Production of color centers in PMMA by ultrashort laser pulses

We report here the creation of color centers in commercial, transparent PMMA samples by ultrashort pulses from a Ti:Sapphire laser emitting at 800 nm, with spatial control. Although the 800 nm photon energy is not sufficient to ionize the polymer, the centers are created following a multiphotonic absorption that causes the ionization. We propose that the free electrons quivering motion on the pulse electric field displaces atoms from its equilibrium positions, creating free radicals and double bonds that coalesce into color centers. The absorption and emission spectra of the centers were measured, but a dose-like curve could not be built due to the presence of damages created along with the centers that scatter the excitation and emission lights due to the commercial sample's poor optical quality.     

Water effects on electron transfer in azurin dimers

Recent experimental and theoretical analyses indicate that water molecules between or near redox partners can significantly affect their electron-transfer (ET) properties. Here, we study the effects of intervening water molecules on the electron self-exchange reaction of azurin (Az) by using a newly developed ab-initio method to calculate transfer integrals between molecular sites. We show that the insertion of water molecules in the gap between the copper active sites of Az dimers slows down the exponential decay of the ET rates with the copper-to-copper distance. Depending on the distance between the redox sites, water can enhance or suppress the electron-transfer kinetics. We show that this behavior can be ascribed to the simultaneous action of two competing effects: the electrostatic interaction of water with the protein subsystem and its ability to mediate ET coupling pathways.     

Versatile low-molecular-weight hydrogelators: achieving multiresponsiveness through a modular design

Multiresponsive low-molecular-weight hydrogelators (LMWHs) are ideal candidates for the development of smart, soft, nanotechnology materials. The synthesis is however very challenging. On the one hand, de novo design is hampered by our limited ability to predict the assembly of small molecules in water. On the other hand, modification of pre-existing LMWHs is limited by the number of different stimuli-sensitive chemical moieties that can be introduced into a small molecule without seriously disrupting the ability to gelate water. Herein we report the synthesis and characterization of multistimuli LMWHs, based on a modular design, composed of a hydrophobic, disulfide, aromatic moiety, a maleimide linker, and a hydrophilic section based on an amino acid, here N-acetyl-L-cysteine (NAC). As most LMWHs, these gelators experience reversible gel-to-sol transition following temperature changes. Additionally, the NAC moiety allows reversible control of the assembly of the gel by pH changes. The reduction of the aromatic disulfide triggers a gel-to-sol transition that, depending on the design of the particular LMWH, can be reverted by reoxidation of the resulting thiol. Finally, the hydrolysis of the cyclic imide moieties provides an additional trigger for the gel-to-sol transition with a timescale that is appropriate for use in drug-delivery applications. The efficient response to the multiple external stimuli, coupled to the modular design makes these LMWHs an excellent starting point for the development of smart nanomaterials with applications that include controlled drug release. These hydrogelators, which were discovered by serendipity rather than design, suggest nonetheless a general strategy for the introduction of multiple stimuli-sensitive chemical moieties, to offset the introduction of hydrophilic moieties with additional hydrophobic ones, in order to minimize the upsetting of the critical hydrophobic-hydrophilic balance of the LMWH.     

Double-differential spectra of the secondary particles in the frame of pre-equilibrium model

An approach was developed to describe the double-differential spectra of secondary particles formed in heavy-ion reactions. Griffin model of nonequilibrium processes was used to account for the nonequilibrium stage of the compound system formation. Simulation of de-excitation of the compound system was carried out using the Monte-Carlo method. Analysis of the probability of neutron, proton, and α-particle emission was performed both in equilibrium, and in the pre-equilibrium stages of the process. Fission and γ-ray emission were also considered after equilibration. The analysis of the experimental data on the double-differential cross sections of p, α particles for the ¹⁶O + ¹¹⁶Sn reaction at the oxygen energy E = 130 and 250 MeV were performed.     

ACTION DES HYDRAZINES ET DE L'HYDROXYLAMINE SUR QUELQUES PHOSPHONATES β, β-BIFONCTIONNALISES: SYNTHESE DE PHOSPHONOAMINOPYRAZOLES ET ISOXAZOLES

Abstract

Reaction of hydrazines and hydroxylamine with β, β-bifunctionalized phosphonates 1 and 1′ leads to phosphoaminopyrazoles and isoxazoles 2 3, 4 and 5. The structure of all obtained products was confirmed by NMR and IR spectroscopy.     

Fixed or invertible calixarene-based directional shuttles

The first examples of rotaxanes based on calixarenes threaded by dialkylammonium ions, which also represent the first examples of calixarene-based molecular shuttles, are reported. The base/acid treatment demonstrated that these systems act as molecular shuttles, which move between three sites on the axle. When small OMe groups are appended at the calix[6]arene lower rim an unprecedented inversion of its shuttling direction is observed, which occurs through a cone-to-cone inversion of the macrocycle.     

Thermo-optical properties of silver and gold nanofluids

This work focuses on the study of thermal diffusivity and physical properties of nanofluids with very low concentrations of silver or gold nanoparticles. Thermal measurements were performed by means of thermal lens spectroscopy in the dual beam configuration. Improvements of 20 and 16 % in the thermal diffusivity were observed for silver and gold nanofluids, respectively, in comparison with pure water. The estimation of the size distribution of the metallic nanoparticles was obtained through the fitting of the extinction spectra via Mie theory and images of field emission gun scanning electron microscopy.     

Geometric scaling effects on instrumental plate height in field flow fractionation

This paper examines geometric scaling models for field flow fractionation systems to understand how channel dimensions affect resolution and retention. Specifically, the changing contribution of the instrumental plate height during miniaturization of field flow fractionation (FFF) systems is reported. The work is directed towards determining the optimal geometrical parameters for miniaturization of field flow fractionation systems. The experimental relationship between channel height in FFF systems and instrumental plate heights is reported. FFF scaling models are modified to: (i) better clarify the dependence of plate height and resolution on channel height in FFF and (ii) include a more complete geometrical scaling analysis and model comparison in the low retention regime. Electrical field flow fractionation has been shown to benefit from miniaturization, so this paper focuses on that subtype, but surprisingly, the results also indicate the possibility of improvement in performance with miniaturization of other field flow fractionation systems including general FFF subtypes in which the applied field does not vary with channel height. This paper also discusses the potential role of more powerful microscale field flow fractionation systems as a new class of sample preparation units for micro-total-analysis systems (mu-TAS).