Latest ArticlesHerein, a site-selective paired electrochemical C–H oxidation of functionalized alkyl arenes promoted by nickel catalyst is disclosed. A Ni(Ⅱ)-dioxygen species formed in situ efficiently enable the oxidation process under mild conditions with a broad substrate scope with excellent functional group compatibilities, such as free carboxylic acid, aldehyde, halogen (including aryl iodide), amide and amino acid. The use of the nickel catalyst in combination with water provides a safe, green and economical method for oxidation of a range of molecules varying in complexity and drug derivatives, demonstrating its potential application in organic synthesis and the pharmaceutical industry. Reaction outcomes and mechanistic studies revealed the key role of the in situ Ni(Ⅱ)-dioxygen species for the subsequent oxidation of C(sp3)–H bonds, and short-lived reactive intermediates (aryl radical cation) was rapidly captured by the combination of a bipolar ultramicroelectrode (BUME) with nano-electrospray ionization mass spectrometry.
Lithium (Li) dendrite issue, which is usually caused by inhomogeneous Li nucleation and fragile solid electrolyte interphase (SEI), impedes the further development of high-energy Li metal batteries. However, the integrated construction of a high-stable SEI layer that can regulate uniform nucleation and facilitate fast Li-ion diffusion kinetics for Li metal anode still falls short. Herein, we designed an artificial SEI with hybrid ionic/electronic interphase to regulate Li deposition by in-situ constructing metal Co clusters embedded in LiF matrix. The generated Co and LiF both enable fast Li-ion diffusion kinetics, meanwhile, the lithiophilic properties of Co clusters can serve as Li-ion nucleation sites, thereby contributing to uniform Li nucleation and non-dendritic growth. As a result, a dendrite-free Li deposition with a low overpotential (16.1 mV) is achieved, which enables an extended lifespan over 750 h under strict conditions. The full cells with high-mass-loading LiFePO4 (11.5 mg/cm2) as cathodes exhibit a remarkable rate capacity of 84.1 mAh/g at 5 C and an improved cycling performance with a capacity retention of 96.4% after undergoing 180 cycles.
Chiroptical switches based on circularly polarized luminescence (CPL) have shown the promising applications in advanced information technologies. Herein, a pair of lanthanide coordination polymer enantiomers [Eu2(LR)3(BTFPO)2]n and [Eu2(LS)3(BTFPO)2]n with light-regulated CPL property are designed, which are assembled by a chiral binuclear triple-stranded Eu3+ helicates [Eu2(LR/S)3] coordinated with two photochromic triphenylphosphine oxides (BTFPO). Upon the alternative UV and 526 nm light irradiation, the complexes show the reversible photochromism, PL and CPL responses. Notably, the luminescence dissymmetry factor, glum of 5D0→7F1 (591 nm) transition shows an obvious increase from 0.19 to 0.29 before and after 275 nm light irradiation. Additionally, the emission from Eu3+ center is not completely quenched in closed-ring state due to the low photocyclization (Фo-c) quantum yield of the polymer. The partial maintenance of emissive intensity is of essential importance for the monitor of CPL signal. More importantly, the CPL photo-switching property of the complexes in solid hybrid film is maintained, and still displays the enhanced CPL emission in photostationary state. Further, the potential applications of the doping film in logic gate and anti-counterfeiting were investigated.
Organofluorine compounds are widely used in the realm of drug discovery and material science. Herein, we developed palladium catalyzed intermolecular aminofluorination and oxy-aminofluorination of gem-difluoroalkenes with N-fluorobenzenesulfonimide (NFSI), in which NFSI was used as the nitrogen source and oxidant. The reaction provides an efficient and straightforward synthesis route of a series of α-trifluoromethyl benzylic amines. Notably, three/four components oxy-aminofluorination processes were realized to give α-trifluoromethyl benzylic ether with a terminal amino group, which proceed through C(sp3)–O bond cleavage of easily available ether and simultaneous introduced a fluorine, an amino and an oxy substituent in one pot with excellent regioselectivity. The divergent reactivity not only included the incorporation of one ether molecular, but also much more challenged two ether insertion with excellent selectivity through succession C(sp3)–O bonds cleavage. This protocol allows for concise synthesis of high value amines with fluoroalkyl-substituents and selectively transformation of easily available ethers by high-valent palladium catalysis.
Ulcerative colitis (UC) is a common progressive inflammatory disease whose incidence has increased rapidly in recent years, and can develop into colorectal cancer in severe cases. There are currently no adequate or effective treatments for UC due to the fact that some patients have found suboptimal results after repeated administration, while others have experienced adverse effects. With the rapid development of nanotechnology, developing innovative colon-targeting platforms is essential to improving efficacy, reducing side effects, and improving patient compliance. In this review, we summarize the pathophysiological characteristics of UC and the most recent status of numerous nanodrug delivery systems based on different targeting mechanisms in treating UC. Oral, intravenous, and rectal drug delivery nanoparticles targeting the colon are discussed, which can provide ideas for the design of colon-targeting nanoparticles for the treatment of colon diseases, especially for the treatment of UC. Last but not least, we provide a glimpse into the future of colon-targeted delivery systems, as well as future advancements in the field.
Activated hepatic stellate cells (aHSCs), the main source of extracellular matrix deposition, are key targets in liver fibrosis. However, no effective drug specific to aHSCs has been clinically applied due to poor drug delivery efficiency. Herein, we designed a CXC chemokine receptor 4 (CXCR4)-targeted reactive oxygen species (ROS)-responsive platform AMD-Dex-ROS-responsive-sorafenib (ARS) based on natural polysaccharide and thioctic acid frame, which can deliver anti-fibrosis drug represented by sorafenib specifically to aHSCs on account of CXCR4 over-expression on aHSCs, and smartly disassemble via ROS-responsive thioketal rupture relying on high intracellular ROS in HSCs, realized on-demand drug release and effective liver fibrosis reversion. Notably, in this platform, the CXCR4 antagonist AMD3100 not only enhanced aHSCs targeting efficiency of sorafenib but also effectively magnified the aHSCs elimination of sorafenib by blocking stroma cell derived factor-1 (SDF-1)/CXCR4-induced aHSCs protection, resulting in synergistic anti-fibrosis effect. The platform provided a new approach for drug delivery system design and liver fibrosis treatment.
Diversity-oriented synthesis is a powerful and interesting synthetic tool for the rapid construction of structurally complex and privileged scaffolds from readily accessible starting materials. To date, diversity-oriented synthesis mostly relies on the employment of versatile reagents. Versatile reagents can be regulated as controllable and flexible building blocks for multipurpose utilizations. Over the past decade, a variety of multifunctional reagents have been developed. However, most versatile reagents usually need multi-step synthesis, thus restricting their wide application to a large extent. In terms of the practicalities and universalities, we prefer to pay more attention to the utilization of simple and practical versatile reagents with multiple reactivities, mainly including atropaldehyde acetals, aryl methyl ketones, vinylene carbonate, vinyl azides, aryldiazonium salts, rongalite, halodifluoromethyl compounds. Most importantly, these versatile reagents can also play different roles simultaneously in the same reaction, in which their different reactivities are converged into the final target products. Such strategy can not only offer more possibilities for the synthesis of several active pharmaceutical ingredients, but also minimize the occurrence of some side reactions by lessening the varieties of materials. Also, a perspective is given at the end of this review.
Modulating surface charge redistribution based on interface and defect engineering has been considered as a resultful means to boost electrocatalytic activity. However, the mechanism of synergistic regulation of heterojunction and vacancy defects remains unclear. Herein, a Vs-CoP-CoS2/C n-n heterojunction with sulfur vacancies is successfully constructed, which manifests superior electrocatalytic activity for oxygen evolution, as demonstrated by a low overpotential of 170 mV to reach 10 mA/cm2. The experimental results and density functional theory calculations testify that the outstanding OER performance of Vs-CoP-CoS2/C heterojunction is owed to the synergistic effect of sulfur vacancies and built-in electric field at n-n heterogeneous interface, which accelerates the electron transfer, induces the charge redistribution, and regulates the adsorption energy of active intermediates during the reaction. This study affords a promising means to regulate the electrocatalytic performance by the construction of heterogeneous interfaces and defects, and in-depth explores the synergistic mechanisms of n-n heterojunction and vacancies.
A bottleneck in biomimetic synthesis consists in the full copy of, for example, the hierarchical structure of proteins directed by weak interactions. By contrast with covalent bonds bearing definite orientation and high stability, weak intermolecular forces within a continuous dynamic equilibrium can be hardly tamed for molecular design. In this endeavor, a ligand-dominated strategy that embodies tunable electrostatic repulsion and π…π stacking was first employed to shape polyoxovanadate-based metal-organic polyhedra (VMOPs). Structural evolution involving transformation, interlock, and discovery of an unprecedented prototype of the Star of David was hence achievable. Not only as a handy tool for the primary structural control over VMOPs, these weak forces allow for an advanced management on the spatial distribution of such manmade macromolecules as well as the associated physicochemical behaviors, representing an ideal model for simulating and interpreting the conformation-function relationship of proteins.
Prostate cancer (PC) biomarker-citrate detection is clinically important to diagnose PC in early stages. Methylquinolinium iodide (Q) conjugated indole-phenylboronic acid (IB) was designed as a red-emissive QIB probe for the detection of citrate through Lewis acid–base reaction and intramolecular charge transfer (ICT) sensing mechanisms. Boronic acid acts as Lewis acid as well as citrate (Lewis base) recognition unit. The probe reacted with citrate, showing enhanced red emissions. Since the probe has excellent water solubility and great biocompatibility, practical application in biological systems is possible. Citrate was monitored precisely in the mitochondria organelle (in vitro) of living cells with a positive charge on QIB. Also, endogenous (in situ) citrate was detected quantitatively to discriminate non-cancerous and PC mice, observed strong and lower (negligible) emission intensity on non-cancerous and cancerous prostate tissues, respectively. Because, the concentration of citrate is higher in healthy prostate compared with PC prostate. Furthermore, the analysis of sliced prostate tissues can give PC-related information for clinical diagnosis to prevent and treat PC in the initial stages. Therefore, we believe that the present probe is a promising biochemical reagent in diagnosing PC.
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