CN109986090A - A kind of double ligand gold nanoparticle aqueous solutions and its preparation method and application - Google Patents
A kind of double ligand gold nanoparticle aqueous solutions and its preparation method and application Download PDFInfo
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- CN109986090A CN109986090A CN201910219691.7A CN201910219691A CN109986090A CN 109986090 A CN109986090 A CN 109986090A CN 201910219691 A CN201910219691 A CN 201910219691A CN 109986090 A CN109986090 A CN 109986090A
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
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Abstract
The present invention discloses a kind of double ligand gold nanoparticle aqueous solutions and its preparation method and application.The preparation method specifically: sulfydryl small molecule compound A aqueous solution is added in solvent, aqueous solution of chloraurate is added under conditions of oil bath and stirring, is stirred to react, dialyses after cooling, obtains single ligand gold nanoparticle aqueous solution；Single ligand gold nanoparticle aqueous solution is added in sulfydryl small molecule compound B aqueous solution, is dialysed after being stirred to react, double ligand gold nanoparticle aqueous solutions are obtained.Synthetic method craft of the present invention is simple, consumes energy low, low in cost, is easy to be mass produced.Double ligand gold nanoparticle aqueous solutions that the present invention synthesizes at least improve 87% or more than the generation singlet oxygen rate of single ligand, show that double ligand gold nanoparticle aqueous solutions inhibit the growth of cancer cell to become apparent under illumination condition than single ligand gold nanoparticle aqueous solution in cancer cell in vitro model.
Description
Technical field
The invention belongs to function optical nano Material Fields, and in particular to a kind of double ligand gold nanoparticle aqueous solutions and its
Preparation method and application.
Background technique
With being continuously increased for global cancer morbidity and the death rate, it is very urgent to develop effective cancer diagnosis and treatment reagent.
In chemotherapy process, usual chemotherapeutics generates more serious side effect and largely drug resistance, curative effect to patient
And not up to ideal effect, tumor recurrence and transfer are relatively conventional.In order to improve the therapeutic effect of patient, different treatment sides
Method is proposed that wherein optical dynamic therapy is a fast-developing anti-cancer therapies extensively.By photosensitizer oxygen and light simultaneously
A kind of singlet oxygen substance with high activity is generated under existence condition, and the structures such as cancer cell internal protein and DNA is promoted to destroy
And then cause apoptosis of tumor cells, while having no effect under subdued light conditions to cancer cell and normal cell.Due to light
The features such as motivation therapy, which has, to have no drug resistance, and lesser side effect and edge tissues damage are small, this method are a kind of great latent
Power oncotherapy means are gradually expanded.
Singlet oxygen currently used for optical dynamic therapy is mainly generated by traditional small organic molecule photosensitizer, but
It is that there is traditional small organic molecule photosensitizer synthesis technology complexity, poorly water-soluble, selective low, dermal toxicity greatly, easily to be dropped by enzyme
The disadvantages of solution, significantly limits its more extensive clinical application.In recent years, the optical material of nanoscale such as metal nano
Particle and semiconductor-quantum-point etc. are reported in succession with the ability for generating singlet oxygen, wherein extra small luminous gold nanoparticle
(AuNPs) with synthesizing, simple, good water solubility, biocompatibility are high, cancer target is high-efficient and the advantages such as stability is good are being faced
Huge potential applicability in clinical practice is shown in terms of bed optical dynamic therapy.For extra small luminous AuNPs, the problem of being primarily present is it
The efficiency for generating singlet oxygen is lower, it is difficult to meet the needs of optical dynamic therapy in clinical treatment.Therefore, exploitation and design have
The AuNPs for efficiently generating singlet oxygen performance has important scientific research and clinical value.
Summary of the invention
In order to promote the efficiency that AuNPs generates singlet oxygen, the present invention provides a kind of simple, easy to operate, promotion effects
Significant method.The primary purpose of the present invention is that providing a kind of double ligand gold nanoparticle aqueous solutions.
Another object of the present invention is to provide the preparation methods of above-mentioned double ligand gold nanoparticle aqueous solutions.
A further object of the present invention is to provide the applications of above-mentioned double ligand gold nanoparticle aqueous solutions.
The AuNPs that this method prepares double ligand surface functionalization can efficiently produce the list of high activity under illumination condition
Line state oxygen, leads to cancer cell death after acting on cancer cell.Therefore, double ligand AuNPs prepared by the present invention are controlled in clinical tumor
Treatment field has biggish application prospect.
The method of the present invention is achieved through the following technical solutions:
A kind of preparation method of double ligand gold nanoparticle aqueous solutions, synthetic reaction formula are as follows:
Specifically includes the following steps:
(1) sulfydryl small molecule compound A is added to the water, configuration obtains sulfydryl small molecule compound A aqueous solution；
(2) sulfydryl small molecule compound A aqueous solution is added in solvent, chlorine gold is added under conditions of oil bath and stirring
Aqueous acid continues stirring and is reacted, and stops reaction when the fluorescence intensity of reaction system, which reaches, not to be further added by by force most, cooling
It is put into bag filter after to room temperature, dialyses in water, after dialysis, obtain single ligand gold nanoparticle aqueous solution；
(3) single ligand gold nanoparticle aqueous solution that step (2) is prepared is added to sulfydryl small molecule compound B water
In solution, reaction is stirred at room temperature, is put into bag filter after the reaction was completed, dialyses in water, after dialysis, obtains double match
Body gold nanoparticle aqueous solution.
Preferably, the molar concentration of step (1) the sulfydryl small molecule compound A aqueous solution be 0.01mol/L~
0.20mol/L。
Preferably, step (1) the sulfydryl small molecule compound A have following structure: R-SH, wherein R be it is nitrogenous or
The alkyl or heterocycle of oxygen atom.
Preferably, step (1) the sulfydryl small molecule compound A is poly glycol monomethyl ether mercaptan, mercapto-polyglycol
One of amino, mercapto-polyglycol carboxyl, glutathione, bovine serum albumin and mercaptopropionic acid.
Preferably, the molar ratio of step (2) the sulfydryl small molecule compound A and gold chloride is 1:1~8:1, gold chloride
Final concentration of 1~5mmol/L in the reaction system.
Preferably, step (2) solvent be ethyl alcohol, methanol, tetrahydrofuran, one of acetonitrile and water, more preferably
For water.
Preferably, the temperature of step (2) described oil bath is 25~95 DEG C.
Preferably, step (2) rate for continuing stirring is 1000rpm/min~1500rpm/min.
Preferably, step (2) room temperature is 4~37 DEG C.
Preferably, the molecular cut off of step (2) described bag filter is 3~10kDa.
Preferably, step (2) dialysis specifically: dialysis is minimum three times, and each time is no less than 6h.
Preferably, step (3) the sulfydryl small molecule compound B is mercaptoethylmaine, mercaptobenzimidazole and mercaptoimidazole
One of.
Preferably, the concentration of step (3) the sulfydryl small molecule compound B aqueous solution is 0.01mmol/L~1mmol/L.
Preferably, the gold atom in step (3) the sulfydryl small molecule compound B and single ligand gold nanoparticle aqueous solution
Molar ratio be 0.1:1~10:1, preferred molar ratio is 3:1, and the gold atom in Dan Peiti gold nanoparticle aqueous solution exists
Final concentration of 0.08mmol/L~20mmol/L in reaction system.
Preferably, the time of step (3) described stirring is 10min~48h, more preferably for 24 hours.
Preferably, step (3) room temperature is 4 DEG C~37 DEG C.
Preferably, the molecular cut off of step (3) described bag filter is 3~10kDa.
Preferably, step (3) dialysis specifically: dialysis is minimum three times, and each time is no less than 6h.
Double ligand gold nanoparticle aqueous solutions that the preparation method of above-mentioned double ligand gold nanoparticle aqueous solutions is prepared.
Above-mentioned double ligand gold nanoparticle aqueous solutions are preparing the application in photosensitizer.
Compared with prior art, the invention has the advantages that and technical effect:
(1) preparation method of the present invention is simple, easy to operate, time-consuming low, low in cost；
(2) preparation method of the present invention is selectively extensive, can be for single ligand gold nanoparticle water such as amination and carboxylated
Solution is implemented；
(3) it utilizes the rate of double ligand gold nanoparticle aqueous solutions generation singlet oxygen of the method for the present invention preparation and singly matches
Body gold nanoparticle aqueous solution proves that it generates list under the conditions of visible light shines compared at least improving 87%, by experiment in vitro
Line state oxygen kills cancer cell, has the larger potentiality for being applied to clinical optical dynamic therapy.
Detailed description of the invention
Fig. 1 is excitation, transmitting and the absorption spectrum for single ligand gold nanoparticle aqueous solution that embodiment 1 is prepared.
Fig. 2 is the transmission electron microscope figure for single ligand gold nanoparticle aqueous solution that embodiment 1 is prepared.
Fig. 3 is x-ray photoelectron spectroscopy (XPS) figure for single ligand gold nanoparticle aqueous solution that embodiment 1 is prepared.
Fig. 4 is single ligand gold nanoparticle aqueous solution that embodiment 1 is prepared and double ligand gold nanoparticle aqueous solutions
Fluorescence spectrum comparative diagram.
Fig. 5 is the transmission electron microscope figure for double ligand gold nanoparticle aqueous solutions that embodiment 1 is prepared.
Fig. 6 is single ligand gold nanoparticle that embodiment 1 synthesizes and double ligand gold nanoparticle aqueous solutions in pH=7.4 item
Zeta electric potential figure under part.
Fig. 7 is the ultravioletvisible absorption light for the mono- ligand gold nanoparticle aqueous solution of 0.1mmol/L that embodiment 1 is prepared
Spectrogram.
Fig. 8 is single ligand gold nano that ABDA and embodiment 1 are prepared during singlet oxygen generates under the conditions of being protected from light
The mixed solution of particle aqueous solution places the ultraviolet-visible absorption spectroscopy figure of different time.
Fig. 9 is single ligand gold nano that ABDA and embodiment 1 are prepared during singlet oxygen generates under illumination condition
The mixed solution of particle aqueous solution places the ultraviolet-visible absorption spectroscopy figure of different time.
Figure 10 is the ultravioletvisible absorption for the bis- ligand gold nanoparticle aqueous solutions of 0.1mmol/L that embodiment 1 is prepared
Spectrogram.
Figure 11 is double ligand Jenners that ABDA and embodiment 1 are prepared during singlet oxygen generates under the conditions of being protected from light
The mixed solution of rice corpuscles aqueous solution places the ultraviolet-visible absorption spectroscopy figure of different time.
Figure 12 is double ligand Jenners that ABDA and embodiment 1 are prepared during singlet oxygen generates under illumination condition
The mixed solution of rice corpuscles aqueous solution places the ultraviolet-visible absorption spectroscopy figure of different time.
Under the conditions of Figure 13 is being protected from light of embodiment 1, blank group ABDA solution places the ultravioletvisible absorption light of different time
Spectrogram.
Figure 14 is under the illumination condition of embodiment 1, and blank group ABDA solution places the ultravioletvisible absorption light of different time
Spectrogram.
Figure 15 be the single ligand that is prepared of embodiment 1 and double ligand gold nanoparticle aqueous solution difference light application times-not
Reaction ABDA accounts for the linear fit comparison diagram of the percentage of initial amount.
Figure 16 is the cell experiment result figure of embodiment 1.
Figure 17 is the fluorescence spectrum control of single ligand that embodiment 2 is prepared and double ligand gold nanoparticle aqueous solutions
Figure.
Figure 18 be the single ligand that is prepared of embodiment 2 and double ligand gold nanoparticle aqueous solution difference light application times-not
Reaction ABDA accounts for the linear fit comparison diagram of the percentage of initial amount.
Figure 19 is the fluorescence spectrum control of single ligand that embodiment 3 is prepared and double ligand gold nanoparticle aqueous solutions
Figure.
Figure 20 be the single ligand that is prepared of embodiment 3 and double ligand gold nanoparticle aqueous solution difference light application times-not
Reaction ABDA accounts for the linear fit comparison diagram of the percentage of initial amount.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiments and drawings, but of the invention
Protection scope and embodiment are without being limited thereto.
In embodiment, the instrument that the change in fluorescence that the gold nanoparticle of single ligand generates in detection synthesis process uses is glimmering
Light/phosphorescence/luminescence spectrophotometer (LS-55, U.S. PerkinElmer), the gold nanoparticle of more single ligand and double ligands
The instrument that uses of generation rate be ultraviolet-visible absorption spectroscopy instrument (UV-1780, Japanese Shimadzu), quantitative list ligand Jenner's grain of rice
The concentration of son uses icp ms (ICP-MS, Thermo Fischer Scient Inc.), and detection cytotoxicity makes
Instrument is automatic microplate reader (ELX800, U.S. Biotek).
Embodiment 1
All glasswares first pass through chloroazotic acid soaking and washing mistake in advance, at room temperature, by 9.0mL polyethyleneglycol first
(concentration 0.05mol/L, poly glycol monomethyl ether thiol molecule amount are 800) to add with 39.5mL deionized water to ether mercaptan aqueous solution
Enter into the three-necked flask of 100mL specification, it is water-soluble that 1.5mL gold chloride is then added under conditions of 90 DEG C of oil baths, magnetic agitations
Liquid (concentration 0.1mol/L) continues to stir under the conditions of stirring rate 1500rpm/min later, until with fluorescent/phosphorescent/hair
The fluorescence intensity of light spectrophotometer detection reaction system stops reacting at once when reaching most strong, and retention is used after being cooled to room temperature
Molecular weight is that the bag filter of 3kDa is dialysed 3 times in deionized water solution, and room temperature, no less than 6h, obtains glassy yellow every time
Single ligand gold nanoparticle aqueous solution.
For subsequent further operating, gained list ligand gold nanoparticle aqueous solution by the super filter tube of molecular weight 3kDa from
The heart (4000rpm/min) is concentrated into 500 μ L, takes out solution into 1.5mL centrifuge tube, 2100g high speed centrifugation removes bottom later
Then bulky grain quantitatively obtains the mono- ligand gold nanoparticle aqueous solution of 50mmol/L using ICP-MS.
Later in the three-necked flask of 100mL specification, the mono- ligand gold nanoparticle aqueous solution of 0.1mL 50mmol/L is taken to add
Entering into 50mL 0.3mmol/L mercaptoethylmaine aqueous solution and reacts, mercaptoethylmaine is the sulfydryl small molecule compound B,
It stirs at room temperature for 24 hours, solution is still yellow.It is saturating in deionized water solution using the bag filter that molecular cut off is 3kDa later
Analysis 3 times, room temperature, no less than 6h, obtains double ligand gold nanoparticle aqueous solutions every time.
For subsequent further operating, the double ligand gold nanoparticle aqueous solutions of gained by the super filter tube of molecular weight 3kDa from
The heart (4000rpm/min) is concentrated into 500 μ L, takes out solution into 1.5mL centrifuge tube, 2100g high speed centrifugation removes bottom later
Then bulky grain quantitatively obtains the bis- ligand gold nanoparticle aqueous solutions of 50mmol/L using ICP-MS.
Fig. 1 is normalized excitation, transmitting and the absorption for single ligand gold nanoparticle aqueous solution that embodiment 1 is prepared
Spectrogram.It follows that the maximum emission wavelength of gold nanoparticle is in 610nm, excitation wavelength 390nm from figure.
Fig. 2 is the transmission electron microscope figure for single ligand gold nanoparticle aqueous solution that embodiment 1 is prepared.From figure
It can be seen that gold nanoparticle is evenly dispersed in water, the partial size of Dan Peiti gold nanoparticle is 0.5~3nm.
Fig. 3 is x-ray photoelectron spectroscopy (XPS) figure for single ligand gold nanoparticle aqueous solution that embodiment 1 is prepared.
It is analyzed by XPS swarming software, swarming is fitted monovalence gold element peak area and zeroth order gold element peak area, is calculated: wherein
The ratio of the total gold element of monovalence gold element Zhan is 44.46%.
Fig. 4 is single ligand gold nanoparticle aqueous solution that embodiment 1 is prepared and double ligand gold nanoparticle aqueous solutions
Fluorescence spectrum comparative diagram.
Fig. 5 is the transmission electron microscope figure for double ligand gold nanoparticle aqueous solutions that embodiment 1 is prepared.From figure
It can be seen that double ligand gold nanoparticles are evenly dispersed in water, the partial size of double ligand gold nanoparticles is 0.5~3nm.
Fig. 6 is single ligand gold nanoparticle that embodiment 1 synthesizes and double ligand gold nanoparticle aqueous solutions in pH=7.4 item
Zeta electric potential figure under part.As can be seen from the figure: Dan Peiti gold nanoparticle is negatively charged, and double ligand gold nanoparticle band portions
Divide positive electricity.
To detect the rate that single ligand gold nanoparticle aqueous solution of above-mentioned synthesis generates singlet oxygen, a kind of list has been used
Line state oxygen specific detection agent: 9,10- anthracene diyl-two (methylene), two malonic acid (abbreviation ABDA, > 99%), UV, visible light
There are four characteristic absorption peak 342,359,378 and 400nm for absorption spectrum tool, and testing principle is once there is singlet oxygen production in solution
Raw, ABDA can capture the singlet oxygen in solution at once, and reaction generates a kind of endogenic oxidation product, leads to four of ABDA
Characteristic absorption peak decline, reaction equation are as follows:
Wherein the fall off rate of ABDA absorption peak corresponds to the generation rate of singlet oxygen.Pass through UV, visible light spectrophotometric
You can get it for the variation of the ultraviolet-visible absorption spectroscopy of measurement examination sample to be tested and ABDA mixed solution under illumination different time
Generate the rate of singlet oxygen.
Detect the method that single ligand gold nanoparticle generates singlet oxygen rate: specific experiment step is, using it is ultraviolet can
After seeing that absorption spectrometer, instrument preheat 15min, add the BR of 500 μ L 0.04mol/L slow respectively in the cuvette of two 700 μ L
It rushes solution (pH 7.4), one is used as sample cell, another sweeps baseline (300~600nm) first, then sweep as reference cell
Blank, it is ensured that blank absorption value at 300~600nm fluctuates within ± 0.0005, shows that sample cell is clean, later in sample
1 μ L is added in pond and determines the measured mono- ligand gold nanoparticle aqueous solution of 50mmol/L, measures single ligand gold nanoparticle aqueous solution
The absorption spectrum (test result such as Fig. 7) of (concentration 0.1mmol/L), is added the 10 μ L configured 10mmol/L of DMSO later
ABDA solution is uniformly mixed, and surveys absorption spectrum every 5min under the conditions of being protected from light, and total 15min takes out be placed into later
In the centrifuge tube of 1.5mL, with laser (450nm 100mW/cm2) illumination list ligand gold nanoparticle and ABDA mixing it is molten
Liquid, every illumination 5min survey an absorption spectrum, continuous light time 15min, test result such as Fig. 8.
Fig. 7 is the ultraviolet-visible absorption spectroscopy figure of single ligand gold nanoparticle aqueous solution of 0.1mmol/L.
Fig. 8 is under the conditions of being protected from light, and singlet oxygen indicator ABDA is prepared with embodiment 1 during singlet oxygen generates
Single ligand gold nanoparticle aqueous solution mixed solution place different time ultraviolet-visible absorption spectroscopy figure.It can be with from figure
Find out: place 5,10,15min is overlapped with 0min line, illustrate that under the condition that is protected from light, list ligand gold nanoparticle does not generate singlet
Oxygen.
Fig. 9 is under illumination condition, and singlet oxygen indicator ABDA is prepared with embodiment 1 during singlet oxygen generates
Single ligand gold nanoparticle aqueous solution mixed solution place different time ultraviolet-visible absorption spectroscopy figure.It can be with from figure
Find out: with the increase of light application time, absorption of the mixed solution in 380nm is gradually reduced, and illustrates single ligand under illumination condition
Gold nanoparticle produces singlet oxygen.
Detect the method that double ligand gold nanoparticles generate singlet oxygen rate: the double ligand gold nanoparticles of detection generate single
The method of line state oxygen rate is identical with single ligand gold nanoparticle generation method of singlet oxygen rate is detected.
Figure 10 is the ultraviolet-visible absorption spectroscopy figure of double ligand gold nanoparticle aqueous solutions of 0.1mmol/L.
Figure 11 is double ligand Jenners that ABDA and embodiment 1 are prepared during singlet oxygen generates under the conditions of being protected from light
The mixed solution of rice corpuscles aqueous solution places the ultraviolet-visible absorption spectroscopy figure of different time.As can be seen from the figure: placement 5,
10,15min is overlapped with 0min line, illustrates that double ligand gold nanoparticles do not generate singlet oxygen under the conditions of being protected from light.
Figure 12 is under illumination condition, and singlet oxygen indicator ABDA is prepared into embodiment 1 during singlet oxygen generates
The mixed solution of the double ligand gold nanoparticle aqueous solutions arrived places the ultraviolet-visible absorption spectroscopy figure of different time.It can from figure
To find out: with the increase of light application time, absorption of the mixed solution in 380nm is gradually reduced, and illustrates double under illumination condition match
Body gold nanoparticle produces singlet oxygen.
Blank group: for the influence for excluding ABDA auto-degradation and causing absorption peak to decline by light degradation, one group of sky is set
White group, blank group adds 1 μ L deionized water, the side of other operations and the rate for detecting single ligand gold nanoparticle generation singlet oxygen
Method equally carries out.
Figure 13 is under the conditions of being protected from light, and the ABDA solution of blank group places the ultraviolet-visible absorption spectroscopy figure of different time.From
In figure it can be seen that place 5,10,15min is overlapped with 0min line, illustrate under the conditions of being protected from light ABDA holding stabilization.
Figure 14 is under illumination condition, and the ABDA solution of blank group places the ultraviolet-visible absorption spectroscopy figure of different time.From
In figure it can be seen that place 5,10,15min be overlapped with 0min line, illustrate that ABDA is equally kept stable under illumination condition, into one
Step instruction sheet ligand gold nanoparticle and double ligand gold nanoparticles are to generate singlet oxygen by illumination ABDA is caused to absorb
Peak decline.
Calculate the enhancing efficiency that double ligand gold nanoparticles generate singlet oxygen: two when generating rate because of detection singlet oxygen
Kind nanoparticle concentration is identical, so the enhancing efficiency of double ligand gold nanoparticles are as follows: double ligand gold nanoparticles and Dan Peiti
Gold nanoparticle leads to the ratio between ABDA descending slope with light application time increase.Illumination different time list ligand gold nano is calculated first
Unreacted ABDA accounts for the percentage of initial amount in particle aqueous solution and ABDA mixed solution, take respectively on every spectrogram of Fig. 9
The absorption value of 380nm deducts the mono- ligand gold nanoparticle of 0.1mmol/L in the absorption (as shown in Figure 7) of 380nm, obtains illumination
The value of different time points represents unreacted ABDA, obtains light multiplied by 100% divided by the value of illumination 0min respectively later
The percentage of initial amount is accounted for according to unreacted ABDA in different time list ligand gold nanoparticle aqueous solution and ABDA mixed solution.
Then it calculates unreacted ABDA in the double ligand gold nanoparticle aqueous solutions of illumination different time and ABDA mixed solution and accounts for starting
The percentage of amount takes the absorption value on every spectrogram of Figure 12 in 380nm respectively, deducts the bis- ligand gold nanoparticles of 0.1mmol/L
In the absorption (as shown in Figure 10) of 380nm, the value for obtaining illumination different time points represents double ligand gold nanoparticle aqueous solutions
With ABDA unreacted in ABDA mixed solution, illumination is obtained not multiplied by 100% divided by the value of illumination 0min respectively later
The percentage of initial amount is accounted for unreacted ABDA in time double ligand gold nanoparticle aqueous solutions and ABDA mixed solution.With light
It is abscissa according to different time (0,5,10,15), the percentage that the unreacted ABDA of illumination different time accounts for initial amount is vertical sit
It is denoted as figure, then Figure 15 is obtained by linear fit.
Figure 15 is single ligand prepared by embodiment 1 and double ligand gold nanoparticle aqueous solution difference light application time-unreacteds
ABDA account for initial amount percentage linear fit comparison diagram.It was found from Figure 15 fitting a straight line: Dan Peiti gold nanoparticle with
Light application time increase causes ABDA amount descending slope to be -4.40, and double ligand gold nanoparticles lead to ABDA with light application time increase
Descending slope is -8.24, is finally calculated: the rate that double ligand gold nanoparticles generate singlet oxygen compares single ligand Jenner
Rice corpuscles, enhancing percentage are (- 8.24- (- 4.40))/(- 4.40)) × 100%=87%.
Cell experiment
Use HeLa cell (HeLa cell line by Nanfang Medical Univ (Guangzhou) provide) as model in vitro, in advance 12
Hour takes intermediate 18 holes, every hole culture 1 × 10 in two piece of 96 orifice plate4A HeLa cell, the training that every hole adds 100 μ L newly to configure
Base is supported, the culture medium newly configured is containing 10% South America (v/v) Uruguay top grade fetal calf serum, 1% (v/v) Pen .- Strep
The high glucose medium (DMEM) of (Invitrogen (Shanghai) Trading Co., Ltd.), one piece of 96 orifice plate is as light group, one piece of conduct
It is protected from light group.After 12 hours, the list that every hole adds 0.4 μ L50mmol/L embodiment 1 to prepare in 6 holes in 96 orifice plates of light group is matched
Body gold nanoparticle aqueous solution, double ligand gold nanoparticle water that every hole adds 0.4 μ L 50mmol/L embodiment 1 to prepare in another 6 hole
Solution, another 6 hole add 0.4 μ L deionized water as the every hole of blank, represent 6 parallel laboratory tests.It is protected from light 96 orifice plates and light group of group
96 orifice plates equally operate.Later two piece of 96 orifice plate be placed in incubator (37 DEG C, 5%CO2) culture 6h, illumination is taken out later
96 orifice plates of group are at room temperature with blue LED lamp illumination (wavelength 450nm, optical density 2.5mW/cm2) 4h, it is protected from light the 96 of group
Orifice plate places room temperature and is protected from light culture 4h, and light group and 96 orifice plates for being protected from light group, which continue to place in incubator, later cultivates 14h, then
The 20 configured 5mg/mL MTT solution of μ L phosphate buffer are added in each hole, light group and 96 orifice plates for being protected from light group continue
Incubator culture 4h is placed, is then all taken the solution in hole away, every hole is added immediately 150 μ L DMSO solutions, with 96 orifice plates
After oscillator vibrates 10min 1000rpm/min, with the absorption value of automatic microplate reader test 490nm, that is, corresponds to and deposit
Cell quantity living.The mean absorbance for calculating 6 parallel laboratory tests, divided by the mean absorbance for the blank being protected from light in group, so
Afterwards multiplied by 100%, i.e. expression cell survival rate (%), test result is as described in Figure 16.
Figure 16 is the cell experiment result figure of embodiment 1.As can be seen from the figure: under the conditions of being protected from light, two kinds of gold nanos
Particle does not have toxicity to cell, and under illumination condition, double ligand gold nanoparticles, which are apparently higher than the toxicity of cell, singly matches
The light group of body gold nanoparticle, blank group does not almost have toxicity to cell.
Embodiment 2
All glasswares first pass through chloroazotic acid soaking and washing mistake in advance, at room temperature, by the poly- second two of 12.0mL sulfydryl
(concentration 0.1mol/L, mercapto-polyglycol amino molecule amount are 1000) to be added with 36.5mL deionized water to alcohol amino aqueous solution
Into the three-necked flask of 100mL specification, 1.5mL aqueous solution of chloraurate is then added under conditions of 95 DEG C of oil baths, magnetic agitations
(concentration 0.1mol/L) continues to stir under the conditions of stirring rate 1500rpm/min later, until with fluorescent/phosphorescent/shine
The fluorescence intensity of spectrophotometer detection reaction system stops reacting at once when reaching most strong, and retention point is used after being cooled to room temperature
The bag filter that son amount is 3kDa is dialysed 3 times in deionized water solution, and room temperature, no less than 6h, obtains glassy yellow list every time
Ligand gold nanoparticle aqueous solution.
For subsequent further operating, gained list ligand gold nanoparticle aqueous solution by the super filter tube of molecular weight 3kDa from
The heart (4000rpm/min) is concentrated into 500 μ L, takes out solution into 1.5mL centrifuge tube, 2100g high speed centrifugation removes bottom later
Then bulky grain quantitatively obtains the mono- ligand gold nanoparticle aqueous solution of 50mmol/L using ICP-MS.
Later in the three-necked flask of 100mL specification, the mono- ligand gold nanoparticle aqueous solution of 0.1mL 50mmol/L is taken to add
Entering into 50mL 0.3mmol/L mercaptoethylmaine aqueous solution and reacts, mercaptoethylmaine is the sulfydryl small molecule compound B,
It stirs at room temperature for 24 hours, solution is still yellow.It is saturating in deionized water solution using the bag filter that molecular cut off is 3kDa later
Analysis 3 times, room temperature, no less than 6h, obtains double ligand gold nanoparticle aqueous solutions every time.
For subsequent further operating, the double ligand gold nanoparticle aqueous solutions of gained by the super filter tube of molecular weight 3kDa from
The heart (4000rpm/min) is concentrated into 500 μ L, takes out solution into 1.5mL centrifuge tube, 2100g high speed centrifugation removes bottom later
Then bulky grain quantitatively obtains the bis- ligand gold nanoparticle aqueous solutions of 50mmol/L using ICP-MS.
Figure 17 is the fluorescence spectrum control of single ligand that embodiment 2 is prepared and double ligand gold nanoparticle aqueous solutions
Figure.
Detect the method and meter of the rate of single ligand and double ligand gold nanoparticle generation singlet oxygens that embodiment 2 synthesizes
It is identical as the method for case study on implementation 1 to calculate the enhancing efficiency that double ligand gold nanoparticles generate singlet oxygen.
Figure 18 is single ligand that embodiment 2 synthesizes and double ligand gold nanoparticle aqueous solution difference light application time-unreacteds
ABDA accounts for the linear fit comparison diagram of the percentage of initial amount.It was found from Figure 18 fitting a straight line: Dan Peiti gold nanoparticle is water-soluble
Liquid causes ABDA descending slope to be -3.04 with light application time increase, and double ligand gold nanoparticle aqueous solutions increase with light application time
Leading to ABDA descending slope is -8.24, is finally calculated: double ligand gold nanoparticle aqueous solutions generate the rate of singlet oxygen
Compared to single ligand gold nanoparticle aqueous solution, enhancing percentage is (- 8.24- (- 3.04))/(- 3.04)) × 100%=
171%.
Embodiment 3
All glasswares first pass through chloroazotic acid soaking and washing mistake in advance, at room temperature, by 4.8mL mercapto-polyglycol
(concentration 0.05mol/L, mercapto-polyglycol carboxyl molecular weight are 1000) to be added with 14.6mL deionized water to carboxyl aqueous solution
Into the three-necked flask of 50mL specification, 0.6mL aqueous solution of chloraurate is then added under conditions of 95 DEG C of oil baths, magnetic agitations
(concentration 0.1mol/L) continues to stir under the conditions of stirring rate 1500rpm/min later, until with fluorescent/phosphorescent/shine
The fluorescence intensity of spectrophotometer detection reaction system stops reacting at once when reaching most strong, and retention point is used after being cooled to room temperature
The bag filter that son amount is 3kDa is dialysed 3 times in deionized water solution, and room temperature, no less than 6h, obtains glassy yellow list every time
Ligand gold nanoparticle aqueous solution.
For subsequent further operating, gained list ligand gold nanoparticle aqueous solution by the super filter tube of molecular weight 3kDa from
The heart (4000rpm/min) is concentrated into 500 μ L, takes out solution into 1.5mL centrifuge tube, 2100g high speed centrifugation removes bottom later
Then bulky grain quantitatively obtains the mono- ligand gold nanoparticle aqueous solution of 50mmol/L using ICP-MS.
Later in the three-necked flask of 100mL specification, the mono- ligand gold nanoparticle aqueous solution of 0.1mL 50mmol/L is taken to add
Entering into 50mL 0.3mmol/L mercaptoethylmaine aqueous solution and reacts, mercaptoethylmaine is the sulfydryl small molecule compound B,
It stirs at room temperature for 24 hours, solution is still yellow.It is saturating in deionized water solution using the bag filter that molecular cut off is 3kDa later
Analysis 3 times, room temperature, no less than 6h, obtains double ligand gold nanoparticle aqueous solutions every time.
For subsequent further operating, the double ligand gold nanoparticle aqueous solutions of gained by the super filter tube of molecular weight 3kDa from
The heart (4000rpm/min) is concentrated into 500 μ L, takes out solution into 1.5mL centrifuge tube, 2100g high speed centrifugation removes bottom later
Then bulky grain quantitatively obtains the bis- ligand gold nanoparticle aqueous solutions of 50mmol/L using ICP-MS.
Figure 19 is the fluorescence spectrum control of single ligand that embodiment 3 is prepared and double ligand gold nanoparticle aqueous solutions
Figure.
Detect the side of single ligand that case study on implementation 3 synthesizes and double ligand gold nanoparticle aqueous solution generation singlet oxygen rates
Method and the enhancing efficiency for calculating double ligand gold nanoparticles generation singlet oxygens are identical as the method for case study on implementation 1.
Figure 20 is single ligand that embodiment 3 synthesizes and double ligand gold nanoparticle aqueous solution difference light application time-unreacteds
ABDA accounts for the linear fit comparison diagram of the percentage of initial amount.It was found from Figure 20 fitting a straight line: Dan Peiti gold nanoparticle is water-soluble
Liquid causes ABDA descending slope to be -1.54 with light application time increase, and double ligand gold nanoparticle aqueous solutions increase with light application time
Leading to ABDA descending slope is -4.63, is finally calculated: double ligand gold nanoparticle aqueous solutions generate the efficiency of singlet oxygen
Compared to single ligand gold nanoparticle aqueous solution, enhancing percentage is (- 4.63- (- 1.54))/(- 1.54)) × 100%=
200%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of double ligand gold nanoparticle aqueous solutions, which comprises the following steps:
(1) sulfydryl small molecule compound A is added to the water, preparation obtains sulfydryl small molecule compound A aqueous solution；
(2) sulfydryl small molecule compound A aqueous solution is added in solvent, it is water-soluble that gold chloride is added under oil bath and stirring condition
Liquid continues stirring and is reacted, stops reaction when the fluorescence intensity of reaction system, which reaches, not to be further added by by force most, be cooled to room temperature
After be put into bag filter, dialyse in water, after dialysis, obtain single ligand gold nanoparticle aqueous solution；
(3) single ligand gold nanoparticle aqueous solution that step (2) is prepared is added to sulfydryl small molecule compound B aqueous solution
In, it is stirred to react, is put into bag filter after the reaction was completed, dialyse in water, after dialysis, obtain double ligand gold nanos
Particle aqueous solution.
2. the preparation method of double ligand gold nanoparticle aqueous solutions according to claim 1, which is characterized in that step (1) institute
The concentration for stating sulfydryl small molecule compound A aqueous solution is 0.01mol/L~0.20mol/L；
The concentration of step (3) the sulfydryl small molecule compound B aqueous solution is 0.01mmol/L~1mmol/L.
3. the preparation method of double ligand gold nanoparticle aqueous solutions according to claim 2, which is characterized in that step (1) institute
Sulfydryl small molecule compound A is stated with following structure: R-SH, wherein R is nitrogenous or oxygen atom alkyl or heterocycle；
Step (3) the sulfydryl small molecule compound B is one of mercaptoethylmaine, mercaptobenzimidazole and mercaptoimidazole.
4. the preparation method of any one double ligand gold nanoparticle aqueous solutions according to claim 1~3, which is characterized in that
The molar ratio of step (2) the sulfydryl small molecule compound A and gold chloride is 1:1~8:1, and gold chloride is dense eventually in the reaction system
Degree is 1~5mmol/L.
5. the preparation method of any one double ligand gold nanoparticle aqueous solutions according to claim 1~3, which is characterized in that
The molar ratio of step (3) the sulfydryl small molecule compound B and the gold atom in single ligand gold nanoparticle aqueous solution is 0.1:1
~10:1；Gold atom in single ligand gold nanoparticle aqueous solution in the reaction system final concentration of 0.08mmol/L~
20mmol/L。
6. the preparation method of any one double ligand gold nanoparticle aqueous solutions according to claim 1~3, which is characterized in that
The molecular cut off of step (2) and step (3) described bag filter is 3~10kDa；
Step (2) and step (3) described dialysis specifically: dialysis is minimum three times, and each time is no less than 6h.
7. the preparation method of any one double ligand gold nanoparticle aqueous solutions according to claim 1~3, which is characterized in that
Step (1) the sulfydryl small molecule compound A is poly glycol monomethyl ether mercaptan, mercapto-polyglycol amino, the poly- second two of sulfydryl
One of alcohol carboxyl, glutathione, bovine serum albumin and mercaptopropionic acid；
Step (2) solvent is ethyl alcohol, methanol, tetrahydrofuran, one of acetonitrile and water.
8. the preparation method of double ligand gold nanoparticle aqueous solutions according to claim 1, which is characterized in that step (2) institute
The temperature for stating oil bath is 25~95 DEG C；
Step (2) rate for continuing stirring is 1000rpm/min~1500rpm/min；
The time of step (3) described stirring is 10min~48h.
9. double ligands that the preparation method of any one of claim 1~8 double ligand gold nanoparticle aqueous solutions is prepared
Gold nanoparticle aqueous solution.
10. double ligand gold nanoparticle aqueous solutions described in claim 9 are preparing the application in photosensitizer.
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