Stem Research Articles

Hidden Impurities Generate False Positives in Single Atom Catalyst Imaging.

Single-atom catalysts (SACs) are an emerging class of materials, leveraging maximum atom utilization and distinctive structural and electronic properties to bridge heterogeneous and homogeneous catalysis. Direct imaging methods, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, are commonly applied to confirm the atomic dispersion of active sites. However, interpretations of data from these techniques can be challenging due to simultaneous contributions to intensity from impurities introduced during synthesis processes, as well as any variation in position relative to the focal plane of the electron beam. To address this matter, this paper presents a comprehensive study on two representative SACs containing isolated nickel or copper atoms. Spectroscopic techniques, including X-ray absorption spectroscopy, were employed to prove the high metal dispersion of the catalytic atoms. Employing scanning transmission electron microscopy imaging combined with single-atom-sensitive electron energy loss spectroscopy, we scrutinized thin specimens of the catalysts to provide an unambiguous chemical identification of the observed single-atom species and thereby distinguish impurities from active sites at the single-atom level. Overall, the study underscores the complexity of SACs characterization and establishes the importance of the use of spectroscopy in tandem with imaging at atomic resolution to fully and reliably characterize single-atom catalysts.

Silver Nanoparticle-Embedded Carbon Nitride: Antifungal Activity on Candida albicans and Toxicity toward Animal Cells.

The development of engineered nanomaterials has been considered a promising strategy to control oral infections. In this study, silver-embedded carbon nitrides (Ag@g-CN) were synthesized and tested against Candida albicans, investigating their antifungal action and biocompatibility in animal cells. Ag@g-CN was synthesized by a simple one-pot thermal polymerization technique and characterized by various analytical techniques. X-ray diffraction (XRD) analysis revealed slight alterations in the crystal structure of g-CN upon the incorporation of Ag. Fourier transform infrared (FT-IR) spectroscopy confirmed the presence of Ag-N bonds, indicating successful silver incorporation and potential interactions with g-CN's amino groups. UV-vis spectroscopy demonstrated a red shift in the absorption edge of Ag@g-CN compared with g-CN, attributed to the surface plasmon resonance effect of silver nanoparticles. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) confirmed the 2D layered sheet like morphology of both materials. The Ag 3d peaks found in X-ray photoelectron spectroscopy (XPS) confirmed the presence of metallic Ag0 nanoparticles in Ag@g-CN. The Ag@g-CN materials exhibited high antifungal activity against reference and oral clinical strains of C. albicans, with minimal inhibitory concentration (MIC) ranges between 16-256 μg/mL. The mechanism of Ag@g-CN on C. albicans was attributed to the disruption of the membrane integrity and disturbance of the biofilm. In addition, the Ag@g-CN material showed good biocompatibility in the fibroblastic cell line and in Galleria mellonella, with no apparent cytotoxicity observed at a concentration up to 1000 μg/mL. These findings demonstrate the potential of the Ag@g-CN material as an effective and safe antifungal agent for the treatment of oral fungal infections.

Synthesis and characterization of hydroxyapatite nanoparticles from calcium hydroxide fouled with gases evolved from smokestack of glass industry

In glass industry, the evolved gases and fumes from burning the gas fuel absorbed in calcium hydroxide to minimize the pollution of environment. After a period of time, the calcium hydroxide fouled with sulphate and carbonate as action of the absorbed SO3 and CO2 gases. Based on our interest to treatment the solid waste materials, this study intended to convert the obtained waste of calcium hydroxide fouled with gases to valuable products. Firstly, this waste was treated with water, caustic soda and acids. The results confirmed the conversion of waste to pure calcium sulfate by treatment with 6 v/v% sulfuric acid. Secondly, the obtained calcium sulfate was reacted with ammonium dihydrogen phosphate solution for preparation of calcium hydroxyapatite (HAp) nanoparticles. The produced HAp sample was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and scanning electron microscopy (SEM), thermal gravimetric analysis (TGA) and N2 adsorption measurements. The obtained findings confirmed that the HAp can be produced after calcination at 700 °C, nanorods-like of sizes ranged from 11 to 15 nm and with main surface functional groups of hydroxyapatite. TGA and DTA data indicated that HAp is thermally stable up to 700 °C. Also, the obtained HAp has Ca/P molar ratio of 1.60 and exhibited high total surface area of 146 m2/g with mesoporous structure which make this material can be used in medical and water purification applications.

The Defects Genome of Janus Transition Metal Dichalcogenides.

Two-dimensional (2D) Janus Transition Metal Dichalcogenides (TMDs) have attracted much interest due to their exciting quantum properties arising from their unique two-faced structure, broken-mirror symmetry, and consequent colossal polarisation field within the monolayer. While efforts have been made to achieve high-quality Janus monolayers, the existing methods rely on highly energetic processes that introduce unwanted grain-boundary and point defects with still unexplored effects on the material's structural and excitonic properties Through High-resolution scanning transmission electron microscopy (HRSTEM), density functional theory (DFT), and optical spectroscopy measurements; this work introduces the most encountered and energetically stable point defects. It establishes their impact on the material's optical properties. HRSTEM studies show that the most energetically stable point defects are single (VS and VSe) and double chalcogen vacancy (VS -VSe), interstitial defects (Mi), and metal impurities (MW) and establish their structural characteristics. DFT further establishes their formation energies and related localized bands within the forbidden band. Cryogenic excitonic studies on h-BN-encapsulated Janus monolayers offer a clear correlation between these structural defects and observed emission features, which closely align with the results of the theory. The overall results introduce the defect genome of Janus TMDs as an essential guideline for assessing their structural quality and device properties. This article is protected by copyright. All rights reserved.

Chiral Stacking Identification of Two-Dimensional Triclinic Crystals Enabled by Machine Learning.

Chiral materials possess broken inversion and mirror symmetry and show great potential in the application of next-generation optic, electronic, and spintronic devices. Two-dimensional (2D) chiral crystals have planar chirality, which is nonsuperimposable on their 2D enantiomers by any rotation about the axis perpendicular to the substrate. The degree of freedom to construct vertical stacking of 2D monolayer enantiomers offers the possibility of chiral manipulation for designed properties by creating multilayers with either a racemic or enantiomerically pure stacking order. However, the rapid recognition of the relative proportion of two enantiomers becomes demanding due to the complexity of stacking orders of 2D chiral crystals. Here, we report the unambiguous identification of racemic and enantiomerically pure stackings for layered ReSe2 and ReS2 using circular polarized Raman spectroscopy. The chiral Raman response is successfully manipulated by the enantiomer proportion, and the stacking orders of multilayer ReSe2 and ReS2 can be completely clarified with the help of second harmonic generation and scanning transmission electron microscopy measurements. Finally, we trained an artificial intelligent Spectra Classification Assistant to predict the chirality and the complete crystallographic structures of multilayer ReSe2 from a single circular polarized Raman spectrum with the accuracy reaching 0.9417 ± 0.0059.

Electronic Properties of W’ Twin Walls in Ferroelastic BiVO4

AbstractTopological defects in ferroic materials can exhibit intrinsic properties that differ from the bulk. Here， structural and electronic variations of non‐prominent (W’) ferroelastic twin domain walls are investigated in BiVO4, a widely investigated photocatalytic material. Using aberration‐corrected scanning transmission electron microscopy (STEM), a kink configuration of the sharp ferroelastic twin wall with an altered electronic structure is revealed. Nanoscale conductivity measurements by conductive atomic force microscopy (c‐AFM) show higher conductivity at twin walls compared to non‐conductive bulk domains. Electronic structure investigation by electron energy loss spectroscopy (EELS) shows a higher density of oxygen vacancies and possible polaron accumulation at the wall. These findings reveal the electronic properties of BiVO4 domain walls, which are interesting for nanoscale‐engineered catalytic concepts of BiVO4 and materials design for photochemistry‐relevant applications.

Superior strength and electrical conductivity synergy of cold‐drawn Al‐Mg‐Si‐Ce‐Cu wires produced by continuous casting and rolling

Al‐Mg‐Si aluminum wires for overhead power transmission have extensive applications in industry and daily life. In this study, superior strength and electrical conductivity combination in the aged cold‐drawn Al‐Mg‐Si‐Ce‐Cu wires fabricated by continuous casting and rolling are achieved. The cold‐drawn wires exhibit high strength and electrical conductivity combinations of 383±2 MPa, 51.16±0.23% IACS; 373±3 MPa, 51.98±0.25% and 357±3 MPa, 53.16±0.11% IACS, respectively, when aged at 160 °C, 170 °C or 180 °C for 24 h. Subgrain boundaries are introduced into alloys by continuous casting and rolling and cold drawing, causing significant lattice distortion within the grains and providing sites for the nucleation of precipitates. Moreover, HADDF‐STEM (high‐angle annular dark‐field scanning transmission electron microscopy) and DFT (density functional theory) results show that Ce atoms could enter the lattice of β” and replace the Si3 sites, which is energetically preferred. The underlying mechanisms for achieving superior strength‐electrical conductivity combination are to introduce subgrain boundaries via continuous casting and rolling and cold drawing for promoting the transformation of solid solution atoms to finely dispersed precipitates, which significantly reduces the scattering of electrons and hence improves the electrical conductivity. This work provides a new strategy for designing high‐strength and high‐conductivity aluminum alloy wire conductors.This article is protected by copyright. All rights reserved.

Antifungal activity of Carica papaya fruit extract against Microsporum canis: in vitro and in vivo study

BackgroundTinea capitis (T. capitis), commonly known as scalp ringworm, is a fungal infection affecting the scalp and hair. Among the causative agents, Microsporum canis (M. canis) stands out, often transmitted from cats to humans (zoonotic disease). In this study, we investigated the efficacy of Carica papaya (C. papaya), fruit extract against dermatophytes, particularly M. canis, both in vitro and in vivo. Additionally, we aimed to identify the active compounds responsible for suppressing fungal growth and assess the toxicity of C. papaya on human cells.MethodologyIt conducted in two parts. First, In Vitro Study include the preparation of C. papaya fruit extract using methanol as the solvent, Phytochemical analysis of the plant extract including Gas chromatography–mass spectrometry (GC–MS) and Fourier-transform infrared spectroscopy (FTIR) was conducted, Cytotoxicity assays were performed using HUH-7 cells, employing the MTT assay (1-(3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide), Antimicrobial activity against M. canis was evaluated, including: Zone of inhibition (ZI), Minimum inhibitory concentration (MIC), Minimum fungicidal concentration (MFC), M. canis cell alterations were observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Second, In Vivo, Albino Wistar male rats were included.ResultsThe phytochemical analysis of the methanolic extract from papaya revealed several functional groups, including hydroxyl, ammonia, alkane, carbonate, and alcohol. Additionally, the GC–MS analysis identified 15 compounds, with xanthosine and decanoic acid being the predominant components. The methanolic extract of papaya fruits demonstrated potent antifungal activity: ZI = 37 mm, MIC = 1,000 μg/mL, MFC = 1900 μg/mL, MTT results indicated lower cytotoxicity of the fruit extract at concentrations of 20 μg/mL, 50 μg/mL, 100 μg/mL, 150 μg/mL, and 200 μg/mL, The IC50 revealed a significant decrease in cell viability with increasing extract concentration. Notably, papaya extract induced considerable alterations in the morphology of M. canis hyphae and spores. In animal tissue, improvements were observed among the group of rats which treated with Papaya extract. This study highlights the potential of C. papaya fruits as a natural antifungal agent, warranting further exploration for clinical applications.

S‐Scheme g‐C3N4/CdS Heterostructures Grafting Single Pd Atoms for Ultrafast Charge Transport and Efficient Visible‐Light‐Driven H2 Evolution

AbstractEmerging step‐scheme (S‐scheme) heterostructures hold unique superiority in steering directional charge transport and reinforcing redox capacity, yet rational modification of S‐scheme heterostructures by single atoms (SAs) for efficient photocatalytic H2 evolution is rarely reported. In this work, Pd SAs‐modulated organic–inorganic g‐C3N4/CdS S‐scheme heterostructures are designed and prepared by a one‐pot mechanochemical approach allowing for g‐C3N4 nanosheets/CdS nanoparticles to confine atomically dispersed Pd co‐catalysts. The g‐C3N4/CdS S‐scheme charge‐transfer pathway is corroborated by a combination of in situ irradiated X‐ray photoelectron spectroscopy, electron paramagnetic resonance, and Kelvin probe force microscopy. Density functional theory (DFT) calculations, high‐angle annular dark‐field scanning transmission electron microscopy, and X‐ray absorption fine structure identify Pd‐S3 and Pd‐N2 atomic moieties underpinned by the electronic interaction between Pd SAs and g‐C3N4/CdS heterostructures, in which the d‐band center of Pd SAs is optimized for proton adsorption thermodynamically. Further, the g‐C3N4/CdS S‐scheme heterostructures alongside Pd SAs in concert boost the rapid migration of photogenerated electrons (1.05 ps) via Pd─S and Pd─N bond‐derived channels. A maximal H2 evolution rate of 85.66 mmol h−1 g−1 is achieved by 1 wt% Pd‐20 wt% g‐C3N4/CdS hierarchical composites. This work may guide the design of high‐efficiency S‐scheme‐based photocatalysts for solar‐to‐H2 conversion and beyond.

How important is carbon sequestration in phytoliths within the soil?

Abstract Background and aims An overlooked fraction of the terrestrial carbon (C) pool is that associated with biogenic silica deposited in plants (phytoliths), so-called PhytOC. This fraction is small compared with the main C pools, but is of interest because it could be a long-term C sink as phytoliths may protect organic C from mineralization. However, the topic is hotly contested and unclear due to both methodological and theoretical limitations. Scope We aim to review this topic, with specific emphasis on: (i) the range of C concentrations associated with phytoliths; (ii) soil phytolith preservation and subsequent organic C mineralization; and (iii) global estimates of C sequestration within PhytOC. Conclusions Recent work has suggested that [PhytOC] could be much greater than currently acknowledged, but also highly variable and dependent on cell silicification types. A short case study using cryo‐Scanning Electron Microscopy (cryo-SEM), X‐ray microanalysis (EDX), plus Focused Ion Beam (FIB) and Scanning Transmission Electron Microscopy (STEM) on the culms of a sedge (Schoenus caespititius) confirmed this thinking. Understanding of both phytolith and PhytOC fates in soil is poor. We suggest that phytolith residence time should be seen as a gradient. Such a continuum is explained by different phytolith sizes, types and chemistry, which will also have contrasting PhytOC. Our estimation of C sequestration as PhytOC each year (11–190 Tg C yr−1) represents between < 1% and 13% of the C that could be sequestered globally in soils (estimated at 1400 Tg C yr−1). We conclude that (1) more research is needed to improve our understanding of the formation and fate of PhytOC in terrestrial ecosystems and (2) it would be unwise to put our faith in PhytOC sequestration or other related methodologies to “solve” the climate crisis.

Atomic-Scale Tracking Topological Phase Transition Dynamics of Polar Vortex-Antivortex Pairs.

Non-trivial topological structures, such as vortex-antivortex (V-AV) pairs, have garnered significant attention in the field of condensed matter physics. However, the detailed topological phase transition dynamics of V-AV pairs, encompassing behaviors like self-annihilation, motion, and dissociation, have remained elusive in real space. Here, we employ polar V-AV pairs as a model system and track their transition pathways with atomic-scale resolution, facilitated by in situ (scanning) transmission electron microscopy and phase field simulations. Our investigation reveals that polar vortices and antivortices can stably coexist as bound pairs at room temperature, and their polarization decreases with heating. No dissociation behavior is observed between the V-AV phase at room temperature and the paraelectric phase at high temperature. However, the application of electric fields can promote the approach of vortex and antivortex cores, ultimately leading to their annihilation near the interface. Revealing the transition process mediated by polar V-AV pairs at the atomic scale, particularly the role of polar antivortex, provides us new insights into understanding the topological phases of matter and their topological phase transitions. Moreover, the detailed exploration of the dynamics of polar V-AV pairs under thermal and electrical fields lays a solid foundation for their potential applications in electronic devices. This article is protected by copyright. All rights reserved.

Antennal chemoreceptors in the European ectoparasitoid Sclerodermus cereicollis (Hymenoptera: Bethylidae).

Sclerodermus cereicollis is a European flat wasp ectoparasitoid of some longhorn beetle species. This species is important as a suitable biological control agent against xylophagous pests. To better understand its chemical ecology, the ultrastructure of the antennal sensilla of the adult was studied using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The sensilla are located mainly in the ventro-medial side of the antennae. We report a clearly sexual dimorphism with respect to antennae length, and to types, number, and distribution of chemosensilla. The antennae in males are significantly longer than those of females. We describe in detail the external and internal structure of different chemoreceptors represented by sensilla placodea, long sensilla basiconica, multiporous sensilla chaetica, grooved sensilla ampullacea, uniporous grooved sensilla chaetica. The potential involvement of the different kinds of chemoreceptors in inter- (mainly sexual recognition and social behavior-kin recognition) or intra-specific communication (mainly host selection) is discussed on the basis of behavioral and electrophysiological investigations performed on other parasitoid species belonging to the same family. Other sensilla with morphology that is not consistent with that of chemoreceptors are represented by grooved pegs, coeloconic pegs, trichoid sensilla. Such detailed ultrastructural investigation of the flagellar chemoreceptors of S. cereicollis, clarifying the number of chemosensory neurons innervating the different sensilla, is crucial for further electrophysiological investigations on this important species. RESEARCH HIGHLIGHTS: Evident sexual dimorphism concerning antennae length, type, number, and distribution of chemosensilla. Long sensilla basiconica (LSB) present only in females could play a role in host location and/or maternal care. Multiporous sensilla chaetica (MSC), significantly longer and mostly represented in males, could play a role in the perception of sexual pheromones. Detailed ultrastructural study is crucial for electrophysiological investigations on this important species.

Is Ba3In2O6 a high-Tc superconductor?

It has been suggested that Ba3In2O6 might be a high-Tc superconductor. Experimental investigation of the properties of Ba3In2O6 was long inhibited by its instability in air. Recently epitaxial Ba3In2O6 with a protective capping layer was demonstrated, which finally allows its electronic characterization. The optical bandgap of Ba3In2O6 is determined to be 2.99 eV in-the (001) plane and 2.83 eV along the c-axis direction by spectroscopic ellipsometry. First-principles calculations were carried out, yielding a result in good agreement with the experimental value. Various dopants were explored to induce (super-)conductivity in this otherwise insulating material. Neither A- nor B-site doping proved successful. The underlying reason is predominately the formation of oxygen interstitials as revealed by scanning transmission electron microscopy and first-principles calculations. Additional efforts to induce superconductivity were investigated, including surface alkali doping, optical pumping, and hydrogen reduction. To probe liquid-ion gating, Ba3In2O6 was successfully grown epitaxially on an epitaxial SrRuO3 bottom electrode. So far none of these efforts induced superconductivity in Ba3In2O6, leaving the answer to the initial question of whether Ba3In2O6 is a high-Tc superconductor to be ‘no’ thus far.

Cluster–Cluster Co‐Nucleation Induced Defective Polyoxometalate‐Based Metal–Organic Frameworks for Efficient Tandem Catalysis

AbstractThe construction of defective sites is one of the effective strategies to create high‐activity Metal–Organic frameworks (MOFs) catalysts. However, traditional synthesis methods usually suffer from cumbersome synthesis steps and disordered defect structures. Herein, a cluster–cluster co‐nucleation (CCCN) strategy is presented that involves the in situ introduction of size‐matched functional polyoxometalates (H6P2W18O62, {P2W18}) to intervene the nucleation process of cluster‐based MOFs (UiO‐66), achieving one‐step inducement of exposed defective sites without redundant post‐processing. POM‐induced UiO‐66 ({P2W18}‐0.1@UiO‐66) exhibits a classical reo topology for well‐defined cluster defects. Moreover, the defective sites and the interaction between POM and skeletal cluster nodes are directly observed by Integrated Differential Phase Contrast in Scanning Transmission Electron Microscopy (iDPC‐STEM). Owing to the molecular‐level proximity between defective sites and POM in the same nano‐reaction space, {P2W18}‐0.1@UiO‐66 exhibits efficient tandem catalysis in the preparation of γ‐valerolactone (γ‐GVL) from laevulinic acid (LA) by the combination of Lewis and Brønsted acids with 11 times higher performance than defective UiO‐66 formed by conventional coordination modulation strategy. The CCCN strategy is applicable to different POM and has the potential to be extended to other cluster‐based MOFs, which will pave a new way for the construction of functional MOFs with multi‐centered synergistic catalysis.

Preparation of palladium-based catalyst by plasma-assisted atomic layer deposition and its applications in CO2 hydrogenation reduction

Supported Pd catalyst is an important noble metal material in recent years due to its high catalytic performance in CO2 hydrogenation. A fluidized-bed plasma assisted atomic layer deposition (FP-ALD) process is reported to fabricate Pd nanoparticle catalyst over γ-Al2O3 or Fe2O3/γ-Al2O3 support, using palladium hexafluoroacetylacetonate as the Pd precursor and H2 plasma as counter-reactant. Scanning transmission electron microscopy exhibits that high-density Pd nanoparticles are uniformly dispersed over Fe2O3/γ-Al2O3 support with an average diameter of 4.4 nm. The deposited Pd-Fe2O3/γ-Al2O3 shows excellent catalytic performance for CO2 hydrogenation in a dielectric barrier discharge reactor. Under a typical condition of H2 to CO2 ratio of 4 in the feed gas, the discharge power of 19.6 W, and gas hourly space velocity of 10000 h−1, the conversion of CO2 is as high as 16.3% with CH3OH and CH4 selectivities of 26.5% and 3.9%, respectively.

Picometer-Scale Atomic Shifts Governing Subdisordered Structures in Diamond

Picometer-Scale Atomic Shifts Governing Subdisordered Structures in Diamond

Non-equivalent Atomic Vibrations at Interfaces in a Polar Superlattice.

In heterostructures made from polar materials, e.g., AlN-GaN-AlN, the non-equivalence of the two interfaces has long been recognized as a critical aspect of their electronic properties, in that they host different two-dimensional carrier gases. Interfaces play an important role in the vibrational properties of materials, where interface states enhance thermal conductivity and can generate unique infrared-optical activity. The non-equivalence of the corresponding interface atomic vibrations, however, has not been investigated so far due to a lack of experimental techniques with both high spatial and high spectral resolution. Herein we experimentally demonstrate the non-equivalence of AlN-(Al0.65Ga0.35)N and (Al0.65Ga0.35)N-AlN interface vibrations using monochromated electron energy-loss spectroscopy in the scanning transmission electron microscope (STEM-EELS) and employ density-functional-theory (DFT) calculations to gain insights in the physical origins of observations. We demonstrate that STEM-EELS possesses sensitivity to the displacement vector of the vibrational modes as well as the frequency, which is as critical to understanding vibrations as polarization in optical spectroscopies. The combination enables direct mapping of the non-equivalent interface phonons between materials with different phonon polarizations. The results demonstrate the capacity to carefully assess the vibrational properties of complex heterostructures where interface states dominate the functional properties. This article is protected by copyright. All rights reserved.

Crystal structures of two new high-pressure oxynitrides with composition SnGe4N4O4, from single-crystal electron diffraction.

SnGe4N4O4 was synthesized at high pressure (16 and 20 GPa) and high temperature (1200 and 1500°C) in a large-volume press. Powder X-ray diffraction experiments using synchrotron radiation indicate that the derived samples are mixtures of known and unknown phases. However, the powder X-ray diffraction patterns are not sufficient for structural characterization. Transmission electron microscopy studies reveal crystals of several hundreds of nanometres in size with different chemical composition. Among them, crystals of a previously unknown phase with stoichiometry SnGe4N4O4 were detected and investigated using automated diffraction tomography (ADT), a three-dimensional electron diffraction method. Via ADT, the crystal structure could be determined from single nanocrystals in space group P63mc, exhibiting a nolanite-type structure. This was confirmed by density functional theory calculations and atomic resolution scanning transmission electron microscopy images. In one of the syntheses runs a rhombohedral 6R polytype of SnGe4N4O4 could be found together with the nolanite-type SnGe4N4O4. The structure of this polymorph was solved as well using ADT.

Silica Biomineralization with Lignin Involves Si-O-C Bonds That Stabilize Radicals.

Plants undergo substantial biomineralization of silicon, which is deposited primarily in cell walls as amorphous silica. The mineral formation could be moderated by the structure and chemistry of lignin, a polyphenol polymer that is a major constituent of the secondary cell wall. However, the reactions between lignin and silica have not yet been well elucidated. Here, we investigate silica deposition onto a lignin model compound. Polyphenyl propanoid was synthesized from coniferyl alcohol by oxidative coupling with peroxidase in the presence of acidic tetramethyl orthosilicate, a silicic acid precursor. Raman, Fourier transform infrared, and X-ray photoelectron spectroscopies detected changes in lignin formation in the presence of silicic acid. Bonds between the Si-O/Si-OH residues and phenoxyl radicals and lignin functional groups formed during the first 3 h of the reaction, while silica continued to form over 3 days. Thermal gravimetric analysis indicated that lignin yields increased in the presence of silicic acid, possibly via the stabilization of phenolic radicals. This, in turn, resulted in shorter stretches of the lignin polymer. Silica deposition initiated within a lignin matrix via the formation of covalent Si-O-C bonds. The silica nucleants grew into 2-5 nm particles, as observed via scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy. Additional silica precipitated into an extended gel. Collectively, our results demonstrate a reciprocal relation by which lignin polymerization catalyzes the formation of silica, and at the same time silicic acid enhances lignin polymerization and yield.

EXPLORING STRENGTHENING MECHANISMS OF ULTRAFINE-GRAINED Fe35Mn27Ni28Co5Cr5 HIGH-ENTROPY ALLOY PROCESSED BY SEVERE COLD ROLLING PROCESS

This study describes the strengthening mechanisms of an ultrafine-grained (UFG) Fe35Mn27Ni28Co5Cr5 high-entropy alloy (HEA) processed by severe cold rolling (SCR) process at room temperature. Microstructural evaluations were performed by field emission scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The findings demonstrated that the development of deformation microstructures consisted of a single face-centered cubic (FCC) phase with stretched grains along the rolling direction and lamellar deformation bands after a 90 % reduction in thickness. Using the Nix-Gao model, the dislocation density was determined by measuring the microhardness indentation size effect. The results indicated that an increase in rolling deformation leads to an increase in dislocation density. The dislocation density increased from 2.28 ×109 cm-2 for as-homogenized specimen to 8.65 ×109 cm-2 after 90 % reduction in thickness. The yield strength of the UFG Fe35Mn27Ni28Co5Cr5 HEA was 5.2 times (1155 MPa) higher than that of the as-homogenized state (225 MPa). Finally, an assessment was conducted on the relative contributions of individual mechanisms, such as dislocation and grain refinement, to the strengthening of the Fe35Mn27Ni28Co5Cr5 HEA.