The molecule‐electrode coupling plays an essential role in photoresponsive devices with photochromic molecules, and the strong coupling between the molecule and the conventional electrodes leads to/ ...the quenching effect and limits the reversibility of molecular photoswitches. In this work, we developed a strategy of using transition metal dichalcogenides (TMDCs) electrodes to fabricate the thiol azobenzene (TAB) self‐assembled monolayers (SAMs) junctions with the eutectic gallium‐indium (EGaIn) technique. The current‐voltage characteristics of the EGaIn/GaOx//TAB/TMDCs photoswitches showed an almost 100% reversible photoswitching behavior, which increased by ∼28% compared to EGaIn/GaOx//TAB/AuTS photoswitches. Density functional theory (DFT) calculations showed the coupling strength of the TAB‐TMDCs electrode decreased by 42% compared to that of the TAB‐AuTS electrode, giving rise to improved reversibility. our work demonstrated the feasibility of 2D TMDCs for fabricating SAMs‐based photoswitches with unprecedentedly high reversibility.
A strategy for fabricating molecular photoswitch devices with the combined self‐assembled monolayers and eutectic gallium‐indium techniques is reported. The current‐voltage characteristics of EGaIn/GaOx//molecule/TMDCs photoswitches exhibit reversibility as excellent as almost 100%. This work demonstrates the promise of transition metal dichalcogenides electrodes (TMDCs) to express the intrinsic molecular properties and opens a new path for the design and fabrication nanoelectronic devices.
Recent progress in addressing electrically driven single‐molecule behaviors has opened up a path toward the controllable fabrication of molecular devices. Herein, the selective fabrication of ...single‐molecule junctions is achieved by employing the external electric field. For molecular junctions with methylthio (–SMe), thioacetate (–SAc), amine (–NH2), and pyridyl (–PY), the evolution of their formation probabilities along with the electric field is extracted from the plateau analysis of individual single‐molecule break junction traces. With the increase of the electric field, the SMe‐anchored molecules show a different trend in the formation probability compared to the other molecular junctions, which is consistent with the density functional theory calculations. Furthermore, switching from an SMe‐anchored junction to an SAc‐anchored junction is realized by altering the electric field in a mixed solution. The results in this work provide a new approach to the controllable fabrication and modulation of single‐molecule junctions and other bottom‐up nanodevices at molecular scales.
The selective fabrication of single‐molecule junctions is achieved by interface engineering under the external electric field. This work offers an unprecedented opportunity to investigate single‐molecule behaviors, manipulate single‐molecule in solution, and integrate functional molecules into the specific sites of molecular devices.
•The construction of deciduous broad-leaved forest having the greatest effect.•PH, soil microbial biomass carbon, and urease activity significantly increased bacterial diversity.•PH and soil ...microbial biomass carbon and nitrogen were the key driving factors of the soil bacterial community.•Sucrase activity can promote the increase of phototrophy functional bacteria.
The karst area in southwestern China is one of the largest and continuous karst landforms in the world, and its ecosystem is highly sensitive and fragile. Appropriate vegetation restoration modes are of great significance for sustaining and improving the stability of the karst ecosystem, the dominant landform type in southwest China. Bacteria, linking soil and plants, play an important role in regulating the succession and restoration of karst vegetation. However, it remains unclear how soil bacterial communities and soil biochemical properties respond to vegetation restoration practices in karst areas. In this study, a 13-year long-term trial was performed using three planting restoration modes of deciduous broad-leaved, mixed evergreen and deciduous broad-leaved forest, and evergreen broad-leaved forests, with controls of natural enclosure. We aimed to investigate the impact of different vegetation restoration modes on the structure of soil microbial communities and their driving mechanisms using 16S rDNA Illumina sequencing, combined with the determination of 11 soil indicators and statistical models. The results showed that artificial restoration can improve soil nutrient contents, enzyme activities and microbial biomass more effectively than natural closure, which is beneficial to the rapid restoration of vegetation after abandoning of farmland. Among them, the effect of deciduous broad-leaved treatment on artificial restoration mode was better than that of mixed evergreen and deciduous broad-leaved forest and evergreen broad-leaved forest. In sequencing results, artificial restoration increased the relative abundance of Proteobacteria, but decreased that of Acidobacteria. In addition, pH, soil microbial biomass carbon, and urease activity significantly increased bacterial diversity. Different vegetation restoration measures significantly changed the soil bacterial community structure. The bacterial community of deciduous broad-leaved forest was the most beneficial to the benign development of soil. Mantel test showed that pH and soil microbial biomass carbon and nitrogen were the key driving factors of the soil bacterial community. FAPROTAX analysis showed a significant positive correlation between sucrase activity and phototrophy functional bacteria. The results demonstrated that compared with natural enclosure, artificial vegetation restoration promoted rapid community succession, and construction of deciduous broad-leaved forest was the most effective way to manage karst areas, improve soil nutrients, alter its key microbial populations, promote ecosystem services, and eventually benefit the restoration of vegetation in karst areas.
Trifluoromethyl cationic carbyne (CF3C+:) possessing dual carbene‐carbocation behavior emulated as trifluoromethyl metal‐carbynoid (CF3C+=M) has not been explored yet, and its reaction ...characteristics are unknown. Herein, a novel α‐diazotrifluoroethyl sulfonium salt was prepared and used in Rh‐catalyzed three‐component 2+1+2 cycloadditions for the first time with commercially available N‐fused heteroarenes and nitriles, yielding a series of imidazo1,5‐a N‐heterocycles that are of interest in medicinal chemistry, in which the insertion of trifluoromethyl Rh‐carbynoid (CF3C+=Rh) into C=N bonds of N‐fused heteroarenes was involved. This strategy demonstrates synthetic applications in late‐stage modification of pharmaceuticals, construction of CD3‐containing N‐heterocycles, gram‐scale experiments, and synthesis of phosphodiesterase 10A inhibitor analog. These highly valuable and modifiable imidazo1,5‐a N‐heterocycles exhibit good antitumor activity in vitro, thus demonstrating their potential applications in medicinal chemistry.
A novel α‐diazotrifluoroethyl sulfonium salt was prepared, and it was applied in Rh‐catalyzed three‐component 2+1+2 cycloadditions for the first time, affording various imidazo1,5‐a N‐heterocycles under mild conditions. This strategy involved a unique trifluoromethyl Rh‐carbynoid (CF3C+=Rh), wherein three new chemical bonds were forged at the α‐carbon of trifluoromethyl in a single step.
Aqueous zinc batteries, that demonstrate high safety and low cost, are considered promising candidates for large‐scale energy storage. However, Zn anodes suffer from rapid performance deterioration ...due to the severe Zn dendrite growth and side reactions. Herein, with a low‐cost ammonium acetate (NH4OAc) additive, a self‐regulated Zn/electrolyte interface is built to address these problems. The NH4+ induces a dynamic electrostatic shielding layer around the abrupt Zn protuberance to make the Zn deposition uniform, and the OAc− acts as an interfacial pH buffer to suppress the proton‐induced side reactions and the precipitation of insoluble by‐products. As a result, in the electrolyte with the NH4OAc additive, Zn anodes exhibit a long cycling stability of 3500 h at 1 mA cm−2, an impressive cumulative areal capacity of 5000 mAh cm−2 at 10 mA cm−2, and a high Coulombic efficiency of ≈99.7%. A prototype full cell coupled with a NH4V4O10 cathode performs much better in terms of capacity retention than the additive‐free case. The findings pave the way for developing practical Zn batteries.
A self‐regulated interface is built using a dual‐functional ammonium acetate additive to address zinc dendrite growth and proton‐induced side reactions simultaneously, thus enabling an Zn anode with long cycling stability of 3500 h, an impressive cumulative areal capacity of 5000 mAh cm−2 at 10 mA cm−2, and a high Coulombic efficiency of 99.7%.
The severe anticancer situation as well as the emergence of multidrug-resistant (MDR) cancer cells has created an urgent need for the development of novel anticancer drugs with different mechanisms ...of action. A large number of natural alkaloids, such as paclitaxel, vinblastine and camptothecin have already been successfully developed into chemotherapy agents. Following the success of these natural products, in this review, twenty-six types of isoquinoline alkaloids (a total of 379 alkaloids), including benzyltetrahydroisoquinoline, aporphine, oxoaporphine, isooxoaporphine, dimeric aporphine, bisbenzylisoquinoline, tetrahydroprotoberberine, protoberberine, protopine, dihydrobenzophenanthridine, benzophenanthridine, benzophenanthridine dimer, ipecac, simple isoquinoline, pavine, montanine, erythrina, chelidonine, tropoloisoquinoline, azafluoranthene, phthalideisoquinoline, naphthylisoquinoline, lycorine, crinane, narciclasine, and phenanthridone, were summarized based on their cytotoxic and MDR reversing activities against various cancer cells. Additionally, the structure-activity relationships of different types of isoquinoline alkaloid were also discussed. Interestingly, some aporphine, oxoaporphine, isooxoaporphine, bisbenzylisoquinoline, and protoberberine alkaloids display more potent anticancer activities or anti-MDR effects than positive control against the tested cancer cells and are regarded as attractive targets for discovery new anticancer drugs or lead compounds.
Triple‐negative breast cancer (TNBC) is the most aggressive and lethal clinical subtype and lacks effective targeted therapies at present. Isobavachalcone (IBC), the main active component of Psoralea ...corylifolia L., has potential anticancer effects. Herein, we identified IBC as a natural sirtuin 2 (SIRT2) inhibitor and characterized the potential mechanisms underlying the inhibition of TNBC. Molecular dynamics analysis, enzyme activity assay, and cellular thermal shift assay were performed to evaluate the combination of IBC and SIRT2. The therapeutic effects, mechanism, and safety of IBC were analyzed in vitro and in vivo using cellular and xenograft models. IBC effectively inhibited SIRT2 enzyme activity with an IC50 value of 0.84 ± 0.22 μM by forming hydrogen bonds with VAL233 and ALA135 within its catalytic domain. In the cellular environment, IBC bound to and stabilized SIRT2, consequently inhibiting cellular proliferation and migration, and inducing apoptosis and cell cycle arrest by disrupting the SIRT2/α‐tubulin interaction and inhibiting the downstream Snail/MMP and STAT3/c‐Myc pathways. In the in vivo model, 30 mg/kg IBC markedly inhibited tumor growth by targeting the SIRT2/α‐tubulin interaction. Furthermore, IBC exerted its effects by inducing apoptosis in tumor tissues and was well‐tolerated. IBC alleviated TNBC by targeting SIRT2 and triggering the reactive oxygen species ROS/β‐catenin/CDK2 axis. It is a promising natural lead compound for future development of SIRT2‐targeting drugs.
In the genus Macleaya, Macleaya cordata and Macleaya microcarpa have been recognized as traditional herbs that are primarily distributed in China, North America, and Europe and have a long history of ...medicinal usage. These herbs have been long valued and studied for detumescence, detoxification, and insecticidal effect. This review aims to provide comprehensive information on botanical, phytochemical, pharmacological, and toxicological studies on plants in the genus Macleaya. Plants from the genus of Macleaya provide a source of bioactive compounds, primarily alkaloids, with remarkable diversity and complex architectures, thereby having attracted attention from researchers. To date, 291 constituents have been identified and/or isolated from this group. These purified compounds and/or crude extract possess antitumor, anti‐inflammatory, insecticidal, and antibacterial activities in addition to certain potential toxicities. Macleaya species hold potential for medicinal applications. However, despite the pharmacological studies on these plants, the mechanisms underlying the biological activities of active ingredients derived from Macleaya have not been thoroughly elucidated to date. Additionally, there is a need for research focusing on in vivo medical effects of Macleaya compounds and, eventually, for clinical trials.
Preparing copper matrix composite coating on Cu substrate by laser cladding method is difficult since high thermal conductivity and low absorption rate of Cu to infrared wavelength along with the ...complex influence of multi-processing parameters. In this work, laser beam power, defocus distance, and scanning speed are considered as the key factors influencing the coating quality, and output response includes the dilution ratio, clad height as well as clad width. By establishing a regression model between processing parameters and output response, an optimized craft to prepare high-quality copper matrix composite coating on the copper substrate was finally provided. Results indicate that the clad height and width increase with enhancing laser beam power but decrease with growing scanning speed. In addition, the dilution ratio increases with enhancing scanning speed and decreasing defocus distance. The mathematical model based on response surface methodology is credible to predict the key laser cladding parameters on dilution ratio, clad height and clad width within the error of 20%. By carrying out optimization via the desirability function, the optimum parameters achieved are laser beam power 1780 W, defocus distance 8.3 mm and scanning speed 789 mm/min.
