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.

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.

Phospholipid-based microemulsions suitable for use in foods

The preparation of nonaqueous microemulsions using food-acceptable components is reported. The effect of oil on the formation of microemulsions stabilized by lecithin (Epikuron 200) and containing propylene glycol as immiscible solvent was investigated. When the triglycerides were used as oil, three types of phase behavior were noted, namely, a two-phase cloudy region (occurring at low lecithin concentrations), a liquid crystalline (LC) phase (occurring at high surfactant and low oil concentrations), and a clear monophasic microemulsion region. The extent of this clear one-phase region was found to be dependent upon the molecular volume of the oil being solubilized. Large molecular volume oils, such as soybean and sunflower oils, produced a small microemulsion region, whereas the smallest molecular volume triglyceride, tributyrin, produced a large, clear monophasic region. Use of the ethyl ester, ethyl oleate, as oil produced a clear, monophasic region of a size comparable to that seen with tributyrin. Substitution of some of the propylene glycol with water greatly reduced the extent of the clear one-phase region and increased the extent of the liquid crystalline region. In contrast, ethanol enhanced the clear, monophasic region by decreasing the LC phase. Replacement of some of the lecithin with the micelle-forming nonionic surfactant Tween 80 to produce mixed lecithin/Tween 80 mixtures of weight ratios (Km) 1:2 and 1:3 did not significantly alter the phase behavior, although there was a marginal increase in the area of the two-phase, cloudy region of the phase diagram. The use of the lower phosphatidylcholine content lecithin, Epikuron 170, in place of Epikuron 200 resulted in a reduction in the LC region for all of the systems investigated. In conclusion, these studies show that it is possible to prepare one-phase, clear lecithin-based microemulsions over a wide range of compositions using components that are food-acceptable.

Fluorinated ionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

The factors influencing the formation of water-in-134a-propellant microemulsions using the fluorinated ionic surfactants ammonium perfluorooctanoate, ammonium perfluoroheptanoate, and sodium perfluorooctanoate has been determined. None of the fluorinated ionic surfactants could be used to prepare clear, one-phase systems when used as sole surfactant, but they could be when combined with a short-chain fluoro- or hydrocarbon alcohol in surfactant:cosurfactant weight-mixing ratios (K(m)) in the range 1:2 to 2:1. When hydrocarbon alcohols were used this clear region extended over a wide range of compositions and was confirmed by means of photon correlation spectroscopy (PCS) to contain microemulsion droplets in the propellant-rich part of the phase diagram. PCS studies performed in the presence of the water-soluble drug terbutaline sulfate showed that it was possible to solubilize the drug within water-in-propellant microemulsion droplets. These studies confirm for the first time that it is possible to prepare water-in-propellant 134a microemulsions using fluorinated ionic surfactants and to solubilize water-soluble drugs within these systems.

Formation of fluorinated nonionic surfactant microemulsions in hydrofluorocarbon 134a (HFC 134a)

A structurally related series of fluorinated nonionic oxyethylene glycol surfactants of the type C(m)F(2m+1)(CH(2))(n)O[(CH(2)CH(2)O)(p)H], denoted C(m.n)E(p) (where m=4, 6, or 7, m=1 or 2, and p=4 or 6) were synthesized and their surface behavior in aqueous solution was characterized. The ability of these surfactants to form water-in-hydrofluorocarbon (HFC) propellant 134a microemulsions suitable for use in the aerosolized delivery of water-soluble drugs has been investigated. Phase studies showed that, regardless of the composition used, clear one-phase systems could not be prepared if a fluorinated nonionic surfactant was used alone, or in combination with a short or medium fluorocarbon alcohol cosurfactant. Clear one-phase systems could, however, be prepared if a short-chain hydrocarbon alcohol, such as ethanol, n-propanol, or n-pentanol, was used as cosurfactant, with the extent of the one-phase region increasing with decreased chain length of the alcohol cosurfactant. Light-scattering studies on a number of the hydrocarbon-alcoholcontaining systems in the propellant-rich part of the phase diagram showed that only systems prepared with C(4.2)E(6) and propanol contained microemulsion droplets (all other systems investigated were considered to be cosolvent systems).

Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

On the structure and dynamics of Indian monsoon depressions

ERA-Interim reanalysis data from the past 35 years have been used with a newly-developed feature tracking algorithm to identify Indian monsoon depressions originating in or near the Bay of Bengal. These were then rotated, centralised and combined to give a fully three-dimensional 106-depression composite structure – a considerably larger sample than any previous detailed study on monsoon depressions and their structure. Many known features of depression structure are confirmed, particularly the existence of a maximum to the southwest of the centre in rainfall and other fields, and a westward axial tilt in others. Additionally, the depressions are found to have significant asymmetry due to the presence of the Himalayas; a bimodal mid-tropospheric potential vorticity core; a separation into thermally cold- (~–1.5K) and neutral- (~0K) cores near the surface with distinct properties; and that the centre has very large CAPE and very small CIN. Variability as a function of background state has also been explored, with land/coast/sea, diurnal, ENSO, active/break and Indian Ocean Dipole contrasts considered. Depressions are found to be markedly stronger during the active phase of the monsoon, as well as during La Niña. Depressions on land are shown to be more intense and more tightly constrained to the central axis. A detailed schematic diagram of a vertical cross-section through a composite depression is also presented, showing its inherent asymmetric structure.