Visible light-driven acridone catalysis for atom transfer radical polymerization

Acridone as a new kind of visible light photocatalyst has been developed to catalyze metal free atom transfer radical polymerization (ATRP). The photocatalyst possess low excited state potential as can undergo an oxidative quenching pathway to initiate ATRP of vinyl monomers. Kinetic study and light on/off reaction demonstrate the “living”/controlled nature of the polymerization by light. Block copolymers can be achieved by using PMMA as macroinitiator to reinitiate polymerization of other vinyl monomers, which shows highly preserved Br chain-end functionality in the synthesized polymers. Moreover, the polymerization can be conducted under air atmosphere as most photocatalysts need anaerobic condition, which may give inspiration of further application of this kind of photocatalyst.     

自掺杂SnO2微球的水热合成及其可见光催化性能

本研究采用水热法,以柠檬酸为螯合剂,通过控制n(Sn⁴⁺)/n(Sn²⁺)的数值,合成了由具有丰富氧空位的SnO₂纳米晶体组装成的微球。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)及UV-Vis漫反射光谱对SnO₂纳米微球进行表征分析,结果表明:在酸性水热条件和柠檬酸的螯合作用下,二氧化锡纳米晶体聚集形成微球;在Sn⁴⁺/Sn²⁺摩尔比例为3:7时,其微球尺寸最小,整体分散性较好;同时适量二价锡离子的掺杂使得该样品氧空位浓度达到最佳,氧空位的存在将使得样品光吸收范围拓展至可见光,因而该样品显示出较强的可见光催化效率,在8 min内完全降解甲基橙。     

Quantum Watermark Algorithm Based on Maximum Pixel Difference and Tent Map

International Journal of Theoretical Physics - A new quantum watermark algorithm is presented by combining maximum pixel difference partitioning with the least significant bit substitution...     

Asymmetric nonlinear-mode-conversion in an optical waveguide withPT symmetry

Asymmetric mode transformation in waveguide is of great significance for on-chip integrated devices with one-way effect, while it is challenging to achieve asymmetric nonlinear-mode-conversion (NMC) due to the limitations imposed by phase-matching. In this work, we theoretically proposed a new scheme for realizing asymmetric NMC by combining frequency-doubling process and periodic PT symmetric modulation in an optical waveguide. By engineering the one-way momentum from PT symmetric modulation, we have demonstrated the unidirectional conversion from pump to second harmonic with desired guided modes. Our findings offer new opportunities for manipulating nonlinear optical fields with PT symmetry, which could further boost more exploration on on-chip nonlinear devices assisted by non-Hermitian optics.     

Sulfonylation of 1,4-Diazabicyclo[2.2.2]octane: Charge-Transfer Complex Triggered C−N Bond Cleavage

A novel charge-transfer complex triggered sulfonylation of 1,4-diazabicyclo[2.2.2]octane (DABCO) with mild reaction conditions has been developed. The formation of a charge-transfer complex between electron-withdrawing (hetero)aryl sulfonyl chloride and DABCO allows the synthesis of N-ethylated piperazine sulfonamide in good yields. The reaction has a high functional group tolerance. Spectroscopic studies confirmed the charge-transfer complex formation between sulfonyl chlorides and DABCO, which facilitates the C−N bond cleavage of DABCO.     

Preparation of erythromycin imprinted polymer by metal-free visible-light–induced ATRP and its application in sensor

Journal of Solid State Electrochemistry - Erythromycin (ERY) molecular imprinted polymer was prepared on the surface of Au electrode modified with Ni and Au nanoclusters (MIP/AuNCs/Ni/Au) via...     

Aluminum alkoxy-catalyzed biomass conversion of glucose to 5-hydroxymethylfurfural: Mechanistic study of the cooperative bifunctional catalysis

Density functional theory calculations were performed to understand the detailed reaction mechanism of aluminum alkoxy-catalyzed conversion of glucose to 5-hydroxymethylfurfural (HMF) using Al(OMe)₃ as catalyst. Potential energy surfaces were studied for aggregates formed between the organic compounds and Al(OMe)₃ and effects of the medium were considered via continuum solvent models. The reaction takes place via two stages: isomerization from glucose to fructose (stage I) and transformation of fructose to HMF (stage II). Stage II includes three successive dehydrations, which begins with a 1,2-elimination to form an enolate (i.e., B), continues with the formation of the acrolein moiety (i.e., D), and ends with the formation of the furan ring (i.e., HMF). All of these steps are facilitated by aluminum alkoxy catalysis. The highest barriers for stage I and stage II are 23.9 and 31.2 kcal/mol, respectively, and the overall catalytic reaction is highly exothermic. The energetic and geometric results indicate that the catalyzed reaction path has feasible kinetics and thermodynamics and is consistent with the experimental process under high temperature (i.e., 120 °C). Remarkably, the released water molecules in stage II act as the product, reactant, proton shuttle, as well as stabilizer in the conversion of fructose to HMF. The metal–ligand functionality of the Al(OMe)₃ catalyst, which combines cooperative Lewis acid and Lewis base properties and thereby enables proton shuttling, plays a crucial role in the overall catalysis and is responsible for the high reactivity. © 2019 Wiley Periodicals, Inc.     

Manipulating the Stacking of Triplet Chromophores in the Crystal Form for Ultralong Organic Phosphorescence

Provided here is evidence showing that the stacking between triplet chromophores plays a critical role in ultralong organic phosphorescence (UOP) generation within a crystal. By varying the structure of a functional unit, and different on‐off UOP behavior was observed for each structure. Remarkably, 24CPhCz, having the strongest intermolecular interaction between carbazole units exhibited the most impressive UOP with a long lifetime of 1.06 s and a phosphorescence quantum yield of 2.5 %. 34CPhCz showed dual‐emission UOP and thermally activated delayed fluorescence (TADF) with a moderately decreased phosphorescence lifetime of 770 ms, while 35CPhCz only displayed TADF owing to the absence of strong electronic coupling between triplet chromophores. This study provides an explanation for UOP generation in crystal and new guidelines for obtaining UOP materials.