Ultrahigh-resolution colorimetric sensor based on thickness gradient responsive film and application thereof

Abstract

The invention discloses an ultra-high resolution colorimetric sensor based on a thickness gradient responsive film and application thereof, the colorimetric sensor comprises a substrate and a responsive biopolymer film formed on the substrate, the thickness of the film is gradually reduced from the center to the edge, the thickness of the center is 300-600nm, and the thickness difference from the center to the edge is 120-200nm; the responsive biopolymer is a protein core-shell structure nanocrystal, a responsive block polymer, a reflective protein, a silk or a cellulose nanocrystal. Compared with the spatial resolution of 18nm in the traditional film interference colorimetric method, the spatial resolution of the sensor disclosed by the invention reaches 0.018 nm, the cost is low, the sensor is convenient to use, and only a simple camera is needed. The preparation of the sensor with the thickness gradient structure can be realized by spin-coating the responsive (biological) polymer on the substrate in two steps, and the sensor can be used for detecting relative humidity and organic amine steam. Compared with a reflection spectrum sensing method based on an optical fiber spectrometer, the method provided by the invention has the advantage that the sensitivity can be improved by 3-8 times.

Description

Technical Field

[0001] The present invention belongs to the technical field of the preparation and application of optical sensors, and particularly relates to a colorimetric sensor with a gradient thickness structure and the application of a color difference spectrum based on the gradient structure. In particular, compared with traditional colorimetric sensors, it can significantly improve the sensing spatial resolution. Background Art

[0002] By reasonably combining responsive assembly units and photonic structures, high-performance structural color sensors can be designed. For example, natural biopolymers such as reflective proteins, bacteriophages, silk, and cellulose nanocrystals have received extensive attention in the creation of structural color sensors due to their good biocompatibility and rapid responsiveness. In the corresponding sensing mechanism, when the target stimulant interacts with the corresponding polymer, the photonic structure swells or deflates, resulting in a color change. Among many photonic structures, thin-film interference is the simplest method to produce structural color and is widely used for the sensing of chemical or physical stimuli. The principle is that when the polymer coating is comparable to the wavelength of visible light, the reflected light beams from the upper interface and the substrate interface of the polymer coating will undergo coherent interference, thus producing structural color. In this color-changing mechanism, when the polymer coating undergoes stimulus-responsive swelling, the wavelengths of coherent enhancement (peak) or cancellation (valley) in the reflection spectrum shift, and the change in the interference color can be observed by the naked eye or a camera. In this sensing method, external interference factors such as brightness and camera white balance will seriously affect the acquisition of chromaticity coordinates (such as RGB and HSV values). In addition, due to the detection limit of the naked eye or a camera for color difference, in colorimetric sensing based on thin-film interference, color-response resolution is quite limited. Generally, this detection limit is defined as the shortest measurable Euclidean distance (△E 00 ) between the color coordinates of the thin film before and after swelling. As the critical condition for perceivable difference, △E 00 must be greater than 2.3 (the corresponding change in the thin-film thickness is about 18 nm) to generate an effective signal. When the concentration of the input stimulus is extremely low, the change in the thin-film thickness is extremely small, which is very likely to make △E 00 less than 2.3, making it difficult to obtain a detectable color change. The leading examples of current colorimetric devices and sensors still heavily rely on the development of spectral or angular optical interrogation techniques and have proposed some strategies to optimize the photonic structure to enhance the reflectance spectral response, such as introducing a reflective coating on a noble metal substrate and constructing a metasurface by lithography. In contrast, there are few reports on improving the color-based sensing performance. Therefore, it is still a great challenge to overcome the above limitations of chromaticity sensing itself by designing and manufacturing advanced photonic structures. Summary of the Invention

[0003] The object of the present invention is to provide an ultra-high resolution colorimetric sensor based on a thickness gradient responsive film. For detecting the thickness change caused by stimulus-response, the sensor can achieve a spatial resolution of 0.018 nm, can realize a 3-8 times sensitivity improvement, and at the same time has the advantages of low cost, easy use, and only requires a simple camera, etc.

[0004] To achieve the above object, the ultra-high resolution colorimetric sensor based on a thickness gradient responsive film provided by the present invention includes a substrate, and a responsive film formed by spin-coating a responsive polymer on the substrate. The thickness of the film shows a gradually decreasing gradient distribution from the center to the edge, the thickness at the center is 300-600 nm, and the thickness difference from the center to the edge is 120-200 nm.

[0005] The above-mentioned responsive polymer is selected from any one of protein core-shell structure nanocrystals, responsive block polymers, reflective proteins, silk, and cellulose nanocrystals.

[0006] The above-mentioned substrate is any one of a silicon substrate, a gold substrate, and a platinum substrate.

[0007] The above-mentioned protein core-shell structure nanocrystals are selected from animal-derived protein core-shell structure nanocrystals or plant-derived protein core-shell structure nanocrystals.

[0008] The above-mentioned animal-derived protein core-shell structure nanocrystals are core-shell structure nanocrystals of at least one of the proteins contained in the following animals:

[0009] (1) Coleoptera, Insecta, Arthropoda: Staphylinidae, Elateridae, Scarabaeoidea, Cerambycidae, Chrysomeloidea, Curculionoidea, Pentatomidae, Haliplidae, Hydrophilidae, Dryopoidea, Buprestoidea, Cicindelidae, Curculionidae, Coccinellidae, Lycidae, Carabidae, Eucnemidae, Throscidae, Ctenostethidae;

[0010] (2) Hymenoptera, Insecta, Arthropoda: Ichneumonidae, Braconidae, Chalcididae, Cynipidae, Sphecidae, Vespidae, Formicidae, Apidae, Tenthredinidae, Diprionidae, Siricidae, Xiphydriidae, Pteromalidae, Eulophidae, Trichogrammatidae, Mymaridae, Proctotrupidae, Diapriidae, Scelionidae, Platygastridae;

[0011] (3) Lepidoptera, Insecta, Arthropoda: Micropterigidae, Cosmopterigidae, Xyloryctidae, Yponomeutoidea, Plutellidae, Glyphipterigidae, Heliodinidae, Tortricidae, Limacodidae, Zygaenidae, Tineidae, Psychidae, Gelechiidae, Yponomeutidae, Sesiidae, Arctiidae, Noctuidae, Bombycidae, Lasiocampidae, Geometridae;

[0012] (4) Class Malacostraca, Phylum Arthropoda: Phyllocarididae, Macrophyllocarididae, Phyllocaridopsidae, Benthosquilloidea, Indosquillidae, Eurysquillidae, Hemisquillidae, Gonodactylidae, Odontodactylidae, Protosquillidae, Pseudosquillidae, Takuidae, Erythrosquillidae, Coronosquillidae, Lysiosquillidae, Nannosquillidae, Tylosquillidae, Squillidae, Eurysquillidae, Parasquillidae;

[0013] (5) Order Araneae, Class Arachnida, Phylum Arthropoda: Araneidae, Argiopidae, Agelenidae, Thomisidae, Lycosidae, Salticidae, Scorpionidae, Ixodidae, Acaridae, Trombiculidae, Tetranychidae, Clubionidae, Amaurobiidae, Tetragnathidae, Theraphosidae, Theridiidae, Latrodectidae, Theraphosidae, Coronatae, Dictynidae;

[0014] (6) Order Scorpiones, Class Arachnida, Phylum Arthropoda: Parabuthidae, Buthidae, Microcharmidae, Chactidae, Buthidae, Euscorpiidae, Hadogenesidae, Vaejovidae, Trichotonidae, Ischnuridae, Bothriuridae, Scorpionidae, Heteroscorpionidae, Diplocentridae, Liochelidae;

[0015] (7) Order Cephalaspidea, Class Gastropoda, Phylum Mollusca: Acteocinidae, Aglajidae, Atyidae, Cymatiidae, Bulimulidae, Glaucidae, Cochlespiridae, Pholadellidae, Pleurobranchaeidae, Janthinidae, Umbraculidae, Philinidae, Retusidae, Ovulidae;

[0016] (8) Order Anaspidea, Class Gastropoda, Phylum Mollusca: Terebridae, Aplysiidae, Phyllidiidae, Haminoeidae, Acteonidae, Janthinidae, Ovulidae, Aplustridae;

[0017] (9) Order Nudibranchia, Class Gastropoda, Phylum Mollusca: Dorididae, Discodorididae, Phyllidiidae, Flabellinidae, Aeolidiidae, Chromodorididae, Dendronotidae, Polyceridae, Dendronotidae, Aeolidiidae, Polyceridae, Hexabranchidae;

[0018] (10) Order Sepiida, Class Cephalopoda, Phylum Mollusca: Sepiidae, Sepiadariidae, Sepiadinae, Sepiolinae;

[0019] (11) Order Octopoda, Class Cephalopoda, Phylum Mollusca: Octopodidae, Enteroctopodidae, Octopodidae, Sepiadariidae, Argonautidae, Haliphronidae, Bathypolypodidae, Octopodidae;

[0020] (12)Phylum Chordata, Class Actinopterygii: Acipenseridae of Acipenseriformes, Elopidae of Elopiformes, Gonorynchidae of Gonorynchiformes, Neoscopelidae of Myctophiformes, Megalopidae of Osteoglossiformes, Anguillidae of Anguilliformes, Notacanthidae of Notacanthiformes, Cyprinidae of Cypriniformes, Thymallinae of Salmoniformes, Salmoninae of Salmoniformes, Clupeidae of Clupeiformes, Coregoninae of Salmoniformes, Rondeletiidae of Cetomimiformes, Barbourisiidae of Cetomimiformes, Cetomimidae of Cetomimiformes, Stephanoberycidae of Cetomimiformes, Siluridae of Siluriformes, Belonidae of Atheriniformes, Exocoetidae of Atheriniformes, Belonidae of Beloniformes, Gadidae of Gadiformes, Ophidiidae of Ophidiiformes, Priacanthidae of Beryciformes, Lophotidae of Lampridiformes, Lophotidae of Lampridiformes, Aulorhynchidae of Syngnathiformes, Syngnathidae of Syngnathiformes, Synbranchidae of Synbranchiformes, Labridae of Perciformes, Clinidae of Perciformes, Scaridae of Perciformes, Pomacentridae of Perciformes, Embiotocidae of Perciformes, Cichlidae of Perciformes;

[0021] (13)Phylum Chordata, Class Amphibia, Order Gymnophiona: Siphonopidae, Actiniidae, Lumbricidae, Hirudinidae, Colubridae, Holothuriidae, Asteriidae, Echinoidea, Helicidae, Unionidae, Veneridae, Caeciliidae;

[0022] (14)Phylum Chordata, Class Amphibia, Order Caudata: Cryptobranchidae, Ambystomatidae, Salamandridae, Hynobiidae, Plethodontidae, Ranidae, Batrachospermaceae, Pleurodelidae, Pachytritonidae, Typhlonectidae, Cryptobranchidae;

[0023] (15)Phylum Chordata, Class Amphibia, Order Anura: Bufonidae, Rhacophoridae, Hylidae, Ceratophryidae, Microhylidae, Leptodactylidae;

[0024] (16)Phylum Chordata, Class Reptilia: Lacertidae of Squamata, Chelidae of Testudines, Dermochelyidae of Testudines, Trionychidae of Testudines, Cheloniidae of Testudines, Testudinidae of Testudines, Crocodylidae of Crocodylia, Alligatoridae of Crocodylia, Gavialidae of Crocodylia;

[0025] (17)Phylum Chordata, Class Aves: Psittaculidae of Psittaciformes, Cacatuidae of Psittaciformes, Loriidae of Psittaciformes, Anatidae of Anseriformes, Anseranatidae of Anseriformes, Anatidae of Anseriformes, Spheniscidae of Sphenisciformes, Passeridae of Passeriformes, Corvidae of Passeriformes, Muscicapidae of Passeriformes, Sylviidae of Passeriformes;

[0026] (18)Phylum Chordata, Class Mammalia: Ornithorhynchidae of Monotremata, Tachyglossidae of Monotremata, Equidae of Perissodactyla, Rhinocerotidae of Perissodactyla, Elephantidae of Proboscidea;

[0027] (19)Phylum Chordata, Class Mammalia, Order Marsupialia: Macropodidae, Phascolarctidae, Peramelidae, Vombatidae, Dasyuridae;

[0028] (20)Phylum Chordata, Class Mammalia, Order Rodentia: Sciuridae, Cricetidae, Rhizomyidae, Gliridae, Dipodidae, Caviidae, Castoridae, Petauristidae, Hystricidae, Lemmidae, Gerbillidae, Hydrochoeridae;

[0029] (21)Phylum Chordata, Class Mammalia, Order Chiroptera: Pteropodidae, Rhinolophidae, Hipposideridae, Vespertilionidae, Miniopteridae, Emballonuridae, Pteropodidae;

[0030] (22)Phylum Chordata, Class Mammalia, Order Carnivora: Felidae, Canidae, Ursidae, Mustelidae, Lutrinae;

[0031] (23)Phylum Chordata, Class Mammalia, Order Primates: Hominidae, Hylobatidae, Lorisidae, Tarsiidae, Lemuridae;

[0032] (24)Phylum Chordata, Class Mammalia, Order Artiodactyla: Camelidae, Suidae, Tayassuidae, Giraffidae, Antilocapridae, Cervidae, Moschidae, Bovidae, Hippopotamidae;

[0033] (25)Phylum Chordata, Class Mammalia, Order Cetacea: Platanistidae, Physeteridae, Ziphiidae, Monodontidae, Delphinidae, Stenidae, Phocoenidae, Balaenopteridae, Eschrichtiidae, Balaenidae, Balaenopteridae, Ziphiidae, Balaenopteridae.

[0034] The above-mentioned plant-derived protein core-shell structure nanocrystals are core-shell structure nanocrystals of at least one of the proteins contained in the following plants:

[0035] (1) Phylum Anthocerotophyta, Class Anthocerotopsida: Order Anthocerotales, Family Anthocerotaceae; Order Dendrocerotales, Family Dendrocerotaceae; Order Notothyladales, Family Notothyladaceae; Order Phaeocerotales, Family Phaeocerotaceae;

[0036] (2) Phylum Bryophyta, Class Bryopsida: Order Archidiales, Family Archidiaceae; Order Leucobryales, Family Leucobryaceae; Order Microlejeuneaceae, Family Microlejeuneaceae; Order Aulacomniaceae, Family Aulacomniaceae; Order Bartramiales, Family Bartramiaceae; Order Bryales, Family Bryaceae; Order Mniaceae, Family Mniaceae; Order Brachytheciales, Family Brachytheciaceae; Order Encalyptales, Family Encalyptaceae; Order Ephemerales, Family Ephemeraceae; Order Gymnostomatales, Family Gymnostomataceae; Order Grimmiales, Family Grimmiaceae; Order Hypnales, Family Hypnaceae; Order Leptodontales, Family Leptodontaceae; Order Leskeales, Family Leskeaceae; Order Meteoriaceae, Family Meteoriaceae; Order Orthotrichales, Family Orthotrichaceae; Order Pterobryales, Family Pterobryaceae; Order Ptychomniales, Family Ptychomniaceae; Order Sematophyllales, Family Sematophyllaceae; Order Thuidiaceae, Family Thuidiaceae; Order Ulotaales, Family Ulotaceae; Order Weissiales, Family Weissiaceae; Order Zygopodiales, Family Zygopodiaceae;

[0037] (3) Phylum Bryophyta, Class Bryopsida, Order Dicranales: Family Andreaeaceae, Family Climaciaceae, Family Calymperaceae, Family Dicranaceae, Family Fissidentaceae;

[0038] (4) Bryophyta, Bryopsida, Hypnales: Amblystegiaceae, Anomodonaceae, Antitrichiaceae, Brachytheciaceae, Calliergonaceae, Climaciaceae, Cryptocoleaceae, Entodontaceae, Fabroniaceae, Fontinalaceae, Helicodontaceae, Hylocomiaceae, Hypnaceae, Hypopterygiaceae, Leucodontaceae, Meteoriaceae, Mniaceae, Orthotrichaceae, Plagiotheciaceae, Pterobryaceae, Rhizogoniaceae, Sematophyllaceae, Thuidiaceae, Trichostomaceae, Weissiaceae, Xiphidriaceae;

[0039] (5) Bryophyta, Bryopsida, Pottiales: Amblystegiaceae, Bartramiaceae, Brachytheciaceae, Bryaceae, Dendroalsiaceae, Pottiaceae, Saxicolaceae, Acanthodaceae, Schistostegaceae;

[0040] (6) Bryophyta, Andreaeobryopsida, Andreaeales, Andreaeaceae; Bryophyta, Oedipodiopsida, Oedipodiales, Oedipodiaceae; Bryophyta, Polytrichopsida, Polytrichales, Polytrichaceae; Bryophyta, Sphagnopsida, Sphagnales, Sphagnaceae; Bryophyta, Sphagnopsida, Sphagnales, Ambuchananiaceae; Bryophyta, Takakiopsida, Takakiales, Takakiaceae; Bryophyta, Tetraphidopsida, Tetraphidales, Tetraphidaceae;

[0041] (7) Chlorophyta, Chlorophyceae: Bryopsidales, Bryopsidaceae; Caulerpales, Caulerpaceae; Caulerpales, Udoteaceae; Chaetophorales, Chaetophoraceae; Cladophorales, Cladophoraceae; Bryopsidales, Derbesiaceae; Cladophorales, Costariaceae; Codiales, Codiaceae; Dasycladales, Dasycladaceae; Dasycladales, Halimedaceae; Dasycladales, Valoniaceae; Oedogoniales, Oedogoniaceae; Ulotrichales, Ulotrichaceae; Ulotrichales, Kützingiaceae; Ulvales, Ulvaceae; Ulvales, Cylindrothecaceae; Ulvales, Kützingiaceae; Ulvales, Monostromataceae;

[0042] (8) Chlorophyta, Chlorophyceae, Acrosiphoniales, Acrosiphoniaceae; Marchantiophyta, Psilophytopsida, Psilophytales, Psilophytaceae; Marchantiophyta, Psilophytopsida, Treubiales, Treubiaceae; Marchantiophyta, Marchantiopsida, Blasiales, Blasiaceae; Marchantiophyta, Marchantiopsida, Lunulariales, Lunulariaceae; Lycopodiophyta, Isoetopsida, Isoetales, Isoetaceae; Lycopodiophyta, Lycopodiopsida, Lycopodiales, Lycopodiaceae; Lycopodiophyta, Selaginellopsida, Selaginellales, Selaginellaceae;

[0043] (9) Marchantiophyta, Jungermanniopsida: Metzgeriales, Calypogeiaceae; Metzgeriales, Metzgeriaceae; Metzgeriales, Makinoaceae; Jungermanniales, Jungermanniaceae; Jungermanniales, Chlorocoleaceae; Pallavicinales, Pallaviciniaceae; Pallavicinales, Monosoleniaceae; Pelliales, Pelliaceae; Porellales, Frullaniaceae; Porellales, Jubulaceae; Porellales, Lejeuneaceae; Porellales, Porellaceae; Porellales, Radulaceae; Ptilidiales, Ptilidiaceae; Ptilidiales, Neotrichocoleaceae;

[0044] (10) Marchantiophyta, Jungermanniopsida, Jungermanniales: Acrobolbaceae, Adelanthaceae, Anastreptaceae, Antheliaceae, Balantiopsidaceae, Blepharostomataceae, Calypogeiaceae, Cephaloziaceae, Cephaloziellaceae, Chiloscyphaceae, Cololejeuneaceae, Coluraceae, Diplophyllaceae, Herbertaceae, Hymenophyllaceae, Jubulaceae, Lepidoziaceae, Lejeuneaceae, Lophoziaceae, Metzgeriaceae, Monosoleniaceae, Neohodgsoniaceae, Nowelliaceae, Pallaviciniaceae, Plagiochilaceae, Plagiochlamydiaceae, Porellaceae, Radulaceae, Ricciaceae, Scapaniaceae, Sphaerocarpaceae, Takakiaceae, Telaranea, Trichocoleaceae, Trichotemnomaceae, Tritomariaceae, Wiesnerellaceae;

[0045] (11) Marchantiophyta, Marchantiopsida, Marchantiales: Aytoniaceae, Asterella, Conocephalaceae, Corsiniaceae, Marchantiaceae, Dumortiera, Fossombroniaceae, Monosoleniaceae, Ricciocarpaceae, Targioniaceae, Wiesnerellaceae;

[0046] (12) Rhodophyta, Florideophyceae: Acrochaetiales, Acrochaetiaceae, Ahnfeltiales, Ahnfeltiaceae, Bangiales, Bangiaceae, Batrachospermales, Batrachospermaceae, Ceramiales, Ceramiaceae, Corallinales, Corallinaceae, Cryptonemiales, Cryptonemiaceae, Delesseriaceae, Gigartinales, Gigartinaceae, Gracilariales, Gracilariaceae, Halymeniales, Halymeniaceae, Hypneales, Hypneaceae, Nemaliales, Nemaliaceae, Palmariales, Palmariaceae, Peyssonneliales, Peyssonneliaceae, Phyllophorales, Phyllophoraceae, Porphyridiales, Porphyridiaceae, Rhodymeniales, Rhodymeniaceae, Rhodoglossales, Rhodoglossaceae, Rhodomelales, Rhodomelaceae, Solieriales, Solieriaceae, Sphacelariales, Sphacelariaceae, Wrangeliales, Wrangeliaceae;

[0047] (13) Rhodophyta, Florideophyceae, Gigartinales: Caulacanthaceae, Chondracanthaceae, Endocladiaceae, Gigartinaceae, Gloiosiphoniaceae, Halymeniaceae, Hypneaceae, Kallymeniaceae, Laurenciaceae, Microcladiaceae, Microglossaceae, Petrocelidaceae, Phyllopeltidaceae, Plocamiaceae, Rhodymeniaceae, Sarcodiaceae, Sphaerococcus, Wrangeliaceae;

[0048] (14) Tracheophyta, Equisetopsida: Cyatheales, Cibotiaceae, Cyatheaceae, Plagiogyriaceae, Equisetales, Equisetaceae, Gleicheniales, Dipteridaceae, Gleicheniaceae, Hymenophyllales, Hymenophyllaceae, Marattiales, Marattiaceae, Ophioglossales, Ophioglossaceae, Osmundales, Osmundaceae, Psilotales, Psilotaceae, Salviniales, Salviniaceae, Schizaeales, Schizaeaceae, Thelypteridales, Thelypteridaceae;

[0049] (15) Tracheophyta, Equisetopsida, Polypodiales: Arthropteridaceae, Aspleniaceae, Athyriaceae, Blechnaceae, Cystopteridaceae, Davalliaceae, Dennstaedtiaceae, Diplaziopsidaceae, Diplaziopsis, Dryopteridaceae, Hypodematiaceae, Lindsaeaceae, Lomariopsidaceae, Lomariopsis, Nephrolepidaceae, Oleandraceae, Onocleaceae, Osmundaceae, Parkeriaceae, Peranemaceae, Phymatodes, Pteridaceae, Pteridrys, Pteris, Pterozonium, Saccoloma, Sphaerostephanos, Stenochlaena, Thelypteridaceae, Vittariaceae;

[0050] (16) Magnoliopsida of Tracheophyta: Acorales: Acoraceae, Arecales: Arecaceae, Austrobaileyales: Schisandraceae, Boraginales: Boraginaceae, Buxales: Buxaceae, Celastrales: Celastraceae, Ceratophyllales: Ceratophyllaceae, Chloranthales: Chloranthaceae, Commelinales: Commelinaceae, Commelinales: Xyridaceae, Commelinales: Pontederiaceae, Cornales: Cornaceae, Cornales: Hydrangeaceae, Cornales: Nyssaceae, Daphniphyllales: Stachyuraceae, Daphniphyllales: Staphyleaceae, Dilleniales: Dilleniaceae, Cucurbitales: Cucurbitaceae, Cucurbitales: Begoniaceae, Cucurbitales: Coriariaceae, Cucurbitales: Tetramelaceae, Dioscoreales: Dioscoreaceae, Dioscoreales: Burmanniaceae, Dioscoreales: Limnanthaceae, Dipsacales: Adoxaceae, Dipsacales: Caprifoliaceae, Escalloniales: Escalloniaceae, Fabales: Fabaceae, Fabales: Polygalaceae, Fabales: Surianaceae, Garryales: Garryaceae, Geraniales: Geraniaceae, Haloragales: Decnepteleaceae, Haloragales: Meliosmaceae, Icacinaceae: Icacinaceae, Laurales: Lauraceae, Laurales: Calycanthaceae, Laurales: Hernandiaceae, Magnoliales: Magnoliaceae, Magnoliales: Annonaceae, Magnoliales: Myristicaceae, Metteniusales: Metteniusaceae, Nymphaeales: Nymphaeaceae, Nymphaeales: Cabombaceae, Oxalidales: Oxalidaceae, Oxalidales: Connaraceae, Oxalidales: Elaeocarpaceae, Petrosaviales: Petrosaviaceae, Piperales: Piperaceae, Piperales: Aristolochiaceae, Piperales: Saururaceae, Trochodendrales: Trochodendraceae, Vitales: Vitaceae, Zygophyllales: Zygophyllaceae;

[0051] (17) Magnoliopsida of Tracheophyta: Alismatales: Alismataceae, Aponogetonaceae, Araceae, Butomaceae, Cymodoceaceae, Hydrocharitaceae, Juncaginaceae, Posidoniaceae, Potamogetonaceae, Ruppiaceae, Scheuchzeriaceae, Tofieldiaceae, Zosteraceae;

[0052] (18) Magnoliopsida of Tracheophyta: Apiales: Apiaceae, Araliaceae, Pittosporaceae, Torricelliaceae;

[0053] (19) Magnoliopsida of Tracheophyta: Aquifoliales: Aquifoliaceae, Cardiopteridaceae, Helwingiaceae, Strasburgeriaceae;

[0054] (20) Magnoliopsida of Tracheophyta: Asparagales: Asparagaceae, Amaryllidaceae, Asphodelaceae, Hypoxidaceae, Iridaceae, Orchidaceae;

[0055] (21) Magnoliopsida of Tracheophyta: Asterales: Asteraceae, Campanulaceae, Goodeniaceae, Menyanthaceae, Pentaphragmataceae, Stylidiaceae;

[0056] (22) Magnoliopsida of Tracheophyta: Brassicales: Brassicaceae, Akaniaceae, Capparaceae, Caricaceae, Cleomaceae, Moringaceae, Resedaceae, Salvadoraceae, Tropaeolaceae;

[0057] (23)Magnoliopsida, Caryophyllales of vascular plants: Caryophyllaceae, Aizoaceae, Amaranthaceae, Ancistrocladaceae, Basellaceae, Cactaceae, Droseraceae, Frankeniaceae, Gisekiaceae, Molluginaceae, Nepenthaceae, Nyctaginaceae, Petiveriaceae, Phytolaccaceae, Plumbaginaceae, Polygonaceae, Portulacaceae, Talinaceae, Tamaricaceae;

[0058] (24)Magnoliopsida, Ericales of vascular plants: Ericaceae, Actinidiaceae, Balsaminaceae, Clethraceae, Diapensiaceae, Ebenaceae, Ericaceae, Lecythidaceae, Mitrastemonaceae, Pentaphylacaceae, Polemoniaceae, Primulaceae, Sapotaceae, Sladeniaceae, Styracaceae, Symplocaceae, Theaceae;

[0059] (25)Magnoliopsida, Fagales of vascular plants: Fagaceae, Betulaceae, Casuarinaceae, Fagaceae, Juglandaceae, Myricaceae;

[0060] (26)Magnoliopsida, Gentianales of vascular plants: Gentianaceae, Apocynaceae, Gelsemiaceae, Gentianaceae, Loganiaceae, Rubiaceae;

[0061] (27)Magnoliopsida, Lamiales of vascular plants: Lamiaceae, Acanthaceae, Bignoniaceae, Carlemanniaceae, Gesneriaceae, Lentibulariaceae, Linderniaceae, Martyniaceae, Mazaceae, Oleaceae, Orobanchaceae, Paulowniaceae, Pedaliaceae, Phrymaceae, Plantaginaceae, Scrophulariaceae, Verbenaceae, Wightiaceae;

[0062] (28)Magnoliopsida, Liliales of vascular plants: Liliaceae, Colchicaceae, Hostaceae, Melanthiaceae, Smilacaceae;

[0063] (29)Magnoliopsida, Malpighiales of vascular plants: Malpighiaceae, Achariaceae, Calophyllaceae, Anthostema, Clusiaceae, Dichapetalaceae, Elatinaceae, Erythroxylaceae, Euphorbiaceae, Hypericaceae, Ixonanthaceae, Linaceae, Ochnaceae, Microdesmaceae, Passifloraceae, Trigoniaceae, Phyllanthaceae, Podostemaceae, Trimeniaceae, Rafflesiaceae, Rhizophoraceae, Salicaceae, Violaceae;

[0064] (30)Magnoliopsida, Malvales of vascular plants: Malvaceae, Bixaceae, Cistaceae, Dipterocarpaceae, Thymelaeaceae;

[0065] (31)Magnoliopsida, Myrtales of vascular plants: Myrtaceae, Combretaceae, Crypteroniaceae, Lythraceae, Melastomataceae, Onagraceae;

[0066] (32)Magnoliopsida, Pandanales of vascular plants: Pandanaceae, Stemonaceae, Triuridaceae, Velloziaceae;

[0067] (33)Magnoliopsida, Poales of vascular plants: Poaceae, Bromeliaceae, Cyperaceae, Eriocaulaceae, Flagellariaceae, Juncaceae, Mayacaceae, Restionaceae, Typhaceae, Xyridaceae;

[0068] (34) Magnoliopsida of Tracheophyta, Proteales: Proteaceae, Nelumbonaceae, Platanaceae, Sabiaceae;

[0069] (35) Magnoliopsida of Tracheophyta, Ranunculales: Ranunculaceae, Berberidaceae, Circaeasteraceae, Eupteleaceae, Lardizabalaceae, Menispermaceae, Papaveraceae;

[0070] (36) Magnoliopsida of Tracheophyta, Rosales: Rosaceae, Cannabaceae, Elaeagnaceae, Moraceae, Rhamnaceae, Rosaceae, Ulmaceae, Urticaceae;

[0071] (37) Magnoliopsida of Tracheophyta, Santalales: Santalaceae, Mitrastemonaceae, Balanophoraceae, Eremosynaceae, Loranthaceae, Olacaceae, Opiliaceae, Santalaceae, Alectryonaceae, Ximeniaceae;

[0072] (38) Magnoliopsida of Tracheophyta, Sapindales: Sapindaceae, Anacardiaceae, Biebersteiniaceae, Burseraceae, Meliaceae, Nitrariaceae, Rutaceae, Simaroubaceae;

[0073] (39) Magnoliopsida of Tracheophyta, Saxifragales: Saxifragaceae, Altingiaceae, Cercidiphyllaceae, Crassulaceae, Cynomoriaceae, Daphniphyllaceae, Grossulariaceae, Haloragaceae, Hamamelidaceae, Myrsinaceae, Paeoniaceae, Penthoraceae, Saxifragaceae;

[0074] (40) Magnoliopsida of Tracheophyta, Solanales: Solanaceae, Convolvulaceae, Hydrophyllaceae, Sphenocleaceae;

[0075] (41) Magnoliopsida of Tracheophyta, Zingiberales: Zingiberaceae, Cannaceae, Costaceae, Marantaceae, Musaceae, Strelitziaceae;

[0076] (42) Pinopsida of Tracheophyta: Araucariales Araucariaceae, Araucariales Podocarpaceae, Pinales Cephalotaxaceae, Pinales Cupressaceae, Pinales Taxaceae, Cycadales Cycadaceae, Ephedrales Ephedraceae, Ginkgoales Ginkgoaceae, Gnetales Gnetaceae, Pinales Pinaceae, Sciadopityales Sciadopityaceae.

[0077] Furthermore, the protein core-shell structured nanocrystals are selected from the core-shell structured nanocrystals of any one of lysozyme, bovine serum albumin, human serum albumin, lactoferrin, lactalbumin, insulin, α-lactalbumin, fibrinogen, β-lactoglobulin, ribonuclease A, cytochrome c, α-amylase, horseradish peroxidase, pepsin, myoglobin albumin, collagen, keratin, hemoglobin, DNA polymerase, casein, soy protein, pea protein isolate, zein, gliadin, gluten, oat protein, potato protein, hemp seed protein, walnut protein, rapeseed protein, hazelnut protein, quinoa protein, sunflower seed protein, pumpkin seed protein, black sesame protein, mushroom protein, red algae protein, legumin, barley protein, wheat protein, glutenin, kidney bean protein, casein, gelatin, catalase, transferrin, and thyroglobulin.

[0078] The preparation method of the protein core-shell structured nanocrystals described in the present invention is as follows: dissolve the protein in ultrapure water to obtain an aqueous protein solution; dissolve the disulfide bond reducing agent in ultrapure water, and adjust the pH to 3-5 with saturated tris to obtain a disulfide bond reducing agent solution; after mixing the protein solution and the disulfide bond reducing agent solution evenly, incubate at 40-50 °C for 7-14 hours to obtain an aqueous solution of protein core-shell structured nanocrystals. Among them, the disulfide bond reducing agent is selected from any one or more of cysteine, tris(2-carboxyethyl)phosphine hydrochloride, reduced glutathione, dithiothreitol, β-mercaptoethanol (2-mercaptoethanol), dimercaptosuccinic acid, sodium sulfite, guanidine hydrochloride, urea, thiourea, selenourea, tellurourea, sodium ferrate, trivalent cobalt salt, chlorate, potassium permanganate, persulfate, potassium dichromate, concentrated sulfuric acid, nitric acid, hydrobromic acid, hydroiodic acid, perchloric acid, ozone, hydrogen peroxide, fluorine gas, chlorine gas, sodium bismuthate, periodic acid, lead dioxide, trifluoroethanol, hexafluoroisopropanol, trifluoroacetic acid, arginine ketone acid, arginine ester, arginine amide, citrulline ketone acid, citrulline ester, citrulline amide, ornithine ketone acid, ornithine ester, ornithine amide, xanthine, hypoxanthine, trioxypurine, theophylline, theobromine, caffeine, and malonamide.

[0079] Furthermore, the responsive block polymer is selected from any one of poly(N-isopropylacrylamide)-polyacrylic acid, poly(N-isopropylacrylamide)-polylactic acid, polyethylene oxide-polypropylene oxide block copolymer, polyacrylic acid-polystyrene, polyhistidine-polyethylene glycol, polyethylene oxide-azobenzene-polystyrene, polymethyl methacrylate-spiropyran, Fe3O4@polypyrrole-polyethylene glycol, polyacrylic acid-polystyrene sulfonic acid, polyethylene glycol containing disulfide bond-polycaprolactone, poly(N-isopropylacrylamide)-polycaprolactone, poly(N-isopropylacrylamide)-polystyrene, polyethylene oxide-polypropylene oxide-polyethylene oxide, polycaprolactone-poly(N-isopropylacrylamide), poly(L-lactic acid)-poly(N-isopropylacrylamide), poly(dimethylaminoethyl methacrylate)-polyethylene glycol, polyvinylcaprolactam-polyethylene glycol, polyethylene glycol-poly(D,L-lactic acid), polyacrylic acid-polystyrene, polyacrylic acid-polyethylene glycol, poly(diethylaminoethyl methacrylate)-polycaprolactone, polymethacrylic acid-polyethylene glycol, poly(2-vinylpyridine)-polystyrene, poly(4-vinylpyridine)-polycaprolactone, polyacrylic acid-poly(dimethylaminoethyl methacrylate), polyethylene glycol-polyaspartic acid, polyethyleneimine-polycaprolactone, azobenzene group-containing polymer-polyethylene glycol, polystyrene-spiropyran photo-responsive block, polyethylene oxide-nitrobenzyl ester photocleavable block, azobenzene-modified poly(dimethylaminoethyl methacrylate), polycaprolactone-spiropyran block, polymethacrylate containing o-nitrobenzyl photocleavable group, polyethylene glycol containing disulfide bond-polylactic acid, polystyrene containing disulfide bond-polyacrylic acid, polyethylene oxide-polymethacrylic acid, polystyrene-polyvinylpyrrolidone, polyethylene glycol-sodium polystyrene sulfonate, polyethylene glycol-poly(N-isopropylacrylamide)-polyacrylic acid, polycaprolactone-poly(N-isopropylacrylamide)-azobenzene, polyethylene glycol containing disulfide bond-poly(dimethylaminoethyl methacrylate), polyacrylic acid containing ferrocene group-poly(N-isopropylacrylamide).

[0080] The preparation method of the ultra-high resolution colorimetric sensor based on the thickness gradient responsive film of the present invention is as follows: The aqueous solution of the responsive polymer is coated on the substrate by a programmed continuous two-step spin coating process to form a film with multiple concentric circular color patterns, that is, the ultra-high resolution colorimetric sensor based on the thickness gradient responsive film is obtained; wherein, the two-step spin coating process is the first low-speed spin coating process and the second high-speed spin coating process. The rotation speed of the first low-speed spin coating process is 800-1200 r / min, and the spin coating time is 90-200 s. The rotation speed of the second high-speed spin coating process is 4000-5000 r / min, and the spin coating time is 240-480 s. The temperature of the spin coating is 5-50 °C.

[0081] In the above preparation method, preferably, the rotation speed of the first-step low-speed spin coating process is 800-1000 r / min, the spin coating time is 90-120 s, the rotation speed of the second-step high-speed spin coating process is 4500-4600 r / min, the spin coating time is 300-360 s, and the temperature of the spin coating is 20-40 °C.

[0082] In the above preparation method, preferably, the viscosity of the aqueous solution of the responsive polymer is 20-50 mPa·s, and the concentration of the responsive polymer is 8-15 mg / mL.

[0083] The present invention also provides the use of the above ultra-high resolution colorimetric sensor based on the thickness gradient responsive film in colorimetric detection of relative humidity.

[0084] Meanwhile, the present invention also provides the use of the above ultra-high resolution colorimetric sensor based on the thickness gradient responsive film in colorimetric detection of organic amine vapors. Among them, the organic amine vapor is any one of methylamine, aniline, ethylamine, dimethylamine, diphenylamine, piperidine, trimethylamine, triethylamine, triphenylamine, tetramethylammonium bromide, benzyltrimethylammonium chloride, n-butylamine, cyclohexylamine, aniline, o-toluidine, pyridine, morpholine, ethylenediamine, hexamethylenediamine, triethylenetetramine, dopamine, putrescine, histamine, tyramine, spermine, spermidine, phenethylamine, cadaverine, ethanolamine, cysteamine, caprolactam, etc.

[0085] The beneficial effects of the present invention are as follows:

[0086] 1. The present invention forms a responsive film with multiple concentric circular color patterns by spin coating a responsive polymer on a substrate through a programmed two-step continuous spin coating process. The thickness distribution of the film can be adjusted by the spin coating time of the first-step low-speed spin coating process. In the first-step low-speed spin coating process, through solvent evaporation, the radius (Rw) of the circular wetting area is reduced below the critical threshold (3.24 mm, obtained by theoretical calculation); in the second-step high-speed rotation process, the droplet undergoes edge-to-center shrinkage drying to generate a responsive film with a thickness gradient (from thick to thin along the center-to-edge direction). When Rw < 3.24 mm in the first-step low-speed spin coating process, different thickness distributions from the edge to the center of the film can be achieved. When Rw > 3.24 mm, the droplet will spread and form a monochromatic film. By this method, a typical thickness gradient is obtained. Therefore, as long as the time of the first-step low-speed spin coating is controlled to make Rw drop below 3.24 mm, the shrinkage drying in the subsequent high-speed spin coating can be controllably adjusted, so as to obtain different thickness gradient distributions from the spin coating center to the edge.

[0087] 2. Compared with the traditional 18 nm spatial resolution based on thin-film interference colorimetry, the colorimetric sensor of the present invention converts the interference signal of the gradient-thickness thin film into a color difference spectrum, and the spatial resolution can reach 0.018 nm. At the same time, it retains the inherent advantages of low cost, easy use, and only requires a simple camera based on colorimetric sensing. In addition, different from the simple colorimetric reading in traditional colorimetric sensing, the color difference spectrum signal obtained by integrating the two-dimensional interference pattern can effectively resist optical interferences such as white balance drift and ambient background brightness. Using an ordinary digital camera, the interference signal of the gradient-thickness thin film can be converted into a color difference spectrum signal. The change rate amplitude of the edge reflectivity response signal with uniform thickness is much lower than that of the color difference integral spectrum response signal in the central circular area with gradient thickness.

[0088] 3. The sensor of the present invention is based on the adsorption-swelling mechanism and the crystallization-swelling mechanism of the responsive thin film, can interact with the target stimulant vapor and cause thickness changes, and is respectively used for the sensing detection of relative humidity and organic amine vapor. Its sensing performance is significantly better than that of other colorimetric sensors. The quantitative stimulation of humidity or organic amine vapor is achieved by mixing two airflows: blowing a dry N2 flow into ultrapure water or an organic amine analyte to generate relative humidity or saturated organic amine vapor, while the other is a dry N2 flow. By controlling the ratio of the sizes of the two airflows, a wide range of relative humidity and amine vapor concentrations can be achieved. At the same time, the sensor can also complete the sensing detection of relative humidity and organic amine vapor at different temperatures (20 - 50 °C). Compared with the reflection spectrum sensor based on an optical fiber spectrometer, the sensor can achieve a sensitivity improvement of 3 - 8 times only by using an ordinary digital camera; compared with the sensor based on reflectivity detection, under the response of relative humidity, the sensor provides a sensitivity enhancement of 3 times, and the relative humidity response value is at least 10 times higher than that of the conventional colorimetric sensor; under the response of organic amine vapor, the sensor provides a sensitivity enhancement of nearly 8 times, and in terms of response time and detection limit, it is superior to other sensors for putrescine detection. Brief Description of the Drawings

[0089] Figure 1 It is a photograph of the lysozyme core-shell structure nanocrystal sol prepared in Example 1.

[0090] Figure 2 It is the phenomenon of the generation of interference colors from the edge to the center during the spin-coating production process of the ultra-high-resolution colorimetric sensor based on the thickness-gradient responsive thin film in Example 1.

[0091] Figure 3 It is a photograph (A) of the thickness-gradient responsive thin film of the ultra-high-resolution colorimetric sensor prepared in Example 1 and an SEM thickness map (B) at different positions from the center.

[0092] Figure 4It is a photo of the thickness-gradient responsive film of the ultra-high resolution colorimetric sensor prepared in Example 2.

[0093] Figure 5 It is a photo of the thickness-gradient responsive film of the ultra-high resolution colorimetric sensor prepared in Example 3.

[0094] Figure 6 It is a photo of the thickness-gradient responsive film of the ultra-high resolution colorimetric sensor prepared in Example 4.

[0095] Figure 7 It is a photo of the thickness-gradient responsive film of the ultra-high resolution colorimetric sensor prepared in Example 5.

[0096] Figure 8 It is a photo of the thickness-gradient responsive film of the ultra-high resolution colorimetric sensor prepared in Example 6.

[0097] Figure 9 It is a photo of the thickness-gradient responsive film of the ultra-high resolution colorimetric sensor prepared in Example 7.

[0098] Figure 10 It is a photo of the thickness-gradient responsive film of the ultra-high resolution colorimetric sensor prepared in Example 8.

[0099] Figure 11 It is a photo of the interference fringes (left figure) on the film and the chromatic aberration integral spectrogram (right figure) of the ultra-high resolution colorimetric sensor based on the thickness-gradient responsive film in Example 1 under different relative humidities.

[0100] Figure 12 It is the response of the ultra-high resolution colorimetric sensor based on the thickness-gradient responsive film in Example 1 to relative humidity at different temperatures.

[0101] Figure 13 It is the amplitude change of the signals detected by different methods and their comparison of the ultra-high resolution colorimetric sensor based on the thickness-gradient responsive film in Example 1 under the responsive relative humidity, where A is the reflectivity response at the edge of the sensor, B is the chromatic aberration integral spectral response of the circular area within 6 mm from the center of the sensor, and C is the sensitivity comparison between the reflectivity response and the chromatic aberration integral spectral response.

[0102] Figure 14 It is the comparison of the relative humidity resolution detected by the ultra-high resolution colorimetric sensor based on the thickness-gradient responsive film and the conventional colorimetric sensor in Example 1.

[0103] Figure 15It is the interference fringe photograph (left figure) and the chromatic aberration integral spectrogram (right figure) of the ultra-high resolution colorimetric sensor based on the thickness gradient responsive film in Example 1 on the film under different putrescine vapor concentrations.

[0104] Figure 16 It is the signal change amplitude and comparison detected by different methods of the ultra-high resolution colorimetric sensor based on the thickness gradient responsive film in Example 1 under the response of putrescine vapor, where A is the chromatic aberration integral spectral response of the circular area within 6 mm from the center of the sensor, B is the reflectivity response at the edge of the sensor, and C is the sensitivity comparison between the reflectivity response and the chromatic aberration integral spectral response.

[0105] Figure 17 It is the comparison of the response time and detection limit of the ultra-high resolution colorimetric sensor based on the thickness gradient responsive film in Example 1 and other colorimetric materials for putrescine detection. Detailed implementation manners

[0106] For the convenience of understanding the present invention, the present invention will be described more comprehensively and meticulously below in conjunction with the accompanying drawings and preferred embodiments, but the protection scope of the present invention is not limited to the following specific embodiments.

[0107] Example 1

[0108] Dissolve 0.4 g of lysozyme powder in 5 mL of ultrapure water to obtain a lysozyme solution; dissolve 0.5712 g of tris(2-carboxyethyl)phosphine hydrochloride (TCEP) in 35 mL of ultrapure water, and add a saturated Tris solution to obtain a TCEP buffer solution with a pH value of 4; then add the lysozyme solution to the TCEP buffer solution and incubate at 47 °C for 12 h to obtain an aqueous solution of lysozyme core-shell structured nanocrystals with a final concentration of lysozyme of 10 mg / mL and a viscosity of 32 mPa·s, as Figure 1 . We found that the kinetically controlled quasi-equilibrium state assembly can inhibit the overly strong interaction between proteins, prompting the short-range ordered β-sheet aggregates to be able to stack orderly to form amyloid-like nanocrystals. That is, by kinetically controlling the protein unfolding-aggregation process, amyloid-like nanocrystals can be obtained. This crystal has a typical core-shell structure, that is, the nanocrystal serves as the core and is embedded in the shell composed of unfolded chains. This step reduces the disulfide bonds in lysozyme by TCEP, causing it to unfold and undergo amyloid-like aggregation to form short-range ordered β-sheet aggregates. The polypeptide chain in the lysozyme molecule unfolds, and lysozyme changes from a natural protein structure rich in α-helix structure to a protein aggregate rich in β-sheet structure. The β-sheet structure further stacks orderly to form a dense crystal nucleus, and the unfolded polypeptide chain forms a continuous phase as the shell, forming a lysozyme nanocrystal sol with a core-shell structure.

[0109] 200 μL of the aqueous solution of lysozyme core-shell structured nanocrystals was coated on a 2×2 cm 2 silicon substrate with the tip of a micropipette, and a thin film with multiple concentric circular color patterns was formed through a programmed two-step spin-coating process. Among them, the two-step spin-coating process was the first low-speed spin-coating process and the second high-speed spin-coating process. The rotation speed of the first low-speed spin-coating process was 900 r / min, and the spin-coating time was 90 s. The rotation speed of the second high-speed spin-coating process was 4500 r / min, and the spin-coating time was 300 s. The spin-coating temperature was 30 °C, and an ultra-high-resolution colorimetric sensor based on a thickness-gradient responsive thin film was obtained, such as Figure 2 . From Figure 3 the cross-sectional scanning electron microscope (SEM) imaging diagram, it can be seen that the thin films of the obtained sensors showed thicknesses of 407 nm, 310 nm, and 232 nm at distances of r = 0 mm, 3 mm, and 6 mm from the center of the sensor, respectively.

[0110] Example 2

[0111] 0.4 g of bovine serum albumin powder was dissolved in 5 mL of ultrapure water to obtain a bovine serum albumin solution; 0.5712 g of TCEP was dissolved in 35 mL of ultrapure water, and a saturated Tris solution was added to obtain a TCEP buffer solution with a pH value of 4; then the bovine serum albumin solution was added to the TCEP buffer solution and incubated at 47 °C for 12 h to obtain an aqueous solution of bovine serum albumin core-shell structured nanocrystals with a final concentration of bovine serum albumin of 10 mg / mL and a viscosity of 32 mPa·s. 200 μL of the aqueous solution of bovine serum albumin core-shell structured nanocrystals was coated on a 2×2 cm 2 silicon substrate with the tip of a micropipette, and a thin film with multiple concentric circular color patterns was formed through a programmed two-step spin-coating process. Among them, the two-step spin-coating process was the first low-speed spin-coating process and the second high-speed spin-coating process. The rotation speed of the first low-speed spin-coating process was 900 r / min, and the spin-coating time was 100 s. The rotation speed of the second high-speed spin-coating process was 4500 r / min, and the spin-coating time was 320 s. The spin-coating temperature was 25 °C, and an ultra-high-resolution colorimetric sensor based on a thickness-gradient responsive thin film was obtained, such as Figure 4 .

[0112] Example 3

[0113] Dissolve 0.48 g of lysozyme powder in 5 mL of ultrapure water to obtain a lysozyme solution; dissolve 0.6854 g of TCEP in 35 mL of ultrapure water, and add a saturated Tris solution to obtain a TCEP buffer solution with a pH value of 4; then add the lysozyme solution to the TCEP buffer solution and incubate at 47 °C for 13 h to obtain an aqueous solution of lysozyme core-shell structured nanocrystals with a final concentration of lysozyme of 12 mg / mL and a viscosity of 34 mPa·s. Coat 200 μL of the aqueous solution of lysozyme core-shell structured nanocrystals on a 2×2 cm 2 silicon substrate with the tip of a micropipette, and form a film with multiple concentric circular color patterns through a programmed continuous two-step spin-coating process. Among them, the two-step spin-coating process is the first low-speed spin-coating process and the second high-speed spin-coating process. The rotation speed of the first low-speed spin-coating process is 900 r / min, the spin-coating time is 90 s, the rotation speed of the second high-speed spin-coating process is 4500 r / min, the spin-coating time is 300 s, and the spin-coating temperature is 30 °C to obtain an ultra-high-resolution colorimetric sensor based on a thickness-gradient responsive film, such as Figure 5 .

[0114] Example 4

[0115] In this example, coat 200 μL of an aqueous solution of lysozyme core-shell structured nanocrystals with a final concentration of lysozyme of 12 mg / mL and a viscosity of 34 mPa·s (the preparation method is the same as that in Example 3) on a 2×2 cm 2 silicon substrate with the tip of a micropipette, and form a film with multiple concentric circular color patterns through a programmed continuous two-step spin-coating process. Among them, the two-step spin-coating process is the first low-speed spin-coating process and the second high-speed spin-coating process. The rotation speed of the first low-speed spin-coating process is 900 r / min, the spin-coating time is 90 s, the rotation speed of the second high-speed spin-coating process is 4500 r / min, the spin-coating time is 300 s, and the spin-coating temperature is 40 °C to obtain an ultra-high-resolution colorimetric sensor based on a thickness-gradient responsive film, such as Figure 6 .

[0116] Example 5

[0117] In this example, coat 200 μL of an aqueous solution of lysozyme core-shell structured nanocrystals with a final concentration of lysozyme of 12 mg / mL and a viscosity of 34 mPa·s (the preparation method is the same as that in Example 3) on a 2×2 cm 2On a silicon substrate, a thin film with multiple concentric circular color patterns is formed by a programmed two-step spin-coating process. Among them, the two-step spin-coating process is the first low-speed spin-coating process and the second high-speed spin-coating process. The rotation speed of the first low-speed spin-coating process is 850 r / min, the spin-coating time is 90 s, the rotation speed of the second high-speed spin-coating process is 4500 r / min, the spin-coating time is 300 s, and the spin-coating temperature is 25 °C, to obtain an ultra-high-resolution colorimetric sensor based on a thickness-gradient-responsive thin film, such as Figure 7 .

[0118] Example 6

[0119] In this example, 200 μL of an aqueous solution of lysozyme core-shell structure nanocrystals with a final concentration of lysozyme of 12 mg / mL and a viscosity of 34 mPa·s (prepared by the same method as in Example 3) was coated on a 2×2 cm 2 silicon substrate. A thin film with multiple concentric circular color patterns is formed by a programmed two-step spin-coating process. Among them, the two-step spin-coating process is the first low-speed spin-coating process and the second high-speed spin-coating process. The rotation speed of the first low-speed spin-coating process is 900 r / min, the spin-coating time is 115 s, the rotation speed of the second high-speed spin-coating process is 4500 r / min, the spin-coating time is 320 s, and the spin-coating temperature is 30 °C, to obtain an ultra-high-resolution colorimetric sensor based on a thickness-gradient-responsive thin film, such as Figure 8 .

[0120] Example 7

[0121] 100 mg of poly(N-isopropylacrylamide)-polyacrylic acid was dissolved in 10 mL of ultrapure water to obtain an aqueous solution of poly(N-isopropylacrylamide)-polyacrylic acid; 200 μL of the aqueous solution of poly(N-isopropylacrylamide)-polyacrylic acid was coated on a 2×2 cm 2 silicon substrate. A thin film with multiple concentric circular color patterns is formed by a programmed two-step spin-coating process. Among them, the two-step spin-coating process is the first low-speed spin-coating process and the second high-speed spin-coating process. The rotation speed of the first low-speed spin-coating process is 900 r / min, the spin-coating time is 90 s, the rotation speed of the second high-speed spin-coating process is 4500 r / min, the spin-coating time is 300 s, and the spin-coating temperature is 30 °C, to obtain an ultra-high-resolution colorimetric sensor based on a thickness-gradient-responsive thin film, such as Figure 9 .

[0122] Example 8

[0123] Dissolve 0.48 g of lactoferrin powder in 5 mL of ultrapure water to obtain a lactoferrin solution; dissolve 0.6854 g of TCEP in 35 mL of ultrapure water, and add a saturated Tris solution to obtain a TCEP buffer solution with a pH value of 4; then add the lactoferrin solution to the TCEP buffer solution and incubate at 47 °C for 13 h to obtain an aqueous solution of lactoferrin core-shell structure nanocrystals with a final concentration of lactoferrin of 12 mg / mL and a viscosity of 32 mPa·s. Coat 200 μL of the aqueous solution of lactoferrin core-shell structure nanocrystals on a 2×2 cm 2 silicon substrate, and form a film with multiple concentric circular color patterns through a programmed two-step spin-coating process. Among them, the two-step spin-coating process is the first low-speed spin-coating process and the second high-speed spin-coating process. The rotation speed of the first low-speed spin-coating process is 900 r / min and the spin-coating time is 90 s. The rotation speed of the second high-speed spin-coating process is 4500 r / min and the spin-coating time is 300 s. The spin-coating temperature is 30 °C to obtain an ultra-high-resolution colorimetric sensor based on a thickness-gradient responsive film, such as Figure 10 .

[0124] Application Example 1

[0125] Application of the ultra-high-resolution colorimetric sensor based on the thickness-gradient responsive film in Example 1 in colorimetric detection of relative humidity.

[0126] Quantitative stimulation of relative humidity is achieved by mixing two airflows with a total flow rate of 200 mL / min: blowing a dry N2 flow into ultrapure water to generate relative humidity, and the other airflow is a dry N2 flow. By controlling the ratio of the flow rates of the two airflows, a wide range of relative humidity can be achieved. Control the flow rates of the dry N2 flow blown into ultrapure water to be 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180 mL / min respectively, and the corresponding flow rates of the other dry N2 flow are 190, 180, 170, 160, 150, 140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20 mL / min respectively, so as to achieve relative humidity flowing into the sensor of RH 5%, RH 10%, RH 15%, RH20%, RH 25%, RH 30%, RH 35%, RH 40%, RH 45%, RH 50%, RH 55%, RH 60%, RH 65%, RH 70%, RH 75%, RH 80%, RH 85%, RH 90% respectively, and then conduct sensing detection, such as Figure 11, which is the response of the colorimetric sensor under different relative humidities. When the environmental relative humidity changes from 5% to 90%, the interference fringes on the thin film expand regularly from the inside out, showing a red shift in the color difference integral spectrum. And due to the reversible adsorption - desorption of water, the humidity response and recovery cycle process are completely repeatable. At the same time, the sensing detection of relative humidity can also be realized at different temperatures (20°C, 30°C, 40°C, 50°C), such as Figure 12 . Using an ordinary digital camera, the interference signal of the thickness - gradient thin film can be converted into a color - difference spectrum signal. The change rate amplitude of the edge reflectivity response signal with uniform thickness is much lower than that of the color - difference integral spectrum response signal in the central circular area of the thickness gradient. Compared with the reflectivity, at the responsive relative humidity, the color - difference integral spectrum response provides a 3 - fold enhancement in sensitivity (such as Figure 13 ), and the relative humidity response value is at least 10 times higher than that of the conventional colorimetric sensors reported in the literature (such as Figure 14 and Table 1).

[0127] Table 1 Comparison of relative humidity detection by different colorimetric sensors

[0128]

[0129]

[0130] Application Example 2

[0131] Application of the ultra - high - resolution colorimetric sensor based on the thickness - gradient responsive thin film in Example 1 for colorimetric detection of organic amine vapors.

[0132] The quantitative stimulation of organic amine vapors is achieved by mixing two gas flows with a total flow rate of 100 mL / min: blowing a dry N2 flow into putrescine to generate putrescine vapor, and the other gas flow is a dry N2 flow. By controlling the ratio of the flow rates of the two gas flows, different putrescine concentrations can be achieved. Control the flow rate of the dry N2 flow blown into putrescine to be 0, 0.25, 0.5, 0.75, 1, 1.25, 1.5, 1.75, 2 mL / min respectively, and the corresponding flow rates of the other dry N2 flow are 100, 99.75, 99.5, 99.25, 99.0, 98.75, 98.5, 98.25, 98 mL / min respectively. Then the putrescine concentrations entering the sensor can be 0 ppm, 0.025 ppm, 0.05 ppm, 0.075 ppm, 0.1 ppm, 0.125 ppm, 0.15 ppm, 0.175 ppm, 0.2 ppm respectively, so as to carry out sensing detection, such as Figure 15, which is the response of the colorimetric sensor at different putrescine concentrations. When the putrescine concentration changes from 0 ppm to 0.2 ppm, the interference fringes on the film expand regularly from the inside out, showing a red shift in the color difference integral spectrum. An ordinary digital camera can convert the interference signal of the thickness gradient film into a color difference spectrum signal. The change rate amplitude of the edge reflectivity response signal with uniform thickness is much lower than that of the color difference integral spectrum response signal in the central circular area with gradient thickness. Compared with the reflectivity, the color difference integral spectrum response provides nearly 8 times higher sensitivity enhancement under the response to putrescine vapor (such as Figure 16 ), and in terms of response time and detection limit, it is superior to other colorimetric materials used for putrescine detection (such as Figure 17 and Table 2).

[0133] Table 2 Comparison of different colorimetric sensors for putrescine detection

[0134]

[0135]

Claims

1. An ultra-high resolution colorimetric sensor based on a thickness gradient responsive film, characterized in that: The colorimetric sensor comprises a substrate, and a responsive film formed by spin coating a responsive polymer on the substrate, wherein the thickness of the film is distributed in a gradient that gradually decreases from the center to the edge, the thickness at the center is 300 to 600 nm, and the thickness difference from the center to the edge is 120 to 200 nm; The responsive polymer is selected from any one of protein core-shell structure nanocrystals, responsive block polymers, reflectin, silk, and cellulose nanocrystals.

2. The ultra-high resolution colorimetric sensor based on a thickness gradient responsive film according to claim 1, characterized in that: The substrate is any one of a silicon substrate, a gold substrate and a platinum substrate.

3. The ultra-high resolution colorimetric sensor based on a thickness gradient responsive film according to claim 1, characterized in that: The protein core-shell structure nanocrystals are selected from animal-derived protein core-shell structure nanocrystals or plant-derived protein core-shell structure nanocrystals; The animal-derived protein core-shell structure nanocrystals are core-shell structure nanocrystals of at least one of the proteins contained in the following animals: (1) Arthropoda, class Insecta, order Coleoptera: Pederidae, Coleoptera, Scarabaeoidea, Cerambycidae, Chrysomeliformes, Curculionoidea, Dermatophytidae, Cynomoroidea, Hydrocharoidea, Mud Beetles, Cerambycidae, Tiger Beetles, Curculionidae, Coccinellidae, Lampyridae, Cloth Beetles, Cryptolabridae, Thick-horned Coleoptera, and Ground Coleoptera; (2) Arthropoda, Insecta, Hymenoptera: Ichneumonidae, Braconidae, Mylidae, Gall-bee Bees, Sphecidae, Vespidae, Formicidae, Apidae, Tenebrioidae, Sawfly, Woodfly, Parasitic Woodfly, Chrysopidae, Enameled Mylidae, Trichogrammatidae, Mylidae, Mylidae, Hammer-horned Mylidae, Marginal Mylidae, and Broad-bellied Mylidae; (3) Arthropoda, Insecta, Lepidoptera: Microptera, Acanthidae, Xylotomidae, Superfamily Lycopodia, Rapeworms, Carpiomorpha, Limulidae, Torcula, Sciaenidae, Schizomysidae, Schizomysidae, Gnaphal ...; (4) Arthropoda, Crustacea, Macacaridae: Phylum Arthropodidae, Macrophyllidae, Pseudophyllidae, Deep-sea Shrimp, Indian Shrimp, Broad Shrimp, Semi-toed Shrimp, Big-toed Shrimp, Toothed Shrimp, Proto-toed Shrimp, Pseudo-shrimp, Trogidae, Red Shrimp, Crown Shrimp, Lycopodidae, Microshrimp, Square Shrimp, Shrimp, Broad Shrimp, Parashrimp; (5) Arthropoda, class Arachnida, order Araneae: Araneidae, Theridiidae, Theridiidae, Lycosauridae, Salticidae, Scorpionidae, Ixodidae, Acaridae, Tickidae, Red Spiders, Theridiidae, Theridiidae, Ocellidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae, Theridiidae; (6) Arthropoda, Arachnida, Scorpionidae: Pseudo-marsh scorpionidae, Pincer scorpionidae, Microscorpionidae, Pig scorpionidae, Marsh scorpionidae, True scorpionidae, Superstitious mountain scorpionidae, Bliss scorpionidae, Hairy scorpionidae, Fearful scorpionidae, Trapped scorpionidae, Semiscorpionidae, Scorpionidae, Heteroscorpionidae, Diploscorpionidae, Thin scorpionidae; (7) Phylum Mollusca, Class Gastropod, Order Cephalopoda: Pseudo-spined Snails, Pseudo-spined Sea Snails, Adidae, Sternidae, Semeno-spined Snails ... (8) Phylum Mollusca, Class Gastropod, Order Aplysia: Cylindrica, Aplysia, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae, Hylostomidae; (9) Phylum Mollusca, Class Gastropod, Order Nudibranch: Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae, Trionychidae; (10) Phylum Mollusca, Class Cephalopoda, Order Sepiidae: Sepiidae, Subfamily Heteropodinae, Subfamily Sakinocephalae, Subfamily Otocephalae; (11) Phylum Mollusca, Class Cephalopoda, Order Octopus: Octopidae, Giant Octopidae, Coleoptera, Cuttlefish, Argonautidae, Heptapodidae, Deep-sea Octopus, Brachycoidea; (12) Chordata: Acipenseridae, Hypophthalmichthys, Hypophthalmichthys, Neophthalmichthys, Osteoglossidae, Anguilla, Anguidae, Acanthodontidae, Cypriniformes, Gnaphalinae, Salmoniformes, Salmoninae, Herpidae, Salmoniformes, Ophiodontidae ... , Siluriformes, Siluridae, Silversides, Gnathophoridae, Silversides, Gnathophoridae, Gnathophoridae, Gadformes, Gadidae, Ophiopods, Ophiopods, Chrysopidae, Ophiopods, Ophiopods, Ophiopods, Ophiopods, Sphenodontidae, Syngnathidae, Syngnathidae, Syngnathidae, Perciformes, Wrasseniidae, Perciformes, Rockfish, Perciformes, Pomacanthidae, Perciformes, Cichlidae; (13) Chordata, Amphibia, Apodidae: Jellyfish, Anemone, Lumbricidae, Leechidae, Snakes, Sea Cucumbers, Asteridae, Echinoidea, Snails, Mussels, Clams, Calycozoidae; (14) Chordata, class Amphibia, order Caudata: Cryptobranchidae, Ambystoma, Eusalidae, Hypoderma, Pulmonary Salamanders, Amphibia, Caviidae, Costidae, Eudontidae, Fat Salamanders, Blind-eyed Lumbricidae, and Megalostomidae; (15) Chordata, Amphibia, Anura: Toads, Rhacophoridae, Hylacidae, Ceratopogonidae, Mylodactylidae, Microdactylidae; (16) Phylum Chordata: Reptiles: Squamata, Testudinidae, Dermatochelydae, Testudinidae, Cheloniformes, Testudinidae, Testudinidae, Crocodilia, Alligators, Alligators, Alligators; (17) Chordata: Psittaciformes, Cockatielidae, Psittaciformes, Lorikeetidae, Anseriformes, Anatidae, Anseriformes, Anseriformes, Spheniscidae, Passeriformes, Passeriformes, Corvidae, Passeriformes, and Passeriformes; (18) Chordata: Monotremes: Platypus, Echidna, Perissodactyla, Rhinoceros, Proboscidea; (19) Chordata, Mammalia, Marsupials: Marmosets, Koalas, Bandicoots, Wombats, and Quetzalcoatlus; (20) Chordata, class Mammalia, order Rodentia: Sciuridae, Cricetidae, Bamboo Rhynchomys, Dormouse, Myrmecophaga, Caviidae, Beaver, Flying Squirrel, Porcupine, Lemming, Gerbil, Capybara; (21) Chordata, Mammalia, Chiroptera: Pteropus, Rhinolophus, Hippodrome, Myotis, Long-winged Bat, Brachypterygidae, Fruit Bat; (22) Chordata, Mammalia, Carnivora: Felidae, Canidae, Ursidae, Mustelidae, Lutradae; (23) Chordata, Mammalia, Primates: Hominidae, Gibbon, Loris, Tarsier, Lemuridae; (24) Chordata, Mammalia, Artiodactyla: Camelidae, Suidae, Peccary, Giraffidae, Pronghorn, Cervidae, Musk Deer, Bovidae, Hippopotamidae; (25) Phylum Chordae, Class Mammalia, Order Cetacea: freshwater dolphins, sperm whales, beaked whales, narwhals, sharp-nosed dolphins, dolphins, porpoises, baleen whales, gray whales, right whales, minke whales, beaked whales, fin whales; The plant-derived protein core-shell structure nanocrystal is a core-shell structure nanocrystal of at least one of the proteins contained in the following plants: (1) Ceratophyllum: Ceratophyllums: Ceratophyllums, ... (2) True Mosses: Axis order, Axis family, Axis order, Hoary moss family, Axis order, Micro-moss family, Corrugated moss order, Corrugated moss family, Beaded moss order, Beaded moss family, True moss order, True moss family, True moss order, Lantern moss family, Shrimp moss order, Shrimp moss family, Tobacco moss order, Tobacco moss family, Brachycera order, Brachycera family, Opposite leaf order, Opposite leaf order, Anti-neon moss family, Gourd moss order, Big cap moss family, Gourd moss order, Gourd moss family, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Purple calyx order, Stone crack moss Mosses, the order of the purple-calyx mosses, the order of the tiger-tail mosses, the order of the yellow-yellow mosses, the order of the oily mosses, the order of the oily mosses, the order of the white mosses, the order of the oily mosses, the order of the velvet-cap mosses, the order of the tree-lime mosses, the order of the tree-lime mosses, the order of the tree-lime mosses, the order of the straight-toothed mosses, the order of the wood-ling mosses, the order of the wood-ling mosses, the order of the ridge-capped mosses, the order of the juniper mosses, the order of the juniper mosses, the order of the water-lichen mosses, the order of the twisted-stem mosses, the order of the water-lichen mosses, the order of the water-lichen mosses, the order of the cold-lichen mosses, the order of the water-lichen mosses, the order of the beautiful-lichen mosses; (3) Eubryophyta, Eubryophyta, Angiospermaceae, Angiospermaceae, Angiospermaceae, Angiospermaceae, Angiospermaceae; (4) True mosses: Onagraceae, Bolognaaceae, Reverse hair mossaceae, Green mossaceae, Wetland mossaceae, Wannian mossaceae, Cryptocapsulariaceae, Silk mossaceae, Brocteraceae, Sphagaceae, Soft tooth mossaceae, Tower mossaceae, Gray mossaceae, Peacock mossaceae, Boat leaf mossaceae, Thin Luo mossaceae, White tooth mossaceae, Crepe mossaceae, Tilapia mossaceae, Golden hair mossaceae, Flat mossaceae, Straight mossaceae, Cotton mossaceae, False fine Luo mossaceae, Axillary mossaceae, Pteridaceae, Golden gray mossaceae, Hairy brocade mossaceae, Heterodontaceae, Weeping mossaceae, Heliconia mossaceae, Brocade mossaceae, Pseudo-thin Luo mossaceae, Sclerophyllaceae, Acanthaceae, Lepiophyllaceae, Thick handle mossaceae; (5) Eubryophytes, Eubryophytes, and Hypobryophytes: Phyllostachys, Candleleafys, Microhylophytes, Botrychnophytes, Arboretum, Hypobryophytes, Thick Lithophytes, Echinopsaceae, and Light Mosses; (6) True mosses: Black mosses, Black mosses, Black mosses, Black mosses, True mosses: Long mosses, Long mosses, Long mosses, True mosses: Golden mosses, Golden mosses, Golden mosses, True mosses: Sphagnum mosses, Sphagnum mosses, True mosses: Sphagnum mosses, True mosses: Sphagnum mosses, True mosses: Algae mosses, Algae mosses, True mosses: Tetradentata mosses, Tetradentata mosses, Tetradentata mosses; (7) Chlorophyta, Chlorophyta: Bryophyceae, ... (8) Chlorophyta, Chlorophyta, Acrophyceae, Acrophyceae, Gymnophyceae, Gymnophyceae, Gymnophyceae, Gymnophyceae, Dauerlys ... (9) Marchantia: Bracteaceae, Microphylla, Microphylla, Nanximeiaceae, Forkleaf, Forkleaf, Greenleaf, Bandleaf, Bandleaf, Mossleaf, Bandleaf, Purpleleaf, Purpleleaf, Light-calyx, Ear-leaf, Light-calyx, Hair-ear, Light-calyx, Fine-scale, Light-calyx, Eye-calyx, Light-calyx, Flat-calyx, Hair-leaf, Hair-leaf, New-leaf; (10) Phyllophyllous order: Acrocalyceae, Cryptocapsulariaceae, Erectleafaceae, Leptocarpaceae, Pocillopora, Eyelashaceae, Capsulariaceae, Macrocalyceae, Pseudo-macrocalyceae, Geocalyceae, Holocyceae, Fusariumaceae, Shearleafaceae, Longicyceae, Armoraceae, Leafmoss, Complexaceae, Fingerleafmoss, Toothcalyceae, Splitleafmoss, Beardmoss, Microcalyceae, Pseudocalyceae, Feathermoss, Pseudo-complexaceae, Scutellariaceae, Synophyllaceae, Diplocoleaceae, Tubemoss, Horizontalleafmoss, Velvetmoss; (11) Phylum Ranunculaceae, Class Ranunculales: Verruco-crown family, Star-hole family, Snake family, Flowery family, Liverwort family, Dioscorea family, Light family, Single-month family, Money family, Leather-leaf family, Wesley family; (12) Rhodophyta: Acrophyceae, Acrophyceae, Ignaec ... (13) Rhodophyta, Rhodophyta, and Taxodium: Stem-spined algae, Gelatophyceae, Endophyceae, Taxodium, Myxocystis, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae, Hyalariaceae; (14) Vascular plants, class Equisetum: Alsophilales, Cyathophytes, family Cyathophytes, family Cyathophytes, family Equisetaceae, family Diplophyllaceae, family Diplophyllaceae, family Diplophyllaceae, family Hymenopterales, family Hymenopterales, family Hymenopterales, family Hymenopteraceae, family Osmanthaceae, family Pinaceae, family Sophora, family Sophora, family Sophora, family Cyperaceae, family Cyperaceae; (15) Vascular plants, class Equisetaceae, order Polypodiaceae: Aspleniaceae, Aspleniaceae, Pterid ... (16) Vascular plants: Acorusales, Acorus family; Palmaceae; Schisandraceae; Boraginaceae; Buxusales, Buxus family; Celastraceae; Ceratophyllum family; Ceratophyllum family; Chrysanthemum family; Commelinaceae; Commelinaceae; Commelinaceae; Commelinaceae; Commelinaceae; Cornaceae; Cornaceae; Hydrangeaceae; Cornaceae; Cyanophyllum family; Tassel family; Tassel family; Pentacarpaceae; Cucurbitaceae; Cucurbitaceae; Begoniaceae; Cucurbitaceae; Moracaceae; Cucurbitaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; Dioscoreaceae; The order Acanthaceae, the order Leguminosae, the order Polygala, the order Merantiaceae, the order Psoralea, the order Psoralea, the order Eucommia, the order Geraniales, the order Decapoda, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Psoralea, the order Vitis, the order Vitis; the order Vitis; (17) Vascular plants: Alismataceae, Araceae, Araceae, Asteraceae, Asteraceae, Asteraceae, Asteraceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae, Aquaticaceae; (18) Vascular plants, Magnoliaceae, Apiaceae, Araliaceae, Pittosporaceae, and Coleopsaceae; (19) Vascular plants, Magnoliaceae, Aquilegiaceae: Aquilegiaceae, Aquilegiaceae, Aquilegiaceae; (20) Vascular plants, Magnoliaceae, Asparagales: Asparagaceae, Amaryllidaceae, Asphodelaceae, Curculigoaceae, Iridaceae, Orchidaceae; (21) Vascular plants: Magnoliaceae, Asterales, Asteraceae, Campanulaceae, Menymaceae, Pentaphyllum, Stylophyllum; (22) Vascular plants, Magnoliaceae, Cruciferae: Cruciferae, Glechomaea, Carica, Caricaceae, Moringaceae, Meliaceae, Echinopsaceae, Nasturtiumaceae; (23) Vascular plants: Caryophyllaceae, Aizoaceae, Amaranthaceae, Uncariaceae, Basella, Cactaceae, Droseraceae, Petalopsis, Pinaceae, Cornaceae, Nepenthesaceae, Mirabilis, Allium, Phytolaccae, Pleurotus, Polygonaceae, Portulaceae, Glechomae, Salicaceae; (24) Vascular plants: Ericaceae, Actinidiaceae, Impatiens, Alnus, Ixigera, Diospyros, Ericaceae, Leydigaceae, Cyperaceae, Pentaphyllum, Allium, Primulaceae, Sapotaceae, Costaceae, Styracaceae, Asteraceae, Theaceae; (25) Vascular plants, Magnoliaceae, Fagales: Fagaceae, Betulaceae, Casuarinaceae, Fagaceae, Juglandaceae, Myricaceae; (26)) Vascular plants, Magnoliaceae, Gentianales: Gentianaceae, Apocynaceae, Gelsemium, Gentianaceae, Loganaceae, Rubiaceae; (27) Vascular plants, Magnoliaceae, Labiatae: Lamiaceae, Acanthaceae, Bignoniaceae, Vanillaceae, Gesneriaceae, Utriculariaceae, Matricariaceae, Ceratoniaceae, Aquilegiaceae, Oleaceae, Orobanchaceae, Paulowniaceae, Sesamaceae, Penicillaceae, Plantaginaceae, Scrophulariaceae, Verbenaceae, and Aglaonema; (28) Vascular plants, Magnoliaceae, Liliales: Liliaceae, Colchicumaceae, Hostaceae, Veratrum, Smilaxaceae; (29) Vascular plants: Malpurinae, Echinopsaceae, Echinopsaceae, Anshenaceae, Garciniaceae, Pomacantha, Stellariaceae, Corydalis, Euphorbiaceae, Hypericaceae, Glutinaceae, Linaceae, Tropaeolaceae, Cyperaceae, Passifloraceae, Arboraceae, Phyllanthaceae, Carexaceae, Drupaceae, Rhizophoraceae, Salicaceae, Violaceae; (30) Vascular plants, Magnoliaceae, Malvaceae: Malvaceae, Malvaceae, Helianthaceae, Dipterocarpaceae, Thymelaeaceae; (31) Vascular plants, Magnoliaceae, Myrtales: Myrtaceae, Combretaceae, Cryptomeriaceae, Lythraceae, Melastomataceae, Onagraceae; (32) Vascular plants, Magnoliales, Pandanaceae: Pandanaceae, Stemonaceae, Mycorrhizae, and Featherleafaceae; (33) Vascular plants: Magnoliaceae, Poaceae, Bromeliaceae, Cyperaceae, Cyperaceae, Cyperaceae, Juncaceae, Sphagaceae, Juncaceae, Typhaceae, and Cyperaceae; (34) Vascular plants, Magnoliaceae, Proteales: Proteaceae, Nelumboceae, Platanaceae, and Ceropegiaceae; (35) Vascular plants, Magnoliaceae, Ranunculales: Ranunculaceae, Berberidaceae, Astrophyllaceae, Akebiaceae, Menispermaceae, Papaveraceae; (36) Vascular plants: Magnoliaceae, Rosaceae, Elaeagnaceae, Moraceae, Rhamnaceae, Rosaceae, Ulmaceae, Urticaceae; (37) Vascular plants: Magnoliaceae, Santalum orders: Santalaceae, Cyperaceae, Cyperaceae, Cyperaceae, Loranthaceae, Aspergillus family, Citronaceae, Santalaceae, Cyperaceae, and Malvaceae; (38) Vascular plants, Magnoliaceae, Sapindaceae: Sapindaceae, Anacardiaceae, Botrytis cinerea, Oleaceae, Meliaceae, Nitraria tanguticaceae, Rutaceae, Simsinaceae; (39) Vascular plants: Magnoliaceae, Saxifragales: Saxifragaceae, Mycorrhizaceae, Cynomorium, Sansevieriaceae, Ribesaceae, Echinochloa, Hamamelidaceae, Myristicaceae, Paeoniaceae, Psoralea, Saxifragaceae; (40) Vascular plants, Magnoliaceae, Solanales: Solanaceae, Convolvulaceae, Acanthaceae, Sphenopalmataceae; (41) Vascular plants, Magnoliaceae, Zingiberales: Zingiberaceae, Cannaceae, Zingiberaceae, Orchidaceae, Marantaceae, Musaceae, Strelitziaceae; (42) Vascular plants: Araucariaces, Araucariaceae, Araucariaces, Podocarpaceae, Cupressaceae, Cupressaceae, Cupressaceae, Taxaceae, Cycadales, Cycadaceae, Ephedales, Ephedraceae, Ginkgoales, Ginkgoaceae, Gnetaceae, Pinaceae, Pinaceae, and Machilaceae.

4. The ultra-high resolution colorimetric sensor based on a thickness gradient responsive film according to claim 1, characterized in that: The protein core-shell structure nanocrystal is selected from any one of the core-shell structure nanocrystals selected from lysozyme, bovine serum albumin, human serum albumin, lactoferrin, whey albumin, insulin, α-lactalbumin, fibrinogen, β-lactoglobulin, ribonuclease A, cytochrome c, α-amylase, horseradish peroxidase, pepsin, myoglobin albumin, collagen, keratin, hemoglobin, DNA polymerase, casein, soy protein, pea protein isolate, zein, gliadin, gluten, oat protein, potato protein, hemp kernel protein, walnut protein, rapeseed protein, hazelnut protein, quinoa protein, sunflower seed protein, pumpkin seed protein, black sesame protein, mushroom protein, red algae protein, legumin, barley protein, wheat protein, glutenin, kidney bean protein, casein, collagen, catalase, transferrin, and thyrolactoglobulin.

5. The ultra-high resolution colorimetric sensor based on a thickness gradient responsive film according to claim 1, characterized in that: The responsive block polymer is selected from poly(N-isopropylacrylamide)-polyacrylic acid, poly(N-isopropylacrylamide)-polylactic acid, polyethylene oxide-polypropylene oxide block copolymer, polyacrylic acid-polystyrene, polyhistidine-polyethylene glycol, polyethylene oxide-azobenzene-polystyrene, polymethyl methacrylate-spiropyran, Fe3O4@polypyrrole-polyethylene glycol, polyacrylic acid-polystyrene sulfonic acid, polyethylene glycol-polycaprolactone containing disulfide bonds, poly(N-isopropylacrylamide)- Polycaprolactone, poly(N-isopropylacrylamide)-polystyrene, polyethylene oxide-polypropylene oxide-polyethylene oxide, polycaprolactone-polyN-isopropylacrylamide, poly-L-lactic acid-poly-N-isopropylacrylamide, poly(dimethylaminoethyl methacrylate)-polyethylene glycol, polyvinyl caprolactam-polyethylene glycol, polyethylene glycol-poly D,L-lactic acid, polyacrylic acid-polystyrene, polyacrylic acid-polyethylene glycol, poly(diethylaminoethyl methacrylate)-polycaprolactone, poly(methacrylic acid)-polyethylene glycol Alcohol, poly 2-vinylpyridine-polystyrene, poly 4-vinylpyridine-polycaprolactone, polyacrylic acid-poly dimethylaminoethyl methacrylate, polyethylene glycol-polyaspartic acid, polyethyleneimine-polycaprolactone, polymer containing azobenzene group-polyethylene glycol, polystyrene-containing spiropyran photoresponsive block, polyethylene oxide-containing nitrophenyl ester photocleavable block, azobenzene-modified poly dimethylaminoethyl methacrylate, polycaprolactone-containing spiropyran block, polymethacrylate containing o-nitrobenzyl photocleavable group , polyethylene glycol-polylactic acid containing disulfide bonds, polystyrene-polyacrylic acid containing disulfide bonds, polyethylene oxide-polymethacrylic acid, polystyrene-polyvinyl pyrrolidone, polyethylene glycol-sodium polystyrene sulfonate, polyethylene glycol-poly(N-isopropylacrylamide)-polyacrylic acid, polycaprolactone-poly(N-isopropylacrylamide)-azobenzene, polyethylene glycol-polymethacrylate dimethylaminoethyl ester containing disulfide bonds, and polyacrylic acid-poly(N-isopropylacrylamide) containing ferrocene groups.

6. The ultra-high resolution colorimetric sensor based on a thickness gradient responsive film according to claim 1, characterized in that: An aqueous solution of a responsive polymer is coated on a substrate through a programmed continuous two-step spin coating process to form a thin film with multiple concentric circular color patterns, thereby obtaining an ultra-high resolution colorimetric sensor based on a thickness gradient responsive film; wherein the two-step spin coating process is a first step low-speed spin coating process and a second step high-speed spin coating process, the first step low-speed spin coating process has a rotation speed of 800-1200 r / min and a spin coating time of 90-200 s, the second step high-speed spin coating process has a rotation speed of 4000-5000 r / min and a spin coating time of 240-480 s, and the spin coating temperature is 5-50°C.

7. The ultra-high resolution colorimetric sensor based on a thickness gradient responsive film according to claim 6, characterized in that: The first step of low-speed spin coating process has a rotation speed of 800-1000 r / min and a spin coating time of 90-120 s, the second step of high-speed spin coating process has a rotation speed of 4500-4600 r / min and a spin coating time of 300-360 s, and the spin coating temperature is 20-40°C.

8. The ultra-high resolution colorimetric sensor based on a thickness gradient responsive film according to claim 6, characterized in that: The viscosity of the aqueous solution of the responsive polymer is 20-50 mPa·s, wherein the concentration of the responsive polymer is 8-15 mg / mL.

9. Use of the ultra-high resolution colorimetric sensor based on thickness gradient responsive film according to claim 1 in colorimetric detection of relative humidity.

10. Use of the ultra-high resolution colorimetric sensor based on the thickness gradient responsive film according to claim 1 in colorimetric detection of organic amine vapor, wherein the organic amine vapor is any one of methylamine, aniline, ethylamine, dimethylamine, diphenylamine, piperidine, trimethylamine, triethylamine, triphenylamine, tetramethylammonium bromide, benzyltrimethylammonium chloride, n-butylamine, cyclohexylamine, aniline, o-toluidine, pyridine, morpholine, ethylenediamine, hexamethylenediamine, triethylenetetramine, dopamine, putrescine, histamine, tyramine, spermine, spermidine, phenylethylamine, cadaverine, ethanolamine, cysteamine, and caprolactam.

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