CN107022090A - A kind of plural gel containing phycoerythrin, preparation method and application - Google Patents
A kind of plural gel containing phycoerythrin, preparation method and application Download PDFInfo
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- CN107022090A CN107022090A CN201710199767.5A CN201710199767A CN107022090A CN 107022090 A CN107022090 A CN 107022090A CN 201710199767 A CN201710199767 A CN 201710199767A CN 107022090 A CN107022090 A CN 107022090A
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- collagen
- solution
- phycoerythrin
- tube
- carbon nano
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- 108010004729 Phycoerythrin Proteins 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 102000008186 Collagen Human genes 0.000 claims abstract description 115
- 108010035532 Collagen Proteins 0.000 claims abstract description 115
- 229920001436 collagen Polymers 0.000 claims abstract description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 80
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 80
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 49
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims description 86
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000007853 buffer solution Substances 0.000 claims description 24
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 22
- 239000003292 glue Substances 0.000 claims description 21
- 206010070834 Sensitisation Diseases 0.000 claims description 20
- 230000008313 sensitization Effects 0.000 claims description 20
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 241000195493 Cryptophyta Species 0.000 claims description 13
- 238000010612 desalination reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000108 ultra-filtration Methods 0.000 claims description 13
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007983 Tris buffer Substances 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 9
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 9
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 9
- 238000010257 thawing Methods 0.000 claims description 8
- 229920001661 Chitosan Polymers 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002109 single walled nanotube Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000000502 dialysis Methods 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 241000251468 Actinopterygii Species 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000000746 purification Methods 0.000 description 9
- 238000002604 ultrasonography Methods 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000005286 illumination Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 206010001497 Agitation Diseases 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000009738 saturating Methods 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- BXGTVNLGPMZLAZ-UHFFFAOYSA-N n'-ethylmethanediimine;hydrochloride Chemical compound Cl.CCN=C=N BXGTVNLGPMZLAZ-UHFFFAOYSA-N 0.000 description 3
- 230000029553 photosynthesis Effects 0.000 description 3
- 238000010672 photosynthesis Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 229910001254 electrum Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- XXOYNJXVWVNOOJ-UHFFFAOYSA-N fenuron Chemical compound CN(C)C(=O)NC1=CC=CC=C1 XXOYNJXVWVNOOJ-UHFFFAOYSA-N 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229960001296 zinc oxide Drugs 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000192700 Cyanobacteria Species 0.000 description 1
- 241000199914 Dinophyceae Species 0.000 description 1
- 108010022355 Fibroins Proteins 0.000 description 1
- 102000010445 Lactoferrin Human genes 0.000 description 1
- 108010063045 Lactoferrin Proteins 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 241000206572 Rhodophyta Species 0.000 description 1
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- CSSYQJWUGATIHM-IKGCZBKSSA-N l-phenylalanyl-l-lysyl-l-cysteinyl-l-arginyl-l-arginyl-l-tryptophyl-l-glutaminyl-l-tryptophyl-l-arginyl-l-methionyl-l-lysyl-l-lysyl-l-leucylglycyl-l-alanyl-l-prolyl-l-seryl-l-isoleucyl-l-threonyl-l-cysteinyl-l-valyl-l-arginyl-l-arginyl-l-alanyl-l-phenylal Chemical compound C([C@H](N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CS)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)NCC(=O)N[C@@H](C)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CS)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(O)=O)C1=CC=CC=C1 CSSYQJWUGATIHM-IKGCZBKSSA-N 0.000 description 1
- 229940078795 lactoferrin Drugs 0.000 description 1
- 235000021242 lactoferrin Nutrition 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NGWSAUQBWVWFCU-UHFFFAOYSA-N n-ethyl-2,3-dimethylbutan-2-amine Chemical compound CCNC(C)(C)C(C)C NGWSAUQBWVWFCU-UHFFFAOYSA-N 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000637 radiosensitizating effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Medicinal Preparation (AREA)
- Peptides Or Proteins (AREA)
Abstract
The invention discloses a kind of plural gel containing phycoerythrin, preparation method and application, the plural gel is phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, phycoerythrin is prepared into the form of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel by suitable preparation method by the present invention, apply it in sensitized cells, improve its electricity conversion.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of plural gel containing phycoerythrin, preparation method and application,
More particularly a kind of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, preparation method and
Using.
Background technology
Solar energy is most abundant sustainable energy resources, and the surface of the earth about obtains 4 × 10 every year from the sun24J's
Solar energy.The photosynthesis of nature is typical application of solar energy more than 3.5 hundred million years.Bioprocess is largest photon
Energy is converted into the process of Gibbs free energy.Since 1990s, the invention of solar cell promotes scientist's profit
The research and application of DSSC are assembled with large biological molecule.Dye-sensitized cell it is inexpensive, environment-friendly
With, make it is simple the characteristics of with good application prospect.Dye-sensitized cell is mainly made up of following components：Lead
Electric basalis, nano titania porous electrode, dye-sensitized layer, electrolyte and photocathode.Up to the present, many biological dyes
Material sensitizing layer is developed, and the exploitation for being based especially on the artificial photovoltaic apparatus of the photosynthetic albumen composition of supermolecule of chlorophyll is the widest
It is general.
Phycobniliprotein is to be present in blue-green algae, red algae, hidden algae and a handful of dinoflagellate to catch photochromic fibroin, can be capture
Luminous energy efficiently pass to photosystem reaction center, for photosynthesis.Wherein, phycoerythrin (PE) is algae distributed more widely
Biliprotein.The phycobniliprotein of these phycoerythrobilins for containing red can absorb the visible ray in the range of from 580nm to 630nm,
And launch red fluorescence 635nm~645nm scopes are intensive.This is provided for the research and utilization of DSSC
Good material.Because phycoerythrin dye-sensitized layer exists in liquid form mostly, its application difficult is caused.And if adopting
With solid-state phycoerythrin biological dye sensitizing layer, then the problems such as causing albuminous degeneration causes the dye-sensitized cell of assembling
Electricity conversion is generally relatively low.
The content of the invention
The problem of for presently, there are, the invention provides a kind of plural gel containing phycoerythrin and preparation method thereof
And application, phycoerythrin is prepared into by phycoerythrin/collagen/carboxylic carbon nano-tube/poly- by suitable preparation method
The form of acrylamide plural gel, is applied it in sensitized cells, improves its electricity conversion.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of plural gel containing phycoerythrin, the plural gel is that phycoerythrin/collagen/carboxylated carbon is received
Mitron/polyacrylamide composite gel.
The above-mentioned plural gel preparation method containing phycoerythrin, comprises the following steps：
(1) collagen aqueous solution that collagen and compound concentration are 5~9mg/mL is extracted；
(2) compound concentration is 10mg/mL carboxylic carbon nano-tube solution；
(3) compound concentration is 0.05~0.3g/mL cross-linking agent solution；
(4) extract phycoerythrin and prepare the phycoerythrin solution of various concentrations；
By the collagen aqueous solution, the carboxylic carbon nano-tube solution and the cross-linking agent solution according to volume ratio
It is well mixed for 1: 1: 2.5 ratio, ultrasonic at room temperature, closed pumping, it is 0.2~1% to be then respectively adding volume fraction
TEMED solution and mass fraction be 10~50mg/mL ammonium persulfate solution, occur polymerisation, obtain collagen/carboxylic
Base carbon nano tube/polyacrylamide composite aquogel；TEMED (tetramethyl diethylamine) solution and ammonium persulfate solution it
With with the volume ratio of the collagen aqueous solution be 5~10: 1；
Collagen/carboxylic carbon nano-tube/polyacrylamide the composite aquogel is added to the phycoerythrin
In solution, EDC (1~(3~dimethylamino-propyl)~3~ethyl-carbodiimide hydrochloride) and NHS (N~hydroxysuccinimidyl is added
Acid imide), lucifuge reaction at room temperature is stayed overnight, and with deionized water rinsing, is removed uncrosslinked phycoerythrin, is obtained algae red egg
In vain/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, EDC the and NHS consumptions sum and the algae red
The mol ratio of albumen is 1: 2~4.
Specifically, it is described extract collagen and be configured to the method for collagen aqueous solution be：
Fish-skin is added into concentration, to remove non-collagen tissue, to be taken off for immersion 24h in the 0.1mol/L NaOH aqueous solution
Fat fish-skin；
The degreasing fish-skin is washed to the acetum that concentration is 0.5mol/L is added after neutrality, homogenate, 4 DEG C of magnetic force are stirred
Extraction 2d is mixed, 30min is centrifuged by 10000r/min of rotating speed, obtained supernatant is acid-soluble collagen；
The NaCl solution that ultimate density is 0.9~1mol/L is added to the acid-soluble collagen, precipitation is collected in centrifugation
Be dissolved in 0.5mol/L acetums, use concentration for 0.1mol/L acetum dialyse 1~3 day, then with distilled water dialyse 2
~6d, the Isin glue collagen is obtained after freezing；
The Isin glue collagen is dissolved in deionized water, pH to 6.0 is adjusted with NaOH solution, Isin glue collagen is adjusted
Concentration obtains collagen aqueous solution to 5mg/mL.
In above-mentioned preparation method, the preparation carboxylic carbon nano-tube solution methods are：It is 10~30 μm, conduction to take length
Performance is more than 90s/cm, purity ＞ 90% carboxylated single-walled carbon nanotube, is dissolved in pure water, then ultrasonic disperse, obtains
Concentration is 10mg/mL carboxylic carbon nano-tube solution.
In above-mentioned preparation method, the method for the preparation cross-linking agent solution is：Acrylamide and methene acrylamide is molten
In pH value is the Tris/HCL buffer solutions that 6.8 concentration are 0.5mol/L, the crosslinking agent that concentration is 0.3g/mL is obtained after filtering molten
Liquid；The mol ratio of acrylamide and the methene acrylamide is 60~75: 1, and the acrylamide and the Tris/HCl are slow
The mol ratio of fliud flushing is 8: 1.
In above-mentioned preparation method, the method for the extraction phycoerythrin is：Purple ball algae frond is placed in buffer solution, repeatedly
Freeze thawing is crushed, and the w/v of frond and buffer solution is 1: 10 (unit when w/v is a smudge cells, tool
Body refers to 1 gram of frond and adds 10 milliliters of buffer solutions), ammonium sulfate when freeze thawing 5~8 times from saturation degree is 20~60% carries out salt
Analysis precipitation after, use mass fraction for 2% chitosan purification via adsorption-based process (the phycoerythrin solution purity after ultrafiltration desalination
A545nm/A280nm ＞ 4.5), then the NaCl through 0.3mol/L elutes to obtain supernatant, most afterwards after ultrafiltration desalination, with pH value
The concentration of phycoerythrin is adjusted for 6.0 PBS, the phycoerythrin solution of various concentrations is obtained.
Phycoerythrin/collagen/carboxylic carbon nano-tube/the polyacrylamide obtained using above-mentioned preparation method is combined
Gel falls within protection scope of the present invention.
Further, the present invention also protects above-mentioned phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide
Application of the plural gel in sensitization solar battery, specifically, the phycoerythrin/collagen/carboxylic carbon nano-tube/
Polyacrylamide composite gel is covered in TiO2On electrode, then collagen and carboxylic carbon nano-tube wiring solution-forming are mixed
In the miscellaneous network structure to polyacrylamide, then it is dipped in phycoerythrin solution, utilizes 1~(3~dimethylamino-propyl)~3
Phycoerythrin is cross-linked to by~ethyl-carbodiimide hydrochloride (EDC) and N~HOSu NHS (NHS) as crosslinking agent
Gel surface.Not only property is stable, intensity is high for the gel composite, conductance is high, and beneficial to encapsulation, so as to can be applicable to algae
In Lactoferrin DSSC.
The invention has the advantages that：
1. above-mentioned phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel has faster electricity
There is a wider absorption band sub- transfer rate, higher quantum efficiency, near infrared region, nontoxic and have good stability.Utilize
The light anode of nanoscale preferably can collect and transmit electronics, and modular technology can be used to reduce cost.With compared with
High photovoltaic property.
2. light-sensitive material PE selected by the present invention is in addition to the photosynthesis in simulation nature, at the same can with it is existing
Some common sensitizations of natural pigment sensitizing dyestuff mixing, increase the scope and absorption efficiency to sun light absorption wavelength.Separate simultaneously
Simple purification is easy, with low cost, and sample purity is high.By carrying out carboxylation to CNT, then activated through EDC/NHS, can
Reacted with the amino with PE, formed and be covalently attached, reach fixed PE purpose.Because CNT has good conduction
Property, electron transmission, the effect of quantum wire can also be taken between PE, the nanotube of PE modifications is strengthened to X-ray, again
The radiosensitizing effect of ion.
3. the present invention using above-mentioned phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel as
Solar energy sensitized cells have cost low made from the large biological molecule of sensitizing dyestuff, and manufacture craft is simple, nontoxic, environment-friendly
The advantages of.
Brief description of the drawings
Fig. 1 is phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation side of the present invention
The flow chart of method；
Fig. 2 for an embodiment phycoerythrin after purification and its all-wave length abosrption spectrogram；
Fig. 3 is the light anode laser confocal microscope under dark field (a) after the sensitization of an embodiment, the bright visual field (b)
Image；
Fig. 4 is light anode ESEM laser confocal microscope image after the sensitization of an embodiment；
Fig. 5 is the structural representation of the solar cell module of an embodiment；
Fig. 6 is 100mW/cm2The I-V test curves of solar cell module under light intensity；
Fig. 7 changes over time situation for the solar cell module short circuit current flow of an embodiment.
Embodiment
The present invention will be described in detail by specific embodiment below.These embodiments are provided to be able to more
Thoroughly understand the present invention, and can by the scope of the present invention completely convey to those skilled in the art.
"comprising" or " comprising " as mentioned in working as in specification in the whole text and claim are an open language, therefore should
It is construed to " include but be not limited to ".Specification subsequent descriptions is implement the better embodiment of the present invention, and so description is
For the purpose of the rule of specification, the scope of the present invention is not limited to.Protection scope of the present invention is when regarding appended power
Profit requires that the person of defining is defined.
Embodiment 1
A kind of preparation method of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, bag
Include following steps：
(1) collagen aqueous solution that collagen and compound concentration are 5mg/mL is extracted；
Take fish-skin to add concentration, to remove non-collagen tissue, to be washed to for immersion 24h in the 0.2mol/L NaOH aqueous solution
Add concentration after neutrality to be homogenized for 0.6mol/L acetum, 4 DEG C of magnetic agitations extract 2d, 12000g centrifugation 30min, upper
NaCl is added in clear liquid, is centrifuged, precipitation is collected and is dissolved in 0.5mol/L acetums, dialysed with 0.1 mol/L acetums
Night, then with distilled water dialysis 1d, freeze to obtain acid-soluble Isin glue collagen.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0, regulation Isin glue collagen concentration to 5mg/ml are adjusted with NaOH.
(2) compound concentration is 10mg/mL carboxylic carbon nano-tube solution；
It is 10~30 μm to take length, and electric conductivity is more than 90s/cm, and purity ＞ 90% carboxylated single-walled carbon nanotube is molten
Xie Yu contains in the pure water of the nonionic surfactant of aromatic group, and then ultrasound makes it fully dissolve, that is, obtains black saturating
Bright carbon nano-tube solution, adjustment content of carbon nanotubes is 10mg/mL.
(3) compound concentration is 0.3g/mL cross-linking agent solution；
Acrylamide 17.46g, methene acrylamide 0.54g are taken, 60 are settled to pH6.8 Tris/HCL buffer solutions
4 DEG C of preservations of brown bottle after ml, filtering.
(4) extract phycoerythrin and prepare the phycoerythrin solution of various concentrations；
Purple ball algae frond is placed in buffer solution, multigelation is crushed, the w/v of frond and buffer solution is 1:
10, freeze thawing 5~8 times, from saturation degree be 20~60% when ammonium sulfate carry out salt precipitation after, use mass fraction for 2%
Chitosan purification via adsorption-based process (phycoerythrin and its all-wave length abosrption spectrogram after purification is shown in Fig. 2), then through 0.3mol/L's
NaCl elutes to obtain supernatant, most afterwards after ultrafiltration desalination, and the concentration of phycoerythrin is adjusted using pH value as 6.0 PBS
For 0.1mg/ml.
(5) by the collagen aqueous solution, the carboxylic carbon nano-tube solution and the cross-linking agent solution according to body
Product for 1: 1: 2.5 ratio than being well mixed, and ultrasonic at room temperature, closed pumping is then respectively adding TEMED solution and mistake
Ammonium sulfate, occurs polymerisation, obtains collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel, described
TEMED solution and ammonium persulfate solution sum and the volume ratio of the collagen aqueous solution are 5: 1.
Above-mentioned collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel is taken out, 10ml algae red eggs are placed in
In white solution, 5mg EDC and 10mg NHS are added, lucifuge reaction at room temperature is stayed overnight.Gel is taken out, with deionized water rinsing,
The phycoerythrin molecule for being not crosslinked into gel surface is removed, phycoerythrin/collagen/carboxylic carbon nano-tube/poly- third is obtained
Acrylamide plural gel.
Embodiment 2
A kind of preparation method of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, bag
Include following steps：
(1) collagen aqueous solution that collagen and compound concentration are 6mg/mL is extracted；
Take fish-skin to add concentration, to remove non-collagen tissue, to be washed to for immersion 14h in the 0.3mol/L NaOH aqueous solution
Add concentration after neutrality to be homogenized for 0.4mol/L acetum, 4 DEG C of magnetic agitations extract 1d, 12000g centrifugation 30min, upper
NaCl is added in clear liquid, is centrifuged, precipitation is collected and is dissolved in 0.6mol/L acetums, dialysed with 0.1 mol/L acetums
Night, then with distilled water dialysis 1d, freeze to obtain acid-soluble Isin glue collagen.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0, regulation Isin glue collagen concentration to 6mg/ml are adjusted with NaOH.
(2) compound concentration is 10mg/mL carboxylic carbon nano-tube solution；
It is 10~30 μm to take length, and electric conductivity is more than 90s/cm, and purity ＞ 90% carboxylated single-walled carbon nanotube is molten
Xie Yu contains in the pure water of the nonionic surfactant of aromatic group, and then ultrasound makes it fully dissolve, that is, obtains black saturating
Bright carbon nano-tube solution (content of carbon nanotubes 1wt%).
(3) compound concentration is 0.205g/mL cross-linking agent solution；
Acrylamide 16g, methene acrylamide 0.4g are taken, 80ml, mistake are settled to pH 6.8 Tris/HCL buffer solutions
4 DEG C of preservations of brown bottle after filter.
(4) the phycoerythrin solution that phycoerythrin and compound concentration are 0.05mg/ml is extracted；
Purple ball algae frond is placed in buffer solution, multigelation is crushed, the w/v of frond and buffer solution is 1:
10, freeze thawing 8 times, from saturation degree be 60% when ammonium sulfate carry out salt precipitation after, use mass fraction for 2% chitosan
Purification via adsorption-based process (the phycoerythrin solution purity A545nm/A280nm ＞ 4.5 after ultrafiltration desalination), then through 0.3mol/L's
NaCl elutes to obtain supernatant, most afterwards after ultrafiltration desalination, and the dense of phycoerythrin is adjusted by 6.0 PBS buffer solutions of pH value
Degree, obtains 0.05mg/ml phycoerythrin solution.
(5) preparation of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel
Collagen solution 3ml, carbon nano-tube solution 2ml, cross-linking agent aqueous solution 5ml are separately added into beaker, is mixed,
Ultrasound 30min, closed pumping 20min, are then respectively adding 1ml 1%TEMED solution and 0.23ml 5% over cure at room temperature
Acid ammonium solution, makes fully dissolving, triggers polymerization, and reaction prepares collagen/carboxylated after 28 DEG C carry out 50min
Carbon nanotube/polypropylene acid amides composite aquogel.
Collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel is taken out, 10ml phycoerythrin is placed in molten
In liquid, 6mgEDC and 14mgNHS is added, lucifuge reaction at room temperature is stayed overnight.Gel is taken out, with deionized water rinsing, is removed not
The phycoerythrin molecule of gel surface is linked to, phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide is obtained
Plural gel.
Embodiment 3
A kind of preparation method of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, bag
Include following steps：
(1) collagen aqueous solution that collagen and compound concentration are 7mg/mL is extracted；
Take fish-skin to add concentration, to remove non-collagen tissue, to be washed to for immersion 48h in the 0.1mol/L NaOH aqueous solution
Add concentration after neutrality to be homogenized for 0.5mol/L acetum, 4 DEG C of magnetic agitations extract 2d, 12000g centrifugation 30min, upper
NaCl is added in clear liquid, is centrifuged, precipitation is collected and is dissolved in 0.8mol/L acetums, dialysed with 0.1 mol/L acetums
Night, then with distilled water dialysis 2d, freeze to obtain acid-soluble Isin glue collagen.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0, regulation Isin glue collagen concentration to 7mg/ml are adjusted with NaOH.
(2) compound concentration is 10mg/mL carboxylic carbon nano-tube solution；
Take length be 20~50 μm, electric conductivity be more than 100s/cm, purity ＞ 90% carboxylated single-walled carbon nanotube,
In the pure water for being dissolved in the nonionic surfactant containing aromatic group, then ultrasound makes it fully dissolve, that is, obtains black
Bright carbon nano-tube solution (content of carbon nanotubes 1wt%).
(3) compound concentration is 0.145g/mL cross-linking agent solution；
Acrylamide 14g, methene acrylamide 0.5g are taken, 100ml, mistake are settled to pH 6.8 Tris/HCL buffer solutions
4 DEG C of preservations of brown bottle after filter.
(4) the phycoerythrin solution that phycoerythrin and compound concentration are 0.4mg/ml is extracted；
Purple ball algae frond is placed in buffer solution, multigelation is crushed, the w/v of frond and buffer solution is 1:
10, freeze thawing 7 times, from saturation degree be 40% when ammonium sulfate carry out salt precipitation after, use mass fraction for 2% chitosan
Purification via adsorption-based process (the phycoerythrin solution purity A545nm/A280nm ＞ 4.5 after ultrafiltration desalination), then through 0.3mol/L's
NaCl elutes to obtain supernatant, most afterwards after ultrafiltration desalination, and the high-purity phycoerythrin obtained by purifying is diluted in 100ml pH
In 6.0 PBS, 0.4mg/ml phycoerythrin solution is obtained.
(5) preparation of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel
Collagen solution 31ml, carbon nano-tube solution 6ml, cross-linking agent aqueous solution 3ml are separately added into beaker, is mixed
Even, ultrasound 50min, closed pumping 15min, are then respectively adding 3ml I%TEMED solution and 0.4ml 5% mistake at room temperature
Ammonium sulfate, makes fully dissolving, triggers polymerization, and reaction prepares collagen/carboxyl after 38 DEG C carry out 15min
Carbon nano tube/polyacrylamide composite aquogel.
Collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel is taken out, 30ml phycoerythrin is placed in molten
In liquid, 5mg EDC and 10mg NHS are added, lucifuge reaction at room temperature is stayed overnight.Gel is taken out, with deionized water rinsing, is removed
The phycoerythrin molecule of gel surface is not crosslinked into, phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide is obtained
Amine plural gel.
Embodiment 4
A kind of preparation method of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, bag
Include following steps：
(1) collagen aqueous solution that collagen and compound concentration are 7mg/mL is extracted；
Take fish-skin to add concentration, to remove non-collagen tissue, to be washed to for immersion 44h in the 0.1mol/L NaOH aqueous solution
Add concentration after neutrality to be homogenized for 0.3mol/L acetum, 4 DEG C of magnetic agitations extract 2d, 12000g centrifugation 30min, upper
NaCl is added in clear liquid, is centrifuged, precipitation is collected and is dissolved in 0.6mol/L acetums, dialysed with 0.2mol/L acetums
Night, then with distilled water dialysis 1d, freeze to obtain acid-soluble Isin glue collagen.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0, regulation Isin glue collagen concentration to 7mg/ml are adjusted with NaOH.
(2) compound concentration is 10mg/mL carboxylic carbon nano-tube solution；
It is 10~30 μm to take length, and electric conductivity is more than 90s/cm, and purity ＞ 90% carboxylated single-walled carbon nanotube is molten
Xie Yu contains in the pure water of the nonionic surfactant of aromatic group, and then ultrasound makes it fully dissolve, that is, obtains black saturating
Bright carbon nano-tube solution (content of carbon nanotubes 1wt%).
(3) compound concentration is 0.103g/mL cross-linking agent solution；
Acrylamide 20g, methene acrylamide 0.7g are taken, 200ml, mistake are settled to pH 6.8 Tris/HCL buffer solutions
4 DEG C of preservations of brown bottle after filter.
(4) the phycoerythrin solution that phycoerythrin and compound concentration are 0.3mg/ml is extracted；
Purple ball algae frond is placed in buffer solution, multigelation is crushed, the w/v of frond and buffer solution is 1:
10, freeze thawing 7 times, from saturation degree be 50% when ammonium sulfate carry out salt precipitation after, use mass fraction for 2% chitosan
Purification via adsorption-based process (the phycoerythrin solution purity A545nm/A280nm ＞ 4.5 after ultrafiltration desalination), then through 0.3mol/L's
NaCl elutes to obtain supernatant, most afterwards after ultrafiltration desalination, and the high-purity phycoerythrin obtained by purifying is diluted in 400ml pH
In 6.0 PBS, 0.3mg/ml phycoerythrin solution is obtained.
(5) preparation of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel：
Collagen solution 5ml, carbon nano-tube solution 5ml, cross-linking agent aqueous solution 6ml are separately added into beaker, is mixed,
Ultrasound 26min, closed pumping 16min, are then respectively adding 1ml 1%TEMED solution and 0.3ml 5% persulfuric acid at room temperature
Ammonium salt solution, makes fully dissolving, triggers polymerization, and reaction prepares collagen/carboxylated carbon after 28 DEG C carry out 30min
Nanotube/polyacrylamide composite aquogel.
Collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel is taken out, 10ml phycoerythrin is placed in molten
In liquid, 15mg EDC and 60mg NHS are added, lucifuge reaction at room temperature is stayed overnight.Gel is taken out, with deionized water rinsing, is removed
The phycoerythrin molecule of gel surface is not crosslinked into, phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide is obtained
Amine plural gel.
Embodiment 5
A kind of preparation method of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, bag
Include following steps：
(1) collagen aqueous solution that collagen and compound concentration are 9mg/mL is extracted；
Take fish-skin to add concentration, to remove non-collagen tissue, to be washed to for immersion 24h in the 0.3mol/L NaOH aqueous solution
Add concentration after neutrality to be homogenized for 0.9mol/L acetum, 4 DEG C of magnetic agitations extract 2d, 12000g centrifugation 30min, upper
NaCl is added in clear liquid, is centrifuged, precipitation is collected and is dissolved in 0.8mol/L acetums, dialysed with 0.1 mol/L acetums
Night, then with distilled water dialysis 3d, freeze to obtain acid-soluble Isin glue collagen.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0, regulation Isin glue collagen concentration to 9mg/ml are adjusted with NaOH.
(2) compound concentration is 10mg/mL carboxylic carbon nano-tube solution；
It is 20~60 μm to take length, and electric conductivity is more than 90s/cm, and purity ＞ 90% carboxylated single-walled carbon nanotube is molten
Xie Yu contains in the pure water of the nonionic surfactant of aromatic group, and then ultrasound makes it fully dissolve, that is, obtains black saturating
Bright carbon nano-tube solution (content of carbon nanotubes 1wt%).
(3) compound concentration is 0.068g/mL cross-linking agent solution；
Acrylamide 40g, methene acrylamide 1g are taken, 600ml is settled to pH 6.8 Tris/HCL buffer solutions, is filtered
4 DEG C of preservations of brown bottle afterwards.
(4) the phycoerythrin solution that phycoerythrin and compound concentration are 0.3mg/ml is extracted；
Purple ball algae frond is placed in buffer solution, multigelation is crushed, the w/v of frond and buffer solution is 1:
10, freeze thawing 5~8 times, from saturation degree be 20~60% when ammonium sulfate carry out salt precipitation after, use mass fraction for 2%
Chitosan purification via adsorption-based process (the phycoerythrin solution purity A545nm/ A280nm ＞ 4.5 after ultrafiltration desalination), then pass through
0.3mol/L NaCl elutes to obtain supernatant, most afterwards after ultrafiltration desalination, and the high-purity phycoerythrin obtained by purifying is diluted in
In 50ml pH 6.0 PBS, 0.3mg/ml phycoerythrin solution is obtained.
(5) preparation of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel
Collagen solution 5ml, carbon nano-tube solution 6ml, cross-linking agent aqueous solution 8ml are separately added into beaker, is mixed,
Ultrasound 70min, closed pumping 20min, are then respectively adding 2ml 1%TEMED solution and 0.2m1 5% over cure at room temperature
Acid ammonium solution, makes fully dissolving, triggers polymerization, and reaction prepares collagen/carboxylated after 28 DEG C carry out 30min
Carbon nanotube/polypropylene acid amides composite aquogel.
Collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel is taken out, 10ml phycoerythrin is placed in molten
In liquid, 5mg EDC and 10mg NHS are added, lucifuge reaction at room temperature is stayed overnight.Gel is taken out, with deionized water rinsing, is removed
The phycoerythrin molecule of gel surface is not crosslinked into, phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide is obtained
Amine plural gel.
Embodiment 6
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is in gel sensitization solar electricity
Application in pond
(1)TiO2The structure of electrode and sensitization
Fluorine tin oxide (FTO) electro-conductive glass is all fixed on using nano-porous structure light anode and as the platinum electrode to electrode
On substrate.Using silk screen print method by the spherical TiO of 20nm particle diameter yardsticks2Particle deposition is sunk in processed FTO glass surfaces
Product thickness is about 12 μm, and area is about 0.24cm2, obtain semiconductor film (light anode).Then 500 DEG C of heating in Muffle furnace
30min, is sintered together titanium dioxide granule, creates an infiltrative conductive network., will be real after prepared by light anode electrode
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel prepared by example 1 is applied to be switched to properly greatly
It is small, it is covered in TiO2On electrode.The electrode obtained can be done directly the conversion of solar energy to electrical under illumination condition, you can as
The electrode of solar cell or optical sensor is used.Light anode, the solid-state of 559nm wavelength are detected with laser confocal microscope
Laser is used to excite fluorescence signal, then obtains the fluoroscopic image of 570nm~670nm wavelength bands, is swept by confocal laser
Retouch 40 times of object lens (Fig. 3) of microscope (Olympus FLUO FV1000, Japan).Including under dark field (a) and the bright visual field (b)
Light anode laser confocal microscope image；The picture of light anode, which is shown, under dark field, after sensitization is randomly distributed and becomes clear
Uneven orange-red fluorescence (Fig. 3 a).Show from micro-meter scale, phycoerythrin compound heterogeneous binding in electrode surface, and
And the absorption of the surface of solids remains its fluorescent characteristic.The photoanode surface after sensitization is characterized with ESEM simultaneously,
Photoanode surface, which forms one, certain thickness gel adsorption layer (Fig. 4).
(2) assembling and performance test of gel sensitization solar battery
Light anode and platinum plating after gel is sensitized is to electrode (0.36cm2) sand that is cut by laser by 7mm diameter of bores
Woods pad is assembled, and center forms closed cavity, and two ends fix triplicity closely, make the electrolyte being subsequently added not permeable
Leakage.The structural representation of solar cell module after assembling is shown in Fig. 5, and electrolyte is injected into this sky by the aperture on platinum electrode
Chamber, and uniformly spread, measured after sealing.The battery assembled is 0.24cm2The TiO of work area2Light anode, at 25 DEG C,
100mW/cm2Standard illumination condition and 75mW/cm2Under relatively low illumination condition, using solar cell IV test systems to assembling
The photovoltaic property of good solar cell is tested, and liquid, solid-state and gel electrolyte layer (present invention) are carried out
Contrast, is as a result shown in Fig. 6, Fig. 7.As a result show, in 100mW/cm2Under light intensity, 0.64mA/cm is measured2Short circuit current flow, 0.55V
Open-circuit voltage.Gel electrolyte layer due to the presence of phycoerythrin CNT plural gel can make the pigment of phycoerythrin with
TiO2The electric conductivity enhancing of electrode surface, makes to excite electronics to the injection of electrode to be more prone to, it is possible to increase photoelectric current.
Embodiment 7
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is in gel sensitization solar electricity
Application in pond
(1) structure of nano-porous structure gold electrode and sensitization
Gold foil using nanoporous (10~100 nanometers) structure is as light anode, and platinum is as to electrode.With ethanol, chlorine
Imitative to carry out after ultrasonic activation processing in 20 minutes, UV ozone is sterilized 10 minutes.After prepared by light anode electrode, by embodiment 1~5
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel prepared by any embodiment is switched to conjunction
Suitable size, is covered in light anode.The electrode obtained can be done directly the conversion of solar energy to electrical under illumination condition, you can make
Electrode for solar cell or optical sensor is used.
(2) assembling and performance test of gel sensitization solar battery, detection method and the basic be the same as Example 6 of result.
Embodiment 8
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is in gel sensitization solar electricity
Application in pond
(1) structure of nano-porous structure electrum electrode and sensitization
Electrum paillon foil using nanoporous (10~100 nanometers) structure is as light anode, and platinum is as to electrode.Use second
Alcohol, chloroform is carried out after ultrasonic activation processing in 20 minutes, and UV ozone is sterilized 10 minutes.After prepared by light anode electrode, it will implement
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel prepared by any embodiment of example 1~5
Suitable size is switched to, is covered in light anode.The electrode obtained can be done directly the conversion of solar energy to electrical under illumination condition,
The electrode that can be used as solar cell or optical sensor is used.
(2) assembling and performance test of gel sensitization solar battery, detection method and the basic be the same as Example 6 of result.
Embodiment 9
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is in gel sensitization solar electricity
Application in pond
(1) structure of zinc-oxide nano line electrode and sensitization
Zinc oxide using nano wire (10~100 nanometers) structure is as light anode, and platinum is as to electrode.With ethanol, chloroform
Carry out after ultrasonic activation processing in 20 minutes, UV ozone is sterilized 10 minutes.After prepared by light anode electrode, by embodiment 1~5
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite aquogel prepared by one embodiment is switched to properly
Size, is covered in light anode.The electrode obtained can be done directly the conversion of solar energy to electrical under illumination condition, you can as
The electrode of solar cell or optical sensor is used.
(2) assembling and performance test of gel sensitization solar battery, detection method and the basic be the same as Example 6 of result.
Although above with general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. a kind of plural gel containing phycoerythrin, it is characterised in that the plural gel be phycoerythrin/collagen/
Carboxylic carbon nano-tube/polyacrylamide composite gel.
2. the plural gel preparation method according to claim 1 containing phycoerythrin, it is characterised in that including following step
Suddenly：
(1) collagen aqueous solution that collagen and compound concentration are 5~9mg/mL is extracted；
(2) compound concentration is 10mg/mL carboxylic carbon nano-tube solution；
(3) compound concentration is 0.05~0.3g/mL cross-linking agent solution；
(4) extract phycoerythrin and prepare the phycoerythrin solution of various concentrations；
By the collagen aqueous solution, the carboxylic carbon nano-tube solution and the cross-linking agent solution according to volume ratio be 1:
1: 2.5 ratio is well mixed, ultrasonic at room temperature, closed pumping, is then respectively adding the TEMED that volume fraction is 0.2~1%
Solution and the ammonium persulfate solution that mass fraction is 10~50mg/mL, occur polymerisation, obtain collagen/carboxylated carbon
Nanotube/polyacrylamide composite aquogel；The TEMED solution and ammonium persulfate solution sum and the collagen are water-soluble
The volume ratio of liquid is 5~10: 1；
Collagen/carboxylic carbon nano-tube/polyacrylamide the composite aquogel is added to the phycoerythrin solution
In, EDC and NHS is added, lucifuge reaction at room temperature is stayed overnight, with deionized water rinsing, remove uncrosslinked phycoerythrin, obtain
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, EDC the and NHS consumptions sum and institute
The mol ratio for stating phycoerythrin is 1: 2~4.
3. preparation method according to claim 2, it is characterised in that the extraction collagen is simultaneously configured to collagen
The method of the aqueous solution is：
Fish-skin is added into concentration to soak 24h in the 0.1mol/L NaOH aqueous solution to remove non-collagen tissue, degreasing fish is obtained
Skin；
The degreasing fish-skin is washed to the acetum that concentration is 0.5mol/L is added after neutrality, homogenate, 4 DEG C of magnetic agitation extractions
2d is taken, 30min is centrifuged under conditions of rotating speed is 10000r/min, obtained supernatant is acid-soluble collagen；
The NaCl solution that ultimate density is 0.9~1mol/L is added to the acid-soluble collagen, centrifugation is collected precipitation and is dissolved in
In 0.5mol/L acetums, use concentration for 0.1mol/L acetum dialyse 1~3 day, then with distilled water dialysis 2~
6d, the Isin glue collagen is obtained after freezing；
The Isin glue collagen is dissolved in deionized water, pH to 6.0 is adjusted with NaOH solution, regulation Isin glue collagen is dense
Degree, obtains collagen aqueous solution.
4. preparation method according to claim 2, it is characterised in that the preparation carboxylic carbon nano-tube solution methods
For：Take length to be more than 90s/cm, purity ＞ 90% carboxylated single-walled carbon nanotube for 10~30 μm, electric conductivity, be dissolved in
In pure water, then ultrasonic disperse, obtains carboxylic carbon nano-tube solution, the concentration of regulation carboxylic carbon nano-tube solution is 10mg/
mL。
5. preparation method according to claim 2, it is characterised in that the method for the preparation cross-linking agent solution is：By third
Acrylamide and methene acrylamide are dissolved in during pH value is the Tris/HCL buffer solutions that 6.8, concentration is 0.5mol/L, are obtained after filtering
Concentration is 0.3g/mL cross-linking agent solution；The mol ratio of acrylamide and the methene acrylamide is 60~75: 1, described third
Acrylamide and the mol ratio of the Tris/HCl buffer solutions are 8: 1.
6. preparation method according to claim 2, it is characterised in that the method for the extraction phycoerythrin is：By purple ball
Algae frond is placed in buffer solution, and multigelation is crushed, and the w/v of frond and buffer solution is 1: 10, freeze thawing 5~8 times, choosing
Salt precipitation is carried out for 20~60% ammonium sulfate with saturation degree, then uses mass fraction pure for 2% chitosan absorption method
Change, then the NaCl solution through 0.3mol/L elutes to obtain supernatant, most afterwards after ultrafiltration desalination, the PBS using pH value as 6.0
The concentration of phycoerythrin is adjusted, the phycoerythrin solution of various concentrations is obtained.
7. preparation method according to claim 5, it is characterised in that the phycoerythrin solution purity after ultrafiltration desalination
A545nm/A280nm ＞ 4.5.
8. phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel according to claim 1
Application in sensitization solar battery.
9. phycoerythrin/collagen/carboxyl that the preparation method according to claim 2~7 any one is prepared
Application of the carbon nano tube/polyacrylamide composite gel in sensitization solar battery.
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