CN109939750A - A kind of microchannel plate of functionalization and bimolecular sensors comprising the microchannel plate - Google Patents
A kind of microchannel plate of functionalization and bimolecular sensors comprising the microchannel plate Download PDFInfo
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- CN109939750A CN109939750A CN201711384070.1A CN201711384070A CN109939750A CN 109939750 A CN109939750 A CN 109939750A CN 201711384070 A CN201711384070 A CN 201711384070A CN 109939750 A CN109939750 A CN 109939750A
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- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 claims abstract description 59
- 239000002073 nanorod Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims description 14
- 230000008020 evaporation Effects 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 238000001465 metallisation Methods 0.000 claims description 3
- 239000002086 nanomaterial Substances 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 238000001883 metal evaporation Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 9
- 239000003550 marker Substances 0.000 abstract description 6
- 238000001069 Raman spectroscopy Methods 0.000 abstract description 4
- 239000000090 biomarker Substances 0.000 abstract description 4
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 abstract description 2
- 230000002463 transducing effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 5
- 230000003321 amplification Effects 0.000 description 4
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
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- 102000004190 Enzymes Human genes 0.000 description 2
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- 238000010899 nucleation Methods 0.000 description 2
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- 241000700605 Viruses Species 0.000 description 1
- 239000000427 antigen Substances 0.000 description 1
- 102000036639 antigens Human genes 0.000 description 1
- 108091007433 antigens Proteins 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000013399 early diagnosis Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 239000005308 flint glass Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004297 night vision Effects 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
A kind of microchannel plate of functionalization, it is characterised in that: microchannel plate is arranged with multiple inclined transparent micropores, and micropore is parallel to each other, and metal nano-rod array is attached in micropore.A kind of bimolecular sensors, it is characterized by comprising have signal amplifying apparatus, transducing head and identification device, microchannel plate as described above is used in the signal amplifying apparatus, realizes the detection to trace marker (concentration :~fg/mL) or even unimolecule concentration；Metal nano-rod is prepared in microchannel plate, based on the surface plasmon resonance of the metal nano-rod array in microchannel plate micropore, utilizes Raman spectroscopic detection biomarker.
Description
Technical field
The present invention relates to a kind of microchannel plate of functionalization and include the bimolecular sensors of the microchannel plate.
Background technique
Biomolecule is the substance undertaker of human physiological activity and the prediction and diagnosis of disease and information carrier.
(such as nucleic acid, protein, virus, unite specific biological molecules below in detection biological sample (including blood, saliva, urine etc.)
Referred to as marker) concentration, for research human normal vital movement rule and disease early diagnosis and personalized treatment
It is of great significance.The substance that predetermined substance can selectively be offered an explanation in organism has enzyme, antibody, tissue, cell
Deng.These molecular recognition function substances can be combined into compound with measured target by identification process, such as the knot of antibody and antigen
It closes, the combination of enzyme and matrix.
Preferably to detect biological sample, people more use biosensor, and biosensor is by molecular recognition portion
Divide (sensing element) and conversion portion (energy converter) to constitute, is sensitive to biological substance and its concentration is converted into electric signal progress
The instrument of detection.
Light, heat, the generation of chemical substance or consumption etc. can generate corresponding variable quantity in sensing element.According to these variations
Amount, can choose energy converter appropriate.Sensing element is frequently necessary to be applied in combination with signal amplifying apparatus, and biomolecule passes at present
Signal amplifying apparatus in sensor is often used microchannel plate.
Microchannel plate is using glass flake as substrate for microchannel plate (Microchannel Plate, MCP), with number on substrate
The micron micropore smaller with hexagonal periodic arrangement aperture ratio space periodic to more than ten microns of space periodic, one piece of microchannel plate
On there are about microchannels up to a million.Since secondary electron can amplify collision multiplication on conduit wall, microchannel plate is as a kind of big
The electron multiplication detector of the high-space resolution of face battle array, is widely used in the multiple fields such as high-performance night vision image intensifier.
As the effective means for identifying substance classes, Raman spectrum is widely used always, and metal surface plasma swashs
Member resonance can effectively enhance Ramam effect.Surface plasmon resonance, i.e., the free electron in metal is under electromagnetic field effect
The oscillation effect that communality occurs, when the frequency of external electromagnetic field is close to this collective oscillation frequency (resonance mode), electromagnetism
Field can be by the sub-wavelength region of local near metal surface, and intensity is very big.The strong laser field and detected material of the local occur
Inelastically scattered intensity increases, to enhance Raman signal.Cu is generally used, the reason of metals such as Ag, Au is their d
The energy gap of electronics and s electronics is bigger, is not susceptible to band-to-band transition, can avoid light absorbing energy due to band-to-band transition occurs
Conversion.
Currently, the microchannel plate that the biosensor in other patents uses, is carried out based on Secondary-emission multipbcation principle
Signal amplification, microchannel plate at this moment need to use flint glass, and the reduction treatment in atmosphere of hydrogen, and not only preparation process is multiple
It is miscellaneous, and cannot effectively enhance the Raman spectrum of marker, lack the enhancing to the specific signals of biomolecule.
Summary of the invention
To solve the above problems, the present invention provides following scheme:
A kind of microchannel plate of functionalization, microchannel plate are arranged with multiple inclined transparent micropores, and micropore is included
Have metal nano-rod array.
Further, in metal nano-rod array metal nano-rod diameter be 50~150nm, length be 100~
700nm；Metal nano-rod distribution density is 103~106/μm2。
Further, the metal nano-rod array is prepared using following methods, before preparing metal nano-rod, is passed through
Sputter coating process is grown one layer of metal on microchannel plate surface to be processed and is existed as preliminary sedimentation lamination, then using metal evaporation technology
Metal nano-rod array is prepared on the preliminary sedimentation lamination；In metal nano-rod array preparation process, microchannel plate bottom surface to be processed is flat
Row is placed in above evaporation material, and is rotated, rotation speed 0-30rpm, and microchannel plate temperature to be processed is 25 DEG C~
70 DEG C, evaporation of metal rate 0.3nm~10nm/s, evaporation material is using any metal and alloy in gold, silver, copper.
Using microchannel plate to be processed as growth substrates, microchannel plate to be processed is placed horizontally above evaporation source,
(substrate and horizontal line angle are greater than 70 at intrinsic inclination angleo) nanostructure is grown for the shadow effect of metal deposition process.It is heavy
Long-pending early period, metal nucleation form island structure；Later growth, since high position has intercepted the supply of metallic vapour, to limit
The growth at the position that it is closed on is made.Finally, foring suitable metal nano-rod array, i.e., since microchannel plate micro-pore wall has
Have an inclination angle, metallic vapour due to micro-pore wall blocking so that the metal nano-rod that internally positioned metallic vapour is formed is shorter, and
It is longer compared with the metal nano-rod in outside positioned at micropore, thus the metal nano-rod array needed for being formed.Above-mentioned metal nano-rod is heavy
Product process is localization inclination angle deposition technique, using this technology when preparing metal nano-rod array, microchannel to be processed
Plate is carried out without being connected on inclined pedestal (or sample stage), reduces evaporation process complexity and evaporated device complexity.,
And prepared metal nano-rod meets demand.
Further, pedestal rotation speed is preferably 5-25rpm.
Further, microchannel plate temperature to be processed is preferably 30-65 DEG C.
Further, evaporation of metal rate is preferably 0.4-9.8nm/s.
A kind of bimolecular sensors include signal amplifying apparatus, are used in signal amplifying apparatus as described above micro-
Channel plate.
The invention has the benefit that
1. preparing metal nano-rod on microchannel plate, is resonated using metal nano-rod metallic surface plasma excimer and effectively increased
Strong Ramam effect, using Raman spectroscopic detection biomarker, instead of the original of Secondary-emission multipbcation used by existing microchannel plate
Reason, enhancing signal amplification effect is, it can be achieved that detection to trace marker (concentration :~fg/mL) or even unimolecule concentration.
2. utilizing localization inclination angle deposition technique, saves and incline to the pedestal (or sample stage) of microchannel plate to be processed
Oblique process, preparation process is easier, and reduces to the configuration requirement of filming equipment.
Detailed description of the invention
Fig. 1, Fig. 3 are schematic structural view of the invention；
Fig. 2 is part A cross-sectional view in Fig. 1；
Fig. 4, Fig. 5, Fig. 6 are the representative metal nano-rod shape appearance figure of scanning electron microscope observation；
Fig. 7 is sensor Ramam effect detection figure.
1. micropore；2. metal nano-rod；3. metallic vapour.
Specific embodiment
Now in conjunction with attached drawing, the present invention is described in detail:
Embodiment 1: as shown in Figure 1-3,
A kind of microchannel plate, microchannel plate are arranged with multiple inclined transparent micropores 1, are attached with gold in micropore 1
Belong to 2 array of nanometer rods, 2 material of metal nano-rod is silver.
The diameter of metal nano-rod 2 is 60nm, length 130nm in metal nano-rod array, and metal nano-rod array is close
Degree is 104/μm2, 2 pattern of metal nano-rod is clear.
2 array of metal nano-rod is using microchannel plate as growth substrates, intrinsic inclination angle (1 wall of micropore and horizontal line
Angle is greater than 70 °) nanostructure is grown for the shadow effect of metal deposition process.Early period is deposited, metal nucleation forms island
Structure；Later growth, since high position has intercepted the supply of metallic vapour, to limit the growth at the position that it is closed on.
Finally, foring suitable 2 array of metal nano-rod, i.e., since microchannel plate micro-pore wall has inclination angle, metallic vapour is due to micro-
The blocking of hole wall so that the metal nano-rod that internally positioned metallic vapour is formed is shorter, and is located at metal of the micropore compared with outside
Nanometer rods are longer, thus the metal nano-rod array needed for being formed.In preparation process, microchannel plate to be processed is placed horizontally at steaming
Above rising, is carried out without being connected on inclined pedestal (or sample stage), reduce evaporation process complexity and evaporated device
Complexity.
Before electron beam evaporation plating metal, one layer of metallic silver can be grown as pre-deposition by sputter coating process by silver
Layer, when preparing metal nano-rod array, microchannel plate rotation speed to be processed is 15r/m, and underlayer temperature is 30 DEG C, evaporation rate
1nm/s, evaporation material is using silver.
A kind of bimolecular sensors include in signal amplifying apparatus described in signal amplifying apparatus using as described above
Microchannel plate.
2 shape appearance figure of representative metal nano-rod of scanning electron microscope observation is as Figure 4-Figure 6.
The signal amplification dress of bimolecular sensors is prepared into using the microchannel plate for being attached with 2 array of metal nano-rod
It sets, Ramam effect has high sensitivity.For using rhodamine B as marker, the sensor based on the invention is obtained
Concentration be 10-4M, Raman spectrum characteristic peak intensity are that concentration is 10 unexpectedly-11~10 times of the bulk solution of M.Such as Fig. 7 institute
Show.
Metal nano-rod is prepared on microchannel plate, being resonated using metal nano-rod metallic surface plasma excimer is effectively enhanced
Ramam effect is visited instead of conventional microchannel plate using Secondary-emission multipbcation principle using Raman spectroscopic detection biomarker
The mode of biomarker is surveyed, enhancing signal amplification effect is, it can be achieved that trace marker (concentration :~fg/mL) or even list
The detection of molecular concentration.
Claims (7)
1. a kind of microchannel plate of functionalization, microchannel plate is arranged with multiple inclined transparent micropores, and micropore is mutual
In parallel, it is characterised in that: metal nano-rod array is attached in micropore.
2. a kind of microchannel plate of functionalization as described in the appended claim 1, it is characterised in that: golden in the metal nano-rod array
The diameter for belonging to nanometer rods is 50~150nm, and length is 100~700nm；Metal nano-rod distribution density is 103~106/μm2。
3. a kind of microchannel plate of functionalization as described in the appended claim 1, it is characterised in that: the metal nano-rod array uses
Following methods preparation grows one on microchannel plate surface to be processed by sputter coating process before preparing metal nano-rod
Layer metal prepares metal nano-rod array on the preliminary sedimentation lamination as preliminary sedimentation lamination, then using metal evaporation technology；Metal is received
In rice stick array preparation process, microchannel plate to be processed is placed horizontally above evaporation source, and is rotated, intrinsic inclination angle
Nanostructure is grown for the shadow effect of metal deposition process, microchannel plate rotation speed to be processed is 0-30rpm, to be processed
Microchannel plate temperature is 25 DEG C~70 DEG C, evaporation of metal rate 0.3nm~10nm/s, and evaporation material is using any in gold, silver, copper
Metal and alloy.
4. a kind of functionalization microchannel plate as claimed in claim 3, it is characterised in that: the microchannel plate rotation speed to be processed
Degree is preferably 5-25rpm.
5. a kind of functionalization microchannel plate as claimed in claim 3, it is characterised in that: the microchannel plate temperature to be processed is excellent
It is selected as 30-65 DEG C.
6. a kind of functionalization microchannel plate as claimed in claim 3, it is characterised in that: the evaporation of metal rate is preferably
0.4‐9.8nm/s。
7. a kind of bimolecular sensors include signal amplifying apparatus, it is characterised in that: using as weighed in signal amplifying apparatus
Benefit requires any microchannel plate in 1-6.
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| CN201711384070.1A CN109939750A (en) | 2017-12-20 | 2017-12-20 | A kind of microchannel plate of functionalization and bimolecular sensors comprising the microchannel plate |
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| CN201711384070.1A CN109939750A (en) | 2017-12-20 | 2017-12-20 | A kind of microchannel plate of functionalization and bimolecular sensors comprising the microchannel plate |
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