Informações essenciais para a caracterização de um sistema de análise em fluxo

Essential aspects for characterization of a flow-based analytical procedure or system are discussed in order to permit the composition of a checklist that will lead to a protocol for reporting results and systems in flow analysis. Aspects more related to chromatographic procedures are not considered. The intent is to present normalized proposals in the field of flow analysis for practitioners and developers.

Análise de praguicidas organofosforados em água por extração em fase sólida (SPE) utilizando discos C18 e cromatografia em fase gasosa: avaliação da contaminação do reservatório de Furnas (MG-Brasil)

Solid phase extraction (SPE) in C18 disks has been optimized and validated for extraction of 5 organophosphorus (OP) pesticides in water. Extraction has been followed by separation and detection by gas chromatography/flame photometry. Excellent linearity was obtained for all compounds (r greater than 0.99), with CVs between 1.0-6.9%, recoveries between 73-95% and quantification limits between 2.5-5.0 µg L-1. Samples from Furnas dam were analyzed monthly during one year and 10% showed OP pesticide residues.

Diazepam e nordiazepam em plasma: métodos de extração líquido-líquido e em fase sólida no pré-tratamento de amostras para análise cromatográfica em fase líquida

Analysis of diazepam (DZP) and its active metabolite nordiazepam (NDZP) in plasma is commonly performed in clinical medicine to ensure proper therapeutic effects while minimizing the incidence of toxicity. This study aimed to optimize analytical parameters and compare two pre-treatment techniques, liquid-liquid (LLE) and solid phase extraction (SPE), as well as liquid chromatographic conditions to analyze simultaneously DZP and NDZP in plasma from 20 patients treated with a daily dose of 10 mg. Both techniques showed to be well in line with the international criteria for analytical validation, which permitted to quantify DZP (66.2 - 1148.6 ng mL-1) and NDZP (138.5 - 808.6 ng mL -1) in all samples. The correlation coefficients between SPE and LLE were respectively 0.9729 for DZP and 0.9643 for NDZP.

Alendronato de sódio: metodologias para análise quantitativa

This paper presents a review of some published proposals for the analysis of sodium alendronate. The drug is an aminobisphosphonate compound used to inhibit the osteoclastic resorption of bone, and different methods were developed for its quantitative determination. These methodologies employed reversed-phase or ion-exchange HPLC analysis, both associated with different detectors: UV and fluorescence detection after derivatization of the drug, conductivity and refractive index detectors, as well as the indirect UV detection. Titrimetry and spectrophotometry (with previous complexation of the drug), which are simpler procedures, were also described, but they showed poor specificity when compared to liquid chromatography.

Análise de fármacos em material biológico: acoplamento microextração em fase sólida "no tubo" e cromatografia líquida de alta eficiência

A new solid phase microextraction (SPME) system, known as in-tube SPME, was recently developed using an open tubular fused-silica capilary column, instead of an SPME fiber, as the SPME device. On-line in-tube SPME is usually used in combination with high performance liquid chromatography. Drugs in biological samples are directly extracted and concentrated in the stationary phase of capillary columns by repeated draw/eject cycles of sample solution, and then directly transferred to the liquid chromatographic column. In-tube SPME is suitable for automation. Automated sample handling procedures not only shorten the total analysis time, but also usually provide better accuracy and precision relative to manual techniques. In-tube SPME has been demonstrated to be a very effective and highly sensitive technique to determine drugs in biological samples for various purposes such as therapeutic drug monitoring, clinical toxicology, bioavailability and pharmacokinetics.

Desenvolvimento de colunas cromatográficas de meios de acesso restrito proteína-imobilizada e suas avaliações para análise de fármacos com injeção direta de plasma humano

A series of bovine serum albumin-immobilized supports have been prepared and used as restricted access media (RAM) columns. Restricted-access supports combine size-exclusion of proteins and other high-molar-mass matrix components with the simultaneous enrichment of low-molar mass analytes. These characteristics were chromatographically evaluated for the columns. The RAM-BSA (Bovine Serum Albumin) columns showed excellent performance for exclusion of human plasma protein with good retention capacity for a series of acidic, basic, and neutral drugs.

Análise quiral por espectrometria de massas através da utilização do método cinético

Novel and quantitative mass spectrometry methods for rapid and accurate enantiomeric excess determination are presented. These methodologies use electrospray ionization (ESI) and mass spectrometry (MS) to detect and analyze, via collision-induced dissociation (CID), mass-selected transition metal complexes that promote enantio especific interactions. The data from CID are conveniently treated by the kinetic method, a sensitive linear free energy method of treating mass spectrometric results. Four different variations of this methodology are described: single ratio method (S R), quotient ratio method (Q R), fixed ligand method (S Rfixed), and quotient ratio method with fixed ligand (Q Rfixed). These individual methods are compared and their main features discussed in detail.

Análise estatística e optimização de perfis de redução termoprogramada (TPR)

The effect of operational variables and their interaction in TPR profiles was studied using a fractional factorial experimental design. The heating rate and the reducing agent concentration were found to be the most important variables determining the resolution and sensitivity of the technique. They showed opposite effects. Therefore, they should be manipulated preferentially in order to obtain optimized TPR profiles. The effect of sample particle size was also investigated. The tests were carried out within a Cu/Zn/Al2O3 catalyst used for the water-gas shift reaction that presented two distinct species of Cu2+ in TPR profiles.

O efeito SERS na análise de traços: o papel das superfícies nanoestruturadas

Surface-Enhanced Raman Scattering - SERS - underwent huge advances since a single-molecule Raman spectrum was obtained in 1997. New theoretical and experimental approaches emerged since then leading to a better understanding of the enhancement mechanisms and to a significant improvement in the Raman signal. This review presents the current status of the SERS effect and the promising ways of designing and preparing high performance SERS-active substrates.

Integração de técnicas analíticas e proposta de experimentos para cursos de graduação em análise instrumental: uso de espectrômetro de absorção atômica para medidas de absorção molecular

Simple experiments are proposed for measuring molecular absorption of chromate and dichromate ions using an atomic absorption spectrometer. The experiments can help undergraduate students in instrumental analysis courses understand important aspects involving conceptual and instrumental similarities and differences between frequently used analytical techniques. Hollow cathode lamps were selected with wavelengths in the region of molecular absorption of chromate and dichromate. Calibration curves were obtained and the linear dynamic range was evaluated. Results were compared with those obtained in a molecular absorption spectrometer. The molar absorptivities obtained were also compared.

Metodologia para análise simultânea de ácido nicotínico, trigonelina, ácido clorogênico e cafeína em café torrado por cromatografia líquida de alta eficiência

A reverse phase liquid chromatography method was developed for simultaneous determination of trigonelline, caffeine, nicotinic and chlorogenic (5-CQA) acids in roasted coffee. A gradient of acetic acid/acetonitrile was used as mobile phase and detection was carried out in the UV. The samples were extracted with acetonitrile/water (5:95 v/v) at 80 ºC/10 min. Good recovery (89 to 104%), repeatability and linearity were obtained. Detection limits of 0.01, 0.15, 0.04 and 0.04 mg mL-1 were observed for nicotinic acid, trigonelline, 5-CQA and caffeine. The method, applied to arabica and robusta coffees with different degrees of roasting, was efficient and fast (~35 min) and also allowed identification of cinnamic acids.

Determinação turbidimétrica de metilbrometo de homatropina em formulações farmacêuticas empregando um sistema de análise por injeção em fluxo

A flow injection turbidimetric procedure exploiting merging zones is proposed for determining homatropine methylbromide (HMB) in pharmaceutical preparations. The determination is based on the precipitation reaction of homatropine methylbromide with AgNO3 solution to form a precipitate, which was measured at 410 nm. The analytical curve was linear in the HMB concentration range from 8.0x10-4 to 1.7x10-3 mol L-1, with a detection limit of 9.5x10-5 mol L-1. The recoveries ranged from 94.9 to 104 %, the sampling frequency was 75 h-1 and relative standard deviations were smaller than 2.0 % for solutions containing 1.2x10-3 and 1.5x10-3 mol L-1 HMB (n=10). The results obtained for commercial formulations using the FIA procedure were in good agreement with those obtained by using a comparative method (r= 0.9983).

Ensaio de proficiência para análise de ditiocarbamatos em polpa de banana

A proficiency assay of the determination of dithiocarbamate pesticide residues in banana was carried out. Fourteen laboratories participated in this study. Homogeneity and stability testing were performed by INCQS on the samples sent to the laboratories. Analytical results supplied by the pesticide residues laboratory of the VWA/KvW, Amsterdam, Holland, were used to define the designated value for the thiram concentration in the study samples. RESULTS: Fifty percent of the participating laboratories had satisfactory results. Efforts are needed to improve the precision of the analytical results and to decrease the number of false negative results observed.

Cafeína: revisão sobre métodos de análise

Gravimetric and Bailey-Andrew methods are tedious and provide inflated results. Spectrofotometry is adequate for caffeine analysis but is lengthy. Gas chromatography also is applied to the caffeine analysis but derivatization is needed. High performance liquid chromatography with ultraviolet detection (HPLC-UV) and reversed phase is simple and rapid for xanthine multianalysis. In HPLC-UV-gel permeation, organic solvents are not used. HPLC-mass spectrometry provides an unequivocal structural identification of xanthines. Capillary electrophoresis is fast and the solvent consumption is smaller than in HPLC. Chemometric methods offer an effective means for chemical data handling in multivariate analysis. Infrared spectroscopy alone or associated with chemometries could predict the caffeine content in a very accurate form. Electroanalytical methods are considered of low cost and easy application in caffeine analysis.

Conseqüências da análise incorreta de experimentos blocados

Errors are always present in experimental measurements so, it is important to identify them and understand how they affect the results of experiments. Statistics suggest that the execution of experiments should follow random order, but unfortunately the complete randomization of experiments is not always viable for practical reasons. One possible simplification is blocked experiments within which the levels of certain factors are maintained fixed while the levels of others are randomized. However this has a cost. Although the experimental part is simplified, the statistical analysis becomes more complex.