Highly active nitrogen-phosphorus co-doped carbon fiber@graphite felt electrode for high-performance vanadium redox flow battery.

Heteroatom-doped electrodes offer promising applications for enhancing the longevity and efficiency of vanadium redox flow battery (VRFB). Herein, we controllably synthesized N, P co-doped graphite fiber electrodes with conductive network structure by introducing protonic acid and combining electrodeposition and high temperature carbonization. H2SO4 and H3PO4 act as auxiliary and dopant, respectively. The synergistic effect between N and P introduces additional defect structures and active sites on the electrodes, thereby enhancing the reaction rate, as confirmed by density functional theory calculations. Furthermore, the conductive network structure of carbon fibers improves electrode-to-electrode connectivity and reduces internal battery resistance. The optimized integration of these strategies enhances VRFB performance significantly. Consequently, the N, P co-doped carbon fiber modified graphite felt electrodes demonstrate remarkably high energy efficiency at 200 mA cm-2, surpassing that of the blank battery by 7.9 %. This integrated approach to in-situ controllable synthesis provides innovative insights for developing high-performance, stable electrodes, thereby contributing to advancements in the field of energy storage.

Superabsorbent starch protective layer modulates zinc anode interface for long-life aqueous zinc ion batteries.

Aqueous zinc ion batteries (AZIBs) have attracted much attention for their safety, low cost and high theoretical capacity. Nevertheless, Zn dendrites and the adverse reactions such as corrosion, hydrogen evolution and passivation on the anode affect the cycle life and stability of AZIBs. Herein, superabsorbent starch (SS) was employed on Zn foil to form an artificial interface protection layer, which inhibited the formation of dendrites by guiding the uniform deposition of Zn2+. SS with a large amount of oxygen-containing functional group is superabsorbent, which can attract the active water around the hydrated Zn2+, promoting the desolvation process of the hydrated Zn2+ and significantly inhibiting the occurrence of hydrogen evolution reaction. In addition, the inherent pore structure of the SS artificial interfacial layer can induce uniform nucleation of Zn2+ and inhibit the dendrites growth. Moreover, compared to bare Zn//MnO2 cell (44.1 %), the capacity retention of Zn@SS//MnO2 cell remained as high as 87.8 % after 1000 cycles at 1.5 A g-1. The simple method provided a new method for the rapid development of AZIBs.

Effects of recrystallization degree on structure and digestibility of debranched starch.

This study developed a novel method for the facile, green and efficient fabrication of highly crystalline and heat-resistant starch via recrystallization with high concentrations of debranched starch (DBS), which greatly reduced the complexity and period compared to conventional preparation methods. The structural, thermal, and digestive properties of recrystallized DBS obtained from different concentrations (0-50 %) have been systematically investigated. For instance, the peak melting temperature of recrystallized DBS increased from around 77.8 °C to 114.7 °C with increasing DBS concentration. Moreover, the crystallinity of the recrystallized DBS increased from around 23.5 % to 73.6 % when the DBS concentration was raised. In addition, the resistant starch content of the recrystallized DBS increased from around 30.8 % to 72.1 % as the DBS concentration increased. These results show that the DBS concentration in water during recrystallization plays a critical role in determining the molecular, physicochemical, and digestion properties of DBS, which may be an economical and effective method for large-scale production of highly crystalline starch and provides a new method for preparing heat-resistant type-3 resistant starch, which can be used in low glycemic index foods designed to prevent diabetes and obesity.

Nanocellulose prepared with γ-valerolactone pretreatment and its enhancement in colored paper.

New techniques are always demanded to pursuit green and economical ways for nanocellulose preparation. We herein proposed to use γ-valerolactone (GVL) to facilitate the nanocellulose preparation from bleached bamboo pulp fibers as a green and sustainable pretreatment. The GVL pretreatment caused the bamboo fibers to destruct, resulting in an obviously increased fine fiber content, which was systematically studied to disclose the influence of different factors on the fiber changes. The optimum GVL pretreatment conditions were determined as reaction time of 4 h, reaction temperature of 140 °C and the ratio of GVL to water of 4:1. Notably, the GVL pretreatment caused negligible changes in the functional groups on cellulose, as well as its crystalline structure. The resultant nanocellulose (i.e. G-CNF) had a width of ca. 47 nm and it showed good adsorption capacity towards RR195 dye since an impressive dye uptake rate of 46.81 % was attained. The incorporation of G-CNF significantly improved the coloring performance and the ∆E (color difference) value reached up to 33.73. Improvements in the mechanical properties of RR195 dyed paper were also observed with the incorporation of G-CNF. This work sheds light on the nanocellulose preparation with GVL pretreatment and demonstrates a feasible way to apply the resultant nanocellulose in the colored paper manufacture.

Preparation of superhydrophobic coatings with excellent durability by synergistic reinforcement of cationic starch and tannic acid.

The intrinsic hydrophilicity of sustainable and environmentally friendly biobased materials like starch and its derivatives limits their potential as hydrophobic functional materials. This study presents an eco-friendly and non-toxic method to create coatings with exceptionally high hydrophobicity. Octadecyltrimethoxysilane (ODS) reacts with nano silica (SiO2) through a silane coupling reaction to form superhydrophobic SiO2. The Si-OH groups generated from ODS hydrolysis can undergo a condensation reaction with tannic acid (TA), which is rich in phenolic hydroxyl groups. This enables the hydrophobic silane to bind indirectly with cationic starch (CS), resulting in a stable superhydrophobic CS-based coating. The coating demonstrates significant hydrophobicity (contact angle >170°), excellent UV light transmittance (<4.05 %), self-cleaning properties, prolonged shelf life (over eight months), antibacterial activity, and encapsulation capability. It also shows a separation efficiency exceeding 99 % after 25 oil-water separation cycles and is easily recoverable. The study elucidates the mechanism behind the preparation process and the factors enhancing hydrophobic properties. The research findings suggest that the novel, cost-effective CS/TA/ODS/SiO2 coating offers a scalable solution for superhydrophobic applications and broadens the horizon for green starch use in hydrophobic materials.

Stabilization of Cuδ+ Sites Within MnO2 for Superior Urea Electro-Synthesis.

Electrocatalytic C-N coupling between NO3 - and CO2 has emerged as a sustainable route for urea production. However, identifying catalytic active sites and designing efficient electrocatalysts remain significant challenges. Herein, the synthesis of Cu-doped MnO2 nanotube (denoted as Cu-MnO2) with stable Cuδ+-oxygen vacancies (Ovs)-Mn3+ dual sites is reported. Compared with pure MnO2, Cuδ+ doping can effectively enhance urea production performance in the co-reduction of CO2 and NO3 -. Thus, Cu-MnO2 catalyst exhibits a maximum Faradaic efficiency (FE) of 54.7% and the highest yield rate of 116.7 mmol h-1 gcat. -1 in a flow cell. Remarkably, the urea yield rate remains over 78 mmol h-1 gcat. -1 across a wide potential range. Further experimental and theoretical results elucidate the unique role of Cu-MnO2 solid-solution for stabilizing Cuδ+ sites in Cuδ+-Ovs-Mn3+, endowing the catalyst with superior structural and electrochemical stabilities. This thermodynamically promotes urea formation and kinetically lowers the energy barrier of C-N coupling.

Preparation of debranched starch with high thermal stability and crystallinity using a novel thermal cycling treatment.

Herein, the effects of temperature cycling (4 °C/50 °C/100 °C) on the recrystallization, physicochemical properties, and digestibility of debranched starch (DBS) were investigated. Temperature cycling involved heating DBS to 100 °C to dissociate weak heat-sensitive crystalline structures and cooling to 4 °C to induce the rapid growth of crystal nuclei, followed by maintaining the temperature at 50 °C to promote orderly crystalline growth. This procedure aimed to increase the degree of crystalline structure in recrystallized DBS, thereby resulting in DBS that was heat- and digestion-resistant. Temperature cycling increased the dissociation temperature of DBS, and temperatures of up to 114.8 °C were attained after five cycling times. With increasing cycles, the crystalline structure of DBS transitioned from B-type to the more robust and compact A-type, and the crystallinity increased to ∼81.9 % (after seven cycles). Raman and Fourier transform infrared (FTIR) spectra indicated that temperature cycling enhanced the short-range ordered structure of DBS. Moreover, in vitro digestion experiments demonstrated that the resistant starch content of DBS increased to ∼61.9 % after eight cycles. To summarize, this study demonstrated a green and effective method for preparing heat-and digestion-resistant recrystallized DBS, which can be used for developing dietary supplements and low gastrointestinal staples.

A novel electrocatalyst from TOCN/CGG hydrogel-supported Fe-rich sludge and its performance in treating azo dyes-contaminated water.

Monolithic electrocatalysts are desired for the electro-Fenton oxidation system. We used a hydrogel consisting of TEMPO-oxidized cellulose nanofibers (TOCN) and cationic guar gum (CGG) to disperse and support Fe-rich sludge and finally obtained a Fe-doped biochar (denoted as C-Sludge@TOCN/CGG) after the freeze-drying and carbonization. This C-Sludge@TOCN/CGG exhibited a porous structure with evenly-distributed Fe due to the inherently three-dimensional porous structure of TOCN/CGG hydrogel and the abundant carbon content. Importantly, Fe and FeO existed in C-Sludge@TOCN/CGG due to the presence of TOCN and CGG during the pyrolysis. The electrochemical properties of C-Sludge@TOCN/CGG demonstrated its good electrocatalytic activity and stability with few side reactions. It had good performance in the electrocatalytic degradation of various azo dyes, attributed to the synergistic integration of TOCN/CGG-derived carbon matrix and carbonized Fe-rich sludge particles. Specifically, two transient radicals (i.e. ·OH and ·O2-) primarily improved the electrocatalytic degradation performance of C-Sludge@TOCN/CGG. This C-Sludge@TOCN/CGG also efficiently degraded a papermill-sourced wastewater containing direct red 23, direct yellow 11, direct black 19 and toner, in which the COD value decreased from 365.12 to 179.13 mg/L within 9 h. This work provides an example of utilizing renewable materials and solid waste to design electrocatalysts to address the wastewater issue.

ANGPTL4-the Link Binding Lipid Metabolism and Inflammation.

BACKGROUND: Angiopoietin-like 4 (ANGPTL4) belongs to the family of angiopoietin- like proteins. The involvement of ANGPTL4 in various aspects of lipid metabolism and inflammation has become an important area of research. METHODS: A thorough search on PubMed related to ANGPTL4, lipid metabolism, and inflammation was performed. RESULTS: Over the past two decades, the recognition of ANGPTL4 as a potent regulator of lipid metabolism has substantially increased. As part of the senescence-associated secretory phenotype, ANGPTL4 also serves as an inflammatory mediator. Considering the advancements in ANGPTL4 research, we have highlighted that ANGPTL4 acts as a key node linking lipid metabolism and inflammation. ANGPTL4 impacts inflammation by regulating lipid metabolism. It affects critical enzymes (lipoprotein lipase, hepatic lipase, endothelial lipase, and acetyl-CoA carboxylase), regulatory factors (AMPK, cAMP, SLC7A11, GPX4, and mTOR), and receptors (LepR, CD36, and PPARγ) of lipid oxidation, synthesis, and peroxidation, thereby affecting immune cells and inflammatory pathways. CONCLUSION: Understanding the potential association and the therapeutic value of ANGPTL4 for regulating lipid metabolism and inflammation could contribute to drug discovery and therapeutic development.

The causal relationship between immune cells and diabetic retinopathy: a Mendelian randomization study.

Purpose: This article explored the causal relationship between immune cells and diabetic retinopathy (DR) using single nucleotide polymorphisms (SNPs) as an instrumental variable and Mendelian randomization (MR). Methods: Statistical data were collected from a publicly available genome-wide association study (GWAS), and SNPs that were significantly associated with immune cells were used as instrumental variables (IVs). Inverse variance weighted (IVW) and MR-Egger regression were used for MR analysis. A sensitivity analysis was used to test the heterogeneity, horizontal pleiotropy, and stability of the results. Results: We investigated the causal relationship between 731 immune cells and DR risk. All the GWAS data were obtained from European populations and from men and women. The IVW analysis revealed that HLA DR on CD14+ CD16- monocytes, HLA DR on CD14+ monocytes, HLA DR on CD33-HLA DR+, HLA DR on CD33+ HLA DR+ CD14- on CD33+ HLA DR+ CD14dim, and HLA DR on myeloid dendritic cells may increase the risk of DR (P<0.05). HLA DR to CD14-CD16- cells, the monocytic myeloid-derived suppressor cell absolute count, the SSC-A count of CD4+ T cells, and terminally differentiated CD4+ T cells may be protective factors against DR (P<0.05). The sensitivity analysis indicated no heterogeneity or pleiotropy among the selected SNPs. Furthermore, gene annotation of the SNPs revealed significant associations with 10 genes related to the risk of developing PDR and potential connections with 12 other genes related to PDR. Conclusion: Monocytes and T cells may serve as new biomarkers or therapeutic targets, leading to the development of new treatment options for managing DR.

Effectiveness of repetitive transcranial magnetic stimulation combined with intelligent Gait-Adaptability Training in improving lower limb function and brain symmetry after subacute stroke: a preliminary study.

OBJECTIVES: Persistent lower limb dysfunction is a major challenge in post-stroke recovery. Repetitive transcranial magnetic stimulation is recognized for addressing post-stroke motor deficits. Our study explores the efficacy of combining rTMS with gait-adaptive training to enhance lower limb function and regulatory mechanisms in subacute stroke. MATERIALS AND METHODS: This randomized controlled trial enrolled 27 patients with subacute hemiparesis, dividing them into experimental and control groups. Both groups underwent gait-adaptability training 5 times/week for 4 weeks, with the experimental group receiving daily low-frequency transcranial magnetic stimulation before training. Primary outcomes included the pairwise derived brain symmetry index, lower-extremity Fugl-Meyer Assessment, 10-meter walk test, and Berg Balance Scale. Assessments occurred before and after the four-week intervention. RESULTS: The experimental and control groups showed significant improvements in the Fugl-Meyer Assessment, 10-meter walk test, and Berg Balance Scale after the 4-week intervention compared to baseline (all p<0.05). However, the experimental group demonstrated significantly greater improvements compared to the control group in the Fugl-Meyer Assessment (p=0.024) and the 10-meter walk test (p=0.033). Additionally, the experimental group exhibited a more pronounced decrease in the pairwise derived brain symmetry index (p=0.026) compared to the control group. Within the experimental group, the cortical subgroup's pairwise derived brain symmetry index was significantly lower than that of the control group (p=0.006). CONCLUSIONS: Combining low-frequency transcranial magnetic stimulation with Gait-Adaptive Training effectively enhances lower limb function and Regulatory mechanisms of the cerebral hemisphere in subacute stroke recovery, and it can provide rapid and effective rehabilitation effect compared with gait adaptation training alone.

Synergistic pectin deconstruction is a prerequisite for mutualistic interactions between honeybee gut bacteria.

The honeybee gut microbiome is crucial for degrading diverse pollen glycans. Yet it is unclear how this process shapes the interactions among bacteria. Here, we demonstrate a conditional mutualistic interaction between strains of two honeybee gut bacteria Bifidobacterium asteroides and Gilliamella apicola. When co-occurring in vitro and in vivo, Bifidobacterium provides complementary demethylation service to promote Gilliamella growth on methylated homogalacturonan, an enriched polysaccharide of pectin. In exchange, Gilliamella shares digestive products with Bifidobacterium, through which a positive interaction is established. This positive interaction vanishes when Bifidobacterium is not required on a non-methylated diet. Results from biochemical and gene expression analyses combined with model simulation further suggest that the ratio change of the two major homogalacturonan breakdown products, galacturonic acid (GalA) and di-GalA, determines the bacterial interaction. This study unravels how glycan metabolism may shape the interactions between honeybee gut bacteria.

Corrigendum: Chemical constituent characterization and determination of Quisqualis fructus based on UPLC-Q-TOF-MS and HPLC combined with fingerprint and chemometric analysis.

[This corrects the article DOI: 10.3389/fpls.2024.1418480.].

Construction of axially chiral molecules enabled by photoinduced enantioselective reactions.

Axially chiral molecular scaffolds are widely found in pharmaceutical molecules, functionalized materials, and chiral ligands. The synthesis of these compounds has garnered considerable interest from both academia and industry. The construction of such molecules, enabled by transition metal catalysis and organocatalysis under thermodynamic conditions, has been extensively studied and well-reviewed. In recent years, photoinduced enantioselective reactions have emerged as powerful methods for the catalytic construction of axial chirality. In this review, we provide an overview of various synthetic strategies for the photoinduced construction of axial chirality, with a specific focus on reaction design and catalytic mechanisms. Additionally, we discuss the limitations of current methods and highlight future directions in this field.

TONSL promotes lung adenocarcinoma progression, immune escape and drug sensitivity.

PURPOSE: The tonsoku-like DNA repair protein (TONSL) encoded by the TONSL gene, located on chromosome 8q24.3, is crucial for repairing DNA double-strand breaks through homologous recombination. However, TONSL overexpression in lung adenocarcinoma (LUAD) promotes tumor development, leading to a poor prognosis. METHODS: TONSL was verified as a reliable prognostic marker for LUAD using bioinformatics, and clinical features related to LUAD prognosis were screened from the TCGA database to establish the relationship between risk factors and TONSL expression. In addition, TONSL expression in normal and LUAD tissues was verified using real-time quantitative polymerase chain reaction and immunohistochemistry. To elucidate the possible functions of TONSL, TONSL-related differentially expressed genes were screened, and functional enrichment analysis was performed. Subsequently, siRNA was used to knock down TONSL expression in lung cancer cells for cytobehavioral experiments. The effects of TONSL expression on tumor immune escape were analyzed using the ESTIMATE algorithm and tumor immune-infiltration analysis. In addition, the half-maximal inhibitory concentration of LUAD with varying TONSL expression levels in response to first-line chemotherapeutic drugs and epidermal growth factor receptor-tyrosine kinase inhibitors was analyzed for drug sensitivity. RESULTS: Up-regulation of TONSL in LUAD promotes the proliferation, migration, and invasion of lung cancer cells, thereby contributing to a poor prognosis. Furthermore, TONSL overexpression promotes immune escape and drug sensitivity in LUAD. CONCLUSION: TONSL serves as a reliable prognostic marker for LUAD, and its up-regulation is associated with increased immune escape and drug sensitivity. These findings suggest that TONSL holds potential as a novel therapeutic target for LUAD.

Molecular Characterization and Classification of HER2-Positive Breast Cancer Inform Tailored Therapeutic Strategies.

HER2-positive breast cancer is an aggressive subtype that accounts for 15-20% of all breast cancers. Recent studies have suggested that HER2-positive breast cancer is a group of heterogeneous diseases with different sensitivities to standard treatment regimens. Revealing the molecular heterogeneity of HER2-positive breast cancer could potentially enable more precise treatment strategies. Here, we performed multiomics profiling on a HER2-positive breast cancer cohort and identified four transcriptome-based subtypes. The classical HER2 (HER2-CLA) subtype comprised 28.3% of the samples and displayed high ERBB2 activation and significant benefit from anti-HER2 therapy. The immunomodulatory (HER2-IM) subtype (20%) featured an immune-activated microenvironment, potentially suitable for de-escalated treatment and immunotherapy. The luminal-like (HER2-LUM) subtype (30.6%) possessed similar molecular features of hormone receptor-positive HER2-negative breast cancer, suggesting endocrine therapy and CDK4/6 inhibitors as a potential therapeutic strategy. Lastly, the basal/mesenchymal-like (HER2-BM) subtype (21.1%), had a poor response to current anti-HER2 dual-targeted therapies and could potentially benefit from tyrosine kinase inhibitors. The molecular characteristics and clinical features of the subtypes were further explored across multiple cohorts, and the feasibility of the proposed treatment strategies was validated in patient-derived organoid and patient-derived tumor fragment models. This study elucidates the molecular heterogeneity of HER2-positive breast cancer and paves the way for a more tailored treatment.

Vanadium Redox Flow Battery: Review and Perspective of 3D Electrodes.

Vanadium redox flow battery (VRFB) has garnered significant attention due to its potential for facilitating the cost-effective utilization of renewable energy and large-scale power storage. However, the limited electrochemical activity of the electrode in vanadium redox reactions poses a challenge in achieving a high-performance VRFB. Consequently, there is a pressing need to assess advancements in electrodes to inspire innovative approaches for enhancing electrode structure and composition. This work categorizes three-dimensional (3D) electrodes derived from materials such as foam, biomass, and electrospun fibers. By employing a flexible electrode design and compositional functionalization, high-speed mass transfer channels and abundant active sites for vanadium redox reactions can be created. Furthermore, the incorporation of 3D electrocatalysts into the electrodes is discussed, including metal-based, carbon-based, and composite materials. The strong interaction and ordered arrangement of these nanocomposites have an influence on the uniformity and stability of the surface charge distribution, thereby enhancing the electrochemical performance of the composite electrodes. Finally, the challenges and perspectives of VRFB are explored through advancements in 3D electrodes, 3D electrocatalysts, and mechanisms. It is hoped that this review will inspire the development of methodology and concept of 3D electrodes in VRFB, so as to promote the future development of scientific energy storage and conversion technology.

Defactinib inhibits FAK phosphorylation and regulates psoriasis via attenuating hyperproliferation of keratinocytes.

Excessive proliferation of keratinocytes is a crucial pathological risk feature of psoriasis. Focal adhesion kinase (FAK) is a non-receptor protein that primarily regulates cell proliferation and migration. However, the expression and regulatory mechanism of FAK in psoriasis remains unclear. This study aimed to investigate the regulation of FAK in psoriasis and examined the potential impact of FAK inhibitor on psoriasis. A small molecular selective FAK inhibitor, defactinib, was used to evaluate the effect of FAK on psoriasis in in vitro and in vivo functional assays. In our experiments, imiquimod (IMQ)-induced psoriasis mice and human keratinocytes cells were used to study the potential roles and mechanisms of FAK in psoriasis. FAK phosphorylation has been weakly detected in normal intact skin and is markedly elevated upon IMQ treatment. By reducing FAK phosphorylation (p-FAK), defactinib treatment could attenuate psoriasiform inflammation and epidermal hyperplasia in IMQ-treated mice compared with IMQ-induced mice treated with the vehicle. In in vitro studies, resiquimod (R848) increased (p-FAK) and promoted cell proliferation in human keratinocytes cells, while defactinib reversed this effect. Mechanistically, defactinib can alleviate the proliferation via JNK/YB1 pathway in vitro and in vivo. Defactinib significantly attenuates psoriasiform inflammation and epidermal hyperproliferation through the inhibition of the FAK-mediated axis. The downregulation of phosphorylated FAK then suppressed the activation of JNK/YB1 protein signaling pathway in psoriasis. Our work highlights targeting FAK as a potentially effective strategy for the treatment of psoriasis.

Development of pea protein nanoparticle/hydrolyzed rice glutelin fibril emulsion gels for encapsulation of curcumin.

The potential of using emulsion gels stabilized by binary plant protein nanoparticle mixtures for the encapsulation and delivery of lipophilic nutraceuticals was evaluated. The particle characteristics, physical stability, water diffusivity, microrheology, large amplitude oscillating shear (LAOS) properties, and in vitro digestion of emulsion gels prepared by different ratios of hydrolyzed rice glutelin fibrils (HRGFs) and pea protein nanoparticle (PNP) were characterized. The emulsion gel with P/H = 2:1 (0.84 µm) exhibited the best storage stability and freeze-thaw stability, as seen by the smaller oil droplet size (1.02 and 1.42 µm, respectively). Low-field pulsed NMR indicated that the majority of water in samples was highly mobile. All the samples were predominantly elastic-like materials. The P/H 2:1 emulsion gel had the lowest FI value (6.21 × 10-4 Hz), the highest MVI value (5.57 s/nm2), G'/ G″ values and enclosed area, showing that it had denser 3D network structures, higher stiffness values, and a high sensitivity to changes in strain. Additionally, P/H 2:1 emulsion gel had a relatively high lipid digestibility (96.1 %), curcumin bioaccessibility (58.9 %), and curcumin stability (94.2 %). This study showed that emulsion gels stabilized by binary protein nanoparticle mixtures (PNP/HRGF) have potential as edible delivery systems for lipophilic nutraceuticals.