Ring-chain interconversion in high-performance polymer systems. 3. Cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex) and entropically driven ring-opening polymerization of the macrocyclic oligomers so produced

A homologous series of macrocyclic oligoamides has been prepared in high yield by reaction of isophthaloyl chloride with m-phenylenediamine under pseudo-high-dilution conditions. The products were characterized by infrared and H-1 NMR spectroscopies, matrix assisted laser desorption-ionization time-of-flight mass spectrometry, and gel permeation chromatography (GPC). A series of linear oligomers was prepared for comparison. The macrocycles ranged in size from the cyclic trimer up to at least the cyclic nonamer (90 ring atoms). The same homologous series of macrocyclic oligomers was prepared in high yield by the cyclodepolymerization of poly(m-phenylene isophthalamide) (Nomex). Cyclodepolymerization was best achieved by treating a 1% w/v solution of the polymer in dimethyl sulfoxide containing calcium chloride or lithium chloride with 3-4 mol % of sodium hydride or the sodium salt of benzanilide at 150 degreesC for 70 h. Treatment of a concentrated solution of the macrocyclic oligomers (25% w/v) with 4 mol % of sodium hydride or the sodium salt of benzanilide in a solution of lithium chloride in dimethyl sulfoxide at 170 degreesC for 6 h resulted in efficient entropically driven ring-opening polymerizations to give poly(m-phenylene isophthalamide), characterized by infrared and H-1 NMR spectroscopies and by GPC. The molecular weights obtained were comparable with those of the commercial polymer.

Microblock ionomers: a new concept in high temperature, swelling-resistant membranes for PEM fuel cells

A novel series of polyaromatic ionomers with similar equivalent weights but very different sulphonic acid distributions along the ionomer backbone has been designed and prepared. By synthetically organising the sequence-distribution so that it consists of fully defined ionic segments (containing singlets, doublets or quadruplets of sulphonic acid groups) alternating strictly with equally well-defined nonionic spacer segments, a new class of polymers which may be described as microblock ionomers has been developed. These materials exhibit very different properties and morphologies from analogous randomly substituted systems. Progressively extending the nonionic spacer length in the repeat unit (maintaining a constant equivalent weight by increasing the degree of sulphonation. of the ionic segment) leads to an increasing degree of nanophase separation between hydrophilic and hydrophobic domains in these materials. Membranes cast from ionomers with the more highly phase-separated morphologies show significantly higher onset temperatures for uncontrolled swelling in water. This new type of ionomer design has enabled the fabrication of swelling-resistant hydrocarbon membranes, suitable for fuel cell operation, with very much higher ion exchange capacities (>2 meq g(-1)) than those previously reported in the literature. When tested in a fuel cell at high temperature (120 degrees C) and low relative humidity (35% RH), the best microblock membrane matched the performance of Nafion 112. Moreover, comparative low load cycle testing of membrane -electrode assemblies suggests that the durability of the new membranes under conditions of high temperature and low relative humidity is superior to that of conventional perfluorinated materials.

Opportunities and challenges in high pressure processing of foods

Consumers increasingly demand convenience foods of the highest quality in terms of natural flavor and taste, and which are freedom additives and preservatives. This demand has triggered the need for the development of a number of nonthermal approaches to food processing, of which high-pressure technology has proven to be very valuable. A number of recent publications have demonstrated novel and diverse uses of this technology. Its novel features, which include destruction of microorganisms at room temperature or lower, have made the technology commerically attractive. Enzymes forming bacteria can be by the application of pressure-thermal combinations. This review aims to identify the opportunities and challenges associated with this technology. In addition to discussing the effects of high pressure on food components, this review covers the combined effects of high pressure processing with: gamma irradiation, alternating current, ultrasound, and carbon dioxide or anti-microbial treatment. Further, the applications of this technology in various sectors-fruits and vegetables, dairy and meat processing-have been dealt with extensively. The integration of high-pressure with other matured processing operations such as blanching, dehydration, osmotic dehydration, rehyrdration, frying, freezing/thawing and solid-liquid extraction has been shown to open up new processing options. The key challenges identified include: heat transfer problems and resulting non-uniformity in processing, obtaining reliable and reproducible data, for process validation, lack of detailed knowledge about the interaction between high pressure, and a number of food constituents, packaging and statutory issues.

Symposium on 'nutrition interventions in high-risk groups' - CVD risk in South Asians: the importance of defining adiposity and influence of dietary polyunsaturated fat

The prevalence of the metabolic syndrome (MetS), CVD and type 2 diabetes (T2D) is known to be higher in populations from the Indian subcontinent compared with the general UK population. While identification of this increased risk is crucial to allow for effective treatment, there is controversy over the applicability of diagnostic criteria, and particularly measures of adiposity in ethnic minorities. Diagnostic cut-offs for BMI and waist circumference have been largely derived from predominantly white Caucasian populations and, therefore, have been inappropriate and not transferable to Asian groups. Many Asian populations, particularly South Asians, have a higher total and central adiposity for a similar body weight compared with matched Caucasians and greater CVD risk associated with a lower BMI. Although the causes of CVD and T2D are multi-factorial, diet is thought to make a substantial contribution to the development of these diseases. Low dietary intakes and tissue levels of long-chain (LC) n-3 PUFA in South Asian populations have been linked to high-risk abnormalities in the MetS. Conversely, increasing the dietary intake of LC n-3 PUFA in South Asians has proved an effective strategy for correcting such abnormalities as dyslipidaemia in the MetS. Appropriate diagnostic criteria that include a modified definition of adiposity must be in place to facilitate the early detection and thus targeted treatment of increased risk in ethnic minorities.

Posttraumatic stress symptoms in London school children following September 11, 2001: an exploratory investigation of peri-traumatic reactions and intrusive imagery

Threatening intrusive images are central to posttraumatic stress disorder. It has been suggested that intrusive imagery in the context of a sense of threat leads to the development and persistence of posttraumatic stress symptoms. This study investigates London school children's (N = 76; age 10-11 years) self-reported posttraumatic stress symptoms in response to viewing the attacks of September 11, 2001 on television. Assessments were made at two time points. A minority of participants reported moderate-severe symptoms with functional impairment at 2 months (14.5%) and 6 months (9.2%) after viewing the September 11events. After controlling for symptom stability, persistent symptoms were associated with peri-traumatic factors, notably perceiving that one's life was in danger. The combined effect of intrusive imagery and peri-traumatic life threat was associated with symptom persistence. Assessments of intrusive image content via checklist and free-report indicated that the images were directly related to September 11 and were fairly stable over time. Implications for treating children's intrusive images following stressful events are explored. (C) 2007 Elsevier Ltd. All rights reserved.

A method for merging flow-dependent forecast error statistics from an ensemble with static statistics for use in high resolution variational data assimilation

The background error covariance matrix, B, is often used in variational data assimilation for numerical weather prediction as a static and hence poor approximation to the fully dynamic forecast error covariance matrix, Pf. In this paper the concept of an Ensemble Reduced Rank Kalman Filter (EnRRKF) is outlined. In the EnRRKF the forecast error statistics in a subspace defined by an ensemble of states forecast by the dynamic model are found. These statistics are merged in a formal way with the static statistics, which apply in the remainder of the space. The combined statistics may then be used in a variational data assimilation setting. It is hoped that the nonlinear error growth of small-scale weather systems will be accurately captured by the EnRRKF, to produce accurate analyses and ultimately improved forecasts of extreme events.

Belowground biomass functions and expansion factors in high elevation Norway spruce

Biomass allocation to above- and belowground compartments in trees is thought to be affected by growth conditions. To assess the strength of such influences, we sampled six Norway spruce forest stands growing at higher altitudes. Within these stands, we randomly selected a total of 77 Norway spruce trees and measured volume and biomass of stem, above- and belowground stump and all roots over 0.5 cm diameter. A comparison of our observations with models parameterised for lower altitudes shows that models developed for specific conditions may be applicable to other locations. Using our observations, we developed biomass functions (BF) and biomass conversion and expansion factors (BCEF) linking belowground biomass to stem parameters. While both BF and BCEF are accurate in belowground biomass predictions, using BCEF appears more promising as such factors can be readily used with existing forest inventory data to obtain estimates of belowground biomass stock. As an example, we show how BF and BCEF developed for individual trees can be used to estimate belowground biomass at the stand level. In combination with existing aboveground models, our observations can be used to quantify total standing biomass of high altitude Norway spruce stands.

Simple solution for a complex problem: Proanthocyanidins, galloyl glucoses and ellagitannins fit on a single calibration curve in high performance-gel permeation chromatography

This study was undertaken to explore gel permeation chromatography (GPC) for estimating molecular weights of proanthocyanidin fractions isolated from sainfoin (Onobrychis viciifolia). The results were compared with data obtained by thiolytic degradation of the same fractions. Polystyrene, polyethylene glycol and polymethyl methacrylate standards were not suitable for estimating the molecular weights of underivatized proanthocyanidins. Therefore, a novel HPLC-GPC method was developed based on two serially connected PolarGel-L columns using DMF that contained 5% water, 1% acetic acid and 0.15 M LiBr at 0.7 ml/min and 50 degrees C. This yielded a single calibration curve for galloyl glucoses (trigalloyl glucose, pentagalloyl glucose), ellagitannins (pedunculagin, vescalagin, punicalagin, oenothein B, gemin A), proanthocyanidins (procyanidin B2, cinnamtannin B1), and several other polyphenols (catechin, epicatechin gallate, epicallocatechin gallate, amentoflavone). These GPC predicted molecular weights represented a considerable advance over previously reported HPLC-GPC methods for underivatized proanthocyanidins. (C) 2011 Elsevier B.V. All rights reserved.

Chaos in high performance digital robot controllers

Active robot force control requires some form of dynamic inner loop control for stability. The author considers the implementation of position-based inner loop control on an industrial robot fitted with encoders only. It is shown that high gain velocity feedback for such a robot, which is effectively stationary when in contact with a stiff environment, involves problems beyond the usual caveats on the effects of unknown environment stiffness. It is shown that it is possible for the controlled joint to become chaotic at very low velocities if encoder edge timing data are used for velocity measurement. The results obtained indicate that there is a lower limit on controlled velocity when encoders are the only means of joint measurement. This lower limit to speed is determined by the desired amount of loop gain, which is itself determined by the severity of the nonlinearities present in the drive system.

Numerical-asymptotic boundary integral methods in high-frequency acoustic scattering

In this article we describe recent progress on the design, analysis and implementation of hybrid numerical-asymptotic boundary integral methods for boundary value problems for the Helmholtz equation that model time harmonic acoustic wave scattering in domains exterior to impenetrable obstacles. These hybrid methods combine conventional piecewise polynomial approximations with high-frequency asymptotics to build basis functions suitable for representing the oscillatory solutions. They have the potential to solve scattering problems accurately in a computation time that is (almost) independent of frequency and this has been realized for many model problems. The design and analysis of this class of methods requires new results on the analysis and numerical analysis of highly oscillatory boundary integral operators and on the high-frequency asymptotics of scattering problems. The implementation requires the development of appropriate quadrature rules for highly oscillatory integrals. This article contains a historical account of the development of this currently very active field, a detailed account of recent progress and, in addition, a number of original research results on the design, analysis and implementation of these methods.