Structure, rheology and shear alignment of Pluronic block copolymer mixtures

The structure and flow behaviour of binary mixtures of Pluronic block copolymers P85 and P123 is investigated by small-angle scattering, rheometry and mobility tests. Micelle dimensions are probed by dynamic light scattering. The micelle hydrodynamic radius for the 50/50 mixture is larger than that for either P85 or P123 alone, Clue to the formation of mixed micelles with a higher association number. The phase diagram for 50/50 mixtures contains regions Of Cubic and hexagonal phases similar to those for the parent homopolymers, however the region of stability of the cubic phase is enhanced at low temperature and concentrations above 40 wt%. This is ascribed to favourable packing of the mixed micelles containing core blocks with two different chain lengths, but similar corona chain lengths. The shear flow alignment of face-centred cubic and hexagonal phases is probed by in situ small-angle X-ray or neutron scattering with simultaneous rheology. The hexagonal phase can be aligned using steady shear in a Couette geometry, however the high modulus Cubic phase cannot be aligned well in this way. This requires the application of oscillatory shear or compression. (C) 2008 Elsevier Inc. All rights reserved.

Nanostructure formation in poly(gamma-benzyl-L-glutamate)-poly(ethylene glycol)-poly(gamma-benzyl-L-glutamate) triblock copolymers in the solid state

The morphology in the solid state of a series of triblock copolymers comprising a poly(ethylene glycol) (PEG) midblock and symmetric poly(gamma-benzyl-L-glutamate) (PBLG) end blocks has been studied using X-ray scattering and microscopy techniques. Transmission electron microscopy (TEM) on samples selectively stained with uranyl acetate provided clear assignment of morphologies for as-cast and annealed samples. The thickness of both PEG and PBLG domains was in good agreement with calculations based on the conformations of the respective chains, allowing for the crystal or amorphous state of PEG and the a-helical or P-sheet structure of the PBLG. Atomic force microscopy provided complementary information on surface morphology for several samples that was in good agreement with the structure observed by TEM. A morphology diagram was constructed. Cylindrical structures were observed for ordered samples with low f(PBLG), whereas at higher f(PLBG) there was evidence for broken lamellar and "hockey puck" nanostructures. Regular lamellae were observed for intermediate compositions.

Block copolymers of ethylene oxide and phenyl glycidyl ether: micellization, gelation, and drug solubilization

Three triblock copolymers of ethylene oxide and phenyl glycidyl ether, type E(m)G(n)E(m), where G = OCH2-CH(CH2OC6H5) and E = OCH2CH2, were synthesized and characterized by gel-permeation chromatography, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, and NMR spectroscopy. Their association properties in aqueous solution were investigated by surface tensiometry and light scattering, yielding values of the critical micelle concentration (cmc), the hydrodynamic radius, and the association number. Gel boundaries in concentrated micellar solution were investigated by tube inversion, and for one copolymer, the temperature and frequency dependence of the dynamic moduli served to confirm and extend the phase diagram and to highlight gel properties. Small-angle X-ray scattering was used to investigate gel structure. The overall aim of the work was to define a block copolymer micellar system with better solubilization capacity for poorly soluble aromatic drugs than had been achieved so far by use of block copoly(oxyalkylene)s. Judged by the solubilization of griseofulvin in aqueous solutions of the E(m)G(n)E(m) copolymers, this aim was achieved.

Solid phases of cyclopentane: combined experimental and simulation study

The phase diagram of cyclopentane has been studied by powder neutron diffraction, providing diffraction patterns for phases I, II, and III, over a range of temperatures and pressures. The putative phase IV was not observed. The structure of the ordered phase III has been solved by single-crystal diffraction. Computational modeling reveals that there are many equienergetic ordered structures for cyclopentane within a small energy range. Molecular dynamics simulations reproduce the structures and diffraction patterns for phases I and III and also show an intermediate disordered phase, which is used to interpret phase II.

High value information in engineering organisations

The management of information in engineering organisations is facing a particular challenge in the ever-increasing volume of information. It has been recognised that an effective methodology is required to evaluate information in order to avoid information overload and to retain the right information for reuse. By using, as a starting point, a number of the current tools and techniques which attempt to obtain ‘the value’ of information, it is proposed that an assessment or filter mechanism for information is needed to be developed. This paper addresses this issue firstly by briefly reviewing the information overload problem, the definition of value, and related research work on the value of information in various areas. Then a “characteristic” based framework of information evaluation is introduced using the key characteristics identified from related work as an example. A Bayesian Network diagram method is introduced to the framework to build the linkage between the characteristics and information value in order to quantitatively calculate the quality and value of information. The training and verification process for the model is then described using 60 real engineering documents as a sample. The model gives a reasonable accurate result and the differences between the model calculation and training judgements are summarised as the potential causes are discussed. Finally, several further issues including the challenge of the framework and the implementations of this evaluation assessment method are raised.

Melt brushes of diblock copolymer

Using self-consistent field theory (SCFT), we investigate the morphologies formed by a melt brush of AB diblock copolymers grafted to a flat substrate by their B ends. In addition to a laterally uniform morphology, SCFT predicts three ordered morphologies exhibiting different periodic patterns at the air surface: a hexagonal array of A-rich dots, an alternating sequence of A- and B-rich stripes, and a hexagonal pattern of B-rich dots. When the phase diagram of the tethered film is plotted as a function of A/B incompatibility, $\chi N$, and diblock composition, $f$, it resembles the bulk phase diagram with the periodic phases converging to a mean-field critical point at weak segregation. The periodic-phase region in the phase diagram shrinks with increasing grafting density and expands when the air surface acquires an affinity for the grafted B blocks.

Stochiometrically governed molecular interactions in drug: Poloxamer solid dispersions

This study probes the molecular interactions between model drugs and poloxamers that facilitate dissolution rate improvements using solid dispersions. Ibuprofen and ketoprofen solid dispersions were prepared at different mole ratios using poloxamers 407 and 188. The carbonyl stretching vibration of the ibuprofen dimer shifted to higher wavenumber in the infrared spectra of 2:1 drug:carrier mole ratio solid dispersions, indicating disruption of the ibuprofen dimer concomitant with hydrogen bond formation between the drug and carrier. Solid dispersions with mole ratios >2:1 drug:carrier (up to 29:1) showed both ibuprofen hydrogen-bonded to the poloxamer, and excess drug present as dimers. X-ray diffraction studies confirmed these findings with no evidence of crystalline drug in 2:1 mole ratio systems whereas higher drug loadings retained crystalline ibuprofen. Similar results were found with ketoprofen-poloxamer solid dispersions. Thermal analysis of ibuprofen-poloxamer 407 solid dispersions and their resultant phase diagram suggested solid solutions and a eutectic system were formed, depending on drug loading. Dissolution studies showed fastest release from the solid solutions; dissolution rates from solid solutions were 12-fold greater than the dissolution of ibuprofen powder whereas the eutectic system gave a 6-fold improvement over the powder. When designing solid dispersions to improve the delivery of poorly-water soluble drugs, the nature of drug:carrier interactions, which are governed by the stochiometry of the composition, can affect the dissolution rate improvement.

Spatiotemporal behavior of the TIGGE medium-range ensemble forecasts

Using the recently-developed mean–variance of logarithms (MVL) diagram, together with the TIGGE archive of medium-range ensemble forecasts from nine different centres, an analysis is presented of the spatiotemporal dynamics of their perturbations, showing how the differences between models and perturbation techniques can explain the shape of their characteristic MVL curves. In particular, a divide is seen between ensembles based on singular vectors or empirical orthogonal functions, and those based on bred vector, Ensemble Transform with Rescaling or Ensemble Kalman Filter techniques. Consideration is also given to the use of the MVL diagram to compare the growth of perturbations within the ensemble with the growth of the forecast error, showing that there is a much closer correspondence for some models than others. Finally, the use of the MVL technique to assist in selecting models for inclusion in a multi-model ensemble is discussed, and an experiment suggested to test its potential in this context.

Modula-2 applied

Programming is a skill which requires knowledge of both the basic constructs of the computer language used and techniques employing these constructs. How these are used in any given application is determined intuitively, and this intuition is based on experience of programs already written. One aim of this book is to describe the techniques and give practical examples of the techniques in action - to provide some experience. Another aim of the book is to show how a program should be developed, in particular how a relatively large program should be tackled in a structured manner. These aims are accomplished essentially by describing the writing of one large program, a diagram generator package, in which a number of useful programming techniques are employed. Also, the book provides a useful program, with an in-built manual describing not only how the program works, but also how it does it, with full source code listings. This means that the user can, if required, modify the package to meet particular requirements. A floppy disk is available from the publishers containing the program, including listings of the source code. All the programs are written in Modula-2, using JPI's Top Speed Modula-2 system running on IBM-PCs and compatibles. This language was chosen as it is an ideal language for implementing large programs and it is the main language taught in the Cybernetics Department at the University of Reading. There are some aspects of the Top Speed implementation which are not standard, so suitable comments are given when these occur. Although implemented in Modula-2, many of the techniques described here are appropriate to other languages, like Pascal of C, for example. The book and programs are based on a second year undergraduate course taught at Reading to Cybernetics students, entitled Algorithms and Data Structures. Useful techniques are described for the reader to use, applications where they are appropriate are recommended, but detailed analyses of the techniques are not given.

A metabolic system-wide characterisation of the pig: a model for human physiology

The pig is a single-stomached omnivorous mammal and is an important model of human disease and nutrition. As such, it is necessary to establish a metabolic framework from which pathology-based variation can be compared. Here, a combination of one and two-dimensional (1)H and (13)C nuclear magnetic resonance spectroscopy (NMR) and high-resolution magic angle spinning (HR-MAS) NMR was used to provide a systems overview of porcine metabolism via characterisation of the urine, serum, liver and kidney metabolomes. The metabolites observed in each of these biological compartments were found to be qualitatively comparable to the metabolic signature of the same biological matrices in humans and rodents. The data were modelled using a combination of principal components analysis and Venn diagram mapping. Urine represented the most metabolically distinct biological compartment studied, with a relatively greater number of NMR detectable metabolites present, many of which are implicated in gut-microbial co-metabolic processes. The major inter-species differences observed were in the phase II conjugation of extra-genomic metabolites; the pig was observed to conjugate p-cresol, a gut microbial metabolite of tyrosine, with glucuronide rather than sulfate as seen in man. These observations are important to note when considering the translatability of experimental data derived from porcine models.

Computational modes and grid imprinting on five quasi-uniform spherical C-grids

Currently, most operational forecasting models use latitude-longitude grids, whose convergence of meridians towards the poles limits parallel scaling. Quasi-uniform grids might avoid this limitation. Thuburn et al, JCP, 2009 and Ringler et al, JCP, 2010 have developed a method for arbitrarily-structured, orthogonal C-grids (TRiSK), which has many of the desirable properties of the C-grid on latitude-longitude grids but which works on a variety of quasi-uniform grids. Here, five quasi-uniform, orthogonal grids of the sphere are investigated using TRiSK to solve the shallow-water equations. We demonstrate some of the advantages and disadvantages of the hexagonal and triangular icosahedra, a Voronoi-ised cubed sphere, a Voronoi-ised skipped latitude-longitude grid and a grid of kites in comparison to a full latitude-longitude grid. We will show that the hexagonal-icosahedron gives the most accurate results (for least computational cost). All of the grids suffer from spurious computational modes; this is especially true of the kite grid, despite it having exactly twice as many velocity degrees of freedom as height degrees of freedom. However, the computational modes are easiest to control on the hexagonal icosahedron since they consist of vorticity oscillations on the dual grid which can be controlled using a diffusive advection scheme for potential vorticity.

Hydrological cycle in the Danube basin in present-day and XXII century simulations by IPCCAR4 global climate models

We present an intercomparison and verification analysis of 20 GCMs (Global Circulation Models) included in the 4th IPCC assessment report regarding their representation of the hydrological cycle on the Danube river basin for 1961–2000 and for the 2161–2200 SRESA1B scenario runs. The basin-scale properties of the hydrological cycle are computed by spatially integrating the precipitation, evaporation, and runoff fields using the Voronoi-Thiessen tessellation formalism. The span of the model- simulated mean annual water balances is of the same order of magnitude of the observed Danube discharge of the Delta; the true value is within the range simulated by the models. Some land components seem to have deficiencies since there are cases of violation of water conservation when annual means are considered. The overall performance and the degree of agreement of the GCMs are comparable to those of the RCMs (Regional Climate Models) analyzed in a previous work, in spite of the much higher resolution and common nesting of the RCMs. The reanalyses are shown to feature several inconsistencies and cannot be used as a verification benchmark for the hydrological cycle in the Danubian region. In the scenario runs, for basically all models the water balance decreases, whereas its interannual variability increases. Changes in the strength of the hydrological cycle are not consistent among models: it is confirmed that capturing the impact of climate change on the hydrological cycle is not an easy task over land areas. Moreover, in several cases we find that qualitatively different behaviors emerge among the models: the ensemble mean does not represent any sort of average model, and often it falls between the models’ clusters.

Outgoing longwave radiation due to directly transmitted surface emission

A frequently used diagram summarizing the annual- and global-mean energy budget of the earth and atmosphere indicates that the irradiance reaching the top of the atmosphere from the surface, through the midinfrared atmospheric window, is 40 W m−2; this can be compared to the total outgoing longwave radiation (OLR) of about 235 W m−2. The value of 40 W m−2 was estimated in an ad hoc manner. A more detailed calculation of this component, termed here the surface transmitted irradiance (STI), is presented, using a line-by-line radiation code and 3D climatologies of temperature, humidity, cloudiness, etc. No assumption is made as to the wavelengths at which radiation from the surface can reach the top of the atmosphere. The role of the water vapor continuum is highlighted. In clear skies, if the continuum is excluded, the global- and annual-mean STI is calculated to be about 100 W m−2 with a broad maximum throughout the tropics and subtropics. When the continuum is included, the clear-sky STI is reduced to 66 W m−2, with a distinctly different geographic distribution, with a minimum in the tropics and local peaks over subtropical deserts. The inclusion of clouds reduces the STI to about 22 W m−2. The actual value is likely somewhat smaller due to processes neglected here, and an STI value of 20 W m−2 (with an estimated uncertainty of about ±20%) is suggested to be much more realistic than the previous estimate of 40 W m−2. This indicates that less than one-tenth of the OLR originates directly from the surface.

On reliability analysis of multi-categorical forecasts

Reliability analysis of probabilistic forecasts, in particular through the rank histogram or Talagrand diagram, is revisited. Two shortcomings are pointed out: Firstly, a uniform rank histogram is but a necessary condition for reliability. Secondly, if the forecast is assumed to be reliable, an indication is needed how far a histogram is expected to deviate from uniformity merely due to randomness. Concerning the first shortcoming, it is suggested that forecasts be grouped or stratified along suitable criteria, and that reliability is analyzed individually for each forecast stratum. A reliable forecast should have uniform histograms for all individual forecast strata, not only for all forecasts as a whole. As to the second shortcoming, instead of the observed frequencies, the probability of the observed frequency is plotted, providing and indication of the likelihood of the result under the hypothesis that the forecast is reliable. Furthermore, a Goodness-Of-Fit statistic is discussed which is essentially the reliability term of the Ignorance score. The discussed tools are applied to medium range forecasts for 2 m-temperature anomalies at several locations and lead times. The forecasts are stratified along the expected ranked probability score. Those forecasts which feature a high expected score turn out to be particularly unreliable.

A metabolic system-wide characterisation of the pig: a model for human physiology

The pig is a single-stomached omnivorous mammal and is an important model of human disease and nutrition. As such, it is necessary to establish a metabolic framework from which pathology-based variation can be compared. Here, a combination of one and two-dimensional 1H and 13C nuclear magnetic resonance spectroscopy (NMR) and high-resolution magic angle spinning (HR-MAS) NMR was used to provide a systems overview of porcine metabolism via characterisation of the urine, serum, liver and kidney metabolomes. The metabolites observed in each of these biological compartments were found to be qualitatively comparable to the metabolic signature of the same biological matrices in humans and rodents. The data were modelled using a combination of principal components analysis and Venn diagram mapping. Urine represented the most metabolically distinct biological compartment studied, with a relatively greater number of NMR detectable metabolites present, many of which are implicated in gut-microbial co-metabolic processes. The major interspecies differences observed were in the phase II conjugation of extra-genomic metabolites; the pig was observed to conjugate p-cresol, a gut microbial metabolite of tyrosine, with glucuronide rather than sulfate as seen in man. These observations are important to note when considering the translatability of experimental data derived from porcine models.