Halogenated natural products in five species of Antarctic sponges: compounds with POP-like properties?

Purified extracts of five species of Antarctic sponges (Demospongiae: Kirkpatrickia variolosa, Artemisina apollinis, Phorbas glaberrima, and Halichondria sp. and Calcarea: Leucetta antarctica) from King George Island were analyzed by GC/MS for the presence of persistent and lipophilic halogenated compounds to identify bioaccumulative halogenated natural products. Sample extracts were prepared using methods identical for the determination of POPs, namely, microwave-assisted extraction with organic solvents, gel permeation chromatography, and column chromatography on deactivated silica. In addition, samples were treated with sulfuric acid to remove acid-destructible compounds. PCBs were not detectable and only traces of lindane, p,p'-DDE, and alpha-HCH were detected in these samples in decreasing order of abundance, underscoring their uncontaminated state. In contrast, 146 brominated compounds were identified by correct isotopic ratios m/z 79 and 81, 50% of which eluted prior to lindane including the most abundant peaks. Each sponge sample contained > or = 35 brominated compounds of natural origin, 14 of which were detected in all species. Estimated concentrations ranged from the high ng/kg to mg/kg (air-dried weights) and relative distributions of the same compounds in different sponges were highly variable. The high abundance of these compounds relative to known anthropogenic pollutants strongly suggests a natural origin. Multiple mode (EI-, ECNI-, and PCI-) GC/MS enabled identification of an aliphatic ketone tentatively identified as 1,1,2-tribromo-oct-1-en-3-one, present in all species but highest in Phorbas glaberrima. Several halogenated phenols including 2,4,6-tribromophenol were also abundant in Phorbas glaberrima as were halogenated anisoles in lower relative abundances. The halogenated phenols were analyzed without derivatization. The sample of Halichondria sp. contained the dibromotrichloro monoterpene MHC-1, a recently described environmental contaminant in fish and seals. Retrospective analysis of other marine samples confirmed that 2,4,6-tribromophenol was present in seal blubber from both the Arctic and the Antarctic. The presence of naturally occurring organohalogens such as 2,4,6-tribromophenol and MHC-1 in Antarctic marine invertebrates thus provides a link to their occurrence in marine mammals.     

Transformation and removal of bisphenol A from aqueous phase via peroxidase mediated oxidative coupling reactions: efficacy, products, and pathways

A systematic investigation of the feasibility of and mechanisms for transformation and removal of bisphenol A (BPA) from aqueous phase via oxidative coupling mediated by horseradish peroxidase is described. It is demonstrated that BPA can be effectively transformed into precipitable solid products in HRP-mediated oxidative coupling reactions. A total of 13 reaction intermediates and products are identified using LC/MS and GC/MS techniques, and with the help of ab initio molecular modeling, detailed reaction pathways are proposed. It is postulated that two BPA radicals are coupled primarily by the interaction of an oxygen atom on one radical and propyl-substituted aromatic carbon atom on another, followed by elimination of an isopropylphenol carboncation. All intermediates or products detected can be interpreted as resulting from either coupling or substitution reactions between BPA and other intermediates or products. The efficacy of the reaction at low substrate concentrations is demonstrated using a sensitive analytical procedure involving solid-phase extractions. The results suggest that catalyzed oxidative coupling reactions may be important natural transformation pathways for estrogenic phenolic compounds and indicate their potential use as an efficient means for removal of estrogenicity from waters and wastewaters.     

Physico‐chemical characterization of starches extracted from potatoes of the group Phureja

Starch was extracted from twenty‐four accessions of Group Phureja cultivated diploid potatoes, and from two commercial potato (Solanum tuberosum) varieties. Extracted starch samples were characterized and compared to industrial potato starch. Starch from Phureja generally exhibited smaller granule sizes and lower phosphorus content than starch from commercial potatoes. Amylose content and thermal properties (gelatinization temperature and enthalpy) were however in the same range for both groups. Starches from Phureja displayed very distinct pasting behavior from that of commercial potato. The former exhibited lower initial pasting viscosity but higher shear resistance. This may be related to lower starch granule size, causing lower swelling power and solubility. Iodine complexation results seem to indicate that phureja potatoes have higher proportion of amylopectin long chains. Phureja thus appears to be a promising new source of starch with specific physico‐chemical and functional properties intermediate between industrial potato and cereal starches.     

Physiologically based persistent organic pollutant accumulation in pig tissues and their edible safety differences: An in vivo study

As one of the most important animal food sources, pigs are an important model in the assessment of human exposure to persistent organic pollutants (POPs). In the present study, the distribution of the administrated polychlorodibenzo-p-dioxin/furan (PCDD/F)–polychlorinated biphenyl (PCB) mixture and polybrominated diphenyl ethers (PBDEs) in the different tissues of pigs, including liver, lung, kidney, subcutaneous fat, mesentery and muscle, for understanding the physiologically based pollutant accumulation in these tissues and their edible safety was investigated. It was found that liver had a much higher potential to accumulate PCDD/Fs and dioxin-like pollutants like PCB-126 than the other tissues, but it did not specifically concentrate PBDE congeners as compared to the other tissues. The different PCDD/F congeners and PCB-126 followed a similar distribution pattern in the different tissues; also the different PBDE congeners have the similar pattern in these tissues. The liver’s higher concentrating potency for dioxin-like pollutants may result from its detoxification function, however, it can concentrate dioxin-like pollutants but not PBDEs may suggest that it is the toxicity but not lipophilic property of these POPs dominated their accumulation in liver tissues. Also the result suggested that liver is a high-risk edible tissue for dioxin-like pollutants. In conclusion, the present study suggested that physiologically based assessments are necessary for evaluating edible tissue safety in animal source foods.     

Studies on the formation of lysinomethylalanine and histidinomethylalanine in milk products

From reaction mixtures consisting ofN-acetyldehydroaminobutyric acid methyl ester andN -acetyl-l-lysine orN -acetyl-l-histidine, respectively, distinct amounts of the cross-link amino acidsN -(2-amino-2-carboxy-l-methylethyl)-l-lysine (lysinomethylalanine, LMeAL) andN -(2-amino-2-carboxy-1-methyl-ethyl)-l-histidine (histidinomethylalanine, HMeAL) were isolated via preparative ion-exchange chromatography and identified by¹H- and¹³C-nuclear magnetic resonance. In the amino acid chromatogram, both compounds eluted clearly separated from other basic amino acids. However, neither LMeAL nor HMeAL could be detected in numerous acid hydrolysates of a range of milk products. In model studies, threonine showed a significantly lower tendency for an alkali-induced -elimination reaction compared to serine. The reactivity of the resulting dehydroaminobutyric acid towards nucleophiles was more than tenfold lower as compared to dehydroalanine. Thus, the formation of LMeAL as well as of HMeAL during food processing is negligible.

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Studien zur Bildung von Lysinomethylalanin und Histidinomethylalanin in Milchprodukten

Zusammenfassung Aus Reaktionsansätzen bestehend ausN-Acetyldehydroaminobuttersäurenthylester undN -Acetyl-l-lysin beziehungsweiseN -Acetyl-l-histidin konnten die Crosslink-AminosäurenN -(2-Amino-2-carboxy-1-methyl-ethyl)-l-lysin (Lysinomethylalanin, LMeAL) undN -(2 amino-2-carboxy-2 -methyl-ethyl)-l-histidin (Histidinomethylalanin, HMeAL) durch präparative Ionenaustauschchromatographie isoliert und anschließend durch 1H-und¹³C-NMR identifiziert werden. Das Aminosäurechromatogramm zeigte eine eindeutige Trennung beider Aminosäurederivate von anderen basischen Aminosäuren. Dennoch konnten in einer großen Zahl von Säurehydrolysaten der verschiedensten Milchprodukte weder LMeAL noch HMeAL nachgewiesen werden. In Modelluntersuchungen erfolgte die -Elimination an Threonin im Vergleich zu Serin in einem deutlich geringeren Maße. Die Reaktivität der dabei entstehenden Dehydroaminobuttersäure gegenüber Nucleophilen war mehr als zehnfach geringer als die von Dehydroalanin. Damit kann die Bildung sowohl von LMeAL als auch von HMeAL bei der Verarbeitung von Nahrungsmitteln als vernachlässigbar gering eingeschätzt werden.

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Dedicated to Prof. Dr. W. Baltes on the occasion of his 65th birthday     

Strain hardening and instability in biaxially streched sheets

This work is concerned with the origins of the two different patterns of failure limits in biaxially stretched sheets which were recently described in Ref. 1: the brass-type in which the limit strain is insensitive to strain state, and that of ferritic steel in which the limit strain increases as the imposed strain-ratio, ρ = ε₂/ε₁, changes from zero (plane-strain tension) toward unity (balanced biaxial tension). An earlier proposal that different slip modes,i.e. wavy in ferrite vs planar in brass, might have contributed to these failurelimit differences was found not to be valid. There were two parts to the main experimental program: the prestraining of small sheets by proportional loading on different paths betweenρ = 0 andρ = 1, followed by tension testing, and a more direct measurement of strain hardening and instability between ρ ≅ — 1/2 (uniaxial tension) andρ = 0. The principal finding was that the overall hardening rate, essentially as it appeared in the material’s effective stress-strain curve, changed with the loading path. Inα brass it decayed as p was increased from ∼—1/2 to 1; in ferritic steel it increased; and in aluminum it was affected very little. Such changes in hardening rate cause similar changes in the material’s capacity for stable flow. The stable flow, in turn, is the base to which a quasistable-flow increment (whenρ is >0) is added in reaching the observed failure limit. Thus a base ofρ-dependent height can account for the failure-limit patterns. There is still no explanation for the ρ dependence of the hardening rate. AMIT K. GHOSH, formerly Graduate Student, Massachusetts Institute of Technology, Cambridge, Mass. 02139, This paper is based upon a thesis submitted by AMIT K. GHOSH in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology.     

The origin of strain-rate sensitivity in OFHC copper

This investigation was conducted to determine the nature of the strain-rate sensitivity of OFHC copper at room temperature. In particular, the relative magnitudes of the dynamic contribution (particle inertia, suppression of thermal assistance, and so forth) and the nondynamic contribution (namely, the accelerated rate of strain hardening observed at high strain rates) to the strain-rate sensitivity were determined. Specimens were dynamically compressed using the Hopkinson pressure bar technique, and then were reloaded quasistatically to determine their respective yield strengths. The dynamic contribution to strainrate sensitivity was taken as the difference between the peak dynamic flow stress and the flow stress of the same specimen when reloaded quasistatically. The nondynamic contribution to strain-rate sensitivity of the flow stress was taken as the difference between the quasistatic flow stress in reloading of a specimen prestrained ε₀ dynamically and the flow stress at ε₀ for a sample deformed in uniaxial quasistatic compression. The room temperature dynamic flow-stress of OFHC copper, deformed at 500s⁻¹, was found to be 25 pct higher than the conventional quasistatic flow stress for this metal over a strain range of 0.08 to 0.20. The nondynamic contribution to strain-rate sensitivity was found to be about 60 pct of the total flow stress increase and has been attributed to a difference in strainhardening at different strain rates. Thus, it appears that in OFHC copper at room temperature and at strain rates of about 500s⁻¹, the nondynamic contribution to strain-rate sensitivity is more significant than the dynamic contribution.     

Facing the issues.

Replies to P. L. Wachtel (see PA, Vol. 51:Issue 5) stating that efforts to achieve integration between psychodynamic and behavioral approaches are appealing, but are unlikely to succeed unless the empirical issues are faced without distortion. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Water Resources: The Delaware Basin

Philadelphia is in competition with New York City and Baltimore in staking a claim for the water resources it will need in the next half century and beyond. A new governmental organization having a delegation of both state and federal powers for continuous planning and for unified management and control of the water resources of the entire Delaware River Basin has been proposed; and a federal-state compact for its establishment is being negotiated.