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AICHE JOURNAL · 2024 ·Vol. 70 ·期 4 ·e18366 · IF 3.5

Kinetic study on the reaction between CO2 and tertiary amine catalyzed by zinc(II) aza-macrocyclic complexes

Meng-Meng Du,Bao-Chang Sun,Bei-Bei Wang,Yong Luo,Liang-Liang Zhang,Guang-Wen Chu,Hai-Kui Zou,Jian-Feng Chen

In this work, the kinetics study on the reaction between CO 2 and tertiary amine catalyzed by zinc(II)-1,4,8,11-tetraazacyclotetradecane complexes (CM) and zinc(II)-1,4,7,10-tetraazacyclododecane complexes (CN) was carried out in a stopped-flow device. The effects of the catalyst concentration, type of tertiary amines, and temperature on the reaction rate ( ν ) and catalytic activity ( φ ) were studied. It was found that the catalyst concentration, tertiary amine with higher p K a , and temperature had positive effects on ν . ν in N -methyl diethanolamine solution with 10.0 mol m −3 CM and CN were 16.62 and 26.05 folds than the uncatalyzed ν at 298 K, respectively. φ increased with increasing catalyst concentration, decreasing temperature and tertiary amine's p K a . In addition, the kinetics behavior of tertiary amine-CM/CN-CO 2 systems conformed to the Michaelis–Menten model. The activation energies in catalytic systems were 4%–15% lower than that in the non-catalytic systems.

研究领域: 化学动力学 · 催化 · 无机化学 · 环境化学
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MACROMOLECULES · 2026 · IF 5.2

Visible-Light-Driven Free Radical Polymerization and 3D Printing with Highly Efficient Carbazole-Substituted Aza-BODIPY Photoinitiators

Chenzhi Yao,Qike Sun,Hui Deng,Gongyang Chen,Heng Xia,Zhengjiang Liu,Timur Borjigin,Jiansong Yin,Jacques Lalevée,Yangyang Xu

Photoinduced radical chemistry is pivotal for synthesizing polymeric materials under light irradiation. In this study, carbazole moieties were incorporated at distinct positions within the aza-boron-dipyrromethene (aza-BODIPY) scaffold, yielding three novel push–pull dyes that function as high-performance photoinitiators for the free radical polymerization of acrylates upon exposure to visible-light LED irradiation. When combined with iodonium salts or amines as co-initiators, these aza-BODIPY derivatives form efficient two-component photoinitiating systems that exhibit outstanding initiation performance. Notably, distinct polymerization kinetics were observed for two benchmark acrylate monomers. Through a combination of experimental investigations and theoretical calculations, a comprehensive photochemical mechanism has been elucidated. Furthermore, these newly developed carbazole-substituted aza-BODIPY-based photoinitiating systems enable the fabrication of high-resolution three-dimensional macroscale architectures via 3D printing. This work advances the fundamental understanding and practical application of visible-light-induced free radical polymerization.

CAS / MDL: 15625-89-5 26570-48-9
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JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY · 2011 ·Vol. 49 ·期 20 ·4458-4467 · IF 3.894

Thieno[3,4-b]pyrazine-based low bandgap photovoltaic copolymers: Turning the properties by different aza-heteroaromatic donors

Qiang Peng,Xiangju Liu,Yuancheng Qin,Dan Zhou,Jun Xu

A new series of low-bandgap copolymers based on electron-accepting thieno[3,4-b]pyrazine (TPZ) and different electron-donating aza-heteroaromatic units, such as carbazole (CZ), dithieno[3,2-b:2′,3′-d]pyrrole (TPR) and dithieno[3,2-b:2′,3′-e]pyridine (TPY), have been synthesized by Suzuki or Stille coupling polymerization. The resulting copolymers were characterized by NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry. UV–vis absorption and cyclic voltammetry measurements show that TPZ-based copolymer with TPR has the best absorption due to the strongest intramolecular charge transfer effect and smallest bandgap. The basic electronic structure of D-A model compounds of these copolymers were also studied by density functional theory (DFT) calculations. The conclusion of calculation agreed also well with the experimental results. The polymer solar cells (PSCs) based on these copolymers were fabricated with a typical structure of ITO/PEDOT:PSS/copolymer:PC 71 BM/Ca/Al under the illumination of AM 1.5G, 100 mW cm −2 . The performance results showed that TPZ-based copolymer with TPR donor segments showed highest efficiency of 1.55% due to enhanced short-circuit current density. The present results indicate that good electronic, optical, and photovoltaic properties of TPZ-based copolymers can be achieved by just fine-tuning the structures of aza-heteroaromatic donor segments for their application in PSCs. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

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SEPARATION AND PURIFICATION TECHNOLOGY · 2018 · IF 3.927

1,3,5-Triazine tetrad-aza cyclophanes coated silica as a novel stationary phase for high performance liquid chromatography

Wenfen Zhang,Fei Wang,Yanhao Zhang,Wuduo Zhao,Yi Guo,Wei Wen,Shusheng Zhang

A new stationary phase (TTCPSP) has been prepared by covalently bonding 1,3,5-triazine tetrad-aza cyclophanes (TTCP) onto silica gel using 3-aminopropyl triethoxysilane as the coupling reagent. The stationary phase developed in this way was characterized by IR spectroscopy, elemental analysis and thermogravimetric analysis. The chromatographic performance and retention mechanisms of the new stationary phase were validated and compared with octadecylsilyl (ODS) stationary phases using a variety of compounds including monosubstituted benzenes, polycyclic aromatic hydrocarbons (PAHs) and flavonoids. The results indicate that the 1,3,5-triazine tetrad-aza cyclophanes (TTCPSP) stationary phase addresses solutes with multiple interactions, such as hydrophobic, hydrogen bonding, π-π, and inclusion interactions. TTCPSP, which shows strong retention ability to compounds containing OH, NH 2 or phenyl conjugate groups, is promising as a type of solid phase extraction sorbent.

研究领域: 分析化学 · 色谱学
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ANALYTICAL CHEMISTRY · 2024 · IF 6.7

Aza-Prilezhaev Aziridination-Enabled Multidimensional Analysis of Isomeric Lipids via High-Resolution U-Shaped Mobility Analyzer–Mass Spectrometry

Yuling Li,Yiming Wang,Kang Guo,Kuo-feng Tseng,Xiaoqiang Zhang,Wenjian Sun

Unsaturated lipids constitute a significant portion of the lipidome, serving as players of multifaceted functions involving cellular signaling, membrane structure, and bioenergetics. While derivatization-assisted liquid chromatography tandem mass spectrometry (LC-MS/MS) remains the gold standard technique in lipidome, it mainly faces challenges in efficiently labeling the carbon–carbon double bond (C═C) and differentiating isomeric lipids in full dimension. This presents a need for new orthogonal methodologies. Herein, a metal- and additive-free aza-Prilezhaev aziridination (APA)-enabled ion mobility mass spectrometric method is developed for probing multiple levels of unsaturated lipid isomerization with high sensitivity. Both unsaturated polar and nonpolar lipids can be efficiently labeled in the form of N–H aziridine without significant side reactions. The signal intensity can be increased by up to 3 orders of magnitude, achieving the nM detection limit. Abundant site-specific fragmentation ions indicate C═C location and sn-position in MS/MS spectra. Better yet, a stable monoaziridination product is dominant, simplifying the spectrum for lipids with multiple double bonds. Coupled with a U-shaped mobility analyzer, identification of geometric isomers and separation of different lipid classes can be achieved. Additionally, a unique pseudo MS3 mode with UMA-QTOF MS boosts the sensitivity for generating diagnostic fragments. Overall, the current method provides a comprehensive solution for deep-profiling lipidomics, which is valuable for lipid marker discovery in disease monitoring and diagnosis.

CAS / MDL: 105838-14-0
研究领域: 分析化学 · 生物化学 · 脂质组学 · 质谱
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Advanced Science · 2026 · IF 14.1

Fluorinated Hypoxia-Responsive Aza-BODIPY for NIR-II FL/19F MR/PA Imaging and Phototherapy of Lung Cancer

Anfeng Li,Fang Wang,Mou Jiang,Yu Li,Xin Zhou,Zhong-Xing Jiang

Tumor hypoxia limits the efficacy of photodynamic therapy (PDT), necessitating photosensitizers with hypoxia-adaptive therapy and imaging. Here, we present a fluorinated N -oxide aza-BODIPY ( OFBD ) nanoemulsion ( OFBD-NP ) for hypoxia-responsive, multimodal imaging-guided phototherapy. OFBD generates robust singlet oxygen under normoxia for PDT, but is reduced by CYP450 enzymes in hypoxic cells to photothermal-potent FBD , enabling switchable PDT/PTT. Co-assembly with fluorinated oil enhances oxygen delivery, boosts 19 F MRI sensitivity, and promotes J -aggregation, shifting fluorescence into the NIR-II window for deep-tissue imaging. The redox conversion also activates photoacoustic signals, enabling responsive tri-modal imaging (NIR-II FLI/ 19 F MRI/PAI). OFBD-NP shows potent cytotoxicity in vitro under both normoxic and hypoxic conditions via apoptosis. In vivo, it selectively accumulates in tumors, offers high-contrast imaging, and leads to complete tumor regression in subcutaneous A549 models after laser irradiation, without systemic toxicity. This work demonstrates a smart nanoplatform that integrates deep-tissue imaging and hypoxia-triggered therapeutic switching, addressing major limitations of conventional photosensitizers in cancer imaging and phototherapy.

CAS / MDL: 8001-22-7
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INFLAMMATION · 2019 ·Vol. 42 ·期 5 ·1705-1718 · IF 2.939

The Hypermethylation of Foxp3 Promoter Impairs the Function of Treg Cells in EAP

Chen Jing,Zhan Changsheng,Zhang Li,Zhang Ligang,Liu Yi,Zhang Yong,Du Hexi,Liang Chaozhao,Chen Xianguo

Treg cells are crucial for maintaining immune homeostasis in CP/CPPS, but the molecular mechanisms underlying the modulation of the function of Treg in CP/CPPS remain unclear. The main purpose of this study is to investigate the relationship between immunosuppressive function of Treg and the methylation level of Foxp3 promoter in experimental autoimmune prostatitis (EAP) mouse model. EAP model was induced by subcutaneous injecting prostate-steroid-binding protein (PSBP) and complete Freund’s adjuvant with NOD mice. Histological analysis revealed that EAP model was successfully induced. The expression of IFN-γ was increased, and TGF-β was decreased in the serum of EAP, respectively. The percentage of Tregs in splenic lymphocyte was increased in EAP. The suppressive ability of Tregs on Teffs was impaired in EAP. The methylation level of Foxp3 promoter was increased, and the expression of Foxp3 was decreased in EAP. By injection AZA which was DNA-methylation inhibitor into EAP mice, prostate inflammation was alleviated, expressions of TGF-β and Foxp3 were increased, and the suppressive function of Tregs was improved in vitro and in vivo . Thus, we concluded that aberrant increased methylation of Foxp3 promoter in Treg cells leads to the impaired suppressive function of Treg cells, exacerbating autoimmune inflammatory injury in EAP.

研究领域: 免疫学 · 分子生物学 · 自身免疫疾病 · 表观遗传学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2014 ·Vol. 32 ·期 3 ·371-376 · IF 1.42

Recovery of PET-quenched fluorescent conjugated polymers with aza-15-crown-5 as pendant groups on interaction with ions

Cao Jing,Feng Jun-xiang,Wu Shi

Novel conjugated polymers with aza-15-crown-5 as pendant groups, P1 were synthesized by the Sonogashira coupling reaction. The polymer P1 was found to show fluorescence enhancement response towards Ba 2+ . The gradual recovery and turning-point of emission intensity of polymers appeared in the addition of Ba 2+ , which provided good evidence for the fluorescence amplification mechanism of conjugated polymers.

研究领域: 材料科学 · 高分子化学 · 分析化学 · 传感器
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POLYMERS FOR ADVANCED TECHNOLOGIES · 2021 ·Vol. 32 ·期 4 ·1802-1812 · IF 3.665

Synthesis of post-modified poly(ester-amino) microspheres via aza-Michael precipitation polymerization and its use for enzyme immobilization

Bo Sun,Shusheng Li,Xubao Jiang,Xiaoli Zhu,Xiang Z. Kong

Uniform poly(ester-amino) microspheres (PEAs) were prepared by catalyst-free aza-Michael addition precipitation polymerization of trihydroxymethylpropyl triacrylate (TMPTA) and piperazine (PA) in acetonitrile. The effects of monomer feed ratio and concentration, polymerization temperature, and time on the size and morphology of PEAs were investigated. Monodisperse PEAs with size about 4 μm were successfully obtained at 2/3 molar ratio of TMPTA/PA and 4°C. The chemical structure of PEAs was characterized. There were amount of unreacted acrylate groups remained on the surface of PEAs prepared at the imino/acrylate molar ratio of 1/1.1, which provide lots of active sites for further chemical modification, especially for bioactivator immobilization. Laccase was used as an example to determine bio-immobilization activity of PEAs. Immobilized laccase exhibited higher tolerance to pH and temperature. The immobilized laccase was used as biocatalyst for degradation of Malachite Green. About 53% of its initial catalytic activity was retained after 4 cycles of reuse.

研究领域: 高分子科学 · 生物技术 · 材料科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2021 · IF 8.128

Functionalized triazine-based covalent organic frameworks containing quinoline via aza-Diels-Alder reaction for enhanced lithium-sulfur batteries performance

Ying Liang,Meng Xia,Yuxiang Zhao,Dong Wang,Yongpeng Li,Zhuyin Sui,Juanxiu Xiao,Qi Chen

The development of functional covalent organic frameworks (COFs) with specific properties is an emerging research field. In the current work, COF-SQ-Ph was synthesized through the aza-Diels-Alder reaction between phenylacetylene and the matrix COF-SQ (triazine-based COF) generated from the organic monomers 2, 4, 6-tris(4-aminophenyl)-1, 3, 5-triazine and 2, 5-dimethoxyterephthalaldehyde in flask. The functionalized COF-SQ-Ph with an extended π-conjugated structure and enhanced structural stability was used as the sulfur loading recipient to prepare sulfur cathodes for lithium-sulfur batteries. Sulfur-impregnated COF-SQ-Ph marked as COF-SQ-Ph-S displayed better cycling stability with a specific capacity of 618 mA h g −1 after 150 cycles due to the lithiophilic interaction between lithium polysulfides and nitrogen atoms from quinoline and triazine moieties in COF-SQ-Ph-S. The functionalization of triazine-based COFs through a cycloaddition reaction in flask could promote the large-scale preparation of tailored COFs and the post-synthesis modification of COF-SQ.

CAS / MDL: 95-50-1 536-74-3
研究领域: 材料科学 · 能源存储
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MACROMOLECULAR CHEMISTRY AND PHYSICS · 2020 ·Vol. 221 ·期 6 ·1900477 · IF 2.335

Aza-Michael Addition Chemistry for Tuning the Phase Separation of PDMS/PEG Blend Coatings and Their Anti-Fouling Potentials

Yunjiao Gu,Shuxue Zhou,Jinlong Yang

Free adjustment of micro/nanophase-separation degrees in coatings is not easily accessible, which is a big handicap in the development of phase-separation-related applications. Here, by utilizing the reactivity difference between two phases, a two-step aza- Michael addition pre-crosslinking strategy, demonstrated by acryloxy-terminated polydimethylsiloxane/polyethylene glycol (PEG) blend coatings, is proposed for the first time to tune microphase separation degrees, and promote compatibility of the biphasic amphiphilic polymer blends. Followed by a systematic study of the two-step pre-crosslinking time, surface morphologies of samples with desired phase-separation degrees are unveiled using optical microscopy, AFM, and XPS. The wettability, and anti-fouling properties — for example, anti-protein and anti-marine bacterial ( Shewanella ) adhesion — of these coatings are assessed. Less protein adsorption is observed on those surfaces with lower receding water contact angles. Shewanella adhesion is efficiently discouraged by the introduction of PEG segments, but the trend evolved with surface wettability and micro/nanophase structure in a complex way.

研究领域: 材料科学 · 生物医学工程
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Facile fabrication of superhydrophobic porous materials using the water-based aza-Michael reaction for high-efficiency oil-water separation

Lei Kang,Lanjie Shi,Longfei Song,Xingpeng Guo

Superhydrophobic porous materials are widely used in oil-water separation due to their water-blocking and oil-passing properties. However, the preparation of most superhydrophobic porous materials is generally energy-intensive and must be performed using organic solvents. In this study, we describe a straightforward and cost-effective strategy for fabricating superhydrophobic coatings on nanosized soil particle-modified stainless steel mesh (SSM). The coating is prepared via the aza-Michael reaction of stearyl acrylate and melamine-urea–formaldehyde (MUF) resin catalysed by methyl cyclodextrin in water. Superhydrophobic meshes with water contact angles (WCAs) exceeding 150° are obtained, exhibiting extraordinary water repellency. The superhydrophobic mesh also effectively prevents surface contamination, creating a self-cleaning surface that is both waterproof and dustproof. Most importantly, the superhydrophobic mesh presents excellent oil separation performance for oil-water mixtures of various compositions, maintaining extremely high separation efficiency (>98%) even after 80 cycles. Additionally, we successfully apply this strategy to the preparation of superhydrophobic melamine sponges with excellent oil adsorption capacity (17.6–44.2 g/g). This innovative study provides an effective strategy for designing biomimetic superhydrophobic surfaces and is a promising development in the field of environmentally friendly oil-water separators.

研究领域: 材料科学 · 环境科学
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