CN1866002A - Self-assembled single molecular layer sensitive film for exploder detection and preparation method thereof - Google Patents
Self-assembled single molecular layer sensitive film for exploder detection and preparation method thereof Download PDFInfo
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- CN1866002A CN1866002A CN 200610026520 CN200610026520A CN1866002A CN 1866002 A CN1866002 A CN 1866002A CN 200610026520 CN200610026520 CN 200610026520 CN 200610026520 A CN200610026520 A CN 200610026520A CN 1866002 A CN1866002 A CN 1866002A
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Abstract
The related self-assembly monomolecular sensitive film for explosive detection comprises: preparing the film with 6-MNA, and forming monomolecular layer on noble metal substrate sensitive to DNT, TNT, RDX, and PETN contained -NO2 or -ONO2. This invention has high sensitivity, fast response, and well specificity, and superior to 4-MBA overseas, and can be used for security check and antiterrorism.
Description
Technical field
The present invention relates to a kind of self assembled monolayer sensitive membrane and preparation method who is used for explosive detection, belong to the chemical sensitisation technical field.
Background technology
Along with the asymmetry differentiation of world structure and the in-depth of various contradictions, the attack of terrorism miscellaneous has constituted real threat to international and domestic security situation.National governments all pay much attention to this, drop into a large amount of manpower and financial resources aspect the Detection Techniques research of explosive.At present, the explosive detection technology mainly is divided into two big classes: body Detection Techniques and " Electronic Nose " technology.
The technology that the body Detection Techniques of explosive are promptly differentiated the overall appearance of explosive.At present, the this respect technology is relatively ripe, mainly comprise scanning imagery Detection Techniques (as: X ray technology, infrared imagery technique etc.), nuclear energy Detection Techniques (as: gamma-rays technology, neutron detection technology) and nuclear quadrupole resonance and supersonic sounding technology etc.The equipment that utilizes these technology to form mainly exist equipment volume big, cost an arm and a leg, shortcoming such as sensitivity is low.And all there is radiation problem in various degree in these technology, be not suitable for the people is checked, so its application are greatly limited.
In recent years, the biochemical sensitive technical research of a kind of being called as " Electronic Nose " has obtained bigger progress.This is that new approach has been opened up in the detection of explosive towards being blended in airborne steam or aerocolloidal detection technique.Simultaneously, the development of modern physics technology, transducer technology and sensitive material technology makes the ultramicron of explosive detect becomes possibility.The Electronic Nose Technology type of various countries research and development is more, and that made product generally has is highly sensitive, volume is little, low cost and other advantages, and these technology also are gradually improved and progressively are applied.
The ion mobility spectrometry technology be in the explosive detection than proven technique, selectivity and stable aspect have very strong advantage, comparatively speaking, its price is still relatively more expensive.Strand fluorescent polymer detection technique is considered to the sensitiveest explosives detection techniques at present, and the detectability of open-air actual detected TNT can reach 10
-15G, but the stability of this technology and selectivity still remain further to be improved [D.S.Moore, Instrumentation for trace detection of high explosives.Rev.Sci.Instrum.75, (2004) 2499-2512.].In recent years, the fast development based on the Electronic Nose Technology of SAW (Surface Acoustic Wave) device and minute mechanical and electrical system provides a new good platform for developing easy, sensitive, reliable, inexpensive explosives detection techniques.U.S.'s Oak Ridge National Laboratory has proposed a kind of new method of utilizing explosive deflagration behavior explosive detection particulate, the explosive arrival specified temp that this method adopts heating to drop on the silicon micro-cantilever makes it that quick-fried right reaction take place, cause the strain and the vibration of semi-girder, thereby judge the existence and the kind [L.A.Pinnaduwage of explosive, A.Gehl, D.L.Hedden, G.Muralidharan, T.Thundat, R.T.Lareau, T.Sulchek, L.Manning, B.Rogers, M.Jones, J.D.Adams, A microsensor for trinitrotoluene vapour.Nature 425, (2003) 474.].Domestic Hefei Institute Of Intelligent Machines Chinese Academy Of Sciences also adopts similar approach, and utilize different solid-state explosive particles to have the characteristic of different melting points and evaporating point, heat by sample being carried out accurate temperature controlling, and adopt the micromechanics temperature-sensing element (device) to measure the kind that the caused temperature variation of heat absorption is come the detection and Identification explosive in explosive particle fusion and the evaporation process.This detection method at explosive particle has higher sensitivity and selectivity, and still, the catching of relevant explosive particle, enrichment etc. remain a problem that urgency is to be solved.
In recent years, also begin to be subjected to researchist's attention gradually towards the detection technique of explosive steam, and embodied very strong technology and cost advantage, have broad application prospects.Because the vapor pressure of general plastic explosives (as: TNT, RDX, PETN etc.) is all very low, thereby to research and develop a kind of be the key that realizes sensitive fast detecting such as TNT to the very sensitive membrane material of explosive steam.2003, the research group of U.S. Oak Ridge National Laboratory Thundat has reported with the self assembly on silicon cantilever of 4-mercaptobenzoic acid and has formed the unimolecule sensitive membrane, realized the Sensitive Detection [L.A.Pinnaduwage of multiple explosive, V.Boiadjiev, J.Hawk, T.Thundat, Sensitive detection of plasticexplosives with self-assembled monolayer-coated microcantilevers, Appl.Phys.Lett.83, (2003) 1471-1473.].At present, the research of this respect still is in the starting stage, is also requiring further improvement aspect the sensitivity of sensitive material and the selectivity.
Summary of the invention
The object of the present invention is to provide a kind of self-composed monomolecular sensitive membrane and preparation method who is used for explosive detection, also promptly the present invention is directed to the preparation and the fixation problem of the sensitive material in the present explosive detection, adopt numerator self-assembly technique to form the unimolecular layer sensitive membrane at precious metal surfaces such as Au, Ag and Pt, can on all kinds of power and mass-sensitive structure, modify and form the Sensitive Detection device, thereby realize the ultramicron fast detecting of explosive molecule.This method is easy and simple to handle, the sensitive membrane stable performance of formation, highly sensitive, advantage such as the response time is fast, specificity is good.
The unimolecular layer sensitive membrane of the present invention's preparation is mainly used in to detect and contains nitro (NO
2) or itrate group (ONO
2) explosive, as: dinitrotoluene (DNT) (DNT), TNT (TNT), hexogen (RDX) and peace (PENT) etc. too.
The main component of the unimolecular layer sensitive membrane of the present invention preparation is a 6-sulfydryl Nicotinicum Acidum (6-MNA), adopt self-assembling method the precious metal surface of sensitive structure realize sensitive material quantitatively, orientation and homogeneous fix.Concrete operations are as follows:
(1) cleaning of substrate surface: the precious metal surface (as Au, Ag, Pt etc.) of using acetone, ethanol and ultrapure water (resistivity＞15M Ω) to clean on the sensitive structure respectively for several times, is used Piranha solution (98% concentration H again
2SO
4/ 30%H
2O
2Volume ratio is 7: 3) embathe precious metal surface 2min, clean device 2 times with ultrapure water rapidly, clean 2 times with ethanol again, dry or N for 80 ℃ then
2Dry up.
(2) preparation of self-assembled film: sensitive structure is immersed in the 6-MNA/ ethanolic solution that concentration is 1 μ M～10mM, and self-assembling reaction 16-24h takes out the back and cleans for several times N with ethanol and ultrapure water
2Dry up standby.
Sensitization principle to the unimolecular layer sensitive membrane is described below:
The present invention utilizes self assembly to form on sensitive structure surface to have certain spatial selectivity-on COOH and the explosive molecule-NO
2Producing hydrogen bond action power, is example with the TNT molecule, and its action principle as shown in Figure 1.
On the TNT molecule-NO
2As on electron donor and the self assembled monolayer-COOH can form hydrogen bond action power, and, from spatial selectivity, two-NO on the intermolecular position of TNT
2Just can with last two different moleculars in surface on-the COOH effect, further strengthened the acting force between sensitive membrane and the TNT molecule, thereby improved the sensitivity and the selectivity of sensitive membrane.
The present invention adopts the 6-MNA self assembled monolayer as the sensitive membrane material, compares with the 4-MBA self-assembled film of the national experiment report of U.S.'s Oak Ridge to have higher sensitivity (seeing embodiment 1 for details).From molecular structure, the difference of the two is that phenyl ring among the 4-MBA is replaced by a pyridine ring.Because the electronegativity of N atom is bigger, make that the cloud density on the ring diminishes, thereby-acidity of COOH strengthens.Therefore, adopt the 6-MNA self assembled monolayer can strengthen the hydrogen bond action power of TNT molecule and surperficial unimolecular layer, raising detection sensitivity as sensitive material.From another angle, reference [C.Raj, S.Behera, Electrochemical studies of 6-mercaptonicotinic acidmonolayer on Au electrode, J.Electroanal.Chem.581 (2005) 61-69; Y.Ji, Q.Zhou, X.Li, Y.Zhou, Y.Zhuang, J.Zheng, Surface-enhanced Ramanspectroscopy of 4-mercaptobenzoic acid, Chinese.J.Anal.Chem.32 (2004) 1050-1052.] reported and tested the surface acidity value pK that records 6-MNA and 4-MBA self assembled monolayer
aBe respectively 5.5 and 5.9.These data show that also the cantilever beam sensor of having modified the 6-MNA self assembled monolayer should have the stronger ability of catching explosive molecules such as TNT than the cantilever beam sensor of having modified the 4-MBA self assembled monolayer.
The self assembled monolayer sensitive membrane of the present invention preparation can and be pacified very much (PETN) etc. to dinitro first stupid (DNT), TNT (TNT), hexogen (RDX) and be contained nitro (NO
2) or itrate group (ONO
2) the explosive sensitivity, can on all kinds of power and mass-sensitive element, carry out self-assembled modifiedly, form the Sensitive Detection device.
The present invention preparation to be that the self assembled monolayer sensitive membrane of main material has highly sensitive, the response time fast, specificity and high repeatability and other advantages with 6-sulfydryl Nicotinicum Acidum, aspect sensitive property, obviously be better than the external stupid formic acid of 4-sulfydryl (4-MBA) unimolecular layer of using.This self assembled monolayer is modified in micro-cantilever sensitive structure surface, can be developed further into a kind of portable sensor, can differentiate the TNT steam of tens ppt magnitudes, can be used for the demand of the safety inspection and the anti-terrorism of multiple occasion.(seeing embodiment 1 and 2 for details)
Description of drawings
The action principle of Fig. 1 TNT molecule and 6-MNA unimolecular layer sensitive membrane.
Two kinds of different self assembled monolayers of Fig. 2 are modified the response curve of semi-girder device to the TNT steam.
(a) unmodified; (b) 4-MBA self-assembled film; (c) 6-MNA self-assembled film.The TNT vapor concentration is 25 ℃ of saturation concentration 7.6ppb under the condition.
The SiO that Figure 36-MNA self assembled monolayer is modified
2The micro-cantilever device is to the response curve of variable concentrations TNT steam.The TNT vapor concentration is respectively 0 ℃, and 5 ℃, 11.5 ℃, the saturation concentration under 19.5 ℃ and the 25 ℃ of conditions.Device noise is about 0.3 μ V.
Embodiment
To further specify actual property characteristics of the present invention and obvious improvement by embodiment below.
Embodiment 1.6-MNA and 4-MBA self assembled monolayer sensitive property are relatively
Experiment is at a kind of pressure drag SiO
2Carry out on two kinds of different unimolecular layers of modification on the micro-cantilever device, relatively its response the TNT steam.Test used SiO
2The micro-cantilever device adopts the standard round blade technolgy to be made.On Sensitive Apparatus, make two micro-cantilevers (long 90 μ m, wide 15 μ m, thick 1 μ m) simultaneously.Wherein adopt the Cr of electron beam evaporation plating one deck 5nm and the Au film of 50nm on a semi-girder, as measuring semi-girder; Another root is as the reference semi-girder.Pressure drag on the semi-girder is connected according to the Wheatstone bridge mode with two reference resistances on being produced on device, can reduces device noise greatly like this.Load 200mV voltage at the electric bridge two ends, detect electric signal and provide by the bridge voltage output that the variation of semi-girder pressure drag causes.
According to method set forth in the present invention micro-cantilever surfaces A u is carried out cleaning, inserting concentration then is in the 4-MBA/ ethanolic solution of 6mM, and self-assembling reaction 24h takes out the back and cleans for several times N with ultrapure water and ethanol
2Dry up.Device is inserted under 25 ℃ of conditions 5min in the TNT saturated vapor, take out then and place air 5min, the response curve of record sensor.Embathe device to remove the 4-MBA unimolecular layer on surface with Piranha solution.Device after the cleaning uses the same method and modifies the 6-MNA unimolecular layer again, and measures its response curve to same concentration TNT.As shown in Figure 2, not modified semi-girder device is to the almost not response of saturated TNT steam, and the response of the device that the 6-MNA unimolecular layer is modified is apparently higher than the device of 4-MBA modification, and the absorption response speed is also faster.After device taken out from the TNT steam, device also can very fast recovery.Though the device that the 6-MNA unimolecular layer is modified is slower than the device that 4-MBA modifies slightly on regeneration rate.But for field quick detection, detection speed is more even more important than resume speed.In this sense, the device performance of 6-MNA unimolecular layer modification is better.
The micro-cantilever device that embodiment 2.6-MNA self assembled monolayer is modified is to the response of variable concentrations TNT steam
According to the above-mentioned SiO that detects at pressure drag with quadrat method
2Modify the 6-MNA unimolecular layer on the micro-cantilever device.Device is inserted respectively between 0～25 ℃ under the condition of different temperatures in the pre-saturated TNT steam, and registering device is to the response curve of TNT steam, and method of operating is with embodiment 1.As shown in Figure 3, this device all has response faster to the TNT steam of various concentration.Along with the rising of TNT concentration, its response is in rising trend.This device has tangible response to the TNT steam of concentration 0.1ppb, and according to device 0.3 μ V noise estimation, device can reach tens ppt magnitudes to the detectability of TNT steam.
Claims (8)
1, a kind of sensitive membrane that is used for explosive detection is characterized in that composition material is a 6-sulfydryl Nicotinicum Acidum.
2, sensitive membrane as claimed in claim 1 is characterized in that described sensitive membrane is that method with self assembly forms unimolecular layer at the bottom of the precious metal-based of gold, silver or platinum.
3, the preparation method that is used for the sensitive membrane of explosive detection as claimed in claim 1 or 2 is characterized in that:
(1) cleaning of substrate surface: respectively with the precious metal surface on acetone, ethanol and the ultrapure water cleaning sensitive structure, embathe noble metal table 2min with Piranha solution again, then clean device 2 times, clean 2 times with ethanol again, then with 80 ℃ of oven dry of device or N with ultrapure water
2Dry up;
(2) preparation of self-assembled film: with the sensitive structure immersion concentration of device in the step (1) is in the 6-MNA/ ethanolic solution of 1 μ M-10mM, and self-assembling reaction 16-24h takes out the back and cleans N with ethanol and ultrapure water
2Dry up.
4, the preparation method who is used for the sensitive membrane of explosive detection as claimed in claim 3 is characterized in that cleaning ultrapure resistivity of water＞15M Ω that sensitive structure is used.
5, the preparation method who is used for the sensitive membrane of explosive detection as claimed in claim 3 is characterized in that described Piranha solution is is 98%H by concentration
2SO
4And 30%H
2O
2Form by 7: 3 weight ratios.
6, the application of sensitive membrane as claimed in claim 1 is characterized in that being used to detect the explosive that contains nitro or itrate group.
7, a kind of application that is used for the sensitive membrane of explosive detection as claimed in claim 6 is characterized in that detecting the described explosive that contains nitro or itrate group and is among dinitrotoluene (DNT), TNT, hexogen and the Tai An any one.
8, as a kind of application that is used for the sensitive membrane of explosive detection as described in claim 5 or 6, it is characterized in that to reach tens ppt magnitudes to the detectability of TNT steam.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101477029B (en) * | 2009-01-16 | 2011-06-08 | 中国科学院上海微系统与信息技术研究所 | Surface stress sensitization method for improving resonance type ultra-thin cantilever beam transducer sensitivity |
| CN101712451B (en) * | 2009-11-18 | 2012-09-05 | 中国科学院上海微系统与信息技术研究所 | One-step method for making carboxylic acid functional monofilm on surface of micro cantilever beam |
| WO2016058229A1 (en) * | 2014-10-13 | 2016-04-21 | 彭碳科技有限公司 | Formula and method for preparing three-dimensional graphene-covered single-particle nanodiamond material |
| CN111044574A (en) * | 2019-12-02 | 2020-04-21 | 东南大学 | Ultra-sensitive plastic bomb detection sensor |
| CN117504840A (en) * | 2023-12-20 | 2024-02-06 | 南方海洋科学与工程广东省实验室(广州) | Self-assembled monomolecular film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5918263A (en) * | 1998-03-31 | 1999-06-29 | Lockheed Martin Energy Research Corporation | Microcantilever detector for explosives |
-
2006
- 2006-05-12 CN CN2006100265205A patent/CN1866002B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101477029B (en) * | 2009-01-16 | 2011-06-08 | 中国科学院上海微系统与信息技术研究所 | Surface stress sensitization method for improving resonance type ultra-thin cantilever beam transducer sensitivity |
| CN101712451B (en) * | 2009-11-18 | 2012-09-05 | 中国科学院上海微系统与信息技术研究所 | One-step method for making carboxylic acid functional monofilm on surface of micro cantilever beam |
| WO2016058229A1 (en) * | 2014-10-13 | 2016-04-21 | 彭碳科技有限公司 | Formula and method for preparing three-dimensional graphene-covered single-particle nanodiamond material |
| CN111044574A (en) * | 2019-12-02 | 2020-04-21 | 东南大学 | Ultra-sensitive plastic bomb detection sensor |
| CN111044574B (en) * | 2019-12-02 | 2022-03-04 | 东南大学 | Ultra-sensitive plastic bomb detection sensor |
| CN117504840A (en) * | 2023-12-20 | 2024-02-06 | 南方海洋科学与工程广东省实验室(广州) | Self-assembled monomolecular film and preparation method and application thereof |
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