CN113125408A - On-site rapid detection method for volatile benzaldehyde in exhaled breath of human body - Google Patents
On-site rapid detection method for volatile benzaldehyde in exhaled breath of human body Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N2021/6417—Spectrofluorimetric devices
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention relates to a rapid on-site detection method of volatile benzaldehyde in exhaled breath of a human body, which comprises the following steps: s1: preparing gold nanospheres modified by p-mercaptoaniline and carbon quantum dots modified by mercaptosuccinic acid; s2: preparing GNPs-CQDs assemblies and GNPs-CQDs @ MOFs core-shell nano materials by adopting electrostatic interaction and a layer-by-layer assembly strategy; s3: depositing GNPs-CQDs @ MOFs core-shell nano materials on a paper base to obtain GNPs-CQDs @ MOFs paper chips; s4: extracting gas benzaldehyde in exhaled breath by using GNPs-CQDs @ MOFs paper chips; s5: and detecting benzaldehyde in a Surface Enhanced Raman Spectroscopy (SERS) and fluorescence double-probe mode by adopting a portable Raman spectrometer and an ultraviolet lamp. Compared with the prior art, the method has the advantages of rapid analysis, high sensitivity, small sample consumption, wide application range, simple and convenient operation and the like.
Description
Technical Field
The invention relates to the technical field of on-site detection, in particular to an on-site rapid detection method for volatile benzaldehyde in human exhaled breath.
Background
The incidence of lung cancer is the first in malignant tumors all over the world, and in many large and medium cities in China, the incidence and the fatality rate of lung cancer are higher than those of common tumors, so that the lung cancer seriously harms the health of human beings. About ten thousand people die of lung cancer every year in China, and the annual survival rate of lung cancer in each stage, especially in the advanced stage, is extremely low. With the continuous development of medical science and technology, the level of diagnosis and treatment of lung cancer has been significantly improved, but still far from meeting the needs of human and clinical work. A large number of researches show that the most effective method for reducing the death rate of lung cancer is to diagnose and treat the lung cancer as soon as possible, and the 5-year survival rate of the early lung cancer patients can reach more than 70 percent. However, lung cancer is latent and has no clinical symptoms in the early stage. At present, most lung cancer is diagnosed in the middle and advanced stages, is easy to spread and transfer, and misses the optimal period of treatment. The prognosis of lung cancer is closely related to the clinical stage at the time of visit. Therefore, the early detection, diagnosis and treatment of lung cancer have great clinical significance. Early detection of lung cancer can only be realized by regular screening, but the current clinical lung cancer detection technology cannot realize large-scale high-risk population screening. Exhaled breath analysis is considered to be a possible alternative method for safe and convenient disease diagnosis, exhaled breath directly originates from the lung, has good specificity on lung diseases, and is suitable for preliminary screening of clinical lung cancer. The content of certain specific biomarkers in the exhaled breath is closely related to the onset of lung cancer, so that the quantitative detection of the lung cancer-related markers has great significance for the early diagnosis and prognosis of lung cancer. Volatile Organic Compounds (VOCs) at concentration levels between 10 and 100ppb were identified as biomarkers for lung cancer. However, among many lung cancer markers, gaseous benzaldehyde in exhaled breath is an important indicator of lung cancer. To date, conventional methods for benzaldehyde determination include gas chromatography-mass spectrometry, ion mobility spectrometry, selected ion flow tube mass spectrometry and chemical sensors. Although many of these methods have high selectivity and sensitivity for the analysis of benzaldehyde in complex samples, most of the above methods are costly, time consuming and labor intensive. A more important challenge is the pre-treatment procedure of complex samples. Therefore, it is not readily applicable to rapid and sensitive in-situ detection of gaseous benzaldehyde in complex matrix samples.
Disclosure of Invention
The invention aims to provide a rapid on-site detection method for volatile benzaldehyde in human exhaled breath, which is rapid, efficient and simple to operate and can directly carry out specific detection on the benzaldehyde.
The purpose of the invention can be realized by the following technical scheme: a rapid on-site detection method for volatile benzaldehyde in exhaled breath of a human body comprises the following steps:
s1: preparing gold nanospheres modified by p-mercaptoaniline and carbon quantum dots modified by mercaptosuccinic acid;
s2: preparing GNPs-CQDs assemblies and GNPs-CQDs @ MOFs core-shell nano materials by adopting electrostatic interaction and a layer-by-layer assembly strategy;
s3: depositing GNPs-CQDs @ MOFs core-shell nano materials on a paper base to obtain GNPs-CQDs @ MOFs paper chips;
s4: extracting gas benzaldehyde in exhaled breath by using GNPs-CQDs @ MOFs paper chips;
s5: and detecting benzaldehyde in a Surface Enhanced Raman Spectroscopy (SERS) and fluorescence double-probe mode by adopting a portable Raman spectrometer and an ultraviolet lamp.
The amino-modified Gold Nanospheres (GNPs) of the present invention and the carboxyl-covered Carbon Quantum Dots (CQDs) can be directly assembled to each other by electrostatic interaction, resulting in fluorescence quenching of the CQDs. After the benzaldehyde is added, Schiff base reaction between aldehyde group of the benzaldehyde and amine group of the GNPs modified p-mercaptoaniline destroys assembly of GNPs-CQDs, leads to recovery of fluorescence signal and enables visualization of the benzaldehyde with naked eyes. In addition, benzaldehyde induces-NH on the surfaces of GNPs2Conversion of the group to a C ═ N group, 1620cm-1The Raman characteristic peak can be used for SERS analysis of the volatile benzaldehyde.
Further, the preparation method of the gold nanosphere modified with p-mercaptoaniline, described in step S1, includes:
the first step is as follows: mixing ultrapure water and a chloroauric acid solution, and heating to boil;
the second step is that: adding a sodium citrate solution to synthesize gold nanoparticles, forming gold nanospheres when the color of the solution is changed from colorless to wine red, adding a polyvinylpyrrolidone solution, and stopping heating;
the third step: filtering the mixed solution by using a filter membrane to obtain a gold nanosphere solution;
the fourth step: adding p-mercaptoaniline into the purified gold nanosphere solution to obtain p-mercaptoaniline modified gold nanospheres;
the preparation method of the mercaptosuccinic acid modified carbon quantum dot comprises the following steps:
and degassing the mixture of the glycerol and the PEG200 by using inert gas, heating to 260-280 ℃, adding mercaptosuccinic acid under vigorous stirring, and reacting for 2.5-3.5 hours to obtain the carbon quantum dot modified by the mercaptosuccinic acid.
Furthermore, the particle size of the gold nanosphere in the third step is 40-60 nm, preferably 50 nm;
purifying the carbon quantum dots modified by the mercaptosuccinic acid, wherein the specific method comprises the following steps: and placing the carbon quantum dot modified by the mercaptosuccinic acid in an aqueous solution for centrifugal purification, and performing dialysis purification by using a cellulose ester membrane bag to remove large particles or agglomerated particles to obtain the purified carbon quantum dot modified by the mercaptosuccinic acid.
The method for preparing the GNPs-CQDs assembly described in step S2 includes: and mixing and stirring the carbon quantum dot solution modified by mercaptosuccinic acid and the gold nanosphere solution modified by p-mercaptoaniline to synthesize the GNPs-CQDs. Controlling the gold nanosphere and carbon quantum dot particle size allows the hybrid assembly to be composed of a single GNPs and multiple CQDs, thus the (multiple donor) - (single acceptor) structure facilitates Fluorescence Resonance Energy Transfer (FRET) between CQDs and GNPs, thereby inducing fluorescence quenching of CQDs.
The method for preparing the GNPs-CQDs @ MOFs core-shell nano material in the step S2 comprises the following steps: dissolving terephthalic acid and aluminum chloride hexahydrate in a mixture of N, N-dimethylformamide and methanol, carrying out ultrasonic treatment, then adding GNPs-CQDs, uniformly stirring, placing in an autoclave, reacting at 140-160 ℃ for 14-16 h, and washing and drying precipitates to obtain the GNPs-CQDs @ MOFs.
The method for depositing the GNPs-CQDs @ MOFs core-shell nano material on the paper base in the step S3 comprises vacuum filtration; the paper substrate includes cellulose-based filter paper. The cellulose-based filter paper is used as the substrate of the paper-based solid phase extraction material, so that the complex pretreatment step of a sample can be avoided, and the method has the advantages of simplicity and convenience in operation, quickness in analysis and the like.
The method for extracting the benzaldehyde from the exhaled breath by using the GNPs-CQDs @ MOFs paper chip in the step S4 comprises the following steps: and introducing the exhaled air sample into a device carrying the GNPs-CQDs @ MOFs paper chip to enrich the benzaldehyde in the exhaled air on the GNPs-CQDs @ MOFs paper chip.
The process of detecting benzaldehyde by Surface Enhanced Raman Spectroscopy (SERS) described in step S5 includes: and performing Raman signal detection on the paper chip after the gas benzaldehyde is extracted by adopting a portable Raman spectrometer to obtain an SERS spectrum, and comparing the SERS spectrum with a spectrum without benzaldehyde so as to realize qualitative and quantitative detection.
Further, the process of detecting benzaldehyde by Surface Enhanced Raman Spectroscopy (SERS) has the excitation wavelength of 785nm, the integration time of 10s and the Raman spectrum peak of 1620cm-1As a basis for determination, 1620. + -.2 cm-1The benzaldehyde content was calculated corresponding to a linear curve between the raman peak intensity and the concentration of benzaldehyde.
Furthermore, the linear curve between the concentration of benzaldehyde and the intensity of Raman signal is formed by the concentration of 1 × 10-4、1×10-3、1×10-2、1×10-1、1×100、1×101、1×102And performing linear fitting on ppm gas benzaldehyde and the corresponding Raman signal intensity to obtain the product. The benzaldehyde with corresponding concentration can be obtained by adopting a mode of combining steam generation (VG) -paper base micro extraction (PBM), and the specific method comprises the following steps: preparing a series of benzaldehyde standard solutions with different concentrations, placing the benzaldehyde standard solutions into a sample bottle, generating negative pressure above the sample bottle under the blowing of inert gas, enabling the benzaldehyde gas to enter an atomizer to be atomized to form aerosol, purifying the aerosol by a purification column, entering a device carrying GNPs-CQDs @ MOFs paper chips, enriching the aerosol on the GNPs-CQDs @ MOFs paper chips to obtain the standard solutions with the concentration of 1 multiplied by 10-4、1×10-3、1×10-2、1×10-1、1×100、1×101、1×102ppm GNPs-CQDs @ MOFs paper chip of gas benzaldehyde.
The process for detecting benzaldehyde by fluorescence comprises the following steps: GNPs-CQDs @ MOFs paper chips with different concentrations of gaseous benzaldehyde extracted by ultraviolet lamp irradiation are used for observing fluorescence intensity.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the fluorescence and Raman dual-probe mode to detect the benzaldehyde, has simple and convenient operation, high response speed and high detection sensitivity, and the Raman detection range is 10-4～102Between ppm and fluorescence detection range of 2X 10-9～2×10-2M is greater than or equal to the total weight of the compound;
2. the core-shell gold nanospheres-carbon quantum dots @ metal organic frameworks (GNPs-CQDs @ MOFs) have excellent absorption capacity and excellent affinity to Volatile Organic Compounds (VOCs), the MOFs not only stabilizes the GNPs, but also effectively attracts target analytes to the surfaces of the GNPs, so that more analytes can interact with the metal surfaces, and the analysis sensitivity of benzaldehyde is improved;
3. the invention has developed a bimodulus fluorescence and SERS detection method, combine VG with PBM, carry on accurate, selectivity and sensitive analysis to volatile benzaldehyde, and is suitable for the visualization of benzaldehyde in the complicated substrate sample, and detect on-the-spot to benzaldehyde in the wider concentration range, in addition, through obtaining the data from two different channels, can lighten the risk of false positive and false negative detection;
4. the steam generation (VG) promotes the separation of volatile substances in a complex matrix sample and the enrichment of target molecules on the surface of a paper chip, the paper-based micro-extraction (PBM) is an economic and rapid field analysis method, is easy to use at one time, can effectively extract analytes, combines the PBM with the VG, and the GNPs-CQDs @ MOFs core-shell nano material serving as an SERS substrate can eliminate matrix interference and improve the analysis sensitivity of benzaldehyde;
5. the method is rapid and efficient, is simple to operate, can directly carry out specificity detection on the benzaldehyde, and can carry out sensitive on-site fluorescence detection and accurate SERS quantitative analysis on the volatile benzaldehyde;
6. the invention can realize the on-site rapid qualitative and quantitative analysis of the volatile benzaldehyde in the exhaled breath of the human body, has the characteristics of rapid analysis, high sensitivity, small sample consumption, wide application range, simple and convenient operation, convenient device carrying and the like compared with the existing on-site rapid detection method, can realize the analysis and detection of the volatile benzaldehyde in the exhaled breath of the human body, and has the detection limit of 0.1 ppb.
Drawings
FIG. 1 is a diagram of a portable VG-PBM device for extracting gaseous benzaldehyde in example 1 of the present invention;
FIG. 2 is a fluorescence spectrum of p-mercaptoaniline modified gold nanospheres (a), mercaptosuccinic acid modified carbon quantum dots (b), GNPs-CQDs @ MOFs core-shell nanomaterial before (c) and after (d) benzaldehyde is added;
FIG. 3 is a graph showing fluorescence spectra of the GNPs-CQDs @ MOFs system according to example 1 of the present invention with increasing benzaldehyde concentration;
FIG. 4 is a fluorescent picture of GNPs-CQDs @ MOFs paper chip according to the invention in example 1, with the increase of benzaldehyde concentration;
FIG. 5 is a Raman spectrum of the GNPs-CQDs @ MOFs paper chip of example 1 of the present invention before (c) and after (d) the extraction of benzaldehyde, with the Raman spectra of GNPs @ MOFs (a) and solid p-mercaptoaniline (b) as reference;
FIG. 6 is a Raman spectrum of the GNPs-CQDs @ MOFs paper chip of example 1 of the present invention with increasing benzaldehyde concentration;
FIG. 7 shows the standard concentration and characteristic peak intensity (1620. + -.2 cm) of benzaldehyde in example 1 of the present invention-1) A schematic diagram of the linear relationship of (1);
FIG. 8 is a flow chart of a detection method according to an embodiment of the present invention;
in the figure: 1-steam generating part, 11-sample bottle, 12-atomizer, 13-purifying column, 2-paper base micro-extraction part and 21-GNPs-CQDs @ MOFs paper chip.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
Example 1
(1) Gold nanosphere modified by p-mercaptoaniline
Into a clean three-necked flask, 100mL of ultrapure water and 1.0mL of 10% chloroauric acid (HAuCl) were added4) The solution is heated to boiling. 1.0mL of 1% sodium citrate solution was then added immediately to synthesize gold nanoparticles having an average diameter of 50 nm. GNPs were formed when the solution changed color from colorless to wine-red, and 1.0mL of 1% polyvinylpyrrolidone (PVP) solution was added and the heating was stopped. After cooling to room temperature, filtration was performed with a 0.45 μ M filter membrane, and finally the prepared Gold Nanosphere Solutions (GNPs) were stored at 4 ℃.
0.5mL of 1mM p-mercaptoaniline was added to 5mL of the purified gold nanosphere solution. The mixture is balanced for 24h at 30 ℃, centrifuged for 5min at 8000rpm, the superfluous p-mercaptoaniline in the mixture is removed, and ultrasonic treatment is carried out for 30min at the same time, so that the solution is fully and uniformly distributed.
(2) Mercaptosuccinic acid modified carbon quantum dots
Typically, 15mL of glycerol and 1g of PEG200 were placed in a 100mL three-necked flask and degassed with argon for 10 minutes. When the temperature rose to 270 ℃, 1g of mercaptosuccinic acid (DMSA) was rapidly added to the hot solution with vigorous stirring, the reaction was maintained at this temperature for 3 hours, and then allowed to cool to room temperature. In a centrifuge (3000 rpm)-120min) and then dialyzed and purified with a cellulose ester membrane bag (Mw 3500) to remove large particles or agglomerated particles. Obtaining the purified mercaptosuccinic acid modified carbon quantum dots.
(3) Preparation of GNPs-CQDs @ MOFs core-shell nano material
0.5mL of mercaptosuccinic acid-modified carbon quantum dots (CQDs/DMSA 0.5. mu.M) solution and 2.0mL of p-mercaptoaniline-modified gold nanospheres (GNPs/PATP 0.8nM) solution were mixed and stirred at room temperature overnight to synthesize a GNPs-CQDs solution. Usually, 0.543g of terephthalic acid (H)2BDC) and 0.724g of aluminium chloride hexahydrate (AlCl)3·6H2O) was dissolved in 30mL of a mixture of N, N-dimethylformamide and methanol (DMF: MeOH ═ 1:1(v/v)), and sonicated for 30 min. Then, 2.5mL of the synthesized GNPs-CQDs colloid is added into the solution and stirred for 30 min; the mixed solution was transferred to a 50mL Teflon-lined autoclave and allowed to stand in an oven at 150 ℃ for 15 hours. After cooling to room temperatureThe resulting pale red solid was collected by centrifugation, washed twice with DMF, and then with methanol to remove unreacted components. The resulting solid was stirred in absolute methanol for 24 hours and finally dried under vacuum at 70 ℃ for 12 hours.
(4) Depositing GNPs-CQDs @ MOFs core-shell nano materials synthesized in the step (3) on 0.22 mu m cellulose-based filter paper (PC, Whatman) through vacuum filtration to form GNPs-CQDs @ MOFs paper chips, and combining steam generation (VG) and paper-based micro extraction (PBM) to design a portable VG-PBM device for extracting gas benzaldehyde, wherein as shown in figure 1, the VG-PBM device comprises a steam generation part 1 and a paper-based micro extraction part 2, the steam generation part 1 comprises a sample bottle 11, an atomizer 12 and a purification column 13 which are sequentially arranged, a benzaldehyde solution is arranged in the sample bottle 11, under the blowing of nitrogen, negative pressure is generated above the sample bottle 11, the gas benzaldehyde enters the atomizer 12 under the action of the negative pressure to be atomized to form aerosol, enters the paper-based micro extraction part 2 after being purified by the purification column 13, the GNPs-MOFs paper chips 21 are arranged in the paper-based micro extraction part 2, the gaseous benzaldehyde is enriched on the GNPs-CQDs @ MOFs paper chip, and the GNPs-CQDs @ MOFs paper chip with the gaseous benzaldehyde of different concentrations can be respectively obtained.
(5) Fluorescence detection of benzaldehyde
The fluorescence intensity of the obtained GNPs-CQDs @ MOFs core-shell nano material is shown in figure 2c, and the fluorescence of the CQDs is quenched after the gold nanospheres are added. And simultaneously preparing a certain amount of benzaldehyde solution, adding the benzaldehyde solution into a mixed system, and recovering fluorescence, wherein the fluorescence intensity is shown as 2 d.
Preparing a series of benzaldehyde standard solutions (2X 10) with different concentrations-9、2×10-8、2×10-7、2×10-6、2×10-5、2×10-4、2×10-3、2×10-2M)。
Adding 50 mu L of prepared benzaldehyde solutions with different concentrations into the GNPs-CQDs @ MOFs core-shell nano material synthesized in the step (3), recording the fluorescence intensity before and after adding the benzaldehyde solution by taking the excitation wavelength as 400nm, wherein the fluorescence intensity gradually increases along with the increase of the concentration of the benzaldehyde, as shown in a figure 3; a fluorescent photograph of the GNPs-CQDs @ MOFs paper chip absorbing benzaldehyde of different concentrations under the irradiation of an ultraviolet lamp is shown in FIG. 4, and the fluorescence intensity gradually increases along with the increase of the concentration of the benzaldehyde.
(6) Raman detection of benzaldehyde
Detecting Raman signals of the GNPs-CQDs @ MOFs paper chip prepared in the step (4) by adopting a portable Raman spectrometer, wherein the excitation wavelength is 785nm, the integration time is 10s, extracting gas benzaldehyde by utilizing a VG-PBM device and the GNPs-CQDs @ MOFs paper chip designed in the step (4), detecting the Raman signals by adopting the same conditions, extracting the benzaldehyde, and then detecting the benzaldehyde at 1620cm-1A new peak appears as shown in fig. 5.
The measurement was performed using a portable raman spectrometer with an excitation wavelength of 785 nm. Extracting gas benzaldehyde (1 x 10) with different concentrations by using VG-PBM device and GNPs-CQDs @ MOFs paper chip designed in step (4)-4、1×10-3、1×10-2、1×10-1、1×100、1×101、1×102ppm), then placing the GNPs-CQDs @ MOFs paper chip after the benzaldehyde is extracted on a Raman instrument, and detecting an SERS signal of the chip. Using Raman spectrum peak 1620cm-1As a basis for the determination. Along with the gradual increase of the concentration of the gaseous benzaldehyde, 1620cm in the Raman spectrogram-1The characteristic peak gradually increases as shown in fig. 6. Selecting at 1620 + -2 cm-1The corresponding peak intensity in combination with the linear curve (fig. 7) can be calculated for the content of benzaldehyde, and the Detection Limit (DL) is calculated from the ratio of the 3-fold measurement blank standard deviation (δ) to the linear curve slope (k) according to the linear relationship between the concentration of benzaldehyde and the raman signal intensity, i.e., DL is 3 δ/k, and the detection limit of benzaldehyde can be obtained and is 0.1 ppb.
The method has important significance for quantitative analysis and trace detection.
Example 2
Detecting volatile benzaldehyde in exhaled breath of human body
Fig. 8 schematically shows a flow chart of benzaldehyde in exhaled breath according to an embodiment of the present invention, and the detection method comprises the following steps:
(1) preparing gold nanospheres modified by p-mercaptoaniline, and the steps are the same as in example 1;
(2) preparing a mercaptosuccinic acid modified carbon quantum dot by the same steps as in example 1;
(3) preparing GNPs-CQDs @ MOFs core-shell nano-materials by the same steps as the step 1;
(4) constructing GNPs-CQDs @ MOFs paper chip and VG-PBM device in the same steps as embodiment 1;
(5) and (3) detecting volatile benzaldehyde in the exhaled breath by fluorescence.
By recruiting 10 volunteers, each participant was asked to take a breath sample using a nitrogen purged 500mL tedlar bag and an additional laryngeal tongue after obtaining their informed consent. Breath sample in the sampling bag was pumped at 0.2L min-1The flow rate of (2) is introduced into the PBM device (i.e. the paper-based micro-extraction part 2) and then captured by the GNPs-CQDs @ MOFs paper chip 21. The reacted GNPs-CQDs @ MOFs paper chip is photographed under a 365nm ultraviolet lamp, and the read fluorescence intensity is compared with the fluorescence intensity in the example 1, so that the approximate concentration of the volatile benzaldehyde in the exhaled breath is obtained.
(6) SERS technology for detecting volatile benzaldehyde in exhaled breath of human body
And (3) detecting Raman signals of the GNPs-CQDs @ MOFs paper chip obtained in the step (5) after different breath samples are extracted by adopting a portable Raman spectrometer, wherein the excitation wavelength is 785nm, the integration time is 10s, and the SERS spectrum of the exhaled breath is obtained and is compared with the standard curve of benzaldehyde, so that the content of volatile benzaldehyde in the exhaled breath of a human body is realized.
A common analytical detection method for benzaldehyde is gas chromatography-mass spectrometry (GC-MS), and the detection results are shown in Table 1.
TABLE 1
| The invention | Gas chromatography-mass spectrometer | |
| Breath sample numbering | Benzaldehyde (ppb) | Benzaldehyde (ppb) |
| 1 | 22.51 | 27.67 |
| 2 | 78.12 | 76.34 |
| 3 | 4.955 | 5.043 |
As can be seen from Table 1, the analysis result of the method has better matching degree with the result of the gas chromatography-mass spectrometry, which shows that the method has better detection accuracy and is expected to be used as a rapid detection method for rapidly analyzing and detecting the lung cancer marker in the exhaled breath of the human body.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A rapid on-site detection method for volatile benzaldehyde in exhaled breath of a human body is characterized by comprising the following steps:
s1: preparing gold nanospheres modified by p-mercaptoaniline and carbon quantum dots modified by mercaptosuccinic acid;
s2: preparing GNPs-CQDs assemblies and GNPs-CQDs @ MOFs core-shell nano materials by adopting electrostatic interaction and a layer-by-layer assembly strategy;
s3: depositing GNPs-CQDs @ MOFs core-shell nano materials on a paper base to obtain GNPs-CQDs @ MOFs paper chips;
s4: extracting gas benzaldehyde in exhaled breath by using GNPs-CQDs @ MOFs paper chips;
s5: and detecting benzaldehyde in a surface enhanced Raman spectrum and fluorescence double-probe mode by adopting a portable Raman spectrometer and an ultraviolet lamp.
2. The method for rapidly detecting the volatile benzaldehyde in the exhaled breath of a human body according to claim 1, wherein the preparation method of the p-mercaptoaniline modified gold nanosphere of step S1 comprises the following steps:
the first step is as follows: mixing ultrapure water and a chloroauric acid solution, and heating to boil;
the second step is that: adding a sodium citrate solution to synthesize gold nanoparticles, forming gold nanospheres when the color of the solution is changed from colorless to wine red, adding a polyvinylpyrrolidone solution, and stopping heating;
the third step: filtering the mixed solution by using a filter membrane to obtain a gold nanosphere solution;
the fourth step: adding p-mercaptoaniline into the purified gold nanosphere solution to obtain p-mercaptoaniline modified gold nanospheres;
the preparation method of the mercaptosuccinic acid modified carbon quantum dot comprises the following steps:
and degassing the mixture of the glycerol and the PEG200 by using inert gas, heating to 260-280 ℃, adding mercaptosuccinic acid under vigorous stirring, and reacting for 2.5-3.5 hours to obtain the carbon quantum dot modified by the mercaptosuccinic acid.
3. The on-site rapid detection method for volatile benzaldehyde in human exhaled breath according to claim 2, wherein the particle size of the gold nanospheres in the third step is 40-60 nm;
purifying the carbon quantum dots modified by the mercaptosuccinic acid, wherein the specific method comprises the following steps: and placing the carbon quantum dot modified by the mercaptosuccinic acid in an aqueous solution for centrifugal purification, and performing dialysis purification by using a cellulose ester membrane bag to remove large particles or agglomerated particles to obtain the purified carbon quantum dot modified by the mercaptosuccinic acid.
4. The method of claim 1, wherein the step S2 of preparing the assembly of GNPs-CQDs comprises: mixing and stirring the carbon quantum dot solution modified by mercaptosuccinic acid and the gold nanosphere solution modified by p-mercaptoaniline to synthesize GNPs-CQDs;
the method for preparing the GNPs-CQDs @ MOFs core-shell nano material in the step S2 comprises the following steps: dissolving terephthalic acid and aluminum chloride hexahydrate in a mixture of N, N-dimethylformamide and methanol, carrying out ultrasonic treatment, then adding GNPs-CQDs, uniformly stirring, placing in an autoclave, reacting at 140-160 ℃ for 14-16 h, and washing and drying precipitates to obtain the GNPs-CQDs @ MOFs.
5. The method for rapidly detecting the volatile benzaldehyde in the exhaled breath of the human body according to claim 1, wherein the step S3 of depositing the GNPs-CQDs @ MOFs core-shell nano-materials on the paper substrate comprises vacuum filtration; the paper substrate includes cellulose-based filter paper.
6. The method for rapidly detecting the volatile benzaldehyde in the exhaled breath of the human body according to claim 1, wherein the method for extracting the gaseous benzaldehyde in the exhaled breath by using the GNPs-CQDs @ MOFs paper chip in step S4 comprises: and introducing the exhaled air sample into a device carrying the GNPs-CQDs @ MOFs paper chip to enrich the benzaldehyde in the exhaled air on the GNPs-CQDs @ MOFs paper chip.
7. The method for rapidly detecting the volatile benzaldehyde in the exhaled breath of human body in the field according to claim 1, wherein the step S5 of detecting the benzaldehyde by surface enhanced raman spectroscopy comprises: and performing Raman signal detection on the paper chip after the gas benzaldehyde is extracted by adopting a portable Raman spectrometer to obtain an SERS spectrum, and comparing the SERS spectrum with a spectrum without benzaldehyde so as to realize qualitative and quantitative detection.
8. The method of claim 7, wherein the excitation wavelength of the process for detecting benzaldehyde by surface enhanced Raman spectroscopy is 785nm, the integration time is 10s, and the Raman spectroscopy peak is 1620cm-1As a basis for determination, 1620. + -.2 cm-1The benzaldehyde content was calculated corresponding to a linear curve between the raman peak intensity and the concentration of benzaldehyde.
9. The method of claim 8, wherein the linear curve of the concentration of benzaldehyde to Raman signal intensity is defined as 1 x 10-4、1×10-3、1×10-2、1×10-1、1×100、1×101，1×102And performing linear fitting on ppm gas benzaldehyde and the corresponding Raman signal intensity to obtain the product.
10. The method of claim 1, wherein the fluorescence detection of benzaldehyde comprises: GNPs-CQDs @ MOFs paper chips for extracting gas benzaldehyde with different concentrations are irradiated by ultraviolet lamps, and the fluorescence intensity is observed.
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