Construction of blackberry polysaccharide nano-selenium particles: Structure features and regulation effects of glucose/lipid metabolism in HepG2 cells.

In this study, blackberry polysaccharide-selenium nanoparticles (BBP-24-3Se) were first prepared via Na2SeO3/Vc redox reaction, followed by coating with red blood cell membrane (RBC) to form core-shell structure polysaccharide-selenium nanoparticles (RBC@BBP-24-3Se). The particle size of BBP-24-3Se (167.1 nm) was increased to 239.8 nm (RBC@BBP-24-3Se) with an obvious core-shell structure after coating with RBC. FT-IR and XPS results indicated that the interaction between BBP-24-3 and SeNPs formed a new C-O···Se bond with valence state of Se0. Bioassays indicated that RBC coating markedly enhanced both the biocompatibility and bioabsorbability of RBC@BBP-24-3Se, and the absorption rate of RBC@BBP-24-3Se in HepG2 cells was 4.99 times higher than that of BBP-24-3Se at a concentration of 10 µg/mL. Compared with BBP-24-3Se, RBC@BBP-24-3Se possessed significantly heightened protective efficacy against oxidative damage and better regulation of glucose/lipid metabolism disorder induced by palmitic acid in HepG2 cells. Mechanistic studies demonstrated that RBC@BBP-24-3Se could effectively improve PI3K/AKT signaling pathway to promote glucose metabolism, inhibit the expression of lipid synthesis genes and up-regulate the expression of lipid-decomposing genes through AMPK signaling pathway to improve lipid metabolism. These results provided a theoretical basis for developing a new type of selenium supplement for the treatment of insulin resistance.

Bacteria-mediated resistance of neutrophil extracellular traps to enzymatic degradation drives the formation of dental calculi.

Dental calculi can cause gingival bleeding and periodontitis, yet the mechanism underlying the formation of such mineral build-ups, and in particular the role of the local microenvironment, are unclear. Here we show that the formation of dental calculi involves bacteria in local mature biofilms converting the DNA in neutrophil extracellular traps (NETs) from being degradable by the enzyme DNase I to being degradation resistant, promoting the nucleation and growth of apatite. DNase I inhibited NET-induced mineralization in vitro and ex vivo, yet plasma DNases were ineffective at inhibiting ectopic mineralization in the oral cavity in rodents. The topical application of the DNA-intercalating agent chloroquine in rodents fed with a dental calculogenic diet reverted NET DNA to its degradable form, inhibiting the formation of calculi. Our findings may motivate therapeutic strategies for the reduction of the prevalence of the deposition of bacteria-driven calculi in the oral cavity.

Ferrocene-functionalized zirconium-oxo clusters for achieving high-performance thermocatalytic redox reactions.

The Zr(IV) ions are easily hydrolyzed to form oxides, which severely limits the discovery of new structures and applications of Zr-based compounds. In this work, three ferrocene (Fc)-functionalized Zr-oxo clusters (ZrOCs), Zr9Fc6, Zr10Fc6 and Zr12Fc8 were synthesized through inhibiting the hydrolysis of Zr(IV) ions, which show increased nuclearity and regular structural variation. More importantly, these Fc-functionalized ZrOCs were used as heterogeneous catalysts for the transfer hydrogenation of levulinic acid (LA) and phenol oxidation reactions for the first time, and displayed outstanding catalytic activity. In particular, Zr12Fc8 with the largest number of Zr active sites and Fc groups can achieve > 95% yield for LA-to-γ-valerolactone within 4 h (130 °C) and > 98% yield for 2,3,6-trimethylphenol-to-2,3,5-trimethyl-p-benzoquinone within 30 min (80 °C), showing the best catalytic performance. Catalytic characterization combined with theory calculations reveal that in the Fc-functionalized ZrOCs, the Zr active sites could serve as substrate adsorption sites, while the Fc groups could act as hydrogen transfer reagent or Fenton reagent, and thus achieve effectively intramolecular metal-ligand synergistic catalysis. This work develops functionalized ZrOCs as catalysts for thermal-triggered redox reactions.

Bridging the Homogeneous and Heterogeneous Catalysis by Supramolecular Metal-Organic Cages with Varied Packing Modes.

Integrating the advantages of homogeneous and heterogeneous catalysis has proved to be an optimal strategy for developing catalytic systems with high efficiency, selectivity, and recoverability. Supramolecular metal-organic cages (MOCs), assembled by the coordination of metal ions with organic linkers into discrete molecules, have performed solvent processability due to their tunable packing modes, endowing them with the potential to act as homogeneous or heterogeneous catalysts in different solvent systems. Here, the design and synthesis of a series of stable {Cu3} cluster-based tetrahedral MOCs with varied packing structures are reported. These MOCs, as homogeneous catalysts, not only show high catalytic activity and selectivity regardless of substrate size during the CO2 cycloaddition reaction, but also can be easily recovered from the reaction media through separating products and co-catalysts by one-step work-up. This is because that these MOCs have varied solubilities in different solvents due to the tunable packing of MOCs in the solid state. Moreover, the entire catalytic reaction system is very clean, and the purity of cyclic carbonates is as high as 97% without further purification. This work provides a unique strategy for developing novel supramolecular catalysts that can be used for homogeneous catalysis and recycled in a heterogeneous manner.

Fullerene-like Niobovanadate Cage Built from {(Nb)V5 } Pentagon.

The striking aesthetic appeal of fullerene-like clusters has captured the interest of researchers. Nevertheless, the assembly of fullerene-like polyoxovadanadate (POV) cages remains a significant challenge due to the scarcity of suitable pentagonal motif. Herein, we have successfully synthesized the first fullerene-like all-inorganic POV cage, {(V2 O)V30 Nb12 O102 (H2 O)12 } (V30 Nb12 ), by introducing Nb into the POVs. V30 Nb12 is assembled by 12 heterometallic {(Nb)V5 } pentagons through sharing V centers with Ih symmetry, reminiscent of C60 . To our knowledge, the fullerene-like V30 Nb12 not only represents the highest-nuclearity POV cage but also stands as the first niobovanadate cluster. Notably, V30 Nb12 exhibits excellent solution stability, as confirmed by ESI-MS, FT-IR and UV/Vis spectra. As there is no protection organic ligand on its outer surface, V30 Nb12 can be further modified with Cu-complexes to form a fullerene-like cluster based zigzag chain (Cu-V30 Nb12 ).

Post-synthetic Rhodium (III) Complexes in Covalent Organic Frameworks for Photothermal Heterogeneous C-H Activation.

Although photocatalytic C-H activation has been realized by using heterogeneous catalysts, most of them require high-temperature conditions to provide the energy required for C-H bond breakage. The catalysts with photothermal conversion properties can catalyze this reaction efficiently at room temperature, but so far, these catalysts have been rarely developed. Here, we construct bifunctional catalysts Rh-COF-316 and -318 to combine photosensitive covalent organic frameworks (COFs) and transition-metal catalytic moiety using a post-synthetic approach. The Rh-COF enable the heterogeneous C-H activation reaction by photothermal conversion for the first time, and exhibit excellent yields (up to 98 %) and broad scope of substrates in [4+2] annulation at room temperature, while maintaining the high stability and recyclability. Significantly, this work is the highest yield reported so far in porous materials catalyzing C(sp2)-C(sp2) formation at room temperature. The excellent performances can be attributed to the COF-316, which enhances the photothermal effect (ΔT=50.9 °C), thus accelerating C-H bond activation and the exchange of catalyst with substrates.

Photocatalytic aerobic oxidation of C(sp3)-H bonds.

In modern industries, the aerobic oxidation of C(sp3)-H bonds to achieve the value-added conversion of hydrocarbons requires high temperatures and pressures, which significantly increases energy consumption and capital investment. The development of a light-driven strategy, even under natural sunlight and ambient air, is therefore of great significance. Here we develop a series of hetero-motif molecular junction photocatalysts containing two bifunctional motifs. With these materials, the reduction of O2 and oxidation of C(sp3)-H bonds can be effectively accomplished, thus realizing efficient aerobic oxidation of C(sp3)-H bonds in e.g., toluene and ethylbenzene. Especially for ethylbenzene oxidation reactions, excellent catalytic capacity (861 mmol g cat-1) is observed. In addition to the direct oxidation of C(sp3)-H bonds, CeBTTD-A can also be applied to other types of aerobic oxidation reactions highlighting their potential for industrial applications.

Laparoscopic hepatectomy for hepatocellular carcinoma in patients with clinically significant portal hypertension: a systematic review and meta-analysis.

OBJECTIVE: To compare the effects of laparoscopic hepatectomy (LH) on the short-term and long-term outcomes in hepatocellular carcinoma (HCC) patients with and without clinically significant portal hypertension (CSPH). METHODS: A systematic literature search of the PubMed, EMBASE, and Cochrane databases was performed for articles published from inception to March 1, 2023. Meta-analysis of surgical and oncological outcomes was performed using a random effects model. Data were summarized as mean difference and risk ratio with 95% confidence intervals. RESULTS: Five cohort studies with a total of 310 HCC patients were included (CSPH 143; Non-CSPH 167). In terms of surgical outcomes, estimated blood loss and the length of hospital stay were significantly lower in the Non-CSPH group than in the CSPH group. There were no significant differences between the two groups regarding other surgical outcomes, including the operative time, ratio of conversion to open surgery, and overall complication rate. In addition, there were also no significant differences between the two groups regarding the oncological outcomes, such as 1-, 3-, and 5-year overall survival. CONCLUSIONS: HCC patients with and without CSPH who underwent LH had comparable surgical and oncological outcomes. LH is a safe and effective treatment for HCC patients with CSPH under the premise of rational screening of patients.

Robotic versus laparoscopic liver resection for liver malignancy: a systematic review and meta-analysis of propensity score-matched studies.

OBJECTIVE: How different surgical procedures, including the robotic-assisted liver resection (RLR) and laparoscopic liver resection (LLR), can affect the prognosis of patients with liver malignancies is unclear. Thus, in this study, we compared the effects of RLR and LLR on the surgical and oncological outcomes in patients with liver malignancies through propensity score-matched cohort studies. METHODS: The PubMed, Embase, and Cochrane databases were searched using Medical Subject Headings terms and keywords from inception until May 31, 2023. The quality of the included studies was assessed using the Newcastle-Ottawa quality assessment scale. The mean difference with 95% confidence interval (95% CI) was used for analysis of continuous variables; the risk ratio with 95% CI was used for dichotomous variables; and the hazard ratio with 95% CI was used for survival-related variables. Meta-analysis was performed using a random-effects model. RESULTS: Five high-quality cohort studies with 986 patients were included (370 and 616 cases for RLR and LLR, respectively). In terms of surgical outcomes, there were no significant differences in the operation time, conversion rate to open surgery, overall complication rate, major complication rate, and length of hospital stay between the RLR and LLR groups. In terms of oncological outcomes, there were no significant differences in the 5-year overall survival and disease-free survival between the two groups. CONCLUSION: Surgical and oncological outcomes are comparable between RLR and LLR on patients with liver malignancies. Therefore, the benefits of applying RLR in patients with liver malignancies need to be further explored.

Transcriptome Profiling of Male Adult Angiostrongylus cantonensis.

Background: The pathogen of angiostrongyliasis is the parasite Angiostrongylus cantonensis, and the transcriptome profiling of the male adult was unclear. We aimed to understand how the male adults adapt, so the expression profile of A. cantonensis adult males was analyzed. Methods: In order to improve the understanding of the transcriptome of adult males, RNA from three groups of male adult A. cantonensis was extracted and reverse transcribed to construct cDNA libraries. After sequencing, annotation of unigenes and transcripts was performed by querying the NR (Non-Redundant Protein Sequence Database), GO (Gene Ontology) and COG/KOG (Clusters of Orthologous Groups of proteins/euKaryotic Ortholog Groups) databases. Results: For each group of adults, 43,260,894 raw reads and 43,200,341 clean reads were obtained. After successful assembly, 87,649 unigenes and 146,895 transcripts were obtained. Annotation of the unigenes and transcripts was identical and male adults expressed a series of genes encoding proteins specific to the male gender at the adult stage, such as proteins involved in energy metabolism, energy synthesis and transport. Expression of the ribosome pathway suggests a relationship with the physical activities during the adult male stage. Conclusion: The transcriptome analysis is a good reference to understand further the expression profile of male adult A. cantonensis.

Green synthesis of bifunctional phthalocyanine-porphyrin cofs in water for efficient electrocatalytic CO2 reduction coupled with methanol oxidation.

Electrocatalytic CO2 reduction (ECR) coupled with organic oxidation is a promising strategy to produce high value-added chemicals and improve energy efficiency. However, achieving the efficient redox coupling reaction is still challenging due to the lack of suitable electrocatalysts. Herein, we designed two bifunctional polyimides-linked covalent organic frameworks (PI-COFs) through assembling phthalocyanine (Pc) and porphyrin (Por) by non-toxic hydrothermal methods in pure water to realize the above catalytic reactions. Due to the high conductivity and well-defined active sites with different chemical environments, NiPc-NiPor COF performs efficient ECR coupled with methanol oxidation reaction (MOR) (Faradaic efficiency of CO (FECO) = 98.12%, partial current densities of CO (jCO) = 6.14 mA cm-2 for ECR, FEHCOOH = 93.75%, jHCOOH = 5.81 mA cm-2 for MOR at low cell voltage (2.1 V) and remarkable long-term stability). Furthermore, experimental evidences and density functional theory (DFT) calculations demonstrate that the ECR process mainly conducts on NiPc unit with the assistance of NiPor, meanwhile, the MOR prefers NiPor conjugating with NiPc. The two units of NiPc-NiPor COF collaboratively promote the coupled oxidation-reduction reaction. For the first time, this work achieves the rational design of bifunctional COFs for coupled heterogeneous catalysis, which opens a new area for crystalline material catalysts.

Expression profiles of lncRNAs, miRNAs, and mRNAs during the proliferative phase of liver regeneration in mice with liver fibrosis.

The role of lncRNAs in the regeneration of fibrotic liver is unclear. To address this issue, we established a 70% hepatectomy model of liver fibrosis in mice, used high-throughput sequencing technology to obtain the expression profiles of lncRNAs, miRNAs, and mRNAs, and constructed a lncRNA-miRNA-mRNA regulatory network. A total of 1329 lncRNAs, 167 miRNAs, and 6458 mRNAs were differentially expressed. On this basis, a lncRNA-miRNA-mRNA ceRNA regulatory network consisting of 38 DE lncRNAs, 24 DE miRNAs, and 299 DE mRNAs was constructed, and a transcription factor (TF) - mRNA regulatory network composed of 20 TFs and 98 DE mRNAs was built. Through the protein network analysis, a core protein interaction network composed of 20 hub genes was derived. Furthermore, Xist/miR-144-3p/Cdc14b and Snhg3/miR-365-3p/Map3k14 axes in the ceRNA regulatory network were verified by Real-Time quantitative PCR. Therefore, we concluded that these new insights may further our understanding of liver regeneration.

Synergistic Metal-Nonmetal Active Sites in a Metal-Organic Cage for Efficient Photocatalytic Synthesis of Hydrogen Peroxide in Pure Water.

Photocatalytic synthesis of hydrogen peroxide (H2 O2 ) is a potential clean method, but the long distance between the oxidation and reduction sites in photocatalysts hinders the rapid transfer of photogenerated charges, limiting the improvement of its performance. Here, a metal-organic cage photocatalyst, Co14 (L-CH3 )24 , is constructed by directly coordinating metal sites (Co sites) used for the O2 reduction reaction (ORR) with non-metallic sites (imidazole sites of ligands) used for the H2 O oxidation reaction (WOR), which shortens the transport path of photogenerated electrons and holes, and improves the transport efficiency of charges and activity of the photocatalyst. Therefore, it can be used as an efficient photocatalyst with a rate of as high as 146.6 µmol g-1 h-1 for H2 O2 production under O2 -saturated pure water without sacrificial agents. Significantly, the combination of photocatalytic experiments and theoretical calculations proves that the functionalized modification of ligands is more conducive to adsorbing key intermediates (*OH for WOR and *HOOH for ORR), resulting in better performance. This work proposed a new catalytic strategy for the first time; i.e., to build a synergistic metal-nonmetal active site in the crystalline catalyst and use the host-guest chemistry inherent in the metal-organic cage (MOC)to increase the contact between the substrate and the catalytically active site, and finally achieve efficient photocatalytic H2 O2 synthesis.

Calix[4]arene-Functionalized Titanium-Oxo Compounds for Perceiving Differences in Catalytic Reactivity Between Mono- and Multimetallic Sites.

While the difference in catalytic reactivity between mono- and multimetallic sites is often attributed to more than just the number of active sites, still few catalyst model systems have been developed to explore more underlying causal factors. In this work, we have elaborately designed and constructed three stable calix[4]arene (C4A)-functionalized titanium-oxo compounds, Ti-C4A, Ti4-C4A, and Ti16-C4A, with well-defined crystal structures, increasing nuclearity, and tunable light absorption capacity and energy levels. Among them, Ti-C4A and Ti16-C4A can be taken as model catalysts to compare the differences in reactivity between mono- and multimetallic sites. Taking CO2 photoreduction as the basic catalytic reaction, both compounds can achieve CO2-to-HCOO- conversion with high selectivity (close to 100%). Moreover, the catalytic activity of multimetallic Ti16-C4A is up to 2265.5 µmol g-1 h-1, which is at least 12 times higher than that of monometallic Ti-C4A (180.0 µmol g-1 h-1), and is the best-performing crystalline cluster-based photocatalyst known to date. Catalytic characterization combined with density functional theory calculations shows that in addition to the advantage of having more metal active sites (for adsorption and activation of more CO2 molecules), Ti16-C4A can effectively reduce the activation energy required for the CO2 reduction reaction by completing the multiple electron-proton transfer process rapidly with synergistic metal-ligand catalysis, thus exhibiting superior catalytic performance to that of monometallic Ti-C4A. This work provides a crystalline catalyst model system to explore the potential factors underlying the difference in catalytic reactivity between mono- and multimetallic sites.

Structural Evolution of Giant Polyoxometalate: From "Keplerate" to "Lantern" Type Mo132 for Improved Oxidation Catalysis.

Structural variants of high-nuclearity clusters are extremely important for their modular assembly study and functional expansion, yet the synthesis of such giant structural variants remains a great challenge. Herein, we prepared a lantern-type giant polymolybdate cluster (L-Mo132 ) containing equal metal nuclearity with the famous Keplerate type Mo132 (K-Mo132 ). The skeleton of L-Mo132 features a rare truncated rhombic triacontrahedron, which is totally different with the truncated icosahedral K-Mo132 . To the best of our knowledge, this is the first time to observe such structural variants in high-nuclearity cluster built up of more than 100 metal atoms. Scanning transmission electron microscopy reveals that L-Mo132 has good stability. More importantly, because the pentagonal [Mo6 O27 ]n- building blocks in L-Mo132 are concave instead of convex in the outer face, it contains multiple terminal coordinated water molecules on its outer surface, which make it expose more active metal sites to display superior phenol oxidation performance, which is more higher than that of K-Mo132 coordinated in M=O bonds on the outer surface.

Integrating Enrichment, Reduction, and Oxidation Sites in One System for Artificial Photosynthetic Diluted CO2 Reduction.

Artificial photosynthetic diluted CO2 reduction directly driven by natural sunlight is a challenging, but promising way to realize carbon-resources recycling utilization. Herein, a three-in-one photocatalytic system of CO2 enrichment, CO2 reduction and H2 O oxidation sites is designed for diluted CO2 reduction. A Zn-Salen-based covalent organic framework (Zn-S-COF) with oxidation and reductive sites is synthesized; then, ionic liquids (ILs) are loaded into the pores. As a result, [Emim]BF4 @Zn-S-COF shows a visible-light-driven CO2 -to-CO conversion rate of 105.88 µmol g-1 h-1 under diluted CO2 (15%) atmosphere, even superior than most photocatalysts in high concentrations CO2 . Moreover, natural sunlight driven diluted CO2 reduction rate also reaches 126.51 µmol g-1 in 5 h. Further experiments and theoretical calculations reveal that the triazine ring in the Zn-S-COF promotes the activity of H2 O oxidation and CO2 reduction sites, and the loaded ILs provide an enriched CO2 atmosphere, realizing the efficient photocatalytic activity in diluted CO2 reduction.

Laparoscopic versus open repeat hepatectomy for recurrent hepatocellular carcinoma: a systematic review and meta-analysis of propensity score-matched cohort studies.

OBJECTIVE: The effectiveness of laparoscopic repeat hepatectomy (LRH) versus open repeat hepatectomy (ORH) on recurrent hepatocellular carcinoma (RHCC) is unclear. We compared the surgical and oncological outcomes of LRH and ORH in patients with RHCC with a meta-analysis of studies based on propensity score-matched cohorts. METHODS: A literature search was conducted on PubMed, Embase, and Cochrane Library with Medical Subject Headings terms and keywords until 30 September 2022. The quality of eligible studies was evaluated with the Newcastle-Ottawa Scale. Mean difference (MD) with a 95% CI was used for the analysis of continuous variables; odds ratio (OR) with 95% CI was used for binary variables; and hazard ratio with 95% CI was used for survival analysis. A random-effects model was used for meta-analysis. RESULTS: Five high-quality retrospective studies with 818 patients were included; 409 patients (50%) were treated with LRH and 409 (50%) with ORH. In most surgical outcomes, LRH was superior to ORH: less estimated blood loss, shorter operation time, lower major complication rate, and shorter length of hospital stay (MD=-225.9, 95% CI=[-360.8 to -91.06], P =0.001; MD=66.2, 95% CI=[5.28-127.1], P =0.03; OR=0.18, 95% CI=[0.05-0.57], P =0.004; MD=-6.22, 95% CI=[-9.78 to -2.67], P =0.0006). There were no significant differences in the remaining surgical outcomes: blood transfusion rate and overall complication rate. In oncological outcomes, LRH and ORH were not significantly different in 1-year, 3-year, and 5-year overall survival and disease-free survival. CONCLUSIONS: For patients with RHCC, most surgical outcomes with LRH were superior to those of ORH, but oncological outcomes with the two operations were similar. LRH may be a preferable option for the treatment of RHCC.

Achieving High-Efficient Photoelectrocatalytic Degradation of 4-Chlorophenol via Functional Reformation of Titanium-Oxo Clusters.

Rational design of crystalline catalysts with superior light absorption and charge transfer for efficient photoelectrocatalytic (PEC) reaction coupled with energy recovery remains a great challenge. In this work, we elaborately construct three stable titanium-oxo clusters (TOCs, Ti10Ac6, Ti10Fc8, and Ti12Fc2Ac4) modified with a monofunctionalized ligand (9-anthracenecarboxylic acid (Ac) or ferrocenecarboxylic acid (Fc)) and bifunctionalized ligands (Ac and Fc). They have tunable light-harvesting and charge transfer capacities and thus can serve as outstanding crystalline catalysts to achieve efficient PEC overall reaction, that is, the integration of anodic organic pollutant 4-chlorophenol (4-CP) degradation and cathodic wastewater-to-H2 conversion. These TOCs can all exhibit very high PEC activity and degradation efficiency of 4-CP. Especially, Ti12Fc2Ac4 decorated with bifunctionalized ligands exhibits better PEC degradation efficiency (over 99%) and H2 generation than Ti10Ac6 and Ti10Fc8 modified with a monofunctionalized ligand. The study of the 4-CP degradation pathway and mechanism revealed that such better PEC performance of Ti12Fc2Ac4 is probably due to its stronger interactions with the 4-CP molecule and better •OH radical production. This work not only presents the effective combination of organic pollutant degradation and simultaneously H2 evolution reaction using crystalline coordination clusters as both anodic and cathodic catalyst but also develops a new PEC application for crystalline coordination compounds.