The antifungal activity of vapour phase of odourless thymol derivate.

Thymol is a substance with a great therapeutic potential possessing antibacterial and antifungal activity, with a characteristic odour that remains long after application but is not pleasant at higher concentrations. In this study, attention has been focused on describing the chemical and biological properties of the simply prepared trimethylsilyl ether of thymol (kubicin). Interestingly, kubicin has similar volatility as thymol, undergoes hydrolysis in the water (moisture; forming thymol and trimethylsilanol) and can be used at 6,000 times higher concentration than thymol without any negative and irritating odour. Kubicin showed diverse fungistatic and fungicidal activities when tested by direct contact assay, or in vapour phase. The volatile vapour of kubicin was effective on all tested fungal strains. These results suggest that vapours of kubicin might provide an alternative way to fight against fungal contamination.

Varietal classification of white wines by fluorescence spectroscopy.

The Slovak Tokaj region is one of the producers of high-quality white wine having protected designations of origin. The main grape varieties of this region are Furmint, Lipovina and Muscat blanc, which have specific sensory characteristics. This research work presents a strategy for the classification of three mentioned varieties of white wines using fluorescence spectroscopy with chemometrics. Emission and synchronous fluorescence spectra were obtained for bulk as well as diluted samples, principal component analysis (PCA) was applied for exploratory analysis and the scores of the selected PCs were used in linear discriminant analysis (LDA). For undiluted samples, the best PCA-LDA models based on either emission spectra excited at 370 nm or synchronous fluorescence spectra obtained at wavelength difference of 40 and 100 nm provided total correct classifications of 100, 100 and 93% for the calibration, validation and prediction steps, respectively. For diluted samples, the best PCA-LDA models (excitation at 280 nm; wavelength difference of 40 nm) again provided total correct classifications as mentioned above.

Coumarins content in wine: application of HPLC, fluorescence spectrometry, and chemometric approach.

In this work, high performance liquid chromatography (HPLC) and fluorescence spectrometry methods for determination of natural coumarins in Tokaj wine were developed and compared. Molecularly imprinted solid phase extraction procedure was applied for sample preparation. The separation of esculin, coumarin, herniarin, 4-methylumbelliferone, scoparone, scopoletin was performed on core-shell C18 type of stationary phase (100 × 4.6 mm, 5 µm) with a gradient elution of mobile phase containing 1% aqueous solution of acetic acid and methanol, UV-VIS (280 nm for coumarin) and fluorescence detection (Ex 320 nm, Em 450 nm for other coumarins). The HPLC method was validated in term of linearity, limit of detection, limit of quantification, precision and accuracy. Fluorescence detection offers high sensitivity with limit of detection in the ng mL-1 range. Scopoletine and 4-methylumbelliferone were identified and quantified in tested wines. Emission spectral data, synchronous fluorescence spectra of coumarins from fluorescence spectrometry and total concentrations of coumarins quantified by the HPLC method were used in the partial least squares regression. The linear regression between the concentrations predicted by the partial least squares model versus true values obtained by HPLC method confirmed good agreement between the two methods.

Comparison of different fluorescence techniques in brandy classification by region of production.

Fluorescence spectrometry coupled with chemometrics was used to discriminate between 44 brandies originating from different countries. The kind of spectrum (emission, total luminescence and synchronous fluorescence), the geometry of sample illumination (front-face and right angle), and the sample type (bulk and diluted) were considered to compare the brandy classification. Firstly, the emission and synchronous fluorescence spectra (SFS) were processed by the principal component analysis (PCA) and the excitation-emission matrix (EEM) fluorescence spectra were modeled by unfolded PCA and parallel factor analysis (PARAFAC). Secondly, the scores of PCA/PARAFAC components were used in the linear discriminant analysis (LDA). Finally, the quality of the PCA-LDA and PARAFAC-LDA models was compared. Total correct classification using emission spectra was poor, regardless of the experimental conditions. The highest total correct classification (95.5%) was achieved by processing the SFS recorded at wavelength difference of 20 and 60nm on the diluted samples. However, 90.9% observed for bulk samples and their SFS at wavelength difference of 20nm in the right angle geometry as well as EEM fluorescence spectra in both geometries is still an acceptable result.

Application of Fluorescence Spectrometry With Multivariate Calibration to the Enantiomeric Recognition of Fluoxetine in Pharmaceutical Preparations.

Fluoxetine is the most prescribed antidepressant chiral drug worldwide. Its enantiomers have a different duration of serotonin inhibition. A novel simple and rapid method for determination of the enantiomeric composition of fluoxetine in pharmaceutical pills is presented. Specifically, emission, excitation, and synchronous fluorescence techniques were employed to obtain the spectral data, which with multivariate calibration methods, namely, principal component regression (PCR) and partial least square (PLS), were investigated. The chiral recognition of fluoxetine enantiomers in the presence of ß-cyclodextrin was based on diastereomeric complexes. The results of the multivariate calibration modeling indicated good prediction abilities. The obtained results for tablets were compared with those from chiral HPLC and no significant differences are shown by Fisher's (F) test and Student's t-test. The smallest residuals between reference or nominal values and predicted values were achieved by multivariate calibration of synchronous fluorescence spectral data. This conclusion is supported by calculated values of the figure of merit.

Determination of geographical origin of alcoholic beverages using ultraviolet, visible and infrared spectroscopy: A review.

The identification of the geographical origin of beverages is one of the most important issues in food chemistry. Spectroscopic methods provide a relative rapid and low cost alternative to traditional chemical composition or sensory analyses. This paper reviews the current state of development of ultraviolet (UV), visible (Vis), near infrared (NIR) and mid infrared (MIR) spectroscopic techniques combined with pattern recognition methods for determining geographical origin of both wines and distilled drinks. UV, Vis, and NIR spectra contain broad band(s) with weak spectral features limiting their discrimination ability. Despite this expected shortcoming, each of the three spectroscopic ranges (NIR, Vis/NIR and UV/Vis/NIR) provides average correct classification higher than 82%. Although average correct classification is similar for NIR and MIR regions, in some instances MIR data processing improves prediction. Advantage of using MIR is that MIR peaks are better defined and more easily assigned than NIR bands. In general, success in a classification depends on both spectral range and pattern recognition methods. The main problem still remains the construction of databanks needed for all of these methods.

Fluorescence spectroscopy as a tool for determination of coumarins by multivariate calibration.

At present, it is necessary to check the quality of many food products in which the content of coumarins is limited. Since a rapid and simple method for the determination of coumarin (COU), 4-hydroxycoumarin (4HC) and dicoumarol (DC) in tea samples was needed, we developed an alternative option to chromatography, i.e., fluorescence spectroscopy with multivariate calibration. The synchronous fluorescence spectra were recorded at constant wavelength differences 70, 80 and 90 nm from 200 to 400 nm. The different experimental parameters affecting the synchronous fluorescence intensities of the analytes were carefully studied and optimized. Partial least squares (PLS) method and multi linear regression (MLR) were compared on determining the concentrations. The best results were obtained by the PLS method on synchronous fluorescence spectra at Δλ = 90 nm. The results from the analysis of herbal tea Melilotus officinalis by synchronous fluorescence spectroscopy with PLS model are equivalent with the results from HPLC. Fisher F-test and Student's t-test confirmed this finding.

Fluorescence spectroscopy and multivariate methods for the determination of brandy adulteration with mixed wine spirit.

The addition of mixed wine spirit to brandy is easy way to adulterate brandy. To avoid the misleading of the consumers, it is necessary to develop reliable method to detect adulteration of brandy. In this work excitation emission matrix fluorescence in combination with parallel factor analysis (PARAFAC) and partial least squares (PLS) regression was used to determine the content of mixed wine spirit in adulterated brandy samples. Excitation emission matrix fluorescence spectra were measured in the emission wavelength range of 485-580 nm and in the excitation wavelength range of 363-475 nm. The model created using PARAFAC-PLS was able to predict the mixed wine spirit level in adulterated brandy with the root mean square error of prediction (RMSEP) value of 1.9% and a square of the correlation (R(2)) between the reference contents and the predicted values of 0.995.

Simultaneous determination of caffeine, caramel and riboflavin in cola-type and energy drinks by synchronous fluorescence technique coupled with partial least squares.

The aim of this work was to develop a multivariate method for the rapid determination of caffeine and Class IV caramel in cola-type soft drinks and of caffeine, Class III caramel and riboflavin in energy drinks using synchronous fluorescence spectra. The synchronous fluorescence spectra were recorded at constant wavelength difference 90 nm from 200 to 500 nm. Reference values of analyte concentrations by high performance liquid chromatography (HPLC) with fluorescence detection combined with the standard addition method were used to create the partial least squares (PLS) models. High coefficients of determination (>0.99) were obtained in 0.2-4.2, 0.25-5.25, 0.4-10.0 and 0.007-0.054 mg L(-1) range for caffeine, Class III caramel, Class IV caramel and riboflavin, respectively. The PLS models were used to determine the concentration of analytes in different drink samples. The method provided comparable results with those found using the HPLC method.

Principal volatile odorants and dynamics of their formation during the production of May Bryndza cheese.

Volatile aroma compounds were investigated along the production of May Bryndza cheese, a traditional Slovakian cheese produced from raw ewes' milk. Solid phase microextraction was used to isolate the volatile fractions, which were subsequently analysed by gas chromatography-olfactometry and gas chromatography-mass spectrometry. Twenty-seven key odorants were found and described in the intermediate product, ewes' curd ripened for 0, 1, 2, 4, and 8days, or in the final product. A major overall increase in the number of aroma-active volatile compounds and in their odour intensity or concentration took place during the first day of ripening of the ewes' curd, and the odour gradually culminated at the end of ripening. During the final technological step of Bryndza cheese production, when the ewes' curd ripened for 10days is decrusted, pressed and milled with NaCl solution, 8 aroma-active volatile compounds disappeared.

Spectrofluorimetric determination of ellagic acid in brandy.

Two spectrofluorimetric methods have been developed for the rapid determination of ellagic acid. The first method is based on the complex formation between ellagic acid and borax in methanol solution. The fluorescence of the complex is monitored at an emission wavelength of 456nm with excitation at 383nm. Linear calibration curve was obtained from 2.5×10(-8) to 7.5×10(-7)molL(-1) and the limit of determination was 4×10(-9)molL(-1). The second method is based on the complex formation between ellagic acid and boric acid in ethanol solution. The fluorescence of the complex is monitored at an emission wavelength of 447nm with excitation at 387nm. Linear calibration curve was obtained from 1.25×10(-7) to 1.00×10(-6)molL(-1) and the limit of determination was 7×10(-9)molL(-1). The methods were successfully applied for the determination of ellagic acid in brandy samples. The results were found to be in good agreement with those obtained by HPLC method.

Amplification of gas chromatographic-olfactometric signal by ethanol.

An indication of the amplifying effect of ethanol vapors from a humidifier on the perceived odor intensity of eluting odorants was discovered in previous GC--olfactometric (GC-O) experiments. In this study were tested 12 volatiles belonging to various chemical classes to confirm this phenomenon. Two methods were used: the normal GC-O design, whereby panelists smell the effluent incessantly during the whole run, and a design applicable in a target-oriented quantitative GC-O, whereby panelists start sniffing just a short time before the olfactory event starts. Two hydroalcoholic solutions and pure water were put into the humidifier and tested in both designs. Continuous aspiration of ethanol vapors caused a decrease of average intensity for most of the selected volatiles. In contrast, a significant amplifying effect of ethanol on panel intensity was observed in the target-oriented design for most of the compounds. This observation was confirmed with an independent panel. The proposed modification of a standard GC-O procedure could remarkably enhance the performance of GC-O studies oriented on a few target chemicals.

Selective extraction of derivates of p-hydroxy-benzoic acid from plant material by using a molecularly imprinted polymer.

Selective SPE of derivates of p-hydroxybenzoic acid (pHBA) from plant extract of Melissa officinalis is presented using a molecularly imprinted polymer (MIP) made with protocatechuic acid (PA) as template molecule. MIP was prepared with acrylamide as functional monomer, ethylene glycol dimethacrylate as crosslinking monomer and ACN as porogen. MIP was evaluated towards six phenolic acids: PA, gallic acid, pHBA, vanillic acid (VA), gentisic acid (GeA) and syringic acid (SyrA), and then steps of molecularly imprinted SPE (MISPE) procedure were optimized. The best specific binding capacity of MIP was obtained for PA in ACN (34.7 microg/g of MIP). Other tested acids were also bound on MIP if they were dissolved in this solvent. ACN was chosen as solvent for sample application. M. officinalis was extracted into methanol/water (4:1, v/v), the extract was then evaporated to dryness and dissolved in ACN before application on MIP. Water and ACN were used as washing solvents and elution of benzoic acids was performed by means of a mixture methanol/acetic acid (9:1, v/v). pHBA, GA, PA and VA were extracted with recoveries of 56.3-82.1% using this MISPE method. GeA was not determined in plant extract.

Determination of organic acids in tobacco by capillary isotachophoresis.

Nine organic acids and phosphate have been separated and quantified in tobacco by capillary isotachophoresis. Two operating systems for the separation were found: hydrochloric acid (10 mmol l(-1)) adjusted with beta-alanine to pH 2.9 plus 0.1% poly(vinylpyrrolidone) was used as the leading electrolyte and 10 mmol l(-1) nicotinic acid as the terminating electrolyte and hydrochloric acid (10 mmol l(-1)) including 5.5 mmol l(-1) 1,3-bis[tris(hydroxymethyl)methylamino]propane plus 0.1% poly(vinylpyrrolidone) was used as the leading electrolyte and 5 mmol l(-1) 2-morpholinoethanesulfonic acid as the terminating electrolyte. Linearity was observed from 0.008 to 0.100 mmol l(-1) with a coefficient of determination (r2) of 0.999. The separation of anions was achieved in less than 16 min. The minimal sample pretreatment and relatively low running cost make isotachophoresis a good alternative to existing methods.

Determination of inorganic anions in saliva by capillary isotachophoresis.

Nitrite, nitrate, iodide and thiocyanate have been quantified in non-smoker and smoker saliva by capillary isotachophoresis (CITP). Hydrochloric acid (10 mmol l(-1)) adjusted with histidine to pH 6.0 plus 6% poly(vinylpyrrolidone) was used as the leading electrolyte (LE) and 5 mmol l(-1) acetic acid as the terminating electrolyte (TE). Linearity was observed from 0.005 to 0.500 mmol l(-1) with a coefficient of determination (r(2)) of 0.999. The separation of anions was achieved in less than 19 min. The minimal sample pretreatment and relatively low running cost make isotachophoresis good alternative to existing methods.