CN106634012A - Method for establishing nano particle small polymers by using indoles dyestuff - Google Patents
Method for establishing nano particle small polymers by using indoles dyestuff Download PDFInfo
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- CN106634012A CN106634012A CN201710003873.1A CN201710003873A CN106634012A CN 106634012 A CN106634012 A CN 106634012A CN 201710003873 A CN201710003873 A CN 201710003873A CN 106634012 A CN106634012 A CN 106634012A
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- nano
- indoles
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- dyestuff
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention discloses a method for establishing nano particle small polymers by using indoles dyestuff. According to the method, an ionic agent with negative charge is assembled on the surfaces of nano particles with certain sizes, and then is combined to indoles dyestuff molecules with positive charge with the aid of effect of static electricity between the negative charge and the positive charge to obtain small polymers such as dipolymers and tripolymers of the ordered nano particles. By an ultraviolet spectrum, a spectral quality changing process of gold particles from mutually independent individuals into the small polymers can be observed, and the dynamic process of formation of the gold particle small polymers is tracked. The nano structures can be used as enhanced bases which are applied to a surface-enhanced Raman spectroscopy technology for a trace amount of sensitive detection.
Description
Technical field
The invention belongs to nano material synthesis technical field, specifically, is related to a kind of structure using indoles dyestuff and is received
The method of the little aggressiveness of rice corpuscles.
Background technology
(conventional aggregate is because of some reasons by multiple nano-particles to the phenomenon that nano-particle is easily reunited in the aqueous solution
And mixed and disorderly unordered combination) problem of nano-particle application presence is always, but the little aggressiveness of some nano-particles is (such as
Silver, gold, copper etc.) substrate that can greatly enhance as signal in SERS application, when some Raman actives
To on the metal surface of specially treated (such as silver, gold, copper), their Raman scattering can be enhanced～10 to Molecular Adsorption4-
106Times, and even can reach 10 in the orderly nanostucture system reunited8-1014Enhancer.Although existing many sections
Grinding controlledly synthesis of the personnel to nano material has carried out many researchs, but how to realize the orderly of the little aggressiveness of nano-particle and can
The synthesis of control still rarely has research.
Much report by the use of the dyestuff with Raman active as the label of nanoparticle surface, but by indoles
Class dyestuff forms " π-π stacking effects " between nano-particle, all can be because of dyestuff point between two neighboring nano-particle
Son presence and reunite each other between particle, therefore formed apart from the little aggressiveness such as controllable dimerization, the trimerization of ordered nano particle this
The work of aspect is not also studied.
The content of the invention
For problem above, it is an object of the invention to provide a kind of stable, controllable utilization indoles dyestuff builds that
Method of this adjacent nano interparticle distance from the little aggressiveness of the nano-particles such as controllable dimerization, trimerization.
To achieve these goals, the technical solution used in the present invention is as follows.
A kind of method that utilization indoles dyestuff builds the little aggressiveness of nano-particle, takes first in nanoparticle surface assembling
Negatively charged ionic agent, then by the electrostatic interaction between negative electrical charge and positive charge, with reference to the indoles with positive charge
Dye molecule, structure obtains the little aggressiveness of nano-particle；Wherein：The indoles dye molecule is indoles cyanines iodide.
In the present invention, the ionic agent of described carrying negative electrical charge is sodium citrate salt.
In the present invention, described nano-particle is less than 100 nanometers of gold particle.
In the present invention, the molecular formula of described indoles cyanines iodide is C31H41IN2Or C29H37IN2Or C27H31IN2。
The method that the present invention builds the little aggressiveness of nano-particle using indoles dyestuff, comprises the following steps that：
1) first the aqueous solution of chloraurate that 1.5～2mL mass fractions are 0.8～1.2wt% is added in 50mL water, and added
Heat to 95～10 degree, then addition 4～6mL mass fractions be the sodium citrate solution of 0.8～1.2wt% as reducing agent, instead
10-15 minutes are answered, that is, obtains various sizes of nano gold sol；
2) 0.02～0.2 micromolar indoles dye solution will be contained and will be added to step 1) the various sizes of nanometer that obtains
In aurosol, acid-base value is adjusted in the range of pH 3～5, be stirred at room temperature 2～5 minutes, obtain the little aggressiveness of nano-particle.
Compared to the prior art, the beneficial effects of the present invention is：
(1) controllability is good.Indoles dye molecule is assembled in nanoparticle surface by the present invention by electrostatic interaction,
The conjugation group contained in indoles molecular structure of dye can form " π-π stacking effects ", phase between nano-particle
Reunite each other between particle because of the presence of dye molecule between adjacent two nano-particles, therefore formed apart from controllable two
The little aggressiveness such as poly-, trimerization.The present invention is observed that gold particle from single body independent of each other to little aggressiveness using ultraviolet spectra
Spectral quality change procedure.
(2) substrate enhancement effect is high.Indoles dyestuff makes it in optics and spectrum because of big π structures present in its molecule
Have using in by special advantage.When indoles dye molecule forms " π-π stacking effects " between nano-particle,
I.e. controllable to define the little aggressiveness of nano-particle, these nanostructureds can be applied to SERS as substrate is strengthened
In etc. technology, can be by the enhanced multiple of Raman scattering from～104-106Lifted again to 108-1014, be conducive to carrying out micro spirit
Quick detection.
(3) method is simple.The ionic agent of negative electrical charge has been introduced in system while synthesizing nano-particle, eliminates
The process of surface modification, it also avoid introducing new pollution.The electropositive that indoles cyanines iodide structure has is mutual by electrostatic
Effect is stably bound in nanoparticle surface with the ionic agent of negative electrical charge, so as to define nano-particle well to each other
Distance, so as to the little aggressiveness system of the nanometer for obtaining a good dispersion.
Description of the drawings
Fig. 1 is the UV-visible spectrum of 12 nano Au particles of embodiment 1.
Fig. 2 is that particle surface of the utilization ultraviolet-visible spectrum of embodiment 2 to indoles dye molecule at 12 nanometers is assembled
The dynamics tracking figure that process is carried out.
Fig. 3 is the UV-visible spectrum of 30 nano Au particles of embodiment 1.
Fig. 4 is that particle surface of the utilization ultraviolet-visible spectrum of embodiment 2 to indoles dye molecule at 30 nanometers is assembled
The dynamics tracking figure that process is carried out.
Specific embodiment
Technical scheme is further described with reference to specific embodiment, but the present invention is not limited to
Following embodiments.
Various raw materials used in various embodiments of the present invention, if no special instructions, are commercially available.
Embodiment 1
Indoles dyestuff builds the operation of the little aggressiveness of nano-particle and sign：
The preparation of (1) 12 nano gold sol：
Mass fraction is that 1% aqueous solution of chloraurate (1.7mL) is added in 50mL water and is heated to 100 degree (holding is stirred
Mix), sodium citrate solution (5mL) that mass fraction is 1% is then rapidly added as reducing agent, react 15 minutes, finally obtain
Obtain the nano gold sol of 12 sizes.
The surface plasma body characteristicses of (2) 12 nano Au particles
Fig. 1 is the UV-visible spectrum of 12 nano Au particles, can substantially observe the absorption maximum shown in this curve
Wavelength (λmax) at 517nm, this size is corresponding to 12 nanometer particle sizes in document report.
(3) indoles dyestuff is assembled on nano-particle：
Add indoles dye solution to cause the two concentration to be respectively 0.084 micromole and 2.5 in Nano sol to receive and rub
You so that the dye molecule in nanoparticle surface reaches 5～10% covering.Using salt acid for adjusting pH～3, fill at room temperature
Divide stirring 3 minutes.
(4) the surface plasma observation of characteristics of the little aggressiveness of nano-particle
Fig. 2 is that the particle surface assembling process to indoles dye molecule at 12 nanometers is carried out using ultraviolet-visible spectrum
Dynamics follow the trail of figure.The more simple Nano sol of the little aggressiveness of nano-particle its surface plasma body characteristics for observing in spectrum
Feature is different, and in～650 nanometer ranges acromion is occurred in that, characterizes the dynamic formation process of the little aggressiveness of nano-particle.Due to
The concentration of nano-particle and dye molecule is certain, thus in theory for nanoparticle agglomeration degree it is also certain.
Embodiment 2
Indoles dyestuff builds the operation of the little aggressiveness of nano-particle and sign：
The preparation of (1) 30 nano gold sol：
Mass fraction is that 1% aqueous solution of chloraurate (1.7mL) is added in 50mL water and is heated to 100 degree (holding is stirred
Mix), sodium citrate solution (5mL) that mass fraction is 1% is then rapidly added as reducing agent, react 15 minutes, according to grain
The needing of footpath adds 2.1mL's after the Au seeds of 0.5mL are mixed at room temperature with the aqueous solution of chloraurate (1%) of 0.5mL
NH2OHHCl solution (40mM) is used as reducing agent, the final nano gold sol for obtaining 30 sizes.
The surface plasma body characteristicses of (2) 30 nano Au particles
Fig. 3 is the UV-visible spectrum of 30 nano Au particles, can substantially observe the absorption maximum shown in this curve
Wavelength (λmax) at 521nm, this size is corresponding to 30 nanometer particle sizes in document report.
(3) indoles dyestuff is assembled on nano-particle：
Add indoles dye solution to cause the two concentration to be respectively 0.0238 micromole and 0.089 in Nano sol to receive
Mole so that the dye molecule in nanoparticle surface reaches 5～10% covering.Using salt acid for adjusting pH～3, at room temperature
It is sufficiently stirred for 3 minutes.
(4) the surface plasma observation of characteristics of the little aggressiveness of nano-particle
Fig. 4 is that the particle surface assembling process to indoles dye molecule at 30 nanometers is carried out using ultraviolet-visible spectrum
Dynamics follow the trail of figure.The more simple Nano sol of the little aggressiveness of nano-particle its surface plasma body characteristics for observing in spectrum
Feature is different, and in 600～700 nanometer ranges acromion is occurred in that, characterizes the dynamic formation process of the little aggressiveness of nano-particle.
Claims (5)
1. a kind of method that utilization indoles dyestuff builds the little aggressiveness of nano-particle, it is characterised in that：First in nanoparticle sublist
The ionic agent of negative electrical charge is carried in the assembling of face, then by the electrostatic interaction between negative electrical charge and positive charge, with reference to positive electricity
The indoles dye molecule of lotus, structure obtains the little aggressiveness of nano-particle；Wherein：The indoles dye molecule is indoles cyanines iodate
Thing.
2. method according to claim 1, it is characterised in that the ionic agent of the carrying negative electrical charge is sodium citrate salt.
3. method according to claim 1, it is characterised in that the nano-particle is less than 100 nanometers of gold particle.
4. method according to claim 1, it is characterised in that the molecular formula of described indoles cyanines iodide is C31H41IN2
Or C29H37IN2Or C27H31IN2。
5. method according to claim 1, it is characterised in that comprise the following steps that：
1) first the aqueous solution of chloraurate that 1.5～2mL mass fractions are 0.8～1.2wt% is added in 50mL water, and is heated to
95～10 degree, then add the sodium citrate solution that 4～6mL mass fractions are 0.8～1.2wt% as reducing agent, react 10-
15 minutes, obtain various sizes of nano gold sol；
2) step 1 will be added to containing 0.02～0.2 micromolar indoles dye solution) the various sizes of nm of gold that obtains
In colloidal sol, acid-base value is adjusted between pH 3～5, be stirred at room temperature 2～5 minutes, obtain the little aggressiveness of nano-particle.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502584A (en) * | 2014-12-18 | 2015-04-08 | 南京基蛋生物科技有限公司 | Dry-type immunochromatographic analysis method based on metal nanoparticle enhanced fluorescence |
| CN104587474A (en) * | 2015-02-02 | 2015-05-06 | 国家纳米科学中心 | Gold-core-composite nano-carrier as well as preparation method and application thereof |
| CN105928923A (en) * | 2016-04-22 | 2016-09-07 | 上海应用技术学院 | Cyanine dye-nanogold SERS probe and preparation method thereof |
| CN106018295A (en) * | 2016-05-11 | 2016-10-12 | 上海应用技术学院 | Measuring method for positive-negative ion pairs needed by surfaces of gold nano particles in phase extraction method |
-
2017
- 2017-01-04 CN CN201710003873.1A patent/CN106634012A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104502584A (en) * | 2014-12-18 | 2015-04-08 | 南京基蛋生物科技有限公司 | Dry-type immunochromatographic analysis method based on metal nanoparticle enhanced fluorescence |
| CN104587474A (en) * | 2015-02-02 | 2015-05-06 | 国家纳米科学中心 | Gold-core-composite nano-carrier as well as preparation method and application thereof |
| CN105928923A (en) * | 2016-04-22 | 2016-09-07 | 上海应用技术学院 | Cyanine dye-nanogold SERS probe and preparation method thereof |
| CN106018295A (en) * | 2016-05-11 | 2016-10-12 | 上海应用技术学院 | Measuring method for positive-negative ion pairs needed by surfaces of gold nano particles in phase extraction method |
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