Chemorheology of photopolymerizable acrylates using a modified Boltzmann sigmoidal model

Experiments were conducted to evaluate the influence of ambient photoconversion on rheology for a range of photopolymerizable urethane dimethacrylate (UDMA) resins containing varying amounts of three comonomers including 1,6 hexane diol‐dimethacrylate (HDDMA), an alkoxylated cyclohexane dimethanol diacrylate monomer (CD‐582), and hydroxyethyl methacrylate (HEMA). Experiments were performed both as a function of composition and time‐dependent dose varying the intensity using a photorheometer. A semilog‐based sigmoidal model allowed the determination of four physical model parameters to define the relationship between reaction kinetics and its dynamic influence on viscosity. We have observed induction times and viscosity changes associated with the model that shows a trend in reaction kinetics in the following order from most to least reactive: UDMA > CD582 > HDDMA > HEMA. With increasing amounts of reactive diluent included in the formulation, the kinetics of reaction was more sluggish. The value of this sigmoidal model is that it could help define formulation and process conditions most likely to control crosslinking to maximize dimensional stability or other thermophysical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2319–2325, 2008     

Computation of electrostatic forces between solvated molecules determined by the Poisson-Boltzmann equation using a boundary element method

A rigorous approach is proposed to calculate the electrostatic forces among an arbitrary number of solvated molecules in ionic solution determined by the linearized Poisson-Boltzmann equation. The variational principle is used and implemented in the frame of a boundary element method (BEM). This approach does not require the calculation of the Maxwell stress tensor on the molecular surface, therefore it totally avoids the hypersingularity problem in the direct BEM whenever one needs to calculate the gradient of the surface potential or the stress tensor. This method provides an accurate and efficient way to calculate the full intermolecular electrostatic interaction energy and force, which could potentially be used in Brownian dynamics simulation of biomolecular association. The method has been tested on some simple cases to demonstrate its reliability and efficiency, and parts of the results are compared with analytical results and with those obtained by some known methods such as adaptive Poisson-Boltzmann solver.     

Modeling the propane combustion process within a micro-catalytic porous combustor by using the lattice Boltzmann method

Journal of Thermal Analysis and Calorimetry - Understanding the micro-catalytic porous combustion mechanisms is vital importance in improving the energy conversion efficiency of a combustion...     

Thermodynamic properties of the Cu-Au system using a face-centered-cubic lattice model with a renormalized potential

A Monte Carlo simulation is carried out to study thermodynamic properties of Cu-Au alloys using a face-centered-cubic (fcc) lattice-gas model. To obtain quantitatively accurate results, a Finnis-Sinclair-type potential, which has been widely used for molecular dynamics (MD) simulations, is employed. To overcome some shortcomings of lattice-gas models such as neglecting vibrational entropy, the potential is mapped onto the fcc lattice using the renormalization technique. The renormalized potential gives an improved Cu-Au phase diagram compared to the original MD potential applied directly on the lattice.     

Coupled solution of a time-dependent collisional-radiative model and Boltzmann equation for atomic hydrogen plasmas: possible implications with LIBS plasmas

A time-dependent collisional-radiative model coupled to the Boltzmann equation for the electron energy distribution function has been developed for atomic hydrogen plasmas. Different non-equilibrium initial conditions have been studied. The results show that in the early stage of the evolution as well as in the recombination phase, both distribution functions of excited states and of electrons deviate from the corresponding equilibrium (Boltzmann and Maxwell) distributions. The possible implications of the results with LIBS plasmas are finally discussed.     

Symmetric random walk on a regular lattice with an elastic barrier: diffusion equation and the boundary condition

We examine here the symmetric random-walk model in which a particle can jump only to adjacent sites on a regular lattice, and discuss, in the light of the works of Chandrasekhar, Goodrich, van Kampen, and Oppenheim, the reduction of the problem of random walk in the presence of an elastic barner to a boundary value problem.     

Selective determination of tryptophan by using a carbon paste electrode modified with an overoxidized polypyrrole film.

We report on the selective determination of tryptophan, using a carbon paste electrode coated with an overoxidized polypyrrole film. Out of 21 protein amino acids, only tryptophan and tyrosine exhibited an oxidative voltammetric response with this electrode. Tryptophan, which was preferentially concentrated to the electrode under an open circuit condition, was determined by the stripping voltammetric technique with a linear response range of 10-100 microM. For the determination of 10 microM tryptophan, interference from a 15-fold excess of tyrosine gave an positive error of 6%, while the other amino acids did not exhibit any detectable interference.     

Impedimetric detection of trinitrotoluene by using a glassy carbon electrode modified with a gold nanoparticle@fullerene composite and an aptamer-imprinted polydopamine

Microchimica Acta - This study introduces a method based on a combination of aptasensing and molecular imprinting for highly sensitive detection of 2,4,6-trinitrotoluene (TNT). An amino-aptamer...     

Silver-selective sensor using an electrode-separated piezoelectric quartz crystal modified with a chitosan derivative.

Silver(I) adsorbed selectively onto a quartz plate modified with N-(2-pyridylmethyl)chitosan in an ammonium chloride buffer solution containing EDTA, and the frequency of the quartz plate increased. It was supposed that the increasing frequency was caused by the desorption of adsorbed water on the chitosan derivative, which was induced from the reaction of silver(I) with the chitosan derivative. The concentration of the buffer, pH, temperature, conductivity and eluent affected the frequency shift resulting from the adsorption of silver(I). The frequency decreased at a conductivity lower than 2.2 mS/cm, and increased with increasing conductivity above this value. The frequency shifts caused by the adsorption of silver(I) were proportional to the concentration over the range 10-80 nM of silver(I), and the correlation coefficient was 0.9969. The detection limit and the relative standard deviation at 50 nM for five times were 6 nM and 3.4%, respectively. The proposed method was simple while showing higher sensitivity and selectivity.     

Optimization and effect of wall conduction on natural convection in a cavity with constant temperature heat source: Using lattice Boltzmann method and neural network algorithm

Journal of Thermal Analysis and Calorimetry - In this paper, the natural convection (NC) of the Al2O3–H2O nanofluids (NFs) in a cavity with a heat source in its center is numerically...     

Determination of Ochratoxin A in apples contaminated with Aspergillus ochraceus by using a microfluidic competitive immunosensor with magnetic nanoparticles

Ochratoxin A (OTA) is a mycotoxin produced by filamentous fungi of the genus Aspergillus and Penicillium that presents carcinogenic, teratogenic and nephrotoxic properties. In this work, we have developed, characterized and applied an immunoassay methodology comprised of magnetic nanoparticles (MNPs) as platform for immobilizing bioactive materials incorporated into a microfluidic system for rapid and sensitive quantification of Ochratoxin A (OTA) in apples (Red Delicious) contaminated with Aspergillus ochraceus. The sensor has the potential for automation and the detection of OTA was carried out using a competitive indirect immunoassay method based on the use of anti-OTA monoclonal antibodies immobilized on 3-aminopropyl-modified MNPs. The total assay time into the microfluidic competitive immunosensor was 16 min, and the calculated detection limit was 0.05 μg kg(-1). Moreover, the intra- and inter-assay coefficients of variation were below 6.5%. The proposed method can be a very promising analytical tool for the determination of OTA in apparently healthy fruits post-harvest and for its application in the agricultural industry.     

Diffuse double layer interaction between two parallel plates with constant surface charge density in an electrolyte solution IV. Numerical calculation of the interaction between similar plates using the non-linear Poisson-Boltzmann equation

Summary A method is presented for numerical calculation of the diffuse double layer interaction between two parallel similar plates with constant surface charge density in a symmetrical electrolyte solution. The non-linear Poisson-Boltzmann equation is used and the influence of the electric field induced within the plates by the overlapping of the double layers is taken into account. Numerical tables are given for the force and potential energy of interaction. The applicability of the Debye-Hückel approximation is also considered.

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Zusammenfassung Es wird eine Methode für numerische Berechnung der Wechselwirkung der diffusen Doppelschichten zwischen zwei parallelen gleichen Platten mit konstanter Oberflächenladungsdichte in einer symmetrischen Elektrolytlösung gezeigt. Die nichtlineare Poisson-Boltzmannsche Gleichung wird benutzt, und der Einfluß des durch die Überlappung der Doppelschichten induzierten elektrischen Feldes innerhalb der Platten wird berücksichtigt. Numerische Tabellen werden für die Kraft und die potentielle Energie der Wechselwirkung gegeben. Die Anwendbarkeit der Debye-Hückel-Näherung wird auch untersucht.

     

A study on the effect of magnetic field and the sinusoidal boundary condition on free convective heat transfer of non-Newtonian power-law fluid in a square enclosure with two constant-temperature obstacles using lattice Boltzmann method

Journal of Thermal Analysis and Calorimetry - In this paper, the flow pattern and thermal characteristics of free convection of a Newtonian magnetohydrodynamic fluid flow inside a square enclosure...     

Determination of dopamine with improved sensitivity by exploiting an accumulation effect at a nano-gold electrode modified with poly(sulfosalicylic acid)

We describe a glassy carbon electrode modified with nano-gold and a film of poly(sulfosalicylic acid) that was obtained by electropolymerization of sulfosalicylic acid. The electrochemical characteristics of the electrode were investigated by using (a) the anionic hexacyanoferrate, and (b) the cationic ruthenium-trisbipyridyl systems as redox probes. The electrode displayed selective and enhanced electroanalytical response towards dopamine (DA), obviously because DA (which is cationic) is accumulated at the electrode, while anions such as ascorbic acid (AA) do not and in fact are being repelled. A 2000-fold molar excess of AA is tolerated after a 120-s accumulation time followed by stripping detection at pH?6.5. Response is linear with the concentration of DA in the range from 0.05 to 5???M, and the detection limit is 7 nM (at an S/N of 3) even in the presence of 100 ??M concentrations of AA.

Multielement x-ray fluorescence analysis of ores and products of their processing using the standard background method with a modified universal equation

A new algorithm is proposed for x-ray fluorescence analysis by the standard background method using a modified universal equation common for all analytes. In the new version of the universal equation, complicating factors can be accounted for by introducing additional correcting members into the analytical parameter. The developed procedure allows the analyst to give up numerous constraint equations, simplify the calibration of spectrometers, and improve the rapidity of the analysis of multielement ores and products of their processing without a drop in the accuracy of the results.     

Monitoring cell cultivation in microfluidic segments by optical pH sensing with a micro flow-through fluorometer using dye-doped polymer particles

Polymer microparticles containing an immobilized pH-sensitive dye are used for determination of pH inside microfluidic segments. The particles possess a hydrophilic surface in order to get a homogenous distribution inside the aqueous phase of microfluidic segments. The dye is coupled to the polymer matrix by a covalent bond. The pH can be determined by the read-out of fluorescence intensity. In contrast to dissolved indicator dyes, the chemical interference of the sensor particles with the surrounding solution is negligible. So, the particle-based sensing can easily be applied to the determination of pH changes during the cultivation of cells inside the microfluidic segments. The typical change of pH during cell cultivation can be used for monitoring the kinetic of cell cultivation inside single volumes in the nanoliter range, so that information about the metabolic activity of the organism can be obtained. An LED-based miniaturized flow-through fluorometer was developed to determine the fluorescence directly inside microtubes of an inner diameter of 0.5 mm. It allows measurement frequencies up to 60 Hz and is suited for characterization of fast moving large sequences of microfluidic segments.     

Characterization of polyolefin melts using the polymer reference interaction site model integral equation theory with a single‐site united atom model

A general approach, based on the polymer reference interaction site model (PRISM) integral equation theory, suitable for characterizing arbitrarily complex polyolefin melts is described. We tested the method by calculating the melt structures of linear polyethylene (PE) and isotactic polypropylene (iPP) and the spinodal decomposition temperatures for PE/iPP blends. The computational expense of the PRISM calculation was reduced with a single‐site united atom model in which the polyolefin CH, CH₂, and CH₃ groups were approximated as chemically equivalent sites with spherically symmetric energetic interactions. The site–site interactions were defined by a potential function comprising a hard core with an attractive Lennard–Jones term. These energetic parameters were optimized with a central composite design strategy that enabled a simultaneous fit of experimental melt density and structure factor data. Values were obtained for PE and iPP individually and for common universal parameters that could potentially be used for all polyolefins. The rotational isomeric state–metropolis Monte Carlo (RMMC) technique was used to generate sets of conformers at specified temperatures covering the melt‐temperature range of the polymers. The characteristic ratio was used to assess the quality of the conformers and the RMMC method. Values of 9.68 for PE and 9.27 for iPP were obtained. The single‐chain structure factors calculated by the RMMC method were used to calculate the total structure factor for each melt. These were validated against published X‐ray diffraction results. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1803–1814, 2001     

Stereoselective separations of chiral phosphinic acid pseudodipeptides by CEC using silica monoliths modified with an anion-exchange-type chiral selector

A nonaqueous CEC method for the simultaneous separation of the four stereoisomers of the N-benzyloxycarbonyl phosphinic pseudodipeptide methyl ester benzyloxycarbonyl-homophenylalanine Z-hPhepsi(PO2HCH2)Phe-OCH3 as well as of the corresponding N-2,4-dinitrophenyl (DNP)-derivative with free C-terminal carboxylic group DNP-hPhepsi(PO2HCH2)Phe-OH was developed. For this purpose, a monolithic silica capillary column modified with a cinchona alkaloid-derived anion-exchange-type chiral selector, namely O-9-(tert-butylcarbamoyl)quinidine (tBuCQD) was prepared. The mobile phase composition (ACN/methanol ratio, counterion type) was thoroughly optimized to end up with baseline resolution of all four stereoisomers with critical resolution of as high as about 2. The CEC method proved to be superior over the corresponding HPLC separations primarily due to significantly enhanced plate numbers (between 200,000 and 600,000 m(-1) in CEC). Diastereoselectivity contributions arising from electrophoretic mobility differences of the diastereomers facilitated the separation of the later eluted diastereomeric peak pair (peaks III and IV), but had a negative influence on the selectivity of the earlier eluted diastereomeric peak pair (peaks I and II). The stereoselective CEC assay allowed the assessment of the stereoisomeric purity of the individual isomers which were obtained by preparative HPLC on a CHIRALPAK QD-AX column that is based on the same tBuCQD selector. The present study demonstrates that there exist problems which are hard to solve by HPLC, yet can be conveniently solved by CEC. Moreover, it was intended to prove by this practical application that CEC with monolithic columns is robust enough to be used for solving real-life problems.