CN102581298A - Gold nanoparticle array with continuously-changed surface charge density - Google Patents
Gold nanoparticle array with continuously-changed surface charge density Download PDFInfo
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Abstract
The invention discloses a gold nanoparticle array with a continuously-changed surface charge density. The gold nanoparticle array consists of 17 types of gold nanoparticles and is obtained by adjusting a ratio of a charged group ligand to a neutral ligand; and a peptide with a plurality of charged groups is used as a ligand molecule to chemically modify the surfaces of the molecule. The gold nanoparticle array provided by the invention not only can be used for researching an action mechanism between the gold nanoparticles and cells and further can be used for indicating the design of a carrier in a biomedical field as applications, such as target carrying drugs, biological development, disease diagnosis, gene treatment and the like.
Description
Technical field
The present invention relates to a kind of gold nano grain array, relate in particular to a kind of surface charge density continually varying gold nano grain array; The functional modification technical field on metal nanometer material surface.
Background technology
Nano material has the ability of passing biological barriers such as cell membrane, and big quantity research has been reported its purposes at a plurality of biomedical aspects such as target carrying medicine, biological developing, medical diagnosis on disease and gene therapies.Simultaneously, the potential source biomolecule toxicity of nano material has also caused concern widely.Therefore, the interaction between detailed understanding nano material and the cell becomes and presses for.These interactions comprise: electrostatic interaction, hydrophobic effect, hydrogen bond action, three-dimensional effect etc.Wherein nano material and intercellular electrostatic interaction have been studied and have been used for carrying gene, enhancing cellular uptake and the escape of endocytosis body etc.The surface charge of the nano material also a lot of biological behavior with it is relevant, for example, organizes diffusion, bio distribution, cellular uptake, cytotoxicity and protein combination etc.In order to study nano material and intercellular electrostatic interaction, be employed in nano-material surface usually and modify charged ligand molecular.But these charged ligand moleculars possibly provide other active forces except electrostatic interaction, thereby the effect that produce to mix has influenced our research to nano material and intercellular electrostatic interaction.For example, it has been generally acknowledged that electronegative nano material can not get into cell, because have Coulomb repulsion between this nano material and the cell membrane; Yet; Some electronegative nano materials, like CNT, polystyrene nanoparticles, having research to report can be by cellular uptake; Though reason is Coulomb repulsion, they can get into cell through hydrophobic effect.The applicant finds can carry out the electrostatic interaction between systematic research nano material and the cell through preparing a surface charge density continually varying gold nano grain array; And there is very little or similar other active force in this array and iuntercellular, and also do not appear in the newspapers through the research of retrieval of similar.
Summary of the invention
Modify the problem that exists to existing nano-material surface, the object of the present invention is to provide a kind of surface charge density continually varying gold nano grain array.
Surface charge density continually varying gold nano grain array of the present invention; Be through regulating the ratio of a charged groups part and a neutral ligand; And use the peptide that has a plurality of electric charge groups as ligand molecular, and the surface of gold nano grain is carried out obtaining after the chemical modification, it is characterized in that: said gold nano grain array is made up of 17 kinds of nano particles; Nano particle wherein is the circular gold nano grain of 5 ± 0.1 nanometers, representes with GNP01～GNP17 respectively; The continuous variation of the surface charge density of said gold nano grain array from the high density positive charge to the high density negative electrical charge, wherein charge density is followed successively by from the positive charge to the negative electrical charge :+2.87 ,+1.85 ,+1.0 ,+1.0; + 0.52 ,+0.29 ,+0.23 ,+0.15,0;-0.13 ,-0.20 ,-0.53 ,-0.73;-1.0 ,-1.0 ,-3.61 ,-4.18.
In the above-mentioned surface charge density continually varying gold nano grain array: said part is single part or two part, and single ligand molecular has 9 kinds, is respectively: peptide CALRRRRR-NH
2(1), peptide CALRRR-NH
2(2), lipoamide propylamine (3, chemical constitution is seen Fig. 1), peptide CALR-NH
2(4), lipoamide (5, chemical constitution is seen Fig. 1), peptide CALEEEE (6), peptide CALEE (7), lipoic acid (8, chemical constitution is seen Fig. 1) and peptide CALE-NH
2(9); Two ligand moleculars are: lipoic acid/lipoamide and lipoamide propylamine/lipoamide, proportion are lipoic acid/lipoamide from 100% to 0%, lipoamide propylamine/lipoamide from 100% to 0%; Said ligand molecular is connected with gold nano grain through golden sulfide linkage, and the number of the ligand molecular that each gold nano grain connects is 144～360.
Concrete, the ligand molecular number of above-mentioned every kind of nano particle is seen table 1, the ligand molecular ratio of every kind of nano particle is seen table 3.Described gold nano grain array sketch map and surface ligand molecular structure are seen Fig. 1 and Fig. 2.
Table 1: gold nano grain surface ligand molecule number and surface charge density
In order to understand essence of the present invention and its value better, below our continuous variation of this nano-grain array surface charge being described with the preparation experiment and the characterization result thereof of gold nano grain and it is in the application of studying nano material and iuntercellular electrostatic interaction.
1. the preparation of gold nano grain array:
Two ligand moleculars of single ligand molecular or different proportion are dissolved in (peptide is soluble in water) among the DMF, gold chloride are added in this solution also at room temperature stirred 30 minutes then.The aqueous solution of sodium borohydride is added dropwise to wherein.At room temperature continue to stir 4 hours.Neutralize the sodium borohydride that has not reacted with hydrochloric acid.The gold nano grain solution of gained carries out purifying with the method for dialysis or ultrafiltration washing.
2. the morphology analysis of gold nano grain array:
Select several kinds of nano particles to carry out the observation of perspective electron microscope as representative.Observed gold nano grain pattern is as shown in Figure 3 under perspective electron microscope, and gold nano grain is sub-circular, and average grain diameter is about 5 nanometers.
3. the elementary analysis of gold nano grain:
Get the gold nano grain of measured quantity, after the drying, it is carried out elementary analysis, results of elemental analyses is seen table 2.
Hydrocarbon nitrogen content in table 2 gold nano grain
4. the quantitative analysis of the ligand molecular iodine cutting method on gold nano grain surface:
The method that employing iodine is cut and high performance liquid chromatography-GC-MS are to the analysis of gold nano grain surface ligand molecular method quantification.Gold nano grain is distributed in the methyl alcohol, and the methanol solution of iodine adds wherein and at room temperature hatched 30 minutes.Naked gold removes through centrifugal, and supernatant injects high performance liquid chromatography/mass spectrum/Nitrogen detector (HPLC/MS/CLND) system and analyzes.Income analysis result sees Fig. 4.
5. surface charge density continually varying gold nano grain array is used to study nano material and iuntercellular electrostatic interaction:
The HeLa cell is cultivated in containing calf serum and antibiotic DMEM culture medium.Cell is inoculated in 12 orifice plates.Be placed on hatch 24 hours in the constant incubator after, sop up each hole culture medium and washing a time with PBS cushioning liquid, the cell culture medium solution with the 1mL nano particle is added in the hole then; Be placed on again hatch 12 hours in the constant incubator after; Sop up each hole culture medium and give a baby a bath on the third day after its birth time with PBS cushioning liquid, the adding pancreatin digests cell at the bottom of the hole; Add culture medium again and stop digestion, the pair cell counting.Each tests parallel doing three times.
The cell that cancellationization is got off adds chloroazotic acid, is placed on 37 ℃ and spends the night and become ion with thorough decomposition nano particle.Get this cell decomposed solution, the concentration of measuring gold in the cell digestion solution with ICP-MS can calculate intracellular nano material amount, like Fig. 6.We find electronegative, and it is less that neutral nano material with the band small positive charge gets into cell concentration, explain a little less than they and the intercellular electrostatic interaction; Along with the increase of positive charge density, the nano material quantitative change that gets into cell is many, explains that electrostatic interaction begins grow; When positive charge density greater than+1.0, the nano material amount that gets into cell no longer increases, the instruction card density of surface charge is full; Increase surface charge density again electrostatic interaction is strengthened, thereby do not have the increase of cellular uptake amount.
Can draw to draw a conclusion by above experimental result:
Cut back liquid chromatogram result according to perspective Electronic Speculum, elementary analysis and iodine, we can calculate the surface ligand molecular number of the gold nano grain array of preparation, thus can calculate the gold nano grain array surface charge density (table 1, Fig. 5).Therefore, surface charge density that we can say the gold nano grain array that the present invention prepares has continuous variation.Find with the iuntercellular electrostatic interaction with this array research nano material, electronegative, neutral and the nano material of being with small positive charge and intercellular electrostatic interaction a little less than; Thereby it is less to get into cell concentration, and along with the increase of positive charge density, electrostatic interaction begins grow; The nano material amount that gets into cell also becomes many; When positive charge density greater than+1.0, increase surface charge density again electrostatic interaction is strengthened, thereby do not have the increase of cellular uptake amount.The nano material amount that gets into cell no longer increases.
The surface charge density continually varying gold nano grain array of the present invention's preparation is made up of 17 kinds of nano particles; Because these nano grain surface charge density are different; Thereby when take place interacting, show different electrostatic interactions with cell; The mechanism of action between nano particle and the cell can be realized studying, the design that is applied to the carrier of biomedical sector as target carrying medicine, biological developing, medical diagnosis on disease and gene therapy etc. can also be instructed.
Description of drawings
Fig. 1: the surface charge density continually varying gold nano grain array and the surface ligand molecular structure of preparation.
Fig. 2: surface charge density continually varying gold nano grain array sketch map of the present invention.
Fig. 3: the gold nano grain diameter characterization of preparation.Wherein:
A: be the picture of GNP01 under transmission electron microscope; Its medium scale is 20nm.
B: be the picture of GNP04 under transmission electron microscope; Its medium scale is 20nm.
C: be the picture of GNP09 under transmission electron microscope; Its medium scale is 20nm.
D: be the picture of GNP13 under transmission electron microscope; Its medium scale is 20nm.
Fig. 4: HPLC/MS/CLND characterizes the molecule of nano-material surface.Wherein:
A: for being connected to the chemical constitution and the corresponding molecular weight of the surperficial ligand molecular of gold nano grain.
B: for corresponding to retention time being the electrospray ionization mass spectrum figure at peak of 3.9 minutes peak and 4.5 minutes.
C: for after ligand molecular separates through high performance liquid chromatography, colleges and universities' liquid phase spectrogram that the nitrogen monitor is write down.
Fig. 5: the continuous variation of gold nano grain array surface charge density.
Fig. 6: the cellular uptake amount of surface charge density continually varying gold nano grain array.
The specific embodiment
The preparation of gold nano grain array:
(attach ratios is seen table 3 with two ligand moleculars of single ligand molecular (0.064mmol) or different proportion; Two molecule total amounts are 0.064mmol) be dissolved in (peptide is dissolved in the 20mL water) among the DMF (20mL); (25.0mg 0.064mmol) is added in this solution and at room temperature stirred 30 minutes with gold chloride then.(7.2mg, aqueous solution 0.19mmol) (12mL) is added dropwise to wherein sodium borohydride.At room temperature continue to stir 4 hours.Neutralize the sodium borohydride that has not reacted with 1N HCl.The gold nano grain solution of gained carries out purifying with the method for dialysis (molecular cut off 3500) or ultrafiltration (molecular cut off 5000) washing.
The ingredient proportion of ligand molecular in the preparation of table 3 gold nano grain array
With perspective electron microscope the gold nano grain array is carried out morphology analysis:
Select GNP01, GNP04, GNP09 and GNP13 carry out the observation of perspective electron microscope as representative.At the JEOL1200EX perspective electron microscope, voltage 80KV, observed gold nano grain pattern is as shown in Figure 3 under the AMT 2k CCD camera lens, and gold nano grain is sub-circular, and average grain diameter is about 5 nanometers.
The elementary analysis of gold nano grain:
To GNP01, GNP02, GNP03, GNP04, GNP09, GNP14, GNP16 and GNP17 carry out elementary analysis.Get measured quantity (2mg) gold nano grain, after the drying, the results of elemental analyses that records is seen table 2.
Method and the high performance liquid chromatography-GC-MS cut through iodine carry out quantitative analysis to the ligand molecular that is connected the gold nano grain surface:
Adopt method that iodine cuts and high performance liquid chromatography-GC-MS to GNP04, GNP05, GNP06, GNP07, GNP08, GNP09, GNP10, GNP11, GNP12 and the analysis of GNP13 surface ligand molecular method quantification.Gold nano grain (2.0mg) is distributed in the methyl alcohol (100 μ L), and the methanol solution of iodine (100 μ L, 10mg/mL) wherein and at room temperature hatched 30 minutes by adding.Naked gold removes through centrifugal (1,3000 rev/min, 30 minutes), and 20 μ L supernatants inject high performance liquid chromatography/mass spectrum/Nitrogen detector (HPLC/MS/CLND) system and analyze.The condition of flowing phase: 0 minute, 10% methyl alcohol; 4.5 minute, 95% methyl alcohol; 5.5 minute, 95% methyl alcohol; 6.5 minute, 10% methyl alcohol; 7 minutes, 10% methyl alcohol.Flow rate 0.7mL/min.Income analysis result sees Fig. 4.
Surface ligand molecular number purpose is calculated:
Result according to elementary analysis can go out GNP01, GNP02, and GNP03, GNP04, GNP09, GNP16 and GNP17 surface ligand molecular number:
Because the ligand molecular of GNP14 8 is nonnitrogenous, so its surface ligand molecular number is just calculated with carbon content.
Peak area (Fig. 2 c) according to the liquid phase spectrogram of GNP04 surface ligand molecular number and its surface ligand molecule can calculate the molecular number of surface ligand 3 and the corresponding relation of peak area.Can calculate GNP05 like this, GNP06, the number of GNP07 and GNP08 surface ligand molecule 3.
In like manner, the peak area (Fig. 4 c) according to the liquid phase spectrogram of GNP09 surface ligand molecular number and its surface ligand molecule can calculate the molecular number of surface ligand 5 and the corresponding relation of peak area.Can calculate GNP05 like this, GNP06, GNP07, GNP08, GNP10, GNP11, the number of GNP12 and GNP13 surface ligand molecule 5.
GNP10, GNP11, the number of GNP12 and GNP13 surface ligand molecule 8 cannot accurately calculate, and supposes that their surface ligand molecules sum is consistent with GNP09 surface ligand molecular number.Cut GNP10, GNP11, the number of GNP12 and GNP13 surface ligand molecule 5 can obtain the number of surface ligand molecule 8.
The surface ligand molecular number of GNP15 is GNP14, the mean value of GNP16 and GNP17 surface ligand molecular number.
Result of calculation is seen table 1.
The calculating of surface charge density:
Because GNP03, GNP04, GNP14 and GNP15 surface ligand molecule all are 100% ligand moleculars with an electric charge group.So the surface charge density of setting GNP03 and GNP04 is+1.0; The surface charge density of GNP14 and GNP15 is-1.0.The surface charge density account form of other nano particle is following:
The surface charge density of GNP01 and GNP02:
The surface charge density of GNP16 and GNP17:
GNP05, GNP06, the surface charge density of GNP07 and GNP08:
The surface charge density of GNP01 and GNP02:
Result of calculation is seen Fig. 5 and table 1.
Cell is cultivated and the cellular uptake nano material:
The HeLa cell is cultivated in containing 10% calf serum and 1% antibiotic DMEM culture medium.Cell is inoculated in 12 orifice plates, and density is 200,000/hole.Be placed on 37 ℃, hatch 24 hours in the constant incubator of 5%CO2 after, sop up each hole culture medium and washing a time with PBS cushioning liquid; Cell culture medium solution (25 μ g/mL or 50 μ g/mL) with the 1mL nano particle is added in the hole then; Be placed on 37 ℃ again, hatch 12 hours in the constant incubator of 5%CO2 after, sop up each hole culture medium and give a baby a bath on the third day after its birth time with PBS cushioning liquid; Add 200 microlitre pancreatin (0.25%); At the bottom of the hole, digest cell, add 200 microlitre culture mediums again and stop digestion, the pair cell counting.
Each tests parallel doing three times.
Measure intracellular nano material amount with ICP-MS:
Get 200 microlitres and digest the cell that gets off, add 400 microlitre chloroazotic acid, be placed on 37 ℃ and spend the night and become ion with thorough decomposition nano particle.Therefrom get the cell decomposed solution of 100 microlitres, with containing 50ppb
236Mark in the Y, the solution of 1% nitric acid is diluted to 5 milliliters.And, make calibration curve with this solution allocation gold concentration standard liquid (1000,500,250,100,50,10,5 and 1ppb), with the concentration of gold in this curve calculation cell digestion solution.Calculate the nano material amount of each cell then, the result sees Fig. 6.
Claims (2)
1. surface charge density continually varying gold nano grain array; Be through regulating the ratio of a charged groups part and a neutral ligand; And use the peptide that has a plurality of electric charge groups as ligand molecular, and the surface of gold nano grain is carried out obtaining after the chemical modification, it is characterized in that: said gold nano grain array is made up of 17 kinds of nano particles; Nano particle wherein is the circular gold nano grain of 5 ± 0.1 nanometers, representes with GNP01～GNP17 respectively; The continuous variation of the surface charge density of said gold nano grain array from the high density positive charge to the high density negative electrical charge, wherein charge density is followed successively by from the positive charge to the negative electrical charge :+2.87 ,+1.85 ,+1.0 ,+1.0; + 0.52 ,+0.29 ,+0.23 ,+0.15,0;-0.13 ,-0.20 ,-0.53 ,-0.73;-1.0 ,-1.0 ,-3.61 ,-4.18.
2. surface charge density continually varying gold nano grain array as claimed in claim 1, it is characterized in that: said part is single part or two part, and single ligand molecular has 9 kinds, is respectively: peptide CALRRRRR-NH
2(1), peptide CALRRR-NH
2(2), lipoamide propylamine (3, chemical constitution is seen Fig. 1), peptide CALR-NH
2(4), lipoamide (5, chemical constitution is seen Fig. 1), peptide CALEEEE (6), peptide CALEE (7), lipoic acid (8, chemical constitution is seen Fig. 1) and peptide CALE-NH
2(9); Two ligand moleculars are: lipoic acid/lipoamide and lipoamide propylamine/lipoamide, proportion are lipoic acid/lipoamide from 100% to 0%, lipoamide propylamine/lipoamide from 100% to 0%; Said ligand molecular is connected with gold nano grain through golden sulfide linkage, and the number of the ligand molecular that each gold nano grain connects is 144～360.
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| CN110373320A (en) * | 2018-04-12 | 2019-10-25 | 苏州天际创新纳米技术有限公司 | Cell separator and its separation method |
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Application publication date: 20120718 |