Luis Portilla

Smoothly tunable surface properties of aluminum oxide core-shell nanoparticles by a mixed-ligand approach.

We present a facile solution-based procedure for tailoring the surface properties of aluminum oxide nanoparticles (AlOx-NPs) by the formation of tunable core-shell systems with self-assembled monolayers. By employing chained molecules with a phosphonic acid anchor group and either hydrophobic or hydrophilic chains the surface properties of the nanoparticles change dramatically. So, the solubility can be tuned orthogonal from trifluorotoluene (CF3-C6H5) for hydrophobic shell to water (H2O) for hydrophilic functionalization respectively. Spray coated films of those functionalized nanoparticles exhibited superhydrophobic or superhydrophilic properties. The surface properties can be tuned smoothly by the formation of a mixed ligand monolayer from corresponding stoichiometric mixtures of the ligands. The core-shell nanoparticles were investigated by means of thermogravimetric analysis, TGA; Fourier transform infrared spectroscopy, FTIR; and static contact angle goniometry, SCA. The effect of different dipole moments of the SAM molecules in mixed shell nanoparticles to their stability in dispersions was studied by zeta potential measurements.

Region‐Selective Deposition of Core–Shell Nanoparticles for 3 D Hierarchical Assemblies by the Huisgen 1,3‐Dipolar Cycloaddition

A method for the region-selective deposition of nanoparticles (NPs) by the Huisgen 1,3-dipolar cycloaddition is presented. The approach enables defined stacking of various oxide NPs in any order with control over layer thickness. Thereby the reaction is performed between a substrate, functionalized with a self-assembled monolayer of an azide-bearing phosphonic acid (PA) and aluminum oxide (AlO(x)) NPs functionalized with an alkyne bearing PA. The layer of alkyne functionalized AlO(x) NPs is then used as substrate for the deposition of azide-functionalized indium tin oxide (ITO) NPs to provide a binary stack. This progression is then conducted with alkyne-functionalized CeO2 NPs, yielding a ternary stack of NPs with three different NP cores. The stacks are characterized by AFM and SEM, defining the region-selectivity of the deposition technique. Finally, these assemblies have been tested in devices as a dielectric to form a capacitor resulting in a dramatic increase in the measured capacitance.

Improving the Performance of Organic Thin-Film Transistors by Ion Doping of Ethylene-Glycol-Based Self-Assembled Monolayer Hybrid Dielectrics.

Tuning the electrostatics of ethylene-glycol-based self-assembled monolayers (SAMs) by doping with ions is shown. Molecular dynamics simulations unravel binding mechanisms and predict dipole strengths of the doped layers. Additionally, by applying such layers as dielectrics in organic thin-film transistors, the incorporated ions are proven to enhance device performance by lowering the threshold voltage and increasing conductivity.

Very Facile Polarity Umpolung and Noncovalent Functionalization of Inorganic Nanoparticles: A Tool Kit for Supramolecular Materials Chemistry.

The facile assembly of shell-by-shell (SbS)-coated nanoparticles [TiO2-PAC16]@shell 1-7 (PAC16 = hexadecylphosphonic acid), which are soluble in water and can be isolated as stable solids, is reported. In these functional architectures, an umpolung of dispersibility (organic apolar versus water) was accomplished by the noncovalent binding of ligands 1-7 to titania nanoparticles [TiO2-PAC16] containing a first covalent coating with PAC16. Ligands 1-7 are amphiphilic and form the outer second shell of [TiO2-PAC16]@shell 1-7. The tailor-designed dendritic building blocks 3-5 contain negative and positive charges in the same molecule, and ligands 6 and 7 contain a perylenetetracarboxylic acid dimide (PDI) core (6/7) as a photoactive reporter component. In the redox and photoactive system [TiO2-PAC16]@shell 7, electronic communication between the inorganic core to the PDI ligands was observed.

Green Processing of Metal Oxide Core–Shell Nanoparticles as Low‐Temperature Dielectrics in Organic Thin‐Film Transistors

TiO2 , Fe3 O4, AlOx , ITO (indium tin oxide), and CeO2 nanoparticles are tailored to exhibit excellent dispersability in deionized water and alcohols. The latter provides an ecofriendly solution for processing metal oxide nanoparticles at a neutral pH. Water-processed dielectrics from the metal oxide nanoparticles are incorporated into organic thin-film transistors fabricated on rigid and flexible substrates.

Enhanced In Vitro Biocompatibility and Water Dispersibility of Magnetite and Cobalt Ferrite Nanoparticles Employed as ROS Formation Enhancer in Radiation Cancer Therapy

Efficient magnetic reactive oxygen species (ROS) formation enhancing agents after X-ray treatment are realized by functionalizing superparamagnetic magnetite (Fe3 O4 ) and Co-ferrite (CoFe2 O4 ) nanoparticles with self-assembled monolayers (SAMs). The Fe3 O4 and CoFe2 O4 nanoparticles are synthesized using Massarts coprecipitation technique. Successful surface modification with the SAM forming compounds 1-methyl-3-(dodecylphosphonic acid) imidazolium bromide, or (2-{2-[2-hydroxy-ethoxy]-ethoxy}-ethyl phosphonic acid provides biocompatibility and long-term stability of the Fe3 O4 and CoFe2 O4 nanoparticles in cell media. The SAM-stabilized ferrite nanoparticles are characterized with dynamic light scattering, X-ray powder diffraction, a superconducting quantum interference device, Fourier transform infrared attenuated total reflectance spectroscopy, zeta potential measurements, and thermogravimetric analysis. The impact of the SAM-stabilized nanoparticles on the viability of the MCF-7 cells and healthy human umbilical vein endothelial cells (HUVECs) is assessed using the neutral red assay. Under X-ray exposure with a single dosage of 1 Gy the intracellular SAM stabilized Fe3 O4 and CoFe2 O4 nanoparticles are observed to increase the level of ROS in MCF-7 breast cancer cells but not in healthy HUVECs. The drastic ROS enhancement is associated with very low dose modifying factors for a survival fraction of 50%. This significant ROS enhancement effect by SAM-stabilized Fe3 O4 and CoFe2 O4 nanoparticles constitutes their excellent applicability in radiation therapy.

Manufacturing Nanoparticles with Orthogonally Adjustable Dispersibility in Hydrocarbons, Fluorocarbons, and Water

Abstract We describe a universal wet‐chemical shell‐by‐shell coating procedure resulting in colloidal titanium dioxide (TiO2) and iron oxide (Fe3O4) nanoparticles with dynamically and reversibly tunable surface energies. A strong covalent surface functionalization is accomplished by using long‐chained alkyl‐, triethylenglycol‐, and perfluoroalkylphosphonic acids, yielding highly stabilized core–shell nanoparticles with hydrophobic, hydrophilic, or superhydrophobic/fluorophilic surface characteristics. This covalent functionalization sequence is extended towards a second noncovalent attachment of tailor‐made nonionic amphiphilic molecules to the pristine coated core–shell nanoparticles via solvophobic (i.e. either hydrophobic, lipophobic, or fluorophobic) interactions. Thereby, orthogonal tuning of the surface energies of nanoparticles via noncovalent interactions is accomplished. As a result, this versatile bilayer coating process enables reversible control over the colloidal stability of the metal oxide nanoparticles in fluorocarbons, hydrocarbons, and water.

Highly Efficient Encapsulation and Phase Separation of Apolar Molecules by Magnetic Shell-by-Shell-Coated Nanocarriers in Water

We report on the development of a supramolecular nanocarrier concept that allows for the encapsulation and separation of small apolar molecules from water. The nanocarriers consist of shell-by-shell-coated nanoparticles such as TiO2 and ferromagnetic Fe3 O4 . The first ligand shell is provided by covalently bound hexadecyl phosphonic acid (PAC16 ) and the second shell by noncovalently assembled amphiphiles rendering the hybrid architecture soluble in water. Agitation of these constructs with water containing the hydrocarbons G1-G4, the fluorescent marker G5, the polychlorinated biphenyl PCB 77, or crude oil leads to a very efficient uptake (up to 411 %) of the apolar contaminant. In case of the hybrids containing a Fe3 O4 core, straightforward phase separation by the action of an external magnet is provided. The load can easily be released by a final treatment with an organic solvent.