Critical swelling of particle-encapsulating vesicles

We consider a ubiquitous scenario where a fluctuating, semipermeable vesicle is embedded in solution while enclosing a fixed number of solute particles. The swelling with increasing number of particles or decreasing concentration of the outer solution exhibits a continuous phase transition from a fluctuating state to the maximum-volume configuration, whereupon appreciable pressure difference and surface tension build up. This criticality is unique to particle-encapsulating vesicles, whose volume and inner pressure both fluctuate. It implies a universal swelling behavior of such vesicles as they approach their limiting volume and osmotic lysis.     

Turing invariant sets and the perfect set property

We show that $\text{◂...▸}\mathsf{ZF}+\mathsf{DC}+\text{“all}\text{Turing}\text{invariant}\text{sets}\text{of}\text{reals}\text{have}\text{the}\text{perfect}\text{set}\text{property”}$ implies that all sets of reals have the perfect set property. We also show that this result generalizes to all countable analytic equivalence relations.     

Perimeter of sets and BMO-type norms

The aim of this note is to announce some recent results showing that an isotropic variant of the BMO-type norm introduced in [3] can be related via a precise formula to the perimeter of sets.     

Reactions of carbonate radical anion with amino-carboxylate complexes of manganese(II) and iron(III)

Abstract

The reaction kinetics of eight amino-carboxylate complexes of Fe(III) and Mn(II) with carbonate radical anion were studied using the pulse radiolysis method and UV-vis spectroscopy. Difference spectra revealed the formation of Fe(IV) and Mn(III) after reaction with CO₃^??. Spectral measurements revealed the first step to be the coordination of carbonate to the metal center. All of these led to the conclusion that the role of coordinated carbonate is essential to the electron transfer process by carbonate radical anion.     

A highly fluorescent nucleoside analog based on thieno[3,4-d]pyrimidine senses mismatched pairing

A highly emissive nucleobase analog, based on a thieno[3,4-d]pyrimidine core, is enzymatically incorporated into RNA oilgonucleotides that function as base discriminating fluorescent probes.     

On the effect of induced electro-osmosis on a cylindrical particle next to a surface

The effect of induced electro-osmosis on a cylindrical particle positioned next to a planar surface (wall) is studied theoretically both under the thin double layer approximation utilizing the Smoluchowski slip velocity approximation and under thick electric double layer conditions by solving the Poisson-Nernst-Planck (PNP) equations. The imposed, undisturbed electric field is parallel to the planar surface. The induced hydrodynamic and electrostatic forces are calculated as functions of the particle's and the medium's dielectric constants and the distance between the particle and the surface. The resultant force acting on the particle is directed normal to and away from the wall. The presence of such a repulsive force may adversely affect the interactions between macromolecules suspended in solution and wall-immobilized molecules and may be significant to near-wall particle imaging velocimetry (PIV) in electrokinetic flows.     

The antioxidant tempamine: in vitro antitumor and neuroprotective effects and optimization of liposomal encapsulation and release

The piperidine nitroxide tempamine (TMN) is a cell-permeable, stable radical having antioxidant, anticancer, and proapoptotic and/or pronecrotic activities, as was demonstrated by us in cell cultures. We also demonstrated synergism between TMN and doxorubicin in doxorubicin-sensitive and doxorubicin-resistant cell lines. Treatment of the C26 mouse colon carcinoma model in vivo also demonstrated synergism between TMN and doxorubicin in sterically stabilized liposomes (SSLs) containing TMN (SSL-TMN) and those containing doxorubicin. The above effects of TMN and SSL-TMN motivated us to develop and optimize the SSL-TMN formulation so that it will be able to reach the disease site with a sufficiently high TMN level and a release rate needed to achieve a therapeutic effect. Because TMN is an amphipathic weak base, it was remote loaded by an intraliposome high/extraliposome low transmembrane ammonium sulfate gradient. The kinetics and level of TMN loading were monitored by cyclic voltammetry (CV) and electron paramagnetic resonance (EPR); the latter also indicates TMN precipitation in the intraliposomal aqueous phase. The regeneration of the original CV and EPR signals by the ionophore nigericin indicates that TMN remained fully intact during loading and release. The cardinal role of the transmembrane ammonium ion gradient in the loading process was proven by the use of the selective ionophores nonactin (for NH4+) and nigericin (for H+). The anion of the ammonium salts affects loading stability and the rate of TMN release, both mediated through the TMN state of aggregation in the intraliposomal aqueous phase. The greater the TMN salt precipitation, the slower the TMN release rate. This was supported by measurement of osmolality, which is inversely related to TMN salt precipitate. Precipitation is in the order SO4(-2)>Cl-1>glucuronate-1. Liposome lipid composition, magnitude of the transmembrane ammonium ion gradient, and type of anion of the ammonium salt determine the amount of TMN loaded and its release rate.     

Premicellar aggregation of amphiphilic molecules

We revisit the problem of amphiphilic aggregation using a simple two-state (monomer-aggregate) thermodynamic model, which allows the study of metastable aggregates of variable size. A sequence of well separated concentrations emerge: c(1), where a metastable aggregated state appears; c(2), above which an appreciable amount of metastable aggregates forms; and c(3), where the aggregated state becomes stable. Of these, c(3) is shown to correspond to the critical micelle concentration (cmc) as commonly measured in macroscopic experiments. Thus, appreciable premicellar aggregation is predicted in the concentration range between c(2) and c(3). We show that, so long as the micelles are not too large, the extent of premicellar aggregation is much larger than that expected from mere finite-size effects. It stems from the variability of the micelle size and the small free energy difference between the metastable state, containing monomers and aggregates, and the pure monomeric one. The aggregate size is found to weakly change with concentration below and above the cmc. The existence of premicellar aggregates and their concentration-insensitive size are in agreement with a recent experiment.     

A novel Ce<Superscript>III</Superscript>-cyclam type complex and its redox chemistry in aqueous solutions

A new Ce^III complex was synthesized by mixing the ligand “dioxocyclam” with Ce^III ions at pH 8.0 and its redox properties were investigated.