A simple synthesis of γ-aminoacids

The addition of dianions of carboxylic acids to bromoacetonitrile, leads, in good yields, to the corresponding γ-cyanoacids that give γ-aminoacids on hydrogenation. This two-step methodology improves the results previously described.     

Properties of two polymerisable surfactants aqueous solutions: dodecylethylmethacrylatedimethylammonium bromide and hexadecylethylmethacrylatedimethylammonium bromide. II. Partial molar volume and micelle hydration

The partial molar volume and hydration number of two micellised polymerisable surfactants (dodecylethylmethacrylatedimethylammonium bromide (C₁₂PS) and hexadecylethylmethacrylatedimethylammonium bromide (C₁₆PS)) were determined. Results support marginally the annular conformation of the polar head group (N⁺(CH₃)₂-CH₂-CH₂-O-CO-C(CH₃)(=CH₂)) proposed in the literature.     

The interaction of electrolytes with non-ionic surfactant micelles

The effect of NaCl and HCl on two non-ionic surfactant micelles was studied using several techniques, including conductivity and ion-selective electrodes. Both surfactants exhibit opposite behaviour. When Tween 20 is titrated with HCl the conductivity notably increases in comparison with water, whereas that of Triton X-100 solutions do not change with respect to water until a certain HCl concentration is reached, when it increases. The hydrogen ion activity is lower in Triton X-100 solutions and higher in Tween 20 solutions than in pure water. Chloride ion activity is higher in Tween 20 solutions than in water, whereas in Triton X-100 the activity does not significantly differ from that in water. The activity of sodium ion is lower in Tween 20 solutions than in water, whereas that in Triton X-100 solutions does not differ from the titration of water. These phenomena are explained by the changes in conformation of the non-ionic headgroups, which capture water, and in some cases ions, modifying the activity of ions in the intermicellar solution.     

Modulation of metal-azolate frameworks for the tunable release of encapsulated glycosaminoglycans

Glycosaminoglycans (GAGs) are biomacromolecules necessary for the regulation of different biological functions. In medicine, GAGs are important commercial therapeutics widely used for the treatment of thrombosis, inflammation, osteoarthritis and wound healing. However, protocols for the encapsulation of GAGs in MOFs carriers are not yet available. Here, we successfully encapsulated GAG-based clinical drugs (heparin, hyaluronic acid, chondroitin sulfate, dermatan sulfate) and two new biotherapeutics in preclinical stage (GM-1111 and HepSYL proteoglycan) in three different pH-responsive metal-azolate frameworks (ZIF-8, ZIF-90, and MAF-7). The resultant GAG@MOF biocomposites present significant differences in terms of crystallinity, particle size, and spatial distribution of the cargo, which influences the drug-release kinetics upon applying an acidic stimulus. For a selected system, heparin@MOF, the released therapeutic retained its antithrombotic activity while the MOF shell effectively protects the drug from heparin lyase. By using different MOF shells, the present approach enables the preparation of GAG-based biocomposites with tunable properties such as encapsulation efficiency, protection and release.

Clinical and pre-clinical GAG-based biotherapeutics were encapsulated within three metal-azolate frameworks (ZIF-8, ZIF-90, and MAF-7). The resulting MOF biocomposites show different loading capacity, biopreservation properties and release profiles.     

Block copolymers of ethylene oxide and phenyl glycidyl ether: micellization, gelation, and drug solubilization

Three triblock copolymers of ethylene oxide and phenyl glycidyl ether, type E(m)G(n)E(m), where G = OCH2CH(CH2OC6H5) and E = OCH2CH2, were synthesized and characterized by gel-permeation chromatography, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, and NMR spectroscopy. Their association properties in aqueous solution were investigated by surface tensiometry and light scattering, yielding values of the critical micelle concentration (cmc), the hydrodynamic radius, and the association number. Gel boundaries in concentrated micellar solution were investigated by tube inversion, and for one copolymer, the temperature and frequency dependence of the dynamic moduli served to confirm and extend the phase diagram and to highlight gel properties. Small-angle X-ray scattering was used to investigate gel structure. The overall aim of the work was to define a block copolymer micellar system with better solubilization capacity for poorly soluble aromatic drugs than had been achieved so far by use of block copoly(oxyalkylene)s. Judged by the solubilization of griseofulvin in aqueous solutions of the E(m)G(n)E(m) copolymers, this aim was achieved.     

Synthesis, characterization and immobilization of Prussian blue nanoparticles. A potential tool for biosensing devices

Prussian blue (PB) particles with the size of ca. 5 nm were synthesized and immobilized in a multilayer structure, as a strategy for the potential development of an amperometric transducer for oxidase-enzyme-based biosensors. Multilayer films composed of PB and poly(allylamine hydrochloride) (PAH) were prepared via layer-by-layer (LbL) sequential deposition. The process was carefully monitored by UV-vis spectroscopy and cyclic voltammetry. The increase of the redox current peaks during the layer-by-layer deposition demonstrated that charge propagation within the film occurs. Linear increase of UV-vis absorbance with the number of deposited bilayers indicates that well-organized systems have been elaborated. ITO electrodes coated with PB/PAH films were used successfully for detecting H2O2, sensitivity being dependent on the number of PB/PAH layers.     

Thermodynamic properties of tetrachlorocyclopropene

A facility is described which incorporates the use of electronic microbalances to follow gravimetric changes due to the formation or spallation of surface oxides on metals or alloys during high temperature oxidation. The outputs from the balances are fed into a data acquisition system which allows easy collection and analysis of the data from more than one microbalance.The sensitivity of the technique is illustrated by reference to the measurements of oxidation and spallation on a 20Cr/25Ni/Nb stabilised stainless steel oxidised in flowing CO₂ based gas at 1 atmosphere pressure and 850°C.     

Monte Carlo molecular simulation of the hydration of K-montmorillonite at 353 K and 625 bar

Monte Carlo molecular simulations of the hydration of K-saturated Wyoming-type montmorillonite at constant stress in the NPzzT ensemble and at constant chemical potential in the grand canonical muVT ensemble, under basin-like conditions of 353 K and 625 bar, show a strong tendency of the K+ ions to adhere to the siloxane surface, forming predominant inner-sphere complexes with tetrahedral oxygen atoms and adsorbed water molecules. Simulations in the grand canonical ensemble predict that none of the K-montmorillonite hydrates, the one-, two-, and three-layer hydrates, are stable in this environment of high depth, temperature, and pressure. The most nearly stable configuration corresponds to the one-layer hydrate, characterized by a d001 spacing of 12.75 A, the adsorbed water being 60 molecules/layer or 180.83 mg of H2O/g of clay, an internal energy of -22.73 kcal/mol, an interlayer density of 0.365 g/mL, and a pressure tensor, Pzz, of 1999.9 bar. The interlayer structure consists of two close layers of water molecules 0.50 A from the midplane, with broad shoulders on the sides, the protons oriented toward the midplane and the siloxane surfaces, and the K+ ions close to the clay surfaces and on the interlayer midplane.     

Surfactant/nonionic copolymer interaction: a SLS, DLS, ITC, and NMR investigation

The interactions between an oxyphenylethylene-oxyethylene nonionic diblock copolymer with the anionic surfactant sodium dodecyl sulfate (SDS) have been studied in dilute aqueous solutions by static and dynamic light scattering (SLS and DLS, respectively), isothermal titration calorimetry (ITC), and 13C and self-diffusion nuclear magnetic resonance techniques. The studied copolymer, S20E67, where S denotes the hydrophobic styrene oxide unit and E the hydrophilic oxyethylene unit, forms micelles of 15.6 nm at 25 degrees C, whose core is formed by the styrene oxide chains surrounded by a water swollen polyoxyethylene corona. The S20E67/SDS system has been investigated at a copolymer concentration of 2.5 g dm(-3), for which the copolymer is fully micellized, and with varying surfactant concentration up to approximately 0.15 M. When SDS is added to the solution, two different types of complexes are observed at various surfactant concentrations. From SLS and DLS it can be seen that, at low SDS concentrations, a copolymer-rich surfactant mixed micelle or complex is formed after association of SDS molecules to block copolymer micelles. These interactions give rise to a strong decrease in both light scattering intensity and hydrodynamic radius of the mixed micelles, which has been ascribed to an effective reduction of the complex size, and also an effect arising from the increasing electrostatic repulsion of charged surfactant-copolymer micelles. At higher surfactant concentrations, the copolymer-rich surfactant micelles progressively are destroyed to give surfactant-rich-copolymer micelles, which would be formed by a surfactant micelle bound to one or very few copolymer unimers. ITC data seem to confirm the results of light scattering, showing the dehydration and rehydration processes accompanying the formation and subsequent destruction of the copolymer-rich surfactant mixed micelles. The extent of interaction between the copolymer and the surfactant is seen to involve as much as carbon 3 (C3) of the SDS molecule. Self-diffusion coefficients corroborated light scattering data.