CN108444542A - The environment network of silver ion content is detected based on gold silver nanometer particle - Google Patents
The environment network of silver ion content is detected based on gold silver nanometer particle Download PDFInfo
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- CN108444542A CN108444542A CN201810567698.3A CN201810567698A CN108444542A CN 108444542 A CN108444542 A CN 108444542A CN 201810567698 A CN201810567698 A CN 201810567698A CN 108444542 A CN108444542 A CN 108444542A
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- G01D—MEASURING 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
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- G—PHYSICS
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
The invention discloses the environment networks that silver ion content is detected based on gold silver nanometer particle, including host node computer (10), are 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 silver ion content is detected based on gold silver nanometer particle, its can the environment of safe and reliable ground-to-ground down tube net carry out comprehensive monitoring, the content of silver 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
Technical field
The present invention relates to Underground Space Environment monitoring technical field, more particularly to based on gold silver nanometer particle detection silver from
The environment network of sub- 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.
Currently, when the environment water in underground pipe network is contaminated, it is easy to dramatically increase containing for the silver ion in water body
Amount.Silver ion is extremely toxic substance, and the toxic action having includes mainly：(1) make the protein of human body and various enzyme denaturations.
(2) the internal silver ion of entrance is more than 0.8g will cause the silver-colored spot of blue to precipitate on the skin.Since silver ion has very by force
Oxidisability, so can also cause the symptoms such as internal organs oedema into the silver ion in human body.Causing death when serious.Human body
Without effectively arranging silver-colored mechanism.So once intake silver ion is just mainly accumulated in bone and liver.And silver ion poisoning does not have
There is effective antidote.Thus, the silver ion content in natural water is the most important thing in environment measuring control, to ensure people
Class health, there is an urgent need to develop quick, sensitive, selected method to detect silver 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 silver 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 silver 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 environment network for detecting silver ion content based on gold silver nanometer particle,
It can the environment of safe and reliable ground-to-ground down tube net carry out comprehensive monitoring, underground pipe network can especially be transmitted
The content of silver ion is effectively detected in water, can reduce the security risk of underground pipe network, ensures that the safety of underground pipe network makes
With being conducive to widely apply, be of great practical significance.
For this purpose, the present invention provides the environment network for detecting silver ion content based on gold silver nanometer particle, including host node
Computer connects between the host node computer and multiple sensors of default type for wireless signal；
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, flow and silver ion content in the water supply line, 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；
Inserted with surface-enhanced Raman SERS chips in the kit, the surface-enhanced Raman SERS chips include two
Silicon chip is aoxidized, multiple gold and silver hybridization modified by DNA and 2- thionaphthols are arranged at intervals in the silicon dioxide substrates and are received
Rice grain distributed areas；
Each gold and silver hybridized nanoparticle distributed areas by the modification of DNA and 2- thionaphthols are correspondingly arranged with a hole
And it is connected；
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, the preparation of the surface-enhanced Raman SERS chips includes the following steps：
First, the gold nano grain solution by the modification of DNA and 2- thionaphthols is prepared；
Secondly, the silver nanoparticle solution by the modification of DNA and 2- thionaphthols is prepared；
Then, by the gold nano grain solution modified by DNA and 2- thionaphthols identified and by DNA and 2- naphthalenes
The silver nanoparticle solution of thiophenol modification, mixes, and completes the hybridization of gold silver nanometer particle, obtains and passes through DNA and 2- naphthalenes
The gold and silver hybridized nanoparticle solution of thiophenol modification；
Finally, silicon dioxide substrates will be coated in by the gold and silver hybridized nanoparticle solution of DNA and 2- thionaphthols modification
On, then be placed in drying box and be dried, the gold and silver by the modification of DNA and 2- thionaphthols is finally formed in silicon dioxide substrates
Hybridized nanoparticle distributed areas prepare surface-enhanced Raman chip.
Wherein, the gold nano grain solution prepared by the modification of DNA and 2- thionaphthols, specifically includes following steps：
The first step, the chlorauric acid solution ebuillition of heated with vigorous stirring for being 0.01% by mass concentration, in stirring
Under be rapidly added 1% trisodium citrate aqueous solution, the volume ratio of 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 system
At liquid be cooled to room temperature, obtain 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 minutes, the gold nanoparticle separating liquid of 2- thionaphthols label is obtained, then centrifuges and rotates according to the speed of 8000 rev/min
10 minutes, remove 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,
In, the volume ratio of phosphate 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, 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；Wherein, the tool of the preset DNA solution
Preparation step is：By DNA (CCACCTGTGAGCTGACT) solution of a concentration of 100uM of molal volume and molal volume concentration
It is mixed for three (2- carboxyethyls) phosphonium salt acid salt solutions of 10mM, wherein DNA solution and three (2- carboxyethyls) phosphonium salt acid salt solutions
Volume ratio 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.
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 gold nano grain obtained by the modification of DNA and 2- thionaphthols is molten
Liquid；
The silver nanoparticle solution prepared by the modification of DNA and 2- thionaphthols, specifically includes 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 40nM 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；The wherein described preset DNA solution it is specific
Preparation process is：By DNA (CCCCCACCTCCCACCCACC) solution and DNA of a concentration of 100uM of molal volume
(CCAGTCAGCTCACAGGT) 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 both DNA solutions and three (2- carboxyethyls) phosphonium salt hydrochlorate (TCEP) solution is 20:3, and both
The volume ratio of DNA solution and the 2- thionaphthols (2NT) in third step is 1:1, then room temperature, which is stood, activates 1 hour, is preset
DNA solution；
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.
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 gold and silver
Nano particle detect silver ion content environment network, can safe and reliable ground-to-ground down tube net environment carry out it is comprehensive
Monitoring, the content of silver ion effectively be detected in the water that can be especially transmitted to underground pipe network, can reduce buried pipe
The security risk of net ensures the safe handling of underground pipe network, is conducive to widely apply, be of great practical significance.
Description of the drawings
Fig. 1 is the structural representation of the environment network provided by the invention that silver ion content is detected based on gold silver nanometer particle
Figure；
Fig. 2 is that the environment network provided by the invention that silver ion content is detected based on gold silver nanometer particle is based on purple honeybee
The data transmission schematic diagram that ZigBee wireless communication techniques are formed；
Fig. 3 is that surface enhanced is drawn in the environment network provided by the invention for detecting silver ion content based on gold silver nanometer particle
The cooperating state simplified schematic diagram of graceful (SERS) water quality sensor and water supply line；
Fig. 4 is that surface enhanced is drawn in the environment network provided by the invention for detecting silver ion content based on gold silver nanometer particle
The structure schematic diagram of graceful (SERS) chip；
Fig. 5 is gold nano in the environment network provided by the invention for detecting silver ion content based on gold silver nanometer particle
Attachment structure schematic diagram between grain, silver nano-grain and DNA chain；
Fig. 6 is that surface enhanced is drawn in the environment network provided by the invention for detecting silver ion content based on gold silver nanometer particle
The Raman signal schematic diagram that graceful (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 gold and silver hybridized nanoparticle distributed areas modified by DNA and 2- thionaphthols；
25 be silicon dioxide substrates；26 be gold nano grain；27 be DNA chain, and 28 be silver nano-grain.
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 network that silver ion content is detected based on gold silver nanometer particle, packets
Host node computer 10 is included, is between the host node computer 10 and multiple sensors (being used as minor node) of default type
Wireless signal (especially by purple honeybee ZigBee wireless communication techniques) connects；
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, flow and silver ion content in the water supply line 6, 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 ZigBee 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 gold and silver hybridized nanoparticle distributed areas 24 of decorations；
Each gold and silver hybridized nanoparticle distributed areas 24 by the modification of DNA and 2- thionaphthols are corresponding with a hole to be set
It sets and is connected, the liquid flowed into from hole can be connected to；
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 silver ion content data radio 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 in water silver-colored
The detection of ion, the principle utilized, which is silver ion, to form " C-Ag with the C bases in DNA2+- C " structures, it is indirect by SERS
Detect the presence of silver ion.Since sulfydryl can form stable Ag-S keys with nano silver, by 5 terminal modified sulfydryls and C can be rich in
Silver nano-grain surface is arrived in DNA (CCCCCACCTCCCACCCACC) modifications of base.But silver nano-grain is oxidized easily, because
This by and gold nano grain combination, to ensure its stability.
In order to form the gold and silver hybridized nanoparticle distribution by the modification of DNA and 2- thionaphthols in silicon dioxide substrates 25
Region 24 prepares surface-enhanced Raman (SERS) chip 19, the gold and silver hybridized nanoparticle modification packet specifically carried out
Include following steps：
First, the gold nano grain solution by the modification of DNA and 2- thionaphthols is prepared；
Secondly, the silver nanoparticle solution by the modification of DNA and 2- thionaphthols is prepared；
Then, by the gold nano grain solution modified by DNA and 2- thionaphthols identified and by DNA and 2- naphthalenes
The silver nanoparticle solution of thiophenol modification, mixes, and completes the hybridization of gold silver nanometer particle, obtains and passes through DNA and 2- naphthalenes
The gold and silver hybridized nanoparticle solution of thiophenol modification；
Finally, silicon dioxide substrates will be coated in by the gold and silver hybridized nanoparticle solution of DNA and 2- thionaphthols modification
On, then be placed in drying box and be dried, the gold by the modification of DNA and 2- thionaphthols is finally formed in silicon dioxide substrates 25
Silver-colored hybridized nanoparticle distributed areas 24 prepare surface-enhanced Raman (SERS) chip 19.
In order to prepare the gold nano grain solution modified by DNA and 2- thionaphthols, following steps are specifically included：
The first step, the chlorauric acid solution ebuillition of heated with vigorous stirring for being 0.01% by mass concentration, in stirring
Under be rapidly added 1% trisodium citrate aqueous solution, the volume ratio of 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 system
At liquid be cooled to room temperature, obtain gold colloid solution.At this time, gold colloid can be stored in black bottle at 4 DEG C
It is spare.
In specific implementation, when the chlorauric acid solution is 50mL, corresponding trisodium citrate aqueous solution is 1.5mL, corresponding
The diameter of gold colloid solution can be 30nm.
Third step, by 2- thionaphthols (2NT) addition of a concentration of 0.01mM of molal volume (i.e. mM every liter) to gold size
Liquid solution mix, be gently mixed 10 minutes, obtain 2- thionaphthols label gold nanoparticle separating liquid, then according to 8000 turns/
Speed centrifugation rotation per minute 10 minutes, removes supernatant, wherein the body of 2- thionaphthols (2NT) and gold colloid solution
Product is than being 1:100；
In specific implementation, when the volume of the 2- thionaphthols (2NT) is 10uL, corresponding gold colloid solution needs 1mL.
4th step uses the phosphate buffer (i.e. PBS, pH value 7) of a concentration of 10mM of 1mL to suspend again, after being suspended
Gold colloid solution, wherein the volume ratio of phosphate buffer and gold colloid solution be 1：1；
In specific implementation, when gold colloid solution is 1mL, selected phosphate buffer is also 1mL.
Preset DNA solution is added in the gold colloid 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 DNA (DNA sequence dna CCACCTGTGAGCTGACT) solution and molal volume of a concentration of 100uM of molal volume
Three (2- carboxyethyls) phosphonium salt hydrochlorate (TCEP) solution of a concentration of 10mM mix, wherein DNA solution and three (2- carboxyethyls) phosphonium salts
The volume ratio of hydrochlorate (TCEP) solution is 20:3, and the volume ratio of DNA solution and the 2- thionaphthols (2NT) in third step is 1:
1, then room temperature, which is stood, activates 1 hour, obtains preset DNA solution.For example, when DNA solution is 10uL, three (2- carboxyethyls)
Phosphonium salt hydrochlorate (TCEP) solution is 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 Jenner by the modification of DNA and 2- thionaphthols
Rice grain solution；
In order to prepare the silver nanoparticle solution modified by DNA and 2- thionaphthols, following steps are specifically included：
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 40nM 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 DNA (DNA sequence dna CCCCCACCTCCCACCCACC) solution and DNA of a concentration of 100uM of molal volume
(CCAGTCAGCTCACAGGT) 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 both DNA solutions and three (2- carboxyethyls) phosphonium salt hydrochlorate (TCEP) solution is 20:3, and both
The volume ratio of DNA solution and the 2- thionaphthols (2NT) in third step is 1:1, then room temperature, which is stood, activates 1 hour, is preset
DNA solution；For example, when DNA (CCCCCACCTCCCACCCACC) and DNA (CCAGTCAGCTCACAGGT) both DNA is molten
When liquid is respectively 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.
As shown in figure 5, being prepared by the above method, the surrounding of any one gold nano grain 26 has closely surrounded multiple silver
Nano particle 28 forms a gold and silver hybridized nanoparticle set, each gold and silver hybridized nanoparticle set and adjacent gold and silver
It is closely joined together by DNA chain 27 between hybridized nanoparticle set 26.
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 silver ion in the drop instilled, gold nano grain passes through " C-Ag2+-
C " structure gold and silver hybridized nanoparticles are reunited, and strong Raman signal are generated after reunion, characteristic peak is predominantly located at
1380cm-1Place, obtains concentration of silver ions by the power of signal, and transmit a signal to host node 7 and handled, passes through gold and silver
The hybridization of nano particle, had not only ensured the good SERS effects of silver nano-grain, but also had ensured that gold nano grain is not easy by oxygen
The characteristic of change, to realize the detection of silver ion 1pg/mL (every milliliter of pik), to ensureing that it is far-reaching that Drinking Water for Residents has safely
Influence, while also become underground pipe gallery security information detection an important ring.
In conclusion compared with prior art, it is provided by the invention that silver ion content is detected based on gold silver nanometer particle
Environment network, can the environment of safe and reliable ground-to-ground down tube net carry out comprehensive monitoring, especially can be to underground
The content of silver ion is effectively detected in the water of pipe network transmission, can reduce the security risk of underground pipe network, ensures buried pipe
The safe handling of net 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 silver ion content based on gold silver nanometer particle, which is characterized in that 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 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), temperature, flow and silver ion content for detecting water 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 and silver hybridized nanoparticle distributed areas (24) of phenol modification；
Each gold and silver hybridized nanoparticle distributed areas (24) by the modification of DNA and 2- thionaphthols are correspondingly arranged with a hole
And it is connected；
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 the preparation packet of the surface-enhanced Raman SERS chips 19
Include following steps：
First, the gold nano grain solution by the modification of DNA and 2- thionaphthols is prepared；
Secondly, the silver nanoparticle solution by the modification of DNA and 2- thionaphthols is prepared；
Then, by the gold nano grain solution modified by DNA and 2- thionaphthols identified and by DNA and 2- thionaphthols
The silver nanoparticle solution of modification, mixes, and completes the hybridization of gold silver nanometer particle, obtains and passes through DNA and 2- thionaphthols
The gold and silver hybridized nanoparticle solution of modification；
Finally, it will be coated in silicon dioxide substrates by the gold and silver hybridized nanoparticle solution of DNA and 2- thionaphthols modification, then
It is placed in drying box and is dried, finally form the gold and silver hybridization by the modification of DNA and 2- thionaphthols in silicon dioxide substrates
Nano particle distributed areas prepare surface-enhanced Raman chip.
10. environment network as claimed in claim 9, which is characterized in that the gold prepared by the modification of DNA and 2- thionaphthols
Nanoparticles solution specifically includes 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；Wherein, the specific system of the preset DNA solution
It is for step：DNA (CCACCTGTGAGCTGACT) solution and molal volume of a concentration of 100uM of molal volume is a concentration of
Three (2- carboxyethyls) phosphonium salt acid salt solutions of 10mM mix, wherein the body of DNA solution and three (2- carboxyethyls) phosphonium salt acid salt solutions
Product is than being 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
Obtain preset DNA solution.
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；
The silver nanoparticle solution prepared by the modification of DNA and 2- thionaphthols, specifically includes 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；The specific preparation of the wherein described preset DNA solution
Step is：By DNA (CCCCCACCTCCCACCCACC) solution and DNA of a concentration of 100uM of molal volume
(CCAGTCAGCTCACAGGT) 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 both DNA solutions and three (2- carboxyethyls) phosphonium salt hydrochlorate (TCEP) solution is 20:3, and both
The volume ratio of DNA solution and the 2- thionaphthols (2NT) in third step is 1:1, then room temperature, which is stood, activates 1 hour, is preset
DNA solution；
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.
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