CN116064031A - Synthesis and application of aggregation-induced emission type gold nanocluster - Google Patents
Synthesis and application of aggregation-induced emission type gold nanocluster Download PDFInfo
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Abstract
The invention discloses a preparation method of aggregation-induced emission type gold nanoclusters and an application thereof to Ag + ，Hg 2+ ，H 2 O 2 GSH detection comprises synthesis of double ligand aggregation-induced emission type gold nanoclusters, fluorescent detection application of silver ions and mercury ions in aqueous solution and continuous colorimetric detection application of hydrogen peroxide and glutathione, and a material for colorimetric-fluorescent dual-mode multi-target detection is provided. The probe is based on aggregation-induced emissionThe mechanism completes the simultaneous detection of the two metal ions. The gold nanocluster also has excellent peroxidase-like activity, and can catalyze and oxidize 3,3', 5' -tetramethyl benzidine. The glutathione is used as a strong reducing agent, so that the system can fade, and free radicals generated in the reaction process are eliminated, thereby realizing continuous colorimetric detection of hydrogen peroxide and glutathione. The invention realizes bimodal multi-target detection and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of nano material synthesis and detection, and particularly relates to synthesis and application of aggregation-induced emission (AIE) gold nanoclusters.
Background
Gold nanoclusters are typically composed of several to several tens of atoms with a core size of 2a nm a, and metallic nanoclusters exhibit a strong quantum size effect due to the size reduction to near the fermi wavelength of electrons between the metal atoms and the nanoparticles. The synthesis method of gold nanoclusters is widely varied, and is generally to select proteins, polypeptides, thiols, polymers and the like as templates or protecting agents to synthesize fluorescent nanoclusters with different wavelength emissions. In general, the metal nanoclusters have strong fluorescence emission, stable fluorescence and adjustable fluorescence wavelength, and can be used as a fluorescent probe for environmental analysis and sensing, including analysis detection and imaging research on heavy metals, biomolecules and the like. [ Jin RC, zeng CJ, zhou M, chen YX. Atomically Precise colloidal metal nanoclusters and nanoparticles: fundamental and reporting technologies, chemical Reviews, 2016, 116 (18): 10346-10413]The gold nanocluster has the advantages of simple preparation method, large Stokes shift, good water solubility, low toxicity, good biocompatibility and the like, and has attracted wide attention in the fields of pollutant monitoring, catalysis, cell imaging, biological analysis sensing and the like. However, most gold nanoclusters have an aggregation-induced quenching effect (ACQ), so that gold nanoclusters tend to exhibit low quantum yields and stability due to an energy-eliminating effect and a self-quenching effect of ligand movement, which greatly limits the application of gold nanoclusters in chemical sensing. Therefore, there is a need to develop a new strategy to improve the luminescence and stability of gold nanoclusters. Due to the general impact of ACQ phenomenon, there is still little research on aggregation-induced emission (AIE) -type gold nanoclusters. The AIE theory provides a new approach to solve the problem of aggregation-induced quenching of fluorogold nanoclusters, and the AIE-type open-type fluorescence sensor has higher compared with the closed-type sensor with ACQ characteristicsSensitivity and selectivity of (a). [ Zhang, L.; xu, Y.; xu, J.; zhang, H.; zhao, T.; jia, L. Intelligent multicolor nano-sensor based on nontoxic dual fluoroprobe and MOFs for colorful consecutive detection of Hg) 2+ and cysteine J. Hazard. Mater 2022, 430, 128478]. Furthermore, the new concept of "single sensor multiple analytes", namely "multiplex detection probes", has attracted a great deal of interest to researchers. The ability to detect multiple targets simultaneously can reduce analysis processing time and cost. Therefore, the design of the fluorescent probe based on the AIE theory, and the realization of the interference-free synchronous detection of different analytes through the conversion between an aggregation state and a dispersion state, is very innovative.
Toxic heavy metals (such as mercury, silver, etc.) can cause serious diseases and environmental pollution problems, and pose a serious threat to human health and ecosystems. In particular silver ions (Ag) + ) And mercury ions (Hg) 2+ ) The water-based biological agent is widely distributed, is easy to accumulate in a food chain and is difficult to biodegrade, so that the water-based biological agent has important significance for concentration tracking in natural water. High dose Ag + The exposure can cause various diseases such as silver poisoning, skin and liver injury, stomach pain, slow growth, heart enlargement, etc. [ An, J.; chen, R.; chen, M. An Ultrasensitive turn-on ratiometric fluorescent probes for detection of Ag ] + based on carbon dots/SiO 2 and gold nanoclusters, sens, operators B chem, 2021, 329, 129097. Mercury is considered more dangerous because all forms of mercury, including elemental and ionic mercury, are ultimately converted to methylmercury by bacterial activity and then enriched in animals via the food chain. Hg of Hg 2+ Can cause neurological and immune system disorders, irreversible injury to the lung, kidney, brain, and even can induce dire diseases such as acrodynia (pink), hunter-Russell syndrome, water, etc. [ Cheng, z.; wei, j.; gu, l.; zou, l.; wang, t.; chen, l.; li, y.; yang, y. DNAzyme-based biosensors for mercury (ii) detection: rational construction, advanced and select, j. Hazard, mater 2022, 431, 128606.]. In view of this, ag in the environment is effectively monitored and accurately detected + And Hg of 2+ Is used for preventing weightMetals have important implications for human health.
Hydrogen peroxide (H) 2 O 2 ) Is an important participant in clinical biochemistry, energy, food, pharmacy, enzyme catalysis and environmental monitoring. H 2 O 2 Abnormal accumulation of (a) causes oxidative stress and serious diseases such as cardiovascular diseases, diabetes, cancer, parkinson and Alzheimer's disease [ Wang, S.; hu, Z.; wei, Q.; zhang, H.; tan, W.; sun, Y.; duan, H.; dai, Z.; liu, Q.; zheng, X. Diatomic active sites nanozymes: enhanced peroxidase-like activity for dopamine and intracellular H) 2 O 2 detection, nano Res.2022, 15, 4266-4273 ]. Glutathione (GSH) is an intracellular thiol that plays a key role in maintaining the redox state in cells, involved in intracellular signal transduction, immune response, regulation of gene transcription, etc. [ Lu, w.; chen, s.; zhang, h.; qiu, j.; liu, x. FeNC single atom nanozymes with dual enzyme-mimicking activities for colorimetric detection of hydrogen peroxide and gluthione, j. Materials 2022, 8 (6), 1251-1259] is also considered a tumor biomarker [ Lu, w.; chen, s.; zhang, h.; qiu, j.; liu, x. FeNC single atom nanozymes with dual enzyme-mimicking activities for colorimetric detection of hydrogen peroxide and gluthione, j. Materials 2022, 8 (6), 1251-1259 ]. Taking into account H 2 O 2 And GSH plays an important role in human health monitoring, and H 2 O 2 Intracellular imbalance with GSH is also closely related to major diseases, and thus, H in blood 2 O 2 And quantitative analysis of GSH are critical to clinical diagnosis.
Disclosure of Invention
The invention aims to provide synthesis and application of aggregation-induced emission (AIE) gold nanoclusters.
Aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs, which is prepared by the following method:
1) Adding 2.43-mM chloroauric acid solution 20-mL into a container, then taking 0.01-0.05M NAC solution 0-5mL and 0.01M GSH solution 0-5mL, rapidly and sequentially adding the solution into the chloroauric acid solution, vigorously stirring at room temperature for 25-35 min, and uniformly mixing; the chloroauric acid: NAC: the ratio of GSH mass amounts to 0.972: (1-5): 1, a step of;
2) Reflux-treating at 60-100 ℃ for 12-36 h to obtain a light yellow NAC/GSH-AuNCs aqueous solution, and cooling to room temperature;
the chloroauric acid: NAC: the ratio of GSH mass amounts to 0.972:1:1, a step of;
the adding amount of the NAC solution is 0.01-M and 5mL;
the addition amount of the GSH solution is 5mL;
the reflux temperature is 80 ℃ and the reflux time is 24 hours.
The aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs is applied to detection of heavy metal ions and biological small molecules;
the heavy metal ion is Ag + And/or Hg 2+ ；
The biological small molecule is H 2 O 2 And/or GSH.
Aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs for detecting Ag + And Hg of 2+ A method of (2), comprising:
1) Drawing a standard curve: mixing NAC/GSH-AuNCs solution with equal volume of ultrapure water, and measuring fluorescence intensity value I of blank group 0 Taking NAC/GSH-AuNCs solution and Ag with different known concentrations + And Hg of 2+ After the solutions are mixed, the fluorescence intensity values I at 600 and nm are respectively measured and the corresponding relative fluorescence intensity values I are calculated 0 I, respectively establishing relative fluorescence intensity values I 0 I and Ag + And Hg of 2+ A standard curve corresponding to the concentration;
2) Fluorescence detection of Ag + : taking NAC/GSH-AuNCs solution and Ag with concentration to be measured + After mixing the solutions, the fluorescence intensity value I is measured and the relative fluorescence intensity value I is calculated 0 Obtaining Ag in the solution to be tested according to the standard curve + Is a concentration of (2);
3) Fluorescent detection of Hg 2+ : taking NAC/GSH-AuNCs solution and Hg with concentration to be measured 2+ After mixing the solutions, the fluorescence was measuredLight intensity value I and calculate relative fluorescence intensity value I 0 Obtaining Hg in the solution to be tested according to the standard curve 2+ Is a concentration of (2);
the different known concentrations of Ag in step 1) + Ag in solution + The concentration range of (2) is 0-10 mu M, and Ag in the solution to be tested + The applicable range of the concentration is 0.001-0.100 mu M;
different known concentrations of Hg in said step 1) 2+ Hg in solution 2+ The concentration of Hg in the solution to be tested is between 0 and 200 mu M 2+ The concentration is 0-100 mu M;
the NAC/GSH-AuNCs solution and Ag + The reaction time is 0-6 min, preferably 1 min;
the NAC/GSH-AuNCs solution and Hg 2+ The reaction time of the solution is 1-10 min, preferably 1 min;
the reactions were all carried out at room temperature.
The fluorescence detection conditions are as follows: excitation wavelength 380 nm, excitation slit and emission slit width 3 nm, recording the emission intensity of NAC/GSH-AuNCs versus Ag at 600 nm + And Hg of 2+ Quantitative analysis was performed.
Aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs detection H 2 O 2 A method of (2), comprising:
1) First 30% H 2 O 2 Dilution of the solution to H of different concentrations 2 O 2 The solution is then treated with equal amounts of H at different concentrations 2 O 2 The solutions are respectively added into blank solutions with the same volume to obtain a plurality of groups of solutions to be tested: wherein the blank solution contains ultrapure water, HAc-NaAc buffer solution, TMB and the gold nanoclusters NAC/GSH-AuNCs;
2) After the system reacts for 5min at room temperature, the absorbance of the solution to be measured is respectively measured;
3) Drawing a standard curve: by H in the solution to be measured 2 O 2 Taking the measured absorbance value at 652 nm as the ordinate, and performing linear fitting to obtain an equation;
4) Will contain unknown concentrations of H 2 O 2 Is added to the solution to be testedAdding the solution into a blank solution, measuring absorbance A, substituting absorbance value according to a linear equation to calculate H in the solution to be measured 2 O 2 Is a concentration of (2);
the dosage of the HAc-NaAc buffer solution is 250 mu L and 0.2M;
the dosage of TMB is 50 mu L, 0-2.00 mM;
the gold nanoclusters NAC/GSH-AuNCs are used in an amount of 0-200. Mu.L, preferably 75. Mu.L.
Different concentrations of H as described in step 1) 2 O 2 In solution, H 2 O 2 Is 0.03-1 mM, H in the solution to be tested 2 O 2 The concentration is 0.03-0.20 mM;
the pH of the HAc-NaAc buffer solution is 3.6-5.6, the TMB concentration is 0-2.0 mM, and the NAC/GSH-AuNCs concentration is 0-200 mu L.
The method for detecting GSH by aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs comprises the following steps:
1) Firstly, preparing GSH solutions with different concentrations, and then respectively adding equal volumes of GSH solutions with different concentrations into blank solutions with the same volumes to obtain a plurality of groups of solutions to be tested: wherein the blank solution contains ultrapure water, HAc-NaAc buffer solution, TMB, H 2 O 2 And the gold nanoclusters NAC/GSH-AuNCs;
2) After the system reacts for 5min at room temperature, the absorbance of the solution to be measured is respectively measured;
3) Drawing a standard curve: taking the addition concentration of GSH in the solution to be measured as an abscissa, taking the absorbance value at 652 and nm as an ordinate, and performing linear fitting to obtain an equation;
4) Adding a solution to be detected containing GSH with unknown concentration into a blank solution, then measuring absorbance A, substituting absorbance values according to a linear equation to calculate the concentration of GSH in the solution to be detected;
the HAc-NaAc buffer solution in the step 1) is used in an amount of 250 mu L and 0.2. 0.2M; the dosage of TMB is 50 mu L,1.80 mM; the H is 2 O 2 The amount of (2) was 50. Mu.L, 1.50 mM;
the usage amount of the gold nanocluster NAC/GSH-AuNCs is 75 mu L;
step (a)1) The concentration of GSH in GSH solution with different concentrations is between 0.50 and 60 mu M, and H in the solution to be tested 2 O 2 The concentration is 0.50-8.00 mu M;
the pH of the HAc-NaAc buffer solution is 3.6-5.6, the TMB concentration is 0-2.0 mM, and the H 2 O 2 The concentration is 0-2.0. 2.0 mM.
Detailed description of the invention:
the invention aims to provide an aggregation-induced emission type fluorescent gold nanocluster and a synthesis method thereof.
Another object of the present invention is to develop a multiplex fluorescence-colorimetric dual-mode probe capable of detecting and distinguishing two heavy metal ions Ag + And Hg of 2+ Is a fluorescent probe of (2); gold nanocluster NAC/GSH-AuNCs as fluorescent probe can realize Ag alignment + And Hg of 2+ And (5) performing multiplex detection. When a certain concentration of Ag is added into the NAC/GSH-AuNCs probe solution + The fluorescence is obviously enhanced when the Hg is added in a certain concentration 2+ A significant quenching of fluorescence occurs, whereby NAC/GSH-AuNCs can realize Ag + And Hg of 2+ Is distinguished from other metal ions, and two detected targets Ag + And Hg of 2+ The phenomenon is completely opposite, and the identification can be distinguished. Relative fluorescence intensity of NAC/GSH-AuNCs fluorescent Probe (I 0 I) and Ag + And Hg of 2+ Has good linear relation between the concentrations, and quantitatively analyzes the unknown concentration sample through a linear relation equation.
Simultaneously has the performance of nano enzyme and can catalyze H 2 O 2 Oxidizing 3,3', 5' -tetramethyl benzidine (TMB) to turn blue to reach colorimetric detection H 2 O 2 And on the basis of this result detecting GSH in the serum by means of a reduction mechanism. For H 2 O 2 And colorimetric detection of GSH, the inherent nano-enzyme activity of the gold nanoclusters plays an important role. Experimental study shows that NAC/GSH-AuNCs has peroxide mimic enzyme activity in H 2 O 2 NAC/GSH-AuNCs can catalyze H in the presence of 2 O 2 Generates hydroxyl radical (∙ OH) by decomposition, thus will not beThe colored TMB substrate oxidizes to soluble oxTMB and the corresponding solution turns blue in color. Adding different concentrations of H to the NAC/GSH-AuNCs-TMB system 2 O 2 The amount of blue oxTMB produced in the system will also vary, so that H can be colorimetrically measured 2 O 2 Is quantitatively determined. However, GSH has strong reducibility as a biological thiol, can inhibit the color development process, and enables NAC/GSH-AuNCs-TMB-H 2 O 2 The system fades. With the addition of GSH with different concentrations, the fading degree of the system is different, so that qualitative and quantitative detection of GSH is carried out by a colorimetric method.
The aggregation-induced emission type gold nanocluster provided by the invention is a gold nanocluster in which N-acetyl-L-cysteine and glutathione are simultaneously used as a reducing agent and a stabilizing agent.
Aggregation-induced emission type gold nanoclusters can detect trace Ag contained in an aqueous solution through a fluorescence mode + And Hg of 2 + H in the aqueous solution sample can be detected by colorimetric mode 2 O 2 And GSH concentration.
The purpose of the present invention is to provide a method for simultaneously detecting Ag in an aqueous solution + And Hg of 2+ Continuous colorimetric detection of H based on its class of peroxidase activity 2 O 2 And GSH methods.
The invention has the following beneficial effects:
1. NAC and GSH used in the invention are used as aggregation-induced emission type gold nanocluster materials protected by double ligands, gold nanoclusters with stable optical performance can be obtained through optimization and regulation, and the gold nanoclusters can be used as a multi-element detection probe to realize Ag detection + 、Hg 2+ Biomolecule H 2 O 2 Detecting GSH;
2. according to the invention, the aggregation state of gold nanocluster particles is regulated by utilizing the metal-philic interaction among silver ions, mercury ions and aggregation-induced emission type gold nanoclusters, so that the emission intensity of the gold nanoclusters is changed, the fluorescence of the gold nanoclusters is obviously enhanced by the silver ions, and the fluorescence of the gold nanoclusters is obviously reduced by the mercury ions; the fluorescence enhancement and quenching phenomenon can be used for detecting silver ions and mercury ions;
3. the invention can be used for Ag + 、Hg 2+ 、H 2 O 2 And GSH, the method has good selectivity, high sensitivity and low detection limit, wherein the detection limit of silver ions can be as low as 0.87 and nM.
Drawings
FIG. 1 is a schematic diagram of aggregation-induced emission type NAC/GSH-AuNCs synthesis and multiplex detection platform principle;
FIG. 2 is a graph of the ultraviolet visible absorption spectrum, normalized fluorescence excitation spectrum, and emission spectrum of NAC/GSH-AuNCs, with inserts of NAC/GSH-AuNCs under natural light and ultraviolet lamp illumination, respectively;
FIG. 3 fluorescence spectra of NAC/GSH-AuNCs, NAC-AuNCs, and GSH-AuNCs;
FIG. 4 TEM image of NAC/GSH-AuNCs;
FIG. 5 TEM images of NAC-AuNCs and GSH-AuNCs;
FIG. 6 NAC/GSH-AuNCs Ag incorporation + Size distribution diagram of the gold cluster aggregate formed before and after;
FIG. 7 NAC/GSH-AuNCs Ag incorporation + Or Hg 2+ A subsequent TEM image;
FIG. 8 XPS spectrum of NAC/GSH-AuNCs;
FIG. 9 is a graph of experimental results of selectivity and interference immunity of NAC/GSH-AuNCs as fluorescent probes;
FIG. 10 addition of different concentrations of (a) Ag + Or (b) Hg 2+ Fluorescence emission spectra of rear NAC/GSH-AuNCs, different concentrations of (c) Ag + Or (d) Hg 2+ And relative fluorescence intensity (I) 0 A standard curve of/I);
FIG. 11 UV-visible absorption spectra and corresponding photographs of TMB, TMB+H, respectively, in different reaction systems 2 O 2 ，TMB+NAC/GSH-AuNCs，TMB+H 2 O 2 + NAC/GSH-AuNCs， H 2 O 2 + NAC/GSH-AuNCs；
FIG. 12 different concentrations H 2 O 2 A standard curve with absorbance values;
FIG. 13 NAC/GSH-AuNCs-TMB-H 2 O 2 A selective experimental result graph of the system as a colorimetric probe;
figure 14 standard curves of GSH concentration versus absorbance value.
Detailed Description
Example 1 preparation of aggregation-induced emission type gold nanoclusters NAC/GSH-AuNCs
2.43 mM HAuCl was taken 4 20mL of (chloroauric acid) solution is added into a round-bottom flask, and then 5mL of 0.01-0.05M NAC (N-acetyl-L-cysteine) solution and 5mL of 0.01M GSH (glutathione) solution are sequentially added into the flask, wherein the chloroauric acid is as follows: NAC: the ratio of GSH mass amounts to 0.972: (1-5): 1, a step of; the reaction was stirred vigorously at room temperature for 0.5h and then refluxed in an oil bath at 60-100deg.C for 12-36-h to give a pale yellow aqueous NAC/GSH-AuNCs solution (FIG. 1).
Example 2 preparation of aggregation-induced emission type gold nanoclusters NAC/GSH-AuNCs
2.43 mM HAuCl was taken 4 20mL of (chloroauric acid) solution was added to a round bottom flask, to which was then added sequentially 5mL of 0.01M NAC solution and 5mL of 0.01M GSH solution, to immobilize chloroauric acid: NAC: the ratio of GSH mass amounts to 0.972:1:1, vigorously stirring at room temperature to react 0.5. 0.5h, and then refluxing in an oil bath at 80 ℃ for 24 hours to obtain a pale yellow NAC/GSH-AuNCs aqueous solution.
Example 3 characterization of aggregation-induced emission gold nanoclusters NAC/GSH-AuNCs
(1) Ultraviolet visible absorption spectrum
From the UV-visible absorbance spectrum, no apparent surface plasmon resonance peak was observed for NAC/GSH-AuNCs at 520 nm, indicating the absence of large-sized gold nanoparticles in NAC/GSH-AuNCs (FIG. 2).
(2) Fluorescence spectrum
From the fluorescence emission spectra of NAC/GSH-AuNCs, it is seen that at the optimum excitation wavelength of 380 nm, there is a strongest emission peak at 600 nm (FIG. 1), while exhibiting strong orange fluorescence at 365 nm UV light source (FIG. 2).
To verify the simultaneous protection of NAC/GSH-AuNCs by dual ligand NAC and GSH, NAC/GSH-AuNCs were fluorescence spectrum tested with single ligand synthesized NAC-AuNCs and GSH-AuNCs (FIG. 3). The result shows that NAC/GSH-AuNCs fluorescence emission is stronger than that of gold nanoclusters prepared by other two independent protective agents, and the primary demonstration of the protective effect of the double ligands promotes the emission efficiency of the gold nanoclusters.
(3) Transmission Electron Microscope (TEM)
Adding Ag to NAC/GSH-AuNCs probe, NAC-AuNCs, GSH-AuNCs and NAC/GSH-AuNCs probe by TEM + And Hg of 2+ The morphology was characterized. Fig. 4 is a TEM image of NAC/GSH-AuNCs, where fig. a and b show that the synthesized NAC/GSH-AuNCs have a distinct aggregation state, with a size of about 26.33 nm (fig. 6a, n=62). As can be seen from fig. 4c, the NAC/GSH-AuNCs aggregates consisted of spherical NAC/GSH-AuNCs with an average particle size of about 1.80 nm (n=100), and the strong luminescence characteristics of NAC/GSH-AuNCs were confirmed to be due to aggregation-induced luminescence mechanism. The high resolution transmission image in fig. 4d shows clear lattice fringes whose lattice spacings 0.235 nm,0.200 nm and 0.140 nm correspond to the (1 1 1), (2 0 0) and (2 2 0) crystal planes of Au (0), respectively, confirming the synthesis of gold clusters. To further demonstrate that dual ligand NAC and GSH are co-involved in gold cluster synthesis, TEM characterization was also performed on single ligand synthesized NAC-AuNCs and GSH-AuNCs. Fig. 5 shows that GSH-AuNCs are spherical in morphology with NAC-AuNCs. NAC-AuNCs having an average particle size of 1.70. 1.70 nm exhibited a degree of agglomeration with greater inter-particle distance of NAC-AuNCs and more dispersed particles than NAC/GSH-AuNCs (FIG. 5 a); GSH-AuNCs had good monodispersity with an average particle size of 5.60 nm (fig. 5 b). The result shows that the aggregation degree of the synthesized gold cluster directly influences the luminous intensity of the gold cluster, and the addition of GSH ligand provides more thiol compounds for the synthesis of the gold cluster, so that the content of Au (I) -SR in the gold cluster is improved, and the emission efficiency of NAC/GSH-AuNCs is further enhanced.
FIGS. 7a and 7b Ag addition to NAC/GSH-AuNCs + The transmitted image was then observed from the image, 10. Mu.M Ag + The NAC/GSH-AuNCs were induced to form larger and more aggregates, with a size of about 33.83 nm (fig. 6b, n=62), and the average particle size of the small spherical NAC/GSH-AuNCs in the aggregates was about 1.72 nm (n=100). As a result, it was found that the change in particle diameter was not significant, but the distance between particles was significantly shortened, resulting in more compact aggregation, so that the fluorescence of NAC/GSH-AuNCs was significantly enhanced, fromAnd the aggregation-induced emission effect was verified. More interestingly, 100. Mu.M Hg 2+ The introduction of (a) causes the NAC/GSH-AuNCs to change from an agglomerated state to a monodisperse state (fig. 7c and 7 d), with an average particle size of about 2.04 nm (n=100). The agglomeration state completely disappeared, and the particle diameter remained basically unchanged, indicating Hg 2+ The addition of (2) also only changes the distance of the particles, so that the particles are more dispersed, and the aggregation-induced quenching effect is eliminated. Transmission image description Ag + And Hg of 2+ Both fluorescence enhancement and quenching phenomena of NAC/GSH-AuNCs after introduction are consistent with aggregation-induced emission mechanisms.
The results of the patterns can prove that the aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs protected by double ligands can be successfully prepared and used for Ag + And Hg of 2+ The fluorescence response of (2) is based on an aggregation-induced emission mechanism, which predicts the applicability as a multiplex probe.
(4) X-ray photoelectron spectroscopy (XPS)
XPS of the test samples verifies the gold valence distribution in NAC/GSH-AuNCs. FIG. 8 shows that the high resolution XPS spectrum of Au has two distinct peaks at 84.5 eV and 88.2 eV, respectively, for Au 4f 7/2 And Au 4f 5/2 A track. The energy difference of spin-orbit splitting was 3.7. 3.7 eV, consistent with the results reported in the literature. Au (0) 4f 7/2 And Au (0) 4f 5/2 Located at 84.2 and 87.9 eV, au (I) 4f, respectively 7/2 And Au (I) 4f 5/2 At 84.6 and 88.3 eV, respectively. The ratio of Au (I) to Au (0) in NAC/GSH-AuNCs is 1.87/1, the content of Au (I) on the surface is higher, the characteristics of high metal oxidation state content in aggregation-induced emission type metal nanoclusters are met, and the property root cause of aggregation-induced emission of the gold clusters is also proved.
Example 4 aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs as fluorescent probe for detection of Ag + And Hg of 2+
Uses aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs as fluorescent probe, and can be used for Ag + And Hg of 2+ Respectively detecting, when a certain concentration of Ag is added into the NAC/GSH-AuNCs probe solution + The fluorescence is obviously enhanced when the Hg is added in a certain concentration 2+ Will be whenA significant quenching of fluorescence occurs, whereby NAC/GSH-AuNCs can realize Ag + And Hg of 2+ Is distinguished from other metal ions, and two detected targets Ag + And Hg of 2+ The phenomenon is completely opposite, and the identification can be distinguished. Relative fluorescence intensity of NAC/GSH-AuNCs fluorescent Probe (I 0 I) and Ag + And Hg of 2+ Has good linear relation between the concentrations, and quantitatively analyzes the unknown concentration sample through a linear relation equation.
(1) Fluorescence method for detecting Ag + And Hg of 2+ Is of (2)
As excellent selectivity and anti-interference capability are important indexes for evaluating the sensing performance of the fluorescent probe, the invention has the advantages of NAC/GSH-AuNCs to Ag + And Hg of 2+ The selectivity and anti-interference ability of the assay were studied (fig. 9). NAC/GSH-AuNCs probe and Ag + Or Hg 2+ Adding 100 mu M Ca possibly coexisting in the solution of (C) 2+ , Pb 2+ , Zn 2+ , Mn 2+ , Ba 2+ , Cr 3+ , Ni 2+ , Mg 2+ , Cu 2+ , Fe 2+ , Co 2+ , Cd 2+ Solution for examining other metal ions to detect Ag by NAC/GSH-AuNCs probe + Or Hg 2+ Is a function of (a) and (b). The results indicate that although the concentration of coexisting metal ions is Ag + Can not independently cause the fluorescence of the probe to obviously change by 10 times, but only exists 10 mu M Ag + When the fluorescent intensity of NAC/GSH-AuNCs is increased by 5 times, and simultaneously, the fluorescent intensity of NAC/GSH-AuNCs is increased by 100 mu M Hg 2+ Leads to obvious fluorescence quenching, the quenching efficiency of the probe is as high as 63%, and the Hg is clearly indicated 2+ Is present. The result shows that the NAC/GSH-AuNCs probe has excellent selectivity and anti-interference capability, and is Ag + And Hg of 2+ Provides a fluorescent analysis strategy of "on" and "off.
(2) Fluorescence method for detecting Ag + And Hg of 2+ Sensitivity assessment of (a)
Ag based on NAC/GSH-AuNCs fluorescent probe pair + And Hg of 2+ Further intensive studies on the NAC/GSH-AuNCs pairAg + And Hg of 2+ Sensitivity of detection (fig. 10). Mixing the solution to be tested with different concentrations with the equal volume of NAC/GSH-AuNCs, reacting for 1 min, and monitoring the concentration of the NAC/GSH-AuNCs on the Ag with different concentrations by fluorescence spectrum + (0-10. Mu.M) and Hg 2+ (0-200. Mu.M) and verifying the sensitivity. As can be seen from fig. 10a and 10b, as Ag + The increase in concentration at 600 nm is accompanied by a slight red shift in fluorescence intensity consistent with the change in fluorescence intensity under UV light, relative fluorescence intensity I 0 The Ag is calculated according to the formula 3σ/K (σ is the standard deviation of the detection method to the blank solution, K is the linear equation slope of the detection method) with good linear relation between I and silver ion concentration in the range of 0.001-0.100 μM (FIG. 10 c) + Can be as low as 0.87. 0.87 nM. Detection of Hg by NAC/GSH-AuNCs 2+ Is analyzed in the same way as the sensitivity of Hg 2+ The increase in concentration, with a continuous decrease in fluorescence intensity at 600 nm, was accompanied by a slight blue shift, consistent with an image of the change in fluorescence intensity under an ultraviolet lamp. In the range of 0.01-100 mu M, the relative fluorescence intensity I is established 0 I and Hg 2 + Linear equation of concentration (fig. 10 d), calculated Hg 2+ The detection limit of (2) was 47.0. 47.0 nM. Therefore, NAC/GSH-AuNCs can be used as detection of Ag based on different response phenomena + And Hg of 2+ Can realize Ag in aqueous solution + And Hg of 2+ Is a simultaneous, multiplex, rapid, accurate, real-time, on-site assay.
(3) Ag in actual water sample + And Hg of 2+ Recovery analysis of (2)
Ag in actual Water sample by NAC/GSH-AuNCs prepared in this example 1 + And Hg of 2+ Is a recovery test of (2). The sample measurement needs simple pretreatment, and the solid impurities in the water are removed by using a filter membrane. Using example 4 step (2) as reference, simulating actual detection by standard addition method, and adding Ag with different concentrations into two water samples respectively + Standard solutions (5.00, 8.00, 10.00, nM) and Hg 2+ Hg of standard solution (0.50,0.80,1.00. Mu.M) 2+ Standard solventAfter adding NAC/GSH-AuNCs solution to the solution and reacting for 1 min at room temperature, the fluorescence intensity value at 600 nm was measured with 380 nm as excitation wavelength. Specific results of the sample recovery test (n=3) are shown in tables 1 and 2.
EXAMPLE 5 research on the mimic enzyme Activity of NAC/GSH-AuNCs and detection of H 2 O 2 And GSH (GSH)
For H 2 O 2 And colorimetric detection of GSH, the inherent nano-enzyme activity of the gold nanoclusters plays an important role. Experimental study shows that NAC/GSH-AuNCs has peroxide mimic enzyme activity in H 2 O 2 NAC/GSH-AuNCs can catalyze H in the presence of 2 O 2 The decomposition produced hydroxyl radicals (∙ OH) which oxidized the colorless TMB substrate to soluble oxTMB, the corresponding solution color changing to blue. Adding different concentrations of H to the NAC/GSH-AuNCs-TMB system 2 O 2 The amount of blue oxTMB produced in the system will also vary, so that H can be colorimetrically measured 2 O 2 Is quantitatively determined. However, GSH has strong reducibility as a biological thiol, can inhibit the color development process, and enables NAC/GSH-AuNCs-TMB-H 2 O 2 The system fades. With the addition of GSH with different concentrations, the fading degree of the system is different, so that qualitative and quantitative detection of GSH is carried out by a colorimetric method.
(1) Peroxide mimetic enzyme Activity of NAC/GSH-AuNCs-TMB
To investigate the enzyme-like catalytic activity of gold nanoclusters, the following control experiments were performed (fig. 11). The results show that only TMB and H 2 O 2 NAC-GSH-AuNCs can catalyze H in the presence of the same 2 O 2 Oxidizing the colorless TMB substrate to blue oxTMB, with a maximum absorbance at 652 nm,however in the absence of H 2 O 2 And NAC/GSH-AuNCs, the color reaction cannot occur, so that the typical absorption peak does not appear. The results demonstrate that NAC-GSH-AuNCs have an enzyme-like catalytic activity that is a peroxidase-like activity, rather than an oxidase-like activity.
(2) Detection of H based on NAC/GSH-AuNCs-TMB system as colorimetric probe 2 O 2 Sensitivity of (2)
When NAC/GSH-AuNCs-TMB system is used as colorimetric detection probe, different concentrations of H are used 2 O 2 The solution (0.03-1.00-mM) was added to the colorimetric probe, and after 5min of reaction, the ultraviolet-visible absorption spectra of the samples were separately tested to verify the sensitivity of the probe. As can be seen from FIG. 12a, the absorbance of this system follows H 2 O 2 The increase in concentration is enhanced, consistent with a color change under natural light. 652 Absorbance at nm versus H 2 O 2 Exhibits good linear relationship in the linear range of 0.03. 0.03 mM to 0.20. 0.20 mM, and H is calculated according to the formula 3σ/K 2 O 2 The detection limit of (a) was 2.9. Mu.M (FIG. 12 b). Therefore, NAC/GSH-AuNCs-TMB system can be used for detecting H 2 O 2 The colorimetric probe of the kit can rapidly and accurately detect H in an aqueous solution 2 O 2 。
(3) NAC/GSH-AuNCs-TMB-H based 2 O 2 System as colorimetric probe for detecting GSH selectivity
Using NAC/GSH-AuNCs-TMB-H 2 O 2 The system is used as a colorimetric probe for respectively detecting GSH, common biomolecules thereof and cations in serum. Under the same conditions, glutathione (GSH), bovine Serum Albumin (BSA), cysteine (Cys), methionine (Met), ascorbic Acid (AA), histidine (His), tryptophan (Trp), glutamic acid (Glu) and 100. Mu.M cation (K) of 4 mM were respectively selected + 、Ca 2+ 、Na + ) The solution was added to the system to observe experimental phenomena, and the ultraviolet visible absorption spectrum was tested to further calculate the absorbance reduction efficiency of the sample solution. FIG. 13 shows that glutathione decreases the absorbance of a solution far more efficiently than other analytes, because it has a strong reducibility,the oxidized oxTMB was reduced, resulting in a gradual change in the color of its oxidized state to colorless. The corresponding photographs also show that the blue solution was completely reduced to colorless only by the addition of GSH, indicating NAC/GSH-AuNCs-TMB-H 2 O 2 The system has good selectivity on GSH detection as a colorimetric probe, and can further extend the detection system to be a GSH detection probe.
(4) NAC/GSH-AuNCs-TMB-H based 2 O 2 Sensitivity of system as colorimetric probe for detecting GSH
Using NAC/GSH-AuNCs-TMB-H 2 O 2 When the system is used as a colorimetric detection probe, GSH solutions (0.50 mu M-60.00 mu M) with different concentrations are added into the colorimetric detection probe, and after the reaction is carried out for 5min, the sensitivity of the detection probe is verified according to the ultraviolet-visible absorption spectrum of a test sample. As can be seen from fig. 14, the higher the concentration of GSH added, the lower the absorbance value of the system, which is the same as the case of solution discoloration under natural light. 652 The absorbance at nm shows a good linear relationship with GSH concentration in the range of 0.50-8.00. Mu.M, and the detection limit of GSH is calculated to be 0.22. Mu.M according to the formula 3 sigma/K and a linear equation. Therefore, NAC/GSH-AuNCs-TMB-H 2 O 2 The system can be used as a colorimetric probe for detecting GSH, can realize visual detection and quantitative analysis of GSH, can complete series detection, and is expected to be applied to monitoring GSH in human serum.
(5) Recovery test of GSH in serum
The NAC/GSH-AuNCs obtained in this example 1 was used to demonstrate the activity of peroxidase-like enzymes, and the serum GSH recovery test was performed according to step (4) of this example, to verify the feasibility. The pretreatment process of the human blood sample is as follows. The sample was centrifuged at 4500 r/min for 10 min and the supernatant separated was serum, diluted 100-fold for use. Then, 50 mM GSH stock solutions were diluted to 4.00,8.00, 10.00. Mu.M with serum samples, respectively, and added to NAC/GSH-AuNCs-TMB-H, respectively 2 O 2 The system, whose absorbance value was determined by the standard recovery test (n=3), was substituted into the linear equation fitted in fig. 14b to calculate its recovery, and the specific results are shown in table 3, which shows thatNAC/GSH-AuNCs probe can detect H 2 O 2 GSH can also be continuously detected on the basis, and the method has good environmental adaptability.
In conclusion, NAC/GSH-AuNCs can be used as a multiplex probe to finish Ag under a fluorescence mode + And Hg of 2+ Is used for simulating the activity of peroxidase to complete H in a colorimetric mode 2 O 2 And continuously detect GSH.
Claims (8)
1. Aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs, which is prepared by the following method:
1) Adding 2.43-mM chloroauric acid solution 20-mL into a container, then taking 0.01-0.05M NAC solution 0-5mL and 0.01M GSH solution 0-5mL, rapidly and sequentially adding the solution into the chloroauric acid solution, vigorously stirring at room temperature for 25-35 min, and uniformly mixing; the chloroauric acid: NAC: the ratio of GSH mass amounts to 0.972: (1-5): 1, a step of;
2) Reflux-treating at 60-100 ℃ for 12-36 h to obtain a light yellow NAC/GSH-AuNCs aqueous solution, and cooling to room temperature.
2. The aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs according to claim 1, characterized in that: the chloroauric acid: NAC: the ratio of GSH mass amounts to 0.972:1:1.
3. the aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs according to claim 2, characterized in that: the adding amount of the NAC solution is 0.01-M and 5mL.
4. The aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs according to claim 3, characterized in that: the addition amount of the GSH solution is 5mL.
5. The aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs according to claim 1, 2, 3 or 4, characterized in that: the reflux temperature is 80 ℃ and the reflux time is 24 hours.
6. The use of the aggregation-induced emission type gold nanocluster NAC/GSH-AuNCs according to claim 1 for detecting heavy metal ions and biological small molecules.
7. The use according to claim 6, characterized in that: the heavy metal ion is Ag + And/or Hg 2+ 。
8. The use according to claim 6, characterized in that: the biological small molecule is H 2 O 2 And/or GSH.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11760928B2 (en) * | 2021-07-06 | 2023-09-19 | Jiangnan University | Enhanced yellow-emitting carbon dots and its preparation method and application |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110300532A1 (en) * | 2009-03-05 | 2011-12-08 | Wilhelm Jahnen-Dechent | Control of the toxicity of gold nanoparticles |
| CN104749151A (en) * | 2015-04-08 | 2015-07-01 | 东南大学 | Application of glutathione-based stable gold nano cluster particles to detection of sulfhydryl compound |
| CN105675556A (en) * | 2016-01-06 | 2016-06-15 | 南京医科大学 | Method for detecting silver ions with glutathione-protected aggregation-induced emission type gold nanoclusters as fluorescent probe |
| CN106706607A (en) * | 2017-02-07 | 2017-05-24 | 福建医科大学 | High-quantum-yield electrochemiluminescence gold nano-cluster probe and preparation method of high-quantum-yield electrochemiluminescence gold nano-cluster probe |
| CN107044978A (en) * | 2017-02-07 | 2017-08-15 | 福建医科大学 | Glutathione electrogenerated chemiluminescence assay method based on gold nano cluster probe |
| US20190175753A1 (en) * | 2016-11-28 | 2019-06-13 | Shenzhen Profound-View Pharma Tech Co., Ltd | Application of AuCs or Substances Containing AuCs in the Preparation of Drugs for Preventing and/or Treating Glaucoma |
| CN110102344A (en) * | 2019-05-07 | 2019-08-09 | 国家纳米科学中心 | A kind of application of gold nanorods of cysteine modified as peroxidase |
| CN110669506A (en) * | 2019-09-25 | 2020-01-10 | 福建医科大学 | Preparation method of water-soluble gold nanocluster fluorescent material jointly protected by cysteamine and N-acetyl L-cysteine |
-
2022
- 2022-12-31 CN CN202211728707.5A patent/CN116064031A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110300532A1 (en) * | 2009-03-05 | 2011-12-08 | Wilhelm Jahnen-Dechent | Control of the toxicity of gold nanoparticles |
| CN104749151A (en) * | 2015-04-08 | 2015-07-01 | 东南大学 | Application of glutathione-based stable gold nano cluster particles to detection of sulfhydryl compound |
| CN105675556A (en) * | 2016-01-06 | 2016-06-15 | 南京医科大学 | Method for detecting silver ions with glutathione-protected aggregation-induced emission type gold nanoclusters as fluorescent probe |
| US20190175753A1 (en) * | 2016-11-28 | 2019-06-13 | Shenzhen Profound-View Pharma Tech Co., Ltd | Application of AuCs or Substances Containing AuCs in the Preparation of Drugs for Preventing and/or Treating Glaucoma |
| CN106706607A (en) * | 2017-02-07 | 2017-05-24 | 福建医科大学 | High-quantum-yield electrochemiluminescence gold nano-cluster probe and preparation method of high-quantum-yield electrochemiluminescence gold nano-cluster probe |
| CN107044978A (en) * | 2017-02-07 | 2017-08-15 | 福建医科大学 | Glutathione electrogenerated chemiluminescence assay method based on gold nano cluster probe |
| CN110102344A (en) * | 2019-05-07 | 2019-08-09 | 国家纳米科学中心 | A kind of application of gold nanorods of cysteine modified as peroxidase |
| CN110669506A (en) * | 2019-09-25 | 2020-01-10 | 福建医科大学 | Preparation method of water-soluble gold nanocluster fluorescent material jointly protected by cysteamine and N-acetyl L-cysteine |
Non-Patent Citations (1)
| Title |
|---|
| HAO-HUA DENG等: "Rational Design of High-Performance Donor−Linker−Acceptor Hybrids Using a Schiff Base for Enabling Photoinduced Electron Transfer", 《ANALYTICAL CHEMISTRY》, vol. 92, 19 December 2019 (2019-12-19), pages 2019 - 2026 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11760928B2 (en) * | 2021-07-06 | 2023-09-19 | Jiangnan University | Enhanced yellow-emitting carbon dots and its preparation method and application |
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