Journal of Cleaner Production
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2023
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IF 11.1
Geliang Xie,Guoqiang Zhu,Yifan Kang,Mingxu Zhu,Qianqian Lu,Chao He,Lujiang Xu,Zhen Fang
Realizing the recovery and valorization of waste polyethylene terephthalate (PET) plastics into value-added products have gained significant importance. This study successfully synthesized aromatic nitriles , specifically terephthalonitrile (TPN), from waste polyethylene terephthalate (PET) plastic through in situ catalytic pyrolysis with urea and γ-Al 2 O 3 catalyst. Based on distributed activation energy model, positive interaction between waste PET and urea is responsible for improved thermal decomposition kinetics. The dosage of urea and pyrolysis temperature significantly influenced TPN production. TPN yield reached 32.5% with ca. selectivity of 85% at 550 °C and equivalent urea dosage. Density functional theory calculations validated the role of active ammonia in reducing energy barriers and thus facilitating PET depolymerization . The study highlights the feasibility of recycling waste PET into valuable aromatic nitriles through in situ catalytic pyrolysis with urea and enhances the understanding of the pyrolysis process.
研究领域:
材料科学
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化学工程
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DOI
高影响因子
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
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2024
·Vol. 171
·期 8
·085501
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IF 3.1
Yinghong Zhu,Minling Zhou,Zhanbang Ge,Yufeng Jiao,Menghui Wang,Wujin Peng
An efficient and transition-metal-free synthesis strategy of aromatic nitriles from corresponding aldehydes with H2SO4(NH2OH)2 as the nitrogen source and Cl−/ClO− as the redox mediator was developed. The redox Cl−/ClO− showed electrochemical reversibility in acidic condition. The possible mechanism involving the transformation of Cl−, the generation and electrochemical reduction of nitrile oxides based on the results of cyclic voltammetry and constant current electrolysis was proposed.
研究领域:
有机化学
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电化学
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DOI
高影响因子
MACROMOLECULES
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2023
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IF 5.5
Jinkang Dou,Minghui Xu,Bojun Tan,Hongchang Mo,Xianming Lu,Bozhou Wang,Ning Liu
Nitrile N-oxide-based click ligation is a very promising technique for polymer crosslinking due to the unique advantages of catalyst-free and byproduct-free reactions. For this technique, nitrile N-oxides that are sufficiently stable at room temperature and have high reactivity under mild conditions are very desirable. Usually, neighboring bulky substituents are introduced to enhance the stability of nitrile N-oxides, which however bring the reactivity down due to the high steric hindrance. Herein, methyl groups, small-sized substituents, were introduced into the o,o′-positions of phenyl nitrile N-oxides to enable high stability and high reactivity. Thus, several novel aromatic nitrile N-oxides were synthesized. Among them, ditopic aromatic nitrile N-oxides were prepared through three simple steps including etherification, oximation, and oxidative dehydrogenation, whereas stable tritopic aromatic nitrile N-oxides were synthesized by directly introducing the nitrile N-oxide functionality into the corresponding trifunctional compounds to avoid undesirable side reactions. These nitrile N-oxides as ligation reagents exhibited very high reactivity, and efficient catalyst-free crosslinking of natural rubber was achieved at room temperature to give elastomers with good mechanical properties, revealing the potential of such nitrile N-oxides as useful crosslinkers for unsaturated bond-containing polymers. This work provides reliable synthesis of stable ditopic/tritopic aromatic nitrile N-oxides, broadening the application of the nitrile N-oxide-based click ligation technique toward catalyst-free and byproduct-free polymer crosslinking.
研究领域:
材料科学
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有机化学
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高影响因子
JOURNAL OF MOLECULAR STRUCTURE
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2023
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IF 3.8
Xian He,Menghao Chen,Jiangbo Lv,Hang Xiao,Hao Wu,Rongtao Zhou,Jianghuai Hu,Ke Zeng,Gang Yang
Aromatic nitriles play an important role in the preparation of high-performance polymers. In order to guide the rational design of new molecules, it is necessary to carry out systematic theoretical research on molecular structures. This article takes a new type of aromatic nitriles, pyrazine-2,3-dicarbonitrile (PQ) and its control group 1,4-dicyanobenzene (PN) as examples to conduct systematic theoretical research on their chemical environments using DFT calculation with experimental verification. Results show that the electronic effect of pyrazine withdraws the electron form cyano to pyrazine, which makes the cyano carbon more exposed and prone to nucleophilic reaction. This electronic deffect also causes the π-electron delocalization from cyano nitrogen to pyrazine, and results in a lower polarity of the cyano and an anomalous law for the 13 C NMR shift of cyano carbon. In addition, pyrazine changes the stacking mechanism of PQ to be dominated by electrostatic force rather than commonly observed dispersion force-dominant π-π stacking in PN. This research method provides important guidance for the design of new crosslinkable aromatic nitrile and help to deepen our understanding of their structure-property relationship.
研究领域:
化学
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材料科学
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DOI
高影响因子
JOURNAL OF CHEMICAL RESEARCH
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2018
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IF 0.668
Xiaoyun Ma,Daqin He,Zhengjian Chen
A simple method for the preparation of nitriles in moderate to good yield has been achieved by treatment of aromatic and heterocyclic aldoximes with malononitrile in water at reflux in the presence of copper acetate as catalyst. Arylaldoximes with an electron-donating group showed the highest reactivity, their conversion being achievable at room temperature.
研究领域:
有机化学
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合成化学
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DOI
高影响因子
ENZYME AND MICROBIAL TECHNOLOGY
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2021
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IF 3.493
Zhiji Chen,Feiying Mao,Haoteng Zheng,Qinjie Xiao,Zhihao Ding,Anming Wang,Xiaolin Pei
Aromatic nitriles are important structural motifs that frequently existed in pharmaceutical drugs. Due to the convenient synthesis of aldoximes from aldehydes, the dehydration of aldoximes to corresponding nitriles by aldoxime dehydratases (Oxds) is considered as a safe and robust enzymatic production route. Although the Oxd genes are widely distributed in microbial kingdom, so far less than ten Oxds were expressed and further characterized. In this study, we found 26 predicted putative Oxd genes from the GenBank database using a genome mining strategy. The Oxd gene from Pseudomonas putida F1 was cloned and functionally expressed in Escherichia coli BL21 (DE3). The amino acid sequence of OxdF1 shows high identities of 33∼85 % to other characterized Oxds, and contained a ferrous heme as the catalytic site. The optimum reaction pH and temperature of recombinant OxdF1 were 7.0 and 35 °C, respectively. OxdF1 was stable in pH 7.0 potassium phosphate buffer at 30 °C, and its half-life was approximately 3.8 h. OxdF1 can efficiently dehydrate aromatic and heterocyclic aldoximes to nitriles, such as 2-bromobenzaldoxime, 2-chloro-6-fluorobenzaldoxime, thiophene-2-carboxaldoxime, and pyridine-3-aldoxime. Therefore, the recombinant OxdF1 shows a potential application in the cyanide-free synthesis of aromatic nitriles.
研究领域:
生物化学
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酶学
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药物化学
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生物技术
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DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）