Regioselective Aromatic Perfluoro-tert-butylation Using Perfluoro-tert-butyl Phenyl Sulfone and Arynes.

The selective introduction of perfluoro-tert-butyl group (PFtB, the bulkier analogue of CF3 group) into arenes has long been sought after but remains a formidable task. We herein report the first general synthetic protocol to realize aromatic perfluoro-tert-butylation. The key to the success is the identification of PFtB phenyl sulfone as a new source of PFtB anion, which reacts with arynes in a highly regioselective manner to afford perfluoro-tert-butylated arenes in high yields. The application of the method is demonstrated by the preparation of sensitive 19F-labeled NMR probes with an extraordinary resolving ability.

More than a Leaving Group: N-Phenyltrifluoroacetimidate as a Remote Directing Group for Highly α-Selective 1,2-cis Glycosylation.

The anomeric configuration can greatly affect the biological functions and activities of carbohydrates. Herein, we report that N-phenyltrifluoroacetimidoyl (PTFAI), a well-known leaving group for catalytic glycosylation, can act as a stereodirecting group for the challenging 1,2-cis α-glycosylation. Utilizing rapidly accessible 1,6-di-OPTFAI glycosyl donors, TMSOTf-catalyzed glycosylation occurred with excellent α-selectivity and broad substrate scope, and the remaining 6-OPTFAI group can be cleaved chemoselectively. The remote participation of 6-OPTFAI is supported by the first characterization of the crucial 1,6-bridged bicyclic oxazepinium ion intermediates by low-temperature NMR spectroscopy. These cations were found to be relatively stable and mainly responsible for the present stereoselectivities. Further application is highlighted in glycosylation reactions toward trisaccharide heparins as well as the convergent synthesis of chacotriose derivatives using a bulky 2,4-di-O-glycosylated donor.

Photonic Crystal of Polystyrene Nanomembrane: Signal Amplification and Low Triggered Potential Electrochemiluminescence for Tetracycline Detection.

In this work, a low triggered potential electrochemiluminescence strategy based on gold-filled photonic crystals (GPCs) electrodes composed of photonic crystals self-assembled with polystyrene spheres and gold nanoparticles embedded in the gaps of the photonic crystals was proposed. The GPCs electrodes served as the detection platform to bind antigen, and Ru(bpy)32+-COOH as a luminophore was labeled on the antibody (Ab). Then, Ru(bpy)32+-COOH/Ab was connected to the immobilized antigen on the surface of the photonic crystals by the immunoreaction to avoid direct contact with the gold nanoparticles surface. ECL emission can only be initiated by electrochemical oxidation of tripropylamine (TPrA) since Ru(bpy)32+-COOH cannot be oxidized directly on the electrode surface. The TPrA·+ and TPrA· radicals generated by the oxidation of TPrA can spread to the vicinity of Ru(bpy)32+-COOH over a short distance and react with the Ru(bpy)32+-COOH, eventually producing ECL emission. The potential of ECL emission caused by TPrA oxidation was about 300 mV lower than that caused by Ru(bpy)32+-COOH oxidation because the oxidation potential of TPrA (0.95 V vs SCE) was lower than Ru(bpy)32+-COOH (1.25 V vs SCE). Furthermore, the photonic crystals nanomembrane has the capability to enhance electrochemiluminescence. Thereafter, tetracycline antibiotic as a model compound was successfully detected via competitive immunoassay on GPCs electrodes with a detection limit of 0.075 pg/mL (S/N = 3), which has broad application prospects in the field of analysis and detection.

Synthesis of Sea Cucumber Saponins with Antitumor Activities.

Holostane glycosides are characteristic metabolites of sea cucumbers, which possess various biological activities. Here, we report the synthesis of two representative congeners, namely, pervicoside B and C, starting from lanosterol with the longest linear sequence of both 34 steps and in 0.3% overall yields. The flexible synthetic approach has enabled us to expeditiously prepare 16 analogues for preliminary studies on the key structural features influencing their antiproliferative activities against tumor cells. A simplified disaccharide is found to be as potent as natural tetrasaccharides, which can be used as a lead for future studies.

Rapid detection of Shiga toxin type II using lateral flow immunochromatography test strips of colorimetry and fluorimetry.

Two types of lateral flow immunochromatographic test strips (LFITS) using gold nanoparticles and fluorescent CdTe quantum dots (QDs) as signal labels, respectively, were developed for Shiga toxin type II (STX2) assays. Under optimal conditions, the corresponding visual detection limits were 25 ng mL-1 and 5 ng mL-1, respectively. The test results of gold based LFITS can be recognized directly by the naked eye, whereas the visualized results of CdTe QDs based LFITS can be observed by the aid of a UV lamp. Both assays showed good specificity and stability. The inexpensive LFITS were promising for the rapid clinical detection of STX2.

Hydrogen-rich saline injection into the subarachnoid cavity within 2 weeks promotes recovery after acute spinal cord injury.

Hydrogen can relieve tissue-damaging oxidative stress, inflammation and apoptosis. Injection of hydrogen-rich saline is an effective method for transporting molecular hydrogen. We hypothesized that hydrogen-rich saline would promote the repair of spinal cord injury induced by Allen's method in rats. At 0.5, 1, 2, 4, 8, 12 and 24 hours after injury, then once daily for 2 weeks, 0.25 mL/kg hydrogen-rich saline was infused into the subarachnoid space through a catheter. Results at 24 hours, 48 hours, 1 week and 2 weeks after injury showed that hydrogen-rich saline markedly reduced cell death, inflammatory cell infiltration, serum malondialdehyde content, and caspase-3 immunoreactivity, elevated serum superoxide dismutase activity and calcitonin gene-related peptide immunoreactivity, and improved motor function in the hindlimb. The present study confirms that hydrogen-rich saline injected within 2 weeks of injury effectively contributes to the repair of spinal cord injury in the acute stage.