CN115015351A - Near-infrared light excited photoelectrochemical sensor and preparation method thereof - Google Patents
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
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- G—PHYSICS
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- G—PHYSICS
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Abstract
The invention discloses a near infrared light excited photoelectrochemical sensor and a preparation method thereof. Firstly, a photoelectrochemical sensor interface containing up-conversion nano particles and a heterojunction semiconductor material is synthesized, and then a Y-type DNA probe is constructed on the photoelectrochemical sensor to identify and detect carcinoembryonic antigen (CEA). Wherein the upconversion material absorbs near infrared wavelengths and emits light of a high energy wavelength as a light source to be converted by the semiconductor material (SnS) 2 ‑ZnIn 2 S 4 CdSe) to generate photocurrent, and realizing high-sensitivity detection of the target carcinoembryonic antigen through the dual signal enhancement effect generated by the response of the Y-type DNA probe to the carcinoembryonic antigen. Semiconductor material (SnS) constructed by the invention 2 /ZnIn 2 S 4 /CdSe) capable of absorbing the emission of the up-converted nanoparticlesUltraviolet light of different wavelengths, in SnS 2 、ZnIn 2 S 4 And heterojunction is formed among different semiconductor materials of CdSe, so that the recombination of electrons and holes is reduced, the photoelectric response is improved, and the detection sensitivity is enhanced.
Description
Technical Field
The invention relates to the technical field of photoelectrochemical signal detection and immunoassay detection, in particular to a near-infrared light excited photoelectrochemical sensor and a preparation method thereof.
Background
Carcinoembryonic antigen (CEA) is the most commonly used tumor-associated antigen, which is an acidic glycoprotein synthesized in small intestine, liver and pancreas at the embryonic stage and present in normal human serum only in a trace amount. CEA is used as a broad-spectrum tumor marker, and has important values for curative effect judgment, disease development, monitoring and prognosis evaluation data of digestive tract tumors and lung cancer.
Upconverters that are excited by low energy light (e.g., near red appearance) to emit high energy light (uv light) are commonly used in biosensor detection. For example, the photoelectric sensing interface is formed by compounding up-conversion materials UCNPs, nanogold and cadmium sulfide quantum dots in Near-extracted Light-Excited Core-Shell UCNP @ Au @ CdSe Upconversion Nanospheres for Ultrasensitive Photoelectrochemical Enzyme Immunoassay, anal chem.2018,90,9568-9575 and is used for biosensing detection. The infrared light excites the up-conversion material, and the emitted light with low wavelength is used as a light source to excite the photoelectric active substance cadmium sulfide quantum dots to generate photoelectric signals. However, a single photoelectric material is likely to cause recombination of electrons and holes, to reduce the photoelectric effect and thus the detection sensitivity, and it is difficult to use all of the light of a plurality of wavelengths emitted from the upconverting material to reduce the use of near-infrared light in natural light.
In order to realize the utilization of the near infrared wavelength by the photoelectric sensing detection and realize the detection of the CEA rapidly and at low cost, a method which can efficiently utilize the near infrared wavelength and does not need amplification is needed to be designed for detecting the CEA.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a near-infrared light excited photoelectrochemical sensor and a preparation method thereof. Firstly, synthesizing a photoelectrochemical sensor interface containing up-conversion nano particles and a heterojunction semiconductor material, and then constructing a Y-shaped DNA probe on the photoelectrochemical sensor to identify and detect CEA. Wherein the upconversion material absorbs near infrared light and the emitted light of high energy wavelength is used as a light source to be converted again by the semiconductor material (SnS) 2 -ZnIn 2 S 4 CdSe) to generate photocurrent, and detecting CEA through photocurrent change generated by response of the Y-type DNA probe to the CEA. Semiconductor material (SnS) constructed by the invention 2 /ZnIn 2 S 4 CdSe) can effectively absorb ultraviolet light with different wavelengths emitted by the upper conversion nanometer material. At the same time, in SnS 2 、ZnIn 2 S 4 And heterojunction is formed among different semiconductor materials of CdSe, so that the recombination of electrons and holes is reduced, and the photocurrent response is improved.
In order to achieve the purpose, the invention relates to a preparation method of a near infrared light excited photoelectrochemical sensor, which specifically comprises the following steps:
(1) SnS 2 Suspension, ZnIn 2 S 4 The suspension and the UCNPs suspension are sequentially dripped on an ITO glass sheet to obtain ITO/SnS 2 /ZnIn 2 S 4 a/UCNPs electrode;
(2) dropping and coating AuNPs suspension on ITO/SnS 2 /ZnIn 2 S 4 Obtaining ITO/SnS on the surface of a/UCNPs electrode 2 /ZnIn 2 S 4 a/UCNPs/Au electrode;
(3) the activated DNA1-CdSe is coated on ITO/SnS by dripping 2 /ZnIn 2 S 4 On the surface of the/UCNPs/Au electrode, the-SH of the DNA1-CdSe terminal is combined with AuNPs on the surface of the electrode through Au-S bond to obtain ITO/SnS 2 /ZnIn 2 S 4 the/UCNPs/Au/DNA 1-CdS electrode has the advantages that due to the hairpin structure of the DNA1, the CdSe at the tail end of the DNA1-CdSe is close to the surface of the electrode, and photoelectric signals are enhanced;
(4) different concentrations of CEA-aptamer and DNA2-SiO 2 NP were mixed and the mixed sample was dropped on ITO/SnS 2 /ZnIn 2 S 4 Heating to 88 ℃ in a humid environment on a/UCNPs/Au/DNA 1-CdSe electrode, incubating for 10min, then gradually cooling to room temperature, developing a hairpin structure of DNA1, and complementarily pairing base pairs of DNA1, CEA-aptamer and DNA2 to form a Y-type DNA probe. In this case, the Y-type DNA probe is made of SiO linked to the DNA2 end 2 Close to the electrode surface, a shielding effect is generated. Meanwhile, the CdSe connected with the tail end of the DNA1 is far away from the surface of the electrode, and the photoelectric signal is weakened under the combined influence of the two functions;
(5) blocking of ITO/SnS Using BSA solution 2 /ZnIn 2 S 4 Adding CEA with different concentrations, incubating at 4 deg.C for 2h, washing with PBS, detecting photoelectric signal change under excitation of near infrared light, combining CEA with CEA-aptamer to destroy Y-type DNA probe, and using SiO to bind to DNA1-CdSe electrode 2 Leaving the surface of the electrode, the DNA1 recovers a hairpin structure, and the CdSe is close to the surface of the electrode, so that under the common influence of the two functions, the photocurrent is greatly enhanced, and the detection of the CEA is realized.
Specifically, the sequence of DNA 1: ATAACTCAACATCATAAGCTGGAAGTTAT, respectively;
CEA-aptamer sequence: CCAGCTTATTCAATTCAGCTA, respectively;
DNA2 sequence: TAGCTGAATTGAATGATGTTGA are provided.
Specifically, UCNPs is Y 3+ ：Yb 3+ ：Er 3+ The upconversion nanoparticles are 78:20:2, and the preparation method of the UCNPs comprises the following steps:
2mmol of LnCl 3 (78％Y 3+ 、20％Yb 3+ 、2％Er 3+ ) And 4mmol NaCl and 0.8g Branched Polyethyleneimine (BPEI) were dissolved in 30mL ethylene glycol at 50 ℃ and reported as solution A; under vigorous stirring, 8.0mmol of NH 4 Dissolving F in 20mL of glycol, and marking as a solution B; dropwise adding the solution B into the solution A under vigorous stirring, stirring at 50 ℃ for 20min, transferring into a 100mL Teflon-lined autoclave, and heating at 200 ℃ for 120 min; finally, BPEI functionalized NaYF 4 Yb, Er upconversion nano particles (BPEI/UCNP) are alternately and centrifugally washed for a plurality of times by ethanol and deionized water, and are dried for 12 hours in vacuum at 50 ℃ to obtain Y 3+ ：Yb 3+ ：Er 3+ Up-converting nanoparticles UCNPs at 78:20: 2.
Further, the preparation method of the DNA1-CdSe comprises the following steps: amino is modified at one end of the DNA1, sulfhydryl is modified at the other end, and bases close to the two ends are complementarily paired to form a hairpin DNA 1; CdSe-COOH QDs were coupled with hairpin DNA1(SH-DNA 1-NH) by carboxyl-amino coupling reaction 2 ) Amide bonds are formed. The method specifically comprises the following steps: 2.0mg EDC and 3.0mg NHS were added to 75. mu.L of purified CdSe-COOH QDs aqueous solution and reacted at room temperature for 1h to activate carboxyl groups; however, the device is not suitable for use in a kitchenThen, 25. mu.L of 40. mu.M hairpin DNA1 was added to the activated CdSe-COOH QDs solution and reacted at 4 ℃ for 6h to give DNA 1-CdSe.
Further, the CdSe-COOH QDs are thioglycollic acid-terminated CdSe QDs, and the preparation method comprises the following steps: first, 453.6mgNaBH was added under magnetic stirring 4 Adding 48mg of Se powder into a three-neck flask, adding into 15mL of deionized water, and continuously stirring for 2h to obtain a clear sodium hydroselenide solution; subsequently, 273.9mg of CdCl 2 ·2.5H 2 Preparation of Cd from O in 285mL of ultrapure water 2+ Adding 95mLCd into the solution in a three-neck flask under magnetic stirring 2+ The solution was then added 74. mu.L TGA solution and the pH adjusted to 9 by the addition of 1.0mol/L NaOH for 30min N 2 To remove oxygen; subsequently, 5mL of the prepared NaHSe was added to the mixture and heated in a water bath at 80 ℃ for 4h to obtain 3-mercaptoacetic acid-terminated CdSe QDs.
Further, DNA2-SiO 2 The preparation method of NP comprises the following steps: modification of-NH at one end of DNA2 2 Single-stranded DNA2 was formed by mixing 10. mu.L of 0.05% glutaraldehyde, 30. mu.L of SiO 2 -NH 2 NPs and 1mL of 2. mu.M single-stranded DNA2 were mixed at room temperature with stirring for 1h, and single-stranded DNA2 and SiO were mixed by glutaraldehyde 2 -NH 2 Synthesis of DNA2-SiO by ligation of two amino groups on NPs 2 An NP conjugate.
Further, the SiO 2 -NH 2 The preparation method of the NPs comprises the following steps: tetraethyl orthosilicate and NH 3 ·H 2 Adding O and ethanol into a beaker, stirring, and then centrifugally washing and dispersing the obtained solution in 5mL of ethanol; then, the (3-aminopropyl) triethoxysilane solution and SiO 2 NP solution was mixed and stirred overnight to give SiO 2 -NH 2 NPs。
Compared with the prior art, the invention has the following beneficial effects:
(1) semiconductor material (SnS) constructed by the invention 2 /ZnIn 2 S 4 /CdSe) in SnS 2 、ZnIn 2 S 4 And a heterojunction is formed between different semiconductor materials of CdSe, so that the recombination of electrons and holes is reduced, and ultraviolet light emitted by the up-conversion material can be efficiently absorbed by a photoactive substance SnS 2 /ZnIn 2 S 4 CdSe absorption.
(2) The Y-type DNA probe constructed by the invention comprises DNA1-CdSe, CEA-aptamer and DNA2-SiO 2 NP is the amino acid. When there is no CEA as the target, because of SiO 2 The double effect of CdSe away from the electrode surface, the photocurrent is low. When CEA is added, SiO causes destruction of the Y-type DNA probe due to CEA-aptamer recognition of CEA 2 Keep away from the electrode surface and CdSe is close to the electrode surface, realize dual signal amplification, increase signal variation intensity, improve and detect the limit.
(3) The invention improves the utilization of the photoelectrochemical sensor to the light with the near infrared wavelength, does not need amplification in the detection process, and has simple steps, convenient operation and low cost.
Drawings
Fig. 1 is a flowchart of a method for producing a near-infrared light-excited photoelectrochemical sensor mentioned in example 1.
FIG. 2 shows the emission spectra of the up-converted nanoparticles and SnS referred to in example 1 2 、ZnIn 2 S 4 And CdSe ultraviolet-visible diffuse reflectance absorption spectrum.
FIG. 3 shows ITO/SnS according to example 1 2 /ZnIn 2 S 4 Mechanism diagram of photocurrent generation on the structure of UCNPs/CdSe heterojunction.
FIG. 4 is a line graph showing the detection of CEA by the near-infrared light-excited photoelectrochemical sensor prepared in example 1.
FIG. 5 is a graph comparing the selectivity of near infrared light-excited photoelectrochemical sensors prepared in example 1 for different biomarkers.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Example 1
The DNA sequences used in this example were:
single-stranded DNA 1: SH-ATAACTCAACATCATAAGCTGGAAGTTAT-NH 2
CEA-aptamer：CCAGCTTATTCAATTCAGCTA
Single-stranded DNA 2: NH (NH) 2 -TAGCTGAATTGAATGATGTTGA
As shown in fig. 1, a method for manufacturing a near-infrared light excited photoelectrochemical sensor according to an embodiment of the present invention includes the following steps:
firstly, preparation work:
(1) nano ZnIn 2 S 4 The synthesis of (2):
1mmol of Zn (CH) 3 COO) 2 ·2H 2 O and 2mmol of InCl 3 ·4H 2 O was dissolved in 60mL of deionized water, and 6mmol of TAA (thioacetamide) was added to the solution. After stirring for 30min, the mixture was transferred to a 100mL Teflon lined autoclave and held at 160 ℃ for 12 h. The product was collected by centrifugation, then washed several times with deionized water and ethanol and dried at 60 ℃ for 12h to obtain ZnIn 2 S 4 A nano-material.
Taking 6.0mg of ZnIn prepared above 2 S 4 Adding the nano material into a centrifugal tube, adding 1.0mL of deionized water, and performing ultrasonic dispersion to obtain 6mg/mL of ZnIn 2 S 4 And (3) suspension.
(2) Nano SnS 2 The synthesis of (2):
adding 2mmol SnCl 4 ·5H 2 O and 4mmol TAA were dissolved in 60mL isopropanol. After stirring vigorously for 30min, the clear solution was transferred to a teflon lined autoclave and heated at 180 ℃ for 24 h. Naturally cooling the autoclave to room temperature, collecting gold precipitate, washing with deionized water and ethanol for several times, and drying at 80 deg.C to obtain SnS 2 And (3) nano materials.
Collecting 6.0mg of SnS prepared above 2 Adding the nano material into a centrifugal tube, adding 1.0mL of deionized water, and performing ultrasonic dispersion to obtain 6mg/mL of SnS 2 And (3) suspension.
(3) Synthesis of upconversion nanoparticles (UCNPs):
2mmol of LnCl 3 (78％Y 3+ 、20％Yb 3+ 、2％Er 3+ ) And 4mmol NaCl and 0.8g BPEI were dissolved in 30mL of ethylene glycol at 50 ℃ and identified as solution A. Under vigorous stirring, 8.0mmol of NH 4 F was dissolved in 20mL of ethylene glycol and was designated as solution B. Solution B was added dropwise to solution A with vigorous stirring, and after stirring at 50 ℃ for a further 20min, the suspension was transferred to a 100mL Teflon-lined autoclave and heated at 200 ℃ for 120 min. Finally, BPEI functionalized NaYF 4 Yb, Er upconversion nano particles (BPEI/UCNP) are washed by ethanol and deionized water alternately and centrifugally for a plurality of times (10000r/min, 10min) and dried for 12h in vacuum at 50 ℃ to obtain Y 3+ ：Yb 3+ ：Er 3+ Up-converting nanoparticles UCNPs at 78:20: 2.
And (3) putting 100mg of the prepared up-conversion nano particle UCNPs into a centrifuge tube, adding 1.0mL of deionized water, and performing ultrasonic dispersion to obtain 100mg/mL UCNPs suspension.
(4) Synthesis of CdSe QDs-labeled DNA1(DNA 1-CdSe):
(401) synthesis of carboxyl-modified CdSe QDs (CdSe-COOH QDs):
first, 453.6mgNaBH was added under magnetic stirring 4 And 48mg of Se powder are added into a three-neck flask, added into 15mL of deionized water, and stirred continuously for 2 hours to obtain a clear sodium hydrogen selenide (NaHSe) solution. Subsequently, 273.9mg of CdCl 2 ·2.5H 2 Preparation of Cd from O in 285mL of ultrapure water 2+ Adding 95mL Cd into a three-neck flask under magnetic stirring 2+ The solution was then added 74. mu.L TGA solution and 1.0mol/LNaOH was added to adjust the pH of the solution to 9. General flow for 30min N 2 To remove oxygen. Subsequently, the prepared 5ml of NaHSe was added to the mixture and heated in a water bath at 80 ℃ for 4 hours to obtain an aqueous solution of CdSe-COOH QDs, which are represented as CdSe QDs having a carboxyl group attached to one end, in this example, 3-mercaptoacetic acid (TGA) -terminated CdSe Quantum Dots (QDs). The prepared CdSe-COOH QDs were washed twice by centrifugation with ethanol and then dispersed in an equal volume of deionized water.
(402) Synthesis of CdSe QDs-labeled hairpin DNA1(DNA 1-CdSe):
one end of DNA1 is modified with amino group, the other end is modified with sulfhydryl group, and the bases near the two ends are complementarily paired to form hairpin structure (also called stem-loop structure).CdSe-COOH QDs were coupled with hairpin DNA1(SH-DNA 1-NH) by classical EDC (1- (3-dimethylamino-propyl) -3-ethylcarbodiimide hydrochloride) and NHS (N-hydroxysuccinimide) carboxy-amino coupling reactions 2 ) Amide bonds are formed.
2.0mg EDC and 3.0mg NHS were added to 75. mu.L of purified CdSe-COOH QDs in water and reacted at room temperature for 1h to activate carboxyl groups. Then, 25. mu.L of hairpin DNA1 (40. mu.M) was added to the activated CdSe-COOH QDs solution and reacted at 4 ℃ for 6h to give CdSe QDs modified hairpin DNA1(DNA 1-CdSe). The mixture was washed by centrifugation (7000rpm/5min) and redispersed in 100. mu.L of ultrapure water. The modified DNA1-CdSe was stored at 4 ℃ until use.
(5) Synthesis of gold nanoparticles (AuNPs):
50mL of 0.01% HAuCl 4 Adding the solution into a three-neck flask, heating to boil under magnetic stirring, keeping the stirring speed unchanged during the heating process, then quickly adding 1.5mL of 0.01% trisodium citrate solution, changing the color of the solution from gray to orange red, shading, continuously refluxing for 30min, and then cooling the solution to room temperature. The resulting gold nanoparticles (AuNPs) were stored at 4 ℃ for further use.
(6)DNA 1 -SiO 2 Preparation of NP conjugates
(601) Amino-modified SiO 2 NPs(SiO 2 -NH 2 NPs) synthesis:
200 μ L of tetraethyl orthosilicate (TEOS), 2mLNH 3 ·H 2 O (28%) and 40mL of ethanol were added to the beaker and stirred for 2 days. Subsequently, the resulting solution was centrifugally washed and dispersed in 5mL of ethanol. Then, 35. mu.L of (3-aminopropyl) triethoxysilane (APTES) (97%) was mixed with 4mL of SiO 2 NP solution is mixed and stirred overnight to obtain SiO modified by amino 2 NPs(SiO 2 -NH 2 NPs). Finally, the SiO is washed centrifugally with ethanol 2 -NH 2 NPs were redispersed in 4mL deionized water three times.
(602)DNA2-SiO 2 Preparation of NP conjugate:
single-stranded DNA2 (NH) 2 DNA2) one-terminal modified amino group.10 μ L glutaraldehyde (0.05%), 30 μ LSiO 2 -NH 2 NPs and 1mL of single-stranded DNA2 (2. mu.M) were mixed at room temperature with stirring for 1h, and single-stranded DNA2 and SiO were mixed by glutaraldehyde 2 -NH 2 Synthesis of DNA2-SiO by ligation of two amino groups on NPs 2 An NP conjugate. Finally, the DNA obtained is subjected to 1 -SiO 2 The NP conjugate was washed with ethanol by centrifugation and redispersed in 1mL PBS (pH 7.4) for use.
Secondly, constructing a photoelectrochemical sensor:
(1) prepared 15 mu L of SnS with the concentration of 6mg/mL 2 The suspension was drop-coated onto an ITO glass plate, dried in an oven at 60 ℃ and then the unattached SnS was rinsed with deionized water 2 . Then, 15. mu.L of 6mg/mL ZnIn was dropped on the surface of the electrode 2 S 4 After washing with deionized water, 15. mu.L of 100mg/mL UCNPs were added dropwise to the electrode and dried at 60 ℃. Finally, the electrode is washed by deionized water for 3 times to obtain ITO/SnS 2 /ZnIn 2 S 4 a/UCNPs electrode.
(2) Dripping 15 mu LAuNPs prepared into ITO/SnS 2 /ZnIn 2 S 4 Drying the electrode surface at 60 ℃ to obtain ITO/SnS 2 /ZnIn 2 S 4 a/UCNPs/Au electrode.
(3) Then 10. mu.L of the DNA1-CdSe (1.0X 10) obtained above was added -5 mol/L) with 90. mu.L of 1.0X 10 -2 Reducing the mol/L TCEP solution for 1h at room temperature, and dripping 25 mu L of activated DNA1-CdSe on ITO/SnS 2 /ZnIn 2 S 4 The electrode is characterized in that the electrode is coated with a/UCNPs/Au electrode surface and is placed in a humid environment for incubation for 1h at 37 ℃, the-SH at the end of the DNA1-CdSe is combined with AuNPs on the electrode surface through Au-S, and the CdSe on the DNA1-CdSe is close to the electrode surface due to the hairpin structure of the DNA 1. Washing with deionized water to remove unreacted DNA1-CdSe and obtain ITO/SnS 2 /ZnIn 2 S 4 the/UCNPs/Au/DNA 1-CdSe electrode.
(4) mu.L of CEA aptamers (CEA-aptamers) at different concentrations and 15. mu.L of 2. mu.M DNA2-SiO 2 NP mixing, dropping the mixed sample on ITO/SnS 2 /ZnIn 2 S 4 Heating the electrode of/UCNPs/Au/DNA 1-CdSe in a humid environmentIncubating at 88 deg.C for 10min, gradually cooling to room temperature, developing hairpin DNA1, complementarily pairing DNA1, CEA-aptamer and DNA2 to form Y-type DNA probe, wherein the Y-type DNA probe is composed of DNA2 terminal connected SiO 2 Near the electrode surface, CdSe attached to the end of DNA1 was remote from the electrode surface.
As shown in FIG. 2, UCNPs of the up-conversion nanoparticles absorb 980nm near-infrared light (curve a), the emitted light is at 520-550nm and 660nm, and SnS 2 (Curve a), ZnIn 2 S 4 (curve b) and CdSe (curve c) have ultraviolet-visible diffuse reflectance (UV-vis DRS) absorption spectra that exactly coincide with the emission of the upconverting nanoparticle. It is stated that the emitted light of the above-mentioned converted nanoparticles can be efficiently converted by SnS 2 /ZnIn 2 S 4 the/CdSe composite material absorbs to generate photocurrent, and the utilization rate of energy is high, so that SnS selected in the embodiment 2 /ZnIn 2 S 4 the/CdSe composite material has good matching with UCNPs.
As shown in fig. 3, SnS 2 、ZnIn 2 S 4 The energy band arrangement and the band gap energy of the CdSe can be well matched to form a heterojunction structure, so that the electron hole recombination is reduced, and the photoelectric conversion efficiency is improved. Thus, the energy of UCNPs can be transferred to SnS by Fluorescence Resonance Energy Transfer (FRET) 2 /ZnIn 2 S 4 The system of/CdSe.
Thirdly, detecting CEA:
the electrode was blocked with 20 μ L of 2% BSA for 2h to eliminate possible active sites on the upconverting nanoparticles, and then the electrode was washed. Adding carcinoembryonic antigen of different concentrations, incubating at 4 deg.C for 2h, washing with PBS, exciting light wavelength of 980nm, constant potential of 0V, and performing i-t curve method at 0.1M Na 2 SO 4 The photocurrent signal was measured in solution.
When the Y-type DNA probe is not formed, the CdSe on the DNA1-CdSe is close to the surface of the electrode, the photocurrent signal is strong, and after the Y-type DNA probe is formed, the SiO connected with the tail end of the DNA2 in the Y-type DNA probe 2 The close proximity of the electrode surface blocks electron transfer, and the CdSe attached to the end of DNA1 is far from the electrode surface, resulting in a much reduced photocurrent due to the dual signal reduction effect. After adding the target CEAThe combination of CEA and CEA-aptamer to destroy the Y-shaped structure, SiO 2 Leaving the electrode surface, DNA2 restored the hairpin structure, CdSe was close to the electrode surface, and photocurrent was recovered. Thereby forming an on-off-on signal variation for detecting the target CEA.
As shown in FIG. 4, the photocurrent signal of the photosensor responds to different concentrations of target CEA, with photocurrent intensity increasing with increasing analyte concentration, with a linear range from 0.001 to 3ng mL –1 。
Detection in four, different biomarkers
Adding 1ng/mL CEA, 100ng/mL alpha-fetoprotein (AFP), 100ng/mL human immunoglobulin (IgG) and 100ng/mL Prostate Specific Antigen (PSA) into the photoelectrochemical sensor constructed in the second step, incubating and washing with PBS, setting the excitation light wavelength to be 980nm and the constant potential to be 0V, and performing an i-t curve method on the light with 0.1M Na 2 SO 4 The photocurrent signal was measured in solution. As shown in fig. 5, the sensor of the present invention is most selective for CEA.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. A preparation method of a near infrared light excited photoelectrochemical sensor is characterized by comprising the following steps:
(1) SnS 2 Suspension, ZnIn 2 S 4 The suspension and the UCNPs suspension are sequentially dripped on an ITO glass sheet to obtain ITO/SnS 2 /ZnIn 2 S 4 a/UCNPs electrode;
(2) dropping coating AuNPs suspension on ITO/SnS 2 /ZnIn 2 S 4 Obtaining ITO/SnS on the surface of a/UCNPs electrode 2 /ZnIn 2 S 4 a/UCNPs/Au electrode;
(3) the activated DNA1-CdSe is coated on ITO/SnS by dripping 2 /ZnIn 2 S 4 On the surface of a/UCNPs/Au electrode, DNA 1-SH at the end of CdSe and AuNPs on the surface of the electrode pass throughAu-S bond bonding to obtain ITO/SnS 2 /ZnIn 2 S 4 the/UCNPs/Au/DNA 1-CdSe electrode has the advantages that due to the hairpin structure of the DNA1, the CdSe at the tail end of the DNA1-CdSe is close to the surface of the electrode, and photoelectric signals are enhanced;
(4) different concentrations of CEA-aptamer and DNA2-SiO 2 NP were mixed and the mixed sample was dropped on ITO/SnS 2 /ZnIn 2 S 4 Heating to 88 ℃ in a humid environment on a/UCNPs/Au/DNA 1-CdSe electrode, incubating for 10min, then gradually cooling to room temperature, developing a hairpin structure of DNA1, and complementarily pairing base pairs of DNA1, CEA-aptamer and DNA2 to form a Y-type DNA probe. In this case, the Y-type DNA probe is made of SiO linked to the DNA2 end 2 Close to the electrode surface, a shielding effect is generated. Meanwhile, the CdSe connected with the tail end of the DNA1 is far away from the surface of the electrode, and the photoelectric signal is weakened under the combined influence of the two functions;
(5) blocking of ITO/SnS Using BSA solution 2 /ZnIn 2 S 4 Adding CEA with different concentrations to incubate for 2h at 4 ℃ and wash with PBS, detecting the change of photoelectric signals under the excitation of near infrared light, combining CEA with CEA-aptamer to destroy Y-type DNA probe, SiO 2 Leaving the surface of the electrode, the DNA1 recovers a hairpin structure, and the CdSe is close to the surface of the electrode, so that under the common influence of the two functions, the photocurrent is greatly enhanced, and the detection of the CEA is realized.
2. The method for preparing a near-infrared light-excited photoelectrochemical sensor according to claim 1, wherein the DNA1 sequence: ATAACTCAACATCATAAGCTGGAAGTTAT, respectively;
CEA-aptamer sequence: CCAGCTTATTCAATTCAGCTA, respectively;
DNA2 sequence: TAGCTGAATTGAATGATGTTGA are provided.
3. The method of claim 1, wherein the UCNPs is Y 3+ ：Yb 3+ ：Er 3+ Up-converting nanoparticles at 78:20: 2.
4. According to the rightThe method for preparing a near-infrared light-excited photoelectrochemical sensor according to claim 3, wherein the method for preparing the UCNPs comprises the following steps: 2mmol of LnCl 3 (78％Y 3+ 、20％Yb 3+ 、2％Er 3+ ) And 4mmol NaCl and 0.8g BPEI were dissolved in 30mL ethylene glycol at 50 ℃ and recorded as solution A; under vigorous stirring, 8.0mmol of NH 4 Dissolving F in 20mL of glycol, and marking as a solution B; dropwise adding the solution B into the solution A under vigorous stirring, stirring at 50 ℃ for 20min, transferring into a 100mL Teflon-lined autoclave, and heating at 200 ℃ for 120 min; finally, BPEI functionalized NaYF 4 Yb, Er upconversion nano particles (BPEI/UCNP) are alternately and centrifugally washed for a plurality of times by ethanol and deionized water, and are dried for 12 hours in vacuum at 50 ℃ to obtain Y 3+ ：Yb 3+ ：Er 3+ Up-converting nanoparticles UCNPs at 78:20: 2.
5. The method for preparing a near-infrared light-excited photoelectrochemical sensor according to claim 1, wherein the DNA1-CdSe is prepared by: modifying amino at one end of the DNA1, modifying sulfydryl at the other end, and forming hairpin DNA1 by complementary pairing of bases close to the two ends; CdSe-COOH QDs were coupled with hairpin DNA1(SH-DNA 1-NH) by carboxyl-amino coupling reaction 2 ) Amide bonds are formed. The method specifically comprises the following steps: 2.0mg EDC and 3.0mg NHS were added to 75. mu.L of purified CdSe-COOH QDs aqueous solution and reacted at room temperature for 1h to activate carboxyl groups; then, 25. mu.L of 40. mu.M hairpin DNA1 was added to the activated CdSe-COOH QDs solution and reacted at 4 ℃ for 6h to give DNA 1-CdSe.
6. The method of claim 5, wherein the CdSe-COOH QDs are thioglycolic acid-terminated CdSe QDs, and the method comprises: first, 453.6mgNaBH was added under magnetic stirring 4 Adding 48mg of Se powder into a three-neck flask, adding into 15mL of deionized water, and continuously stirring for 2h to obtain a clear sodium hydroselenide solution; subsequently, 273.9mg of CdCl 2 ·2.5H 2 Preparation of Cd from O in 285mL of ultrapure water 2+ Solution under magnetic stirring95mL of Cd was added to a three-necked flask 2+ The solution was then added 74. mu. LTGA solution, adjusted to pH 9 by the addition of 1.0mol/L NaOH and passed through for 30min N 2 To remove oxygen; subsequently, 5mL of the prepared NaHSe was added to the mixture and heated in a water bath at 80 ℃ for 4h to obtain 3-mercaptoacetic acid-terminated CdSe QDs.
7. The method for preparing a near-infrared light-excited photoelectrochemical sensor according to claim 1, wherein the DNA2-SiO is 2 The preparation method of NP comprises the following steps: modification of-NH at one end of DNA2 2 Single-stranded DNA2 was formed by mixing 10. mu.L of 0.05% glutaraldehyde, 30. mu.L SiO 2 -NH 2 NPs and 1mL of 2. mu.M single-stranded DNA2 were mixed at room temperature with stirring for 1h, and single-stranded DNA2 and SiO were mixed by glutaraldehyde 2 -NH 2 Synthesis of DNA2-SiO by ligation of two amino groups on NPs 2 An NP conjugate.
8. The method of claim 7, wherein the SiO is deposited on the substrate 2 -NH 2 The preparation method of the NPs comprises the following steps: tetraethyl orthosilicate and NH 3 ·H 2 Adding O and ethanol into a beaker, stirring, and then centrifugally washing and dispersing the obtained solution in 5mL of ethanol; then, the (3-aminopropyl) triethoxysilane solution and SiO 2 NP solution was mixed and stirred overnight to give SiO 2 -NH 2 NPs。
9. A near-infrared light excited photoelectrochemical sensor produced by the method of any one of claims 1 to 8.
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