Cranberry: Chemical Composition, Antioxidant Activity and Impact on Human Health: Overview.

Cranberries are a rich source of bioactive compounds that comprise a healthy diet. Cranberry is abundant in nutritional components and many bioactive compounds that have antioxidant properties. Both American (Vaccinium macrocarpon) and European (Vaccinium oxycoccus) cranberry species are rich in polyphenols such as phenolic acids, anthocyanins and flavonoids, and is one of the few fruits that is high in proanthocyanidins, which is linked to many health benefits. The review systematizes information on the chemical composition of cranberry, its antioxidant effect, and the beneficial impact on human health and disease prevention after cranberry consumption, and in particular, its effect against urinary tract inflammation with both adults and children, cardiovascular, oncology diseases, type 2 diabetes, metabolic syndrome, obesity, tooth decay and periodontitis, Helicobacter pylori bacteria in the stomach and other diseases. Additional research needs to study cranberry proteomics profiling, polyphenols interaction and synergism with other biologically active compounds from natural ingredients and what is important in formulation of new functional foods and supplements.

Predicting the absence of an unknown compound in a mass spectral database.

Only a small subset of known organic compounds (amenable for gas chromatography/mass spectrometry) is present in the largest mass spectral databases (such as NIST or Wiley). Nevertheless, library search algorithms available in the market are not able to predict the absence of a compound in the database. In the present work, we have tried to implement such prediction by means of supervised classification. Training and validation set contained 1500 and 750 compounds, respectively. Two prediction sets (containing 750 and about 3000 mass spectra) were considered. The easiest-to-use models were built with only one input variable: match factor of the best candidate or InLib factor (both parameters were calculated within MS Search (NIST) software). Multivariate classification models were built by partial least squares discriminant analysis (PLS-DA); match factors of top n candidates were used as input variables. PLS-DA was found to be the most effective approach. The prediction efficiency strongly depended on the 'uniqueness' of mass spectra presented in the test set. PLS-DA model was able to correctly predict the absence of a compound in the database in 29.9% for prediction set #1 and in 74.4% for prediction set #2 (only 1.3% and 2.5% of compounds actually presented in the database were wrongly classified).

Letter: Fast detection of polycyclic aromatic hydrocarbons in complex mixtures of organic compounds based on gas chromatography-mass spectrometry with atmospheric pressure photoionization.

The research is devoted to the investigation of the selectivity detection of 16 polycyclic aromatic hydrocarbons (PAHs) using gas chromatography-mass spectrometry (GC-MS), electron ionization (EI) GC-MS with atmospheric pressure photoionization (APPhI) and GC-MS atmospheric pressure photochemical ionization (APPhCI) when vapors of different substances (benzene, toluene, and naphthalene) were used as gas reagents. Capillary columns of different lengths were used for the separation of the components of the mixture of 44 semivolatile organic compounds. It was shown that the most-selective detection of 16 PAHs in a 44- component mixture was possible when GC-MS APPhCI was used. Only 16 PAHs were registered on the respective mass chromatograms and a fast detection of them was possible. The respective APPhI and APPhCI mass spectra consisted of only peak of the respective molecular ion, M⁺⁺ - the radical cation. Detection limits were 3 pg µL⁻¹ to 15 pg µL.

Evaluation of mass spectral library search algorithms implemented in commercial software.

Performance of several library search algorithms (against EI mass spectral databases) implemented in commercial software products ( acd/specdb, chemstation, gc/ms solution and ms search) was estimated. Test set contained 1000 mass spectra, which were randomly selected from NIST'08 (RepLib) mass spectral database. It was shown that composite (also known as identity) algorithm implemented in ms search (NIST) software gives statistically the best results: the correct compound occupied the first position in the list of possible candidates in 81% of cases; the correct compound was within the list of top ten candidates in 98% of cases. It was found that use of presearch option can lead to rejection of the correct answer from the list of possible candidates (therefore presearch option should not be used, if possible). Overall performance of library search algorithms was estimated using receiver operating characteristic curves.

Distinguishing by principal component analysis of o-xylene, m-xylene, p-xylene and ethylbenzene using electron ionization mass spectrometry.

The possibility of distinguishing between o-, m-, p-xylene and ethylbenzene on the basis of only their 70 eV electron ionization (EI) mass spectra has been investigated. These four isomers were distinguished by principal component analysis (PCA) of respective EI mass spectra (recorded under identical conditions). Considered mass spectra contained either eleven or five m/z values, which had intensity greater than 5% or 10% of base peak, respectively.

Fast quantitation of 5-hydroxymethylfurfural in honey using planar chromatography.

An approach for rapid quantitation of 5-hydroxymethylfurfural (HMF) in honey using planar chromatography is suggested for the first time. In high-performance thin-layer chromatography (HPTLC) the migration time is approximately 5 min. Detection is performed by absorbance measurement at 290 nm. Polynomial calibration in the matrix over a range of 1:80 showed correlation coefficients, r, of ≥ 0.9997 for peak areas and ≥ 0.9996 for peak heights. Repeatability in the matrix confirmed the suitability of HPTLC-UV for quantitation of HMF in honey. The relative standard deviation (RSD, %, n = 6) of HMF at 10 ng/band was 2.9% (peak height) and 5.2% (peak area); it was 0.6% and 1.0%, respectively, at 100 ng/band. Other possible detection modes, for example fluorescence measurement after post-chromatographic derivatization and mass spectrometric detection, were also evaluated and can coupling can be used as an additional tool when it is necessary to confirm the results of prior quantitation by HPTLC-UV. The confirmation is provided by monitoring the HMF sodium adduct [M + Na](+) at m/z 149 followed by quantitation in TIC or SIM mode. Detection limits for HPTLC-UV, HPTLC-MS (TIC), and HPTLC-MS (SIM) were 0.8 ng/band, 4 ng/band, and 0.9 ng/band, respectively. If 12 µL honey solution was applied to an HPTLC plate, the respective detection limits for HMF in honey corresponded to 0.6 mg kg(-1). Thus, the developed method was highly suitable for quantitation of HMF in honey at the strictest regulated level of 15 mg kg(-1). Comparison of HPTLC-UV detection with HPTLC-MS showed findings were comparable, with a mean deviation of 5.1 mg kg(-1) for quantitation in SIM mode and 6.1 mg kg(-1) for quantitation in TIC mode. The mean deviation of the HPTLC method compared with the HPLC method was 0.9 mg kg(-1) HMF in honey. Re-evaluation of the same HPTLC plate after one month showed a deviation of 0.5 mg kg(-1) HMF in honey. It was demonstrated that the proposed HPTLC method is an effective method for HMF quantitation in honey. Figure Fast quantitation of 5-hydroxymethylfurfural in honey.

Increasing the accuracy of determination of nc/nH ratios by gas chromatography-atomic emission detection.

The influence of oxygen content in helium on the accuracy of nc/nH ratio determination for model mixtures of aliphatic and polyaromatic hydrocarbons and polychlorinated biphenyls was studied. The best accuracy was achieved at the oxygen content ca. 9%, which was the maximal possible oxygen content in helium for this GC-atomic emission detection (helium flow rate was 25 ml min(-1)). Using the maximal oxygen flow in plasma the nC/nH ratio determination accuracy improvement was accompanied by 10-fold increase in detection limit.

Improving the accuracy of carbon-to-hydrogen ratio determination for P, N, S, O, Cl, and Br-containing organic compounds using atomic emission detection.

The objective of this work was to investigate the dependence of atomic emission detector C and H response on microwave-induced plasma conditions and to improve the accuracy of carbon-to-hydrogen ratio determination for trialkylphosphates, herbicides, chlorophenols, and sulfur-containing organic compounds. Compounds which differed structurally from the analytes were used as reference compounds. It was found that when the oxygen concentration in the helium was the maximum for the instrument (9%) relative errors in carbon-to-hydrogen ratio determination were 3-8%, irrespective of analyte and reference compound structure, whereas when working in the mode of operation recommended by the manufacturer of the instrument (1.5% oxygen in helium) the respective errors were 10-20% or higher. This improvement in the accuracy of carbon-to-hydrogen ratio determination was accompanied by a factor of ten decrease in sensitivity.

Simultaneous determination of fatty, dicarboxylic and amino acids based on derivatization with isobutyl chloroformate followed by gas chromatography-positive ion chemical ionization mass spectrometry.

Gas chromatography-mass spectrometry (GC-MS) with positive ion chemical ionization (PICI) using isobutane as reagent gas was applied for analysis of isobutoxycarbonyl/isobutyl derivatives of 13 fatty, 6 dicarboxylic and 13 amino acids in a single run. For all investigated compounds (except several amino acids) the quasimolecular ions [MH](+) were registered. Asparagine underwent fragmentation via decarboxylation followed by elimination of OC(4)H(9) ([M-117](+)), whereas serine and tyrosine produced the cluster ions [M+C(4)H(9)OCO](+). Estimated detection limits were 6-250 pg in the total ion current (TIC) mode and 3-10 times lower using the selected-ion monitoring (SIM) mode.

Electron ionization mass spectra and their reproducibility for trialkylsilylated derivatives of organic acids, sugars and alcohols.

Mass spectra of trialkylsilyl derivatives of fatty acids, dicarboxylic acids, hydroxyacids, oxoacids, sugars, amino acids and alcohols were obtained. Amino acids were analyzed as tert-butyldimethylsilyl derivatives; all other model compounds were analyzed as trimethylsilyl derivatives. Reproducibility of the electron ionization (EI) mass spectra for the derivatives obtained was discussed. It was shown that, for many investigated derivatives, composition of the respective mass spectra depended greatly on ion source contamination. The trimethylsilylated alpha-tocopherol mass spectrum composition was most significantly influenced by ion source contamination. This compound can be used to test ion source contamination.

Electron ionization and atmospheric pressure photochemical ionization in gas chromatography-mass spectrometry analysis of amino acids.

The mass spectra of tert-butyldimethylsilyl (TBDMS) derivatives of 17 amino acids were obtained using electron ionization (EI) and atmospheric pressure photochemical ionization (APPhCI) mass spectrometry. The APPhCI mass spectra for all of the derivatives except arginine were shown to consist of only molecular [M](+.) and quasimolecular [MH](+) ions whereas, in the case of EI, the compounds in question underwent a drastic fragmentation. The application of APPhCI to gas chromatography-mass spectrometry enables a reliable identification of the TBDMS derivatives of amino acids in a mixture, even if its components are only partially resolved, due to the unique molecular masses for each compound. Comparison of the respective positive-ion chemical ionization (PICI) mass spectra available in the literature with APPhCI spectra has shown that, in the case of PICI, unlike APPhCI, noticeable fragmentation occurs.

Determination of polychlorinated dibenzo-p-dioxins, dibenzofurans, and biphenyls by gas chromatography/mass spectrometry in the negative chemical ionization mode with different reagent gases.

Reagent gases that are used in mass spectrometry in the NCI mode for the determination of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) are discussed. Ion-molecule reactions and respective characteristic ions that form while using reagent gases (CH(4), O(2), i-C(4)H(10), NH(3), H(2), He, Ar, Xe, SF(6)) or gas mixtures (CH(4)/O(2), Ar/CH(4), CH(4)/H(2)O, Ar/O(2), i-C(4)H(10)/CH(2)Cl(2)/O(2)) are reviewed. It is shown that only CH(4), O(2), CH(4)/O(2), and CH(4)/N(2)O are widely used and well studied, even though-in the case of these reagent gases-there are contradictions between the publications of various authors. Such reagent gases as NH(3) and He are not well studied, but further investigations of their use for the determination of organochlorine pollutants could be of interest. The possibilities of more sensitive and selective determination of PCDDs, PCDFs, and PCBs are discussed.