Simultaneous determination of furanocoumarins in infusions and decoctions from Carapia (Dorstenia species) by high-performance liquid chromatography

The use of furanocoumarins, which are photosensitizing compounds, combined with exposure to UV-A radiation is a common treatment for vitiligo, psoriasis, and a number of other skin diseases. Although furanocoumarins plus UV-A treatment is highly effective, several studies have shown that exposure to high doses increases the risk to development of cutaneus carcinoma. Several Dorstenia species are used in folk medicine, mainly against skin diseases, because of the presence of biologically active compounds. We present here analysis of the chemical composition of furanocoumarins from infusion and decoction of Carapia (Dorstenia species), which is used in Brazil against several diseases. We have employed high-performance liquid chromatography (HPLC) procedures for the quantitative determination of psoralen, bergapten, and isopimpinellin. The contents of furanocoumarins revealed an insignificant difference between infusion and decoction. Dorstenia tubicina and D. asaroides contained psoralen and bergapten only in the rhizomes, whereas D. vitifolia shows solely isopimpinellin in both rhizomes and aerial parts.

Determination of oligoelements in parenteral formulations by planar chromatography and spectrophotometry

The authors have studied the chromatographic behavior of parenteral preparations for pediatric use containing inorganic cations. After separation and identification by thin-layer chromatography, Mn2+, Zn2+, and Cu2+ were analyzed by a method based on reaction with an appropriate reagent and extraction with an organic solvent which yielded elution and preconcentration, resulting in an appropriate solution for colorimetric quantitation. Cr3+ cation was determined by atomic absorption spectrophotometry after appropriate chromatographic separation, using microcrystalline cellulose (adsorbent) and an acetone:water:hydrochloric acid mixture (80:5:8) as the mobile phase.

Determination of acetaldehyde in fuel ethanol by high-performance liquid chromatography with electrochemical detection

The cyclic voltammetric behavior of acetaldehyde and the derivatized product with 2,4-dinitrophenylhydrazine (DNPHi) has been studied at a glassy carbon electrode. This study was used to optimize the best experimental conditions for its determination by high-performance liquid chromatographic (HPLC) separation coupled with electrochemical detection. The acetaldehyde-2,4-dinitrophenyl.hydrazone (ADNPH) was eluted and separated by a reversed-phase column, C-18, under isocratic conditions with the mobile phase containing a binary mixture of methanol/LiCl(aq) at a concentration of 1.0 x 10(-3) M (80:20 v/v) and a flow rate of 1.0 mL min(-1). The optimum condition for the electrochemical detection of ADNPH was +1.0 V vs. Ag/AgCl as a reference electrode. The proposed method was simple, rapid (analysis time 7 min) and sensitive (detection limit 3.80 mu g L-1) at a signal-to-noise ratio of 3:1. It was also highly selective and reproducible [standard deviation 8.2% +/- 0.36 (n = 5)]. The analytical curve of ADNPH was linear over the range of 3-300 mg L-1 per injection (20 mu L), and the analytical recovery was > 99%.

Use of chemically modified silica with beta-diketoamine groups for separation of alpha-lactoalbumin from bovine milk whey by affinity chromatography

Silica gel surface was chemically modified with beta-diketoamine groups by reacting the silanol from the silica surface with 3-aminopropyl-triethoxysilane and 3-bromopentanedione, With this material, copper ions were adsorbed from aqueous solutions, the chemical analysis of the silica-gel-immobilized acetylacetone provided a quantity of 0.67 mmol g(-1) of organic groups attached to the support and 0.63 mmol g(-1) of copper, This material was used as a stationary phase in IMAC (immobilized metal affinity chromatography), to separate alpha-lactoalbumin from bovine milk whey, the results showed an efficient separation in the chromatographic column, the possibility of reutilization of the stationary phase was also investigated. (C) 1997 Academic Press

Determination of rice herbicides, their transformation products and clofibric acid using on-line solid-phase extraction followed by liquid chromatography with diode array and atmospheric pressure chemical ionization mass spectrometric detection

A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 mi of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the S-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples. (C) 2000 Elsevier B.V. B.V. All rights reserved.

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.

Determination of aldehydes and ketones in fuel ethanol by high-performance liquid chromatography with electrochemical detection

A new methodology was developed for analysis of aldehydes and ketones in fuel ethanol by high-performance liquid chromatography (HPLC) coupled to electrochemical detection. The electrochemical oxidation of 5-hydroxymetkylfurfural, 2-furfuraldehyde, butyraldehyde, acetone and methyl ethyl ketone derivatized with 2,4-dinitrophenylhydrazine (DNPH) at glassy carbon electrode present a well defined wave at +0.94 V; +0.99 V; +1.29 V; +1.15 V and +1.18 V, respectively which are the basis for its determination on electrochemical defector. The carbonyl compounds derivatized were separated by a reverse-phase column under isocratic conditions with a mobile phase containing a binary mixture of methanol /LiClO4(aq) at a concentration of 1.0 x 10(-3) mol L-1 (80:20 v/v) and a flow-rate of 1.1 mL min(-1). The optimum potential for the electrochemical detection of aldehydes-DNPH and ketones-DNPH was +1.0 V vs. Ag/AgCl. The analytical curve of aldehydes-DNPH and ketones-DNPH presented linearity over the range 5.0 to 400.0 ng mL(-1), with detection limits of 1.7 to 2.0 ng mL(-1) and quantification limits from 5.0 to 6.2 ng mL(-1), using injection volume of 20 mu L. The proposed methodology was simple, low time-consuming (15 min/analysis) and presented analytical recovery higher than 95%.

Pharmacokinetic Study of Nobiletin and Tangeretin in Rat Serum by High-Performance Liquid Chromatography-Electrospray Ionization-Mass Spectrometry

Nobiletin (NOB) and tangeretin (TAN), two of the main polymethoxylated flavones (PMFs) in citrus, influence a number of key biological pathways in mammalian cells. Although the impacts of NOB and TAN on glucose homeostasis and cholesterol regulation have been investigated in human clinical trials, much information is still lacking about the metabolism and oral bioavailability of these compounds in animals. In this study, NOB and TAN were administered to rats by gavage and intraperitoneal (ip) injection, and the blood serum concentrations of these compounds and their main metabolites were monitored by high-performance liquid chromatography-electrospray ionization-mass spectrometry (HPLC-ESI-MS). In addition to the administered compounds, two metabolites of TAN and eight metabolites of NOB were detected and measured over 24 h. With identical oral doses, nearly 10-fold higher absorption of NOB occurred compared to TAN. For both compounds, maximum levels of glucuronidated metabolites occurred in the blood serum at later time points (similar to 5-8 h) compared to the earlier T(max) a values for NOB and TAN. In most cases the glucuronides occurred at substantially higher concentrations than the aglycone metabolites. Low levels of NOB and TAN and their metabolites were detectable in rat blood serum even at 24 h after treatment.

Determination of the sodium monofluoroacetate in serum by gas chromatography

Sodium monofluoroacetate (NAFAc) has been widely used for vertebrate pest control, such as rabbits in Australia. However NAFAc is extremely toxic to all vertebrates and its use is restricted. Although this compound is stringently restricted, the occurrence of accidental and homicidal poisoning is no ever-present possibility.The method developed in this work shows the applicability of SPE with alumina cartridges for the extraction of NAFAc from serum samples. The method is efficient with recoveries of at least 96.8% from spiked serum. The samples were subsequently derivatized with dicyclohexylcabodiimide (DCC), using 2,4-dichloroaniline (DCA), to make the product volatile for GC analysis.

Determination of organochlorine pesticides and polychlorinated biphenyls residues in municipal solid waste compost by gas chromatography with electron-capture detection

A simple and efficient method for the simultaneous gas chromatographic determination of ten organochlorine pesticides (alpha-HCH, beta-HCH, gamma-HCH, p,p'-DDT, o,p'-DDT, p,p'-DDD, p,p'-DDE, aldrin, endrin, and dieldrin) and six congeners of PCBs (PCB 28, 52, 118, 138, 153, and 180) in municipal solid waste compost is described. The procedure involves a solid-phase dispersion matrix using celite as dispersant sorbent, alumina as clean up sorbent and hexane-dichloromethane (7:3, v/v) mixture as eluting solvent. An additional purification step with copper was necessary to eliminate sulphur. Analysis of the sample was performed by GC-ECD. The method was validated with fortified samples at two concentration levels (0.025 and 0.05 mg kg(-1)). Average recovery ranged from 77 to 121% with relative standard deviation between 1 and 18%. The detection limits, which ranged from 0.003 to 0.01 mg kg-1, were lower than those established by the Baden-Wurttemberg directive (0.033 mg kg(-1)).

High resolution ultra high pressure liquid chromatography-time-of-flight mass spectrometry dereplication strategy for the metabolite profiling of Brazilian Lippia species

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Counterion effects on the structure and solubilization properties of anionic detergents. Role of hydrophobic cations in stabilizing micelles and attenuating their solvent properties

A series of alkyl sulfate detergents has been investigated in the presence of the cations Na +, methylviologen(2+) (MV 2+), 4-(cyanomethyl)pyridinium(1+) (CMP +), and tetramethylammonium (TMA +). The binding of these ions to the aqueous micellar assemblies has been measured through studies of luminescence quenching with the extramicellar probe, RuL 34-, where L = 4,4′-dicarboxy-2,2′-bipyridine. A general comparison of the alkyl sulfate aggregates with the nonquenching cations Na + and TMA + shows that the latter ion reduces the critical micelle concentration but at the same time depresses the ability of the detergent assemblies to bind or solubilize the hydrophobic quencher cations MV 2+ or CMP +. The reduced binding ability of the TMA + aggregates compared to that of the corresponding Na + soaps shows up largely in the form of a reduced favorable ΔS° for the solubilization in the case of the former. The results are in accord with a picture of the TMA + micelle as being more stable and more disordered than the corresponding assembly with Na + as the counterion. © 1989 American Chemical Society.