Structural and Electrochemical Properties of Lutetium Bis-Octachloro-Phthalocyaninate Nanostructured Films. Application as Voltammetric Sensors

Thin films of the bis[2,3,9,10,16,17,23,24-octachlorophthalocyaninate] lutetium(III) complex (LuPc2Cl32) have been prepared by the Langmuir-Blodgett and the Langmuir-Schaefer (LS) techniques. The influence of the chlorine substituents in the structure of the films and in their spectroscopic, electrochemical and sensing properties has been evaluated. The pi-A isotherms exhibit a monolayer stability greater than the observed in the unsubstituted analogue (LuPc2), being easily transferred to solid substrates, also in contrast to LuPc2. The LB and LS films present a linear growth forming stratified layers, monitored by UV-VIS absorption spectroscopy. The latter also revealed the presence of LuPc2Cl32 in the form of monomers and aggregates in both films. The FTIR data showed that the LuPc2Cl32 molecules present a non-preferential arrangement in both films. Monolayers of LB and LS were deposited onto 6 nm Ag island films to record surface-enhanced resonance Raman scattering (SERRS), leading to enhancement factors close to 2 x 10(3). Finally, LB and LS films deposited onto ITO glass have been successfully used as voltammetric sensors for the detection of catechol. The improved electroactivity of the LB and LS films has been confirmed by the reduction of the overpotential of the oxidation of catechol. The enhancement of the electrocatalytic effect observed in LB and LS films is the result of the nanostructured arrangement of the surface which increases the number of active sites. The sensors show a limit of detection in the range of 10(-5) mol/L.

Hypofibrinogenemia and liver disease: a new case of Aguadilla fibrinogen and review of the literature.

INTRODUCTION Fibrinogen storage disease (FSD) is characterized by hypofibrinogenemia and hepatic inclusions due to impaired release of mutant fibrinogen which accumulates and aggregates in the hepatocellular endoplasmic reticulum. Liver disease is variable. AIM We studied a new Swiss family with fibrinogen Aguadilla. In order to understand the molecular peculiarity of FSD mutations, fibrinogen Aguadilla and the three other causative mutations, all located in the γD domain, were modelled. METHOD The proband is a Swiss girl aged 4 investigated because of fatigue and elevated liver enzymes. Protein structure models were prepared using the Swiss-PdbViewer and POV-Ray software. RESULTS The proband was found to be heterozygous for fibrinogen Aguadilla: FGG Arg375Trp. Familial screening revealed that her mother and maternal grandmother were also affected and, in addition, respectively heterozygous and homozygous for the hereditary haemochromatosis mutation HFE C282Y. Models of backbone and side-chain interactions for fibrinogen Aguadilla in a 10-angstrom region revealed the loss of five H-bonds and the gain of one H-bond between structurally important amino acids. The structure predicted for fibrinogen Angers showed a novel helical structure in place of hole 'a' on the outer edge of γD likely to have a negative impact on fibrinogen assembly and secretion. CONCLUSION The mechanism by which FSD mutations generate hepatic intracellular inclusions is still not clearly established although the promotion of aberrant intermolecular strand insertions is emerging as a likely cause. Reporting new cases is essential in the light of novel opportunities of treatment offered by increasing knowledge of the degradation pathway and autophagy.

Geochemistry and mineralogy of sediments from the Atlantis II Fracture Zone

Thirteen sediment samples, including calcareous ooze, sandy clay, volcanic sand, gravel, and volcanic breccia, from Ocean Drilling Program (ODP) Sites 732B, 734B, 734G and Conrad Cruise 27-9, Station 17, were examined. Contents of major and trace elements were determined using XRF or ICP (on samples <0.5 g). Determinations of rare earth elements (REE) were performed using ICP-MS. Mineralogy was determined using XRD. On the basis of the samples studied, the sediments accumulating in the Atlantis II Fracture Zone are characterized by generally high MgO, Cr, and Ni contents compared with other deep-sea sediments. A variety of sources are reflected in the mineralogy and geochemistry of these sediments. Serpentine, brucite, magnetite, and high MgO, Cr, and Ni contents indicate derivation from ultramafic basement. The occurrence of albite, analcime, primary mafic minerals, and smectite/chlorite in some samples, coupled with high SiO2, Al2O3, TiO2, Fe2O3, V, and Y indicate contribution from basaltic basement. A third major sediment source is characterized as biogenic material and is reflected primarily in the presence of carbonate minerals, and high CaO, Sr, Pb, and Zn in certain samples. Kaolinite, illite, quartz, and some chlorite are most likely derived from continental areas or other parts of the ocean by long-distance sediment transport in surface or other ocean currents. Proportions of source materials in the sediments reflect the thickness of the sediment cover, slope of the seafloor, and the nature of and proximity to basement lithologies. REE values are low compared to other deep-sea sediments and indicate no evidence of hydrothermal activity in the Atlantis II Fracture Zone sediments. This is supported by major- and trace-element data.

Composition of suspended matter and bottom sediments from the Atlantic Ocean and its seas

The book summarizes data on distribution and composition of sedimentary material suspended in waters of the Atlantic Ocean and its seas. Results of observations of Soviet and foreign expeditions are given. Distribution of suspended matter in sections across the ocean, as well as in the most studied seas are shown. New data on grain size, mineral and chemical composition of suspended matter are published. Summary of history of investigation of bottom sediments from the Atlantic Ocean from the first scientific cruises to the present is done. A brief description of sediment types in the ocean and a detailed description of Mediterranean Sea sediments are given.

Chemical and mineral compositions of bottom sediments and ferromanganese crusts and nodules near Iceland

Results of study of bottom sediments near Iceland and on the Jan Mayen Island are reported. It was found that in recent sediments chemical elements are mainly associated with pyro- and volcanoclastics. In some areas adjusted to deep-seated faults ancient iron-manganese crusts and sediments occur. They are rich in Ni, Co, V, Cu, Mo, Cd and other elements associated with endogenic matter.

Researching in ancient engineering physical and chemical analysis in hidraulic roman mortars

Around ten years ago investigation of technical and material construction in Ancient Roma has advanced in favour to obtain positive results. This process has been directed to obtaining some dates based in chemical composition, also action and reaction of materials against meteorological assaults or post depositional displacements. Plenty of these dates should be interpreted as a result of deterioration and damage in concrete material made in one landscape with some kind of meteorological characteristics. Concrete mixture like calcium and gypsum mortars should be analysed in laboratory test programs, and not only with descriptions based in reference books of Strabo, Pliny the Elder or Vitruvius. Roman manufacture was determined by weather condition, landscape, natural resources and of course, economic situation of the owner. In any case we must research the work in every facts of construction. On the one hand, thanks to chemical techniques like X-ray diffraction and Optical microscopy, we could know the granular disposition of mixture. On the other hand if we develop physical and mechanical techniques like compressive strength, capillary absorption on contact or water behaviour, we could know the reactions in binder and aggregates against weather effects. However we must be capable of interpret these results. Last year many analyses developed in archaeological sites in Spain has contributed to obtain different point of view, so has provide new dates to manage one method to continue the investigation of roman mortars. If we developed chemical and physical analysis in roman mortars at the same time, and we are capable to interpret the construction and the resources used, we achieve to understand the process of construction, the date and also the way of restoration in future.

The Endogenous and Cell Cycle-dependent Phosphorylation of tau Protein in Living Cells: Implications for Alzheimer’s Disease

In Alzheimer’s disease the neuronal microtubule-associated protein tau becomes highly phosphorylated, loses its binding properties, and aggregates into paired helical filaments. There is increasing evidence that the events leading to this hyperphosphorylation are related to mitotic mechanisms. Hence, we have analyzed the physiological phosphorylation of endogenous tau protein in metabolically labeled human neuroblastoma cells and in Chinese hamster ovary cells stably transfected with tau. In nonsynchronized cultures the phosphorylation pattern was remarkably similar in both cell lines, suggesting a similar balance of kinases and phosphatases with respect to tau. Using phosphopeptide mapping and sequencing we identified 17 phosphorylation sites comprising 80–90% of the total phosphate incorporated. Most of these are in SP or TP motifs, except S214 and S262. Since phosphorylation of microtubule-associated proteins increases during mitosis, concomitant with increased microtubule dynamics, we analyzed cells mitotically arrested with nocodazole. This revealed that S214 is a prominent phosphorylation site in metaphase, but not in interphase. Phosphorylation of this residue strongly decreases the tau–microtubule interaction in vitro, suppresses microtubule assembly, and may be a key factor in the observed detachment of tau from microtubules during mitosis. Since S214 is also phosphorylated in Alzheimer’s disease tau, our results support the view that reactivation of the cell cycle machinery is involved in tau hyperphosphorylation.

Analyzation of marine snow and fecal pellets collected in sediment trap CBi-2 off Cape Blanc, Mauritania

We analyzed size-specific dry mass, sinking velocity, and apparent diffusivity in field-sampled marine snow, laboratory-made aggregates formed by diatoms or coccolithophorids, and small and large zooplankton fecal pellets with naturally varying content of ballast materials. Apparent diffusivity was measured directly inside aggregates and large (millimeter-long) fecal pellets using microsensors. Large fecal pellets, collected in the coastal upwelling off Cape Blanc, Mauritania, showed the highest volume-specific dry mass and sinking velocities because of a high content of opal, carbonate, and lithogenic material (mostly Saharan dust), which together comprised ~80% of the dry mass. The average solid matter density within these large fecal pellets was 1.7 g cm**-3, whereas their excess density was 0.25 ± 0.07 g cm**-3. Volume-specific dry mass of all sources of aggregates and fecal pellets ranged from 3.8 to 960 µg mm**-3, and average sinking velocities varied between 51 and 732 m d**-1. Porosity was >0.43 and >0.96 within fecal pellets and phytoplankton-derived aggregates, respectively. Averaged values of apparent diffusivity of gases within large fecal pellets and aggregates were 0.74 and 0.95 times that of the free diffusion coefficient in sea water, respectively. Ballast increases sinking velocity and, thus, also potential O2 fluxes to sedimenting aggregates and fecal pellets. Hence, ballast minerals limit the residence time of aggregates in the water column by increasing sinking velocity, but apparent diffusivity and potential oxygen supply within aggregates are high, whereby a large fraction of labile organic carbon can be respired during sedimentation.

Heterogeneity of physico-chemical properties in structured soils and its consequences

Structured soils are characterized by the presence of inter- and intra-aggregate pore systems and aggregates, which show varying chemical, physical, and biological properties depending on the aggregate type and land use system. How far these aspects also affect the ion exchange processes and to what extent the interaction between the carbon distribution and kind of organic substances affect the internal soil strength as well as hydraulic properties like wettability are still under discussion. Thus, the objective of this research was to clarify the effect of soil aggregation on physical and chemical properties of structured soils at two scales: homogenized material and single aggregates. Data obtained by sequentially peeling off soil aggregates layers revealed gradients in the chemical composition from the aggregate surface to the aggregate core. In aggregates from long term untreated forest soils we found lower amounts of carbon in the external layer, while in arable soils the differentiation was not pronounced. However, soil aggregates originating from these sites exhibited a higher concentration of microbial activity in the outer aggregate layer and declined towards the interior. Furthermore, soil depth and the vegetation type affected the wettability. Aggregate strength depended. on water suction and differences in tillage treatments.

Peptide bundles: Loops, helices, strands and sheets

Protein-protein interactions are central to all biological processes. The creation of small molecules that can structurally mimic the fundamental units of protein architecture (helices, strands, turns, and their combinations) could potentially be used to reproduce important bioactive protein surfaces and interfere in biological processes. Although this field is still in relative infancy, substantial progress is being made in creating small molecules that can mimic these individual secondary structural elements of proteins. However the generation of compounds that can reproduce larger protein surfaces, composed of multiple structural elements of proteins, has proven to be much more challenging. This presentation will describe some densely functionalised small molecules that do constrain multiple peptide motifs in defined structures such as loop bundles, helix bundles, strand and sheet bundles. An example of a helix bundle that undergoes conformational changes to a beta sheet bundle and aggregates into multi-micron length peptide nanofibre 'rope' will be described.

Ionized cluster beam deposition: Modeling, cluster size measurement and applications

Clusters are aggregations of atoms or molecules, generally intermediate in size between individual atoms and aggregates that are large enough to be called bulk matter. Clusters can also be called nanoparticles, because their size is on the order of nanometers or tens of nanometers. A new field has begun to take shape called nanostructured materials which takes advantage of these atom clusters. The ultra-small size of building blocks leads to dramatically different properties and it is anticipated that such atomically engineered materials will be able to be tailored to perform as no previous material could.^ The idea of ionized cluster beam (ICB) thin film deposition technique was first proposed by Takagi in 1972. It was based upon using a supersonic jet source to produce, ionize and accelerate beams of atomic clusters onto substrates in a vacuum environment. Conditions for formation of cluster beams suitable for thin film deposition have only recently been established following twenty years of effort. Zinc clusters over 1,000 atoms in average size have been synthesized both in our lab and that of Gspann. More recently, other methods of synthesizing clusters and nanoparticles, using different types of cluster sources, have come under development.^ In this work, we studied different aspects of nanoparticle beams. The work includes refinement of a model of the cluster formation mechanism, development of a new real-time, in situ cluster size measurement method, and study of the use of ICB in the fabrication of semiconductor devices.^ The formation process of the vaporized-metal cluster beam was simulated and investigated using classical nucleation theory and one dimensional gas flow equations. Zinc cluster sizes predicted at the nozzle exit are in good quantitative agreement with experimental results in our laboratory.^ A novel in situ real-time mass, energy and velocity measurement apparatus has been designed, built and tested. This small size time-of-flight mass spectrometer is suitable to be used in our cluster deposition systems and does not suffer from problems related to other methods of cluster size measurement like: requirement for specialized ionizing lasers, inductive electrical or electromagnetic coupling, dependency on the assumption of homogeneous nucleation, limits on the size measurement and non real-time capability. Measured ion energies using the electrostatic energy analyzer are in good accordance with values obtained from computer simulation. The velocity (v) is measured by pulsing the cluster beam and measuring the time of delay between the pulse and analyzer output current. The mass of a particle is calculated from m = (2E/v$\sp2).$ The error in the measured value of background gas mass is on the order of 28% of the mass of one N$\sb2$ molecule which is negligible for the measurement of large size clusters. This resolution in cluster size measurement is very acceptable for our purposes.^ Selective area deposition onto conducting patterns overlying insulating substrates was demonstrated using intense, fully-ionized cluster beams. Parameters influencing the selectivity are ion energy, repelling voltage, the ratio of the conductor to insulator dimension, and substrate thickness. ^

Age determination and sedimentology on profile Lz1020 from Lake Hoare, Antarctica

Up to 2.3 m long sediment sequences were recovered from the deepest part of Lake Hoare in Taylor Valley, southern Victoria Land, Antarctica. Sedimentological, biogeochemical, and mineralogical analyses revealed a high spatial variability of these parameters in Lake Hoare. Five distinct lithological units were recognized. Radiocarbon dating of bulk organic carbon samples from the sediment sequences yielded apparently too old ages and significant age reversals, which prevented the establishment of reliable age-depth models. However, cross correlation of the sedimentary characteristics with those of sediment records from neighbouring Lake Fryxell indicates that the lowermost two units of the Lake Hoare sediment sequences were probably deposited during the final phase of proglacial Lake Washburn, which occupied Taylor Valley during the late Pleistocene and early Holocene. High amounts of angular gravel and the absence of fine-grained material imply a complete desiccation with subaerial conditions in the Lake Hoare basin in the middle of the Holocene. The late Holocene (< c. 3300 calendar yr BP) is characterized by the establishment of environmental conditions similar to those existing today. A late Holocene desiccation event, such as proposed in former studies, is not indicated in the sediment sequences recovered.

Granulometry, mineralogy and organic matter content of permafrost core 5011-3

The combination of permafrost history and dynamics, lake level changes and the tectonical framework is considered to play a crucial role for sediment delivery to El'gygytgyn Crater Lake, NE Russian Arctic. The purpose of this study is to propose a depositional framework based on analyses of the core strata from the lake margin and historical reconstructions from various studies at the site. A sedimentological program has been conducted using frozen core samples from the 141.5 m long El'gygytgyn 5011-3 permafrost well. The drill site is located in sedimentary permafrost west of the lake that partly fills the El'gygytgyn Crater. The total core sequence is interpreted as strata building up a progradational alluvial fan delta. Four macroscopically distinct sedimentary units are identified. Unit 1 (141.5-117.0 m) is comprised of ice-cemented, matrix-supported sandy gravel and intercalated sandy layers. Sandy layers represent sediments which rained out as particles in the deeper part of the water column under highly energetic conditions. Unit 2 (117.0-24.25 m) is dominated by ice-cemented, matrix-supported sandy gravel with individual gravel layers. Most of the Unit 2 diamicton is understood to result from alluvial wash and subsequent gravitational sliding of coarse-grained (sandy gravel) material on the basin slope. Unit 3 (24.25-8.5 m) has ice-cemented, matrix-supported sandy gravel that is interrupted by sand beds. These sandy beds are associated with flooding events and represent near-shore sandy shoals. Unit 4 (8.5-0.0 m) is ice-cemented, matrix-supported sandy gravel with varying ice content, mostly higher than below. It consists of slope material and creek fill deposits. The uppermost metre is the active layer (i.e. the top layer of soil with seasonal freeze and thaw) into which modern soil organic matter has been incorporated. The nature of the progradational sediment transport taking place from the western and northern crater margins may be related to the complementary occurrence of frequent turbiditic layers in the central lake basin, as is known from the lake sediment record. Slope processes such as gravitational sliding and sheet flooding occur especially during spring melt and promote mass wasting into the basin. Tectonics are inferred to have initiated the fan accumulation in the first place and possibly the off-centre displacement of the crater lake.

Interactive effects of ocean acidification and neighboring corals on the growth of Pocillopora verrucosa

The physical and chemical environment around corals, as well as their physiology, can be affected by interactions with neighboring corals. This study employed small colonies (4 cm diameter) of Pocillopora verrucosa and Acropora hyacinthus configured in spatial arrays at 7 cm/s flow speed to test the hypothesis that ocean acidification (OA) alters interactions among them. Interaction effects were quantified for P. verrucosa using three measures of growth: calcification (i.e., weight), horizontal growth, and vertical growth. The study was carried out in May-June 2014 using corals from 10 m depth on the outer reef of Moorea, French Polynesia. Colonies of P. verrucosa were placed next to conspecifics or heterospecifics (A. hyacinthus) in arrangements of two or four colonies (pairs and aggregates) that were incubated at ambient and high pCO2 (1000 µatm) for 28 days. There was an effect of pCO2, and arrangement type on multivariate growth (utilizing the three measures of growth), but no interaction between the main effects. Conversely, arrangement and pCO2 had an interactive effect on calcification, with an overall 23 % depression at high pCO2 versus ambient pCO2 (i.e., pooled among arrangements). Within arrangements, there was a 34-45 % decrease in calcification for solitary and paired conspecifics, but no effect in conspecific aggregates, heterospecific pairs, or heterospecific aggregates. Horizontal growth was negatively affected by pCO2 and arrangement type, while vertical growth was positively affected by arrangement type. Together, our results show that conspecific aggregations can mitigate the negative effects of OA on calcification of colonies within an aggregation.