Sensitive monitoring of penicillin antibiotics in milk and honey treated by stir bar sorptive extraction based on monolith and LC‐electrospray MS detection

In the present study, a convenient and sensitive method for determination of six penicillin antibiotics (amoxicillin, ampicillin, penicillin G, oxacillin, cloxacillin, and dicloxacillin) in milk and honey samples was developed. Milk and honey samples were diluted with water, then directly treated by stir bar sorptive extraction based on poly (vinylimidazole‐divinylbenzene) monolithic material as coating. The analytes were analyzed by LC/ESI‐ MS/MS. Several extraction parameters including extraction and desorption time, pH value, and ionic strength in sample matrix were investigated in detail. Under the optimized extraction conditions, the calculated detection limits for the target compounds were as low as 0.23–2.66 ng/kg in milk and 0.18–1.42 ng/kg in honey, respectively. Good linearity was obtained for analytes with the correlation coefficients (R²) above 0.997. Excellent method reproducibility was achieved in terms of intraday and interday precisions, indicated by the RSDs of <5.0 and <10.0%, respectively. Finally, the proposed method was successfully applied to the determination of penicillin antibiotics residues in different milk and honey samples.     

Determination of five booster biocides in seawater by stir bar sorptive extraction–thermal desorption–gas chromatography–mass spectrometry

Stir bar sorptive extraction (SBSE) and thermal desorption (TD)–gas chromatography–mass spectrometry (GC–MS) have been optimized for the determination of five organic booster biocides (Chlorothalonil, Dichlofluanid, Sea-Nine 211, Irgarol 1051 and TCMTB) in seawater samples. The parameters affecting the desorption and absorption steps were investigated using 10 mL seawater samples. The optimised conditions consisted of an addition of 0.2 g mL⁻¹ KCl to the sample, which was extracted with 10 mm length, 0.5 mm film thickness stir bars coated with polydimethylsiloxane (PDMS), and stirred at 900 rpm for 90 min at room temperature (25 °C) in a vial. Desorption was carried out at 280 °C for 5 min under 50 mL min⁻¹ of helium flow in the splitless mode while maintaining a cryotrapping temperature of 20 °C in the programmed-temperature vaporization (PTV) injector of the GC–MS system. Finally, the PTV injector was ramped to a temperature of 280 °C and the analytes were separated in the GC and detected by MS using the selected-ion monitoring (SIM) mode. The detection limits of booster biocides were found to be in the range of 0.005–0.9 μg L⁻¹. The regression coefficients were higher than 0.999 for all analytes. The average recovery was higher than 72% (R.S.D.: 7–15%). All these figures of merit were established running samples in triplicate. This simple, accurate, sensitive and selective analytical method may be used for the determination of trace amounts of booster biocides in water samples from marinas.     

Fe2O3/Al2O3氧载体用于甲烷化学链燃烧：负载量与制备方法的影响

以不同方法制备了系列Fe₂O₃/Al₂O₃氧载体,采用XRD、H₂-TPR、CH₄-TPR、O₂-TPD和BET等分析技术对氧载体进行了表征。研究了不同Fe₂O₃负载量氧载体的甲烷化学链燃烧性能,考察了不同制备方法对Fe₂O₃/Al₂O₃氧载体结构、反应性和产物选择性的影响。结果表明,Fe₂O₃负载量对氧载体活性及产物中CO₂选择性的影响较大,负载量较低时氧载体活性较低且引起甲烷部分氧化产物CO含量增加。制备方法亦对氧载体与甲烷的反应活性有所影响,整体上共沉淀法制备的质量分数60％Fe₂O₃/Al₂O₃氧载体具有较高的氧化活性和化学链循环稳定性。其在反应温度850℃、反应时间15 min、30次循环后甲烷转化率及产物中CO₂选择性均未见明显降低。     

Mechanistic Insights into Copper‐Catalyzed Sonogashira–Hagihara‐Type Cross‐Coupling Reactions: Sub‐Mol % Catalyst Loadings and Ligand Effects

An efficient catalytic system for Sonogashira–Hagihara‐type reactions displaying ligand acceleration in the copper‐catalyzed formation of C(sp²)? C(sp) bonds is described. The structure of the ligand plays a key role for the coupling efficiency. Various copper sources show excellent catalytic activity, even in sub‐mol % quantities. A wide variety of substituents is tolerated in the substrates. Mechanistic details have been revealed by kinetic measurements and DFT calculations.     

三维介孔氨基三亚甲基膦酸锆的合成及其担载铁催化剂的甲醛催化氧化活性

以氧氯化锆和氨基三亚甲基膦酸(ATMP)为原料合成了一种新型介孔材料氨基三亚甲基膦酸锆(NTAZP)。使用XRD、FTIR、TG-DTA和SEM等手段对所合成的介孔材料进行了结构表征和形貌分析。然后以NTAZP为载体,用Fe(NO3)3水溶液处理,得到担载Fe3+的氨基三亚甲基膦酸锆。研究结果表明,Fe3+被吸附到载体孔道中后,NTAZP结构未被破坏,Fe3+离子与NTAZP孔壁骨架上的N发生了配位作用。铁担载NTAZP(NTAZP-Fe3+)对甲醛氧化具有良好的催化活性,催化反应条件温和,催化剂稳定性良好。以载体NTAZP担载铁还避免了Fe3+进入水体,催化剂得以回收利用,避免造成二次污染。NTAZP-Fe3+是一种高效绿色的新型小分子醛类化合物氧化催化剂。     

Headspace stir bar sorptive extraction followed by thermal desorption and gas chromatography with mass spectrometry to determine musk fragrances in sludge samples without sample pretreatment

A direct, simple and solvent‐free method based on headspace stir bar sorptive extraction and thermal desorption gas chromatography with mass spectroscopy was developed to determine 13 musk fragrances (six polycyclic musks, three nitro musks and four macrocyclic musks) in sludge without sample treatment. The optimal headspace stir bar sorptive extraction conditions were achieved when a polydimethylsiloxane stir bar was exposed for 45 min in the headspace of a 10 mL vial filled with 100 mg of sludge mixed with 0.2 mL of water stirred at 750 rpm at 80°C. The stir bar was then desorbed in the thermal desorption gas chromatography and mass spectrometry system, obtaining limits of detection between 5 and 30 ng/g. The method applicability was tested with sewage sludge from two urban wastewater treatment plants and from a potable water treatment plant. Results showed galaxolide and tonalide to be the most abundant musk fragrances found in wastewater treatment plants with maximal concentrations of 9240 and 7500 ng/g, respectively. Maximum concentration levels between 35 and 635 ng/g were found for musk ketone, musk moskene, traseolide, phantolide and celestolide in this kind of samples. Concentrations below the limits of quantitation of phantolide, galaxolide, tonalide and musk ketone were found in sludge from a potable water treatment plant.     

Loading characteristics and chemical stability of headgroup‐functionalized poly(ethylene glycol)‐lipid ligand tethers on polypropylene capillary‐channeled polymer fibers

Polypropylene capillary‐channeled polymer fibers have been modified by adsorption of headgroup‐functionalized poly(ethylene glycol)‐lipids to generate a species‐specific stationary phase. In order to study ligand binding characteristics, a fluorescein‐labeled poly(ethylene glycol)‐lipid was used as a model system. Breakthrough curves and frontal analysis were employed to characterize the surface loading characteristics across a range of lipid concentrations and mobile phase flow rates. Efficient mass transfer and fluid transport yield a linear adsorption isotherm up to the maximum loading concentration of 3 mg/mL, at a linear velocity of 57.1 mm/s. Under these conditions, the dynamic binding capacity was found to be 1.52 mg/g of fiber support. Variation of the linear velocity from 8.6 to 57.1 mm/s showed only small changes in breakthrough volume. The maximum capacity of 1.8 mg/g is found under conditions of a load velocity of 34.2 mm/s and a concentration of 3 mg/mL lipid. Exposure of the lipid modified fibers to several challenge solvents reveals a chemically robust system, with only 50% acetonitrile and hexanes able to disrupt the lipid adsorption. The straightforward capillary‐channeled polymer fiber surface modification with headgroup‐functionalized lipids provides both a diverse yet practically robust ligand tethering system.     

高分散还原态Pt基催化剂的制备及其NO氧化的催化性能

Pt⁰被认为是NO氧化的活性物种,而催化剂的制备方法对活性物种的含量起着决定性作用。本文采用非惰性气氛保护的改性醇还原-浸渍法(MARI)合成了高分散高Pt⁰含量的1% (w, 质量分数) Pt/SiO₂-Al₂O₃催化剂(MA-Pt/SA)。X射线粉末衍射(XRD)、CO-漫反射傅里叶变换红外吸收光谱(CO-DRIFTS)和透射电镜(TEM)表征证实在550 ℃焙烧3 h后催化剂的Pt颗粒仅有3.8 nm。同时,X射线光电子能谱(XPS)和H₂-程序升温还原(H₂-TPR)结果表明催化剂具有高Pt⁰含量(60.3%)。模拟柴油车尾气气氛进行活性测试,并与传统浸渍法制备的1% (w) Pt/SiO₂-Al₂O₃催化剂(C-Pt/SA)对比,结果显示MA-Pt/SA具有优异的催化氧化性能,其NO最大转化率高达74%,比C-Pt/SA的NO转化率高了23%。经670 ℃高温老化15 h后,老化的MA-Pt/SA的NO转化率仍然高达69%。此外NO + O₂共吸附原位漫反射傅里叶变换红外吸收光谱(in situ DRIFTS of NO + O₂ co-adsorption)表明高的Pt分散度和高Pt⁰含量能够促进中间物种桥式硝酸盐的生成及分解,进而导致了优异的NO氧化活性。最后,利用同样方法将Pt的负载量降低至0.5% (w)制备催化剂,NO转化率仍达64%。这种制备方法能够获得低贵金属高性能的Pt基催化剂。     

基于氮掺杂活性炭催化氧化合成氮甲基氧化吗啉的研究

以三聚氰胺为氮源,商用活性炭为研究对象,通过“浸渍吸附+高温热处理”的方式制得系列氮掺杂活性炭,并用于催化氧化合成氮甲基氧化吗啉（NMMO）。采用N₂吸附/脱附、Raman、XPS等对氮掺杂活性炭的孔结构和表面性质进行了表征。结果表明：随着三聚氰胺负载量的增大,氮掺杂活性炭的表面碱性含氮官能团含量增大,进而体现出更好的催化氧化合成NMMO活性。最佳催化剂（ACO850-20N）在催化剂加量为0.02 wt%,反应温度70 ℃和反应时间4 h的工艺条件下,氮甲基吗啉的转化率和NMMO收率可达99.76%和94.31%。      

Robust nickel silicate catalysts with high Ni loading for CO2 methanation

CO₂ is the main component of greenhouse gases and also an important carbon source. The hydrogenation of CO₂ to methane using Ni-based catalysts can not only alleviate CO₂ emissions but also obtain useful fuels. However, Ni-based catalysts face one major problem of the sintering of Ni nanoparticles in the process of CO₂ methanation. Thus, this work has synthesized a series of efficient and robust nickel silicate catalysts (NiPS−X) with different nickel content derived from nickel phyllosilicate by the hydrothermal method. It was found that the Ni loading plays a critical role in the structure and catalytic performance of the NiPS−X catalysts. The catalytic performance gradually increases with the increase of Ni loading. In particular, the highly dispersed NiPS-1.6 catalyst with a high Ni loading of 34.3 wt% could obtain the CO₂ conversion greater than 80%, and the methane selectivity was close to 100% for 48 h at 330 °C and the GHSV of 40,000 mL g⁻¹ h⁻¹. The excellent catalytic property can be assigned to the high dispersion of Ni nanoparticles and the strong interaction between the active component and the carrier, which is derived from a unique layered silicate structure with lots of nickel phyllosilicate and a large number of Lewis acid sites.