Latest ArticlesComputational tools on top of first principle calculations have played an indispensable role in revealing the molecular details, thermodynamics, and kinetics in catalytic reactions. Here we proposed a highly efficient dynamic strategy for the calculation of thermodynamic and kinetic properties in heterogeneous catalysis on the basis of efficient potential energy surface (PES) and MD simulations. Taking CO adsorbate on Ru(0001) surface as the illustrative model system, we demonstrated the PES-based MD can efficiently generate reliable two-dimensional potential-of-mean-force (PMF) surfaces in a wide range of temperatures, and thus temperature-dependent thermodynamic properties can be obtained in a comprehensive investigation on the whole PMF surface. Moreover, MD offers an effective way to describe the surface kinetics such as adsorbate on-surface movement, which goes beyond the most popular static approach based on free energy barrier and transition state theory (TST). We further revealed that the dynamic strategy significantly improves the predictions of both thermodynamic and kinetic properties as compared to the popular ideal statistic mechanics approaches such as harmonic analysis and TST. It is expected that this accurate yet efficient dynamic strategy can be powerful in understanding mechanisms and reactivity of a catalytic surface system, and further guides the rational design of heterogeneous catalysts.
Since the discovery of aggregation induced emission (AIE) phenomenon, various stimuli-responsive materials have been rapidly developed, but there are still great challenges in the application of ink printing due to the bad water solubility. In this research, a new cationic amphiphilic TPE-functionalized pyridine salt (TPE-OTs) was designed, which shows good water solubility and hydrochromic properties. The optical properties of the compound have been studied, which is equipped with the typical AIEE characteristics and TICT effect. The compound can self-assemble to form aggregates with a particle size of about 30 nm in water. What is more, the compound is responsive to the environmental humidity, whose fluorescent color changes from green to yellow as the humidity gradually increased. Based on this characteristic, we applied it to the fluorescent anti-counterfeiting ink, realizing the protection and encryption of information.
Accurate detection of important biomarkers with ultra-low levels in complex biological matrix is one of the frontier scientific issues because of possible signal interference of potential reductive agents and protein molecules. Herein, a self-powered anti-interference photoelectrochemical (PEC) immunosensor was explored for sensitive and specific detection of model target of cardiac troponin I (cTnI). Specifically, a novel ternary heterojunction served as the photocathode to offer a remarkable current output and a zwitterionic peptide was introduced to build a robust antifouling biointerface. CuInS2 (CIS) film with porous network nanostructure was first prepared and then modified in order with ZnIn2S4 (ZIS) nanocrystals and Au nanoparticles to fabricate the Au/ZIS/CIS heterojunction photocathode. After capture cTnI antibody (Ab) was immobilized, the zwitterionic peptide KAEAKAEAPPPPC was then anchored to compete the immunosensor. The elaborated PEC immunosensor exhibited high sensitivity for target cTnI antigen (Ag) detection, with good anti-interference against reductive agents and nonspecific proteins. This integration strategy of heterojunction photocathode with zwitterionic peptide provides a new sight to develop advanced PEC immunosensors applying in practical biosamples.
Recent advances in epoxy resins have been forward to achieving high mechanical performance, thermal stability, and flame retardancy. However, seeking sustainable bio-based epoxy precursors and avoiding introduction of additional flame-retardant agents are still of increasing demand. Here we report the synthesis of p-hydroxycinnamic acid-derived epoxy monomer (HCA-EP) via a simple one-step reaction, and the HCA-EP can be cured with 4, 4′-diaminodiphenylmethane (DDM) to prepare epoxy resins. Compared with the typical petroleum-based epoxy resin, bisphenol A epoxy resin, the HCA-EP-DDM shows a relatively high glass transition temperature (192.9 ℃) and impressive mechanical properties (tensile strength of 98.3 MPa and flexural strength of 158.9 MPa). Furthermore, the HCA-EP-DDM passes the V-1 flammability rating in UL-94 test and presents the limiting oxygen index of 32.6%. Notably, its char yield is as high as 31.6% under N2, and the peak heat rate release is 60% lower than that of bisphenol A epoxy resin. Such findings provide a simple way of using p-hydroxycinnamic acid instead of bisphenol A to construct high-performance bio-based thermosets.
Cisplatin is the first-line drug for treatment of various solid tumors including breast cancer due to the broad anti-tumor spectrum and strong anti-tumor effect. However, serious side effects and long-term medication of reduced sensitivity by high GSH in tumor cells have severely restricted its further clinical application. Herein, a GSH-depleted Pt(Ⅳ) prodrug (Platin B) based on cisplatin and 4-carboxylphenylboronic acid pinacol ester was prepared to solve the problems. As an excellent GSH scavenger, 4-carboxylphenylboronic acid pinacol ester could be activated by intracellular redox reactions to release quinone methide, thereby amplifying oxidative stress and leading to breast cancer ferroptosis therapy. Interestingly, the consumption of GSH can also reduce cisplatin inactivation, enhance the sensitivity of tumor cells to cisplatin and efficiently induce apoptosis/ferroptosis. This work highlights the use of GSH scavenger for triggering ferroptotic cell death in breast cancer.
Construction of two RuⅢ cations and six lacunary Keggin fragments resulted in a novel Ru2W12-cluster {(RuO6)2(WO3)12(H2O)12} bridged polyoxometalate, NaH11[(RuO6)(AsW9O33)3{(W6O3)(H2O)6}]2 53H2O (NaH11·1·53H2O), which represent the largest cluster in all the Ru-containing polyoxometalates. The most interesting characteristic is that the symmetry-related Ru2W12-cluster-based hexamers contain two windmill-shaped [(RuO6)(AsW9O33)3{(W6O3)(H2O)6}] trimers or the Ru2W12 cluster was tightly wrapped by six segments of B-β-AsW9O33. The other remarkable feature is that there have one intriguing cubane structure: which is composed of the Ru(1, 2) and W(1, 28, 50, 51, 52, 53) atoms. The oxygenation reactions of anilines to azoxybenzenes was evaluated when NaH11·1·53H2O served as effective catalyst by probing various reaction. The inherent redox property of oxygen-rich polyoxometalate surfaces and high photocatalytic activity of the Ru-containing metal cluster imbedded in NaH11·1·53H2O provide sufficient driving force for the photocatalytic transformation from anilines to azoxybenzenes. The oxidation of anilines can be realized with higher selectivity to afford various azoxybenzene compounds. The durability test shows that Ru-doping catalyst displays excellent chemical stability during the photocatalytic process.
For more than a decade, the exfoliation of graphene and other layered materials has led to a tremendous amount of research in two-dimensional (2D) materials, among which 2D transition metal chalcogenides (TMCs) nanomaterials have attracted much attention in a wide range of applications including photoelectric devices, lithium-ion batteries, catalysis, and energy conversion and storage owing to their unique photoelectric physical properties. With such large specific surface area, strong near-infrared (NIR) absorption and abundant chemical element composition, 2D TMCs nanomaterials have become good candidates in biomedical imaging and cancer treatment. This review systematically summarizes recent progress on 2D TMCs nanomaterials, which includes their synthesis methods and applications in cancer treatment. At the end of this review, we also highlight the future prospects and challenges of 2D TMCs nanomaterials. It is expected that this work can provide the readers with a detailed overview of the synthesis of 2D TMCs and inspire more novel functional biomaterials based on 2D TMCs for cancer treatment in the future.
Small-molecule organic solar cells (SMOSCs) have attracted considerable attention owing to the merits of small molecules, such as easy purification, well-defined chemical structure. To achieve high-performance SMOSCs, the rational design of well-matched donor and acceptor materials is extremely essential. In this work, two new small molecular donor materials with subtle change in the conjugated side thiophene rings are synthesized. The subtle change significantly affects the photovoltaic performance of molecular donors. Compared with chlorinated molecule MDJ-Cl, the non-chlorinated analogue MDJ exhibits decreased miscibility with the non-fullerene acceptor Y6, can more efficiently quench the excitons of Y6. As a result, a improved PCE of 11.16% is obtained for MDJ: Y6 based SMOSCs. The results highlight the importance of fine-tuning the molecular structure to achieve high-performance SMOSCs.
The conversion of methane to syngas (H2 and CO) is an important route to produce high value-added products. Oxidize methane into syngas in the absence of gaseous oxidants is an economical route. In this work, NiO-MgO composite is successfully synthesized via an impregnation method. At 764 K, methane is directly converted to syngas on the NiO-MgO without gaseous oxidants. A synergistic effect of NiO and MgO was observed, in which NiO induced lattice oxygen of MgO mobility to oxidize methane and suppressed the formation of intermediates for side reaction. As a result, NiO-MgO exhibited enhancement of catalytic activity with the H2 production rate of 1241.0 μmol g-1 min-1, which was 3.4 times higher than that of pure MgO. This work provides a direct guidance to understand of methane oxidation via lattice oxygen under low temperature (< 773 K).
Divergent synthesis of medium-sized rings with controllable ring sizes represents a longstanding challenge in organic synthesis. Herein, we developed a transition-metal-catalyzed switchable divergent cycloaddition of para-quinone methides and vinylethylene carbonates by controlling the steric hindrance of substituent. Different from reported alkoxide-triggered annulations, this process undergoes a regiodivergent allylation of para-quinone methides followed by 1, 6-addition reaction, providing a new route to selectively synthesize seven- to ten-membered nitrogen-containing heterocycles in high yields with excellent regioselectivities. This protocol features a broad substrate scope, wide functional group tolerance as well as operational simplicity. The reaction mechanism was investigated by conducting a series of control experiments as well as DFT calculations and the origins of the regioselectivities of the cycloaddition process were rationalized.
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