阅读说明：本技术 一种基于三元拉曼报告分子的sers防伪标签 (SERS anti-counterfeit label based on ternary Raman reporter molecule ) 是由 李秋瑾 刘凯璇 张健飞 于 2021-09-09 设计创作，主要内容包括：本发明涉及一种基于三元拉曼报告分子的SERS防伪标签,属于SERS光谱编码领域。本发明首先按一定比例混合不同拉曼报告分子,将三元拉曼报告分子封装在金纳米棒的核壳间隙内,以制备包覆有多元报告分子的双层金棒(Au@Au NRs),然后使用油水界面自组装的方法将Au@Au NRs组装成规律有序的金纳米膜。在这项工作中,我们利用双层金棒的良好SERS效应构建防伪标签,其中识别信息是从金核壳间隙内的拉曼报告分子的SERS信号中获得的。根据三元报告分子的特征峰波数和强度进行编码,对每个SERS信号进行数字化,得到两组代码序列,对这两组代码序列进行组合并进行进一步的编码转换,生成防伪标签。三元拉曼报告分子SERS标签可以使得SERS信号具有高度特异性和极高的识别精度,编码可以进一步增加信息的保密度和不可复制性,为开发新型防伪技术提供了思路。(The invention relates to a SERS anti-counterfeiting label based on a ternary Raman reporter molecule, and belongs to the field of SERS spectral coding. The method comprises the steps of mixing different Raman reporter molecules according to a certain proportion, packaging a ternary Raman reporter molecule in a core-shell gap of a gold nanorod to prepare a double-layer gold rod (Au @ Au NRs) coated with the ternary reporter molecule, and then assembling the Au @ Au NRs into a gold nano-film with a regular order by using an oil-water interface self-assembly method. In this work, we constructed anti-counterfeit labels using the good SERS effect of the double-layer gold rods, where the identification information was obtained from the SERS signal of the raman reporter molecule within the gap of the gold core-shell. And coding according to the characteristic peak wave number and the intensity of the ternary reporter molecule, digitizing each SERS signal to obtain two groups of code sequences, combining the two groups of code sequences, and performing further coding conversion to generate the anti-counterfeiting label. The ternary Raman reporter molecule SERS tag can enable an SERS signal to have high specificity and extremely high identification precision, and the code can further increase the information density and the non-replicability, so that a thought is provided for developing a novel anti-counterfeiting technology.)

1. A SERS anti-counterfeiting label based on a ternary Raman reporter molecule comprises the following steps:

(1) determination of raman reporter SERS signal: taking core-shell gold nanorods (Au @ Au NRs) as an SERS enhancement substrate, respectively encapsulating three Raman reporter molecules in core-shell gaps of the gold nanorods to prepare double-layer gold nanorods coated with different Raman reporter molecules, performing SERS scanning on several double-layer gold nanorods with different Raman reporter molecules to obtain SERS signals of different Raman reporter molecules, and taking characteristic peaks of the Raman reporter molecules as information for coding;

(2) determination of the SERS signal of the ternary raman reporter: firstly, blending three Raman reporter molecule solutions to form a ternary Raman reporter molecule, directly attaching the ternary Raman reporter molecule to the surface of a single-layer gold nanorod, then packaging a gold shell layer, self-assembling the gold nanorod into a nano film by using an oil-water interface self-assembly method to obtain a gold film with the ternary Raman reporter molecule, and performing SERS scanning on the gold film to obtain an SERS signal of the ternary Raman reporter molecule;

(3) and (3) encoding the wave number of the SERS spectrum of the ternary Raman reporter molecule: sequencing the characteristic peak wave numbers respectively corresponding to the ternary Raman reporter molecules according to a certain mode, and respectively marking the characteristic peak wave numbers with codes, thereby forming anti-counterfeiting information of a first dimension;

(4) encoding the intensity of the SERS spectrum of the ternary Raman reporter molecule: the SERS spectrogram of the ternary Raman reporter molecule is normalized so as to unify the peak intensity, and then the peak intensity is divided and respectively expressed by codes, so that the anti-counterfeiting information of the second dimension is formed.

2. The method for encoding anti-counterfeiting by SERS spectroscopy based on the ternary Raman reporter molecule according to claim 1, wherein the Raman reporter molecule in the step (1) is DTNB, BDT and 4-ATP, and is not limited to these three Raman reporter molecules.

3. The method for encoding anti-counterfeit by SERS spectroscopy based on a ternary Raman reporter according to claim 1, wherein the characteristic peaks of the Raman reporter in the step (1) are 1-10 peaks such as a major characteristic peak and a minor characteristic peak.

4. The method for encoding anti-counterfeiting by SERS spectroscopy based on ternary Raman reporter molecules as claimed in claim 1, wherein the mixing ratio in the step (2) is 1: 1 and 1: 2: 1.

5. The method for encoding anti-counterfeiting by SERS spectroscopy based on ternary Raman reporter molecules as claimed in claim 1, wherein the sorting method in the step (3) is that the sorting is performed from small to large according to wave numbers, and the codes are numbers 1-100 and letters A-Z.

6. The method for encoding anti-counterfeiting by SERS spectroscopy based on ternary Raman reporter molecules as claimed in claim 1, wherein the intensity of the peak in the step (4) is divided from weak to strong according to the peak intensity, and the codes are numbers 1-100 and letters A-Z.

Technical Field

The invention relates to a SERS anti-counterfeiting label based on a ternary Raman reporter molecule, and belongs to the field of SERS spectral coding.

Background

Counterfeit goods pose an increasingly serious threat to social economy and public safety. Over the past several decades, various anti-counterfeiting and security technologies have been developed to combat counterfeiting, such as printing, anti-counterfeiting inks, watermarks and holograms. However, as technology has evolved, some security labels are known to counterfeiters and are easily reproduced. In view of the present, there is a continuing need to develop new, more secure security tags to better support product authentication. Surface Enhanced Raman Scattering (SERS) can provide a one-to-one correspondence of specific "fingerprint" signals to raman reporter molecules on the surface of metal nanoparticles, resulting in a unique fingerprint raman spectrum of the reporter molecules. By mixing various Raman reporter molecules in different proportions, the generated SERS label is one of powerful tools for anti-counterfeiting, is easy to generate due to inherent randomness, and is difficult to reproduce. The SERS tag can provide a potential platform and realize indestructible anti-counterfeiting.

The spectral wave number-intensity combined coding method related by the patent is characterized in that a core-shell gold nanorod (Au @ AuNRs) containing a plurality of Raman reporter molecules mixed according to a certain proportion is self-assembled into a film in the preparation process to obtain a gold film with a ternary Raman reporter molecule, SERS signals of the Raman reporter molecules in the gold film are coded and converted, and the obtained result is combined with the gold film to have the potential of being applied to anti-counterfeiting and identity information identification and authentication.

Disclosure of Invention

The method comprises the steps of mixing three Raman reporter molecules according to a certain proportion to form a multi-element Raman reporter molecule, packaging the multi-element Raman reporter molecule in a core-shell gap of a gold nanorod to prepare a double-layer gold rod (Au @ Au NRs) coated with a multi-element probe, and then assembling the Au @ Au NRs into a gold nano-film with ordered regularity by using an oil-water interface self-assembly method. In this work, we constructed anti-counterfeit labels using the good SERS effect of the double-layer gold rods, where the identification information was obtained from the SERS signal of the raman reporter molecule within the gap of the gold core-shell. The signal corresponds to the change of the type of the used probe and the mixing proportion, has obvious regular change, simultaneously has extremely high identification precision and non-replicability, is coded by two dimensions of characteristic peak wave number and intensity, and then the coding result is further converted, so that the obtained result has the potential of being applied to the anti-counterfeiting aspect.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

(1) determination of raman reporter SERS signal: taking core-shell gold nanorods (Au @ Au NRs) as an SERS enhancement substrate, respectively encapsulating three Raman reporter molecules in core-shell gaps of the gold nanorods to prepare double-layer gold nanorods coated with different Raman reporter molecules, performing SERS scanning on several double-layer gold nanorods with different Raman reporter molecules to obtain SERS signals of different Raman reporter molecules, and taking characteristic peaks of the Raman reporter molecules as information for coding;

(2) determination of the SERS signal of the ternary raman reporter: firstly, blending three Raman reporter molecule solutions to form a ternary Raman reporter molecule, directly attaching the ternary Raman reporter molecule to the surface of a single-layer gold nanorod, then packaging a gold shell layer, self-assembling the gold nanorod into a nano film by using an oil-water interface self-assembly method to obtain a gold film with the ternary Raman reporter molecule, and performing SERS scanning on the gold film to obtain an SERS signal of the ternary Raman reporter molecule;

(3) and (3) encoding the wave number of the SERS spectrum of the ternary Raman reporter molecule: sequencing the characteristic peak wave numbers respectively corresponding to the ternary Raman reporter molecules according to a certain mode, and respectively marking the characteristic peak wave numbers with codes, thereby forming anti-counterfeiting information of a first dimension;

(4) encoding the intensity of the SERS spectrum of the ternary Raman reporter molecule: the SERS spectrogram of the ternary Raman reporter molecule is normalized so as to unify the peak intensity, and then the peak intensity is divided and respectively expressed by codes, so that the anti-counterfeiting information of the second dimension is formed.

The Raman probe molecules in the step (1) are DTNB, BDT and 4-ATP, and are not limited to the three Raman reporter molecules;

the characteristic peaks of the probe molecule in the step (1) are 1-10 peaks such as a main characteristic peak, a minor characteristic peak and the like;

the mixing ratio in the step (2) is 1: 1 and 1: 2: 1;

the sorting method in the step (3) is that sorting is carried out according to wave numbers from small to large, and codes used are numbers 1-100 and letters A-Z;

the intensity of the peak in the step (4) is divided according to the intensity of the peak from weak to strong, and the used codes are numbers 1-100 and letters A-Z.

The invention has the advantages that:

the Au @ Au NRs containing the multivariate Raman reporter molecules has excellent SERS activity and specific SERS signals, and has great advantages when being used for anti-counterfeiting identification. The nano-film obtained by changing the type and the adding proportion of the composite Raman reporter can further improve the confidentiality of SERS signals. By the encoding method that the characteristic peak wave number and the intensity show regular changes along with different mixing ratios, a large number of anti-counterfeiting labels can be created by using a small number of Raman reporter molecules, and the information has high specific correspondence and irreproducibility, thereby providing a new idea for the future anti-counterfeiting technology.

Drawings

The drawings are only for purposes of illustrating and explaining the present invention and are not to be construed as limiting the scope of the present invention. Wherein:

FIG. 1: is a graph showing the results of example 1 of the present invention.

FIG. 2: is a graph showing the results of example 2 of the present invention.

FIG. 3: is a graph showing the results of example 3 of the present invention.

Detailed Description

The invention is described below in connection with specific embodiments with the attached figures. Unless otherwise specified, the technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.

Example 1: scanning an SERS spectrogram of the gold nano-film coated with the Raman reporter molecule DTNB. As shown in fig. 1, the SERS spectrum of the raman probe is simpler, broader, and sharper than other chemicals, and the core-shell structure of Au @ Au NRs can ensure that the raman probe generates enhanced, stable, and repeatable SERS signals.

Example 2: scanning SERS spectrogram of Au @ Au NRs gold nano-film coated with Raman reporter BDT. As shown in fig. 2, the SERS signal of the raman reporter is concentrated near the characteristic peak of the raman reporter used.

Example 3: scanning an SERS spectrogram of the gold nano-film coated with the Raman reporter molecule 4-ATP. As shown in fig. 3, raman reporter molecules provide a concept for the development of novel anti-counterfeiting technologies.