Development of a Continuous Emulsion Copolymerization Process in a Tubular Reactor

This contribution describes the development of a continuous emulsion copolymerization processs for vinyl acetate and n-butyl acrylate in a tubular reactor. Special features of this reactor include the use of oscillatory (pulsed) flow and internals (sieve plates) to prevent polymer fouling and promote good radial mixing, along with a controlled amount of axial mixing. The copolymer system studied (vinyl acetate and butyl acrylate) is strongly prone to composition drift due to very different reactivity ratios. An axially dispersed plug flow model, based on classical free radical copolymerization kinetics, was developed for this process and used successfully to optimize the lateral feeding profile to reduce compositional drift. An energy balance was included in the model equations to predict the effect of temperature variations on the process. The model predictions were validated with experimental data for monomer conversion, copolymer composition, average particle size, and temperature measured along the reactor length.

Coarse-grid higher order finite-difference time-domain algorithm with low dispersion errors

Higher order (2,4) FDTD schemes used for numerical solutions of Maxwell`s equations are focused on diminishing the truncation errors caused by the Taylor series expansion of the spatial derivatives. These schemes use a larger computational stencil, which generally makes use of the two constant coefficients, C-1 and C-2, for the four-point central-difference operators. In this paper we propose a novel way to diminish these truncation errors, in order to obtain more accurate numerical solutions of Maxwell`s equations. For such purpose, we present a method to individually optimize the pair of coefficients, C-1 and C-2, based on any desired grid size resolution and size of time step. Particularly, we are interested in using coarser grid discretizations to be able to simulate electrically large domains. The results of our optimization algorithm show a significant reduction in dispersion error and numerical anisotropy for all modeled grid size resolutions. Numerical simulations of free-space propagation verifies the very promising theoretical results. The model is also shown to perform well in more complex, realistic scenarios.

Root Water Extraction under Combined Water and Osmotic Stress

Using a numerical implicit model for root water extraction by a single root in a symmetric radial flow problem, based on the Richards equation and the combined convection-dispersion equation, we investigated some aspects of the response of root water uptake to combined water and osmotic stress. The model implicitly incorporates the effect of simultaneous pressure head and osmotic head on root water uptake, and does not require additional assumptions (additive or multiplicative) to derive the combined effect of water and salt stress. Simulation results showed that relative transpiration equals relative matric flux potential, which is defined as the matric flux potential calculated with an osmotic pressure head-dependent lower bound of integration, divided by the matric flux potential at the onset of limiting hydraulic conditions. In the falling rate phase, the osmotic head near the root surface was shown to increase in time due to decreasing root water extraction rates, causing a more gradual decline of relative transpiration than with water stress alone. Results furthermore show that osmotic stress effects on uptake depend on pressure head or water content, allowing a refinement of the approach in which fixed reduction factors based on the electrical conductivity of the saturated soil solution extract are used. One of the consequences is that osmotic stress is predicted to occur in situations not predicted by the saturation extract analysis approach. It is also shown that this way of combining salinity and water as stressors yields results that are different from a purely multiplicative approach. An analytical steady state solution is presented to calculate the solute content at the root surface, and compared with the outputs of the numerical model. Using the analytical solution, a method has been developed to estimate relative transpiration as a function of system parameters, which are often already used in vadose zone models: potential transpiration rate, root length density, minimum root surface pressure head, and soil theta-h and K-h functions.

Influence of egg pre-storage heating period and storage length on incubation results

This experiment aimed at evaluating the influence of different heating times of settable eggs of Cobb 500 (R) broiler breeders before submitting them to different storage periods on egg weight loss, embryo mortality, and hatchability. A total number of 1,980 eggs were distributed in a completely randomized experimental design with a 3 x 3 factorial arrangement, comprising nine treatments with 22 replicates of 10 eggs each. The following factors were analyzed: pre-storage heating periods (0, 6, 12 hours at 36.92 degrees C) and storage periods (4, 9, 14 days at 12.06 degrees C). After storage, eggs were incubated under usual conditions, and were transferred to the hatcher at 442 hours of incubation. Eggs were weighed before heating, incubation, and transference to determine weight loss. Partial hatchability was determined at 480 hours, and total hatchability at 498 hours of incubation. Embryo mortality was determined in non-hatched eggs. It was concluded that heating eggs for six hour before storage improves incubation results as it decreases incubation length and late embryo mortality, therefore its use can be indicated in commercial operations. Storing eggs for 14 days and pre-heating for 14 days and pre-heating for 12 hours severely impair incubation results, and therefore are not recommended.

Influence of egg pre-storage heating period and storage length on the digestive tract of newly-hatched broiler chicks

An experiment was carried out to evaluate the effect of different heating times of settable eggs of Cobb 500 (R) broiler breeders before submitting them to different storage periods on body weight, digestive tract organ weights, and intestinal mucosa morphology of newly-hatched chicks. Settable eggs were distributed in a completely randomized experimental design with a 3 x 3 factorial arrangement: pre-storage heating periods (0, 6, 12 hours at 36.92 degrees C) and storage periods (4, 9, 14 days at 12.06 degrees C). Body weight and relative weights of the yolk sac, heart, liver, proventriculus+gizzard, and intestinal segments were measured in chicks hatching at 480 and 498 hours of incubation. Villi height, width and perimeter, and crypt depth < im) were measured in duodenal histological sections. It was concluded that pre-storage healing for six hours of eggs stored for four or nine days increases small intestine weight of newly-hatched chicks, but does not influence the morphology of the duodenal mucosa. Pre-storage heating for 12 hours negatively influences body weight and duodenal mucosa development, and therefore this practice is not recommended. Storage length does not have consistent effect on body weight and development of the gastrointestinal tract.

Detection of the TLR4 1196C > T Polymorphism by Mismatched-Polymerase Chain Reaction Using Plasmid DNA as Internal Control in Restriction Fragment Length Polymorphism Assays

Background: Restriction fragment length polymorphism (RFLP) is a common molecular assay used for genotyping, and it requires validated quality control procedures to prevent mistyping caused by impaired endonuclease activity. We have evaluated the usefulness of a plasmid-based internal control in RFLP assays. Results: Blood samples were collected from 102 individuals with acute myocardial infarction (AMI) and 108 non-AMI individuals (controls) for DNA extraction and laboratory analyses. The 1196C> T polymorphism in the toll-like receptor 4 (TLR4) gene was amplified by mismatched-polymerase chain reaction (PCR). Amplicons and pBluescript II SK-plasmid were simultaneously digested with endonuclease HincII. Fragments were separated on 2% agarose gels. Plasmid was completely digested using up to 55.2 nmL/L DNA solutions and 1 mu L PCR product. Nevertheless, plasmid DNA with 41.4 nM or higher concentrations was incompletely digested in the presence of 7 mL PCR product. In standardized conditions, TLR4 1196C> T variant was accurately genotyped. TLR4 1196T allele frequency was similar between AMI (3.1%) and controls (2.0%, p = 0.948). TLR4 SNP was not associated with AMI in this sample population. In conclusion, the plasmid-based control is a useful approach to prevent mistyping in RFLP assays, and it is validate for genetic association studies such as TLR4 1196C> T.

Turbulent Time and Length Scale Measurements in High-Velocity Open Channel Flows

In high-velocity open channel flows, the measurements of air-water flow properties are complicated by the strong interactions between the flow turbulence and the entrained air. In the present study, an advanced signal processing of traditional single- and dual-tip conductivity probe signals is developed to provide further details on the air-water turbulent level, time and length scales. The technique is applied to turbulent open channel flows on a stepped chute conducted in a large-size facility with flow Reynolds numbers ranging from 3.8 E+5 to 7.1 E+5. The air water flow properties presented some basic characteristics that were qualitatively and quantitatively similar to previous skimming flow studies. Some self-similar relationships were observed systematically at both macroscopic and microscopic levels. These included the distributions of void fraction, bubble count rate, interfacial velocity and turbulence level at a macroscopic scale, and the auto- and cross-correlation functions at the microscopic level. New correlation analyses yielded a characterisation of the large eddies advecting the bubbles. Basic results included the integral turbulent length and time scales. The turbulent length scales characterised some measure of the size of large vortical structures advecting air bubbles in the skimming flows, and the data were closely related to the characteristic air-water depth Y90. In the spray region, present results highlighted the existence of an upper spray region for C > 0.95 to 0.97 in which the distributions of droplet chord sizes and integral advection scales presented some marked differences with the rest of the flow.

Turbulence in Small Sub-Tropical Estuary with Semi-Diurnal Tides

In natural estuaries, contaminant transport is driven by the turbulent momentum mixing. The predictions of scalar dispersion can rarely be predicted accurately because of a lack of fundamental understanding of the turbulence structure in estuaries. Herein detailed turbulence field measurements were conducted at high frequency and continuously for up to 50 hours per investigation in a small subtropical estuary with semi-diurnal tides. Acoustic Doppler velocimetry was deemed the most appropriate measurement technique for such small estuarine systems with shallow water depths (less than 0.5 m at low tides), and a thorough post-processing technique was applied. The estuarine flow is always a fluctuating process. The bulk flow parameters fluctuated with periods comparable to tidal cycles and other large-scale processes. But turbulence properties depended upon the instantaneous local flow properties. They were little affected by the flow history, but their structure and temporal variability were influenced by a variety of mechanisms. This resulted in behaviour which deviated from that for equilibrium turbulent boundary layer induced by velocity shear only. A striking feature of the data sets is the large fluctuations in all turbulence characteristics during the tidal cycle. This feature was rarely documented, but an important difference between the data sets used in this study from earlier reported measurements is that the present data were collected continuously at high frequency during relatively long periods. The findings bring new lights in the fluctuating nature of momentum exchange coefficients and integral time and length scales. These turbulent properties should not be assumed constant.

Flow and axial dispersion simulation for traveling axisymmetric Taylor vortices

Numerical experiments using a finite difference method were carried out to determine the motion of axisymmetric Taylor vortices for narrow-gap Taylor vortex flow. When a pressure gradient is imposed on the flow the vortices are observed to move with an axial speed of 1.16 +/- 0.005 times the mean axial flow velocity. The method of Brenner was used to calculate the long-time axial spread of material in the flow. For flows where there is no pressure gradient, the axial dispersion scales with the square root of the molecular diffusion, in agreement with the results of Rosen-bluth et al. for high Peclet number dispersion in spatially periodic flows with a roll structure. When a pressure gradient is imposed the dispersion increases by an amount approximately equal to 6.5 x 10(-4) (W) over bar(2)d(2)/D-m, where (W) over bar is the average axial velocity in the annulus, analogous to Taylor dispersion for laminar flow in an empty tube.

The effect of protein binding on the hepatic first pass of O-acyl salicylate derivatives in the rat

In this work the in-situ perfused rat liver has been used to examine the effect of changing the protein content of the perfusate on the hepatic extraction of O-acyl esters of salicylic acid. The hepatic availability (F) of these solutes was studied at a flow-rate of 30 mt min(-1) with perfusate albumin concentrations of 0, 2, and 4% w/v. The hepatic availability of the esters was shown to decrease with increasing carbon-chain length in the O-acyl group; for all the esters the hepatic availability increased with increasing albumin concentration in the perfusate. The dispersion-model-derived efficiency number (R-N) Of the esters was shown to increase with increasing lipophilicity and decrease with increasing albumin concentration in the perfusate. The unbound fraction (f(u),) of the esters decreased with lipophilicity. R-N/f(u), for acetylsalicylic acid remained relatively constant as the albumin concentration was increased. However, R-N/f(u), for n-pentanoyl- and n-hexanoylsalicylic acids increased significantly as albumin concentration increased from 0% to 4%. Thus, for the more lipophilic solutes (n-pentanoyl- and n-hexanoylsalicylic acids) the presence of albumin apparently facilitates the uptake of unbound solute relative to acetylsalicylic acid.

Optics of the developing fish eye: comparisons of Matthiessen's ratio and the focal length of the lens in the black bream Acanthopagrus butcheri (Sparidae, Teleostei)

Matthiessen's ratio (distance from centre of lens to retina: lens radius) was measured in developing black bream, Acanthopagrus butcheri (Sparidae, Teleostei). The value decreased over the first 10 days post-hatch from 3.6 to 2.3 along the nasal and from four to 2.6 along temporal axis. Coincidentally, there was a decrease in the focal ratio of the lens (focal length:lens radius). Morphologically, the accommodatory retractor lentis muscle appeared to become functional between 10-12 days post-hatch. The results suggest that a higher focal ratio compensates for the relatively high Matthiessen's ratio brought about by constraints of small eye size during early development. Combined with differences in axial length, this provides a means for larval fish to focus images from different distances prior to the ability to accommodate. (C) 1999 Elsevier Science Ltd. All rights reserved.

Modeling of hepatic elimination and organ distribution kinetics with the extended convection-dispersion model

The conventional convection-dispersion (also called axial dispersion) model is widely used to interrelate hepatic availability (F) and clearance (Cl) with the morphology and physiology of the liver and to predict effects such as changes in liver blood flow on F and Cl. An extended form of the convection-dispersion model has been developed to adequately describe the outflow concentration-time profiles for vascular markers at both short and long times after bolus injections into perfused livers. The model, based on flux concentration and a convolution of catheters and large vessels, assumes that solute elimination in hepatocytes follows either fast distribution into or radial diffusion in hepatocytes. The model includes a secondary vascular compartment, postulated to be interconnecting sinusoids. Analysis of the mean hepatic transit time (MTT) and normalized variance (CV2) of solutes with extraction showed that the discrepancy between the predictions of MTT and CV2 for the extended and conventional models are essentially identical irrespective of the magnitude of rate constants representing permeability, volume, and clearance parameters, providing that there is significant hepatic extraction. In conclusion, the application of a newly developed extended convection-dispersion model has shown that the unweighted conventional convection-dispersion model can be used to describe the disposition of extracted solutes and, in particular, to estimate hepatic availability and clearance in booth experimental and clinical situations.

Synthesis of silica films at the air/water interface: Effect of template chain length and ionic strength

We have grown surfactant-templated silicate films at the air-water interface using n-alkyltrimethylammonium bromide and chloride in an acid synthesis with tetraethyl orthosilicate as the silicate source. The films have been grown with and without added salt (sodium chloride, sodium bromide) and with n-alkyl chain lengths from 12 to 18, the growth process being monitored by X-ray reflectometry. Glassy, hexagonal, and lamellar structures have been produced in ways that are predictable from the pure surfactant-water phase diagrams. The synthesis appears to proceed initially through an induction period characterized by the accumulation of silica-coated spherical micelles near the surface. All syntheses, except those involving C(12)TACl, show a sudden transformation of the spherical micellar phase to a hexagonal phase. This occurs when the gradually increasing ionic strength and/or changing ethanol concentration is sufficient to change the position of boundaries within the phase diagram. A possible mechanism for this to occur may be to induce a sphere to rod transition in the micellar structure. This transformation, as predicted from the surfactant-water phase diagram, can be induced by addition of salts and is slower for chloride than bromide counteranions. The hexagonal materials change in cell dimension as the chain length is changed in a way consistent with theoretical model predictions. All the materials have sufficiently flexible silica frameworks that phase interconversion is observed both from glassy to hexagonal and from hexagonal, to lamellar and vice versa in those surfactant systems where multiple phases are found to exist.

Commentary: Using the convection-dispersion model and transit time density functions in the analysis of organ distribution kinetics

The convection-dispersion model and its extended form have been used to describe solute disposition in organs and to predict hepatic availabilities. A range of empirical transit-time density functions has also been used for a similar purpose. The use of the dispersion model with mixed boundary conditions and transit-time density functions has been queried recently by Hisaka and Sugiyanaa in this journal. We suggest that, consistent with soil science and chemical engineering literature, the mixed boundary conditions are appropriate providing concentrations are defined in terms of flux to ensure continuity at the boundaries and mass balance. It is suggested that the use of the inverse Gaussian or other functions as empirical transit-time densities is independent of any boundary condition consideration. The mixed boundary condition solutions of the convection-dispersion model are the easiest to use when linear kinetics applies. In contrast, the closed conditions are easier to apply in a numerical analysis of nonlinear disposition of solutes in organs. We therefore argue that the use of hepatic elimination models should be based on pragmatic considerations, giving emphasis to using the simplest or easiest solution that will give a sufficiently accurate prediction of hepatic pharmacokinetics for a particular application. (C) 2000 Wiley-Liss Inc. and the American Pharmaceutical Association J Pharm Sci 89:1579-1586, 2000.

Decompositions of complete multipartite graphs into cycles of even length

Necessary and sufficient conditions for the existence of an edge-disjoint decomposition of any complete multipartite graph into even length cycles are investigated. Necessary conditions are listed and sufficiency is shown for the cases when the cycle length is 4, 6 or 8. Further results concerning sufficiency, provided certain small decompositions exist, are also given for arbitrary even cycle lengths.