Alessandra L.M.C. da Cunha

Determination of enrofloxacin by room-temperature phosphorimetry after solid phase extraction on an acrylic polymer sorbent.

A phosphorimetric method was developed to enable the determination of enrofloxacin using photochemical derivatization which was used to both improve detection limits and to minimize the uncertainty of measurements. Phosphorescence was induced on cellulose containing TlNO(3). Absolute limit of detection at the ng range and linear analytical response over three orders of magnitude were achieved. A metrological study was made to obtain the combined uncertainty value and to identify that the precision was mainly affected by the changing of substrates when measuring the signal from each replicate. Pharmaceutical formulations containing enrofloxacin were successfully analyzed by the method and the results were similar to the ones achieved using a HPLC method. A solid phase extraction on an acrylic polymer was optimized to separate enrofloxacin from interferents such as diclofenac and other components from biological matrices, which allowed the successful use of the method in urine analysis.

Laser induced fluorescence and photochemical derivatization for trace determination of camptothecin.

Laser-excited fluorescence was used for the selective determination of camptothecin in samples containing anti-cancer camptothecin-analogs (irinotecan and topotecan). The selectivity of the method was based on the UV photochemical derivatization in basic solution which increased the analyte fluorescence (337/450 nm) and eliminated fluorescence from the two campthotecin-analogs. The influence of UV exposure time and sodium hydroxide concentration was studied using an experimental design. Limit of detection was 4 × 10(-10) mol L(-1) with linear fluorescence response up to 1 × 10(-6)mol L(-1). Average recoveries of camptothecin (added to the samples to simulate a contamination) were 92 ± 4 and 94 ± 6% (n=3) respectively in irinotecan and topotecan based pharmaceuticals.

Spectrofluorimetric determination of tetrabenazine after photochemical derivatization in basic medium.

Photochemical derivatization is proposed for the spectrofluorimetric determination of tetrabenazine (TBZ). A central composite design was used to adjust experimental conditions (60 min of UV in a 0.45 mol L(-1) NaOH solution) enabling the improvement of the analyte signal-to-blank ratio of one order of magnitude, when compared to the TBZ original fluorescence. Limit of quantification was 4.7×10(-8) mol L(-1) but the detection power can be improved at least 10 times using solid phase extraction that also allows the separation of the analyte from matrix components, enabling the analysis of biologic fluids. Linear range covered at least three orders of magnitude. The combined uncertainty of the determination (at a 5×10(-6) mol L(-1)) was 16%. Recoveries of TBZ in the analyses of a pharmaceutical formulation were in agreement with the ones obtained using a HPLC method. Recovery in saliva (5×10(-7) mol L(-1) of TBZ) was 90±3% (n=3). The procedure minimizes the use of toxic chemical derivatization reagents and the generation of hazardous waste.

Voltammetric determination of sibutramine in beverages and in pharmaceutical formulations

A simple and sensitive method has been proposed for the determination of sibutramine-HCl in energy drinks, green tea and pharmaceutical formulations using differential pulse voltammetry performed on a hanging mercury drop electrode. In the chosen experimental condition (Mcllvaine pH 4.0 buffer, 50 mV pulse amplitude and 40 mV s-1 scan velocity), sibutramine-HCl presented a reversible behavior and a peak maximum at -80 mV. Detection limit was 0.4 mg L-1 and the working linear range extended up to 33.3 mg L-1 (r = 0.99). Analysis of real and fortified samples enabled recoveries between 91 and 102%. The electroanalytical method was compared with a HPLC method which indicated it accuracy.

Selective Spectrofluorimetric Method and Uncertainty Calculation for the Determination of Camptothecin in the Presence of Irinotecan and Topotecan

A selective fluorimetric method was developed to quantify camptothecin (CPT) in irinotecan (CPT-11) and in topotecan (TPT) based anti-cancer drugs. Selectivity was achieved by experimental optimization and using synchronized scanning and second-order spectral derivatization. The limits of quantification for CPT were in the order of 1 × 10−7 mol L−1 with a linear response up to 1 × 10−5 mol L−1. The combined uncertainty associated with the CPT fluorescence measurement at a 5 × 10−7 mol L−1 level were 10.9% and 6% of the reference level, respectively, for TPT and CPT-11 based pharmaceutical formulations. The CPT recoveries of 95 ± 12% and 91 ± 5.6% (n = 3) were achieved, respectively, in samples containing CPT-11 and TPT.

Determination of the Camptothecin Derivatives CPT-11 and SN-38 in Urine and Saliva by Micellar Electrokinectic Chromatography

The anti-cancer synthetic drug irinotecan (CPT-11) and its active metabolite SN-38 have been determined by micellar electrokinetic capillary chromatography (MEKC). The detection of the analytes was made at 368 nm and their separation took less than 7 min using a borate buffer (pH 8.8 at 25 mmol L−1) solution containing sodium dodecyl sulfate (45 mmol L−1) and acetonitrile (13.5% v/v). On-line analyte concentration (normal stacking mode) and the use of a highly sensitive cell (Z shaped cell) improved detection limits (at the 10−8 mol L−1 level). Recovery in fortified human saliva was 108 ± 5%, in agreement with the result achieved with the reference HPLC method. For the analysis of urine from rats submitted to a single dose of CPT-11 and SN-38, camptothecin was used as internal standard enabling recoveries close to 100% when compared to the results achieved using HPLC.

Photochemical derivatization of amitriptyline using a green chemistry approach: fluorimetric determination and photochemical reaction mechanism

Intense fluorescence from amitriptyline (AMT) was achieved after photochemical derivatization in an acidic aqueous medium (60 min of UV irradiation of solutions containing 0.027 mol L−1 HCl). After the reaction, fluorescence was significantly enhanced enabling the indirect fluorimetric determination of AMT in drugs and in a pharmacopoeia reference material. The limit of quantification (LOQ) was 1.3 × 10−7 mol L−1 and measurement uncertainty was about 6% at the concentrations close to the LOQ and less than 4% at higher concentrations. The mechanism of the photoreaction was proposed based on the identification of the products and on its kinetics. Studies aiming at the determination of AMT in human serum indicate the potential of the approach as a cheap and simple screening procedure for tricyclic antidepressants.

Pesticide dispersion by spraying under tropical conditions

ABSTRACT Pesticide air pollution by spraying was evaluated under different temperature, humidity and wind climatic conditions in Brazil. Field experiments were performed with application towards the soil and in guava orchards, where spray dispersion was monitored by adding p-aminobenzoic acid (PABA), a fluorescent substance, as a tracer to the water contained in the spray tanks. Samples were collected with filter membranes (Whatman 180025), and the PABA was extracted from the filters by shaking with water in a Petri dish and measured in a spectrofluorometer. A spray aimed towards the soil with filters positioned on the ground and hung at different heights did not show different upward dispersion as observed when lateral pulverization was conducted. In this case, a tractor with a sprayer moved through a 3 m high and 6 m wide frame with filter membranes mounted at 60 cm intervals. Spray dispersion patterns were modified by guava leaf resistance. No influence of temperature and humidity was observed in this short-lived spraying process. Nevertheless, wind drift can occur during airborne dispersion and is an important pesticide pollution source which requires control. Droplets with PABA powered by assisted spraying upwards returned to the ground by gravity and, therefore, did not constitute a vertical source of atmospheric pollution.

Synchronous scanning phosphorimetry for the selective determination of chrysene: a metrological study

Room-temperature phosphorimetry was used to quantify trace levels of chrysene in sugar-cane spirits and in fish bile. A selective phosphorescence enhancer (AgNO3) and synchronous scanning allowed the detection of ng amounts of chrysene. Accuracy (113 ± 17%) and selectivity was evaluated using the CRM-NIST-1647d - Priority Pollutant Polycyclic Aromatic Hydrocarbons in acetonitrile. Analysis of sugar-cane spirit samples enabled recovery of 108 ± 18% which agreed with the one achieved using HPLC. Methods uncertainty was equivalent to 3.4 ng of the analyte, however, the analyte pre-concentration (SPE) improved sensibility and minimized the relative uncertainty. Characterization and homogeneity studies in fish bile were also performed.