Cycloreversion of azetidines via oxidative electron transfer. steady-state and time-resolved studies

Cycloreversion of cis- and trans-1,2,3-triphenylazetidine (c-2 and t-2) is achieved by electron transfer to (tris(4-bromophenyl)aminium radical cation (5 (*+)). Stepwise C-N and C-C bond cleavage of azetidine radical cations leads to cis- and trans-stilbene, together with N-benzylideneaniline, as final products. Mechanistic evidence is provided by quenching studies, using laser flash photolysis to generate 5 (*+) from its neutral precursor.     

Stereoselective NaN3-catalyzed halonitroaldol-type reaction of azetidine-2,3-diones in aqueous media

Azetidine-2,3-diones (alpha-oxo-beta-lactams) and bromonitromethane undergo coupling in aqueous media in the presence of catalytic amounts of sodium azide. The stereoselectivity of the process was generally good, proceeding with reasonable anti : syn ratios under substrate control. On this basis, a simple and fast protocol for the synthesis of the potentially bioactive 3-substituted 3-hydroxy-beta-lactam moiety has been developed. Besides, 2-azetidinone-tethered 1-halo-1-nitroalkan-2-ols are quite useful building blocks; for example, reactions of the above nitrobromohydrins provided spiranic and fused bicyclic-beta-lactams.     

A rapid and reliable size-exclusion chromatographic method for determination of kojic dipalmitate in skin-whitening cosmetic products

A size-exclusion chromatographic method has been developed to determine the relatively novel skin-whitening agent called kojic dipalmitate (KDP) in skin-whitening cosmetic products. Preliminary experiments were carried out in order to select the solvent for standard and sample solution, and also for mobile phase composition. A PLGel Mixed-D (polystyrene/divinylbenzene co-polymer) column and isocratic mobile phase of pure tetrahydrofuran (at 1.5 mL min(-1) flow rate) were used. Detection was carried out by means of an UV/vis spectrometry detector set at 248 nm. A study of interferences reveals that KDP can be determined without interferences coming from cosmetic matrices. Most other cosmetic ingredients usually employed in skin-whitening cosmetic products, such as other whitening agents and common UV filters, do not interfere. The accuracy and precision of the proposed method was tested by the analysis of six laboratory-made and five commercial skin-whitening cosmetic samples. The sensitivity and limit of detection (3 microg mL(-1)) obtained are suitable for the analysis of this type of samples. The chromatographic run takes less than 8 min to complete. All these features make the method easy to apply to quality control in the cosmetic industry.     

Annulation of internal alkynes through a hydroamination/aza-Heck reaction sequence for the regioselective synthesis of indoles

Highly regioselective annulation reactions of unsymmetrically substituted alkynes by primary 2-bromo or 2-chloroanilines are achieved with an efficient one-pot protocol, which relies on a regioselective TiCl₄-catalyzed intermolecular hydroamination and a subsequent palladium-catalyzed intramolecular aza-Heck reaction. The use of unsymmetrically substituted alkynes in this strategy enables the synthesis of diversely functionalized indoles, with a regioselectivity that is complementary to the one obtained when employing Larock's annulation reaction.     

Preparation and evaluation of butyl acrylate-based monolithic columns for CEC using ammonium peroxodisulfate as a chemical initiator

Acrylate-ester-based monoliths for CEC using peroxodisulfate as a chemical initiator were prepared. The influence of two ternary porogenic solvents on the physical and chromatographic properties of butyl acrylate monolithic stationary phases was investigated. The composition and the ratio of porogenic solvent were adjusted to obtain highly permeable rigid monoliths with adequate column efficiency. Among the prepared butyl acrylate monoliths, those polymerized from a ternary porogenic solvent of acetonitrile/ethanol/water exhibited the most promising performance with a minimum plate height for naphthalene of 10.5 microm and a bed permeability of 7.3 x 10(-14) m(2). A comparison in terms of efficiency and permeability with thermal and UV initiation using alpha,alpha'-AIBN was also performed. The resulting monolithic stationary phases were evaluated in terms of reproducibility, giving RSD values below 5.1% in the electrochromatographic properties studied.     

Development of intermolecular potential models for electrolyte solutions using an electrolyte SAFT-VR Mie equation of state

ABSTRACT

We present a theoretical framework and parameterisation of intermolecular potentials for aqueous electrolyte solutions using the statistical associating fluid theory based on the Mie interaction potential (SAFT-VR Mie), coupled with the primitive, non-restricted mean-spherical approximation (MSA) for electrolytes. In common with other SAFT approaches, water is modelled as a spherical molecule with four off-centre association sites to represent the hydrogen-bonding interactions; the repulsive and dispersive interactions between the molecular cores are represented with a potential of the Mie (generalised Lennard-Jones) form. The ionic species are modelled as fully dissociated, and each ion is treated as spherical: Coulombic ion–ion interactions are included at the centre of a Mie core; the ion–water interactions are also modelled with a Mie potential without an explicit treatment of ion–dipole interaction. A Born contribution to the Helmholtz free energy of the system is included to account for the process of charging the ions in the aqueous dielectric medium. The parameterisation of the ion potential models is simplified by representing the ion–ion dispersive interaction energies with a modified version of the London theory for the unlike attractions. By combining the Shannon estimates of the size of the ionic species with the Born cavity size reported by Rashin and Honig, the parameterisation of the model is reduced to the determination of a single ion–solvent attractive interaction parameter. The resulting SAFT-VRE Mie parameter sets allow one to accurately reproduce the densities, vapour pressures, and osmotic coefficients for a broad variety of aqueous electrolyte solutions; the activity coefficients of the ions, which are not used in the parameterisation of the models, are also found to be in good agreement with the experimental data. The models are shown to be reliable beyond the molality range considered during parameter estimation. The inclusion of the Born free-energy contribution, together with appropriate estimates for the size of the ionic cavity, allows for accurate predictions of the Gibbs free energy of solvation of the ionic species considered. The solubility limits are also predicted for a number of salts; in cases where reliable reference data are available the predictions are in good agreement with experiment.     

Structure–Function Relationships in Unsymmetrical Zinc Phthalocyanines for Dye‐Sensitized Solar Cells

Let it shine! The impact of the anchoring group on photovoltaic performance by a series of phthalocyanine sensitisers (see figure) has been demonstrated.