CN117589687A - Optical cavity container based on air-wrapped liquid, application and spectrum detection method - Google Patents

Optical cavity container based on air-wrapped liquid, application and spectrum detection method Download PDF

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Publication number
CN117589687A
CN117589687A CN202410074326.2A CN202410074326A CN117589687A CN 117589687 A CN117589687 A CN 117589687A CN 202410074326 A CN202410074326 A CN 202410074326A CN 117589687 A CN117589687 A CN 117589687A
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optical cavity
cavity container
container
optical
liquid
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CN117589687B (en
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杨燕婷
吴孟璠
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Chengdu Aliebn Science And Technology Co ltd
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Abstract

The invention belongs to the technical field of instrument analysis, and particularly relates to an optical cavity container based on air-wrapped liquid, application and a spectrum detection method. The optical cavity container is based on an air-wrapped liquid/air interface and an inner wall material structure of the optical cavity container, so that a liquid sample in the optical cavity container becomes an optical resonant cavity similar to a lens and used for concentrating and amplifying light. According to the invention, through the inner wall material structure of the optical cavity container, an air layer with low refractive index can be efficiently formed between the liquid and the optical cavity container, and an air/liquid interface with abrupt refractive index is obtained, so that the sample liquid becomes an optical resonant cavity similar to a lens and used for concentrating amplified light, and efficient transmission of a spectrum signal generated by the liquid to a light detector is realized. The optical cavity container has the advantages of good self-cleaning capability, reusability, good stability, suitability for various spectrum detection methods and the like.

Description

Optical cavity container based on air-wrapped liquid, application and spectrum detection method
Technical Field
The invention belongs to the technical field of instrument analysis, and particularly relates to an optical cavity container with air almost completely wrapping liquid.
Background
A method of qualitatively and quantitatively analyzing a substance by using the spectrum of the substance is called spectroscopic analysis. In most cases, the object of the spectrum analysis is a liquid sample, and the information of the substance, structure, concentration and the like of the sample to be detected can be clearly obtained by analyzing the absorbance, optical rotation, fluorescence, phosphorescence, raman, terahertz and other spectrums of the liquid sample. While the container carrying the liquid to be measured is generally referred to as a cuvette and in optical analysis is generally referred to as a cuvette. According to the application, the color matching device can be divided into an ultraviolet cuvette, a visible light cuvette, an infrared cuvette, a fluorescent cuvette and the like. According to the materials, the materials can be classified into glass cuvettes, quartz cuvettes, plastic cuvettes and the like.
Along with the development of society, a sample pool is also continuously developed into new categories according to the needs of the times. The innovations for sample cells are still primarily improved and optimized from the standpoint of self-material, geometry, size, etc. Although various liquid sample cells for spectroscopic analysis have been developed in the prior art, the sample cells have been mainly responsible for the container function since the invention as an indispensable key component in spectroscopic analysis. During excitation, generation, and transmission of the spectroscopic analysis signal, not much is contributed to the spectroscopic signal control. In some studies, researchers have conducted some signal enhancement studies on sample cells in order to boost the contribution of the Chi Duiguang spectral signal of the sample. For example, in the literature, "drive up to Liu Guxiang, li Zhengang, et al," study [ J ]. Spectrometry and Spectrometry based on liquid Raman Spectroscopy enhancement method for novel sample cells, 2023, 43 (3): 712-717 ], the spectral signal is enhanced from a geometric optics perspective by changing the material of the sample cell to a mirror capable of reflecting light, and changing the bottom of the circular sample cell to a concave mirror with light reflection. However, this method has limited spectral signal enhancement effect and has high requirements on the flatness, material and arrangement position of the mirror surface. And the optical mirror surface with high reflection has higher cost and poorer universality, and is difficult to popularize on a large scale.
In general, there are few prior art liquid sample reservoirs for optical enhancement, and there is a need in the art to develop new liquid optical cavity containers with optical enhancement.
Disclosure of Invention
The invention aims at the problems in the prior art and provides an air-wrapped optical cavity container so as to enhance a spectrum signal during spectrum analysis.
The invention is based on an optical cavity container of air-wrapped liquid, and the optical cavity container is based on an air-wrapped liquid/air interface and an inner wall material structure of the optical cavity container, so that a liquid sample in the optical cavity container becomes an optical resonant cavity, and the optical resonant cavity has the same function of concentrating and amplifying light as a lens. Wherein the material of the optical cavity container is at least one selected from metal, glass, quartz, PMMA plastic, PS plastic, PET plastic, PTFE plastic, ABS plastic or 3D printing resin.
Preferably, the inner surface of the optical cavity container is provided with a super-wetting hydrophobic structure, and when the optical cavity container is used for optical signal detection, an air layer wrapping the liquid sample is formed between the liquid sample and the inner wall of the container, and an air/liquid interface with abrupt refractive index changes is obtained.
Preferably, the thickness of the super-wetted hydrophobic structure is 10-500 μm.
Preferably, the super-wetting hydrophobic structure is prepared by adopting a method of spraying, coating, spin coating, photoetching, nanoimprint or vapor deposition.
Preferably, the super-wetting hydrophobic structure is prepared by adhering hydrophobic nano-particles on the inner surface of the optical cavity container through an adhesive.
Preferably, the hydrophobic nanoparticle is selected from at least one of hydrophobic nanosilica or hydrophobic nanosilica; and/or the adhesive is at least one of polyacrylate adhesive, polyurethane adhesive, polytetrafluoroethylene adhesive, rubber adhesive or phenolic resin adhesive.
Preferably, the optical cavity container is a square optical cavity container, a round optical cavity container, an annular optical cavity container, a U-shaped optical cavity container, a Y-shaped optical cavity container, a multi-channel optical cavity container, a flat bottom configuration optical cavity container, an elliptic bottom configuration optical cavity container or a conical sharp bottom configuration optical cavity container.
Preferably, the optical cavity container is used for detection of fluorescence spectrum, raman spectrum, ultraviolet spectrum or X-ray spectrum.
The invention also provides the application of the optical cavity container for air-wrapped liquid in spectrum detection.
The invention also provides a spectrum detection method, which carries out spectrum detection after the optical cavity container carries the liquid sample.
The inner surface of the optical cavity container is of a super-infiltration hydrophobic structure, the super-infiltration hydrophobic structure can efficiently form an air layer with low refractive index between liquid and the optical cavity container, the liquid sample is almost completely wrapped by air, and an air/liquid interface with abrupt refractive index is obtained. The sample liquid is an optical resonant cavity similar to a lens and used for concentrating amplified light based on air layer wrapping of an optical cavity container and design of liquid geometric structure, so that efficient transmission of spectrum signals generated by the liquid to a light detector is realized. In addition, the internal surface structure and materials of the container can influence the photophysical properties of the solute by changing the arrangement state of water molecules on the surface of the liquid sample and the hydration shell structure formed by water and the solute. For example, in a fluorescence mode, the absolute fluorescence quantum yield of the solute in the liquid sample can be significantly improved and a significant fluorescence enhancement can be exhibited. Whereas the light detector receives only a small signal when the air without the container wraps around the liquid.
In addition, the optical cavity container has the advantages of good self-cleaning capability, reusability, good stability, suitability for various spectrum detection methods and the like. Therefore, the invention has good application prospect.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
Fig. 1 is an optical enhancement schematic diagram of the optical cavity container of embodiment 1, wherein a is a flow chart of the use of the optical cavity container, b is a schematic diagram of the optical enhancement principle of the optical cavity container, and c is a schematic diagram of the optical cavity container in the prior art.
Fig. 2 is a schematic diagram and a characterization result of a super-wetted hydrophobic structure of the optical cavity container in example 1, wherein a is a structural perspective view of the optical cavity container, b is an enlarged view of inner wall details of the super-wetted hydrophobic structure, c is a scanning electron microscope image of inner wall details of the super-wetted hydrophobic structure, and d is a water contact angle test image of the super-wetted hydrophobic structure.
FIG. 3 is a graph showing the fluorescence signal enhancement effect of the optical cavity container of example 1 in a fluorescence imaging system.
Fig. 4 is a graph showing the fluorescence signal enhancement effect of the optical cavity container of example 1 in a multifunctional microplate reader.
Fig. 5 is a graph showing the raman spectral signal enhancement effect of the optical cavity container of example 1 in a raman spectrometer.
Fig. 6 is a graph showing the ultraviolet-visible spectrum signal enhancement effect of the optical cavity container of example 1 in a multifunctional microplate reader.
Fig. 7 is a comparison of self-cleaning performance of the optical cavity container of example 1 and a commercial plastic optical cavity container.
Detailed Description
The reagents and raw materials used in the following examples were commercially available, which were not specifically described.
Example 1 air-wrap liquid based optical cavity Container
The invention is based on an optical cavity container of air-wrapped liquid, and the optical cavity container is based on an air-wrapped liquid/air interface and an inner wall material structure of the optical cavity container, so that a liquid sample in the optical cavity container becomes an optical resonant cavity, and the optical resonant cavity has the function of concentrating and amplifying light like a lens. Wherein the material of the optical cavity container is at least one selected from metal, glass, quartz, PMMA plastic, PS plastic, PET plastic, PTFE plastic, ABS plastic or 3D printing resin.
The inner surface of the optical cavity container is provided with a super-wetting hydrophobic structure, the thickness of the super-wetting hydrophobic structure is 10-500 mu m, and the super-wetting hydrophobic structure is prepared by adopting a spraying, coating, spin coating, photoetching, nanoimprint or vapor deposition method. When the optical cavity container is used for optical signal detection, an air layer which almost completely wraps the liquid sample is formed between the liquid sample and the inner wall of the container, and an air/liquid interface with abrupt refractive index changes is obtained.
The super-wetting hydrophobic structure is prepared by adhering hydrophobic nano particles on the inner surface of the optical cavity container through an adhesive. Wherein,
the hydrophobic nano particles are selected from at least one of hydrophobic nano silicon dioxide or hydrophobic nano titanium dioxide; and/or the adhesive is at least one of polyacrylate adhesive, polyurethane adhesive, polytetrafluoroethylene adhesive, rubber adhesive or phenolic resin adhesive.
The optical cavity container is a square optical cavity container, a round optical cavity container, an annular optical cavity container, a U-shaped optical cavity container, a Y-shaped optical cavity container, a multi-channel optical cavity container, a flat bottom configuration optical cavity container, an elliptic bottom configuration optical cavity container or a conical sharp bottom configuration optical cavity container.
The optical cavity container is used for detecting fluorescence spectrum, raman spectrum, ultraviolet spectrum or X-ray spectrum.
The method and principle of using the optical cavity container provided in this embodiment are shown in fig. 1, and the structure and characterization result are shown in fig. 2. Specifically, the cell body of the optical cavity container can be any optical cavity container in the prior art, and in the spectrum test of this embodiment, if the excitation light is from top to bottom and the signal is received from top, the conical pointed bottom optical cavity container is selected; if the excitation light is from bottom to top and the signal is received at the upper part, a conical pointed-bottom-shaped optical cavity container with a small hole (aperture 1.5 and mm and through arrangement) at the center of the bottom and capable of avoiding liquid leakage due to the surface tension of liquid is selected; the material of the optical cavity container is selected to be photosensitive resin (transparent photosensitive resin special for Dongguan Jun Yi SLA).
The super-wetted hydrophobic structure is prepared by spraying in this example, specifically, a hydrophobic silica nanoparticle solution (model: 260, solid content 20 wt% of Aba Ding Shiji company) containing an adhesive is sprayed 3 times (100 μl of each spray amount) into an optical cavity container (inner surface area of 2.5 cm) 2 ) Standing until the nano coating is completely cured, and preserving for standby (the thickness of the cured nano coating is 50 μm). The adhesive can be selected from various existing high-molecular adhesive solvents with strong adhesive force, and the embodiment is specifically selected from polypropylene resin. The characterization results of the nano coating (super-wetting hydrophobic structure) are shown in fig. 2c and 2d, and the results show that the prepared nano coating has a rough surface and good super-hydrophobic performance.
When the optical cavity container of the embodiment is used, due to the super-infiltration performance of the inner surface of the optical cavity container, a thin air layer can be formed between the liquid sample and the optical cavity container, and the interface and the geometrical constraint of the optical cavity container are utilized to realize the almost complete package of the air on the liquid sample. That is to say that the liquid sample actually has a very small area of direct contact with the optical cavity vessel, similar to the pattern of contact of a lotus leaf with a bead, which pattern is referred to in the theory of surface wettability as the Cassie-Baxter state. In a conventional optical cavity vessel, the spectroscopic analysis process is as follows: excitation light enters the liquid sample to interact with the liquid sample and generate a spectrum signal, and then the spectrum signal passes through the liquid phase directly through the optical cavity container and enters the optical detector. In the optical cavity container of this embodiment, the spectral signal passes through the air layer with low refractive index after passing through the liquid phase, and is refracted and reflected repeatedly at the interface from high refractive index to low refractive index, and the design of the liquid geometry is combined to make the sample liquid become an optical resonant cavity similar to a lens for concentrating amplified light. And then into an optical detector. Therefore, the invention realizes the obvious enhancement and regulation of the optical signal by the influence of the spontaneously formed optical cavity and the liquid/air interface on the water molecule arrangement and the hydration shell structure based on the air layer and the liquid drop geometric configuration of the optical cavity container.
Example 2 Spectrum detection method
The present embodiment provides a spectroscopic detection method for performing spectroscopic detection using the optical cavity container provided in embodiment 1 carrying a liquid sample. Other supplements and devices for spectroscopic detection are the same as in the prior art.
In order to compare the optical enhancement and self-cleaning capabilities, this example provided, in addition to the detection results of the optical cavity containers of example 1 as an experimental group, an optical cavity container using an existing optical cavity container (i.e., an optical cavity container in which a super-wetted hydrophobic structure was not prepared by the method of example 1) as a control group.
FIG. 3 provides a comparison of fluorescence signal enhancement effects in a Invitrogen iBright 1500 fluorescence imaging system with excitation light from top to bottom, signal received on top, detection samples water, rhodamine 6G (10. Mu.M) and rhodamine B (10. Mu.M). It can be seen from the figure that the optical cavity container provided in example 1 has a remarkable enhancement effect on fluorescence intensity.
FIG. 4 provides a comparison of fluorescence signal enhancement effects in a PerkinElmer EnVision multifunctional microplate reader, with excitation light from top to bottom, signal received on top, and sample tested as water and tetraphenyl ethylene (2.5. Mu.M) fluorochrome. It can be seen from the figure that the optical cavity container provided in example 1 has a remarkable enhancement effect on fluorescence intensity.
Fig. 5 provides a graph of raman spectral signal enhancement effect in a Horiba HR Evolution raman spectrometer with excitation light from top to bottom, signal received on top, and rhodamine 6G (0.5 μm) as the test sample. It can be seen from the figure that the optical cavity container provided in example 1 has a significant enhancement effect on raman signal intensity.
FIG. 6 provides a graph of the enhancement effect of the ultraviolet-visible spectrum signal in a PerkinElmer EnVision multifunctional microplate reader, wherein the excitation light is from bottom to top, the signal is received from top, and the detection sample is rhodamine B (10 mu M). There are two kinds of optical cavity containers for the control group, wherein the control group 1 is a conventional commercial optical cavity container (Corning 42592), and the control group 2 is a commercial ultraviolet analysis optical cavity container (Corning 3635). As can be seen from fig. 6, the optical cavity container of example 1 has a significant uv-vis enhancement capability, and in the uv band less than 290, 290 nm, the analysis capability has been completely lost due to the strong absorption of uv by the conventional PS cuvette, while the air cuvette is still able to be used normally, comparable to a commercial uv optical cavity container. The bottom of the optical cavity container of example 1 has a small hole with a diameter of 1.5 and mm, the background signal is lower based on the super-wetted hydrophobic structure and geometric constraint (because of air wrapping and no absorption of excitation light by other materials), and based on the optical enhancement principle, the optical cavity container has very low background noise and obvious ultraviolet-visible spectrum enhancement capability in the detection mode of the excitation light from bottom to top, and the ultraviolet analysis window range can be widened from 290 nm to 230 nm.
In order to further verify that the optical cavity containers of the present invention have good self-cleaning properties, the following experiments were performed: 50. Mu.L of BODIPY fluorescent dye (100 nM) was added to two different optical chamber containers, and after standing for 1 minute, the solutions in the two optical chamber containers were poured out, and then the fluorescent signal of the residue in the optical chamber containers was measured. The results are shown in fig. 7, where the nanointerface air-wrap optical cavity container has significant self-cleaning capability relative to commercially available commercial optical cavity containers, yet retains background interference from the substrate over 100 cycles. This shows that the self-cleaning performance of the super-wetted hydrophobic structure prepared in the optical cavity container of this example 1 is significantly improved.
It can be seen from the above embodiments that the present invention provides a new optical cavity container that by design of the container structure and materials forms a nearly fully encapsulated air layer between the liquid sample and the inner wall of the container. On one hand, the invention makes light have multiple refraction and reflection on the water/air interface, and then combines the design of the liquid geometry to make the sample liquid become an optical resonant cavity similar to a lens for concentrating and amplifying light; on the other hand, the photophysical process of the solute is affected by the molecular arrangement state of water on the three-phase contact interface of the water/air/container hydrophobic interface and the difference of the hydration shell structure formed by water and the solute. A significant enhancement of the spectral signal is finally achieved. In addition, the liquid optical cavity container has the advantages of good self-cleaning capability, reusability, good stability, suitability for various spectrum detection methods and the like. Therefore, the invention has good application prospect in spectrum detection.

Claims (10)

1. Optical cavity container based on air parcel liquid, its characterized in that: the optical cavity container is based on an air-wrapped liquid/air interface and an inner wall material structure of the optical cavity container, so that a liquid sample in the optical cavity container becomes an optical resonant cavity, and the optical resonant cavity has the effect of amplifying light intensively.
2. The optical cavity receptacle of claim 1, wherein: the inner surface of the optical cavity container is provided with a super-wetting hydrophobic structure, and when the optical cavity container is used for optical signal detection, an air layer wrapping the liquid sample is formed between the liquid sample and the inner wall of the container, and an air/liquid interface with abrupt refractive index changes is obtained.
3. An optical cavity receptacle according to claim 2, wherein: the thickness of the super-wetting hydrophobic structure is 10-500 mu m.
4. An optical cavity receptacle according to claim 2, wherein: the super-wetting hydrophobic structure is prepared by adopting methods of spraying, coating, spin coating, photoetching, nanoimprint or vapor deposition.
5. An optical cavity receptacle according to claim 2, wherein: the super-wetting hydrophobic structure is prepared by adhering hydrophobic nano particles on the inner surface of the optical cavity container through an adhesive.
6. The optical cavity receptacle of claim 5, wherein: the hydrophobic nano particles are selected from at least one of hydrophobic nano silicon dioxide or hydrophobic nano titanium dioxide;
and/or the adhesive is at least one of polyacrylate adhesive, polyurethane adhesive, polytetrafluoroethylene adhesive, rubber adhesive or phenolic resin adhesive.
7. The optical cavity receptacle of claim 1, wherein: the optical cavity container is a square optical cavity container, a round optical cavity container, an annular optical cavity container, a U-shaped optical cavity container, a Y-shaped optical cavity container, a multi-channel optical cavity container, a flat bottom configuration optical cavity container, an elliptic bottom configuration optical cavity container or a conical sharp bottom configuration optical cavity container.
8. The optical cavity receptacle of claim 1, wherein: the optical cavity container is used for detecting fluorescence spectrum, raman spectrum, ultraviolet spectrum or X-ray spectrum.
9. Use of the optical cavity vessel according to any of claims 1-8 in spectroscopic detection.
10. A method of spectral detection, characterized by: spectroscopic testing of a liquid sample carried by an optical cavity container according to any of claims 1-8.
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