Loss and formation of malodorous volatile sulfhydryl compounds during wine storage.

Volatile sulfur compounds (VSCs), particularly low molecular weight sulfhydryls like hydrogen sulfide (H2S) and methanethiol (MeSH), are often observed in wines with sulfurous off-aromas. Recent work has shown both H2S and MeSH can increase up to a few µM (> 40 µg/L) during anoxic storage, but the identity of the latent sources of these sulfhydryls is still disputed. This review critically evaluates the latent precursors and pathways likely to be responsible for the loss and formation of these sulfhydryls during wine storage based on the existing enology literature as well as studies from food chemistry, geochemistry, biochemistry, and synthetic chemistry. We propose that three precursor classes have sufficient concentration and metastability to serve as latent sulfhydryl precursors in wine: 1) transition metal-sulfhydryl complexes, particularly those formed following Cu(II) addition, which are released under anoxic conditions through an unknown mechanism; 2) asymmetric disulfides, polysulfanes, and (di)organopolysulfanes formed through transition-metal mediated oxidation (e.g., Cu(II)) of sulfhydryls or pesticide degradation, and released through sulfitolysis, metal-catalyzed thiol-disulfide exchange or related reactions; 3) S-alkylthioacetates, primarily formed during fermentation, and releasable hydrolytically. Some evidence also exists for S-amino acids serving as precursors. Based on these findings, we propose a "decision tree" approach to choosing appropriate strategies for managing wines with sulfurous off-aromas.

Liberation of Hydrogen Sulfide from Dicysteinyl Polysulfanes in Model Wine.

Diorganopolysulfanes can be generated when hydrogen sulfide (H2S) and thiols are oxidized in the presence of Cu(II) under conditions usually aimed at removing H2S from wine. This work sought to understand if polysulfanes could act as latent sources of H2S during postbottling storage. The stability of the polysulfanes formed in situ in model wine containing cysteine, H2S, and transition metals was dependent both on the number of sulfur linking atoms (Sn) and on the presence of a reducing agent, such as sulfur dioxide or ascorbic acid. A polysulfane containing three linking sulfur atoms was the most stable, with 84% of the relative initial amount remaining in solution after six months, compared to polysulfanes containing four or more linking sulfur atoms that decomposed rapidly, with 26% remaining after six months. Importantly, sulfur dioxide was associated with the rapid degradation of polysulfanes and subsequent liberation of H2S. Three cysteine- S-sulfonates were also tentatively identified, which gives insight into the possible release mechanisms involved with H2S reappearance.

Copper(II)-Mediated Hydrogen Sulfide and Thiol Oxidation to Disulfides and Organic Polysulfanes and Their Reductive Cleavage in Wine: Mechanistic Elucidation and Potential Applications.

Fermentation-derived volatile sulfur compounds (VSCs) are undesirable in wine and are often remediated in a process known as copper fining. In the present study, the addition of Cu(II) to model and real wine systems containing hydrogen sulfide (H2S) and thiols provided evidence for the generation of disulfides (disulfanes) and organic polysulfanes. Cu(II) fining of a white wine spiked with glutathione, H2S, and methanethiol (MeSH) resulted in the generation of MeSH-glutathione disulfide and trisulfane. In the present study, the mechanisms underlying the interaction of H2S and thiols with Cu(II) is discussed, and a prospective diagnostic test for releasing volatile sulfur compounds from their nonvolatile forms in wine is investigated. This test utilized a combination of reducing agents, metal chelators, and low-oxygen conditions to promote the release of H2S and MeSH, at levels above their reported sensory thresholds, from red and white wines that were otherwise free of sulfidic off-odors at the time of addition.

Removal of fumonisin B1 and B2 from model solutions and red wine using polymeric substances.

Fumonisins are a group of mycotoxins found in various foods whose consumption is known to be harmful for human health. In this study, we evaluated the ability of three polymers (Polyvinylpolypyrrolidone, PVPP; a resin of N-vinyl-2-pyrrolidinone with ethylene glycol dimethacrylate and triallyl isocyanurate, PVP-DEGMA-TAIC; and poly(acrylamide-co-ethylene glycol-dimethacrylate), PA-EGDMA) to remove fumonisin B1 (FB1) and fumonisin B2 (FB2) from model solutions and red wine. Various polymer concentrations (1, 5 and 10mgmL-1) and contact times (2, 8 and 24h) were tested, with all polymers exhibiting fumonisin removal capacities (monitored by LC-MS). The impact of all polymers on polyphenol removal was also assessed. PA-EGDMA showed to be the most promising polymer, removing 71% and 95% of FB1, and FB2, respectively, with only a 22.2% reduction in total phenolics.

Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 1: Copper-Catalyzed Oxidation.

Sulfidic off-odors as a result of hydrogen sulfide (H2S) and low-molecular-weight thiols are commonly encountered in wine production. These odors are usually removed by the process of Cu(II) fining, a process that remains poorly understood. The present study aims to elucidate the underlying mechanisms by which Cu(II) interacts with H2S and thiol compounds (RSH) under wine-like conditions. Copper complex formation was monitored along with H2S, thiol, oxygen, and acetaldehyde concentrations after the addition of Cu(II) (50 or 100 µM) to air-saturated model wine solutions containing H2S, cysteine, 6-sulfanylhexan-1-ol, or 3-sulfanylhexan-1-ol (300 µM each). The presence of H2S and thiols in excess to Cu(II) led to the rapid formation of ∼1.4:1 H2S/Cu and ∼2:1 thiol/Cu complexes, resulting in the oxidation of H2S and thiols and reduction of Cu(II) to Cu(I), which reacted with oxygen. H2S was observed to initially oxidize rather than form insoluble copper sulfide. The proposed reaction mechanisms provide insight into the extent to which H2S can be selectively removed in the presence of thiols in wine.

Reaction Mechanisms of Metals with Hydrogen Sulfide and Thiols in Model Wine. Part 2: Iron- and Copper-Catalyzed Oxidation.

Sulfidic off-odors arising during wine production are frequently removed by Cu(II) fining. In part 1 of this study ( 10.1021/acs.jafc.6b00641 ), the reaction of H2S and thiols with Cu(II) was examined; however, the interaction of iron and copper is also known to play an important synergistic role in mediating non-enzymatic wine oxidation. The interaction of these two metals in the oxidation of H2S and thiols (cysteine, 3-sulfanylhexan-1-ol, and 6-sulfanylhexan-1-ol) was therefore examined under wine-like conditions. H2S and thiols (300 µM) were reacted with Fe(III) (100 or 200 µM) alone and in combination with Cu(II) (25 or 50 µM), and concentrations of H2S and thiols, oxygen, and acetaldehyde were monitored over time. H2S and thiols were shown to be slowly oxidized in the presence of Fe(III) alone and were not bound to Fe(III) under model wine conditions. However, Cu(II) added to model wine containing Fe(III) was quickly reduced by H2S and thiols to form Cu(I) complexes, which then rapidly reduced Fe(III) to Fe(II). Oxidation of Fe(II) in the presence of oxygen regenerated Fe(III) and completed the iron redox cycle. In addition, sulfur-derived oxidation products were observed, and the formation of organic polysulfanes was demonstrated.

Efficient routes towards a series of 5,5'-bithiazolidinylidenes as π-electron acceptors.

Different approaches have been studied in order to prepare efficiently the sulfur rich electron acceptor, DEBTTT. Among the various routes used, the one going through the synthesis of a bicyclic derivative, where the thiazole-2-chalcogenone is fused with a 1,3-dithiole-2-one, leads to the target molecule under milder conditions and better yield. Thus, this approach has been explored for the synthesis of a series of acceptors either by modifying the substituent on the thiazole core or by changing the exocyclic chalcogen atoms. All these sulfur rich electron acceptors exhibit short intra- and intermolecular SS contacts in the solid state. Electrochemical investigations show that the nature of the exocyclic chalcogen atom of the thiazole ring has a significant influence on the accepting ability as a cathodic shift of about 220 mV is observed just by changing sulfur for oxygen. This structural modification enables the tuning of the redox properties.

Effect of metal chelators on the oxidative stability of model wine.

Oxidation is a major problem with respect to wine quality, and winemakers have few tools at their disposal to control it. In this study, the effect of exogenous Fe(II) (bipyridine; Ferrozine) and Fe(III) chelators (ethylenediaminetetraacetic acid, EDTA; phytic acid) on nonenzymatic wine oxidation was examined. The ability of these chelators to affect the formation of 1-hydroxyethyl radicals (1-HER) and acetaldehyde was measured using a spin trapping technique with electron paramagnetic resonance (EPR) and by HPLC-PDA, respectively. The chelators were then investigated for their ability to prevent the oxidative loss of an important aroma-active thiol, 3-mercaptohexan-1-ol (3MH). The Fe(II)-specific chelators were more effective than the Fe(III) chelators with respect to 1-HER inhibition during the early stages of oxidation and significantly reduced oxidation markers compared to a control during the study. However, although the addition of Fe(III) chelators was less effective or even showed an initial pro-oxidant activity, the Fe(III) chelators proved to be more effective antioxidants compared to Fe(II) chelators after 8 days of accelerated oxidation. In addition, it is shown for the first time that Fe(II) and Fe(III) chelators can significantly inhibit the oxidative loss of 3MH in model wine.

Investigation of ethyl radical quenching by phenolics and thiols in model wine.

In the present study, the reaction between 1-hydroxyethyl radicals (1-HER) and various wine-related phenolics and thiols, including gallic acid, caffeic acid, ferulic acid, 3-mercaptohexan-1-ol (3MH), cysteine (Cys), and glutathione (GSH), was studied using competitive spin trapping with electron paramagnetic resonance (EPR) and mass spectrometry. Previous studies have reported several important reactions occurring between quinones and other wine components, but the fate of 1-HER within the context of wine oxidation is less understood. Furthermore, the ability of these compounds to prevent formation of acetaldehyde, a known nonenzymatic oxidation product of ethanol, was measured. The hydroxycinnamic acids and thiol compounds tested at 5 mM concentrations significantly inhibited spin adduct formation, indicating their reactivity toward 1-HER. In addition, we confirm that loss of 3MH under model wine conditions is due to quinone trapping as well as 1-HER-induced oxidation.

Correlation of MRI-derived apparent diffusion coefficients in newly diagnosed gliomas with [18F]-fluoro-L-dopa PET: what are we really measuring with minimum ADC?

BACKGROUND AND PURPOSE: There is significant interest in whether diffusion-weighted MR imaging indices, such as the minimum apparent diffusion coefficient, may be useful clinically for preoperative tumor grading and treatment planning. To help establish the pathologic correlate of minimum ADC, we undertook a study investigating the relationship between minimum ADC and maximum FDOPA PET uptake in patients with newly diagnosed glioblastoma multiforme. MATERIALS AND METHODS: MR imaging and FDOPA PET data were acquired preoperatively from 15 patients who were subsequently diagnosed with high-grade brain tumor (WHO grade III or IV) by histopathologic analysis. ADC and SUVR normalized FDOPA PET maps were registered to the corresponding CE MR imaging. Regions of minimum ADC within the FDOPA-defined tumor volume were anatomically correlated with areas of maximum FDOPA SUVR uptake. RESULTS: Minimal anatomic overlap was found between regions exhibiting minimum ADC (a putative marker of tumor cellularity) and maximum FDOPA SUVR uptake (a marker of tumor infiltration and proliferation). FDOPA SUVR measures for tumoral regions exhibiting minimum ADC (1.36±0.22) were significantly reduced compared with those with maximum FDOPA uptake (2.45±0.88, P=.0001). CONCLUSIONS: There was a poor correlation between minimum ADC and the most viable/aggressive component of high-grade gliomas. This study suggests that other factors, such as tissue compression and ischemia, may be contributing to restricted diffusion in GBM. Caution should be exercised in the clinical use of minimum ADC as a marker of tumor grade and the use of this index for guiding tumor biopsies preoperatively.

Apatite forming ability and cytocompatibility of pure and Zn-doped bioactive glasses.

The use of bone grafts permits the filling of a bone defect without risk of virus transmission. In this work, pure bioactive glass (46S6) and zinc-doped bioactive glass (46S6Zn10) with 0.1 wt% zinc are used to elaborate highly bioactive materials by melting and rapid quenching. Cylinders of both types of glasses were soaked in a simulated body fluid (SBF) solution with the aim of determining the effect of zinc addition as a trace element on the chemical reactivity and bioactivity of glass. Several physico-chemical characterization methods such as x-ray diffraction, Fourier transform infrared spectroscopy and nuclear magnetic resonance methods, with particular focus on the latter, were chosen to investigate the fine structural behaviour of pure and Zn-doped bioactive glasses as a function of the soaking time of immersion in SBF. Inductively coupled plasma-optical emission spectroscopy (ICP-OES) was used to measure the concentrations of Ca and P ions in the SBF solution after different durations of immersion. The effect of the investigated samples on the proliferation rate of human osteoblast cells was assessed by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay, and tested on two different sizes of pure and zinc-doped glasses in powder form, with particle sizes that ranged between 40 to 63 µm and 500 to 600 µm. The obtained results showed the delay release of ions by Zn-doped glass (46S6Zn10) and the slower CaP deposition. Cytotoxicity and cell viability were affected by the particle size of the glass. The release rate of ions was found to influence the cell viability.

New evidence for the role of TNF-alpha in liver ischaemic/reperfusion injury.

BACKGROUND: Tumour necrosis factor-alpha (TNF-alpha) plays a key role in causing ischaemia/reperfusion (I/R) injury. I/R also causes activation of xanthine oxidase and dehydrogenase (XDH + XO) system that, via generated free radicals, causes organ damage. We investigated the effect of ischaemia, reperfusion and non-ischaemic prolonged perfusion (NIP) on TNF-alpha and XDH + XO production in an isolated perfused rat liver model. MATERIALS AND METHODS: Rat livers underwent 150 min NIP (control group) or two hours of ischaemia followed by reperfusion (I/R group). TNF-alpha (TNF-alpha mRNA and protein level), XDH + XO production and bile secretion were determined in tissue and effluent at baseline, at 120 min of ischaemia, after 30 min of reperfusion (I/R group) and after 120 and 150 min of prolonged perfusion (control). RESULTS: Unexpectedly, neither ischaemia nor reperfusion had any effect on TNF-alpha production. TNF-alpha in effluent was 11 +/- 4.8 pg mL(-1) at baseline, 7 +/- 3.2 pg mL(-1) at the end of ischaemia, and 13 +/- 5.3 pg mL(-1) after 30 min of reperfusion. NIP, however, caused a significant increase of TNF-alpha synthesis and release. TNF-alpha effluent level after 120 and 150 min of perfusion was 392 +/- 78.7 pg mL(-1) and 408 +/- 64.3 pg mL(-1), respectively. TNF-alpha mRNA in tissue was also significantly elevated compared to baseline levels (1.31 +/- 0.2 P < 0.001 and 1.38 P < 0.002, respectively). Decrease of liver function (expressed by bile secretion) during I/R and NIP was accompanied by significant XDH + XO elevation. CONCLUSION: This is the first evidence that NIP, and not I/R, is the decisive trigger for TNF-alpha production. This study leads to a better understanding of pathogenesis of liver I/R and perfusion damage.

Responses of apple fruit size to tree water status and crop load.

The combined effects of irrigation rate and crop load on apple yield and fruit size were examined in two commercial apple orchards (cv. Golden Delicious) in a semi-arid zone. The irrigation rates applied were 1, 3 and 7 mm day(-1), and the two fruit thinning treatments involved adjusting crop load to 100 and 300 fruits per tree at Ortal and 50 and 150 fruits per tree at Matityahu. Unthinned trees served as the control. The fruit from each tree was picked separately, and fruit size distribution was determined with a commercial grading machine. Midday stem water potentials varied from -0.9 to -2.8 MPa, crop load varied from 80,000 to 1,900,000 fruit ha(-1) and crop yield varied from 10 to 144 Mg ha(-1). Midday stem water potential decreased with increasing crop load in all irrigation treatments at Matityahu, but only in the 1 mm day(-1) treatment at Ortal. The extent of the lowering of midday stem water potential by crop load decreased with increasing soil water availability. At both orchards, a similar response of total crop yield to crop load on a per hectare basis was observed. Mean fruit mass and relative yield of fruit > 70 mm in diameter increased with midday stem water potential, with the low crop loads having similar but steeper slopes than the high crop load. The responses of mean fruit mass and relative yield of fruit > 70 mm in diameter to midday stem water potential were similar at both orchards, perhaps indicating that thresholds for irrigation scheduling are transferable to other orchards within a region. Factors that may limit the transferability of these thresholds are discussed.

Technical aspects of harvesting the radial artery with the harmonic scalpel.

BACKGROUND: Harvesting the radial artery (RA) with ultrasonic dissection with the Harmonic Scalpel reduces spasm induced by surgical handling. Topical exposure to phentolamine methanesulphonate (Regitine) exerts an additional effect of vasodilatation. METHODS: Between January and December 2002, the RA was harvested as a pediculated vessel with the Harmonic Scalpel in 145 consecutive patients undergoing myocardial revascularization. A fasciotomy of the pedicle was performed after harvest ing. A composite graft with the reverse free RA on the in situ left internal thoracic artery (ITA) was prepared before the construction of distal coronary anastomoses. The RA was then placed in a syringe filled with Regitine (0.07 microg/mL) for 10 minutes. \par RESULTS: The mean number of grafts/patient was 3.0. The mean number of RA anastomoses was 2.0/patient. Left ITA free flow was 105 +/- 34 mL/min. Regitine increased the RA free flow from 60 +/- 35 mL/min to 82 +/- 30 mL/min (P <.05). Fourteen patients underwent postoperative coronary angiography. All RA anastomoses were patent. CONCLUSION: The compound effect of RA harvesting with the Harmonic Scalpel and topical treatment with the alpha- blocking agent Regitine increases the RA free flow and significantly decreases intraoperative spasticity.

Inhibition of marine bacteria by extracts of macroalgae: potential use for environmentally friendly antifouling paints.

Although a total ban on the use of TBT coatings is not expected in the short term, there is a growing need for environmentally safe antifouling systems. A search for new non-toxic antifoulants has been carried out among marine macroalgae. Antifouling activity of aqueous, ethanolic and dichloromethane extracts from 30 marine algae from Brittany coast (France) was examined in vitro against 35 isolates of marine bacteria. About 20% of the extracts were found to be active. The high levels of inhibitory activities against bacteria recorded in some extracts and the absence of toxicity on the development of oyster and sea urchin larvae and to mouse fibroblast growth suggests a potential for novel active ingredients in antifouling preparations.

A randomized, controlled clinical trial of the homeopathic medication TRAUMEEL S in the treatment of chemotherapy-induced stomatitis in children undergoing stem cell transplantation.

BACKGROUND: Stomatitis is a common consequence of chemotherapy and a condition for which there is little effective treatment. Although the management of patients with other chemotherapy-related toxicities has improved in recent years, the incidence of stomatitis is increasing because of more intensive treatment and is often a dose limiting factor in chemotherapy. The authors assessed the efficacy of a homeopathic remedy, TRAUMEEL S(R), in the management of chemotherapy-induced stomatitis in children undergoing bone marrow transplantation. METHODS: A randomized, placebo-controlled, double-blind clinical trial was conducted in 32 patients ages 3-25 years who had undergone allogeneic (16 patients) or autologous (16 patients) stem cell transplantation. Of the 30 evaluable patients, 15 were assigned placebo, and 15 were assigned TRAUMEEL S both as a mouth rinse, administered five times daily from 2 days after transplantation for a minimum of 14 days, or until at least 2 days after all signs of stomatitis were absent. Stomatitis scores were evaluated according to the World Health Organization grading system for mucositis. RESULTS: A total of five patients (33%) in the TRAUMEEL S treatment group did not develop stomatitis compared with only one patient (7%) in the placebo group. Stomatitis worsened in only 7 patients (47%) in the TRAUMEEL S treatment group compared with 14 patients (93%) in the placebo group. The mean area under the curve stomatitis scores were 10.4 in the TRAUMEEL S treatment group and 24.3 in the placebo group. This difference was statistically significant (P < 0.01). CONCLUSIONS: This study indicates that TRAUMEEL S may reduce significantly the severity and duration of chemotherapy-induced stomatitis in children undergoing bone marrow transplantation.

Inhibition of the development of microorganisms (bacteria and fungi) by extracts of marine algae from Brittany, France.

The inhibitory effects of aqueous, ethanolic and dichloromethane fractions from 16 marine algae from the Atlantic shores of North-East Brittany, France, have been investigated against microorganisms frequently associated with immersed surfaces. The extracts were tested in vitro against isolates of marine fungi, bacteria and yeasts potentially involved at different stages in the formation of biofilms in the sea. The high levels of inhibitory activity of nine extracts against marine fungi and Gram-positive bacteria and their apparent absence of toxicity against larvae of oysters and sea urchins suggests a potential for novel active ingredients.

Coordinated changes of adenylate energy charge and ATP/ADP: use in ecotoxicological studies.

The coordinated variations of the adenylate energy charge and ATP/ADP ratio were modeled and a function that depends on the numerical value of the adenylate kinase-catalyzed reaction has been derived. The model allows sensitive detection of the effects of xenobiotics on adenylate kinase and its cellular environment and offers a robust estimation of the direct or indirect effects of pollutants on the adenylate kinase system: data obtained in laboratory studies on shrimp exposed to cadmium and in field studies on oysters either exposed to polychloro-biphenyl compounds or located in a heavily polluted area indicate that xenobiotics affect the adenylate kinase reaction directly or by changing its cellular environment. These results demonstrate that application of the model to the treatment of ecotoxicological data allows detection of energetic changes that would have been missed by simple analysis of the usual energetic parameters, and should overcome problems encountered in using energetic parameters during assessment of pollution monitoring.

Secretagogues and Growth Factors in Fish and Crustacean Protein Hydrolysates.

: The search for new molecules in fish protein hydrolysates is of great interest in animal feeding as it is in aquaculture, fertilizer, cosmetic, and pharmacologic domains. Different sources of hydrolysates such as shrimp waste (Pandalus borealis), cod (Gadus morhua) head, and head and viscera of sardine (Sardina pilchardus), obtained after hydrolysis or autolysis, were tested on fibroblast cell cultures and by gastrin radioimmunoassay. The level of hydrolysis seems to play an important role in the presence of biological peptides. Elution profile on a gel filtration Sephadex G-50 column was used to estimate the degree of hydrolysis of the fractions studied. Growth-factor-like activities were found in less-hydrolyzed fractions. Conversely, the most-hydrolyzed fractions showed gastrin and cholecystokinin immunoreactivity.