Mathematical modeling and the estimation of parameters for the melt viscosity of polyamides

Capillary rheometry data of a range of commercial polyamide engineering materials was obtained from a mould-flow analysis material database, from which melt viscosity data was obtained at different temperatures, which made comparison of the viscosities difficult. In an attempt to make a reasonable comparison between the melt viscosities of the various polyamide materials at different temperatures, it was necessary to obtain the mathematical functions which describe the relationships between: (i) the melt viscosity and the shear rate, (ii) the melt viscosity and temperature and (iii) the melt viscosity and the combined effect of the shear rate and temperature of each of the polyamides studied. Therefore, melt viscosity was modelled as a function of shear rate at the three temperatures (275°C, 295°C and 315°C), at which the viscosities were determined. The function obtained represented smoothed versions of the experimental data, eliminating the experimental noise and enabling the generation of melt viscosity data at the six different shear rates of the original data. It was established that the melt viscosity as a function of shear rate at constant temperature, in the shear rate range 500-700 s m 1 , is incorrectly described by the Ostwald-de-Waele's model, \eta_{\rm T}={\rm f}({\dot \gamma})={\rm K}({\dot \gamma})^{({\rm n}-1)} , while the melt viscosity of the polyamides studied, as a function of temperature, is correctly described by the model \eta_{\dot \gamma}={\rm g}{(\rm T)}={\rm Pe}^{\left (\rm {QT/R}\right )} . But the response-surface melt viscosity is effectively described as a function of both shear rate and temperature by the model: \eta=\vert {\dot \gamma}\vert^{(\rm n-1)}{\rm Ae}^{(\rm ET/R)} . The parameters A, E and n are highly interrelated as they all influence the average melt viscosity. All are temperature sensitive and also, to some degree, shear sensitive.     

Structural modeling of the pro-ocytocin-neurophysin precursor

The hormonal precursor pro-ocytocin-neurophysin is activated by selectivecleavage at Arg2-Ala13, producing mature ocytocin and neurophysin. Tounderstand the cleavage mechanism better, and in particular the recognitionof the cleavage site, it is necessary to characterize the three-dimensionalstructure of the precursor molecule. Here we combine a variety ofexperimental data with molecular modeling and dynamics calculations toderive possible precursor conformations. In the models obtained, theN-terminus of the precursor, corresponding to the ocytocin segment, ishydrogen bonded in a pocket of the neurophysin moiety in a similar mannerto a crystallographically obtained non-covalent complex between the twomolecules. The calculations suggest that although the ocytocin segment isrelatively flexible, it adopts a stable, broad loop structure in thevicinity of the cleavage region, which may constitute the structuralelement recognized by the cleaving enzyme. The calculations also suggest apossible widening of the distance between the two neurophysin domains inthe precursor relative to that in the non-covalent neurophysin- ocytocincomplex.     

Development and evaluation of an improved soil test for phosphorus: 1. The influence of phosphorus fertilizer solubility and soil properties on the extractability of soil P

The objective of this work was to develop and evaluate a soil test suitable for estimating the phosphorus status of soils whether they were fertilized with soluble or sparingly soluble P fertilizers or both. Four New Zealand soils of contrasting P sorption capacity and exchangeable Ca content were incubated alone or with monocalcium phosphate (MCP), reactive North Carolina (NC) phosphate rock or unreactive Florida (FRD) rock, at 240 mg P kg^–1 soil, to allow the P sources of different solubilities to react with each soil and provide soil samples containing different amounts of extractable P, Ca and residual phosphate rock. The phosphorus in the incubated soils was fractionated into alkali soluble and acid soluble P fractions using a sequential extraction procedure to assess the extent of phosphate rock dissolution. Eight soil P tests [three moderately alkaline — Olsen (0.5M NaHCO₃) modified Olsen (pretreatment with 1M NaCl) and Colwell; three acid tests — Bray 1, modified Bray 1 and Truog; and two resin tests — bicarbonate anion exchange resin (AER) and combined AER plus sodium cation exchange resin (CER)] were assessed in their ability to extract P from the incubated soils.The 0.5M NaHCO₃ based alkaline tests could not differentiate between the Control and FRD treatments in any soil nor between the Control, NC and FRD treatments in the high P sorption soils. The acid extractants appeared to be affected by the P sorption capacity of the soil probably because of reabsorption of dissolved P in the acid medium. The AER test gave results similar to Olsen. Only the combined AER + CER test extracted P in amounts related to the solubility of the P sources incubated with each soil. Furthermore, when soil samples were spiked with FRD and NC and extracted immediately, the P extracted by the AER + CER test, over and above the control soils, increased with the amount and chemical reactivity of the rocks. There was no extraction of rock P by any of the alkaline extractions.Increases in the amounts of P extracted (P) by each soil test from the fertilized soils, over and above the control soils were compared with the amounts ofP dissolved from the fertilizers during incubation (measured by P fractionation). Soil P sorption capacity had least influence on the amounts of P extracted by the AER + CER and Colwell tests. However, the Colwell test was unable to differentiate between all P sources in all four soils and suffered from the disadvantage of producing coloured extracts. The AER + CER test appeared to have the potential to assess the available P status of soils better than the other tests used because of its ability to extract a representative portion of residual PR (in accordance with the amount and reactivity) and dissolved P, and thus to differentiate between fertilizer treatments in all four soils.     

Process-based mass-balance modeling of soil phosphorus availability in a grassland fertilized with N and P

Modeling changes in plant-available soil P in relation to P budgets should integrate the isotopic kinetic approach, which describes the dynamics of P ion transfer at the solid-to-solution interface. We tested a process-based mass-balance model that uses the quantity of P ions in solution, the diffusive P ions (Pr) in the solid phase, and the annual P budget to describe the soil P availability of a timothy (Phleum pratense L.) grassland that received additions of annual P and N fertilizer. An experiment was established on a gravely-sandy loam soil in 1998, with combinations of P (0, 15, 30, and 45 kg ha^?1) and N (0, 60, 120, and 180 kg ha^?1) applied annually from 1999 to 2006. An isotopic dilution analysis was performed on soils sampled in 2006 to calibrate the Freundlich kinetic equation which describes the dynamics of Pr transfer at the solid-to-solution interface as a function of time (t) and concentration of P ions in solution (Cp). Model simulations were performed over 9 years (1999–2007). Measurements of Cp from soils sampled between 2001 and 2007 were compared with simulated values to evaluate model performance. The amount of Pr was estimated for two transfer periods, of 2 and 3 months, to evaluate the extent and contribution of slow P ion reactions. The Freundlich kinetic equation was defined as: Pr = 7.78 × Cp^0.41 × t ^0.36 (with Pr < Pr_LIMIT, 192 observations, Adj. R ² = 1.0, P < 0.001). Simulated Pr values were 74 and 84% of total inorganic soil P for the transfer periods of 2 and 3 months, respectively. For the two transfer periods, and for each combination of N and P additions, simulations accurately reflected the long-term effects of P and N fertilization on the trends of measured Cp with root mean square deviation (RMSD) between measured and simulated values of less than 0.17. Across P applications, the simulations were slightly improved with a 2-month transfer period for limiting N conditions (0 and 60 kg N ha^?1; Y = 0.95X + 0.06, R² = 0.76, RMSD = 0.08) and a 3-month transfer period for non-limiting conditions (120 and 180 kg N ha^?1; Y = 0.86X + 0.04, R² = 0.78, RMSD = 0.06). This approach needs to be tested in various soil types and diverse cropping systems because the estimation of Pr value can be quite sensitive to the extent of rapid and slow reactions, hence the transfer periods. For this gravely-sandy loam soil, the proposed approach accurately describes the functioning of P cycling and confirms the agronomic importance of solution and solid phase P ions in managed grasslands.     

Mathematical modeling for the estimation of lipase activity by agar diffusion method

A mathematical model was developed to estimate the lipase activities from the experimentally obtained physical dimension of halo, formed by a diffusing lipase through agar media. A diffusion equation based upon the mass balance was derived in cylindrical coordinates, the integration of which was carried out by using finite difference method. A regressional analysis of the experimental data using the proposed model has brought the values for the hindered diffusivity of lipase through agar media and the minimum effective lipase concentration of 0.817 × 10⁻⁶ cm² /s and 2.86 unit/ cm³, respectively. The procedures, delineated in this work are considered to be useful for the quantitative analysis of haloforming enzymes at predetermined standard conditions.     

Thermodynamic modeling of vapor-liquid equilibria and excess properties of the binary systems containing diethers and n-alkanes by cubic equation of state

A comparison of the performances of two different approaches of cubic equations of state models, based on a classical van der Waals and mixing rules incorporating theG ^E equation, was carried out for correlation of Vapor-Liquid Equilibria (VLE), H^E and C _P ^E data alone, and simultaneous correlation of VLE+H^E, VLE+C _P ^E , H^E +C _P ^E and VLE+H^E +C _P ^E data for the diethers (1,4-dioxane or 1,3-dioxolane) with n-alkane systems. For all calculations the Peng-Robinson-Stryjek-Vera cubic equation of state (PRSV CEOS) was used. A family of mixing rules for the PRSV CEOS based on the Modified van der Waals one-fluid mixing rule (MvdW1) and two well-known CEOS/G^E mixing rules (MHV1 and MHV2), was considered. The NRTL equation, as the G^E model with linear or reciprocal temperature dependent parameters, was incorporated in the CEOS/G^E models. The results obtained by the CEOS/G^E models exhibit significant improvement in comparison to the MvdW1 models.     

Structural basis for the difference in thermodynamic properties between the two cysteine proteinase inhibitors human stefins A and B

Homology modelling has been used to model stefin A based onthe X-ray structure of stefin B. Several models have been producedby interactive modelling or positioning of the side chains byMonteCarlo procedure with simulated annealing.The quality of modelswas evaluated by calculation of the free energy of hydration,3D-1D potential or buried area of surface accessibility. StefinA is a thermostable protein, exhibiting a two-state denaturation,while stefin B denaturesat a 40°C lower temperature andforms a stable molten globule intermediate under mild denaturingconditions. From the tertiary structures, thermodynamic functionswere predicted, conforming closely to the experimental calorimetrkresults. Polar and apolar buried areas of surface accessibilitywere obtained by structural deconvolution of the thermograms.It is suggested that the bask difference between the stefinsis the domination of hydrophobic interaction in the stabilizationof stefin B, which is due to its non-specific nature leadingto the formation of a molten globule intermediate. Modellingof stefin A predicts increased numbers of hydrogen bonds whichstabilize it and the increase the cooperativity of its denaturation.     

Structural properties of magnetic nanoparticles determine their heating behavior - an estimation of the in vivo heating potential

Magnetically induced heating of magnetic nanoparticles (MNP) in an alternating magnetic field (AMF) is a promising minimally invasive tool for localized tumor treatment by sensitizing or killing tumor cells with the help of thermal stress. Therefore, the selection of MNP exhibiting a sufficient heating capacity (specific absorption rate, SAR) to achieve satisfactory temperatures in vivo is necessary. Up to now, the SAR of MNP is mainly determined using ferrofluidic suspensions and may distinctly differ from the SAR in vivo due to immobilization of MNP in tissues and cells. The aim of our investigations was to study the correlation between the SAR and the degree of MNP immobilization in dependence of their physicochemical features.In this study, the included MNP exhibited varying physicochemical properties and were either made up of single cores or multicores. Whereas the single core MNP exhibited a core size of approximately 15 nm, the multicore MNP consisted of multiple smaller single cores (5 to 15 nm) with 65 to 175 nm diameter in total. Furthermore, different MNP coatings, including dimercaptosuccinic acid (DMSA), polyacrylic acid (PAA), polyethylenglycol (PEG), and starch, wereinvestigated. SAR values were determined after the suspension of MNP in water. MNP immobilization in tissues was simulated with 1% agarose gels and 10% polyvinyl alcohol (PVA) hydrogels.The highest SAR values were observed in ferrofluidic suspensions, whereas a strong reduction of the SAR after the immobilization of MNP with PVA was found. Generally, PVA embedment led to a higher immobilization of MNP compared to immobilization in agarose gels. The investigated single core MNP exhibited higher SAR values than the multicore MNP of the same core size within the used magnetic field parameters. Multicore MNP manufactured via different synthesis routes (fluidMAG-D, fluidMAG/12-D) showed different SAR although they exhibited comparable core and hydrodynamic sizes. Additionally, no correlation between ζ-potential and SAR values after immobilization was observed.Our data show that immobilization of MNP, independent of their physicochemical properties, can distinctly affect their SAR. Similar processes are supposed to take place in vivo, particularly when MNP are immobilized in cells and tissues. This aspect should be adequately considered when determining the SAR of MNP for magnetic hyperthermia.     

Correlations between surface properties of graphite and the first cycle specific charge loss in lithium-ion batteries

We report the influence of two surface parameters, the active surface area (ASA) and the surface chemistry (oxygen functional groups) on the first electrochemical reduction of graphite. The experimental results highlight two important points. One, the ASA is the determining parameter which controls the exfoliation during the first electrochemical cycle. An ASA limit (ca. 0.2 m² g⁻¹) above which the exfoliation is suppressed was experimentally found. Below or above this limit, the specific charge loss remains almost constant even if the ASA changes. Two, for a sample having an ASA value higher than 0.2 m² g⁻¹, it is shown that the presence of oxygen groups at the surface is critical for the formation of an efficient solid electrolyte interphase (SEI) layer. The lack of oxygen groups during the first electrochemical reduction cycle hinders the electrolyte reduction process, and consequently increases the specific charge loss via exfoliation of the graphite electrode. This was confirmed by TPD measurement where significant release of CO gas occured above 400 °C, suggesting the presence of high-thermal-stable surface oxygen-containing groups of different natures in the as-received - SLX50 sample. Finally, it was found that H₂ treatment avoids the formation of oxygen-containing groups during air contact leading to exfoliation of the graphite sample.     

土体标度分布参数与其物理力学性质的关系研究

土体标度分布参数可以客观地表达土体颗粒组成的整体特征,便于建立其与土体物理力学性质之间的定量关系,具有重要的理论意义和实际应用价值.以土体的标度分布理论为基础,结合土体渗透实验和直剪实验,研究了土体标度分布参数与其渗透系数、抗剪强度指标(黏聚力、内摩擦角)的关系,结果表明:土体渗透系数K与标度分布参数μ呈负对数关系,与...     

A new model for estimation of the critical properties of alkanes

A simple model is proposed to estimate the critical properties of alkanes—temperature, pressure, and volume. This model is dependent on normal boiling and molecular weight of hydrocarbons. The model has been expanded based on a Taylor series in the form of a polynomial function of normal boiling. Because methane has the simplest structure among hydrocarbons, this model has been calculated around methane. The coefficients of this model were assumed in the form of a linear function of molecular weight. These parameters can be obtained from regression between experimental results and results from this model. By a comparison of this model and previous models, it is shown that this model is suitable to use for estimation of the critical properties of alkanes.From Teoreticheskie Osnovy Khimicheskoi Tekhnologii, Vol. 39, No. 1, 2005, pp. 80–82. Original English Text Copyright © 2005 by Pazuki, Mokhatab, Jahanshahi.This article was submitted by the authors in English.     

Structural basis for the properties of two single-site proline mutants of CYP102A1 (P450BM3)

The crystal structures of the haem domains of Ala330Pro and Ile401Pro, two single‐site proline variants of CYP102A1 (P450_BM3) from Bacillus megaterium, have been solved. In the A330P structure, the active site is constricted by the relocation of the Pro329 side chain into the substrate access channel, providing a basis for the distinctive C? H bond oxidation profiles given by the variant and the enhanced activity with small molecules. I401P, which is exceptionally active towards non‐natural substrates, displays a number of structural similarities to substrate‐bound forms of the wild‐type enzyme, notably an off‐axial water ligand, a drop in the proximal loop, and the positioning of two I‐helix residues, Gly265 and His266, the reorientation of which prevents the formation of several intrahelical hydrogen bonds. Second‐generation I401P variants gave high in vitro oxidation rates with non‐natural substrates as varied as fluorene and propane, towards which the wild‐type enzyme is essentially inactive. The substrate‐free I401P haem domain had a reduction potential slightly more oxidising than the palmitate‐bound wild‐type haem domain, and a first electron transfer rate that was about 10 % faster. The electronic properties of A330P were, by contrast, similar to those of the substrate‐free wild‐type enzyme.     

Automation of group-contribution techniques for estimation of thermophysical properties

A computer algorithm is presented which predicts thermophysical properties of mixtures using only two-dimensional chemical structures. It applies a combination of techniques for the analysis of group contributions and other characteristics of a chemical structure in a table-driven format. These techniques are used to examine the error behavior for predictions of critical properties and saturated properties. UNIFAC predictions of activity coefficients are combined with pure-component properties to demonstrate that accurate estimates of azeotrope behavior and K-values can be obtained.     

Relationships between soil urease activity and other properties of some tropical wetland rice soils

Ten Philippine wetland rice soils differing widely in pH, texture and organic matter were studied to determine relationships between urease activity and other soil properties. Simple correlation analyses of urease activity with soil properties indicated that urease activity was correlated highly significantly with total N (r = 0.91)^**, and organic C (r = 0.89^**) but was not significantly correlated with CEC, Clay, pH active Fe or active Mn content. From multiple regression analyses it was observed that organic matter content of soils measured by organic C and total N accounted for most of the variation in urease activity.     

Influence of soil organic carbon on the interpretation of soil test P for wheat grown on alkaline soils

Organic carbon is known to alter crop response to applied phosphorus (P) but that fact has not been incorporated in soil test interpretations. To achieve this objective, field experiments with wheat were conducted for four years on alkaline soils of Punjab, India. The experimental soils ranged from loamy sand to loam in texture, 7.4 to 9.6 in pH, 0.16 to 0.75% in organic carbon (OC) and 2 to 40 mg Olsen extractable P kg^–1 soil. Response of wheat to fertilizer phosphorus application was related to the combined effect of Olsen P and soil OC content. At a given Olsen P level, wheat yield was a function of soil OC content. Multiple regression analysis of the data showed that OC content <0.2% did not affect yield significantly. At values >0.6%, OC along with Olsen P accounted for 97% of the variation in yield and there was no response to applied fertilizer P. Yield isoquants for 4 and 5 tons grains ha^–1 showed that for a given Olsen P level, as OC content increased the amount of fertilizer P required to achieve a yield target decreased. It was shown that OC may be used to approximate the contribution of organic P mineralization to plant available soil P during a growing season. The reliability of fertilizer recommendations based on Olsen P may be improved on some alkaline soils by consideration of soil OC content.     

A composite equation of state for the modeling of sonic carbon dioxide jets in carbon capture and storage scenarios

The development of a novel composite two‐phase method to predict the thermodynamic physical properties of carbon dioxide (CO₂) above and below the triple point, applied herein in the context of Reynolds‐Averaged Navier–Stokes computational modeling has been detailed here. A number of approaches have been combined to make accurate predictions in all three phases (solid, liquid, and gas) and at all phase changes for application in the modeling of releases of CO₂ at high pressure into the atmosphere. Predictions of a free release of CO₂ into the atmosphere from a reservoir at a pressure of 10 MPa and a temperature of 283 K, typical of transport conditions in carbon capture and storage scenarios, is examined. A comparison of the results shows that the sonic CO₂ jet that forms requires a three‐phase equation of state including the latent heat of fusion to realistically simulate its characteristics. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3928–3942, 2013