Frank H. Quina

Interactions of neutral molecules with ionic micelles

The interactions of neutral molecules with ionic micelles are analyzed. The cell and mass action models are presented in order to provide a semi-quantitative description of the solubilization process. Both approaches are discussed from a thermodynamic and kinetic point of view and the different definitions of solute incorporation constants are also discussed and compared. An extensive compilation of standard free energies of transfer from water to micelles is provided and the basis of the employed methods to obtain them is presented. Several aspects of the solubilization process such as its dynamics, the effect of additives, the probe microenvironment and its dependence with the solute mean occupation number are reviewed and critically discussed. The effect of solute incorporation upon the micelle shape and size is also briefly reviewed.

Effects of temperature and lipid composition on the serum albumin-induced aggregation and fusion of small unilamellar vesicles

Small unilamellar vesicles of egg phosphatidylcholine (PC) or dimyristoylphosphatidylcholine, mixed with small unilamellar vesicles labelled with 2-(10-(1-pyrene)decanoyl)phosphatidylcholine, exhibit a constant average size and excimer to monomer (E/M) ratio for several hours when incubated at pH 3.6 at a temperature higher than the phase transition temperature (Tc) of the lipids. Addition of bovine serum albumin to this system produces a transient turbidity increase, a fast decrease in the E/M ratio, a partial loss of vesicle-entrapped [14C]sucrose and a measurable leak-in of externally added sucrose. Sepharose 4B filtration of the system demonstrates that the E/M ratio decrease is strictly paralleled by the formation of liposomes which exhibit a low E/M ratio and a hydrodynamic radius larger than that of small unilamellar vesicles. These data demonstrate that the E/M ratio decrease can be unequivocally ascribed to a vesicle-vesicle fusion process induced by serum albumin. The rate of serum-albumin induced fusion of small unilamellar vesicles is: (a) maximal at a stoichiometric ratio of approx. 2 albumins per vesicle; (b) sensitive to the nature of the lipid and; (c) not altered when human serum albumin replaces bovine serum albumin. The rate of albumin-induced fusion of dimyristoylphosphatidylcholine small unilamellar vesicles is higher below the Tc of the lipid and increases with temperature above the Tc. The formation of protein-bound aggregates with defined stoichiometries and a high local vesicle concentration, as well as changes in the local degree of hydration, are proposed to be the driving forces for the protein-induced vesicle fusion in this system.

New Perspectives in Micellar Liquid Chromatography

Abstract This paper will summarize several new findings obtained in our laboratory on the use of micellar mobile phases in liquid chromatography. The topics to be addressed include (i) stationary phase modification by the mobile phase surfactant in micellar liquid chromatography, (ii) investigation of the retention mechanism in micellar liquid chromatography (MLC) using an alkyl-benzene homologous series, (iii) evaluation of the effects of organic additives upon retention and efficiency in MLC, and (iv) preliminary characterization of several new classes of surfactant molecules for use in MLC. The information gained from these studies provides new insights into the dynamics of MLC and demonstrates their potential usefulness in several new separation applications including the resolution of optical isomers.

Formation of closed vesicles from a simple phosphate diester. Preparation and some properties of vesicles of dihexadecyl phosphate

Abstract Upon sonication in water above 55°, dihexadecyl phosphate forms aqueous dispersions. Gel filtration, substrate entrapment and electron microscopic investigations indicate that these dispersions consist of closed vesicles possessing the characteristics of single bilayer liposomes. These dispersions are quite sensitive to the presence of salts. These wholly synthetic phosphate diester vesicles provide one of the simplest models for the mimicry of membrane and transport functions.

Efficient sonochemical synthesis of novel 3,5-diaryl-4,5-dihydro-1H-pyrazole-1-carboximidamides

An ultrasound-assisted preparation of a series of novel 3,5-diaryl-4,5-dihydro-1H-pyrazole-1-carboximidamides that proceeds via the efficient reaction of chalcones with aminoguanidine hydrochloride under clean conditions is described.

Ruthenium(II) tris(bipyridyl) ion as a luminescent probe for oxygen uptake

The present work describes an alternative technique for following the rate of oxygen uptake by chemical and enzymatic systems. This method is based on spectrofluorometric monitoring of the well-known quenching effect of molecular oxygen on the emission of the photoexcited [Ru(bpy)3]2+ ion, added to the reaction mixtures. The rate of oxygen consumption determined using the present method agrees with that obtained by conventional polarographic techniques in all of the following systems: ascorbate/Cu2+, glucose/glucose oxidase (EC 1.1.3.4), and propanal/horseradish peroxidase (EC 1.11.1.7); in the last case, agreement was observed both in the presence and absence of serum albumin and of chloroplasts. Spectrofluorometric data for amphotericin autoxidation in dimethyl sulfoxide are in accord with the rate of decay of the ESR signal of a spin trap added to the reaction mixture. The advantages and limitations of the present spectrofluorometric technique relative to conventional polarographic monitoring of dissolved oxygen are discussed.

Environmentally friendly sonocatalysis promoted preparation of 1-thiocarbamoyl-3,5-diaryl-4,5-dihydro-1H-pyrazoles

An efficient and green synthesis of thiocarbamoyl-3,5-diaryl-4,5-dihydro-1H-pyrazoles via the condensation of chalcones with thiosemicarbazide in ethanol and KOH under ultrasound irradiation is reported. The products were isolated in good yields after short reaction times.

On the use of 2,1,3-benzothiadiazole derivatives as selective live cell fluorescence imaging probes

Newly designed 2,1,3-benzothiadiazole-containing fluorescent probes with four excited state intramolecular proton transfer (ESIPT) sites were successfully tested in live cell-imaging assays using a confluent monolayer of human stem-cells (tissue). All tested dyes were compared with the commercially available DAPI and gave far better results.

Photochemistry of anthocyanins and their biological role in plant tissues

Anthocyanins, the major red, purple, and blue pigments of plants, absorb visible as well as UV radiation and are effective antioxidants and scavengers of active oxygen species. In plant leaves, one of the functional roles proposed for anthocyanins is protection of the photosynthetic apparatus from the effects of excess incident visible or UV-B radiation and photooxidative stress. In essence, a photoprotective role requires that the excited singlet states of both complexed and uncomplexed anthocyanins deactivate back to the ground state so quickly that intersystem crossing, photoreaction, and diffusion-controlled quenching processes cannot compete. Studies of the photochemical properties of synthetic analogs of anthocyanins and of several naturally occurring anthocyanins show that this is indeed the case, uncomplexed anthocyanins decaying back to the ground state via fast (subnanosecond) excited-state proton transfer (ESPT) and anthocyanin-copigment complexes by fast (subpicosecond) charge-transfer-mediated internal conversion.

Novel chiral separation techniques based on surfactants

Abstract Aqueous solutions of three different general types of chiral organized surfactant media are characterized and evaluated as mobile phases in micellar liquid chromatography (MLC), or as the transport vehicle in liquid membrane (LM) based separations. The surfactant systems examined included bile salts (e.g., sodium cholate, sodium deoxylcholate, sodium taurocholate), mixed surfactant systems containing a chiral surfactant additive (e.g., sodium dodecyl sulfate with octyl glucopyranoside or digitonin), and a chiral quaternary ammonium ionene polyelectrolyte. The preliminary data indicate that all of these surfactant organized assemblies can function as either chiral mobile phase additives or the active component of liquid membranes for the resolution of optical isomers, in addition to separating other isomeric and routine compounds. Specifically, the bile salt aggregates are useful in the separation of substituted binaphthyl enantiomers, whereas mixed micellar systems such as sodium dodecyl sulfate/chiral nonionic surfactant media appear to be effective in the separation of some derivatized amino acid optical isomers and anomeric saccharides. The ionene media can function as the enantioselective discriminating agent in the liquid membrane based separation of enantiomeric dansyl amino acids. Our preliminary results on these systems are summarized in this paper. The salient features, advantages, limitations, and potential applications of these new chiral surfactant-mediated separation techniques are discussed.