Integrative Analysis of Lactylome and Proteome of Hypertrophic Scar To Identify Pathways or Proteins Associated with Disease Development.

Lactylation (Kla), a recently discovered post-translational modification derived from lactate, plays crucial roles in various cellular processes. However, the specific influence of lactylation on the biological processes underlying hypertrophic scar formation remains unclear. In this study, we present a comprehensive profiling of the lactylome and proteome in both hypertrophic scars and adjacent normal skin tissues. A total of 1023 Kla sites originating from 338 nonhistone proteins were identified based on lactylome analysis. Proteome analysis in hypertrophic scar and adjacent skin samples revealed the identification of 2008 proteins. It is worth noting that Kla exhibits a preference for genes associated with ribosome function as well as glycolysis/gluconeogenesis in both normal skin and hypertrophic scar tissues. Furthermore, the functional enrichment analysis demonstrated that differentially lactyled proteins are primarily involved in proteoglycans, HIF-1, and AMPK signaling pathways. The combined analysis of the lactylome and proteome data highlighted a significant upregulation of 14 lactylation sites in hypertrophic scar tissues. Overall, our investigation unveiled the significant involvement of protein lactylation in the regulation of ribosome function as well as glycolysis/gluconeogenesis, potentially contributing to the formation of hypertrophic scars.

Recent Progress of Transition Metal Selenides for Electrochemical Oxygen Reduction to Hydrogen Peroxide: From Catalyst Design to Electrolyzers Application.

Hydrogen peroxide (H2O2) is a highly value-added and environmental-friendly chemical with various applications. The production of H2O2 by electrocatalytic 2e- oxygen reduction reaction (ORR) has emerged as a promising alternative to the energy-intensive anthraquinone process. High selectivity Catalysts combining with superior activity are critical for the efficient electrosynthesis of H2O2. Earth-abundant transition metal selenides (TMSs) being discovered as a classic of stable, low-cost, highly active and selective catalysts for electrochemical 2e- ORR. These features come from the relatively large atomic radius of selenium element, the metal-like properties and the abundant reserves. Moreover, compared with the advanced noble metal or single-atom catalysts, the kinetic current density of TMSs for H2O2 generation is higher in acidic solution, which enable them to become suitable catalyst candidates. Herein, the recent progress of TMSs for ORR to H2O2 is systematically reviewed. The effects of TMSs electrocatalysts on the activity, selectivity and stability of ORR to H2O2 are summarized. It is intended to provide an insight from catalyst design and corresponding reaction mechanisms to the device setup, and to discuss the relationship between structure and activity.

Highly Dispersed Mn-Doped Ceria Supported on N-Doped Carbon Nanotubes for Enhanced Oxygen Reduction Reaction.

The weak adsorption of oxygen on transition metal oxide catalysts limits the improvement of their electrocatalytic oxygen reduction reaction (ORR) performance. Herein, a dopamine-assisted method is developed to prepare Mn-doped ceria supported on nitrogen-doped carbon nanotubes (Mn-Ce-NCNTs). The morphology, dispersion of Mn-doped ceria, composition, and oxygen vacancies of the as-prepared catalysts were analyzed using various technologies. The results show that Mn-doped ceria was formed and highly dispersed on NCNTs, on which oxygen vacancies are abundant. The as-prepared Mn-Ce-NCNTs exhibit a high ORR performance, on which the average electron transfer number is 3.86 and the current density is 24.4% higher than that of commercial 20 wt % Pt/C. The peak power density of Mn-Ce-NCNTs is 68.1 mW cm-2 at the current density of 138.9 mA cm-2 for a Zn-air battery, which is close to that of 20 wt % Pt/C (69.4 mW cm-2 at 106.1 mA cm-2). Density functional theory (DFT) calculations show that the oxygen vacancy formation energies of Mn-doped CeO2(111) and pure CeO2(111) are -0.55 and 2.14 eV, respectively. Meanwhile, compared with undoped CeO2(111) (-0.02 eV), Mn-doped CeO2(111) easily adsorbs oxygen with the oxygen adsorption energy of only -0.68 eV. This work provides insights into the synergetic effect of Mn-doped ceria for facilitating oxygen adsorption and enhancing ORR performance.

Effects of oxygen vacancies and interfacial strain on the metal-insulator transition of VO2 nanobeams.

The role of oxygen vacancies and interfacial strain on the metal-insulator transition (MIT) behavior of high-quality VO2 nanobeams (NBs) synthesized on SiO2/Si substrates employing V2O5 as a precursor has been investigated in this research. Selective oxygen vacancies have been generated by argon plasma irradiation. The MIT is progressively suppressed as the duration of plasma processing increases; in addition, the temperature of MIT (TMIT) drops by up to 95 K relative to the pristine VO2 NBs. Incorporating oxygen vacancies into VO2 may increase its electron concentration, which might shift the Fermi levels upward, strengthen the electronic orbital overlap of the V-V chains, and further stabilize the metallic phase at lower temperatures, based on first-principles calculations. Furthermore, in order to evaluate the influence of substrate-induced strain in our situation, the MIT in two distinct types of VO2 NB samples is examined without metal contacts by using the distinctive light scattering characteristics of the metal (M) and insulator (I) phases (i.e., M/I domains) by optical microscopy. It is found that the domain structures in the "clamped" NBs persisted up to ∼453 K, while the "released" NBs (transferred to a new substrate) did not exhibit any domain structures and turned into an entirely M phase with a dark contrast above ∼348 K. When combined with first-principles calculations, the electronic orbital occupancy in the rutile phase contributes to explaining the interfacial strain-induced modulation of MIT. The current findings shed light on how interfacial strain and oxygen vacancies impact MIT behavior. It also suggests several types of control strategies for MIT in VO2 NBs, which are essential for a broader spectrum of VO2 NB applications.

Avoiding Sabatier's Limitation on Spatially Correlated Pt-Mn Atomic Pair Sites for Oxygen Electroreduction.

The development of highly active and low-cost oxygen reduction reaction (ORR) catalysts is crucial for the practical application of hydrogen fuel cells. However, the linear scaling relation (LSR) imposes an inherent Sabatier's limitation for most catalysts including the benchmark Pt with an insurmountable overpotential ceiling, impeding the development of efficient electrocatalysts. To avoid such a limitation, using earth-abundant metal oxides with different crystal phases as model materials, we propose an effective and dynamic reaction pathway through constructing spatially correlated Pt-Mn pair sites, achieving an excellent balance between high activity and low Pt loading. Experimental and theoretical calculations demonstrate that manipulating the intermetallic distance and charge distribution of Pt-Mn pairs can effectively promote O-O bond cleavage at these sites through a bridge configuration, circumventing the formation of *OOH intermediates. Meanwhile, the dynamic adsorption configuration transition from the bridge configuration of O2 to the end-on configuration of *OH improves *OH desorption at the Mn site within such pairs, thereby avoiding Sabatier's limitation. The well-designed Pt-Mn/ß-MnO2 exhibits outstanding ORR activity and stability with a half-wave potential of 0.93 V and barely any activity degradation for 70 h. When applied to the cathode of a H2-O2 anion-exchange membrane fuel cell, this catalyst demonstrates a high peak power density of 287 mW cm-2 and 500 h of stability under a cell voltage of 0.6 V. This work reveals the adaptive bonding interactions of atomic pair sites with multiple reactant/intermediates, offering a new avenue for rational design of highly efficient atomic-level dispersed ORR catalysts beyond the Sabatier optimum.

Tracking the Role of Defect Types in Co3O4 Structural Evolution and Active Motifs during Oxygen Evolution Reaction.

Dynamic reconstruction of catalyst active sites is particularly important for metal oxide-catalyzed oxygen evolution reaction (OER). However, the mechanism of how vacancy-induced reconstruction aids OER remains ambiguous. Here, we use Co3O4 with Co or O vacancies to uncover the effects of different defects in the reconstruction process and the active motifs relevant to alkaline OER. Combining in situ characterization and theoretical calculations, we found that cobalt oxides are converted to an amorphous [Co(OH)6] intermediate state, and then the mismatched rates of *OH adsorption and deprotonation lead to irreversible catalyst reconstruction. The stronger *OH adsorption but weaker deprotonation induced by O defects provides the driving force for reconstruction, while Co defects favor dehydrogenation and reduce the reconstruction rate. Importantly, both O and Co defects trigger highly OER-active bridge Co sites in reconstructed catalysts, of which Co defects induce a short Co-Co distance (3.38 Å) under compressive lattice stress and show the best OER activity (η10 of 262 mV), superior to reconstructed oxygen-defected Co3O4-VO (η10 of 300 mV) and defect-free Co3O4 (η10 of 320 mV). This work highlights that engineering defect-dependent reconstruction may provide a rational route for electrocatalyst design in energy-related applications.

Pd/Fe2O3 with Electronic Coupling Single-Site Pd-Fe Pair Sites for Low-Temperature Semihydrogenation of Alkynes.

Dispersing single palladium atoms on a support is promising to minimize the usage of palladium and improve the selectivity for alkyne semihydrogenation, but its activity is often very low as a result of unfavorable H2 activation. Here, we load palladium onto α-Fe2O3(012) to construct highly active and stable single-site Pd-Fe pairs with luxuriant d-electron domination near the Fermi level driven by strong electronic coupling and prove that Pd-Fe pairs cooperatively adsorb H2 and dissociate an H─H bond, whereas solo Pd sites enable preferential desorption of C═C intermediate, thus achieving both high activity and high selectivity for alkyne hydrogenation. This catalyst exhibits state-of-the-art performance in purifying acetylene of ethylene stream, with 99.6% and 100% conversion and 96.7% and 94.7% selectivity at 353 and 393 K, respectively, and excellent stability with negligible activity decay after a 200 h test. This single-site pair inherits the advantage but overcomes the weakness of both Pd ensemble and single Pd atoms, enabling ultralow-Pd-loading catalysts for selective hydrogenation.

Surface Design Strategy of Catalysts for Water Electrolysis.

Hydrogen, a new energy carrier that can replace traditional fossil fuels, is seen as one of the most promising clean energy sources. The use of renewable electricity to drive hydrogen production has very broad prospects for addressing energy and environmental problems. Therefore, many researchers favor electrolytic water due to its green and low-cost advantages. The electrolytic water reaction comprises the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Understanding the OER and HER mechanisms in acidic and alkaline processes contributes to further studying the design of surface regulation of electrolytic water catalysts. The OER and HER catalysts are mainly reviewed for defects, doping, alloying, surface reconstruction, crystal surface structure, and heterostructures. Besides, recent catalysts for overall water splitting are also reviewed. Finally, this review paves the way to the rational design and synthesis of new materials for highly efficient electrocatalysis.

Manipulating the Conversion Kinetics of Polysulfides by Engineering Oxygen p-Band of Halloysite for Improved Li-S Batteries.

Polar oxides are widely used as the cathodes to impede the shuttle effect in lithium-sulfur batteries, but suffer from the sluggish desorption and conversion of polysulfides due to too strong affinity of polysulfides on oxygen sites. Herein, employing halloysite as a model, an approach to overcome these shortcomings is proposed via engineering oxygen p-band center by loading titanium dioxide nanoparticles onto Si-O surface of halloysite. Using density functional theory calculations, it is predicted that electron transfer from titanium dioxide nanoparticles to interfacial O sites results in downshift of p-band center of O sites that promote desorption of polysulfides and the cleavage of Li-S and S-S, accelerating the conversion kinetics of polysulfides. The designed composite cathode material delivers outstanding electrochemical performance in Li-S batteries, outperforming the recently reported similar cathodes. The concept could provide valuable insight into the design of other catalysts for Li-S batteries and beyond.

Interface Engineering of Conjugated Polymer-Based Composites for Photocatalysis.

Photocatalysis can create a green way to produce clean energy resources, degrade pollutants and achieve carbon neutrality, making the construction of efficient photocatalysts significant in solving environmental issues. Conjugated polymers (CPs) with adjustable band structures have superior light-absorption capacity and flexible morphology that facilitate contact with other components to form advanced heterojunctions. Interface engineering can strengthen the interfacial contact between the components and further enlarge the interfacial contact area, enhance light absorption, accelerate charge transfer and improve the reusability of the composites. In order to throw some new light on heterojunction interface regulation at a molecular level, herein we summarize CP-based composites with improved photocatalytic performance according to the types of interactions (covalent bonding, hydrogen bonding, electrostatic interactions, π-π stacking, and other polar interactions) between the components and introduce the corresponding interface building methods, identifying techniques. Then the roles of interfaces in different photocatalytic applications are discussed. Finally, we sum up the existing problems in interface engineering of CP-based composites and look forward to the possible solutions.

A Piezo-Fenton System with Rapid Iron Cycling and Hydrogen Peroxide Self-Supply Driven by Ultrasound.

The piezo-Fenton system has attracted attention not only because it can enhance the Fenton reaction activity by mechanical energy input, but also because it is expected to realize a class of stimuli-responsive advanced oxidation systems by regulating energy input and hydrogen peroxide self-supply, thus greatly enriching the application possibilities of Fenton chemistry. In this work, a series of Fe-doped g-C3 N4 (g-C3 N4 -Fe) as a piezo-Fenton system were synthesized where the iron stably immobilized through Fe-N interaction. The piezo-induced electrons generate on g-C3 N4 matrix support the conversion of Fe(III) to Fe(II) and promote rate-limiting step of Fenton reaction. With the optimal Fe loading, g-C3 N4 -0.5Fe can achieve methylene blue (MB) degradation under ultrasonic treatment with first-order kinetic rate constants of 75×10-3  min-1 . Most importantly, the g-C3 N4 -Fe can maintain good catalytic activity in a wide pH range (pH=2.0∼9.0) and be cyclic used without iron leaching to solution (<0.001 µg ⋅ L-1 ), overcoming the disadvantage of traditional Fe-based Fenton catalysts that can only be applied under acidic conditions and prone to secondary pollution. In addition, g-C3 N4 -0.5Fe also exhibits antibacterial properties of Escherichia coli and Staphylococcus aureus under ultrasound. Hydroxyl radicals mainly contribute to the degradation of MB and the sterilization process. Our work is an attempt to clarify the role of g-C3 N4 -Fe in the conversion of mechanical energy to ROS and provide inspirations for the piezo-Fenton system design.

2D MOF with Compact Catalytic Sites for the One-pot Synthesis of 2,5-Dimethylfuran from Saccharides via Tandem Catalysis.

One pot synthesis of 2,5-dimethylfuran (2,5-DMF) from saccharides under mild conditions is of importance for the production of biofuel and fine chemicals. However, the synthesis requires a multitude of active sites and suffers from slow kinetics due to poor diffusion in most composite catalysts. Herein, a metal-acid functionalized 2D metal-organic framework (MOF; Pd/NUS-SO3 H), as an ultrathin nanosheet of 3-4 nm with Lewis acid, Brønsted acid, and metal active sites, was prepared based on the diazo method for acid modification and subsequent metal loading. This new composite catalyst gives substantially higher yields of DMF than all reported catalysts for different saccharides (fructose, glucose, cellobiose, sucrose, and inulins). Characterization suggests that a cascade of reactions including polysaccharide hydrolysis, isomerization, dehydration, and hydrodeoxygenation takes place with rapid molecular interactions.

Hydrogen-Catalyzed Acid Transformation for the Hydration of Alkenes and Epoxy Alkanes over Co-N Frustrated Lewis Pair Surfaces.

Hydrogen (H2) is widely used as a reductant for many hydrogenation reactions; however, it has not been recognized as a catalyst for the acid transformation of active sites on solid surface. Here, we report the H2-promoted hydration of alkenes (such as styrenes and cyclic alkenes) and epoxy alkanes over single-atom Co-dispersed nitrogen-doped carbon (Co-NC) via a transformation mechanism of acid-base sites. Specifically, the specific catalytic activity and selectivity of Co-NC are superior to those of classical solid acids (acidic zeolites and resins) per micromole of acid, whereas the hydration catalysis does not take place under a nitrogen atmosphere. Detailed investigations indicate that H2 can be heterolyzed on the Co-N bond to form Hδ--Co-N-Hδ+ and then be converted into OHδ--Co-N-Hδ+ accompanied by H2 generation via a H2O-mediated path, which significantly reduces the activation energy for hydration reactions. This work not only provides a novel catalytic method for hydration reactions but also removes the conceptual barriers between hydrogenation and acid catalysis.

Synergy of Iron Doping and Cyano Groups for Enhanced Photocatalytic Hydrogen Production over C3 N4.

Improving the insufficient carrier separation dynamics is still of significance in carbon nitride (C3 N4 ) research. Extensive research has been devoted to improving the carrier separation efficiency through a single strategy, while ignoring the synergistic enhancement effect produced by coupling two or more conventional strategies. Herein, we reported the fabrication of cyano group-containing Fe-doped C3 N4 porous materials via direct co-calcination of iron acetylacetonate and melamine for synergistically improving the photocatalytic performance. Iron acetylacetonate can promote the generation of cyano groups and form Fe-doping in C3 N4 , thereby increasing the visible-light absorption and reactive sites. Further, the internal donor-acceptor system formed by cyano groups and Fe-doped sites promoted charge carrier separation and inhibited the radiation recombination of e- -h+ pairs. The optimized photocatalytic activity of Fe-CN-2 sample was 4.5 times of bulk C3 N4 (BCN).

Ultra-low thermal conductivity and high thermoelectric performance of monolayer BiP3: a first principles study.

The thermoelectric properties of monolayer triphosphide BiP3 are studied via first principles calculations and Boltzmann transport equation. First, the Seebeck coefficient, electrical conductivity and electron thermal conductivity at different temperatures are calculated using the Boltzmann transport equation with relaxation time approximation. It has been observed that BiP3 has a large power factor (265 × 10-4 W K-2 m-1, 700 K). Then, by analyzing the second-order interatomic force constant (IFCS), the atomic structure and phonon dispersion were studied, and the thermal conductivity of monolayer BiP3 was predicted in the temperature range of 300-800 K, and it was found that it had a very low thermal conductivity (2.13 W m-1 K-1) at room temperature. The thermal conductivity is mainly contributed by the branches of acoustics along in-plane transverse (TA). Finally, the maximum ZT value of monolayer BiP3 is 3.06 at 700 K, when the electron doping concentration is 2.35 × 1011 cm-2, which indicates that it is a promising thermoelectric material.

Mie-type GaAs nanopillar array resonators for negative electron affinity photocathodes.

This paper presents modeling results of Mie-type GaAs nanopillar array resonant structures and the design of negative electron affinity photocathodes based on Spicer's three-step model. For direct-bandgap GaAs with high intrinsic absorption coefficient in the 500 ∼ 850 nm spectral range, photoelectrons were found to be highly localized inside the nanopillars near the top and side surfaces where electrons can be efficiently transported and emitted into vacuum, and the light reflectance can be reduced to ∼1% level at resonance wavelengths. Predictions of spectrally resolved photoemission indicate that these nanophotonics resonators, when properly optimized, can increase the photo-electron emission quantum efficiency at resonance wavelengths to levels limited only by the surface-electron escape probability, significantly outperforming traditional flat wafer photocathodes. Ultrafast photoelectric response is also expected from these nanostructured photocathodes due to the much shorter photoelectron transport distance in nanopillars compared to flat wafers. Given these unique optoelectronic properties, GaAs nanophotonic resonance structured photocathodes represent a very promising alternative to photocathodes with flat surfaces that are widely used in many applications today.

A Grey Model and Mixture Gaussian Residual Analysis-Based Position Estimator in an Indoor Environment.

As the progress of electronics and information processing technology continues, indoor localization has become a research hotspot in wireless sensor networks (WSN). The adverse non-line of sight (NLOS) propagation usually causes large measurement errors in complex indoor environments. It could decrease the localization accuracy seriously. A traditional grey model considers the motion characteristics but does not take the NLOS propagation into account. A robust interacting multiple model (R-IMM) could effectively mitigate NLOS errors but the clipping point is hard to choose. In order to easily cope with NLOS errors, we present a novel filter framework: mixture Gaussian fitting-based grey Kalman filter structure (MGF-GKFS). Firstly, grey Kalman filter (GKF) is proposed to pre-process the measured distance, which can mitigate the process noise and alleviate NLOS errors. Secondly, we calculate the residual which is the difference between the filtered distance of GKF and the measured distance. Thirdly, a soft decision method based on mixture Gaussian fitting (MGF) is proposed to identify the propagation condition through residual value and give the degree of membership. Fourthly, weak NLOS noise is further processed by unscented Kalman filter (UKF). The filtered results of GKF and UKF are weighted using the degree of membership. Finally, a maximum likelihood (ML) algorithm is applied to get the coordinate of the target. MGF-GKFS is not supported by any of the priori knowledge. Full-scale simulations and an experiment are conducted to compare the localization accuracy and robustness with the state-of-the-art algorithms, including robust interacting multiple model (R-IMM), unscented Kalman filter (UKF) and interacting multiple model (IMM). The results show that MGF-GKFS could achieve significant improvement compared to R-IMM, UKF and IMM algorithms.

Regulating the Spin State of FeIII by Atomically Anchoring on Ultrathin Titanium Dioxide for Efficient Oxygen Evolution Electrocatalysis.

Ferric oxides and (oxy)hydroxides, although plentiful and low-cost, are rarely considered for oxygen evolution reaction (OER) owing to the too high spin state (eg filling ca. 2.0) suppressing the bonding strength with reaction intermediates. Now, a facile adsorption-oxidation strategy is used to anchor FeIII atomically on an ultrathin TiO2 nanobelt to synergistically lower the spin state (eg filling ca. 1.08) to enhance the adsorption with oxygen-containing intermediates and improve the electro-conductibility for lower ohmic loss. The electronic structure of the catalyst is predicted by DFT calculation and perfectly confirmed by experimental results. The catalyst exhibits superior performance for OER with overpotential 270 mV @10 mA cm-2 and 376 mV @100 mA cm-2 in alkaline solution, which is much better than IrO2 /C and RuO2 /C and is the best iron-based OER catalyst free of active metals such as Ni, Co, or precious metals.

Efficient band structure modulations in two-dimensional MnPSe3/CrSiTe3 van der Waals heterostructures.

As a research upsurge, van der Waals (vdW) heterostructures give rise to numerous combined merits and novel applications in nanoelectronics fields. Here, we systematically investigate the electronic structure of MnPSe3/CrSiTe3 vdW heterostructures with various stacking patterns. Then, particular attention of this work is paid on the band structure modulations in MnPSe3/CrSiTe3 vdW heterostructures via biaxial strain or electric field. Under a tensile strain, the relative band edge positions of heterostructures transform from type-I (nested) to type-II (staggered). The relocation of conduction band minimum also brings about a transition from indirect to direct band gap. Under a compressive strain, the electronic properties change from semiconducting to metallic. The physical mechanism of strain-dependent band structure may be ascribed to the shifts of the energy bands impelled by different superposition of atomic orbitals. Meanwhile, our calculations manifest that band gap values of MnPSe3/CrSiTe3 heterostructures are insensitive to the electric field. Even so, by applying a suitable intensity of negative electric field, the band alignment transition from type-I to type-II can also be realized. The efficient band structure modulations via external factors endow MnPSe3/CrSiTe3 heterostructures with great potential in novel applications, such as strain sensors, photocatalysis, spintronic and photoelectronic devices.

Spin splitting and p-/n-type doping of two-dimensional WSe2/BiIrO3(111) heterostructures.

The electronic structure of monolayer WSe2/BiIrO3(111) interfaces is investigated by first-principles calculations. The different polar directions of bilayer BiIrO3(111) can induce the p- or n-type doping of WSe2, indicating that the conductivity of monolayer WSe2 can be effectively modulated by switching the polarization of bilayer BiIrO3(111). Meanwhile, in B1 and B4 models, the spin splitting energies of WSe2 are 413.7 and 416.6 meV, which decrease by 52.9 and 50.0 meV compared to that of pristine monolayer WSe2 of 466.6 meV. Additionally, by applying a perpendicular electric field of 0.1 V nm-1, the spin splitting can be increased from 413.7 to 421.5 meV. However, spin splitting shows robustness against large electric fields. The results are useful in the design of novel two-dimensional transition metal dichalcogenide devices.