CN104353845B - The method of different-shape nano gold grain prepared by the tryptophan of pentanedial decoration - Google Patents
The method of different-shape nano gold grain prepared by the tryptophan of pentanedial decoration Download PDFInfo
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- CN104353845B CN104353845B CN201410670997.1A CN201410670997A CN104353845B CN 104353845 B CN104353845 B CN 104353845B CN 201410670997 A CN201410670997 A CN 201410670997A CN 104353845 B CN104353845 B CN 104353845B
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- tryptophan
- glutaraldehyde
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Abstract
The invention discloses the method that different-shape nano gold grain prepared by the tryptophan of pentanedial decoration, it is characterised in that comprise the steps: that (1) prepares the aqueous solution of tryptophan glutaraldehyde compound；(2) in the aqueous solution of tryptophan glutaraldehyde compound, chlorauric acid solution is added.The present invention can prepare different-shape nano gold grain without adding crystal seed and surfactant.
Description
Technical field
The present invention relates to nanogold particle fabricating technology field, receive particularly to different-shape
The preparation method of rice gold grain.
Background technology
Gold nano grain has unique physics and chemical property is widely used in catalysis, photoelectricity
Equipment, chemical sensitisation and biomedicine field.Gold nano grain, ring is synthesized by biological method
Border is friendly, be widely used.Application biomolecule synthesis gold nano grain mainly use protein and
Amino acid, because these molecules contain amino, carboxyl or sulfydryl, it is possible to tie with gold grain surface
Close, improve the stability of gold grain.Method two kinds conventional now, one is by amino acid and goes back
Former dose adds gold chloride and prepares gold nano grain, and one is to be added as reducing agent by amino acid
Gold nano grain prepared by stabilizer.But, in prior art in the preparation process of gold nano grain,
Need to add crystal seed and surfactant, and the nanogold particle of different morphologies can not be prepared.
Summary of the invention
In view of this, the invention reside in offer can prepare without adding crystal seed and surfactant
Different-shape nano gold prepared by the tryptophan of the pentanedial decoration going out different-shape nano gold grain
The method of grain.
For solving the problems referred to above, the present invention provides following technical scheme: the look ammonia of pentanedial decoration
The method of different-shape nano gold grain is prepared in acid, comprises the steps:
(1) aqueous solution of tryptophan-glutaraldehyde compound is prepared；
(2) in the aqueous solution of the tryptophan of variable concentrations-glutaraldehyde compound, gold chloride is added molten
Liquid.
The method of different-shape nano gold grain prepared by the tryptophan of above-mentioned pentanedial decoration, in step
Suddenly in (1): glutaraldehyde water solution and the tryptophan aqueous solution are mixed, stirs under room temperature, mixing
Solution becomes light yellow from colourless, and reaction completes, and is then centrifuged by mixed solution, and supernatant is i.e.
The aqueous solution for tryptophan-glutaraldehyde compound.
The method of different-shape nano gold grain prepared by the tryptophan of above-mentioned pentanedial decoration, in step
Suddenly in (1): in glutaraldehyde water solution, glutaraldehyde mass fraction is 10%, in the tryptophan aqueous solution
Tryptophan concentration is 4mg/mL；Glutaraldehyde water solution is 1 with the volume ratio of the tryptophan aqueous solution:
500。
The method of different-shape nano gold grain prepared by the tryptophan of above-mentioned pentanedial decoration, in step
Suddenly in (1): stir under room temperature 24 hours, then mixed solution is centrifuged under 8000rpm
15 minutes.
The method of different-shape nano gold grain prepared by the tryptophan of above-mentioned pentanedial decoration, in step
Suddenly in (1): by glutaraldehyde water solution and 5mL that 0.01mL glutaraldehyde mass fraction is 10%
Tryptophan concentration is the tryptophan aqueous solution mixing of 4mg/mL, stirs 24 hours under room temperature, mixed
Closing solution and become light yellow from colourless, reaction completes, then by mixed solution under 8000rpm
Centrifugal 15 minutes, supernatant was the aqueous solution of tryptophan-glutaraldehyde compound, is labeled as A
Solution, parallel produces four parts of solution A；
Take first part of solution A and be diluted with water to calculate concentration with the mass body volume concentrations of tryptophan and be
1.5mg/mL, is labeled as B solution；Take second part of solution A and be diluted with water to the matter with tryptophan
Amount volumetric concentration calculates concentration 0.8mg/mL, is labeled as C1 solution；Take the 3rd part of solution A to use
Water is diluted to calculate concentration 0.8mg/mL with the mass body volume concentrations of tryptophan, is labeled as C2 molten
Liquid；4th part of solution A retains；The most respectively to the 4th part of solution A, B solution, C1 solution
With in C2 solution add 1mL absolute ethyl alcohol, standby after stirring；
In step (2): add in solution A, B solution, C1 solution and C2 solution respectively
Enter the chlorauric acid solution 0.1mL that concentration is 10 mMs every liter, then first three portion of mixed liquor is existed
3 hours are stood, after finally portion mixed solution stirs 10 minutes again in reactor in reactor
Standing 3 hours, four parts of solution colours are no longer changed by colourless overstrike and color, exist respectively
It is centrifuged 10 minutes under 8000rpm, then washes lower sediment thing respectively with water, prepare gold respectively
Nanometer spherical particle, gold nano sheet-like particle, with long arborescence gold nano star particle and
Gold nano star particle with short and thick arborescence.
Technical scheme obtains the most useful technique effect:
The present invention is mixed by amino acid and gold chloride, prepares three kinds of shapes by mol ratio regulation
The nanogold particle of looks.
The present invention selects tryptophan remove reduction gold chloride as reducing agent, is because: 1) look
Propylhomoserin is except can effectively stablize gold nano grain containing amino and carboxyl possibly together with heteroaromatic group；
2) tryptophan has had water solubility and strong reducing power.In order to gold grain is stablized by tryptophan
Property, glutaraldehyde is combined with tryptophan, forms the compound with two heteroaromatic groups.
This compound is as reducing agent and protective agent, in the situation without adding crystal seed and surfactant
Under, the gold nano grain of spherical, sheet and star is prepared out.Sheet and the Jenner of star
Rice grain display surface strengthens Raman coefficient, it is possible to as the label of surface-enhanced Raman.
Accompanying drawing explanation
The XPS spectrum of Fig. 1 Trp-GA.
The FTIR spectrum of Fig. 2 Trp-GA and the Trp-GA FTIR reacted with gold chloride
Spectrum.
Fig. 3-Fig. 5 is variable concentrations tryptophan-glutaraldehyde mixed liquor and the reacted electricity of gold chloride
Mirror photo.
The electromicroscopic photograph of the gold nano spheric granules that Fig. 3 solution A obtains after reacting with gold chloride
(gold nano spherical particle diameters is about 65nm).
The electromicroscopic photograph of the gold nano star particle that Fig. 4 C2 solution obtains after reacting with gold chloride
(stirring 10 minutes after mixing, with the gold nano star particle of short and thick arborescence, core is about
186nm, brachyplast about length 61nm).
The electromicroscopic photograph of the gold nano star particle that Fig. 5 C1 solution obtains after reacting with gold chloride
(do not stir after mixing, with the gold nano star particle of long arborescence, core about 520 nm,
Long shoot about length 160nm).
The Flied emission scanning of the gold nano sheet-like particle that Fig. 6 B solution obtains after reacting with gold chloride
Electronic Speculum (FSEM) [gold nano sheet particle diameter about 580nm, thickness 22.5nm].
Fig. 7 is the partial enlarged drawing of Fig. 6.
Fig. 8 gold nano spheric granules, gold nano sheet-like particle and the Jenner with short and thick arborescence
The XPS spectrum of rice star gold grain.
Fig. 9 gold nano spheric granules, gold nano sheet-like particle and the gold with short and thick arborescence
The ultra-violet absorption spectrum of nanometer star gold grain.
The integral experiment schematic diagram that in Figure 10 present invention prepared by different-shape nano gold grain
The spherical gold grain of 60nm of preparation, the present invention in the pure 4-ATP of Figure 11, prior art
Gold nano star with short and thick arborescence prepared by the gold nano sheet-like particle of preparation and the present invention
(SER signal of gold nano grain is that 4-ATP is adsorbed onto gold nano grain product to particle SERS signal
Raw SERS signal).
Detailed description of the invention
For understanding the scheme in the explanation present invention, preferred embodiment is given below and combines accompanying drawing
Describe in detail.
The tryptophan of the present embodiment pentanedial decoration prepares the method for different-shape nano gold grain such as
Under:
1. the preparation of tryptophan-glutaraldehyde compound
By dense to glutaraldehyde water solution and 5mL tryptophan that 0.01mL glutaraldehyde mass fraction is 10%
Degree for 4mg/mL the tryptophan aqueous solution mixing, under room temperature stir 24 hours, mixed solution from
Colourless becoming light yellow, reaction completes, then by mixed solution under 8000rpm centrifugal 15
Minute, supernatant is the aqueous solution of tryptophan-glutaraldehyde compound, is labeled as solution A, flat
Row produces four parts of solution A.Tryptophan and glutaraldehyde generation chemical reaction generate tryptophan-glutaraldehyde
The chemical equation of compound is as shown in formula I:
Two aldehyde radicals of glutaraldehyde are condensed with the amino of tryptophan respectively, the XPS spectrum of Trp-GA
As shown in Figure 1,284.6eV, 286.0eV are the most corresponding with three peaks at 288.4eV
C-C, C-N and C=N, it was demonstrated that the existence of C=N in Trp-GA.The FTIR spectrum of Trp-GA,
Trp-GA is with the reacted FTIR spectrum of gold chloride as shown in Figure 2.
Taking first part of solution A and being diluted with water to concentration is the 1.5mg/mL[mass body with tryptophan
Volume concentrations calculates], it is labeled as B solution；Take second part of solution A and be diluted with water to concentration
0.8mg/mL[calculates with the mass body volume concentrations of tryptophan], it is labeled as C1 solution；Take the 3rd
Part solution A is diluted with water to concentration 0.8mg/mL[and calculates with the mass body volume concentrations of tryptophan],
It is labeled as C2 solution；4th part of solution A retains；Molten to the 4th part of solution A, B the most respectively
Liquid, C1 solution and C2 solution add 1mL absolute ethyl alcohol, standby after stirring.
2. prepared by different-shape nano gold grain
Adding concentration respectively in the 4th part of solution A, B solution, C1 solution and C2 solution is
The chlorauric acid solution 0.1mL of 10 mMs every liter, then by first three portion of mixed liquor in reactor
Stand 3 hours, stand in being placed on reactor again after being stirred 10 minutes by last a mixed solution
3 hours, four parts of solution colours were no longer changed by colourless overstrike and color, exist respectively
It is centrifuged 10 minutes under 8000rpm, then washes lower sediment thing respectively with water, prepare gold respectively
Nanometer spherical particle, gold nano sheet-like particle, with long arborescence gold nano star particle and
Gold nano star gold grain [as shown in Fig. 3 to Fig. 7] with short and thick arborescence.Respectively will system
Standby go out gold nano spheric granules, gold nano sheet-like particle, gold nano star with long arborescence
Particle and the gold nano star gold grain with short and thick arborescence are distributed in the pure water of 2mL standby
With.
As it is shown in figure 9, the ultraviolet absorption peak of gold nano spheric granules is only at 540nm, peak shape is narrow,
Instruction sheet good dispersion, granular size and pattern are uniform.And gold nano sheet-like particle at 700nm
Have wider peak, this due to the anisotropy of gold nano sheet-like particle cause electronics in face from
Territory, surface plasma resonance red shift.With gold nano spheric granules and the purple of gold nano sheet-like particle
Outer absorption difference, the gold nano star gold grain with short and thick arborescence has two UV, visible lights to inhale
Receive peak, one at 540nm, one at 750nm.The two absorption band correspondence gold nano star
The core of grain and short and thick arborescence.
By HAuCl4Add solution A, mixed solution color rapidly from the colourless azarin that becomes, but
Mixed solution in nanometer sheet and nanometer star preparation process is until 30 minutes all change without color.
The impact of gold nano grain pattern is mainly formed specific by Trp-GA concentration by intermolecular force
Template, thus cause the difference of pattern.
SERS technology is widely used in biochemical analysis and imaging.Anisotropic metal nanoparticle
As SERS substrate.Have been reported that and think that the SERS signal that 60nm gold nano grain has had strengthens
Effect.We according to document prepare 60nm gold nano spheric granules [G.Frens, Nature 241,
20(1973).].SERS spectra is gold grain solution to be dripped to film forming on silicon chip be then dipped into
4-ATP (1mM) the most then surveys SERS spectra.Result shows (as shown in figure 11): this
The gold nano sheet-like particle of bright preparation and the gold nano star gold grain with short and thick arborescence
SERS signal intensity, higher than the 60nm nanosphere of preparation in above-mentioned document, is the 8 of nanosphere respectively
Again with 12 times.This explanation gold nano sheet-like particle of preparing of the present invention and with short and thick arborescence
Gold nano star gold grain can be as SERS marking substrates for bio-imaging and biochemistry detection.
Above-described embodiment is only for clearly demonstrating the invention example, and not
Restriction to the invention detailed description of the invention.Those of ordinary skill in the field are come
Say, can also make other changes in different forms on the basis of the above description.This
In without also cannot all of embodiment be given exhaustive.All in the spirit and principles in the present invention
Within any obvious change extended out or variation want still in the invention right
Among the protection domain asked.
Claims (5)
1. the method that different-shape nano gold grain prepared by the tryptophan of pentanedial decoration, it is characterised in that
Comprise the steps:
(1) aqueous solution of tryptophan-glutaraldehyde compound is prepared；
(2) in the aqueous solution of the tryptophan of variable concentrations-glutaraldehyde compound, chlorauric acid solution is added.
Different-shape nano gold grain prepared by the tryptophan of pentanedial decoration the most according to claim 1
Method, it is characterised in that in step (1): glutaraldehyde water solution and the tryptophan aqueous solution are mixed,
Stirring under room temperature, mixed solution becomes light yellow from colourless, and reaction completes, and is then centrifuged by mixed solution,
Supernatant is the aqueous solution of tryptophan-glutaraldehyde compound.
Different-shape nano gold grain prepared by the tryptophan of pentanedial decoration the most according to claim 2
Method, it is characterised in that in step (1): in glutaraldehyde water solution, glutaraldehyde mass fraction is 10%,
In the tryptophan aqueous solution, Tryptophan concentration is 4mg/mL；Glutaraldehyde water solution and the volume of the tryptophan aqueous solution
Ratio is 1:500.
Different-shape nano gold grain prepared by the tryptophan of pentanedial decoration the most according to claim 3
Method, it is characterised in that in step (1): under room temperature stir 24 hours, then by mixed solution
It is centrifuged 15 minutes under 8000rpm.
Different-shape nano gold grain prepared by the tryptophan of pentanedial decoration the most according to claim 4
Method, it is characterised in that in step (1): be the penta of 10% by 0.01mL glutaraldehyde mass fraction
The dialdehyde aqueous solution and the tryptophan aqueous solution mixing that 5mL Tryptophan concentration is 4mg/mL, stir 24 under room temperature
Hour, mixed solution becomes light yellow from colourless, and reaction completes, then by mixed solution at 8000rpm
Under be centrifuged 15 minutes, supernatant is the aqueous solution of tryptophan-glutaraldehyde compound, is labeled as solution A,
Parallel produce four parts of solution A；
Take first part of solution A and be diluted with water to calculate concentration with the mass body volume concentrations of tryptophan and be
1.5mg/mL, is labeled as B solution；Taking second part of solution A, to be diluted with water to the quality volume with tryptophan dense
Degree calculates concentration 0.8mg/mL, is labeled as C1 solution；Take the 3rd part of solution A to be diluted with water to tryptophan
Mass body volume concentrations calculate concentration 0.8mg/mL, be labeled as C2 solution；4th part of solution A retains；So
Rear addition 1mL absolute ethyl alcohol in the 4th part of solution A, B solution, C1 solution and C2 solution respectively, stirs
Mix rear standby；
In step (2): adding concentration respectively in solution A, B solution, C1 solution and C2 solution is
The chlorauric acid solution 0.1mL of 10 mMs every liter, then stands 3 in reactor by first three portion of mixed liquor
Hour, last a mixed solution stands 3 hours after stirring 10 minutes again in reactor, four parts of solution
Color is no longer changed by colourless overstrike and color, is centrifuged 10 minutes respectively, then divides under 8000rpm
Do not wash lower sediment thing with water, thus obtain being prepared gold nano spheric granules, by B solution by solution A
Prepare gold nano sheet-like particle, prepared by C1 solution the gold nano star particle with long arborescence and
C2 solution prepares the gold nano star particle with short and thick arborescence.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7608461B1 (en) * | 2005-09-16 | 2009-10-27 | Sandia Corporation | Surface engineered nanoparticles for improved surface enhanced Raman scattering applications and method for preparing same |
| CN102211204A (en) * | 2011-05-06 | 2011-10-12 | 中国科学院化学研究所 | Method for preparing nano-gold |
| CN102225470A (en) * | 2011-06-20 | 2011-10-26 | 江西农业大学 | Method for preparing gold nanoparticles based on environmentally-friendly chemical method |
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| US7585349B2 (en) * | 2002-12-09 | 2009-09-08 | The University Of Washington | Methods of nanostructure formation and shape selection |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7608461B1 (en) * | 2005-09-16 | 2009-10-27 | Sandia Corporation | Surface engineered nanoparticles for improved surface enhanced Raman scattering applications and method for preparing same |
| CN102211204A (en) * | 2011-05-06 | 2011-10-12 | 中国科学院化学研究所 | Method for preparing nano-gold |
| CN102225470A (en) * | 2011-06-20 | 2011-10-26 | 江西农业大学 | Method for preparing gold nanoparticles based on environmentally-friendly chemical method |
Non-Patent Citations (1)
| Title |
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| Role of Surfactant in the Formation of Gold Nanoparticles in Aqueous Medium;Abhishek Das et al.;《Journal of Nanoparticles》;20140910;第1-7页 * |
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