CN103126977A - Intelligent nano-silver hydrogel - Google Patents
Intelligent nano-silver hydrogel Download PDFInfo
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- CN103126977A CN103126977A CN2013100703002A CN201310070300A CN103126977A CN 103126977 A CN103126977 A CN 103126977A CN 2013100703002 A CN2013100703002 A CN 2013100703002A CN 201310070300 A CN201310070300 A CN 201310070300A CN 103126977 A CN103126977 A CN 103126977A
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Abstract
The invention discloses intelligent nano-silver hydrogel. A preparation process of the intelligent nano-silver hydrogel comprises the following steps of: 1, dissolving silver nitrate and hydroxypropyl methyl cellulose used as raw materials into purified water to prepare a hydroxypropyl methyl cellulose-silver nitrate complex; and 2, on the basis of taking a complex solution as a precursor, reducing silver ions in the precursor solution by using hydrate electrons and free radicals produced by ultraviolet irradiation to prepare nano-silver gel, coating nano-silver by the hydroxypropyl methyl cellulose through the action of sulfydryl and silver, and forming hydrogel by amino and carboxylic acid of the hydroxypropyl methyl cellulose as hydrophilic residue network water molecules to prepare the nano-silver hydrogel. Compared with the nano-silver hydrogel prepared by using the traditional method, the intelligent nano-silver hydrogel disclosed by the invention has the advantages of few raw materials, simple preparation method, good antibacterial effect, good stability and the like and can have no remarkable change after being exposed in air for one year.
Description
Technical field
The present invention relates to the medical aquogel compositions, be specially a kind of intelligent nano silver hydrogel for gyniatrics.
Background technology
Along with a large amount of uses of the chemicalses such as antibiotic, disinfectant and antibacterial, more and more by the microbial variation population that drug resistance causes.Nanometer silver is as inorganic antibacterial material, and the pathogenic microorganism such as kill bacteria, fungus, mycoplasma, have the incomparable antibacterial activity of other anti-biotic materials effectively.Nanometer silver has broad-spectrum antibacterial property, high efficiency, effect and lastingly, is not subjected to the advantages such as pH value affects, safety and environmental protection, more and more is familiar with, and becomes desirable anti-biotic material.
Generally, hydrogel is to introduce a part of hydrophobic group and hydrophilic residue in the water soluble polymer of cross-linked network with having, and hydrophilic residue and water molecules are connected to netted inner formation with hydrone.Hydrogel is mainly by the hydrophilic macromolecule network system at present: comprise polysaccharide (starch, cellulose, alginic acid, hyaluronic acid, chitosan etc.), polypeptide class (collagen, poly-L-lysine, poly-L-glutamic acid etc.) and synthesizing polyethylene, acrylic acid derivative (polyacrylic acid, polymethylacrylic acid, polyacrylamide, poly-N-poly-are for acrylamide etc.) consist of.
Owing to having good bio-compatibility and field of medicaments huge applications potentiality, proteins and peptides class hydrogel becomes study hotspot in recent years.As (Zohuriaan-Mehr, M. work, Pourjavadi, A+Salimi, H.﹠amp; Kurdtabar, M.Protein-and homo p01y (amino acid)-based hydrogels with super-swellingproperties.P01ym Advan Techn01,2009,20,655-671.), (Seliktar, D.DesigningCell-Compatible Hydrogels for Biomedicai ApplicatiOns.Science, 2012,336,1124-1128.) etc. many pieces of papers are studying and are summing up proteins and peptides in great detail and forming the condition of hydrogel.In recent years, scientists is by simplifying and optimize polypeptide structure, by the oligopeptide non-covalent hydrogel prepared of the dipeptides of two aminoacid connections even, and is applied to the field such as in-vitro antibacterial drug controllable release.
The preparation of the nanometer silver of broad-spectrum antiseptic is become hydrogel will have broad application prospects at field of medicaments.Can find out from the patent of invention of the present world and the domestic research paper of delivering and application, elementary tactics is that the first silver ion that reduces under the high-temperature liquid-phase condition prepares nano-Ag particles, then synthetic nanometer silver is added in the polymeric gel agent that can prepare hydrogel, " chitosan nano silver hydrogel adhesive and application thereof ", number of patent application is: 200810016256.6 " and " a kind of nanometer Ag antibiotic gent for women and preparation method thereof ", number of patent application 200810123375.1 " etc.Above method needs multistep synthetic, need to add a large amount of reducing agents, stabilizing agent, polymeric gel agent etc. when making, and has increased processing technology, raw material and cost.
Summary of the invention
Patent of the present invention is for the deficiencies in the prior art, provides a kind of and adopts that raw material is few, processing technology simple, good antimicrobial effect and the micelle footpath narrow distribution range that makes, uniform a kind of intelligent nano silver hydrogel.
For solving the problems of the technologies described above technical scheme provided by the invention be:
A kind of intelligent nano silver hydrogel comprises that following method makes:
The first step: prepare hydroxypropyl emthylcellulose-silver ion coordination compound as material dissolution take silver nitrate and hydroxypropyl emthylcellulose in pure water;
Second step: as precursor, utilize in hydrated electron that ultraviolet light irradiation produces and radical pair precursor solution silver ion to reduce the preparation nano silver colloidal sol this complex solution; Hydroxypropyl emthylcellulose is used for being coated with nanometer silver by sulfydryl and silver; The amino of hydroxypropyl emthylcellulose and carboxylic acid form hydrogel as hydrophilic residue network hydrone, thereby make the nanometer silver hydrogel.
Described hydroxypropyl emthylcellulose comprises a kind of in both of D type, L-type, and perhaps D type and L-type mixes.
The concentration conditions of described formation hydrogel be the hydroxypropyl emthylcellulose quality account for the hydrogel gross mass 0.1%-0.15%.
The molar concentration rate of described silver nitrate and hydroxypropyl emthylcellulose is 1.5:1.
Described ultraviolet light, preferred 100 watts of high voltage mercury lamp irradiations.
Described exposure time is 2.5h.
Patent of the present invention is compared with existing nanometer silver hydrogel preparation method, has the following advantages:
(1) raw materials is few: in precursor solution, hydroxypropyl emthylcellulose is used as the chelating agent of silver ion in the present invention; The sulfydryl that silver ion is reduced rear hydroxypropyl emthylcellulose is combined with nanometer silver as the stabilizing agent of nanometer silver; In gelation process, the hydrophilic amino of hydroxypropyl emthylcellulose and carboxyl are as the bonding agent of network hydrone.
(2) preparation method is simple: preparation only needs uviol lamp get final product, and equipment less demanding easily realized production in enormous quantities.
(3) good antimicrobial effect, good stability: the nanometer silver particle size distribution range that makes is narrow, even, and regular shape is spheroidal; The nanometer silver hydrogel exposes 1 year without significant change in air, antibacterial consumption is few, good antimicrobial effect.
The present invention utilizes under ultraviolet light the lower solution of irradiation to generate to have reproducibility and secondary free radical becomes silver atoms with silver ion reduction, the preparation nanometer silver; Utilization has the three functions group, and (-COOH) hydroxypropyl emthylcellulose utilizes it-the interactional function nano-Ag particles of SH and noble silver for-SH ,-NH2; Utilization-NH2 and-hydrogen bond network lock water that COOH forms forms hydrogel.Patent of the present invention has and adopts that raw material is few, productive rate is high.
Product of the present invention is being liquid condition lower than 20 ℃ of temperature, and convenient drug administration dispersibility jiao zi can be penetrated into vagina, any deep, uterus fold place as water, kill pathogen, contact body temperature is after 3-5 minutes, and gelling becomes gel, temperature is higher, gel strength is larger, and adhesion is stronger.Infection and inflammation part temperature are higher, and this preparation can intelligently form the high intensity hydrogel film that contains medicine at patient part, be covered in patient part, is difficult for overflowing, and has guaranteed to greatest extent action time and the activity of medicine and patient part.
In addition, product of the present invention also possesses following advantage for gyniatrics:
Liquid form is conducive to the medicine free permeation and conceals the antibacterial place to vagina, uterus gauffer, and this place is the main cause that causes reproductive tract infection repeatedly to show effect.Be in a liquid state before administration or semi-solid state due to temperature-sensitive hydrogel, has the free-flow performance, can with medicine by pressure deliver to existing administrator send less than the degree of depth, and by vagina, uterus fold place (the fold place pathogen is more not reach the root of recurrence) that mobility makes drug osmotic can not be penetrated into to general solid gel, kill thoroughly, fast pathogen.
Foreign sense, not pollution clothes: solid gel enters in body with the lumps form, disperses inhomogeneously, is difficult to be penetrated into the deep fold place.Intelligent gel enters in body in the curtain coating mode, can form at mucomembranous surface the film of even thickness, and the foreign body sensation and the large quantity of fluid that form without solid gel flow out, and avoid pollution clothes, bed accessory etc.
Mechanical strength is large: adhesion is strong, the effect patient part time is long: with conventional solid gel phase ratio, the mechanical strength of intelligent gel is large, gel rubber system is difficult for bursting and collapses, bio-adhesive, and property is strong, can firmly attach to vaginal mucosa continues more than 16 hours, avoided gynecological lotion, short drawback of solid gel agent local action time, solid gel holdup time of patient part approximately 2-3Jj, the time, lotion approximately 30 minutes.
Clean and comfortable: the effective entity composition of solid gel is only 1% left and right; 99% is water; effective entity composition of intelligence thermosensitive hydrogel is up to 40%; can form the high film of mechanical strength at mucomembranous surface, flow out without large quantity of fluid, reduce and pollute; do not affect; sexual intercourse sensation, and due to the increase of entity composition, greatly strengthened spreadability protection and lubricity to mucosa.
The specific embodiment:
Embodiment 1:
At ambient temperature, the 0.12g hydroxypropyl emthylcellulose is dissolved in the 100mL distilled water, forming molar concentration is the Gonak of 0.01m1; The 0.17g silver nitrate is dissolved in the l0mL distilled water, and forming molar concentration is the silver nitrate solution of 0.1m01/L; Get l0mL Gonak and 1.5mL silver nitrate solution mix homogeneously, making its mol ratio is 1:1.5.Mixed solution is placed on 100W shines 2.5h under ballast fluorescent high-voltage hydrargyrum, thereby make the nanometer silver hydrogel.
Embodiment 2:
The present embodiment is the structural characterization to the antibacterial material of silver nanoparticle in embodiment 1, and is specific as follows: adopt in Tecnai G2F20 S-Twin 200 KV field transmission determination of electron microscopy nanometer silver hydrogels the shape and element of silver nano-grain to form and characterize.Sample preparation is that the nanometer silver hydrogel is dissolved in ultra-pure water, is dispersed on the TEM copper mesh after the dehydrated alcohol precipitation.Can be found out by TEM figure, the particle diameter of nanometer silver is between 5-10nm, and granular size is more even, mainly contains Ag, S, C, 0 four kinds of elements in sample.20 values that X-x ray diffraction records the characteristic diffraction peak of sample are followed successively by 38.2 ', 44.4 ', 64.5 ', 77.5 ', the diffraction crystal face that shows is respectively (111), (200), (220) and (311) and standard crystalline state silver card sheet (PDFg04-0783) contrast, the diffraction peak energy of the diffraction maximum that records and standard diagram is well coincide, and illustrates that prepared sample is Nano silver grain.Fourier transform infrared spectroscopy is measured and is obtained containing in the nanometer silver hydrogel L-hydroxypropyl emthylcellulose major function group.
Embodiment 3:
The present embodiment is selected be bacillus coli and staphylococcus aureus as the representative of gram negative bacteria and positive bacteria, embodiment 1 has been carried out the test of biocidal property.
The operating procedure of inhibition zone test is as follows: pour in sterilized culture dish after the sterilization of LB Solid agar culture is dissolved, after the culture medium cooled and solidified, adding respectively 2mL concentration is the bacterium liquid of 1XiOGCFU/mL, then with aseptic spreading rod with its coating evenly, use again aseptic nipper gripping Oxford cup, be placed on gently dull and stereotyped centre, then that it is for a moment standing, can be fixed on flat board.And then the nanometer silver hydrogel solution that pipettes 2mL joins in the cup of Oxford, and with sterilized water as blank, every kind of thalline is done three Duplicate Samples.Culture medium as for cultivating 24h in the incubator of 37 ℃, is then measured respectively the diameter of inhibition zone with ruler, then average.Through checking that the nanometer silver hydrogel has obvious fungistatic effect
Embodiment 4:
The minimal inhibitory concentration (MIC) of nanometer rice silver hydrogel and minimal bactericidal concentration (MBC) test: adopt doubling dilution and plating method to measure respectively the nanometer silver hydrogel to minimal inhibitory concentration and the minimal bactericidal concentration of bacillus coli and staphylococcus aureus, concrete process of the test is as follows:
Get 10 sterilized test tubes, each pipe adds LB fluid medium 2mL, then adds the nanometer silver hydrogel solution 2mL of 0.70mg/mL (being 0.05mol) to the 1st pipe, draws 2mL after mixing and joins in the 2nd pipe.By that analogy, be diluted to the 9th pipe according to the method always, then abandon it with drawing 2mL in the 9th pipe, the 10th pipe adds the sterilized water of 2mL as the blank group in test tube, after mixing, draw 2mL, abandons it.Adding respectively concentration in above-mentioned 10 test tubes is the bacillus coli suspension 0.2mL of 1X106CFU/mL, after shaking up, is placed in 37 ℃ of constant incubators and cultivates 24 hours, then perusal result.Concentration concentration minimum and the obviously not muddy contained nanometer silver hydrogel of test tube is the minimal inhibitory concentration of this antibacterial material.
Experiment shows that nanometer silver hydrogel of the present invention has very strong bacteriostasis and sterilization ability, and all can produce significant inhibitory action to common gram positive bacteria and negative bacterium; Pay when the concentration of nanometer silver hydrogel reaches 0.35mg/mL, can kill most common antibacterials.
The above is only embodiments of the invention, is not limited to patent of invention, and for a person skilled in the art, the present invention can have various modifications and variations.All within the spirit and principle of invention, any modification of doing, be equal to replacement, improvement etc., within all should being included in the claim scope of invention.
Claims (3)
1. intelligent nano silver hydrogel, it is characterized in that: making step is as follows
The first step: prepare hydroxypropyl emthylcellulose-silver ion coordination compound as material dissolution take silver nitrate and hydroxypropyl emthylcellulose in pure water;
Second step: as precursor, utilize in hydrated electron that ultraviolet light irradiation produces and radical pair precursor solution silver ion to reduce the preparation nano silver colloidal sol this complex solution; Hydroxypropyl emthylcellulose is used for being coated with nanometer silver by sulfydryl and silver; The amino of hydroxypropyl emthylcellulose and carboxylic acid form hydrogel as hydrophilic residue network hydrone, thereby make the nanometer silver hydrogel.
2. a kind of intelligent nano silver hydrogel according to claim 1 is characterized in that: described hydroxypropyl emthylcellulose comprises a kind of in both of D type, L-type, and perhaps D type and L-type mixes; The concentration conditions of described formation hydrogel be the hydroxypropyl emthylcellulose quality account for the hydrogel gross mass 0.1%-0.15%.
3. a kind of intelligent nano silver hydrogel according to claim 1, it is characterized in that: described ultraviolet light is 100 watts of high voltage mercury lamp irradiations.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104907582A (en) * | 2015-06-23 | 2015-09-16 | 南开大学 | Synthetic method of hydroxypropyl methyl cellulose-clad nanometer silver material |
| CN107522875A (en) * | 2016-06-20 | 2017-12-29 | 中国科学院宁波材料技术与工程研究所 | Hydrogel, its preparation method and the application of Nano silver grain crosslinking |
| CN108913015A (en) * | 2017-04-05 | 2018-11-30 | 中国科学院宁波材料技术与工程研究所 | Dual network silicone hydrogels/nano silver composite material, preparation method and application |
| CN112315976A (en) * | 2020-11-16 | 2021-02-05 | 山西大同大学 | Injectable antibacterial composite hydrogel crosslinked by silver-loaded attapulgite, and preparation method and application thereof |
| CN112869948A (en) * | 2021-01-12 | 2021-06-01 | 香港理工大学 | Intelligent moisture-responsive compression fabric, preparation method thereof and intelligent moisture-responsive compression bandage |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101999412A (en) * | 2010-11-19 | 2011-04-06 | 佘振定 | Nano-silver solution and preparation method thereof |
| CN102698313A (en) * | 2012-01-11 | 2012-10-03 | 北京大学 | Nano-silver antibacterial hydrogel and preparation method thereof |
-
2013
- 2013-03-06 CN CN2013100703002A patent/CN103126977A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101999412A (en) * | 2010-11-19 | 2011-04-06 | 佘振定 | Nano-silver solution and preparation method thereof |
| CN102698313A (en) * | 2012-01-11 | 2012-10-03 | 北京大学 | Nano-silver antibacterial hydrogel and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104907582A (en) * | 2015-06-23 | 2015-09-16 | 南开大学 | Synthetic method of hydroxypropyl methyl cellulose-clad nanometer silver material |
| CN107522875A (en) * | 2016-06-20 | 2017-12-29 | 中国科学院宁波材料技术与工程研究所 | Hydrogel, its preparation method and the application of Nano silver grain crosslinking |
| CN108913015A (en) * | 2017-04-05 | 2018-11-30 | 中国科学院宁波材料技术与工程研究所 | Dual network silicone hydrogels/nano silver composite material, preparation method and application |
| CN108913015B (en) * | 2017-04-05 | 2020-08-04 | 中国科学院宁波材料技术与工程研究所 | Double-network organic silicon hydrogel/nano-silver composite material, preparation method and application |
| CN112315976A (en) * | 2020-11-16 | 2021-02-05 | 山西大同大学 | Injectable antibacterial composite hydrogel crosslinked by silver-loaded attapulgite, and preparation method and application thereof |
| CN112315976B (en) * | 2020-11-16 | 2022-10-11 | 山西大同大学 | Injectable antibacterial composite hydrogel crosslinked by silver-loaded attapulgite, and preparation method and application thereof |
| CN112869948A (en) * | 2021-01-12 | 2021-06-01 | 香港理工大学 | Intelligent moisture-responsive compression fabric, preparation method thereof and intelligent moisture-responsive compression bandage |
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Application publication date: 20130605 |