Solvent- and Wavelength-Dependent Photolysis of Estrone.

The direct photolysis of estrone in solvents ranging from water to cyclohexane is reported. The photodegradation is dominated by lumiestrone, an epimer of estrone resulting from the inversion of the methyl group at carbon 13, regardless of solvent and photolysis wavelength in the range 254-320 nm. Solvent addition products are also observed in lesser amounts. The photodegradation rate in water is an order of magnitude slower than in nonaqueous solvents. Short wavelength excitation enhances photodegradation. Together, these results suggest complicated photophysics underlie the photochemistry with implications for the remediation of environmental estrogens.

A fast-response two-photon fluorescent probe for imaging endogenous H2O2 in living cells and tissues.

As a second messenger, hydrogen peroxide plays significant roles in numerous physiological and pathological processes and is related to various diseases including inflammatory disease, diabetes, neurodegenerative disorders, cardiovascular disease and Alzheimer's disease. Two-photon (TP) fluorescent probes reported for the detection of endogenous H2O2 are rare and most have drawbacks such as slow response and low sensitivity. In this report, we demonstrate a simple H2O2-specific TP fluorescent probe (TX-HP) containing a two-photon dye 6-hydroxy-2,3,4,4a-tetrahydro-1H-xanthen-1-one (TX) on the modulation of the ICT process. The probe exhibits a rapid fluorescent response to H2O2 in 9min with both high sensitivity and selectivity. The probe can detect exogenous H2O2 in living cells. Furthermore, the probe is successfully utilized for imaging H2O2 in liver tissues.

The contribution of wine-derived monoterpene glycosides to retronasal odour during tasting.

This study investigated the sensory significance of monoterpene glycosides during tasting, by retronasal perception of odorant aglycones released in-mouth. Monoterpene glycosides were isolated from Gewürztraminer and Riesling juices and wines, chemically characterised and studied using sensory time-intensity methodology, together with a synthesised monoterpene glucoside. When assessed in model wine at five times wine-like concentration, Gewürztraminer glycosides and geranyl glucoside gave significant fruity flavour, although at wine-like concentrations, or in the presence of wine volatiles, the effect was not significant. Gewürztraminer glycosides, geranyl glucoside and guaiacyl glucoside were investigated using a sensory panel (n=39), revealing large inter-individual variability, with 77% of panellists responding to at least one glycoside. The study showed for the first time that grape-derived glycosides can contribute perceptible fruity flavour, providing a means of enhancing flavour in wines, and confirms the results of previous studies that the effect is highly variable across individuals.

Structural characterization of reaction products of caftaric acid and bisulfite present in a commercial wine using high resolution mass spectrometric and nuclear magnetic resonance techniques.

Reaction products of bisulfite and caftaric acid were found in wines containing sulfites as a preservative. Acidic compounds were separated from wine and analyzed by HPLC combined with DAD and QTOF mass spectrometer. HPLC chromatograms of the expected [M-H]- ion and UV absorption revealed the presence of five possible reaction products (a-e). These compounds were isolated then characterized by NMR and confirmed to be the reaction products as follows; 5-sulfo-(E)-caftaric acid (a), 2-sulfo-(Z)-caftaric acid (b), 2-sulfo-(E)-caftaric acid (c), (E)-caftaric acid-4-O-sulfate (d) and (E)-caftaric acid-3-O-sulfate (e). UV spectra and high resolution product ion spectra of the five compounds also supported their identity. The reaction products were confirmed to be commonly present in commercial wines across four vintages and two varieties. Their concentration was found to be as much as that of 2-S-glutathionyl caftaric acid, suggesting that bisulfite consistently competes as a nucleophile with glutathione for the o-quinone of caftaric acid.

Quantitative analysis by GC-MS/MS of 18 aroma compounds related to oxidative off-flavor in wines.

A quantitation method for 18 aroma compounds reported to contribute to "oxidative" flavor in wines was developed. The method allows quantitation of the (E)-2-alkenals ((E)-2-hexenal, (E)-2-heptenal, (E)-2-octenal, and (E)-2-nonenal), various Strecker aldehydes (methional, 2-phenylacetaldehyde, 3-methylbutanal, and 2-methylpropanal), aldehydes (furfural, 5-methylfurfural, hexanal, and benzaldehyde), furans (sotolon, furaneol, and homofuraneol), as well as alcohols (methionol, eugenol, and maltol) in the same analysis. The aldehydes were determined after derivatization directly in the wine with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride; the formed oximes along with the underivatized aroma compounds were isolated by solid-phase extraction and analyzed by means of GC-MS/MS. The method was used to investigate the effect of different closures (synthetic closures, natural corks, and screw cap) on the formation of oxidation-related compounds in 14 year old white wine. Results showed a significant increase in the concentration of some of the monitored compounds in the wine, particularly methional, 2-phenylacetaldehyde, and 3-methylbutanal.

Determination of the importance of in-mouth release of volatile phenol glycoconjugates to the flavor of smoke-tainted wines.

The volatile phenols guaiacol, 4-methylguaiacol, syringol, 4-methylsyringol, o-, m-, and p-cresol, as well as their glycoconjugates, have previously been shown to be present in elevated concentrations in smoke-tainted wine. Sensory descriptive analysis experiments, with addition of free volatile phenols in combination with their glycosidically bound forms, were used to mimic smoke taint in red wines. The addition of volatile phenols together with glycoconjugates gave the strongest off-flavor. The hydrolysis of glycosidically bound flavor compounds in-mouth was further investigated by in vitro and in vivo experiments. The results indicate that enzymes present in human saliva are able to release the volatile aglycones from their glycoconjugates even under low pH and elevated ethanol conditions, confirming that in-mouth breakdown of monosaccharide and disaccharide glycosides is an important mechanism for smoke flavor from smoke affected wines, and that this mechanism may play an important general role in the flavor and aftertaste of wine.

Assessing the impact of smoke exposure in grapes: development and validation of a HPLC-MS/MS method for the quantitative analysis of smoke-derived phenolic glycosides in grapes and wine.

Bushfires occur frequently in the vicinity of grape growing regions, resulting in smoke drifting over the vineyards. Wine made from smoked grapes is often downgraded or unfit for sale due to negative sensory characters. To manage or avoid the risk of producing smoke-affected wine, a diagnostic assay was developed for assessing the extent of smoke exposure in grapes and the resulting wines. The method relies on the quantitation of the glycosidic grape metabolites that are formed from major volatile phenols present in smoke. Using HPLC-MS/MS with APCI, a quantitation method for phenolic glycosides as smoke marker compounds was developed and validated. The method was confirmed to be of sufficient sensitivity and reliability to use as a diagnostic assay. On the basis of phenolic glycoside concentrations, grapes or wine can be assessed as smoke exposed or not, and the relative intensity of smoke exposure can be determined.

Effects on 3-mercaptohexan-1-ol precursor concentrations from prolonged storage of Sauvignon blanc grapes prior to crushing and pressing.

Formation of wine thiol precursors is a dynamic process, which can be influenced by vineyard and winery processing operations. With the aim of increasing thiol precursor concentrations, a study of the effects of storing machine-harvested Sauvignon blanc grapes prior to crushing and pressing was undertaken on a commercial scale. 3-Mercaptohexan-1-ol (3-MH) precursors, 2-S-glutathionylcaftaric acid (grape reaction product, GRP), glutathione (GSH) and a number of C6 compounds were assessed at several time points during the experiment. The concentration of the cysteine precursor to 3-MH doubled within 8 h and tripled after 30 h while the GSH and cysteinylglycine precursors increased in concentration roughly 1.5 times. (E)-2-Hexenal and GSH levels decreased as thiol precursors, GRP and C6 alcohols increased during storage. Principal component analysis revealed that precursors contributed to most of the variation within the samples over the storage period, with additional influence, primarily from GSH and GRP, as well as (E)-2-hexenal and (Z)-3-hexen-1-ol. Early storage time points were associated with higher concentrations of GSH and some unsaturated C6 compounds while longer storage times were most closely associated with higher thiol precursor and GRP concentrations. This study provides a detailed overview of interactions related to thiol precursor formation on a commercial scale and highlights the ability to manipulate precursor concentrations prior to grape crushing.

Contribution of several volatile phenols and their glycoconjugates to smoke-related sensory properties of red wine.

Guaiacol and 4-methylguaiacol are well-known as contributors to the flavor of wines made from smoke-affected grapes, but there are other volatile phenols commonly found in smoke from forest fires that are also potentially important. The relationships between the concentration of a range of volatile phenols and their glycoconjugates with the sensory characteristics of wines and model wines were investigated. Modeling of the attribute ratings from a sensory descriptive analysis of smoke-affected wines with their chemical composition indicated the concentrations of guaiacol, o-cresol, m-cresol, and p-cresol were related to smoky attributes. The best-estimate odor thresholds of these compounds were determined in red wine, together with the flavor threshold of guaiacol. Guaiacol ß-D-glucoside and m-cresol ß-D-glucoside in model wine were found to give rise to a smoky/ashy flavor in-mouth, and the respective free volatiles were released. The study indicated that a combination of volatile phenols and their glycosides produces an undesirable smoke flavor in affected wines. The observation of flavor generation from nonvolatile glycoconjugates in-mouth has potentially important implications.

Glycosylation of smoke-derived volatile phenols in grapes as a consequence of grapevine exposure to bushfire smoke.

The presence of glycosides of smoke-derived volatile phenols in smoke-affected grapes and the resulting wines of Chardonnay and Cabernet Sauvignon was investigated with the aid of high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). All volatile phenols studied (phenol, p-, m-, and o-cresols, methylguaiacol, syringol, and methylsyringol) could be detected as glycosylated metabolites in smoke-affected grapes in a similar fashion to that previously reported for guaiacol. These phenolic glycosides were found in smoke-affected grapes and wines at significantly elevated levels compared to those in non-smoked control grapes and wines. The extraction of these glycosides from grapes into wine was estimated to be 78% for Chardonnay and 67% for Cabernet Sauvignon. After acid hydrolysis, a large proportion of these phenolic glycosides in grapes (50%) and wine (92%) disappeared but the concentrations of volatile phenols determined by gas chromatography-mass spectrometry (GC-MS) were lower than expected. In the case of wine, the majority of the glycosides of phenol, cresols, guaiacol, and methylguaiacol were decomposed upon acid hydrolysis without releasing their respective aglycones, while syringol and methylsyringol were more effectively released.

3-D lanthanide metal-organic frameworks: structure, photoluminescence, and magnetism.

A series of isostructural three-dimensional metal-organic frameworks [Pr(2)(N-BDC)(3)(dmf)(4)](infinity) (1), {[Eu(2)(N-BDC)(3)(dmf)(4)] x 2DMF}(infinity) (2 x 2DMF), [Gd(2)(N-BDC)(3)(dmf)(4)](infinity) (3), {[Tb(2)(N-BDC)(3)(dmf)(4)] x 2DMF}(infinity) (4 x 2DMF), {[Dy(2)(N-BDC)(3)(dmf)(4)] x 2DMF}(infinity) (5 x 2DMF) (N-H(2)BDC = 2-amino-1,4-benzenedicarboxylic acid; DMF = N,N'-dimethylformamide) with cubic 4(12) x 6(3) topology have been synthesized using solvothermal conditions. The networks were generated via formation of a dinuclear Ln(2) secondary building block, involving the dicarboxylate ligand as a bridge. The luminescent properties of the Tb(III) and Eu(III) complexes were studied and showed characteristic emissions at room temperature. Antiferromagnetic interactions between Ln(III) ions were observed from magnetic susceptibility data.

Activator of G protein signaling 3 null mice: I. Unexpected alterations in metabolic and cardiovascular function.

Activator of G protein signaling (AGS)-3 plays functional roles in cell division, synaptic plasticity, addictive behavior, and neuronal development. As part of a broad effort to define the extent of functional diversity of AGS3-regulated-events in vivo, we generated AGS3 null mice. Surprisingly, AGS3 null adult mice exhibited unexpected alterations in cardiovascular and metabolic functions without any obvious changes in motor skills, basic behavioral traits, and brain morphology. AGS3 null mice exhibited a lean phenotype, reduced fat mass, and increased nocturnal energy expenditure. AGS3 null mice also exhibited altered blood pressure control mechanisms. These studies expand the functional repertoire for AGS3 and other G protein regulatory proteins providing unexpected mechanisms by which G protein systems may be targeted to influence obesity and cardiovascular function.

A coordination polymer strategy for anion encapsulation: anion-pi interactions in (4,4) nets formed from Ag(I) salts and a flexible pyrimidine ligand.

Anions encapsulated by a uniform mode of anion-pi binding in isomorphous (4,4) nets formed from Ag(I) salts and bis(4-pyrimidylmethyl)sulfide appear to be structurally directing.

Probing anion-pi interactions in 1-D Co(II), Ni(II), and Cd(II) coordination polymers containing flexible pyrazine ligands.

Two flexible thioether-containing heterocyclic ligands bis(2-pyrazylmethyl)sulfide (L1) and 2-benzylsulfanylmethylpyrazine (L2) have arene rings with differing pi-acidities which were used to probe anion-pi binding in five 1-D coordination polymers formed from the metal salts Co(ClO4)2, Ni(NO3)2, and Cd(NO3)2. In {[Co(L1)(MeCN)2](ClO4)2}infinity (1), {[Ni(L1)(NO3)2]}infinity (2), and {[Cd2(L1)(MeCN)(H2O)(NO3)4].H2O}infinity (3.H2O), the symmetrical ligand L1 was bound facially to the metal center and was bridged through a pyrazine donor to an adjacent metal forming a polymer chain. The folding of L1 formed U-shaped pi-pockets in 1 and 3.H2O which encapsulated free and bound anions, respectively. The anions interacted with the pi-acidic centers in a variety of different binding modes including anion-pi-anion and pi-anion-pi sandwiching. A wider pi-pocket was formed in 2 which also contained anion-pi interactions. The polymer chains in 2 were interdigitated through a rare type of complementary T-shaped N(pyrazine)...pi interaction. In {[Co(L2)(H2O)3](ClO4)2.H2O}infinity (4.H2O) and {[Cd(L2)(H2O)(NO3)2]}infinity (5), the unsymmetrical ligand L2 chelated the metal center and bridged through a pyrazine donor to an adjacent metal forming a polymer chain. The ligand arrangement resulted in the anions in both structures being involved in only anion-pi-anion sandwich interactions. In 4.H2O, the noncoordinated ClO4- anions interacted with only one chain while in 5 the coordinated NO3- anions acted as anion-pi supramolecular synthons between chains. Comparison between the polymers formed with ligands L1 and L2 showed that only the more pi-acidic ring was involved in the anion-pi interactions.