Observation of early childhood educators??? interaction style and child experience ??? opportunities for training in context

Monogr??fico con el t??tulo: " Formaci??n de profesores. Perspectivas de Brasil, Colombia, Espa??a y Portugal"

In situ observation of lithium hydride hydrolysis by DRIFT spectroscopy

Polycrystalline LiH was studied in situ using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy to investigate the effect water vapour has on the rate of production of the corrosion products, particularly LiOH. The reaction rate of the formation of surface LiOH was monitored by measurement of the hydroxyl (OH) band at 3676 cm(-1). The initial hydrolysis rate of LiH exposed to water vapour at 50% relative humidity was found to be almost two times faster than LiH exposed to water vapour at 2% relative humidity. The hydrolysis rate was shown to be initially very rapid followed by a much slower, almost linear rate. The change in hydrolysis rate was attributed to the formation of a coherent layer of LiOH on the LiH surface. Exposure to lower levels of water vapour appeared to result in the formation of a more coherent corrosion product, resulting in effective passivation of the surface to further attack from water. Crown Copyright (c) 2007 Published by Elsevier B.V. All rights reserved.

SAXS observation of RCM1 under cyclical shear

A cylinder forming poly(styrene-b-butadiene-b-styrene) triblock copolymer melt is cyclically processed through a capillary at a high shear rate in the Cambridge Multipass Rheometer (MPR). In situ X-ray diffraction experiments enable observation of the effect of the shear on the block copolymer (BCP) nanophase orientation, both during and after processing. Temporal resolution of the X-ray exposures is increased, whilst retaining intensity, by exploiting the cyclical nature of the shear and the material's response to it; short exposures from many cycles, individually having few counts, are added together to produce well resolved X-ray patterns. Orientation of the cylinders reduces during processing, then increases during pauses between processing. The loss of orientation is attributed to the high shear rate deforming the melt faster than the structure can respond, whilst it is believed that melt relaxation, linked to the compressibility of the material, produces much lower shear rates after mechanical processing has ceased, which induces strong orientation of the nanostructure.

Observation of carbonyl oxygen-pi interaction in a metal complex

X-ray crystallography shows that [Ag2L2(H2O)(2)](BF4)(2) where L is a 1:1 condensate of 1,2-diphenylethane-1,2-dione and 2-(2-aminoethyl pyridine), contains an Ag(I)-Ag(I) bond of length 2.979(2) angstrom and an angular, intraligand interaction of the keto O with the pi cloud of the pyridine moiety (O-pyridine centroid = 3.12 angstrom). Model MP2/6-311++G(d,p) calculations indicate that the observed lone pair-pi type interaction is stabilising and not merely a tolerated short contact. (C) 2008 Elsevier B.V. All rights reserved.

Mixed ligand binuclear copper(I) complexes containing (Cu2N8)-N-I chromophores. Observation of emissions from MLCT excited states involving two different ligands

Using the 1:2 condensate (L) of diethylenetriamine and benzaldehyde as the main ligand, binuclear copper(l) complexes [Cu2L2(4,4'-bipyridine)](CIO4)(2).0.5H(2)O (1a) and [Cu2L2(1,2-bis(4-pyridyl)ethane)](CIO4)(2) (1b) are synthesised. The two metal ions in la are bridged by 4,4'-bipyridine and those in 1b by 1,2-bis(4-pyridyl)ethane, From the X-ray crystal structure of la, each metal ion is found to be bound to three N atoms of L and one of the two N atoms of the bridging ligand in a distorted tetrahedral fashion. The Cu(I)-N bond lengths in la lie in the range of 1.998(5)-2.229(6) Angstrom. Electrochemical studies in dichloromethane (DCM) show that the (Cu2N8)-N-I moieties in la and 1b are composed of two essentially non-interacting (CuN4)-N-I cores with Cu-II/I potential of 0.44 V vs. SCE. While la displays metal induced quenching of the inherent emission of 4,4'-bipyridine in DCM solution, 1b exhibits two weak emission bands in DCM solution at 425 and 477 nm (total quantum yield = 3.59 x 10(-5)) originating from MLCT excited states. With the help of Extended Huckel calculations it is established that the higher energy emission in 1b is from Cu(I) --> bridging-ligand charge transfer excited state and the lower energy one in 1b from Cu(I) --> L charge transfer excited state.

Computer simulations of structures, energetics and dynamics of myoglobin center dot center dot center dot ligand complexes

Myoglobin has been studied in considerable detail using different experimental and computational techniques over the past decades. Recent developments in time-resolved spectroscopy have provided experimental data amenable to detailed atomistic simulations. The main theme of the present review are results on the structures, energetics and dynamics of ligands ( CO, NO) interacting with myoglobin from computer simulations. Modern computational methods including free energy simulations, mixed quantum mechanics/molecular mechanics simulations, and reactive molecular dynamics simulations provide insight into the dynamics of ligand dynamics in confined spaces complementary to experiment. Application of these methods to calculate and understand experimental observations for myoglobin interacting with CO and NO are presented and discussed.

Direct observation of time-resolved polymorphic states in the self-assembly of end-capped heptapeptides

Amyloid fibrils resulting from uncontrolled peptide aggregation are associated with several neurodegenerative diseases. Their polymorphism depends on a number of factors including pH, ionic strength, electrostatic interactions, hydrophobic interactions, hydrogen bonding, aromatic stacking interactions, and chirality. Understanding the mechanism of amyloid fibril formation can improve strategies towards the prevention of fibrillation processes and enable a wide range of potential applications in nanotemplating and nanotechnology.

Multispacecraft observation of magnetic cloud erosion by magnetic reconnection during propagation

During propagation, Magnetic Clouds (MC) interact with their environment and, in particular, may reconnect with the solar wind around it, eroding away part of its initial magnetic flux. Here we quantitatively analyze such an interaction using combined, multipoint observations of the same MC flux rope by STEREO A, B, ACE, WIND and THEMIS on November 19–20, 2007. Observation of azimuthal magnetic flux imbalance inside a MC flux rope has been argued to stem from erosion due to magnetic reconnection at its front boundary. The present study adds to such analysis a large set of signatures expected from this erosion process. (1) Comparison of azimuthal flux imbalance for the same MC at widely separated points precludes the crossing of the MC leg as a source of bias in flux imbalance estimates. (2) The use of different methods, associated errors and parametric analyses show that only an unexpectedly large error in MC axis orientation could explain the azimuthal flux imbalance. (3) Reconnection signatures are observed at the MC front at all spacecraft, consistent with an ongoing erosion process. (4) Signatures in suprathermal electrons suggest that the trailing part of the MC has a different large-scale magnetic topology, as expected. The azimuthal magnetic flux erosion estimated at ACE and STEREO A corresponds respectively to 44% and 49% of the inferred initial azimuthal magnetic flux before MC erosion upon propagation. The corresponding average reconnection rate during transit is estimated to be in the range 0.12–0.22 mV/m, suggesting most of the erosion occurs in the inner parts of the heliosphere. Future studies ought to quantify the influence of such an erosion process on geo-effectiveness.

CLSM method for the dynamic observation of pH change within polymer matrices for oral delivery

If acid-sensitive drugs or cells are administered orally, there is often a reduction in efficacy associated with gastric passage. Formulation into a polymer matrix is a potential method to improve their stability. The visualization of pH within these materials may help better understand the action of these polymer systems and allow comparison of different formulations. We herein describe the development of a novel confocal laser-scanning microscopy (CLSM) method for visualizing pH changes within polymer matrices and demonstrate its applicability to an enteric formulation based on chitosan-coated alginate gels. The system in question is first shown to protect an acid-sensitive bacterial strain to low pH, before being studied by our technique. Prior to this study, it has been claimed that protection by these materials is a result of buffering, but this has not been demonstrated. The visualization of pH within these matrices during exposure to a pH 2.0 simulated gastric solution showed an encroachment of acid from the periphery of the capsule, and a persistence of pHs above 2.0 within the matrix. This implies that the protective effect of the alginate-chitosan matrices is most likely due to a combination of buffering of acid as it enters the polymer matrix and the slowing of acid penetration.

Direct observation of membrane insertion by enveloped virus matrix proteins by phosphate displacement

Enveloped virus release is driven by poorly understood proteins that are functional analogs of the coat protein assemblies that mediate intracellular vesicle trafficking. We used differential electron density mapping to detect membrane integration by membrane-bending proteins from five virus families. This demonstrates that virus matrix proteins replace an unexpectedly large portion of the lipid content of the inner membrane face, a generalized feature likely to play a role in reshaping cellular membranes.

Selecting algorithms for Earth observation of climate within the European Space Agency Climate Change initiative: introduction to a special issue

This special issue is focused on the assessment of algorithms for the observation of Earth’s climate from environ- mental satellites. Climate data records derived by remote sensing are increasingly a key source of insight into the workings of and changes in Earth’s climate system. Producers of data sets must devote considerable effort and expertise to maximise the true climate signals in their products and minimise effects of data processing choices and changing sensors. A key choice is the selection of algorithm(s) for classification and/or retrieval of the climate variable. Within the European Space Agency Climate Change Initiative, science teams undertook systematic assessment of algorithms for a range of essential climate variables. The papers in the special issue report some of these exercises (for ocean colour, aerosol, ozone, greenhouse gases, clouds, soil moisture, sea surface temper- ature and glaciers). The contributions show that assessment exercises must be designed with care, considering issues such as the relative importance of different aspects of data quality (accuracy, precision, stability, sensitivity, coverage, etc.), the availability and degree of independence of validation data and the limitations of validation in characterising some important aspects of data (such as long-term stability or spatial coherence). As well as re- quiring a significant investment of expertise and effort, systematic comparisons are found to be highly valuable. They reveal the relative strengths and weaknesses of different algorithmic approaches under different observa- tional contexts, and help ensure that scientific conclusions drawn from climate data records are not influenced by observational artifacts, but are robust.

Could in-home sensors surpass human observation of people with Parkinson’s at high risk of falling? An ethnographic study

Self-report underpins our understanding of falls among people with Parkinson’s (PwP) as they largely happen unwitnessed at home. In this qualitative study, we used an ethnographic approach to investigate which in-home sensors, in which locations, could gather useful data about fall risk. Over six weeks, we observed five independently mobile PwP at high risk of falling, at home. We made field notes about falls (prior events and concerns) and recorded movement with video, Kinect, and wearable sensors. The three women and two men (aged 71 to 79 years) having moderate or severe Parkinson’s were dependent on others and highly sedentary. We most commonly noted balance protection, loss, and restoration during chair transfers, walks across open spaces and through gaps, turns, steps up and down, and tasks in standing (all evident walking between chair and stairs, e.g.). Our unobtrusive sensors were acceptable to participants: they could detect instability during everyday activity at home and potentially guide intervention. Monitoring the route between chair and stairs is likely to give information without invading the privacy of people at high risk of falling, with very limited mobility, who spend most of the day in their sitting rooms.