Chemical modification of the surface of cellulosic fibres. 2. Introduction of alkenyl moieties via condensation reactions involving isocyanate functions

Various cellulosic substrates including powders, long fibres and sheets were treated with isocyanates bearing an alkenyl function in a non-swelling medium. These heterogeneous reactions introduced a small but significant number of polymerizable moieties at the surface of the cellulose. In a second step, the free radical polymerization of styrene or methyl methacrylate was carried out in the presence of these modified cellulosics. It was shown that the alkenyl functions appended onto their surface took part in the chain growth thus giving a continuous path of covalent bonds between the solid substrate and the polymer matrix. 0969--0239 © 1998 Blackie Academic & Professional     

Structure of phosphorus-selenium glasses: results from ab initio molecular dynamics simulations

Car-Parrinello molecular dynamics calculations have been carried out for phosphorus-selenium mixtures of compositions corresponding to overall stoichiometrics PSe and P₂Se. Comparison of the calculated structure factors with those obtained in neutron scattering experiements suggests that the real materials are characterized by the presence of substantial numbers of well defined molecular units.     

Limit Analysis of Structures with Stochastic Strength Variations∗

On the basis of a probabilistic fomulation of the fundamental theorems of “limit analysis,” a procedure is developed which allows, with a very limited amount of computing work, the determination of a domain containing the probability distribution curve of the collapse load factor of any structure that satisfies the usual conditions for validity of the limit analysis, but has randomly distributed limit strengths.

Further improvements of the bounds thus obtained can be achieved by the equivalent of either the equilibrium or the kinematic methods of limit analysis.     

A STUDY OF SOME POLYPYRIDYLRUTHENIUM(II) COMPLEXES AS DNA BINDERS AND PHOTOCLEAVAGE REAGENTS

The nature of the binding of several ruthenium polypyridyl complexes containing 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (DMB), 1,10-phenanthroline (phen), 4,7-diphenyl-1,10-phenanthroline (DPP), 2,2',2"-terpyridine (terpy), 2,2'-biquinoline (biq), 1,4,5,8-tetraazaphenanthrene (TAP) and 1,4,5,8,9,12-hexaazatriphenylene (HAT), with calf thymus DNA, poly[d(A-T)] and poly[d(G-C)] were studied by absorption and emission spectroscopy, DNA melting techniques, and emission lifetime measurements. In low ionic strength phosphate buffer, spectroscopic changes and DNA stabilization depended on the polypyridyl ligands present, and indicated binding that varied from substantially electrostatic to intercalative. Ru(bipy)2(HAT)2+ and Ru(phen)3(2+), which bind by partial intercalation, also show a strong preference for poly[d(A-T)]. The emission quantum yields for most complexes were increased in the presence of DNA. An exception was Ru(TAP)3(2+) which has a markedly reduced emission quantum yield and lifetime in the presence of poly[d(G-C)] or CT-DNA, due to photoredox interaction with quanines. Emission decays of the complexes generally showed multiexponential behaviour. The ability of the ruthenium complexes to sensitise DNA cleavage was determined using pBR322 plasmid DNA. Ru(TAP)3(2+) is the most efficient sensitiser while uncharged complexes and complexes with very short-lived excited states do not cleave DNA.     

In vivo SPECTROPHOTOMETRIC EVALUATION OF NEOPLASTIC AND NON-NEOPLASTIC SKIN PIGMENTED LESIONS–I. REFLECTANCE MEASUREMENTS

Reflectance spectrophotometry from 400 to 800 nm on different cutaneous pigmented lesions, including primary and metastatic malignant melanoma, pigmented nevi, lentigo and seborrhoeic keratosis, has been performed by using an external integrating sphere coupled to a spectrophotometer. Measurements show that reflectance spectra of the different lesions manifest dissimilar patterns, particularly in the near IR region. Comparison of reflectance of nevi with that of malignant melanomas results in a highly significant difference (P less than 10(-6)) between the two samples. Though interpretation of the spectra remains difficult as a result of the complexity of the optical processes of scattering and absorption, our results suggest that a detailed analysis of the reflectance spectrum may give clinically useful information, and could be utilized as an aid in clinical diagnosis of cutaneous pigmented lesions, especially where malignant melanoma is concerned.     

An Improvement in the Static Method for Limit Analysis of Structures with Stochastic Strength Variations

On the basis of the static and kinematic theorems of probabilistic limit analysis [1-3], a new procedure to study the random strength of rigid-plastic structures is developed. This procedure leads to upper bounds to the failure probability, which show a remarkable improvement when compared with similar results so far obtained from “static” considerations. As an example, extensive numerical calculations carried out for a simple portal frame with random limit moments are presented and some observations are formulated.     

EFFECT OF SPANWISE SYSTEM ROTATION ON SPATIALLY DEVELOPING DEAN VORTICES

Three-dimensional spatially developing Navier–Stokes calculations are carried out to simulate the flow in a curved, rotating channel. The competition between centrifugal and Coriolis forces, expressed by the ratio of the Dean number to the rotation number, gives rise to a variety of possible instability modes characterized by the presence of streamwise vortices. Cases in which the force produced by system rotation enhances or opposes the centrifugal force are treated and the effect on the ensuing instability are analysed. Evidence for a generalized Eckhaus instability of rotating Dean vortices is presented.     

The surface chemical modification of cellulosic fibres in view of their use in composite materials

The surface modification of various cellulosic materials was studied in heterogeneous conditions using different grafting agents bearing anhydride or isocyanate reactive groups. Some of these reagents were oligomeric, others polymeric and most were chosen so as to provide a non-polar character to the surface of the fibres in view of their possible use as reinforcing agents in composites based on polymeric matrices. The success of these chemical modifications was assessed by Fourier-transform Infrared Spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and elemental analysis. The accessibility of the superficial OH groups varied as a function of the coupling agent in terms of both molecular size and chemical nature and ranged between 1 and 3% of the total hydroxy groups borne by the initial cellulose sample. This revised version was published online in August 2006 with corrections to the Cover Date.     

Reduced Kinetic Schemes of Complex Reaction Systems: Fossil and Biomass‐Derived Transportation Fuels

The kinetic modeling of the pyrolysis and combustion of liquid transportation fuels is a very complex task for two different reasons: the challenging characterization of the complex mixture of several hydrocarbon isomers and the complexity of the oxidation mechanisms of large hydrocarbon and oxygenated molecules. While surrogate mixtures of reference components allow to tackle the first difficulty, the complex behavior of the oxidation mechanisms is mostly overcome by reducing the total number of involved species by adopting a lumping approach. After a first investigation of the different liquid fuels (gasoline, kerosene, and diesel fuels), a short discussion on the lumping techniques allows to highlight the advantages of this approach. The lumped POLIMI pyrolysis and oxidation mechanism of hydrocarbon and oxygenated fuels is then used for generating several skeletal mechanisms for typical surrogate mixtures, moving from pure n‐heptane up to heavy diesel fuels. These skeletal models are simply reduced with a reaction flux analysis, and they involve between 100 and 200 species. While these sizes already allow detailed computational fluid dynamics (CFD) calculations in internal combustion engines, further reduction phases are necessary when the interest is toward more complex CFD computations. To maintain the standard structure of the skeletal mechanisms, successive reduction phases are not considered. Moreover, new regulations pushed toward a greater use of renewable fuels. For these reasons, the skeletal models are also extended to biogasolines including methanol, ethanol, and n‐butanol. Similarly, skeletal models of diesel and biodiesel fuels, including methyl esters, are also provided. Several comparisons with experimental data and complete validations in the operating range of internal combustion engines are also reported. The whole set of comparisons with experimental data obtained in a wide range of conditions not only validate the reduced models of specific transportation fuels but also the complete kinetic scheme POLIMI_1404.