CN114951677B - Gold nano material assembly with adjustable assembly structure, and preparation method and application thereof - Google Patents

Gold nano material assembly with adjustable assembly structure, and preparation method and application thereof Download PDF

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CN114951677B
CN114951677B CN202210335757.0A CN202210335757A CN114951677B CN 114951677 B CN114951677 B CN 114951677B CN 202210335757 A CN202210335757 A CN 202210335757A CN 114951677 B CN114951677 B CN 114951677B
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刘锦斌
周凯
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South China University of Technology SCUT
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Abstract

The invention discloses a gold nano material assembly with an adjustable assembly structure, and a preparation method and application thereof. The preparation method comprises the following steps: transferring aqueous chloroauric acid into an organic phase, and stirring the chloroauric acid of the organic phase and a sulfhydryl ligand in organic solvent methanol for reaction; adding a reducing agent, and stirring for reaction; removing the organic solvent by rotary evaporation, and transferring to an aqueous phase; self-assembling to obtain the gold nano material assembly with adjustable assembled structure. The invention realizes that the fluorescence emission wavelength is adjustable in a near infrared first region (750-900 nm) and a near infrared second region (1000-1700 nm) through the assembly structure change of the gold nano material. The structural change of the assembly induces the difference of the singlet oxygen generation rate, can be applied to photodynamic therapy, and has the advantages of high efficiency, low toxicity, good biocompatibility and the like. The gold nano material assembly has the advantages of simple preparation method, low cost, easy industrial production and good application prospect in the fields of tumor photodynamic therapy and the like.

Description

Gold nano material assembly with adjustable assembly structure, and preparation method and application thereof
Technical Field
The invention belongs to the field of functional optical nano materials, and particularly relates to a gold nano material assembly with an adjustable assembly structure, and a preparation method and application thereof.
Background
With the increasing incidence and mortality of tumor-related diseases worldwide, the development of effective tumor imaging and therapeutic agents is urgent. The gold nanoparticles modified by the sulfhydryl ligand can be used as a very important nanoscale optical material, and can simultaneously have tumor imaging and tumor treatment capabilities.
The gold nano particles have the advantages of good biocompatibility, stable optical property, easy functional modification and the like, and are widely applied to the research fields of fluorescence imaging, disease treatment, biosensing and the like. Compared with the defects of high radiation dosage, low resolution, poor sensitivity and the like of Computer Tomography (CT), positron Emission Tomography (PET) and Magnetic Resonance Imaging (MRI), the gold nanoparticle fluorescence imaging has the advantages of high resolution, high sensitivity, simple operation, rapid feedback and the likeThe method has been widely applied to the research fields of life science, biomedicine and the like. In particular, the fluorescence wavelength of the near infrared two region (NIR-II, 1000-1700 nm) is longer, the photon absorption level and photon flash are lower, so that the space-time resolution and the penetration depth of the fluorescence of the near infrared two region are further obviously enhanced compared with those of the near infrared one region (NIR-I, 750-900 nm), and the fluorescence imaging effect is better. Therefore, the design and control of the fluorescence emission wavelength of the gold nanoparticles has practical application value. Meanwhile, the luminous gold nano-particles can be used as an important nano-scale photosensitizer to generate singlet oxygen 1 O 2 Is applied to photodynamic therapy. Currently used for photodynamic therapy 1 O 2 The organic light-sensitive agent is mainly produced by the traditional organic micromolecular light-sensitive agent, but the traditional organic micromolecular light-sensitive agent has more defects, has the defects of poor water solubility, complex synthesis process, easy enzyme degradation, large toxic and side effects and the like, and greatly limits the transformation of clinical application. Thus research and control of gold nanoparticle production 1 O 2 The performance method has good scientific research and clinical application value.
According to the report of jianing Xie et al, aggregation of gold nanoparticles in an organic phase was achieved such that the luminescence wavelength was gradually red shifted from 820nm to 987nm, but this aggregation process occurred in the organic phase and was subsequently not applicable in vivo. And the red shift amplitude of the luminescence wavelength after the aggregation of the gold nanoparticles is not large enough and does not reach a near infrared two-region (1000-1700 nm) (Wu Z, yao Q, chai O J H, et al Unlaveling the impact of gold (I) -thiolate motifs on the aggregation-induced emission of gold nanoclusters [ J)]Angewandte Chemie,2020,132 (25): 10020-10025.). Therefore, by assembling gold nanoparticles in water and regulating and controlling the assembly structure of the gold nanoparticles, the fluorescence emission wavelength of the gold nanoparticle assembly moves between a near infrared first region and a near infrared second region, and simultaneously, the gold nanoparticle assembly can be regulated and controlled 1 O 2 The purpose of generating the rate has very important scientific research and clinical application values.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention provides a preparation method of an assembled gold nano material assembly with an adjustable assembled structure and a method for adjusting fluorescence emission wavelength and singlet oxygen generation rate. The maximum emission wavelength of the gold nano material provided by the invention is in a near infrared first region before assembly, and the maximum emission wavelength after assembly can move between the near infrared first region and a near infrared second region along with the change of an assembly structure. And the rate of generating singlet oxygen by the gold nano material assembly varies with the change of the assembly structure. Under the condition of certain structure assembly, the assembly prepared by the method can efficiently generate high-activity singlet oxygen under the condition of illumination to carry out photodynamic therapy. Therefore, the gold nano material assembly with adjustable assembled structure prepared by the invention has a great application prospect in the field of clinical tumor treatment.
The aim of the invention is achieved by the following technical scheme:
a preparation method of a gold nano material assembly with an adjustable assembly structure comprises the following steps:
(1) Adding the silane mercapto ligand A into an organic phase to prepare a solution of the silane mercapto ligand A;
(2) Adding another sulfhydryl ligand B into the organic phase to prepare a sulfhydryl ligand B solution;
(3) Transferring chloroauric acid from the aqueous phase to the organic phase with a phase transfer agent;
(4) Stirring chloroauric acid to react with a solution of silane mercapto ligand A and a solution of another mercapto ligand B;
(5) Adding a reducing agent, and stirring for reaction;
(6) Transferring the reactant from the organic phase to the water phase, self-assembling the gold nano material in the water phase, and then filtering, ultrafiltering and purifying to obtain the gold nano material assembly with adjustable assembled structure.
Preferably, the silane mercapto ligand A in the step (1) is more than one of 3-mercaptopropyl trimethoxysilane and 3-mercaptopropyl triethoxysilane.
Preferably, the molar concentration of the solution of the silane mercapto ligand A in the step (1) is 0.01mol/L to 0.10mol/L.
Preferably, the other sulfhydryl ligand B in the step (2) is more than one of sulfhydryl polyethylene glycol amino, polyethylene glycol monomethyl ether mercaptan and sulfhydryl polyethylene glycol carboxyl.
Preferably, the molar concentration of the solution of the mercapto ligand B in the step (2) is 0.01mol/L to 0.10mol/L.
Preferably, the phase transfer agent in the step (3) is tetraoctylammonium bromide, and the ratio of the amount of the phase transfer agent to the amount of the chloroauric acid is 1.05:1-1.2:1.
Preferably, the phase transfer time in step (3) is 15-60min.
Preferably, the ratio of the amount of chloroauric acid to the total thiol ligand (R-SH) material of step (4) is 1:3-1:7; the total mercapto ligand is the sum of silane mercapto ligand A and another mercapto ligand B; the ratio of the amounts of the substances of the silane mercapto ligand A and of the other mercapto ligand B is from 1:3 to 3:1.
Preferably, the temperature of the stirring reaction in the step (4) is room temperature, the stirring speed is 100-1500rpm, and the stirring time is 10-60min.
Preferably, the reducing agent in the step (5) is more than one of tetrabutylammonium borohydride, sodium borohydride, dimethylamine borane and tetrakis (hydroxymethyl) phosphonium chloride.
Preferably, the ratio of the chloroauric acid of step (4) to the reducing agent of step (5) is 1:6-1:9.
Preferably, the stirring reaction temperature in the step (5) is 20-50 ℃, and the stirring reaction time is 8-24h.
Preferably, in the step (6), the reactant is transferred from the organic phase to the water phase, the organic matters are removed by rotary evaporation, the rotary evaporation temperature is 10-50 ℃, the rotary evaporation time is 5-15min, and the volume of added water is 1-5 times of the volume of the original reaction liquid.
Preferably, the purification in the step (6) is to filter the assembled solution to remove large-size assemblies and solid particles with poor water solubility, and then ultrafilter and centrifuge the solution by using an ultrafiltration tube to remove unreacted substrate and concentrate the solution.
Preferably, the organic phase in step (1) to step (6) is methanol.
Further preferably, the filtration of step (6) is filtration using a 0.22 μm disposable needle filter; the ultrafiltration centrifugation temperature is 4-20 ℃, the ultrafiltration centrifugation rotating speed is 2000-4000rpm, and the ultrafiltration centrifugation time is 10-30min; the pore size of the membrane of the ultrafiltration tube is 3-50kDa.
The gold nano material assembly with adjustable assembled structure prepared by the preparation method is a monodisperse nano particle with the particle size of 0.5-3nm when the gold nano material is not assembled in an organic phase; the gold nano material is a spherical assembly body after being assembled in water, and the particle size is 30-110nm.
The gold nanomaterial assembly with adjustable assembled structure prepared by the preparation method has the maximum fluorescence emission wavelength of 800nm when the gold nanomaterial is not assembled; after the gold nano material is assembled to form a spherical assembly, the maximum fluorescence emission wavelength of the gold nano material moves between 800nm and 1100nm along with the change of an assembly structure.
The invention also provides application of the gold nano material assembly with the adjustable assembly structure in preparation of a photosensitizer. The gold nano material assembly with adjustable assembled structure is used for generating singlet oxygen, and the structural change of the assembly induces the change of the generation rate of the singlet oxygen.
The method for producing singlet oxygen by using the gold nano material assembly with adjustable assembled structure comprises the following steps:
and uniformly mixing the gold nano material assembly with an adjustable assembly structure with the singlet oxygen specific detection agent ABDA, carrying out laser illumination, and testing the ABDA absorption spectrum of the mixed solution along with the illumination time by using an ultraviolet-visible light spectrometer.
Preferably, the concentration of the gold nano material assembly with the adjustable assembly structure is 0.01-1uM, the laser illumination wavelength is 450-808nm, the illumination time is 15-60min, and the laser power is 50-500mW/cm 2 。
Compared with the prior art, the invention has the following advantages and effects:
(1) The gold nano material assembly with adjustable assembled structure prepared by the method has the advantages of simple synthesis method, easy operation, high yield and easy industrial production;
(2) The gold nanomaterial assembly with adjustable assembly structure prepared by the method has wide emission wavelength range, realizes that fluorescence emission wavelength is adjustable in a near infrared first region (750-900 nm) and a near infrared second region (1000-1700 nm) through the assembly structure change of the gold nanomaterial, and has wide application field;
(3) The gold nano material assembly with adjustable assembled structure prepared by the method has good biocompatibility and low toxicity;
(4) The gold nano material assembly with adjustable assembled structure prepared by the method has the potential of clinical application of photodynamic therapy by inducing the difference of singlet oxygen generation rate through the structural change of the assembly. The singlet oxygen has high generation efficiency, so that the singlet oxygen has good application prospect in the fields of tumor photodynamic therapy and the like.
Drawings
FIG. 1 is an absorption spectrum of gold nanoparticles prepared in example 1 when not assembled.
FIG. 2 is a normalized excitation and emission spectrum of the gold nanoparticles prepared in example 1 when not assembled.
FIG. 3 is a transmission electron microscope image of the gold nanoparticles prepared in example 1 when not assembled.
FIG. 4 is a graph showing the particle diameter statistics of the gold nanoparticles prepared in example 1 when not assembled.
Fig. 5 is an absorption spectrum of the assembled gold nanomaterial assembly with adjustable assembled structure prepared in example 2.
FIG. 6 shows normalized excitation and emission spectra of an assembled gold nanomaterial with adjustable assembled structure prepared in example 2.
Fig. 7 is a transmission electron microscope image of an assembly process of gold nanomaterial with adjustable assembly structure prepared in example 2.
FIG. 8 is an emission spectrum of gold nanoparticles prepared in example 3 after assembly.
FIG. 9 is an emission spectrum of gold nanoparticles prepared in example 4 after assembly.
FIG. 10 is an emission spectrum of gold nanoparticles prepared in example 5 after assembly.
FIG. 11 is a graph showing the emission spectrum of gold nanoparticles prepared in example 6 during the assembly process in a water/methanol mixture.
Fig. 12 is a transmission electron microscope image of the gold nanoparticle assembly prepared in example 7 assembled for different times at ph=4, with the scale bars being 500nm.
Fig. 13 is a transmission electron microscope image of assembly time of 1h and 72h of the gold nanoparticle assembly prepared in example 7 at ph=4.
Fig. 14 is a statistical graph of particle diameters of transmission electron microscopes for assembling the gold nanoparticle assemblies prepared in example 7 at ph=4 for different times.
Fig. 15 is a graph showing statistical trend of particle diameters of gold nanoparticle assemblies prepared in example 7 assembled for different times at ph=4.
Fig. 16 is a graph showing the trend of the hydrated particle size change of the gold nanoparticle assembly prepared in example 7 assembled for different times at ph=4.
Fig. 17 is an ultraviolet-visible light absorption spectrum of the gold nanoparticle assembly prepared in example 7 assembled for different times at ph=4.
Fig. 18 is an emission spectrum of the gold nanoparticle assembly prepared in example 7 assembled for various times at ph=4.
Fig. 19 is an X-ray photoelectron spectrum of the gold nanoparticle assembly prepared in example 8 when assembled for 1 hour at ph=4.
Fig. 20 is an X-ray photoelectron spectrum of the gold nanoparticle assembly prepared in example 8 assembled for 72 hours at ph=4.
Figure 21 is a schematic view of a light source in a light condition, 1 O 2 the mixed solution of ABDA and the DPBS buffer solution of the blank control group is placed for different times in the generation process to obtain ultraviolet-visible absorption spectrograms.
Figure 22 is a schematic view of a light source in a light condition, 1 O 2 ultraviolet-visible absorption spectra of the mixed solution of ABDA and the assembly prepared in example 7 (ph=4 assembled for 1 h) were taken for different times during the production.
Figure 23 is a schematic diagram showing a schematic diagram of a light source, 1 O 2 ultraviolet-visible absorption spectra of the mixed solution of ABDA and the assembly prepared in example 7 (ph=4 assembly for 18 h) were taken for different times during the production.
Figure 24 is a schematic view of a light source in a light condition, 1 O 2 ultraviolet-visible absorption spectra of the mixed solution of ABDA and the assembly prepared in example 7 (ph=4 assembly for 72 h) were set for different times during the production.
FIG. 25 is a graph showing a comparison of the fit of the assembly of gold nanoparticles of example 9 at various times of assembly versus the percentage of unreacted ABDA to the initial amount at various times of illumination.
FIG. 26 is a schematic diagram of luminescence of an assembled gold nanomaterial with an adjustable assembled structure prepared by the present invention.
Detailed Description
The technical scheme of the present invention is described in further detail below with reference to specific examples and drawings, but the scope and embodiments of the present invention are not limited thereto.
In the following examples, chloroauric acid was purchased from Shanghai Michel chemical technologies Inc., silane sulfhydryl ligand A was purchased from Sigma Aldrich (Shanghai) trade Inc., and another sulfhydryl ligand B was purchased from Beijing Hua Weirui chemical Co. The detection instrument for observing the material property of the gold nano material assembly with the adjustable assembly structure and the singlet oxygen thereof mainly comprises a Simer flight transmission electron microscope Talos F200X, a Markov laser particle sizer ULTRA, a Perkin Elmer fluorescence/phosphorescence/luminescence spectrophotometer LS-55 in the U.S., a Chrosos DFD transient spectrometer ISS in the U.S., a Shimadzu ultraviolet-visible absorption spectrometer UV-2600 and the like.
FIG. 26 is a schematic diagram of luminescence of an assembled gold nanomaterial with an adjustable assembled structure prepared by the present invention. The principle of the emission wavelength change of the assembly is as follows: the hydrolysis of the silane mercapto ligand A on the surface of the gold nanoparticles leads to the formation of Si-O-Si cross-links between adjacent gold nanoparticles, so that the gold nanoparticles are aggregated from a monodisperse state to form a spherical assembly. This aggregation state may cause the Au (I) -SR complex length on the surface of the gold nanoparticle to be compressed, thereby shortening the Au (I) -Au inside the gold nanoparticle and between the gold nanoparticles(I) The distance of interaction, thereby resulting in a red shift of the maximum emission wavelength of the assembly from the near infrared first region to the near infrared second region. Thus changing how tightly the assemblies are assembled directly affects the magnitude of the red shift of the assemblies. As can be seen from the figures: when the assembly body is changed from a tightly packed aggregation state to a loosely packed aggregation state, 1 O 2 generating a rate rise, the emitted light being in the near infrared region; as the assembled structure changes, when the assembled body changes from loose aggregation state to tight aggregation state, 1 O 2 the rate of production decreases and the emitted light is converted into light in the near infrared region. The invention is illustrated that the fluorescence can realize the adjustable emission wavelength in the near infrared first region (750-900 nm) and the near infrared second region (1000-1700 nm) through the change of the assembly structure of the gold nano material.
Example 1
The preparation method for assembling the precursor gold nanoparticle by the gold nanomaterial assembly with adjustable assembled structure comprises the following steps:
565uL of 20mM chloroauric acid was added to a reaction flask containing 12.9mL of methanol at room temperature, and after stirring and mixing 565uL of 50mM 3-mercaptopropyl trimethoxysilane solution (the solvent was methanol) and 565uL of 50mM polyethylene glycol monomethyl ether thiol solution (the solvent was methanol), stirring was carried out at 1000rpm for 30 minutes at room temperature, when the solution turned from yellow to colorless and transparent, 400uL of sodium borohydride solution (dissolved in methanol, 7eq relative to chloroauric acid) was added, and immediately the solution turned to brown yellow, and stirring was carried out at 20℃for 12 hours until the reaction was completed.
FIG. 1 is an absorption spectrum of gold nanoparticles prepared in example 1 when not assembled. From the figures it can be derived that: the gold nano particles have characteristic absorption at 400nm, 450nm and 660nm, and the positions of the gold nano particles are consistent with the positions of the absorption peaks of Au25 nanoclusters reported in the literature.
FIG. 2 is a graph showing normalized excitation and emission spectra of gold nanoparticles prepared in example 1 when the gold nanoparticles were not assembled. From the figures it can be derived that: the maximum emission wavelength of the gold nanoparticle is 800nm, and the excitation wavelength is 335nm.
FIG. 3 is a transmission electron microscope image of the gold nanoparticles prepared in example 1 when not assembled. As can be seen from the figures: gold nanoparticles are monodisperse particles, and are counted by particle size analysis software (Nano measurer 1.2.5), as shown in FIG. 4, and the particle size is 0.6-1.8 nm.
Example 2
The preparation steps of the gold nano material assembly with adjustable assembly structure are as follows:
the gold nanoparticles before assembly were prepared according to the procedure of example 1, after the reaction in the organic solvent was completed, the reaction stock solution was transferred to a round bottom flask, and the organic solvent was removed by spin-steaming at 20 ℃ for 10min. 30mL of water was added, the reaction was transferred from the organic phase to the aqueous phase, and the gold nanomaterial self-assembled in the aqueous phase. Then filtering with a disposable needle filter with 0.22um, ultrafiltering with a 10kDa ultrafilter tube at 3750rpm for 10min, removing unreacted substrate, and purifying to obtain gold nanomaterial assembly with adjustable assembled structure.
FIG. 5 is an absorption spectrum of the gold nanomaterial assembly prepared in example 2. It can be seen from the figure that the absorption of the gold nanoparticles after assembly is consistent with the absorption before assembly, which indicates that the structure of the gold nanoparticles is not changed during the assembly process.
FIG. 6 is a normalized excitation and emission spectrum of the gold nanomaterial assembly prepared in example 2. From the figures it can be derived that: the gold nanoparticles have a maximum emission wavelength of 1070nm and excitation wavelength of 465nm. The maximum emission wavelength after assembly is red shifted by 270nm from the near infrared first region to the near infrared second region.
FIG. 7 is a transmission electron microscope image of the gold nanomaterial assembly prepared in example 2. As can be seen from the figures: the gold nano particles are assembled together, and the particle size is 100nm.
Example 3
The preparation process of the gold nano material assembly with adjustable assembly structure adopts the preparation steps of different ratios of chloroauric acid and ligand total mercapto ligand as follows:
565uL of 20mM chloroauric acid was added to a reaction flask containing 12.9mL of methanol at room temperature, and after stirring and mixing, 3 equivalents, 5 equivalents, and 7 equivalents of total thiol amount of ligand were added, respectively:
(1) 339uL of 50mM 3-mercaptopropyl trimethoxysilane solution (methanol as solvent) and 339uL of 50mM polyethylene glycol monomethyl ether mercaptan solution (methanol as solvent) (1:3);
(2) 565uL of a 50mM solution of 3-mercaptopropyl trimethoxysilane (methanol as solvent) and 565uL of a 50mM solution of polyethylene glycol monomethyl ether mercaptan (methanol as solvent) (1:5);
(3) 791uL of a 50mM solution of 3-mercaptopropyl trimethoxysilane (methanol as solvent) and 791uL of a 50mM solution of polyethylene glycol monomethyl ether mercaptan (methanol as solvent) (1:7);
when the solution turns from yellow to colorless and transparent, 400uL of sodium borohydride solution (dissolved in methanol, 7 equivalents relative to chloroauric acid) was added and the solution immediately turned brown yellow, stirring at 20 ℃ for 12h to complete the reaction.
FIG. 8 is an emission spectrum of gold nanoparticles prepared in example 3 after assembly. From the figures it can be derived that: when the ratio of chloroauric acid to total sulfhydryl ligand is 1:5, the fluorescence emission intensity value of the gold nanoparticle assembly is the largest, and the optimal ratio is 1:5.
Example 4
The preparation process of the gold nano material assembly with the adjustable assembly structure adopts the preparation steps of different ratios of 3-mercaptopropyl trimethoxy silane to polyethylene glycol monomethyl ether mercaptan as follows:
565uL of 20mM chloroauric acid is added into a reaction bottle containing 12.9mL of methanol at room temperature, and 3-mercaptopropyl trimethoxysilane and polyethylene glycol monomethyl ether mercaptan with different proportions are added after stirring and mixing:
(1) 847.5uL of 50mM 3-mercaptopropyl trimethoxysilane solution (methanol as solvent) and 282.5uL of 50mM polyethylene glycol monomethyl ether mercaptan solution (methanol as solvent) (3:1);
(2) 565uL of 50mM 3-mercaptopropyl trimethoxysilane solution (methanol as solvent) and 565uL of 50mM polyethylene glycol monomethyl ether mercaptan solution (methanol as solvent) (1:1);
(3) 282.5uL of a 50mM solution of 3-mercaptopropyl trimethoxysilane (methanol as solvent) and 847.5uL of a 50mM solution of polyethylene glycol monomethyl ether mercaptan (methanol as solvent) (1:3);
when the solution turns from yellow to colorless and transparent, 400uL of sodium borohydride solution (dissolved in methanol, 7 equivalents relative to chloroauric acid) was added and the solution immediately turned brown yellow, stirring at 20 ℃ for 12h to complete the reaction.
FIG. 9 is an emission spectrum of gold nanoparticles prepared in example 4 after assembly. From the figures it can be derived that: when the ratio of the 3-mercaptopropyl trimethoxy silane to the polyethylene glycol monomethyl ether mercaptan is 1:1, the fluorescence emission intensity value of the gold nanoparticle assembly is the largest, and the optimal ratio is 1:1.
Example 5
The preparation process of the gold nano material assembly with the adjustable assembly structure adopts the preparation steps of different ratios of chloroauric acid to sodium borohydride as follows:
565uL of 20mM chloroauric acid was added to a reaction flask containing 12.9mL of methanol at room temperature, and after stirring and mixing, 565uL of 50mM 3-mercaptopropyl trimethoxysilane solution (solvent: methanol) and 565uL of 50mM polyethylene glycol monomethyl ether mercaptan solution (solvent: methanol) were added, and stirring was carried out at 1000rpm for 30 minutes at room temperature, and when the solution turned from yellow to colorless and transparent, 343uL, 400uL, 457uL, 514uL of sodium borohydride solution (dissolved in methanol) were added in a molar ratio of chloroauric acid to sodium borohydride of 1:6, 1:7, 1:8, 1:9, respectively, and the solution was immediately changed to brown yellow at 20℃until the reaction was completed.
FIG. 10 is an emission spectrum of gold nanoparticles prepared in example 5 after assembly. From the figures it can be derived that: when the ratio of chloroauric acid to sodium borohydride is 1:7, the fluorescence emission intensity value of the gold nanoparticle assembly is the largest, and the optimal ratio is 1:7.
Example 6
The gold nanoparticles before assembly were prepared according to the procedure of example 1, after the reaction in the organic solvent was completed, the reaction stock solution was transferred to a round bottom flask, and the organic solvent was removed by spin-steaming at 20 ℃ for 10min. To slow the assembly rate, the assembly was performed in a water/methanol mixture. 30mL of a water/methanol mixture (water/methanol=9:1, v/v) was added, and the gold nanomaterial self-assembled in the mixed phase and then filtered with a 0.22um disposable needle filter. The change in fluorescence over time during assembly was monitored with a transient spectrometer ISS.
FIG. 11 is a graph showing the emission spectrum of gold nanoparticles prepared in example 6 during the assembly process in a water/methanol mixture. From the figures it can be derived that: as the assembly proceeds, the fluorescence maximum emission wavelength of the assembly is gradually red shifted from the near infrared first region to the near infrared second region.
Example 7
The assembly steps of the gold nano material assembly with adjustable assembly structure are as follows:
in this example, gold nanoparticles before assembly were prepared according to the procedure of example 1, and after the reaction in an organic solvent was completed, the reaction stock solution was transferred to a round-bottomed flask, and the organic solvent was removed by spin-steaming at 20 ℃ for 10min. 30mL of water was added, the reaction was transferred from the organic phase to the aqueous phase, and the gold nanomaterial self-assembled in the aqueous phase. Then filtered through a 0.22um disposable needle filter. After the filtration was completed, 8uL of 1M hydrochloric acid solution was added, the aqueous solution was adjusted to ph=4, and the assembly process was monitored with transient spectrometers ISS, uv-vis absorption spectrometers, transmission electron microscopy, malvern laser particle sizer at different time points (1 h, 3h, 6h, 18h, 48h, 72 h).
Fig. 12 is a transmission electron microscope image of the gold nanoparticle assembly prepared in example 7 assembled at ph=4 for various times. From the figures it can be derived that: under acidic conditions, as the assembly proceeds, the particle size of the assembly becomes smaller and the degree of tightness of the assembly becomes looser from tight. As shown in fig. 14 and 15, the particle size of the gold nanoparticle assembly gradually decreased from-102.98 nm for assembly 1h to-34.98 nm for assembly 72h at ph=4, as determined by particle size analysis.
Fig. 13 is a transmission electron microscope image of assembly time of 1h and 72h of the gold nanoparticle assembly prepared in example 7 at ph=4. Because in acidic media, the protonated silanol preferentially condenses with the least acidic silanol end-groups, silanes tend to be less branched and more linear polymeric assembled; on the other hand, under neutral or basic conditions, deprotonated silanol attacks more acidic silanol groups, forming branches and polymerizing a tighter package. Thus, by adjusting the assembly time in the ph=4 assembly environment, gold nanoparticles can be induced to assemble into assemblies of different aggregation degrees. From the figures it can be derived that: when assembled for 1h at ph=4, the assembly assumes a tightly aggregated state; when assembled for 72h at ph=4, the assembly assumed a loose aggregation state.
Fig. 16 is a graph showing the trend of the hydrated particle size change of the gold nanoparticle assembly prepared in example 7 assembled for different times at ph=4. From the figures it can be derived that: under acidic conditions, the assembly particle size becomes smaller as the assembly proceeds, and at ph=4, the hydration particle size decreases from-128 nm for assembly 1h to-70 nm for assembly 72 h.
Fig. 17 is an ultraviolet-visible light absorption spectrum of the gold nanoparticle assembly prepared in example 7 assembled for different times at ph=4. From the figures it can be derived that: at ph=4, as the assembly proceeds, the absorption value of the assembly decreases, consistent with the trend of the particle size change of the assembly.
Fig. 18 is an emission spectrum graph (near infrared two-zone detector test) of the gold nanoparticle assembly prepared in example 7 assembled at ph=4 for different times. The test instrument is a Chronos DFD transient spectrometer ISS, and the detection wavelength is 900-1700nm. From the figures it can be derived that: under an acidic condition, as the assembly proceeds, the maximum fluorescence emission wavelength of the assembly gradually shifts from the near infrared second region (1055 nm) to the near infrared first region (800 nm), and by combining fig. 12, 13 and 16, it can be presumed that the fluorescence emission wavelength shifts to the near infrared second region in red when the assembly presents a tightly aggregated situation; when the assembly is in a loose aggregation state, the fluorescence emission wavelength is blue shifted to the near infrared region, and the fluorescence intensity is enhanced.
Example 8
The gold nanoparticles before assembly were prepared according to the procedure of example 1, after the reaction in the organic solvent was completed, the reaction stock solution was transferred to a round bottom flask, and the organic solvent was removed by spin-steaming at 20 ℃ for 10min. 30mL of water was added, the reaction was transferred from the organic phase to the aqueous phase, and the gold nanomaterial self-assembled in the aqueous phase. Then filtered through a 0.22um disposable needle filter. After the filtration is completed, adding 8uL of 1M hydrochloric acid solution, adjusting the pH value of the aqueous solution to be=4, respectively assembling for 1h and 72h, ultrafiltering and centrifuging to concentrate a sample, wherein the ultrafiltering and centrifuging temperature is 20 ℃, the ultrafiltering and centrifuging speed is 3750rpm, and the ultrafiltering and centrifuging time is 10min; the membrane pore size of the ultrafiltration tube was 10kDa. The concentrated samples were dropped drop by drop on tinfoil, dried, and the assembly was analyzed for Au (I) and Au (0) content at different assembly times using X-ray photoelectron spectroscopy (XPS) using Thermo Scientific K-alpha+.
Fig. 19 is an X-ray photoelectron spectrum of the gold nanoparticle assembly prepared in example 8 when assembled for 1 hour at ph=4. From the figures it can be derived that: when the assembly was assembled at ph=4 for 1 hour, the content of Au (I) was 39.35%, and the content of Au (0) was 60.65%.
Fig. 20 is an X-ray photoelectron spectrum of the gold nanoparticle assembly prepared in example 8 assembled for 72 hours at ph=4. From the figures it can be derived that: when the assembly was assembled at ph=4 for 72 hours, the content of Au (I) was 39.11%, and the content of Au (0) was 60.89%. As can be seen from a comparison of FIG. 19, the contents of Au (I) and Au (0) were substantially unchanged when assembling for 1h and 72 h.
Example 9
To detect the rate at which the above-described synthetic aqueous solution of single ligand gold nanoparticles generates singlet oxygen, a singlet oxygen-specific detection reagent was used: the ultraviolet-visible light absorption spectrum of 9, 10-anthracenediyl-bis (methylene) malonic acid (ABDA for short, > 99%) has four characteristic absorption peaks 348 nm, 356 nm,378nm and 400nm, and the detection principle is as follows: once singlet oxygen is generated in the solution, the ABDA immediately captures the singlet oxygen in the solution, and reacts to generate an endogenous oxidation product, so that four characteristic absorption peaks of the ABDA are reduced, and the reaction formula is as follows:
Figure BDA0003576673840000101
wherein the rate of decrease of the ABDA absorption peak corresponds to the rate of singlet oxygen production. And testing the change of the ultraviolet-visible light absorption spectrum of the sample to be tested and the ABDA mixed solution under different illumination time by an ultraviolet-visible spectrophotometer to obtain the rate of generating singlet oxygen.
The step of detecting the singlet oxygen rate generated by the gold nanoparticle assembly is as follows:
using an ultraviolet-visible absorption spectrometer, preheating the instrument for 15min, respectively adding 400 mu L of 50nM gold nanoparticle assembly samples (assembled for 1h, 18h and 72h under the condition of pH=4) into two 700 mu L cuvettes, taking one as a sample cell and the other as a reference cell, firstly sweeping a baseline (300-600 nM), then sweeping a blank to ensure that the absorption value of the blank at 300-600 nM is within +/-0.0005, indicating that the sample cell is clean, then adding 5 mu L of 7.3mmol/L ABDA solution prepared by DMSO, uniformly mixing, testing the absorption spectrum, marking as illumination for 0min, and then using a laser (450 nM,100mW/cm 2 ) And (3) illuminating the mixed solution of the gold nanoparticle assembly and the ABDA, and measuring an absorption spectrum once every 10min of illumination, wherein the illumination time lasts for 30min. Under the same conditions, the above procedure was repeated as a blank by replacing 400 μl of the above 400 μl of 50nM assembly sample with 400 μl of DPBS buffer (ph=7.4).
Figure 21 is a schematic view of a light source in a light condition, 1 O 2 the mixed solution of ABDA and the DPBS buffer solution of the blank control group is placed for different times in the generation process to obtain ultraviolet-visible absorption spectrograms. From the figures it can be derived that: and (3) overlapping the light irradiation lines for 10min, 20min and 30min with the light irradiation lines for 0min, which shows that the ABDA solution without the assembly is stable under the light irradiation condition.
Figure 22 is a schematic view of a light source in a light condition, 1 O 2 ultraviolet-visible absorption spectra of the mixed solution of ABDA and the assembly prepared in example 7 (ph=4 assembled for 1 h) were taken for different times during the production. From the figures it can be derived that: the absorption intensity of ABDA at 378nm gradually decreases after illumination for 10min, 20min and 30min, and 46% decrease after illumination for 30min, which indicates that assembly for 1h under the condition of pH=4 under illumination produces 1 O 2 。
Figure 23 is a schematic diagram showing a schematic diagram of a light source, 1 O 2 production of ABDA from example 7The resulting mixed solution of the assembly (ph=4 assembly 18 h) was left for various times of uv-vis absorption spectrum.
From the figures it can be derived that: the absorbance of ABDA at 378nm gradually decreases for 10min, 20min, and 30min, and 70% after 30min, indicating that 18h assembly under pH=4 under illumination resulted in 1 O 2 。
Figure 24 is a schematic view of a light source in a light condition, 1 O 2 ultraviolet-visible absorption spectra of the mixed solution of ABDA and the assembly prepared in example 7 (ph=4 assembly for 72 h) were set for different times during the production. From the figures it can be derived that: the absorbance of ABDA at 378nm gradually decreases for 10min, 20min, and 30min, and 87% after 30min, indicating that assembly for 72h under pH=4 under illumination resulted in an assembly 1 O 2 。
FIG. 25 is a graph showing a comparison of the fit of the assembly of gold nanoparticles of example 9 at various times of assembly versus the percentage of unreacted ABDA to the initial amount at various times of illumination. As can be seen from fig. 25: the increase of the gold nanoparticle assembly assembled for 1h under the condition of pH=4 with the light time resulted in the decrease of the ABDA amount of-1.53, the increase of the gold nanoparticle assembly assembled for 18h under the condition of pH=4 with the light time resulted in the decrease of the ABDA amount of-2.33, the increase of the gold nanoparticle assembly assembled for 72h under the condition of pH=4 with the light time resulted in the decrease of the ABDA amount of-2.90, the rate of singlet oxygen generation of the gold nanoparticle assembly assembled for 72h under the condition of pH=4 was compared with the gold nanoparticle assembly assembled for 1h under the condition of pH=4, and the enhancement percentage thereof was (-2.90) - (-1.53)/(-1.53) ×100% = 90%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the gold nano material assembly with the adjustable assembly structure is characterized by comprising the following steps of:
(1) Adding the silane mercapto ligand A into an organic phase to prepare a solution of the silane mercapto ligand A;
(2) Adding another sulfhydryl ligand B into the organic phase to prepare a sulfhydryl ligand B solution;
(3) Transferring chloroauric acid from the aqueous phase to the organic phase with a phase transfer agent;
(4) Stirring chloroauric acid to react with a solution of silane mercapto ligand A and a solution of another mercapto ligand B;
(5) Adding a reducing agent, and stirring for reaction;
(6) Transferring reactants from an organic phase to a water phase, self-assembling the gold nano material in the water phase, and then filtering, ultrafiltering and purifying to obtain a gold nano material assembly with an adjustable assembled structure;
the silane mercapto ligand A in the step (1) is more than one of 3-mercaptopropyl trimethoxy silane and 3-mercaptopropyl triethoxy silane;
the other sulfhydryl ligand B in the step (2) is more than one of polyethylene glycol monomethyl ether mercaptan, sulfhydryl polyethylene glycol carboxyl and sulfhydryl polyethylene glycol amino;
the mass ratio of chloroauric acid to the total mercapto ligand in the step (4) is 1:3-1:7; the total mercapto ligand is the sum of silane mercapto ligand A and another mercapto ligand B; the ratio of the amounts of the substances of the silane mercapto ligand A and of the other mercapto ligand B is from 1:3 to 3:1.
2. The method for preparing an assembled gold nanomaterial assembly with adjustable assembled structure according to claim 1, wherein the molar concentration of the solution of the silane mercapto ligand a in the step (1) is 0.01mol/L to 0.10mol/L; the molar concentration of the solution of the sulfhydryl ligand B in the step (2) is 0.01mol/L-0.10mol/L; the phase transfer agent in the step (3) is tetraoctyl ammonium bromide; the reducing agent in the step (5) is more than one of sodium borohydride, dimethylamine borane, tetrabutylammonium borohydride and tetrakis (hydroxymethyl) phosphonium chloride; the organic phase in the steps (1) to (6) is methanol.
3. The method for preparing an assembled gold nanomaterial assembly with adjustable assembled structure according to claim 1, wherein the ratio of the amount of the phase transfer agent to the amount of chloroauric acid in the step (3) is 1.05:1-1.2:1; the ratio of the chloroauric acid in the step (4) to the reducing agent in the step (5) is 1:6-1:9.
4. The method for preparing the gold nanomaterial assembly with the adjustable assembled structure according to claim 1, wherein the temperature of the stirring reaction in the step (4) is room temperature, the stirring rotation speed is 100-1500rpm, and the stirring time is 10-60min; the temperature of the stirring reaction in the step (5) is 20-50 ℃, and the stirring reaction time is 8-24 hours; and (3) transferring the reactant from the organic phase to the water phase, removing the organic matters by rotary evaporation, wherein the rotary evaporation temperature is 10-50 ℃, the rotary evaporation time is 5-15min, and the volume of added water is 1-5 times of the volume of the original reaction liquid.
5. The method of preparing an assembly of gold nanomaterial with adjustable assembled structure according to claim 1, wherein the filtering in step (6) is performed by using a disposable needle filter of 0.22 μm; the ultrafiltration purification step (6) is to filter the assembled solution to remove oversized assemblies and solid particles with poor water solubility, and then to remove unreacted substrates by ultrafiltration tube ultrafiltration centrifugation and concentrate; the ultrafiltration centrifugation temperature is 4-20 ℃, the ultrafiltration centrifugation rotating speed is 2000-4000rpm, and the ultrafiltration centrifugation time is 10-30min; the pore size of the membrane of the ultrafiltration tube is 3-50kDa.
6. The gold nanomaterial assembly with adjustable assembled structure prepared by the preparation method of any one of claims 1-5 is characterized in that the gold nanomaterial is monodisperse nanoparticles when not assembled in an organic phase, and the particle size of each nanoparticle is 0.5-3nm; the gold nano material is a spherical assembly body after being assembled in water, and the particle size is 30-110nm.
7. The gold nanomaterial assembly with adjustable assembly structure according to claim 6, wherein the maximum fluorescence emission wavelength of the gold nanomaterial is 800nm when the gold nanomaterial is not assembled; after the gold nano material is assembled to form a spherical assembly, the maximum fluorescence emission wavelength of the gold nano material moves between 800nm and 1100nm along with the change of an assembly structure.
8. Use of an assembled structured tunable gold nanomaterial assembly according to claim 6 for the preparation of a photosensitizer, wherein the assembled structured tunable gold nanomaterial assembly is used for generating singlet oxygen, and wherein the structural change of the assembly induces a change in the singlet oxygen generation rate.
9. Use of an assembly of assembled gold nanomaterial with adjustable structure according to claim 8 for the preparation of a photosensitizer, characterized in that the method of assembled gold nanomaterial with adjustable structure for generating singlet oxygen comprises the steps of:
and uniformly mixing the gold nano material assembly with an adjustable assembly structure with the singlet oxygen specific detection agent ABDA, carrying out laser illumination, and testing the ABDA absorption spectrum of the mixed solution along with the illumination time by using an ultraviolet-visible light spectrometer.
10. The application of the gold nano material assembly with the adjustable assembled structure in the preparation of the photosensitizer, according to claim 9, wherein the concentration of the gold nano material assembly with the adjustable assembled structure is 0.01-1uM, the laser illumination wavelength is 450-808nm, the illumination time is 15-60min, and the laser power is 50-500mW/cm 2 。
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