Photoswitchable Sol–Gel Transitions and Catalysis Mediated by Polymer Networks with Coumarin-Decorated Cu24L24 Metal–Organic Cages as Junctions

Photoresponsive materials that change in response to light have been studied for a range of applications. These materials are often metastable during irradiation, returning to their pre-irradiated state after removal of the light source. Herein, we report a polymer gel comprising poly(ethylene glycol) star polymers linked by Cu₂₄L₂₄ metal–organic cages/polyhedra (MOCs) with coumarin ligands. In the presence of UV light, a photosensitizer, and a hydrogen donor, this “polyMOC” material can be reversibly switched between Cu^II, Cu^I, and Cu⁰. The instability of the MOC junctions in the Cu^I and Cu⁰ states leads to network disassembly, forming Cu^I/Cu⁰ solutions, respectively, that are stable until re-oxidation to Cu^II and supramolecular gelation. This reversible disassembly of the polyMOC network can occur in the presence of a fixed covalent second network generated in situ by copper-catalyzed azide-alkyne cycloaddition (CuAAC), providing interpenetrating supramolecular and covalent networks.     

四卤化锰(Ⅱ)配合物的结构调控及力致发光性能

力致发光是一种力刺激诱导的发光现象。由于其独特的发光方式,使得力致发光材料在结构损伤检测、压力传感、显示和安全标记等方面展现出了巨大的应用价值。目前已报道的力致发光材料大多基于无机材料体系,而有机力致发光材料体系相对较少,并且人们对其发光机理的认识仍不清晰。在本文中,我们发现锰(Ⅱ)配合物[BPP]2[Mn Br4]具有力致发光特性,并在此基础上设计合成了一系列具有力致发光性质的四卤化锰(Ⅱ)配合物。改变有机阳离子配体或者卤素阴离子可对其光物理性质进行有效调控。固态下,这些锰(Ⅱ)配合物均显示出了较强的光致发光现象,同时表现出了明显的力致发光特性。晶体结构分析表明,分子内/分子间强的C―H…X (X=Br或Cl)相互作用对锰(Ⅱ)配合物的力致发光起到了至关重要的作用,它可在较大程度上降低由分子振动和旋转造成的能量损失。本工作将为力刺激响应型材料体系的拓展提供一定的参考价值。     

Insights into the interactions between DNA and an infinite clamp-like copper (II) complex

Transition Metal Chemistry - A Cu(II) complex [Cu2(phen)2(NAB)2(HO)]n (phen?=?1, 10-phenanthroline and NABH?=?p-N, N-(2-hydroxyethyl)amino benzoic acid) was synthesized, and...     

Visible‐Light‐Enabled Stereodivergent Synthesis of E‐ and Z‐Configured 1,4‐Dienes by Photoredox/Nickel Dual Catalysis

A stereodivergent reductive coupling reaction between allylic carbonates and vinyl triflates to furnish both E‐ and Z‐configured 1,4‐dienes has been achieved by visible‐light‐induced photoredox/nickel dual catalysis. The mild reaction conditions allow good compatibility of both vinyl triflates and allylic carbonates. Notably, the stereoselectivity of this synergistic cross‐electrophile coupling can be tuned by an appropriate photocatalyst with a suitable triplet‐state energy, providing a practical and stereodivergent means to alkene synthesis. Preliminary mechanistic studies shed some light on the coupling step as well as the control of the stereoselectivity step.     

Direct diazotization of graphite nanoplatelets with melamine and their favorable application in epoxy resins

The ease of undesirable agglomeration and a low efficiency are two problems that restrict the application of graphite nanoplatelets (GNPs) in epoxy resins (EP). Herein, a new strategy with melamine (MEL) as the precursor to functionalize GNPs chemically, which form a bonding layer that is compatible with epoxy matrix, is reported. The MEL fragments with secondary amine groups were grafted uniformly on the GNPs surface by covalent junctions to exploit the diazonium chemistry. This behavior led to a better dispersion and a stronger interaction with the epoxy matrix and resulted in an enhanced glass transition temperature and bending strength, compared with the pure EP. When only 1 wt% functionalized GNPs (f‐GNPs) was used, the Tg of the modified EP raised of about 15°C compared with pure EP, and the bending strength increased by approximately 39%. The dielectric constant of the EP with f‐GNPs was impacted slightly, and the dielectric loss decreased. At 10⁵ Hz, the dielectric loss of the EP with 1 wt% f‐GNPs decreased by approximately 11% compared with pure EP. Therefore, diazotization modification of the GNPs is a useful approach to improve the compatibility in nanoparticle networks.     

Theoretical calculation on the substituent effect of strontium para-tetraphenyl porphyrins

Structural Chemistry - A series of strontium para-tetraphenyl porphyrins (SrTRPPs) with different electron property substituents (R?=?-NH2, -OCH3, -H, -F, -COOH, -NO2) on the...     

An Fe2+‐ and α‐Ketoglutarate‐Dependent Halogenase Acts on Nucleotide Substrates

While halogenated nucleosides are used as common anticancer and antiviral drugs, naturally occurring halogenated nucleosides are rare. Adechlorin (ade) is a 2′‐chloro nucleoside natural product first identified from Actinomadura sp. ATCC 39365. However, the installation of chlorine in the ade biosynthetic pathway remains elusive. Reported herein is a Fe²⁺‐α‐ketoglutarate halogenase AdeV that can install a chlorine atom at the C2′ position of 2′‐deoxyadenosine monophosphate to afford 2′‐chloro‐2′‐deoxyadenosine monophosphate. Furthermore, 2′,3′‐dideoxyadenosine‐5′‐monophosphate and 2′‐deoxyinosine‐5′‐monophosphate can also be converted, albeit 20‐fold and 2‐fold, respectively, less efficiently relative to the conversion of 2′‐deoxyadenosine monophosphate. AdeV represents the first example of a Fe²⁺‐α‐ketoglutarate‐dependent halogenase that converts nucleotides into chlorinated analogues.     

Iridoid,phenylethanoid and flavonoid glycosides from Forsythia suspensa

Abstract

As part of our continuing efforts to explore bioactive compounds from natural resources, a new iridoid glycoside, adoxosidic acid-6′-oleuroperic ester (1), together with one known phenylethanoid glycoside (2) and two known flavonoid glycosides (3–4) were isolated from the fruit of Forsythia suspensa. The structure of the new compound (1) was elucidated through 1D and 2D NMR spectroscopic data and HR-ESIMS. Interestingly, compound 1 was a monoterpene ester of one iridoid glycoside. Compounds 2–4 were identified as calceolarioside A (2), kaempferol-3-O-rutinoside (3), kampferol-3-O-robinobioside (4) on the basis of NMR spectroscopic data analyses and comparison with the data reported in the literature. The antiviral activity aganisist influenza A (H5N1) virus of compound 1 was studied as well.