CN108444540A - The environment network of mercury ion content is detected based on aldehyde radical chip and silver nano-grain - Google Patents

The environment network of mercury ion content is detected based on aldehyde radical chip and silver nano-grain Download PDF

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CN108444540A
CN108444540A CN201810567680.3A CN201810567680A CN108444540A CN 108444540 A CN108444540 A CN 108444540A CN 201810567680 A CN201810567680 A CN 201810567680A CN 108444540 A CN108444540 A CN 108444540A
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solution
dna
silver
concentration
sensor
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邹强
李鑫
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Tianjin University
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Tianjin University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01DMEASURING NOT SPECIALLY ADAPTED FOR A SPECIFIC VARIABLE; ARRANGEMENTS FOR MEASURING TWO OR MORE VARIABLES NOT COVERED IN A SINGLE OTHER SUBCLASS; TARIFF METERING APPARATUS; MEASURING OR TESTING NOT OTHERWISE PROVIDED FOR
    • G01D21/00Measuring or testing not otherwise provided for
    • G01D21/02Measuring two or more variables by means not covered by a single other subclass
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65Raman scattering
    • G01N21/658Raman scattering enhancement Raman, e.g. surface plasmons

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Abstract

The invention discloses the environment networks that mercury ion content is detected based on aldehyde radical chip and silver nano-grain, including host node computer (10), it is connect for wireless signal between the host node computer (10) and multiple sensors of default type;Multiple sensors of the default type are mounted in the heat distribution pipeline (3) being laid in the underground space (100) and water supply line (6) 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.The environment network disclosed by the invention that mercury ion content is detected based on aldehyde radical chip and silver nano-grain, its can the environment of safe and reliable ground-to-ground down tube net carry out comprehensive monitoring, the content of mercury ion is effectively detected in the water that can be especially transmitted to underground pipe network, the security risk of underground pipe network can be reduced, ensure the safe handling of underground pipe network, be conducive to widely apply, be of great practical significance.

Description

The environment network of mercury ion content is detected based on aldehyde radical chip and silver nano-grain
Technical field
The present invention relates to Underground Space Environment monitoring technical fields, more particularly to based on aldehyde radical chip and silver nano-grain Detect the environment network of mercury ion content.
Background technology
Currently, underground pipe network is the most important thing in Chinese Urbanization construction process, it is to play city function, it is ensured that city Economy, Community health, coordinated development important substance basis, be presented intricate, mutually overlapping stereoscopic features, city Lower pipe network is the important component of urban infrastructure construction, be a city energy conveying, mass transfer, information transmit, The important carrier that water drainage mitigation and waste dump.
In view of current mercury and mercuric compounds to health there are many harm, be present in mercury in environment water be even more can be with It threatens to large-scale natural environment and humans and animals.Mercury is arranged in the form of solid waste, exhaust gas and waste water respectively It is put into environment, and arranges also be recycled back to dampening to the mercury of air and soil and be included into water body, cause long-term in environment water Mercury pollution repeatedly.Mercury can be accumulated in vivo, and the mercury in water body can be entered by food chain, especially aquatic products Into the human body.The mercury of accumulation in human body is difficult to be discharged by own metabolism, and Trace Mercury can generate liver kidney and other organs Toxicity causes oral inflammation, hand tremor, nerve problems and chronic mercury poisoning.With increasing for mercury cumulant, to human body Influence becomes apparent, and shows as serious irreversible cranial nerve lesions, it might even be possible to lead to brain death.Thus, natural water In mercury content environment measuring control in be the most important thing, for ensure human health, there is an urgent need to develop it is quick, sensitive, Selected method detects mercury ion.
But China has quite a few city not carry out unified allocation plan and management, underground to underground pipe network The management work of pipe network does things in his own way, lacks link up mutually, unordered controlled state is in, compared with urban construction speed.Pipe Reason is serious to fall behind, and accident is frequent occurrence.Cut off the water caused by accident, have a power failure, stopping the supple of gas or steam, the consequences such as communicating interrupt, fire explosion, no Only highly impact the quality of life and life security of the people, at the same also influence economic construction and national defense construction it is normal into Row.
For current underground pipe network, the problem of being primarily present, is:It, can not since the space structure of underground pipe network is complicated Comprehensive monitoring carried out to the environment of underground pipe network, in the water that can not be especially transmitted to underground pipe network the content of mercury ion into Row effectively detection ensures the safe handling of underground pipe network to reduce the security risk of underground pipe network.
Therefore, at present there is an urgent need to develop going out a kind of technology, can the environment of safe and reliable ground-to-ground down tube net carry out Comprehensive monitoring especially can effectively detect the content of mercury ion in the water of underground pipe network transmission, can be reduced The security risk of underground pipe network ensures the safe handling of underground pipe network.
Invention content
In view of this, the object of the present invention is to provide the rings for detecting mercury ion content based on aldehyde radical chip and silver nano-grain Border network, can the environment of safe and reliable ground-to-ground down tube net carry out comprehensive monitoring, especially can be to underground pipe network The content of mercury ion is effectively detected in the water of transmission, can be reduced the security risk of underground pipe network, be ensured underground pipe network Safe handling, is conducive to widely apply, be of great practical significance.
For this purpose, the present invention provides the environment network for detecting mercury ion content based on aldehyde radical chip and silver nano-grain, packet Host node computer is included, is connected for wireless signal between the host node computer and multiple sensors of default type;
Multiple sensors of the default type be mounted on the underground space in be laid with heat distribution pipeline and water supply line 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.
Wherein, multiple sensors of the default type include:First temperature sensor, second flow sensor and surface Enhance Raman SERS water quality sensors;
First temperature sensor, second flow sensor and surface-enhanced Raman SERS water quality sensors are mounted on institute It states in water supply line, for detecting the temperature of water in the water supply line, flow and mercury ion content, is then sent to main section Point computer.
Wherein, multiple sensors of the default type further include:First pressure sensor, first flow sensor and Two temperature sensors;
The first pressure sensor, first flow sensor and second temperature sensor are mounted on the heat distribution pipeline In, pressure, flow and temperature for detecting institute's transmission medium in the heat distribution pipeline are then sent to host node computer.
Wherein, multiple sensors of the default type further include:Oxygen sensor, carbon monoxide transducer, hydrogen sulfide Sensor, Temperature Humidity Sensor and NOx sensor;
The oxygen sensor, carbon monoxide transducer, hydrogen sulfide sensor, Temperature Humidity Sensor and nitrogen oxides sensing Device is separately mounted on the side wall of the underground space, dense for collecting the oxygen gas concentration in the underground space, CO gas Degree, sulfureted hydrogen gas concentration, temperature, humidity and nitrous oxides concentration are then sent to host node computer.
Wherein, further include:First monitoring camera and the second monitoring camera;
First monitoring camera is located at the upper right side of the second monitoring camera;
First monitoring camera and the second monitoring camera are mounted on the side wall of the underground space, are respectively used to acquire The image of institute overlay area, is then sent to host node computer.
Wherein, the host node computer, including:Data memory module, data processing module and wireless data transmission mould Block, wherein:
Data memory module, the detection data of the underground space for acquiring multiple sensors of the default type, It is stored in real time;
Data processing module is connected with data memory module, for acquiring multiple sensors of the default type The underground space detection data, be compared respectively with preset, corresponding normal value range, if positioned at it is preset, Within corresponding normal value range, then corresponding data qualifier is judged, otherwise, then judge corresponding defect of data, meanwhile, Comparable situation is sent to the computer of ground base station by wireless data transfer module in real time;
Data processing module is additionally operable to, by first monitoring camera and the second monitoring camera acquired image, lead to Cross the computer that wireless data transfer module is sent to ground base station.
Wherein, further include:Crusing robot, the ground that the crusing robot is arranged between heat distribution pipeline and water supply line On face.
Wherein, the surface-enhanced Raman SERS water quality sensors include kit and detection switch, wherein:
Detection switch is mounted on the water supply line;
The kit is located at the lower section of detection switch, and the top of the kit has multiple holes;
Include inserted with surface-enhanced Raman SERS chips, the surface-enhanced Raman SER S chips in the kit Silicon dioxide substrates are arranged at intervals with multiple silver nanoparticles modified by DNA and 2- thionaphthols in the silicon dioxide substrates Grain distributed areas;
The surface spraying of the silicon dioxide substrates has silver nanoparticle film, and DNA is coated on the silver nanoparticle film;
Each silver nano-grain distributed areas by the modification of DNA and 2- thionaphthols are correspondingly arranged and are connected with a hole It is logical;
The kit is arranged above a fibre-optical probe, the fibre-optical probe by an optical fiber and one just The formula Raman detector of taking is connected;
It is provided with antenna in the portable Raman detector.
Wherein, prepare has the silica that DNA is also coated on silver nanoparticle film and silver nanoparticle film in surface spraying Substrate, specific preparation process include 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 hydroxyl Change.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 trimethoxies containing 5% mass solubility In the methanol solution of radical siloxane 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 with Amino reaction occurs for the APTMS of substrate 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 (TTTTTCTTTGTTTCTTTGTTTC) 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 cleaning removing three times is carried out wherein to substrate The DNA chain of non-specific binding;
Finally, the bovine serum albumin solution for being 2.5% with mass concentration wraps up on spot and blocking dna on DNA Then active site is cleaned with ultra-pure water, drying box is used in combination to dry, and final acquisition surface spraying has silver nanoparticle film and silver is received The silicon dioxide substrates of DNA are also coated on rice film.
Wherein, the preparation of the surface-enhanced Raman SERS chips includes the following steps:
The first step, by the citric acid three of the silver nitrate solution of a concentration of 1mM of molal volume and a concentration of 40n M of molal volume Sodium solution mixing is put into container, and with vigorous stirring, the sodium borohydride solution of a concentration of 112mM of molal volume is added dropwise Enter, mixed solution gradually becomes khaki from transparent, obtains silver colloidal solution, wherein silver nitrate solution, citric acid three sodium solution Volume ratio is 50 between sodium borohydride solution:4:1;
Second step, the silver colloidal solution aging 24 hours by acquisition, make the sodium borohydride in silver colloidal solution decompose;
Third walks:The 2- thionaphthols of a concentration of 0.01mM of molal volume are added to silver colloidal solution and are mixed, wherein 2- naphthalenes The volume ratio of thiophenol and silver colloidal solution is:1:100, it is then gently mixed 10 minutes, obtains the silver nanoparticle of 2- thionaphthols label Particle separating liquid;
4th step:The Nano silver grain separating liquid that 2- thionaphthols are marked turns according to the speed centrifugation of 8000 rev/min It is 10 minutes dynamic, supernatant is removed, then suspended with the phosphate buffer of a concentration of 10mM of molal volume, the elargol after being suspended Liquid solution, wherein the volume ratio of phosphate buffer and gold and silver colloidal solution is 1:1;
Preset DNA solution is added in the silver colloidal solution after suspending 5th step, reacts 12 hours, is then added The sodium chloride solution salinization of a concentration of 0.1M of molal volume 30 minutes, then be placed in 4 degrees Celsius of temperature and continue salinization 6 hours, Obtain 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 and rubs It suspends in the phosphate buffer that your volumetric concentration is 10mM, the silver nano-grain obtained by the modification of DNA and 2- thionaphthols is molten Liquid;
7th step will be coated in silicon dioxide substrates by the silver nano-grain of DNA and 2- thionaphthols modification, then be placed in It is dried in drying box, finally forms the silver nano-grain point by the modification of DNA and 2- thionaphthols in silicon dioxide substrates Cloth region prepares surface-enhanced Raman SERS chips;
Wherein, in the 5th step, the specific preparation process of the preset DNA solution is as follows:
By the 5 of a concentration of 100uM of molal volume terminal modified sulfydryl DNA (TTTTTGTTTCTTTG TTTCTTTG) solution with Three (2- carboxyethyls) phosphonium salt acid salt solutions of a concentration of 10mM of molal volume mix, wherein DNA solution and three (2- carboxyethyls) phosphines The volume ratio of HCI solution is 20:3, and the volume ratio of DNA solution and the 2- thionaphthols in third step is 1:1, room temperature is quiet Activation 1 hour is set, preset DNA solution is obtained.
By the above technical solution provided by the invention as it can be seen that compared with prior art, the present invention provides based on aldehyde radical Chip and silver nano-grain detection mercury ion content environment network, can safe and reliable ground-to-ground down tube net environment into The comprehensive monitoring of row especially can effectively detect the content of mercury ion in the water of underground pipe network transmission, can be subtracted The security risk of few underground pipe network, ensures the safe handling of underground pipe network, is conducive to widely apply, and has great production real Trample meaning.
Description of the drawings
Fig. 1 is the knot of the environment network provided by the invention that mercury ion content is detected based on aldehyde radical chip and silver nano-grain Structure schematic diagram;
Fig. 2 is that the environment network provided by the invention that mercury ion content is detected based on aldehyde radical chip and silver nano-grain is based on The data transmission schematic diagram that purple honeybee ZigBee wireless communication techniques are formed;
Fig. 3 is table in the environment network provided by the invention for detecting mercury ion content based on aldehyde radical chip and silver nano-grain Face enhances the cooperating state simplified schematic diagram of Raman (SERS) water quality sensor and water supply line;
Fig. 4 is table in the environment network provided by the invention for detecting mercury ion content based on aldehyde radical chip and silver nano-grain Face enhances the structure schematic diagram of Raman (SERS) chip;
Fig. 5 is silver in the environment network provided by the invention for detecting mercury ion content based on aldehyde radical chip and silver nano-grain Attachment structure schematic diagram between nano particle and DNA chain;
Fig. 6 is table in the environment network provided by the invention for detecting mercury ion content based on aldehyde radical chip and silver nano-grain The Raman signal schematic diagram that face enhancing Raman (SERS) chip obtains when being detected to liquid;
In figure, 1 is the first monitoring camera;2 be the second monitoring camera;3 be heat distribution pipeline;4 sense for first pressure Device;5 be the first temperature sensor;6 be water supply line;7 be crusing robot;8 be first flow sensor;9 be second flow Sensor;10 be main node computer;11 be second temperature sensor;12 be surface-enhanced Raman (SERS) water quality sensor; 13 be oxygen sensor;14 be carbon monoxide transducer;15 be hydrogen sulfide sensor;16 be Temperature Humidity Sensor;17 be nitrogen oxygen Compound sensor;
18 be detection switch;19 be surface-enhanced Raman (SERS) chip;20 be kit;21 be portable Raman detection Instrument;22 be antenna;23 be fibre-optical probe;24 be the silver nano-grain distributed areas modified by DNA and 2- thionaphthols;25 be two Aoxidize silicon chip;26 be silver nano-grain;27 be DNA chain.
Specific implementation mode
In order to make those skilled in the art understand the present invention program with replacing, below in conjunction with the accompanying drawings with embodiment to this Invention is described in further detail.
Referring to Fig. 1 to Fig. 6, the present invention provides the environment that mercury ion content is detected based on aldehyde radical chip and silver nano-grain Network, including host node computer 10, the host node computer 10 and multiple sensors of default type (are used as partial node Point) between for wireless signal (especially by purple honeybee ZigBee wireless communication techniques) connect;
Multiple sensors of the default type are mounted on the heating power being laid in the underground space 100 (i.e. underground pipe network space) In pipeline 3 and water supply line 6 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, for example, temperature passes Sensor is used to detect the temperature data of institute's installation site.
In the present invention, in specific implementation, multiple sensors of the default type include:First temperature sensor 5, Two flow sensors 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 are installed In the water supply line 6, for detecting the temperature of water in the water supply line 6, flow and mercury ion content, then send Give host node computer 10 (especially by purple honeybee ZigBee wireless communication techniques).
In the present invention, in specific implementation, multiple sensors of the default type further include:First 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 thermal pipe In road 3, pressure, flow and temperature for detecting institute's transmission medium (such as hot water or steam) in the heat distribution pipeline 3, so After be sent to host node computer 10 (especially by purple honeybee Z igBee wireless communication techniques, such as ZigBee ad hoc network).
It should be noted that heat distribution pipeline is the transmission pipeline of high-temperature gas or high-temp liquid, for example, it is warm in city Feed channel.
In the present invention, in specific implementation, multiple sensors of the default type further include:Oxygen sensor 13, one Aoxidize carbon sensor 14, hydrogen sulfide sensor 15, Temperature Humidity Sensor 16 and NOx sensor 17;
The oxygen sensor 13, carbon monoxide transducer 14, hydrogen sulfide sensor 15, Temperature Humidity Sensor 16 and nitrogen oxygen Compound sensor 17 is separately mounted on the side wall of the underground space, is collected for the integrated environment information to the underground space, Specifically for collecting the oxygen gas concentration in the underground space, carbon monoxide gas concentration, sulfureted hydrogen gas concentration, temperature, wet Degree and nitrous oxides concentration, are then sent to host node computer 10 (especially by purple honeybee ZigBee wireless communication techniques, such as ZigBee ad hoc network).
In the present invention, in specific implementation, Underground Space Environment provided by the invention monitors network, further includes:First prison Control 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 second monitoring camera 2 is mounted on the side wall of the underground space, is respectively used to adopt The image for collecting institute overlay area, is then sent to host node computer 10 (especially by purple honeybee ZigBee wireless communication techniques, such as ZigBee ad hoc network), institute overlay area is monitored in real time to realize.
In specific implementation, first monitoring camera, 1 and second monitoring camera 2 can be monitoring gunlock.
It should be noted that specific implementation on, first monitoring camera 1 can be with 15 meters of pipe network entrance located underground at Furred ceiling supports 360 degree of infrared real time monitoring.Side wall at 18 meters of second monitoring camera, 2 pipe network entrance located underground, Institute overlay area can be monitored in real time.
It should be noted that for the present invention, in multiple sensors of the default type, each sensor includes Power supply module, central control module, environment acquisition module and wireless communication module.
For the present invention, the host node computer 10, including:Data memory module, data processing module and without line number According to transmission module, wherein:
Data memory module, the underground for acquiring multiple sensors (i.e. as minor node) of the default type are empty Between detection data, stored in real time, to form database;
Data processing module is connected with data memory module, for (making multiple sensors of the default type For minor node) detection data of the underground space of acquisition, it is (such as preset with preset, corresponding normal value range respectively Temperature value range, preset humidity range) be compared, if positioned at preset, corresponding normal value range it It is interior, then judge corresponding data qualifier, otherwise, then judges corresponding defect of data, meanwhile, comparable situation is passed through into nothing in real time Line data transmission module is sent to the computer of ground base station so that the staff on ground is recognized that the underground space Every environmental parameter situation, obtains the environmental information of the underground space, realizes the real time monitoring of underground pipe network.In addition, data processing Module is additionally operable to, by 1 and second monitoring camera of the first monitoring camera, 2 acquired image, pass through wireless data transmission Module is sent to the computer of ground base station.
For the present invention, in order to which more preferably ground-to-ground down space is monitored, Underground Space Environment network provided by the invention Further include:Crusing robot 7, the crusing robot 7 are arranged on the ground between heat distribution pipeline 3 and water supply line 6.
It should be noted that the crusing robot 7 is mainly used for carrying out the security information monitoring of underground utilities, collect ground The security information of underground pipelines.The bottom of the crusing robot has wheel, can be equipped with infrared thermography, visible thereon Light video camera head and laser navigation module (existing laser navigation module);
Wherein, by infrared thermography, temperature change can be detected, so as to monitor heat distribution pipeline 3 in real time and supply The leakage problem of the underground utilities such as waterpipe 6;
Visible image capturing head monitors in real time for the image to the underground space, for ensureing that pipeline performance has safely Important role.
Laser navigation module, the route planning for ensureing crusing robot 7 and intelligent detecting.
It should be noted that the crusing robot 7 is used to move and carry out the agent structure of environmental monitoring, it is existing The structure of crusing robot is not unfolded to describe herein herein similarly to the prior art.
In specific implementation, the data memory module, data processing module and wireless data transfer module are located at host node The lower part of computer 10.
It should be noted that for the present invention, the data of all minor nodes can be transmitted to master by zigbee network In node computer, data are collected, handle, compare and are retrieved by each data module of host node computer, most The environmental information that will be obtained afterwards can be transferred out by zigbee wireless communication modules.Acquired by the data of whole system, Storage, processing and transmission, realize the comprehensive utilization of underground pipe gallery information, are carried for the overall planning and integrated dispatch of the underground space For strong data supporting.
As shown in figure 3, for the present invention, surface-enhanced Raman (SERS) water quality sensor 12 includes 20 He of kit Detection switch 18, wherein:
Detection switch 18 is mounted on the water supply line 6;It is specifically as follows an electromagnetic switch valve;
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) chip 19, surface-enhanced Raman (SERS) core in the kit 20 Piece 19 includes silicon dioxide substrates 25, and multiple DNA and 2- thionaphthols that pass through are arranged at intervals in the silicon dioxide substrates 25 and are repaiied The silver nano-grain distributed areas 24 of decorations;
The surface spraying of the silicon dioxide substrates 25 has silver nanoparticle film, is coated on the silver nanoparticle film (specific For:Coated by point) DNA;
Each silver nano-grain distributed areas 24 by the modification of DNA and 2- thionaphthols are correspondingly arranged with a hole and phase Connection, can be connected to the liquid flowed into from hole;
The kit 20 is arranged above a fibre-optical probe 23, the fibre-optical probe 23 by an optical fiber with One portable Raman detector 21 is connected;
Antenna 22 (being specifically as follows purple honeybee ZigBee antennas) is provided in the portable Raman detector 21.
In specific implementation, the portable Raman detector 21 can be a kind of existing portable Raman detector.Example Such as, may refer to it is application No. is CN201621206981.6, in the Chinese utility model patent Shen that on November 9th, 2016 announces Please《A kind of portable multi-function Raman detector》The portable Raman detector that prospectus is recorded.
Therefore, for the present invention, due to installing detection switch 18 below water supply line 6, when starting detection, inspection is opened Slowdown monitoring switch 18 will instill in the SERS detection chips 19 in kit 20 from the dropping liquid drop that water supply line 6 flows out, to occur Reaction, different pollutant monitorings will be instilled in different holes and are detected.The laser that fibre-optical probe 23 can send out 532nm carries out Raman detection is simultaneously handled in portable Raman detector 21, finally by 21 detected water of portable Raman detector Middle mercury ion content data radios to host node computer 10 by antenna 22.
For the present invention, it should be noted that surface-enhanced Raman (SERS) water quality sensor 12 is mainly used for mercury in water The detection of ion, the principle utilized, which is mercury ion, to form " T-Hg with the T bases in DNA2+- T " structures, it is indirect by SERS Detect the presence of mercury ion.
(it is specially to prepare to have also to be coated on silver nanoparticle film and silver nanoparticle film in surface spraying:By spot printing On) silicon dioxide substrates 25 of DNA, specific preparation process includes the following steps:
First, using the sheet glass of pre-set dimension as substrate, in the Piranha solution (body wherein between sulfuric acid and hydrogen peroxide Product is than being 7:3) it is impregnated 30 minutes in, makes its surface hydroxylation;
Then, by surface hydroxylation, substrate rich in hydroxyl immerse the 3- aminopropyl trimethoxies containing 5% mass solubility In the methanol solution of radical siloxane (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 with Amino reaction occurs for the APTMS of substrate 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 (DNA of 5 terminal modified amino Sequence is:TTTTTCTTTGTTTCTTTGTTTC) on the substrate surface after solution paint point to processing, it is small that 4 are reacted at room temperature When;
It is cleaned with phosphate buffer solution (PBS) solution of a concentration of 0.1M of molal volume and cleaning removing three times is carried out to substrate The wherein DNA chain of non-specific binding;
Finally, bovine serum albumin(BSA) (BSA) solution for being 2.5% with mass concentration wraps up spot and blocking dna on DNA On active site, then clean with ultra-pure water (also known as UP water), drying box is used in combination to dry, final acquisition surface spraying has Yin Na It is also coated on rice film and silver nanoparticle film and (is specially:Coated by point) silicon dioxide substrates 25 of DNA.At this time, may be used To continue to preserve to spare in 4 degree of environment.
In order to form the silver nano-grain distributed areas by the modification of DNA and 2- thionaphthols in silicon dioxide substrates 25 24, surface-enhanced Raman (SERS) chip 19 is prepared, the modified by silver nanoparticles process specifically carried out includes the following steps:
The first step, by the citric acid three of the silver nitrate solution of a concentration of 1mM of molal volume and a concentration of 40n M of molal volume Sodium solution mixing is put into container, and with vigorous stirring, the sodium borohydride solution of a concentration of 112mM of molal volume is added dropwise Enter, mixed solution gradually becomes khaki from transparent, illustrates to generate Nano silver grain, obtains silver colloidal solution, wherein nitric acid Volume ratio is 50 between silver-colored solution, citric acid three sodium solution and sodium borohydride solution:4:1;
Before the first step, it may be implemented to needing container to be used to handle, specially:Take the conical flask of 100mL It is first washed with water totally, is dried for standby with being cleaned after chloroazotic acid soaked overnight.
In specific implementation, when silver nitrate solution is 20mL, corresponding citric acid three sodium solution is 1.6mL, corresponding boron Sodium hydride solution is 0.4mL, and the diameter of the corresponding silver colloidal solution obtained can be 30nm.
Second step, the silver colloidal solution aging 24 hours by acquisition, make the sodium borohydride in silver colloidal solution decompose;At this moment It waits, can also be placed under 4 degrees Celsius of environment and save backup.
Third walks:The 2- thionaphthols (2NT) of a concentration of 0.01mM of molal volume are added to silver colloidal solution and are mixed, In, 2- thionaphthols (2NT) and the volume ratio of silver colloidal solution are:1:100, it is then gently mixed 10 minutes, obtains 2- thionaphthols The Nano silver grain separating liquid of label;
In specific implementation, when 2- thionaphthols (2NT) are 10uL, corresponding silver colloidal solution is 1mL.
4th step:The Nano silver grain separating liquid that 2- thionaphthols are marked turns according to the speed centrifugation of 8000 rev/min It is 10 minutes dynamic, supernatant is removed, then suspended with the phosphate buffer (i.e. PBS, pH value 7) of a concentration of 10mM of molal volume, Silver colloidal solution after being suspended, wherein the volume ratio of phosphate buffer and gold and silver colloidal solution is 1:1;
In specific implementation, when gold and silver colloidal solution is 1mL, selected phosphate buffer is also 1mL.
Preset DNA solution is added in the silver colloidal solution after suspending 5th step, reacts 12 hours, is then added The sodium chloride solution salinization of a concentration of 0.1M of molal volume (i.e. mole every liter) 30 minutes, then it is placed in 4 degrees Celsius of temperature relaying Continuous salinization 6 hours, obtains mixture, wherein the volume ratio of 2- thionaphthols (2NT) and sodium chloride solution is 1:2;
In the 5th step, in specific implementation, when the volume of the 2- thionaphthols (2NT) is 10uL, sodium chloride solution Volume is 20uL.
In specific implementation, the specific preparation process of the preset DNA solution is as follows:
By the 5 of a concentration of 100uM of molal volume terminal modified sulfydryl DNA, (DNA sequence dna is:TTTT TGTTTCTTTGTTTCTTTG) three (2- carboxyethyls) phosphonium salt hydrochlorate (TCEP) solution of solution and a concentration of 10mM of molal volume are mixed It closes, wherein the volume ratio of DNA solution and three (2- carboxyethyls) phosphonium salt hydrochlorate (T CEP) solution is 20:3, and DNA solution and The volume ratio of 2- thionaphthols (2NT) in three steps is 1:1, then room temperature, which is stood, activates 1 hour, obtains preset DNA solution.Example Such as, when DNA solution is 10uL, three (2- carboxyethyls) phosphonium salt hydrochlorate (TCEP) solution are 1.5uL.
6th step centrifuges mixture 30 minutes under 8000 rpms of rotating speed, removes supernatant, is subsequently placed in and rubs It suspends in the phosphate buffer (pH value 7) that your volumetric concentration is 10mM, obtains the Yin Na by the modification of DNA and 2- thionaphthols Rice grain solution;
7th step will be coated in silicon dioxide substrates by the silver nano-grain of DNA and 2- thionaphthols modification, then be placed in It is dried in drying box, finally forms the silver nano-grain by the modification of DNA and 2- thionaphthols in silicon dioxide substrates 25 Distributed areas 24 prepare surface-enhanced Raman (SERS) chip 19.
As shown in figure 5, being prepared by the above method, any one silver nano-grain 26 passes through 27, CHO acid of DNA chain Base is closely joined together with silicon dioxide substrates 25, and the surface spraying of the silicon dioxide substrates 25 has silver nanoparticle film, described It is coated on silver nanoparticle film and (is specially:Coated by point) DNA.
As shown in fig. 6, abscissa is Raman shift, wave-number difference of the light relative to incident light is exactly scattered, ordinate is light Sub-count exactly scatters the intensity of light.In the presence of having mercury ion in the drop instilled, silver nano-grain passes through " T-Hg2+- Silver nano-grain is adsorbed onto SERS chip surfaces by T " structures, compared to hanging in the silver nano-grain of chip, can be generated strong Strong Raman signal, characteristic peak are predominantly located at 1380cm-1Place obtains ion concentration of mercury by the power of signal, and by signal Host node computer 10 is transferred to be handled.The present invention innovatively utilizes the specific reaction of mercury ion and T bases, and designs Unique structure detection mercury ion realizes the microscratch detection of mercury ion, strong for having in terms of drinking water safety It ensures, and is suitable for underground space monitoring network, push its digitized development.
In conclusion compared with prior art, it is provided by the invention that mercury is detected based on aldehyde radical chip and silver nano-grain The environment network of ion concentration, can the environment of safe and reliable ground-to-ground down tube net carry out comprehensive monitoring, especially can The content of mercury ion is effectively detected in the enough water transmitted to underground pipe network, can reduce the security risk of underground pipe network, is protected The safe handling for demonstrate,proving underground pipe network, is conducive to widely apply, be of great practical significance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (10)

1. detecting the environment network of mercury ion content based on aldehyde radical chip and silver 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 silver nano-grain distributed areas (24) of phenol modification;
The surface spraying of the silicon dioxide substrates (25) has silver nanoparticle film, and DNA is coated on the silver nanoparticle film;
Each silver 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 preparation has silver nanoparticle film in surface spraying and silver is received 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 (TTTTTCTTTGTTTCTTTGTTTC) 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 silver nanoparticle film and silver nanoparticle 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:
It is the first step, the silver nitrate solution of a concentration of 1mM of molal volume and the trisodium citrate of a concentration of 40nM of molal volume is molten Liquid mixing is put into container, and with vigorous stirring, the sodium borohydride solution of a concentration of 112mM of molal volume is added dropwise, Mixed solution gradually becomes khaki from transparent, obtains silver colloidal solution, wherein silver nitrate solution, citric acid three sodium solution with Volume ratio is 50 between sodium borohydride solution:4:1;
Second step, the silver colloidal solution aging 24 hours by acquisition, make the sodium borohydride in silver colloidal solution decompose;
Third walks:The 2- thionaphthols of a concentration of 0.01mM of molal volume are added to silver colloidal solution and are mixed, wherein 2- thionaphthols Volume ratio with silver colloidal solution is:1:100, it is then gently mixed 10 minutes, obtains the Nano silver grain of 2- thionaphthols label Separating liquid;
4th step:The Nano silver grain separating liquid that 2- thionaphthols are marked, according to the speed centrifugation rotation 10 of 8000 rev/min Minute, supernatant is removed, then suspended with the phosphate buffer of a concentration of 10mM of molal volume, the silver colloid after being suspended is molten Liquid, wherein the volume ratio of phosphate buffer and gold and silver colloidal solution is 1:1;
Preset DNA solution is added in the silver colloidal 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 silver nanoparticle solution by the modification of DNA and 2- thionaphthols;
7th step will be coated in silicon dioxide substrates by the silver nano-grain of DNA and 2- thionaphthols modification, then be placed in drying It is dried in case, finally forms the silver nano-grain distributed area by the modification of DNA and 2- thionaphthols in silicon dioxide substrates Domain prepares surface-enhanced Raman SERS chips;
Wherein, in the 5th step, the specific preparation process of the preset DNA solution is as follows:
By the 5 of a concentration of 100uM of molal volume terminal modified sulfydryl DNA (TTTTTGTTTCTTTGTTTCTTTG) solution and mole body Three (2- carboxyethyls) phosphonium salt acid salt solutions mixing of a concentration of 10mM of product, wherein DNA solution and three (2- carboxyethyls) phosphonium salt hydrochlorates The volume ratio of solution 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, obtain preset DNA solution.
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