TW200944212A - Antibacterial nano silver particle/clay compound and the manufacturing method thereof - Google Patents

Abstract

The present invention provides an antibacterial nano silver particle/clay compound and a manufacturing method thereof, which comprises mainly metal particles and flake-like inorganic clay, wherein the flake-like inorganic clay has a length to diameter ratio of 10-100,000 and serves as a carrier for the metal particles to realize nano-grade dispersion of the metal particles. The antibacterial nano metal particle/inorganic clay compound has a dimension of 5-100 nm. The present invention also provides a manufacturing method for the antibacterial nano silver particle/clay compound, which can be obtained by mixing a metal ion compound, flake-like inorganic clay and a reducing agent in water to undergo reduction reaction. The inorganic clay serves as a dispersing agent or a protecting agent for the metal to allow the metal to realize nano-grade dispersion. The present invention further provides an antibacterial preparation, which comprises the above-mentioned nano metal particle/inorganic clay compound and a solvent, wherein the solid content of antibacterial nano metal particle/inorganic clay compound in the solution is greater than 0.01 wt%.

Description

200944212 IX. Description of the Invention: [Technical Field] The present invention relates to a nano silver particle/clay composite for antibacterial use and a method for producing the same, which can be applied to materials, medicines, chemicals, chemicals, materials And other fields, such as antibacterial and health care. [Prior Art] Nano silver particles have a recognized antibacterial effect and can kill more than 6 kinds of bacteria. In the case of multiple dilutions, nano silver has a 99.99% inhibition effect on the gut g, Staphylococcus aureus, Salmonella and Pseudomonas aeruginosa. When the bacteria are killed by silver ions, The silver ions will be freed from the dead bacteria. 'Continue to repeat the action on the live fine g until all the bacteria (4) n. This is known to be a long-acting antibacterial agent. Silver is a non-toxic substance, and pure nano-silver is also edible, so it is harmless to the human body. Through the current popular nano technology, the activity of the nano-filament can be increased, the surface area is increased, and the sterilization function is enhanced to about 200 times that of silver. Silvazine is a commercially available nano silver commodity, the main component of which is Silver Sulfadiazine e. The figure i shows the inhibitory effect of Silvazine on staphylococcus aureus under multiple dilution conditions. . At present, the method for preparing nano particles includes: (1) cracking the macroscopic substance into a nanometer-sized particle by a high-energy laser; (2) gasifying the gold-state substance into a silk metal vapor, and then condensing and integrating the metal into a metal Naiyu? (3) Weaving nano silver with a lion liquid paste oxidation county. However, the above process is not only complicated in operation, but also requires expensive equipment. In the process of operation or manufacturing, the concentration must be carried out at a scale of _. If the concentration of silver ions is to be increased, silver particles are easily aggregated during the reduction. The scope is limited. The organic solvents and organic surfactants used are also a burden on the environment. In order to stabilize the nano metal particles and to produce a condensate image, it is usually necessary to add a dispersant or a protective agent during the preparation of the metal nanoparticles 200944212. The mode of action of the protective agent includes: (1) by electrostatic repulsion force, the surface of the particle is adsorbed to form an electric double layer, and the surface of the particle carries the same electric charge, then when the two particles are close to each other, the regenerative force will increase, preventing Particles condense. If the anion adsorbed on the surface is replaced by a neutral adsorbate, the surface charge will decrease and the van der Waals force will agglomerate the particles. In addition, under the high concentration of particles or the strong increase of the solution ions, due to the dielectric strength, the electric double layer is compressed, which is unsatisfactory for the stability of the particles; (2) by the steric hindrance, if there is an adsorption protectant on the surface of the particles, The formation of a protective agent layer on the surface of the metal particles by the organic molecules and the inhibition of the aggregation of the particles are called steric stabilization. Commonly used protective agents include: water-soluble polymers (such as pvp, pVA, p〇lymethylvinylether, pAA, etc.), surfactants, S-site or chelating agents. © In order to solve many problems of the conventional process, the present invention uses clay as a dispersant or a protective agent for metal particles to prepare a nano metal particle/inorganic clay composite by a chemical reduction method. [Summary of the Invention] The particle training - the silk screen / sticky domain silk of the inspection, so that the nano silver pull can not enter the inside of the cell, so it can avoid destroying the cells.另 Another object of the present invention is to provide a method for defensive resistance, which has a simple procedure and does not require the use of an organic solvent or an surfactant. Clay complex. The second thing is to provide a kind of anti-reagent, which can be used in biology, medicine, chemical, chemical, materials and other fields, such as antibacterial and medical care. This hair-like enchanting butterfly particle/inorganic clay composite mainly consists of metal particles and a piece of cut, and the length-to-diameter ratio of the medium-grained soil is 1 (HQM(10), ===tr her butterfly side and can = 1 The anti-agent of the present invention comprises the above-mentioned anti-bacterial nano metal particle solid content 200944212, 嶋, ι峨, preferably silver. The aspect ratio of the above-mentioned flaky inorganic clay is (10) soil-), Montmorillonite, synthetic mica, kaolin soil (5) melting, bell-shaped double hydroxide (10)), preferably with a face-to-face gift of moonstone, attapulgite, insect to stone, layer rebellion to have a face Body. The face of the human body is about 2:1. ❹ Ο The ion has no soil weight and the balance is 1: victory over 1. The heart of the heart-woven clay The father changed the volume «for the 〇. 丨 岭 岭 5. G _iv / g. Ion of metal particles The ratio of the cation exchange equivalent of the flaky inorganic clay is 0. In the δ 财 ft 制造 manufacturing method, the metal compound may be _3, AgC test, edge performance or uCl4 · 3 rib, or any suitable metal. The reducing agent may be methanol, ethanol, propanol, butanol, formaldehyde alcohol , propylene glycol, butanediol, glycerol, m (p〇iyvinyiaic 〇 (10) 视 (10) 崎 (8) g ycoi), PPG (P〇lyp clear lene glyc 〇 1), dodecyl alcohol or sodium borohydride (_ small miscellaneous The temperature should preferably be 25.t:, the reaction _ preferably w peak is to obtain a smaller particle size of the metal particles / no silk soil composite m lying can be carried out under the sound _ fall. A drying step may be included to obtain a nanoparticle/inorganic clay composite for antibacterial use in the form of a powder. The present invention is applied to a silk metal particle/inorganic clay composite for anti-caries, which is mainly used for inhibiting gram positive Growth of bacteria, gram-negative bacteria or multi-drug resistant Staphylococcus aureus. The anti-resolving agent of the present invention comprises a nano-particle/inorganic clay composite of a therapeutically effective dose and a solution (4). The solution is preferably water. The shot is used for antibacterial Nailai metal particles/inorganic clay composites. The solid content is greater than 001wt%. Generally, the solid content used to inhibit Gram-positive bacteria is greater than that of 〇. 05 w微佳's 雠 雠 雠 阴性 negative thief has a strong resistance to Staphylococcus aureus More preferably, it is more than 0.01 wt%. 200944212 [Embodiment] The present invention proposes an antibacterial mechanism of a novel nano-particle (Agnanoparticle), which adsorbs nano-silver particles by using clay as a carrier. The barrier causes the nano-silver particles to fail to enter the cell interior and avoid destroying the cells. See Figure 2, (a) shows that only the glutinous rice silver particles can directly enter the interior of the cell; (b) shows the negative charge by the clay surface. The nano-silver particles are adsorbed, so that the nano-silver particles can not enter the cell, so that the cells can be avoided. The materials used in the preferred embodiments and the application examples include: 1. Nano-plate: nanosilicate platelet (NSP), It can be obtained by delamination of sodium ion montmorillonite (Na-MMT); for detailed preparation methods, please refer to the Republic of China Patent Nos. 280261, 284138, 270529 and the announcement numbers 577904, 593480, etc. 2 Bentonite. A synthetic layered dreaming clay mineral obtained from c〇_〇p Chemicai Co. 'brand name is blue, cation exchange capacity (CEC) = 〇. 67 mequiv/g. 3. AgNCb: exchange replaces Na+ between clay layers, and forms nano silver particles after reduction to form e 1 NaBH4: strong reducing agent, which can quickly reduce silver ions.

5. Methanol: CHsOH, 95%, is a weak reducing agent, nano silver at 30~150 °C. 6. Glycol: C2H4(0H)2, is a weak reducing agent, 30~15 (TC can slowly reduce silver ions into nano silver. 7. Sulfonamide: silver sulfadiazine, provided by Xinghui Pharmaceutical Co., Ltd. , the trade name Silvazine, its silver content of 2. 6 mM, equivalent to 0.5 wt% of AgNP / SWN. 8. Species: Staphylococcus aureus 71 (431; 10781), Streptococcus pyogenes Rob 193-2), Pseudomonas aeruginosa, Salmonella (Salinonel la 4650; 4653) and Escherichia coli are all wild isolates provided by Dr. Lin Junhong, Taiwan Institute of Animal Science and Technology; 200944212 Acinetobacter Baumannii was provided by Dr. Huang Jiechen from the Department of Life Sciences of National Chung Hsing University; 10 strains of multi-drug resistant Staphylococcus aureus were collected by the physician of the Taichung Veterans General Hospital, Huang Fangliang, for the 'fungi Penicillium, TrichodermaHA, Fusarium, Cladosporium, Aspergillus 9. Preparation of standard bacterial solution: The overnight culture solution was added to fresh 1111^3_this 1_1^1^ (LB) liquid medium for about three hours in a volume of 1/1 ,, and then measured with a spectrophotometer. After the culture, the absorbance of the bacterial solution in 〇Dm〇, select the bacterial liquid with ODmd between 0.4 and 0.6, which is the standard bacterial liquid. 10. Preparation of the fungal spore suspension··Inoculate the corn glutamate财加dextr〇se agar, ❹ PDA) on solid medium and cultured at 28. (: three days of colonies, 〇. 〇 8 % tween 80 flushed down the medium into the test tube 'shock surplus' to disperse the spores, then Blood count ^ Calculate the number of arms ' and dilute this spore suspension to 1 sp 5 spores / ml, and finally mix this suspension with 1:1 of potato dextrose biOth (PDB) liquid medium Is the test spore suspension (5x104 spores/ml). The natural or synthetic clays that can be used in the present invention include: 1. Synthetic fluoride mica: synthetic flU0rine mica, for example (4) p plus - (7). Trade name somASIF manufactured ME-100, CEC = 1.20 mequiv/g. 2. Bentonite: laponite, a synthetic layered Wei salt clay mineral, CEC=〇. 69 m_v/g. 3. [An.nH2〇]inter : M11 is a divalent metal ion such as Mg, Ni, Cu or Zn H valent metal ion such as M, I, Fe Ga ; ^ CO^ >NOa*; (anionic exchange opacity > AEC) = 2.00~4. 00 mequiv/g 〇200944212 Example 1 Step (a) Reaction of Ag+ in place of clay layer Na+ was prepared by first preparing SWN solution (5 wt%) and AgN〇3 solution (5 wt%). Then, AgN〇3 (aq) (〇. 68g) was added, and the SWN solution (30 g) was slowly added to make Ag+/CEC=0.2/1.0, and the solution was pale beige. Step (b) Reducing interlayer silver ions with a reducing agent methanol. Adding the solution of step (a) to a sufficient amount of sterol (Me〇H, about 6-8 mL), heating to 5 ° C in water, and the solution starts to react. The color slowly changes. After 2 to 3 hours of reaction, the solution appeared red, and after mixing, it was the product AgNP/SWN.实施 Example 2 Step (a) Reaction of Na+ in the Ag+ Substituted Clay Layer SWN solution (5 wt%) and AgNOa solution (5 wt%) were prepared. Then, AgN〇3 <aq) (3.4143 g) was added, and the SWN solution (30 g) was slowly added to make Ag+/CEC = 1.0/1.0, and the solution immediately appeared beige. Step (b) Reducing interlayer silver ions with a reducing agent sterol The solution of step (a) is added to a sufficient amount of sterol (MeOH, about 6 to 8 mL), heated to 5 (TC) by water, and reacted for 2 to 3 hours. After the 'solution is red, after the oscillation is the product AgNP / SWN. 〇 Example 3 Step (a) Ag + substituted clay layer Na + reaction First prepare SWN solution (5 wt%) and AgN〇3 solution (5 wt%) 〇 Then take _〇3 («〇(6.8g), slowly add to the SWN solution (30g), make Ag+/CEC=2.0/l.〇, the solution will immediately appear beige. Step (b) Reductive silver with reducing agent methanol The solution of step (a) is added with a sufficient amount of methanol (MeOH, about 15-20 mL). At this time, the solution does not change, and it still shows pale beige. After heating to 70-80 t by water, the solution starts to react. Slowly change the 'reaction 2~3 hours' solution is dark red wine, after shaking, it is the product AgNp / s eggs. 200944212 Example 4 Step (a) Ag + substitution of clay layer Na + reaction _ 4 preparation of SWN solution (1 wt %) and AgN〇3 solution (1 wt%). Then take AgN0_(3.4143g) and slowly add it to SWN solution (30g) to make Ag+/CEC=1.0 /1.0, the solution immediately appeared beige. Step (b) Reducing interlayer silver ions with reducing agent methanol. Add the solution of step (a) to a sufficient amount of methanol (MeOH, about 6~8 mL). 'The solution did not produce any change at this time' Still showing pale beige. In the environment of sonic agitation, it is heated to ~8 by water (rc, the solution starts to react, the color changes slowly, and the product is AgNP/SWN after shaking). Example 5 Step (a) Ag+ Prepare SWN solution (1 wt%) and AgN〇3 solution (1 wt%) by replacing Na+ between clay layers. Then take AgN〇3(aa) (3.4143g) and slowly add it to SWN solution (3〇g). The ratio of AgVCEC is 1·0/1. 0, Ag+ replaces Na+ between the clay layers, and the solution will be pale beige. Step (b) Reducing interlayer silver ions with reducing agent 8114 © powdered NaBH4 (0. 0375g) The solution of step (a) is added in portions, and the solution will immediately show a deep yellow-green color. After stirring and shaking, the solution is the product AgNP/SWN. Example 6 Step (a) Ag+ Substituting Na+ in the clay layer NSP solution (1 wt%) and AgN〇3 solution (1 wt%).

AgN〇3Uq)(3. 5l6〇g) ' Slowly added to the MMT solution (30g), the ratio of AgVCEC is 1. 0/1. 〇, Ag replaces the Na+ between the clay layers, and the solution will appear milky white. Step (b) Reducing interlayer silver ions with reducing agent ethylene glycol 200944212 The solution of step (a) is added with a sufficient amount of ethylene glycol (EG, about 〇. Bu 5 mL), at which time the solution does not change, and still appears milky white. . In the environment of sonic agitation, it is heated to 4〇~8〇艽 by water, and the solution begins to react. The color changes slowly. After shaking, it is the product AgNP/NSP. Table 1 Example Clay Clay Initial Concentration AgNOs Initial Concentration AgVCEC Reducing Agent 1 SWN 5 wt% 5 wt% 0.2/1.0 Methanol 2 SWN 5 wt% 5 wt% 1. 0/1.0 Methanol 3 SWN 5 wt% 5 wt% 2.0/1.0 Methanol 4 SWN 1 wt% 1 wt% 1. 0/1.0 methyl alcohol 5 SWN 1 wt% 1 wt% 1.0/1.0 NaBH4 6 NSP 1 wt% 1 wt% 1.0/1.0 Ethylene glycol The present invention is made of clay As a carrier and a protective agent, the silver after reduction is uniformly dispersed and does not aggregate. The obtained nano silver particles are dried, and the silver particles are still adsorbed by the clay and uniformly dispersed on the carrier. Figs. 3 and 4 are SEM images of silver particles obtained by reducing silver ions with MeOH and NaBH4, respectively, and having an average particle diameter of about 20 nm. The nano silver particles obtained by the decyl alcohol reduction method are superior to the NaBH4 reduction method in uniformity and particle size. Fig. 5 is an SEM image of the nano silver particles obtained in Example 4, the particle size of which is further reduced to only about 10 nm, and is still uniformly attached to the surface of the clay. From this, it can be seen that in the reduction reaction, the acoustic wave is mixed, and since the energy is increased, the molecules have a large interference behavior with each other, so that the particle diameter of the formed particles tends to become small. In order to verify the antibacterial effect of the nano silver particle/clay composite of the present invention, the AgNP/SWN and AgNP/NSP prepared in the above Examples 4 and 6 were prepared to prepare test solutions of different concentrations. A test solution having a concentration of 0.5 wt% was compared in the following tests. The test methods and results are as follows: -12- 200944212 A_Inhibition of bacterial growth ability in solid medium The AgNP/NSP (or AgNP/SWN) aqueous solution was added to the unsolidified LB solid medium at different ratios to make different Concentration of 1 hmLB solid medium. 1 〇 fresh broth was evenly spread on LB solid medium containing different concentrations of AgNp/Nsp (or Na/p/SWN). The amount of colony formation was calculated after further incubation at 37 ° C for 16 hours. The colony is calculated by equally dividing the disk into 8 or 16 blocks, and selecting the number of cells to calculate the growth, and multiplying by the number of divisions, which is the total number of colony growth. The results are as follows: 1. Gram-positive bacteria 〇1·1 AgNP/SWN (S. aureus 71, 43 Bu 1078 S. pyogenes) The results are shown in Fig. 6, and the vertical axis is the percentage of the number of colony growth. Because the difference in the number of g-falls grown by different strains is quite large, the average value of the sages is the picture, showing the relative ratio of the number of growing ages in each group. The towel containing AgNp/SWN (G.丨wt%) had the best inhibitory effect on both bacteria, and AgNP/SWN (〇.〇1 wt%) was similar to the results of the control group of Shaw SWN alone and no addition. 1. 2 AgNP/NSP (S. aureus 71, Streptococcus pyogenes) The results are shown in Figure 7, in which AgNp/NSP (0.1 wt%) has the best inhibitory effect on both bacteria; AgNP/NSP ( The inhibitory effect of 0.05 wt0/〇, AgNP/NSP (0.03 wt%) on Staphylococcus aureus was second; AgNP/NSP (0.01 wt%) was similar to the results of SWN alone and no added control group. . 袼 阴性 negative bacteria ' 2.1 AgNP / SWN ( Escherichia coli, Pseudomonas aeruginosa, Salmonella 4653, 4650, Acinetobacter baumannii) The results are shown in Figure 8 where AgNP / STO (〇. 1 wt%) for various The inhibitory effect of the bacteria was the best, and the concentration was 0·01 wt%, which was similar to the result of using SWj alone and the control group without added. 2.2 AgNP/NSP (Escherichia coli, Pseudomonas aeruginosa, Salmonella 4653, 4650, Bower Acinetobacter) •13· 200944212 The results are shown in Figure 9, in which AgNP/NSP (0.1 wt%) has the best inhibitory effect on various bacteria.

AgNP/NSP (0.05 wt%), AgNP/NSP (0.03 wt%), and AgNP/NSP (0.01 wt%) were similar to those of the SWN alone and the control group without addition. B. For the growth resistance inhibition test of multi-drug resistant Staphylococcus aureus, the test method is the same as A, and the test results are as follows:

1. The AgNP/SWN results are shown in Figure 10, where AgNP/SWN (0.1 wt%) has the best inhibitory effect. When the concentration is ❹0·G1 wt%, it is the same as SWN and no added control group. The results are similar.

2. AgNP/NSP results ^ Figure 11 shows that _P/NSP (0.1 ritual) has the best inhibitory effect, AgNP/Nsp (〇· 05 wt/O second' concentration is 〇. 〇3%, 〇. The % of 〇1 is similar to the result of using Nsp alone and the control group without addition. C· _ growth ability inhibition test in liquid medium _ liquid medium test is divided into six groups, including different concentrations AgNP/NSP (or "NSP (or let) with no silver nanoparticles, siivazine (as a positive control)) was given to the control group, and the total amount of LB liquid medium and drug mixture after each group was 1 meb In the 2+ 2+ group, 1M1 standard bacterial solution was added and then cultured at 37 〇C, and then 0, 0.5, «-h ^ 1^"* 10 ^1 60 ^ ^ LB ®^ ° Hours' counts the number of secrets formed by each coffee. The results are as follows: 1. Gram-positive bacteria (Staphylococcus aureus)

1.1 AgNP/SWN, where the number of @fall growth is the vertical axis' compares its bacteriostatic effect. The result is as shown in Figure 12.

Although the silver content of Zlne is equivalent to AgNP/SWN (0.5% wt), the inhibitory effect is not 200944212 such as AgNP/SWN (0.5 rt%). The effect of AgNP/SWN (0_ 1 wt%) was second; AgNP/SWN (〇. 〇 (礼礼), SWN (0.5 wt%), the positive control group containing Silvazine, and the control group without any drug were similar. 》

1. 2 AgNP/NSP • ^ . ► Results As shown in Figure 13, the silver content of Silvazine is equivalent to AgNP/NSP (0.5% wt), but the inhibition effect is not as good as AgNP/NSP (0.5 wt% ). The effect of AgNP/NSP (〇·1 wt%) was second; AgNP/NSP (0.011 wt%) 'NSP (0.5 wt%), the positive control group containing Silvazine and the control group without any drug were effective. similar. 2. Gram-negative bacteria (Pseudomonas aeruginosa)

2.1 AgNP/NSP results are shown in Figure 14, where AgNP/NSP (0.5% wt) is still superior to Silvazine. However, the initial inhibitory effect of AgNP/NSP (0.1%%wt) was slightly inferior to that of siivazine and AgNP/NSP (0.5%wt), but good inhibition was achieved after 12 hours. The inhibitory effect of AgNP/NSP (0.01% by weight) was similar to that of the control test using SWN alone and without addition.

2.2 AgNP/SWN 0 The results are shown in Figure 15, where AgNP/NSP (0.5%wt), AgNP/NSP (0.1%wt), and Silvazine have slightly different inhibitory effects in the first hour, but 1 After a few hours, there is a good inhibition effect. * The inhibitory effect of AgNp/SWN (0.01 wt%) is similar to that of the control test which is still used alone and without addition. D. AgNP/NSP inhibition test of fungal spore germination ability 1. In a liquid medium, the spore suspension of Aspergillus was directly mixed with different concentrations of AgNp/NSp, and cultured in PDB medium at 28 ° C for 16 hours. -15- 200944212 = As shown in the 16th _ shows 'AgNP/NSP ((U wt%) medium, no bacteria L, shape 'and almost no suspended stalks' are indicated] The domain doctors, - and A_SP (10) 〗 〖fft%) may be due to the lower concentration, the formation of hyphae can be found at the beginning, but also see the AgNP/NSP fiber planting _ Wei. A large number of hyphae can be seen in the Lai. The blocky substance in the figure and the substance on the surface are AgNP/NSP. 2. In a solid medium, a fixed amount of _ sub (Planus, Trichoderma HA, Fusarium, Cladosporium, Aspergillus) ❹ 洋 洋 洋 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有〇1 _, foot (〇 ^

Wt%) was not cultured on pM solid medium of any drug (control group) at room temperature for about several hours. None of these media contain any nutrients. As a result, no hyphae were found in the group (峨·1 wt%), and the other three groups were able to see the formation of the ride. Calculate the ratio of the five true g and _ fresh germination to the current (four), as shown in Figure 17. Ε. Effect of AgNP/SWN mixed in different ratios on bacterial growth inhibition ❹ Example 1 (Ag+/CEC=〇.2/1.0), Example 2 (Ag+/CEC=1.0/l.〇), Example 3 (AgVCEC=2. 0/1. 〇) The prepared AgNp/SWN is formulated into an aqueous solution of 〇.i (iv), 〇. 〇5 _, 〇. 〇iw. After fixing the silver content, it was added to the LB solid medium to carry out a bacterial growth inhibition experiment, thereby understanding whether the amount of the clay component has an influence on the ability to inhibit bacterial growth. As a result, as shown in Fig. 18, the three ratios of AgNP/SWN were good at the concentration of 0.1 wt%, 〇. 〇5%. However, when Handu is 〇. 〇1 wt%, the higher the ratio of Ag+/CEC, the better the bacteriostatic effect. In other words, too high a clay content may promote the growth of bacteria. F. Nude mouse burns the scald with iron plate to heat the scalpel metal shank (the temperature is set to post on the back of the nude mouse plus seconds. With the 200944212 scalpel blade to scrape the upper surface of the scald and transparent, so that the dermis is exposed. 0D cans of Staphylococcus aureus (l〇〇Al) in 〇.4~〇.6, evenly dripped on the surface of each nude mouse except the control group. After the bacteria, the wound was wrapped with Tegaderm waterproof breathable dressing. After 24 hours, the inflammatory condition was observed as follows: Table 2 Group 1 Drug dosage, concentration result 1 〇AgNP/iNJSP 100"1,1 wt% No hair _ inflammation Phenomenon L 〇AgNP/layer 100/z 1 * 1 wt% No inflammatory phenomenon 6 A Renewed amine silver Silvazine 100//1 » 0.19 wt% No inflammation occurred 4 Γ JnSP 100"1 Significant inflammatory phenomenon 0 η 8 There was a significant inflammation in the i-liquid. No inflammation was observed without any bacterial solution and drugs. As above, the control group without any treatment did not produce inflammation, but the negative control group (negative CQntrQl) ), it produces obvious inflammation, so To determine that our experiments are not contaminated by bacteria in the environment. On the other hand, it can be seen that Na (10) and AgNP/SWN can avoid the occurrence of inflammation in the animal body and the main component of the commercially available burnt cream. 'Also, SP alone cannot inhibit the growth of bacteria, and thus inflammation occurs. From the above test results, it can be found that the nano silver particles/inorganic clay composite of the present invention has the following characteristics: 1. Adsorption of naphthalene by clay domain The silver-colored particles, due to the steric obstacles caused by the clay, prevent the nano-silver particles from entering the cell and avoid destroying the cells. 2. AgNP·(〇.! wt %) and AgNp/Nsp (〇.! 听%) In the case of solid culture, it can inhibit the above bribe growth. At the same time, it can also inhibit the germination of real coffee. •17. 200944212 3. Add water or other suitable solvent or carrier to form a stable water-based composite for daily use. Disinfected antibacterial spray and scald medicinal agent for medical use. Appropriate and more long-acting and sub-filament fiber (also (4) content is not produced), so the machine is transported and produced. And more The blackness of 'black' does not produce occupational accumulation for more than half a year, and maintains the unique golden yellow, which will not be oxidized. 200944212 The illustration is simple: Figure 1 shows the inhibitory effect of the commercially available Silvazine on staphylococci. In the case of clay, the behavior of nano-silver particles on the cell surface. Figures 3 and 4 show the SEM images of the nano-silver particles obtained by successively reducing the silver ions. Figure 5 shows the SEM of the nano-silver particles obtained under the acoustic wave. Figure. = 图显向^面加人晴, 嫩嫩_阳罐长抑制试验结❹=清娜卿SP加人LB _培撕糊阳阳罐长抑制试验结结=_ shows the addition of AgNP/SWN to LB _ medium In the middle of the rat _ growth inhibition test showed that AgN earned into the LB solid medium for the growth inhibition test of gram-negative bacteria t == T into 16 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Figures 12 and 13 of Qinghuang's golden yellow grapes show that AgNP/S is added to LB liquid medium for bacterial growth inhibition test, and Figure 15 shows that AgNP/NSP is added to LB liquid medium for bacterial growth inhibition test. , ^ fruit. Figure 16 shows the results of inhibition of fungal spore germination ability by adding _/朦 to PDB medium. Figure W shows a quantification of the results of the inhibition of the bud ability by adding AgNP/NSP to the acacia-like medium without any nutrients. The digraph shows the effect of different ratios of iAgNP/SWN on bacterial growth inhibition. •19·

Claims (1)

200944212 X. Patent application scope: '--Teng Teng antibacterial nano metal particles/age-free soil composites, including metal particles and #-like inorganic clays, wherein the aspect ratio of the flake inorganic clay is 1 (H(9), _, And as the body of the metal particles, so that the metal particles reach the dispersion of the surface, the size of the antibacterial nano metal particles/inorganic composite is 5 to 100 nm. · 'Replication 2. As claimed in item i The metal particles described in the antibacterial nano metal particle/inorganic clay composite have a spherical structure. 〇❹ 3. The anti-g silk metal particle/inorganic paper composite as described in claim i. The metal particles in the material are gold, silver, copper or iron. 4. The aspect ratio of the flake inorganic clay in the antibacterial nano metal particle/inorganic clay composite according to the scope of claim [1] is 100. 〜1,〇〇〇., 5. The flaky inorganic clay used for antibacterial nano metal particles/inorganic clay compound as described in the scope of claim i is metazo, cinnabar, montmorillonite Synthetic mica, kaolin, slippery , attapulgite, vermiculite and layered double hydroxide (LDH). ^, 6. The antibacterial nano metal particle/inorganic clay composite as described in claim i, wherein the sheet The inorganic clay has a tetrahedron: the structure of the octahedron is about 2: 丨. ', 7. The nanoparticle/inorganic clay composite for antibacterial as described in the scope of the patent application, wherein The weight ratio of the nano metal particles to the clay is 1:1 〇〇 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The cation exchange capacity range is 〇·! mequiv/g~5. 〇脉(四)心., 9. The anti-bacterial Nailai metal particle/inorganic clay compound as described in claim 1 of the patent application, in which Sto The ratio of the ion amount of the particle to the age of the silk of the grain of the money is 4 for the antibacterial nano metal particle/inorganic clay compound described in the scope of claim patent, and the eight series are used to suppress the gran Positive g, growth of Gram-negative thief fungus. The antibacterial nano metal particle/inorganic clay composite described in item i, 200944212 f is used for inhibiting Staphylococcus aureus, Streptococcus pyogenes, Pseudomonas aeruginosa, Salmonella, Escherichia coli, Acinetobacter baumannii , multi-drug resistant Staphylococcus aureus, fungus growth 12. Ganru as claimed in the scope of the application for the antibacterial nano metal particles / inorganic clay complex of a powder. a preparation comprising a therapeutically effective amount of a nano-particle/inorganic clay composite according to the above-mentioned patent scope, and a solvent or carrier. H. An antibacterial preparation wherein the solvent is water. The antibacterial preparation of claim 13, wherein the antibacterial nano metal particle/inorganic clay composite has a solid content of more than 0.01 wt%. The anti- _, as described in claim 13 of the patent application scope, is used for inhibiting gram-positive bacteria when the solid 2 is greater than 0.05, and the solid content of the gram-negative bacteria or the multi-drug resistant Staphylococcus aureus is greater than 0.01 wt%. Π A method for the synthesis of a heterogeneous metal ion compound, a flaky inorganic clay and a reducing agent in water, wherein the ratio is 10,0,000, which is A dispersant or protectant for the metal to achieve nano-dispersion of the metal. 18. The method of claim 17, wherein the metal is gold, silver, copper or iron. The method of claim 17, wherein the metal compound is Na Na Na, AgBr, AuBr3, AuCl or HAuCh · 3 shame. The method according to item 17, wherein the sheet is The aspect ratio of the inorganic clay is as described in claim 17, wherein the flaky inorganic clay is terracotta, =: synthetic mica, high-strength, talc, attapulgite, feldspar and A layered double gas oxide 22, as in the method of claim 17, wherein the flaky inorganic clay has a structure of about 2:1 of the octahedron. -2K 200944212 23. The method of claim 17, wherein the weight ratio of the nano metal particles to the clay is 1:100 to 100:1. 24. The method of claim 17, wherein the cation exchange capacity of the flaky inorganic clay The range is 0·1 mequiv/g~5. 0 mequiv/g. 25. The method of claim 17, wherein the ratio of the equivalent of the metal ion compound to the cation exchange equivalent of the flaky inorganic clay is 〇.b. 26. If the scope of patent application is 17 The method, wherein the reducing agent is methanol, ethanol, propanol, butanol, methyl ketone, ethylene glycol, propylene glycol, butylene glycol, glycerol, pvA (p〇lyvinyi aic〇h (4), ❹ (PQlyethylene glycGl , PPG (Polypropylene glycol) dodecyl alcohol or sodium borohydride (NaBH 〇. 7. The method of claim 17, wherein the reduction reaction is carried out under ankle boots, the reaction time is 1 to 20 hours =. For example, the patent application is followed by the method described in item 17, wherein the reduction reaction is carried out under the mixing of silk. The surface of the invention is claimed in paragraph 17 of the patent, and the towel comprises a dry step after the reduction reaction to obtain a powder form. Product. 方法 Side method of the 17th item, the fine (4) Zhishou 31 it system is used to inhibit the growth of gram-positive bacteria and fine-grained. The method of clay compounding Particles/inorganic strontium is used to inhibit the growth of Staphylococcus aureus, Streptococcus pyogenes, Pseudomonas aeruginosa, Salmonella 'Gana' multi-drug resistant Staphylococcus aureus, fungi. • 22- 200944212 VII. Designated representative map: (1 The designated representative of the case is . (B) of FIG. (B) This reference numerals of FIG. Representative briefly described: 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 200944212 Patent description of the invention. The date of the year is another correction page (this). (The format and order of this manual> Change, ※Do not fill in the mark part) Concentrate 1卩<:Classification I, invention name: (Chinese/English) Nano silver particle/clay composite for antibacterial and its manufacturing method II. Applicant: (Total 1 person) ※Application number··mk Λ3 (200,^ ※Application for Japan: to .-. Embed 1卩<: High seas: (1) k S 005.01^ Name or Name: (Chinese / English) National Taiwan University National Taiwan University Representative: (Chinese / English) Li Wei Si-chen Lee Residence or Business Office Address: (Chinese / English) Section 4, Roosevelt Road, Zhongzheng District, Taipei No. 1, Sec. 4, Roosevelt Road, Taipei, 10617 Taiwan Nationality: (Chinese/English) Republic of China' III. Inventor: (4 in total) Name: (Chinese/English) 1. Lin Jiangzhen 2. Zhou Zhicheng 3. Su Honglin 4. Hongda as a nationality: (Chinese / English) 1-Chinese People's Republic 2 - Republic of China 3 - Republic of China 4 - Republic of China