CN106176807A - A kind of industrialized preparing process of nanometer gold antibacterial - Google Patents
A kind of industrialized preparing process of nanometer gold antibacterial Download PDFInfo
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- CN106176807A CN106176807A CN201610576325.3A CN201610576325A CN106176807A CN 106176807 A CN106176807 A CN 106176807A CN 201610576325 A CN201610576325 A CN 201610576325A CN 106176807 A CN106176807 A CN 106176807A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention provides the industrialized preparing process of a kind of nanometer gold antibacterial, the method comprises the following steps: chlorauric acid solution is mixed by (1) with containing aminopyrimidine micromolecular and the solution of amino micromolecular or potassium chloroplatinate solution, obtains mixed solution；(2) in described mixed solution, under agitation rapidly join the solution of reducing agent, fully i.e. obtain described nanometer gold antibacterial after reaction；Wherein, the volume of described nanometer gold antibacterial is more than 5L, preferably 5～100L, and the joining day of reducing agent was less than 5 minutes, preferably more than 1 minute, more preferably 10～60 seconds.Additionally provide the nanometer gold antibacterial produced by the method, and the method or the application of nanometer gold antibacterial.
Description
Technical field
The present invention relates to the preparation method of a kind of nanometer gold antibacterial, be specifically related to the industrialization of a kind of nanometer gold antibacterial
Production method, and the nanometer gold antibacterial prepared by the method.
Background technology
Nanometer silver (AgNPs) is widely used due to excellent anti-microbial property, but due to nanometer silver unstability with
And relatively big to the toxicity of human body cell, limit it at medical some aspect such as grade and use.In recent years, stability is more preferable, to human body
The less nanometer gold of cytotoxicity is gradually in the news as the research of antibacterial.Nanometer gold (AuNPs) as novel antibacterial,
Most research is prepared the scale of nanometer gold antibacterial and is in the small-scale stage of laboratory, and preparation process is more complicated, it is difficult to
Industrialization, the antibacterial effect of the nanometer gold antibacterial of some research reports is not very good.The mercapto of patent CN102188383A report
The nanometer gold antibacterial that yl pyrimidines is modified is poor to the antibacterial effect of gram positive bacteria, such as staphylococcus aureus.Hong-
Zheng Lai(Lai H Z,Chen W Y,Wu C Y,et al.Potent antibacterial nanoparticles
for pathogenic bacteria[J].ACS applied materials&interfaces,2015,7(3):2046-
2054.) the nanometer gold antibacterial that report vancomycin is modified is compared to simple vancomycin, and antibiotic property has had bigger proposing
Height, but antibiotic vancomycin present on nanometer gold, due to the problem of bacterial drug resistance, its use still to the mankind and from
So there is hidden danger.(Zhao Y, the Jiang X.Multiple strategies to activate gold such as Zhao yuyun
Nanoparticles as antibiotics [J] .Nanoscale, 2013,5 (18): 8340-8350. and Zhao Y, Ye C,
Liu W,et al.Tuning the composition of AuPt bimetallic nanoparticles for
antibacterial application[J].Angewandte Chemie International Edition,2014,53
(31): 8127-8131.) the nanometer gold antibacterial of the double-component drug modification of the aminopyrimidine reported/containing the little molecule of amino and receiving
Rice gold platinum bimetallic antibacterial has the strongest broad spectrum antibacterial, its to the toxicity of human body cell well below nanometer silver, and not
Bacterial drug resistance can be produced, be the most promising antibacterial of class, but its reducing agent NaBH in preparation process4It is to drip
The mode added joins in reaction solution, and during large-scale production, this will be the most time-consuming, it is not easy to realize, and secondly, nanometer gold reacts
After complete, need to dialyse with bag filter, be still difficulty with during commercial production.
Therefore, by researched and developed have excellence broad spectrum antibacterial, without bacterial drug resistance, to little the receiving of human body cell toxicity
Meter Jin still has problems in the process realize industrialized production to be needed to solve.
Summary of the invention
Therefore, it is an object of the invention to overcome drawbacks described above of the prior art, it is provided that a kind of technique is simple, efficiency more
The industrialized preparing process of nanometer gold antibacterial high, with low cost, and the nanometer gold antibacterial prepared by the method.
For achieving the above object, the invention provides the industrialized preparing process of a kind of nanometer gold antibacterial, the method bag
Include following steps:
(1) by chlorauric acid solution with containing aminopyrimidine micromolecular and the solution of amino micromolecular or potassium chloroplatinate solution
Mixing, obtains mixed solution.
(2) in described mixed solution, under agitation rapidly join the solution of reducing agent, fully i.e. obtain described after reaction
Nanometer gold antibacterial.
Wherein, the volume of described nanometer gold antibacterial can be more than 5L, it may be preferred to be 5～100L, such as, can be
50～100L.And the joining day of reducing agent can be less than 5 minutes, it may be preferred to less than 1 minute, can be more preferably
10s～60s.The joining day of reducing agent can change according to different reaction volumes, but the time can recorded selected from the present invention
Scope, such as, can be 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s etc..
It should be readily apparent to one skilled in the art that for the gold chloride raw material preparing chlorauric acid solution it can is that four hydration chlorine are golden
Acid.
The method according to the invention, wherein, the mean diameter containing gold nano grain in described nanometer gold antibacterial be 1～
20nm, preferably 1～10nm, such as 2～10nm.It is highly preferred that described containing gold nano grain dense in nanometer gold antibacterial
Degree is 10～2000ppm, preferably 400～2000ppm, more preferably 800～2000ppm, and such as 400～1000ppm,
Or 800～1000ppm.Wherein, 1ppm generally can be scaled 1mg/L.
The method according to the invention, wherein, relative to the cumulative volume of described nanometer gold antibacterial, the concentration of described gold chloride
May be about 10～2000ppm, preferably 400～2000ppm, more preferably 800～2000ppm.
The method according to the invention, wherein, described reducing agent is sodium borohydride, sodium ascorbate or sodium citrate.Preferably
Rubbing of ground, described reducing agent and the mol ratio of gold chloride or described reducing agent and gold chloride and potassium chloroplatinate (total mole number)
That ratio is 1:1～10:1, preferably 2:1～3:1.It is further preferred that the response time in step (2) is 0.5～3 hour,
Reaction temperature is below room temperature, such as can be below 25 DEG C, such as 20～25 DEG C.
The method according to the invention, wherein, when chlorauric acid solution and containing aminopyrimidine micromolecular and amino micromolecular
Solution mixing time, at gained nanometer gold antibacterial containing in gold nano grain, aminopyrimidine micromolecular rubs with gold element
Your content ratio is for 0.5:1～2:1, such as 1:1, and the molar content of amino micromolecular and gold element ratio is for 0.5:1～2:1, example
Such as 1:1.The mole of described gold element can correspond to the mole of gold chloride.Preferably, described aminopyrimidine micromolecular
One in 2-sulfydryl-4,6-di-amino-pyrimidine, 2-sulfydryl-4-aminopyrimidine and 2,4-diaminourea-6-mercaptopyrimidine or
Multiple.It is highly preferred that described amino micromolecular is selected from guanidine, metformin, metformin hydrochloride, 1-(3-chlorophenol) biguanide, chlorine
One or more in quinoline, hydrochloric acid acetylcholine and tripolycyanamide.It is further preferred that when chlorauric acid solution and potassium chloroplatinate
Solution mixing time, at gained nanometer gold antibacterial containing in gold nano grain, the atomic percent of platinum is 10～65%.
The method according to the invention, wherein, in the described solution containing aminopyrimidine micromolecular and amino micromolecular also
Comprise organic acid or mineral acid, preferably acetic acid, propanoic acid or hydrochloric acid.It is highly preferred that described organic acid or mineral acid are received described
Mass percent in rice gold antibacterial is 0.05%～10%.Can be such as 0.1～0.2%.
The method according to the invention, wherein, in the described solution containing aminopyrimidine micromolecular and amino micromolecular also
Comprise nonionic surfactant, preferably tween or Polyethylene Glycol.It is highly preferred that nonionic surfactant is in described nanometer
Mass percent in gold antibacterial is 0.01%～10%.Can be such as 0.01～0.1%.
The method according to the invention, wherein, described chlorauric acid solution, containing aminopyrimidine micromolecular and amino micromolecular
The solvent of solution of solution, potassium chloroplatinate solution or reducing agent be each independently water, can be such as deionized water.
The method according to the invention, wherein, described method does not comprise the step of nanometer gold antibacterial described in purification.Preferably
, the step of nanometer gold antibacterial described in purification includes processing with bag filter dialysis treatment or centrifugal filtration.In other words, the present invention
Production method need not carry out purification containing gold nano grain by modes such as bag filter dialysis treatment or centrifugal filtration process.As more entering
The restriction of one step, the production method of the present invention can also be expressed as being made up of step (1) and step (2).
Present invention also offers a kind of nanometer gold antibacterial, this nanometer gold antibacterial is prepared by the said method of the present invention.
The industrialized preparing process or the above-mentioned nanometer gold that present invention also offers the above-mentioned nanometer gold antibacterial of the present invention resist
Microbial inoculum application in preparing antimicrobial product or medicine.Preferably, described antimicrobial product or medicine can be antibacterial and/or sterilization
Product or medicine.It is highly preferred that described antibacterials can be used for treating burn, scald, decubital ulcer infection, scytitis,
Gynaecopathia or the medicine of anal and intestinal disease.
Compared with prior art, the industrialized preparing process of nanometer gold antibacterial that the present invention provides have but be not limited to
Lower beneficial effect:
1, the present invention is applicable to reaction solution volume at more than 5L, the production rule of preferably more than 10L, even more than 100L
Mould, production method technique is simple, cost is relatively low for this, and the nanometer gold antibacterial produced has excellent antibacterial effect and thin to human body
Born of the same parents' low toxicity.
2. use in the nanometer gold antibacterial that produced of the inventive method containing gold nano grain than the grain of small-scale production
Footpath is less, and size is more homogeneous, and no significant difference in terms of antibacterial effect, and antibacterial effect is close with nanometer silver.
3, document is reported as obtaining that granule is little and the nano-particle of size uniformity, have employed dropping reducing agent (such as hydroboration
Sodium or sodium citrate) mode of solution.Such as, relative to the mixed solution of 25mL, the reductant solution of 5mL needed at 2 minutes
Drip off.If being also adopted by which in large-scale production, such as when volume is 100L scale, then dropping reductant solution time
Between then need a couple of days, this can greatly reduce production efficiency, is not suitable for industrialized production.By contrast, at the producer of the present invention
In method, the solution of reducing agent is disposably to rapidly join (i.e. during 100L, the joining day is no more than 5 minutes) to reactant liquor (this
The mixed solution of invention) in, the most more save the time, contribute to improving production efficiency.
4. use disposably rapidly join reductant solution and drip reductant solution compare, obtained nanometer gold is antibacterial
In agent containing gold nano grain equal no significant difference in terms of particle diameter, size uniformity degree, and also without bright in terms of antibacterial effect
Significant difference is different.
5, needing after the reaction containing gold nano grain in document report is dialysed 24 to 48 hours with bag filter, and industry
Dialysis technique during metaplasia is produced is extremely complex, and dialysis machine is much more expensive.Production method of the present invention need not dialyse with bag filter
The modes such as process or centrifugal filtration process are carried out purification and are contained gold nano grain, and therefore technique is the simplest, reduces production cost, enters
One step improves production efficiency.
6. the present invention does not use the nanometer gold antibacterial prepared by the purification steps such as dialysis anti-with the nanometer gold of dialysis treatment
Microbial inoculum is compared, and antibacterial effect is the most excellent, and the lowest to the toxicity of human body cell, and resists well below commercially available nanometer silver
Microbial inoculum and silver nitrate.
Accompanying drawing explanation
Hereinafter, describe embodiment of the present invention in detail in conjunction with accompanying drawing, wherein:
Fig. 1 show embodiments of the invention 1～2 with in the nanometer gold antibacterial of comparative example 1～2 containing gold nano grain
TEM figure；
Fig. 2 show embodiments of the invention 3 with in the nanometer gold antibacterial of comparative example 3～5 containing gold nano grain
TEM figure (using nanometer silver AgNPs as comparison)；
Fig. 3 show the nanometer gold antibacterial of embodiments of the invention 4, comparative example 6 cytotoxicity figure (with nanometer silver and
Silver nitrate is as comparison).
Detailed description of the invention
The present invention is further illustrated below by specific embodiment, it should be understood, however, that, these embodiments are only
It is used for specifically describing in more detail, and is not to be construed as limiting in any form the present invention.
This part to the present invention test used in material and test method carry out general description.Although it is
Realize many materials that the object of the invention used and operational approach is to it is known in the art that but the present invention still uses up at this
May describe in detail.It will be apparent to those skilled in the art that within a context, if not specified, material therefor of the present invention and behaviour
It is well known in the art as method.
The reagent and the instrument that use in following example are as follows:
Reagent:
Instrument:
Inductively coupled plasma atomic emission spectrometer (ICP-OES), model iCAP 6300, U.S. Thermo
Scientific company.
Transmission electron microscope (TEM), model Tecnai G2 20S-TWIN, FEI Co. of the U.S..
Embodiment 1
The present embodiment is for illustrating the industrialized preparing process of the nanometer gold antibacterial of the present invention and being prepared by the method
Nanometer gold antibacterial.
The preparation method that the present embodiment uses is:
(1) the four hydration gold chlorides of 80g are dissolved in the deionized water of 20L, obtain chlorauric acid solution.By a certain amount of 2-
Sulfydryl-4,6-di-amino-pyrimidine and metformin hydrochloride are dissolved in the deionized water of 20L, are additionally added a certain amount of Tween 80 and second
Acid, is completely dissolved in water helping lend some impetus to aminopyrimidine micromolecular and amino micromolecular, obtains containing Aminopyrimidines
Little molecule and the solution of amino micromolecular.By two solution mixing, obtain mixed solution.
(2) a certain amount of sodium borohydride is dissolved in the deionized water of 10L, under agitation by fast for above-mentioned sodium borohydride solution
Speed add (1 minute used time) in above-mentioned mixed solution, 1 hour stirred below of room temperature to fully reaction, be not required to use dialysis
Deng purifying process, the concentration i.e. obtaining about 50L is about (calculating according to rate of charge) nanometer gold antibacterial of 800ppm.
According to rate of charge, 2-sulfydryl-4, the molar content of 6-di-amino-pyrimidine and gold element (or gold chloride) ratio for 1:1,
The molar content of metformin hydrochloride and gold element (or gold chloride) ratio for 1:1, borane reducing agent sodium hydride and gold chloride mole
Content ratio is for 3:1, and it is 0.1% that acetic acid accounts for the mass percent of nanometer gold antibacterial, and surface active agent tween 80 accounts for nanometer gold and resists
The mass percent of microbial inoculum is 0.01%.
Recorded by ICP-OES, this nanometer gold antibacterial contain concentration be about 800ppm containing gold nano grain (i.e. 2-mercapto
The nanogold particle that base-4,6-di-amino-pyrimidine and metformin hydrochloride double-component are modified).Nanogold particle is recorded by TEM
Particle diameter is about 2～6nm, is specifically shown in Fig. 1.
Embodiment 2
The present embodiment is for illustrating the industrialized preparing process of the nanometer gold antibacterial of the present invention and being prepared by the method
Nanometer gold antibacterial.
The preparation method of the nanometer gold antibacterial of embodiment 2 is the most same as in Example 1, and difference is, each reagent (includes
Raw material and solvent etc.) consumption the most scaled, so that the volume of gained nanometer gold antibacterial is 5L.
Wherein, by ICP-OES record the nanometer gold antibacterial (5L) of embodiment 2 containing concentration be about 800ppm containing Jenner
Rice grain (i.e. the nanogold particle that 2-sulfydryl-4,6-di-amino-pyrimidine and metformin hydrochloride double-component are modified), is recorded by TEM
The particle diameter of nanogold particle is about 3～7nm, is specifically shown in Fig. 1.
According to rate of charge, 2-sulfydryl-4, the molar content of 6-di-amino-pyrimidine and gold element (or gold chloride) ratio for 1:1,
The molar content of metformin hydrochloride and gold element (or gold chloride) ratio for 1:1, borane reducing agent sodium hydride and gold element mole
Content is than for 3:1.
Comparative example 1～2
Prepare the nanometer gold antibacterial of comparative example 1,2 respectively according to preparation method same as in Example 1, its difference exists
In, the consumption of each reagent (including raw material and solvent etc.) is the most scaled, so that the volume of gained nanometer gold antibacterial is respectively
For 250mL, 25mL.
By ICP-OES record the nanometer gold antibacterial (250mL) of comparative example 1 containing concentration be about 800ppm containing gold nano
Granule (i.e. the nanogold particle that 2-sulfydryl-4,6-di-amino-pyrimidine and metformin hydrochloride double-component are modified), is recorded by TEM and receives
The particle diameter of rice gold grain is about 5～10nm, is specifically shown in Fig. 1.
According to rate of charge, 2-sulfydryl-4, the molar content of 6-di-amino-pyrimidine and gold element (or gold chloride) ratio for 1:1,
The molar content of metformin hydrochloride and gold element (or gold chloride) ratio is for 1:1.
By ICP-OES record the nanometer gold antibacterial (25mL) of comparative example 2 containing concentration be about 800ppm containing gold nano
Granule (i.e. the nanogold particle that 2-sulfydryl-4,6-di-amino-pyrimidine and metformin hydrochloride double-component are modified), is recorded by TEM and receives
The particle diameter of rice gold grain is about 5～10nm, is specifically shown in Fig. 1.
Measuring according to rate of charge, 2-sulfydryl-4,6-di-amino-pyrimidine with the molar content ratio of gold element (or gold chloride) is
1:1, the molar content of metformin hydrochloride and gold element (or gold chloride) ratio is for 1:1.
Test example 1
According to micropore dilution process (National Committee for Clinical Laboratory
Standards., Methodsfor determining bactericidal activity of antimicrobial
Agents, M26-A, 1999.) measure minimal inhibitory concentration (MIC): by nanometer gold antibacterial or the nanometer of 100 μ L variable concentrations
Silver joins in 96 microwell plates, and the inoculum of 10 μ L same concentrations (104CFU/mL) adds in each micropore, 37 DEG C of cultivations
Observing after 24 hours, nanometer gold antibacterial minimum in the micropore of the bacterial growth that not can be seen that or the concentration of nanometer silver are
Minimal inhibitory concentration (MIC), this sample anti-microbial property of the least proof of MIC is the best.
Method described above measure embodiment 1～2 and the nanometer gold antibacterial of comparative example 1～2 (with nanogold particle AuNPs
Densitometer) MIC, and make comparisons with the MIC of commercially available nanometer silver (AgNPs) (purchased from Zhangjiagang Nai Er nanometer company).Carefully
Bacteria culture fluid is respectively E.coli (escherichia coli), S.aureus (staphylococcus aureus) and P.aeruginosa (green pus bar
Bacterium), measure three groups, the results are shown in Table 1.
Table 1 embodiment 1～2 and the anti-microbial property of nanometer gold antibacterial of comparative example 1～2 compare and (make with commercially available nanometer silver
Comparison)
As known from Table 1, the nanometer gold antibacterial that the scale (such as 5L, 50L) using volume to be more than 5L produces and small-scale
The nanometer gold antibacterial that (25mL, 250mL) produces without substantially changing, wherein have also appeared some effect and carries in terms of anti-microbial property
Rise.Such as, embodiment 1 (50L) is better than comparative example 1 and 2 to the antibacterial ability of staphylococcus aureus, and embodiment 2 (5L) is to green
The antibacterial ability of pus bacillus is better than comparative example 1 (250mL).
Embodiment 3
The present embodiment is for illustrating the industrialized preparing process of the nanometer gold antibacterial of the present invention and being prepared by the method
Nanometer gold antibacterial.
The preparation method that the present embodiment uses is:
(1) the four hydration gold chlorides of 20g are dissolved in the deionized water of 2L, obtain chlorauric acid solution.By a certain amount of 2-
Sulfydryl-4-aminopyrimidine and 1-(3-chlorophenol) biguanide are dissolved in the water of 2L, are additionally added a certain amount of Polyethylene Glycol and acetic acid, to have
Help promote that aminopyrimidine micromolecular and amino micromolecular are completely dissolved in water, obtain containing aminopyrimidine micromolecular and
The solution of amino micromolecular.By two solution mixing, obtain mixed solution.
(2) a certain amount of sodium citrate is dissolved in the deionized water of 1L, under agitation by fast for above-mentioned sodium citrate solution
Speed add (10 seconds used times) in above-mentioned mixed solution, 0.5 hour stirred below of room temperature (such as 25 DEG C) to fully reaction, be not required to
Use the purifying process such as dialysis, i.e. obtain the nanometer gold antibacterial of about 5L.
Recorded by ICP-OES, this nanometer gold antibacterial contain concentration be about 2000ppm containing gold nano grain (i.e. 2-mercapto
The nanogold particle that base-4-aminopyrimidine and 1-(3-chlorophenol) biguanide double-component are modified).The grain of nanogold particle is recorded by TEM
Footpath is about 3～7nm, is specifically shown in Fig. 2.
According to rate of charge, the molar content of 2-sulfydryl-4-aminopyrimidine and gold element is than for 1:1,1-(3-chlorophenol) biguanide
With the molar content of gold element than for 1:1, the molar content of reducing agent sodium citrate and gold chloride is than for 3:1, and acetic acid accounts for nanometer
The mass percent of gold antibacterial is 0.2%, and surfactant polyethylene accounts for the mass percent of nanometer gold antibacterial and is
0.1%.
Comparative example 3～5
The preparation method of the nanometer gold antibacterial of comparative example 3～5 is the most same as in Example 3, and difference is, sodium citrate
Addition (can the use dropping mode) time of solution is respectively 2 minutes, 20 minutes and 200 minutes.
Wherein, ICP-OES the nanometer gold antibacterial (2 minutes) recording comparative example 3 is about containing of 2000ppm containing concentration
Gold nano grain (i.e. the nanogold particle that 2-sulfydryl-4-aminopyrimidine and 1-(3-chlorophenol) biguanide double-component are modified), is surveyed by TEM
The particle diameter obtaining nanogold particle is about 5～8nm, is specifically shown in Fig. 2.According to rate of charge, 2-sulfydryl-4-aminopyrimidine and gold element
Molar content than the molar content for 1:1,1-(3-chlorophenol) biguanide and gold element than for 1:1.
By ICP-OES record the nanometer gold antibacterial (20 minutes) of comparative example 4 containing concentration be about 2000ppm containing Jenner
Rice grain (i.e. the nanogold particle that 2-sulfydryl-4-aminopyrimidine and 1-(3-chlorophenol) biguanide double-component are modified), is recorded by TEM and receives
The particle diameter of rice gold grain is about 6～9nm, is specifically shown in Fig. 2.According to rate of charge, 2-sulfydryl-4-aminopyrimidine and gold element mole
Content than the molar content for 1:1,1-(3-chlorophenol) biguanide and gold element than for 1:1.
By ICP-OES record the nanometer gold antibacterial (200 minutes) of comparative example 5 containing concentration be about 2000ppm containing gold
Nano-particle (i.e. the nanogold particle that 2-sulfydryl-4-aminopyrimidine and 1-(3-chlorophenol) biguanide double-component are modified), is recorded by TEM
The particle diameter of nanogold particle is about 7～10nm, is specifically shown in Fig. 2.According to rate of charge, 2-sulfydryl-4-aminopyrimidine and gold element
Molar content than the molar content for 1:1,1-(3-chlorophenol) biguanide and gold element than for 1:1.
Test example 2
The nanometer gold antibacterial of embodiment 3 and comparative example 3～5 is measured (to receive according to the same procedure described in test example 1
The densitometer of rice gold grain AuNPs) MIC, and (have purchased from Zhangjiagang Nai Er nanosecond science and technology with commercially available nanometer silver (AgNPs)
Limit company) MIC make comparisons.Inoculum is respectively E.coli (escherichia coli), S.aureus (staphylococcus aureus)
With P.aeruginosa (bacillus pyocyaneus), measure three groups, the results are shown in Table 2.
The anti-microbial property of the nanometer gold antibacterial of table 2 embodiment 3 and comparative example 3～5 compares (opposes with commercially available nanometer silver
According to)
| Sample | E.coli | S.aureus | P.aeruginosa |
| Embodiment 3 (10s) | 1.439 | 2.878 | 2.878 |
| Comparative example 3 (2min) | 1.416 | 5.666 | 2.838 |
| Comparative example 4 (20min) | 2.842 | 5.684 | 5.684 |
| Comparative example 5 (200min) | 2.780 | 5.559 | 5.559 |
| AgNPs | 1.834 | 3.667 | 3.667 |
As known from Table 2, the nanometer gold antibacterial disposably rapidly joining reducing agent (as embodiment 1 uses 10s) and produce
Compared with the nanometer gold antibacterial that the longer joining day (such as 2min, 20min, 200min or longer) produces, although the used time is significantly
Shorten, but anti-microbial property is without significant difference, the most also presents effect promoting.Such as, embodiment 3 (10s) is to greatly
Enterobacteria, the antibacterial ability of bacillus pyocyaneus are better than comparative example 4 (20min) and comparative example 5 (200min), to staphylococcus aureus
Antibacterial ability the most optimal.
Embodiment 4
The present embodiment is for illustrating the industrialized preparing process of the nanometer gold antibacterial of the present invention and being prepared by the method
Nanometer gold antibacterial.
The preparation method that the present embodiment uses is:
(1) four hydration gold chlorides and the 55g potassium chloroplatinate of 25g are dissolved in the deionized water of 60L, obtain mixed solution.
(2) a certain amount of sodium borohydride is dissolved in the deionized water of 40L, under agitation by fast for above-mentioned sodium borohydride solution
Speed add (60 seconds used times) in above-mentioned mixed solution, 3 hours stirred below of room temperature to fully reaction, be not required to use dialysis etc.
Purifying process, i.e. obtains the nanometer gold antibacterial of about 100L.
According to rate of charge, the molar content of borane reducing agent sodium hydride and gold chloride and potassium chloroplatinate is than for 2:1, the atom of platinum
Percentage ratio is 65%, and therefore this gold-Pt nanoparticle is represented by Au35Pt65Nano-particle.
Recorded by ICP-OES, this nanometer gold antibacterial contain concentration be 400ppm containing gold-Pt nanoparticle (i.e. gold-platinum
Bimetallic component nano-particle).The particle diameter being recorded nanogold particle by TEM is about 7～10nm.
Comparative example 6 and test example 3
Test example 3 is for comparing the antibacterial effect of the nanometer gold antibacterial using and not using dialysis obtained by purification process
Really.
Preparing comparative example 6 according to the method for embodiment 4, it differs only in, by reacted solution cutoff
Bag filter for 3KDa is dialysed 48 hours in pure water, within every 6 hours, changes a water, obtains the nanometer gold containing gold-Pt nanoparticle
Antimicrobial, as a comparison case 6.
The nanometer gold antibacterial of embodiment 4 and comparative example 6 is measured (with containing gold according to the same procedure described in test example 1
The densitometer of nano-particle) MIC.Inoculum is respectively E.coli (escherichia coli), S.aureus (Staphylococcus aureus
Bacterium) and P.aeruginosa (bacillus pyocyaneus), measure three groups, the results are shown in Table 3.
The anti-microbial property of the nanometer gold antibacterial of table 3 embodiment 4 and comparative example 6 compares
Test example 4
This test example is for comparing the cell toxicant of the nanometer gold antibacterial using and not using dialysis obtained by purification process
Property (compare with commercially available nanometer silver and silver nitrate solution) simultaneously.
Cell toxicity test operating process: Human umbilical vein endothelial cells (HUVEC) is clear containing 10% N of fetal blood
The Eagle culture medium (DMEM) that Dulbecco improves is cultivated.10 are added in each hole of 96 microwell plates4Individual HUVEC cell,
Each hole adds the nanometer gold antibacterial of the embodiment 4 of variable concentrations, the nanometer gold antibacterial of comparative example 6, commercialization nanometer
Silver, silver nitrate solution are to 200 microlitres.Microporous medium is cultivated 48 hours at 37 DEG C, does not add the HUVEC cell of antibacterial
As comparison.After having cultivated, the phosphate buffer solution (PBS, 0.01mol/L, pH 7.4) of the solution in micropore is washed once, adds
The CCK-8 solution of 10% (v/v), in microporous medium, is cultivated 2 hours at 37 DEG C.Survey at enzyme-linked immunosorbent assay instrument 450nm
Amount various kinds sample wells and the light absorption value of control wells.Calculate each sample well cell relative viability.Each sample porocyte relative activity
It is defined as: light absorption value × 100% of each hole light absorption value/control wells.Result of the test is shown in Fig. 3.
Knowable to the result of the test shown in Fig. 3, the present invention does not uses the nanometer gold antibacterial of dialysis treatment different dense
Cytotoxicity under Du is all significantly lower than nanometer silver and silver nitrate solution.
Although present invention has been a certain degree of description, it will be apparent that, without departing from the spirit and scope of the present invention
Under the conditions of, the suitable change of each condition can be carried out.It is appreciated that and the invention is not restricted to described embodiment, and be attributed to right
The scope required, it includes the equivalent of described each factor.
Claims (10)
1. the industrialized preparing process of a nanometer gold antibacterial, it is characterised in that the method comprises the following steps:
(1) chlorauric acid solution is mixed with containing aminopyrimidine micromolecular and the solution of amino micromolecular or potassium chloroplatinate solution
Close, obtain mixed solution；
(2) in described mixed solution, under agitation rapidly join the solution of reducing agent, fully i.e. obtain described nanometer after reaction
Gold antibacterial；
Wherein, the volume of described nanometer gold antibacterial is more than 5L, preferably 5～100L, and the joining day of reducing agent is not
More than 5 minutes, preferably more than 1 minute, more preferably 10～60 seconds.
Method the most according to claim 1, it is characterised in that the putting down containing gold nano grain in described nanometer gold antibacterial
All particle diameters are 1～20nm, preferably 1～10nm；It is highly preferred that the described concentration containing gold nano grain in nanometer gold antibacterial
It is 10～2000ppm, preferably 400～2000ppm, more preferably 800～2000ppm.
Method the most according to claim 1 and 2, it is characterised in that described reducing agent be sodium borohydride, sodium ascorbate or
Sodium citrate；Preferably, the mol ratio of described reducing agent and gold chloride or described reducing agent and gold chloride and potassium chloroplatinate
Mol ratio is 1:1～10:1, preferably 2:1～3:1；It is further preferred that the response time in step (2) is 0.5～3 little
Time, reaction temperature is below room temperature.
The most according to the method in any one of claims 1 to 3, it is characterised in that when chlorauric acid solution and containing aminopyrimidine
Micromolecular and amino micromolecular solution mixing time, at gained nanometer gold antibacterial containing in gold nano grain, amino is phonetic
The molar content of pyridine micromolecular and gold element is than for 0.5:1～2:1, preferably 1:1, and amino micromolecular rubs with gold element
Your content ratio is for 0.5:1～2:1, preferably 1:1；Preferably, described aminopyrimidine micromolecular is selected from 2-sulfydryl-4,6-diamino
One or more in yl pyrimidines, 2-sulfydryl-4-aminopyrimidine and 2,4-diaminourea-6-mercaptopyrimidine；It is highly preferred that described ammonia
Base micromolecular is selected from guanidine, metformin, metformin hydrochloride, 1-(3-chlorophenol) biguanide, chloroquine, hydrochloric acid acetylcholine and trimerization
One or more in cyanamide；It is further preferred that when chlorauric acid solution mixes with potassium chloroplatinate solution, in gained nanometer
Gold antibacterial containing in gold nano grain, the atomic percent of platinum is 10～65%.
Method the most according to any one of claim 1 to 4, it is characterised in that described containing aminopyrimidine micromolecular and
The solution of amino micromolecular also comprises organic acid or mineral acid, preferably acetic acid, propanoic acid or hydrochloric acid；It is highly preferred that it is described
Organic acid or mineral acid mass percent in described nanometer gold antibacterial are 0.05%～10%, preferably 0.1～
0.2%.
Method the most according to any one of claim 1 to 5, it is characterised in that described containing aminopyrimidine micromolecular and
The solution of amino micromolecular also comprises nonionic surfactant, preferably tween or Polyethylene Glycol；It is highly preferred that non-from
Sub-surface activating agent mass percent in described nanometer gold antibacterial is 0.01%～10%, preferably 0.01～0.1%.
Method the most according to any one of claim 1 to 6, it is characterised in that described chlorauric acid solution, containing aminopyrimidine
The solvent of the solution of micromolecular and the solution of amino micromolecular, potassium chloroplatinate solution or reducing agent is each independently water.
Method the most according to any one of claim 1 to 7, it is characterised in that described method does not comprise described in purification to be received
The step of rice gold antibacterial；Preferably, the step of nanometer gold antibacterial described in purification includes by bag filter dialysis treatment or centrifugal
Filtration treatment.
9. a nanometer gold antibacterial, it is characterised in that this nanometer gold antibacterial is by according to any one of claim 1 to 8
Method prepares.
10. described in the industrialized preparing process of the nanometer gold antibacterial according to any one of claim 1 to 8 or claim 9
The application in preparing antimicrobial product or medicine of the nanometer gold antibacterial；Preferably, described antimicrobial product or medicine be antibacterial and/
Sterilization product or medicine；It is highly preferred that described antibacterials are for being used for treating burn, scald, decubital ulcer infection, dermatitis
The medicine of disease, gynaecopathia or anal and intestinal disease.
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| CN108785728A (en) * | 2017-05-05 | 2018-11-13 | 国家纳米科学中心 | Antiseptic dressing, preparation method and the application of the nanogold of drug containing intermediate modification |
| CN114177198A (en) * | 2021-10-29 | 2022-03-15 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano-gold antibacterial agent and preparation method and application thereof |
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| CN108785728A (en) * | 2017-05-05 | 2018-11-13 | 国家纳米科学中心 | Antiseptic dressing, preparation method and the application of the nanogold of drug containing intermediate modification |
| CN107598185A (en) * | 2017-08-29 | 2018-01-19 | 重庆和其美科技有限公司 | A kind of preparation method of the antiseptic containing nanogold |
| CN107598185B (en) * | 2017-08-29 | 2020-07-28 | 重庆和其美科技有限公司 | Preparation method of antibacterial agent containing nanogold |
| CN108210515A (en) * | 2018-01-18 | 2018-06-29 | 南京林业大学 | A kind of novel nano gold complex antimicrobials and preparation method thereof |
| CN114177198A (en) * | 2021-10-29 | 2022-03-15 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano-gold antibacterial agent and preparation method and application thereof |
| CN114177198B (en) * | 2021-10-29 | 2023-06-23 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano gold antibacterial agent and preparation method and application thereof |
| CN114539625A (en) * | 2022-02-28 | 2022-05-27 | 广东粤港澳大湾区国家纳米科技创新研究院 | Nano-gold antibacterial powder, antibacterial plastic master batch or material, preparation method and application |
| CN114539625B (en) * | 2022-02-28 | 2023-12-05 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial nano gold powder, antibacterial plastic master batch or material, preparation method and application |
| CN115363050A (en) * | 2022-09-29 | 2022-11-22 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial colloid containing anthocyanin and preparation method and application thereof |
| CN115363050B (en) * | 2022-09-29 | 2024-01-30 | 广东粤港澳大湾区国家纳米科技创新研究院 | Antibacterial colloid containing anthocyanin and preparation method and application thereof |
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