SCIENCE OF THE TOTAL ENVIRONMENT
·
2024
·
IF 8.2
Yizhou Feng,Daohui Lin,Kun Yang,Wenhao Wu
Knowledge of antibiotic desorption from high-temperature biochar is essential for assessing their environmental risks, and for the successful application of biochar to remove antibiotics. In previous studies, irreversible pore deformation, formation of charge-assisted hydrogen bonds or amide bonds were individually proposed to explain the desorption hysteresis of antibiotics on biochars, leading to a debate on hysteresis mechanism. In this study, desorption of sulfamethoxazole (SMX), ciprofloxacin (CFX) and tetracycline (TET) on a wood chip biochar produced at 700 °C (WBC700) and its oxidized product (O-WBC700) was investigated to explore the underlying hysteresis mechanism. Significant desorption hysteresis was observed for SMX, CFX and TET on WBC700 and O-WBC700. Hysteresis index (HI) of each antibiotic was higher on O-WBC700 with more oxygen-containing groups than WBC700, and was higher at lower equilibrium concentration. HI of antibiotics on WBC700 (or O-WBC700) increased in the order of SMX < CFX < TET. The calculated adsorption enthalpy of each antibiotic on WBC700 was positive, indicating an endothermic process. These phenomena together with FTIR, XPS spectra confirmed that the desorption hysteresis mechanism of antibiotics on high-temperature biochar is the formation of amide bonds by amidation reaction, but not the pore deformation or the hydrogen bond. Moreover, antibiotic can form amide bonds with WBC700 only if the amine group with p K a > 4.0, and the HI values were positively correlated with their p K a values. Amine group of antibiotics with higher p K a value show more nucleophilicity and could form stronger amide bonds with carboxyl group of biochar. The obtained results could help to solve the debate on desorption hysteresis mechanism of antibiotics on high-temperature biochars, and provide a new insight into the role of amine groups and amidation reaction on the hysteresis.
研究领域:
环境科学
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化学
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产品关联
DOI
PubMed
高影响因子
Science China-Chemistry
·
2023
·Vol. 67
·期 1
·374-382
·
IF 9.6
Luo Zhongfeng,Jiang Jingxing,Zou Lifang,Zhou Xiaoyu,Liu Junshan,Ke Zhuofeng,Chen Fengjuan,Jiang Huanfeng,Zeng Wei
We disclose the development of the Rh-catalyzed amine-directed remote 5,6-carboamination protocol of pyridines via dual Csp 2 –H functionalizations. A variety of readily available 2-aminopyridines and 1,2,3-triazoles are allowed for coupling cyclization to access polyfunctionalized azaindoles. Mechanistic studies including DFT calculations unveil that relay carbenoid-electrophilic addition to pyridines and the sequential pyridyl Csp 2 –H amination are involved in this transformation. The post-synthetic utility of this methodology is showcased by versatile and site-selective modification of azaindoles.
研究领域:
有机化学
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催化化学
✓ 已验证
DOI
高影响因子
ChemCatChem
·
2021
·Vol. 13
·期 8
·2074-2085
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IF 5.686
Kuo Zhou,Ruihong Xie,Meiting Xiao,Darun Guo,Zhuodi Cai,Shimin Kang,Yongjun Xu,Jinjia Wei
Graphical Hydrogen borrowing : An efficient NiAl hydrotalcite-derived nickel catalyst has been developed for the direct amination of biomass-based furfuryl alcohol and 5-(aminomethyl)-2-furanmethanol with NH 3 via the “hydrogen borrowing” strategy. The synergistic catalysis of Ni 0 and Al δ+ -Al-O δ− site was of vital importance for the amination of alcohols into corresponding primary amines. A series of hydrotalcite-derived nickel catalysts were synthesized and employed for the direct amination of biomass-based furfuryl alcohol with NH 3 via the hydrogen borrowing strategy. The effects of the Ni/Al molar ratio and calcination temperature of the NiAl hydrotalcite-like precursors on the performance of the Ni x Al-CT catalyst were investigated. The systematic characterization showed that the synergistic catalysis of the metal and acid-base sites was of vital importance for the amination of alcohols. In particular, the Ni 2 Al-600 catalyst with high amount of Ni 0 sites (1.26 mmol g −1 ) and suitable density of acid-base sites (0.71 mmol g −1 and 1.10 mmol g −1 , respectively) exhibited the best dehydrogenation capability and therefore excellent catalytic activity. An 84.1 % yield of furfurylamine with complete conversion of furfuryl alcohol was obtained under the reaction conditions of 180 °C and 0.4 MPa NH 3 in 36 h. The presence of Ni 3 N in the spent catalyst, confirmed by XRD, TEM and XPS characterizations, was demonstrated to be responsible for the deactivation of the Ni x Al-CT catalyst. In addition, the Ni 2 Al-600 catalyst exhibited satisfactory performance toward another important biomass-related transformation of 5-(aminomethyl)-2-furanmethanol to 2,5-bis(aminomethyl)furan, with a yield of 70.5 %.
研究领域:
化学工程
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催化科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yue Wu,Cailing Chen,Zhuo Xiong,Meng Xu,Yue Zhao,Yihu Dai,Yu Han,Yu Zhou,Xiaoling Liu,Jun Wang
Direct hydrogen transfer amination of alcohols with amines is an environmentally friendly and atom-economical route for the synthesis of N-alkylamines. Noble metal species are highly catalytic active sites, but the exorbitant price makes the urgency to boost the atom efficiency with stable recyclability. Herein, we demonstrated that encapsulation of Ru nanoparticles (NPs) within BEA zeolite through direct hydrothermal approach greatly promoted the catalytic efficiency in the N-alkylation of aromatic alcohols and amines under additive- and solvent-free conditions, resulting in the high yield (∼93 %), maximum turnover number (TON) of 12,822 and turnover frequency (TOF) of 9012 h −1 , with stable recyclability and extendable substrate scope. The kinetic studies and in-situ characterizations revealed that the synergy of confined Ru NPs and adjacent acid sites of BEA zeolite significantly promoted the C–H bond activation in the rate-determining step of alcohol dehydrogenation into aldehydes. Besides, the acid sites also accelerated the condensation of aldehyde intermediates and anilines to promote the kinetic equilibrium, while the moderate strength of the Ru–H bond resulting from the confined Ru NPs is advantageous to balance the dehydrogenation and hydrogenation steps to reach the fascinating H-transfer process.
研究领域:
催化化学
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材料科学
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有机合成
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产品关联
DOI
高影响因子
CHINESE CHEMICAL LETTERS
·
2016
·
IF 1.947
Meng-Meng Liu,Qiong Mei,Yi-Xiao Zhang,Peng Bai,Xiang-Hai Guo
A concise and efficient approach was developed for the synthesis of mono-substituted and di-substituted pyrimidines products via palladium-catalyzed amination of chloro-substituted 5-nitropyrimidines and amines. This synthetic methodology can produce various di-substituted pyrimidines in high yields with good functional group tolerance, and provide a complementary tool for the syntheses of important intermediates of nucleosides and purines with bioactivities.
研究领域:
有机化学
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药物化学
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DOI
高影响因子
ACS Omega
·
2019
·
IF 2.584
Chao Sun,Wubing Yao,Xu Chen,Yiwen Zhao,Qiqi Wei,Zishuang Chen,Jiashou Wu,Feiyue Hao,Huiping Xie
An environmentally benign, highly efficient, and base-promoted selective amination of various polyhalogenated pyridines including the challenging pyridine chlorides to 2-aminopyridine derivatives using water as solvent has been developed. Featuring the use of the new method, the reaction is extended to the transformation on a large scale. Mechanistic studies indicate that the pathway involving a base aidant dissociation of N,N-dimethylformamide to generate dimethylamine is likely.
研究领域:
有机化学
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环境化学
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产品关联
DOI
PubMed
高影响因子
CHEMOSPHERE
·
2019
·
IF 5.108
Shisheng Zhang,Tao Lin,Wei Chen,Hang Xu,Hui Tao
The residues of pharmaceuticals and personal care products (PPCPs) in environmental waters have been widespread concerned. Metronidazole (MNZ), normally employed to treat inflammation and infection, was chosen as one model PPCP. The degradation of MNZ by chlorination could be fitted by pseudo-first-order kinetics as the observed pseudo-first-order rate constants increasing from 0.0302 min −1 to 0.2872 min −1 . However, the kinetics during chloramination of MNZ followed pseudo-second-order reaction, whose estimated half-live was approximately 6–8 times longer than chlorination. The chlor(am)ination of MNZ especially formed chloroform (CF), dicholoacetamide (DCAcAm), tricholoacetamide (TCAcAm) and dichloroacetonitrile (DCAN), and their yields were overall lower under chloramination than chlorination. During chlorination, the yield of CF was increased from 0.35 ± 0.02% to 2.06 ± 0.12% with 1–20 chlorine/MNZ molar ratio, whereas the formations of DCAcAm, TCAcAm and DCAN increased firstly and then decreased. Increasing chloramine dosage promoted the concentrations of scheduled disinfection byproducts (DBPs). CF and TCAcAm kept continuous generation in chlor(am)ination versus reaction time. Compared with the chlorination, the chloramination of MNZ was more dependent on pH value due to the self-degradation of chloramine. Faintly acidic condition favored N-DBPs' formation in MNZ when it was subjected to chlor(am)ination. The chloramination of MNZ produced cytotoxicity and genotoxicity by 10–15 folds lower than chlorination, and DCAN formed during chloramination dominated both DBPs' yields and toxicity contribution. Opposite to chlorination, the integrated toxicity of MNZ during chloramination varied linearly versus N-DBPs' yields.
研究领域:
环境科学
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毒理学
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产品关联
DOI
PubMed
高影响因子
ChemistrySelect
·
2022
·Vol. 7
·期 45
·e202204136
·
IF 2.307
Yue-Yue Du,Bo Jiang,Guo-Zhi Han
Graphical We report a new strategy of anti-Markovnikov hydroamination of vinyl pyridine with various amine compounds along with high selectivity. The highest yield of target product can reach 93 % in gram-scale reaction. On the basis, we proposed a kind of aza-Michael-type free radical addition mechanism, which was well supported by deuterium labeling studies and reference experiments. In this paper, we report a new and facile protocol for anti-Markovnikov hydroamination of vinyl pyridines under mild condition. In the presence of organic peroxide, pyridylethylation of a wide variety of aryl/alkyl amines with different substituent and electronic characteristics by intermolecular anti-Markovnikov hydroamination was successfully carried out. Furthermore, moderate to excellent yields were obtained along with high selectivity through condition optimization. The highest yield of target product can reach 93 % in gram-scale reaction. On the basis, we proposed a kind of aza-Michael-type free radical addition mechanism, which was well supported by deuterium labeling studies and reference experiments.
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
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS
·
2019
·Vol. 52
·期 2
·99-108
·
IF 1.417
Man-Yu Wang,Hong-Ze Gang,Lei Zhou,Jin-Feng Liu,Bo-Zhong Mu,Shi-Zhong Yang
The amidation of long-chain fatty acids is the key step for preparing surfactants with excellent interfacial activity. Gas chromatography–mass spectrometry was employed to detect the reactants and products in the direct amidation reactions. The conversion and the concentration of the amides in the reaction process were also investigated to determine the best catalyst, the reaction rate constants, and activation energy. It was identified that the amidation reaction of the long-chain phenyl fatty acid was a zero-order reaction and 3,4,5-trifluorophenylboronic acid was the most effective catalyst by which the activation energy reduced to 55.79 kJ/mol from 95.44 kJ/mol. The method can be applied to other long-chain fatty acids, saturated or unsatureated. The turning-over-temperature was 156°C, over which high yields can be achieved without any catalyst. These provide a reference for the preparation of long-chain fatty acid amides.
研究领域:
有机化学
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催化化学
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产品关联
DOI
高影响因子
Food Frontiers
·
2025
·Vol. 6
·期 2
·1058-1078
·
IF 6.9
Haolin Zhang,Jingjing Zhang,Hui Cao,Petra Högger,Randolph Arroo,Mohamed A. Farag,Avi Shpigelman,Jianbo Xiao,Chunlin Li
A class of flavonoid aminated derivatives that had been consistently overlooked in literature was shown to be formed as artefacts in cell culture medium. In this study, 34 flavonoids from different subclasses were incubated in Dulbecco's modified Eagle's Medium (DMEM) at 37°C for 2 h to identify the reaction mechanism behind aminated derivatives formation from flavonoids. Baicalein, scutellarein, dihydromyricetin, (−)-gallocatechin (GC), (−)-epigallocatechin (EGC), (−)-GC gallate, and (−)-EGC gallate were found to yield corresponding nitrogenous derivatives in both DMEM and amino acid solution. The nitrogen source of these seven flavonoid -aminated derivatives was revealed to be amino acids in DMEM. The pyrogallol group of the flavonoids was a key structural motif, being first oxidized into quinone and then further reacting with amino acids (Strecker degradation) to yield aminated flavonoids and corresponding aldehydes. A slightly alkaline environment accelerated the amination of flavonoids, possibly via the formation of flavonoid quinone. These results provide the mechanistic evidence for the in vitro generation of flavonoid -aminated derivatives, yet to be tested using in vivo assays.
研究领域:
生物化学
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药理学
✓ 已验证
产品关联
DOI
高影响因子
TETRAHEDRON
·
2013
·
IF 2.803
Run-Lin Li,Gong-Qing Liu,Wei Li,Yu-Mei Wang,Lin Li,Lili Duan,Yue-Ming Li
3-Chloropiperidine compounds were obtained via Cu(II)-promoted one-pot intramolecular chloroamination of N -benzyl-4-penten-1-amines and subsequent rearrangement. The reaction conditions leading to this skeleton were studied, and the structure of the product was confirmed by NMR as well as X-ray diffraction experiments.
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
TETRAHEDRON LETTERS
·
2012
·
IF 2.683
Gong-Qing Liu,Wei Li,Yu-Mei Wang,Zhen-Ying Ding,Yue-Ming Li
Zinc halide-promoted hydroamination of 4-penten-1-amine compounds was studied. Preliminary results indicated that both steric and electronic factors are crucial for this Lewis acid-promoted reaction. ZnI 2 gave the most promising results and the reactivity could be further increased upon addition of a suitable ligand. Up to 95% isolated yields were obtained when the reactions were carried out in 1,4-dioxane in the presence of 10 mol % of ZnI 2 and 8-hydroxyquinoline.
研究领域:
有机化学
·
催化反应
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）