Patent Application
20230312342
The subject matter of the invention is a method of preparation of zinc-oxygen-based nanoparticles, zinc peroxide nanoparticles (ZnO2 NPs) without the addition of any stabilizing agent or zinc peroxide nanoparticles coated with an organic shell composed of anionic or neutral ligands, or mixtures thereof obtained by the said method as well as their use.
Zinc peroxide (ZnO2) is a white or slightly yellowish, odorless semiconductor material (Eg = 3,3 - 4,6 eV[1,2]) with properties described as transition between ionic and covalent-type compounds.[3] This inorganic compound from the group of peroxides exhibits powerful oxidizing properties and the ability to generate free radicals and/or other reactive oxygen species. Zinc peroxide crystallizes in the cubic Pa3 space group. The crystal structure of ZnO2 is characterized by irregular octahedrons with a central Zn2+ ion surrounded by O ions located at the vertices of these polyhedrons. The distance between the two oxygen atoms is 1.47 Å, which is 0.64 Å shorter than the Zn—O bond length (2.11 Å).[4] This structure implies the occurrence of local charge balance disturbances in the ZnO2 crystal lattice and causes structural instability of this material to, for example, high temperature (which explains the relatively low temperature of decomposition of ZnO2 into ZnO[1,5,6]), and sensitivity to the pH changes in the solution.[7]
The above-described electronic and structural characteristics of ZnO2 make it a promising material for various industrial applications and, constantly supplemented with further discoveries, constitute the basis for new implementations and technologies. This material is used in the rubber and plastics processing industry,[8] in cosmetics, pharmaceutical and medical industries (among others as antiseptic[9,10] and antibacterial[7,11,12] agent as well as wound healing aid[13] or a new type of nanotherapeutic[14,15]), and as a component of pyrotechnic compositions,[16] and even as an agent for removing pollutants from the water[17-19] as well as for neutralizing combat gases.[20] In addition, ZnO2 nanostructures are also used as efficient photocatalysts,[21-23] materials for the construction of sensors[24] or electronic devices,[25] reagents in the oxidation of organic compounds[26-29] as well as single-source inorganic precursors of nanoparticulate forms of ZnO.[5,30,31]
A zinc peroxide compound was first obtained by L. Tenar in 1818.[32] There are several methods of synthesis of zinc peroxide nanostructures that are currently commonly known and used, among which we can distinguish two main groups: physical methods allowing for the production of thin layers or thin films (e.g., electrolytic deposition[6] and pulsed laser ablation (PLA)[33]) and chemical methods, which due to the nature of the applied precursor can be divided into procedures using inorganic or organometallic precursors.[1,34] The main assumption of the commonly used wet-inorganic methods is the preparation of macroscopic and/or nanocrystalline ZnO2 as a result of the direct reaction between selected precursor (i.e., Zn,[35,36] ZnO,[2,23,27,35-39] Zn(OH)2,[30,42] Zn(OOCCH3)2,[4,5,7,11,13-15,17,24,26,43-58] ZnSO4,[3,21,22,43] Zn(NO3)2,[43] ZnCl2,[20,32,43] Zn5(CO3)2(OH)6,[59,60] zinc carbamate of the formula Zn(OCONHC4H9)2[61]) and hydrogen peroxide (in the form of hydrogen peroxide aqueous solutions at concentration of 3% or 30%, or ammonia hydroxide solution). This process is usually carried out at elevated temperature (in the temperature range from ca. 60° C.[11,48] to 150° C.[2,23]) or in the presence of supporting agents such as the catalytic amount of acetic acid,[35] irradiation[11,24,44,48-50] or ultrasounds.[11] Among the chemical methods based on inorganic precursors, we can distinguish, for example, precipitation method,[13,20,23,32] colloidal synthesis,[52] hydrothermal route,[4,5,26,46,47] microemulsion method,[62] oxidation-hydrolysis-precipitation procedure,[45] sol-gel process,[11,44] reaction using high-pressure impinging-jet reactor[7,57] or “green synthesis” based on Leidenfrost phenomenon.[58] An interesting example of a chemical method for the preparation of ZnO2 thin films is the successive ionic layer adsorption and reaction technique (SILAR method[63]). In a few cases, the authors attempted to stabilize the surface of a nanocrystalline product with the use of low- (e.g., glucose-1-phosphate,[57] 2-(methacryloyloxy)ethyl phosphate[7]) or high-molecular-weight (e.g., polyethylene glycol - PEG,[45,61] sodium polyphosphate,[32] polyvinylpyrrolidone- PVP[15,61]) organic compounds acting as surfactants. The main goal of such treatments is the preparation of homogeneous nanostructures, improving their stability, and, in the case of bi- or multifunctional compounds, the possibility of post-synthetic surface modification. The type and the quantity of the additional stabilizing agent affect, among others, the yield of the reaction, the degree of precursor conversion, as well as composition, structure, morphology, and oxidizing properties of the final product.[7,57] For example, using an additional long-chain stabilizer - PEG200 - in the inorganic synthesis leads to the formation of aggregated ZnO2 nanoparticles with a core size of ca. 10 nm, which decompose into ZnO at 233° C.[45] Moreover, the size and the stability of the ZnO2 NPs dispersion are strongly related to the type and the concentration of the applied polymer; in the case of a polymer with a higher molecular weight, it is possible to obtain ZnO2 nanoparticles with a smaller core size and a narrow size distribution.[61]
The use of submicron ZnO powder as a precursor in the synthesis of ZnO2 leads to the formation of structures that differ in terms of morphology, i.e., from nanometric objects (5 -18 nm)[2,27] to bigger (100 - 200 nm) microspheres,[37] crystallites with a size of ca. 1 µm[41] or polycrystalline layers[38-40] of zinc peroxide. However, the purity of the resulting material depends on the temperature of the process. Too low (ca. 50° C.) or too high (> 150° C.) temperature leads to a mixture of ZnO and ZnO2 phases, which is not desirable in the context of obtaining homogeneous and high purity nanomaterials.[2] Most of the above-mentioned inorganic processes also suffer from a low degree of crystallinity and impurities in the final material, e.g., in the form of an unreacted precursor and/or other reactants[4,44] or the presence of a Zn(OH)2 by-product.[2,4] It has also been proven that the physicochemical properties of the final material depend on both the applied method and conditions of the reaction between selected precursor and hydrogen peroxide; reaction rate depends on factors such as temperature, time, pressure, amount and type of solvent, type of the applied precursor, presence and nature of the stabilizing agent, and concentration of the H2O2 solution. Among the inorganic methods, we can also distinguish the mechanochemical approach (i.e., solvent-free) based on grinding of zinc acetate in a ball mill with the addition of a H2O2 aqueous solution of 20% and repeating this operation several times until the product in the form of zinc peroxide is obtained.[54] All of the mentioned synthetic methods lead to the formation of nanostructured materials of irregular shape,[2,45,52] which tend to aggregate and/or agglomerate and thus afford heterogeneous materials with high polydispersity and moderate stability.[2,5,11,17,20,23,26,28,33,45,46,52-57]
An alternative to the above-described methods for the preparation of ZnO2 is an organometallic approach. The first reference in the literature to the utility of organozinc compounds relates to the fabrication of macroscopic-type ZnO2 hydrate from Et2Zn.[34] On the other hand, nanoparticles with paramagnetic properties and characterized by homogeneity and small size (ca. 3 nm) can be obtained from the in situ generated precursor from the mixture of octylamine, ZnCl2, and RMgCl.[1,64] However, the mentioned method did not allow for the preparation of nanoparticulate forms of ZnO2 with a well-defined structure and coated with a wide spectrum of organic ligands (i.e., anionic X-type ligands, neutral L-type ligands and their mixtures).
Due to the fact that the properties of ZnO2 strongly depend on the applied synthetic procedure, effective methods of preparation of nanocrystalline zinc peroxide with desired properties and physicochemical parameters are still being sought. Moreover, the developed technologies should be characterized by the synthetic procedure’s high repeatability, reproducibility, and simplicity.
Zinc oxide (ZnO) belongs to the group of II-VI fluorescent semiconductors and exhibits interesting physicochemical properties. The energy gap of this material at room temperature is 3.37 eV and the exciton bond energy is ca. 60 meV, which makes this material similar to the commonly used in optoelectronics gallium nitride (GaN).[65] There are a number of methods for the synthesis of nanocrystalline ZnO, among which we can distinguish physical processes and chemical methods. Due to the nature of the applied precursor, chemical methods can be divided into procedures using inorganic (i.e., simple zinc salts) and organometallic (i.e., dialkyl[67] and alkylzinc[68,69] compounds) precursors. Typical inorganic methods (e.g., sol-gel process and precipitation methods) lead to the formation of ZnO nanoparticles (NPs) characterized by significant heterogeneity and relatively wide size distribution, which may also be contaminated with alkali metal ions and/or ionic-type by-products. In addition, the properties of the resulting nanoparticles depend on the applied process conditions, such as temperature, type of solvent, concentration and pH.[66] The organometallic approach is based on reactions between organozinc compounds and oxygen or water, which are usually very fast and strongly exothermic. Both the appropriate process conditions (low concentrations and reduced temperature) and the usage of stabilizing ligands, which reduce the reactivity of the organometallic compound and finally stabilize the surface of the resulting ZnO nanostructures, could control these reactions.
A competitive method to the above-mentioned synthetic procedures, in which inorganic or organozinc precursor is only a source of Zn, while O atoms are delivered in the form of hydroxide, O2 and/or H2O (i.e., by slow diffusion of water and oxygen from the air, controlled introduction of water in the form of solutions in organic solvents or together with a stabilizing ligand) is the use of the so-called single-source precursors, which contain all the elements of the synthesized nanomaterial in their molecular structure.[70] Examples of such precursors are, for example, alkyl(alkoxy)zinc compounds[70a-c] and alkyl(hydroxy)zinc compounds.[70d] An alternative is also the use of ZnO2 as a single-source precursor of nanoparticulate forms of ZnO,[5,30,31] however, there are no methods of fabrication of homogeneous ZnO2 nanostructures of appropriate quality, which then would allow for the production of homogeneous ZnO nanoparticles.
The subject matter of the invention is a method of preparation of zinc-oxygen-based nanoparticles, in which an organozinc precursor is treated with an oxidizing agent, wherein the organozinc precursor is a compound of the formula
where:
Preferably achiral, optically active or organic compounds with an additional positive charge located at the nitrogen (N), phosphorus (P) or sulfur (S) atom are used as L- and X-type ligands.
Preferably the method of the invention leads to the preparation of zinc peroxide (ZnO2) nanoparticles or zinc oxide (ZnO) nanoparticles, more preferably zinc peroxide (ZnO2) nanoparticles.
Preferably the method of the invention leads to the preparation of uncoated zinc-oxygen-based nanoparticles and zinc-oxygen-based nanoparticles coated with an organic shell composed of at least one organic ligand, more preferably composed of two or more organic ligands selected from X and L, wherein X and L are defined above.
Preferably zinc-oxygen-based nanoparticles with a diameter less than or equal to 5 nm are prepared.
Preferably dialkyl- or diarylzinc compound of the formula R2Zn, where R is straight, branched or cyclic C1-C10 alkyl group or straight, branched or cyclic C1-C10 alkenyl group, benzyl group, phenyl group, mesityl group, in which any hydrogen atom may be substituted with fluorine, chlorine, bromine or iodine atom is used as organozinc precursor.
Also preferably the organozinc precursor is a compound produced by the reaction between dialkyl- or diarylzinc compound of the formula R2Zn and an organic L- or X-H-type compound, or a mixture of two or more of these compounds, wherein:
Preferably the organozinc precursor formed by the reaction between a dialkyl- or diarylzinc compound of the formula R2Zn and an organic L- or X-H-type compound, or a mixture of two or more of these compounds, is generated in situ.
Preferably the in situ generated organozinc precursor is stored under an inert gas atmosphere for 0 minutes to 48 hours prior to exposure to the oxidizing agent.
Preferably a homoligand precursor or a heteroligand precursor, or mixtures thereof is used as organozinc precursor.
Preferably a pure solid-state compound or its solution in an aprotic organic solvent is used as dialkyl- or diarylzinc compound.
Preferably diethylzinc, dimethylzinc, di-iso-propylzinc, di-tert-buthylzinc, dicyclopentylzinc, dicyclohexylzinc or dicyclopentadienylzinc is used as dialkylzinc compound.
Preferably diphenylzinc or bis(pentafluorophenyl)zinc is used as diarylzinc compound.
Preferably a compound belonging to the purity category ranges from technical purity (90 - 99%) to spectral purity (99.999 - 99.9999%) is used as dialkyl- or diarylzinc compound.
Preferably hydrogen peroxide in the form of an aqueous solution or in the form of solid-state peroxide adducts is used as oxidizing agent.
Preferably hydrogen peroxide is used in the form of the aqueous solution at a concentration in the range from 1 to 75%, more preferably at a concentration in the range from 3 to 30%, and the most preferably at the concentration of 30%.
Preferably hydrogen peroxide-urea adduct (CO(NH2)2·H2O2) or sodium percarbonate (Na2CO3·1.5H2O2) is used as peroxide adduct.
Preferably ozone is supplied from the ozone generator, which produces it at a capacity in the range from 0.1 g/h to 50 g/h.
Preferably a molar ratio of the organozinc precursor to the oxidizing agent ranges from 1: 1 to 1:4, more preferably 1: 1, is used.
Preferably the method of the invention is carried out at temperature in the range from -78° C. to 70° C., more preferably in the range from -78° C. to 40° C.
Preferably the method of the invention is carried out for 5 seconds to 25 hours.
Preferably the method of the invention is carried out by treating the organozinc precursor with the oxidizing agent at a temperature in the range from -78° C. to 30° C. for 5 seconds to 1 hour and followed by heating the reaction mixture to a temperature in the range from 10° C. to 70° C. and then the reaction is continued for 15 minutes to 24 hours.
Preferably the organozinc precursor is treated with the oxidizing agent in an aprotic organic solvent.
Preferably anhydrous or water-containing solvent is used as aprotic organic solvent.
Preferably concentration of water in the solvent is less than 0.5%.
Preferably tetrahydrofuran, toluene, xylene, benzene, dimethylsulfoxide, dichloromethane, dioxane, acetonitrile, chloroform, hexane, acetone, diethyl ether or mixtures thereof are used as aprotic organic solvent.
Preferably molar concentration of the organozinc precursor in the reaction mixture ranges from 0.01 mol/L to 0.5 mol/L.
Preferably when using solid-state reactants, the method of the invention is carried out by a mechanochemical, i.e., solvent-free approach, preferably by grinding the organozinc precursor and the oxidizing agent in a glass reactor, in a mortar or in a ball mill.
Preferably the solvent-free approach comprises adding a dispersing agent.
Preferably an organic solvent which does not dissolve both the organozinc precursor and the oxidizing agent is added as the dispersing agent, more preferably hexane, dimethylsulfoxide, toluene, dioxane or mixtures thereof is used.
Preferably the method of the invention comprises at least one washing step of the as-prepared zinc-oxygen-based nanoparticles using an organic solvent to remove an excess of organic ligand as well as in order to obtain high-quality material, more preferably the washing step is performed twice.
Preferably hexane, ethanol, methanol, acetone, toluene, benzene, xylene, tetrahydrofuran, dioxane, diethyl ether, dichloromethane or mixtures thereof is the organic solvent used in the washing step.
Preferably the method of the invention comprises one of the additional post-processing steps selected from:
Preferably grinding of ZnO2 is carried out under anaerobic or aerobic conditions.
Preferably grinding of ZnO2 is carried out in a glass reactor, in a ball mill or in a mortar, more preferably in a ball mill at a vibration frequency from 15 Hz to 30 Hz.
Preferably annealing is carried out under anaerobic or aerobic conditions.
Preferably annealing is carried out at a temperature in the range from 100° C. to 1000° C. for 1 minute to 48 hours.
The invention also relates to zinc peroxide nanoparticles prepared by the above-defined method.
Preferably zinc peroxide nanoparticles are uncoated or coated with an organic shell.
Preferably the organic shell is composed of at least one organic ligand selected from X and L, wherein
Preferably L- and X-type ligands are selected from achiral, optically active or organic compounds with an additional positive charge located at the nitrogen (N), phosphorus (P) or sulfur (S) atom.
Preferably the organic shell is composed of at least one organic ligand selected from X and L, wherein X and L are defined as above.
Preferably the diameter of zinc peroxide nanoparticles is less than or equal to 5 nm.
The invention also relates to the use of above-defined zinc peroxide nanoparticles as antibacterial and bacteriostatic materials, as a component of pyrotechnic compositions, photocatalyst, and single-source inorganic precursors of nanoparticulate forms of zinc oxide (ZnO).
The method of the invention leads to the preparation of zinc-oxygen-based nanoparticles without the addition of any stabilizing agent or zinc-oxygen-based nanoparticles coated with an organic shell composed of anionic X-type, neutral L-type ligands or mixtures thereof, characterized by high purity and crystallinity, stability, uniformity in shape and size. Preferably, the method of the invention leads to the formation of zinc peroxide nanoparticles; however, it is also possible to obtain nanocrystalline ZnO directly (i.e., by using an appropriate source of H2O2 and/or the molar ratio of the applied reactants) or indirectly (by a transformation of the resulting peroxide materials). The use of suitable, well-defined organozinc precursors and the use of hitherto not considered organic and inorganic peroxide adducts made it possible to solve the problems associated with the synthetic processes described in the prior art.
In the method of the invention dialkyl- ir diarylzinc compounds of the formula R2Zn as well as organometallic R2ZnLy— and RZnX-type compounds were used, which may occur in a monomeric or an aggregated form. The applied R2ZnLy-type precursors contain in their structure R2Zn species, which are stabilized by neutral aprotic ligands. In turn, the [RZnX]-type precursors may be considered as homo- or heteroligand complexes obtained in the direct reaction of the compound X-H with dialkyl- or diarylzincs, which lead to the formation of nanoparticles stabilized with one- or multi-component organic shell. The method of the invention makes it possible to obtain the following types of nanocrystalline ZnO2 with a core size within a few nanometers (from 1 nm to 10 nm): i) uncoated nanoparticles, i.e., without the addition of surface stabilizing agents; ii) nanoparticles coated with organic L-type ligands; also including ligands derived from the applied peroxide adducts; iii) nanoparticles coated with monoanionic X-type organic ligands; iv) mixed-ligand shell nanoparticles, i.e., nanoparticles stabilized with a multi-component organic shell composed of two or more types of ligands (e.g. X+L) or composed of two or more different ligands of the same type (e.g., X1+X2, L1+L2). It also allows for the determination of relationship between the properties of the resulting nanoparticles and their structure as well as significantly facilitates the design of new nanomaterials with a defined structure and desired physicochemical properties. In addition, the use of anionic ligands allows for better control of nanoparticle growth. In the above-described systems, the anionic X-type ligands and the neutral L-type ligands are connected to the zinc-oxygen-based core by strong covalent or donor-acceptor bonds, respectively. As a result, a better stabilization of the nanocrystalline ZnO2 core and thus increased stability as well as limited aggregation and/or agglomeration of the resulting nanoparticles is provided. It is worth noting that the literature-derived data indicated that the stabilization of the cores and the degree of aggregation of the nanoparticles prepared using low- or high-molecular-weight surfactants occurs through weaker and more labile interactions, which results in irregularly shaped nanoparticles with moderate stability, high polydispersity and tendency to aggregation and/or agglomeration. ZnO2 NPs are a promising material used as a solid-state oxygen reservoir as well as a source of reactive oxygen species in both solid-state and in solution. The resulting ZnO2 nanoparticles could also be used as antibacterial and bacteriostatic materials, as a component of pyrotechnic compositions, photocatalyst, and single-source inorganic precursors of nanoparticulate forms of zinc oxide. An appropriate selection of the process conditions (i.e., annealing temperature, vibration frequency of grinding and pH) allows for a controlled decomposition of the peroxide bond and transformation into uniform in shape and size zinc oxide nanoparticles. The method of the invention also allows to obtaining nanocrystalline ZnO by the direct method, i.e., by reacting an organometallic precursor with ozone or by using an appropriate molar ratio of the organozinc compound to the oxidizing agent in the form of inorganic peroxide adduct. Nanocrystalline ZnO can also be obtained using a reaction medium with coordinating properties in a direct reaction between dialkylzinc compound and H2O2.
The method of the invention opens up new possibilities in the design and the synthesis of new zinc-oxygen-based functional nanomaterials based on ZnO2 or ZnO.
The results concerning zinc-oxygen-based nanoparticles prepared by the method of the invention are shown in the figure, where:
The following examples present the subjects of the invention.
In all examples, anhydrous solvents pre-dried over molecular sieves, heated with a potassium-sodium alloy and distilled in an atmosphere of dry and oxygen-free inert gas or purified in a solvent purification system (SPS) were used, and depending on the cleaning conditions, they may contain insignificant amounts of water, i.e., less than 0.5%. In all examples, except for Example 4, commercially available dialkyl- or diarylzinc compounds were used with the purity declared by the manufacturer as technical grade (90-99%). The applied in the examples term ambient temperature means a temperature in the range from 10° C. to 30° C., and room temperature means a temperature in the range from 22° C. to 27° C. The resulting materials were characterized by a wide range of analytical techniques, such as transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and dynamic light scattering (DLS).
The abbreviations ZnO2 NPs and ZnO NPs used throughout the description refer to nanoparticles of zinc peroxide and nanoparticles of zinc oxide, respectively.
10 mL of anhydrous solvent - tetrahydrofuran (THF) was introduced into a Schlenk vessel (V = 100 cm3) equipped with a magnetic stir bar and cooled to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (30% aqueous solution of H2O2, 1 mmol H2O2) were then added dropwise via a syringe and under an inert gas atmosphere. Initially the reaction was carried out at -78° C. for ca. 10 minutes. Then the reaction mixture was allowed to gradually warm to room temperature and left at this temperature for additional 30 minutes. After this time, the product in the form of a white precipitate, which is nanocrystalline ZnO2 (from now on termed ZnO2(1) NPs), was obtained and characterized. TEM micrographs of the resulting ZnO2 nanoparticles as well as size distribution of ZnO2(1) NPs are shown in
iPr2Zn (1 mL of a 1 M solution in toluene, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were successively added dropwise to 10 mL of solvent mixture (5 mL of THF + 5 mL of hexane) placed in a Schlenk vessel, vigorously stirred with a magnetic stir bar and cooled to -10° C. The reaction was carried out at -10° C. for ca. 5 minutes. Then the reaction mixture was allowed to reach room temperature and stirred at this temperature for additional 24 hours. As a result, nanocrystalline ZnO2 (from now on termed ZnO2(2) NPs) was obtained and the crystal structure of the resulting product was then confirmed using PXRD (Error! Reference source not found. a; the average size of nanocrystallites is 3.36 ± 0.37 nm). Nanocrystalline ZnO2(2) decomposes into ZnO at 214° C. (Error! Reference source not found. b). Similar results have been obtained using other dilalkylzinc compounds such as dimethylzinc, di-tert-butylzinc, dicyclopentylzinc, dicyclohexylzinc or dicyclopentadienylzinc.
Et2Zn (1 mL of a 1 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were successively added dropwise to 10 mL of hexane placed in a Schlenk vessel, vigorously stirred with a magnetic stir bar and cooled to -78° C. The reaction mixture was left at -78° C. for a few minutes and then warmed to room temperature and stirred for additional 30 minutes. ZnO2(3) nanoparticles were obtained as a white solid, which was then decanted and dried under vacuum. PXRD analysis confirmed the nanocrystalline cubic crystal structure of ZnO2(3) (Error! Reference source not found. a; the average size of nanocrystallites is 2.26 ± 0.24 nm). Thermolysis of ZnO2(3) NPs occurs with a maximum decomposition rate at 158° C. and the decomposition process is finished at ca. 400° C. (
The reaction between high purity Et2Zn (99.9998%) and perhydrol was carried out according to the procedure described in Example 3 leads to the formation of nanocrystalline ZnO2 (from now on termed ZnO2(4) NPs) with physicochemical properties similar to ZnO2(1) and ZnO2(3)NPs. The average size of nanocrystallites calculated from Scherrer’s formula is 3.2 ± 0.21 nm. The lack of additional diffraction peaks proves the high purity of the tested material (Error! Reference source not found. a). FTIR analysis revealed the presence of IR bands characteristic of Zn—O (403 cm-1) and O—O (1487 and 1376 cm-1) species that are present in the structure of ZnO2(4). The thermal stability of the product was determined by thermogravimetric analysis. Decomposition of nanocrystalline ZnO2(4) occurs with a maximum decomposition rate at 210° C., which indicates the quantitative transformation of ZnO2 to ZnO (Error! Reference source not found. b).
282 mg (3 mmol) of hydrogen peroxide-urea adduct (CO(NH2)2·H2O2) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) was then added dropwise via a syringe and under an inert gas atmosphere. The reaction was carried out at -78° C. for ca. 20 minutes. Then the reaction mixture was allowed to spontaneously warm to ambient temperature and stirred at this temperature for additional 24 hours. Hereby, the product was obtained as a yellow precipitate, which was then decanted, purified by washing the resulting product two times with a small portions of ethanol and centrifugated (9000 rpm, 10 minutes). Nanocrystalline zinc peroxide (ZnO2(5) NPs) with a mean core size of 1.71 ± 0.21 nm was identified by PXRD (Error! Reference source not found. a). The lack of additional peaks on the diffraction pattern proves the high purity of the tested sample. Slight changes in the intensity and the bands’ position corresponding to C═O and N—H moieties, respectively, demonstrate the possible coordination of both the carbonyl and the amine groups on the surface of the resulting ZnO2 NPs (Error! Reference source not found. b). Thermogravimetric analysis of ZnO2(5) NPs indicates more complex nature of the decomposition profile of the tested system compared to those presented in the previous examples. Thermal decomposition of urea (which is a compound with a low melting point, i.e., ~133° C., and quickly decomposes at higher temperatures) occurs at 149° C., while the transformation of ZnO2 to ZnO begins at higher temperatures with a maximum decomposition rate at 214° C. (
88 mg (1 mmol) of butyric acid (C3H7COOH) or 214 mg (1 mmol) of heptafluorobutyric acid (C3F7COOH) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. After a while, the cooling bath was removed and the reaction mixture was allowed to spontaneously warm to ambient temperature and stirred at this temperature for additional 24 hours. A clear stable colloidal solution of ZnO2 nanoparticles (ZnO2(6) NPs) was obtained. The reaction product was precipitated from the post-reaction system using hexane (ca. 5 mL) and isolated by centrifugation (9000 rpm, 10 minutes). The resulting sediment was then washed with a small portion of hexane (2 mL), re-centrifuged and dried under vacuum. PXRD analysis (Error! Reference source not found.) confirmed the nanocrystalline cubic crystal structure of ZnO2(6) NPs and the average core size was determined to be 2.29 ± 0.31 nm. The lack of additional peaks on the diffraction pattern proves the high purity of the tested sample. Similar results have been obtained using glycine and 2-hydroxypropanoic acid. DLS analysis showed that the average solvodynamic diameter of the ZnO2(6) nanoparticles is 4.63 nm. Moreover, a low degree of polydispersity index (PdI = 0.157) indicated a narrow size distribution and high colloidal stability of ZnO2(6) NPs (Error! Reference source not found.). FTIR analysis confirmed the presence of an organic shell composed of deprotonated butyric acid molecules on the surface of nanocrystalline ZnO2 (Error! Reference source not found. a). Absence of a band characteristic for C═O stretching vibrations in the butyric acid molecule (1712 cm-1) and the appearance of the asymmetric vas(COO-) and the symmetric vs(COO-) stretches at 1569 and 1406 cm-1 (Δv = 163 cm-1), respectively, indicates that monoanionic carboxylate moieties bound to the ZnO2(6) NPs surface and act as bridging bidentate µ2-type ligands. The decomposition temperature of ZnO2 into ZnO is 204° C. We also noted that at higher temperatures (i.e., above 250° C.) the organic shell of ZnO2(6) NPs decomposes (Error! Reference source not found. b).
In the first step, 88 mg (1 mmol) of butyric acid in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. and Et2Zn (0.34 mL of a 3 M solution in hexane, 1 mmol) was then added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at a reduced temperature and then it was allowed to gradually warm to room temperature and stirred at this temperature for additional 3 hours. After this time, the molecular structure of the resulting product in the form of an ethylzinc derivative of butyric acid was confirmed by spectroscopic methods. In the next step, 0.1 mL of 30% aqueous solution of H2O2 (1 mmol) was added dropwise to the as-prepared organozinc precursor solution cooled to the temperature of a dry ice - isopropyl alcohol cooling bath. The reaction mixture was allowed to gradually warm to room temperature and stirred at this temperature for additional 12 hours. Then a clear stable solution was obtained. Product in the form of nanocrystalline ZnO2 (from now on termed ZnO2(7) NPs) was isolated from the post-reaction mixture and purified according to the method described in Example 6. TEM micrographs of the resulting ZnO2 nanoparticles as well as the size distribution of ZnO2(7) NPs are shown in Error! Reference source not found.. The micrographs show quasi-spherical ZnO2 nanocrystallites with a core size of a few nanometers (ca. 2 - 5.5 nm) and a mean core diameter of 3.66 ± 0.79 nm (Error! Reference source not found. f). The average core size of ZnO2(7) determined by PXRD (Error! Reference source not found.) is 2.11 ± 0.19 nm. Similar results have been obtained using glycine and 2-hydroxypropanoic acid.
136 mg (1 mmol) of phenylacetic acid (C7H7COOH) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice -isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. The reaction was carried out at -78° C. for ca. 10 minutes. Then the reaction mixture was allowed to spontaneously warm to ambient temperature and stirred at this temperature for additional 24 hours. A clear, stable solution was obtained. The reaction product was isolated and purified according to the method described in Example 6 as well as identified as nanocrystalline zinc peroxide (from now on termed (ZnO2(8) NPs) (Error! Reference source not found.). The average core size of ZnO2 is 2.24 ± 0.23 nm. DLS analysis in THF confirmed the monodispersity of the tested system (PdI = 0.168) and the solvodynamic diameter equal to 5.55 nm (Error! Reference source not found.). FTIR analysis revealed the presence of an organic shell composed of deprotonated phenylacetic acid molecules attached to the surface of the nanocrystalline ZnO2 core (Error! Reference source not found. a). The thermal decomposition of this material shown in
134 mg (1 mmol) 2-methoxyethoxy)acetic acid (CH3OCH2CH2OCH2COOH) or 117 mg (1 mmol) of betaine (i.e., zwitterion compound with an positively charged cationic functional quaternary ammonium group - (CH3)3N+CH2CO2-) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled to 0° C. and Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. The reaction was carried out at 0° C. for ca. 1 hour. Then the reaction mixture was allowed to reach ambient temperature and stirred at this temperature for additional 24 hours. After this time, a stable slightly turbid colloid was obtained and nanocrystalline ZnO2 (from now on termed ZnO2(9) NPs) was precipitated after the addition of 5 mL of ethanol and isolated from the resulting mixture by centrifugation (9000 rpm, 10 minutes). The resulting sediment was washed with a small portion of ethanol (2 mL), re-centrifuged and dried under vacuum. PXRD analysis confirmed the nanocrystalline, cubic crystal structure of the resulting ZnO2 and the average core size of crystallites is 1.96 ± 0.17 nm (Error! Reference source not found.). Solvodynamic diameter of ZnO2(9) NPs is 4.83 nm (PdI = 0.082) (Error! Reference source not found.). The presence of a stable and strongly bound protective layer on the surface of ZnO2 composed of carboxylate ligands was confirmed by FTIR method. ZnO2(9) NPs form stable colloidal solutions or stable suspensions in organic solvents such as THF, toluene, hexane, methanol, ethanol, DMSO, dichloromethane, ethyl acetate, diethyl ether and acetone as well as in water (Error! Reference source not found.). Likewise, betaine-coated ZnO2 NPs form stable dispersions in a wide range of organic solvents and water.
In the first step, 137 mg (1 mmol) of S-(+)-2-amino-1-phenylethanol (C6H5CH(OH)CH2(NH2) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. Then the resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. and Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were then added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at -78° C. for ca. 10 minutes and then it was allowed to gradually warm to room temperature and stirred at this temperature for additional 24 hours. After this time, the molecular structure of the resulting product in the form of an ethyl zinc derivative of S-(+)-2-amino-1-phenylethanol was confirmed by spectroscopic methods. In the next step, 0.1 mL of 30% aqueous solution of H2O2 (1 mmol) was added dropwise to the as-prepared organozinc precursor solution cooled to the temperature of a dry ice - isopropyl alcohol cooling bath. Then the reaction mixture was allowed to gradually warm to room temperature and stirred at ambient temperature for additional 24 hours (note that the reaction time can be shortened by heating the reaction mixture at reflux temperature, i.e., 65° C. - 70° C. for 3 - 4 hours). After that, a stable slightly turbid colloid was obtained. The product in the form of nanocrystalline ZnO2 (from now on termed ZnO2(10) NPs) was isolated from the post-reaction mixture and purified according to the method described in Example 6. The average core size of ZnO2(10) determined by PXRD (Error! Reference source not found.) is 2.55 ± 0.33 nm and the solvodynamic diameter of the associates present in the solution is 25.54 nm (PdI = 0.169) (Error! Reference source not found.). TGA profile shown in Error! Reference source not found. exhibits two main decomposition steps with maximum decomposition rates at 214° C. and 439° C., respectively, and the thermolysis is finished at ~ 450° C. with a total weight loss of 44.24%.
250 mg (1 mmol) of diphenyl phosphate ((C6H5O)2P(O)OH) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Similar results can be obtained using a crystalline organozinc precursor of the formula [tBuZn(O2P(OPh)2]4. Initially the reaction was carried out at -78° C. for ca. 10 minutes and then it was allowed to gradually warm to ambient temperature and stirred at this temperature for additional 4 hours. After this time, a colorless solution was obtained. The reaction product was then isolated and purified according to the method described in Example 6 and identified as nanocrystalline zinc peroxide (from now on termed ZnOz(11) NPs) with a small core size equal to 1.60 ± 0.10 nm (Error! Reference source not found.). Similar results have been obtained using other organophosphorous compounds such as phenyl dihydrogen phosphate, diphenylphosphinic acid or phenylphosphonic acid.
In the first step, 228 mg (1 mmol) of myristic acid (CH3(CH2)12COOH) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. and Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) was then added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at the temperature of the cooling bath and then it was allowed to gradually warm to room temperature and stirred at this temperature for additional 5 hours. After this time, the molecular structure of the resulting product in the form of an ethyl zinc derivative of myristic acid was confirmed by spectroscopic methods. In the next step, 0.2 mL of 15% aqueous solution of H2O2 (1 mmol) was added dropwise to the as-prepared organozinc precursor cooled to the temperature of a dry ice - isopropyl alcohol cooling bath. Then the reaction mixture was allowed to gradually warm to room temperature and stirred at ambient temperature for one day. After this time, a clear solution was obtained. Product in the form of nanocrystalline ZnO2 (from now on termed ZnO2(12) NPs) was isolated from the post-reaction mixture and purified according to the method described in Example 6. PXRD analysis (Error! Reference source not found.) confirmed the nanocrystalline structure of the resulting nanoparticles and the average core size was determined to be 2.01 ± 0.13 nm. The solvodynamic diameter of ZnO2(12) NPs in THF is 5.98 nm and the resulting solution is characterized by high colloidal stability and monodispersity (PdI = 0.122) (Error! Reference source not found.). Absence of a band characteristic for C=O stretching vibrations in the myristic acid molecule (~ 1700 cm-1) and the appearance of the asymmetric vas(COO-) and the symmetric vs(COO-) stretches at 1581 and 1416 cm-1 (Δv = 165 cm-1), respectively, indicates the presence of monoanionic carboxylate ligand bound to the surface of ZnO2(12) NPs.
In the first step, 73 mg (1 mmol) of propionamide (CH3CH2CONH2) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C., and Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) was then added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at a reduced temperature and then it was allowed to gradually warm to ambient temperature and stirred at this temperature for additional 3 hours. After this time, the molecular structure of the resulting [EtZn—X]—type precursor (where X - monoanionic propionamide ligand) was confirmed by spectroscopic methods. In the next step, 1 mL of a 3% aqueous solution of H2O2 (1 mmol) was added dropwise to the in situ generated organozinc precursor cooled to the temperature of a dry ice - isopropyl alcohol cooling bath. Then the reaction mixture was allowed to gradually warm to room temperature and stirred at ambient temperature for one day. After this time, nanocrystalline ZnO2 (from now on termed ZnO2(13) NPs) was obtained in the form of a precipitate, which was isolated from the post-reaction mixture by centrifugation (9000 rpm, 10 minutes). Similar ZnO2 NPs have been obtained using phthalimide, dicyclohexylurea and cysteine. The resulting sediment was then washed two times with a small portion of hexane (2 mL), re-centrifuged and dried under reduced pressure. The average core size of ZnO2(13) NPs determined by PXRD (Error! Reference source not found.) is 2.48 ± 0.29 nm. Thermolysis of nanocrystalline ZnO2(13) is a complex and multi-stage process. TGA profile shown in
In the first step, 88 mg (1 mmol) of 2,2-dimethyl-1-propanol ((CH3)3CCH2OH) or 182 mg (0.25 mmol) of [EtZn(OCH2C(CH3)3)]4 in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar and cooled in a dry ice - isopropyl alcohol bath. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at out at the temperature of the cooling bath for ca. 15 minutes and then it was allowed to gradually warm to room temperature and stirred at this temperature for additional 24 hours. After this time, product as a precipitate falling to the vessel’s bottom was obtained and then purified according to the procedure described in Example 6. Based on PXRD, the reaction product was identified as nanocrystalline zinc peroxide (from now on termed ZnO2(14) NPs) with a relatively small core size equal to 3.03 ± 0.10 nm (Error! Reference source not found.) and coated with organic shell (Error! Reference source not found.). DLS measurements for the colloidal solution of ZnO2(14) NPs in DMSO confirmed the presence of associates with an average size of 133.6 nm and the polydispersity index equal to 0.161 (Error! Reference source not found.). The presence of IR band located in the area of 3300 cm-1 corresponds to O—H stretching vibrations, which indicates the adsorption of water molecules and the parent alcohol on the surface of nanoparticles. Thermal decomposition shown in
164 mg (1 mmol) of triethylene glycol monomethyl ether (CH3O(CH2CH2O)3CH2CH2OH) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at a reduced temperature and then it was allowed to gradually warm to room temperature and stirred at this temperature for additional 24 hours. Nanocrystalline zinc peroxide (ZnO2(15) NPs) was obtained as a precipitate falling to the vessel’s bottom and then purified according to the procedure described in Example 6. The average size of nanocrystallites calculated from Scherrer’s formula is 2.29 ± 0.16 nm, and the lack of additional peaks on the diffraction pattern proves the high purity of the tested material (Error! Reference source not found.). DLS measurements confirmed that the solvodynamic diameter of ZnO2 NPs dispersed in DMSO is 68.2 nm, which indicates the presence of small soft-type associates. The colloidal solution of ZnO2(15) NPs is characterized by monodispersity (PdI ═ 0.095) and high stability both in organic solvents and in water (Error! Reference source not found.).
222 mg (1 mmol) of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (C8H22N2O3Si2) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Immediately after mixing the reactants (i.e., after ca. 5 seconds) the reaction mixture was allowed to gradually warm to ambient temperature and stirred for additional hour. The reaction product was obtained as a precipitate falling to the vessel’s bottom, which was then purified according to the procedure described in Example 6 and identified as nanocrystalline zinc peroxide (ZnO2(16) NPs) (Error! Reference source not found.). Broadening of diffraction peaks indicates the relatively small size of the resulting nanocrystallites (d < 1 nm). Example 17.
167 mg (1 mmol) of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (C8H22N2O3Si2) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.75 mL of a 2 M solution in hexane, 1.5 mmol) and 0.15 mL of perhydrol (1.5 mmol of H2O2) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at -78° C. and then it was allowed to gradually warm to room temperature and stirred at this temperature for an additional one hour. The reaction product was obtained as a precipitate falling to the vessel’s bottom, which was then purified according to the procedure described in Example 6 and identified as nanocrystalline zinc peroxide (ZnO2(17) NPs) (Error! Reference source not found. a) with a mean core size equal to 1.56 ± 0.24 nm. FTIR analysis revealed the presence of IR bands corresponding to the Si—O vibrations (1044, 1013 cm-1) and thus confirmed the presence of the ligand shell on the surface of nanocrystalline ZnO2 (Error! Reference source not found. b).
78 mg (1 mmol) of dimethylsulfoxide ((CH3)2SO) in 10 mL of anhydrous THF was placed in a Schlenk vessel equipped with a magnetic stir bar. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) was then added dropwise using a syringe and under an inert gas atmosphere and the resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Then 0.1 mL of 30% aqueous solution of H2O2 (1 mmol H2O2) was added dropwise to the system. Initially the reaction was carried out at the temperature of the cooling bath, which was removed after ca. 20 minutes, and then the reaction mixture was allowed to reach ambient temperature and stirred at this temperature for additional 24 hours. After this time, a stable suspension was obtained. In order to isolate ZnO2, 5 mL of acetone was added to the post-reaction mixture and centrifugated (9000 rpm, 10 minutes). Then the resulting precipitate was washed with a small portion of acetone (2 mL), re-centrifuged and dried. Nanocrystalline zinc peroxide (ZnO2(18) NPs) with a core size of 2.39 ± 0.22 nm was identified usig PXRD (Error! Reference source not found. a). The lack of additional peaks on the diffraction pattern proves the high purity of the tested product. FTIR analysis indicated the presence of —OH groups/water molecules and DMSO molecules coordinated to the surface of ZnO2(18) NPs. The quantitative thermal decomposition of ZnO2 into ZnO is at 196° C. (Error! Reference source not found. b). Similar results can be obtained using 1 mmol of acetone, fluoroacetone or diethyl ether, which also act as L-type stabilizing ligands, insted of dimethylsulfoxide.
262 mg (1 mmol) of triphenylphosphine ((C6H5)3P) or 278 mg (1 mmol) of triphenylphosphine oxide ((C6H5O)3P) in 10 mL of anhydrous THF was placed in a Schlenk vessel equipped with a magnetic stir bar. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol (1 mmol of H2O2) were then sequentially added dropwise using a syringe at room temperature (ca. 22 - 27° C.) and under an inert gas atmosphere. The reaction mixture was stirred for one day. Then product was isolated from the post-reaction mixture and purified according to the procedure described in Example 6. PXRD data confirmed that nanocrystalline ZnO2 (from now on termed ZnO2(19) NPs) with a cubic crystal structure was obtained (Error! Reference source not found. a). Broadening of diffraction peaks indicates the relatively small size of the resulting nanocrystallites (d < 1 nm). FTIR analysis confirmed the presence of an organic shell composed of triphenylphosphine molecules as well as water molecules adsorbed of the surface of ZnO2(19) NPs (Error! Reference source not found. b).
In the first step, 222 mg (1 mmol) of N-[3-(trimethoxysilyl)propyl]ethylenediamine ((CH3O)3Si(CH2)3NHCH2CH2NH2) in 10 mL of anhydrous THF was placed in a Schlenk vessel equipped with a magnetic stir bar. Then the resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. and Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) was then added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at a reduced temperature and then it was allowed to gradually warm to room temperature and stirred at this temperature for additional 24 hours. After this time, the structure of the as-prepared product was confirmed by spectroscopic methods. In the next step, 0.1 mL of 30% aqueous solution of H2O2 (1 mmol) was added dropwise to the solution of the organozinc precursor cooled to the temperature of a dry ice - isopropyl alcohol cooling bath. Immediately after adding the oxidizing agent, the reaction mixture was warmed to room temperature and stirred at this temperature for additional 24 hours. Nanocrystalline ZnO2 (from now on termed ZnO2(20) NPs) in the form of a precipitate was isolated using centrifugation (9000 rpm, 10 minutes) and then washed with a small portion of hexane (2 mL), re-centrifugated and dried. The inorganic core of ZnO2(20) NPs is characterized by a relatively small size of ca. 1 nm. (
129 mg (1 mmol) of octylamine (CH3(CH2)7NH2) in 10 mL of anhydrous THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 0.1 mL of perhydrol were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at a reduced temperature and then it was allowed to gradually warm to room temperature and stirred at this temperature for 1 hour. The reaction product was isolated and purified according to the procedure described in Example 6 and then identified as nanocrystalline ZnO2 (ZnO2(21) NPs) using PXRD (Error! Reference source not found.). The average core size of ZnO2(21) nanoparticles is 2.15 ± 0.17 nm (Error! Reference source not found.) and the solvodynamic diameter measured in DMSO is 81.3 nm (PdI = 0.150) (Error! Reference source not found.). FTIR analysis (Error! Reference source not found.) confirmed the presence of an organic shell on the surface of nanocrystalline ZnO2(21) NPs.
136 mg (1 mmol) of phenylacetic acid (C7H7COOH) and 88 mg (1 mmol) of 2,2-dimethyl-1-propanol in 10 mL of anhydrous THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled to -78° C. and Et2Zn (1 mL of a 2 M solution in hexane, 2 mmol) and 0.2 mL of perhydrol (2 mmol of H2O2) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at -78° C. for several minutes and then it was allowed to gradually warm to room temperature and stirred at this temperature for additional 24 hours. After this time, a colorless solution was obtained and nanocrystalline ZnO2 (from now on termed ZnO2(22) NPs) was precipitated using 5 mL of hexane and isolated from the post-reaction mixture by centrifugation (9000 rpm, 10 minutes). The resulting precipitate was washed with a small portion of hexane (2 mL), re-centrifuged and dried. PXRD analysis confirmed the nanocrystalline, cubic crystal structure of the resulting ZnO2 with a crystallite size of 2.10 ± 0.15 nm (
In the first step, organometallic precursors were prepared according to the following procedure. 136 mg (1 mmol) of phenylacetic acid (C7H7COOH) and 88 mg (1 mmol) of 2,2-dimethyl-1-propanol in 10 mL of anhydrous THF were placed in a separate Schlenk vessels (100 cm3) equipped with a magnetic stir bars. Reagents were cooled in a dry ice - isopropyl alcohol bath to -78° C. and Et2Zn (1 mL of a 2 M solution in hexane, 2 mmol) was then added dropwise to each vessel. Initially the reaction was carried out at out at the temperature of the cooling bath and then it was allowed to gradually warm to room temperature and stirred at this temperature for additional 2 hours. After this time, the entire volume of the reaction mixture containing the ethylzinc derivative of phenylacetic acid was transferred to the reaction mixture containing the ethylzinc derivative of 2,2-dimethyl-1-propanol using a disposable syringe and under inert conditions. Similar results could be obtained by using the appropriate amounts of the respective crystalline organozinc precursors, i.e., [EtZn(O2H7C8)]n and [EtZn(OCH2C(CH3)3)]4 dissolved in the appropriate amount of an organic solvent (THF or toluene). The mixture with a final volume of 10 mL was stored at room temperature for additional 24 h. After this time, 0.2 mL of perhydrol (2 mmol of H2O2) was added to the reaction mixture cooled to -78° C. Then the reaction system was allowed to gradually warm to room temperature and left at this temperature for 24 hours (in the case of toluene, the reaction were carried out at 40° C. for 8 hours). The as-prepared ZnO2 nanoparticles are similar to ZnO2(22) NPs.
136 mg (1 mmol) of phenylacetic acid (C7H7COOH) and 88 mg (1 mmol) of 2,2-dimethyl-1-propanol in 10 mL of anhydrous THF was placed in a Schlenk vessel equipped with a magnetic stir bar. Reagents were cooled in a dry ice - isopropyl alcohol bath to -78° C. and Et2Zn (1 mL of a 2 M solution in hexane, 2 mmol) was then added dropwise. Initially the reaction was carried out at the temperature of the cooling bath for ca. 1 hour and then the reaction mixture was allowed to gradually warm to room temperature and stirred at this temperature for additional 2 hours. After this time, the molecular structure of the resulting product in the form of heteroligand organozinc compound was confirmed by spectroscopic methods. In the next step, 0.1 mL of 30% aqueous solution of H2O2 (2 mmol) was added dropwise to the as-prepared organozinc precursor solution cooled to the temperature of a dry ice - isopropyl alcohol cooling bath. Then the reaction mixture was allowed to gradually warm to room temperature (ca. 3 h) and stirred at ambient temperature for additional 24 hours. In the above reaction, a product similar to ZnO2(22) NPs was obtained.
136 mg (1 mmol) of phenylacetic acid (C7H7COOH) and 129 mg (1 mmol) of octylamine in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 2 mmol) and 0.1 mL of 75% aqueus solution of H2O2 (2 mmol) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Initially the reaction was carried out at -78° C. for ca. 10 minutes and then it was allowed to gradually warm to ambient temperature and stirred at this temperature for additional 24 hours. After this time, a colorless solution was obtained. The reaction product was purified according to the method described in Example 6 and identified as nanocrystalline zinc peroxide (from now on termed ZnO2(23) NPs) wit a core size equal to 2.06 ± 0.17 nm (Error! Reference source not found.) and solvodynamic diameter equal to 4.79 nm (PdI = 0.123) (Error! Reference source not found.). FTIR analysis shown in
129 mg (1 mmol) of octyalmine and 262 mg (1 mmol) of triphenylphosphine in 10 mL of anhydrous THF (the usage of water-containing solvent does not affect the properties of the resulting) was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 2 mmol) and 0.2 mL of 30% aqueous solution of H2O2 (2 mmol) were then sequentially added dropwise using a syringe and under an inert gas atmosphere. Then the reaction mixture was allowed to gradually warm to room temperature and stirred at this temperature for additional 24 hours. The reaction product was isolated and then purified according to the method described in Example 6. The presence of nanocrystalline ZnO2 (from now on termed ZnO2(24) NPs) with a mean core size equal to 1.97 ± 0.22 nm was confirmed using PXRD. The composition of the organic shell was determined on the basis of the IR spectrum shown in
0.2 mL (1 mmol) of peracetic acid solution (concentration = 40%; CH3COOOH) in 10 mL of THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 2 mmol) or Cy2Zn (1 mL of a 1 M solution in toluene, 1 mmol) was then added dropwise using a syringe and under an inert gas atmosphere. The reaction was carried out at -78° C. for ca. 40 minutes and then the reaction mixture was allowed to gradually warm to room temperature and stirred at this temperature for additional 1 hour. The resulting product in the form of sediment was purified according to the method described in Example 6. As a result, nanocrystalline ZnO2 (from now on termed ZnO2(25) NPs) was obtained and then the crystal structure of the resulting product was confirmed using PXRD (Error! Reference source not found. a). The average core size of ZnO2(25) is equal to 2.20 ± 0.15 nm, and FTIR analysis indicates the presence of acetate ligands bound to the surface of the as-prepared nanoparticles (Error! Reference source not found. b). Nanocrystalline ZnO2(25) decomposes into ZnO at 210° C. (with a total weight loss of ca. 15.4%), which is shown in Error! Reference source not found..
20 mg of ZnO2 NPs prepared according to the procedure described in Example 3 was placed in a glass vial and introduced into an oven pre-heated to a temperature of 200° C. The material was annealed at this temperature for 30 minutes. This process can be carried out both under anaerobic and aerobic conditions, without affecting the properties of the final product. The resulting material was allowed to gradually cool down to ambient temperature and characterized using PXRD. PXRD analysis revealed the presence of nanocrystalline ZnO with a wurtzite-type crystal structure and a crystallite size of 7.57 ± 0.94 nm (Error! Reference source not found.). The as-prepared ZnO NPs exhibit fluorescent properties both in the solid state as well as dispersed in a selected organic solvent. TEM micrographs of the resulting ZnO nanoparticles as well as their size distribution are shown in Error! Reference source not found.. The micrographs show single quasi-spherical ZnO nanocrystallites with a core size of a few nanometers (ca. 3.5 - 12 nm) as well as their bigger aggregates. Both the time and the temperature of annealing are parameters that should be adjusted to the starting ZnO2-type material and the values presented in this example are optimal for a larger group of nanocrystalline forms of ZnO2 (note that the annealing temperature should be in the range from 100° C. to 1000° C. and the time in the range from 1 minutes to 48 hours).
100 mg of ZnO2 NPs and steel ball with a diameter of 1 cm, acting as the grinding element, were placed in a steel ball mill with a capacity of 15 cm3. The mechanochemical transformation was carried out at a frequency of 30 Hz for 30 minutes (the mechanosynthesis process can be carried out both under anaerobic and aerobic conditions, since it does not affect the properties of the final product). Then the as-prepared product in the form of a white solid exhibiting luminescent under UV light irradation was characterized using PXRD. PXRD analysis confirmed the presence of both nanocrystalline ZnO with a wurtzite-type crystal structure and the residual phase of nanocrystalline zinc peroxide (
20 mg of ZnO2 NPs prepared according to the procedure described in Example 5 was placed in a glass vial and introduced into an oven pre-heated to a temperature of 200° C. The material was annealed at this temperature for 1 hour. As a result of high temperature treatment, the powder changed its color from light yellow to brown, which evidences, among others, partial degradation or the condensation reaction of the ligand on the NPs surface. The resulting material was gradually cool down to ambient temperature and characterized using PXRD (Error! Reference source not found. a). The resulting ZnO NPs exhibit fluorescence both in the solid state as well as dispersed in a selected organic solvent. Despite the partial decomposition of the organic layer, FTIR analysis (Error! Reference source not found. b) confirmed the presence of urea or its deriveatised in the tetsted material.
20 mg of ZnO2 NPs prepared according to the procedure described in Example 6 was placed in a glass vial and introduced into an oven pre-heated to a temperature of 180° C. The material was annealed at this temperature for 30 minutes and then allowed to reach ambient temperature. As a result of high temperature treatment, the powder changed its color from white to dark gray, which evidences, among others, partial degradation of the ligand on the NPs surface. The resulting product was cheracterized using PXRD. Diffractogram analysis indicated the presence of the nanocrystalline, wurtzite-type ZnO structure with a crystallite size of 7.31 ± 0.3 nm (Error! Reference source not found. a). The lack of diffraction pattern characteristic for the ZnO2 phase proves the complete decomposition of ZnO2 NPs into ZnO. Despite the partial decomposition of the organic layer, FTIR analysis confirmed the presence of an organic shell composed of deprotonated butyric acid molecules on the surface of nanocrystalline ZnO core (Error! Reference source not found. b), which is evidenced by the presence of relatively weak IR bands characteristic for the carboxylate ligands bound to the nanoparticles surface (1557 cm-1 and 1410 cm-1).
20 mg of ZnO2 NPs prepared according to the procedure described in Example 8 was placed in a glass vial and introduced into an oven pre-heated to a temperature of 200° C. The material was annealed at this temperature for 30 minutes and then allowed to reach ambient temperature. The resulting product was cheracterized using PXRD (Error! Reference source not found. a). Diffractogram analysis indicated the presence of the nanocrystalline, wurtzite-type ZnO structure with a crystallite size of 3.35 ± 0.58 nm as well as the lack of diffraction pattern characteristic for the ZnO2. FTIR analysis confirmed the presence of an organic shell composed of deprotonated phenylacetate acid molecules on the surface of nanocrystalline ZnO core (Error! Reference source not found. b), which is evidenced by the presence of two bands characteristic for COO- group (1544 cm-1 and 1398 cm-1).
20 mg of ZnO2(25) NPs prepared according to the procedure described in Example 27 was placed in a glass vial and introduced into an oven pre-heated to a temperature of 400° C. The material was annealed at this temperature for 20 minutes (similar results can be obtained by changing both the time and the temperature of annealing, while the annealing temperature should not be lower than 100° C.). Then the resulting material was allowed to gradually reach ambient temperature and was cheracterized using PXRD. Diffractogram analysis (Error! Reference source not found. a) indicated the presence of the nanocrystalline, wurtzite-type ZnO structure with a crystallite size of 7.03 ± 1.06 nm. The lack of diffraction pattern characteristic for the ZnO2 phase proves the complete decomposition of ZnO2 NPs into ZnO. The resulting ZnO NPs exhibit fluorescence properties both in solid state and dispersed in selected organic solvent. Absorption and emission spectra of the dispersion of ZnO NPs in DMSO are shown in Error! Reference source not found. b. ZnO NPs reveald a broad absorption with a maximum located at λ = 343 nm and characteristic for ZnO emission centered at λ = 567 nm (Error! Reference source not found. b). FTIR analysis confirmed the presence of an organic shell composed of deprotonated acetic acid molecules on the surface of nanocrystalline ZnO core.
5 mL of dimethylsulfoxide (water-containing commercially available DMSO was used as received, i.e, without purification) was placed in a Schlenk vessel equipped with a magnetic stir bar. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) and 3 mL of 1% aqueus solution of H2O2 (1 mmol) were then sequentially added dropwise via a syringe at ambient temperature and under an inert gas atmosphere. The oxidizing agent was added in small portions for about an hour. Then the reaction mixture was stirred at ambient temperature for 24 hours. After this time, a fluorescent suspension was obtained. Afterwards 5 mL of acetone was added to the reaction mixture and the resulting precipitate was separated by centrifugation (9000 rpm, 10 minutes), washed with acetone (2 mL), re-centrifuged and dried. PXRD analysis (Error! Reference source not found. a) confirmed the nanocrystalline wurtzite-type structure of ZnO NPs. The average size of nanocrystallites is 9.23 ± 1.6 nm, and the lack of additional peaks on the diffraction pattern proves the high purity of the tested sample. Absorption and emission spectra of the dispersion of ZnO NPs in DMSO are shown in Error! Reference source not found.. FTIR analysis confirmed the presence of an organic layer composed of DMSO and/or water molecules on the surface of nanocrystalline ZnO (Error! Reference source not found. b).
157 mg (1 mmol) of sodium percarbonate (Na2CO3·1.5H2O2) in 10 mL of anhydrous THF or in THF/hexane mixture was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.75 mL of a 2 M solution in hexane, 1 mmol) was then added dropwise via a syringe at ambient temperature and under an inert gas atmosphere. The reaction was carried out at -78° C. for several minutes and then the reaction mixture was allowed to spontaneously warm to ambient temperature and stirred at this temperature for additional 24 hours. The resulting sediment showed luminescent properties immediately after air exposure and under UV light irradiation. The resulting product was purified by washing two times with small portions of ethanol and then isolated from the reaction mixture by centrifugation (9000 rpm, 10 minutes). The product in form of white solid (Error! Reference source not found. a) was identified as the nanocrystalline wurtzite-type crystal structure of ZnO NPs with a core size equal to 6.16 ± 0.60 nm using PXRD. The lack of additional peaks on the diffraction pattern proves the acceptable purity of the tested sample. The as-prepared NPs revealed a broad and well-formed absorption band with a maximum at λ = 337 nm and relatively broad emission band with a maximum in the visible light range λem = 540 nm (Error! Reference source not found. b).
315 mg (2 mmol) of sodium percarbonate (Na2CO3·1.5H2O2) in 10 mL of anhydrous THF was placed in a Schlenk vessel equipped with a magnetic stir bar. The resulting solution was cooled in a dry ice - isopropyl alcohol bath to -78° C. Et2Zn (0.5 mL of a 2 M solution in hexane, 1 mmol) or Me2Zn (1 mL of 1 M solution in toluene, 1 mmol) was then added dropwise via a syringe and under an inert gas atmosphere. The reaction was carried out at -78° C. for several minutes and then the reaction mixture was allowed to spontaneously warm to ambient temperature and stirred at this temperature for additional 24 hours. The resulting precipitate was separated from the post-reaction mixture and purified according to the procedure described in Example 35 and it was identified as nanocrystalline ZnO with a wurtzite-type crystal structure (
Nanocrystalline zinc peroxide - ZnO2(3) NPs — prepared according to the procedure described in Example 3 was placed in 5 glass vials (50 mg each) with a capacity of 25 mL and equipped with magnetic stir bars. Then 10 mL of deionized water (MilliQ) with different pH values (i.e., 6; 6.5; 7; 7.5; 8) was added to each vial and the resulting mixtures were stirred for additional 24 h. After this time, all samples were centrifugated (9000 rpm, 5 min), and the resulting sediments were dried. The as-prepared materials were characterized using PXRD (
Et2Zn (1 mL of a 1 M solution in hexane, 1 mmol) was added dropwise to 10 mL of THF placed in a Schlenk vessel, vigorously stirred with a magnetic stir bar and cooled to -20° C. (an ice bath with a sodium chloride was used). Subsequently, the reaction vessel was connected to an ozone generator (ozone production was 3.5 g/h) and exposed to ozone for 3 minutes. Then the reaction mixture was allowed to gradually warm to room temperature and stirred at this temperature for additional 24 hours. The resulting product in the form of a precipitate was washed two times with small portions of hexane (2 mL), isolated using centrifugation (9000 rpm, 10 minutes) and dried. Nanocrystalline ZnO was obtained and the crystal structure of the resulting product was confirmed using PXRD (Error! Reference source not found.). The average size of ZnO nanocrystallites is 3.70 ± 0.48 nm. Similar results have been obtained using dimethylzinc or by dissolving 220 mg of Ph2Zn (1 mmol) in 20 mL of toluene or THF.
220 mg of Ph2Zn (1 mmol) or 400 mg of (C6F5)2Zn (1 mmol) and 282 mg of hydrogen peroxide-urea adduct (CO(NH2)2·H2O2) and steel ball with a diameter of 1 cm, acting as the grinding element, were placed in a steel ball mill with a capacity of 15 cm3 under an inert gas atmosphere. The mechanochemical transformation was carried out at a frequency of 30 Hz for 30 minutes. Thus product as a black solid was obtained. PXRD analysis confirmed the presence of a nanocrystalline zinc peroxide phase stabilized with urea resulting from the hydrogen peroxide-urea adduct decomposition (
Magnetic stir bars and 10 mg of selected nanocrystalline zinc peroxide - i.e., ZnO2(3) NPs (sample marked as 1), ZnO2(9) NPs (sample marked as 10) and ZnO2(15) NPs (sample marked as 19), which were prepared according to the procedures described in Example 3, Example 9 and Example 15, respectively - were placed in glass vials of the capacity of 25 mL. Then 10 mL of deionized water (MilliQ) with different pH values (i.e., 6 and 7) was added to each vial and the resulting mixtures were stirred for additional 24 h. Additional solutions with concentrations ranges from 5 µg/mL to 100 µg/L were prepared by the method of successive dilutions. Microbiological tests were performed using the disc diffusion method. In order to determine the bacteriostatic/bactericidal properties of ZnO2 NPs against gram(+) - Staphylococcus aureus and gram(-) - Pseudomonas aeruginosa bacteria, the materials selected for tests in the form of an aqueous solution with a specific pH were spotted on a filter paper (350 µl) and then the as-obtained disc was placed on a plate inoculated with bacterial isolate. Tests were performed for the nanomaterial concentration from 5 µg/mL to 100 µg/L in solutions with a pH of 6 and 7. The representative results are shown in
Magnetic stir bars and 10 mg of selected nanocrystalline zinc peroxide - ZnO2(1) NPs and ZnO2(16) NPs, which were prepared according to the procedures described in Example 1 and Example 16, respectively - were placed in glass vials of the capacity of 25 mL. Then 10 mL of deionized water (MilliQ) was added for each vial and sonicated for 10 minutes. Additional solutions with concentrations of 1 mg/mL (for ZnO2(16) NPs) and 10 mg/mL (for ZnO2(1) NPs and for ZnO2(16) NPs) were prepared by the method of successive dilutions. The antibacterial properties of the tested nanomaterials were determined in accordance with the ISO 22196:2011/JIS Z 2801:2010 test method. ZnO2 NPs in the form of aqueous solutions with a specific concentration were evenly applied in the form of a thin layer on the entire surface of a sterile glass square plates (5 cm x 5 cm). Then as-prepared plates were dried at 40° C. The whole process was repeated three times, and the total volume of material suspension applied on each glass plate was 1 mL. For each bacterial strain (i.e., gram(+) - Staphylococcus aureus, gram(-) -Pseudomonas aeruginosa and gram(-) - Escherichia coli) the inoculum was prepared as described in the test method. Inoculum concentration ranged between 2.5 × 105 and 1.0 × 106 CFU/mL. Each test sample (both control samples that are not covered with any material and those that contain a tested nanomaterial layer) was inoculated with 0.4 mL of the inoculum. Then the as-prepared samples were covered with sterile plastic in order to ensure direct contact between viable bacteria and tested nanomaterial. Control sample, immediately after inoculation, was washed using neutralizing solution (broth SCDLP) in a volume of 10 mL per sample and then plated on the propagation medium at serial dilutions from 100 do 10-4. Thest samples were incubated for 24 h at 35° C. and a relative humidity of not lover than 90%. After this time, samples were washed with a neutralizing solution and plated on the propagation medium at dilutions from from 100 do 10-4. The study was carried out in triplicate, separately for each of the mentioned bacterial strains. After 72 h of incubation, bacterial colonies were counted for each test sample and the survival of bacterial cells on each of the test samples was calculated according to the formulas described in ISO 22196/JIS Z 2801 test method. The value of antibacterial activity (R) was calculated according to the formulaR = Bt — Ct (where: Bt— average of logarithm numbers of viable bacteria from control sample at time = 24 hour; Ct— average of logarithm numbers of viable bacteria from treated sample at time = 24 hour). According to the ISO 22196/JIS Z 2801 standard sufficient antibacterial effectiveness is reached when the antibacterial activity (R) is rated 2 or more. Both ZnO2(1) NPs and ZnO2(16) NPs show a very good antibacterial effectiveness against selected bacterial strains (i.e., R is equal to 6.04 (S. aureus), 6.20 (E. coli) and 6.49 (P. aeruginosa) and R is equal to 7.84 (S. aureus), 7.53 (E . coli) and 6.43 (P. aeruginosa) for ZnO2(1) and ZnO2(16) NPs) concentration of 10 mg/mL, respectively). In addition, ZnO2(16) NPs at concentration of 1 mg/mL is also characterized by a very good antibacterial effectiveness against P. aeruginosa (R = 8.93) and S. aureus (R = 3.39).
ZnO2 nanoparticles were prepared according to the procedure described in Example 16 and prepared for testing according to the method described in Example 41. The biocidal properties of ZnO2 were determined by comparing the number of viable bacterial/fungal cells deposited from the air on the surface of sterile glass square plates (5 cm x 5 cm) protected with a thin layer of ZnO2(16) NPs and on a control (uncovered) plates. Material was applied to the glass square plates according to the procedure described in Example 41. The as-prepared test samples (both control samples and those that contain a tested nanomaterial layer) were placed in sterile Petri dishes and left in the room for the specified time (in this study, three different exposure times of 5, 30 and 60 minutes, respectively, were carried out). Immediately after exposure, the samples were washed with a neutralizing solution (SCDLP broth) in a volume of 10 mL per sample and plated on bacterial and fungal media at serial dilutions from 100 to 10-4. After 72 h of incubation, bacterial/fungal colonies were counted for each test sample and the number of microbial cells was calculated per 1 m3 of air. The value of the antibacterial efectiveness was determined according to the formula: L = a × 1000 / B × k (where: L: average number of bacterial/fungal cells deposited on the plate per 1 m3 of air; R: number of microorganisms in 1 m3 of air; a: number of colonies microorganisms grown on appropriate media; B: area of the tested material sample [cm2]; k: exposure time factor of the tested material; k = t (exposure time in minutes) × ⅕. Results (L < 10 for all tested cases, where L - the average number of bacterial/fungal cells deposited on the plate per 1 m3 of air; data averaged for three different exposure times) confirm that ZnO2(16) NPs show strong antimicrobial effect on the surface exposed to free deposition of bacteria and fungi from the air.
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| Number | Date | Country | Kind |
|---|---|---|---|
| P.434715 | Jul 2020 | PL | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/PL2021/050054 | 7/16/2021 | WO |
