CN104237185B - PH value measurement method based on N-acetyl-L-cysteine-gold nanocluster - Google Patents
PH value measurement method based on N-acetyl-L-cysteine-gold nanocluster Download PDFInfo
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- CN104237185B CN104237185B CN201410464563.6A CN201410464563A CN104237185B CN 104237185 B CN104237185 B CN 104237185B CN 201410464563 A CN201410464563 A CN 201410464563A CN 104237185 B CN104237185 B CN 104237185B
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Abstract
The invention discloses a pH value measurement method based on an N-acetyl-L-cysteine-gold nanocluster, and in particular relates to a method for measuring the pH value of a solution with the N-acetyl-L-cysteine-gold nanocluster sensitive to pH as a fluorescence probe. The method is characterized in that the pH value of a solution is measured according to the change of a feature of a solution fluorescence emission spectrum of the N-acetyl-L-cysteine-gold nanocluster under the condition of different pH values. The linear measurement range is 6.05-6.4. The pH value measurement method can be used for high-sensitivity pH measurement in an environment and life science system.
Description
Technical field
The present invention relates to pH sensitivity N-acetyl-L-cysteine-gold nano cluster and its pH value of solution as fluorescent probe
Values determination method, belongs to analytical chemistry and field of nanometer technology.
Background technology
PH value is a conventional important indicator in chemistry and biosystem, and it affects its many chemical reaction and biochemistry
Reaction.Medically, the change of internal pH value develops along with a lot of diseases.Therefore, the mensure of pH value is in chemistry and life
Thing field has great importance.At present, the measuring method of pH is broadly divided into indicator method, metal electrode method（Hydrogen electeode method, quinone
Quinhydrone electrode method, antimony electrode method）With glass electrode method etc..The assay method developing new pH value of solution is still particularly significant.
Nano material provides new opportunity due to its unique physics and optical property for the structure of pH sensor.In recent years
Come, many nano materials, including polymer nano granules, graphene oxide, single, nano SiO 2 particle, amount
Sub- point, gold nano grain and magnetic nanoparticle etc., have been reported with pH response property.Recently, some metal nano groups
Clustered materials（As copper nanocluster, ag nano-cluster, gold copper nanocluster）Also it is found to have the property sensitive to pH value of solution
Matter.
The present invention, using the sensitive N-acetyl-L-cysteine-gold nano cluster of pH as fluorescent probe, establishes pH value of solution
The new method that value measures.
Content of the invention
It is an object of the invention to provide a kind of N-acetyl-L-cysteine-gold nano cluster sensitive based on pH and its work
Solution ph assay method for fluorescent probe.
To achieve these goals, the present invention employs the following technical solutions：
The sensitive fluorescence gold nano cluster of pH of the present invention, is characterized in that being made up of following reactions steps：By concentration
N-acetyl-L-cysteine solution for 0.02 ~ 0.18 mol/L and concentration are the sodium hydroxide solution of 0.1 ~ 0.8 mol/L
It is added in the chlorauric acid solution that concentration is 0.01 ~ 0.1 g/L, mixes, be placed in 20 ~ 70 °C of constant temperature water baths and react 0 ~ 3.5 hour,
React the bag filter being 3500 with molecular cut off after terminating and dialysis purification process is carried out to reactant liquor, obtain N- acetyl-L- half
Cystine-fluorescent au nanocluster material aqueous solution, described N-acetyl-L-cysteine-fluorescent au nanocluster material is water-soluble
The fluorescent characteristicss of liquid change with the pH value of solution and change.
The present invention is with N-acetyl-L-cysteine as reducing agent and protective agent preparation.
Reduce the method preparation of gold chloride using N-acetyl-L-cysteine：The hydrogen that 0.6 mL concentration is 0.5 mol/L
Sodium hydroxide solution and 0.4 mL concentration are that the chlorauric acid solution of 0.02 g/L is added to the N- second that 4 mL concentration are 0.08 mol/L
In acyl-L-Cysteine solution, mix, be placed in 37 °C of constant temperature water baths and react 2.5 hours, reactant liquor is changed into no from light yellow
Color, reacts the bag filter being 3500 with molecular cut off after terminating and carries out purification process to reactant liquor, obtain N- acetyl-L- half Guang
Propylhomoserin-gold nano cluster solution；4 °C of dark places preserve, and can keep the relatively stable of at least one month.
The sensitive fluorescence gold nano cluster of pH of the present invention, can produce red fluorescence, maximum excitation wavelength is
335nm, maximum emission wavelength is 650nm.
The pH value assay method of N-acetyl-L-cysteine-gold nano cluster of the present invention, is characterized in that utilizing N-
The change of acetyl-L-Cysteine-gold nano cluster fluorescence emission spectrum signature in different pH value, to measure solution ph.
Using emitted luminescence intensity value at 650 nm for the N-acetyl-L-cysteine-gold nano cluster（F650）Molten to judge
Liquid pH value.
The excitation wavelength being used is 355 nm.
F in 6.05 ~ 6.4 pH value range650Linear with solution ph.
After N-acetyl-L-cysteine-gold nano cluster fluorescent quenching, N-acetyl-L-cysteine-gold nano cluster
Zeta electric potential reduces, and particle diameter increases, but the valence state of gold does not change.
Specifically, the technical solution used in the present invention is：
（One）The preparation of fluorescent au nanocluster material
Used in procedure below, all glass drying ovens all soak through chloroazotic acid, and use distilled water thoroughly cleaning, dry.Gold
The preparation method of nanocluster fluorescent material is as follows：By 0.6 mL concentration be 0.5 mol/L sodium hydroxide solution and 0.4 mL
Concentration is that the chlorauric acid solution of 0.02 g/L is added to the N-acetyl-L-cysteine solution that 4 mL concentration are 0.08 mol/L
In, mix, be placed in 37 °C of constant temperature water baths and react 2.5 hours, reactant liquor is become colorless by light yellow.Reaction is used after terminating and is divided
The bag filter that son is measured as 3500 carries out purification process to reactant liquor, and gold nano cluster solution after purification is positioned over 4 °C of refrigerators and keeps away
Light preserves.
（Two）The mensure of solution ph：
0.2 milliliter of step is added in 0.2 milliliter of sample solution（One）Preparation gold nano cluster solution, after mix homogeneously
25 °C are reacted 10 minutes.After reaction terminates, with 355 nm as excitation wavelength, measure the emitted luminescence intensity value at 650 nm
（F650）, by F650Standard curve carries out the mensure of pH.
Advantages of the present invention：
（1）It is probe that the present invention uses the gold nano cluster material of N-acetyl-L-cysteine protection, the changing of solution ph
Become and be converted into optical signal it is easy to perusal and Instrument measuring.
（2）The gold nano cluster material of the N-acetyl-L-cysteine protection that the present invention uses itself has pH response
Property is it is not necessary to any front modification step.
（3）Method constructed by the present invention measures sensitivity height, and response range is 0.35 pH.
（4）The pH response interval of the method constructed by the present invention is in physiological change scope（5.0~7.4）Within, it is more beneficial for
It is applied to biology, medical science and pharmaceutical field.
Brief description
Fig. 1 is outside drawing under uviol lamp for the gold nano cluster solution under different pH condition.In figure：（A）pH=6.0；
（B）pH=6.5.
Fig. 2 is the launching light spectrogram of gold nano cluster solution under different pH condition.In figure：（A）pH=6.0；（B）pH=
6.5.
Fig. 3 is the UV-visible absorption spectrum of gold nano cluster solution under different pH condition.
Fig. 4 is the x-ray photoelectron energy spectrum diagram of gold nano cluster solution under different pH condition.In figure：（A）pH=6.0；
（B）pH=6.5.
Fig. 5 is the Zeta electric potential figure of gold nano cluster solution under different pH condition.In figure：（A）pH=6.0；（B）pH=
6.5.
Fig. 6 is the dynamic light scattering diagram of gold nano cluster solution under different pH condition.In figure：（A）pH=6.0；（B）pH=
6.5.
Fig. 7 is the emitted luminescence intensity value of gold nano cluster solution（F650）Graph of a relation and solution ph between.
Fig. 8 is the emitted luminescence intensity value of gold nano cluster solution（F650）Linear relationship chart and solution ph between.
Specific embodiment
Example 1：
The preparation process of fluorescent au nanocluster material is as follows：The sodium hydroxide that 0.6 mL concentration is 0.5 mol/L is molten
Liquid and the chlorauric acid solution that 0.4 mL concentration is 0.02 g/L are added to N- acetyl-L- half Guang that 4 mL concentration are 0.08 mol/L
In propylhomoserin solution, mix, be placed in 37 °C of constant temperature water baths and react 2.5 hours.React the retention molecule of the reactant liquor after terminating
Measure the bag filter for 3500 and carry out dialysis purification process.It is colourless under obtained gold nano cluster solution visible ray, uviol lamp
Irradiate the strong red fluorescence of lower generation.4 °C of dark places preserve, and can keep the relatively stable of at least one month.
Example 2：
The gold nano cluster solution obtained by 0.2 milliliter of example 1 is taken to be added to the phosphoric acid of 0.2 milliliter of pH=6.0 and pH=6.5
Salt buffer solution（20 mmol/L）In, it is placed in isothermal reaction 10 minutes in 25 °C of water-baths after mix homogeneously.Under uviol lamp
Observe, gold nano cluster solution manifests red fluorescence in pH=6.0（A in Fig. 1）, and red fluorescence occurs in pH=6.5
Quenching（B in Fig. 1）.Fig. 2 is gold nano cluster solution in pH=6.0（A in Fig. 2）And pH=6.5（B in Fig. 2）When glimmering
Optical emission spectroscopy figure.
Example 3：
The gold nano cluster solution obtained by 0.2 milliliter of example 1 is taken to be added to the phosphate-buffered of 0.2 milliliter of different pH value
Solution（20 mmol/L）In, it is placed in isothermal reaction 10 minutes in 25 °C of water-baths after mix homogeneously.After reaction terminates, measure it
UV-visible absorption spectrum.From the figure 3, it may be seen that the rising with pH（On the left of in figure arrow, the numerical value of instruction is pH value）, Jenner
The backscatter of rice cluster solution is gradually increased, and shows that gold nano cluster there occurs gathering with the rising of pH.
Example 4：
The gold nano cluster solution obtained by 0.2 milliliter of example 1 is taken to be added to the phosphoric acid of 0.2 milliliter of pH=6.0 or pH=6.5
Salt buffer solution（20 mmol/L）In, it is placed in isothermal reaction 10 minutes in 25 °C of water-baths after mix homogeneously.After reaction terminates,
Freeze-drying process obtains gold nano cluster powder, takes gained powder to carry out X-ray photoelectron spectroscopic analysis.As shown in Figure 4, Jenner
The rice valence state in pH6.0 with pH6.5 for the cluster is identical.（A in Fig. 4 is the Au 4f figure of gold nano cluster during pH6.0；In Fig. 4
B be pH6.5 when gold nano cluster Au 4f figure）.
Example 5：
The gold nano cluster solution obtained by 0.2 milliliter of example 1 is taken to be added to the phosphoric acid of 0.2 milliliter of pH=6.0 or pH=6.5
Salt buffer solution（20 mmol/L）In, it is placed in isothermal reaction 10 minutes in 25 °C of water-baths after mix homogeneously.Take reacted molten
Liquid carries out Zeta electric potential analysis.As shown in Figure 5, during pH6.5, the Zeta electric potential of gold nano cluster reduces.（A in Fig. 5 is pH6.0
When gold nano cluster Zeta electric potential figure, the B in Fig. 5 be pH6.5 when gold nano cluster Zeta electric potential figure）.
Example 6：
The gold nano cluster solution obtained by 0.2 milliliter of example 1 is taken to be added to the phosphoric acid of 0.2 milliliter of pH=6.0 or pH=6.5
Salt buffer solution（20 mmol/L）In, it is placed in isothermal reaction 10 minutes in 25 °C of water-baths after mix homogeneously.Take reacted molten
Liquid carries out dynamic scattering analysis.It will be appreciated from fig. 6 that the particle diameter of gold nano cluster significantly increases during pH6.5.（A in Fig. 6 is
The dynamic light scattering diagram of gold nano cluster during pH6.0, the B in Fig. 6 is the dynamic light scattering diagram of gold nano cluster during pH6.5）.
Example 7：
0.2 milliliter of different pH value is added in the gold nano cluster that 0.2 milliliter of embodiment 1 is obtained（5.5~7.5）Phosphoric acid
Salt buffer（20 mmol/L）In, 25 °C are reacted 10 minutes, measure solution emitted luminescence intensity value F650.As shown in fig. 7, pH value of solution
During for 5.5 ~ 6.0, F650Change is inconspicuous；When pH value of solution is 6.05 ~ 6.5, F650Drastically decline；When pH value of solution is more than 6.50, F650
Tend towards stability.
Example 8：
0.2 milliliter of different pH value is added in the gold nano cluster that 0.2 milliliter of embodiment 1 is obtained（6.05~6.4）Phosphoric acid
Salt buffer（20 mmol/L）In, 25 °C are reacted 10 minutes, measure solution emitted luminescence intensity value F650.As shown in figure 8,6.05
F in the range of ~ 6.4pH value650Linear with solution ph, linear equation is F=17.53-2.73pH, r=0.998.To pH=
The relative standard deviation that 6.1 solution parallel assay is 6 times is 2.3%.
Claims (8)
1. a kind of sensitive fluorescence gold nano cluster of pH, is characterized in that being made up of following reactions steps：Concentration is 0.1 ~ 0.8
The sodium hydroxide solution of mol/L and the chlorauric acid solution that concentration is 0.01 ~ 0.1 g/L are added to concentration for 0.02 ~ 0.18 mol/
In the N-acetyl-L-cysteine solution of L, mix, be placed in 20 ~ 70 °C of constant temperature water baths and react 2.5 hours, reaction is used after terminating
Molecular cut off is that 3500 bag filter carries out dialysis purification process to reactant liquor, obtains N-acetyl-L-cysteine-gold nano
Cluster fluorescent material aqueous solution, the water-soluble liquid energy of described N-acetyl-L-cysteine-fluorescent au nanocluster material produces red glimmering
Light, maximum excitation wavelength is 335nm, and maximum emission wavelength is 650nm, and described N-acetyl-L-cysteine-gold nano cluster is glimmering
The fluorescent characteristicss of luminescent material aqueous solution change with the pH value of solution and change, in 6.05 ~ 6.4 pH value range at 650 nm
Emitted luminescence intensity value F650Linear with solution ph.
2. the sensitive fluorescence gold nano cluster of pH according to claim 1, it is characterized in that with N-acetyl-L-cysteine be
Reducing agent and protective agent preparation.
3. the sensitive fluorescence gold nano cluster of pH according to claim 1 and 2, is characterized in that using N- acetyl-L- half Guang
Propylhomoserin reduces the method preparation of gold chloride：The sodium hydroxide solution that 0.6 mL concentration is 0.5 mol/L with 0.4 mL concentration is
The chlorauric acid solution of 0.02 g/L is added in the N-acetyl-L-cysteine solution that 4 mL concentration are 0.08 mol/L, mixes,
It is placed in 37 °C of constant temperature water baths and reacts 2.5 hours, reactant liquor is become colorless by light yellow, reaction uses molecular cut off after terminating
Bag filter for 3500 carries out purification process to reactant liquor, obtains N-acetyl-L-cysteine-gold nano cluster solution；4 °C dark
Place preserves, and can keep the relatively stable of at least one month.
4. a kind of pH value assay method of the fluorescence gold nano cluster sensitive based on the arbitrary described pH of claim 1-3, it is special
Levying is change using N-acetyl-L-cysteine-gold nano cluster fluorescence emission spectrum signature in different pH value, to measure
Solution ph.
5. the pH value assay method of the fluorescence gold nano cluster sensitive based on pH according to claim 4, is characterized in that profit
With emitted luminescence intensity value at 650 nm for the N-acetyl-L-cysteine-gold nano cluster（F650）To judge solution ph.
6. the pH value assay method of the fluorescence gold nano cluster sensitive based on pH according to claim 4 or 5, is characterized in that
The excitation wavelength being used is 355 nm.
7. the pH value assay method of the fluorescence gold nano cluster sensitive based on pH according to claim 4 or 5, is characterized in that
F in 6.05 ~ 6.4 pH value range650Linear with solution ph.
8. the pH value assay method of the fluorescence gold nano cluster sensitive based on pH according to claim 4 or 5, is characterized in that
After N-acetyl-L-cysteine-gold nano cluster fluorescent quenching, the Zeta electric potential of N-acetyl-L-cysteine-gold nano cluster
Reduce, particle diameter increases, but the valence state of gold does not change.
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| CN105670612B (en) * | 2016-02-26 | 2017-09-05 | 湖北大学 | A kind of preparation method of the fluorescence nano copper cluster gel sensitive to pH |
| CN106872546B (en) * | 2017-02-07 | 2018-12-04 | 福建医科大学 | Electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe |
Citations (3)
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| CN101875132A (en) * | 2010-05-31 | 2010-11-03 | 武汉大学 | Method for bionically preparing water-soluble gold nanoclusters |
| CN103196883A (en) * | 2013-04-19 | 2013-07-10 | 中国科学院化学研究所 | Method for detecting activity of chymotrypsin by adopting gold nanoclusters |
| CN103616363A (en) * | 2013-12-08 | 2014-03-05 | 福建医科大学 | Copper ion rapid determination method adopting gold nanocluster protected by methionine as fluorescent probe |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875132A (en) * | 2010-05-31 | 2010-11-03 | 武汉大学 | Method for bionically preparing water-soluble gold nanoclusters |
| CN103196883A (en) * | 2013-04-19 | 2013-07-10 | 中国科学院化学研究所 | Method for detecting activity of chymotrypsin by adopting gold nanoclusters |
| CN103616363A (en) * | 2013-12-08 | 2014-03-05 | 福建医科大学 | Copper ion rapid determination method adopting gold nanocluster protected by methionine as fluorescent probe |
Non-Patent Citations (2)
| Title |
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| Same ligand-Different binding: A Way to control the binding of N-acetyl-cystein (NAC) to Pt clusters;Sebastian Kunz等;《Journal of Colloid and Interface Science》;20140419(第426期);第267页第2栏第1段-第268页第1栏第1段 * |
| 新型荧光金纳米粒子的制备及Cu2+检测;汪松美，宋晓朋;《安徽农业大学学报》;20130228;第40卷(第1期);第156页第1栏第4段-第157页第1栏第1段，及图3 * |
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