CN108020504A - Optical measuring instrument and sample refractive index, optical rotatory spectrum and chiral molecules Enantiomeric excess measurement analysis method based on the weak measurement of quantum - Google Patents
Optical measuring instrument and sample refractive index, optical rotatory spectrum and chiral molecules Enantiomeric excess measurement analysis method based on the weak measurement of quantum Download PDFInfo
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Abstract
本发明公开了一种基于量子弱测量的光学测量仪以及样品折射率、旋光谱和手性分子对映体含量测量分析方法,本发明基于量子弱测量技术,在测量光路中,以入射光路中的前选择量子态与反射光路中的第一后选择量子态之间构造第一量子弱测量光路,以入射光路中的前选择量子态与折射光路中的第二后选择量子态之间构造第二量子弱测量光路,通过调整入射光束、反射光束和折射光束偏振态,可以使反射光束自旋分裂值和折射光束自旋分裂值扩大至少103倍,从而实现对样品折射率极小改变、微弱手征光信号(例如旋光角)、手性分子对映体含量的测定,有望在单分子层面实现对手性药物的分析;在生物医学工程、生命科学、分析化学等多个学科领域具有重要应用价值。
The invention discloses an optical measuring instrument based on quantum weak measurement and a method for measuring and analyzing sample refractive index, spin spectrum and chiral molecule enantiomer content. The invention is based on quantum weak measurement technology. Construct the first quantum weak measurement optical path between the pre-selected quantum state and the first post-selected quantum state in the reflected optical path, and construct the second quantum weak measurement optical path between the pre-selected quantum state in the incident optical path and the second post-selected quantum state in the refracted optical path The two-quantum weak measurement optical path, by adjusting the polarization state of the incident beam, reflected beam and refracted beam, can expand the spin splitting value of the reflected beam and the spin splitting value of the refracted beam by at least 10 3 times, thereby achieving minimal changes in the refractive index of the sample, The determination of weak chiral optical signals (such as optical rotation angle) and enantiomeric content of chiral molecules is expected to realize the analysis of chiral drugs at the single molecule level; it is of great importance in biomedical engineering, life sciences, analytical chemistry and other disciplines. Value.
Description
技术领域technical field
本发明涉及光学仪器技术,具体涉及一种基于量子弱测量的光学测量仪,采用该光学测量仪,能够同时测定液态、气态或固态透明样品的折射率和旋光谱,特别是较低浓度、较少手性分子溶液的折射率和旋光谱;采用该光学测量仪,还可以实现对含有手性分子物质的溶液中对映体含量的测定,该基于量子弱测量的光学测量仪可适用于高精度手性药物分析、手性化学分析,并可用于制作高灵敏度手性分子传感器等。The invention relates to optical instrument technology, in particular to an optical measuring instrument based on quantum weak measurement. The optical measuring instrument can simultaneously measure the refractive index and rotational spectrum of liquid, gaseous or solid transparent samples, especially those with lower concentrations and relatively low concentrations. Refractive index and rotational spectrum of a solution with few chiral molecules; with this optical measuring instrument, the determination of enantiomer content in a solution containing chiral molecular substances can also be realized. The optical measuring instrument based on quantum weak measurement can be applied to high Accurate chiral drug analysis, chiral chemical analysis, and can be used to make high-sensitivity chiral molecular sensors, etc.
背景技术Background technique
自然界中的化学分子和生物大分子如DNA、蛋白质、多糖、核酸等都具有手性特征,导致化学和生物学(物质的生化)过程常伴随着分子构型的变化,并关联着弱手征光信号改变。而人体中的药物靶点本身具有手性特征(如各种受体、酶、蛋白质等都由L-型氨基酸组成),当与手性药物的对映体发生作用时,相应的药理活性、代谢过程及毒性等存在显著的差异,甚至表现出相反的药理学活性。因此,现在药物在研制成功后,都要经过严格的手征活性和毒性实验,以避免其中所含的另一种手性分子对人体健康产生不良影响。Chemical molecules and biological macromolecules in nature, such as DNA, protein, polysaccharide, nucleic acid, etc., all have chiral characteristics, resulting in chemical and biological (biochemical) processes often accompanied by changes in molecular configuration and associated with weak chirality The light signal changes. However, the drug targets in the human body have chiral characteristics (such as various receptors, enzymes, proteins, etc. are composed of L-type amino acids), when they interact with the enantiomers of chiral drugs, the corresponding pharmacological activity, There are significant differences in metabolic process and toxicity, and even show opposite pharmacological activities. Therefore, now, after the drug is successfully developed, it must undergo strict chiral activity and toxicity tests to avoid adverse effects of another chiral molecule contained therein on human health.
鉴于对手性药物在药理活性、生理作用即代谢过程中差异的充分认识,人们加大了对手性药物的研发力度,使其得到蓬勃发展,已占据当今世界常用化学药物研发的三分之二以上。精确的手性药物分析技术是手性药物研发的重要基石,而手性分子对映体含量的精确测定时是手性药物分析和手性化学分析的技术核心及关键瓶颈。In view of the full understanding of the differences in pharmacological activity, physiological effects, and metabolic processes of chiral drugs, people have increased the research and development of chiral drugs, making them flourish, accounting for more than two-thirds of the research and development of commonly used chemical drugs in the world today. . Accurate chiral drug analysis technology is an important cornerstone of chiral drug research and development, and the accurate determination of the enantiomer content of chiral molecules is the technical core and key bottleneck of chiral drug analysis and chiral chemical analysis.
目前,测定物质的手征光信号(圆二色谱和旋光角)是检测药物分子光学活性、确定分子对映体绝对构型的有效方法。然而,手征光信号(Chiroptical)是一种非常弱的光学效应,通常情况下,只有非手性背景吸收信号的10-6~10-4量级(对于弱手性药物或生物分子相互作用过程,手征光信号更加微弱),采用现有的光学测量设备直接测量比较困难,美国鲁道夫公司旋光仪Autopol系列,通过偏振消光的方法对旋光度的测量精度最高到达0.002°,但由于传统基于光强的测量技术受到光源稳定性、环境噪声、温度等固有因素的影响,其测量精度已与仪器噪声水平相当,很难再进一步提高。此外,现有的旋光测量设备尚不具备测量不同手性对映体含量的功能。At present, the determination of chiral optical signals (circular dichroism and optical rotation angle) of substances is an effective method to detect the optical activity of drug molecules and determine the absolute configuration of molecular enantiomers. However, the chiroptical optical signal (Chiroptical) is a very weak optical effect, usually only on the order of 10 -6 ~ 10 -4 of the achiral background absorption signal (for weak chiral drugs or biomolecular interactions process, the chiral optical signal is even weaker), it is difficult to directly measure with existing optical measuring equipment, and the Autopol series of polarimeters from Rudolph Company in the United States can measure the optical rotation with the highest accuracy of 0.002° through the method of polarization extinction, but due to the traditional The measurement technology based on light intensity is affected by inherent factors such as light source stability, environmental noise, temperature, etc., and its measurement accuracy is already equivalent to the noise level of the instrument, and it is difficult to further improve it. In addition, the existing optical polarimetry equipment does not yet have the function of measuring the content of different chiral enantiomers.
发明内容Contents of the invention
本发明的目的旨在首先提供一种基于量子弱测量的光学测量仪,不仅能够实现对透明或半透明样品的折射率和旋光谱的测量分析,还可以实现对手性分子对映体含量的测量分析。The purpose of the present invention is to firstly provide an optical measuring instrument based on quantum weak measurement, which can not only realize the measurement and analysis of the refractive index and rotational spectrum of transparent or translucent samples, but also can realize the measurement of the enantiomer content of chiral molecules analyze.
本发明的第二个目的在于基于上述基于量子弱测量的光学测量仪,提供一种基于量子弱测量的样品折射率和旋光谱测量分析方法。The second object of the present invention is to provide a method for measuring and analyzing the refractive index and rotational spectrum of a sample based on quantum weak measurement based on the above-mentioned optical measuring instrument based on quantum weak measurement.
本发明的第三个目的在于针对现有技术中缺乏精确测定手性分子对映体含量技术手段的问题,提供一种基于量子弱测量的手性分子对映体含量测量分析方法。The third purpose of the present invention is to provide a method for measuring and analyzing the enantiomer content of chiral molecules based on quantum weak measurement, aiming at the lack of technical means for accurately measuring the enantiomer content of chiral molecules in the prior art.
本发明的思路,将待测样品的折射率和旋光谱转换为与光子自旋分裂相关的测量量,由于光子自旋分裂对折射率和旋光度都非常敏感,却对光源的波动性和环境噪声不敏感,因此可以很好的抑制噪声,提高测量精度。光子的自旋分裂可通过量子弱测量放大(表现为通过前、后偏振态后,探测器上光斑的质心位置移动距离,光斑的质心位置即光斑依据能量分布计算得到的能量重心位置),进行精确测定,从而同时获得待测样品高精度的折射率和旋光谱,并通过这两个参数得到样品中对映体的含量。基于上述分析,本发明旨在研发一种装置,光束入射到样品介质表面、经样品介质表面反射或折射,通过调整入射光束、反射光束或折射光束的偏振态或相位差,使与偏振态或相位差相关联的自旋分裂值(即反射光束质心或折射光束质心相对于样品介质界面处光束能量重心的横移距离,简称反射光束质心横移距离或折射光束质心横移距离)扩大,从而可以对其进行精确测定,再依据测定的反射光束或折射光束的自旋分裂值,计算获得样品的折射率和旋光谱。对于含有手性分子物质的溶液,手性分子对映体含量与溶液折射率和旋光度相关,而溶液折射率和旋光度可以由与偏振态或相位差相关联的自旋分裂值计算得到,因此可以基于量子弱测量技术确定的自旋分裂值来精确测定手性分子对映体含量。The idea of the present invention is to convert the refractive index and rotation spectrum of the sample to be measured into the measurement quantity related to the photon spin splitting. Since the photon spin splitting is very sensitive to the refractive index and optical rotation, it is not sensitive to the fluctuation of the light source and the environment. The noise is insensitive, so it can suppress the noise very well and improve the measurement accuracy. The spin splitting of photons can be amplified by quantum weak measurement (expressed as the moving distance of the center of mass position of the light spot on the detector after passing through the front and rear polarization states, and the position of the center of mass of the light spot is the position of the energy center of gravity of the light spot calculated according to the energy distribution). Accurate measurement, so as to obtain high-precision refractive index and rotational spectrum of the sample to be tested at the same time, and obtain the content of the enantiomer in the sample through these two parameters. Based on the above analysis, the present invention aims to develop a device in which the light beam is incident on the surface of the sample medium, reflected or refracted by the surface of the sample medium, by adjusting the polarization state or phase difference of the incident light beam, reflected light beam or refracted light beam, so that the polarization state or The spin splitting value associated with the phase difference (that is, the traversing distance of the center of mass of the reflected beam or the center of mass of the refracted beam relative to the center of gravity of the beam energy at the interface of the sample medium, referred to as the traversing distance of the center of mass of the reflected beam or the traversing distance of the center of mass of the refracted beam) expands, thereby It can be accurately measured, and then the refractive index and spin spectrum of the sample can be calculated according to the spin splitting value of the measured reflected beam or refracted beam. For solutions containing chiral molecular species, the enantiomeric content of chiral molecules is related to the solution refractive index and optical rotation, which can be calculated from the spin-splitting values associated with polarization states or phase differences, The enantiomeric content of chiral molecules can thus be precisely determined based on the spin-splitting values determined by quantum weak measurement techniques.
本发明提供的一种基于量子弱测量的光学测量仪,包括光发生装置、偏振态制备器、棱镜、样品、第一偏振态选择器、第二偏振态选择器、第一光接收装置、第二光接收装置;所述样品设计有光入射面和光出射面,其光入射面与棱镜的一个侧面相贴合;由光发生装置出射的光束经偏振态制备器、棱镜入射到样品的光入射面,产生反射光束和折射光束,反射光束经第一偏振态选择器由第一光接收装置接收,折射光束经第二偏振态选择器由第二光接收装置接收;入射到样品光入射面的光束偏振态为前选择量子态,反射光束经第一偏振态选择器后的光束偏振态为第一后选择量子态,折射光束经第二偏振态选择器后的光束偏振态为第二后选择量子态;入射光路中的前选择量子态与反射光路中的第一后选择量子态之间构成第一量子弱测量光路部分,入射光路中的前选择量子态与折射光路中的第二后选择量子态之间构成第二量子弱测量光路部分。An optical measuring instrument based on quantum weak measurement provided by the present invention includes a light generating device, a polarization state preparation device, a prism, a sample, a first polarization state selector, a second polarization state selector, a first light receiving device, and a second polarization state selector. Two light-receiving devices; the sample is designed with a light incident surface and a light exit surface, and its light incident surface is attached to one side of the prism; the light beam emitted by the light generating device enters the light incident of the sample through the polarization state preparation device and the prism The reflected beam and the refracted beam are generated on the surface, the reflected beam is received by the first light receiving device through the first polarization state selector, and the refracted beam is received by the second light receiving device through the second polarization state selector; The polarization state of the beam is the pre-selected quantum state, the beam polarization state of the reflected beam after passing through the first polarization state selector is the first post-selection quantum state, and the beam polarization state of the refracted beam after passing through the second polarization state selector is the second post-selection state Quantum state; the pre-selected quantum state in the incident light path and the first post-selected quantum state in the reflection light path constitute the first quantum weak measurement light path part, the pre-selected quantum state in the incident light path and the second post-selection in the refraction light path The second quantum weak measurement optical path is formed between the quantum states.
上述基于量子弱测量的光学测量仪,通过调整前选择量子态与第一后选择量子态之间的夹角或者前选择量子态与第二后选择量子态之间的夹角,可以扩大得到的反射光束自旋分裂值或折射光束自旋分裂值,从而确保对溶液折射率测定或旋光角测定精度;当所述第一后选择量子态与前选择量子态之间的夹角为90°±△’(△’不大于5°)时,反射光束自旋分裂值相对于入射光束自旋分裂值可以扩大至少103倍;当所述第二后选择量子态与前选择量子态之间的夹角为90°±△’(△’不大于5°),折射光束自旋分裂值相对于入射光束自旋分裂值可以扩大至少103倍。The above-mentioned optical measuring instrument based on quantum weak measurement can expand the obtained Spin-splitting value of reflected beam or spin-splitting value of refracted beam, so as to ensure the measurement accuracy of solution refractive index or optical rotation angle; when the angle between the first post-selected quantum state and the pre-selected quantum state is 90°± When △'(△' is not greater than 5°), the spin splitting value of the reflected beam can be enlarged by at least 10 3 times relative to the spin splitting value of the incident beam; when the second post-selection quantum state and the pre-selection quantum state The included angle is 90°±△'(△' is not greater than 5°), and the spin splitting value of the refracted beam can be enlarged by at least 10 3 times relative to the spin splitting value of the incident beam.
上述基于量子弱测量的光学测量仪,所针对的样品为透明或半透明的固体、液体或气体;当样品为液体或气体时,测量时需要将其放入透明、半透明容器(容器折射率已知)中。The above-mentioned optical measuring instrument based on quantum weak measurement is aimed at a transparent or translucent solid, liquid or gas; when the sample is liquid or gas, it needs to be placed in a transparent or translucent container (container refractive index known).
上述基于量子弱测量的光学测量仪,所述光发生装置包括光源发生器以及设置于光源发生器出射光路上的能量调节器和第一光束变换器;所述光源发生器用于提供偏振光源,可以为激光器、激光二极管、超辐射发光二极管、白光发生器、量子光源发生器;所述能量调节器用于对由光源发生器发出的光束能量进行调节,可以为二分之一波片或中性衰减片;对于二分之一波片,通过调节其透振方向与入射光偏振方向的夹角实现对光能量的调节;所述第一光束变换器用于光束汇聚,可以为单个透镜或多个透镜组成的透镜组。In the above-mentioned optical measuring instrument based on quantum weak measurement, the light generating device includes a light source generator and an energy regulator and a first beam converter arranged on the outgoing light path of the light source generator; the light source generator is used to provide a polarized light source, which can It is a laser, a laser diode, a superluminescent light emitting diode, a white light generator, and a quantum light source generator; the energy regulator is used to adjust the beam energy emitted by the light source generator, and can be a half-wave plate or a neutral attenuation plate; for a half-wave plate, the light energy can be adjusted by adjusting the angle between the vibration transmission direction and the polarization direction of the incident light; the first beam converter is used for beam convergence and can be a single lens or multiple lenses composed of lens groups.
上述基于量子弱测量的光学测量仪,所述偏振态制备器用于构造合适的前选择量子态,所述第一偏振态选择器和第二偏振态选择器用于构造合适的后选择量子态,并使后选择量子态与前选择量子态接近垂直,夹角为90°±△’,△’不大于5°,以保证足够的量子弱值放大效应,实现高精度和高灵敏度的测量;所述偏振态制备器为偏振器或者偏振器与四分之一波片、相位补偿器(例如巴比涅相位补偿器)组合中的一种,四分之一波片或相位补偿器位于偏振器的后面;所述第一偏振态选择器、第二偏振态选择器结构相同或者不同,为偏振器或者偏振器与四分之一波片、相位补偿器(例如巴比涅相位补偿器)组合中的一种,四分之一波片或相位补偿器位于偏振器的前面;所述偏振器为格兰激光偏振棱镜或偏振分光镜(例如沃拉斯棱镜)。In the aforementioned optical measuring instrument based on quantum weak measurement, the polarization state preparer is used to construct a suitable pre-selected quantum state, the first polarization state selector and the second polarization state selector are used to construct a suitable post-selected quantum state, and The post-selected quantum state is close to perpendicular to the pre-selected quantum state, and the included angle is 90°±△', and △' is not greater than 5°, so as to ensure sufficient quantum weak value amplification effect and realize high-precision and high-sensitivity measurement; The polarization state preparation device is a combination of a polarizer or a polarizer with a quarter-wave plate and a phase compensator (such as a Babinet phase compensator), and the quarter-wave plate or phase compensator is located at the polarizer In the back; the first polarization state selector and the second polarization state selector have the same or different structures, and are in the combination of a polarizer or a polarizer and a quarter-wave plate and a phase compensator (such as a Babinet phase compensator) A quarter-wave plate or a phase compensator is located in front of the polarizer; the polarizer is a Glan laser polarizing prism or a polarizing beam splitter (such as a Wolas prism).
上述基于量子弱测量的光学测量仪,所述棱镜用于在样品入射界面产生合适的入射角度,在优选的方式中,经棱镜后的入射光束在样品入射界面产生布鲁斯特角反射或全反射等,棱镜可以为三棱镜、四棱镜、五棱镜等。In the above-mentioned optical measuring instrument based on quantum weak measurement, the prism is used to generate a suitable incident angle at the sample incident interface. In a preferred mode, the incident beam after passing through the prism produces Brewster angle reflection or total reflection at the sample incident interface. , the prism can be a triangular prism, a quadrangular prism, a pentaprism, etc.
上述基于量子弱测量的光学测量仪,所述第一光接收装置包括第一光电探测器以及位于第一光电探测器前方的第二光束变换器;所述第二光接收装置包括第二光电探测器以及位于第二光电探测器前方的第三光束变换器;所述第一光电探测器、第二光电探测器用于实现弱光探测,两者可以结构相同或者不同,为电荷耦合元件、光谱仪、光电倍增管、位置敏感探测器、四象限探测器中的一种;所述第二光束变换器和第三光束变换器用于将光束调节为平行光束,两者结构可以相同或者不同,为单个透镜或多个透镜组成的透镜组;所述第二光束变换器的等效焦距大于第一光束变换器的等效焦距,第一光束变换器与第二光束变换器构成共焦系统;所述第三光束变换器的等效焦距大于第一光束变换器的等效焦距,第一光束变换器与第三光束变换器构成共焦系统。In the above-mentioned optical measuring instrument based on quantum weak measurement, the first light receiving device includes a first photodetector and a second beam converter located in front of the first photodetector; the second light receiving device includes a second photodetector device and a third beam converter located in front of the second photodetector; the first photodetector and the second photodetector are used to realize weak light detection, and the two may have the same or different structures, which are charge-coupled elements, spectrometers, One of photomultiplier tubes, position-sensitive detectors, and four-quadrant detectors; the second beam converter and the third beam converter are used to adjust the beam to a parallel beam, and the structures of the two can be the same or different, and they are a single lens or a lens group composed of multiple lenses; the equivalent focal length of the second beam converter is greater than the equivalent focal length of the first beam converter, and the first beam converter and the second beam converter form a confocal system; the second beam converter The equivalent focal length of the three beam converters is greater than that of the first beam converter, and the first beam converter and the third beam converter constitute a confocal system.
本发明进一步提供了一种基于量子弱测量的样品折射率和旋光谱测量分析方法,采用上述基于量子弱测量的光学测量仪,测量分析步骤如下:The present invention further provides a sample refractive index and rotational spectrum measurement and analysis method based on quantum weak measurement. Using the above-mentioned optical measuring instrument based on quantum weak measurement, the measurement and analysis steps are as follows:
(1)由光发生装置发出的光经偏振态制备器、棱镜入射到样品入射界面产生反射光束和折射光束,反射光束经第一偏振态选择器由第一光接收装置接收,折射光束经第二偏振态选择器由第二光接收装置接收;通过第一光接收装置记录反射光束质心横移距离,将其作为反射光束光子自旋分裂值<yr>;通过第二光接收装置记录折射光束质心横移距离,将其作为折射光束光子自旋分裂值<yt>;(1) The light emitted by the light generating device enters the incident interface of the sample through the polarization state preparation device and the prism to generate reflected light beams and refracted light beams. The reflected light beams are received by the first light receiving device through the first polarization state selector, and the refracted light beams pass through the first polarization state selector. The two polarization state selectors are received by the second light receiving device; the center of mass traversing distance of the reflected beam is recorded by the first light receiving device, which is used as the photon spin splitting value <y r > of the reflected beam; the refraction is recorded by the second light receiving device Transverse distance of the beam center of mass, which is used as the photon spin splitting value <y t > of the refracted beam;
(2)根据如下公式(i)获得入射到样品光入射面的入射光束前选择量子态:(2) According to the following formula (i), the quantum state selected before the incident beam incident on the light incident surface of the sample is obtained:
其中,为入射光束的横向波矢,为入射光束的波型函数,i代表入射光束,|ψi>为入射光束经偏振态制备器后的偏振态;in, is the transverse wave vector of the incident beam, is the wave mode function of the incident beam, i represents the incident beam, |ψ i > is the polarization state of the incident beam after it passes through the polarization state generator;
(3)根据如下公式(ii)获得反射光束经第一偏振态选择器后的第一后选择量子态以及折射光束经第二偏振态选择器后的第二后选择量子态:(3) According to the following formula (ii), the first post-selected quantum state of the reflected beam after passing through the first polarization state selector and the second post-selected quantum state of the refracted beam after passing through the second polarization state selector are obtained:
其中,v=r,t分别表示反射光路和折射光路,|Ψv>为反射光束经第一偏振态选择器前或者折射光束经第二偏振态选择器前的量子态,为反射光束或折射光路的横向波矢,为反射光束或折射光束的波型函数,|ψv>为反射光束经第一偏振态选择器前或者折射光束经第二偏振态选择器前的偏振态;为的共轭,为反射光束经第一偏振态选择器后或者折射光束经第二偏振态选择器后的偏振态, H>为偏振态沿水平方向,|V>为偏振态沿垂直方向,Δ为样品在指定波长下的旋光角;Among them, v=r, t represent the reflected light path and the refracted light path respectively, |Ψ v > is the quantum state of the reflected beam before passing through the first polarization state selector or the refracted light beam before passing through the second polarization state selector, is the transverse wave vector of the reflected beam or refracted light path, is the wave mode function of the reflected beam or the refracted beam, |ψ v > is the polarization state of the reflected beam before passing through the first polarization state selector or the refracted beam before passing through the second polarization state selector; for the conjugate of is the polarization state of the reflected beam passing through the first polarization state selector or the refracted beam passing through the second polarization state selector, H> is the polarization state along the horizontal direction, |V> is the polarization state along the vertical direction, Δ is the optical rotation angle of the sample at the specified wavelength;
(4)|ψv>和|ψi>满足以下关系式:(4) |ψ v > and |ψ i > satisfy the following relationship:
其中in
从光发生装置出射的光束经过棱镜及样品各个界面发生反射和折射,m=1,2,3,4,5表示的是对应于入射角θm的界面;表示的是对应于入射角θm的折射角;其Fresnel折射系数和分别表示为;km是中心波矢,是光束在y方向的分量; 为旋转矩阵,α为偏振态制备器设定的光轴与水平方向之间的夹角;rp,rs是光从棱镜进入样品时,在棱镜和样品表面发生反射时的Fresnel反射系数, 样品折射率 The light beam emitted from the light generating device is reflected and refracted by each interface of the prism and the sample, and m=1, 2, 3, 4, 5 represent the interface corresponding to the incident angle θ m ; Represents the refraction angle corresponding to the incident angle θ m ; its Fresnel refraction coefficient and Respectively expressed as; k m is the central wave vector, is the component of the beam in the y direction; is the rotation matrix, α is the angle between the optical axis set by the polarization state generator and the horizontal direction; r p , rs are the Fresnel reflection coefficients when the light enters the sample from the prism and is reflected on the prism and the sample surface, Sample Refractive Index
(5)根据计算光子自旋分裂值<yv>:(5) According to Calculate the photon spin splitting value <y v >:
(6)根据步骤(1)记录的<yr>和<yt>,联立(i)~(viii)计算得出样品折射率n和样品在指定波长下的旋光角Δ,样品在不同波长下的旋光角构成旋光谱。(6) According to <y r > and <y t > recorded in step (1), calculate the refractive index n of the sample and the optical rotation angle Δ of the sample at the specified wavelength by combining (i) to (viii). The rotation angle at the wavelength constitutes the rotation spectrum.
上述基于量子弱测量的样品折射率和旋光谱测量分析方法,当由光发生装置发出的光经偏振态制备器、棱镜,以布鲁斯特角入射到样品介质入射界面产生反射光束和折射光束,这样可以保证对样品折射率和旋光谱测量的最佳敏感性。In the above-mentioned sample refractive index and rotational spectrum measurement and analysis method based on quantum weak measurement, when the light emitted by the light generating device passes through the polarization state preparation device and the prism, it is incident on the incident interface of the sample medium at the Brewster angle to generate reflected beams and refracted beams, so that Optimum sensitivity to sample refractive index and rotational spectroscopic measurements is guaranteed.
上述基于量子弱测量的样品折射率和旋光谱测量分析方法,调整光发生装置、棱镜和样品、第一光接收装置和/或第二光接收装置,使反射光束和折射光束的传播方向分别与样品反射光束出射面和折射光束出射面垂直或接近垂直,实现较大的弱测量放大效果。In the method for measuring and analyzing sample refractive index and rotational spectrum based on quantum weak measurement, the light generating device, the prism and the sample, the first light receiving device and/or the second light receiving device are adjusted so that the propagation directions of the reflected light beam and the refracted light beam are respectively in line with the The exit surface of the reflected beam of the sample and the exit surface of the refracted beam are vertical or close to vertical, so as to achieve a large weak measurement amplification effect.
上述基于量子弱测量的样品折射率和旋光谱测量分析方法,还可以在步骤(1)~(6)基础上,进一步包括:The above method for measuring and analyzing sample refractive index and rotational spectroscopy based on quantum weak measurement may further include:
(7)配制一系列不同浓度的标样,重复步骤(1)~(6),获得一系列标样的反射光束质心横移距离-折射率变化曲线以及折射光束质心横移距离-旋光角变化曲线;(7) Prepare a series of standard samples with different concentrations, repeat steps (1) to (6), and obtain a series of standard samples of the reflected beam centroid traverse distance-refractive index change curve and the refracted beam centroid traverse distance-optical rotation angle change curve;
(8)按照步骤(1)测量待测样品的反射光束质心横移距离和反射光束质心横移距离,再根据步骤(7)获得的反射光束质心横移距离-折射率变化曲线以及折射光束质心横移距离-旋光角变化曲线,便可得出待测样品的浓度、折射率及旋光角,待测样品在不同波长下的旋光角构成旋光谱。(8) According to step (1), measure the reflected beam centroid traverse distance and the reflected beam centroid traverse distance of the sample to be tested, and then obtain the reflected beam centroid traverse distance-refractive index change curve and the refracted beam centroid obtained in step (7). The concentration, refractive index and optical rotation angle of the sample to be tested can be obtained by moving the distance-optical rotation angle change curve. The optical rotation angle of the sample to be tested at different wavelengths constitutes the rotation spectrum.
在建立反射光束质心横移距离-折射率变化曲线以及折射光束质心横移距离-旋光角变化曲线基础上,对于较低浓度溶液,只需要通过光学测量仪器对待测溶液进行测试,记录反射光束质心横移距离和折射光束质心横移距离,便可精确获得溶液折射率、旋光谱以及溶液浓度,从而实现对低浓度溶液浓度及光学性能的高精度测量,并提高了测量效率。On the basis of establishing the reflected beam centroid traverse distance-refractive index change curve and the refracted beam centroid traverse distance-optical rotation angle change curve, for solutions with lower concentrations, it is only necessary to test the solution to be measured by an optical measuring instrument and record the reflected beam centroid The lateral movement distance and the lateral movement distance of the center of mass of the refracted beam can accurately obtain the solution refractive index, rotational spectrum and solution concentration, thereby realizing high-precision measurement of low-concentration solution concentration and optical properties, and improving measurement efficiency.
本发明进一步提供了一种基于量子弱测量的手性分子对映体含量测量分析方法,采用上述的基于量子弱测量的光学测量仪,所述样品为含有手性分子的物质的溶液,步骤如下:The present invention further provides a method for measuring and analyzing the enantiomer content of chiral molecules based on quantum weak measurement. The above-mentioned optical measuring instrument based on quantum weak measurement is used, and the sample is a solution containing a substance containing chiral molecules. The steps are as follows :
(1)由光发生装置发出的光经偏振态制备器、棱镜入射到样品入射界面产生反射光束和折射光束,反射光束经第一偏振态选择器由第一光接收装置接收,折射光束经第二偏振态选择器由第二光接收装置接收;通过第一光接收装置记录反射光束质心横移距离,将其作为反射光束光子自旋分裂值<yr>;通过第二光接收装置记录折射光束质心横移距离,将其作为折射光束光子自旋分裂值<yt>;(1) The light emitted by the light generating device enters the incident interface of the sample through the polarization state preparation device and the prism to generate reflected light beams and refracted light beams. The reflected light beams are received by the first light receiving device through the first polarization state selector, and the refracted light beams pass through the first polarization state selector. The two polarization state selectors are received by the second light receiving device; the center of mass traversing distance of the reflected beam is recorded by the first light receiving device, which is used as the photon spin splitting value <y r > of the reflected beam; the refraction is recorded by the second light receiving device Transverse distance of the beam center of mass, which is used as the photon spin splitting value <y t > of the refracted beam;
(2)依据步骤(1)得的反射光束光子自旋分裂值<yr>,折射光束光子自旋分裂值<yt>,含有手性分子的物质的溶液中与左旋物质旋光谱和折射率属性相关比例k1、k3,含有手性分子的物质的溶液中与右旋物质旋光谱和折射率属性相关比例k2、k4,按照如下公式(ix)和(x)联立计算得出溶液中左旋物质含量x和右旋物质含量y:(2) According to the reflected beam photon spin splitting value <y r > and the refracted beam photon spin splitting value <y t > obtained in step (1), the spin spectrum and refraction The ratios k 1 and k 3 related to the rate attribute, and the ratios k 2 and k 4 related to the spectrum and refractive index attribute of the right-handed substance in the solution containing chiral molecules, are calculated according to the following formulas (ix) and (x) simultaneously The content x of the left-handed substance and the content y of the right-handed substance in the solution are obtained:
k1x-k2y=<yt> (ix)k 1 xk 2 y=<y t > (ix)
k3x+k4y=<yr> (x)k 3 x+k 4 y=<y r > (x)
所述k1为单一左旋物质存在时,折射光束光子自旋分裂值随含有单一左旋物质溶液浓度或旋光角的变化系数;所述k2为单一右旋物质存在时,折射光束光子自旋分裂值随含有单一右旋物质溶液浓度或旋光角的变化系数;所述k3为单一左旋物质存在时,反射光束光子自旋分裂值随含有单一左旋物质溶液浓度或折射率的变化系数;所述k4为单一右旋物质存在时,反射光束光子自旋分裂值随含有单一右旋物质溶液浓度或折射率的变化系数。When said k 1 is a single left-handed substance exists, the photon spin splitting value of the refracted beam varies with the concentration or optical rotation angle of the solution containing a single left-handed substance ; value with the coefficient of variation of the solution concentration or optical rotation angle containing a single dextrorotatory substance; when said k 3 is a single levorotatory substance exists, the reflected beam photon spin splitting value follows the variation coefficient of the solution concentration or refractive index of a single dextrorotatory substance; k 4 is the variation coefficient of the reflected beam photon spin splitting value with the concentration or refractive index of the solution containing a single right-handed substance in the presence of a single right-handed substance.
上述基于量子弱测量的手性分子对映体含量测定方法,所述含有单一左旋物质或单一右旋物质的溶液旋光角和折射率通过前面给出的基于量子弱测量的样品折射率和旋光谱测量分析方法得到,具体为首先配制一系列不同浓度的含有单一左旋物质的溶液标样,按照基于量子弱测量的样品折射率和旋光谱测量分析方法步骤(1)~(6)测量不同浓度标样的折射率和在指定波长下的旋光角,然后依据不同浓度条件下的反射光束质心横移距离(或折射光束质心横移距离)和折射率(旋光角),获得一系列标样的反射光束质心横移距离-折射率变化曲线(或折射光束质心横移距离-旋光角变化曲线),反射光束质心横移距离-折射率变化曲线(或折射光束质心横移距离-旋光角变化曲线)斜率即为系数k3(或k1);对于含有单一右旋物质溶液,其操作步骤相同,最终得到的反射光束质心横移距离-折射率变化曲线(或折射光束质心横移距离-旋光角变化曲线)斜率即为系数k4(或k2)。In the method for determining the enantiomer content of chiral molecules based on quantum weak measurement, the optical rotation angle and refractive index of the solution containing a single left-handed substance or a single right-handed substance are determined by the sample refractive index and rotation spectrum based on quantum weak measurement given above. The measurement and analysis method is obtained. Specifically, a series of solution standard samples containing a single levorotatory substance of different concentrations are firstly prepared, and the samples with different concentrations are measured according to steps (1) to (6) of the sample refractive index and spin spectrum measurement and analysis method based on quantum weak measurement. According to the refractive index of the sample and the optical rotation angle at the specified wavelength, and then according to the reflected beam centroid traverse distance (or refracted beam centroid traverse distance) and refractive index (optical rotation angle) under different concentration conditions, a series of reflections of the standard sample are obtained. Beam centroid traverse distance-refractive index change curve (or refracted beam centroid traverse distance-optical rotation angle change curve), reflected beam centroid traverse distance-refractive index change curve (or refracted beam centroid traverse distance-optical rotation angle change curve) The slope is the coefficient k 3 (or k 1 ); for a solution containing a single dextrorotatory substance, the operation steps are the same, and the finally obtained reflected beam centroid traverse distance-refractive index change curve (or refracted beam centroid traverse distance-optical rotation angle Change curve) slope is the coefficient k 4 (or k 2 ).
目前现有技术中,样品光学性能(例如折射率、旋光谱等)主要是通过宏观测量分析得到,而对于信号微弱的手征光信号(只有非手性背景吸收信号的10-6~10-4量级),直接测量比较困难,且精度较低,更无法获取含有手性分子物质(例如手性药物)中手性分子对映体的含量。 In the current existing technology, the optical properties of samples (such as refractive index, rotational spectrum, etc.) 4 magnitude), direct measurement is difficult, and the accuracy is low, and it is impossible to obtain the content of chiral molecular enantiomers in substances containing chiral molecules (such as chiral drugs).
与现有技术相比,本发明具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
1、本发明基于量子弱测量技术,在测量光路中,以入射光路中的前选择量子态与反射光路中的第一后选择量子态之间构造第一量子弱测量光路,通过调整入射光束和反射光束偏振态,可以使反射光束自旋分裂值扩大至少103倍,从而实现对样品折射极小改变的测量,为研制高灵敏度折射率传感器提供了很好的研发思路,具有良好的应用前景;1. The present invention is based on quantum weak measurement technology. In the measurement optical path, the first quantum weak measurement optical path is constructed between the pre-selected quantum state in the incident optical path and the first post-selected quantum state in the reflected optical path. By adjusting the incident light beam and The polarization state of the reflected beam can expand the spin splitting value of the reflected beam by at least 10 3 times, so as to realize the measurement of the minimal change in the refraction of the sample, which provides a good research and development idea for the development of a high-sensitivity refractive index sensor and has a good application prospect ;
2、本发明基于量子弱测量技术,在测量光路中,以入射光路中的前选择量子态与折射光路中的第二后选择量子态之间构造第二量子弱测量光路,通过调整入射光束和折射光束偏振态,可以使折射光束自旋分裂值扩大至少103倍,从而实现对样品微弱手征光信号(例如旋光角)的测量,可作为光学高精度偏振态测量手段,具有良好的应用前景;2. The present invention is based on quantum weak measurement technology. In the measurement optical path, a second quantum weak measurement optical path is constructed between the pre-selected quantum state in the incident optical path and the second post-selected quantum state in the refracted optical path. By adjusting the incident light beam and The polarization state of the refracted beam can expand the spin splitting value of the refracted beam by at least 10 3 times, thereby realizing the measurement of the weak chiral optical signal (such as the optical rotation angle) of the sample, which can be used as an optical high-precision polarization state measurement method and has good applications prospect;
3、本发明不仅可以同时实现对样品折射率和手征光信号(例如旋光角)的测量,还可以依据含有手性分子物质的溶液中左旋物质、右旋物质含量与折射率和旋光谱相关性以及溶液折射率和旋光谱变化所引起的自旋分裂来测定溶液中手性分子对映体含量,从而突破本领域中手性化学分析的瓶颈;3. The present invention can not only realize the measurement of the refractive index of the sample and the chiral optical signal (such as the optical rotation angle) at the same time, but also can be based on the correlation between the content of the left-handed substance and the right-handed substance in the solution containing the chiral molecular substance and the refractive index and the rotation spectrum. Determining the enantiomer content of chiral molecules in solution by using the spin splitting caused by the change of refraction index and spin spectrum of the solution, so as to break through the bottleneck of chiral chemical analysis in this field;
4、本发明提供的量子弱测量技术是一种新型的无损的直接量子态测量技术,专注于可观测物理量(例如光子自旋)本身引起的量子态改变,而对外界的干扰不敏感,使其在测量过程中引入的扰动非常小,实现手性药物在其自然状态(溶液环境)下高精度、高灵敏度的测量,有望在单分子层面实现对手性药物的分析;4. The quantum weak measurement technology provided by the present invention is a new type of non-destructive direct quantum state measurement technology, which focuses on the quantum state change caused by the observable physical quantity (such as photon spin) itself, and is insensitive to external interference, so that The disturbance introduced in the measurement process is very small, which can achieve high-precision and high-sensitivity measurement of chiral drugs in their natural state (solution environment), and is expected to realize the analysis of chiral drugs at the single-molecule level;
5、本发明在药物分析及药物开发领域将发挥重要作用,在生物医学工程、生命科学、分析化学等多个学科领域也具有重要应用价值。5. The present invention will play an important role in the field of drug analysis and drug development, and also has important application value in multiple disciplines such as biomedical engineering, life science, and analytical chemistry.
附图说明Description of drawings
图1为本发明基于量子弱测量的光学测量仪结构示意图;其中,1、光发生装置,11、光源发生器,12、能量调节器,13、第一光束变换器,2、偏振态制备器,3、棱镜,4、样品,5、第一偏振态选择器,6、第一光接收装置,61、第二光束变换器,62、第一光电探测器,7、第二偏振态选择器,8、第二光接收装置,81、第三光束变换器,82、第二光电探测器。Fig. 1 is the structural schematic diagram of the optical measuring instrument based on quantum weak measurement of the present invention; Wherein, 1, light generating device, 11, light source generator, 12, energy conditioner, 13, first light beam converter, 2, polarization state preparer , 3, prism, 4, sample, 5, the first polarization state selector, 6, the first light receiving device, 61, the second beam converter, 62, the first photodetector, 7, the second polarization state selector , 8, the second light receiving device, 81, the third beam converter, 82, the second photodetector.
图2为本发明入射光束在棱镜与样品表面经多次界面反射、折射的光路原理图。Fig. 2 is a schematic diagram of the optical path of the incident beam of the present invention through multiple interface reflections and refractions on the surface of the prism and the sample.
图3为入射光束和反射光束质心横移距离随含有手性分子物质的溶液浓度或折射率与旋光角变化曲线示意图,其中(a)为单一葡萄糖溶液时,折射光束质心横移距离随葡萄糖溶液浓度或旋光角变化曲线示意图,(b)为单一葡萄糖溶液时,反射光束质心横移距离随葡萄糖溶液浓度或折射率系数变化曲线示意图,(c)为单一果糖溶液时,折射光束质心横移距离随果糖溶液浓度或旋光角变化曲线示意图,(d)为单一果糖溶液时,反射光束质心横移距离随果糖溶液浓度或折射率变化曲线示意图。Fig. 3 is a schematic diagram of the variation curve of the center of mass of the incident beam and the reflected beam with the solution concentration or refractive index and the optical rotation angle containing chiral molecular substances, wherein (a) is a single glucose solution, the center of mass of the refracted beam moves with the glucose solution Schematic diagram of the change curve of concentration or optical rotation angle, (b) when it is a single glucose solution, the schematic diagram of the lateral movement distance of the center of mass of the reflected beam with the concentration of glucose solution or the change of the refractive index coefficient, (c) when it is a single fructose solution, the lateral movement distance of the center of mass of the refracted beam Schematic diagram of the change curve with the concentration of fructose solution or optical rotation angle, (d) is a schematic diagram of the change curve of the center of mass of the reflected beam with the concentration of fructose solution or the change of refractive index in the case of a single fructose solution.
图4为葡萄糖和果糖混合溶液旋光角随折射光束质心横移距离变化曲线(a)和葡萄糖和果糖混合溶液折射率系数随反射光束质心横移距离变化曲线(b)示意图。Figure 4 is a schematic diagram of the variation curve (a) of the optical rotation angle of the mixed solution of glucose and fructose with the distance of the center of mass of the refracted beam (a) and the change of the refractive index coefficient of the mixed solution of glucose and fructose with the distance of the center of mass of the reflected beam (b).
具体实施方式Detailed ways
以下将结合附图给出本发明实施例,并通过实施例对本发明的技术方案进行进一步的清楚、完整说明。显然,所述实施例仅仅是本发明的一部分实施例,而不是全部的实施例。基于本发明内容,本领域普通技术人员在没有做出创造性劳动的前提下所得到的所有其它实施例,都属于本发明所保护的范围The embodiments of the present invention will be given below in conjunction with the accompanying drawings, and the technical solutions of the present invention will be further clearly and completely described through the embodiments. Apparently, the embodiments described are only some of the embodiments of the present invention, but not all of them. Based on the contents of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative work belong to the protection scope of the present invention
实施例1Example 1
本实施例提供的基于量子弱测量的光学测量仪,结构如图1所示,该仪器包括光发生装置1、偏振态制备器2、棱镜3、样品4、第一偏振态选择器5、第二偏振态选择器7、第一光接收装置6、第二光接收装置8。所述光发生装置1由光源发生器11、能量调节器12和第一光束变换器13组合而成,其中光源发生器11为准直激光器,能量调节器12为二分之一波片,第一光束变换器13为凸透镜。所述偏振态制备器2为格兰激光偏振棱镜,用于构造合适的量子态。所述棱镜3为直角三棱镜,用于在待测溶液表面以布鲁斯特角入射。所述样品4为待测葡萄糖和果糖的混合溶液,该混合液盛放于玻璃容器中,玻璃容器的形状用于保证最终折射光束垂直或接近垂直于出射面,棱镜3的一个侧面与盛放样品4的玻璃容器相贴合。所述第一偏振态选择器5和第二偏振态选择器7均由相位补偿器和格兰激光偏振棱镜组合而成,用于构造合适的量子态。所述第一光接收装置6由第二光束变换器61和第一光探测器62组合而成,第二光接收装置8由第三光束变换器81和第二光探测器82而成,第一光探测器62和第二光探测器82均为用于探测弱的光强度信号的电荷耦合元件CCD,第二光束变换器61和第三光束变换器81均为凸透镜,第二光束变换器61的焦距大于第一光束变换器13的焦距,第一光束变换器13与第二光束变换器61构成共焦系统,第三光束变换器81的焦距大于第一光束变换器13的焦距,第一光束变换器13与第三光束变换器81构成共焦系统。The optical measuring instrument based on quantum weak measurement provided in this embodiment has a structure as shown in Fig. Two polarization state selectors 7 , a first light receiving device 6 , and a second light receiving device 8 . The light generating device 1 is composed of a light source generator 11, an energy adjuster 12 and a first beam converter 13, wherein the light source generator 11 is a collimated laser, and the energy adjuster 12 is a half-wave plate. A beam converter 13 is a convex lens. The polarization state generator 2 is a Glan laser polarization prism, which is used to construct a suitable quantum state. The prism 3 is a right-angled triangular prism, which is used for incident at the Brewster angle on the surface of the solution to be measured. The sample 4 is a mixed solution of glucose and fructose to be tested, and the mixed solution is contained in a glass container. The shape of the glass container is used to ensure that the final refracted light beam is perpendicular or nearly perpendicular to the exit surface. The glass container of sample 4 fit together. Both the first polarization state selector 5 and the second polarization state selector 7 are composed of a phase compensator and a Glan laser polarization prism for constructing a suitable quantum state. The first light receiving device 6 is composed of a second beam converter 61 and a first photo detector 62, and the second light receiving device 8 is composed of a third beam converter 81 and a second photo detector 82. A photodetector 62 and a second photodetector 82 are both charge-coupled device CCDs for detecting weak light intensity signals, the second beam converter 61 and the third beam converter 81 are convex lenses, and the second beam converter The focal length of 61 is greater than the focal length of the first beam converter 13, the first beam converter 13 and the second beam converter 61 constitute a confocal system, the focal length of the third beam converter 81 is greater than the focal length of the first beam converter 13, the second A beam converter 13 and a third beam converter 81 form a confocal system.
上述基于量子弱测量的光学测量仪工作原理为:由光源发生器11发出的激光依次经能量调节器12、第一光束转换器13、偏振态制备器2、棱镜3以布鲁斯特角入射到样品4的光入射面,产生反射光束和折射光束,从棱镜反射出的反射光束依次经第一偏振态选择器5、第二光束变换器61由第一光探测器62接收,透过样品、从样品出射面发出的折射光束依次经第二偏振态选择器7、第三光束变换器81由第二光探测器82接收。The working principle of the above-mentioned optical measuring instrument based on quantum weak measurement is as follows: the laser light emitted by the light source generator 11 is incident on the sample at the Brewster angle through the energy regulator 12, the first beam converter 13, the polarization state preparation device 2, and the prism 3 in sequence. The light incident surface of 4 generates reflected light beam and refracted light beam, and the reflected light beam reflected from the prism is received by the first light detector 62 through the first polarization state selector 5 and the second light beam converter 61 in turn, and then passes through the sample, from The refracted light beam emitted from the exit surface of the sample is received by the second photodetector 82 through the second polarization state selector 7 and the third beam converter 81 in sequence.
入射到样品4光入射面的光束偏振态为前选择量子态,反射光束经第一偏振态选择器5后的光束偏振态为第一后选择量子态,折射光束经第二偏振态选择器7后的光束偏振态为第二后选择量子态;入射光路中的前选择量子态与反射光路中的第一后选择量子态之间构成实现样品折射率测量的第一量子弱测量光路部分,入射光路中的前选择量子态与折射光路中的第二后选择量子态之间构成实现样品旋光谱测量的第二量子弱测量光路部分;调整偏振态制备器2、第一偏振态选择器5和第二偏振态选择器7,从而使后选择量子态与前选择量子态接近垂直,夹角为90°±△’(△’不大于5°)。The polarization state of the beam incident on the light incident surface of the sample 4 is the pre-selected quantum state, the polarization state of the reflected beam after passing through the first polarization state selector 5 is the first post-selected quantum state, and the refracted beam passes through the second polarization state selector 7 The last beam polarization state is the second post-selected quantum state; the first quantum weak measurement optical path part for realizing the sample refractive index measurement is formed between the pre-selected quantum state in the incident optical path and the first post-selected quantum state in the reflected optical path, and the incident optical path The second quantum weak measurement optical path part that realizes the sample rotation spectrum measurement is formed between the pre-selected quantum state in the optical path and the second post-selected quantum state in the refracted optical path; adjust the polarization state preparation device 2, the first polarization state selector 5 and The second polarization state selector 7 makes the post-selected quantum state nearly perpendicular to the pre-selected quantum state, and the included angle is 90°±△′ (△′ is not greater than 5°).
实施例2Example 2
本实施例基于量子弱测量技术,采用实施例1提供的基于量子弱测量的光学测量仪,对上述葡萄糖和果糖混合溶液样品折射率和旋光谱进行测量分析,步骤如下:This embodiment is based on the quantum weak measurement technology, and the optical measuring instrument based on the quantum weak measurement provided in Example 1 is used to measure and analyze the refractive index and rotational spectrum of the glucose and fructose mixed solution sample. The steps are as follows:
(1)由光源发生器11发出的激光依次经能量调节器12、第一光束转换器13、偏振态制备器2、棱镜3以布鲁斯特角入射到样品4的光入射面,产生反射光束和折射光束,从棱镜反射出的反射光束依次经第一偏振态选择器5、第二光束变换器61由第一光探测器62接收,透过样品、从样品出射面发出的折射光束依次经第二偏振态选择器7、第三光束变换器81由第二光探测器82接收;通过第一光探测器62记录光强,读取反射光束质心横移距离,将其作为反射光束光子自旋分裂值<yr>;通过第二光探测器82记录光强,读取折射光束质心横移距离,将其作为折射光束光子自旋分裂值<yt>。(1) The laser light emitted by the light source generator 11 is incident on the light incident surface of the sample 4 at the Brewster angle through the energy conditioner 12, the first beam converter 13, the polarization state preparation device 2, and the prism 3 to generate reflected light beams and The refracted beam, the reflected beam reflected from the prism passes through the first polarization state selector 5, the second beam converter 61 and is received by the first photodetector 62, and the refracted beam transmitted through the sample and emitted from the sample exit surface sequentially passes through the second The two polarization state selectors 7 and the third beam converter 81 are received by the second photodetector 82; the light intensity is recorded by the first photodetector 62, and the distance of the center of mass of the reflected beam is read, which is used as the photon spin of the reflected beam Splitting value <y r >; light intensity is recorded by the second photodetector 82, and the centroid traverse distance of the refracted beam is read, which is used as the photon spin splitting value <y t > of the refracted beam.
(2)根据如下公式(i)获得入射到样品光入射面的入射光束前选择量子态:(2) According to the following formula (i), the quantum state selected before the incident beam incident on the light incident surface of the sample is obtained:
其中,为入射光束的横向波矢,为入射光束的波型函数,本实施例采用高斯光束,i代表入射光束,|ψi>为入射光束经偏振态制备器所后的偏振态,本实施例中,|ψi>=|H>入射光束经偏振态制备器后的偏振态沿水平方向。in, is the transverse wave vector of the incident beam, is the wave type function of the incident beam, and this embodiment adopts a Gaussian beam, i represents the incident beam, and |ψ i > is the polarization state of the incident beam passing through the polarization state preparation device. In this embodiment, |ψ i >=|H> the polarization state of the incident beam passing through the polarization state preparation device is along the horizontal direction .
(3)根据如下公式(ii)获得反射光束经第一偏振态选择器后的第一后选择量子态以及折射光束经第二偏振态选择器后的第二后选择量子态:(3) According to the following formula (ii), the first post-selected quantum state of the reflected beam after passing through the first polarization state selector and the second post-selected quantum state of the refracted beam after passing through the second polarization state selector are obtained:
其中,v=r,t分别表示反射光路和折射光路,|Ψv>为反射光束经第一偏振态选择器前或者折射光束经第二偏振态选择器前的量子态,为反射光束或折射光路的横向波矢,为反射光束或折射光束的波型函数,由于本实施例采用高斯光束,|ψv>为反射光束经第一偏振态选择器前或者折射光束经第二偏振态选择器前的偏振态;为的共轭,为反射光束经第一偏振态选择器后或者折射光束经第二偏振态选择器后的偏振态, 为光束偏振态沿水平方向,|V>为光束偏振态沿垂直方向,Δ为样品在指定波长下的旋光角。Among them, v=r, t represent the reflected light path and the refracted light path respectively, |Ψ v > is the quantum state of the reflected beam before passing through the first polarization state selector or the refracted light beam before passing through the second polarization state selector, is the transverse wave vector of the reflected beam or refracted light path, Be the mode function of reflected light beam or refracted light beam, because this embodiment adopts Gaussian light beam, |ψ v > is the polarization state of the reflected beam before passing through the first polarization state selector or the refracted beam before passing through the second polarization state selector; for the conjugate of is the polarization state of the reflected beam passing through the first polarization state selector or the refracted beam passing through the second polarization state selector, is the polarization state of the beam along the horizontal direction, |V> is the polarization state of the beam along the vertical direction, and Δ is the optical rotation angle of the sample at the specified wavelength.
(4)从偏振态制备器2出射的光束入射经棱镜3入射到样品介质界面需要经过多次界面反射和折射,最终从棱镜出射界面和样品出射界面射出得到反射光束和折射光束,其过程如图2所示,入射到棱镜界面①的光束经折射进入棱镜到达样品介质界面②,光束在此发生折射和反射,反射光束到达棱镜出射界面⑤经折射形成光路2,折射光束到达样品介质出射界面③经折射进入玻璃容器介质到达其界面④并经折射形成光路1;形成的光路2和光路1即是最终的反射光束和折射光束,两者之间的偏振态满足|ψv>和|ψi>满足以下关系式:(4) The beam incident from the polarization state generator 2 is incident on the sample medium interface through the prism 3 and needs to undergo multiple interface reflections and refractions, and finally the reflected beam and the refracted beam are obtained from the exit interface of the prism and the exit interface of the sample. The process is as follows As shown in Figure 2, the light beam incident on the prism interface ① is refracted and enters the prism to reach the sample medium interface ②, where the light beam is refracted and reflected, and the reflected beam reaches the prism exit interface ⑤ after refraction to form an optical path 2, and the refracted beam reaches the sample medium exit interface ③ enters the glass container medium through refraction to reach its interface ④ and forms optical path 1 through refraction; the formed optical path 2 and optical path 1 are the final reflected beam and refracted beam, and the polarization state between the two satisfies |ψ v > and |ψ i >Satisfy the following relationship:
其中in
从光发生装置出射的光束经过棱镜及样品各个界面发生反射和折射,m=1,2,3,4,5表示的是对应于入射角θm的界面;表示的是对应于入射角θm的折射角;其Fresnel折射系数和分别表示为;km是中心波矢,是光束在y方向的分量; 为旋转矩阵,α为偏振态制备器设定的光轴与水平方向之间的夹角;rp,rs是光从棱镜进入样品时,在棱镜和样品表面发生反射时的Fresnel反射系数, 样品折射率 The light beam emitted from the light generating device is reflected and refracted by each interface of the prism and the sample, and m=1, 2, 3, 4, 5 represent the interface corresponding to the incident angle θ m ; Represents the refraction angle corresponding to the incident angle θ m ; its Fresnel refraction coefficient and Respectively expressed as; k m is the central wave vector, is the component of the beam in the y direction; is the rotation matrix, α is the angle between the optical axis set by the polarization state generator and the horizontal direction; r p , rs are the Fresnel reflection coefficients when the light enters the sample from the prism and is reflected on the prism and the sample surface, Sample Refractive Index
(5)根据|Ψfv>计算光子自旋分裂值<yv>:(5) Calculate the photon spin splitting value <y v > according to |Ψ fv >:
(6)根据步骤(1)记录的<yr>和<yt>,联立(i)~(viii)计算得出样品折射率n和样品在指定波长下的旋光角Δ,样品在不同波长下的旋光角构成旋光谱。(6) According to <y r > and <y t > recorded in step (1), calculate the refractive index n of the sample and the optical rotation angle Δ of the sample at the specified wavelength by combining (i) to (viii). The rotation angle at the wavelength constitutes the rotation spectrum.
本实施例依次配制浓度为3mg/ml、4mg/ml、5mg/ml、6mg/ml、7mg/ml、8mg/ml、9mg/ml的葡萄糖和果糖的混合溶液标样,根据步骤(1)~(6)获得每种浓度标样对应的反射光束质心横移距离、折射光束横移距离以及折射率和旋光角。为了便于说明本发明提供的折射率测量分析方法实现对样品折射极小改变的测量,本实施例中将获得的每种浓度标样的折射率减去去离子水折射率(n0=1.33250)得到每种浓度标样相对于去离子水的折射率系数变化Δn。每种浓度标样对应的折射率系数变化Δn随反射光束质心横移距离以及旋光角随折射光束质心横移距离变化的实验结果见图4(a)和(b)所示。This embodiment prepares the mixed solution standard sample of glucose and fructose that concentration is 3mg/ml, 4mg/ml, 5mg/ml, 6mg/ml, 7mg/ml, 8mg/ml, 9mg/ml successively, according to step (1)~ (6) Obtain the reflected beam centroid traverse distance, refracted beam traverse distance, refractive index and optical rotation angle corresponding to each concentration standard sample. In order to facilitate the description that the refractive index measurement analysis method provided by the present invention realizes the measurement of minimal changes in sample refraction, in this embodiment, the refractive index of each concentration standard sample obtained is subtracted from the refractive index of deionized water (n 0 =1.33250) Obtain the refractive index change Δn of each concentration standard sample relative to deionized water. Figure 4(a) and (b) show the experimental results of the refractive index change Δn corresponding to each concentration standard sample with the distance of the center of mass of the reflected beam and the variation of the optical rotation angle with the distance of the center of mass of the refracted beam.
利用所得每种浓度标样对应的反射光束质心横移距离及其相对于去离子水的相对折射率绘制出反射光束质心横移距离-折射率变化曲线,利用所得每种浓度标样对应的折射光束质心横移距离及其旋光角绘制出折射光束质心横移距离-旋光角变化曲线。在建立反射光束质心横移距离-折射率变化曲线以及折射光束质心横移距离-旋光角变化曲线基础上,对于未知浓度的葡萄糖和果糖混合溶液(待测样品),可以先按照步骤(1)测量待测样品的反射光束质心横移距离<yr>和反射光束质心横移距离<yt>,再根据获得的反射光束质心横移距离-折射率变化曲线以及折射光束质心横移距离-旋光角变化曲线,便可得出待测样品的浓度、折射率及旋光角,待测样品在不同波长下的旋光角构成旋光谱。Use the center of mass traversing distance of the reflected beam corresponding to each concentration standard sample and its relative refractive index relative to deionized water to draw the center of mass traversing distance of the reflected beam-refractive index change curve, and use the refraction index corresponding to the standard sample of each concentration obtained The beam centroid traversing distance and its optical rotation angle are used to draw the refracted beam centroid traversing distance-optical rotation angle change curve. On the basis of establishing the reflected beam centroid traverse distance-refractive index change curve and the refracted beam centroid traverse distance-optical rotation angle change curve, for a mixed solution of glucose and fructose (sample to be tested) with an unknown concentration, you can first follow step (1) Measure the reflected beam centroid traverse distance <y r > and reflected beam centroid traverse distance <y t > of the sample to be tested, and then according to the obtained reflected beam centroid traverse distance-refractive index change curve and refracted beam centroid traverse distance- The concentration, refractive index and optical rotation angle of the sample to be tested can be obtained from the change curve of the optical rotation angle, and the optical rotation angle of the sample to be tested at different wavelengths constitutes the rotation spectrum.
实施例3Example 3
本实施例基于量子弱测量技术,采用实施例1提供的基于量子弱测量的光学测量仪,对上述葡萄糖和果糖混合溶液样品中左旋物质和右旋物质含量进行测量分析,步骤如下:This embodiment is based on the quantum weak measurement technology, and the optical measuring instrument based on the quantum weak measurement provided in Example 1 is used to measure and analyze the content of the left-handed substance and the right-handed substance in the glucose and fructose mixed solution sample. The steps are as follows:
(1)分别配制一系列纯的葡萄糖溶液标样和果糖溶液标样,葡萄糖溶液标样浓度为1mg/ml、2mg/ml、3mg/ml、4mg/ml、5mg/ml、6mg/ml、7mg/ml、8mg/ml、9mg/ml,果糖溶液标样浓度为1mg/ml、2mg/ml、3mg/ml、4mg/ml、5mg/ml、6mg/ml、7mg/ml、8mg/ml、9mg/ml。(1) Prepare a series of pure glucose solution standard samples and fructose solution standard samples respectively, the concentrations of glucose solution standard samples are 1mg/ml, 2mg/ml, 3mg/ml, 4mg/ml, 5mg/ml, 6mg/ml, 7mg /ml, 8mg/ml, 9mg/ml, fructose solution standard concentration is 1mg/ml, 2mg/ml, 3mg/ml, 4mg/ml, 5mg/ml, 6mg/ml, 7mg/ml, 8mg/ml, 9mg /ml.
(2)按照实施例2中步骤(1)~(6),获得每种浓度标样对应的反射光束质心横移距离、折射光束横移距离以及折射率和旋光角。为了便于说明本发明提供的折射率测量分析方法实现对样品折射极小改变的测量,本实施例中将获得的每种浓度标样的折射率减去去离子水折射率(n0=1.33250)得到每种浓度标样相对于去离子水的折射率系数变化Δn。利用所得每种浓度标样对应的折射光束质心横移距离及其旋光角绘制出折射光束质心横移距离-旋光角变化曲线【如图3(a)和(c)所示,(a)为葡萄糖,(c)为果糖】,利用所得每种浓度标样对应的反射光束质心横移距离及其相对于去离子水的折射率系数变化Δn绘制出反射光束质心横移距离-折射率变化曲线【如图3(b)和(d)所示,(b)为葡萄糖,(d)为果糖】。图3(a)中折射光束光子自旋分裂值随葡萄糖溶液旋光角的变化系数(曲线斜率)为k1,图3(c)中折射光束光子自旋分裂值随果糖溶液旋光角的变化系数(曲线斜率)为k2,图3(b)中反射光束光子自旋分裂值随葡萄糖溶液折射率的变化系数(曲线斜率)为k3,图3(d)中反射光束光子自旋分裂值随果糖溶液折射率的变化系数(曲线斜率)为k4。(2) According to steps (1) to (6) in Example 2, obtain the centroid traverse distance of the reflected beam, the traverse distance of the refracted beam, and the refractive index and optical rotation angle corresponding to each concentration standard sample. In order to facilitate the description that the refractive index measurement analysis method provided by the present invention realizes the measurement of minimal changes in sample refraction, in this embodiment, the refractive index of each concentration standard sample obtained is subtracted from the refractive index of deionized water (n 0 =1.33250) Obtain the refractive index change Δn of each concentration standard sample relative to deionized water. Utilize the centroid traverse distance of the refracted beam corresponding to each concentration standard sample and its optical rotation angle to draw the centroid traverse distance of the refracted beam-optical rotation angle change curve [as shown in Figure 3 (a) and (c), (a) is Glucose, (c) is fructose], draw the reflected beam centroid traverse distance-refractive index change curve by using the reflected beam centroid traverse distance corresponding to each concentration standard sample and its refractive index change Δn relative to deionized water [As shown in Figure 3(b) and (d), (b) is glucose and (d) is fructose]. The variation coefficient (curve slope) of the photon spin splitting value of the refracted beam with the optical rotation angle of the glucose solution in Fig. 3(a) is k 1 , and the variation coefficient of the photon spin splitting value of the refracted beam with the optical rotation angle of the fructose solution in Fig. 3(c) (curve slope) is k 2 , the variation coefficient (curve slope) of the reflected beam photon spin splitting value with the glucose solution refractive index in Figure 3(b) is k 3 , and the reflected beam photon spin splitting value in Figure 3(d) The coefficient of variation (slope of the curve) of the refractive index with the fructose solution is k 4 .
(3)对于葡萄糖和果糖混合溶液(待测样品1、2、3);可以先按照实施例2的步骤(1)测量待测样品的反射光束质心横移距离<yr>和反射光束质心横移距离<yt>,然后结合步骤(2)得到的k1、k2、k3、k4根据公式k1x-k2y=<yt>(ix)和k3x+k4y=<yr>(x)计算得到待测样品中的左旋物质含量和右旋物质含量,结果见表1所示。(3) For the mixed solution of glucose and fructose (test samples 1, 2, 3); you can first measure the reflected beam centroid traverse distance <y r > and the reflected beam centroid of the sample to be tested according to the step (1) of embodiment 2 Traversing distance <y t >, and then k 1 , k 2 , k 3 , k 4 obtained in step (2) according to the formula k 1 xk 2 y=<y t >(ix) and k 3 x+k 4 y =<y r >(x) calculates the content of left-handed substances and right-handed substances in the sample to be tested, and the results are shown in Table 1.
表1.混合溶液中葡萄糖和果糖含量的测定Table 1. Determination of glucose and fructose content in mixed solution
注:待测样品1、2、3是提前用葡萄糖和果糖配制好的混合溶液,混合溶液中的葡萄糖和果糖浓度已知(即准备的葡萄糖和果糖浓度),再通过本实施例提供的手性分子对映体含量测量分析方法对混合溶液中的葡萄糖和果糖溶液浓度(即测量的葡萄糖和果糖浓度),从而对本实施例提供的手性分子对映体含量测量方法可行性得以印证。Note: Samples 1, 2, and 3 to be tested are mixed solutions prepared in advance with glucose and fructose. The analysis method for measuring and analyzing the enantiomer content of chiral molecules is based on the concentration of glucose and fructose in the mixed solution (that is, the measured glucose and fructose concentrations), so that the feasibility of the method for measuring the enantiomer content of chiral molecules provided in this example is confirmed.
从上述表格中可以看出,待测样品1-3测量得到的混合溶液中葡萄糖浓度和果糖浓度与配制时的葡萄糖浓度和果糖浓度十分接近,误差很小,因此采用本发明提供的基于弱测量的光学测量仪可以实现较低浓度混合溶液中左旋物质和右旋物质含量的测定,依次类推,也可以实现较低浓度溶液中手性分子对映体含量的测定。As can be seen from the above table, the glucose concentration and the fructose concentration in the mixed solution measured by the sample 1-3 to be tested are very close to the glucose concentration and the fructose concentration when preparing, and the error is very small. The optical measuring instrument can realize the determination of the content of left-handed substances and right-handed substances in the mixed solution of lower concentration, and by analogy, it can also realize the determination of the content of chiral molecule enantiomers in the solution of lower concentration.
此外,k1、k2、k3、k4确定以后,可以根据公式k1x-k2y=<yt>(ix)和k3x+k4y=<yr>(x)确定任一左旋物质含量x和右旋物质含量y对应的<yr>和<yt>,从而得到图4(a)和(b)中的反射光束质心横移距离-混合溶液浓度变化以及折射光束质心横移距离-混合溶液浓度变化的理论预测曲线(实线),由于溶液浓度与折射率和旋光角是一一对应的,所以得到的也是反射光束质心横移距离-折射率变化以及折射光束质心横移距离-旋光角变化的理论预测曲线。从图中可以看出,实施例(2)中每种浓度标样对应的折射率系数变化Δn随反射光束质心横移距离以及旋光角随折射光束质心横移距离变化的实验结果与理论预测曲线非常吻合,由此可以看出,本发明提供的基于量子弱测量的样品折射率和旋光谱测量分析方法可以实现对样品折射率极小改变以及样品微弱手征光信号(例如旋光角)的测量,可作为光学高精度偏振态测量手段,具有良好的应用前景。 In addition , after k 1 , k 2 , k 3 , and k 4 are determined, any <y r > and <y t > corresponding to the left-handed substance content x and the right-handed substance content y, so as to obtain the center of mass traverse distance of the reflected beam in Figure 4(a) and (b)-the concentration change of the mixed solution and the refracted beam The theoretical prediction curve (solid line) of centroid traverse distance-mixed solution concentration change. Since the solution concentration corresponds to the refractive index and optical rotation angle one by one, the centroid traverse distance of the reflected beam-refractive index change and the refracted beam are also obtained. Theoretical prediction curve of centroid traverse distance-optical rotation angle change. As can be seen from the figure, the experimental results and theoretical prediction curves of the variation of the refractive index coefficient Δn corresponding to each concentration standard sample in embodiment (2) vary with the distance of the center of mass of the reflected beam and the variation of the optical rotation angle with the distance of the center of mass of the refracted beam It is very consistent, so it can be seen that the sample refractive index and rotation spectrum measurement and analysis method based on quantum weak measurement provided by the present invention can realize the measurement of a very small change in the sample refractive index and a weak chiral optical signal (such as optical rotation angle) of the sample , can be used as an optical high-precision polarization state measurement method, and has a good application prospect.
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