Water‐soluble/dispersible carbazole‐containing random and block copolymers by nitroxide‐mediated radical polymerisation

A series of carbazole‐containing water‐dispersible poly(acrylic acid)‐b‐(9‐(4‐vinylbenzyl)‐9H‐carbazole) block copolymers (poly(AA)‐b‐poly(VBK)) and water‐soluble poly(methacrylic acid‐ran‐(9‐(4‐vinylbenzyl)‐9H‐carbazole)) (poly(MAA‐ran‐VBK)) random copolymers were synthesised in a controlled manner (i.e. low polydispersities $(\overline {M_{{\rm w}} } /\overline {M_{n} } < 1.3)$ by nitroxide‐mediated polymerisation (NMP) using an SG1‐based alkoxyamine initiator, BlocBuilder. Poly(AA)‐b‐poly(VBK) block copolymers were most easily accessed by using poly(AA) in its protected form as the macroinitiator for the 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK) block. Controlled polymerisation of MAA was accomplished using an excess of 10 mol.% SG1 relative to BlocBuilder with VBK as controlling co‐monomer (initial molar feed content f_VBK,0 = 0.03–0.20) in dimethylformamide at 80°C. Poly(MAA‐ran‐VBK) copolymers with a final VBK molar composition of F_VBK < 0.30 resulted in water‐soluble copolymers. In addition, as macroinitiators, poly(MAA‐ran‐VBK)s were sufficiently pseudo‐living to reinitiate a second batch of monomer (90 mol.% methyl methacrylate with styrene) in organic solvent and by ab initio, surfactant‐free emulsion polymerisation. In both cases, low polydispersity, amphiphilic block copolymers resulted $(\overline {M_{{\rm w}} } /\overline {M_{{\rm n}} } < 1.3)$ . © 2012 Canadian Society for Chemical Engineering     

Internal configurations for a multi-product dividing wall column

This paper addresses possibilities and peculiarities associated with establishing the most beneficial internal configuration of a complex dividing wall column (DWC), using as a base case the separation of a multicomponent aromatics mixture into four or five product streams. As expected, the V_min-diagram method proved to be an appropriate tool in such a study, as a means for identifying and assessing promising configurations and at the same time to provide the necessary inputs and reliable initial guesses for detailed simulation-based determination of energy and stage requirements. A new, energy efficient two-top product configuration is introduced that appears to be an interesting option for a four-product DWC.     

Regulated fractionally integrated processes

Regulated (bounded) integrated time series are of significant practical importance and a recent development in the time series literature. Although regulated integrated series are characterized by asymptotic distributions that differ substantially from their unregulated counterparts, most inferential exercises continue to be performed with complete disregard for this potential feature of time series data. To date, only Cavaliere (2005) and Cavaliere and Xu (2011) have attempted to develop a theory for regulated integrated time series, particularly in the context of unit root testing. Unfortunately, no such theory has been developed for regulated fractionally integrated series, which are particularly important in financial time series and also in some unit root testing literature. This article achieves just this: it establishes a framework for regulated fractionally integrated processes and develops their functional central limit distributions. In addition, this article presents some simulation evidence and discusses several algorithms for obtaining the limiting distributions for these processes.     

Spray-dried nanoparticle-loaded pectin microspheres for dexamethasone nasal delivery

Abstract

In this study, we present the development of an innovative dry powder dexamethasone (Dex) nasal delivery system comprising Dex-loaded lipid/alginate nanoparticles incorporated within pectin microspheres (Dex/NPs-loaded pectin microspheres; DNM). DNM microspheres were characterized by the mean diameter of 2.76?±?0.10?µm, zeta-potential of –36.2?±?1.1?mV, and drug loading of 3.3?±?0.3%. The morphology study revealed irregular microsphere surface forming external voids. In contact with simulated nasal fluid, DNM microspheres demonstrated desirable property of moderate swelling and ensured stronger mucoadhesion compared with conventional Dex-loaded pectin microspheres. The strategy of Dex incorporation within the lipid/alginate NPs resulted in prolonged Dex release in relation to Dex being directly entrapped within the conventional pectin microspheres. DNM microspheres showed excellent biocompatibility and rendered Dex permeation across the selected epithelial cell model similar to that of Dex solution. In conclusion, balanced biopharmaceutical properties of the proposed nasal Dex delivery system provides the potential for prolonged contact time with nasal mucosa, prolonged therapeutic effect, and improved patient compliance.     

THE INFLUENCE OF PRESSURE AND TEMPERATURE ON THE KINETICS OF VACUUM DRYING OF KETOPROFEN

ABSTRACT

This paper explores the influence of temperature and pressure on drying kinetics of 2-(3-benzoylphenil propionic acid) ketoprofen, in a vacuum dryer on laboratory scale, Experimentally determined relations between moisture content and drying rate vs time, were approximated with an exponential model. Model parameters were correlated with drying conditions (temperature, pressure) and defined by functions of their potentions.

From an energy balance of the process, a mathematical model for simulating dependence of sample temperature vs drying time, and moisture content of material, has been developed.

Simulation of the drying kinetics and sample temperature, by use of those functional dependencies shows good agreement with experimental results.     

MODELLING GAS-SOLID FLOW IN A PNEUMATIC-FLASH DRYER

ABSTRACT

Investigations of aerodynamics of gas-solid flow in a pneumatic-flash dryer in semiindustrial scale have been carried out. Apparatus was composed of three elements with varying cross-sectional area connected together, i.e. expanding cone, decreasing cone and a vertical pipe with constant diameter. A mathematical model of the dryer is based on the continuity equations for both gas and solid phase and on differential equations for momentum balance of the gas-solid mixture and momentum balance of the solid phase. The model has been solved by means of Gear's numerical method. The effect of various empirical correlations for the solid-wall friction factor has been shown. Distributions, resulting from the model, for pressure, gas velocity, panicle velocity, voidage and residence time of panicle along the axis of apparatus have been presented. The results of numerical calculations have been verified on the basis of measurements in pan.     

π-ELECTRON CONTENTS OF RINGS IN THE DOUBLE-HEXAGONAL-CHAIN HOMOLOGOUS SERIES (PYRENE,ANTHANTHRENE AND OTHER ACENOACENES)

Abstract

Recently three methods for calculating the π-electron content of rings of benzenoid hydrocarbons were put forward: one based on the consideration of Kekuléstructural formulas, and the other two based on an analogous treatment of the Clar aromatic sextet formulas. These three methods are applied to the homologous series consisting of two condensed acene chains (whose first members are pyrene, anthanthrene, peri-naphthacenonaphthacene, …), leading to basically identical results. In contrast to acenes (in which the partition of π-electrons into rings is uniform), in the double-hexagonal-chain species the partition of π-electrons is highly non-uniform. The electron content monotonically decreases, in opposite directions, along the two acene chains, being maximal in the least annelated rings. Some other generally valid regularities in the π-electron properties of the double–hexagonal–chain benzenoids are also pointed out.     

Mechanochemical and Low‐Temperature Synthesis of Nanocrystalline Fluorohydroxyapatite/Fluorapatite

Low‐temperature synthesis of fluorapatite/fluorohydroxyapatite with precursor mixture previously mechanochemically treated is described in this article. Ethylene vinylacetate/versatate copolymer as a surface active substance was mechanically treated to obtain a core‐shell system with strongly controlled grain size. Despite usual behavior of mechanically activated systems, only an amorphous phase formed from precursor ions present in the mixture composed of β‐Ca₂P₂O₇, CaCO₃, CaF₂, and unreacted Ca(OH)₂ was obtained during milling for 5 min to 8 h. The mixture contained depots of labile F^? ions conserved in micelles cages, which are useful for teeth protection from carries. For transformation of these amorphous phases into fluorapatite, an additional low thermal treatment was necessary. The mechanism of the precursor mixture transformation into fluorapatite during milling and thermal treatment was investigated using FTIR spectroscopy and X‐ray diffraction. The morphology and size distribution of the obtained powders was studied using SEM and TEM.     

Analysis of the strain and hardness in self-cured and light-cured self-adhesive resin based cement

The study showed an application of the 3?D Digital Image Correlation Method (3?D-DIC) for detection of von Mises strain in samples of the self-etch, self-adhesive resin based cement (RBC). The aim was to determine and compare strain in the self-cured and light-cured Maxcem Elite, furthermore to investigate the hardness of these two cement-types. The experiment was carried out using two groups of Maxcem Elite (Kerr, Orange, CA, USA) samples; each tested group includes five (ø5?×?2?mm sized) samples, for both self-curing and light-curing mode. All samples were prepared by filling teflon ring-type molds. In addition, Vickers micro-hardness was measured for all samples. Maxcem Elite showed similar maximum strain values from 10% to 12% for both groups. Besides the maximum strain value, the 3?D-DIC method also enabled monitoring the change of strain field even after the recommended polymerization time. This method has shown that the polymerization shrinkage continues even after 10?min which disagreed with manufacturer’s suggestion. Group II showed maximum strain values of 12% in the peripheral zone after 10?min, in the last Stage (Stage 60). Statistically significant difference was not found in the overall strain between self- and light-cured Maxcem Elite neither peripherally (p?=?0.118) nor centrally (p?=?0.879). However, statistical significance was found in strain regarding central and peripheral zone in both, self-cured (p?=?0.020) and light-cured (p?=?0.002) Maxcem Elite. The mean von Mises strain values in the periphery of the samples (Section 0) were significantly higher compared to strain values in the center of the samples (for Section 1 and 2). The last stage (Stage 60) of the light-cured Maxcem Elite polymerization showed significantly higher values of von Mises strain compared to initial stage (Stage 0). Higher values of micro-hardness were noticed on the surfaces directly exposed to LED lamp after performing measurements of micro-hardness on light-cured samples.