JP2019510202A - System and method for multi-parameter spectroscopy - Google Patents

Abstract

An apparatus for detecting a substance in a sample includes a light emitting unit that directs at least one light beam through the sample. The plurality of units receive the light beam that has passed through the sample, and perform spectroscopic analysis of the sample based on the received light beam. Each of the plurality of units analyzes different parameters for the sample and provides separate output signals for the analysis. A processor detects the substance for each supplied separate output signal.

Description

[Cross-reference of related applications]
This application is US Provisional Application No. 62 / 278,186 (Attorney Docket No. NXGN-32968) filed on January 13, 2016 entitled “MULTI-PARAMETER SPECTROSCOPY”, “RAMAN SPECTROSCOPY WITH ORBITAL ANGULAR MOMENTUM” US Provisional Application No. 62 / 322,507 filed on April 14, 2016 (Attorney Docket No. NXGN-33094), US Provisional Application No. 62 / 365,486 (INCE-GAUSSIAN SPECTROSCOPY) Benefits of Attorney Docket Number NXGN-33217) and US Provisional Application No. 62 / 081,846 (Attorney Docket Number NXGN-32424) filed on November 19, 2014 entitled "DISTINCT SIGNATURES FOR CONCENTRATION MEASUREMENTS" The entirety of these applications are hereby incorporated by reference.

  This application is a US patent application No. 14 / 339,836 filed July 24, 2014 entitled “SYSTEM AND METHOD FOR MAKING CONCENTRATION MEASUREMENTS WITHIN A SAMPLE MATERIAL USING ORBITAL ANGULAR MOMENTUM”. Published on September 17, 2015 as No. 0260650, and is a continuation-in-part of Proxy Number NXGN-32196). This application is US patent application Ser. No. 14 / 875,507 filed Oct. 5, 2015 entitled “SYSTEM AND METHOD FOR EARLY DETECTION OF ALZHEIMERS BY DETECTING AMYLOID-BETA USING ORBITAL ANGULAR MOMENTUM”. NXGN-32776). U.S. Patent Application Nos. 14 / 339,836 and 14 / 875,507, and U.S. Patent Application Publication No. 2015-0260650 are hereby incorporated by reference in their entirety.

[Technical field]
The present invention relates to the detection of substances in a sample, more specifically to the detection of substances in a sample based on multi-parameter spectroscopy.

[background]
Measuring the concentration of organic and non-organic substances and detecting their presence is of great interest in many applications. In one example, the detection of substances in human tissue is becoming an increasingly important aspect of individual health care. The development of non-invasive assays that monitor biological and metabolic factors in human tissues is an important aspect of diagnostic therapy for various human diseases and may play an important role in appropriate disease management. The development of non-invasive assays that monitor biological and metabolic factors in human tissues is an important aspect of diagnostic therapy for various human diseases and may play an important role in appropriate disease management. One such substance that has been implicated in Alzheimer's disease is amyloid-β. Thus, an improved amyloid-β detection scheme is needed to better improve early stage detection of Alzheimer's disease.

Another example of a biological factor that can be monitored in human tissue is glucose. Glucose (C ₆ H ₁₂ O ₆ ) is a monosaccharide and is one of the most important carbohydrate nutrient sources. Glucose is essential for almost all biological processes and is required for the production of ATP adenosine triphosphate and other essential cellular components. The normal range of glucose concentration in human blood is 70 mg / dl to 160 mg / dl depending on the time of the last meal, physical tolerance and other factors. Free circulating glucose molecules stimulate the release of insulin from the pancreas. Insulin helps glucose molecules penetrate the cell wall by binding to two specific receptors within the normally non-glucose permeable cell membrane.

  One disease associated with problems with glucose concentration is diabetes. Diabetes is a disorder resulting from a decrease in insulin production or a reduced ability to utilize insulin and transport glucose through the cell membrane. As a result, high concentrations of glucose that are potentially dangerous during disease can accumulate in the blood (hyperglycemia). Therefore, maintaining blood glucose levels within the normal range is very important to prevent possible severe physiological complications.

  One important role of physiological glucose monitoring is the diagnosis and management of several metabolic diseases, such as diabetes mellitus (or simply diabetes). A number of invasive and non-invasive techniques are currently used for glucose monitoring. A problem with existing non-invasive glucose monitoring methods is that a clinically acceptable process has not yet been determined. Standard techniques with blood analysis currently include individual finger punctures and subsequent analysis of blood samples taken from the fingers. In recent decades, non-invasive blood glucose monitoring has become an increasingly important topic of investigation in the biomedical field. In particular, the introduction of optical approaches has made some progress in this field. Advances in optics have focused attention on the development of optical imaging techniques and non-invasive imaging systems. Application of optical methods to monitoring in cancer diagnostics and treatment is also a growing area because of the simplicity and low risk of optical detection methods. In addition to the medical field, detection of various types of substances in various other environments can be readily apparent.

  Many optical techniques for detecting various tissue metabolites and glucose in living tissue have been developed over the past 50 years. These methods were based on fluorescence spectroscopy, near infrared and mid-infrared spectroscopy, Raman spectroscopy, photoacoustic methods, optical coherence tomography, and other techniques. However, none of these attempted techniques has proven to be completely satisfactory.

  Another organic component suitable for optical substance concentration detection is human skin. The defense mechanism of human skin is based on the action of antioxidants such as carotenoids, vitamins and enzymes. β-carotene and lycopene account for more than 70% of human carotenoids. Local or systemic application of β-carotene and lycopene is a general strategy to improve the human defense system. Evaluation and optimization of this treatment requires measurement of b-carotene and lycopene concentrations in human tissues, particularly human skin that is a barrier to the environment.

  Thus, improved non-invasive techniques that allow the detection of the concentration and presence of various substances in the human body or other types of samples may have numerous applications in the medical field.

[summary]
The present invention includes, in one aspect thereof, an apparatus for detecting a substance in a sample comprising a light emitting unit that directs at least one light beam through the sample, as disclosed and described herein. The plurality of spectroscopic units receive the light beam that has passed through the sample, and perform spectroscopic analysis of the sample based on the received light beam. Each of the plurality of spectroscopic units analyzes different parameters for the sample and provides separate output signals for the analysis. A processor detects the substance for each supplied separate output signal.

  For a more complete understanding, reference is now made to the following description, taken in conjunction with the accompanying drawings, in which:

It is a figure which shows the aspect which detects presence of the substance in a sample using an orbital angular momentum signature. It is a figure which shows the aspect in which an OAM generator produces | generates an OAM twist beam. It is a figure which shows the light beam to which the orbital angular momentum was provided. It is a figure which shows a series of parallel wave fronts. It is a figure which shows the wave front which has the pointing vector which turns around the propagation direction of a wave front helically. It is a figure which shows a plane wave front. It is a figure which shows a helical wave front. It is a figure which shows the plane wave which has only the fluctuation | variation of a spin vector. It is a figure which shows application of the natural orbital angular momentum to a wave. It is a figure which shows the signal to which the orbital angular momentum different from FIG. 10B and FIG. 10C was applied. It is a figure which shows the signal to which the orbital angular momentum different from FIG. 10A and FIG. 10C was applied. It is a figure which shows the signal to which the orbital angular momentum different from FIG. 10A and FIG. 10B was applied. It is a figure which shows the propagation of the pointing vector about various eigenmodes. It is a figure which shows a helical phase plate. FIG. 2 is a block diagram of an apparatus that provides concentration measurement and presence detection of various substances using orbital angular momentum. FIG. 12 shows an emitter of the system of FIG. FIG. 12 shows a fixed orbital angular momentum generator of the system of FIG. It is a figure which shows one hologram used for application of an orbital angular momentum to a plane wave signal. It is a figure which shows one hologram used for application of an orbital angular momentum to a plane wave signal. It is a figure which shows one hologram used for application of an orbital angular momentum to a plane wave signal. It is a figure which shows one hologram used for application of an orbital angular momentum to a plane wave signal. It is a figure which shows the relationship between Hermitian-Gaussian mode and Laguerre-Gaussian mode. FIG. 3 shows superimposed holograms for applying orbital angular momentum to signals. FIG. 12 shows an adjustable orbital angular momentum generator used in the system of FIG. FIG. 3 is a block diagram of an adjustable orbital angular momentum generator that includes a plurality of hologram images. It is a figure which shows the aspect which can fluctuate the output of an OAM generator by applying a different orbital angular momentum. FIG. 6 illustrates an alternative manner in which a Hermite-Gaussian beam can be converted to a Laguerre-Gaussian beam by an OAM generator. It is a figure which shows the aspect which can twist a light beam with the hologram in an OAM generator. FIG. 6 shows how a sample receives an OAM torsional wave and provides an output wave with a specific OAM signature. It is a figure which shows the aspect in which an orbital angular momentum interacts with the molecule | numerator around the beam axis. It is a block diagram of the matching circuit structure which amplifies the received orbital angular momentum signal. FIG. 6 illustrates how a matching module can use a nonlinear crystal to generate a higher order orbital angular momentum light beam. It is a block diagram of an orbital angular momentum detector and a user interface. It is a figure which shows the influence of a sample density | concentration with respect to the spin angle polarization | polarized-light and orbital angle polarization of the light beam which passes a sample. It is a figure which shows more specifically the process of changing the orbital angular momentum polarization of the light beam which passes a sample. FIG. 13 is a block diagram of a user interface of the system of FIG. It is a figure which shows the network structure which distribute | circulates the data collected by the device as shown in FIG. FIG. 2 is a block diagram of a more specific embodiment of an apparatus for measuring glucose concentration and presence using orbital angular momentum. It is a figure which shows the optical system which detects the specific OAM signature of the signal which passes the sample to be tested. It is a figure which shows the aspect from which the ellipticity of an OAM intensity diagram changes after passing a sample. It is a figure which shows the aspect which the gravity center of an intensity | strength figure shifts after passing a sample. It is a figure which shows the aspect which the axis | shaft of an intensity | strength figure shifts after passing a sample. It is a figure which shows the OAM signature of the sample which consists only of water. It is a figure which shows the OAM signature of the sample of 15% glucose aqueous solution. It is a figure which shows the interferogram of the sample which consists only of water. It is a figure which shows the interferogram of the sample of 15% glucose aqueous solution. It is a figure which shows the amplitude of an OAM beam. It is a figure which shows the phase of an OAM beam. Figure 6 is a graph showing the ellipticity of the beam versus the output of the cuvette for three different OAM modes. It is a figure which shows the propagation by the annular beam about a cuvette. It is a figure which shows the propagation by the ring-shaped beam about water. It is a figure which shows the propagation by the annular beam about glucose. FIG. 5 shows OAM propagation through water for various drive voltages. It is a figure which shows the example of the light beam changed with the hologram in order to generate | occur | produce an OAM twist beam. FIG. 4 is a diagram illustrating various OAM modes generated by a spatial light modulator. It is a figure which shows an ellipse. FIG. 5 is a flow diagram illustrating a process for analyzing an intensity image. It is a figure which shows an ellipse fitting algorithm. It is a figure which shows the production | generation of a non-integer orthogonal state. FIG. 4 illustrates the use of a spatial light modulator for generation of non-integer OAM beams. It is a figure which shows the one aspect | mode which produces | generates a non-integer OAM beam using the superimposed Laguerre Gaussian beam. FIG. 5 illustrates the decomposition of non-integer OAM beams into integer OAM states. It is a figure which shows the aspect which can produce | generate the hologram which supplies a non-integer OAM beam with a spatial light modulator. It is a figure which shows the production | generation of the hologram for generating a non-integer OAM beam. FIG. 6 is a flow diagram illustrating generation of a hologram that generates a non-integer OAM beam. It is a figure which shows the intensity profile and phase profile of a non-integer OAM beam. FIG. 3 is a block diagram illustrating a non-integer OAM beam for OAM spectroscopy analysis. It is a figure which shows the example of an OAM state profile. It is a figure which shows the aspect which performs a multi-parameter spectroscopic analysis combining several various spectroscopic techniques. It is the schematic of the specification parameter for performing the relative measurement of an optical spectrum. It is a figure which shows an electromagnetic spectrum. It is a figure which shows the infrared spectrum of water vapor | steam. It is a figure which shows the expansion-contraction and bending vibration mode of water. Is a diagram showing stretch and bending vibration mode of the CO _2. It is a figure which shows the infrared spectrum of a carbon dioxide. It is a figure which shows the energy of the anharmonic oscillator as a function of interatomic distance. It is a figure which shows the energy curve of a vibration spring and a quantization energy level. It is a figure which shows Rayleigh scattering and Raman scattering by Stokes resonance and anti-Stokes resonance. It is a figure which shows the circuit which performs a polarization Raman method. It is a figure which shows the circuit structure which combines polarization | polarized-light Raman spectroscopy and non-polarization Raman spectroscopy. It is a figure which shows the combination of polarization Raman spectroscopy and non-polarization Raman spectroscopy, and an optical vortex. It is a figure which shows the electromagnetic wave attenuation by the water of air | atmosphere with respect to a frequency and a wavelength. It is a figure which shows the sequence of absorption and light emission linked | related by the fluorescence spectroscopy. It is a figure which shows the absorption spectrum of various substances. It is a figure which shows the fluorescence spectrum of various substances. FIG. 6 shows a pump-probe spectroscopy setup. It is a figure which shows an enhancement Raman signal. FIG. 6 shows a pump-probe OAM spectroscopy setup. It is a figure which shows the eccentricity of the measured OAM beam. It is a figure which shows the combination of OAM spectroscopy for the production | generation of a difference signal, and Raman spectroscopy. It is a flowchart of the alignment procedure. FIG. 4 is a diagram illustrating a symmetry detection scheme. It is a figure which shows an ellipse coordinate system. It is a figure which shows the trace of the ellipse using the constant (xi). It is a figure which shows the trace of the hyperbola using constant (eta). It is a figure which shows an even ins polynomial. It is a figure which shows an even ins polynomial. It is a figure which shows the mode and phase of an even ins mode. It is a figure which shows an odd ins polynomial. It is a figure which shows an odd ins polynomial. It is a figure which shows the mode and phase of an odd ins mode. It is a figure which shows dual comb spectroscopy. FIG. 2 shows a wearable multi-parameter spectroscopy device.

[Detailed description]
Referring now to the drawings, wherein like reference numerals are used throughout this specification to designate like elements, various aspects of systems and methods for detecting materials using orbital angular momentum signatures and Embodiments are described and described, and other possible embodiments are described. The figures are not necessarily drawn to scale, and the drawings may be exaggerated and / or simplified in some places for illustrative purposes only. Many possible uses and variations will be appreciated by those skilled in the art based on the following examples of possible embodiments.

  Referring now to the drawings (more specifically, FIG. 1), an embodiment is shown for detecting the presence of a particular substance in a sample based on an intrinsic orbital angular momentum signature applied to a signal passing through the sample. An optical signal 102 having a series of plane waves is applied to a device that applies an orbital angular momentum (OAM) signal to the optical signal 102 (eg, a spatial light modulator (SLM) 104). Although this embodiment contemplates the use of optical signal 102, other types of signals having other orbital angular momentum or other quadrature signals may be utilized in alternative embodiments. The SLM 104 generates an output signal 106 that applies a known OAM twist. The OAM twist has a known characteristic that is the baseline before the output signal 106 is applied to the sample 108. The sample 108 may include a substance placed in a storage container such as a cuvette, or may be a natural state such as a patient's eye or body, or a substance in a naturally occurring position. The sample 108 merely indicates that the particular substance or element of interest is detected by the described system. As it passes through the sample 108, the unique OAM signature is applied to the output signal 106 and provided as an OAM characteristic signature signal 110. It has been observed that OAM beams exhibit a unique topological evolution by interacting with chiral solutions. While it has been found that chiral molecules produce a unique OAM signature as the OAM beam passes through a sample of chiral material, it can also result in the generation of a unique OAM signature from a signal passing through a non-chiral molecule / material. Given these unique topological features, it is possible to detect the presence of molecules in a given solution with a specific signature in both amplitude and phase measurements. This characteristic signature signal 110 can then be examined (eg, using the camera 112) to detect the applied unique signal characteristics and to determine the material in the sample based on this unique signature. Multi-parameter spectroscopy for the detection of various molecules, nanoscale materials development for various industries (food (identification of food spoilage), defense and national security, chemical industry, non-invasive solutions) (Including but not limited to the pharmaceutical and medical industries for essential testing, infection, cancer cells, organic compounds and many other specific medical and dental industries). The particular substance represented by the unique signature can, in one embodiment, be determined by comparing the signature with a unique database of signatures that include known signatures associated with the particular substance or concentration. The manner of creating such a database may be known to those skilled in the art.

  Referring now to FIG. 2, the manner in which the OAM torsion beam 222 can be generated by the OAM generator 220 is shown. OAM generator 210 uses any number of devices (including holograms with amplitude masks, holograms with phase masks, spatial light modulators (SLMs) or digital light processors (DLPs)) that generate torsional beams 222 can do. The OAM generator 220 receives a light beam 221 (eg, from a laser) that includes a series of plane waves. The OAM generator 220 applies orbital angular momentum to the beam 222. Beam 222 includes a single OAM mode as shown in intensity diagram 223. The OAM torsion beam 222 passes through the sample 224 that contains the substance to be detected. As described above, the sample 224 may be in a container or in its naturally occurring position. The presence of material in sample 224 results in a new OAM mode level in intensity diagram 225. As the beam 222 passes through the sample 224, three characteristic signatures are associated with the output beam 226 based on the detection of a particular substance at a particular concentration. These signatures include an intensity pattern eccentricity change 228, a shift or translation 230 at the center of the intensity pattern, and a rotation 232 in three general directions (α, β, γ) of the ellipsoid intensity pattern output. included. Each of these characteristic signature indicators can occur in any configuration, and each characteristic signature provides a unique indication of the presence of specific substances and the concentration of these detection substances. These three characteristic signatures appear when the molecule to be measured is detected, and the manner in which these signatures change represents the concentration level. Detection of the helicity spectrum from the beam passing through the sample 224 includes detecting helical wave scattering (forward and backward) from the sample material.

  The use of optical OAM to measure glucose, amyloid β and other chiral substances has been demonstrated using the above configuration. It is observed that the OAM beam exhibits a unique topological evolution by interacting with the chiral solution in a 3 cm optical path link. It should be understood that inherent topological developments can also be brought about by non-chiral materials. It has been observed that chiral solutions (amyloid-β, glucose, etc.) exhibit an inherent topological evolution when an orbital angular momentum (OAM) beam interacts with it. OAM is typically not retained in naturally scattered photons. This makes the use of a torsion beam more accurate in identifying the helicity of chiral molecules since the OAM has no ambient light scattering (noise) upon detection. Thus, the unique OAM signature imparted by the material is not interfered by ambient light scattering (noise) that does not carry the OAM in the naturally scattered photons, making detection much more accurate. Given these unique topological features, the presence and concentration of amyloid-β in a given sample can be detected based on a specific signature in both amplitude and phase measurements. Molecular chirality refers to the structural handedness associated with discrepancies in spatial reversal or in a combination of reversal and rotation, and corresponds to the usual criterion of lack of any suitable axis of rotation. If something cannot be made identical to its reflection, it is chiral. Chiral molecules that are not superimposable with a mirror image are known as enantiomers. Conventionally, this is related to circularly polarized light even in the case of optical rotation, and the interpretation of this phenomenon generally requires understanding the state of plane polarization as a superposition of circularly polarized light having opposite rotational properties. Is done. For circularly polarized light, the left and right shapes indicate the inherent spin angular momentum sign ± h, and also the helicity of the trajectory represented by the associated electromagnetic field vector. For this reason, its interaction with the substance is enantiomerically specific.

  A continuous symmetry scale (CSM) is used to assess the symmetry or chirality of a molecule. This value is in the range of 0-100. The higher the symmetry value of a molecule, the higher the symmetry distortion of the molecule and the more chiral the molecule. The measurement is based on the shortest distance between the chiral molecule and the nearest achiral molecule.

Ｑ_ｋ：元の構造

：対称操作した構造
Ｎ：頂点の数
ｄ：サイズ正規化係数
^＊スケールは０〜１（０〜１００）である：
Ｓ（Ｇ）が大きいほど、Ｇ対称性からの偏差は高くなる A continuous symmetry measure can be obtained according to the following equation:

Q _k : original structure

: Symmetrically manipulated structure N: Number of vertices d: Size normalization coefficient
^* Scale is 0-1 (0-100):
The larger S (G), the higher the deviation from G symmetry.

Ｇ：Ｓ（Ｇ）を最小にするアキラル対称点群
アキラル分子：Ｓ（Ｇ）＝０ The continuous chirality measure SG can be determined according to:

G: Achiral symmetry point group that minimizes S (G) Achiral molecule: S (G) = 0

  Achiral molecules have a value of S (G) = 0. The more chiral the molecule is, the higher the value of S (G).

  Interest in orbital angular momentum has increased considerably due to the possibility of designing optical vortices. Here, helicity exists in the wave-front surface of the electromagnetic field, and the associated angular momentum is called the “orbit”. The radiation itself is commonly referred to as a “twisted” or “helical” beam. In most cases, optical vortices have been studied only for their interaction with achiral materials. The only obvious exception is some recent work on liquid crystals. Assess what new features (if any) can be expected when such a beam is used to investigate any system whose photoresponse is associated with an enantiomerically specific molecule It is timely and interesting to do.

  First, the criteria for the development of chirality in optical interactions is constructed in a generalized form. For simplicity, materials with inherent enantiomeric specificity are assumed. This material exhibits chirality (unique and common to all molecular components (or chromophores) involved in the light response). The results for this kind of system also apply to single molecule studies. Longer distance translation / rotation orders can also generate chirality (eg, as in twisted nematic crystals), but such mesoscopic chirality cannot directly generate enantiomerically specific interactions. The only exception is when the light wave probes two or more molecules or chromogenic groups (those that are electronically distinguishable, asymmetrically oriented and essentially achiral).

  Chiroptical interactions can be distinguished by their electromagnetic origin. Normal singlet electronic ground state molecular systems involve spatial variations in the electric and magnetic fields corresponding to the input of optical radiation. This spatial variation can be coupled with adjacent chromophore groups arranged di-symmetrically (Kirkwood's two-part model with limited application) or, more generally, the corresponding electric and magnetic fields. Can be understood to be related to chirality, either by coupling to individual groups. Chirality means local destruction of parity, allowing electrical and magnetic interaction interference. Even in the case of two groups, the paired electrical interactions correspond to the single body electrical and magnetic interactions that the two groups contain. For this reason, in the following the term “chiral center” is used for convenience to denote either a chromophoric group or a molecule.

With the advent of lasers, the Gaussian beam solution of the wave equation has become a general engineering term, and two higher-order laser modes that are extensions, Hermitian Gaussian for Cartesian symmetry, Laguerre Gaussian for cylindrical symmetry, etc. are in the laboratory. Participated in the optical operation at. Higher order Laguerre Gaussian beam modes exhibit a helical or helical phase plane. Thus, the propagation vector or eikonal of the beam (and hence the momentum of the beam) includes the orbital angular momentum, i.e. the oscillation about the sea axis, in addition to the spin angular momentum. This phenomenon is often referred to as vorticity. The representation of the Laguerre Gaussian beam is given in cylindrical coordinates:

  Here, w (x) is the beam spot size, and q (c) is a complex beam parameter including the development of the spherical wavefront and the spot size. The integers p and m are the radial mode and the azimuth mode, respectively. The exp (imθ) term represents a helical phase plane.

と、波面に垂直な光ビーム軸３０４に沿って指向された線形運動量

とを有する。周波数とは独立して、光ビーム内の各光子３０２は、光ビーム伝搬の方向に平行又は逆平行に整列した

のスピン角運動量３０６を有する。光子３０２のスピンの全ての整列により円偏光ビームが生じる。円偏光に加えて、光ビームは、円偏光に依存せず、したがって光子スピンに依存しない軌道角運動量３０８を保有していてもよい。 With further reference now to FIG. 3, one embodiment of a beam for use with the system is shown. The light beam 300 consists of a stream of photons 302 within the light beam 300. Each photon is energy

And the linear momentum directed along the light beam axis 304 perpendicular to the wavefront

And have. Independent of frequency, each photon 302 in the light beam is aligned parallel or antiparallel to the direction of light beam propagation.

Of the spin angular momentum 306. All alignment of the spins of photons 302 produces a circularly polarized beam. In addition to circularly polarized light, the light beam may possess an orbital angular momentum 308 that does not depend on circularly polarized light and therefore does not depend on photon spin.

  In optical experiments, lasers are widely used as a source of a light beam having a predetermined frequency and good behavior. A laser can be used to provide the light beam 300. The energy flux in any light beam 300 is given by a pointing vector that can be calculated from the vector product of the electric and magnetic fields in the light beam. In a vacuum or any isotropic material, the pointing vector is parallel to the wave number vector and perpendicular to the wavefront of the light beam. In ordinary laser light, the wavefront 400 is parallel as shown in FIG. The photon wave vector and linear momentum are directed along the z-direction 402 axis. The electric field distribution of such a light beam is a paraxial solution to Maxwell's wave equation, and these simple beams are most common, but other possibilities exist.

  For example, a beam having l entangled helical surfaces is also a solution to the wave equation. These complex beam structures are difficult to visualize, but their shapes are well known from l = 3 fusilli pasta. Most importantly, the wavefront has a pointing vector and a wave vector that spirals around the direction of propagation of the optical beam axis as shown at 502 in FIG.

  The pointing vector has an azimuthal component on the wavefront and has a non-zero result when integrated over the beam cross section. The spin angular momentum of circularly polarized light can be interpreted similarly. A beam having a circularly polarized plane wavefront does not have orbital angular momentum but has a pointing vector azimuth component proportional to the radial intensity gradient. When this is integrated over the cross section of the light beam, a finite value is obtained. When the beam is linearly polarized, there is no azimuthal component to the pointing vector, and hence no spin angular momentum.

によって与えられるため、動径ベクトルｒ内の方位角成分のクロス積をとると、光子６０２についての軌道運動量

が得られる。波数ベクトルの方位角成分がｌ／ｒであり、波長とは独立していることにも留意されたい。 For this reason, the momentum of each photon 302 in the light beam 300 has an azimuth component. Detailed calculation of momentum requires all of the electric and magnetic fields in the light beam (especially the electric and magnetic fields in the direction of beam propagation). For points in the beam, the ratio of azimuth and z components of momentum has been found to be l / kr (where l = helicity or orbital angular momentum; k = wave number 2π / λ; r = radial vector). The linear momentum of each photon 302 in the light beam 300 is

Therefore, if the cross product of the azimuth angle components in the radial vector r is taken, the orbital momentum about the photon 602

Is obtained. Note also that the azimuth angle component of the wave vector is l / r and is independent of wavelength.

である。 With reference now to FIGS. 6 and 7, a plane wavefront and a helical wavefront are shown. Usually, a laser beam having a plane wavefront 602 is characterized in Hermitian-Gaussian mode. These modes have rectangular symmetry and are represented by two mode indices m 604 and n 606. There are m nodes in the x direction and n nodes in the y direction. In summary, the combined mode of the x direction and the y direction is displayed as HG _mn 608. In contrast, as shown in FIG. 7, a beam having a helical wavefront 702 is represented by a Laguerre-Gaussian mode (exponent I 703, number of intertwined helices 704, and p (number of radial nodes 706). The best). The Laguerre-Gaussian mode is displayed as LG _mn 710. When l ≠ 0, the phase singularity on the light beam 300 is 0 in the axial intensity. When the light beam 300 having a helical wavefront is further circularly polarized, the angular momentum has an orbital component and a spin component, and the total angular momentum of the light beam is per photon.

It is.

ここで、∇はデル演算子であり、Ｅは電場強度であり、Ｂは磁束密度である。これらの方程式を用いて、マクスウェルの元の方程式から２３個の対称性／保存量を導き出すことができる。しかしながら、よく知られた保存量は１０個しかなく、これらのうち数個しか商業的に使用されていない。歴史的には、マクスウェルの方程式が元の四元数の形式を維持していれば、対称性／保存量を観測することはより容易であったと考えられるが、ヘヴィサイドによって現在のベクトル形式に修正されたことから、マクスウェルの方程式においてかかる固有の対称性を観測することがより困難となった。 The orbital angular momentum state of the transmitted energy signal can be used to embed physical information in the electromagnetic radiation transmitted by the signal. The Maxwell-Heaviside equation can be expressed as:

Here, ∇ is the Dell operator, E is the electric field strength, and B is the magnetic flux density. Using these equations, 23 symmetries / conservations can be derived from Maxwell's original equations. However, there are only 10 well-known storage quantities, and only a few of these are used commercially. Historically, it would have been easier to observe symmetry / conservation if Maxwell's equations maintained the original quaternion form, but heaviside changed to the current vector form. This has made it more difficult to observe this inherent symmetry in Maxwell's equations.

Conserved quantities and electromagnetic fields can be represented by the conservation of system energy and the conservation of linear momentum of the system. Time symmetry, or conservation of system energy, can be expressed using the Pointing theorem according to the following equation:

Spatial symmetry, ie the conservation of the linear momentum of the system representing the electromagnetic Doppler shift, can be expressed by the following equation:

The conservation of the energy center of the system is represented by the following equation:

Similarly, the conservation of angular momentum in a system that produces an azimuth Doppler shift is represented by the following equation:

For a radiation beam in free space, the EM field angular momentum J ^em can be separated into two parts:

For each singular Fourier mode in real number display:

The first part is the EM spin angular momentum S ^em , whose classical representation is wave polarization. The second part is the EM orbital angular momentum ^Lem , and its classical representation is wave helicity. In general, both the EM linear momentum P ^em and the EM angular momentum J ^em = L ^em + S ^em are emitted to the far field.

ここで、Ｓはポインティングベクトル

であり、Ｕはエネルギー密度

であり、Ｅ及びＨはそれぞれ電場及び磁場を含み、ε及びμ_０はそれぞれ媒質の誘電率及び透磁率である。次いで、以下の方程式に従い、光渦度Ｖを光学速度の回転（curl）によって決定することができる：

By using the pointing theorem, the optical vorticity of the signal can be determined according to the following optical velocity equation:

Where S is a pointing vector

Where U is the energy density

Where E and H include an electric field and a magnetic field, respectively, and ε and μ ₀ are the dielectric constant and permeability of the medium, respectively. The optical vorticity V can then be determined by the optical velocity curl according to the following equation:

  Referring now to FIGS. 8 and 9, in a plane wave situation where only the spin vector changes (FIG. 8), and the spin and orbital vectors change so that the pointing vector spirals around the propagation direction. In the situation (FIG. 9), the manner in which the signal and the corresponding pointing vector of the signal vary is shown.

  In the situation of the plane wave shown in FIG. 8 (only the spin vector of the plane wave changes), the transfer signal can take one of three configurations. If the spin vectors are in the same direction, a linear signal is provided, generally as shown at 804. 804 shows a spin vector that changes only in the x direction to provide a linear signal. On the other hand, note that the spin vector can be varied in the y direction to provide a linear signal that is similar to that shown at 804 but appears in a direction perpendicular to the signal shown at 804. For linearly polarized light as shown at 804, the signal vectors are in the same direction and have the same magnitude.

  In the circular polarization shown at 806, the signal vectors 812 are 90 degrees relative to each other but have the same magnitude. This causes the signal to propagate as shown at 806, resulting in the circularly polarized light 814 shown in FIG. In elliptically polarized light 808, the signal vectors 816 are likewise 90 degrees relative to each other but have different magnitudes. This results in elliptically polarized light 818 as shown in signal propagation 408. For the plane wave shown in FIG. 8, the pointing vector is maintained in a fixed direction with the various signal configurations shown in the figure.

The situation in FIG. 9 shows the case where the natural orbital angular momentum is applied to the signal. When this occurs, the pointing vector S 910 spirals around the overall propagation direction 912 of the signal. The pointing vector 910 has three axial components S _φ , S _p, and S _z , and these vary so that the vector spirals around the signal propagation direction 912. By changing the value of various vectors, including the pointing vector 910, the pointing vector helix can be varied to transmit signals at the same wavelength or frequency, as described in more detail herein. It becomes possible. Additionally, the value of the orbital angular momentum indicated by the pointing vector 910 can be measured to determine the presence of a particular material to be processed by the scanning mechanism and the concentration corresponding to the particular material.

  10A-10C show the difference in signals with different helicities (i.e. applied orbital angular momentum). Different helicities indicate different substances and concentrations of substances in the sample that are passed through the beam. By determining a specific orbital angular momentum signature associated with the signal, a specific substance and the amount of substance concentration can be determined. Each of the spiral pointing vectors associated with signals 1002, 1004 and 1006 provides a different shaped signal. Signal 1002 has an orbital angular momentum of +1, signal 1004 has an orbital angular momentum of +3, and signal 1006 has an orbital angular momentum of -4. Each signal has a characteristic orbital angular momentum and a corresponding pointing vector, allowing the signal to be indicative of a particular substance and substance concentration corresponding to the detected orbital angular momentum. This makes it possible to determine the substance and the concentration of various types of substances from the signal. This is because orbital angular momentum can be detected separately and provides a specific indicator of the specific substance and the concentration of the specific substance that has influenced the orbital angular momentum of the signal transmitted through the sample material.

  FIG. 11A shows pointing vector propagation for various eigenmodes. Each of the rings 1120 represents a different natural mode or twist that represents a different orbital angular momentum. Each of the different orbital angular momentums is associated with a specific substance and a specific concentration of a specific substance. The detection of orbital angular momentum provides an indication of the presence and concentration of the relevant substance detected by the device. Each of the rings 1120 represents the concentration of different substances and / or selected substances that are monitored. Each of the eigenmodes has a pointing vector 1122 that produces a ring indicating a different substance and substance concentration.

  The topological charge can be multiplexed for either linearly or circularly polarized frequencies. In the case of linear polarization, the topological charge is multiplexed with vertical and horizontal polarization. In the case of circularly polarized light, the topological charge is multiplexed with left circularly polarized light and right circularly polarized light. Topological charge is another name for helicity index “I” or the amount of twist or OAM applied to the signal. The helicity index may be positive or negative.

  Topological charge l is a spiral phase plate (SPP) (using an appropriate material with a specific index of refraction) and the ability to machine or phase mask holograms created from the new material, as shown in FIG. 11B. And can be generated using The helical phase plate can convert an RF plane wave (l = 0) into a specific helicity torsional wave (ie, l = + 1).

  Referring now to FIG. 12, a block diagram of an apparatus that provides for the detection of the presence of a substance and the measurement of the concentration of various substances in accordance with the orbital angular momentum detected by the apparatus in accordance with the principles described hereinabove. Indicated. Emitter 1202 transmits wave energy 1204 including a series of plane waves. Emitter 1202 can provide a series of plane waves such as those described above with respect to FIG. Orbital angular momentum generation circuitry 1206 generates a series of waves having orbital angular momentum applied to the wave 1208 in a known manner. The orbital angular momentum generation circuitry 1206 can utilize a hologram or some other type of orbital angular momentum generation process, as described in more detail herein below. The OAM generation circuitry 1206 can be generated by transmitting a plane wave through a spatial light modulator (SLM), amplitude mask, or phase mask. An orbital angular momentum torsion wave 1208 is applied to the sample material 1210 to be tested. Sample material 1210 contains a material, and the presence and concentration of the material is determined by a detection device according to the process described herein. The sample material 1210 may be in a container or in its natural naturally occurring position (such as an individual's body).

  A series of output waves 1212 from the sample material 1210 exit the sample and are given a specific orbital angular momentum as a result of the concentration of the material in the sample material 1210 and the specific material under study. The output wave 1212 is applied to a matching module 1214 that includes a mapping aperture that amplifies a particular orbital angular momentum generated by a particular research material. The alignment module 1214 amplifies the orbital angular momentum associated with the particular substance and substance concentration detected by the device. The amplified OAM wave 1216 is supplied to the detector 1218. The detector 1218 detects OAM waves related to substances and substance concentrations in the sample and provides this information to the user interface 1220. Detector 1218 can utilize a camera to detect characteristic topological features from the beam passing through the sample. User interface 1220 interprets the information and provides an indication of the type and concentration of the associated substance to the individual or recording device.

  Referring now to FIG. 13, the emitter 1202 is shown more specifically. The emitter 1202 can emit many types of energy waves 1204 to the OAM generation module 1206. Emitter 1202 may emit light wave 1300, electromagnetic wave 1302, sound wave 1304, or any other type of particle wave 1306. The emitted wave 1204 is a plane wave such as that shown in FIG. 4 where no orbital angular momentum is applied and can be generated from various types of light emitting devices and may contain information. In one embodiment, the light emitting device may comprise a laser. Plane waves have parallel wavefronts with no torsion or helicity applied, and the orbital angular momentum of the waves is equal to zero. The pointing vector in the plane wave is completely coincident with the wave propagation direction.

  The OAM generation module 1206 processes the incident plane wave 1204 and imparts a known orbital angular momentum to the plane wave 1204 supplied from the emitter 1202. The OAM generation module 1206 generates torsional or helical electromagnetic waves, light waves, sound waves, or other types of particle waves from the plane wave of the emitter 1202. As shown in FIG. 14, the helical wave 1208 does not match the wave propagation direction, but travels around the propagation direction. The OAM generation module 1206 may include a fixed orbital angular momentum generator 1402 as shown in FIG. 14 in one embodiment. The fixed orbit angular momentum generator 1402 receives the plane wave 1204 from the emitter 1202 and generates an output wave 1404 to which the fixed orbit angular momentum is applied.

  Fixed orbital angular momentum generator 1402 may include a holographic image that, in one embodiment, applies fixed orbital angular momentum to plane wave 1204 to generate OAM torsional wave 1404. Various types of holographic images can be generated to generate a desired orbital angular momentum twist for the optical signal applied to the orbital angular momentum generator 1402. Various examples of these holographic images are shown in FIGS. 15A-15D. In one embodiment, conversion of the plane wave signal emitted from the emitter 1202 by the orbital angular momentum generation circuitry 1206 may be accomplished using a holographic image.

Most commercially available lasers emit an HG ₀₀ (Hermitian-Gaussian) mode 1602 (FIG. 16) having a plane wavefront and a lateral intensity represented by a Gaussian function. Although a number of methods have been used to successfully convert the HG ₀₀ Hermite-Gaussian mode 1602 to Laguerre-Gaussian mode 1604, the use of holograms is most easily understood.

ここで、ｚ_Ｒはレイリー範囲であり、ｗ（ｚ）はビームの半径であり、Ｌ_Ｐはラゲール多項式であり、Ｃは定数であり、ビームウエストはｚ＝０である。 The cylindrically symmetric solution u _pl (r, φ, z) describing the Laguerre-Gaussian beam is given by the following equation:

Here, z _R is the Rayleigh range, w (z) is the radius of the beam, L _P is a Laguerre polynomial, C is a constant, the beam waist is z = 0.

  A computer generated hologram, in its simplest form, is generated from a calculated interference pattern (which occurs when the desired beam intersects a conventional laser beam at a small angle). This calculated pattern is transferred to a high resolution holographic film. When the developed hologram is placed in the original laser beam, a diffraction pattern results. This primary has the desired amplitude and phase distribution. This is one aspect of implementing the OAM generation module 1206. Numerous examples of holographic images used in the OAM generation module are shown with respect to FIGS. 15A-15D.

  Hologram design is refined at various levels. A hologram that contains only black and white regions and has no gray scale is called a binary hologram. In binary holograms, the relative intensities of the two interfering beams have no role, and the transmission of the hologram is set to zero when the calculated phase difference is between zero and π. When the phase difference is between π and 2π, the unit amount is set. The limitation of binary holograms is that the incident power hardly reaches the first-order diffraction spot (although it can be partially overcome by grating blazing). If modal purity is particularly important, it is possible to create more sophisticated holograms in which the contrast of the pattern varies with radius so that the diffracted beam has the required radial profile.

  A plane wave irradiated through the holographic image 1502 is subjected to a predetermined orbital angular momentum shift after passing through the holographic image 1502. The OAM generator 1202 is fixed in the sense that the same image is used and applied to the beam passing through the holographic image. Since the holographic image 1502 does not change, the same orbital angular momentum is always applied to the beam that passes through the holographic image 1502. A number of embodiments of various holographic images that can be utilized in the orbital angular momentum generator 1202 are shown in FIGS. 15A-15D, but to achieve the required orbital angular momentum in the beam illuminated through the image 1502. It should be understood that any type of holographic image 1502 can be utilized.

  In another example of a holographic image shown in FIG. 17, a hologram is shown that utilizes two separate holograms combined in a lattice fashion to generate multiple orbital angular momentums (l). The superimposed holograms of FIG. 17 have orbital angular momentum of l = 1 and l = 3, and are superimposed on each other to form a composite vortex grating 1702. The holograms used are combined with each other in the form of a lattice, and various numbers of orbital angular momentum (l) (two holograms are not only linear (l = + 1, l = 0, l = -1), but many May be constructed in such a manner as to generate a square shape that can more easily specify the variable of For this reason, in the example of FIG. 17, the orbital angular momentum fluctuates from +4 to +1 and −2 along the upper end, and fluctuates from +2 to −1 and −4 at the lower end. Similarly, the orbital angular momentum along the left end varies from +4 to +3 and +2, and at the right end varies from −2 to −3 and −4. The orbital angular momentum given across the horizontal center of the hologram varies from +3 to 0 and -3, and varies from +1 to 0 and -1 along the vertical axis. For this reason, various orbital angular momentums can be realized according to the portion of the grating through which the beam can pass.

  Referring now to FIG. 18, in addition to the fixed orbital angular momentum generator, the orbital angular momentum generation circuit configuration 1206 may include an adjustable orbital angular momentum generator circuit configuration 1802. Adjustable orbital angular momentum generator 1802 receives input plane wave 1204 and additionally receives one or more adjustment parameters 1804. The adjustment parameter 1804 adjusts the adjustable OAM generator 1802 and applies the selected orbital angular momentum so that the selected orbital angular momentum value is applied to the adjusted OAM wave 1806 output from the OAM generator 1802. Is done.

  This can be achieved in various ways. In one embodiment shown in FIG. 22, adjustable orbital angular momentum generator 1802 may include a plurality of hologram images 2202 within adjustable OAM generator 1802. The adjustment parameter 1804 enables selection of one of the holographic images 2206 and provides the desired OAM wave twist output signal 1806 via the selector circuit 2204. Alternatively, a lattice holographic image as described in FIG. 16 can be used to irradiate a portion of the lattice image with the beam to provide the desired OAM output. The adjustable OAM generator 1802 has the advantage that it is controlled to apply a specific orbital angular momentum to the output orbital angular momentum wave 1806 in response to the supplied input parameter 1804. This makes it possible to monitor the presence and concentration of different substances, or alternatively to monitor different concentrations of the same substance.

  Referring now to FIG. 19, a block diagram of the adjustable orbital angular momentum generator 1802 is more specifically implemented. Generator 1802 includes a plurality of holographic images 1902 that provide various types of orbital angular momentum for the supplied optical signal. These holographic images 1902 are selected according to a selector circuit configuration 1904 that is responsive to input adjustment parameters 1804. The selected filter 1906 includes the holographic image selected in response to the selector controller 1904, receives the input plane wave 1204, and provides an adjusted orbital angular momentum wave output 1206. In this aspect, a signal having a desired orbital angular momentum can be output from the OAM generation circuit configuration 1206.

は、出力信号内の１光子当たりのビームの軌道角運動量である。各々のｌについて、左の列２００２は光ビームの瞬時位相である。中央の列２００４は角度強度プロファイルを含み、右の列２００６は、かかるビームが平面波に干渉して、らせん状の強度パターンを発生させる場合に生じる状態を示している。これは、図２３の様々な行において軌道角運動量−１、０、１、２及び３について示される。 Referring now to FIG. 20, the manner in which the output of the OAM generator 1206 can vary the signal by applying different orbital angular momentum is shown. FIG. 20 shows a helical phase plane in which the pointing vector is no longer parallel to the beam axis (and thus orbital angular momentum has been applied). Within any fixed radius within the beam, the pointing vector follows a helical trajectory around the axis. Rows are denoted by l and orbital angular momentum quantum numbers

Is the orbital angular momentum of the beam per photon in the output signal. For each l, the left column 2002 is the instantaneous phase of the light beam. The middle column 2004 contains the angular intensity profile, and the right column 2006 shows what happens when such a beam interferes with a plane wave to produce a helical intensity pattern. This is shown for orbital angular momentum-1, 0, 1, 2, and 3 in the various rows of FIG.

  Referring now to FIG. 21, the OAM generator 1206 uses the mode converter 2104 and the dove prism 2110 to convert the Hermitian-Gaussian beam output from the emitter 1202 into a Laguerre-Gaussian beam with orbital angular momentum. Alternative embodiments that can be converted are shown. A Hermitian-Gaussian mode plane wave 2102 is supplied to the π / 2 mode converter 2104. The π / 2 mode converter 2104 generates a Laguerre-Gaussian mode beam 2106. A Laguerre-Gaussian mode beam 2106 is applied to either a π-mode converter 2108 or a dove prism 2110 (which reverses the mode and produces an inverse Laguerre-Gaussian mode signal 2112).

  Referring now to FIG. 22, the manner in which the hologram in the OAM generator 1206 generates a twisted light beam is shown. The hologram 2202 can generate a light beam 2204 and a light beam 2206 having a helical wavefront and an associated orbital angular momentum of 1h per photon. A suitable hologram 2202 can be calculated or generated from the interference pattern between the desired beam shape 2204, 2206 and the plane wave 2208. The resulting holographic pattern in hologram 2202 resembles a diffraction grating but has l-forks on the beam axis. When a plane wave 2208 is applied to the hologram, the first order diffracted beams 2204 and 2206 have the desired helical wavefront to provide the desired first order diffracted beam representation 2210.

  Referring now to FIG. 23, a sample 1210 receives an input OAM torsional wave 1208 supplied from an OAM generator 1206 and depends on a particular OAM signature (depending on the concentration of a substance in the sample 1210 or a particular monitored substance). The manner in which the output OAM wave 1212 associated with) is supplied is shown more specifically. Sample 1210 can include any sample under study and can be in solid, liquid or gaseous form. The sample material 1210 that can be detected using the systems described herein can include a variety of different materials. As previously mentioned, the substance may comprise a liquid such as blood, water, oil or chemicals. Various types of carbon bonds such as C—H, C—O, C—P, C—S, or C—N can be subjected to detection. The system can detect various types of bonds between carbon atoms (eg, single bonds (methane or isooctane), double bond elements (butadiene and benzene), or triple bond carbon elements such as acetylene).

Sample 1210 is a detectable element such as an organic compound (carbohydrate, lipid (cylcerol and fatty acid), nucleic acid (C, H, O, N, P) (RNA and DNA), or polymer of amino NH ₂ and carboxyl COOH. Various types of proteins, including amino acids such as tryptophan, tyrosine and phenylalanine). Various chains in the sample 1210 such as monomers, isomers and polymers can also be detected. Enzymes such as ATP and ADP in the sample can be detected. Substances produced or released by the body's glands are present in the sample and may be detected. These substances include elements released by exocrine glands via tubes / conduit, endocrine glands released directly into blood samples, or hormones. Various types of glands that can detect secretions in sample 1210 include hypothalamus, pineal gland, pituitary gland, parathyroid, thyroid, thymus, torso adrenal and pancreas, and male or female ovary Or contains hormones released from the testis.

  Sample 1210 can also be used to detect various types of biochemical markers in the blood and urine of individuals such as melanocytes and keratinocytes. Sample 1210 can include various parts of the body to detect protective substances. For example, for skin, sample 1210 can be used to detect carotenoids, vitamins, enzymes, b-carotene and lycopene. Regarding eye pigments, melanin / eumelanin, dihydroxyindole or carboxylic groups can be detected. The system may also detect various types of substances within the body's biosynthetic pathway, including hemoglobin, myoglobin, cytochrome, porphyrin molecules (such as protoporphyrin, coporphyrin, uroporphyrin and hematoporphyrin) in sample 1210. it can. The sample 1210 may contain various bacteria to be detected, such as propionic acid bacteria and acne. Various types of plaque bacteria (such as porphyromonos gingivitis, prevotella intremedi, and prevotella nigrescens) may also be detected. . Sample 1210 can also be used to detect glucose in insulin in blood sample 1210. Sample 1210 may contain amyloid-β to be detected. In that case, detection of amyloid-β in the sample can be used to determine early Alzheimer's disease. Higher levels of amyloid-β can provide an indication of an early stage of Alzheimer's disease. The sample 1210 can include any material that it is desired to detect that imparts an inherent OAM twist to the signal passing through the sample.

  The orbital angular momentum in the beam provided in the sample 1210 can be transferred from light to the material molecules in response to the rotation of the material molecules. When a circularly polarized laser beam with a helical wavefront traps molecules in the angular ring of light around the beam axis, transmission of both orbital angular momentum and spin angular momentum can be observed. Capture is in the form of optical tweezing that is achieved without mechanical constraints due to the intensity gradient of the ring. The orbital angular momentum transmitted to the molecule causes the molecule to circulate around the beam axis, as shown at 2402 in FIG. The spin angular momentum causes the molecule to spin on its own axis, as shown at 2404.

  An orbital angular momentum different from the orbital angular momentum given to the input OAM wave 1208 is associated with the output OAM wave 1212 from the sample 1210. The difference in the output OAM wave 1212 depends on the substances contained in the sample 1210 and the concentration of these substances in the sample 1210. A unique orbital angular momentum is associated with each of various substances at different concentrations. Thus, by analyzing the particular orbital angular momentum signature associated with the output OAM wave 1212, a determination can be made regarding the substances present in the sample 1210 and the concentration of these substances in the sample can also be determined. Can do.

  Referring now to FIG. 25, the matching module 1214 receives an output orbital angular momentum wave 1212 associated with a particular signature based on the orbital angular momentum imparted to the wave passing through the sample 1210 from the sample 1210. The matching module 1214 amplifies the specific orbital angular momentum of the target and provides an amplified wave (amplified desired orbital angular momentum 1216 of the target). The matching module 1214 may include a matching aperture that amplifies the detected orbital angular momentum associated with a particular substance or property under study. The matching module 1214 may comprise a holographic filter as described with respect to FIGS. 15A-15D, in one embodiment, to amplify the desired orbital angular momentum wave of interest. An alignment module 1214 is established based on the particular material of interest that the system attempts to detect. The alignment module 1214 may include a fixed module using holograms as shown in FIGS. 15A-15D or an adjustable module in a manner similar to that discussed with respect to the OAM generation module 1206. In this case, a number of different orbital angular momentums can be amplified by the matching module to detect different substances or different substance concentrations in the sample 1210. Other examples of components of the matching module 1214 include the use of quantum dots, nanomaterials, or metamaterials to amplify any desired orbital angular momentum values in the waveform received from the sample 1210.

  Referring now to FIG. 26, the matching module 1214 does not use the holographic image to amplify the desired orbital angular momentum signal, but to generate a higher orbital angular momentum light beam. -linear crystal) can be used. By using the nonlinear crystal 2602, the fundamental component orbital angular momentum beam 2604 can be applied to the nonlinear crystal 2602. Nonlinear crystal 2602 produces a second harmonic signal 2606.

  Referring now to FIG. 27, detector 1218 (in contrast, amplified orbital angular momentum wave 1216 from matching circuit 1214 so that detector 1218 can extract the desired OAM measurement value 2602) is more specific. Shown in A detector 1218 receives the amplified OAM wave 1216 and detects and measures an observable change in the orbital angular momentum of the emitted wave due to the presence of a particular substance in the sample 1210 and the concentration of a particular substance under study. . Detector 1218 can measure an observable change in emitted amplified OAM wave 1216 from the state of input OAM wave 1208 applied to sample 1210. The extracted OAM measurement value 2702 is applied to the user interface 1220. The detector 618 includes an orbital angular momentum detector 2104 that determines a profile of the orbital angular momentum state of the orbital angular momentum in the orbital angular momentum signal 616, and a substance in the sample according to the detection profile of the orbital angular momentum state of the orbital angular momentum. And a processor 2106 for determining. The manner in which the difference in orbital angular momentum can be detected by the detector 1218 is more specifically shown with respect to FIGS.

  FIG. 28 shows a difference in influence between spin angle polarization and orbit angle polarization caused by passing a light beam through the sample 2802. In the sample 2802a, an aspect in which the spin angle polarization changes according to the beam passing through the sample 2802a is shown. The polarization of the wave having a particular spin angular momentum 2804 passing through the sample 2802a rotates from position 2804 to a new position 2806. The rotation occurs in the same polarization plane. Similarly, as shown for sample 2802b, the image generally appears as shown at 2808 before passing through sample 2802b. As the image passes through sample 2802b, the image rotates from the position shown at 2810 to the rotated position shown at 2812. The amount of rotation depends on the presence of the substance detected in the sample 2802 and the concentration level of the substance detected. Thus, as seen for sample 2802 in FIG. 28, both spin angular polarization and orbital angular momentum change based on the presence and concentration of the substance in sample 2802. By measuring the amount of image rotation caused by changes in orbital angular momentum, the presence and concentration of a particular substance can be determined.

ここで、ｌは軌道角運動量数であり、Ｌは試料の経路長であり、Ｃは検出される物質の濃度である。 This whole process can be illustrated more specifically in FIG. The light source 2902 emits a light beam through the magnifying optical component 2904. The expanded light beam is applied to a metalab generated hologram 2906 that imparts orbital angular momentum to the beam. The torsion beam from the hologram 2906 is irradiated through a sample 2908 having a specific length L. As described above, the sample 2908 may be in a container or in its naturally occurring state. This produces a torsion beam on the output side of the sample 2908, resulting in a large number of detectable waves associated with various orbital angular momentum 2910. The image 2912 associated with the light beam applied to the sample 2908 rotates by an angle φ depending on the presence and concentration of the substance in the sample 2908. The rotation φ of the image 2912 is different for each value −l or + l of the orbital angular momentum. The change in image rotation Δφ can be described according to the following equation:

Here, l is the orbital angular momentum number, L is the path length of the sample, and C is the concentration of the substance to be detected.

  For this reason, the sample length L is known and the orbital angular momentum can be determined using the process described herein, so the concentration of the substance in the given sample is calculated from these two pieces of information. Can be possible.

  The above equations can be utilized in the user interface specifically illustrated by FIG. The user interface 1220 processes the OAM measurements 3002 using an internal algorithm 3002 to generate substance and / or concentration information 3004 that can be displayed on some type of user display. The algorithm, in one embodiment, utilizes the equations described herein above and determines the substance and / or concentration based on the sample length and the detected variation in orbital angular momentum. The process of calculating substances and / or concentrations can be performed in a laboratory situation (information may be communicated wirelessly to the laboratory or user interface, personal cloud or public cloud via local area network or wide area network The user interface may be associated with a wearable device connected to a mobile phone or meter running an application on the mobile phone connected to the mobile phone). The device user interface 3020 may have either a wired or wireless connection utilizing Bluetooth, ZigBee or other wireless protocols.

  Referring now to FIG. 31, the manner in which various data collected in the user interface 1220 collected in the manner described hereinabove can be stored and utilized for higher level analysis. Is shown. Various devices 3102 that collect data can communicate via the private network cloud 3104 or the public cloud 3106 as described herein above. When communicating with the private cloud 3104, the device 3102 simply stores information associated with a particular user device that is used in connection with analysis of the user associated with that user device. Thus, individual users can monitor and store information regarding current glucose concentrations in order to monitor and manage their diabetes.

  Alternatively, if information is aggregated from multiple devices 3102 in the public cloud 3106, this information is provided to the public cloud 3106 directly from individual devices 3102 or via the private cloud 3104 of the associated network device 3102. can do. Using this information in the public cloud 3106, a large database can be established in the server 3108 associated with the public cloud 3106, and various information associated with the processed information from each of the individual devices 3102 can be established. Allows large-scale analysis of health-related issues. This information can be used to analyze public health issues.

  Thus, the user interface 1220 not only includes an algorithm 3002 that determines substance and / or concentration information 3004, but also communicates the collected information wirelessly via a public or private cloud, as described with respect to FIG. It includes a wireless interface 3006 that enables Alternatively, the user interface may include a storage database 3008 that allows the collected information to be stored locally rather than transmitted wirelessly to a remote location.

  Referring now to FIG. 32, a specific example of a block diagram of a specific apparatus for measuring the presence and concentration of glucose using photon orbital angular momentum of a light beam irradiated through a glucose sample is shown. Although this example relates to the detection of glucose, those skilled in the art will appreciate that this example is applicable to the detection of the presence and concentration of any substance. In this process, the second harmonic is generated by a helical light beam using a nonlinear crystal as described with respect to FIG. The light emitting module 2402 generates a planar electromagnetic wave supplied to the OAM generation module 3204. The OAM generation module 3204 generates a light wave to which orbital angular momentum is applied using a hologram in order to generate a wave having an electromagnetic vortex. An OAM torsion wave is applied to the sample 3206 under study and the glucose and glucose concentration in the sample is detected. The rotated signature exits the sample 3206 in the manner described above with respect to FIGS. 28 and 29 and is provided to the alignment module 3208. The matching module 3208 amplifies the orbital angular momentum so that the observed concentration can be calculated from the orbital momentum of the glucose signature. These amplified signals are supplied to a detection module 3210 (which measures the radius of the beam w (z) or the rotation of the image imparted to the sample by the light beam). This detected information may be provided to a user interface (including a wired sensor interface or a wireless Bluetooth or ZigBee connection) to provide a substance to a reading meter or user phone that displays concentration information about the sample. It becomes possible. In this way, the concentration of the various types of substances described herein can be determined utilizing the orbital angular momentum signature of the sample under study, and the concentration of these substances or their concentration in the sample. Detection is determined as described.

  A Laguerre Gaussian beam representing orbital angular momentum (OAM) is determined as the basis for spatial division multiplexing (SDM) in communication applications (eg, using mux-demux optical element designs), subject to the orthogonality of Laguerre polynomials. Yes. OAM beams are also of interest in quantum information science. OAM also allows probing of solutions of chiral and non-chiral molecules.

  FIG. 33 shows a further optical arrangement for transmitting and detecting information. The twisted nematic LCOS SLM 3302 is implemented with a 1024 x 768 array (covering the visible wavelength range (430 nm to 650 nm) and easily interfaced via VGA connection) with 9 μm pitch and 8-bit resolution . A programmable SLM 3302 allows for the generation of beams of various designs. A twisted nematic (TN) liquid crystal (LCOS) SLM on silicon is particularly useful for implementing holograms that modulate the phase plane of the input plane wave 102 (FIG. 1) or Gaussian beam. The SLM is computer addressable using a common software package such as Matlab or Mathematica, for example, to define any two-dimensional phase shift imprinted on the beam input using a hologram.

The collimated input beam is reflected from the display and appropriately encoded by a phase retarding fork diffraction grating or hologram. The generation equation for a forked grating can be expressed as a Fourier series as follows:

Here, r and φ are coordinates, l is the degree of vorticity, and D is the period of the linear diffraction grating away from the fork pole. The weight t _m of the Fourier component of the phase grating can be expressed as an integer order Bessel function as follows:

Here, kα biases the phase of the fork type diffraction grating, and kβ modulates the phase of the fork type diffraction grating. Typically, only a portion of this series is needed to generate an OAM beam. For example, the following transfer patterns have been successful:

  Referring now again to FIG. 33, an optical arrangement for detecting the unique signature of the signal passing through the sample 3303 to be tested is shown. Sample 3303 may be in a container or in its naturally occurring state. At a high level, this instrument is equipped with a Mach-Zehnder interferometer. One arm of the interferometer propagates the reference beam 3310. A reference beam 3310 is generated by a laser 3304 that generates a light beam that includes a plurality of plane waves transmitted through a telescope 3306. The plane wave light beam from the telescope 3306 passes through the first beam splitter 3308. A beam splitter 3308 generates a reference beam 3310 that is reflected from the mirror 3311 to the interference circuit 3312. The reference beam 3310 may be a plane wave, or a spherical wavefront may be realized by adding a lens. This arm is interrupted for amplitude-only measurements.

  In the second arm, the separated plane wave beam from the beam splitter 3308 is combined with the beam supplied from the spatial light modulator 3302 by the beam combiner 3314. Spatial light modulator 3302 includes fork hologram 3316 and provides a light beam. A beam combiner 3314 combines the fork hologram beam 3318 from the SLM 3302 and the plane wave beam 3320 from the laser 3304 to produce an OAM or other orthogonal function twisted beam of known signature. This beam is reflected by a series of mirrors 3322 and focused on a pinhole aperture 3324 and then a beam with a known orbital angular momentum passes through the sample 3303 to be tested.

  Sample torsion beam 3326 is interfered by reference beam 3310 at signal combiner 3312. This interference image can then be recorded by a camera or recording device 3328. This provides a unique OAM signature 3330 that can be analyzed to detect substances in the sample 3303 under test. As can be seen, the unique OAM signature 3330 is different from the transmit beam signature 3332. The manner in which the signature changes is described in more detail below.

  In the second arm, the collimated plane wave input beam 3320 is converted into an OAM encoded beam using the LCOS SLM 3302. The SLM 3302 is driven by the Matlab program on the extended laptop display and displays any l or ρ fork hologram. Following the SLM 3302, the beam is reflected by three mirrors 3322 to provide a sufficient distance for separation of the diffractive OAM mode, thereby selecting the desired mode through the sample 3303 to be tested by the pinhole aperture 3324 can do.

  Several substances of interest can be detected by OAM signature using the setup of FIG. Examples of these substances include acetone, isopropyl alcohol, sucrose, amyloid-β and glucose (steam distilled water). A spectroscopic grade soda lime glass cuvette (1 cm × 2.5 cm × 3 cm) or a larger custom circular cuvette with a BK7 cover glass in the cap can be used to accommodate the sample 3303 to be tested.

  A sample 3303 to be tested is placed on a translation stage. The translation stage is arranged to allow rapid and repeatable positioning in and out of the beam path by either movement of the sample or movement of the beam projector. In addition, back reflections from the sample service are carefully monitored and blocked by a throttling so that no false secondary interactions occur. Since the optical power through the sample is low (less than 25 μW), a temperature gradient in solution that depends on the refractive index is avoided.

  Inserting waveplates, variable retarders and polarizers before and after the sample to be tested produced no significant results. It is well known that glucose has an optical rotation response at these wavelengths, but the product of concentration and path length is too small to cause a significant shift in polarization state. This suggests that OAM and glucose are more prominent responses than the optical rotation of the molecule.

  A beam image 3330 at the output of the instrument is recorded using a high resolution DSLR camera 3328. The high resolution DSLR camera 3328 is fixedly mounted perpendicular to the beam propagation direction and is remotely activated to prevent instrument vibration or movement. The ellipticity measurement is performed using Photoshop and Matlab (or software or application that measures and processes similar types of images).

  Using this instrument, changes in the OAM state imparted to the input beam by the sample 3303 to be tested can be quantified in terms of both intensity and phase. A series of experiments was conducted mainly using an aqueous glucose solution. The 15% stock solution was diluted to various desired concentrations. Since various isomers of sugars interact with each other before reaching equilibrium, new or altered solutions require settling time. The solution was allowed to equilibrate overnight (approximately 15 hours, much longer than the recommended 2 hours) in a capped cuvette to prevent evaporation.

  As described above with respect to FIG. 1, the passage of the sample 3303 imparts a unique OAM signature to the light beam passing through the sample. This unique OAM signature identifies the presence of the substance in the sample and the concentration of the substance in the sample. This unique OAM signature has a number of differences from the OAM signal signature input to the sample 3303. The characteristics of the unique OAM signature are shown in FIGS. FIG. 34 shows an aspect in which the ellipticity of the OAM intensity diagram changes after passing through the sample 3303. Initially, as shown at 3402, the intensity diagram has a substantially circular shape (from a plane wave OAM beam prior to passing through the sample 3303). After passing through sample 3303, the intensity diagram has a much more elliptical shape, generally as shown at 3404. The shape of this ellipse is a unique characteristic that varies depending on the substance to be detected and the concentration of the substance to be detected. By detecting the ellipticity of the intensity diagram, the presence of a particular substance in the sample can be determined.

  FIG. 35 shows further properties of the OAM signature that can be changed by passing through the sample 3303. In this case, the center of gravity of the intensity diagram is shifted. A position 3502 indicates the initial position of the center of gravity of the intensity diagram before passing through the sample 3303. After passing through the sample 3303, the center of gravity moves to position 3504, which is a significant shift from the original position before passing through the sample. The shift is uniquely affected by various substances. Thus, the centroid shift can also be used as an OAM signature signature, where the centroid shift indicates the presence of a particular substance and the concentration of the substance. Based on an analysis of the shift of the center of gravity of the intensity diagram, the presence and / or concentration of the substance can be determined.

  The last characteristic OAM signature characteristic is shown in FIG. In this case, the elliptical main axis 3602 of the intensity diagram shifts from the first position 3602 to the second position 3604 at an angle θ 3606. The main axis of the ellipse in the intensity diagram rotates from position 3602 to position 3604 based on the substance to be detected. The angle θ is inherently related to the specific substance to be detected and the concentration of the substance. For this reason, a substance can be detected based on the angle θ determined in the intensity diagram.

ここで、ａ、ｂ、ｃは楕円の寸法である。 A mathematical model can be used to represent the unique OAM signature given by each of eccentricity change, centroid shift or translation, and axis rotation. The change in eccentricity can be expressed by:

Here, a, b, and c are the dimensions of an ellipse.

The change in centroid can be represented by a shift or translation in the space of the vector v according to the following matrix:

The rotation of each axis can be represented by the following series of matrices showing three different orientations of rotation:

  In the example shown in FIGS. 37A and 37B, application of an OAM beam to a sample consisting only of water (FIG. 37A) and water having a 15% glucose concentration (FIG. 37B) is shown. An l = 7 OAM beam at 543 nm propagates through a 3 cm cuvette with water only, resulting in the intensity diagram shown in FIG. 37A. The intensity diagram shown in FIG. 37B is obtained when a 1 = 7 OAM beam passes through a 15% aqueous glucose solution. The OAM signature appears as an ellipticity induced on the normal circular beam amplitude shown in the intensity diagram of FIG. 37A. The effect of the characteristic signature can also be observed in the phase diagrams as shown in FIGS. 38A and 38B. 38A and 38B show interferograms of a l = 2 OAM beam at 633 nm propagating through a 3 cm cuvette of water (FIG. 38A) and a 3 cm cuvette of 15% aqueous glucose (FIG. 38B). . For this particular interference, the reference beam has the same spherical wavefront. For this reason, an essentially helical pattern is observed in the phase measurement. In particular, note the twist shift in one of the two helices of the sample phase plane propagating through the glucose solution. The helical pattern shift is the signature of the interaction in this experiment.

  The unperturbed OAM mode propagates in free space of several meters. The glucose sample appears to impart a phase perturbation to the OAM beam, thereby topologically relating the OAM mode to the propagation direction. This effect enables measurement with higher sensitivity. FIG. 39 shows the amplitude of the OAM beam, and FIG. 40 shows the phase of the OAM beam. The beam is an OAM l = beam and is perturbed as it passes through a 3 cm cuvette of 5% glucose solution and a plane 4 meters above the cuvette. The ellipticity of the beam is much more pronounced for both amplitude and phase measurements.

  The OAM signature is non-linear with respect to glucose concentration and under certain conditions appears to be somewhat periodic with concentration. The ellipticity as a function of glucose concentration is plotted in FIG. 41 for glucose concentrations of 5% to 9% in water in OAM modes 1 = 5, 6, 7 using a 3 cm cuvette. Although the initial data is noisy, this trend persists over several OAM modes.

  A broad absorption band of glucose is seen centered around 750 nm and having a FWHM (full width at half maximum) of approximately 250 nm, as will be appreciated by those skilled in the art. Considering that the absorbance of glucose at 543 nm is a quarter of the absorbance at 633 nm, it is interesting that the formal wavelength results in a stronger OAM response. This suggests that the interaction is based on the real part χ ′ of the susceptibility rather than the imaginary part χ ″ of the susceptibility. Note that in another characterization of the optical rotation of glucose, a specific optical rotation of 50% greater than 633 nm was measured at 543 nm using a 20 cm long sample cell. However, in the OAM study, no discernable change was seen in the effect due to polarization, and no change in the polarization state of the beam through the 3 cm sample was observed. This is consistent with previous OAM polarization studies using chiral molecules.

  To confirm if the vorticity of the OAM beam is important to the effect, a simple ring of light was projected through the glucose sample using an annulus. An annular pattern was printed on a conventional plastic transparency sheet and irradiated with an expanded collimated parallel 543 nm laser beam. As evident in FIGS. 42A-42C, no distortion or signature was observed through the cuvette of water (FIG. 42B) or glucose (FIG. 42C) solution. Changing the ring diameter did not change these results for larger diameters than typical OAM beams. Obvious clipping was observed when the ring diameter was larger than the cuvette. The beam output level in this test was on the order of the OAM experiment. For this reason, the thermal effect will be emphasized.

  Since an aqueous glucose solution was used in the experiment, the study of OAM propagation in water is important. Steam distilled water, the solvent used for dilution, was placed in new cells with various connections and cross-sections and the propagation of various OAM beams through this medium was measured. No discernable difference was observed in the OAM mode propagating through the dry cell, the sample with a path length of 0.5 cm and the sample with 8 cm water.

  Another negative result was observed in experiments where the OAM beam was propagated through a liquid crystal variable retarder. In FIG. 43, reference numerals 4302, 4304, and 4306 indicate 1 = 7 OAM modes at the output of the variable wave plate for various drive voltages from 0.1V to 6V.

  It should be noted that the eccentricity of the intensity image generated by irradiating the sample with an orthogonal function processed beam can vary due to a number of different factors. FIG. 44 shows an example in which the light beam generated by laser 4402 is changed by a hologram provided by SLM 4404 to generate OAM twisted beam 4406. In addition to varying with the OAM function, the OAM torsion beam may be processed using a Hermitian Gaussian function, a Laguerre Gaussian function, or any other type of orthogonal function. The OAM torsion beam is focused through a lens and mirror system 4408 and the beam is directed through a mode classifier 4410. The beam is regenerated by the mode classifier 4412 and separated into the respective modes, and the intensity image can be registered by the camera 4414.

  The beam from laser 4402 has an intrinsic eccentricity of approximately 0.15. As shown in FIG. 45, the various OAM modes generated by the SLM are shown in column 4502 for l = 5, 4, 3, 2, 1. As can be seen, there is a difference between the eccentricity of the mode generated by the SLM and the eccentricity of the mode regenerated by the second mode classifier 4412.

ここで、ｘ_ｉは楕円中のピクセルのｘ位置であり、ｙ_ｉは楕円中のピクセルのｙ位置であり、Ｎは楕円中のピクセルの数である。 Measure eccentricity using Photoshop and Matlab to identify specific signatures. Referring now to FIG. 46, an example of an ellipse 4602 having a radius “a” along the major axis, a radius “b” along the minor axis, and a distance “c” to the focal point 4604 of the ellipse is shown. The eccentricity of the ellipse is expressed by the equation of eccentricity = c / a. The eccentricity varies from 0 to 1, with 0 representing a circle and 1 representing a line. The eccentricity equation is calculated according to the following equation:

Here, x _i is the x position of the pixel in the ellipse, y _i is the y position of the pixel in the ellipse, and N is the number of pixels in the ellipse.

  It has been found that the eccentricity is greater than zero when the sample is not in the cuvette. A number of factors contribute to this non-zero eccentricity. It has been found that the OAM twist signal results in different eccentricities based on a number of different factors that can affect the refractive index. These factors include the sample distribution of the material in the cuvette due to gravity, the distance of the camera from the spatial light modulator, the camera angle of the camera from the spatial light modulator, and the like. Other factors that affect the eccentricity are cuvette positioning, refractive index variation with the sample, cuvette shape, and the incident and exit angles of the beam from the cuvette.

  Several image processing factors have also been found not to cause out-of-tolerance changes. Changes based on software processing errors, non-OAM circular masks, sample sitting time, or sample interaction with the glass or plastic containing the sample container may result in a change in eccentricity, but this change is dependent on the cuvette's It is not due to optical obstructions caused by orientation, camera alignment, etc. Although these factors cause some change in eccentricity, they are within tolerances and are based on molecular signatures where the majority of eccentricity changes are detected.

  Referring now to FIG. 47, a flow diagram for analyzing the intensity image taken by the camera 4414 is shown. A threshold double precision amplitude is applied to the intensity image, and the ring can be clearly seen in step 4702 without extra pixels outside the ring. Next, at step 4701, both the columns and rows are scanned for the entire image. For the largest two peaks, the peaks and their positions are determined at step 4706. At step 4008, ellipses are fitted for all peak positions found. Finally, in step 4710, the major and minor axes of the ellipse, the focal point of the ellipse, the geometric center of the ellipse, the eccentricity and the orientation are determined.

に従って決定される。工程４８１０で、楕円の向きを戻し、楕円の中心点を決定する。最後に工程４８１２で、円錐方程式が楕円を表すかの決定を行う。楕円の場合、パラメータＡ及びＢが存在し、同じ符号を有するが、等しくはならない。この分析に基づいて、最大１ｍｍの横方向シフトが、最大０．２のクリッピングにより、測定される離心率において顕著な変化を引き起こし得ることが決定される。 FIG. 48 shows a flowchart of the ellipse fitting algorithm. At step 4802, X and Y pixel locations are entered for all found peaks. At step 4804, an initial guess is made for the conic equation parameters. The conic equation parameters include parameters A, B, C, D, and E for the equation Ax ² + By ² + Cx + Dy + E = 0. At step 4806, a conjugate gradient algorithm is used to find the cone equation parameters that result in the best fit. The orientation of the ellipse is determined at step 4808 and moved to determine the major and minor axes. Step 4808 determines the equation

Determined according to. In step 4810, the orientation of the ellipse is returned and the center point of the ellipse is determined. Finally, at step 4812, a determination is made whether the conic equation represents an ellipse. In the case of an ellipse, parameters A and B are present and have the same sign but not equal. Based on this analysis, it is determined that a lateral shift of up to 1 mm can cause a significant change in the measured eccentricity with a maximum of 0.2 clipping.

[Non-integer OAM signal]
Molecular spectroscopy using an OAM torsional beam can produce fractional OAM states with other intensity signatures (ie, eccentricity, center of mass shift and elliptical intensity rotation), and phase signature (ie, the phase of the scattered beam). Change) and certain types of publicity distributed spectra can be utilized as molecular signatures. Optical orientation of electronics with circularly polarized photons is often used to study spin angular momentum in solid state materials. This process relies on spin-orbit coupling to transfer angular momentum from proton spins to electron spins, and to study the dynamics of optically excited spend pump- It is incorporated in the probe car and Faraday rotation experiments. This strategy plays a role in the development of semiconductor spintronics by enabling studies by spin decoherence, transport and interaction.

  Proposed spectroscopic techniques instead focus on localized orbital angular momentum (OAM) and solids. Specifically, delocalized OAM associated with envelope wave functions that can be macroscopic in spatial extent, and typically associated with atomic sites incorporated into the effects of spin and related electronic states It can be distinguished from the local OAM generated. The former type of angular momentum is a fundamental object of orbital fleet coherent systems (eg quantum hole layers, superconductors and topological insulators). Techniques for studying nonequilibrium delocalized OAMs in these and other systems provide an opportunity to improve the understanding of scattering and quantum coherence of chiral electronic states and may influence material discovery.

  Interaction of light with glucose in β-amyloid and related OAM spectroscopy applications. Additionally, transmission of OAM between acoustic and photonic modes in elliptical fibers, generation of Raman sidebands with OAM, OAM using a Pleasant Monica lens, patterned Study of optically coherent OAM in excitons using wave mixing in the application of linear polarization to generate 2D Pleasant moniker analogs for OAM light in sin metal films, and for efficient semiconductors The possibility of OAM light to produce a spin polarized vote to electronics can also be used for these techniques.

  Referring now to FIG. 49, in order to alleviate the problems associated with integer OAM states and to allow the use of stable states for non-integer OAMs for purposes similar to those described above, nested non-integer OAM states are used. One embodiment to use is shown. In this case, the input signal 4902 is supplied to the non-integer OAM generation circuit configuration 4904. Non-integer OAM generation circuitry 4904 generates an output signal 4906 having non-integer orthogonal states, which can be subsequently applied or detected as discussed herein.

の軌道角運動量（ＯＡＭ）を有する。これらの光ビームは、ビームの位相を操作する、らせん位相板又はホログラム等の光学デバイスによって実験室内で生成することができる。かかるデバイスにより整数値のｍを有する光ビームが生成する場合、得られる位相構造は、等しい位相の｜ｍ｜個の絡み合ったヘリックスの形態を有する。整数値のｍについては、光学デバイスによって生成する位相ステップの選ばれる高さは、得られるビームにおけるＯＡＭの平均値に等しい。 The orbital angular momentum of the light beams is a result of their azimuthal phase structure. The light beam has a phase factor exp (imφ), where m is an integer and φ is the azimuth angle, and per photon along the beam axis

Orbital angular momentum (OAM). These light beams can be generated in the laboratory by optical devices such as helical phase plates or holograms that manipulate the phase of the beam. When such a device produces a light beam having an integer value m, the resulting phase structure has the form of | m | entangled helices of equal phase. For an integer value m, the chosen height of the phase step generated by the optical device is equal to the average value of OAM in the resulting beam.

  Recently, helical phase steps with non-integer step heights and spatial holograms have been used to generate light beams with non-integer OAM states. In these implementations, the generating optical device causes a phase change of exp (iMφ), where M is not limited to an integer value. Such a beam phase structure exhibits a much more complex pattern. A series of optical vortices with alternating charges occur in the dark line across the direction of the phase discontinuity imprinted by the optical device. To obtain the average value of the orbital angular momentum of these beams, it is necessary to average the vortex pattern. This average value matches the phase step only for integer and half integer values. There is certainly more relation between optics and quantum theory to represent beams with non-integer OAM as quantum states.

  The theoretical description of optical modes with non-integer OAM is based on generating optical devices. For integer OAM values, there may be a theoretical explanation that provides a way to treat the angle itself as a quantum mechanical Hermitian operator. This explanation gives the basic theory of a secure quantum communication system and can form an uncertainty relationship for angle and angular momentum. This theory can be generalized for non-integer values of M, thereby explaining non-integer OAM quantum mechanically. Such exact formulas are of particular interest, and half-integer helical phase plates are used to study higher dimensional entanglements. Non-integer OAM states are characterized not only by the phase step height, but also by the phase shift orientation α. For M with an odd half integer value (M mod 1 = 1/2), the states having the same M and different α by π are orthogonal. In view of the recent application of integer OAM to quantum key distribution in the conversion of spin to orbital angular momentum in optical media, a strict formula is important for the possible application of non-integer OAM to quantum communications.

The components of OAM in the propagation direction L _z and the azimuth rotation angle form a pair of conjugate variables (similar to time-frequency or space-momentum). Both differ from the linear position and momentum defined on an unbounded continuous state space, and the OAM and rotational angle state spaces are essentially different. The OAM eigenstates form a discrete set of states, and m takes all integer values. Since it is physically impossible to distinguish rotation angles that differ by less than 2π radians, the eigenstates of the angle operator are limited to 2π radians. The characteristics of the angle operator are arbitrarily large, but are strictly derived in a finite 2L + 1 dimensional state space. This space spans the angular momentum state | m>, where m is −L, −L + 1,. . . L range. Therefore, the 2π radian interval [θ0, θ0 + 2π) is θn = θ0 + 2πn / (2L + 1) over 2L + 1 orthogonal angle states | θn>. Here, the starting point of the interval is determined by θ ₀ , thereby determining a specific angle operator φ ^ θ. Only if the physical result is computed in this state space, L may go towards infinity, so that an infinite but countable OAM ground state and a dense set of angular states within 2π radians. Will be reproduced.

重要なことには、αは０≦α＜２πによって制限され、不連続の向きが常にθ_０から測定されるように理解されることに留意されたい。この構成では、非整数状態｜Ｍ〉は、以下のように表すことができる：

Quantum states with non-integer OAM are denoted by | M>, where M = m + μ, m is an integer part, and μ∈ [0,1) is a fractional part. State | M> is decomposed into angular states according to:

Importantly, it is understood that α is limited by 0 ≦ α <2π and that the discontinuity orientation is always measured from θ ₀ . In this configuration, the non-integer state | M> can be expressed as:

  For integer-based OAM generation applications, the light beam can be generated using a helical phase plate. However, a light beam generated using a helical phase plate with non-integer phase steps is unstable during propagation. However, light with non-integer orbital angular momentum beams can be generated by Laguerre-Gaussian mode synthesis, rather than the phase step of a helical phase plate. This can be achieved using a spatial light modulator 5002 as shown in FIG. An input signal 5004 is provided to the spatial light modulator 5002 and used for generation of a non-integer OAM beam 5006. The spatial light modulator 5002 synthesizes the Laguerre Gaussian mode rather than using the phase step of the helical phase plate. By limiting the number of Gui phases in the superposition, a light beam can be generated from an SLM 5002 that is well characterized for its propagation. Non-integer OAM light beams from these SLMs are ideal for communications using non-integer OAM states because of structural stability. In addition, as described herein below, the beam is useful for measuring the concentration of various organic materials.

  A spatial light modulator 5002 can be used to generate a light beam with non-integer OAM as a general superposition of optical modes with different values of m. As shown in FIG. 51, a superposition process 5104 can be applied to various Laguerre-Gaussian beam modes 5102 by a spatial light modulator 5002 to produce a non-integer beam output 5106. By using correspondence between optics and quantum theory, OAM can be expressed as a quantum state. As shown generally in FIG. 52, this quantum state 5202 can be decomposed into bases of integer OAM states 5204. Only the OAM index m is determined by the decomposition, but the index of the number of concentric rings remains unspecified in the superposition of the LG beams. Thus, to increase propagation stability, this flexibility can be used to find representations of non-integer OAM states for superimposed LG beams with a minimum number of Gui phases. These beams can be generated using a spatial light modulator 5002 to study their propagation and vortex structure. In a light beam constructed in this manner, non-integer OAM states are well realized and are more stable during propagation and generation of light from non-integer face steps of the helical phase plate.

Referring now to FIG. 53, an aspect is shown in which an SLM can be programmed to obtain a non-integer OAM beam. Programming a single SLM 5302 with a hologram 5304 that sets the phase structure 5306 and the intensity structure 5308 to produce a superposition rather than using multiple optical elements that individually generate each Laguerre Gaussian mode Can do. A blazed diffraction grating 5310 is also included in the hologram 5304 for angular separation of the first order non-integer order. The formula for the resulting phase distribution of the hologram 5304 and the linear coordinate Ф (x, y) _holo is given by:

  In this equation, the Ф (x, y) beam is a superposed phase profile at the beam waist for z = 0, and the Ф (x, Λ) grating is a blazed diffraction that depends on the grating period Λ. It is a phase profile of a grating. Add the two phase distributions to modulo 2π, subtract π, and then multiply by the intensity mask. In the low intensity region, the intensity mask reduces the effect of the blazed diffraction grating 5310, which reduces the intensity of the first order diffraction order. The mapping between phase depth and desired intensity is not linear and is given by a triangular sinc function.

  Referring now to FIGS. 54 and 55, the steps required to generate a hologram that generates a non-integer OAM beam are shown. First, in step 5502, the carrier phase representing the blazed diffraction grating 5402 is added to the phase 5404 of the superposition modulo 2π. This composite phase 5406 is multiplied by an intensity mask 5408 that takes into account the exact mapping between phase depth and diffraction intensity 3010 in step 5504. The hologram 5412 obtained in step 5506 is a hologram having the phase and intensity profile required for the desired non-integer OAM beam.

  Referring now to FIG. 56, the intensity profile and phase profile during propagation for 10 modes and M = 6.5 superposition are shown. Intensity and phase profiles 5602, 5604 and 5606 show a series of numerical plots for three different propagation distances z = 0, z = 2zR and z = 4zR, with the phase and phase during propagation from the waist plane to the far field. Shows the change in intensity. Various cross sections are plotted over a range of ± 3 w (z) for each z value. Profiles 5608, 5610 and 5612 show corresponding experimental profiles.

  The use of non-integer OAM beams can be utilized in a number of ways. In one embodiment, a non-integer OAM beam may be generated from a non-integer OAM beam generator 5702, as shown in FIG. These non-integer OAM beams are then shown through sample 5704 in a manner similar to that discussed herein above. The OAM spectroscopy detection circuitry 5706 can then be used to detect certain OAM non-integer state profiles caused by the OAM beam illuminated through the sample 5704. A particular OAM non-integer state has a particular non-integer OAM state characteristic produced by sample 5704. This process works in the same manner as described herein above.

  FIG. 58 shows an example of an OAM state profile that can be used to identify a particular substance in a sample. In this case, the maximum number of OAM states is indicated by L = 3. Additional state levels are also indicated by L = 1.5; L = 2.75; L = 3.5 and L = 4. This specific OAM state profile is uniquely associated with a particular substance and can be used to identify the substance in the sample when that profile is detected. The interaction of the Laguerre Gaussian light beam with glucose and β-amyloid was an early spectroscopic application of OAM for sample types.

  OAM transfer between acoustic and photon modes in optical fibers, generation of Raman sidebands with OAM, OAM using plasmon lenses, study of optically coherent OAM in excitons using four-wave mixing, Other considerations include the application of linearly polarized light to create 2D plasmonic analog for OAM light in patterned metal thin films, and the possibility of OAM light to generate spin-polarized photoelectrons for efficient semiconductors. For obtaining spectroscopic applications.

  Other means for generating and detecting OAM state profiles can also be utilized. For example, a pump-probe magnetic orbital approach can be used. In this embodiment, orbital angular momentum is imparted to the electronic state of matter by Laguerre-Gaussian optical pump pulses, and the subsequent dynamics are studied with femtosecond time resolution. The excitation uses a vortex mode in which angular momentum is distributed in a macroscopic region determined by the spot size, and the chiral imbalance of the vortex mode reflected from the sample by the optical probe is studied. Clearly different from population and spin relaxation, there are transient signals that evolve on a long-lasting time scale.

[Multi-parameter spectroscopy]
Further applications of OAM spectroscopy can be further improved by identifying elements using a number of different types of spectroscopy to obtain a more definitive analysis. Referring now to FIG. 59, generally a multi-parameter spectroscopy system 5900 is shown. Multiple different spectroscopy parameters 5902 can be tracked and analyzed individually. The group of parameters is then analyzed together using a multi-parameter spectroscopic processor or system 5904 to determine and identify the sample with output 5906. Different spectroscopic techniques receive a light beam generated from a light source 5908, eg, a laser, and passed through the sample 5910, and the substance or concentration of the substance in the sample is detected. While the light source of FIG. 59 shows a single laser and light beam, multiple light beams may be provided by multiple light sources, or multiple light beams may be provided using a single light source. . In one example, the development of a single optical spectroscopy system that fully characterizes the physical and electronic properties of a small amount of sample in real time can be accomplished using light polarization, wavelength and orbital angular momentum (OAM). it can. A polarized light source is used to characterize the atomic and molecular structure of the sample. Depending on the wavelength of the light source, the electronic properties of the sample atoms and molecules, including the degree of polarizability, are characterized. Although the OAM properties of the light source are mainly used to characterize molecular chirality, such new techniques are not limited to chiral molecules or samples, but can also be applied to non-chiral molecules or samples. Combining these three spectroscopic dimensions greatly improves the process of identifying the composition of matter. When incorporated into a small handheld spectrometer, 3D or multi-parameter spectroscopy allows consumers many uses, including useful real-time chemical and biological information. In combination with other pump-probe spectroscopy techniques, 3D / multi-parameter spectroscopy is expected to provide new possibilities in ultrafast, highly selective molecular spectroscopy. The following discussion discusses a number of different spectroscopic techniques that can be implemented in the multiparameter spectroscopic system 5900, but it is understood that other spectroscopic techniques can be combined to provide the multiple spectroscopic analysis system of the present disclosure. I want to be.

[Optical spectroscopy]
Spectroscopy is a measurement of the interaction of light with various substances. Light can be absorbed or emitted by the substance. By analyzing the amount of light absorbed or emitted, the composition and amount of the substance can be determined.

  Part of the energy of light is absorbed by the material. A given wavelength of light interacting with a substance can be emitted at a different wavelength. This occurs in phenomena such as fluorescence, luminescence and phosphorescence. The effect of light on matter depends on the wavelength and intensity of light and the physical interaction with molecules and atoms.

  FIG. 60 shows a schematic diagram of a spectrometer that performs relative measurement in the optical spectral region of the electromagnetic spectrum and uses light spectrally dispersed by a dispersive element. In particular, the device 6002 (monochromator, polychromator, interferometer, etc.) selects a specific wavelength from the light source 6004. This single wavelength light interacts with the sample 6006. A detector 6008 is used to measure the spectrum of light produced by this interaction. By sweeping the detector 6008 over a wavelength range, the change in absorbance or intensity of the resulting light 6010 is measured. A. Hind, “Agilent 101: An Introduction to Optical Spectroscopy”, 2011. (http://www.agilent.com/labs/features/2011_101_spectroscopy.html) (incorporated herein by reference in its entirety). A variety of different spectroscopic techniques have been developed based on these basic measurements, as discussed in: Infrared spectroscopy, Raman spectroscopy, terahertz spectroscopy, fluorescence spectroscopy and orbital angular momentum spectroscopy. Focus on molecular spectroscopy techniques, including methods.

[Molecular spectroscopy]
[Infrared spectroscopy]
Various types of molecular spectroscopy techniques can also be used in a multi-parameter spectroscopy system. These techniques include infrared spectroscopy.

ここで、ｃは光速（３×１０^１０ｃｍ／秒）である。 The infrared frequency is generated between the visible region and the microwave region of the electromagnetic spectrum as shown in FIG. The frequency ν measured in hertz (Hz) and the wavelength λ 6102 typically measured in centimeters (cm) are inversely proportional according to the following equation:

Here, c is the speed of light (3 × 10 ¹⁰ cm / sec).

ここで、ｈはプランク定数（ｈ＝６．６×１０^−３４Ｊ・ｓ）である。 The energy of light is related to λ and ν by:

Here, h is a Planck's constant (h = 6.6 × 10 ⁻³⁴ J · s).

The infrared (IR) spectrum 6104 is divided into three regions: near infrared, mid infrared, and far infrared. The mid-infrared region includes a wavelength of 3 × 10 ⁻⁴ cm to ³ × 10 ⁻³ cm.

  In the course of infrared spectroscopy, IR radiation is absorbed by organic molecules. Molecular vibration occurs when the infrared energy matches the energy of a particular molecular vibration mode. Photons are absorbed by the material at these frequencies, but photons of other frequencies are transmitted through the material.

  The IR spectra of various materials typically include intrinsic transmission T, peaks and absorbance troughs (occurring at various frequencies such as the measured IR spectrum of water vapor shown in FIG. 62).

各々の物質が、その固有分子振動モードによって決まる固有の赤外スペクトルフィンガープリント又はシグネチャを示し、ＩＲ分光法による物質の組成の特定が可能になる。例えば、水蒸気の場合（図６２）、水分子は２つの狭い赤外波長帯内のエネルギーを吸収し、これが吸光度トラフ値６２０２として現れる。 Absorbance A is related to transmission by:

Each substance exhibits a unique infrared spectral fingerprint or signature that depends on its intrinsic molecular vibration mode, allowing the composition of the substance to be determined by IR spectroscopy. For example, in the case of water vapor (FIG. 62), water molecules absorb energy in two narrow infrared wavelength bands, which appear as absorbance trough values 6202.

[Molecular vibration]
Referring now to FIG. 63, water molecules exhibit two types of molecular vibrations, stretching and bending. A molecule 6302 composed of n atoms 6308 has 3n degrees of freedom. In a non-linear molecule such as water, three of these degrees of freedom are rotations, three are translations, and the rest correspond to fundamental vibrations. In the linear molecule 6302, two degrees of freedom are rotations, and three are translations. Thus, the net number of fundamental vibrations for non-linear and linear molecules is 3n-6 and 3n-5, respectively.

  For water vapor, there are two strong absorbance trough values 6202 (FIG. 62) that occur at approximately 2.7 μm and 6.3 μm, respectively, as a result of the two stretching vibration modes 6304 and bending modes 6306 of water vapor. In particular, the symmetric stretch mode and the asymmetric stretch mode 6304 absorb at frequencies very close to each other (2.734 μm and 2.662 μm, respectively), and in FIG. 62 a single relatively broad absorption between multiple trough values 6202. Appears as a belt.

Carbon dioxide CO ₂ exhibits two scissor and bending vibrations 6402, 6404 (FIG. 64, which are equivalent and therefore have the same degenerate frequency). This degeneration appears in the infrared spectrum of FIG. 65 at λ = 15 μm. The symmetric stretching vibration mode 6404 of CO ₂ is inert in the infrared because it does not perturb the dipole moment of the molecule. However, the asymmetric stretching mode 6402 of CO ₂ perturbs the dipole moment of the molecule and produces an absorbance at 4.3 μm in CO ₂ as shown in FIG.

  Both molecular stretching and bending vibration modes (FIGS. 63 and 64) of a molecule can be predicted to a useful theoretical approximation using a simple classical mechanical model.

ここで、ｋはばねの力定数であり、ｍは原子の質量である。 [Extension vibration]
By treating it as a simple classical harmonic oscillator consisting of two equal masses connected by a spring, the stretching frequency of molecular bonds can be approximated by Hooke's law as follows:

Here, k is the force constant of the spring, and m is the mass of the atom.

ここで、ｘはばねの変位である。しかしながら、フックの法則の古典的モデルは、任意の周波数のエネルギーが吸収されることが示唆されるために、分子によるエネルギーの吸光度と矛盾する。実際の分子では、振動運動は、以下のように量子力学的表現によって量子化され、適切にモデル化される：

ここで、ｎは各々の許容エネルギー準位に特徴的な主量子数（ｎ＝０、１、２、３．．．）である。 In a classical harmonic oscillator, the energy depends on the extent to which the spring is stretched or compressed as follows:

Here, x is the displacement of the spring. However, the classical model of Hook's law is inconsistent with the absorbance of energy by molecules, as it is suggested that energy of any frequency is absorbed. In a real molecule, the vibrational motion is quantized by a quantum mechanical representation as follows and is modeled appropriately:

Here, n is a main quantum number (n = 0, 1, 2, 3,...) Characteristic of each allowable energy level.

The lowest energy level is E ₀ = 1/2 hν, followed by E ₁ = 3/2 hν. Only the transition to the next energy level is allowed by the selection rule. Subsequently, the molecule absorbs photon energy in integer increments of hν. However, for photon absorption energy of 2hν or 3hν, the resulting absorption band is called infrared spectrum overtones and is less intense than the fundamental vibration band.

  Intramolecular atomic bonds can break when stretched extremely and cannot be compressed beyond a certain point. Therefore, the molecule is actually an anharmonic oscillator. The energy of the anharmonic oscillator as a function of interatomic distance is shown in FIG. 66, with the energy minimum occurring at the normal bond length 6602 (equal to a relaxed classical mechanical spring). As the interatomic distance increases, the quantization energy levels 6604 become more dense and the energy reaches a maximum. The allowed transition hv is smaller, resulting in lower harmonic energy than expected using the simple harmonic oscillator theory illustrated in FIG.

  This mathematical framework is a useful approximation, if not simple, but the vibrational activity between two atoms in a large molecule cannot be separated from the vibrational behavior of other atoms in the molecule. The vibrations of two bonds in a molecule can be linked in such a way that one contracts or expands and the other contracts like an asymmetric stretching vibration or a symmetrical stretching vibration. When this happens, different absorption frequency bands are observed rather than superimposed or degenerate bands (as observed when two similar atoms in a bond vibrate with the same force constant).

  Infrared spectroscopy is used to identify species by their unique vibrational and rotational optical signatures. A complementary spectroscopic technique, Raman spectroscopy, is used to identify materials by their unique light scattering signature as discussed in the next section.

[Raman spectroscopy]
Raman spectroscopy is a technique used to characterize materials by the amount of scattered light. Raman spectroscopy complements infrared spectroscopy, which instead measures the amount of light absorbed by a material. Raman spectroscopy and infrared spectroscopy can be further used in combination with OAM and polarization spectroscopy to further improve the analytical results. When light interacts with matter, changes in the dipole moment of the molecule result in infrared absorption bands, and changes in their polarizabilities generate Raman bands. The sequence of observed energy bands arises from specific molecular vibrations that collectively produce a unique spectral signature indicative of each molecular type. Certain vibration modes that occur in Raman spectroscopy are forbidden in infrared spectroscopy, but other vibration modes can be observed using both techniques or multi-parameter techniques using OAM. If these latter modes are common to both techniques, their strengths are significantly different.

  The most common interaction between photons and molecules results in Rayleigh scattering, where the photons elastically scatter as a result of the excited electrons falling to their original energy level. As a result, Rayleigh scattered photons have the same energy as incident photons.

  The discovery of inelastic photon scattering in 1928 by CV Raman and KS Krishnan established Raman spectroscopy as a practical chemical analysis useful for characterizing a wide range of chemical species, including solid, liquid and gaseous samples. It was. Solid crystal lattice vibrations are typically active in Raman spectroscopy, and their spectra appear in polymer and semiconductor samples. The gas sample exhibits a rotating structure that can be characterized by vibrational transitions.

  Approximately 1 percent of the incident photons scatter inelastically, resulting in lower energy photons. Raman scattering is caused by changes in the vibrational energy, rotational energy, or electronic energy of the molecule. The vibrational energy of the scattered molecules is equal to the difference between the incident photons and the Raman scattered photons. This form of vibronic spectroscopy is often classically regarded as a perturbation of the electric field of a molecule when the incident photons interact with the electric dipole of the molecule. However, quantum mechanically, a scattering event is described as an excitation to a virtual energy state that is lower in energy than the actual electronic transition, and a nearly simultaneous level drop and vibrational energy change. Such spectroscopy can be successful in conjunction with incident photons having OAM. In Raman spectroscopy, incident photons excite electrons to a final energy level that is different from their original energy level (FIG. 68).

  Because the intensity of Raman scattering is low, the heat generated by the dissipation of vibrational energy does not cause an increase in perceivable material temperature. Such Raman spectroscopy can work in conjunction with incident photons having OAM. At room temperature, the vibrationally excited population is small. Since the excited vibrational state is low at room temperature and electrons are generated in the ground state, the Stokes shift scattering event shown in FIG. 68 is usually observed in Raman spectroscopy. The inelastic Raman scattered photon 6802 has a lower energy than the incident photon 6804 because the electrons decay to an energy level 6806 that is higher than the original ground state 6808. Anti-Stokes shift scattering events 6810 are caused by a small fraction of molecules that are initially in a vibrationally excited state (FIG. 68), placing them in the ground state 6812, resulting in higher energy Raman scattered photons. At room temperature, since the Stokes spectrum and anti-Stokes spectrum have the same frequency information, the anti-Stokes shift Raman spectrum is always weaker than the Stokes shift spectrum. For this reason, most Raman spectroscopy focuses only on the Stokes shift scattering phenomenon.

  Force constants that can model vibrational mode energy can be affected by molecular structure including atomic mass, molecular species, bond order, and molecular geometry. However, Raman scattering occurs when the polarizability of the molecule can be affected.

The polarizability α of the molecule appears as a proportional constant between the electric field and the induced dipole moment as follows:

ここで、Ｑは振動に垂直な方向であり、ラマン活性振動の選択規則とみなされる。 Induced dipoles scatter photons at the frequency of the incident photons (Rayleigh scattering). However, molecular vibrations can change the polarizability and cause inelastic Raman scattering of photons. The change in polarizability can be expressed by:

Here, Q is a direction perpendicular to the vibration, and is regarded as a selection rule of the Raman active vibration.

  Raman active vibrations do not exist in the infrared for molecules having a center of symmetry, and the presence of a perturbed center of symmetry (eg, a permanent dipole moment) indicates the absence of infrared active vibrations.

したがって、双極子モーメントを僅かに誘起する入射光子は、非常に小さな強度を有するラマン帯をもたらす。より強いラマン散乱系は、分極(polarization)の影響を受けやすい、より広く分布した電子を示す二重炭素結合を有する分子のように、より高いαの値を有するものである。続いて、ラマン分光法によって測定可能な化学濃度の範囲は、散乱強度が濃度に正比例すると仮定すると、大幅に広い。 The intensity of the Raman band is proportional to the square of the induced dipole moment or the spatial change in polarizability, as follows:

Thus, an incident photon that slightly induces a dipole moment results in a Raman band with very small intensity. Stronger Raman scattering systems are those that have higher values of α, such as molecules with double carbon bonds that exhibit more widely distributed electrons that are susceptible to polarization. Subsequently, the range of chemical concentrations that can be measured by Raman spectroscopy is significantly wider, assuming that the scattering intensity is directly proportional to the concentration.

  Raman spectroscopy exhibits several advantages over other spectroscopic techniques. The Raman band shows a good signal-to-noise ratio for detection of its fundamental vibration mode. Thus, the Raman signature of the sample being measured is typically more pronounced and deterministic.

  While the Raman spectrum of water is weak and unnoticeable, the infrared spectrum of water is very strong and more complex, so Raman spectroscopy is more useful than infrared spectroscopy for the analysis of aqueous solutions. In organic and inorganic chemistry, the presence of a covalent bond results in an intrinsic Raman signature. The Raman spectroscopy setup requires only a suitable laser source incident on the material and a detector that collects scattered photons that minimize the need for careful sample preparation. Raman spectroscopy is non-destructive because it merely irradiates the material with a laser. Since the Raman effect is weak, the efficiency and optimization of the Raman spectroscopic instrument is extremely important in order to produce very low molecular concentration measurements in the shortest possible time.

このフレームワークでは、振動周波数ω＿０及び正常モード振幅ｑ（分子振動の生成消滅演算子に関して表すことができる）を用いて、

となり、電気双極子モーメントμを用いて、

となる。これにより、

が得られる。 [Spontaneous Raman spectroscopy]
The intensity of spontaneous Raman scattering is linearly dependent on the incident intensity of light, but is extremely weak. By treating the light-matter interaction quantum mechanically, the total Hamiltonian can be expressed in terms of the energy associated with the molecular vibration mode H_ν, the light vibration mode H_γ, and their interaction H_νγ:

In this framework, using vibration frequency ω_0 and normal mode amplitude q (which can be expressed in terms of molecular vibration generation and annihilation operators)

And using the electric dipole moment μ,

It becomes. This

Is obtained.

ここで、ｅ＿（ｋ＿λ）は場の偏光単位ベクトル場であり、Ｖ＿ｉｎｔは相互作用体積である。この場合、光のハミルトニアンは、以下となる：

電気双極子近似の一次摂動を用いることで、相互作用ハミルトニアンを、以下のように局所座標系ｑにおける分子の分極率αに関して得ることができる：

初項によりレイリー散乱が特性化される。残りの一次ラマン散乱項は、それぞれストークス場及びアンチストークス場“Ｅ”＿Ｓ及び“Ｅ”＿ＡＳに加えてコヒーレントレーザ場“Ｅ”＿Ｌを含む自発ラマン散乱を特性化するために必要とされる。ｑ及びＥ＿γをこの式に代入することで、以下が得られる：

ここで、Ｈ＿γＳ及びＨ＿γＡＳは、それぞれストークス及びアンチストークス分岐の相互作用ハミルトニアンである。 Using the light annihilation operators a ^ † and a, field quantization is obtained as follows:

Where e_ (k_λ) is the polarization unit vector field of the field and V_int is the interaction volume. In this case, the Hamiltonian of light is:

Using first order perturbations of the electric dipole approximation, an interacting Hamiltonian can be obtained for the molecular polarizability α in the local coordinate system q as follows:

The first term characterizes Rayleigh scattering. The remaining first order Raman scattering terms are required to characterize spontaneous Raman scattering, which includes the coherent laser field “E” _L in addition to the Stokes and anti-Stokes fields “E” _S and “E” _AS, respectively. Substituting q and E_γ into this equation gives:

Here, H_γS and H_γAS are the interaction Hamiltonians of Stokes and anti-Stokes branches, respectively.

単純な調和振動子の描写では、励起量子ｎ＿νによる固有状態｜ｎ＿ν〉は、生成消滅演算子によって作用され、以下のようにストークス及びアンチストークス遷移速度が得られる：

したがって、線形従属を仮定すると、ｎ＿νをラマン信号強度から決定することは容易である。 The steady-state transition speed between the initial state | i> and the final state | f> is given according to Fermi's golden rule as follows:

In the depiction of a simple harmonic oscillator, the eigenstate | n_ν> due to the excited quantum n_ν is acted on by the creation and annihilation operator, resulting in Stokes and anti-Stokes transition velocities as follows:

Therefore, assuming linear dependence, it is easy to determine n_ν from the Raman signal strength.

  Using the Raman intensity from each vibration level, the natural vibrational molecular mode is identified and the composition of the material is characterized.

ここで、Ａはラマン断面積である。ボルツマン分布を用いることに加え、Ｉ＿ＡＳを同じモードの室温ストークス信号に関して正規化すると、以下のようになる：

ここで、Ｅ＿Ｒ＾０はラマンモードの室温（Ｔ＿０）エネルギーである。概して、ｈν＿Ｒ≫ｋＴ＿０である。そのため、〈ｎ＿ν〉＿０＝０であり、正規化アンチストークス信号は、およそ〈ｎ＿ν〉であり、

である。
異なる振動モードと関連する正規化散乱強度を比較することによって、赤外励起後の異なる分子モードにわたるエネルギーの分布を得ることができる。 The integrated anti-Stokes intensity of the Raman mode is proportional to the average vibrational quantum number <n_ν> of the mode as follows:

Here, A is a Raman cross-sectional area. In addition to using the Boltzmann distribution, normalizing I_AS with respect to the room temperature Stokes signal of the same mode yields:

Here, E_R ^ 0 is room temperature (T_0) energy of Raman mode. In general, hν_R >> kT_0. Therefore, <n_ν> _0 = 0, and the normalized anti-Stokes signal is approximately <n_ν>,

It is.
By comparing the normalized scattering intensities associated with different vibration modes, the energy distribution over different molecular modes after infrared excitation can be obtained.

[Induced Raman spectroscopy]
The stimulated Raman intensity depends nonlinearly on the incident intensity of the photon, but the magnitude does not change much. Inelastic scattering of photons by optical phonons resulting from the finite response time of the third-order nonlinear polarization of matter is characteristic of Raman scattering. Monochromatic light propagating in an optical material results in spontaneous Raman scattering in which some photons transition to a new frequency. The polarization of the scattered photons can be parallel or orthogonal when the pump beam is linearly polarized. Stimulated Raman scattering occurs when the scattered intensity of photons at shifted frequencies is enhanced by existing photons already present at these shifted frequencies. As a result, in stimulated Raman scattering, simultaneous photons at the downshift frequency provide gain that can be utilized, for example, in a Raman amplifier or effectively in molecular spectroscopy.

  Stimulated Raman scattering (SRS) has been observed in glass fibers and Raman gain has been measured in single mode fibers. Raman amplification has become a mature technology with the availability of sufficiently high power pump lasers.

並びに自発ラマン散乱断面積に関するラマン利得係数ｇ＿Ｒに比例して増大する。したがって、ラマン散乱の確率は、ポンプ波の光子密度及びラマン断面積に直接的に関係する。 In classical electromagnetic frameworks, stimulated Raman scattering signal strength is pump strength and signal strength:

In addition, it increases in proportion to the Raman gain coefficient g_R related to the spontaneous Raman scattering cross section. Therefore, the probability of Raman scattering is directly related to the photon density and Raman cross section of the pump wave.

  Stokes and pump waves should overlap in space and time, resulting in stimulated emission. Since the Raman process involves vibration modes of molecules in the material, the composition of the material is determined by its intensity spectrum. For example, in an amorphous material, vibrational energy levels tend to fuse to form a band, and the pump frequency can be different from the Stokes frequency over a wide range. However, in crystalline materials, the intensity peak has a narrow bandwidth and therefore tends to be well separated.

ポンプ波強度について、

（ここで、ω＿Ｐ及びω＿Ｓは、それぞれポンプ周波数及びストークス周波数である）が挙げられる。後方散乱については、ｄＩ＿Ｓ／ｄｚ→−ｄＩ＿Ｓ／ｄｚである。損失がない場合には、これらの式は、

に縮小され、誘導ラマン散乱過程中のストークス波及びポンプ波における光子数の保存が具体化される。 As the coupled wave equation of forward Raman scattering, the Stokes intensity using the Stokes attenuation coefficient α_S,

About pump wave intensity

(Where ω_P and ω_S are the pump frequency and Stokes frequency, respectively). About backscattering, it is dI_S / dz-> dI_S / dz. In the absence of loss, these equations are

To preserve the number of photons in the Stokes and pump waves during the stimulated Raman scattering process.

If the stimulated gain exceeds the linear loss (which causes a threshold output that must be overcome to initiate stimulated Raman scattering), the stimulated scattering intensity increases. In a material system in which forward scattering and back scattering occur, the molecular vibration involved in increasing the scattered wave amplitude is driven by the beat frequency. Second, the increase in wave amplitude enhances molecular vibrations as part of a positive feedback loop that provides stimulated Raman scattering effects. For the forward scattering process, removing the pump decay term:

が与えられ、ここで実効光路長が以下によって与えられる：

誘導ラマン散乱は、物質の光路長全体にわたって生じる散乱事象によって増強され、分子分光法技術に有用である。 By solving this equation, I_P (z) = I_0 e ^ (− α_P z) is obtained, and the stimulated Stokes scattering intensity is obtained.

Where the effective optical path length is given by:

Stimulated Raman scattering is enhanced by scattering events that occur throughout the optical path length of matter and is useful for molecular spectroscopy techniques.

[Resonance Raman spectroscopy]
The Raman effect in classical Raman spectroscopy depends only on the frequency of the incident light, and as discussed above, the scattering intensity depends on ν_0 ^ 4. If the vibrational mode of the molecular absorption transition exactly matches the energy of the incident light, the observed scattering intensity can be the same as about ν_0 ^ 6. This resonance Raman effect enables highly sensitive spectroscopic identification of molecular species (such as a chromophore in a protein embedded in a biological membrane) in a complex material medium.

  In resonance Raman spectroscopy, only a few molecular vibration modes are enhanced. In the simplest scenario, only one electronic state is resonant. In this case, the resonant Raman signal is the result of nuclear motion caused by molecular distortion while the molecule transitions between ground and excited states when resonance is induced by incident light.

  The functional component of most biochromophoric groups consists of atoms conjugated by specific electronic transitions that are selectively sensitive to resonance Raman spectroscopy. Information about the vibration structure of the electronic state involved in the transition used for the induction of resonance is obtained by the frequency of the resonance Raman band to be measured. Scattering intensity gives information on the nature of mode coupling due to electronic transitions.

によって与えられ、ここで電場の振幅

は、

によって与えられ、ここで、ｍ、ｒ及びｎは、それぞれ初期、中間及び最終エネルギー状態Ｅ＿ｍ、Ｅ＿ｒ、Ｅ＿ｎの量子数である。 [Raman effect in vortex light]
A molecule in the vibronic state m subjected to plane-polarized incident light of frequency ν_0 and intensity I_0 is perturbed to a new vibronic state n. Due to this interaction, the frequency of light is shifted by ν_mn = ν_m−ν_n and scattered at a frequency ν_0 + ν_mn over a solid angle of 4π. The scattering intensity at the transition from m to n is

Where is the amplitude of the electric field

Is

Where m, r and n are the quantum numbers of the initial, intermediate and final energy states E_m, E_r and E_n, respectively.

の振幅

と、シフトした散乱放射により誘導されるトルク（shifted scattered radiation induced torque）に関連付けられたその振幅

との間で、

は、散乱テンソルＡ＿ｍｎ＝（α_ρσ）＿ｍｎに関して、

の形で、又は、成分表現では

で、表すことができるテンソル関係式であり、散乱テンソルＡ＿ｍｎは、

として表すことができる。 Electric field strength

Amplitude of

And its amplitude associated with shifted scattered radiation induced torque

Between

Is the scattering tensor A_mn = (α_ρσ) _mn,

Or in the component representation

Is a tensor relational expression that can be expressed, and the scattering tensor A_mn is

Can be expressed as

はＭ＿ｒｎ Ｍ＿ｍｒを含むため、ｍからｎへの遷移についての分極率テンソルαの各ρσ番目の行列要素は、以下のように中間的なバイブロニック状態に関して表すことができる：

ここで、（Ｍ＿ρ）＿ｍｎは、放射演算子ｍ＾＿ρの存在下での振動準位ｍ及びｎの間の遷移行列であり、

Expressed in terms of dyadic components of tensor A_mn

Since M_rn M_mr, each ρσ th matrix element of the polarizability tensor α for the transition from m to n can be expressed in terms of an intermediate vibronic state as follows:

Here, (M_ρ) _mn is a transition matrix between vibration levels m and n in the presence of the radiation operator m ^ _ρ,

のスカラーベクトル成分（Ｍ＿ｌ）＿ｒｎ及び（Ｍ＿σ）＿ｍｒの通常の積である。３つの相互に垂直な方向で空間的に固定したｌ，σ＝１，２，３では、以下のようになる：

入射強度Ｉ＿０＝（ｃ／２π）Ａ＾２を用いると、

Here, (M_l) _rn (M_σ) _mr is a unit vector

Is a normal product of scalar vector components (M_l) _rn and (M_σ) _mr. For l, σ = 1, 2, 3 spatially fixed in three mutually perpendicular directions:

Using the incident intensity I_0 = (c / 2π) A ^ 2,

の全位置で平均化するか、又は固定入射波方向及び偏光での散乱分子の全モードで平均化することによって、

Therefore, the total scattering intensity depends on the polarization state of the excitation light.

Or by averaging over all modes of the scattering molecule in a fixed incident wave direction and polarization,

ここで、ρ＝ｘ，ｙ，ｚ及びσ＝ｘ＾’，ｙ＾’，ｚ’は、それぞれ独立して入射光子及び散乱光子の分子の固定座標系である。 Finally, for m → n electronic transitions per molecule, the average total intensity of the scattered radiation is obtained as follows:

Here, ρ = x, y, z and σ = x ^ ′, y ^ ′, z ′ are independently fixed coordinate systems of molecules of incident photons and scattered photons.

に関してガウス包絡線を用いて数学的に特性化することができる。ローレンツ−ゲージにおいては、ラゲール−ガウスビームのベクトルポテンシャルは、（ρ，φ，ｚ）座標系において、

であり、ここでｗ（ｚ）は、ラジアル振幅が１／ｅとなるビームウエスト（半径）である。簡単にするために、ｐ＝０のみが通例選ばれる。双極子近似においては、項ｅ＾ｉｋｚは無視することができ、それによりラゲール−ガウスビームの放射演算子を、以下のように表すことができる：

ここで、ｅ＾ｉωｔは光子放出と関連し、ｅ＾（−ｉωｔ）は光子吸収と関連する。 [Raman effect selection rules using vortex light]
A particular solution set of Maxwell's equations in the paraxial approximation is interesting for studying the Raman effect using vortex light. Generalized Laguerre polynomial for vortex beam by Laguerre-Gauss function

Can be mathematically characterized using a Gaussian envelope. In Lorentz-Gauge, the Laguerre-Gauss beam vector potential is in (ρ, φ, z) coordinate system,

Where w (z) is the beam waist (radius) at which the radial amplitude is 1 / e. For simplicity, only p = 0 is typically chosen. In the dipole approximation, the term e ^ ikz can be ignored, so that the Laguerre-Gaussian beam radiation operator can be expressed as:

Here, e ^ iωt is associated with photon emission, and e ^ (− iωt) is associated with photon absorption.

  The following generalized framework that defines a set of selection rules to measure the unique OAM Raman signatures of different materials is applied to the intensity profiles associated with both stimulated and spontaneous Raman spectroscopy.

であり、ｈ＿（ｅ，ｓ）＾ａ、（Ｍ＿ρ）＿（ｇ，ｅ）及び（Ｍ＿σ）＿（ｇ，ｓ）はゼロでない。σ番目のフォノンのｊ番目の分岐を表すために、指数Γ＿ｊ＾σを有するラマンテンソルＰ＿αβγδ（Γ＿ｊ＾σ）を導入し、単一指数ａを置き換えることで、入射光子指数ρを（α，β）、散乱光子指数σを（γ，δ）に同様に置き換える。 The relations in the irreducible representations Γ_α, Γ_ρ and Γ_σ of phonons, incident photons and scattered photons required to ensure that the matrix elements of A_ (l, p) that are never zero are

H_ (e, s) ^ a, (M_ρ) _ (g, e) and (M_σ) _ (g, s) are not zero. In order to represent the j-th branch of the σ-th phonon, the Raman tensor P_αβγδ (Γ_j ^ σ) with the index Γ_j ^ σ is introduced and the single index a is replaced, so that the incident photon index ρ is (α, β ), And the scattered photon index σ is similarly replaced with (γ, δ).

次に、３つ全ての表現についてＰ＿αβγδ（Γ＿ｊ＾σ）をクレブシュ−ゴルダン係数によって決定することができる：

Because the photon's orbital angular momentum remains unperturbed in the interaction between light and matter in the Raman scattering process, the incident and scattered photons can be represented in the following ways:

Next, P_αβγδ (Γ_j ^ σ) for all three representations can be determined by the Krebsch-Gordan coefficient:

For crystalline materials, the 3 × 3 Raman tensor is reduced to 2 × 2 in the special case of forward scattering. In this case, the Raman tensors for l ≧ 2 excitation are all of the same form. Thus, due to symmetry considerations, the l dependence is zero for l ≧ 2. Since the constants a, b, c, d and e depend on l and crystal symmetry, non-zero OAM yields Γ ₂ phonons for l ≧ 2 photon excitation and Γ ₃ phonons for l ≧ 1 photon excitation. The two Raman tensors are separated.

  OAM Raman spectroscopy demonstrates the ability to characterize the atomic and molecular composition of crystalline materials. More complex selection rules are needed to obtain a complete OAM Raman signature of chiral materials that exhibit their own atomic and molecular symmetry.

のように表すことができ、基底状態ψ＿（ｇ，ｋ）と励起状態ψ＿（ｅ，ｋ）とを関連付ける電子遷移モーメントは、以下のように表すことができる：

この場合、ｌ＝０による一次テイラー展開は、

For example, in the case of highly symmetric crystalline materials, this approach is somewhat simpler. Considering the periodic lattice potential, the electrons in the crystalline solid are Bloch waves.

The electronic transition moment that associates the ground state ψ_ (g, k) with the excited state ψ_ (e, k) can be expressed as follows:

In this case, the primary Taylor expansion with l = 0 is

  Since h_ (e, S) ^ α, Q_α, and ΔE_es depend only on the characteristics of the crystal and not l, only M influences the scattering intensity when using vortex light. Subsequently, the electron wave function and l remain as relative values of Μ (l ≠ 0) with respect to M (l = 0) for the Raman effect due to the interaction of vortex light with the crystalline solid.

  The Raman scattering intensity increase can be identified by choosing an appropriate value of l, for example in the case of zinc blende crystals, for l = 30 based on symmetry considerations using the approach presented above. The maximum value is reported. In practice, the focusing of the laser that generates the vortex light has little effect on the increase in intensity of M, given its similarity to the focused light in normal Raman scattering measurements.

[Polarized Raman spectroscopy]
Assuming that the polarizabilities of the molecules are spatially different with respect to the distribution of molecules in the sample, characterize the atomic structure of the crystal and the molecular structure of the polymer film, crystal and liquid crystal using a plane polarized Raman source. Can do.

  Referring now to FIG. 69, the polarization Raman method is a polarizer between sample 6904 and spectrometer 6908 oriented either parallel (平行) or perpendicular (⊥) to the polarization state of laser light source 6902. 6906 is included. Similarly, a polarization optical system 6910 may be inserted between the laser 6902 and the sample 6904 in order to select an appropriate state of polarized light incident on the sample.

ここで、Ｉ＿⊥及びＩ＿‖は、レーザ光源６９０２の偏光状態に対してそれぞれ垂直及び平行の偏光を有するラマンスペクトル帯強度である。 The symmetry properties of bond vibrations in molecules are characterized as follows by evaluating the degree of polarization reduction ρ of a specific intensity peak by polarization Raman spectroscopy:

Here, I_⊥ and I_‖ are Raman spectrum band intensities having polarizations perpendicular and parallel to the polarization state of the laser light source 6902, respectively.

  As shown in FIG. 70, the information obtained by polarized Raman spectroscopy 7002 can be used to supplement the atomic and molecular information obtained by non-polarized Raman spectroscopy 7004. A single integral spectroscopy unit 7006 that exploits both polarized and non-polarized Raman effects, provides an overall view of the information obtained by spectroscopically processing data from a sample using multiple types of spectroscopic analysis. Integrated result processing 7008 is used to improve quality and quantity.

を有する基本モードで動作するガウスレーザであり、ここで、

は偏光ベクトルである。かかる光源によって発生する光は、ｚ方向に電場成分を有しない横断（ｘ，ｙ）面に限定される直線偏光又は円偏光を有する。対象の誘起双極子モーメントは、この場合Ｐ_ｘ及びＰ_ｙのみである。 [Raman spectroscopy using optical vortices]
A typical Raman source is an electric field flowing in the z direction

A Gaussian laser operating in a fundamental mode having:

Is a polarization vector. The light generated by such a light source has linearly or circularly polarized light limited to the transverse (x, y) plane that has no electric field component in the z direction. The induced dipole moments of interest are only P _x and P _{y in} this case.

In the longitudinal mode along the z direction incident on the molecule, light that completely describes the polarizability of the molecule including P_z is scattered. The electric field with the z component is a radially polarized beam with the following polarization vector:

There are several ways to generate a radial polarization field with a longitudinal component when strongly focused. In Raman spectroscopy, the induced dipole moment P _z is a result of E _z (not only generates new vibration modes that have not been observed so far in conventional Raman spectroscopy, but can also increase the intensity of the vibration modes. thing). As shown in FIG. 71, the information obtained by the Raman vortex 7102 provided with the optical vortex adds a third-order spectroscopic capability in combination analysis 7108 with polarization Raman spectroscopy 7104 and non-polarization Raman spectroscopy 7106. . Such Raman spectroscopy can also be successful when combined with incident photons carrying the OAM.

[THz spectroscopy]
Terahertz spectroscopy is performed in the far-infrared frequency range of the electromagnetic spectrum (FIG. 61) and is therefore useful for identifying far-infrared vibration modes in molecules. THz spectroscopy can provide a higher signal-to-noise ratio and a wider dynamic range than far-infrared spectroscopy due to the use of bright light sources and sensitive detectors. This results in the selective detection of weak intermolecular and intramolecular vibrational modes that are not effective in IR spectroscopy, generally occurring in biological and chemical processes. THz spectroscopy can also be used in conjunction with incident photons carrying the OAM. Terahertz waves pass through opaque media in the visible and near infrared spectrum and are strongly absorbed by the aqueous environment (see FIG. 72).

  In THz spectroscopy, there has historically been an obstacle to the lack of a suitably high power light source. However, the practical use of THz spectroscopy in the far-infrared range has been made possible by the generation of THz lines based on picosecond and femtosecond laser pulses. Today, THz light sources include short pulse modes (eg photoconductive antennas, optical rectifiers) or continuous wave (CW) modes with a wide range of effective power (nanowatts to 10 watts).

  Several different types of THz light sources are used today to investigate biological, chemical and solid state processes. Light sources in the 1 THz to 3.5 THz range are frequently used to investigate molecular structural changes, for example in biology and medicine. THz spectroscopy is used today as often as Raman spectroscopy.

[Terahertz time domain spectroscopy]
Terahertz time domain spectroscopy (THz-TDS) is one of the most widely used THz methods, including coherent emission of single cycle THz pulses as provided by femtosecond lasers. These pulses are detected at a repetition rate of about 100 MHz.

  The two-dimensional THz absorption characteristics of the sample are characterized by the THz imaging method. This technique has been demonstrated in systems designed for THz-TDS based on picosecond pulses and systems utilizing continuous wave (CW) light sources such as THz wave parametric oscillators, quantum cascade lasers or optically pumped terahertz lasers. . THz spectroscopy can be used in conjunction with incident photons carrying the OAM.

  THz pulse imaging provides a wide range of image frequency information from 0.1 THz to 5 THz, while THz CW imaging can be performed in real time, is frequency sensitive and has a higher dynamic range due to significantly higher spectral power density. Have. In both pulsed THz imaging and CW THz imaging, the characteristics of the light source (coherence, power and stability) are important. A THz spectrometer can mechanically scan a sample in two dimensions, with each scan time corresponding to the sample size. Real-time THz imaging is often performed using an array of THz wave detectors composed of electro-optic crystals or pyroelectric cameras. Such THz spectroscopy can be used in conjunction with incident photons carrying the OAM.

  THz imaging has the problem of low transmission through apertures that result in low resolution and low sensitivity as estimated for diffraction limits below 1 millimeter. To exceed the diffraction limit, near-field microscopy that achieves subwavelength resolution is used, but low transmittance remains a problem.

[Fluorescence spectroscopy]
By being perturbed by incident light, the electrons in the molecule are excited from the lowest vibration energy level 7302 in the electronic ground state to the first (S_1) vibration state 7304 or the second (S_2) vibration state 7306 at room temperature ( FIG. 73) may occupy any one of several vibrational sublevels. Since each vibrational sublevel has many adjacent rotational energy levels, the energy transitions between the sublevels are so close that they are almost indistinguishable. As a result, most molecular compounds have a broad absorption spectrum (except for those with negligible rotational properties (such as planar compounds and aromatic compounds)).

  In fluorescence spectroscopy, the molecule absorbs energy from incident photons, obtains a higher vibrational energy sublevel (S_1 or S_2) in the excited state, and then loses excess vibrational energy due to collision, resulting in the lowest vibrational sublevel in the excited state. Return to level. Most molecules occupying electronic states above S_2 have undergone a level drop and internal conversion due to collision, and from the lowest vibrational energy sublevel of the upper state, the higher vibrational sublevel of the lower excited state having the same energy. It reaches the rank. The electrons continue to lose energy until they occupy the lowest vibrational energy sublevel 7308 of S_1. A molecular level drop to any vibrational energy sublevel in the ground state causes the emission of fluorescent photons.

  If the absorption and emission processes are different from this sequence, the quantum efficiency is less than 1. The “0-0” transition from the lowest vibrational ground state sublevel to the lowest vibrational S_1 sublevel 7308 is common to both absorption and emission phenomena, but all other absorption transitions are any transitions in fluorescence emission. Only caused by more energy. The emission spectrum then overlaps with the absorption spectrum at the incident photon frequency corresponding to this “0-0” transition, with the remainder of the emission spectrum having less energy and equally occurring at lower frequencies. Given the slight loss of energy due to the interaction of the molecule with surrounding solvent molecules, the “0-0” transitions in the absorption and emission spectra rarely match exactly.

  Therefore, the vibrational sub-level distributions in S_1 and S_2 are very similar since the incident photon energy does not substantially affect the shape of the molecule. The energy difference between bands in the emission spectrum is the same as that in the absorption spectrum, and the emission spectrum is often a mirror image of the absorption spectrum. Since the emission of fluorescent photons always occurs from the lowest vibrational energy sublevel of S_1, the shape of the emission spectrum is always the same despite the shift of the incident photon frequency from the frequency of the incident radiation. If the intensity of the incident radiation that produces excitation remains constant even when the frequency is shifted, the emission spectrum is considered to be a corrected excitation spectrum.

  The quantum efficiency of most complex molecules is independent of the frequency of the incident photons, and the emission directly correlates with the molecular extinction coefficient of the compound. In other words, the corrected excitation spectrum of the substance is the same as its absorption spectrum. The intensity of the fluorescence emission is directly proportional to the incident radiation intensity.

  Fluorescence spectroscopy produces an emission spectrum and an excitation spectrum. In emission fluoroscopy, the excitation radiation is held at a fixed wavelength and the emitted fluorescence intensity is measured as a function of the emission wavelength. In excitation fluoroscopy, the emission wavelength is held fixed and the fluorescence intensity is measured as a function of the excitation wavelength. This type of fluorescence spectroscopy can also be used in conjunction with incident photons carrying the OAM. By combining the emission spectrum and the excitation spectrum, a spectrum map of the substance to be investigated can be obtained. The target substance may contain many phosphors, and the absorption spectrum and emission spectrum (for tryptophan, elastin, collagen, nicotinamide, adenine dinucleotide (NADH) and flavin) are as shown in FIGS. 74A and 74B. In addition, different excitation wavelengths are required to study different molecules.

  In a fluorescence spectrometer, the spectral distribution (fluorescence emission spectrum) of light emitted from a sample is analyzed using either a continuously variable interference filter or a monochromator. In monochromators used in more sophisticated spectrometers, excitation radiation is selected and the emission spectrum of the sample is analyzed. With such an instrument, it is also possible to measure fluctuations in emission intensity by the excitation wavelength (fluorescence excitation spectrum).

  One of the advantages of fluorescence spectroscopy compared to equivalent absorption methods is the considerable loss of accuracy due to the simple fluorometer geometry in which only a small central area of the cuvette is examined by the detector. Without exception, the sample can be placed in a simple test tube rather than a precision cuvette. Therefore, the overall size of the cuvette is not so important.

  The sensitivity of fluorescence spectroscopy is highly dependent on the properties of the sample being measured and is typically measured in parts per billion or trillions for most materials. This significant sensitivity allows for reliable detection of very small sample size fluorescent materials (eg, chlorophyll and aromatic hydrocarbons).

  Fluorescence spectroscopy is very specific and less susceptible to interference because there is little material that absorbs or emits light (fluoresces) and rarely emits at the same frequency as the compound in the target material.

  Fluorescence measurements directly correspond to sample concentrations over a wide frequency range and can be performed over a concentration range of up to about six orders of magnitude without sample dilution or sample cell changes. Additionally, the sensitivity and specificity of fluoroscopy speeds up the analysis by reducing or eliminating the need for costly and time consuming sample preparation procedures. Overall, fluoroscopy is a low-cost material identification method because of its high sensitivity (small sample size requirements).

[Pump-probe spectroscopy]
Pump-probe spectroscopy is used to study ultrafast phenomena, where the pump beam pulse perturbs the atomic and molecular components of the sample and the probe beam pulse is used to examine the perturbed sample after an adjustable time . This optical technique is a type of transient spectroscopy that can investigate the electronic and structural properties of transient transient states of photochemically or photophysically related molecules. The resulting excited state is examined by monitoring properties related to the probe beam, including reflectivity, absorption, emission and Raman scattering properties. Electronic and structural changes that occur in the femtosecond to picosecond timeframe can be studied using this technique.

  In general, the pump-induced state is a higher energy form of the molecule. These higher energy molecular forms differ from the lowest ground state energy states, including electron and / or nuclear redistribution.

  A basic pump probe configuration is shown schematically in FIG. A pulse train generated by the laser 7502 is divided into a pump pulse 7506 and a probe pulse 7508 using a beam splitter 7504. Pump pulse 7506 interacts with atoms and molecules in sample 7510. Probe pulse 7508 is used to probe changes that occur in the sample after a short time (between the pulse train and the probe pulse train). By changing the delay time between pulse trains with an optical delay line, the absorption spectrum, reflectivity, Raman scattering and emission of the probe beam are obtained by studying changes caused by the pump pulse train of the sample with a detector 7512. can do. By monitoring the probe train 7508 as a function of relative time delay, it is possible to obtain information about the level drop of pump-induced excitation. The probe train 7508 is typically averaged over many pulses and the high speed photodetector 7512 is not required. The time resolution of measurements in pump-probe spectroscopy is limited only by the pulse width of each train. In general, timing uncertainty needs to be smaller than the time scale of the structure or electronic process induced by the pump train.

  In two-color pump-probe spectroscopy, the pump beam 7506 and probe beam 7508 have different wavelengths generated by two synchronized light sources. While this technique provides additional capabilities in ultrafast spectroscopy, it is essential to ensure accurate source synchronization with very little relative timing jitter.

Compared to the spontaneous Raman scattering intensity, the scattering intensity provided by the pump-probe Raman spectroscopy technique can be greatly enhanced by different pump and probe frequencies Ω and ω, as shown in FIG. The frequency of the pump beam is changed, but the frequency of the probe beam is fixed. The pump beam is used to induce Raman emission, and the probe beam serves to reveal the Raman mode. Both the pump beam and the probe beam pass collinearly through the Raman active medium. When the difference between the pump frequency and the probe frequency matches the Raman vibration mode frequency ν of the medium, weak spontaneous Raman light is amplified by several digits (10 to 10 ⁴ ) due to the pump photon flux. Gain is achieved as shown in FIG.

  The pump beam is basically designed to provide various perturbation excitations in a wide range of samples. Thus, pump-probe spectroscopy is applicable for use in the context of other spectroscopic techniques, including the use of pump beams provided with orbital angular momentum, which will be discussed in the next section.

[Orbital angular momentum (OAM) spectroscopy]
Chiral optics has traditionally been accompanied by circularly polarized light. In this context, the plane polarization state is understood as a superposition of a plurality of circularly polarized lights having rotational properties opposite to each other. The right and left rotational properties of circularly polarized light indicate its spin angular momentum (SAM), ± h, in addition to polarized light, and the associated electromagnetic field vector helicity can be used. Its interaction with the substance is enantiomerically specific. Combination techniques have specific signatures for various substances.

  As described in more detail herein above, the optical vortex that occurs in the beam of light introduces helicity into the wavefront surface of the electromagnetic field, and the associated angular momentum is considered the “orbit”. The orbital angular momentum (OAM) of photon radiation is often referred to as the “twisted” or “helical” property of the beam. Most studies of the interaction between light and matter given OAM are directed to achiral molecules.

  Delocalized OAMs in solid materials associated with Bloch framework envelope wave functions, which can be macroscopic in spatial extent, can be distinguished from local OAMs associated with atoms. The latter is associated with the Lande g-factor and the effective spin portion of the electronic state, while the former is the subject of orbital coherent systems (eg, quantum Hall layers, superconductors and topological insulators). The development of these techniques presents opportunities to improve the understanding of scattering and quantum coherence of chiral electronic states and has potential implications for material discovery and quantum information. For this purpose, a theoretical configuration describing OAM-material interactions such as those using dielectrics is useful.

The beam of light provided with OAM has been used to induce such delocalized OAM states in solids using a time-resolved pump-probe scheme using LG beams, and bulk n-doped. Dichroism sensitive to OAM of GaAs (3 × 10 ¹⁶ cm ⁻³ Si) and undoped GaAs (held in the cryostat at 5K) is utilized. Using this method, an electronic “vortex” was induced and measured by a time-delayed probe beam (its OAM component detected at a balanced photodiode bridge). Research has shown that time-resolved OAM decay rates (picoseconds to nanoseconds) depend on doping, and differ from spin and population lifetimes, and “Time-resolved orbital angular momentum spectroscopy” by MA Noyan and JM Kikkawa (Appl. Phys Lett. 107 032406 (2015)), which is incorporated by reference herein in its entirety, is demonstrated to be longer than expected.

  A simple pump-probe OAM spectrometer is shown schematically in FIG. 77, where an OAM pump beam 7702 is circulated between l = + 1 and l = −1 at a certain frequency ν_l and l = ± 1 Laguerre-Gauss. It is a beam. The pump beam 7702 perturbs the target molecule in the sample 7704 and the direct probe beam 7406 is used to examine the resulting perturbation. The sample can be a crystalline solid, an amorphous solid, a liquid, a living organism, or an inorganic substance.

  The interaction of chiral molecules with light indicative of OAM (momentum-oriented photon flow) is the subject of several recent theoretical and experimental reports. On the one hand, it is speculated that the strength of the interaction is negligible, but on the other hand, not only such an interaction exists, but also the conventional optical rotation measurement experiment (the direction of linearly polarized light incident on the solution is the direction of the solution itself). It may be stronger than the interaction that occurs in (rotates with certain angular characteristics). Several limited experimental studies suggest that the theoretical part of the former study is correct and that this interaction is negligible.

  Nevertheless, various light-matter interactions using an OAM-provided optical beam can result in spectroscopic (OAM transmission between acoustic and photon modes in an optical fiber, Raman sideband with OAM. And the manipulation of colloidal particles using optical OAM “tweezers”).

[OAM spectroscopy of chiral molecules]
Recent experiments with various integer azimuthal degree l Laguerre-Gaussian (LG) beams moving through short optical path lengths of various concentrations of glucose suggest the existence of measurable OAM light-matter interactions. The theoretical part of the research is supported. These experiments suggest that not only is the interaction present, but the interaction appears stronger than with optical rotation measurements. This is because the OAM beam has a much shorter path length (1 cm to 3 cm) than the path length (greater than 10 cm) generally required in conventional optical rotation measurement studies to obtain a measurable perturbation of linear polarization. This is because perturbation occurs.

  The Gaussian beam solution of the wave equation and its extension to higher order laser modes including Hermite-Gauss (HG) are commonly studied in optical laboratories. It is particularly interesting that the LG mode exhibits a helical or helical phase plane. In addition to the spin angular momentum, the propagation vector includes an orbital angular momentum (OAM) component (often referred to as vorticity).

  Spatial light modulators (SLMs) are frequently used to implement holograms that modulate the phase plane of a Gaussian beam, and there is new interest in beams designed for various purposes.

ただし、ｗ（ｚ）はビームスポットサイズであり、ｑ（ｚ）は、球波面及びスポットサイズの展開を含む複素ビームパラメータであり、整数ｐ及びｌは、それぞれ径方向モード及び方位角モードの指標である。ｅｘｐ（ｉｌθ）項は、らせん位相面を表す。コリメートされたビームが、位相遅延フォーク型回折格子又はホログラム（図１５Ａ〜図１５Ｄに示すようなもの）によって適切に符号化されたＳＬＭから反射される。フォーク型ホログラムについての生成方程式は、フーリエ級数として表すことができる：

ここで、ｒ及びφは座標であり、ｌは渦度の次数であり、Ｄはフォーク型極から離れた直線回折格子の周期である。フーリエ成分の重みｔ＿ｍは、以下のように整数次のベッセル関数で表すことができる：

ここで、ｋαはフォーク型回折格子の位相にバイアスをかけ、ｋβはフォーク型回折格子の位相を変調する。ＯＡＭビームの生成には、幾つかの項しか必要でなく（例えば−１≦ｍ≦１）、、

The formula for the electric field of the LG beam in cylindrical coordinates is as follows:

Where w (z) is the beam spot size, q (z) is a complex beam parameter including the development of the spherical wavefront and spot size, and the integers p and l are indices of the radial and azimuthal modes, respectively. It is. The exp (ilθ) term represents a helical phase plane. The collimated beam is reflected from an SLM appropriately encoded by a phase retarding fork diffraction grating or hologram (as shown in FIGS. 15A-15D). The generation equation for a folk hologram can be expressed as a Fourier series:

Here, r and φ are coordinates, l is the degree of vorticity, and D is the period of the linear diffraction grating away from the fork-type pole. The Fourier component weight t_m can be expressed as an integer-order Bessel function as follows:

Here, kα biases the phase of the fork type diffraction grating, and kβ modulates the phase of the fork type diffraction grating. Only a few terms are needed to generate an OAM beam (eg, −1 ≦ m ≦ 1),

  As shown in FIG. 78 for OAM mode orders l = 5, 6 and 7 propagated through 3 cm cuvettes containing various concentrations of glucose, the OAM signature was found to be non-linear with respect to concentration. Although this preliminary data is noisy, this trend persisted over several OAM orders and was repeatable on a daily basis and after several setup readjustments and other changes made for convenience.

  Glucose shows a broad optical absorption band at about 750 nm and FWHM is about 250 nm. A stronger OAM response was observed at 543 nm, where the absorbance is a quarter of the absorbance at 633 nm. This suggests an interaction based on the real part χ ^ ′ of the susceptibility rather than the imaginary part χ ″ of the susceptibility. In another glucose optical rotation measurement experiment using a 20 cm long cuvette, a specific rotation of 50% greater at 543 nm than at 633 nm was measured. Consistent with previous OAM optical rotation measurements using chiral molecules in solution, no discernible polarization state change was observed using an OAM beam through a sample of 3 cm or less.

  Although glucose is known to have an optical rotation response at these wavelengths, the concentration-path length product, cl, was too small to generate a measurable shift in polarization state in this OAM study. Observation of topological changes reported using a beam given OAM suggests that the interaction between the OAM beam and the chiral molecule is more pronounced than the interaction associated with conventional optical rotation measurements. The interaction between OAM beams and chiral molecules can lead to new metrology techniques and possibly a better understanding of the few light-matter interactions. Of particular interest is the interaction of light with molecules that exhibit varying degrees of chirality. This is the subject of the next chapter.

ここで、Ｇは特定の対称性群であり、Ｐ_ｉは元の構成の点であり、

は、最近接Ｇ対称構成において対応する点であり、ｎは構成点の総数である。 [Molecular chirality]
Molecular chirality is its “handedness” geometric property characterized by various spatial rotation, inversion and mirroring operations. Traditionally, the degree of molecular chirality has been clearly limited to molecules that are “chiral” or “achiral” in addition to being “left-handed” or “right-handed”. However, this binary binary scale is not suitable for detailed spectroscopic studies of millions of molecular systems that can be studied. Instead, a continuous scale of 0-100 called the continuous chirality scale (CCM) has been realized in the last 20 years. Basically, this continuous measure of chirality includes a continuous symmetry measure (CSM) function as follows:

Where G is a specific symmetry group, P _i is the point of the original configuration,

Are the corresponding points in the nearest G symmetric configuration, and n is the total number of configuration points.

The objective is to identify a point set P _i having the desired G symmetry such that the total normalized displacement from the original point set P _i is minimized. The symmetry range 0 ≦ S ′ (G) ≦ 1 can be expanded so that S = 100S ′. The advantages of CCM over other chiral scale schemes include a wide range of chiral structures (including distorted tetrahedra, helicenes, fullerenes, frozen rotamers, knots) and their chiral reaction coordinates Ease of application and being measured without reference to the ideal shape. The intrinsic chirality value is obtained with reference to the nearest symmetry group (σ or S _2n ), and thus can be directly compared with a wide range of geometric shapes.

  In addition, the new technique described above considers the use of stimulated Raman spectroscopy or resonant Raman spectroscopy with vector beams (ie, beams with “twistedness” + polarized light), making this technique chiral. It is equally applicable to both molecules and non-chiral molecules.

[Raman by orbital angular momentum]
The influence of orbital angular momentum on the Raman scattering spectrum of glucose was investigated. Changes in the Raman spectrum were observed with L = 2 (helical beam) compared to L = 0 (Gaussian beam), especially at 2950 cm ⁻¹ . It is an innovation that when the sugar molecule has some kind of chiral symmetry 7908, the differential signal 7902 (FIG. 79) can be seen using OAM spectroscopy 7904 and Raman spectroscopy 7906. The Raman spectra of glucose, sucrose, and fructose have already been collected from the argon ion laser source and the helium neon laser source for three laser wavelengths of 488 nm, 514.5 nm, and 632.8 nm, and the signals are listed, and each vibration matches Is justified using the other two laser lines. Since there was no direct electron absorption by these energies, the expected resonance was not observed. However, the Raman spectrum is sensitive to the local and global symmetry of the molecule at any wavelength. The differential Raman signal provides basic information about the interaction between the chiral electromagnetic field and the sugar molecule, and may result in selective symmetric resonances for low level glucose detection in the blood.

  The system used for these measurements is a confocal microscope attached to a 75 cm single stage spectrometer using a diffraction grating blazed at 500 nm and a groove density of 1200 lines / mm. The microscope objective used was 10 times magnified. In order to generate an OAM beam with an angular momentum value L = 2, a Q plate was incorporated into the system.

  Referring now to FIG. 80, an alignment procedure is shown. A linear polarizer is inserted into the beam path at step 8002 and rotated until maximum transmission intensity is achieved at step 8004. The Q plate is inserted into the beam path at step 8006 and the center at which the OAM beam is generated is positioned (by observation of the donut) at step 8008. A circular polarizer is inserted in front of the Q plate at step 8010. A linear polarizer is placed after the Q plate in step 8012 and the four-lobe structure is observed. Finally, the circular polarizer is rotated at step 8014 until the output from the final linear polarizer shows a donut at all angles of the final linear polarization. This procedure is repeated to adjust the applied voltage to the Q plate (approximately 4 volts) and the square wave drive frequency (approximately 2 KHz). The measurement is performed without using the final linear polarizer.

The L = 2 spectrum obtained with the L = 0 spectrum (no element in the beam path) (in each case normalized to the maximum value which is a Raman signal near 2800 cm ⁻¹ ) 81 and FIG. These measurements show that there is an intensity difference between two different excitations. Approximately 50% of the increase in the scattering intensity at 400 cm ^-1 and 550 cm ^-1 were observed, the spectrum of the L = 2 show some additional shoulder of each of these lines. The intensity ratio of doublets around 2950 cm ⁻¹ is most prominent.

  The Raman system used for these measurements is limited in alignment. Incorporating an additional wave plate causes a slight walk-off that results in a significant reduction in collection intensity in the confocal system. Presumably, normalization solves any alignment strength problem, but signal-to-noise worsens and longer integration is required. Long integration times are not always possible or appropriate.

  These measurements need to be repeated for glucose and also for fructose. It is also necessary to confirm the response to purely circularly polarized light without OAM. It should be possible to optimize the Q plate operation using alignment. The OAM L = 1 and L = 20 values should also be used. With this promising result, a quarter wave plate is used for 488 nm since this laser generates the best spectrum with the shortest acquisition time in the system.

  Higher energy Raman signals are not unique to glucose because they represent the common carbon and carbon hydrogen bonds present in many organic systems, but may prove to be unique to chiral systems. In addition, as the system is better optimized for the Q plate, the lower energy modes that are more specific to glucose may show better differentiation from OAM.

[Optical activity by single crystal rock sugar]
The optical activity of sugar molecules has been well studied and is the result of the chiral symmetry of the molecule resulting in the polarization of the sugar system imparting a slight rotation of the incident light, so that the final transmitted beam is at the concentration of the molecule present. Depending on having rotation. An experiment was started to develop a versatile and sensitive system for detecting polarization changes due to transmission or reflection of matter using orbital angular momentum. This system is ideal for use with SLMs and can in principle generate any type of beam. As a starting point, samples of rock sugar each having a thickness of several millimeters were obtained, showing high crystallinity and regular cleavage planes. These rock sugar samples can be polished to optically finish the surface, but previous internal defects prevent clear transmission measurements and the signal is collected as forward scatter. The crystal is cleaved into three pieces that exhibit a clear symmetry of the crystal plane, and the z-axis of the crystal is oblique to the cleavage plane. When starting these measurements, the data is also compared for Q plate output. This measurement system will be a balanced lock-in detection optical system for future polarization sensitive measurements and stimulated Raman measurements.

  Access to multiple monitors is required for an SLM on a properly configured computer capable of performing SLM, Matlab and video capture simultaneously.

  Referring now to FIG. 81, the output of the HeNe laser is chopped around 1 kHz and sent to a single mode fiber. The output is collimated by two biconvex lenses, sent through a half-wave plate, and the polarization incident on the Hamamatsu LCOS SLM 8102 is adjusted at an incident angle of less than 10 degrees according to the operating specifications of the SLM. The SLM 8102 displays a forked diffraction grating or a helical phase pattern hologram generated using the MATLAB code, and generates a desired OAM beam. The reflected beam carries the OAM and a characteristic “donut” shape with zero intensity is seen along the beam axis. This beam is then sent to a detector 8106 through a pair of crossed polarizers 8104 for lock-in detection. We will also explore experimental systems that employ symmetrical detectors.

Experiments have shown an approximately 20 degree shift in the intensity curve for these polished sugar crystals. A series of measurements are made after the detection scheme is finished. These include the following:
1. Optical activity throughout the polished crystal.
2. Optical activity through each of the cleaved pieces independently to investigate whether there is an additive / subtractive effect of optical activity at different cutting directions, and which direction is sensitive to OAM .

[Raman detection of glycated protein]
Hb and Hb-A1ca proteins can also be investigated by Raman spectroscopy using OAM. Mammalian blood is considered connective tissue because of its cellular organization, its embryonic origin, and the origin and presence of colloidal proteins in plasma. Red blood cells and plasma proteins are the main components of blood. These connective tissue components are targets of metabolic stress in disease states, resulting in chemical changes. All blood components are subject to excessive metabolic stress in hyperglycemic conditions. Blood serves as the primary transporter of nutrients, gases and excreta. Plasma serves as the primary transporter of glucose to tissues. Normal pre-prandial plasma glucose levels are between 80 mg / dl and 130 mg / dl, and normal post-prandial plasma glucose is less than 180 mg / dl. The renal threshold of glucose (RTG) is the physiological maximum of plasma glucose beyond which the kidney cannot reabsorb glucose and glucose is excreted in the urine. This is a condition called diabetes. Diabetes is a major feature of diabetes mellitus (DM). High plasma glucose in DM causes an increase in the level of glycosylated hemoglobin, also known as HbA1c. Under normal physiological conditions, HbA1c levels are less than 7%, which is also expressed as eAG and should be less than 154 mg / dl in normoglycemia.

[Glycation of plasma protein in DM]
Glycation is defined as a non-enzymatic random non-specific covalent linkage of glucose or other hexose sugar moiety to a protein. Blood glucose levels in healthy individuals have glycated hemoglobin (HbA1c) levels of less than 7% in blood, but under hyperglycemic conditions such as DM, the levels increase. Higher blood glucose levels may induce glycation of other major proteins in plasma such as albumin.

[Advantages of glycated protein measurement in DM]
Measuring blood glucose levels only gives information at a specific point in time about the subject's blood glucose status. That is, a diabetic with an uncontrolled blood sugar level over several months may obtain normal blood glucose levels when tested on a particular day under fasting conditions or with low carbohydrate intake. However, measurement of glycated hemoglobin (HbA1c) levels in the blood provides information about the patient's average blood glucose level over the past 2 to 3 months. Therefore, in the past decade, measuring glycated hemoglobin in DM patients has become standard clinical practice due to the development of sensitive and reliable laboratory analysis. We have detected the detection of specific Raman fingerprints, which can be caused by non-enzymatic glycation of major blood proteins hemoglobin, plasma albumin, etc. in natural and altered physical states In order to propose the use of Raman spectroscopy studies for diabetic blood and its components. Glycation processes in proteins induce chemical changes, structural modifications, and conformational changes. Any or all of these can cause special Raman spectral changes and can be used as clinical markers.

  Measurements were made using a small desktop OceanOptics Raman system with 532 nm excitation.

[Raman spectroscopy of tryptophan]
Because hemoglobin (tetramer) has a 6-residue tryptophan, hemoglobin is a fluorescent protein. Tryptophan undergoes glycation and can cause conformational changes in hemoglobin. Tryptophan alterations can be identified by using Raman studies (Masako Na-Gai et al. Biochemistry, 2012, 51 (30), pp 59325941, incorporated herein by reference). To understand the change in Raman spectra induced by saccharification at tryptophan residues, Raman spectra are obtained from analytical grade amorphous tryptophan using 532 nm OceanOptics Raman.

[Raman spectrum of protein]
Solid amorphous powders of albumin and glycated albumin samples were subjected to Raman measurements using the OceanOptic 532 nm Raman system and confocal Raman systems using 488 nm, 514.5 nm and 632.8 nm. No Raman signal was observed from these samples. Therefore, it is necessary to retest in a solution with a physiological pH of 7.4.

The next steps are as follows:
1. NIR Raman: Since blood and its components have strong fluorescence in the visible range, NIR Raman can help reduce fluorescence and can yield good Raman signals from target protein molecules.
2. OceanOptics 532 nm Raman: This can be used to detect some of the glycated derivatives in the blood. Normal blood and diabetic blood from either a human subject or animal model is required. Also, by using this system, a reference spectrum of a synthetic saccharification product can be obtained, and this can be compared later with a Raman signal derived from a blood sample.
3. In vivo animal model: In order to succeed in future experiments for in vivo blood glucose and diabetes testing, Raman measurements need to be performed in a rat diabetes animal model.

[Raman OAM for detection of food freshness, damage and organic matter]
Another aspect investigated is concerns about food safety due to damage to meat, agricultural products, dairy products and cereals, and determination using Raman and OAM to determine whether the labeled food is organic. Social and personal concerns have led to both government regulations and commercial requirements for quality, stability, and food shelf life safety. Furthermore, food degradation that causes food damage results in not only health problems but also economic losses to food production and related industries. Thus, it is desirable to minimize food damage, determine food freshness, or maximize food shelf life.

  In addition, the United States Department of Agriculture (“USDA”) established guidelines and national standards for the term “organic” in 2000. For example, organic food as defined by the USDA guidelines means that food must be produced without sewage sludge fertilizers, synthetic fertilizers and pesticides, genetic modification, growth hormone, radiation, and antibiotics.

  The physical characteristics of conventional food damage such as unpleasant odor, unpleasant taste, color change, texture change and mold growth often appear after biochemical processes that compromise food quality or safety. As a result, these are not appropriate indicators to determine acceptable criteria for use with respect to food freshness, storage and damage.

  For this reason, previous work includes the identification of so-called “biomarkers” of food damage. This study involves the identification of biochemical mechanisms that generate certain chemical by-products associated with the physical characteristics of food damage. These mechanisms include physical mechanisms (eg, temperature, pH, light, mechanical damage), chemical mechanisms (eg, enzymatic reactions, non-enzymatic reactions, rancidity, chemical interactions), microbial-based mechanisms (eg, Bacteria, viruses, yeasts, molds), or other mechanisms (eg, insects, rodents, animals, birds).

  One aspect of the study is to use OAM and Raman techniques to identify these so-called biomarkers and their associated concentrations and to better determine the shelf life of basic food categories. Additionally, another aspect of the present invention is to investigate the chemicals that are used that make a food product unable to be considered “organic”. For example, Table 1 below shows some studied biochemical processes and chemical by-products associated with food damage mechanisms associated with common food groups.

  Those skilled in the art will recognize a variety of other mechanisms and biochemical indicators (other reactions associated with food damage, or volatile or non-volatile organic compounds (VOCs)) that are evidence of food damage to common food products. (Including product) is well understood. Similarly, regardless of whether grain, dairy products, agricultural products, or meat are being investigated, those skilled in the art are well aware of the chemicals and additives that make a food product non-organic.

  Conventional spectroscopic techniques are unsuitable for identifying these biomarkers in real time or at appropriate concentrations in any meaningful manner to determine the shelf life of food samples or the organicity of the food in question. . For the purposes of this survey and invention, to classify, identify and quantify the various biomarkers and common chemicals in the above table (those that make foods not considered organic as defined by federal regulations) The above Raman and OAM methods are used.

  Such techniques are equally applicable regardless of whether the biomarker or chemical is a chiral or non-chiral molecule. In that case, such data can be correlated with the sampled food group degradation concentrations to determine acceptable minimum and maximum concentrations for food freshness, damage, organic quality and safety.

[Ins-Gauss spectroscopy]
Another type of spectroscopic technique that can be combined with one or more other spectroscopic techniques is in-Gaussian spectroscopy. An Insgaussian (IG) beam is a paraxial beam solution in an elliptical coordinate system. IG beams are orthogonal eigenstate third calls that can probe the chirality structure of the sample. Since the IG mode has favorable symmetry (long axis vs. short axis), it is possible to probe the chirality better than the Laguerre Gaussian or Hermitian Gaussian mode. Thereby, it is possible to propagate more IG modes in an elliptical core fiber than Laguerre Gaussian mode or Hermitian Gaussian mode. For this reason, the IG mode can be used as a program signal for spectroscopy in the same manner as using the Laguerre Gaussian mode or the Hermitian Gaussian mode. As a result, the type of substance and the concentration of the substance can be detected using the IG mode probe signal.

Ｅ（ｘ，ｙ，ｚ）は、ｚ方向においてゆっくり変化する包絡線及び急速に変化する部分で表すことができる複素場振幅である。

The wave equation can be expressed as a Helmholtz equation in Cartesian coordinates as follows:

E (x, y, z) is the complex field amplitude that can be represented by an envelope that changes slowly in the z direction and a rapidly changing part.

The paraxial wave approximation can be determined by substituting our assumptions into the Helmholtz equation.

これは近軸波動方程式を含む。 Next, get a slowly changing envelope approximation:

This includes the paraxial wave equation.

The elliptical-cylindrical coordinate system can be defined as shown in FIG.

The constant value curve of ξ traces the confocal ellipse as shown in FIG.

With the constant value of η, a confocal hyperbola is obtained as shown in FIG.

ここで、ｈ_ξ、ｈ_ηはスケール因子である：

Next, an ellipsoid-cylindrical coordinate system can be defined as follows:

Where h _ξ and h _η are scale factors:

Next, the solution of the paraxial wave equation can be made into elliptical coordinates. The paraxial wave equation in elliptic cylindrical coordinates is defined as follows:

Ｅ、Ｎ及びＺは実関数である。これらは、ψ_ＧＢと同じ波面を有するが、異なる強度分布を有する。 Assume a separable solution as a modulated fundamental Gaussian beam.

E, N and Z are real functions. They have the same wavefront as ψ _GB but have a different intensity distribution.

ここで、ａ及びｐは分離定数であり、

A separate differential equation is defined as follows:

Where a and p are separation constants,

偶数インス多項式の周波数が図８５Ａ及び図８５Ｂに示され、モード及びそれらの位相が図８６に示される。 The even solution of the Ins-Gauss equation is as follows:

The frequency of the even ins polynomial is shown in FIGS. 85A and 85B, and the modes and their phases are shown in FIG.

奇数インス多項式の周波数が図８７Ａ及び図８７Ｂに示され、モード及びそれらの位相が図８８に示される。 The odd solution of the Ins-Gauss equation is:

The frequencies of the odd ins polynomials are shown in FIGS. 87A and 87B, and the modes and their phases are shown in FIG.

  Thus, as discussed above with respect to FIG. 59, by combining two or more different types of spectroscopic techniques, different types of different parameters can be monitored and used to determine the type and concentration of sample material. it can. The use of multiple types of spectroscopic parameter analysis allows for a more accurate and detailed analysis of sample type and concentration. For this reason, any number of spectroscopic techniques (optical spectroscopy, infrared spectroscopy, Raman spectroscopy, spontaneous Raman spectroscopy, stimulated Raman spectroscopy, resonance Raman spectroscopy, polarization Raman spectroscopy, optical vortex were used. Raman spectroscopy, THz spectroscopy, terahertz time domain spectroscopy, fluorescence spectroscopy, pump probe spectroscopy, OAM spectroscopy or Insgaussian spectroscopy, etc.) in any number of different combinations and sample types at concentrations Better detection of. It should be understood that the types of spectroscopy discussed herein are not limited to any combination of spectroscopic techniques and can be utilized for the analysis of sample material.

[Multi-parameter dual-comb spectroscopy using OAM]
Precision spectroscopy using a pairing optical frequency comb that can improve the results can be performed. Referring now to FIG. 89, in broadband frequency comb spectroscopy, the signal from the optical frequency comb is transmitted by a conventional spectrometer, but referred to as a technique called dual comb spectroscopy (speed and resolution of the conventional spectrometer 8902 and instrumentation). The restrictions are removed). Instead, the second frequency comb 8904 takes over the work previously done by the spectrometer 8902. A dramatic increase in data acquisition speed, spectral resolution and sensitivity can result. These techniques can be used in conjunction with multi-parameter spectroscopy 8906 (utilizing wavelength, polarization and OAM spectroscopy 8908).

[Optical frequency comb]
The optical frequency comb 8904 is a spectrum consisting of hundreds of thousands or millions of well-spaced well-similar lines with a very large number of continuous wave (CW) lasers that emit simultaneously at various equally spaced frequencies. An optical comb can be generated in many ways. The most common method uses a phase stabilized mode-locked ultrashort pulse laser. In the time domain, the laser generates a specific repetition rate pulse train with a specific increasing additional carrier-envelope phase (with each successive pulse). When both the repetition rate of the pulse train and the carrier-envelope phase are stabilized against a radio or optical frequency reference, the Fourier transform of the periodic pulse train of the laser exhibits a distinct comb-like spectrum in the frequency domain.

  If the frequency comb is sufficiently stabilized and calibrated against an absolute frequency standard such as an atomic clock, the comb spectrum becomes a very precise ruler for measuring optical frequencies. This ruler applies to a wide range of scientific problems: high-resolution frequency measurements of atoms, ions or molecular transitions (to answer basic physics problems); detection of trace Doppler shifts; and attoseconds Other applications in physics, ultra high purity microwave generation, long range time-frequency transfer, manipulation of atomic qubits, and many others.

  One of the most active research areas on frequency combs is broadband molecular spectroscopy. Com's millions of equally spaced lines provide the opportunity to measure complex broadband molecular signatures with high spectral resolution and sensitivity. However, to take advantage of these advantages, a sufficiently high resolution spectrometer is required to resolve each comb line. One approach may be the use of a spectrometer based on a virtual imaging phased array (VIPA) disperser in combination with a diffraction grating. In another common scheme, analytical chemistry, a Michelson Fourier Transform spectrometer is used, and a conventional broadband, usually incoherent light source is replaced with a frequency comb.

  In this approach to frequency comb spectroscopy, the frequency comb pulse train is divided into each interferometer arm (one of which comprises a mechanically scanned mirror) and two pulse trains are analyzed. Sent through. As the mirror is scanned, a series of interferograms are recorded with a single receiver and digitizer. The spectrum is generated by the Fourier transform of the interferogram, but the resolution is determined by the maximum optical path length difference of the interferometer.

[Advantages of Dualcom]
The main disadvantage of performing frequency comb spectroscopy using the described Michelson-type setup is speed. The scan speed of the setup, which is limited by the speed of the scanning mirror, is generally only on the order of Hz. In dual comb spectroscopy, this disadvantage is mitigated by providing a delay time using a second frequency comb rather than a moving mirror. A significant improvement in spectrometer performance can be obtained as a result.

  In a dual comb setup, the pulse train forms a second comb at a slightly different pulse repetition rate than the first comb and is spatially combined with the train from the first comb. The combined pulse train passes through the sample to be analyzed and is detected by the photoreceiver. The result is a repeating sequence of interferometer signals, such as a cross-correlation function, between pulses in the time domain (with a time difference that steadily increases based on the difference in repetition rate between the two combs). For this reason, the dual comb interferogram has the same characteristics as the conventional Michelson type Fourier transform spectrometer, but since the dual comb setup does not depend on the mechanical movement of the mirror, the scanning speed is the Michelson type. An order of magnitude faster than an interferometer.

  Another advantage of dual comb spectroscopy appears in the frequency domain. Here, by mixing two optical combs with slightly different repetition rates, a third, down-converted radio frequency (RF) comb (the spacing between the teeth is the difference in repetition rate between the two optical combs). Is obtained). Thus, the sample response is encoded on this downconverted RF comb, and the beat measurement between the two optical combs generates a multi-heterodyne signal that can be recovered from the RF comb. In summary, the downconverted comb inherits the coherence characteristics of the optical frequency comb and allows broadband spectroscopy with high resolution and accuracy, with the advantages of RF heterodyne detection speed and digital signal processing.

[Small wearable device]
A small wearable optical device based on Raman and NIR absorption for detecting changes in physiological chemical levels in the body can also be implemented. In addition to new detection schemes, small integrated electron-photon systems (and ultimately integrated silicon photonics systems) are also being developed. The wearable device 9000 includes the following components as shown in FIG. An MCU (micro controller) 9002 controls all operations of the wearable device 9000. A BLE (Bluetooth low energy) transmitter / receiver 9004 communicates signals to and from the wearable device 9000. Trans-impedance amplifier (TIA) that amplifies the signal internally. Driver 9008 that drives the LED / laser in device 9000. The high resolution ADC 9010 performs analog-to-digital conversion. The flash memory 9012 stores data in the wearable device 9000. Real time clock 9014 controls internal clocking operations.

The main requirements are low quiescent current for all components, ability to enter deep sleep mode, low current consumption in operating mode, low frequency mode / low power operation of real-time clock, and MCU and BLE Single battery operation (blue-tooth low energy). The 2013-2015 model MCU + BLE chipset gives you a choice of the following components:
a) EFM32 (MCU Silicon Laboratories) + CC2541 (BLE chip Texas Instruments) or BCM20732 (Broadcom), or
b) Nordic Semiconductor NRF51822 in the form of a single chip solution (with similar Cortex M0 core and BLE radio). The BLE stack is realized by a basic Nordic original OS (Soft Device) that occupies about 100 kB of chip memory.

Either of these two solutions is used in 90% of modern BLE wearable devices. In this case, the preferred embodiment uses a single chip solution from Nordic Semiconductor. The main features are as follows:
1) External crystal for real-time clock,
2) 256 kb memory (256 kb to 100 kb (Soft Device) = 156 kb for program and storage)
3) Sleep mode in 1uA range 4) Support for all standard BLE profiles and adjustable radio power up to 4dBm.
It also supports the ANT protocol, which can be useful for future development.

  The near-infrared laser diode system provides approximately 30 1570 nm-1600 nm controllable channels and 1450-1600 additional adjustable light sources.

  Similar portable devices can be used for the other embodiments and applications described above, including protein detection and detection of food damage or food organic biomarkers by various biochemical mechanisms associated with food damage. it can.

[OAM body imaging]
Imaging of the entire body and parts thereof is essential to most biomedical optical techniques. Past studies have developed imaging and spectroscopy in the selective transmission window of the NIR, where glucose and protein have strong absorption, but water has reduced absorption. Optical detection of glucose or other chemical compounds often needs to be in areas where there is no strong absorption from other molecules, and is performed using an OAM beam, so the body tissue, brain, bone and Skin imaging can be used. Possible investigation methods are ballistic transport of OAM through scattering media in phase contrast and dark field imaging, NIR and birefringence imaging. Diode lasers available for wearable devices may be incorporated into NIR OAM imaging after obtaining and testing a suitable detector. Single channel detectors in NIR are less expensive than 2D CCD arrays, but scanning systems and image construction software are required for imaging with single channel detectors.

[Potential use]
A small handheld 3D spectrometer capable of simultaneously operating polarization, wavelength and OAM spectroscopy, operating in a wide electromagnetic frequency range, can be used for food and air quality, household biological contaminants, pharmaceutical identification, health related issues, etc. Give consumers a huge amount of useful information about real-time information, etc.). This chapter gives an overview of some potential applications of 3D spectroscopy.

[Food industry]
Food substances mainly consist of water, fat, protein and carbohydrates. The molecular structure and concentration of food substances influence their functional properties. The quantification of these characteristics is the quality of food (including chemical, biological and microbial factors that can affect parameters such as their shelf life) with respect to minimum standards for human edible or exposure suitability. decide. Recent advances in the industrialization of food supply chains and changes in consumer eating habits place greater demands on the speed with which food should be analyzed for safety and quality. This requirement requires an appropriate analytical tool such as spectroscopy.

  Food spectroscopy is a desirable analytical method because it requires minimal or no sample preparation and even rapid production line measurements. Given the nature of spectroscopic analysis, multiple tests may be performed on a sample.

  Beyond food supply industrialized production lines, novel spectroscopic techniques can be used at the individual consumer level. For example, individual consumers can use a pocket-sized laser-based spectrometer to spectroscopically measure sugar concentration in food, overall food quality, maturity, or watermelons can be found at local grocery stores. Can be identified as rotten.

[Development of nanoscale materials for defense and national security]
The development of nanoscale materials for defense and national security technologies generally requires binding sites to recognize the target of interest. Some spectroscopic techniques are currently based on absorption, scattering (of light), such as electronic absorption (UV-vis), photoluminescence (PL), infrared (IR) absorption and Raman scattering. More advanced techniques include single molecule spectroscopy, sum frequency generation and luminescence upconversion. These spectroscopic techniques are useful in the manufacturing process of nanoscale material structures used as biosensors and chemical sensors.

[Chemical industry]
Gas sensor optical spectroscopy is useful in a variety of environmental, industrial, medical, scientific and home applications. Gases are harmful to human health, can be air pollutants, or can be important with regard to their concentrations for industrial or medical purposes. Apart from issuing an alarm, it is often desirable to measure the exact real-time concentration of a particular target gas (often in a mixture with other gases). Consumers are responsible for the monitoring of air for biological or chemical hazards, such as airborne bacteria or carbon monoxide, and monitoring of surfactant contamination in children's playgrounds, toys and bedrooms and their surroundings. Can be used. Such devices are useful in school classrooms, offices and shopping malls to alert facility managers of potential health hazards. Additional devices may be useful in various industrial environments, such as chemical and / or petrochemical plants (including but not limited to the use of near infrared spectroscopy). In addition to improving the environmental benefits of detecting various gas leaks, such detection provides plant operators with various economic benefits that identify the source of the leak to increase product recovery and reduce government fines. .

[Pharmaceutical industry]
The manufacturing process for high precision drug concentrations in pills, capsules and liquids requires close real-time monitoring as can be done by optical spectroscopy techniques. Once manufactured and distributed, consumers can easily identify pills and pharmaceuticals at home using advanced real-time spectroscopic techniques built into portable devices.

[Medical industry]
There is a strong interest in developing more sophisticated photogrammetric techniques that detect disease non-invasively. These techniques can be performed by spectroscopy that allows an optical biopsy to be performed without the need to remove tissue from the patient's body. Such techniques can be developed to create photonic finger imagers for accurate prostate examinations, breast mammograms and other cancer detection procedures. A pocket-sized skin spectrometer provides personal real-time information to the patient, which can be combined with the patient's medical records for discussion with a medical professional.

  The use of a small handheld optical spectrometer can be incorporated into the patient's daily health maintenance schedule. An example is the early detection of chemicals associated with Alzheimer's disease and Parkinson's disease by spectroscopic detection in routine eye examinations.

[Dental]
Daily personal dental care requires small tools and equipment (such as toothbrushes and dental floss). A toothbrush-sized optical spectrometer detects the occurrence of small caries (caries and holes) and alerts the consumer to schedule a visit to his or her dentist May be useful).

[Biomedical photonics]
These technologies are used in neuroimaging applications (such as optical spectroscopy and correlation methods to measure oxygen and blood flow); the ability to improve the quantitative interpretation of brain activity and psychological measurements using functional near-infrared spectroscopy It can be applied to the development of new microscopes for imaging; the development of techniques such as diffusion correlation spectroscopy for measuring blood flow; and the development of multispectral optical imaging of hemoglobin in the brain.

  Those skilled in the art having the benefit of this disclosure will recognize the present system and method for detecting the presence of a substance in a sample based on a unique signature. It should be understood that the drawings and detailed description herein are to be regarded as illustrative rather than restrictive, and are not intended to be limited to the particular forms and examples disclosed. On the other hand, any further modifications, changes, rearrangements, substitutions, alternatives, design choices and embodiments apparent to those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims Is included. Thus, it is intended that the appended claims be construed to include all such further modifications, variations, rearrangements, substitutions, alternatives, design choices and embodiments.

Claims (30)

An apparatus for detecting a substance in a sample,
A light emitting unit for directing at least one light beam through the sample;
A plurality of spectroscopic units that receive the light beam that has passed through the sample, wherein the plurality of spectroscopic units perform spectroscopic analysis of the sample based on the received light beam, and each of the plurality of spectroscopic units A plurality of spectroscopic units that analyze different parameters for the sample and provide separate output signals for the analysis;
A processor for detecting the substance for each of the supplied separate output signals;
An apparatus comprising: The plurality of spectroscopic units are
A first spectroscopic unit that receives the light beam that has passed through the sample and performs polarization wave analysis to generate a polarization parameter output signal;
A second spectroscopic unit that receives the light beam that has passed through the sample and performs wavelength analysis to generate a wavelength parameter output signal;
A third spectroscopic unit that receives the light beam that has passed through the sample and performs orbital angular momentum (OAM) spectroscopic analysis to generate an OAM parameter output signal;
The apparatus of claim 1, further comprising: The plurality of spectroscopic units are
A first spectroscopic unit that receives the light beam that has passed through the sample and performs Raman spectroscopic analysis to generate a Raman parameter output signal;
A second spectroscopic unit that receives the light beam that has passed through the sample and performs infrared spectroscopic analysis to generate an infrared parameter output signal;
A third spectroscopic unit that receives the light beam that has passed through the sample and performs orbital angular momentum (OAM) spectroscopic analysis to generate an OAM parameter output signal;
A fourth spectroscopic unit that receives the light beam that has passed through the sample and performs polarization wave analysis to generate a polarization parameter output signal;
The apparatus of claim 1, further comprising: At least one of the plurality of spectroscopy units comprises a dual comb spectroscopy unit;
The dual comb spectroscopy unit receives a pair of coherent frequency combs to receive the light beam from the sample and perform dual comb spectroscopy to generate an output signal;
The apparatus of claim 1. The plurality of spectroscopic units are
A first spectroscopic unit that receives the light beam and performs Raman sideband spectroscopic analysis to generate a first output signal;
A second spectroscopic unit that receives the light beam and performs colloidal particle manipulation using OAM tweezers;
The light beam includes a light beam provided with OAM,
The apparatus of claim 1. At least one of the plurality of spectroscopic units is
A first spectroscopic unit that receives the light beam and performs OAM spectroscopic analysis to detect delocalized OAM associated with an envelope wave function of the Bloch framework;
A second spectroscopic unit that receives the light beam and performs OAM spectroscopic analysis to detect local OAM associated with atoms in the sample;
The apparatus of claim 1, comprising: The plurality of spectroscopic units are
A first spectroscopic unit that receives the light beam that has passed through the sample and performs polarization wave analysis to generate a polarization parameter output signal;
A second spectroscopic unit that receives the light beam that has passed through the sample and performs orbital angular momentum (OAM) spectroscopic analysis to generate an OAM parameter output signal;
The apparatus of claim 1, further comprising: the processor detecting a unique signature for the substance in the sample indicated by the polarization parameter output signal and the OAM parameter output signal. The plurality of spectroscopic units are
A first spectroscopic unit that receives the light beam that has passed through the sample and performs orbital angular momentum (OAM) spectroscopic analysis to generate an OAM parameter output signal;
A second spectroscopic unit that receives the light beam that has passed through the sample and performs fluorescence spectroscopic analysis, detects an emission spectrum and an excitation spectrum in the sample, and generates a fluorescence parameter output signal;
The apparatus of claim 1, comprising:   9. The apparatus of claim 8, wherein the fluorescence spectroscopic analysis maintains excitation radiation at a fixed wavelength and measures emitted fluorescence intensity as a function of emission wavelength. The plurality of spectroscopic units are
A first spectroscopic unit that receives the light beam that has passed through the sample and performs orbital angular momentum (OAM) spectroscopic analysis to generate an OAM parameter output signal;
A second spectroscopic unit that receives the light beam that has passed through the sample and performs terahertz (THz) spectroscopic analysis to generate a fluorescence parameter output signal;
The apparatus of claim 1, comprising:   11. The apparatus of claim 10, wherein the THz spectroscopy provides selective detection of weak intermolecular vibration modes and weak intramolecular vibration modes that cannot be detected by infrared spectroscopy.   The apparatus of claim 10, wherein the THz spectroscopic analysis detects a two-dimensional THz absorption characteristic.   The apparatus of claim 10, wherein the THz spectroscopic analysis scans the sample multiple times in two dimensions, each scan being scaled by sample size. The plurality of spectroscopic units are
A first spectroscopic unit that receives the light beam that has passed through the sample and performs orbital angular momentum (OAM) spectroscopic analysis to generate an OAM parameter output signal;
A second spectroscopic unit that receives the light beam that has passed through the sample and performs Raman spectroscopic analysis to generate a Raman parameter output signal;
A third spectroscopic unit that receives the light beam, performs polarization Raman spectroscopic analysis, and generates a third output signal;
A fourth spectroscopic unit that receives the light beam, performs non-polarized Raman spectroscopic analysis, and generates a fourth output signal;
Further comprising
The apparatus of claim 1, wherein the Raman spectroscopic analysis of the second spectroscopic unit further detects optical vortices in the received light beam. A method for detecting a substance in a sample, comprising:
Directing at least one light beam through the sample;
Receiving the light beam that has passed through the sample with a plurality of spectroscopic units;
Performing spectroscopic analysis of the sample by analyzing different parameters for the sample based on the light beam received by each of the plurality of spectroscopic units;
Providing a separate output signal for the analysis at each of the plurality of spectroscopic units;
Detecting the substance in the sample for each of the supplied discrete output signals;
Including a method. The step of performing the spectroscopic analysis includes
Performing polarization wave analysis and generating a polarization parameter output signal;
Performing wavelength analysis and generating a wavelength parameter output signal;
Performing orbital angular momentum (OAM) spectroscopic analysis and generating an OAM parameter output signal;
16. The method of claim 15, further comprising: The step of performing the spectroscopic analysis includes
Performing Raman spectroscopy and generating a Raman parameter output signal;
Performing infrared spectroscopy and generating an infrared parameter output signal;
Performing orbital angular momentum (OAM) spectroscopic analysis and generating an OAM parameter output signal;
Performing polarization wave analysis and generating a polarization parameter output signal;
The method of claim 16, further comprising:   The method of claim 15, wherein performing the spectroscopic analysis further comprises performing dual comb spectroscopic analysis and generating an output signal. The step of performing the spectroscopic analysis includes
Performing a Raman sideband spectroscopic analysis and generating a first output signal;
Performing colloidal particle manipulation using OAM tweezers;
16. The method of claim 15, wherein the light beam comprises a light beam provided with OAM. The step of performing the spectroscopic analysis includes
Performing OAM spectroscopy to detect delocalized OAM associated with the Bloch framework envelope wave function;
Performing OAM spectroscopy to detect local OAM associated with the atoms in the sample;
16. The method of claim 15, further comprising: The step of performing the spectroscopic analysis includes
Performing polarization wave analysis and generating a polarization parameter output signal;
Performing orbital angular momentum (OAM) spectroscopic analysis and generating an OAM parameter output signal;
Further including
16. The method of claim 15, wherein the detecting step further comprises detecting a unique signature for the substance in the sample indicated by the polarization parameter output signal and the OAM parameter output signal. The step of performing the spectroscopic analysis includes
Performing orbital angular momentum (OAM) spectroscopic analysis and generating an OAM parameter output signal;
Performing fluorescence spectroscopy, detecting an emission spectrum and an excitation spectrum in the sample, and generating a fluorescence parameter output signal;
16. The method of claim 15, further comprising: Performing the fluorescence spectroscopic analysis,
Holding the excitation radiation at a fixed wavelength;
Measuring the emitted fluorescence intensity as a function of the emission wavelength;
The method of claim 22, further comprising: The step of performing the spectroscopic analysis includes
Performing orbital angular momentum (OAM) spectroscopic analysis and generating an OAM parameter output signal;
Performing terahertz (THz) spectroscopic analysis and generating a fluorescence parameter output signal;
16. The method of claim 15, further comprising:   25. The method of claim 24, wherein performing the THz spectroscopy further comprises providing selective detection of weak intermolecular vibration modes and weak intramolecular vibration modes that cannot be detected by infrared spectroscopy.   25. The method of claim 24, wherein performing the THz spectroscopic analysis further comprises detecting a two-dimensional THz absorption characteristic.   25. The method of claim 24, wherein performing the THz spectroscopy further comprises scanning the sample multiple times in two dimensions, each scan being scaled by sample size. The step of performing the spectroscopic analysis includes
Performing orbital angular momentum (OAM) spectroscopic analysis and generating an OAM parameter output signal;
Performing Raman spectroscopy, generating a Raman parameter output signal, detecting a light vortex in the received light beam;
Performing polarization Raman spectroscopy and generating a third output signal;
Performing non-polarized Raman spectroscopy and generating a fourth output signal;
16. The method of claim 15, further comprising: An apparatus for detecting a substance in a sample,
A light emitting unit for directing at least one light beam through the sample;
A first spectroscopic unit that receives the at least one light beam that has passed through the sample and performs orbital angular momentum (OAM) spectroscopic analysis to generate an OAM parameter output signal;
At least one second spectroscopic unit for receiving the at least one light beam that has passed through the sample and performing spectroscopic analysis of the sample based on the received at least one light beam, the at least one second spectroscopic unit; Each of the spectroscopic units analyzes a parameter other than orbital angular momentum and provides a separate output signal for said analysis;
A processor for detecting the substance with respect to the OAM parameter output signal and each of the supplied separate output signals;
An apparatus comprising: A method for detecting a substance in a sample, comprising:
Directing at least one light beam through the sample;
Receiving the light beam that has passed through the sample with a plurality of spectroscopic units;
Performing orbital angular momentum (OAM) spectroscopy,
Generating an OAM parameter output signal in response to the OAM spectroscopic analysis;
Performing at least one spectroscopic analysis of the sample based on the received at least one light beam, wherein each of the at least one spectroscopic analysis analyzes parameters other than orbital angular momentum And doing
Providing a separate output signal at each of the plurality of spectroscopic units for the spectroscopic analysis;
Detecting the substance in the sample for each of the supplied discrete output signals;
Including a method.

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