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DYES AND PIGMENTS · 2021 · IF 4.889

A pH-dependent fluorescent and colouring macrocycle for the high selective detection of arginine in pure water

Kui Wang,Qi-Qi Wang,Mi-Ni Wang,Ya-Jing Xie,Xuan Qiao,Siyang Xing,Bolin Zhu

In this work, a water-soluble fluorescent and colouring macrocycle deprotonated-calixpyridinium was obtained by a simple pH modulatory strategy. This type of fluorescent and colouring macrocyclic skeleton as host will be certainly applied in a large number of fields, especially in the sensing area. Herein, a near white-light emission was carried out by an innovative method of deprotonated-calixpyridinium-based host–guest interactions employing camptothecin sodium as the guest. Moreover, the pH-responsive luminescence color change of calixpyridinium–camptothecin sodium complex was further applied for the high selective detection of arginine in pure water and real samples, which is quite important in the accurate diagnosis of various disorders. The newfound pH-dependent luminescent and colouring properties of calixpyridinium will also provide an alternative idea for the development of other novel fluorescent and colorimetric macrocyclic sensors.

研究领域: 分析化学 · 生物传感 · 医学诊断
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Science China-Chemistry · 2017 ·Vol. 60 ·期 9 ·1191-1196 · IF 4.132

Selenium containing macrocycles: transformation between Se–N/Se–S/Se–Se bonds

Ji Shaobo,El Mard Hicham,Smet Mario,Dehaen Wim,Xu Huaping

Macrocycles possess potential applications in supramolecular chemistry and biosystems. Thus development of new kinds of macrocycles is of significance. Herein, novel macrocycles containing Se–Se/Se–S bonds were synthesized via transformation between selenium related dynamic covalent bonds. A monomer containing two ebselen moieties was synthesized ( M1 ). The Se–N bonds in M1 were reduced by dithiothreitol, forming Se–S linked dimer ( D1 ). To realize the transformation from Se–S bonds to Se–Se bonds, guest molecules were added as template, triggering the formation of Se–Se linked dimer ( D2 ). The formation of these two new kinds of macrocycles was determined by 1 H NMR and 77 Se NMR, and the necessity of guest molecules was also confirmed. The introduction of ebselen moieties and Se–S bonds or Se–Se bonds into macrocycles may endow it with new responsiveness and bioactivities, as well as new types of host-guest chemistry.

研究领域: 超分子化学 · 生物化学
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DYES AND PIGMENTS · 2023 · IF 4.5

Turn-on circularly polarized luminescence for dynamical-racemic and large-hollow AIE macrocycle based on selective recognition for ursolic acid

Shibing Chen,Minqian Zhu,Xiangfei Xu,Hongyu Guo,Fafu Yang

The macrocycles with the features of large cavity, optical property and CPL response to guest simultaneously are rarely reported but very attractive based on their potential application. Herein, a macrocycle ( BiCDB-MC ) with dynamically racemic feature, inwardly directed functional groups, a large hollow with size of 1.3 nm and fluorescent property was designed and synthesized. BiCDB-MC was found to have two equally chiral conformations and was dynamically racemic in solution based on their rapidly interconvertion via macrocycle flipping. It was interesting that BiCDB-MC exhibited a selective turn-on CPL response with g lum  = 0.00248 toward ursolic acid since one of the stable chiral conformations could form a more stable inclusion complex. This kind of turn-on CPL emission for dynamical-racemic macrocycle with CPL recognition for complicated natural chiral compound was described for the first time.

研究领域: 有机化学 · 超分子化学 · 材料科学
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POLYMER · 2015 · IF 3.562

Synthesis of graft copolymer with pendant macrocycles via combination of ATRP and click chemistry

Min Li,Chao Liu,Chun-Yan Hong,Cai-Yuan Pan

Graft copolymers with pendant macrocycles were synthesized via “graft onto” method. First, cyclic polystyrene (PS) was achieved by the combination of atom transfer radical polymerization (ATRP) and Cu-catalyzed azide–alkyne cycloaddition (CuAAc), and then an alkynyl group was introduced to cyclic PS. Meanwhile, poly(3-azide-2-hydroxypropyl methacrylate) (PGMA-N 3 ) was synthesized by ATRP of glycidyl methacrylate (GMA) and successive ring-opening of pendant epoxide ring with NaN 3 . The graft copolymer was achieved by the following click reaction between PGMA-N 3 and alkynyl-containing cyclic PS. GPC and 1 H NMR were utilized to characterize the obtained graft copolymers, and a maximal grafting density of 20% was observed. Thermal behaviors of linear PS, cyclic PS and PGMA grafted with cyclic PS (PGMA-g-cPS) were investigated by differential scanning calorimeter (DSC), and T g of PGMA-g-cPS is higher than those of linear and cyclic PS.

研究领域: 高分子化学 · 材料科学
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MACROMOLECULES · 2018 · IF 5.914

Porous Organic Polymer from Aggregation-Induced Emission Macrocycle for White-Light Emission

Zhen Wang,Sen Yan,Huang-Chen Cui,Guang Cheng,Hui Ma,Qing-Mei Zhang,Qing-Pu Zhang,Jun-Min Liu,Bien Tan,Chun Zhang

A tetraphenylethylene-based oxacalixarene macrocycle (TOM) with high fluorescence quantum yield (70%) was used as monomer to construct a fluorescent macrocycle-based porous organic polymer (pTOM). With high surface area, specific pore size, and emissive properties, the blue-greenish fluorescent pTOM can be developed into white-light-emission materials by adsorbing guests of tris(bipyridine)ruthenium with complementary emission color by the Förster resonance energy transfer (FRET) effect.

研究领域: 材料科学 · 光学
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JOURNAL OF CHROMATOGRAPHY A · 2021 · IF 4.759

Fabrication and evaluation of tetraazahexaphenylmacrocycle-bonded stationary phase with multiple retention mechanisms

Junnan Li,Yaming Sun,Longhui Liu,Hailiang Zhao,Wenjie Zhao,Lijun He,Shusheng Zhang

A 34-membered tetraazahexaphenylmacrocycle (N 4 Ph 6 ) with a rigid π-conjugated moiety was chemically bonded to silica gel with 3-chloropropyltrimethoxysilane as the coupling agent to prepare a novel SiO 2 @N 4 Ph 6 stationary phase. Several common organic analytes, including alkylbenzenes , polycyclic aromatic hydrocarbons , anilines, phenols, phthalates , and folic acid , were selected as probes to investigate its chromatographic performance. The as-developed SiO 2 @N 4 Ph 6 stationary phase showed superiority retention and high selectivity for probe molecules through multiple interactions, including hydrophobic, π–π, hydrogen-bonding, and steric interactions. Density functional theory calculation results using folic acid as model solute provided an intuitive and a quantitative description of the multiple retention mechanisms.

CAS / MDL: 62-53-3 59-30-3 108-95-2
研究领域: 分析化学 · 材料科学
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ELECTROCHIMICA ACTA · 2019 · IF 5.383

How does the ligands structure surrounding metal-N4 of Co-based macrocyclic compounds affect electrochemical reduction of CO2 performance?

Bihua Hu,Weiwei Xie,Ruchun Li,Zhangweihao Pan,Shuqin Song,Yi Wang

Metal-N x -C based materials have emerged as one of the most promising electrocatalysts for electrochemical reduction of carbon dioxide (ERCD). Co-based macrocyclic compounds have shown unique performance, however, of which the relationship between the ligands structure surrounding Co–N 4 centers and reaction mechanism remains vague. To explore this issue, here, a series of Co-based macrocyclic compounds are elaborately chosen as model catalysts, including phthalocyanine cobalt (CoPc), cobalt (II) meso-Tetraphenylporphine (CoTp) and cobalt tetramethoxyphenylporphyrin (CoTop), which possess well-defined Co-N 4 coordinated centers but different ligands structure surrounding Co-N 4 . Electrochemical measurements show that CoPc possesses higher activity and selectivity for CO with Faradaic efficiency (FE) above 62% at −0.7 V ( vs. RHE) relative to those of CoTp and CoTop. Combining density functional theory (DFT) calculations, it can be further confirmed that CoPc is more favorable for ERCD to CO due to the rapid formation of key intermediate COOH* and the desorption of CO, demonstrating that the structure of ligands (phthalocyanine) surrounding Co-N 4 plays a crucial role in the high CO selectivity. It can be anticipated that an exclusive strategy will pave a new avenue for further understanding the ERCD mechanism of Co-N x -C catalysts.

研究领域: 材料科学 · 电催化 · 理论计算
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BIOCONJUGATE CHEMISTRY · 2024 · IF 4

Legumain-Triggered Macrocyclization of Radiofluorinated Tracer for Enhanced PET Imaging

Xiaoqing Gao,Qianhui Wang,Xiaofeng Yang,Jing Fang,Huirong Li,Hongjie Xi,Jianguo Lin,Ling Qiu

Enhancing the accumulation and retention of small-molecule probes in tumors is an important way to achieve accurate cancer diagnosis and therapy. Enzyme-stimulated macrocyclization of small molecules possesses great potential for enhanced positron emission tomography (PET) imaging of tumors. Herein, we reported an 18F-labeled radiotracer [18F]AlF-RSM for legumain detection in vivo. The tracer was prepared by a one-step aluminum-fluoride-restrained complexing agent ([18F]AlF-RESCA) method with high radiochemical yield (RCY) (88.35 ± 3.93%) and radiochemical purity (RCP) (>95%). More notably, the tracer can be transformed into a hydrophobic macrocyclic molecule under the joint action of legumain and reductant. Simultaneously, the tracer could target legumain-positive tumors and enhance accumulation and retention in tumors, resulting in the amplification of PET imaging signals. The enhancement of radioactivity enables PET imaging of legumain activity with high specificity. We envision that, by combining this highly efficient 18F-labeled strategy with our intramolecular macrocyclization reaction, a range of radiofluorinated tracers can be designed for tumor PET imaging and early cancer diagnosis in the future.

研究领域: 医学成像 · 癌症研究 · 放射药物化学 · 分子生物学
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Tetraphenylethene-based macrocycles: Visualized monitoring the hydrolysis of silicon-oxygen bond and their tunable luminescent properties

Mingxue Feng,Junying Zhang,Hong-Tian Ji,Xing-Dong Xu,Shengyu Feng

The preparation of silicone material is generally carried out by hydrolytic condensation, and various methods have been tried so far to study the kinetics of silicon-oxygen bond hydrolysis. However, the process and kinetics of silicon-oxygen bond hydrolysis cannot be efficiently monitored in real-time due to the limitations of traditional testing methods. In the present study, we have successfully designed and synthesized a series of circular tetraphenylethylene (TPE) derivatives connected with different lengths of the siloxanes chain. As the chain length gets longer, the restriction on phenyl rotation in TPE derivatives becomes weaker, which induced fluorescence quenching gradually at the molecular level. Hence, it provides the most direct and convincing evidence for the effect of chain lengths in the popular restricted intramolecular rotation (RIR) mechanism with aggregation-induced emission (AIE) phenomenon. The strong fluorescent molecule was used to monitor the kinetics of silicon-oxygen bond hydrolysis in real-time successfully by the AIE method with the RIR mechanism. The high sensitivity and efficiency of fluorescence provide an unparalleled “visualization” window for real-time monitoring of the kinetic control of Si-O bond hydrolysis. Furthermore, the half-life and reaction kinetic data of Si-O bond-breaking reaction by different pH are obtained to provide a reference for scientists and engineers not only in fundamental research but also in industrial production. Finally, the aggregation-induced color-tunable emission was obtained with the different aggregation forms of molecules, exhibiting a promising potential for intelligent luminescent materials.

研究领域: 材料科学 · 化学 · 分析化学 · 物理化学
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