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To prepare different types of lutein nanostructured lipid carriers (LNLs) using chitosan (CS), chitosan-epigallocatechin gallate covalent (C-CS-EGCG), and chitosan-epigallocatechin gallate ester non-covalent (Non-C-CS-EGCG) modifications combined with high-pressure microfluidization. A simulated colonic digestion model was established to investigate the stability and interaction with gut microbiota of these modified lutein nanostructured lipid carriers. Results showed that after 24 hours of simulated in vitro colonic fermentation, the lutein content in CS-LNLs significantly decreased (P

To prepare different types of lutein nanostructured lipid carriers (LNLs) using chitosan (CS), chitosan-epigallocatechin gallate covalent (C-CS-EGCG), and chitosan-epigallocatechin gallate ester non-covalent (Non-C-CS-EGCG) modifications combined with high-pressure microfluidization. A simulated colonic digestion model was established to investigate the stability and interaction with gut microbiota of these modified lutein nanostructured lipid carriers. Results showed that after 24 hours of simulated in vitro colonic fermentation, the lutein content in CS-LNLs significantly decreased (P<0.05) compared to other treatment groups. Except for lutein and CS-LNLs, the total sugar content in the fermentation supernatant significantly decreased (P<0.05) in other treatment groups, while the total polyphenol content in C-CS-EGCG-LNLs and Non-C-CS-EGCG-LNLs showed an opposite trend. After 24 hours of fermentation, the production of acetic acid and propionic acid significantly increased (P<0.05) in all treatment groups except the LUT group, with the acetic acid concentration reaching 17.18±0.60 mmol/L in the C-CS-EGCG-LNLs group. The lactic acid concentration reached 2.87±0.05 mmol/L, significantly higher (P<0.05) than the blank control group (BLK) by 7.55 times. The three different types of modified lutein nanostructured lipid carriers had a significant impact on the gut microbiota structure. The relative abundance of Bacteroides, Bifidobacterium, and Faecalibacterium significantly increased (P<0.05) in CS-LNLs, C-CS-EGCG- LNLs, and Non-C-CS-EGCG-LNLs, while C-CS-EGCG-LNLs enriched more Veillonella. Conclusion: Compared to other modification groups, C-CS-EGCG-LNLs had significant intestinal microbial structural differentiation in the colon digestive phase of nanoliposomes. [ABSTRACT FROM AUTHOR]

Electrochemical reduction of N2 to NH3 provides an alternative to the Haber‐Bosch process for sustainable NH3 production driven by renewable electricity. Here, we reported carbon nanotubes (CNTs) covalently modified with boron carbide (B4C) as a nonmetallic catalyst for efficient electrochemical nitrogen reduction reaction (NRR) under ambient conditions. The structure of the catalyst was characterized by transmission electron microscopy (TEM), X‐ray diffraction (XRD), elemental mapping, X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The catalyst held a superior selectivity for NRR with high Faraday efficiency of 78.2 % accompanying with NH3 yield rate of 14.0 μg mg−1cat. h−1 under the condition of 0.1 M Na2SO4 and −0.6 V vs. RHE. Electrochemical experiments including cyclic voltammetry, electrochemical impedance spectroscopy and Tafel polarization curves were performed to explain the best electrochemical properties of B4C/CNTs among the samples. This work demonstrates that the strategy of covalent modification plays an important role to improve the selectivity of electrochemical NRR catalyst, thus allowing the reactions to proceed more efficiently. [ABSTRACT FROM AUTHOR]

Brainoid computing using 2D atomic crystals and their heterostructures, by emulating the human brain's remarkable efficiency and minimal energy consumption in information processing, poses a formidable solution to the energy‐efficiency and processing speed constraints inherent in the von Neumann architecture. However, conventional 2D material based heterostructures employed in brainoid devices are beset with limitations, performance uniformity, fabrication intricacies, and weak interfacial adhesion, which restrain their broader application. The introduction of novel 2D atomic‐molecular heterojunctions (2DAMH), achieved through covalent functionalization of 2D materials with functional molecules, ushers in a new era for brain‐like devices by providing both stability and tunability of functionalities. This review chiefly delves into the electronic attributes of 2DAMH derived from the synergy of polymer materials with 2D materials, emphasizing the most recent advancements in their utilization within memristive devices, particularly their potential in replicating the functionality of biological synapses. Despite ongoing challenges pertaining to precision in modification, scalability in production, and the refinement of underlying theories, the proliferation of innovative research is actively pursuing solutions. These endeavors illuminate the vast potential for incorporating 2DAMH within brain‐inspired intelligent systems, highlighting the prospect of achieving a more efficient and energy‐conserving computing paradigm. [ABSTRACT FROM AUTHOR]

Efficient recovery of gallium (Ga) from vanadium slag processing residue (VSPR) solution is of great significance for environmental protection and resource utilization, but improving its selective adsorption against the coexisting Sc3+ and In3+ is still challenging. Herein, a novel adsorbent consisting of 4-amino-3-hydrazino-1,2,4-triazol-5-thiol (AHTZT)-modified graphene oxide (GO-AHTZT) was successfully synthesized that exhibits a higher adsorption selectivity for Ga3+ in VSPR solution with coexisting Sc3+ and In3+. Under optimal conditions, the adsorption capacity of GO-AHTZT for Ga3+ can reach 23.92 mg g−1, which is 4.9 and 12.6 times higher than that for Sc3+ (4.87 mg g−1) and In3+ (1.90 mg g−1) adsorption, indicating the excellent anti-interference ability of GO-AHTZT against Sc3+ and In3+. The process and mechanism of Ga3+ adsorption onto GO-AHTZT was also studied and discussed in detail. By measuring the adsorption process and by characterizing the adsorbent before and after adsorption, we demonstrate that the selective interaction between the Ga3+- and N-containing groups in AHTZT is the main reason for the improved adsorption selectivity. This work opens up an avenue for the design and synthesis of highly selective adsorbents for Ga3+ in complex VSPR solutions. [ABSTRACT FROM AUTHOR]

AbstractToll-like receptor (TLR) innate immunity signalling protects against pathogens, but excessive or prolonged signalling contributes to a range of inflammatory conditions. Structural information on the TLR cytoplasmic TIR (Toll/interleukin-1 receptor) domains and the downstream adaptor proteins can help us develop inhibitors targeting this pathway. The small molecule o-vanillin has previously been reported as an inhibitor of TLR2 signalling. To study its mechanism of action, we tested its binding to the TIR domain of the TLR adaptor MAL/TIRAP (MALTIR). We show that o-vanillin binds to MALTIR and inhibits its higher-order assembly in vitro. Using NMR approaches, we show that o-vanillin forms a covalent bond with lysine 210 of MAL. We confirm in mouse and human cells that o-vanillin inhibits TLR2 but not TLR4 signalling, independently of MAL, suggesting it may covalently modify TLR2 signalling complexes directly. Reactive aldehyde-containing small molecules such as o-vanillin may target multiple proteins in the cell.

Efficient recovery of gallium (Ga) from vanadium slag processing residue (VSPR) solution is of great significance for environmental protection and resource utilization, but improving its selective adsorption against the coexisting Sc3+ and In3+ is still challenging. Herein, a novel adsorbent consisting of 4-amino-3-hydrazino-1,2,4-triazol-5-thiol (AHTZT)-modified graphene oxide (GO-AHTZT) was successfully synthesized that exhibits a higher adsorption selectivity for Ga3+ in VSPR solution with coexisting Sc3+ and In3+. Under optimal conditions, the adsorption capacity of GO-AHTZT for Ga3+ can reach 23.92 mg g−1, which is 4.9 and 12.6 times higher than that for Sc3+ (4.87 mg g−1) and In3+ (1.90 mg g−1) adsorption, indicating the excellent anti-interference ability of GO-AHTZT against Sc3+ and In3+. The process and mechanism of Ga3+ adsorption onto GO-AHTZT was also studied and discussed in detail. By measuring the adsorption process and by characterizing the adsorbent before and after adsorption, we demonstrate that the selective interaction between the Ga3+- and N-containing groups in AHTZT is the main reason for the improved adsorption selectivity. This work opens up an avenue for the design and synthesis of highly selective adsorbents for Ga3+ in complex VSPR solutions.

Boron nitride nano mate rials are usually added to polymers to adjust and improve the performance of polymer matrix composites due to their good mechanical properties, insulation properties, oxidation resistance and excellent thermal conductivity. However, the incompatibility between inorganic boron nitride nanomaterials and organic polymer materials will weaken the mechanical and thermal properties of nanocomposites, making it difficult to give full play to their superior properties. Therefore, it is urgent to study the functional modification of boron nitride nano mate rials to improve the interface compatibility, improve the material dispersion ability and adjust the surface properties of nanomate rials. The research progress of functionalized modified boron nitride nanomate rials was reviewed. The structural characteristics, physical and chemical properties of boron nitride were introduced in detail. The application of functionalized modified boron nitride in polymer matrix composites was summarized. Finally, the development trend of functionalized modified boron nitride nanomaterials was prospected. [ABSTRACT FROM AUTHOR]

The significant role of papain-like cysteine proteases, including papain, cathepsin L and SARS-CoV-2 PLpro, in biomedicine and biotechnology makes them interesting model systems for sensor development. These enzymes have a free thiol group that is suitable for many sensor designs including strong binding to gold nanoparticles or low-molecular-weight inhibitors. Focusing on the importance of the preservation of native protein structure for inhibitor-binding and molecular-imprinting, which has been applied in some efficient examples of sensor development, the aim of this work was to examine the effects of the free-thiol-group's reversible blocking on papain denaturation that is the basis of its activity loss and aggregation. To utilize biophysical methods common in protein structural transitions characterization, such as fluorimetry and high-resolution infrared spectroscopy, low-molecular-weight electrophilic thiol blocking reagent S-Methyl methanethiosulfonate (MMTS) was used in solution. MMTS binding led to a two-fold increase in 8-Anilinonaphthalene-1-sulfonic acid fluorescence, indicating increased hydrophobic residue exposure. A more in-depth analysis showed significant transitions on the secondary structure level upon MMTS binding, mostly characterized by the lowered content of α-helices and unordered structures (either for approximately one third), and the increase in aggregation-specific β-sheets (from 25 to 52%) in a dose-dependant manner. The recovery of this inhibited protein showed that reversibility of inhibition is accompanied by reversibility of protein denaturation. Nevertheless, a 100-fold molar excess of the inhibitor led to the incomplete recovery of proteolytic activity, which can be explained by irreversible denaturation. The structural stability of the C-terminal β-sheet rich domain of the papain-like cysteine protease family opens up an interesting possibility to use its foldamers as a strategy for sensor development and other multiple potential applications that rely on the great commercial value of papain-like cysteine proteases. [ABSTRACT FROM AUTHOR]

Copyright of Wool Textile Journal is the property of National Wool Textile Science & Technology Information Center and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The effects of carbon nanomaterials on the kinetics of gas hydrate formation are reviewed in de- tail. The influence of parameters such as growth cycle is introduced. The effects of the concentration of nanomaterials on the kinetics of hydrate production and the separation of CO2 in the gas mixture were a nalyzed. For non-covalently modified nanomaterials, the effects of surfactant modification and polymer modification on the kinetics of hydrate formation were expounded. In terms of covalent modification, the stability of the nanomaterials after redox modification and nano-metal ion modification and the formation characteristics of hydrate were analyzed. It is suggested that the key problem of promoting the formation of hydrates by carbon nanomaterials at this stage should be broken through from the two aspects of the stable dispersion of synthetic nanomaterials and the recycling performance of synthetic materials. [ABSTRACT FROM AUTHOR]

Antarctic krill is a consumption resource with great exploitation potential. Previous study has found that carrageenan contributed to the improvement of texture characteristics of Antarctic krill surimi, but the specific synergistic mechanism remains unclear. This study aimed to evaluate and map the synergistic effect of κ-carrageenan on the quality properties of the myofibrillar protein complex gels of Antarctic krill and its potential modification sites. The analysis of physical quality, structure and molecular force showed that the incorporation of κCG induced the unfolding of myofibrillar proteins, resulting in alterations in the spatial conformation of the proteins, exposure of side-chain groups, and enhancement of intramolecular or intermolecular interactions in the gel system, which increased crosslinking of the MP-κCG composite gel networks. The higher degree of cross-linking facilitated the formation of denser network structures with higher storage and loss moduli, ultimately leading to improved gel quality properties. Notably, κCG plays a dual role in the gel network: it can not only support and stabilize the network structure of gel protein by filling the gaps, but also directly participate in the formation of gels by non-covalent and covalent interactions. Through the identification of the potential modification sites of κCG on Antarctic krill proteins, it was found that the main modified protein was myosin heavy chain and actin. Furthermore, lysine, arginine, threonine, serine and histidine were found to have high adduction quantities and reaction efficiencies. These findings are helpful to guide the quality control of Antarctic krill meat in the application process. [Display omitted] • The gelling property of Antarctic krill MP was enhanced. • LC-MS/MS was used to investigate potential κCG modification sites. • κCG was involved in gel formation via noncovalent and covalent interactions. • The major modifiers of κCG were myosin heavy chain and actin. • Lysine and arginine had higher adduction quantities and reaction efficiencies. [ABSTRACT FROM AUTHOR]

Graphene and its derivatives have achieved great attention in nearly every field of engineering and science due to mechanical, thermal, and physical features. It is frequently necessary to disperse graphene into aqueous or organic fluids in order to take use of its remarkable properties. It is necessary to attain dispersion at a concentration and stability suitable for the intended use. Unfortunately, graphene disperses poorly in all but a few high boiling organic solvents due to the strong interactions between graphene sheets. This review summarizes the techniques for enhancing dispersions and the established mechanisms. The graphene and its derivatives, their structure, and dispersions methods with and without surface modification, along with their applications, are discussed in this review. [Display omitted] • Introduction to graphene and its derivatives, their structure, and dispersion parameters. • Comprehensive overview of covalent and non-covalent modifications of graphene and their impact. • Applications of graphene: polymer composites, graphene inks, environmental uses, sensors, and industrial perspectives. • Current challenges and future perspectives for graphene dispersions in various applications. [ABSTRACT FROM AUTHOR]

Acute kidney injury (AKI) is a sudden kidney dysfunction caused by aberrant reactive oxygen species (ROS) metabolism that results in high clinical mortality. The rapid development of ROS scavengers provides new opportunities for AKI treatment. Herein, the use of hydrogen‐terminated germanene (H‐germanene) nanosheets is reported as an antioxidative defense nanoplatform against AKI in mice. The simulation results show that 2D H‐germanene can effectively scavenge ROS through free radical adsorption and subsequent redox reactions. In particular, the H‐germanene exhibits high accumulation in injured kidneys, thereby offering a favorable opportunity for treating renal diseases. In the glycerol‐induced murine AKI model, H‐germanene delivers robust antioxidative protection against ROS attack to maintain normal kidney function indicators without negative influence in vivo. This positive in vivo antioxidative defense in living animals demonstrates that the present H‐germanene nanoplatform is a powerful antioxidant against AKI and various anti‐inflammatory diseases. [ABSTRACT FROM AUTHOR]

Vanadomolybdates (VMos), comprised of Mo and V in high valences with O bridges, are one of the most important types of polyoxometalates (POMs), which have high activity due to their strong capabilities of gaining/losing electrons. Compared with other POMs, the preparation of VMos is difficult due to their relatively low structural stability, especially those with unclassical architectures. To overcome this shortcoming, in this study, triol ligands were applied to synthesize VMos through a beaker reaction in the presence of V2O5, Na2MoO4, and organic species in the aqueous solution. The single-crystal X-ray diffraction results indicate that two VMo clusters, Na4{V5Mo2O19[CH3C(CH2O)3]}∙13H2O and Na4{V5Mo2O19[CH3CH2C(CH2O)3]}∙13H2O, with a similar architecture, were synthesized, which were both stabilized by triol ligand and {MoO6} polyhedron. Both clusters are composed of five V ions and one Mo ion in a classical Lindqvist arrangement with an additional Mo ion, showing an unprecedented hepta-nuclear VMo structure. The counter Na+ cations assemble into one-dimensional channels, which facilitates the transport of protons and was further confirmed by proton conductivity experiments. The present results provide a new strategy to prepare and stabilize VMos, which is applicable for developing other compounds, especially those with untraditional architectures. [ABSTRACT FROM AUTHOR]

Graphene shows ultrafast carrier relaxation dynamics and ultra-broadband resonate nonlinear optical (NLO) response due to its extended π-conjugate system and the linear dispersion relation holding for its electronic band structure. In comparison with graphene, functionalized graphene derivatives would be expected to show more excellent NLO and optical limiting (OL) performance. By using as-synthesized graphene carbanions as initiator in the anionic polymerization, poly(Nvinylcarbazole)- covalently functionalized reduced graphene oxide (RGO) derivative (RGO-PVK) was in situ synthesized. RGO-PVK was characterized by infrared spectroscopy, X-ray electron spectroscopy and UV-Vis absorption spectroscopy. This soluble material was embedded into an optically nonactive transparent polymethylmethlacrylate (PMMA) matrix to produce the PMMA-based RGO-PVK film. The NLO and OL properties of RGO, RGO-PVK, and annealed RGO-PVK films under 532 nm and 1 064 nm laser irradiation were also investigated using the open-aperture Z-scan technique.The results show that in contrast to RGO, the covalent grafting of PVK chains to the RGO surface significantly improve NLO and broadband OL performance of the resultant material. Upon excitation with laser light, the achieved nonlinear coefficients and OL thresholds of the annealed RGO-PVK/PMMA film are 306.17 cm/GW and 0.37 GW/cm2 at 532 nm, and 350.32 cm/GW and 0.31 GW/cm² at 1 064 nm, respectively. These findings would make it suitable for protecting the human eyes, optical sensors and optoelectronic devices from the laser beam in the visible and near-infrared spectral region. [ABSTRACT FROM AUTHOR]

Selenium is a potent nucleophile essential for selenoenzymes, such as glutathione peroxidase (also known as GSH-Px; GPX; GPx) and selenoprotein P (also known as SelP; SEPP1; SELENOP; SeP). SeP is predominantly secreted from the liver and functions as a selenium carrier in plasma. We previously found that sulforaphane (SFN), an electrophilic phytochemical, reduces SeP production in cultured hepatocytes and mouse liver, however, the effect of electrophilic modification of SeP by SFN on selenium transport and metabolism remains unclear. In the present study, we demonstrate that sulforaphane covalently modifies selenocysteine/cysteine residues of SeP using an acidic biotin PAEC 5 maleimide labeling assay, which allows for focused-labeling of selenocysteine residues. Although the SFN-SeP adduct can be taken up by HepG2 cells and degraded by the lysosome, it was less effective in inducing GPx expression. Our findings indicate that SFN disrupts the selenium supply pathway through the formation of the SeP-SFN adduct., Competing Interests: Declaration of competing interests The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Takashi Tyama reports financial support was provided by Japan Society for the Promotion of Science. Yoshiro Saito reports financial support was provided by japan society for the promotion of science. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Inc. All rights reserved.)

A variety of proteins interact with DNA and RNA, including polymerases, histones, ribosomes, transcription factors, and repair enzymes. However, the transient non-covalent nature of these interactions poses challenges for analysis. Introducing a covalent bond between proteins and DNA via photochemical activation of a photosensitive functional group introduced onto nucleic acids offers a means to stabilize these often weak interactions without significantly altering the binding interface. Consequently, photoactivatable oligonucleotides are powerful tools for investigating nucleic acid-protein interactions involved in numerous biological and pathological processes. In this review, we provide a comprehensive overview of the chemical tools developed so far and the different strategies used for incorporating the most commonly used photoreactive reagents into oligonucleotide probes or nucleic acids. Furthermore, we illustrate their application with several examples including protein binding site mapping, identification of protein binding partners, and in cell studies., (© 2024 The Author(s). ChemBioChem published by Wiley-VCH GmbH.)

Abstract In order to improve the dispersion of graphene oxide (GO) in polymers, we synthesized polyurethane (PU) chains with long polydimethylsiloxane (PDMS) chains as the “soft segment” and hexamethylene diisocyanate (HDI) as the “hard segment”, then the PU chains were grafted onto GO. The results of compatibility in solvents and TEM images of composites indicated that the modified GO (GO‐PU) would present two different shapes in non‐polar and polar solvents (cocoon‐like shape and stretched shape, respectively). The two shapes made it have a good dispersion in both non‐polar and polar polymers, it was expected to be applied in both non‐polar and polar polymer matrixes. This provided a method for covalent modification of GO.

Abstract Acute kidney injury (AKI) is a sudden kidney dysfunction caused by aberrant reactive oxygen species (ROS) metabolism that results in high clinical mortality. The rapid development of ROS scavengers provides new opportunities for AKI treatment. Herein, the use of hydrogen‐terminated germanene (H‐germanene) nanosheets is reported as an antioxidative defense nanoplatform against AKI in mice. The simulation results show that 2D H‐germanene can effectively scavenge ROS through free radical adsorption and subsequent redox reactions. In particular, the H‐germanene exhibits high accumulation in injured kidneys, thereby offering a favorable opportunity for treating renal diseases. In the glycerol‐induced murine AKI model, H‐germanene delivers robust antioxidative protection against ROS attack to maintain normal kidney function indicators without negative influence in vivo. This positive in vivo antioxidative defense in living animals demonstrates that the present H‐germanene nanoplatform is a powerful antioxidant against AKI and various anti‐inflammatory diseases.

The significant role of papain-like cysteine proteases, including papain, cathepsin L and SARS-CoV-2 PLpro, in biomedicine and biotechnology makes them interesting model systems for sensor development. These enzymes have a free thiol group that is suitable for many sensor designs including strong binding to gold nanoparticles or low-molecular-weight inhibitors. Focusing on the importance of the preservation of native protein structure for inhibitor-binding and molecular-imprinting, which has been applied in some efficient examples of sensor development, the aim of this work was to examine the effects of the free-thiol-group’s reversible blocking on papain denaturation that is the basis of its activity loss and aggregation. To utilize biophysical methods common in protein structural transitions characterization, such as fluorimetry and high-resolution infrared spectroscopy, low-molecular-weight electrophilic thiol blocking reagent S-Methyl methanethiosulfonate (MMTS) was used in solution. MMTS binding led to a two-fold increase in 8-Anilinonaphthalene-1-sulfonic acid fluorescence, indicating increased hydrophobic residue exposure. A more in-depth analysis showed significant transitions on the secondary structure level upon MMTS binding, mostly characterized by the lowered content of α-helices and unordered structures (either for approximately one third), and the increase in aggregation-specific β-sheets (from 25 to 52%) in a dose-dependant manner. The recovery of this inhibited protein showed that reversibility of inhibition is accompanied by reversibility of protein denaturation. Nevertheless, a 100-fold molar excess of the inhibitor led to the incomplete recovery of proteolytic activity, which can be explained by irreversible denaturation. The structural stability of the C-terminal β-sheet rich domain of the papain-like cysteine protease family opens up an interesting possibility to use its foldamers as a strategy for sensor development and other multiple potential applications that rely on the great commercial value of papain-like cysteine proteases.

MXene quantum dots (MQDs) have excellent photoelectrochemical properties and are attracting considerable attention in the academic field. In this study, we synthesized amino-rich MQDs on the surface by modifying the Ti3C2 nanosheets with 3-aminopropyltriethoxysilane (APTES) and then cutting the functional nanosheets into quantum dots by hydrothermal reaction. The N-MQDs were characterized by UV–vis spectrophotometry, Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The prepared N-MQDs had an average particle size of 8.63 nm. The N-MQDs exhibited excellent linearity and sensitivity for the detection of Fe3+ and Cu2+ ions over a concentration range of 0.5–500 μM. The limits of detection (LODs) for the Fe3+ and Cu2+ ions were calculated to be 0.17 and 0.15 μM, respectively. Compared with previous N-doped Ti3C2 MQDs, our prepared N-MQDs possessed lower LOD for the detection of Cu2+ ions. The quantum dot showed a potential to detect Cu2+ ions in water samples with sodium hexametaphosphate (SHPP) as a Fe3+ions masking agent. N-doped MQDs can enhance the fluorescence quantum yield and detection sensitivity for metal ions over that of MQDs without amination. N-MQDs prepared by the method with active amino groups and high stability than previous works, which can expand the application of MQDs in other fields. This study also opens an avenue for the covalent modification of MXene QDs materials and surface engineering fields. [ABSTRACT FROM AUTHOR]

This review presents an update on nanotube functionalization, including an investigation of their methods and applications. The review starts with the discussion of microscopy and spectroscopy investigations of functionalized carbon nanotubes (CNTs). The results of transmission electron microscopy and scanning tunnelling microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, Raman spectroscopy and resistivity measurements are summarized. The update on the methods of the functionalization of CNTs, such as covalent and non-covalent modification or the substitution of carbon atoms, is presented. The demonstrated applications of functionalized CNTs in nanoelectronics, composites, electrochemical energy storage, electrode materials, sensors and biomedicine are discussed. [ABSTRACT FROM AUTHOR]

It is of great urgency to eliminate nitroaromatic compounds (NACs) in wastewater due to their high residue and toxicity. Photocatalysis reduction is considered to be an efficient technology for converting NACs to their corresponding aromatic amines. In this work, a visible-light-driven hybrid photocatalyst was synthesized by covalently doping Fe phthalocyanine (FePc) into graphitic carbon nitride skeleton. Compared to the pristine gCN, the optimized gCN-FePc-1 photocatalyst showed enhanced absorption in visible light region, which promoted photogenerated charge transfer and separation. Using p-nitrophenol (p-NP) as the model pollutant, the CN-FePc-1 effectively reduced it to p-aminophenol (p-AP), with the photocatalytic reaction rate being 18 and 3 times higher, respectively, than those of the pristine gCN and the mechanically mixed photocatalyst of gCN/FePc. Moreover, excellent photocatalytic universality for other NACs, high stability, and good reusability also were confirmed. Based on the band structure of the gCN-FePc-1 photocatalyst, a plausible mechanism was proposed to illustrate the photocatalytic reduction process of p-NP to p-AP. This study demonstrates that the covalent modification of FePc into gCN skeleton is an effective strategy to modulate the electronic structure, and the hybrid gCN-FePc is a potential visible-light-driven photocatalyst that potentially can be used for eliminating NAC contamination in wastewater. [ABSTRACT FROM AUTHOR]

Antimicrobial and anticancer activities of the milk whey protein isolate covalently modified with phenolic compounds, chlorogenic acid and rosmarinic acid were studied. The findings indicated that, the oxidized phenolic compounds, at alkaline conditions (pH9) in open air and at room temperature, were covalently bound to whey protein as confirmed by the decrease in tryptophan content. Where, the ratio of tryptophan decrease was higher in the whey protein modified with rosmarinic acid compared to which modified with chlorogenic acid. Moreover, these interactions were characterized by the RP-HPLC and the results showed that the amount of covalently attached rosmarinic acid to whey protein was higher than the amount of chlorogenic acid. WP modified by RA and CA showed a change in the WP modified with RA showed better antioxidant activity when compared with the unmodified WP and WP modified with CA. [ABSTRACT FROM AUTHOR]

Three kinds of silylated-salicylaldimine transition metal complexes functionalized nano-silica catalysts were prepared with silylated-salicylaldimine transition metal complexes as precursors and with nano-silica as support. Three kinds of heterogeneous catalysts were characterized by elemental analysis，FT-IR， SEM and ICP. The effect of the reaction parameters and the kinds of catalytic active center on the catalytic properties of the three heterogeneous catalysts were investigated with methylaluminoxane（MAO）as the cocatalyst. The results show that when the precatalyst dosage is 7 μmol，the molar ratio of Al/M（M=Cr， Ni，Co）is 500，the reaction temperature is 35 ℃，the reaction pressure is 0. 5 MPa and the reaction time is 30 min，the catalytic activities for Si-Schiff-SiO2-Cr，Si-Schiff-SiO2-Ni and Si-Schiff-SiO2-Co in ethylene oligonerization are 1. 92×105 g（/ mol Cr·h），2. 17×105 g（/ mol Ni·h） and 2. 07×105 g（/ mol Co·h）， respectively，and the main oligomers are C4 and C6 olefin. Si-Schiff-SiO2-M has lower catalytic activity and narrower product distribution compared to the corresponding homogeneous catalyst due to the low loading of metal active center and the confinement effect of the support. Si-Schiff-SiO2-M has the good repeatability and the better thermal stability，and the activity of the recovered catalyst is up to 1. 39×105 g（/ mol Cr·h）， 1. 68×105 g（/ mol Ni·h）and 1. 42×105 g（/ mol Co·h），respectively after three oligomerization reactions. [ABSTRACT FROM AUTHOR]

We prepared the β -lactoglobulin (BLG)–ferulic acid (FA)–glucose (Glu) conjugates by alkaline method and Maillard reaction to assess the allergenicity. FA and Glu can form a ternary covalent conjugate with BLG, as evidenced by the shortening of SEC retention time, upward migration of SDS-PAGE protein bands, considerable decrease in free amino and sulfhydryl content, and changes in multistructure. BLG–Glu–FA conjugates weakly bound to immunoglobulin E in allergic sera was weak, reduced interleukin 4 and tumor necrosis factor α levels in RBL-2H3 cells and histamin and interleukin 6 secretion levels in KU812 cells, and inhibited the nuclear factor-κB signaling pathway. In vivo experiments showed that the conjugates regulated T-cell homeostasis in mouse splenic and mesenteric lymphocytes and attenuated splenic and duodenal immune injury. Therefore, the conjugates of BLG with FA combined with Glu altered the epitope structure and exhibited low allergenicity. [Display omitted] • The conjugates inhibited NF-κB signaling pathway. • The conjugates improved T-cell homeostasis and internal organ of mice injury. • BLG - ferulic acid - glucose conjugates exhibited a low allergenicity. [ABSTRACT FROM AUTHOR]

Formaldehyde is a human carcinogen that readily binds to nucleophiles, including proteins and DNA. To investigate whether exogenous formaldehyde produces adducts in extracellular fluids, we characterized modifications to human serum albumin (HSA) following incubation of whole blood, plasma, and saliva with formaldehyde at concentrations of 1, 10 and 100μM. The only HSA locus that showed the presence of formaldehyde modifications was Lys199. A N(6)-Lys adduct with added mass of 12Da, representing a putative intramolecular crosslink, was detected in biological fluids that had been incubated with formaldehyde but not in control fluids. An adduct representing N(6)-Lys formylation was detected in all fluids, but levels did not increase above control values over the tested range of formaldehyde concentrations. An adduct representing N(6)-Lys199 acetylation was also measured in all samples. We then applied the assay to repeated samples of human plasma from 6 nonsmoking volunteer subjects (from Berkeley, CA), and single samples of serum from 15 workers exposed to airborne formaldehyde at about 1.5ppm in a production facility and 15 control workers from Tianjin, China. Although all human plasma/serum samples contained basal levels of the products of N(6)-Lys formylation and acetylation, the putative crosslink product was not detected. Since the putative crosslink was observed in plasma incubated with formaldehyde at 1μM, this suggests that the endogenous concentration of formaldehyde in serum was much lower than reported in the literature. Furthermore, concentrations of the formyl adduct were not higher in workers exposed to formaldehyde at about 1.5ppm than in controls. Follow-up in vitro experiments with gaseous formaldehyde at 1.4ppm detected the putative crosslink in plasma but not whole blood. This combination of results suggests that N(6) formylation occurs within cells with subsequent release of adducted HSA to the systemic circulation. Comparing across human samples, levels of N(6)-Lys199 formyl adducts were present at similar concentrations in subjects from California and China (about 1mmol/mol HSA), but N(6)-Lys199 acetyl adducts were present at higher concentrations in Chinese subjects (0.34 vs. 0.13mmol/mol HSA).

Globins, such as myoglobin (Mb) and neuroglobin (Ngb), are ideal protein scaffolds for the design of functional metalloenzymes. To date, numerous approaches have been developed for enzyme design. This review presents a summary of the progress made in the design of functional metalloenzymes based on Mb and Ngb, with a focus on the exploitation of covalent interactions, including coordination bonds and covalent modifications. These include the construction of a metal-binding site, the incorporation of a non-native metal cofactor, the formation of Cys/Tyr-heme covalent links, and the design of disulfide bonds, as well as other Cys-covalent modifications. As exemplified by recent studies from our group and others, the designed metalloenzymes have potential applications in biocatalysis and bioconversions. Furthermore, we discuss the current trends in the design of functional metalloenzymes and highlight the importance of covalent interactions in the design of functional metalloenzymes. [Display omitted] • Progress has been made in the design of functional metalloenzymes based on myoglobin (Mb)/Neuroglobin (Ngb) by exploring covalent interactions. • A metal-binding site has been constructed in Mb to generate enzymes with a hetero-dinuclear center. • Mb has been reconstituted with non-native metal cofactor to generate artificial enzymes. • The formation of Cys/Tyr-heme covalent links regulates the structure and function of Mb/Ngb. • The design of disulfide bonds in Mb/Ngb confers functional heme enzymes for biocatalysis. [ABSTRACT FROM AUTHOR]

[Display omitted] • SDS-PAGE showed that TF modification increased the molecular weight of LYZ. • Multispectral experiments showed that TF modification changed the secondary structure. • TF modification increased the antioxidant capacity and thermal stability of LYZ. • TF modification decreased the enzymatic activity and antimicrobial properties of LYZ. Proteins modified by polyphenols have more advantages. In this study, we investigated the effect of covalent conjugation of egg white lysozyme (LYZ) with theaflavin (TF) on its structure and related functions. The LYZ-TF covalent conjugation was prepared by an alkaline method (pH 9.0) with a branching rate of about 80%. The results such as SDS-PAGE and UV spectroscopy proved the formation of the covalent conjugation. The results of fluorescence and infrared spectroscopy showed that the conformation of the LYZ-TF coupling was altered, with an increase in α-helix content by more than 10% and an increase in surface hydrophobicity compared to LYZ. The results of relevant functional characterization experiments showed the thermal stability and antioxidant properties of LYZ modified by TF, but its enzymatic activity and in vitro antimicrobial properties were inhibited. Notably, the amount of TF addition also affected the structure and function of the conjugates. These results provide some theoretical guidance for the development of novel food functional materials with enhanced properties. [ABSTRACT FROM AUTHOR]

FAPbI 3 perovskite solar cells (PSCs) have attracted widespread research attention. The interfacial properties play a crucial role in perovskite defect passivation and interfacial carrier transport, significantly influencing the power conversion efficiency (PCE) and stability of devices. Here, a novel interface modification strategy of in-situ reaction on perovskite surface is proposed. A molecule N,N′-bis(4-isocyanatophenyl)-N,N′-di-p-tolyl-[1,1′-biphenyl]-4,4′-diamine (TPD-NCO), involving a hole-transporting unit TPD was synthesized. The highly reactive isocyanate (NCO) groups addition-reacted with formamidine ions (FA+) from the FAPbI 3 surface, forming urea with firm covalent bonds. The resulting stable modification smoothened the interface, and its urea groups coordinated with Pb2+ and formed hydrogen bonds with I-, thereby passivating the surface defects and inhibiting ion migration. Moreover, the hole-transporting units were firstly anchored through this covalent modification as a p-type dopant to lower the interface energy barrier for hole extraction. The PCE of target devices increased from 22.82% to 24.46%, which also remained 93% for 5460 h under high humidity (65% RH), 87% for 1060 h under 75 °C, and 77% for 420 h under maximum power point (MPP) operation at 50 °C, indicating both excellent efficiency and long-term stabilities. This work displays the value of both firm and hole-conductive features in in-situ reactive interface modification. [Display omitted] • A TPD derivative (N,N′-bis(4-isocyanatophenyl)-N,N′-di-p-tolyl-[1,1′-biphenyl]-4,4′-diamine, TPD-NCO) was synthesized. • The reaction between -NCO and FA+ covalently modified the FAPbI 3 perovskite surface with smoothened interface and reduced defect density. • The TPD units benefit P-type doping on the perovskite surface, which promotes interfacial band alignment. • The TPD-NCO modified devices achieved a remarkable PCE of 24.46%, as well as excellent humid, thermal and MPP stabilities. [ABSTRACT FROM AUTHOR]

[Display omitted] • The soy protein isolate covalently bound to hydroxytyrosol by alkaline method. • The addition of HT transformed the structure of SPI into a disordered one. • SPI-HT adducts have enhanced emulsifying, foaming and antioxidant properties. • The adducts with different concentrations of HT have different optimal properties. This study investigated the effect of different concentrations of hydroxytyrosol (HT) covalently bound to soy protein isolate (SPI) by the alkaline method on the structure and function of the adducts. The amount of polyphenol bound to SPI first increased to a maximum of 42.83 % ± 1.08 % and then decreased. After the covalent binding of HT to SPI, turbidity and in vitro protein digestibility increased and decreased significantly with increasing concentrations of HT added, respectively, and the structure of SPI was changed. The adducts had a maximum solubility of 52.52 % ± 0.33 %, and their water holding capacity reached a maximum of 8.22 ± 0.11 g/g at a concentration of 50 μmol/g of HT. Covalent modification with HT significantly increased the emulsifying and foaming properties and antioxidant activity of SPI; the DPPH and ABTS radical scavenging rates increased by 296.89 % and 33.80 %, respectively, at a concentration of 70 μmol/g of HT. [ABSTRACT FROM AUTHOR]

Toll-like receptor (TLR) innate immunity signalling protects against pathogens, but excessive or prolonged signalling contributes to a range of inflammatory conditions. Structural information on the TLR cytoplasmic TIR (Toll/interleukin-1 receptor) domains and the downstream adaptor proteins can help us develop inhibitors targeting this pathway. The small molecule o-vanillin has previously been reported as an inhibitor of TLR2 signalling. To study its mechanism of action, we tested its binding to the TIR domain of the TLR adaptor MAL/TIRAP (MAL TIR ). We show that o-vanillin binds to MAL TIR and inhibits its higher-order assembly in vitro . Using NMR approaches, we show that o-vanillin forms a covalent bond with lysine 210 of MAL. We confirm in mouse and human cells that o-vanillin inhibits TLR2 but not TLR4 signalling, independently of MAL, suggesting it may covalently modify TLR2 signalling complexes directly. Reactive aldehyde-containing small molecules such as o-vanillin may target multiple proteins in the cell.

Transparent films of single-walled carbon nanotubes (SWCNTs) were prepared by modified CVD synthesis, and their structure was investigated at the atomic level. The composition of organic impurities that formed a moss-like coating around the nanotubes was determined by gas chromatography–mass spectrometry (GC–MS) analysis. It was found that the films had clearly pronounced Van Hove singularities, which indicated a high concentration of single-walled nanotubes in them. Under gamma-irradiation, the walls of the nanotubes were covalently modified by impurities that formed a moss-like coating around them. [ABSTRACT FROM AUTHOR]

In the last years, the development of nano-formulations for cancer treatment represents one of the major challenges of the scientific research. The prodrug strategy, that combines chemotherapeutic agents with nanocarriers such as halloysite nanotubes (HNTs), is a promising strategy both to improve the biological activity of the drug molecules and to reduce the side effects of drugs. Herein we report the synthesis and characterization of a HNTs prodrug based on 1,2,3-triazole units covalently linked to HNTs external surface, bearing different positively charged moieties, which could present interesting pharmacological activities. [ABSTRACT FROM AUTHOR]

The autophagic ubiquitin‐like protein LC3 functions through interactions with LC3‐interaction regions (LIRs) of other autophagy proteins, including autophagy receptors, which stands out as a promising protein–protein interaction (PPI) target for the intervention of autophagy. Post‐translational modifications like acetylation of Lys49 on the LIR‐interacting surface could disrupt the interaction, offering an opportunity to design covalent small molecules interfering with the interface. Through screening covalent compounds, we discovered a small molecule modulator of LC3A/B that covalently modifies LC3A/B protein at Lys49. Activity‐based protein profiling (ABPP) based evaluations reveal that a derivative molecule DC‐LC3in‐D5 exhibits a potent covalent reactivity and selectivity to LC3A/B in HeLa cells. DC‐LC3in‐D5 compromises LC3B lipidation in vitro and in HeLa cells, leading to deficiency in the formation of autophagic structures and autophagic substrate degradation. DC‐LC3in‐D5 could serve as a powerful tool for autophagy research as well as for therapeutic interventions. [ABSTRACT FROM AUTHOR]

SARS-CoV-2 main protease is a possible target for protection against viral infection. This study examined the inhibitory effect of food phytochemicals on the main protease of SARS-CoV-2 by determining a cleaved product after chromatographic separation. First, 37 phytochemicals, including glycosides and metabolites, were screened at 20 µM; epigallocatechin gallate, myricetin, theaflavin, herbacetin, piceatannol, myricitrin, and isothiocyanates inhibited the enzyme in varying degrees. The IC50 values were estimated from 0.4 to 33.3 µM against the 0.5-µM enzyme. The dose-dependent adduction of epigallocatechin gallate and myricetin was confirmed by quinone staining of protein blotted onto a membrane. The enzyme activity was decreased by increasing the concentration of the two phytochemicals, accompanied by increasing the respective adducted molecule estimated by intact mass spectrometry. Reduced glutathione canceled the formation of conjugate and the inhibitory effect of epigallocatechin gallate or myricetin on the enzyme, suggesting that the formation of the quinone moiety in the phytochemicals is critical for the inhibition. The covalent binding of epigallocatechin gallate or myricetin to the cysteine residue at the active site was confirmed by analyzing peptides from the chymotrypsin-digested main protease.

Covalently modified polyoxometalates (POMs), which benefit from the synergistic effect between POMs and covalently grafted moieties, have received increasing attention in various fields. Recent studies on covalently modified POMs mainly focus on function-directed POM assemblies. This review summarizes the latest progress (2017–2022) concerning covalently modified POMs from a functional perspective, which can be classified as assembly chemistry, photochemistry, electrochemistry, homogeneous and heterogeneous catalysis, and biological applications. The roles of POMs and covalently grafted moieties in these hybrids, especially the rational design for specific applications, were considered and emphasized.

Three-dimensional (3D) printing has showed great potential for the construction of electrochemical sensor devices. However, reported 3D-printed biosensors are usually constructed by physical adsorption and needed immobilizing reagents on the surface of functional materials. To construct the 3D-printed biosensors, the simple modification of the 3D-printed device by non-expert is mandatory to take advantage of the remote, distributed 3D printing manufacturing. Here, a 3D-printed electrode was prepared by fused deposition modeling (FDM) 3D printing technique and activated by chemical and electrochemical methods. A glucose oxidase-based 3D-printed nanocarbon electrode was prepared by covalent linkage method to an enzyme on the surface of the 3D-printed electrode to enable biosensing. X-ray photoelectron spectroscopy and scanning electron microscopy were used to characterize the glucose oxidase-based biosensor. Direct electrochemistry glucose oxidase-based biosensor with higher stability was then chosen to detect the two biomarkers, hydrogen peroxide and glucose by chronoamperometry. The prepared glucose oxidase-based biosensor was further used for the detection of glucose in samples of apple cider. The covalently linked glucose oxidase 3D-printed nanocarbon electrode as a biosensor showed excellent stability. This work can open new doors for the covalent modification of 3D-printed electrodes in other electrochemistry fields such as biosensors, energy, and biocatalysis. [ABSTRACT FROM AUTHOR]

Chemical treatments are used to introduce active functional groups and/or to increase the surface roughness of carbon fibres (CF) aiming to improve their interaction with polar polymeric matrices in composites. Considering the new challenges in the field of composite materials, such as the processing of hybrid composites and the growing use of thermoplastic structural composites, the modification of the CF surface has been increasingly studied. In this paper, the effect of various chemical treatments (with HCl, HNO3, H2SO4, CH3COOH, NH4OH, or H2O2) on the thermal stability, chemical composition, and microstructural parameters of a polyacrylonitrile‐based carbon fibre was investigated. Raman results indicated greater degree of crystallinity at the surface for the fibres treated (at 80°C for 1 h) with HCl, HNO3, H2SO4, and H2O2. The treatment with HCl at 80°C for 1 h was effective in reducing disturbance of the carbon structure, as indicated by the higher FWHMG value compared with those of the as‐received, acetone pretreated, and the other chemically treated carbon fibres. Fourier transform infrared (FTIR) showed that some treatments promoted an increase in CF polarity (H2SO4 at 80°C/1 h and NH4OH at 20°C/1 h), with the incorporation of organic polar groups (i.e., –OH). The apparent roughness of pretreated carbon fibre increased when treated with HNO3 at 80°C/1 h and H2SO4 at 80°C/1 h, as observed in the AFM analyses. AFM, FTIR, and Raman results suggest that the fibres treated with HNO3, H2SO4, and NH4OH were the most promising as reinforcement in high‐performance polymer composites. [ABSTRACT FROM AUTHOR]

In order to improve the dispersion of graphene oxide (GO) in polymers, we synthesized polyurethane (PU) chains with long polydimethylsiloxane (PDMS) chains as the "soft segment" and hexamethylene diisocyanate (HDI) as the "hard segment", then the PU chains were grafted onto GO. The results of compatibility in solvents and TEM images of composites indicated that the modified GO (GO‐PU) would present two different shapes in non‐polar and polar solvents (cocoon‐like shape and stretched shape, respectively). The two shapes made it have a good dispersion in both non‐polar and polar polymers, it was expected to be applied in both non‐polar and polar polymer matrixes. This provided a method for covalent modification of GO. [ABSTRACT FROM AUTHOR]

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Vanadomolybdates (VMos), comprised of Mo and V in high valences with O bridges, are one of the most important types of polyoxometalates (POMs), which have high activity due to their strong capabilities of gaining/losing electrons. Compared with other POMs, the preparation of VMos is difficult due to their relatively low structural stability, especially those with unclassical architectures. To overcome this shortcoming, in this study, triol ligands were applied to synthesize VMos through a beaker reaction in the presence of V2O5, Na2MoO4, and organic species in the aqueous solution. The single-crystal X-ray diffraction results indicate that two VMo clusters, Na4{V5Mo2O19[CH3C(CH2O)3]}∙13H2O and Na4{V5Mo2O19[CH3CH2C(CH2O)3]}∙13H2O, with a similar architecture, were synthesized, which were both stabilized by triol ligand and {MoO6} polyhedron. Both clusters are composed of five V ions and one Mo ion in a classical Lindqvist arrangement with an additional Mo ion, showing an unprecedented hepta-nuclear VMo structure. The counter Na+ cations assemble into one-dimensional channels, which facilitates the transport of protons and was further confirmed by proton conductivity experiments. The present results provide a new strategy to prepare and stabilize VMos, which is applicable for developing other compounds, especially those with untraditional architectures.

Graphene-based nanocomposites constitute an interesting and promising material for various applications. Intensive progress in the development of this group of materials offers an opportunity to create new systems useful for drinking water decontamination or other biotechnological applications. Nanohybrid structures of graphene-ceramic systems can be obtained using covalent graphene surface modification with nanoparticles (NPs) of ceramic and/or co-deposition of metals with selected morphology and chemistry. The present paper systematizes the associated bio-related knowledge and inspires future development of graphene/NPs systems. Emerging knowledge and unique research techniques are reviewed within designing the required nanocomposite structure and chemical composition, development and optimization of new methods of covalent surface modification of graphene with NPs as well as analysis of mechanisms governing the formation of covalent bonding. Further, innovative research tools and methodologies are presented regarding the adjustment of functionalities of materials used for the application in drinking water decontamination or biocidal composites. This study provides a comprehensive base for rational development of more complex, hybrid graphene-based nanomaterials with various bio-functionalities that can be further applied in industrial practice.

Biphasic calcium phosphate (BCP) materials are widely employed as bone substitute materials due to their resorption/degradation properties. Inflammation after implantation of such materials represents a prerequisite for bone tissue repair and regeneration but can be also problematic if it is not only transient and if it is followed by fibrosis and scarring. Here, we modified BCP covalently with hyaluronan (HA) and heparin (Hep), glycosaminoglycans that possess anti‐inflammatory properties. Beside the characterization of particle surface properties, the focus was on in vivo tissue response after subcutaneous implantation in mice. Histological analysis revealed a decrease in signs of inflammatory response to BCP when modified with either HA or Hep. Reduced vascularization after 30 days was noticed when BCP was modified with either HA or Hep with greater cellularity in all examined time points. Compared to plain BCP, expression of endothelial‐related genes Flt1 and Vcam1 was higher in BCP‐HA and BCP‐Hep group at day 30. Expression of osteogenesis‐related genes Sp7 and Bglap after 30 days was the highest in BCP group, followed by BCP‐Hep, while the lowest expression was in BCP‐HA group which correlates with collagen amount. Hence, coating of BCP particles with HA seems to suppress inflammatory response together with formation of new bone‐like tissue, while the presence of Hep delays the onset of inflammatory response but permits osteogenesis in this subcutaneous bone‐forming model. Transferring the results of this study to other coated materials intended for biomedical application may also pave the way to reduction of inflammation after their implantation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Construction of robust polymer coating for micro-sized SiO x based a polydopamine-mediated strategy. • Interfacial effect of polymer coating for micro-sized SiO x to suppress electrolyte corrosion and stable solid-electrolyte interface layer. • Remarkable improvement in cycling performance of pouch-cells with the functional polymer-coated SiO x. Functional polymer coating is one of effective strategies to achieve high performance Si-based anodes for lithium-ion batteries (LIBs). Unfortunately, many functional polymers are incompatible with carbon layer which are important for electrical conductivity of Si-based composites, especially for carbon-coated SiO x microparticles (SiOC). Here, we present a polydopamine (PDA)-mediated strategy that enables a robust polyacrylamide (PAM) polymer to effectively couple with SiOC microparticles through the PDA bridge. As a robust barrier, the PDA-PAM coating effectively inhibits electrolyte corrosion while promoting the formation of a stable solid electrolyte interface layer. The resulting SiOC@PDA-PAM microparticles display enhanced cycling stability without sacrificing their rate performance. The pouch cell incorporated with 10 wt% SiOC@PDA-PAM in graphite anode has a superior capacity retention of 85.1% after 800 cycles and an improved storage performance due to the stable interfacial chemistry of SiOC@PDA-PAM. Considering the strong adhesion and easy functionalization of PDA for surface modification, this work spotlights the prospect of developing more functional polymer coating to extend the cycling life of Si-based anodes. [ABSTRACT FROM AUTHOR]

Enzymes of the enolase superfamily share a conserved structure and a common partial reaction (i.e. , metal-assisted, Brønsted base-catalyzed enol(ate) formation). The architectures of the enolization apparatus at the active sites of the mandelate racemase (MR)-subgroup members MR and l -fuconate dehydratase (FucD) are almost indistinguishable at the structural level. Tartronate and 3-hydroxypyruvate (3-HP) recognize the enolization apparatus and can be used to interrogate the active sites for differences that may not be apparent from structural data. We report a circular dichroism-based assay of FucD activity that monitors the change in ellipticity at 216 nm (Δ[Θ] S – P = 8985 ± 87 deg cm2 mol−1) accompanying the conversion of l -fuconate to 2-keto-3-deoxy- l -fuconate. Tartronate was a linear mixed-type inhibitor of FucD (K i = 8.4 ± 0.7 mM, α K i = 63 ± 11 mM), binding 18-fold weaker than l -fuconate, compared with 2-fold weaker binding of tartronate by MR relative to mandelate. 3-HP irreversibly inactivated FucD (k inact / K I = 0.018 ± 0.002 M−1s−1) with an efficiency that was ∼4.6 × 103-fold less than that observed with MR. The inactivation arose predominantly from modifications at multiple sites and Tris-HCl, but not l -fuconate, afforded protection against inactivation. Similar to the reaction of 3-HP with MR, 3-HP modified the Brønsted base catalyst (Lys 220) at the active site of FucD, which was facilitated by the Brønsted acid catalyst His 351. Thus, the interactions of tartronate and 3-HP with MR and FucD revealed differences in binding affinity and reactivity that differentiated between the enzymes' enolization apparatuses. • Tartronate is a linear mixed-type inhibitor of l -fuconate dehydratase (Xc FucD). • A continuous, circular dichroism-based assay for Xc FucD activity was developed. • 3-Hydroxypyruvate (3-HP) slowly inactivates Xc FucD (k inact / K I = 0.018 M−1s−1). • Inactivation rates depend on Tris-HCl buffer, but not l -fuconate, concentrations. • Mandelate racemase & Xc FucD may be distinguished using tartronate and 3-HP. [ABSTRACT FROM AUTHOR]

MOF‐74 is one of the most explored metal–organic frameworks (MOFs), but its functionalization is limited to the dative post‐synthetic modification (PSM) of the monodentate solvent site. Owing to the nature of the organic ligand and framework structure of MOF‐74, the covalent PSM of MOF‐74 is very demanding. Herein, we report, for the first time, the covalent PSM of amine‐tagged defective Ni‐MOF‐74, which is prepared by de novo solvothermal synthesis by using aminosalicylic acid as a functionalized fragmented organic ligand. The covalent PSM of the amino group generates metal binding sites, and subsequent post‐synthetic metalation with PdII ions affords the PdII‐incorporated Ni‐MOF‐74 catalyst. This catalyst exhibits highly efficient, size‐selective, and recyclable catalytic activity for the Suzuki–Miyaura cross‐coupling reaction. This strategy is also useful for the covalent modification of amine‐tagged defective Ni2(DOBPDC), an expanded analogue of MOF‐74. [ABSTRACT FROM AUTHOR]