Two novel Co (II)-coordination polymers as bifunctional materials for efficient photocatalytic degradation of dyes and electrocatalytic water oxidation

Two novel Co (II)- coordination polymers (CPs) based on 2,5-bis(4-carboxylpheny)-1,3,4-oxadiazole (bcpo), namely [Co/(bcpo)_0.5(tib)(H₂O)₂]_n (1) and [Co (bcpo)_0.5(bidpe)(H₂O)₂]_n (2) (tib = 1,3,5-tirs(1-imidazolyl)benzene, bidpe = 4,4′-bis (imidazolyl)diphenyl ether) have been synthesized under solvothermal conditions and characterized by powder X-ray diffraction (PXRD), single crystal X-ray diffraction, photochemistry as well as electrochemistry. The investigation of the photo-degradation methyl blue and methyl violet (MB, MV) properties of CPs 1–2 demonstrates that CP 1 shows great performance for the degradation of MB, and CP 2 could efficiently degrade MB/MV. Meanwhile, the possible photo-degradation mechanism has been proposed and explored. Simultaneously, electrochemistry studies show that both CPs 1 and 2 can catalyze water oxidation under an alkaline condition at the potential around 1.20 V vs. NHE with relatively low overpotential of 330–510 mV vs. NHE.     

Metal-Free,Visible-Light-Induced Selective C−C Bond Cleavage of Cycloalkanones with Molecular Oxygen

A metal-free, visible-light-induced oxidative C−C bond cleavage of cycloketones with molecular oxygen is described. Cooperative Brønsted-acid catalysis and photocatalysis enabled selective C−C bond cleavage of cycloketones to generate an array of γ-, δ- and ϵ-keto esters under very mild conditions. Mechanistic studies indicate that singlet molecular oxygen (¹O₂) is responsible for this transformation.     

二氧化硅包覆芒硝基相变储能微胶囊制备及性能表征

将四乙氧基硅烷(TEOS)和3-氨丙基三乙氧基硅烷(APTES)作为硅源,芒硝基相变储能微胶囊作为芯材,通过乳液聚合的方法制备了二氧化硅包覆的芒硝基相变储能微胶囊.测得芒硝基相变储能微胶囊的熔化焓和凝固焓分别为136.4 J/g和76.9 J/g,融化和凝固温度分别为23.6℃和17.6℃.微胶囊的核-壳结构减轻了无机水合盐固液分离程度,抑制了相分层现象的发生.在100次循环后,熔化焓为64.3 J/g,具有较好的循环稳定性,可用于热能存储等领域.     

Biodegradable Black-Phosphorus-Nanosheet-Based Nanoagent for Enhanced Chemo-Photothermal Therapy

Black phosphorus nanosheet (BPNS) is a promising multifunctional material in the biomedical field with biodegradability and low side effects, however its features are always weakened severely owing to its poor stability. Here, a novel method is developed for improving the defect of BPNS based on the effective protection of poly(lactic-co-glycolic acid) (PLGA), which preserves the stable photothermal therapy (PTT) effect of BPNS and biodegradability of the material. Meanwhile, doxorubicin (DOX) is loaded on BPNS/PLGA to get BPNS/PLGA/DOX for further chemotherapy and preventing the recurrence of tumor after PTT. The presented combined therapeutic strategy exploits the strengths and improves the defects of BPNS, thus developing an efficient and safe nanoagent for cancer therapy, which affords and reveals the great potential of BPNS in nanomedicine.     

Cephalotanins A–D,Four Norditerpenoids Represent Three Highly Rigid Carbon Skeletons from Cephalotaxus sinensis

Four polycyclic norditerpenoids, cephalotanins A–D ( 1 – 4 ) representing three unprecedented carbon skeletons with highly rigid ring systems, were isolated from Cephalotaxus sinensis and structurally characterized by a combination of various methods. Compounds 1 and 2 are new skeletal norditerpenoid trilactones, while 3 and 4 are two norditerpenoids featuring different new carbon skeletons. Biosynthetic pathways for 1 – 4 were proposed by involving diverse and very fascinating chemical events with the coexisting cephalotane troponoids as the precursors. Compound 1 exhibited good NF‐κB inhibition with an IC₅₀ value of 4.12±0.61 μΜ.     

Metal‐Free Reaction of ortho‐Carbonylated Alkynyl‐Substituted Arylaldehydes with Common Amines: Selective Access to Functionalized Isoindolinone and Indenamine Derivatives

Herein we describe a reaction of ortho‐carbonylated alkynyl‐substituted arylaldehydes with common primary amines that can provide functionalized isoindolinone and 3‐hydroxylindenamine products in high yields. Depending on the substituent size of primary amines, two distinct reaction pathways were exploited selectively, that are, an initial aza‐conjugate addition followed by hydrogen transfer to access isoindolinone framework and a unique oxa‐conjugate addition followed by Petasis–Ferrier rearrangement to afford indenamine derivatives. In the presence of Et₃N, the reaction property of small primary amines was changed, proceeding to afford 3‐hydroxylindenamine derivatives efficiently. These products contain interesting substructures that exist in many natural products and bioactive molecules. The reaction features contain the use of transition‐metal‐free catalysts, simple operation, broad substrate scope, and product diversity.     

Copper‐Catalyzed Reaction Cascade of Thiophenol Hydroxylation and S‐Arylation through Disulfide‐Directed C−H Activation

Copper‐catalyzed thiophenol C?H activation is described. Through an initial attempt to conduct C‐arylation with arylboronic acid, a rather surprising sequential C?H activation and S‐arylation was discovered. Mechanistic investigation revealed the disulfide intermediate as the key component in directing C?H oxidation. The overall reaction proceeded under mild conditions with molecular oxygen as the oxidant. Discovery of disulfide as the directing group provides a potential new direction for catalytic C?H functionalization under mild conditions.     

Getting to the bottom morphology of block copolymer thin films

We demonstrate a general approach for attaining the bottom morphology of block copolymer(BCP) thin films. In our former measurements on PS-b-PMMA films, surface morphology maps of the BCP films revealed distinct ordering regimes where the cylinders orient predominantly perpendicular or parallel to the interface and an ‘intermediate' regime where these morphologies coexist. However, this earlier work did not explore the bottom morphology of BCP thin films. In this study, we investigated the block copolymer morphology near the solid substrate in the cast block copolymer film having a perpendicular cylinder morphology on the surface.     

Generation of Oxazolidine‐2,4‐diones Bearing Sulfur‐Substituted Quaternary Carbon Atoms by Oxothiolation/Cyclization of Ynamides

A novel method for metal‐free oxothiolation of ynamides to construct oxazolidine‐2,4‐diones bearing sulfur‐substituted quaternary carbon atoms has been developed. It represents a rare C?O bond cleavage of ynamides, as well as a facile and tandem approach for the formation of C?O, C?S, and C?Cl bonds. This redox‐neutral protocol can be applied to the synthesis of multisubstituted oxazolidine‐2,4‐diones with good chemoselectivity and good yields of isolated products under mild conditions.