Metal oxides have gained significant interest aspseudocapacitor electrodes due to reversible faradaicsurface reactions that allow for high power density andgreater energy storage than carbon based electric doublelayer capacitors. However, classically investigatedmaterials like RuO2, MnO2, and Ni(OH)2 suffer from highcost, low life cycles, or limited potential windows,respectively.1-3 As such, there is growing demand for newmaterials with improved energy storage and stability.Herein, we demonstrate the capacitive characteristics ofthree lanthanum based perovskite type oxides, LaMnO3,LaNiO3, and LaCoO3. Based on the inherent nature ofperovskites to contain oxygen vacancies, we demonstratethrough cyclic voltammetry that perovskites store chargethrough anions in alkaline electrolytes, likely in the formof hydroxides. This hypothesis was tested by inducingextrinsic oxygen vacancies in LaMnO3 through a lowtemperature reduction in H2/Ar. It was found thatsubstoichiometric LaMnO3-δ exhibits ~20% greatercapacitance, highlighting the significance of oxygenvacancies as charge-storage sites in these perovskite typeoxides. Importantly, due to the well-known oxide andproton ionic conduction characteristics of perovskites, wedemonstrate that charge storage is not limited to thesurface of these materials. Rather, it may extend into thebulk of the structure, leading to higher energy storagethan traditional psuedocapacitors which are inherentlylimited by surface confined reactions. As the first study ofthese materials for pseudocapacitor applications, onlymoderate structural and electrochemical optimizationshave been carried out. As such, the high specificcapacitances of >500F/g and high cycling stability for thematerials of this study imply a promising future forperovskite structured pseudocapacitors.
Perovskite catalysts are of great interest as replacements for precious metals and oxides used in the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Perovskite electrocatalysts have been shown to have greater specific activities than precious metals and their oxides, but high mass activities have not yet been realized due to vague or incomplete mechanistic understanding of catalysts active sites coupled with inadequate synthesis techniques which often result in unwanted phase impurities and micron-scale materials. Herein, we demonstrated precise control over the synthesis of essentially phase pure perovskite nanocrystals with mass activities exceeding that of IrO2 and possessing comparable or greater bifunctional character than leading precious metals such as Ir and Pt. The robust aqueous synthesis of ABO3 perovskites such as LaCoO3, LaMnO3, LaNixFe1-xO3 and Ba0.5Sr0.5Co0.8Fe0.2O3-δ will be demonstrated, and the resulting electrocatalytic activities of these materials will be presented. We will examine these results in the context of proposed perovskite activity descriptors, surface hydroxylation, oxygen vacancies and mechanistic pathways for the OER and ORR. Catalytic activity is determined using electroanalytical techniques such as rotating disk electrochemistry and cyclic voltammetry in conjunction with materials characterization enabled by dynamic light scattering, electron microscopy, nitrogen sorption, X-ray photoelectron spectroscopy and X-ray diffraction. It is demonstrated that these highly active perovskite catalysts are an emerging replacement for the precious metals used not just for the OER and ORR, but also for the chlor-alkali and oxygen depolarized cathode industries as well.
A magnetic nanoparticle suitable for imaging a geological structure having one or more magnetic metal or metal oxide nanoparticles with a polymer grafted to the surface to form a magnetic nanoparticle, wherein the magnetic nanoparticle displays a colloidal stability under harsh salinity conditions or in a standard API brine.
A method for preparing poorly water soluble drug particles is disclosed. The method comprises dissolving a drug in at least one organic solvent to form a drug/organic mixture, spraying the drug/organic mixture into an aqueous solution and concurrently evaporating the organic solvent in the presence of the aqueous solution to form an aqueous dispersion of the drug particles. The resulting drug particles are in the nanometer to micrometer size range and show enhanced dissolution rates and reduced crystallinity when compared to the unprocessed drug. The present invention additionally contemplates products and processes for new drug formulations of insoluble drug particles having high dissolution rates and extremely high drug-to-excipient ratios
Foams used for mobility control in CO2 flooding, and for more secure sequestration of anthropogenic CO2, can be stabilized with nanoparticles, instead of surfactants, bringing some important advantages. The solid nature of the nanoparticles in stabilized foams allows them to withstand the high-temperature reservoir conditions for extended periods of time. They also have more robust stability because of the large adsorption energy required to bring the nanoparticles to the bubble interface.
Silica nanoparticle-stabilized CO2-in-brine foams were generated by the co-injection of CO2 and aqueous nanoparticle dispersion through beadpacks, and through unfractured and fractured sandstone cores. Foam flow in rock matrix and fracture, both through Boise and Berea sandstones, was investigated. The apparent viscosity measured from foam flow in various porous media was also compared with that measured in a capillary tube, installed downstream of beadpacks and cores.
The domain of foam stability and the apparent foam viscosity in beadpacks was first investigated with focus on how the surface wettability of nanoparticles affects the foam generation. A variety of silica nanoparticles without any surface coating and with different coatings were tested, and the concept of hydrophilic/CO2-philic balance (HCB) was found to be very useful in designing surface coatings that provide foams with robust stability. Opaque, white CO2-in-water foams (bubble diameter < 100 µm) were generated with either polyethyleneglycol-coated silica or methylsilyl-modified silica nanoparticles with CO2 densities between 0.2 and 0.9 g/cc. The synergistic interactions at the surface of nanoparticles (bare colloidal silica) and surfactant (caprylamidopropyl betaine) in generating stable CO2 foams were also investigated.
The common and distinct requirements to generate stable CO2 foams with 5-nm silica nanoparticles, in rock matrices and in fractures, were characterized by running foam generation experiments in Boise and Berea sandstone cores. The threshold shear rates for foam generation in matrix and in fracture, both in Boise and Berea sandstones, were characterized. The ability of nanoparticles to generate foams only above a threshold shear rate is advantageous, because high shear rates are associated with high permeability zones and fractures. Reducing CO2 mobility in these zones with foam diverts CO2 into lower permeability regions that still contain unswept oil.
Perovskites are of great interest as replacements for precious metals and oxides used in bifunctional air electrodes involving the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, we report the synthesis and activity of a phase-pure nanocrystal perovskite catalyst that is highly active for the OER and ORR. The OER mass activity of LaNiO3, synthesized by the calcination of a rapidly dried nanoparticle dispersion and supported on nitrogen-doped carbon, is demonstrated to be nearly 3-fold that of 6 nm IrO2 and exhibits no hysteresis during oxygen evolution. Moreover, strong OER/ORR bifimctionality is shown by the low total overpotential (1.02 V) between the reactions, on par or better than that of noble metal catalysts such as Pt (1.16 V) and Ir (0.92 V). These results are examined in the context of surface hydroxylation, and a new OER cycle is proposed that unifies theory and the unique surface properties of LaNiO3.
Magnetic nanoparticles that can be transported in subsurface reservoirs at high salinities and temperatures are expected to have a major impact on enhanced oil recovery, carbon dioxide sequestration, and electromagnetic imaging. Herein we report a rare example of steric stabilization of iron oxide (10) nanoparticles (NPs) grafted with poly(2-acrylamido-2-methylpropanesulfonate-co-acrylic acid) (poly-(AMPS-co-AM) that not only display colloidal stability in standard American Petroleum Institute (API) brine (8% NaCI + 2% CaCl2 by weight) at 90 C for 1 month but also resist undesirable adsorption on silica surfaces (0.4% monolayer NPs). Because the AMPS groups interacted weakly with Ca2+, they were sufficiently well solvated to provide steric stabilization. The PAA groups, in contrast, enabled covalent grafting of the poly(AMPS-co-AA) chains to amine-functionalized 10 NPs via formation of amide bonds and prevented polymer desorption even after a 40000-fold dilution. The aforementioned methodology may be readily adapted to stabilize a variety of other functional inorganic and organic NPs at high salinities and temperatures.
Solutions of therapeutic proteins often gel and become too viscous to deliver via subcutaneous injection at high protein concentrations (>200 mg ml(-1)). Herein, we demonstrate that protein molecules can be crowded into colloidally stable dispersions of distinct nanoclusters that exhibit equilibrium hydrodynamic diameters without gelation at very high concentrations (up to 320 mg ml(-1)). The nanoclusters form spontaneously upon concentration of protein solutions in the presence of a crowding agent, for example trehalose. Remarkably nanoclusters of the same size are produced by dilution of protein powder in buffer. Nanocluster size is stable for extended time periods, and upon frozen storage and thawing. Thus, the nanocluster diameter appears to be governed by equilibrium behavior arising from a balance of short and long-ranged monomer-monomer, monomer-cluster and cluster-cluster interactions, as calculated by a free energy model.
Inhalation of low-density porous particles enables deep lung delivery with less dependence on device design and patient inspiration. The purpose of this study was to implement Thin Film Freezing (TFF) to investigate a novel approach to dry powder inhalation. Powders produced by TFF were evaluated for aerodynamic and geometric particle size by cascade impaction and laser light scattering, respectively. Density measurements were conducted according to USP methods and calculated using data from particle size measurements. Excipient inclusion and its effect on moisture sorption was measured by Dynamic Vapor Sorption (DVS). TFF-produced brittle matrix powders were sheared apart into respirable microparticles using a passive DPI device, producing fine particle fractions (FPF) up to 69% and mass median aerodynamic diameters (MMAD) as low as 2.6 mu m. Particles had a mean geometric diameter ranging from 25 mu m to 50 mu m and mass densities of approximately 0.01 g/cm(3). Powders were susceptible to moisture-induced matrix collapse, capillary forces and electrostatic charging; although formulations containing mannitol or no sugar excipient proved to be more robust. Aerosolized brittle matrices produced by TFF may prove to be a useful platform for highly efficient pulmonary delivery of thermally labile, highly potent, and poorly soluble drugs.
A series of sulfonated random and block copolymers were adsorbed on the surface of similar to 100 nm iron oxide (IO) nanoparticles (NPs) to provide colloidal stability in extremely concentrated brine composed of 8% wt NaCl + 2% wt CaCl2 (API brine; 1.4 M NaCl + 0.2 M CaCl2) at 90 degrees C. A combinatorial materials chemistry approach, which employed Ca2+-mediated adsorption of anionic acrylic acid-containing sulfonated polymers to preformed citrate-stabilized IO nanoclusters, enabled the investigation of a large number of polymer coatings. Initially a series of poly(2-methyl-2-acrylamidopropanesulfonate-co-acrylic acid) (poly(AMPS-co-AA)) (1:8 to 1:1 mcl:mol), poly(styrenesulfonate-block-acrylic acid) (2.4:1 mol:mol), and poly(styrenesulfonate-alt-maleic acid) (3:1 mol:mol) copolymers were screened for solubility in API brine at 90 degrees C. The ratio of AMPS to AA groups was varied to balance the requirement of colloid dispersibility at high salinity (provided by AMPS) against the need for anchoring of the polymers to the iron oxide surface (via the AA). Steric stabilization of IO NPs coated with poly(AMPS-co-AA) (1:1 mol:mol) provided colloidal stability in API brine at room temperature and 90 degrees C for up to 1 month. The particles were characterized before and after coating at ambient and elevated temperatures by a variety of techniques including colloidal stability experiments, dynamic light scattering, zeta potential, and thermogravimetric analysis.
Although sub-100 nm nanoclusters of metal nanoparticles are of interest in many fields including biomedical imaging, sensors, and catalysis, it has been challenging to control their morphologies and chemical properties. Herein, a new concept is presented to assemble equilibrium Au nanoclusters of controlled size by tuning the colloidal interactions with a polymeric stabilizer, PLA(1k)-b-PEG(10k)-b-PLA(1k). The nanoclusters form upon mixing a dispersion of similar to 5 nm Au nanospheres with a polymer solution followed by partial solvent evaporation. A weakly adsorbed polymer quenches the equilibrium nanocluster size and provides steric stabilization. Nanocluster size is tuned from similar to 20 to similar to 40 nm by experimentally varying the final Au nanoparticle concentration and the polymer/Au ratio, along with the charge on the initial Au nanoparticle surface. Upon biodegradation of the quencher, the nanoclusters reversibly and fully dissociate to individual similar to 5 nm primary particles. Equilibrium cluster size is predicted semiquantitatively with a free energy model that balances short-ranged depletion and van der Waals attractions with longer-ranged electrostatic repulsion, as a function of the Au and polymer concentrations. The close spacings of the Au nanoparticles In the clusters produce strong NIR extinction over a broad range of wavelengths from 650 to 900 nm, which is of practical interest in biomedical imaging.
A homologous series of Au coated iron oxide nanoparticles with hydrodynamic diameters smaller than 60 nm was synthesized with very low Au-to-iron mass ratios, as low as 0.15. The hydrodynamic diameter was determined by dynamic light scattering and the composition by atomic absorption spectroscopy and energy dispersive x-ray spectroscopy. Unusually low Au precursor supersaturation levels were utilized to nucleate and grow Au coatings on iron oxide relative to the formation of pure Au nanoparticles. This approach produced unusually thin coatings by lowering autocatalytic growth of Au on Au, as shown by transmission electron microscopy. Nearly all of the nanoparticles were attracted by a magnet, indicating a minimal number of pure Au particles. The coatings were sufficiently thin to shift the surface plasmon resonance to the near infrared with large extinction coefficients, despite the small particle hydrodynamic diameters observed from dynamic light scattering to be less than 60 nm.
The concept of hydrophilic/CO2-philic balance (HCB) was extended to describe stabilization of carbon dioxide-in-water (C/W) foams (also called emulsions) with silica nanoparticles adsorbed at the CO2-water interface. Opaque, white C/W foams (bubble diameter <100 mu m) were generated with either PEG-coated silica or methylsilyl modified silica nanoparticles in a beadpack with CO2 densities between 0.2 and 0.9 g mL(-1). For methylsilyl modified silica nanoparticles, 50% SiOH modification provided an optimal HCB for generation and stabilization of viscous C/W foams with high stability. The apparent viscosity measured with a capillary tube viscometer reached 120-fold that of a CO2-water mixture without nanoparticles, a consequence of the small bubble size and the energy required to deform a high density of aqueous lamellae between CO2 bubbles. Air-in-water (A/W) foams stabilized with nanoparticles were used to gain insight into the relationship between nanoparticle surface properties and adsorption of the nanoparticles at various types of interfaces. With suitable nanoparticles, A/W foams were stable for at least 7 days and C/W foams were stable for at least 23 h. The ability to achieve long term stability for nanoparticle stabilized C/W foams could offer an alternative to conventional surfactants, which are known to have much lower adsorption energies. (C) 2012 Elsevier Inc. All rights reserved.
Stable dispersions of graphene oxide nanoplatelets were formed in water at pH 2-10 even with 5 wt% NaCl. For these conditions, oil-in-water emulsions stabilized with graphene oxide nanoplatelets remained partially stable for 1 year. The droplet sizes were as small as similar to 1 mu m with a low nanoplatelet concentration of 0.2 wt%. The emulsions were stable even for nanoplatelet concentrations down to 0.001 wt%. The stabilities of the emulsions even at high salinity may be attributed to the high anion density at the graphene oxide nanoplatelet edges which protrude into the water phase. Furthermore, the graphene oxide nanoplatelets are shown to adsorb on the surfaces of the oil droplets. The conceptual picture of graphene oxide nanoplatelets adsorbed to a greater extent on the water side of the oil/water interface, along with the high density of anions on their edges, cause the oil/water interface to curve about the oil phase, resulting in oil-in-water emulsion droplets. The dispersion stability with a very small amount of graphene oxide-based stabilizer, offers an intriguing opportunity for applications including CO2 sequestration and enhanced oil recovery in deep subsurface formations, which generally contain high-salinity brines. (C) 2013 Elsevier Inc. All rights reserved.
Though gold nanoparticles have been considered bio-inert, recent studies have questioned their safety. To reduce the potential for toxicity, we developed a nanoclustering of gold and iron oxide as a nanoparticle (nanorose) which biodegrades into subunits to facilitate rapid excretion. In this present study, we demonstrate acid and macrophage lysosomal degradation of nanorose via loss of the near-infrared optical shift, and clearance of the nanorose in vivo following i.v. administration in C57BL/6 mice by showing gold concentration is significantly reduced in 11 murine tissues in as little as 31 days (P < 0.01). Hematology and chemistry show no toxicity of nanorose injected mice up to 14 days after administration. We conclude that the clustering design of nanorose does enhance the excretion of these nanoparticles, and that this could be a viable strategy to limit the potential toxicity of gold nanoparticles for clinical applications. From the Clinical Editor: The potential toxicity of nanomaterials is a critically important limiting factor in their more widespread clinical application. Gold nanoparticles have been classically considered bio-inert, but recent studies have questioned their safety. The authors of this study have developed a clustering gold and iron oxide nanoparticle (nanorose), which biodegrades into subunits to facilitate rapid excretion, resulting in reduced toxicity. Published by Elsevier Inc.
Freezing of protein solutions perturbs protein conformation, potentially leading to aggregate formation during long-term storage in the frozen state. Macroscopic protein concentration profiles in small cylindrical vessels were determined for a monoclonal antibody frozen in a trehalose-based formulation for various freezing protocols. Slow cooling rates led to concentration differences between outer edges of the tank and the center, up to twice the initial concentration. Fast cooling rates resulted in much smaller differences in protein distribution, likely due to the formation of dendritic ice, which traps solutes in micropockets, limiting their transport by convection and diffusion. Analysis of protein stability after more than 6 months storage at either 10 degrees C or 20 degrees C [above glass transition temperature (Tg)] or 80 degrees C (below Tg) revealed that aggregation correlated with the cooling rate. Slow-cooled vessels stored above Tg exhibited increased aggregation with time. In contrast, fast-cooled vessels and those stored below Tg showed small to no increase in aggregation at any position. Rapid entrapment of protein in a solute matrix by fast freezing results in improved stability even when stored above Tg. (c) 2013 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 102:11941208, 2013
The adsorption of even a single serum protein molecule on a gold nanosphere used in biomedical imaging may increase the size too much for renal clearance. In this work, we designed charged similar to 5 nm Au, nanospheres coated with binary mixed-charge ligand monolayers that do not change in size upon incubation in pure fetal bovine serum (FBS). This lack of protein adsorption was unexpected in view of the fact that the Au surface was moderately charged. The mixed-charge monolayers were composed of anionic citrate ligands modified by place exchange with naturally occurring amino acids: either cationic lysine or zwitterionic cysteine ligands. The zwitterionic tips of either the lysine or cysteine ligands interact weakly with the proteins and furthermore increase the distance between the "buried" charges closer to the Au surface and the interacting sites on the protein surface. The nm nanospheres were assembled into similar to 20 nm diameter nanoclusters with strong near-IR absorbance (of interest in biomedical imaging and therapy) with a biodegradable polymer, PLA(1k)-b-PEG(10k)-b-PLA(1k). Upon biodegradation of the polymer in acidic solution, the nanoclusters dissociated into primary similar to 5 nm Au nanospheres, which also did not adsorb any detectable serum protein in undiluted FBS.
Transport of metal oxide nanoparticles in porous rock is of interest for imaging and oil recovery in subsurface reservoirs, which often contain concentrated brine. Various copolymers composed of acrylic acid and either 2-acrylamido-2-methylpropanesulfonate or styrenesulfonate were synthesized and adsorbed on iron oxide nanoclusters to provide colloidal stability and to achieve low adsorption on silica in high salinity brine composed of 8% wt. NaCl + 2% wt. CaCl2. Furthermore, the degree of adsorption of the nanoparticles on silica was controlled by modifying the acrylic acid groups in the copolymers with a series of diamines and triamines to add hydrophobicity. The adsorption on colloidal silica microparticles ranged from <1 mg/m(2) for highly charged hydrophilic surfaces on the iron oxide nanoparticles to 22 mg/m(2) for the most hydrophobic amine-modified surfaces, corresponding to monolayer coverages that ranged from 0.2% to 11.5%, respectively. The specific adsorption (mg-IO/m(2)-silica), monolayer coverage, and parameters for Langmuir isotherms were evaluated for various 10 nanoclusters as a function of the properties of the copolymers on their surfaces. (C) 2013 Elsevier Inc. All rights reserved.