Quantitative Determination of Acrolein in Cider by 1H NMR Spectrometry.

Acrolein occasionally appears in cider, completely spoiling its quality due to its bitter taste. It is crucial to detect it in the early steps, before the taste is severely affected, to apply the appropriate treatment. A simple and rapid analytical method to determine this compound in cider is therefore desirable. In this work, a quantitative determination method of acrolein in cider is proposed using the proton nuclear magnetic resonance technique (1H NMR). Acrolein produces a doublet signal in the spectrum at 9.49 ppm, whose area is used to determine the concentration of this compound. Importantly, 3-(Trimethylsilyl)-2,2,3,3-d4-propionic acid sodium salt is added to the cider as a reference for 0.00 ppm and 1,3,5-benzenetricarboxylic acid as an internal standard for acrolein determination. The method is validated by gas chromatography (GC). There is a good correlation between the acrolein concentrations obtained by 1H NMR and by gas chromatography in different commercial ciders (Pearson coefficient 0.9994). The 95% confidence interval for the intercept is 0.15 ± 0.49 (includes 0) and for the slope is 0.98 ± 0.03 (includes 1). When applying the paired t test, no significant difference is observed. The proposed method is direct, and no prior derivatization is needed.

Quantitative determination of carboxylic acids, amino acids, carbohydrates, ethanol and hydroxymethylfurfural in honey by (1)H NMR.

A method using (1)H NMR spectroscopy has been developed to quantify simultaneously thirteen analytes in honeys without previous separation or pre-concentration steps. The method has been successfully applied to determine carboxylic acids (acetic, formic, lactic, malic and succinic acids), amino acids (alanine, phenylalanine, proline and tyrosine), carbohydrates (α- and ß-glucose and fructose), ethanol and hydroxymethylfurfural in eucalyptus, heather, lavender, orange blossom, thyme and rosemary honeys. Quantification was performed by using the area of the signal of each analyte in the honey spectra, together with external standards. The regression analysis of the signal area against concentration plots, used for the calibration of each analyte, indicates a good linearity over the concentration ranges found in honeys, with correlation coefficients higher than 0.985 for the thirteen quantified analytes. The recovery studies give values over the 93.7-105.4% range with relative standard deviations lower than 7.4%. Good precision, with relative standard deviations over the range of 0.78-5.21% is obtained.

Polyphenolic profile in cider and antioxidant power.

BACKGROUND: The aim of this work was to find the effect of polyphenolic compounds in Basque ciders on the following parameters: antioxidant activity, browning, protein-precipitating capacity, turbidity and reduction potential. These five parameters are highly important, as they affect the taste, the visual aspect and the preservation of cider, and are mainly related to polyphenolic compounds. RESULTS: Procyanidin B1 and procyanidin B2 showed a significant positive effect on antioxidant activity. p-Coumaric acid, (-)-epicatechin and hyperin had a significant positive effect on protein-precipitating capacity. Tyrosol had a significant negative effect on reduction potential. CONCLUSION: Procyanidin B1 and procyanidin B2 are the most powerful antioxidants in Basque cider, while p-coumaric acid, (-)-epicatechin and hyperin are those with greatest capacity to precipitate proteins. Ciders with higher tyrosol concentration will have less reduction potential and higher antioxidant reservoir.

Quantitative determination of caffeine, formic acid, trigonelline and 5-(hydroxymethyl)furfural in soluble coffees by 1H NMR spectrometry.

A quantitative method for the determination of caffeine, formic acid, trigonelline and 5-(hydroxymethyl)furfural (5-HMF) in soluble coffees by applying the proton nuclear magnetic resonance technique ((1)H NMR) is proposed. Each of these compounds records a singlet signal at the 7.6-9.5 ppm interval of the spectrum, and its area is used to determine the concentration. 3-(Trimethylsilyl)-2,2,3,3-tetradeuteropropionic acid is added in an exact known concentration as a reference for delta=0.00 ppm and as an internal standard. The method is applied to commercial soluble coffees and satisfactorily compared with results obtained by standard methods. The limits of detection and the coefficients of variation (N=10) are, respectively, 1.32 mg/g of solid product and 4.2% for caffeine, 0.45 mg/g and 2.6% for formic acid, 0.58 mg/g and 2.4% for trigonelline, and 0.30 mg/g and 7.3% for 5-HMF. The described method is direct and no previous derivatization is needed.

CCD detectors for molecular absorption spectrophotometry. A theoretical and experimental study on characteristics and performance.

Uncertainty in charge-coupled devices (CCDs) as UV-vis spectrophotometric detectors is studied here considering that it highly affects the limit of detection of analytical methods. Opposite to photomultiplier-type detectors (PMDs) and diode-array detectors (DADs), where uncertainty is mainly dependent on the photonic signal (shot noise), in CCD detectors uncertainty may come from both independent and dependent effects upon the photonic signal. Shot noise is specially important for high photonic signals in the detector (those for low absorbances) while the uncertainty that is independent of the signal is specially important for low photonic signals in the detector (those for high absorbances). That is, the main source of uncertainty is different depending on the value of the experimental measurement. On the other hand, temperature does not practically affect absorbance measurements, though it is very important for emission measurements (fluorescence, Raman, scattering, etc.). Mathematical equations for uncertainty are proposed with excellent fittings to the experimental data. The equation parameters can be experimentally determined from non-linear regression analysis and used to characterize spectrometers or to test their performance. In order to help buyers and users, some recommendations are finally given considering, among others, cooling, slit, attenuator or fiber optic assemblies.

Detection limit estimator for multivariate calibration by an extension of the IUPAC recommendations for univariate methods.

A methodology is proposed to estimate the limit of detection (LOD) of analytical methods when multivariate calibration is applied. It tries to follow the same premises as the IUPAC methodology for univariate calibration. The mathematical support is given and algorithms such as partial least squares (PLS) regression, PLS2 and principal component regression (PCR) are used. Only multivariate raw data are used; that is, no surrogate univariate signal is deduced. Non-linearities are allowed. Near infrared (NIR) data of 5 component pseudo-gasoline samples together with simulated fluorescence synchronous spectra of binary mixtures (first order data) are used for evaluation. Experimental verification is performed using different kinds of data, namely: binary mixtures of bentazone and fenamiphos (very overlapped spectra, second order data) obtained by sequential injection (SI), and kinetic data of the reaction between the Fenton's reagent (FR) and pesticides such as atrazine, bentazone and alachlor (individual or binary mixtures, second order data). Results are always compared with independent methods previously proposed in the literature, based in the use of surrogate univariate signals. In general, similar results are found and no statistically significant differences seem to be present, except in a few cases when complex chemical systems are involved.

Interference modelling, experimental design and pre-concentration steps in validation of the Fenton's reagent for pesticides determination.

The determination of atrazine in real samples (commercial pesticide preparations and water matrices) shows how the Fenton's reagent can be used with analytical purposes when kinetic methodology and multivariate calibration methods are applied. Also, binary mixtures of atrazine-alachlor and atrazine-bentazone in pesticide preparations have been resolved. The work shows the way in which interferences and the matrix effect can be modelled. Experimental design has been used to optimize experimental conditions, including the effect of solvent (methanol) used for extraction of atrazine from the sample. The determination of pesticides in commercial preparations was accomplished without any pre-treatment of sample apart from evaporation of solvent; the calibration model was developed for concentration ranges between 0.46 and 11.6 x 10(-5) mol L(-1) with mean relative errors under 4%. Solid-phase extraction is used for pre-concentration of atrazine in water samples through C(18) disks, and the concentration range for determination was established between 4 and 115 microg L(-1) approximately. Satisfactory results for recuperation of atrazine were always obtained.