Chem Catalysis
·
2022
·
IF 0
Xianhao Zhang,Huijuan Jing,Shiming Chen,Bing Liu,Liang Yu,Jianping Xiao,Dehui Deng
Summary Cyclohexanone oxime (CHO), a key C=N organic compound in the manufacture of nylon 6, is conventionally synthesized via a multistep process that consumes expensive NH 3 and H 2 under harsh conditions. Herein, we report the direct electro-synthesis of CHO from low-cost NO, H 2 O, and cyclohexanone over a carbon catalyst under ambient conditions. A high Faradaic efficiency of 44.8% and a formation rate of 10.7 mg cm −2 h −1 for CHO were achieved at −0.4 V versus the reversible hydrogen electrode through optimizing the surface hydrophobicity of the catalyst to facilitate diffusion of reactants. Controlled experiments and 15 N-labeling tests verified that the nitrogen in the CHO product originates from NO. Density functional theory calculations showed that the armchair edge of carbon could be the active site with a reaction mechanism following NO → NO∗ → HNO∗ → HNOH∗ → NH 2 OH → CHO. This work suggests a direct, green, and low-cost synthesis strategy for high-value CHO from pollutant NO.
研究领域:
化学工程
·
环境科学
✓ 已验证
DOI
ACS Catalysis
·
2022
·
IF 13.7
Chunning Zhao,Ao Zhu,Shan Gao,Lijing Wang,Xiang Wan,Ansheng Wang,Wei-Hua Wang,Tao Xue,Shikuan Yang,Deyan Sun,Weichao Wang
A phonon is the medium a bulk material used to exchange energy with the environment and is thus crucial for heterogeneous catalysis. However, a physical correlation between phonons and catalytic processes has not been established yet. Herein, by combining various in situ characterization techniques, we discovered the intrinsic correlations between phonon modes and the vibrations of reactant intermediates during NO oxidation on the mullite catalyst YMn2O5. It was found that the active phonon modes (350 (Ag(5)) and 670 cm–1 (B1g(12))) are strongly correlated with the vibrational frequencies of the adsorbed −O2 and −O–NO2 intermediates. The resulting resonance will transfer the superposed energy (nℏω) of the high-energy phonons to reactants one by one via the unit energy (ℏω) and then increase the vibrational amplitude along the reaction direction, contributing to the increase in the entropy of the surface reactants and thus the reduction of the Gibbs energy of activation. Phonon resonance catalysis (PRCAT) was thus proposed based on this discovery. This work provides insights into the bidirectional selection of catalysts and precise chemical reactions by matching catalyst phonons with reactant vibrational frequencies.
研究领域:
催化
·
材料科学
·
表面化学
·
物理化学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2025
·
IF 4.7
Hongrui Lan,Qiuyu Wu,Jingyu Huang,Jianbo Ding,Xianghong Li,Chunya Li
Based on [Ru(dfppy)(bpy)(CH 3 CN)NO](PF 6 ) 2 (complex 1 , where Hdfppy= 2-(2,4-difluorophenyl)pyridine, bpy=2,2′-bipyridine), three new cyclometalated ruthenium nitrosyl complexes [Ru(dfppy)(L)(CH 3 CN)NO](PF 6 ) 2 ( 2 − 4 , where L = 2,2’-bipyridine derivatives) were synthesized by grafting methoxy or dimethyl ester groups onto the 2,2’-bipyridine ligand. These complexes were fully characterized by NMR, IR, MS and single-crystal X-ray diffraction spectra, confirming the {Ru II −NO + } 6 electronic configuration for all complexes. Together with the pronounced changes in their UV−Vis absorption spectra under irradiation, the MS and 1 HNMR spectra of the photolysis products suggested a photoinduced homolysis-reduction process. ESR spectra exhibited the photorelease of NO and 1 O 2 . Notably, complex 3 with dimethyl esters at the 4,4’-position of bipyridine demonstrated the shortest N−O bond length of 1.129(13) Å and the longest Ru−N(O) bond length of 1.767(9) Å, indicating a weakened Ru–NO linkage that facilitates NO release upon irradiation. Consistently, complex 3 displayed the highest photolysis rate ( k NO =3.1 × 10 −2 min −1 ) in the series and the most efficient NO release, reaching a concentration of 5.32 μmol/L after 30 min of irradiation (365 nm LED, 13 mW/cm 2 ) as determined by the Griess assay. Furthermore, CCK8 assays indicated that all the complexes exhibit low dark toxicity and desirable phototoxicity towards 4T1 cells. Among them, complex 3 displayed the strongest phototoxicity due to its excellent photo-sensitive NO release capacity.
研究领域:
无机化学
·
光化学
·
药物化学
·
生物无机化学
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产品关联
DOI
高影响因子
ENERGY & FUELS
·
2019
·
IF 3.021
Shujun Sun,Suxia Ma,Bingchuan Yang,Rongji Cui,Jie Wang
NO removal from flue gas was conducted on a self-made bubbling reactor with ClO2. Results indicated that ClO2 has excellent oxidizing power to NO, and its actual reaction molar ratio is close to the theoretical molar ratio. At the temperature of 80 °C and ClO2/NO = 0.6, the NO removal efficiency can reach 96.7%. The electron spin resonance and inhibitor (sodium formate and isopropanol) addition experiments indicated that the ClO2 and ·OH radical in the solution played an important role in NO oxidation. The mechanism of NO removal by ClO2 was proposed through the analysis of oxidation products and relative references.
研究领域:
环境工程
·
大气污染控制
·
化学工程
·
环境化学
·
工业废气治理
✓ 已验证
DOI
高影响因子
Science China-Chemistry
·
2026
·
IF 9.8
Dai Huan,Yang Mingyu,Yang Hongkun,Liu Haiquan,Ke Zunjian,He Dong,Xiao Xiangheng
Electrochemical nitrate reduction (NO 3 RR) represents an environmentally sound pathway for converting nitrate ions (NO
− 3
) to ammonia in wastewater. However, the mechanism governing NO
− 3
hydrogenation under altered liquid-phase conditions remains poorly understood. This study enhances the reactivity of CeO 2 toward nitrate hydrogenation by loading it with transition metals and further modifying the composition of alkali metal cations in the electrolyte. This approach regulates the continuity of both interfacial water and hydrogen-bond networks, facilitating NO
− 3
-proton coupling and thereby boosting NO 3 RR reactivity. Furthermore, the incorporation of diverse surfactants into the electrolyte confirms that alterations in the liquid-phase environment influence interfacial water distribution, ultimately improving NO 3 RR reactivity. This study deepens our understanding of interfacial water’s role in NO 3 RR, providing a theoretical basis for developing more efficient electrocatalysts.
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2016
·
IF 5.31
Yi Zhao,Han Wang,Tianhao Wang
Two kinds of molecularly imprinted adsorbents (MIPa and MIPb) prepared by acid functional monomers and basic functional monomers respectively were used to capture NO by physical adsorption at different conditions, and the effects of O 2 , SO 2 , and CO 2 on NO adsorption were investigated. The results showed that MIPa had better NO adsorption capacity than MIPb, and increasing the temperature, flow rate and NO concentration could affect NO adsorption breakthrough time. The NO adsorption capacities of MIPa and MIPb were nearly unaffected by O 2 , however, SO 2 and CO 2 in simulated flue gas could have more negative effects to adsorption capacity of MIPb than that of MIPa. The calculation results of the overall mass transfer coefficient of MIPb and MIPa indicated that the external diffusion was the controlling step of NO adsorption.
研究领域:
环境科学
·
化学工程
·
吸附技术
✓ 已验证
DOI
高影响因子
Acta Biomaterialia
·
2023
·
IF 9.7
Mengsi Zhang,Hao Jin,Yi Liu,Lanlan Wan,Shuwei Liu,Hao Zhang
NO gas therapy is a supplementary approach for tumor treatment due to the advantages of minimal invasion, little drug resistance, low side effect and amplified efficacy. l -Arginine (L-Arg), a natural NO source with good biocompatibility, can release NO under the stimulation of H 2 O 2 in tumor microenvironment. However, the conventional l -Arg delivery systems via noncovalent loading usually lead to inevitable premature leakage of nano-cargos during blood circulation. In this work, an efficient l -Arg self-delivery supramolecular nanodrug (SDSND) for tumor treatment is demonstrated by combining Mannich reaction and π-π stacking. l -Arg links to (-)-epigallocatechin gallate (EGCG) with the assistance of formaldehyde through Mannich reaction, and then assembles into nanometer-sized particles via π-π stacking. The guanidine group of l -Arg and the phenolic hydroxyl groups of EGCG are preserved in the SDSNDs, which allows for accomplishing gas therapy by provoking tumor cell apoptosis and combining with EGCG to amplify apoptosis, respectively. In addition, the SDSNDs exhibit high biocompatibility and avoid the premature leakage of l -Arg in blood circulation, providing an alternative l -Arg delivery system for NO gas therapy. Statement of significance NO gas therapy has attracted emerging interest in tumor treatment. However, the controlled NO release and the avoidance of premature leakage of NO donors remain challenging. In this work, L-Arginine (L-Arg) self-delivery supramolecular nanodrug for efficient tumor therapy is demonstrated through the Mannich reaction of L-Arg, (-)-epigallocatechin gallate (EGCG) and formaldehyde. Stimulated by tumor microenvironment, the guanidine groups of L-Arg allow for accomplishing NO release and thus provoking tumor cell apoptosis. The nanodrug also avoids the premature leakage of L-Arg in blood circulation. Moreover, the preserved phenolic hydroxyl groups of EGCG combine with L-Arg to amplify apoptosis. The nanodrug exhibits high biocompatibility and good therapeutic effect, providing an alternative L-Arg delivery system for NO gas therapy.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Acta Biomaterialia
·
2021
·
IF 8.947
Xue Liu,Yulin Liu,Avnesh S. Thakor,Bhavesh D. Kevadiya,Jiamin Cheng,Manling Chen,Yang Li,Qian Xu,Qiuhua Wu,Yang Wu,Guolin Zhang
Carbon nanodots based on L-arginine (L-Arg) were developed for enhanced nitric oxide (NO) gas therapy for cancer. The L-Arg-based carbon nanodots (Arg-dots) produced high levels of NO in the tumor environment rich in endogenous H 2 O 2 . In vitro cell experiments revealed that the Arg-dots could kill tumor cells (including human breast cancer cell line MCF-7, female gastric cancer cell line BGC-823, male lung cancer cell line A549, and female leukemic cell line K562) but did not affect the activity of normal cells (human normal lung epithelial cell line BEAS-2B). The Arg-dots produced twice the amount of NO for an equivalent amount of L-Arg. Theoretical calculations showed that the carbonization structure of the Arg-dots promoted significantly more electrons toward the guanidinium groups of L-Arg and boosted the adsorption of H 2 O 2 molecules. In vitro and in vivo investigations confirmed that the Arg-dots reduced the multidrug resistance (MDR) effect of the tumor cells (MCF-7/ADR cells) and produced a combined antitumor efficacy with traditional chemotherapeutic drugs (adriamycin [ADR]). The fluorescence property (quantum yield, 6.88%) allows the Arg-dots to be used as a suitable fluorescent probe for fluorescence imaging of tumor cells. The ultra-small size of the Arg-dots (diameter: ca. 2.5 nm) enables them not only to penetrate deep tumors and provide enhanced antitumor activity but also to be removed through kidney filtration and have a renal clearance property. Statement of significance Nitric oxide (NO), which serves as a biological messenger, can be used in gas therapy for cancer. The development of a safe and efficient NO cancer therapy is, however, challenging because of the low NO release amount and poor tumor specificity of most NO donors. Many efforts have been made to overcome these drawbacks, but solving both these limitations through a single approach has been seldom achieved. In the present work, carbon nanodots (Arg-dots) from L-arginine were used for gas therapy of cancer. The Arg-dots produced NO in the H 2 O 2 -rich tumor environment. Theoretical calculations were consistent with the mechanism of enhanced NO release amount. The Arg-dots also reduced the multidrug resistance effect in cancer chemotherapy. In vivo and in vitro toxicity assessments confirmed that the Arg-dots have excellent biosafety.
✓ 已验证
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Tong Zhang,Hui Li,Zhi Yang,Fengren Cao,Liang Li,Haijun Chen,Hui Liu,Ka Xiong,Jie Wu,Zhanglian Hong,Weichao Wang
Nanofiber catalysts are potentially promising to be equipped in the lean-burned vehicle exhaust emission system considering its facile synthesis, low-cost, long durability in contrast to the traditionally complicated powder based catalyst. Here, via electrospinning method, we synthesized YMn 2 O 5 nanofibers (average diameter: ˜93 nm) including nanowire stacked with particles, and hollow tubes with or without inside nanowires. The morphologies remained even after hydrothermal aging at 800 ℃ for 10 h with 10% H 2 O stream. X-ray photoelectron spectrum revealed Mn 4+ /Mn 3+ ratio 0.589 on the surface of YMn 2 O 5 catalyst (YMO), indicating the existence of oxygen vacancies. The highest conversion of electrospun mullite fibers at 310 ℃ is ˜18% higher than powder-based YMO at 352 ℃ in the presence of 5% H 2 O at WHSV = 240,000 ml g −1 h −1 . The extracted activation energy from NO-to-NO 2 conversion curves of YMO nanofiber (61.68 kJ/mol) is slightly lower than that of powder-based mullite (91.45 kJ/mol), consistent with calculated 68.16 kJ/mol on the fiber YMO surface (121) with a rate-limiting step of the NO 2 desorption. The catalytic activity can be attributed to the unit occupy of the e g ( d z 2 and d x 2 -y 2 ) orbitals of Mn-dimer atoms around fermi level based on the combination of the theoretical calculations and DRIFTS spectra analysis. Importantly, after the hash hydrothermal-aging, the highest NO oxidation conversion of powder-based mullite is less than 50%, while the fiber maintains a conversion of 62%. Moreover, the fresh YMO fiber maintained superior oxidation stability for 12 h at its maximum conversion of 66%. This work provides the possibility for mullite oxide fibers to replace powder-based precious metal catalyst coating on monolith converter.
✓ 已验证
产品关联
DOI
高影响因子
FUEL PROCESSING TECHNOLOGY
·
2017
·
IF 3.752
Tiantian Cao,Zijian Zhou,Qian Chen,Zhen Li,Shengming Xu,Jianlong Wang,Minghou Xu,Teresa Bisson,Zhenghe Xu
A novel class of magnetically responsive catalytic sorbents are proposed and synthesized with a potential application to simultaneous removal of Hg 0 and NO at low temperature from the flue gases of coal-fired power plants. The catalytic sorbent consists of magnetite (Fe 3 O 4 ), molecular sieve (HZSM-5), supported silver nanoparticles and catalytically reactive component of V 2 O 5 . Each of these materials provides a unique function for the purpose of capturing mercury, removing NO, and separation from fly ash. After separation from the fly ash, the spent sorbent can be regenerated and reused, leaving an uncontaminated fly ash product. The successful synthesis as designed was confirmed and properties of the catalytic sorbent were characterized by several methods. The synthesized catalytic sorbent was able to completely capture Hg 0 at 150 °C with a capture capacity as high as 32.4 μg·g −1 , while achieving 84% removal of NO at 150 °C. Even at a relatively high space velocity, the catalytic sorbent achieved 97% Hg 0 and 80% NO removal simultaneously, while maintaining a good stability after repetitive regeneration and recycle. The magnetically responsive catalytic composite was shown to be a promising candidate for multi-pollutant emission control from coal-fired power plants.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2020
·
IF 10.652
Ruiyang Zhang,Aili Zhang,Yuehan Cao,Shuyan Wang,Fan Dong,Ying Zhou
Oxygen as an economic and ubiquitous oxidant plays a significant role in catalysis environmental remediation. However, the high thermodynamic stability of O 2 limits the practical application. Herein, we reported a novel Mo doped carbon nitride (Mo-CN/g-CN) homojunction via the in-situ growth strategy. The strong interaction between Mo-CN and g-C 3 N 4 enhanced visible-light response and photogenerated electrons and holes pairs separation, which were beneficial for photocatalytic activity. Importantly, theoretical calculation and experiments confirmed that Mo atoms on the surface of Mo-CN/g-CN could provide abundant electrons to the adsorbed O 2 to promote the generation of O 2 − , thus enhancing the photocatalytic performance. Consequently, the obtained Mo-CN/g-CN reveals excellent photocatalytic NO removal activity, demonstrating its promise for air purification. This current work gives a novel insight for O 2 activation in the application of photocatalytic environmental remediation.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
高影响因子
ARCHIVES OF PHARMACAL RESEARCH
·
2015
·Vol. 39
·期 2
·154-160
·
IF 2.046
Ma Wei,Zhang Yue,Ding Yun-Yun,Liu Feng,Li Ning
Bioactivity guided phytochemical investigation of the ethanol extract of the medullae of Juncus effusus resulted in the isolation of two new phenanthrenes, 8-hydroxymethyl-2-hydroxyl-1-methyl-5-vinyl-9,10-dihydrophenanthrene ( 1 ), and 5-(1-methoxyethyl)-1-methyl-phenanthren-2,7-diol ( 2 ) together with 15 known phenanthrenoids ( 3 – 17 ). The chemical structures of 1 and 2 were established by a combination of spectroscopic techniques. Compounds 1 – 15 and 17 were evaluated for their cytotoxic activities against five human cancer cell lines (SHSY-5Y, SMMC-7721, HepG-2, Hela and MCF-7) by CCK-8 assay, and their anti-inflammatory activities were also evaluated by inhibition on NO production in LPS-activated murine macrophage RAW 264.7 cells.
研究领域:
植物化学
·
药理学
·
肿瘤学
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）