Optimization of photo-polymerized sol gel monolithic stationary phases prepared in polyacrylate-coated fused-silica capillaries for capillary electrochromatography

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Alternative methodologies for the determination of aldehydes by capillary electrophoresis

This paper describes 2 alternative methodologies for the determination of selected aldehydes (formaldehyde, acetaldehyde, propionaldehyde, acrolein, and benzaldehyde) by capillary electrophoresis (CE), the first approach is based on the formation of aldehyde-bisulfite adducts and employs free solution CE with reversed electroosmotic flow and indirect detection, using 10 mmol/L 3,5-dinitrobenzoic acid (pH 4.5) containing 0.2 mmol/L cetyltrimethylammonium bromide as the electrolyte. This novel methodology showed a fairly good sensitivity to concentration, with detection limits with respect to a single aldehyde on the order of 10-40 mu g/L, a reasonable analysis time (separation was achieved in <8 min), and no need for sample manipulation. A second approach was proposed in which 2,4-dinitrophenylhydrazine derivatives of the aldehydes were detected in a micellar electrolyte medium (20 mmol/L berate buffer containing 50 mmol/L sodium dodecyl sulfate and 15 mmol/L beta-cyclodextrin). This latter methodology included a laborious sample preconcentration step and showed much poorer sensitivity (0.5-2 mg/L detection limit, with respect to a single aldehyde), despite the use of sodium chloride to promote sample stacking. Both methodologies proved adequate to evaluate aldehyde levels in vehicular emissions. Samples from the tailpipe exhaust of a passenger car vehicle without a catalytic converter and operated with an ethanol-based fuel were collected and analyzed; the results showed high levels of formaldehyde and acetaldehyde (0.41-6.1 ppm, v/v). The concentrations estimated by the 2 methodologies, which were not in good agreement, suggest the possibility of striking differences in sample collection efficiency, which was not the concern of this work.

Quantitative determination of furocoumarins in samples of Carapia by capillary gas chromatography

The occurrence of furocoumarins in the Moraceae has already been demonstrated. We present here the results concerning the chemical composition and quantification of furocoumarins from carapia (Dorstenia species, Moraceae) employed in Brazil because of its medicinal properties against skin diseases. A capillary gas chromatographic procedure is described for the simultaneous determination of the furocoumarins (psoralen, bergapten, pimpinellin, and isopimpinellin) in rhizomes and aerial parts of Dorstenia tubicina, Dorstenia asaroides and Dorstenia vitifolia and in commercial samples. The method is shown to be sensitive and reproducible, and may have application in the analysis of carapia crude drugs.

Analysis of the inflammatory reaction induced by the catfish (Cathorops spixii) venoms

Cathorops spixii is one of the most abundant venomous fish of the southeastern coast of the State of São Paulo, and consequently causes a great part of the accidents seen there. The accidents affect mainly fishermen, swimmers and tourists and are characterized by punctiform or wide wounds, erythema, edema, pain, sudoresis, indisposition, fever, nausea, vomiting and secondary infection. The objective of this work was to characterize the inflammatory response induced in mice by both venoms (mucus and sting) of the catfish C spixii. Our results demonstrated that both venoms induced a great number of rolling and adherent leukocytes in the post-capillary venules of cremaster muscle of mice, and an increase in the vascular permeability in peritoneal cavity. Mucus induced the recruitment of neutrophils immediately after injection followed later by macrophage infiltration. In contrast, the cellular infiltration elicited by sting venom was rapidly resolved. The peritonitis reaction provoked by venoms was characterized by cytokine (IL-6), chemokines (MCP-1 and KC) or lipid mediator (LTB4) production in the peritoneal cavity. The macrophages from 7-day mucus venom-induced exudates upon in vitro mucus venom stimulation, expressed CD1 Ic x MHC class II and release bioactive IL-12p70. on the other hand, sting venom-elicited peritoneal macrophages lost the ability to differentiate into dendritic cells, following re-stimulation in vitro with sting venom, they do not express CD11c, nor do they exhibit sufficient levels of MHC class II. In conclusion, both types of venoms (mucus or sting) promote inflammatory reaction with different profiles, and the inflammatory reaction induced by the first was characterized by antigen persistence in peritoneal cavity that allowed the activation of phagocytic cells with capacity of antigenic presentation. (C) 2007 Elsevier Ltd. All rights reserved.

Indirect determination of chloride and sulfate ions in alcohol fuel by capillary electrophoresis

A capillary zone electrophoresis method using indirect UV detection for the analysis of chloride and sulfate in alcohol fuel samples was developed. The anions were analyzed in less than 3 min using an electrolyte containing 10 mmol 1(-1) chromate and 0.75 mmol 1(-1) hexamethonium bromide (HMB) as electroosmotic flow modifier. Coefficients of variation were better than 0.6% for migration time (n = 10) and between 2.05 and 2.82% for peak area repeatabilities. Analytical curves of peak area versus concentration in the range of 0.065-0.65 mg kg(-1) for chloride and 0.25-4.0 mg kg(-1) for sulfate were linear with coefficients of correlation higher than 0.9996. The limits of detection for sulfate and chloride were 0.033 and 0.041 mg kg(-1), respectively. Recovery values ranged from 85 to 103%. The method was successfully applied for the quantification of sulfate and chloride in five alcohol fuel samples. The concentration of sulfate varied from 0.45 to 3.12 mg kg(-1). Chloride concentrations were below the method's LOD.

Gas chromatographic analysis of indole alkaloids from Tabernaemontana hilariana

A fast and efficient procedure was elaborated to identify the alkaloid constituents from Tabernaemontana hilariana (Apocynaceae). The strategy based on fractioning of the crude alkaloid fraction in small silica cartridges followed by thin-layer chromatography (TLC), capillary gas chromatography-flame ionization detection as well as high-resolution gas chromatography-mass spectrometry afforded voacangine, coronaridine, ibogamine, voacangine pseudoindoxyl, voacangine hydroxyindolenine, 3-hydroxycoronaridine and 3-(2-oxopropyl)coronaridine. (C) 1997 Elsevier B.V. B.V.

Application of low-pressure gas chromatography-ion-trap mass spectrometry to the analysis of the essential oil of Turnera diffusa (Ward.) Urb.

Turnera diffusa Willd. var. afrodisiaca (Ward) Urb. (syn. T. aphrodisiaca) belongs to the family of Turneraceae and is an aromatic plant growing wild in the subtropical regions of America and Africa. It is widely used in the traditional medicine as e.g. anti-cough, diuretic, and aphrodisiac agent. This work presents a 3 min chromatographic analysis using low-pressure (LP) gas chromatography (GC)-ion-trap (IT) mass spectrometry (MS). The combination of a deactivated 0.6 m x 0.10 mm i.d., restrictor with a wide-bore CP-Wax 52 capillary column (10 m x 0.53 mm i.d., 1 mum) reduces the analysis time by a factor of 3-7 in comparison to the use of a conventional narrow bore column. Chromatographic conditions have been optimized to achieve the fastest separation with the highest signal/noise ratio in MS detection. These results allow fast and reliable quality control of the essential oil to be achieved. (C) 2003 Elsevier B.V. All rights reserved.

Nonlinear dynamics of short traveling capillary-gravity waves

We establish a Green-Nagdhi model equation for capillary-gravity waves in (2+1) dimensions. Through the derivation of an asymptotic equation governing short-wave dynamics, we show that this system possesses (1 + 1) traveling-wave solutions for almost all the values of the Bond number θ (the special case θ=1/3 is not studied). These waves become singular when their amplitude is larger than a threshold value, related to the velocity of the wave. The limit angle at the crest is then calculated. The stability of a wave train is also studied via a Benjamin-Feir modulational analysis. ©2005 The American Physical Society.

Recent applications of analytical techniques for quantitative pharmaceutical analysis: A review

The intension of this paper was to review and discuss some of the current quantitative analytical procedures which are used for quality control of pharmaceutical products. The selected papers were organized according to the analytical technique employed. Several techniques like ultraviolet/visible spectrophotometry, fluorimetry, titrimetry, electroanalytical techniques, chromatographic methods (thin-layer chromatography, gas chromatography and high-performance liquid chromatography), capillary electrophoresis and vibrational spectroscopies are the main techniques that have been used for the quantitative analysis of pharmaceutical compounds. In conclusion, although simple techniques such as UV/VIS spectrophotometry and TLC are still extensively employed, HPLC is the most popular instrumental technique used for the analysis of pharmaceuticals. Besides, a review of recent works in the area of pharmaceutical analysis showed a trend in the application of techniques increasingly rapid such as ultra performance liquid chromatography and the use of sensitive and specific detectors as mass spectrometers.

Capillary blood glucose and venous blood glucose measured with portable digital glucometer in diabetic dogs

This study aimed to compare the glycemic values obtained with a glucometer with those determined by a colorimetric enzymatic assay in venous blood as well as to evaluate the possibility of using capillary blood samples of dogs with diabetes mellitus. A group with 30 diabetic dogs was formed and from each dog three blood samples were obtained for glycemic evaluations by different methods and blood collection sites. The mean glycemic values showed no significant difference between the different sites of blood collection and methods (P=0.90). Venous, pinna and carpal pad blood glucose showed excellent correlation with the colorimetric enzymatic assay (r=0.98; r=0.95 and r=0.96 respectively) and the obtained values fit properly the clinically acceptable intervals in the error grid analysis. The present study revealed that carpal pad, venous and pinna glucose measurements are clinically acceptable and this method is feasible for use in hospitalized diabetic dogs. The sample attainment of carpal pad proved to be effective and a viable alternative. Further work is necessary to assess the utility of this technique in a home environment.

Determination of 2-methylimidazole and 4-methylimidazole in caramel colors by capillary electrophoresis

The use of chemical preservative compounds is common in the food products industry. Caramel color is the most usual additive used in beverages, desserts, and breads worldwide. During its fabrication process, 2- and 4-methylimidazole (MeI), highly carcinogenic compounds, are generated. In these cases, the development of reliable analytical methods for the monitoring of undesirable compounds is necessary. The primary procedure for the analysis of 2- and 4-MeI is using LC- or GC-MS techniques. These procedures are time-consuming and require large amounts of organic solvents and several pretreatment steps. This prevents the routine use of this procedure. This paper describes a rapid, efficient, and simple method using capillary electrophoresis (CE) for the separation and determination of 2- and 4-MeI in caramel colors. The analyses were performed using a 75 μm i.d. uncoated fused-silica capillary with an effective length of 40 cm and a running electrolyte consisting of 160 mmol L-1 phosphate plus 30% acetonitrile. The pH was adjusted to 2.5 with triethylamine. The analytes were separated within 6 min at a voltage of 20 kV. Method validation revealed good repeatability of both migration time (<0.8% RSD) and peak area (<2% RSD). Analytical curves for 2- and 4-MeI were linear in the 0.4-40 mg L-1 concentration interval. Detection limits were 0.16 mg L-1 for 4-MeI and 0.22 mg L-1 for 2-MeI. The extraction recoveries were satisfactory. The developed method showed many advantages when compared to the previously used method. © 2013 American Chemical Society.

Determination of sildenafil and vardenafil by capillary zone electrophoresis using capacitively coupled contactless conductivity detection

A method based on capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D) for determination of two important phosphodiesterase type-5 inhibitors (sildenafil and vardenafil) is introduced. The background electrolyte (BGE) consisted of an aqueous solution of 500 mmol L-1 acetic acid, and the capillary was previously treated with polybrene solution to prevent cationic analytes from adsorbing onto the inner surface. Although the analytes migrate in the counter flow, the total time is short. An instrument with two C4D detectors allowed a seamless transition from a fast method (less than one minute) but of low-efficiency using the first detector to a more efficient method using the second detector. The analysis of commercial tablets showed no significant difference between CE-C4D and HPLC methods. Conductivity detection is a well-known low selectivity detection scheme, which in conjunction with the high mobility of the co-ion in the BGE (hydroxonium) allows one to predict that other cationic analogues of sildenafil can also be detected. This is an interesting feature given the increasing number of compounds in this class. © 2013 The Royal Society of Chemistry.

Facies analysis of the Codó formation (Late Aptian) in the Grajaú area, Southern São Luís-Grajaú Basin

Facies descriptions of the Codó Formation in the Grajaú area are provided for the first time, and its sedimentary characteristics compared to those from the Codó area to allow paleoenvironmental reconstructions. Deposits in the Grajaú area include evaporites, limestones and argillites bearing features indicative of a shallow, low energy, subaqueous, saline environment exposed to meteoric and/or capillary conditions. Floodingevaporative concentration-desiccation cycles suggest a saline pan complex surrounded by extensive evaporitic mudflats. The location of the system, whether coastal or inland, is a matter open for debate. However, the later hypothesis is favored considering: 1. Sr isotopic data, with values higher than those expected for Late Aptian marine waters; 2. calcitic composition of limestones (instead of dolomitic and/or magnesitic as expected in coastal settings); and 3. presence of continental ostracods and lack of marine fauna. This interpretation is consistent with that proposed for UpperAptian deposits of the Codó area, but the depositional system there was one dominated by more stable, well-stratified, anoxic waters and evaporite precipitation in central lacustrine areas, while in the Grajaú area the salt pan was more oxygenated and ephemeral, with salt precipitation mainly in marginal areas or along surrounding mudflats.

A simple and rapid screening method for sulfonamides in honey using a flow injection system coupled to a liquid waveguide capillary cell

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