Bitterstoffe beim Erhitzen von Saccharose, Maltose und Prolin 2. Mitteilung

Summary In addition to the mono- and dipyrrolidinohexosereductones described recently (Z Lebensm Unters Forsch (1984) 178:356) two further bittertasting compounds were isolated from heated mixtures of proline and sucrose (molar ratio 3: 1, 190 °C, 30 min) and also synthesized, namely 2,3-bis-(1-pyrrolidinyl)2-cyclopenten-l-one and 2,3-bis(1-pyrrolidinyl)-5methyliden-2-cyclopenten-l-one. The recognition thresholds (mmol/1) are 0.15–0.25 and 0.06–0.12 respectively. Both compounds have a burning bitter taste character. From a maltose-proline reaction mixture 2--glucosyl-5-hydroxy-5-methyl-4-piperidinyl-2-cyclopenten-1-one was isolated. When the dihydroxypyranone VI was heated with proline, 2,5-dihydroxy-5-methyl-4-prohnyl-2-cyclopenten-1-one and the cyclopent(b)azepinones XI and XII were among the compounds formed. These compounds also have a bitter taste character.Zusammenfassung Zusätzlich zu den kürzlich beschriebenen Mono- and Dipyrrolidinohexosereduktionen (Z Lebensm Unters Forsch (1984) 178:356) wurden zwei weitere bittere Verbindungen aus erhitzten Mischungen von Prolin and Saccharose (Molverhältnis 3:1, 190 °C, 30 min) isoliert and synthetisiert. Es handelt sich um 2,3-Bis-(1-Pyrrolidinyl)-2-cyclopenten-1-on und 2,3-Bis-(1-Pyrrolidinyl)-5-methyliden-2-cyclopenten-1-on. Die Erkennungsschwellenwerte (mmol/1) sind 0,15-0,25 and 0,06-0,12. Beide Verbindungen haben einen brennend-bitteren Geschmack. Aus einem Maltose-Prolin-Umsetzungsgemisch gelang die Isolierung des 2--Glucosyl-5-hydroxy-5-methyl-4-piperidinyl-2-cyclopenten-1-ons. Bei der Reaktion des Dihydropyranons VI mit Prolin wurden u. a. das 2,5-Dihydroxy-5-methyl-4-prolinyl2-cyclopenten-1-on sowie die Cyclopent(b)azepinone XI and XII gebildet. Diese Verbindungen sind ebenfalls mehr oder weniger stark bitter.     

Oxidation of Hydrogen Sulfide by Quinones: How Polyphenols Initiate Their Cytoprotective Effects

We have shown that autoxidized polyphenolic nutraceuticals oxidize H₂S to polysulfides and thiosulfate and this may convey their cytoprotective effects. Polyphenol reactivity is largely attributed to the B ring, which is usually a form of hydroxyquinone (HQ). Here, we examine the effects of HQs on sulfur metabolism using H₂S- and polysulfide-specific fluorophores (AzMC and SSP4, respectively) and thiosulfate sensitive silver nanoparticles (AgNP). In buffer, 1,4-dihydroxybenzene (1,4-DB), 1,4-benzoquinone (1,4-BQ), pyrogallol (PG) and gallic acid (GA) oxidized H₂S to polysulfides and thiosulfate, whereas 1,2-DB, 1,3-DB, 1,2-dihydroxy,3,4-benzoquinone and shikimic acid did not. In addition, 1,4-DB, 1,4-BQ, PG and GA also increased polysulfide production in HEK293 cells. In buffer, H₂S oxidation by 1,4-DB was oxygen-dependent, partially inhibited by tempol and trolox, and absorbance spectra were consistent with redox cycling between HQ autoxidation and H₂S-mediated reduction. Neither 1,2-DB, 1,3-DB, 1,4-DB nor 1,4-BQ reduced polysulfides to H₂S in either 21% or 0% oxygen. Epinephrine and norepinephrine also oxidized H₂S to polysulfides and thiosulfate; dopamine and tyrosine were ineffective. Polyphenones were also examined, but only 2,5-dihydroxy- and 2,3,4-trihydroxybenzophenones oxidized H₂S. These results show that H₂S is readily oxidized by specific hydroxyquinones and quinones, most likely through the formation of a semiquinone radical intermediate derived from either reaction of oxygen with the reduced quinones, or from direct reaction between H₂S and quinones. We propose that polysulfide production by these reactions contributes to the health-promoting benefits of polyphenolic nutraceuticals.     

Rationally designed inhibitors as tools for comparing the mechanism of squalene-hopene cyclase with oxidosqualene cyclase

The inhibition of squalene-hopene cyclase (SHC) (E.C. 5.4.99.-), an enzyme of bacterial membranes catalyzing the formation of pentacyclic sterol-like triterpenes, was studied by using different classes of compounds originally developed as inhibitors of oxidosqualene cyclase (OCS) (E.C. 5.4.99.7), the enzyme of eukaryotes responsible for the formation of tetracyclic precursors of sterols. The mechanism of cyclization of squalene by SHC, beginning with a protonation of the 2,3 double bond by an acidic residue of the enzyme, followed by a series of electrophilic additions of the carbocationic intermediates to the double bonds, is similar to the mechanism of cyclization of 2,3-oxidosqualene by OSC. The inhibitors studied included: (i) analogs of the carbocationic intermediates formed during cyclization, such as aza-analogs of squalene and 2,3-oxidosqualene; (ii) affinity-labeling inhibitors bearing a methylidene reactive group; and (iii) vinyldioxidosqualenes and vinylsulfide derivatives of the substrates. Comparison of the results obtained with the two enzymes, SHC and OSC, showed that many of the most effective inhibitors of OSC were also able to inhibit SHC, while some derivatives acted as specific inhibitors. Differences could be easily explained on the basis of the different substrate specificity of the two enzymes.     

Darstellung,Struktur und Reaktivität quartärer Ammoniumcellulosate

Tetraalkylammonium cellulosates were prepared by means of an exchange reaction between cellulose and tetraalkylammonium methoxides in anhydrous methanol and dimethylsulfoxide up to a degree of substitution of about 0,7 without chain degradation. The course of this reaction and the structure of the cellulosates in comparison to lithium and sodium cellulosate has been studied. The reaction rate and the equilibrium substitution decreased with increasing size of the cation in the methoxide. The distribution of the alcoholate groups in equilibrium at C-2, C-3 and C-6 of the glucopyranosyl unit in the cellulosates, which was investigated by methylation, hydrolysis of the methylcelluloses, and analysis of the methylglucoses by gas chromatography, was independent of the nature of the cation. Under the given reaction conditions the hydroxyl group at C-2 was more acidic than those at C-3 and C-6, while for the latter practically no difference was found. The tetraalkylammonium cellulosates are highly reactive intermediates for the preparation of cellulose derivatives. The reactivity of the cellulosates increased with increasing size of the cation, Li^⊕ < Na^⊕ < N(CH₃)₄^⊕ <[(CH₃)₃N? CH₂? C₆H₅]^⊕.     

Über das Spreiten von Lipiden auf der Haut

On the Spreading of Lipids on the Skin The spontaneous spreading of liquid lipids on human skin is an important property for the use value of such products in cosmetic and pharmaceutical preparations. A comparative evaluation procedure based on an impression method is described, by means of which it is possible to determine the spreading rates in a reproducible manner. The standardized spreading values of a number of lipids are discussed in comparison with their chemical structure and physico-chemical data such as viscosity and surface tension. None of these data series correlates entirely with the spreading rates of all the lipids tested. However, it is possible to assess relative spreading rates within similarly structured groups of compounds.     

Anwendung von statistischen Prüfverfahren im Bereich der Mischtechnik

Application of statistical testing to mixing. Assessment of the homogeneity of mixtures of solids and determination of the necessary mixing times are performed with the aid of statistical testing methods. The results from the basis for necessary decisions. Since reliable statements are fundamentally impossible in mathematical statistics, all such decisions are, with a certain probability, false, i.e. involve some risk. In studies of mixing, the first kind of error concerns the risk of rejecting a mixture although its homogeneity satisfies requirements, while the second kind of error concerns the risk of accepting a mixture although its homogeneity is insufficient. It is shown that barriers can be introduced for both kinds of error, and how to do this. Both the sample size and the limits of the acceptance range for the sample variance are thus laid down. If no decision is to be made concerning acceptance or rejection of a given mixture, but information is merely required about the mixing quality after a given time then this is accomplished by statement of confidence intervals.