Modular Total Synthesis of (–)‐Palmyrolide A and (+)‐(5S,7S)‐Palmyrolide A via Ring‐Closing Metathesis and Alkene Isomerization†

A pentamodule assembly approach has been established for total synthesis of the naturally occurring (–)‐palmyrolide A and (+)‐5,7‐epi‐palmyrolide A. By using the racemic tert‐butyl carbinol‐containing alkyl iodide, the two diastereoisomeric macrolides could be obtained from the same sequence of reactions, demonstrating the flexibility of the multimodule assembly strategy for diverted total synthesis.     

Two-photon dual-channel fluorogenic probe for in situ imaging the mitochondrial H2S/viscosity in the brain of drosophila Parkinson’s disease model

H₂S is an essential gas signal molecule in cells, and viscosity is a key internal environmental parameter. Recent studies have shown that H₂S acts as a cytoarchitecture agent and gas transmitter in many tissues, e.g., as a regulator of neuroendocrine in the brain for mediating vascular tone in blood vessels. Mitochondrial viscosity is an important parameter for judging whether mitochondrial function is normal. It has been reported that oxidative stress and mitochondrial dysfunction are connected with Parkinson’s disease (PD), and the protective role of H₂S in PD models has been extensively demonstrated. Herein, Mito-HS, a new two-photon fluorescent probe was demonstrated to detect cross-talk between the two channels of mitochondrial viscosity and H₂S content. Moreover, this probe could detect the relative amount of and changes in mitochondrial H₂S in situ due to the reduced mitochondrial targeting ability after reaction with H₂S. The results show that H₂S in mitochondria is inversely related to viscosity. The PD model has a lower H₂S in mitochondria and a higher mitochondrial viscosity than did the normal. This result is important for our deep understanding of PD and its causes.     

Enhanced Sensitive Electrochemical Sensor for Simultaneous Catechol and Hydroquinone Detection by Using Ultrasmall Ternary Pt-based Nanomaterial

The simple and effective method for the novel synthesis of Pt-based nanoparticle was presented with high efficiency. The sensitive catalyst for the simultaneous detection of catechol and hydroquinone was prepared by depositing ternary metal complex on fluorine-doped tin-oxide (FTO). The composition and morphology of nanomaterials were characterized by TEM, HRTEM, XRD, XPS, and EDS (energy dispersive spectroscopy). The size of the Pt-based nanomaterial was about 5±1 nm. The electrochemical performance of the modified catalyst was studied by CV, DPV, and EIS. The modified PtNiCu@FTO catalyst possessed good electro-oxidation activity for hydroquinone and catechol and used for simultaneous detection of catechol and hydroquinone at scan rate of 20 mV s⁻¹ (vs. Ag/AgCl). Detection responses were found in the ranges of 5–2900 μM for hydroquinone and 5–3000 μM for catechol. The detection limits (LOD) for HQ and CC were observed as 0.35 and 0.29 μM, respectively. The sensitivity of HQ and CC were 1515.55 and 1485 μA mM⁻¹ cm⁻², respectively. The prepared nanomaterial were effectively applied for the determination of CC and HQ in real samples.     

Surface tension of supercooled graphene oxide nanofluids measured with acoustic levitation

Journal of Thermal Analysis and Calorimetry - The surface tensions of graphene oxide nanofluids of five mass concentrations were measured by the oscillation droplet method in an acoustic levitator....     

Synthesis and Anti-Hepatocarcinoma Effect of Amino Acid Derivatives of Pyxinol and Ocotillol

Aiming at seeking an effective anti-hepatocarcinoma drug with low toxicity, a total of 24 amino acid derivatives (20 new along with 4 known derivatives) of two active ocotillol-type sapogenins (pyxinol and ocotillol) were synthesized. Both in vitro and in vivo anti-hepatocarcinoma effects of derivatives were evaluated. At first, the HepG2 human cancer cell was employed to evaluate the anti-cancer activity. Most of the derivatives showed obvious enhanced activity compared with pyxinol or ocotillol. Among them, compound 2e displayed the most excellent activity with an IC₅₀ value of 11.26 ± 0.43 µM. Next, H22 hepatoma-bearing mice were used to further evaluate the anti-liver cancer activity of compound 2e. It was revealed that the growth of H22 transplanted tumor was significantly inhibited when treated with compound 2e or compound 2e combined with cyclophosphamide (CTX) (p < 0.05, p < 0.01), and the inhibition rates of tumor growth were 35.32% and 55.30%, respectively. More importantly, compound 2e caused limited damage to liver and kidney in contrast with CTX causing significant toxicity. Finally, the latent mechanism of compound 2e was explored by serum and liver metabolomics based on ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometry (UPLC-QTOF-MS) technology. A total of 21 potential metabolites involved in 8 pathways were identified. These results suggest that compound 2e is a promising agent for anti-hepato-carcinoma, and that it also could be used in combination with CTX to increase efficiency and to reduce toxicity.     

Defect Engineering on Boron Nitride for O2 Activation and Subsequent Oxidative Desulfurization

The rational design of highly active hexagonal boron nitride (h-BN) catalysts at the atomic level is urgent for aerobic reactions. Herein, a doping impurity atom strategy is adopted to increase its catalytic activities. A series of doping systems involving O, C impurities and B, N antisites are constructed and their catalytic activities for molecular O₂ have been studied by density functional theory (DFT) calculations. It is demonstrated that O₂ is highly activated on O_N and B_N defects, and moderately activated on C_B and C_N defects, however, it is not stable on N_B and O_B defects. The subsequent application in oxidative desulfurization (ODS) reactions proves the O_N and C-doped (C_B, C_N) systems to be good choice for sulfocompounds oxidization, especially for dibenzothiophene (DBT). While the B_N antisite is not suitable for such aerobic reaction due to the extremely stable B−O^*−B species formed during the oxidation process.     

An efficient label-free immunosensor based on ce-MoS2/AgNR composites and screen-printed electrodes for PSA detection

Journal of Solid State Electrochemistry - Label-free electrochemical immunosensors (EIs) are simple and sensitive in cancer diagnosis. Electrode materials which can offer a large specific area and...     

Nickel-Catalyzed Cross-Coupling of Ethyl Chlorofluoroacetate with Aryl Bromides

A combinatorial nickel-catalyzed monofluoroalkylation of aryl bromides with the industrial raw regent ethyl chlorofluoroacetate has been developed. The two key factors to successful conversion are the combination of nickel with readily available nitrogen and phosphine ligands and the using of a mixture of different solvents. Mechanistic investigations indicated a new zinc regent might generated in situ and be involved in the reaction process.