Latest ArticlesDue to the serious harm of diabetes to human health, development of sensitive assays for glucose level is of high significance for early prevention and treatment of diabetes. Currently, most conventional enzyme-based glucose sensors suffer from high cost and low stability due to the inherent defects of natural enzymes. Herein, we develop a pure nanozyme-based glucose detection method using Ag@Au core/shell triangular nanoplates (TNPs), which combines glucose oxidase (GOD)-and horseradish peroxidase (HRP)-like activities of the Au shell and inherent plasmonic properties of Ag TNPs. The sensing mechanism is based on the fact that the Au shell possessed GOD-like activity, enabling the oxidation of glucose to produce H2O2, which can further etch the silver core, leading to the decrease of absorbance at 800 nm and the color change from blue to colorless. Compared with the previous nanozymes-based glucose sensors, our method avoids the use of enzymes and organic chromogenic agent. Moreover, the stability of the Ag@Au core/shell TNPs is much better than that of Ag TNPs due to the protection by the coating of the Au shell. This method was successfully applied to the detection of urine samples from patients with diabetes, indicating its practical applicability for real sample analysis.
The rigidity of nanoparticles was newly reported to influence their oral delivery. Semi-elastic nanoparticles can enhance the penetration in mucus and uptake by epithelial cells. However, it is still challenging and unclear that the semi-elastic core-shell nanoparticles can enhance the oral bioavailability of peptide drugs. This study was for the first time to validate the semi-elastic coreshell poly(lactic-co-glycolic acid) (PLGA)-lipid nanoparticles (LNPs) as the carrier of the oral peptide drug. The antihypertensive peptide Val-Leu-Pro-Val-Pro (VP5) loaded LNPs (VP5-LNPs) were prepared by a modified thin-film ultrasonic dispersion method. Uptake experiment was performed in Caco-2 and HT-29 cells and monitored by high content screening (HCS) and flow cytometric (FCM). Pharmacokinetics of VP5-LNPs was carried out in Sprague-Dawley (SD) rats and analyzed by DAS 2.0. The optimal VP5-LNPs had an average particle size of 247.3±3.8 nm, zeta potential of -6.57±0.45 mV and excellent entrapment efficiency (EE) of 89.88%±1.23%. Transmission electron microscope (TEM) and Differential scanning calorimeter (DSC) further confirmed the core-shell structure. VP5-LNPs could increase the cellular uptake in vitro and have a 2.55-fold increase in AUC0-72 h, indicating a great promotion of the oral bioavailability. The semi-elastic LNPs remarkably improved the oral availability of peptide and could be a promising oral peptide delivery system for peptide drugs in the future.
Dracomolphesin A-E (1-5), five 3, 4-seco-phenylpropanoids featuring an aromatic ring opened framework, were isolated from the aerial parts of Dracocephalum moldavica. The structures with absolute configurations were determined by spectroscopic methods coupled with Mosher method. Notably, these compounds represented an example of aromatic ring cleavage products of phenylpropanoids. The possible biosynthetic pathway of these compounds was proposed. Compounds 1, 2, 4 and 5 were demonstrated to be Nrf2 pathway activators.
Mesoporous semiconducting metal oxides (SMOs) heterojunctions are appealing sensors for gas detecting. However, due to the different hydrolysis and condensation mechanism of every metal precursor and the contradiction between high crystallinity and high surface area, the synthesis of mesoporous SMOs heterojunctions with highly ordered mesostructures, highly crystallized frameworks, and high surface area remains a huge challenge. In this work, we develop a novel "acid-base pair" adjusted solvent evaporation induced self-assembly (EISA) strategy to prepare highly crystallized ordered mesoporous TiO2/WO3 (OM-TiO2/WO3) heterojunctions. The WCl6 and titanium isopropoxide (TIPO) are used as the precursors, respectively, which function as the "acid-base pair", enabling the coassembly with the structure directing agent (PEO-b-PS) into highly ordered mesostructures. In addition, PEO-b-PS can be converted to rigid carbon which can protect the mesostructures from collapse during the crystallization process. The resultant OM-TiO2/WO3 heterojunctions possess primitive cubic mesostructures, large pore size (~21.1 nm), highly crystalline frameworks and surface area (~98 m2/g). As a sensor for acetone, the obtained OM-TiO2/WO3 show excellent response/recovery performance (3 s/5 s), good linear dependence, repeatability, selectivity, and long-term stability (35 days).
An ultrasensitive detection and effective removal material was successfully developed by using a pillar[n] arene-based supramolecular polymer gel (MTP5⊃HB). The MTP5⊃HB can ultrasensitively recognize Cu2+ and Fe3+, and the limits of detection (LODs) for Cu2+ and Fe3+ are 1.55 and 2.68 nmol/L, respectively. Additionally, the in-situ generated metallogel MTP5⊃HB-Cu can exclusively detect CN-, and the LOD for CN- is 1.13 nmol/L. Noticeably, the xerogel of MTP5⊃HB-Cu can effectively remove CN- from aqueous solution with 94.40% removal rate. Test kit based on MTP5⊃HB-Cu is also prepared for convenient detection of CN-.
For organnoboron compounds, the substituents on boron atoms are very important because they not only impact on the molecular stability but also significantly modulate the electronic structures and properties. In this manuscript, we synthesized two new B←N-containing azaacenes with propynyl groups on boron atoms through one-step Grignard reaction. Replacing fluorine atoms by propynyl groups greatly impacts on the electronic energy levels, especially enhancing the HOMO levels, thus leading to the narrowed HOMO-LUMO bandgaps. These B←N-containing azaacenes exhibit the NIR light-absorption (λabs=706 nm for 2a and 762 nm for 2b) and fluorescence properties (λem=740 nm for 2a and 802 nm for 2b), as well as multiple reversible redox behaviors, which are significantly different from the analogs with fluorine atoms. This study thus provides a functional substituent of boron atom, which may lead to new organoboron materials with fascinating properties.
An Ir8Pd4-heteronuclear metal-organic cage (MOC-51) was assembled from bipodal metalloligand[Ir(ppy)2(qpy)(BF4)] (qpy=4, 4':2', 2":4", 4"'-quaterpyridine; ppy=2-phenylpridine) with Pd(Ⅱ) salt. The cubic barrel shaped MOC shows one-photon and two-photon excited deep-red emission, as well as large singlet oxygen quantum yields under visible light irradiation, therefore exhibiting great potentials in organelles-targeted cell imaging and photodynamic therapy (PDT). Compared with the Ir(Ⅲ) metalloligand, the Ir8Pd4-MOC showed less dark toxicity and higher mitochondria-targeting efficiency. The localization in mitochondria overcomes the limitation of short lifetime and diffusion distance of ROS in cell, thus improved PDT effect can be obtained in low light dose usage of the MOC. This study presents the first case of Ir-based metal-organic cages for bio-applications in successful integration of imaging diagnosis and photodynamic therapy
Hyperinoids A (1) and B (2), two prenylated acylphloroglucinol related meroterpenoids, were isolated from Hypericum patulum. Compound 1 incorporates an unprecedented 11, 12-dioxatetracyclo[5.4.3.01, 7.04, 14]tetradecane system, while 2 possesses a unique 10, 11-dioxatetracyclo[5.3.3.01, 7.04, 13] tridecane system. Their structures were established by spectroscopic analysis and X-ray crystallographic data. Compounds 1 and 2 were identified as potent NF-κB inhibitors and suppressed the LPS-induced inflammatory responses in RAW 246.7 macrophages and primary mouse BMDM cells
Accurate quantitation of site-specific mRNA mutation in single cells or in peripheral blood is of great significance for both biological and biomedical studies. How to eliminate the false-positive interference from the abundant normal mRNA is still a big challenge. Herein, we have proposed an LNA (locked nucleic acid)-assisted high-specificity strategy which can selectively guide the RNase H to cleave only the wildtype mRNA (wtRNA) while the mutant mRNA (mutRNA) will remain intact. The intact mutRNA can be amplified and detected by real-time reverse transcription (RT)-PCR but the disconnected wtRNA will be not replicated at all. Based on the highly selective depletion of wtRNA, this elegant design effectively avoids the false-positive interference from the high background of normal mRNA and thus can guarantee the accurate and reliable detection of rare mutRNA in real biomedical samples. Besides for the excellent specificity, ultrahigh sensitivity is also achieved for this proposed assay, which allows the quantification of mutRNA at single molecule and single cell level. Due to its easy design, high sensitivity and specificity, the established LNA probe-assisted RT-PCR strategy provides a powerful tool for studying the function of mutRNA at the single cell level and for the mutRNA-associated liquid biopsy.
Because of their high capacity and low potential, lithium metal anodes are considered to be promising candidates for next generation electrode materials. However, the safety concerns and limited cycling life associated with uncontrollable dendrite growth hamper practical applications. In this work, the acidified cellulose ester, which is a mixed fiber microporous membrane film, was used as a novel electrolyte additive that effectively improves the cycle stability of the lithium metal anode and inhibits dendrite growth. The focus of this paper is on inhibiting the formation and growth of lithium dendrites. The coulombic efficiency of a Li|Cu battery with this acidified cellulose ester additive remains stable at 99% after 500 cycles under a current density of 1 mA/cm2. Symmetric batteries also remain stable after 500 cycles (1000 h) under a current density of 1 mA/cm2. These superior properties can be ascribed to the induced nucleation and the uniform distribution of lithium ion flux. This study uncovers an approach for effectively enabling stable cycling of dendrite-free lithium metal anodes.
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