Effect of lipid oxidation and frozen storage on muscle proteins of Atlantic mackerel (Scomber scombrus)

The effect of storage on the lipids and proteins in Atlantic mackerel stored for up to 24 months at ?20 and ?30 °C was studied. Traditional methods including the peroxide value, thiobarbituric acid‐reactive substances (TBARS) and a reverse phase HPLC method were used to determine the primary and secondary lipid oxidation products. All tests showed an increase in lipid oxidation products with storage time and at a higher storage temperature of ?20 °C compared with samples stored at ?30 °C. Antioxidants had a significant effect (P < 0.01) on the inhibition of lipid oxidation, as shown by the reduction in peroxide value and hydroxides, and malondialdehyde formation. Similarly, deterioration of protein structure and functionality in mackerel stored for 3, 6, 12 and 24 months was greater at ?20 than ?30 °C. ATPase activity in the myosin extract of Atlantic mackerel showed a significant decrease (P < 0.01) with progressive frozen storage. Protein solubility in high salt concentration (0.6 M NaCl) decreased (P < 0.01) during storage at both ?20 and ?30 °C but was greater at ?20 °C. Interestingly, antioxidants BHT, vitamin C and vitamin E protected the proteins against complete loss of ATPase activity and protein solubility to a significant level (P < 0.01) for up to 1 year at ?20 °C compared with samples stored without antioxidants. This study confirms the deleterious effect of lipid oxidation products on protein structure and function in frozen fatty fish. © 2002 Society of Chemical Industry     

ACE-Asia intercomparison of a thermal-optical method for the determination of particle-phase organic and elemental carbon

A laboratory intercomparison of organic carbon (OC) and elemental carbon (EC) measurements of atmospheric particulate matter samples collected on quartz filters was conducted among eight participants of the ACE-Asia field experiment The intercomparison took place in two stages: the first round of the intercomparison was conducted when filter samples collected during the ACE-Asia experiment were being analyzed for OC and EC, and the second round was conducted after the ACE-Asia experiment and included selected samples from the ACE-Asia experiment Each participant operated ECOC analyzers from the same manufacturer and utilized the same analysis protocol for their measurements. The precision of OC measurements of quartz fiber filters was a function of the filter's carbon loading but was found to be in the range of 4-13% for OC loadings of 1.0-25 microg of C cm(-2). For measurements of EC, the precision was found to be in the range of 6-21% for EC loadings in the range of 0.7-8.4 microg of C cm(-2). It was demonstrated for three ambient samples, four source samples, and three complex mixtures of organic compounds that the relative amount of total evolved carbon allocated as OC and EC (i.e., the ECOC split) is sensitive to the temperature program used for analysis, and the magnitude of the sensitivity is dependent on the types of aerosol particles collected. The fraction of elemental carbon measured in wood smoke and an extract of organic compounds from a wood smoke sample were sensitive to the temperature program used for the ECOC analysis. The ECOC split for the three ambient samples and a coal fly ash sample showed moderate sensitivity to temperature program, while a carbon black sample and a sample of secondary organic aerosol were measured to have the same split of OC and EC with all temperature programs that were examined.     

Phenolics of Vaccinium berries and other fruit crops

The concentrations and profiles of phenolics of selected fruit crops common in the Western diet, including several Vaccinium species, were examined to better understand how these crops may be useful sources of phenolic phytochemicals. Vaccinium fruit had a high phenolic concentration compared to non‐Vaccinium fruit. Some Vaccinium fruit were particularly rich in certain phenolic subgroups, especially anthocyanins and pro‐anthocyanidins. Among the pro‐anthocyanidin oligomers measured using fluorometric and mass spectroscopic detection, the trimers and tetramers were most abundant, while pro‐anthocyanidins with a degree of polymerization greater than 8 were least abundant. As biomedical studies determine which phenolic structures are associated with particular bioactivities, information on the phenolic concentration and profile of selected species will be useful in developing specific uses for fruit crops in human health. Methods were compared to assess the usefulness of simpler versus more sophisticated means of phenolic analysis. The phenolic components of fruit extracts were purified approximately 20‐fold, and not qualitatively altered, by C18 solid‐phase extraction. However, fruit extracts obtained from C18 solid‐phase extraction differed in their relative abundance of phenolic components. Colorimetric and HPLC‐DAD measures of phenolic concentration were correlated (R² = 0.79), as was pro‐anthocyanidin concentration detected fluorometrically and by mass spectrometry (R² = 0.44). Copyright © 2007 Crown in the right of Canada and Society of Chemical Industry     

Sesquiterpenes in grapes and wines: Occurrence,biosynthesis, functionality,and influence of winemaking processes

Grapes are an important global horticultural product, and are mainly used for winemaking. Typically, grapes and wines are rich in various phytochemicals, including phenolics, terpenes, pyrazines, and benzenoids, with different compounds responsible for different nutritional and sensory properties. Among these compounds, sesquiterpenes, a subcategory of the terpenes, are attracting increasing interest as they affect aroma and have potential health benefits. The characteristics of sesquiterpenes in grapes and wines in terms of classification, biosynthesis pathway, and active functions have not been extensively reviewed. This paper summarizes 97 different sesquiterpenes reported in grapes and wines and reviews their biosynthesis pathways and relevant bio‐regulation mechanisms. This review further discusses the functionalities of these sesquiterpenes including their aroma contribution to grapes and wines and potential health benefits, as well as how winemaking processes affect sesquiterpene concentrations.     

Effects of insertions and deletions in a beta-bulge region of Escherichia coli dihydrofolate reductase

The role of a beta-bulge in Escherichia coli dihydrofolate reductase (DHFR) has been explored by a series of insertion and deletion mutations. Insertion of a seven amino acid sequence from a structurally equivalent 'beta-blowout' sequence from human DHFR destabilizes E. coli DHFR by 3.6 kcal/mol and decreases catalytic efficiency (kcat/K(m)) 34- fold. Deletion of F137, delta 137, the looped out residue in the bulge, also destabilizes E. coli DHFR by 2.8 kcal/mol but only decreases catalytic efficiency threefold. Concurrent deletion of F137 and mutation of, V136 to proline to try and maintain the strand twist associated with the beta-bulge decreases protein stability by 3.4 kcal/mol and decreases catalytic efficiency 84-fold. These insertion/deletion mutations were also constructed in a D27S DHFR background. The D27S mutation has been described previously and proposed to remove the catalytic acid from the active site. The delta 137 mutation partially suppresses the effect of the D27S mutation as it decreases the K(m) for substrate, dihydrofolate, twofold. Non-additive effects are observed for the insertion/deletion mutations in wild-type versus D27S DHFR backgrounds, consistent with structural changes.      

Direct Staudinger–Phosphonite Reaction Provides Methylphosphonamidates as Inhibitors of CE4 De‐N‐acetylases

De‐N‐acetylases of β‐(1→6)‐D ‐N‐acetylglucosamine polymers (PNAG) and β‐(1→4)‐D ‐N‐acetylglucosamine residues in peptidoglycan are attractive targets for antimicrobial agents. PNAG de‐N‐acetylases are necessary for biofilm formation in numerous pathogenic bacteria. Peptidoglycan de‐N‐acetylation facilitates bacterial evasion of innate immune defenses. To target these enzymes, transition‐state analogue inhibitors containing a methylphosphonamidate have been synthesized through a direct Staudinger–phosphonite reaction. The inhibitors were tested on purified PgaB, a PNAG de‐N‐acetylase from Escherichia coli, and PgdA, a peptidoglycan de‐N‐acetylase from Streptococcus pneumonia. Herein, we describe the most potent inhibitor of peptidoglycan de‐N‐acetylases reported to date (K_i=80 μM ). The minimal inhibition of PgaB observed provides insight into key structural and functional differences in these enzymes that will need to be considered during the development of future inhibitors.     

Long-wavelength stability of an unsupported multilayer liquid film falling under gravity

The long-wavelength stability of an unsupported multilayer liquid film falling under the effects of gravity and surface tension is investigated. By considering the Navier–Stokes equations for two fluid layers in the high-Reynolds-number and small-aspect-ratio limits the steady-state solutions are obtained. The stability criterion found by Lin (J Fluid Mech 104:111–118, 1981) for a one-layer fluid curtain is generalised to the two-layer case and the criterion for an n-layer curtain is established.     

Impact of the presence of amines on the degradation of vinylidene chloride copolymers

Because of the prominence of vinylidene chloride/methyl acrylate copolymers in barrier plastic packing applications, the degradation of these materials continues to be the focus of much interest. The prominent degradation process at moderate temperature (<200°C) is dehydrochlorination. This reaction is a typical radical chain process with distinct initiation, propagation, and termination phases. A principal defect structure responsible for the initiation of degradation is unsaturation along the polymer backbone. Although most stabilization packages for these polymers contain basic components to absorb hydrogen chloride as it is generated, materials sufficiently basic to abstract hydrogen chloride might actually enhance the rate of degradation by introducing double bonds into the polymer structure. That this is the case has been established by the thermogravimetric examination of the degradation of a methyl acrylate (5 mol%)/ vinylidene chloride copolymer in the presence of amines of varying base strengths. In general, the initiation rate constant, k_t, for the degradation process is enhanced in the presence of amine.     

Phytoplankton and benthic algal response to ecosystem engineers and multiple stressors in the nearshore of Lake Huron

Resurgence of nuisance benthic algae in the Great Lakes, despite substantial efforts to reduce phosphorus loading, has stimulated renewed interest in exploring the diverse drivers of near-shore water quality. Interestingly, broad similarity in the underlying causes of shore fouling by benthic algae in Lakes Ontario, Erie, and Michigan appear to contrast with Lake Huron where system productivity and dreissenid abundance are lower. While total phosphorus was the primary predictor of chlorophyll concentrations (70–90% of variation) in the water column, we identified a series of spatial patterns that underpin this relationship (up to 28% of variation) and which integrate catchment processes, tributary influences, shoreline complexity, and distance from shore. Dreissenid mussels were the most important predictors of benthic algae cover and biomass in our models, explaining between 20 and 52% of variation. Spatial patterns explained an additional 21–48% of the variation in benthic algae cover and biomass and highlight the importance of site-specific spatial heterogeneity in benthic algae growth. Our results are consistent with the nearshore shunt hypothesis, wherein higher algal cover and biomass coincided with higher mussel density and biomass, although correlative effects with lake depth and loss of algal and mussel biomass due to physical disturbance must also be considered. These results underscore the difficulty associated with identifying the potential drivers of nearshore water quality as the diverse processes of nutrient loading, changes in catchment land use, and ecosystem change associated with invasion by dreissenids all vary in relative influence over a range of spatial scales.