Gold-platinum based bi-metallic nanocrystal suspensions, electrochemical manufacturing processes therefor and uses for the same
Inventors
Dorfman, Adam R. • Bryce, David A. • Grace, Maxwell A. • Pierce, D. Kyle • Merzliakov, Mikhail • Mortenson, Mark G.
Assignees
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Publication Number
US-9387225-B2
Publication Date
2016-07-12
Expiration Date
Abstract
The present invention relates to novel gold-platinum based bi-metallic nanocrystal suspensions that have nanocrystal surfaces that are substantially free from organic or other impurities or films associated with typical chemical reductants/stabilizers and/or raw materials used in nanoparticle formation processes. Specifically, the surfaces are “clean” relative to the surfaces of metal-based nanoparticles made using chemical reduction (and other) processes that require organic (or other) reductants and/or surfactants to grow (and/or suspend) metal nanoparticles from metal ions in a solution. The invention includes novel electrochemical manufacturing apparatuses and techniques for making the bi-metallic nanocrystal suspensions. The techniques do not require the use or presence of chlorine ions/atoms and/or chlorides or chlorine-based materials for the manufacturing process/final suspension. The invention further includes pharmaceutical compositions thereof and the use of the bi-metallic nanocrystals or suspensions or colloids thereof for the treatment or prevention of diseases or conditions for which metal-based therapy is already known, including, for example, for cancerous diseases or conditions.
Core Innovation
The invention provides a process for forming gold-platinum bi-metallic nanocrystals suspended in water by an electrochemical manufacturing approach with a plasma process and an electrode/electrical arrangement in the presence of a processing enhancer. Platinum species are formed in water and then used to enable the formation of Au-Pt nanocrystals, including embodiments in which a second electrochemical reaction at a gold electrode results in Au-Pt nanocrystals. The process is described with a trough/flow architecture and a container partially filled with water.
A central concept is the sequential creation of platinum species using plasma formed near platinum-based plasma-forming electrodes spaced apart from a water surface, followed by subsequent contact with electrode sets comprising gold to form gold-platinum bi-metallic nanocrystals suspended in water. The processing includes passing water and an inorganic processing enhancer through trough members, forming plasma in spaces between electrodes and the respective water or water-platinum species liquid, and contacting the water-platinum species liquid with gold electrodes after flow past the gold-based plasma-forming electrode.
The disclosed processing enhancers include sodium hydrogen carbonate, KOH, KBr, Na3PO4, KH2PO4, NaCl, and CaCl2, with dependent refinements based on enhancer chemistry. The framework supports forming gold-platinum nanocrystals, alloys, and heteroaggregates with controlled size, shapes, and extended low-index planes, and it avoids chlorine ions, chlorides, and chlorine-based materials as part of the processing. The document further describes characterization references including TEM, UV-Vis spectroscopy, DLS/Zetasizer, AAS, pH, and zeta potential.
Claims Coverage
The document contains three independent claims, each directed to forming gold-platinum bi-metallic nanocrystals suspended in water using electrochemical plasma stages and electrode sets. Across the independent claims, the core coverage centers on sequential plasma-driven formation of platinum species followed by gold contact to produce gold-platinum nanocrystals, with additional refinements relating to processing enhancers and electrode configurations.
Sequential platinum-species plasma then gold-contact nanocrystal formation
A process forming gold-platinum bi-metallic nanocrystals suspended in water by creating a first plasma near platinum-based plasma-forming electrodes spaced apart from a surface of water to form platinum species, providing the water-platinum species liquid to a second trough member, creating a second plasma near gold-based plasma-forming electrodes spaced apart from the water-platinum species liquid, and causing gold electrodes to form gold-platinum bi-metallic nanocrystals after the liquid has flowed past the gold-based plasma-forming electrode.
Electrochemically forming platinum species using water lysis product then gold reaction
A process forming gold-platinum bi-metallic nanocrystals suspended in water by electrochemically forming at least one platinum species in water and at least one lysis product of water to create a water-platinum species liquid, then contacting the water-platinum species liquid with at least one set of electrodes comprising gold and causing a second electrochemical reaction to form a bi-metallic gold-platinum nanocrystal suspension.
Container-based plasma at an upper surface using platinum electrode then gold contacting
A process forming gold-platinum bi-metallic nanocrystals in water by providing a container with water comprising at least one processing enhancer, providing a first electrode set with at least one platinum-based plasma-forming electrode spaced apart from an upper surface of the water and at least one platinum electrode at least partially immersed in the water, forming at least one plasma between at least a portion of the upper surface of the water and the platinum-based plasma-forming electrode to create platinum species in the water, and subsequently contacting at least one second electrode set comprising gold with the water after plasma contact to form and suspend gold-platinum bi-metallic nanocrystals.
Across the independent claims, the inventive subject matter is centered on electrochemically forming platinum species in water using platinum electrode-driven plasma, followed by contacting gold electrodes or electrode sets with the platinum-species-containing water to form gold-platinum bi-metallic nanocrystals suspended in water, optionally incorporating specific inorganic processing enhancers.
Stated Advantages
Produces substantially clean nanocrystal surfaces described as largely free of organic/reduction-derived impurities.
Avoids chlorine ions, atoms, chlorides, and chlorine-based materials.
Enables controlled pH and stability as reflected by zeta potential being more negative at higher stability.
Supports formation of gold-platinum nanocrystals with controlled size and varied shapes and extended low-index planes.
Documented Applications
Biomedical use including anti-cancer indications, including discussion of cancer treatment/prevention and xenograft tests references.
Catalytic use is referenced in the documented content.
In vitro biological evaluation using multiplexed cytotoxicity across 30 human tumor cell lines comparing concentrated Au and Au-Pt, including reported trends in EC50/IC50 and apoptosis/mitosis indicators.
In vivo xenograft studies using HCT116 and Balb/C immunodeficient mice, with oral administration described as drinking water and intratumoral administration, and tumor volume/weight outcomes compared to controls and cisplatin.
Longer-duration monitoring in Swiss Webster mice for behavior and quality-of-life, including observations of no observed consumption/weight-gain differences.
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