Search

CN-116297393-B - Qualitative and quantitative detection method for nicotine concentration based on surface enhanced Raman scattering technology and application thereof

CN116297393BCN 116297393 BCN116297393 BCN 116297393BCN-116297393-B

Abstract

The invention discloses an Au@PATP@Ag NRs nano material and a preparation method and application thereof. The invention also discloses a method for qualitatively and quantitatively detecting the nicotine concentration based on the surface enhanced Raman scattering technology and application thereof, wherein Au@PATP@Ag NRs nano particles are used as an active substrate material for SERS, a Raman spectrometer is used for analyzing and detecting a target object, according to the linear relation equation of the ratio of the obtained nicotine solutions with different concentrations to the SERS signal intensity of the characteristic peaks of the nicotine and the internal standard substance, the content of the nicotine in the solution to be detected can be obtained, and the detection sensitivity of the nicotine is greatly improved. And the internal standard molecules are introduced into the core-shell structure, so that the accuracy of the quantitative detection of nicotine is improved. The invention also has great application in the sensitive detection of nicotine in cigarette and environmental cigarette smoke. In addition, the invention has the advantages of simple principle, rapidness, simple pretreatment, high selectivity, high detection sensitivity and the like.

Inventors

  • WEI WEI
  • CHEN YUHUI
  • ZHUANG YURONG
  • PU YUEPU
  • ZHANG JUAN

Assignees

  • 东南大学

Dates

Publication Date
20260505
Application Date
20230228

Claims (15)

  1. 1. The Au@PATP@Ag NRs nano material is characterized by comprising an Au@Ag NRs core-shell structure and p-amino thiophenol in the Au@PATP@Ag NRs nano material.
  2. 2. The au@patp@ag NRs nanomaterial of claim 1, wherein the au@patp@ag NRs nanomaterial is of a core-molecule-shell nanorod structure, and the au@patp@ag NRs nanomaterial has an average length of 34.22±3.57 nm and a width of 12.92±1.42 nm.
  3. 3. The preparation method of the Au@PATP@Ag NRs nanomaterial according to any one of claims 1 to 2, which is characterized by comprising the following steps of: 1) Mixing CTAB, HAuCl 4 、AgNO 3 , hydroquinone and NaBH 4 solution to obtain a reaction solution, carrying out a constant-temperature water bath reaction, and centrifugally washing a reaction product to obtain Au NRs; 2) Adding an internal standard solution into part of the prepared Au NRs solution, carrying out constant-temperature shaking incubation on a shaking table, and centrifugally washing a reaction product to obtain Au@PATP NRs; 3) AgCl, au@PATP NRs and ascorbic acid solution are respectively added into the CTAC solution to obtain reaction solution, the reaction solution reacts in a constant-temperature water bath, and the reaction product is centrifugally washed to obtain Au@PATP@Ag NRs nano particles.
  4. 4. The method for preparing the Au@PATP@Ag NRs nanomaterial according to claim 3, wherein in the step 1), the final concentrations of CTAB, HAuCl 4 、AgNO 3 , hydroquinone and NaBH 4 in the reaction solution are respectively 0.1M, 0.4mM, 0.08-0.10 mM, 5-6 mM, 0.01-0.03 mM, the water bath temperature is 30-35 ℃, and the reaction time is 11-13 h.
  5. 5. The method for preparing the Au@PATP@Ag NRs nanomaterial according to claim 3, wherein the internal standard solution in the step 2) is a p-aminophenylthiophenol solution with the concentration of 0.01-0.03 mM, the constant-temperature shaking incubation time on a shaking table is 60-90 min, and the incubation temperature is 25-40 ℃.
  6. 6. The method for preparing the Au@PATP@Ag NRs nanomaterial according to claim 3, wherein in the step 3), final concentrations of CTAC, agCl and ascorbic acid solutions in the reaction solution are respectively 50-70 mM, 0-0.375 mM and 40-100 mM, the volume of the Au@PATP NRs is 1 mL, the temperature of the water bath reaction is 30-35 ℃, and the time of the water bath reaction is 3-4 h.
  7. 7. The use of the au@patp@ag NRs nanomaterial of any one of claims 1-2 in qualitative and/or quantitative detection of nicotine.
  8. 8. The use according to claim 7, wherein the use comprises detecting the nicotine content of a cigarette or an ambient cigarette smoke.
  9. 9. A method for qualitatively detecting nicotine based on a surface-enhanced Raman scattering technology is characterized by comprising the following steps of mixing and incubating the Au@PATP@Ag NRs nano material according to any one of claims 1-2 with nicotine solutions with different concentrations in equal volumes, taking part of samples after incubation, dripping the samples on a silicon wafer, drying at room temperature, then using the samples for SERS detection, and qualitatively analyzing nicotine according to peak positions in a Raman spectrum.
  10. 10. The method for qualitatively detecting nicotine based on Surface Enhanced Raman Scattering (SERS) as claimed in claim 9, wherein the incubation time is 10-30 min and the volume of the sample dropped on the silicon wafer is 10-20 μl.
  11. 11. The method for quantitatively detecting the nicotine concentration based on the surface enhanced Raman scattering technology is characterized by comprising the following steps of: A1 Mixing and incubating the Au@PATP@Ag NRs solution according to any one of claims 1-2 with nicotine solutions with different concentrations in equal volume, taking part of samples after incubation, dripping the samples on a silicon wafer, and drying at room temperature for SERS detection; a2 Qualitative and quantitative analysis is carried out on the dried sample adsorbed on the surface of the SERS active substrate by a Raman spectrometer, and a corresponding standard curve is established according to the relation between the measured ratio of the SERS signal intensity of the characteristic peak of the nicotine and the internal standard substance and the concentration of the nicotine; a3 And (2) replacing the nicotine standard solution with different concentrations in the step A1) with the sample to be detected, repeating the subsequent steps, carrying out qualitative analysis on the nicotine according to the peak position in the Raman spectrogram, and respectively checking the concentration of the nicotine in the sample to be detected on the standard curve in the step A2) according to the obtained Raman signal intensity ratio of the characteristic peaks of the object to be detected and the internal standard substance, thereby carrying out quantitative analysis on the nicotine.
  12. 12. The method for quantitatively detecting nicotine concentration based on the surface-enhanced raman scattering technique according to claim 11, wherein the incubation time is 10-30 min, and the volume of the sample dropped on the silicon wafer is 10-20 μl.
  13. 13. The method of claim 11, wherein the nicotine concentration is 10 −8 -10 −3 M, and wherein the method further comprises detecting the nicotine content of the cigarette and/or ambient cigarette smoke.
  14. 14. The method according to claim 13, wherein the method for detecting nicotine in cigarette and/or ambient cigarette smoke comprises: B1 The method comprises the steps of dripping nicotine standard solutions with different concentrations into cigarettes, drying, igniting the cigarettes, pumping smoke into ultrapure water at a constant flow rate by using an air pump, using diluted samples for SERS detection, and calculating an extraction Efficiency (ER) formula according to the method, wherein ER (%) = is shown in the formula The method comprises the steps of (1) calculating the nicotine content before and after the nicotine standard solution is added in the obtained cigarette by using a standard adding method, wherein (x 100), m before and m after are respectively the nicotine content before and after the nicotine standard solution is added in the obtained cigarette, and m spiked is the added nicotine content; b2 The method comprises the steps of collecting smoke generated after cigarette combustion in a closed device, absorbing the collected smoke into ultrapure water at a constant speed, using diluted samples for SERS detection, calculating the nicotine content in the smoke of the cigarettes in the closed space according to a corresponding linear fitting equation and the flow rate of an air pump, and finally, collecting the smoke generated after cigarette combustion with different numbers in the closed device respectively, and repeating the following steps to obtain the linear relation between the number of cigarettes and the nicotine content.
  15. 15. The method according to claim 14, wherein in step B1) the concentration of the nicotine standard solution is 0M, 10 -3 M,5×10 -3 M,10 -2 M, the volume is 1.1 mL, and in step B2) the flow rate of the pump is 1.1L/min and the pump time is 2 min.

Description

Qualitative and quantitative detection method for nicotine concentration based on surface enhanced Raman scattering technology and application thereof Technical Field The invention belongs to the technical field of analysis and sensing, and particularly relates to a method for qualitatively and quantitatively detecting nicotine concentration based on a surface enhanced Raman scattering technology and application thereof. Background Nicotine, also known as nicotine, is an alkaloid present in plants of the Solanaceae family (Solanum), and is also an important component in tobacco and cigarette smoke. Nicotine promotes the release of neurotransmitters (e.g., dopamine, etc.), makes a person pleasant, regulates the person's emotion, etc. At the same time, nicotine can cause addiction or dependency, and excessive exposure to nicotine can cause various diseases including lung injury, nausea, emesis, headache, memory deterioration, urinary incontinence, etc., and even death in severe cases. To date, various methods have been reported for qualitative and quantitative analysis of nicotine, such as spectrophotometry, fluorescence, electrochemistry, electrochemiluminescence, liquid chromatography and capillary electrophoresis. However, these methods have the disadvantages of complicated sample preparation process, high cost, poor selectivity and low detection sensitivity in the detection of nicotine, which seriously hampers the large-scale application of nicotine detection in actual tobacco and cigarette smoke. The Surface Enhanced Raman Scattering (SERS) has the advantages of rapidness, no damage, safety, high sensitivity, simple sample pretreatment, fingerprint specificity and the like, and plays a positive role in the fields of food safety, environmental protection, medical detection and the like. SERS generally refers to adsorption of molecules to be detected on a rough surface of a nano metal material (such as Au, ag or Cu), so that raman signals of an object to be detected can be enhanced by 10 6-1015 times, and the sensitivity is very high. The choice of SERS-active substrate is important to obtain a higher raman enhancement signal. Generally, pure nano silver has weak chemical stability and is easy to oxidize, and pure nano gold has relatively poor SERS enhancement effect and is limited in application in some fields. Meanwhile, due to uneven distribution of plasma hot spots on the SERS active substrate, different enhancement effects and poor measurement reproducibility, quantitative analysis of SERS has great problems. Therefore, the high-sensitivity qualitative and quantitative detection method of nicotine based on the surface enhanced Raman scattering technology is very important, and has great significance for detecting the nicotine content in daily tobacco and cigarette smoke. Disclosure of Invention The invention aims to solve the technical problem of providing the Au@PATP@Ag NRs nano material which is used as an SERS active substrate and can be used for sensitively and rapidly detecting nicotine. The invention also solves the technical problem of providing a preparation method and application of Au@PATP@Ag NRs nano material with simple principle, rapidness and simple pretreatment. The invention also solves the technical problem of providing a method for qualitatively and/or quantitatively detecting the nicotine concentration based on the surface enhanced Raman scattering technology, which has the advantages of high sensitivity, simple and rapid detection method, simple pretreatment and high selectivity. The invention provides an Au@PATP@Ag NRs nano material, which comprises an Au@Ag NRs core-shell structure and p-amino thiophenol in the Au@PATP@Ag NRs core-shell structure. The Au@PATP@Ag NRs nano material is of a core-molecule-shell nano rod structure, the average length of the Au@PATP@Ag NRs nano material is 34.22+/-3.57 nm, the width of the Au@PATP@Ag NRs nano material is 12.92+/-1.42 nm, and the core-molecule-shell nano rod structure has very high surface plasmon resonance, so that the detection sensitivity of nicotine is greatly improved. Wherein, the concentration of the p-aminophenylthiophenol IS 0.01-0.03mM, PATP IS introduced into the core-shell structure as an internal standard molecule (IS), so that the quantitative detection of nicotine IS more accurate. The invention also discloses a preparation method of the Au@PATP@Ag NRs nano material, which comprises the following steps of: 1) Mixing CTAB, HAuCl 4、AgNO3, hydroquinone and NaBH 4 solution, carrying out constant-temperature water bath reaction, and centrifugally washing a reaction product to obtain Au NRs; 2) Adding an internal standard solution into part of the prepared Au NRs solution, carrying out constant-temperature shaking incubation on a shaking table, and centrifugally washing a reaction product to obtain Au@PATP NRs; 3) AgCl, au@PATP NRs and ascorbic acid solution are respectively added into the CTAC solution, the reaction is carried