[go: up one dir, main page]

WO2022177534A1 - Procédé d'analyse d'adultération et d'authenticité de matières et substances organiques par spectroscopie térahertz - Google Patents

Procédé d'analyse d'adultération et d'authenticité de matières et substances organiques par spectroscopie térahertz Download PDF

Info

Publication number
WO2022177534A1
WO2022177534A1 PCT/TR2022/050129 TR2022050129W WO2022177534A1 WO 2022177534 A1 WO2022177534 A1 WO 2022177534A1 TR 2022050129 W TR2022050129 W TR 2022050129W WO 2022177534 A1 WO2022177534 A1 WO 2022177534A1
Authority
WO
WIPO (PCT)
Prior art keywords
thz
sample
formula
path
analysis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/TR2022/050129
Other languages
English (en)
Inventor
Turgut ÖZTÜRK
Adnan Fatih DAĞDELEN
Furkan Türker SARICAOĞLU
Tuğba ŞİMŞEK
Hande HAYRABOLULU
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bursa Teknik Universitesi
Original Assignee
Bursa Teknik Universitesi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bursa Teknik Universitesi filed Critical Bursa Teknik Universitesi
Priority to US18/547,186 priority Critical patent/US20240142372A1/en
Publication of WO2022177534A1 publication Critical patent/WO2022177534A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • G01N21/17—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
    • G01N21/3577—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing liquids, e.g. polluted water
    • 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
    • G01N21/84—Systems specially adapted for particular applications
    • G01N21/85—Investigating moving fluids or granular solids

Definitions

  • the invention relates to the THz-TDS system, a sample preparation and chemometric-based analysis method that enables the determination of quality control, adulteration and authenticity of all organic substances and materials, especially samples with high water content.
  • THz waves in the electromagnetic spectrum are called electromagnetic waves, which generally vary in the range of 0.1-10 THz electromagnetic spectrum and whose limits are not fully determined. Although these electromagnetic waves are located in a very wide region, systems based on THz waves stand out as a technology open to innovations and new research areas. Today, THz waves have many usage areas such as health, defense, food, pharmaceutical industry, imaging, communication, internet of things. The most important reason for the great development in THz technology in recent years is the developments in electronic and optical technologies.
  • the THz region can be named differently such as sub-mm, T-rays, Terahertz waves (Nagatsuma et al., 2016; Pawar et al., 2013; Jones et al. , 2006; Verme 2007; Akkas, 2018).
  • THz waves passing through most materials are absorbed in water and water vapor, and are reflected by metals. These waves are harmless compared to X-rays due to their non-ionizing feature of biological tissues and can be used for medical imaging, although they do not cause any chemical reaction.
  • THz wave vibrate the molecules of the substance it passes through at certain frequencies and it becomes difficult for THz waves to pass through these molecules. This creates a spectral fingerprint that helps identify the material.
  • THz time-domain spectroscopy (TDS) technique has been used in the fields of medical diagnosis, defense and security, safety, and quality control in medicine and food, and successful results have been obtained so far.
  • the THz-TDS system both generates and detects THz signals in a coherent and time-triggered method using a femto-second laser.
  • This system has advantages over traditional far-IR (FTIR) or conventional THz systems with its high signal-to-noise ratio (SNR). While only the amplitude is obtained in traditional THz methods, the amplitude and phase information of the spectral components of the THz signal are obtained with the THz-TDS method. Thus, the refractive index of the studied sample and its complex dielectric and magnetic properties are determined.
  • the THz-TDS system has no radiation risk. Since it does not ionize biological molecules, it does not harm living organisms and is transparent to non-polar materials such as paper, plastic, ceramics. In addition, many chemical materials have unique fingerprint signals in this region.
  • THz-TDS systems have two optical arms, generation and detection, both of which are in the same experimental setup.
  • Ultra-fast lasers are used as the beam source and the incoming beam is divided into two branches. One of them produces THz radiation.
  • the THz waveform can be obtained as a function of time while scanning the sensory beam with interferometric steps.
  • the first measurement of the THz waveform is used as a reference.
  • FT Fourier transform
  • spectroscopic information about the sample is revealed.
  • the time shift of the main THz peak is related to the refractive index and the change in amplitude is related to the power absorption of the sample. This is the direct result of both amplitude and phase measurements of the THz electric field (Zhang and Xu, 2010).
  • the schematic view of the THz-TDS system (S) is given in Figure-1.
  • the light beam (I) emerging from the beam source (1) is split into two with the help of the beam splitter (3).
  • the rays (I), are directed by reflective mirrors (2).
  • the beam (I), which follows two paths called the generation path ( ) and the detector path (I2), are focused on the photoconductive antennas (THz emitter antenna (5a) and THz detector antenna (5b)) with the help of the objective lens (4).
  • the rays (I) emanating from the THz emitter antenna (5a) are directed to the sample holder (7) with the help of parabolic mirrors (6).
  • the signals released as a result of the interaction with the sample beam (I) and the beam coming from the detection path (I2) are also collected at the THz detector antenna (5b).
  • the lock-in amplifier (9) With the aid of the lock-in amplifier (9), the relationship between the excitant beam intensity and the THz electric field is obtained as a function of the delay time.
  • FIG-2 the graph of the THz signal (pulse) obtained from the THz-TDS system (S) is illustrated.
  • area 2 corresponds to the main THz signal.
  • Area 1 indicates the noise level and is used to calculate the noise since the THz signal has not yet been measured.
  • Area 3 represents oscillations in the electric field due to the absorption of the THz field.
  • the peaks of the reference (R) and the sample (S) and the voltage change and time delay that can be measured in line with these peaks can be calculated.
  • Figure-3 the power spectrum of the THz signal of the reference (R) and the sample (S) is given.
  • reflection type measurement, transmission type measurement and attenuated total reflection (ATR) type measurement methods as alternatives to THz-TDS system (S) are preferred for different purposes as they give positive results for their usage purposes.
  • reflection type measurement is used to determine sample thickness and deformation on pills in the pharmaceutical industry as well as imaging processes
  • transmission type measurement is frequently preferred in material characterization and plays an important role in detecting the determinant fingerprint in the THz frequency domain by also analyzing liquids in the form of thin films (100 pm).
  • the ATR method which has recently been used as an alternative to these two measurement systems, is mostly used in the analysis of liquids.
  • Patent application JP2012117966A describes a method developed for detecting organic matter suspended in a medium using terahertz spectroscopy. Mentioned organic substance is preferably a sugar, more preferably a monosaccharide or a disaccharide. It is stated in the application that the medium containing the organic material can be dried and preferably most of the water is removed from the sample by the drying process.
  • EP3087371B1 a method for the classification and grading of seeds is mentioned.
  • the invention relates to method for classifying and/or grading seeds using terahertz domain radiation, for example by terahertz time domain spectroscopy.
  • the present invention relates to the adulteration and authenticity analysis method of organic substances and materials by terahertz spectroscopy, which meets the above-mentioned requirements, eliminates all disadvantages and brings some additional advantages.
  • the purpose of the invention is to introduce a sample preparation and chemometric-based analysis method that enables the determination of quality control, adulteration and authenticity of all organic substances and materials, especially samples with high water content, by terahertz (THz) spectroscopy.
  • THz terahertz
  • the purpose of the invention is to develop an analysis method in which measurements are made in the THz electromagnetic region and the reliability of the measurement results with chemometric calculations is increased.
  • the purpose of the invention is to provide a simple, practical, fast and non-destructive sample preparation.
  • the purpose of the invention is to reduce the analysis time and cost.
  • the purpose of the invention is to create an analysis method of which sensitivity and accuracy is at least as good as known analysis methods.
  • One purpose of the invention is to present an ergonomic analysis method with a high potential for widespread use and application.
  • One purpose of the invention is to determine the origin of the sugar used in beverages with a simple, fast, accurate, and non-destructive method developed.
  • One purpose of the invention is to develop and use specific compounds that will create a complex with the analyse to provide more sensitive and accurate results.
  • the invention includes the process stages of: a.
  • the beam coming out of the beam source is split into two by arriving at the beam splitte by means of fiber cables used to reduce beam losses, b. the beam, which follows two paths, called the generation path and the detector path, focuses on the THz emitter antenna and the THz detector antenna with the help of the objective lens, c. applying an optical delay line in the detector path beam path using a moving stage to change the path length, d.
  • the rays coming from the generation path beam path and out of the THz emitter antenna are directed to the sample holder with the help of parabolic mirrors, e.
  • the signal information collected in the locking amplifier is analyzed with the help of the data processing program in the computer, and the refractive index of the sample is calculated with formula 1, the frequency-dependent calculation of the refractive index with formula 2 and the absorption with formula 3.
  • FIG. 1 It is the schematic view of the THz-TDS system
  • Figure-2 It is the graph of the THz signal (pulse) obtained from the THz-TDS system.
  • Figure-3 It is the power spectrum of the reference and sample THz signal
  • THz emitter antenna 5b THz detector antenna
  • Lock-in amplifier 10. Computer . Generation path l ⁇ . Detector path I. Ray N. Sample
  • the invention relates to the THz-TDS system (S), a sample preparation and chemometric- based analysis method that enables the determination of quality control, adulteration and authenticity of all organic substances and materials, especially samples with high water content.
  • S THz-TDS system
  • Sample preparation method to reduce losses in THz beam caused by high moisture content of organic samples includes the process steps of;
  • the rays (I) coming out of the beam source (1) are directed by reflective mirrors (2).
  • c is the speed of light (3x10 11 mm/s)
  • d is the sample thickness (mm)
  • At is the time difference (s).
  • / denotes frequency (Hz) and f phase (rad).
  • chemometric models are mathematical and statistical techniques that distinguish different groups from each other, exclude unnecessary data, and reveal the desired information.
  • multivariate data analysis methods used in qualitative data analysis are as follows:
  • RMSEC Root Mean Squared Error of Calibration
  • RMSECV Root Mean Squared Error of Cross-Validation
  • RMSEP Root Mean Squared Error of Prediction
  • the RMSE value is one of the quality parameters that expresses the difference between the value predicted by the model (ci) and the actually measured value (ci).
  • n indicates the number of concentrations studied.
  • Formula 4 is used to calculate three basic error values (RMSEC, RMSECV and RMSEP) to be used in comparing the performances of chemometric methods (PCA, PLS-DA, PLSR, PCR, MLR). Thanks to the sample preparation and chemometric-based analysis method developed with the invention, a fast, economical, accurate, sensitive, non-destructive, practical, and ergonomic method has been provided alternative to the analysis methods used to determine quality and adulteration.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Toxicology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

L'invention concerne le système (S) THz-TDS, une préparation d'échantillon et un procédé d'analyse basé sur la chimiométrie qui permet de déterminer la qualité, l'adultération et l'authenticité de toutes les substances et matières organiques, en particulier des échantillons ayant une teneur élevée en eau.
PCT/TR2022/050129 2021-02-19 2022-02-15 Procédé d'analyse d'adultération et d'authenticité de matières et substances organiques par spectroscopie térahertz Ceased WO2022177534A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/547,186 US20240142372A1 (en) 2021-02-19 2022-02-15 Adulteration and authenticity analysis method of organic substances and materials by terahertz spectroscopy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2021/002360 2021-02-19
TR202102360 2021-02-19

Publications (1)

Publication Number Publication Date
WO2022177534A1 true WO2022177534A1 (fr) 2022-08-25

Family

ID=82931822

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TR2022/050129 Ceased WO2022177534A1 (fr) 2021-02-19 2022-02-15 Procédé d'analyse d'adultération et d'authenticité de matières et substances organiques par spectroscopie térahertz

Country Status (1)

Country Link
WO (1) WO2022177534A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080165364A1 (en) * 2006-12-31 2008-07-10 Ziran Zhao Method and apparatus for assessing purity of vegetable oils by means of terahertz time-domain spectroscopy
US20110133090A1 (en) * 2009-12-09 2011-06-09 Encore Corporation Method of Detecting Organic Materials Using Terahertz Spectroscopy
DE102010050595A1 (de) * 2010-11-05 2012-05-10 Emcore Corp. Verfahren zum Detektieren organischer Materialien unter Verwendung der Terahertz Spektroskopie

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080165364A1 (en) * 2006-12-31 2008-07-10 Ziran Zhao Method and apparatus for assessing purity of vegetable oils by means of terahertz time-domain spectroscopy
US20110133090A1 (en) * 2009-12-09 2011-06-09 Encore Corporation Method of Detecting Organic Materials Using Terahertz Spectroscopy
DE102010050595A1 (de) * 2010-11-05 2012-05-10 Emcore Corp. Verfahren zum Detektieren organischer Materialien unter Verwendung der Terahertz Spektroskopie

Similar Documents

Publication Publication Date Title
JP6266719B1 (ja) テラヘルツ時間領域分光装置
US7652769B2 (en) Method and apparatus for assessing purity of vegetable oils by means of terahertz time-domain spectroscopy
Hsu Infrared spectroscopy
US9182282B2 (en) Multi-analyte optical computing system
US11408823B2 (en) Terahertz spectrum measurement method and system based on unequal optical path method
CN101419157B (zh) 一种利用太赫兹时域谱精确测定食用油光学参数的方法
CN106442401B (zh) 一种结合拉曼光谱和近红外光谱的探测装置及探测方法
KR20150037977A (ko) 이중 분광계
WO2008057913A2 (fr) Traitement de signal amélioré destiné à un système informatique
US20190277755A1 (en) Device and method for tissue diagnosis in real-time
CN109030406B (zh) 太赫兹频谱校准系统及方法
Indrayanto et al. The use of FTIR spectroscopy combined with multivariate analysis in food composition analysis
CN106442424A (zh) 利用石墨烯太赫兹表面等离子效应的酒精浓度测量装置及其方法
CN108918458B (zh) 一种确定材料太赫兹吸收峰的方法
WO2020130942A1 (fr) Système non destructif et procédé servant à déterminer la qualité d'une herbe chinoise par spectroscopie térahertz dans le domaine temporel
Pope Near-infrared spectroscopy of wood products
CN114152588A (zh) 反射式太赫兹时域光谱复合材料自参考光学参量测量方法
CN115561202B (zh) 一种绝缘油中甲醇的快速测量方法及装置
US20240142372A1 (en) Adulteration and authenticity analysis method of organic substances and materials by terahertz spectroscopy
WO2022177534A1 (fr) Procédé d'analyse d'adultération et d'authenticité de matières et substances organiques par spectroscopie térahertz
Gandhi et al. Infrared (IR) spectroscopy
US6411388B1 (en) System and method for frequency domain interferometric second harmonic spectroscopy
CN112229814B (zh) 太赫兹光谱测量装置、测量方法及其用途
binti Ishak et al. Non-destructive detection of fructose solutions via Terahertz spectroscopy enhanced by Frequency Selective Surface (FSS)
Cozzolino Fourier transform spectroscopy

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22756656

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 18547186

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22756656

Country of ref document: EP

Kind code of ref document: A1