Transformation of Lipid Vesicles into Micelles by Adding Nonionic Surfactants: Elucidating the Structural Pathway and the Intermediate Structures.

The phospholipid lecithin (L) and the nonionic surfactant Tween 80 (T) are used together in various contexts, including in drug delivery and oil spill remediation. There is hence a need to elucidate the nanostructures in LT mixtures, which is the focus of this paper. We study these mixtures using cryogenic transmission electron microscopy (cryo-TEM), coupled with dynamic light scattering and small-angle neutron scattering.

Using Microemulsion Phase Behavior as a Predictive Model for Lecithin-Tween 80 Marine Oil Dispersant Effectiveness.

Marine oil dispersants typically contain blends of surfactants dissolved in solvents. When introduced to the crude oil-seawater interface, dispersants facilitate the breakup of crude oil into droplets that can disperse in the water column. Recently, questions about the environmental persistence and toxicity of commercial dispersants have led to the development of "greener" dispersants consisting solely of food-grade surfactants such as l-α-phosphatidylcholine (lecithin, L) and polyoxyethylenated sorbitan monooleate (Tween 80, T).

Surface Activity of Poly(ethylene glycol)-Coated Silver Nanoparticles in the Presence of a Lipid Monolayer.

We have investigated the surface activity of poly(ethylene glycol) (PEG)-coated silver nanoparticles (Ag-PEG) in the presence or absence of lipid monolayers comprised of monounsaturated dioleoylphosphocholine and dioleoylphosphoglycerol (DOPC/DOPG; 1:1 mol ratio). Dynamic measurements of surface pressure demonstrated that Ag-PEG were surface-active at the air/water interface. Surface excess concentrations suggested that at high Ag-PEG subphase concentrations, Ag-PEG assembled as densely packed monolayers in the presence and absence of a lipid monolayer.

Tuning the Multifunctionality of Iron Oxide Nanoparticles Using Self-Assembled Mixed Lipid Layers.

We present an approach to tuning the multifunctionality of iron oxide nanoparticles (IONs) using mixed self-assembled monolayers of cationic lipid and anionic polyethylene glycol (PEG) lipid. By forming stable, monodispersed lipid-coated IONs (L-IONs) through a solvent-exchange technique, we were able to demonstrate the relationship between surface charge, the magnetic transverse relaxivity (r from T-weighted images), and the binding capacity of small interfering ribonucleic acids (siRNAs) as a function of the cationic-to-anionic (PEG) lipid ratio. These properties were controlled by the cationic charge and the PEG conformation; relaxivity and siRNA binding could be varied in the mushroom and brush regimes but not at high brush densities.

Development of Aerosol Phospholipid Microparticles for the Treatment of Pulmonary Hypertension.

Pulmonary arterial hypertension (PAH) is an incurable cardiovascular disease characterized by high blood pressure in the arteries leading from the heart to the lungs. Over two million people in the USA are diagnosed with PAH annually and the typical survival rate is only 3 years after diagnosis. Current treatments are insufficient because of limited bioavailability, toxicity, and costs associated with approved therapeutics.

Hydrophobic Nanoparticles Modify the Thermal Release Behavior of Liposomes.

Understanding the effect of embedded nanoparticles on the characteristics and behavior of lipid bilayers is critical to the development of lipid-nanoparticle assemblies (LNAs) for biomedical applications. In this work we investigate the effect of hydrophobic nanoparticle size and concentration on liposomal thermal release behavior. Decorated LNAs (D-LNAs) were formed by embedding 2 nm (GNP2) and 4 nm (GNP4) dodecanethiol-capped gold nanoparticles into DPPC liposomes at lipid to nanoparticle ratios (L:N) of 25,000:1, 10,000:1, and 5,000:1.

Cyclodextrin-promoted Diels Alder reactions of a polycyclic aromatic hydrocarbon under mild reaction conditions.

Reported herein is the effect of cyclodextrins on the rates of aqueous Diels Alder reactions of 9-anthracenemethanol with a variety of -substituted maleimides. These reactions occurred under mild reaction conditions (aqueous solvent, 40 °C), and were most efficient for the reaction of -cyclohexylmaleimide with a methyl-β-cyclodextrin additive (94% conversion in 24 hours). These results can be explained on the basis of a model wherein the cyclodextrins bind the hydrophobic substituents on the maleimides and activate the dienophile via electronic modulation of the maleimide double bond.

Oxidative Cross-Coupling of sp(3)- and sp(2)-Hybridized C-H Bonds: Vanadium-Catalyzed Aminomethylation of Imidazo[1,2-a]pyridines.

The vanadium-catalyzed oxidative coupling of substituted 2-arylimidiazo[1,2-a]pyridines to N-methylmorpholine oxide, which acts as both a coupling partner and an oxidant, has been achieved. This reaction was applied to various substituted imidiazo[1,2-a]pyridine and indole substrates, resulting in yields as high as 90%. Mechanistic investigations indicate that the reaction may proceed via a Mannich-type process.

Rapid and efficient pesticide detection via cyclodextrin-promoted energy transfer.

Cyclodextrins facilitate non-covalent fluorescence energy transfer from a variety of pesticides to high quantum-yield fluorophores, resulting in a rapid, sensitive detection scheme for these compounds with detection limits as low as two micromolar. Such a facile detection tool has significant potential applications in agriculture and public health research.

Array-based detection of persistent organic pollutants via cyclodextrin promoted energy transfer.

We report herein the selective array-based detection of 30 persistent organic pollutants via cyclodextrin-promoted energy transfer. The use of three fluorophores enabled the development of an array that classified 30 analytes with 100% accuracy and identified unknown analytes with 96% accuracy, as well as identifying 92% of analytes in urine.

Efficient extraction and detection of aromatic toxicants from crude oil and tar balls using multiple cyclodextrin derivatives.

Herein we report the efficient extraction of aromatic analytes from crude oil and tar balls using multiple cyclodextrin derivatives. The known propensity of the cyclodextrins to bind hydrophobic guests in their hydrophobic interiors enhanced the extraction of aromatic analytes from the oil layer to the aqueous layer, with methyl-β-cyclodextrin and β-cyclodextrin providing the most significant enhancement in extraction efficiencies of aromatic toxicants (69% aromatic toxicants in aqueous layer in the presence of methyl-β-cyclodextrin compared to 47% in cyclodextrin-free solution for tar ball oil extraction), and provide optimal tunability for developing efficient extraction systems. The cyclodextrin derivatives also promoted efficient energy transfer in the aqueous solutions, with up to 86% efficient energy transfer observed in the presence of γ-cyclodextrin compared to 50% in the absence of cyclodextrin for oil spill oil extraction.

Highly efficient detection of hydrogen peroxide in solution and in the vapor phase via fluorescence quenching.

Herein we report the highly efficient and sensitive detection of hydrogen peroxide in both aqueous solution and in the vapor phase via fluorescence quenching (turn-off mechanism) of the amplified fluorescent conjugated polymer-titanium complex induced by hydrogen peroxide. Inter- and intra-polymer energy migration leads to extremely high sensitivity.

Synthesis of a β-CCT-lanthanide conjugate for binding the dopamine transporter.

The development of a β-CCT-lanthanide conjugate that binds the dopamine transporter (DAT) with high affinity (K(d) = 303 nM) is described. Contrast agents such as the one described herein could be used as molecular probes to directly study the binding of small molecules to receptors such as DAT via MRI, PET or SPECT.

Regioselective gold-catalyzed oxidative C-N bond formation.

A novel protocol for the regioselective intermolecular amination of various arenes has been developed. By using an I(III) oxidant in the presence of a Au(I) catalyst, a direct and novel route for regioselectively accessing a variety of substituted aniline moieties has been achieved with yields as high as 90%. Mechanistic insight suggests that regioselectivity can be predicted based on electrophilic aromatic metalation patterns.

Gas-phase reactions of alcohols with hexamethylene triperoxide diamine (HMTD) under atmospheric pressure chemical ionization conditions.

Rationale: Hexamethylene triperoxide diamine (HMTD) is a sensitive peroxide explosive first synthesized in 1885. HMTD exhibits an unusual gas-phase phenomenon in the presence of alcohols that has been previously observed, but incorrectly resolved. We are attempting to determine this specific mechanism.

Electroless plating of thin gold films directly onto silicon nitride thin films and into micropores.

A method to directly electrolessly plate silicon-rich silicon nitride with thin gold films was developed and characterized. Films with thicknesses <100 nm were grown at 3 and 10 °C between 0.5 and 3 h, with mean grain sizes between ∼20 and 30 nm.

Iron-catalyzed arylation of heterocycles via directed C-H bond activation.

The iron-catalyzed arylation of aromatic heterocycles, such as pyridines, thiophenes, and furans, has been achieved. The use of an imine directing group allowed for the ortho functionalization of these heterocycles with complete conversion in 15 min at 0 °C. Yields up to 88% were observed in the synthesis of 15 heterocyclic biaryls.

Cyclodextrin-promoted energy transfer for broadly applicable small-molecule detection.

Reported herein is the development of non-covalent, proximity-induced energy transfer from small-molecule toxicants to organic fluorophores bound in the cavity of γ-cyclodextrin. This energy transfer occurs with exceptional efficiency for a broad range of toxicants in complex biological media, and is largely independent of the spectral overlap between the donor and acceptor. This generally applicable phenomenon has significant potential in the development of new turn-on detection schemes.

Cyclodextrin-enhanced extraction and energy transfer of carcinogens in complex oil environments.

Reported herein is the use of γ-cyclodextrin for two tandem functions: (a) the extraction of carcinogenic polycyclic aromatic hydrocarbons (PAHs) from oil samples into aqueous solution and (b) the promotion of highly efficient energy transfer from the newly extracted PAHs to a high-quantum-yield fluorophore. The extraction proceeded in moderate to good efficiencies, and the resulting cyclodextrin-promoted energy transfer led to a new, brightly fluorescent signal in aqueous solution. The resulting dual-function system (extraction followed by energy transfer) has significant relevance in the environmental detection and cleanup of oil-spill-related carcinogens.

Speciation of the products of and establishing the role of water in the reaction of TNT with hydroxide and amines: structure, kinetics, and computational results.

The reaction of trinitrotoluene (TNT) with bases has been investigated by NMR and visible spectroscopy methods. Hydroxide ion was found to react in one of two ways, either by deprotonation of the methyl group or by nucleophilic attack on the aromatic ring to form a σ adduct. The rate of each mode of reaction depends upon the polarity of the solvent.

Sensitive and selective detection of cesium via fluorescence quenching.

Herein we report a robust and easy method for detecting cesium metal ion (Cs(+)) in partially aqueous solutions using the fluorescence quenching of 2,4-bis[4-(N,N-dihydroxyethylamino)phenyl]squaraine. This squaraine dye was found to be both highly sensitive (low limits of detection) and selective (limited response to other metals) for cesium ion detection. The detection is likely based on the metal complexing to the dihydroxyethanolamine moieties, which disrupts the donor-acceptor-donor architecture and leads to efficient quenching.

Nanopore surface coating delivers nanopore size and shape through conductance-based sizing.

The performance of nanopore single-molecule sensing elements depends intimately on their physical dimensions and surface chemical properties. These factors underpin the dependence of the nanopore ionic conductance on electrolyte concentration, yet the measured, or modeled, dependence only partially illuminates the details of geometry and surface chemistry. Using the electrolyte-dependent conductance data before and after selective surface functionalization of solid-state nanopores, however, introduces more degrees of freedom and improves the performance of conductance-based nanopore characterizations.

Chiral cationic polyamines for chiral microcapsules and siRNA delivery.

Reported herein is the use of chiral cationic polyamines for two intriguing applications: fabrication of chiral covalently-linked microcapsules, and enantiospecific delivery of siRNA to Huh 7 cells. The microcapsules are easily fabricated from homochiral polymers, and the resulting architectures can be used for supramolecular chiral catalysis and many other potential applications. Enantiospecific delivery of siRNA to Huh 7 cells is seen by one 'enantiomer' of the polymers delivering siRNA with significantly improved transfection efficiency and reduced toxicity compared to the 'enantiomeric' polymer and commercially available transfection reagents.

Highly efficient non-covalent energy transfer in all-organic macrocycles.

The use of aromatic organic macrocycles as supramolecular hosts for non-covalent energy transfer is reported herein. These macrocycles lead to stronger binding and more efficient energy transfer compared to commercially available γ-cyclodextrin. This energy transfer was particularly efficient for the highly toxic benzo[a]pyrene with a fluorescent BODIPY acceptor, with up to a 5-fold increase in the fluorophore emission observed.

Insight into the palladium catalyzed oxidative arylation of benzofuran: Heteropoly acid oxidants evoke a Pd(II)/Pd(IV) mechanism.

The effects of oxidant and organic acid additives on the oxidative cross-coupling reactions of electron rich heterocycles such as benzofuran with benzene were studied. Both regioselectivity and reaction rate could be controlled by varying the condition parameters. Furthermore, mechanistic insight was achieved via kinetic studies which indicate that reactions that are oxidized by the heteropoly acid HPMoVO operate via a Pd(II)/Pd(IV) mechanisms, while reactions oxidized by either AgOAc or Cu(OAc) operate by a Pd(II)/Pd(0) mechanism.