CN114392738B - Covalent heteroligand, alkynyl hyperbranched polyethyleneimine mineralization method for modulating gold nanoclusters, method and application - Google Patents
Covalent heteroligand, alkynyl hyperbranched polyethyleneimine mineralization method for modulating gold nanoclusters, method and application Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/18—Gold
Abstract
The invention provides a covalent heteroligand and alkynyl hyperbranched polyethyleneimine mineralization method for modulating gold nanoclusters, and a method and application thereof. The method can directly, greenly and mildly synthesize the gold nanocluster by using the near-spherical macromolecular heteroligand. Specifically, a certain amount of alkynyl is connected to hyperbranched polyethyleneimine by a click-like method to obtain a monomolecular heteroligand, and then the monomolecular heteroligand is mixed and stirred in water or a water-alcohol mixed solvent and a chloroauric acid solution for several hours to directly obtain magic gold nanoclusters of which each particle only contains 8 gold atoms. The nano-cluster has a large amount of active amino groups, is stable under the conventional environmental condition and is convenient to be used for fluorescent marking. If the glycidyl ether end-capped polyethylene oxide is further connected to the amino, the fluorescent nanocluster which is soluble in water and oil can be obtained, and the efficient catalytic action is shown.
Description
Technical Field
The invention belongs to the field of fluorescent labeling and catalytic materials, and particularly relates to preparation and application of a fluorescent gold nanocluster prepared by modulating an alkynyl hyperbranched polyamine spherical heteroligand.
Background
Gold nanoclusters are ultra-small particles with a size of 0.1-2.3nm and have a size-dependent fluorescence spectrum. Compared with semiconductor quantum dots with the size of 1-10nm, the gold nanoclusters are smaller in size, lower in toxicity and have certain advantages in biomedical labeling, although the width and symmetry of a fluorescence spectrum are inferior to those of the semiconductor quantum dots. The catalytic efficiency of gold nanoclusters tends to be more prominent due to the high specific surface and high surface atomic ratio. In addition, the gold nanoclusters have outstanding photothermal conversion properties and have great potential in the aspect of biological treatment.
The challenge in synthesizing gold nanoclusters is mainly derived from the instability due to the high specific surface; stringent requirements for ligand/modulator; controllability of gold nanocluster growth kinetics. In view of these stringent requirements, synthetic gold nanoclusters often use thiols as ligands/modulators and employ a two-phase approach. The gold nanoclusters synthesized by the method have the following defects: gold nanoclusters are generally available only in oil-soluble, but not water-soluble form; the gold nanocluster composite material needs to be functionalized again; the synthetic method is non-green; the small molecule mercaptan-passivated gold nanoclusters limit the catalytic spectrum thereof; meanwhile, the monovalent thiol ligand is easy to migrate and fall off, so that the labeling is disadvantageous.
Gold particle catalysts rely primarily on surface gold atoms for catalysis, so the smaller the particle, the higher the efficiency. However, there are many challenges to making particles small, stable, and at the same time highly catalytically active. The method for preparing the gold nanocluster catalyst by using the ligand with medium strength and the encapsulation effect is a worthy direction.
Disclosure of Invention
In response to the deficiencies of the prior art, it is a primary object of the present invention to design and synthesize a water-soluble polyvalent non-thiol ligand.
The second purpose of the present invention is to modulate water-soluble gold nanoclusters using the ligand.
The third purpose of the invention is to utilize the active amino groups on the surface of the gold nanocluster to carry out functionalization so as to endow the gold nanocluster composite material with wider application.
In order to achieve the purpose, the solution of the invention is as follows:
1. and covalently integrating alkynyl onto the subsphaeroidal hyperbranched polyethyleneimine to obtain the monomolecular covalent heteroligand.
Preferably, in the step (1), the hyperbranched polyethyleneimine and the propargyl glycidyl ether are mixed in ethanol and reacted for 1 to 4 hours at the temperature ranging from room temperature to micro reflux temperature to obtain the covalent heteroligand. The covalent heteroligands can be removed from the solvent, redissolved in water, and used as an aqueous solution.
Preferably, the molecular weight of the hyperbranched polyethyleneimine in step 1 is between 1800 and 10000 daltons.
Preferably, in step 1, the dosage of propargyl glycidyl ether is alkynyl/amino =0.33/1 to 0.52/1 (molar ratio).
2. And mixing and stirring the chloroauric acid aqueous solution and the covalent heteroligand aqueous solution to obtain the gold nanocluster.
Preferably, in the step (2), the gold nanocluster solution is obtained by stirring for 8 hours at room temperature. The solvent water may be replaced by a mixed solvent of ethanol/water (1 volume ratio). It is also possible to operate at higher temperatures, for example by raising the temperature to 60 ℃ and controlling the reaction time to be around 10 minutes, depending on the complete blue-shift time of the electron absorption spectrum.
Preferably, in the step (2), the input amount of the chloroauric acid is between Au/hyperbranched polyethyleneimine =3/1 and 5/1 (molar ratio);
3. the gold nanoclusters are further modified by polyethylene oxide (solvent can be water or lower alcohol) capped by monoglycidyl ether, so that a catalyst which is soluble in both oil and water and has higher stability is obtained, and the gold nanoclusters are characterized in that the feeding amount is monoglycidyl ether groups/residual amino hydrogen =0.8/1 to 1/1 (mole).
4. The material prepared by the step 3 is used for oil phase or water phase catalytic reaction.
5. The gold nanoclusters obtained by the scheme are used for fluorescent labeling.
Due to the adoption of the scheme, the invention has the beneficial effects that:
firstly, due to the application of the spherical macromolecular heteroligand, the water-soluble gold nanocluster can be directly prepared by a green chemical method, which is similar to biological mineralization; the gold nanoclusters are actually encapsulated by spherical ligands.
Secondly, because of covalent polyvalent ligand, the gold nano-cluster is difficult to migrate and fall off; meanwhile, the compound contains a large number of active amino groups, is very suitable for chemical derivatization, and is easily connected to a labeled substance through a chemical group.
Thirdly, the method can prepare the gold nanocluster on a large scale at low cost.
Drawings
FIG. 1 shows the ultraviolet-visible spectrum (a) and the fluorescence spectrum evolution diagram (b) of a covalent heteroligand (PEI-yne-0.375) modulated gold nanocluster.
FIG. 2 XPS plot of gold nanoclusters.
FIG. 3 is an ultraviolet-visible spectrum evolution diagram of a gold nanocluster for catalyzing the reduction of 4-nitrophenol.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1 (Synthesis of alkynylated polyamine heteroligands)
Synthesis of alkynylated polyethyleneimine (PEI-yne-0.375, 0.375 denotes 0.375 of each amino repeat unit is functionalized with an alkynyl group). Polyethyleneimine (PEI, molecular weight 2000,0.5g,11.6mmol NH) and propargyl glycidyl ether (0.487g, 4.35mmol, corresponding to 37.5mol% of the PEI repeat units) were mixed in ethanol and stirred at room temperature for 6h. And (5) rotary steaming and drying.
Re-dissolving in deuterated methanol, and performing nuclear magnetic characterization: 1 H NMR(400MHz,d4-MeOH)δ/ppm,4.21(m,2H,OCH 2 C≡CH),3.8-4.0(m,1H,HOCHCH 2 O),3.4-3.6(m,2H,HOCHCH 2 O,CHOH),2.5-3.0(m,13.7H,NCH 2 CH 2 N,NCH 2 CHOH,C≡CH).
13 C NMR(101MHz,d4-MeOH)δ/ppm,80.50(C≡CH),76.51(C≡CH),73.60(HOCHCH 2 O),69.67(CHOH),59.35(OCH 2 C≡CH),53-56(NCH 2 -).
example 2 (gold nanocluster preparation)
PEI-yne-0.375 (54.5 mg, containing 0.24mmol of alkynyl) was dissolved in water (8 mL), stirred, and HAuCl was added 4 (1.36mg, 8 mL. Times.5 mM) were mixed. Alkynyl in mixture Au = 6. The mixture was stirred at room temperature for more than 8 hours and the progress of the reaction was followed by UV-Vis spectroscopy and fluorescence spectroscopy (FIG. 1). As can be seen from FIG. 1, a new peak at 369nm appears immediately after mixing of the heteroligand with chloroauric acid, which is attributed to the electrostatic complex of chloroaurate and quaternary ammonium ion. Generally, the absorption peak of the amine after complexing with Au (III) ions is still about 320 nm. There is a clear red-shift that probably gold ions are encapsulated by PEI. Because the polarity in the capsule is relatively lower, the electrostatic induction effect is stronger, and the chloroauric acid radical spectrum has a red shift phenomenon. Over time, the signal at 369nm disappeared after about 3 hours, instead a new peak at 345nm appeared, indicating that the gold ions were fully reduced. XPS detection of finding signal correspondencesThe gold element has only one valence state (fig. 2), and the corresponding electronic binding energies of Au4f are 84.6 and 88.3eV. This binding energy is much higher than that of the zero-valent bulk gold (84.0 and 87.7 eV). Generally, the smaller the size of the gold nanoclusters, or the electron acceptor (e.g., alkynyl in this case) as the ligand, the significantly improved binding energy will be. Further from the fluorescence test, it was found that the fluorescence peak appeared at 460nm (corresponding to gold nanoclusters around 8 gold atoms). And the signal is always enhanced, even if the gold ions are completely reduced, the fluorescence signal is still enhanced, and the signal is also generated by the gold nanoclusters (Nano Lett.2010,10, 2568-2573). The enhanced fluorescence signal is attributed to the positive charge on the gold nanoclusters due to oxidation. On the other hand, ultraviolet absorption mainly occurs at 400nm or less, which also means that the number of gold atoms in the gold nanocluster is 12 gold atoms or less. Since 8 gold atoms belong to magic clusters, which are relatively stable, the probability of 8 atom clusters occurring is the greatest. Although PEI itself also has fluorescent properties and oxidation enhances its fluorescence, control experiments show that pure PEI has little change in fluorescence upon stirring for several days at room temperature, indicating that the fluorescence enhancement comes primarily from the formation and further oxidation of gold nanoclusters.
The tracking of the electron absorption spectrum shows that the spectrum hardly has red shift when the nano-gold is stored for two months at room temperature, which indicates that the nano-gold cluster is not aged; after 6 months of storage, the system becomes dark in color, and the absorption appears in the long wave direction of more than 400nm, which indicates that the gold nanoclusters are aged.
Example 3 (gold nanocluster modification)
In example 2, after the reaction time of the system was 4 hours, polyethylene oxide monoglycidyl ether (molecular weight: 2058,0.53mmol,1.10g, synthesized according to the literature: macromol. Chem. Phys.2013,214, 1817-1828) was further added and stirring was continued for 24 hours or more. The obtained gold nanoclusters are not discolored after being stored in an aqueous solution at room temperature for 4 months. The gold nanoclusters can be subjected to ethanol dialysis, rotary evaporation and vacuum drying to obtain the solid catalytic material. The content of gold is 3.4 × 10 -8 mol/g。
Example 4 (catalytic application)
An aqueous solution (20 mL) containing 4-nitrophenol (0.06 mM) and sodium borohydride (0.5 g) was purged with nitrogen for 15 minutes, and then the catalyst (0.01 g) prepared in example 3 was charged and stirred. The solution changed from red to colorless in 10 seconds (FIG. 3), indicating that the 4-nitrophenol had been sufficiently reduced.
Example 5 (marking)
(1) Biotin (0.244g, 1mmol) and N-hydroxysuccinimide (0.115g, 1mmol) were mixed with dicyclohexylcarbodiimide solution (0.206g, 1mmol) in chloroform (20 mL) and stirred for 8 hours, and the precipitate was filtered off.
(2) PEI-yne-0.375 (145 mg, containing 0.64mmol of alkynyl) was dissolved in ethanol (16 mL), stirred, and HAuCl was added 4 (2.72mg, 16mL. Times.5 mM) and stirred for 4 hours. Polyethylene oxide monoglycidyl ether (molecular weight: 2058,0.53mmol, 1.10g) was added thereto and the mixture was stirred for 8 hours. Dialyzing the large amount of ethanol for 12 hours, and replacing the ethanol once in the middle. The ethanol was removed by rotary evaporation, dissolved in chloroform (10 mL), and the chloroform solution of step (1) was mixed and stirred for 8 hours, concentrated, and precipitated with diethyl ether. The precipitate was redissolved once. The product is a biotin-labeled oil-water-soluble gold nanocluster. The fluorescence characteristics and the electron absorption spectrum are similar to those of FIG. 1.
Claims (9)
1. A method for preparing gold nanoclusters by using water-soluble polyvalent non-thiol ligands is characterized in that alkynyl is covalently integrated on subsphaeroidal hyperbranched polyethyleneimine to obtain monomolecular covalent heteroligands;
modulating and synthesizing the obtained monomolecular covalent heteroligand into a gold nanocluster by using the covalent heteroligand;
the specific implementation steps are as follows:
step 1, mixing hyperbranched polyethyleneimine and propargyl glycidyl ether in ethanol, and reacting for 1-4 hours at room temperature to micro reflux temperature to obtain a covalent heteroligand; the solution is directly used, or the solvent is removed to re-dissolve the covalent heteroligand in water for use;
step 2, mixing a chloroauric acid aqueous solution and the covalent heteroligand aqueous solution, and stirring at room temperature for 2-8 hours to obtain a gold nanocluster solution; or carrying out similar reaction in an ethanol/water mixed solvent, wherein the volume ratio of ethanol/water is 1:1;
and 3, modifying the polyethylene oxide capped by the monoglycidyl ether to obtain the catalyst which is soluble in both oil and water and has higher stability, wherein the molecular weight of the polyethylene oxide is more than 2000.
2. The method according to claim 1, wherein the hyperbranched polyethyleneimine has a molecular weight of 1800 to 10000 dalton.
3. The process of claim 1, wherein the propargyl glycidyl ether is fed in a molar ratio of alkynyl/amino =0.33/1 to 0.52/1.
4. The method according to claim 1, characterized in that said step 2: if the temperature is raised to 60 ℃, the reaction time should be controlled within 10 minutes, depending on the disappearance of the absorption above 410nm in the electron absorption spectrum.
5. The method according to claim 1, characterized in that said step 2:
the input amount of the chloroauric acid is the mole ratio of Au/hyperbranched polyethyleneimine molecules =3/1 to 5/1.
6. The method according to claim 1, wherein said step 3:
the charge is in moles of monoglycidyl ether groups/residual amino hydrogens =0.7/1 to 1/1.
7. A material prepared by the method of any one of claims 1 to 6.
8. Material according to claim 7, characterized by being used for homogeneous catalytic reactions of oil or water phase.
9. The material of claim 7, wherein the prepared gold nanoclusters are used for fluorescent labeling.
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| CN101402965A (en) * | 2008-11-12 | 2009-04-08 | 中国科学院长春应用化学研究所 | Nano-golden particle-containing non-virogene carrier, production method and uses thereof |
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