Sodium dodecyl sulfate coated γ-alumina support modified by a new Schiff base for solid phase extraction and flame-AAS determination of lead and copper ions

A simple and fast approach for solid phase extraction is herein described, and used to determine trace amounts of Pb2+ and Cu2+ metal ions. The solid phase support is sodium dodecyl sulfate (SDS)-coated γ-alumina modified with bis(2-hydroxy acetophenone)-1,6-hexanediimine (BHAH) ligand. The adsorbed ions were stripped from the solid phase by 6 mL of 4 M nitric acid as eluent. The eluting solution was analyzed by flame atomic absorption spectrometry (FAAS). The sorption recovery of metal ions was investigated with regard to the effects of pH, amount of ligand, γ-alumina and surfactant and the amount and type of eluent. Complexation of BHAH with Pb2+ or Cu2+ ions was examined via spectrophotometry using the HypSpec program. The detection limit for Cu2+ was 7.9 µg L-1 with a relative standard deviation of 1.67%, while that for Pb2+ was 6.4 µg L-1 with a relative standard deviation of 1.64%. A preconcentration factor of 100 was achieved for these ions. The method was successfully applied to determine analyte concentrations in samples of liver, parsley, cabbage, and water.

Solid phase extraction of zinc with octadecyl silica membrane disks modified by N,N'-disalicylidene-1,2-phenylendiamine and determination by flame atomic absorption spectrometry

A procedure for separation and preconcentration of trace amounts of Zn(II) from aqueous media is proposed. The procedure is based on the adsorption of Zn2+ on octadecyl bonded silica membrane disk modified with N,N'-disalicylidene-1,2-phenylendiamine at pH 7. The retained zinc ions were then stripped from the disk with a minimal amount of 1.5 mol L-1 hydrochloric acid solution as eluent, and determined by flame atomic absorption spectrometry. Maximum capacity of the membrane disk modified with 5 mg of the ligand was found to be 226 µg Zn2+. The relative standard deviation of zinc for ten replicate extraction of 10 µg zinc from 1000 mL samples was 1.2%. The limit of detection of the proposed method was 14 ng of Zn2+ per 1000 mL. The method was successfully applied to the determination of zinc in natural water samples and accuracy was examined by recovery experiments and independent analysis by graphite furnace atomic absorption spectrometry (GFAAS).

Hydrodynamics Characteristics and Gas-Liquid Mass Transfer in a Three Phase Fluidized Bed Reactor

This paper presents the experimental characterization of hydrodynamics and gas-liquid mass transfer in a three-phase fluidized bed containing polystyrene and nylon particles. The influence of gas and liquid velocities on phase holdups and volumetric gas-liquid mass transfer coefficient was investigated for flow conditions similar to those applied in biotechnological process. The phase holdups were obtained by the pressure profile technique. The volumetric gas-liquid mass transfer coefficient was obtained adjusting the experimental concentration profiles of dissolved oxygen in the liquid phase with the predictions of the axial dispersion model. According to experimental results the liquid holdup increases with the gas velocity, whereas the solid holdup decreases. The gas holdup increases significantly with the increase in gas velocity, and it shows for the three-phase fluidized bed comparable values or larger than those of bubble column. The volumetric gas-liquid mass transfer coefficient increases significantly with an increase in the air velocity for both bubble column and fluidized beds. In addition, in the operational condition of high liquid velocity, the presence of low-density particles in the bed increased the gas-liquid mass transfer, and thus the volumetric mass transfer coefficient values obtained in the fluidized bed were comparable or larger than those of bubble column.

Ion mobility spectrometry in liquid analysis

Ion mobility spectrometry (IMS) is a straightforward, low cost method for fast and sensitive determination of organic and inorganic analytes. Originally this portable technique was applied to the determination of gas phase compounds in security and military use. Nowadays, IMS has received increasing attention in environmental and biological analysis, and in food quality determination. This thesis consists of literature review of suitable sample preparation and introduction methods for liquid matrices applicable to IMS from its early development stages to date. Thermal desorption, solid phase microextraction (SPME) and membrane extraction were examined in experimental investigations of hazardous aquatic pollutants and potential pollutants. Also the effect of different natural waters on the extraction efficiency was studied, and the utilised IMS data processing methods are discussed. Parameters such as extraction and desorption temperatures, extraction time, SPME fibre depth, SPME fibre type and salt addition were examined for the studied sample preparation and introduction methods. The observed critical parameters were extracting material and temperature. The extraction methods showed time and cost effectiveness because sampling could be performed in single step procedures and from different natural water matrices within a few minutes. Based on these experimental and theoretical studies, the most suitable method to test in the automated monitoring system is membrane extraction. In future an IMS based early warning system for monitoring water pollutants could ensure the safe supply of drinking water. IMS can also be utilised for monitoring natural waters in cases of environmental leakage or chemical accidents. When combined with sophisticated sample introduction methods, IMS possesses the potential for both on-line and on-site identification of analytes in different water matrices.

Polysiloxane/PVA-glutaraldehyde hybrid composite as solid phase for immunodetections by ELISA

We developed an efficient method to prepare a hybrid inorganic-organic composite based on polyvinyl alcohol (PVA) and polysiloxane using the sol-gel disc technique. Antigen obtained from Yersinia pestis was covalently immobilized onto these discs with glutaraldehyde and used as solid phase in ELISA for antibody detection in serum of rabbits experimentally immunized with plague. Using 1.25 µg antigen per disc, a peroxidase conjugate dilution of 1:4,000 and a serum dilution of 1:200 were adequate for the establishment of the procedure. These values are similar to those used for PVA-glutaraldehyde discs, plasticized filter paper discs and the polyaniline-Dacron composite discs. This procedure is comparable to that which utilizes the adsorption of the antigen to conventional PVC plates, with the amount of antigen being one fourth that employed in conventional PVC plates (5 µg/well). In addition to the performance of the polysiloxane/PVA-glutaraldehyde disc as a matrix for immunodetection, its easy synthesis and low cost are additional advantages for commercial application.

Volatile compounds in noni (Morinda citrifolia L.) at two ripening stages

The volatile components of noni at two ripening stages were isolated by headspace solid-phase microextraction using 65 µm Polydimethylsiloxane-Divinylbenzene (PDMS/DVB) fibers and analyzed using GC/MS. Both maturation stages had several compounds in common. Ninety-six compounds were identified, from which octanoic acid ( 70% of total extract) and hexanoic acid ( 8% of total extract) were found to be the major constituents. Due to noni maturation, octanoic acid, decanoic acid and 2E-nonenal decreased their concentrations, while some esters (methyl hexanoate, methyl octanoate, ethyl octanoate and methyl 4E-decenoate), which their fruity odor notes, increased their contents. Two unsaturated esters, reported for the first time in this fruit, 3-methyl-3-buten-1-yl hexanoate and 3-methyl-3-buten-1-yl octanoate, significantly decreased their concentration in the ripe to over-ripe fruits.

Head Space Solid Phase Micro-Extraction (HS - SPME) of volatile organic compounds produced by Sporidiobolus salmonicolor (CBS 2636)

The aim of the present study was the assessment of volatile organic compounds produced by Sporidiobolus salmonicolor (CBS 2636) using methyl and ethyl ricinoleate, ricinoleic acid and castor oil as precursors. The analysis of the volatile organic compounds was carried out using Head Space Solid Phase Micro-Extraction (HS - SPME). Factorial experimental design was used for investigating extraction conditions, verifying stirring rate (0-400 rpm), temperature (25-60 ºC), extraction time (10-30 minutes), and sample volume (2-3 mL). The identification of volatile organic compounds was carried out by Gas Chromatography with Mass Spectrum Detector (GC/MSD). The conditions that resulted in maximum extraction were: 60 ºC, 10 minutes extraction, no stirring, sample volume of 2.0 mL, and addition of saturated KCl (1:10 v/v). In the bio-production of volatile organic compounds the effect of stirring rate (120-200 rpm), temperature (23-33 ºC), pH (4.0-8.0), precursor concentration (0.02-0.1%), mannitol (0-6%), and asparagine concentration (0-0.2%) was investigated. The bio-production at 28 ºC, 160 rpm, pH 6,0 and with the addition of 0.02% ricinoleic acid to the medium yielded the highest production of VOCs, identified as 1,4-butanediol, 1,2,2-trimethylciclopropilamine, beta-ionone; 2,3-butanodione, pentanal, tetradecane, 2-isononenal, 4-octen-3-one, propanoic acid, and octadecane.

Volatile profile and physical, chemical, and biochemical changes in fresh cut watermelon during storage

Existing data about the aroma of fresh-cut watermelon and the metabolic changes that occur with minimal processing are scarce. Given the close relationship that exists between aroma, texture, and quality characteristics, it is necessary to investigate the changes in the volatile profile and texture of watermelon, a fruit extensively sold in supermarket chains throughout Brazil. The objective of this work was to analyze the volatile profile using solid phase microextraction (SPME) as well as texture changes in fresh-cut watermelon stored at 5 °C for ten days. Chromatography associated with sensory analysis (sniffing) led us to conclude that 9-carbon (C9) alcohols and aldehydes are the major responsible for the flavor and aroma of minimally processed watermelon stored at 5 ± 1 °C/90 ± 5% RH for ten days, and also that the aroma diminishes in intensity with storage, but it does not affect the final quality of the product. It was noted that the amount of drained liquid, soluble pectin, and weight loss increased during storage concurrently with a reduction in firmness and a structural breakdown of the cells. Pectin methyl esterase activity remained constant and polygalacturonase activity was not detected.

Optimization of the HS-SPME-GC/MS technique for determining volatile compounds in red wines made from Isabel grapes (Vitis labrusca)

Abstract Brazilian wine production is characterized by Vitis labrusca grape varieties, especially the economically important Isabel cultivar, with over 80% of its production destined for table wine production. The objective of this study was to optimize and validate the conditions for extracting volatile compounds from wine with the solid-phase microextraction technique, using the response surface method. Based on the response surface analysis, it can be concluded that the central point values maximize the process of extracting volatile compounds from wine, i.e., an equilibrium time of 15 minutes, an extraction time of 35 minutes, and an extraction temperature of 30 °C. Esters were the most numerous compounds found under these extraction conditions, indicating that wines made from Isabel cultivar grapes are characterized by compounds that confer a fruity aroma; this finding corroborates the scientific literature.

Investigations into the extraction and the determination of polycyclic aromatic hydrocarbons (PAHs) from water by solid-phase extraction and capillary gas chromatography/ mass spectrometry

Factors affecting the detennination of PAHs by capillary GC/MS were studied. The effect of the initial column temperature and the injection solvent on the peak areas and heights of sixteen PAHs, considered as priority pollutants, USillg crosslinked methyl silicone (DB!) and 5% diphenyl, 94% dimethyl, 1% vinyl polysiloxane (DBS) columns was examined. The possibility of using high boiling point alcohols especially butanol, pentanol, cyclopentanol, and hexanol as injection solvents was investigated. Studies were carried out to optimize the initial column temperature for each of the alcohols. It was found that the optimum initial column temperature is dependent on the solvent employed. The peak areas and heights of the PAHs are enhanced when the initial column temperature is 10-20 c above the boiling point of the solvent using DB5 column, and the same or 10 C above the boiling point of the solvent using DB1 column. Comparing the peak signals of the PAHs using the alcohols, p-xylene, n-octane, and nonane as injection solvents, hexanol gave the greatest peak areas and heights of the PAHs particularly the late-eluted peaks. The detection limits were at low pg levels, ranging from 6.0 pg for fluorene t9 83.6 pg for benzo(a)pyrene. The effect of the initial column temperature on the peak shape and the separation efficiency of the PARs was also studied using DB1 and DB5 columns. Fronting or splitting of the peaks was obseIVed at very low initial column temperature. When high initial column temperature was used, tailing of the peaks appeared. Great difference between DB! and.DB5 columns in the range of the initial column temperature in which symmetrical.peaks of PAHs can be obtained is observed. Wider ranges were shown using DB5 column. Resolution of the closely-eluted PAHs was also affected by the initial column temperature depending on the stationary phase employed. In the case of DB5, only the earlyeluted PAHs were affected; whereas, with DB1, all PAHs were affected. An analytical procedure utilizing solid phase extraction with bonded phase silica (C8) cartridges combined with GC/MS was developed to analyze PAHs in water as an alternative method to those based on the extraction with organic solvent. This simple procedure involved passing a 50 ml of spiked water sample through C8 bonded phase silica cartridges at 10 ml/min, dried by passing a gentle flow of nitrogen at 20 ml/min for 30 sec, and eluting the trapped PAHs with 500 Jll of p-xylene at 0.3 ml/min. The recoveries of PAHs were greater than 80%, with less than 10% relative standard deviations of nine determinations. No major contaminants were present that could interfere with the recognition of PAHs. It was also found that these bonded phase silica cartridges can be re-used for the extraction of PAHs from water.

OFFLINE AND ONLINE SOLID PHASE EXTRACTION/PRECONCENTRATION OF INORGANICS

Solid phase extraction (SPE) is a powerful technique for preconcentration/removal or separation of trace and ultra trace amounts of toxic and nutrient elements. SPE effectively simplifies the labour intensive sample preparation, increase its reliability and eliminate the clean up step by using more selective extraction procedures. The synthesis of sorbents with a simplified procedure and diminution of the risks of errors shows the interest in the areas of environmental monitoring, geochemical exploration, food, agricultural, pharmaceutical, biochemical industry and high purity metal designing, etc. There is no universal SPE method because the sample pretreatment depends strongly on the analytical demand. But there is always an increasing demand for more sensitive, selective, rapid and reliable analytical procedures. Among the various materials, chelate modified naphthalene, activated carbon and chelate functionalized highly cross linked polymers are most important. In the biological and environmental field, large numbers of samples are to be analysed within a short span of time. Hence, online flow injection methods are preferred as they allow extraction, separation, identification and quantification of many numbers of analytes. The flow injection online preconcentration flame AAS procedure developed allows the determination of as low as 0.1 µg/l of nickel in soil and cobalt in human hair samples. The developed procedure is precise and rapid and allows the analysis of 30 samples per hour with a loading time of 60 s. The online FI manifold used in the present study permits high sampling, loading rates and thus resulting in higher preconcentration/enrichment factors of -725 and 600 for cobalt and nickel respectively with a 1 min preconcentration time compared to conventional FAAS signal. These enrichment factors are far superior to hitherto developed on line preconcentration procedures for inorganics. The instrumentation adopted in the present study allows much simpler equipment and low maintenance costs compared to costlier ICP-AES or ICP-MS instruments.

Electrical conductivity and thermally stimulated current in the paraelectric phase of (NH4)2SO4

Anomalous variations of d.c. electrical conductivity with temperature are observed in ammonium sulphate single crystals, suggesting a possible phase transition at 150°C. Measurements of thermally stimulated current also support these results. The mechanism of electrical conduction is explained on the basis of studies made on doped and quenched crystals.

Numerical model of solid phase transformations governed by nucleation and growth: microstructure development during isothermal crystallization

A simple numerical model which calculates the kinetics of crystallization involving randomly distributed nucleation and isotropic growth is presented. The model can be applied to different thermal histories and no restrictions are imposed on the time and the temperature dependences of the nucleation and growth rates. We also develop an algorithm which evaluates the corresponding emerging grain-size distribution. The algorithm is easy to implement and particularly flexible, making it possible to simulate several experimental conditions. Its simplicity and minimal computer requirements allow high accuracy for two- and three-dimensional growth simulations. The algorithm is applied to explore the grain morphology development during isothermal treatments for several nucleation regimes. In particular, thermal nucleation, preexisting nuclei, and the combination of both nucleation mechanisms are analyzed. For the first two cases, the universal grain-size distribution is obtained. The high accuracy of the model is stated from its comparison to analytical predictions. Finally, the validity of the Kolmogorov-Johnson-Mehl-Avrami model SSSR, is verified for all the cases studied

Solid-phase synthesis of an A-B loop mimetic of the C epsilon 3 domain of human IgE: macrocyclization by Sonogashira coupling

The solid-phase synthesis of a cyclic peptide containing the 21-residue epitope found in the A-B loop of the Cepsilon3 domain of human immunoglobulin E has been carried out. The key macrocyclization step to form the 65-membered ring is achieved in similar to15% yield via an "on-resin" Sonogashira coupling reaction which concomitantly installs a diphenylacetylene amino acid conformational constraint within the loop.

Acrylamide and pyrazine formation in model systems containing asparagine

The effect of different sugars and glyoxal on the formation of acrylamide in low-moisture starch-based model systems was studied, and kinetic data were obtained. Glucose was more effective than fructose, tagatose, or maltose in acrylamide formation, whereas the importance of glyoxal as a key sugar fragmentation intermediate was confirmed. Glyoxal formation was greater in model systems containing asparagine and glucose rather than fructose. A solid phase microextraction GC-MS method was employed to determine quantitatively the formation of pyrazines in model reaction systems. Substituted pyrazine formation was more evident in model systems containing fructose; however, the unsubstituted homologue, which was the only pyrazine identified in the headspace of glyoxal-asparagine systems, was formed at higher yields when aldoses were used as the reducing sugar. Highly significant correlations were obtained for the relationship between pyrazine and acrylamide formation. The importance of the tautomerization of the asparagine-carbonyl decarboxylated Schiff base in the relative yields of pyrazines and acrylamide is discussed.