CN107213462A - Nanogold particle of method and ICG cladding a kind of of enhancing ICG singlet oxygen yield and preparation method thereof - Google Patents
Nanogold particle of method and ICG cladding a kind of of enhancing ICG singlet oxygen yield and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of method of enhancing ICG singlet oxygen yield, and methods described hatches ICG using positive charge molecules.The present invention also provides a kind of nanogold particle of ICG claddings and preparation method thereof.The method of the enhancing ICG singlet oxygen yield, enhances its photo and thermal stability and realizes the enhancing of ICG singlet oxygen yield, nanogold particle of the ICG claddings and preparation method thereof, realizes the enhancing of ICG carrier band and singlet oxygen yield in biosystem.
Description
Technical field
The invention belongs to medicinal chemistry art, it is related to a kind of method of enhancing ICG singlet oxygen yield and receiving for ICG claddings
Rice gold grain and preparation method thereof.
Background technology
Indocyanine green (ICG) is that a kind of of Food and Drug Administration (FDA) approval is used for clinical near infrared imaging
Agent.ICG is a kind of three carbon cyanine dye, and absworption peak and fluorescence emission peak are all near infrared region, because the tissue of near infrared light is worn
Saturating depth is larger, smaller by background influence, as a kind of diagnosis reagent blood volume, cardiac output, liver function, retina,
Choroidal vascular system can play good booster action when being diagnosed.In addition, ICG can convert light energy into heat energy or
Singlet oxygen is produced, has potential application foreground in photo-thermal therapy (PTT) and optical dynamic therapy (PDT)
(Biotechnol.Adv.,2016,34,758-789).ICG monomers photo and thermal stability in water is poor, causes in its During Illumination
Based on non-singlet light degradation approach, singlet oxygen low yield.ICG easily forms aggregation in water, can significantly increase its photo-thermal
Stability;But the ability that aggregation produces singlet oxygen is also lower than monomer, it is unfavorable for the related application of singlet oxygen.It is many at present
Research is devoted to strengthen ICG stability.
ICG is embedded in liposome by John C.Kraft etc. by hydrophobic interaction, makes ICG water-soluble using liposome
Dissolubility strengthens in liquid, and then obtains stronger ICG fluorescence, improve imaging efficiency (Biochemistry, 2014,53,
1275-1283).Lee Y. etc. wrap up ICG using di-block copolymer, stability and then raising again by enhancing ICG
ICG singlet oxygens yield (Sci.Rep., 2017,7,46688).The golden rod of Silica-coated such as Li Y. passes through mesoporous
Suction-operated load ICG, using silica strengthen ICG stability, and using golden rod absorption cross-section it is big the characteristics of reduce ICG
Light degradation (ACS Nano, 2014,11,11529-11542).Also some research and utilization electrostatic interactions load ICG
In nano material, enhancing ICG stability (Colloids Surf B Biointerfaces, 2015,136,402-412;
Langmuir, 2015,31,6202-6210), but most of research concentrates on ICG photo-thermal effect, the application of optical dynamic therapy
It is less.Main cause is also due to that unstability in ICG water and light degradation are serious, and singlet oxygen yield is very low, how to increase
Strong ICG singlet oxygen yield is that ICG is applied to the major issue that optical dynamic therapy faces.
The content of the invention
For technical problem present in prior art, the present invention provides a kind of method of enhancing ICG singlet oxygen yield
And a kind of nanogold particle of ICG claddings and preparation method thereof, the method for the enhancing ICG singlet oxygen yield enhances it
Photo and thermal stability and the enhancing for realizing ICG singlet oxygen yield, the nanogold particle of the ICG claddings and preparation method thereof,
Realize the enhancing of ICG carrier band and singlet oxygen yield in biosystem.
To reach above-mentioned purpose, the present invention uses following technical scheme:
One of the object of the invention is to provide a kind of method of enhancing ICG singlet oxygen yield, incubated using positive charge molecules
Change ICG.
Methods described passes through electrostatic interaction using positively charged surfactant molecule or cationic polyelectrolyte
ICG formation aggregations are promoted to enhance its photo and thermal stability and realize the enhancing of ICG singlet oxygen yield.
Wherein, the hatching is to add to be placed in preference temperature water-bath after mixing in same solution by several compositions to place.
As currently preferred technical scheme, the positive charge molecules include cationic surfactant and/or positive electricity
Lotus polyelectrolyte.
Preferably, the cationic surfactant includes cetyl trimethylammonium bromide and/or cetyl front three
Ammonium chloride.
Preferably, the positive charge polyelectrolyte is diallyl dimethyl ammoniumchloride.
As currently preferred technical scheme, the positive charge molecules and ICG mol ratio are (1~100):1, such as 1:
1、2:1、5:1、8:1、10:1、15:1、20:1、25:1、30:1、40:1、50:1、60:1、80:1 or 100:1 etc., but simultaneously not only
It is limited to other unrequited numerical value in cited numerical value, the number range equally applicable.
As currently preferred technical scheme, the temperature of the hatching is 20~40 DEG C, such as 20 DEG C, 21 DEG C, 22 DEG C, 25
DEG C, 28 DEG C, 30 DEG C, 32 DEG C, 35 DEG C, 38 DEG C, 39 DEG C or 40 DEG C etc., it is not limited to cited numerical value, the number range
Other interior unrequited numerical value are equally applicable.
Preferably, the time of the hatching is 3~10min, such as 3min, 4min, 5min, 6min, 7min, 8min, 9min
Or 10min etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, the hatching is carried out under the conditions of lucifuge.
The two of the object of the invention are to provide a kind of nanogold particle of ICG claddings, and the nanogold particle is from inside to outside
Positive charge molecules layer and ICG layers are coated successively.
Nanogold particle used in the present invention is to use to prepare well known to a person skilled in the art preparation method,
This is repeated no more.
Wherein, a diameter of 10~20nm of the nanogold particle.
The three of the object of the invention are to provide a kind of preparation method of the nanogold particle of ICG claddings, the preparation method
Comprise the following steps:
(1) hatch nanogold particle using positive charge molecules, obtain the nanogold particle solution of positive charge molecules cladding;
(2) the nanogold particle solution of the positive charge molecules cladding obtained step (1) is mixed with ICG, is hatched, is received
The ICG of rice gold grain load.
As currently preferred technical scheme, step (1) positive charge molecules and mole of the nanogold particle
Than for (105~106):1, such as 1 × 105:1、2×105:1、3×105:1、4×105:1、5×105:1、6×105:1、7×105:
1、8×105:1、9×105:1 or 1 × 106:1 etc., it is not limited to other are not arranged in cited numerical value, the number range
The numerical value of act is equally applicable.
Preferably, the temperature of step (1) described hatching be 20~40 DEG C, such as 20 DEG C, 21 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30
DEG C, 32 DEG C, 35 DEG C, 38 DEG C, 39 DEG C or 40 DEG C etc., it is not limited to other are not arranged in cited numerical value, the number range
The numerical value of act is equally applicable.
Preferably, the time of step (1) described hatching be 3~10min, such as 3min, 4min, 5min, 6min, 7min,
8min, 9min or 10min etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
It is applicable.
9th, as currently preferred technical scheme, when step (1) described positive charge molecules are diallyl dimethyl
During ammonium chloride, step (1 ') is carried out before step (1), first hatches gold nano grain using cetyl trimethylammonium bromide, then
Hatch gold nano grain using kayexalate, obtain the gold nano grain of kayexalate cladding.
Preferably, the mol ratio of step (1 ') cetyl trimethylammonium bromide and the nanogold particle for (1 ×
105~2 × 107):1, such as 1 × 105:1、3×105:1、5×105:1、7×105:1、2×106:1、4×106:1、6×106:1、
8×106:1、1×107:1 or 2 × 107:1 etc., it is not limited to other are unrequited in cited numerical value, the number range
Numerical value it is equally applicable.
Preferably, the temperature of step (1 ') cetyl trimethylammonium bromide hatching is 20~40 DEG C, such as 20 DEG C, 21
DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30 DEG C, 32 DEG C, 35 DEG C, 38 DEG C, 39 DEG C or 40 DEG C etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range.
Preferably, the time of step (1 ') cetyl trimethylammonium bromide hatching is 3~10min, such as 3min,
4min, 5min, 6min, 7min, 8min, 9min or 10min etc., it is not limited in cited numerical value, the number range
Other unrequited numerical value are equally applicable.
Preferably, the quality mol ratio of step (1 ') kayexalate and the gold nanosphere for (200~
20000):1mg/nmol, such as 200:1、400:1、600:1、1000:1、2000:1、3000:1、5000:1、10000:1、
15000:1、18000:1 or 20000:1 etc., it is not limited to other are unrequited in cited numerical value, the number range
Numerical value is equally applicable.
Preferably, the temperature of step (1 ') hatching be 20~40 DEG C, such as 20 DEG C, 21 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30
DEG C, 32 DEG C, 35 DEG C, 38 DEG C, 39 DEG C or 40 DEG C etc., it is not limited to other are not arranged in cited numerical value, the number range
The numerical value of act is equally applicable.
Preferably, the time of step (1 ') hatching is more than or equal to 3h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h
Deng it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
As currently preferred technical scheme, when step (1) described positive charge molecules are diallyl dimethyl chlorine
When changing ammonium, the quality mol ratio of the diallyl dimethyl ammoniumchloride and the gold nanosphere is (200~20000):
1mg/nmol, such as 200:1、400:1、600:1、1000:1、2000:1、3000:1、5000:1、10000:1、15000:1、
18000:1 or 20000:1 etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
It is applicable.
Preferably, when step (1) described positive charge molecules are diallyl dimethyl ammoniumchloride, step (1) is described
The temperature of hatching is 20~40 DEG C, such as 20 DEG C, 21 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30 DEG C, 32 DEG C, 35 DEG C, 38 DEG C, 39 DEG C or 40
DEG C etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, when step (1) described positive charge molecules are diallyl dimethyl ammoniumchloride, step (1) is described
The time of hatching is more than or equal to 3h, such as 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h, it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range.
As currently preferred technical scheme, the ICG of step (2) positive charge molecules cladding and nanogold particle
Mol ratio is (104~105):1, such as 1 × 104:1、2×104:1、3×104:1、4×104:1、5×104:1、6×104:1、7×
104:1、8×104:1、9×104:1 or 1 × 105:1 etc., it is not limited to cited numerical value, in the number range other
Unrequited numerical value is equally applicable.
Preferably, the temperature of step (2) described hatching be 20~40 DEG C, such as 20 DEG C, 21 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30
DEG C, 32 DEG C, 35 DEG C, 38 DEG C, 39 DEG C or 40 DEG C etc., it is not limited to other are not arranged in cited numerical value, the number range
The numerical value of act is equally applicable.
Preferably, the time of step (2) described hatching be 3~10min such as 3min, 4min, 5min, 6min, 7min,
8min, 9min or 10min etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
It is applicable.
Compared with prior art, the present invention at least has the advantages that:
(1) present invention provides a kind of method of enhancing ICG singlet oxygen yield, and methods described enhances its photo and thermal stability
And realize the enhancing of ICG singlet oxygen yield;
(2) present invention also provides a kind of nanogold particle of ICG claddings and preparation method thereof, and methods described realizes biology
The enhancing of ICG carrier band and singlet oxygen yield in system.
Brief description of the drawings
Fig. 1 a be in comparative example 1 the lower NaA mixed with without the CTAB ICG hatched of laser irradiation degrade between when adding light
The extinction spectra figure of change;
Fig. 1 b be in embodiment 2 the lower NaA mixed with through the CTAB ICG hatched of laser irradiation degrade with anaplasia when adding light
The extinction spectra figure of change;
Fig. 1 c be in embodiment 4 the lower NaA mixed with through the CTAB ICG hatched of laser irradiation degrade with anaplasia when adding light
The extinction spectra figure of change;
Fig. 2 is that NaA degradation amounts are at any time at 50 DEG C of dark-state and in embodiment 1-4 for comparative example 1, comparative example 2, comparative example 2
Between variation diagram;
Fig. 3 a be in embodiment 5 the lower NaA mixed with through the CTAC ICG hatched of laser irradiation degrade with anaplasia when adding light
The extinction spectra figure of change;
Fig. 3 b be in embodiment 6 the lower NaA mixed with through the PDDAC ICG hatched of laser irradiation degrade between when adding light
The extinction spectra figure of change;
Fig. 3 c be in comparative example 3 the lower NaA mixed with through the PSS ICG hatched of laser irradiation degrade with anaplasia when adding light
The extinction spectra figure of change;
Fig. 3 d be in comparative example 4 the lower NaA mixed with through the SDS ICG hatched of laser irradiation degrade with anaplasia when adding light
The extinction spectra figure of change;
Fig. 4 a are the gold nanospheres coated through CTAB in comparative example 5, the delustring light for the NaA that degraded under the irradiation of 808nm laser
Spectrogram;
Fig. 4 b are the gold nanospheres through CTAB and ICG claddings in embodiment 11, the degraded NaA under the irradiation of 808nm laser
Extinction spectra figure;
Fig. 4 c are the gold nanospheres through PDDAC and ICG claddings in embodiment 12, the degraded NaA under the irradiation of 808nm laser
Extinction spectra figure.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, of the invention is typical but non-limiting
Embodiment is as follows:
NaA, can be by singlet oxygen oxidation Decomposition as a kind of reducing agent, and the present invention is using NaA degraded come indirect table
Show the yield of ICG singlet oxygens, NaA degradation amount is calculated by the reduction of NaA characteristic absorption peaks at 265nm.
Agents useful for same and instrument are as follows in each embodiment and comparative example:Tetra chlorauric acid (HAuCl4), silver nitrate
(AgNO3), hexadecyltrimethylammonium chloride (CTAC), dodecyl sodium sulfate (SDS) have purchased from Chinese medicines group chemical reagent
Limit company;Sodium borohydride (NaBH4), cetyl trimethylammonium bromide (CTAB), kayexalate (PSS), Vitamin C
Sour (AA) is purchased from Alfa Aesar;Diallyl dimethyl ammoniumchloride (PDDAC), sodium ascorbate (NaA) are purchased from Sigma
Aldrich;Sulfuric acid (H2SO4) it is purchased from Beijing Chemical Plant;Uv-visible absorption spectra is measured on Varian Cary 50, Zeta
Potential is measured on Zetasizer Nano ZS.
Embodiment 1
A kind of method of enhancing ICG singlet oxygen yield:
CTAB solution (final concentration of 10 μ of CTAB that 10 μ l concentration are 1mM are added in 1ml concentration is 5 μM of ICG solution
M), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 5min in 30 DEG C of water-baths, will be mixed after stirring molten
Liquid is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Embodiment 2
A kind of method of enhancing ICG singlet oxygen yield:
CTAB solution (final concentration of 50 μ of CTAB that 10 μ l concentration are 5mM are added in 1ml concentration is 5 μM of ICG solution
M), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 5min in 30 DEG C of water-baths, will be mixed after stirring molten
Liquid is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Embodiment 3
A kind of method of enhancing ICG singlet oxygen yield:
CTAB solution (final concentration of 100 μ of CTAB that 10 μ l concentration are 10mM are added in 1ml concentration is 5 μM of ICG solution
M), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 5min in 30 DEG C of water-baths, will be mixed after stirring molten
Liquid is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Embodiment 4
A kind of method of enhancing ICG singlet oxygen yield:
CTAB solution (final concentration of 500 μ of CTAB that 10 μ l concentration are 50mM are added in 1ml concentration is 5 μM of ICG solution
M), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 5min in 30 DEG C of water-baths, will be mixed after stirring molten
Liquid is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Embodiment 5
A kind of method of enhancing ICG singlet oxygen yield:
CTAC solution (final concentration of 500 μ of CTAC that 10 μ l concentration are 50mM are added in 1ml concentration is 5 μM of ICG solution
M), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 5min in 30 DEG C of water-baths, will be mixed after stirring molten
Liquid is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Embodiment 6
A kind of method of enhancing ICG singlet oxygen yield:
Adding the PDDAC solution that 50 μ l concentration are 20mg/ml in 1ml concentration is 5 μM of ICG solution, (PDDAC end is dense
Spend for 1mg/mL), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 5min in 30 DEG C of water-baths, after stirring
Mixed solution is added in sample cell, the measurement range of ultraviolet specrophotometer is 200~1100nm.
Embodiment 7
A kind of method of enhancing ICG singlet oxygen yield:
CTAB solution (final concentration of 500 μ of CTAB that 10 μ l concentration are 50mM are added in 1ml concentration is 5 μM of ICG solution
M), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 3min in 40 DEG C of water-baths, will be mixed after stirring molten
Liquid is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Embodiment 8
A kind of method of enhancing ICG singlet oxygen yield:
CTAB solution (final concentration of 500 μ of CTAB that 10 μ l concentration are 50mM are added in 1ml concentration is 5 μM of ICG solution
M), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 10min in 20 DEG C of water-baths, will be mixed after stirring molten
Liquid is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Embodiment 9
A kind of preparation method of the nanogold particle of ICG claddings, the preparation method comprises the following steps:
(1) gold nanosphere that 1ml concentration is 0.1nM is taken, the CTAB solution that 1 μ l concentration is 0.1M is added, in 30 DEG C of water-baths
Middle hatching 5min, obtains the nanogold particle solution of CTAB claddings;
(2) it is 500 μM by nanogold particle and 10 μ l concentration that 1mL concentration is the CTAB claddings that 0.1nM steps (1) are obtained
ICG solution mixing, in 30 DEG C of water-baths lucifuge hatch 5min, obtain nanogold particle load ICG.
Embodiment 10
A kind of preparation method of the nanogold particle of ICG claddings, the preparation method comprises the following steps:
(1) gold nanosphere that 1ml concentration is 0.1nM is taken, the CTAB solution that 0.1 μ l concentration is 0.1M is added, in 40 DEG C of water
Hatch 3min in bath, obtain the nanogold particle solution of CTAB claddings;
(2) it is 500uM by nanogold particle and 20 μ l concentration that 1mL concentration is the CTAB claddings that 0.1nM steps (1) are obtained
ICG solution mixing, in 40 DEG C of water-baths lucifuge hatch 3min, obtain nanogold particle load ICG.
Embodiment 11
A kind of preparation method of the nanogold particle of ICG claddings, the preparation method comprises the following steps:
(1) gold nanosphere that 1ml concentration is 0.1nM is taken, the CTAB solution that 0.5 μ l concentration is 0.1M is added, in 20 DEG C of water
Hatch 10min in bath, obtain the nanogold particle solution of CTAB claddings;
(2) it is 500 μM by nanogold particle and 10 μ l concentration that 1mL concentration is the CTAB claddings that 0.1nM steps (1) are obtained
ICG solution mixing, in 20 DEG C of water-baths lucifuge hatch 10min, obtain nanogold particle load ICG.
Embodiment 12
A kind of preparation method of the nanogold particle of ICG claddings, the preparation method comprises the following steps:
(1 ') takes the gold nanosphere that 1ml concentration is 0.5nM, the CTAB solution that 5ul concentration is 0.1M is added, in 30 DEG C of water-baths
Middle hatching 5min.The concentration for adding 50 μ l NaCl containing 60mM is 20mg/ml PSS solution, is put into 30 DEG C of water-bath hatching 3h,
12000rpm adds isometric three water dissolving after centrifuging 5min, abandoning supernatant, and the nanogold particle for obtaining PSS claddings is molten
Liquid;
(1) 50 μ l NaCl containing 60mM concentration is added in the solution obtained to step (1 ') molten for 20mg/ml PDDAC
Liquid, it is rapid to mix, it is put into after 3h, 12000rpm centrifugation 5min, abandoning supernatant are hatched in 30 DEG C of water-baths and adds isometric three times
Water dissolves, and obtains the nanogold particle solution of PSS and PDDAC claddings;
(2) ICG for adding that 10ul concentration is 500 μM in the gold nanosphere for having coated PDDAC that 1mL concentration is 0.1nM is taken
Solution, lucifuge hatches 5min in 30 DEG C of water-baths, obtains the ICG of nanogold particle load.
Embodiment 13
A kind of preparation method of the nanogold particle of ICG claddings, except the concentration of gold nanosphere in step (1 ') is
0.05nM, CTAB concentration are that other conditions are identical with embodiment 12 outside 0.2M.
Embodiment 14
A kind of preparation method of the nanogold particle of ICG claddings, except the concentration of gold nanosphere in step (1 ') is 5nM
Outside, other conditions are identical with embodiment 12.
Comparative example 1
The NaA solution that 5 μ l concentration are 10mM is added in 1ml concentration is 5 μM of ICG solution, will mixing after stirring
Solution is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Comparative example 2
The CTAB solution (final concentration of 500 μM of CTAB) that 10 μ l concentration are 50mM is added in tri- water of 1ml, is added afterwards
5 μ l concentration are 10mM NaA solution, are added mixed solution in sample cell after stirring, the survey of ultraviolet specrophotometer
Amount scope is 200~1100nm.
Comparative example 3
Adding the PSS solution that 50 μ l concentration are 20mg/ml in 1ml concentration is 5 μM of ICG solution, (PSS's is final concentration of
1mg/mL), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 5min in 30 DEG C of water-baths, will be mixed after stirring
Close solution to add in sample cell, the measurement range of ultraviolet specrophotometer is 200~1100nm.
Comparative example 4
SDS solution (final concentration of 500 μ of SDS that 10 μ l concentration are 50mM are added in 1ml concentration is 5 μM of ICG solution
M), the NaA solution that 5 μ l concentration are 10mM is added after lucifuge hatching 5min in 30 DEG C of water-baths, will be mixed after stirring molten
Liquid is added in sample cell, and the measurement range of ultraviolet specrophotometer is 200~1100nm.
Comparative example 5
Methods described is in addition to without step (2), and other conditions are identical with embodiment 11.
The present invention is based on four basic experimental phenomenas:(1) ICG can produce singlet oxygen under the irradiation of 808nm laser, single
The yield of line state oxygen can indirectly be reflected by the effect for aoxidizing NaA.(2) by after the CTAB hatchings of ICG and various concentrations, laser shines
Degraded NaA ability enhancing after penetrating, and enhanced effect and CTAB concentration positive correlations.(3) be equally positively charged macromolecule
CTAC, PDDAC can also strengthen the effect that ICG produces singlet oxygen, and electronegative SDS, PSS do not interfere with ICG single lines then
State oxygen yield.(4) ICG can be loaded with electrostatic with the gold nanosphere for covering CTAB or PDDAC, can equally realizes singlet oxygen
The enhancing of yield.
First, NaA, can be by singlet oxygen oxidation Decomposition as a kind of reducing agent, and the present invention is using NaA degraded come between
The yield for representing ICG singlet oxygens is connect, NaA degradation amount is calculated by the reduction of NaA characteristic absorption peaks at 265nm.In wavelength
For under 808nm continuous laser irradiation, ICG can make NaA degrade, and with ICG light degradation, NaA degradation speed is slack-off.
Add after cationicsurfactants, ICG degradeds NaA ability enhancing.In order to probe into this enhancing and CTAB concentration
Whether related, the CTAB and ICG that 10 μM/50 μM/100 μM/500 μM of five concentration have been respectively adopted are hatched, and contrast them
The difference of NaA degradeds in 3 minutes is irradiated in 2W/808nm continuous laser, it can be seen that CTAB can strengthen NaA oxygen really
Change degraded, i.e. the singlet oxygen that CTAB can improve ICG is produced, and singlet oxygen yield raising and CTAB amount into positive
Close (Fig. 1, Fig. 2).
In order to probe into whether this effect is that the present invention also distinguishes because CTAB molecules generate special reaction with ICG
Hatch ICG, wherein CTAC and PDDAC positively chargeds with CTAC, PDDAC, PSS, SDS and PSS and SDS are negatively charged.As a result (Fig. 3)
It can be seen that, the enhancing of this singlet oxygen yield is not only occurred in CTAB solution, but a kind of positive charge macromolecular chain is universal
Effect, electronegative macromolecular chain can not influence ICG singlet oxygen yield.From the uv-visible absorption spectras of ICG in itself
It can be seen that (Fig. 1), with the increase of CTAB concentration, ICG monomer peak (at 780nm) diminishes, and is inhaled in long wave side and shortwave side
Receive peak and become strong, this change of absworption peak shows that, due to the electrostatic interaction with positive charge macromolecular chain, ICG forms more
Aggregation (J.Photochem.Photobiol.B:Biol., 1998,47,155-164), increasing for this aggregation plays
A kind of protective effect (ACS Nano, 2014,11,11529-11542) to ICG, makes the increase of ICG singlet oxygens yield.
, it is necessary to which ICG is transported into vivo by carrier when ICG is applied as a kind of sensitising agent.It is last to be sent out to realize in the present invention
The existing practical application to ICG singlet oxygen yield enhancing effects, with gold nano grain as carrier, surface respectively with CTAB and
PDDAC coats (table 1), after gold-nanoparticle-supported, list consistent when can show to hatch with equal amount macromolecular chain ICG
After line state oxygen enhancing effect (Fig. 4 b/c), the gold-nanoparticle-supported ICG coated with CTAB, it can cause during oxidative degradation NaA
The reunion of gold grain, this phenomenon does not occur in the case where not loading ICG, is the ICG for being supported on gold nano grain surface
Photodegradation Products result in the reunion (Fig. 4 a/b) of gold grain, further demonstrate that the successful load to ICG.
Table 1
Surface potential (mV) | CTAB | PSS | PDDAC |
AuS | 31.6±3.2 | -41.5±2.4 | 54.1±5.1 |
AuS-ICG | 17.7±1.4 | - | 42.6±4.3 |
Applicant states that the present invention illustrates the detailed construction feature of the present invention by above-described embodiment, but the present invention is simultaneously
Above-mentioned detailed construction feature is not limited to, that is, does not mean that the present invention has to rely on above-mentioned detailed construction feature and could implemented.Institute
Belong to those skilled in the art it will be clearly understood that any improvement in the present invention, to the equivalence replacement of part selected by the present invention
And increase, the selection of concrete mode of accessory etc., within the scope of all falling within protection scope of the present invention and being open.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of method of enhancing ICG singlet oxygen yield, it is characterised in that hatch ICG using positive charge molecules.
2. according to the method described in claim 1, it is characterised in that the positive charge molecules include cationic surfactant
And/or positive charge polyelectrolyte;
Preferably, the cationic surfactant includes cetyl trimethylammonium bromide and/or cetyl trimethyl chlorine
Change ammonium;
Preferably, the positive charge polyelectrolyte is diallyl dimethyl ammoniumchloride.
3. method according to claim 1 or 2, it is characterised in that the positive charge molecules and ICG mol ratio for (1~
100):1。
4. the method according to claim any one of 1-3, it is characterised in that the temperature of the hatching is 20~40 DEG C;
Preferably, the time of the hatching is 3~10min;
Preferably, the hatching is carried out under the conditions of lucifuge.
5. a kind of nanogold particle of ICG claddings, it is characterised in that the nanogold particle coats positive charge successively from inside to outside
Molecular layer and ICG layers.
6. the preparation method for the nanogold particle that ICG described in a kind of claim 5 is coated, it is characterised in that the preparation method
Comprise the following steps:
(1) hatch nanogold particle using positive charge molecules, obtain the nanogold particle solution of positive charge molecules cladding;
(2) the nanogold particle solution of the positive charge molecules cladding obtained step (1) is mixed with ICG, is hatched, is obtained nanogold
The ICG of particulate load.
7. preparation method according to claim 6, it is characterised in that step (1) positive charge molecules and the nanometer
The mol ratio of gold grain is (105~106):1;
Preferably, the temperature of step (1) described hatching is 20~40 DEG C;
Preferably, the time of step (1) described hatching is 3~10min.
8. preparation method according to claim 6, it is characterised in that when step (1) described positive charge molecules are polydiene
During diallyidimethylammonium chloride, step (1 ') is carried out before step (1), first hatches Jenner using cetyl trimethylammonium bromide
Rice grain, reuses kayexalate hatching gold nano grain, obtains the gold nano grain of kayexalate cladding;
Preferably, the mol ratio of step (1 ') cetyl trimethylammonium bromide and the nanogold particle is (1 × 105~
2×107):1;
Preferably, the temperature of step (1 ') the cetyl trimethylammonium bromide hatching is 20~40 DEG C;
Preferably, the time of step (1 ') the cetyl trimethylammonium bromide hatching is 3~10min;
Preferably, the quality mol ratio of step (1 ') kayexalate and the gold nanosphere for (200~
20000):1mg/nmol;
Preferably, the temperature of step (1 ') the kayexalate hatching is 20~40 DEG C;
Preferably, the time of step (1 ') the kayexalate hatching is more than or equal to 3h.
9. preparation method according to claim 8, it is characterised in that when step (1) described positive charge molecules are polydiene
During diallyidimethylammonium chloride, the quality mol ratio of the diallyl dimethyl ammoniumchloride and the gold nanosphere is (200
~20000):1mg/nmol;
Preferably, when step (1) described positive charge molecules are diallyl dimethyl ammoniumchloride, step (1) hatching
Temperature be 20~40 DEG C;
Preferably, when step (1) described positive charge molecules are diallyl dimethyl ammoniumchloride, step (1) hatching
Time be more than or equal to 3h.
10. the preparation method according to claim any one of 6-9, it is characterised in that step (2) ICG and positive charge
The mol ratio of the nanogold particle of molecule cladding is (104~105):1;
Preferably, the temperature of step (2) described hatching is 20~40 DEG C;
Preferably, the time of step (2) described hatching is 3~10min.
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