Monolayers of polyethilenimine on flat glass: a versatile platform for cations coordination and nanoparticles grafting in the preparation of antibacterial surfaces

A polyethylenimine (PEI) self-assembled monolayer (SAM) is prepared, capable of complexing silver and copper cations and of anchoring silver nanoparticles, exerting antibacterial activity against Escherichia coli and Staphylococcus aureus. Functionalized glassy surfaces have been fully characterized through spectroscopic techniques (UV-Vis spectroscopy, spectroscopic ellipsometry), atomic force microscopy imaging and quantitative Ag and Cu analysis (ICP optical emission spectroscopy).     

Solid-state NMR crystallography through paramagnetic restraints

Pseudocontact shifts (PCSs) measured by solid-state NMR spectroscopy (SS-NMR) on microcrystalline powders of a paramagnetic metalloprotein permit NMR crystallography. Along with other restraints for SS-NMR experiments, the protein molecular structure as well as the correct crystal packing are obtained.     

The quantum field as a quantum computer

It is supposed that at very small scales a quantum field is an infinite homogeneous quantum computer. On a quantum computer the information cannot propagate faster than c=a/τ, a and τ being the minimum space and time distances between gates, respectively. For one space dimension it is shown that the information flow satisfies a Dirac equation, with speed v=ζc and ζ=ζ(m) mass-dependent. For c the speed of light ζ−1 is a vacuum refraction index that increases monotonically from ζ−1(0)=1 to ζ−1(M)=∞, M being the Planck mass for 2a the Planck length. The Fermi anticommuting field can be entirely qubitized, i.e. it can be written in terms of local Pauli matrices and with the field interaction remaining local on qubits. Extensions to larger space dimensions are discussed.     

A Functional Equation Whose Unknown is \mathcal{P}([0,1]) Valued

We study a functional equation whose unknown maps a Euclidean space into the space of probability distributions on [0,1]. We prove existence and uniqueness of its solution under suitable regularity and boundary conditions, we show that it depends continuously on the boundary datum, and we characterize solutions that are diffuse on [0,1]. A canonical solution is obtained by means of a Randomly Reinforced Urn with different reinforcement distributions having equal means. The general solution to the functional equation defines a new parametric collection of distributions on [0,1] generalizing the Beta family.     

Physicochemical characterization of acrylamide/bisacrylamide hydrogels and their application for the conservation of easel paintings

Acrylamide chemical gels have been synthesized to obtain systems with mechanic and hydrophilic properties suitable for the cleaning of works of art. The gel characteristics were tailored by changing the polymer percentage present in the final hydrogel formulation from 2 to 10% w/w. Two different hydrogels have been selected in this interval for an in depth characterization (i.e., S 4% w/w and H 6% w/w). Water retention properties of the gels along with the free water index have been determined by the combination of standard dehydration tests and differential scanning calorimetry (DSC) measurements. The gels' structure has been determined by scanning electron microscopy (SEM) and small angle X-ray scattering (SAXS). The water retention capacity of hydrogel, H, was also determined. Cleaning tests on easel painting replicas, performed with both hydrogels loaded with an aqueous detergent system, showed good results in the removal of a widely used synthetic adhesive and hence offered these gels as a real alternative to the widely applied physical gel methodology with the advantage of being a residue-free technique. A preliminary SAXS investigation confirms the persistence of the detergent system nanostructure inside the hydrogel.     

Ultrastrong coupling regime and plasmon polaritons in parabolic semiconductor quantum wells

Ultrastrong coupling is studied in a modulation-doped parabolic potential well coupled to an inductance-capacitance resonant circuit. In this system, in accordance to Kohn's theorem, strong reduction of the energy level separation caused by the electron-electron interaction compensates the depolarization shift. As a result, a very large ratio of 27% of the Rabi frequency to the center resonance frequency as well as a polariton gap of width 2π × 670 GHz are observed, suggesting parabolic quantum wells as the system of choice in order to explore the ultrastrong coupling regime.     

A multi-analytical approach to studying binding media in oil paintings

This article presents a multi-analytical approach to investigating the drying, polymerisation and oxidative degradation of linseed oil, which had undergone various treatments known to be undertaken during the nineteenth century in preparation for painting. The oil was mechanically extracted from the same seed lot then processed by different methods: water washing, heat treatments, and the addition of driers, with and without heat. The oil was prepared in 1999 within the framework of the MOLART project. We compared thermogravimetric analysis (TG), which yields macromolecular information, with gas-chromatography mass-spectrometry (GC/MS) and direct exposure mass spectrometry (DE-MS), which provide molecular information. This comparison enabled us to elucidate the role of pre-treatment on the composition of the oil. TG and oxygen uptake curves registered at a constant temperature helped us to identify the different physical behaviour of the oil samples, thus highlighting the presence of hydrolysed, oxidised and crosslinked fractions, as a consequence of the different pre-treatments. GC/MS was used to characterise the soluble and non-polymeric fraction of the oil, to calculate the ratios of palmitic to stearic acid (P/S), and azelaic to palmitic acid (A/P), and to further evaluate the effects of oil pre-treatments. DE-MS using chemical ionisation with CH₄, enabled us to establish the chemical composition of the oil in different stages of ageing. DE-MS proved to be a useful tool for a simultaneous semi-quantitative characterisation of the free fatty acids, monoglycerids, diglycerides and triglycerides present in each sample. The combination of thermal analysis with GC/MS and DE-MS enabled a model to be developed, which unravelled how oil pre-treatments produce binders with different physical–chemical qualities.     

Rounding-based heuristics for nonconvex MINLPs

We propose two primal heuristics for nonconvex mixed-integer nonlinear programs. Both are based on the idea of rounding the solution of a continuous nonlinear program subject to linear constraints. Each rounding step is accomplished through the solution of a mixed-integer linear program. Our heuristics use the same algorithmic scheme, but they differ in the choice of the point to be rounded (which is feasible for nonlinear constraints but possibly fractional) and in the linear constraints. We propose a feasibility heuristic, that aims at finding an initial feasible solution, and an improvement heuristic, whose purpose is to search for an improved solution within the neighborhood of a given point. The neighborhood is defined through local branching cuts or box constraints. Computational results show the effectiveness in practice of these simple ideas, implemented within an open-source solver for nonconvex mixed-integer nonlinear programs.     

Modelling of Enzyme Properties in Organic Solvents

Summary.  In this article we review how molecular modeling techniques can be used to shed some light on the influence of organic solvents on the molecular characteristics of proteins and enzymes. Molecular dynamic simulations on bovine pancreas trypsin inhibitor, chymotrypsin, and subtilisin make it possible to get a deeper understanding into how increased intramolecular interactions improve conformational rigidity, thus explaining the lower reactivity and the higher thermostability of enzymes in non-aqueous media. The application of thermodynamics-based models allows first qualitative predictions on the selectivity of many reaction types; however, the application of quantum mechanical/molecular mechanical methods is required for the development of quantitative models of actual reactivity patterns. Received November 18, 1999. Accepted (revised) February 8, 2000     

Optical Properties of M(II) Schiff-base Complexes Dispersed in Ethylene based Polymers

Summary: Several salicylaldiminate M(II) complexes of Nickel, Copper and Cobalt have been prepared and mixed with ethylene based polymers in order to prepare new composite materials with interesting morphological and optical properties by profiting of the presence of alkyl chains and push-pull substituents connected to the ligand structure. The phase dispersion behaviour of the binary films has been studied by scanning electron microscopy (SEM) and x-ray microanalysis, whereas the optical properties of the composite samples have been evaluated by UV-vis and fluorescence spectroscopy. The results in absorption have been analysed in terms of the anisotropy induced by the mechanical orientation of the polymer matrix and by the role of the metal centre according to the different strength of the complexes transition dipole moment. The luminescence behaviour have been discussed in terms of potential developments aimed at preparing polymeric supported Schiff base ligands for metal ions sensor applications.