In‐line near infrared spectroscopy monitoring of pharmaceutical powder moisture in a fluidised bed dryer: An efficient methodology for chemometric model development

This work proposes a novel chemometric methodology for in‐line near infrared spectroscopy (NIRS) monitoring of pharmaceutical powder moisture in a fluidised‐bed dryer. The collected spectra are analysed by multivariate chemometrics involving the preparation of numerous laboratory samples. A different methodology, using only plant samples, was tested in real‐time. A specially designed probe tip, allowing for robust in‐situ spectral acquisition, was designed. The results prove that NIRS can be as efficient as traditional quality analyses, e.g. loss‐on‐drying, in measuring powder moisture content in a fluidised bed dryer with a calibration model based only on plant samples. © 2011 Canadian Society for Chemical Engineering     

Effect of Oxime Ether Incorporation in Acyl Indole Derivatives on PPAR Subtype Selectivity

Compounds that simultaneously activate peroxisome proliferator‐activated receptor (PPAR) subtypes α and γ have the potential to effectively treat dyslipidemia and type 2 diabetes (T2D) in a single pharmaceutically active molecule. The frequently observed side effects of selective PPARγ agonists, such as edema and weight gain, were expected to be overcome by using additive PPARα activity, leading to dual PPARα/γ agonists with balanced activity for both subtypes. Herein we report the discovery, synthesis, and optimization of a new series of α‐ethoxyphenylpropionic acid bearing 5‐ or 6‐substituted indoles. The incorporation of oxime ethers on the carbonyl portion of the benzoyl group can bring the PPARα/γ potency ratio equal to or slightly greater than one, as is the case for compounds 20 c and 21 a . Compound 20 c shows high efficacy in an ob/ob mouse model of T2D and dyslipidemia, similar to that of rosiglitazone and tesaglitazar, but with a significant increase in body weight gain. In contrast, compound 21 a , less potent as a dual PPARα/γ activator than 20 c , showed an interesting pharmacological profile, as it elicits a decrease in body weight relative to reference compounds.     

Barrier effect of flame retardant systems in poly(methyl methacrylate): Study of the efficiency of the surface treatment by octylsilane of silica nanoparticles in combination with phosphorous fire retardant additives

In this work, flame retardant systems comprising ammonium polyphosphate (AP423) and hydrophilic (A200) or hydrophobic (R805) nanometric silica were incorporated into PMMA. The following techniques were performed to detail the fire behaviour of the composites: mass loss cone calorimetry, pyrolysis‐combustion flow calorimetry, pyrolysis‐gas chromatography–mass spectrometry, thermogravimetric analysis, X‐ray diffraction analysis, Fourier transform infrared spectroscopy and microscopic observations. The best fire behaviour was obtained with the surface‐treated silica in the presence of AP423. The formation of a new crystalline phase from the interactions between AP423 and R805 silica and a strong barrier effect due to a layered residue were the main modes of action of this system. Moreover, we have shown that the difference between the AP423 + R805 and AP423 + A200 systems was due to poor dispersion of the silica into the PMMA matrix in the latter formulation. Copyright © 2011 John Wiley & Sons, Ltd.     

Reactivity between liquid Si or Si alloys and graphite

The fundamental issues of the reaction at liquid Si/graphite interfaces between Si melting point (1412 °C) and 1600 °C are studied on the basis of results obtained with polycrystalline graphite concerning the growth kinetics of the interfacial reaction layer and the microstructure and morphology of this layer. Experiments were also performed using vitreous carbon substrates. Results are also reported for Si–Al alloys at 1000 °C. The elementary process controlling the growth kinetics is determined and a model is proposed to describe the different stages of the interfacial reaction.     

Thiol-ene “clickable” carbon-chain polymers based on diallyl cyclopropane-1,1-dicarboxylate

A novel type of clickable polymers with a very high local density of allyl side groups was developed. These polymers were obtained by the anionic ring-opening (co)polymerization of diallyl cyclopropane-1,1-dicarboxylate using as an initiating system a protic precursor whose acid–base reaction with the t-BuP₄ phosphazene base generated the initiator in situ. The obtained polymers display geminated allyl groups on every third carbon alongside the macromolecular backbone. Homopolymers as well as block and statistical copolymers have been synthesized, with controlled molecular weights and narrow molecular weight distributions. The coupling of mercaptans with the allyl CC double bonds has been investigated both thermally and photochemically, with the influence of the type of initiation on the efficiency of the polymer modification being discussed in comparison with other “clickable” systems. Further functionalization by several thiols was performed, leading to a range of functional poly(cyclopropane-1,1-dicarboxylate)s.     

Polyamide 66 microspheres metallised with in situ synthesised gold nanoparticles for a catalytic application

A simple concept is proposed to metallise polyamide 66 (PA66) spherulite structures with in situ synthesised gold nanoparticles (Au NPs) using a wet chemical method. This cost-effective approach, applied to produce a PA66/Au NP hybrid material, offers the advantages of controlling the nanoparticle size, the size distribution and the organic-inorganic interactions. These are the key factors that have to be controlled to construct consistent Au nanostructures which are essential for producing the catalytic activities of interest. The hybrid materials obtained are characterised by means of scanning electron microscopy, transmission electron microscopy, attenuated total reflection-Fourier transform infrared spectrometry and X-ray diffraction spectrometry. The results show that PA66 microspheres obtained via the crystallisation process are coated with Au NPs of 13 nm in size. It was found that controlling the metal coordination is the key parameter to template the Au NPs on the spherulite surfaces. The preparation processes and the key factors leading to the formation of PA66 spherulites coated with Au NPs are discussed. Moreover, the efficiency of the coated spherulites as a potential catalyst is proved by demonstrating the reduction of methylene blue via UV-visible spectrometry.     

A new class of organosilane-modified polycarboxylate superplasticizers with low sulfate sensitivity

It is well-established that a competitive adsorption exists between polycarboxylate superplasticizers (SP) and sulfate ions solubilized in the interstitial solution of cement paste, which may cause a loss of the dispersing properties. This has been explained by competitive weak ionic interactions between functional carboxyl groups and sulfate ions with cement grains. In this study, SPs including trialkoxysilane functional groups have been synthesized. Adsorption and dispersing properties of these SPs were evaluated in the presence of different concentrations of Na₂SO₄ added in aqueous solution. It appeared that a partial substitution of carboxyl groups by trialkoxysilane in the polymer makes them more resistant to sulfate ions. We suggested that the high adsorption capacity of these SPs results from the formation of strong bonds between hydroxysilane groups and calcium silicate hydrate phases. The improved compatibility of these new silylated SPs has been demonstrated through the formulation of two different concrete equivalent mortars.     

Bifunctional DNA Duplexes Permit Efficient Incorporation of pH Probes into Liposomes

Enzyme-mediated proton transport across biological membranes is critical for many vital cellular processes. pH-sensitive fluorescent dyes are an indispensable tool for investigating the molecular mechanism of proton-translocating enzymes. Here, we present a novel strategy to entrap pH-sensitive probes in the lumen of liposomes that has several advantages over the use of soluble or lipid-coupled probes. In our approach, the pH sensor is linked to a DNA oligomer with a sequence complementary to a second oligomer modified with a lipophilic moiety that anchors the DNA conjugate to the inner and outer leaflets of the lipid bilayer. The use of DNA as a scaffold allows subsequent selective enzymatic removal of the probe in the outer bilayer leaflet. The method shows a high yield of insertion and is compatible with reconstitution of membrane proteins by different methods. The usefulness of the conjugate for time-resolved proton pumping measurements was demonstrated by using two large membrane protein complexes.     

Effect of surface resistance on cyclohexane uptake curves in Silicalite-1 crystals

Adsorption kinetics of cyclohexane in a variety of Silicalite-1 samples were measured by gravimetric uptake experiments. The kinetic appears as dependent upon the history of the crystals. Samples stored for several months before calcination (with their micropores full of template) exhibit a kinetic drop by almost an order of magnitude. Surprisingly, physico-chemicals analysis do not show any differences between these samples (no modification of their crystallinity or morphology, and no residual carbon is detected in the pore network). The kinetic drop is therefore attributed to a modification of the crystals surface, induced by a long-time contact with the template or cyclohexane molecules.Aged and as-synthesized (non-calcined) samples were etched by an HF solution, so as to “purify” the surface of the crystals. After a few minutes of treatment, the aged samples recover their initial adsorption kinetic, confirming that the kinetic drop is induced by the partial blocking of the entrance of the pores. Moreover, some of the as-synthesized crystals also show a rise of their adsorption kinetic, showing that surface resistance can be present ab initio, depending on the synthesis conditions.In an attempt to produce an accelerated aging effect, hydrothermal treatments were performed on non-calcined crystals. However, the treatments conditions are too severe, and induce variations in the crystal structure.     

Graded evolution of anisotropic microstructure during sintering from crystal-oriented powder compact

Anisotropic sintering, including shrinkage and grain growth, was examined for c-axis-oriented (Sr,Ca)₂NaNb₅O₁₅ (SCNN) ceramics, which were prepared by colloidal processing under a magnetic field. In the c-axis-oriented SCNN powder compact, shrinkage and grain growth along the c-axis were higher than those along the a-axis. The anisotropic microstructural development was clearly associated with anisotropic sintering shrinkage. X-ray diffraction, scanning electron microscopy, and energy back scattering diffraction showed that the grain growth of oriented particles by including random grains contribute to the development of the oriented microstructure. Finally, the highly crystal-oriented SCNN ceramics with a densified microstructure were obtained through anisotropic sintering. These results clearly showed the potential to develop a well-defined anisotropic microstructure during sintering by designing and controlling the particle packing structure in a powder compact.