The effect of cooking on acrylamide and its precursors in potato, wheat and rye

The relationship between acrylamide and its precursors, namely free asparagine and reducing sugars, was studied in simple cakes made from potato flake, wholemeal wheat and wholemeal rye, cooked at 180 degrees C, from 5 to 60 min. Between 5 and 20 min, large losses of asparagine, water and total reducing sugars were accompanied by large increases in acrylamide, which maximized in all three products between 25 and 30 min, followed by a slow linear reduction. Acrylamide formation did not occur to any extent until the moisture contents of the cakes fell below 5%. A comparison of each type of cake with a commercial product, made from the same food material, showed that acrylamide levels in all three commercial products were well below the maximum levels in the cooked cakes.

Measurement of acrylamide and its precursors in potato, wheat, and rye model systems

The relationship between acrylamide and its precursors, namely, free asparagine and reducing sugars, was studied in cakes made from potato flake, wholemeal wheat, and wholemeal rye, cooked at 180 degreesC, from 5 to 60 min. Between 5 and 20 min, major losses of asparagine, water, and total reducing sugars were accompanied by large increases in acrylamide, which maximized in all three products between 25 and 30 min, followed by a slow linear reduction. Acrylamide formation did not occur to a large degree until the moisture contents of the cakes fell below 5%. Linear relationships were observed for acrylamide formation with the residual levels of asparagine and reducing sugars for all three food materials.

Asymmetric phase-transfer-catalyzed synthesis of five-membered cyclic gamma-Amino acid precursors

The first example of an intramolecular enantioselective Michael addition of nitronates onto conjugated systems utilizing a chiral phase-transfer catalyst is described. A range of five-membered gamma-nitro esters with up to three stereocentres have been prepared and the relative and absolute configurations proven by chemical and crystallographic methods. The products are rapidly obtained and are precursors to five-membered cyclic gamma-amino acids.

Determination of some water-soluble aroma precursors in goat meat and their enrolment on flavour profile of goat meat

Selected water-soluble precursors, including sugars, free amino acids and nucleotides, were quantified in raw and cooked goat meat, as a part of a study which the main aim was to better understand the aroma formation in goat meat. When compared with the same precursors in beef, lamb and chicken, levels in goat meat were generally similar, except for fructose and glycine, which were present at higher concentrations in goat meat. Fructose, glucose, IMP, and cysteine suffered the greatest losses during the cooking process and seem to be most involved in aroma formation in goat meat. The effects of these precursor changes on the volatile compound composition and formation process of them on cooked goat meat are discussed.

Structure of adsorbed organometallic rhodium: model single atom catalysts

We have determined the structure of a complex rhodium carbonyl chloride [Rh(CO)(2)Cl] molecule adsorbed on the TiO2 (110) surface by the normal incidence x-ray standing wave technique. The data show that the technique is applicable to reducible oxide systems and that the dominant adsorbed species is undissociated with Rh binding atop bridging oxygen and to the Cl found close to the fivefold coordinated Ti ions in the surface. A minority geminal dicarboryl species, where Rh-Cl bond scission has occurred, is found bridging the bridging oxygen ions forming a high-symmetry site.

A synthetic route to fully substituted chiral cyclopentylamine derivatives: precursors of carbanucleosides

Removal of silyl protection from D-glucose derived substrate 6 afforded 7, which upon acetonide deprotection followed by reaction with N-benzylhydroxylamine furnished two isomeric isoxazolidinocyclopentane derivatives via spontaneous cyclization of an in situ generated nitrone. The methyl xanthate derivative of the tertiary hydroxyl group of one isomer was isolated and subjected to radical deoxygenation reaction to form epimeric products, while with the other isomer it underwent spontaneous 1,2-elimination to form a mixture of the two possible endocyclic olefins. Hydrogenolytic cleavage of the isoxazolidine rings of the purified products followed by insertion of 5-amino-4-chloropyrimidine moiety and purine ring construction smoothly afforded structurally unique carbanucleoside analogues. Various spectroscopic methods on the synthesized compounds and X-ray analysis on one important intermediate were used to assign the structures and stereochemistry of the products.

Rhodium cationic complexes using dithioethers as chiral ligands. Application in styrene hydroformylation

Addition of the dithioethers (−)-DIOSR2 (R=Me, iPr) (2,3-O-isopropylidene-1,4-dimethyl (and diisopropyl) thioether-L-threitol) to a dichloromethane solution of [Rh(COD)2]ClO4 (COD=1,5-cyclooctadiene) yielded the mononuclear complexes [Rh(COD)(DIOSR2)]ClO4. X-ray diffraction methods showed that the [Rh(COD)(DIOSiPr2)]ClO4 complex had an square-planar coordination geometry at the rhodium atom with the iPr groups in anti position. Cyclooctadiene complexes react with carbon monoxide to form dinuclear tetracarbonylated complexes [(CO)2Rh(μ-DIOSR2)2(CO)2](ClO4)2. [Rh(COD)(DIOSR2)]ClO4 are active catalyst precursors in styrene hydroformylation at 30 atm and 65°C which give conversions of up to 99% with a regioselectivity in 2-phenylpropanal as high as 74%. In all cases enantioselectivities are low.

Anticancer activity of organometallic compounds. 3. The reaction of dimethyltin dichloride with nucleosides under biologically relevant conditions

This paper reports the reaction of SnMe2Cl2 with adenosine, guanosine and inosine in aqueous solution at pH 4.5. The nucleosides give probably polymeric species in which there is monodentate coordination to O2′ of the ribose ring as indicated by 80 MHz PMR.

How vegetation impacts affect climate metrics for ozone precursors

We examine the effect of ozone damage to vegetation as caused by anthropogenic emissions of ozone precursor species and quantify it in terms of its impact on terrestrial carbon stores. A simple climate model is then used to assess the expected changes in global surface temperature from the resulting perturbations to atmospheric concentrations of carbon dioxide, methane, and ozone. The concept of global temperature change potential (GTP) metric, which relates the global average surface temperature change induced by the pulse emission of a species to that induced by a unit mass of carbon dioxide, is used to characterize the impact of changes in emissions of ozone precursors on surface temperature as a function of time. For NOx emissions, the longer-timescale methane perturbation is of the opposite sign to the perturbations in ozone and carbon dioxide, so NOx emissions are warming in the short term, but cooling in the long term. For volatile organic compound (VOC), CO, and methane emissions, all the terms are warming for an increase in emissions. The GTPs for the 20 year time horizon are strong functions of emission location, with a large component of the variability owing to the different vegetation responses on different continents. At this time horizon, the induced change in the carbon cycle is the largest single contributor to the GTP metric for NOx and VOC emissions. For NOx emissions, we estimate a GTP20 of −9 (cooling) to +24 (warming) depending on assumptions of the sensitivity of vegetation types to ozone damage.

1,1′-Bis(diphenylphosphino)ferrocene bridging two mono(cyclopentadienyl) cobalt moieties: synthesis, structure, electrochemistry and DFT studies

Reaction of [Co(eta(5)-C5H5)(CO)(2)], 1, with 1,1'-bis(diphenylphosphino)ferrocene (dppf) yields the new trinuclear complex [Co(eta(5)-C5H5)(CO)](2)(mu-dppf), 2, which was structurally characterised by single crystal X-ray diffraction and showed two Co(eta(5)-C5H5)(CO) moieties covalently linked by a dppf bridge. Electrochemical studies in dichloromethane revealed that both Co(I) and Fe(II) in the precursors were oxidized to Co(II)/Co(III) and Fe(III), respectively. On the other hand, in 2 the two first oxidation waves were assigned to Co, the Fe(II) centre requiring a higher potential than in free dppf. DFT calculations showed that the HOMOs of 2 were localised in the Co fragments, owing to the destabilisation of the Co(eta(5)-C5H5)(CO) orbitals after binding dppf.

Quantifying the climatological relationship between extratropical cyclone intensity and atmospheric precursors

We introduce a novel technique in which linear regression analysis is applied to clusters of tracked cyclones to statistically assess the factors controlling cyclone development. We illustrate this technique by evaluating the differences between cyclones forming in the west and east North Atlantic (herein termed west and east Atlantic cyclones). Enhanced cyclone intensity 2 days after genesis is found to be associated with deeper upper-level troughs upstream of the cyclone center at the genesis time in both west and east Atlantic cyclones. However, whilst west Atlantic cyclones are also enhanced by the presence of strong fronts, east Atlantic cyclones are not. Instead, east Atlantic cyclones exhibit an enhancement when diabatically generated midlevel potential vorticity is present (with the enhancement being of approximately equal magnitude to that associated with the potential vorticity in the upper-level trough). This is consistent with the paradigm of latent heat release in the warm conveyor belt region playing an important role in the development of east Atlantic cyclones.