The Use of Poly(Sodium N-Undecanoyl-l-Leucylvalinate), Poly(Sodium N-Undecanoyl-l-Leucinate) and Poly(Sodium N-Undecanoyl-l-Valinate) Surfactants as Chiral Selectors for Determination of Enantiomeric Composition of Samples by Multivariate Regression Modeling of Fluorescence Spectral Data

Steady-state fluorescence spectroscopy was employed to investigate the use of chiral polymeric surfactants as chiral selectors in chiral analysis by multivariate regression modeling of spectral data. Partial-least-squares regression modeling (PLS-1) was used to correlate changes in the fluorescence spectral data of 1,1'-bi-2-naphthol (BOH), 1,1'-binaphthyl-2,2'-diamine (BNA), or 2,2,2-trifluoroanthrylethanol (TFA) in the presence of poly(sodium N-undecanoyl-L-leucylvalinate), poly(sodium N-undecanoyl-L-leucinate) or poly(sodium N-undecanoyl-L-valinate) as the enantiomeric composition of the chiral analytes was varied. The regression models produced from the spectral data were validated by determining the enantiomeric composition of independently prepared test solutions. The ability of the model to correctly predict the enantiomeric composition of future samples was evaluated using the root-mean-square percent-relative error (RMS%RE) of prediction. In terms of RMS%RE, the ability of the model to accurately predict the enantiomeric composition of future samples was dependent on the chiral analyte, the polymeric surfactant used, and the surfactant medium, and ranged between 1.57 and 6.10%. Chiral analyte concentrations as low as 5 x 10(-6) M were found to give regression models with good predictability.     

PEO‐Covered Nanoparticles by Emulsion Inversion Point (EIP) Method

This study reports the first PEO‐coated polymer nanoparticles synthesis by miniemulsion polymerization of nano‐emulsions prepared by the low‐energy emulsification method called EIP. The surfactant used was Brij 98, a PEO based non ionic commercial surfactant. The partial phase diagram of the system water/Brij 98/styrene was first determined. The Emulsion Inversion Point technique was then used on the water/Brij 98/styrene system to the formation of styrene‐in‐water nano‐emulsions. After miniemulsion polymerization, particle sizes as low as 36 nm were obtained. To the best of our knowledge, this method had not been used for polymerizable system up to now.

     

A new efficient numerical method for contact mechanics of rough surfaces

In this work, a numerical method has been developed to investigate the adhesionless contact mechanics between rough surfaces. To solve the elastic problem a boundary elements approach is used with self-equilibrated square elements. The domain of integration is discretized developing an “intelligent” adaptive mesh and obtaining a considerable memory saving. The numerical convergence of the method has been verified by comparing the results with the Hertzian solution and by checking the stress probability distribution at the contact interface. The methodology has been then utilized to analyse the contact between an elastic flat substrate and a periodic numerically generated self-affine fractal rigid surface. The fractal surface has been generated by employing spectral methods. The results of our investigation supports the findings of some analytical theories (Persson, 2001) and numerical findings (Yang et al., 2006, Hyun et al., 2004, Carbone and Bottiglione, 2008, Campana and Muser, 2007) in terms of linearity between contact area and load and stress probability distributions.     

The influence of the statistical properties of self-affine surfaces in elastic contacts: A numerical investigation

In the last years, an increasing number of papers has been published in the field of contact mechanics between rough fractal surfaces. The increase in research is motivated by the wide variety of natural and industrial processes that involve formation of rough surfaces and interfaces, characterized by self-similarity or self-affine properties on multiple scales. In this paper, the contact between a linear elastic half-space and a rough self-affine fractal rigid surface is studied by employing a numerical method recently developed by the authors (Putignano et al., 2012). The paper aims at investigating the influence of surface parameters as fractal dimensions, mean square slope and mean square roughness on the relation between the contact area, the load and the average separation. The results show that, for relatively small loads, the real contact area–load relationship coefficient of proportionality $\kappa$ takes the universal value $\kappa =2$ independent of the statistical properties and fractal dimension D_f of the rough surface. This universal constant is just in between the two values predicted respectively by Bush et al. (1975) and Persson (2001). We also find that the average separation vs. load relation is affected by the fractal dimension D_f of the rough surface, as higher D_f lead to an increase of the average separation. Finally, in this work, we also study the behavior of the power spectral densities of the elastically deformed surface and of the distribution of local separations. We find that the trend of this quantities is in agreement with recent theoretical predictions.     

All organic host-guest crystals based on a dumb-bell-shaped conjugated host for light harvesting through resonant energy transfer

Together we glow: Fully organic host-guest crystals with two dyes inserted in their parallel nanochannels display broad emission in the visible range thanks to resonant energy transfer. The conjugated host crystal provides light harvesting in the UV region.     

Electronic states of moiré modulated Cu films

We examined by low-energy electron diffraction and scanning tunneling microscopy the surface of thin Cu films on Pt(111). The Cu/Pt lattice mismatch induces a moiré modulation for films from 3 to about 10?ML thickness. We used angle-resolved photoemission spectroscopy to examine the effects of this structural modulation on the electronic states of the system. A series of hexagonal- and trigonal-like constant energy contours is found in the proximity of the Cu(111) zone boundaries. These electronic patterns are generated by Cu sp-quantum well state replicas, originating from multiple points of the reciprocal lattice associated with the moiré superstructure. Layer-dependent strain relaxation and hybridization with the substrate bands concur to determine the dispersion and energy position of the Cu Shockley surface state.     

RNA and DNA association to zwitterionic and charged monolayers at the air-liquid interface

The objective of this work is to establish under which conditions short RNA molecules (similar to miRNA) associate with zwitterionic phospholipids and how this differs from the association with cationic surfactants. We study how the base pairing (i.e., single stranded versus double stranded nucleic acids) and the length of the nucleic acid and the charge of the lipid/surfactant monolayer affect the association behavior. For this purpose, we study the adsorption of nucleic acids to monolayers composed of dipalmitoyl phosphatidylcholine (DPPC) or dioctadecyl-dimethyl-ammoniumbromide (DODAB) using the surface film balance, neutron reflectometry, and fluorescence microscopy. The monolayer studies with the surface film balance suggested that short single-stranded ssRNA associates with liquid expanded zwitterionic phospholipid monolayers, whereas less or no association is detected for double-stranded dsRNA and dsDNA. In order to quantify the interaction and to determine the location of the nucleic acid in the lipid/surfactant monolayer we performed neutron reflectometry measurements. It was shown that ssRNA adsorbs to and penetrates the liquid expanded monolayers, whereas there is no penetration of nucleic acids into the liquid condensed monolayer. No adsorption was detected for dsDNA to zwitterionic monolayers. On the basis of these results, we propose that the association is driven by the hydrophobic interactions between the exposed hydrophobic bases of the ssRNA and the hydrocarbon chains of the phospholipids. The addition of ssRNA also influences domain formation in the DPPC monolayer, leading to fractal-like interconnected domains. The experimental results are discussed in terms of the implication for biological processes and new leads for applications in medicine and biotechnology.     

The low-pressure focal plane detector of the MAGNEX spectrometer

The focal plane detector of the MAGNEX large acceptance magnetic spectrometer is presented. It is based on a large low-pressure gas-filled tracker followed by a wall of silicon detectors to stop the particles. It has been designed for the stringent requirements from the ion optics and the foreseen use with heavy ions. The performances of the device are demonstrated using 4MeV/u oxygen beams. The results of the tests are described and discussed in view of the application of the particle identification and trajectory reconstruction techniques to recover the kinematic properties of the reaction products. They demonstrate the suitability of such detector in a wide range of experiments where low-energy thresholds, large-accepted solid angle, precise momentum measurement and good particle identification are needed.     

Rossinone-related meroterpenes from the Antarctic ascidian Aplidium fuegiense

The chemical analysis of the ascidian Aplidium fuegiense resulted in the isolation of three novel meroterpenoids 2–4, structurally related to the main co-occurring known rossinone B (1). The structures of the new compounds were determined by interpretation of spectroscopic data. Compounds 1–4 were found to be selectively localized in the viscera of the ascidian.