CN102600478A - Surface self-assembled gold nano-cephalosporin as well as preparation method and application of same - Google Patents
Surface self-assembled gold nano-cephalosporin as well as preparation method and application of same Download PDFInfo
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- CN102600478A CN102600478A CN2012100099130A CN201210009913A CN102600478A CN 102600478 A CN102600478 A CN 102600478A CN 2012100099130 A CN2012100099130 A CN 2012100099130A CN 201210009913 A CN201210009913 A CN 201210009913A CN 102600478 A CN102600478 A CN 102600478A
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- 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
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Abstract
The invention discloses surface self-assembled gold nano-cephalosporin as well as a preparation method and an application of the same. The surface self-assembled gold nano-cephalosporin disclosed by the invention is shown in the following structural formula. The surface self-assembled gold nano-cephalosporin is characterized in that antibiotics are connected with the surfaces of gold nano-particles via a ligand with a structure of HS-(CH2CH2O)n-CH2-RH; and the gold nano-particles are connected with the sulfydryl end of HS-(CH2CH2O)n-CH2-RH. Experimental test indicates that the surface self-assembled gold nano-cephalosporin with efficient antibacterial performance disclosed by the invention can realize low-concentration efficient antibacterial action on gram-negative bacterium, so that the surface self-assembled gold nano-cephalosporin can be widely applied as a novel nano-antibiotic.
Description
Technical field
The present invention relates to a kind of surperficial self assembly gold nano cephalo and preparation method thereof and application.
Background technology
Nano-particle has caused people's extensive concern because of its distinctive physics and chemical property, and in biological every field, particularly is widely used as the pharmaceutical carrier aspect.Wherein, be the nano-antibacterial element of preparing carriers with the nano-particle, not only shown higher antibacterial effect, and effect has preferably also been arranged for abusing caused bacterial drug resistance owing to antibiotic.As: Jiang Xingyu etc. [Jiang, et.al.J.Am.Chem.Soc., 2010,132,12349-12356.].Discover, the antibiotic monomer is self-assembled to nano grain surface after, thereby the permeability that can improve cell membrane significantly improves antibacterial effect, this nanometer antibiotic also has the obvious suppression effect for fastbacteria simultaneously.People's such as Perry [Perry, et.al.J.Mater.Chem., 2010,20,6789-6798.] research can produce higher antibacterial effect after also finding antibiotics self-assembled to the nanogold particle surface equally.Yet these are seen in the nanometer antibiotic of report at present, and its preparation method all concentrates on and directly adopts antibiotic that nanogold particle is reduced preparation, and this makes and when biologic applications, often is subject to higher cytotoxicity of nano-particle and low biocompatibility.
Summary of the invention
The purpose of this invention is to provide a kind of surperficial self assembly gold nano cephalo and preparation method thereof and application.
The invention provides a kind of surperficial self assembly gold nano cepham compound of following structure:
R is-CH
2-NH-,-CH
2-O-or-CO-O-, n is the integer of 0-11, the integer of preferred 1-3, x is the integer of 1-7, preferred 1 or 2.
In the above-mentioned surperficial self assembly gold nano cepham compound, the mean diameter of gold nano grain is 1-6nm, preferred 4.5-4.6nm;
The mean diameter of said surperficial self assembly gold nano cepham compound is 1-6nm, preferred 4.5-4.6nm;
Gold atom in the said gold nano grain and-S-(CH
2CH
2O)
n-CH
2The mol ratio of-R-and antibiotics cephalo base is 4-15: 1-3: 1, and preferred 4: 1: 1;
Said antibiotics cephalo base is following group:
The method of the above-mentioned surperficial self assembly gold nano cepham compound of preparation provided by the invention comprises the steps:
1) with HS-(CH
2CH
2O)
n-CH
2The gold nano grain of-RH and the protection of four octyl group ammonium bromide carries out the aglucon exchange reaction, and reaction finishes and obtains the gold nano grain of mercaptan protection;
Said HS-(CH
2CH
2O)
n-CH
2Among-the RH, R is-CH
2-NH-,-CH
2-O-or-CO-O-, n is the integer of 0-11, the integer of preferred 1-3;
2) gold nano grain and the acylting agent with antibiotics cepham compound shown in the formula II, the protection of said step 1) gained mercaptan carries out acylation reaction, and reaction finishes and obtains said surperficial self assembly gold nano cepham compound,
In the said aglucon exchange reaction of the said step 1) of this method step, HS-(CH
2CH
2O)
n-CH
2The molar ratio of the gold nano grain of-RH and the protection of four octyl group ammonium bromide is 1-3: 1, and preferred 1: 1; Temperature is 0-40 ℃, and preferred 20-30 ℃, the time is 4-48 hour, preferred 12-24 hour; The mean diameter of the gold nano grain of said four octyl group ammonium bromide protection is 1-6nm, preferred 4.5-4.6nm.
Said step 2) in the said acylation reaction step, said acylting agent is selected from N, at least a in N-dicyclohexyl carbon imidodicarbonic diamide (DCC), 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride (EDCI) and the triethylamine.The gold nano grain of antibiotics cepham compound shown in the said formula II, the protection of said step 1) gained mercaptan and the molar ratio of acylting agent are 1-2: 1-2: 1-5, preferred 1: 1: 3;
In the said acylation reaction step, temperature is 20-25 ℃, and the time is 6-48 hour, preferred 24 hours.
The said aglucon exchange reaction of said step 1) is to carry out in the mixed liquor formed of 1: 1 dichloromethane and methanol mixed at dichloromethane or by volume ratio;
Said step 2) carries out at least a in oxolane, dimethyl formamide and dichloromethane of said acylation reaction.
In the said method, the gold nano grain of the reactant four octyl group ammonium bromide of said step 1) protection can get according to following method preparation: get 5mL HAuCl
4The toluene solution (50mM) of aqueous solution (30.0mM) and 14mL four octyl group quaternary amines mixes each other, stirs and makes HAuCl in 30 minutes
4Under the assistance of four octyl groups, fully get into organic layer, final water layer is transparent and toluene layer becomes claret, adds continued fully and stirs 2 hours until reacting completely.Separate organic layer, become ruby red under the room temperature.Under intense stirring condition, dropwise add 8 milliliters of excessive sodium borohydrides (0.2M) then, along with the carrying out that drips, toluene layer takes place to be dried up by ruby red-Bai-ash-brown-dark nitrogen gradually, obtains the gold nano grain of four octyl group ammonium bromide protection.
In addition, with the above-mentioned surperficial self assembly gold nano cephalo provided by the invention antibiotics that is active component and should the application of surface self assembly gold nano cephalo in preparation antibiotic (especially escherichia coli) element, also belong to protection scope of the present invention.
Surperficial self assembly gold nano cephalo provided by the invention is through HS-(CH on the gold nano grain surface
2CH
2O) n-CH
2The aglucon of-RH structure is connected with antibiotics shown in the formula II; Said gold nano grain and HS-(CH
2CH
2O) n-CH
2The sulfydryl end of-RH is connected.Experiment test shows that the surperficial self assembly gold nano cephalo with high-efficiency antimicrobial performance provided by the invention can be realized the low concentration high-efficiency antimicrobial to gram negative bacteria, thereby can be used as a kind of novel nano-antibacterial element and be widely used.
Description of drawings
Fig. 1 is the ultraviolet spectrogram of embodiment 2 preparation gained surface self assembly gold nano cepham compounds
Fig. 2 is the infrared spectrum of embodiment 2 preparation gained surface self assembly gold nano cepham compounds
Fig. 3 is the inhibition zone experiment of embodiment 2 preparation gained surface self assembly gold nano cepham compounds
The specific embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration, but the present invention is not limited to following examples.Said method is conventional method if no special instructions.Said reactant all can get from open commercial sources if no special instructions.Polyethylene glycol groups mercaptan amino or hydroxyl all is to get according to the preparation of the method among the Chinese patent ZL200910081175.9 among the embodiment.
Embodiment 1, the surperficial self assembly gold nano cepham compound of preparation
1, the preparation of the gold nano grain of four octyl group ammonium bromide protection
Get 5mL HAuCl
4The toluene solution (50mM) of aqueous solution (30.0mM) and 14mL four octyl group quaternary amines mixes each other, stirs and makes HAuCl in 30 minutes
4Under the assistance of four octyl groups, fully get into organic layer, final water layer is transparent and toluene layer becomes claret, adds continued fully and stirs 2 hours until reacting completely.Separate organic layer, become ruby red under the room temperature.Under intense stirring condition, dropwise add 8 milliliters of excessive sodium borohydrides (0.2M) then; Along with the carrying out that drips; Toluene layer takes place to be dried up by ruby red-Bai-ash-brown-dark nitrogen gradually; Obtain the gold nano grain of four octyl group ammonium bromide protection, wherein, the mean diameter of gold nano grain is 4.5nm.
2, omega-amino-four preparation of gold nano grain of three dithioglycols protections of contracting
The gold nano grain 0.05mM that step 1 is obtained is dissolved in 5 milliliters of dichloromethane, again with 0.1mMHS-(CH
2CH
2O)
n-CH
2-CH
2OH (n=3), under nitrogen atmosphere stirring at room 6-24 hour complete until the aglucon exchange reaction.The crude product that removes after desolvating gold nano grain is dissolved in methanol, separates through polydextran gel Sephadex LH-20 post and removes by-product, excessive TOAB and remaining sulfydryl aglucon.Surperficial self assembly gold nano grain after the purification is subsequent use in-20 ℃ with the stored in form of dry powder.
3, the preparation of surperficial self assembly gold nano cepham compound
Above-mentioned gold nano grain (2mM) is dissolved in 5mL solvent N, in the dinethylformamide, then to wherein adding antibiotics cepham compound shown in the formula II (2mM), DCC (4mM), triethylamine 2mM.Room temperature (20-25 ℃) is reaction 24h down, remove DMF after, dissolve with methanol, Sephadex LH-20 separate product 5mg.
The structural confirmation data of this product are following:
At 1710 places strong C=O absworption peak is arranged on its infrared spectrum, explain to be connected with cephalo on the gold nano grain; X-ray photoelectron power spectrum (XPS) result shows that the mol ratio of the plain cephalo base of gold atom and antibacterial surface in the surperficial self assembly gold nano cepham compound is 5: 1, and transmission electron microscope (TEM) result shows that the mean diameter of this surface self assembly gold nano cepham compound is 4.5 ± 0.5nm.
By on can know that this product structure is correct, be the chemical compound of following structure:
R is-CH
2-O-, x=2, n are 3, the mol ratio of the plain cephalo base of gold atom and antibacterial surface is 5: 1,
Said antibiotics cephalo base is following group:
Embodiment 2, the surperficial self assembly gold nano cepham compound of preparation
1) preparation such as the embodiment 1 of the gold nano grain of four octyl group ammonium bromide protection.
2) the gold nano grain 0.1mM that step 1 is obtained is dissolved in 5 ml methanol, again with 0.1mMHS-(CH
2CH
2O)
n-CH
2-NH
2(n=2), under nitrogen atmosphere stirring at room 6-24 hour complete until the aglucon exchange reaction.The crude product that removes after desolvating gold nano grain is dissolved in methanol, separates through polydextran gel Sephadex LH-20 post and removes by-product, excessive TOAB and remaining sulfydryl aglucon.Surperficial self assembly gold nano grain after the purification is subsequent use in-20 ℃ with the stored in form of dry powder.
3) method for preparing of surperficial self assembly gold nano cepham compound such as embodiment 1.
The structural confirmation data of products therefrom are following:
Fig. 1 is the ultraviolet spectra of this product, and Fig. 2 is an infrared spectrum, can know that by figure this product has strong C=O absworption peak at 1730 places, explains to be connected with antibiotics cephalo base on the gold nano grain; X-ray photoelectron power spectrum (XPS) result shows that the mol ratio of the plain cephalo base of gold atom and antibacterial surface in this surface self assembly gold nano cepham compound is 5: 1, and transmission electron microscope (TEM) result shows that the mean diameter of this surface self assembly gold nano cepham compound is 4.5 ± 0.5nm.
By on can know that this product structure is correct, be the chemical compound of following structure:
R is-CH
2-NH-, x=1, n are 2, the mol ratio of the plain cephalo base of gold atom and antibacterial surface is 5: 1,
Said antibiotics cephalo base is following group:
The surperficial self assembly gold nano cephalo that embodiment 3, preparation have the high-efficiency antimicrobial performance
1) preparation such as the embodiment 1 of the gold nano grain of four octyl group ammonium bromide protection.
2) the gold nano grain 0.05mM that step 1 is obtained is dissolved in 5 milliliters of dichloromethane, again with 0.1mMHS-(CH
2CH
2O)
n-CH
2-OH (n=1), under nitrogen atmosphere stirring at room 6-24 hour complete until the aglucon exchange reaction.The crude product that removes after desolvating gold nano grain is dissolved in methanol, separates through polydextran gel Sephadex LH-20 post and removes by-product, excessive TOAB and remaining sulfydryl aglucon.Surperficial self assembly gold nano grain after the purification is subsequent use in-20 ℃ with the stored in form of dry powder.
3) method for preparing of surperficial self assembly gold nano cepham compound such as embodiment 1.
The structural confirmation data of products therefrom are following:
At 1720 places strong C=O absworption peak is arranged on its infrared spectrum, explain to be connected with antibiotics cephalo base on the gold nano grain; X-ray photoelectron power spectrum (XPS) result shows that the mol ratio of the plain cephalo base of gold atom and antibacterial surface in this surface self assembly gold nano cepham compound is 3: 1, and transmission electron microscope (TEM) result shows that the mean diameter of this surface self assembly gold nano cepham compound is 4.5 ± 0.5nm.
By on can know that this product structure is correct, be the chemical compound of following structure:
R is-CH
2-O-, x=2, n are 1, gold atom is 3: 1 with mol ratio with the plain cephalo base of antibacterial surface;
Said antibiotics cephalo base is following group:
represents gold nano grain.
The minimum inhibitory concentration experiment of the surperficial self assembly gold nano cepham compound of embodiment 4, embodiment 1 preparation
Adopt broth dilution method to antibiotics cepham compound test shown in prepared surperficial self assembly gold nano cepham compound of embodiment 1 and the formula II its (deposit number is ATCC 11775 for escherichia coli; China common micro-organisms culture presevation administrative center) minimum inhibitory concentration, concrete steps are following:
1. micro-drug sensitive plate preparation: 2 kinds of medicines are dissolved in 100% dimethyl sulfoxide respectively, and making mass concentration is 1mg/mL, the dilution of reuse 1640 culture medium; 10 grades of doubling dilutions make initial concentration 0.1 μ g/mL then, and end level is 20 μ g/mL; The corresponding adding in the aseptic 96 hole ELISA Plates, every hole 100 μ L, the 11st hole adds not 1640 liquid bases, the 100 μ L of pastille; The 12nd hole adds and does not contain medicinal liquid base 200 μ L, and positive control is made in the 11st hole, blank is made in the 12nd hole.It is subsequent use to put-70 ℃ of refrigerators.
2. bacterium liquid preparation: with the strain subject escherichia coli from 4 ℃ of taking-ups; Change after the activation and plant, cultivate 12h for 37 ℃, be injected on the PDA inclined-plane with the physiological saline solution 1mL that contains 0.05% Tween 80 in the PDA culture medium; Collect bacteria suspension, arrive (2～4) * 10 with the whole concentration of 1640 liquid keynotes
4Cfu/mL, put 4 ℃ subsequent use.
3. bacterium liquid inoculation: drug sensitive plate takes out from-70 ℃ and melts, and the every hole of the bacteria suspension of each bacterial strain is added 100 μ L, and 12 holes do not add, and this step makes the bacterial concentration dilution be (1～2) * 10
4Cfu/mL, drug quality concentration is 0.002～1 μ g/mL.
4. cultivate, add developer and first lysate: drug sensitive plate is put 28 ℃ of cultivations behind the inoculation bacterium liquid, observes growing state every day.Behind the well-grown of positive control hole, each hole adds MTT 20 μ L, puts 28 ℃ of incubator 4h.Then in each Kong Jiajia lysate 100 μ L.
5. the result judges: respectively at adding 18h behind the methanol solution, 24h, 30h; With ELIASA (DG3022A type; East China Electronics Co., Ltd pipe factory) in the 550nm place, survey each hole absorbance with the blank well zeroing, be the MIC terminal point to compare the lowest drug concentration hole of absorbance decline more than 90% with the growth control hole.
The result finds: the minimum inhibitory concentration of gold nano cephalo is 2 μ g mL; And the minimum inhibitory concentration of embodiment 1 preparation gained surface self assembly gold nano cephalo is 8 μ g mL
-1, antibacterial effect has improved four times.Fig. 3 is the inhibition zone result of the test, and wherein, the antibacterial circle diameter of the surperficial self assembly gold nano cepham compound that embodiment 1 is prepared is 2.3cm, and the antibacterial circle diameter of the cepham compound of antibiotics shown in the formula II is 1.1cm.
Claims (10)
1. the surperficial self assembly gold nano cepham compound of a following structure:
R is-CH
2-NH-,-CH
2-O-or-CO-O-, n is the integer of 0-11, x is the integer of 1-7.
2. surperficial self assembly gold nano cepham compound according to claim 1, it is characterized in that: n is the integer of 1-3, x is 1 or 2;
In the said surperficial self assembly gold nano cepham compound, the mean diameter of gold nano grain is 1-6nm, preferred 4.5-4.6nm;
The mean diameter of said surperficial self assembly gold nano cepham compound is 1-6nm, preferred 4.5-4.6nm;
Gold atom in the said gold nano grain and-S-(CH
2CH
2O)
n-CH
2The mol ratio of-R-and antibiotics cephalo base is 4-15: 1-3: 1, and preferred 4: 1: 1;
Said antibiotics cephalo base is following group:
3. a method for preparing claim 1 or 2 arbitrary described surperficial self assembly gold nano cepham compounds comprises the steps:
1) with HS-(CH
2CH
2O)
n-CH
2The gold nano grain of-RH and the protection of four octyl group ammonium bromide carries out the aglucon exchange reaction, and reaction finishes and obtains the gold nano grain of mercaptan protection;
Said HS-(CH
2CH
2O)
n-CH
2Among-the RH, R is-CH
2-NH-,-CH
2-O-or-CO-O-, n is the integer of 0-11;
2) gold nano grain and the acylting agent with antibiotics cepham compound shown in the formula II, the protection of said step 1) gained mercaptan carries out acylation reaction, and reaction finishes and obtains said surperficial self assembly gold nano cepham compound,
Formula II.
4. method according to claim 3 is characterized in that: in the said aglucon exchange reaction of the said step 1) step, and HS-(CH
2CH
2O)
n-CH
2The molar ratio of the gold nano grain of-RH and the protection of four octyl group ammonium bromide is 1-3: 1, and preferred 1: 1;
Temperature is 0-40 ℃, and preferred 20-30 ℃, the time is 4-48 hour, preferred 12-24 hour;
The mean diameter of the gold nano grain of said four octyl group ammonium bromide protection is 1-6nm, preferred 4.5-4.6nm;
Said HS-(CH
2CH
2O)
n-CH
2Among-the RH, n is the integer of 1-3.
5. according to the arbitrary described method of claim 3-4; It is characterized in that: said step 2) in the said acylation reaction step; Said acylting agent is selected from N, at least a in N-dicyclohexyl carbon imidodicarbonic diamide, 1-ethyl-3-(3-dimethylamino-propyl) carbodiimide hydrochloride and the triethylamine.
6. according to the arbitrary described method of claim 3-5; It is characterized in that: said step 2); The gold nano grain of the cepham compound of antibiotics shown in the formula II, the protection of said step 1) mercaptan and the molar ratio of acylting agent are 1-2: 1-2: 1-5, preferred 1: 1: 3.
In the said acylation reaction step, temperature is 20-25 ℃, and the time is 6-48 hour, preferred 12 hours.
7. according to the arbitrary described method of claim 3-6, it is characterized in that: the said aglucon exchange reaction of said step 1) is to carry out in the mixed liquor formed of 1: 1 dichloromethane and methanol mixed at dichloromethane or by volume ratio;
Said step 2) said acylation reaction is at oxolane, N, carries out at least a in dinethylformamide and the dichloromethane.
8. be the antibiotics of active component with claim 1 or 2 arbitrary said surperficial self assembly gold nano cepham compounds.
9. claim 1 or the 2 arbitrary said surperficial self assembly gold nano cepham compounds application in preparation antibiotics.
10. application according to claim 9 is characterized in that: said bacterium is escherichia coli.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107412780A (en) * | 2016-05-23 | 2017-12-01 | 国家纳米科学中心 | A kind of antiseptic based on gold nano grain surface modification azacyclo- small molecule |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525342A (en) * | 2009-04-03 | 2009-09-09 | 中国科学院化学研究所 | Surface self-assembly gold nanoprobe with free radical capture performance and preparing method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525342A (en) * | 2009-04-03 | 2009-09-09 | 中国科学院化学研究所 | Surface self-assembly gold nanoprobe with free radical capture performance and preparing method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107412780A (en) * | 2016-05-23 | 2017-12-01 | 国家纳米科学中心 | A kind of antiseptic based on gold nano grain surface modification azacyclo- small molecule |
| CN107412780B (en) * | 2016-05-23 | 2022-04-15 | 国家纳米科学中心 | Antibacterial agent based on gold nanoparticle surface modified nitrogen heterocyclic micromolecules |
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Application publication date: 20120725 |