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Synthesis of antibacterial poly(o-chloroaniline)/chromium hybrid composites with enhanced electrical conductivity. 抗菌增强导电性聚邻氯苯胺/铬杂化复合材料的合成。
Q1 Chemistry Pub Date : 2018-04-26 DOI: 10.1186/s13065-018-0416-3
Mirza Nadeem Ahmad, Fakher Rafique, Faisal Nawaz, Tahir Farooq, Muhammad Naveed Anjum, Tajamal Hussain, Sajjad Hassan, Madeeha Batool, Hamad Khalid, Khurram Shehzad

Electrically conductive polyorthochloroaniline/chromium nanocomposites (POC/Cr NCs) were prepared by in situ chemical oxidative polymerization of orthochloroaniline in the presence of Cr nanoparticles (Cr NPs). The load percentage of Cr nanofiller was varied in POC matrix to investigate the effect of Cr nanoparticles on the properties of the nanocomposites. The composition, structure, and morphology of POC and its composites were examined by Scanning electron microscopy, Fourier transform infrared spectroscopy, and UV-visible spectroscopic analysis. The antibacterial potential of POC and its composites was evaluated by the disc diffusion method against Escherichia coli and Bacillus subtilis. The results showed the improved antibacterial potential with the increase in the load percentage of nanofiller. The electrical conductivity of polymer and its composites was measured and correlated with the load percentage. The results showed that electrical conductivity of the composites was enhanced with the increase in load percentage of Cr nanoparticles.

采用原位化学氧化聚合法制备了导电聚氯苯胺/铬纳米复合材料(POC/Cr nc)。通过在POC基体中加入不同比例的Cr纳米填料,研究了Cr纳米填料对复合材料性能的影响。采用扫描电镜、傅里叶变换红外光谱和紫外可见光谱分析对POC及其复合材料的组成、结构和形貌进行了表征。采用圆盘扩散法评价了POC及其复合材料对大肠杆菌和枯草芽孢杆菌的抑菌潜力。结果表明,随着纳米填料用量的增加,其抑菌潜力有所提高。测量了聚合物及其复合材料的电导率,并与负载百分比进行了相关性分析。结果表明,复合材料的电导率随着纳米铬负载量的增加而提高。
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引用次数: 5
The determination of Ochratoxin A based on the electrochemical aptasensor by carbon aerogels and methylene blue assisted signal amplification. 碳气凝胶-亚甲基蓝辅助信号放大电化学感应传感器测定赭曲霉毒素A。
Q1 Chemistry Pub Date : 2018-04-25 DOI: 10.1186/s13065-018-0415-4
Min Wei, Wenyang Zhang

In this work, a novel aptamer-based electrochemical biosensor was developed for the determination of Ochratoxin A (OTA) by using carbon aerogels (CAs) and methylene blue (MB) as signal amplification strategy. CAs was used as carrier to load the abundant of complementary DNA (cDNA), which could enhance the hybridization between CAs-cDNA and aptamer immobilized on the electrode surface, thus provide more double-stranded DNA for MB intercalation. The current of MB on the CAs-cDNA/apt/AuE sensor was twice that on the cDNA/apt/AuE sensor, which indicated that the CAs with high surface area enabled a higher loading of the cDNA and absorbed more MB, thus realized the signal amplification strategy. The optimum experimental conditions including MB incubation time of 15 min, aptamer concentration of 4.0 μmol/L, hybridization time of 2.0 h, and OTA incubation time of 18 min were obtained. The change of peak current was linearly proportional to the OTA concentration in the range of 0.10-10 ng/mL with the actual detection limit of 1.0 × 10-4 ng/mL. The experimental results showed that the prepared CAs-cDNA/apt/AuE exhibited good specificity, acceptable reproducibility and repeatability. This sensor was applied to detect OTA in the spiked corn samples, and obtained an acceptable average recovery of 89%.

本文采用碳气凝胶(CAs)和亚甲基蓝(MB)作为信号放大策略,建立了一种新型的适体电化学生物传感器,用于赭曲霉毒素a (OTA)的检测。利用CAs作为载体,装载丰富的互补DNA (cDNA),可以增强CAs-cDNA与固定在电极表面的适体的杂交,从而为MB嵌入提供更多的双链DNA。MB在CAs-cDNA/apt/AuE传感器上的电流是cDNA/apt/AuE传感器上的两倍,说明高表面积的CAs使cDNA的负载更高,吸收了更多的MB,从而实现了信号放大策略。最佳实验条件为MB孵育时间15 min,适体浓度4.0 μmol/L,杂交时间2.0 h, OTA孵育时间18 min。在0.10 ~ 10 ng/mL范围内,峰值电流的变化与OTA浓度成线性关系,实际检出限为1.0 × 10 ~ 4 ng/mL。实验结果表明,制备的CAs-cDNA/apt/AuE具有良好的特异性、可重复性和可重复性。该传感器用于检测玉米样品中的OTA,获得了89%的可接受平均回收率。
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引用次数: 14
Preparation and application of melamine cross-linked poly ammonium as shale inhibitor. 三聚氰胺交联聚铵页岩抑制剂的制备及应用。
Q1 Chemistry Pub Date : 2018-04-25 DOI: 10.1186/s13065-018-0410-9
Li Zhang, Tiehu Li, Lei Huang, Zhengqin Ye, Zhongbin Ye, Xin Yan, Lili Li, Qiang Deng, Gang Chen, Jie Zhang, Zhifang Zhang

In this paper, a series of poly ammonium shale inhibitors were prepared from diethylamine, epichlorohydrin, and melamine (DEM) and their inhibition to shale were evaluated by bentonite linear expansion test, anti-swelling experiments, and mud ball experiments. Additionally, other properties of drilling fluid treated by poly ammonium were evaluated. Anti-swelling results showed that anti-swelling rate of DEM-8 reaches up to 97.8% when its concentration reaches to 0.8%. Mud ball experiment and drilling fluid evaluation showed DEM-8 has strong inhibitive capability to bentonite hydration swelling and controlling the particle size of bentonite in a large scale. The inhibition mechanism of DEM-8 was studied by thermogravimetric analysis and scanning electron microscope. The results demonstrate that DEM-8 can be adsorbed on clay surface through electrostatic interaction and hydrogen bonds by an anchoring effect and a hydrophobic effect.

以二乙胺、环氧氯丙烷和三聚氰胺(DEM)为原料,制备了一系列聚铵型页岩抑制剂,并通过膨润土线性膨胀试验、抗膨胀试验和泥球试验评价了其对页岩的抑制作用。此外,还对经聚铵处理的钻井液的其他性能进行了评价。抗肿胀结果表明,当其浓度达到0.8%时,DEM-8的抗肿胀率可达97.8%。泥浆球实验和钻井液评价表明,DEM-8对膨润土水化膨胀具有较强的抑制作用,对膨润土粒径具有较大的控制作用。通过热重分析和扫描电镜研究了DEM-8的抑制机理。结果表明,DEM-8可以通过静电相互作用和氢键吸附在粘土表面,并具有锚定效应和疏水效应。
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引用次数: 13
Identification of characteristic aroma compounds in raw and thermally processed African giant snail (Achatina fulica). 生非洲巨蜗牛和热处理非洲巨蜗牛特征香气化合物的鉴定。
Q1 Chemistry Pub Date : 2018-04-24 DOI: 10.1186/s13065-018-0413-6
Ola Lasekan, Megala Muniady, Mee Lin, Fatma Dabaj

Background: Food flavor appreciation is one of the first signals along with food appearance and texture encountered by consumers during eating of food. Also, it is well known that flavor can strongly influence consumer's acceptability judgment. The increase in the consumption of snail meat across the world calls for the need to research into the aroma compounds responsible for the distinctive aroma notes of processed snail meat.

Results: The odorants responsible for the unique aroma notes in thermally processed giant African snail meats were evaluated by means of aroma extract dilution analysis (AEDA), gas chromatography-olfactometry (GC-O) and odor activity values (OAVs) respectively. Results revealed significant differences in the aroma profiles of the raw and thermally processed snail meats. Whilst the aroma profile of the raw snail meat was dominated with the floral-like β-ionone and β-iso-methyl ionone, sweaty/cheesy-like butanoic acid, and the mushroom-like 1-octen-3-one, the boiled and fried samples were dominated with the thermally generated odorants like 2-methylpyrazine, 2,5-dimethylpyrazine, 2-acetylthiazole and 2-acetylpyridine.

Conclusion: Finally, results have shown that sotolon, 2-acetyl-1-pyrroline, 2-furanmethanethiol, 2-methylbutanal, 1-octen-3-one, octanal, furanone, 2-methoxyphenol, 2-acetylpyridine, 2-acetylthiazole, and 2-methylpyrazine contributed to the overall aroma of the thermally processed snail meat.

背景:食品风味鉴赏是消费者在食用食品过程中遇到的与食品外观和质地一起的第一个信号。此外,众所周知,风味会强烈影响消费者的可接受性判断。随着世界范围内蜗牛肉消费量的增加,有必要对加工过的蜗牛肉产生独特香味的香气化合物进行研究。结果:采用香气提取液稀释分析(AEDA)、气相色谱-嗅觉测定(GC-O)和气味活性值(OAVs)对热加工非洲巨螺肉中产生独特香气的气味剂进行了评价。结果显示,生蜗牛肉和热处理蜗牛肉的香气分布有显著差异。生螺肉的香气以花香型的β-离子酮和β-异甲基离子酮、汗状/干酪状的丁酸和蘑菇状的1-辛-3-酮为主,而煮熟和煎熟的样品则以热生成的2-甲基吡嗪、2,5-二甲基吡嗪、2-乙酰噻唑和2-乙酰吡啶为主。结论:最后,结果表明:sotolon、2-乙酰基-1-吡咯啉、2-呋喃甲硫醇、2-甲基丁醇、1-辛烷-3-酮、辛烷酮、2-甲氧基酚、2-乙酰吡啶、2-乙酰噻唑和2-甲基吡嗪对热加工蜗牛肉的整体香气有影响。
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引用次数: 12
Targeting matrix metalloproteinases with novel diazepine substituted cinnamic acid derivatives: design, synthesis, in vitro and in silico studies. 新型二氮卓类肉桂酸衍生物靶向基质金属蛋白酶的设计、合成、体外和硅片研究
Q1 Chemistry Pub Date : 2018-04-20 DOI: 10.1186/s13065-018-0411-8
Dharmender Rathee, Viney Lather, Ajmer Singh Grewal, Harish Dureja

Lung cancer is the notable cause of cancer associated deaths worldwide. Recent studies revealed that the expression of matrix metalloproteinases (MMPs) is extremely high in lung tumors compared with non-malignant lung tissue. MMPs (-2 and -9) play an important part in tumor development and angiogenesis, which suggests that creating potent MMP-2 and -9 inhibitors, should be an important goal in lung cancer therapy. In the present study, an effort has been made to develop new anti-metastatic and anti-invasive agents, wherein a series of novel diazepine substituted cinnamic acid derivatives were designed, synthesized and assayed for their inhibitory activities on MMP-2 and MMP-9. These derivatives were prepared via microwave assisted reaction of tert-butyl (3-cinnamamidopropyl)carbamate derivatives mixed with 2,3-dibromopropanoic acid and potassium carbonate was added to obtain 4-(tert-butoxycarbonyl)-1-cinnamoyl-1,4-diazepane-2-carboxylic acid derivatives. The newly synthesized compounds were characterized by IR, NMR and mass spectroscopy. All the tested compounds showed good to excellent cytotoxic potential against A549 human lung cancer cells. The active compounds displaying good activity were further examined for the inhibitory activity against MMPs (-2 and -9). In addition, the structure and anticancer activity relationship were further supported by in silico docking studies of the active compounds against MMP-2 and MMP-9.

肺癌是全球癌症相关死亡的主要原因。近年来的研究表明,与非恶性肺组织相比,基质金属蛋白酶(MMPs)在肺肿瘤中的表达非常高。MMPs(-2和-9)在肿瘤发展和血管生成中起着重要作用,这表明创造有效的MMP-2和-9抑制剂应该是肺癌治疗的重要目标。本研究旨在开发新的抗转移和抗侵袭药物,设计、合成了一系列新的二氮卓类肉桂酸衍生物,并测定了它们对MMP-2和MMP-9的抑制活性。采用微波辅助法制备了叔丁基(3-肉桂酰胺丙基)氨基甲酸酯衍生物与2,3-二溴丙酸混合,加入碳酸钾制得4-(叔丁基羰基)-1-肉桂酰-1,4-二氮杂烷-2-羧酸衍生物。用红外光谱、核磁共振光谱和质谱对新合成的化合物进行了表征。所有化合物对A549人肺癌细胞均表现出良好或优异的细胞毒性。进一步检测活性良好的活性化合物对MMPs(-2和-9)的抑制活性。此外,针对MMP-2和MMP-9的活性化合物的硅对接研究进一步支持了结构和抗癌活性之间的关系。
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引用次数: 14
Exploration of Phyllanthus acidus mediated silver nanoparticles and its activity against infectious bacterial pathogen. 余甘子酸介导的纳米银及其抗感染性细菌病原体活性的研究。
Q1 Chemistry Pub Date : 2018-04-20 DOI: 10.1186/s13065-018-0412-7
Cherukuri Sowmya, Vuppalapati Lavakumar, Narayanan Venkateshan, Velayutham Ravichandiran, D V R Saigopal

In our present investigation, synthesis of nontoxic, eco friendly and cost effective silver nanoparticles, Phyllanthus acidus (P. acidus) was used as starting material. The influence of phyto-constituents present in aqueous extracts of Phyllanthus acidus was found to be effective in reduction of silver nitrate to free silver nanoparticles (PA-AgNPs). HPTLC finger print analysis reveals the presence of flavonoid, quercetin in aqueous extracts of Phyllanthus acidus. Surface plasmon racemonance exhibited λ max at 462 nm through UV-Vis spectroscopy. Zeta size revealed that the size of nanoparticles were with in the range of 65-250 nm with polydisperse index (PDI) of 0.451. The negative charge of zeta potential value (- 16.4) indicates repulsion among PA-AgNPs with their excellent stability. FESEM-EDAX, XRD and TEM analysis confirmed the presence of nano-crystalline PA-AgNPs with different morphological textures. Further, PA-AgNPs has shown potent antibacterial effect on E. coli cells. The greater antibacterial effect (viable and dead cells) of PA-AgNPs were confirmed by using acridine orange (AO) dye which can able to provide insight of healthy as well as damaged DNA. Live cells emit florescence green and dead cells (treated with PA-AgNPS at 20 and 40 µg/ml) appear as pale orange red colour. Post treatment, investigations of PA-AgNPs on E. coli cells under SEM was found to be effective against cell membrane damages which leads to cell death or cell growth arrest. Hence, from the above findings, we strongly recommend silver nanoparticles from Phyllanthus acidus can be used as a potential source for antimicrobial agent for chronic infections and also against other harmful microorganisms.

本研究以叶兰酸(Phyllanthus acidus, P. acidus)为原料合成无毒、环保、经济的纳米银。研究发现,叶兰酸提取物中存在的植物成分对硝酸银还原成游离银纳米粒子(PA-AgNPs)的影响是有效的。hplc指纹图谱分析表明,余甘子水提物中含有黄酮类化合物、槲皮素。表面等离子体外消旋在462 nm处表现出λ max。Zeta尺寸表明,纳米颗粒的尺寸在65 ~ 250 nm之间,多分散指数(PDI)为0.451。zeta电位值的负电荷(- 16.4)表明PA-AgNPs之间存在排斥力,具有良好的稳定性。FESEM-EDAX、XRD和TEM分析证实了不同形貌结构的纳米晶PA-AgNPs的存在。此外,PA-AgNPs对大肠杆菌细胞有较强的抗菌作用。使用吖啶橙(AO)染料证实了PA-AgNPs具有更强的抗菌作用(活细胞和死细胞),可以提供健康和受损DNA的洞察力。活细胞发出荧光绿色,死细胞(用20和40µg/ml的PA-AgNPS处理)呈现淡橙红色。处理后,在扫描电镜下对大肠杆菌细胞进行PA-AgNPs的研究发现,PA-AgNPs对导致细胞死亡或细胞生长停滞的细胞膜损伤有效。因此,根据上述研究结果,我们强烈建议,从酸梅中提取的银纳米颗粒可以作为慢性感染和其他有害微生物的潜在抗菌剂来源。
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引用次数: 15
Simultaneous identification and determination of flavonoids in Dendrobium officinale. 铁皮石斛中黄酮类化合物的同时鉴定与测定。
Q1 Chemistry Pub Date : 2018-04-12 DOI: 10.1186/s13065-018-0403-8
Chunhua Zhou, Zhenshan Xie, Zhouxi Lei, Yuechun Huang, Gang Wei

Background: The quality of material medicine resources has had a considerable impact on the development of the health industry, which has created a bottleneck for traditional Chinese medicine (TCM). Dendrobium officinale, which has been widely used for health prevention in TCM, has become a high-nutritive health food that is strongly recommended by many white-collar workers and people who pay more attention to their health. The aim of this study was to develop a method to authenticate and evaluate D. officinale from different origins via simultaneous qualitative and quantitative analyses of flavonoid glycosides. Ultra-high-performance liquid chromatography-electrospray ionization/mass spectrometry was used for the structural elucidation of the compounds.

Results: 9 characteristic peaks, including those representing 7 flavonoid C-glycosides and 2 flavonoid O-glycosides, were identified. Additionally, the contents of 5 representative flavonoid glucosides in 25 batches of D. officinale from different sources were determined. To further investigate the different sources of the 25 batch samples, principal component analysis (PCA) and hierarchical cluster analysis (HCA) were carried out. A study on the methodology revealed that all results were reliable.

Conclusions: This method is an efficient tool for the rapid identification of the different geographical origins of D. officinale and provides references for the quality evaluation of other natural products.

背景:药材资源的质量对健康产业的发展产生了相当大的影响,成为中医药发展的瓶颈。铁皮石斛在中医中被广泛用于保健,已成为一种高营养的保健食品,被许多白领和注重健康的人群强烈推荐。本研究的目的是建立一种同时定性和定量分析黄酮苷的方法来鉴别和评价不同产地的铁皮石斛。采用超高效液相色谱-电喷雾电离/质谱法对化合物进行了结构分析。结果:共鉴定出9个特征峰,分别代表7个类黄酮c糖苷和2个类黄酮o糖苷。测定了25批不同来源的铁皮石斛中5种具有代表性的黄酮类苷的含量。为了进一步了解25批样品的不同来源,我们进行了主成分分析(PCA)和层次聚类分析(HCA)。对方法的研究表明,所有结果都是可靠的。结论:该方法是快速鉴别铁皮石斛不同产地的有效工具,可为其他天然产品的质量评价提供参考。
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引用次数: 29
Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid. 脂肪酶催化从不饱和植物油中提取的脂肪酸甲酯在无羧酸条件下的环氧化反应。
Q1 Chemistry Pub Date : 2018-04-11 DOI: 10.1186/s13065-018-0409-2
Alejandro Sustaita-Rodríguez, Víctor H Ramos-Sánchez, Alejandro A Camacho-Dávila, Gerardo Zaragoza-Galán, José C Espinoza-Hicks, David Chávez-Flores

Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1H NMR, 13C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

如今,工业化学反应依赖于绿色技术。酶如脂肪酶在各种化学过程中的应用越来越广泛。植物油酯交换得到的环氧化脂肪酸甲酯近年来在聚合物增塑剂、农化、化妆品、药品和食品添加剂等方面得到了广泛的应用。本研究以葡萄籽油、牛油果油和橄榄油为原料,采用天然高含量的单不饱和脂肪酸和多不饱和脂肪酸为原料,制备了不饱和脂肪酸甲酯。以固定化南极念珠菌B型脂肪酶为催化剂,过氧化氢为供氧剂,在温和的温度和压力条件下,研究了月桂酸作为活性氧载体对不饱和脂肪酸甲酯环氧化反应的影响。经1H NMR、13C NMR和GC-MS证实,酶催化反应中不需要添加月桂酸,烯烃转化为环氧化物。结果发现,在没有羧酸的情况下,定量转化是可能的。
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引用次数: 12
Therapeutic potential of heterocyclic pyrimidine scaffolds. 杂环嘧啶支架的治疗潜力。
Q1 Chemistry Pub Date : 2018-04-04 DOI: 10.1186/s13065-018-0406-5
Sanjiv Kumar, Balasubramanian Narasimhan

Heterocyclic compounds offer a high degree of structural diversity and have proven to be broadly and economically useful as therapeutic agents. Comprehensive research on diverse therapeutic potentials of heterocycles compounds has confirmed their immense significance in the pathophysiology of diseases. Heterocyclic pyrimidine nucleus, which is an essential base component of the genetic material of deoxyribonucleic acid, demonstrated various biological activities. The present review article aims to review the work reported on therapeutic potentials of pyrimidine scaffolds which are valuable for medical applications during new generation.

杂环化合物具有高度的结构多样性,已被证明是一种广泛而经济的治疗药物。对杂环化合物多种治疗潜力的全面研究证实了其在疾病病理生理中的巨大意义。杂环嘧啶核是脱氧核糖核酸遗传物质的重要碱基成分,具有多种生物活性。本文综述了近年来嘧啶类支架在新一代医学应用方面的研究进展。
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引用次数: 109
The highly selective oxidation of cyclohexane to cyclohexanone and cyclohexanol over VAlPO4 berlinite by oxygen under atmospheric pressure. 常压下氧在VAlPO4沸石上高选择性氧化环己烷生成环己酮和环己醇。
Q1 Chemistry Pub Date : 2018-04-04 DOI: 10.1186/s13065-018-0405-6
Yun Hong, Dalei Sun, Yanxiong Fang

Background: The oxidation of cyclohexane under mild conditions occupies an important position in the chemical industry. A few soluble transition metals were widely used as homogeneous catalysts in the industrial oxidation of cyclohexane. Because heterogeneous catalysts are more manageable than homogeneous catalysts as regards separation and recycling, in our study, we hydrothermally synthesized and used pure berlinite (AlPO4) and vanadium-incorporated berlinite (VAlPO4) as heterogeneous catalysts in the selective oxidation of cyclohexane with molecular oxygen under atmospheric pressure. The catalysts were characterized by means of by XRD, FT-IR, XPS and SEM. Various influencing factors, such as the kind of solvents, reaction temperature, and reaction time were investigated systematically.

Results: The XRD characterization identified a berlinite structure associated with both the AlPO4 and VAlPO4 catalysts. The FT-IR result confirmed the incorporation of vanadium into the berlinite framework for VAlPO4. The XPS measurement revealed that the oxygen ions in the VAlPO4 structure possessed a higher binding energy than those in V2O5, and as a result, the lattice oxygen was existed on the surface of the VAlPO4 catalyst. It was found that VAlPO4 catalyzed the selective oxidation of cyclohexane with molecular oxygen under atmospheric pressure, while no activity was detected on using AlPO4. Under optimum reaction conditions (i.e. a 100 mL cyclohexane, 0.1 MPa O2, 353 K, 4 h, 5 mg VAlPO4 and 20 mL acetic acid solvent), a selectivity of KA oil (both cyclohexanol and cyclohexanone) up to 97.2% (with almost 6.8% conversion of cyclohexane) was obtained. Based on these results, a possible mechanism for the selective oxidation of cyclohexane over VAlPO4 was also proposed.

Conclusions: As a heterogeneous catalyst VAlPO4 berlinite is both high active and strong stable for the selective oxidation of cyclohexane with molecular oxygen. We propose that KA oil is formed via a catalytic cycle, which involves activation of the cyclohexane by a key active intermediate species, formed from the nucleophilic addition of the lattice oxygen ion with the carbon in cyclohexane, as well as an oxygen vacancy formed at the VAlPO4 catalyst surface.

背景:环己烷在温和条件下的氧化反应在化学工业中占有重要地位。几种可溶过渡金属作为均相催化剂广泛应用于环己烷的工业氧化。由于多相催化剂在分离和回收方面比均相催化剂更易于管理,因此在本研究中,我们采用水热合成的方法,将纯白沸石(AlPO4)和含钒白沸石(VAlPO4)作为多相催化剂,在常压下用分子氧选择性氧化环己烷。采用XRD、FT-IR、XPS和SEM对催化剂进行了表征。对溶剂种类、反应温度、反应时间等影响因素进行了系统的研究。结果:通过XRD表征,确定了AlPO4和VAlPO4催化剂均具有berlinite结构。FT-IR结果证实了VAlPO4的berlinite框架中含有钒。XPS测量结果表明,VAlPO4结构中的氧离子比V2O5结构中的氧离子具有更高的结合能,因此在VAlPO4催化剂表面存在晶格氧。结果表明,常压条件下,AlPO4能催化环己烷与分子氧的选择性氧化,而AlPO4则无活性。在最佳反应条件下(100 mL环己烷,0.1 MPa O2, 353 K, 4 h, 5 mg VAlPO4和20 mL乙酸溶剂),KA油(环己醇和环己酮)的选择性高达97.2%(环己烷转化率近6.8%)。基于这些结果,提出了环己烷在VAlPO4上选择性氧化的可能机理。结论:作为一种多相催化剂,VAlPO4对环己烷与分子氧的选择性氧化具有高活性和强稳定性。我们提出KA油是通过催化循环形成的,其中包括环己烷被一个关键的活性中间物质激活,由环己烷中的晶格氧离子与碳的亲核加成形成,以及在VAlPO4催化剂表面形成氧空位。
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引用次数: 18
期刊
Chemistry Central Journal
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