Analytical methods for vancomycin determination in biological fluids and in pharmaceuticals

Vancomycin is a glycopeptide antibiotic employed in the treatment of infections caused by certain methicillin-resistant staphylococci. It is indicated also for patients allergic to penicillin or when there is no response to penicillins or cephalosporins. The adequate vancomycin concentration levels in blood serum lies between 5 and 10 mg/L. Higher values are toxic, causing mainly nephrotoxicity and ototoxicity. Various analytical methods are described in the literature: spectrophotometric, immunologic, biologic and chromatographic methods. This paper reviews the main analytical methods for vancomycin determination in biological fluids and in pharmaceutical preparations.

Determination of chemical elements in africanized Apis mellifera (Hymenoptera: Apidae) honey samples from the State of Piauí, Brazil

Honey is a food used since the most remote times, appreciated for its characteristic flavor, considerable nutritional value and medicinal properties; however, little information exists about the presence of chemical elements in it. The objectives of this work were to determine the chemical elements present in 38 honey samples, collected directly from beekeepers from the State of Piauí, Brazil and to verify whether they presented any contamination. The chemical elements were determined by means of Total Reflection X-ray Fluorescence. The means of three replicates were: K (109.671 ± 17.487), Ca (14.471 ± 3.8797), Ti (0.112 ± 0.07), Cr (0.196 ± 0.11), Mn (0.493 ± 0.103), Fe (1.722 ± 0.446), Co (0.038), Ni (0.728 ± 0.706), Cu (0.179 ± 0.0471), Zn (0.967 ± 0.653), Se (not detected), Br (not detected), Rb (0.371 ± 0.097), Sr (0.145 ± 0.45), Ba (11.681), Hg (not detected), and Pb (0.863) µg g-1.

Determination of cocaine in brazilian paper currency by capillary gas chromatography/mass spectrometry

The presence of illicit drugs such as cocaine and marijuana in US paper currency is very well demonstrated. However, there is no published study describing the presence of cocaine and/or other illicit drugs in Brazilian paper currency. In this study, Brazilian banknotes were collected from nine cities, extracted and analyzed by capillary gas chromatography/mass spectrometry, in order to investigate the presence of cocaine. Bills were extracted with deionized water followed by ethyl acetate. Results showed that 93% of the bills presented cocaine in a concentration range of 2.38-275.10 µg/bill.

Reversed phase HPLC determination of tamoxifen in dog plasma and its pharmaco-kinetics after a single oral dose administration

The analytical method developed to evaluate tamoxifen in dog plasma samples was precise, accurate, robust and linear in the range of 5-200 ng/mL. The limits of detection and quantification were 0.981 ng/mL and 2.97 ng/mL, respectively. Besides, the intra-day precision and accuracy variations were 8.78 and 10.16%, respectively. Tamoxifen concentrations were analyzed by combined reversed phase liquid chromatography and UV detection (lambda=280 nm). The study was conducted using an open randomized 2-period crossover balanced design with a 1-week washout period between the doses. This simple, rapid and selective method is suitable for pharmacokinetic, bioavailability and bioequivalence studies.

Cloud point extraction for the determination of copper in environmental samples by flame atomic absorption spectrometry

A simple cloud point extraction procedure is presented for the preconcentration of copper in various samples. After complexation by 4-hydroxy-2-mercapto-6-propylpyrimidine (PTU), copper ions are quantitatively extracted into the phase rich in Triton X-114 after centrifugation. Methanol acidified with 0.5 mol L-1 HNO3 was added to the surfactant-rich phase prior to its analysis by flame atomic absorption spectrometry (FAAS). Analytical parameters including concentrations for PTU, Triton X-114 and HNO3, bath temperature, centrifugation rate and time were optimized. The influences of the matrix ions on the recoveries of copper ions were investigated. The detection limits (3SDb/m, n=4) of 1.6 ng mL-1 along with enrichment factors of 30 for Cu were achieved. The proposed procedure was applied to the analysis of environmental samples.

Heavy atom enhanced room-temperature phosphorimetry for ultratrace determination of harmane

Harmane has been proposed for the treatment of epilepsy, AIDS and leshmaniosis. Its room-temperature phosphorescence was induced using either AgNO3 or TlNO3, enabling absolute limits of detection of 0.12 and 2.4 ng respectively, with linear dynamic ranges extending up to 456 ng (AgNO3) and 911 ng (TlNO3). Relative standard deviations around 3% were observed for substrates containing 46 ng of harmane. Such sensitivity and precision are needed because harmane intake must be strictly controlled to achieve proper therapeutic response. Interference studies were performed using thalidomide, reserpine and yohimbine. Recovery of 104±6% was achieved using solid surface room-temperature phosphorimetry. The result was comparable to the one obtained by micellar electrokinetic chromatography.

Simultaneous determination of B-Group vitamins in enriched cookies

The objective of this research was to determine the levels of enrichment of vitamins B1, B2, B6 and B3 in different types and brands of enriched cookies. The chromatographic separation was performed in a C18 column with gradient elution and UV detection at 254 and 287 nm. The results show that only 5 of the 24 brands evaluated are in accordance with the Brazilian legislation with respect to the vitamin content declared on the labels. However, consumption of approximately 100-150 g of most of the brands supplies the recommended dietary intake for children and adults of the vitamins evaluated.

Determination of etoricoxib in human plasma using automated on-line solid-phase extraction coupled with LC-APCI/MS/MS

A liquid chromatography-tandem mass spectrometry method with atmospheric pressure chemical ionization (LC-APCI/MS/MS) was validated for the determination of etoricoxib in human plasma using antipyrin as internal standard, followed by on-line solid-phase extraction. The method was performed on a Luna C18 column and the mobile phase consisted of acetonitrile:water (95:5, v/v)/ammonium acetate (pH 4.0; 10 mM), run at a flow rate of 0.6 mL/min. The method was linear in the range of 1-5000 ng/mL (r²>0.99). The lower limit of quantitation was 1 ng/mL. The recoveries were within 93.72-96.18%. Moreover, method validation demonstrated acceptable results for the precision, accuracy and stability studies.

Saako historiasta selvää? Monikulttuuriset yläkoululaiset historian lähteillä historian taidot motiivien, seurauksien, historian tulkintojen ja lähteiden luotettavuuden arvioinneissa

The research assesses the skills of upper comprehensive school pupils in history. The focus is on locating personal motives, assessing wider reasons hidden in historical sources and evaluating source reliability. The research also questions how a wide use of multiple sources affects pupils’ holistic understanding of historical phenomena. The participants were a multicultural group of pupils. The origins of their cultures can be traced to the Balkan, the Middle East, Asia and Europe. The number of native Finnish speakers and pupils speaking Finnish as their second language was almost equal. The multicultural composition provides opportunities to assess how culturally responsive learning history from sources is. The intercultural approach to learning in a multicultural setting emphasizes equality as a precondition for learning. In order to set assignments at least to some extent match with all participants only those answers were taken into account which were produced by pupils who had studied history for a similar period of time in the Finnish comprehensive school system. Due to the small number of participants (41), the study avoids wide generalizations. Nevertheless, possible cultural blueprints in pupils’ way of thinking are noted. The first test examined the skills of pupils to find motives for emigration. The results showed that for 7th graders finding reasons is not a problematic task. However, the number of reasons noticed and justifications varied. In addition, the way the pupils explained their choices was a distinguishing factor. Some pupils interpreted source material making use of previous knowledge on the issue, while other pupils based their analysis solely on the text handed and did not try to add their own knowledge. Answers were divided into three categories: historical, explanatory and stating. Historical answers combined smoothly previously learned historical knowledge to one’s own source analysis; explanatory answers often ignored a wider frame, although they were effective when explaining e.g. historical concepts. The stating answers only noticed motives from the sources and made no attempts to explain them historically. Was the first test culturally responsive? All pupils representing different cultures tackled the first source exam successfully, but there were some signs of how historical concepts are understood in a slightly different way if the pupil’s personal history has no linkage to the concepts under scrutiny. The second test focused on the history of Native Americans. The test first required pupils to recognize whether short source extracts (5) were written by Indians or Caucasians. Based on what they had already learned from North American history, the pupils did not find it hard to distinguish between the sources. The analysis of multiphase causes and consequences of the disputes between Native Americans and white Americans caused dispersion among pupils. Using two historical sources and combining historical knowledge from both of them simultaneously was cumbersome for many. The explanations of consequences can be divided into two groups: the ones emphasizing short term consequences and those placing emphasis on long term consequences. The short term approach was mainly followed by boys in every group. The girls mainly paid attention to long term consequences. The result suggests that historical knowledge in sources is at least to some extent read through role and gender lenses. The third test required pupils to explain in their own words how the three sources given differed in their account of living conditions in Nazi Germany, which turned out to be demanding for many pupils. The pupils’ stronghold was rather the assessment of source reliability and accounts why the sources approached the same events differently. All participants wrote critical and justified comments on reliability and aspects that might have affected the content of the sources. The pupils felt that the main reasons that affected source reliability were the authors’ ethnic background, nationality and profession. The assessment showed that pupils were well aware that position in a historical situation has an impact on historical accounts, but in certain cases the victim’s account was seen as a historical truth. The account of events by a historian was chosen most often as the most reliable source, but it was often justified leniently with an indication to professionalism rather than with clear ideas of how historians conduct accounts based on sources. In brief, the last source test demonstrates that pupils have a strong idea that the ethnicity or nationalism determines how people explained events of the past. It is also an implication that pupils understand how historical knowledge is interpretative. The results also imply that history can be analyzed from a neutral perspective. One’s own membership in an ethnical or religious group does not automatically mean that a person’s cultural identity excludes historical explanations if something in them contradicts with his or her identity. The second method of extracting knowledge of pupils’ historical thinking was an essay analysis. The analysis shows that an analytical account of complicated political issues, which often include a great number of complicated political concepts, leads more likely to an inconsistent structure in the written work of pupils. The material also demonstrates that pupils have a strong tendency to take a critical stance when assessing history. Historical empathy in particular is shown if history somehow has a linkage to young people, children or minorities. Some topics can also awake strong feelings, especially among pupils with emigrant background, if there is a linkage between one’s own personal history and that of the school; and occasionally a student’s historical experience or thoughts replaced school history. Using sources during history lessons at school seems to have many advantages. It enhances the reasoning skills of pupils and their skills to assess the nature of historical knowledge. Thus one of the main aims and a great benefit of source work is to encourage pupils to express their own ideas and opinions. To conclude, when assessing the skills of adolescents in history - their work with sources, comments on history, historical knowledge and finally their historical thinking - one should be cautious and avoid cut off score evaluations. One purpose of pursuing history with sources is to encourage pupils to think independently, which is a useful tool for further identity construction. The idea that pupils have the right to conduct their own interpretations of history can be partially understood as part of a wider learning process, justification to study history comes from extrinsic reasons. The intrinsic reason is history itself; in order to understand history one should have a basic understanding of history as a specific domain of knowledge. Using sources does not mean that knowing history is of secondary importance. Only a balance between knowing the contextual history, understanding basic key concepts and working with sources is a solid base to improve pupils’ historical understanding.

Determination of moisture content and water activity in algae and fish by thermoanalytical techniques

The water content in seafoods is very important since it affects their sensorial quality, microbiological stability, physical characteristics and shelf life. In this study, thermoanalytical techniques were employed to develop a simple and accurate method to determine water content (moisture) by thermogravimetry (TG) and water activity from moisture content values and freezing point depression using differential scanning calorimetry (DSC). The precision of the results suggests that TG is a suitable technique to determine moisture content in biological samples. The average water content values for fish samples of Lutjanus synagris and Ocyurus chrysurus species were 76.4 ± 5.7% and 63.3 ± 3.9%, respectively, while that of Ulva lactuca marine algae species was 76.0 ± 4.4%. The method presented here was also successfully applied to determine water activity in two species of fish and six species of marine algae collected in the Atlantic coastal waters of Bahia, in Brazil. Water activity determined in fish samples ranged from 0.946 - 0.960 and was consistent with values reported in the literature, i.e., 0.9 - 1.0. The water activity values determined in marine algae samples lay within the interval of 0.974 - 0.979.

Simultaneous spectrophotometric determination of ezetimibe and simvastatin in pharmaceutical preparations using chemometric techniques

Two spectrophotometric methods are described for the simultaneous determination of ezetimibe (EZE) and simvastatin (SIM) in pharmaceutical preparations. The obtained data was evaluated by using two different chemometric techniques, Principal Component Regression (PCR) and Partial Least-Squares (PLS-1). In these techniques, the concentration data matrix was prepared by using the mixtures containing these drugs in methanol. The absorbance data matrix corresponding to the concentration data matrix was obtained by the measurements of absorbances in the range of 240 - 300 nm in the intervals with Δλ = 1 nm at 61 wavelengths in their zero order spectra, then, calibration or regression was obtained by using the absorbance data matrix and concentration data matrix for the prediction of the unknown concentrations of EZE and SIM in their mixture. The procedure did not require any separation step. The linear range was found to be 5 - 20 µg mL-1 for EZE and SIM in both methods. The accuracy and precision of the methods were assessed. These methods were successfully applied to a pharmaceutical preparation, tablet; and the results were compared with each other.

Moisture sorption isotherms and isosteric heat determination in Chilean papaya (Vasconcellea pubescens)

The moisture sorption isotherms of Chilean papaya were determined at 5, 20, and 45 ºC, over a relative humidity range of 10-95%. The GAB, BET, Oswin, Halsey, Henderson, Smith, Caurie and Iglesias-Chirife models were applied to the sorption experimental data. The goodness of fit of the mathematical models was statistically evaluated by means of the determination coefficient, mean relative percentage deviation, sum square error, root-mean-square error, and chi-square values. The GAB, Oswin and Halsey models were found to be the most suitable for the description of the sorption data. The sorption heats calculated using the Clausius-Clapeyron equation were 57.35 and 59.98 kJ·mol-1, for adsorption and desorption isotherms, respectively.

Determination of Cd and Pb in fuel ethanol by filter furnace electrothermal atomic absorption spectrometry

A method was developed for quantification of Cd and Pb in ethanol fuel by filter furnace atomic absorption spectrometry. Filter furnace was used to eliminate the need for chemical modification, to stabilize volatile analytes and to allow the application of short pyrolysis step. The determinations in samples were carried out against calibration solutions prepared in ethanol. Recovery tests were made in seven commercial ethanol fuel samples with values between 90 and 120%. Limits of detection were 0.1 µg L-1 for Cd and 0.3 µg L-1 for Pb. Certified water samples (APS 1071, APS 1033, NIST 1643d, NIST 1640) were also used to evaluate accuracy and recoveries from 86.8% to115% were obtained.

Performance characteristics of bioassay UV-spectrophotometry and high perfomance liquid chromatographic determination of gatifloxacin in tablets

The microbiological bioassay, UV-spectrophotometry and HPLC methods for assaying gatifloxacin in tablets were compared. Validation parameters such as linearity, precision, accuracy, limit of detection and limit of quantitation were determined. Beer's law was obeyed in the ranges 4.0-14.0 μg/mL for HPLC and UV-spectrophotometric method, and 4.0-16.0 μg/mL for bioassay. All methods were reliable within acceptable limits for antibiotic pharmaceutical preparations being accurate, precise and reproducible. The bioassay and HPLC are more specific than UV-spectrophotometric analysis. The application of each method as a routine analysis should be investigated considering cost, simplicity, equipment, solvents, speed, and application to large or small workloads.

Flow analysis-hydride generation-gas phase derivative molecular absorption spectrophotometric determination of antimony in antileishmanial drugs

In the present work, the development of a method based on the coupling of flow analysis (FA), hydride generation (HG), and derivative molecular absorption spectrophotometry (D-EAM) in gas phase (GP), is described in order to determine total antimony in antileishmanial products. Second derivative order (D²224nm) of the absorption spectrum (190 - 300 nm) is utilized as measurement criterion. Each one of the parameters involved in the development of the proposed method was examined and optimized. The utilization of the EAM in GP as detection system in a continuous mode instead of atomic absorption spectrometry represents the great potential of the analytic proposal.