP) technique. The influence of particle addition during FSP on microstructural and mechanical properties has been investigated. Composite plates of 5, 10, and 15 vol. % AlN were synthesized using two-pass FSP with an axial force of 10 KN, a tool travel speed of 40 mm/min, and a tool rotation speed of 1200 rpm. The AZ91/AlN surface composites were analyzed microscopically with the use of an optical microscope, an x-ray diffractometer, and a scanning electron microscope. The prepared composites were tested for hardness and tensile strength. Micrographs taken in the stir zone revealed a consistent distribution of AlN particles throughout the AZ91 matrix. The AZ91/AlN surface composites were tested for hardness and tensile strength, and the findings showed that the AlN particles improved the mechanical properties without significantly decreasing ductility. The fracture surfaces of the composites were studied, and the mechanisms of fracture were identified.

Surface composition and electronic properties of Co-Cu mixed oxalates: A detailed XPS analysis

X-ray photoelectron spectroscopy and X-ray diffraction were employed to characterize the structure, surface composition, atoms’ chemical state and electronic structure of bimetallic Co-Cu oxalates with a nominal composition of Co0.75Cu0.25C2O4, Co0.5Cu0.5C2O4 and Co0.33Cu0.67C2O4. High-resolution core-level spectra of the components, X-ray induced Cu L3VV Auger spectra and valence band spectra are presented for these oxalates along with a detailed analysis of a number of spectral parameters in comparison with those for monometallic Co and Cu oxalates. A consistent variation of different spectral parameters is considered in terms of changes in the strength of Me–O bonding. Due to charge transfer processes, Co-rich Co0.75Cu0.25C2O4 (Co/Cu = 3) oxalate displays the highest degree of covalency of Co–O bonds and ionicity of Cu–O bonds compared to CoC2O4, CuC2O4 and the other Co-Cu oxalates. The role of Cu1+ ions either initially present in Cu-containing oxalates or progressively accumulated during their X-ray irradiation is discussed in terms of strengthening/weakening of interatomic Me–O bonds.

A SEM/EDS evaluation of debris removal of used rotary Ni-Ti endodontic files by four different cleaning solutions

PurposeThe aim of this study was to compare the efficacies levels of four cleaning solutions for removing debris from rotary Nickel-Titanium (Ni–Ti) endodontic instruments. Materials and methodsTwelve instruments that fractured during ex vivo instrumentation were used. Fractured surfaces were investigated by SEM before and after 3, 6 and 9 min of ultrasonic cleaning in 17 % EDTA.3NaOH (Group A), 2.5 % NaOCl (Group B), Dentasept 3H Rapide (Group C) and ZymeX™ (Group D) solutions. EDS analyses of selected files from all four groups of untreated and ultrasonically cleaned samples were performed to assess the elemental composition of the alloy surfaces. ResultsSEM analysis revealed that after 9 min of ultrasonic agitation, all four investigated solutions had cleaned fractured surfaces. However, some low-atomic-number regions exhibited random distributions on the fractured surfaces. EDS analyses indicated that only C was retained on surface after 9 min of ultrasonic cleaning. This finding was common in all tested groups. ConclusionsAll four investigated solutions substantially removed debris from the surfaces of the Ni–Ti files and were considered appropriate for clinical practice.

Ni-W composite coating reinforced with CrN nanoparticles on X80 pipeline steel: Preparation and characterization

X80 pipeline steel is crucial for oil and gas pipelines. Friction between particulate matter and the inner wall causes abrasive wear during transport, while corrosive environments further degrade the pipeline, leading to leaks. In this study, a nanoscale Ni-W-CrN composite coating was successfully prepared on X80 steel via electrodeposition for protection. The coating's surface morphology, microstructure, and composition were analyzed. The effects of CrN nanoparticle concentration and deposition temperature on the coating's structure, wear, and corrosion resistance were investigated. At 10 g/L CrN and 60°C, the Ni-W-CrN film showed a fine-grained surface with 8.13 wt% CrN, achieving 810 HV microhardness and improving wear and corrosion resistance by 81 % and 89 % compared to Ni-W coatings.

Electrochemical development and characterisation of nanostructured Ni–Fe alloy coatings for corrosion protection

ABSTRACT Nanostructured Ni–Fe alloy coatings were developed galvanostatically using a new low-concentration bath. The composition and operating parameters of the bath were optimised by taking the benefit of the conventional Hull cell method. Ni–Fe alloy coatings were developed at different current densities (2.0 to 5.0 A dm−2), keeping pH = 2.5. The corrosion behaviour of electrodeposited alloy coatings was evaluated in 3.5% NaCl solution, using Electrochemical Impedance Spectroscopy (EIS) and potentiodynamic polarisation methods. Ni–Fe alloy coating, deposited at 2.0 A dm−2 exhibited a lesser corrosion rate (14.71 × 10−2 mm y−1) than those at higher current densities. The lowest corrosion rate was attributed to its least crystallite size (10.4 nm), evidenced by an X-Ray Diffraction (XRD) study. The corrosion performance of Ni–Fe alloy coatings was discussed in the light of their surface morphology and composition, evidenced by SEM and Energy-Dispersive X-ray spectroscopy (EDS) analysis, respectively.

Tuning Stainless Steel Oxide Layers through Potential Cycling─AEM Water Electrolysis Free of Critical Raw Materials.

Anion exchange membrane water electrolyzers (AEMWEs) have an intrinsic advantage over acidic proton exchange membrane water electrolyzers through their ability to use inexpensive, stable materials such as stainless steel (SS) to catalyze the sluggish oxygen evolution reaction (OER). As such, the study of active oxide layers on SS has garnered great interest. Potential cycling is a means to create such active oxide layers in situ as they are readily formed in alkaline solutions when exposed to elevated potentials. Cycling conditions in the literature are rife with unexplained variations, and a complete account of how these variations affect the activity and constitution of SS oxide layers remains unreported, along with their influence on AEMWE performance. In this paper, we seek to fill this gap in the literature by strategically cycling SS felt (SSF) electrodes under different scan rates and ranges. The SSF anodes were rapidly activated within the first 50 cycles, as shown by the 10-fold decline in charge transfer resistance, and the subsequent 1000 cycles tuned the metal oxide surface composition. Cycling the Ni redox couple (RC) increases Ni content, which is further enhanced by lowering the cycling rate, while cycling the Fe RC increases Cr content. Fair OER activity was uncovered through cycling the Ni RC, while Fe cycling produced SSF electrodes active toward both the OER and the hydrogen evolution reaction (HER). This indicates that inert SSF electrodes can be activated to become efficient OER and HER electrodes. To this effect, a single-cell AEMWE without any traditional catalyst or ionomer generated 1.0 A cm-2 at 1.94 V ± 13.3 mV with an SSF anode, showing a fair performance for a cell free of critical raw materials.

Impact of Surface Composition Changes on the CO2-Reduction Performance of Au-Cu Aerogels.

Over the past decades, the electrochemical CO2-reduction reaction (CO2RR) has emerged as a promising option for facilitating intermittent energy storage while generating industrial raw materials of economic relevance such as CO. Recent studies have reported that Au-Cu bimetallic nanocatalysts feature a superior CO2-to-CO conversion as compared with the monometallic components, thus improving the noble metal utilization. Under this premise and with the added advantage of a suppressed H2-evolution reaction due to absence of a carbon support, herein, we employ bimetallic Au3Cu and AuCu aerogels (with a web thickness ≈7 nm) as CO2-reduction electrocatalysts in 0.5 M KHCO3 and compare their performance with that of a monometallic Au aerogel. We supplement this by investigating how the CO2RR-performance of these materials is affected by their surface composition, which we modified by systematically dissolving a part of their Cu-content using cyclic voltammetry (CV). To this end, the effect of this CV-driven composition change on the electrochemical surface area is quantified via Pb underpotential deposition, and the local structural and compositional changes are visually assessed by employing identical-location transmission electron microscopy and energy-dispersive X-ray analyses. When compared to the pristine aerogels, the CV-treated samples displayed superior CO Faradaic efficiencies (≈68 vs ≈92% for Au3Cu and ≈34 vs ≈87% for AuCu) and CO partial currents, with the AuCu aerogel outperforming the Au3Cu and Au counterparts in terms of Au-mass normalized CO currents among the CV-treated samples.

Systematic testing, verification and validation of laser treatments for unglazed earthenware affected by lichens and fungi biodeterioration

In recent years, there has been a growing interest in exploring environmentally friendly and healthy alternatives to conventional solvent cleaning and biocides in the conservation of stone artworks. Here, we focus on the potential of laser-based photonic methods for treating biodeteriorated earthenware artefacts. The investigation was conducted on Roman dolia (jars) of the International Museum of Ceramics, Faenza, Italy. Three removal methods were tested and compared: (i) brushing using a soft-bristled electric brush and water, referred to as brush cleaning; (ii) a combination of brushing and laser ablation; and (iii) biocide and brushing. Four laser systems with different wavelengths and optimized pulse durations in nanosecond or microsecond regimes were used in the tests. Systematic irradiation tests were conducted to determine the damage thresholds and define safe laser irradiation levels. The characterizations of the surfaces under treatment were carried out pre- and post-laser irradiation using optical microscopy, 3D photogrammetry, and Pulse-Amplitude-Modulated Chlorophyll-Fluorometry. Furthermore, spectroscopic methods based on FTIR, Raman, and LIBS techniques were used to assess the effectiveness of the removal process and the composition of uncovered surfaces. Results have indicated that gentle brushing and water is the most effective approach for safely removing around 60% of the bio-colonization weakly anchored to the substrate over the area under treatment. This comprised viable species, whereas the remaining 40% of the area included endolithic species, mostly thalli of Verrucaria nigrescens and rock-dwelling fungi. The eradication of the latter was the real conservation concern requiring attention. Following the experimentation, the optimal method for safely uncovering the earthenware surface was a combination of water-assisted brushing and 1064 nm laser irradiation as a finishing treatment.

“Microwave approach and thermal decomposition: A sustainable way to produce ZnO nanoparticles with different chemo-physical properties”

Two different synthetic approaches such as thermal decomposition method and microwave-assisted procedure were compared for the synthesis of nanosized ZnO. The two procedures were tested using zinc acetate as precursor as is, or in the presence of two coadjutants, one of anthropic origin (melamine) and one derived from the reuse of agricultural waste (wine extracts). All the samples were physico-chemically characterized in order to evaluate the influence of the synthesis conditions on the properties of the materials that were characterized by N2 adsorption/desorption at 77 K and Field Emission-Scanning Electron microscopy measurements for evaluating the morphology, X-ray diffraction for examining the crystalline structure and X-Ray photoelectron spectroscopy for evidencing the surface composition of the nanoparticles. In order to verify the influence of the synthesis procedure on the electrical and optical properties of the ZnO nanoparticles, forecasting their use in photocatalytic applications, also the band gap of materials was evaluated by means of UV–Vis spectroscopy and Tauc plot. A final comparison of all the results allowed to evidence advantages and disadvantages of the procedures under study pointing out the importance of deepen the study of microwave-based synthetic approaches.

Characterizing oxidation, thickness, and composition of metallic glass thin films with combined electron probe microanalysis and X-ray photoelectron spectroscopy

Metallic glass thin films (MGTFs) are a recently developed class of alloy coatings with potential applications ranging from biomedical devices to electrical components. Their tribological performance in service conditions is dictated by MGTF bulk composition but can be limited by the native oxide surface that inevitably forms upon exposure to atmosphere. Surface oxidation, thickness, and composition of ZrCuNiAl MGTFs were characterized using a combination of X-ray photoelectron microscopy (XPS) and electron probe microanalysis (EPMA). MGTF samples with nominal thicknesses of 50, 500, and 1500 nm were sputtered onto Si and SiN wafer substrates within a high vacuum deposition chamber and their amorphicity was confirmed by X-ray diffraction. XPS depth profiling identified the thin film composition and showed that the surface oxide was dominated by a mixed layer of mostly ZrO2, a little oxidized Al, and some metallic Zr. EPMA X-ray intensities were acquired as a function of beam energy to excite characteristic X-rays from different depths of the MGTFs and reconstructed using open-source thin film analysis software BadgerFilm, to determine the composition and thickness of sample layers. EPMA results constrain the composition to be Zr54Cu29Al10Ni7 within 0.7 at. % variation and total thicknesses to be 49, 470, and 1546 nm. Using the oxide composition identified from XPS depth profiling as an input for BadgerFilm analysis, EPMA results indicate the surface oxidation layer on each of the thin film samples was 6.5 ± 1.1 nm thick and uniform across a 0.25 mm region of the film.

Unraveling the Heat- and UV-Induced Degradation of Mixed Halide Perovskite Thin Films via Surface Analysis Techniques.

In recent years, organic-inorganic hybrid perovskite materials have become one of the most promising materials in the new generation of solar cells. These perovskites can provide excellent photoelectric properties after a simple fabrication process. Although perovskite solar cells have achieved high power conversion efficiency, instability concerns regarding material exposure to heat, moisture, air, and UV light present hindrances to commercialization. In this study, three kinds of perovskites (MAPbI3, MAPbI3-xBrx, and MAPbI3-xClx) were used to investigate the crystal stability upon exposure to heat and UV light. SEM, XRD, and FTIR were used to observe the surface morphology, crystal structure, and functional groups of the perovskite thin films. XPS was used to examine the surface composition and chemical state of the perovskite thin films under different conditions. Among these three types of perovskites, it was found that the MAPbI3-xBrx crystal demonstrated the best stability. ToF-SIMS was used to confirm the molecular distribution of the MAPbI3-xBrx films upon exposure to heat and UV light at different depths. ToF-SIMS revealed that [Pb]+ and [PbI]+ aggregated at the interface between the perovskite and ITO substrate after 14 days of thermal treatment. On the other hand, [Pb]+ and [PbI]+ were distributed uniformly after 3 days of UV exposure. This study systematically analyzed and revealed the thermal- and UV-induced degradation process of three perovskite films by using surface analysis techniques. It was concluded that bromine-doped perovskite films had better stability, and UV light caused more severe damage than heat.

Dual role of the peptide-loading complex as proofreader and limiter of MHC-I presentation

Antigen presentation via major histocompatibility complex class I (MHC-I) molecules is essential for surveillance by the adaptive immune system. Central to this process is the peptide-loading complex (PLC), which translocates peptides from the cytosol to the endoplasmic reticulum and catalyzes peptide loading and proofreading of peptide-MHC-I (pMHC-I) complexes. Despite its importance, the impact of individual PLC components on the presented pMHC-I complexes is still insufficiently understood. Here, we used stoichiometrically defined antibody-nanobody complexes and engineered soluble T cell receptors (sTCRs) to quantify different MHC-I allomorphs and defined pMHC-I complexes, respectively. Thereby, we uncovered distinct effects of individual PLC components on the pMHC-I surface pool. Knockouts of components of the PLC editing modules, namely tapasin, ERp57, or calreticulin, changed the MHC-I surface composition to a reduced proportion of HLA-A*02:01 presentation compensated by a higher ratio of HLA-B*40:01 molecules. Intriguingly, these knockouts not only increased the presentation of suboptimally loaded HLA-A*02:01 complexes but also elevated the presentation of high-affinity peptides overexpressed in the cytosol. Our findings suggest that the components of the PLC editing module serve a dual role, acting not only as peptide proofreaders but also as limiters for abundant peptides. This dual function ensures the presentation of a broad spectrum of antigenic peptides.