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Nose Angioleiomyoma: A rare Source of Epistaxis.
Novel approaches for N- and O-desulfonylation under room temperature (rt) and transition-metal-free conditions have been developed. The first methodology involves the transformation of a variety of N-sulfonyl heterocycles and phenyl benzenesulfonates to the corresponding desulfonylated products in good to excellent yields using only KO t Bu in dimethyl sulfoxide (DMSO) at rt. Alternately, a visible light method has been used for deprotection of N-methyl-N-arylsulfonamides with Hantzsch ester (HE) anion serving as the visible-light-absorbing reagent and electron and hydrogen atom donor to promote the desulfonylation reaction. The HE anion can be easily prepared in situ by reaction of the corresponding HE with KO t Bu in DMSO at rt. Both protocols were further explored in terms of synthetic scope as well as mechanistic aspects to rationalize key features of desulfonylation processes. Furthermore, the HE anion induces reductive dehalogenation reaction of aryl halides under visible light irradiation.Copper nanoclusters (Cu NCs) as emerging luminescent metal NCs are gaining increasing attention owing to the comparatively low cost and high abundance of the Cu element in nature. However, it remains challenging to manipulate the optical properties of Cu NCs. Unlike most dispersed Cu NCs, whose luminescence efficiency was restricted by nonexcited relaxation, the Cu NCs confined in a porous poly-l-cysteine (poly-l-Cys) film were generated controllably with enhanced electrochemiluminescence (ECL) by in situ electrochemical reduction. Specifically, poly-l-Cys provided a porous structure to regulate the generation of Cu NCs within its holes, which not only increased the restriction on the intramolecular vibration and rotation of the ligands but also expedited the electron transfer near the electrode surface, reflecting in an enhancement of the ECL signal and efficiency. As an application of the confined Cu NCs, an ECL biosensor with high performance was constructed skillfully for highly sensitive detection of alkaline phosphatase (ALP), which adopted Cu NCs as the ECL luminophore and poly-l-Cys as a coreaction accelerator in a novel ECL ternary system (Cu NCs/S2O82-/poly-l-Cys). Furthermore, an ingenious target amplification based on the combination of a DNA walker and click chemistry was developed to convert ALP to DNA strands efficiently, achieving great improvement in the recognition efficiency. As a result, the biosensor had a low detection limit (9.5 × 10-7 U·L-1) and a wide linear range (10-8-10-2 U·L-1) for ALP detection, which showed great promise for the detection of non-nucleic acid targets and the diagnosis of diseases.A practical Cu-catalyzed oxidation of α-diazoesters to α-ketoesters using molecular oxygen as an oxidant has been developed. Both electron-poor and electron-rich aryl α-diazoesters are suitable substrates and provide the α-ketoesters in good yields. In this oxidative system, α-diazo-β-ketoesters are also compatible as substrates but unexpectedly furnish α-ketoesters via C-C bond cleavage, rather than the vicinal tricarbonyl products.Biodegradable polymers have been often used in place of conventional nondegradable polymers for industrial and medical applications. In particular, polylactide (PLA) has been regarded as a popular ecofriendly plastic and has many advantages like good biocompatibility and processability. Yet, it still has some drawbacks in mechanical properties. Here, we prepared Ti-infiltrated PLA by mimicking the gelatinous jaw of a seaworm whose mechanical properties are toggled up and down by the tiny amount of metal ions, expecting to prepare a new type of alternative. Ti induced significant chemical and microstructural changes in the PLA, which led to a notable improvement in the mechanical properties as compared to the neat PLA. The Ti-infiltrated PLA exhibited high resistance to rapid degradation. More importantly, the toxicity assessment demonstrated that the resulting PLA is still biocompatible and nontoxic. Consequently, we proved that the Ti-infiltrated PLA has high mechanical properties comparable to conventional nondegradable polymers and good biocompatibility as well as delayed biodegradability. We anticipate the current Ti-infiltrated PLA to be an ecofriendly replacement of some conventional plastics, which helps preserve a green environment.Herein, we report a convenient organocatalytic asymmetric tandem cyclization/Michael addition protocol for the synthesis of diastereomerically pure and highly enantioenriched perfluoroalkyl-containing N,O-acetal derivatives starting from racemic N-perfluoroacyl amino acids under mild conditions. This efficient atom economic reaction leads to highly enantioselective and diastereoselective construction of N,O-acetal derivatives containing oxazolone and perfluoroalkyl moieties containing vicinal quaternary and tertiary stereocenters (up to 97% yield, up to 96% ee, and up to >201 dr).Three-dimensional (3D) covalent organic frameworks (COFs) are rare because there is a limited choice of organic building blocks that offer multiple reactive sites in a polyhedral geometry. Here, we synthesized an organic cage molecule (Cage-6-NH 2 ) that was used as a triangular prism node to yield the first cage-based 3D COF, 3D-CageCOF-1. This COF adopts an unreported 2-fold interpenetrated acs topology and exhibits reversible dynamic behavior, switching between a small-pore (sp) structure and a large-pore (lp) structure. It also shows high CO2 uptake and captures water at low humidity ( less then 40%). This demonstrates the potential for expanding the structural complexity of 3D COFs by using organic cages as the building units.The interaction mechanism of (-)-epigallocatechin gallate (EGCG) with Amadori compound (Amadori rearrangement product, ARP) in xylose-alanine model reaction systems was investigated. The adducts between ARP and EGCG were identified as two ARP-EGCG isomers, two ARP-EGCG-H2O isomers, and multiple ARP-deoxypentosone (DP)-EGCG isomers. Chidamide chemical structure The structure of an isolated and purified ARP-EGCG adduct was analyzed by means of Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, liquid chromatography-time-of-flight (TOF)-mass spectrometry (LC-TOF-MS), and nuclear magnetic resonance (NMR). Using the two-dimensional NMR analyses, the structure of ARP-EGCG adducts was clarified to consist of a covalent linkage between the C12 position of the ARP and the C8 position of the A-ring of EGCG, presumably generated by the nucleophilic nature of the EGCG or aromatic substitution reactions. The results showed that slightly alkaline pH and higher temperature could facilitate this reaction. Additionally, the thermal stability of ARP-EGCG and its degradation products revealed that the decomposition pathways of this adduct altered the classic decomposition pathway of ARP, resulting in a lower browning rate and blocking the subsequent Maillard reaction.
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