WO2022267229A1 - 农产品、食品质量无损检测的包装材料、制备和检测方法 - Google Patents

农产品、食品质量无损检测的包装材料、制备和检测方法 Download PDF

Info

Publication number
WO2022267229A1
WO2022267229A1 PCT/CN2021/117104 CN2021117104W WO2022267229A1 WO 2022267229 A1 WO2022267229 A1 WO 2022267229A1 CN 2021117104 W CN2021117104 W CN 2021117104W WO 2022267229 A1 WO2022267229 A1 WO 2022267229A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
agricultural products
sample
food
packaging material
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/CN2021/117104
Other languages
English (en)
French (fr)
Inventor
谢丽娟
王英力
应义斌
刘湘江
李麟
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.)
Zhejiang University
Original Assignee
Zhejiang University
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 Zhejiang University filed Critical Zhejiang University
Priority to US18/034,089 priority Critical patent/US12280929B2/en
Publication of WO2022267229A1 publication Critical patent/WO2022267229A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5873—Removal of material
    • 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
    • G01N21/65—Raman scattering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the invention relates to a preparation and detection method of a packaging material used for non-destructive testing of agricultural products and food quality, in particular to the preparation of a packaging material that can amplify spectral signals and the quality inspection of food in the package when the food package is complete. method of detection.
  • Food packaging materials refer to paper, bamboo, wood, metal, enamel, ceramics, plastic, rubber, natural fiber, chemical fiber, glass and other products used for packaging and containing food or food additives, and coatings that directly contact food or food additives.
  • packaging materials In order to maintain the quality of food, prevent food from deteriorating during storage, distribution, and sales, prevent microbial contamination, and prevent superchemical and physical changes, all kinds of food must be packaged. In order to meet the needs of food packaging, it varies according to the type of food. As far as packaging materials are classified, there are: metal can packaging, glass bottle packaging, paper container packaging, plastic packaging, etc. However, these materials can only provide protection for food and do not have the function of detection.
  • the traditional detection method is manual sampling, which requires pre-processing of samples, and the packaging of food must be destroyed, which not only causes waste of samples, but also takes a long time to detect and cannot be detected online in real time.
  • Spectral detection technology has the advantages of short detection time, simple operation, non-destructive, etc., and is widely used in non-destructive testing of agricultural products and food quality.
  • the requirements of spectral detection are not considered in the production of ordinary food packaging materials, and spectral detection cannot be performed directly. If the signal of the spectrum can be enhanced by designing the corresponding packaging materials, the non-destructive quality inspection of the food in the food packaging can be directly carried out. This greatly improves the efficiency of food testing, and can also maintain the integrity of food without affecting secondary sales.
  • the technical problem to be solved by the present invention is to overcome the shortcomings of the above-mentioned background technology.
  • the food packaging materials can cooperate with spectral detection, so as to realize the quality inspection of food without opening the packaging.
  • the packaging material also has the characteristics of flexibility, high sensitivity, fast and convenient detection.
  • the invention also develops a matching spectral imaging method, which is simple and quick to operate, and is suitable for various detection requirements.
  • the packaging material of the present invention can use the structure of the packaging material to amplify the detection signal when the packaging is intact, so as to realize the function of non-destructive detection of agricultural products and food quality; the method of the present invention can also image food packaging, which is easy and fast to operate, and is suitable for various detection requirements.
  • the technical scheme that the present invention adopts comprises the steps:
  • a packaging material for non-destructive testing of agricultural products and food quality is provided.
  • the film material is mainly composed of a flexible base layer, an adhesive layer, a transparent conductive layer, and a nanostructure layer arranged sequentially from outside to inside.
  • the nanostructure layer is close to the inner side, and the flexible base layer is close to the surface.
  • the flexible base layer is a polydimethylsiloxane layer
  • the adhesive layer is a polyimide layer
  • the transparent conductive layer is an indium tin oxide layer
  • the nanostructure layer is Silver nanoparticle layer.
  • a layer of polyimide is spin-coated on the flexible base layer of polydimethylsiloxane, and then a layer of indium tin oxide film is sputtered on the polyimide to form a transparent conductive layer, and the nanoparticles self-assemble
  • the nanostructure layer is formed on the transparent conductive layer, and the spectral signal is amplified through the transparent conductive layer and the nanoparticle layer, so that it can be used for non-destructive testing of agricultural products and food quality.
  • the terahertz spectrum signal is amplified through the transparent conductive layer, and the Raman spectrum signal is amplified through the nanoparticle layer.
  • the flexible base layer, adhesive layer and transparent conductive layer are all transparent.
  • Indium tin oxide film has good electrical conductivity and optical transparency, and is generally produced by sputtering deposition technology. Ordinary flexible substrates are not resistant to the highest temperature, and direct sputtering deposition of indium tin oxide will cause deformation such as wrinkles.
  • the present invention uses polyimide as an adhesive layer to bond the flexible base layer and the transparent conductive layer, and the flexible base covered with the polyimide layer is not easily deformed during sputtering deposition of indium tin oxide, and at the same time it can realize High temperature resistant and transparent.
  • packaging materials used for non-destructive testing of agricultural products and food quality.
  • the packaging materials are produced in the following manner:
  • PDMS polydimethylsiloxane
  • a layer of indium tin oxide with a thickness of 200nm is deposited by sputtering on the surface of the adhesive layer as a transparent conductive layer;
  • the adhesive layer, the transparent conductive layer and the nanostructure layer are etched according to the preset metamaterial pattern, and the flexible base layer is not etched, so that the designed pattern is formed.
  • the nanostructure layer is obtained through the method of self-assembling nano particles, and the material of the nano particles is gold or silver, and the size is 10-80nm.
  • the material of the transparent conductive layer includes but is not limited to indium tin oxide, graphene, carbon nanowires, metal nanowires, etc.;
  • the manufacturing method of the transparent conductive layer includes but not limited to methods such as sputtering deposition, evaporation, deposition, spin coating and spray coating;
  • the etching techniques include, but are not limited to, photoetching, X-ray etching, electron beam etching, ion beam etching, wet etching, and laser engraving.
  • the thickness of the polydimethylsiloxane in the packaging layer is 10-200 ⁇ m; the thickness of the polyimide in the adhesive layer is 0.5-5 ⁇ m.
  • Changing the material, shape, and size of nanoparticles can still realize the function of spectral detection; adjusting the preset pattern can still realize the function of spectral detection.
  • the preset pattern is formed by a plurality of basic unit arrays arranged at intervals, and each basic unit is composed of a flexible base layer, an adhesive layer, a transparent conductive layer, and a nanostructure layer arranged sequentially from outside to inside.
  • the packaging materials used for non-destructive testing of agricultural products and food quality can be used for Raman spectrum detection and terahertz spectrum detection, but not limited to these two kinds of spectrum detection, but also include ultraviolet spectrum, visible light spectrum, infrared spectrum, fluorescence spectrum, hyperspectral Wait.
  • the terahertz time-domain spectra of the sample to be tested and the reference sample are collected respectively, and the terahertz frequency-domain signal is calculated according to the terahertz time-domain spectrum, and the reflection intensity between the sample to be tested and the reference sample at a specific frequency is calculated.
  • the difference is used as the detection signal, thereby realizing the amplification of the sample signal; select the required detection range for terahertz imaging, and judge the concentration and position of the sample according to the detection signal at a specific frequency;
  • samples correspond to different frequencies.
  • Pseudomonas aeruginosa corresponds to 0.8THz
  • other samples may correspond to 0.7THz.
  • the concentration and position of the sample can be judged according to the magnitude of the terahertz reflection intensity in the detection signal.
  • the Raman spectrometer uses a confocal microscope to focus on the sample to be tested, select the excitation light as 633nm, and the laser intensity as 0.5mW, and randomly collect 4 point Raman signals to realize Raman spectrum detection ; Adjust the sample stage of the Raman spectrometer to a horizontal state, select the required detection range and step size for Raman spectral imaging, and judge the concentration and position of the sample according to the intensity of the Raman spectral signal.
  • the concentration of the sample is judged according to the intensity of the Raman characteristic peak.
  • the amount of the sample solution added each time is 15 ⁇ L, and the drying temperature is 60-80° C.
  • the range of the time domain signal is 30 ps; the position of the frequency domain signal is 0.1-1.2 THz.
  • the sample solution includes, but is not limited to, sample solutions such as Pseudomonas aeruginosa and pyocyanin.
  • Raman spectroscopy can be used to detect pyocyanin, and terahertz spectroscopy can be used to detect Pseudomonas aeruginosa.
  • the packaging material can be directly attached to agricultural products and food for detection; a layer of edible gel can also be added on the nanostructure layer of the packaging material, so as to prevent the nano particles from contacting the agricultural products and food without affecting the detection results.
  • the DC184 polydimethylsiloxane solution produced by Dow Corning can be used, but not limited thereto.
  • the adhesive layer of the present invention includes but not limited to polyethersulfone (PES), polyetheretherketone (PEEK), polyimide (PI), polyamideimide (PAI) and other materials.
  • PES polyethersulfone
  • PEEK polyetheretherketone
  • PI polyimide
  • PAI polyamideimide
  • the preferred terahertz time-domain spectroscopy system of the present invention in specific implementation is recommended to adopt the terahertz time-domain spectroscopy system of model z3 produced by z-omega company.
  • the preferred Raman spectrum of the present invention in concrete implementation recommends adopting the model that HORIBA Jobin Yvon company produces is the Raman spectrometer of LABRAM HR Evolution.
  • the packaging material used for non-destructive testing of agricultural products and food quality of the present invention is a nanostructure layer-transparent conductive layer-flexible base layer structure.
  • Ordinary packaging materials have single functions and do not have the ability to amplify spectral signals.
  • the transparent conductive layer and the nanostructure layer can excite corresponding resonance peaks through the surface plasmon resonance effect, enhance the interaction between the spectrum and the substance, and then improve the detection sensitivity of the spectrum.
  • the outstanding advantage of the present invention is that the packaging material of the present invention has the ability to amplify spectral signals, and can perform quality inspection on internal food without damaging the packaging, without affecting sales.
  • the packaging material of the present invention can use the structure of the packaging material to amplify the detection signal when the packaging is intact, so as to realize the function of non-destructive detection of agricultural products and food quality; the method of the present invention can also image food packaging, which is easy and fast to operate, and is suitable for various detection requirements.
  • the present invention prepares the packing material technology of micro-nano structure, and its beneficial effect is:
  • the packaging material prepared by the invention utilizes its micro-nano structure to amplify spectral signals to realize spectral detection.
  • the invention utilizes the characteristic of spectral transmission of the packaging material to perform spectral detection on the food without opening the food packaging.
  • the packaging material used in the present invention can use a spectrometer to image the intact packaged food, thereby judging the internal conditions of the packaging material.
  • the method of the present invention realizes the quality detection of packaged food by preparing special packaging materials, increases the function of food packaging, and greatly improves the efficiency of food detection;
  • the method of the invention can use the metamaterial structure to amplify the spectrum signal, greatly improving the detection sensitivity; the method of the invention can image the packaged food, thereby ensuring the reliability of the detection result. Moreover, the method is simple and fast to operate, and can meet the increasing demand for rapid detection.
  • Fig. 1 is a schematic structural view of the packaging material used for non-destructive testing of agricultural products and food quality according to the present invention.
  • Fig. 2 is the terahertz spectrum of the packaging material used for non-destructive testing of agricultural products and food quality in Example 1 of the present invention with/without Pseudomonas aeruginosa.
  • Fig. 3 is a Raman spectrogram of the packaging material used for non-destructive testing of agricultural products and food quality in Example 1 of the present invention with/without pyocyanin molecules.
  • a flexible base layer (1) an adhesive layer (2), a transparent conductive layer (3), and a nanostructure layer (4).
  • Polyimide is spin-coated on the surface of the flexible substrate and cured by heating. Polyimide is used as an adhesive for bonding packaging and transparent conductive layers;
  • the LB film analyzer is used to monitor the tension of the water surface, so that the uniform and dense monomolecular layer of the nano-silver squares is completely transferred to the surface of the transparent conductive layer.
  • the nano-silver square layer will be used as a nano-structure layer to amplify Raman signals.
  • the adhesive layer, transparent conductive layer and nanostructure layer are etched into desired patterns.
  • the schematic diagram of the packaging material structure is shown in Figure 1.
  • the packaging material on the sample rack for testing and fill the terahertz time-domain system with nitrogen gas, so that the humidity inside the system drops below 0.1% before testing can be started; when the humidity is ⁇ 0.1%, collect the same The terahertz time-domain spectrum of the test sample point and the reference sample point on a multi-scale metamaterial in the 0.1-2THz interval, and then collect the terahertz time-domain spectrum of the calibration reference point; use the above method to obtain the terahertz time domain of each sample The terahertz time-domain spectrum data set of all sample points is obtained.
  • the time-domain signal of the terahertz spectrum of the sample is converted into a frequency-domain signal by fast Fourier transform, and the reflectivity of the sample point to be measured is obtained by using the frequency-domain signal. Find the intensity corresponding to the maximum value of the absorption peak, and subtract the intensity value of the sample point to be tested from the intensity value of the reference sample point to obtain the change in the intensity of the absorption peak.
  • Drop pyocyanin on the packaging materials used for non-destructive testing of agricultural products and food quality adjust the laser intensity, adjust the level of the sample, and collect the Raman of the sample points to be tested on the packaging materials used for non-destructive testing of agricultural products and food quality spectrum.
  • the Raman spectra of packaging materials used for non-destructive testing of agricultural products and food quality with or without pyocyanin are shown in Figure 3.
  • the packaging material prepared by the method of the present invention has a micro-nano structure, so that the food packaging material can cooperate with spectral detection, and the quality inspection of the packaged food can be carried out without opening the package.
  • the packaging material also has the characteristics of flexibility, high sensitivity, fast and convenient detection.
  • the invention also develops a matching spectral imaging method, which is simple and quick to operate, and can meet the growing demand for rapid detection.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Biochemistry (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

本发明公开了一种用于农产品、食品质量无损检测的包装材料的制备和检测方法。包括包装在农产品或者食品外的膜材料，是由从外到内依次层叠布置的柔性基底层、粘合层、透明导电层、纳米结构层构成，柔性基底层为聚二甲基硅氧烷层，粘合层为聚酰亚胺层，透明导电层为氧化铟锡层，纳米结构层为银纳米颗粒层；聚二甲基硅氧烷薄膜上旋涂聚酰亚胺固化，溅射氧化铟锡，将银纳米颗粒自组装到透明导电层上，按照图案刻蚀分离取下。本发明包装材料可以在包装完好的情况下利用包装材料自身结构放大检测信号，实现农产品、食品质量无损检测的功能；本发明方法还可以对食品包装成像，操作简便快速，适合多种检测需求。

Description

农产品、食品质量无损检测的包装材料、制备和检测方法 技术领域
本发明涉及一种用于农产品、食品质量无损检测的包装材料的制备和检测方法，尤其涉及一种可以放大光谱信号的包装材料的制备和在食品包装完整的情况下对包装中的食品进行质量检测的方法。
背景技术
食品包装材料指包装、盛放食品或者食品添加剂用的纸、竹、木、金属、搪瓷、陶瓷、塑料、橡胶、天然纤维、化学纤维、玻璃等制品和直接接触食品或者食品添加剂的涂料。为了保持食品的品质，使食品在保藏、流通、销售过程中不致变质，防止微生物的污染，防止超化学、物理变化，各种食品都必须采用包装。为了满足食品包装的需要，根据食品的种类不同。就包装材料分类，有：金属罐包装、玻璃瓶包装、纸容器包装、塑料包装等。然而这些材料只能为食品提供保护，不具备检测的功能。为了确保包装内农产品、食品的质量及可食用性，对农产品、食品包装内农产品、食品的检测变得尤其重要。传统检测方式是人工抽样，需要样品的提前处理，必须要破坏食品的包装，不仅造成样品的浪费，而且检测时间较长、无法在线实时检测。
光谱检测技术具有检测时间短、操作简单、无损等优点，被广泛用于农产品、食品质量无损检测。但普通的食品包装材料制作时并没有考虑光谱检测的要求，无法直接进行光谱检测。如果能够通过设计相应的包装材料增强光谱的信号，就可以直接对食品包装中的食品进行无损的质量检测。这大大提高了食品检测的效率，而且也能保持食品的完整性，不影响二次销售。
发明内容
本发明所要解决的技术问题是克服上述背景技术的不足，通过制备特殊的包装材料，使食品包装材料能够配合光谱检测，实现在不打开包装的前提下对食品进行质量检测。该包装材料还具有柔性、灵敏度性高、检测快速方便的特点。本发明还开发了配套的光谱成像方法，操作简便快速，适合多种检测需求。
本发明包装材料可以在包装完好的情况下利用包装材料自身结构放大检测信号，实现农产品、食品质量无损检测的功能；本发明方法还可以对食品包装成像，操作简便快速，适合多种检测需求。
本发明采用的技术方案包括如下步骤：
一、一种用于农产品、食品质量无损检测的包装材料：
包括包装在农产品或者食品外的膜材料，膜材料主要由从外到内依次层叠布置的柔性基底层、粘合层、透明导电层、纳米结构层构成，纳米结构层靠近内侧，柔性基底层靠近外侧，所述的柔性基底层为聚二甲基硅氧烷层，所述的粘合层为聚酰亚胺层，所述的透明导电层为氧化铟锡层，所述的纳米结构层为银纳米颗粒层。
本发明中，在聚二甲基硅氧烷的柔性基底层上旋涂一层聚酰亚胺，然后在聚酰亚胺上面溅射一层氧化铟锡膜形成透明导电层，纳米颗粒自组装形成在透明导电层上而形成纳米结构层，通过透明导电层和纳米颗粒层放大光谱信号，实现用于农产品、食品质量无损检测。
具体是通过透明导电层放大太赫兹光谱信号，通过纳米颗粒层放大拉曼光谱信号。
所述的柔性基底层、粘合层、透明导电层均为透明。
氧化铟锡膜具有良好的导电性和光学透明性，一般采用溅射沉积技术的制作。普通的柔性基底不耐最高温，直接溅射沉积氧化铟锡会产生皱褶等形变。本发明采用聚酰亚胺作为粘合层，用来粘合柔性基底层和透明导电层，覆盖聚酰亚胺层的柔性基底在溅射沉积氧化铟锡时也不易产生形变，同时也能实现耐高温透明。
二、用于农产品、食品质量无损检测的包装材料的制备方法，所述包装材料采用以下方式制作：
1)包装材料层的制备；
在清洗后的玻璃片旋涂一层聚二甲基硅氧烷(PDMS)混合液，加热固化形成柔性基底层，将柔性基底层从玻璃片上分离取下；
2)粘合层的制备；
先把柔性基底层进行等离子清洗，然后在柔性基底层上旋涂一层聚酰亚胺，在200℃下固化2h，形成粘合层；
3)透明导电层的制备：
在粘合层的表面溅射沉积厚度200nm的氧化铟锡层，作为透明导电层；
4)纳米结构层的制备；
合成银纳米颗粒，将银纳米颗粒在透明导电层上自组装成为纳米结构层；
5)制作超材料图案：
按照预设的超材料图案对粘合层、透明导电层和纳米结构层进行刻蚀，柔 性基底层不进行刻蚀，使形成所设计的图案。
所述纳米结构层为通过自组装纳米颗粒的方法得到的，纳米颗粒的材质为金或银，大小为10-80nm。
所述透明导电层的材料包括但不限于氧化铟锡、石墨烯、碳纳米线、金属纳米线等；
所述透明导电层的制作方法包括但不限于溅射沉积、蒸镀、沉积、旋涂和喷涂等方法；
所述刻蚀技术包括但不限于光刻蚀、X射线刻蚀、电子束刻蚀、离子束刻蚀、湿法刻蚀和激光雕刻等。
所述的包装层的聚二甲基硅氧烷的厚度是10-200μm；所述的粘合层的聚酰亚胺的厚度是0.5-5μm。
改变纳米颗粒的材质、形貌、尺寸仍然可以实现光谱检测的功能；调整预设的图案仍然可以实现光谱检测的功能。
所述预设的图案是由多个基本单元阵列间隔排布而成，每个基本单元均由从外到内依次层叠布置的柔性基底层、粘合层、透明导电层、纳米结构层构成。
所述用于农产品、食品质量无损检测的包装材料可用于拉曼光谱检测和太赫兹光谱检测，但不仅限于这两种光谱检测，也包括紫外光谱、可见光光谱、红外光谱、荧光光谱、高光谱等。
S1、包装材料滴加样品溶液：
配置所需的样品溶液，将样品溶液滴加在包装材料上，具体是滴加到纳米结构层上，并在60℃下干燥，获得待测样本；取未滴加样品溶液的包装材料作为参考样本；
S2、太赫兹光谱成像检测：
在湿度<0.1RH时，分别采集待测样本和参考样本的太赫兹时域光谱，根据太赫兹时域光谱计算太赫兹频域信号，以待测样本和参考样本之间在特定频率下反射强度的差值作为检测信号，由此实现对样品信号的放大；选取所需检测的范围进行太赫兹成像，根据特定频率下的检测信号来判断样品的浓度和位置；
特定意思是不同的样品对应不同的频率。比如绿脓杆菌对应的0.8THz，其他的样品对应的可能是0.7THz。根据该频率下，根据检测信号中太赫兹反射强度的大小判断样品的浓度和位置。
S3、拉曼光谱成像检测：
将待测样本放在拉曼光谱仪样品台上，使用共聚焦显微镜对待测样本进行对焦，选择激发光为633nm，激光强度为0.5mW，随机采集4个点拉曼信号， 从而实现拉曼光谱检测；将拉曼光谱仪样品台调节至水平状态，选取所需检测的范围和步长进行拉曼光谱成像，根据拉曼光谱信号的强度来判断样品的浓度和位置。
具体是根据拉曼特征峰强度的大小判断样品的浓度。拉曼特征峰强度越大，样品的浓度越高，根据成像可以看出样品的位置。
所述S1中，样品溶液的每次滴加量为15μL，干燥温度60-80℃。
所述S2中，时域信号的范围是30ps；频域信号的位置为0.1-1.2THz。
所述的样品溶液包括但不限于绿脓杆菌和绿脓菌素等样品溶液，可以利用拉曼光谱检测绿脓菌素，利用太赫兹光谱检测绿脓杆菌。
所述的包装材料可以直接贴合农产品和食品进行检测；也可以在包装材料的纳米结构层上添加一层食用凝胶，从而避免纳米颗粒接触农产品和食品，这样也不影响检测结果。
优选的本发明聚二甲基硅氧烷溶液具体实施中可选用道康宁公司生产的型号为DC184的聚二甲基硅氧烷溶液，但不限于此。
本发明的粘合层包括但不限于聚醚砜(PES)、聚醚醚酮(PEEK)、聚酰亚胺(PI)、聚酰胺酰亚胺(PAI)等材料。
具体实施中优选的本发明的太赫兹时域波谱系统推荐采用z-omega公司生产的型号为z3的太赫兹时域波谱系统。
具体实施中优选的本发明的拉曼光谱推荐采用HORIBA Jobin Yvon公司生产的型号为LABRAM HR Evolution的拉曼光谱仪。
本发明的用于农产品、食品质量无损检测的包装材料是一种纳米结构层-透明导电层-柔性基底层结构。普通的包装材料功能单一，不具有放大光谱信号的能力。透明导电层和纳米结构层可通过表面等离子体共振效应激发出相应的共振峰，增强光谱与物质的相互作用，进而提升光谱的检测灵敏度。本发明的突出优势在于本发明方法的包装材料具有放大光谱信号的能力，可以在不破坏包装的情况下对内部食品进行质量检测，不影响销售。
本发明包装材料可以在包装完好的情况下利用包装材料自身结构放大检测信号，实现农产品、食品质量无损检测的功能；本发明方法还可以对食品包装成像，操作简便快速，适合多种检测需求。由此，本发明制备微纳结构的包装材料技术，其具有的有益效果是：
本发明制备的包装材料，利用其微纳结构放大光谱信号，实现光谱检测。
本发明同时利用包装材料光谱透过的特性，在不打开食品包装的情况下对食品进行光谱检测。
本发明采用的包装材料，可利用光谱仪对完好的包装食品成像，从而判断包装材料内部的情况。
与传统的包装材料相比，本发明方法通过制备特殊的包装材料，从而实现包装食品的质量检测，增加了食品包装的功能，大大的提高了食品检测的效率；
与普通的光谱检测相比，本发明方法能利用超材料结构放大光谱信号，大大提高检测灵敏度；本发明方法能对包装食品进行成像，从而保证检测结果的可靠性。并且本方法操作简便快速，能满足日益增长的快速检测需求。
附图说明
图1为本发明用于农产品、食品质量无损检测的包装材料的结构示意图。
图2为本发明实施例1中用于农产品、食品质量无损检测的包装材料在有/无绿脓杆菌情况下的太赫兹光谱图。
图3为本发明实施例1中用于农产品、食品质量无损检测的包装材料在有/无绿脓素分子情况下的拉曼光谱图。
图中：柔性基底层(1)、粘合层(2)、透明导电层(3)、纳米结构层(4)。
具体实施方式
下面结合实施实例对本发明作进一步说明，但本发明并不限于以下实施例。
本发明的实施例如下：
实施例1
(1)柔性基底层的制作；
取平整的石英片或者硅片放在丙酮、乙醇和水中各超声清洗5min，将其干燥后，在表面旋涂聚二甲基硅氧烷并加热固化，聚二甲基硅氧烷作为柔性基底层；
(2)粘合层的制作；
在柔性基底表面旋涂聚酰亚胺并加热固化，聚酰亚胺作为粘合，用于粘合包装和透明导电层；
(3)透明导电层的制作；
在聚酰亚胺上面蒸镀200nm的氧化铟锡作为透明导电层。
(4)纳米结构层的制作；
首先合成43nm的纳米银方块；配置0.1mg/mL的PEG-SH的三氯甲烷溶液；将纳米银方块溶液、PEG-SH的三氯甲烷溶液、甲醇溶液以1:1:1的体积比充分混合。将混合液以8000rpm的转速离心15min，抛弃上清液，用三氯甲烷溶液将沉淀复溶至原来的三分之一；在以8000rpm的转速离心15min，抛弃上 清液，用三氯甲烷溶液将沉淀复溶至原来的三分之一；在以8000rpm的转速离心15min，抛弃上清液，用三氯甲烷溶液将沉淀复溶至原来的十分之一。利用注射器以0.4mL/min的速度缓慢注射至水溶液表面。利用LB膜分析仪监测水面的张力，从而将纳米银方块均一致密的单分子层并且完整的转移到透明导电层表面。纳米银方块层将作为纳米结构层，用以放大拉曼信号。
(5)超材料结构的制作；
将粘合层、透明导电层和纳米结构层刻蚀成为所需要的图案。包装材料结构示意图如图1所示。
(6)获取绿脓杆菌及其分泌物绿脓菌素；
取培养12小时的绿脓杆菌液1mL，本实施实例中细菌OD 600＝1
(7)包装材料表面滴加绿脓杆菌溶液；
取15μL绿脓杆菌溶液，滴加在包装材料表面，在60℃下烘干，以上步骤重复三次，获得三个待测样品点，每个待测样品点的检测面积约为20mm 2；并设置三个参考样品点(仅包装材料，没有滴加任何物质)。
(8)采集包装材料表面的待测样品点和参考样品点的太赫兹时域波谱；
开启太赫兹时域系统的电源箱和电脑。打开采集板电源和延迟线开关。打开太赫兹系统的控制软件，设置延迟线分辨率0.5um，延迟线速度等级设置为2，延迟线范围起始位置设为50000，结束位置设置为40000。打开激光器电源，开始采集信号。将包装材料放到检测的样品架上，并且给太赫兹时域系统内充入氮气，使系统内部的湿度降至0.1％以下后才可以开始检测；湿度<0.1％的情况下，分别采集同一多尺度超材料上待测样品点与参考样品点在0.1-2THz区间内的太赫兹时域波谱，然后采集校准参照点的太赫兹时域光谱；用以上方法获取每一个样本的太赫兹时域波谱，得到所有样品点的太赫兹时域波谱数据组。利用快速傅里叶变换将样品的太赫兹波谱时域信号转换到频域信号，利用频域信号得到待测样品点的反射率。寻找吸收峰最大值对应的强度，并将待测样品点的该强度值与参考样品点的该强度值相减，得到吸收峰强度的变化。
用于农产品、食品质量无损检测的包装材料在有/无绿脓杆菌情况下的吸收谱线如图2所示。
(7)采集用于农产品、食品质量无损检测的包装材料表面的绿脓菌素的拉曼光谱信号；
在用于农产品、食品质量无损检测的包装材料上滴加绿脓菌素，调节激光强度，将样品调节水平，分别采集用于农产品、食品质量无损检测的包装材料上待测样品点的拉曼光谱。用于农产品、食品质量无损检测的包装材料在有/无 绿脓菌素情况下的拉曼光谱如图3所示。
由此上述实施可见，本发明方法制备的包装材料具有微纳结构，使食品包装材料能够配合光谱检测，在不打开包装的前提下可以对包装食品进行质量检测。该包装材料还具有柔性、灵敏度性高、检测快速方便的特点。本发明还开发了配套的光谱成像方法，操作简便快速，能满足日益增长的快速检测需求。上述具体实施方式用来解释说明本发明，而不是对本发明进行限制，在本发明的精神和权利要求的保护范围内，对本发明做出的任何修改和改变，都落入本发明的保护范围。

Claims (10)

  1. 一种用于农产品、食品质量无损检测的包装材料，其特征在于：包括包装在农产品或者食品外的膜材料，膜材料主要由从外到内依次层叠布置的柔性基底层(1)、粘合层(2)、透明导电层(3)、纳米结构层(4)构成，所述的柔性基底层为聚二甲基硅氧烷层，所述的粘合层为聚酰亚胺层，所述的透明导电层为氧化铟锡层，所述的纳米结构层为银纳米颗粒层。
  2. 根据权利要求1所述的一种用于农产品、食品质量无损检测的包装材料，其特征在于：在聚二甲基硅氧烷的柔性基底层上旋涂一层聚酰亚胺，然后在聚酰亚胺上面溅射一层氧化铟锡膜形成透明导电层，纳米颗粒自组装形成在透明导电层上而形成纳米结构层，通过透明导电层和纳米颗粒层放大光谱信号，实现用于农产品、食品质量无损检测。
  3. 根据权利要求1所述的一种用于农产品、食品质量无损检测的包装材料，其特征在于：所述的柔性基底层(1)、粘合层(2)、透明导电层(3)均为透明。
  4. 一种权利要求1所述的用于农产品、食品质量无损检测的包装材料的制备方法，其特征在于：所述包装材料采用以下方式制作：
    1)包装材料层的制备；
    在清洗后的玻璃片旋涂一层聚二甲基硅氧烷(PDMS)混合液，加热固化形成柔性基底层，将柔性基底层从玻璃片上分离取下；
    2)粘合层的制备；
    先把柔性基底层进行等离子清洗，然后在柔性基底层上旋涂一层聚酰亚胺，在200℃下固化2h，形成粘合层；
    3)透明导电层的制备：
    在粘合层的表面溅射沉积厚度200nm的氧化铟锡层，作为透明导电层；
    4)纳米结构层的制备；
    合成银纳米颗粒，将银纳米颗粒在透明导电层上自组装成为纳米结构层；
    5)制作超材料图案：
    按照预设的超材料图案对粘合层、透明导电层和纳米结构层进行刻蚀，使形成所设计的图案。
  5. 根据权利要求4所述的用于农产品、食品质量无损检测的包装材料的制备方法，其特征在于：
    所述纳米结构层为通过自组装纳米颗粒的方法得到的，纳米颗粒的材质为 金或银，大小为10-80nm。
  6. 根据权利要求4所述的用于农产品、食品质量无损检测的包装材料包装材料的制备方法，其特征在于：所述的包装层的聚二甲基硅氧烷的厚度是10-200μm；所述的粘合层的聚酰亚胺的厚度是0.5-5μm。
  7. 根据权利要求4所述的用于农产品、食品质量无损检测的包装材料的制备方法，其特征在于：所述预设的图案是由多个基本单元阵列间隔排布而成，每个基本单元均由从外到内依次层叠布置的柔性基底层、粘合层、透明导电层、纳米结构层构成。
  8. 权利要求1所述用于农产品、食品质量无损检测的包装材料的光谱成像检测方法，其特征在于：方法包括：
    S1、包装材料滴加样品溶液：
    配置所需的样品溶液，将样品溶液滴加在包装材料上，具体是滴加到纳米结构层上，并在60℃下干燥，获得待测样本；取未滴加样品溶液的包装材料作为参考样本；
    S2、太赫兹光谱成像检测：
    在湿度<0.1RH时，分别采集待测样本和参考样本的太赫兹时域光谱，根据太赫兹时域光谱计算太赫兹频域信号，以待测样本和参考样本之间在特定频率下反射强度的差值作为检测信号；选取所需检测的范围进行太赫兹成像，根据特定频率下的检测信号来判断样品的浓度和位置；
    S3、拉曼光谱成像检测：
    将待测样本放在拉曼光谱仪样品台上，使用共聚焦显微镜对待测样本进行对焦，选择激发光为633nm，激光强度为0.5mW，随机采集4个点拉曼信号，从而实现拉曼光谱检测；将拉曼光谱仪样品台调节至水平状态，选取所需检测的范围和步长进行拉曼光谱成像，根据拉曼光谱信号的强度来判断样品的浓度和位置。
  9. 根据权利要求8所述用于农产品、食品质量无损检测的包装材料的光谱成像检测方法，其特征在于：所述S1中，样品溶液的每次滴加量为15μL，干燥温度60-80℃。
  10. 根据权利要求9所述用于农产品、食品质量无损检测的包装材料的光谱成像检测方法，其特征在于：所述的包装材料可以直接贴合农产品和食品进行检测；也可以在包装材料的纳米结构层上添加一层食用凝胶，从而避免纳米颗粒接触农产品和食品，这样也不影响检测结果。
PCT/CN2021/117104 2021-06-24 2021-09-08 农产品、食品质量无损检测的包装材料、制备和检测方法 Ceased WO2022267229A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US18/034,089 US12280929B2 (en) 2021-06-24 2021-09-08 Packaging material for non-destructive detection of food quality, preparation method of packaging material, and detection method using packaging material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110704597.8 2021-06-24
CN202110704597.8A CN113459616B (zh) 2021-06-24 2021-06-24 农产品、食品质量无损检测的包装材料、制备和检测方法

Publications (1)

Publication Number Publication Date
WO2022267229A1 true WO2022267229A1 (zh) 2022-12-29

Family

ID=77872782

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/117104 Ceased WO2022267229A1 (zh) 2021-06-24 2021-09-08 农产品、食品质量无损检测的包装材料、制备和检测方法

Country Status (3)

Country Link
US (1) US12280929B2 (zh)
CN (1) CN113459616B (zh)
WO (1) WO2022267229A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116433097A (zh) * 2023-04-19 2023-07-14 北京市永康药业有限公司 一种注射剂包装质量检测方法及系统

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115856016A (zh) * 2022-12-30 2023-03-28 浙江理工大学 一种基于复合材料表面导电层的主动式红外检测方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101137898A (zh) * 2005-03-07 2008-03-05 3M创新有限公司 具有金属纳米颗粒涂层的热塑性薄膜
CN101716839A (zh) * 2009-11-23 2010-06-02 南京大学 一种表面增强拉曼用大面积金属纳米结构衬底及其制备方法
US20120276549A1 (en) * 2011-04-29 2012-11-01 The Board of Trustees of the University of Illinois SRU Biosystems, Inc. Photonic biosensors incorporated into tubing, methods of manufacture and instruments for analyziing the biosensors
CN109060762A (zh) * 2018-07-27 2018-12-21 山东师范大学 基于银纳米颗粒的复合柔性表面增强拉曼基底及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003709A (en) * 1975-10-02 1977-01-18 Visual Spoilage Indicator Company Visual spoilage indicator for food containers
US4285697A (en) * 1978-09-26 1981-08-25 Neary Michael P Food spoilage indicator
US5407829A (en) * 1990-03-27 1995-04-18 Avl Medical Instruments Ag Method for quality control of packaged organic substances and packaging material for use with this method
US8330951B2 (en) * 2006-04-28 2012-12-11 Hewlett-Packard Development Company, L.P. Nano-enhanced Raman spectroscopy substrate packaging structure
WO2008091858A2 (en) * 2007-01-23 2008-07-31 President & Fellows Of Harvard College Non-invasive optical analysis using surface enhanced raman spectroscopy
US8865402B2 (en) * 2009-08-26 2014-10-21 Clemson University Research Foundation Nanostructured substrates for surface enhanced raman spectroscopy (SERS) and detection of biological and chemical analytes by electrical double layer (EDL) capacitance
CN102628807B (zh) * 2012-03-31 2015-12-02 中国科学院合肥物质科学研究院 基于表面增强拉曼光谱探测痕量生物分子电离辐射分解反应的方法
JP2015105837A (ja) * 2013-11-28 2015-06-08 学校法人早稲田大学 光学デバイスおよび分析装置
US10241099B2 (en) * 2014-03-20 2019-03-26 Agency For Science, Technology And Research Film sensor
CN104251852A (zh) * 2014-08-28 2014-12-31 苏州佳因特光电科技有限公司 一种基于无电沉积法构建的表面增强拉曼散射基底及其制备方法和应用
US20190002179A1 (en) * 2015-08-26 2019-01-03 Åbo Akademi Nanostructured latex film for controlling and monitoring bacterial cell growth in food packaging
CN113463020B (zh) * 2021-06-24 2022-04-29 浙江大学 一种多波段可调多尺度超材料的制备方法和光谱检测方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101137898A (zh) * 2005-03-07 2008-03-05 3M创新有限公司 具有金属纳米颗粒涂层的热塑性薄膜
CN101716839A (zh) * 2009-11-23 2010-06-02 南京大学 一种表面增强拉曼用大面积金属纳米结构衬底及其制备方法
US20120276549A1 (en) * 2011-04-29 2012-11-01 The Board of Trustees of the University of Illinois SRU Biosystems, Inc. Photonic biosensors incorporated into tubing, methods of manufacture and instruments for analyziing the biosensors
CN109060762A (zh) * 2018-07-27 2018-12-21 山东师范大学 基于银纳米颗粒的复合柔性表面增强拉曼基底及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116433097A (zh) * 2023-04-19 2023-07-14 北京市永康药业有限公司 一种注射剂包装质量检测方法及系统
CN116433097B (zh) * 2023-04-19 2023-11-21 北京市永康药业有限公司 一种注射剂包装质量检测方法及系统

Also Published As

Publication number Publication date
CN113459616B (zh) 2022-06-17
US20230391521A1 (en) 2023-12-07
CN113459616A (zh) 2021-10-01
US12280929B2 (en) 2025-04-22

Similar Documents

Publication Publication Date Title
CN114018857B (zh) 一种超表面传感器及其制备方法
CN104568849B (zh) 三维亚波长金属腔体结构光谱多带光完美吸收等离激元传感器及其制备方法与用途
CN111766221A (zh) 一种基于Fano共振太赫兹超表面生物传感器及其制备方法
Shi et al. Synthesis of flexible and stable SERS substrate based on Au nanofilms/cicada wing array for rapid detection of pesticide residues
US12292377B2 (en) Multi-waveband-tunable multi-scale meta-material and preparation method and spectral detection method thereof
CN108827903B (zh) 太赫兹非双各向异性超构材料无标记传感器及制备和用途
TWI404930B (zh) Biochemical sensing wafer substrate and its preparation method
CN113459616B (zh) 农产品、食品质量无损检测的包装材料、制备和检测方法
CN108169171B (zh) 一种基于表面等离子激元共振的折射率测试及其制作方法
CN110208245A (zh) 一种纸基柔性表面增强拉曼散射效应基片及其制备方法
CN104764732A (zh) 基于特异材料超吸收体的表面增强拉曼散射基底及其制备方法
CN115818554B (zh) Ag/Ag2O/Ag纳米球阵列SERS基底、制备方法及应用
Li et al. Antenna enhanced infrared photoinduced force imaging in aqueous environment with super-resolution and hypersensitivity
CN106556587A (zh) 基于二维硒化锡纳米片的表面增强拉曼基底及制备方法
CN114199828B (zh) 一种基于金属-石墨烯杂化超表面生物传感器及其制备方法
CN108827933A (zh) 一种表面增强拉曼散射基底及其制备方法和应用
Sun et al. Preparation and gas-sensing property of a nanosized titania thin film towards alcohol gases
CN105911013A (zh) 一种分子检测用硫系玻璃薄膜生物传感芯片及其制备方法
CN110132936A (zh) 一种Al/Ag层状纳米结构的大面积SERS基底、制备方法及应用
CN116837324B (zh) 一种以铝为蒸发材料制备表面等离子体共振芯片的方法
CN118145590A (zh) 一种用于电磁场增强的纳米阵列及其制备方法和应用
CN212904522U (zh) 一种光学各向异性生物传感芯片
Westwood et al. Combined QCMD and AFM studies of lysozyme and poly-l-lysine–poly-galacturonic acid multilayers
US9365420B2 (en) Three-dimensional dispersible nanoresonator structure for biological, medical and environmental applications and method for manufacture thereof
Hassan et al. Surface plasmon resonance studies on spin coated films of azobenzene-substituted calix-4-resorcinarene molecules

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: 21946713

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 18034089

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: 21946713

Country of ref document: EP

Kind code of ref document: A1

WWG Wipo information: grant in national office

Ref document number: 18034089

Country of ref document: US