CN108444538A - The environment network of mercury ion content is detected based on aldehyde radical chip and gold nano grain - Google Patents

Abstract

The invention discloses an environmental network for detecting mercury ion content based on aldehyde-based chips and gold nanoparticles, including a master node computer (10), and wireless signal connections between the master node computer (10) and a plurality of preset types of sensors A plurality of sensors of the preset type are installed in the thermal pipeline (3) and the water supply pipeline (6) laid in the underground space (100) and on the side wall of the underground space; the plurality of sensors of the preset type are used It is used to collect the detection data of the corresponding underground space. The environmental network for detecting mercury ion content based on aldehyde-based chips and gold nanoparticles disclosed by the present invention can safely and reliably monitor the environment of underground pipe networks in all directions, especially the mercury ions in water transported by underground pipe networks Effective detection of the content of the underground pipe network can reduce the safety hazards of the underground pipe network and ensure the safe use of the underground pipe network, which is conducive to wide application and has great practical significance in production.

Description

An Environmental Network Based on Aldehyde Chip and Gold Nanoparticles to Detect Mercury Ion Content

technical field

The invention relates to the technical field of underground space environment monitoring, in particular to an environmental network for detecting mercury ion content based on aldehyde-based chips and gold nanoparticles.

Background technique

At present, the underground pipe network is the top priority in the process of urbanization in my country. It is an important material basis for exerting urban functions and ensuring urban economic and social health and coordinated development. It presents intricate and overlapping three-dimensional characteristics. Pipe network is an important part of urban infrastructure construction, and an important carrier of energy transmission, material transmission, information transmission, drainage and disaster reduction, and waste disposal in a city.

In view of the fact that mercury and its compounds have multiple hazards to human health, mercury present in environmental waters can even pose a threat to a wide range of natural environments, humans and animals. Mercury is discharged into the environment in the form of solid waste, waste gas and wastewater, and the mercury discharged to the atmosphere and soil will also return to the water body with the water cycle, causing long-term and repeated mercury pollution in the environmental water body. Mercury can accumulate in organisms, and mercury in water can enter the human body through the food chain, especially aquatic products. The mercury accumulated in the human body is difficult to excrete through its own metabolism, and a trace amount of mercury can cause toxicity to the liver, kidney and other organs, causing oral inflammation, hand tremors, nervous system disorders and chronic mercury poisoning. With the increase of mercury accumulation, its impact on the human body is more obvious, manifested as severe irreversible brain nerve damage, and even brain death. Therefore, the mercury content in natural water bodies is the top priority in environmental detection and control. In order to protect human health, it is urgent to develop a fast, sensitive, and well-selected method to detect mercury ions.

However, a considerable number of cities in my country have not carried out unified layout planning and management of underground pipe networks. The management of underground pipe networks is fragmented, lacks communication with each other, and is in a state of disordered management. Compared with the speed of urban construction. Management is seriously backward and accidents often occur. The consequences of water cuts, power cuts, gas cuts, communication interruptions, fires and explosions caused by accidents not only seriously affect the quality of life and life safety of the people, but also affect the normal progress of economic construction and national defense construction.

For the current underground pipe network, the main problems are: due to the complex spatial structure of the underground pipe network, it is impossible to monitor the environment of the underground pipe network in all directions, especially the content of mercury ions in the water transported by the underground pipe network. Effective detection can reduce the potential safety hazards of the underground pipe network and ensure the safe use of the underground pipe network.

Therefore, there is an urgent need to develop a technology that can safely and reliably monitor the environment of the underground pipe network in all directions, especially the effective detection of the mercury ion content in the water transmitted by the underground pipe network, which can reduce the underground Potential safety hazards of the pipeline network to ensure the safe use of the underground pipeline network.

Contents of the invention

In view of this, the purpose of the present invention is to provide an environmental network based on aldehyde-based chips and gold nanoparticles to detect the content of mercury ions, which can safely and reliably monitor the environment of the underground pipe network in all directions, especially the ability to monitor the environment of underground pipe networks. Effective detection of the content of mercury ions in the water transmitted by the network can reduce the safety hazards of the underground pipe network and ensure the safe use of the underground pipe network. It is conducive to wide application and has great practical significance in production.

For this reason, the present invention provides an environmental network based on aldehyde-based chips and gold nanoparticles to detect mercury ion content, including a master node computer, which is connected by a wireless signal to a plurality of sensors of preset types;

A plurality of sensors of the preset type are installed in the heating pipes and water supply pipes laid in the underground space and on the side walls of the underground space;

The multiple sensors of the preset type are used to collect detection data of the corresponding underground space.

Wherein, the multiple sensors of the preset type include: a first temperature sensor, a second flow sensor and a surface-enhanced Raman SERS water quality sensor;

The first temperature sensor, the second flow sensor and the surface-enhanced Raman SERS water quality sensor are installed in the water supply pipeline to detect the temperature, flow rate and mercury ion content of the water in the water supply pipeline, and then send them to the master node computer.

Wherein, the multiple sensors of the preset type also include: a first pressure sensor, a first flow sensor and a second temperature sensor;

The first pressure sensor, the first flow sensor and the second temperature sensor are installed in the thermal pipeline for detecting the pressure, flow and temperature of the medium transported in the thermal pipeline, and then sending them to the master node computer.

Wherein, the multiple sensors of the preset type also include: oxygen sensor, carbon monoxide sensor, hydrogen sulfide sensor, temperature and humidity sensor and nitrogen oxide sensor;

The oxygen sensor, carbon monoxide sensor, hydrogen sulfide sensor, temperature and humidity sensor and nitrogen oxide sensor are installed on the side wall of the underground space respectively, and are used to collect the oxygen gas concentration, carbon monoxide gas concentration, hydrogen sulfide gas concentration, Temperature, humidity, and nitrogen oxide concentration are then sent to the master node computer.

Wherein, it also includes: a first monitoring camera and a second monitoring camera;

The first monitoring camera is located at the upper right of the second monitoring camera;

The first monitoring camera and the second monitoring camera are installed on the side wall of the underground space, and are respectively used to collect images of the covered areas, and then send them to the master node computer.

Wherein, the master node computer includes: a data storage module, a data processing module and a wireless data transmission module, wherein:

The data storage module is used to store the detection data of the underground space collected by the plurality of sensors of the preset type in real time;

The data processing module is connected with the data storage module, and is used to compare the detection data of the underground space collected by the plurality of sensors of the preset type with the preset and corresponding normal value ranges respectively. If it is within the corresponding normal value range, the corresponding data is judged to be qualified, otherwise, the corresponding data is judged to be unqualified, and at the same time, the comparison situation is sent to the computer of the ground base station through the wireless data transmission module in real time;

The data processing module is also used to send the images collected by the first monitoring camera and the second monitoring camera to the computer of the ground base station through the wireless data transmission module.

Wherein, it also includes: an inspection robot, and the inspection robot is arranged on the ground between the thermal pipeline and the water supply pipeline.

Wherein, the surface-enhanced Raman SERS water quality sensor includes a test kit and a detection switch, wherein:

A detection switch is installed on the water supply pipeline;

The reagent box is located below the detection switch, and the top of the reagent box has a plurality of holes;

A surface-enhanced Raman SERS chip is inserted into the kit, and the surface-enhanced Raman SERS chip includes a silicon dioxide substrate, and a plurality of DNA and 2-naphthylthiol-modified chips are arranged at intervals on the silicon dioxide substrate. The distribution area of gold nanoparticles;

The surface of the silicon dioxide substrate is sprayed with a gold nano film, and the gold nano film is coated with DNA;

Each gold nanoparticle distribution area modified by DNA and 2-naphthylthiol is correspondingly set and communicated with a hole;

An optical fiber probe is arranged directly above the kit, and the optical fiber probe is connected to a portable Raman detector through an optical fiber;

The portable Raman detector is provided with an antenna.

Wherein, preparation is sprayed on the surface and is coated with gold nano film and the silicon dioxide substrate that is also coated with DNA on the gold nano film, and specific preparation process comprises the following steps:

First, a glass sheet with a predetermined size was used as a substrate, soaked in piranha solution for 30 minutes to make its surface hydroxylated. The volume ratio between sulfuric acid and hydrogen peroxide in the piranha solution is 7:3;

Next, immerse the surface hydroxylated and hydroxyl-rich substrate in a methanol solution containing 5% mass solubility of 3-aminopropyltrimethoxysiloxane APTMS, and react at room temperature for 12 hours;

Next, continue to immerse the substrate in a glutaraldehyde solution with a mass concentration of 2.5% for 4 hours, so that the glutaraldehyde solution reacts with the APTMS modified on the surface of the substrate to generate an aldehyde-based surface;

Next, the substrate of the substrate was washed with ultrapure water and dried with a nitrogen stream. Then apply the 5-terminal amino modified DNA (CCCCCACCTCCCACCCACC) solution onto the treated substrate surface, and react at room temperature for 4 hours;

Wash the substrate three times with a phosphate buffer solution solution with a molar volume concentration of 0.1M to remove non-specifically bound DNA strands;

Finally, the spots on the DNA were wrapped with a bovine serum albumin solution with a mass concentration of 2.5% and the active sites on the DNA were blocked, then washed with ultrapure water, and dried in a drying oven to finally obtain a gold nano-film sprayed on the surface and The gold nano film is also coated with a silicon dioxide substrate with DNA.

Wherein, the preparation of the surface-enhanced Raman SERS chip comprises the following steps:

The first step, the chloroauric acid solution that is 0.01% by mass concentration is heated and boiled under vigorous stirring, and 1% trisodium citrate aqueous solution is added rapidly under stirring state, the chloroauric acid solution and trisodium citrate aqueous solution The volume ratio is 100:3;

The second step, continue heating and boiling for 15 minutes, so that the light yellow solution gradually turns into a stable crimson, and then the prepared liquid is cooled to room temperature to obtain gold colloid;

The third step is to add 2-naphthylthiol with a molar volume concentration of 0.01mM to the gold colloidal solution and mix it gently for 10 minutes to obtain 2-naphthylthiol-labeled gold nanoparticle separation liquid, and then follow the 8000 rpm Minute speed centrifugation for 10 minutes, remove the supernatant, wherein, the volume ratio of the 2-naphthol and gold colloidal solution is 1:100;

The fourth step is to suspend with 1 mL of phosphate buffer with a concentration of 10 mM to obtain the suspended gold colloid solution, wherein the volume ratio of phosphate buffer and gold colloid solution is 1:1;

Step 5: Add the preset DNA solution to the suspended gold colloid solution, react for 12 hours, then add a sodium chloride solution with a molar volume concentration of 0.1M for 30 minutes, and then place it at a temperature of 4 degrees Celsius Continue salinization for 6 hours to obtain a mixture, wherein the volume ratio of 2-naphthylthiol to sodium chloride solution is 1:2;

The sixth step, the mixture was centrifuged at 8000 rpm for 30 minutes, the supernatant was removed, and then placed in a phosphate buffer with a molar volume concentration of 10 mM to suspend to obtain DNA and 2-naphthylthiol-modified Gold nanoparticle solution;

The seventh step is to coat the gold nanoparticles modified with DNA and 2-naphthalenethiol on the silica substrate, and then place it in a drying oven for drying treatment, and finally form a gold nanoparticle modified with DNA and 2-naphthalene on the silica substrate. The distribution area of thiophenol-modified gold nanoparticles is prepared to obtain a surface-enhanced Raman SERS chip;

In the fifth step, the specific preparation steps of the preset DNA solution are as follows:

A DNA (CCCCCACCTCCCTCCCACCT) solution with a molar volume concentration of 100uM is mixed with a tris(2-carboxyethyl)phosphine hydrochloride solution with a molar volume concentration of 10mM, wherein the DNA solution is mixed with tris(2-carboxyethyl)phosphine hydrochloride The volume ratio of the solution is 20:3, and the volume ratio of the DNA solution to 2-naphthylthiol in the third step is 1:1, and the DNA solution is obtained by standing at room temperature for 1 hour for activation.

It can be seen from the above technical solutions provided by the present invention that compared with the prior art, the present invention provides an environmental network based on aldehyde-based chips and gold nanoparticles to detect mercury ion content, which can safely and reliably monitor the environment of underground pipe networks. All-round monitoring, especially the effective detection of the content of mercury ions in the water transported by the underground pipe network, can reduce the safety hazards of the underground pipe network and ensure the safe use of the underground pipe network, which is conducive to wide application and has great production potential Practical significance.

Description of drawings

Fig. 1 is the structural representation of the environmental network that detects mercury ion content based on aldehyde-based chip and gold nanoparticle that the present invention provides;

2 is a schematic diagram of data transmission based on ZigBee wireless communication technology to form an environmental network based on aldehyde-based chips and gold nanoparticles to detect mercury ion content provided by the present invention;

Fig. 3 is the synoptic schematic diagram of the cooperative working state of surface-enhanced Raman (SERS) water quality sensor and water supply pipeline in the environmental network that detects mercury ion content based on aldehyde-based chip and gold nanoparticle that the present invention provides;

Fig. 4 is the structural schematic diagram of surface-enhanced Raman (SERS) chip in the environmental network that detects mercury ion content based on aldehyde-based chip and gold nanoparticle that the present invention provides;

5 is a schematic diagram of the connection structure between gold nanoparticles and DNA chains in the environmental network based on aldehyde-based chips and gold nanoparticles to detect mercury ion content provided by the present invention;

6 is a schematic diagram of Raman signals obtained when a surface-enhanced Raman (SERS) chip detects liquids in an environmental network based on aldehyde-based chips and gold nanoparticles to detect mercury ion content provided by the present invention;

In the figure, 1 is the first monitoring camera; 2 is the second monitoring camera; 3 is the thermal pipeline; 4 is the first pressure sensor; 5 is the first temperature sensor; 6 is the water supply pipeline; 7 is the inspection robot; 8 is the second A flow sensor; 9 is the second flow sensor; 10 is the main node computer; 11 is the second temperature sensor; 12 is the surface enhanced Raman (SERS) water quality sensor; 13 is the oxygen sensor; 14 is the carbon monoxide sensor; 15 is the hydrogen sulfide Sensor; 16 is a temperature and humidity sensor; 17 is a nitrogen oxide sensor;

18 is a detection switch; 19 is a surface-enhanced Raman (SERS) chip; 20 is a kit; 21 is a portable Raman detector; 22 is an antenna; 23 is an optical fiber probe; The distribution area of gold nanoparticles; 25 is the silicon dioxide substrate; 26 is the gold nanoparticles; 27 is the DNA chain.

Detailed ways

In order to enable those skilled in the art to better understand the solution of the present invention, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.

1 to 6, the present invention provides an environmental network based on aldehyde-based chips and gold nanoparticles to detect mercury ion content, including a master node computer 10, the master node computer 10 and a plurality of sensors of preset types (i.e. as Secondary nodes) are connected by wireless signals (specifically through ZigBee wireless communication technology);

A plurality of sensors of the preset type are installed in the thermal pipeline 3 and the water supply pipeline 6 laid in the underground space 100 (ie, the underground pipe network space) and on the side walls of the underground space;

The multiple sensors of the preset type are used to collect detection data of the corresponding underground space, for example, a temperature sensor is used to detect temperature data of the installed location.

In the present invention, in specific implementation, the multiple sensors of the preset type include: a first temperature sensor 5, a second flow sensor 9 and a surface-enhanced Raman SERS water quality sensor 12;

The first temperature sensor 5, the second flow sensor 9 and the surface-enhanced Raman SERS water quality sensor 12 are installed in the water supply pipeline 6 for detecting the temperature, flow rate and mercury ion content of the water in the water supply pipeline 6, Then send to the master node computer 10 (specifically through ZigBee wireless communication technology).

In the present invention, in terms of specific implementation, the multiple sensors of the preset type also include: a first pressure sensor 4, a first flow sensor 8 and a second temperature sensor 11;

The first pressure sensor 4, the first flow sensor 8 and the second temperature sensor 11 are installed in the thermal pipeline 3 for detecting the pressure of the medium (such as hot water or steam) in the thermal pipeline 3, The flow and temperature are then sent to the master node computer 10 (specifically through ZigBee wireless communication technology, such as ZigBee ad hoc network).

It should be noted that a thermal pipeline is a transmission pipeline for high-temperature gas or liquid, such as a heating pipeline in a city.

In the present invention, in specific implementation, the multiple sensors of the preset type also include: an oxygen sensor 13, a carbon monoxide sensor 14, a hydrogen sulfide sensor 15, a temperature and humidity sensor 16 and a nitrogen oxide sensor 17;

The oxygen sensor 13, the carbon monoxide sensor 14, the hydrogen sulfide sensor 15, the temperature and humidity sensor 16 and the nitrogen oxide sensor 17 are respectively installed on the side walls of the underground space for collecting the overall environmental information of the underground space, specifically for Collect the oxygen gas concentration, carbon monoxide gas concentration, hydrogen sulfide gas concentration, temperature, humidity and nitrogen oxide concentration in the underground space, and then send them to the master node computer 10 (specifically through ZigBee wireless communication technology, such as ZigBee ad hoc network) .

In the present invention, in specific implementation, the underground space environment monitoring network provided by the present invention further includes: a first monitoring camera 1 and a second monitoring camera 2;

The first monitoring camera is located at the upper right of the second monitoring camera 2;

The first monitoring camera 1 and the second monitoring camera 2 are installed on the side wall of the underground space, and are respectively used to collect images of the covered area, and then send them to the master node computer 10 (specifically through ZigBee wireless communication technology, such as ZigBee ad hoc network), so as to realize real-time monitoring of the covered area.

In specific implementation, the first surveillance camera 1 and the second surveillance camera 2 may be surveillance bolts.

It should be noted that, in terms of specific implementation, the first monitoring camera 1 can be placed on the ceiling 15 meters from the entrance of the underground pipe network, and supports 360-degree infrared real-time monitoring. The second monitoring camera 2 is located on the side wall at 18 meters from the entrance of the underground pipe network, and can monitor the covered area in real time.

It should be noted that, for the present invention, among the plurality of preset types of sensors, each sensor includes a power supply module, a central control module, an environment collection module and a wireless communication module.

For the present invention, the master node computer 10 includes: a data storage module, a data processing module and a wireless data transmission module, wherein:

The data storage module is used to store the detection data of the underground space collected by the plurality of sensors of the preset type (i.e. as secondary nodes) in real time to form a database;

The data processing module is connected with the data storage module, and is used for detecting the detection data of the underground space collected by a plurality of sensors of the preset type (i.e. as secondary nodes), respectively with the preset and corresponding normal value range ( For example, comparing the preset temperature value range and the preset humidity value range), if it is within the preset and corresponding normal value range, it is judged that the corresponding data is qualified; otherwise, it is judged that the corresponding data is unqualified, At the same time, the comparison situation is sent to the computer of the ground base station through the wireless data transmission module in real time, so that the staff on the ground can understand the various environmental parameters of the underground space, obtain the environmental information of the underground space, and realize the real-time monitoring of the underground pipe network . In addition, the data processing module is also used to send the images collected by the first monitoring camera 1 and the second monitoring camera 2 to the computer of the ground base station through the wireless data transmission module.

For the present invention, in order to better monitor the underground space, the underground space environment network provided by the present invention also includes: an inspection robot 7, which is arranged on the ground between the thermal pipeline 3 and the water supply pipeline 6 .

It should be noted that the inspection robot 7 is mainly used for monitoring safety information of underground pipelines and collecting safety information of underground pipelines. The bottom of described inspection robot has wheel, can be installed with infrared thermal imager, visible light camera and laser navigation module (existing laser navigation module gets final product) on it;

Among them, the infrared thermal imager can detect temperature changes, so that the leakage of underground pipelines such as thermal pipeline 3 and water supply pipeline 6 can be monitored in real time;

Visible light cameras are used for real-time monitoring of images in underground spaces, which play an important role in ensuring the safety of pipeline operations.

The laser navigation module is used to ensure the route planning and intelligent detection of the inspection robot 7.

It should be noted that the main structure of the inspection robot 7 for moving and monitoring the environment is the structure of the existing inspection robot, which is similar to the prior art and will not be described here.

In terms of specific implementation, the data storage module, data processing module and wireless data transmission module are located at the lower part of the master node computer 10 .

It should be noted that, for the present invention, the data of all secondary nodes can be transmitted to the main node computer through the zigbee network, and the data are collected, processed, compared and retrieved through each data module of the main node computer, and finally the obtained Environmental information can be transmitted through the zigbee wireless communication module. Through the data collection, storage, processing and transmission of the whole system, the comprehensive utilization of underground pipe gallery information is realized, and strong data support is provided for the overall planning and comprehensive scheduling of underground space.

As shown in Figure 3, for the present invention, described Surface Enhanced Raman (SERS) water quality sensor 12 comprises reagent box 20 and detection switch 18, wherein:

The detection switch 18 is installed on the water supply pipeline 6; specifically, it can be an electromagnetic switch valve;

The reagent box 20 is located below the detection switch 18, and the top of the reagent box 20 has a plurality of holes;

Surface-enhanced Raman (SERS) chip 19 is inserted in the reagent box 20, and described surface-enhanced Raman (SERS) chip 19 comprises silicon dioxide substrate 25, and on described silicon dioxide substrate 25, intervals are provided with multiple A gold nanoparticle distribution area 24 modified by DNA and 2-naphthylthiol;

The surface of the silicon dioxide substrate 25 is spray-coated with a gold nano film, and the gold nano film is coated with (specifically: coated with) DNA;

Each gold nanoparticle distribution area 24 modified by DNA and 2-naphthylthiol is correspondingly arranged and communicated with a hole, that is, it can receive the liquid flowing in from the hole;

An optical fiber probe 23 is arranged directly above the reagent box 20, and the optical fiber probe 23 is connected to a portable Raman detector 21 through an optical fiber;

The portable Raman detector 21 is provided with an antenna 22 (specifically, it may be a ZigBee antenna).

In terms of specific implementation, the portable Raman detector 21 may be an existing portable Raman detector. For example, you can refer to the portable Raman detector described in the publication specification of the Chinese Utility Model Patent Application "A Portable Multifunctional Raman Detector" published on November 9, 2016 with the application number CN201621206981.6.

Therefore, for the present invention, since the detection switch 18 is installed below the water supply pipeline 6, when the detection is started, the detection switch 18 is turned on, and a drop of liquid that flows out from the water supply pipeline 6 will drop on the SERS detection chip 19 in the reagent box 20, As a result, a reaction occurs, and different pollutants are detected by dropping into different holes for detection. The fiber optic probe 23 can emit a 532nm laser for Raman detection and process it in the portable Raman detector 21, and finally transmit the mercury ion content data in the water detected by the portable Raman detector 21 to the master node computer wirelessly through the antenna 22 10.

For the present invention, it should be noted that the surface-enhanced Raman (SERS) water quality sensor 12 is mainly used for the detection of mercury ions in water, and the principle of utilization is that mercury ions can form "T-Hg ²⁺ - T” structure, which indirectly detects the presence of mercury ions by SERS.

In order to prepare the silicon dioxide substrate 25 that is spray-coated with gold nano film on the surface and also coated with (specifically: coated with) DNA on the gold nano film, the specific preparation process may include the following steps:

First, a glass sheet with a predetermined size is used as a substrate, soaked in a piranha solution (where the volume ratio between sulfuric acid and hydrogen peroxide is 7:3) for 30 minutes to make the surface hydroxylated;

Next, immerse the surface hydroxylated and hydroxyl-rich substrate in a methanol solution containing 5% by mass of 3-aminopropyltrimethoxysiloxane (APTMS), and react at room temperature for 12 hours;

Next, continue to immerse the substrate in a glutaraldehyde solution with a mass concentration of 2.5% for 4 hours, so that the glutaraldehyde solution reacts with the APTMS modified on the surface of the substrate to generate an aldehyde-based surface;

Next, the substrate of the substrate was washed with ultrapure water and dried with a nitrogen stream. Then apply the solution of DNA (sequence CCCCCACCTCCCACCCACC) with modified amino group at the 5-terminal to the surface of the treated substrate, and react at room temperature for 4 hours;

Wash the substrate three times with a phosphate buffered solution (PBS) solution with a molar volume concentration of 0.1M to remove non-specifically bound DNA strands;

Finally, use the bovine serum albumin (BSA) solution with mass concentration of 2.5% to coat the spots on the DNA and block the active sites on the DNA, then wash with ultrapure water (also known as UP water), and dry with a drying oven, Finally, a silicon dioxide substrate 25 with a gold nanofilm sprayed on its surface and DNA coated (specifically: dot-coated) on the gold nanofilm is finally obtained. At this time, you can continue to store it in a 4-degree environment for later use.

In order to form a gold nanoparticle distribution area 24 modified with DNA and 2-naphthylthiol on a silicon dioxide substrate 25, and prepare a surface-enhanced Raman (SERS) chip 19, the specific gold nanoparticle modification process includes the following steps :

The first step, the chloroauric acid solution that is 0.01% by mass concentration is heated and boiled under vigorous stirring, and 1% trisodium citrate aqueous solution is added rapidly under stirring state, the chloroauric acid solution and trisodium citrate aqueous solution The volume ratio is 100:3;

The second step, continue heating and boiling for 15 minutes, so that the light yellow solution gradually becomes a stable crimson, and then the prepared liquid is cooled to room temperature to obtain a gold colloidal solution. At this point, the gold colloid can be stored in a black bottle at 4°C for later use.

In terms of specific implementation, when the chloroauric acid solution is 50 mL, the corresponding trisodium citrate aqueous solution is 1.5 mL, and the corresponding gold colloid solution may have a diameter of 30 nm.

The third step is to add 2-naphthol (2NT) with a molar volume concentration of 0.01mM (mmol per liter) to the gold colloidal solution and mix it gently for 10 minutes to obtain 2-naphthol-labeled gold nanoparticles. The particle separation liquid is then centrifuged at a speed of 8000 rpm for 10 minutes, and the supernatant is removed, wherein the volume ratio of the 2-naphthylthiol (2NT) to the gold colloidal solution is 1:100;

In terms of specific implementation, when the volume of the 2-naphthylthiol (2NT) is 10uL, the corresponding gold colloidal solution needs 1mL.

The fourth step is to suspend with phosphate buffered saline (i.e. PBS, pH 7) with a molar volume concentration of 10 mM to obtain the suspended gold colloidal solution, wherein the volume ratio of the phosphate buffered saline and the gold colloidal solution is 1 :1;

Specifically, when the gold colloid solution is 1 mL, the selected phosphate buffer is also 1 mL.

Step 5, add the preset DNA solution into the suspended gold colloid solution, react for 12 hours, then add a sodium chloride solution with a molar volume concentration of 0.1M (that is, moles per liter) for 30 minutes, and then place Saltification was continued for 6 hours at a temperature of 4 degrees Celsius to obtain a mixture, wherein the volume ratio of 2-naphthylthiol (2NT) to sodium chloride solution was 1:2;

In the fifth step, specifically, when the volume of the 2-naphthylthiol (2NT) is 10 uL, the volume of the sodium chloride solution is 20 uL.

In terms of specific implementation, the specific preparation steps of the preset DNA solution are as follows:

The DNA (DNA sequence is CCCCCACCTCCCTCCCACCT) solution with a molar volume concentration of 100uM is mixed with a solution of tris(2-carboxyethyl)phosphine hydrochloride (TCEP) with a molar volume concentration of 10mM, wherein the DNA solution is mixed with tris(2-carboxyethyl) The volume ratio of base) phosphine hydrochloride (TCEP) solution is 20:3, and the volume ratio of DNA solution and 2-naphthylthiol (2NT) in the third step is 1:1, and then stand at room temperature for activation for 1 hour , to obtain a preset DNA solution. For example, when the DNA solution is 10uL, the tris(2-carboxyethyl)phosphine hydrochloride (TCEP) solution is 1.5uL.

The sixth step, the mixture was centrifuged at a speed of 8000 rpm for 30 minutes, the supernatant was removed, and then suspended in phosphate buffer (pH 7) with a molar volume concentration of 10 mM to obtain DNA and 2 -Naphthol-modified gold nanoparticle solution;

The seventh step is to coat the gold nanoparticles modified with DNA and 2-naphthol on the silica substrate, then place them in a drying oven for drying treatment, and finally form a gold nanoparticle modified with DNA and 2-naphthol on the silica substrate 25. - Naphthalenethiol-modified gold nanoparticle distribution region 24 to prepare a surface-enhanced Raman (SERS) chip 19 .

As shown in Figure 5, prepared by the above-mentioned method, any gold nanoparticle 26 is tightly connected together with a silicon dioxide substrate 25 through a DNA chain 27, a CHO acid group, and the surface of the silicon dioxide substrate 25 is sprayed with gold. A nano film, the gold nano film is coated with (specifically: coated by dots) DNA.

As shown in Figure 6, the abscissa is the Raman shift, which is the wavenumber difference of the scattered light relative to the incident light, and the ordinate is the photon count, which is the intensity of the scattered light. When there are mercury ions in the droplet, the gold nanoparticles will adsorb the gold nanoparticles to the surface of the SERS chip through the "C-Ag ²⁺ -C" structure, resulting in a strong Raman signal, and its characteristic peak is mainly located at 1380cm At ^-1 , the silver ion concentration is obtained through the intensity of the signal, and the signal is transmitted to the master node computer 10 for processing. The invention can realize specific and high-precision measurement of silver ions, and can realize real-time in-situ measurement, so it has far-reaching influence on promoting the development of underground space monitoring informatization.

In summary, compared with the prior art, the environmental network based on the aldehyde-based chip and gold nanoparticles to detect the content of mercury ions provided by the present invention can safely and reliably monitor the environment of the underground pipe network in all directions. In particular, it can effectively detect the content of mercury ions in the water transported by the underground pipe network, which can reduce the safety hazards of the underground pipe network and ensure the safe use of the underground pipe network. It is conducive to wide application and has great practical significance in production.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

1. detecting the environment network of mercury ion content based on aldehyde radical chip and gold nano grain, which is characterized in that including host node Computer (10) is connect between the host node computer (10) and multiple sensors of default type for wireless signal；

Multiple sensors of the default type are mounted on the heat distribution pipeline (3) and water supply line being laid in the underground space (100) (6) in and on the side wall of the underground space；

Multiple sensors of the default type are used to acquire the detection data of the corresponding underground space.

2. environment network as described in claim 1, which is characterized in that multiple sensors of the default type include：First Temperature sensor (5), second flow sensor (9) and surface-enhanced Raman SERS water quality sensors (12)；

First temperature sensor (5), second flow sensor (9) and surface-enhanced Raman SERS water quality sensors (12) peace In the water supply line (6), for detecting the temperature of water, flow and mercury ion content in the water supply line (6), so After be sent to host node computer (10).

3. environment network as claimed in claim 2, which is characterized in that multiple sensors of the default type further include：The One pressure sensor (4), first flow sensor (8) and second temperature sensor (11)；

The first pressure sensor (4), first flow sensor (8) and second temperature sensor (11) are mounted on the heating power In pipeline (3), pressure, flow and temperature for detecting institute's transmission medium in the heat distribution pipeline (3) are then sent to main section Point computer (10).

4. environment network as claimed in claim 3, which is characterized in that multiple sensors of the default type further include：Oxygen Gas sensor (13), carbon monoxide transducer (14), hydrogen sulfide sensor (15), Temperature Humidity Sensor (16) and nitrogen oxides pass Sensor (17)；

The oxygen sensor (13), carbon monoxide transducer (14), hydrogen sulfide sensor (15), Temperature Humidity Sensor (16) and NOx sensor (17) is separately mounted on the side wall of the underground space, dense for collecting the oxygen gas in the underground space Degree, carbon monoxide gas concentration, sulfureted hydrogen gas concentration, temperature, humidity and nitrous oxides concentration, are then sent to host node Computer (10).

5. environment network as claimed in claim 4, which is characterized in that further include：First monitoring camera (1) and the second monitoring Camera (2)；

First monitoring camera is located at the upper right side of the second monitoring camera (2)；

First monitoring camera (1) and the second monitoring camera (2) are mounted on the side wall of the underground space, are respectively used to adopt The image for collecting institute overlay area, is then sent to host node computer (10).

6. environment network as claimed in claim 5, which is characterized in that the host node computer (10), including：Data store Module, data processing module and wireless data transfer module, wherein：

Data memory module, the detection data of the underground space for acquiring multiple sensors of the default type, in real time It is stored；

Data processing module is connected with data memory module, the ground for acquiring multiple sensors of the default type The detection data of down space is compared with preset, corresponding normal value range respectively, if positioned at preset, corresponding Normal value range within, then judge corresponding data qualifier, otherwise, then judge corresponding defect of data, meanwhile, in real time Comparable situation is sent to the computer of ground base station by wireless data transfer module；

Data processing module is additionally operable to first monitoring camera (1) and the second monitoring camera (2) acquired image, The computer of ground base station is sent to by wireless data transfer module.

7. such as environment network according to any one of claims 1 to 6, which is characterized in that further include：Crusing robot (7), institute It states on the ground that crusing robot (7) is arranged between heat distribution pipeline (3) and water supply line (6).

8. environment network as claimed in claim 2, which is characterized in that the surface-enhanced Raman SERS water quality sensors (12) Including kit (20) and detection switch (18), wherein：

Detection switch (18) is mounted on the water supply line (6)；

The kit (20) is located at the lower section of detection switch (18), and the top of the kit (20) has multiple holes；

Inserted with surface-enhanced Raman SERS chips (19), the surface-enhanced Raman SERS chips in the kit (20) (19) include silicon dioxide substrates (25), be arranged at intervals on the silicon dioxide substrates (25) multiple by DNA and 2- naphthalene sulphur The gold nano grain distributed areas (24) of phenol modification；

The surface spraying of the silicon dioxide substrates (25) has gold nanometer film, and DNA is coated on the gold nanometer film；

Each gold nano grain distributed areas (24) by the modification of DNA and 2- thionaphthols are correspondingly arranged and are connected with a hole It is logical；

The kit (20) is arranged above a fibre-optical probe (23), and the fibre-optical probe (23) passes through an optical fiber It is connected with a portable Raman detector (21)；

It is provided with antenna (22) on the portable Raman detector (21).

9. environment network as claimed in claim 8, which is characterized in that prepare has gold nanometer film and Jenner in surface spraying The silicon dioxide substrates of DNA are also coated on rice film, specific preparation process includes the following steps：

First, it using the sheet glass of pre-set dimension as substrate, is impregnated 30 minutes in Piranha solution, makes its surface hydroxylation. Volume ratio in Piranha solution between sulfuric acid and hydrogen peroxide is 7：3；

Then, by surface hydroxylation, substrate rich in hydroxyl immerse the 3- aminopropyl trimethoxy silicon containing 5% mass solubility In the methanol solution of oxygen alkane APTMS, 12h is reacted at room temperature；

Then, continue to dip the substrate into the glutaraldehyde solution 4 hours that mass concentration is 2.5% so that glutaraldehyde solution and substrate Amino reaction occurs for the APTMS of surface modification, generates aldehyde radical surface；

Then, it cleans the substrate of substrate with ultra-pure water and is dried with nitrogen stream.Then by the DNA of 5 terminal modified amino (CCCCCACCTCCCACCCACC) it on the substrate surface after solution paint point to processing, reacts 4 hours at room temperature；

It is cleaned with the phosphate buffer solution solution of a concentration of 0.1M of molal volume and the wherein non-spy of cleaning removing three times is carried out to substrate The DNA chain that the opposite sex combines；

Finally, the bovine serum albumin solution for being 2.5% with mass concentration wraps up the spot on DNA and the activity on blocking dna Then site is cleaned with ultra-pure water, drying box is used in combination to dry, and final acquisition surface spraying has gold nanometer film and gold nano is thin The silicon dioxide substrates of DNA are also coated on film.

10. environment network as claimed in claim 8, which is characterized in that the preparation packet of the surface-enhanced Raman SERS chips Include following steps：

The first step, the chlorauric acid solution ebuillition of heated with vigorous stirring for being 0.01% by mass concentration, it is fast under stirring The volume ratio of the trisodium citrate aqueous solution of speed addition 1%, the chlorauric acid solution and trisodium citrate aqueous solution is 100:3；

Second step continues to heat and boil 15 minutes, and lurid solution is made to gradually become stable peony, then will be manufactured Liquid is cooled to room temperature, and obtains gold colloid；

The 2- thionaphthols of a concentration of 0.01mM of molal volume are added to gold colloid solution mixing third step, are gently mixed 10 points Clock obtains the gold nanoparticle separating liquid of 2- thionaphthols label, then according to 10 points of the speed of 8000 rev/min centrifugation rotation Clock removes supernatant, wherein the volume ratio of the 2- thionaphthols and gold colloid solution is 1:100；

4th step uses the phosphate buffer of a concentration of 10mM of 1mL to suspend again, the gold colloid solution after being suspended, wherein phosphorus The volume ratio of phthalate buffer and gold colloid solution is 1：1；

Preset DNA solution is added in the gold colloid solution after suspending 5th step, reacts 12 hours, then addition mole The sodium chloride solution salinization that volumetric concentration is 0.1M 30 minutes, then be placed in 4 degrees Celsius of temperature and continue salinization 6 hours, it obtains Mixture, wherein the volume ratio of 2- thionaphthols and sodium chloride solution is 1:2；

6th step centrifuges mixture 30 minutes under 8000 rpms of rotating speed, removes supernatant, is subsequently placed in a mole body It suspends in the phosphate buffer of a concentration of 10mM of product, obtains the gold nano grain solution by the modification of DNA and 2- thionaphthols；

7th step will be coated in silicon dioxide substrates by the gold nano grain of DNA and 2- thionaphthols modification, then be placed in drying It is dried in case, finally forms the gold nano grain distributed area by the modification of DNA and 2- thionaphthols in silicon dioxide substrates Domain prepares surface-enhanced Raman SERS chips；

In the 5th step, the specific preparation process of the preset DNA solution is as follows：

By DNA (CCCCCACCTCCCTCCCACCT) solution of a concentration of 100uM of molal volume and a concentration of 10mM of molal volume The mixing of three (2- carboxyethyls) phosphonium salt acid salt solutions, the wherein volume ratio of DNA solution and three (2- carboxyethyls) phosphonium salt acid salt solutions It is 20:3, and the volume ratio of DNA solution and the 2- thionaphthols in third step is 1:1, room temperature stands activation 1 hour, obtains pre- If DNA solution.