WO2020259490A1 - 一种在近红外光照下发荧光桑蚕丝的制备方法及产品 - Google Patents

一种在近红外光照下发荧光桑蚕丝的制备方法及产品 Download PDF

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WO2020259490A1
WO2020259490A1 PCT/CN2020/097679 CN2020097679W WO2020259490A1 WO 2020259490 A1 WO2020259490 A1 WO 2020259490A1 CN 2020097679 W CN2020097679 W CN 2020097679W WO 2020259490 A1 WO2020259490 A1 WO 2020259490A1
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nanoparticles
infrared light
mulberry
under near
silk
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French (fr)
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杨明英
王捷
陈玉银
张颖
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Zhejiang University ZJU
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K67/00—Rearing or breeding animals, not otherwise provided for; New or modified breeds of animals
    • A01K67/30—Rearing or breeding invertebrates
    • A01K67/34—Insects
    • A01K67/35—Silkworms
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K10/00—Animal feeding-stuffs
    • A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/105—Aliphatic or alicyclic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/142—Amino acids; Derivatives thereof
    • A23K20/147—Polymeric derivatives, e.g. peptides or proteins
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/20—Inorganic substances, e.g. oligoelements
    • A23K20/22—Compounds of alkali metals
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K40/00—Shaping or working-up of animal feeding-stuffs
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K50/00—Feeding-stuffs specially adapted for particular animals
    • A23K50/90—Feeding-stuffs specially adapted for particular animals for insects, e.g. bees or silkworms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y99/00—Subject matter not provided for in other groups of this subclass
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent materials, e.g. electroluminescent or chemiluminescent
    • C09K11/08—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials
    • C09K11/77—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent materials, e.g. electroluminescent or chemiluminescent containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7772—Halogenides
    • C09K11/7773—Halogenides with alkali or alkaline earth metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery

Definitions

  • the invention belongs to the field of silk fiber production and processing, and specifically relates to a preparation method for preparing fluorescent mulberry silk under near-infrared light.
  • Silk cellulose has the reputation of "fiber queen", its mechanical properties are excellent, the fabric formed is smooth, bright in color, and has good air permeability and heat insulation. Therefore, silk fiber has played an important role in my country's economic development.
  • the traditional sericulture textile industry is facing severe challenges.
  • researchers have introduced or modified functionalized macromolecules into silk fibers by different means to improve the properties of silk fibers and enhance their application value. At present, there are researches on transforming silk into fluorescent silk fibers for use in in vivo imaging and detection.
  • Up-conversion nanoparticles are luminous bodies composed of rare earth ions, which can convert long-wavelength near-infrared light into short-wavelength visible light, with stable luminescence and high signal-to-noise ratio.
  • up-conversion nanoparticles Compared with common luminescent materials such as anthocyanins and quantum dot particles, up-conversion nanoparticles have stable properties, low biological toxicity, and high luminescence intensity, and they have a wide range of applications in the fields of biomedical detection and imaging. Therefore, combining up-conversion nanoparticles with silk fibers and seeking fiber modification can enhance the practical feasibility of silk fibers in the field of in vivo imaging and detection.
  • up-conversion nanoparticles are mixed with regenerated silk protein, and electrospinning is used to produce luminous silk fibers.
  • the electrospinning method takes a long time and the output is low, and mass production cannot be realized.
  • the surface-modified up-conversion nanoparticles are often unevenly distributed and easily fall off. Therefore, it is necessary to develop a new method that can simply and mass obtain up-conversion nanoparticles containing mulberry silk that emits fluorescence under near-infrared light.
  • the present invention provides a method for preparing mulberry silk that is excited by near-infrared light and fluoresces. This method can not only improve the fluorescent silk fiber with high fluorescence intensity, strong penetrating power and good biocompatibility, but also suitable for mass production without pollution to the environment.
  • a method for preparing fluorescent mulberry silk under near-infrared light including the following steps:
  • step (1) Disperse the up-conversion nanoparticles in step (1) uniformly in water, and formulate a concentration of up-conversion nanoparticles in an aqueous solution;
  • step (3) Picking the mature mulberry leaves, immersing the mulberry leaves in the nanoparticle aqueous solution system of step (2), removing them, draining the water and drying them naturally;
  • step (3) After the silkworm grows to a set time, feed the mulberry leaves of step (3) to the silkworm until the silkworm spins and cocoons;
  • a flat plate can be used to induce it to spit flat silk or to reel the silk after the cocoon is formed on it. Both methods can obtain the mulberry silk that fluoresces under near-infrared light. Finally, the modified mulberry silk that fluoresces under near-infrared light is obtained, which can be used for in vivo imaging and detection analysis in medical and biological fields.
  • the up-conversion nanoparticles have a core-shell structure.
  • up-conversion nanoparticles with core-shell structure have higher fluorescence intensity (Figure 1).
  • the present invention can select polyacrylic acid (PAA) modified core-shell structure upconversion nanoparticles.
  • PAA polyacrylic acid
  • the present invention synthesizes and prepares polyacrylic acid (PAA) modified core-shell structure upconversion nanoparticles (UCNPs), introduces concanavalin (ConA), and uses crosslinking agent 1-ethyl-3-(3-dimethyl Aminopropyl)-carbodiimide (EDC/NHS) grafted concanavalin to the surface of upconversion nanoparticles to form a composite copolymer.
  • the method of preparing polyacrylic acid (PAA) modified core-shell structure upconversion nanoparticles is as follows:
  • the core-shell structure up-conversion nanoparticles ( ⁇ -NaYF 4 :Yb, Er@ ⁇ -NaYF 4 ) are prepared by the existing method, and dispersed in a n-hexane solution.
  • the surface of the nanoparticles was grafted with polyacrylic acid (PAA) by the ligand exchange method, and 1 mL of the upconversion nanoparticle solution was blended with 5 mL of dimethylformamide (DMF), and then 4 mL of n-hexane was added and stirred for 3 hours. Add 5-10 mL of isopropanol for precipitation and wash with DMF several times.
  • the precipitate was resuspended in PAA/DMF solution with a PAA concentration of 10 mg/mL (5-10 mL), stirred overnight and washed by centrifugation.
  • the method of surface modification with concanavalin is as follows:
  • the up-conversion nanoparticles that can be used in the present invention include but are not limited to ⁇ -NaYF 4 :Yb, Er@ ⁇ -NaYF 4 up-conversion nanoparticles, and can also be obtained by other preparation methods such as NaGdF4:Yb/Er@NaGdF4: Yb/Nd or NaYF4: Yb, Er without shell structure or up-conversion nanoparticles with red fluorescence, etc.
  • the concentration of the up-conversion nanoparticle aqueous solution is 1 to 5 g/L.
  • the silk gland cells of the silkworm become larger. Most of the mulberry leaves that are eaten are converted to synthesize silk protein. Before this, the mulberry leaves are only the nutrients learned for growth or are excreted. In order to improve the feeding efficiency, it is preferred.
  • the silkworm grows to the third day of the fifth instar, the silkworm is fed with the mulberry leaves of step (3). Feed ordinary mulberry leaves to 1 to 4 instar silkworms.
  • the average diameter of the modified up-conversion nanoparticles obtained in step (1) is 50-100 nm.
  • the emitted light color can be green, red, or yellow.
  • the mulberry leaf treatment method in step (3) is leaching and drying, which can make the nanoparticles more evenly distributed on the front and back surfaces of the mulberry leaves, enabling effective comparison Analysis has avoided the defect of uneven distribution of traditional spray methods. In addition, it is more accurate when the concentration is quantitatively processed, and the efficiency of silkworm intake is improved.
  • the mulberry leaf immersion time is 2-5 min.
  • step (5) the silkworm silk is collected by using an induced silkworm flat plate.
  • the obtained silk can be directly used in practical applications.
  • the concanavalin in the step (1) is a tetrameric globulin that can precipitate a variety of sugars including glucan, fructan, and immunoglobulins and blood group substances.
  • a variety of glycoproteins can bind or react with a variety of cells.
  • the invention introduces concanavalin-modified up-conversion nanoparticles, which aims to improve the affinity of the nanoparticles and the cells in the silkworm body, participate in silk protein synthesis more effectively, and form fluorescent silk fibers.
  • the hydrophilic upconversion nanoparticles are prepared, and therefore, they have good dispersibility in an aqueous solution system.
  • a mulberry silk that emits fluorescence under near-infrared light is characterized by being prepared by the method described in any of the above technical solutions.
  • the invention can perform fluorescence detection through near-infrared light excitation, and in addition, detect the content of rare earth elements constituting UCNPs in nanofibers by inductively coupled plasma mass spectrometry (ICP-MS).
  • ICP-MS inductively coupled plasma mass spectrometry
  • the up-conversion material selected in the present invention has the defects of being easier to be quenched, short fluorescence maintenance time, and the up-conversion material has longer light stability.
  • the traditional feeding method simply feeding rhodamine, fluorescein sodium and other fluorescent chemicals, the fluorescence produced is usually only distributed in the sericin, rarely in the silk fibroin, and no fluorescence after degumming. Due to the modification of concanavalin, the present invention can enhance the affinity between the feeding material and the silk gland cells and improve the fluorescence effect of the silk fibroin.
  • the invention discloses a preparation method of fluorescent mulberry silk under near-infrared light.
  • the present invention first prepares core-shell structure upconversion nanoparticles, and uses concanavalin for surface modification to obtain nanoparticle copolymers; disperse the upconversion nanoparticles in water to prepare an aqueous solution with a concentration of 1 to 5 g/L; Fresh mulberry leaves are immersed in the nano-particle aqueous solution for 2 to 5 minutes, and they are taken out and dried naturally; then when the silkworm grows to the fifth instar and the third day, the mulberry leaves treated with nano-particles are fed to them until silking and cocoon formation; Modified mulberry silk is obtained by the method of plate induction or silkworm cocoon reeling. After being excited by near-infrared light with a wavelength of 980nm, the modified mulberry silk can emit bright
  • the present invention has the following outstanding advantages:
  • up-conversion nanoparticles are used as food supplements. Compared with other fluorescent quantum dot feeding treatments, up-conversion nanoparticles can emit fluorescence under the irradiation of more penetrating near-infrared light, which has better applications for deep tissue imaging. In addition, compared with fluorescent quantum dots, up-conversion nanoparticles have more stable properties, higher biological safety, stronger signal-to-noise ratio, and wider application range.
  • the present invention introduces concanavalin for modification, which can improve the combination of nanoparticles and silk protein, and make up for the defects of fewer fluorescent silk particles produced by traditional feeding methods and poor effect.
  • the present invention adopts the extraction method to process the fed mulberry leaves, so that the nano-particle coverage is more uniform, and effective quantitative comparison can be performed.
  • Figure 1 shows the fluorescence pictures of non-core-shell structure upconversion nanoparticles and core-shell structure upconversion nanoparticles under 980nm laser excitation. (On the left is the non-core-shell structure upconversion nanoparticles, and the right is the core-shell structure upconversion nanoparticles)
  • Fig. 2 is a fluorescence graph of the flat filament obtained in Example 1 under 980nm laser irradiation.
  • the existing method J.Am.Chem.Soc.128,6426-6436. was used to prepare the core-shell structure upconversion nanoparticles ( ⁇ -NaYF 4 :Yb, Er@ ⁇ -NaYF 4 ) and dispersed in the normal In alkane solution.
  • a ligand exchange method was used to graft polyacrylic acid (PAA) onto the surface of the nanoparticles.
  • PAA polyacrylic acid
  • 1 mL of the upconverting nanoparticle solution was blended with 5 mL of dimethylformamide (DMF), and then 4 mL of n-hexane was added and stirred for 3 hours. Add 5-10 mL of isopropanol for precipitation and wash with DMF several times.
  • the precipitate was resuspended in PAA/DMF solution with a PAA concentration of 10 mg/mL (5-10 mL), stirred overnight and washed by centrifugation. Disperse 10mg of PAA-modified nanoparticles in 1mL aqueous solution, add 1mg each of EDC and NHS, stir for 3-6h, then 30uL concanavalin aqueous solution (3-10mg/mL), stir overnight, centrifuge and wash to obtain Concanavalin modified upconversion nanoparticles;
  • step (2) Disperse the up-conversion nanoparticles synthesized in step (1) with water to prepare a dispersion solution with a concentration of 2 g/L;
  • step (3) Picking the mature mulberry leaves, soaking them in the nanoparticle solution of step (2), soaking for 2 minutes and then removing them, and let them dry naturally.
  • step (3) feed the mulberry leaves of step (3) to the silkworm until it spins and cocoons.
  • the existing method J. Phys. Chem. C, Vol. 113, No. 44, 2009 was used to prepare red fluorescence up-conversion nanoparticles (NaYF 4 : 1% Er, 1% Tm), and dispersed in n-hexane In solution.
  • the surface of the nanoparticles was grafted with polyacrylic acid (PAA) by the ligand exchange method, and 1 mL of the upconversion nanoparticle solution was blended with 5 mL of dimethylformamide (DMF), and then 4 mL of n-hexane was added and stirred for 3 hours. Add 5-10 mL of isopropanol for precipitation and wash with DMF several times.
  • the precipitate was resuspended in PAA/DMF solution with a PAA concentration of 10 mg/mL (5-10 mL), stirred overnight and washed by centrifugation. Disperse 10mg of PAA-modified nanoparticles in 1mL aqueous solution, add 1mg each of EDC and NHS, stir for 3-6h, then 30uL concanavalin aqueous solution (3-10mg/mL), stir overnight, centrifuge and wash to obtain Concanavalin-modified up-conversion nanoparticles;
  • step (2) Disperse the up-conversion nanoparticles synthesized in step (1) with water to prepare a dispersion solution with a concentration of 5 g/L;
  • step (3) Picking the mature mulberry leaves, soaking them in the nanoparticle solution of step (2), soaking for 2 minutes and then removing them, and let them dry naturally.
  • step (3) feed the mulberry leaves of step (3) to the silkworm until it spins and cocoons.
  • step (2) Disperse the up-conversion nanoparticles synthesized in step (1) with water to prepare a dispersion solution with a concentration of 5 g/L;
  • step (3) Picking the mature mulberry leaves, soaking in the nanoparticle solution of step (2), soaking for 5 minutes, removing them, and drying them naturally.
  • step (3) feed the mulberry leaves of step (3) to the silkworm until it spins and cocoons.
  • the mulberry silk prepared in Example 3 was used as sample 1.
  • Table 1 is a comparison table of the rare earth element content in ordinary mulberry silk and modified mulberry silk measured by ICP-MS in Example 3.
  • Table 1 shows that the nano-particles we added food can be detected in the final silk, indicating that the food efficiency is relatively high.

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Abstract

本发明公开了一种在近红外光照下发荧光桑蚕丝的制备方法，包括：(1)制备上转换纳米颗粒，并用伴刀豆球蛋白进行表面修饰，获得修饰后的上转换纳米颗粒；(2)将修饰后的上转换纳米颗粒在水中均匀分散，配制成上转换纳米颗粒水溶液；(3)摘取成熟桑叶，将桑叶浸没于纳米颗粒水溶液体系中，将水沥净后自然晾干；(4)待家蚕生长至设定时间后，对家蚕饲喂处理后桑叶，直至家蚕吐丝结茧；(5)收集蚕丝，得到近红外光照下发荧光桑蚕丝。本发明选用能够在穿透力更强的近红外光照射下发射荧光的上转换纳米颗粒，对于深层组织成像有更好的应用。且上转换纳米颗粒性质更加稳定、生物安全性更高，信噪比更强，适用范围更加广阔。

Description

一种在近红外光照下发荧光桑蚕丝的制备方法及产品 技术领域
本发明属于蚕丝纤维生产和加工领域，具体是涉及一种制备近红外光照下发荧光桑蚕丝的制备方法。
背景技术
蚕丝纤维素有“纤维皇后”之美誉，其力学性能优异，形成的织物手感顺滑、色泽鲜明，并且具有良好的透气性和隔热性。因此，蚕丝纤维在我国经济发展历程中发挥了重要的作用。然而，随着人造纤维工业化合成技术的迅猛发展，传统的蚕桑纺织行业正遭受严峻的挑战。近年来，对天然蚕丝改性的研究受到越来越多的关注，研究者将功能化大分子通过不同手段导入或修饰于蚕丝纤维，使蚕丝纤维性能改善，提升其应用价值。目前，有研究将蚕丝改造成具有荧光的蚕丝纤维，运用于体内成像和检测。然而，在实际应用中发现，普通的蚕丝纤维具有很强的自发荧光，在紫光和绿光照射下能散发黄色和红色荧光，严重干扰检测应用。另一方面，目前获得的荧光蚕丝都是在可见光激发条件下，而可见光穿透性能差，很难达到体内深层组织，被激发的荧光也极易猝灭，限制其体内活体成像的应用。因此，寻求合适的方法改性蚕丝纤维，使其具备实用价值显得尤为重要。
上转换纳米颗粒是由稀土离子构成的发光体，能够将长波长的近红外光转换成短波长的可见光，发光稳定、信噪比高。与常见的发光材料如花青素类、量子点粒子相比，上转换纳米颗粒性质稳定、生物毒性小、发光强度高，在生物医学检测、成像领域具有广泛的应用。因此，将上转换纳米颗粒与蚕丝纤维结合，寻求纤维改性，能够增强蚕丝纤维在体内成像和检测领域的实用可行性。在现有技术中，有将上转换纳米颗粒与再生蚕丝蛋白混合，通过静电纺丝制成发光蚕丝纤维。然而，静电纺丝方法耗时长，产量低，无法实现批量化生产。此外，有技术对蚕丝纤维进行上转换纳米 颗粒表面修饰，表面修饰的上转换纳米颗粒往往分布不均匀，极易脱落。因此，有必要研发出一种能简单、大批量获得含有上转换纳米颗粒的新型方法，使其在在近红外光照下发出荧光的桑蚕丝。
发明内容
为了克服现有制备荧光蚕丝技术中存在的荧光特异性低、激发光穿透力弱，成像、检测应用困难等缺陷，本发明提供了一种制备近红外光激发发荧光的桑蚕丝制备方法，这种方法不仅能提高荧光强度高、穿透力强、生物相容性好的荧光蚕丝纤维，而且适合大量生产，对环境无污染。
一种在近红外光照下发荧光桑蚕丝的制备方法，包括如下步骤：
(1)制备上转换纳米颗粒，并用伴刀豆球蛋白进行表面修饰，获得修饰后的上转换纳米颗粒；
(2)将步骤(1)的上转换纳米颗粒在水中均匀分散，配制成浓度为上转换纳米颗粒水溶液；
(3)摘取成熟桑叶，将桑叶浸没于步骤(2)的纳米颗粒水溶液体系中，后捞出，将水沥净后自然晾干；
(4)待家蚕生长至设定时间后，对家蚕饲喂步骤(3)的桑叶，直至家蚕吐丝结茧；
(5)收集蚕丝，得到近红外光照下发荧光桑蚕丝。
本发明可以采用平板诱导其吐平板丝或者待其上蔟结茧后缫丝，两种方法均可获得近红外光照下发荧光的桑蚕丝。最终获得近红外光照下发荧光的改性桑蚕丝，可用于医学、生物领域的体内成像和检测分析。
作为优选，所述上转换纳米颗粒为核壳结构。实验表明，核壳结构的上转换纳米颗粒荧光强度更高(如图1)。
作为优选，本发明可以选择聚丙烯酸(PAA)修饰的核壳结构上转换纳米颗粒。
本发明合成并制备聚丙烯酸(PAA)修饰的核壳结构上转换纳米颗粒(UCNPs)，引入伴刀豆球蛋白(ConA)，利用交联剂1-乙基-3-(3-二甲基氨丙基)-碳化二亚胺(EDC/NHS)将伴刀豆球蛋白接枝到上转换纳米 颗粒表面，形成复合共聚体。制备聚丙烯酸(PAA)修饰的核壳结构上转换纳米颗粒的方法如下：
采用现有的方法制备核壳结构上转换纳米颗粒(β-NaYF 4:Yb,Er@β-NaYF 4)，将其分散在正己烷溶液中。采用配体交换法对纳米颗粒表面进行聚丙烯酸(PAA)接枝，将1mL上转换纳米颗粒溶液与5mL二甲基甲酰胺(DMF)共混，随后再加入4mL正己烷，3小时搅拌。添加5-10mL异丙醇进行沉淀并用DMF洗涤数次。将沉淀重悬在PAA/DMF溶液中，PAA浓度10mg/mL(5-10mL)，过夜搅拌后离心洗涤。
作为优选，用伴刀豆球蛋白进行表面修饰的方法如下：
取10mg PAA修饰的纳米颗粒分散在1mL水溶液中，分别加入EDC和NHS各1mg,搅拌反应3-6h，随后30uL伴刀豆角蛋白水溶液(3-10mg/mL)，搅拌过夜，离心洗涤后可得到伴刀豆角蛋白修饰的上转换纳米颗粒。
作为优选，本发明可以使用的上转换纳米颗粒包括但不限于β-NaYF 4:Yb,Er@β-NaYF 4上转换纳米颗粒，还可以通过其他制备方法获得如NaGdF4:Yb/Er@NaGdF4:Yb/Nd或无壳结构的NaYF4:Yb,Er或发红色荧光的上转换纳米颗粒等。
作为优选，所述上转换纳米颗粒水溶液的浓度为1～5g/L。
家蚕从五龄第三天开始丝腺细胞变大，吃进去的桑叶大部分进行转换合成蚕丝蛋白，而在这之前桑叶只是生长所学营养或者被排泄，为了提高喂食效率，作为优选，待家蚕生长至五龄第三天时，对家蚕饲喂步骤(3)的桑叶。对于1～4龄蚕喂食普通桑叶。
作为优选，步骤(1)得到的修饰后的上转换纳米颗粒的平均直径为50～100nm。发射光颜色可为绿色、红色或黄色等。
相比于传统采用喷洒的方式处理桑叶，所述步骤(3)桑叶处理方式为浸提晾干处理，能使纳米颗粒更为均匀的分布于桑叶正反表面，能够进行有效的比较分析，避免了传统喷淋方式分布不均的缺陷。且进行浓度定量处理时也更加精确，且提高家蚕摄取效率。作为优选，步骤(3)中，桑叶浸没时间为2～5min。
作为优选，步骤(5)中，采用诱导家蚕平板吐丝收集蚕丝。获得的蚕丝可以直接进行实际应用。
本发明中，所述步骤(1)中的伴刀豆球蛋白是一种四聚体球蛋白，能够沉淀包括葡聚糖、果聚糖等多种糖类，以及免疫球蛋白和血型物质等多种糖蛋白，能够与多种细胞结合或反应。该发明中引入伴刀豆球蛋白修饰上转换纳米颗粒，旨在提高纳米颗粒与家蚕体内的细胞亲和力，更有效的参与丝蛋白合成，形成荧光蚕丝纤维。
所述步骤(2)中制备的是亲水性上转换纳米颗粒，因此，在水溶液体系中具有良好的分散性。
一种在近红外光照下发荧光桑蚕丝，其特征在于，由上述任一技术方案所述的方法制备得到。
本发明可通过近红外光激发进行荧光检测，此外通过电感耦合-等离子体质谱(ICP-MS)检测纳米纤维中组成UCNPs的稀土元素含量。
本发明选择上转换材料，相比于传统的荧光素钠具有更容易被猝灭，荧光维持时间短的缺陷，上转换材料有更长的光稳定性。
传统饲喂方法，单纯饲喂罗丹明、荧光素钠等荧光化学物，产生的荧光往往只分布在丝胶蛋白中，很少在丝素蛋白出现，脱胶后就不再有荧光。而本发明由于伴刀豆角蛋白的修饰，能够增强添食材料与丝腺细胞之间的亲和力，提高了丝素蛋白的荧光效果。
我们通过添加引入伴刀豆球蛋白进行修饰，提高家蚕体内纳米颗粒与丝蛋白的结合，弥补传统饲喂方法生产的荧光蚕丝目的颗粒少，效果差等缺陷。
本发明公开了一种在近红外光照下发荧光桑蚕丝的制备方法。目前，还没有一种简单工艺能够直接获得在近红外光激发下散发荧光的桑蚕丝。本发明首先制备核壳结构上转换纳米颗粒，并用伴刀豆球蛋白进行表面修饰，获得纳米颗粒共聚体；将上转换纳米颗粒分散在水中，配制成浓度为1～5g/L的水溶液；将新鲜桑叶浸没于纳米颗粒水溶液中2～5min，捞出后自然晾干；然后待家蚕生长至五龄第三天时，对其进行饲喂纳米颗粒处理后的桑叶直至吐丝结茧；采用平板诱导或者蚕茧缫丝的方法获得改性桑 蚕丝。用980nm波长的近红外光激发后，改性桑蚕丝能够发不同颜色的明亮荧光，可用于体内成像观察以及生物分子的有效检测。
与现有技术相比，本发明具有以下突出优点：
(1)本发明选用上转换纳米颗粒作为添食制剂。与其他荧光量子点添食处理相比，上转换纳米颗粒能够在穿透力更强的近红外光照射下发射荧光，对于深层组织成像有更好的应用。此外，与荧光量子点相比，上转换纳米颗粒性质更加稳定、生物安全性更高，信噪比更强，适用范围更加广阔。
(2)本发明引入伴刀豆球蛋白进行修饰，能够提高纳米颗粒与丝蛋白的结合，弥补传统饲喂方法生产的荧光蚕丝目的颗粒少，效果差等缺陷。
(3)本发明采用浸提法对饲喂桑叶进行处理，使纳米颗粒覆盖更加均匀，并能进行有效的定量比较。
附图说明
图1为非核壳结构上转换纳米颗粒和核壳结构的上转换纳米颗粒在980nm激光激发下的荧光图片。(左侧为非核壳结构上转换纳米颗粒，右侧为核壳结构上转换纳米颗粒)
图2为实施例1中获得的平板丝在980nm激光照射下的荧光图。
具体实施方式
下面通过实施例对本发明做进一步的详细说明，以下实施例是对本发明的解释而本发明并不局限于以下实施例。
本发明的实施例如下：
实施例1
(1)利用水热法制备激发绿色荧光的核壳结构上转换纳米颗粒(β-NaYF4:Yb,Er@β-NaYF4)，直径约50nm，进行表面聚丙烯酸(PAA)修饰后接枝伴刀豆球蛋白，作为添食原料,合成方法如下：
采用现有的方法(J.Am.Chem.Soc.128,6426–6436.)制备核壳结构上转换纳米颗粒(β-NaYF 4:Yb,Er@β-NaYF 4)，将其分散在正己烷溶液中。采用配体交换法对纳米颗粒表面进行聚丙烯酸(PAA)接枝，将1mL 上转换纳米颗粒溶液与5mL二甲基甲酰胺(DMF)共混，随后再加入4mL正己烷，3小时搅拌。添加5-10mL异丙醇进行沉淀并用DMF洗涤数次。将沉淀重悬在PAA/DMF溶液中，PAA浓度10mg/mL(5-10mL)，过夜搅拌后离心洗涤。取10mg PAA修饰的纳米颗粒分散在1mL水溶液中，分别加入EDC和NHS各1mg,搅拌反应3-6h，随后30uL伴刀豆角蛋白水溶液(3-10mg/mL),搅拌过夜，离心洗涤后可得到伴刀豆角蛋白修饰的上转换纳米颗粒；
(2)将步骤(1)合成的上转换纳米颗粒用水分散，配制成浓度为2g/L的分散溶液；
(3)摘取成熟桑叶，浸泡于步骤(2)的纳米颗粒溶液中，浸泡2min后捞出，自然晾干。
(4)待家蚕5龄第三天时，对家蚕饲喂步骤(3)的处理桑叶，直至其吐丝结茧。
(5)待家蚕成熟至吐丝阶段，将蚕转移至光滑平板表面，诱导其吐平板丝，随后收集。
(6)对所获得的桑蚕丝用980nm近红外激光照射，平板桑蚕丝发出明亮绿色荧光(转化为灰度图，绿色荧光部分转化为灰白色部分)，如图2所示，从而得到近红外光照下发荧光桑蚕丝。
实施例2
(1)利用水热法制备激发红色荧光的上转换纳米颗粒(NaYF 4：1％Er,1％Tm)，直径约60nm，进行表面聚丙烯酸修饰后接枝伴刀豆球蛋白，作为添食原料，合成方法如下：
采用现有的方法(J.Phys.Chem.C,Vol.113,No.44,2009)制备红色荧光上转换纳米颗粒(NaYF 4：1％Er,1％Tm)，将其分散在正己烷溶液中。采用配体交换法对纳米颗粒表面进行聚丙烯酸(PAA)接枝，将1mL上转换纳米颗粒溶液与5mL二甲基甲酰胺(DMF)共混，随后再加入4mL正己烷，3小时搅拌。添加5-10mL异丙醇进行沉淀并用DMF洗涤数次。将沉淀重悬在PAA/DMF溶液中，PAA浓度10mg/mL(5-10mL)，过夜搅拌后离心洗涤。取10mg PAA修饰的纳米颗粒分散在1mL水溶液中，分 别加入EDC和NHS各1mg,搅拌反应3-6h，随后30uL伴刀豆角蛋白水溶液(3-10mg/mL),搅拌过夜，离心洗涤后可得到伴刀豆角蛋白修饰的上转换纳米颗粒；
(2)将步骤(1)合成的上转换纳米颗粒用水分散，配制成浓度为5g/L的分散溶液；
(3)摘取成熟桑叶，浸泡于步骤(2)的纳米颗粒溶液中，浸泡2min后捞出，自然晾干。
(4)待家蚕5龄第三天时，对家蚕饲喂步骤(3)的处理桑叶，直至其吐丝结茧。
(5)待家蚕吐丝结茧后，取家蚕蚕茧进行缫丝处理，获得近红外光激发发红色荧光的桑蚕丝。
实施例3
(1)利用水热法制备激发绿色荧光的核壳结构上转换纳米颗粒(NaGdF4:Yb/Er@NaGdF4:Yb/Nd)，直径约50nm，进行表面聚丙烯酸修饰后接枝伴刀豆球蛋白，作为添食原料；
(2)将步骤(1)合成的上转换纳米颗粒用水分散，配制成浓度为5g/L的分散溶液；
(3)摘取成熟桑叶，浸泡于步骤(2)的纳米颗粒溶液中，浸泡5min后捞出，自然晾干。
(4)待家蚕5龄第三天时，对家蚕饲喂步骤(3)的处理桑叶，直至其吐丝结茧。
(5)待家蚕吐丝结茧后，取家蚕蚕茧进行缫丝处理，获得近红外光激发发绿色荧光的桑蚕丝，且荧光强度更高。
实施例3制备得到的桑蚕丝作为样品1；按照实施例3相同的方法，不同之处在于，将步骤(2)中的分散溶液的浓度稀释两倍，得到样品2；样品3为普通桑叶喂食得到的桑蚕丝；用ICP-MS对桑蚕丝中稀土元素含量进行定量分析，对比普通桑蚕丝和改性桑蚕丝中上转换纳米颗粒含量，分析比较如表1所示。
表1为实施例3中用ICP-MS测得的普通桑蚕丝和改性桑蚕丝中稀土 元素含量对比表。
序号 样品含量 Y(％) Er(％) Yb(％) Na(％)
1 样品1 2.0×10 -4 6.5×10 -4 5.0×10 -4 6.37
2 样品2 5.1×10 -4 3.0×10 -4 1.49×10 -3 9.0
3 样品3 3.3×10 -6 7.3×10 -6 6.7×10 -6 6.8
表1说明了我们添食的纳米颗粒能够在最终的蚕丝中得到含量检测说明添食效率比较高。
最后，还需要注意的是，以上列举的仅是本发明的具体实施例子。显然，本发明不限于以上实施例子，还可以有许多变形。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。

Claims (12)

  1. 一种在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，包括如下步骤：
    (1)制备上转换纳米颗粒，并用伴刀豆球蛋白进行表面修饰，获得修饰后的上转换纳米颗粒；
    (2)将步骤(1)的上转换纳米颗粒在水中均匀分散，配制成浓度为上转换纳米颗粒水溶液；
    (3)摘取成熟桑叶，将桑叶浸没于步骤(2)的纳米颗粒水溶液体系中，后捞出，将水沥净后自然晾干；
    (4)待家蚕生长至设定时间后，对家蚕饲喂步骤(3)的桑叶，直至家蚕吐丝结茧；
    (5)收集蚕丝，得到近红外光照下发荧光桑蚕丝。
  2. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，所述上转换纳米颗粒为核壳结构。
  3. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，所述上转换纳米颗粒包括β-NaYF 4:Yb,Er@β-NaYF 4上转换纳米颗粒、NaGdF4:Yb/Er@NaGdF4:Yb/Nd、NaYF4:Yb/Er或发红色荧光的上转换纳米颗粒中的一种或多种。
  4. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，所述上转换纳米颗粒为聚丙烯酸修饰的核壳结构上转换纳米颗粒。
  5. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，所述上转换纳米颗粒的制备方法如下：制备聚丙烯酸修饰的核壳结构上转换纳米颗粒，引入伴刀豆球蛋白，利用交联剂1-乙基-3-(3-二甲基氨丙基)-碳化二亚胺将伴刀豆球蛋白接枝到上转换纳米颗粒表面，形成复合共聚体。
  6. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，用伴刀豆球蛋白进行表面修饰的方法如下：
    采用配体交换法对上转换纳米颗粒表面进行聚丙烯酸接枝，离心获得沉淀；取10mg聚丙烯酸修饰的纳米颗粒分散在1mL水溶液中，分别加入EDC和NHS各1mg，搅拌反应3-6h，随后加入30μL伴刀豆角蛋白水溶液，该伴刀豆球蛋白水溶液的浓度为3-10mg/mL，搅拌过夜，离心洗涤后可得到伴刀豆角蛋白修饰的上转换纳米颗粒。
  7. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，所述上转换纳米颗粒水溶液的浓度为1～5g/L。
  8. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，待家蚕生长至五龄第三天时，对家蚕饲喂步骤(3)的桑叶。
  9. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，步骤(1)得到的修饰后的上转换纳米颗粒的平均直径为50～100nm。
  10. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，步骤(3)中，桑叶浸没时间为2～5min。
  11. 根据权利要求1所述的在近红外光照下发荧光桑蚕丝的制备方法，其特征在于，步骤(5)中，采用诱导家蚕平板吐丝收集蚕丝。
  12. 一种在近红外光照下发荧光桑蚕丝，其特征在于，由权利要求1～11任一所述的方法制备得到。
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CN110367209B (zh) * 2019-06-26 2020-06-23 浙江大学 一种在近红外光照下发荧光桑蚕丝的制备方法及产品
CN113564726B (zh) * 2020-04-28 2022-10-21 西南大学 一种高比电容的碳化脱胶蚕丝
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CN115656122B (zh) * 2022-10-11 2025-07-22 浙江大学 基于上转换纳米颗粒-丝素蛋白纳米探针体系检测抗生素的方法
CN119014499B (zh) * 2024-10-28 2025-03-11 内蒙古工业大学 一种具有正交激发-发射特性的彩色发光蚕丝及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003088274A (ja) * 2001-09-19 2003-03-25 National Institute Of Agrobiological Sciences 休眠卵を産生するカイコ品種へのポリヌクレオチドの導入方法
KR20090046616A (ko) * 2007-11-06 2009-05-11 인하대학교 산학협력단 마이크로에멀젼을 이용한 실크 피브로인 나노입자의 제조방법
CN102677182A (zh) * 2012-05-16 2012-09-19 东华大学 一种利用活体蚕直接吐丝制备天然功能蚕丝的方法
CN107446581A (zh) * 2017-09-17 2017-12-08 赵兵 一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝
CN107558187A (zh) * 2017-09-17 2018-01-09 赵兵 一种氧化石墨烯包覆的上转换荧光蚕丝
CN109588375A (zh) * 2018-11-02 2019-04-09 大连工业大学 基于鲅鱼内脏和桑叶复合碳点的荧光蚕丝制备方法
CN110367209A (zh) * 2019-06-26 2019-10-25 浙江大学 一种在近红外光照下发荧光桑蚕丝的制备方法及产品

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120039813A1 (en) * 2009-02-17 2012-02-16 Natalia Chendrawati Tansil Intrinsically colored, luminescent silk fibroin and a method of producing the same
WO2014011118A1 (en) * 2012-07-12 2014-01-16 National University Of Singapore An upconversion fluorescent nanoparticle

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003088274A (ja) * 2001-09-19 2003-03-25 National Institute Of Agrobiological Sciences 休眠卵を産生するカイコ品種へのポリヌクレオチドの導入方法
KR20090046616A (ko) * 2007-11-06 2009-05-11 인하대학교 산학협력단 마이크로에멀젼을 이용한 실크 피브로인 나노입자의 제조방법
CN102677182A (zh) * 2012-05-16 2012-09-19 东华大学 一种利用活体蚕直接吐丝制备天然功能蚕丝的方法
CN107446581A (zh) * 2017-09-17 2017-12-08 赵兵 一种层层自组装稀土掺杂上转换纳米材料的荧光蚕丝
CN107558187A (zh) * 2017-09-17 2018-01-09 赵兵 一种氧化石墨烯包覆的上转换荧光蚕丝
CN109588375A (zh) * 2018-11-02 2019-04-09 大连工业大学 基于鲅鱼内脏和桑叶复合碳点的荧光蚕丝制备方法
CN110367209A (zh) * 2019-06-26 2019-10-25 浙江大学 一种在近红外光照下发荧光桑蚕丝的制备方法及产品

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