CN102398027A - Chitosan-modified gold nanorod and manufacturing method thereof - Google Patents
Chitosan-modified gold nanorod and manufacturing method thereof Download PDFInfo
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- CN102398027A CN102398027A CN201010280569XA CN201010280569A CN102398027A CN 102398027 A CN102398027 A CN 102398027A CN 201010280569X A CN201010280569X A CN 201010280569XA CN 201010280569 A CN201010280569 A CN 201010280569A CN 102398027 A CN102398027 A CN 102398027A
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Abstract
The invention relates to a gold nanorod and a manufacturing method thereof. The manufacturing method comprises the following steps of: a, providing a mixed solution which comprises chitosan and a multi-alkyl trimethyl ammonium bromide-modified gold nanorod; b, chemically bonding the chitosan with the gold nanorod; and c, centrifuging to obtain a chitosan-modified gold nanorod. In the method, multi-alkyl trimethyl ammonium bromide is replaced by the chitosan, so that the aim of improving the biocompatibility of the gold nanorod is fulfilled.
Description
Technical field
The present invention relates to a kind of nano material and manufacturing approach thereof, relate in particular to a kind of gold nano post and manufacturing approach thereof.
Background technology
The peculiar property of nano material (like optics, electricity and magnetic properties) is main relevant with its size and shape; The research of nano material is flourish in recent years; And be applied to various fields gradually, like waste-water purification, antibiotic paint, cell developing technology and anti-cancer technology etc.
Gold nano-material has perspective in cell application medically.Be accompanied by the variation of external form; The gold nano-material surface plasma resonant absorbs the position and also can change; The most apneusis receipts wavelength can grow to ultrared wave-length coverage, because ultrared penetration power is strong, so gold nano-material can borrowed the potentiality that absorb infrared ray and have the cancer cell heat therapy.On the other hand, borrowing the strong scattering ability of gold nano-material, can in the detecting of details in a play not acted out on stage, but told through dialogues optics, strengthen the contrast of cell edges to be measured, reaching the effect of strengthening image light.
Yet the practice development of most nano materials still is subject to synthetic degree of difficulty and the toxicity that itself had.With regard to the gold nano post; In preparation for gold nano-material is dispersed in the solution; Often need add the interface activating agent; But interface activating agent (softex kw) commonly used at present often has like disadvantageous speciality such as cytotoxicities, thereby has limited the utilization of gold nano post on biomedicine.
In order to solve interface activating agent adverse effect in the technology, the method that adopts is usually further modified the gold nano post through softex kw for using kayexalate (polystyrene sulfonate).The principle of its modification is to borrow electrostatic interaction to make kayexalate cover softex kw and cover its toxicity.Though this method warp in vitro cell experiment confirms to have the Cytotoxic effect of covering softex kw really; Yet; Intravital environment is often complicatedly and can not expect external than live body; Therefore can not get rid of in the utilization in vivo, still have and expose softex kw and cause Cytotoxic risk.In addition, the selling at exorbitant prices of kayexalate also is unfavorable for the universal utilization of gold nano post on biomedicine.
In sum, consider the potentiality of gold nano post in the biomedicine utilization, the utmost point needs a suitable and effective method on the industry, to solve the shortcoming of softex kw bio-toxicity.
Summary of the invention
For solving the problems of the technologies described above, main purpose of the present invention is to provide a kind of gold nano post and preparation method thereof, and it is to replace the bio-compatibility that softex kw improves the gold nano post through chitin.
For achieving the above object, the invention provides a kind of manufacturing approach of gold nano post, it comprises following steps: a, a mixed liquor is provided, it comprises the gold nano post that chitin and many alkyl trimethyl ammonium bromides are modified; B, make said chitin and said gold nano post form chemical bonded refractory; Reach c, centrifugal treating to obtain the gold nano post that chitin is modified.
In above-mentioned manufacturing approach, preferably, said mixed liquor also comprises acid solution.
In above-mentioned manufacturing approach, preferably, said acid solution is to be used for the pH value of said mixed liquor is controlled in 2.0-7.0.
In above-mentioned manufacturing approach, preferably, said acid solution is in order to as the agent of leaving away.
In above-mentioned manufacturing approach, preferably, said acid solution is hydrochloric acid, acetic acid or its combination.
In above-mentioned manufacturing approach, preferably, said many alkyl trimethyl ammonium bromides are many alkyl trimethyl ammonium bromides of 3-40 for the alkyl number.
In above-mentioned manufacturing approach, preferably, said many alkyl trimethyl ammonium bromides are softex kw.
In above-mentioned manufacturing approach, preferably, the amino of said chitin and said gold nano post form said chemical bonded refractory.
The gold nano post that the present invention also provides a kind of chitin to modify, it comprises: the gold nano post; And chitin, itself and said gold nano post form chemical bonded refractory.
According to concrete technical scheme of the present invention, preferably, the amino of said gold nano post and said chitin forms said chemical bonded refractory.
According to concrete technical scheme of the present invention, preferably, the gold nano post that said chitin is modified is prepared by the manufacturing approach of above-mentioned gold nano post.
In sum; The invention provides a kind of gold nano post and manufacturing approach thereof, wherein, borrowing chitin and gold nano post directly to form chemical bonded refractory; Originally modified many alkyl trimethyl ammonium bromides and replace, reached the purpose of the bio-compatibility that improves the gold nano post in the gold nano post.
Description of drawings
Figure 1A is the tunnel formula of the wearing electron microscope picture of the gold nano post of softex kw modification;
Figure 1B is the tunnel formula of the wearing electron microscope picture of the chitin-gold nano post of the embodiment of the invention 1;
Fig. 2 is the ultraviolet-visible spectrogram in order to the surface plasma resonant absworption peak of the chitin-gold nano post that shows the gold nano post that softex kw is modified and the embodiment of the invention 1;
Fig. 3 is the chitin-Nai Mi gold particle of embodiment 1 and the infared spectrum of pure chitin;
Fig. 4 is the cell toxicity test result of the gold nano post of softex kw modification;
Fig. 5 is the cell toxicity test result of the chitin-gold nano post of the embodiment of the invention 1.
The specific embodiment
Because chitin (chitosan) possesses high bio-compatibility, inanimate object toxicity, cheap, advantage such as mechanical strength is good and is extensively applied in industry and the biomedicine.Chitin is to be the formed polysaccharides of monomer with N-acetyl-D-amino glucose, and it has a plurality of amino." chitin modification " of the present invention is meant with chitin and forms chemical bonded refractory.
" the gold nano post (chitin-gold nano post) that chitin is modified " described in the embodiment of the present invention is meant the gold nano post that forms chemical bonded refractory with chitin; More clearly, be meant the gold nano post that forms chemical bonded refractory with the amino of chitin.
The pH value that in the present invention, will contain the solution of chitin adjust between the 2.0-7.0 so that chitin be dispersed among this solution.One of ordinary skill in the art for instance, add acid solution to adjust the said pH value that contains the solution of chitin when adopting diverse ways to adjust the said pH value that contains the solution of chitin according to circumstances.Said acid solution includes, but are not limited to: hydrochloric acid, acetic acid or its combination; More clearly, said acid solution includes, but are not limited to: the hydrochloric acid of 1-10wt%, the acetic acid of 1-10wt% or its combination.Said acid solution can be used as the agent of leaving away of many alkyl trimethyl ammonium bromides simultaneously, to promote the carrying out of chitin substitution reaction.The use amount of said acid solution need not limit; One of ordinary skill in the art work as the use amount that can adjust acid solution according to circumstances makes chitin be dispersed in the purpose in this solution to reach, and/or reaches the effect of improving as the agent of leaving away of many alkyl trimethyl ammonium bromides.
" many alkyl trimethyl ammonium bromides " of the present invention is meant that the alkyl number is many alkyl trimethyl ammonium bromides of 3-40, more clearly, is softex kw.
" preparation of chitin-gold nano post "
The preparation method of chitin of the present invention-gold nano post comprises: the solution that at first provides the chitin solution and one of a 1-10wt% to contain the gold nano post that many alkyl trimethyl ammonium bromides modify, and it evenly is mixed into a mixed liquor.
Then, said mixed liquor is left standstill under 20-30 ℃, make said chitin and said gold nano post form chemical bonded refractory; More clearly, the amino of said chitin and said gold nano post form chemical bonded refractory, and this chitin is as substituting group, replaces originally to modify the many alkyl trimethyl ammonium bromides in said gold nano post.Preferably, further in said mixed liquor, add acid solution,, promote the substitution reaction of chitin with the agent of leaving away as said many alkyl trimethyl ammonium bromides; Preferably, the said agent of leaving away accounts for the 1-5% (v/v) of said mixed liquor.
In affiliated field, be softex kw through said " the many alkyl trimethyl ammonium bromides " that is usually used in modifying the gold nano post; But one of ordinary skill in the art; The content that specification discloses according to the present invention; All can under notion of the present invention, be replaced when understanding the gold nano post of modifying through many alkyl trimethyl ammonium bromides, and be not limited to gold nano post through the softex kw modification by chitin.
At last, carry out centrifugation step the crystalline solid in the said mixed liquor is separated, promptly obtain chitin of the present invention-gold nano post.Said centrifugation step is under 5000-15000rpm centrifugal 5-30 minute, repeats said centrifugation step 1-5 time according to circumstances.One of ordinary skill in the art are when understanding, and the purpose of said centrifugation step is separated in said mixed liquor for making crystalline solid, as long as therefore can reach this purpose, the rotating speed of said centrifugation step, time and number of times all can change according to circumstances.
Following examples are to be used for further understanding advantage of the present invention, are not to be used to limit claim protection domain of the present invention.
Embodiment 1: the preparation of chitin of the present invention-gold nano post
The pH value of chitin solution that with a concentration is 1wt% after hydrochloric acid is adjusted into pH=2, with one contain the gold nano post (shown in Figure 1A) that softex kw modifies solution evenly be mixed into a mixed liquor.
Then, the hydrochloric acid that adds 3wt% as the agent of leaving away after, make this mixed liquor be statically placed in room temperature following 6 hours.
At last, this mixed liquor in 10000rpm centrifugal treating 3 times, so that the crystalline solid in the mixed liquor is separated, is promptly obtained the chitin-gold nano post (shown in Figure 1B) of present embodiment.
Relatively Figure 1A and Figure 1B show according to the method for the invention, make chitin replacement softex kw and make chitin-gold nano post to change the face shaping of gold nano post originally.Because the peculiar property (like optics, electricity and magnetic properties) of nano material is main relevant with its size and face shaping; Therefore; Can know by Figure 1A and Figure 1B; Not only improve the bio-compatibility of gold nano post according to the prepared chitin of the inventive method-gold nano post, also do not influence the gold nano post in biomedical function.
Embodiment 2: identify chitin of the present invention-gold nano post
At first, through the standard absorption peak position of ultraviolet-visible spectrum with the chitin-gold nano post of the gold nano post observing softex kw and modify and embodiment 1 gained.
Please refer to Fig. 2, curve A shows that the minor axis absworption peak of the gold nano post that softex kw is modified is 530 nanometers, and the major axis absworption peak is 690 nanometers.Curve B then shows the minor axis and the major axis absworption peak of chitin-gold nano post.Generally speaking, the absorbing wavelength of chitin-gold nano post does not significantly change, and the peak type is also very close.
Then, confirm the key junction relationship of the amino of gold nano post described in the method for the present invention and said chitin.Please refer to Fig. 3, wherein, curve A and B are respectively the infrared ray collection of illustrative plates (IR) of above-mentioned chitin-gold nano post and pure chitin.Curve A in the comparison diagram 3 and B can know, the key knotting strength (v of the amino of chitin
C-N, arrow indication place among the figure) because produce chemical bonded refractory and variation to some extent, proved in the method for the present invention that the amino of said gold nano post and said chitin forms the key junction relationship of said chemical bonded refractory with gold.
Then, the cytotoxicity of the chitin-gold nano post of the gold nano post of comparison softex kw modification and embodiment 1 gained.
Because nano material is easy to invade human body through breathing the mode of eating in suction or oral cavity, therefore adopts human mouth epithelial cells (S-G), oral cavity fibroblast (OMF) or pulmonary epithelial cells (BEAS-2B) to carry out Cytotoxic test.Briefly; The solution of the chitin-gold nano post that contains gold nano post that softex kw modifies and embodiment 1 gained of different volumes (0,0.01,0.1,1,10 μ L) is added in the nutrient solution of said cell; Observation of cell survival rate again, result of the test is respectively like Fig. 4 and shown in Figure 5.
Please refer to Fig. 4, the result shows three kinds of cells of the gold nano post solution co-incubation of modifying with the softex kw of 1 μ L, has all presented the hundred-percent death rate nearly.Please refer to Fig. 5, in all experiment volumes, the gold nano post that chitin is modified does not all cause any cytotoxicity to three kinds of cells.Said result shows the gold nano post of modifying with chitin replacement softex kw through the inventive method, and the gold nano post of modifying than softex kw commonly used significantly has more security, is more suitable in biomedical utilization.
One of ordinary skill in the art work as and can understand, under spirit of the present invention, and the various variations that foundation embodiment of the present invention can carry out.Therefore, obvious listed embodiment is not in order to restriction the present invention, but attempt is covered by the modification of being made in spirit of the present invention and the category under the definition of accompanying claims protection domain.
Claims (11)
1. the manufacturing approach of a gold nano post, it comprises following steps:
A, a mixed liquor is provided, it comprises the gold nano post that chitin and many alkyl trimethyl ammonium bromides are modified;
B, make said chitin and said gold nano post form chemical bonded refractory; And
C, centrifugal treating are to obtain the gold nano post that chitin is modified.
2. the method for claim 1, wherein said mixed liquor also comprises acid solution.
3. method as claimed in claim 2, wherein, said acid solution is to be used for the pH value of said mixed liquor is controlled in 2.0-7.0.
4. method as claimed in claim 2, wherein, said acid solution is in order to as the agent of leaving away.
5. method as claimed in claim 2, wherein, said acid solution is hydrochloric acid, acetic acid or its combination.
6. the method for claim 1, wherein said many alkyl trimethyl ammonium bromides are many alkyl trimethyl ammonium bromides of 3-40 for the alkyl number.
7. method as claimed in claim 6, wherein, said many alkyl trimethyl ammonium bromides are softex kw.
8. the method for claim 1, wherein the amino of said chitin and said gold nano post form said chemical bonded refractory.
9. the gold nano post modified of a chitin, it comprises:
The gold nano post; And
Chitin, itself and said gold nano post form chemical bonded refractory.
10. the gold nano post that chitin as claimed in claim 9 is modified, wherein, the amino of said gold nano post and said chitin forms said chemical bonded refractory.
11. the gold nano post that chitin as claimed in claim 9 is modified, it is prepared by each described method of claim 1-8.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380473A (en) * | 2008-10-14 | 2009-03-11 | 上海师范大学 | Gold nano-bar based medicine carrier and preparation technique and use thereof |
| CN101444847A (en) * | 2008-12-04 | 2009-06-03 | 上海交通大学 | Method for preparing PAMAM dendrimer-modified gold nanorod composite carrier |
| CN101785784A (en) * | 2010-01-15 | 2010-07-28 | 浙江大学 | Compound of gold nanorods and zwitter ion molecules for photo-thermal therapy of cancer and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101380473A (en) * | 2008-10-14 | 2009-03-11 | 上海师范大学 | Gold nano-bar based medicine carrier and preparation technique and use thereof |
| CN101444847A (en) * | 2008-12-04 | 2009-06-03 | 上海交通大学 | Method for preparing PAMAM dendrimer-modified gold nanorod composite carrier |
| CN101785784A (en) * | 2010-01-15 | 2010-07-28 | 浙江大学 | Compound of gold nanorods and zwitter ion molecules for photo-thermal therapy of cancer and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《化学通报》 20100331 杨玉东等 金纳米棒的表面改性及其在生物医学领域的应用 , 第3期 * |
| 杨玉东等: "金纳米棒的表面改性及其在生物医学领域的应用", 《化学通报》, no. 3, 31 March 2010 (2010-03-31) * |
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