Silver nanoplate compositions and methods

0001Priority application reference built-in This application claims the priority benefit of US Patent Provisional Application No. 61 / 795,149 filed October 11, 2012, the full text of which is incorporated by reference.

0002Parties to the joint research agreement The invention described herein was created by a joint research agreement between Sienna Labs, Inc. and nanoComposix, Inc.

0003background Field of invention The present invention relates to a method for preparing a solution of high optical density silver platelet nanoparticles (eg, nanoplates), as well as nanoparticles, solutions and substrates prepared by the method.

0004Description of related technology Nanoparticles can be synthesized from a variety of materials, including nanospheres, nanorods, nanowires, nanocubes, nanoplates, and other shapes. In one embodiment, the plate nanoparticles are nanoplates. Nanoparticles made from metals such as gold and silver are unique in that they can be tuned to interact with light throughout the electromagnetic spectrum due to the localized surface plasmon resonance supported by these nanomaterials. It has optical properties. Techniques that utilize the unique optical properties of silver nanoparticles include, but are not limited to, diagnostic techniques, optical communication techniques, medical techniques, and shielding techniques. Subsets of these techniques, including photothermal tumor removal, hair removal, acne treatment, wound healing, and antibacterial applications, among others, may use solutions of nanoparticles with high optical concentrations. Silver nanoplates, also known as colloidal silver nanoparticles or nanoprisms, are of particular interest in techniques that utilize the optical properties of nanoparticles because of their adjustable spectral peaks and extremely high optical efficiency. Photoconversion (Jin et al. 2001; Jin et al.2003), pH-controlled photoconversion (Xue 2007), thermal growth (Hao et al.2004; Hao 2002; He 2008; Metraux 2005), template growth (Hao et al.2004; Hao 2002), and seed-mediated growth. (Aherne 2008; Chen; Carroll 2003; Chen; Carroll 2002, 2004; Chen et al. 2002; He 2008; Le Guevel 2009; Xiong et al. 2007) have developed methods for the preparation of silver nanoplates. Method produces a relatively dilute solution with correspondingly low visibility and near-infrared optical density.

<p num="0005"><nplcit num="1"><text>Jin et al. 2001</text></nplcit><nplcit num="2"><text>Jin et al. 2003</text></nplcit><nplcit num="3"><text>Xue 2007</text></nplcit><nplcit num="4"><text>Hao et al. 2004</text></nplcit><nplcit num="5"><text>Hao 2002</text></nplcit><nplcit num="6"><text>He 2008</text></nplcit><nplcit num="7"><text>Metraux 2005</text></nplcit><nplcit num="8"><text>Aherne 2008;</text></nplcit><nplcit num="9"><text>Chen; Carroll 2003</text></nplcit><nplcit num="10"><text>Chen; Carroll 2002, 2004</text></nplcit><nplcit num="11"><text>Chen et al. 2002</text></nplcit><nplcit num="12"><text>Le Guevel 2009</text></nplcit><nplcit num="13"><text>Xiong et al. 2007</text></nplcit></p>

<p num="0006"> For many silver nanoplate applications, a more concentrated solution of silver nanoplates may be useful and particularly advantageous. In some examples, when the as-prepared solution of silver nanoparticles is concentrated under the methods developed so far to obtain higher particle concentrations, the shape of the nanoparticles is subject to change and is optically optical. It can bring about changes in properties, such as optical density. In many cases, these changes result in an undesired deterioration of the optical properties of the nanoparticles. Therefore, some embodiments of the present invention provide a method of preparing a silver nanoplate solution having an increased optical concentration at a higher concentration while reducing the deterioration of the optical properties of the silver nanoplate. In various embodiments, the methods of the invention are of silver nanoplates that substantially or completely preserve the shape and optical properties of the prepared silver nanoplates when the particle concentration is increased. It is provided that a high optical concentration solution is prepared from a dilute silver nanoplate solution.</p>

<p num="0007"> Various embodiments of the present invention provide methods for preparing high optical concentration solutions of silver nanoplates, as well as nanoparticles and solutions prepared by those methods. In one embodiment, the method comprises one or more original components (eg, chemical or biological agents) that are bound or otherwise linked to the nanoparticle surface with a stabilizer. Including replacement. In another embodiment, the stabilizer does not replace the original ingredient, but rather supplements or alters the original ingredient. Stabilizers can be biological or chemical agents that stabilize the nanoplates before, during, and / or after concentration, thereby allowing the production of stable, highly optical concentrations of silver nanoplates. .. In one embodiment, the method also includes a method of increasing the concentration of silver nanoplates in solution and thus increasing the optical concentration of the solution. In some embodiments, the stability of the high optical concentration solution (eg, the characteristics of the nanoparticles in the solution, such as shape, size, optical properties, peak response, plasmon properties, etc.) is determined during the method. Unaffected or substantially unaffected. Some embodiments of the invention include a high optical concentration solution of silver nanoplates stabilized by stabilizers (eg, surface binding molecules, chemical agents, and / or biological agents). In one embodiment, the invention is surfaced by a chemical or biological agent that is physically adsorbed on the surface, molecularly attached to the surface through specific interactions, or encapsulates each nanoparticles. Contains a solution of functionalized silver nanoparticles.</p><p num="0008"> In one embodiment, the high optical concentration solution of silver nanoplates associates with the substrate. In one embodiment, a portion of the nanoplates in solution binds to the substrate to create a nanoplate-substrate composite. A high optical concentration solution of silver nanoplates can come into contact with the substrate to produce a nanoplate composite in which a significant portion of the surface area of the substrate is covered with nanoplates. In some embodiments, the substrate is a fiber, fabric, mesh, bandage, socks, wrap, other clothing, sponge, highly porous substrate, particles with edge lengths greater than 1 micron, beads, hair, Includes skin, paper, absorbent polymers, foams, wood, corks, slides, rough surfaces, biocompatible substrates, filters, and / or medical implants.</p><p num="0009"> In some embodiments, a method for increasing the optical density of a stable silver nanoplate solution comprises (i) multiple silver nanoplates having a plate shape, 0.1-10 cm.^-1Prepare a solution with a peak optical concentration between; (ii) add a stabilizer to the solution; (iii) add a buffer to the solution; and (iv) add a solution containing the buffer. Containing to form a concentrated solution, wherein the concentrated solution contains a plurality of silver nanoplates having a plate shape, and the concentrated solution is 10 cm.^-1Has a higher peak optical density than.</p><p num="0010"> In some embodiments, the method for producing a stable silver nanoplate high optical concentration solution is as follows: (i) adding a stabilizer to the silver nanoplate solution, (ii) buffer solution. Adding (for example, a buffer containing a water-soluble salt) to the solution of the silver nanoplate, (iii) the stabilizer and the buffer and the silver nanoplate, on the surface of the silver nanoplate Mix for a time sufficient to interact with the water soluble salt in the buffer, as well as (iv) 10 cm solution.^-1Higher peak optical density (eg 50-1500 cm)^-1) Includes concentration.</p><p num="0011"> Stabilizers include sodium citrate, water-soluble polymers (eg sodium polystyrene sulfonate and / or hydrocarbon polymers derivatized with sulfonate), polyvinyl-based polymers (eg polyvinyl alcohol (PVA) and / or Polyvinylpyrrolidone (PVP), etc.), polyethylene glycol, polyacrylic acid, or one or more of dextran may be included. Water-soluble salts can include one or more of sulfates, carbonates, chromates, borates, phosphates, and sulfites, acetates, and nitrates. In various embodiments, the combination of the stabilizer and a buffer containing one or more water-soluble salts provides stabilization for the nanoplate formulation, in which one of the components of the salt stabilizes. It can interact with the agent to crosslink the stabilizer and improve the stability of the coating on the silver nanoplate. In one embodiment, the solution of the first silver nanoplate can be made from a solution containing one or more stabilizers and a silver source (eg, silver salt, silver seed, etc.), in which the silver source is Chemicals, biological agents, mixtures, electromagnetic rays, and / or heat are used for reduction (eg, photoexchange, pH controlled photoexchange, thermal growth, template growth, and / or seed-mediated growth). ..</p><p num="0012"> In various embodiments, the method for concentrating the solution of silver nanoplates is 10 cm.^-1Lower than (eg 0.1 ~ 9.9 cm^-1, 1 ~ 9cm^-1, 3 ~ 7cm^-1, 1 ~ 5cm^-1, And / or 5 ~ 10cm^-1) A step of preparing a solution containing multiple silver nanoplates with peak optical concentration, a step of adding a stabilizer to the solution, a step of adding a buffer solution containing a water-soluble salt to the solution, and a step of adding the solution to 10 cm.^-1Higher peak optical density (eg 80-150 cm)^-1, 900 ~ 1100cm^-1, 100cm^-1, 1000cm^-1Or more) includes the step of concentrating. In various embodiments, the peak optical density is increased by 10%, 50%, 100%, 200%, 500%, 1,000%, 10,000% or more and / or 1: 1.5, 1: 2, 1: 1. Increases at a ratio of 5, 1:10 or higher, and / or doubles 1, 1.5, 2, 5, 10, 25, 50, 100, 1000 times or more.</p><p num="0013"> In various embodiments, the silver nanoplate has an aspect ratio between 1.5-50 (eg, 1.5-10, 25-50). In one embodiment, the silver nanoplate comprises an edge length between 10 nm and 300 nm (eg, 50-250, 65-100 nm). In various embodiments, the stabilizer comprises at least one water-soluble polymer selected from the group consisting of sodium citrate, or a hydrocarbon polymer derivatized with sodium polystyrene sulfonate and a sulfonate. In some embodiments, the water soluble salt comprises one or more of sulfates, carbonates, chromates, borates, phosphates, and sulfites, acetates, and nitrates. In one embodiment, the stabilizer comprises at least one of the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyacrylic acid, and dextran. In one embodiment, the stabilizer comprises a thiol-containing molecule. The thiol-containing molecule may include dihydrolipoic acid or a derivative thereof. The method optionally includes the steps of isolating the concentrated nanoplates and encapsulating the isolated concentrated nanoplates (eg, with silica or another material). In one embodiment, the method includes encapsulating nanoplates of 10 cm.^-1Higher optical density (eg 100 cm^-1, 1000cm^-1Or more) includes the step of concentrating. Stabilizers are added prior to the formation of silver nanoplates. In one embodiment, the nanoplates are concentrated by tangential filtration. In one embodiment, the silver concentration is higher than 1.0 mg / mL (eg, 1-1000, 10-300 mg / mL).</p><p num="0014"> In various embodiments, methods for producing silver nanoplates coated with metal oxides are provided. This method includes peak absorption spectra between 500-1500 nm (eg 600-1400, 800-1200 nm) and 10 cm.^-1Higher optical density (eg 100 cm^-1, 1000cm^-1The step of preparing a solution of silver nanoplates with (or more), and an amount of this solution sufficient to form a metal oxide film on the outer surface of the silver nanoplate with a solution of metal oxide or metal oxide precursor. May include the step of contacting with. In certain embodiments, the silver nanoplate is a stabilized polymer (eg, polyvinylpyrrolidone, polyvinyl), such as by placing the stabilizing polymer on the outer surface of the silver nanoplate prior to contact with the metal oxide precursor. Meet with alcohol (or a combination thereof). In various embodiments, the metal oxide is or comprises silica.</p><p num="0015"> In various embodiments, the method for producing a solution of silver nanoplates involves preparing a solution containing a reducing agent, a stabilizer, a water-soluble polymer, and a silver salt, from which a plurality of silver seeds are added. A step of forming, a step of growing a plurality of silver seeds into a plurality of silver nanoplates in a solution to form a silver nanoplate solution, a step of adding a stabilizer to the silver nanoplate solution, a buffer containing a water-soluble salt. The process of adding the solution to the silver nanoplate solution, and 10 cm of the silver nanoplate solution^-1Higher peak optical density (eg 100 cm^-1, 1000cm^-1Or more) includes the step of concentrating.</p><p num="0016"> In various embodiments, the composition comprises or becomes essentially a solution of silver nanoplates, the silver nanoplates comprising a polyvinyl polymer. In some embodiments, the polyvinyl polymer comprises polyvinylpyrrolidone or polyvinyl alcohol. In some embodiments, the composition (eg, solution) is composed of one or more salts, such as water soluble salts (eg, sulfates, carbonates, chromates, borates, phosphates, and sulfites). , Acetate, and nitrate) and the like.</p><p num="0017"> In various embodiments, the polyvinyl polymer associates with the salt, the polyvinyl polymer covers at least a portion of the silver nanoplate, and / or the polyvinyl polymer is located on the outer surface of the silver nanoplate. In one embodiment, the solution comprises silver nanoplates at a concentration effective for adhering to the non-metal coating material present in the solution. The solution may be formulated to be concentrated. In some embodiments, the optical density of the solution or silver nanoplate is 10 cm.^-1Higher than (eg 100 cm^-1, 1000cm^-1Or more). The solution contains salts (sulfates, carbonates, chromate, borates, phosphates, and sulfites, acetates, and nitrates) in concentrations higher than 0.1 mM (eg, 0.1 mM to 10 mM). You can do it. In one embodiment, the solution has a pH greater than 7 (eg, 8-13). In some embodiments, the absorption spectrum of the silver nanoplate comprises peak wavelengths between 500 and 1500 nm (eg, 600 to 1400, 550 to 1100, 810 to 830, 1000 to 1100 nm). In one embodiment, the solution comprises bicarbonate. The silver nanoplate may be coated with silica. Silver nanoplates can have edge lengths between 10 nm and 500 nm (eg, 50-300, 100-150 nm).</p><p num="0018"> In various embodiments, the composition comprises or becomes essentially a solution of silver nanoplates attached to a shell material containing a polyvinyl polymer. In one embodiment, the silver nanoplates are substantially coated with a polyvinyl polymer. In various embodiments, the composition comprises a metal oxide, the metal oxide comprises silica, the polyvinyl polymer comprises polyvinyl alcohol or polyvinylpyrrolidone, and the silver nanoplates are attached to polyvinyl alcohol and silica. And / or silver nanoplates are attached to polyvinylpyrrolidone and silica or any combination thereof. In one embodiment, the composition comprises one moiety selected from an amine moiety and a mercapto moiety. In one embodiment, this moiety is attached to silica. In one embodiment, the composition comprises aluminum. In one embodiment, the optical concentration of the solution is 10 cm.^-1Higher than (eg 100-1100 cm^-1, Or more). In one embodiment, the optical density of the silver nanoplate is 10 cm.^-1Higher than (eg 100 cm^-1, 1000cm^-1, 11 ~ 5000cm^-1, Or more). In some embodiments, the solution contains water-soluble salts such as sulfates, carbonates, chromates, borates, phosphates, and sulfites, acetates, and nitrates above 0.1 mM. Includes in concentration (eg 0.5 mM to 2 mM, 0.1 mM to 10 mM). In one embodiment, the pH is greater than 7 (eg, 8, 9, 10, 11, 12, 13). In one embodiment, the silver nanoplate comprises peak wavelengths between 500 and 1500 nm (eg, 700 to 1300, 810 to 830, 1000 to 1100 nm).</p><p num="0019"> In various embodiments, the composition comprises silver nanoplates that are at least partially coated with a shell material containing a polyvinyl polymer, wherein the average thickness of the shell material is between 1 nm and 50 nm (eg,). , 5, 15, 40 nm). In one embodiment, the silver nanoplate has at least one edge length between 10 nm and 500 nm (eg, 25, 100, 250, 300 nm).</p><p num="0020"> In various embodiments, the kit is 10 cm^-1Higher optical density (eg 100 cm^-1, 1000cm^-1Includes or essentially one or more containers containing nanoplates (or more), solutions suitable for coating nanoplates with a shell of metal oxide, and instructions thereof. In one embodiment, the nanoplate comprises a polyvinyl polymer. In one embodiment, the polyvinyl polymer interacts with water-soluble salts (eg, sulfates, carbonates, chromates, borates, phosphates, and sulfites, acetates, and nitrates) (eg, sulfates). Bridge or otherwise combine).</p><p num="0021"> In various embodiments, the solution comprises silver nanoplates that are at least partially coated with a silica coating, wherein the silver nanoplates are 10 cm.^-1Higher than (eg 11-5000 cm)^-1, 90 ~ 1100cm^-1, Or more) Includes peak optical density. In one embodiment, the silica coating has a shell thickness between 2-100 nm (eg, 10-70, 30-90, 40-60 nm). In one embodiment, the solution contains water-soluble salts (eg, sulfates, carbonates, chromates, borates, phosphates, and sulfites, acetates, and nitrates) in concentrations greater than 0.1 mM (eg, sulfates, carbonates, chromate, borates, phosphates, and sulfites) For example, it is included in 0.1 mM to 10 mM). In one embodiment, the solution has a pH greater than 7 (eg, 9, 12, 13). In one embodiment, the silver nanoplate has a peak absorption spectrum that includes a peak wavelength between 500 nm and 1500 nm (eg, 800-1400 nm). In one embodiment, the silica coating is placed on the outer surface of the silver nanoplate. In one embodiment, the coating comprises an amine moiety or a mercapto moiety. In one embodiment, the coating further comprises aluminum. In one embodiment, the coating comprises bicarbonate. In one embodiment, the coating comprises polyvinylpyrrolidone. In one embodiment, the silver nanoplate has a thickness between 1 nm and 50 nm (eg, 10-40, 15-25, 5-30). In one embodiment, the silver nanoplate comprises at least one edge length between 10 nm and 500 nm (eg, 20-400, 50-250, 300-450).</p><p num="0022"> In some embodiments, methods for producing a solution of silver nanoplates with extremely high optical concentrations include (i) adding a concentration stabilizing chemical to the solution or precursor reagent of the silver nanoplates. (ii) Includes the step of increasing the concentration of silver nanoplates to increase the optical concentration of the solution.</p><p num="0023"> In various embodiments, the silver nanoplate has an aspect ratio between 1.5 and 25 (eg, 1.5 to 10, 1.5 to 5, 10 to 30, 25 to 50); and / or the nanoplate is about. It has an edge length between 10 nm and 250 nm (eg, 25-180, 50-150 nm); and / or the nanoplate has a triangular cross section; and / or the nanoplate has a circular cross section. In one embodiment, the perimeter of the nanoplate cross section has an edge between 4-8 (eg, 5, 6, 7). In various embodiments, the solution of the silver nanoplate is a solution of a solution containing a photoconverter, a pH controlled photoconverter, a thermal growth method, a seed-mediated growth method, and / or one or more shape stabilizers and a silver source. Formed using one or more. In various embodiments, chemical or biological agents, and / or electromagnetic rays, and / or heat, or a combination thereof, are used to reduce the silver source. In one embodiment, the silver nanoplate solution is formed from a combination of a reducing agent, a shape stabilizer, a light source, a heat source, and a portion of the silver source.</p><p num="0024"> In one embodiment, an acid, base, or buffer (also referred to as a "buffer") is added to change the pH of the solution. In various embodiments, concentration-stabilizing chemicals are added before, during, and / or after the formation of silver nanoplates. In one embodiment, the concentration stabilizing chemical acts as a shape stabilizer. In one embodiment, the concentration stabilizing chemical agent acts as a reducing agent. In one embodiment, the concentration stabilizing chemical acts as an agent that alters the pH of the solution.</p><p num="0025"> In one embodiment, the concentration stabilizing chemical agent is a water soluble polymer. In various embodiments, the polymer is one or more of a polysulfonate, a derivative of sodium polystyrene sulfonate, a derivative of a vinyl polymer, and polyvinyl alcohol (PVA). In various embodiments, the PVA has a molecular weight of less than about 80,000 daltons, between about 80,000 daltons and 120,000 daltons, and / or greater than about 120,000 daltons. In one embodiment, the polymer is polyvinylpyrrolidone (PVP). In various embodiments, the PVP has a molecular weight of less than about 20,000 daltons, greater than about 20,000 daltons, between about 20,000 daltons to 60,000 daltons, and / or greater than about 60,000 daltons. In one embodiment, the polymer is an ethylene oxide derivative.</p><p num="0026"> In one embodiment, the polymer is polyethylene glycol (PEG). In various embodiments, the PEG has a molecular weight of less than about 5,000 daltons, between about 5,000 daltons and 10,000 daltons, and / or greater than about 10,000 daltons. In one embodiment, the PEG contains a single functional group. In one embodiment, PEG contains two functional groups. According to some embodiments, the one or more functional groups are: amines, thiols, acrylates, alkynes, maleimides, silanes, azides, hydroxyls, lipids, disulfides, fluorescent molecules, and / or biotin, Or consists of one or more of its combinations. In one embodiment, the functional group may be one or more of amines, thiols, acrylates, alkynes, maleimides, silanes, azides, hydroxyls, lipids, disulfides, fluorescent molecules, and / or biotin. .. In one embodiment, the concentration stabilizer is a carbohydrate derivative. In various embodiments, the polymer is a monosaccharide, disaccharide, oligosaccharide, polysaccharide, and / or dextran. In various embodiments, the dextran is less than about 2000 daltons (eg, 500, 1000, 1500 daltons), between about 2000 daltons and 5000 daltons (eg, 3000, 4000 daltons), and / or greater than about 5000 daltons. It has a molecular weight (eg, 6000, 8000, 10000 daltons or more).</p><p num="0027"> In various embodiments, the concentration stabilizing chemicals are phenol, monomeric phenol, dimeric phenol, trimer phenol, polyphenol, tannic acid, gum arabic, biomolecule, protein, bovine serum albumin, streptavidin, biotin, One or more of peptides, oligonucleotides, naturally occurring oligonucleotides, synthetic oligonucleotides, metal or semi-metal oxides, and / or silicon dioxide shells. In one embodiment, the silicon dioxide shell ranges from less than about 1 nm to about 100 nm (eg, 2 to 90, 5 to 25, 30 to 70). In one embodiment, a combination of stabilizers is used.</p><p num="0028"> In various embodiments, the solvent can be one or more of water, alcohol, ethanol, isopropyl alcohol, t-butanol, a mixture of water and alcohol.</p><p num="0029"> In one embodiment, the concentration of silver nanoplates is increased using tangential flow filtration. In one embodiment, tangential flow filtration is performed using a tangential flow filtration membrane. In one embodiment, the tangential flow membrane is made of a cellulose ester or a mixture of cellulose esters.</p><p num="0030"> In various embodiments, the tangential flow membrane is made of one or more polyethersulfone and / or polysulfone. In various embodiments, the tangential flow membrane is less than about 10 kD (eg, 1, 5, 8 kD), between about 10 kD and 500 kD (eg, 50, 250, 400 kD), and greater than about 500 kD (eg, 750,). 1000, 5000 kD or more), less than about 0.05 μm (eg 0.01, 0.03 μm), between about 0.05 μm to 0.5 μm (eg 0.1, 0.25, 0.4 μm), and / or more than about 0.5 μm It has a molecular weight cutoff (eg, 1.0, 2, 5, 10, 100 μm).</p><p num="0031"> In various embodiments, the silver nanoplate solution is concentrated to about 10 cm.^-1Higher than, about 50 cm^-1Higher than, about 75 cm^-1Higher than, about 100 cm^-1Higher and / or about 500 cm^-1Higher than (eg 100-1000, 100-2000 cm^-1) Produce a solution with optical concentration.</p><p num="0032"> In one embodiment, the solvent in the concentrated solution is exchanged using tangential filtration. In one embodiment, the concentrated solution is treated to remove residual chemicals using tangential filtration.</p><p num="0033"> In various embodiments, a solution of nanoparticles, including silver nanoparticles, is 100 cm.^-1Higher than (eg 200, 500, 700, 1500 cm^-1, Or more) Coated with a polymer with optical density. In one embodiment, the solution of silver nanoplates is incubated with the substrate. In one embodiment, the substrate is removed from the solution of silver nanoplates and dried.</p><p num="0034"> One embodiment of the present invention provides a method for making a solution of plasmon nanoparticles, such as silver nanoparticles, suitable for performing thermal modulation of a target tissue region. Thermal modulation of the target tissue is delivered from the excited surface plasmon resonance source in an effective amount to induce thermal modulation of the domain of the target tissue region with an effective amount of plasmon nanoparticles localized in the domain of the target tissue region. This can be achieved when a composition comprising a plurality of plasmon nanoparticles is administered to a subject under conditions that expose the target tissue region to energy. In various embodiments, the materials described herein are useful for performing target heating with or without excision of tissue. For example, in one embodiment, (i) the step of topically administering a composition of plasmon nanoparticles containing silver nanoparticles to the skin surface of a subject; (ii) redistributing the plasmon particles from the skin surface to the components of the skin tissue. Target heating with or without excision of tissue, including (iii) light-induced irradiation of the skin surface, to provide a means of penetration for mammalian subjects in need of treatment. Methods are provided to carry out for treatment.</p><p num="0035"> In some embodiments, the present invention is accessible by the use of nanoparticles to the skin and underlying tissue, or other, when used with light-based energy sources in appropriate administration and excitation methods. Contains compositions that can achieve non-invasive or minimally invasive treatment of tissue space. The use of plasmon nanoparticles, eg optical concentration solutions such as silver nanoplates, with short pulse width laser excitation (eg 0.1 ms ~ 1 s pulse width) can create steep and temporary thermal gradients. , It is a structure within several cell layers where particles are localized, such as hair follicle sebaceous gland units for acne treatment and pore size reduction, skin resurfacing and targeting for tissue repair of small outer scars. Selectively target heat with or without excision to the epithelial and sebaceous layers and hair follicles for permanent hair removal. Treatments include, but are not limited to, hair loss, hair growth and regrowth, and skin rejuvenation or resurfacing, acne removal or shrinkage, wrinkle reduction, pore shrinkage, cellulite and other skin lipid deposits. Removal, removal of irritation and fungi, thinning or removal of hypertrophic scars, atrophic scars, and scars containing keloids, abnormal pigmentation (eg Portwine mother's spots), removal of tattoos, and / or skin failure Consistency (eg, texture, color, tone, elasticity, hydration) can be mentioned. Other treatments or prophylaxis include, but are not limited to, hyperhidrosis, anhidrosis, Fly syndrome (taste sweating), Hornel syndrome, and Ross syndrome, actinic keratosis, Treatments include actinic keratosis, dermatitis, white spots, psoriasis, psoriasis, lichen planus, eczema, alopecia, psoriasis, malignant or non-malignant skin tumors.</p><p num="0036"> Further objects, features, and advantages of the present invention will become apparent from the following detailed description, along with the accompanying drawings showing embodiments that illustrate the invention, and the following is a description of the drawings. These drawings are examples and are not used to limit embodiments. Moreover, the enumeration of embodiments with the stated features does not exclude other embodiments with additional features or other embodiments incorporating different combinations of the stated features. In addition, the features of one embodiment (eg, in one figure) may be combined with the description (and figures) of the other embodiment.</p>

0037<figref num="1">It is a figure explaining the optical spectrum of the silver nanoplate solution prepared by using the optical conversion method according to one Embodiment of this invention. As prepared, these silver nanoplates, in one embodiment, are 1 cm.^-1Less than (eg about 0.8 cm^-1) Has a peak optical density.</figref><figref num="2">It is a figure explaining the optical spectrum of the silver nanoplate solution prepared by using the seed growth method according to one Embodiment of this invention. As prepared, these silver nanoplates are 3 cm^-1Has a peak optical density of less than.</figref><figref num="3A">It is a figure which shows the transmission electron microscope image of the silver nanoplate solution prepared by using the optical conversion method according to one Embodiment of this invention.</figref><figref num="3B">It is a figure which shows the transmission electron microscope image of the silver nanoplate solution prepared by using the seed growth method according to one Embodiment of this invention.</figref><figref num="4">It is a figure which shows the optical spectrum of the silver nanoplate which did not add a stabilizer and a water-soluble salt according to one Embodiment of this invention before and after tangential flow enrichment.</figref><figref num="5">FIG. 5 shows a normalized optical spectrum of silver nanoplates without the addition of stabilizers and water-soluble salts, according to one embodiment of the invention, before and after tangential flow concentration.</figref><figref num="6">It is a figure which shows the optical spectrum according to one Embodiment of the silver nanoplate combined with polyvinyl alcohol and a water-soluble salt before and after concentration.</figref><figref num="7">It is a figure which shows the normalized optical spectrum according to one Embodiment of the silver nanoplate combined with polyvinyl alcohol and a water-soluble salt before and after concentration.</figref><figref num="8">It is a figure which shows the optical quenching spectrum of the high optical density nanoplate solution processed by the method described in various embodiments of this invention.</figref><figref num="9">It is a figure which shows the process for making one embodiment of a silver nanoplate by preparing a silver nanoplate, adding a stabilizer, concentrating the nanoplate, and optionally coating the nanoplate with silica. ..</figref>

0038Detailed description of preferred embodiments Some embodiments of the present invention include methods for making a solution of plasmon nanoparticles containing silver nanoparticles suitable for performing thermal modulation of a target tissue region. In one embodiment, the thermal modulation of the target tissue is such that the composition comprising the plurality of plasmon nanoparticles is administered to the subject under conditions such that an effective amount of the plasmon nanoparticles are localized in the domain of the target tissue region. Can be achieved if. The target tissue region is exposed to the energy sent from the excited surface plasmon resonance source. Energy is delivered in an effective amount to induce thermal modulation of the domain of the target tissue region.

0039Optical Density (OD) is used herein as a synonym for absorbance and is defined as the logarithmic ratio of radiation incident on a material to radiation transmitted through the material (OD = -log).₁₀(I₁/ I₀), Where I₁Is the intensity of transmitted light, I₀Is the intensity of the incident light). For solutions, optical concentration is a function of the path length through the liquid sample, cm.^-1It is expressed in units of. In some examples, the optical density is in cm^-1Is expressed without the use of (for example, in the example where a standard route length of 1 cm is used). In some conventional methods of producing silver nanoplates, the maximum optical density of silver nanoplates in as-synthesized solution without further treatment is generally 10 cm.^-1Less than (eg 0.1 ~ 9.9 cm^-1, 1 ~ 9cm^-1, 3 ~ 7cm^-1, 1 ~ 5cm^-1, And / or 5 ~ 10cm^-1). However, according to some embodiments of the present invention, silver nanoplates with increased optical density can be produced. Generally, the optical concentration of a solution containing plasmon particles containing silver nanoplates is 10 cm.^-1Higher than (eg 11-5000 cm)^-1, 15 ~ 2000cm^-1, 20 ~ 1000cm^-1, 80 ~ 150cm^-1, 90 ~ 110cm^-1, 900 ~ 1100cm^-1, 100cm^-1, 1000cm^-1Most effective at optical concentrations (or higher), formulated in pharmaceutical or cosmetic carriers, stable for days, months, weeks or years without changes in particle shape and / or properties. .. In one embodiment, the optical concentration of the solution containing plasmon particles containing silver nanoplates is 10 cm.^-1Greater than (eg 11-5000 cm)^-1, 15 ~ 2000cm^-1, 20 ~ 1000cm^-1, 80 ~ 150cm^-1, 90 ~ 110cm^-1, 900 ~ 1100cm^-1, 100cm^-1, 1000cm^-1Or more), formulated in pharmaceutical or cosmetic carriers, stable for days, months, weeks or years without changes in particle shape and / or properties. In one embodiment, the carrier and composition are suitable for topical administration to the skin of a mammalian subject, resulting in the presence of plasmon nanoparticles in an amount effective for selective thermal modulation of skin components.

0040In some embodiments, the nanoparticle formulation is a sponge applicator, cloth applicator, direct contact with a hand or gloved hand, spray, aerosol, vacuum suction, high pressure airflow, or high pressure liquid flow, rollers, brushes. , Planar surface, semi-planar surface, wax, aerosol and other sonic forces, mechanical vibration, hair shaft manipulation (including pulling, massaging), physical force, thermal manipulation, and / or other Formulated for application by the treatment of. In some embodiments, the treatment of the nanoparticle formulation is performed alone, in combination, sequentially, or repeated 1 to 24 times or more. In other embodiments, the plasmon nanoparticles can be selectively localized to a first component of the skin, where physical massage or pressure, ultrasound, or heat can be applied to this first component. Increases the selective localization of nanoparticles. Moreover, nanoparticles can be selectively removed from skin components other than the first component, such removal as acetone, alcohol, water, air, skin exfoliation, chemical peels, waxing, or plasmons. It can be achieved by reducing the compound. In addition, in some embodiments, the nanoparticles have a coat layer that increases the solubility of the nanoparticles in the carrier and / or reduces "stickiness" and accumulation at non-target sites. In one embodiment, at least a portion of the outer surface of the nanoparticles is, for example, a polymer, polar monomer, non-polar monomer, biological compound, metal (eg, metal thin film, metal composite material, metal oxide, or metal salt), dielectric. Modified to include layers of body or semiconductor. In one embodiment, the exterior modifications are polar, non-polar, charged, ionic, basic, acidic, reactive, hydrophobic, hydrophilic, operative, and / or antagonistic. In one embodiment, at least one dimension of at least one nanoparticle in a solution of plasmon nanoparticles is less than 50-100 nm (eg, 1, 5, 10, 25, 40, 60, 75, 90 nm). Particle dimensions 50-100 nm or more (eg 75, 80, 110, 140, 200) , 800 nm), the nanoparticle surface can be coated with a matrix (eg silica) with a thickness of 10-100 nm or more (eg 20, 50, 75, 150, 200, 500 nm). .. This increased dimensional size can increase delivery of all nanoparticles to target areas (eg, hair follicles, pores, skin, etc.) and limit delivery to non-target areas (eg, dermis).

0041In various embodiments, the materials described herein are useful for performing target heating with or without excision of tissue. For example, in one embodiment, (i) the step of topically administering a composition of plasmon nanoparticles comprising silver nanoplates to the skin surface of a subject; (ii) redistributing the plasmon particles from the skin surface to the components of the skin tissue. With or with excision of tissue to treat a mammalian subject in need of treatment, including the steps of providing a means of penetration for; and (iii) resulting in irradiation of the skin surface with light. No method is provided for performing target heating. In a further or additional embodiment, methods are provided in which the light source comprises mercury, xenone, dehydrogen, or metal halide, phosphorescence, incandescent light, light emitting, light emitting diodes, or excitation of sunlight. In yet additional or additional embodiments, the permeation means are high frequency ultrasound, low frequency ultrasound, massage, ion introduction, high pressure airflow, high pressure liquid flow, vacuum, pretreatment by split photothermal decomposition or skin excision, Alternatively, a method including a combination thereof is provided. In a further embodiment, the irradiation is between about 200 nm and about 10,000 nm (eg, 300 to 9000, 700 to 1300, 800 to 1200, 800 to 1300, 900 to 1100, 550 to 1100, 810 to 830, 1000 to 1000 ~. 1100 nm) light wavelength, about 1 to about 100 joules / cm²Fluence (eg 5-20, 40-70, 10-90), pulse width of about 1 femtosecond to about 1 second, and about 1Hz to about 1THz (eg 1-10, 10-100, 100-1000) , 1000 to 10000, 10000 to 100,000 Hz or higher), and methods comprising light having a repetition frequency of 1000 to 10000, 10000 to 100,000 Hz or higher) are provided.

0042An object of one embodiment of the subject matter described herein is, by use of nanoparticles, the skin and underlying tissue, or when used with a light-based energy source in appropriate administration and excitation methods. It is to provide a composition capable of achieving non-invasive and minimally invasive treatment of other accessible tissue spaces. The use of plasmon nanoparticles, eg optical concentration solutions such as silver nanoplates, with short pulse width laser excitation (eg 0.1 ms ~ 1 s pulse width) can create steep and temporary thermal gradients. , It is a structure within several cell layers where particles are localized, such as hair follicle sebaceous gland units for acne treatment and pore size reduction, targets for skin resurfacing and tissue repair of small outer scars. Selectively target heat with or without excision to the transformed epithelial and sebaceous layers and hair follicles for permanent hair loss. Treatments include, but are not limited to, hair loss, hair growth and regrowth, and skin rejuvenation or resurfacing, acne removal or shrinkage, wrinkle reduction, pore shrinkage, cellulite and other skin lipid deposits. Removal, removal of irritation and fungi, thinning or removal of hypertrophic scars, atrophic scars, and scars containing keloids, abnormal pigmentation (eg Portwine mother's spots), removal of tattoos, and / or skin failure Consistency (eg, texture, color, tone, elasticity, hydration) can be mentioned. Other treatments or prophylaxis include, but are not limited to, hyperhidrosis, anhidrosis, Fly syndrome (taste sweating), Hornel syndrome, and Ross syndrome, actinic keratosis, and folliculous keratin. Treatments include treatment of hyperhidrosis, dermatitis, leukoplakia, psoriasis, psoriasis, lichen planus, eczema, alopecia, psoriasis, malignant or non-malignant skin tumors.

0043<u style="single">Physical description of silver nanoplates</u> In one embodiment, nanoplates, such as silver nanoplates, are characterized by lengths along three spindles: two of the spindles have at least two axial lengths of the shortest spindle. Double the largest and shortest spindle length is less than about 500 nm (eg 450. 400, 350, 300, 250, 100, 150, 50, 30, 20, 10 nm). The "edge length" of a nanoplate is defined as the average of the lengths of two long spindles. The "thickness" of the nanoplate is defined as the shortest spindle.

0044The ratio of edge length to thickness is called the "aspect ratio". In various embodiments, the average aspect ratio of the silver nanoplates is greater than 1.5, 2, 3, 4, 5, 7, 10, 20, 30, or 50 and any range thereof. In one embodiment, the average aspect ratio of the silver nanoplates is between 1.5-25, between 2-25, between 1.5-50, between 2-50, between 3-25, and / or between 3-50. Between.

0045In various embodiments, the edge length of the nanoplate is less than 500 nm, 250 nm, 200 nm, 150 nm, 100 nm, 80 nm, 60 nm or 50 nm. In one embodiment, the edge length of the nanoplate is greater than 5 nm, 10 nm, 20 nm, 30 nm, 50 nm or 100 nm. In various embodiments, the edge lengths are 30 nm-100 nm, 20 nm-150 nm, 10 nm-200 nm, 10 nm-300 nm. In various embodiments, the nanoplate has a thickness smaller than 500 nm, 300 nm, 200 nm, 100 nm, 80 nm, 60 nm, 50 nm, 40 nm, 30 nm, 20 nm, and / or 10 nm and any range thereof. In various embodiments, the nanoplate thickness is 5 nm-20 nm, 5 nm-30 nm, 10 nm-30 nm, 10 nm-50 nm, 10 nm-100 nm.

0046Various embodiments of silver nanoplates have a variety of different cross-sectional shapes, including, but not limited to, circular, triangular, or shapes with any number of distinct edges. In a non-limiting embodiment, the nanoplate can be shaped as a circle, ellipse, square, rectangle, rod, star, tube, pyramid, prism, triangle, branch, or consists of a planar surface. be able to. In various embodiments, the nanoplate has edges less than 20, 15, 10, 8, 6, 5, or 4, and / or any number of edges between 20 and 1. In various embodiments, the nanoplate can have an edge between 1-20, 15, 10, 8, 6, 5, 4, or 3. In one embodiment, the nanoplate has more than 2, 3, 4, or 5 edges. In some embodiments, the silver nanoplates have sharp corners, and in other embodiments, these corners are rounded. In some embodiments of silver nanoplates, there are a variety of different cross-sectional shapes within the same sample. In other embodiments of the silver nanoplate solution, more than 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% of the number of particles in the solution. Many are silver nanoplates, and other particles have different shapes, including, but not limited to, spherical, cubic, and irregular shapes. In various embodiments, the silver nanoplate solution is a constant percentage of silver nanoplates and other particles in the solution having different shapes, including, but not limited to, spherical, cubic, and irregular shapes. Has. In various embodiments, the silver nanoplate solution is 5% -100%, 10% -50%, 50% -100%, 30% -60%, 60% -100%, 40% -100%, 70%. It has a number of particles of ~ 100%, 50% -80%, 80% -100%, 60% -100%, and / or 90% -100% in solution, these are limited to silver nanoplates. Other particles with different shapes, including spherical, cubic, and irregular shapes, but not. one In the embodiment of the part, the method retains at least 50%, 60%, 70%, 80%, 90%, 95%, 98% or more of the silver nanoplate shape during the concentration process. However, the stability of the silver nanoplate can be enhanced and the increase in optical density can be promoted. In some embodiments, the method is 50%, 40%, 30%, 25%, 20%, 10%, 5%, 3,%, 2% of silver nanoplates while undergoing a concentration process. , Less than 1%, enhances the stability of silver nanoplates and promotes increased optical density while changing shape from nanoplates to different shapes (eg spherical, cubic, and / or irregular) can do. In various embodiments, the nanoplate can have one, two, or more flat surfaces. In another embodiment, the nanoplate is pyramidal in shape.

0047Silver nanoplates have distinct advantages over other plasmon nanoparticle shapes and compositions. For example, silver nanoplates have advantages over plasmon nanoparticle shapes and compositions, including gold nanoshells and gold nanorods, due to the potential for low manufacturing costs (low reaction waste and low material costs). In addition, because the planar surface of the nanoplate resonates with both polarized light of the incident light, the optical density (OD) per weight of the metal is randomly oriented in solution and when irradiated with non-polarized light. Larger for silver nanoplates compared to gold nanorods. Moreover, the absorbance of silver nanoplates is higher than that of gold nanoshells for the same weight of metal because it scatters due to the nanoplate structure compared to nanoshells, whereas it absorbs more light. For many applications, these benefits of cost and absorbance can only be realized if the nanoplates are stable at high concentrations for long periods of time. This is the subject of one embodiment of the present invention.

0048<u style="single">Preparation of silver nanoplates</u> Modern nanoparticle synthesis techniques have enabled the development of materials with unique optical properties for a wide range of applications, including diagnostic, shielding, and therapeutic applications. Silver nanoplates as prepared by current conventional methods, including light exchange, pH controlled light exchange, thermal growth, and / or seed-mediated growth methods, are generally 0.1 to 10 cm.^-1(For example, 0.1 ~ 9.9 cm^-1, 1 ~ 9cm^-1, 3 ~ 7cm^-1, 1 ~ 5cm^-1, And / or 5 ~ 10cm^-1Has optical density. Several techniques are looking for solutions with higher optical concentrations of silver nanoplates. Some embodiments of the present invention describe novel and non-trivial methods for concentrating silver nanoplates to produce higher optical density silver nanoplate solutions. For example, in various embodiments, the method is 10 cm of an optical concentration solution of silver nanoplates.^-1, 20cm^-1, 30cm^-1, 50cm^-1, 80cm^-1, 100cm^-1, 150cm^-1, 200cm^-1, 300cm^-1, 400cm^-1, 500cm^-1, 600cm^-1, 700cm^-1, 800cm^-1, 900cm^-1, And / or 1000 cm^-1Can be increased to higher or higher.

0049Silver nanoplates are photoconverted (Jin et al. 2001; Jin et al. 2003), pH controlled photoconverted (Xue 2007), thermal growth (Hao et al. 2004; Hao 2002; He 2008; Metraux 2005), templates. Growth (Hao et al. 2004; Hao 2002), Seed-mediated growth ((Aherne 2008; Chen; Carroll 2003; Chen; Carroll 2002, 2004; Chen et al. 2002; He 2008; Le Guevel 2009; Xiong et al. 2007) ) (All incorporated herein by reference), or otherwise prepared using alternative methods, one or more stabilizers and silver sources according to various embodiments of the invention. Examples include the method of forming silver nanoplates from the containing solution and reducing the silver source using chemicals, biological agents, mixtures, electromagnetic rays, and / or heat.

0050The optical spectrum of the silver nanoplate prepared using one embodiment of the photoconversion method is shown in FIG. The peak wavelength of the optical spectrum (100) is 0.74 cm.^-1It has a wavelength of 775 nm at the optical density of. The optical spectrum of silver nanoplates prepared using one embodiment of the seed-mediated growth method is shown in FIG. The peak wavelength of the optical spectrum (200) is 2.58 cm^-1It has a wavelength of 930 nm at the optical density of. A transmission electron microscope image of a silver nanoplate prepared using the photoconversion method is shown in FIG. 3A. A transmission electron micrograph of silver nanoplates made using the seed-mediated growth method is shown in Figure 3B.

0051In one embodiment, when the as-prepared nanoplates are concentrated using tangential filtration, many shapes of the nanoplates can be transformed into nanospheres, with peak photoresonance of spherical silver nanoparticles. It reduces the effectiveness of the formulation, as evidenced by an increase in peak height of about 400 nm. FIG. 4 shows the optical concentrations of one embodiment of the nanoplate solution in the absence of concentration stabilizers before (400) and after concentration (410). The photoresonance peak corresponding to the plasmon resonance of the nanoplate changes from 815 nm (420) to 745 nm (430), indicating a decrease in the average edge length of the nanoplate.

0052FIG. 5 shows a normalized plot of the nanoplate spectrum shown in FIG. For this solution of nanoplates, peak intensities in the 700 nm to 850 nm range correlate with the number of nanoplates in the solution. The peak intensity in the 400 nm range correlates with the number of spherical particles in the solution. Before enrichment, the ratio of long wavelength peaks (520) to short wavelength peaks (540) is 3. After enrichment, the ratio of long wavelength peaks (530) to short wavelength peaks (550) is 0.8. This changing ratio indicates that the silver nanoplates are changing shape and that the number of nanoplates in solution is decreasing.

0053In one embodiment, the nanoplate solution can be stabilized. FIG. 6 shows the optical concentration of one embodiment of a solution of nanoplates stabilized with polyvinyl alcohol in a solution of borate (eg, sodium borate, potassium tetraborate, etc.). The peak wavelength of the nanoplate peak is the same for both the unconcentrated (620) and concentrated (630) solutions, and the edge length of the nanoplate is the same before (600) and after concentration (610). Is shown. FIG. 7 shows a normalized spectrum showing that the shape of the peak spectrum does not change before (700) and after enrichment (710), whereby in one embodiment the surface coating is nano. It is shown to be sufficient to prevent the shape of the particles from changing. In various embodiments, more than 10%, more than 20%, more than 30%, or more than 50% of silver nanoplates change shape without surface protection. In other embodiments, less than 20%, less than 10%, or less than 5% of silver nanoplates undergo shape changes when the nanoplates are coated with a protective surface coating. In one embodiment, about 900 cm^-1The spectrum of the nanoplate solution concentrated to have the peak optical density of is shown in FIG.

0054In one embodiment, silver nanoplates are formed in a multi-step process. In one embodiment, the steps of concentrating the nanoplates are shown in FIG. 9, a step of preparing silver nanoplates (900), a step of adding stabilizers (910), a step of concentrating nanoplates (920) and If desired, it comprises the step of coating the nanoplate with silica (930). In various embodiments, these steps can be performed in any order. In one embodiment, the first step is to form a silver seed from an aqueous solution containing a reducing agent, a stabilizer, a water soluble polymer and a silver salt. The reducing agent, stabilizer and water soluble polymer may be mixed prior to the addition of the silver source. In various embodiments, the reducing agent used in the silver seed forming step is formaldehyde, sodium borohydride, another boron borohydride, hydrogen gas, carbon monoxide gas, hydrazine, or a reducing sugar, or a combination thereof. possible. In various embodiments, the reducing agent may be present at a concentration of at least 0.1 mM, 1 mM, or 3 mM. In various embodiments, the reducing agent may be present in concentrations of 0.1 mM to 1 mM, 0.3 mM to 3 mM, 0.5 mM to 2 mM, 0.1 mM to 2 mM, 0.1 mM to 10 mM.

0055In various embodiments, the stabilizer may be a salt, polymer, or biomolecule. In one embodiment, the stabilizer is trisodium citrate or another citrate derivative.

0056In one embodiment, the water-soluble polymer is a polyanionic polymer, which is, but is not limited to, a polymer derivatized with a sulfonate, a polystyrene sulfonate such as an inorganic salt of a polystyrene sulfonate. Or a monovalent salt of polystyrene sulfonate. In one embodiment, the water soluble polymer is poly (sodium styrene sulfonate) (PSSS). In one embodiment, the molecular weight of PSSS is between about 3 kDa and about 1,000 kDa. In various embodiments, the molecular weights of PSSS are 3kDa to 10kDa, 5kDa to 50kDa, 10kDa to 100kDa, 30kDa to 300kDa, 50kDa to 500kDa, 100kDa to 1000kDa, 300kDa to 100kDa, 500kDa to 1000kDa.

0057In various embodiments, the silver salt may be any water-soluble silver salt, including, but not limited to, silver acetate, silver perchlorate, silver nitrate, silver trifluoroacetate, or silver triflate. Can be mentioned.

0058In one embodiment, the steps for compounding the silver nanoplates include growing the seeds into silver nanoplates in an aqueous solution containing silver seeds, an acid reducing agent and a silver salt. In one embodiment, the acid reducing agent is citric acid or ascorbic acid. The silver salt for the step of growing the seed into silver nanoplates may be any water soluble silver salt, including silver acetate, silver perchlorate, silver nitrate, silver trifluoroacetate, silver triflate, or a combination thereof. ..

0059In one embodiment, the silver nanoplate is 1s^-1~ 100,000s^-1Between (for example, at least 10, 50, 100, 200, 300, 400, 500, 1000, 2000, 5000, 10000, 20000, 50000, 75000, 90000s^-1) Is agitated at the shear flow rate. In various embodiments, the silver nanoplates are 10s.^-1~ 100s^-1During, 50s^-1~ 500s^-1During 100s^-1~ 300s^-1During, 200s^-1~ 500s^-1During 100s^-1~ 400s^-1During, 500s^-1~ 1000s^-1During 1000s^-1~ 10000s^-1During 2000s^-1~ 5000s^-1During 1000s^-1~ 2000s^-1During 5000s^-1And / or 10000s^-1It is agitated at the shear flow rate of.

0060<u style="single">Silver nanoplate coating</u> In one embodiment, the silver nanoplate has molecules that are adsorbed or otherwise bound to the surface of the particles. Molecules on the surface are synthetic reactants or reactant by-products. One object of the present invention is to partially or completely replace molecules bound to the surface of a silver nanoplate with other molecules that more completely prevent the particles from changing shape during concentration. Another object of the present invention is to use a stabilizer that produces a plate shape during preparation and stabilizes the plate during subsequent concentration.

0061In various embodiments, the stabilizers that may be utilized are physically adsorbed on the surface (eg, adsorbed by non-molecular binding forces), molecularly bound to the surface through specific interactions. Examples include chemical or biological agents that are present (eg, thiol or amine) or encapsulated on the surface (eg, metal oxide or semi-metal oxide shell). In one embodiment, the particular chemical agent of interest comprises a polymer. In one embodiment, the particular chemical agent of interest includes a polymer such as polysulfonate. In one preferred embodiment, the stabilized polymer is derivatized with a sulfonate. In some embodiments, vinyl polymers, carbohydrates, ethylene oxide, phenol, and carbohydrates may be used. Specific examples of these polymers include sodium polystyrene sulfonate, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polysaccharides, phenols, tannic acid, dextran, and one or more chemical groups (eg, amines). , Thiols, acrylates, alkins, maleimides, silanes, azides, hydroxyls, lipids, disulfides, fluorescent molecules, or polyethylene glycols (PEGs) containing PEG molecules containing biomolecular moieties. Specific molecules of interest include proteins, peptides, oligonucleotides, biomolecules, alcanthiol, lipoic acid and dihydrolipoic acid and derivatives of these acids, bovine serum albumin, streptavidin, neutravidin, wheat germ aggregates, naturally Includes oligonucleotides and peptides present, as well as synthetic oligonucleotides with one or more chemical functional groups (eg, amine, thiol, dithiol, acrylic phosphoramidite, azide, digoxygenin, alkin, or biomolecular moieties). Synthetic oligonucleotides and peptides include. For specific encapsulation chemicals of interest, SiO₂And TiO₂Includes metal oxide shells such as. Stabilizers may be added prior to the formation of silver nanoplates, during the formation of silver nanoplates, or after the formation of silver nanoplates. A further chemical of interest is gum arabic. In some embodiments, the stabilizer also alters the pH of the solution.

0062<u style="single">Carrier solution</u> In one embodiment of the invention, silver nanoplates are prepared in aqueous solution. In other embodiments, the silver nanoplates are prepared in other solutions, including ethanol, isopropanol, or organic solvents such as heptane, toluene, or butanol.

0063In one embodiment, an acid, base or buffer is added to change the pH of the solution either before, during or after the addition of the stabilizer. In one embodiment, a buffer solution generally containing a water-soluble salt is added. In one embodiment, the water soluble salt comprises borate. In one embodiment, the water soluble salt comprises sodium borate. In one embodiment, the nanoplate is suspended in sodium bicarbonate buffer or sodium borate buffer. In one embodiment, the pH of the solution after the addition of the pH regulator is greater than pH6, pH7, pH8, pH9, or pH10. In various embodiments, the pH of the solution after the addition of the pH regulator is pH 6 to pH 8, pH 6.0 to pH 9, pH 7 to pH 10, pH 7 to pH 11, pH 8 to pH 10, pH 8 to pH 11, or pH 7 to pH 12. ..

0064In one embodiment, the combination of nanoplate coating and water soluble salt present in the buffer provides stabilization for the nanoplate formulation. In some embodiments, one of the components of the salt can interact with the nanoplate coating or stabilizer to crosslink the coating and increase the stability of the coating. In various embodiments, such cross-linking involves non-covalent bonds (eg, ionic bonds, hydrophobic interactions, hydrogen bonds, and dispersion attraction, dipole-dipole interactions and dipole-induced dipole interactions. Van der Waals forces including action) and / or may include covalent bonds between nanoplate surfaces, water-soluble salts, and / or coating materials / stabilizers. In some embodiments, the presence of the water-soluble salt present in the buffer with the stabilizer or coating material and the nanoplate surface, for example, by altering the zeta potential and / or the charge on the surface of the nanoplate. Changes the binding affinity of. In other embodiments, the water-soluble salt present in the buffer alters the binding affinity of the stabilizer or coating material with itself by covalent or non-covalent bonding. In some embodiments, the presence of the water-soluble salt mediates the binding of the stabilizer to the surface of the particle by causing physical adsorption to the particle surface upon association with the stabilizer. In a further embodiment, the water-soluble salt is a polymer by associating with a stabilizer or unit of coating material and reducing the free energy required for the coating material to align on or around the surface of the nanoplate. Mediates the connection between and itself. In one embodiment, the nanoplate coating is a polymer and cross-linking produces a viscoelastic gel that surrounds all or part of the nanoplate. In other embodiments, the stabilizer is mixed with a buffer containing the water-soluble salt, and both the stabilizer and one component of the water-soluble salt bind to the surface of the nanoplate. In one embodiment, a polyvinyl-based polymer such as polyvinyl alcohol or polyvinylpyrrolidone is mixed with a borate such as sodium borate. Polyvinyl alcohol and borate are complexed via hydrogen bonds Can form gels (Schultz 1969). In one embodiment, FIGS. 6 and 7 show the effect of stabilizing silver nanoplates with polyvinyl alcohol and sodium borate prior to concentration to preserve the shape of the nanoparticles.

0065<u style="single">Surface stabilization</u> In various embodiments, the stabilizer can be a solid or liquid formulation added to the silver nanoplate solution. Stabilizers have an affinity for the surface of silver nanoplates and have the ability to associate with the plate surface in a wide range of relative concentrations. In some embodiments, the binding molecules on the silver nanoplates are replaced by stabilizers. Alternatively, stabilizers, such as polymers, are covalently attached to silver atoms present on the surface of the nanoplate. The polymer coating may cover all or part of the outer surface of the silver nanoplate. For example, at least 5%, 10%, 15%, 20%, 25%, 50%, 75%, 80%, 90%, 95%, 99%, 99.9%, or 99.9% or more of the outer surface of silver nanoplates. , Covered with one polymer or several different polymer species. In one embodiment, the stabilizer is added prior to the formation of the silver nanoplate, while in another embodiment the stabilizer is added after the synthesis of the silver nanoplate. Therefore, compositions containing polymer-coated silver nanoplates are provided, and solutions containing these compositions are 10 cm.^-1It may have the following optical densities. Alternatively, such a solution is a polymer-coated silver nanoplate and 10 cm.^-1It has higher optical densities; these solutions can be achieved by concentrating or by purifying polymer-coated silver nanoplates that are present in dilute solutions. In some embodiments, stabilizers are added to the prepared silver nanoplate solution. In other embodiments, the solution in the nanoplate is washed or otherwise residual reactants are removed. In some embodiments, the suspension solution is one or more times with one or more solutions, for example, to wash the nanoplate or to change the pH of the solution, before the stabilizer is added. Will be exchanged. Also in one or more containers, 10 cm^-1Contains nanoplates in solution with higher optical densities and metal oxide-containing or metal oxide precursor-containing solutions suitable for coating the nanoplates with a metal oxide shell (or coating). A kit is also provided. Preferably, the container is provided with its instruction manual. In some embodiments, the kit contains a nanoplate with a coating containing a polyvinyl polymer. In other embodiments, the polyvinyl polymer contains a borate. Nanoplates with stabilizer coatings are described herein or otherwise known in the art, such as particle analyzers or luminescence detectors such as NMR, Fourier transform spectroscopy, mass spectrometry. , Or by a similar assay or the like.

0066Once the stabilizer is added, the mixture of stabilizer and silver nanoplates can be heated, boiled, boiled and refluxed, rotary evaporation, vacuum, agitation, agitation with a magnetic stir bar, agitation with an overhead mixer, agitation with a homogenizer, shaking, It can undergo a number of different processes, including microfluidization, refrigeration, and freezing.

0067<u style="single">Cleaning and concentration</u> In one embodiment, after the stabilization step is complete, the silver nanoplates can be washed to remove residual reactants or replace the solution with another solution. Solution exchange can be accomplished using dialysis, centrifugation, filtration, or tangential flow filtration (also known as cross-flow filtration). In various embodiments, the number of wash volumes exchanged within the sample is 0, 1, 2, 3, 4, 5, 1 and 5, 5-10, 10-20, or 20 or greater. The amount of cleaning.

006810 cm^-1Higher optical density (eg 11-5000 cm)^-1, 15 ~ 2000cm^-1, 20 ~ 1000cm^-1, 80 ~ 150cm^-1, 90 ~ 110cm^-1, 900 ~ 1100cm^-1, 100cm^-1, 1000cm^-1Nanoparticle solutions with (or more) can be prepared using centrifugation, evaporation, filtration, dialysis or tangential filtration. One embodiment of the present invention utilizes tangential flow filtration as a process for concentrating a silver nanoplate solution. The filtration membrane utilized may be formed from a variety of materials. In various embodiments, specific filtration membrane materials of interest may include cellulose esters, polysulfones, and polyethersulfones. In various embodiments, the filtration membranes utilized are pores with a molecular weight cutoff of less than about 10 kD, between 10 kD and 500 kD, or greater than about 500 kD, and / or less than about 0.05 μm, 0.05 μm to 0.5 μm. It may have a pore size of more than about 0.5 μm or between. In various embodiments, the filtration membrane utilized is a pore with a molecular weight cutoff between 10kD-100kD, 10kD-500kD, 20kD-500kD, 20kD-250kD, and / or 0.02 μm. It may have a pore size between ~ 0.1 μm, between 0.05 μm and 0.2 μm, between 0.05 μm and 0.5 μm, between 0.10 μm and 0.2 μm, and between 0.1 μm and 0.5 μm. It is also possible to use tangential flow filtration to change the solvent in which the silver nanoplates are dispersed. In various embodiments, specific solvents of interest include water and alcohols (eg, t-butanol, ethanol, and isopropyl alcohol), as well as other polar or non-polar solvents. Moreover, tangential flow filtration can be used to remove residual chemicals. Figure 8 shows 930 cm^-1An embodiment of a solution of nanoplates concentrated to the peak absorbance of is shown.

0069In various embodiments, the concentration of the silver nanoplate solution is increased to about 5 cm.^-1Higher than, about 10 cm^-1Higher than, about 50 cm^-1Higher than, about 75 cm^-1Higher than, about 100 cm^-1Higher than, about 500 cm^-1Higher and / or about 1000 cm^-1Produces a final solution with a higher optical density. In various embodiments, the concentration of the silver nanoplate solution is increased to 10 cm.^-1~ 100cm^-1Between 30 cm^-1~ 300cm^-1Between 50 cm^-1~ 500cm^-1Between 100 cm^-1~ 1000cm^-1Between 300 cm^-1~ 3000cm^-1Between or 500 cm^-1~ 5000cm^-1Produces a final solution with an optical concentration between. In one embodiment of the invention, the silver nanoplate solution concentration is 10 per milliliter.⁶、10⁷、10⁸、10⁹、10¹⁰、10¹¹、10¹²Or 10¹³Increased to more than one particle. In various embodiments, the silver nanoplate solution concentration is 10 per milliliter.⁶~10¹³Between 10⁷~10¹³Between 10⁸~10¹³Between 10⁹~10¹³Between 10¹⁰~10¹³Between 10¹¹~10¹³Between or 10¹²~10¹³Increased to particles between. In various embodiments, the silver concentration is higher than 0.1, 1.0, 2, 4, 5, 7, 8, 9, and / or 10 mg / mL. In various embodiments, the silver concentration is 0.1 to 1.0, 0.3 to 3.0, 0.5 to 5.0, 1.0 to 10.0, 3.0 to 30.0, 5.0 to 50.0, 10.0 to 200.0, 1.0 to 200.0, 1.0 to 500.0, or 10.0 to 500.0. Between mg / mL.

0070<u style="single">Silica coating and shelling</u> In one embodiment, the concentrated silver nanoplates are encapsulated in a silica shell. The coating may cover all or part of the outer surface of the silver nanoplate. For example, at least 5%, 10%, 15%, 20%, 25%, 50%, 75%, 80%, 90%, 95%, 99%, 99.9%, or 99. More than 9% is coated with silica. The concentrated plate can be mixed with alcohol (eg ethanol or isopropanol). In one embodiment, aminosilane or mercaptosilane is added to the solution to attach the silane molecule to the surface of the nanoplate. The binding of silane molecules to the surface of the nanoplate is unique to the surface coating on the nanoplate. The coating of some nanoparticles that stabilizes the nanoplate during treatment is incompatible with the formation of silica shells. In one embodiment, the surface of the nanoplate is coated with molecules that have an affinity for silane molecules in solution. In one embodiment, a polyvinyl-based polymer such as polyvinyl alcohol or polyvinylpyrrolidone is attached to the surface of the nanoplate prior to the addition of the silane molecule. In other embodiments, the polyvinyl-based polymer surface is a water-soluble salt (eg, one or more sulfates, carbonates, chromates, borates, etc.) present in the buffer prior to the addition of the silane molecule. Phosphate, and complex with sulfite, acetate, and nitrate). In other embodiments, mercaptohexadecanoic acid, mercaptoundecanoic acid, or other thiol-containing acid is attached to the surface of the nanoplate. If the initial silane bound to the surface of the nanoplate is present, additional silane can be added to the solution in the presence of a base to form a silica shell. In one embodiment, the silica shell coated nanoplates can be transferred to water and concentrated using a concentration method such as tangential filtration. In another embodiment, the silica shell is mixed with a solution of an aluminum salt such as aluminum chloride, a stabilizing polymer such as polyvinylpyrrolidone, or a buffer solution such as bicarbonate.

0071An object of the present invention is to prepare a solution containing a concentrated solution of silver nanoplates coated with a silica shell. In one embodiment, the peak optical concentration of the solution measured in a 1 cm path length cuvette is greater than 10, 20, 50, 100, 500, or 1000. In various embodiments, the peak optical concentration of the solution measured in a 1 cm path length cuvette is between 10-100, 20-200, 30-300, 50-500, 100-1000. Between, between 200 and 1000, between 300 and 1000, between 500 and 1000, and / or between 200 and 2000, and any combination within them. In another embodiment, the silver concentration is greater than 0.1 mg / mL, greater than 1 mg / mL or greater than 10 mg / mL. In some embodiments, the silver concentration is between 0.1 and 1.0, between 0.3 and 3.0, between 0.5 and 5.0, between 1.0 and 10.0, between 3.0 and 30.0, between 5.0 and 50.0, and 10.0 to 200.0. Between 1.0 and 200.0, between 1.0 and 500.0, and / or between 10.0 and 500. Between 0 mg / mL and any combination within them. In one embodiment, the thickness of the silica shell is between 2 and 100 nm, and in another embodiment it is between 5 and 50 nm. In various embodiments, the thickness of the silica shell is between 3-20 nm, 5-20 nm, 10-20 nm, 10-50 nm, 10-100 nm, 1-10 nm, 3 Between ~ 30 nm, between 5-50 nm, and / or between 5 and 200 nm, and any combination within them. The silica shell can be prepared from a mixture of silanes, including, but not limited to, aminopropyltriethoxysilane, mercaptopropyltriethoxysilane and tetraethylorthosilicate. The silica shell can contain nitrogen or sulfur atoms. The silica shell can contain an amine moiety or a mercapto moiety. The silica shell can contain aluminum or sodium atoms.

0072In another embodiment, the solution contains a buffer, which contains a water-soluble salt (eg, one or more sulfates, carbonates, chromates, borates, phosphates, and sulfites, Acetates, and nitrates) are included in concentrations higher than 0.1 mM, 1.0 mM or 10.0 mM. In various embodiments, the concentration of water-soluble salts is 0.1 mM to 1 mM, 0.3 mM to 3 mM, 0.5 mM to 5 mM, 1 mM to 10 mM, 1 mM to 30 mM, 1 mM to 50 mM, 1 mM to 1000 mM, and any of them. It may be a combination of. The solution peaks between 500 nm and 1500 nm, 500 nm to 1200 nm, 500 nm to 1000 nm, 600 nm to 1200 nm, 700 nm to 1200 nm, 700 nm to 1500 nm, 700 nm to 900 nm, and / or 900 to 1100 nm, and any combination within them. It may have an absorption wavelength.

0073<u style="single">storage</u> In various embodiments, the concentrated particles are stored at temperatures below -10, 0, 4, 6, 10, or 20 ° C. In one embodiment, the particles are frozen and vacuum dried. In one embodiment, the particles are freeze-dried. In one embodiment, the particles are supercritically dried. In one embodiment, additional stabilizers or other antifreezes are added to the solution before the particles are heat dried or freeze dried.

0074<u style="single">Composite material</u> In one embodiment of the invention, the high optical concentration solution of silver nanoplates associates with the substrate. In various embodiments, examples of substrates include fibers, fabrics, meshes, bandages, socks, wraps, other clothing, sponges, highly porous substrates, particles with edge lengths greater than 1 micron, beads, etc. Hair, skin, paper, absorbent polymers, foams, wood, corks, slides, rough surfaces, biocompatible substrates, filters, or medical implants. In various embodiments, a solution of silver nanoplates at a concentration of at least 1 mg / mL, 10 mg / mL, and / or 100 mg / mL is incubated with the substrate. In some embodiments, the silver nanoplate concentrations incubated with the substrate are 0.1-1.0, 0.3-3.0, 0.5-5.0, 1.0-10.0, 3.0-30.0, 5.0-50.0, 10.0-20.0, 5.0-50.0, It is between 3.0 to 50.0, 1.0 to 100.0 mg / mL, 10.0 to 100.0, 20.0 to 100.0, and 30.0 to 100.0 mg / mL. In another embodiment, the solution of silver nanoplates incubated with the substrate is 10 per milliliter.⁶~10¹³Between 10⁷~10¹³Between 10⁸~10¹³Between 10⁹~10¹³Between 10¹⁰~10¹³Between 10¹¹~10¹³Between 10¹²~10¹³Between or 10¹³These are the above particles. In another embodiment, the silver nanoplates are at least 10, 20, 50, 100, 300, 500, 1000 and / or 2000 cm before being incubated with the substrate.^-1It is prepared with the optical density of. In various embodiments, the silver nanoplates are between 10-100, 20-200, 30-300, 50-500, 100-1000, 200-1000, 300-1000. It is prepared with an optical density of between 500 and 1000, or between 200 and 2000. In another embodiment, the substrate is chemically treated to increase the bond between the nanoplate and the substrate. For example, the substrate can be functionalized by molecules that result in a positively or negatively charged surface. In another embodiment, the pH of the incubation solution is selected to optimize binding. In another embodiment, the silver nanoplate covers at least 5%, 10%, 20%, 30%, 50% or 75% of the substrate. In various embodiments, the silver nanoplates are between 5% to 10% of the substrate, between 10% and 100%, between 10% and 50%, between 50% and 100%, and between 30% and 100%. Between 30% to 70%, between 40% and 80%, between 50% and 90%, between 60% and 100%, between 70% and 100%, between 80% and 100% , 90% -100%, 0% -5%, 0% -10%, 0% -20%, 0% -30%, or 0% -50% cover. In another embodiment, another solvent or chemical is added to the incubation solution. In another embodiment, a biological linker (eg, antibody, peptide, DNA) is used to bind the high optical density silver nanoplate to the surface of the substrate. In one embodiment, the incubation is between less than 1 minute, 5 minutes, 20 minutes, 60 minutes, or 120 minutes. In various embodiments, the incubation is between 0 and 1 minutes, between 1 and 120 minutes, between 5 and 120 minutes, between 20 and 120 minutes, between 60 and 120 minutes, and 5 minutes. Between ~ 60 minutes, between 10 and 60 minutes, between 20 and 60 minutes, between 0 and 10 minutes, between 0 and 20 minutes, or between 0 and 5 minutes.

0075In one embodiment, the substrate is separated from the incubation solution and dried. The substrate can be dried using air drying, heat drying, lyophilization, or supercritical drying. In another embodiment, the dried substrate is further treated by immersing the substrate in another material, coating the substrate with another material, or exposing the substrate to another material in the gas phase. be able to.

0076Other embodiments of the invention will be apparent to those skilled in the art given the specification and practice of the invention disclosed herein. The specification and examples are intended to be considered only as disclosing a particular embodiment of the invention, the true scope and spirit of the invention is set forth in the claims below.

0077The subject matter described herein may be embodied in other particular forms without departing from its spiritual or essential characteristics. As such, the aforementioned embodiments are considered descriptive rather than restrictive in all respects. Embodiments are susceptible to various modifications and alternatives, examples of which are set forth in these drawings and described in detail herein. However, the invention is not limited to the particular embodiments or methods disclosed, and contrary to this, the invention is within the spirit and scope of the various embodiments described and the appended claims. It is of course understood to cover all modifications, equivalents, and alternative forms of. None of the methods disclosed herein need be performed in the order listed.

0078The methods disclosed herein include the specific actions taken by a practitioner; however, they may also include, expressly or implicitly, third party instructions for those actions. For example, actions such as "identifying a target area of skin tissue" include "instructing the identification of a target area of skin tissue".

0079The scope disclosed herein also includes all overlaps, subranges, and combinations thereof. Words such as "maximum," "at least," "greater than," "less than," "between," and the like include the numbers listed. Numbers that precede terms such as "about" or "approximately" or "substantially" include the numbers listed. For example, "about 3 minutes" includes "3 minutes". The terms "approximately", "about" and / or "substantially" are used herein in an amount or feature close to the stated amount or feature that still performs the desired function or achieves the desired result. Represents. For example, the terms "approximately," "about," and "substantially" include less than 10%, less than 5%, less than 1%, less than 0.1%, and less than 0.01% of the stated amount or feature. You may refer to the amount inside.

<p num="0080"> The description of the specific examples below is for illustration purposes only and does not limit the scope of the invention disclosed herein.</p><p num="0081"><u style="single">Example 1: Silver nanoplate</u> Silver nanoplates were synthesized using silver seeds prepared by reducing silver nitrate with sodium borohydride in the presence of sodium tribasic sodium citrate and sodium polystyrene sulfonate under aqueous conditions. Preparation of silver seeds: 21.3 mL of 2.5 mM aqueous sodium tribasic citrate was mixed under magnetic agitation. A 1 mL 2 g / L polystyrene sulfonate (PSSS) solution was then prepared in a separate beaker. Next, 21.3 mL of 0.5 mM silver nitrate solution was prepared by dissolving the salt in water. Once the above solution was prepared, 1.33 mL of 0.5 mM sodium borohydride solution was prepared in water at 4 ° C. Hydrogen borate and PSSS solutions were then added to the beaker containing the citrate and mixed. The silver nitrate solution was then poured into the citrate solution using a peristaltic pump at a rate of 100 mL / min. The seed solution was then stirred at room temperature overnight. Silver nanoplates were prepared by mixing 1530 mL of Milli-Q water with 35 mL of 10 mM ascorbic acid solution. Once the solutions were well mixed, the prepared silver seeds were added to the reactor. A 353 mL 2 mM silver nitrate solution was poured into the reactor at a rate of 100 mL / min. The reaction was mixed for 2 hours. TEM analysis showed that over 70% of the particles were nanoplates. The optical concentration of the solution is 2.8 cm^-1Met.</p><p num="0082"><u style="single">Example 2: Concentrated silver nanoplates</u> About 5 cm^-1A 15 L silver nanoplate with a peak optical density of 3100 cm was mixed with 3.5 g of polyvinyl alcohol (PVA) and sodium borate.²Concentrated using tangential filtration using a 500 kD polysulfone tangential flow membrane with a surface area of. The solution was concentrated for about 90 minutes and the final solution volume was reduced from 15 L to 0.5 L. Optical density of silver nanoplate solution is about 150 cm^-1Increased to. Therefore, according to one embodiment, the silver nanoplate solution is 5 cm.^-1From 150 cm^-1Methods for increasing to (eg, roughly 30-fold increase in optical density) include adding PVA and sodium borate to the silver nanoplate, and concentrating the solution by tangential filtration .</p><p num="0083"><u style="single">Example 3: Concentrated silver nanoplates</u> An example of concentrating silver nanoplates is about 4 cm^-1A 1.2 L silver nanoplate with a peak optical concentration of was mixed with 4 L absolute ethanol and about 49 mL ammonium hydroxide solution. 0.6 mL of diluted aminopropyltriethoxysilane (APTES) was added to the solution. After a 15 minute incubation, 6.5 mL of tetraethyl orthosilicate (TEOS) solution was added. After 24 hours, 1 L of solution, 1050 cm²Concentrated using a 500 kD polysulfone tangential flow membrane with a surface area of. The final solution volume was reduced to 150 mL, and the optical concentration of the silver nanoparticle solution was reduced to about 40 cm.^-1Increased to. Therefore, according to one embodiment, the silver nanoplate solution is 4 cm.^-1From 40 cm^-1Methods for increasing up to (eg, roughly 10-fold increase in optical density) include absolute ethanol, ammonium hydroxide solution, aminopropyltriethoxysilane (APTES), and tetraethyl orthosilicate (TEOS) on silver nanoplates. It includes a step of adding and a step of concentrating the solution by tangential flow filtration.</p><p num="0084"><u style="single">Example 4: Nanoplate with silica shell</u> Silica shells were grown on the surface of silver nanoplates capped with 800 nm resonant (edge length about 75 nm) polyvinylpyrrolidone (PVP). 2 mg / mL (OD20 cm)^-1), A solution of silver nanoplates capped with 800 nm resonance PVP was added to 2.3 L of reagent grade ethanol and 190 mL of Milli-Q water under constant stirring. 4.3 mL of diluted aminopropyltriethoxysilane (215 uL APTES in 4.085 mL isopropanol) was then added to the solution, followed immediately by 44 mL of 30% ammonium hydroxide. After a 15 minute incubation, 31 mL of diluted tetraethyl orthosilicate (1.55 mL TEOS in 29.45 mL isopropanol) was added to the solution. The solution was then stirred overnight. The nanoplates were then centrifuged in an Ultracentrifuge at 17000 RCF for 15 minutes, reconstituted in Milli-Q water each time and repeated twice. The thickness of the silica shell was 15 nm. The optical density of the concentrated material is 2040 cm^-1Met.</p><p num="0085"><u style="single">Example 5</u> 40 mL of a 40 O.D. solution of concentrated silver nanoplates stabilized with polyvinyl alcohol and sodium borate was spun at 3000 RCF for 30 minutes. The supernatant was removed and the pellet was redispersed by bath sonication. The concentrated silver nanoplates had higher optical densities than 900 O.D. as shown in FIG.</p><p num="0086"><u style="single">Example 6: Concentrated nanoplates on a substrate</u> 5 mL of 1000 O.D. silver nanoplate solution, 3 "x3" sections (Ab) of absorbent cloth Added to sorber Synthetic Drying Chamois, Clean Tools). After the addition, the substrate was air-dried. Upon drying, the silver nanoplates bound to the surface of the absorbent cloth, after which the cloth became moist and was not released when the water was removed by applying pressure.</p><p num="0087"> Each of the above references is incorporated by reference in its entirety.</p>