Boosting 5-Hydroxymethylfurfural Electrooxidation by Porous Biochar via Loading Numerous Surface-Exposed Cobalt Phosphonates.

The electrooxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) demonstrated its unique superiority, not only in reducing overpotential and improving energy conversion efficiency for green hydrogen production but also in utilizing abundant biomass resources and producing high-value-added chemicals. However, designing highly efficient electrocatalysts for HMF electrooxidation (HMF-EOR) with low cost and high performance for large-scale production remained a huge challenge. Herein, we introduced an easy one-step activation process to produce P-doped porous biochar loaded with multiple crystal surfaces exposed to CoP2O6 catalysts (CoP2O6@PC), which exhibited outstanding electrooxidation performance. To achieve a current density of 50 mA cm-2, only a low overpotential of 200 mV was needed for the electrooxidation of HMF in 1.0 M KOH + 10 mM HMF. This performance far surpassed that of other similar materials. CoP2O6@PC exhibited outstanding HMF-EOR performance with high conversion (nearly 100%), selectivity (97.1%), faradaic efficiency (95.3%), and robust stability. This work represents a promising strategy to fabricate macroscale and low-cost HMF-EOR electrocatalysts and achieve potential industrial applications of HMF-EOR.

Synergy of metallic Co and oxygen vacancy sites in Co/Ce-MOF catalysts for efficiently promoting lignin derived phenols and macromolecular lignin hydrodeoxygenation.

The enhanced utilization of biomass-derived chemicals for the generation of high value aromatics through an advanced catalytic strategy has captured considerable attention within the realm of eco-friendly manufacturing. This work presented four innovative three-dimensional rod-shaped mesoporous Ce-based MOF materials, which were coupled with a H-donor solvent to facilitate vanillin hydrodeoxygenation and macromolecular lignin. Under the optimized conditions (30 mg CoCe@C catalyst, 2 MPa N2 pressure, 15 mL isopropanol, 190 °C, and 5 h), the CoCe@C catalyst achieved nearly complete conversion of vanillin and demonstrated 87.8 % selectivity in the hydrogen-donor solvent. The characterization findings suggested that the synergy between metallic Co and oxygen vacancy sites enabled the effective activation of CHO group in vanillin, leading to formation of reactive product MMP. In addition, the optimal CoCe@C catalyst could also achieve macromolecular lignin hydrodeoxygenation to obtain high yield of lignin oil products with narrower molecular weight distribution. This study presented a viable approach for the concurrent utilization of lignin derivatives in the generation of high value fuels and chemicals.

Tumor-associated macrophage-induced circMRCKα encodes a peptide to promote glycolysis and progression in hepatocellular carcinoma.

The tumor-associated macrophages (TAMs) play multifaceted roles in the progression of hepatocellular carcinoma (HCC). However, the involvement of circular RNAs in the interplay between TAMs and HCC remains unclear. Based on Transwell co-culturing and circular RNA sequencing, this study revealed that TAMs enhanced tumor glycolysis and progression by upregulating circMRCKα in HCC cells. Patients with HCC who exhibited elevated circMRCKα levels presented significantly reduced overall survival and greater cumulative recurrence. Notably, we identified a novel functional peptide of 227 amino acids named circMRCKα-227aa, encoded by circMRCKα. Mechanistically, circMRCKα-227aa bound to USP22 and enhanced its protein level to obstruct HIF-1α degradation via the ubiquitin-proteasome pathway, thereby augmenting HCC glycolysis and progression. In clinical HCC samples, a positive correlation was observed between the expression of circMRCKα and the number of infiltrating CD68+ TAMs and expression of USP22. Furthermore, circMRCKα emerged as an independent prognostic risk factor both individually and in conjunction with CD68+ TAMs and USP22. This study illustrated that circMRCKα-227aa, a novel TAM-induced peptide, promotes tumor glycolysis and progression via USP22 binding and HIF-1α upregulation, suggesting that circMRCKα and TAMs could be combined as therapeutic targets in HCC.

The Effect of Sports Game Intervention on Children's Fundamental Motor Skills: A Systematic Review and Meta-Analysis.

The purpose of the present study was to carry out a systematic review and a meta-analysis determining the effects of sports game intervention on fundamental motor skills in children. This paper presented a systematic review from 2001 to 2020, including the databases of Web of Science, EBSCO, Science, PubMed and Springer. (1) Participants comprised 1701 children age 3-12 years; (2) sports game interventions were investigated; (3) only studies using a Test of Gross Motor Skills assessment were included; (4) RCT were chosen as the study design to assess the impact of sports game interventions on children's motor skills; (5) only culture-based sports game studies in the English and Chinese language were included. Two researchers independently reviewed and assessed the eligibility criteria. Out of the initial 1826 references, 12 studies with a total of 1608 participants were included in the meta-analysis. All interventions were implemented in preschool (kindergarten) or primary school populations, and all studies followed a randomized controlled trial design. The results demonstrated significantly superior development of fundamental motor skills in the intervention groups compared to the control groups (standardized mean difference = 0.30, p < 0.0001). The methodological quality of the included studies ranged from fair to excellent, and no evidence of publication bias was observed. Among them, the 12-week sports game intervention of 35 min each time three to four times a week had a better intervention effect, promoting children's physical health and fundamental motor skills.

A highly sensitive fluorescence probe for on-site detection of nerve agent mimic diethylchlorophosphonate DCP.

Nerve agents are the most toxic chemical warfare agents that pose severe threat to human health and public security. In this work, we developed a novel fluorescent probe NZNN based on naphthylimide and o-phenylenediamine to detect nerve agent mimic diethylchlorophosphonate (DCP). DCP underwent a specific nucleophilic reaction with the o-phenylenediamine group of NZNN to produce a significant fluorescence turn-on response with high selectivity, exceptional linearity, bright fluorescence, rapid response (<6 s) and a low detection limit (30.1 nM). Furthermore, a portable sensing device was fabricated for real-time detection of DCP vapor with excellent performance. This portable and sensitive device is favorable for monitoring environmental pollution and defense against chemical warfare agents.

Design of Single-Atom Catalysts for E lectrocatalytic Nitrogen Fixation.

The Electrochemical nitrogen reduction reaction (ENRR) can be used to solve environmental problems as well as energy shortage. However, ENRR still faces the problems of low NH3 yield and low selectivity. The NH3 yield and selectivity in ENRR are affected by multiple factors such as electrolytic cells, electrolytes, and catalysts, etc. Among these catalysts are at the core of ENRR research. Single-atom catalysts (SACs) with intrinsic activity have become an emerging technology for numerous energy regeneration, including ENRR. In particular, regulating the microenvironment of SACs (hydrogen evolution reaction inhibition, carrier engineering, metal-carrier interaction, etc.) can break through the limitation of intrinsic activity of SACs. Therefore, this Review first introduces the basic principles of NRR and outlines the key factors affecting ENRR. Then a comprehensive summary is given of the progress of SACs (precious metals, non-precious metals, non-metallic) and diatomic catalysts (DACs) in ENRR. The impact of SACs microenvironmental regulation on ENRR is highlighted. Finally, further research directions for SACs in ENRR are discussed.

CD168+ macrophages promote hepatocellular carcinoma tumor stemness and progression through TOP2A/ß-catenin/YAP1 axis.

Liver cancer stem-like cells (LCSCs) are the main cause of heterogeneity and poor prognosis in hepatocellular carcinoma (HCC). In this study, we aimed to explore the origin of LCSCs and the role of the TOP2A/ß-catenin/YAP1 axis in tumor stemness and progression. Using single-cell RNA-seq analysis, we identified TOP2A+CENPF+ LCSCs, which were mainly regulated by CD168+ M2-like macrophages. Furthermore, spatial location analysis and fluorescent staining confirmed that LCSCs were enriched at tumor margins, constituting the spatial heterogeneity of HCC. Mechanistically, TOP2A competitively binds to ß-catenin, leading to disassociation of ß-catenin from YAP1, promoting HCC stemness and overgrowth. Our study provides valuable insights into the spatial transcriptome heterogeneity of the HCC microenvironment and the critical role of TOP2A/ß-catenin/YAP1 axis in HCC stemness and progression.

Deciphering photocatalytic degradation of methylene blue by surface-tailored nitrogen-doped carbon quantum dots derived from Kraft lignin.

Lignin in black liquor can be used to manufacture carbon nanomaterials on a large scale. However, the effect of nitrogen doping on the physicochemical properties and photocatalytic performance of carbon quantum dots (NCQDs) remains to be explored. In this study, NCQDs with different properties were prepared hydrothermally by using kraft lignin as the raw material and EDA as a nitrogen dopant. The amount of EDA added affects the carbonization reaction and surface state of NCQDs. Raman spectroscopy showed that the surface defects increased from 0.74 to 0.84. Photoluminescence spectroscopy (PL) showed that NCQDs had different intensities of fluorescence emission at 300-420 nm and 600-900 nm. Meanwhile, NCQDs can photo-catalytically degrade 96 % of MB under simulated sunlight irradiation within 300 min. After three months of storage, the fluorescence intensity of NCQDs remained above 94 %, showing remarkable fluorescence stability. After four times of recycling, the photo-degradation rate of NCQDs was maintained above 90 %, confirming its outstanding stability. As a result, a clear understanding of the design of carbon-based photo-catalyst fabricated from the waste of the paper-making industry has been gained.

Development of Engineered CAR T Cells Targeting Tumor-Associated Glycoforms of MUC1 for the Treatment of Intrahepatic Cholangiocarcinoma.

Intrahepatic cholangiocarcinoma (ICC) is a common malignancy arising from the liver with limited 5-year survival. Thus, there is an urgency to explore new treatment methods. Chimeric antigen receptor T (CAR T) cell therapy is a very promising cancer treatment. Though, several groups have investigated CAR T cells targeting MUC1 in solid cancer models, Tn-MUC1-targeted CAR T cells have not yet to be reported in ICC. In this study, we confirmed Tn-MUC1 as a potential therapeutic target for ICC and demonstrated that its expression level was positively correlated with the poor prognosis of ICC patients. More importantly, we successfully developed effective CAR T cells to target Tn-MUC1-positive ICC tumors and explored their antitumor activities. Our results suggest the CAR T cells could specifically eliminate Tn-MUC1-positive ICC cells, but not Tn-MUC1-negative ICC cells, in vitro and in vivo. Therefore, our study is expected to provide new therapeutic strategies and ideas for the treatment of ICC.

Elevated STIL predicts poor prognosis in patients with hepatocellular carcinoma.

Overexpression of SCL/TAL1 interrupting locus (STIL) has been observed in various cancer types. However, the clinical significance of STIL in hepatocellular carcinoma (HCC) remains unknown. Cox regression and Kaplan-Meier survival analyses were performed to evaluate the prognostic value of STIL. Go and Kyoto encyclopedia of genes and genomes (KEGG) enrichment analyses were also carried out. Immune infiltrates analyses were conducted based on TIMER (Tumor Immune Estimation Resource) and GAPIA databases. STIL expression was highly expressed in HCC tissues, based on multiple databases. KEGG and GO enrichment analysis showed STIL-related to tumorigenesis and progress. Furthermore, STIL was significantly correlated with immune infiltration. STIL serves as a biomarker for the prediction of patient survival.

Analysis of the microscopic interactions between processed Polygonatum cyrtonema polysaccharides and water.

The dissolution and microscopic interactions of processed Polygonatum cyrtonema polysaccharides in water are extremely important because they strongly influence the process to extract these polysaccharides from water. In this paper, molecular dynamics simulation methods were used to analyse the influence of extraction temperature, concentration and molecular weight on the radial distribution function (RDF), mean square displacement (MSD), diffusion coefficient (D), radius of gyration (Rg), and microstructure of processed Polygonatum cyrtonema polysaccharides in water as well as the intrinsic viscosity (η), hydrogen bond characteristics and microscopic interactions in the solutions. The research results showed that the extraction temperature, concentration and molecular weight of the polysaccharides had important effects on the RDF, MSD, D, Rg, η, hydrogen bond characteristics and the microstructure of the polysaccharide molecules, but there were some major differences. The order of the influence of the factors affecting the dissolution of polysaccharides in water was temperature > concentration > molecular weight. Extraction temperature, material fluid ratio and molecular weight had greater influence on the fluidity and dissolution state of the polysaccharides in water. As the solute concentration and molecular weight increased, hydrogen bonds between polysaccharides and water inhibited their dissolution and diffusion. Properly increasing the temperature, reducing the concentration and selecting low molecular weight polysaccharides enhanced the dissolution and diffusion of the polysaccharides in the solution system. Molecular weight was the main factor affecting the η of the polysaccharide solutions. These results can provide theoretical guidance for the extraction or tea brewing process of Polygonatum cyrtonema polysaccharides in future work.

Self-Adhesive and Conductive Dual-Network Polyacrylamide Hydrogels Reinforced by Aminated Lignin, Dopamine, and Biomass Carbon Aerogel for Ultrasensitive Pressure Sensor.

Conductive hydrogels have attracted extensive interest owing to its potential in soft robotics, electronic skin, and human monitoring. However, insufficient mechanical properties, lower adhesivity, and unsatisfactory conductivity seriously hinder potential applications in this emerging field. Herein, a highly elastic conductive hydrogel with a combination of favorable mechanical properties, self-adhesiveness, and excellent electrical performance was achieved by the synergistic effect of aminated lignin (AL), polydopamine (PDA), polyacrylamide (PAM) chains, and biomass carbon aerogel (C-SPF). In detail, AL was applied to induce slow oxidative polymerization of DA for preparing the sticky hydrogel containing PDA. Then, C-SPF carbon aerogel was used as a matrix to construct a dual-network structured composite hydrogel by combining with the hydrogels derived from PDA, AL, and PAM. The as-prepared conductive hydrogel displayed excellent mechanical performance, strong adhesive strength, and repeatable adhesivity. The prepared hydrogel-based pressure sensor possessed fast response (0.6 s loading and 0.8 s unloading stress time), high response (maximum RCR = 1.8 × 104), wide working pressure range (from 0 to 240.0 kPa), and excellent durability (stable 500 compression cycles with 30% deformation). In addition, the prepared sensor also displayed ultrahigh sensitivity (170 kPa-1), which was near 4 orders of magnitude higher than the conventional lignin-modified PAM hydrogels. The multiple interactions between hydrogel components and the mechanical properties of hydrogel were also verified by molecular dynamics investigation. Moreover, the excellent cytocompatibility and antibacterial activity of this composite hydrogel ensured high potential in various applications such as human/machine interaction, artificial intelligence, personal healthcare, and wearable devices.

A facile and novel lignin isolation procedure - Methanolic hydrochloric acid treatment at ambient temperature.

Lignin is the most naturally abundant source of aromatics for phenolic chemicals, bioenergy sources, and functional materials. Recent works are devoted to the acid-catalyzed organosolv extraction for improving the lignin valorization. However, ß-aryl ethers are mostly cleaved to form carbon-carbon bonds under the acidic condition. In this work, lignin isolated with methanolic hydrochloric acid (MHL) was compared with conventional milled wood lignin (MWL). The methanol incorporated into lignin as α-OCH3 to prevent the cleavage of ß-aryl ethers. As a result, the yield of MHL was over 12 times that of MWL. The MHL appeared a regular granular structure with an average diameter of 100 nm. Analysis of 13C-1H HSQC NMR spectra showed that MHL contained 42.6 % ß-O-4 linkages whereas 35.9 % for the MWL, as well as 6.5 % ß-5 and 3.2 % ß-ß, which was less than MWL. Moreover, 13C NMR spectroscopy confirmed that MHL was mainly isolated by the cleavage of the associated carbohydrates rather than the degradation of ß-aryl ether bonds. Therefore, MHL can be utilized more as a native lignin representative than MWL for studying the physicochemical properties and the interior structures of the protolignin.

DNA Topoisomerase II-α Regulated by miR-22-5p Promotes Hepatocellular Carcinoma Invasion and Migration through the Hippo Pathway.

DNA topoisomerases (TOPs) are dysregulated in various types of cancer. However, how TOP II-alpha (TOP2A) contributes to hepatocellular carcinoma (HCC) progression remains elusive. Cohort analysis revealed that the increased expression of TOP2A was associated with poor clinical outcomes and TOP2A was significantly upregulated in HCC tissues and cell lines. In vitro, TOP2A expression level is related to cell invasion and migration, which may be due to the alteration of epithelial-mesenchymal transition by the TOP2A. Moreover, we used verteporfin (a Hippo inhibitor) to test how the Hippo pathway promotes the effect of TOP2A on the HCC phenotype and found that TOP2A induces tumor progression through the Hippo pathway. Finally, miR-22-5p inhibited tumor progression by sponging TOP2A.

Molten Salt-Assisted Synthesis of Co/N-Doped Carbon Hybrids for Aqueous-Phase Aerobic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid.

A resource-efficient and facile method of synthesizing 2,5-furandicarboxylic acid (FDCA) from biomass-derived platform chemical 5-hydroxymethylfurfural (HMF) was explored using cobalt and nitrogen-doped carbon catalysts (Co/N-C). A molten salts-assisted method proved to be effective in improving the surface area of the catalysts as well as uniformity and dispersibility of the Co species. Detailed investigation of different combinations of precursors revealed that the formation of Co-Nx species was imperative for high FDCA selectivity, and the nitrogen-doped carbon matrix enhanced the catalytic activity by providing good electron mobility. A significant observation was made regarding the change in reaction mechanism with the heating rate of Co/N-C. High HMF conversion of 99 % with 68 % FDCA yield was achieved at 120 °C in water at 24 h. This study shows an eco-friendly and cost-effective method of FDCA production with high yield that overcomes the use of precious metal-based catalysts, organic solvents, and severe reaction conditions.

Stretchable and conductive cellulose hydrogel electrolytes for flexible and foldable solid-state supercapacitors.

In this study, the anti-freezing conductive hydrogel electrolytes with outstanding mechanical properties were synthesized by a facile and feasible method. The mechanical and anti-freezing properties of the synthesized polyacrylamide/lithium lhloride/water soluble cellulose acetate (PAM/LiCl/WSCA) hydrogels are significantly enhanced with the addition of WSCA and LiCl. The tensile strength and toughness of the gels were gradually increased to 341 KPa and 1.2 MJ/m3, respectively. The hydrogel electrolyte can remain soft and flexible at -80 °C, displaying certain elasticity and electrical conductivity. In addition, the super-capacitor assembled with PAM/LiCl/WSCA hydrogel as electrolyte showed excellent stability in capacitance retention after 500 times of folding cycles and 10,000 times of charge and discharge tests. The capacitor still maintains 64.64 % of its capacity at -40 °C. This facile strategy to fabricate anti-freezing conductive hydrogel electrolyte provides a new idea and way to the application of hydrogels as electrolytes in extreme cold environments.

Single-cell RNA Sequencing Analysis Reveals New Immune Disorder Complexities in Hypersplenism.

Hypersplenism (HS) is a concomitant symptom of liver or blood disease. Not only does the treatment of HS face challenges, but the transcriptome of individual cells is also unknown. Here, the transcriptional profiles of 43,037 cells from four HS tissues and one control tissue were generated by the single-cell RNA sequencing and nine major cell types, including T-cells, B-cells, NK cells, hematopoietic stem cells, neutrophil cells, mast cells, endothelial cells, erythrocytes, and dendritic cells were identified. Strikingly, the main features were the lack of CCL5+ B-cells in HS and the presence of SESN1+ B cells in HS with hepatocellular carcinoma (HS-HCC). In cell-cell interaction analysis, CD74-COPA and CD94-HLA-E in HS were found to be up-regulated. We further explored HS-specifically enriched genes (such as FKBP5, ADAR, and RPS4Y1) and found that FKBP5 was highly expressed in HCC-HS, leading to immunosuppression. Taken together, this research provides new insights into the genetic characteristics of HS via comprehensive single-cell transcriptome analysis.

Prefoldin and prefoldin-like complex subunits as predictive biomarkers for hepatocellular carcinoma immunotherapy.

BACKGROUND: Prefoldin complex subunits (PFDNs) and prefoldin-like complex subunits (PFDLNs) collaborate in protein folding, modulate endoplasmic reticulum stress. The association between PFDN/PFDLN and the immune microenvironment of HCC remains unclear. We investigated the biological significance of PFDNs and PFDLNs in HCC using bioinformatics. METHODS: The relationship between PFDNs/PFDLNs and HCC was analysed using TCGA, and Human Protein Atlas. The protein-protein interaction (PPI) network was performed through String and Cytoscape. In addition, mutations in PFDNs and PFDLNs were analysed using cBioPortal. Clinical correlation analysis, survival analysis was conducted by using UALCAN and Kaplan-Meier analysis. The protein-protein interaction (PPI) network was performed through String and Cytoscape. The GO and KEGG enrichment analyses were also carried out. CCK-8 and Flow cytometry analysis were used to detect the proliferation and apoptosis of PFDN1 and UXT knockdown HCC cells. Immune infiltrates analyses was were conducted using the TIMER and TISIDB to determine whether PFDNs/PFDLNs are predictive biomarkers of immune cell infiltration. RESULTS: We observed that PFDNs and PFDLNs were significantly overexpressed in HCC tissues compared to normal liver tissues. This abnormal expression was associated with worse clinicopathological features and negatively affected patient survival. PFDNs and PFDLNs have varying degrees of mutations in HCC, which may be related to their abnormal expression. In addition, up-regulated PFDN1 and UXT were found to promote HCC proliferation and inhibit apoptosis in vitro. Finally, the expression of certain PFDNs and PFDLNs in the tumour microenvironment was positively correlated with the level of tumour-infiltrating immune cells and significantly enhanced the infiltration of immune cells in the microenvironment. CONCLUSIONS: PFDNs and PFDLNs are valuable predictive biomarkers for immune infiltration in HCC and may assist in tumour immunotherapy research and prognosis prediction in the future.

Design of a Superhydrophobic Strain Sensor with a Multilayer Structure for Human Motion Monitoring.

A flexible strain sensor is of significant importance in wearable electronics since it can help monitor the physical signals from the human body. Among various strain sensors, the polyurethane (PU)-based ones have received widespread attention owing to their excellent toughness, large working range, and nice gas permeability. However, the hydrophobicity of these sensors is not good enough, which may affect their use life and sensitivity. In this work, a high-performance strain sensor composed of PU, reduced graphene oxide (rGO), polydopamine (PDA), and 1H,1H,2H,2H-perfluorodecane-thiol (PFDT) was designed and prepared. The results revealed that this PU/rGO/PDA/PFDT device possessed good superhydrophobicity with a water contact angle of 153.3°, a wide working strain range of 590%, and an outstanding gauge factor as high as 221 simultaneously. Because of these above advantages, the sensor worked effectively in detecting both subtle and large human movements (such as joint motion, finger motion, and vocal cord vibration) even in a high humidity environment. This strain sensor with high sensitivity, wide working range, and suitable modulus may have great potential in the field of flexible and wearable electronics in the near future.

MicroRNA-203-3p inhibits the proliferation, invasion and migration of pancreatic cancer cells by downregulating fibroblast growth factor 2.

Aberrant expression of fibroblast growth factor 2 (FGF2) is a major cause of poor prognosis in patients with pancreatic cancer. MicroRNA (miRNA/miR) miR-203-3p is a newly identified miRNA that can affect the biological behavior of tumors. The present study investigated the function of miR-203-3p on the regulation of FGF2 expression, and its role in pancreatic cancer cell proliferation, apoptosis, invasion and migration. Reverse transcription-quantitative PCR was used to determine the mRNA expression levels of miR-203-3p and FGF2 in vitro. Cell Counting Kit-8, Annexin V-APC/7-AAD double-staining Apoptosis Detection kit, wound healing and Transwell assays were used to determine the proliferation, apoptosis, migration and invasion of pancreatic cancer cells. The binding of miR-203-3p to FGF2 was assessed by a luciferase reporter assay. The results demonstrated that miR-203-3p expression was downregulated in pancreatic cancer cells. Gain- and loss-of-function experiments indicated that miR-203-3p inhibited the proliferation, migration and invasion, and promoted the apoptosis of pancreatic cancer cells in vitro. In addition, it was found that alteration of miR-203-3p abolished the promoting effects of FGF2 on pancreatic cancer cells. The present study demonstrated that FGF2 significantly promoted the proliferation, invasion and migration of pancreatic cancer cells. The mechanism involved the binding of miR-203-3p to the 3'-untranslated region of FGF2 mRNA, resulting in the downregulation of FGF2. In conclusion, miR-203-3p inhibited FGF2 expression, regulated the proliferation and inhibited the invasion and migration of pancreatic cancer cells.