Wein und Gesundheit

Recently, very interesting findings have been revealed in wine, and scientific research on some well known natural ingredients has shown that they possess previously unknown positive significance for the wine consumer. On the one hand residues of crop protection agents (special botryticides with carbodiimide structure, the insecticide Orthene®) are dealt with, then an atypical aging flavor (2-aminoacetophenone), and some novel principles and flavors, and finally the occurrence of mycotoxines (Ochratoxin A) as consequence of low hygiene in wine making, are reported. On the other hand Resveratrol, a phytoalexin, displays cancer chemopreventive activities, and has been found as well in German wines in varying quantities.     

Synthesis,structure, and properties of isomeric polyaminoacetophenones

In terms of the ability for electrochemical transformations in acidic medium, the reactivity decreases in the order o-aminoacetophenone > p-aminoacetophenone > m-aminoacetophenone > aniline. The products of electrochemical polycondensation of the ortho and para isomers are conductors. Oxidative polycondensation of o-aminoacetophenone forms emeraldin hydrosulfate, and with p- and m-aminoacetophenones, emeraldin and leucoemeraldin are formed. In terms of thermal stability, polyacetoaminophenones can be ranked in the order poly-o-aminoacetophenone > poly-m-aminoacetophenone > poly-p-aminoacetophenone.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 12, 2004, pp. 2012–2018.Original Russian Text Copyright © 2004 by Stratan, Kovalchuk, Blazejowski.This revised version was published online in April 2005 with a corrected cover date.     

Cobalt(II) complexes with 2-aminoacetophenone N(4)-substituted thiosemicarbazones

Cobalt(II) complexes with 2-aminoacetophenone thiosemicarbazone and three N(4)-substituted thiosemicarbazones have been prepared in EtOH solution and characterized by physical and spectral methods. I.r. and electronic spectra of the thiosemicarbazones and their complexes, along with physical properties of the complexes, have been obtained. The 2-aminoacetophenone thiosemicarbazones coordinate both as neutral and anionic ligands via the thiosemicarbazone moiety's imine nitrogen and thione/thiolato sulfur [on loss of the N(2) hydrogen].     

Pattern Recognition of Nebbiolo Wine as a Function of the Fungicide Treatment of the Grape

ABSTRACT

Principal component analysis and classification techniques were used to investigate the effect on the properties of wine of different fungicide treatments performed on the grapes. 55 variables were determined, 17 on the grape just-collected and the others on the wines. 27 samples of grape and wine were considered, produced in 1992, 1993" acceptdate="and 1994. The wines were classified as a function of the production year but no important correlation was found between fungicide treatment and the wine features. The classification was performed by a SIMCA method.

Clustering analysis, on the other hand, allowed a separation of the wine samples in three clusters, relative to three main kinds of grape treatments, i.e. based on i) copper sulfate, ii) copper hydroxide and iii) Mancozeb (the only one that does not contain Cu). The treatments based on copper oxychloride and the blank, that are the less active or characterized treatments, gave mixed results within the three clusters.     

Nickel(II) complexes of 2-aminoacetophenone N(4)-substituted thiosemicarbazones

Mononuclear nickel(II) complexes with 2-aminoacetophenone thiosemicarbazones and three N(4)-substituted thiosemicarbazones have been prepared in EtOH solution and characterized by physical and spectral methods. I.r. and electronic spectra of the thiosemicarbazones and their complexes, along with physical properties of the complexes, have been obtained. The 2-aminoacetophenone thiosemicarbazones coordinate both as neutral and anionic ligands via the thiosemicarbazone moiety's azomethine nitrogen and thione/thiolato sulfur [on loss of the N(2) hydrogen].     

‘Untypical aging off-flavor’ in wine: formation of 2-aminoacetophenone and evaluation of its influencing factors

2-Aminoacetophenone (AAP) is known as the character impact compound responsible for the so called untypical ‘aging off-flavor’ (UTA) in Vitis vinifera wines. The formation of AAP is caused by an oxidative degradation of the phytohormone indole-3-acetic acid (IAA), triggered by sulfuration after fermentation. Using different radical generating systems (hydroxyl and/or superoxide radical generating systems) it could be shown especially that superoxide radicals are responsible for the formation of AAP. Hereby, a pyrrole ring cleavage of IAA yields 3-(2-formylaminophenyl)-3-oxo-propionic acid (FAPOP), N-formyl-2-aminoacetophenone (FAP), and AAP. Analysis of 32 grape musts and their corresponding wines revealed that wines with a higher superoxide radical scavenger activity are less prone to UTA formation. However, UTA is not correlated with the IAA content of the must or wine. Differences in the release of IAA during fermentation of musts derived from early and late harvested grapes indicate a correlation between the ripeness of the processed grapes, the IAA content at the time of sulfuration, and the UTA formation.     

Synthesis of amino derivatives of quinoline and 5, 6-benzoquinoline

3-Aminocinchophen and 2-phenyl-3-aminoquinolines were synthesized by the reaction of isatin and 5-, 6-, and 7-methylisatins with -aminoacetophenone in alkaline media. A number of 3-amino-5,6-benzoquinoline derivatives were obtained by the condensation of azomethines from aromatic aldehydes and -naphthylamine with -aminoacetophenone.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 525–526, April, 1972.     

Spectroscopic evaluation of manganese(II) complexes derived from semicarbazones and thiosemicarbazones

Manganese(II) complexes having the general composition Mn(L)2X2 [where L=isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and 4-aminoacetophenone thiosemicarbazone (LLD) and X=Cl-, 1/2SO(4)2-] have been synthesized. All the complexes were characterized by elemental analyses, molar conductance, magnetic moment susceptibility, EI-mass, 1H NMR, IR, EPR and electronic spectral studies. All the complexes show magnetic moments corresponding to five unpaired electrons. The possible geometries of the complexes were assigned on the basis of EPR, electronic and infrared spectral studies.     

Use of multiple headspace solid-phase microextraction and pervaporation for the determination of off-flavours in wine

The occurrence of off-flavours in wines and especially the so-called "cork taint defect" represents one of the most serious problem in wine industry in which 2,4,6-trichloroanisole has been blamed as the main responsible. The development of analytical methods for haloanisoles determination in wine/cork represent a challenge, mainly due to food matrix complexity and low taste and odour (T&O) threshold levels which are generally beyond the sensitivity of the analytical systems. In this work, a method based on the combined use of the recently developed multiple headspace solid-phase microextraction (MHS-SPME) and gas chromatography-ion-trap mass spectrometry has been optimised for the determination of haloanisoles in wines. This powerful analytical methodology is compared with several analytical approaches based on pervaporation, an innovative membrane-based technique similar to dynamic headspace. Analytical features of the methods assayed reveal their suitability for the appraisal of haloanisoles in this matrix in which threshold odor concentrations are in the range 4-40 ng l(-1). The analytical approaches have been applied to the analysis of haloanisoles in different Spanish white and red wines, in which spiking experiments showed good recoveries for the methodologies assayed.     

Preparation,characterization and morphological study of poly(<Emphasis Type="Italic">m</Emphasis>-toluidine-<Emphasis Type="Italic">co</Emphasis>-<Emphasis Type="Italic">m</Emphasis>-aminoacetophenone) conductive copolymer

A new series of copolymers of poly(m-toluidine-co-m-aminoacetophenone) were synthesized by the chemical oxidative method in acid medium. The copolymers were characterized by UV–Vis and FTIR spectroscopy. X-ray diffraction analysis revealed the partial crystalline nature of copolymer. The morphological study by SEM analysis indicated that the surface of the copolymer had the granular structure of agglomerated morphology with average particle size of 200 nm. The conductivity of the copolymers ranged from 2 × 10^–4 to 3.3 × 10^–8 S/cm and the conductivity decreased with the increase of comonomer concentration. The resultant copolymers showed an enhanced solubility and an improved processability when compared with pure polyaniline.     

Analysis of selected carbonyl oxidation products in wine by liquid chromatography with diode array detection

A high performance liquid chromatography (HPLC) method for the detection and quantitation of acetaldehyde, glyceraldehyde, pyruvic acid, 2-ketoglutaric acid, and formaldehyde in wine, based on the formation of the 2,4-dinitrophenylhydrazones, is presented. These carbonyl compounds often result from the chemical oxidation of major wine components, and are known to affect flavor and color stability. Their analysis in wine is complicated due to their instability and their tendency to react reversibly with bisulfite to form α-hydroxysulfonates. Published methods that break down the sulfonates for the quantitation of total carbonyls in wine involve alkaline hydrolysis of sulfite-bound carbonyls, but we show, for the first time, that this alkaline treatment step significantly increases the concentration of carbonyls during analysis. A solution based on oxygen exclusion is described. The technique offers good specificity, reproducibility (%RSD 0.45-10.6), and limits of detection (1.29-7.53 μg L⁻¹). The method was successfully used to monitor concentration changes of these compounds in both white and red wines.     

Multiple headspace solid-phase microextraction for eliminating matrix effect in the simultaneous determination of haloanisoles and volatile phenols in wines

This paper proposes a multiple headspace solid-phase microextraction (MHS-SPME) method coupled to gas chromatography-tandem mass spectrometry detection (GC/MS/MS) for the simultaneous determination of 2,4,6-trichloroanisole, 2,3,4,6-tetrachloroanisole, pentachloroanisole, 2,4,6-tribromoanisole, 4-ethylphenol, 4-ethylguaiacol, 4-vinylphenol and 4-vinylguaiacol in wines. These compounds are involved in the presence of "cork taint" and Brett character in wines. The MHS-SPME method is a modification of SPME developed for quantitative analysis that avoids possible matrix effects based on an exhaustive analyte extraction from the sample. After demonstrating the existence of matrix effect in the analysis of the target compounds by HS-SPME with a divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fibre, the MHS-SPME method was developed and validated. The proposed method showed satisfactory linearity, precision and detection limits, all below the odour detection thresholds of the compounds in wine matrices. Good recoveries were observed for all compounds, always above 90%, and the repeatability obtained was considered acceptable, ranging between 2 and 11%. After checking the applicability of the method by comparing the results recorded with those obtained with the standard addition method, the method was applied successfully to the analysis of wine samples. To our knowledge, this is the first time that MHS-SPME combined with GC/MS/MS has been applied to simultaneously determine haloanisoles and volatile phenols in wine.     

Metabolic fingerprinting based on high-resolution tandem mass spectrometry: a reliable tool for wine authentication?

Ultra-high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (MS) and an alternative technology represented by direct analysis in real time coupled with quadrupole time-of-flight MS were investigated for metabolic fingerprinting of 343 red and white wine samples. Direct injection of pure wine and an extraction procedure optimized for isolation of polyphenols were used to compare different analytical and data handling strategies. After data processing and data pretreatment, principal component analysis was initially used to explore the data structure. Initially, the unsupervised models revealed a notable clustering according to the grape varieties, and therefore supervised orthogonal partial least squares discriminant analysis models were created and validated for separation of red and white wines according to the grape variety. The validated orthogonal partial least squares discriminant analysis models based on data (ions) recorded in positive ionization mode were able to classify correctly 95 % of samples. In parallel, authentication parameters, such as origin and vintage, were evaluated, and they are discussed. A tentative identification of markers was performed using accurate mass measurement of MS and MS/MS spectra, different software packages and different online libraries. In this way, different flavonol glucosides and polyphenols were identified as wine markers according to the grape varieties.     

Spectroscopic and biological studies on newly synthesized nickel(II) complexes of semicarbazones and thiosemicarbazones

Nickel(II) complexes, having the general composition Ni(L)2X2, have been synthesized [where L: isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and 4-aminoacetophenone thiosemicarbazone (LLD) and X=Cl-, 1/2SO(4)2-]. All the Ni(II) complexes reported here have been characterized by elemental analyses, magnetic moments, IR, electronic and mass spectral studies. All the complexes were found to have magnetic moments corresponding to two unpaired electrons. The possible geometries of the complexes were assigned on the basis of electronic and infrared spectral studies. Newly synthesized ligand and its nickel(II) complexes have been screened against different bacterial and fungal growth.     

EPR, mass, IR, electronic, and magnetic studies on copper(II) complexes of semicarbazones and thiosemicarbazones

Copper(II) complexes having the general composition Cu(L)(2)X(2) [where L = isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC), and 4-aminoacetophenone thiosemicarbazone (LLD) and X = Cl(-), 1/2SO(4)(2-)] have been synthesized. All the Cu(II) complexes reported here have been characterized by elemental analyses, molar conductance, magnetic moment susceptibility, EI mass, (1)H NMR, IR, EPR, and electronic spectral studies. All the complexes were found to have magnetic moments corresponding to one unpaired electrons. The possible geometries of the complexes were assigned on the basis of EPR, electronic, and infrared spectral studies.     

2a,4a-Diazacyclopenta[c,d]Azulenes

A method of preparing 5-aryl-1,2-pentaniethyleneimidazoles from O-methylcaprolactim and -aminoacetophenone hydrochlorides is described. It is shown that 1, 2-tri-, -tetra-, and -pentamethyleneirrüdazoles and phenacyl bromide give the corresponding quaternary imidazolium salts, cyclization of which in the presence of base gives the previously unknown 5,6, 78-tetrahydro-2a, 4a-diazacyclopenta(c,dJazulenes (IVa-i).T. G. Shevchenko National Unkiversity, Kiev 254017. T. G. Shevchenko Educational Institute, Chernigov 250037. Translated from Khimiya Geterotskilicheskikh Soedinenii, No. 8, pp. 1072–1077, August, 1996. Original article submitted February 27, 1996; revision submitted June 27, 1996.     

多波长叠加近红外吸收光谱法直接测定酒精饮料中的乙醇

利用乙醇在１３８２ｎｍ，１６９１ｎｍ和１７３０ｎｍ处的吸光度值，采用多波长叠加近红外吸收光谱法测定乙醇的含量。结果表明，乙醇在０％～２４％（Ｖ／Ｖ）浓度范围内呈良好的线性关系；回归方程为： Ａ＝ ０． ０１７５４＋ ０． ０４７４７Ｃ；相关系数ｒ＝０． ９９９４。用该法可直接测定葡萄酒、啤酒和黄酒中乙醇的含量，６次平行测定的ＲＳＤ分别为；葡萄酒４．０％，啤酒２．５％，黄酒２．４％。回收率为９７．５％～１０５．０％，本方法具有操作简便，准确和快速等优点。     

Analytical characterization of wine and its precursors by capillary electrophoresis

The accurate determination of marker chemical species in grape, musts, and wines presents a unique analytical challenge with high impact on diverse areas of knowledge such as health, plant physiology, and economy. Capillary electromigration techniques have emerged as a powerful tool, allowing the separation and identification of highly polar compounds that cannot be easily separated by traditional HPLC methods, providing complementary information and permitting the simultaneous analysis of analytes with different nature in a single run. The main advantage of CE over traditional methods for wine analysis is that in most cases samples require no treatment other than filtration. The purpose of this article is to present a revision on capillary electromigration methods applied to the analysis of wine and its precursors over the last decade. The current state of the art of the topic is evaluated, with special emphasis on the natural compounds that have allowed wine to be considered as a functional food. The most representative revised compounds are phenolic compounds, amino acids, proteins, elemental species, mycotoxins, and organic acids. Finally, a discussion on future trends of the role of capillary electrophoresis in the field of analytical characterization of wines for routine analysis, wine classification, as well as multidisciplinary aspects of the so-called "from soil to glass" chain is presented.     

Copper(II) complexes of 2-aminoacetophenone N(4)-substituted thiosemicarbazones

Mononuclear copper(II) complexes with 2-aminoacetophenone thiosemicarbazone and three N(4)-substituted thiosemicarbazones have been prepared in ethanolic solution and characterized by physical and spectral methods. I.r., electronic and e.s.r. spectra of the complexes, as well as i.r., electronic, and ¹H- and ¹³C-n.m.r. spectra of the thiosemicarbazones, have been obtained. The 2-aminoacetophenone thiosemicarbazones coordinate as neutral ligands via the thiosemicarbazone moiety's azomethine nitrogen and thione sulfur, except for the piperidylthiosemicarbazone, which undergoes deprotonation and coordinates via the thiolato sulfur, as well as through the azomethine nitrogen. Complexes formed in the presence of triethylamine also form complexes with the anionic form of these thiosemicarbazones.