Tumour microenvironment-responded Fe-doped carbon dots-sensitized cubic Cu2O for Z-scheme heterojunction-enhanced sono-chemodynamic synergistic tumor therapy.

The efficacy of electron-hole separation in a single sonosensitizer and the complexities of the tumor microenvironment (TME) present significant challenges to the effectiveness of sonodynamic therapy (SDT). Designing efficient sonosensitizers to enhance electron-hole separation and alleviate TME resistance is crucial yet challenging. Herein, we introduce a novel Z-scheme heterojunctions (HJs) sonosensitizer using Fe-doped carbon dots (CDs) as auxiliary semiconductors to sensitize cubic Cu2O (Fe-CDs@Cu2O) for the first time. Fe-CDs@Cu2O demonstrated enhanced SDT effects due to improved electron-hole separation. Additionally, the introduction of Fe ions in CDs synergistically enhances Fenton-like reactions with Cu ions in Cu2O, resulting in enhanced chemodynamic therapy (CDT) effects. Moreover, Fe-CDs@Cu2O exhibited rapid glutathione (GSH) depletion, effectively mitigating TME resistance. With high rates of 1O2 and OH generated by Fe-CDs@Cu2O, coupled with strong GSH depletion, single drug injection and ultrasound (US) irradiation effectively eliminate tumors. This innovative heterojunction sonosensitizer offers a promising pathway for clinical anti-tumor treatment.

Amino-Functionalized Graphdiyne Derivative as a Cathode Interface Layer with High Thickness Tolerance for Highly Efficient Organic Solar Cells.

Efficient cathode interfacial materials (CIMs) are essential components for effectively enhancing the performance of organic solar cells (OSCs). Although high-performance CIMs are desired to meet the requirements of various OSCs, potential candidates for CIMs are scarce. Herein, an amino-functionalized graphdiyne derivative (GDY-N) is developed, which represents the first example of GDY that exhibits favorable solubility in alcohol. Utilizing GDY-N as the CIM, an outstanding champion PCE of 19.30% for devices based on the D18-Cl:L8-BO (certified result: 19.05%) is achieved, which is among the highest efficiencies reported to date in OSCs. Remarkably, the devices based on GDY-N exhibit a thickness-insensitive characteristic, maintaining 95% of their initial efficiency even with a film thickness of 25 nm. Moreover, the GDY-N displays wide universality and facilitates exceptional stability in OSCs. This work not only enriches the diversity of GDY derivatives, but also demonstrates the feasibility of GDY derivatives as CIMs with high thickness tolerance in OSCs.

Nanotubular Fe2O3 and Mn3O4 with hierarchical porosity as high-performance anode materials for lithium-ion batteries.

Developing eco-friendly and low-cost advanced anode materials, such as Fe2O3 and Mn3O4, is fundamental to improve the electrochemical performance of lithium-ion batteries (LIBs). The rational engineering of the microstructure of Fe2O3 and Mn3O4 to endow it with one-dimensionally and hierarchically porous architecture is a feasible way to further improve and optimize the electrochemical performance of the anode materials. Herein, we demonstrate a facile strategy to prepare nanotubular Fe2O3 and Mn3O4 as advanced anode materials for high-performance LIBs. By combining the merits of the one-dimensionally nanotubular morphology and hierarchically porous structure, limitations in the lithiation activity of Mn3O4 and Fe2O3 anode materials, such as low electrical conductivity, large volume expansion, and sluggish lithium-ion diffusion within the materials, have been effectively overcome. When used as anode materials, t-Fe2O3 and t-Mn3O4 exhibited outstanding electrochemical performances, including a high reversible discharge capacity (859.7 and 901.4 mA h g-1 for t-Fe2O3 and t-Mn3O4, respectively), excellent rate performance, and ultra-stable cycling stability. Such superior electrochemical performances proved the exceptional potential of the materials for the real-world application in LIBs.

Targeting PTGES/PGE2 axis enhances sensitivity of colorectal cancer cells to 5-fluorouracil.

Insensitivity and resistance to 5-fluorouracil (5FU) remain as major hurdles for effective and durable 5FU-based chemotherapy in colorectal cancer (CRC) patients. In this study, we identified prostaglandin E synthase (PTGES)/prostaglandin E2 (PGE2) axis as an important regulator for 5FU sensitivity in CRC cells. We found that PTGES expression and PGE2 production are elevated in CRC cells in comparison to normal colorectal epithelial cells. Depletion of PTGES significantly enhanced the inhibitory effect of 5FU on CRC cell viability that was fully reverted by exogenous supplement of PGE2. Inhibition of PTGES enzymatic function, by either inducing loss-of-function mutant or treatment with selective inhibitors, phenocopied the PTGES depletion in terms of 5FU sensitization. Mechanistically, PTGES/PGE2 axis modulates glycolysis in CRC cells, thereby regulating the 5FU sensitivity. Importantly, high PTGES expression is correlated with poor prognosis in 5FU-treated CRC patients. Thus, our study defines PTGES/PGE2 axis as a novel therapeutic target for enhancing the efficacy of 5FU-based chemotherapy in CRC.

Pore Environment Optimization of Microporous Metal-Organic Frameworks with Huddled Pyrazine Pillars for C2H2/CO2 Separation.

Metal-organic frameworks (MOFs) have been proven promising in addressing many critical issues related to gas separation and purification. However, it remains a great challenge to optimize the pore environment of MOFs for purification of specific gas mixtures. Herein, we report the rational construction of three isostructural microporous MOFs with the 4,4',4"-tricarboxyltriphenylamine (H3TCA) ligand, unusual hexaprismane Ni6O6 cluster, and functionalized pyrazine pillars [PYZ-x, x = -H (DZU-10), -NH2 (DZU-11), and -OH (DZU-12)], where the building blocks of Ni6O6 clusters and huddled pyrazine pillars are reported in porous MOFs for the first time. These building blocks have enabled the resulting materials to exhibit good chemical stability and variable pore chemistry, which thus contribute to distinct performances toward C2H2/CO2 separation. Both single-component isotherms and dynamic column breakthrough experiments demonstrate that DZU-11 with the PYZ-NH2 pillar outperforms its hydrogen and hydroxy analogues. Density functional theory calculations reveal that the higher C2H2 affinity of DZU-11 over CO2 is attributed to multiple electrostatic interactions between C2H2 and the framework, including strong C≡C···H-N (2.80 Å) interactions. This work highlights the potential of pore environment optimization to construct smart MOF adsorbents for some challenging gas separations.

Research Progress on Small Molecular Inhibitors of the Type 3 Secretion System.

The overuse of antibiotics has led to severe bacterial drug resistance. Blocking pathogen virulence devices is a highly effective approach to combating bacterial resistance worldwide. Type three secretion systems (T3SSs) are significant virulence factors in Gram-negative pathogens. Inhibition of these systems can effectively weaken infection whilst having no significant effect on bacterial growth. Therefore, T3SS inhibitors may be a powerful weapon against resistance in Gram-negative bacteria, and there has been increasing interest in the research and development of T3SS inhibitors. This review outlines several reported small-molecule inhibitors of the T3SS, covering those of synthetic and natural origin, including their sources, structures, and mechanisms of action.

A Polyvinyl Alcohol-Tannic Acid Gel with Exceptional Mechanical Properties and Ultraviolet Resistance.

Design and preparation of gels with excellent mechanical properties has garnered wide interest at present. In this paper, preparation of polyvinyl alcohol (PVA)-tannic acid (TA) gels with exceptional properties is documented. The crystallization zone and hydrogen bonding acted as physical crosslinkages fabricated by a combination of freeze-thaw treatment and a tannic acid compound. The effect of tannic acid on mechanical properties of prepared PVA-TA gels was investigated and analyzed. When the mass fraction of PVA was 20.0 wt% and soaking time was 12 h in tannic acid aqueous solution, tensile strength and the elongation at break of PVA-TA gel reached 5.97 MPa and 1450%, respectively. This PVA-TA gel was far superior to a pure 20.0 wt% PVA hydrogel treated only with the freeze-thaw process, as well as most previously reported PVA-TA gels. The toughness of a PVA-TA gel is about 14 times that of a pure PVA gel. In addition, transparent PVA-TA gels can effectively prevent ultraviolet-light-induced degradation. This study provides a novel strategy and reference for design and preparation of high-performance gels that are promising for practical application.

Interpenetrated metal-organic frameworks with enhanced photoluminescence for selective recognition of m-xylene from xylene isomers.

Two novel luminescent metal-organic frameworks (MOFs), [Zn3(TCA)2(BPB)2]n (DZU-101, where H3TCA = 4,4',4''-tricarboxyltriphenylamine and BPB = 1,4-bis(pyrid-4-yl)benzene) and [Zn3(TCA)2(BPB)DMA]n (DZU-102), based on the same ligands and metal ions were synthesized by regulating the amount of water in the solvothermal reaction system. Structural analyses show that the two MOFs have pillar-layered frameworks with Zn3 clusters connected by the TCA3- and BPB ligands. Interestingly, DZU-102 possessed a two-fold interpenetrated framework distinct from the individual network of DZU-101. As a result, DZU-102 showed a visual fluorescence color change from chartreuse to azure in m-xylene, while the fluorescence color was turquoise in p-/o-xylene with no change. Furthermore, compared with p/o-xylene, the fluorescence emission peak of DZU-102 in m-xylene suspension produced an obvious blue shift. Moreover, selective fluorescence sensing experiments were also carried out, which demonstrated that the degree of peak shift was related to the concentration of m-xylene, indicating the potential application of DZU-102 in fluorescence sensing of m-xylene from xylene isomers and further revealed the application of structural interpenetration for luminescence tuning of MOFs.

Pillar-Layered Metal-Organic Frameworks Based on a Hexaprismane [Co6(µ3-OH)6] Cluster: Structural Modulation and Catalytic Performance in Aerobic Oxidation Reaction.

Embedding a functional metal-oxo cluster within the matrix of metal-organic frameworks (MOFs) is a feasible approach for the development of advanced porous materials. Herein, three isoreticular pillar-layered MOFs (Co6-MOF-1-3) based on a unique [Co6(µ3-OH)6] cluster were designed, synthesized, and structurally characterized. For these Co6-MOFs, tuning of the framework backbone was facilitated due to the existence of second ligands, which results in adjustable apertures (8.8 to 13.4 Å) and high Brunauer-Emmett-Teller surfaces (1896-2401 m2 g-1). As the [Co6(µ3-OH)6] cluster has variable valences, these MOFs were then utilized as heterogeneous catalysts for the selective oxidation of styrene and benzyl alcohol, showing high conversion (>90%) and good selectivity. The selectivity of styrene to styrene oxide surpassed 80% and that of benzyl alcohol to benzaldehyde was up to 98%. The calculated TOF values show that the increase of reaction rate is positively correlated with the enlargement of pore sizes in these MOFs. Further, a stability test and cycling experiment proved that these Co6-MOFs have well-observed stability and recyclability.

Ultrafine Ru species within confined space: An efficient adsorbent for ultra-deep desulfurization of benzene.

The ultra-deep adsorptive desulfurization (ppb level) of benzene remains a challenging subject with the need to construct efficient adsorbent systems. Herein, a kind of ruthenium-based adsorbent functionalized with bimetallic Ru-Al was rationally designed using Al2O3 as support (denoted as 0.8%Ru-1.2%Al/Al2O3). It was found that the co-anchoring of Ru and Al species endows the Ru-based adsorbent unique adsorption capability, which is able to completely eliminate sulfur compounds in benzene, and exhibiting a much higher breakthrough sulfur capacity than that of the 0.8%Ru/Al2O3. Remarkably, under the industrial experiment conditions, 0.8%Ru-1.2%Al/Al2O3 exhibited excellent long-term stability for more than 1200 h, showing the potential for industrial application. Various characterization techniques, including BET, XRD, SEM, TEM, TPD-MS, TPR and XPS, were used to investigate the correlation between the adsorption performance and the microstructure of the adsorbents. Over 0.8%Ru-1.2%Al/Al2O3, the ultra-thin aluminum additive is beneficial to improve the dispersion of Ru species, which therefore exhibits desirable desulfurization efficiency. Moreover, the enhanced performance is also correlated to the presence of the suitable Ru active centers generated from the selective coverage by Al species. It leads to an optimal exposure of the Ru active centers, which would facilitate the interaction of S-Ru and the improvement of the desulfurization activity.

Combining unsaturated metal sites and narrow pores within a Co(ii)-based MOF towards CO2 separation and transformation.

A Co(ii)-based MOF, {[Co3(L)2(bpb)(DMA)(H2O)]·Solvents}n (RH-1), with a unique interpenetrated framework has been solvothermally prepared. Because of its unsaturated metal sites and narrow pores inside the framework, RH-1 demonstrated excellent selective CO2 adsorption over N2 and CH4 and good performance in catalytic CO2 conversion to cyclic carbonates under mild conditions.

Predictive value of IL-18 and IL-10 in the prognosis of patients with colorectal cancer.

Predictive value of serum interleukin 10 (IL-10) and interleukin 18 (IL-18) expression in patients with colorectal cancer (CRC) was investigated. This study retrospectively analyzed the medical records of 146 patients with CRC admitted to the Binzhou Medical University Hospital as the study group, and collected the physical examination data of 82 volunteers as the control group. The expression levels of IL-10 and IL-18 in the serum were measured by enzyme-linked immunosorbent assay (ELISA). A 60-month follow-up on patients in the study group was performed to make records of their prognosis. The expressions of IL-10 and IL-18 were statistically different in patients with different Dukes stages, tumor sizes, histological grades, and different situations of distant metastasis of cancer cells (P<0.05); with a gradual downward trend following the operation. The expression levels of serum IL-10 and IL-18 in the study group 7 days after the operation were lower than the levels before the operation (P<0.05), and the expression levels of IL-10 and IL-18 of patients in the study group on the day of discharge were lower than the expression levels 7 days after the operation (P<0.05). The expressions of IL-10 and IL-18 of patients with reoccurred CRC after the operation were significantly higher than that of patients without recurrence of CRC in the study group (P<0.05). Thus, IL-10 and IL-18 are highly expressed in the serum of CRC patients, which makes IL-10 and IL-18 useful to serve as indicators to determine the prognosis of CRC patients. The lower the expression levels of IL-10 and IL-18, the lower the cancer recurrence rate, the better the prognosis and the longer the survival time.

Nanocage-Based Porous Metal-Organic Frameworks Constructed from Icosahedrons and Tetrahedrons for Selective Gas Adsorption.

Two isostructural nanocage-based porous Ni/Co(II)-MOFs have been hydrothermally synthesized, which were interestingly composed of icosahedron and tetrahedron cages with a new (3,8)-connected 3D topology. Moreover, the stable Ni-MOF exhibits good selective CO2/CH4 and CO2/N2 adsorption owing to its exposed nitrogen active sites.

Structure modulation from unstable to stable MOFs by regulating secondary N-donor ligands.

Four new Zn(ii)/Cd(ii)-based metal-organic frameworks (MOFs), namely {[Cd(tmdb)(bib)0.5]·solvents}n (YZ-7, YZ stands for the initials of the author Yong-Zheng Zhang), {[Cd(tmdb)(bmib)0.5]·solvents}n (YZ-8), {[Zn2(tmdb)2(bmib)]·solvents}n (YZ-9) and {[Zn2(tmdb)2(bmip)2]·solvents}n (YZ-10) have been solvothermally synthesized by using a semi-rigid ligand, 4,4'-(H-1,2,4-triazol-1-yl)methylene-dibenzoic acid (H2tmdb), and a series of secondary bis-imidazole ligands (bib = 1,4-bis(1H-imidazol-1-yl)benzene, bmib = 1,4-bis(2-methyl-1H-imidazol-1-yl)benzene, and bmip = 1,3-bis(2-methyl-1H-imidazol-1-yl)propane). By tuning the flexibility of the auxiliary ligands, these MOFs could be modulated from unstable (YZ-7-YZ-9) to stable (YZ-10) frameworks. Therefore, the gas adsorption properties of YZ-10 are further studied. Interestingly, it shows excellent CO2 selective uptake over CH4 and N2. At 298 K, both selectivities of CO2/CH4 and CO2/N2 show increasing trends and significantly reach 133.2 and 19.9 at 1 atm, respectively. Also, YZ-10 shows uncommon H2 selective uptake over N2 at 77 K. Moreover, the luminescence properties of YZ-8-YZ-10 were studied in the solid state at room temperature.

Facile synthesis of ultrafine cobalt oxides embedded into N-doped carbon with superior activity in hydrogenation of 4-nitrophenol.

Design and synthesis of low-cost catalysts with high activity and stability for hydrogenation reactions is an important research area of applied catalysis. In this work, we present a kind of ultrafine cobalt oxides encapsulated by N-doped carbon (donated as CoOx/CN) as efficient catalysts for hydrogenation of 4-nitrophenol (4-NP) process. The CoOx/CN was fabricated through a pyrolysis strategy using an N-containing metal-organic framework (Co-MOF) as precursor followed by a fine thermal-treatment. With an optimized pyrolysis temperature of 500 °C, the CoOx species present as ultrafine particles highly dispersed in the obtained catalyst (CoOx/CN-500). CoOx/CN-500 exhibits excellent activity and stability in hydrogenation of 4-NP at ambient conditions. The activity is much higher than that of not only bulk cobalt oxides, but also carbon supported CoOx catalysts. It could be used for more than 8 times without obvious fading in activity. In addition, the concrete role of Co-MOF precursor and pyrolysis condition in the catalyst design was investigated in detail. The interaction between organic ligands and Co ions and the confinement of the crystalline structure of Co-MOF could restrain the aggregation of Co ions during pyrolysis and lead to high dispersion of ultrafine CoOx species. Meanwhile, the N-containing ligands could be transformed into doped N species (pyridinic and pyrrolic N), endowing the CoOx species with high electron density and promoting the formation of active sites for the hydrogenation reaction.

CeO2 nanorods anchored on mesoporous carbon as an efficient catalyst for imine synthesis.

CeO2 nanorods anchored on mesoporous carbon exhibit high activity and stability in aerobic oxidative coupling of alcohols and amines to imines. The abundant surface Ce3+ and the suitable interaction between CeO2 nanorods and the carbon support should be responsible for the excellent catalytic behaviors.

Highly-efficient cocatalyst-free H2-evolution over silica-supported CdS nanoparticle photocatalysts under visible light.

A silica-supported CdS nanoparticle photocatalyst exhibits excellent visible-light driven H2 evolution activity without the use of a cocatalyst. The apparent quantum yield can reach 42% under 420 nm light illumination.

Correlation between the microstructures of graphite oxides and their catalytic behaviors in air oxidation of benzyl alcohol.

A series of graphite oxide (GO) materials were obtained by thermal treatment of oxidized natural graphite powder at different temperatures (from 100 to 200 °C). The microstructure evolution (i.e., layer structure and surface functional groups) of the graphite oxide during the heating process is studied by various characterization means, including XRD, N2 adsorption, TG-DTA, in situ DRIFT, XPS, Raman, TEM and Boehm titration. The characterization results show that the structures of GO materials change gradually from multilayer sheets to a transparent ultrathin 2D structure of the carbon sheets. The concentration of surface COH and HOCO groups decrease significantly upon treating temperature increasing. Benzyl alcohol oxidation with air as oxidant source was carried out to detect the catalytic behaviors of different GO materials. The activities of GO materials decrease with the increase of treating temperatures. It shows that the structure properties, including ultrathin sheets and high specific surface area, are not crucial factors affecting the catalytic activity. The type and amount of surface oxygen-containing functional groups of GO materials tightly correlates with the catalytic performance. Carboxylic groups on the surface of GO should act as oxidative sites for benzyl alcohol and the reduced form could be reoxidized by molecular oxygen.

Highly dispersed iron oxides on mesoporous carbon for selective oxidation of benzyl alcohol with molecular oxygen.

Highly dispersed iron oxide supported catalysts, prepared using HNO3-treated CMK-3 mesoporous carbons as supports, exhibit relatively high catalytic activity in selective oxidation of benzyl alcohol with oxygen.