CN104557948B - Method for preparing monodispersed porphyrin molecule particles by water droplet templating method - Google Patents
Method for preparing monodispersed porphyrin molecule particles by water droplet templating method Download PDFInfo
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- CN104557948B CN104557948B CN201310466855.9A CN201310466855A CN104557948B CN 104557948 B CN104557948 B CN 104557948B CN 201310466855 A CN201310466855 A CN 201310466855A CN 104557948 B CN104557948 B CN 104557948B
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- C07—ORGANIC CHEMISTRY
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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Abstract
The invention relates to a method for preparing monodispersed porphyrin molecule particles by a water droplet templating method. The method comprises the following steps: firstly dissolving porphyrin molecules in a good solvent which has good dissolvability of porphyrin molecules so as to obtain a porphyrin solution, and dispersing the porphyrin solution in a poor solvent to obtain a porphyrin molecule suspension; dispersing the porphyrin molecule suspension on a water droplet template, drying in an environment with a certain temperature and humidity, and letting the porphyrin molecules in the porphyrin molecule suspension aggregate and assemble on the surface of the water droplet template so as to finally form the monodispersed porphyrin molecule particles (which are shaped as solid or hollow spheres, solid or hollow hemispheres and jars or petals, etc.). The obtained monodispersed porphyrin molecule particles can be further assembled to form porphyrin molecule photonic crystals with Bragg diffraction performance. Due to close packing of the water droplet template, an ordered arrangement structure is formed, and finally aggregation of the monodispersed porphyrin molecule particles is realized to form an ordered arrangement structure which shows the Bragg diffraction performance, namely photonic crystal performance.
Description
Technical field
The present invention relates to the controllable method for preparing of Porphyrin Molecule aggregated structure, more particularly to using water droplet template to porphyrin point
The size and morphology control of sub- aggregated structure, realizes the aggregation of Porphyrin Molecule, prepares single dispersing Porphyrin Molecule particle, and enters
One step is assembled into Porphyrin Molecule photonic crystal.
Background technology
Porphyrin（Porphyrin）It is the pigment general name with pyrrole ring as basic structure, its basic chemical structure is by 4 first
Alkene bridge (CH=）The macromole heterocyclic compound for connecting 4 pyrrole rings and being formed.Porphyrin ring has 26 pi-electrons, is that a height is total to
The system of yoke.The supramolecular structure that these are made up of porphyrin ring is in electronics, information Store, light-energy conversion and catalyst system and catalyzing side
The accumulation shape that face has very many applications, Porphyrin Molecule affects very big to its final photoelectric properties.By designing porphyrin
The structure of molecule, regulatory molecule inside and intermolecular conjugation assembling effect, so as to regulate and control its molecule assembling, prepare and have
The Porphyrin Molecule aggregated structure of definite shape, size and pattern and device are research themes in recent years.1996,
Schenning, A et al. realize the preparation of Porphyrin Molecule annular aggregated structure（JACS,1996,118(36),8549-8552）.
1997, Komatsu et al. realized the preparation of Porphyrin Molecule imitated vesicle structure（JACS,1997,119,11660).2004,
Wang et al. has prepared Porphyrin Molecule lamellar aggregated structure（JACS,2004,126(49),15954-15955）.2005, porphin
The tubulose of quinoline molecule and bar-shaped aggregated structure are also produced（JACS, 2005,127 (48), 17090-17095).2009, in
Good et al. spherical and Y tube aggregated structure the preparations for realizing Porphyrin Molecule of academy of science of state chemistry institute Li Yu
（Advanced Materials2009,21(17),1721）.2010, Liu Ming China of Institute of Chemistry, Academia Sinica et al. was real
The preparation of the bat shape aggregated structure of Porphyrin Molecule is showed（JACS 2010,132(28),9644-9652）.The same year, Shelnutt
Seminar has prepared the quatrefoil shape aggregation knot of Porphyrin Molecule by introducing anion and cation in Porphyrin Molecule end group
Structure（JACS,2010,132(23),8194-8201).In the CN201310308655.0 of applicant in this case, by regulating and controlling porphyrin
Baking temperature of the molecular suspension liquid on base material, realizes the controllable standby of Porphyrin Molecule aggregated structure.The present invention has developed logical
The method as template using water droplet is crossed, Porphyrin Molecule suspension is induced in the aggregation of water droplet template surface, so as to realize single point
The controllable standby of scattered Porphyrin Molecule particle, the shape of involved single dispersing Porphyrin Molecule particle includes（It is hollow）Spherical,（It is empty
The heart）Hemispherical, doliform or petal etc..In the presence of water droplet template, the present invention is further by the single dispersing porphin for preparing
Quinoline molecular particle is assembled into the Porphyrin Molecule photonic crystal with photonic crystal performance.The method of the present invention for Porphyrin Molecule and
The controllable standby of the aggregated structure of other conjugated molecules provides new approaches.
The content of the invention
An object of the present invention is to provide a kind of simple preparation method, easily low cost, operation, the utilization of easy scale
Water droplet template regulates and controls the coherent condition of Porphyrin Molecule, so as to realize the aggregation of Porphyrin Molecule, controllable standby single dispersing porphyrin point
The method of seed.
The second object of the present invention is to provide the single dispersing Porphyrin Molecule particle prepared by purpose one.
The three of the purpose of present aspect are to provide a kind of porphin formed by the single dispersing Porphyrin Molecule particle assembling for preparing
Quinoline molecule photonic crystal.
The present invention is using water droplet template method, with water droplet as template, with Porphyrin Molecule suspension as raw material, in a constant temperature
It is dried in the environment of degree and humidity, is assembled by the Porphyrin Molecule in Porphyrin Molecule suspension and group on the surface of water droplet template
Dress, final aggregation forms single dispersing Porphyrin Molecule particle（Single dispersing Porphyrin Molecule particle is shaped as solid spherical, hollow ball
Shape, solid hemi-spherical, hollow hemispheric, doliform or petal etc.）；When the relative humidity of system is more than 60%, due to water droplet mould
The orderly close packed array structure of plate, finally realizes that the single dispersing Porphyrin Molecule particle that multiple aggregations are formed has orderly row
Array structure.Gained single dispersing Porphyrin Molecule particle can be assembled to form the Porphyrin Molecule photonic crystal with photonic crystal performance（Porphin
Quinoline molecule photonic crystal is by being shaped as solid spherical, hollow ball shape, solid hemi-spherical, hollow hemispheric, doliform or petal etc.
Single dispersing Porphyrin Molecule particle ordered fabrication is obtained）, and multiple had by what multiple single dispersing Porphyrin Molecule particle assemblings were formed
The Porphyrin Molecule photonic crystal of photonic crystal performance also has the structure of ordered arrangement.The preparation method of the present invention is simple, cost
It is low, be easily controlled, for regulation and control Porphyrin Molecule aggregated structure and development Porphyrin Molecule in terms of high performance photoelectric device
Using significant.
The method that the utilization water droplet template of the present invention prepares single dispersing Porphyrin Molecule particle：It is right that Porphyrin Molecule is dissolved in
Porphyrin Molecule has in the good solvent of good solubility and obtains porphyrin solution, and the porphyrin solution for obtaining is dispersed in Porphyrin Molecule
In the poor poor solvent of dissolubility, Porphyrin Molecule suspension is obtained；By the Porphyrin Molecule suspension for obtaining dispersion（Including drop
Apply, spraying or spraying dispersion etc.）It is on the surface of the water droplet template on solid substrate surface and dry, or water droplet template is disperseed
（Including drop coating, spraying or spraying dispersion etc.）It is on the surface of the Porphyrin Molecule suspension on solid substrate surface and dry, or
By the dispersion of Porphyrin Molecule suspension（Including drop coating, spraying or spraying dispersion etc.）The table of the water droplet template on solid substrate surface
After on face, then water droplet template is disperseed（Including drop coating, spraying or spraying dispersion etc.）It is on Porphyrin Molecule suspension and dry；
In dry process, with the evaporation of the good solvent in water and Porphyrin Molecule suspension and poor solvent, Porphyrin Molecule can be with water
Drip for template, assemble and be assembled in the surface of water droplet template, aggregation forms single dispersing Porphyrin Molecule particle.Due to water droplet template
Arrangement in good order, can cause the single dispersing Porphyrin Molecule particle that multiple aggregations are formed to have orderly arrangement architecture.
The formation of the water droplet template on described solid substrate surface is that solid substrate is placed in less than 8 DEG C of environment,
Then again solid substrate moved to into room temperature（Such as 25 DEG C）In environment, on the surface of solid substrate water droplet is obtained；Or by solid
Vaporific water is sprayed on the surface of base material, and on the surface of solid substrate water droplet is obtained；Or with water as ink, by the side of inkjet printing
Method, on the surface of solid substrate water droplet is obtained.
The shape of the single dispersing Porphyrin Molecule particle that the method for the present invention is prepared is with the porphin in Porphyrin Molecule suspension
Quinoline solution is regulated and controled with the change of the volume ratio of poor solvent；The size chi of preparation-obtained single dispersing Porphyrin Molecule particle
The very little size dimension by water droplet template is determined.
The concentration of described porphyrin solution is 1 μM～1M.
Described porphyrin solution is 1 with the volume ratio of poor solvent:5～3:1.
On the surface of the described water droplet template that the Porphyrin Molecule suspension for obtaining is dispersed on solid substrate surface simultaneously
It is dried, after the good solvent in water and Porphyrin Molecule suspension and poor solvent evaporating completely, can causes to assemble single point for being formed
Scattered Porphyrin Molecule particle forms spherical structure, obtains the single dispersing Porphyrin Molecule particle of spherical aggregated structure, wherein：When described
Porphyrin solution in Porphyrin Molecule suspension is 1 with the volume ratio of poor solvent:1～3:1, and the concentration of porphyrin solution is 1M
When, obtain the single dispersing Porphyrin Molecule particle of solid spherical aggregated structure；When the porphyrin in described Porphyrin Molecule suspension it is molten
Liquid is 1 with the volume ratio of poor solvent:1～3:1, and the concentration of porphyrin solution is 1 μM≤concentration<During 1M, hollow ball shape is obtained
The single dispersing Porphyrin Molecule particle of aggregated structure.Gather because the contact portion of water droplet template and solid substrate hinders Porphyrin Molecule
Collection in this place, thus can cause to assemble the single dispersing Porphyrin Molecule particle formation gap structure for being formed, and so as to assemble doliform is formed
Structure, can finally prepare the single dispersing Porphyrin Molecule particle of doliform aggregated structure, wherein：When described porphyrin solution and not
The volume ratio of good solvent is 1:5<Volume ratio<1:1, and the concentration of described porphyrin solution be 1 μM～1M when, obtain doliform aggregation
The single dispersing Porphyrin Molecule particle of structure.
It is on the surface of the described Porphyrin Molecule suspension that water droplet template is dispersed on solid substrate surface and dry, by
The evaporation of good solvent and poor solvent in Porphyrin Molecule suspension can cause temperature to reduce, and dew condensation thus can be caused to exist
The surface of Porphyrin Molecule suspension, the Porphyrin Molecule in Porphyrin Molecule suspension can assemble the surface for being dispersed in water droplet template, from
And form hollow ball shape, solid spherical, hollow hemispheric, the single dispersing Porphyrin Molecule particle of solid hemi-spherical aggregated structure.Its
In：When the volume ratio of the porphyrin solution in described Porphyrin Molecule suspension and poor solvent is 1:1～3:1, and described porphin
When the concentration of quinoline solution is 1M, the single dispersing Porphyrin Molecule particle of solid spherical aggregated structure is obtained；When described Porphyrin Molecule
Porphyrin solution in suspension is 1 with the volume ratio of poor solvent:1～3:1, and the concentration of described porphyrin solution be 1 μM≤
Concentration<During 1M, the single dispersing Porphyrin Molecule particle of hollow ball shape aggregated structure is obtained；When described porphyrin solution and poor solvent
Volume ratio be 1:5≤volume ratio<1:1, and the concentration of described porphyrin solution is 1 μM≤concentration<During 1M, hollow hemisphere is obtained
The single dispersing Porphyrin Molecule particle of shape aggregated structure；When the volume ratio of described porphyrin solution and poor solvent is 1:5≤volume
Than<1:1, and the concentration of described porphyrin solution be 1M when, obtain the single dispersing Porphyrin Molecule grain of solid hemi-spherical aggregated structure
Son.
After on the surface of the described water droplet template that Porphyrin Molecule suspension is dispersed on solid substrate surface, then by water
Drop template is dispersed on Porphyrin Molecule suspension and is dried；Due to the effect of water droplet template, and due to Porphyrin Molecule suspension
In good solvent and poor solvent evaporation, temperature can be caused to reduce, thus can cause the water droplet on Porphyrin Molecule suspension two sides
It is condensate in the two sides of Porphyrin Molecule suspension respectively, the Porphyrin Molecule in Porphyrin Molecule suspension can be assembled and be dispersed in Porphyrin Molecule
The surface of the condensing drip on suspension two sides forms many single dispersing Porphyrin Molecule particles, and the single dispersing porphin of these formation
Quinoline molecular particle merges mutually accumulation, so as to form the single dispersing Porphyrin Molecule particle of petal aggregated structure, wherein：When described
The volume ratio of porphyrin solution and poor solvent be 1:5≤volume ratio<3:1, and the concentration of described porphyrin solution be 1 μM≤it is dense
Degree<During 1M, the single dispersing Porphyrin Molecule particle of petal aggregated structure is obtained.
The bore of the single dispersing Porphyrin Molecule particle of described doliform aggregated structure connects with the solid substrate surface for being used
The increase of feeler and diminish；Or reduce with the Porphyrin Molecule in porphyrin solution with the increase of the volume ratio of good solvent.And it is described
Hollow hemispheric, the draw ratio of the single dispersing Porphyrin Molecule particle of solid hemi-spherical aggregated structure only by the porphin in porphyrin solution
Quinoline molecule reduces with the reduction of the volume ratio of good solvent.
The temperature of described drying is preferably -10～30 DEG C.Described relative humidity when being dried is 5%～95%.
The single dispersing Porphyrin Molecule particle of above-mentioned different aggregated structures, because water droplet template is tight orderly accumulation,
In the presence of water droplet template, relative humidity of the single dispersing Porphyrin Molecule particle that described aggregation is formed when being dried be 60%～
When 95%, assembling the single dispersing Porphyrin Molecule particle for being formed can assemble to form the crystalline substance of the Porphyrin Molecule photon with photonic crystal performance
Body.
Described Porphyrin Molecule passes through methine bridge selected from a class by the alpha -carbon atom of four pyroles subunits（=CH-）Mutually
The macromole heterocyclic compound for joining and being formed（Such as：Naphthalene porphyrin ethyl n-butyrate. zinc, 5- is to the Rhizoma Kaempferiae of ethyl n-butyrate. Oxy-1 0,15,20-
Base porphyrin, iron porphyrin etc.）In one kind.
One or more of described good solvent in chloroform, dichloromethane, toluene, dimethylbenzene etc..
The one kind or several of described poor solvent in isopropanol, ethanol, propanol, glycerol hexamethylene, normal hexane etc.
Kind.
Described solid substrate is the solid substrate with hydrophobic low-adhesiveness, with super-hydrophobic and low-adhesiveness
Solid substrate.
The described solid substrate with hydrophobic low-adhesiveness is poly tetrafluoroethylene or PDMS membrane；Or
Person is the solid substrate that Jing silicon fluorides are processed, and the solid substrate that described Jing silicon fluorides are processed is by selected clean solid-based
Material is placed in 3～8 hours in 80 DEG C of the baking oven with silicon fluoride atmosphere and obtains, and its clean solid substrate is preferably selected from common glass
Glass piece, polymeric film（Described polymeric film selected from polystyrene film, polymethyl methacrylate film, polyvinyl acetate film,
One kind in polyethylene film, polychloroethylene film, PET film）, it is piezoid, copper sheet, aluminium flake, a kind of in silicon chip.
Described is by clean and coarse solid substrate Jing fluorine silicon with super-hydrophobic and low-adhesiveness solid substrate
The solid substrate of alkane process；The solid substrate that described Jing silicon fluorides are processed is to put selected clean and coarse solid substrate
Obtain within 3～8 hours in 80 DEG C of the baking oven with silicon fluoride atmosphere, there should be super-hydrophobic and low-adhesiveness solid substrate
The contact angle of surface and water be 150～160 °；Described coarse solid substrate be by solid substrate be placed in concentration for 0.8～
The SiO of 5wt%2Immersion in aqueous dispersions is obtained for 1～3 minute, and its solid substrate is preferably selected from common glass sheet, polymeric film（Institute
The polymeric film stated is selected from poly tetrafluoroethylene, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, poly-
One kind in dimethyl siloxane film, polyethylene film, polychloroethylene film, PET film）, piezoid, copper sheet, aluminium flake, one in silicon chip
Kind.
The equipment of described inkjet printing is piezoelectric ink jet printer or industrial dispenser system etc., the hole of their shower nozzle
Footpath is preferably 10 μm, 20 μm, 50 μm or 150 μm.
The present invention is, with water droplet as template, to be first dissolved in Porphyrin Molecule and have the good molten of good solubility to Porphyrin Molecule
Porphyrin solution is obtained in agent, then porphyrin solution is dispersed in the poor solvent poor to Porphyrin Molecule dissolubility is obtained porphyrin point
Fullness over the chest during pregnancy supernatant liquid；Subsequently, prepared Porphyrin Molecule suspension is disperseed（Including drop coating, spraying or spraying dispersion etc.）To solid-based
On the surface of the water droplet template on material surface, or Porphyrin Molecule suspension water droplet template being distributed on solid substrate surface
On surface, or above two method is combined；Then solid substrate is placed on the environment of uniform temperature and relative humidity
In be dried；The evaporation conditionses of Porphyrin Molecule suspension when being dried by regulation and control（Mainly evaporating temperature, evaporating moisture）,
Porphyrin Molecule suspension is with the carrying out of evaporation process, and the good solvent therein evaporation produced in evaporation with poor solvent is right
Stream effect can induce Porphyrin Molecule therein can with water droplet as template, water droplet template surface aggregation and be assembled in water droplet template
Surface, formed single dispersing Porphyrin Molecule particle, and further by single dispersing Porphyrin Molecule particle assembling is formed with photon crystalline substance
The Porphyrin Molecule photonic crystal of body performance.Due to the orderly close packed array structure of water droplet template, eventually result in multiple poly-
The single dispersing Porphyrin Molecule particle that collection is formed has orderly arrangement architecture；Simultaneously according to the concentration and porphin of Porphyrin Molecule suspension
The ratio of each component is different in quinoline molecular suspension liquid, and the single dispersing Porphyrin Molecule particle that final aggregation is formed is solid spherical, sky
The single dispersing Porphyrin Molecule particle of bulbus cordis shape, solid hemi-spherical, hollow hemispheric, doliform or the shape such as petal；And by multiple
Multiple Porphyrin Molecule photonic crystals with photonic crystal performance that single dispersing Porphyrin Molecule particle assembling is formed also have orderly
The structure of arrangement, the Porphyrin Molecule photonic crystal with photonic crystal performance is also by solid spherical, hollow ball shape, solid hemisphere
The single dispersing Porphyrin Molecule particle assembling of shape, hollow hemispheric, doliform or the shape such as petal is obtained.The preparation method of the present invention
It is prepared by simply, low cost, easily operation, easily batch.The present invention is for the aggregated structure of regulation and control Porphyrin Molecule and for Porphyrin Molecule
And the package assembly of other conjugated polymer molecules provides new approaches, and to develop Porphyrin Molecule in high performance photoelectric device side
The application in face is significant.
Description of the drawings
The utilization water droplet template of Fig. 1 a. present invention, by Porphyrin Molecule suspension the water on solid substrate surface is dispersed in
It is on the surface of drop template and dry, assemble the schematic diagram of the single dispersing Porphyrin Molecule particle for being formed.
The utilization water droplet template of Fig. 1 b. present invention, by water droplet template the Porphyrin Molecule on solid substrate surface is dispersed in
It is on the surface of suspension and dry, assemble the schematic diagram of the single dispersing Porphyrin Molecule particle for being formed.
Fig. 2. the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of the doliform aggregated structure that the embodiment of the present invention 1 is prepared
Stereoscan photograph, wherein a are the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of single doliform aggregated structure, and b is multiple doliforms
The single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of aggregated structure.
Fig. 3. the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc of the preparation-obtained hollow ball shape aggregated structure of the embodiment of the present invention 1
The stereoscan photograph of particle.Wherein a is high magnification photo, and b is low range photo.
Fig. 4. the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc granule of the preparation-obtained petal aggregated structure of the embodiment of the present invention 3
The stereoscan photograph of son；Wherein a is the full face of the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of petal aggregated structure,
B is back side photo.
Fig. 5. the large-area single dispersing naphthalene porphyrin butanoic acid of the preparation-obtained petal aggregated structure of the embodiment of the present invention 3
The stereoscan photograph of ethyl ester zinc particles.
Specific embodiment
Embodiment 1.
According to shown in Fig. 1 a, at room temperature, naphthalene porphyrin ethyl n-butyrate. zinc is dissolved in chloroform, obtains the naphthalene porphyrin of 1mM
Ethyl n-butyrate. zinc chloroformic solution, by prepared naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution isopropanol is dispersed in respectively（Naphthalene porphyrin
Ethyl n-butyrate. zinc chloroformic solution is 3 with the volume ratio of isopropanol:1）, ethanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution and ethanol
Volume ratio be 0.9:1）, propanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is 2 with the volume ratio of propanol:1）And glycerol（Naphthalene
Porphyrin ethyl n-butyrate. zinc chloroformic solution is 1 with the volume ratio of glycerol:4）In, respectively obtain four kinds of naphthalene porphyrin ethyl n-butyrate. zinc and hang
Supernatant liquid；The above-mentioned four kinds of naphthalenes porphyrin ethyl n-butyrate. zinc suspension liquid for obtaining is distinguished into drop coating in the glass with hydrophobic low-adhesiveness
Piece, piezoid, silicon chip, copper sheet, aluminium flake, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, polyethylene
On the surface of the water droplet template on each solid substrate surface of film, polychloroethylene film and PET film；Then by gained sample point
Temperature is not placed in for -10 DEG C, relative humidity be 95% climatic chamber in place and be dried for 24 hours；And it is respectively placed in temperature
Spend for 30 DEG C, relative humidity be 10% climatic chamber in place and be dried for 24 hours.Above-mentioned water droplet template is will be described
Each solid substrate with hydrophobic low-adhesiveness be placed in temperature for -10 DEG C, relative humidity be 95% environment in it is cold
It is solidifying, then again described each solid substrate with hydrophobic low-adhesiveness moved to into room temperature（Such as 25 DEG C）In environment
Arrive；It is that selected clean solid substrate is placed in into 80 DEG C that each above-mentioned has the solid substrate of hydrophobic low-adhesiveness
Obtain within 3～8 hours in baking oven with silicon fluoride atmosphere.
It is -10 DEG C in temperature and temperature is that the result being dried at 30 DEG C finds, the aggregation of naphthalene porphyrin ethyl n-butyrate. zinc
Shape is unrelated with temperature and relative humidity when being dried, only with the naphthalene porphyrin ethyl n-butyrate. in naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid
Zinc chloroformic solution becomes with the change of the volume ratio of poor solvent isopropanol used, ethanol, propanol or glycerol.
It is after -10 DEG C and temperature are to be dried at 30 DEG C, to be dissolved in chloroform by naphthalene porphyrin ethyl n-butyrate. zinc in temperature
The naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution for preparing is dispersed in respectively isopropanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution with
The volume ratio of isopropanol is 3:1）And propanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is 2 with the volume ratio of propanol:1）Middle preparation
The naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid for obtaining, respectively drop coating is in the sheet glass with hydrophobic low-adhesiveness, piezoid, silicon
Piece, copper sheet, aluminium flake, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, polyethylene film, polychloroethylene film
On the surface of the water droplet template on each solid substrate surface of PET film, can be in sheet glass, piezoid, silicon chip, copper
Piece, aluminium flake, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, polyethylene film, polychloroethylene film and PET
The single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of hollow ball shape aggregated structure are obtained on film.It is dissolved in by naphthalene porphyrin ethyl n-butyrate. zinc
The naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution prepared in chloroform is dispersed in respectively ethanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution with
The volume ratio of ethanol is 0.9:1）And glycerol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is 1 with the volume ratio of glycerol:4）In
The naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid for preparing, respectively drop coating the sheet glass with hydrophobic low-adhesiveness, piezoid,
Silicon chip, copper sheet, aluminium flake, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, polyethylene film, polrvinyl chloride
On the surface of the water droplet template on each solid substrate surface of film and PET film, can be in sheet glass, piezoid, silicon chip, copper
Piece, aluminium flake, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, polyethylene film, polychloroethylene film and PET
The single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of doliform aggregated structure are obtained on film, and the bore of doliform is with naphthalene porphyrin fourth therein
Naphthalene porphyrin ethyl n-butyrate. zinc in acetoacetic ester zinc chloroformic solution reduces with the increase of the volume ratio of chloroform.
Fig. 2 is dispersed in ethanol for naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution and second
The volume ratio of alcohol is 0.9:1）In the naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid that obtains, drop coating is in the silicon with hydrophobic low-adhesiveness
On the surface of the water droplet template on piece surface, be placed in temperature for -10 DEG C, relative humidity be 95% climatic chamber in place
The stereoscan photograph of the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of the doliform aggregated structure obtained after being dried for 24 hours,
The mouth of wherein doliform is wide close 1.5 microns.A in Fig. 2 is the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc of single doliform aggregated structure
Particle, b is the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of multiple doliform aggregated structures.
Fig. 3 is dispersed in propanol for naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution and third
The volume ratio of alcohol is 2:1）In the naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid that obtains, drop coating is in the polyphenyl with hydrophobic low-adhesiveness
On the surface of the water droplet template on vinyl film surface, temperature is placed in for -10 DEG C, relative humidity is in 95% climatic chamber
The scanning of the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of the hollow ball shape aggregated structure that placement is obtained after being dried for 24 hours
Electromicroscopic photograph, which show the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of the multiple hollow ball shape aggregated structures for preparing
With arrangement architecture in good order, and show that these have the list of the hollow ball shape aggregated structure of arrangement architecture in good order
Dispersion naphthalene porphyrin ethyl n-butyrate. zinc particles have photonic crystal performance.A in Fig. 3 is high magnification photo, and b is low range photo.
Embodiment 2.
According to shown in Fig. 1 b, at room temperature, naphthalene porphyrin ethyl n-butyrate. zinc is dissolved in chloroform, obtains the naphthalene porphyrin of 1mM
Ethyl n-butyrate. zinc chloroformic solution, by prepared naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution isopropanol is dispersed in respectively（Naphthalene porphyrin
Ethyl n-butyrate. zinc chloroformic solution is 3 with the volume ratio of isopropanol:1）, ethanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution and ethanol
Volume ratio be 0.9:1）, propanol（Naphthalene porphyrin ethyl n-butyrate. zinc solution is 2 with the volume ratio of propanol:1）And glycerol（Naphthalene porphyrin
Ethyl n-butyrate. zinc solution is 1 with the volume ratio of glycerol:3）In, respectively obtain four kinds of naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid；Will
The above-mentioned four kinds of naphthalenes porphyrin ethyl n-butyrate. zinc suspension liquid for obtaining distinguishes drop coating to sheet glass, quartz with hydrophobic low-adhesiveness
Piece, silicon chip, copper sheet, aluminium flake, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, polyethylene film, polychlorostyrene
On each solid substrate of vinyl film and PET film（Each above-mentioned have the solid substrate of hydrophobic low-adhesiveness be by
Selected clean solid substrate is placed in 3～8 hours in 80 DEG C of the baking oven with silicon fluoride atmosphere and obtains）, beaten by ink-jet
Print injection water droplet, by water droplet be dispersed in it is above-mentioned each there is naphthalene porphyrin fourth on the solid substrate surface of hydrophobic low-adhesiveness
On the surface of acetoacetic ester zinc suspension liquid；Then gained sample is respectively placed in into temperature for 30 DEG C, relative humidity is 95% constant temperature perseverance
Place in wet tank and be dried for 24 hours；And be respectively placed in temperature for 30 DEG C, relative humidity be 10% climatic chamber in place
It is dried within 24 hours；After sample drying, respectively in sheet glass, piezoid, silicon chip, copper sheet, aluminium flake, polystyrene film, poly- first
Naphthalene porphyrin butanoic acid second has been obtained in base acrylic acid methyl ester. film, polyvinyl acetate film, polyethylene film, polychloroethylene film and PET film
The hollow ball shape of ester zinc or the aggregated structure of hollow hemispheric.As a result aggregation shape and the drying of naphthalene porphyrin ethyl n-butyrate. zinc are found
When temperature and relative humidity it is unrelated, only with the naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution in naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid
Must change with the volume ratio of poor solvent isopropanol used, ethanol, propanol or glycerol and become.
Water droplet is dispersed in into above-mentioned sheet glass, piezoid, silicon chip, copper sheet, aluminium flake, polystyrene film, polymethylacrylic acid
It is molten by naphthalene porphyrin ethyl n-butyrate. zinc on methyl ester film, polyvinyl acetate film, polyethylene film, polychloroethylene film and PET film surface
The naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution that solution is prepared in chloroform is dispersed in respectively isopropanol（Naphthalene porphyrin ethyl n-butyrate. zinc
Chloroformic solution is 3 with the volume ratio of isopropanol:1）And propanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is with the volume ratio of propanol
2:1）In on the surface of naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid for preparing, obtained single point of hollow ball shape aggregated structure
Scattered naphthalene porphyrin ethyl n-butyrate. zinc particles.
Water droplet is dispersed in into above-mentioned sheet glass, piezoid, silicon chip, copper sheet, aluminium flake, polystyrene film, polymethylacrylic acid
It is molten by naphthalene porphyrin ethyl n-butyrate. zinc on methyl ester film, polyvinyl acetate film, polyethylene film, polychloroethylene film and PET film surface
The naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution that solution is prepared in chloroform is dispersed in respectively ethanol（Naphthalene porphyrin ethyl n-butyrate. zinc chlorine
Imitative solution is 0.9 with the volume ratio of ethanol:1）And glycerol（The volume ratio of naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution and glycerol
For 1:3）In on the surface of naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid for preparing, obtained hollow hemispheric aggregated structure
Single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles, and the draw ratio of hollow hemispheric is molten with naphthalene porphyrin ethyl n-butyrate. zinc chloroform therein
Naphthalene porphyrin ethyl n-butyrate. zinc in liquid increases with the increase of the volume ratio of chloroform.
Embodiment 3.
According to shown in Fig. 1 a, at room temperature, naphthalene porphyrin ethyl n-butyrate. zinc is dissolved in chloroform, obtains the naphthalene porphyrin of 1mM
Ethyl n-butyrate. zinc chloroformic solution, by prepared naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution isopropanol is dispersed in respectively（Naphthalene porphyrin
Ethyl n-butyrate. zinc chloroformic solution is 3 with the volume ratio of isopropanol:1）, ethanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution and ethanol
Volume ratio be 0.9:1）, propanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is 2 with the volume ratio of propanol:1）And glycerol（Naphthalene
Porphyrin ethyl n-butyrate. zinc chloroformic solution is 1 with the volume ratio of glycerol:3）In, respectively obtain four kinds of naphthalene porphyrin ethyl n-butyrate. zinc and hang
Supernatant liquid；The above-mentioned four kinds of naphthalenes porphyrin ethyl n-butyrate. zinc suspension liquid for obtaining is distinguished into drop coating to the glass with hydrophobic low-adhesiveness
Piece, piezoid, silicon chip, copper sheet, aluminium flake, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, polyethylene
On the surface of the water droplet template on each solid substrate surface of film, polychloroethylene film and PET film, obtain in water droplet template
Dispersion on surface has the sample of naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid；Above-mentioned water droplet template is with hydrophobic low adhesion by described
Each solid substrate of performance is placed in temperature for -10 DEG C, relative humidity be 95% environment in condense, then again will be described
Each solid substrate with hydrophobic low-adhesiveness moves to room temperature（Such as 25 DEG C）Obtain in environment.Then again by water droplet template
It is dispersed on the naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid on the surface of the water droplet template on above-mentioned each solid substrate surface, the water
Drop template is that temperature is placed in as the sample by obtained by for 5 DEG C, relative humidity be 60% climatic chamber in place after, make water droplet
It is condensate on the surface of naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid and obtains.Then by gained in naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid
Two sides is respectively the sample of water droplet template and is respectively placed in temperature for 30 DEG C, relative humidity be 95% climatic chamber in place 24
Hour is dried；And be respectively placed in temperature for 30 DEG C, relative humidity be 10% climatic chamber in place and done for 24 hours
It is dry.After sample drying, respectively in sheet glass, piezoid, silicon chip, copper sheet, aluminium flake, polystyrene film, polymethyl methacrylate
The single dispersing naphthalene of petal aggregated structure is obtained in film, polyvinyl acetate film, polyethylene film, polychloroethylene film and PET film
Porphyrin ethyl n-butyrate. zinc particles.
It is to be placed in selected clean solid substrate that each above-mentioned has the solid substrate of hydrophobic low-adhesiveness
Obtain within 3～8 hours in 80 DEG C of the baking oven with silicon fluoride atmosphere.
As a result find that the petal aggregated structure of naphthalene porphyrin ethyl n-butyrate. zinc is unrelated with the temperature and humidity of system, only with naphthalene porphin
Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution in quinoline ethyl n-butyrate. zinc suspension liquid and poor solvent isopropanol used, ethanol, third
The change of the volume ratio of alcohol or glycerol and become.When the ratio of the naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution in system is less, obtain
The petal number of the particle for arriving is more.
Fig. 4,5 show and the naphthalene porphyrin ethyl n-butyrate. zinc chlorine prepared in chloroform are dissolved in by naphthalene porphyrin ethyl n-butyrate. zinc
Imitative solution is dispersed in isopropanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is 3 with the volume ratio of isopropanol:1）The suspension for obtaining
The result of the petal obtained after drying.
Embodiment 4.
According to shown in Fig. 1 a, at room temperature, naphthalene porphyrin ethyl n-butyrate. zinc is dissolved in dichloromethane, obtains the naphthalene of 1mM
Porphyrin ethyl n-butyrate. zinc chloroformic solution, by prepared naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution isopropanol is dispersed in respectively（Naphthalene
Porphyrin ethyl n-butyrate. zinc chloroformic solution is 0.9 with the volume ratio of isopropanol:1）, hexamethylene（Naphthalene porphyrin ethyl n-butyrate. zinc chloroform is molten
Liquid is 1.1 with the volume ratio of hexamethylene:5）, normal hexane（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is with the volume ratio of normal hexane
2:1）And glycerol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is 1 with the volume ratio of glycerol:3）In, respectively obtain four kinds of naphthalenes
Porphyrin ethyl n-butyrate. zinc suspension liquid；The above-mentioned four kinds of naphthalenes porphyrin ethyl n-butyrate. zinc suspension liquid for obtaining is sprayed to respectively with hydrophobic
On the surface of the water droplet template on the PDMS membrane and poly tetrafluoroethylene surface of low-adhesiveness, and spray to
Clean common glass sheet, silicon chip, copper sheet, polystyrene film, polymethyl methacrylate film, poly-vinegar that Jing silicon fluorides were processed
On the surface of the water droplet template on each solid substrate surface of vinyl acetate film, polyethylene film and polychloroethylene film（It is described
Jing silicon fluorides process, be that selected clean above-mentioned solid substrate is placed in 3 in 80 DEG C of the baking oven with silicon fluoride atmosphere
Obtain within～8 hours）；Wherein water droplet template is that the vaporific water droplet of injection is obtained.Then gained sample is respectively placed in into temperature for -10
DEG C, relative humidity be 5% climatic chamber in be dried；After sample drying, dichloro is dissolved in by naphthalene porphyrin ethyl n-butyrate. zinc
The naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution obtained in methane is dispersed in respectively isopropanol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution
It is 0.9 with the volume ratio of isopropanol:1）, hexamethylene（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is with the volume ratio of hexamethylene
1.1:5）And glycerol（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution is 1 with the volume ratio of glycerol:3）In the naphthalene porphyrin fourth that obtains
Acetoacetic ester zinc suspension liquid sprays to respectively the above-mentioned PDMS membrane with hydrophobic low-adhesiveness and politef
On the surface of the water droplet template on film surface, and spray to clean each described solid-based that Jing silicon fluorides were processed
On the surface of the water droplet template on the surface of material, the single dispersing naphthalene porphyrin ethyl n-butyrate. zinc of doliform aggregated structure is obtained after being dried
Particle.Wherein the bore of doliform reduces with the ratio of naphthalene porphyrin ethyl n-butyrate. zinc dichloride dichloromethane in suspension and increases.
And normal hexane is dispersed in by naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution（Naphthalene porphyrin ethyl n-butyrate. zinc chloroformic solution with just
The volume ratio of hexane is 2:1）In the naphthalene porphyrin ethyl n-butyrate. zinc suspension liquid that obtains spray to respectively it is above-mentioned with hydrophobic low adhesion
On the surface of the water droplet template on the PDMS membrane and poly tetrafluoroethylene surface of performance, and spray to Jing fluorine silicon
On the surface of the water droplet template on the surface of clean each described solid substrate that alkane was processed, after being dried sky is obtained
The single dispersing naphthalene porphyrin ethyl n-butyrate. zinc particles of bulbus cordis shape aggregated structure.
Embodiment 5.
According to shown in Fig. 1 a, at room temperature, 5- is dissolved in into first to the naphthyl porphyrin of ethyl n-butyrate. Oxy-1 0,15,20- tri-
In benzene, the 5- of 1M is obtained to the naphthyl porphyrin toluene solution of ethyl n-butyrate. Oxy-1 0,15,20- tri-, by prepared 5- to butanoic acid
The naphthyl porphyrin toluene solutions of ethyl ester Oxy-1 0,15,20- tri- are dispersed in respectively isopropanol（5- to ethyl n-butyrate. Oxy-1 0,15,
The naphthyl porphyrin toluene solutions of 20- tri- are 2 with the volume ratio of isopropanol:1）, hexamethylene（5- is to ethyl n-butyrate. Oxy-1 0,15,20-
Three naphthyl porphyrin toluene solutions are 1 with the volume ratio of hexamethylene:3）, normal hexane（5- is to ethyl n-butyrate. Oxy-1 0,15,20- tri-
Naphthyl porphyrin toluene solution is 2 with the volume ratio of normal hexane:1）And glycerol（5- is to ethyl n-butyrate. Oxy-1 0,15,20- Rhizoma Kaempferiae
Base porphyrin toluene solution is 1 with the volume ratio of glycerol:3）In, four kinds of 5- are respectively obtained to ethyl n-butyrate. Oxy-1 0,15,20-
Three naphthyl porphyrin suspensions；By the above-mentioned four kinds of 5- for obtaining to the naphthyl porphyrin suspensions of ethyl n-butyrate. Oxy-1 0,15,20- tri- point
Not as ink-jet printing ink, each ink-jet printing ink in obtain four kinds of ink-jet printing inks is loaded into into respectively 4
In the print cartridge of platform ink-jet printer（The aperture of inkjet printer head is respectively 10 μm, 20 μm, 50 μm, 150 μm)；Then by institute
The ink-jet printing ink stated is ejected into respectively with super-hydrophobic and low-adhesiveness common glass sheet, piezoid, copper sheet, aluminum
Piece, silicon chip, polystyrene film, polymethyl methacrylate film, polyvinyl acetate film and PDMS membrane it is each
Plant on the surface of the water droplet template on solid substrate upper surface（Place with super-hydrophobic and low-adhesiveness above-mentioned solid substrate
Reason method is：Selected clean and coarse solid substrate is placed in 3～8 hours in 80 DEG C of the baking oven with silicon fluoride atmosphere
Obtain, there should be the surface of super-hydrophobic and low-adhesiveness solid substrate to be 150～160 ° with the contact angle of water；Described is thick
Rough solid substrate is that solid substrate is placed in into the SiO that concentration is 0.8～5wt%2Immersion in aqueous dispersions is obtained for 1～3 minute）；
In this experiment, water droplet template is to be placed in temperature with super-hydrophobic and low-adhesiveness each solid substrate by described
For -10 DEG C, relative humidity be 95% environment in condense, then again by described with super-hydrophobic and low-adhesiveness each
Plant solid substrate and move to room temperature（Such as 25 DEG C）Obtain in environment.Then gained sample is respectively placed in into temperature for -5 DEG C, it is relatively wet
Spend in the climatic chamber for 10% and be dried；And temperature is respectively placed in for 0 DEG C, relative humidity is in 80% climatic chamber
It is dried.
After sample drying, isopropanol is dispersed in the naphthyl porphyrin toluene solution of ethyl n-butyrate. Oxy-1 0,15,20- tri- by 5-
（5- is 2 to the volume ratio of the naphthyl porphyrin toluene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- and isopropanol:1）, normal hexane（5-
It is 2 to the volume ratio of the naphthyl porphyrin toluene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- and normal hexane:1）In obtain 5- pair
The naphthyl porphyrin suspension of ethyl n-butyrate. Oxy-1 0,15,20- tri-, difference inkjet printing is to above-mentioned with super-hydrophobic and low-adhesion
On the surface of the water droplet template on each solid substrate surface of energy, obtain with solid spherical aggregated structure after being dried
5- is to the naphthyl porphyrin particles of ethyl n-butyrate. Oxy-1 0,15,20- tri-.
Hexamethylene is dispersed in the naphthyl porphyrin toluene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- by 5-（5- is to butanoic acid second
The naphthyl porphyrin toluene solutions of ester Oxy-1 0,15,20- tri- are 1 with the volume ratio of hexamethylene:3）And glycerol（5- is to ethyl n-butyrate.
The naphthyl porphyrin toluene solutions of Oxy-1 0,15,20- tri- are 1 with the volume ratio of glycerol:3）In the 5- that obtains to ethyl n-butyrate. oxygen
Base -10,15,20- tri- naphthyl porphyrin suspensions, respectively inkjet printing to it is above-mentioned with it is super-hydrophobic and low-adhesiveness each
On the surface of the water droplet template on solid substrate surface, the 5- with doliform aggregated structure is obtained to ethyl n-butyrate. oxygen after being dried
The naphthyl porphyrin particles of base -10,15,20- three.
Embodiment 6.
According to shown in Fig. 1 b, at room temperature, 5- is dissolved in into two to the naphthyl porphyrin of ethyl n-butyrate. Oxy-1 0,15,20- tri-
In toluene, the 5- of 1M is obtained to the naphthyl porphyrin xylene solution of ethyl n-butyrate. Oxy-1 0,15,20- tri-, by prepared 5- pair
The naphthyl porphyrin xylene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- are dispersed in respectively isopropanol（5- to ethyl n-butyrate. epoxide-
The naphthyl porphyrin xylene solutions of 10,15,20- tri- are 2 with the volume ratio of isopropanol:1）, hexamethylene（5- to ethyl n-butyrate. epoxide-
The naphthyl porphyrin xylene solutions of 10,15,20- tri- are 1 with the volume ratio of hexamethylene:3）, normal hexane（5- to ethyl n-butyrate. epoxide-
The naphthyl porphyrin xylene solutions of 10,15,20- tri- are 2 with the volume ratio of normal hexane:1）And glycerol（5- to ethyl n-butyrate. epoxide-
The naphthyl porphyrin xylene solutions of 10,15,20- tri- are 1 with the volume ratio of glycerol:3）In, four kinds of 5- are respectively obtained to butanoic acid second
The naphthyl Porphyrin Molecule suspensions of ester Oxy-1 0,15,20- tri-；By the above-mentioned four kinds of 5- for obtaining to ethyl n-butyrate. Oxy-1 0,15,
The naphthyl porphyrin suspensions of 20- tri- spray each in obtain four kinds of ink-jet printing inks respectively as ink-jet printing ink
Black marking ink is loaded into respectively in the print cartridge of 4 industrial dispenser systems（The aperture of its shower nozzle is respectively 10 μm, 20 μm, 50 μm,
150μm)；Then ink-jet printing ink is ejected into respectively Jing silicon fluorides process the sheet glass with hydrophobic low-adhesiveness,
On each solid substrate of piezoid, aluminium flake and silicon chip（Described Jing silicon fluorides are processed, and being will be selected clean above-mentioned solid
Body base material is placed in 3～8 hours in 80 DEG C of the baking oven with silicon fluoride atmosphere and obtains）；Then the vaporific water droplet of fill-before-fire is to upper
State each and there is the 5- on the solid substrate surface of hydrophobic low-adhesiveness to the naphthyls of ethyl n-butyrate. Oxy-1 0,15,20- tri-
On the surface of porphyrin suspension.Then gained sample is respectively placed in into temperature for 5 DEG C, relative humidity is 10% climatic chamber
In be dried；And be respectively placed in temperature for 10 DEG C, relative humidity be 5% climatic chamber in be dried；Sample drying
Afterwards, on sheet glass, piezoid, aluminium flake and silicon chip 5- has been obtained to the naphthyl porphyrin of ethyl n-butyrate. Oxy-1 0,15,20- tri- respectively
Aggregated structure.
Wherein isopropanol is dispersed in respectively to the naphthyl porphyrin xylene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- by 5-
（5- is 2 to the volume ratio of the naphthyl porphyrin xylene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- and isopropanol:1）, normal hexane
（5- is 2 to the volume ratio of the naphthyl porphyrin xylene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- and normal hexane:1）In obtain
, to the naphthyl Porphyrin Molecule suspension of ethyl n-butyrate. Oxy-1 0,15,20- tri-, difference ink-jet is to above-mentioned with hydrophobic low-adhesion for 5-
On each solid substrate surface of energy, then water droplet template is ejected into into 5- to the naphthyl porphyrin of ethyl n-butyrate. Oxy-1 0,15,20- tri-
On the surface of molecular suspension liquid, the 5- of solid spherical aggregated structure is obtained to ethyl n-butyrate. Oxy-1 0,15,20- tri- after being dried
Naphthyl porphyrin particle.
And hexamethylene is dispersed in respectively to the naphthyl porphyrin xylene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- by 5-（5-
It is 1 to the volume ratio of the naphthyl porphyrin xylene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- and hexamethylene:3）, glycerol（5-
It is 1 to the volume ratio of the naphthyl porphyrin xylene solutions of ethyl n-butyrate. Oxy-1 0,15,20- tri- and glycerol:3）In the 5- that obtains
To the naphthyl Porphyrin Molecule suspension of ethyl n-butyrate. Oxy-1 0,15,20- tri-, difference ink-jet is to above-mentioned with hydrophobic low-adhesiveness
Each solid substrate surface on, then water droplet template is ejected into into 5- to the naphthyl porphyrin of ethyl n-butyrate. Oxy-1 0,15,20- tri-
On the surface of molecular suspension liquid, the 5- of solid hemi-spherical aggregated structure is obtained to ethyl n-butyrate. Oxy-1 0,15,20- after being dried
Three naphthyl porphyrin particles.
Claims (7)
1. a kind of method that utilization water droplet template prepares single dispersing Porphyrin Molecule particle, is characterized in that：Porphyrin Molecule is dissolved
Porphyrin solution is obtained in good solvent, the porphyrin solution for obtaining is dispersed in poor solvent, obtain Porphyrin Molecule suspension；Will
The Porphyrin Molecule suspension for obtaining is dispersed on the surface of the water droplet template on solid substrate surface and is dried, or by water droplet template
It is dispersed on the surface of the Porphyrin Molecule suspension on solid substrate surface and is dried, or Porphyrin Molecule suspension is dispersed in solid
After on the surface of the water droplet template on body substrate surface, then water droplet template is dispersed on Porphyrin Molecule suspension and is dried；
To the single dispersing Porphyrin Molecule particle that aggregation is formed；The single dispersing Porphyrin Molecule particle that multiple described aggregations are formed has orderly
Arrangement architecture；
The concentration of described porphyrin solution is 1 μM～1M；
Described porphyrin solution is 1 with the volume ratio of poor solvent:5～3:1；
One or more of described good solvent in chloroform, dichloromethane, toluene, dimethylbenzene；
One or more of described poor solvent in isopropanol, ethanol, propanol, glycerol, hexamethylene, normal hexane；
Single dispersing Porphyrin Molecule particle that described aggregation is formed is shaped as solid spherical, hollow ball shape, solid hemi-spherical, sky
Heart hemispherical, doliform or petal；
It is on the surface of the described water droplet template that the Porphyrin Molecule suspension for obtaining is dispersed on solid substrate surface and dry,
Wherein：When the volume ratio of the porphyrin solution in described Porphyrin Molecule suspension and poor solvent is 1:1～3:1, and porphyrin is molten
When the concentration of liquid is 1M, the single dispersing Porphyrin Molecule particle of solid spherical aggregated structure is obtained；When described Porphyrin Molecule suspends
Porphyrin solution in liquid is 1 with the volume ratio of poor solvent:1～3:1, and the concentration of porphyrin solution is 1 μM≤concentration<During 1M,
Obtain the single dispersing Porphyrin Molecule particle of hollow ball shape aggregated structure；When described porphyrin solution and the volume ratio of poor solvent are
1:5<Volume ratio<1:1, and the concentration of described porphyrin solution be 1 μM～1M when, obtain the single dispersing porphyrin of doliform aggregated structure
Molecular particle；
It is on the surface of the described Porphyrin Molecule suspension that water droplet template is dispersed on solid substrate surface and dry, wherein：
When the volume ratio of the porphyrin solution in described Porphyrin Molecule suspension and poor solvent is 1:1～3:1, and described porphyrin is molten
When the concentration of liquid is 1M, the single dispersing Porphyrin Molecule particle of solid spherical aggregated structure is obtained；When described Porphyrin Molecule suspends
Porphyrin solution in liquid is 1 with the volume ratio of poor solvent:1～3:1, and the concentration of described porphyrin solution is 1 μM≤concentration<
During 1M, the single dispersing Porphyrin Molecule particle of hollow ball shape aggregated structure is obtained；When described porphyrin solution and the body of poor solvent
Product is than being 1:5≤volume ratio<1:1, and the concentration of described porphyrin solution is 1 μM≤concentration<During 1M, hollow hemispheric is obtained
The single dispersing Porphyrin Molecule particle of aggregated structure；When the volume ratio of described porphyrin solution and poor solvent is 1:5≤volume ratio<
1:1, and the concentration of described porphyrin solution be 1M when, obtain the single dispersing Porphyrin Molecule particle of solid hemi-spherical aggregated structure；
After on the surface of the described water droplet template that Porphyrin Molecule suspension is dispersed on solid substrate surface, then by water droplet mould
Plate is dispersed on Porphyrin Molecule suspension and is dried；Wherein：When the volume ratio of described porphyrin solution and poor solvent is 1:5≤
Volume ratio<3:1, and the concentration of described porphyrin solution is 1 μM≤concentration<During 1M, the single dispersing of petal aggregated structure is obtained
Porphyrin Molecule particle.
2. method according to claim 1, is characterized in that：The temperature of described drying is -10～30 DEG C；Described drying
When relative humidity be 5%～95%.
3. method according to claim 1, is characterized in that：Described Porphyrin Molecule is selected from a class by four pyroles subunits
The alpha -carbon atom macromole heterocyclic compound that interconnects and formed by methine bridge in one kind.
4. method according to claim 1, is characterized in that：Described solid substrate is consolidating with hydrophobic low-adhesiveness
Body base material or with super-hydrophobic and low-adhesiveness solid substrate.
5. method according to claim 4, is characterized in that：The described solid substrate with hydrophobic low-adhesiveness is poly-
Tetrafluoroethylene or PDMS membrane；Or the solid substrate that Jing silicon fluorides are processed, described Jing silicon fluorides process
Solid substrate be to be placed in selected clean solid substrate in 80 DEG C of the baking oven with silicon fluoride atmosphere 3～8 hours
Arrive；Clean solid substrate selected by it is a kind of in common glass sheet, polymeric film, piezoid, copper sheet, aluminium flake, silicon chip；
Described polymeric film is selected from polystyrene film, polymethyl methacrylate film, polyvinyl acetate film, polyethylene film, polychlorostyrene
One kind in vinyl film, PET film；
Described is by clean and coarse solid substrate Jing silicon fluorides with super-hydrophobic and low-adhesiveness solid substrate
The solid substrate of reason；The solid substrate that described Jing silicon fluorides are processed is that selected clean and coarse solid substrate is placed in into 80
DEG C the baking oven with silicon fluoride atmosphere in obtain within 3～8 hours, should have super-hydrophobic and low-adhesiveness solid substrate table
Face is 150～160 ° with the contact angle of water；Described coarse solid substrate be by solid substrate be placed in concentration for 0.8～
The SiO of 5wt%2Immersion in aqueous dispersions is obtained for 1～3 minute, and its solid substrate is selected from common glass sheet, polymeric film, quartz
It is a kind of in piece, copper sheet, aluminium flake, silicon chip；Described polymeric film is selected from poly tetrafluoroethylene, polystyrene film, polymethyl
One kind in sour methyl ester film, polyvinyl acetate film, PDMS membrane, polyethylene film, polychloroethylene film, PET film.
6. method according to claim 1, is characterized in that：The single dispersing Porphyrin Molecule particle that described aggregation is formed is dry
When relative humidity when dry is 60%～95%, assembling the single dispersing Porphyrin Molecule particle for being formed can assemble to form brilliant with photon
The Porphyrin Molecule photonic crystal of body performance.
7. method according to claim 6, is characterized in that：The described Porphyrin Molecule photon with photonic crystal performance is brilliant
Body is shaped as solid spherical, hollow ball shape, solid hemi-spherical, hollow hemispheric, doliform or petal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310466855.9A CN104557948B (en) | 2013-10-09 | 2013-10-09 | Method for preparing monodispersed porphyrin molecule particles by water droplet templating method |
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| CN1706844A (en) * | 2004-06-04 | 2005-12-14 | 中国科学院化学研究所 | Metal porphyrin nanotube and nanoline and their prepn process |
| US8012278B2 (en) * | 2006-04-28 | 2011-09-06 | University of Pittsburgh—of the Commonwealth System of Higher Education | End-to-end joining of nanotubes |
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| CN1706844A (en) * | 2004-06-04 | 2005-12-14 | 中国科学院化学研究所 | Metal porphyrin nanotube and nanoline and their prepn process |
| US8012278B2 (en) * | 2006-04-28 | 2011-09-06 | University of Pittsburgh—of the Commonwealth System of Higher Education | End-to-end joining of nanotubes |
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| 两亲性金属卟啉界面和溶液有序组装结构的研究;王丽丽;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20100515;B014-35 * |
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