CN106092906B - A kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence - Google Patents
A kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/19—Dichroism
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- G—PHYSICS
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/41—Refractivity; Phase-affecting properties, e.g. optical path length
- G01N21/4133—Refractometers, e.g. differential
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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
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
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Abstract
The present invention relates to a kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence.The continuous light of wide range of Supercontinuum source outgoing whole beam after the first lens obtains directional light, it is modulated into the linearly polarized light with One Dimension Periodic metal slot structure at first angle through the adjustable polarizer, is incident to the light transmitted after the chiral sample to be measured for being attached to One Dimension Periodic metallic channel body structure surface after the second lens focus by spectrometer collection；Adjusting the adjustable polarizer again is modulated into directional light with One Dimension Periodic metal slot structure into the linearly polarized light with first angle at the second angle of apposing symmetric angle, is again incident on the light transmitted after chiral sample to be measured after the second lens focus by spectrometer collection；According to the transmitted spectrum acquired twice, the circular dichroism signal and refractive index for obtaining chiral sample to be measured can be calculated.Test method of the present invention is simple, and the element that the present invention uses all is universal elements, therefore the complete machine cost of invention system is very low, has very big promotional value.
Description
Technical field
The present invention relates to Molecular Spectroscopy field, especially a kind of circular dichroism spectra and refractive index based on linearly polarized light incidence
Measuring system.
Background technique
In many drug molecules, the molecular formula of enantiomter is identical, but wherein atom or atomic radical in space
Configuration it is different, mirror image each other.Our this molecules that cannot be overlapped with itself mirror-image structure are referred to as chiral molecules.Many biologies
Molecule such as protein, DNA, amino acid etc. makes them can not mirror image weight with oneself due to their space structure structural properties
It closes, they are also chiral molecules.The space chirality feature of these molecules is directly and the function of molecule is closely bound up therefore chiral
The chiral analysis of molecule is most important.
The most directly effective technology of molecular chiral analysis at present is circular dichroism (circular dichroism, CD).
The principle of the technology is that chiral molecules absorbs difference to left and right circular polarisation.When the monochromatic left-handed circularly polarized light irradiation with dextrorotation is a certain
When kind chirality sample, the chirality sample is different to the absorption (absorption, A) of left and right rounding polarised light.This chiral molecules
Difference is absorbed at different wavelengths is known as circular dichroism spectra.
As can be seen that circular dichroism detection most essential steps are to generate chiral opposite left and right circularly polarized light.Quotient at present
Circularly polarised wave in the circular dichroism instrument of industry is generated by light ball modulator.Light ball modulator is mainly suitable by one piece
When translucent material (such as fused quartz or calcirm-fluoride etc.) be attached on piezoelectric transducer and form.Using photoelastic effect, it can make
Linearly polarized light becomes the left circularly polarized light and right-circularly polarized light of the higher-order of oscillation.In this way when incident linearly polarized light is by monochromator
After monochromatization, alternate left-handed and right-circularly polarized light, irradiating sample and sample have been reformed into after modulating by photoelastic modulation
Interaction.If chiral sample, then different to the absorption of left and right rounding polarised light, lead to the light transmissive light of left and right circular polarisation
Energy is different, finally by collecting stable circular dichroism by lock-in amplifier again after the amplification to faint transmission difference signal
Signal.Since light ball modulator can only once work to a wavelength, step motor control monochromator must also be passed through
Length scanning is carried out, the circular dichroism in the broadband of the sample can have just been obtained.
Although traditional round dichrometer device has had commercial product, traditional circular dichroism instrument have it is certain not
Foot limits its extensive use.First, it there are certain requirements sample, usually need solution example being put into Centimeter Level
It is measured in long sample cell, the light and sample to guarantee incident have enough the interaction distances.In this way to sample have one most
The requirement of low amounts, therefore it cannot achieve the measurement to few chiral sample；Second, since the light ball modulator of use is primary only
Modulating action can be played to a specific wavelength, therefore to obtain the circular dichroism signal on wide range, incident light has to pass through list
Color device carries out length scanning, and the circular dichroism value under each wavelength of scanning survey causes the circular dichroism of entire wide spectrum to be surveyed in this way
Try time increase.Third, traditional round dichroscope spectra system is complicated, and there are many optical device used, therefore is commercialized instrument price
Valuableness, and regular maintenance cost is very high, and common laboratory can not be born.4th, usual chiral molecules solution example in addition to
It measures and also needs to measure its other optical parameters such as refractive index outside its circular dichroism, but traditional round dichroscope spectrometer device is not
The function of having refractive index detection.This causes to test the same sample, needs again by other instruments, this is very big to measurement band
Inconvenience makes test period elongated.
Exactly because there are disadvantages mentioned above, the detections of more cheap, convenient and fast circular dichroism for traditional round dichroscope spectrometer
Method is always the hot spot of scientific circles' research.Therefore, it is cheaper and be able to achieve circular dichroism and sample to design a kind of cost
The system of the dual measurement of refractive index goes to be of great importance instead of the import business circular dichroism instrument of existing valuableness.
Summary of the invention
The purpose of the present invention is to provide a kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence, should
System detection method is simple, and the element that the present invention uses all is universal elements, therefore the complete machine cost of invention system is very low,
With very big promotional value.
To achieve the above object, the technical scheme is that a kind of circular dichroism spectra and folding based on linearly polarized light incidence
Penetrate rate measuring system, including Supercontinuum source, the first lens, the adjustable polarizer, One Dimension Periodic metal slot structure, the second lens,
Spectrometer；The continuous light of wide range of the Supercontinuum source outgoing whole beam after the first lens obtains directional light, then through adjustable
Inclined device is modulated into the linearly polarized light with One Dimension Periodic metal slot structure at first angle, is incident to and is attached to One Dimension Periodic metallic channel knot
The chiral sample to be measured on structure surface, the light then transmitted is after the second lens focus by the spectrometer collection；Adjusting again can
Adjust the polarizer make directional light be modulated into One Dimension Periodic metal slot structure at first angle at apposing symmetric angle second
The linearly polarized light of angle is incident to the chiral sample to be measured for being attached to One Dimension Periodic metallic channel body structure surface, the light warp then transmitted
By the spectrometer collection after second lens focus；It is to be measured can to calculate acquisition according to the transmitted spectrum acquired twice for spectrometer
The circular dichroism signal and refractive index of chiral sample.
In an embodiment of the present invention, the first angle and second angle are respectively+45 ° and -45 °, -30 ° and+30 °
Or -60 ° and+60 °.
In an embodiment of the present invention, spectrometer is according to the transmitted spectrum acquired twice, the absorption spectrum being calculated
Difference, i.e., the circular dichroism signal of chiral sample to be measured.
In an embodiment of the present invention, spectrometer is maximum in the absorption spectrum being calculated according to the transmitted spectrum of acquisition
Absorb the refractive index that position detects chiral sample to be measured to external dielectric environment sensitivity characteristic.
In an embodiment of the present invention, the One Dimension Periodic metal slot structure is single-layer or multi-layer.
In an embodiment of the present invention, the One Dimension Periodic metal slot structure is support surface plasma resonance efficiency
Noble metal, including gold, silver, aluminium.
In an embodiment of the present invention, the size of the One Dimension Periodic metal slot structure is sub-wavelength magnitude.
Compared to the prior art, the invention has the following advantages: present system, with metal under linearly polarized light incidence
Micro-nano sensing arrangement generates the chiral electric field of local on the surface of sensor structure, for measuring micro chiral sample；The system
It does not need to use the expensive circular polarization polarizer (such as light ball modulator) by the incident beam modulated as traditional round dichroscope spectra system
It interacts again with sample for circularly polarized light, and obtains the light field and sample of different chiralitys only by incident polarization angle is changed
Effect, so that it may obtain the circular dichroism signal of sample, test method is simple；Simultaneously using sensing arrangement absorption maximum position to Jie
Electrical environment sensitivity characteristic realizes the refractive index sensing to sample using the crest location variation of absorption spectra, and of the invention is
System has the ability of circular dichroism and refractive index dual sensing, and measurement method is novel；Include in scheme disclosed by the invention
Element is all universal elements, therefore the complete machine cost of invention system is very low, has very big promotional value.
Detailed description of the invention
Fig. 1 is linear polarization incidence circular dichroism measuring system schematic diagram proposed by the present invention.
Fig. 2 is the structure chart of One Dimension Periodic multiple layer metal sensor slot employed in embodiment.
Fig. 3 is the difference of the absorption spectra of+45 ° and -45 ° of linear polarization incidence after filling different chiral samples in embodiment, namely
The circular dichroism signal of sample.
Fig. 4 is the knot that One Dimension Periodic multiple layer metal sensor slot senses different refractivity sample employed in embodiment
Fruit figure.
Specific embodiment
With reference to the accompanying drawing, technical solution of the present invention is specifically described.
A kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence of the present invention, including Supercontinuum source,
First lens, the adjustable polarizer, One Dimension Periodic metal slot structure, the second lens, spectrometer；The width of the Supercontinuum source outgoing
It composes continuous light whole beam after the first lens and obtains directional light, be then modulated into and One Dimension Periodic metal slot structure through the adjustable polarizer
At the linearly polarized light of first angle, it is incident to the chiral sample to be measured for being attached to One Dimension Periodic metallic channel body structure surface, is then transmitted
Light after the second lens focus by the spectrometer collection；Adjust again the adjustable polarizer make directional light be modulated into it is one-dimensional
Period metal slot structure is incident at the linearly polarized light with first angle at the second angle of apposing symmetric angle and is attached to one-dimensional week
The chiral sample to be measured of phase metallic channel body structure surface, the light then transmitted is after the second lens focus by the spectrometer collection；
Spectrometer can calculate the circular dichroism signal for obtaining chiral sample to be measured and refraction according to the transmitted spectrum acquired twice
Rate.
The first angle and second angle be respectively+45 ° with -45 °, -30 ° and+30 ° or -60 ° and+60 ° etc. at opposite
Claim angle.
Spectrometer is according to the transmitted spectrum acquired twice, the difference for the absorption spectrum being calculated, i.e., chiral sample to be measured
Circular dichroism signal.Spectrometer is according to the transmitted spectrum of acquisition, and absorption maximum position is external in the absorption spectrum being calculated
Portion's dielectric environment sensitivity characteristic detects the refractive index of chiral sample to be measured.
The One Dimension Periodic metal slot structure is single-layer or multi-layer.The One Dimension Periodic metal slot structure is support surface etc.
The noble metal of gas ions resonance efficiency, including gold, silver, aluminium.The size of the One Dimension Periodic metal slot structure is sub-wavelength magnitude.
The following are specific implementation process of the invention.
Refering to Figure 1, Fig. 1 is that linear polarization incidence One Dimension Periodic multiple layer metal sensor slot provided by the invention is realized
The system structure diagram of circular dichroism measurement and refractive index sensing, the system include:
LS is continuous white light source, uses its emergent light after the polarizer becomes linearly polarized light as the light of sample test
Source；Lens L1 is used to the light source LS light issued becoming directional light, and P is the adjustable linear polarization polarizer, for will be incident non-
Polarised light is adjusted to the linearly polarized light with periodic slots in senser element at+45 ° and -45 ° directions；Sensor Sensor is one-dimensional week
Phase micro-nano multiple layer metal slot structure is the core sensing arrangement of system, total for generating plasma with incident light interaction
Shaking and generating in body structure surface enhances chiral electromagnetic field, and chiral sample interaction；Lens L2 for handle and sensor and its
Transmitted light after the interaction of surface sample, which focuses, is convenient for subsequent spectrometer collection；SP is spectrometer, for measuring
Penetrate spectrum；PC is the computer for connecting spectrum, is analyzed for data processing and signal.
The continuous light of wide range of light source hair obtains directional light by the whole beam of lens, then passes through the linear polarization in an adjustable direction
The polarizer obtains the linearly polarized light of specific direction, and linearly polarized light is incident on period multiple layer metal slot sensing arrangement and structure is mutual
Act on excitating surface plasma resonance effect.Since the subsidiary effect delay of plasma resonance causes to occur on sensing arrangement surface
The enhancing chirality electromagnetic field of height local.Sample is attached to the surface of sensing arrangement, just can be excited chirality electricity
Magnetic field interaction.By changing incident polarization direction, the chirality of available local electromagnetic field is different, so using twice
Incident realize of different polarization light measures the circular dichroism of same sample.In addition, due to surface plasma resonance position pair
The dielectric environment of sensor surrounding is very sensitive, and since utmostly local in inside configuration causes to tie electric field at resonance
Structure has a significant losses to incident light, this significant losses shows as wave crest in absorption spectrum, therefore can use absorption
Compose sensing of the medium wave peak to the realization of external dielectric environment sensitivity characteristic to sample dielectric parameter such as refractive index.
The concrete operations of present system in two steps, adjust polarization direction and biography that the polarizer (P) makes incident light first
The multiple layer metal slot of sensor be in+45 °, due to plasma resonance effect and its caused by phase delay effect can be in sensor surface
Nearby generating chiral electromagnetic field that is to say similar left elliptically polarized light.Tested chirality sample is put into sensor surface and participates in and generate
Chiral electric field interaction, the light then transmitted after over-focusing be collected；Second step, the adjustment polarizer (P) make incidence
The polarization direction of light be and sensor multiple layer metal slot is at -45 ° of apposing symmetric angle actuated sensor part again, due to changing
Become to incident polarization direction, opposite chiral electromagnetic field namely similar right elliptically polarized light are then generated in sensor surface, is swashed
Transmission is by spectrometer collection after the sample interaction of the opposite chiral electromagnetic field and sensor surface of hair.It is recorded twice difference
Transmitted spectrum T (+45 °) and T (- 45 °) under polarization angle, the absorption spectrum measured twice by A=1-T formula, A (+
45 °) and A (- 45 °).
One Dimension Periodic multiple layer metal sensor slot can realize that tested chiral sample exists by other additional devices such as stream ponds
Multiple layer metal slot sensing surface adequately immerses contact.The chiral electromagnetic field phase of the tested chiral sample and excitation of sensor surface
Interaction, due to right+45 ° of chiral sample it is different with the opposite-handed light field absorption generated under -45 ° of polarisation excitations ,+45 °
Difference is had with the absorption spectrum of -45 ° of polarized incident situations namely Δ A=A (+45 °)-A (- 45 °) is not zero, this difference signal
Caused by Δ A is the chirality as the sample filled, the circular dichroism signal of the sample measured that is to say.
The surface plasma resonance wavelength that the crest location of absorption spectra excites this, it and sample refractive index have an a pair
The relationship answered, therefore can use the position of absorption spectrum medium wave peak to detect the variation of the refractive index of sample.
It is the One Dimension Periodic multiple layer metal sensor slot structural schematic diagram in embodiment shown in attached drawing 2.On sensor structure
Face is the sandwich structure for exciting chiral electric field, and here is the matrix of transparent to light.Every thickness degree is all in sandwich structure
It is 100nm, structural cycle is 450nm, groove width 225nm.The material of upper layer and lower layer structure is the metal for supporting plasma resonance, this
In preferably gold, middle layer is dielectric material.Matrix is optically transparent material, selects silica here.
After attached drawing 3 assumes that the different chiral samples of attached sensor surface filling shown in Fig. 2 ,+45 ° and -45 ° obtained are partially
Absorption spectrum difference signal Δ A under vibration.According to being analyzed above, this difference signal that is to say the circular dichroism light of tested chiral sample
Spectrum.Result assumes that the chiral sample being filled is enantiomer in figure, their dielectric parameter ε=1+0.01i, their chiral phase
The Pasteur parameter of pass is κ=+ 0.001i and κ=- 0.001i respectively.The difference of the symbology chirality sample of κ value is chiral.By
Figure it can be seen that the circular dichroism spectra of enantiomer (opposite-handed) sample that present system obtains be it is symmetrical about zero curve, this and
Practical theory is consistent, to also demonstrate the feasibility of the present invention program.
Influence of the sample refractive index to sensor absorption maximum spectral position in 4 present system of attached drawing.As can be seen that with
The absorption maximum spectral position that the change system of sample refractive index measures is also with change.Moreover, as shown in embedded figure, sample
Refractive index and absorption maximum spectrum wavelength position have a very high linear correlation degree, sensing sensitivity reaches the refraction of 207nm per unit
Rate, this has absolutely proved that this system can be used for the refractive index sensing to test sample simultaneously.
From above-described embodiment as can be seen that system provided by the invention can measure the circular dichroism light of chiral sample really
Spectrum.Its structure is simple, low in cost, easy to operate.Meanwhile it is quick to sample dielectric parameter using absorption maximum position in absorption spectra
The dual sensing to sample refractive index may be implemented in sense characteristic.Due to only needing for sample to be attached to the table of sensor micro-nano structure
Face, therefore the invention system is particularly suitable for the analysis application to denier sample, there is very big application value in practice.
Particular embodiments described above is to have carried out to the purpose of the present invention, technical scheme and beneficial effects further in detail
It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all
Within the spirit and principle of invention, any modification, equivalent substitution, improvement and etc. made are (as changed sensor micro-nano structure ruler
Very little, shape, material), it should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence, it is characterised in that: including super continuum light
Source, the first lens, the adjustable polarizer, One Dimension Periodic metal slot structure, the second lens, spectrometer；The Supercontinuum source outgoing
The continuous light of wide range after the first lens whole beam obtain directional light, be then modulated into and One Dimension Periodic metallic channel through the adjustable polarizer
Knot constitutes the linearly polarized light of first angle, is incident to the chiral sample to be measured for being attached to One Dimension Periodic metallic channel body structure surface, then
The light of transmission is after the second lens focus by the spectrometer collection；Adjust again the adjustable polarizer make directional light be modulated into
One Dimension Periodic metal slot structure is incident at the linearly polarized light with first angle at the second angle of apposing symmetric angle and is attached to one
The chiral sample to be measured of period metallic channel body structure surface is tieed up, the light then transmitted is adopted after the second lens focus by the spectrometer
Collection；Spectrometer can calculate the circular dichroism signal and folding for obtaining chiral sample to be measured according to the transmitted spectrum acquired twice
Penetrate rate；The first angle and second angle are respectively+45 ° and -45 °, -30 ° and+30 ° or -60 ° and+60 °.
2. a kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence according to claim 1, special
Sign is: spectrometer is according to the transmitted spectrum acquired twice, the difference for the absorption spectrum being calculated, i.e., the circle of chiral sample to be measured
Dichroscope spectrum signal.
3. a kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence according to claim 1, special
Sign is: spectrometer is according to the transmitted spectrum of acquisition, and absorption maximum position is to external dielectric collar in the absorption spectrum being calculated
Border sensitivity characteristic detects the refractive index of chiral sample to be measured.
4. a kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence according to claim 1, special
Sign is: the One Dimension Periodic metal slot structure is single-layer or multi-layer.
5. a kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence according to claim 1, special
Sign is: the One Dimension Periodic metal slot structure is the noble metal of support surface plasma resonance efficiency, including gold, silver, aluminium.
6. a kind of circular dichroism spectra and refractometry system based on linearly polarized light incidence according to claim 1, special
Sign is: the size of the One Dimension Periodic metal slot structure is sub-wavelength magnitude.
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| US11506602B2 (en) * | 2018-05-15 | 2022-11-22 | The Administrators Of The Tulane Educational Fund | Refractive-index sensor and method |
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| CN109387481A (en) * | 2018-11-28 | 2019-02-26 | 同济大学 | A kind of apparatus and method detecting circular dichroism |
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| CN106092906A (en) | 2016-11-09 |
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