Method for producing plasmonic silver or gold nanoparticles stabilized by functional hyperbranched polyorganoalkoxysiloxane matrices for formation of covalently bonded metal-polymer nanocomposite coatings, and nanocomposite coatings based thereon

Abstract

FIELD: production of metal-containing nanocomposite coatings.SUBSTANCE: method for producing plasmonic silver or gold nanoparticles stabilized by functional hyperbranched polyorganoalkoxysiloxane matrices for forming covalently bonded metal-polymer nanocomposite coatings, wherein photochemical reduction of the corresponding metal ions is carried out under the action of UV radiation or X-ray radiation in an alcohol solution, while poly(3-(4-((dimethylamino)methyl)-1H-1,2,3-triazol-1-yl)propyl)ethoxysiloxane of formula (I) or poly[3-(2-aminoethylamino)propyl]methoxysiloxane of formula (II) is used as the hyperbranched organosilicon polymer matrix, wherein the molar ratio of the functional groups in the initial hyperbranched polymer matrices and the silver or gold metal ions is from 6:1 to 80:1; a method for producing a covalently bonded metal-polymer nanocomposite coating based on a solution of silver or gold nanoparticles and a covalently bonded metal-polymer nanocomposite coating based on silver or gold nanoparticles.EFFECT: formation on the surface of the material of covalently bonded nanocomposite metal-polymer coatings containing finely dispersed silver and gold nanoparticles with sizes of 1-20 nm and possessing the effect of surface plasmon resonance.10 cl, 18 dwg, 10 ex

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[0001] The invention relates to the field of polymer metal-organic and organosilicon chemistry and the technology for producing metal-polymer nanocomposite plasmonic coatings containing stabilized metallic nanoparticles of silver or gold of controlled size (1-20 nm), obtained by photochemical reduction of the corresponding transition metal salts in a series of alcohols (methanol, ethanol, isopropanol, butanol or tert-butanol) using functional organosilicon polymers of hyperbranched molecular structure, acting simultaneously as stabilizing matrices, ensuring uniform distribution of finely dispersed metallic nanoparticles, and chemical modifiers of the material surface.

[0002] The invention can be used to produce optically active materials and coatings, antibacterial and catalytically active materials and coatings. LEVEL OF TECHNOLOGY

[0003] Due to a number of unique physicochemical properties, metal nanoparticles are widely used in the creation of nanocomposite materials in modern high-tech fields of optics, electronics, catalysis, optics, medicine, etc. [Petridis C. et al. Laser generated nanoparticles based photovoltaics / / Journal of Colloid and Interface Science. - 2017. - Vol. 489. - Pp. 28-37; Atwater HA, Polman A. Plasmonics for improved photovoltaic devices / / Nature materials. - 2010. - Vol. 9. - No. 3. - Pp. 205-213].

[0004] Currently, various methods for producing metal nanoparticles are known, which can be conditionally divided into chemical and physical methods. Physical methods for producing nanoparticles include metal-steam evaporation, laser ablation, crushing, mechanical dispersion, etc. Chemical methods for producing include condensation of metal vapors, obtaining sols by liquid-phase reduction, matrix synthesis, as well as photochemical reduction, pyrolysis, etc.). [Pomogaylo A.F. Polymer-immobilized nanosized and cluster particles. - Uspekhi Chemii, 1997, Vol. 66, No. 8, - P. 750; Revina A.A., Egorova E.M. Radiation-chemical nanostructural technology for the synthesis of stable metal and bimetallic clusters. Abstracts of the International Conference "Advanced Technologies on the Threshold of the 21st Century", ICAT 98, Moscow, 1998, Part II, p. 411; Pileni M. et al. Nanostructured Particles in Colloidal Systems. Langmuir, 1997, Vol. 13, p. 3266; Sergeev G.B.Nanochemistry: textbook / G.B. Sergeev. - 3rd ed. - M.: KDU, 2009. - 336 p.: ill.; Rambidi N.G. Physical and chemical foundations of nanotechnology / N.G. Rambidi, A.V. Berezkin. - M.: FIZMATLIT, 2008. - 456 p.; Suzdalev I.P. Nanotechnology: physical chemistry of nanoclusters, nanostructures and nanomaterials / I.P. Suzdalev. - M.: Com. Book, 2006. - 597 pp.].

[0005] Among chemical methods, the so-called citrate method or Turkevich method is a classic method for obtaining gold nanoparticles [Turkevich, J. A study of the nucleation and growth processes in the synthesis of colloidal gold / J. Turkevich, P.C. Stevenson, J. Hillier / / Discussions of the Faraday Society. - 1951. - Vol. 11. - P. 55-75]. The essence of the method lies in heating an aqueous solution of chloroauric acid, where sodium citrate is used as a reducing agent and simultaneously a stabilizer. This method allows for the production of spherical gold nanoparticles with sizes greater than 10 nm.

[0006] The Turkevich method is also used to synthesize silver nanoparticles, using an aqueous solution of silver nitrate as the nanoparticle precursor. This method produces spherical silver nanoparticles; however, a drawback is the undesirable aggregation of the nanoparticles.

[0007] The borohydride method for synthesizing silver nanoparticles has become widely used today. AgNO3 is most often used as the precursor salt in this method, and The reducing agent is an excess of NaBH4 solution. The nanoparticles are reduced in a cooled salt solution with vigorous stirring. The advantage of this method is the production of silver nanoparticles that can be stabilized in the size range of 1–10 nm. [Yusuf, M. (2019). Silver Nanoparticles: Synthesis and Applications. In: Martínez, L., Kharissova, O., Kharisov, B. (eds) Handbook of Ecomaterials. Springer, Cham]

[0008] A method for producing silver nanoparticles in the presence of aqueous solutions of silver nitrate and L-cysteine ​​is known. The resulting solutions are mixed and maintained at a temperature of 15-55°C for 0.34-48 hours in the absence of light. Silver ions are reduced with an aqueous solution of sodium borohydride. Silver nanoparticles with an average size of 20 nm are obtained. [RU2526390C1, published on August 20, 2014].

[0009] The disadvantage of this method is the complexity of implementation and the duration of the synthesis.

[0010] A known method for producing silver nanoparticles involves synthesizing Ag nanoparticles by reducing them to the zero-valent state from a solution of its salts in ion-exchange resins. Synthesis is carried out in a cation-exchange matrix of KU-2-8 hydrogel, using AgNO3 as the silver salt and a solution of hydrazine in sodium hydroxide or a solution of tin chloride in hydrochloric acid as the reducing agent [RU 2385293 C2, publication date 27.03.2010].

[0011] The disadvantage of this method is the complexity of the technological process.

[0012] An electrochemical method for producing nanosized, highly uniform (10-20 nm) silver particles in an aqueous medium is known. The invention describes a method for producing silver nanoparticles in an aqueous medium that can be stabilized in the size range of 1 to 20 nm [RU2654860C1, publication date 23.05.2018].

[0013] The disadvantage of this method is that the environment used contains, in addition to water, reaction products, hydrogen peroxide and ammonia residues; there is no purification stage.

[0014] A method for producing a composition containing colloidal silver or gold is known, which consists of incubating probiotic bacteria selected from the species Lactobacillus fermentum with an aqueous solution containing silver nitrate or gold chloride [RU2460797C2, publication date 09 / 10 / 2012].

[0015] The disadvantage of the method is the inability to control the size of nanoparticles.

[0016] A method for producing colloidal silver nanoparticles from an aqueous solution of silver nitrate using gamma radiation and a stabilizer in the form of carboxymethyl chitin is known [RU 2474471 C2, published 10.02.2013]. This method is distinguished by the absence of additional reducing agents. The process is complicated by the need to use an inert gas and gamma radiation, which is hazardous to humans, requiring expensive equipment.

[0017] A method for producing silver nanocomposites based on synthetic water-soluble polymers is known [RU2485051C1, published June 20, 2013]. The method is distinguished by the use of copolymers of 2-dihydroxy-2-methacrylamido-D-glucose with 2-dimethylaminoethyl methacrylate or 2-diethylaminoethyl methacrylate as a stabilizer-reducing agent, as well as the reduction of silver ions under natural light. The disadvantages of this method include a lengthy reduction process, ranging from three hours to several days.

[0018] Photochemical and radiation-chemical methods for reducing metal ions to nanosized particles using ultraviolet and X-ray radiation are known. Photochemical reduction of metal salts has been studied for decades as a sustainable method for producing metal nanoparticles without the use of toxic reducing agents [Jara N. et al. Photochemical synthesis of gold and silver nanoparticles—A review / / Molecules. - 2021. - Vol. 26. - No. 15. - P. 4585; K Guo K., Baidak A., Yu Z. Recent advances in green synthesis and modification of inorganic nanomaterials by ionizing and non-ionizing radiation / / Journal of Materials Chemistry A. - 2020. - Vol. 8. - No. 44. - P. 23029-23058; Belloni J. et al. Radiation-induced synthesis of mono-and multi-metallic clusters and nanocolloids / / New Journal of Chemistry. – 1998. – T. 22. – No. 11. – pp. 1239-1255; Cubová K., Cuba V.Synthesis of inorganic nanoparticles by ionizing radiation – a review / / Radiation Physics and Chemistry. – 2020. – Vol. 169. – P. 108774; Sakamoto M., Fujistuka M., Majima T. Light as a construction tool of metal nanoparticles: Synthesis and mechanism / / Journal of Photochemistry and Photobiology C: Photochemistry Reviews. – 2009. – Vol. 10. – No. 1. – P. 33-56]. The method may be of interest due to the control over the parameters of the resulting nanoparticles – for example, exposure time and radiation intensity.

[0019] Compared with other methods for producing nanoparticles, the photochemical method is environmentally friendly and cost-effective because it avoids the use of toxic or harmful compounds, does not require expensive equipment, and can be carried out at room temperature and atmospheric pressure [Elsupikhe RF et al. Photochemical reduction as a green method for the synthesis and size control of silver nanoparticles in κ-carrageenan / / IEEE Transactions on Nanotechnology. - 2016. - Vol. 15. - No. 2. - P. 209-213; Dong SA, Zhou SP Photochemical synthesis of colloidal gold nanoparticles / / Materials Science and Engineering: B. - 2007. - Vol. 140. - No. 3. - P. 153-159; Mukha I. et al. Light-driven formation of gold / tryptophan nanoparticles / / Applied Nanoscience. – 2020. – T. 10. – P. 2827-2833; LeNH et al.Photo-induced generation of size controlled Au nanoparticles on pure siliceous ordered mesoporous silica for catalytic applications / / Microporous and Mesoporous Materials. – 2020. – Т. 295. – С. 109952; Gabriel J. S. et al. Photochemical synthesis of silver nanoparticles on chitosans / montmorillonite nanocomposite films and antibacterial activity / / Carbohydrate polymers. – 2017. – Т. 171. – С. 202-210.].

[0020] Methods based on the reduction of metal ions in the presence of stabilizers, which often use functional polymer matrices, are also widely used to obtain metal nanoparticles. Among others, the use of polymers with a hyperbranched molecular architecture is particularly effective [Bruchmann B., Voit B. Applications of hyperbranched polymers in coatings, as additives, and in nanotechnology / / Hyperbranched Polymers: Synthesis, Properties, and Applications. - 2011. - Pp. 415-440..Saliba S. et al. Hyperbranched polymers for the formation and stabilization of ZnO nanoparticles / / Chemistry of Materials. - 2010. - Vol. 22. - No. 23. - Pp. 6301-6309; Zhang Y. et al. Hyperbranched poly (amidoamine) as the stabilizer and reductant to prepare colloid silver nanoparticles in situ and their antibacterial activity / / The Journal of Physical Chemistry C. - 2008. - T. 112. - No. 7. – pp. 2330-2336; Liu X. et al.Green and facile synthesis of highly stable gold nanoparticles via hyperbranched polymer in-situ reduction and their application in Ag+ detection and separation / / Polymers. – 2018. – T. 10. – No. 1. – P. 42; Dong H. et al. The influence of amine structures on the stability and catalytic activity of gold nanoparticles stabilized by amine-modified hyperbranched polymers / / Nanotechnology. – 2018. – T. 29. – No. 5. – S. 055705; Kurniasih IN, Keilitz J., Haag R. Dendritic nanocarriers based on hyperbranched polymers / / Chemical Society Reviews. – 2015. – T. 44. – No. 12. – P. 4145-4164].

[0021] Various methods can be used to modify material surfaces with metal nanoparticles, each with its own advantages depending on the substrate and intended application.

[0022] The main methods for modifying the surface of a material with metal nanoparticles include methods such as vapor deposition or metal vapor synthesis (MVS), based on the condensation of metal vapors, often in the presence of organic ligands or matrices. The advantages of this method include the absence of by-products and toxic reducing agents, as well as the possibility of modifying a wide range of different materials. However, uncontrolled aggregation of nanoparticles, leading to their uneven distribution over the surface of the material, is a disadvantage of this method [Schmidt, E., Klabunde, KJ, Ponce, A., Smetana, A. and Heroux, D. (2006). Metal Vapor Synthesis of Transition Metal Compounds. In Encyclopedia of Inorganic Chemistry (eds RB King, RH Crabtree, CM Lukehart, DA Atwood and RA Scott). [https: / / doi.org / 10.1002 / 0470862106.ia137]

[0023] Electrochemical deposition involves applying an electric current to reduce metal ions on a substrate. This method allows for precise control of the size and distribution of nanoparticles, but can only be effectively used on conductive substrates such as carbon nanotubes or metals [EP 3382063A2, publication date 03.10.2018]. HERE

[0012] ?

[0024] A chemical approach involving the use of metal ion reducing agents to deposit metal nanoparticles from solution onto material surfaces is a widely used method for producing nanocomposite coatings. In this case, to improve adhesion and stabilize metal nanoparticles, the material surface is often pre-chemically modified with functional coordinating molecules containing amine, carboxyl, or thiol groups [Choma, J., Jamioła, D., Ludwinowicz, J., & Jaroniec, M. (2012). Deposition of silver nanoparticles on silica spheres and rods. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 411, 74–79; Liang, M., Zhang, G., Feng, Y., Li, R., Hou, P., Zhang, J., & Wang, J. (2018). Facile synthesis of silver nanoparticles on amino-modified cellulose paper and their catalytic properties. Journal of Materials Science, 53(2), 1568-1579.

[0025] The multi-stage process and the use of toxic chemical reducing agents are serious disadvantages of this method.

[0026] One of the standard chemical methods for modifying the surface of a material with metal nanoparticles consists of sequential modification of the surface of the material with functional binders such as AGM-9 and subsequent reduction of metal salts on its surface, which occurs in a heterogeneous system [Aslan, K., Holley, P., & Geddes, CD (2006). Metal-enhanced fluorescence from silver nanoparticle-deposited polycarbonate substrates. Journal of Materials Chemistry, 16(27), 2846–2852; Salem, MA, Elsharkawy, RG, Ayad, MI et al. Silver nanoparticles deposition on silica, magnetite, and alumina surfaces for effective removal of Allura red from aqueous solutions. J Sol-Gel Sci Technol 91, 523–538 (2019)]. DISCLOSURE OF THE INVENTION

[0027] The technical problem solved by the claimed invention is the creation of a new method for producing plasmonic nanoparticles of silver or gold and a method for producing metal-polymer nanocomposite coatings chemically bonded to the surface of the material and containing stabilized narrow-dispersed metallic plasmonic nanoparticles of silver or gold.

[0028] The technical result achieved by implementing the claimed invention consists in obtaining plasmonic silver or gold nanoparticles of controlled sizes (1-20 nm) and nanocomposite coatings based on them, covalently bonded to the surface of the material and containing narrowly dispersed uniformly distributed metallic silver or gold nanoparticles of controlled sizes (1-20 nm).

[0029] The technical result is achieved due to the fact that the method for producing plasmonic nanoparticles of silver or gold in the presence of organosilicon polymer matrices of a hyperbranched structure is characterized by the fact that photochemical reduction of the ions of the corresponding metals in an alcohol solution is carried out under the influence of UV or X-ray radiation, while poly(3-(4-((dimethylamino)methyl)-1H-1,2,3-triazol-1-yl)propyl)ethoxysiloxane of formula (I) is used as organosilicon polymer matrices of a hyperbranched structure. or poly[3-(2-aminoethylamino)propyl]methoxysiloxane of formula (II) In this case, the molar ratio of functional groups in hyperbranched polymers and silver or gold metal ions ranges from 6:1 to 80:1.

[0030] Unlike known approaches, the claimed method, which involves modifying the surface of a material with pre-formed and pre-stabilized metal nanoparticles in a functional hyperbranched organosilicon polymer matrix, enables the production of nanocomposites with finely dispersed metal nanoparticles. This is due to the nanoparticle formation stage occurring in a homogeneous medium in the presence of an effective stabilizer. The sizes of the resulting silver or gold nanoparticles are controlled by the conditions and parameters of UV and ionizing radiation and the molar ratio of the functional groups of the hyperbranched polymers to the metal ions. Furthermore, the presence of functional alkoxy groups in the polymer matrices used enables chemical adaptation of these heteroorganic polymers and polymer composites based on them to the surfaces of various materials.

[0031] In addition, in a particular case of implementing the invention, alcohols selected from the group: methanol, ethanol, isopropanol, butanol or tert-butanol are used as a solvent.

[0032] In addition, in a particular case of the invention, metal nanoparticles are obtained by photochemical reduction of silver or gold ions from salts selected from the group: AgBF4, AgNO3, AgClO4, AgSO4, [Ag(NH3)2]OH, KAuCl4, HAuCl4⋅3H2O.

[0033] In addition, in a particular case of the invention, the silver or gold nanoparticles have sizes of 1–20 nm.

[0034] The technical result is also achieved through a method for producing a covalently bonded metal-polymer nanocomposite coating based on a solution of silver or gold nanoparticles stabilized by organosilicon functional polymer matrices, obtained according to any of paragraphs 1-4, characterized in that the surface of the material being modified is treated with a solution of silver or gold nanoparticles stabilized by organosilicon functional polymer matrices, by dispersing the modified material in this solution using ultrasound, followed by filtration and drying the material under reduced pressure, or by applying silver or gold nanoparticles stabilized by organosilicon functional polymer matrices to the surface of the material being modified and its subsequent drying.

[0035] In addition, in a particular case of the invention’s implementation, silica gel or silica obtained by the Stober method, or glass, or cotton fabric are used as modified materials.

[0036] Modification of the surface of various materials with metallic nanoparticles of silver or gold makes it possible to obtain chemically covalently bonded to the surface of the material nanocomposite polymer coatings of formula (III) with uniformly distributed narrowly dispersed metallic nanoparticles of controlled sizes (1-20 nm) (Fig. 9-12) [III]BRIEF DESCRIPTION OF DRAWINGS

[0037] The essence of the invention is explained by graphic materials, where: Fig. 1 shows the UV spectrum of poly(DMA-1,2,3-triazole-propyl)ethoxysiloxane / Ag-NPs obtained according to Example 1; Fig. 2 shows the UV spectrum of poly(EDA-propyl)methoxysiloxane / Ag-NPs obtained according to Example 2; Fig. 3 shows the UV spectrum of poly(EDA-propyl)methoxysiloxane / Au-NPs obtained according to Example 3; Fig. 4 shows the TEM photo and the size distribution of poly(DMA-1,2,3-triazole-propyl)ethoxysiloxane / Ag-NPs obtained according to Example 1; Fig. 5 shows the TEM photo and the size distribution of poly(EDA-propyl)methoxysiloxane / Ag-NPs obtained according to Example 2; Fig. 6 shows the TEM photo and size distribution of poly(EDA-propyl)methoxysiloxane / Ag-NPs obtained according to Example 3; Fig. 7 shows the TEM photo and size distribution of poly(EDA-propyl)methoxysiloxane / Ag-NPs obtained according to Example 4; Fig. 8 shows the TEM photo and size distribution of poly(EDA-propyl)methoxysiloxane / Au-NPs obtained according to Example 5; Fig.9 shows the TEM photo and size distribution of poly(EDA-propyl)methoxysiloxane / AuNPs obtained according to Example 6; Fig. 10 shows. 1 The H NMR spectrum of poly(DMA-1,2,3-triazolepropyl)ethoxysiloxane / AgNPs in D2O, obtained according to Example 1, is shown; Fig. 11 shows 1H NMR spectrum of poly(EDA-propyl)methoxysiloxane / Ag-NPs in DMSO-d6 obtained according to Example 2; Fig. 12 shows the TEM photo and size distribution of poly(DMA-1,2,3-triazolepropyl)ethoxysiloxane / AgNPs / silica gel obtained according to Example 8; Fig. 13 shows the TEM photo and size distribution of poly(EDA-propyl)methoxysiloxane / AuNPs / silica gel in the ratio 8 / 1 obtained according to Example 8; Fig. 14 shows the TEM photo and size distribution of poly(EDA-propyl)methoxysiloxane / AuNPs / silica gel in the ratio 80 / 1 obtained according to Example 8; Fig. 15 shows the TEM photo and size distribution poly(DMA-1,2,3-triazolepropyl)ethoxysiloxane / AgNPs / Stober silica obtained according to Example 9; Fig. 16 shows the UV spectrum of poly(DMA-1,2,3-triazolepropyl)ethoxysiloxane / AgNPs / glass obtained according to Example 10; Fig. 17 shows the UV spectrum of poly(EDA-propyl)methoxysiloxane / AuNPs / glass obtained according to Example 10; Fig.18 shows SEM / EDX of poly(DMA-1,2,3-triazolepropyl)ethoxysiloxane / AgNPs / cotton fabric obtained according to Example 11; IMPLEMENTATION OF THE INVENTION.

[0038] The implementation of the invention is explained by a detailed description and specific examples of implementation.

[0039] In general, the synthesis of metallic silver or gold nanoparticles in an alcohol solution as a result of photochemical reduction of the corresponding transition metal salts according to formula (IV), stabilized in functional poly(3-(4-((dimethylamino)methyl)-1H-1,2,3-triazol-1-yl)propyl)ethoxysiloxane of formula (I) or poly[3-(2-aminoethylamino)propyl]methoxysiloxane of formula (II).

[0040] Photochemical reduction of silver or gold ions occurs according to the general reaction scheme (IV) in the presence of hyperbranched polyorganoalkoxysiloxanes of formula (I) and (II). The general reaction scheme is as follows (IV): (IV) where ethylenediamine or N,N-dimethylamine-1,2,3-triazole- are used as R; silver (Ag) or gold (Au) ions are used as M, x;y;z=5-20.

[0041] In general, the method for producing nanocomposites based on plasmonic silver and gold nanoparticles using cotton fabric, silica, glass, and aluminosilicates as modified materials follows the scheme (V). The general reaction scheme is as follows (V): (V)where ethylenediamine or N,N-dimethylamine-1,2,3-triazole are used as R; silver (Ag) or gold (Au) nanoparticles are used as Me,

[0042] Alcohols (methanol, ethanol, isopropanol, butanol or tert-butanol) are used as solvent.

[0043] Metal nanoparticles are obtained by photochemical reduction of silver and gold ions from AgBF salts 4,AgNO3, AgClO₄, AgSO₄, [Ag(NH3)2]OH, KAuCl4, HAuCl4·3H2O under the influence of X-ray or UV radiation. A UV lamp or X-ray unit is used as a light source.

[0044] The implementation of the invention is confirmed by the examples given below, which do not exhaust all the possibilities for obtaining and using the systems described in this invention.

[0045] Example 1. Obtaining a solution containing nanosized silver particles, a polymer stabilizer of poly(DMA-1,2,3-triazole-propyl)ethoxysiloxane in an ethyl alcohol medium.

[0046] Prepare a solution of 50 mg of poly-dimethylamino-1,2,3-triazolesiloxane (1 wt%) in 5 ml of ethanol (M w (link = 221 g / mol) add 4.4 mg of silver tetrafluoroborate (AgBF4) in the molar ratio "polymer - AgBF4" 10:1, purged with argon for 10 minutes. Then the resulting solution is exposed to ultraviolet (254-365 nm (15-80 W) / X-ray (22-33 keV) irradiation for 10-30 minutes.

[0047] The presence of silver nanoparticles, as well as their stability, are monitored spectrophotometrically by measuring changes in the optical density at the maximum of the plasmonic absorption band characteristic of the resulting silver nanoparticles in the 410-420 nm region (Figure 1). The size and shape of the resulting silver nanoparticles are examined using transmission electron microscopy (TEM) (Figure 4). The silver nanoparticle solution contains uniformly shaped nanoparticles measuring 1-5 nm.

[0048] Example 2. Obtaining a solution containing nanosized silver particles, a polymer stabilizer of poly(EDA-propyl)methoxysiloxane in an ethyl alcohol solution.

[0049] Prepare a solution of 50 mg of poly(EDA-propyl)methoxysiloxane (1 wt%) in 5 ml of ethanol (M wзвена = 176 g / mol) 5.5 mg of silver tetrafluoroborate (AgBF4) are added in the molar ratio "polymer - AgBF4" 10:1, purged with argon for 10 minutes. Then the resulting solution is exposed to ultraviolet (254-365 nm (15-80 W) / X-ray (22-33 keV) irradiation for 10-30 minutes.

[0050] The presence of silver nanoparticles, as well as their stability, are monitored spectrophotometrically by measuring changes in the optical density at the maximum of the plasmonic absorption band characteristic of the resulting silver nanoparticles in the 410-420 nm region (Fig. 2). The size and shape of the resulting silver nanoparticles are examined using transmission electron microscopy (TEM) (Fig. 5). The silver nanoparticle solution contains uniformly shaped particles with an average particle diameter of 3.4 nm.

[0051] Example 3. Obtaining a solution containing nanosized silver particles, a polymer stabilizer of poly(DMA-1,2,3-triazole-propyl)ethoxysiloxane in an ethyl alcohol medium.

[0052] Prepare a solution of 150 mg of poly-dimethylamino-1,2,3-triazolesiloxane (1 wt%) in 5 ml of ethanol (M wзвена= 221 g / mol) add 1.3 mg of silver tetrafluoroborate (AgBF4) in the molar ratio "polymer - AgBF4" 80:1, purged with argon for 10 minutes. Then the resulting solution is exposed to ultraviolet (254-365 nm (15-80 W) / X-ray (22-33 keV) irradiation for 10-30 minutes.

[0053] The size and shape of the resulting silver nanoparticles are examined using transmission electron microscopy (TEM) (Fig. 6). The silver nanoparticle solution contains uniformly shaped nanoparticles measuring 1–3 nm.

[0054] Example 4. Obtaining a solution containing nanosized silver particles, a polymer stabilizer of poly(EDA-propyl)methoxysiloxane in an ethyl alcohol solution.

[0055] Prepare a solution of 50 mg of poly(EDA-propyl)methoxysiloxane (1 wt%) in 5 ml of ethanol (M wзвена = 176 g / mol) 5.5 mg of silver tetrafluoroborate (AgBF4) are added in the molar ratio "polymer - AgBF4" 6:1, purged with argon for 10 minutes. Then the resulting solution is exposed to ultraviolet (254-365 nm (15-80 W) / X-ray (22-33 keV) irradiation for 10-30 minutes.

[0056] The size and shape of the resulting silver nanoparticles are examined using transmission electron microscopy (TEM) (Fig. 7). The silver nanoparticle solution contains particles ranging in size from 2 to 20 nm.

[0057] Example 5. Obtaining a solution containing nanosized gold particles, a polymer stabilizer of poly(EDA-propyl)methoxysiloxane in an ethyl alcohol medium.

[0058] Prepare a solution of 50 mg of poly(EDA-propyl)methoxysiloxane (1 wt%) in 5 ml of ethanol (M wзвена =176 g / mol) add 14.0 mg of chloroauric acid (HAuCl4⋅3H2O) in the molar ratio "polymer - Au 3+ "8:1, flush with argon for 10 minutes. Then, the resulting solution is exposed to X-rays (22-33 keV) for 20 minutes.

[0059] The presence of gold nanoparticles, as well as their stability, are monitored spectrophotometrically by measuring changes in the optical density at the maximum of the plasmonic absorption band characteristic of the resulting gold nanoparticles in the 534 nm region (Fig. 3). The size and shape of the resulting gold nanoparticles are examined using transmission electron microscopy (TEM) (Fig. 8). The gold nanoparticle solution contains uniformly shaped particles with an average particle diameter of 2.9 nm.

[0060] Example 6. Obtaining a solution containing nanosized gold particles, a polymer stabilizer of poly(EDA-propyl)methoxysiloxane in an ethyl alcohol medium.

[0061] Prepare a solution of 50 mg of poly(EDA-propyl)methoxysiloxane (1 wt%) in 5 ml of ethanol (M wзвена =176 g / mol) add 1.4 mg of chloroauric acid (HAuCl4•3H2O) in the molar ratio "polymer - Au 3+"80:1, flushed with argon for 10 minutes. Then the resulting solution is exposed to X-rays (22-33 keV) for 20 minutes.

[0062] The presence of gold nanoparticles, as well as their stability, are monitored spectrophotometrically by measuring changes in the optical density at the maximum of the plasmonic absorption band characteristic of the resulting gold nanoparticles in the 534 nm region (Fig. 3). The size and shape of the resulting gold nanoparticles are examined using transmission electron microscopy (TEM) (Fig. 9). The gold nanoparticle solution contains uniformly shaped particles with an average particle diameter of 1.5 nm.

[0063] Example 7. Obtaining a nanocomposite coating on the surface of silica gel containing nanosized silver particles (Ag 0 ) or gold (Au 0 ) and hyperbranched poly(DMA-1,2,3-triazole-propyl)ethoxysiloxane / poly(EDA-propyl)methoxysiloxane

[0064] 100 mg of silica gel was added to the prepared polymer solution with silver or gold metal nanoparticles according to Examples 1, 5, and 6, and the mixture was evaporated under reduced pressure. 3 ml of tetrahydrofuran (THF) was added to the remaining mixture, which was sonicated for 2 hours and then left overnight with stirring. The mixture was then filtered under reduced pressure, washed with THF, and the resulting composite was dried in vacuum (1 mbar) for 1 hour at 50°C. The resulting materials with the nanocomposite coating were studied using TEM and UV-visible spectroscopy.

[0065] The size and shape of silver or gold nanoparticles are examined using transmission electron microscopy (TEM). The silver or gold nanoparticle solution contains uniformly shaped particles with an average particle diameter of 2.5, 4.6, and 1.7 nm (4.6, 2.5, and 1.7 nm) (Figs. 12–14).

[0066] Example 8. Obtaining a nanocomposite coating on the surface of silica synthesized by the Stöber method [Stöber W., Fink A., Bohn E. Controlled growth of monodisperse silica spheres in the micron size range / / Journal of colloid and interface science. - 1968. - Vol. 26. - No. 1. - Pp. 62-69], containing nanosized silver particles (Ag 0 ) or gold (Au 0 ) and hyperbranched poly(DMA-1,2,3-triazole-propyl)ethoxysiloxane / poly(EDA-propyl)methoxysiloxane

[0067] 100 mg of silica obtained by the Stober method was added to the polymer solution prepared with silver or gold metal nanoparticles as described in Example 1. The mixture was then evaporated under reduced pressure, and the remaining mass was dried under vacuum (1 mbar) for 1 hour at 50°C.

[0068] The size and shape of silver or gold nanoparticles are studied using TEM, DLS (dynamic light scattering), and UV-visible spectroscopy. The nanoparticle solution contains particles of uniform shape (Fig. 15).

[0069] Example 9. Obtaining a nanocomposite coating on a glass surface containing nanosized silver particles Ag 0 or gold Au 0 and hyperbranched poly(DMA-1,2,3-triazole-propyl)ethoxysiloxane

[0070] A polymer solution with metallic silver or gold nanoparticles according to Examples No. 1, 5 is applied to the glass surface and dried at room temperature.

[0071] The presence of silver nanoparticles Ag 0 or gold Au 0 are controlled by the spectrophotometric method based on the change in optical density at the maximum of the plasmonic absorption band characteristic of the resulting nanoparticles (Fig. 16, 17).

[0072] Example 10. Obtaining a nanocomposite coating on the surface of cotton fabric containing nanosized silver particles Ag 0 or gold Au 0 , hyperbranched poly(DMA-1,2,3-triazole-propyl)ethoxysiloxane / poly(EDA-propyl)methoxysiloxane

[0073] 50 mg of bandage was added to the prepared polymer solution with silver or gold metal nanoparticles as described in Example 2. The mixture was then evaporated under reduced pressure, and the resulting bandage was dried under vacuum (1 mbar) for 1 hour at 50°C.

[0074] The size of silver or gold nanoparticles and their shape were examined by SEM, energy dispersive X-ray spectroscopy (EDX) and their antibacterial and antifungal activities were visually assessed. (Fig. 18).

Claims

1. A method for producing plasmonic silver or gold nanoparticles stabilized by functional hyperbranched polyorganoalkoxysiloxane matrices for the formation of covalently bonded metal-polymer nanocomposite coatings, characterized in that photochemical reduction of the corresponding metal ions is carried out under the influence of UV radiation or X-ray radiation in an alcohol solution, while poly(3-(4-((dimethylamino)methyl)-1H-1,2,3-triazol-1-yl)propyl)ethoxysiloxane of formula (I) is used as the hyperbranched organosilicon polymer matrix. or poly[3-(2-aminoethylamino)propyl]methoxysiloxane of formula (II), In this case, the molar ratio of functional groups in the initial hyperbranched polymer matrices and silver or gold metal ions ranges from 6:1 to 80:

1.

2. The method according to paragraph 1, characterized in that alcohols are used as the solvent: methanol or ethanol, or isopropanol, or butanol, or tert-butanol.

3. The method according to claim 1, characterized in that the photochemical reduction of silver or gold ions is carried out from the salts AgBF4, or AgNO3, or AgClO4, or AgSO4, or [Ag(NH3)2]OH, or KAuCl4, or HAuCl4⋅3H2O.

4. The method according to claim 1, characterized in that the silver or gold nanoparticles have dimensions of 1–20 nm.

5. A method for producing a covalently bonded metal-polymer nanocomposite coating based on a solution of silver or gold nanoparticles stabilized by organosilicon functional polymer matrices obtained according to any of paragraphs 1-4, characterized in that the surface of the material to be modified is treated with a solution of silver or gold nanoparticles stabilized by organosilicon functional polymer matrices by dispersing the modified material in this solution using ultrasound, followed by filtration and drying the material under reduced pressure, or by applying silver or gold nanoparticles stabilized by organosilicon functional polymer matrices to the surface of the material to be modified and subsequently drying it.

6. The method according to paragraph 5, characterized in that silica gel is used as the material being modified.

7. The method according to paragraph 5, characterized in that silica obtained by the Stober method is used as the modified material.

8. The method according to paragraph 5, characterized in that cotton fabric is used as the modified material.

9. The method according to paragraph 5, characterized in that glass is used as the material being modified.

10. A covalently bonded metal-polymer nanocomposite coating based on silver or gold nanoparticles of 1-20 nm in size, stabilized by organosilicon functional polymer matrices, obtained according to any of paragraphs 5-9.

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