CN107144557A - A kind of detection method of silicon substrate SERS chips and preparation method thereof and TNT - Google Patents
A kind of detection method of silicon substrate SERS chips and preparation method thereof and TNT Download PDFInfo
- Publication number
- CN107144557A CN107144557A CN201710253748.6A CN201710253748A CN107144557A CN 107144557 A CN107144557 A CN 107144557A CN 201710253748 A CN201710253748 A CN 201710253748A CN 107144557 A CN107144557 A CN 107144557A
- Authority
- CN
- China
- Prior art keywords
- tnt
- silicon
- solution
- chip
- silicon wafer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to public safety detection field, disclose a kind of silicon substrate surface enhancing Raman scattering (Surface enhanced Raman spectroscopy for being used to detect TNT, SERS) chip and preparation method thereof, and one built with the portable Raman instruments of 785nm detects TNT portable stage when participating in the cintest.The silver nitrate reduction method that the silicon base chip is aided in by hydrofluoric acid, silver nano-grain is modified on silicon chip in situ, then the compound (such as p-aminophenyl thiophenol) interacted in the surface modification of chip with TNT, capture and the enhancing of SERS signal for TNT.The silicon substrate SERS chips that the present invention is built have excellent sensitivity, and test limit is less than~1pM (~45.4fg/cm2), and with preferable SERS signal reappearance, relative standard deviation (relative standard deviation, RSD) is less than 15%.Importantly, the constructed portable stage for detecting TNT when participating in the cintest, it is adaptable to the TNT of trace in qualitative analysis actual environment sample.
Description
Technical field
The invention belongs to public safety detection field, relate generally to a kind of silicon substrate SERS chips and preparation method thereof and
TNT detection method.
Background technology
2,4,6 ﹣ trinitrotoluenes (TNT) are a kind of the most frequently used dangerous explosives, can not only cause security threat, and
Also result in problem of environmental pollution.If the mankind are chronically exposed in TNT, TNT can be absorbed by skin, it is possible to cause anaemia
With dysfunction of liver (referring to：J.Am.Chem.Soc.2008,130,9726-9733).Importantly, Environmental Protection Agency USA
Point out, if comprising more than 88nM TNT residues in a daily drinking water of child, it is possible to the trouble of a ten thousandth can be increased
Cancer risk (referring to：2012Edition of the drinking water standards and health
advisories,United States Environmental Protection Agency,Washington,DC,2012)。
Even more noteworthy, the equipment that transport hub increasingly demand can quickly and accurately detect recessive explosive, this demand
The structure of detection trace TNT portable analysis platform is when participating in the cintest promoted.At present, many ripe, traditional detection method applications
In detecting various explosives, including gas-chromatography, ion mobility spectrometry, neutron excites analysis and electrochemical method.Although these
Method is generally acknowledged, but they still have some shortcomings --- it is time-consuming, and need skilled artisan to operate
Large-scale instrument (Nat.Commun.2013,4,1636).
In order to solve these problems, researchers have been developed various optical sensors, successfully realized
Quickly, simple and inexpensive TNT analyses detection, these sensors include colorimetric, fluorescence and Raman sensor etc. (referring to：
Chem.Soc.2016,138,3302-3305；J.Am.Chem.Soc.2016,138,4685-4692；Nat.Commun.2016,
7,12189).In these sensors, because it has abundant " fingerprint " information, noiseless and lossless detection, small sample
These features with portable qualitative analysis in situ are prepared, portable Raman explosives sensor has obtained huge concern.However,
Raman sensor is there is also some shortcomings, and Raman signal is extremely faint, it is easy to which, by hyperfluorescence ambient interferences, spectral resolution is poor.
Fortunately, SERS technologies can solve these problems, and when molecule is distributed or during close to focus, Raman signal is exaggerated several
The order of magnitude is in single molecules level, and this method can be used for highly sensitive detection sample.
At present, increasing people begins to focus on the portable SERS sensors of development or chip and is combined with hand-held Raman instrument
When participating in the cintest detection platform, expect realize when participating in the cintest detection practical systems in trace TNT.However, there is no in the prior art on
TNT portable SERS sensors and detection platform of being come personally associated with hand-held Raman instrument is detected in practical systems.
The content of the invention
In view of this, it is an object of the invention to construct associated with a kind of silicon substrate SERS chips and portable Raman instrument
Detection platform when participating in the cintest.
To achieve the above object, the present invention constructs a kind of preparation method of silicon substrate SERS chips, comprises the steps：
Silicon wafer is cleaned for the first time, surface removal of impurities, then carry out second of cleaning；
Silicon wafer surface after being cleaned at described second carries out silicon hydrogenation, obtains the silicon wafer for having Si -- H bond to surface
Piece；
The surface there is into the silicon wafer of Si -- H bond in Ag+Reduction reaction is carried out under environment, silver nanoparticle ion modification is obtained
Silicon wafer AgNPs@Si；
Take modified compound to be reacted with AgNPs Si, third time cleaning is carried out after reaction, silicon base chip is obtained.
It is preferred that, the surface removal of impurities is specially：
Silicon wafer after the first time is cleaned soaks in the concentrated sulfuric acid and mixed solution of hydrogen peroxide.
It is preferred that, described hydrogenperoxide steam generator mass concentration is 30%, the concentrated sulfuric acid and the hydrogen peroxide volume
Than for 1:(0.01~100).
It is preferred that：The silicon hydrogenation is specifically, the silicon wafer after described second is cleaned is in hydrogen fluoride solution
Immersion；
Described hydrogen fluoride solution mass concentration is 1~40%.
It is preferred that, the reduction reaction is specially：
The silicon wafer that there is Si -- H bond on the surface is soaked in the strong acid salt of silver and the mixed solution of hydrogen fluoride；Described
The strong acid concentration of salt solution of silver is 1M, and hydrogen fluoride solution mass concentration is 1~40%, silver-colored strong acid salting liquid and hydrogen fluoride solution
Volume ratio=1:(0.01~100).
It is preferred that, the modified compound is selected from:P-aminophenyl thiophenol, 4- sulfydryls toluene, 4- mercaptobenzoic acids and 2- first
One or more in epoxide benzenethiol.
It is preferred that, the concentration of the modified compound solution is 10-3﹣ 10-7M。
Present invention also offers a kind of silicon base chip, it is prepared from by described preparation method.
A kind of TNT detection method, described silicon base chip is placed in sample solution, the sample solution concentration range
For：10-7﹣ 10-11M；
The SERS chips are incubated in the sample solution of various concentrations, the time of incubation：10~30min.
Chip after the incubation is detected in Raman instrument, the concentration of TNT in sample is obtained；The Raman
The laser of device is 785nm, and laser power is 300mW, and it detects that TNT concentration range is：10-4﹣ 10-7M。
The invention discloses chip prepared by a kind of preparation method of silicon substrate SERS chips and this method, by AgNPs@
Modified compound (PABT) on Si surface, successfully constructs silicon substrate SERS chips.Because sulfydryl, institute is not present in TNT molecules
So that AgNPs Si surface can not be connected to by Ag-S keys, strengthen from being unable to cause corresponding Raman signal.Compare
For, electron-defect compound TNT and Donor compound PABT can form TNT-PABT compounds by electro transfer, and
PABT Raman signal enhancing is produced, so as to realize the analysis detection to TNT.It is worth mentioning that, when the TNT of various concentrations is molten
When liquid reacts with constructed silicon substrate SERS chips, because TNT concentration is higher, formed with certain density PABT molecular actions
TNT-PABT compounds it is more, caused Raman signal enhancing is more obvious.TNT sample solutions can be carried out from 10-11Arrive
10-7The detection of the M ranges of linearity, test limit can reach~1pM (~45.4fg/cm2)；The chip has preferable SERS signal
Reappearance (RSD：＜ 15%)；In addition, after the chip is used in conjunction with the portable Raman instruments of 785nm, can fast and effeciently detect
The TNT of trace, realizes portable and in situ detection TNT in environmental sample (such as lake water, spirits, soil and envelope etc.).
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing is briefly described, it should be apparent that, the accompanying drawing for the present invention in describing below is only the one of the present invention
A little embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to these
Accompanying drawing obtains other accompanying drawings.
Fig. 1 is that the silicon substrate SERS chips of the present invention detect real with the portable stage when participating in the cintest constructed by portable Raman instrument
The TNT of trace schematic diagram in the system of border；
Fig. 2 is the ESEM (a) for the silicon substrate SERS chips that the present invention is prepared, AFM (b) sign photograph
The size of piece, wherein silver nano-grain is about 170nm, uniform to fix on silicon；
Fig. 3 is SERS experimentalists and technicians of the silicon substrate SER multifunction chips of the invention prepared to various concentrations TNT solution
As a result spectrogram and corresponding Raman mapping scheme；
Fig. 4 is the portable stage for detecting TNT when participating in the cintest based on silicon substrate SERS chips constructed by the present invention, for contacting
Property detection practical systems (such as lake water, spirits, soil and envelope) in trace TNT.A figures are silicon substrate SERS chips and 785nm
The TNT principles of trace in portable Raman instrument combination contact detection practical systems (such as lake water, spirits, soil and envelope)
Figure.B, c, d and e figure are the SERS spectra figure for detecting TNT in lake water, spirits, soil and envelope this four samples respectively.
Fig. 5 is the portable stage for detecting TNT when participating in the cintest of the silicon substrate SERS chips constructed by the present invention, for untouchable
Detect the TNT of trace in practical systems (such as lake water, spirits).A figures are silicon substrate SERS chips and the portable Raman instruments of 785nm
The TNT schematic diagrams of trace in the untouchable detection practical systems (such as lake water, spirits) of combination.B and c figures are detection lake water respectively
With the SERS spectra figure of TNT in spirits the two samples.
Embodiment
With reference to deficiency of the prior art, inaccurate or undetectable problem is detected to the TNT of low concentration, the present invention is carried
A kind of silicon base chip has been supplied, and has disclosed the preparation method of the chip and is combined the method that portable Raman instrument detects TNT.
The invention solves the problems that a kind of preparation method of silicon substrate SERS chips, comprises the steps：
Silicon wafer is cleaned for the first time, surface removal of impurities, then carry out second of cleaning；Silicon wafer after being cleaned at described second
Piece surface carries out silicon hydrogenation, obtains the silicon wafer for having Si -- H bond to surface；The surface there is into the silicon wafer of Si -- H bond in Ag+
Reduction reaction is carried out under environment, the silicon wafer AgNPs@Si of silver nanoparticle ion modification are obtained；Take modified compound and AgNPs@Si
Reaction, carries out third time cleaning, obtains silicon base chip after reaction.
According to the present invention, silicon wafer is subjected to first time cleaning first in above-mentioned steps, the system cleans specific for the first time
To be carried out being cleaned by ultrasonic 10~20min successively with deionized water, acetone, surface removal of impurities is then carried out again, dense sulphur is specially added
The mixed solution of acid and hydrogen peroxide soaks 20~35min to silicon wafer, and second of cleaning is finally carried out again, will with deionized water
Silicon wafer is cleaned up；Described hydrogenperoxide steam generator mass concentration is 20~40%, preferably 30%, the concentrated sulfuric acid and institute
It is 1 to state hydrogen peroxide volume ratio:(0.01~100).
The silicon wafer cleaned up for the second time is put into hydrogen fluoride solution and carries out silicon hydrogenation, surface is obtained and is formed greatly
Measure the silicon wafer of Si -- H bond；It is preferred that, described hydrogen fluoride solution mass concentration is 1~40%.
According to the present invention, the silicon wafer that there is Si -- H bond on the surface Ag has been put into+Reduction reaction is carried out under environment, preferably
Be put into the mixed solution of silver nitrate and hydrogen fluoride and carry out reduction reaction, silver ion can silicon wafer surface reduction into one layer
Even Nano silver grain, obtains AgNPs@Si；The reduction reaction is preferably that the surface is had into the silicon wafer of Si -- H bond in silver
Soaked in the mixed solution of strong acid salt and hydrogen fluoride；Described silver-colored strong acid concentration of salt solution is 1M, and hydrogen fluoride solution quality is dense
Spend for 1~40%, silver-colored strong acid salting liquid and hydrogen fluoride solution volume ratio=1:(0.01~100).
Obtain after AgNPs@Si, modified compound and the AgNPs@Si are reacted, the modified compound is preferably pair
One or more in aminothiophenol, 4- sulfydryls toluene, 4- mercaptobenzoic acids and 2- methoxybenzene thiols.Due to described
There are mercapto groups in modified compound, can be modified by Ag-S keys on the surface of silver nano-grain, and other groups energy and TNT
It is combined, so TNT samples can be detected preferably；More preferably p-aminophenyl thiophenol (p-aminobenzenethiol,
PABT), it is preferred that the concentration of the modified compound solution is 10-3﹣ 10-7M。
The silicon base chip is subjected to third time cleaning, is specially washed with deionized several times, then blown with nitrogen
It is dry, obtain PABT modification AgNPs@Si silicon substrate SERS chips.
It is preferred that, the obtained chip is placed in a series of TNT sample solutions of various concentrations, wherein TNT molecules
It can be interacted, be dried up afterwards with nitrogen by electric charge transfer with PABT molecules, finally be drawn using laser co-focusing
Graceful instrument carries out analysis detection to it, and the sample solution concentration range is preferably：10-7﹣ 10-11M；
The chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest is built, detection is real
TNT in the system of border.Choose actual environment sample (such as lake water, spirits, soil and envelope) to be tested, be added dropwise to core
On piece, after being dried up with nitrogen, carried out detecting when participating in the cintest with portable Raman instrument.
Detection method be specially the SERS chips are incubated in the sample solution of various concentrations, incubation when
Between：10~30min.
Chip after the incubation is detected in Raman instrument, the concentration of TNT in sample is obtained；The Raman
The laser of device is 785nm, and laser power is 300mW.It detects that TNT concentration range is：10-4﹣ 10-7M。
The invention also discloses a kind of silicon base chip, it is prepared from according to the method described above.
Below in conjunction with the accompanying drawing in the embodiment of the present invention, detailed retouch is carried out to the technical scheme in the embodiment of the present invention
State.
Raw material used in the present invention can freely be bought by market, be that analysis is pure；
Embodiment 1
Take 0.5 × 0.5cm2Single silicon wafer of size 3~6, put into clean beaker spent respectively in Ultrasound Instrument from
Sub- water, acetone ultrasound 15 minutes, obtain the clean silicon chip in surface standby.Then silicon chip is immersed in 40mL sulfuric acid and hydrogen peroxide
Mixed solution in the 30 minutes impurity to remove wherein indissoluble, finally clean up silicon wafer with deionized water standby.
The silicon chip of wash clean is placed in 10wt% hydrofluoric acid dips 20min, allows it to carry out silicon hydrogenation, makes the table of silicon chip
Face formed Si -- H bond, then treated silicon chip is placed in culture dish, smooth surface upward, be then placed in 1M silver nitrate and
Mixed solution (volume ratio=1 of 40wt% hydrogen fluoride:50) reduction reaction is carried out in, silver ion can be reduced by Si -- H bond, in silicon
The surface of piece forms the Nano silver grain of one layer of uniform growth in situ, obtains the silicon wafer of Surface Modified Ag Nanoparticles
(AgNPs@Si).Put it into afterwards containing 10-3Concussion reaction 30min in M p-aminophenyl thiophenol solution, remove afterwards not with silver
The p-aminophenyl thiophenol molecule of nano particle effect, with deionized water rinsing 3 times, finally dries up surface, you can obtain with nitrogen
Silicon substrate SERS multifunction chips.
Prepared silicon substrate SERS chips are placed in 10-7M TNT solution immersion, wherein TNT molecules can be logical with PABT molecules
Cross electric charge transfer to be interacted, react 20min, dried up afterwards with nitrogen, finally using laser co-focusing Raman
Can device carries out analysis detection to it, be interacted to investigate TNT with p-aminophenyl thiophenol, strengthen Raman signal.
Prepared chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest is built,
Detect the TNT of trace in practical systems.Four environmental samples are have chosen to be tested, including lake water, spirits, soil and envelope.
For untouchable detection, 10 are added in 900 μ L lake water and 900 μ L spirits first-4M TNT solution, then takes respectively
50 μ L solution are added in our homemade small containers, be stained with silicon substrate SERS chips below the lid of container, container is covered tightly afterwards,
45 DEG C, after a period of time are heated to, chip is taken out, is carried out detecting when participating in the cintest with portable Raman instrument, each sample is measured three times.
For contact detection, the TNT solution of various concentrations is added in 900 μ L lake water and 900 μ L spirits, while also existing
The TNT solution of various concentrations is added in 600mg soil and 150mg envelope, then with 900 μ L absolute methanols to soil and letter
TNT molecules in envelope are extracted, and 50 μ L solution are finally taken out respectively and are added drop-wise on chip, allow solution fully to be contacted with chip,
After being dried up with nitrogen, then carried out with portable Raman instrument detecting when participating in the cintest, each sample is measured three times.
Embodiment 2
Take 0.5 × 0.5cm2Single silicon wafer of size 3~6, put into clean beaker spent respectively in Ultrasound Instrument from
Sub- water, acetone ultrasound 15 minutes, obtain the clean silicon chip in surface standby.Then silicon chip is immersed in 40mL sulfuric acid and hydrogen peroxide
Mixed solution in the 30 minutes impurity to remove wherein indissoluble, finally clean up silicon wafer with deionized water standby.
The silicon chip of wash clean is placed in 20wt% hydrofluoric acid dips 20min, allows it to carry out silicon hydrogenation, makes the table of silicon chip
Face formed Si -- H bond, then treated silicon chip is placed in culture dish, smooth surface upward, be then placed in 1M silver nitrate and
Mixed solution (volume ratio=1 of 40wt% hydrogen fluoride:50) reduction reaction is carried out in, silver ion can be reduced by Si -- H bond, in silicon
The surface of piece forms the Nano silver grain of one layer of uniform growth in situ, obtains the silicon wafer of Surface Modified Ag Nanoparticles
(AgNPs@Si).Put it into afterwards containing 10-4Concussion reaction 40min in M p-aminophenyl thiophenol solution, remove afterwards not with silver
The p-aminophenyl thiophenol molecule of nano particle effect, with deionized water rinsing 3 times, finally dries up surface, you can obtain with nitrogen
Silicon substrate SERS multifunction chips.
Prepared silicon substrate SERS chips are placed in 10-8M TNT solution immersion, wherein TNT molecules can be logical with PABT molecules
Cross electric charge transfer to be interacted, react 20min, dried up afterwards with nitrogen, finally using laser co-focusing Raman
Can device carries out analysis detection to it, be interacted to investigate TNT with p-aminophenyl thiophenol, strengthen Raman signal.
Prepared chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest is built,
Detect the TNT of trace in practical systems.Four environmental samples are have chosen to be tested, including lake water, spirits, soil and envelope.
For untouchable detection, 10 are added in 900 μ L lake water and 900 μ L spirits first-4M TNT solution, then takes respectively
50 μ L solution are added in our homemade small containers, be stained with silicon substrate SERS chips below the lid of container, container is covered tightly afterwards,
45 DEG C, after a period of time are heated to, chip is taken out, is carried out detecting when participating in the cintest with portable Raman instrument, each sample is measured three times.
For contact detection, the TNT solution of various concentrations is added in 900 μ L lake water and 900 μ L spirits, while also existing
The TNT solution of various concentrations is added in 600mg soil and 150mg envelope, then with 900 μ L absolute methanols to soil and letter
TNT molecules in envelope are extracted, and are finally taken 50 μ L solution to be added drop-wise on chip, are allowed solution fully to be contacted with chip, use nitrogen
After drying, then carried out with portable Raman instrument detecting when participating in the cintest, each sample is measured three times.
Embodiment 3
Take 0.5 × 0.5cm2Single silicon wafer of size 3~6, put into clean beaker spent respectively in Ultrasound Instrument from
Sub- water, acetone ultrasound 15 minutes, obtain the clean silicon chip in surface standby.Then silicon chip is immersed in 40mL sulfuric acid and hydrogen peroxide
Mixed solution in the 30 minutes impurity to remove wherein indissoluble, finally clean up silicon wafer with deionized water standby.
The silicon chip of wash clean is placed in 30wt% hydrofluoric acid dips 20min, allows it to carry out silicon hydrogenation, makes the table of silicon chip
Face formed Si -- H bond, then treated silicon chip is placed in culture dish, smooth surface upward, be then placed in 1M silver nitrate and
Mixed solution (volume ratio=1 of 40wt% hydrogen fluoride:100) reduction reaction is carried out in, silver ion can be reduced by Si -- H bond, in silicon
The surface of piece forms the Nano silver grain of one layer of uniform growth in situ, obtains the silicon wafer of Surface Modified Ag Nanoparticles
(AgNPs@Si).Put it into afterwards containing 10-5Concussion reaction 30min in M p-aminophenyl thiophenol solution, remove afterwards not with silver
The p-aminophenyl thiophenol molecule of nano particle effect, with deionized water rinsing 3 times, finally dries up surface, you can obtain with nitrogen
Silicon substrate SERS multifunction chips.
Prepared silicon substrate SERS chips are placed in 10-9M TNT solution immersion, wherein TNT molecules can be logical with PABT molecules
Cross electric charge transfer to be interacted, react 30min, dried up afterwards with nitrogen, finally using laser co-focusing Raman
Can device carries out analysis detection to it, be interacted to investigate TNT with p-aminophenyl thiophenol, strengthen Raman signal.
Prepared chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest, inspection is built
Survey the TNT of trace in practical systems.Four environmental samples are have chosen to be tested, including lake water, spirits, soil and envelope.It is right
In untouchable detection, 10 are added in 900 μ L lake water and 900 μ L spirits first-5M TNT solution, then takes 50 μ respectively
L solution is added in our homemade small containers, is stained with silicon substrate SERS chips below the lid of container, container is covered tightly afterwards, plus
Heat is to 45 DEG C, after a period of time, takes out chip, is carried out detecting when participating in the cintest with portable Raman instrument, each sample is measured three times.It is right
In contact detection, the TNT solution of various concentrations is added in 900 μ L lake water and 900 μ L spirits, while also in 600mg
Soil and 150mg envelope in add various concentrations TNT solution, then with 900 μ L absolute methanols in soil and envelope
TNT molecules extracted, finally take 50 μ L solution to be added drop-wise on chip, allow solution fully to be contacted with chip, dried up with nitrogen
Afterwards, then with portable Raman instrument carry out detecting when participating in the cintest, each sample is measured three times.
Embodiment 4
Take 0.5 × 0.5cm2Single silicon wafer of size 3~6, put into clean beaker spent respectively in Ultrasound Instrument from
Sub- water, acetone ultrasound 15 minutes, obtain the clean silicon chip in surface standby.Then silicon chip is immersed in 40mL sulfuric acid and hydrogen peroxide
Mixed solution in the 30 minutes impurity to remove wherein indissoluble, finally clean up silicon wafer with deionized water standby.
The silicon chip of wash clean is placed in 40wt% hydrofluoric acid dips 30min, allows it to carry out silicon hydrogenation, makes the table of silicon chip
Face formed Si -- H bond, then treated silicon chip is placed in culture dish, smooth surface upward, be then placed in 1M silver nitrate and
Mixed solution (volume ratio=1 of 40wt% hydrogen fluoride:100) reduction reaction is carried out in, silver ion can be reduced by Si -- H bond, in silicon
The surface of piece forms the Nano silver grain of one layer of uniform growth in situ, obtains the silicon wafer of Surface Modified Ag Nanoparticles
(AgNPs@Si).Put it into afterwards containing 10-6Concussion reaction 50min in M p-aminophenyl thiophenol solution, remove afterwards not with silver
The p-aminophenyl thiophenol molecule of nano particle effect, with deionized water rinsing 3 times, finally dries up surface, you can obtain with nitrogen
Silicon substrate SERS multifunction chips.
Prepared silicon substrate SERS chips are placed in 10-10M TNT solution immersion, wherein TNT molecules can be with PABT molecules
Interacted by electric charge transfer, react 20min, dried up afterwards with nitrogen, finally using laser co-focusing Raman
Can instrument carries out analysis detection to it, be interacted to investigate TNT with p-aminophenyl thiophenol, strengthen Raman signal.
Prepared chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest, inspection is built
Survey the TNT of trace in practical systems.Four environmental samples are have chosen to be tested, including lake water, spirits, soil and envelope.It is right
In untouchable detection, 10 are added in 900 μ L lake water and 900 μ L spirits first-6M TNT solution, then takes 50 μ respectively
L solution is added in our homemade small containers, is stained with silicon substrate SERS chips below the lid of container, container is covered tightly afterwards, plus
Heat is to 45 DEG C, after a period of time, takes out chip, is carried out detecting when participating in the cintest with portable Raman instrument, each sample is measured three times.It is right
In contact detection, the TNT solution of various concentrations is added in 900 μ L lake water and 900 μ L spirits, while also in 600mg
Soil and 150mg envelope in add various concentrations TNT solution, then with 900 μ L absolute methanols in soil and envelope
TNT molecules extracted, finally take 50 μ L solution to be added drop-wise on chip, allow solution fully to be contacted with chip, dried up with nitrogen
Afterwards, then with portable Raman instrument carry out detecting when participating in the cintest, each sample is measured three times.
Embodiment 5
Take 0.5 × 0.5cm2Single silicon wafer of size 3~6, put into clean beaker spent respectively in Ultrasound Instrument from
Sub- water, acetone ultrasound 15 minutes, obtain the clean silicon chip in surface standby.Then silicon chip is immersed in 40mL sulfuric acid and hydrogen peroxide
Mixed solution in the 30 minutes impurity to remove wherein indissoluble, finally clean up silicon wafer with deionized water standby.
The silicon chip of wash clean is placed in 10wt% hydrofluoric acid dips 30min, allows it to carry out silicon hydrogenation, makes the table of silicon chip
Face formed Si -- H bond, then treated silicon chip is placed in culture dish, smooth surface upward, be then placed in 1M silver nitrate and
Mixed solution (volume ratio=1 of 40wt% hydrogen fluoride:100) reduction reaction is carried out in, silver ion can be reduced by Si -- H bond, in silicon
The surface of piece forms the Nano silver grain of one layer of uniform growth in situ, obtains the silicon wafer of Surface Modified Ag Nanoparticles
(AgNPs@Si).Put it into afterwards containing 10-7Concussion reaction 1h in M p-aminophenyl thiophenol solution, removes do not received with silver afterwards
The p-aminophenyl thiophenol molecule of rice grain effect, with deionized water rinsing 3 times, finally dries up surface, you can obtain silicon with nitrogen
Base SERS multifunction chips.
Prepared silicon substrate SERS chips are placed in 10-11M TNT solution immersion, wherein TNT molecules can be with PABT molecules
Interacted by electric charge transfer, react 20min, dried up afterwards with nitrogen, finally using laser co-focusing Raman
Can instrument carries out analysis detection to it, be interacted to investigate TNT with p-aminophenyl thiophenol, strengthen Raman signal.
Prepared chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest, inspection is built
Survey the TNT of trace in practical systems.Four environmental samples are have chosen to be tested, including lake water, spirits, soil and envelope.It is right
In untouchable detection, 10 are added in 900 μ L lake water and 900 μ L spirits first-7M TNT solution, then takes 50 μ respectively
L solution is added in our homemade small containers, is stained with silicon substrate SERS chips below the lid of container, container is covered tightly afterwards, plus
Heat is to 45 DEG C, after a period of time, takes out chip, is carried out detecting when participating in the cintest with portable Raman instrument, each sample is measured three times.It is right
In contact detection, the TNT solution of various concentrations is added in 900 μ L lake water and 900 μ L spirits, while also in 600mg
Soil and 150mg envelope in add various concentrations TNT solution, then with 900 μ L absolute methanols in soil and envelope
TNT molecules extracted, finally take 50 μ L solution to be added drop-wise on chip, allow solution fully to be contacted with chip, dried up with nitrogen
Afterwards, then with portable Raman instrument carry out detecting when participating in the cintest, each sample is measured three times.
Embodiment 6
Take 0.5 × 0.5cm2Single silicon wafer of size 3~6, put into clean beaker spent respectively in Ultrasound Instrument from
Sub- water, acetone ultrasound 15 minutes, obtain the clean silicon chip in surface standby.Then silicon chip is immersed in 40mL sulfuric acid and hydrogen peroxide
Mixed solution in the 30 minutes impurity to remove wherein indissoluble, finally clean up silicon wafer with deionized water standby.
The silicon chip of wash clean is placed in 10wt% hydrofluoric acid dips 30min, allows it to carry out silicon hydrogenation, makes the table of silicon chip
Face formed Si -- H bond, then treated silicon chip is placed in culture dish, smooth surface upward, be then placed in 1M silver nitrate and
Mixed solution (volume ratio=1 of 40wt% hydrogen fluoride:50) reduction reaction is carried out in, silver ion can be reduced by Si -- H bond, in silicon
The surface of piece forms the Nano silver grain of one layer of uniform growth in situ, obtains the silicon wafer of Surface Modified Ag Nanoparticles
(AgNPs@Si).Put it into afterwards containing 10-3Concussion reaction 30min in M p-aminophenyl thiophenol solution, remove afterwards not with silver
The p-aminophenyl thiophenol molecule of nano particle effect, with deionized water rinsing 3 times, finally dries up surface, you can obtain with nitrogen
Silicon substrate SERS multifunction chips.
Prepared silicon substrate SERS chips are placed in 10-7M TNT solution immersion, wherein TNT molecules can be logical with PABT molecules
Cross electric charge transfer to be interacted, react 20min, dried up afterwards with nitrogen, finally using laser co-focusing Raman
Can device carries out analysis detection to it, be interacted to investigate TNT with p-aminophenyl thiophenol, strengthen Raman signal.
Prepared chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest, inspection is built
Survey the TNT of trace in practical systems.Four environmental samples are have chosen to be tested, including lake water, spirits, soil and envelope.It is right
In untouchable detection, 10 are added in 900 μ L lake water and 900 μ L spirits first-4M TNT solution, then takes 50 μ respectively
L solution is added in our homemade small containers, is stained with silicon substrate SERS chips below the lid of container, container is covered tightly afterwards, plus
Heat is to 45 DEG C, after a period of time, takes out chip, is carried out detecting when participating in the cintest with portable Raman instrument, each sample is measured three times.It is right
In contact detection, the TNT solution of various concentrations is added in 900 μ L lake water and 900 μ L spirits, while also in 600mg
Soil and 150mg envelope in add various concentrations TNT solution, then with 900 μ L absolute methanols in soil and envelope
TNT molecules extracted, finally take 50 μ L solution to be added drop-wise on chip, allow solution fully to be contacted with chip, dried up with nitrogen
Afterwards, then with portable Raman instrument carry out detecting when participating in the cintest, each sample is measured three times.
Embodiment 7
Take 0.5 × 0.5cm2Single silicon wafer of size 3~6, put into clean beaker spent respectively in Ultrasound Instrument from
Sub- water, acetone ultrasound 15 minutes, obtain the clean silicon chip in surface standby.Then silicon chip is immersed in 40mL sulfuric acid and hydrogen peroxide
Mixed solution in the 30 minutes impurity to remove wherein indissoluble, finally clean up silicon wafer with deionized water standby.
The silicon chip of wash clean is placed in 20wt% hydrofluoric acid dips 30min, allows it to carry out silicon hydrogenation, makes the table of silicon chip
Face formed Si -- H bond, then treated silicon chip is placed in culture dish, smooth surface upward, be then placed in 1M silver nitrate and
Mixed solution (volume ratio=1 of 40wt% hydrogen fluoride:100) reduction reaction is carried out in, silver ion can be reduced by Si -- H bond, in silicon
The surface of piece forms the Nano silver grain of one layer of uniform growth in situ, obtains the silicon wafer of Surface Modified Ag Nanoparticles
(AgNPs@Si).Put it into afterwards containing 10-4Concussion reaction 2h in M p-aminophenyl thiophenol solution, removes do not received with silver afterwards
The p-aminophenyl thiophenol molecule of rice grain effect, with deionized water rinsing 3 times, finally dries up surface, you can obtain silicon with nitrogen
Base SERS multifunction chips.
Prepared silicon substrate SERS chips are placed in 10-8M TNT solution immersion, wherein TNT molecules can be logical with PABT molecules
Cross electric charge transfer to be interacted, react 50min, dried up afterwards with nitrogen, finally using laser co-focusing Raman
Can device carries out analysis detection to it, be interacted to investigate TNT with p-aminophenyl thiophenol, strengthen Raman signal.
Prepared chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest, inspection is built
Survey the TNT of trace in practical systems.Four environmental samples are have chosen to be tested, including lake water, spirits, soil and envelope.It is right
In untouchable detection, 10 are added in 900 μ L lake water and 900 μ L spirits first-5M TNT solution, then takes 50 μ respectively
L solution is added in our homemade small containers, is stained with silicon substrate SERS chips below the lid of container, container is covered tightly afterwards, plus
Heat is to 45 DEG C, after a period of time, takes out chip, is carried out detecting when participating in the cintest with portable Raman instrument, each sample is measured three times.It is right
In contact detection, the TNT solution of various concentrations is added in 900 μ L lake water and 900 μ L spirits, while also in 600mg
Soil and 150mg envelope in add various concentrations TNT solution, then with 900 μ L absolute methanols in soil and envelope
TNT molecules extracted, finally take 50 μ L solution to be added drop-wise on chip, allow solution fully to be contacted with chip, dried up with nitrogen
Afterwards, then with portable Raman instrument carry out detecting when participating in the cintest, each sample is measured three times.
Embodiment 8
Take 0.5 × 0.5cm2Single silicon wafer of size 3~6, put into clean beaker spent respectively in Ultrasound Instrument from
Sub- water, acetone ultrasound 15 minutes, obtain the clean silicon chip in surface standby.Then silicon chip is immersed in 40mL sulfuric acid and hydrogen peroxide
Mixed solution in the 30 minutes impurity to remove wherein indissoluble, finally clean up silicon wafer with deionized water standby.
The silicon chip of wash clean is placed in 30wt% hydrofluoric acid dips 30min, allows it to carry out silicon hydrogenation, makes the table of silicon chip
Face formed Si -- H bond, then treated silicon chip is placed in culture dish, smooth surface upward, be then placed in 1M silver nitrate and
Mixed solution (volume ratio=1 of 40wt% hydrogen fluoride:100) reduction reaction is carried out in, silver ion can be reduced by Si -- H bond, in silicon
The surface of piece forms the Nano silver grain of one layer of uniform growth in situ, obtains the silicon wafer of Surface Modified Ag Nanoparticles
(AgNPs@Si).Put it into afterwards containing 10-5Concussion reaction 2h in M p-aminophenyl thiophenol solution, removes do not received with silver afterwards
The p-aminophenyl thiophenol molecule of rice grain effect, with deionized water rinsing 3 times, finally dries up surface, you can obtain silicon with nitrogen
Base SERS multifunction chips.
Prepared silicon substrate SERS chips are placed in 10-9M TNT solution immersion, wherein TNT molecules can be logical with PABT molecules
Cross electric charge transfer to be interacted, react 2h, dried up afterwards with nitrogen, finally using laser co-focusing Raman instrument pair
Can it carries out analysis detection, be interacted to investigate TNT with p-aminophenyl thiophenol, strengthen Raman signal.
Prepared chip and portable Raman instrument are combined, a portable stage for detecting TNT when participating in the cintest, inspection is built
Survey the TNT of trace in practical systems.Four environmental samples are have chosen to be tested, including lake water, spirits, soil and envelope.It is right
In untouchable detection, 10 are added in 900 μ L lake water and 900 μ L spirits first-6M TNT solution, then takes 50 μ respectively
L solution is added in our homemade small containers, is stained with silicon substrate SERS chips below the lid of container, container is covered tightly afterwards, plus
Heat is to 45 DEG C, after a period of time, takes out chip, is carried out detecting when participating in the cintest with portable Raman instrument, each sample is measured three times.It is right
In contact detection, the TNT solution of various concentrations is added in 900 μ L lake water and 900 μ L spirits, while also in 600mg
Soil and 150mg envelope in add various concentrations TNT solution, then with 900 μ L absolute methanols in soil and envelope
TNT molecules extracted, finally take 50 μ L solution to be added drop-wise on chip, allow solution fully to be contacted with chip, dried up with nitrogen
Afterwards, then with portable Raman instrument carry out detecting when participating in the cintest, each sample is measured three times.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit is required rather than described above is limited, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It may be appreciated other embodiment.
Claims (9)
1. a kind of preparation method of silicon substrate SERS chips, it is characterised in that comprise the steps：
Silicon wafer is cleaned for the first time, surface removal of impurities, then carry out second of cleaning；
Silicon wafer surface after being cleaned at described second carries out silicon hydrogenation, obtains the silicon wafer for having Si -- H bond to surface；
The surface there is into the silicon wafer of Si -- H bond in Ag+Reduction reaction is carried out under environment, the silicon wafer of silver nanoparticle ion modification is obtained
Piece AgNPs@Si；
Take modified compound to be reacted with AgNPs Si, third time cleaning is carried out after reaction, silicon base chip is obtained.
2. preparation method according to claim 1, it is characterised in that the surface removal of impurities is specially：
Silicon wafer after the first time is cleaned soaks in the concentrated sulfuric acid and mixed solution of hydrogen peroxide.
3. preparation method according to claim 2, it is characterised in that described hydrogenperoxide steam generator mass concentration is
30%, the concentrated sulfuric acid and the hydrogen peroxide volume ratio are 1:(0.01~100).
4. preparation method according to claim 1, it is characterised in that the silicon hydrogenation is specifically, by described second
Silicon wafer after secondary cleaning soaks in hydrogen fluoride solution；
Described hydrogen fluoride solution mass concentration is 1~40%.
5. preparation method according to claim 1, it is characterised in that the reduction reaction is specially：
The silicon wafer that there is Si -- H bond on the surface is soaked in the strong acid salt of silver and the mixed solution of hydrogen fluoride；Described is silver-colored
Strong acid concentration of salt solution is 1M, and hydrogen fluoride solution mass concentration is 1~40%, silver-colored strong acid salting liquid and hydrogen fluoride solution volume
Than=1:(0.01~100).
6. preparation method according to claim 1, it is characterised in that the modified compound is selected from:P-aminophenyl thiophenol,
One or more in 4- sulfydryls toluene, 4- mercaptobenzoic acids and 2- methoxybenzene thiols.
7. preparation method according to claim 6, it is characterised in that the concentration of the modified compound solution is 10-3﹣
10-7M。
8. a kind of silicon base chip, it is characterised in that：It is prepared from by the preparation method described in any one of claim 1~7.
9. a kind of TNT detection method, it is characterised in that：Silicon base chip described in claim 8 is placed in sample solution, institute
Stating sample solution concentration range is：10-7﹣ 10-11M；
The SERS chips are incubated in the sample solution of various concentrations, the time of incubation：10~30min.
Chip after the incubation is detected in Raman instrument, the concentration of TNT in sample is obtained；The Raman instrument
Laser is 785nm, and laser power is 300mW, and it detects that TNT concentration range is：10-4﹣ 10-7M。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710253748.6A CN107144557A (en) | 2017-04-18 | 2017-04-18 | A kind of detection method of silicon substrate SERS chips and preparation method thereof and TNT |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710253748.6A CN107144557A (en) | 2017-04-18 | 2017-04-18 | A kind of detection method of silicon substrate SERS chips and preparation method thereof and TNT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107144557A true CN107144557A (en) | 2017-09-08 |
Family
ID=59774477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710253748.6A Pending CN107144557A (en) | 2017-04-18 | 2017-04-18 | A kind of detection method of silicon substrate SERS chips and preparation method thereof and TNT |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107144557A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108827941A (en) * | 2018-08-21 | 2018-11-16 | 厦门斯贝克科技有限责任公司 | A method of quickly detecting TNT in water based on Surface enhanced Raman spectroscopy |
| CN109738415A (en) * | 2019-03-20 | 2019-05-10 | 合肥学院 | A kind of preparation method of the nano silver SERS probe for TNT detection |
| CN110082340A (en) * | 2019-05-30 | 2019-08-02 | 合肥工业大学 | The flexible detection method that orderly micro-nano patterned films detect trace TNT |
| CN112113950A (en) * | 2020-09-09 | 2020-12-22 | 浙江大学 | Method for rapidly detecting sulfur dioxide residue in traditional Chinese medicine for sulfur fumigation |
| KR20210107421A (en) * | 2020-02-24 | 2021-09-01 | 국방과학연구소 | Substrate for detecting chemical gas and Method for manufacturing the same |
| CN115586168A (en) * | 2022-09-16 | 2023-01-10 | 中国人民解放军国防科技大学 | Explosive RDX detection method based on surface enhanced Raman scattering |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103604796A (en) * | 2013-11-29 | 2014-02-26 | 苏州大学 | Preparation method for silicon-based surface-enhanced Raman scattering (SERS) substrate |
| CN104237203A (en) * | 2014-09-28 | 2014-12-24 | 苏州大学 | SERS sensor for quantitatively detecting concentration of mercury ions in water sample and preparation method of SERS sensor |
| CN104697977A (en) * | 2015-03-23 | 2015-06-10 | 苏州大学 | Silicon-based SERS multifunctional chip and preparation method thereof |
-
2017
- 2017-04-18 CN CN201710253748.6A patent/CN107144557A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103604796A (en) * | 2013-11-29 | 2014-02-26 | 苏州大学 | Preparation method for silicon-based surface-enhanced Raman scattering (SERS) substrate |
| CN104237203A (en) * | 2014-09-28 | 2014-12-24 | 苏州大学 | SERS sensor for quantitatively detecting concentration of mercury ions in water sample and preparation method of SERS sensor |
| CN104697977A (en) * | 2015-03-23 | 2015-06-10 | 苏州大学 | Silicon-based SERS multifunctional chip and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HAIBO ZHOU ET AL.: "SERS Detection of Bacteria in Water by in Situ Coating with Ag Nanoparticles", 《ANALYTICAL CHEMISTRY》 * |
| JIANPING WANG ET AL.: "Inkjet-Printed Silver Nanoparticle Paper Detects Airborne Species", 《ANALYTICAL CHEMISTRY》 * |
| 王建萍: "SERS基底的理性设计及其在检测中的应用", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108827941A (en) * | 2018-08-21 | 2018-11-16 | 厦门斯贝克科技有限责任公司 | A method of quickly detecting TNT in water based on Surface enhanced Raman spectroscopy |
| CN108827941B (en) * | 2018-08-21 | 2021-06-18 | 启东科赛尔纳米科技有限公司 | Method for rapidly detecting TNT in water based on surface enhanced Raman spectroscopy |
| CN109738415A (en) * | 2019-03-20 | 2019-05-10 | 合肥学院 | A kind of preparation method of the nano silver SERS probe for TNT detection |
| CN109738415B (en) * | 2019-03-20 | 2021-06-15 | 合肥学院 | Preparation method of nano-silver SERS (surface enhanced Raman Scattering) probe for TNT (trinitrotoluene) detection |
| CN110082340A (en) * | 2019-05-30 | 2019-08-02 | 合肥工业大学 | The flexible detection method that orderly micro-nano patterned films detect trace TNT |
| KR20210107421A (en) * | 2020-02-24 | 2021-09-01 | 국방과학연구소 | Substrate for detecting chemical gas and Method for manufacturing the same |
| KR102298184B1 (en) | 2020-02-24 | 2021-09-07 | 국방과학연구소 | Substrate for detecting chemical gas and Method for manufacturing the same |
| CN112113950A (en) * | 2020-09-09 | 2020-12-22 | 浙江大学 | Method for rapidly detecting sulfur dioxide residue in traditional Chinese medicine for sulfur fumigation |
| CN115586168A (en) * | 2022-09-16 | 2023-01-10 | 中国人民解放军国防科技大学 | Explosive RDX detection method based on surface enhanced Raman scattering |
| CN115586168B (en) * | 2022-09-16 | 2024-05-14 | 中国人民解放军国防科技大学 | Explosive RDX detection method based on surface enhanced Raman scattering |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107144557A (en) | A kind of detection method of silicon substrate SERS chips and preparation method thereof and TNT | |
| Kishore et al. | Evolution of lock-in amplifier as portable sensor interface platform: A review | |
| Sikirzhytskaya et al. | Forensic identification of blood in the presence of contaminations using Raman microspectroscopy coupled with advanced statistics: effect of sand, dust, and soil | |
| Gross et al. | Cyclic-voltammetry-based solid-state gas sensor for methane and other VOC detection | |
| Hu et al. | Identification of mine water inrush using laser-induced fluorescence spectroscopy combined with one-dimensional convolutional neural network | |
| CN102539742B (en) | Method for detecting heavy metals in carbohydrate agricultural products and application thereof | |
| Feng et al. | Reorientation of the “free OH” group in the top-most layer of air/water interface of sodium fluoride aqueous solution probed with sum-frequency generation vibrational spectroscopy | |
| CN110082341B (en) | Preparation of SERS substrate based on nanosphere etching and application of SERS substrate in explosive TNT detection | |
| CN103411956A (en) | Method for rapidly detecting iodate by surface enhanced Raman spectroscopy and application of method | |
| TWI612288B (en) | A heavy metal detecting device and the fabricating method thereof | |
| CN104445985A (en) | Method for preparing surface enhanced Raman substrate for rapid field detection of explosives and powders | |
| CN103940878B (en) | A kind of without reagent electrochemical luminous sensor and preparation method thereof | |
| CN105084348B (en) | Method for preparing water-phase dispersible conductive graphene dispersion slurry or solid | |
| CN106556587A (en) | Surface enhanced Raman substrate and preparation method based on two-dimentional Tin diselenide. nanometer sheet | |
| CN106442411A (en) | Graphene surface wave based high-sensitivity ultrafast refractive index detecting device and method | |
| El Khoury et al. | A Combined far‐infrared spectroscopic and electrochemical approach for the study of iron–sulfur proteins | |
| CN104697980B (en) | A kind of method that quantitative determination is carried out to mercury ion based on the change of raman characteristic peak peak position | |
| Ruch et al. | A portable potentiometric electronic tongue leveraging smartphone and cloud platforms | |
| CN104614421B (en) | A kind of electrochemical method for detecting 2,4,6 trichlorophenol, 2,4,6,-Ts | |
| Bassous et al. | Significance of Various Sensing Mechanisms for Detecting Local and Atmospheric Greenhouse Gases: A Review | |
| Wang et al. | Analysis of nitrogen dioxide in environment | |
| CN108318472A (en) | A kind of preparation method for the surface enhanced Raman scattering substrate that high sensitivity is quickly analyzed | |
| CN102954956A (en) | Enhanced Raman spectroscopy test piece device and test piece manufacturing method | |
| CN109060768A (en) | A method of based on Surface enhanced Raman spectroscopy trace detection erythrosine concentration | |
| CN107037093A (en) | A kind of tyrosinase electrochemica biological sensor and its preparation, application process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170908 |
|
| RJ01 | Rejection of invention patent application after publication |