Asymmetric cellulose nanocrystals: thiolation of reducing end groups via NHS–EDC coupling

Cellulose nanocrystals (CNC) were functionalized in aqueous media at the reducing, aldehyde ends of cellulose. CNC oxidation to produce carboxyl groups was followed by carbodiimide-mediated reaction to install thiol groups. The selectivity and extent of thiolation at the reducing ends was qualitatively confirmed by imaging (transmission electron microscopy) silver nanoparticles that tagged the CNC termini and by X-ray photoelectron spectroscopy, respectively. The adsorption of thiolated CNC onto gold surfaces as well as the viscoelastic property of the formed adlayer was investigated by using quartz crystal microgravimetry. The thiolated CNC chemisorbed on the surfaces were further analyzed for surface density and distribution by using atomic force microscopy. Overall we introduce a facile, mild asymmetric thiolation procedure as an efficient alternative to conventional reductive amination.     

Self-assembling and phase coexistence of SW trimers as complex amphiphile analogues. I. Simulations

We analyse by discrete molecular dynamics the self-assembly of SW trimer particles that contain a different number of attractive and repulsive spheres. They also have different geometries: linear, obtuse, rectangular and equilateral. We identify that some of these molecules exhibit liquid–vapour equilibria while others do not. For all of them, we show the morphological phase diagram built up from the different supra-molecular structures formed by each type of trimer. We simulated 14 different systems with a total of 321 states. The main features of the supra-molecular structures depend only on the composition and geometry of the trimer: triple SW trimers do not form supra-structures, double SW trimers and single SW trimers form monolayers, bilayers and worm-like micelles. The liquid–vapour coexistence properties are also exhibited. These trimers can be used to model complex amphiphiles beyond the standard ones, such as the Gemini and the Bola surfactants as well as colloidal particles.     

ZnSe films deposited on crystalline GaAs and amorphous quartz substrates by means of pulsed laser ablation technique

ZnSe films were deposited by pulsed laser ablation on a crystalline GaAs substrate and on an amorphous quartz substrate. The deposition process was performed with the same growth parameters. The films were investigated by means of X-ray diffraction, reflectance and photoluminescence spectroscopy. The X-ray diffraction spectra have demonstrated that the films grow in a highly oriented way but having different orientations, i.e. the films deposited on GaAs grow (100)-oriented and the films deposited on quartz grow (111)-oriented. Reflectance spectra as a function of the temperature have been analysed by means of the classical oscillator model, in order to obtain the temperature dependence of the band gap energy. This gives results comparable to those of ZnSe single crystals for ZnSe on GaAs, but it is red-shifted for ZnSe on quartz, because of lattice and thermal strains. The photoluminescence measurements at T = 10 K confirm the better quality of ZnSe deposited on GaAs and show that pulsed laser ablation is a promising technique to grow films having intrinsic luminescence even on an amorphous substrate. Received 29 May 2002 Published online 31 October 2002 RID="a" ID="a"e-mail: giuseppe.perna@ba.infn.it     

Stereoselective synthesis of alpha-C-glucosyl serine and alanine via a cross-metathesis/cyclization strategy

C-Glycosyl amino acids represent stable mimics of monomeric units within natural O-linked glycoproteins. Olefin cross-metathesis has been used to provide alkene precursors for a mercury(II)-mediated cyclization, yielding alpha-C-glucosyl serine and alanine.     

Probing decoherence with electromagnetically induced transparency in superconductive quantum circuits

Superconductive quantum circuits comprise quantized energy levels that may be coupled via microwave electromagnetic fields. Described in this way, one may draw a close analogy to atoms with internal (electronic) levels coupled by laser light fields. In this Letter, we present a superconductive analog to electromagnetically induced transparency that utilizes superconductive quantum circuit designs of present day experimental consideration. We discuss how a superconductive analog to electromagnetically induced transparency can be used to establish macroscopic coherence in such systems and, thereby, be utilized as a sensitive probe of decoherence.     

Role of excitons in electron- and photon-stimulated desorption of neutrals from alkali halides

Low-energy (5-15 eV) electron- and photon-stimulated desorption of KI(100) yields I2P3/2 and 2P1/2 with hyperthermal (0.3 eV) and thermal velocity components. The desorption threshold for both components is 5.3 eV and is correlated with the gamma3/2-exciton long-wavelength edge. Exciton decay at the surface directly produces I2P3/2 and 2P1/2 with hyperthermal velocity and is in competition with self-trapping. Spin memory of the gamma-exciton hole-component is also evident in the hyperthermal channel. An exciton mediated desorption mechanism is presented which is general in alkali halides.     

The Bootstrap Methodology in Statistics of Extremes—Choice of the Optimal Sample Fraction

The main objective of statistics of extremes is the prediction of rare events, and its primary problem has been the estimation of the tail index , usually performed on the basis of the largest k order statistics in the sample or on the excesses over a high level u. The question that has been often addressed in practical applications of extreme value theory is the choice of either k or u, and an adaptive estimation of . We shall be here mainly interested in the use of the bootstrap methodology to estimate adaptively, and although the methods provided may be applied, with adequate modifications, to the general domain of attraction of G, , we shall here illustrate the methods for heavy right tails, i.e. for > 0. Special relevance will be given to the use of an auxiliary statistic that is merely the difference of two estimators with the same functional form as the estimator under study, computed at two different levels. We shall also compare, through Monte Carlo simulation, these bootstrap methodologies with other data-driven choices of the optimal sample fraction available in the literature.