WO2017123926A1 - Système et procédé de spectroscopie à paramètres multiples - Google Patents

Système et procédé de spectroscopie à paramètres multiples Download PDF

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WO2017123926A1
WO2017123926A1 PCT/US2017/013408 US2017013408W WO2017123926A1 WO 2017123926 A1 WO2017123926 A1 WO 2017123926A1 US 2017013408 W US2017013408 W US 2017013408W WO 2017123926 A1 WO2017123926 A1 WO 2017123926A1
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oam
sample
spectroscopic
output signal
analysis
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PCT/US2017/013408
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English (en)
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Solyman Ashrafi
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Nxgen Partners Ip, Llc
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Priority to JP2018536888A priority Critical patent/JP2019510202A/ja
Priority to EP17739034.1A priority patent/EP3403067A4/fr
Priority to CN201780016835.8A priority patent/CN108780042A/zh
Publication of WO2017123926A1 publication Critical patent/WO2017123926A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/0059—Measuring for diagnostic purposes; Identification of persons using light, e.g. diagnosis by transillumination, diascopy, fluorescence
    • A61B5/0075—Measuring for diagnostic purposes; Identification of persons using light, e.g. diagnosis by transillumination, diascopy, fluorescence by spectroscopy, i.e. measuring spectra, e.g. Raman spectroscopy, infrared absorption spectroscopy
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/14532—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue for measuring glucose, e.g. by tissue impedance measurement
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/1455—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue using optical sensors, e.g. spectral photometrical oximeters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/021—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using plane or convex mirrors, parallel phase plates, or particular reflectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0224—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using polarising or depolarising elements
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/02—Details
    • G01J3/0205—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows
    • G01J3/0229—Optical elements not provided otherwise, e.g. optical manifolds, diffusers, windows using masks, aperture plates, spatial light modulators or spatial filters, e.g. reflective filters
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/2803—Investigating the spectrum using photoelectric array detector
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/30—Measuring the intensity of spectral lines directly on the spectrum itself
    • G01J3/36—Investigating two or more bands of a spectrum by separate detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28—Investigating the spectrum
    • G01J3/44—Raman spectrometry; Scattering spectrometry ; Fluorescence spectrometry
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/21—Polarisation-affecting properties
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3581—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N2021/1734—Sequential different kinds of measurements; Combining two or more methods
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N2021/6417—Spectrofluorimetric devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/65—Raman scattering
    • G01N2021/653—Coherent methods [CARS]
    • G01N2021/655—Stimulated Raman
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3581—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
    • G01N21/3586—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation by Terahertz time domain spectroscopy [THz-TDS]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/636—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited using an arrangement of pump beam and probe beam; using the measurement of optical non-linear properties
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2201/00—Features of devices classified in G01N21/00
    • G01N2201/06—Illumination; Optics
    • G01N2201/067—Electro-optic, magneto-optic, acousto-optic elements
    • G01N2201/0675—SLM

Definitions

  • the present invention relates to the detection of materials within a sample, and more particularly, to the detection of materials within a sample based multi-parameter spectroscopy.
  • glucose Another example of a biological agent that may be monitored for within human tissue is glucose.
  • Glucose is a monosaccharide sugar and is one of the most
  • Glucose is fundamental to 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 within human blood is 70-160 mg/dl depending on the time of the last meal, the extent of physical tolerance and other factors. Freely circulating glucose molecules stimulate the release of insulin from the pancreas. Insulin helps glucose molecules to penetrate the cell wall by binding two specific receptors within cell membranes which are normally impermeable to glucose.
  • Diabetes is a disorder caused by the decreased production of insulin, or by a decreased ability to utilize insulin and transport the glucose across cell membranes. As a result, a high potentially dangerous concentration of glucose can accumulate within the blood (hyperglycemia) during the disease. Therefore, it is of great importance to maintain blood glucose concentration within a normal range in order to prevent possible severe physiological complications.
  • diabetes mellitus or simply diabetes.
  • Another organic component lending itself to optical material concentration sensing involves is human skin.
  • the defense mechanisms of human skin are based on the action of antioxidant substances such as carotenoids, vitamins and enzymes.
  • Beta carotene and lycopene represent more than 70% of the carotenoids in the human organism.
  • the topical or systematic application of beta carotene and lycopene is a general strategy for improving the defense system of the human body.
  • the evaluation and optimization of this treatment requires the measurement of the b-carotene and lycopene concentrations in human tissue, especially in the human skin as the barrier to the environment.
  • the present invention in one aspect thereof, comprise an apparatus for detecting a material within a sample includes a light emitting unit for directing at least one light beam through the sample.
  • a plurality of spectroscopic units receive the light beam that has passed through the sample and performs a spectroscopic analysis of the sample based on the received light beam.
  • Each of the plurality of spectroscopic units analyze a different parameter with respect to the sample, provide a separate output signal with respect to the analysis.
  • a processor detects the material with respect each of the provided separate output signals.
  • Fig. 1 illustrates the manner for using an Orbital Angular Momentum signature to detect the presence of a material within a sample
  • Fig. 2 illustrates the manner in which an OAM generator generates an OAM twisted beam
  • Fig. 3 illustrates a light beam having orbital angular momentum imparted thereto
  • Fig. 4 illustrates a series of parallel wavefronts
  • Fig. 5 illustrates a wavefront having a Poynting vector spiraling around a direction of propagation of the wavefront
  • Fig. 6 illustrates a plane wavefront
  • Fig. 7 illustrates a helical wavefront
  • Fig. 8 illustrates a plane wave having only variations in the spin vector
  • Fig. 9 illustrates the application of a unique orbital angular momentum to a wave
  • Figs. 1 OA- IOC illustrate the differences between signals having different orbital angular momentum applied thereto
  • Fig. 11 A illustrates the propagation of Poynting vectors for various eigenmodes
  • Fig. 1 IB illustrates a spiral phase plate
  • Fig. 12 illustrates a block diagram of an apparatus for providing concentration measurements and presence detection of various materials using orbital angular momentum
  • Fig. 13 illustrates an emitter of the system of Fig. 11;
  • Fig. 14 illustrates a fixed orbital angular momentum generator of the system of Fig. 11 ;
  • Figs. 15A-15D illustrate various holograms for use in applying an orbital angular momentum to a plane wave signal
  • Fig. 16 illustrates the relationship between Hermite-Gaussian modes and Laguerre-Gaussian modes
  • Fig. 17 illustrates super-imposed holograms for applying orbital angular momentum to a signal
  • Fig. 18 illustrates a tunable orbital angular momentum generator for use in the system of Fig. 11;
  • Fig. 19 illustrates a block diagram of a tunable orbital angular momentum generator including multiple hologram images therein;
  • Fig. 20 illustrates the manner in which the output of the OAM generator may be varied by applying different orbital angular momentums thereto;
  • Fig. 21 illustrates an alternative manner in which the OAM generator may convert a Hermite-Gaussian beam to a Laguerre-Gaussian beam
  • Fig. 22 illustrates the manner in which holograms within an OAM generator may twist a beam of light
  • Fig. 23 illustrates the manner in which a sample receives an OAM twisted wave and provides an output wave having a particular OAM signature
  • Fig. 24 illustrates the manner in which orbital angular momentum interacts with a molecule around its beam axis;
  • Fig. 25 illustrates a block diagram of the matching circuitry for amplifying a received orbital angular momentum signal;
  • Fig. 26 illustrates the manner in which the matching module may use non-linear crystals in order to generate a higher order orbital angular momentum light beam
  • Fig. 27 illustrates a block diagram of an orbital angular momentum detector and user interface
  • Fig. 28 illustrates the effect of sample concentrations upon the spin angular polarization and orbital angular polarization of a light beam passing through a sample
  • Fig. 29 more particularly illustrates the process that alters the orbital angular momentum polarization of a light beam passing through a sample
  • Fig. 30 provides a block diagram of a user interface of the system of Fig. 12;
  • Fig. 31 illustrates a network configuration for passing around data collected via devices such as that illustrated in Fig. 15;
  • FIG. 32 provides a block diagram of a more particular embodiment of an apparatus for measuring the concentration and presence of glucose using orbital angular momentum
  • Fig. 33 illustrates an optical system for detecting a unique OAM signature of a signal passing through a sample under test
  • Fig. 34 illustrates the manner in which the ellipticity of an OAM intensity diagram changes after passing through a sample
  • Fig. 35 illustrates the manner in which a center of gravity of an intensity diagram shifts after passing through a sample
  • Fig. 36 illustrates the manner in which an axis of the intensity diagram shifts after passing through a sample
  • Fig. 37A illustrates an OAM signature of a sample consisting only of water
  • Fig. 37B illustrates an OAM signature of a sample of 15% glucose in water
  • Fig. 38 A illustrates an interferogram of a sample consisting only of water
  • Fig. 38B illustrates an interferogram of a sample of 15% glucose in water
  • Fig. 39 shows the amplitude of an OAM beam
  • Fig. 40 shows the phase of an OAM beam
  • Fig. 41 is a chart illustrating the ellipticity of a beam on the output of a Cuvette for three different OAM modes
  • Figs. 42A-42C illustrates the propagation due to and annulus shaped beam for a Cuvette, water and glucose
  • Fig. 43 illustrates OAM propagation through water for differing drive voltages
  • Fig. 44 illustrates an example of a light beam that is altered by a hologram to produce an OAM twisted beam
  • Fig. 45 illustrates various OAM modes produced by a spatial light modulator
  • Fig. 46 illustrates an ellipse
  • Fig. 47 is a flow diagram illustrating a process for analyzing intensity images
  • Fig. 48 illustrates an ellipse fitting algorithm
  • Fig. 49 illustrates the generation of fractional orthogonal states
  • Fig. 50 illustrates the use of a spatial light modulator for the generation of fractional OAM beams;
  • Fig. 51 illustrates one manner for the generation of fractional OAM beam using superimposed Laguerre Gaussian beams;
  • Fig. 52 illustrates the decomposition of a fractional OAM beam into integer OAM states
  • Fig. 53 illustrates the manner in which a spatial light modulator may generate a hologram for providing fractional OAM beams
  • Fig. 54 illustrates the generation of a hologram to produce non-integer OAM beams
  • Fig. 55 is a flow diagram illustrating the generation of a hologram for producing non-integer OAM beams
  • Fig. 56 illustrates the intensity and phase profiles for noninteger OAM beams
  • Fig. 57 is a block diagram illustrating fractional OAM beams for OAM spectroscopy analysis
  • Fig. 58 illustrates an example of an OAM state profile
  • Fig. 59 illustrates the manner for combining multiple varied spectroscopy techniques to provide multiparameter spectroscopy analysis
  • Fig. 60 illustrates a schematic drawing of a spec parameter for making relative measurements in an optical spectrum
  • Fig. 61 illustrates an electromagnetic spectrum
  • Fig. 62 illustrates the infrared spectrum of water vapor
  • Fig. 63 illustrates the stretching and bending vibrational modes of water
  • Fig. 64 illustrates the stretching and bending vibrational modes for C0 2 ;
  • Fig. 65 illustrates the infrared spectrum of carbon dioxide;
  • Fig. 66 illustrates the energy of an anharmonic oscillator as a function of the interatomic distance
  • Fig. 67 illustrates the energy curve for a vibrating spring and quantized energy level
  • Fig. 68 illustrates Rayleigh scattering and Ramen scattering by Stokes and anti- Stokes resonance
  • Fig 69 illustrates circuits for earn ing out polarized Rahman techniques
  • Fig. 70 illustrates circuitry for combining polarized and non-polarized Rahman spectroscopy
  • Fig. 71 illustrates a combination of polarized and non-polarized Rahman spectroscopy with optical vortices
  • Fig. 72 illustrates the electromagnetic wave attenuation by atmospheric water versus frequency and wavelength
  • Fig. 73 illustrates the absorption and emission sequences associated with fluorescence spectroscopy
  • Fig. 74A illustrates the absorption spectra of various materials
  • Fig. 74B illustrates the fluorescence spectra of various materials
  • Fig. 75 illustrates a pump-probe spectroscopy set up
  • Fig. 76 illustrates an enhanced Ramen signal
  • Fig. 77 illustrates a pump-probe OAM spectroscopy set up;
  • Fig. 78 illustrates measured eccentricities of OAM beams;
  • Fig. 79 illustrates a combination of OAM spectroscopy with Ramen spectroscopy for the generation of differential signals
  • Fig. 80 illustrates a flow diagram of an alignment procedure
  • Fig. 81 illustrates a balanced detection scheme
  • Fig. 82 illustrates an elliptical coordinate system
  • Fig. 83 illustrates a tracing the lips with constant
  • Fig. 84 illustrates tracing hyperbolas with constant
  • Figs. 85A and 85B illustrates even Ince Polynomials
  • Fig. 86 illustrates modes and phases for even Ince mode
  • Figs. 87A and 87B illustrates odd Ince Polynomials
  • Fig. 88 illustrates modes and phases for odd Ince mode
  • Fig. 89 illustrates dual comp spectroscopy
  • Fig. 90 illustrates a wearable multi-parameter spectroscopy device.
  • An optical signal 102 having a series of plane waves therein is applied to a device for applying an orbital angular momentum (OAM) signal to the optical signal 102 such as a spatial light modulator (SLM) 104.
  • OAM orbital angular momentum
  • SLM spatial light modulator
  • the SLM 104 generates an output signal 106 having a known OAM twist applied to the signal.
  • the OAM twist has known characteristics that act as a baseline prior to the application of the output signal 106 to a sample 108.
  • the sample 108 may comprise a material contained within a holding container, such as a cuvette, or may be a material in its natural state, such as the eye or body of a patient or its naturally occurring location in nature.
  • the sample 108 only indicates that a particular material or item of interest is being detected by the describe system.
  • the output signal 106 While passing through the sample 108, the output signal 106 has a unique OAM signature applied thereto that is provided as an OAM distinct signature signal 110.
  • OAM beams have been observed to exhibit unique topological evolution upon interacting with chiral solutions. While it has been seen that chiral molecules create unique OAM signatures when an OAM beam is passed through a sample of the chiral material, the generation of unique OAM signatures from signals passing through non-chiral molecules/material may also be provided.
  • This distinct signature signal 110 may then be examined using for example a camera 112 in order to detect the unique signal characteristics applied thereto and determine the material within the sample based upon this unique signature.
  • Application of multi-parameter spectroscopy for the detection of different molecules can be applied to different industries including, but not limited to, food (identification of food spoilage), Nanoscale Material development for defense and national security, chemical industries, pharma and medical industries for testing where non-invasive solutions are critical, medical and dental industry for identification of infections, cancer cells, organic compounds and many others.
  • the determination of the particular material indicated by the unique signature may be determined in one embodiment by comparison of the signature to a unique database of signatures that include known signatures that are associated with a particular material or concentration.
  • a unique database of signatures that include known signatures that are associated with a particular material or concentration. The manner of creating such a database would be known to one skilled in the art.
  • FIG. 2 illustrates the manner in which an OAM generator 220 may generate an OAM twisted beam 222.
  • the OAM generator 210 may use any number of devices to generate the twisted beam 222 including holograms with an amplitude mask, holograms with a phase mask, Spatial Light Modulators (SLMs) or Digital Light Processors (DLPs).
  • the OAM generator 220 receives a light beam 221 (for example from a laser) that includes a series of plane waves.
  • the OAM generator 220 applies an orbital angular momentum to the beam 222.
  • the beam 222 includes a single OAM mode as illustrated by the intensity diagram 223.
  • the OAM twisted beam 222 is passed through a sample 224 including material that is being detected.
  • the sample 224 may be in a container or its naturally occurring location. The presence of the material within the sample 224 will create new OAM mode levels within the intensity diagram 225.
  • the output beam 226 will have three distinct signatures associated therewith based on a detection of a particular material at a particular concentration. These signatures include a change in eccentricity 228 of the intensity pattern, a shift or translation 230 in the center of gravity of the intensity partem and a rotation 232 in three general directions ( ⁇ , ⁇ , ⁇ ) of the ellipsoidal intensity partem output. Each of these distinct signature indications may occur in any configuration and each distinct signature will provide a unique indication of the presence of particular materials and the concentrations of these detected materials.
  • the detection of the helicity spectrums from the beam passing through the sample 224 involves detecting the helical wave scatters (forward and backward) from the sample material.
  • OAM orbital angular momentum
  • the unique OAM signatures imparted by a material is not interfered with by ambient light scattering (noise) that does not carry OAM in naturally scattered photons making detection much more accurate.
  • ambient light scattering noise
  • Molecular chirality signifies a structural handedness associated with variance under spatial inversion or a combination of inversion and rotation, equivalent to the usual criteria of a lack of any proper axes of rotation. Something is chiral when something cannot be made identical to its reflection. Chiral molecules that are not superimposable on their mirror image are known as Enantiomers.
  • the continuous symmetry measure is used to evaluate the degree of symmetry of a molecule, or the chirality. This value ranges from 0 to 100. The higher the symmetry value of a molecule the more symmetry distorted the molecule and the more chiral the molecule. The measurement is based on the minimal distance between the chiral molecule and the nearest achiral molecule.
  • the continuous symmetry measure may be achieved according to the equation:
  • SG as a continuous chirality measure may be determined according to:
  • Chiroptical interactions can be distinguished by their electromagnetic origins: for molecular systems in their usual singlet electronic ground state, they involve the spatial variation of the electric and magnetic fields associated with the input of optical radiation. This variation over space can be understood to engage chirality either through its coupling with di-symmetrically placed, neighboring chromophore groups (Kirkwood's two-group model, of limited application) or more generally through the coupling of its associated electric and magnetic fields with individual groups. As chirality signifies a local breaking of parity it permits an interference of electric and magnetic interactions. Even in the two group case, the paired electric interactions of the system correspond to electric and magnetic interactions of the single entity which the two groups comprise. Thus, for convenience, the term 'chiral center' is used in the following to denote either chromophore or molecule.
  • the Gaussian beam solution to the wave equation came into common engineering parlance, and its extension two higher order laser modes, Hermite Gaussian for Cartesian symmetry; Laguerre Gaussian for cylindrical symmetry, etc., entered laboratory optics operations. Higher order Laguerre Gaussian beam modes exhibit spiral, or helical phase fronts.
  • the propagation vector, or the eikonal of the beam, and hence the beams momentum includes in addition to a spin angular momentum, an orbital angular momentum, i.e. a wobble around the sea axis. This phenomenon is often referred to as vorticity.
  • the expression for a Laguerre Gaussian beam is given in cylindrical coordinates:
  • w (x) is the beam spot size
  • q(c) is the complex beam parameter comprising the evolution of the spherical wave front and the spot size.
  • Integers p and m are the radial and azimuthal modes, respectively.
  • the term describes the spiral phase fronts.
  • a light beam 300 consists of a stream of photons 302 within the light beam 300.
  • Each photon has an energy ⁇ hGD and a linear momentum of ⁇ hk which is directed along the light beam axis 304 perpendicular to the wavefront.
  • each photon 302 within the light beam has a spin angular momentum 306 of ⁇ h aligned parallel or antiparallel to the direction of light beam propagation. Alignment of all of the photons 302 spins gives rise to a circularly polarized light beam.
  • the light beams also may carry an orbital angular momentum 308 which does not depend on the circular polarization and thus is not related to photon spin.
  • Lasers are widely used in optical experiments as the source of well-behaved light beams of a defined frequency.
  • a laser may be used for providing the light beam 300.
  • the energy flux in any light beam 300 is given by the Poynting vector which may be calculated from the vector product of the electric and magnetic fields within the light beam.
  • the Poynting vector In a vacuum or any isotropic material, the Poynting vector is parallel to the wave vector and perpendicular to the wavefront of the light beam.
  • the wavefronts 400 are parallel as illustrated in Fig. 4.
  • the wave vector and linear momentum of the photons are directed along the axis in a z direction 402.
  • the field distributions of such light beams are paraxial solutions to Maxwell's wave equation but although these simple beams are the most common, other possibilities exist.
  • beams that have / intertwined helical fronts are also solutions of the wave equation.
  • the wavefront has a Poynting vector and a wave vector that spirals around the light beam axis direction of propagation as illustrated in Fig. 5 at 502.
  • a Poynting vector has an azimuthal component on the wave front and a non-zero resultant when integrated over the beam cross-section.
  • the spin angular momentum of circularly polarized light may be interpreted in a similar way.
  • the beam is linearly polarized, there is no azimuthal component to the Poynting vector and thus no spin angular momentum.
  • the momentum of each photon 302 within the light beam 300 has an azimuthal component.
  • a detailed calculation of the momentum involves all of the electric fields and magnetic fields within the light beam, particularly those electric and magnetic fields in the direction of propagation of the beam.
  • the linear momentum of each photon 302 within the light beam 300 is given by so if we take the cross product of the azimuthal component within a radius vector, r, we obtain an orbital momentum for a photon 602 of Ih.
  • the azimuthal component of the wave vectors is l/r and independent of the wavelength.
  • Figs. 6 and 7 there are illustrated plane wavefronts and helical wavefronts.
  • laser beams with plane wavefronts 602 are characterized in terms of Hermite-Gaussian modes. These modes have a rectangular symmetry and are described by two mode indices m 604 and n 606. There are m nodes in the x direction and n nodes in the y direction. Together, the combined modes in the x and y direction are labeled HG mn 608. In contrast, as shown in Fig.
  • beams with helical wavefronts 702 are best characterized in terms of Laguerre-Gaussian modes which are described by indices / 703, the number of intertwined helices 704, and p, the number of radial nodes 706.
  • the Laguerre-Gaussian modes are labeled LG mn 710.
  • LG mn 710 For / ⁇ 0, the phase singularity on a light beam 300 results in 0 on axis intensity.
  • the angular momentum has orbital and spin components, and the total angular momentum of the light beam is (/ ⁇ h) per photon.
  • the EM field angular momentum can be separated into two parts:
  • the first part is the EM spin angular momentum S em , its classical manifestation is wave polarization.
  • the second part is the EM orbital angular momentum L em its classical manifestation is wave helicity.
  • both EM linear momentum P em , and EM angular momentum are radiated all the way to the far field.
  • the optical vorticity of the signals may be determined according to the optical velocity equation: where S is the Poynting vector
  • Figs. 8 and 9 there are illustrated the manner in which a signal and an associated Poynting vector of the signal vary in a plane wave situation (Fig. 8) where only the spin vector is altered, and in a situation wherein the spin and orbital vectors are altered in a manner to cause the Poynting vector to spiral about the direction of propagation (Fig. 9). [00136] In the plane wave situation, illustrated in Fig. 8) where only the spin vector is altered, and in a situation wherein the spin and orbital vectors are altered in a manner to cause the Poynting vector to spiral about the direction of propagation (Fig. 9). [00136] In the plane wave situation, illustrated in Fig.
  • the transmitted signal may take on one of three configurations.
  • a linear signal is provided as illustrated generally at 804.
  • 804 illustrates the spin vectors being altered only in the x direction to provide a linear signal
  • the spin vectors can also be altered in the y direction to provide a linear signal that appears similar to that illustrated at 804 but in a perpendicular orientation to the signal illustrated at 804.
  • linear polarization such as that illustrated at 804
  • the vectors for the signal are in the same direction and have a same magnitude.
  • the signal vectors 812 are 90 degrees to each other but have the same magnitude.
  • the signal vectors 816 are also 90 degrees to each other but have differing magnitudes. This provides the elliptical polarizations 818 illustrated for the signal propagation 408.
  • the Poynting vector is maintained in a constant direction for the various signal configurations illustrated therein.
  • Fig. 9 The situation in Fig. 9 illustrates when a unique orbital angular momentum is applied to a signal.
  • Poynting vector S 910 will spiral around the general direction of propagation 912 of the signal.
  • the Poynting vector 910 has three axial components S ⁇ p, S p and S z which vary causing the vector to spiral about the direction of propagation 912 of the signal.
  • the changing values of the various vectors comprising the Poynting vector 910 may cause the spiral of the Poynting vector to be varied in order to enable signals to be transmitted on a same wavelength or frequency as will be more fully described herein.
  • the values of the orbital angular momentum indicated by the Poynting vector 910 may be measured to determine the presence of particular materials and the concentrations associated with particular materials being processed by a scanning mechanism.
  • Figs. l OA-lOC illustrate the differences in signals having a different helicity (i.e., orbital angular momentum applied thereto).
  • the differing helicities would be indicative of differing materials and concentration of materials within a sample that a beam was being passed through.
  • the particular material and concentration amounts of the material could be determined.
  • Each of the spiraling Poynting vectors associated with a signal 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
  • signal 1006 has an orbital angular momentum of -4.
  • Each signal has a distinct orbital angular momentum and associated Poynting vector enabling the signal to be indicative of a particular material and concentration of material that is associated with the detected orbital angular momentum. This allows determinations of materials and concentrations of various types of materials to be determined from a signal since the orbital angular momentums are separately detectable and provide a unique indication of the particular material and the concentration of the particular material that has affected the orbital angular momentum of the signal transmitted through the sample material.
  • Fig. 11A illustrates the propagation of Poynting vectors for various Eigen modes.
  • Each of the rings 1 120 represents a different Eigen mode or twist representing a different orbital angular momentum.
  • Each of the different orbital angular momentums is associated with particular material and a particular concentration of the particular material. Detection of orbital angular momentums provides an indication of the a presence of an associated material and a concentration of the material that is being detected by the apparatus.
  • Each of the rings 1 120 represents a different material and/or concentration of a selected material that is being monitored.
  • Each of the Eigen modes has a Poynting vector 1122 for generating the rings indicating different materials and material concentrations.
  • Topological charge may be multiplexed to the frequency for either linear or circular polarization. In case of linear polarizations, topological charge would be multiplexed on vertical and horizontal polarization. In case of circular polarization, topological charge would multiplex on left hand and right hand circular polarizations.
  • the topological charge is another name for the helicity index "I" or the amount of twist or OAM applied to the signal. The helicity index may be positive or negative.
  • the topological charges l s can be created using Spiral Phase Plates (SPPs) as shown in Fig. 1 1B using a proper material with specific index of refraction and ability to machine shop or phase mask, holograms created of new materials.
  • FIG. 12 there is illustrated a block diagram of the apparatus for providing detection of the presence of a material and concentration measurements of various materials responsive to the orbital angular momentum detected by the apparatus in accordance with the principles described herein above.
  • An emitter 1202 transmits wave energy 1204 that comprises a series of plane waves.
  • the emitter 1202 may provide a series of plane waves such as those describes previously with respect to Fig. 7.
  • the orbital angular momentum generation circuitry 1206 generates a series of waves having an orbital angular momentum applied to the waves 1208 in a known manner.
  • the orbital angular momentum generation circuitry 1206 may utilize holograms or some other type of orbital angular momentum generation process as will be more fully described herein below.
  • the OAM generation circuitry 1206 may be generated by transmitting plane waves through a spatial light modulator (SLM), an amplitude mask or a phase mask.
  • SLM spatial light modulator
  • the orbital angular momentum twisted waves 1208 are applied to a sample material 1210 under test.
  • the sample material 1210 contains a material, and the presence and concentration of the material is determined via a detection apparatus in accordance with the process described herein.
  • the sample material 1210 may be located in a container or at its naturally occurring location in nature such as an individual's body.
  • the output waves 1212 are applied to a matching module 1214 that includes a mapping aperture for amplifying a particular orbital angular momentum generated by the specific material under study.
  • the matching module 1214 will amplify the orbital angular momentums associated with the particular material and concentration of material that is detected by the apparatus.
  • the amplified OAM waves 1216 are provided to a detector 1218.
  • the detector 1218 detects OAM waves relating to the material and the concentration of a material within the sample and provides this information to a user interface 1220.
  • the detector 1218 may utilize a camera to detect distinct topological features from the beam passing through the sample.
  • the user interface 1220 interprets the information and provides relevant material type and concentration indication to an individual or a recording device.
  • the emitter 1202 may emit a number of types of energy waves 1204 to the OAM generation module 1206.
  • the emitter 1202 may emit optical waves 1300, electromagnetic waves 1302, acoustic waves 1304 or any other type of particle waves 1306.
  • the emitted waves 1204 are plane waves such as those illustrated in Fig. 4 having no orbital angular momentum applied thereto and may come from a variety of types of emission devices and have information included therein.
  • the emission device may comprise a laser. Plane waves have wavefronts that are parallel to each other having no twist or helicity applied thereto, and the orbital angular momentum of the wave is equal to 0.
  • the OAM generation module 1206 processes the incoming plane wave 1204 and imparts a known orbital angular momentum onto the plane waves 1204 provided from the emitter 1202.
  • the OAM generation module 1206 generates twisted or helical electromagnetic, optic, acoustic or other types of particle waves from the plane waves of the emitter 1202.
  • a helical wave 1208 is not aligned with the direction of propagation of the wave but has a procession around direction of propagation as shown in Fig. 14.
  • the OAM generation module 1206 may comprise in one embodiment a fixed orbital angular momentum generator 1402 as illustrated in Fig. 14.
  • the fixed orbital angular momentum generator 1402 receives the plane waves 1204 from the emitter 1202 and generates an output wave 1404 having a fixed orbital angular momentum applied thereto.
  • the fixed orbital angular momentum generator 1402 may in one embodiment comprise a holographic image for applying the fixed orbital angular momentum to the plane wave 1204 in order to generate the OAM twisted wave 1404.
  • Various types of holographic images may be generated in order to create the desired orbital angular momentum twist to an optical signal that is being applied to the orbital angular momentum generator 1402.
  • Various examples of these holographic images are illustrated in Fig. 15A-15D.
  • the conversion of the plane wave signals transmitted from the emitter 1202 by the orbital angular momentum generation circuitry 1206 may be achieved using holographic images.
  • HGoo Hermite-Gaussian
  • Fig. 16 a planar wave front and a transverse intensity described by a Gaussian function.
  • a number of different methods have been used to successfully transform an HGoo Hermite-Gaussian mode 1602 into a Laguerre-Gaussian mode 1604, the simplest to understand is the use of a hologram.
  • z R is the Rayleigh range
  • w(z) is the radius of the beam
  • L P is the Laguerre polynomial
  • C is a constant
  • a computer generated hologram is produced from the calculated interference pattern that results when the desired beam intersects the beam of a conventional laser at a small angle.
  • the calculated pattern is transferred to a high resolution holographic film.
  • a diffraction pattern results.
  • This is one manner for implementing the OAM generation module 1206.
  • a number of examples of holographic images for use within a OAM generation module are illustrated with respect to Figs. 15A-15D.
  • holograms that comprise only black and white areas with no grayscale are referred to as binary holograms.
  • binary holograms the relative intensities of the two interfering beams play no role and the transmission of the hologram is set to be zero for a calculated phase difference between zero and ⁇ , or unity for a phase difference between ⁇ and 2 ⁇ .
  • a limitation of binary holograms is that very little of the incident power ends up in the first order diffracted spot, although this can be partly overcome by blazing the grating.
  • mode purity is of particular importance, it is also possible to create more sophisticated holograms where the contrast of the pattern is varied as a function of radius such that the diffracted beam has the required radial profile.
  • a plane wave shining through the holographic images 1502 will have a predetermined orbital angular momentum shift applied thereto after passing through the holographic image 1502.
  • OAM generator 1202 is fixed in the sense that a same image is used and applied to the beam being passed through the holographic image. Since the holographic image 1502 does not change, the same orbital angular momentum is always applied to the beam being passed through the holographic image 1502. While Figs. 15A-15D illustrate a number of embodiments of various holographic images that might be utilized within the orbital angular momentum generator 1202, it will be realized that any type of holographic image 1502 may be utilized in order to achieve the desired orbital angular momentum within an beam being shined through the image 1502.
  • a hologram that utilizes two separate holograms that are gridded together to produce a rich number of orbital angular momentum (/).
  • the orbital angular momentums along the top edge vary from +4 to +1 to -2 and on the bottom edge from +2 to -1 to -4.
  • the orbital angular momentums vary from +4 to +3 to +2 and on the right edge from -2 to -3 to -4.
  • the orbital angular momentums provided vary from +3 to 0 to -3 and along the vertical axis vary from +1 to 0 to -1.
  • the orbital angular momentum generation circuitry 1206 may also comprise a tunable orbital angular momentum generator circuitry 1802.
  • the tunable orbital angular momentum generator 1802 receives the input plane wave 1204 but additionally receives one or more tuning parameters 1804.
  • the tuning parameters 1804 tune the tunable OAM generator 1802 to apply a selected orbital angular momentum so that the tuned OAM wave 1806 that is output from the OAM generator 1802 has a selected orbital angular momentum value applied thereto.
  • the tunable orbital angular momentum generator 1802 may include multiple hologram images 2202 within the tunable OAM generator 1802.
  • the tuning parameters 1804 enable selection of one of the holographic images 2206 in order to provide the desired OAM wave twisted output signal 1806 through a selector circuit 2204.
  • the gridded holographic image such as that described in Fig. 16 may be utilized and the beam shined on a portion of the gridded image to provide the desired OAM output.
  • the tunable OAM generator 1802 has the advantage of being controlled to apply a particular orbital angular momentum to the output orbital angular momentum wave 1806 depending upon the provided input parameter 1804. This enables the presence and concentrations of a variety of different materials to be monitored, or alternatively, for various different concentrations of the same material to be monitored.
  • the generator 1802 includes a plurality of holographic images 1902 for providing orbital angular momentums of various types to a provided light signal. These holographic images 1902 are selected responsive to a selector circuitry 1904 that is responsive to the input tuning parameters 1804.
  • the selected filter 1906 comprises the holographic image that has been selected responsive to the selector controller 1904 and receives the input plane waves 1204 to provide the tuned orbital angular momentum wave output 1206. In this manner, signals having a desired orbital angular momentum may be output from the OAM generation circuitry 1206.
  • Fig. 20 illustrates helical phase fronts in which the Poynting vector is no longer parallel to the beam axis and thus has an orbital angular momentum applied thereto.
  • the left column 2002 is the light beam's instantaneous phase.
  • the center column 2004 comprises the angular intensity profiles and the right column 2006 illustrates what occurs when such a beam interferes with a plane wave and produces a spiral intensity pattern. This is illustrated for orbital angular momentums of -1, 0, 1, 2 and 3 within the various rows of Fig. 23.
  • the OAM generator 1206 may convert a Hermite-Gaussian beam output from an emitter 1202 to a Laguerre-Gaussian beams having imparted therein an orbital angular momentum using mode converters 2104 and a Dove prism 2110.
  • the Hermite-Gaussian mode plane waves 2102 are provided to a ⁇ /2 mode converter 2104.
  • the ⁇ /2 mode converter 2104 produce beams in the Laguerre-Gaussian modes 2106.
  • the Laguerre-Gaussian modes beams 2106 are applied to either a ⁇ mode converter 2108 or a dove prism 2110 that reverses the mode to create a reverse Laguerre-Gaussian mode signal 2112.
  • a hologram 2202 can produce light beam 2204 and light beam 2206 having helical wave fronts and associated orbital angular momentum Ih per photon.
  • the appropriate hologram 2202 can be calculated or generated from the interference pattern between the desired beam form 2204, 2206 and a plane wave 2208.
  • the resulting holographic pattern within the hologram 2202 resembles a diffraction grating, but has a 1-pronged dislocation at the beam axis.
  • the first-order diffracted beams 2204 and 2206 have the desired helical wave fronts to provide the desired first ordered diffracted beam display 2210.
  • the sample 1210 may comprise any sample that is under study and may be in a solid form, liquid form or gas form.
  • the sample material 1210 that may be detected using the system described herein may comprise a variety of different materials. As stated previously, the material may comprise liquids such as blood, water, oil or chemicals.
  • the various types of carbon bondings such as C-H, C-O, C-P, C-S or C-N may be provided for detection.
  • the system may also detect various types of bondings between carbon atoms such as a single bond (methane or Isooctane), dual bond items (butadiene and benzene) or triple bond carbon items such as acetylene.
  • the sample 1210 may include detectable items such as organic compounds including carbohydrates, lipids (cylcerol and fatty acids), nucleic acids (C,H,0,N,P) (RNA and DNA) or various types of proteins such as poly our of amino NH 2 and carboxyl COOH or aminos such as tryptophan, tyrosine and phenylalanine.
  • Various chains within the samples 1210 may also be detected such as monomers, isomers and polymers. Enzymes such as ATP and ADP within the samples may be detected.
  • Substances produced or released by glands of the body may be in the sample and detected. These include items released by the exocrine glands via tube/ducts, endocrine glands released directly into blood samples or hormones.
  • glands that may have their secretions detected within a sample 1210 include the hypothalamus, pineal and pituitary glands, the parathyroid and thyroid and thymus, the adrenal and pancreas glands of the torso and the hormones released by the ovaries or testes of a male or female.
  • the sample 1210 may also be used for detecting various types of biochemical markers within the blood and urine of an individual such as melanocytes and keratinocytes.
  • the sample 1210 may include various parts of the body to detect defense substances therein.
  • the sample 1210 may be used to detect carotenoids, vitamins, enzymes, b-carotene and lycopene.
  • the melanin/eumelanin, dihydroxyindole or carboxylic may be detected.
  • the system may also detect various types of materials within the body's biosynthetic pathways within the sample 1210 including hemoglobin, myoglobin, cytochromes, and porphyrin molecules such as protoporphyrin, coporphyrin, uroporphyrin and nematoporphyrin.
  • the sample 1210 may also contain various bacterias to be detected such as propion bacterium, acnes. Also various types of dental plaque bacteria may be detected such as porphyromonos gingivitis, prevotella intremedi and prevotella nigrescens.
  • the sample 1210 may also be used for the detection of glucose in insulin within a blood sample 1210.
  • the sample 1210 may also include amyloid- beta detection.
  • the sample 1210 may comprise any material that is desired to be detected that provides a unique OAM twist to a signal passing through the sample.
  • the orbital angular momentum within the beams provided within the sample 1210 may be transferred from light to matter molecules depending upon the rotation of the matter molecules.
  • a circularly polarized laser beam with a helical wave front traps a molecule in an angular ring of light around the beam axis, one can observe the transfer of both orbital and spin angular momentum.
  • the trapping is a form of optical tweezing accomplished without mechanical constraints by the ring's intensity gradient.
  • the orbital angular momentum transferred to the molecule makes it orbit around the beam axis as illustrated at 2402 of Fig. 24.
  • the spin angular momentum sets the molecule spinning on its own axis as illustrated at 2404.
  • the output OAM wave 1212 from the sample 1210 will have an orbital angular momentum associated therewith that is different from the orbital angular momentum provided on the input OAM wave 1208.
  • the difference in the output OAM wave 1212 will depend upon the material contained within the sample 1210 and the concentration of these materials within the sample 1210. Differing materials of differing concentration will have unique orbital angular momentums associated therewith.
  • determinations may be made as to the materials present within the sample 1210 and the concentration of these materials within the sample may also be determined.
  • the matching module 1214 receives the output orbital angular momentum wave 1212 from the sample 1210 that has a particular signature associated therewith based upon the orbital angular momentum imparted to the waves passing through the sample 1210.
  • the matching module 1214 amplifies the particular orbital angular momentum of interest in order to provide an amplified wave having the desired orbital angular momentum of interest 1216 amplified.
  • the matching module 1214 may comprise a matching aperture that amplifies the detection orbital angular momentum associated with a specific material or characteristic that is under study.
  • the matching module 1214 may in one embodiment comprise a holographic filter such as that described with respect to Figs.
  • the matching module 1214 is established based upon a specific material of interest that is trying to be detected by the system.
  • the matching module 1214 may comprise a fixed module using holograms as illustrated in Figs. 15A-15D or a tunable 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 could be amplified by the matching module in order to detect differing materials or differing concentrations of materials within the sample 1210.
  • Other examples of components for the matching module 1214 include the use of quantum dots, nanomaterials or metamaterials in order to amplify any desired orbital angular momentum values within a received wave form from the sample 1210.
  • the matching module 1214 rather than using holographic images in order to amplify the desired orbital angular momentum signals may use non-linear crystals in order to generate higher orbital angular momentum light beams.
  • a first harmonic orbital angular momentum beam 2604 may be applied to a non-linear crystal 2602.
  • the non-linear crystal 2602 will create a second order harmonic signal 2606.
  • Fig. 27 there is more particularly illustrated the detector 1218 to which the amplified orbital angular momentum wave 1216 from the matching circuit 1214 in order that the detector 1218 may extract desired OAM measurements 2602.
  • the detector 1218 receives the amplified OAM waves 1216 and detects and measures observable changes within the orbital angular momentum of the emitted waves due to the presence of a particular material and the concentration of a particular material under study within the sample 1210.
  • the detector 1218 is able to measure observable changes within the emitted amplified OAM wave 1216 from the state of the input OAM wave 1208 applied to the sample 1210.
  • the extracted OAM measurements 2702 are applied to the user interface 1220.
  • the detector 618 includes an orbital angular momentum detector 2104 for determining a profile of orbital angular momentum states of the orbital angular momentum within the orbital angular momentum signal 616 and a processor 2106 for determining the material within the sample responsive to the detected profile of the orbital angular momentum states of the orbital angular momentum.
  • the manner in which the detector 1218 may detect differences within the orbital angular momentum is more particularly illustrates with respect to Fig. 28-30.
  • Fig. 28 illustrates the difference in impact between spin angular polarization and orbital angular polarization due to passing of a beam of light through a sample 2802.
  • sample 2802a there is illustrated the manner in which spin angular polarization is altered responsive to a beam passing through the sample 2802a.
  • the polarization of a wave having a particular spin angular momentum 2804 passing through the sample 2802a will rotate from a position 2804 to a new position 2806. The rotation occurs within the same plane of polarization.
  • an image appears as illustrated generally at 2808 before it passes through the sample 2802b.
  • the expanded light beam is applied through a metalab generated hologram 2906 that imparts an orbital angular momentum to the beam.
  • the twisted beam from the hologram 2906 is shined through a sample 2908 having a particular length L.
  • the sample 2908 may be located in a container or in its naturally occurring state. This causes the generation of a twisted beam on the output side of the sample 2908 to create a number of detectable waves having various orbital angular momentums 2910 associated therewith.
  • the image 2912 associated with the light beam that is applied to sample 2908 will rotate an angle ⁇ depending upon the presence and concentration of the material within the sample 2908.
  • the rotation ⁇ of the image 2912 is different for each value orbital angular momentum -/ or +/.
  • the change in rotation of the image ⁇ may be described according to the equation:
  • L is the path length of the sample and C is the concentration of the material being detected.
  • the orbital angular momentum may be determined using the process described herein, these two pieces of information may be able to calculate a concentration of the material within the provided sample.
  • the above equation may be utilized within the user interface more particularly illustrated in Fig. 30.
  • the user interface 1220 processes the OAM measurements 3002 using an internal algorithm 3002 that provides for the generation of material and/or concentration information 3004 that may be displayed in some type of user display.
  • the algorithm would in one embodiment utilize that equation described herein above in order to determine the material and/or concentration based upon the length of a sample and the detected variation in orbital angular momentum.
  • the process for calculating the material and/or concentration may be done in a laboratory setting where the information is transmitted wirelessly to the lab or the user interface can be associated with a wearable device connected to a meter or cell phone running an application on the cell phone connected via a local area network or wide area network to a personal or public cloud.
  • the user interface 3020 of the device can either have a wired or wireless connection utilizing Bluetooth, ZigBee or other wireless protocols.
  • Fig. 31 there is illustrated the manner in which the various data accumulated within the user interface 1220 that has been collected in the manner described herein above may be stored and utilized for higher level analysis.
  • Various devices 3102 for collecting data as described herein above may communicate via private network clouds 3104 or with a public cloud 3106. When communicating with a private cloud 3104, the devices 3102 merely store information that is associated with a particular user device that is for use with respect to analysis of the user associated with that user device. Thus, an individual user could be monitoring and storing information with respect to their present glucose concentrations in order to monitor and maintain their diabetes.
  • the user interface 1220 in addition to including the algorithm 3002 for determining material and/or concentration information 3004 will include a wireless interface 3006 enabling the collected information to be wirelessly transmitted over the public or private cloud as described with respect to Fig. 31.
  • the user interface may comprise a storage database 3008 enabling the collected information to be locally stored rather than transmitted wirelessly to a remote location.
  • Fig. 32 there is illustrated a particular example of a block diagram of a particular apparatus for measuring the presence an concentration of glucose using the orbital angular momentum of photons of a light beam shined through a glucose sample. While the present example is with respect to the detection of glucose, one skilled in the art would realize that the example would be applicable to the detection of the presence and concentration of any material.
  • the process creates a second-order harmonic with helical light beam using a non-linear crystal such as that described with respect to Fig. 25.
  • the emission module 2402 generates plane electromagnetic waves that are provided to an OAM generation module 3204.
  • the OAM generation module 3204 generates light waves having an orbital angular momentum applied thereto using holograms to create a wave having an electromagnetic vortex.
  • the OAM twisted waves are applied to the sample 3206 that is under study in order to detect the glucose and glucose concentration within a sample.
  • a rotated signature exits the sample 3206 in the manner described previously with respect to Figs. 28-29 and is provided to the matching module 3208.
  • the matching module 3208 will amplify the orbital angular momentum such that the observed concentrations may be calculated from the orbital momentum of the signature of the glucose.
  • These amplified signals are provided to detection module 3210 which measures the radius of the beam w(z) or the rotation of the image provided to the sample via the light beam.
  • This detected information is provided to the user interface that includes a sensor interface wired or wireless Bluetooth or ZigBee connection to enable the provision of the material to a reading meter or a user phone for the display of concentration information with respect to the sample.
  • concentrations of various types of material as describe herein may be determined utilizing the orbital angular momentum signatures of the samples under study and the detection of these materials or their concentrations within the sample determine as described.
  • OAM orbital angular momentum
  • Fig. 33 illustrates a further optical configuration for transmitting and detecting information.
  • the twisted nematic LCOS SLM 3302 implements a 1024 x 768 array with 9 ⁇ pitch and 8-bit resolution covering the visible wavelength range (430-650 nm) and readily interfaced via a VGA connection.
  • a programmable SLM 3302 allows for the generation of a variety of engineered beams.
  • a twisted nematic (TN) liquid crystal on silicon (LCOS) SLM is particularly useful in realizing the holograms that modulate the phase front of the input plane wave 102 (Fig. 1) or Gaussian beam.
  • An SLM is computer addressable using common software packages such as Matlab or Mathematica to define an arbitrary two- dimensional phase shift imprinted onto the beam input using, for example, a hologram.
  • a collimated input beam is reflected off of a display appropriately encoded by a phase retarding forked gratings, or hologram.
  • the generating equation for the forked gratings may be written as a Fourier series:
  • the weights, t m , of the Fourier components of the phase grating may be written in terms of Bessel functions of integer order:
  • the instrument comprises a Mach Zehnder interferometer.
  • One arm of the interferometer propagates a reference beam 3310.
  • the reference beam 3310 is created by a laser 3304 generating a light beam including a plurality of plane waves that is transmitted through a telescope 3306.
  • the plane wave light beam from the telescope 3306 passes through a first beam splitter 3308.
  • the beam splitter 3308 generates the reference beam 3310 that is reflected from a mirror 3311 to an interfering circuit 3312.
  • the reference beam 3310 may be a plane wave or, with the addition of a lens, a spherical wavefront may be implemented. This arm is blocked for amplitude only measurements.
  • the split plane wave beam from the beam splitter 3308 is combined at a beam combiner 3314 with the beam provided from the spatial light modulator 3302.
  • the spatial light modulator 3302 provides a light beam including the forked hologram 3316.
  • the beam combiner 3314 combines the forked hologram beam 3318 from the SLM 3302 and a plane wave beam 3320 from the laser 3304 to generate an OAM or other orthogonal function twisted beam of a known signature. This beam is reflected through a series of mirrors 3322 and focused on a pinhole aperture 3324 before passing the beam having the known orbital angular momentum through the sample under test 3303.
  • the sample twisted beam 3326 has been interfered at the signal combiner 3312 with the reference beam 3310. This interfered image may then be recorded by a camera or recording device 3328. This provides a unique OAM signature 3330 that may be analyzed in order to detect materials within the sample under test 3303. As can be seen, the unique OAM signature 3330 is different from the signature 3332 of the transmitted beam. The manner in which the signature is altered will be more fully described herein below.
  • the LCOS SLM 3302 is used to transform a collimated plane wave input beam 3320 into an OAM encoded beam.
  • the SLM 3302 is driven by a Matlab programs on an extended laptop display to provide a display of a forked hologram of any i or p. Following the SLM 3302, the beam is reflected through three mirrors 3322 to provide a sufficient distance for the separation of the diffracted OAM modes such that a pinhole iris aperture 3324 may select the desired mode to pass through a sample under test 3303.
  • Several materials of interest may be detected with OAM signatures using the setup of Fig. 33. Examples of these materials include acetone, isopropyl alcohol, sucrose, amyloid- beta, and glucose in steam distilled water. Spectroscopic grade soda lime glass cuvettes (1 cm x 2.5 cm x 3 cm) or larger custom-made circular cuvettes having BK7 cover glass in caps may be utilized for containing the sample under test 3303.
  • the sample under test 3303 is mounted on a translation stage arranged to allow quick and repeatable positioning in and out of the beam path either by movement of the sample or movement of the beam projection apparatus. Additionally, back reflections from the sample services are monitored carefully and blocked by irises so no spurious, secondary interactions occur.
  • the optical power through samples is low (less than 25 ⁇ ) to avoid any refractive index dependent thermal gradients in the solution.
  • Images 3330 of the beam at the output of the instrument are recorded using the high-resolution DSLR camera 3328 that is securely mounted perpendicular to the beam propagation direction and remotely triggered to prevent vibration or shift in the instrument. Measurement of ellipticity is performed using Photoshop and Matlab or similar types of image measuring and processing software or applications.
  • Fig. 34 illustrates the manner in which the ellipticity of the OAM intensity diagram changes after passing through the sample 3303. Initially, as illustrated at 3402, the intensity diagram has a substantially circular shape from the plane wave OAM beam before passing through the sample 3303.
  • the intensity diagram After passing through the sample 3303, the intensity diagram has a much more elliptical shape as illustrated generally at 3404. This elliptical shape is a unique characteristic that is different depending upon a material being detected and the concentration of the substance being detected. By detecting the ellipticity of the intensity diagram, a determination may be made of the presence of a particular material within the sample.
  • Fig. 35 illustrates a further characteristic of the OAM signature that may be altered by passing through a sample 3303.
  • the center of gravity of the intensity diagram has been shifted.
  • Position 3502 illustrates the initial position of the center of gravity of the intensity diagram before passing through a sample 3303.
  • the center of gravity moves to location 3504 that is a noticeable shift from the original position prior to passing through the sample.
  • the shift is uniquely affected by different materials.
  • the shift in center of gravity may also be used as an OAM distinct signature characteristic with the center of gravity shift indicating the presence of a particular material and the concentration of the material. Based upon an analysis of the shift in the center of gravity of the intensity diagram, a determination of the presence and/or concentration of a material may be made.
  • FIG. 36 A final distinct OAM signature characteristic is illustrated in Fig. 36.
  • the major axis 3602 of the intensity diagram ellipse shifts from a first position 3602 to a second position 3604 over an angle ⁇ 3606.
  • the major axis of the intensity diagram ellipse rotates from a position 3602 to position 3604 based upon the material being detected.
  • the angle ⁇ is uniquely associated with a particular substance and concentration of the substance being detected.
  • a material may be detected based upon a determined angle ⁇ within the intensity diagram.
  • a mathematical model may be used to represent the unique OAM signatures provided by each of changes in eccentricity, shift or translation of the center of gravity in rotation of the axis.
  • the change in eccentricity may be represented by:
  • the change in the center of gravity may be represented by a shift or translation in space of a vector v according to the matrix:
  • the rotations of the axis may be represented by a series of matrices showing rotations in 3 -different orientations:
  • FIGs. 37A and 37B there is shown the application of an OAM beam to a sample consisting only of water (Fig. 37A) and of water including a 15% glucose concentration (Fig. 37B).
  • the OAM signature manifests itself as an induced ellipticity on the ordinary circular beam amplitude illustrated in the intensity diagram of Fig. 37 A.
  • the distinct signature effect may also be observed in phase diagrams such as that illustrated in Figs. 38A and 38B.
  • the reference beams have the same spherical wave fronts. This is why essentially spiral pattern is observed in the phase measurements. Note in particular, the torsional shift in one of the 2 spirals of the phase front of the sample propagating through the glucose solution. The shift in the spiral pattern is the signature of the interaction in this experiment.
  • Glucose samples appear to impart a phase perturbation on an OAM beam causing the OAM mode to topologically be involved in the propagation direction. This effect allows for more sensitive metrology.
  • Fig. 39 shows the amplitude of an OAM beam
  • Fig. 40 shows the phase of an OAM beam.
  • the OAM signature is nonlinear with respect to glucose concentrations and under some conditions, appears to be somewhat periodic with concentration.
  • annulus was used to project a simple ring of light through a glucose sample.
  • the annulus pattem was printed on a traditional plastic transparency sheet and illuminated with a magnified and collimated 543 nm laser beam.
  • Figs. 42A-42C no distortion or signature was observed through Cuvette's of water (Fig. 42B) or Glucose (Fig. 42C) solution. Varying the ring diameter did not change these no results, even for diameters larger than the typical OAM beam.
  • the annulus diameter was larger than the Cuvette, obvious clipping was observed.
  • the power level of the beams in this test was as much in order of magnitude higher than in the OAM experiments. Thus, any thermal effects would have been accentuated.
  • Fig. 44 illustrates an example wherein a light beam produced by a laser 4402 is altered by a hologram provided by an SLM 4404 to generate an OAM twisted beam 4406.
  • the OAM twisted beam in addition to being altered by OAM functions may also be processed using Hermite Gaussian functions, Laguerre Gaussian functions or any other type of orthogonal function.
  • the OAM twisted beam is focused through a system 4408 of lenses and mirrors to direct the beam through a mode sorter 4410.
  • the beam is separated into its different modes when regenerated at mode sorter 4412 and the intensity images may be registered by a camera 4414.
  • the beam from the laser 4402 has an inherent eccentricity of approximately 0.15.
  • Fig. 46 there is illustrated an example of an ellipse 4602 having a radius "a" along its long axis, a radius "b” along a short axis and a distance "c" to the foci 4604 of the ellipse.
  • 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 equations:
  • Fig. 47 there is illustrated a flow diagram for analyzing intensity images taken by the camera 4414.
  • the intensity image has applied thereto threshold double precision amplitude to enable the ring to be clearly seen without extra pixels outside of the ring at step 4702.
  • step 4701 both columns and rows are scanned along for the entire image.
  • the peaks of the two largest hills and their locations are determined at step 4706.
  • An ellipse is fit at step 4008 for all peak locations found.
  • step 4710 a determination is made of the major and minor axis of the ellipse, the focal point of the ellipse, the centroid, eccentricity and orientation of the ellipse.
  • Fig. 48 illustrates an ellipse fitting algorithm flowchart.
  • the X and Y pixel locations are input at step 4802 for all peaks that are found.
  • An initial guess is provided at step 4804 for the conic equation parameters.
  • the conjugate gradient algorithm is used at step 4806 to find conic equation parameters that provide an optimal fit.
  • An orientation of the ellipse is determined at step 4808 and moved to determine the major and minor axis.
  • Molecular spectroscopy using OAM twisted beams can leverage fractional OAM states as a molecular signature along with other intensity signatures (i.e. eccentricity, shift of center of mass and rotation of the elliptical intensity) as well as phase signatures (i.e. changes in the phase of the scattered beam) and specific formation of publicity distributed spectrum.
  • intensity signatures i.e. eccentricity, shift of center of mass and rotation of the elliptical intensity
  • phase signatures i.e. changes in the phase of the scattered beam
  • the method of optical orientation of electronics was by circularly polarized photons has been heavily used to study spin angular momentum in solid state materials.
  • the process relies on spin-orbit coupling to transfer angular momentum from the spin of protons to the spin of electrons and has been Incorporated into pump-probe Kerr and Faraday rotation experiments to study the dynamics of optically excited spends.
  • the proposed spectroscopy technique focuses instead on localized orbital angular momentum (OAM) and solids. Specifically, one can distinguish between delocalized OAM associated with the envelope wave function which may be macroscopic in spatial extent, and local OAM associated with atomic sites, which typically is incorporated into the effect of spin and associated electronic states.
  • OAM orbital angular momentum
  • the former type of angular momentum is a fundamental interest to orbital fleet coherent systems, for example, quantum Hall layers, superconductors and topological insulators.
  • Fig. 49 one manner for using nested fractional OAM states to alleviate the problems associated with integer OAM states and to enable the use of stable states of fractional OAM for similar purposes as those described herein above.
  • the input signals 4902 are provided to fractional OAM generation circuitry 4904.
  • the fractional OAM generation circuitry 4904 generates output signals 4906 having fractional orthogonal states which may then be further applied or detected as discussed herein.
  • the orbital angular momentum of light beams is a consequence of their azimuthal phase structure. Light beams have a phase factor , where m is an integer and ⁇ is
  • OAM orbital angular momentum
  • These light beams can be generated in the laboratory by optical devices, such as spiral phase plates or holograms, which manipulate the phase of the beam.
  • the resulting phase structure has the form of ⁇ m ⁇ intertwined helices of equal phase.
  • the chosen height of the phase step generated by the optical device is equal to the mean value of the OAM in the resulting beam.
  • M mod 1 1/2
  • the component of the OAM in the propagation direction Lz and the azimuthal rotation angle form a pair of conjugate variables (just like time-frequency or space-momentum).
  • the state spaces for OAM and the rotation angle are different in nature.
  • the OAM eigenstates form a discrete set of states with m taking on all integer values.
  • Eigenstates of the angle operator are restricted to a 2 ⁇ radian interval since it is physically impossible to distinguish between rotation angles differing by less than 2 ⁇ radians.
  • the properties of the angle operator are rigorously derived in an arbitrarily large, yet finite state space of 2L + 1 dimensions.
  • This space is spanned by the angular momentum states ⁇ m) with m ranging from—L, —L + 1, . . , L.
  • the 2 ⁇ radian interval [ ⁇ 0, ⁇ 0 +2 ⁇ ) is spanned by 2L+1 orthogonal angle states
  • ⁇ ) with ⁇ ⁇ 0 +27rn/(2L+l).
  • ⁇ determines the starting point of the interval and with it a particular angle operator ⁇ " ⁇ . Only after physical results have been calculated within this state space is L allowed to tend to infinity, which recovers the result of an infinite but countable number of basis states for the OAM and a dense set of angle states within a 2 ⁇ radian interval.
  • light beams may be generated using a spiral phase plate.
  • light beams generated using a spiral phase plate with a non-integer phase step are unstable on propagation.
  • Input signals 5004 are provided to the spatial light modulator 5002 and used for the generation of fractional OAM beams 5006.
  • the spatial light modulator 5002 synthesizes Laguerre Gaussian modes rather than using a phase step of a spiral phase plate.
  • a light beam with fractional OAM may be produced as a generic superposition of light modes with different values of m.
  • various Laguerre-Gaussian beam modes 5102 may have a superposition process 5104 applied thereto by the spatial light modulator 5002 in order to generate the fractional beam outputs 5106.
  • OAM can be represented as a quantum state.
  • This quantum state 5202 can be decomposed into a basis of integer OAM states 5204 as generally illustrated in Fig. 52. The decomposition only determines the OAM index m which in a superposition of LG beams leaves the index for the number of concentric rings unspecified.
  • Fig. 53 there is illustrated the manner in which an SLM may be programmed to provide fractional OAM beams.
  • a single SLM 5302 may be programmed with a hologram 5304 that sets the phase structure 5306 and intensity structure 5308 for generating the superposition.
  • a blazed grating 5310 is also included in the hologram 5304 to separate angularly the first fractional order. The formula for the resulting phase distribution of the hologram 5304 and rectilinear coordinates is given by:
  • beam is the phase profile of the superposition at the beam waist for grating is the phase profile of the blazed grating
  • the two phase distributions are added to modulo 2 ⁇ and, after subtraction of ⁇ are multiplied by an intensity mask. In regions of low intensity the intensity mask reduces the effect of the blazed grating 5310, which in turn leads to reduced intensity in the first diffraction order.
  • the mapping between the phase depth and the desired intensity is not linear but rather given by the trigonometric sine function.
  • a carrier phase representing a blazed grating 5402 is added to the phase 5404 of the superposition modulo 2 ⁇ , This combined phase 5406 is multiplied at step 5504 by an intensity mask 5408 which takes account of the correct mapping between the phase depth and diffraction intensity 3010.
  • the resulting hologram 5412 at step 5506 is a hologram containing the required phase and intensity profiles for the desired non-integer OAM beam.
  • the various cross-sections are plotted over a range of ⁇ 3w(z) for each value of z.
  • Profiles 5608, 5610 and 5612 show the corresponding experimental profiles.
  • fractional OAM beams may be generated from a fractional OAM beam generator 5702. These fractional OAM beams are then shown through a sample 5704 in a manner similar to that discussed herein above.
  • OAM spectroscopy detection circuitry 5706 may then be used to detect certain OAM fraction state profiles caused by the OAM beam shining through the sample 5704. Particular OAM fraction states will have a particular fractional OAM state characteristics caused by the sample 5704. This process would work in the same manner as that described herein above.
  • Fig. 58 illustrates one example of a OAM state profile that may be used to identify a particular material within a sample.
  • This particular OAM state profile would be uniquely associated with a particular material and could be used to identify the material within a sample when the profile was detected.
  • the interaction of Laguerre Gaussian light beams with glucose and beta amyloid have been the initial spectroscopy application of OAM to sample types.
  • OAM state profiles may also be utilized.
  • a pump-probe magneto-orbital approach may be used.
  • Laguerre-Gaussian optical pump pulses impart orbital angular momentum to the electronic states of a material and subsequent dynamics are studied with femto second time resolution.
  • the excitation uses vortex modes that distribute angular momentum over a macroscopic area determined by the spot size, and the optical probe studies the chiral imbalance of vortex modes reflected off of a sample. There will be transients that evolve on timescales distinctly different from population and spin relaxation but with large lifetimes.
  • a further application of the OAM spectroscopy may be further refined by identifying items using a number of different types of spectroscopy to provide a more definitive analysis.
  • Fig. 59 there is generally illustrated a multi-parameter spectroscopy system 5900.
  • a plurality of different spectroscopy parameters 5902 may be tracked and analyzed individually.
  • the group of parameters is then analyzed together using multi-parameter spectroscopy analysis processor or system 5904 to determine and identify a sample with output 5906.
  • the different spectroscopic techniques receive a light beam generated from a light source 5908, for example a laser, that has passed through a sample 5910 that a material or concentration of material therein that is being detected. While the light source of Fig.
  • multiple light sources may provide multiple light beams or a single source may be used to provide multiple light beams.
  • development of a single optical spectroscopy system to fully characterize the physical and electronic properties of small samples in real time may be accomplished using the polarization, wavelength, and orbital angular momentum (OAM) of light.
  • a polarized optical source is used to characterize the atomic and molecular structure of the sample.
  • the wavelength of the source characterizes the atomic and molecular electronic properties of the sample including their degree of polarizability.
  • OAM properties of the source are principally used to characterize the molecular chirality, but such new techniques are not limited to chiral molecules or samples and can be applied to non-chiral molecules or samples.
  • 3D or multiparameter spectroscopy empowers consumers with numerous applications including useful real time chemical and biological information.
  • 3D/muti-parameter spectroscopy promises new possibilities in ultrafast, highly-selective molecular spectroscopy. While the following description discusses a number of different spectroscopy techniques that may be implemented in multi-parameter spectroscopy system 5900, it should be realized that other spectroscopy techniques may be combined to provide the multi-spectroscopy analysis system of the present disclosure.
  • Spectroscopy is the measurement of the interaction of light with various materials.
  • the light may either be absorbed or emitted by the material. By analyzing the amount of light absorbed or emitted, a materials composition and quantity may be determined.
  • Some of the light's energy is absorbed by the material. Light of a given wavelength interacting with a material may be emitted at a different wavelength. This occurs in phenomena like fluorescence, luminescence, and phosphorescence. The effect of light on a material depends on the wavelength and intensity of the light as well as its physical interaction with the molecules and atoms.
  • FIG. 60 A schematic of a spectrometer which makes relative measurements in the optical spectral region of the electromagnetic spectrum uses light that is spectrally dispersed by a dispersing element is shown in Fig. 60.
  • a device 6002 such as a monochromator, polychromator, or interferometer, selects a specific wavelength from a light source 6004. This single-wavelength light interacts with a sample 6006.
  • a detector 6008 is used to measure the spectrum of light resulting from this interaction.
  • a change in the absorbance or intensity of the resulting light 6010 is measured as the detector 6008 sweeps across a range of wavelengths.
  • a range of different spectroscopic techniques, based on these fundamental measurements, have been developed such as those discussed in A.
  • Infrared frequencies occur between the visible and microwave regions of the electromagnetic spectrum as shown in Fig. 61.
  • the frequency, v, measured in Hertz (Hz), and wavelength, ⁇ , 6102 typically measured in centimeters (cm) are inversely related according to the equations:
  • the infrared (IR) spectrum 6104 is divided into three regions: the near-, mid-, and far-IR.
  • the mid IR region includes wavelengths between
  • IR radiation is absorbed by organic molecules.
  • Molecular vibrations occur when the infrared energy matches the energy of specific molecular vibration modes. At these frequencies, photons are absorbed by the material while photons at other frequencies are transmitted through the material.
  • the IR spectrum of different materials typically includes unique transmittance, T, peaks and absorbance troughs occurring at different frequencies such as the measured IR spectrum of water vapor shown in Fig. 62.
  • the absorbance, A is related to the transmittance by
  • Each material exhibits a unique infrared spectral fingerprint, or signature, determined by its unique molecular vibration modes which permit identification of the material's composition by IR spectroscopy.
  • IR spectroscopy In the case of water vapor (Fig. 62), for example, the water molecules absorb energy within two narrow infrared wavelengths bands that appear as absorbance troughs 6202.
  • Fig. 63 water molecules exhibit two types of molecular vibrations: stretching and bending.
  • a molecule 6302 consisting of n atoms 6308 has 3n degrees of freedom. In a nonlinear molecule like water, three of these degrees are rotational, three are translational, and the remaining correspond to fundamental vibrations. In a linear molecule 6302, two degrees are rotational and three are translational. The net number of fundamental vibrations for nonlinear and linear molecules is therefore, 3n— 6 and 3n— 5, respectively.
  • Fig. 6 For water vapor, there are two strong absorbance troughs 6202 (Fig.
  • the symmetric and asymmetric stretching modes 6304 absorb at frequencies in very close proximity to each other (2.734 im and 2.662 im, respectively) and appear as a single, broader absorbance band in Fig. 62 between the troughs 6202.
  • Carbon dioxide, CO2 exhibits two scissoring and bending vibrations 6402, 6404 (Fig. 64) that are equivalent and therefore, have the same degenerate frequency. This degeneracy appears in the infrared spectrum of Fig. 65 at The symmetrical
  • stretching vibrational mode 6404 of CO2 is inactive in the infrared because it doesn't perturb its molecular dipole moment. However, the asymmetrical stretching vibration mode 6402 of CO2 does perturb the molecule's dipole moment and causes an absorbance in CO2 at 4.3 im as shown in Fig. 65.
  • the stretching frequency of a molecular bond may be approximated by Hooke's Law when treated as a simple classical harmonic oscillator consisting of two equal masses bound by a spring
  • k is the force constant of the spring and m is the mass of an atom.
  • Infrared spectroscopy is used to identify material species by their unique vibrational and rotational optical signatures.
  • a complementary spectroscopy technique, Raman spectroscopy is used to identify materials by their unique light-scattering signatures as discussed in the next section.
  • Raman spectroscopy is a technique used to characterize a material by the amount of light it scatters.
  • Raman spectroscopy complements infrared spectroscopy which instead measures the amount of light absorbed by a material.
  • Raman and infrared spectroscopy may further be used in conjunctions with OAM and polarization spectroscopy to further improve analysis results.
  • OAM and polarization spectroscopy When light interacts with matter, changes in the dipole moment of its molecules yield infrared absorption bands while changes in their polarizability produce Raman bands.
  • the sequence of observed energy bands arises from specific molecular vibrations which collectively produce a unique spectral signature indicative of each type of molecule.
  • Raman spectroscopy was established as a practical chemical analysis method useful to characterize a wide variety of chemical species including solid, liquid, and gaseous samples. Solid crystal lattice vibrations are typically active in Raman spectroscopy and their spectra appear in polymeric and semiconductor samples. Gaseous samples exhibit rotational structures that may be characterized by vibrational transitions. [0207] Approximately one percent of incident photons scatter inelastically, and yield lower energy photons. Raman scattering results from changes in the vibrational, rotational, or electronic energy of a molecule.
  • the vibrational energy of the scattering molecule is equivalent to the difference between incident and Raman scattered photons.
  • incident photon interacts with the electric dipole of a molecule
  • this form of vibronic spectroscopy is often classically viewed as a perturbation of the molecule's electric field.
  • the scattering event is described as an excitation to a virtual energy state lower in energy than a real electronic transition with nearly coincident decay and change in vibrational energy.
  • Such spectroscopy can work in conjunction with incident photons that carry OAM.
  • incident photons excite electrons to a different final energy level than its original energy level (Fig. 68).
  • Anti-Stokes shifted scattering events 6810 result from a small fraction of molecules originally in vibrationally excited states (Fig. 68) which leave them in the ground state 6812 and results in Raman scattered photons with higher energy.
  • Fig. 68 vibrationally excited states
  • Raman scattered photons with higher energy.
  • anti-Stokes shifted Raman spectra are always weaker than Stokes-shifted spectrum since the Stokes and anti-Stokes spectra contain the same frequency information. Most Raman spectroscopy focuses exclusively on Stokes-shifted scattering phenomena for this reason.
  • the force constant by which the vibrational mode energy may be modeled is affected by molecular structure including atomic mass, molecular species, bond order, and the geometric arrangement of molecules.
  • Raman scattering occurs when the polarizability of molecules may be affected.
  • the polarizability, a, of a molecule appears as a proportionality constant between the electric field and the induced dipole moment,
  • Raman-active vibrations are non-existent in the infrared for molecules having a center of symmetry while the existence of a perturbed symmetry center (e.g. permanent dipole moment) indicates the absence of infrared-active vibrations.
  • the intensity of a Raman band is proportional to the square of the spatial change of polarizability, or the induced dipole moment
  • Raman spectroscopy exhibits several advantages over other spectroscopy techniques. Raman bands exhibit good signal-to-noise ratios owing to its detection of fundamental vibrational modes. Hence, the Raman signature of measured samples is typically more pronounced and definitive.
  • Raman spectroscopy is more useful for analyzing aqueous solutions than infrared spectroscopy since the Raman spectrum of water is weak and unobtrusive while the infrared spectrum of water is very strong and more complex. In organic and inorganic chemistries, the existence of covalent bonds yields a unique Raman signature.
  • a Raman spectroscopy setup only requires an appropriate laser source incident on a material and a detector to collect scattered photons which minimizes the need for elaborate sample preparation. Raman spectroscopy is non-destructive as the material is merely illuminated with a laser. Because the Raman effect is weak, the efficiency and optimization of a Raman spectroscopy instrument is critically important to providing measurements of the slightest molecular concentrations within the shortest possible time.
  • the intensity of spontaneous Raman scattering is linearly dependent on the incident intensity of light but of several orders of magnitude less intense. Treating the light- matter interaction quantum mechanically, the total Hamiltonian may be expressed in terms of the energy associated with the vibrational modes of the molecule, H_v, the light, ⁇ _ ⁇ , and their interaction, ⁇
  • vibrational frequency and the normal mode amplitude q which may be expressed in
  • the interaction Hamiltonian may be obtained in terms of the molecule's polarizability, a,
  • the first term characterizes Rayleigh scattering.
  • the remaining first order Raman scattering term is needed to characterize spontaneous Raman scattering including the coherent laser field, "E" _L, in addition to the Stokes and anti-Stokes fields, respectively. Substituting q and E_y into this expression yields
  • n_v the eigenstates, ⁇ n_v) with excitation quanta n_v are acted upon by creation and annihilation operators to yield the Stokes and anti-Stokes transition rates Hence, it is easy to determine n_v from the Raman signal intensity given a linear dependence.
  • the integrated anti-Stokes intensity of a Raman mode is proportional to the average vibrational quantum number of the mode
  • A is the Raman cross section. Normalizing I_AS with respect to the room temperature Stokes signal of the same mode in addition to using the Boltzmann distribution,
  • Stimulated Raman intensity is nonlinearly dependent on the incident intensity of photons but of similar magnitude.
  • Inelastic scattering of a photon with an optical phonon originating from a finite response time of the third order nonlinear polarization of a material is characteristic of Raman scattering.
  • Monochromatic light propagating in an optical material yields spontaneous Raman scattering in which some photons are transitioned to new frequencies.
  • the polarization of scattered photons may be parallel or orthogonal if the pump beam is linearly polarized.
  • Stimulated Raman scattering occurs when the scattering intensity of photons at shifted frequencies is enhanced by existing photons already present at these shifted frequencies. Consequently, in stimulated Raman scattering, a coincident photon at a downshifted frequency receives a gain which may be exploited in Raman amplifiers, for example, or usefully employed in molecular spectroscopy.
  • SRS Stimulated Raman scattering
  • the probability of Raman scattering is directly related to the photon density in the pump wave and the Raman cross section.
  • the Stokes and pump waves must overlap spatially and temporally to generate stimulated emission. Since, the Raman process involves vibrational modes of molecules within a material; its intensity spectrum determines the material composition. In amorphous materials, for example, the vibrational energy levels tend to merge and form bands and the pump frequency may differ from the Stokes frequency over a wide range. In crystalline materials, however, the intensity peaks tend to be well-separated as they have narrow bandwidths.
  • the coupled wave equations for forward Raman scattering include for Stokes intensities with a_S the Stokes attenuation coefficient, and
  • Stimulated scattering intensity increases when the stimulated gain exceeds the linear loss which is the source of the threshold power which must be overcome to initiate stimulated Raman scattering.
  • a beat frequency drives molecular oscillations responsible for increasing the scattered wave amplitude.
  • the increasing wave amplitude enhances the molecular oscillations as part of a positive feedback loop that results in the stimulated Raman scattering effect.
  • the pump depletion term is removed,
  • the observed scattered intensity may be as intense as This resonance
  • Raman effect permits highly sensitive spectroscopic discrimination of a molecular species within a complex material medium such as chromophores within proteins embedded in a biological membrane.
  • the functional component of most biological chromophores consist of atoms conjugated with the particular electronic transition to which resonance Raman spectroscopy is selectively sensitive.
  • the frequency of measured resonance Raman bands yields information about the vibrational structure of the electronic states involved in the transition used for inducing the resonance.
  • the scattering intensities provide information about the nature of mode coupling with the electronic transition.
  • a molecule in vibronic state m subjected to a plane-polarized incident light of frequency v_0 and intensity /_0 is perturbed into a new vibronic state n.
  • the scattering intensity during the transition from m to n is given by
  • each path matrix element of the polarizability tensor, a, for a transition from m to n may be written in terms of intermediate vibronic states
  • the total scattering intensity is therefore dependent on the state of polarization of the exciting light.
  • Laguerre-Gaussian functions may mathematically characterize a beam of vortex light in terms of generalized Laguerre polynomials, with a Gaussian envelope.
  • the special case of forward scattering reduces 3 x3 Raman tensors to 2 x2.
  • the Raman tensors for £ ⁇ 2 excitations all have the same form. So from symmetry considerations, the ⁇ -dependence vanishes for £ ⁇ 2. Since the constants a, b, c, d, and e depend on £ and the symmetry of the crystal, non-zero OAM yields a ⁇ 2 phonon for £ ⁇ 2 photon excitation and decouples the two Raman tensors for the ⁇ 3 phonon for £ ⁇ 1 photon excitation.
  • OAM Raman spectroscopy exhibits the capacity to characterize the atomic and molecular composition of a crystalline material. More complicated selection rules are needed to fully obtain an OAM Raman signature of chiral materials which present their own unique atomic and molecular symmetry properties.
  • a plane-polarized Raman source may be used to characterize the atomic structure of crystals and molecular structure of polymeric films, crystals, and liquid crystals.
  • polarized Raman techniques involve a polarizer 6906 between the sample 6904 and the spectrometer 6908 oriented either parallel (II) or perpendicular (1) to the polarization state of the laser source 6902.
  • polarizing optics 6910 may be inserted between the laser 6902 and sample 6904 to select an appropriate state of polarization incident on the sample.
  • /_ 1 and /_ II are the Raman spectral band intensities with polarizations perpendicular and parallel, respectively, to the state of polarization of the laser source 6902.
  • polarized Raman spectroscopy 7002 can be used to supplement atomic and molecular information gained by non-polarized Raman spectroscopy 7004.
  • a single integrated spectroscopy unit 7006 exploiting both polarized and non-polarized Raman effects using combined results processing 7008 that improves overall quality and amount of information gained by spectroscopically processing data from a sample using multiple types of spectroscopic analysis.
  • the typical Raman source is a Gaussian laser operating in its fundamental mode with an electric field
  • a longitudinal mode along the z-direction incident on a molecule scatters light that completes the picture of the molecule's polarizability to include P_z.
  • An electric field having a z-component is a radially -polarized beam with a polarization vector
  • Terahertz spectroscopy is conducted in the far-infrared frequency range of the electromagnetic spectrum (Fig. 61) and is therefore useful for identifying far-infrared vibrational modes in molecules.
  • THz spectroscopy can provide a higher signal-to-noise ratio and wider dynamic range than far-infrared spectroscopy due the use of bright light sources and sensitive detectors. This provides for selective detection of weak inter- and intra- molecular vibrational modes commonly occurring in biological and chemical processes which are not active in IR-spectroscopy.
  • THz spectroscopy may also be used in conjunction with incident photons that carry OAM.
  • Terahertz waves pass through media that are opaque in the visible and near-IR spectra and are strongly absorbed by aqueous environments (see Fig. 72).
  • THz spectroscopy was historically hindered by a lack of appropriately high powered light sources. However, access to practical THz spectroscopy in the far-infrared range was permitted by the generation of THz rays based on picosecond and femtosecond laser pulses.
  • THz sources include either short pulse mode (e.g. photoconductive antennas, optical rectifiers) or continuous wave (CW) mode having a wide range of available output power (nano watts to 10 watts).
  • THz sources are used today to interrogate biological, chemical and solid state processes. Sources in the 1 -3.5 THz range are frequently used in biology and medicine, for example, to investigate conformational molecular changes. THz spectroscopy is used today as frequently as Raman spectroscopy.
  • THz-TDS Terahertz time-domain spectroscopy
  • THz absorption properties of samples are characterized by a THz imaging technique. This technique was demonstrated in systems designed for THz-TDS based on picosecond pulses as well as systems utilizing continuous -wave (CW) sources such as a THz-wave parametric oscillator, quantum cascade laser, or optically pumped terahertz laser. THz spectroscopy can be used in conjunction with incident photons that carry OAM.
  • CW continuous -wave
  • THz pulse imaging provides broad image frequency information between 0.1 -5 THz while THz CW imaging may be performed in real-time, is frequency-sensitive, and has a higher dynamic range due to significantly higher spectral power density.
  • the characteristics of the light source are important.
  • a THz spectrometer may mechanically scan a sample in two dimensions, but the time of each scan scales with sample size.
  • Real time THz imaging is often conducted with an array of THz wave detectors composed of electro-optic crystals or a pyroelectric camera. Such THz spectroscopy can be used in conjunction with incident photons that carry OAM.
  • THz imaging suffers from poor resolution as estimated in terms of its diffraction limit which is less than a millimeter and from low transmission through an aperture resulting in low sensitivity. To exceed the diffraction limitation near-field microscopy is used to achieve sub-wavelength resolution, though low transmission remains an issue.
  • vibrational energy level 7302 of the electronic ground state Perturbed by incident light, electrons in molecules at room temperature are excited from the lowest vibrational energy level 7302 of the electronic ground state to either the first (S_l) 7304 or second (S_2) 7306 vibrational state (Fig. 73) and may occupy any one of several vibrational sub-levels.
  • Each vibrational sub-level has many neighboring rotational energy levels in such close proximity that inter-sub-level energy transitions are almost indistinguishable. Consequently, most molecular compounds have broad absorption spectra with the exception of those having negligible rotational characteristics such as planar and aromatic compounds.
  • the quantum efficiency is less than unity.
  • the "0 - 0" transition from the lowest vibrational ground state sub-level to the lowest vibrational S_l sub-level 7308 is common to both the absorption and emission phenomena while all other absorption transitions occur only with more energy than any transition in the fluorescence emission.
  • the emission spectrum subsequently overlaps the absorption spectrum at the incident photon frequency corresponding to this "0 - 0" transition while the rest of the emission spectrum will have less energy and equivalently occurs at a lower frequency.
  • the "0 - 0" transition in the absorption and emission spectra rarely coincide exactly given a small loss of energy due to interaction of the molecule with surrounding solvent molecules.
  • the quantum efficiency of most complex molecules is independent of the frequency of incident photons and the emission is directly correlated to the molecular extinction coefficient of the compound.
  • the corrected excitation spectrum of a substance will be the same as its absorption spectrum.
  • the intensity of fluorescence emission is directly proportional to the incident radiation intensity.
  • Fluorescence spectroscopy results in emission and excitation spectra.
  • emission fluoroscopy the exciting radiation is held at a fixed wavelength and the emitted fluorescent intensity is measured as a function of emission wavelength.
  • 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 may also be used in conjunction with incident photons that carry OAM. Performing both emission and excitation spectra together yields a spectral map of the material under interrogation. Materials of interest may contain many fluorophores, and different excitation wavelengths are required to interrogate different molecules as shown in Figs.
  • Fluorescence spectrometers analyze the spectral distribution of the light emitted from a sample (the fluorescence emission spectrum) by means of either a continuously variable interference filter or a monochromator. Monochromators used in more sophisticated spectrometers select the exciting radiation and analyze the sample emission spectra. Such instruments are also capable of measuring the variation of emission intensity with exciting wavelength (the fluorescence excitation spectrum).
  • Sensitivity of fluorescence spectroscopy depends largely on the properties of the measured sample and is typically measured in parts per billion or trillion for most materials. This remarkable degree of sensitivity permits reliable detection of very small sample sizes of fluorescent materials (e.g. chlorophyll and aromatic hydrocarbons).
  • Fluorescence spectroscopy is exceptionally specific and less prone to interference because few materials absorb or emit light (fluoresce) and rarely emit at the same frequency as compounds in the target material.
  • Fluorescence measurements scale directly with sample concentration over a broad frequency range and can be performed over a range of concentrations of up to about one six orders of magnitude without sample dilution or alteration of the sample cell. Additionally, the sensitivity and specificity of fluoroscopy reduces or eliminates the need for costly and time-consuming sample preparation procedures, thus expediting the analysis. Overall, fluoroscopy represents a low-cost material identification technique owing to its high sensitivity (small sample size requirement).
  • Pump-probe spectroscopy is used to study ultrafast phenomena in which a pump beam pulse perturbs atomic and molecular constituents of a sample and a probe beam pulse is used to interrogate the perturbed sample after an adjustable period of time.
  • This optical technique is a type of transient spectroscopy in which the electronic and structural properties of short-lived transient states of photochemically or photophysically relevant molecules may be investigated. The resulting excited state is examined by monitoring properties related to the probe beam including its reflectivity, absorption, luminescence, and Raman scattering characteristics. Electronic and structural changes occurring within femto- to pico-second timeframes may be studied using this technique.
  • FIG. 75 A basic pump probe configuration is shown schematically in Fig. 75.
  • a pulse train generated by a laser 7502 is split into a pump pulse 7506 and a probe pulse 7508 using a beamsplitter 7504.
  • the pump pulse 7506 interacts with the atoms and molecules in a sample 7510.
  • the probe pulse 7508 is used to probe the resulting changes within the sample after a short period of time between the pulse train and the probe pulse train.
  • a spectrum of absorption, reflectivity, Raman scattering, and luminescence of the probe beam may be acquired after the sample to study the changes made by the pump pulse train at detector 7512. It is possible to obtain information concerning the decay of the pump-induced excitation by monitoring the probe train 7508 as a function of the relative time delay.
  • the probe train 7508 is typically averaged over many pulses and doesn't require a fast photodetector 7512.
  • the temporal resolution of measurements in pump-probe spectroscopy is limited only by the pulse durations of each train. In general, the uncertainty in timing must be smaller than the timescale of the structural or electronic process induced by the pump train.
  • the pump 7506 and probe 7508 beams have different wavelengths produced by two synchronized sources. While this technique provides additional capabilities in ultrafast spectroscopy, it's essential to ensure precise source synchronization with a very low relative timing jitter.
  • the scattered intensities provided by a pump-probe Raman spectroscopy technique may be tremendously enhanced with different pump and probe frequencies, ⁇ and ⁇ , as shown in Fig. 76.
  • the frequency of the pump beam is changed, while the frequency of the probe beam is fixed.
  • the pump beam is used to induce Raman emission, while the probe beam serves to reveal Raman modes.
  • Both the pump and the probe beam traverse a Raman-active medium in collinearity.
  • the difference between the pump and probe frequencies coincide with a Raman vibrational mode frequency, v, of the medium
  • the weak spontaneous Raman light is amplified by several orders of magnitude (10— 10 4 ) due to the pump photon flux. Gain is achieved as shown in Fig. 76.
  • the pump beam is essentially engineered to provide a variety of perturbative excitations within a wide range of samples.
  • Pump-probe spectroscopy is therefore applicable to use within the context of other spectroscopy techniques including the use of a pump beam endowed with orbital angular momentum as discussed in the next section.
  • Chiral optics conventionally involved circularly polarized light in which a plane polarized state is understood as a superposition of circular polarizations with opposite handedness.
  • the right- and left- handedness of circularly polarized light indicates its spin angular momentum (SAM), ⁇ h in addition to the polarization one can use the helicity of the associated electromagnetic field vectors. Its interaction with matter is enantiomerically specific. The combined techniques would have specific signatures for different materials.
  • SAM spin angular momentum
  • OAM Orbital angular momentum
  • Delocalized OAM within solid materials associated with the envelope wavefunction in a Bloch framework may be distinguished from local OAM associated with atoms.
  • the latter is associated with the Lande g-factor of electronic states and part of the effective spin while the former is of interest to orbitally coherent systems (e.g. quantum Hall layers, superconductors, and topological insulators).
  • orbitally coherent systems e.g. quantum Hall layers, superconductors, and topological insulators.
  • OAM-endowed beams of light have been used to induce such delocalized OAM- states in solids using a time-resolved pump-probe scheme using LG beams in which the
  • FIG. 77 A simple pump-probe OAM spectroscopy instrument is shown schematically in Fig. 77 in which the OAM pump beam 7702 is an Laguerre-Gaussian beam cycled between at some frequency, The pump beam 7702 perturbs target
  • the interaction of light exhibiting OAM, an azimuthal photonic flow of momentum, with chiral molecules is the subject of several recent theoretical and experimental reports. On one hand, the strength of the interaction has been conjectured as negligible, while on the other hand, not only does such an interaction exist, it may be stronger than the interactions occurring in conventional polarimetry experiments in which the direction of linearly polarized light incident on a solution is rotated by some angle characteristic of the solution itself. A few limited experimental studies have suggested that the former theoretical body of work is correct - that such an interaction is negligible.
  • the Gaussian beam solution to the wave equation and its extension to higher order laser modes including Hermite-Gaussian (HG) and commonly studied in optics labs.
  • LG modes exhibit spiral, or helical, phase fronts.
  • the propagation vector includes an orbital angular momentum (OAM) component often referred to as vorticity.
  • OAM orbital angular momentum
  • a spatial light modulator (SLM) is frequently used to realize holograms that modulate the phase front of a Gaussian beam and has renewed interest in engineered beams for a variety of purposes.
  • SLM spatial light modulator
  • a phase retarding forked grating, or hologram like the one shown in Figs 15A-15D.
  • the generating equation for the forked hologram may be written as a Fourier series,
  • r and ⁇ are coordinates
  • £ is the order of vorticity
  • D is the rectilinear grating period far from the forked pole.
  • Weights, t_m, of the Fourier components may be written in terms of integer-order Bessel functions, where ka and /e/? bias and modulate the grating phase, respectively. Only a few terms are needed to generate OAM beams, such as
  • Glucose exhibits a broad optical absorption band at ⁇ 750 nm with FWHM
  • the chirality of a molecule is a geometric property of its "handedness” characterized by a variety of spatial rotation, inversion, and reflection operations. Conventionally, the degree of chirality of molecules was starkly limited to a molecule being either “chiral” or “achiral” in addition to being “left-handed” or “right-handed”. However, this binary scale of chirality doesn't lend well to detailed spectroscopic studies of millions of molecular systems that may be studied. In its place, a continuous scale of 0 through 100 has been implemented for the past two decades called the Continuous Chirality Measure (CCM). Essentially, this continuous measure of chirality involves the Continuous Symmetry Measure (CSM) function,
  • n is the total number
  • the objective is to identify a point set, having a desired G-symmetry such that
  • chiral measure schemes include its ease of application to a wide variety of chiral structures including distorted tetrahedra, helicenes, fullerenes, frozen rotamers, knots, and chiral reaction coordinates, as well as being a measured without reference to an ideal shape.
  • Unique chirality values are made with reference to nearest symmetry groups ( ⁇ or S 2n ), thus allowing for direct comparison with a wide variety of geometric.
  • the Raman spectra of glucose, sucrose and fructose have already been collected for the three laser wavelengths 488, 514.5 and 632.8 nm from argon-ion and helium neon laser sources, the signals have been tabulated and the agreement of each vibration is justified with the other two laser lines. No resonances were observed as would be expected since there is no direct electronic absorption with these energies.
  • the Raman spectra are sensitive to local and global symmetries of the molecule at any wavelength. Differential Raman signals will give fundamental information about the interaction of a chiral electromagnetic field with the sugar molecules, as well as potentially lead to a selected symmetry resonance 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 grating blazed at 500 nm and 1200 lines/mm groove density.
  • the microscope objective used was 1 OX magnification.
  • To generate the OAM beam with angular momentum value L 2, a Q plate was incorporated into the system.
  • FIG. 80 there is illustrated the alignment procedure.
  • a linear polarizer is inserted at step 8002 into the beam path and rotated at step 8004 until maximum transmission intensity is achieved.
  • the circular polarizer is inserted at step 8010 before the Q-Plate.
  • the linear polarizer is placed at step 8012 after the Q-plate to observe the 4 lobed structure.
  • Fig. 81 the output of a HeNe laser is chopped around 1 kHz and sent into a single mode fiber.
  • the output is collimated with two biconvex lenses, sent through a half wave plate to adjust the polarization incident onto the Hamamatsu LCOS SLM 8102 with an angle of incidence of ⁇ 10 degrees per operation specifications of SLM.
  • the SLM 8102 displays forked diffraction grating or spiral phase pattern holograms generated using the MATLAB code in order to generate the desired OAM beam.
  • the reflected beam carries OAM and a characteristic "donut" shape is seen, with zero intensity along the beam axis.
  • This beam is then sent through a pair of crossed polarizers 8104 and to the detector 8 1 06 for lock-in detection.
  • Hb and Hb-A l e a proteins by Raman spectroscopy using OAM may also be investigated.
  • Mammalian blood is considered as connective tissue because of its cellular composition and due to its embryonic origin and also due to the origin and presence of colloidal proteins in its plasma.
  • Red Blood cells and Plasma proteins are the major constituents of blood.
  • These connective tissue components are targets for metabolic stress under disease conditions and result in the chemical alterations. All the blood components are subjected to excessive metabolic stress under hyperglycemic states. Blood acts a primary transporter of nutrients, gases and wastes. Blood plasma acts as a primary carrier for glucose to the tissues.
  • Normal pre-prandial plasma glucose levels are 80 mg/dl to 130 mg/dl and normal postprandial plasma glucose is ⁇ 180 mg/dl.
  • the Renal Threshold for Glucose (RTG) is the physiologic maximum of plasma glucose beyond which kidneys fail to reabsorb the glucose and get excreted in urine. This is a condition called glycosuria.
  • Glycosuria is the key characteristic of Diabetes mellitus (DM). High plasma glucose in DM will cause increased levels of Glycosylated Hemoglobin also known as HbAlc. Under normal physiological conditions HbAlc levels are ⁇ 7%, this also expressed as eAG which should be below 154mg/ dl in Normo-glycemic condition.
  • Glycation of Plasma proteins in DM is defined as the non- enzymatic random nonspecific covalent linking of glucose or other hexose sugar moieties to the proteins.
  • Glycation is defined as the non- enzymatic random nonspecific covalent linking of glucose or other hexose sugar moieties to the proteins.
  • HbAl c Glycated Hemoglobin
  • Hemoglobin (tetramer) has 6 residues of Tryptophan therefore Hemoglobin is a fluorescent protein. Tryptophan can undergo glycation and result in conformational changes in Hemoglobin. The tryptophan changes can be identified by using Raman studies (Masako Na- Gai et al. Biochemistry, 2012, 51 (30), pp 59325941) which is incorporated herein by reference. In order to understand the glycation induced Raman spectral changes in Tryptophan residues Raman spectra is obtained from analytical grade amorphous Tryptophan using 532 nm OceanOptics Raman Raman spectra of Proteins :
  • NIR Raman Blood and its components have intense fluorescence in visible range so NIR Raman may help reduce fluorescence and get good
  • Glycation derivatives in blood This needs normal and diabetic blood either from human subjects or animal models. And also Reference spectra of synthetic glycation products can be obtained by using this system, which can later be compared with the Raman signal from blood samples.
  • biomarkers of food spoilage.
  • This research includes identification of the biochemical mechanisms that produce certain chemical by-products that are associated with the physical characteristics of food spoilage. These mechanisms can be physical (e.g., temperature, pH, light, mechanical damage); chemical (e.g., enzymatic reaction, non-enzymatic reaction, rancidity, chemical interaction); microorganism-based (e.g., bacteria, viruses, yeasts, molds); or other (e.g., insects, rodents, animals, birds).
  • OAM and Raman techniques to identify these so-called biomarkers and their associated concentrations to better determine shelf life of basic food categories.
  • another aspect of the invention is to investigate the chemicals used that would fail to qualify foodstuffs as "organic.”
  • Table 1 shows several researched biochemical processes and chemical by-products associated with food spoilage mechanisms associated with common food groups:
  • a person skilled in the art would be well aware of various other mechanisms and biochemical indicators evidencing food spoilage of common foodstuffs, including other reactions or volatile or non-volatile organic compound (VOC) by-products associated with food spoilage.
  • VOC volatile or non-volatile organic compound
  • biomarker or chemical is a chiral or non-chiral molecule.
  • concentration of degradation of the sampled food group can then be correlated to concentration of degradation of the sampled food group to determine minimum and maximum concentrations acceptable to food freshness, spoilage, organic quality, and safety.
  • Ince Gaussian (IG) beams are the solutions of paraxial beams in an elliptical coordinate system.
  • IG beams are the third calls of orthogonal Eigen states and can probe the chirality structures of samples. Since IG modes have a preferred symmetry (long axis versus short axis) this enables it to probe chirality better than Laguerre Gaussian or Hermite Gaussian modes. This enables the propagation of more IG modes within an elliptical core fiber than Laguerre Gaussian modes or Hermite Gaussian modes.
  • IG modes can be used as a program signal for spectroscopy in the same manner that Laguerre Gaussian modes or Hermite Gaussian modes are used. This enables the detection of types of materials and concentration of materials using an IG mode probe signal.
  • the wave equation can be represented as a Helmholtz equation in Cartesian coordinates as follows
  • E(x, y, z) is complex field amplitude which can be expressed in terms of its slowly varying envelope and fast varying part in z-direction.
  • a Paraxial Wave approximation may be determined by substituting our assumption in the Helmholtz Equation.
  • the elliptical-cylindrical coordinate system may be define as shown in Fig. 82.
  • ⁇ 8i Z are real functions. They have the same wave-fronts as but different intensity distribution.
  • Figs. 85A and 85B The frequency of the even Ince Polynomials are illustrated in Figs. 85A and 85B and the modes and their phases are illustrated in Fig. 86.
  • Figs. 87A and 87B The frequency af the odd Ince Polynomials are illustrated in Figs. 87A and 87B and the modes and their phases are illustrated in Fig. 88.
  • any number of spectroscopic techniques such as optical spectroscopy, infrared spectroscopy, Ramen spectroscopy, spontaneous Ramen spectroscopy, simulated Ramen spectroscopy, resonance Ramen spectroscopy, polarized Ramen spectroscopy, Ramen spectroscopy with optical vortices, THz spectroscopy, terahertz time domain spectroscopy, fluorescence spectroscopy, pump probe spectroscopy, OAM spectroscopy, or Ince Gaussian spectroscopy may be used in any number of various combinations in order to provide better detection of sample types in concentrations. It should be realized that the types of spectroscopy discussed herein are not limiting in any combination of spectroscopic techniques may be utilized in the analysis of sample materials.
  • Fig. 89 in broadband frequency comb spectroscopy, the signal from an optical frequency comb is read by a conventional spectrometer, but in a technique called dual-comb spectroscopy, that conventional spectrometer 8902 and the instrument's limitations on speed and resolution are removed. Instead, a second frequency comb 8904 takes on the work previously done by the spectrometer 8902. The result can be dramatic gains in data acquisition speed, spectral resolution and sensitivity. These techniques can be used in conjunction with muti-parameter spectroscopy 8906 leveraging wavelength, polarization and OAM spectroscopy 8908.
  • An optical frequency comb 8904 is a spectrum consisting of hundreds of thousands or millions of equally spaced, sharp lines-analogous having a great many continuous-wave (CW) lasers simultaneously emitting at different, equally spaced frequencies.
  • Optical combs 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 produces a pulse train at a specific repetition rate, and with a specific, increasing additional carrier-envelope phase with each successive pulse. When the repetition rate and carrier-envelope phase of the pulse train are both stabilized against radio- or optical-frequency references, a Fourier transformation of the laser's periodic pulse train shows a sharp, comb-like spectrum in the frequency domain.
  • the frequency comb is well stabilized and referenced to an absolute frequency standard, such as an atomic clock, the comb spectrum becomes an extremely precise ruler for measuring optical frequencies. That ruler has found applications in a wide variety of scientific problems: high-resolution frequency measurements of atomic, ionic or molecular transitions to answer fundamental questions in physics; the detection of tiny amounts of Doppler shift; and other applications in attosecond physics, ultrapure microwave generation, time-frequency transfer over long distances, manipulation of atomic qubits, and many others.
  • the frequency comb pulse train s split into interferometer arms, one of which includes a mechanically scanned mirror, and the two pulse trains are sent through the sample to be analyzed.
  • a series of interferograms is recorded with a single photo-receiver and a digitizer: Fourier transformation of the interferograms generates the spectrum, with a resolution determined by the maximum optical-path-length difference of the
  • a key drawback of doing frequency comb spectroscopy with the Michelson- type setup described is speed: the scan rate of the setup, which is limited by the velocity of the scanning mirror, is commonly only on the order of Hz. Dual-comb spectroscopy eases this disadvantage by using a second frequency comb, rather than a moving mirror, to supply the delay time. The result can be a significant enhancement of the spectrometer's performance.
  • the pulse train forms a second comb, with a slightly different pulse repetition rate from the first, that is spatially combined with the train from the first comb.
  • the combined pulse train is passed through the sample to be analyzed, and detected by a photo-receiver.
  • the result in the time domain, is a repeated series of cross-correlation-like interferometric signals between the pulses, with a steadily increasing time difference based on the difference in repetition rate between the two combs.
  • the dual-comb interferograms thus have characteristics similar to those of a conventional Michelson-type Fourier transform spectrometer but because the dual- comb setup does not depend on the mechanical motion of a mirror, its scanning rate is several orders of magnitude faster than that of the Michelson-type interferometer.
  • Another advantage of dual-comb spectroscopy emerges in the frequency domain.
  • the mixing of the two optical combs, with slightly different repetition rates results in a third, down-converted radio-frequency (RF) comb, with spacing between teeth equivalent to the repetition rate difference between the two optical combs.
  • the sample's response is thus encoded on this down- converted RF comb, and the beat measurement between the two optical combs generates a multi-heterodyne signal that can be recovered from the RF comb.
  • the down-converted comb inherits the coherence property of the optical frequency combs, enabling broadband spectroscopy with a high resolution and accuracy with the speed and digital signal processing advantages of RF heterodyne detection.
  • a wearable device 9000 should include the following components as shown in Fig. 90.
  • An MCU (microcontroller) 9002 controls overall operation of the wearable device 9000.
  • BLE (Bluetooth low energy) transmitter / receiver 9004 transmits signals to and from the wearable device 9000.
  • Trance- impedance amplifier (TIA) for internally amplifying signals.
  • Drivers 9008 for driving LED/lasers within the device 9000.
  • High resolution ADC 9010 performs analog to digital conversions. Flash memory 9012 stores data within the wearable device 9000.
  • Real-time clock 9014 controls internal clocking operations.
  • MCU + BLE chipsets of 2013-2015 model year provide the following component options: a) EFM32 (MCU Silicon Laboratories) + CC2541 (BLE chip Texas Instruments) or BCM20732 (Broadcom), or b) Single chip solution form Nordic Semiconductors NRF51822 which includes similar Cortex M0 core and BLE radio, BLE stack is realized via underling Nordic proprietary OS (SoftDevice) which occupies about 100 kB of chips memory.
  • the near infrared laser diode system provides approximately 30 controllable channels between 1570 and 1600 nm, as well as an additional tunable source between 1450 and 1600.
  • Imaging through and parts of the body is critical for most biomedical optical technology.
  • Past work has developed imaging and spectroscopy in select transmission windows in the NIR where glucose and proteins have strong absorptions while water has reduced absorption. Since optical detection of glucose or other chemical compounds will most likely need to be in a region free of strong absorptions from other molecules, and will take place with OAM beams, imaging of the body tissues, brain, bone and skin with OAM may be used. Possible routes to investigate would be phase contrast and dark field imaging, ballistic transport of OAM through scattering media in the NIR and birefringent imaging.
  • the diode lasers available for the wearable device can also be incorporated into the NIR OAM imaging once a suitable detector is acquired and tested. Single channel detectors in the NIR are cheaper than 2D CCD arrays, however a scanning system and image construction software would be needed when imaging with a single channel detector.
  • a compact, handheld 3D spectrometer capable of simultaneous polarization, wavelength, and OAM-spectroscopy operated in a broad electromagnetic frequency range empowers consumers with tremendous amounts of useful information about such things as their food and air quality, household biological contaminants, medicinal identification, and health-related issues such as real-time information about dental caries.
  • This section serves as an outline of some of the potential applications of 3D spectroscopy.
  • Food substances primarily consist of water, fat, proteins, and carbohydrates.
  • the molecular structure and concentration of food substances govern their functional properties. Quantification of these properties dictates the quality of food in terms of minimum standards of suitability for human consumption or exposure which include chemical, biological, and microbial factors that may impact such parameters as their shelf-life.
  • Recent advances in industrialization of our food supply chains and changes in consumer eating habits have placed greater demand on the rapidity with which our food must be analyzed for safety and quality. This demand requires appropriate analytical tools such as spectroscopy.
  • Food spectroscopy is a desirable analysis method because it requires minimal or no sample preparation as well rapid, production-line measurements. Given the nature of spectroscopic analysis, multiple tests may be done on the sample. [0352] Outside the industrialized production line of our food supply, novel spectroscopic techniques could be employed at the level of individual consumers. For example, an individual consumer may spectroscopically measure the sugar concentration in his foods, overall food quality, ripeness, or identify a watermelon in the local grocery store as having been spoiled using a pocket size laser-based spectrometer. Nanoscale Material Development for Defense and National Security
  • Nanoscale material development for defense and national security technologies generally necessitates the binding site to recognize the target of interest.
  • spectroscopic techniques are currently based on absorption, scattering, of light, such as electron absorption (UV-vis), photoluminescence (PL), infrared (IR) absorption, and Raman scattering while more advanced techniques include single molecule spectroscopy, sum frequency generation, and luminescence up-conversion. These spectroscopy technologies aid in the fabrication process of nanoscale material architectures employed as biological and chemical sensors.
  • Optical spectroscopy of gas sensors is useful for a variety of environmental, industrial, medical, scientific and household applications.
  • the gas may be hazardous to human health, an atmospheric pollutant, or important in terms of its concentration for industrial or medical purposes. Aside from triggering an alarm, it is frequently desirable to measure accurate, real-time concentrations of a particular target gas, which is often in a mixture of other gases.
  • Consumers may use household units to monitor air for biological or chemical hazards such as airborne germs or carbon monoxide as well as surfactant contaminations on and around children's play areas, toys, and bedrooms. Such units would be useful in school classrooms, business offices, and shopping malls to alert to facilities managers to potential health hazards.
  • Further units may be useful in various industrial settings, including for example, chemical and/or petrochemical facilities, including but not limited to, using near-infrared spectroscopy.
  • detection presents various economic benefits for industrial operators to fix fugitive emission sources for increases in product recovery and abatement of governmental fines.
  • a toothbrush-size optical spectrometer would be useful to detect the onset of small dental caries (tooth decay and cavities) and alert the consumer to schedule a visit to the family dentist who may have been sent tooth-specific information before the scheduled visit.
  • neuro-imaging applications such as optical spectroscopy and correlation methods to measure oxygen and blood flow
  • development of new microscopes for functional imaging to improve the quantitative interpretation of measurement of brain activities and psychology using functional near-infrared spectroscopy
  • development technologies such as diffuse correlation spectroscopy to measure blood flow
  • development of multi-spectral optical imaging of cerebral hemoglobin can be applied to, and not limited to, neuro-imaging applications such as optical spectroscopy and correlation methods to measure oxygen and blood flow; the development of new microscopes for functional imaging to improve the quantitative interpretation of measurement of brain activities and psychology using functional near-infrared spectroscopy
  • the development technologies such as diffuse correlation spectroscopy to measure blood flow
  • multi-spectral optical imaging of cerebral hemoglobin can be applied to, and not limited to, neuro-imaging applications such as optical spectroscopy and correlation methods to measure oxygen and blood flow

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Abstract

L'invention concerne un appareil de détection d'un matériau dans un échantillon, qui comprend une unité électroluminescente pour diriger au moins un faisceau de lumière à travers l'échantillon. Une pluralité d'unités reçoivent le faisceau lumineux qui est passé à travers l'échantillon et effectuent une analyse spectroscopique de l'échantillon sur la base du faisceau lumineux reçu. Chacune de la pluralité d'unités analyse un paramètre différent par rapport à l'échantillon et fournit un signal de sortie séparé par rapport à l'analyse. Un processeur détecte le matériau par rapport à chacun des signaux de sortie séparés fournis.
PCT/US2017/013408 2016-01-13 2017-01-13 Système et procédé de spectroscopie à paramètres multiples WO2017123926A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2018536888A JP2019510202A (ja) 2016-01-13 2017-01-13 多重パラメータ分光法のためのシステム及び方法
EP17739034.1A EP3403067A4 (fr) 2016-01-13 2017-01-13 Système et procédé de spectroscopie à paramètres multiples
CN201780016835.8A CN108780042A (zh) 2016-01-13 2017-01-13 用于多参数光谱的系统和方法

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CN111157109A (zh) * 2020-01-10 2020-05-15 中国计量大学 一种基于等效张量重构法的关联涡旋识别装置
CN111209524A (zh) * 2020-01-14 2020-05-29 西安理工大学 一种拓扑绝缘体粒子对涡旋光散射特性的计算方法
WO2022032218A1 (fr) * 2020-08-07 2022-02-10 Endectra, Llc Spectromètre portatif pour l'interrogation de biomolécules dans un tissu biologique
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CN113884448A (zh) * 2021-09-29 2022-01-04 深圳市比特原子科技有限公司 水中溶解性总固体和氢离子浓度的检测装置及检测方法
CN114993965A (zh) * 2022-05-13 2022-09-02 中煤嘉沣(湖南)环保科技有限责任公司 一种污染源自动识别方法以及系统

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