CN109520977A - A kind of dendritic gold of super infiltration nanometer/graphene microchip for many body system detection - Google Patents
A kind of dendritic gold of super infiltration nanometer/graphene microchip for many body system detection Download PDFInfo
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Abstract
The present invention relates to complex function chip technology fields, provide a kind of dendritic gold of super infiltration nanometer/graphene microchip, preparation and application for many body system detection；Electrochemistry, fluorescence and surface Raman enhancement (SERS) multi signal output detection disease marker are carried out on single super infiltration microchip；By electrochemical deposition, solvent modification, photomask blank etching and solution-evaporation obtain the multi-functional super dendritic gold of infiltration nanometer/graphene microchip；This microchip combines the functionalization advantage of the advantages of super infiltration system liquid drop control and graphene and the dendritic gold of nanometer, is compared verifying by three kinds of testing result output means, improves the accuracy of detection, it is possible to prevente effectively from false positive diagnoses.
Description
Technical field
Complex function chip technology field of the present invention, in particular to a kind of super infiltration nanometer for many body system detection are dendritic
Gold/graphene microchip, preparation and application.
Background technique
Regulation of the generation of most of disease all along with internal certain specific biomarkers is unbalance, by these
The monitoring of biomarker can efficiently control prevention, these diseases are even thoroughly cured in early diagnosis.Now by blood
The detection of biomarker in liquid can early diagnose part disease, but cumbersome testing process and expensive check fee
With making it be difficult to popularize.In order to solve these problems, scientist has developed portable device by sweat, saliva, urine
Quickly cheap detection is carried out to disease marker with exhaled gas etc..These equipment significantly reduce detection time and at
This, and since body fluid, these interior Specific marker concentration of exhaled gas are too low in addition for the detection means of tables of equipment one, it is non-specific
Property detection and the factors such as environment cause detection accuracy to reduce, easily there is false positive diagnosis.
Many body system detection is to combine such as electrochemistry and SERS by two or more detection technique to combine, fluorescence and
Colorimetric combination etc. carries out multi signal output detection to detectable substance of the same race.A variety of detections are not interfere with each other, and testing result is mutually confirmed,
Greatly solve non-specific detection, detectable substance concentration it is low with environmental factor etc. caused by the low problem of detection accuracy.It is more
The detection of system is very high to detection chip requirement, to be suitable for a variety of detection devices, respond to multi-signal, to detection liquid
Crawl is fixed, to low concentration detectable substance signal amplification etc..Current most of detection chips only respond a kind of signal, greatly
Ground limits the development and application of many body system detection.
Super infiltration microchip, which refers to, to be prepared on microchip surface with super hydrophilic and super-hydrophobic two parts region, is passed through
Two kinds of extreme interface states are by droplet capture and are fixed on super hydrophilic region.Super infiltration microchip can be by reducing hydrophilic region
Area fixes micro updating drop, enrichment and quickly detection.
Summary of the invention
The object of the invention is to overcome the deficiencies of the prior art and provide it is a kind of for many body system detection super infiltration receive
Meter Zhi Zhuan gold/graphene microchip, preparation and application solves in quickly detection body fluid, the single inspection of when biological disease marker
Survey means are by environment, the problems such as detection accuracy bottom caused by the problems such as equipment influences and big error, by fluorescence, electrochemistry and
Tri- kinds of means of SERS carry out many body system detection to same drop body fluid, and three kinds of testing results are mutually authenticated raising detection accuracy, have
Effect avoids the diagnosis of false positive.
Technical scheme is as follows:
A kind of dendritic gold of super infiltration nanometer/graphene microchip for many body system detection, the microchip are used for fluorescence, electrification
It learns and SERS many body system detects；The microchip successively includes: electro-conductive glass substrate, titanium layer, plane layer gold, nanometer from top to bottom
Dendritic layer gold, super hydrophobic surface, the super hydrophobic surface are provided with super hydrophilic array, and super hydrophilic array is the dendritic gold/stone of nanometer
Mertenyl bottom.
Further, the titanium layer, plane layer gold pass through method modification the leading to the electro-conductive glass of magnetron sputtering
Electric side；The dendritic layer gold of nanometer is with the method modification of electrochemical deposition to the plane layer gold；To the dendritic gold of the nanometer
Layer carries out hydrophobic treatment, obtains the super hydrophobic surface；Super hydrophilic array is formed in the super hydrophobic surface；Graphene is water-soluble
Drop is added in super hydrophilic array hole, and the dendritic gold of nanometer/graphene-based bottom is obtained after evaporation.
Further, the super hydrophilic array etches to obtain by carrying out mask plate method in the super hydrophobic surface.
A kind of dendritic gold of super infiltration nanometer/graphene microchip preparation method for many body system detection, including it is as follows
Step:
Step 1: nanometer it is dendritic gold preparation: electro-conductive glass is sufficiently cleaned, conductive side difference one layer of titanium layer of magnetron sputtering and
Layer gold deposits 1000 s in chlorauric acid solution using electrochemical deposition method with -1.8 V voltages and obtains super hydrophilic nanometer
Dendritic gold structure；
Step 2: the modification on super infiltration surface: the dendritic golden structure of the nanometer that step 1 is obtained carries out hydrophobic treatment, obtains super thin
Water surface；Super hydrophobic surface is destroyed in ultraviolet light or plasma etching by mask plate, obtains super hydrophilic array；
Step 3: the dendritic gold of nanometer/graphene-based bottom preparation: graphene aqueous solution is added drop-wise to the super hydrophilic battle array of step 2 preparation
It arranges in hole, the dendritic gold of nanometer/graphene-based bottom is obtained after evaporation.
A kind of above-mentioned dendritic gold of super infiltration nanometer/graphene microchip for many body system detection is in biological stigmata
Application in the fluorescence detection of object, the adsorbable single stranded DNA of graphene are modified the DNA probe for having fluorescent marker dendritic to nanometer
Gold/graphene-based bottom, after the miRNA of detection is added, miRNA forms double-strand in conjunction with DNA probe, and graphene adsorbs double-strand
Power is weaker, and double-strand is discharged into supernatant, and as miRNA concentration increases, fluorescence signal is gradually increased.
A kind of above-mentioned dendritic gold of super infiltration nanometer/graphene microchip for many body system detection is in biological stigmata
Application in the Electrochemical Detection of object modifies the DNA probe of a terminal modified ferrocene to the dendritic gold of nanometer/graphene-based bottom,
After the miRNA of detection is added, miRNA forms double-strand in conjunction with DNA probe, and graphene is weaker to double-strand adsorption capacity, by double-strand
It is discharged into supernatant, the dendritic gold of nanometer/graphene-based bottom ferrocene quantity is reduced, and utilizes dendritic golden hypersensitive electrochemical signals
Response carries out electrochemistry miRNA detection, and as miRNA concentration increases, electric signal is gradually decreased.
A kind of above-mentioned dendritic gold of super infiltration nanometer/graphene microchip for many body system detection is in biological stigmata
Application in the SERS detection of object modifies the DNA probe of a terminal modified Raman signal to the dendritic gold of nanometer/graphene-based bottom,
After the miRNA of detection is added, miRNA forms double-strand in conjunction with DNA probe, and graphene is weaker to double-strand adsorption capacity, by double-strand
It is discharged into supernatant, is carried out by reinforcing effect of the dendritic gold of nanometer to Raman signal at the dendritic gold of nanometer/graphene-based bottom
SERS detection, as miRNA concentration increases, SERS signal is gradually reduced.
A kind of above-mentioned dendritic gold of super infiltration nanometer/graphene microchip for many body system detection is in biological stigmata
Object many body system detection in application, the terminal modified electrochemical signals molecule ferrocene of DNA probe one, another terminal modified Raman with it is glimmering
Light characteristic signal molecule ROX, DNA probe is simultaneously to fluorescence, electrochemistry and SERS response.
Further, the biological disease marker includes albumen, miRNA and ctDNA.
The invention has the benefit that solution impregnates and the obtained super infiltration nanometer of solution-evaporation is dendritic by electro-deposition
Gold/graphene microchip (biosensor) has been implemented in combination with by the dendritic golden excellent properties of graphene and nanometer and has been marked to biology
The fluorescence of will object, electrochemistry and the detection of SERS many body system；The invention detects same detection liquid by many body system, solves now
Marker concentration is too low when quickly directly detecting disease by body fluid, and detection device and environment influence asking for caused accuracy bottom
Topic, three kinds of testing results are compared the accuracy that verifying improves detection, effectively avoid false positive detection；Microchip is raw
Production. art is simple, has a extensive future.
Detailed description of the invention
Fig. 1 a show the dendritic golden scanning electron microscope phenogram of nanometer.
Fig. 1 b show the dendritic gold of nanometer/graphene scanning electron microscope phenogram.
Fig. 2 a show super-hydrophobic dendritic golden microchip contact angle characterization picture.
Fig. 2 b show super hydrophilic dendritic gold/graphene microchip contact angle characterization picture.
Fig. 3 show the super dendritic gold of infiltration nanometer/graphene microchip pictorial diagram.
Fig. 4 show graphene deposition process schematic diagram.
Fig. 5 a show water and rinses the dendritic gold of nanometer/graphene-based bottom pictorial diagram.
Fig. 5 b show ethyl alcohol and rinses the dendritic gold of nanometer/graphene-based bottom pictorial diagram.
Fig. 6 show different base electrochemical signals comparison diagram.
Fig. 7 show the micrograph of different volumes graphene deposition.
Fig. 8 a show the Electrochemical Detection comparison diagram of different graphene amount microchips.
Fig. 8 b show the fluorescence detection comparison diagram of different graphene amount microchips.
Fig. 8 c show the SERS detection comparison diagram of different graphene amount microchips.
Fig. 9 show the super dendritic gold of infiltration nanometer/graphene microchip many body system detection schematic diagram.
Figure 10 a show the super dendritic gold of infiltration nanometer/graphene microchip fluorescence detection various concentration miRNA standard curve
Figure.
Figure 10 b show the super dendritic gold of infiltration nanometer/graphene microchip SERS detection various concentration miRNA standard curve
Figure.
It is bent that Figure 10 c show the super dendritic gold of infiltration nanometer/graphene microchip Electrochemical Detection various concentration miRNA standard
Line chart.
Specific embodiment
Below in conjunction with specific attached drawing the present invention is described in detail specific embodiment.It should be noted that in following embodiments
The combination of the technical characteristic or technical characteristic of description is not construed as isolated, they can be combined with each other to reaching
To superior technique effect.In the drawings of the following embodiments, the identical label that each attached drawing occurs represent identical feature or
Person's component, can be apply to different embodiments.
Following inventive embodiments are that marker concentration is too low when solving quickly directly to detect disease by body fluid now, detection
The problem of accuracy bottom caused by device and environment influence.
Embodiment 1
1, the dendritic gold substrate preparation of nanometer: electro-conductive glass piece is cut into 1.5 × 2.5 cm specifications, in Piranha washing lotion (98%
H2SO4: 30% H2O2, V/V=3:1) and 1 h of middle immersion, takes out sheet glass and is immersed in acetone respectively, ultrasound is clear in ethyl alcohol and ultrapure water
It washes 30-40 min, takes out sheet glass with being dried with nitrogen.It determines that glass conduction one faces upward by multimeter, is placed on oxygen plasma
4-5 min is cleaned in cleaning device.One layer of titanium is deposited in conductive side with magnetic control sputtering device behind thorough cleaning surface, one is deposited again
Layer gold will not fall off with the dendritic gold for guaranteeing next step.Nanometer dendritic golden (Fig. 1 a) is by electrochemical deposition method modification to leading
On electric glass, wherein electro-conductive glass is as working electrode, and platinized platinum is to electrode, and Ag/AgCl electrode is reference electrode, deposits liquid
For 1 mg/mL chlorauric acid solution, deposition voltage is -1.8 V, and sedimentation time is 1800 S, obtains required super hydrophilic nanometer branch
Shape gold substrate, it is stand-by with ethyl alcohol and ultrapure water substrate.
2, the obtained dendritic gold substrate of super hydrophilic nanometer the preparation of super-hydrophobic-super hydrophilic array: is immersed in hydrophobic modification
In liquid (tert-dodecyl mercaptan: ethyl alcohol, V/V=1:9), sealing reaction 12-24 h, mercaptan passes through golden sulfide linkage and dendritic golden stable bond,
The mercaptan removed on unmodified is sufficiently cleaned with ethyl alcohol, and the dendritic golden material (Fig. 2 a) of super-hydrophobic nano is obtained after air-drying.It will be customized
The aluminum mask plate of 2.5 × 1.5 cm cover and clamped in hydrophobic chip surface with binder clip, have 2 × 3 sizes identical in template
Diameter be 1 mm circular hole, chip is placed on to 1-2 min in plasma cleaning instrument with mask plate together with, at circular hole modification
Mercaptan is decomposed to form hydrophilic site (Fig. 2 b) by plasma cleaning instrument, thus prepares the surface of super-hydrophobic-super hydrophilic array
Material (Fig. 3).
3, the dendritic gold of nanometer/graphene-based bottom preparation: 5 mg graphenes are added in 10 mL water, are placed on ultrasonic clear
Washing 30-40 min in instrument makes graphene fully dispersed in water, in the hydrophilic site that graphene aqueous solution is added to,
Dendritic gold surface (Fig. 4) is sunk to moisture natural air drying graphene, obtains the dendritic gold of nanometer/graphene-based bottom (Fig. 1 b).
To the super dendritic gold of infiltration nanometer/graphene microchip many body system detection feasibility judgement and optimization analysis:
(1) dendritic gold/graphene-based bottom stability is studied.Hydrophilic inner hole deposition is washed away with water (Fig. 5 a) and ethyl alcohol (Fig. 5 b) respectively
Long-pending graphene, stable being present in hydrophilic pores of graphene will not fall off, it is thus identified that answer at the dendritic gold of nanometer/graphene-based bottom
With the feasibility of detection.
(2) influence of the dendritic gold/graphene to Electrochemical Detection is studied.Using two electrode systems, microchip is work electricity
Pole, Ag/AgCl are to electrode and reference electrode, and it (includes 0.1M KCL and 5mM K that a drop detection liquid, which is added dropwise, in working electrode3
[Fe(CN)6]/K4[Fe(CN)6] 0.01 M phosphate buffer) carry out cyclic voltammetry scan, compare electro-conductive glass, plane
Gold, dendritic gold and dendritic gold/graphene-based bottom electrochemical signals (Fig. 6), four substrates can all measure complete cyclic voltammetric
Curve, dendritic gold are remarkably reinforced with dendritic gold/graphene-based bottom electrochemical signals compared to electro-conductive glass and plane gold, explanation
The dendritic relatively large specific surface area of gold improves the sensitivity and detection limit in Electrochemical Detection.It is added dropwise in hydrophilic site point different
The dendritic gold that the graphene aqueous solution of volume (2 μ L, 4 μ L, 6 μ L, 8 μ L, 10 μ L) obtains/graphene-based bottom (Fig. 7) electrification
It is almost the same with dendritic gold substrate (Fig. 8 a) to learn signal, illustrates that the amount of graphene does not influence the detection of substrate electrochemical signals.
(3) dendritic gold/influence of the graphene-based bottom to fluorescence detection is studied.The DNA probe for being 10 μM by 10 μ L concentration
It is added drop-wise to dendritic gold/graphene-based bottom with different graphene amounts respectively and uses ultrapure water after the evaporation of DNA probe solution is dry
The unadsorbed DNA probe in dendritic gold/graphene-based bottom is cleaned, 100 μ L are diluted to and detects supernatant under 578 nm excitation wavelengths
Liquid fluorescence intensity determines the amount of adsorption of DNA, and 6 μ L stones are added in obtained fluorogram comparative illustration in 1 mm hydrophilic pores of diameter
The amount of the DNA probe adsorbed when black aqueous solution reaches maximum value (Fig. 8 b).
(4) influence that SERS is detected at dendritic gold/graphene-based bottom is studied.The rhodamine R6G for being 1 μM by 10 μ L concentration
It is added drop-wise to the dendritic gold of the nanometer with different graphene amounts (2 μ L, 4 μ L, 6 μ L, 8 μ L, 10 μ L)/graphene-based bottom, benefit
With the Raman signal of 532 nm excitation light detection different base, Raman map show the increase Raman signal with graphene amount by
Decrescence weak (Fig. 8 c).
Embodiment 2
The super infiltration dendritic gold of nanometer/graphene microchip (biosensor) fluorescence, electrochemistry and SERS many body system detection biology
Disease marker, by taking prostate cancer marker miRNA-375 as an example:
(1) testing principle: DNA probe sequence is 5 '-ROX- TCACGCGAGCCGAACGAAC AAA-Ferrocene-3 ', inspection
The miRNA sequence of survey is 5 '-UUUGUUCGUUCGGCUCGCGUG A-3 '.The terminal modified ROX of probe sequence one is a kind of Luo Dan
Signaling molecule that is bright, fluorescence and Raman double-bang firecracker being answered, it is another it is terminal modified be ferrocene, can be corresponding to electrochemical signals
Molecule.When DNA probe is added to the dendritic gold of nanometer/graphene-based bottom, single-stranded DNA probe can be adsorbed to graphene-based
On bottom, it is possible thereby to detect very strong SERS signal and electrochemical signals, and supernatant is because of the not presence inspection of DNA probe
Fluorescence signal is not detected.After the miRNA of detection is added, the miRNA of detection is combined with DNA probe, and graphene can be by double-strand
Be discharged into supernatant, at this time the dendritic gold/graphene-based bottom of nanometer due to DNA probe obtain quantity reduce so that electrochemical signals and
SERS signal weakens, and fluorescence signal enhances in supernatant.It is possible thereby to by one drop miRNA detect liquid by three kinds of signals come
Determine miRNA concentration (Fig. 9) in detection liquid.
(2) DNA probe that the concentration of 10 μ L is 10 μM detecting step: is added drop-wise to the dendritic gold/graphene of hydrophilic
In array hole, it is placed on after at room temperature evaporating moisture and rinses hydrophilic pores with water flow, wash unadsorbed DNA probe, it will
With the diluted various concentration (10 of PBS-9M, 10-10M, 10-11M, 10-12M, 10-13M, 10-14M miRNA-375 solution)
It is added drop-wise in hydrophilic pores, reacting 1.5 h in 37 DEG C of climatic chambers hybridizes DNA sufficiently with miRNA.It will be upper in hydrophilic pores
Clear liquid, which is put into fluorescence ware, is diluted to 100 μ L, and various concentration miRNA-375 is added in detection under the exciting light of 578 nm wavelength
The fluorescence intensity of supernatant integrates various concentration fluorescence intensity curves and draws standard curve (Figure 10 a).Supernatant will be removed
Dendritic gold/graphene array the hole of nanometer carries out Raman detection under 633 nm exciting lights, integrates the Raman curve under various concentration
Map obtains canonical plotting (Figure 10 b).Hydrophobic substrate after SERS detection is added dropwise 10 μ L and contains 100 mM sodium chloride
The phosphate buffer of 0.01 M is integrated to obtain standard curve (figure with the electrochemical profiles that differential pulse method measures various concentration
10c).
Biological disease marker is not limited only to miRNA, can also be albumen or ctDNA, can obtain preferably detecting knot
Fruit.
Although having been presented for several embodiments of the present invention herein, it will be appreciated by those of skill in the art that
Without departing from the spirit of the invention, the embodiments herein can be changed.Above-described embodiment is only exemplary, no
It should be using the embodiments herein as the restriction of interest field of the present invention.
Claims (9)
1. a kind of dendritic gold of super infiltration nanometer/graphene microchip for many body system detection, which is characterized in that the microchip
It is detected for fluorescence, electrochemistry and SERS many body system；The microchip successively include: from top to bottom electro-conductive glass substrate, titanium layer,
The dendritic layer gold of plane layer gold, nanometer, super hydrophobic surface, the super hydrophobic surface are provided with super hydrophilic array, and super hydrophilic array is
The dendritic gold of nanometer/graphene-based bottom.
2. the dendritic gold of super infiltration nanometer/graphene microchip for many body system detection, feature exist as described in claim 1
In the method that the titanium layer, plane layer gold pass through magnetron sputtering is modified to the conductive side of the electro-conductive glass；The nanometer
Dendritic layer gold is with the method modification of electrochemical deposition to the plane layer gold；Hydrophobic treatment is carried out to the dendritic layer gold of the nanometer,
Obtain the super hydrophobic surface；Super hydrophilic array is formed in the super hydrophobic surface；Graphene aqueous solution is added drop-wise to super hydrophilic
The dendritic gold of nanometer/graphene-based bottom is obtained in array hole, after evaporation.
3. the dendritic gold of super infiltration nanometer/graphene microchip for many body system detection, feature exist as claimed in claim 2
In the super hydrophilic array etches to obtain by carrying out mask plate method in the super hydrophobic surface.
4. the dendritic gold of super infiltration nanometer/graphene microchip as described in any one of claims 1-3 for many body system detection
Preparation method, which comprises the steps of:
Step 1: nanometer it is dendritic gold preparation: electro-conductive glass is sufficiently cleaned, conductive side difference one layer of titanium layer of magnetron sputtering and
Layer gold deposits 1000 s in chlorauric acid solution using electrochemical deposition method with -1.8 V voltages and obtains super hydrophilic nanometer
Dendritic gold structure；
Step 2: the modification on super infiltration surface: the dendritic golden structure of the nanometer that step 1 is obtained carries out hydrophobic treatment, obtains super thin
Water surface；Super hydrophobic surface is destroyed in ultraviolet light or plasma etching by mask plate, obtains super hydrophilic array；
Step 3: the dendritic gold of nanometer/graphene-based bottom preparation: graphene aqueous solution is added drop-wise to the super hydrophilic battle array of step 2 preparation
It arranges in hole, the dendritic gold of nanometer/graphene-based bottom is obtained after evaporation.
5. the dendritic gold of super infiltration nanometer/graphene microchip as described in any one of claims 1-3 for many body system detection
Application in the fluorescence detection of biological disease marker, which is characterized in that the adsorbable single stranded DNA of graphene will have fluorescence mark
The DNA probe modification of note is to the dendritic gold of nanometer/graphene-based bottom, and after the miRNA of detection is added, miRNA is in conjunction with DNA probe
Double-strand is formed, graphene is weaker to double-strand adsorption capacity, double-strand is discharged into supernatant, as miRNA concentration increases, fluorescence letter
It number gradually increases.
6. the dendritic gold of super infiltration nanometer/graphene microchip as described in any one of claims 1-3 for many body system detection
Application in the Electrochemical Detection of biological disease marker, which is characterized in that modify the DNA probe of a terminal modified ferrocene
To the dendritic gold of nanometer/graphene-based bottom, after the miRNA of detection is added, miRNA forms double-strand, graphene in conjunction with DNA probe
It is weaker to double-strand adsorption capacity, double-strand is discharged into supernatant, the dendritic gold of nanometer/graphene-based bottom ferrocene quantity is reduced, benefit
Electrochemistry miRNA detection is carried out with dendritic golden hypersensitive electrochemical signals response, as miRNA concentration increases, electric signal is gradually
It reduces.
7. the dendritic gold of super infiltration nanometer/graphene microchip as described in any one of claims 1-3 for many body system detection
Application in the SERS detection of biological disease marker, which is characterized in that modify the DNA probe of a terminal modified Raman signal
To the dendritic gold of nanometer/graphene-based bottom, after the miRNA of detection is added, miRNA forms double-strand, graphene in conjunction with DNA probe
It is weaker to double-strand adsorption capacity, double-strand is discharged into supernatant, the reinforcing effect of Raman signal is being received by nanometer dendritic gold
Meter Zhi Zhuan gold/graphene-based bottom carries out SERS detection, and as miRNA concentration increases, SERS signal is gradually reduced.
8. the dendritic gold of super infiltration nanometer/graphene microchip as described in any one of claims 1-3 for many body system detection
Application in many body system detection of biological disease marker, which is characterized in that the terminal modified electrochemical signals molecule of DNA probe one
Ferrocene, another terminal modified Raman and fluorescent characteristics signaling molecule ROX, DNA probe simultaneously ring fluorescence, electrochemistry and SERS
It answers.
9. application as claimed in claim 8, which is characterized in that the biology disease marker include albumen, miRNA and
ctDNA。
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| CN109975271A (en) * | 2019-04-24 | 2019-07-05 | 西南交通大学 | The base material and its application method of high reproducibility Surface enhanced Raman scattering |
| CN110186975A (en) * | 2019-06-17 | 2019-08-30 | 北京科技大学 | Microlayer model electrochemical sensor and preparation method for food-borne microorganism detection |
| CN110412008A (en) * | 2019-07-23 | 2019-11-05 | 北京科技大学 | A kind of adhesive tape base portable SERS sensor and its preparation method and application |
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