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Two-dimensional (2D) crystals have renewed opportunities in design and assembly of artificial lattices without the constraints of epitaxy. However, the lack of thickness control in exfoliated van der Waals (vdW) layers prevents realization of repeat units with high fidelity. Recent availability of uniform, wafer-scale samples permits engineering of both electronic and optical dispersions in stacks of disparate 2D layers with multiple repeating units. Here we present optical dispersion engineering in a superlattice structure comprising alternating layers of 2D excitonic chalcogenides and dielectric insulators. By carefully designing the unit cell parameters, we demonstrate greater than 90% narrow band absorption in less than 4 nm of active layer excitonic absorber medium at room temperature, concurrently with enhanced photoluminescence in square-centimetre samples. These superlattices show evidence of strong light–matter coupling and exciton–polariton formation with geometry-tuneable coupling constants. Our results demonstrate proof of concept structures with engineered optical properties and pave the way for a broad class of scalable, designer optical metamaterials from atomically thin layers. Square-centimetre scale, multilayer superlattice structures based on atomically thin two-dimensional chalcogenide monolayers enable the realization of excitonic metamaterials.

Dilute alloy catalysts have the potential to enhance selectivity and activity for large-scale reactions. Highly dilute Pd-in-Au nanoparticle alloys partially embedded in porous silica (“raspberry colloid templated” (RCT)-SiO2) prove to be robust and selective catalysts for oxidative coupling of methanol. Palladium concentrations in the bimetallic nanoparticles as low as ~3.4 at.% catalyze the production of methyl formate with a selectivity of ~95% at conversions of ~55%, whereas conversions are low (

Platinum is the primary catalyst for many chemical reactions in the field of heterogeneous catalysis. However, platinum is both expensive and rare. Therefore, it is advantageous to combine Pt with another metal to reduce cost while also enhancing stability. To that end, Pt is often combined with Co to form Co-Pt nanocrystals. However, dynamical restructuring effects that occur during reaction in Co-Pt ensembles can impact catalytic properties. In this study, model Co2Pt3 nanoparticles supported on carbon were characterized during a redox cycle with two in situ approaches, namely, X-ray absorption spectroscopy (XAS) and scanning transmission electron microscopy (STEM) using a multimodal microreactor. The sample was exposed to temperatures up to 500 °C under H2, and then to O2 at 300 °C. Irreversible segregation of Co in the Co2Pt3 particles was seen during redox cycling, and substantial changes of the oxidation state of Co were observed. After H2 treatment, a fraction of Co could not be fully reduced and incorporated into a mixed Co-Pt phase. Reoxidation of the sample increased Co segregation, and the segregated material had a different valence state than in the fresh, oxidized sample. This in situ study describes dynamical restructuring effects in CoPt nanocatalysts at the atomic scale that are crucial to understand in order to improve the design of catalysts used in major chemical processes.

We report IR and UV/Vis spectroscopic signatures that allow discriminating between the oxidation states of the manganese-based water oxidation catalyst [(Mn4 O4 )(V4 O13 )(OAc)3 ]3- . Simulated IR spectra show that V=O stretching vibrations in the 900-1000 cm-1 region shift consistently by about 20 cm-1 per oxidation equivalent. Multiple bands in the 1450-1550 cm-1 region also change systematically upon oxidation/reduction. The computed UV/Vis spectra predict that the spectral range above 350 nm is characteristic of the managanese-oxo cubane oxidation state, whereas transitions at higher energy are due to the vanadate ligand. The presence of absorption signals above 680 nm is indicative of the presence of MnIII atoms. Spectroelectrochemical measurements of the oxidation from [Mn 2III Mn 2IV ] to [Mn 4IV ] showed that the change in oxidation state can indeed be tracked by both IR and UV/Vis spectroscopy.

Plastics waste has become a major environmental threat, with polyethylene being one of the most produced and hardest to recycle plastics. Hydrogenolysis is potentially the most viable catalytic technology for recycling. Ruthenium (Ru) is one of the most active hydrogenolysis catalysts but yields too much methane. Here we introduce ruthenium supported on tungstated zirconia (Ru-WZr) for hydrogenolysis of low-density polyethylene (LDPE). We show that the Ru-WZr catalysts suppress methane formation and produce a product distribution in the diesel and wax/lubricant base-oil range unattainable by Ru-Zr and other Ru-supported catalysts. Importantly, the enhanced performance is showcased for real-world, single-use LDPE consumables. Reactivity studies combined with characterization and density functional theory calculations reveal that highly dispersed (WO x )n clusters store H as surface hydroxyls by spillover. We correlate this hydrogen storage mechanism with hydrogenation and desorption of long alkyl intermediates that would otherwise undergo further C-C scission to produce methane.

One of the primary factors limiting further research and commercial use of the two-dimensional (2D) titanium carbide MXene Ti3C2, as well as MXenes in general, is the rate at which freshly made samples oxidize and degrade when stored as aqueous suspensions. Here, we show that including excess aluminum during synthesis of the Ti3AlC2 MAX phase precursor leads to Ti3AlC2 grains with improved crystallinity and carbon stoichiometry (termed Al-Ti3AlC2). MXene nanosheets (Al-Ti3C2) produced from this precursor are of higher quality, as evidenced by their increased resistance to oxidation and an increase in their electronic conductivity up to 20 000 S/cm. Aqueous suspensions of stoichiometric single- to few-layer Al-Ti3C2 flakes produced from the modified Al-Ti3AlC2 have a shelf life of over ten months, compared to 1 to 2 weeks for previously published Ti3C2, even when stored in ambient conditions. Freestanding films made from Al-Ti3C2 suspensions stored for ten months show minimal decreases in electrical conductivity and negligible oxidation. Furthermore, oxidation of the improved Al-Ti3C2 in air initiates at temperatures that are 100-150 °C higher than that of conventional Ti3C2. The observed improvements in both the shelf life and properties of Al-Ti3C2 will facilitate the widespread use of this material.

The selective oxidation of methane to methanol at ambient conditions has the potential to enable the use of natural gas obtained in remote areas. We performed multivariate statistical analysis of 1...

Al2O3-supported Pt/Pd bimetallic catalysts were studied using in situ atmospheric pressure and ex situ transmission electron microscopy. Real-time observation during separate oxidation and reduction processes provides nanometer-scale structural details – both morphology and chemistry – of supported Pt/Pd particles at intermediate states not observable through typical ex situ experiments. Significant metal vaporization was observed at temperatures above 600 °C, both in pure oxygen and in air. This behavior implies that material transport through the vapor during typical catalyst aging processes for oxidation can play a more significant role in catalyst structural evolution than previously thought. Concomitantly, Pd diffusion away from metallic nanoparticles on the surface of Al2O3 can also contribute to the disappearance of metal particles. Electron micrographs from in situ oxidation experiments were mined for data, including particle number, size, and aspect ratio using machine learning image segmentation. Under oxidizing conditions, we observe not only a decrease in the number of metal particles but also a decrease in the surface area to volume ratio. Some of the metal that diffuses away from particles on the oxide support can be regenerated and reappears back on the catalyst support surface under reducing conditions. These observations provide insight on how rapid cycling between oxidative and reductive catalytic operating conditions affects catalyst structure.

Ferroelectric switching was studied in 20 nm thick Al0.68Sc0.32N and Al0.64Sc0.36N films (with ~4 nm surface oxides) on platinized silicon wafers by multiple electrical characterization methods. Positive up negative down (PUND) measurements were conducted using 100 $\mu \text{s}$ monopolar triangular waveform excitation. At room temperature, Al0.68Sc0.32N exhibited an apparent remanent polarization, $\text{P}_{\text {r}} = {140}\,\,\mu \text{C}$ /cm2 and a coercive field, $\text{E}_{\text {c}} = {6.5}$ MV/cm, while film leakage prevented quantitative measurement of the Al0.64Sc0.36N ferroelectric properties. Remanent polarizations of $75~\mu \text{C}$ /cm2 for Al0.68Sc0.32N and $25\mu \text{C}$ /cm2for Al0.64Sc0.36N were measured at 120 K. Partial ferroelectric switching was confirmed at room temperature for both materials via the measured transverse piezoelectric coefficients (e31, f) of −1.3 C/m2 (down-switching) and −0.3 C/m2 (up-switching) for Al0.68Sc0.32N, and −0.9 C/m2 (down-switching) and −0.7 C/m2 (up-switching) for Al0.64Sc0.36N.

Recently, materials with hierarchical nanoporous architectures have been proposed to enhance the performance of alloy-type lithium-ion battery (LIB) and sodium-ion battery (SIB) anodes. However, th...

Like all macroorganisms, plants have to control bacterial biofilm formation on their surfaces. On the other hand, biofilms are highly tolerant against antimicrobial agents and other stresses. Consequently, biofilms are also involved in human chronic infectious diseases, which generates a strong demand for anti-biofilm agents. Therefore, we systematically explored major plant flavonoids as putative anti-biofilm agents using different types of biofilms produced by Gram-negative and Gram-positive bacteria. In Escherichia coli macrocolony biofilms, the flavone luteolin and the flavonols myricetin, morin and quercetin were found to strongly reduce the extracellular matrix. These agents directly inhibit the assembly of amyloid curli fibres by driving CsgA subunits into an off-pathway leading to SDS-insoluble oligomers. In addition, they can interfere with cellulose production by still unknown mechanisms. Submerged biofilm formation, however, is hardly affected. Moreover, the same flavonoids tend to stimulate macrocolony and submerged biofilm formation by Pseudomonas aeruginosa. For Bacillus subtilis, the flavonone naringenin and the chalcone phloretin were found to inhibit growth. Thus, plant flavonoids are not general anti-biofilm compounds but show species-specific effects. However, based on their strong and direct anti-amyloidogenic activities, distinct plant flavonoids may provide an attractive strategy to specifically combat amyloid-based biofilms of some relevant pathogens.

Further understanding of how nanoparticle catalyst composition influences the yield of carbon nanotubes (CNTs) is key to their scalable, cost-effective manufacture. In particular, the role of trace carbon deposits on promoting CNT nucleation from the catalyst has been studied recently by our team. Here, we show that deposition of solid carbon onto an iron catalyst film prior to dewetting effectively amplifies the CNT yield. We investigated the effect of the amount of C and Fe on particle formation and reduction, and growth kinetics using a combination of in situ techniques – Raman spectroscopy, X-ray photoelectron spectroscopy and environmental transmission electron microscopy. We found that CNT growth rate and yield are maximized for specific relative thicknesses of C and Fe (∼0.2 and 0.8 nm, respectively). The presence of carbon causes accelerated dewetting of the catalyst, and more rapidly forms a population of metallic Fe particles that grow CNTs at a higher yield. These factors also cumulatively result in a lower incubation time and improved yield. Therefore, loading of catalyst particles with solid carbon is a straightforward and practical route towards boosting CNT yield and improving the efficiency of CNT growth by chemical vapor deposition.

Because of their high conductivity and potential to utilize lithium metal, lithium thiophosphate electrolytes have attracted significant attention to realize solid-state batteries for vehicle appli...

At the moment, climatic conditions are a primary problem of the exploitation of copper ore. The efficiency of preventive actions in order to improve climatic conditions is connected with the knowle...

Selective oxidation of methane into energy-dense liquid derivatives at low temperature and pressure is critical for enabling the use of vast natural gas reserves around the world. This has been rec...

During recent years, mid-infrared (MIR) spectroscopy has matured into a versatile and powerful sensing tool for a wide variety of analytical sensing tasks. Attenuated total reflection (ATR) techniques have gained increased interest due to their potential to perform non-destructive sensing tasks close to real time. In ATR, the essential component is the sampling interface, i.e., the ATR waveguide and its material properties interfacing the sample with the evanescent field ensuring efficient photon-molecule interaction. Gallium arsenide (GaAs) is a versatile alternative material vs. commonly used ATR waveguide materials including but not limited to silicon, zinc selenide, and diamond. GaAs-based internal reflection elements (IREs) are a new generation of semiconductor-based waveguides and are herein used for the first time in direct spectroscopic applications combined with conventional Fourier transform infrared (FT-IR) spectroscopy. Next to the characterization of the ATR waveguide, exemplary surface reactions were monitored, and trace-level analyte detection via signal amplification taking advantage of surface-enhanced infrared absorption (SEIRA) effects was demonstrated. As an example of real-world relevance, the mycotoxin aflatoxin B1 (AFB1) was used as a model analyte in food and feed safety analysis.

The study's aim was to identify the 3-D surface spatial parameters that describe the 3-D surface microtexture of the nickel–carbon (Ni–C) nanocomposite thin films composed of Ni nanoparticles with different average sizes embedded in amorphous hydrogenated carbon, prepared by the combining radio frequency magnetron sputtering technique and plasma-enhanced chemical vapor deposition (RF-PECVD). The deposition time was varied at 7, 10 and 13 min, respectively. The sample investigation was performed using an atomic force microscope, and the obtained data were analyzed and visualized using MountainsMap® Premium software to determine their stereometric surface engineering characteristics. The results from this study provide not only fundamental insights into the texture characteristics, but also directions toward their implementation in nanotribological models.

The combination of complementary, noncovalent interactions is a key principle for the design of multistimuli responsive hydrogels. In this work, an amphiphilic peptide, supramacromolecular hydrogelator which combines metal-ligand coordination induced gelation and thermoresponsive toughening is reported. Following a modular approach, the incorporation of the triphenylalanine sequence FFF into a structural (C3EG ) and a terpyridine-functionalized (C3Tpy ) C3 -symmetric monomer enables their statistical copolymerization into self-assembled, 1D nanorods in water, as investigated by circular dichroism (CD) spectroscopy and transmission electron microscopy (TEM). In the presence of a terpyridine functionalized telechelic polyethylene glycol (PEG) cross-linker, complex formation upon addition of different transition metal ions (Fe2+ , Zn2+ , Ni2+ ) induces the formation of soft, reversible hydrogels at a solid weight content of 1 wt% as observed by linear shear rheology. The viscoelastic behavior of Fe2+ and Zn2+ cross-linked hydrogels are basically identical, while the most kinetically inert Ni2+ coordinative bond leads to significantly weaker hydrogels, suggesting that the most dynamic rather than the most thermodynamically stable interaction supports the formation of robust and responsive hydrogel materials.

The terminal pathway of complement is implicated in the pathology of multiple diseases and its inhibition is, therefore, an attractive therapeutic proposition. The practicalities of inhibiting this pathway, however, are challenging, as highlighted by the very few molecules in the clinic. The proteins are highly abundant, and assembly is mediated by high-affinity protein–protein interactions. One strategy is to target neoepitopes that are present transiently and only exist on active or intermediate complexes but not on the abundant native proteins. Here, we describe an antibody discovery campaign that generated neoepitope-specific mAbs against the C5b6 complex, a stable intermediate complex in terminal complement complex assembly. We used a highly diverse yeast-based antibody library of fully human IgGs to screen against soluble C5b6 antigen and successfully identified C5b6 neoepitope-specific antibodies. These antibodies were diverse, showed good binding to C5b6, and inhibited membrane attack complex (MAC) formation in a solution-based assay. However, when tested in a more physiologically relevant membrane-based assay these antibodies failed to inhibit MAC formation. Our data highlight the feasibility of identifying neoepitope binding mAbs, but also the technical challenges associated with the identification of functionally relevant, neoepitope-specific inhibitors of the terminal pathway.

The paper presents comprehensive mineralogical and geochemical characteristics of Dominican amber-bearing sediments from Siete Cañadas, Hato Mayor Province of the Eastern Mining District (EMD) in the Cordillera Oriental. The characteristics of rocks collected from the borehole in Siete Cañadas area (EMD) were compared with petrography of coaly shales from La Cumbre in the Northern Mining District (NMD). The mineralogy of the rocks was determined using transmitted and reflected light microscopy, scanning electron microscopy, Powder X-ray diffraction and Fourier Transform Raman Spectroscopy. Biomarker analyses by the gas chromatography–mass spectrometry were used to trace the genetic source and transformation stage of organic matter hosted in the core sediments. In this study, the characteristics of rocks from La Cumbre were supplemented with the petrographic data from our studies reported earlier. Based on the findings, it has been concluded that the basins in the investigated parts of the EMD and NMD regions were likely characterized by different, isolated palaeosettings. Transformation and maturation of terrigenous material were affected by locally occurring physicochemical conditions. In both amber deposits, the sedimentation of clastic and organic material proceeded in the presence of marine conditions. In case of the La Cumbre deposit (NMD area), the sedimentation underwent probably in the conditions of the lagoon environment, a shallow maritime lake or periodically flooded plain that facilitated organic matter decomposition and carbonation from meta-lignite to sub-bituminous coal (random reflectance of coal—Rro = 0.39%). In the Siete Cañadas (EMD region), the sedimentation took place in a shallow saltwater basin, where terrigenous material was likely mixed with material found in situ (fauna fossils, carbonate-group minerals) to form the mudstones enriched in bituminous substance of low maturity. The organic matter found in the rocks from both deposits is of mixed terrestrial/marine origin and was deposited in the presence of low oxygen concentration and reducing and/or dysoxic conditions.

Producing acetaldehyde, an important industrial chemical, by direct catalytic non-oxidative dehydrogenation of ethanol presents many advantages over current production methods, including generating hydrogen. However, a stable, active, and selective catalyst is currently unavailable. This work demonstrates that the high activity and selectivity of nanoporous (np) NiCu for this reaction can be stabilized by keeping the catalyst in a metastable (“kinetically trapped”) state. Using a combination of in situ ambient-pressure and ex situ X-ray photoelectron spectroscopy, environmental transmission electron microscopy, and density functional theory calculations enabled correlating changes in surface composition with the changes in activity and stability upon treatment of np NiCu with H2 and O2. Reduction of Ni-doped nanoporous Cu by H2 exposure enhanced the initial activity but led to complete catalyst deactivation within ∼40 hours. In contrast, O2 pretreatment of the same catalyst increased both activity and long-term stability, with only 15% activity loss over 40 hours. The stability of np NiCu as a catalyst inversely correlates with the amount of metallic Ni at the surface, which is enriched by the H2 pretreatment, while the O2 pretreatment leads to a kinetically trapped Ni2+ subsurface state. This work emphasizes that detailed understanding of pretreatment-induced nanoscale structural and compositional changes is necessary to optimize catalyst performance.

Chitosan biocoatings were successfully deposited on the Ti15Mo alloy surface via cataphoretic deposition from a solution of 1 g dm−3 of chitosan in 4% (aq) citric acid. The influence of the cataphoretic deposition parameters on quality and morphology of the obtained coatings were investigated using fluorescence and scanning electron microscopy. The functional groups' presence in chitosan chine were confirmed by ATR-FTIR methods. X-ray analysis revealed the amorphous structure of the chitosan coatings on the Ti15Mo alloy surface. The conducted studies also include assessing the abrasion resistance and adhesion to the substrate of the obtained chitosan coatings. The results show that utilizing the citric acid as a solvent results in the formation of pore free coatings. The yield of the electrophoretic deposition process was in the range of 2–10 mg of deposited chitosan per 1 cm2. The obtained coatings through the unique properties of chitosan are a promising biomaterial for application in medicine.

The interactions between Ni and LaFeO3 were studied on catalysts prepared by Atomic Layer Deposition (ALD) of 0.5-nm films of LaFeO3 on MgAl2O4. Scanning Transmission Electron Microscopy showed that the films covered the support uniformly, even after 5 redox cycles at 1073 K, and X-Ray Diffraction showed that the films had the perovskite structure. Equilibrium between Ni and NiO was studied using coulometric-titration and flow-titration measurements on 5-wt% Ni catalysts, with and without LaFeO3. While equilibrium constants for Ni/MgAl2O4 were similar to that expected for bulk Ni, equilibrium P O 2 were shifted to significantly lower values in the presence of LaFeO3. In studies of Methane Dry Reforming, the shift in equilibrium resulted in catalyst deactivation due to Ni oxidation at low CO:CO2 ratios, even though Ni/LaFeO3/MgAl2O4 otherwise showed a high reaction rate and excellent tolerance against coking.

The morphological stability of silicon single crystal wafers was investigated, after performing cleaning surface treatments based on moderate temperature annealing and plasma sputtering. The wafer surfaces were measured by Tapping mode atomic force microscopy in air, before and after the different treatments. The 3D images were segmented by watershed algorithm identifying the local peaks, and the stereometric parameters were extracted thereof. The analysis of variance allowed to better assess the statistically significant differences. All the resulting quantities were critically discussed. It appeared that the different cleaning treatments affected differently the surface morphology changes occurring between pristine and treated surfaces, making them distinguishable in these terms. The presented combination of measurement technique and analyzing protocol potentially allows one to assess the structural differences of the surfaces of interest, when assumptions are made about the physical origin of the emerging topographical features. In the present case, if no etching is assumed, it appears that all cleaning protocols actually worsen the surface quality. The effect of these morphological differences on the functional properties of the surface should be ascertained independently.

Activating pretreatments are used to tune surface composition and structure of bimetallic-alloy catalysts. Herein, the activation-induced changes in material properties of a nanoporous Ag0.03Au0.97 alloy and their subsequent evolution under steady-state CH3OH oxidation conditions are investigated. Activation using O3 results in AgO and Au2O3, strongly enriching the near-surface region in Ag. These oxides reduce in the O2/CH3OH mixture, yielding CO2 and producing a highly Ag-enriched surface alloy. At the reaction temperature (423 K), Ag realloys gradually with Au but remains enriched (stabilized by surface O) in the top few nanometers, producing methyl formate selectively without significant deactivation. At higher temperatures, bulk diffusion induces sintering and Ag redistribution, leading to a loss of activity. These findings demonstrate that material properties determining catalytic activity are dynamic and that metastable (kinetically trapped) forms of the material may be responsible for catalysis, providing guiding principles concerning the activation of heterogeneous catalysts for selective oxidation.

Improving the selectivity for catalytic hydrogenation of alkynes is a key step in upgrading feedstocks for olefin polymerization. Herein, dilute PdxAu1–x alloy nanoparticles embedded in raspberry c...

Carbon‐carbon bond formation is a fundamental transformation in both synthetic chemistry and biosynthesis. Enzymes catalyze such reactions with exquisite selectivity which often cannot be achieved using non‐biological methods but may suffer from an intolerance of high temperature and the presence of organic solvents limiting their applications. Here we report the thermodynamic and kinetic stability of the β‐barrel natural Diels‐Alderase AbyU, which catalyzes formation of the spirotetronate core of the antimicrobial natural product abyssomicin C, with creation of 3 new asymmetric centers. This enzyme is shown to catalyze [4 + 2] cycloadditions at elevated temperature (up to 65 oC), and in the presence of organic solvents (MeOH, CH3CN and DMSO) and the chemical denaturant guanidinium hydrochloride, revealing that AbyU has potential widespread value as a biocatalyst.

Limited understanding of the factors influencing the yield of carbon nanotubes (CNTs) relative to the number of catalyst particles remains an important barrier to their large-scale production with high quality, and to tailoring CNT properties for applications. This lack of understanding is evident in the frequent use of Edisonian approaches to give high-yield CNT growth, and in the sometimes-confusing influence of trace residues on the reactor walls. In order to create conditions wherein CNT yield is reproducible and to enable large-scale and reliable CNT synthesis, it is imperative to understand-fundamentally-how these common practices impact catalytic activity and thus CNT number density. Herein, we use ambient pressure-X-ray photoelectron spectroscopy (AP-XPS) to reveal the influence of carbon and hydrogen on the coupling between catalyst reduction and CNT nucleation, from an iron catalyst film. We observe a positive correlation between the degree of catalyst reduction and the density of vertically aligned CNTs (forests), verifying that effective catalyst reduction is critical to CNT nucleation and to the resulting CNT growth yield. We demonstrate that the extent of catalyst reduction is the reason for low CNT number density and for lack of self-organization, lift-off, and growth of CNT forests. We also show that hydrocarbon byproducts from consecutive growths can facilitate catalyst reduction and increase CNT number density significantly. These findings suggest that common practices used in the field-such as reactor preconditioning-aid in the reduction of the catalyst population, thus improving CNT number density and enabling the growth of dense forests. Our results also motivate future work using AP-XPS and complementary metrology tools to optimize CNT growth conditions according to the catalyst chemical state.

The development of a suitable catalyst for the oxygen reduction reaction (ORR), the cathode reaction of proton exchange membrane fuel cells (PEMFC), is necessary to push this technology toward widespread adoption. There have been substantial efforts to utilize bimetallic Pt-M alloys that adopt the ordered face-centered tetragonal (L1

The interfacial electronic distribution in transition-metal oxide thin films is crucial to their interfacial physical or chemical behaviors. Core-loss electron energy-loss spectroscopy (EELS) may potentially give valuable information of local electronic density of state at high spatial resolution. Here, we studied the electronic properties at the interface of Pb(Zr0.2Ti0.8)O3 (PZT)/4.8 nm La0.8Sr0.2MnO3 (LSMO)/SrTiO3 (STO) using valance-EELS with a scanning transmission electron microscope. Modeled with dielectric function theory, the charge transfer in the vicinity of the interfaces of PZT/LSMO and LSMO/STO was determined from the shifts of plasma peaks of valence EELS (VEELS), agreeing with theoretical prediction. Our work demonstrates that the VEELS method enables a high-efficient quantification of the charge transfer at interfaces, shedding light on the charge-transfer issues at heterogenous interfaces in physical and chemical devices.

Batteries with conversion-type electrodes exhibit higher energy storage density but suffer much severer capacity fading than those with the intercalation-type electrodes. The capacity fading has been considered as the result of contact failure between the active material and the current collector, or the breakdown of solid electrolyte interphase layer. Here, using a combination of synchrotron X-ray absorption spectroscopy and in situ transmission electron microscopy, we investigate the capacity fading issue of conversion-type materials by studying phase evolution of iron oxide composited structure during later-stage cycles, which is found completely different from its initial lithiation. The accumulative internal passivation phase and the surface layer over cycling enforce a rate−limiting diffusion barrier for the electron transport, which is responsible for the capacity degradation and poor rate capability. This work directly links the performance with the microscopic phase evolution in cycled electrode materials and provides insights into designing conversion-type electrode materials for applications., Conversion electrodes possess high energy density but suffer a rapid capacity loss over cycling compared to their intercalation equivalents. Here the authors reveal the microscopic origin of the fading behavior, showing that the formation and augmentation of passivation layers are responsible.

In this study, the impact of supported Pt particles on the thermal and photocatalytic activity of well-defined anatase TiO2 (A-TiO2) nanocrystals (NCs) was investigated. Pt-decorated NCs were characterized using scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The activity of the Pt-decorated NCs for the thermal and photocatalytic reactions of acetaldehyde was then studied using temperature-programmed desorption in ultrahigh vacuum. The bare TiO2 NCs demonstrated thermal activity primarily for aldol condensation, partial oxidation, and reductive coupling pathways. For the Pt-decorated NCs, the Pt deposits were found to act mainly as a site blocker for the thermal aldol condensation and partial oxidation pathways, as well as acting as recombination centers for photogenerated electrons and holes at the surface, suppressing the photocatalytic activity of the NCs. Upon pretreating with O2, however, the photocatalytic activity of the Pt-deco...

Interactions between a metal and its oxide support can influence CO and CH4 oxidation, but promotion by the support can be difficult to study because oxides can have different surface structures and surface areas. To focus on the chemical aspects of support promotion for CO and CH4 oxidation, this study investigated the effect of support composition on Pd catalysts by preparing uniform films of NiO, Co3O4, Fe2O3, MnO2, CeO2, and ZrO2 on γ-Al2O3 using Atomic Layer Deposition (ALD). The structure of the films was characterized by XRD and STEM, and catalysts with ~ 1-wt% Pd were examined for CO and CH4 oxidation. CeO2/γ-Al2O3 was unique among the supports in greatly stabilizing the Pd dispersion to 1173 K. Rates for CO oxidation were enhanced by the presence of CeO2, Fe2O3, and MnO2, while the other oxides had no promotional effect. For CH4 oxidation, only NiO and Co3O4 were modest promoters, while the other reducible oxides even showed a negative effect on rates. Possible reasons for the differences between CH4 and CO oxidation activities are discussed.

The bottom-up approach has been widely used for large-scale synthesis of carbon nanodots (CNDs). However, the structure and origin of photoluminescence in CNDs synthesized by the bottom-up approach is still a subject of debate. Here, using a series of separation techniques like solvent extraction, column chromatography, gel electrophoresis and dialysis, we present three distinct fluorescent components in CNDs synthesized from pyrene, a well-known precursor molecule. The separated components have qualitative and quantitatively different absorption and emission spectral features including quantum yield (QY). Optical and vibrational spectroscopy techniques combined with electron microscopy indicate that a subtle balance between the extent of graphitization and the presence of molecular fluorophores determines the nature of fluorescence emission. Substantial difference in photons/cycle, single particle fluorescence blinking, on-off photoswitching strongly supports the distinct nature of the components.

The bottom-up approach has been the preferred route for large-scale synthesis of graphene quantum dots (GQDs). However, the structure and origin of photoluminescence in these dots synthesized by the bottom-up approach are still a subject of debate. Here, using a series of separation techniques like solvent extraction, column chromatography, gel electrophoresis and dialysis, we present three distinct fluorescent materials in GQDs synthesized from pyrene, a well-known precursor molecule. The subtle balance between the extent of graphitization and molecular fluorophores determines the nature of fluorescence emission in GQDs verified using a suite of optical and vibrational spectroscopy techniques in combination with electron microscopy. The single-particle level emission properties strongly support our observation. Using cell imaging studies, we also verify that all three materials are suitable for fluorescent staining of biological samples. Our results resolve a long-standing debate on the true structural character of GQDs and their source of emission.

Simple Summary The glycocalyx (GCX) is a hydrated, gel-like layer of biological macromolecules attached to the cell membrane. The GCX acts as a barrier and regulates the entry of external substances into the cell. The function of the GCX is highly dependent on its structure and composition. Pathogenic factors can affect the protective structure of the GCX. We know very little about the three-dimensional organization of the GXC. The tiny and delicate structures of the GCX are difficult to study by microscopic techniques. In this study, we evaluated a method to preserve and label sensitive GCX components with antibodies for high-resolution microscopy analysis. High-resolution microscopy is a powerful tool because it allows visualization of ultra-small components and biological interactions. Our method can be used as a tool to better understand the role of the GCX during the development and progression of diseases, such as viral infections, tumor invasion, and the development of atherosclerosis. Abstract The glycocalyx (GCX), a pericellular carbohydrate rich hydrogel, forms a selective barrier that shields the cellular membrane, provides mechanical support, and regulates the transport and diffusion of molecules. The GCX is a fragile structure, making it difficult to study by transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM). Sample preparation by conventional chemical fixation destroys the GCX, giving a false impression of its organization. An additional challenge is to process the GCX in a way that preserves its morphology and enhanced antigenicity to study its cell-specific composition. The aim of this study was to provide a protocol to preserve both antigen accessibility and the unique morphology of the GCX. We established a combined high pressure freezing (HPF), osmium-free freeze substitution (FS), rehydration, and pre-embedding immunogold labeling method for TEM. Our results showed specific immunogold labeling of GCX components expressed in human monocytic THP-1 cells, hyaluronic acid receptor (CD44) and chondroitin sulfate (CS), and maintained a well-preserved GCX morphology. We adapted the protocol for antigen localization by CLSM and confirmed the specific distribution pattern of GCX components. The presented combination of HPF, FS, rehydration, and immunolabeling for both TEM and CLSM offers the possibility for analyzing the morphology and composition of the unique GCX structure.

The patho-mechanism of changes in the thyroid gland, including carcinogenesis, is a complex process, which involves oxidative stress. The goal of our investigation was to verify the extent of stress in the thyroid gland related to glycation. The study samples were comprised of blood sera, thyroid, and adipose tissue sections probed from 37 patients diagnosed with thyroid cancers and goiter. Using immuno-enzymatic and fluorometric assays we analyzed the content of advanced glycation end-products (AGEs), pentosidine, receptors for advanced glycation end-products (RAGE), scavenger receptor class (SR)-A, SR-B, glutathione, malondialdehyde and nitric oxide synthase. In addition to classic AGEs, a recent study detected the melibiose-derived glycation (MAGE) product. We demonstrated the presence of AGEs, MAGE and their receptors of the RAGE and SR-A. In addition, in the control samples of thyroid glands SR-B groups were detected as well as of pathological groups without noticeable tendency to antigen concentration in the area of carcinogenesis. Fluorescent AGEs correlate positively with glutathione, which supports the assumption that glycation stress leads to augmentation of oxidative stress and increase of the intensity of antioxidant mechanisms.

Inhibition of the protein neddylation process by the small-molecule inhibitor MLN4924 has been recently indicated as a promising direction for cancer treatment. However, the knowledge of all biological consequences of MLN4924 for cancer cells is still incomplete. Here, we report that MLN4924 inhibits tumor necrosis factor-alpha (TNF-α)-induced matrix metalloproteinase 9 (MMP9)-driven cell migration. Using real-time polymerase chain reaction (PCR) and gelatin zymography, we found that MLN4924 inhibited expression and activity of MMP9 at the messenger RNA (mRNA) and protein levels in both resting cells and cells stimulated with TNF-α, and this inhibition was closely related to impaired cell migration. We also revealed that MLN4924, similar to TNF-α, induced phosphorylation of inhibitor of nuclear factor kappa B-alpha (IκB-α). However, contrary to TNF-α, MLN4924 did not induce IκB-α degradation in treated cells. In coimmunoprecipitation experiments, nuclear IκB-α which formed complexes with nuclear factor kappa B p65 subunit (NFκB/p65) was found to be highly phosphorylated at Ser32 in the cells treated with MLN4924, but not in the cells treated with TNF-α alone. Moreover, in the presence of MLN4924, nuclear NFκB/p65 complexes were found to be enriched in c-Jun and cyclin dependent kinase inhibitor 1 A (CDKN1A/p21) proteins. In these cells, NFκB/p65 was unable to bind to the MMP9 gene promoter, which was confirmed by the chromatin immunoprecipitation (ChIP) assay. Taken together, our findings identified MLN4924 as a suppressor of TNF-α-induced MMP9-driven cell migration in esophageal squamous cell carcinoma (ESCC), likely acting by affecting the nuclear ubiquitin–proteasome system that governs NFκB/p65 complex formation and its DNA binding activity in regard to the MMP9 promoter, suggesting that inhibition of neddylation might be a new therapeutic strategy to prevent invasion/metastasis in ESCC patients.

The ability to stabilize very small Pt crystallites in supported-metal catalysts following harsh treatments is an important industrial problem. Here, we demonstrate that Pt particles can be maintained in the 1- to 2-nm range following multiple oxidation and reduction cycles at 1073 K when the particles are supported on 0.5-nm LaFeO3 films that have been deposited onto MgAl2O4 using atomic layer deposition. Characterization by scanning transmission electron microscopy suggests that when the catalyst is oxidized at 1073 K, the Pt crystallites are oriented with respect to the underlying LaFeO3. X-ray absorption spectroscopy also shows evidence of changes in the Pt environment. CO-oxidation rates for the reduced catalyst remain unchanged after five redox cycles at 1073 K. Epitaxial growth of Pt clusters and the consequent strong metal-support interaction between Pt and LaFeO3 are suggested to be the main reasons for the enhanced catalytic performances.

A patient’s body accepting a bone implant depends not only on the biomaterial used, but also on its surface, which allows it to properly interact with bone cells. Therefore, research has focused on improving the bioactive and tribological properties of titanium and its alloys. Commercially pure titanium (cp-Ti) is widely used as a biomedical material. However, it is characterized by unsuitable tribological properties. In this work, yttria-stabilized zirconia (YSZ) was deposited on a cp-Ti substrate via plasma spray–physical vapor deposition (PS-PVD). The structural characteristics were determined using X-ray analysis (XRD). Additionally, the lattice parameters of each phase were determined using Rietveld’s method. High-resolution scanning microscopy (HR-SEM) showed a typical column structure of coatings that can be used with PS-PVD. Depending on the process parameters, the coatings differed in thickness in the range of 2.4–9.0 µm. The surface roughness also varied. The samples were subjected to nano-indenter testing. A slight change in hardness after deposition of the coating was observed, in addition to a significant decrease in the Young’s modulus. The Young’s modulus in relation to the metallic substrate was reduced to 58 or 78 GPa depending on the parameters of the spray-coating process.

Despite their technological importance for water splitting, the reaction mechanisms of most water oxidation catalysts (WOCs) are poorly understood. This paper combines theoretical and experimental methods to reveal mechanistic insights into the reactivity of the highly active molecular manganese vanadium oxide WOC [Mn4V4O17(OAc)3]3− in aqueous acetonitrile solutions. Using density functional theory together with electrochemistry and IR-spectroscopy, we propose a sequential three-step activation mechanism including a one-electron oxidation of the catalyst from [Mn23+Mn24+] to [Mn3+Mn34+], acetate-to-water ligand exchange, and a second one-electron oxidation from [Mn3+Mn34+] to [Mn44+]. Analysis of several plausible ligand exchange pathways shows that nucleophilic attack of water molecules along the Jahn–Teller axis of the Mn3+ centers leads to significantly lower activation barriers compared with attack at Mn4+ centers. Deprotonation of one water ligand by the leaving acetate group leads to the formation of the activated species [Mn4V4O17(OAc)2(H2O)(OH)]− featuring one H2O and one OH ligand. Redox potentials based on the computed intermediates are in excellent agreement with electrochemical measurements at various solvent compositions. This intricate interplay between redox chemistry and ligand exchange controls the formation of the catalytically active species. These results provide key reactivity information essential to further study bio-inspired molecular WOCs and solid-state manganese oxide catalysts., Combined theoretical and experimental studies shed light on the initial steps of redox-activation of a molecular manganese vanadium oxide water oxidation catalyst.

Alloying is a long-established strategy to tailor properties of metals for specific applications, thus retaining or enhancing the principal elemental characteristics while offering additional functionality from the added elements. We propose a similar approach to the control of properties of two-dimensional transition metal carbides known as MXenes. MXenes (Mn+1Xn) have two sites for compositional variation: elemental substitution on both the metal (M) and carbon/nitrogen (X) sites presents promising routes for tailoring the chemical, optical, electronic, or mechanical properties of MXenes. Herein, we systematically investigated three interrelated binary solid-solution MXene systems based on Ti, Nb, and/or V at the M-site in a M2XTx structure (Ti2-yNbyCTx, Ti2-yVyCTx, and V2-yNbyCTx, where Tx stands for surface terminations) showing the evolution of electronic and optical properties as a function of composition. All three MXene systems show unlimited solubility and random distribution of metal elements in the metal sublattice. Optically, the MXene systems are tailorable in a nonlinear fashion, with absorption peaks from ultraviolet to near-infrared wavelength. The macroscopic electrical conductivity of solid solution MXenes can be controllably varied over 3 orders of magnitude at room temperature and 6 orders of magnitude from 10 to 300 K. This work greatly increases the number of nonstoichiometric MXenes reported to date and opens avenues for controlling physical properties of different MXenes with a limitless number of compositions possible through M-site solid solutions.