CN110077033B

CN110077033B - Magnetic red-green bicolor fluorescent double-anisotropic conductive Janus tube

Info

Publication number: CN110077033B
Application number: CN201910298146.1A
Authority: CN
Inventors: 董相廷; 齐海娜; 于文生; 马千里; 谢云蕊; 王进贤; 李丹; 刘桂霞
Original assignee: Changchun University of Science and Technology
Current assignee: Changchun University of Science and Technology
Priority date: 2019-04-15
Filing date: 2019-04-15
Publication date: 2021-12-17
Anticipated expiration: 2039-04-15
Also published as: CN110077033A

Abstract

The invention relates to a magnetic red-green double-color fluorescent double-anisotropic conductive Janus tube and a preparation method thereof, belonging to the technical field of functional material preparation. The invention comprises three steps: (1) preparing a spinning solution; (2) preparing a magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus film, and preparing by adopting parallel electrospinning and uniaxial electrospinning technologies; (3) preparing a magnetic red and green bicolor fluorescent bi-anisotropic conductive Janus tube, and rolling the prepared magnetic red and green bicolor fluorescent bi-anisotropic conductive Janus film according to a certain strategy to obtain 4 types of Janus tubes. The prepared Janus tube has good magnetic, red-green double-color fluorescent and double-anisotropic conductive properties. The method is simple and easy to implement, can be used for batch production, and the novel photoelectric and electromagnetic multifunctional material has wide application prospect.

Description

Magnetic red-green bicolor fluorescent double-anisotropic conductive Janus tube

Technical Field

The invention relates to the technical field of functional material preparation, in particular to a magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus tube and a preparation method thereof.

Background

Anisotropic conductive materials have been widely used in the electronics industry. The development of new anisotropic conductive materials and the provision of multifunctional properties are important developments in their research.

The Janus nanoribbon refers to two chemical compositions which have definite partition structures in the same nanoribbon and have two or more properties, for example, one side of the nanoribbon has a light-emitting function, the other side of the nanoribbon has a conductive function, the Janus nanoribbons are directionally arranged to obtain a Janus nanoribbon array film, and the array film has the double functions of light emitting and conductive.

Rare earth complex Eu (BA)₃phen and Tb (BA)₃phen, wherein Eu³⁺Is europium ion, Tb³⁺Is terbium ion, BA is benzoic acid, phen is phenanthroline, and is a red and green fluorescent material widely used. Polyaniline PANI is a widely used conductive polymer material. Fe₃O₄Nanocrystals are good magnetic materials. Utilizing europium terbium complex, PANI and Fe₃O₄The nano-crystalline is an ideal raw material for constructing the photoelectric and electromagnetic multifunctional material.

When dark green conductive polyaniline PANI and black Fe₃O₄The direct mixing contact of the nanocrystalline and the rare earth complex can obviously reduce the luminous effect of the rare earth complex, so that Eu (BA) is required to obtain good luminous effect of the rare earth complex₃phen and Tb (BA)₃phen with PANI and Fe₃O₄The effective separation of the nanocrystals is achieved. If the polymethyl methacrylate PMMA is mixed with the conductive polyaniline PANI to prepare the nano belt, the conductive PANI is continuous in the nano belt to ensure the high conductivity of the nano belt, and one side of the Janus nano belt is conductive, while Eu (BA)₃phen is dispersed in PMMA to prepare a nano belt, and the other side of the nano belt serving as Janus nano belt has red light emitting characteristic to form [ PMMA/PANI]//[PMMA/Eu(BA)₃phen]Conductive red fluorescent dual function Janus nanoribbon, thereby enabling PANI and Eu (BA)₃phen is effectively separated, and a good luminous effect is obtained. If special devices are used, it is also possibleTo obtain a Janus nanoribbon array film, which is highly conductive along the length of the nanoribbon, and perpendicular to the length of the nanoribbon, due to the non-conductive PMMA/Eu (BA)₃phen structural unit, which makes the direction have insulation and thus have anisotropic conductivity, so that [ PMMA/PANI ] can be obtained]//[PMMA/Eu(BA)₃phen]An anisotropic conductive red fluorescent Janus nanoribbon array film; also, PMMA, PANI and Tb (BA) can be utilized₃Phen construction [ PMMA/PANI]//[PMMA/Tb(BA)₃phen]The two array films are firmly combined together to form a left structure and a right structure to obtain the Janus array film with the left structure and the right structure, and the length directions of the nanoribbons are vertical in the left half side and the right half side of the Janus array film, namely the conductive directions are vertical, so that the Janus array film with the left structure and the right structure has a double-anisotropy conductive red-green double-color fluorescent function. Forming a layer of Fe on the first layer of the Janus array film₃O₄The non-array magnetic film formed by PMMA nano-belts is used as a second layer, the first layer and the second layer are tightly combined to form a Janus film with an upper structure and a lower structure, and the magnetic Fe is realized₃O₄The Janus film has good magnetic red-green double-color fluorescence double-anisotropy conductive characteristics due to the effective separation of the nanocrystalline and the rare earth luminescent complex. The Janus film is rolled up by adopting different strategies to obtain 4 Janus tubes with novel structures, and the Janus tubes also have magnetic red-green double-color fluorescent double-anisotropic conductive characteristics. The special Janus tube has important application prospect in the fields of electronic industry and nanotechnology. At present, no relevant literature report is found.

Disclosure of Invention

The invention is realized by that aniline, camphor sulfonic acid, ammonium persulfate, PMMA, N-dimethyl formamide DMF and chloroform CHCl₃Mixing, polymerizing aniline to form polyaniline to obtain spinning solution 1, and mixing with Eu (BA)₃phen, PMMA, DMF and CHCl₃The mixed solution of (2) was prepared as a 2 nd spinning solution containing Tb (BA)₃phen, PMMA, DMF and CHCl₃The mixed solution of (1) is used as a 3 rd spinning solution, and Fe is coated by oleic acid₃O₄Nanocrystal of PMMA, DMF and CHCl₃The mixed solution is used as a 4 th spinning solution, and the control of the viscosity of the spinning solution is very important. Adopting parallel electrospinning technology to obtain [ PMMA/PANI ] under the optimal process conditions]//[PMMA/Tb(BA)₃phen]An anisotropic conductive green fluorescent Janus nanoribbon array film is constructed by utilizing a secondary parallel electrospinning technology]//[PMMA/Eu(BA)₃phen]Forming the Janus array films with left and right structures by using the anisotropic conductive red fluorescent Janus nanobelt array film, and constructing Fe on the Janus array films with the left and right structures by using a triple uniaxial electrospinning technology₃O₄The method comprises the steps of forming a Janus film with an upper structure and a lower structure by a PMMA nanobelt non-array magnetic film, and obtaining 4 Janus pipes with novel structures by adopting left-right rolling and up-down rolling of the Janus film, wherein each Janus pipe consists of an inner pipe and an outer pipe, is a double-wall Janus pipe and has the double-anisotropy conductive characteristic of magnetic red-green double-color fluorescence. The method comprises the following steps:

(1) preparing spinning solution

Dissolving 0.6000g of PMMA, 0.4200g of aniline and 0.5238g of camphorsulfonic acid in a mixed solvent of 8.0000g of chloroform and 1.0000g of DMF, stirring at normal temperature, marking the solution as solution A, adding 1.5000g of DMF into 1.0200g of ammonium persulfate, stirring for 2 hours to obtain a solution marked as solution B, placing the solution A and the solution B in a refrigerator, placing the solution A and the solution B at 0 ℃ for 1 hour, slowly adding the solution B into the solution A, stirring the mixed solution in an ice-water bath for 3.5 hours, and then placing the mixed solution in a refrigerating chamber of the refrigerator at 0 ℃ for refrigeration for 36 hours to obtain spinning solution 1; to a mixed solvent of 7.2000g of chloroform and 0.8000g of DMF were added 0.5000g of PMMA and 0.0750g of Eu (BA)₃phen and stirring for 12h to obtain spinning solution 2; to a mixed solvent of 7.2000g of chloroform and 0.8000g of DMF were added 0.5000g of PMMA and 0.0750g of Tb (BA)₃phen and stirring for 12h to obtain spinning solution 3; coating 0.5000g oleic acid-coated Fe with a diameter of 10nm₃O₄Adding the nanocrystalline into a mixed solvent of 0.7200g of DMF and 8.0000g of chloroform, ultrasonically dispersing for 30min, adding 0.5000g of PMMA, and stirring for 18h to obtain a spinning solution 4;

(2) preparation of magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus film

Two parallel spinning nozzles are adopted, two 5mL syringes are arranged on the spinning nozzles, and 3 isPouring 5mL of spinning solution 1 and spinning solution 3 into two syringes, performing parallel electrospinning in a vertical spraying mode, wherein a receiving device is a horizontally-placed cylindrical aluminum rotary drum with the length of 20cm and the diameter of 7cm, the rotating speed is 1500 rpm, the spinning voltage is 7kV, the spinning distance is 15cm, the ambient temperature is 20-25 ℃, the relative humidity is 20% -25%, and after the spinning solution is exhausted, obtaining the [ PMMA/PANI ]]//[PMMA/Tb(BA)₃phen]An anisotropic conductive green fluorescent Janus nanoribbon array film; mixing the [ PMMA/PANI ]]//[PMMA/Tb(BA)₃phen]The anisotropic conductive green fluorescent Janus nanoribbon array film is taken off from an aluminum drum, cut into a rectangle with the Janus nanoribbon arrangement direction of 2.2cm and the nanoribbon arrangement direction perpendicular to the Janus nanoribbon arrangement direction of 4cm, fixed on the aluminum drum after rotating the film for 90 degrees, and covered by aluminum foil with the thickness of 2 multiplied by 4cm²Area of (2), the remaining 0.2X 4cm²The area of the solution is used as the connecting surface of a secondary electro-spinning film, 3.5mL of spinning solution 1 and 3.5mL of spinning solution 2 are poured into two syringes, the spinning parameters are the same as those of the first parallel electro-spinning process, the second parallel electro-spinning is carried out, and the [ PMMA/PANI ] is obtained after the spinning solution is exhausted]//[PMMA/Eu(BA)₃phen]The anisotropic conductive red fluorescent Janus nanobelt array membrane is cut after being taken off from an aluminum rotary drum to obtain 4 multiplied by 4cm²The left and right structure Janus array membranes of (1); fixing the Janus array membranes with the left and right structures on an iron wire net, putting the spinning solution 4 into a 5mL syringe, performing single-shaft electrospinning in a vertical spraying mode, wherein the spinning parameters are the same as those of the first parallel electrospinning, and obtaining Fe on the Janus array membranes with the left and right structures after the spinning solution is exhausted₃O₄Cutting PMMA nanobelt non-array magnetic film to obtain 4 × 4cm²The magnetic red-green double-color fluorescent double-anisotropic conductive Janus film;

(3) preparation of magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus tube

When the magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus film is curled left and right, the film is curled downwards to obtain an I-type Janus tube, and is curled upwards to obtain a II-type Janus tube; when the double-wall Janus tube is vertically coiled, the double-wall Janus tube is downwards coiled to obtain a III type Janus tube, and upwards coiled to obtain an IV type Janus tube, wherein the Janus tubes are respectively compounded by an isotropic magnetic tube and a red-green bicolor fluorescent bi-anisotropic conductive tube which are respectively used as an inner tube and an outer tube, and the double-wall Janus tube is a double-wall Janus tube and has magnetic red-green bicolor fluorescent bi-anisotropic conductive characteristics.

The circumference of the magnetic red-green bicolor fluorescent double-anisotropic conductive Janus tube prepared in the process is 4cm, the length of the tube is 4cm, and the isotropic magnetic tube is made of Fe₃O₄The PMMA nano-belt is composed of a width of about 3.3 mu m, a thickness of about 489nm, a saturation magnetization of 18.52emu/g, and a red and green bicolor fluorescent double-anisotropic conductive tube, wherein a red fluorescent conductive part is composed of [ PMMA/PANI [ ]]//[PMMA/Eu(BA)₃phen]Janus nano-belt array, the width of Janus nano-belt is about 8.3 μm, the thickness is about 890nm, under the excitation of 291nm ultraviolet light, bright red light with main peak at 615nm is emitted, the conduction is carried out along the arrangement direction of nano-belt, the average conductance is 3.78 multiplied by 10^-2S, and an average conductance of 1.89X 10 along the direction perpendicular to the alignment of the nanoribbons^-10S, the ratio of the conductance in the conducting direction to the conductance in the insulating direction is 2.00X 10⁸Anisotropic conductive properties; the green fluorescent conducting part consists of [ PMMA/PANI]//[PMMA/Tb(BA)₃phen]Janus nano-belt array, the width of Janus nano-belt is about 8.3 μm, the thickness is about 900nm, under the excitation of 293nm ultraviolet light, the Janus nano-belt emits bright green light with main peak at 545nm, the conduction is carried out along the arrangement direction of the nano-belt, the average conductance is 4.37 multiplied by 10^-2S, and an average conductance of 1.78X 10 along the direction perpendicular to the alignment of the nanoribbons^-10S, the ratio of the conductance in the conducting direction to the conductance in the insulating direction is 2.45X 10⁸Anisotropic conductive properties; for a type I Janus tube, an inner tube is an isotropic magnetic tube, an outer tube is an anisotropic left and right structure tube, the left and right structures have red and green fluorescence respectively, the left side is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction perpendicular to the nanoribbon arrangement direction, the right side is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction perpendicular to the nanoribbon arrangement direction, the left and right sides have anisotropic conductivity respectively, the conductive directions are perpendicular, and the left and right sides have double-anisotropic conductivity; the outer pipe is an isotropic magnetic pipe, the inner pipe is an anisotropic left and right structural pipe, and the left pipe is a type II Janus pipeThe right structure has red and green fluorescence respectively, the left side is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction perpendicular to the nanoribbon arrangement direction, the right side is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction perpendicular to the nanoribbon arrangement direction, the left side and the right side have anisotropic conductivity respectively, the conductivity direction is perpendicular, and the right side has double anisotropic conductivity; the type III Janus tube is characterized in that an inner tube is an isotropic magnetic tube, an outer tube is an anisotropic upper and lower structure tube, the upper and lower structures are respectively provided with green fluorescence and red fluorescence, the upper side of the upper structure tube is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction vertical to the nanoribbon arrangement direction, the lower side of the upper structure tube is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction vertical to the nanoribbon arrangement direction, the upper and lower parts are respectively provided with anisotropic conductivity, the conductive directions are vertical, and the upper and lower parts have double-anisotropic conductivity; the IV-type Janus tube is characterized in that the outer tube is an isotropic magnetic tube, the inner tube is an anisotropic upper and lower structure tube, the upper and lower structures are respectively provided with green fluorescence and red fluorescence, the upper side of the upper structure tube is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction perpendicular to the nanoribbon arrangement direction, the lower side of the upper structure tube is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction perpendicular to the nanoribbon arrangement direction, the upper and lower parts are respectively provided with anisotropic conductivity, the conductive direction is perpendicular, and the upper and lower parts have double-anisotropic conductivity. The prepared 4 Janus tubes have good magnetic red-green double-color fluorescent double-anisotropy conductive characteristics, and the purpose of the invention is realized.

Drawings

FIG. 1 is an XRD pattern of an isotropic magnetic tube in a magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus tube;

FIG. 2 is a hysteresis loop diagram of an isotropic magnetic tube in a magnetic red-green bi-color fluorescent bi-anisotropic conductive Janus tube;

FIG. 3 is a line analysis energy dispersion spectrum of Janus nanoribbons in a red fluorescent conducting part in a magnetic red-green bicolor fluorescent bi-anisotropic conducting Janus tube;

FIG. 4 is a spectrum of the emission of the red fluorescent conducting part in the magnetic red-green dual-color fluorescent bi-anisotropic conducting Janus tube;

FIG. 5 is a line analysis energy dispersion spectrum of Janus nanoribbons in the green fluorescent conducting part of a magnetic red-green dual-color fluorescent dual-anisotropic conducting Janus tube;

FIG. 6 is a graph of the emission spectrum of the green fluorescent conducting part in a magnetic red-green two-color fluorescent bi-anisotropic conducting Janus tube.

FIG. 7 is a photograph of a magnetic red-green two-color fluorescent bi-anisotropic conductive Janus tube taken as a real object and a schematic diagram, which is also taken as an abstract figure.

Detailed Description

The europium oxide Eu selected by the invention₂O₃And terbium oxide Tb₄O₇The purity of the compound is 99.99%, and the compound is N, N-dimethylformamide, chloroform, nitric acid, benzoic acid, phenanthroline, absolute ethyl alcohol, ammonia water, aniline, camphorsulfonic acid, dibenzoyl peroxide, methyl methacrylate, ammonium persulfate, ferric trichloride hexahydrate, ferrous sulfate heptahydrate, ammonium nitrate, polyethylene glycol with the molecular weight of 20000, oleic acid and argon gas which are all commercially available analytical pure products; europium and terbium complex and oleic acid coated Fe₃O₄Nanocrystalline, PMMA and deionized water are manufactured by laboratories; the glassware and equipment used are those commonly used in the laboratory.

Example (b): dissolving 0.6000g of PMMA, 0.4200g of aniline and 0.5238g of camphorsulfonic acid in a mixed solvent of 8.0000g of chloroform and 1.0000g of DMF, stirring at normal temperature, marking the solution as solution A, adding 1.5000g of DMF into 1.0200g of ammonium persulfate, stirring for 2 hours to obtain a solution marked as solution B, placing the solution A and the solution B in a refrigerator, placing the solution A and the solution B at 0 ℃ for 1 hour, slowly adding the solution B into the solution A, stirring the mixed solution in an ice-water bath for 3.5 hours, and then placing the mixed solution in a refrigerating chamber of the refrigerator at 0 ℃ for refrigeration for 36 hours to obtain spinning solution 1; to a mixed solvent of 7.2000g of chloroform and 0.8000g of DMF were added 0.5000g of PMMA and 0.0750g of Eu (BA)₃phen and stirring for 12h to obtain spinning solution 2; to a mixed solvent of 7.2000g of chloroform and 0.8000g of DMF were added 0.5000g of PMMA and 0.0750g of Tb (BA)₃phen and stirring for 12h to obtain spinning solution 3; coating 0.5000g oleic acid-coated Fe with a diameter of 10nm₃O₄Nanocrystals, added to 0.720Carrying out ultrasonic dispersion on 0g of DMF and 8.0000g of chloroform in a mixed solvent for 30min, adding 0.5000g of PMMA, and stirring for 18h to obtain a spinning solution 4; adopting two parallel spinning heads, installing two 5mL injectors on the spinning heads, pouring 3.5mL of spinning solution 1 and 3 into the two injectors, adopting a vertical spraying mode to carry out parallel electrospinning, wherein a receiving device is a horizontally placed cylindrical aluminum revolving drum with the length of 20cm and the diameter of 7cm, the rotating speed is 1500 revolutions per minute, the spinning voltage is 7kV, the spinning distance is 15cm, the environmental temperature is 20-25 ℃, the relative humidity is 20-25%, and after the spinning solution is exhausted, obtaining the [ PMMA/PANI ]]//[PMMA/Tb(BA)₃phen]An anisotropic conductive green fluorescent Janus nanoribbon array film; mixing the [ PMMA/PANI ]]//[PMMA/Tb(BA)₃phen]The anisotropic conductive green fluorescent Janus nanoribbon array film is taken off from an aluminum drum, cut into a rectangle with the Janus nanoribbon arrangement direction of 2.2cm and the nanoribbon arrangement direction perpendicular to the Janus nanoribbon arrangement direction of 4cm, fixed on the aluminum drum after rotating the film for 90 degrees, and covered by aluminum foil with the thickness of 2 multiplied by 4cm²Area of (2), the remaining 0.2X 4cm²The area of the solution is used as the connecting surface of a secondary electro-spinning film, 3.5mL of spinning solution 1 and 3.5mL of spinning solution 2 are poured into two syringes, the spinning parameters are the same as those of the first parallel electro-spinning process, the second parallel electro-spinning is carried out, and the [ PMMA/PANI ] is obtained after the spinning solution is exhausted]//[PMMA/Eu(BA)₃phen]The anisotropic conductive red fluorescent Janus nanobelt array membrane is cut after being taken off from an aluminum rotary drum to obtain 4 multiplied by 4cm²The left and right structure Janus array membranes of (1); fixing the Janus array membranes with the left and right structures on an iron wire net, putting the spinning solution 4 into a 5mL syringe, performing single-shaft electrospinning in a vertical spraying mode, wherein the spinning parameters are the same as those of the first parallel electrospinning, and obtaining Fe on the Janus array membranes with the left and right structures after the spinning solution is exhausted₃O₄Cutting PMMA nanobelt non-array magnetic film to obtain 4 × 4cm²The magnetic red-green double-color fluorescent double-anisotropic conductive Janus film; when the magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus film is curled left and right, the film is curled downwards to obtain an I-type Janus tube, and is curled upwards to obtain a II-type Janus tube; when the tube is curled up and down, the tube is curled down to obtain a type III Janus tube, and the tube is curled up to obtain a type IV Janus tube, and the Janus tubes are respectively formed by the tubesThe isotropic magnetic tube and the red-green bicolor fluorescent bi-anisotropic conductive tube are respectively used as an inner tube and an outer tube to be compounded, and the double-wall Janus tube is formed. The isotropic magnetic tube in the prepared magnetic red-green bicolor fluorescent double-anisotropic conductive Janus tube contains Fe₃O₄Nanocrystals, shown in figure 1; the isotropic magnetic tube is made of Fe₃O₄PMMA nanobelt with width of about 3.3 μm, thickness of about 489nm, saturation magnetization of 18.52emu/g, as shown in FIG. 2; in the red and green bicolor fluorescent bi-anisotropic conductive tube, the red fluorescent conductive part consists of [ PMMA/PANI]//[PMMA/Eu(BA)₃phen]The distribution of S and Eu elements can respectively reflect polyaniline and Eu (BA)₃phen distribution, the S element is distributed on only one side of the Janus nanoribbon, and the Eu element is distributed on the other side of the Janus nanoribbon, which is consistent with the structure of the Janus nanoribbon, as shown in FIG. 3, the width of the Janus nanoribbon is about 8.3 μm, the thickness is about 890nm, under the excitation of 291nm ultraviolet light, bright red light with a main peak at 615nm is emitted, which corresponds to the Eu ion⁵D₀→⁷F₂Transition, as shown in FIG. 4, along the direction of nanoribbon alignment conduction with an average conductance of 3.78X 10^-2S, and an average conductance of 1.89X 10 along the direction perpendicular to the alignment of the nanoribbons^-10S, the ratio of the conductance in the conducting direction to the conductance in the insulating direction is 2.00X 10⁸Anisotropic conductive properties; the green fluorescent conducting part consists of [ PMMA/PANI]//[PMMA/Tb(BA)₃phen]The distribution of S and Tb elements can respectively reflect polyaniline and Tb (BA)₃phen distribution, S element only on one side of Janus nano-belt, Tb element on the other side of Janus nano-belt, which is consistent with the structure of Janus nano-belt, as shown in FIG. 5, Janus nano-belt width is about 8.3 μm, thickness is about 900nm, under 293nm ultraviolet excitation, it emits bright green light with main peak at 545nm, which corresponds to Tb ion⁵D₄→⁷F₅The transition, shown in FIG. 6, conducts along the nanoribbon alignment direction with an average conductance of 4.37X 10^-2S, and an average conductance of 1.78X 10 along the direction perpendicular to the alignment of the nanoribbons^-10S, the ratio of the conductance in the conducting direction to the conductance in the insulating direction is 2.45X 10⁸Anisotropic conductive properties; a real object diagram and a schematic diagram of the prepared magnetic red-green bicolor fluorescent double-anisotropic conductive Janus tube are shown in FIG. 7, wherein the circumference of the Janus tube is 4cm, the length of the Janus tube is 4cm, for the I-type Janus tube, the inner tube is an isotropic magnetic tube, the outer tube is an anisotropic left and right structural tube, the left and right structures are respectively provided with red and green fluorescent lights, the left side is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the nanoribbon arrangement direction, and the right side is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the nanoribbon arrangement direction, and the left and right sides are respectively provided with anisotropic conductivity, are vertical in the conductive direction, and have the double-anisotropic conductive property; the type II Janus tube is characterized in that the outer tube is an isotropic magnetic tube, the inner tube is an anisotropic left and right structure tube, the left and right structures respectively have red and green fluorescence, the left side is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction perpendicular to the nanoribbon arrangement direction, the right side is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction perpendicular to the nanoribbon arrangement direction, the left and right sides are respectively provided with anisotropic conductivity, the conductivity direction is perpendicular, and the double-anisotropic conductivity characteristic is achieved; the type III Janus tube is characterized in that an inner tube is an isotropic magnetic tube, an outer tube is an anisotropic upper and lower structure tube, the upper and lower structures are respectively provided with green fluorescence and red fluorescence, the upper side of the upper structure tube is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction vertical to the nanoribbon arrangement direction, the lower side of the upper structure tube is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction vertical to the nanoribbon arrangement direction, the upper and lower parts are respectively provided with anisotropic conductivity, the conductive directions are vertical, and the upper and lower parts have double-anisotropic conductivity; the IV-type Janus tube is characterized in that the outer tube is an isotropic magnetic tube, the inner tube is an anisotropic upper and lower structure tube, the upper and lower structures are respectively provided with green and red fluorescence, the upper side is conductive along the axial direction, namely the nanoribbon arrangement direction, and insulated along the circumference, namely the direction vertical to the nanoribbon arrangement direction, the lower side is conductive along the circumference, namely the nanoribbon arrangement direction, and insulated along the axial direction, namely the direction vertical to the nanoribbon arrangement direction, the upper and lower parts are respectively provided with anisotropic conductivity,the conductive direction is vertical, the prepared 4 Janus tubes have the double-anisotropic conductive property of magnetic red-green double-color fluorescence.

The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims

1. The magnetic red-green double-color fluorescent double-anisotropy conductive Janus tube is characterized by comprising [ Fe [ [ Fe ]₃O₄/PMMA]// {{[PMMA/PANI]//[PMMA/Tb(BA)₃phen]}⊥{[PMMA/PANI]//[PMMA/Eu(BA)₃phen]The magnetic red and green bicolor fluorescent double-anisotropic conductive Janus film is curled downwards to obtain an I-type Janus tube when being curled left and right, is curled upwards to obtain an II-type Janus tube, is curled downwards to obtain a III-type Janus tube when being curled up and down, and is curled upwards to obtain an IV-type Janus tube, the Janus tubes are respectively compounded by an isotropic magnetic tube and a red and green bicolor fluorescent double-anisotropic conductive tube which are respectively used as an inner tube and an outer tube, and are double-wall Janus tubes which have magnetic red and green bicolor fluorescent double-anisotropic conductive characteristics, wherein the circumference of each Janus tube is 4cm, and the length of each Janus tube is 4 cm; the magnetic red-green double-color fluorescent double-anisotropic conductive Janus film is made of Fe₃O₄The PMMA nanobelt film is formed by compounding an upper layer and a lower layer of a red-green bicolor fluorescent bi-anisotropic conductive part, and the red-green bicolor fluorescent bi-anisotropic conductive part is composed of { [ PMMA/PANI { []//[PMMA/Tb(BA)₃phen]Green fluorescent anisotropic conductive Janus nanoribbon array in the same plane vertical { [ PMMA/PANI ]]//[PMMA/Eu(BA)₃phen]The left and right structures of the red fluorescence anisotropic conductive Janus nanoribbon array are compounded, and Fe₃O₄PMMA nanoribbon with width of 3.3 μm and thickness of 489nm, [ PMMA/PANI]//[PMMA/Tb(BA)₃phen]The width of Janus green fluorescence anisotropic conductive Janus nano-belt is 8.3 μm, the thickness is 900nm, [ PMMA/PANI]//[PMMA/Eu(BA)₃phen]Red fluorescence anisotropic conductive Janus nanoribbonHas a width of 8.3 μm and a thickness of 890 nm.

2. The preparation method of the magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus tube as claimed in claim 1, wherein the magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus tube is prepared by adopting a parallel electrospinning technology, a uniaxial electrospinning technology and a curling method, and the steps are as follows:

(1) preparing spinning solution

Dissolving 0.6000g of PMMA, 0.4200g of aniline and 0.5238g of camphorsulfonic acid in a mixed solvent of 8.0000g of chloroform and 1.0000g of DMF, stirring at normal temperature, marking the solution as solution A, adding 1.5000g of DMF into 1.0200g of ammonium persulfate, stirring for 2 hours to obtain a solution marked as solution B, placing the solution A and the solution B in a refrigerator, placing the solution A and the solution B at 0 ℃ for 1 hour, slowly adding the solution B into the solution A, stirring the mixed solution in an ice-water bath for 3.5 hours, and then placing the mixed solution in a refrigerating chamber of the refrigerator at 0 ℃ for refrigerating for 36 hours to obtain spinning solution 1; to a mixed solvent of 7.2000g of chloroform and 0.8000g of DMF were added 0.5000g of PMMA and 0.0750g of Eu (BA)₃phen and stirring for 12h to obtain spinning solution 2; to a mixed solvent of 7.2000g of chloroform and 0.8000g of DMF were added 0.5000g of PMMA and 0.0750g of Tb (BA)₃phen and stirring for 12h to obtain spinning solution 3; coating 0.5000g oleic acid-coated Fe with a diameter of 10nm₃O₄Adding the nanocrystalline into a mixed solvent of 0.7200g of DMF and 8.0000g of chloroform, ultrasonically dispersing for 30min, adding 0.5000g of PMMA, and stirring for 18h to obtain a spinning solution 4;

Adopting two parallel spinning heads, installing two 5mL syringes on the spinning heads, pouring 3.5mL of spinning solution 1 and 3 into the two syringes, adopting a vertical spraying mode to carry out parallel electrospinning, wherein a receiving device is a horizontally placed cylindrical aluminum revolving drum with the length of 20cm and the diameter of 7cm, the rotating speed is 1500 revolutions per minute, the spinning voltage is 7kV, the spinning distance is 15cm, and the environmental temperature is 20-25^oC, the relative humidity is 20% -25%, and after the spinning solution is exhausted, [ PMMA/PANI ] is obtained]//[PMMA/Tb(BA)₃phen]An anisotropic conductive green fluorescent Janus nanoribbon array film; mixing the [ PMMA/PANI ]]//[PMMA/Tb(BA)₃phen]The anisotropic conductive green fluorescent Janus nanoribbon array film is taken off from an aluminum drum, cut into a rectangle with the Janus nanoribbon arrangement direction of 2.2cm and the nanoribbon arrangement direction perpendicular to the Janus nanoribbon arrangement direction of 4cm, fixed on the aluminum drum after rotating the film for 90 degrees, and covered by aluminum foil with the thickness of 2 multiplied by 4cm²Area of (2), the remaining 0.2X 4cm²The area of the solution is used as the connecting surface of a secondary electro-spinning film, 3.5mL of spinning solution 1 and 3.5mL of spinning solution 2 are poured into two syringes, the spinning parameters are the same as those of the first parallel electro-spinning process, the second parallel electro-spinning is carried out, and the [ PMMA/PANI ] is obtained after the spinning solution is exhausted]//[PMMA/Eu(BA)₃phen]The anisotropic conductive red fluorescent Janus nanobelt array membrane is cut after being taken off from an aluminum rotary drum to obtain 4 multiplied by 4cm²The left and right structure Janus array membranes of (1); fixing the Janus array membranes with the left and right structures on an iron wire net, putting the spinning solution 4 into a 5mL syringe, performing single-shaft electrospinning in a vertical spraying mode, wherein the spinning parameters are the same as those of the first parallel electrospinning, and obtaining Fe on the Janus array membranes with the left and right structures after the spinning solution is exhausted₃O₄Cutting PMMA nanobelt non-array magnetic film to obtain 4 × 4cm²The magnetic red-green double-color fluorescent double-anisotropic conductive Janus film;

When the magnetic red-green bicolor fluorescent bi-anisotropic conductive Janus film is curled left and right, the film is curled downwards to obtain an I-type Janus tube, and is curled upwards to obtain a II-type Janus tube; the method comprises the following steps of downwards curling to obtain a III-type Janus tube when the Janus tube is curled up and down, upwards curling to obtain an IV-type Janus tube, compounding the Janus tubes respectively serving as an inner tube and an outer tube by using an isotropic magnetic tube and a red-green bicolor fluorescent bi-anisotropic conductive tube as the inner tube and the outer tube, wherein the Janus tubes are double-wall Janus tubes, the circumference of each Janus tube is 4cm, the length of each Janus tube is 4cm, and the isotropic magnetic tube is made of Fe₃O₄The PMMA nano-belt consists of a width of 3.3 mu m, a thickness of 489nm, a saturation magnetization of 18.52emu/g, and a red and green bicolor fluorescent double-anisotropic conductive tube, wherein a red fluorescent conductive part consists of [ PMMA/PANI [ ]]//[PMMA/Eu(BA)₃phen]Janus nano-belt array, the width of Janus nano-belt is 8.3 μm, the thickness is 890nm, under the excitation of 291nm ultraviolet light, bright red light with main peak at 615nm is emitted, the conduction is carried out along the arrangement direction of nano-belt, the average conductance is 3.78 multiplied by 10^-2S, and an average conductance of 1.89X 10 along the direction perpendicular to the alignment of the nanoribbons^-10S, the ratio of the conductance in the conducting direction to the conductance in the insulating direction is 2.00X 10⁸Anisotropic conductive properties; the green fluorescent conducting part consists of [ PMMA/PANI]//[PMMA/Tb(BA)₃phen]Janus nano-belt array, the width of Janus nano-belt is 8.3 μm, the thickness is 900nm, under the excitation of 293nm ultraviolet light, it emits bright green light whose main peak is 545nm, and conducts electricity along the nano-belt arrangement direction, and the average conductance is 4.37 x 10^-2S, and an average conductance of 1.78X 10 along the direction perpendicular to the alignment of the nanoribbons^-10S, the ratio of the conductance in the conducting direction to the conductance in the insulating direction is 2.45X 10⁸Anisotropic conductive properties; for a type I Janus tube, an inner tube is an isotropic magnetic tube, an outer tube is an anisotropic left and right structure tube, the left and right structures have red and green fluorescence respectively, the left side is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction perpendicular to the nanoribbon arrangement direction, the right side is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction perpendicular to the nanoribbon arrangement direction, the left and right sides have anisotropic conductivity respectively, the conductive directions are perpendicular, and the left and right sides have double-anisotropic conductivity; the type II Janus tube is characterized in that the outer tube is an isotropic magnetic tube, the inner tube is an anisotropic left and right structure tube, the left and right structures respectively have red and green fluorescence, the left side is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction perpendicular to the nanoribbon arrangement direction, the right side is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction perpendicular to the nanoribbon arrangement direction, the left and right sides are respectively provided with anisotropic conductivity, the conductivity direction is perpendicular, and the double-anisotropic conductivity characteristic is achieved; the type III Janus tube has an inner tube of isotropic magnetic material, an outer tube of anisotropic upper and lower structure having green and red fluorescence, and upper side along axial direction, i.e. nanobeltThe arrangement direction is conductive and insulated along the perimeter, namely the direction vertical to the nanoribbon arrangement direction, the lower side is conductive along the perimeter, namely the nanoribbon arrangement direction, and insulated along the axial direction, namely the direction vertical to the nanoribbon arrangement direction, the upper side and the lower side are respectively provided with anisotropic conductivity, the conductive direction is vertical, and the double anisotropic conductive property is realized; the IV type Janus tube is characterized in that the outer tube is an isotropic magnetic tube, the inner tube is an anisotropic upper and lower structure tube, the upper and lower structures are respectively provided with green fluorescence and red fluorescence, the upper side of the upper structure tube is conductive along the axial direction, namely the nanoribbon arrangement direction, and is insulated along the circumference, namely the direction perpendicular to the nanoribbon arrangement direction, the lower side of the upper structure tube is conductive along the circumference, namely the nanoribbon arrangement direction, and is insulated along the axial direction, namely the direction perpendicular to the nanoribbon arrangement direction, the upper and lower structures are respectively provided with anisotropic conductivity, the conductive directions are perpendicular, and the upper and lower structures have double-anisotropic conductivity, and the prepared 4 Janus tubes have good magnetic red-green double-color fluorescence double-anisotropic conductivity.