Amphiphilic sorbents based on polysiloxanes crosslinked by an N,N′‐heterocycle

New amphiphilic sorbents have been synthesized by crosslinking of the chloromethyl side‐functionalized polysiloxanes with piperazine. Three structures, differing by the crosslinking degree, have been synthesized as potential sensitive materials for humidity sensors able to work at high humidity or as metal sorbents. Correlations between structure and morphology of the polymeric matrix, as well as their swelling capacity in solvents with different polarities, are discussed. Copyright © 2006 John Wiley & Sons, Ltd.     

Impurities in commercial phytantriol significantly alter its lyotropic liquid-crystalline phase behavior

The lyotropic liquid-crystalline phase behavior of phytantriol is receiving increasing interest in the literature as a result of similarities with glyceryl monooleate, despite its very different molecular structure. Some differences in the phase-transition temperature for the bicontinuous cubic to reverse hexagonal phase have been reported in the literature. In this study, we have investigated the influence that the commercial source and hence the purity has on the lyotropic phase behavior of phytantriol. Suppression of the phase-transition temperatures (by up to 15 degrees C for the bicontinuous cubic to reverse hexagonal phase transition) is apparent with lower-purity phytantriol. In addition, the composition boundaries were also found to depend significantly on the source and purity of phytantriol, with the bicontinuous cubic phase + excess water boundary occurring at a water content above that reported previously (i.e., >5% higher). Both the temperature and compositional changes in phase boundaries have significant implications on the use of these materials and highlight the impact that subtle levels of impurities can play in the phase behavior of these types of materials.     

Elucidation of the Key Role of [Ru(bpy)3]2+ in Photocatalyzed RAFT Polymerization

Photocatalysis reactions using [Ru^II(bpy)₃]²⁺ were studied on the example of visible‐light‐sensitized reversible addition–fragmentation chain transfer (RAFT) polymerization. Although both photoinduced electron‐ and energy‐transfer mechanisms are able to describe this interaction, no definitive experimental proof has been presented so far. This paper investigates the actual mechanism governing this reaction. A set of RAFT agents was selected, their redox potentials measured by cyclic voltammetry, and relaxed triplet energies calculated by quantum mechanics. Gibbs free‐energy values were calculated for both electron‐ and energy‐transfer mechanisms. Quenching rate constants were determined by laser flash photolysis. The results undoubtedly evidence the involvement of a photoinduced energy‐transfer reaction. Controlled photopolymerization experiments are discussed in the light of the primary photochemical process and photodissociation ability of RAFT agent triplet states.     

Structure, stability and guest affinity of tris(3-ureidobenzyl)amine capsules in solution

In non-competitive solvents, the tris(3-ureidobenzyl)amines 1 a-c form dimeric assemblies in which guests such as CH(3)CN, CH(3)NO(2), CH(2)Cl(2), CH(3)I, CH(2)BrCl, CH(2)Br(2), CHCl(3) and C(6)H(6) can be encapsulated. Variable temperature (1)H and (1)H,(1)H-ROESY NMR spectroscopy, as well as pulsed-gradient spin-echo (PGSE) diffusion measurements were used to investigate the encapsulation within 1 a1 a (1 a: tris{3-[N'-(4-butylphenyl)ureido]benzyl}amine). Kinetic parameters for the encapsulation of CH(3)NO(2), CH(2)Cl(2) and CH(3)I, both in CDCl(3) and in [D(8)]toluene have been obtained by using magnetisation transfer methods. These data are discussed together with the thermodynamic parameters. The affinity between guest and capsule seems to be dictated mainly by the electronic, size and shape complementarity between cavity and guest. A gating mechanism for guest exchange is proposed.     

Investigation of single-molecule kinetics mediated by weak hydrogen bonds within a biological nanopore

The study of factors essential for protein-peptide interactions and protein pore-mediated peptide transport are of particular relevance in biology. Wild-type α-hemolysin was adopted as a "nanoreactor" in which perturbations of the current through a protein containing a lumen-residing, aryl-capped antimicrobial peptide were seen for the first time and studied at the single-molecule level. Energy and steric considerations hint that Met-aryl interactions between aromatic residues placed at a peptide's extremities and any of the methionines lining the α-hemolysin constriction region may be the primary cause of peptide stabilization within the lumen and may be particularly important to the peptide-α-hemolysin interaction.     

Providing Support in Favor of the Existence of a PdII/PdIV Catalytic Cycle in a Heck‐Type Reaction

The complex [Pd(O,N,C‐L)(OAc)], in which L is a monoanionic pincer ligand derived from 2,6‐diacetylpyridine, reacts with 2‐iodobenzoic acid at room temperature to afford the very stable pair of Pd^IV complexes (OC‐6‐54)‐ and (OC‐6‐26)‐[Pd(O,N,C‐L)(O,C‐C₆H₄CO₂‐2)I] (1.5:1 molar ratio, at ?55 °C). These complexes and the Pd^II species [Pd(O,N,C‐L)(OX)] and [Pd(O,N,C‐L′)(NCMe)]ClO₄, (X=MeC(O) or ClO₃, L′=another monoanionic pincer ligand derived from 2,6‐diacetylpyridine), are precatalysts for the arylation of CH₂?CHR (R?CO₂Me, CO₂Et, Ph) using IC₆H₄CO₂H‐2 and AgClO₄. These catalytic reactions have been studied and a tentative mechanism is proposed. The presence of two Pd^IV complexes was detected by ESI(+)‐MS during the catalytic process. All the data obtained strongly support a Pd^II/Pd^IV catalytic cycle.     

From Graftable Biphotonic Chromophores to Water‐Soluble Organic Nanodots for Biophotonics: The Importance of Environmental Effects

The photophysical and two‐photon absorption (TPA) properties of biphotonic chromophores with one or two phenol pendant units were studied and compared with that of a model biphotonic quadrupolar chromophore. A water‐soluble dendritic structure was then synthesized by using the pendant moieties as starting points for the construction of dendritic branches. We show that the polarity of the environment significantly modulates both the fluorescence and the TPA responses of the different chromophoric derivatives. This extends to more subtle effects that involve phenol pendant moieties that were found to act as discrete solvating units and to modify both the photophysics and the TPA response of the chromophore. This demonstrates the high sensitivity of the TPA response of quadrupolar derivatives to minute alterations in the environment. Moreover, the dendritic branches were found to behave as a peculiar cybotactic environment that was able to tune the fluorescence and TPA response of the inner chromophore by creating a polar environment. This reveals a new direction for exploiting such effects by playing on the dendritic architecture (e.g., the nature and shape of the building blocks, the geometry and position of the chromophore) to modulate the TPA responses.     

One-pot preparation of piperazines by regioselective ring-opening of non-activated arylaziridines

Herein we report a new straightforward synthesis of cis and trans 2,5-disubstituted N,N-dialkylpiperazines, even in enantioenriched form, by reacting non-activated N-alkyl arylaziridines in the presence of a catalytic amount of a Lewis acid. A stereochemical and NMR investigation revealed useful mechanistic insights for this process.     

Micellization Process in Poly(Ether Urethane) Solutions

Poly(ether urethane)s containing different hard segments were investigated by viscometry, fluorescence spectra, polarizing optical microscopy, and scanning electron microscopy. The polarity dependence of the vibrational structure of the pyrene emission spectrum indicated the formation of aggregates at concentrations that are significantly below the critical concentrations that define the separation of dilute‐semidilute domains. Unlike the sample with 4,4'‐methylene diphenylene diisocyanate, the sample with 2,4‐tolylene diisocyanate in hard segments gives a fluorescence spectra in which the pyrene excimer appears. Supermolecular structures associated with the form of spherulites or of spherical micelles were detected by scanning electron microscopy. The results are discussed in correlation with viscometric data and optical microscopy.     

The Study of Zeolite ZSM-5 by a Dielectric Spectroscopy Method

The dielectric absorption spectrum of zeolite ZSM-5, in the range of frequencies 100 c - 10 Mc, was studied. The influence of the crystallization degree and influence of the Si/Al ratio on the amplitude of the dielectric absorption were analysed. It was observed that _max depends on the Si/Al ratio in an exponential form. An excess of Et.OH in the mixture of crystallization influences favorably the kinetics of the process.