Determinação simultânea de topiramato, carbamazepina, fenitoína e fenobarbital em plasma empregando cromatografia a gás com detector de nitrogênio e fósforo

Topiramate and the other frequently co-administered antiepileptic drugs carbamazepine, phenytoin and phenobarbital were determined in 100 µL plasma samples by gas chromatography with nitrogen phosphorus detection (GC-NPD), after a one-step liquid-liquid extraction with ethyl acetate, followed by flash methylation with trimethylphenylammonium hydroxide. Total chromatographic run time was 12.5 min. Intra-assay and inter-assay precision was 2.5-7.3% and 1.6-5.2%, respectively. Accuracy was 100.1-104.2%. The limit of quantitation was 1 µg mL-1 for all analytes, proving suitable for routine application in therapeutic drug monitoring of antiepileptic drugs.

Improved method to obtain pfaffic acid as a marker for quality control

Pfaffic acid, a marker of Hebanthe eriantha (Brazilian ginseng), was first isolated in 1983 but is not yet commercially available. This lack of availability compromises the quality control of this plant and its derivatives. This paper proposes a process for pfaffic acid isolation from roots of H. eriantha at a purity suitable for analytical purposes. The steps involved in this process included extraction, hydrolysis, fractionation and purification by preparative HPLC. This process led to isolation of pfaffic acid with a chromatographic purity of 98.5% in a 0.25% yield from dried roots of H. eriantha; this yield is more than forty times higher than that of the current method in the literature.

Determinação espectrofotométrica de sulfato em álcool etílico combustível empregando dibromosulfonazo III

A sensitive spectrophotometric method was developed for sulphate determination in automotive ethanol fuel. The method based on the reaction of the analyte with barium-dibromosulphonazo(III) complex lead to a decrease in the magnitude of the absorbance signals monitored at 649 nm. No sample pretreatment is required and the proposed method allows sulphate determination in the 0.45 - 6.50 mg L-1 range with R.S.D. < 2% and limit of detection of 0.14 mg L-1. The method has been successfully applied for sulphate determination in automotive ethanol fuel and the results agreed with the reference chromatographic method.

Simultaneous and accurate determination of water- and fat-soluble vitamins in multivitamin tablets by using an RP-HPLC method

In the present study, a reversed-phase high-performance liquid chromatographic (RP-HPLC) procedure was developed and validated for the simultaneous determination of seven water-soluble vitamins (thiamine, riboflavin, niacin, cyanocobalamin, ascorbic acid, folic acid, and p-aminobenzoic acid) and four fat-soluble vitamins (retinol acetate, cholecalciferol, α-tocopherol, and phytonadione) in multivitamin tablets. The linearity of the method was excellent (R² > 0.999) over the concentration range of 10 - 500 ng mL-1. The statistical evaluation of the method was carried out by performing the intra- and inter-day precision. The accuracy of the method was tested by measuring the average recovery; values ranged between 87.4% and 98.5% and were acceptable quantitative results that corresponded with the label claims.

Preparação, caracterização e aplicação de fases estacionárias tipo C8 modificadas por óxidos metálicos para cromatografia líquida

This work describes three C8-stationary phases for high performance liquid chromatography based on silica metallized with ZrO2, TiO2 or Al2O3 layers, having poly(methyloctylsiloxane) immobilized onto their surfaces. The stationary phases were characterized using XRF, XAS, FTIR, SEM and elemental analysis to determine the physical characteristics of the oxide and polysiloxane layers formed on the surfaces and chromatographically to evaluate the separation parameters. The results show the changes on the silica surface and allowed proposing a structure for the oxide layer, being observed tetrahedral and octahedral structures, what is completely new in the literature. The formation of a homogeneous layer of metallic oxide (TiO2 and ZrO2) was observed on the silica. The C8-titanized and C8-aluminized stationary phases presented good chromatographic performances, with good values of asymmetry and efficiency. All stationary phase presented few loss of the polymeric layer after the HPLC, indicating that this layer is well attached on the metalized support.

Composição química e atividade anticolinesterásica de uma fração ativa do extrato de folhas de Citrus limon (L.) Burm

This paper describes the chemical composition and acetylcholinesterase inhibition of an active chromatographic fraction of the EtOAc extract of Citrus limon leaves. The composition of the active fraction presented a mixture of two coumarins, 5,8-dimethoxy-psoralen and 5,7- dimethoxycoumarin, identified by ¹H and ¹³C NMR data analysis, including DEPT, COSY, HMBC and HSQC experiments. It was also demonstrated that this mixture presents qualitative and quantitative AChE inhibition. In vitro studies indicated a CE50 value of 340 µg/mL with 95% of confidence. In vivo studies (10 and 25 mg/kg) revealed inhibition of 30.09 and 30.06% of AChE activity in relation to neostigmine, respectively.

Miniprojeto para ensino de Química Orgânica Experimental baseado no acoplamento catalítico N-C promovido por micro-ondas

This paper describes a three-week mini-project for an Experimental Organic Chemistry course. The activities include N-C cross-coupling synthesis of N-(4-methoxyphenyl) benzamide in an adapted microwave oven by a copper catalyst (CuI). Abilities and concepts normally present in practical organic chemistry courses are covered: use of balances, volumetric glassware, separation of mixtures (liquid-liquid extraction and filtration), chromatographic techniques, melting point determination and stoichiometric calculations.

Metabolômica, uma abordagem otimizada para exploração da biodiversidade brasileira: estado da arte, perspectivas e desafios

Brazilian biodiversity is a colossal source of secondary metabolites with remarkable structural features, which are valuable in further biodiscovery studies. In order to fully understand the relations and interactions of a living system with its surroundings, efforts in natural product chemistry are directed toward the challenge of detecting and identifying all the molecular components present in complex samples. It is plausible that this endeavor was born out of recent technological sophistication in secondary metabolite identification with sensitive spectroscopic instruments (MS and NMR) and higher resolving power of chromatographic systems, which allow a decrease in the amount of required sample and time to acquire data. Nevertheless, the escalation of data acquired in these analyses must be sorted with statistical and multi-way tools in order to select key information. Chromatography is also of paramount importance, more so when selected compounds need to be isolated for further investigation. However, in the course of pursuing a "greener" environment, new policies, with an aim to decrease the use of energy and solvents, are being developed and incorporated into analytical methods. Metabolomics could be an effective tool to answer questions on how living organisms in our huge biodiversity work and interact with their surroundings while also being strategic to the development of high value bio-derived products, such as phytotherapeutics and nutraceuticals. The incorporation of proper phytotherapeutics in the so-called Brazilian Unified Health System is considered an important factor for the urgent improvement and expansion of the Brazilian national health system. Furthermore, this approach could have a positive impact on the international interest toward scientific research developed in Brazil as well as the development of high value bio-derived products, which appear as an interesting economic opportunity in national and global markets. Thus, this study attempts to highlight the recent advances in analytical tools used in detection of secondary metabolites, which can be useful as bioproducts. It also emphasizes the potential avenues to be explored in Brazilian biodiversity, known for its rich chemical diversity.

Resíduos de medicamentos veterinários em leite e ovos

The use of veterinary drugs in food producing animals may result in the presence of residues in foods, including milk and eggs. Immunoassay or microbiological tests are used to screen for residues, but chromatographic methods are needed to confirm positive results. In most methods, the sample is extracted with acetonitrile, submitted to clean up or directly analyzed by LC-MS/MS. Results of the Brazilian governmental monitoring programs from 2006 to 2011 have shown that the antiparasitic ivermectin was the drug most frequently found in milk. Residues in eggs are only monitored by one of the programs, and few studies have reported the incidence of veterinary drugs in this matrix in Brazil.

LC/ESI-MS method applied to characterization of flavonoids glycosides in B. forficata subsp. pruinosa

Bauhinia forficata is used in folk medicine for its hypoglycemiant effect. In the south of Brazil, the subspecies pruinosa is found in a region with the characteristic flora, pampa biome. This species has been consumed by the local population as a tea for diabetes treatment. We studied the chemical composition of hydroethanolic extracts using LC/ESI-MS. The leaf extracts were prepared by percolation with 50% (v/v) ethanol. The chromatographic analyses were performed using a reverse-phase system, gradient elution with acetonitrile:phosphoric acid 0.05%, and ESI-MS in the positive ion mode. The chemical profile of the flavonoids was suggested to involve four quercetin and kaempferol glycosides.

Caracterização físico-química de resíduos oleosos do saneamento e dos óleos e graxas extraídos visando a conversão em biocombustíveis

Oily waste from sanitation processes was characterized for its potential use in the generation of biofuels. The waste residues studied showed high levels of oil and grease, reaching up to 87% (m/m) in a grease trap of a food company, showing that these residues can be utilized for the production of biofuels. The results revealed high levels of moisture and saponification as well as high levels of free fatty acids (FFA). Analysis of chromatographic profiles (HPLC) showed great heterogeneity of the fatty acids contained in the sample, and a predominance of palmitic, oleic, linoleic and linolenic acids.

Determination of flavonoids in stamen, gynoecium, and petals of Magnolia grandiflora L. and their associated antioxidant and hepatoprotection activities

Chromatographic analysis of flavonoids in ethyl acetate fractions of the stamen, gynoecium, and petal of Magnolia grandiflora L. by HPLC-PDA-MS/MS-ESI in the negative ionization mode was performed in this study. The results revealed the presence of eight flavonoids: apigenin 8-C-glucoside, luteolin 8-C-glucoside, quercetin 3-O-rutinoside, quercetin 3-O-galactoside, quercetin, 3-O-glucoside, kaempferol 3-O-rutinoside, isorhamnetin 3-O-glucoside, and isorhamnetin. Their quantification revealed that luteolin 8-C-glucoside is the major flavonoid and that the total phenolic content is concentrated primarily in the stamen. The antioxidant and hepatoprotective effects of ethanolic extract of the flower organs were evaluated against hepatotoxicity induced by CCl4, compared with the effects of silymarin.

Terpanos pentacíclicos como indicadores de heterogeneidades composicionais em reservatório de petróleo biodegradado

Reservoir geochemistry has been effectively used to evaluate compositional heterogeneity in petroleum reservoirs by employing oil fingerprinting technique to assess reservoir continuity, primarily in paraffin oil accumulations. In-reservoir biodegradation has resulted in vast deposits of heavy oils globally; therefore, the application of reservoir geochemistry to such accumulations becomes necessary. We recommend the use of pentacyclic terpanes instead of lower molecular compounds, which are less resistant to biodegradation. Using oil fingerprinting technique in this novel way enabled the differentiation of oil composition among sedimentary facies of tar sands (Pirambóia Formation, Paraná Basin).

Phytochemical investigation of Wissadula periplocifolia (L.) C. Presl and evaluation of its antibacterial activity

A phytochemical study on the aerial parts of Wissadula periplocifolia using chromatographic techniques has led to the isolation of sitosterol (1a), stigmasterol (1b), sitosterol 3-O-β-D-glucopyranoside (2a), stigmasterol 3-O-β-D-glucopyranoside (2b), phaeophytin A (3), 13²-hydroxy-(13²-S)-phaeophytin A (4), phaeophytin B (5), 17³-ethoxyphaeophorbide (6), 3,4-seco-urs-4(23),20(30)-dien-3-oic acid (7), 3-oxo-21β-H-hop-22(29)-ene (8), dammaradienone (9a), and taraxastenone (9b). The isolated compounds were characterised by spectroscopic analysis. A preliminary assay to evaluate the antibacterial activity of W. periplocifolia extracts and fractions showed that the dichloromethane, ethyl acetate, and n-butanol fractions were active against Enterococcus faecalis.

Cromatografia gasosa quiral na resolução de enantiômeros envolvidos em flavours de frutas

This work addresses the use of chiral gas chromatography in resolving optically active stereoisomers and racemates found in fruit flavours. It presents the types of chiral selectors applied to terpene-derived metal coordination compounds, polysiloxane-linked α-amino acid and mixed chiral stationary phases, and focuses on derivatized cyclodextrins, the most popular chiral stationary phases presently used in chromatographic analysis. Knowledge about the techniques involved in chiral recognition and enantiomer identification in the fruit flavour field is given along with examples from the latest studies.