Effective Reduction of CO2 with Aromatic Amines into N-Formamides Triggered by Noble-Free Metal-Organic Framework Catalysts Under Mild Conditions.

The reductive transformation of carbon dioxide (CO2) into high-valued N­formamides matches well with the atom economy and the sustainable development intention. Nevertheless, developing a noble-free metal catalyst under mild reaction conditions is desirable and challenging. Herein, a caged metal-organic framework (MOFs) [H2N(CH3)2]2{[Ni3(µ3-O)(XN)(BDC)3]·6DMF}n (1) (XN = 6″-(pyridin-4-yl)-4,2″:4″,4″'-terpyridine), H2BDC = terephthalic acid) is harvested, presenting high thermal and chemical stabilities. Catalytic investigation reveals that 1 as a renewable noble-free MOFs catalyst can catalyze the CO2 reduction conversion with aromatic amines tolerated by broad functional groups at least ten times, resulting in various formamides in excellent yields and selectivity under the mildest reaction system (room temperature and 1 bar CO2). Density functional theory (DFT) theoretical studies disclose the applicable reaction path, in which the CO2 hydrosilylation process is initiated by the [Ni3] cluster interaction with CO2 via η2-C, O coordination mode. This work may open up an avenue to seek high-efficiency noble-free catalysts in CO2 chemical reduction into high value-added chemicals.

Exploring Carbonization Temperature to Create Closed Pores for Hard Carbon as High-Performance Sodium-Ion Battery Anodes.

Biomass-derived porous carbon materials are meaningful to employ as a hard carbon precursor for anode materials of sodium-ion batteries (SIBs) from a sustainability perspective. Here, a straightforward approach is proposed to develop rich closed pores in pinenut-derived carbon, with the aim of improving Na+ plateau storage by adjusting the pyrolysis temperature. The optimized sample, namely the pinenut-derived carbon at 1300 °C, demonstrates remarkable reversible specific capacity of 278 mAh g-1, along with a high initial Coulomb efficiency of 85% and robust cycling stability (with a capacity retention of 89% after 800 cycles at 0.2 A g-1). In situ and ex situ analyses unveil that the developed closed pores play a significant role in enhancing the plateau capacity, providing compelling evidence for the "adsorption-filling" mechanism. Moreover, the corresponding full-cell achieves a high energy density of 245.7 Wh kg-1 (based on the total weight of both electrode active materials) and exhibits outstanding rate capability (191.4 mAh g-1 at 3 A g-1).

CoFeSe2 @DMSA@FA Nanocatalyst for Amplification of Oxidative Stress to Achieve Multimodal Tumor Therapy.

Nanomedicine has significantly advanced precise tumor therapy, providing essential technical blessing for active drug accumulation, targeted consignment, and mitigation of noxious side effects. To enhance anti-tumor efficacy, the integration of multiple therapeutic modalities has garnered significant attention. Here, we designed an innovative CoFeSe2 @DMSA@FA nanocatalyst with Se vacancies (abbreviated as CFSDF), which exhibits synergistic chemodynamic therapy (CDT) and photothermal therapy (PTT), leading to amplified tumor oxidative stress and enhanced photothermal effects. The multifunctional CFSDF nanocatalyst exhibits the remarkable ability to catalyze the Fenton reaction within the acidic tumor microenvironment, efficiently converting hydrogen peroxide (H2 O2 ) into highly harmful hydroxyl radicals (⋅OH). Moreover, the nanocatalyst effectively diminishes GSH levels and ameliorates intracellular oxidative stress. The incorporation of FA modification enables CFSDF to evade immune detection and selectively target tumor tissues. Numerous in vitro and in vivo investigations have consistently demonstrated that CFSDF optimizes its individual advantages and significantly enhances therapeutic efficiency through synergistic effects of multiple therapeutic modalities, offering a valuable and effective approach to cancer treatment.

Improving the performance of reference-frame-independent quantum key distribution with advantage distillation technology.

The reference-frame-independent quantum key distribution (RFI-QKD) has the advantage of tolerating reference frames that slowly vary. It can generate secure keys between two remote users with slowly drifted and unknown reference frames. However, the drift of reference frames may inevitably compromise the performance of QKD systems. In the paper, we employ the advantage distillation technology (ADT) to the RFI-QKD and the RFI measurement-device-independent QKD (RFI MDI-QKD), and we then analyze the effect of ADT on the performance of decoy-state RFI-QKD and RFI MDI-QKD in both asymptotic and nonasymptotic cases. The simulation results show that ADT can significantly improve the maximum transmission distance and the maximum tolerable background error rate. Furthermore, the performance of RFI-QKD and RFI MDI-QKD in terms of the secret key rate and maximum transmission distance are still greatly improved when statistical fluctuations are taken into account. Our work combines the merits of the ADT and RFI-QKD protocols, which further enhances the robustness and practicability of QKD systems.

Nitrogen Deposition Effects on Invasive and Native Plant Competition: Implications for Future Invasions.

Nitrogen (N) deposition has increased dramatically in recent decades, which is significantly affecting the invasion and growth of exotic plants. Whether N deposition leads to invasive alien species becoming competitively superior to native species remains to be investigated. In the present study, an invasive species (Oenothera biennis L.) and three co-occurring native species (Artemisia argyi Lévl. et Vant., Inula japonica Thunb., and Chenopodium album L.) were grown in a monoculture (two seedlings of the same species) or mixed culture (one seedling of O. biennis and one seedling of a native species) under three levels of N deposition (0, 6, and 12 g∙m-2∙year-1). Nitrogen deposition had no effect on soil N and P content. Nitrogen deposition enhanced the crown area, total biomass, leaf chlorophyll content, and leaf N to phosphorus ratio in both invasive and native plants. Oenothera biennis dominated competition with C. album and I. japonica due to its high resource acquisition and absorption capacity (greater height, canopy, leaf chlorophyll a to chlorophyll b ratio, leaf chlorophyll content, leaf N content, leaf mass fraction, and lower root-to-shoot ratio). However, the native species A. argyi exhibited competitive ability similar to O. biennis. Thus, invasive species are not always superior competitors of native species; this depends on the identities of the native species. High N deposition enhanced the competitive dominance of O. biennis over I. japonica by 15.45% but did not alter the competitive dominance of O. biennis over C. album. Furthermore, N deposition did not affect the dominance of O. biennis or A. argyi. Therefore, the species composition of the native community must be considered when preparing to resist future biological invasions. Our study contributes to a better understanding of the invasion mechanisms of alien species under N-loading conditions.

Research Progress Regarding the Effect and Mechanism of Dietary Polyphenols in Liver Fibrosis.

The development of liver fibrosis is a result of chronic liver injuries may progress to liver cirrhosis and liver cancer. In recent years, liver fibrosis has become a major global problem, and the incidence rate and mortality are increasing year by year. However, there are currently no approved treatments. Research on anti-liver-fibrosis drugs is a top priority. Dietary polyphenols, such as plant secondary metabolites, have remarkable abilities to reduce lipid metabolism, insulin resistance and inflammation, and are attracting more and more attention as potential drugs for the treatment of liver diseases. Gradually, dietary polyphenols are becoming the focus for providing an improvement in the treatment of liver fibrosis. The impact of dietary polyphenols on the composition of intestinal microbiota and the subsequent production of intestinal microbial metabolites has been observed to indirectly modulate signaling pathways in the liver, thereby exerting regulatory effects on liver disease. In conclusion, there is evidence that dietary polyphenols can be therapeutically useful in preventing and treating liver fibrosis, and we highlight new perspectives and key questions for future drug development.

Gold-catalyzed cycloadditions of allenes via metal carbenes.

In recent years, gold-catalyzed cycloadditions of allenes, especially those involving a gold carbene intermediate, have received significant interest, as they avoid the utilization of potentially hazardous and inaccessible diazo compounds as starting materials for carbene generation. Cycloaddition reactions consisting of the uncomplicated addition of two or more unsaturated functional groups are one of the most efficient synthetic methodologies for the rapid assembly of carbo- and heterocyclic structures from simple acyclic precursors. In this review, we introduce an overview of the advances in the gold-catalyzed cycloaddition of allenes via a metal carbene intermediate and categorize these reactions according to the reaction types of the cycloadditions.

Circ_0030998 Restrains Cisplatin Resistance Through Mediating miR-1323/PDCD4 Axis in Non-small Cell Lung Cancer.

We aimed to explore the underlying mechanism behind the cisplatin (DDP) resistance of non-small cell lung cancer (NSCLC) cells to identify novel potential therapeutic targets to overcome chemoresistance. Real-time quantitative polymerase chain reaction (RT-qPCR) and Western blot assay were applied to analyze RNA and protein expression, respectively. Cell Counting Kit-8 (CCK8) assay was conducted to analyze the DDP resistance of NSCLC cells. Colony formation assay and 5-Ethynyl-2'-deoxyuridine (EdU) assay were performed to analyze cell proliferation ability. Flow cytometry was applied to assess cell apoptosis. Cell migration and invasion were assessed by transwell assays. Cell glycolytic metabolism was analyzed using commercial kits. Dual-luciferase reporter assay and RNA immunoprecipitation (RIP) assay were performed to test the intermolecular target relations. Circular RNA_0030998 (circ_0030998) was down-regulated in DDP-resistant NSCLC tissues and cell lines. Circ_0030998 overexpression restrained the DDP resistance, proliferation, migration, invasion and glycolytic metabolism and triggered the apoptosis of NSCLC cells. Circ_0030998 overexpression contributed to the anti-tumor effect of DDP in the growth of xenograft tumor in vivo. MicroRNA-1323 (miR-1323) was a molecular target of circ_0030998 in NSCLC cells. Circ_0030998 overexpression-mediated effects on the DDP resistance and malignant properties of NSCLC cells were largely based on its negative regulation of miR-1323. MiR-1323 interacted with programmed cell death 4 (PDCD4). Circ_0030998 positively regulated PDCD4 expression partly through sponging miR-1323. MiR-1323 silencing restrained DDP resistance and progression of NSCLC partly through up-regulating PDCD4. Circ_0030998 suppressed DDP resistance and NSCLC progression depending on the regulation of miR-1323/PDCD4 axis.

Security Analysis of Sending or Not-Sending Twin-Field Quantum Key Distribution with Weak Randomness.

Sending-or-not sending twin-field quantum key distribution (SNS TF-QKD) has the advantage of tolerating large amounts of misalignment errors, and its key rate can exceed the linear bound of repeaterless quantum key distribution. However, the weak randomness in a practical QKD system may lower the secret key rate and limit its achievable communication distance, thus compromising its performance. In this paper, we analyze the effects of the weak randomness on the SNS TF-QKD. The numerical simulation shows that SNS TF-QKD can still have an excellent performance under the weak random condition: the secret key rate can exceed the PLOB boundary and achieve long transmission distances. Furthermore, our simulation results also show that SNS TF-QKD is more robust to the weak randomness loopholes than the BB84 protocol and the measurement-device-independent QKD (MDI-QKD). Our results emphasize that keeping the randomness of the states is significant to the protection of state preparation devices.

Selectively Regulating Lewis Acid-Base Sites in Metal-Organic Frameworks for Achieving Turn-On/Off of the Catalytic Activity in Different CO2 Reactions.

Regulating Lewis acid-base sites in catalysts to investigate their influence in the chemical fixation of CO2 is significant but challenging. A metal-organic framework (MOF) with open metal Co sites, {(NH2 Me2 )[Co3 (µ3 -OH)(BTB)2 (H2 O)]⋅9 H2 O⋅5 DMF}n (1), was obtained and the results of the catalytic investigation show that 1 can catalyze cycloaddition of CO2 and aziridines to give 99 % yield. The efficiency of the cyclization of CO2 with propargyl amines is only 32 %. To improve the catalytic ability of 1, ligand XN with Lewis base sites was introduced into 1 and coordinated with the open Co sites, resulting in a decrease of the Lewis acid sites and an increase in the Lewis base sites in a related MOF 2 ({(NH2 Me2 )[Co3 (µ3 -OH)(NHMe2 )(BTB)2 (XN)]⋅8 H2 O⋅4 DMF}n ). Selective regulation of the type of active centers causes the yield of oxazolidinones to be enhanced by about 2.4 times, suggesting that this strategy can turn on/off the catalytic activity for different reactions. The catalytic results from 2 treated with acid solution support this conclusion. This work illuminates a MOF-construction strategy that produces efficient catalysts for CO2 conversion.

A Facile Strategy to Obtain Low-Cost and High-Performance Gold-Based Catalysts from Artificial Electronic Waste by [Zr48 Ni6 ] Nano-Cages in MOFs for CO2 Electroreduction to CO.

Expensive gold-based catalysts are frequently used for electrochemical CO2 reduction into CO. A feasible approach to obtain low-cost Au-based catalysts is needed. Herein, a novel framework 1 assembled from [Zr48 Ni6 ] nano-cages is prepared. It exhibits a high BET surface area of 1569 m2 g-1 and high solvents/pH stability. 1 can not only selectively extract AuCl4 - from artificial electronic waste, but can then be transformed into low-cost catalyst Au nanoparticle@1-x (Au NPs@1-x, x=1, 2, 3, 4) with tuneable Au NPs sizes. The CO2 RR investigations revealed that the Au NPs@1-3 displayed an excellent FECO of 95.2 % with a current density of 102.9 mA cm-2 at -1.1 V, and such high catalytic activity can be maintained for at least 15 h without obvious decrease because the confinement effect of [Zr48 Ni6 ] nano-cages prevents Au NPs agglomeration. This work offers a facile strategy to obtain low-cost and high-performance Au-based catalysts for various reactions activated by Au.

Applications of MOFs as Luminescent Sensors for Environmental Pollutants.

The environmental pollution has become a serious issue because the pollutants can cause permanent damage to the DNA, nervous system, and circulating system, resulting in various incurable diseases, such as organ failure, malformation, angiocardiopathy, and cancer. The effective detection of environmental pollutants is urgently needed to keep them far away from daily life. Among the reported pollutant sensors, luminescent metal-organic frameworks (LMOFs) with tunable structures have attracted remarkable attention to detect the pollutants because of their excellent selectivity, sensitivity, and recyclability. Although lots of metal-organic framework (MOF)-based luminescent sensors have been summarized and discussed in previous reviews, the detection of environmental pollutants, especially radioactive ions and heavy metal ions, still have not been systematically presented. Here, the sensing mechanisms and construction principles of luminescent MOFs are discussed, and the state-of-the-art MOF-based luminescent sensors of environmental pollutants, including pesticides, antibiotics, explosives, VOCs, toxic gas, toxic small molecules, radioactive ions, and heavy metal ions are highlighted. This comprehensive review may further guide the development of luminescent MOFs and promote their practical applications for sensing environmental pollutants.

Recent progress towards the transition-metal-catalyzed Nazarov cyclization of alkynes via metal carbenes.

In recent years, transition-metal-catalyzed tandem cyclization reactions of alkynes, especially those involving a metal carbene intermediate, have received worthwhile interest, as this type of reaction does not require the use of risky and potentially explosive diazo compounds as starting materials for carbene generation. A significant and general strategy for the stereospecific synthesis of 5-membered cycles is Nazarov cyclization based on the 4π-conrotatory electrocyclization of a conjugated pentadienyl cation to afford a cyclopentenyl cation. In this review, we introduce an overview of recent advances in the transition-metal-catalyzed Nazarov cyclization of alkynes via a metal carbene intermediate, and categorize these reactions according to the structure of the metal carbene. Our aim is to accelerate advancements in this enchanting area of research.

A Facile Strategy for Constructing a Carbon-Particle-Modified Metal-Organic Framework for Enhancing the Efficiency of CO2 Electroreduction into Formate.

Electrocatalytic reduction of CO2 by metal-organic frameworks (MOFs) has been widely investigated, but insufficient conductivity limits application. Herein, a porous 3D In-MOF {(Me2 NH2 )[In(BCP)]⋅2 DMF}n (V11) with good stability was constructed with two types of channels (1.6 and 1.2 nm diameter). V11 exhibits moderate catalytic activity in CO2 electroreduction with 76.0 % of Faradaic efficiency for formate (FEHCOO- ). Methylene blue molecules of suitable size and pyrolysis temperature were introduced and transformed into carbon particles (CPs) after calcination. The performance of the obtained CPs@V11 is significantly improved both in FEHCOO- (from 76.0 % to 90.1 %) and current density (2.2 times). Control experiments show that introduced CPs serve as accelerant to promote the charges and mass transfer in framework, and benefit to sufficiently expose active sites. This strategy can also work on other In-MOFs, demonstrating the universality of this method for electroreduction of CO2 .

Green Conversion of CO2 and Propargylamines Triggered by Triply Synergistic Catalytic Effects in Metal-Organic Frameworks.

Cyclization of propargylamines with CO2 to obtain 2-oxazolidone heterocyclic compounds is an essential reaction in industry but it is usually catalyzed by noble-metal catalysts with organic bases as co-catalysts under harsh conditions. We have synthesized a unique CuI /CuII mixed valence copper-based framework {[(CuI 6 I5 )Cu3 II L6 (DMA)3 ](NO3 )⋅9DMA}n (1) with good solvent and thermal stability, as well as a high density of uncoordinated amino groups evenly distributed in the large nanoscopic channels. Catalytic experiments show that 1 can effectively catalyze the reaction of propargylamines with CO2 , and the yield can reach 99 %. The turnover frequency (TOF) reaches a record value of 230 h-1 , which is much higher than that of reported noble-metal catalysts. Importantly, this is the first report of heterogeneously catalyzed green conversion of propargylamines with CO2 without solvents and co-catalysts under low temperature and atmospheric pressure. A mechanistic study reveals that a triply synergistic catalytic effect between CuI /CuII and uncoordinated amino groups promotes highly efficient and green conversion of CO2 . Furthermore, 1 directly catalyzes this reaction with high efficiency when using simulated flue gas as a CO2 source.

Highly Sensitive and Selective Luminescence Sensor Based on Two-Fold Interpenetrated MOFs for Detecting Glutamate in Serum.

Glutamate is a biomarker for many nervous system diseases, and sensitively detecting glutamate is meaningful in the clinic. Therefore, a unique 3D framework of Cd-MOF (1) is synthesized and characterized. A single-crystal X-ray study reveals that it is a two-fold interpenetration (4,4)-connected framework with a PtS topology, where a large 1D rhombic channel with a size of 8 × 14 Å exists and the total potential void volume can reach 62%. Luminescence results demonstrate that 1 has good luminescence stability and can sensitively detect glutamate in water with a detection limit of 1.15 × 10-7 mol/L, which makes it the most sensitive MOF-based luminescence sensor of glutamate to date. More importantly, it also can serve as a luminescence sensor to detect glutamate in serum, and the quenching concentration needs to be only 43.1 µmol/L, which is much lower than the harmful level of glutamate (400 µmol/L) in glioma patients' blood. Compound 1 can be used at least five cycles. These results show that 1 has a potential application in monitoring glutamate in clinical scenarios.

Luminescent Detection of Colchicine by a Unique Indium-Organic Framework in Water with High Sensitivity.

Colchicine is highly toxic to creatures, and sensitively detecting colchicines is of profound significance in the pharmaceutical, clinical, food, and breeding industries. We herein designed and constructed a unique luminescent indium-organic framework {[(CH3)2NH2][In(L)]·9DMF}n (V105) via an in situ ligand-mediated method, which possesses a 2-fold interpenetrated 3D anionic framework. Due to the large channels that exist in the framework with the size of 12 Å × 14 Å, V105 can rapidly remove harmful cationic dyes from water in a few minutes. Importantly, luminescent experiments demonstrate that V105 can selectively detect colchicine with high sensitivity in water, and the limit of detection can reach 1.0 × 10-7 M. To our knowledge, this is the first example of a metal-organic framework-based luminescent sensor for detecting colchicine.

Triple-Interpenetrated Lanthanide-Organic Framework as Dual Wave Bands Self-Calibrated pH Luminescent Probe.

pH value is a key parameter in reflecting the health status, reaction process, and water quality. The construction of highly sensitive pH luminescent ratiometric is important but challenging. Herein we designed and synthesized a unique triple-interpenetrated luminescent lanthanide-organic framework {[Eu(PPTA)0.5(NO3)(DMF)2]·H2O} n(V104) based on an amphoteric ligand 4,4',4'',4'''-(1,4-phenylenebis(pyridine-4,2,6-triyl))tetrabenzoic acid (H4PPTA). Compound V104 possesses high solvent and acid/alkaline stabilities. Luminescent investigations reveal that V104 exhibits dual emission peaks at 390 and 480 nm, and these two peaks can separately detect OH- and H+ among various anions and cations. Importantly, V104 can serve as a self-calibrated pH ratiometric to quantitatively detect pH value, and the sensitivity can reach 403.2% per pH for OH-, and 129.5% per pH for H+. Furthermore, by encapsulating magnetic γ-Fe2O3 nanoparticles in V104, the pH sensor can be readily separated from the analyte by external magnet and recycled at least four times, suggesting as-synthesized γ-Fe2O3@V104 has potential for monitoring pH fluctuations in water. To our knowledge, this is the first self-calibrated ratiometric pH-sensor based on two responsive wave bands which can separately detect OH- and H+.

A Noble-Metal-Free Metal-Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO2 with Propargylic Alcohols.

Cyclization of propargylic alcohols with CO2 is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO2 without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between CuI and InIII plays a key role in the conversion of CO2 .

Interpenetration-Dependent Luminescent Probe in Indium-Organic Frameworks for Selectively Detecting Nitrofurazone in Water.

Two novel anionic In-MOFs V101 and V102 were synthesized and structurally characterized. The structrual transformation from 2-fold interpenetration to noninterpenetration was completed by changing solvent from DMF to DEF. Luminescence investigations reveal that only V102 not V101 can sensitively and selectively detect traces of antibiotics nitrofurazone in water solution via an environmentally friendly manner, and the detection limit can reach to 0.2 ppm. The luminescent difference between V101 and V102 mainly originates from the divergence of interpenetration structures. Namely, through interpenetration-control, the luminescent probe can switch on or off to detect nitrofurazone. This is the first example of interpenetration-dependent MOFs-based luminescent probe.