Design of high fastness acid dyes for silk: a chemometric approach

A chemometric strategy tor the design of acid dyes for silk is reported. A small set of representative dyes was selected by the technique of fractional factorial design, using the principal properties of the substituents as design variables. The selected dyes were synthesised and fastness properties on silk were measured. Wash fastness and light fastness values were related to the chemical structure by the partial least squares (PLS) method. The models were used to predict the fastness of new dyes of the same class and to optimise the structure.     

Size-controlled synthesis and NMR characterization of mesitylene-vinylsiloxanes stabilized Pt nanoparticles in solution

Pt nanoclusters have been generated by reaction of Pt vapour and mesitylene vapour and the role of the mesitylene/platinum ratio and the Pt particle size has been evaluated, quenching the resulting mesitylene solvated Pt atoms with 1,3-divinyltetramethyldisiloxane (DVS) as additional ligand. The Pt particle sizes have been estimated on the basis of DOSY (Diffusion-Ordered SpectroscopY) analysis and information on their structure features have been obtained by combined use of 2D NMR techniques.     

Thermal Explosion of Powder Mixtures: Numerical Approach

A numerical approach to investigate the heating and the ignition of powder mixtures by radiant energy is presented. The ignition study is based on the possibility of separating the initiation transient from the propagation process, by operating in thermal explosion mode.     

Determination of correlations to predict the minimum agitation speed for complete solid suspension in agitated vessels

Experiments were conducted to determine the effects of impeller clearance, impeller diameter, and other operating variables on the minimum agitation speed for off-bottom solid suspension in agitated vessels, N_js, for disc turbines (DTs) and flat-blade turbines (FBTs). Only data for which the impellers produced recirculation flows above and below the impeller (the so-called “double-eight” flow pattern) were considered. Regression equations for N_js were obtained, in which explicit terms for impeller clearance and vessel diameter-to-impeller diameter ratio (T/D) were included. Modified Zwietering equations (Zwietering, 1958) were also obtained, in which Zwietering's parameter S was mathematically expressed as a function of vessel diameter-to-impeller clearance ratio and T/D ratio. When used together with the correlations of Armenante and Uehara Nagamine (1998) for impellers close to the vessel bottom, the equations presented here can be used to calculate N_js for DTs and FBTs for any typical impeller clearance.     

Composites Between Alumina and an Ester‐Ether‐Ester Bioresorbable Copolymer

Composites between alumina and the bioresorbable poly(ε‐caprolactone)‐block‐poly(oxyethylene)‐block‐poly(ε‐caprolactone) copolymer were obtained by reacting ε‐caprolactone with preformed poly(ethylene glycol), in the presence of ceramic alumina powder, at 185°C under vacuum. The mechanical properties, tested by compression and flexural strengths and Young's modulus, show that the copolymer interacts poorly with the alumina grains. Both scanning electron and atomic force microscopy show a scarce wettability between alumina and copolymer, as well as the aggregation of alumina micro‐particles into clusters of big size. Both mechanical and morphological tests seem to indicate a stronger interaction between the alumina micro‐particles than between the alumina surface and the reaction mixture during the polymerization, as well as a “compacting effect” by alumina on the forming copolymer. The FT‐IR spectra of the composites show both copolymer and alumina absorption bands. The FT‐IR analysis on the fractions of an extraction with CHCl₃ indicates the presence of traces of poly(ε‐caprolactone), stably linked to alumina. The polymerization of ε‐caprolactone with alumina alone in the same conditions gives poly(ε‐caprolactone), mainly free and in minor part linked to the alumina surface. Two polymerization mechanisms, simultaneously occurring, are proposed. The most relevant result of this work is the lack of chemical inertness of alumina towards ε‐caprolactone, which leads to reconsider also the use of alumina as a biochemically inert material.     

Preparation and thermal behavior of random poly(butylene terephthalate/azelate) copolyesters

Poly(butylene terephthalate), poly(butylene azelate), and poly(butylene terephthalate/butylene azelate) random copolymers of various compositions were synthesized in bulk using the well‐known two‐stage polycondensation procedure, and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. As far as the thermal stability is concerned, it was found to be rather similar for all copolymers and homopolymers investigated. All the copolymers were found to be partially crystalline, and the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to pure homopolymers. Flory's equation was found to describe the T_m–composition data and permitted to calculate the melting temperatures (T^°_m ) and the heats of fusion (ΔH_u) of both the completely crystalline homopolymers. Owing to the high crystallization rate, the glass transition was observable only for the copolymers containing from 30 to 70 mol % of the terephthalate units; even though the samples cannot be frozen in a completely amorphous state, the data obtained confirmed that the introduction of the aromatic units gave rise to an increase of T_g, due to a chain stiffening. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2694–2702, 1999     

Multilayer nanoencapsulation. New approach for immune protection of human pancreatic islets

Immune protection of artificial tissue by means of pancreatic islet microencapsulation is a very ambitious new approach to avoid life-long immune suppression. But the success in the utilization of the alginate-beads with incorporated islets is unfortunately limited. Some of the problems cannot be solved by a two-component system, so polymer encapsulation of the microbeads was tested to improve the properties. In the present paper a pure nanoencapsulation multilayer approach was tested in order to reduce the size of the capsule and possibly apply in the future a multilayer capsule with individual properties in each layer or region of the capsule. Different polycations were attached in a self-assembly process. The advantage in using the surface charge of islets as binding site for the polyions is the guarantee of complete coverage after the second layer. Release of insulin was determined to characterize the function of the islets after encapsulation as well as the permeability of the capsule. Fluorescence microscopy was used to visualize the polyelectrolyte layers. Finally by means of an immune assay, the protection capability of the capsule was proved. In these first measurements the encapsulation with a multilayer nanocapsule was shown to be a possible alternative to the more space-consuming and random islet-trapping microencapsulation.     

The alpha-to-beta conformational transition of Alzheimer's Abeta-(1-42) peptide in aqueous media is reversible: a step by step conformational analysis suggests the location of beta conformation seeding

Current views of the role of beta-amyloid (Abeta) peptide fibrils range from regarding them as the cause of Alzheimer's pathology to having a protective function. In the last few years, it has also been suggested that soluble oligomers might be the most important toxic species. In all cases, the study of the conformational properties of Abeta peptides in soluble form constitutes a basic approach to the design of molecules with "antiamyloid" activity. We have experimentally investigated the conformational path that can lead the Abeta-(1-42) peptide from the native state, which is represented by an alpha helix embedded in the membrane, to the final state in the amyloid fibrils, which is characterized by beta-sheet structures. The conformational steps were monitored by using CD and NMR spectroscopy in media of varying polarities. This was achieved by changing the composition of water and hexafluoroisopropanol (HFIP). In the presence of HFIP, beta conformations can be observed in solutions that have very high water content (up to 99 % water; v/v). These can be turned back to alpha helices simply by adding the appropriate amount of HFIP. The transition of Abeta-(1-42) from alpha to beta conformations occurs when the amount of water is higher than 80 % (v/v). The NMR structure solved in HFIP/H2O with high water content showed that, on going from very apolar to polar environments, the long N-terminal helix is essentially retained, whereas the shorter C-terminal helix is lost. The complete conformational path was investigated in detail with the aid of molecular-dynamics simulations in explicit solvent, which led to the localization of residues that might seed beta conformations. The structures obtained might help to find regions that are more affected by environmental conditions in vivo. This could in turn aid the design of molecules able to inhibit fibril deposition or revert oligomerization processes.