CN105504957B - Application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing - Google Patents
Application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing Download PDFInfo
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- CN105504957B CN105504957B CN201510997097.2A CN201510997097A CN105504957B CN 105504957 B CN105504957 B CN 105504957B CN 201510997097 A CN201510997097 A CN 201510997097A CN 105504957 B CN105504957 B CN 105504957B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
- B41M5/04—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet using solvent-soluble dyestuffs on the master sheets, e.g. alcohol-soluble
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/14—Printing inks based on carbohydrates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
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Abstract
The invention discloses a kind of a kind of applications carrying out micro-contact printing on polymethyl methacrylate base bottom as new compound ink using α cyclodextrin and ferrocene, using α cyclodextrin and solution of ferrocene as the print paste of micro-contact printing, the pattern of PDMS seals is transferred to the polymethyl methacrylate base bottom of carboxylated, obtain exquisite metal pattern in substrate by the method for chemical plating again, by regarding α cyclodextrin and ferrocene composite solution as micro-contact printing ink metal pattern is prepared in the common polymethyl methacrylate base bottom surface of electronics industry, new approaches are provided for micro-contact printing industry.
Description
Technical field
It is the invention belongs to modern electronic technology field, more particularly to a kind of using alpha-cyclodextrin and ferrocene as composite green
Application of the color Environment-friendlyink ink in micro-contact printing.
Background technology
The micro- constructing technology in surface is just gradually being embodied in significant application value, especially microcontact printing techniques, can
The micro-patterning in small size is of great significance in multiple fields especially modern electronic technology field.It is available at present
Micro-contact printing ink it is less, also limited to the material that surface can carry out micro-contact printing, a large amount of material can not be connect with micro-
The method for touching printing prepares picture on surface.Ink that is new, stablizing thus is developed to have a very big significance.
In order to adapt to requirement of the ink of new generation for environmental protection and health, it is necessary to which further exploitation cyclodextrin is micro-
Application in contact printing.Cyclodextrin is nontoxic, has good human compatibility.Alpha-cyclodextrin and ferrocene composite solution performance
Stablize, quality of forming film is high, and the micro-contact printing of surfaces of various materials can be applied to as a kind of ink of stabilization.α-ring at present
Dextrin and ferrocene composite solution have not been reported as the application of micro-contact printing ink.
Invention content
The object of the present invention is to provide a kind of using alpha-cyclodextrin and ferrocene as a kind of new compound ink in poly- first
The application of micro-contact printing is carried out in base methyl acrylate substrate.
In order to realize purposes and other advantages according to the present invention, provide using alpha-cyclodextrin and ferrocene as compound
Application of the ink in micro-contact printing, including：
Step 1 prepares alpha-cyclodextrin and ferrocene composite solution, and alpha-cyclodextrin is obtained a concentration of 3-6g/ with water dissolution
The alpha-cyclodextrin aqueous solution of L, alpha-cyclodextrin aqueous solution in ferrocene is added, in ultrasonic vibration 30-60min, obtain α-ring
Dextrin and ferrocene composite solution；
PDMS seals are soaked in 30-40s in alpha-cyclodextrin and ferrocene composite solution, taken out in nitrogen stream by step 2
Middle dry 30-60s obtains the PDMS seals for being coated with alpha-cyclodextrin and ferrocene composite solution, and the PDMS seals is placed on
In the polymethylacrylic acid substrate of carboxylated, PDMS seal designs are transferred to substrate surface, obtain printing figuratum poly-
Methacrylic acid substrate；
Step 3 will print figuratum polymethylacrylic acid substrate in PdCl210-30s is impregnated in solution, taking-up is put into use
In the solution of electroless copper, 1-10min is impregnated, metal copper pattern can be obtained after taking-up in polymethylacrylic acid substrate.
Preferably, the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, step
The usage ratio of alpha-cyclodextrin and ferrocene is that 0.8g ferrocene is added in every liter of alpha-cyclodextrin aqueous solution in rapid one.
Preferably, the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing gathers
The carbonylation process of methacrylic acid is：Polymethylacrylic acid substrate is impregnated into 30- in the isopropanol water solution of 45-55%
60min, then 15-20min is impregnated with 2-3mol/L sulfuric acid, it takes out after cleaning, 60-65 DEG C of vacuum drying obtains the poly- first of carboxylated
Base acrylic bottom.
Preferably, the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, makes
Temperature control is at 55-65 DEG C when impregnating polymethylacrylic acid with sulfuric acid.
Preferably, the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, step
PdCl in rapid three2A concentration of 0.1-0.2g/L of solution.
Preferably, the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, step
Solution in rapid three for electroless copper is made of following raw material：4-6wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% hydrogen
The distilled water of sodium oxide molybdena, 32wt% formaldehyde and surplus forms.
The present invention includes at least following advantageous effect：
1, alpha-cyclodextrin intramolecule is a V-shaped hydrophobic cavities, and cavity heights 0.79nm is a diameter of
0.47nm is suitble to receiving ferrocene molecule to enter and be fixed on alpha-cyclodextrin intramolecule；It is combined using the coordination of iron and carboxyl
PDMS seal designs are transferred to substrate surface by effect, obtain printing figuratum substrate.
2, the alpha-cyclodextrin and ferrocene composite solution have good biocompatibility, and iron is indispensable in human body
One of element can meet requirement of the ink of new generation for environmental protection and health.
3, alpha-cyclodextrin and ferrocene composite solution raw material are easy to get, are at low cost, is stable, environmentally protective, in commercial Application
With prodigious potentiality.
4, commonly gathered in electronics industry by regarding alpha-cyclodextrin and ferrocene composite solution as micro-contact printing ink
Methyl methacrylate substrate surface prepares metal pattern, and new approaches are provided for micro-contact printing industry.
Specific implementation mode
The present invention is described in further detail below, to enable those skilled in the art being capable of evidence with reference to specification word
To implement.
Application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, including：
Step 1, substrate carboxylated, substrate are polymethyl methacrylate, by the isopropanol of base material 45-55%
Aqueous solution soaking 30-60min, then 15-20min is impregnated under the conditions of 55-65 DEG C with 2-3mol/L sulfuric acid, then wash with water,
60-65 DEG C of vacuum drying, obtains carboxylated substrate.
Step 2 prepares alpha-cyclodextrin and ferrocene composite solution, and alpha-cyclodextrin is obtained a concentration of 3-6g/ with water dissolution
The alpha-cyclodextrin aqueous solution of L, is added 0.8g ferrocene in above-mentioned every liter of solution, and 20kHz ultrasound 30-60min are uniformly divided
Scattered alpha-cyclodextrin and ferrocene composite solution.
PDMS seals are soaked in 30-40s in alpha-cyclodextrin and ferrocene composite solution, taken by step 3, micro-contact printing
In N after going out2Dry 30-60s, carboxylated base is placed on by the PDMS seals for being coated with alpha-cyclodextrin and ferrocene composite solution in air-flow
On bottom, 10-20s is gently pressed, PDMS seal designs are transferred to substrate surface, obtains printing figuratum substrate.
Step 4, chemical plating will print figuratum substrate and be soaked in 0.1g/L PdCl210-30s in solution is put after taking-up
It is formed in the distilled water by 4-6wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides, 32wt% formaldehyde and surplus
Chemical bronze plating liquid in carry out chemical plating, time 1-10min.Exquisite metallic copper figure can be obtained after taking-up in substrate
Case.
Embodiment 1
Application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, including：
Step 1, substrate carboxylated, substrate are polymethyl methacrylate, and base material is water-soluble with 45% isopropanol
Liquid impregnates 30min, then impregnates 15min under the conditions of 55 DEG C with 3mol/L sulfuric acid, then washes with water, and 60 DEG C of vacuum drying obtain
To carboxylated substrate.
Step 2 prepares alpha-cyclodextrin and ferrocene composite solution, and alpha-cyclodextrin is obtained a concentration of 6g/L with water dissolution
Alpha-cyclodextrin aqueous solution, 0.8g ferrocene is added in above-mentioned every liter of solution, 20kHz ultrasound 30min obtain evenly dispersed
Alpha-cyclodextrin and ferrocene composite solution.
PDMS seals are soaked in 30s in alpha-cyclodextrin and ferrocene composite solution by step 3, micro-contact printing, are taken out
Afterwards in N2Dry 30s, the PDMS seals for being coated with alpha-cyclodextrin and ferrocene composite solution are placed in carboxylated substrate in air-flow,
PDMS seal designs are transferred to substrate surface, obtain printing figuratum substrate by light pressure 10s.
Step 4, chemical plating will print figuratum substrate and be soaked in 0.1g/L PdCl210s in solution is put in after taking-up
The change being made of 4wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides, 32wt% formaldehyde and 51wt% distilled water
It learns in copper plating bath and carries out chemical plating, time 5min.Exquisite metal copper pattern can be obtained after taking-up in substrate.
Embodiment 2
Application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, including：
Step 1, substrate carboxylated, substrate are polymethyl methacrylate, and base material is water-soluble with 50% isopropanol
Liquid impregnates 50min, then impregnates 18min under the conditions of 60 DEG C with 2mol/L sulfuric acid, then washes with water, and 65 DEG C of vacuum drying obtain
To carboxylated substrate.
Step 2 prepares alpha-cyclodextrin and ferrocene composite solution, and alpha-cyclodextrin is obtained a concentration of 3g/L with water dissolution
Alpha-cyclodextrin aqueous solution, 0.8g ferrocene is added in above-mentioned every liter of solution, 20kHz ultrasound 40min obtain evenly dispersed
Alpha-cyclodextrin and ferrocene composite solution.
PDMS seals are soaked in 35s in alpha-cyclodextrin and ferrocene composite solution by step 3, micro-contact printing, are taken out
Afterwards in N2Dry 40s, the PDMS seals for being coated with alpha-cyclodextrin and ferrocene composite solution are placed in carboxylated substrate in air-flow,
PDMS seal designs are transferred to substrate surface, obtain printing figuratum substrate by light pressure 15s.
Step 4, chemical plating will print figuratum substrate and be soaked in 0.1g/L PdCl220s in solution is put in after taking-up
The change being made of 6wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides, 32wt% formaldehyde and 49wt% distilled water
It learns in copper plating bath and carries out chemical plating, time 8min.Exquisite metal copper pattern can be obtained after taking-up in substrate.
Embodiment 3
Application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, including：
Step 1, substrate carboxylated, substrate are polymethyl methacrylate, and base material is water-soluble with 55% isopropanol
Liquid impregnates 60min, then impregnates 20min under the conditions of 55-65 DEG C with 2.5mol/L sulfuric acid, then washes with water, and 65 DEG C of vacuum are dry
It is dry, obtain carboxylated substrate.
Step 2 prepares alpha-cyclodextrin and ferrocene composite solution, and alpha-cyclodextrin is obtained a concentration of 5g/L with water dissolution
Alpha-cyclodextrin aqueous solution, 0.8g ferrocene is added in above-mentioned every liter of solution, 20kHz ultrasound 60min obtain evenly dispersed
Alpha-cyclodextrin and ferrocene composite solution.
PDMS seals are soaked in 40s in alpha-cyclodextrin and ferrocene composite solution by step 3, micro-contact printing, are taken out
Afterwards in N2Dry 60s, the PDMS seals for being coated with alpha-cyclodextrin and ferrocene composite solution are placed in carboxylated substrate in air-flow,
PDMS seal designs are transferred to substrate surface, obtain printing figuratum substrate by light pressure 20s.
Step 4, chemical plating will print figuratum substrate and be soaked in 0.1g/L PdCl230s in solution is put in after taking-up
The change being made of 5wt% copper sulphate, 7wt% potassium sodium tartrates, 6wt% sodium hydroxides, 32wt% formaldehyde and 50wt% distilled water
It learns in copper plating bath and carries out chemical plating, time 1min.Exquisite metal copper pattern can be obtained after taking-up in substrate.
Embodiment 4
Human normal epidermal cell HaCaT is incubated at Dahl Burke Improved Eagle Medium (DMEM) culture solution (to contain
10% newborn bovine serum) in, set 37 DEG C, 5%CO2Under the conditions of cultivate, 1~2d changes 1 culture solution.When cell growth to logarithmic phase
Untreated polymethyl methacrylate base bottom is added respectively, 1,2 and 3 gained of embodiment is printed on the poly- methyl of metal copper pattern
Methyl acrylate base treatment.Cell is placed in 37 DEG C, 5%CO with 0.25% tryptose, 96 orifice plate2Incubator culture.2~4h
Afterwards, every piece of culture plate, which is separately added into obtained by untreated polymethyl methacrylate base bottom and embodiment 1-3, is printed on metallic copper
The polymethyl methacrylate base bottom of pattern and the cell of complete culture solution culture as a control group and experimental group, are free of cell
Culture plate is moved into 37 DEG C, 5%CO by the culture solution with sample as blank control2Incubator culture.After for 24 hours, culture solution is abandoned,
2- (2- methoxyl group -4- nitrobenzophenones) -3- (4- nitrobenzophenones) -5- (2,4- bis- is added in phosphate buffer (PBS) board-washing 2 times
Sulfonic acid benzene) -2H- tetrazolium list sodium (CCK-8) 10 μ l.Continue in 37 DEG C, 5%CO2At incubator 2~4h of culture, microplate reader 550nm
Survey each hole optical density (D values).Cell survival rate (%)=[(experimental port D values-blank well D values)/(control wells D values-blank well D
Value)] × 100%, experimental result is as shown in table 1.
Table 1
As it can be seen from table 1 the cell survival rate at polymethyl methacrylate base bottom of the present invention after electroless copper
It is apparently higher than untreated polymethyl methacrylate base bottom, illustrates alpha-cyclodextrin and ferrocene composite solution as micro- contact
Printing ink good biocompatibility, cytotoxicity is low, safe and non-toxic, and harm to the human body is small.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details.
Claims (5)
1. a kind of application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing, which is characterized in that packet
Include following steps：
Step 1 prepares alpha-cyclodextrin and ferrocene composite solution, and alpha-cyclodextrin is obtained a concentration of 3-6g/L's with water dissolution
Alpha-cyclodextrin aqueous solution, is added ferrocene in alpha-cyclodextrin aqueous solution, and ultrasonic vibration 30-60min obtains alpha-cyclodextrin and two
Luxuriant iron composite solution；Wherein, the usage ratio of alpha-cyclodextrin and ferrocene is that 0.8g bis- is added in every liter of alpha-cyclodextrin aqueous solution
Luxuriant iron；
PDMS seals are soaked in 30-40s in alpha-cyclodextrin and ferrocene composite solution, take out and done in nitrogen stream by step 2
Dry 30-60s obtains the PDMS seals for being coated with alpha-cyclodextrin and ferrocene composite solution, and the PDMS seals is placed on
On the polymethyl methacrylate base bottom of carboxylated, PDMS seal designs are transferred to substrate surface, obtain printing figuratum poly-
Methyl methacrylate substrate；
Step 3 will print figuratum polymethyl methacrylate base bottom in PdCl210-30s is impregnated in solution, taking-up is put into use
In the solution of electroless copper, 1-10min is impregnated, metallic copper figure can be obtained after taking-up on polymethyl methacrylate base bottom
Case.
2. the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing as described in claim 1,
It is characterized in that, the carbonylation process of polymethyl methacrylate is：By polymethyl methacrylate base bottom in the different of 45-55%
30-60min is impregnated in aqueous propanol solution, then impregnates 15-20min with 2-3mol/L sulfuric acid, is taken out after cleaning, 60-65 DEG C of vacuum
It is dry, obtain carboxylated polymethyl methacrylate base bottom.
3. the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing as claimed in claim 2,
It is characterized in that, temperature control is at 55-65 DEG C when impregnating polymethyl methacrylate using sulfuric acid.
4. the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing as described in claim 1,
It is characterized in that, PdCl in step 32A concentration of 0.1-0.2g/L of solution.
5. the application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing as described in claim 1,
It is characterized in that, the solution in step 3 for electroless copper is made of following raw material：4-6wt% copper sulphate, 7wt% tartaric acid
Sodium potassium, 6wt% sodium hydroxides, 32wt% formaldehyde and surplus distilled water composition.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510997097.2A CN105504957B (en) | 2015-12-28 | 2015-12-28 | Application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510997097.2A CN105504957B (en) | 2015-12-28 | 2015-12-28 | Application using alpha-cyclodextrin and ferrocene as compound ink in micro-contact printing |
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| CN105504957B true CN105504957B (en) | 2018-09-21 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6306204B1 (en) * | 1999-11-24 | 2001-10-23 | Xerox Corporation | Ink jet ink compositions and printing processes |
| CN103298894A (en) * | 2010-11-12 | 2013-09-11 | 录象射流技术公司 | Method of printing on a film substrate |
| CN104387835A (en) * | 2014-11-05 | 2015-03-04 | 广西师范学院 | Water-soluble double-sandwich-type La metalloporphyrin complex and application thereof in micro-contact printing technique |
| CN104447820A (en) * | 2014-11-05 | 2015-03-25 | 广西师范学院 | Water-soluble double-layer sandwich-type Ce metalloporphyrin complex and application of complex in microcontact printing technique |
-
2015
- 2015-12-28 CN CN201510997097.2A patent/CN105504957B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6306204B1 (en) * | 1999-11-24 | 2001-10-23 | Xerox Corporation | Ink jet ink compositions and printing processes |
| CN103298894A (en) * | 2010-11-12 | 2013-09-11 | 录象射流技术公司 | Method of printing on a film substrate |
| CN104387835A (en) * | 2014-11-05 | 2015-03-04 | 广西师范学院 | Water-soluble double-sandwich-type La metalloporphyrin complex and application thereof in micro-contact printing technique |
| CN104447820A (en) * | 2014-11-05 | 2015-03-25 | 广西师范学院 | Water-soluble double-layer sandwich-type Ce metalloporphyrin complex and application of complex in microcontact printing technique |
Non-Patent Citations (1)
| Title |
|---|
| 《二茂铁基聚合物超分子体系构建和性能的研究进展》;周建华等;《高分子通报》;20061130(第11期);第1-11,43页 * |
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| CN105504957A (en) | 2016-04-20 |
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