Otimização de metodologia para determinação de hidrocarbonetos policíclicos aromáticos pela técnica de extração por líquido pressurizado e sua aplicação a diferentes solos brasileiros

Os hidrocarbonetos policíclicos aromáticos (HPA) representam hoje grande preocupação à comunidade científica devido a sua comprovada ação cancerígena e mutagênica, assim tornam-se necessárias metodologias mais eficientes para suas determinações. O presente trabalho desenvolveu a técnica de extração por líquido pressurizado com a etapa de clean-up simultânea a extração, com sílica e alumina como adsorventes dentro da cela do equipamento ASE-350. A metodologia desenvolvida foi comparada com a tradicional extração por Sohxlet através de material de referência certificado. A extração por Soxhlet, apesar de eficiente, mostrou-se dispendiosa pelo gasto enorme de tempo, solvente e adsorventes quando comparada a extração por líquido pressurizado. De maneira geral a extração por líquido pressurizado apresentou-se mais vantajosa que a tradicional extração por Soxhlet. A eficiência da metodologia desenvolvida também foi testada através de quatro diferentes tipos de solos brasileiros fortificados com solução padrão de HPA. Os solos utilizados foram dos seguintes locais: Nova Lima MG, Lavras MG, Casimiro de Abreu RJ e Luiz Eduardo Magalhães BA. Todos possuíam características granulométricas e químicas diferentes entre si. Dois solos foram classificados em latossolos vermelhos, um em vermelho-amarelo e um em planossolo. Houve diferença significativa na eficiência de recuperação de alguns HPA quando comparados os quatro tipos de solos, já para outros HPA não evidenciou-se influência da tipologia do solo

Treatment of Phaeodactylum tricornutum cells with papain facilitates lipid extraction.

Triacylglycerols (TAGs) from microalgae have the potential to be used for biodiesel, but several technical and economic hurdles have to be overcome. A major challenge is efficient extraction of intracellular TAGs from algae. Here we investigate the use of enzymes to deconstruct algal cell walls/membranes. We describe a rapid and simple assay that can assess the efficacy of different enzyme treatments on TAG-containing algae. By this means crude papain and bromelain were found to be effective in releasing TAGs from the diatom Phaeodactylum tricornutum, most likely because of their cysteine protease activity. Pre-treating algal biomass with crude papain enabled complete extraction of TAGs using heptane/isopropyl alcohol. Heptane as a single solvent was also effective, although complete recovery of TAG was not obtained. Economic implications of these findings are discussed, with the aim to reduce the complexity of, and energy needed in, TAG extraction.

Treatment of Phaeodactylum tricornutum cells with papain facilitates lipid extraction

Triacylglycerols (TAGs) from microalgae have the potential to be used for biodiesel, but several technical and economic hurdles have to be overcome. A major challenge is efficient extraction of intracellular TAGs from algae. Here we investigate the use of enzymes to deconstruct algal cell walls/membranes. We describe a rapid and simple assay that can assess the efficacy of different enzyme treatments on TAG-containing algae. By this means crude papain and bromelain were found to be effective in releasing TAGs from the diatom Phaeodactylum tricornutum, most likely because of their cysteine protease activity. Pre-treating algal biomass with crude papain enabled complete extraction of TAGs using heptane/isopropyl alcohol. Heptane as a single solvent was also effective, although complete recovery of TAG was not obtained. Economic implications of these findings are discussed, with the aim to reduce the complexity of, and energy needed in, TAG extraction. © 2012 Elsevier B.V.

Extraction of genomic DNA using a new amino silica monolithic column

A new amino silica monolithic column was developed for DNA extraction in a miniaturized format. The monolithic column was prepared in situ by polymerization of tetraethoxysilane (TEOS) and N-(beta-aminoethyl)-gamma-aminopropylmethyldimethoxysilane (AEAPMDMS). DNA was loaded in 50 mM tris(hydroxylmethyl)aminomethane-EDTA buffer at pH 7.0 and eluted with 300 mM potassium phosphate solution at pH 10.0. Under optimal condition, a 6.0-cm monolithic column provided a capacity of 56 ng DNA with an extraction efficiency of 71 +/- 5.2% (X +/- RSD). When the amino silica monolithic column was applied to extract genomic DNA from the whole blood of crucian carp, an extraction efficiency of 52 +/- 5.6% (X +/- SD) was obtained by three extractions. Since the chaotropic-based sample loading and organic solvent wash steps were avoided in this procedure, the purified DNA was suitable for downstream processes such as PCR. This amino silica monolithic column was demonstrated to allow rapid and efficient DNA purification in microscale.

Optimization of an effective extraction procedure for the analysis of microcystins in soils and lake sediments

Microcystin analysis in sediments and soils is considered very difficult due to low recovery for extraction. This is the primary limiting factor for understanding the fate of toxins in the interface between water and sediment in both the aquatic ecosystem as well as in soils. In the present study, a wide range of extraction solvents were evaluated over a wide range of pH, extraction approaches and equilibration time to optimize an effective extraction procedure for the analysis of microcystins in soils and lake sediments. The number of extractions required and acids in extraction solutions were also studied. In this procedure, EDTA-sodium pyrophosphate solution was selected as an extraction solvent based on the adsorption mechanism study. The optimized procedure proved to be highly efficient and achieved over 90% recovery. Finally, the developed procedure was applied to field soil and sediment sample collected from Chinese lakes during bloom seasons and microcystins were determined in six of ten samples. (c) 2005 Elsevier Ltd. All rights reserved.

Physical design of the new extraction system for SFC

The HIRFL (Heavy Ion Research Facility at Lanzhou) is a cyclotron complex. Its injector is a cector focusing cyclotron with K=69. Since the HIRFL started the operation in 1989, two bigger items of improvements have been finished, the species and intensity of the accelerated particles are increased obviously. But due to the lower extraction efficiency of the SFC, on one hand, a lot of beam lost, and on other hand, outgas from the surface of the electrostatic deflector is serious because of beam hitting. Even sometimes the vacuum press is destroyed. In the paper a new physical design is made to get an extraction system of the SFC with a higher efficiency.

New Organic Sensitizer for Stable Dye-Sensitized Solar Cells with Solvent-Free Ionic Liquid Electrolytes

We report a high molar extinction coefficient metal-free sensitizer composed of a triarylamine donor in combination with the 2-(2,2'-bithiophen-5-yl)acrylonitrile conjugation unit and cyanoacrylic acid as an acceptor. In conjugation with a volatile acetonitrile-based electrolyte or a solvent-free ionic liquid electrolyte, we have fabricated efficient dye-sensitized solar cells showing a corresponding 7.5% or 6.1% efficiency measured under the air mass 1.5 global sunlight. The ionic liquid cell exhibits excellent stability during a 1000 h accelerated test under the light-soaking and thermal dual stress. Intensity-modulated photocurrent and photovolatge spectroscopies were employed along with the transient photoelectrical decay measurements to detail the electron transport in the mesoporous titania films filled with these two electrolytes.

Reversed micellar solubilization extraction and separation of thorium(IV) from rare earth(III) by primary amine N1923 in ionic liquid

The extraction behavior of thorium(IV) sulfate by primary amine N1923 in imidazolium-based ionic liquid (IL) namely 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)mim]PF6) was systematically studied in this paper. Results showed that the extraction behavior was quite different from that using conventional solvent as diluent. A reversed micellar solubilization extraction mechanism was proposed for the extraction of thorium(IV) by N1923/[C(8)mim]PF6 via slope analysis method and polarized optical microscopy (POM)/transmission electron microscopy (TEM) observation. The salt-out agent, Na2SO4, was demonstrated to prompt this extraction mechanism.

Solvent impregnated resin prepared using task-specific ionic liquids for rare earth separation

A novel bifunctional task-specific ionic liquid (TSIL), i.e. [trialkylmethylammonium][sec-nonylphenoxy acetate] ([A336] [CA-100]) was impregnated on intermediate polarized XAD-7 resin, and the prepared solvent impreganated resin (SIR) was studied for rare earth (RE) separation. Adsorption ability of the SIR was indicated to be obviously higher than that prepared by [A336][NO3] because of the functional anion of [A336][CA-100]. Adsorption kinetics, adsorption isotherm, separation and desorption of the SIR were also studied.

Isothermal crystallization behavior of the poly(L-lactide) block in poly(L-lactide)-poly(ethylene glycol) diblock copolymers: Influence of the PEG block as a diluted solvent

Isothermal crystallization kinetics and morphology of the poly(L-lactide) block in poly(L-lactide)poly(ethylene glycol) diblock copolymers were studied by differential scanning calorimetry (DSC) and polarized optical microscopy (POM), respectively. The results were compared with that of the PLLA homopolymer. The introduction of the PEG block accelerated the crystallization rate of the PLLA block and promoted to form ring-banded spherulites. The analysis of isothermal crystallization kinetics has shown that the PLLA homopolymer accorded with the Avrami equation. But the PLLA block of the diblock copolymers deviated from the Avrami equation, which resulted from increasing of the crystallization rate and occurring of the second crystallization process. The equilibrium melting temperature (T,,) of the PLLA block fell with its molecular weight decreasing. The conditions to obtain more regular ring-banded spherulites were below: the sample was the PLLA block of LA(5) EG(5); the crystallization temperature was about from 95 degrees C to 100 degrees C, which almost corresponded to regime II.

High efficient extraction of M@C-2n (M = La, Ce) by a high pressure and high temperature method

A high pressure and high temperature method was used to efficiently extract on a large scale metallofullerenes M@C-2n (M=La,Ce) in a closed vessel under argon gas protection. With pyridine as the HPHT solvent, about 60-80% M@C-2n and 30-55% M@C-82 can be enriched, M@C-82 is dissolved selectively; With toluene as the HPHT solvent, M@C-2n can also be efficiently extracted, especially M@C-74, which is a new member of M@C-2n soluble species. (C) 1998 Elsevier Science Ltd. All rights reserved.

Two-step-method extraction of endohedral metallofullerenes

A new and efficient extraction method of endohedral metallofullerenes, especially of rare-earth elements encapsulated metallofullerenes, has been reported in this paper. Soxhlet-extraction of raw soot with toluene was used in the first step to wash away most accompanying C-60, C-70. Then pyridine was chosen as solvent to obtain high-temperature and high pressure extract. Two kinds of extract were analysed by DEI-MS and LDI-MS, the results indicate that this two-step method can provide the extract which has the highest fraction of endohedral metallofullerenes. So it will greatly simplify the following separation and purification processes of metallofullerenes.

An efficient combination of supercritical fluid extraction and high-speed counter-current chromatography to extract and purify homoisoflavonoids from Ophiopogon japonicus (Thunb.) Ker-Gawler

Supercritical fluid extraction (SFE) was used to extract homoisoflavonoids from Ophiopogon japonicus (Thunb.) Ker-Gawler. The optimization of parameters was carried out using an orthogonal test L-9 (3)(4) including pressure, temperature, dynamic extraction time and the amount of modifier. The process was then scaled up by 100 times with a preparative SFE system under the optimized conditions of 25 MPa, 55 degrees C, 4.0 h and 25% methanol as a modifier. Then crude extracts were separated and purified by high-speed counter-current chromatography (HSCCC) with a two-phase solvent system composed of n-hexane/ethyl acetate/methanol/ACN/water (1.8:1.0:1.0:1.2:1.0 v/v). There three homoisoflavonoidal compounds including methylophiopogonanone A 6-aldehydo-isoophiopogonone A, and 6-formyl-isoophiopogonanone A, were successfully isolated and purified in one step. The collected fractions were analyzed by HPLC. In each operation, 140 mg crude extracts was separated and yielded 15.3 mg of methylophiopogonanone A (96.9% purity), 4.1 mg of 6-aldehydo-isoophiopogonone A (98.3% purity) and 13.5 mg of 6-formyl-isoophiopogonanone A (97.3% purity) respectively. The chemical structure of the three homoisoflavonoids are identified by means of ESI-MS and NMR analysis.

The extraction of pigments from fresh Laminaria japonica

The pigments in Laminaria japonica was extracted with six organic solvents and analyzed in spectroscopy analysis. The extractions conditions were screened by an orthogonal test and the quantity of extracted pigments was determined spectroscopically. The results show that: (1) among the six organic solvents, acetone was the most effective one for the extraction; (2) the optimum extraction conditions were as follows: the ratio of S/M (solvent volume/ material weight) was 30 ml/g; fresh seaweed was extracted 2 times in 2 h; (3) the average total content of pigments was 1.85 mg/g (calculated with dry L. japonica).

Application of accelerated carbonation with a combination of Na2CO3 and CO2 in cement-based solidification/stabilization of heavy metal-bearing sediment

The efficient remediation of heavy metal-bearing sediment has been one of top priorities of ecosystem protection. Cement-based solidification/stabilization (s/s) is an option for reducing the mobility of heavy metals in the sediment and the subsequent hazard for human beings and animals. This work uses sodium carbonate as an internal carbon source of accelerated carbonation and gaseous CO2 as an external carbon source to overcome deleterious effects of heavy metals on strength development and improve the effectiveness of s/s of heavy metal-bearing sediment. In addition to the compressive strength and porosity measurements, leaching tests followed the Chinese solid waste extraction procedure for leaching toxicity - sulfuric acid and nitric acid method (HJ/T299-2007), German leaching procedure (DIN38414-S4) and US toxicity characteristic leaching procedures (TCLP) have been conducted. The experimental results indicated that the solidified sediment by accelerated carbonation was capable of reaching all performance criteria for the disposal at a Portland cement dosage of 10 wt.% and a solid/water ratio of 1: 1. The concentrations of mercury and other heavy metals in the leachates were below 0.10 mg/L and 5 mg/L, respectively, complying with Chinese regulatory level (GB5085-2007). Compared to the hydration, accelerated carbonation improved the compressive strength of the solidified sediment by more than 100% and reduced leaching concentrations of heavy metals significantly. It is considered that accelerated carbonation technology with a combination of Na2CO3 and CO2 may practically apply to cement-based s/s of heavy metal-bearing sediment. (C) 2008 Elsevier B.V. All rights reserved.