CN111595828B - Method for monitoring dissolution of nano zinc oxide - Google Patents

Method for monitoring dissolution of nano zinc oxide Download PDF

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CN111595828B
CN111595828B CN201910131126.5A CN201910131126A CN111595828B CN 111595828 B CN111595828 B CN 111595828B CN 201910131126 A CN201910131126 A CN 201910131126A CN 111595828 B CN111595828 B CN 111595828B
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zinc oxide
solution
nano zinc
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fluorescence spectrum
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CN111595828A (en
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王文雄
梁俊镒
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HKUST Shenzhen Research Institute
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material

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Abstract

The invention provides a method for monitoring dissolution of nano zinc oxide, which comprises the following steps: s1, dispersing nano zinc oxide particles into an experimental solution to obtain a monitored solution; s2, taking a corresponding test sample from the monitored solution at each monitoring moment; then adding a fluorescent probe material into the test sample, and detecting the test sample added with the fluorescent probe material by using a fluorescence spectrometer to obtain a fluorescence spectrum curve of the test sample; and finally, processing the fluorescence spectrum curve of the test sample to obtain the corresponding zinc ion concentration. The method for monitoring the dissolution of the nano zinc oxide can realize real-time monitoring of the dissolution process of the nano zinc oxide; simple operation and high sensitivity.

Description

Method for monitoring dissolution of nano zinc oxide
Technical Field
The invention relates to the field of environmental analytical chemistry, in particular to a method for monitoring dissolution of nano zinc oxide.
Background
Nano zinc oxide is an inorganic particle having a particle size of 1nm to 100nm, and exhibits many specific physicochemical properties, so that it is widely used in various fields such as rubber, cosmetics, textiles, and electronics industries. With the increasing production, use and treatment processes of nano zinc oxide in industry, the risk of discharging the nano particles to the water environment is increased, and the nano particles have potential influence on aquatic organisms. The main behaviors of the nano zinc oxide after entering the water environment are dissolution and agglomeration, and zinc ions can be dissolved out from the nano zinc oxide to the surrounding environment in the dissolution process. Various studies indicate that the toxicity of nano-zinc oxide to aquatic organisms is mainly due to the dissolved zinc ions. Therefore, understanding the dissolution process of nano zinc oxide in water environment is particularly important for performing ecotoxicological studies on nano zinc oxide.
The quantitative analysis of the dissolution of nano zinc oxide in Water environment by the combined technology of Ultrafiltration centrifugation (Centrifugal Ultrafiltration) and inductively coupled plasma mass spectrometry (ICP-MS) is a common method at present (Li, W. -M.and Wang, W. -X., water Research,2013,47, 895-902). In the ultrafiltration and centrifugation process, the eluted zinc ions are separated from the nano zinc oxide, and the concentration of the eluted zinc ions can be measured by using ICP-MS, thereby obtaining the elution degree of the nano zinc oxide. The technology has the advantage of high accuracy, but has certain limitation on the dissolution process of the nano zinc oxide. The dissolution process of the nano zinc oxide after entering the water environment is rapid, and the reaction balance can be achieved generally within about minutes to hours under different conditions (such as the size, the shape and the concentration of nano particles, the pH value of the water environment and the like), even the nano zinc oxide is completely dissolved. The process of ultrafiltration and centrifugation generally takes about 30 to 40 minutes, and the nano zinc oxide may reach reaction equilibrium in the process, so that the key dissolution process of the nano zinc oxide is difficult to derive from the method.
Recently, fluorescent probes have been widely used to monitor and measure metal ions (Carter, p.k., young, a.m. and Palmer, a.e., chemical Reviews,2014,114, 4564-4601), and are simple and convenient to operate while providing highly accurate results. The fluorescent probe is applied to monitoring the dissolution process of the nano zinc oxide in real time, and has important significance for researching the relation between the dissolution of the nano zinc oxide and the toxicity to organisms.
Disclosure of Invention
The invention provides a method for monitoring dissolution of nano zinc oxide aiming at the technical problems.
The technical scheme provided by the invention is as follows:
the invention provides a method for monitoring dissolution of nano zinc oxide, which comprises the following steps:
s1, dispersing nano zinc oxide particles into an experimental solution to obtain a monitored solution;
s2, taking a corresponding test sample from the monitored solution at each monitoring moment; then adding a fluorescent probe material into the test sample, and detecting the test sample added with the fluorescent probe material by using a fluorescence spectrometer to obtain a fluorescence spectrum curve of the test sample; and finally, processing the fluorescence spectrum curve of the test sample to obtain the corresponding zinc ion concentration.
In the above monitoring method of the present invention, the method for monitoring elution of nano zinc oxide further includes:
s0, detecting by using a fluorescence spectrometer to obtain a fluorescence spectrum curve of the fluorescent probe material under experimental solutions with different zinc ion concentrations, and recording the fluorescence spectrum curve as a fluorescence spectrum standard curve of the fluorescent probe material under the experimental solutions with different zinc ion concentrations;
the step S2 comprises the following steps:
and comparing the fluorescence spectrum curve of the test sample with the fluorescence spectrum standard curve to obtain the zinc ion concentration corresponding to the fluorescence spectrum curve of the test sample.
In the above monitoring method of the present invention, step S1 includes:
s11, adding nano zinc oxide particles into ultrapure water, and then performing ultrasonic dispersion to obtain a nano zinc oxide stock solution;
and S12, adding the nano zinc oxide stock solution into the experimental solution, and stirring to obtain the monitored solution.
In the above monitoring method of the present invention, step S0 includes:
dispersing zinc nitrate with different masses into the experimental solution to obtain the experimental solution with different zinc ion concentrations.
In the monitoring method of the invention, the experimental solution is a daphnia magna culture solution.
In the monitoring method of the invention, the daphnia magna culture solution comprises 2.29mM NaHCO 3 0.52mM MgSO 4 KCl 0.11mM and CaSO 0.70mM 4
In the monitoring method of the invention, the concentration of the nano zinc oxide stock solution is 1gZn/L.
In the above monitoring method of the present invention, the excitation wavelength detected by the fluorescence spectrometer is 373nm, and the emission wavelength detected by the fluorescence spectrometer is 380nm-580nm.
In the above monitoring method of the present invention, the fluorescent probe material is AMBPA.
The method for monitoring the dissolution of the nano zinc oxide utilizes the different fluorescence intensities of the fluorescent probe materials under different zinc ion concentrations to test the concentration of the zinc ions dissolved out of the nano zinc oxide, thereby realizing the monitoring of the dissolution of the nano zinc oxide. The method for monitoring the dissolution of the nano zinc oxide can realize real-time monitoring of the dissolution process of the nano zinc oxide; the operation is simple and convenient, and the result can be obtained in a short time only by putting the experimental solution into a fluorescence spectrometer; the sensitivity is high.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 shows a flow chart of a method for monitoring dissolution of nano zinc oxide according to a preferred embodiment of the present invention;
FIG. 2 shows the fluorescence spectrum of AMBPA in a methanol solution containing zinc ions, nano zinc oxide and neither;
FIG. 3 shows fluorescence spectra of AMBPA in experimental solutions with different zinc ion concentrations;
FIG. 4 shows a fit graph of AMBPA emission peak at 423nm with good linear relationship to different zinc ion concentrations;
fig. 5 shows a graph of the results of the concentration of zinc ions eluted from the nano zinc oxide at different monitoring times.
Detailed Description
The technical problem to be solved by the invention is as follows: the dissolving-out process of the nano zinc oxide after entering the water environment is rapid, and the reaction balance can be achieved generally within about several minutes to several hours under different conditions (such as the size, the shape and the concentration of nano particles, the pH value of the water environment and the like), even the nano zinc oxide is completely dissolved. The ultrafiltration and centrifugation process generally takes about 30 to 40 minutes, and the nano zinc oxide may reach the reaction equilibrium in the process, so that the key dissolution process of the nano zinc oxide is difficult to obtain from the method. The technical idea of the invention for solving the technical problem is as follows: the concentration of zinc ions dissolved out of the nano zinc oxide is tested by utilizing the different fluorescence intensities of the fluorescent probe materials under different zinc ion concentrations, so that the dissolution monitoring of the nano zinc oxide is realized.
Specifically, the invention provides a method for monitoring dissolution of nano zinc oxide, which comprises the following steps:
s1, dispersing nano zinc oxide particles into an experimental solution to obtain a monitored solution;
s2, taking a corresponding test sample from the monitored solution at each monitoring moment; then adding a fluorescent probe material (9-Anthrylmethyl-bis (2-picolyl) amine, (9-Anthrylmethyl) bis (2-pyridylmethyl) -amine, and detecting the test sample added with the fluorescent probe material by using a fluorescence spectrometer to obtain a fluorescence spectrum curve of the test sample; and finally, processing the fluorescence spectrum curve of the test sample to obtain the corresponding zinc ion concentration.
Further, in the present invention, the method for monitoring elution of nano zinc oxide further comprises:
s0, detecting by using a fluorescence spectrometer to obtain a fluorescence spectrum curve of the fluorescent probe material in experimental solutions with different zinc ion concentrations, and recording the fluorescence spectrum curve as a fluorescence spectrum standard curve of the fluorescent probe material in the experimental solutions with different zinc ion concentrations;
the step S2 comprises the following steps:
and comparing the fluorescence spectrum curve of the test sample with the fluorescence spectrum standard curve to obtain the zinc ion concentration corresponding to the fluorescence spectrum curve of the test sample.
Further, step S1 includes:
step S11, adding nano zinc oxide particles into ultrapure water, and then performing ultrasonic dispersion to obtain a nano zinc oxide stock solution;
and S12, adding the nano zinc oxide stock solution into the experimental solution, and then stirring to obtain the monitored solution.
Further, step S0 includes:
dispersing zinc nitrate with different masses into the experimental solution to obtain the experimental solution with different zinc ion concentrations.
Further, the experimental solution is a daphnia magna culture solution. Preferably, the daphnia magna culture solution comprises 2.29mM NaHCO 3 0.52mM MgSO 4 KCl 0.11mM and CaSO 0.70mM 4
Furthermore, the concentration of the nano zinc oxide stock solution is 1gZn/L.
Furthermore, the excitation wavelength detected by the fluorescence spectrometer is 373nm, and the emission wavelength detected by the fluorescence spectrometer is 380nm-580nm.
In order to make the technical purpose, technical solutions and technical effects of the present invention more clear and facilitate those skilled in the art to understand and implement the present invention, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, fig. 1 is a flow chart illustrating a method for monitoring elution of nano zinc oxide according to a preferred embodiment of the present invention, and the method for monitoring elution of nano zinc oxide includes the following steps:
preparation of test solutions
The experimental solution is daphnia magna culture solution comprising 2.29mM NaHCO 3 0.52mM MgSO 4 KCl 0.11mM and CaSO 0.70mM 4 . Meanwhile, the pH of the test solution was adjusted by 0.1M NaOH and 0.1M HCl, and in this example, the pH of the test solution was 8.2-8.4.
Preparation of nano zinc oxide stock solution
Adding a proper amount of 70nm nano zinc oxide particles into about 10mL of ultrapure water, and uniformly dispersing the nano zinc oxide particles into the ultrapure water through 30min of ultrasonic treatment, thereby preparing the nano zinc oxide stock solution with the concentration of 1g Zn/L.
Preparation of Zinc ion stock solution
Adding proper amount of zinc nitrate (Zn (NO) 3 ) 2 ) Dispersed into about 10mL of the experimental solution to prepare a zinc ion stock solution with a concentration of 1g Zn/L.
Confirmation of specificity of fluorescent Probe Material (AMBPA) for Zinc ions
Adding 2 muL AMBPA with the concentration of 10mM into 2mL of methanol solution containing zinc ions, nano zinc oxide and neither of the zinc ions and the nano zinc oxide respectively; the fluorescence characteristics of AMBPA under different conditions are measured by a fluorescence spectrometer (the excitation wavelength is 373nm, and the emission wavelength is 380nm-580 nm). The fluorescence characteristic of AMBPA under the influence of nano zinc oxide is the same as that of a blank group, and the AMBPA has an obvious emission peak in the presence of zinc ions, which shows that the AMBPA has better specificity on the zinc ions, as shown in figure 2.
Establishing the correlation between the zinc ion concentration and the AMBPA fluorescence characteristic
Preparing experimental solutions with different zinc ion concentrations by adopting a zinc ion stock solution and the experimental solutions; respectively adding 2 mu L of AMBPA with the concentration of 10mM into 2mL of experimental solutions with different zinc ion concentrations; the fluorescence characteristics of AMBPA under different zinc ion concentrations are measured by a fluorescence spectrometer (the excitation wavelength is 373nm, and the emission wavelength is 380-580 nm). Under different zinc ion concentrations, AMBPA has a strong emission peak at about 423nm, and the emission peak at 423nm has a good linear relationship with different zinc ion concentrations (y =0.8892x +43.6811 2 = 0.9997), as shown in fig. 3-4.
Experiment for monitoring dissolution process of nano zinc oxide in real time by using fluorescent probe
Adding 50 mu L of nano zinc oxide stock solution with the volume of 1g Zn/L into 100mL of experimental solution to prepare experimental solution containing 500 mu g Zn/L of nano zinc oxide; the experimental solution was gently stirred to ensure that the nano zinc oxide was uniformly dispersed in the experimental solution. At each monitoring time (e.g., 1 minute, 5 minutes, 10 minutes after the addition of nano zinc oxide \8230;) a volume of 2mL was taken from the test solution to the cuvette, and 2. Mu.L of AMBPA at a concentration of 10mM was added to the cuvette; the fluorescence characteristics of AMBPA in the experimental solution were measured by fluorescence spectrometer (excitation wavelength 373nm, emission wavelength 380nm-580 nm).
Determination of concentration of zinc ions dissolved out from nano zinc oxide
In the experimental solution, AMBPA has a strong emission peak (I) at about 423nm 423 ) Using the previously established linear relationship between zinc ion concentration and AMBPA fluorescence characteristics, I can be expressed 423 The concentration of zinc ions dissolved out from the nano zinc oxide is obtained at each monitoring time by converting the concentration of zinc ions into the corresponding concentration of zinc ions, as shown in fig. 5.
Compared with the traditional method, the method for monitoring the dissolution process of the nano particles in real time by using the fluorescent probe is simpler, more convenient and faster, and has high sensitivity, and particularly for nano zinc oxide with higher dissolution speed, the fluorescent probe technology can accurately describe the key dissolution process.
Fluorescent probes have been widely used in various fields as an index, including for measuring various metal ions. Fluorescent probes are typically optimized to be specific for a particular metal ion to reduce interference with other metal ions. The interaction between the fluorescent probe (AMBPA) with specificity to zinc ions and the zinc ions can generate fluorescence, and the linear relation between the zinc ions with different concentrations and the fluorescence characteristics of the AMBPA can be established by utilizing the intensity change of the fluorescence generated by the zinc ions with different concentrations to the AMBPA with constant concentration. And the characteristic that the fluorescence characteristic of the AMBPA is not changed in the presence of the nano zinc oxide is proved, so that the fluorescence change of the AMBPA used for monitoring the dissolution of the nano zinc oxide is from dissolved zinc ions, and the feasibility of applying the AMBPA to monitoring the dissolution process of the nano zinc oxide in real time is established. The concentration of zinc ions dissolved out from the nano zinc oxide at each time point can be obtained by adding the AMBPA into an experimental solution containing the nano zinc oxide at each target time point and corresponding the fluorescence intensity measured by a fluorescence spectrometer to the previously established linear relationship between the zinc ions with different concentrations and the fluorescence characteristics of the AMBPA. Based on the sample processing and determination process is rapid, the real-time monitoring of the dissolution process of the nano zinc oxide can be realized.
The invention provides a rapid and accurate analysis method, which can realize real-time monitoring of the dissolution process of the nano zinc oxide; compared with the prior art, the method has the following advantages:
1. the method requires lower instrument cost;
2. the method has quick treatment time on the experimental solution, and can realize real-time monitoring on the dissolution process of the nano zinc oxide;
3. the method is simple and convenient to operate, and results can be obtained in a short time only by putting the experimental solution into a fluorescence spectrometer;
4. high sensitivity, and the detection limit of AMBPA to zinc ions can be as low as 10 mug/L.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.

Claims (6)

1. A method for monitoring dissolution of nano zinc oxide is characterized by comprising the following steps:
s1, dispersing nano zinc oxide particles into an experimental solution to obtain a monitored solution;
s2, taking a corresponding test sample from the monitored solution at each monitoring moment; then adding a fluorescent probe material into the test sample, and detecting the test sample added with the fluorescent probe material by using a fluorescence spectrometer to obtain a fluorescence spectrum curve of the test sample; finally, the concentration of zinc ions corresponding to the fluorescence spectrum curve of the test sample is obtained by processing the fluorescence spectrum curve;
the experimental solution is daphnia magna culture solution comprising 2.29mM NaHCO 3 0.52mM MgSO 4 KCl 0.11mM and CaSO 0.70mM 4 (ii) a The pH value adopted by the experimental solution is 8.2-8.4;
the fluorescent probe material was 10mM (9-anthracenemethyl) -bis (2-picolyl) amine.
2. The monitoring method according to claim 1, further comprising, before step S1, step S0; step S0 is: detecting by using a fluorescence spectrometer to obtain a fluorescence spectrum curve of the fluorescent probe material in experimental solutions with different zinc ion concentrations, and recording the fluorescence spectrum curve as a fluorescence spectrum standard curve of the fluorescent probe material in the experimental solutions with different zinc ion concentrations;
the step S2 comprises the following steps:
and comparing the fluorescence spectrum curve of the test sample with the fluorescence spectrum standard curve to obtain the zinc ion concentration corresponding to the fluorescence spectrum curve of the test sample.
3. The monitoring method according to claim 2, wherein step S1 comprises:
step S11, adding nano zinc oxide particles into ultrapure water, and then performing ultrasonic dispersion to obtain a nano zinc oxide stock solution;
and S12, adding the nano zinc oxide stock solution into the experimental solution, and then stirring to obtain the monitored solution.
4. The monitoring method according to claim 2, wherein step S0 comprises:
dispersing zinc nitrate with different masses into the experimental solution to obtain the experimental solution with different zinc ion concentrations.
5. The method of claim 3, wherein the stock solution of nano zinc oxide has a concentration of 1gZn/L.
6. The method of claim 1, wherein the fluorescence spectrometer detects an excitation wavelength of 373nm and an emission wavelength of 380nm to 580nm.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2631832A1 (en) * 2005-12-21 2007-06-28 Boehringer Ingelheim International Gmbh Improved process for the preparation of 4-(benzimidazolylmethylamino)-benzamides and the salts thereof
CN105284740A (en) * 2015-10-27 2016-02-03 长江大学 Method for quickly identifying sex of young daphnia of daphnia magna
CN106442456A (en) * 2016-11-25 2017-02-22 清华大学 Method of detecting zinc ions by utilizing near-infrared second region fluorescence quantum dot probe

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2631832A1 (en) * 2005-12-21 2007-06-28 Boehringer Ingelheim International Gmbh Improved process for the preparation of 4-(benzimidazolylmethylamino)-benzamides and the salts thereof
CN105284740A (en) * 2015-10-27 2016-02-03 长江大学 Method for quickly identifying sex of young daphnia of daphnia magna
CN106442456A (en) * 2016-11-25 2017-02-22 清华大学 Method of detecting zinc ions by utilizing near-infrared second region fluorescence quantum dot probe

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Distinct biokinetic behavior of ZnO nanoparticles in Daphnia magna quantified by synthesizing 65Zn tracer;Wei-Man Li et al.;《Water Research》;20121120;895-902 *
食品中氧化锌纳米颗粒与其他食品添加剂的复合毒性研究;袁露露;《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》;20160315(第3期);B024-52 *

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