Ratio of Diene/Triene of sediment core NBP01-01-JPC24

Micropaleontological and biomarker data from two high-accumulation marine sites from the Coastal and Continental Shelf Zone (CCSZ) off East Antarctica (Adélie Land at w140°E and eastern Prydz Bay at w77°E) are used to reconstruct Holocene changes in sea ice and wind stress at the basin-wide scale. These data demonstrate congruent increase in sea-ice concentration/persistence and wind stress-related sea-surface turbulence in the two regions since 7 cal ka BP, with a particularly strong signal since 4.5 - 3.5 cal ka BP. Comparison of these high latitude records with sea ice and turbulence records from the southern mid-latitudes highlights distinctive climatic evolutions according to the different latitudinal bands. Sea-ice persistence and turbulence increase in East Antarctica CCSZ are opposite to sea-surface warming and sea-ice retreat recorded after 4.5 - 3.5 cal ka BP in the East Atlantic and Indian sector between 55 and 45°S. At the same period, paleodata suggest SST cooling in all major coastal upwelling systems of the southern hemisphere, caused by the northward transport of subpolar surface waters as a response to southern Westerlies reinforcement. We therefore propose, as suggested for the northern hemisphere, that Holocene changes in the latitudinal insolation gradient, primarily forced by obliquity and precession and amplified by sea-ice and glacial-ice expansions in the Antarctic realm, are responsible for the observed contrasted latitudinal patterns of southern latitudes.

Tableau de la littérature espagnole depuis le 12e siècle jusquà̓ nos jours. Précédé du̓ne introduction sur l'origine de la langue espagnole /

Biographical essays of each author in French; selections in Spanish

Gjenmaele mod anmaeldelsen af C.C. Rafns oversaettelse af Jomsvikinga og Knytlinga i "Maanedsskrift for literatur, IIer aarg. 12e hæfte."

Mode of access: Internet.

Tableau de la littérature espagnole depuis le 12e siècle, précédé d'une introduction sur l'origine de la langue espagnole.

Mode of access: Internet.

Reactive processing of polymers:functionalisation of ethylene-propylene diene terpolymer (EPDM) in the presence and absence of a co-agent and effect of functionalised EPDM on compatibilisation of poly(ethylene terephthalate)/EPDM blends

Ethylene-propylene diene terpolymer (EPDM) was functionalized with glycidyl methacrylate (GMA) during melt processing by free radical grafting with peroxide initiation in the presence and absence of a reactive comonomer trimethylolpropane triacrylate (Tris). Increasing the peroxide concentration resulted in an increase in the GMA grafting yield, albeit the overall grafting level was low and was accompanied by higher degree of crosslinking of EPDM which was found to be the major competing reaction. The presence of Tris in the grafting system gave rise to higher grafting yield produced at a much lower peroxide concentration though the crosslinking reactions remained high but without the formation of GMA-homopolymer in either of the two systems. The use of these functionalized EPDM (f-EPDM) samples with PET as compatibilisers in binary and ternary blends of PET/EPDM/f-EPDM was evaluated. The influence of the different functionalisation routes of the rubber phase (in presence and absence of Tris) and the effect of the level of functionality and microstructure of the resultant f-EPDM on the extent of the interfacial reaction, morphology and mechanical properties was also investigated. It is suggested that the mechanical properties of the blends are strongly influenced by the performance of the graft copolymer, which is in turn, determined by the level of functionality, molecular structure of the functionalized rubber and the interfacial concentration of the graft copolymer across the interface. The cumulative evidence obtained from torque rheometry, scanning electron microscopy, SEM, dynamic mechanical analysis (DMA), tensile mechanical tests and Fourier transform infrared (FTIR) supports this. It was shown that binary and ternary blends prepared with f-EPDM in the absence of Tris and containing lower levels of g-GMA effected a significant improvement in mechanical properties. This increase, particularly in elongation to break, could be accounted for by the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET that would result in a graft copolymer which could, most probably, preferentially locate at the interface, thereby acting as an 'emulsifier' responsible for decreasing the interfacial tension between the otherwise two immiscible phases. This is supported by results from FTIR analysis of the fractionated PET phase of these blends which confirm the formation of an interfacial reaction, DMA results which show a clear shift in the T s of the blend components and SEM results which reveal very fine morphology, suggesting effective compatibilisation that is concomitant with the improvement observed in their tensile properties. Although Tris has given rise to highest amount of g-GMA, it resulted in lower mechanical properties than the optimized blends produced in the absence of Tris. This was attributed to the difference in the microstructure of the graft and the level of functionality in these samples resulting in less favourable structure responsible for the coarser dispersion of the rubber phase observed by SEM, the lower extent of T shift of the PET phase (DMA), the lower height of the torque curve during reactive blending and FTIR analysis of the separated PET phase that has indicated a lower extent of the interfacial chemical reaction between the phases in this Tris-containing blend sample. © 2005 Elsevier Ltd. All rights reserved.

Ratio of Diene/Triene of sediment core MD03-2601

Micropaleontological and biomarker data from two high-accumulation marine sites from the Coastal and Continental Shelf Zone (CCSZ) off East Antarctica (Adélie Land at w140°E and eastern Prydz Bay at w77°E) are used to reconstruct Holocene changes in sea ice and wind stress at the basin-wide scale. These data demonstrate congruent increase in sea-ice concentration/persistence and wind stress-related sea-surface turbulence in the two regions since 7 cal ka BP, with a particularly strong signal since 4.5 - 3.5 cal ka BP. Comparison of these high latitude records with sea ice and turbulence records from the southern mid-latitudes highlights distinctive climatic evolutions according to the different latitudinal bands. Sea-ice persistence and turbulence increase in East Antarctica CCSZ are opposite to sea-surface warming and sea-ice retreat recorded after 4.5 - 3.5 cal ka BP in the East Atlantic and Indian sector between 55 and 45°S. At the same period, paleodata suggest SST cooling in all major coastal upwelling systems of the southern hemisphere, caused by the northward transport of subpolar surface waters as a response to southern Westerlies reinforcement. We therefore propose, as suggested for the northern hemisphere, that Holocene changes in the latitudinal insolation gradient, primarily forced by obliquity and precession and amplified by sea-ice and glacial-ice expansions in the Antarctic realm, are responsible for the observed contrasted latitudinal patterns of southern latitudes.

(Ultra)fast catalyst-free macromolecular conjugation in aqueous environment at ambient temperature

Tailor-made water-soluble macromolecules, including a glycopolymer, obtained by living/controlled RAFT-mediated polymerization are demonstrated to react in water with diene-functionalized poly(ethylene glycol)s without pre- or post-functionalization steps or the need for a catalyst at ambient temperature. As previously observed in organic solvents, hetero-Diels-Alder (HDA) conjugations reached quantitative conversion within minutes when cyclopentadienyl moieties were involved. However, while catalysts and elevated temperatures were previously necessary for open-chain diene conjugation, additive-free HDA cycloadditions occur in water within a few hours at ambient temperature. Experimental evidence for efficient conjugations is provided via unambiguous ESI-MS, UV/vis, NMR, and SEC data.

Bisresorcinol Derivatives from Grevillea glauca

Seven new and three known bisresorcinols, grevirobstol A(=5,5'-((6Z,9Z)-hexadeca-6,9-diene-1,16-diyl)bisresorcinol; 8), 5,5'-[(8Z)-hexadec-8-ene-1,16-diyl]bisresorcinol (9), and 2-methyl-5,5'-[8Z)-hexadec-8-ene-1,16-diyl] bisresorcinol (10) were isolated from the stems of Grevillea glauca. The new compounds were identified on the basis of spectroscopic data as (Z)-6,7-didehydroglaucone A (1), glaucones A and B (2 and 3, resp.), 2-(3-hydroxyisopentyl)bisnorstriatol (4), 2-(3-methylbut-2-en-1-yl)bisnorstriatol (5), 2'-methylgrebustol A (6), and glaucane (7).

Competitive charge-remote and anion-induced fragmentations of the non-8-enoate anion. A charge-remote reaction which co-occurs with hydrogen scrambling

The non-8-enoate anion undergoes losses of the elements of C3H6, C4H8 and C6H12 on collisional activation, The mechanisms of these processes have been elucidated by a combination of product ion and labelling (H-2 and C-13) studies, together with a neutralisation reionisation mass spectrometric study. These studies allow the following conclusions to be made. (i) The loss of C3H6 involves cyclisation of the enolate anion of non-8-enoic acid to yield the cyclopentyl carboxylate anion and propene. (ii) The loss of 'C4H8' is a charge-remote process (one which proceeds remote from the charged centre) which yields the pent-4-enoate anion, butadiene and dihydrogen. This process co-occurs and competes with complex H scrambling. (iii) The major loss of 'C6H12' occurs primarily by a charge-remote process yielding the acrylate anion, hexa-1,5-diene and dihydrogen, but in this case no H scrambling accompanies the process. (iv) It is argued that the major reason why the two charge-remote processes occur in preference to anion-induced losses of but-l-ene and hex-l-ene from the respective 4- and 2-anions is that although these anions are formed, they have alternative and lower energy fragmentation pathways than those involving the losses of but-l-ene and hex-l-ene; viz. the transient 4-anion undergoes facile proton transfer to yield a more stable anion, whereas the 2-(enolate) anion undergoes preferential cyclisation followed by elimination of propene [see (i) above].

λ-orthogonal pericyclic macromolecular photoligation

A photochemical strategy enabling λ-orthogonal reactions is introduced to construct macromolecular architectures and to encode variable functional groups with site-selective precision into a single molecule by the choice of wavelength. λ-Orthogonal pericyclic reactions proceed independently of one another by the selection of functional groups that absorb light of specific wavelengths. The power of the new concept is shown by a one-pot reaction of equimolar quantities of maleimide with two polymers carrying different maleimide-reactive endgroups, that is, a photoactive diene (photoenol) and a nitrile imine (tetrazole). Under selective irradiation at λ=310–350 nm, any maleimide (or activated ene) end-capped compound reacts exclusively with the photoenol functional polymer. After complete conversion of the photoenol, subsequent irradiation at λ=270–310 nm activates the reaction of the tetrazole group with functional enes. The versatility of the approach is shown by λ-orthogonal click reactions of complex maleimides, functional enes, and polymers to the central polymer scaffold.