CN110764171A - Nanorod heterogeneous structure independent of polarization direction of excitation light and application thereof - Google Patents
Nanorod heterogeneous structure independent of polarization direction of excitation light and application thereof Download PDFInfo
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- CN110764171A CN110764171A CN201910993752.5A CN201910993752A CN110764171A CN 110764171 A CN110764171 A CN 110764171A CN 201910993752 A CN201910993752 A CN 201910993752A CN 110764171 A CN110764171 A CN 110764171A
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Abstract
The invention belongs to the technical field of molecular recognition and nanoprobes in life science, and particularly relates to a nanorod isomeric structure independent of the polarization direction of excitation light and application thereof. The infrared performance of the nanorod missing in the short axis direction is compensated through the LSPR resonance coupling effect of the nanorod and another core-shell nanoparticle, so that the dependence of the nanorod on the polarization state is removed, the parallel relation between the polarization state of exciting light and the long axis is not required to be matched, and the optimal near-infrared band absorption of the nanorod is automatically obtained.
Description
Technical Field
The invention belongs to the technical field of molecular recognition and nanoprobes in life science, and particularly relates to a heterogeneous dimer nanoparticle structure insensitive to the polarization state of excitation light and application thereof.
Background
Precious metal nanostructures such as gold, silver, platinum and the like exhibit strong absorption properties in the visible-near infrared band due to their unique Local Surface Plasmon Resonance (LSPR), so that these nanostructured particles are of great interest in life science research. Particularly, the gold nanostructure has the advantages of easy chemical modification on the surface, good biocompatibility and the like, and has wide application prospect in the related biomedical fields of nano probes such as biosensing, biological imaging, surface enhanced Raman scattering, photothermal diagnosis and treatment, drug delivery and the like.
Among a plurality of nanostructures with LSPR effect, the gold nanorod can generate strong absorption in a Near Infrared (NIR) waveband, has strong penetrability to tissue cells, and is especially suitable for eyes in basic and application research of nano biomedicine in recent years, for example, the gold nanorod replaces a contrast agent to cooperate with X-ray CT imaging by utilizing the strong absorption characteristic; the molecular interaction between the cells and the hybridized gold nanorods is observed under a dark field microscope, and the near infrared characteristic of the cells can effectively replace errors generated by the autofluorescence characteristic; irradiation with a specific wavelength low power laser in the cancer cell study that has deteriorated, using photothermal effects also leads to death of gold nanorod-labeled malignant cells.
The LSPR performance of the noble metal nanostructure strongly depends on its own structural parameters, including geometric size, particle shape and spacing, dielectric constant of the environment, etc., and by adjusting the above structural parameters, a specific LSPR absorption peak wavelength can be artificially selected. Generally, for spherical solid nanoparticles with a diameter of less than 60nm, the peak absorption wavelength is about 532nm, and it is difficult to largely red-shift the absorption wavelength to the near infrared band with such a simple structure. The wave band of 700 nm-1200 nm is an ideal optical window in the biomedical research, because the wave band can well avoid the absorption interference of water. One of the main reasons why gold nanorods are favored for a lot of research is their optical properties in the near infrared band. The properties depend on the structural parameters of the nano-rods, and the long axis length and the long-short axis ratio of the nano-rods are simply controlled, so that the peak absorption wavelength can be greatly red-shifted to the near infrared wavelength.
But the absorption of the nanorod in the optimal near-infrared band needs to match the polarization state of the excitation light parallel to the long axis of the nanorod. For example, a cylindrical gold nanorod with a diameter of 50nm and an axial length of 136nm has an LSPR absorption peak wavelength of about 880nm when the polarization state is parallel to the axis, an excited LSPR absorption peak of about 520nm when the polarization state is perpendicular to the axis, and when the polarization state forms an angle with the long axis of the nanorod, the absorption intensity of 880nm decreases rapidly as the component of the polarization state in the long axis direction decreases. In order to obtain the optimum absorption performance at 880nm, it is necessary to control the polarization state of the excitation light to be parallel to the long axis. When the gold nanorods are applied to the biomedical related field as the nanoprobe, the natural postures of the gold nanorods are random, and the accurate direction of the nanorods is difficult to obtain, so that the method which is not limited by the direction of the polarization state of the excitation light and can automatically excite the optimal near-infrared performance of the nanorods is very expected in the related field, but related researches are rarely reported. Based on the structure, the heterogeneous double-particle structure based on the nano rod compensates the missing infrared performance in the short axis direction through the LSPR resonance coupling effect of the nano rod and another particle, and therefore the dependence of the nano rod on the polarization state is removed.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a nanorod-based heterogeneous double-particle structure, and the infrared performance missing in the short axis direction is compensated through the LSPR resonance coupling effect of a nanorod and another core-shell nanoparticle, so that the dependence of the nanorod on the polarization state is removed. The nanorod isomeric dimer structure optimizes the near-infrared performance of a single nanorod and can be effectively applied to the application field with the requirement of an optical window.
The technical scheme of the invention is as follows:
a nanorod heterogeneous structure independent of the polarization direction of excitation light is characterized in that the resonance wavelength of the nanorod is overlapped with the absorption peak of a long axis through a plasma mode of a short axis of a red shift nanorod under the resonance coupling action of surface plasmas between a nanorod and core-shell nanoparticles, so that the dependence of a near-infrared mode of the long axis on the polarization state is removed; the characteristics of the nanorod isomeric structure are as follows:
i. the structure is a heterogeneous dimer structure formed by nanorods and core-shell nanoparticles;
the binding point of the two particles is located at the midpoint of the long axis of the nanorod;
III, respectively generating LSPR absorption peaks lambda of the nanorods under the action of exciting light along with the polarization state parallel or perpendicular to the long axis1And λ2The determination principle of the core-shell nanoparticle structure parameters is as follows: the core-shell nano particles and the nano rods are subjected to LSPR coupling action and can convert lambda into2Red shift of peak to lambda1。
In the nanorod isomeric structure, the structure of the core-shell nanoparticles can evolve, and the evolvable structure comprises a solid gold sphere structure, a hollow core-shell structure, a solid half-shell structure and the like so as to meet the requirements of different absorption wave bands.
The optical properties of the nano-rod and the core-shell nanoparticle are different from those of the heterodimer nanoparticle formed by combining the nano-rod and the core-shell nanoparticle, and the change of the optical properties is used for high-specificity detection and identification of single molecules.
The invention has the beneficial effects that: the invention provides a nanorod-based heterogeneous double-particle structure, which can automatically obtain the optimal near-infrared band absorption of a nanorod under any included angle without matching the parallel relation between the polarization state of exciting light and a long axis.
Drawings
FIG. 1 shows the absorption spectrum characteristic curves of a single gold nanorod structure, a nanorod and a hollow core-shell heterodimer structure;
FIG. 2 is a variation curve of absorption spectrum characteristics of a single gold nanorod rotating along the polarization direction of incident light, wherein the angle is an included angle between the long axis of the nanorod and the electric field direction of linearly polarized light;
FIG. 3 is an absorption spectrum characteristic change curve of gold nanorod core-shell heterodimer rotating along with the polarization direction of incident light, and the angle is the included angle between the long axis of the nanorod and the electric field direction of the linearly polarized light.
Detailed Description
The embodiments are described in detail below with reference to the drawings and technical solutions. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
FIG. 1 shows the absorption characteristic curve of a single gold nanorod and the absorption characteristic curve of a heterogeneous dimer after compensation by using hollow core shell particles, wherein the geometric dimension of the gold nanorod is a structure with a short axis radius of 25nm and a long axis of 136nm, and the gold nanorod is a hollow structure with an outer diameter of 60nm and a shell thickness of 5 nm. As shown in fig. 1, when the long axis center line of the gold nanorod is parallel to the linearly polarized electric field direction, the optimal optical characteristic at the wavelength of the absorption peak is obtained, and the peak value of the absorption peak is significantly reduced as the included angle is increased to 90 degrees; and the peak value of the compensated isomeric dimer at the wavelength of the absorption peak is almost unchanged along with the rotation of the linearly polarized light electric field direction.
The long axis direction of the nanorod particles is set as the Y-axis direction, the plane where the center line of the long axis and the center point of the core shell are located is a YZ plane, exciting light is incident in the negative direction of the X axis, the direction of the linearly polarized light electric field rotates in the YZ plane, when the direction of the linearly polarized light electric field is parallel to the Y axis, namely the long axis direction of the nanorod, the angle of 0 degree is set, and the included angle between the direction of the linearly polarized light electric field and the Y axis is. When theta is 0 degrees and 90 degrees in the absorption spectrum of a single gold nanorod, two absorption peaks of 865nm and 520nm are obtained respectively. When theta is 0 degree in the absorption spectrum of the isomeric dimer, the optical characteristics of the exciting light and the long axis direction are matched, and the characteristic is represented as an absorption peak 880nm of the long axis of the nanorod; in order to compensate and optimize the optical characteristics of the nano-rod in the short axis direction (namely when theta is 90 degrees), the middle point of the short axis side of the nano-rod is combined with a hollow core-shell particle with the distance of 1nm, so that LSPR coupling resonance is generated between two heterogeneous nano-particles, and the absorption peak is greatly red-shifted to 880nm when the short axis direction is matched with the polarization state of exciting light; during the process that theta is increased from 0 DEG to 90 DEG, the component of the polarization state in the short axis direction excites the coupling of the heterodimer, so that the absorption cross section of the heterodimer at 880nm is rapidly increased, and the reduction of the component of the polarization state in the long axis direction is compensated to cause the reduction of the absorption cross section at 880 nm. The invention discloses an isomeric dimer nanoparticle structure insensitive to the polarization state of excitation light, which is shown by dotted lines in figure 1, and realizes compensation of optical performance missing at 880nm on the short axis side of the polarization state of the excitation light of a single gold nanorod particle structure by utilizing local surface plasmon resonance coupling between two nanoparticles with different structures, thereby removing the dependence of the absorption performance of the nanorod particle on the polarization state of the excitation light.
Claims (3)
1. A nanorod heterogeneous structure independent of the polarization direction of excitation light is characterized in that a plasma mode of a nanorod short axis is red-shifted through the surface plasma resonance coupling effect between a nanorod and core-shell nanoparticles, so that the resonance wavelength of the nanorod short axis coincides with the absorption peak of the long axis, and the dependence of the near-infrared mode of the long axis on the polarization state is removed; the characteristics of the nanorod isomeric structure are as follows:
i. the structure is a heterogeneous dimer structure formed by nanorods and core-shell nanoparticles;
the binding point of the two particles is located at the midpoint of the long axis of the nanorod;
III, respectively generating LSPR absorption peaks lambda of the nanorods under the action of exciting light along with the polarization state parallel or perpendicular to the long axis1And λ2The determination principle of the core-shell nanoparticle structure parameters is as follows: the core-shell nano particles and the nano rods are subjected to LSPR coupling action and can convert lambda into2Red shift of peak to lambda1。
2. The nanorod isomeric structure without depending on the polarization direction of the excitation light as claimed in claim 1, wherein the evolving structure of the core-shell nanoparticle is a solid gold sphere structure, a hollow core-shell structure, a solid core-shell structure or a solid half-shell structure to adapt to different absorption band requirements.
3. The use of the nanorod isomeric structure independent of the polarization direction of the excitation light according to claim 1 or 2, wherein the nanorods and the core-shell nanoparticles each have optical properties different from those of a heterodimeric nanoparticle formed by combining the nanorods and the core-shell nanoparticles, and the change in the optical properties is used for highly specific detection and recognition of single molecules.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896325A (en) * | 2012-10-12 | 2013-01-30 | 江南大学 | Preparation method of small molecule inorganic salt-based chiral self-assembly material of gold nanorods |
| CN108594341A (en) * | 2018-06-13 | 2018-09-28 | 中国工程物理研究院应用电子学研究所 | The preparation of gold-nano-piece-gold nanosphere dimer and its application resonated in strong polarization independent method promise |
| CN109358037A (en) * | 2018-10-23 | 2019-02-19 | 大连理工大学 | The isomery double nano grain structure and its application insensitive to excitation polarization state |
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- 2019-10-18 CN CN201910993752.5A patent/CN110764171A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896325A (en) * | 2012-10-12 | 2013-01-30 | 江南大学 | Preparation method of small molecule inorganic salt-based chiral self-assembly material of gold nanorods |
| CN108594341A (en) * | 2018-06-13 | 2018-09-28 | 中国工程物理研究院应用电子学研究所 | The preparation of gold-nano-piece-gold nanosphere dimer and its application resonated in strong polarization independent method promise |
| CN109358037A (en) * | 2018-10-23 | 2019-02-19 | 大连理工大学 | The isomery double nano grain structure and its application insensitive to excitation polarization state |
Non-Patent Citations (2)
| Title |
|---|
| 柯善林 等: "金纳米棒的光学性质研究进展", 《物理化学学报》 * |
| 洪昕 等: "芯帽纳米颗粒的光热性质", 《物理学报》 * |
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