Modeling the molecular weight distribution of block copolymer formation in a reversible addition-fragmentation chain transfer mediated living radical polymerization

Block copolymers have become an integral part of the preparation of complex architectures through self-assembly. The use of reversible addition-fragmentation chain transfer (RAFT) allows blocks ranging from functional to nonfunctional polymers to be made with predictable molecular weight distributions. This article models block formation by varying many of the kinetic parameters. The simulations provide insight into the overall polydispersities (PDIs) that will be obtained when the chain-transfer constants in the main equilibrium steps are varied from 100 to 0.5. When the first dormant block [polymer-S-C(Z)=S] has a PDI of 1 and the second propagating radical has a low reactivity to the RAFT moiety, the overall PDI will be greater than 1 and dependent on the weight fraction of each block. When the first block has a PDI of 2 and the second propagating radical has a low reactivity to the RAFT moiety, the PDI will decrease to around 1.5 because of random coupling of two broad distributions. It is also shown how we can in principle use only one RAFT agent to obtain block copolymers with any desired molecular weight distribution. We can accomplish this by maintaining the monomer concentration at a constant level in the reactor over the course of the reaction. (c) 2005 Wiley Periodicals, Inc.

Modeling nitrogen adsorption in spherical pores of siliceous materials by density functional theory

Adsorption of nitrogen in spherical pores of FDU-1 silica at 77 K is considered by means of a nonlocal density functional theory (NLDFT) accounting for a disordered structure of pore walls. Pore size distribution analysis of various FDU-1 samples subject to different temperatures of calcination revealed three distinct groups of pores. The principal group of pores is identified as ordered spherical mesopores connected with each other by smaller interconnecting pores and irregular micropores present in the mesopore walls. To account for the entrances (connecting pores) into spherical mesopores, a concept of solid mass distribution with respect to the apparent density was introduced. It is shown that the introduction of the aforementioned distribution was sufficient to quantitatively describe experimental adsorption isotherms over the entire range of relative pressures spanning six decades.

Scaling and non-scaling of muscle activity, kinematics, and dynamics in sit-ups with different degrees of difficulty

The purpose of this study was to investigate how the CNS adjusts motor patterns for variants of a complex axial movement-the situp. Adjustments were induced by changing the support surface contact and mass distribution of the body. Healthy adults performed straight-legged sit-ups, 3 s in duration, with support added to or removed from the lumbar trunk, or with mass added to the head or to the legs. Each of these interventions either increased or decreased the difficulty of the task. The study addressed the extent to which changes in sit-up difficulty are compensated by scaling of muscle activity, kinematics, and dynamics versus the extent to which they are compensated by changing discretely the motor pattern. The analysis of muscle activity, kinematics, and dynamics focused on the first 30-40% of the sit-up-the trunk flexion phase-since this is the most critical part of the movement. Our results demonstrate that, in some respects, sit-up kinematics and dynamics scaled with difficulty, but in other respects, they did not. Muscle activity also scaled, in many respects, but in more difficult sit-ups, abdominal flexor activity decreased instead of increased. Non-scaling changes in these parameters suggest that complex movements, such as the sit-up, may require discrete changes in motor pattern in order to deal with large loads, which challenge the available leverage. (C) 2005 Elsevier Ltd. All rights reserved.

Electrochemical deposition of cupric ions for the determination of mass transfer rates to a stepped rotating cylinder electrode

The stepped rotating cylinder electrode (SRCE) geometry has been developed as a simple aid to the practical study of the flow-enhanced corrosion and applied electrochemistry problems commonly observed under conditions of disturbed, turbulent flow. The electrodeposition of cupric ions from an acid sulphate plating bath has been used to characterise differential rates of mass transfer to the SRCE. The variation in thickness of electrodeposited copperfilms has allowed the mapping of local rates of mass transfer over the active surface of this geometry. Both optical and scanning electron microscopy were used for the examination of metallographic sections to provide a high resolution evaluation of the distribution of mass transfer coefficient. Results are also discussed using the convective-diffusion model in combination with the existing direct numerical flow simulation (DNS) data for this geometry.

Nutrient partitioning during treatment of tuberculosis: gain in body fat mass but not in protein mass

Background: Tuberculosis is an important cause of wasting. The functional consequences of wasting and recovery may depend on the distribution of lost and gained nutrient stores between protein and fat masses. Objective: The goal was to study nutrient partitioning, ie, the proportion of weight change attributable to changes in fat mass (FM) versus protein mass (PM), during anti mycobacterial treatment. Design: Body-composition measures were made of 21 men and 9 women with pulmonary tuberculosis at baseline and after 1 and 6 mo of treatment. All subjects underwent dual-energy X-ray absorptiometry and deuterium bromide dilution tests, and a four-compartment model of FM, total body water (TBW), bone minerals (BM), and PM was derived. The ratio of PM to FM at any time was expressed as the energy content (p-ratio). Changes in the p-ratio were related to disease severity as measured by radiologic criteria. Results: Patients gained 10% in body weight (P < 0.001) from baseline to month 6. This was mainly due to a 44% gain in FM (P < 0.001); PM, BM, and TBW did not change significantly. Results were similar in men and women. The p-ratio decreased from baseline to month 1 and then fell further by month 6. Radiologic disease severity was not correlated with changes in the p-ratio. Conclusions: Microbiological cure of tuberculosis does not restore PM within 6 mo, despite a strong anabolic response. Change in the p-ratio is a suitable parameter for use in studying the effect of disease on body composition because it allows transformation of such effects into a normal distribution across a wide range of baseline proportion between fat and protein mass.

Determination of external and internal mass transfer limitation in nitrifying microbial aggregates

In this article we present a study of the effects of external and internal mass transfer limitation of oxygen in a nitrifying system. The oxygen uptake rates (OUR) were measured on both a macro-scale with a respirometric reactor using off-gas analysis (Titrimetric and Off-Gas Analysis (TOGA) sensor) and on a micro-scale with microsensors. These two methods provide independent, accurate measurements of the reaction rates and concentration profiles around and in the granules. The TOGA sensor and micro-sensor measurements showed a significant external mass transfer effect at low dissolved oxygen (DO) concentrations in the bulk liquid while it was insignificant at higher DO concentrations. The oxygen distribution with anaerobic or anoxic conditions in the center clearly shows major mass transfer limitation in the aggregate interior. The large drop in DO concentration of 22 - 80% between the bulk liquid and aggregate surface demonstrates that the external mass transfer resistance is also highly important. The maximum OUR even for floccular biomass was only attained at much higher DO concentrations ( approximate to 8 mg/L) than typically used in such systems. For granules, the DO required for maximal activity was estimated to be > 20mg/L, clearly indicating the effects of the major external and internal mass transfer limitations on the overall biomass activity. Smaller aggregates had a larger volumetric OUR indicating that the granules may have a lower activity in the interior part of the aggregate. (C) 2004 Wiley Periodicals, Inc.

Flow regime, hydrodynamics, floc size distribution and sludge properties in activated sludge bubble column, air-lift and aerated stirred reactors

This paper presents a comparative study how reactor configuration, sludge loading and air flowrate affect flow regimes, hydrodynamics, floc size distribution and sludge solids-liquid separation properties. Three reactor configurations were studied in bench scale activated sludge bubble column reactor (BCR), air-lift reactor (ALR) and aerated stirred reactor (ASR). The ASR demonstrated the highest capacity of gas holdup and resistance, and homogeneity in flow regimes and shearing forces, resulting in producing large numbers of small and compact floes. The fluid dynamics in the ALR created regularly directed recirculation forces to enhance the gas holdup and sludge flocculation. The BCR distributed a high turbulent flow regime and non-homogeneity in gas holdup and mixing, and generated large numbers of larger and looser floes. The sludge size distributions, compressibility and settleability were significantly influenced by the reactor configurations associated with the flow regimes and hydrodynamics.

Intercluster filaments of galaxies programme: Abundance and distribution of filaments in the 2dFGRS catalogue

Filaments of galaxies are known to stretch between galaxy clusters at all redshifts in a complex manner. In this Letter, we present an analysis of the frequency and distribution of intercluster galaxy filaments selected from the 2dF Galaxy Redshift Survey. Out of 805 cluster-cluster pairs, we find at least 40 per cent have bona fide filaments. We introduce a filament classification scheme and divide the filaments into several types according to their visual morphology: straight (lying on the cluster-cluster axis; 37 per cent), warped or curved (lying off the cluster-cluster axis; 33 per cent), sheets (planar configurations of galaxies; 3 per cent), uniform (1 per cent) and irregular (26 per cent). We find that straight filaments are more likely to reside between close cluster pairs and they become more curved with increasing cluster separation. This curving is toward a larger mass concentration in general. We also show that the more massive a cluster is, the more likely it is to have a larger number of filaments. Our results are found to be consistent with a cold dark matter cosmology.

The large scale distribution of galaxies in the Shapley Supercluster

We present new results of our wide-field redshift survey of galaxies in a 182 square degree region of the Shapley Supercluster (SSC) based on observations with the FLAIR-II spectrograph on the UK Schmidt Telescope (UKST). In this paper we present new measurements to give a total sample of redshifts for 710 bright (R less than or equal to 16.6) galaxies, of which 464 are members of the SSC (8000 < υ < 18 000 km s(-1)). Our data reveal that the main plane of the SSC (upsilon approximate to 14 500 km s(-1)) extends further than previously realised, filling the whole extent of our survey region of 10 degrees by 20 degrees on the sky (35 Mpc by 70 Mpc, for H-0 = 75 km s(-1) Mpc(-1)). There is also a significant structure associated with the slightly nearer Abell 3571 cluster complex (upsilon approximate to 12 000 km s(-1)) with a caustic structure evident out to a radius of 6 Mpc. These galaxies seem to link two previously identified sheets of galaxies and establish a connection with a third one at (V) over bar = 15 000 km s(-1) near RA = 13(h). They also tend to fill the gap of galaxies between the foreground Hydra-Centaurus region and the more distant SSC. We calculate galaxy overdensities of 5.0+/-0.1 over the 182 square degree region surveyed and 3.3+.-0.1 in a 159 square degree region excluding rich clusters. Over the large region of our survey the inter-cluster galaxies make up 46 per cent of all galaxies in the SSC region and may contribute a similar amount of mass to the cluster galaxies.

Distribution of major health risks: findings from the global burden of disease study

Background Most analyses of risks to health focus on the total burden of their aggregate effects. The distribution of risk-factor-attributable disease burden, for example by age or exposure level, can inform the selection and targeting of specific interventions and programs, and increase cost-effectiveness. Methods and Findings For 26 selected risk factors, expert working groups conducted comprehensive reviews of data on risk-factor exposure and hazard for 14 epidemiological subregions of the world, by age and sex. Age-sex-subregion-population attributable fractions were estimated and applied to the mortality and burden of disease estimates from the World Health Organization Global Burden of Disease database. Where possible, exposure levels were assessed as continuous measures, or as multiple categories. The proportion of risk-factor-attributable burden in different population subgroups, defined by age, sex, and exposure level, was estimated. For major cardiovascular risk factors (blood pressure, cholesterol, tobacco use, fruit and vegetable intake, body mass index, and physical inactivity) 43%-61% of attributable disease burden occurred between the ages of 15 and 59 y, and 87% of alcohol-attributable burden occurred in this age group. Most of the disease burden for continuous risks occurred in those with only moderately raised levels, not among those with levels above commonly used cut-points, such as those with hypertension or obesity. Of all disease burden attributable to being underweight during childhood, 55% occurred among children 1-3 standard deviations below the reference population median, and the remainder occurred among severely malnourished children, who were three or more standard deviations below median. Conclusions Many major global risks are widely spread in a population, rather than restricted to a minority. Population-based strategies that seek to shift the whole distribution of risk factors often have the potential to produce substantial reductions in disease burden.

Influence of charge size distribution on net-power draw of tumbling mill based on DEM modelling

Modelling and optimization of the power draw of large SAG/AG mills is important due to the large power draw which modern mills require (5-10 MW). The cost of grinding is the single biggest cost within the entire process of mineral extraction. Traditionally, modelling of the mill power draw has been done using empirical models. Although these models are reliable, they cannot model mills and operating conditions which are not within the model database boundaries. Also, due to its static nature, the impact of the changing conditions within the mill on the power draw cannot be determined using such models. Despite advances in computing power, discrete element method (DEM) modelling of large mills with many thousands of particles could be a time consuming task. The speed of computation is determined principally by two parameters: number of particles involved and material properties. The computational time step is determined by the size of the smallest particle present in the model and material properties (stiffness). In the case of small particles, the computational time step will be short, whilst in the case of large particles; the computation time step will be larger. Hence, from the point of view of time required for modelling (which usually corresponds to time required for 3-4 mill revolutions), it will be advantageous that the smallest particles in the model are not unnecessarily too small. The objective of this work is to compare the net power draw of the mill whose charge is characterised by different size distributions, while preserving the constant mass of the charge and mill speed. (C) 2004 Elsevier Ltd. All rights reserved.

Effect of body mass index changes between ages 5 and 14 on blood pressure at age 14 - Findings from a birth cohort study

Weight reduction in clinical populations of severely obese children has been shown to have beneficial effects on blood pressure, but little is known about the effect of weight gain among children in the general population. This study compares the mean blood pressure at 14 years of age with the change in overweight status between ages 5 and 14. Information from 2794 children born in Brisbane, Australia, and who were followed up since birth and had body mass index (BMI) and blood pressure measurements at ages 5 and 14 were used. Systolic and diastolic blood pressure at age 14 was the main outcomes and different patterns of change in BMI from age 5 to 14 were the main exposure. Those who changed from being overweight at age 5 to having normal BMI at age 14 had similar mean blood pressures to those who had a normal BMI at both time points: age- and sex-adjusted mean difference in systolic blood pressure 1.54 ( - 0.38, 3.45) mm Hg and in diastolic blood pressure 0.43 ( - 0.95, 1.81) mm Hg. In contrast, those who were overweight at both ages or who had a normal BMI at age 5 and were overweight at age 14 had higher blood pressure at age 14 than those who had a normal BMI at both times. These effects were independent of a range of potential confounding factors. Our findings suggest that programs that successfully result in children changing from overweight to normal-BMI status for their age may have important beneficial effects on subsequent blood pressure.

Differential distribution of ammonia- and nitrite-oxidising bacteria in flocs and granules from a nitrifying/denitrifying sequencing batch reactor

A lab-scale sequencing batch reactor was operated with alternating anoxic/aerobic conditions for nitrogen removal. Flocs and granules co-existed in the same reactor, with distinct aggregate structure and size, for over 180 days of reactor operation' Process data showed complete nitrogen removal, with temporary nitrite accumulation before full depletion of ammonia in the aerobic phase. Microbial quantification of the biomass by fluorescence in situ hybridisation showed that granules contained most of the nitrite-oxidising bacteria (NOB) whereas the ammonium-oxidising bacteria (AOB) seemed to be more abundant in the flocs. This was supported by microsensor measurements, which showed a higher potential of NO2- uptake than NH4 uptake in the granules. The segregation is possibly linked to the different growth rates of the two types of nitrifiers and the reactor operational conditions, which produced different sludge retention time for flocs and granules. The apparent physical separation of AOB and NOB in two growth forms could potentially affect mass transfer of NO2- from AOB to NOB, but the data presented here shows that it did not impact negatively on the overall nitrogen removal. (c) 2006 Elsevier Inc. All rights reserved.