Laponite clay in homopolymer and tri-block copolymer matrices

Macromolecule/laponite nanomaterials were studied by DSC and X-ray diffraction techniques. The matrices are poly(ethylene) glycols at various molecular masses and poly(ethylene oxides)-poly(propylene oxides)-poly(ethylene oxides) tri-block copolymers. The latter were tuned by modulating the molecular masses, at constant hydrophilic/hydrophobic ratio, and the hydrophilicity. For all the investigated systems, the enthalpy of melting (ΔH _m) is nearly constant up to a given composition thereafter it increases monotonically reaching the value of the pure macromolecule. We proposed a model to interpret the DSC data. Briefly, it was invoked a mechanism of interaction following which some segments of the adsorbed macromolecule are anchored to the laponite (RD) particles and the remaining segments are radiating away from the surface. The portion of the macromolecule in contact with RD does not contribute to ΔH _m whereas that radiating away from the clay does. Once that the RD surface is saturated, the excess of the macromolecule behaves like the pure one. The proposed model allowed to compute successfully the ΔH _m values. The X-ray diffraction experiments ruled out the polymer intercalation between the silicate sheets.     

High-performance liquid chromatographic determination of BRB-I-28, a novel antiarrhythmic agent, in dog plasma and urine.

A sensitive reversed-phase high-performance liquid chromatographic (HPLC) technique with ultraviolet detection has been developed to determine the concentration of BRB-I-28 (I), a novel antiarrhythmic agent, in dog plasma and urine. The mobile phase was acetonitrile-methanol-37.5 mM phosphate buffer, pH 6.8-triethylamine (50:50:75:0.1, v/v). The compound was extracted from dog plasma and urine with chloroform after alkalinization with sodium hydroxide. The extraction recovery was 83% from plasma and 84% from urine. Good linearity (r > 0.996) was observed throughout the ranges 0.1-12.0 micrograms/ml (plasma) and 0.1-8.0 micrograms/ml (urine). Intra- and inter-assay variabilities were less than 4%. The lower limit of quantitation was 0.08 microgram/ml in either plasma or urine. HPLC analysis of plasma and urine samples from a dog treated with I has demonstrated that the method was accurate and reproducible.     

Effects of concentration on the partitioning of macromolecule mixtures in agarose gels

To test the effects of solute concentration on the equilibrium partitioning of single macromolecules and macromolecule mixtures between bulk solutions and gels, the partition coefficient in agarose was measured for BSA and for four narrow fractions of Ficoll with Stokes radii of 30-59 A. Solutions of each test macromolecule were equilibrated with a known volume of gel, final liquid concentrations measured, and partition coefficients (gel concentration divided by bulk concentration) calculated by applying a material balance. The partition coefficient of each macromolecule was measured in 4 and 6% gels under dilute conditions and with BSA present at initial concentrations up to 13.5 g/dl. As expected, the partition coefficients decreased with increasing agarose concentration and with increasing macromolecular size. Moreover, increasing the BSA concentration increased the partition coefficient of BSA itself and that of all four Ficolls. This effect was most pronounced for the largest test solutes. Measurements at two ionic strengths confirmed that electrostatic interactions were negligible under the conditions used. The experimental results were compared with predictions from a previously developed excluded volume theory for the partitioning of mixtures of rigid, spheroidal macromolecules in fibrous media. Agarose was represented as a randomly oriented array of cylindrical fibers, BSA as a prolate spheroid, and Ficoll as a sphere. The quantitative agreement between the model predictions and the data was generally quite good, indicating that steric interactions among solute molecules and between solute molecules and gel fibers could explain the partitioning results. The theory is simple enough computationally to be applied to a variety of processes that are influenced by the equilibrium partitioning of macromolecules.     

Preparation of solvent-free, pore-spanning lipid bilayers: modeling the low tension of plasma membranes

Plasma membrane tension, produced by the underlying cytoskeleton, governs many dynamic processes such as fusion, blebbing, exo- and endocytosis, cell migration, and adhesion. Here, a new protocol is introduced to model this intricate and often overlooked aspect of the plasma membrane. Lipid bilayers spanning pores of 600 nm radius were prepared by adsorption and spreading of giant unilamellar vesicles (GUVs) on moderately hydrophilic porous substrates prepared by gold-coating and subsequent self-assembly of a mercaptoethanol monolayer. Rupture of GUVs formed tens of micrometer sized pore-spanning membrane patches displaying low tension of σ ≤ 3.5 mN m(-1) and lateral diffusion constants of about 8 μm(2) s(-1). Site-specific force indentation experiments were performed to determine membrane tension as a function of lipid composition: for pure DOPC bilayers, a tension of 1.018 ± 0.014 mN m(-1) was measured, which was increased by the addition of cholesterol to 3.50 ± 0.15 mN m(-1). Compared to DOPC, POPC bilayers displayed a larger tension of 2.00 ± 0.09 mN m(-1). Addition and subsequent partitioning of 2-propanol was shown to significantly reduce the membrane tension as a function of its concentration.     

Determination of As(III) by anodic stripping voltammetry using a lateral gold electrode: experimental conditions, electron transfer and monitoring of electrode surface

The aim of this work is to evaluate the efficiency of the determination of As(III) by anodic stripping voltammetry (ASV) using a lateral gold electrode and to study the modifications of the electrode surface during use. Potential waveforms (differential pulse and square wave), potential scan parameters, deposition time, deposition potential and surface cleaning procedure were examined for they effect on arsenic peak intensity and shape. The best responses were obtained with differential pulse potential wave form and diluted 0.25 M HCl as supporting electrolyte. The repeatability, linearity, accuracy and detection limit of the procedure and the interferences of cations and anions in solution were evaluated. The applicability of the procedure for As(III) determination in drinking waters was tested. Cyclic voltammetry (CV) was used to study the electrochemical behaviour of As(III) and for the daily monitoring of electrode surface. Also scanning electron microscopy (SEM) analysis was used to control the electron surface. Finally we evaluated the possibility to apply the equations valid for flow systems also to a stirred system, in order to calculate the number of electrons transferred per molecule during the stripping step.     

Aggregation in aqueous media of tri-block copolymers tuned by the molecular selectivity of cyclodextrins

The water + cyclodextrin + poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) mixtures have been investigated to explore the temperature effect on the aggregation of the copolymer in the presence of cyclodextrins (CDs). The CDs with different cavity sizes were chosen because they may include either the hydrophilic poly(ethylene oxides) block or both kinds of blocks. The differential scanning calorimetry and viscosity experiments straightforwardly evidenced that the critical micellar temperature is shifted to larger values by adding a CD which is able to include the middle poly(propylene oxide) block while it is not influenced by the presence of CD which is selective to the poly(ethylene oxide) block. The enthalpy of aggregation decreases upon the CD addition for all the investigated systems.     

Mirror symmetry breaking and chiral amplification in foldamer-based supramolecular helical aggregates

Spontaneous asymmetric generation of supramolecular chiral fibers was observed in the folding induced self-assembly of a lock-washer shaped foldamer. A secondary nucleation growth mechanism is proposed to explain the observed chiral amplification or deracemization of these supramolecular fibers.     

Gold nanoparticles stabilized by modified halloysite nanotubes for catalytic applications

A highly sustainable prototype of a flow system based on gold nanoparticles (4.2 nm) supported on thiol‐functionalized halloysite nanotubes (HNTs) was developed for catalytic applications. The catalytic performances were evaluated using the reduction of 4‐nitrophenol to 4‐aminophenol as a model system. Under the best experimental conditions (0.0001 mol%, 1.97 × 10^?8 mg of Au nanoparticles), an impressive apparent turnover frequency value up to 2 204 530 h^?1 was achieved and the halloysite‐based catalyst showed full recyclability even after ten cycles. The high catalytic activity confirms the importance of the use of HNTs as support for Au nanoparticles that can exert a synergistic effect both as medium for transfer of electrons from borohydride ions to 4‐nitrophenol and by modulating interfacial electron transfer dynamics. With the application of flow technology, the obtained heterogeneous HNT@Au catalyst was fully recovered and reused for at least one month.