Frost jacking of joint blocks above Cwm Idwal, in North Wales

The in situ development of ground ice is a major mechanism in rock breakdown. Where well-jointed rock has been streamlined through glacial abrasion, subsequent growth of subsurface intrusive ice may lead to the uplift of individual blocks and disruption of the ice erosional landform. This jacking' mechanism is likely to be a progressive process. Following climatic change and allied ground ice decay, the degree of subsequent settlement will be controlled by the degree to which individual blocks become wedged against their neighbours. Possibly the first example to be identified in Britain is described here. It dates from a severe phase of periglaciation occurring between the Last Glacial Maximum and the Flandrian Interglacial (c. 22-11.6 ka BP). Where identified in currently temperate regions, frost-jacked blocks may be interpreted as evidence for palaeopermafrost.

Co-kriging when the soil and ancillary data are not co-located

Data such as digitized aerial photographs, electrical conductivity and yield are intensive and relatively inexpensive to obtain compared with collecting soil data by sampling. If such ancillary data are co-regionalized with the soil data they should be suitable for co-kriging. The latter requires that information for both variables is co-located at several locations; this is rarely so for soil and ancillary data. To solve this problem, we have derived values for the ancillary variable at the soil sampling locations by averaging the values within a radius of 15 m, taking the nearest-neighbour value, kriging over 5 m blocks, and punctual kriging. The cross-variograms from these data with clay content and also the pseudo cross-variogram were used to co-krige to validation points and the root mean squared errors (RMSEs) were calculated. In general, the data averaged within 15m and the punctually kriged values resulted in more accurate predictions.

Frost jacking of joint blocks above Cwm Idwal, in North Wales

The in situ development of ground ice is a major mechanism in rock breakdown. Where well-jointed rock has been streamlined through glacial abrasion, subsequent growth of subsurface intrusive ice may lead to the uplift of individual blocks and disruption of the ice erosional landform. This jacking' mechanism is likely to be a progressive process. Following climatic change and allied ground ice decay, the degree of subsequent settlement will be controlled by the degree to which individual blocks become wedged against their neighbours. Possibly the first example to be identified in Britain is described here. It dates from a severe phase of periglaciation occurring between the Last Glacial Maximum and the Flandrian Interglacial (c. 22-11.6 ka BP). Where identified in currently temperate regions, frost-jacked blocks may be interpreted as evidence for palaeopermafrost.

Formation of triple helical nanofibers using self-assembling chiral benzene-1,3,5-tricarboxamides and reversal of the nanostructure's handedness using mirror image building blocks

Intertwining triple helical nanofibers with an overall handedness have been formed from self-assembling chiral benzene-1,3,5-tricarboxamides 1, 2 and 3, whereas the achiralbenzene-1,3,5-tricarboxamide 4 upon self-association gives rise to straight nanofibers without any twist and transmission electron microscopy images of chiral compounds clearly demonstrate that the handedness of the triple helical nanofibers can be reversed by using the enantiomeric benzene-1,3,5-tricarboxamide building blocks.

Construction of Helical Nanofibers from Self-Assembling Pseudopeptide Building Blocks: Modulating the Handedness and Breaking the Helicity

Helical nanofibers are successfully constructed from suitable self-assembling pseudopeptide-based molecular building blocks. The handedness of these nanofibers can be reversed by using mirror-imaged pseudopeptide-based building blocks. Straight nanofibers are also constructed by modulating the molecular and supramolecular structures by the proper choice of the stereochemical nature of the molecular scaffolds. This study demonstrates that molecular structure and chirality are not the only determining factors for tuning the morphology and chirality of nanostructures; the nature of the supramolecular structures formed from the corresponding molecular scaffolds also plays a key role in dictating the shape and chirality of nanostructures. Helical nanofibers are suitable templates for fabricating dipeptide-capped gold nanoparticles, indicating a possible use of these nanofibers in the construction of arrays of gold nanoparticles.

Melt structure and its transformation by sequential crystallization of the two blocks within poly(L-lactide)-block-poly(epsilon-caprolactone) double crystalline diblock copolymers

Sequential crystallization of poly(L-lactide) (PLLA) followed by poly(epsilon-caprolactone) (PCL) in double crystalline PLLA-b-PCL diblock copolymers is studied by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). Three samples with different compositions are studied. The sample with the shortest PLLA block (32 wt.-% PLLA) crystallizes from a homogeneous melt, the other two (with 44 and 60% PLLA) from microphase separated structures. The microphase structure of the melt is changed as PLLA crystallizes at 122 degrees C (a temperature at which the PCL block is molten) forming spherulites regardless of composition, even with 32% PLLA. SAXS indicates that a lamellar structure with a different periodicity than that obtained in the melt forms (for melt segregated samples). Where PCL is the majority block, PCL crystallization at 42 degrees C following PLLA crystallization leads to rearrangement of the lamellar structure, as observed by SAXS, possibly due to local melting at the interphases between domains. POM results showed that PCL crystallizes within previously formed PLLA spherulites. WAXS data indicate that the PLLA unit cell is modified by crystallization of PCL, at least for the two majority PCL samples. The PCL minority sample did not crystallize at 42 degrees C (well below the PCL homopolymer crystallization temperature), pointing to the influence of pre-crystallization of PLLA on PCL crystallization, although it did crystallize at lower temperature. Crystallization kinetics were examined by DSC and WAXS, with good agreement in general. The crystallization rate of PLLA decreased with increase in PCL content in the copolymers. The crystallization rate of PCL decreased with increasing PLLA content. The Avrami exponents were in general depressed for both components in the block copolymers compared to the parent homopolymers. Polarized optical micrographs during isothermal crystalli zation of (a) homo-PLLA, (b) homo-PCL, (c) and (d) block copolymer after 30 min at 122 degrees C and after 15 min at 42 degrees C.

Self-organisation in the assembly of gels from mixtures of different dendritic peptide building blocks

This paper investigates dendritic peptides capable of assembling into nanostructured gels, and explores the effect on self-assembly of mixing different molecular building blocks. Thermal measurements, small angle Xray scattering (SAXS) and circular dichroism (CD) spectroscopy are used to probe these materials on macroscopic, nanoscopic and molecular length scales. The results from these investigations demonstrate that in this case, systems with different "size" and "chirality" factors can self-organise, whilst systems with different "shape" factors cannot. The "size" and "chirality" factors are directly connected with the molecular information programmed into the dendritic peptides, whilst the shape factor depends on the group linking these peptides together-this is consistent with molecular recognition hydrogen bond pathways between the peptidic building blocks controlling the ability of these systems to self-recognise. These results demonstrate that mixtures of relatively complex peptides, with only subtle differences on the molecular scale, can self-organise into nanoscale structures, an important step in the spontaneous assembly of ordered systems from complex mixtures.

Genistein blocks homocysteine-induced alterations in the proteome of human endothelial cells

Dietary isoflavones from soy are suggested to protect endothelial cells from damaging effects of endothelial stressors and thereby to prevent atherosclerosis. In search of the molecular targets of isoflavone action, we analyzed the effects of the major soy isoflavone, genistein, on changes in protein expression levels induced by the endothelial stressor homocysteine (Hcy) in EA.hy 926 endothelial cells. Proteins from cells exposed for 24 h to 25 mu M Hcy alone or in combination with 2.5 mu M genistein were separated by two-dimensional gel electrophoresis and those with altered spot intensities were identified by peptide mass fingerprinting, Genistein reversed Hcy-induced changes of proteins involved in metabolism, detoxification, and gene regulation: and some of those effects can be linked functionally to the antiatherosclerotic properties of the soy isoflavone. Alterations of steady-state levels of cytoskeletal proteins by genistein suggested an effect oil apoptosis. As a matter of fact genistein caused inhibition of Hcy-mediated apoptotic cell death as indicated by inhibition of DNA fragmentation and chromatin condensation. In conclusion, proteome analysis allows the rapid identification of cellular target proteins of genistein action in endothelial cells exposed to the endothelial stressor Hcy and therefore enables the identification of molecular pathways of its antiatherosclerotic action

The cannabinoid CB1 receptor antagonist SR141716 blocks the orexigenic effects of intrahypothalamic ghrelin

The paraventricular nucleus (PVN) of the hypothalamus plays a key role in the control of appetite and energy balance. Both ghrelin and cannabinoid receptor agonists increase food intake when administered into this nucleus: this study investigated possible interactions between the two systems in relation to eating. The orexigenic effect of ghrelin (100 pmol) when infused in to the PVN was reversed by a small, systemic dose of the CB1 cannabinoid receptor antagonist SR141716 (1 mg kg(-1)). This is the first demonstration of a functional relationship between brain ghrelin and endocannabinoid systems, and, although it needs to be further investigated, the effect of ghrelin on food intake when injected into the PVN seems to be mediated by stimulation of cannabinoid release.

Construction of supramolecular helices and breaking the helicity by forming supramolecular β-sheet structures using suitable self-assembling pseudopeptide building blocks

Bis-valine derivatives or malonamide (Guha,S.; Drew, M.G.B. Small 2008, 4, 1993-2005) and a bis-valine derivative of 1,1-cyclopropone dicarboxamide were used as building blocks for the construction of supramolecular helical structures. The six-membered intramolecular hydrogen-bonded scaffold is formed, and this acts as a unique supramolecular synthon for the construction of a pseudopeptide-based supramolecular helical structure. However, in absence of this intramolecular hydrogen bond. intermolecular hydrogen bonds are formed among the peptide strands. This leads to a supramolecular beta-sheet structure. Proper selection of the supramolecular synthon (six-membered intramolecular hydrogenbonded scaffold) promotes supramolecular helix formation, and a deviation from this molecular structure dictates the disruption of supramolecular helicity. In this study, six crystal structures have been used to demonstrate that a change in the central angle and/or the central core structure of dicarboxamides can be used to design either a supramolecular helix or a beta-sheet.

Fibrils and nanotubes assembled from a modified amyloid-β peptide fragment differ in the packing of the same β-sheet building blocks

The peptide AAKLVFF assembles into fibrils in water and nanotubes in methanol. Solid-state NMR data are consistent with fibrils constructed from β-sheet bilayers and nanotubes bounded by a wall of offset β-sheet monolayers. Remarkably distinct morphologies are thus traced to subtle differences in the arrangement of the same fundamental building blocks.

Gallium-sulphide supertetrahedral clusters as building blocks of covalent organic-inorganic networks

The synthesis and characterisation of novel covalent organic-inorganic architectures containing organically-functionalised supertetrahedra is described. The structures of these unique materials consist of one-dimensional zigzag chains or of honeycomb-type layers, in which gallium-sulfide supertetrahedral clusters and dipyridyl ligands alternate.

Palaeoenvironmental changes during the Valanginian: new insights from variations in phosphorus contents and bulk- and clay mineralogies in the western Tethys

Paleoenvironmental and paleoclimatic changes during the Valanginian carbon isotopic excursion (CIE) have been investigated in the western Tethys. For this purpose, bulk-rock and clay mineralogies, as well as phosphorus (P) contents were evaluated in a selection of five sections located in the Vocontian Basin (Angles, SE France; Alvier, E Switzerland; Malleval, E France), and the Lombardian Basin (Capriolo, N Italy; Breggia, S Switzerland). Within the CIE interval, bulk-rock and clay mineralogies are inferred to reflect mostly climate change. The onset of the CIE (Busnardoites campylotoxus ammonite Zone) is characterized by higher detrital index (DI: sum of the detrital minerals divided by calcite contents) values and the presence of kaolinite in their clay-mineral assemblages. In the late Valanginian (from the Saynoceras verrucosum Zone up to the end of the Valanginian), the samples show relatively variable DI and lower values or the absence of kaolinite. The variation in the mineralogical composition is interpreted as reflecting a change from a climate characterized by optimal weathering conditions associated with an increase in terrigenous input on the southern European margin during the CIE towards an overall unstable climate associated with drier conditions in the late Valanginian. This is contrasted by a dissymmetry (proximal vs distal) along the studied transect, the northern Tethyan margin being more sensitive to changes in continental input compared to the distal environments. P accumulation rates (PAR) present similar features. In the Vocontian basin, P content variations are associated with changes in terrigenous influx, whereas in the Lombardian basin (i.e. Capriolo and Breggia), PAR values are less well correlated. This is mainly because the deeper part of the Tethys was less sensitive to changes in continental inputs. The onset of the CIE (top of the B. campylotoxus Zone) records a general increase in PAR suggesting an increase in marine nutrient levels. This is linked to higher continental weathering rates and the enhanced influx of nutrients into the ocean. In the period corresponding to the shift itself, P contents show a dissymmetry between the Vocontian and Lombardian basins (proximal vs distal). For the sections of Malleval, Alvier and Angles, a decrease in P concentrations associated to a decrease in detrital input is observed. In Capriolo and Breggia, PAR show maximum values during the plateau, indicating a more complex interaction between different P sources. The time interval including the top of S. verrucosum Zone up to the end of the Valanginian is characterized by variable PAR values, suggesting variable nutrient influxes. These changes are in agreement with an evolution towards seasonally contrasted conditions in the late Valanginian.