Molecular Catalysis
·
2019
·
IF 2.938
Haibin Wang,Shaodong Liu,Tingting Sun,Zhanao Lv,Zhen Zhan,Guochuan Yin,Zhuqi Chen
In catalytic double bond migration reaction, E -configuration olefins were normally generated as the dominant product because E -configuration was thermodynamically favored. However, Z-configuration products are sometimes desired in pharmaceutical chemistry owing to the structure-activity relationship. In this paper, we have demonstrated a new strategy that Lewis acid promoted an widely employed and convenient ruthenium(II) complex for the catalytic isomerization of O-allylethers, leading to thermodynamic-unfavored Z-product under mild conditions. The model substrate of allyl phenyl ether can be simply scaled up to 20 mmol to produce Z-product with TON of 2453 and TOF of 13,430 h −1 at 40–60 °C. The system of Ru(II)/Lewis Acid catalysts was suitable for various substituted O -allylethers and other types of substrates. Through mechanism study including kinetic study, ligand inhibition effect and molecular spectroscopy, the dissociation of PPh 3 ligand by the addition of Lewis acid, and the formation a five-membered Ru complex from anchimeric assistance were both recognized as essential steps to improve the reactivity and to control the stereoselectivity of catalytic double bond migration reaction through metal hydride addition-elimination mechanism. This new strategy may provide a new opportunity to produce thermodynamic-unfavored product in heterocyclic compounds for pharmaceutical chemistry.
研究领域:
有机化学
·
药物化学
✓ 已验证
产品关联
DOI
高影响因子
MATERIALS & DESIGN
·
2022
·
IF 9.417
Yanfang Zhou,Piaoyi Chen,Mianrong Chen,Jiesong Li,Xufeng Li,Lingyin Lin,Yingying Lun,Qiuxia Li,Qinglin Xiao,Yugang Huang,Xianshu Wang,Hongzhi Zou,Guodong Ye
Traditional magnetothermal nanoparticles showed great limitations for the diagnosis of tumor location in a dynamic physiological environment in vivo . Here, we show an one-step photo-click method based on the composite structure of γ-Fe 2 O 3 @Poly(sucrose allyl ether) magnetic microspheres to meet this challenge. The advantages are to prepare the magnetic microspheres not in extreme conditions and using sucrose as the polymeric matrix to prevent Fe 2 O 3 nanoparticles from agglomeration. A series of in vitro and in vivo experiments showed that γ-Fe 2 O 3 @PSAE has excellent stability in biological medium and inappreciable cytotoxicity. Moreover obvious tumor magnetic resonance imaging contrasts were observed based on response of γ-Fe 2 O 3 @PSAE. Under an alternating magnetic field, the heat generated by the magnetic microspheres γ-Fe 2 O 3 @PSAE thermally ablated H 22 hepatoma cells from Kunming male mice, thereby inhibiting tumors. The histopathological studies showed that the tumor growth was significantly inhibited with the increase in the dosage of γ-Fe 2 O 3 @PSAE.
研究领域:
生物医学工程
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纳米医学
·
肿瘤学
✓ 已验证
DOI
高影响因子
CHEMOSPHERE
·
2024
·
IF 8.1
Xintong Li,Baocheng Qu,Jingyao Wang,Hongxia Zhao
Tetrabromobisphenol A bis (allyl ether) (TBBPA-BAE) represents an extensively used brominated flame retardant (BFRs) in the production of many fields and their phototransformation in natural water is still unclear. The environmentally persistent free radicals (EPFRs) with preserved activities could exist in the environment for a long time and involve in the phototransformation of many organic pollutants. Here, the photodegradation of TBBPA-BAE with the degradation rate constant ( k = 0.060 h −1 ) under simulate sunlight and the promoting effect of EPFRs on TBBPA-BAE photodegradation ( k = 0.135 h −1 ) were investigated. According to the detected photogenerated electrons (e − ) and singlet oxygen ( 1 O 2 ) rather than hydroxyl radicals (•OH) by the electron paramagnetic resonance (EPR), the effect mechanism may not be related to the typical •OH induced by EPFRs. The possible transformation pathways of the ether cleavage, hydrolysis and hydroxylation of propenyl bond and the debromination were proposed by the primary byproducts identified by UPLC-Q-Exactive Orbitrap MS. EPFRs caused a further debromination and ether cleavage and probably be due to EPFRs directly providing electrons to TBBPA-BAE which promoted the photodegradation of TBBPA-BAE, and their reaction mechanism needed further attention. Overall, this study provided useful information to understand the role of EPFRs on phototransformation of TBBPA-BAE in water.
研究领域:
环境科学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POLYMER SCIENCE
·
2024
·
IF 3.9
Lingyin Lin,Runxing Lin,Xufeng Li,Yanfang Zhou,Xiaotian Zhao,Wanqiu Huang,Qiuxia Li,Yugang Huang,He Wang,Guodong Ye
Interventional embolotherapy is widely used in clinical treatment of conservative liver cancer. This method has many advantages, such as good targeting, mild trauma, and low complications. The operation of transcatheter arterial embolization is to inject embolic microspheres into the arterial blood vessels of diseased organs, so as to occlude them and interrupt the blood supply, thus achieving the therapeutic purpose. However, there are still some deficiencies in clinical materials, for example catheter obstruction or vascular regeneration. In this study, pentaerythritol triallyl ether (APE) and its esterified product APEAA were used to prepare new polymeric amorphous embolic granules (PAPE and PAPEAA). The purpose is to overcome the excessive swelling problems of traditional polyvinyl alcohol granules (PVA). We verified that PAPE and PAPEAA were quickly and efficiently polymerized by photo-driven radical-mediated [3 + 2] cyclopolymerization mechanism (PRMC). RT-FTIR was used to explore the best route of photopolymerization initiated by four photoinitiators. Four physical properties experiments all prove that the particle has good physical properties. In vivo animal experiments, it is confirmed that the particles can achieve the expected effect and have good biological safety. The results show that the amorphous granules can meet the requirements of clinical injection and can be used as a new embolic material. Graphical
研究领域:
医学
·
肿瘤学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF POLYMER SCIENCE
·
2019
·Vol. 38
·期 1
·72-83
·
IF 2.804
Han Yue,Tang Dong-Hao,Wang Guang-Xing,Sun Ya-Nan,Guo Ying,Zhou Heng,Qiu Wen-Feng,Zhao Tong
Vanillin was used as sustainable source for phthalonitrile monomer synthesis, and allyl/propargyl ether moieties were introduced to improve the processability at the minimal cost of thermal properties. The synthesis route was optimized to minimize side-reactions and simplify post-processing, and the monomers were obtained in high purity and good yields. The curing behavior, mechanism, and processability of the monomers were studied, and the thermal properties of cured polymers were evaluated. Of the two monomers, the allyl ether-containing one exhibited a wide processing window of 185 °C, and was mainly cured into phthalocyanine and linear aliphatic structures through self-catalytic curing process. Also, the glass transition temperature was higher than 500 °C. In contrast, the propargyl ether-containing monomer could only be partially cured, and heat resistance was found to be compromised. Compared with traditional petroleum-based phthalonitrile resins, the bio-based monomers could be cured without the addition of catalysts, and improvement in processability was achieved at no cost of thermal performances.
研究领域:
材料科学
·
高分子化学
·
可持续材料
·
有机化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）