CN107022090B - 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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- CN107022090B CN107022090B CN201710199767.5A CN201710199767A CN107022090B CN 107022090 B CN107022090 B CN 107022090B CN 201710199767 A CN201710199767 A CN 201710199767A CN 107022090 B CN107022090 B CN 107022090B
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- 108010004729 Phycoerythrin Proteins 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 102000008186 Collagen Human genes 0.000 claims abstract description 114
- 108010035532 Collagen Proteins 0.000 claims abstract description 114
- 229920001436 collagen Polymers 0.000 claims abstract description 114
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 81
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 81
- 239000000499 gel Substances 0.000 claims abstract description 67
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 48
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 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 27
- 239000000872 buffer Substances 0.000 claims description 24
- 239000000017 hydrogel Substances 0.000 claims description 22
- 239000003292 glue Substances 0.000 claims description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 20
- 206010070834 Sensitisation Diseases 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 230000008313 sensitization Effects 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 241000195493 Cryptophyta Species 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 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
- 238000000746 purification Methods 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
- 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
- 239000000284 extract Substances 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 238000010257 thawing Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000007853 buffer solution Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000000502 dialysis Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 2
- 241000251468 Actinopterygii Species 0.000 claims 1
- 102000001554 Hemoglobins Human genes 0.000 claims 1
- 108010054147 Hemoglobins Proteins 0.000 claims 1
- 150000004676 glycans Chemical class 0.000 claims 1
- -1 propylene Amide Chemical class 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 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
- 229920001661 Chitosan Polymers 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 239000002109 single walled nanotube Substances 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
- 230000005611 electricity Effects 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
- 230000008901 benefit Effects 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
- 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
- 238000010521 absorption reaction Methods 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
- 235000019441 ethanol Nutrition 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
- 238000010586 diagram Methods 0.000 description 2
- 229910001254 electrum Inorganic materials 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
- 238000004519 manufacturing process Methods 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
- 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
- GLWKVDXAQHCAIO-REYDXQAISA-N 3-[(2z,5z)-2-[[3-(2-carboxyethyl)-5-[[(2r)-4-ethenyl-3-methyl-5-oxo-1,2-dihydropyrrol-2-yl]methyl]-4-methyl-1h-pyrrol-2-yl]methylidene]-5-[[(3z,4r)-3-ethylidene-4-methyl-5-oxopyrrol-2-yl]methylidene]-4-methylpyrrol-3-yl]propanoic acid Chemical compound C\C=C1\[C@@H](C)C(=O)N=C1\C=C(/N\1)C(C)=C(CCC(O)=O)C/1=C/C1=C(CCC(O)=O)C(C)=C(C[C@@H]2C(=C(C=C)C(=O)N2)C)N1 GLWKVDXAQHCAIO-REYDXQAISA-N 0.000 description 1
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 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
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 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
- IGJXAXFFKKRFKU-UHFFFAOYSA-N Phycoerythrobilin Natural products CC=C/1C(NC(C1C)=O)=Cc2[nH]c(C=C3/N=C(CC4NC(=O)C(=C4C)C=C)C(=C3CCC(=O)O)C)c(CCC(=O)O)c2C IGJXAXFFKKRFKU-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
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000001879 gelation Methods 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 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
- 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
- 239000002245 particle Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 108010012759 phycoerythrobilin Proteins 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
- 238000003756 stirring Methods 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
-
- 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
Abstract
The invention discloses a kind of plural gels containing phycoerythrin, preparation method and application, the plural gel is phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, the present invention is by way of phycoerythrin is prepared into phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel by suitable preparation method, it applies it in sensitized cells, improves its incident photon-to-electron conversion efficiency.
Description
Technical field
The invention belongs to chemical fields, 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 technique
Solar energy is the most abundant sustainable energy resources, and the surface of the earth about obtains 4 × 10 from the sun every year24J's
Solar energy.The photosynthesis of nature is more than 3.5 hundred million years typical application of solar energy.Bioprocess is largest photon
Energy is converted into the process of Gibbs free energy.Since the 1990s, the invention of solar battery promotes scientist's benefit
With the research and application of large biological molecule assembling dye-sensitized solar cells.Dye-sensitized cell it is inexpensive, environmental-friendly
Simple feature is with good application prospect with production.Dye-sensitized cell is mainly made of following components: being led
Electric basal layer, nano titania porous electrode, dye-sensitized layer, electrolyte and photocathode.Up to the present, many biology 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 cyanobacteria, red algae, hidden algae and a handful of dinoflagellate to catch photochromic fibroin, can be capture
Luminous energy efficiently pass to photosystem reaction center, be used for photosynthesis.Wherein, phycoerythrin (PE) is algae distributed more widely
Biliprotein.These phycobniliprotein for containing red phycoerythrobilin can absorb the visible light from 580nm to 630nm in range,
And intensively launch red fluorescence in 635nm~645nm range.This is provided for the research and utilization of dye-sensitized solar cells
Good material.Since 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, the problems such as it will cause albuminous degenerations, lead to the dye-sensitized cell of assembling
Incident photon-to-electron conversion efficiency is generally relatively low.
Summary of the invention
Presently, there are aiming at the problem that, the present invention provides a kind of plural gel and preparation method thereof containing phycoerythrin
And application, phycoerythrin is prepared by phycoerythrin/collagen/carboxylic carbon nano-tube/poly- by suitable preparation method
The form of acrylamide plural gel, applies it in sensitized cells, improves its incident photon-to-electron conversion efficiency.
To achieve the above object, the present invention adopts the following technical scheme that:
A kind of plural gel containing phycoerythrin, the plural gel are that phycoerythrin/collagen/carboxylated carbon is received
Mitron/polyacrylamide composite gel.
The above-mentioned plural gel preparation method containing phycoerythrin, comprising the following steps:
(1) collagen and compound concentration are extracted as the collagen aqueous solution of 5~9mg/mL；
(2) compound concentration is the carboxylic carbon nano-tube solution of 10mg/mL；
(3) compound concentration is the cross-linking agent solution of 0.05~0.3g/mL；
(4) it extracts phycoerythrin and prepares the phycoerythrin solution of various concentration；
By the collagen aqueous solution, the carboxylic carbon nano-tube solution and the cross-linking agent solution according to volume ratio
It is uniformly mixed for 1: 1: 2.5 ratio, ultrasonic at room temperature, closed pumping, being then respectively adding volume fraction is 0.2~1%
TEMED solution and mass fraction be 10~50mg/mL ammonium persulfate solution, occur polymerization reaction, obtain collagen/carboxylic
Base carbon nano tube/polyacrylamide composite hydrogel；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 hydrogel is added to the phycoerythrin
In solution, EDC (1~(3~dimethylamino-propyl)~3~ethyl-carbodiimide hydrochloride) and NHS (N~hydroxysuccinimidyl is added
Acid imide), it is protected from light at room temperature overnight, is rinsed with deionized water, remove uncrosslinked phycoerythrin, obtain algae red egg
White/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, the sum of described EDC and NHS dosage and the algae red
The molar ratio of albumen is 1: 2~4.
Specifically, the method extracted collagen and be configured to collagen aqueous solution are as follows:
Fish-skin is added in the NaOH aqueous solution that concentration is 0.1mol/L and is impregnated for 24 hours to remove non-collagen tissue, is taken off
Rouge fish-skin；
The degreasing fish-skin is washed to after neutrality, the acetum that concentration is 0.5mol/L, homogenate is added, 4 DEG C of magnetic force stir
Extraction 2d is mixed, is that 10000r/min is centrifuged 30min with revolving 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, precipitating is collected in centrifugation
Be dissolved in 0.5mol/L acetum, use concentration for 0.1mol/L acetum dialyse 1~3 day, then with distilled water dialysis 2
~6d obtains the Isin glue collagen after freeze-drying；
The Isin glue collagen is dissolved in deionized water, pH to 6.0 is adjusted with NaOH solution, adjusts Isin glue collagen
Concentration obtains collagen aqueous solution to 5mg/mL.
In above-mentioned preparation method, the preparation carboxylic carbon nano-tube solution methods are as follows: take length for 10~30 μm, conduction
Performance is greater than the carboxylated single-walled carbon nanotube of 90s/cm, purity > 90%, is dissolved in pure water, then ultrasonic disperse, obtains
Concentration is the carboxylic carbon nano-tube solution of 10mg/mL.
In above-mentioned preparation method, the method for preparing cross-linking agent solution are as follows: acrylamide and methene acrylamide is molten
It is that it is molten that the crosslinking agent that concentration is 0.3g/mL is obtained after filtering in Tris/HCL buffer that 6.8 concentration are 0.5mol/L in pH value
Liquid；The molar ratio of the acrylamide and methene acrylamide is 60~75: 1, and the acrylamide and the Tris/HCl are slow
The molar ratio of fliud flushing is 8: 1.
In above-mentioned preparation method, the method for extracting phycoerythrin are as follows: purple ball algae frond is placed in buffer, repeatedly
Freeze thawing is broken, and the w/v of frond and buffer is 1: 10 (unit when w/v is a smudge cells, tool
Body refers to that 10 milliliters of buffers are added in 1 gram of frond), freeze thawing 5~8 times, ammonium sulfate when selection saturation degree is 20~60% carries out salt
Analysis precipitating 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 buffer solution, obtains the phycoerythrin solution of various concentration.
Phycoerythrin/collagen/carboxylic carbon nano-tube/the polyacrylamide obtained using above-mentioned preparation method is compound
Gel also belongs to 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
It is miscellaneous to be then dipped in phycoerythrin solution into polyacrylamide network structure, utilize 1~(3~dimethylamino-propyl)~3
~ethyl-carbodiimide hydrochloride (EDC) and N~HOSu NHS (NHS) are used as crosslinking agent, and phycoerythrin is cross-linked to
Gel surface.Not only property is stable, intensity is high for the gel composite, conductivity is high, but also is conducive to encapsulation, to can be applicable to algae
In Lactoferrin dye-sensitized solar cells.
The present invention has the advantage that
1. above-mentioned phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel has electricity faster
There are a wider absorption band in sub- transfer rate, higher quantum efficiency, near infrared region, nontoxic and have good stability.It utilizes
The light anode of nanoscale preferably can collect and transmit electronics, and modular technology can be used reduce cost.With compared with
High photovoltaic property.
2. light-sensitive material PE selected by the present invention is other than the photosynthesis in simulation nature, at the same can with it is existing
Some natural pigment sensitizing dyestuff mixing sensitizations altogether, increase the range and absorption efficiency to sun light absorption wavelength.It separates simultaneously
Simple purification is easy, low in cost, and sample purity is high.It, can by then being activated through EDC/NHS to carbon nanotube progress carboxylation
To be reacted with the amino of PE, is formed and be covalently attached, achieve the purpose that fixed PE.Since carbon nanotube has good conduction
Property, electron transmission, the effect of quantum wire can also be taken between PE, the nanotube of PE modification 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 made from the large biological molecule of sensitizing dyestuff have at low cost, and manufacture craft is simple, nontoxic, environmental-friendly
The advantages that.
Detailed description of the invention
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 is the phycoerythrin after purification and its all-wave length abosrption spectrogram of an embodiment；
Fig. 3 is dark field (a) after the sensitization of an embodiment, the light anode laser confocal microscope under the bright visual field (b)
Image；
Fig. 4 is light anode scanning electron microscope laser confocal microscope image after the sensitization of an embodiment；
Fig. 5 is the structural schematic diagram of the solar cell module of an embodiment；
Fig. 6 is 100mW/cm2The I-V test curve of solar cell module under light intensity；
Fig. 7 is that the solar cell module short circuit current of an embodiment changes over time situation.
Specific embodiment
The present invention will be described in detail by specific embodiment below.These embodiments are provided to be to be able to more
Thoroughly understand the present invention, and the scope of the present invention can be fully disclosed to those skilled in the art.
"comprising" or " comprising " as mentioned throughout the specification and claims are an open language, therefore are answered
It is construed to " including but not limited to ".Specification subsequent descriptions are to implement better embodiment of the invention, and so description is
For the purpose of the rule of specification, the range that is not intended to limit the invention.Protection scope of the present invention is when the appended power of view
Benefit requires subject to institute's defender.
Embodiment 1
A kind of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation method, packet
Include following steps:
(1) collagen and compound concentration are extracted as the collagen aqueous solution of 5mg/mL；
It takes fish-skin to be added in the NaOH aqueous solution that concentration is 0.2mol/L to impregnate for 24 hours to remove non-collagen tissue, be washed to
The acetum that concentration is 0.6mol/L is added after neutrality to be homogenized, 4 DEG C of magnetic agitations extract 2d, and 12000g is centrifuged 30min, upper
NaCl is added in clear liquid, is centrifuged, collects precipitating and is dissolved in 0.5mol/L acetum, dialysed with 0.1 mol/L acetum
Night, then with distilled water dialyse 1d, acid-soluble Isin glue collagen is lyophilized to obtain.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0 is adjusted with NaOH, adjusts Isin glue collagen concentration to 5mg/ml.
(2) compound concentration is the carboxylic carbon nano-tube solution of 10mg/mL；
Taking length is 10~30 μm, and electric conductivity is greater than 90s/cm, and the carboxylated single-walled carbon nanotube of purity > 90% is molten
Xie Yu contains in the pure water of the nonionic surfactant of aromatic group, and then ultrasound dissolves it sufficiently to get saturating to black
Bright carbon nano-tube solution, adjustment content of carbon nanotubes are 10mg/mL.
(3) compound concentration is the cross-linking agent solution of 0.3g/mL；
Acrylamide 17.46g, methene acrylamide 0.54g are taken, is settled to 60 with the Tris/HCL buffer of pH6.8
Ml, 4 DEG C of brown bottle preservations after filtering.
(4) it extracts phycoerythrin and prepares the phycoerythrin solution of various concentration；
Purple ball algae frond is placed in buffer, multigelation is broken, and the w/v of frond and buffer is 1:
10, freeze thawing 5~8 times, after ammonium sulfate when selection saturation degree is 20~60% carries out salt precipitation, 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, and most afterwards after ultrafiltration desalination, the concentration of phycoerythrin is adjusted with the PBS buffer solution that pH value is 6.0
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 uniformly mixed, and ultrasonic at room temperature, closed pumping is then respectively adding TEMED solution and mistake
Ammonium sulfate occurs polymerization reaction, obtains collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel, described
The volume ratio of the sum of TEMED solution and ammonium persulfate solution and the collagen aqueous solution is 5: 1.
Above-mentioned collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel is taken out, 10ml algae red egg is placed in
In white solution, 5mg EDC and 10mg NHS is added, is protected from light at room temperature overnight.Gel is taken out, is rinsed with deionized water,
Removal is not crosslinked into the phycoerythrin molecule of gel surface, obtains phycoerythrin/collagen/carboxylic carbon nano-tube/poly- third
Acrylamide plural gel.
Embodiment 2
A kind of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation method, packet
Include following steps:
(1) collagen and compound concentration are extracted as the collagen aqueous solution of 6mg/mL；
It takes fish-skin to be added in the NaOH aqueous solution that concentration is 0.3mol/L and impregnates 14h to remove non-collagen tissue, be washed to
The acetum that concentration is 0.4mol/L is added after neutrality to be homogenized, 4 DEG C of magnetic agitations extract 1d, and 12000g is centrifuged 30min, upper
NaCl is added in clear liquid, is centrifuged, collects precipitating and is dissolved in 0.6mol/L acetum, dialysed with 0.1 mol/L acetum
Night, then with distilled water dialyse 1d, acid-soluble Isin glue collagen is lyophilized to obtain.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0 is adjusted with NaOH, adjusts Isin glue collagen concentration to 6mg/ml.
(2) compound concentration is the carboxylic carbon nano-tube solution of 10mg/mL；
Taking length is 10~30 μm, and electric conductivity is greater than 90s/cm, and the carboxylated single-walled carbon nanotube of purity > 90% is molten
Xie Yu contains in the pure water of the nonionic surfactant of aromatic group, and then ultrasound dissolves it sufficiently to get saturating to black
Bright carbon nano-tube solution (content of carbon nanotubes 1wt%).
(3) compound concentration is the cross-linking agent solution of 0.205g/mL；
Acrylamide 16g, methene acrylamide 0.4g are taken, is settled to 80ml, mistake with the Tris/HCL buffer of pH 6.8
4 DEG C of brown bottle preservations after filter.
(4) phycoerythrin and compound concentration are extracted as the phycoerythrin solution of 0.05mg/ml；
Purple ball algae frond is placed in buffer, multigelation is broken, and the w/v of frond and buffer is 1:
10, freeze thawing 8 times, select 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, adjusts the dense of phycoerythrin with the PBS buffer that pH value is 6.0
Degree, obtains the phycoerythrin solution of 0.05mg/ml.
(5) phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel preparation
It is separately added into collagen solution 3ml, carbon nano-tube solution 2ml, cross-linking agent aqueous solution 5ml in beaker, mixes,
Ultrasound 30min at room temperature, closed pumping 20min are then respectively adding the 1%TEMED solution of 1ml and 5% over cure of 0.23ml
Acid ammonium solution makes sufficiently to dissolve, and causes polymerization, reacts after 28 DEG C of progress 50min, that is, collagen/carboxylated is prepared
Carbon nanotube/polypropylene amide composite hydrogel.
Collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel is taken out, it is molten to be placed in 10ml phycoerythrin
In liquid, 6mgEDC and 14mgNHS is added, is protected from light at room temperature overnight.Gel is taken out, is rinsed with deionized water, removal is not
It is linked to the phycoerythrin molecule of gel surface, obtains phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide
Plural gel.
Embodiment 3
A kind of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation method, packet
Include following steps:
(1) collagen and compound concentration are extracted as the collagen aqueous solution of 7mg/mL；
It takes fish-skin to be added in the NaOH aqueous solution that concentration is 0.1mol/L and impregnates 48h to remove non-collagen tissue, be washed to
The acetum that concentration is 0.5mol/L is added after neutrality to be homogenized, 4 DEG C of magnetic agitations extract 2d, and 12000g is centrifuged 30min, upper
NaCl is added in clear liquid, is centrifuged, collects precipitating and is dissolved in 0.8mol/L acetum, dialysed with 0.1 mol/L acetum
Night, then with distilled water dialyse 2d, acid-soluble Isin glue collagen is lyophilized to obtain.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0 is adjusted with NaOH, adjusts Isin glue collagen concentration to 7mg/ml.
(2) compound concentration is the carboxylic carbon nano-tube solution of 10mg/mL；
Take length be 20~50 μm, electric conductivity be greater than 100s/cm, the carboxylated single-walled carbon nanotube of purity > 90%,
It is dissolved in the pure water of the nonionic surfactant containing aromatic group, then ultrasound dissolves it sufficiently to get black is arrived
Bright carbon nano-tube solution (content of carbon nanotubes 1wt%).
(3) compound concentration is the cross-linking agent solution of 0.145g/mL；
Acrylamide 14g, methene acrylamide 0.5g are taken, is settled to 100ml, mistake with the Tris/HCL buffer of pH 6.8
4 DEG C of brown bottle preservations after filter.
(4) phycoerythrin and compound concentration are extracted as the phycoerythrin solution of 0.4mg/ml；
Purple ball algae frond is placed in buffer, multigelation is broken, and the w/v of frond and buffer is 1:
10, freeze thawing 7 times, select 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, purifies resulting high-purity phycoerythrin and is diluted in 100ml pH
In 6.0 PBS buffer solution, the phycoerythrin solution of 0.4mg/ml is obtained.
(5) phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel preparation
It is separately added into collagen solution 31ml, carbon nano-tube solution 6ml, cross-linking agent aqueous solution 3ml in beaker, mixes
Even, ultrasound 50min, closed pumping 15min are then respectively adding the I%TEMED solution of 3ml and 5% mistake of 0.4ml at room temperature
Ammonium sulfate makes sufficiently to dissolve, and causes polymerization, reacts after 38 DEG C of progress 15min, that is, collagen/carboxyl is prepared
Carbon nano tube/polyacrylamide composite hydrogel.
Collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel is taken out, it is molten to be placed in 30ml phycoerythrin
In liquid, 5mg EDC and 10mg NHS is added, is protected from light at room temperature overnight.Gel is taken out, is rinsed with deionized water, is removed
It is not crosslinked into the phycoerythrin molecule of gel surface, obtains phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide
Amine plural gel.
Embodiment 4
A kind of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation method, packet
Include following steps:
(1) collagen and compound concentration are extracted as the collagen aqueous solution of 7mg/mL；
It takes fish-skin to be added in the NaOH aqueous solution that concentration is 0.1mol/L and impregnates 44h to remove non-collagen tissue, be washed to
The acetum that concentration is 0.3mol/L is added after neutrality to be homogenized, 4 DEG C of magnetic agitations extract 2d, and 12000g is centrifuged 30min, upper
NaCl is added in clear liquid, is centrifuged, collects precipitating and is dissolved in 0.6mol/L acetum, dialysed with 0.2mol/L acetum
Night, then with distilled water dialyse 1d, acid-soluble Isin glue collagen is lyophilized to obtain.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0 is adjusted with NaOH, adjusts Isin glue collagen concentration to 7mg/ml.
(2) compound concentration is the carboxylic carbon nano-tube solution of 10mg/mL；
Taking length is 10~30 μm, and electric conductivity is greater than 90s/cm, and the carboxylated single-walled carbon nanotube of purity > 90% is molten
Xie Yu contains in the pure water of the nonionic surfactant of aromatic group, and then ultrasound dissolves it sufficiently to get saturating to black
Bright carbon nano-tube solution (content of carbon nanotubes 1wt%).
(3) compound concentration is the cross-linking agent solution of 0.103g/mL；
Acrylamide 20g, methene acrylamide 0.7g are taken, is settled to 200ml, mistake with the Tris/HCL buffer of pH 6.8
4 DEG C of brown bottle preservations after filter.
(4) phycoerythrin and compound concentration are extracted as the phycoerythrin solution of 0.3mg/ml；
Purple ball algae frond is placed in buffer, multigelation is broken, and the w/v of frond and buffer is 1:
10, freeze thawing 7 times, select 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, purifies resulting high-purity phycoerythrin and is diluted in 400ml pH
In 6.0 PBS buffer solution, the phycoerythrin solution of 0.3mg/ml is obtained.
(5) phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel preparation:
It is separately added into collagen solution 5ml, carbon nano-tube solution 5ml, cross-linking agent aqueous solution 6ml in beaker, mixes,
Ultrasound 26min at room temperature, closed pumping 16min are then respectively adding the 1%TEMED solution of 1ml and 5% persulfuric acid of 0.3ml
Ammonium salt solution makes sufficiently to dissolve, and causes polymerization, reacts after 28 DEG C of progress 30min, that is, collagen/carboxylated carbon is prepared
Nanotube/polyacrylamide composite hydrogel.
Collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel is taken out, it is molten to be placed in 10ml phycoerythrin
In liquid, 15mg EDC and 60mg NHS is added, is protected from light at room temperature overnight.Gel is taken out, is rinsed with deionized water, is removed
It is not crosslinked into the phycoerythrin molecule of gel surface, obtains phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide
Amine plural gel.
Embodiment 5
A kind of phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel preparation method, packet
Include following steps:
(1) collagen and compound concentration are extracted as the collagen aqueous solution of 9mg/mL；
It takes fish-skin to be added in the NaOH aqueous solution that concentration is 0.3mol/L to impregnate for 24 hours to remove non-collagen tissue, be washed to
The acetum that concentration is 0.9mol/L is added after neutrality to be homogenized, 4 DEG C of magnetic agitations extract 2d, and 12000g is centrifuged 30min, upper
NaCl is added in clear liquid, is centrifuged, collects precipitating and is dissolved in 0.8mol/L acetum, dialysed with 0.1 mol/L acetum
Night, then with distilled water dialyse 3d, acid-soluble Isin glue collagen is lyophilized to obtain.Acid Isin glue collagen is taken to be dissolved in deionized water,
PH to 6.0 is adjusted with NaOH, adjusts Isin glue collagen concentration to 9mg/ml.
(2) compound concentration is the carboxylic carbon nano-tube solution of 10mg/mL；
Taking length is 20~60 μm, and electric conductivity is greater than 90s/cm, and the carboxylated single-walled carbon nanotube of purity > 90% is molten
Xie Yu contains in the pure water of the nonionic surfactant of aromatic group, and then ultrasound dissolves it sufficiently to get saturating to black
Bright carbon nano-tube solution (content of carbon nanotubes 1wt%).
(3) compound concentration is the cross-linking agent solution of 0.068g/mL；
Acrylamide 40g, methene acrylamide 1g are taken, is settled to 600ml with the Tris/HCL buffer of pH 6.8, is filtered
4 DEG C of brown bottle preservations afterwards.
(4) phycoerythrin and compound concentration are extracted as the phycoerythrin solution of 0.3mg/ml；
Purple ball algae frond is placed in buffer, multigelation is broken, and the w/v of frond and buffer is 1:
10, freeze thawing 5~8 times, after ammonium sulfate when selection saturation degree is 20~60% carries out salt precipitation, 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
The NaCl of 0.3mol/L elutes to obtain supernatant, most afterwards after ultrafiltration desalination, purifies resulting high-purity phycoerythrin and is diluted in
In the PBS buffer solution of 50ml pH 6.0, the phycoerythrin solution of 0.3mg/ml is obtained.
(5) phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel preparation
It is separately added into collagen solution 5ml, carbon nano-tube solution 6ml, cross-linking agent aqueous solution 8ml in beaker, mixes,
Ultrasound 70min at room temperature, closed pumping 20min are then respectively adding the 1%TEMED solution of 2ml and 5% over cure of 0.2m1
Acid ammonium solution makes sufficiently to dissolve, and causes polymerization, reacts after 28 DEG C of progress 30min, that is, collagen/carboxylated is prepared
Carbon nanotube/polypropylene amide composite hydrogel.
Collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel is taken out, it is molten to be placed in 10ml phycoerythrin
In liquid, 5mg EDC and 10mg NHS is added, is protected from light at room temperature overnight.Gel is taken out, is rinsed with deionized water, is removed
It is not crosslinked into the phycoerythrin molecule of gel surface, obtains phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide
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 building and sensitization of electrode
Fluorine tin oxide (FTO) electro-conductive glass is all fixed on by 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 partial size scale2Particle deposition is sunk in processed FTO glass surface
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.It, will be real after the preparation of light anode electrode
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel 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, can be used as
The electrode of solar battery or optical sensor uses.Light anode, the solid-state of 559nm wavelength are detected with laser confocal microscope
Then laser obtains the fluorescent image of 570nm~670nm wavelength band, is swept by confocal laser for exciting fluorescence signal
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；Under dark field, the picture of light anode shows irregular distribution and becomes clear after sensitization
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 scanning electron microscope 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 bore
Woods gasket is assembled, and center forms closed cavity, and the fixed triplicity in both ends is close, keeps the electrolyte being then added not permeable
Leakage.The structural schematic diagram of solar cell module after assembling is shown in Fig. 5, and electrolyte is injected this sky by the aperture on platinum electrode
Chamber, and uniformly spread, it is measured after sealing.Assembled battery is 0.24cm2The TiO of work area2Light anode, at 25 DEG C,
100mW/cm2Standard illumination condition and 75mW/cm2Under lower illumination condition, using solar battery IV test macro to assembling
The photovoltaic property of good solar battery is tested, and is carried out to liquid, solid-state and gel electrolyte layer (present invention)
Comparison, is as a result shown in Fig. 6, Fig. 7.The results show that in 100mW/cm2Under light intensity, 0.64mA/cm is measured2Short circuit current, 0.55V
Open-circuit voltage.Gel electrolyte layer due to the presence of phycoerythrin carbon nanotube plural gel can make the pigment of phycoerythrin with
TiO2The electric conductivity of electrode surface enhances, and makes that injection of the electronics to electrode is excited to be more easier, can be improved photoelectric current.
Embodiment 7
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is in gel sensitization solar electricity
Application in pond
(1) building and sensitization of nano-porous structure gold electrode
Using the gold foil of nanoporous (10~100 nanometers) structure as light anode, platinum is used as to electrode.With ethyl alcohol, chlorine
After imitative progress ultrasonic activation processing in 20 minutes, UV ozone is sterilized 10 minutes.After the preparation of light anode electrode, by Examples 1 to 5
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel 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, Ji Kezuo under illumination condition
For the use of the electrode of solar battery or optical sensor.
(2) assembling and performance test of gel sensitization solar battery, detection method and result are substantially the same as embodiment 6.
Embodiment 8
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is in gel sensitization solar electricity
Application in pond
(1) building and sensitization of nano-porous structure electrum electrode
Using the electrum paillon of nanoporous (10~100 nanometers) structure as light anode, platinum is used as to electrode.Use second
Alcohol, after chloroform carries out ultrasonic activation processing in 20 minutes, UV ozone is sterilized 10 minutes.After the preparation of light anode electrode, it will implement
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel prepared by 1~5 any embodiment of example
It is switched to suitable size, 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 battery or optical sensor uses.
(2) assembling and performance test of gel sensitization solar battery, detection method and result are substantially the same as embodiment 6.
Embodiment 9
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel is in gel sensitization solar electricity
Application in pond
(1) building and sensitization of zinc-oxide nano line electrode
Using the zinc oxide of nano wire (10~100 nanometers) structure as light anode, platinum is used as to electrode.With ethyl alcohol, chloroform
After carrying out ultrasonic activation processing in 20 minutes, UV ozone is sterilized 10 minutes.After the preparation of light anode electrode, Examples 1 to 5 is appointed
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite hydrogel 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, can be used as
The electrode of solar battery or optical sensor uses.
(2) assembling and performance test of gel sensitization solar battery, detection method and result are substantially the same as embodiment 6.
Although above having used 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 without departing from theon the basis of the spirit of the present invention are fallen within the scope of the claimed invention.
Claims (6)
1. a kind of plural gel containing phycoerythrin, which is characterized in that the plural gel be phycoerythrin/collagen/
Carboxylic carbon nano-tube/polyacrylamide composite gel, and the preparation method of the plural gel, comprising the following steps:
(1) collagen and compound concentration are extracted as the collagen aqueous solution of 5~9mg/mL；
(2) compound concentration is the carboxylic carbon nano-tube solution of 10mg/mL；
(3) compound concentration is the cross-linking agent solution of 0.05~0.3g/mL；The preparation method of the cross-linking agent solution are as follows: by propylene
Amide and methene acrylamide are dissolved in the Tris/HCL buffer that pH value is 6.8, concentration is 0.5mol/L, are obtained after filtering dense
Degree is the cross-linking agent solution of 0.3g/mL；The molar ratio of the acrylamide and methene acrylamide is 60~75:1, the propylene
The molar ratio of amide and the Tris/HCl buffer is 8:1；
(4) it extracts phycoerythrin and prepares the phycoerythrin solution of various concentration；
By the collagen aqueous solution, the carboxylic carbon nano-tube solution and the cross-linking agent solution according to volume ratio be 1:
The ratio of 1:2.5 is uniformly mixed, ultrasonic at room temperature, closed pumping, is then respectively adding the TEMED that volume fraction is 0.2~1%
The ammonium persulfate solution that solution and mass fraction are 10~50mg/mL, occurs polymerization reaction, obtains collagen/carboxylated carbon
Nanotube/polyacrylamide composite hydrogel；The sum of the TEMED solution and ammonium persulfate solution are water-soluble with the collagen
The volume ratio of liquid is 5~10:1；
Collagen/carboxylic carbon nano-tube/polyacrylamide the composite hydrogel is added to the phycoerythrin solution
In, EDC and NHS is added, is protected from light at room temperature overnight, is rinsed with deionized water, remove uncrosslinked phycoerythrin, obtain
Phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide composite gel, the sum of described EDC and NHS dosage and institute
The molar ratio for stating phycoerythrin is 1:2~4.
2. the plural gel according to claim 1 containing phycoerythrin, which is characterized in that the extraction collagen is simultaneously
The method for being configured to collagen aqueous solution are as follows:
Fish-skin is added in the NaOH aqueous solution that concentration is 0.1mol/L and is impregnated for 24 hours to remove non-collagen tissue, degreasing fish is obtained
Skin；
The degreasing fish-skin is washed to after neutrality, the acetum that concentration is 0.5mol/L is added, homogenate, 4 DEG C of magnetic agitation extractions
2d is taken, is centrifuged 30min under conditions of revolving 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 precipitating and is dissolved in
In 0.5mol/L acetum, use concentration for 0.1mol/L acetum dialyse 1~3 day, then with distilled water dialysis 2~
6d obtains the Isin glue collagen after freeze-drying；
The Isin glue collagen is dissolved in deionized water, pH to 6.0 is adjusted with NaOH solution, it is dense to adjust Isin glue collagen
Degree, obtains collagen aqueous solution.
3. the plural gel according to claim 1 containing phycoerythrin, which is characterized in that the preparation carboxylated carbon is received
Mitron solution methods are as follows: taking length is 10~30 μm, electric conductivity is greater than 90s/cm, the carboxylated single wall carbon of purity > 90% is received
Mitron is dissolved in pure water, then ultrasonic disperse, obtains carboxylic carbon nano-tube solution, adjusts carboxylic carbon nano-tube solution
Concentration is 10mg/mL.
4. the plural gel according to claim 1 containing phycoerythrin, which is characterized in that the extraction phycoerythrin
Method are as follows: purple ball algae frond is placed in buffer, multigelation is broken, and the w/v of frond and buffer is 1:10,
Freeze thawing 5~8 times, select saturation degree be 20~60% ammonium sulfate carry out salt precipitation, then use mass fraction for 2% shell
Glycan purification via adsorption-based process, then the NaCl solution through 0.3mol/L elute to obtain supernatant, most afterwards after ultrafiltration desalination, are with pH value
The concentration of 6.0 PBS buffer solution adjustment phycoerythrin, obtains the phycoerythrin solution of various concentration.
5. the plural gel according to claim 4 containing phycoerythrin, which is characterized in that the algae after ultrafiltration desalination
Hemoglobin solution purity A545nm/A280nm > 4.5.
6. phycoerythrin/collagen/carboxylic carbon nano-tube/polyacrylamide described in Claims 1 to 5 any one is multiple
It closes gel and is preparing the application in sensitization solar battery.
Priority Applications (1)
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| CN111499757B (en) * | 2020-04-13 | 2022-03-11 | 鲁东大学 | Material based on carbon nanotube coupled phycoerythrin and application thereof |
| CN112812689B (en) * | 2021-01-28 | 2021-12-07 | 浙江大学 | Iontophoresis electrode based on collagen/nano-carbon composite drug-loaded conductive coating and preparation method thereof |
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