Comparison of hot Soxhlet and accelerated solvent extractions with microwave and supercritical fluid extractions for the determination of polycyclic aromatic hydrocarbons and nitrated derivatives strongly adsorbed on soot collected inside a diesel particulate filter

Several methods of extraction were optimized to extract polycyclic aromatic hydrocarbons (PAHs), their nitrated derivatives and heavy n-alkanes from a highly adsorptive particulate matter resulting from the combustion of diesel fuel in a diesel engine. This particular carbonaceous particulate matter, collected at high temperatures in cordierite diesel particulate filters (DPF), which are optimized for removing diesel particles from diesel engine exhaust emissions, appeared extremely refractory to extractions using the classical extracting conditions for these pollutants. In particular, the method of accelerated solvent extraction (ASE) is described in detail here. Optimization was performed through experimental design to understand the impact of each factor studied and the factors’ possible interactions on the recovery yields. The conventional extraction technique, i.e., Soxhlet extraction, was also carried out, but the lack of quantitative extractions led us to use a more effective approach: hot Soxhlet. It appeared that the extraction of the heaviest PAHs and nitroPAHs by either the optimized ASE or hot Soxhlet processes was far from complete. To enhance recovery yields, we tested original solvent mixtures of aromatic and heteroaromatic solvents. Thereafter, these two extraction techniques were compared to microwave-assisted extraction (MAE) and supercritical fluid extraction (SFE). In every case, the only solvent mixture that permitted quantitative extraction of the heaviest PAHs from the diesel soot was composed of pyridine and diethylamine, which has a strong electron-donor character. Conversely, the extraction of the nitrated PAHs was significantly improved by the use of an electron-acceptor solvent or by introducing a small amount of acetic acid into the pyridine. It was demonstrated that, for many desirable features, no single extraction technique stound out as the best: ASE, MAE or SFE could all challenge hot Soxhlet for favourable extractions. Consequently, the four optimized extraction techniques were performed to extract the naturally polluted diesel soot collected inside the DPF. Comparisons with the NIST standard reference material SRM 1650b showed that the soot collected from the DPF contained 50% fewer n-alkanes, and also markedly lower levels of PAHs (44 less concentrated) than SRM 1650b, and that the ratio of nitroPAHs to PAHs was increased. These results were attributed to the high temperatures reached inside the particulate filter during sampling runs and to the contribution of the catalytic DPF to aromatic and aliphatic hydrocarbons abatement.     

A new kind of organophosphorus compounds as an efficient catalyst for asymmetric C-C bond formation reactions

A new class of chiral pyrrolidine-phosphite organocatalysts, available from commercially starting materials, has been synthesized and shown to be good catalytic activity for asymmetric Michael and Aldol reactions. The reactions proceeded to give the products in good yield and in a highly selective manner. Ionic liquid [Bmim][BF₄] as an efficient green solvent has been employed in the Michael addition.     

Pressurised hot water extraction followed by simultaneous derivatization and headspace solid-phase microextraction and gas chromatography-tandem mass spectrometry for the determination of aliphatic primary amines in sewage sludge

In this paper we describe an environmentally friendly and sensitive method for the determination of ten primary amines in sewage sludge. The method is based on pressurised hot water extraction (PHWE) followed by simultaneous derivatization with pentafluorobenzaldehyde (PFBAY) and headspace solid-phase microextraction (HS-SPME) and subsequent gas-chromatography ion-trap tandem mass spectrometry (GC-IT-MS-MS) analysis. The influence of the main factors on the PHWE of sludge was optimized by a central composite design. For all species the optimal conditions were water at pH 4 as the extracting solvent, an extraction temperature of 100 °C and an extraction time of 15 min. The separation and detection of the ten amines by GC-IT-MS-MS took just 10 min and the entire process took approximately 1 h. Repeatability and reproducibility between days, expressed as RSD (%) (n = 5), were less than 19 and 24%, respectively. The average limit of detection (LOD) was of 65 μg kg⁻¹ s (range found 9-135) and the average limit of quantification (LOQ) was of 230 μg kg⁻¹ (range found 50-450) of dry weight (d.w.). Under optimized conditions we used this method to determine the compounds in industrial and municipal sewage sludge samples and in sludge from a potable water treatment plant. Methylamine and isobutylamine showed the highest levels in one of the industrial sewage sludge samples (404 and 543 mg kg⁻¹ (d.w.), respectively). To our knowledge, this paper presents for the first time the determination of ten primary amines in sewage sludge samples using PHWE.     

New cyclic phosphonium salts derived from the reaction of phosphine-aldehydes with acid

Various cyclic phosphonium structures are formed in high yield by the deprotection of unstable phosphine-aldehydes in acidic solution. When there is a methylene spacer between the phosphine and the aldehyde, a phosphonium ion [PHR₂CH₂CH(OEt)₂]Br₂, R=iPrOH, Et is obtained. Reaction of these phosphonium salts with water produces the dimers [-PR₂CH₂CH(OH)-]₂[Br]₂ R = iPr, Et. When there is an ethylene spacer as in PPh₂CH₂CH₂CH(OCH₂CH₂O), a remarkable tetramer with a 16-membered ring [-PPh₂CH₂CH₂CH (OH)-]₄[Cl]₄ forms as one diastereomer in hydrochloric acid solution. Reaction of HCl with the protected phosphine-aldehyde with a propylene spacer (PPh₂CH₂CH₂CH₂CH(OCH₂CH₂O)) results in the formation of the monomeric phosphonium salt [-PPh₂ CH₂CH₂CH₂CH(OH)-]Cl with a 5-membered ring. Solid state structures of different ring types were determined using X-ray diffraction experiment.     

Experimental design in the optimization of a microwave acid digestion procedure for the determination of metals in biomorphic ceramic samples by inductively coupled plasma mass spectrometry and atomic absorption spectrometry

In the present paper, we have synthesized a biomorphic ceramic material from oak wood as biological template structure and infiltration with zirconia-sol. After the material characterization, we have optimized the sample dissolution by acid attack in an oven under microwave irradiation. Experimental designs were used as a multivariate strategy for the effect's evaluation of varying several variables. This article describes the development by response surface methodology (RSM) of a procedure for zirconium determination, and other ions, such as copper and nickel by inductively coupled plasma mass spectrometry (ICP-MS) and others, such as iron, calcium and magnesium determination by flame atomic absorption spectrometry (FAAS) in the synthesized sample after digestion. A full factorial design (3³) was used to find optimal conditions for the procedure through response surface study. Three variables (time, HNO₃ volume and HF volume) were regarded as factors and as response to the concentration of different metal ions in the optimization study.     

印制板中地线正确连接原则的讨论

印制板的接地方式非常重要,如果地线布线不合理,就可能引起不可接受的测量误差。本文通过一个典型的热电偶数字测温系统的地线连接的分析,来说明PCB中地线正确连接的重要性和接地原则。文章说明了在模拟和数字信号混合系统中连接PCB地线时,应该防止有较大的地电流,特别是应防止数字电路中大的脉冲地电流流入模拟电路的地线中,尤其不应流入小信号模拟电路的地线中。     

网络教育平台的设计与实现研究

网络教育平台是开展现代远程教育的支撑核心。本文对网络教育平台的业务需求进行了分析,并对网络教育平台的设计开发原则,开发模式等问题进行了研究和探讨。     

基于能力培养的实验设计模式研究

传统基础型实验的设计缺陷,一定程度上制约了实践教学改革的深入。本文提出了一种基于能力培养的实验设计模式。该模式既保留了传统基础型实验内容,又充分体现以能力培养为核心的实践教学理念。教学实施表明,将该模式运用于基础型实验的教学,是一种训练学生基本实验技能和提升实践能力的有效途径。     

电机设备检修综合试验与检测平台

本文综述了电机综合试验与检测平台的主要结构,从电气主回路系统、电气控制系统和测量子系统三个部分,讨论了试验平台的总体设计及测控对象的方案设计。平台采用多台PLC分散控制和虚拟仪器结合的检测模式,通过工业以太网与控制台联系,既可相对独立工作,又可组合运行,可减小设备出现故障时的修复时间,并提高设备的工作效率。平台还拥有完善的系统安全保护功能。系统运行情况表明,该检测平台设计合理、功能完善,对于电机专业课教学具有实际意义。     

研究性教学在程序设计课程中的应用

程序设计课程的意义不仅在于传授一门计算机语言,更在于使学生掌握一种新的思维方法,并培养学生自主学习能力和创新实践能力。本项改革通过改革教学模式和实践教学方法,有效改变学生被动学习习惯,激发学生自主学习潜能,并通过分层次教学实现个性化培养。经过为期一年的学习和训练,学生较好地掌握了研究性学习的方法,学习能力得到较大提高。