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WO2011045627A1 - Agents virucides avec des matériaux biocatalyseurs nanostructurés de dioxyde de titane (tio2) et de dioxyde de silicium (sio2) avec du platine et de l'iridium modifiés et dispersés sur la surface - Google Patents

Agents virucides avec des matériaux biocatalyseurs nanostructurés de dioxyde de titane (tio2) et de dioxyde de silicium (sio2) avec du platine et de l'iridium modifiés et dispersés sur la surface Download PDF

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Publication number
WO2011045627A1
WO2011045627A1 PCT/IB2009/007188 IB2009007188W WO2011045627A1 WO 2011045627 A1 WO2011045627 A1 WO 2011045627A1 IB 2009007188 W IB2009007188 W IB 2009007188W WO 2011045627 A1 WO2011045627 A1 WO 2011045627A1
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WO
WIPO (PCT)
Prior art keywords
nanostructured
platinum
iridium
materials
viricide
Prior art date
Application number
PCT/IB2009/007188
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English (en)
Inventor
Tessy Maria Lopez Goerne
Original Assignee
Arce Macias, Carlos, Francisco
MUÑOZ OCHOA, José, Francisco
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Arce Macias, Carlos, Francisco, MUÑOZ OCHOA, José, Francisco filed Critical Arce Macias, Carlos, Francisco
Priority to PCT/IB2009/007188 priority Critical patent/WO2011045627A1/fr
Publication of WO2011045627A1 publication Critical patent/WO2011045627A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group

Definitions

  • M silicium, titanium or a mix of both
  • the particle size of the nanostructured matrix, acidity, mean pore size of the matrix and platinum, iridium or platinum-indium particle size can be controlled since the synthesis.
  • Nanostructured materials can be use as viricide.
  • Biosynthesis of nanoparticles as an emerging highlight of the intersection of nanotechnology and biotechnology has received increased attention due to a growing need to develop environmentally benign technologies in material syntheses. Biomolecules as reluctant are found to have a significant advantage over their counterparts as protecting agents (7 13) .
  • the properties of the materials can change notably when its particle size is reduced to particles in the scale of nanometers.
  • particle is a general term to describe small solid objects with sizes ranging from atomic scale (10 "1 ° m) to the microscopic scale (10 3 m). However, the particle size often lies between 10 "9 -10 "5 m. Large particles (> 10 "6 ) are commonly called grains (i. e. zeolites, carbon, Raney metals) and small particles ( ⁇ 15 nm) are frequently added (metals) to mixed oxides, i.e. Ti02-Si0 2 , S1O2 or TiO2 (14"20) . All materials consist of grains (particles) formed by the agglomeration of nanoparticles ( Figure 1 ).
  • the grains have a size ranging from 100 micrometers to millimeters (mm), while the Nanomaterials particles are in the order of a one billionth of a meter (10 9 ).
  • a nanometer is around the average diameter of human hair.
  • the radius of an atom is 1 to 3 Angstrom (A) and a nanometer is equal to 10 A.
  • Nanomaterials are rigid solid, resistant and are ductile at high temperatures, are resistant to degradation, erosion and corrosion, are also very chemically active.
  • the physical and chemical properties of each nanomaterial or nanostructured material are determined by the type of interactions compounds that functionalized the nanoparticles; as well the electronic density and hydroxyl concentration in the net have an important role in the DNA cracking.
  • One of the areas in which nanoparticles have increased the importance is in the field of catalysis and biocatalysis, in order to obtain a distribution of particles with well defined shape and size to improve the catalytic activity.
  • the structure includes a solid area, pore size, as well as the shape and volume of the pores.
  • Titanium dioxide occurs in nature in three crystalline phases; anatase, rutile and brookite (Fig. 2).
  • the anatase and brookite can transform into rutile at high temperatures.
  • the anatase to rutile can be irreversibly transformed by heating.
  • There are several factors that influence the phase shift such as particle size, crystal morphology, but in particular influence of the poisoning ions to the network.
  • the literature indicates that the three phases, the anatase has a great chemical stability, resistance to corrosion, is inert from biological agents and has high specific surface area.
  • the commercial titania Is a mix (Degussa P25) and contains 60 to 80% anatase.
  • the problem only to produce the anatase phase is due to the rutile phase is thermodynamically more stable. Therefore by the sol- gel process is possible to obtain pure anatase and pure rutile.
  • the structure of anatase and rutile are tetragonal, whereas brookite is orthorhombic, each titanium atom is attached to 6 oxygen atoms almost equidistant and each oxygen atom is linked to three atoms of titanium.
  • silica sol-gel is an amorphous material with high specific area and high concentration of hydroxyl groups in its surface. Recently, the need for disinfectants, bactericides and viricides with confirmed efficiency against various microorganisms like virus and bacteria has increased (Fig. 3).
  • Nanomedicine will have a profound impact on infectious disease in several ways, for improved diagnostics and detection, targeted therapies, and antibacterial or antiviral surfaces. Diagnostic technologies combine a recognition system and a detection system, from tiny cantilever that move on binding antigen to nanowires that detect current from immune-cell binding. For prevention, nanotechnology-based microbicides against HIV are now in early clinical trials.
  • Sol-gel derived silica and titania have a specific interaction with many biological molecules, microbes, algae, cells and living tissue. The specific interactions mean that they differ from common reactions between non-viable materials and biomolecules or living tissues and the interactions are mostly beneficial from the viewpoint of biotechnical applications.
  • Peptides and proteins may preserve their activity and bacteria, algae and cells may preserve their viability and viruses their infectivity as encapsulated in sol-gel derived silica.
  • Silica and titania are known to form a direct bond with living tissue which can be utilized in the biomaterial applications.
  • Other application areas of silica and titania are in biosensing, tissue engineering, gene therapy, controlled delivery of therapeutic agents and environmental protection* 21"30 '.
  • U.S. Pat. No. 6 124 367 This patent protects reservoirs used in the Fischer Tropsch reactions from sintering by imparting a higher degree of mechanical strength to the reservoir. It incorporates S1O2 and Al 2 0 3 into the reservoir and claims a rutile-anatase ratio of 1/9. It is a porous reservoir with either a spherical or a cylindrical shape. It is made by extrusion, spray drying or tableting.
  • U.S. Pat. No. 6117814 This patent describes a titania reservoir which also incorporates silica and alumina as a binder into the structure.
  • the purpose of the binder is to impart better mechanical properties to the reservoir.
  • the size range of this reservoir is from between 20 to 120 microns.
  • the reservoir is approximately 50% binder, which is fabricated by a sol-gel process.
  • the invention relates to a titanium oxide-based polymer composition.
  • Said polymer which has a one-dimensional (1 D) structure, is made from concentrically-wound fibres having a periodicity, which is deduced from the spacing between said fibres, of between 3.5 A and 4 A.
  • Each fibre comprises Ti0 6 octahedrons and each ⁇ octahedron shares two opposite edges with two adjacent octahedrons (2 x 2.92 A) in order to form infinite chains which develop along the axis of a fibre.
  • two adjacent chains form double lines as a result of the shared edges (2 x 3.27 A).
  • the inventive polymer is suitable for use as a photosensitive element in a photovoltaic cell, such as a sunscreen for a window.
  • the invention relates to a method of preparing a stable oxide ceramic precursor sol-gel solution based on lead, titanium, zirconium and lanthanide(s).
  • the invention comprises the following successive steps consisting in: a) preparing a sol-gel solution by bringing a molecular lead precursor, a molecular titanium precursor, a molecular zirconium precursor and a molecular lanthanide precursor into contact with a medium comprising a diol solvent and optionally an aliphatic mono-alcohol; b) leaving the solution thus obtained to stand for a sufficient period of time in order to obtain a solution having an essentially-constant viscosity; and c) diluting the solution obtained in the preceding step with a diol solvent identical to that used in step a or a solvent that is miscible with said solvent, at a predetermined rate.
  • the invention can be used to prepare an oxide ceramic material comprising lead, a lanthanide metal, titanium and zirconium.
  • Sol-gel nanostructured titania reservoirs for use in the controlled release of drugs in the central nervous system and method of synthesis.
  • the invention is related to a sol- gel nanostructured titania reservoir and its synthesis which is biocompatible with brain tissue.
  • the pore size distribution, crystallite size and the extent of the crystalline phase distribution of anatase, brookite and rutile can be fully controlled.
  • This device may be used to contain neurological drugs. It may be inserted directly into brain tissue for the purpose of the controlled time release of drugs over a period of from 6 months to three years.
  • Novel coating materials for biomedical applications particularly for use on biomedical implants, the coating material containing gel-derived titania where the material is capable of inducing calcium phosphate formation onto its surface under in vitro conditions, e.g. in a simulated body fluid and/or under in vivo conditions, processes for the preparation of the coating materials as well as their use in biomedical implant technology.
  • nanostructured biomaterials for use like viricide.
  • optimization of these nanomaterials to enable control of the following parameters: acidity of the support, BET area, pore size distribution, particle size, degree of functionalization, electronic density, dispersion of the metal or metals on the support.
  • the materials will consist of nanostructured titania, silica or mixed oxides titania-silica prepared using sol-gel methods. These materials are functionalized and have high dispersed Pt or Pt-lr with a small particle size (2- 10 nm).
  • the present invention is related to novel nanostructured materials (silica, titania and titania-silica) synthesized by the sol-gel process. 2. This nanomaterials are gels partially hydroxylated, with a Ti:Si ratio between 0: 100 and 100:0.
  • the nanoparticulate materials were functionalized with phosphate, ammonia, • carboxyl and hydroxyl groups, which are stable and linked to the surface after drying. Using ammonium sulphate, ammonium phosphate, phosphoric acid, sulfuric acid, GABA, acetate and acetilacetonate. 6. The polymerization continues for a long period of time after the gelacion. Both the titania (T1O2) and silica (S1O2) or a mixture of both (Ti02-Si02) are functionalized from the start of the reaction to achieve biocompatible materials.
  • nanostructured materials obtained have been replaced the Si or Ti atoms for platinum (Pt) and iridium (Ir) atoms from 0.01 % to 5%.
  • Pt platinum
  • Ir iridium
  • the biocatalytic activity of nanostructured biomaterials depends on the particle size of titania or silica or mixed oxides, the particle size of iridium and platinum supported on the surface and the density of acid sites. .
  • the electronic structure of nanostructured biocatalysts is controlled in order to generate point defects in the network of biocatalysts leads to free radicals that accelerate the cracking of C-C and C-N links in the RNA bases, and in the proteins of the virus.
  • Both the titania (Ti0 2 ) and silica (S1O2) or a mixture of both (Ti0 2 -Si02) have hydroxyl, carboxyl, ammine, sulphate and phosphate functional groups linked to the nanoparticle surface to be recognized by the virus.
  • the molar alkoxide solvent from 1 :8 to 1 :70.
  • the solvent used is polar or non- polar, aprotic or protic.
  • the synthesis of pure titanium, pure silica or a mixture of both is performed via sol-gel process with constant agitation at a temperature from ambient to 70°C. 16.
  • the kinetics of the process of cracking links biocatalytic C-C and C-N show a direct dependence of the particle size from 1 nm to 200 nm.
  • the order of the kinetics reaction and the activity of biocatalysts depend of the platinum ligands, iridium ligands, specific area and mean pore size, acidity and electronic distribution of the matrix (Si0 2 , Ti0 2 and Si0 2 -Ti0 2 ).
  • the order of the kinetics reaction and the activity of biocatalysts depend or the virus conformation.
  • sol-gel process using metal alkoxides At the functional group level, three reactions are generally used to describe the sol-gel process: hydrolysis, alcohol condensation, and water condensation.
  • the characteristics and properties of a particular sol-gel inorganic network are related to a number of factors that affect the rate of hydrolysis and condensation reactions, such as, pH, temperature and time of reaction, reagent concentrations, catalyst nature and concentration, H 2 0/M molar ratio (R), aging temperature and time, and drying.
  • pH, nature and concentration of catalyst, H 2 O/M molar ratio (R), and temperature have been identified as most important.
  • Values for a ranged from 0.5 to 1.0, which indicates a linear or lightly branched 5 molecule or chain.
  • the hydrolysis reaction (Eq. 2), through the addition of water, replaces alkoxide groups (OR) with hydroxyl groups (OH). Subsequent ) 5 condensation reactions are made, involving the silanol groups (Si-OH) produce siloxane bonds (Si-O-Si) plus the by-products water or alcohol in the case of silica. Under most conditions, condensation commences before hydrolysis is complete. However, conditions such as, pH, H 2 0/Si molar ratio (R), and catalyst can force completion of hydrolysis before condensation begins. Additionally, because water and alkoxides are immiscible, a mutual solvent is utilized.
  • Acid-Catalyzed HydrolvsisBased-Catalyzed Mechanism Base-catalyzed hydrolysis of silicon alkoxides proceeds much more slowly than acid-catalyzed hydrolysis at an equivalent catalyst concentration.
  • Basic alkoxide oxygens tend to repel the nucleophile, -OH.
  • hydrolysis of the forming polymer is more sterically hindered than the hydrolysis of a monomer.
  • Pt(NH 3 ) 4 Cl2 was dissolved in ethanol and distilled water. The solution was stirred continuously under constant reflux. Following the complete dissolution of the salt, tetraethoxysilane (TEOS), ⁇ -Aminobutyric acid (GABA), phosphoric acid and ammonium phosphate were added to the solution. The resulting sol was maintained under constant flux and continual stirring until the gel was formed. The evaporation of the solvent and water was performed at room temperature. The dry solid was crushed and subsequently used to perform characterization studies.
  • TEOS tetraethoxysilane
  • GABA ⁇ -Aminobutyric acid
  • phosphoric acid and ammonium phosphate were added to the solution.
  • the resulting sol was maintained under constant flux and continual stirring until the gel was formed. The evaporation of the solvent and water was performed at room temperature. The dry solid was crushed and subsequently used to perform characterization studies.
  • Rotavirus is a genus of double-stranded RNA virus in the family Reoviridae (Double-stranded (ds) RNA viruses are a diverse group of viruses that vary widely in host range (humans, animals, plants, fungi, and bacteria), genome segment number (one to twelve), and virion organization (T- number, capsid layers, or turrets).
  • ds double-stranded
  • RNA viruses are a diverse group of viruses that vary widely in host range (humans, animals, plants, fungi, and bacteria), genome segment number (one to twelve), and virion organization (T- number, capsid layers, or turrets).
  • Influenza commonly referred to as the flu
  • the influenza A virus particle or virion is 80-120 nm in diameter and usually roughly spherical, although filamentous forms can occur.
  • the influenza A genome is not a single piece of nucleic acid; instead, it contains eight pieces of segmented negative-sense RNA (13.5 kilobases total), which encode 11 proteins (HA, NA, NP, M1 , M2, NS1 , NEP, PA, PB1 , PB1-F2, PB2).
  • the best-characterised of these viral proteins are hemagglutinin and neuraminidase, two large glycoproteins found on the outside of the viral particles.
  • the nanostructured and functionalized biocatalysts of this patent break the RNA bonds and the protein structure of the virus of this kind.
  • the 4 supernatants were neutralized with bicarbonate, to adapt to the environment of the cells.
  • the crystal violet stains only cells that remain attached to the monolayer on the bottom of the well. When cells flow is indicative of losing their adhesion ability, i.e. they approach death. This method is very useful because there is a directly correlation between the amount of blue violet and healthy cells.
  • the virus was incubated with nanoparticles and activated for one hour and then applied to healthy cells.
  • Viruses with cells without nanoparticles were used as reference and to differentiate the activity of the infection with and without nanoparticles.
  • Other controls of nanoparticles with cells were used to confirm the viability of these.
  • Actuators B Chemical, 126- 2, (2007) 562-572.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Medicinal Preparation (AREA)

Abstract

Cette invention concerne la synthèse de matériaux inorganiques nanostructurés représentés par la formule générale MaLbBc02(b+c)(OH)x(PO4)y(SO4)z dans laquelle M représente le silicium, le titane ou un mélange des deux et L représente l'iridium et B le platine, B + L < M, b + c = 1 et b est différent de c. La taille des particules de la matrice nanostructurée, l'acidité, la taille moyenne des pores de la matrice et la taille des particules de platine, d'iridium ou de platine-iridium peuvent être ajustées depuis la synthèse. Les matériaux nanostructurés peuvent être utilisés comme virucide.
PCT/IB2009/007188 2009-10-12 2009-10-12 Agents virucides avec des matériaux biocatalyseurs nanostructurés de dioxyde de titane (tio2) et de dioxyde de silicium (sio2) avec du platine et de l'iridium modifiés et dispersés sur la surface WO2011045627A1 (fr)

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WO2016049131A1 (fr) 2014-09-23 2016-03-31 Attostat, Inc. Compositions antimicrobiennes et procédés
US10137503B2 (en) 2011-07-01 2018-11-27 Attostat, Inc. Method and apparatus for production of uniformly sized nanoparticles
WO2019016724A2 (fr) 2017-07-20 2019-01-24 GÓMEZ-LÓPEZ, Wenceslao Formulation comprenant une matière nanostructurée, biocompatible et biocatalytique pour le traitement de plaies et d'infections
WO2019016725A2 (fr) 2017-07-20 2019-01-24 GÓMEZ-LÓPEZ, Wenceslao Formulation de nettoyage personnel, de matériau et de surface comprenant des particules nanostructurées
US10201571B2 (en) 2016-01-25 2019-02-12 Attostat, Inc. Nanoparticle compositions and methods for treating onychomychosis
WO2019156118A1 (fr) * 2018-02-09 2019-08-15 株式会社フルヤ金属 Matière poreuse antibactérienne, produit antibactérien la contenant et procédé antibactérien la mettant en œuvre
WO2019156122A1 (fr) * 2018-02-09 2019-08-15 株式会社フルヤ金属 Matière poreuse anti-moisissure, produit anti-moisissure la contenant, et procédé anti-moisissure associé
CN110720469A (zh) * 2019-10-09 2020-01-24 中国科学院上海硅酸盐研究所 一种磷酸根修饰的二氧化钛光催化抗病毒涂层及其制备方法和应用
US10774429B2 (en) 2015-04-13 2020-09-15 Attostat, Inc. Anti-corrosion nanoparticle compositions
US10953043B2 (en) 2015-04-01 2021-03-23 Attostat, Inc. Nanoparticle compositions and methods for treating or preventing tissue infections and diseases
US11018376B2 (en) 2017-11-28 2021-05-25 Attostat, Inc. Nanoparticle compositions and methods for enhancing lead-acid batteries
EP3654949A4 (fr) * 2017-07-20 2021-08-25 Gómez-López, Wenceslao Biocatalyseurs nanostructurés et biocompatibles utilisables dans le traitement du cancer
CN114354558A (zh) * 2022-01-07 2022-04-15 中国科学院长春应用化学研究所 一种比率型荧光纳米探针、制备方法及定量检测基质金属蛋白酶-7活性的方法
WO2022129983A1 (fr) 2020-12-14 2022-06-23 LÓPEZ MACÍAS, Javier Eduardo Nanosystèmes basés sur des nanocomposites et des extraits naturels
US11473202B2 (en) 2015-04-13 2022-10-18 Attostat, Inc. Anti-corrosion nanoparticle compositions
US11646453B2 (en) 2017-11-28 2023-05-09 Attostat, Inc. Nanoparticle compositions and methods for enhancing lead-acid batteries
US12115250B2 (en) 2019-07-12 2024-10-15 Evoq Nano, Inc. Use of nanoparticles for treating respiratory infections associated with cystic fibrosis

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US10610934B2 (en) 2011-07-01 2020-04-07 Attostat, Inc. Method and apparatus for production of uniformly sized nanoparticles
US10137503B2 (en) 2011-07-01 2018-11-27 Attostat, Inc. Method and apparatus for production of uniformly sized nanoparticles
EP3197279A4 (fr) * 2014-09-23 2018-04-18 Attostat, Inc. Compositions antimicrobiennes et procédés
WO2016049131A1 (fr) 2014-09-23 2016-03-31 Attostat, Inc. Compositions antimicrobiennes et procédés
US10953043B2 (en) 2015-04-01 2021-03-23 Attostat, Inc. Nanoparticle compositions and methods for treating or preventing tissue infections and diseases
US11473202B2 (en) 2015-04-13 2022-10-18 Attostat, Inc. Anti-corrosion nanoparticle compositions
US10774429B2 (en) 2015-04-13 2020-09-15 Attostat, Inc. Anti-corrosion nanoparticle compositions
US10201571B2 (en) 2016-01-25 2019-02-12 Attostat, Inc. Nanoparticle compositions and methods for treating onychomychosis
CN111093631A (zh) * 2017-07-20 2020-05-01 文塞斯劳·戈麦斯-洛佩斯 包含纳米结构的颗粒的表面、材料和个人的清洁制剂
WO2019016725A2 (fr) 2017-07-20 2019-01-24 GÓMEZ-LÓPEZ, Wenceslao Formulation de nettoyage personnel, de matériau et de surface comprenant des particules nanostructurées
WO2019016724A2 (fr) 2017-07-20 2019-01-24 GÓMEZ-LÓPEZ, Wenceslao Formulation comprenant une matière nanostructurée, biocompatible et biocatalytique pour le traitement de plaies et d'infections
EP3654944A4 (fr) * 2017-07-20 2021-08-25 Gómez-López, Wenceslao Formulation comprenant une matière nanostructurée, biocompatible et biocatalytique pour le traitement de plaies et d'infections
EP3654949A4 (fr) * 2017-07-20 2021-08-25 Gómez-López, Wenceslao Biocatalyseurs nanostructurés et biocompatibles utilisables dans le traitement du cancer
CN111093630A (zh) * 2017-07-20 2020-05-01 文塞斯劳·戈麦斯-洛佩斯 用于治疗创伤和感染的包含纳米结构、生物可相容且生物催化的材料的制剂
WO2019016724A3 (fr) * 2017-07-20 2019-02-28 GÓMEZ-LÓPEZ, Wenceslao Formulation comprenant une matière nanostructurée, biocompatible et biocatalytique pour le traitement de plaies et d'infections
WO2019016725A3 (fr) * 2017-07-20 2019-02-28 GÓMEZ-LÓPEZ, Wenceslao Formulation de nettoyage personnel, de matériau et de surface comprenant des particules nanostructurées
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