Chromatographic characterization of high‐boiling petroleum fractions

Detailed investigation of solvent‐separated fractions of petroleum vacuum residues is necessary for understanding the separation mechanism using different solvents and to prepare better feedstocks for secondary conversion processes. The efficiency of different solvents to remove polars and insolubles from vacuum residues (of two Indian crude oils) has been studied. The solvents used were n‐heptane, n‐hexane, and n‐pentane (non‐polar) and ethyl acetate (polar). Soluble fractions were characterized for hydrocarbon group type analysis using high performance liquid chromatography (HPLC), average molecular weights using size exclusion chromatography (SEC), and boiling point distribution using high temperature gas chromatography (HTGC). Method development for HPLC analysis involved the study of parameters such as columns, solvent polarity, detectors, model compounds study, calibration, flow, and solvent gradient programming. The study demonstrated that ultimate soluble fractions have the least content of polar structures of the kind which can cause problems, during cracking and are least prone to cracking. The HPLC, SEC, and simulated distillation (SIMDIS) methods developed and standardized are simple, accurate, and suitable for the rapid assay needed for quick compositional surveys.     

Intrinsic Fluorescence of Actin

In this work actin is used to illustrate connection of protein fluorescence characteristics with its structure. On one hand, it has been demonstrated what kind of information about the contribution of each tryptophan residues to the bulk fluorescence spectrum can be obtained from the special analysis of protein three-dimensional structure. On the other hand, potentials of intrinsic fluorescence for elucidation of proteins structure, dynamics and processes of folding-unfolding are shown. In particular, using this method a new essentially unfolded kinetic intermediate state of actin was detected and characterized, and the place of inactivated actin and its kinetic predecessor in the process of folding-unfolding was determined. It has been revealed that inactivated actin is not intermediate state between the native and completely unfolded states, as it has been accepted before, but a result of protein misfolding. On the basis of the obtained data a new model of actin folding-unfolding pathway has been proposed.     

Gas chromatographic trace analysis of underivatized nitrophenols

Summary A method for the gas chromatographic trace analysis of underivatized nitrophenols in ground-water is presented. Using a highly de-activated separation system a satisfactory precision for their quantitative GC analysis could be achieved by avoiding condensation of the solvent and by fast injection of the sample. The reproducibility of the peak areas of eleven nitrophenols in ethylacetate was <5 % RSD. Using a nitrogen-phosphorus detector detection limits were in a range from 10 to 30 pg. Within the concentration range from 0.1 to 10 ng μl⁻¹ the calibrations were linear with correlation coefficients >0.992. The approach described was applied to the analysis of nitrophenols in ground-water near a former ammunition plant, after preconcentration by continuous liquid/liquid extraction with ethylacetate. Using a GC-MS technique and retention times various nitrophenols were identified and then quantified in the μg/L-range by applying NPD.     

Determination of Organochlorine Pesticides in Sediments from Authie Bay Using Microwave Assisted Solvent Extraction

The aim of this study was to develop an analytical method to determine the organochlorine concentrations in sediments. Combination of Microwave assisted Solvent Extraction (MASE) and capillary gas chromatography with specific detection (electron capture detector) was a viable approach for the determination of pesticides in solid matrixes. In this study, MASE development was focused on the selection of a suitable extraction solvent for all the target analytes. MASE procedure was validated by comparison with conventional methods such as Soxhlet and sonication extraction. The proposed method was then applied to determine the organochlorine insecticides concentrations in samples from Authie Bay (France). Environmental water samples were analysed and five target analytes were detected in concentrations from 0.03 to 0.56 ng/g of dry sediment. These investigations showed the accumulation and the persistency of these products in sediments in spite of the fact they were banned a few decades ago.     

Composting of urban solid residues (USR) by different dispositions

The thermal behavior and non-isothermal kinetics of thermal decomposition of three different kinds of composting of the USR like: stack with drilled PVC tubes (ST), revolved stack (SR) and stack with material of structure (SM), from the usine of composing of Araraquara city, Săo Paulo state, Brazil, within a period of 132 days of composting were studied. Results from TG, DTG and DSC curves obtained on inert atmosphere indicated that the cellulosic fraction present, despite the slow degradation during the composting process, is thermally less stable than other substances originated from that process. Due to that behavior, the cellulosic fraction decomposition could be kinetically evaluated through non-isothermal methods of analysis. The values obtained were: average activation energy, Ea=248, 257 and 259 kJ mol^-1 and pre- exponential factor, logA=21.4, 22.5, 22.7 min^-1, to the ST, SR and SM, respectively. From Ea and logA values and DSC curves, Málek procedure could be applied, suggesting that the SB (Šesták-Berggren) kinetic model is the appropriated one to the first thermal decomposition step. This revised version was published online in July 2006 with corrections to the Cover Date.     

GC-MS法测定粮谷及油料中55种有机磷农药残留量

采用ASE-300快速溶剂萃取仪提取样品中农药残留量,提取液经二氯甲烷液-液分配、凝胶色谱柱（GPC）净化,固相萃取柱（活性炭）再净化,浓缩定容后,用气相色谱-质谱仪（GC-MS）测定,外标法定量.采用选择离子检测进行阳性确证.选择玉米、糙米、大豆、花生为实验样品、敌敌畏等55种农药添加水平在0.5～2.00 mg/kg时,该方法回收率为68%～117%;精密度为4.04%～11.76%;方法测定低限为0.005～0.100 mg/kg,各项指标均满足有关要求.     

A rapid method for the determination of methoprene in tobacco by high performance liquid chromatography

Summary A rapid sample preparation procedure combined with a short reversed-phase HPLC separation for the quantitation of methoprene residue in tobacco samples is described. A ground tobacco sample of 0.5 g is mixed with 3 mL of 2-propanol. The mixture is extracted for twelve minutes with the aid of sonication at an elevated temperature (45–55°C) and then filtered through a 0.45 m disposable filter prior to injection on HPLC. No sample cleanup or solvent evaporation step is required. Chromatographic analysis is performed on a C-18 column and the analysis time is 12.5 minutes. The detection limit for methoprene in tobacco samples is one part per million (g/g).     

Isolation of essential oils from tobacco by gas co-distillation/solvent extraction

Summary The essential oils have been isolated from tobacco leaves using a simple gas co-distillation apparatus. The method involves co-distillation with water under the continuous stream of an inert gas with subsequent single solvent extraction of the distillate. The extract is analysed on GC and GC/MS in splitless injection mode without further concentration. The method was evaluated for reproducibility using n-octadecane as an internal standard. The distillation-extraction procedure was reporducible with an average deviation of ±3% for the major constituents. The present method was applied to the analyses of the essential oils of other agricultural products.Dedicated to Dr. L. S. Ettre on the occasion of his 60th birthday.     

Dynamic ultrasound-assisted extraction of polyphenols in tobacco

A novel extraction method, namely dynamic ultrasound-assisted extraction, is investigated. This technique is efficient with respect to both time and solvent consumption because it utilizes ultrasonic energy in dynamic mode during extraction. Polyphenols (chlorogenic acid, esculetin, rutin, scopoletin, and quercitrin) are extracted from a tobacco (Nicotina tobaccum L.) sample for 10 min with 6 mL of solvent. Fresh solvent is continuously pumped through the sample, with which the analytes can be rapidly extracted, and the possibility of degradation efficiently avoided. Methanol involving 0.5% w/v ascorbic acid was used as extraction solvent; optimal flow rate and extraction time were investigated. The extract was cleaned up by C18 disposable cartridge. The spiked and nonspiked tobacco samples were used for the evaluation of the proposed method. Recoveries obtained were varied from 96 to 108% and RSDs from 2.0 to 4.6%. This extraction technique was revealed to recover larger amounts of polyphenols from tobacco, compared to the static ultrasound-assisted extraction method.     

Supercritical fluid extraction of oxadixyl from food crops

Summary This work describes the study of a degradation curve of Oxadixyl in field-treated potato and tomato samples. The residues were extracted using classical and supercritical fluid (SFE) extraction methods and analyzed by HRGC/ECD. The extraction techniques were compared and the results indicate the advantages of using SFE as an alternative method for pesticide analyses in these samples.