CN115639184A - Preparation method and application of enrichment Raman enhancement active substrate for small molecule screening - Google Patents
Preparation method and application of enrichment Raman enhancement active substrate for small molecule screening Download PDFInfo
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- CN115639184A CN115639184A CN202211312030.7A CN202211312030A CN115639184A CN 115639184 A CN115639184 A CN 115639184A CN 202211312030 A CN202211312030 A CN 202211312030A CN 115639184 A CN115639184 A CN 115639184A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
Abstract
The invention relates to a preparation method and application of a Raman-enhanced active substrate for small molecule screening and enrichment, wherein the preparation method comprises the following steps: treating the glass sheet by using zinc acetate to enable the surface of the glass sheet to be paved with a zinc oxide seed crystal layer, then growing a zinc oxide nanowire on the surface of the glass by using a growth solution prepared from the zinc acetate and hexamethyltetramine, thermally evaporating a silver layer on the surface of the glass on which the zinc oxide nanowire grows, and finally wrapping a layer of zif-8 on the zinc oxide nanowire. The Raman-enhanced active substrate for small molecule screening and enrichment, which is prepared by the invention, not only can directly detect small molecules in a complex solution environment, but also has high detection sensitivity, and the minimum detection concentration of the substrate can reach 10 ‑9 M。
Description
Technical Field
The invention belongs to the field of molecular signal detection, and relates to a preparation method and application of an enriched Raman enhancement active substrate for small molecule screening.
Background
The information disclosed in this background of the invention is only for the purpose of increasing an understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person skilled in the art.
In recent years, SERS detection has been widely used as a specific detection means in various fields because of its high efficiency, high accuracy and high sensitivity. However, in practical applications, the simple SERS detection method suffers from many problems. When the sample is subjected to low-concentration and impurity molecule-containing detection objects, the conditions of uneven molecular enrichment, poor sample affinity and influence on detection by interfering molecules occur, which greatly hinders the wide application of SERS.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a preparation method and application of an enrichment Raman enhancement active substrate for small molecule screening, and the substrate can realize enrichment and screening of target molecules when a detected object with low concentration and impurity interference is detected.
In order to realize the purpose, the technical scheme of the invention is as follows:
in a first aspect, a preparation method for a small molecule screening and enriching raman-enhanced active substrate comprises the following steps:
(1) Soaking the glass sheet in an ethanol solution of zinc acetate, and then drying the soaked glass sheet to form a seed crystal layer of zinc oxide on the surface of the glass sheet;
(2) Putting the obtained glass sheet into a mixed aqueous solution of zinc acetate and hexamethylenetetramine, and then heating in a water bath to grow a zinc oxide nanowire on the surface of the glass;
(3) Thermally evaporating a silver layer on the surface of the glass sheet on which the zinc oxide nanowires grow;
(4) Soaking the silver-plated zinc oxide glass sheet in a methanol mixed solution of zinc nitrate hexahydrate and dimethylimidazole to grow zif-8 on the surface of the silver layer; the substrate can be used as a Raman substrate after being washed by methanol and fully dried.
Further, in the step (1), the glass sheet is washed by acetone, ethanol and deionized water respectively to remove impurities on the surface of the glass sheet.
Further, the zinc acetate ethanol solution with the concentration of 0.002-0.01M is used for growing the zinc oxide seed crystal layer; the concentration is preferably 0.005M.
Further, in the step (1), the soaking time is 10-20s, preferably 15s.
Further, the zinc oxide nanowire is grown on the seed crystal layer by using a mixed aqueous solution of zinc acetate and hexamethylenetetramine with a concentration of 0.005-0.02M, preferably 0.01M.
Further, heating in water bath at 80-100 deg.C for 0.5-2 hr, preferably 95 deg.C for 1 hr.
Further, the conditions of thermal evaporation were: the evaporation current is 60-80A, the deposition rate is 0.11-0.13nm/s, and the deposition time is 280-440s.
Further, zif-8 is grown by using a mixed methanol solution of 0.01 to 0.03M zinc nitrate hexahydrate and 0.01 to 0.03M 2-methylimidazole, each preferably having a concentration of 0.025M.
Experiments prove that the enrichment Raman enhanced active substrate for small molecule screening, which is prepared by the invention, can realize the enrichment and screening of small molecules aiming at a complex mixed solution taking the small molecules as a detection object, has high detection sensitivity, and can reach the minimum detection concentration of 4-mercaptopyridine of 10 -9 M。
In a second aspect, the application of the substrate for small molecule screening, enrichment and Raman enhancement active substrate in heavy metal detection is provided. Preferably, the detection is directed to mercury ions; more preferably, the detection is performed on mercury ions in human urine, animal waste and plant culture soil.
In a third aspect, a method for detecting mercury ions. Soaking the substrate for small molecule screening and enrichment Raman enhancement activity in a 4-mercaptopyridine solution to ensure that the 4-mercaptopyridine is fully attached to the silver nanowires; and soaking the soaked substrate used for small molecule screening and enrichment Raman enhancement active substrate into a solution containing mercury ions, and then taking out the substrate for Raman detection.
Further, after being taken out, 4-mercaptopyridine not attached to the raman substrate was washed away with alcohol.
Due to the enrichment effect of zif-8, more mercury ions can be enriched on the silver nanowire, and the mercury ions can be connected with the 4-mercaptopyridine, so that the Raman signal intensity of the 4-mercaptopyridine is increased due to the connection, and the detection of the mercury ions is achieved.
The invention has the beneficial effects that:
the invention prepares an enrichment Raman enhanced active substrate for small molecule screening, and the substrate has the enrichment capacity on small molecules and the capacity of inhibiting the interference of macromolecules by growing zif-8 on the surface of a silver nanowire and fully utilizing the characteristics of small aperture, high porosity and large specific surface area of the zif-8. Can be used for directly detecting pollutants containing large-particle interferents. Moreover, zif-8 will give the substrate a higher detection sensitivity. The lowest detected concentration of 4-mercaptopyridine on a substrate without zif-8 was 10 -8 M, but the lowest detection concentration of 4-mercaptopyridine on the substrate with zif-8 can reach 10 -9 And M. The method is simple to operate, short in time consumption, low in cost and suitable for being applied to multiple fields.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a Scanning Electron Microscope (SEM) image of a Raman-enhanced active substrate prepared according to example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a Raman-enhanced active substrate prepared in example 2 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of a Raman-enhanced active substrate prepared in example 3 of the present invention;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a Raman-enhanced active substrate prepared in example 4 of the present invention;
FIG. 5 is a Scanning Electron Microscope (SEM) image of a Raman-enhanced active substrate prepared in example 5 of the present invention;
FIG. 6 is a graph showing the comparison of the sensitivity of the Raman-enhanced active substrate prepared in examples 1 to 5 of the present invention to the sensitivity of R6G detection;
FIG. 7 is a graph showing the comparison of the sensitivity of Raman-enhanced active substrates prepared in examples 1 to 5 of the present invention to 4-ATP detection;
FIG. 8 is a graph representing the sensitivity of a Raman-enhanced active substrate prepared in example 1 of the present invention to 4-MPY detection;
FIG. 9 is a graph representing the sensitivity of a Raman-enhanced active substrate prepared in example 3 of the present invention to 4-MPY detection;
FIG. 10 is a graph showing the sensitivity of a Raman-active substrate prepared in example 3 of the present invention to mercury ion detection after being modified by 4-MPY;
fig. 11 is a characterization diagram of the anti-interference (interference from other heavy metals) performance of the raman active substrate prepared in example 3 of the present invention after being modified by 4-MPY for mercury ion detection;
FIG. 12 shows the detection of mercury ions in human urine after 4-MPY modification of the Raman-active substrate prepared in example 3 of the present invention;
FIG. 13 shows the detection of mercury ions in soil after 4-MPY modification of a Raman active substrate prepared in example 3 of the present invention;
fig. 14 shows the detection of mercury ions in chicken manure after the raman active substrate prepared in example 3 of the present invention is modified by 4-MPY.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In view of the defect that the conventional SERS is easily influenced by macromolecules or particles with large particle sizes when detecting small molecules, the invention provides the Raman enhancement active substrate for screening and enriching small molecules, and the preparation method and the application thereof.
The invention provides a typical implementation mode of an enrichment Raman enhancement active substrate for small molecule screening and a preparation method thereof, wherein a water bath is used for heating to enable zinc oxide nanowires to grow on the surface of glass, then a silver layer is thermally evaporated on the surface of the glass on which the zinc oxide nanowires grow, and then a plurality of layers of zif-8 are grown.
According to the invention, raman signals are increased by thermally evaporating the silver layer, and then the macromolecules cannot reach the electromagnetic enhancement region of the Raman substrate through zif-8 by growing zif-8.
In one or more embodiments of this embodiment, the zinc oxide seed layer is grown using a 0.005M ethanol solution of zinc acetate, and the subsequent growth of the zinc oxide nanowires on the seed layer is performed using a 0.01M aqueous solution of a mixture of zinc acetate and hexamethylenetetramine, using a 95 ° water bath heating temperature.
In one or more embodiments of this embodiment, the conditions for thermal evaporation are: the evaporation current is 60-80A, the deposition rate is about 0.11-0.13nm/s, and the deposition time is 280-440s.
In one or more examples of this embodiment, zif-8 is grown using a mixed methanol solution of 0.025M zinc nitrate hexahydrate and 2-methylimidazole.
In this series of examples, the drying process was carried out using a nitrogen stream.
In another embodiment of the invention, a raman-enhanced active substrate capable of screening small molecules is provided, which is obtained by the preparation method.
Experiments prove that the Raman enhanced active substrate capable of screening small molecules, which is prepared by the invention, not only can be used for directly detecting complex solution, but also has higher detection sensitivity, and the lowest detection concentration of the Raman enhanced active substrate on 4-MPY can reach 10 -9 M。
In a third embodiment of the invention, an application of the enrichment raman-enhanced active substrate for small molecule screening in detecting mercury ions is provided. And the mercury ions of human urine, chicken manure and soil are detected.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
The materials used in the examples of the invention are as follows:
hexamethylenetetramine (C) 6 H 12 N 4 99%) chemical reagent purchased from Chinese medicineLimited company, zinc acetate (C) 4 H 6 O 4 Zn, 99%), rhodamine 6G (C) 28 H 31 N 2 O 3 Cl, AR), methanol (CH) 3 OH) from national chemical reagent, inc., ethanol (C) 2 H 5 OH) from national Chemicals, inc., 2-methylimidazole (C) 4 H 6 N 2 ) Zinc nitrate pentahydrate (ZnNO) 3 ·5H 2 O), 4-mercaptopyridine (C) 5 H 5 NS), p-aminophenol (C) 6 H 6 NS)。
Sodium ion standard sample, silver ion standard sample, nickel ion standard sample, lead ion standard sample, cadmium ion standard sample, chromium ion standard sample, zinc ion standard sample, cobalt ion standard sample, calcium ion standard sample, copper ion standard sample, barium ion standard sample, magnesium ion standard sample, mercury ion standard sample (purchased from China center for Standard substance)
Example 1
Growth of a zinc oxide seed crystal layer:
A2X 2cm glass slide was washed successively with acetone, ethanol and deionized water for 15 minutes and dried with a stream of nitrogen.
And soaking the cleaned glass sheet in a zinc acetate ethanol solution (0.005M) for 15S, and then placing the glass sheet on a heating table at 270 ℃ to dry for 30 min. Then soaking and drying are repeated twice. And uniformly growing a seed crystal layer on the surface of the glass sheet.
Growing the zinc oxide nanowire:
firstly, preparing a mixed aqueous solution of 0.01M zinc acetate dehydrate and 0.01M hexamethylenetetramine, pouring the prepared solution into a sealable container, then vertically placing a glass sheet with a zinc oxide seed crystal layer grown on the surface into the container, and placing the container into a water bath kettle with the temperature of 95 ℃ for water bath heating to enable a zinc oxide nanowire to grow on the surface of the glass sheet. After the reaction had proceeded for one hour, the glass slide was removed, rinsed with deionized water, and dried with a stream of nitrogen after rinsing.
Thermally evaporating the silver coating:
a thin layer of silver was deposited on the surface of the copper mesh by thermal evaporation. The evaporation material was high purity Ag particles, the evaporation current was set at 70A, the deposition rate was about 0.12nm/s, the deposition time was 375s, and a raman-enhanced active substrate was obtained. The Scanning Electron Microscope (SEM) image is shown in FIG. 1.
Example 2
Growth of a zinc oxide seed crystal layer:
A2X 2cm glass slide was washed successively with acetone, ethanol and deionized water for 15 minutes and dried with a stream of nitrogen.
And soaking the cleaned glass sheet in a zinc acetate ethanol solution (0.005M) for 15S, and then placing the glass sheet on a heating table at 270 ℃ to dry for 30 min. Then soaking and drying are repeated twice. And uniformly growing a seed crystal layer on the surface of the glass sheet.
Growing the zinc oxide nanowire:
firstly, preparing a mixed aqueous solution of 0.01M zinc acetate dehydrate and 0.01M hexamethylenetetramine, pouring the prepared solution into a sealable container, then vertically placing a glass sheet with a zinc oxide seed crystal layer growing on the surface into the container, and placing the container into a water bath kettle at 95 ℃ for water bath heating to enable a zinc oxide nanowire to grow on the surface of the glass sheet. After one hour of reaction, the glass slide was removed, rinsed with deionized water, and dried with a stream of nitrogen after rinsing.
Thermally evaporating the silver coating:
a thin layer of silver was deposited on the surface of the copper mesh by thermal evaporation. The evaporation material was high purity Ag particles, the evaporation current was set at 70A, the deposition rate was about 0.125nm/s, and the deposition time was 360s.
Growth of zif-8 film:
respectively preparing 0.025M zinc nitrate methanol solution and 0.025M dimethyl imidazole methanol solution, fully mixing the two prepared solutions, vertically putting the Raman substrate into the solutions, and growing a layer of zif-8 film on the surface of the substrate. After the reaction had proceeded for 30 minutes, the substrate was taken out, rinsed with methanol and dried with a stream of nitrogen. Thus obtaining the enrichment Raman enhancement active substrate for small molecule screening. The Scanning Electron Microscope (SEM) image is shown in FIG. 2.
Example 3
Growth of a zinc oxide seed crystal layer:
A2X 2cm glass slide was washed successively with acetone, ethanol and deionized water for 15 minutes and dried with a stream of nitrogen.
And soaking the cleaned glass sheet in an ethanol solution (0.005M) of zinc acetate for 15S, and then drying the glass sheet on a heating table at 270 ℃ for 30 minutes. Then soaking and drying are repeated twice. And uniformly growing a seed crystal layer on the surface of the glass sheet.
Growing the zinc oxide nanowire:
firstly, preparing a mixed aqueous solution of 0.01M zinc acetate dehydrate and 0.01M hexamethylenetetramine, pouring the prepared solution into a sealable container, then vertically placing a glass sheet with a zinc oxide seed crystal layer growing on the surface into the container, and placing the container into a water bath kettle at 95 ℃ for water bath heating to enable a zinc oxide nanowire to grow on the surface of the glass sheet. After one hour of reaction, the glass slide was removed, rinsed with deionized water, and dried with a stream of nitrogen after rinsing.
Thermally evaporating the silver coating:
a thin layer of silver was deposited on the surface of the copper mesh by thermal evaporation. The evaporation material was high purity Ag particles, the evaporation current was set at 70A, the deposition rate was about 0.12nm/s, and the deposition time was 375s.
Growth of zif-8 film:
respectively preparing 0.025M zinc nitrate methanol solution and 0.025M dimethyl imidazole methanol solution, fully mixing the two prepared solutions, vertically putting the Raman substrate into the solutions, and growing a layer of zif-8 film on the surface of the substrate. After the reaction had proceeded for 30 minutes, the substrate was taken out, rinsed with methanol and dried with a stream of nitrogen. And then repeatedly growing a second layer of zif-8 film to obtain the enrichment Raman enhancement active substrate for small molecule screening. The Scanning Electron Microscope (SEM) image is shown in FIG. 3.
Example 4
Growth of a zinc oxide seed crystal layer:
A2X 2cm glass slide was washed successively with acetone, ethanol and deionized water for 15 minutes and dried with a stream of nitrogen.
And soaking the cleaned glass sheet in a zinc acetate ethanol solution (0.005M) for 15S, and then placing the glass sheet on a heating table at 270 ℃ to dry for 30 min. Then soaking and drying are repeated twice. And (5) uniformly growing a seed crystal layer on the surface of the glass sheet.
Growing the zinc oxide nanowire:
firstly, preparing a mixed aqueous solution of 0.01M zinc acetate dehydrate and 0.01M hexamethylenetetramine, pouring the prepared solution into a sealable container, then vertically placing a glass sheet with a zinc oxide seed crystal layer grown on the surface into the container, and placing the container into a water bath kettle with the temperature of 95 ℃ for water bath heating to enable a zinc oxide nanowire to grow on the surface of the glass sheet. After the reaction had proceeded for one hour, the glass slide was removed, rinsed with deionized water, and dried with a stream of nitrogen after rinsing.
Thermally evaporating the silver coating:
a thin layer of silver was deposited on the surface of the copper mesh by thermal evaporation. The evaporation material was high purity Ag particles, the evaporation current was set at 70A, the deposition rate was about 0.12nm/s, and the deposition time was 375s.
Growth of zif-8 film:
respectively preparing a 0.025M zinc nitrate methanol solution and a 0.025M dimethyl imidazole methanol solution, fully mixing the two prepared solutions, vertically putting the Raman substrate into the solutions, and growing a layer of zif-8 film on the surface of the substrate. After the reaction had proceeded for 30 minutes, the substrate was taken out, rinsed with methanol and dried with a stream of nitrogen. And then repeatedly growing a second layer and a third layer of zif-8 thin film to obtain the substrate for small molecule screening and enrichment Raman enhancement activity. The Scanning Electron Microscope (SEM) image is shown in FIG. 4.
Example 5
Growth of a zinc oxide seed crystal layer:
A2X 2cm glass slide was washed successively with acetone, ethanol and deionized water for 15 minutes and dried with a stream of nitrogen.
And soaking the cleaned glass sheet in a zinc acetate ethanol solution (0.005M) for 15S, and then placing the glass sheet on a heating table at 270 ℃ to dry for 30 min. Then soaking and drying are repeated twice. And uniformly growing a seed crystal layer on the surface of the glass sheet.
Growing the zinc oxide nanowire:
firstly, preparing a mixed aqueous solution of 0.01M zinc acetate dehydrate and 0.01M hexamethylenetetramine, pouring the prepared solution into a sealable container, then vertically placing a glass sheet with a zinc oxide seed crystal layer grown on the surface into the container, and placing the container into a water bath kettle with the temperature of 95 ℃ for water bath heating to enable a zinc oxide nanowire to grow on the surface of the glass sheet. After the reaction had proceeded for one hour, the glass slide was removed, rinsed with deionized water, and dried with a stream of nitrogen after rinsing.
Thermally evaporating the silver coating:
a thin layer of silver was deposited on the surface of the copper mesh by thermal evaporation. The evaporation material was high purity Ag particles, the evaporation current was set at 70A, the deposition rate was about 0.12nm/s, and the deposition time was 375s.
Growth of zif-8 film:
respectively preparing 0.025M zinc nitrate methanol solution and 0.025M dimethyl imidazole methanol solution, fully mixing the two prepared solutions, vertically putting the Raman substrate into the solutions, and growing a layer of zif-8 film on the surface of the substrate. After the reaction had proceeded for 30 minutes, the substrate was taken out, rinsed with methanol and dried with a stream of nitrogen. And then repeatedly growing a second layer, a third layer and a fourth layer of zif-8 film to obtain the substrate for small molecule screening and enrichment Raman enhancement activity. The Scanning Electron Microscope (SEM) image is shown in FIG. 5.
In order to characterize the raman enhancement effect of the zif-8 film on the raman enhancement active substrate, 5 μ L of 4-MPY solution dissolved in ethanol was respectively dropped on the surfaces of the raman enhancement active substrate prepared in example 1 and example 3, and a raman test was performed after natural drying. The test results are shown in FIGS. 8 to 9, and FIG. 8 shows the surface-enhanced Raman spectra of the Raman-enhanced active substrate without the zif-8 thin film for different concentrations of 4-MPY, which shows that the lowest detection concentration for 4-MPY can reach 10 -8 M, has higher sensitivity; FIG. 9 is a surface-enhanced Raman spectrum of a Raman-enhanced active substrate with zif-8 thin film for different concentrations of 4-MPY, showing that the lowest detected concentration of 4-MPY can reach 10 -9 M, has higher sensitivity.
The raman-enhanced active substrate prepared in example 3 was used to detect mercury ions in solution:
1. mercury ion detection mechanism: the Raman active substrate is modified by 4-MPY and then soaked in a mercury ion solution to detect mercury ions, when the Raman active substrate modified by 4-MPY is soaked in the mercury ion solution, the interaction between the mercury ions and nitrogen atoms on the 4-MPY changes the electron distribution on a pyridine ring, so that the reorientation of 4-MPY molecules tends to be in an adsorption mode more vertical to the surface of the silver nanowire, and the Raman signal of the 4-MPY is enhanced. We detected mercury ions in solution by the enhancement of the 4-MPY signal.
2.4-modification of MPY: it can be seen from FIG. 9 that the Raman-active substrate 10 has undergone sufficient adsorption -5 The Raman signal measured by the 4-MPY of M is the strongest, and we can consider 10 -5 After sufficient adsorption time, the M4-MPY can be attached to the Raman active substrate to the maximum extent. So we choose10 o -5 M4-MPY was used to modify the Raman-active substrate. We dip 10 a raman active substrate -5 Among the 4-MPY of M, the Raman substrate was taken out after sufficient adsorption (15 minutes) and the 4-MPY not attached to the Raman substrate was washed away with alcohol.
Hg ion detection:
the modified Raman active substrate is soaked in Hg ion solutions with different concentrations respectively, and detection is carried out after full adsorption (30 minutes).
The sample is placed into a Raman confocal micro spectrometer (LabRAM HR Evolution) for detection, fifteen points are randomly selected in the testing process, parameters are set to be that signals are acquired every 8s, the detector is repeatedly exposed twice, a real-time collected image is displayed every second, the light intensity is set to be 0.5%, the laser selects 532nm wavelength, and the grating is set to be 1800gr/mm.
The detection result is shown in FIG. 10, and the minimum detection concentration of the Raman-enhanced active substrate is 10 -10 M。
Interference immunity detection of Hg detection
The modified Raman active substrates are respectively arranged at 10 -6 And (3) soaking the M in mercury ion, sodium ion solution, silver ion solution, nickel ion solution, lead ion solution, cadmium ion solution, chromium ion solution, zinc ion solution, cobalt ion solution, calcium ion solution, copper ion solution, barium ion solution and magnesium ion solution, and detecting after full adsorption (30 minutes).
The sample is placed into a Raman confocal micro spectrometer (LabRAM HR Evolution) for detection, fifteen points are randomly selected in the testing process, parameters are set to be that signals are acquired every 8s, the detector is repeatedly exposed twice, a real-time collected image is displayed every second, the light intensity is set to be 0.5%, the laser selects 532nm wavelength, and the grating is set to be 1800gr/mm.
As shown in FIG. 11, it can be seen that the Raman signal of 4-MPY is also enhanced when other ions are detected, but the enhancement degree is much larger when Hg ions are detected. Therefore, we can see that the Raman active substrate modified by 4-MPY can specifically detect Hg ions.
The raman-enhanced active substrate prepared in example 3 was used to detect mercury ions in human urine, chicken manure, and soil:
preparing a soil detection solution containing mercury ions: 2g of soil were weighed first, poured into 8ml of alcohol and then 2ml of 10 -4 M4-MPY, and subjecting the mixed solution to ultrasonic treatment for 15 minutes.
Preparing a chicken manure detection liquid containing mercury ions: 2g of chicken manure are weighed first, poured into 8ml of alcohol and then 2ml of 10 ml of solution -4 M Mercury ion solution, and subjecting the mixed solution to ultrasonic treatment for 15 minutes.
Preparing human urine detection liquid containing mercury ions: taking 8ml of human urine, and pouring 2ml 10 into the solution -4 M Mercury ion solution, and subjecting the mixed solution to ultrasonic treatment for 15 minutes.
We dip 10 a raman active substrate -5 In M4-MPY, after sufficient adsorption (15 minutes), the Raman substrate was taken out and the 4-MPY not attached to the Raman substrate was rinsed off with alcohol. The sample is placed into a Raman confocal micro spectrometer (LabRAM HR Evolution) for detection, fifteen points are randomly selected in the testing process, parameters are set to be that signals are acquired every 8s, the detector is repeatedly exposed twice, a real-time collected image is displayed every second, the light intensity is set to be 0.5%, the laser selects 532nm wavelength, and the grating is set to be 1800gr/mm. (Raman signal of 4-MPY stored on Raman substrate before detection of Mercury ion)
The modified Raman active substrate is respectively soaked in soil detection liquid containing mercury ions, chicken manure detection liquid containing mercury ions and human urine detection liquid containing mercury ions for sufficient time.
The sample is placed into a Raman confocal micro spectrometer (LabRAM HR Evolution) for detection, fifteen points are randomly selected in the testing process, parameters are set to be that signals are acquired every 8s, the detector is repeatedly exposed twice, a real-time collected image is displayed every second, the light intensity is set to be 0.5%, the laser selects 532nm wavelength, and the grating is set to be 1800gr/mm.
The results of human urine, soil and chicken manure are shown in fig. 12, 13 and 14.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method for a small molecule screening and enrichment Raman enhancement active substrate is characterized by comprising the following steps:
(1) Soaking the glass sheet in an ethanol solution of zinc acetate, and then drying the soaked glass sheet to form a seed crystal layer of zinc oxide on the surface of the glass sheet;
(2) Putting the obtained glass sheet into a mixed aqueous solution of zinc acetate and hexamethylenetetramine, and then heating in a water bath to grow zinc oxide nanowires on the surface of the glass;
(3) Thermally evaporating a silver layer on the surface of the glass sheet on which the zinc oxide nanowire grows;
(4) Soaking the silver-plated zinc oxide glass sheet in a methanol mixed solution of zinc nitrate hexahydrate and dimethyl imidazole to grow zif-8 on the surface of the silver layer; the substrate can be used as a Raman substrate after being washed by methanol and fully dried.
2. The method according to claim 1, wherein in step (1), the glass sheet is first washed with acetone, ethanol, and deionized water, respectively, to remove impurities on the surface.
3. The method of claim 1, wherein the step of growing the zinc oxide seed layer is performed by using a zinc acetate ethanol solution having a concentration of 0.002-0.01M; the concentration is preferably 0.005M.
4. The method according to claim 1, wherein the soaking time in step (1) is 10 to 20s, preferably 15s.
5. The method of claim 1, wherein the zinc oxide nanowire is grown on the seed layer by using a mixed aqueous solution of zinc acetate and hexamethylenetetramine at a concentration of 0.005-0.02M, preferably at a concentration of 0.01M.
6. The process according to claim 1, wherein the heating is carried out in a water bath at 80-100 ℃ for 0.5-2h, preferably 95 ℃ for 1h.
7. The production method according to claim 1, wherein the conditions of thermal evaporation are: the evaporation current is 60-80A, the deposition rate is 0.11-0.13nm/s, and the deposition time is 280-440s;
for the growth of zif-8, a mixed methanol solution of 0.01-0.03M zinc nitrate hexahydrate and 0.01-0.03M 2-methylimidazole is used, each preferably at a concentration of 0.025M.
8. The enriched Raman-enhanced active substrate prepared by the preparation method according to any one of the preceding claims and used for small molecule screening.
9. Use of the enriched raman-enhanced active substrate for small molecule screening according to claim 8 in the detection of heavy metals, preferably in the detection of mercury ions; more preferably, the detection is performed on mercury ions in human urine, animal waste and plant culture soil.
10. The method for detecting mercury ions is characterized in that the substrate for screening, enriching and Raman enhancing the small molecules is soaked in a 4-mercaptopyridine solution, so that the 4-mercaptopyridine is fully attached to a silver nanowire; and soaking the soaked substrate used for the small molecule screening and enrichment Raman enhancement active substrate into a solution containing mercury ions, and then taking out the substrate for Raman detection.
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| CN115855928A (en) * | 2023-02-27 | 2023-03-28 | 合肥工业大学 | Mercury ion detection method and kit based on nucleic acid macroarray and bifunctional molecules |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115855928A (en) * | 2023-02-27 | 2023-03-28 | 合肥工业大学 | Mercury ion detection method and kit based on nucleic acid macroarray and bifunctional molecules |
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