[go: up one dir, main page]

US20020051823A1 - Nanosilver-containing antibacterial and antifungal granules and methods for preparing and using the same - Google Patents

Nanosilver-containing antibacterial and antifungal granules and methods for preparing and using the same Download PDF

Info

Publication number
US20020051823A1
US20020051823A1 US09/840,906 US84090601A US2002051823A1 US 20020051823 A1 US20020051823 A1 US 20020051823A1 US 84090601 A US84090601 A US 84090601A US 2002051823 A1 US2002051823 A1 US 2002051823A1
Authority
US
United States
Prior art keywords
solution
nag
nags
nanosilver particles
nanosilver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US09/840,906
Other versions
US6379712B1 (en
Inventor
Jixiong Yan
Jiachong Cheng
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LEGEND WIN FINANCE Corp
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US09/840,906 priority Critical patent/US6379712B1/en
Assigned to GLOBOASIA L.L.C. reassignment GLOBOASIA L.L.C. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHENG, JIACHONG, YAN, JIXIONG
Application granted granted Critical
Publication of US6379712B1 publication Critical patent/US6379712B1/en
Publication of US20020051823A1 publication Critical patent/US20020051823A1/en
Assigned to LEGEND WIN FINANCE CORPORATION reassignment LEGEND WIN FINANCE CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GLOBOASIA, LLC
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/38—Silver; Compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the present invention relates to nanosilver particles-containing antibacterial and antifungal granules (NAGs).
  • the nanosilver particles are attached to the surfaces and pores of stalk marrow of Juncus effuses L , which acts as an inert carrier for nanosilver.
  • Each of the nanosilver particles contains a metallic silver core which is surrounded by silver oxide.
  • the size of the nanosilver particle is between 1-100 nm in diameter.
  • the present invention also relates to methods for preparing the NAGs and for using the NAGs.
  • the NAGs can be used in a variety of healthcare, medicinal and industrial products.
  • Silver is generally a safe and effective antimicrobial metal.
  • Silver ions function in adversely affecting cellular metabolism to inhibit bacterial cell growth. When silver ions are absorbed into bacterial cells, silver ions suppress respiration, basal metabolism of the electron transfer system, and transport of substrate in the microbial cell membrane. Silver ions also inhibit bacterial growth by producing active oxygen on the surface of silver powder and silver-plated articles. Silver has been studied for antibacterial purposes in the form of powder, metal-substituted zeolite, metal-plated non-woven fabric, and crosslinked compound.
  • U.S. Pat. No. 5,785,972 discloses a therapeutically active composition
  • a therapeutically active composition comprising a solution of colloidal silver, helichrysum angustifolium or helichrysum italicum oil, and raw honey emulsified with water soluble lecithin.
  • the contact between microbial cells and silver ions is not ensured as the silver ions quickly become eluted in the solution.
  • Silver ions in solution are difficult to handle and therefore of limited use.
  • U.S. Pat. No. 5,709,870 discloses a silver-containing antimicrobial agent comprising a silver salt of carboxymethylcellulose and having a degree of substitution of carboxymethyl group of not less than 0.4.
  • Chinese Patent No. 87100231A discloses an antibacterial dressing made from nitrilon crosslinked with copper salts in alkaline medium. The resulted cloth shows antibacterial activity on ten (10) bacteria including Staphylococcus aureus (MRSA).
  • MRSA Staphylococcus aureus
  • Japan Process Technique Vol. 17, No. 7, teaches a nitrilon fiber manufactured from copper and sulfur salts.
  • the fiber has bacteriostatic effects on Escherichia coli, Staphylococcus aureus, Bacillus subtilis , and Epidennophyton.
  • Japanese Patent No. 3-136649 discloses an anti-bacterial cloth used for washing breasts of milk cow.
  • the Ag + ions in AgNO 3 were crosslinked with polyacrylonitrile and it had anti-bacterial activity on six (6) bacteria including Streptococcus and Staphylococcus.
  • Japanese Patent No. 54-151669 discloses a fiber treated with a solution of a compound of copper and silver. The solution is evenly distributed on the fiber. The fiber is used as an anti-bacterial lining inside boots, shoes, and pants.
  • U.S. Pat. No. 4,828,832 discloses a composition for treating skin lesions which is made up of metallic silver particles having a diameter of 1 to 10 ⁇ m and an optional oxidizing agent randomly disbursed within a carrier of inert filler such as kaolin or talc.
  • U.S. Pat. No. 5,824,267 discloses a plastic material having a bactericidal surface on which a number of ceramic or base metal particles of a mean diameter of 0.01 to 0.5 ⁇ m are embedded under the condition that a portion of each particle is exposed over the surface, and the ceramic or base metal particles have bactericidal metal particles of mean diameter of 0.0001 to 0.1 ⁇ m dispersively fixed thereon.
  • Such solid supports using synthetic polymer materials have been not widely adapted for medical and healthcare purposes. These materials usually require bonding or cross-linking of the silver or silver ions to the polymers. Such bonding or cross-linking may invoke allergic reactions in patients. These materials also do not have sufficiently high antibacterial activity due to the lack of sufficient surface contact with the bacteria. Additionally, the bactericidal activity of these materials rapidly diminishes as the silver ions become separated from the solid supports, thus, these materials do not show bactericidal activity over a prolonged period of time. Lastly, the processes for making these materials are complicated and time-consuming.
  • the present invention provides nanosilver-containing antibacterial and antifungal granules (NAGs).
  • the NAGs are made of stalk marrow of Juncus effuses L. (as a carrier) with nanosilver particles evenly dispersed on the surfaces and pores of the stalk marrow. These NAGs display longlasting bactericidal and fungicidal activities.
  • the NAGs of the present invention are safe to use for medical and healthcare purposes as well as used in industrial products.
  • the present invention also provides a method for making the NAG which is suitable and feasible for large scale industrial production.
  • the present invention is an improvement over Chinese Patent Nos. CN 1034090, CN 1093004, and CN 1123665, which are herein incorporated by reference.
  • CN 1034090 discloses a method of attaching nanosilver particles to textile.
  • CN 1093004 discloses a suture or medical thread containing nanosilver particles.
  • CN 1123665 discloses a granule containing nanosilver particles attached to stalk marrow which can be used to disinfect tooth brush, for treatment of acne and pimples, and as cleansing agents to prevent gynecological infections such as vaginitis.
  • the method for making the NAGs and the utility of using the NAGs described in the present invention are different from those described in CN 1034090, CN 1093004, and CN 1123665.
  • the present invention provides nanosilver-containing antibacterial and antifiungal granules (NAGS) which comprise nano silver particles which are firmly and evenly attached to stalk marrow of Juncus effuses L .
  • the nanosilver particles are about 1-100 nm in diameter.
  • the individual nanosilver particle has a metallic silver core surrounded by silver oxide.
  • the NAGs display longstanding inhibitory effect on a broad spectrum of bacteria and fungi.
  • bacteria and fungi include, but are not limited to, Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus , Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus ( Salmonella morgani ), Pseudomonas maltophila, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B , Citrobacter, and Salmonella paratyphi C.
  • the NAGs are produced by (1) cutting the stalk marrow of Junicus effuses L . into pieces; (2) immersing the cut stalk marrow in a solution containing nanosilver particles to allow the attachment of the nanosilver particles to the cut stalk marrow; (3) after the attachment, drying the nanosilver particles-attached stalk marrow; and (4) grinding the nanosilver particles-containing stalk marrow to appropriate size to produce the NAGs. Before drying the nanosilver particles-containing stalk marrow, the stalk marrow is optionally washed with hot and cold water.
  • the nanosilver particles are made by dissolving silver nitrate in a solution containing concentrated ammonia water, glucose or ascorbic acid (as reducing agent), and an oxidizing agent.
  • a solution containing concentrated ammonia water, glucose or ascorbic acid (as reducing agent), and an oxidizing agent can be added to the solution to adjust the pH, and ethanol can be added to the solution to improve the solubility of the solution.
  • the preferred oxidizing agent is hydrogen peroxide (H 2 O 2 ).
  • the present invention also provides a method for preparing the NAGs.
  • the method comprises the following steps: (1) cutting the stalk marrow of Junicus effuses L , into pieces (about 0.5 to 2 cm at length); (2) preparing a nanosilver particles-containing solution; (3) immersing and thoroughly mixing the cut stalk marrow pieces in the nanosilver particles-containing solution to allow the attachment of the nanosilver particles to the cut stalk marrow pieces; (4) washing the cut stalk marrow pieces (preferably first with hot water, then with cold water); (5) drying the cut stalk marrow pieces; and (6) grinding the dried cut stalk marrow pieces to the desirable size(s) of the NAGs.
  • the NAGs have a size which is capable of passing through a No. 200 sieve. It is preferred to boil the cut stalk marrow pieces to remove unwanted water-soluble materials, followed by heat drying the boiled stalk marrow pieces, before soaking the stalk marrow pieces in the nanosilver particle-containing solution. It is also preferred to treat the nanosilver soaked stalk marrow pieces with heat until the stalk marrow pieces turn brown, before washing the stalk marrow pieces with hot and cold water.
  • the nanosilver solution is prepared by the following step-wise procedure: (1) dissolving silver nitrate (AgNO 3 ) crystal in a concentrated ammonia water solution; (2) adding glucose or ascorbic acid (as reducing agent) to the solution; and (3) adding an oxidizing agent to the solution.
  • the preferred oxidizing agent is hydrogen peroxide (H 2 O 2 ).
  • NaOH and ethanol can be added to the nanosilver solution to adjust the pH and improve the solubility of the nanosilver solution, respectively.
  • the present invention provides methods of using the NAGs.
  • the NAGs can be used in a variety of healthcare, medicinal, and industrial products.
  • the NAGs can be added to ointments, lotions, and/or solutions for treating humans or animals with skin trauma, such as acne or pimples, wound, burns, skin with bacterial or fungal infections.
  • the NAGs can be used in hygiene products, such as women gynecological washing solution, tooth brush soaking solution, or facial cleansing solution.
  • the NAGs can also be used as food preservatives (e.g., for preserving fruits and vegetables), water disinfectants, paper disinfectants (e.g., for preventing mold build-up in book, newspaper, certificate, envelope, stationary, money, paper food containers, etc.), and in construction filling materials to prevent mold formation.
  • food preservatives e.g., for preserving fruits and vegetables
  • paper disinfectants e.g., for preventing mold build-up in book, newspaper, certificate, envelope, stationary, money, paper food containers, etc.
  • construction filling materials to prevent mold formation.
  • the NAGs can be used as medicines to treat patients with gastrointestinal infection, sexually transmitted diseases, and eye diseases.
  • FIG. 1 shows the inhibitory effect of the NAGs on Staphylococcus aureus .
  • the horizontal axis of the curve is the treatment time, the vertical axis is the amount of the bacteria remained (measured by CFU (colony forming units)) after being immersed in the NAGs-containing solution.
  • Open circle indicates no NAGs. Close circle indicates with NAGs.
  • FIG. 2 shows the inhibitory effect of the NAGs on Escherichia coli .
  • the horizontal axis of the curve is the treatment time, the vertical axis is the amount of the bacteria remained (measured by CFU (colony forming units)) after being immersed in the NAGs-containing solution. Open circle indicates no NAGs. Close circle indicates with NAGs.
  • FIG. 3 shows the inhibitory effect of the NAGs on Pseudomonas aeruginosa .
  • the horizontal axis of the curve is the treatment time, the vertical axis is the amount of the bacteria remained (measured by CFU (colony forming units)) after being immersed in the NAGs-containing solution. Open circle indicates no NAGs. Close circle indicates with NAGs.
  • FIG. 4 is a flow chart indicating the process for making the NAGs in an industrial scale manufacturing.
  • chambers which are: (1) selection chamber; (2) separation chamber; (3) spraying chamber; (4) water removal chamber; (5) heat reaction chamber; (6) washing and soaking chamber; (7) drying chamber; and (8) grinding chamber.
  • the function of each chamber will be described in the following section (infra).
  • the present invention is directed to sustained-effect, broad-spectrum nanosilver containing antibacterial and antifungal granules (NAGs) and the process of manufacturing and using NAGs.
  • the NAGs of the present invention are made by attaching nanosilver particles to small pieces of stalk marrow of the plant Juncus effuses L .
  • the attachment of nanosilver particles to the NAGs have been confirmed by scanning electromicroscopy using AMRAY1910FE and TN-8502, which shows that the nanosilver particles on the NAGs were about 25 nm in diameter.
  • the nanosilver particles were shown evenly distributed on the NAGs.
  • the content of the nanosilver particles in the NAGs were analyzed by silver titrimetric method (see infra) to contain about 20-100 mg of silver per g of the NAGs. Also, due to the fact that the surface of the nanosilver particles was dark brown, which is a characteristic of silver oxidation, the surface of the nanosilver particles were identified to be silver oxide.
  • Juncus or rush pith “Deng Xin Cao” in Chinese, has the pharmaceutical name Medulla Junci effusi , botanical name Juncus effusus L . var. decipiens Buchen .
  • the plant belongs to the family of Juncaceae and is grown in the provinces of Jiangsu, Sichuan, Yunnan, and Guizhou in China. Juncus is harvested at the end of summer through autumn. There is no known major active ingredients in the plant. Because of its inert characteristics, the stalk marrow of Juncus is suitable for use as a carrier for nanosilver particles.
  • the NAGs of the present invention have demonstrated high antibacterial and antifungal effects. They are also non-toxic, non-stimulative, and non-allergic, so that they can be safely used in a large variety of healthcare, medicinal, and industrial products.
  • AgNO3+reducing agent Glucose or Ascorbic Acid
  • Silver ion is an effective antiseptic and germicide, and its organic salts, particularly in the form of nitrates, are commonly used with furazolidones and antibiotics in the treatment of bums.
  • Silver nitrate is one of the most powerful chemical germicides and is widely used as a local astringent and germicide. However, the nitrates irritate the skin.
  • the metallic silver as demonstrated in the second (2) reaction, is then undergone an oxidation to produce silver oxide (Ag 2 O) in the presence of an oxidizing agent.
  • the NAGs has a broad spectrum of antibacterial and antifungal activity.
  • the NAGs of the present invention had bactericidal and fungicidal effects on more than twenty (20) common pathogens, which include, but are not limited to, Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus , Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus ( Salmonella morgani ), Pseudomonas altophila , Arizona, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B
  • FIGS. 1 - 3 Examples of the antibacterial activity of the NAGs were demonstrated in FIGS. 1 - 3 .
  • FIG. 1 shows the effect of the NAGs on Staphylococcus aureus . The data demonstrate that within 8 hours of treatment with the NAGs, all of the S. aureus were killed.
  • FIG. 2 shows the effect of the NAGs on Escherichia coli . The data also demonstrate that within 8 hours of treatment with the NAGs, all of the E. coli were killed.
  • FIG. 3 shows the effect of the NAGs on Pseudomonas aeruginosa . The data show that within 12 hours of treatment with the NAGs, all of the P. aeruginosa were killed.
  • the NAGs were prepared by first cutting the stalk marrow of Juncus effuses L . into pieces of 0.5 to 2 cm at length. These small pieces of stalk marrow were washed, followed by boiling in water to remove any unwanted water soluble materials. The boiled stalk marrow pieces were than dried for later use.
  • a nanosilver particles-containing solution was prepared by first dissolving AgNO 3 in ammonia water, followed by adding glucose (as reducing agent) to the reaction solution. An oxidizing agent, preferably H 2 O 2 , was then added to the reaction solution.
  • the quantity or volume of each of the ingredients used in the nanosilver particle-containing solution is listed in Table 1.
  • Nanosilver Particles-Containing Solution Ingredients Quantity or Volume AgNO 3 15 Kg Ammonia Water 15 L Glucose 3 Kg Ethanol (95%) 5 L NaOH 0.5 Kg Oxidizing Agent (e.g., H 2 O 2 ) 100 ml Distilled Water up to 1000 L
  • FIG. 4 shows a flow chart of industrial production of the NAGs. The process was operated in the following chambers: (1) selection chamber; (2) separation chamber; (3) spraying chamber; (4) water removal chamber; (5) heat reaction chamber; (6) washing and soaking chamber; (7) drying chamber; and (8) grinding chamber.
  • stalk marrow of Juncus effuses L were cut into pieces, preferably at a length of about 0.5 to 2 cm.
  • the small pieces of stalk marrow were sieved through a selection process and transferred to the “separation” chamber, where the stalk marrow pieces were boiled and dried.
  • the small pieces of dried stalk marrow were then transferred to the “spraying” chamber where the nanosilver particles-containing solution was evenly sprayed and dispersed onto the small pieces of dried stalk marrow.
  • the small pieces of stalk marrow were further soaked with the nanosilver particles-containing solution in the “spraying” chamber for an adequate amount of time.
  • the small pieces of stalk marrow with attached nanosilver particles were then transferred to the “water removal” chamber where excess solution was removed from the pieces.
  • the heat-reacted stalk marrow pieces were transferred to the “soaking and washing” chamber, where the pieces were soaked and washed first with hot water, then with cold water, to remove any unattached nanosilver particles and water-soluble substances.
  • the washed nanosilver particles-attached stalk marrow pieces were then dried under heat in the “drying” chamber, and finally transferred to the “grinding” chamber to be ground to proper NAG sizes.
  • the final NAGs should contain no water-soluble substances other than silver.
  • Examples of the NAGs used in healthcare products include, but are not limited to, ointments, lotions, or spraying solutions for treating all kinds of injuries and/or bums, bacterial and fungal infections (including gynecological infections such as vaginitis), cleansing agents for clothing, women hygiene, acne or pimples, and soaking solution for tooth brush.
  • Examples of the NAGs used in medicinal products include, but are not limited to, internal medicines for treating gastrointestinal bacterial infection, sexually transmitted diseases, or as an eye drop for treating eye diseases.
  • Examples of the NAGs used in industrial products include, but are not limited to, food preservatives especially for fruits and vegetables, drinking water disinfectants, paper and construction filling materials preservation (especially to prevent mold formation).
  • Solvent HNO 3 solution.
  • the solution was prepared by mixing nitric acid with water at ratio 1:1 (v/v).
  • the concentration of nitric acid in the solution was 6N.
  • T Ag Ag amount in Ag standard solution/[(mean volume of the triplicates)-blank](The unit for T Ag is mg/ml.)
  • V was the volume of the NH 4 SCN solution added to the titration flask after the blank was deducted.
  • T Ag was in the unit of mg Ag/ml.
  • W was the weight of the NAG sample in mg.
  • the silver content of the NAGs was about 2-8%.
  • NAGs-containing solution Five (5) g of the NAGs were suspended in 500 ml of water and stayed in the solution for 24 hrs to obtain an NAGs-containing solution.
  • M-H liquid and solid culture media were used for activation and culture of the bacteria.
  • Staphylococcus aureus stock M120, Escherichia coli stock E109, and Pseudomonas aeruginosa stock PS208 were used for the testing. These stocks were provided by the Microbiology Teaching and Research Section at Henan Medical University.
  • the frozen stocks of bacteria were seeded onto solid culture media. Single colonies were picked and inoculated respectively in 2 ml liquid culture medium and cultured at 37° C. for eight (8) hours. Then, the liquid culture medium was diluted at 1:1000 and stored in refrigerator (around 0° C.) until ready for use. The solution contained about 10 5 CFU/ml bacterial stock.
  • the NAGs-containing solution was added to three (3) flasks, each containing 100 ml of the solution.
  • One (1) ml of the bacterial stocks of E. coli, S. aureus , or P. aeruginosa was then added to the three flasks, respectively.
  • the control was prepared by adding the bacterial stocks in the flasks containing water.
  • the inhibitory effect of the NAGs on the three different bacteria was conducted over a period of eight (8) hours.
  • the solution was diluted and plated on a culture plate to measure the number of remaining bacteria.
  • the solution containing the NAGs more than 99% of all the tested bacteria were killed, which demonstrated that the NAGs-containing solution was very effective as bactericide and could be used as disinfectant.
  • M-H liquid and solid culture media were used for activation and culture of the bacteria.
  • Staphylococcus aureus stock M120, Escherichia coli stock E109, and Pseudomonas aeruginosa stock PS208 were provided by the Microbiology Teaching and Research Section at Henan Medical University. The stocks were cultured in an incubator at 37° C. for 24 hours.
  • the frozen stocks of bacteria were seeded to a culture plate. Single colonies were chosen and inoculated in 2 ml liquid culture medium, respectively, where they were cultured at 37° C. for eight (8) hours. Then, the liquid culture medium was diluted at 1:1000 and stored in the refrigerator (around 0° C.) until ready for use. The solution contained about 10 5 CFU/ml bacterial stock.
  • Staphylococcus aureus stock M120 was provided by the Microbiology Teaching and Research Section at Henan Medical University. The stock was cultured in an incubator at 37° C. for 24 hours.
  • the frozen stock of bacteria was seeded to a culture plate. A single colony was chosen and inoculated in 2 ml liquid culture medium, respectively, where the bacteria were cultured at 37° C. for eight (8) hours. Then, the liquid culture medium was diluted at 1:1000 and stored in the refrigerator (around 0° C.) until ready for use. The solution contained about 10 5 CFU/ml bacterial stock.
  • a half of a toothbrush was immersed in 30 ml of a solution containing the NAGs for eight (8) hours.
  • the other half of the toothbrush was immersed in 30 ml of saline solution.
  • One (1) ml of each of the solutions was taken out after the 8 hours incubation, diluted, and tested for bacteria counts on plate. This method tested the natural existence of germs on the toothbrush and the effect of the NAGs on inhibiting the growth of the germs.
  • a half of the toothbrush was immersed in 30 ml solution containing the NAGs.
  • One (1) ml of the bacterial stock containing Staphylococcus aureus was added to the solution. At the end of the 8 hours incubation, 1 ml of the solution was taken out and tested for bacteria counts on plate.
  • the other half of the toothbrush was immersed in 30 ml of saline solution.
  • One (1) ml of each of the solutions was taken out after the 8 hours incubation, diluted, and tested for bacteria counts on plate. This method tested the bactericidal effect of the NAGs on toothbrush where known amount of S. aureus was inoculated in the solution
  • the bactericidal efficiency for the NAGs was about 95%.
  • the bactericidal efficiency for the NAGs was about 98%.
  • the NAGs were given to normal, healthy rats in a dose of 925 mg/kg of body weight per day for fourteen (14) days. This dose was more than 4,625 fold of the dose generally recommended to humans. The activities of rats were monitored. At the end of the 14 days period, no rats were dead or sick, which indicated that the NAGs were safe and non-toxic to rats.
  • a 5% (w/v) NAGs-containing solution was applied to the skin of the rabbits.
  • the rabbits were monitored at 1 hr, 24 hrs, and 48 hrs intervals. No rash, bruise, or any irritating reaction was observed on the rabbit skins, which indicated that the NAGs were safe and not creating any allergic reaction on the skins.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to nanosilver-containing antibacterial and antifungal granules (“NAGs”). The NAGs have longlasting inhibitory effect on a broad-spectrum of bacteria and fungi, which include, but are not limited to, Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus, Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus (Salmonella morgani), Pseudomonas maltophila, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B, Citrobacter, and Salmonella paratyphi C. The NAGs contain ground stalk marrow of the plant Juncus effuses L. which has been dispersed with nanosilver particles. The nanosilver particles are about 1-100 mn in diameter. Each of the nanosilver particles contain a metallic silver core which is surrounded by silver oxide. The present invention also provides a process for making the NAGs. The NAGs can be used in a variety of healthcare and industrial products. Examples of the healthcare products include, but are not limited to, ointments or lotions to treat skin trauma, soaking solutions or cleansing solutions for dental or women hygiene, medications for treating gastrointestinal bacteria infections, sexual related diseases, and eye diseases. Examples of industrial products include, but are not limited to, food preservatives, water disinfectants, paper disinfectants, construction filling materials (to prevent mold formation).

Description

    RELATED APPLICATION
  • This application claims the priority of U.S. Provisional Application No. 60/230,925, filed on Sep. 13, 2000, which is herein incorporated by reference.[0001]
    • FIELD OF THE INVENTION
  • The present invention relates to nanosilver particles-containing antibacterial and antifungal granules (NAGs). The nanosilver particles are attached to the surfaces and pores of stalk marrow of [0002] Juncus effuses L, which acts as an inert carrier for nanosilver. Each of the nanosilver particles contains a metallic silver core which is surrounded by silver oxide. The size of the nanosilver particle is between 1-100 nm in diameter. The present invention also relates to methods for preparing the NAGs and for using the NAGs. The NAGs can be used in a variety of healthcare, medicinal and industrial products.
    • DESCRIPTION OF THE RELATED ART
  • Metals including silver, copper, mercury, and zinc are known for anti-bacterial properties. Bacteria treated by these metals do not acquire resistance to the metals. Therefore, the bactericidal metals have advantages over the conventional antibiotics which often cause the selection of antibiotic-resistant microorganism. [0003]
  • Silver is generally a safe and effective antimicrobial metal. Silver ions function in adversely affecting cellular metabolism to inhibit bacterial cell growth. When silver ions are absorbed into bacterial cells, silver ions suppress respiration, basal metabolism of the electron transfer system, and transport of substrate in the microbial cell membrane. Silver ions also inhibit bacterial growth by producing active oxygen on the surface of silver powder and silver-plated articles. Silver has been studied for antibacterial purposes in the form of powder, metal-substituted zeolite, metal-plated non-woven fabric, and crosslinked compound. [0004]
  • U.S. Pat. No. 5,785,972 discloses a therapeutically active composition comprising a solution of colloidal silver, helichrysum angustifolium or helichrysum italicum oil, and raw honey emulsified with water soluble lecithin. However, the contact between microbial cells and silver ions is not ensured as the silver ions quickly become eluted in the solution. Silver ions in solution are difficult to handle and therefore of limited use. [0005]
  • To solve the problem in liquid state, various crosslinked agents and solid supports for silver ions have been developed. For example, U.S. Pat. No. 5,709,870 discloses a silver-containing antimicrobial agent comprising a silver salt of carboxymethylcellulose and having a degree of substitution of carboxymethyl group of not less than 0.4. [0006]
  • Chinese Patent No. 87100231A discloses an antibacterial dressing made from nitrilon crosslinked with copper salts in alkaline medium. The resulted cloth shows antibacterial activity on ten (10) bacteria including [0007] Staphylococcus aureus (MRSA).
  • Japan Process Technique, Vol. 17, No. 7, teaches a nitrilon fiber manufactured from copper and sulfur salts. The fiber has bacteriostatic effects on [0008] Escherichia coli, Staphylococcus aureus, Bacillus subtilis, and Epidennophyton.
  • Japanese Patent No. 3-136649 discloses an anti-bacterial cloth used for washing breasts of milk cow. The Ag[0009] + ions in AgNO3 were crosslinked with polyacrylonitrile and it had anti-bacterial activity on six (6) bacteria including Streptococcus and Staphylococcus.
  • Japanese Patent No. 54-151669 discloses a fiber treated with a solution of a compound of copper and silver. The solution is evenly distributed on the fiber. The fiber is used as an anti-bacterial lining inside boots, shoes, and pants. [0010]
  • U.S. Pat. No. 4,828,832 discloses a composition for treating skin lesions which is made up of metallic silver particles having a diameter of 1 to 10 μm and an optional oxidizing agent randomly disbursed within a carrier of inert filler such as kaolin or talc. [0011]
  • U.S. Pat. No. 5,824,267 discloses a plastic material having a bactericidal surface on which a number of ceramic or base metal particles of a mean diameter of 0.01 to 0.5 μm are embedded under the condition that a portion of each particle is exposed over the surface, and the ceramic or base metal particles have bactericidal metal particles of mean diameter of 0.0001 to 0.1 μm dispersively fixed thereon. [0012]
  • Such solid supports using synthetic polymer materials have been not widely adapted for medical and healthcare purposes. These materials usually require bonding or cross-linking of the silver or silver ions to the polymers. Such bonding or cross-linking may invoke allergic reactions in patients. These materials also do not have sufficiently high antibacterial activity due to the lack of sufficient surface contact with the bacteria. Additionally, the bactericidal activity of these materials rapidly diminishes as the silver ions become separated from the solid supports, thus, these materials do not show bactericidal activity over a prolonged period of time. Lastly, the processes for making these materials are complicated and time-consuming. [0013]
  • The present invention provides nanosilver-containing antibacterial and antifungal granules (NAGs). The NAGs are made of stalk marrow of [0014] Juncus effuses L. (as a carrier) with nanosilver particles evenly dispersed on the surfaces and pores of the stalk marrow. These NAGs display longlasting bactericidal and fungicidal activities. The NAGs of the present invention are safe to use for medical and healthcare purposes as well as used in industrial products.
  • The present invention also provides a method for making the NAG which is suitable and feasible for large scale industrial production. The present invention is an improvement over Chinese Patent Nos. CN 1034090, CN 1093004, and CN 1123665, which are herein incorporated by reference. CN 1034090 discloses a method of attaching nanosilver particles to textile. CN 1093004 discloses a suture or medical thread containing nanosilver particles. CN 1123665 discloses a granule containing nanosilver particles attached to stalk marrow which can be used to disinfect tooth brush, for treatment of acne and pimples, and as cleansing agents to prevent gynecological infections such as vaginitis. The method for making the NAGs and the utility of using the NAGs described in the present invention are different from those described in CN 1034090, CN 1093004, and CN 1123665. [0015]
    • SUMMARY OF THE INVENTION
  • The present invention provides nanosilver-containing antibacterial and antifiungal granules (NAGS) which comprise nano silver particles which are firmly and evenly attached to stalk marrow of [0016] Juncus effuses L. The nanosilver particles are about 1-100 nm in diameter. The individual nanosilver particle has a metallic silver core surrounded by silver oxide.
  • The NAGs display longstanding inhibitory effect on a broad spectrum of bacteria and fungi. Examples of the bacteria and fungi include, but are not limited to, [0017] Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus, Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus (Salmonella morgani), Pseudomonas maltophila, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B, Citrobacter, and Salmonella paratyphi C.
  • The NAGs are produced by (1) cutting the stalk marrow of [0018] Junicus effuses L. into pieces; (2) immersing the cut stalk marrow in a solution containing nanosilver particles to allow the attachment of the nanosilver particles to the cut stalk marrow; (3) after the attachment, drying the nanosilver particles-attached stalk marrow; and (4) grinding the nanosilver particles-containing stalk marrow to appropriate size to produce the NAGs. Before drying the nanosilver particles-containing stalk marrow, the stalk marrow is optionally washed with hot and cold water.
  • The nanosilver particles are made by dissolving silver nitrate in a solution containing concentrated ammonia water, glucose or ascorbic acid (as reducing agent), and an oxidizing agent. Optionally, NaOH can be added to the solution to adjust the pH, and ethanol can be added to the solution to improve the solubility of the solution. The preferred oxidizing agent is hydrogen peroxide (H[0019] 2O2).
  • The present invention also provides a method for preparing the NAGs. The method comprises the following steps: (1) cutting the stalk marrow of [0020] Junicus effuses L, into pieces (about 0.5 to 2 cm at length); (2) preparing a nanosilver particles-containing solution; (3) immersing and thoroughly mixing the cut stalk marrow pieces in the nanosilver particles-containing solution to allow the attachment of the nanosilver particles to the cut stalk marrow pieces; (4) washing the cut stalk marrow pieces (preferably first with hot water, then with cold water); (5) drying the cut stalk marrow pieces; and (6) grinding the dried cut stalk marrow pieces to the desirable size(s) of the NAGs. It is preferred that the NAGs have a size which is capable of passing through a No. 200 sieve. It is preferred to boil the cut stalk marrow pieces to remove unwanted water-soluble materials, followed by heat drying the boiled stalk marrow pieces, before soaking the stalk marrow pieces in the nanosilver particle-containing solution. It is also preferred to treat the nanosilver soaked stalk marrow pieces with heat until the stalk marrow pieces turn brown, before washing the stalk marrow pieces with hot and cold water.
  • The nanosilver solution is prepared by the following step-wise procedure: (1) dissolving silver nitrate (AgNO[0021] 3) crystal in a concentrated ammonia water solution; (2) adding glucose or ascorbic acid (as reducing agent) to the solution; and (3) adding an oxidizing agent to the solution. The preferred oxidizing agent is hydrogen peroxide (H2O2). Optionally, NaOH and ethanol can be added to the nanosilver solution to adjust the pH and improve the solubility of the nanosilver solution, respectively.
  • Additionally, the present invention provides methods of using the NAGs. The NAGs can be used in a variety of healthcare, medicinal, and industrial products. The NAGs can be added to ointments, lotions, and/or solutions for treating humans or animals with skin trauma, such as acne or pimples, wound, burns, skin with bacterial or fungal infections. In addition, the NAGs can be used in hygiene products, such as women gynecological washing solution, tooth brush soaking solution, or facial cleansing solution. The NAGs can also be used as food preservatives (e.g., for preserving fruits and vegetables), water disinfectants, paper disinfectants (e.g., for preventing mold build-up in book, newspaper, certificate, envelope, stationary, money, paper food containers, etc.), and in construction filling materials to prevent mold formation. Finally, the NAGs can be used as medicines to treat patients with gastrointestinal infection, sexually transmitted diseases, and eye diseases. [0022]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 shows the inhibitory effect of the NAGs on [0023] Staphylococcus aureus. The horizontal axis of the curve is the treatment time, the vertical axis is the amount of the bacteria remained (measured by CFU (colony forming units)) after being immersed in the NAGs-containing solution. Open circle indicates no NAGs. Close circle indicates with NAGs.
  • FIG. 2 shows the inhibitory effect of the NAGs on [0024] Escherichia coli. The horizontal axis of the curve is the treatment time, the vertical axis is the amount of the bacteria remained (measured by CFU (colony forming units)) after being immersed in the NAGs-containing solution. Open circle indicates no NAGs. Close circle indicates with NAGs.
  • FIG. 3 shows the inhibitory effect of the NAGs on [0025] Pseudomonas aeruginosa. The horizontal axis of the curve is the treatment time, the vertical axis is the amount of the bacteria remained (measured by CFU (colony forming units)) after being immersed in the NAGs-containing solution. Open circle indicates no NAGs. Close circle indicates with NAGs.
  • FIG. 4 is a flow chart indicating the process for making the NAGs in an industrial scale manufacturing. There are eight (8) chambers associated with the process, which are: (1) selection chamber; (2) separation chamber; (3) spraying chamber; (4) water removal chamber; (5) heat reaction chamber; (6) washing and soaking chamber; (7) drying chamber; and (8) grinding chamber. The function of each chamber will be described in the following section (infra).[0026]
    • DETAILED DESCRIPTION OF THE INVENTION
  • The present invention is directed to sustained-effect, broad-spectrum nanosilver containing antibacterial and antifungal granules (NAGs) and the process of manufacturing and using NAGs. The NAGs of the present invention are made by attaching nanosilver particles to small pieces of stalk marrow of the plant [0027] Juncus effuses L. The attachment of nanosilver particles to the NAGs have been confirmed by scanning electromicroscopy using AMRAY1910FE and TN-8502, which shows that the nanosilver particles on the NAGs were about 25 nm in diameter. The nanosilver particles were shown evenly distributed on the NAGs. The content of the nanosilver particles in the NAGs were analyzed by silver titrimetric method (see infra) to contain about 20-100 mg of silver per g of the NAGs. Also, due to the fact that the surface of the nanosilver particles was dark brown, which is a characteristic of silver oxidation, the surface of the nanosilver particles were identified to be silver oxide.
  • Juncus or rush pith, “Deng Xin Cao” in Chinese, has the pharmaceutical name [0028] Medulla Junci effusi, botanical name Juncus effusus L. var.decipiens Buchen. The plant belongs to the family of Juncaceae and is grown in the provinces of Jiangsu, Sichuan, Yunnan, and Guizhou in China. Juncus is harvested at the end of summer through autumn. There is no known major active ingredients in the plant. Because of its inert characteristics, the stalk marrow of Juncus is suitable for use as a carrier for nanosilver particles.
  • The NAGs of the present invention have demonstrated high antibacterial and antifungal effects. They are also non-toxic, non-stimulative, and non-allergic, so that they can be safely used in a large variety of healthcare, medicinal, and industrial products. [0029]
  • The antibactial and antifungal effects of the NAGs can be explained in the following four (4) chemical process: [0030]
  • (1) AgNO3+reducing agent (Glucose or Ascorbic Acid)→Ag; [0031]
  • (2) Ag+O[0032] 2 (oxidizing agent) Ag2O;
  • (3) Ag[0033] 2O (at the surface of the particles)+H2O→2Ag++2OH−;
    Figure US20020051823A1-20020502-C00001
  • Silver ion is an effective antiseptic and germicide, and its organic salts, particularly in the form of nitrates, are commonly used with furazolidones and antibiotics in the treatment of bums. Silver nitrate is one of the most powerful chemical germicides and is widely used as a local astringent and germicide. However, the nitrates irritate the skin. Thus, it is preferable to reduce the silver nitrate to metallic silver in the first (1) reaction. The metallic silver, as demonstrated in the second (2) reaction, is then undergone an oxidation to produce silver oxide (Ag[0034] 2O) in the presence of an oxidizing agent. When silver oxide is interacted with water, as shown in the third (3) reaction, it undergoes ionization to produce silver ion (Ag+). Finally, as shown in the fourth reaction (4), when the silver ion interacts with the sulfhydryl group (−SH) of an enzyme, it forms a -SAg linkage, which effectively blocks the enzyme activity. Therefore, the antibacterial and antifungal activity of the NAGs appears to be even more prominent when the NAGs are in contact with water.
  • The NAGs has a broad spectrum of antibacterial and antifungal activity. The NAGs of the present invention had bactericidal and fungicidal effects on more than twenty (20) common pathogens, which include, but are not limited to, [0035] Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus, Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus (Salmonella morgani), Pseudomonas altophila, Arizona, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B, Citrobacter, Salmonella paratyphi C.
  • Examples of the antibacterial activity of the NAGs were demonstrated in FIGS. [0036] 1-3. FIG. 1 shows the effect of the NAGs on Staphylococcus aureus. The data demonstrate that within 8 hours of treatment with the NAGs, all of the S. aureus were killed. FIG. 2 shows the effect of the NAGs on Escherichia coli. The data also demonstrate that within 8 hours of treatment with the NAGs, all of the E. coli were killed. FIG. 3 shows the effect of the NAGs on Pseudomonas aeruginosa. The data show that within 12 hours of treatment with the NAGs, all of the P. aeruginosa were killed.
  • The NAGs were prepared by first cutting the stalk marrow of [0037] Juncus effuses L. into pieces of 0.5 to 2 cm at length. These small pieces of stalk marrow were washed, followed by boiling in water to remove any unwanted water soluble materials. The boiled stalk marrow pieces were than dried for later use. In the meantime, a nanosilver particles-containing solution was prepared by first dissolving AgNO3 in ammonia water, followed by adding glucose (as reducing agent) to the reaction solution. An oxidizing agent, preferably H2O2, was then added to the reaction solution. The quantity or volume of each of the ingredients used in the nanosilver particle-containing solution is listed in Table 1.
    TABLE 1
    The Nanosilver Particles-Containing Solution
    Ingredients Quantity or Volume
    AgNO3 15 Kg
    Ammonia Water 15 L
    Glucose 3 Kg
    Ethanol (95%) 5 L
    NaOH 0.5 Kg
    Oxidizing Agent (e.g., H2O2) 100 ml
    Distilled Water up to
    1000 L
  • The above quantity of the nanosilver particles-containing solution was aimed at large scale industrial manufacturing use. The quantity could be scaled down proportionally for research and laboratory testing. [0038]
  • FIG. 4 shows a flow chart of industrial production of the NAGs. The process was operated in the following chambers: (1) selection chamber; (2) separation chamber; (3) spraying chamber; (4) water removal chamber; (5) heat reaction chamber; (6) washing and soaking chamber; (7) drying chamber; and (8) grinding chamber. [0039]
  • As shown in FIG. 4, in the “selection” chamber, stalk marrow of [0040] Juncus effuses L. were cut into pieces, preferably at a length of about 0.5 to 2 cm. The small pieces of stalk marrow were sieved through a selection process and transferred to the “separation” chamber, where the stalk marrow pieces were boiled and dried. The small pieces of dried stalk marrow were then transferred to the “spraying” chamber where the nanosilver particles-containing solution was evenly sprayed and dispersed onto the small pieces of dried stalk marrow. The small pieces of stalk marrow were further soaked with the nanosilver particles-containing solution in the “spraying” chamber for an adequate amount of time. The small pieces of stalk marrow with attached nanosilver particles were then transferred to the “water removal” chamber where excess solution was removed from the pieces.
  • The small pieces of stalk marrow were then transferred to the “heat reaction” chamber, where the nanosilver-attached stalk marrow pieces were treated with heat. [0041]
  • The heat-reacted stalk marrow pieces were transferred to the “soaking and washing” chamber, where the pieces were soaked and washed first with hot water, then with cold water, to remove any unattached nanosilver particles and water-soluble substances. The washed nanosilver particles-attached stalk marrow pieces were then dried under heat in the “drying” chamber, and finally transferred to the “grinding” chamber to be ground to proper NAG sizes. The final NAGs should contain no water-soluble substances other than silver. These NAGs could be used in various healthcare, medicinal and industrial products to disinfect, inhibit the growth of bacteria or fungi, and/or prevent mold formation. [0042]
  • Examples of the NAGs used in healthcare products include, but are not limited to, ointments, lotions, or spraying solutions for treating all kinds of injuries and/or bums, bacterial and fungal infections (including gynecological infections such as vaginitis), cleansing agents for clothing, women hygiene, acne or pimples, and soaking solution for tooth brush. Examples of the NAGs used in medicinal products include, but are not limited to, internal medicines for treating gastrointestinal bacterial infection, sexually transmitted diseases, or as an eye drop for treating eye diseases. Examples of the NAGs used in industrial products include, but are not limited to, food preservatives especially for fruits and vegetables, drinking water disinfectants, paper and construction filling materials preservation (especially to prevent mold formation). [0043]
  • The following examples are illustrative, but not limiting the scope of the present invention. Reasonable variations, such as those occur to reasonable artisan, can be made herein without departing from the scope of the present invention. [0044]
    • EXAMPLE 1 Titrimetric Analysis of Silver in NAGs
  • The content of the silver in the NAGs was analyzed by a titrimetric analysis as follows: [0045]
  • A. Basic chemical reactions [0046]
  • The basic chemical reactions involved in the volumetric analysis were:[0047]
  • Ag++SCN−→AgSCN↓
  • Fe+3+6SCN−→Fe(SCN)6 −3 (light brownish red)(end point)
  • B. Preparation of solutions [0048]
  • (1). Solvent: HNO[0049] 3 solution. The solution was prepared by mixing nitric acid with water at ratio 1:1 (v/v). The concentration of nitric acid in the solution was 6N.
  • (2). Indicator: 10% NH[0050] 4Fe(SO4)2 aqueous solution (w/v).
  • (3). Titrant: NH[0051] 4SCN standardized solution.
  • 0.75 g NH[0052] 4SCN was weighed and dissolved in 1000 ml water in a volumetric flask. The flask was gently shaken to evenly distribute NH4SCN in the solution. The solution was standardized by a standard Ag solution.
  • (4). Standard Ag solution: [0053]
  • 1.0000 g of clean and dry silver shreds or flakes was weighed and cut into small pieces. The pieces were placed in a 1000 ml brown volumetric flask and completely dissolved in 100 ml 6 N HNO[0054] 3 by heat in water bath. The flask was covered with filter paper during the heating process. After the flask cooled down, the volume of solution was brought up to 1000 ml by water. The flask was shaken to disperse the solute. The final concentration of the solution was 1 mg/ml.
  • C. Standardizing NH[0055] 4SCN solution
  • Ten (10) ml of standard Ag solution (1 mg/ml) as shown in B(4) was measured and poured into a 200 ml volumetric flask. For the blank control, 10 ml of water was poured into the 200 ml volumetric flask. Then, 6N HNO[0056] 3 was added to the flask (the acidic level of nitric acid was between 1-10%), followed by adding 1-2 ml of 10% NH4Fe(SO4)2 aqueous solution to the flask as the indicator. Water was then added along the wall of the flask until the volume was kept at 80-100 ml. NH4SCN solution prepared in B(3) was used as titrant to react with silver solution until a stable light brownish red appeared, which signaled the end of the reaction. The titrimetric analysis was conducted in triplicates to get a mean value. The standard deviation (SD) of the mean values should be less than 0.10 ml. The silver titer value, TAg, was calculated:
  • T[0057] Ag=Ag amount in Ag standard solution/[(mean volume of the triplicates)-blank](The unit for TAg is mg/ml.)
  • D. Titrimetric analysis of the NAGs [0058]
  • 100.0 mg of the NAGs, after being dried in a desiccator for 2 to 4 hours, was precisely measured and placed in a 200 ml flask. Then, 20-30 ml of 6N HNO[0059] 3 were added into the flask, and the flask was placed on a low-heat thermoelectrical plate until the solution was slightly boiling, where the solution was maintained at this stage until the solution became colorless. Then, the flask was cooled down and diluted to 100 ml. 1-2 ml indicator was added to the solution. The solution was analyzed by titration using the standardized NH4SCN solution. When the solution was stable in a color of light brownish red, it was the end point of the titration.
  • E. Results [0060]
  • The content of the silver in the NAGs was calculated by the following equation.[0061]
  • Ag% in the NAGs=(V×T Ag /W)×100%
  • Where V was the volume of the NH[0062] 4SCN solution added to the titration flask after the blank was deducted. TAg was in the unit of mg Ag/ml. W was the weight of the NAG sample in mg.
  • From the above calculation, the silver content of the NAGs was about 2-8%. [0063]
    • EXAMPLE 2 Antibacterial Effect of the Solution Containing the NAGs
  • The antibacterial effect of the NAGs in the solution was tested as follows: [0064]
  • A. Preparation of the NAGs solution [0065]
  • Five (5) g of the NAGs were suspended in 500 ml of water and stayed in the solution for 24 hrs to obtain an NAGs-containing solution. [0066]
  • B. Preparation of bacteria [0067]
  • M-H liquid and solid culture media were used for activation and culture of the bacteria. [0068] Staphylococcus aureus stock M120, Escherichia coli stock E109, and Pseudomonas aeruginosa stock PS208 were used for the testing. These stocks were provided by the Microbiology Teaching and Research Section at Henan Medical University.
  • The frozen stocks of bacteria were seeded onto solid culture media. Single colonies were picked and inoculated respectively in 2 ml liquid culture medium and cultured at 37° C. for eight (8) hours. Then, the liquid culture medium was diluted at 1:1000 and stored in refrigerator (around 0° C.) until ready for use. The solution contained about 10[0069] 5 CFU/ml bacterial stock.
  • C. Treatment of bacterial stocks in the solution [0070]
  • Under sterile condition, the NAGs-containing solution was added to three (3) flasks, each containing 100 ml of the solution. One (1) ml of the bacterial stocks of [0071] E. coli, S. aureus, or P. aeruginosa was then added to the three flasks, respectively. The control was prepared by adding the bacterial stocks in the flasks containing water. The inhibitory effect of the NAGs on the three different bacteria was conducted over a period of eight (8) hours.
  • D. Results of the experiment [0072]
  • At the end of the eight hours study, the solution was diluted and plated on a culture plate to measure the number of remaining bacteria. In the solution containing the NAGs, more than 99% of all the tested bacteria were killed, which demonstrated that the NAGs-containing solution was very effective as bactericide and could be used as disinfectant. [0073]
    • EXAMPLE 3 Time Course of Antibacterial Effects of the NAGs
  • A time course study of the antibacterial effects of the NAGs in a solution was conducted as follows: [0074]
  • A. Preparation of bacterial stocks [0075]
  • M-H liquid and solid culture media were used for activation and culture of the bacteria. [0076] Staphylococcus aureus stock M120, Escherichia coli stock E109, and Pseudomonas aeruginosa stock PS208 were provided by the Microbiology Teaching and Research Section at Henan Medical University. The stocks were cultured in an incubator at 37° C. for 24 hours.
  • The frozen stocks of bacteria were seeded to a culture plate. Single colonies were chosen and inoculated in 2 ml liquid culture medium, respectively, where they were cultured at 37° C. for eight (8) hours. Then, the liquid culture medium was diluted at 1:1000 and stored in the refrigerator (around 0° C.) until ready for use. The solution contained about 10[0077] 5 CFU/ml bacterial stock.
  • B. The effect of the NAGs on [0078] E. coli, S. aureus, and P. aeruginosa
  • Under sterile condition, three (3) flasks, which contained 100 ml of the NAGs-containing solution in each flask, were inoculated with [0079] E. coli, S. aureus, or P. aeruginosa, respectively, with about 104-105 bacteria per ml in the solution. A time course was studied at 2, 4, 8, 12, and 24 hours intervals, each with 0.5 ml of sample. The viable number of the bacteria was counted. The control study was conducted with the same number of bacteria incubated at the same condition in a 100 ml of water rather than the NAGs-containing solution.
  • C. Results [0080]
  • As shown in FIG. 1, after inoculating [0081] S. aureus in a solution containing the NAGs, the number of S. aureus reduced to 0.01% of the starting number during the first two hours after the inoculation. Eight (8) hours after the inoculation, all of the bacteria were killed.
  • As shown in FIG. 2, after inoculating [0082] E. coli in a solution containing the NAGs, the number of E. coli reduced to 0.1% of the starting number during the first two hours after the inoculation. Eight (8) hours after the inoculation, all of the bacteria were killed.
  • As shown in FIG. 3, after inoculating [0083] P. aeruginosai in a solution containing the NAGs, the number of E. coli reduced to 1% of the starting number during the first two hours after the inoculation. Twelve (12) hours after the inoculation, all of the bacteria were killed
  • The results of this study indicate that the NAGs had inhibitory effects on [0084] E. coli, S. aureus, and P. aeruginosa.
    • EXAMPLE 4 Antibacterial Effect of the NAGs on Toothbrush
  • The antibacterial effect of the NAGs was tested on toothbrush as follows: [0085]
  • A. Preparation of bacteria [0086]
  • M-H liquid and solid culture media were used for activation and culture of the bacteria. [0087] Staphylococcus aureus stock M120 was provided by the Microbiology Teaching and Research Section at Henan Medical University. The stock was cultured in an incubator at 37° C. for 24 hours.
  • The frozen stock of bacteria was seeded to a culture plate. A single colony was chosen and inoculated in 2 ml liquid culture medium, respectively, where the bacteria were cultured at 37° C. for eight (8) hours. Then, the liquid culture medium was diluted at 1:1000 and stored in the refrigerator (around 0° C.) until ready for use. The solution contained about 10[0088] 5 CFU/ml bacterial stock.
  • B. Treatment of toothbrush [0089]
  • The bactericidal activity of the NAGs on toothbrush was tested by two (2) methods: [0090]
  • (1). Treatment of toothbrush in its natural state [0091]
  • A half of a toothbrush was immersed in 30 ml of a solution containing the NAGs for eight (8) hours. The other half of the toothbrush was immersed in 30 ml of saline solution. One (1) ml of each of the solutions was taken out after the 8 hours incubation, diluted, and tested for bacteria counts on plate. This method tested the natural existence of germs on the toothbrush and the effect of the NAGs on inhibiting the growth of the germs. [0092]
  • (2). Treatment of toothbrush in use with added [0093] Staphylococcus aureus
  • A half of the toothbrush was immersed in 30 ml solution containing the NAGs. One (1) ml of the bacterial stock containing [0094] Staphylococcus aureus was added to the solution. At the end of the 8 hours incubation, 1 ml of the solution was taken out and tested for bacteria counts on plate. The other half of the toothbrush was immersed in 30 ml of saline solution. One (1) ml of each of the solutions was taken out after the 8 hours incubation, diluted, and tested for bacteria counts on plate. This method tested the bactericidal effect of the NAGs on toothbrush where known amount of S. aureus was inoculated in the solution
  • C. Results [0095]
  • (1). Treatment of toothbrush in its natural state [0096]
  • The bactericidal efficiency for the NAGs was about 95%. [0097]
  • (2). Treatment of toothbrush in use with added [0098] Staphylococcus aureus
  • The bactericidal efficiency for the NAGs was about 98%. [0099]
  • The results show that the NAGs were effective against bacteria which were grown on the toothbrush. Therefore, the NAGs could be effectively used as a disinfectant for toothbrush. [0100]
    • EXAMPLE 5 Testing of the Toxicity of the NAGs on Rats
  • The NAGs were given to normal, healthy rats in a dose of 925 mg/kg of body weight per day for fourteen (14) days. This dose was more than 4,625 fold of the dose generally recommended to humans. The activities of rats were monitored. At the end of the 14 days period, no rats were dead or sick, which indicated that the NAGs were safe and non-toxic to rats. [0101]
    • EXAMPLE 6 Skin Allergic Test of the NAGs on Rabbits
  • A 5% (w/v) NAGs-containing solution was applied to the skin of the rabbits. The rabbits were monitored at 1 hr, 24 hrs, and 48 hrs intervals. No rash, bruise, or any irritating reaction was observed on the rabbit skins, which indicated that the NAGs were safe and not creating any allergic reaction on the skins. [0102]
  • While the invention has been described by way of examples and in terms of the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications as would be apparent to those skilled in the art. Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications. [0103]

Claims (23)

What is claimed is:
1. A nanosilver-containing antibacterial and antiflngal granule (NAG) comprising:
nanosilver particles attached to stalk marrow of Juncus effuses L.;
wherein each of said nanosilver particles comprises a metallic silver core surrounded by silver oxide.
2. The NAG according to claim 1, wherein said nanosilver particles are 1-100 nm in diameter.
3. The NAG according to claim 1, wherein said NAG inhibits growth of bacteria and fungi, which are ones selected from the group consisting of Escherichia coli, Methicillin resistant Staphylococcus aureus, Chlamydia trachomatis, Providencia stuartii, Vibrio vulnificus, Pneumobacillus, Nitrate-negative bacillus, Staphylococcus aureus, Candida albicans, Bacillus cloacae, Bacillus allantoides, Morgan's bacillus (Salmonella morgani), Pseudomonas maltophila, Pseudomonas aeruginosa, Neisseria gonorrhoeae, Bacillus subtilis, Bacillus foecalis alkaligenes, Streptococcus hemolyticus B, Citrobacter, and Salmonella paratyphi C.
4. The NAG according to claim 1, wherein said NAG is produced by:
cutting the stalk marrow of Junicus effuses L. into pieces;
immersing the cut stalk marrow in a solution containing nanosilver particles to attach the nanosilver particles to the cut stalk marrow;
drying the nanosilver particles-attached stalk marrow; and
grinding the nanosilver particles-containing stalk marrow to produce NAG.
5. The NAG according to claim 4, wherein said nanosilver particles-containing solution comprises:
silver nitrate (AgNO3), a concentrated ammonia water solution; glucose or ascorbic acid; and an oxidizing agent.
6. The NAG according to claim 5, wherein said oxidizing agent is hydrogen peroxide (H2O2).
7. The according to claim 5, further comprising adding ethanol and NaOH to the solution.
8. A method for preparing the NAG according to claim 1, comprising:
cutting the stalk marrow of Junicus effuses L. into pieces;
preparing a nanosilver particles-containing solution;
mixing and heating said cut stalk marrow with said nanosilver particles-containing solution to induce attachment of said nanosilver particles to said cut stalk marrow;
washing said nanosilver particles-attached cut stalk marrow;
drying said washed nanosilver particles-attached cut stalk marrow; and
grinding said dried nanosilver particles-attached cut stalk marrow to form NAG.
9. The method according to claim 8, wherein said nanosilver particles solution is prepared by:
dissolving silver nitrate (AgNO3) crystal in a concentrated ammonia water solution;
adding glucose or ascorbic acid to the solution; and
adding an oxidizing agent to the solution.
10. The method according to claim 9, wherein said oxidizing agent is hydrogen peroxide.
11. A method for treating humans or animals with a skin trauma site, comprising:
applying the NAG according to claim 1 to the skin trauma site of said humans or animals, wherein said NAG is contained in a solution.
12. The method according to claim 11, wherein said skin trauma site is one selected from the group consisting of acne, wound, burns, skin with bacterial infection, and skin with fungal infection.
13. A method for applying the NAG according to claim 1 to a hygiene product, comprising:
putting said NAG in a solution; and
applying said NAG-containing solution to said hygiene product.
14. The method according to claim 13, wherein said hygiene product is one selected from the group consisting of women gynecological washing solution, tooth brush soaking solution, and facial cleansing solution.
15. A method for preserving food comprising:
putting the NAG according to claim 1 in a solution; and
spraying said NAG-containing solution to food.
16. The method according to claim 15, wherein said food is one selected from the group consisting of fruits and vegetables.
17. A method for disinfecting paper comprising:
putting the NAG according to claim 1 in a solution; and
spraying said NAG-containing solution to paper.
18. The method according to claim 18, wherein said paper is one selected from the group consisting of book, newspaper, certificate, envelope, stationary, money, paper food container.
19. A method for disinfecting drinking water comprising:
adding the NAG according to claim 1 to the drinking water.
20. A method for treating patients with gastrointestinal bacterial infection comprising:
orally administering the NAG according to claim 1 to said patients.
21. A method for treating patients with sexually transmitted diseases comprising:
orally administering the NAG according to claim 1 to said patients.
22. A method for treating patients with eye diseases comprising:
administering the NAG acccording to claim 1 in an eye drop to treat said patients with eye diseases.
23. A method for preventing mold formation in construction filling materials comprising:
spraying the NAG according to claim 1 to the construction filling materials.
US09/840,906 2000-09-13 2001-04-25 Nanosilver-containing antibacterial and antifungal granules and methods for preparing and using the same Expired - Lifetime US6379712B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09/840,906 US6379712B1 (en) 2000-09-13 2001-04-25 Nanosilver-containing antibacterial and antifungal granules and methods for preparing and using the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US23092500P 2000-09-13 2000-09-13
US09/840,906 US6379712B1 (en) 2000-09-13 2001-04-25 Nanosilver-containing antibacterial and antifungal granules and methods for preparing and using the same

Publications (2)

Publication Number Publication Date
US6379712B1 US6379712B1 (en) 2002-04-30
US20020051823A1 true US20020051823A1 (en) 2002-05-02

Family

ID=26924689

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/840,906 Expired - Lifetime US6379712B1 (en) 2000-09-13 2001-04-25 Nanosilver-containing antibacterial and antifungal granules and methods for preparing and using the same

Country Status (1)

Country Link
US (1) US6379712B1 (en)

Cited By (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030203046A1 (en) * 2000-07-27 2003-10-30 Burrell Robert E. Solutions and aerosols of metal-containing compounds
WO2004074388A1 (en) * 2003-02-18 2004-09-02 Otto Schildhauer Method for treating tubular goods
US20040180093A1 (en) * 2003-03-12 2004-09-16 3M Innovative Properties Company Polymer compositions with bioactive agent, medical articles, and methods
US20040191329A1 (en) * 2000-07-27 2004-09-30 Burrell Robert E. Compositions and methods of metal-containing materials
US20040239004A1 (en) * 2003-05-31 2004-12-02 Kim Jin Soo Method for producing an injection-molded material with an antibacterial function
WO2005000324A3 (en) * 2003-06-03 2005-03-24 American Biotech Labs Colloidal silver composition having antimicrobial properties
US20050061678A1 (en) * 1999-06-01 2005-03-24 American Biotech Labs Treatment of humans with colloidal silver composition
US20050123621A1 (en) * 2003-12-05 2005-06-09 3M Innovative Properties Company Silver coatings and methods of manufacture
US20050124724A1 (en) * 2003-12-05 2005-06-09 3M Innovative Properties Company Polymer compositions with bioactive agent, medical articles, and methods
US20060035039A1 (en) * 2004-08-12 2006-02-16 3M Innovative Properties Company Silver-releasing articles and methods of manufacture
US20060034899A1 (en) * 2004-08-12 2006-02-16 Ylitalo Caroline M Biologically-active adhesive articles and methods of manufacture
US20060147502A1 (en) * 2004-12-30 2006-07-06 Kimberly-Clark Worldwide, Inc. Methods for controlling microbial pathogens on currency and mail
US20060233889A1 (en) * 2005-04-14 2006-10-19 3M Innovative Properties Company Silver coatings and methods of manufacture
EP1779855A1 (en) * 2005-10-28 2007-05-02 Abdula Kurkayev Nanoparticles of a heterocrystal mineral for use as a medicament and method of producing the same
US20070098806A1 (en) * 2002-05-02 2007-05-03 Ismail Ashraf A Polymer-Based Antimicrobial Agents, Methods of Making Said Agents, and Products Incorporating Said Agents
US20070166399A1 (en) * 2006-01-13 2007-07-19 3M Innovative Properties Company Silver-containing antimicrobial articles and methods of manufacture
US20070190174A1 (en) * 1999-06-01 2007-08-16 American Silver Llc Antiviral Colloidal Silver Composition
US20080085326A1 (en) * 2006-10-04 2008-04-10 Hai Xiong Ruan Antimicrobial material compositions enriched with different active oxygen species
US20080213328A1 (en) * 2007-03-02 2008-09-04 Yao-Nien Chung Nanosilver-containing preservation articles, and the preparation process and the uses thereof
US7445799B1 (en) 2000-06-21 2008-11-04 Icet, Inc. Compositions for microbial and chemical protection
US20090047475A1 (en) * 2007-08-17 2009-02-19 Sun Mi Jeon Composition for coating wiper blade rubbers, coating method using the same, and wiper blade rubbers made therefrom
US20090130161A1 (en) * 2000-06-21 2009-05-21 Icet, Inc. Material compositions for microbial and chemical protection
US20100098949A1 (en) * 2006-10-18 2010-04-22 Burton Scott A Antimicrobial articles and method of manufacture
US20100137822A1 (en) * 2007-02-15 2010-06-03 Huaide Chen Far infrared anion complex sanitary napkin/pad
EP1880213A4 (en) * 2005-01-05 2010-06-23 Robert Holladay Silver/water, silver gels and silver-based compositions; and methods for making and using the same
US20110123578A1 (en) * 2009-11-20 2011-05-26 Wenzel Scott W Cooling Substrates With Hydrophilic Containment Layer and Method of Making
US20110123584A1 (en) * 2009-11-20 2011-05-26 Jeffery Richard Seidling Temperature Change Compositions and Tissue Products Providing a Cooling Sensation
US8795717B2 (en) 2009-11-20 2014-08-05 Kimberly-Clark Worldwide, Inc. Tissue products including a temperature change composition containing phase change components within a non-interfering molecular scaffold
WO2016161348A1 (en) * 2015-04-01 2016-10-06 Attostat, Inc. Nanoparticle compositions and methods for treating or preventing tissue infections and diseases
US10137503B2 (en) 2011-07-01 2018-11-27 Attostat, Inc. Method and apparatus for production of uniformly sized nanoparticles
US10201571B2 (en) 2016-01-25 2019-02-12 Attostat, Inc. Nanoparticle compositions and methods for treating onychomychosis
US10774429B2 (en) 2015-04-13 2020-09-15 Attostat, Inc. Anti-corrosion nanoparticle compositions
US11018376B2 (en) 2017-11-28 2021-05-25 Attostat, Inc. Nanoparticle compositions and methods for enhancing lead-acid batteries
US11473202B2 (en) 2015-04-13 2022-10-18 Attostat, Inc. Anti-corrosion nanoparticle compositions
CN115227718A (en) * 2022-08-04 2022-10-25 广东省农业科学院动物卫生研究所 Application of nano-silver in inhibiting streptococcus suis
US11646453B2 (en) 2017-11-28 2023-05-09 Attostat, Inc. Nanoparticle compositions and methods for enhancing lead-acid batteries
US12115250B2 (en) 2019-07-12 2024-10-15 Evoq Nano, Inc. Use of nanoparticles for treating respiratory infections associated with cystic fibrosis
US12456759B2 (en) 2021-03-30 2025-10-28 Evoq Nano, Inc. Nanoparticle-enhanced lead-acid electrode paste and improved lead-acid batteries made therefrom

Families Citing this family (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030185889A1 (en) * 2002-03-27 2003-10-02 Jixiong Yan Colloidal nanosilver solution and method for making the same
US6979491B2 (en) * 2002-03-27 2005-12-27 Cc Technology Investment Co., Ltd. Antimicrobial yarn having nanosilver particles and methods for manufacturing the same
US6924325B2 (en) * 2002-06-21 2005-08-02 Kerr Corporation Silver-containing dental composition
KR100656169B1 (en) * 2002-12-23 2006-12-12 삼성전자주식회사 Method to give antimicrobial property to the surface of object using nano sized metal particles
CA2460585A1 (en) * 2003-05-16 2004-11-16 Exciton Technologies Inc. Deposition products, composite materials and processes for the production thereof
RU2248941C1 (en) * 2004-01-08 2005-03-27 Каркищенко Николай Николаевич Method for production of silver ion-containing disinfectant solution
US7507701B2 (en) 2005-02-25 2009-03-24 Solutions Biomed, Llc Aqueous disinfectants and sterilants including transition metals
US7473675B2 (en) * 2005-02-25 2009-01-06 Solutions Biomed, Llc Disinfectant systems and methods comprising a peracid, alcohol, and transition metal
US7553805B2 (en) * 2005-02-25 2009-06-30 Solutions Biomed, Llc Methods and compositions for treating viral, fungal, and bacterial infections
US7534756B2 (en) * 2005-02-25 2009-05-19 Solutions Biomed, Llc Devices, systems, and methods for dispensing disinfectant solutions comprising a peroxygen and transition metal
US7511007B2 (en) * 2005-02-25 2009-03-31 Solutions Biomed, Llc Aqueous sanitizers, disinfectants, and/or sterilants with low peroxygen content
US7504369B2 (en) * 2005-02-25 2009-03-17 Solutions Biomed, Llc Methods and compositions for decontaminating surfaces exposed to chemical and/or biological warfare compounds
MX2008015347A (en) 2005-02-25 2008-12-16 Solutions Biomed Llc Aqueous disinfectants and sterilants.
US7462590B2 (en) * 2005-02-25 2008-12-09 Solutions Biomed, Llc Aqueous disinfectants and sterilants comprising a peroxide/peracid/transition metal mixture
KR100767714B1 (en) 2005-04-19 2007-10-19 양원동 Silver Nano Metal Tooth Restorative
US7381686B2 (en) * 2005-04-27 2008-06-03 Taikong Corp. Composite for inhibiting algae growth and use therof
US20060254988A1 (en) * 2005-05-10 2006-11-16 Confirm Monitoring Systems, Inc. Methods and compositions for the treatment of water
US8119548B2 (en) * 2005-05-18 2012-02-21 Building Materials Investment Corporation Nanosilver as a biocide in building materials
TWM286648U (en) * 2005-10-06 2006-02-01 Wu-Lang Jang Toothbrush receptacle with disinfection function
US20070154505A1 (en) * 2005-12-30 2007-07-05 Manico Joseph A Antimicrobial agent to inhibit the growth of microorganisms on building materials
US20070154506A1 (en) * 2005-12-30 2007-07-05 Patton David L Antimicrobial agent to inhibit the growth of microorganisms on disposable products
US20070161936A1 (en) * 2006-01-06 2007-07-12 Svetlik Harvey E Wound treatment-dressing and method of manufacture
KR100788997B1 (en) 2006-03-10 2007-12-28 김주영 Process for producing antimicrobial wet dressing material chemically bonded with silver and its wet dressing material
WO2007140573A1 (en) * 2006-04-24 2007-12-13 Axcelon Biopolymers Corporation Nanosilver coated bacterial cellulose
US7661430B2 (en) * 2006-05-19 2010-02-16 Richard Mason Antimicrobial dental appliances including mouthguards and mouthpieces
US20070286878A1 (en) * 2006-06-07 2007-12-13 Harruna Issifu I Removable films for sanitizing substrates and methods of use thereof
US8455226B2 (en) * 2006-07-05 2013-06-04 Janssen Pharmaceutica N.V. Method for producing metal nanoparticles
US7635552B2 (en) * 2006-07-25 2009-12-22 Endicott Interconnect Technologies, Inc. Photoresist composition with antibacterial agent
WO2008036225A2 (en) 2006-09-20 2008-03-27 Entek Manufacturing, Inc. Conformable structured therapeutic dressing
BRPI0719208A2 (en) 2006-10-12 2017-09-26 C 3 Int Llc methods for obtaining prophylactic surface treatment for fluid processing systems and components thereof.
US7892317B2 (en) * 2007-07-11 2011-02-22 Jafar Rahman Nia Preparation of colloidal nanosilver
WO2009032203A1 (en) * 2007-08-30 2009-03-12 Solutions Biomed, Llc Colloidal metal-containing skin sanitizer
GB0800081D0 (en) * 2008-01-04 2008-02-13 Univ Gent Silver nanoparticles with specific surface area and/or isoelectric point and a method for producing them
WO2009114754A1 (en) * 2008-03-14 2009-09-17 Solutions Biomed, Llc Multi-chamber container system for storing and mixing fluids
US8623301B1 (en) 2008-04-09 2014-01-07 C3 International, Llc Solid oxide fuel cells, electrolyzers, and sensors, and methods of making and using the same
WO2010056881A1 (en) * 2008-11-12 2010-05-20 Solutions Biomed, Llc Multi-chamber container system for storing and mixing liquids
WO2010056871A2 (en) 2008-11-12 2010-05-20 Solutions Biomed, Llc Two-part disinfectant system and related methods
US20100120913A1 (en) * 2008-11-12 2010-05-13 Larson Brian G Resin catalyzed and stabilized peracid compositions and associated methods
US20120195838A1 (en) * 2009-09-04 2012-08-02 National University Corporation Kumamoto University Oral composition for denture wearers
CA2789281C (en) 2010-02-10 2015-11-24 C3 International, Llc Low temperature electrolytes for solid oxide cells having high ionic conductivity
CN102895315B (en) * 2012-09-28 2014-02-26 南昌大学 A nano-silver antibacterial composition containing forsythia extract
CN103044611B (en) * 2012-12-17 2015-06-10 上海师范大学 Preparation of polymer antibacterial nano-particles and magnetic antibacterial nano-particles containing halamine functional groups
US9446079B2 (en) 2013-07-11 2016-09-20 Links Medical Products, Incorporated Honey and silver nitrate composition, composition dressing and methods of making same
US9905871B2 (en) 2013-07-15 2018-02-27 Fcet, Inc. Low temperature solid oxide cells
TWI551739B (en) 2015-05-11 2016-10-01 Acelon Chem & Fiber Corp Method for preparing nano silver blended natural cellulose spunbonded non-woven fabric
TWI565853B (en) 2015-05-11 2017-01-11 Acelon Chem & Fiber Corp Preparation of nano - silver blended natural cellulose melt - blown non - woven
TWI565852B (en) 2015-05-11 2017-01-11 Acelon Chem & Fiber Corp Preparation of Nano silver blended natural cellulose fibers method

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4828832A (en) 1983-09-07 1989-05-09 Laboratorios Biochemie De Mexico Method of manufacturing a composition for treating skin lesions
US5824267A (en) 1994-08-01 1998-10-20 Kawasumi Laboritories, Inc. Metallic bactericidal agent
JP3121503B2 (en) 1994-10-18 2001-01-09 レンゴー株式会社 Antibacterial agent
US5973050A (en) 1996-07-01 1999-10-26 Integrated Cryoelectronic Inc. Composite thermoelectric material
US5785972A (en) 1997-01-10 1998-07-28 Tyler; Kathleen A. Colloidal silver, honey, and helichrysum oil antiseptic composition and method of application

Cited By (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060182813A1 (en) * 1999-06-01 2006-08-17 Holladay Robert J Colloidal silver composition having microbial properties
US8535728B2 (en) * 1999-06-01 2013-09-17 American Silver, Llc Colloidal silver composition having antimicrobial properties
US8753691B2 (en) * 1999-06-01 2014-06-17 American Silver, Llc Antiviral colloidal silver composition
US20070190174A1 (en) * 1999-06-01 2007-08-16 American Silver Llc Antiviral Colloidal Silver Composition
US7135195B2 (en) * 1999-06-01 2006-11-14 American Silver, Llc Treatment of humans with colloidal silver composition
US20050061678A1 (en) * 1999-06-01 2005-03-24 American Biotech Labs Treatment of humans with colloidal silver composition
US7445799B1 (en) 2000-06-21 2008-11-04 Icet, Inc. Compositions for microbial and chemical protection
US8192765B2 (en) 2000-06-21 2012-06-05 Icet, Inc. Material compositions for microbial and chemical protection
US20090130161A1 (en) * 2000-06-21 2009-05-21 Icet, Inc. Material compositions for microbial and chemical protection
US7078060B2 (en) 2000-07-27 2006-07-18 Nucryst Pharmaceuticals Corp. Solutions and aerosols of metal-containing compounds
US20030203046A1 (en) * 2000-07-27 2003-10-30 Burrell Robert E. Solutions and aerosols of metal-containing compounds
US20040191329A1 (en) * 2000-07-27 2004-09-30 Burrell Robert E. Compositions and methods of metal-containing materials
US20070098806A1 (en) * 2002-05-02 2007-05-03 Ismail Ashraf A Polymer-Based Antimicrobial Agents, Methods of Making Said Agents, and Products Incorporating Said Agents
US7951853B2 (en) 2002-05-02 2011-05-31 Smart Anti-Microbial Solutions, Llc Polymer-based antimicrobial agents, methods of making said agents, and products incorporating said agents
US20060018967A1 (en) * 2003-02-18 2006-01-26 Otto Schildhauer Method for treating pipelines
WO2004074388A1 (en) * 2003-02-18 2004-09-02 Otto Schildhauer Method for treating tubular goods
US20040180093A1 (en) * 2003-03-12 2004-09-16 3M Innovative Properties Company Polymer compositions with bioactive agent, medical articles, and methods
EP1481783A3 (en) * 2003-05-31 2005-11-23 Daewoo Electronics Corporation Method for producing an injection-molded material with an antibacterial function
US20040239004A1 (en) * 2003-05-31 2004-12-02 Kim Jin Soo Method for producing an injection-molded material with an antibacterial function
WO2005000324A3 (en) * 2003-06-03 2005-03-24 American Biotech Labs Colloidal silver composition having antimicrobial properties
US20050123621A1 (en) * 2003-12-05 2005-06-09 3M Innovative Properties Company Silver coatings and methods of manufacture
US8193267B2 (en) 2003-12-05 2012-06-05 3M Innovative Properties Company Polymer compositions with bioactive agent, medical articles, and methods
EP1689456B1 (en) * 2003-12-05 2012-02-22 3M Innovative Properties Company Polymer compositions with bioactive agent, medical articles, and methods
US20050124724A1 (en) * 2003-12-05 2005-06-09 3M Innovative Properties Company Polymer compositions with bioactive agent, medical articles, and methods
US20100233273A1 (en) * 2003-12-05 2010-09-16 3M Innovative Properties Company Polymer compositions with bioactive agent, medical articles, and methods
US7745509B2 (en) 2003-12-05 2010-06-29 3M Innovative Properties Company Polymer compositions with bioactive agent, medical articles, and methods
US20060034899A1 (en) * 2004-08-12 2006-02-16 Ylitalo Caroline M Biologically-active adhesive articles and methods of manufacture
US20060035039A1 (en) * 2004-08-12 2006-02-16 3M Innovative Properties Company Silver-releasing articles and methods of manufacture
US20060147502A1 (en) * 2004-12-30 2006-07-06 Kimberly-Clark Worldwide, Inc. Methods for controlling microbial pathogens on currency and mail
EP1880213A4 (en) * 2005-01-05 2010-06-23 Robert Holladay Silver/water, silver gels and silver-based compositions; and methods for making and using the same
US20060233889A1 (en) * 2005-04-14 2006-10-19 3M Innovative Properties Company Silver coatings and methods of manufacture
US8399027B2 (en) 2005-04-14 2013-03-19 3M Innovative Properties Company Silver coatings and methods of manufacture
WO2007048634A3 (en) * 2005-10-28 2007-12-06 Abdula Kurkayev Nanoparticles of a heterocrystal mineral for use as a medicament and method of producing the same
EP1779855A1 (en) * 2005-10-28 2007-05-02 Abdula Kurkayev Nanoparticles of a heterocrystal mineral for use as a medicament and method of producing the same
US20090226526A1 (en) * 2005-10-28 2009-09-10 Abdula Kurkayev Nanoparticles of a heterocrystal mineral for use as a medicament and method of producing the same
WO2007048634A2 (en) 2005-10-28 2007-05-03 Abdula Kurkayev Nanoparticles of a heterocrystal mineral for use as a medicament and method of producing the same
US8192764B2 (en) 2006-01-13 2012-06-05 3M Innovative Properties Company Silver-containing antimicrobial articles and methods of manufacture
US9289450B2 (en) 2006-01-13 2016-03-22 3M Innovative Properties Company Silver-containing antimicrobial articles and methods of manufacture
US20070166399A1 (en) * 2006-01-13 2007-07-19 3M Innovative Properties Company Silver-containing antimicrobial articles and methods of manufacture
US20080279960A1 (en) * 2006-01-13 2008-11-13 Burton Scott A Silver-Containing Antimicrobial Articles and Methods of Manufacture
US20080085326A1 (en) * 2006-10-04 2008-04-10 Hai Xiong Ruan Antimicrobial material compositions enriched with different active oxygen species
US20100098949A1 (en) * 2006-10-18 2010-04-22 Burton Scott A Antimicrobial articles and method of manufacture
AU2008215041B9 (en) * 2007-02-15 2014-01-16 Shenzhen Yuelang Techno-Industrial Co., Ltd. A far-infrared anion compound sanitary napkin and pad
US20100137822A1 (en) * 2007-02-15 2010-06-03 Huaide Chen Far infrared anion complex sanitary napkin/pad
AU2008215041B2 (en) * 2007-02-15 2013-09-12 Shenzhen Yuelang Techno-Industrial Co., Ltd. A far-infrared anion compound sanitary napkin and pad
US20080213328A1 (en) * 2007-03-02 2008-09-04 Yao-Nien Chung Nanosilver-containing preservation articles, and the preparation process and the uses thereof
US8304068B2 (en) * 2007-08-17 2012-11-06 Adm21 Co., Ltd. Composition for coating wiper blade rubbers, coating method using the same, and wiper blade rubbers made therefrom
US20090047475A1 (en) * 2007-08-17 2009-02-19 Sun Mi Jeon Composition for coating wiper blade rubbers, coating method using the same, and wiper blade rubbers made therefrom
US8894814B2 (en) 2009-11-20 2014-11-25 Kimberly-Clark Worldwide, Inc. Cooling substrates with hydrophilic containment layer and method of making
US8795717B2 (en) 2009-11-20 2014-08-05 Kimberly-Clark Worldwide, Inc. Tissue products including a temperature change composition containing phase change components within a non-interfering molecular scaffold
US20110123584A1 (en) * 2009-11-20 2011-05-26 Jeffery Richard Seidling Temperature Change Compositions and Tissue Products Providing a Cooling Sensation
US9181465B2 (en) 2009-11-20 2015-11-10 Kimberly-Clark Worldwide, Inc. Temperature change compositions and tissue products providing a cooling sensation
US20110123578A1 (en) * 2009-11-20 2011-05-26 Wenzel Scott W Cooling Substrates With Hydrophilic Containment Layer and Method of Making
US9545365B2 (en) 2009-11-20 2017-01-17 Kimberly-Clark Worldwide, Inc. Temperature change compositions and tissue products providing a cooling sensation
US8480852B2 (en) 2009-11-20 2013-07-09 Kimberly-Clark Worldwide, Inc. Cooling substrates with hydrophilic containment layer and method of making
US10137503B2 (en) 2011-07-01 2018-11-27 Attostat, Inc. Method and apparatus for production of uniformly sized nanoparticles
US10610934B2 (en) 2011-07-01 2020-04-07 Attostat, Inc. Method and apparatus for production of uniformly sized nanoparticles
WO2016161348A1 (en) * 2015-04-01 2016-10-06 Attostat, Inc. Nanoparticle compositions and methods for treating or preventing tissue infections and diseases
US10953043B2 (en) 2015-04-01 2021-03-23 Attostat, Inc. Nanoparticle compositions and methods for treating or preventing tissue infections and diseases
US11473202B2 (en) 2015-04-13 2022-10-18 Attostat, Inc. Anti-corrosion nanoparticle compositions
US10774429B2 (en) 2015-04-13 2020-09-15 Attostat, Inc. Anti-corrosion nanoparticle compositions
US10201571B2 (en) 2016-01-25 2019-02-12 Attostat, Inc. Nanoparticle compositions and methods for treating onychomychosis
US11018376B2 (en) 2017-11-28 2021-05-25 Attostat, Inc. Nanoparticle compositions and methods for enhancing lead-acid batteries
US11646453B2 (en) 2017-11-28 2023-05-09 Attostat, Inc. Nanoparticle compositions and methods for enhancing lead-acid batteries
US12119456B2 (en) 2017-11-28 2024-10-15 Evoq Nano, Inc. Nanoparticle compositions and methods for enhancing lead-acid batteries
US12115250B2 (en) 2019-07-12 2024-10-15 Evoq Nano, Inc. Use of nanoparticles for treating respiratory infections associated with cystic fibrosis
US12456759B2 (en) 2021-03-30 2025-10-28 Evoq Nano, Inc. Nanoparticle-enhanced lead-acid electrode paste and improved lead-acid batteries made therefrom
CN115227718A (en) * 2022-08-04 2022-10-25 广东省农业科学院动物卫生研究所 Application of nano-silver in inhibiting streptococcus suis

Also Published As

Publication number Publication date
US6379712B1 (en) 2002-04-30

Similar Documents

Publication Publication Date Title
US6379712B1 (en) Nanosilver-containing antibacterial and antifungal granules and methods for preparing and using the same
RU2422137C1 (en) Method of obtaining biocidal polyguanidine and biocidal polyguanidine
EP1490543B1 (en) Antimicrobial yarn having nanosilver particles and methods for manufacturing the same
CN101389221B (en) Silver/water, silver gel and silver-based compositions and methods for making and using same
US20100003296A1 (en) Manufacturing methods and applications of antimicrobial plant fibers having silver particles
RU2407289C1 (en) Nanostructured biocide composition
US20180168165A1 (en) Silver iodate compounds having antimicrobial properties
EP2874671A1 (en) Anti-microbial gel formulations containing a silver (i) periodate
WO2003080231A1 (en) Colloidal nanosilver solution and method for making the same
KR20130010880A (en) Antiseptic ointment comprising bentonite intercalated with silver, copper or zinc for external application
WO2001072642A1 (en) Silver ion-containing solution and use thereof
US9723843B2 (en) Family of silver (I) periodate compounds having broad microbial properties
CN1082645A (en) Long-acting broad-spectrum antiseptic fabric and preparation method thereof
RU2408755C1 (en) Composition for antiseptic treatment of woven materials
EP2170081B1 (en) Antimicrobial compositions
US11000502B2 (en) Antimicrobial compositions comprising copper-hydroxypyrone complexes
RU2525545C2 (en) Method of production of antimicrobial argentiferous cellulosic material
CN108938559B (en) A kind of DNA gel sterilization material and preparation method thereof and application as sterilization material
CN1177092C (en) A kind of preparation method of metal complex type antibacterial fiber
CN110974776A (en) Iodine-starch aerogel and preparation method and application thereof
JP2005002033A (en) Antimicrobial and degerming agent
KR200391561Y1 (en) Silver Nano Banban Line
CN118286324A (en) Antibacterial agent for animal cultivation and preparation method and application thereof
WO2023131855A1 (en) Antimicrobial composition
HK1207528A1 (en) Information medium with biocidal properties and method for manufacturing the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: GLOBOASIA L.L.C., MARYLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YAN, JIXIONG;CHENG, JIACHONG;REEL/FRAME:011738/0953

Effective date: 20010420

STCF Information on status: patent grant

Free format text: PATENTED CASE

AS Assignment

Owner name: LEGEND WIN FINANCE CORPORATION, VIRGIN ISLANDS, BR

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GLOBOASIA, LLC;REEL/FRAME:013531/0503

Effective date: 20021125

REMI Maintenance fee reminder mailed
FPAY Fee payment

Year of fee payment: 4

SULP Surcharge for late payment
REMI Maintenance fee reminder mailed
FPAY Fee payment

Year of fee payment: 8

SULP Surcharge for late payment

Year of fee payment: 7

FPAY Fee payment

Year of fee payment: 12