Release of proteins and enzymes from vesicular compartments by alternating magnetic fields.

The magnetic release of catalytically active enzymes from vesicular compartments within aggregated nanomaterials has been demonstrated. These nanomaterials, magnetic nanoparticle-vesicle aggregates (MNPVs), were formed by the self-assembly of biotinylated silica-coated Fe3O4 nanoparticles, biotinylated vesicles and tetrameric avidin. The unique features of nanoscale magnetite allow adhesion between membranes to be combined with magnetically triggered transit of reagents across membranes. Adding short spacers between the adhesive biotin groups and the nanoparticle or vesicle surfaces was found to strengthen binding to avidin, with binding of avidin to biotinylated bilayers and biotinylated nanoparticles monitored by quartz crystal microgravimetry with dissipation (QCM-D). Three different reagents were released from the vesicle compartments of MNPVs by a pulse of alternating magnetic field, with the release of a dye modelling the release of small molecule substrates, and the release of cytochrome c modelling the release of biological polymers, such as enzymes. To confirm that enzymes could be released and maintain activity, trypsin was encapsulated and shown to digest casein after magnetically triggered release.

Fructose controlled ionophoric activity of a cholate-boronic acid.

Wulff-type boronic acids have been shown to act as ionophores at pH 8.2 by transporting Na(+) through phospholipid bilayers. A cholate-boronic acid conjugate was synthesised and shown to be an ionophore, although the hydroxyl-lined face of the cholate moiety did not enhance ion transport. Mechanistic studies suggested a carrier mechanism for Na(+) transport. The addition of fructose (>5 mM) strongly inhibited ionophoric activity of the cholate-boronic acid conjugate, mirrored by a strong decrease in the ability of this compound to partition into an organic phase. Modelling of the partitioning and ion transport data, using a fructose/boronic acid binding constant measured at pH 8.2, showed a good correlation with the extent of fructose/boronic acid complexation and suggested high polarity fructose/boronic acid complexes are poor ionophores. The sensitivity of ion transport to fructose implies that boronic acid-based antibiotic ionophores with activity modulated by polysaccharides in the surrounding environment may be accessible.

Influence of the solvent and metal center on supramolecular chirality induction with bisporphyrin tweezer receptors. Strong metal modulation of effective molarity values.

We describe the synthesis of a bisporphyrin tweezer receptor 1·H(4) and its metalation with Zn(II) and Rh(III) cations. We report the thermodynamic characterization of the supramolecular chirality induction process that takes place when the metalated bisporphyrin receptors coordinate to enantiopure 1,2-diaminocyclohexane in two different solvents, toluene and dichloromethane. We also performed a thorough study of several simpler systems that were used as models for the thermodynamic characterization of the more complex bisporphyrin systems. The initial complexation of the chiral diamine with the bisporphyrins produces a 1:1 sandwich complex that opens up to yield a simple 1:2 complex in the presence of excess diamine. The CD spectra associated with the 1:1 and 1:2 complexes of both metalloporphyrins, 1·Zn(2) and 1·Rh(2), display bisignate Cotton effects when the chirogenesis process is studied in toluene solutions. On the contrary, in dichloromethane solutions, only 1·Zn(2) yields CD-active 1:1 and 1:2 complexes, while the 1:2 complex of 1·Rh(2) is CD-silent. In both solvents, porphyrin 1·Zn(2) features a stoichiometrically controlled chirality inversion process, which is the sign of the Cotton effect of the 1:1 complex is opposite to that of the 1:2 complex. In contrast, porphyrin 1·Rh(2) affords 1:1 and 1:2 complexes in toluene solutions with the same sign for their CD couplets. Interestingly, in both solvents, the signs of the CD couplets associated with the 1:1 sandwich complexes of 1·Zn(2) and 1·Rh(2) are opposite. The amplitudes of the CD couplets are higher for 1·Zn(2) than for 1·Rh(2). This observation is in agreement with 1·Rh(2) having a smaller extinction coefficient than 1·Zn(2). We performed DFT-based calculations and assigned molecular structures to the 1:1 and 1:2 complexes that explain the observed signs for their CD couplets. Unexpectedly, the quantification of the thermodynamic stability of the two metallobisporphyrin/diamine 1:1 sandwich complexes revealed the existence of interplay between effective molarity values (EM) and the strength of the intermolecular interaction (K(m); N···Zn or N···Rh) used in their assembly. The EM for the N···Rh(III) intramolecular interaction is 3 orders of magnitude smaller than that for the N···Zn(II) interaction, both of which are embedded in the same scaffold of the 1·M(2) bisporphyrin receptor.

Supramolecular inclusion complexes of two cyclic zinc bisporphyrins with C60 and C70: structural, thermodynamic, and photophysical characterization.

The formation of thermodynamically stable inclusion complexes between two cyclic zinc bisporphyrins, differing in the saturation degree of the hydrocarbon linkers that connect their porphyrin units, and the fullerenes C(60) and C(70) is described. Binding and photophysical studies were performed in two solvents of very different polarity: toluene and dichloromethane. UV/Vis and fluorescence titration experiments showed π-π interactions between the cyclic zinc bisporphyrins and the fullerenes. Solid-state structures were determined by X-ray diffraction analysis and gave valuable insight into the different complexation behaviors of the two macrocyclic systems towards the fullerenes. NMR titrations were also helpful in understanding the geometry of the complexes in solution. Upon fullerene complexation, the two macrocyclic bisporphyrins adopt very distinct conformations. Charge-transfer absorption bands point to ground-state interactions, and quenching of the porphyrin component luminescence indicates fast reactivity in the excited states. Energy transfer plus HOMO-HOMO and LUMO-LUMO electron-transfer processes occur within the complexes. Charge-separated states characterized by a reduced fullerene and an oxidized porphyrin radical, with lifetimes in the order of several hundred picoseconds, are detected.

TTF-based bent-core liquid crystals.

The synthesis and characterization of bent-core liquid crystals which incorporate TTF groups is reported; different bent-core mesophases are induced depending on the molecular structure and properties derived from their compact packing have been studied.

Experimental test of curvature-driven dynamics in the phase ordering of a two dimensional liquid crystal.

We study electric field driven deracemization in an achiral liquid crystal through the formation and coarsening of chiral domains. It is proposed that deracemization in this system is a curvature-driven process. We test this prediction using the recently obtained exact result for the distribution of hull-enclosed areas in two-dimensional coarsening with nonconserved scalar order parameter dynamics [J. J. Arenzon et al., Phys. Rev. Lett. 98, 145701 (2007)]. The experimental data are in very good agreement with the theory. We thus demonstrate that deracemization in such bent-core liquid crystals belongs to the Allen-Cahn universality class, and that the exact formula, which gives us the statistics of domain sizes during coarsening, can also be used as a strict test for this dynamic universality class.