Population Balance Model for Miniemulsion Polymerization, 2

Summary: The predictions of the model developed in Part 1 of this series are compared with experimental values taken from literature. Initially, the method of solution of the population balance equation and the simulation algorithm are given. Various radical entry mechanisms are discussed in adequate detail. Plausible arguments are given to identify the correct radical entry mechanism. An expression to evaluate the radical exit coefficient is given. Model predictions of a number of variables are discussed. These include average number of radicals per particle, particle phase monomer volume fraction, average number of radicals averaged over all particles, monomer volume fraction averaged over all particles, variation of nucleation rate, variation of fraction of droplets nucleated, variation of average diameter, variation of standard deviation, variation of polydispersity index, and development of particle size distribution with time. Finally, model predictions for the variation of conversion with time for five different initiator concentrations, number average diameter, standard deviation and full distribution are compared with experimental values.

Variation in the average number of radicals per particle with time, at different collocation points.     

Rubidium uranium trisulphate: A new chemical assay standard for uranium

Rubidium uranium trisulphate [Rb₂U(SO₄)₃] was prepared as a high purity compound of uranium in different lots of 250 g each. The compound was characterised and evaluated by chemical, atomic spectrosopic, infrared, X-ray diffraction and thermogravimetric methods for its use as a chemical assay standard for uranium. The compound is stoichiometric, pure, homogeneous and stable in atmospheric conditions. The solubility studies showed that Rb₂U(SO₄)₃ is easily soluble in mineral acids. An experiment based on Randomised Block Design was carried out to assign a value to the uranium content in Rb₂U(SO₄)₃ from the statistically analysed chemical data. The assigned value of [34.167±0.042]% to the uranium content is in close agreement with the theoretical value of 34.152%. Based on these studies, Rb₂U(SO₄)₃ is recommended as a chemical assay standard for uranium.     

Imaging in turbid media using quasi-ballistic photons

We study by means of experiments and Monte Carlo simulations, the scattering of light in random media, to determine the distance up to which photons travel along almost undeviated paths within a scattering medium, and are therefore capable of casting a shadow of an opaque inclusion embedded within the medium. Such photons are isolated by polarisation discrimination wherein the plane of linear polarisation of the input light is continuously rotated and the polarisation preserving component of the emerging light is extracted by means of a Fourier transform. This technique is a software implementation of lock-in detection. We find that images may be recovered to a depth far in excess of that predicted by the diffusion theory of photon propagation. To understand our experimental results, we perform Monte Carlo simulations to model the random walk behaviour of the multiply scattered photons. We present a new definition of a diffusing photon in terms of the memory of its initial direction of propagation, which we then quantify in terms of an angular correlation function. This redefinition yields the penetration depth of the polarisation preserving photons. Based on these results, we have formulated a model to understand shadow formation in a turbid medium, the predictions of which are in good agreement with our experimental results.     

Rhodium(III) catalyzed oxidation of cyclic ketones by alkaline hexacyanoferrate(III)

The kinetics of the oxidation of 2-methyl cyclohexanone and cycloheptanone with Fe(CN)₆ ³⁻ catalyzed by RhCl₃ in alkaline medium was investigated at four temperatures. The rate follows direct proportionality with respect to lower concentrations of hexacyanoferrate(III) ion, but tends to become zero order at higher concentrations of the oxidant, while the reaction shows first-order kinetics with respect to hydroxide ion and cyclic ketone concentrations. The rate shows a peculiar nature with respect to RhCl₃ concentrations in that it increases with increase in catalyst at low catalyst concentrations but after reaching a maximum, further increase in concentration retards the rate. An increase in the ionic strength of the medium increases the rate, while increase in the Fe(CN)₆ ⁴⁻ concentration decreases the rate.     

Synthesis and characterization of titanates of the formula MTiO3 (M = Mn,Fe, Co,Ni and Cd) by co-precipitation of mixed metal oxalates

When divalent metal chloride solutions of Mn, Fe, Co, Ni and Cd were mixed with potassium titanyl oxalate solution, mixed metal oxalates were obtained in the case of Fe, Co and Ni at room temperature in the pH range 1.5–3. In the case of manganese, heating was found to be necessary to induce precipitation and complete precipitation occurred at 80 °C. Mixed cadmium and titanyl oxalate precipitation was complete at a pH of 3 at room temperature. Various physico-chemical techniques were employed to characterize the as-dried oxalate precursors and the final MTiO₃ oxide powders (M = Mn, Fe, Co, Ni and Cd) obtained on thermal decomposition. All these experimental results relating to the synthesis and characterizations of MTiO₃ oxides are presented in this paper. The results suggest that the reaction of potassium titanyl oxalate and metal chloride solutions may not lead to the formation of a single molecular precursor by direct salt elimination reaction in the pH range 1.5–3.     

Polyaniline nanotubes for impedimetric triglyceride detection

Polyaniline nanotubes (PANI-NT) based film electrophoretically deposited onto indium–tin–oxide (ITO) coated glass plate has been utilized for covalent immobilization of lipase (LIP), via glutaraldehyde (Glu), for triglyceride detection using impedimetric technique. It is shown that fatty acid molecules produced during triglyceride hydrolysis result in change in charge transfer resistance (R_CT) of PANI-NT film with varying triglyceride concentration. LIP/Glu/PANI-NT/ITO bioelectrode has linearity as 25–300 mg dL^?1, sensitivity as 2.59 × 10^?3 KΩ^?1 mg^?1 dL, response time as 20 s and regression coefficient as 0.99. A low value of apparent Michaelis–Menten constant (～0.62 mM) indicates high enzyme affinity to tributyrin. The LIP/Glu/PANI-NT/ITO bioelectrode has been utilized to estimate triglyceride in serum samples.     

Pronounced variation in the collective dynamics of highly correlated lightest liquid alkali metal: Lithium

Recently measured inelastic X-ray spectra (IXS) of detailed coherent dynamical structure factor S(κ, ω) and hence the equilibrium collective dynamics, of the lightest liquid alkali metal, lithium at 475 K, have been successfully explained using the modified microscopic theory of the collective dynamics of a simple liquid, in a huge wave-vector, κ, range: 1.4 nm^?1 ≤ κ ≤ 110.0 nm^?1, ?κ is the linear momentum transfer. The role of single particle motion in the collective dynamics of the liquid changes from diffusive for smaller values of wave-vector, κ < 21 nm^?1 to that of a free particle for higher κ-values, 21 nm^?1 ≤ κ ≤ 110 nm^?1. The quantum correction due to detailed balance condition in S(κ, ω) for liquid Li, whose dynamics, unlike that of quantum liquid ⁴He, is essentially classical, yields results in better agreement with the corresponding experimental S(κ, ω) and the quantum correction becomes significant for higher values of κ and ω. The wave-vector dependent variation of longitudinal viscosity, η_l, is in good agreement with the corresponding results obtained from memory function approach. The wave-vector dependent variation of single characteristic relaxation time lies in between the variation of two relaxation times of memory function approach.     

Structure of poly(propyl ether imine) dendrimer from fully atomistic molecular dynamics simulation and by small angle x-ray scattering

We study the structure of carboxylic acid terminated neutral poly(propyl ether imine) (PETIM) dendrimer from generations 1-6 (G1-G6) in a good solvent (water) by fully atomistic molecular dynamics (MD) simulations. We determine as a function of generation the structural properties such as radius of gyration, shape tensor, asphericity, fractal dimension, monomer density distribution, and end-group distribution functions. The sizes obtained from the MD simulations have been validated by small angle x-ray scattering experiment on dendrimer of generations 2-4 (G2-G4). A good agreement between the experimental and theoretical value of radius of gyration has been observed. We find a linear increase in radius of gyration with the generation. In contrast, Rg scales as approximately Nx with the number of monomers. We find two distinct exponents depending on the generations, x=0.47 for G1-G3 and x=0.28 for G3-G6, which reveal their nonspace filling nature. In comparison with the amine terminated poly(amidoamine) (PAMAM) dendrimer, we find that Rg of Gth generation PETIM dendrimer is nearly equal to that of (G+1)th generation of PAMAM dendrimer as observed by Maiti et al. [Macromolecules 38, 979 (2005)]. We find substantial back folding of the outer subgenerations into the interior of the dendrimer. Due to their highly flexible nature of the repeating branch units, the shape of the PETIM dendrimer deviates significantly from the spherical shape and the molecules become more and more spherical as the generation increases. The interior of the dendrimer is quite open with internal cavities available for accommodating guest molecules, suggesting the use of PETIM dendrimer for guest-host applications. We also give a quantitative measure of the number of water molecules present inside the dendrimer.     

Off-resonance binomial preparatory pulse technique for high sensitivity MRI of H2O17

H2O17 is a freely diffusible tracer and naturally occurring isotope of O16 detectable by MRI and has been shown to be useful for assessing cerebral perfusion in animal studies using direct and indirect MR detection techniques. However, earlier MR techniques are either not sensitive to changes in small concentrations of tissue H2O17 or are not practical for use on clinical scanners. In this work, a novel method for detecting H2O17 with high sensitivity has been proposed that uses a short, intense, binomial preparatory spin lock pulse with resonance offsets for high sensitive rapid, multislice imaging of tissue H2O17. Two sets of phantom experiments were performed on the 1.5 T and repeated on 3.0 T to assess the feasibility of the proposed technique. The phantom was constructed using ovalbumin and doped with 0.4 atom% and 1.0 atom% H2O17. After obtaining initial parameters, the proposed technique was validated in an anesthetized primate model that was injected with 1.8 cc of 40 atom% H2O17. Phantom experiments showed that the proposed technique was able to detect H2O17 with relatively high sensitivity and high B1 amplitude (and small offsets) preparatory pulses produced similar results as low B1 amplitude (and larger offsets). Primate brain study showed a 42.97% difference in mean signal intensity between pre- and post-H2O17 injection. The proposed technique was successfully implemented on a clinical scanner and was able to detect H2O17 with relatively high sensitivity. Primate study has shown that such a technique can be successfully used for human imaging applications to investigate and assess cerebral perfusion.