CN109187775B - Solid-phase micro-extraction probe of nanogold-modified wood stick and application thereof - Google Patents
Solid-phase micro-extraction probe of nanogold-modified wood stick and application thereof Download PDFInfo
- Publication number
- CN109187775B CN109187775B CN201810778221.XA CN201810778221A CN109187775B CN 109187775 B CN109187775 B CN 109187775B CN 201810778221 A CN201810778221 A CN 201810778221A CN 109187775 B CN109187775 B CN 109187775B
- Authority
- CN
- China
- Prior art keywords
- solid
- nanogold
- wood stick
- modified wood
- probe
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a solid-phase micro-extraction probe of a nanogold-modified wood stick and application thereof. The solid-phase micro-extraction probe of the nanogold-modified wood stick comprises a carrier and an adsorption material, wherein the carrier is a wood stick material with a porous surface, the adsorption material is gold nanoparticles, and the adsorption material is attached to a pore channel on the surface of the carrier through van der Waals force. The process for preparing the nanogold modified wood stick solid-phase micro-extraction probe is simple and rapid, low in preparation difficulty, convenient in material obtaining and low in cost, and the solid-phase micro-extraction probe prepared by the method has the characteristics of strong enrichment capacity, good reproducibility and the like.
Description
Technical Field
The invention belongs to the field of environmental analytical chemistry, and relates to a solid-phase micro-extraction probe of a nanogold-modified wood stick and application thereof.
Background
Mercury is a persistent toxic pollutant which has great influence on human health, and after the Japanese outbreak of the last 50 th century "water break" illness ", the environmental pollution problem of mercury is greatly concerned globally. Human mercury exposure is mainly from dietary mercury-contaminated water and mercury-contaminated fish. Mercury levels of about 50% in 100,000 sweden lakes have been reported to exceed international health limits, resulting in local government recommendations that pregnant women do not eat fish in sweden lakes. Therefore, the mercury pollution monitoring of the water body is very important and is a prerequisite for environmental evaluation and effective treatment.
The content of mercury ions entering the water environment is extremely low, but the mercury ions can be converted into methyl mercury with higher toxicity and biological enrichment and amplification capacity under the action of microorganisms or photochemistry, so that a method for quickly detecting trace mercury ions in water is needed to be developed. At present, atomic fluorescence spectroscopy and inductively coupled plasma mass spectrometry are main instrument means for mercury detection, and have the characteristics of high sensitivity, good selectivity and the like, but the atomic fluorescence spectroscopy and inductively coupled plasma mass spectrometry are extremely expensive, large in size, required to be equipped with special carrier gas and poor in portability, so that the atomic fluorescence spectroscopy and inductively coupled plasma mass spectrometry are not suitable for field or field application.
Solid Phase Micro Extraction (SPME) is a sample pretreatment method following the green chemical principle, has the characteristics of simple operation, rapidness, sensitivity, capability of being used together with a portable instrument and simultaneously realizing the collection, separation, concentration and analysis of a sample, and the like, and is very suitable for the field in-situ sampling analysis of mercury in water. Currently SPME technology has been successfully applied to the analysis of mercury in environmental, food and biological samples. However, commercial extraction heads generally have the defects of high cost (about 900 yuan/count), limited service life (about 100-300 times), incapability of replacing the extraction heads after the extraction capacity of the fiber coatings is reduced, scrapping of the whole extraction heads, incapability of recycling and the like, and the application of the extraction heads in daily environmental monitoring of mercury is severely limited. Therefore, research groups at home and abroad develop novel SPME extraction fibers with higher coating material adsorption performance and lower probe preparation cost. The gold nanoparticles gradually become a preferred adsorption material for preparing the SPME probe special for mercury by virtue of unique physicochemical characteristics, such as high specific surface area, remarkable amalgamation effect and the like. However, in an experiment, a gold layer is usually formed on a stainless steel or other metal wire substrate by adopting technologies such as electroplating, spraying, vapor deposition and the like, the preparation process is complicated, the time consumption is long (1-2 hours), the preparation cost is high, and the special mercury SPME probe is difficult to popularize and apply on a large scale in practical analysis.
Disclosure of Invention
The invention aims to provide a solid-phase micro-extraction probe of a nanogold-modified wood stick and application thereof.
In order to achieve the above object, the technical solution of the present invention is as follows:
the invention provides a solid-phase micro-extraction probe of a nanogold-modified wood stick, which comprises a carrier and an adsorption material, wherein the carrier is a wood stick material with a porous surface, the adsorption material is gold nanoparticles, and the adsorption material is attached to a pore channel on the surface of the carrier through van der Waals force. The diameter of the tip of the wood stick carrier material is 0.3-0.5 mm.
The invention also provides a preparation method of the solid-phase micro-extraction probe of the nanogold-modified wood stick, which comprises the following steps:
(1) reducing chloroauric acid by using sodium borohydride to prepare a nano gold solution;
(2) selecting a wood stick with the length of 2-5 cm and the tip diameter of 0.3-0.5 mm as a carrier;
(3) and (3) completely immersing the wood stick in the step (2) into the nano-gold solution prepared in the step (1), keeping for 1.0-20 min, taking out, and standing for 10-30 min at room temperature to obtain the solid-phase micro-extraction probe of the nano-gold modified wood stick.
In practice, a commercial two-tipped wood toothpick without any treatment (about 5cm in length, about 2mm in diameter, and about 0.5mm in diameter at the tip) was selected and broken off from the middle to obtain two-segment one-tipped wood toothpicks as the nano-gold particle carrier.
The invention selects the wood toothpick and the nano-gold particles as a supporting medium and a mercury selective adsorption material respectively. Firstly, nano-gold particles are embedded into a pore canal of the surface of a wood stick in three-dimensional communication through a physical soaking method, a novel nano-gold modified wood stick solid-phase micro-extraction probe which is low in cost, good in stability and strong in enrichment capacity and is suitable for headspace enrichment of mercury in water is prepared, headspace extraction enrichment of mercury in water is carried out, and rapid detection of trace mercury in water is realized through combination with a portable mercury detector.
Preferably, the specific preparation steps of the nanogold solution in the step (1) are as follows: adding ultrapure water and a sodium citrate solution into chloroauric acid at room temperature, stirring for 5-10 min, dropwise adding a sodium borohydride solution into the mixed solution, gradually changing the solution into wine red from light yellow, and continuing stirring for 7-15 min after the solution added with sodium borohydride becomes wine red, so as to obtain the nano-gold solution.
Preferably, the concentration of the nanogold prepared by the sodium borohydride reduction method is 150-200 mg/L.
The invention also provides application of the solid-phase micro-extraction probe of the nanogold-modified wood stick, and the solid-phase micro-extraction probe is particularly applied to determination of mercury ions in a water sample. The method for determining the mercury ions in the water sample is very suitable for large-scale field application scenes, the probe and the portable instrument are convenient to operate and use, the portable emergency monitoring requirement of field trace amount of mercury can be met, and the method has wide application potential and market popularization prospect.
Preferably, the determination of mercury ions in a water sample comprises the following steps:
(1) measuring 5.0-10.0 mL of mercury standard solution or water sample to be detected in a headspace bottle, adding 0.5-1.0 mL of stannous chloride solution with the mass fraction of 1% -10%, and quickly screwing down a headspace bottle cap;
(2) penetrating the prepared solid-phase microextraction probe through a silica gel diaphragm pad on the headspace bottle cap, wherein the length of a wood stick carrier of the solid-phase microextraction probe exposed outside the headspace bottle is 5.0-20 mm, and extracting the headspace bottle at an oscillation speed of 150-300 r/min for 5.0-30 min;
(3) and taking out the solid-phase micro-extraction probe after the enrichment in the headspace bottle, and measuring mercury ions.
Preferably, the specific determination step of step (3) is: and taking out the solid-phase micro-extraction probe of the nanogold-modified wood stick after the enrichment of the headspace bottle is finished, transferring the solid-phase micro-extraction probe of the nanogold-modified wood stick to a quartz sample-feeding boat of a thermal desorption module of the portable mercury detector, and determining mercury ions, wherein the thermal desorption temperature is set to be 680-740 ℃, the thermal desorption is carried out for 1min, the airflow velocity is 0.8-1.2L/min, and the quantity is determined by an external standard method.
The invention has the beneficial effects that:
(1) the invention adopts nano gold particles with super-strong mercury binding capacity as an adsorbent, and the nano gold particles are embedded into three-dimensional communicating pore channels on the surface of a commercial wooden toothpick in a physical dipping mode to prepare the novel solid-phase micro-extraction probe. And the headspace mode is adopted for extraction, so that the mercury enrichment efficiency and the matrix interference resistance in water are greatly improved.
(2) The process for preparing the nanogold modified wood stick solid-phase micro-extraction probe is simple and rapid, low in preparation difficulty, convenient in material obtaining and low in cost, and the solid-phase micro-extraction probe prepared by the method has the characteristics of strong enrichment capacity, good reproducibility and the like. In addition, the solid phase micro-extraction probe prepared by the invention is disposable, can be used at any time, is convenient and quick, is easy to carry, and simultaneously overcomes the problems of mercury residue on the probe and the like.
(3) The solid phase micro-extraction probe prepared by the invention is combined with a portable mercury detector, is convenient to operate and use, can be suitable for on-site, rapid, accurate and portable emergency monitoring of mercury in water, and has wide application potential and market popularization prospect.
Description of the drawings:
FIG. 1 is an SEM image of the surface of a wood toothpick loaded with nano-gold particles in example 1, wherein the image A is an SEM image magnified by 20 times, the image B is an SEM image magnified by 100 times, and the image C is an SEM image magnified by 500 times;
FIG. 2 is a spectrum of the wood toothpick with gold nanoparticles loaded on the surface in example 1;
FIG. 3 is the optimized result of the extraction conditions of the micro-extraction probe of example 4, wherein a is the influence of oscillation speed on the extraction efficiency, b is the influence of extraction temperature on the extraction efficiency, c is the examination of extraction equilibrium time, and d is the influence of solution pH and salinity on the extraction efficiency;
FIG. 4 is a graph of atomic absorption spectra of standard solutions of mercury at a concentration of 1 μ g/L using 8 solid phase microextraction probes prepared in example 1 in combination with a portable mercury porosimeter using headspace extraction.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.
Unless otherwise specified, reagents, raw materials and equipment used in the present invention are commercially available from the public.
Reagent: mercury Standard solution (1000mg/L, National Standard Material Centre of China, China); chloroauric acid, sodium citrate, sodium borohydride, stannous chloride (Aladdin Chemical co., ltd., China).
Raw materials: wood pick (birch toothpick).
The instrument comprises the following steps: portable mercury analyzer, available from Lumex corporation (russia), model: RA-915+(containing PYRO-915)+Thermal desorption module). The technical principle of measuring mercury by the instrument is to adopt a high-frequency polarization Zeeman effect background correction technology and carry out quantitative analysis on mercury based on the absorption principle of mercury atoms on 254nm resonance emission lines.
Example 1
The preparation method of the solid-phase micro-extraction probe of the nanogold-modified wood stick comprises the following steps:
(1) reducing chloroauric acid by using sodium borohydride to prepare a nanogold solution: firstly, soaking all glassware in aqua regia to remove possible residual reducing substances on the wall of a container, accurately weighing 8.8mg of chloroauric acid in a 50mL beaker at room temperature, then adding 30mL of ultrapure water and 1.0mL of sodium citrate (the concentration of the sodium citrate is 40mmol/L) solution in the beaker, violently stirring for 5min, dropwise adding 0.5mL of newly prepared sodium borohydride (the concentration of the sodium borohydride is 40mmol/L) solution into the mixed solution, adding the sodium borohydride into the mixed solution, gradually changing the color of the solution from light yellow to purple gray, finally turning into wine red, continuing stirring for 10min after the solution becomes wine red, and obtaining a nano-gold solution, standing the synthesized nano-gold solution for 2h at room temperature, storing at 4 ℃, wherein the concentration of the nano-gold synthesized by the method is 167 +/-3.2 mg/L.
(2) Selecting a commercialized dicksia polycephala toothpick without any treatment (the length is 5.0cm, the diameter is 2.0mm), and breaking off the commercial dicksia polycephala toothpick from the middle to obtain two sections of dicksia polycephala toothpicks as nano-gold particle carriers;
(3) and (3) completely immersing the toothpick obtained in the step (2) into the nano-gold solution obtained in the step (1), keeping for 1.0min, taking out, standing at room temperature for 10min, and air-drying to obtain the solid-phase micro-extraction probe of the nano-gold modified wood pick.
FIG. 1 is a Scanning Electron Micrograph (SEM) of a solid phase microextraction probe prepared in this example, showing that, at a magnification of 100 (FIG. 1B), the surface of the wood stick is wrinkled and porous, with a tip diameter of about 0.5 mm. At 500 x magnification (fig. 1C), the porous structure of the wood stick is more evident and the distribution of particulate matter within the channels can be seen. Fig. 2 is an energy spectrum (EDS) of the solid-phase microextraction probe prepared in this example, and elemental analysis of the prepared solid-phase microextraction probe by EDS can clearly show a signal of gold, and at the same time can show that the mass percentage of gold is 1.45%, which proves that there is a gold nanoparticle cluster attached to the wood-stick substrate.
Example 2
The same as example 1, except that:
the specific steps of the step (1) are that sodium borohydride is adopted to reduce chloroauric acid to prepare nano gold solution: firstly, soaking all glassware in aqua regia to remove possible residual reducing substances on the wall of a container, accurately weighing 8.8mg of chloroauric acid in a 50mL beaker at room temperature, then adding 30mL of ultrapure water and 1.0mL of sodium citrate (the concentration of the sodium citrate is 40mmol/L) solution into the beaker, after vigorously stirring for 10min, dropwise adding 0.5mL of newly prepared sodium borohydride (the concentration of the sodium borohydride is 40mmol/L) solution into the mixed solution, gradually changing the color of the solution after the sodium borohydride is added into the mixed solution from light yellow to purple gray, and finally obtaining wine red, and continuing stirring for 15min after the solution becomes wine red to obtain a nanogold solution;
and (3) completely immersing the toothpick obtained in the step (2) into the nano-gold solution obtained in the step (1), keeping for 20min, taking out, standing at room temperature for 30min, and air-drying to obtain the solid-phase micro-extraction probe of the nano-gold modified wood stick.
Example 3
Headspace extraction and micro-extraction probe portable mercury detector combined with environment water sample mercury ion determination
The headspace extraction comprises the following steps:
(1) measuring 5mL of mercury standard solution or water sample to be detected in a 20mL universal threaded-mouth headspace bottle, adding 1.0mL of stannous chloride hydrochloric acid solution with the mass fraction of 5%, and quickly screwing down a headspace bottle cap;
(2) quickly piercing a silica gel diaphragm pad on a headspace bottle cap by using the solid-phase microextraction probe of the nanogold-modified wood stick prepared in the embodiment 1, wherein the length of the solid-phase microextraction probe exposed in the headspace is 15.0 mm;
(3) the headspace bottle was placed on a reciprocal shaker and extracted at room temperature at a shaking speed of 250r/min for 10 min.
And (3) analyzing by using a micro-extraction probe portable mercury detector:
and taking out the solid-phase micro-extraction probe which is completely enriched in the headspace bottle, and transferring the solid-phase micro-extraction probe to a quartz sample-feeding boat of a thermal desorption module of the portable mercury detector. Carrier gas type: air; flow rate of carrier gas: 1.0L/min; absorption line wavelength: 253.7 nm; total detection optical length: 40 cm; integration time: 30s, quantification by external standard method.
Example 4
Headspace extraction condition optimization study
Mercury ions (2. mu.g/L) were added to ultrapure water to investigate the effect of different extraction conditions (oscillation speed, extraction temperature, extraction time, solution pH and solution salinity) on the extraction efficiency (FIG. 3). Wherein the extraction efficiency is expressed as peak area.
This example investigated the extraction efficiency at different shaking speeds (0rpm, 60rpm, 120rpm, 150rpm, 180rpm, 210rpm, 240rpm, 270rpm, 300 rpm). As shown in fig. 3a, the extraction efficiency increases with increasing oscillation speed.
This example simultaneously investigated the extraction efficiency at different extraction temperatures (25 ℃, 35 ℃, 45 ℃, 55 ℃, 65 ℃, 75 ℃). As shown in fig. 3b, increasing the temperature properly is beneficial to increase the extraction efficiency, but when a certain temperature is reached (55 ℃), the extraction efficiency decreases as the temperature continues to increase, indicating that the partition coefficient between the micro-extraction probes and the mercury vapor decreases.
This example also investigated the effect of extraction time (FIG. 3 c). The extraction efficiency is improved along with the increase of the extraction time, and dynamic equilibrium is reached until 10 min.
This example finally investigated the effect of solution pH (4, 5, 6, 7, 8, 9) and salinity conditions (0, 1%, 3%, 5%, 10%, 15%, 20%) on extraction efficiency. As shown in fig. 3d, pH and salinity had no significant effect on extraction efficiency.
Example 5
Headspace extraction method performance study
Mercury ions with the concentration range of 0.2-10 mug/L are added into ultrapure water, and the linear range, the lowest detection limit and the quantitative limit of the extraction method are researched. The result shows that the method has good linear relation and correlation coefficient (r)2) Is 0.9999. The lowest detection limit and the limit of quantitation were 0.06. mu.g/L and 0.19. mu.g/L, respectively (determined by continuously measuring the peak concentrations at 3 times and 10 times the standard deviation of 11 blank solutions). Table 1 compares the performance of the direct mercury measurement method with other methods, and it is found that the solid phase microextraction probe used in the method can reach or even exceed the mercury measurement capability of conventional laboratory instruments. In addition, the solid phase micro-extraction technology related to the method integrates sample sampling, extraction and preconcentration, and devices such as a chemical vapor generation device, a gas-liquid separator and the like which are relatively complex in configuration are not needed, so that the portability and the field operation performance of experimental equipment are further improved.
TABLE 1
The reproducibility of the different probes was investigated by adding mercury ions at a concentration of 1 μ g/L to ultrapure water, and 8 different micro-extraction probes were prepared as described in example 1, and the experimental results in fig. 4 show that the method has good reproducibility with RSDs of 2.1%.
The embodiment also researches the anti-interference capability of the micro-extraction probe, and adopts 15 ions such as alkali metal, alkaline earth metal, transition metal ions and the like widely existing in the environmental water body as the matrix for interference. These cations in water tend to form metallic states or corresponding metal colloids to adsorb mercury during reductive derivatization, thereby affecting extraction efficiency. In the experiment, when the concentration of mercury ions is 2 mug/L and the concentration of other 15 interference ions (potassium, calcium, sodium, magnesium, iron, aluminum, nickel, copper, zinc, manganese, cobalt, chromium, cadmium, antimony and arsenic) is 5mg/L, the recovery rate of the mercury ions is examined. Experimental results show that under the condition of coexistence of interfering ions, the headspace extraction recovery rate of mercury ions is 92.9% -101.8%.
The result shows that the micro-extraction probe provided by the invention meets the analysis requirement of trace mercury ions in the environmental water body.
Example 6
Research on extraction capability of water sample in actual environment
The solid phase micro-extraction probe prepared in example 1 is used for extracting standard water samples GBW080042 and GSB 07-3173-:
TABLE 2
From the experimental results in table 2, it can be seen that the measured values of the standard water samples are highly consistent with the certified values, no mercury ions are detected in tap water, lake water, seawater and wastewater, and when the sample loading concentration is 1 μ g/L, the loading recovery rate is 91.3% to 106%, indicating that the solid phase microextraction probe prepared in example 1 is suitable for measuring mercury in water samples of different substrate environments.
The detailed description is specific to possible embodiments of the invention, which are not intended to limit the scope of the invention, but rather are intended to include equivalent implementations or modifications within the scope of the invention.
Claims (5)
1. A solid phase micro-extraction probe of a nanogold-modified wood stick is characterized by comprising a carrier and an adsorption material, wherein the carrier is made of a wood stick material, the adsorption material is gold nanoparticles, and the adsorption material is attached to a pore channel on the surface of the carrier through Van der Waals force;
the preparation method of the solid-phase micro-extraction probe of the nanogold-modified wood stick comprises the following steps:
(1) adding ultrapure water and a sodium citrate solution into chloroauric acid at room temperature, stirring for 5-10 min, dropwise adding a sodium borohydride solution into the mixed solution, gradually changing the solution into wine red from light yellow, and continuing stirring for 7-15 min after the solution added with sodium borohydride becomes wine red, so as to obtain a nanogold solution;
(2) selecting a wood stick with the length of 2-5 cm and the tip diameter of 0.3-0.5 mm as a carrier;
(3) and (3) completely immersing the wood stick in the step (2) into the nano-gold solution prepared in the step (1), keeping for 1.0-20 min, taking out, and standing for 10-30 min at room temperature to obtain the solid-phase micro-extraction probe of the nano-gold modified wood stick.
2. The solid-phase microextraction probe of the nanogold-modified wood stick according to claim 1, wherein the concentration of the nanogold prepared by the sodium borohydride reduction method is 150-200 mg/L.
3. The use of the solid-phase microextraction probe of the nanogold-modified wood stick according to claim 1.
4. The application of the solid-phase microextraction probe of the nanogold-modified wood stick according to claim 3 is applied to determination of mercury ions in a water sample.
5. The application of the solid-phase microextraction probe for the nanogold-modified wood stick according to claim 4 is characterized in that the determination of mercury ions in a water sample comprises the following steps:
(1) measuring 5.0-10.0 mL of mercury standard solution or water sample to be detected in a headspace bottle, and adding 0.5-1.0 mL of stannous chloride solution with the mass fraction of 1% -10%;
(2) penetrating the prepared solid-phase microextraction probe of the nanogold-modified wood stick through the silica gel diaphragm pad on the headspace bottle cap, wherein the length of the wood stick carrier of the solid-phase microextraction probe of the nanogold-modified wood stick, which is exposed outside the headspace bottle, is 5.0-20 mm, and extracting the headspace bottle at the oscillation speed of 150-300 r/min for 5.0-30 min;
(3) and taking out the solid-phase micro-extraction probe of the nanogold-modified wood stick after the headspace bottle is completely enriched, transferring the solid-phase micro-extraction probe of the nanogold-modified wood stick to a quartz sample-feeding boat of a thermal desorption module of the portable mercury detector, and measuring mercury ions, wherein the thermal desorption temperature is set to be 680-740 ℃, and the airflow speed is set to be 0.8-1.2L/min.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810778221.XA CN109187775B (en) | 2018-07-16 | 2018-07-16 | Solid-phase micro-extraction probe of nanogold-modified wood stick and application thereof |
| PCT/CN2018/100677 WO2020015041A1 (en) | 2018-07-16 | 2018-08-15 | Solid phase micro-extraction probe of nanogold modified wooden stick and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810778221.XA CN109187775B (en) | 2018-07-16 | 2018-07-16 | Solid-phase micro-extraction probe of nanogold-modified wood stick and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109187775A CN109187775A (en) | 2019-01-11 |
| CN109187775B true CN109187775B (en) | 2020-09-25 |
Family
ID=64936673
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810778221.XA Active CN109187775B (en) | 2018-07-16 | 2018-07-16 | Solid-phase micro-extraction probe of nanogold-modified wood stick and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109187775B (en) |
| WO (1) | WO2020015041A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114236072B (en) * | 2021-12-06 | 2024-06-11 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Method for rapidly determining mercury form in water |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107226882A (en) * | 2017-05-11 | 2017-10-03 | 佛山科学技术学院 | A kind of surface modification molecular blotting solid phase microextraction probe and its preparation and application |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101216494B (en) * | 2008-01-11 | 2011-06-22 | 东南大学 | Sensor for detecting enzyme activity based on cuttlebone organic matter and method for making same |
| CN102608108A (en) * | 2012-02-21 | 2012-07-25 | 温州医学院 | Nano biosensor method and kit for rapid detection of Hg ions |
| CN103439267B (en) * | 2013-08-28 | 2018-12-11 | 中国科学院宁波材料技术与工程研究所 | A kind of test reagent combination and detection method of dimercurion |
| CN104134606B (en) * | 2014-07-30 | 2017-04-19 | 中山大学 | Microextraction probe electrospray ion source and manufacturing method and application of microextraction probe electrospray ion source |
| CN104233828B (en) * | 2014-09-16 | 2016-02-17 | 四川大学 | A kind of nano particle is fixed on the method on polymer superfine fibre surface |
| CN106908595A (en) * | 2015-12-23 | 2017-06-30 | 周勇 | A kind of test paper of quick detection mercury ion and preparation method thereof |
| CN106770255A (en) * | 2017-01-12 | 2017-05-31 | 青岛科技大学 | Mercury ion detecting test paper and preparation method thereof and detection method |
| CN106990178B (en) * | 2017-03-29 | 2020-09-11 | 中国科学院生态环境研究中心 | Method for detecting content of antimony ions by modifying nanogold optical probe |
| CN109187384B (en) * | 2018-08-14 | 2021-02-05 | 广东省测试分析研究所（中国广州分析测试中心） | Mercury enrichment material in water sample and headspace mercury enrichment and measurement method |
-
2018
- 2018-07-16 CN CN201810778221.XA patent/CN109187775B/en active Active
- 2018-08-15 WO PCT/CN2018/100677 patent/WO2020015041A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107226882A (en) * | 2017-05-11 | 2017-10-03 | 佛山科学技术学院 | A kind of surface modification molecular blotting solid phase microextraction probe and its preparation and application |
Non-Patent Citations (3)
| Title |
|---|
| Self-assembled Gold Nanoparticles Coating for Solid-Phase Microextraction of Ultraviolet Filters in Environmental Water;LIU Hai-Xia et al.;《CHINESE JOURNAL OF ANALYTICAL CHEMISTRY》;20151231;第43卷(第2期);摘要，第208页 * |
| 固相微萃取技术及其在有机锡和有机汞分析中的应用;刘援燕 等;《分析化学评述与进展》;19991031;第27卷(第10期);第1227页 * |
| 纳米金溶胶的制备及表征;张爱春 等;《雪莲杯第10届功能性纺织品及纳米技术应用研讨会》;20110318;第58页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109187775A (en) | 2019-01-11 |
| WO2020015041A1 (en) | 2020-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102408094B (en) | Preparation method for highly repetitive surface enhanced Raman spectrum (SERS) active substrate | |
| Chu et al. | Enhanced stripping voltammetric response of Hg2+, Cu2+, Pb2+ and Cd2+ by ZIF-8 and its electrochemical analytical application | |
| Zhang et al. | In situ hydrothermal growth of ZnO/g-C3N4 nanoflowers coated solid-phase microextraction fibers coupled with GC-MS for determination of pesticides residues | |
| Bağ et al. | Determination of Cu, Zn, Fe, Ni and Cd by flame atomic absorption spectrophotometry after preconcentration by Escherichia coli immobilized on sepiolite | |
| Zhao et al. | Sensitive determination of trace Cd (ii) and Pb (ii) in soil by an improved stripping voltammetry method using two different in situ plated bismuth-film electrodes based on a novel electrochemical measurement system | |
| Dang et al. | Selective electrochemical detection of hydroquinone and catechol at a one-step synthesised pine needle-like nano-CePO 4 modified carbon paste electrode | |
| CN110975807A (en) | Preparation method and application of magnetic biomass charcoal material | |
| CN114226709A (en) | Nano porous bismuth and preparation method and application thereof | |
| CN109187775B (en) | Solid-phase micro-extraction probe of nanogold-modified wood stick and application thereof | |
| CN110540203A (en) | preparation method and application of badam shell-based nitrogen-doped nano porous carbon material | |
| Xu et al. | Controllable synthesis of zeolitic imidazolate frameworks and the peanut shell carbon composite for sensitive and selective detection of Pb2+ and Cd2+ ions | |
| Peng et al. | In-atomizer atom trapping on gold nanoparticles for sensitive determination of mercury by flow injection cold vapor generation atomic absorption spectrometry | |
| CN112666151A (en) | Method for rapidly, qualitatively and quantitatively analyzing trace bromide ions | |
| CN109613087B (en) | Method for preparing electrochemical sensor for lead ion detection from wax gourd and milk | |
| CN108956727B (en) | Electrode modification material for simultaneously detecting hydroquinone and catechol in seawater | |
| CN108072641B (en) | Preparation method of surface enhanced Raman scattering substrate material and gas detection method | |
| CN114354582B (en) | Preparation method of dual-signal amplification electrochemiluminescence aptamer sensor and Pb detection method thereof 2+ Applications of (2) | |
| CN113390809B (en) | Method for detecting low-concentration methylmercury | |
| CN112126427B (en) | Water-soluble fluorescent carbon dot, preparation method thereof and application of water-soluble fluorescent carbon dot in detection of multiple heavy metals | |
| Zhu et al. | Determination of water-soluble nitrate ions in PM2. 5 particles using UiO-67 modified glassy carbon electrode | |
| CN114113023A (en) | Preparation method and application of nitrogen-doped carbon dots based on listeria monocytogenes source | |
| Tian et al. | A silver fibre prepared by a facile method for solid-phase microextraction of polycyclic aromatic hydrocarbons | |
| Yao et al. | Design of highly defective Zn-doped CeO2 solid solution quantum dots for accurate monitoring of ciprofloxacin | |
| CN109254067B (en) | Rhodamine b/reduced graphene oxide modified glassy carbon electrode and preparation and application thereof | |
| Dang et al. | The construction of an electrochemical sensing interface based on nano-CeO 2 cubes for highly sensitive detection of bisphenol A |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 510070 Guangzhou City, Guangzhou, Guangdong, No. 34 Patentee after: Institute of testing and analysis, Guangdong Academy of Sciences (Guangzhou analysis and testing center, China) Address before: 510070 Building 34, No. 100 Xianlie Middle Road, Yuexiu District, Guangzhou City, Guangdong Province Patentee before: GUANGDONG INSTITUTE OF ANALYSIS (CHINA NATIONAL ANALYTICAL CENTER, GUANGZHOU) |