Wine Storage at Cellar vs. Room Conditions: Changes in the Aroma Composition of Riesling Wine

Storage temperature is one of the most important factors affecting wine aging. Along with bottling parameters (type of stopper, SO₂ level and dissolved O₂ in wine), they determine how fast wine will evolve, reach its optimum and decline in sensory quality. At the same time, lowering of the SO₂ level in wine has been a hot topic in recent years. In the current work, we investigated how Riesling wine evolved on the molecular level in warm (~25 °C) and cool (~15 °C) conditions depending on the SO₂ level in the wine (low, medium and high), flushing of the bottle’s headspace with CO₂ and three types of stoppers (Diam 30, Diam 30 origin and Diam 5) with different OIR levels (0.8–1.3 mg) and OTR levels (0.3–0.4 mg/year). It was demonstrated that the evolution of primary and secondary aromas, wine color and low molecular weight sulfur compounds (LMWSCs) during the two years of aging mainly depended on the storage temperature. Variation in the SO₂ level and CO₂ in the headspace affected mostly certain LMWSCs (H₂S, MeSH) and β-damascenone. New aspects of C₁₃-norisprenoids and monoterpenoids behavior in Riesling wine with different levels of SO₂ and O₂ were discussed. All three types of stoppers showed very close wine preservation properties during the two years of storage. The sensory analysis revealed that, after only six months, the warm stored wines with a low SO₂ level were more oxidized and different from the samples with medium and high SO₂ levels. A similar tendency was also observed for the cool stored samples.     

Formation of volatile selenium species in synthetic seawater under light and dark experimental conditions

Experiments were performed in the laboratory on synthetic seawater spiked with different selenium species at trace levels to study the formation of volatile selenium compounds under dark or controlled simulated sunlight conditions. Spiking the reaction media with inorganic and organic selenium compounds demonstrated that several volatile selenium species could be formed under these simulated conditions. Selenoamino acids react to produce significant amounts of volatile selenium species in both light and dark conditions. Products formed include dimethyl selenide (DMSe), dimethyl selenyl sulphide (DMSeS) and dimethyl diselenide (DMDSe). Inorganic selenium oxyanions added to the synthetic reaction media did not form volatile species via abiotic reactions despite the presence of strong methylating agents. These results suggest that the formation of stable volatile species from bio‐organic selenium compounds can occur via abiotic reactions in the marine photic zone. Copyright © 2000 John Wiley & Sons, Ltd.     

Asymmetric Syntheses of New Polyhydroxylated Quinolizidines: Cross‐Aldol Reactions of 7‐Oxabicyclo[2.2.1]heptan‐2‐one and 3a,4a,7a,7b‐Tetrahydro[1,3]dioxolo[4,5]furo[2,3‐d]isoxazole‐3‐carbaldehyde Derivatives

The cross‐aldolization of (−)‐(1S,4R,5R,6R)‐6‐endo‐chloro‐5‐exo‐(phenylseleno)‐7‐oxabicyclo[2.2.1]heptan‐2‐one ((−)‐ 25 ) and of (+)‐(3aR,4aR,7aR,7bS)‐ ((+)‐ 26 ) and (−)‐(3aS,4aS,7aS,7bR)‐3a,4a,7a,7b‐tetrahydro‐6,6‐dimethyl[1,3]dioxolo[4,5]furo[2,3‐d]isoxazole‐3‐carbaldehyde ((−)‐ 26 ) was studied for the lithium enolate of (−)‐ 25 and for its trimethylsilyl ether (−)‐ 31 under Mukaiyama's conditions (Scheme 2). Protocols were found for highly diastereoselective condensation giving the four possible aldols (+)‐ 27 (`anti'), (+)‐ 28 (`syn'), 29 (`anti'), and (−)‐ 30 (`syn') resulting from the exclusive exo‐face reaction of the bicyclic lithium enolate of (−)‐ 25 and bicyclic silyl ether (−)‐ 31 . Steric factors can explain the selectivities observed. Aldols (+)‐ 27 , (+)‐ 28 , 29 , and (−)‐ 30 were converted stereoselectively to (+)‐1,4‐anhydro‐3‐{(S)‐[(tert‐butyl)dimethylsilyloxy][(3aR,4aR,7aR,7bS)‐3a,4a,7a,7b‐tetrahydro‐6,6‐dimethyl[1,3]dioxolo[4,5]‐furo[2,3‐d]isoxazol‐3‐yl]methyl}‐3‐deoxy‐2,6‐di‐O‐(methoxymethyl)‐α‐D ‐galactopyranose ((+)‐ 62 ), its epimer at the exocyclic position (+)‐ 70 , (−)‐1,4‐anhydro‐3‐{(S)‐[(tert‐butyl)dimethylsilyloxy][(3aS,4aS,7aS,7bR)‐3a,4a,7a,7b‐tetrahydro‐6,6‐dimethyl[1,3]dioxolo[4,5]furo[2,3‐d]isoxazol‐3‐yl]methyl}‐3‐deoxy‐2,6‐di‐O‐(methoxymethyl)‐α‐D ‐galactopyranose ((−)‐ 77 ), and its epimer at the exocyclic position (+)‐ 84 , respectively (Schemes 3 and 5). Compounds (+)‐ 62 , (−)‐ 77 , and (+)‐ 84 were transformed to (1R,2R,3S,7R,8S,9S,9aS)‐1,3,4,6,7,8,9,9a‐octahydro‐8‐[(1R,2R)‐1,2,3‐trihydroxypropyl]‐2H‐quinolizine‐1,2,3,7,9‐pentol ( 21 ), its (1S,2S,3R,7R,8S,9S,9aR) stereoisomer (−)‐ 22 , and to its (1S,2S,3R,7R,8S,9R,9aR) stereoisomer (+)‐ 23 , respectively (Schemes 6 and 7). The polyhydroxylated quinolizidines (−)‐ 22 and (+)‐ 23 adopt `trans‐azadecalin' structures with chair/chair conformations in which H−C(9a) occupies an axial position anti‐periplanar to the amine lone electron pair. Quinolizidines 21 , (−)‐ 22 , and (+)‐ 23 were tested for their inhibitory activities toward 25 commercially available glycohydrolases. Compound 21 is a weak inhibitor of β‐galactosidase from jack bean, of amyloglucosidase from Aspergillus niger, and of β‐glucosidase from Caldocellum saccharolyticum. Stereoisomers (−)‐ 22 and (+)‐ 23 are weak but more selective inhibitors of β‐galactosidase from jack bean.     

Thermodynamic asymmetric induction: a new approach to the development of rules for the determination of absolute configurations

The absolute configurations of chiral primary amines can be determined using the optical rotations of the corresponding N-p-toluenesulfonyl-N-2,4-dinitrobenzensulfenyl derivatives.     

Two Photon‐Induced Electron Injection From a Nanotrigger in Native Endothelial NO‐Synthase

We have recently designed a nanotrigger (NT), a photoactive molecule addressing the NADPH sites of proteins. This nanotrigger has a 10³ times larger two‐photon cross‐section compared to the ubiquitous NADPH cofactor. In this work, we tested whether two‐photon excitation of the bound NT to NADPH sites may be used to initiate enzymatic catalysis by appropriate electron injection. To establish proof of principle, we monitored the ultrafast absorption of NT bound to the fully active endothelial NO‐Synthase (eNOS) following excitation by one and two‐photons at 405 and 810 nm, respectively. Electron injection from NT* to FAD in eNOS initiated the catalytic cycle in 15±3 ps at both exciting wavelengths. The data proved for the first time that electron transfer can be promoted by two‐photon excitation. We also show that the nanotrigger decays faster in homogeneous solvents than in the NADPH site of proteins, suggesting that hindered environments modified the natural decay of NT. The nanotrigger provides a convenient way of synchronizing an ensemble of proteins in solution with a femtosecond laser pulse. The ability of NT to initiate NOS catalysis by two‐photon excitation may be exploited for controlled and localized release of free NO in cells with enhanced spatial and temporal resolution.     

Highly efficient and economic synthesis of new substituted amino-bispyridyl derivatives via copper and palladium catalysis

A convenient route for the synthesis of a variety of amino-bispyridyl compounds is introduced. Bispyridylamines were prepared in three steps from commercially available 2,6-dibromopyridine, via a copper mediated alkylation followed by two consecutive N-arylation reactions catalyzed by copper and palladium, respectively.     

Pump Effect of a Capillary Discharge in Electrically Conductive Liquids

Among the configurations to generate plasma in electrically conductive liquids only the diaphragm and the capillary discharge schemes allow to generate plasma which is not in contact with one of the electrodes. Based on this concept, this work reports for the first time the development of an underwater plasma pump, in which the periodic electrical breakdown inside an asymmetrical (sub-)millimetre hole results in a net flow of aqueous solution through the hole without the use of any moving parts such as valves or diaphragms typically used in micropumps. Certain capillary geometries feature very stable flow rates and even allow altering flow direction by changing the power. By varying the hole’s dimensions, the range of time-independent flow rates covers more than one order of magnitude and as the discharge produces some of the strongest oxidants available, we believe that this concept might find application in fields as water decontamination and sterilization.