CN114887862A - nanoparticle-hPDA-TDNT material and preparation method and application thereof - Google Patents

nanoparticle-hPDA-TDNT material and preparation method and application thereof Download PDF

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CN114887862A
CN114887862A CN202210504350.6A CN202210504350A CN114887862A CN 114887862 A CN114887862 A CN 114887862A CN 202210504350 A CN202210504350 A CN 202210504350A CN 114887862 A CN114887862 A CN 114887862A
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tdnt
hpda
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CN114887862B (en
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伍欣宙
殷志斌
徐汉虹
陈东
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South China Agricultural University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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Abstract

The invention discloses a nanoparticle-hPDA-TDNT material and a preparation method and application thereof. The nano particle-hPDA-TDNT material has nano-scale surface uniformity, improved photothermal conversion efficiency and higher desorption/ionization efficiency. The nano particle-hPDA-TDNT material can be used for high-sensitivity detection of amino acids, fatty acids, saccharides, amines, dye drugs, nucleosides, polypeptides, contraband, polyethylene glycol and other substances. The nano particle-hPDA-TDNT material disclosed by the invention is simple in preparation method, convenient to use and free from complex tissue sample pretreatment. The spectrogram formed by using the nanoparticle-hPDA-TDNT material as a base material of SALDI has almost no background interference and high spectrogram signal-to-noise ratio. The nanoparticle-hPD A-TDNT material can be simultaneously suitable for a positive and negative ion detection mode, has wide universality and commercialization prospect, and can be widely matched with commercial MALDI-MS or LDI-MS instruments in the market.

Description

nanoparticle-hPDA-TDNT material and preparation method and application thereof
Technical Field
The invention relates to the field of nano materials, in particular to a nano particle-hPDA-TDNT material and a preparation method and application thereof.
Background
Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has become the most popular soft ionization mass spectrometry method, especially for analysis of biomacromolecules and synthetic polymers, due to its advantages of high sensitivity, high salt tolerance, and low sample consumption since the invention in the late 20 th century and 80 s. Therefore, the MALDI-MS technique has been widely used in leading fields of life sciences, drug synthesis, environmental analysis, and the like.
However, the conventional MALDI method has many disadvantages, for example, the use of organic matrices such as DHB, HCCA, etc. can cause severe background interference of spectral peaks in the low m/z range of mass spectra, which hinders the detection and identification of small molecule metabolites. Meanwhile, the uneven matrix deposition and co-crystallization often cause large spectrum signal fluctuation, poor reproducibility and the like. Although inorganic nano materials are gradually developed in recent years to solve the defects of the traditional matrix and partially solve the problems of spectrum peak background interference and matrix crystallization unevenness, the nano materials and liquid to be detected need to be mixed in advance and then subjected to spotting in actual analysis, and high-throughput analysis cannot be realized.
For this reason, Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) based on nano-substrate materials has been gradually developed. Due to the advantages of high specific surface area, high electrical conductivity, low thermal conductivity, good photo-thermal effect and the like, the nano-substrate material shows unique analysis performance in mass spectrometry of small molecular compounds. Compared with a sample preparation mode that matrix spraying or sublimation to the surface of a sample is often required in MALDI-MS, the SALDI-MS method can carry out mass spectrum sampling and analysis only by dripping the sample on the surface of the material, and the sample preparation time is greatly shortened. However, most SALDI materials are usually of a single chemical composition or surface modification, and are difficult to satisfy for highly sensitive detection and analysis of a wide variety of small molecule compounds in daily life. And the current commercialized nano-substrate material has the defects of complicated preparation process, long preparation period, high price and the like, and the application of the nano-substrate material in SALDI-MS is limited to a certain extent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a nanoparticle-hPDA-TDNT material. The material is used as a base material of SALDI to form a spectrogram which almost has no background interference and has high spectrogram signal-to-noise ratio, and is suitable for the analysis of various small molecular compounds.
The invention also aims to provide a preparation method of the nanoparticle-hPDA-TDNT material.
The invention also aims to provide application of the nanoparticle-hPDA-TDNT material.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a nanoparticle-hPDA-TDNT material is characterized by comprising the following steps:
s1, preparing TiO 2 Nanotube array TDNT: carrying out anodic oxidation reaction on the titanium sheet to prepare the TiO 2 A nanotube array TDNT;
s2, in TiO 2 Preparing a polydopamine PDA coating on the surface of the nanotube array TDNT: TiO of S1 2 The nanotube array TDNT is placed in a Tris buffer solution containing dopamine hydrochloride to be heated for reaction, and the PDA-TDNT material is prepared;
s3, performing hydrophobic modification on the surface of the PDA-TDNT material: s2, spraying a hydrophobic silane solution on the surface of the obtained PDA-TDNT material to form a hydrophobic layer on the surface of the PDA-TDNT material, and preparing the hPD A-TDNT material;
s4, performing nano particle modification on the surface of the hPDA-TDNT material: and uniformly spraying the nanoparticle solution on the hPD A-TDNT material to obtain the nanoparticle-hPD A-TDNT material.
The invention proceeds from the above-mentioned processIn TiO of 2 The surface of the nanotube array TDNT is sequentially provided with a PDA coating, a hydrophobic layer and a nanoparticle modification layer, and the nanoparticle-hPDA-TDNT material has nanoscale surface uniformity, improved photothermal conversion efficiency and higher desorption/ionization efficiency, and can effectively solve the problems of high background peak interference, nonuniform recrystallization, easy imaging artifact and the like of the traditional organic matrix.
In step S1, the TiO is 2 The nanotube array TDNT can be prepared by a conventional method.
Preferably, in step S1, the TiO is 2 The nanotube array is prepared by placing titanium sheet in NaF and Na 2 SO 4 Carrying out anodic oxidation reaction in the mixed solution to obtain the catalyst.
Preferably, in the step S1, the concentration of NaF is 0.001-0.02 g/mL, Na 2 SO 4 The concentration of (b) is 0.1-0.2 g/mL.
Preparation of the NaF and Na 2 SO 4 The solvent of the mixed solution is preferably ultrapure water.
Preferably, in the step S1, the voltage of the anodic oxidation reaction is 3-30V. Most preferably, the voltage of the anodic oxidation reaction in step s1. is 20V.
Preferably, in the step S1, the time of the anodic oxidation reaction is 0.5-4 h. Most preferably, the time of the anodic oxidation reaction in step s1. is 1 h.
Preferably, in the step S2, the concentration of the dopamine hydrochloride in the Tris buffer solution containing the dopamine hydrochloride is 0.5-5 mg/mL. When the concentration of the dopamine hydrochloride is in the range, a better mass spectrum signal can be obtained. More preferably, the concentration of the dopamine hydrochloride in the Tris buffer solution containing the dopamine hydrochloride is 1-4 mg/mL. Within this range, the signal intensity can be further improved for most of the compounds tested. Most preferably, the concentration of the dopamine hydrochloride in the Tris buffer containing the dopamine hydrochloride is 3 mg/mL.
Generally, a Tris buffer containing dopamine hydrochloride is prepared by adding a target concentration of dopamine hydrochloride to a Tris buffer. Typically, the Tris buffer concentration is 10mM, pH 8.5.
Preferably, in the step S2, the heating temperature is 80-99 ℃. Most preferably, in step s2, the temperature of the heating is 90 ℃.
Preferably, in the step S2, the reaction time is 1-4 h. Most preferably, step s2, the reaction time in step s is 3 h.
Preferably, in step s2, the reaction is carried out under stirring.
In the step S3, the thickness of the hydrophobic layer can be adjusted by controlling parameters such as the concentration of the hydrophobic silane solution, the spraying flow rate, the spraying times and the like.
Preferably, in the step S3, the concentration of the hydrophobic silane solution is 0.001-0.010 mol/L; the flow rate of the spraying is 0.1-5 mL/min; the spraying frequency of the spraying is 1-20 times.
Most preferably, the concentration of the hydrophobic silane solution is 2.5 μ L/mL; the flow rate of the spraying is 1 mL/min; the spraying frequency of the spraying is 10 times.
Preferably, in step s4, the nanoparticles are any one of Au, Ag, Pt, Pd, Co, Cu, C, Ge, or Si nanoparticles.
More preferably, in step s4, the nanoparticles are metal nanoparticles selected from any one of Au, Ag, Pt, Pd, Co, Cu or G e nanoparticles.
Most preferably, in step s4, the nanoparticles are Au nanoparticles.
Preferably, in step s4, the shape of the nanoparticles is spherical, rod-like, star-like, linear, porous and/or sheet-like.
Preferably, the concentration of the nanoparticle dispersion liquid in the step S4 is 0.01-10 g/L. More preferably, the concentration of the nanoparticle dispersion liquid in the step S4 is 0.1-1 g/L.
Preferably, in the step S4, the diameter distribution of the nanoparticles is 1-200 nm. Within the diameter range, the obtained nanoparticle-hPDA-TDNT material has a good resonance enhancement effect at 355 nm.
More preferably, in the step S4, the diameter distribution of the nanoparticles is 60-80 nm. Within the diameter range, the obtained nanoparticle-hPDA-TDNT material has better resonance enhancement effect at 355 nm.
Preferably, in the step s4, the spraying manner is ultrasonic spraying and uniform spraying.
Preferably, in the step S4, the flow rate of the ultrasonic spraying at the uniform speed is 0.01-0.09 mL/min. Most preferably, the flow rate of the ultrasonic spraying uniform spraying in the step S4 is 0.03 mL/min.
Preferably, in the step S4, the spraying times are 50-500. In this range, a better signal can be obtained. Most preferably, the number of spraying in step s4. is 250. Under the numerical value, the time required by spraying can be reduced, and a better mass spectrum signal enhancement effect can be achieved.
The nanoparticle-hPDA-TDNT material prepared by the preparation method.
The nano particle-hPDA-TDNT material is applied to a chip material for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry detection.
Preferably, the nanoparticle-hPDA-TDNT is used as a chip material for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and the molecular weight range of a compound to be analyzed is preferably 1-1500 Da.
The compounds may be present in liquid residues, deposits, colloids, and the like.
The compounds that can be analyzed by the invention include, but are not limited to, amino acids, fatty acids, saccharides, amines, dyes, drugs, nucleosides, polypeptides, contraband, polyethylene glycol and the like.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a nano particle-hPDA-TDNT material which has nano-scale surface uniformity, improved photo-thermal conversion efficiency and higher desorption/ionization efficiency. The nano particle-hPDA-TDNT material can be used for high-sensitivity detection of amino acids, fatty acids, saccharides, amines, dye drugs, nucleosides, polypeptides, contraband, polyethylene glycol and other substances. The nano particle-hPDA-TDNT material disclosed by the invention is simple in preparation method, convenient to use and free from complex tissue sample pretreatment. The spectrogram formed by using the nanoparticle-hPDA-TDNT material as a base material of SALDI has almost no background interference and high spectrogram signal-to-noise ratio. The nanoparticle-hPD A-TDNT material can be simultaneously suitable for a positive and negative ion detection mode, has wide universality and commercialization prospect, and can be widely matched with commercial MALDI-MS or LDI-MS instruments in the market.
Drawings
FIG. 1 is a schematic diagram of the synthesis of AuNP-hPDA-TDNT material according to example 1 of the present invention, and each symbol is: 1-metallic titanium sheet, 2-TDNT material, 3-PDA-TDNT material, 4-hPDA-TDNT material, 5-AuNP-hPDA-TDNT material and 6-mass spectrometry.
FIG. 2 shows the characterization results of AuNP-hPDA-TDNT material and its synthetic precursor material, (A) electron micrograph, (B) ultraviolet-visible absorption spectrogram, (C) mass spectrogram for detection of Raffinose, Glycerol triol, Histidine, and Oxytocin.
FIG. 3 is a comparison of mass spectra of amino acid mixtures analyzed in positive ion mode using (i) CHCA matrix, (ii) TDNT, (iii) PDA-TDNT, (iv) hPD-TDNT, (v) AuNP-hPD-TDNT material, wherein background interference peaks.
FIG. 4 is a comparison of mass spectra of fatty acid mixtures analyzed in negative ion mode (i)9-AA matrix, (ii) TDNT, (iii) PDA-TDNT, (iv) hPD-TDNT, (v) AuNP-hPD-TDNT material, wherein background interference peaks.
Fig. 5 is a mass spectrum comparison of the AuNP-hPDA-TDNT material of the present invention for (a) saccharide mixture, (B) dye drug mixture, (C) polypeptide mixture, (D) amine mixture, (E) polyethylene glycol mixture, (F) nucleotide mixture in positive ion mode, wherein background interference peak is.
Fig. 6 is a mass spectrum comparison of the AuNP-hPDA-TDNT material of the present invention in positive ion mode for pesticide mixture, where is a background interference peak;
fig. 7 is a comparison of mass spectra of the AuNP-hPDA-TDNT material of the present invention for two forbidden drugs, namely (a) Cotinine (Cotinine) and (B) nicontine (Nicotine), in positive ion mode, where x is a background interference peak.
FIG. 8 shows the detection limits of AuNP-hPDA-TDNT material in positive ion mode for four compounds (A) Rhodamine 6G (Rhodamine 6G), (B) Leu-enkephalin, (C) histidine and (D) tetracosanic acid (negative ion mode).
FIG. 9 shows the dot-to-dot and batch-to-batch reproducibility of AuNP-hPDA-TDNT material of the present invention for three compounds (A) Rhodamine 6G, (B) Leu-enkephalin and (C) histidine in positive ion mode.
FIG. 10 shows the results of signal intensity comparison of Rhodamine 6G, Leu-enkephalin and histidine (C) after being left for 40 days in positive ion mode for AuNP-hPDA-TDNT material of the present invention, measured every 4 days.
FIG. 11 is a drawing showing the electron micrographs of the surface micro-nano structure of TDNT after treatment at 5V, 10V and 20V (example 1), wherein (a), (b) and (c) respectively correspond to 5V and 35,000, 80,000 and 200,000 Xmagnifications, and (d), (e) and (f) respectively correspond to 10V and 35,000, 80,000 and 200,000 Xmagnifications, and (g), (h) and (i) respectively correspond to 10V and 35,000, 80,000 and 200,000 Xmagnifications.
FIG. 12 is a comparison graph of mass spectrum signal enhancement of histidine, leucine enkephalin and rhodamine 6G in positive ion mode for AuNP-hPDA-TDNT materials prepared by different anodic oxidation voltages.
FIG. 13 is a surface micro-nano structure characterization electron microscope image of the PDA-TDNT after stirring for 1.5h, 2h, and 3h (example 1), wherein (a), (b), and (c) correspond to electron microscope images at 35,000, 80,000, and 200,000 Xs for 1.5h, respectively, (d), (e), and (f) correspond to electron microscope images at 35,000, 80,000, and 200,000 Xs for 2h, respectively, and (g), (h), and (i) correspond to electron microscope images at 35,000, 80,000, and 200,000 Xs for 3h, respectively.
FIG. 14 is a graph showing the mass spectrum signal enhancement comparison of AuNP-hPDA-TDNT material prepared under different stirring time to histidine, leucine enkephalin and rhodamine 6G under positive ion mode.
Fig. 15 is a surface micro-nano structure characterization electron microscope image of AuNP-hPDA-TDNT material after 50, 100, 150, 200 (example 1) and 250 treatments, wherein (a), (b) and (c) correspond to electron microscope images at 50 times with magnifications of 35,000 ×, 80,000 ×, 200,000 ×, (d), (e) and (f) correspond to electron microscope images at 100 times with magnifications of 35,000 ×, 80,000 ×, 200,000 ×, and (g), (h) and (i) correspond to electron microscope images at 150 times with magnifications of 35,000 ×, 80,000 ×, 200,000 ×. (j) And (k) and (l) are shown by electron microscopy at 35,000, 80,000 and 200,000 Xmagnifications for 200 times, respectively. (m), (n), and (o) are shown by electron microscopy at 35,000, 80,000, and 200,000 Xmagnifications for 250 times, respectively.
FIG. 16 is a comparison graph of mass spectrum signal enhancement of histidine, leucine enkephalin and rhodamine 6G in positive ion mode for AuNP-hPDA-TDNT materials prepared by different AuNP spraying times.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It is to be understood that these examples are provided for illustrative purposes only and are not meant to limit the present invention. The following examples are examples of test methods in which specific conditions are not specified, and the apparatus is generally commercially available according to the conventional conditions. Unless otherwise indicated, percentages and parts are by weight.
Example 1
The synthesis steps of the AuNP-hPDA-TDNT material can refer to FIG. 1.
A preparation method of the AuNP-hPDA-TDNT material comprises the following steps:
s1, placing a titanium sheet (figure 1-1) in a container containing 0.005g/mL NaF and 0.142g/mL Na 2 SO 4 The aqueous solution is subjected to anodic oxidation reaction for 1 hour at 20V direct current voltage to obtain TiO 2 Nanotube array (TDNT) sheet (fig. 1-2).
S2, taking down the TDNT sheet, slightly ultrasonically cleaning the TDNT sheet in ultrapure water for 1min, and then placing the TDNT sheet in 10M Tris buffer solution containing 3mg/mL dopamine hydrochloride, and stirring the mixture for 3h at 90 ℃ to obtain the polydopamine modified titanium dioxide nanotube (PDA-TDNT) material (shown in a figure 1-3).
S3, sequentially and ultrasonically cleaning the PDA-TDNT in absolute ethyl alcohol and ultrapure water for 0.5min, and then uniformly spraying 2.5 mu L/mL absolute ethyl alcohol solution of perfluorooctyl trichlorosilane onto the surface of the PDA-TDNT for 10 times by an ultrasonic sprayer at the flow rate of 1mL/min to obtain the poly-dopamine modified titanium dioxide nanotube (hPDA-TDNT) subjected to hydrophobic treatment (figures 1-4).
S4, preparing nano gold (AuNP) with the diameter of 60-80 nm into a dispersion liquid with the concentration of 0.1mg/mL, and uniformly spraying the dispersion liquid on the surface of the hPD-TDNT for 200 times at the flow rate of 0.03mL/min to obtain the AuNP-hPD-TDNT material (shown in a figure 1-5).
After the AuNP-hPDA-TDNT material is prepared, the mixed solution of the analyte is directly dripped into the AuNP-hPDA-TDNT material, and after the AuNP-hPDA-TDNT material is dried, the AuNP-hPDA-TDNT material is stuck on a target plate and sent into a mass spectrometer for detection (figures 1-6).
Characterization of the product of example 1
FIG. 2 reflects the characterization results of AuNP-hPDA-TDNT material. The TiO can be seen from the electron micrograph 2 The tube diameter of the nanotube is about 64.1 +/-12.4 nm, and the AuNPs on the surface are uniformly distributed; from the ultraviolet visible absorption spectrogram, the conversion efficiency between light energy and heat energy can be obviously improved along with the highest absorbance of the AuNP-hPDA-TDNT material under the wavelength of 355nm laser commonly used by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, so that the ionization efficiency is improved; the mass spectrometry analysis result shows that the AuNP-hPDA-TDNT material has the highest spectrogram signal-to-noise ratio and a clear spectrogram background compared with the traditional organic matrix and the common unmodified metal material.
Detection of Small molecular weight Compound 1
FIG. 3 reflects the positive ion mode detection of 15 mixed samples of (i) CHCA matrix, (ii) TDNT, (iii) PDA-TDNT, (iv) hPDA-TDNT, (v) AuNP-hPDA-TDNT nanocore material for glycine (Gly), alanine (Ala), gamma-aminobutyric acid (GABA), serine (Ser), proline (Pro), valine (Val), threonine (Thr), leucine (Leu), lysine (Lys), methionine (Met), histidine (His), phenylalanine (Phe), arginine (Arg), tyrosine (Tyr), tryptophan (Trp). The result shows that compared with the traditional CHCA organic matrix, the SALDI spectrogram almost has no background interference and has high spectrogram signal-to-noise ratio, and the AuNP-hPDA-TDNT material can be used as an SALDI chip material and used for analyzing small molecular amino acid mixed samples in a positive ion mode.
Detection of Small molecular weight Compounds 2
Fig. 4 reflects the negative ion mode detection of (i)9-AA matrix, (ii) TDNT, (iii) PDA-TDNT, (iv) hPDA-TDNT, (v) AuNP-hPDA-TDNT nanochip material for 15 mixed samples of pelargonic acid (C9), capric acid (C10), undecanoic acid (C11), dodecanoic acid (C12), tridecanoic acid (C13), tetradecanoic acid (C14), pentadecanoic acid (C15), palmitic acid (C16), heptadecanoic acid (C17), stearic acid (C18), nonadecanoic acid (C19), arachidic acid (C20), heneicosanoic acid (C21), docosanoic acid (C22), tetracosanoic acid (C24), etc. The result shows that compared with the traditional 9-AA organic matrix, the SALDI spectrogram almost has no background interference and has high spectrogram signal-to-noise ratio, and the AuNPs-hPDA-TDNT material can be used as an SALDI chip material and is used for analyzing small molecular fatty acid mixed samples in an anion mode.
Detection of Small molecular weight Compounds 3
FIG. 5 reflects the use of AuNP-hPDA-TDNT nanosheet material for (A) carbohydrate mixtures (xyloses), Glucose (Glucose), Sucrose, raffinose), (B) dye drug mixtures (Proflavine (propofol), ethacrine (Ethacridine), Berberine (Berberine), Crystal violet (Crystal violet), Rhodamine 6G (Rhodamine 6G)), (C) polypeptide mixtures (Leu-enkephalin), heptapeptides (GLLEVER) (commercially available, synthesized by Biotech Inc.), Oxytocin (Oxytocin), octapeptides (QFLPYY) (commercially available, synthesized by Biotech Inc.), (D) amine mixtures (Tyramine (Tyramine), Spermidine (Spermidine), Tryptamine (Tryptamine), Spermin (YPE), (Cys, 600), Adridine (PEG), Adridine (Adridine), Glycine (PEG), Glycine (Glucose), Glycine (Glycine) (commercially available, Glycine (Glycine) (Glyc, Guanosine (Guanosine)), and the like. The result shows that when the AuNP-hPDA-TDNT material is used as the material of the SALDI chip, the spectrogram almost has no background interference and has high spectrogram signal-to-noise ratio.
Detection of Small molecular weight Compounds 4
Fig. 6 reflects that AuNP-hPDA-TDNT nanosheet material was used for positive ion mode detection of pesticide mixtures (Acephate, Dinotefuran, Thiamethoxam, Spirotetramat, Rotenone, Azoxystrobin, Cyantraniliprole, Chlorantraniliprole, Abamectin), etc. The result shows that when the AuNP-hPDA-TDNT material is used as the SALDI chip material, all 9 mixed pesticides in a spectrogram can be detected, and the AuNP-hPDA-TDNT material has wide application prospect and universality.
Detection of Small molecular weight Compounds 5
FIG. 7 reflects the positive ion mode detection results of AuNP-hPDA-TDNT material for two forbidden drugs, namely (A) Cotinine (Cotinine) and (B) Nicotinine (Nicotine). The result shows that compared with the TDNT material, the AuNP-hPDA-TDNT material can obtain the mass spectrum signal of the forbidden drug, the spectrogram signal-to-noise ratio is higher, and no background interference peak exists.
Detection of Small molecular weight Compounds 6
FIG. 8 shows the linear quantitative results of AuNP-hPDA-TDNT materials for four compounds (A) Rhodamine 6G, (B) Leu-enkephalin, (C) histidine and (D) tetracosanic acid (negative ion mode), with detection limits (S/N. gtoreq.3) of 11amol, 1fmol, 0.9pmol and 9pmol (negative ion mode), respectively.
Detection of Small molecular weight Compounds 7
FIG. 9 shows that the AuNP-hPDA-TDNT material has good reproducibility between dots and between batches with a relative standard deviation of less than 5% for three compounds (A) Rhodamine 6G, (B) Leu-enkephalin and (C) histidine.
Detection of Small molecular weight Compounds 8
FIG. 10 shows the results of signal intensity comparison of (A) Rhodamine 6G, (B) Leu-enkephalin and (C) histidine in AuNP-hPDA-TDNT material after 40 days of storage, measured every 4 days. The result shows that the AuNP-hPDA-TDNT nano chip material can be stored for a long time without influencing the sensitivity of the AuNP-hPDA-TDNT nano chip material to small molecule mass spectrum detection, and the AuNP-hPDA-TDNT nano chip material has wide universality and commercialization prospect and can be widely matched with commercial MALDI-MS or LDI-MS instruments in the market.
Examples 2 to 5 Effect of different anodic Oxidation voltages
According to the method and parameters of the embodiment 1, only in the S1, the direct current voltage is respectively modified into 5V, 10V, 15V and 25V; preparation examples 2 to 5. Wherein, a surface micro-nano structure characterization electron microscope image of the TDNT treated by 5V, 10V, and 20V (example 1) is shown in fig. 11, and mass spectrum signal enhancement comparison of AuNP-hPDA-TDNT prepared from TDNT obtained at each anodic oxidation voltage for histidine, Leu-enkephalin (leucine enkephalin), and Rhodamine 6G (Rhodamine 6G) is shown in fig. 12. As can be seen in FIG. 12, the AuNP-hPDA-TDNT prepared under the condition of the common anodic oxidation voltage of 5-25V shows the mass spectrum signal enhancement effect, and the mass spectrum signal enhancement effect on histidine, leucine enkephalin and rhodamine 6G is the best under the condition of the anodic oxidation voltage of 20V.
Examples 6-9 Effect of different dopamine reaction times
According to the method and parameters of the embodiment 6-9, only in the S2, the stirring time is changed into 1.5h, 2h, 2.5h and 3 h; preparation examples 6 to 9. Wherein, a surface micro-nano structure characterization electron microscope image of the PDA-TDNT treated for 1.5h, 2h and 3h (example 1) is shown in fig. 13, and the AuNP-hPDA-TDNT prepared by the PDA-TDNT obtained under different stirring time is used for mass spectrum signal enhancement comparison of histidine, Leu-enkephalin (leucine enkephalin) and Rhodamine 6G (Rhodamine 6G), which is shown in fig. 14. As can be seen in FIG. 14, the PDA stirring time has little influence on the mass spectrum signal enhancement effect, and the mass spectrum signal enhancement effect on histidine, leucine enkephalin and rhodamine 6G is the best under the condition that the PDA stirring time is 3 h.
Examples 10-13 Effect of different AuNP spray times
According to the method and parameters of the embodiment 1, only in the S4, the spraying times of the nano gold sprayed on the surface of the hPD-TDNT are respectively modified into 50 times, 100 times, 150 times and 250 times; wherein, the surface micro-nano structure characterization electron microscope images of the AuNP-hPDA-TDNT treated 50 times, 100 times, 150 times, 200 times (example 1) and 250 times are shown in figure 15, and the AuNP-hPDA-TDNT obtained by different spraying times are used for mass spectrum signal enhancement comparison of histidine, Leu-enkephalin (leucine enkephalin) and Rhodamine 6G (Rhodamine 6G), which is shown in figure 16. As can be seen from fig. 16, the mass spectrum signal enhancement effect on histidine, leucine enkephalin and rhodamine 6G is close under the condition of spraying AuNP dispersion liquid for 200-250 times. However, after the signal enhancement amplitude and the substrate preparation time are comprehensively considered, spraying the AuNP dispersion liquid for 200 times is adopted as the optimized preparation condition.
The above embodiments are only one of the embodiments of the present invention, and any other changes, modifications, substitutions, combinations, and simplifications which are made without departing from the principles and spirit of the present invention are all equivalent replacements within the protection scope of the present invention.

Claims (10)

1. A preparation method of a nanoparticle-hPDA-TDNT material is characterized by comprising the following steps:
s1, preparing TiO 2 Nanotube array TDNT: carrying out anodic oxidation reaction on the titanium sheet to prepare the TiO 2 A nanotube array TDNT;
s2, in TiO 2 Preparing a polydopamine PDA coating on the surface of the nanotube array TDNT: TiO of S1 2 The nanotube array TDNT is placed in a Tris buffer solution containing dopamine hydrochloride to be heated for reaction, and the PDA-TDNT material is prepared;
s3, performing hydrophobic modification on the surface of the PDA-TDNT material: s2, spraying a hydrophobic silane solution on the surface of the obtained PDA-TDNT material to form a hydrophobic layer on the surface of the PDA-TDNT material, and preparing the hPD A-TDNT material;
s4, performing nano particle modification on the surface of the hPDA-TDNT material: and uniformly spraying the nanoparticle dispersion liquid on the hPD A-TDNT material to obtain the nanoparticle-hPD A-TDNT material.
2. The preparation method according to claim 1, wherein in step S2. the concentration of dopamine hydrochloride in the Tris buffer containing dopamine hydrochloride is 0.5-5 mg/mL.
3. The method according to claim 1, wherein the heating temperature in step S2 is 80-99 ℃.
4. The preparation method according to claim 1, wherein in step S3, the concentration of the hydrophobic silane solution is 0.001-0.01 mol/L; the flow rate of the spraying is 0.1-5 mL/min; the spraying frequency of the spraying is 1-20 times.
5. The preparation method according to claim 1, wherein in step S4, the nanoparticles are any one of Au, Ag, Pt, Pd, Co, Cu, C, Ge or Si nanoparticles.
6. The method according to claim 1, wherein in step S4, the nanoparticles are in the shape of spheres, rods, stars, wires, pores and/or sheets.
7. The preparation method according to claim 1, wherein in step S4, the nanoparticles have a diameter distribution of 1 to 200 nm.
8. The preparation method according to claim 1, wherein in step S4, the spraying manner is ultrasonic spraying and uniform spraying.
9. A nanoparticle-hPDA-TDNT material prepared by the preparation method of any one of claims 1 to 8.
10. The application of the nanoparticle-hPDA-TDNT material in claim 9 as a chip material for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry detection.
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