Core-shell nanocomposites prepared by hierarchical co-assembly: the role of the carbon shell in catalytic wet peroxide oxidation processes

The diffraction pattern of Fe3O4 (not shown) confirmed the presence of only one phase, corresponding to magnetite with a lattice parameter a = 8.357 Å and a crystallite size of 16.6 ± 0.2 nm. The diffraction pattern of MGNC (not shown) confirmed the presence of a graphitic phase, in addition to the metal phase, suggesting that Fe3O4 nanoparticles were successfully encapsulated within a graphitic structure during the synthesis of MGNC. The core-shell structure of MGNC is unequivocally demonstrated in the TEM micrograph shown in Fig. 1b. Characterization of the MGNC textural and surface chemical properties revealed: (i) stability up to 400 oC under oxidizing atmosphere; (ii) 27.3 wt.% of ashes (corresponding to the mass fraction of Fe3O4); (iii) a micro-mesoporous structure with a fairly well developed specific surface area (SBET = 330 m2 g-1); and (iv) neutral character (pHPZC = 7.1). In addition, the magnetic nature of MGNC (Fig. 2) is an additional advantage for possible implementation of in situ magnetic separation systems for catalyst recovery.

The fiscal compact - Europe's "hard core" based on German economic conditions. OSW Commentary No. 71, 2012-03-07

On 2 March, the leaders of 25 EU member states signed the Treaty on stability, coordination and governance in the economic and monetary union. It will introduce new fiscal constraints and officially vest new competences in the eurozone countries. Thus, their right to coordinate economic policy among them will be sanctioned. So far, the Lisbon Treaty has only provided for organisation of informal Eurogroup meetings, to be attended by representatives of the European Commission. The principles introduced by the compact, if the eurozone countries are really determined to observe its provisions, will create a new way of managing the single currency. Within the next few years, the most indebted countries will have to carry out radical reforms to boost their competitiveness and adjust it to German standards. During this period the Federal Republic of Germany will most probably decide to offer higher loan guarantees to relieve these countries’ budgets. The compact’s political consequences are also of great significance, especially considering how the treaty was finalised. The eurozone states have in fact accepted that the direction for changes will be devised by France and Germany, and the role of European institutions such as the Commission or the Parliament may weaken. From the perspective of eurozone candidate countries, the introduction of the fiscal compact means expanding the scope of conditions they must meet to become members of the single currency area. In the future, a country, in order to adopt the single currency, will have to meet the structural deficit criterion, and also most probably carry out economic reforms such as unifying its fiscal system. These goals will be achieved across the eurozone gradually, in the subsequent stages of the economic governance reform.

Age model, radiocarbon dates and dinoflagellate cyst measurements from sediment core DA06-139G

A marine sediment core from Vaigat in Disko Bugt, West Greenland, has been analysed in terms of lithology, dinoflagellate cysts and foraminifera in order to evaluate the influence of oceanographic variability on West Greenland glacier stability. The data show that during the past 5200 years the Atlantic foraminiferal abundance in the subsurface waters of the West Greenland Current (WGC) episodically increased, indicating periods of increases in the inflow of subsurface warm Atlantic water at 2000 - 1500 cal. yr BP and 1300 cal. yr BP as well as periods of less pronounced increased bottom-water temperatures around 4700 - 4000 cal. yr BP, 3100 - 2800, 2600, 1000 - 800, 500 - 400, and at 200 cal. yr. The sedimentological and dinoflagellate cyst data indicate that these episodes with enhanced advection of Irminger Sea-derived waters are accompanied by increased iceberg rafting, which we link to increased iceberg calving in relation to destabilization of the Jakobshavn Isbrae. The long-term trend in the data documents the end of a late-Holocene Thermal Maximum between 5200 and 4300 cal. yr BP and a final onset of the Neoglaciation at 3500 cal. yr BP. Increased responses of the iceberg rafting after 3500 cal. yr BP, reflects a westward/seaward advance of the glacier margin in relation to onset of Neoglaciation and a development of the glacier into a floating tongue after 2000 cal. yr BP. A comparison of our record with a record from the eastern North Atlantic indicates that a NAO-like anomaly pattern between subsurface waters in West Greenland and atmospheric temperature in the Eastern North Atlantic may have been operating during most of the late Holocene. However, during the past 1000 years the NAO signal may have weakened as some other mode of climate variability overprints the anti-phase climate signal in this region.

Table 1. Radiocarbon dates from TPC522 and box core surface samples from BC521 and BC523

Recent intensification of wind-driven upwelling of warm upper circumpolar deep water (UCDW) has been linked to accelerated melting of West Antarctic ice shelves and glaciers. To better assess the long term relationship between UCDWupwelling and the stability of theWest Antarctic Ice Sheet, we present a multi-proxy reconstruction of surface and bottom water conditions in Marguerite Bay, West Antarctic Peninsula (WAP), through the Holocene. A combination of sedimentological, diatom and foraminiferal records are, for the first time, presented together to infer a decline in UCDW influence within Marguerite Bay through the early to mid Holocene and the dominance of cyclic forcing in the late Holocene. Extensive glacial melt, limited sea ice and enhanced primary productivity between 9.7 and 7.0 ka BP is considered to be most consistent with persistent incursions of UCDW through Marguerite Trough. From 7.0 ka BP sea ice seasons increased and productivity decreased, suggesting that UCDW influence within Marguerite Bay waned, coincident with the equatorward migration of the Southern Hemisphere Westerly Winds (SWW). UCDW influence continued through the mid Holocene, and by 4.2 ka BP lengthy sea ice seasons persisted within Marguerite Bay. Intermittent melting and reforming of this sea ice within the late Holocene may be indicative of episodic incursions of UCDW into Marguerite Bay during this period. The cyclical changes in the oceanography within Marguerite Bay during the late Holocene is consistent with enhanced sensitively to ENSO forcing as opposed to the SWW-forcing that appears to have dominated the early to mid Holocene. Current measurements of the oceanography of the WAP continental shelf suggest that the system has now returned to the early Holocene-like oceanographic configuration reported here, which in both cases has been associated with rapid deglaciation.

(Table 1) Detrital modes for sand grains in sediment core CRP-3

Detrital modes determined on 68 sandstone samples from CRP-3 drillcore indicate a continuation of the dynamic history of uplift-related erosion and unroofing previously documented in CRP-1 and CRP-2/2A. The source area is identified very strongly with the Transantarctic Mountains (TAM) Dry Valleys block in southern Victoria Land. Initial unroofing of the TAM comprised removal of much of a former capping sequence of Jurassic Kirkpatrick basalts, which preceded the formation of the Victoria Land Basin. Erosion of Beacon Supergroup outcrops took place during progressive uplift of the TAM in the Oligocene. Earliest CRP-3 Oligocene samples above 788 metres below the sea floor (mbsf) were sourced overwhelmingly in Beacon Supergroup strata, including a recognisable contribution from Triassic volcanogenic Lashly Formation sandstones (uppermost Victoria Group). Moving up-section, by 500 mbsf, the CRP-3 samples are depauperate quartz arenites dominantly derived from the quartzose Devonian Taylor Group. Between c. 500 and 450 mbsf, the modal parameters show a distinctive change indicating that small outcrops of basement granitoids and metamorphic rocks were also being eroded along with the remaining Beacon (mainly Taylor Group) sequence. Apart from enigmatic fluctuations in modal indices above 450 mbsf, similar to those displayed by samples in CRP-2/2A, the CRP-3 modes are essentially constant (within a broad data scatter) to the top of CRP-3. The proportion of exposed basement outcrop remained at < 20 %, indicating negligible uplift (i.e. relative stability) throughout that period.

Thermal, chemical, and enzymatic stability of the cyclotide kalata B1: The importance of the cyclic cystine knot

The cyclotides constitute a recently discovered family of plant-derived peptides that have the unusual features of a head-to-tail cyclized backbone and a cystine knot core. These features are thought to contribute to their exceptional stability, as qualitatively observed during experiments aimed at sequencing and characterizing early members of the family. However, to date there has been no quantitative study of the thermal, chemical, or enzymatic stability of the cyclotides. In this study, we demonstrate the stability of the prototypic cyclotide kalata B1 to the chaotropic agents 6 M guanidine hydrochloride (GdHCl) and 8 M urea, to temperatures approaching boiling, to acid, and following incubation with a range of proteases, conditions under which most proteins readily unfold. NMR spectroscopy was used to demonstrate the thermal stability, while fluorescence and circular dichroism were used to monitor the chemical stability. Several variants of kalata B1 were also examined, including kalata 132, which has five amino acid substitutions from B1, two acyclic permutants in which the backbone was broken but the cystine knot was retained, and a two-disulfide bond mutant. Together, these allowed determinations of the relative roles of the cystine knot and the circular backbone on the stability of the cyclotides. Addition of a denaturant to kalata B1 or an acyclic permutant did not cause unfolding, but the two-disulfide derivative was less stable, despite having a similar three-dimensional structure. It appears that the cystine knot is more important than the circular backbone in the chemical stability of the cyclotides. Furthermore, the cystine knot of the cyclotides is more stable than those in similar-sized molecules, judging by a comparison with the conotoxin PVIIA. There was no evidence for enzymatic digestion of native kalata B1 as monitored by LC-MS, but the reduced form was susceptible to proteolysis by trypsin, endoproteinase Glu-C, and thermolysin. Fluorescence spectra of kalata B1 in the presence of dithiothreitol, a reducing agent, showed a marked increase in intensity thought to be due to removal of the quenching effect on the Trp residue by the neighboring Cys5-Cys17 disulfide bond. In general, the reduced peptides were significantly more susceptible to chemical or enzymatic breakdown than the oxidized species.