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JOURNAL OF CHROMATOGRAPHY A · 2016 · IF 3.926

Chiral separation of acidic compounds using an O-9-(tert-butylcarbamoyl)quinidine functionalized monolith in micro-liquid chromatography

Qiqin Wang,Peijie Zhu,Meng Ruan,Huihui Wu,Kun Peng,Hai Han,Govert W. Somsen,Jacques Crommen,Zhengjin Jiang

An O -9-( tert -butylcarbamoyl) quinidine (t-BuCQD) functionalized polymeric monolithic capillary column was prepared by the in situ copolymerization method. The physicochemical properties of the optimized monolithic column were characterized by scanning electron microscopy and micro-LC. Satisfactory column permeability, efficiency, stability and reproducibility were obtained for this monolithic column. The chiral recognition ability of the resulting monolith was also evaluated using 47 N -derivatized amino acids, eight N -derivatized dipeptides, and two herbicides. Under the selected conditions, the enantiomers of all chiral analytes were baseline separated with exceptionally high selectivity and resolution using micro-LC. It is worth noting that this chiral stationary phase (CSP) containing quinidine with a tert -butyl carbamate residue as chiral selector exhibits much higher enantioselectivity and diastereoselectivity than the previously developed O -9-[2-(methacryloyloxy)-ethylcarbamoyl]-10,11-dihydroquinidine (MQD) based CSP for N -derivatized amino acids and dipeptides. These results indicate that this novel quinidine-based polymeric monolith can be used as an effective tool for the enantioseparation of chiral acidic compounds.

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JOURNAL OF APPLIED MICROBIOLOGY · 2016 ·Vol. 121 ·期 6 ·1616-1626 · IF 2.156

Biodegradation of phenanthrene by Rhizobium petrolearium SL‐1

Huang X.,Shi J.,Cui C.,Yin H.,Zhang R.,Ma X.,Zhang X.

AimsWe aimed to investigate the phenanthrene degradation characteristics and possible phenanthrene degradation pathways of Rhizobium petrolearium SL‐1.Methods and ResultsUsing high‐performance liquid chromatography (HPLC), UV‐visible and gas chromatography‐mass spectrometry (GC‐MS) analysis, the phenanthrene‐degrading properties and metabolites of Rh. petrolearium SL‐1 were analysed, and then combined with genome‐based analysis to elucidate the possible biodegradation pathway of phenanthrene in Rh. petrolearium SL‐1. The results of the analyses showed that phenanthrene (100 mg l−1) was completely degraded by strain SL‐1 at 35°C, 0·02% salinity and pH 9·0 within 3 days. A wide range of polycyclic aromatic hydrocarbons, including naphthalene, fluorene, anthracene and pyrene, could also be degraded by this strain.ConclusionsBased on the identified metabolites, the utilization of probable intermediates and the presence of putative phenanthrene catabolic genes, we concluded that phenanthrene was degraded via two different routes, namely the ‘naphthalene’ and the ‘phthalic acid’ routes.Significance and Impact of the StudyFor the first time, this study shows the degradation pathway of phenanthrene by a Rhizobium strain. Because of its excellent stress resistance, metabolic versatility, high degradation efficiency and potential application in phytoremediation, Rh. petrolearium SL‐1 is a potential candidate for the bioremediation of polycyclic aromatic hydrocarbons‐contaminated areas.

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JOURNAL OF CHROMATOGRAPHY A · 2016 · IF 3.926

Graphene-ZIF8 composite material as stationary phase for high-resolution gas chromatographic separations of aliphatic and aromatic isomers

Xiaohong Yang,Changxia Li,Meiling Qi,Liangti Qu

This work presents the separation performance of graphene-ZIF8 (G-Z) composite material as stationary phase for capillary gas chromatography (GC). The G-Z stationary phase achieved high column efficiency of 5000 plates/m determined by n -dodecane ( k   =   1.22) at 120   °C and showed weakly polar nature. Importantly, it exhibited high selectivity and resolving capability for branched alkane isomers and aromatic positional isomers, showing clear advantages over the reported neat graphene and ZIF8. In addition, it attained high resolution for geometric cis -/ trans -isomers. The G-Z column exhibited good column thermal stability up to 300   °C and column repeatability with RSD values of retention times in the range of 0.01–0.19% for intra-day, 0.05–0.88% for inter-day and 0.66–5.6% for between-column, respectively, Moreover, the G-Z column was employed for the determination of minor impurity isomers in real reagent samples, which demonstrates its promising potential in GC applications .

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CHEMOSPHERE · 2017 · IF 4.208

Presence, distribution and risk assessment of polycyclic aromatic hydrocarbons in rice-wheat continuous cropping soils close to five industrial parks of Suzhou, China

Yong Li,Ling Long,Jing Ge,Li-xuan Yang,Jin-jin Cheng,Ling-xiang Sun,Changying Lu,Xiang-yang Yu

Polycyclic aromatic hydrocarbons (PAHs) accumulated in agricultural soils are likely to threaten human health and ecosystem though the food chain, therefore, it is worth to pay more attention to soil contamination by PAHs. In this study, the presence, distribution and risk assessment of 16 priority PAHs in rice-wheat continuous cropping soils close to industrial parks of Suzhou were firstly investigated. The concentrations of the total PAHs ranged from 125.99 ng/g to 796.65 ng/g with an average of 352.94 ng/g. Phenanthrene (PHE), fluoranthene (FLT), benzo [a] anthracene (BaA) and pyrene (PYR) were the major PAHs in those soil samples. The highest level of PAHs was detected in the soils around Chemical plant and Steelworks, followed by Printed wire board, Electroplate Factory and Paper mill. The composition of PAHs in the soils around Chemical plant was dominated by 3-ring PAHs, however, the predominant compounds were 4, 5-ring PAHs in the soils around other four factories. Meanwhile, the concentration of the total PAHs in the soils close to the factories showed a higher level of PAHs in November (during rice harvest) than that in June (during wheat harvest). Different with other rings of PAHs, 3-ring PAHs in the soils around Chemical plant and Steelworks had a higher concentration in June. The results of principal component analysis and isomeric ratio analysis suggested that PAHs in the studied areas mainly originated from biomass, coal and petroleum combustion. The risk assessment indicated that higher carcinogenic risk was found in those sites closer to the industrial park.

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JOURNAL OF CHROMATOGRAPHY A · 2016 · IF 3.926

Graphitic carbon nitride as high-resolution stationary phase for gas chromatographic separations

Yunzhong Zheng,Meiling Qi,Ruonong Fu

This work presents the first example of utilization of graphitic carbon nitride (g-C 3 N 4 ) as stationary phase for capillary gas chromatographic (GC) separations. The statically coated g-C 3 N 4 column showed the column efficiencies of 3760 plates/m and weak polarity. Its resolving capability and retention behaviours were investigated by using the Grob test mixture, and mixtures of diverse types of analytes, and structural and positional isomers. The results showed superior separation performance of the g-C 3 N 4 stationary phase for some critical analytes and preferential retention for aromatic analytes. Specifically, it exhibited high-resolution capability for aromatic and aliphatic isomers such as methylnaphthalenes and dimethylnaphthalenes , phenanthrene and anthracene and alkane isomers. In addition, g-C 3 N 4 column showed excellent thermal stability up to 280   °C and good repeatability with relative standard deviation (RSD) values less than 0.09% for intra-day, below 0.23% for inter-day and in the range of 1.9–8.4% for between-column, respectively. The advantageous separation performance shows the potential of g-C 3 N 4 and related materials as stationary phase in GC and other separation technologies.

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BIORESOURCE TECHNOLOGY · 2016 · IF 4.917

Multifaceted effects of HZSM-5 (Proton-exchanged Zeolite Socony Mobil-5) on catalytic cracking of pinewood pyrolysis vapor in a two-stage fixed bed reactor

Yimeng Wang,Jie Wang

The pinewood was pyrolyzed in the first reactor at a heating rate of 10   °C   min −1 from room temperature to 700   °C, and the vapor was allowed to be cracked through the second reactor in a temperature range of 450–750   °C without and with HZSM-5. Attempts were made to determine a wide spectrum of gaseous and liquid products, as well as the mass and element partitions to gas, water, bio-oil, coke and char. HZSM-5 showed a preferential deoxygenation effect via the facilitated decarbonylation and decarboxylation with the inhibited dehydration at 550–600   °C. This catalyst also displayed a high selectivity for the formations of aromatic hydrocarbons and olefins by the promoted hydrogen transfer to these products at 550–600   °C. The bio-oil produced with HZSM-5 at 500–600   °C had the yields of 14.5–16.8%, the high heat values of 39.1–42.4   MJ   kg −1 , and the energy recoveries of 33–35% (all dry biomass basis).

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TALANTA · 2016 · IF 4.035

Green synthesis of mesoporous molecular sieve incorporated monoliths using room temperature ionic liquid and deep eutectic solvents

Li-Shun Zhang,Qing-Li Zhao,Xin-Xin Li,Xi-Xi Li,Yan-Ping Huang,Zhao-Sheng Liu

A hybrid monolith incorporated with mesoporous molecular sieve MCM-41 of uniform pore structure and high surface area was prepared with binary green porogens in the first time. With a mixture of room temperature ionic liquids and deep eutectic solvents as porogens, MCM-41 was modified with 3-(trimethoxysilyl) propyl methacrylate (γ-MPS) and the resulting MCM-41-MPS was incorporated into poly (BMA-co-EDMA) monoliths covalently. Because of good dispersibility of MCM-41-MPS in the green solvent-based polymerization system, high permeability and homogeneity for the resultant hybrid monolithic columns was achieved. The MCM-41-MPS grafted monolith was characterized by scanning electron microscopy, energy dispersive spectrometer area scanning, transmission electron microscopy, FT-IR spectra and nitrogen adsorption tests. Chromatographic performance of MCM-41-MPS grafted monolith was characterized by separating small molecules in capillary electrochromatography , including phenol series, naphthyl substitutes, aniline series and alkyl benzenes. The maximum column efficiency of MCM-41-MPS grafted monolith reached 209,000 plates/m, which was twice higher than the corresponding MCM-41-MPS free monolith. Moreover, successful separation of non-steroidal anti-inflammatory drugs and polycyclic aromatic hydrocarbons demonstrated the capacity in broad-spectrum application of the MCM-41-MPS incorporated monolith. The results indicated that green synthesis using room temperature ionic liquid and deep eutectic solvents is an effective method to prepare molecular sieve-incorporated monolithic column.

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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY · 2016 · IF 4.179

Catalytic transfer hydrogenation of ethyl levulinate into γ-valerolactone over mesoporous Zr/B mixed oxides

Jian He,Hu Li,Yanxiu Liu,Wenfeng Zhao,Tingting Yang,Wei Xue,Song Yang

A series of mesoporous acid–base bifunctional Zr/B mixed oxides with different molar ratios were prepared by a sol–gel method, and developed for conversion of ethyl levulinate (EL) to γ -valerolactone (GVL) by using alcohol as hydrogen source. The morphological structures and physico-chemical characteristics of the synthesized materials were identified by various techniques. A high GVL yield of 88.5% was achieved from EL in 2-propanol when Zr 1 B 1 was used. And acid–base sites played a synergic role in synthesizing GVL from EL as evident by poisoning experiments. Furthermore, the catalyst could be reused several times without significant loss of its catalytic activity.

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JOURNAL OF HAZARDOUS MATERIALS · 2017 · IF 6.065

Generation and application of a novel transgenic zebrafish line Tg(cyp1a:mCherry) as an in vivo assay to sensitively monitor PAHs and TCDD in the environment

Shao-Lin Xie,Muhammad Junaid,Wan-Ping Bian,Juan-Juan Luo,Jabir Hussain Syed,Chao Wang,Wen-Xu Xiong,Yan-Bo Ma,Aping Niu,Xiao-Jun Yang,Ji-Xing Zou,De-Sheng Pei

The polycyclic aromatic hydrocarbons (PAHs) and 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) are classified as human carcinogens, and can also cause serious health problems. To develop a convenient bio-monitoring tool for the detection of PAHs and TCDD in the environment, we generated a transgenic zebrafish line Tg(cyp1a:mCherry) with cyp1a promoter driving mCherry expression. Here, Tg(cyp1a:mCherry) embryos were treated with different concentrations of TCDD and five US EPA priority PAHs congeners. The results showed that the expressions of mCherry and endogenous cyp1a were consistent with the PAHs exposure concentrations and were largely induced by TCDD and ≥4-ring PAHs. Moreover, the sensitivity of Tg(cyp1a:mCherry) embryos was also evaluated through monitoring of the PAHs contamination in the water and soil samples. The elevated red fluorescent signals and cyp1a expression levels were observed in Tg(cyp1a:mCherry) zebrafish after exposure to water samples and soil organic extracts with higher concentrations of ≥4-ring PAHs. These results further strengthen our findings of concentration- and congener-dependent response of the newly established zebrafish. Taken together, the newly established zebrafish line will prove as a sensitive, efficient and convenient tool for monitoring PAHs and TCDD contamination in the environment.

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MICROCHIMICA ACTA · 2017 ·Vol. 184 ·期 7 ·2171-2180 · IF 4.58

Single layer graphitic carbon nitride-modified graphene composite as a fiber coating for solid-phase microextraction of polycyclic aromatic hydrocarbons

Wu Tong,Wang Juntao,Liang Weiqian,Zang Xiaohuan,Wang Chun,Wu Qiuhua,Wang Zhi

The authors describe a three-dimensional single layer graphitic carbon nitride-modified graphene composite (g-C 3 N 4 @G) deposited on a stainless steel wire by a sol-gel technique. The coated fiber was applied to direct immersion solid-phase microextraction of trace levels of polycyclic aromatic hydrocarbons (PAHs) from cosmetics samples prior to their determination by gas chromatography with mass spectrometry (GC-MS). Due to π stacking interaction and hydrophobic interaction between the g-C 3 N 4 @G coating and the analytes (naphthalene, acenaphthene, fluorene, phenanthrene, fluoranthene and pyrene), the fiber displays an excellent adsorption capability for the analytes. Under optimized conditions, the method has a wide linear range, low LODs (from 1.0 to 2.0 ng L −1 ), good repeatability and high recoveries. It was successfully applied to the determination of PAHs in cosmetics. The g-C 3 N 4 @G fiber also exhibited good durability. Schematic of a three-dimensional single layer graphitic carbon nitride-modified graphene composite (g-C 3 N 4 @G) that was coated onto a stainless steel wire for the direct-immersion solid phase microextraction of trace levels of polycyclic aromatic hydrocarbons prior to gas chromatography-mass spectrometric detection.

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RSC Advances · 2016 ·Vol. 6 ·期 103 ·100891-100898 · IF 3.289

Phosphatidic acid-functionalized monolithic stationary phase for reversed-phase/cation-exchange mixed mode chromatography

Kun Peng,Qiqin Wang,Weijia Chen,Donghai Xia,Zhengyin Zhou,Yuqiang Wang,Zhengjin Jiang,Fuhai Wu

A novel phosphatidic acid functionalized polymeric monolithic column was prepared through the thermally initiated co-polymerization of 12-methacryloyl dodecylphosphatidic acid (MDPA) and ethylene glycol dimethacrylate (EDMA) in the presence of 1,4-butanediol and isopropanol as porogens within 100 μm I.D. capillaries. The polymerization conditions of monolithic columns were systematically optimized in order to obtain good permeability, stability and column efficiency. The reproducibility of the optimized monolithic column was also satisfactory. The physicochemical properties of the monolithic column were evaluated by use of instrumental techniques including scanning electron microscopy, Fourier transform infrared spectra, ζ-potential analysis and micro-HPLC. A series of test compounds such as small peptides, alkylphenones, etc., were employed to investigate the retention mechanism on the poly(MDPA-co-EDMA) monolithic column. The results demonstrate that both hydrophobic and cation-exchange interactions could contribute to the overall retention of analytes. Furthermore, the novel reversed-phase/cation-exchange mixed mode monolithic column was applied to the separations of small peptides, phenols, water-soluble vitamins B, and pharmaceutical compounds. The successful applications indicate the potential of the poly(MDPA-co-EDMA) monolithic column in complex sample analysis.

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JOURNAL OF CHROMATOGRAPHY A · 2016 · IF 3.926

A solid-phase microextraction coating of sol–gel-derived perhydroxy cucurbit[6]uril and its application on to the determination of polycyclic aromatic hydrocarbon

Nan Dong,Tao Li,Yujie Luo,Lin Shao,Zhu Tao,Chun Zhu

A novel solid-phase microextraction coating that contains perhydroxy cucurbit[6]uril((OH) 12 Q[6]) was prepared by a sol–gel method. (OH) 12 Q[6] was used as a starting coating material with hydroxy-terminated poly(dimethylsiloxane) (OH-PDMS) to bond chemically to a fused-silica substrate using 3-(2-cyclooxypropoxyl)propyltrimethoxysilane as cross-linking agent; hydrolysis and polycondensation reactions then led to the formation of a (OH) 12 Q[6]/PDMS-coating. The coating has a high thermal stability (360   °C), long lifetime and can withstand organic and inorganic solvent rinsing because of the chemical binding between the coating and silica substrate. Its performance was tested by headspace (HS) solid-phase microextraction fiber coupled with gas chromatography to determine polycyclic aromatic hydrocarbon (PAHs) compounds in water samples. The (OH) 12 Q[6]/PDMS-coated fiber exhibited higher enrichment factors from fourfold for naphthalene to tenfold for pyrene compared with commercial PDMS fiber, and the enrichment factors increased with the number of condensed PAH rings. The strong adsorption affinity is believed to be attributed to hydrogen bonding and C H⋯π interactions between PAHs and (OH) 12 Q[6], according to the results of quantum chemical calculations. In the PAH analysis, the (OH) 12 Q[6]-coated fiber showed a good repeatability (<   4.7%) and reproducibility between fibers (<   9.4%), low detection limits (0.03–0.15   μg   L −1 ), and a wide linearity (0.1–1000   μg   L −1 ) under optimized conditions. This method was used for the simultaneous determination of seven PAHs with satisfactory recoveries of 90.56%–107.4% for Huaxi river water samples and 90.23%–109.5% for local wastewater samples, respectively.

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