Application of metal-organic frameworks and their derivates for thermal-catalytic C1 molecules conversion.

One-carbon (C1) catalysis refers to the conversion of compounds with a single carbon atom, especially carbon monoxide (CO), carbon dioxide (CO2), and methane (CH4), into clean fuels and valuable chemicals via catalytic strategy is crucial for sustainable and green development. Among various catalytic strategies, thermal-driven process seems to be one of the most promising pathways for C1 catalysis due to the high efficiency and practical application prospect. Notably, the rational design of thermal-driven C1 catalysts plays a vital role in boosting the targeted products synthesis of C1 catalysis, which relies heavily on the choice of ideal active site support, catalyst fabrication precursor, and catalytic reaction field. As a novel crystalline porous material, metal-organic frameworks (MOFs) has made significant progress in the design and synthesis of various functional nanomaterials. However, the application of MOFs in C1 catalysis faces numerous challenges, such as thermal stability, mechanical strength, yield of MOFs, and so on. To overcome these limitations and harness the advantages of MOFs in thermal-driven C1 catalysis, researchers have developed various catalyst/carrier preparation strategies. In this review, we provide a concise overview of the recent advancements in the conversion of CO, CO2, and CH4 into clean fuels and valuable chemicals via thermal-catalytic strategy using MOFs-based catalysts. Furthermore, we discuss the main challenges and opportunities associated with MOFs-based catalysts for thermal-driven C1 catalysis in the future.

Construction of phenolic acids grafted chitosan bioactive microspheres to reduce oxidation and iron absorption in meat digestion.

Although iron in meat is an important trace element for human diet, its presence also induces postprandial oxidative stress and aggravates the condition of patients with iron overload. To overcome this situation, a type of new tunable Fe-absorption bioactive materials was constructed in this study. First, four phenolic acids (Caffeic acid, Gallic acid, Protocatechuic acid, Chlorogenic acid) were grafted onto chitosan. Then, the copolymers were prepared into micron-level microspheres by emulsification method, which were characterized in adsorption isotherms (Langmuir model), swelling behavior and digestion characteristics. In order to verify the practical application effect of microspheres, Protocatechuic acid grafted chitosan microspheres as the representative were used in sirloin powder to observe their effects in vitro digestion and rat experiment. In the present study, microspheres were innovatively applied in meat consumption, which significantly inhibited the oxidation of meat in the process of digestion and effectively controlled the iron absorption. These results are expected to play an important role in promoting the healthy consumption of meat around the world, improving gastrointestinal redox status through dietary assistance, and treating diseases related to iron overload.

Design, synthesis, antibacterial evaluation of isopropylamine linked with different substituted phenol and piperazine novel derivatives.

BACKGROUND: Xanthomonas oryzae pv. oryzae (Xoo) is often considered one of the most destructive bacterial pathogens causing bacterial leaf blight (BLB), resulting in significant yield and cost losses in rice. In this study, a series of novel derivatives containing the isopropanolamine moiety linked to various substituted phenols and piperazines were designed, synthesized and screened. RESULTS: Antibacterial activity results showed that most compounds had good inhibitory effects on Xoo, among which compound W2 (EC50 = 2.74 µg mL-1) exhibited the most excellent inhibitory activity, and W2 also had a certain curative effect (35.89%) on rice compared to thiodiazole copper (TC) (21.57%). Scanning electron microscopy (SEM) results indicated that compound W2 could cause rupture of the Xoo cell membrane. Subsequently, proteomics and quantitative real-time polymerase chain reaction revealed that compound W2 affected the physiological processes of Xoo and may exert antibacterial activity by targeting the two-component system pathway. Interestingly, W2 upregulated Xoo's methyltransferase to impact on its pathogenicity. CONCLUSION: The present study offers a promising phenolic-piperazine-sopropanolamine compound as an innovative antibacterial strategy by specifically targeting the two-component system pathway and inducing upregulation of methyltransferase to effectively impact Xoo's pathogenicity. © 2024 Society of Chemical Industry.

Adjustable strength and toughness of dual cross-linked nanocellulose films via spherical cellulose as soft-phase.

Nanocellulose films possess numerous merits ascribing to their inherent biocompatibility, non-toxic and biodegradability properties. The potential for practical applications would be improved if their mechanical strength and toughness requirements could be met simultaneously. Herein, dual cross-linked nanocellulose (DC) film was fabricated by the treatments of chemical and physical cross-linking, which was mechanically superior to pure nanocellulose (CNF) films. To further increase the toughness of DC films, spherical cellulose (Sph) was incorporated into DC film (DC-Sph film), and analyzed under different humidity conditions (RH) (from 10 % to 90 %). The changes of functional groups of CNF, DC and DC-Sph films were detected by FTIR and XPS spectrum. The epichlorohydrin and Sph content were optimized, followed by the investigation of RH on the toughness of films. The highest tensile strength (146.6 ± 4.6 MPa) was obtained in DC film at 50 % RH, while the DC-Sph film showed the largest toughness (40.3 ± 3.7 kJ/m2) at 70 % RH. Furthermore, the possible toughening mechanism of DC-Sph film was also discussed.

CO2 hydrogenation over Fe-Co bimetallic catalysts with tunable selectivity through a graphene fencing approach.

Tuning CO2 hydrogenation product distribution to obtain high-selectivity target products is of great significance. However, due to the imprecise regulation of chain propagation and hydrogenation reactions, the oriented synthesis of a single product is challenging. Herein, we report an approach to controlling multiple sites with graphene fence engineering that enables direct conversion of CO2/H2 mixtures into different types of hydrocarbons. Fe-Co active sites on the graphene fence surface present 50.1% light olefin selectivity, while the spatial Fe-Co nanoparticles separated by graphene fences achieve liquefied petroleum gas of 43.6%. With the assistance of graphene fences, iron carbides and metallic cobalt can efficiently regulate C-C coupling and olefin secondary hydrogenation reactions to achieve product-selective switching between light olefins and liquefied petroleum gas. Furthermore, it also creates a precedent for CO2 direct hydrogenation to liquefied petroleum gas via a Fischer-Tropsch pathway with the highest space-time yields compared to other reported composite catalysts.

Candidate molecules as alternative nitric oxide donors with better antibacterial property against Escherichia coli and Staphylococcus aureus.

AIMS: Four nitric oxide (NO) donors, S-nitrosoglutathione (GSNO), S-nitrosocysteine (CySNO), S-nitroso-N-acetylcysteine (SNAC), and 2-(2-S-nitroso propionamide) acetic acid (GAS) were prepared and their physicochemical characteristics were analyzed. Besides, the antibacterial properties of NO donors were investigated against Escherichia coli and Staphylococcus aureus. METHODS AND RESULTS: UV-visible absorption spectrum and Fourier transform infrared spectrum verified the successful preparation of RSNOs. All NO donors (10 mmol l-1) could release NO continuously, and the amount of NO release was from 80.22 µmol l-1 to 706.63 µmol l-1, in which the release of NO from SNAC was the highest, and the release of NO from NaNO2 was the least. The inhibition zone indicated that all NO donors showed stronger antibacterial activity against E. coli and S. aureus, and the antibacterial ability was in the order of SNAC > GSNO > CySNO > GAS > NaNO2 for both E. coli and S. aureus (P < 0.05). Scanning electron microscopy(SEM) showed that all NO donors could result in varying degrees of damage to cell wall and membrane of both E. coli and S. aureus and the damage of E. coli was more severe. CONCLUSION: Four alternative NO donors were successfully synthesized. All alternative NO donors showed better antibacterial properties against E. coli and S. aureus than NaNO2.

Copper-Bridge-Enhanced p-Band Center Modulation of Carbon-Bismuth Heterojunction for CO2 Electroreduction.

Bismuth-based catalysts have advanced CO2 electroreduction to formic acid, but their intrinsic electronic structure remains a key obstacle to achieving a high catalytic performance. Herein, a copper bridge strategy is proposed to enhance electronic modulation effects in bismuth/carbon composites. Density functional theory calculations prove the novel p-d-p hybrid orbitals on the carbon-copper-bismuth heterojunction structure (Bi-Cu/HMCS) could stabilize the HCOO* intermediate and lower the thermodynamic barrier from CO2 to formic acid. With the rapid electron-supplying effect of "copper bridge", the faradaic efficiency of formate reaches 100% (±2%) at a low overpotential of 500 mV and remains above 90% within a wide potential range. Using a solid-state electrolyte device, pure 0.6 M HCOOH is produced at a stable current density of 100 mA cm-2 within 7.5 h, boasting an impressive energy efficiency of 53.8%. This work offers a new strategy for optimizing electronic structure of metal/carbon composite electrocatalysts.

Overview of the effects and mechanisms of NO and its donors on biofilms.

Microbial biofilm is undoubtedly a challenging problem in the food industry. It is closely associated with human health and life, being difficult to remove and antibiotic resistance. Therefore, an alternate method to solve these problems is needed. Nitric oxide (NO) as an antimicrobial agent, has shown great potential to disrupt biofilms. However, the extremely short half-life of NO in vivo (2 s) has facilitated the development of relatively more stable NO donors. Recent studies reported that NO could permeate biofilms, causing damage to cellular biomacromolecules, inducing biofilm dispersion by quorum sensing (QS) pathway and reducing intracellular bis-(3'-5')-cyclic dimeric guanosine monophosphate (c-di-GMP) levels, and significantly improving the bactericidal effect without drug resistance. In this review, biofilm hazards and formation processes are presented, and the characteristics and inhibitory effects of NO donors are carefully discussed, with an emphasis on the possible mechanisms of NO resistance to biofilms and some advanced approaches concerning the remediation of NO donor deficiencies. Moreover, the future perspectives, challenges, and limitations of NO donors were summarized comprehensively. On the whole, this review aims to provide the application prospects of NO and its donors in the food industry and to make reliable choices based on these available research results.

Effects of Covalent or Noncovalent Binding of Different Polyphenols to Acid-Soluble Collagen on Protein Structure, Functionality, and Digestibility.

In this study, the structure, function, and digestibility of noncovalent complexes and covalent conjugates formed by acid-soluble collagen with polyphenols of different structures (quercetin, epicatechin, gallic acid, chlorogenic acid, procyanidin, and tannic acid) were investigated. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that polyphenols were covalently bound to collagen by laccase catalytic oxidation. Biolayer interferometry revealed that the noncovalent binding strength of polyphenols to collagen from high to low was quercetin > gallic acid > chlorogenic acid > epicatechin, which was consistent with the trend of covalent polyphenol binding. Procyanidin and tannic acid had strong noncovalent binding, but their covalent binding ability was weak. Compared with the pure collagen, the complexes improved emulsification and antioxidant properties (more than 2.5 times), and the conjugates exhibited better thermal stability (99.4-106.8 °C) and antidigestion ability (reduced by more than 37%). The finding sheds new light on the use of collagen as a functional food ingredient in the food industry.

Advances in the authentication of collagen products based on DNA technology.

Collagenous products are making their way into consumer markets such as foods, nutraceuticals, cosmetics and pharmaceuticals increasingly. Collagen in a large family of proteins is ubiquitous in metazoan. The most effective way to identify biological samples including collagen is DNA technology indisputably. However, the DNA content of collagen mostly derived from connective tissue is relatively less, and commercial collagen products are usually subjected to some harsh treatments in the production process, which makes DNA damage more serious, thus tracing their origin becomes a huge challenge. At present, DNA enrichment mainly relies on silica based centrifugal columns after extraction by classical phenol chloroform method. For improving the amplification of DNA fragments, small amplicons are designed based on more stable mitochondrial genes, such as cytochrome b gene (cytb). In addition to conventional PCR for DNA amplification, some new PCR techniques have also been developed, such as DNA barcoding techniques, PCR-Southern hybridization and fluorescent PCR. These PCR techniques have their pros and cons, and are mainly used in the identification of gelatin at present. The development of a complete set of DNA authentication is of great significance for the control of collagen products quality and will contribute to sustainable development of collagen industry.

Carbon-Based Electron Buffer Layer on ZnOx -Fe5 C2 -Fe3 O4 Boosts Ethanol Synthesis from CO2 Hydrogenation.

The conversion of CO2 into ethanol with renewable H2 has attracted tremendous attention due to its integrated functions of carbon elimination and chemical synthesis, but remains challenging. The electronic properties of a catalyst are essential to determine the adsorption strength and configuration of the key intermediates, therefore altering the reaction network for targeted synthesis. Herein, we describe a catalytic system in which a carbon buffer layer is employed to tailor the electronic properties of the ternary ZnOx -Fe5 C2 -Fe3 O4 , in which the electron-transfer pathway (ZnOx →Fe species or carbon layer) ensures the appropriate adsorption strength of -CO* on the catalytic interface, facilitating C-C coupling between -CHx * and -CO* for ethanol synthesis. Benefiting from this unique electron-transfer buffering effect, an extremely high ethanol yield of 366.6 gEtOH kgcat -1 h-1 (with CO of 10 vol % co-feeding) is achieved from CO2 hydrogenation. This work provides a powerful electronic modulation strategy for catalyst design in terms of highly oriented synthesis.

Tailoring the CO2 Hydrogenation Performance of Fe-Based Catalyst via Unique Confinement Effect of the Carbon Shell.

Even though Fe-based catalysts have been widely employed for CO2 hydrogenation into hydrocarbons, oxygenates, liquid fuels, etc., the precise regulation of their physicochemical properties is needed to enhance the catalytic performance. Herein, under the guidance of the traditional concept in heterogeneous catalysis-confinement effect, a core-shell structured catalyst Na-Fe3 O4 @C is constructed to boost the CO2 hydrogenation performance. Benefiting from the carbon-chain growth limitation, tailorable H2 /CO2 ratio on the catalytic interface, and unique electronic property that all endowed by the confinement effect, the selectivity and space-time yield of light olefins (C2 = -C4 = ) are as high as 47.4 % and 15.9 g molFe -1  h-1 , respectively, which are all notably higher than that from the shell-less counterpart. The function mechanism of the confinement effect in Fe-based catalysts are clarified in detail by multiple characterization and density functional theory (DFT). This work may offer a new prospect for the rational design of CO2 hydrogenation catalyst.

Using nanocellulose to improve heat-induced cull cow meat myofibrillar protein gels: effects of particle morphology and content.

BACKGROUND: Enhancing protein gel properties is essential to improve the texture of meat products. In this study, the improvement effects of three types of nanocellulose, i.e. rod-like cellulose nanocrystals (CNC), long-chain cellulose nanofibers (CNF) and spherical cellulose nanospheres (CNS) with different concentrations (1, 3, 5, 10, 15 and 20 g kg-1 ), on cull cow meat myofibrillar protein (MP) gel were investigated. RESULTS: Compared with needle-shaped CNC and spherical CNS, the addition of 10 and 20 g kg-1 long-chain CNF had the most significant improvement effect on gel hardness and water-holding capacity, respectively (P < 0.05), increasing to 160.1 g and 97.8%, respectively. In addition, the incorporation of long-chain CNF shortened the T2 relaxation time and induced the formation of the densest network structure and promoted the phase transition of the gel. However, excessive filling of nanocellulose would destroy the structure of the gel, which was not conducive to the improvement of gel properties. Fourier transform infrared results showed that there was no chemical reaction between the three nanocellulose types and MP, but the addition of nanocellulose was conducive to gel formation. CONCLUSION: The improvement of MP gel properties by adding nanocellulose mainly depends on its morphology and concentration. Nanocellulose with higher aspect ratio is more beneficial to the improvement of gel properties. For each nanocellulose type, there is an optimal addition amount for MP gel improvement. © 2023 Society of Chemical Industry.

Discovery and Mechanism of Novel 7-Aliphatic Amine Tryptanthrin Derivatives against Phytopathogenic Bacteria.

Rice bacterial leaf blight is a destructive bacterial disease caused by Xanthomonas oryzae pv. oryzae (Xoo) that seriously threatens crop yields and their associated economic benefits. In this study, a series of improved dissolubility 7-aliphatic amine tryptanthrin derivatives was designed and synthesized, and their potency in antibacterial applications was investigated. Notably, compound 6e exhibited excellent activity against Xoo, with an EC50 value of 2.55 µg/mL, compared with the positive control bismerthiazol (EC50 = 35.0 µg/mL) and thiodiazole copper (EC50 = 79.4 µg/mL). In vivo assays demonstrated that 6e exhibited a significant protective effect on rice leaves. After exposure, the morphology of the bacteria was partially atrophied by SEM. Furthermore, 6e increased the accumulation of intracellular reactive oxygen species, causing cell apoptosis and the formation of bacterial biofilms. All the results indicated that 6e could be a potential agrochemical bactericide for controlling phytopathogenic bacteria.

Inhibition of α-amylase and amyloglucosidase by cellulose nanofibrils with different surface charge and spectroscopic analysis of their interaction mechanism.

We investigated the inhibition effect of carboxymethylated cellulose nanofibrils with four different surface chargeon α-amylase and amyloglucosidase via enzyme activity inhibition assay, fluorescence spectra and secondary structure change analysis. These results revealed that cellulose nanofibril with lowest surface charge displayed the greatest inhibition effects against α-amylase (9.81 mg/mL) and amyloglucosidase (13.16 mg/mL). All cellulose nanofibrils in starch model significantly (p < 0.05) inhibited the starch digestion, where the inhibition effect was negatively correlated with the magnitude of particle surface charge. Cellulose nanofibrils could bind α-amylase or amyloglucosidase to form new complex in the manner of static quenching. The thermodynamic parameters demonstrated that the cellulose nanofibrils-starch hydrolase (α-amylase or amyloglucosidase) complexes were formed spontaneously via hydrophobic effects. Additionally, Fourier transform Infrared spectra exhibited the changes in the fraction of secondary structures of starch hydrolase after the interactions with carboxymethylated cellulose nanofibrils. These data provide a convenient and simple method tailor gastrointestinal digestion of starch by changing cellulose surface charge, to control postprandial serum glucose upsurge.

Boosting Methanol-Mediated CO2 Hydrogenation into Aromatics by Synergistically Tailoring Oxygen Vacancy and Acid Site Properties of Multifunctional Catalyst.

Even though the direct hydrogenation of CO2 into aromatics has been realized via a methanol-mediated pathway and multifunctional catalyst, few works have been focused on the simultaneously rational design of each component in multifunctional catalyst to improve the performance. Also, the structure-function relationship between aromatics synthesis performance and the different catalytic components (reducible metal oxide and acidic zeolite) has been rarely investigated. Herein, we increase the oxygen vacancy (Ov ) density in reducible Cr2 O3 by sequential carbonization and oxidation (SCO) treatments of Cr-based metal-organic frameworks. Thanks to the enriched Ov , Cr2 O3 -based catalyst affords high methanol selectivity of 98.1 % (without CO) at a CO2 conversion of 16.8 % under high reaction temperature (350 °C). Furthermore, after combining with the acidic zeolite H-ZSM-5, the multifunctional catalyst realizes the direct conversion of CO2 into aromatics with conversion and selectivity as high as 25.4 % and 80.1 % (without CO), respectively. The property of acid site in H-ZSM-5, especially the Al species that located at the intersection of straight and sinusoidal channels, plays a vital role in enhancing the aromatics selectivity, which can be precisely controlled by varying the hydrothermal synthesis conditions. Our work provides a synergistic strategy to boost the aromatics synthesis performance from CO2 hydrogenation.

Hofmeister anion effects synergize with microbial transglutaminase to enhance the techno-functional properties of pea protein.

Pea protein are emerging as the most potential alternative for meat products, but its application was hindered by their weaker gelling properties. Here, the feasibility of combining the Hofmeister anion (CO32-, Citrate3-, and SO42-) effect with microbial transglutaminase (MTG) cross-linking strategy to improve the techno-functional properties of pea protein was studied. Hofmeister anions or/and MTG treatment of pea protein caused a clear shift in far-UV CD spectra towards ß-turn and random coil structures. Furthermore, Hofmeister anion and MTG-induced crosslinking caused a reduction of surface hydrophobicity in contrast with anions-treated. Compared to CO32- and SO42-, Citrate3- treatment can better improve the efficiency of MTG-crosslinking, as demonstrated by a reduction in free amino group contents and an increase in mean diameter size. Using MTG in combination with Hofmeister anions showed significantly improved foam property and gel hardness as well as decrease gelation temperature of pea protein, specifically Citrate3- treatment. Thus, this research provides a novel and effective method to improve the effect of MTG-cross-linked pea protein, which will play an essential role in future food production.

Novel 2-Amino-1,4-Naphthoquinone Derivatives Induce A549 Cell Death through Autophagy.

A series of 1,4-naphthoquinone derivatives containing were synthesized as anti-cancer agents and the crystal structure of compound 5a was confirmed by X-ray diffraction. In addition, the inhibitory activities against four cancer cell lines (HepG2, A549, K562, and PC-3) were tested, respectively, and compound 5i showed significant cytotoxicity on the A549 cell line with the IC50 of 6.15 µM. Surprisingly, in the following preliminary biological experiments, we found that compound 5i induced autophagy by promoting the recycling of EGFR and signal transduction in the A549 cell, resulting in the activation of the EGFR signal pathway. The potential binding pattern between compound 5i and EGFR tyrosine kinase (PDB ID: 1M17) was also identified by molecular docking. Our research paves the way for further studies and the development of novel and powerful anti-cancer drugs.

Dysregulation of immune and metabolism pathways in maternal immune activation induces an increased risk of autism spectrum disorders.

AIMS: Maternal immune activation (MIA) via infection during pregnancy is known to be an environmental risk factor for neurodevelopmental disorders and the development of autism spectrum disorders (ASD) in the offspring, but it still remains elusive that the molecular relevance between infection-induced abnormal neurodevelopmental events and an increased risk for ASD development. MAIN METHODS: Fully considering the extremely high genetic heterogeneity of ASD and the universality of risk-gene with minimal effect-sizes, the gene and pathway-based association analysis was performed with the transcriptomic and DNA methylation landscapes of temporal human embryonic brain development and ASD, and the time-course transcriptional profiling of MIA. We conducted the transcriptional profiling of mouse abnormal neurodevelopment two days following induced MIA via LPS injection at E10.5. KEY FINDINGS: A novel evidence was proved that illustrated altering four immune and metabolism-related risk pathways, including starch and sucrose metabolism, ribosome, protein processing in endoplasmic reticulum, and retrograde endocannabinoid signaling pathway, which were prominent involvement in the process of MIA regulating abnormal fetal brain development to induce an increased risk of ASD. Here, we have observed that almost all key genes within these risk pathways are significantly differentially expressed at embryonic days (E) 10.5-12.5, which is considered to be the optimal coincidence window of mouse embryonic brain development to study the intimate association between MIA and ASD using mouse animal models. SIGNIFICANCE: There search establishes that MIA causes dysregulation of immune and metabolic pathways, which leads to abnormal embryonic neurodevelopment, thus promoting development of ASD symptoms in offspring.

Trace Ionic Liquid-Assisted Orientational Growth of Cu2 O (110) Facets Promote CO2 Electroreduction to C2 Products.

Cu2 O has great advantages for CO2 electroreduction to C2 products, of which the activity and selectivity are closely related to its crystal facets. In this work, density functional theory calculation indicated that the (110) facets of Cu2 O had a lower energy barrier for the C-C coupling compared to the (100) and (111) facets. Therefore, Cu2 O(110) facets were successfully synthesized with the assistance of trace amounts of the ionic liquid 1-butyl-3-methylimidazolium ([Bmim]BF4 ) by a sample wet-chemical method. A high faradaic efficiency of 71.1 % and a large current density of 265.1 mA cm-2 toward C2 H4 and C2 H5 OH were achieved at -1.1 V (vs. reversible hydrogen electrode) in a flow cell. The in situ and electrochemical analysis indicated that it possessed the synergy effects of strong adsorption of *CO2 and *CO, large active area, and excellent conductivity. This study provided a new way to enhance the C2 selectivity of CO2 electroreduction on Cu2 O by crystal structure engineering.