Evaluation of asymmetric liposomal nanoparticles for encapsulation of polynucleotides

Conventional lipid bilayer liposomes have similar inner and outer leaflet compositions; asymmetric liposomes have different lipid leaflet compositions. The goal of this work is to place cationic lipids in the inner leaflet to encapsulate negatively charged polynucleotides and to place neutral/anionic lipids on the outer leaflet to decrease nonspecific cellular uptake/toxicity. Inverse emulsion particles have been developed with a single lipid leaflet of cationic and neutral lipids surrounding an aqueous core containing a negatively charged 21-mer DNA oligo. The particles are accelerated through an oil-water interface, entrapping a second neutral lipid to form oligo encapsulated unilamellar liposome nanoparticles. Inverse emulsion particles can be consistently produced to encapsulate an aqueous environment containing negatively charged oligo. The efficiency of encapsulated liposome formation is low and depends on the hydrocarbon used as the oil phase. Dodecane, mineral oil, and squalene were tested, and squalene, a branched hydrocarbon, yielded the highest efficiency.     

Reverse micellar microextraction for rapid analysis of thiol-containing peptides and amino acids by atmospheric-pressure matrix-assisted laser desorption/ionization ion trap and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Simple, rapid and inexpensive one-step reverse micellar microextraction (RMME) procedures were combined with matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) for the determination of thiol-containing peptides and amino acids. In this investigation, a thiol-containing peptide (HW6) was chosen as model compound to understand the mechanism of RMME. The electrostatic interactions between the thiol-containing peptide and reverse micelles were proposed to be reason for the transfer of analytes from the aqueous phase to the organic phase. Reverse micelles were formed by the cationic surfactant, methyltrioctylammonium chloride (MTOAC). The best extraction efficiency of HW6 was obtained under the following conditions: pH 11.0, ionic strength 5.0 mM of KCl and micelle concentration 7.0 mM of MTOAC. The limits of detection (LODs) obtained for HW6 in water, urine and plasma samples were 0.15, 0.19 and 0.28 microM, respectively, with relative standard deviation (RSD) values in the range +/-8.8-10.5%. The sensitivity obtained in water by the present method was 45-fold higher than that of the conventional use of atmospheric-pressure (AP)-MALDI MS. Furthermore, the applicability of the proposed approach was extended for the determination of thiol-containing amino acids in sample solutions by using MALDI time-of-flight (TOF) MS.     

Electronic and structural investigations of gold clusters doped with copper: Aun-1Cu- (n=13-19)

We have obtained the ground state and the equilibrium geometries of Au(n) (-) and Au(n-1)Cu(-) in the size range of n=13-19. We have used first principles density functional theory within plane wave and Gaussian basis set methods. For each of the cluster we have obtained at least 100 distinct isomers. The anions of gold clusters undergo two structural transformations, the first one from flat cage to hollow cage and the second one from hollow cage to pyramidal structure. The Cu doped clusters do not show any flat cage structures as the ground state. The copper doped systems evolve from a general 3D structure to hollow cage with Cu trapped inside the cage at n=16 and then to pyramidal structure at n=19. The introduction of copper atom enhances the binding energy per atom as compared to gold cluster anions.     

Ethylene glycol promoted catalyst-free pseudo three-component green synthesis of bis(coumarin)s and bis(3-methyl-1-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-5-ol)s

An ethylene glycol promoted catalyst-free practically efficient and sustainable approach has been developed for the synthesis of several benzylidene-bis-(4-hydroxycoumarin)s and 4,\(4^{\prime }\)-(arylmethylene)-bis(3-methyl-1-phenyl-1H-pyrazol-5-ol)s by the pseudo three-component reaction of an aldehyde with 4-hydroxycoumarin and 3-methyl-1-phenylpyrazol-5-one, respectively. Inexpensive, non-toxic, and easily available ethylene glycol used as the reaction solvent and promoter renders an efficient protocol in terms of catalyst-free reaction conditions, short reaction time, high yield, practical utility, and green approach.     

DABCO-catalyzed synthesis of 3-substituted-3-hydroxyindolin-2-ones in aqueous media

An efficient and greener protocol for easy access to 3-susbstituted-3-hydroxy-2-oxindoles by the reaction with various substituted isatins and acetophenones is described. This protocol is widely applicable for a variety of isatins and acetophenones using water as a reaction media and 1,4-diazabicyclo[2.2.2]octane (DABCO) as catalyst with shorter reaction time and good to excellent yield of products.     

Understanding surfactant aided aqueous dispersion of multi-walled carbon nanotubes

Dispersions of multi-walled carbon nanotubes (MWNTs) assisted by surfactant adsorption were prepared for a number of ionic and non-ionic surfactants including sodium 4-dodecylbenzenesulfonate (NaDDBS), hexadecyl(trimethyl)azanium bromide (CTAB), sodium dodecane-1-sulfonate (SDS), Pluronic? F68, Pluronic? F127, and Triton? X-100 to examine the effects of nanotube diameter, surfactant concentration, and pH on nanotube dispersability. Nanotube diameter was found to be an important role in surfactant adsorption rendering single-walled carbon nanotube studies as unreliable in predicting MWNT dispersive behavior. Similar to other reports, increasing surfactant concentrations resulted in a solubility plateau. Quantification of nanotube solubility at these plateaus demonstrated that CTAB is the best surfactant for MWNTs at neutral pH conditions. Deviations from neutral pH demonstrated negligible influence on non-ionic surfactant adsorption. In contrast, both cationic and anionic surfactants were found to be poor dispersing aids for highly acidic solutions while, CTAB remained a good surfactant under strongly basic conditions. These pH dependent results were explained in the context of nanotube surface ionization and Debye length variation.