CN101293909B - Nucleic acid bionic nano material with electric potential gradient, preparation method and application thereof - Google Patents
Nucleic acid bionic nano material with electric potential gradient, preparation method and application thereof Download PDFInfo
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- 0 *c1cc(C(N(*)C(c2ccc3-c(cc4)c5c6c4C(N4*)=N)=C)=O)c2c3c1-c5ccc6C4=O Chemical compound *c1cc(C(N(*)C(c2ccc3-c(cc4)c5c6c4C(N4*)=N)=C)=O)c2c3c1-c5ccc6C4=O 0.000 description 1
- BPNOCGHVMFCYQO-UHFFFAOYSA-N CC1=C(C)C2=N/C1=N\c([nH]1)c(cccc3)c3c1/N=C\N=C\N=C(\c1c3cccc1)/N/C3=N2 Chemical compound CC1=C(C)C2=N/C1=N\c([nH]1)c(cccc3)c3c1/N=C\N=C\N=C(\c1c3cccc1)/N/C3=N2 BPNOCGHVMFCYQO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of nanometer photoelectric materials, particularly relates to a nucleic acid bionic nanometer material utilizing nucleic acids and a simulated molecular system thereof and a photoelectric conversion nanometer material. The nucleic acid bionic nanometer material has double spiral electric potential gradient formed along a nucleic acid molecule or a simulated nucleic acid molecule; and is prepared by designing a base sequence using solid-phase synthesis method, orderly arranging natural bases T, C, A and G with different electric properties along a nucleic acid chain or a simulated nucleic acid chain according to the sequence from higher to lower with respect to reduction potential or oxidation potential with different intervals from one end to the other end to obtain a nucleic acid molecule or a simulated nucleic acid molecule, and hybridizing with a nucleic acid or a simulated nucleic acid with the complementary sequence. The inventive material can be used for preparing the photoelectric conversion nanometer material with unidirectional charge transfer characteristic.
Description
Technical field
The invention belongs to the sub-field of materials of nano photoelectric, particularly utilized the nucleic acid bionic nano material and the opto-electronic conversion field of nanometer material technology of nucleic acid and nucleic acid model molecule system.
Background technology
Photoelectric conversion material is to be applied to solar energy photoelectric conversion; With solar energy converting is one type of functional materials of electric energy, the organic small molecule material that comprises inorganic semiconductor materials such as silicon single crystal/non-crystalline silicon, Cadmium Sulfide/cadmium telluride, has the macromolecular material of narrow band gap and have high specific absorbance in the Visible-to-Near InfaRed district.Traditionally, both all belong to the organic photoelectric transition material after.At present, the solar cell on the market mainly is to be photoelectric conversion material with silicon single crystal, and its efficiency of conversion is about 20%; But the high price of silicon single crystal has limited its widespread use, and polysilicon is considered to follow-on photoelectric conversion material; Its efficient has also reached more than 15%, and still, its price and efficient still can not meet the demands; Especially the maximum light stream sub-band of its band gap and sunshine is not close; Therefore, be that inorganic semiconductor material representative, that have narrow band gap has obtained attention with Cadmium Sulfide, gallium arsenide and CIS, its photoelectric transformation efficiency has also reached or near the level of silicon single crystal.Yet no matter be silicon based material or inorganic semiconductor material, identical shortcoming is arranged all, complicated such as the raw material complete processing, raw material weight is heavy, raw material sources are single etc., thereby, limited its widespread use.
Organic materials is then different, has advantages such as raw material sources are extensive, in light weight, the structure modifiability strong, flexible foldable, thereby is considered to the most promising photoelectric conversion material.Since the 60 to 70's of last century, organic materials has obtained a large amount of research always.Photronic efficiency of conversion based on the polymkeric substance photoelectric conversion material is subject to limited chargeseparated efficient and carrier transport efficient always, its efficiency of conversion always very low (10
-3～10
-1%), up to C
60Appearance and form " bulk heterojunction " (Bulk Heterojunction) type photoelectric conversion material as the mixed with polymers of electron acceptor(EA) and electron donor(ED) type, its efficiency of conversion is just brought up to (G.Yu, J.Gao more than 1%; J.C.Hummelen; F.Wudl, A.J.Heeger, Polymer Photovoltaic Cells:Enhanced Efficiencies via a Network of InternalDonor-Acceptor Heterojunctions; Science; 1995,270:1789～1791), this is because C
60Introducing can improve chargeseparated efficient greatly, the life-span of its chargeseparated attitude can reach μ s～ms magnitude (N.S.Sariciftci, L.Smilowitz; A.J.Heeger, F.Wudl, Photoinduced ElectronTransfer from a Conducting Polymer to Buckminsterfullerene; Science; 1992,258,1474～1476).Along with C
60The progress of chemically modified is based on C
60The photronic photoelectric transformation efficiency of verivate and electron donor(ED) type polymkeric substance is progressively brought up to about 5%, still, because C
60The consistency of verivate and polymkeric substance is bad, is prone to assemble, and has limited effective transmission of photic current carrier, therefore, has limited photoelectric transformation efficiency.And organic small molecule material, such as, cyanine dye since its maximum absorption wavelength between 400～1000nm; And have very high specific absorbance, as far back as the eighties in last century, just be used to opto-electronic conversion research; Its efficiency of conversion is about about 1% (A.K.Ghosh, T.Feng, Merocyanine Organic Solar Cell; J.App.Phys.1978,49,5982-5989; D.L.Morel, A.K.Ghosh, T.Feng, E.L.Stogryn, P.E.Purwin, R.F.Shaw, C.Fishman, High-Efficiency Organic Solar Cell, App.Phys.Lett.1978,32,495～497).Subsequently; The efficiency of conversion in the double-deck organic photoelectric pond of constructing as photoelectric conversion material with Dian Shou Ti perylene diimides and electron donor(ED) copper phthalocyanine also reaches 1% (C.W.Tang, Two-Layer Organic Photovoltaic Cell, App.Phys.Lett.1986; 48,183～185).Yet, owing to reasons such as chargeseparated efficient and carrier transport efficient are low, when through the gas phase codeposition technique; with perylene diimides and copper phthalocyanine common deposited formation " bulk heterojunction ", and combine improved annealing technology, when putting forward high perylene diimides or the copper phthalocyanine degree that is separated in " bulk heterojunction "; Stoped uneven surface formation, thereby the photoelectric transformation efficiency of perylene diimides and copper phthalocyanine has been brought up to about 1.5% (P.Peumans, S.Uchida; S.R.Forrest; Efficient bulk heteroj unction photovoltaic cells using smallmolecular-weightorganic thin films, Nature, 2003; 425,158～162).This is that the improvement of surfaceness then helps the foundation of charge transfer passage because the raising of the degree that is separated helps effective separation of quantity of photogenerated charge, thereby improves charge transfer efficiency.
In nature; Photosynthesis of plants is efficiently to utilize the model of luminous energy; Photosynthetic reaction center is through a series of molecular regulation mechanism; Particularly photic positive and negative charge shifts and directed isolating molecular mechanism along charge transferring channel step by step, has avoided the compound of electric charge effectively, and realizes the high-level efficiency of transform light energy.DNA as the genetic code carrier not only has the controlled assembling characteristic based on molecular recognition and recognition sequence; Also has charge transmission based on base stacking; Discover that photic electronics or hole can be that springboard is grown Distance Transmission (can reach tens
) by base T or bases G; Its transfer mechanism is mainly electronics jump mechanism (C.-S.Liu, G.B.Schuster, Base Sequence Effects in Radical CationMigration in Duplex DNA:Support for the Polaron-Like Hopping Model; J.Am.Chem.Soc.; 2003,125,6098～6102; C.Behrens, L.T.Burgdorf, A.Schw
gler; T.Carell; Weak Distance Dependence of Excess Electron Transfer in DNA, Angew.Chem.Int.Ed., 2002; 41,1763～1766).Utilize the jump transfer mechanism of electric charge along nucleic acid chains; Through introduce the base group of different electric potential at the different positions of nucleic acid chains; Constructing the electric charge that has that can simulate natural photosynthesis system shifts and directed isolating transfering channel step by step; Realize the unidirectional transfer of quantity of photogenerated charge, construct nucleic acid bionic nano material with the unidirectional transfer characteristics of electric charge.And further pass through covalent linkage with photoelectric functional group and above-mentioned nucleic acid bionic nano material couplings such as perylene diimides or copper phthalocyanines; Realize that the long lifetime chargeseparated attitude of organic molecule electron donor-acceptor (EDA) separates with high efficiency charge, thereby obtain novel opto-electronic conversion nano material.
In order to realize the high thermal stability of above-mentioned materials, it is necessary that introducing can form the high nucleic acid model molecule of thermostability, and these nucleic acid model molecules comprise: (peptide nucleic acid, PNA see document: Nielsen, P.E. to PNAG3; Egholm, M.; Berg, R.H.; Buchardt, O., Sequence selectiverecognition of DNA by strand displacement with a thymine-substitute polyamide, Science; 1991,254,1498～1500) or lock nucleic acid (locked nucleic acid, LNA; See document: S.K.Singh, P.Nielsen, A.A.Koshkin, J.Wengel; LNA (locked nucleic acids): synthesis and high-affinity nucleic acid recognition, Chem.Commun., 1998,455～456) or own carbon alcohol nucleic acid (hexitol nucleic acid; HNA sees document: A.V.Aerschot, I.Verheggen, C.Hendrix; P.Herdewijn, 1,5-Anhydrohexitol Nucleic Acids; A NewPromising Antisense Construct, Angew Chem.Int.Ed.EngI.1995.34.1338～1339), their molecular structure is as follows:
Wherein: Base is a base.
Summary of the invention
One of the object of the invention provides the nucleic acid bionic nano material with electric potential gradient.
Two of the object of the invention provides the preparation method of the nucleic acid bionic nano material with electric potential gradient.
Three of the object of the invention provides the purposes of the nucleic acid bionic nano material with electric potential gradient, is applied to prepare the opto-electronic conversion nano material with the unidirectional transfer characteristics of electric charge.
Four of the object of the invention provides the method that the nucleic acid bionic nano material preparation with electric potential gradient has the opto-electronic conversion nano material of the unidirectional transfer characteristics of electric charge of using.
Nucleic acid bionic nano material with electric potential gradient of the present invention is: the base T of different electric performance, C, A or G are along nucleic acid (DNA) and/or nucleic acid model molecule chain; Press reduction potential or oxidizing potential from high or low; The natural base of different numbers that passes through is at interval arranged in an orderly manner, forms the electric potential gradient with the duplex chain that constitutes along nucleic acid and/or nucleic acid model molecule.
The diameter of described nucleic acid bionic nano material is 2nm.
Described nucleic acid model molecule be PNAG3 (peptide nucleic acid, PNA), lock nucleic acid (lockednucleic acid, LNA) or own carbon alcohol nucleic acid (hexitol nucleic acid, HNA).
The number of the base T of described different electric performance, C, A or G is 2～20.
The base T of described different electric performance, C, A or G are natural base T, C, A, G or their verivate.
The verivate of described natural base T is:
Wherein X is O or S.
The verivate of described natural base C is:
Wherein X is O or S.
The verivate of described natural base A is:
Wherein X is Cl, Br, I, OH, NH
2Or N (CH
3)
2
The verivate of described natural bases G is:
Wherein X is Cl, Br, I, OH, NH
2Or N (CH
3)
2
Described natural base T, C, A, G or their verivate can be the commercially available prod, or obtain through synthetic from corresponding marketable material.
The interval number of the natural base of the different numbers in described interval is 0～5.
Described natural base is to be selected among base T, C, A, the G one or more.
Preparing method with nucleic acid bionic nano material of electric potential gradient of the present invention is:
Utilize solid phase synthesis process; (solid phase synthesis process of lock nucleic acid and own carbon alcohol nucleic acid is similar to the solid phase synthesis process of nucleic acid, referring to document: M.H.Caruthers Chemical synthesis of DNA and DNAanalogs, Acc.Chem.Res.1991; 24 (9), 278～284; The solid phase synthesis process of PNAG3, referring to document: Wang Wenhao, Xu Ping, the solid phase synthesis process of PNAG3; Foreign medical science (pharmacy fascicle), 2002,3; 1 and Nielsen, P.E., Peptide nucleic Acids:Methodes and Protocols.Copenhagen:Humana Press; Totowa, New Jersey, United Sates; 2002) according to the base sequence that designs; Nucleic acid or nucleic acid model molecule monomer with base T, C, A or the G of different electric performance; Press reduction potential or oxidizing potential from high or low; Along nucleic acid or nucleic acid model molecule chain; The natural base of different numbers that passes through is at interval arranged in an orderly manner and is formed nucleic acid or nucleic acid model molecule, and with this nucleic acid or nucleic acid model molecule the nucleic acid or the nucleic acid model molecule of complementary sequence relation to be arranged be the ratio hydridization of 1:1 with the mol ratio, and separation and purification obtains having the nucleic acid bionic nano material of the electric potential gradient of the duplex chain that constitutes along nucleic acid and/or nucleic acid model molecule after the hydridization.The hydridization process is: under 35～40 ℃ of conditions; Nucleic acid or nucleic acid model molecule with above-mentioned formation; There are the nucleic acid of complementary sequence relation or ratio that the nucleic acid model molecule with the mol ratio is 1:1 in incubator, to cultivate 10 minutes～3 hours with this nucleic acid or nucleic acid model molecule; Perhaps be rapidly heated to 80～100 ℃, keep in 5～60 minutes time, being cooled to room temperature after 1～10 minute from room temperature.
The monomeric number of the base T of described different electric performance, C, A or G is 2～20.
The monomeric interval of the natural base number of the different numbers in described interval is 0～5.
The preparation of the nucleic acid bionic nano material with electric potential gradient of the present invention is following:
(1) according to solid phase synthesis process, with 2～10 reduction potentials-0.8～-the base T of 1.2V (vs NHE) presses reduction potential, along nucleic acid or nucleic acid model molecule chain, order (T from low to high
1, T
2); Ordered arrangement forms nucleic acid or nucleic acid model molecule; And with the nucleic acid or the nucleic acid model molecule hydridization of this molecular assembly row complementary relationship, form the nucleic acid bionic nano material of electric potential gradient after the hydridization with the duplex chain that constitutes along nucleic acid and/or nucleic acid model molecule.
(2) according to solid phase synthesis process; On the basis of scheme (1), after the whenever synthetic base T, be docile and obedient preface and connect 1～5 with a kind of urao base; To the last a base T stops; Obtain nucleic acid or nucleic acid model molecule, and with the nucleic acid or the nucleic acid model molecule hydridization of this molecular assembly row complementary relationship, form the nucleic acid bionic nano material of electric potential gradient after the hydridization with the duplex chain that constitutes along nucleic acid and/or nucleic acid model molecule.
(3), 2～10 oxidizing potentials are pressed oxidizing potential in the bases G of 0.5～1.8V (vs SCE), along nucleic acid or nucleic acid model molecule chain, order (G from low to high according to solid phase synthesis process
1, G
2); Ordered arrangement forms nucleic acid or nucleic acid model molecule; And with the nucleic acid or the nucleic acid model molecule hydridization of this molecular assembly row complementary relationship, form the nucleic acid bionic nano material of electric potential gradient after the hydridization with the duplex chain that constitutes along nucleic acid and/or nucleic acid model molecule.
(4) according to solid phase synthesis process; On the basis of scheme (3), after the whenever synthetic bases G, be docile and obedient preface and connect 1～5 with a kind of urao base; To the last a bases G stops; Obtain nucleic acid or nucleic acid model molecule, and with the nucleic acid or the nucleic acid model molecule hydridization of this molecular assembly row complementary relationship, form the nucleic acid bionic nano material of electric potential gradient after the hydridization with the duplex chain that constitutes along nucleic acid and/or nucleic acid model molecule.
Nucleic acid bionic nano material with electric potential gradient of the present invention can be used for preparing the opto-electronic conversion nano material with the unidirectional transfer characteristics of electric charge.
Described opto-electronic conversion nano material be at the two ends of nucleic acid bionic nano material respectively with organic electronic donor and the coupling of organic electronic acceptor, obtain having the opto-electronic conversion nano material of the unidirectional transfer characteristics of electric charge.
Described two ends at nucleic acid bionic nano material respectively with organic electronic donor and the coupling of organic electronic acceptor, the opto-electronic conversion nano material that obtains having the unidirectional transfer characteristics of electric charge is:
(1). the intermediate product---nucleic acid or the nucleic acid model molecule that obtain when preparation is had the nucleic acid bionic nano material along the electric potential gradient of duplex chain; 3 of nucleic acid or nucleic acid model molecule ' or C end or 5 ' or the N end pass through the bridged bond coupling with organic electronic acceptor and organic electronic donor; And, obtain nucleic acid or nucleic acid model molecule that coupling has the photoelectric functional group through HPLC and mass spectrum separation and purification;
(2). the synthetic coupling that obtains of step (1) there are the nucleic acid or the nucleic acid model molecule of photoelectric functional group; There are sequence complementary nucleic acid or nucleic acid model molecule to be the ratio hydridization of 1:1 in molar ratio with this nucleic acid or nucleic acid model molecule, obtain having the opto-electronic conversion nano material of the unidirectional stalling characteristic of quantity of photogenerated charge after the hydridization.The hydridization process is: under 35～40 ℃ of conditions; The nucleic acid or the nucleic acid model molecule that coupling are had the photoelectric functional group; In incubator, cultivated 10 minutes～3 hours with sequence complementary nucleic acid or nucleic acid model molecule; Perhaps be rapidly heated to 80～100 ℃, keep in 5～60 minutes time, being cooled to room temperature after 1～10 minute from room temperature.
Described bridged bond is alkyl chain or ether chain or 0～3 benzene of 1～20 atomicity or the oligomer that thiophene unit is formed.
Organic electronic donor in the described opto-electronic conversion nano material is phthalocyanine, phthalocyanine derivates or oligomerization styrene derivatives; Organic electronic acceptor Shi perylene diimides verivate;
The structural formula of described phthalocyanine or phthalocyanine derivates is:
Wherein: R is alkyl chain or ether chain or 0～3 benzene of 1～20 atomicity or the oligomer that thiophene unit is formed;
The structural formula of described oligomerization styrene derivatives is:
Wherein: R
1, R
2, R
3Be alkyl chain or ether chain or 0～3 benzene of 1～20 atomicity or the oligomer that thiophene unit is formed independently;
The structural formula of Suo Shu De perylene diimides is:
Wherein: R
1, R
2, R
3, R
4Be alkyl chain or ether chain or 0～3 benzene of 1～20 atomicity or the oligomer that thiophene unit is formed independently.
Nucleic acid bionic nano material with electric potential gradient of the present invention shows the unidirectional transfer performance of electric charge with after organic electronic is connected to acceptor, and its chargeseparated attitude life-span reaches μ s magnitude, and expection can be applicable to the opto-electronic conversion nano material.
Embodiment
Embodiment 1.
With commercially available 2-amino-5 methyl-phenylformic acid (151mg, 1mmol, compound 1) and urea (600mg; 10mmol) be blended in the round-bottomed flask of a 10mL, 160 ℃ of following heated overnight cool to 100 ℃; Add 5mL water, stir after 10 minutes, filter; Collecting precipitation obtains compound 2 (150mg), productive rate 85%.
Embodiment 2.
With commercially available furans 3,4-dioctyl phthalate methyl esters (10mmol) is dissolved in the 50mL ethanol, and logical ammonia was removed ethanol after 5 hours, used washed with dichloromethane, and collecting precipitation obtains compound 4 (680mg), productive rate 50%.
KOH (1.48g) is dissolved in the 7mL water, is cooled to 0 ℃ with ice-water bath, and the adding bromine (0.186mL, 3.63mmol); Stir after 10 minutes, add compound 4 (482mg, 2.86mmol) and 10mL1, the 4-dioxane; After the stirring at room 1 hour, be warmed up to 53 ℃ and keep 45 minutes after, add 1mL acetate, stir 20 minutes again after; Cool to room temperature adds KOH (0.64g), and dichloromethane extraction is used in the back; Cross post with 300 order silica gel, use volume ratio to obtain compound 5 (300mg), productive rate 75% as the petrol ether/ethyl acetate drip washing of 1:1.
Compound 5 (300mg) is scattered in the 10mL2N NaOH aqueous solution, heats after 1 hour, using the 2N hydrochloric acid pH value that neutralizes is 3, and filtration obtains compound 6 (260mg), productive rate 95%.
According to the identical preparation method of embodiment 1, be raw material with compound 6, obtain compound 7, productive rate 80%.
Embodiment 3.
Compound 8 (810mg, 5.36mmol) be dissolved in anhydrous tetrahydro furan (THF, 50mL), under the room temperature, be added dropwise to Vinyl chloroformate (1.0mL, 9.75mmol), post-heating refluxed 22 hours, postcooling is to room temperature.To be dissolved in the anhydrous diethyl ether except that the brown solid that obtains after desolvating, and adding PBr3 (0.31mL, 3.25mmol), under nitrogen protection; Refluxed 24 hours, and, filtered collecting precipitation, and use sherwood oil with the ice-water bath cooling; The methylene chloride washing of 1:1 obtains compound 9 (900mg, 95%).
With compound 9 (810mg2.70mmol), Na
2CO
3(500mg, 4.00mmol) and S-methylisothiourea hemisulfate (447mg; 3.200mmol) be dissolved in the mixed solvent (4mL/1mL) of acetonitrile/water, post-heating refluxed 2 hours, occurred brown precipitate behind the cool to room temperature; Filter and collect and to precipitate; And use acetonitrile/water (20mL) washing of volume ratio as 5:1, obtain compound 10 (725mg, 90%).
Embodiment 4.
According to the identical preparation method of embodiment 3: with compound 11 is raw material, prepares compound 13 from compound 11.
Embodiment 5.
Press document (K.L.Dueholm, M.Egholm, C.Behrens, L.Christensen; H.F.Hansen, T.Vulpius, K.H.Petersen, R.H.Berg; P.E.Nielsen, O.Buchardt, Synthesis of Peptide Nucleic Acid Monomers Containing the Four NaturalNucleobases:Thymine; Cytosine, Adenine, and Guanineand TheirOligomerization; J.Org.Chem.1994,595767～5773) preparation method, the PNA monomer of synthetic non-natural base.
Embodiment 6.
Synthesizing of PNAG3
With PNA:H-T
10-T
9T
8T
7-T
6T
5T
4-T
3T
2T
1-Ala is example, wherein T
10, T
9, T
8, T
7, T
6, T
5, T
4, T
3, T
2, T
1Be respectively the base of different electric performance, the electrical property order from high to low that reduction potential is pressed in the Arabic numeral representative.
PNA monomer from embodiment 5 preparations; Synthesize pna molecule by the PNA solid phase synthesis process: choosing the Boc-L-Ala-MBHA resin is start element; Handle 3 times with 2mL trifluoroacetic acid (TFA), each 3 minutes, use the 2mL mol ratio to wash 3 times then respectively as DMF (N)/DCM (methylene dichloride) of 1:1; The 2mL pyridine washes twice, adds the PNA monomer (T through dehydration catalyst (HBTU) and diisopropyl ethyl amine (DIEA) activatory embodiment 5 preparations
1) DMF solution (about 125 μ L), react after 20 minutes, use the DMF washed twice, with capping reagent (diacetyl oxide) handle and washing after, accomplish first circulation, get into second circulation according to circulation 1 identical operations process, by that analogy base T to the last
10Then, use 5mL TFA and 5mL (trifluoromethayl sulfonic acid) TFMSA solution-treated 2～3 times respectively, and, obtain unpurified pna molecule with the ETHYLE ACETATE deposition.
Above-mentioned unpurified pna molecule is dissolved among the 2mL DMF, is injected in the high pressure liquid chromatograph (HPLC), use TFA/H
2O (volume ratio 0.5%) and CH
3CN/H
2The mixed solvent wash-out of O (volume ratio 0.5%) is collected elutriant, confirm required product with mass spectrum (TOF-MS) after, lyophilize, the solid that obtains is confirmed as required product with HPLC and TOF-MS again.
Embodiment 7.
Synthesizing of PNAG3
With PNA:H-T
5-GGT
4-GGT
3-GGT
2-GGT
1-Ala is an example, presses the electrical property order from high to low of reduction potential.
PNA monomer from embodiment 5 preparations; Synthesize pna molecule by the PNA solid phase synthesis process: choosing the Boc-L-Ala-MBHA resin is start element, after the swelling, handles 3 times with 2mL TFA; Each 3 minutes; Use the 2mL mol ratio to wash 3 times as the DMF/DCM of 1:1 then respectively, the 2mL pyridine washes twice, adds the PNA monomer (T for preparing through dehydration catalyst (HBTU) and DIEA activatory embodiment 5
1) DMF solution (about 125 μ L), react after 20 minutes, use the DMF washed twice; After capping reagent (diacetyl oxide) processing and washing; Accomplish first circulation, can get into second circulation according to circulation 1 identical operations process, by that analogy base T to the last
5Then, use 5mL TFA and 5mL TFMSA solution-treated 2～3 times respectively, and, obtain unpurified pna molecule with the ETHYLE ACETATE deposition.
Above-mentioned unpurified pna molecule is dissolved among the 2mL DMF, is injected in the high pressure liquid chromatograph (HPLC), use TFA/H
2O (volume ratio 0.5%) and CH
3CN/H
2The mixed solvent wash-out of O (volume ratio 0.5%) is collected elutriant, confirm required product with mass spectrum (TOF-MS) after, lyophilize, the solid that obtains is confirmed as required product with HPLC and TOF-MS again.
Embodiment 8.
Synthesizing of PNAG3
With PNA:H-G
10-G
9G
8G
7-G
6G
5G
4-G
3G
2G
1-Ala is example, wherein G
10, G
9, G
8, G
7, G
6, G
5, G
4, G
3, G
2, G
1Be respectively the base of different electric performance, the electrical property order from high to low that oxidizing potential is pressed in the Arabic numeral representative.
PNA monomer from embodiment 5 preparations; Synthesize pna molecule by the PNA solid phase synthesis process: choosing the Boc-L-Ala-MBHA resin is start element; Handle 3 times with 2mL TFA, each 3 minutes, use the 2mL mol ratio to wash 3 times then respectively as the DMF/DCM of 1:1; The 2mL pyridine washes twice, adds the PNA monomer (T through dehydration catalyst (HBTU) and DIEA activatory embodiment 5 preparations
1) DMF solution (about 125 μ L), react after 20 minutes, use the DMF washed twice; After capping reagent (diacetyl oxide) processing and washing; Accomplish first circulation, can get into second circulation according to circulation 1 identical operations process, by that analogy bases G to the last
10Then, use 5mL TFA and 5mL TFMSA solution-treated 2～3 times respectively, and, obtain unpurified pna molecule with the ETHYLE ACETATE deposition.
Above-mentioned unpurified pna molecule is dissolved among the 2mL DMF, is injected in the high pressure liquid chromatograph (HPLC), use TFA/H
2O (volume ratio 0.5%) and CH
3CN/H
2The mixed solvent wash-out of O (volume ratio 0.5%) is collected elutriant, confirm required product with mass spectrum (TOF-MS) after, lyophilize, the solid that obtains is confirmed as required product with HPLC and TOF-MS again.
Embodiment 9.
Synthesizing of PNAG3
With PNA:H-G
5-TTG
4-TTG
3-TTG
2-TTG
1-Ala is an example, presses the electrical property order from high to low of oxidizing potential.
PNA monomer from embodiment 5 preparations; Synthesize pna molecule by the PNA solid phase synthesis process: choosing the Boc-L-Ala-MBHA resin is start element; Handle 3 times with 2mL TFA, each 3 minutes, use the 2mL mol ratio to wash 3 times then respectively as the DMF/DCM of 1:1; The 2mL pyridine washes twice, adds the PNA monomer (T through dehydration catalyst (HBTU) and DIEA activatory embodiment 5 preparations
1) DMF solution (about 125 μ L), react after 20 minutes, use the DMF washed twice; After capping reagent (diacetyl oxide) processing and washing; Accomplish first circulation, can get into second circulation according to circulation 1 identical operations process, by that analogy bases G to the last
5Then, use 5mL TFA and 5mL TFMSA solution-treated 2～3 times respectively, and, obtain unpurified pna molecule respectively with the ETHYLE ACETATE deposition.
Above-mentioned unpurified pna molecule is dissolved among the 2mL DMF, is injected in the high pressure liquid chromatograph (HPLC), use TFA/H
2O (volume ratio 0.5%) and CH
3CN/H
2The mixed solvent wash-out of O (volume ratio 0.5%) is collected elutriant, confirm required product with mass spectrum (TOF-MS) after, lyophilize, the solid that obtains is confirmed as required product with HPLC and TOF-MS again.
Embodiment 10.
Preparation with nucleic acid bionic nano material of electric potential gradient
Is that the ratio of 1:1 is dissolved in the solution of 50 μ L water and 50 μ LNaCl (200mM/L) with the arbitrary pna molecule for preparing among the embodiment 6～9 with the mol ratio with the dna molecular of commercially available sequence complementary relationship; Place 37 ℃ incubator to cultivate 30 minutes, obtain having the nucleic acid bionic nano material of electric potential gradient based on the DNA/PNA system.
Embodiment 11.
Preparation with nucleic acid bionic nano material of electric potential gradient
Is that the ratio of 1:1 is dissolved in the solution of 50 μ L water and 50 μ LNaCl (200mM/L) with the arbitrary pna molecule for preparing among the embodiment 6～9 with the mol ratio with the pna molecule of commercially available sequence complementary relationship; Place 37 ℃ incubator to cultivate 1 hour, obtain having the nucleic acid bionic nano material of electric potential gradient based on the PNA/PNA system.
Embodiment 12.
Preparation with nucleic acid bionic nano material of electric potential gradient
Is that the ratio of 1:1 is dissolved in the solution of 50 μ L water and 50 μ LNaCl (200mM/L) with the arbitrary pna molecule for preparing among the embodiment 6～9 with the mol ratio with the LNA molecule of commercially available sequence complementary relationship; Be rapidly heated to 85 ℃ from room temperature; Keep after 10 minutes; In 30 minutes time, be cooled to room temperature, obtain having the nucleic acid bionic nano material of electric potential gradient based on the LNA/PNA system.
Embodiment 13.
Preparation with nucleic acid bionic nano material of electric potential gradient
Is that the ratio of 1:1 is dissolved in the solution of 50 μ L water and 50 μ LNaCl (200mM/L) with the arbitrary pna molecule for preparing among the embodiment 6～9 with the mol ratio with the HNA molecule of commercially available sequence complementary relationship; Place 37 ℃ cultivation stove to cultivate 3 hours, obtain having the nucleic acid bionic nano material of electric potential gradient based on the HNA/PNA system.
Embodiment 14.
Press document (A.A.Koshkin, S.K.Singh, P.Nielsen, V.K.Rajwanshi; R.Kumar, M.Meldgaard, C.E.Olsen, J.Wengel; LNA (Locked Nucleic Acids): Synthesis oftheadenine, cytosine, guanine, 5-methylcytosine; Thymineanduracilbicyclonucleoside monomers, oligomerisation, and unprecedented nucleic acidrecognition, Tetrahydon; 1998,54,3607～3630) preparation method, the LNA monomer of synthetic non-natural base.
Embodiment 15.
Press document (I.Verheggen, A.Van Aerschot, S.Toppet, R.Snoeck; G.Janssen, J.Balzarini, E.D.Clercq; P.Herdewijn, Synthesis and antiherpes virus activity of1,5-anhydrohexitol nucleosides.J.Med.Chem.1993; 36 (14), 2033～2040) preparation method, the HNA monomer of synthetic non-natural base.
Embodiment 16.
Press the synthetic monomeric similar approach of LNA of document, the dna single body of synthetic non-natural base.
Embodiment 17.
According to the method for DNA solid phase synthesis, on automatic dna synthesizer, according to synthetic required DNA, LNA or the HNA of designed sequence order.
For example: DNA:5 '-T
10-T
9T
8T
7-T
6T
5T
4-T
3T
2T
1-3 ',
DNA：5′-T
5-GGT
4-GGT
3-GGT
2-GGT
1-3′、
DNA：5′-G
10-G
9G
8G
7-G
6G
5G
4-G
3G
2G
1-3′、
DNA：5′-G
5-TTG
４-TTG
3-TTG
2-TTG
1-3′、
LNA：5′-T
10-T
9T
8T
7-T
6T
5T
4-T
3T
2T
1-3′、
LNA：5′-T
5-GGT
4-GGT
3-GGT
2-GGT
1-3′、
LNA：5′-G
10-G
9G
8G
7-G
6G
5G
4-G
3G
2G
1-3′、
LNA：5′-G
5-TTG
4-TTG
3-TTG
2-TTG
1-3′、
HNA：5′-T
10-T
9T
8T
7-T
6T
5T
4-T
3T
2T
1-3′、
HNA：5′-T
5-GGT
4-GGT
3-GGT
2-GGT
1-3′
HNA：5′-G
10-G
9G
8G
7-G
6G
5G
4-G
3G
2G
1-3′、
Or HNA:5 '-G
5-TTG
4-TTG
3-TTG
2-TTG
1-3 ' etc.
Embodiment 18.
Preparation with nucleic acid bionic nano material of electric potential gradient
With PNA, DNA, LNA or the HNA of the arbitrary DNA for preparing among the embodiment 17, LNA or HNA molecule and commercially available sequence complementary relationship together; According to the method for embodiment 10～13, prepare corresponding nucleic acid bionic nano material with electric potential gradient based on nucleic acid and nucleic acid model molecule system.
Embodiment 19.
Synthesizing of Bu Dui Cheng perylene diimides, structural formula is as follows:
Wherein: R
1And R
2Be the alkyl chain of 9 carbon independently, R
3And R
4Be 3 independently, 5-di-t-butyl phenoxy.
(790mg 2mmol) is scattered in the 20mL98% vitriol oil, and (0.2ml 4mmol), after 12 hours, filters, and collecting precipitation obtains compound 15 (950mg, productive rate 67%) to add simple substance bromine at 100 ℃ with commercially available De perylene tetracid acid anhydride.
With compound 15 (712mg, 1mmol), 3, the 5-DI-tert-butylphenol compounds (1.13g, 5.45mmol) and Cs
2CO
3(1.24g 3.8mmol) is dispersed among the 15ml DMF, refluxes after 1 hour, uses the ice bath cool to room temperature, adds 10ml acetate, stirs after 1 hour, filters, and uses acetate and methanol wash respectively, and collecting precipitation obtains compound 16 (850mg, productive rate 85%).
Primary amine (C
19-NH
2, 244mg, 1mmol), L-Ala (89mg; 1mmol) with the compound 15 that obtains (768mg, 1mmol) perylene tetracid acid anhydride mix suspending adds the triethylamine of 2mmol in quinoline; Reflux 10 hours is poured in the 1N hydrochloric acid soln, filters; Deposition is crossed pillar with 300 purpose silica gel, uses the chloroform/ethanol drip washing of mol ratio as 5:1, obtains compound 17 (PBI) (productive rate 40%).
Embodiment 20.
With compound 18 (2.4mg, 20mmol), monobromethane (4.6g, 40mmol) and Na
2CO
3(4.6g 40mmol) is dispersed among the 15ml DMF, refluxes after 1 hour, uses the ice bath cool to room temperature, pours in the 100mL1N hydrochloric acid, filters, and collecting precipitation obtains compound 19 (3.4g, productive rate 95%).
Under nitrogen protection, and POCl3 (5mL, (3.4mL is 4.4mmol) and in the anhydrous chloroform (6mL), in said mixture 5mmol) to join dry DMF; Adding compound 19 (1.8g, 10mmol), reflux was reduced to room temperature after 48 hours; Reaction solution is poured in the 100mL frozen water, stirs after 1 hour, uses extracted with diethyl ether, after collected organic layer also removes and desolvates; Cross pillar with 300 purpose silica gel, use the sherwood oil/chloroform drip washing of volume ratio, obtain compound 20 (1.7g, productive rate 80%) as 2:1.
(6mmol), (300mg, 2mmol) (0.9g, 5mmol) in the anhydrous tetracol phenixin of 50mL, reflux is after 1 hour, cool to room temperature after-filtration, collecting precipitation with compound 20 for Diisopropyl azodicarboxylate for NBS, 1.1g to add the tetrahydrobenzene imide.Deposition is dissolved in the 50mL anhydrous tetrahydro furan (THF) again, and (1.1g, 6mmol), reflux behind the cool to room temperature, was removed THF after 1 hour, with the normal hexane deposition, filtered, and used ethyl alcohol recrystallization, obtained compound 21 (0.8g, productive rate 50%) to add NBS.
Triethyl phosphate (1.0g, 6mmol) with compound 21 (1.7g, 5mmol) mix after, 160 ℃ of heating 1.5 hours, boil off monobromethane after, be cooled to 75 ℃, remove excessive triethyl phosphate with underpressure distillation, obtain compound 22 (1.9g, productive rate 100%).
Under nitrogen protection, with compound 20 (1.4g, 10mL DMF solution 5mmol) join compound 22 (1.9g, 5mmol) and potassium tert.-butoxide (0.7g; In 7mL DMF solution 6mmol), stirring at room was poured in the 30g ice after 8 hours; And add 8mL5M hydrochloric acid, then, use chloroform extraction; Collected organic layer obtains compound 23 (1.6g, productive rate 70%) after removing organic solvent.
(2.2g 5mmol) is dissolved in the 40mL anhydrous diethyl ether, under-10 ℃, slowly adds the hexane solution of the n-Butyl Lithium of 5mL1.6M with compound 23; After the stirring at room 5 minutes, behind the adding 2mL DMF, continue to stir 1 hour; The back adds 10mL hydrochloric acid (6N), after organic layer respectively washs once with saturated aqueous sodium carbonate and water, remove organic solvent after; Use methyl alcohol and the ether recrystallization of volume ratio, obtain compound 24 (1.6g, productive rate 80%) as 5:1.
With compound 22 and 24 is raw material, according to the compound method of compound 23, obtains compound 25, productive rate 80%.
With right-(N-trimethyl carbinol carbonic ether (Boc)-aniline (and 208mg, 1mmol), compound 25 (640mg, 1mmol) and anhydrous Na
2CO
3(110mg 1mmol) is scattered among the 10mL DMF, and 1 hour postcooling of reflux is poured in the 100mL water to room temperature, filters, and collecting precipitation obtains compound 26 (OPV) (600mg, productive rate 92%).
Embodiment 21.
Opto-electronic conversion nano material with the unidirectional transfer characteristics of electric charge.
With PNA:PBI-Ala-T
5-GGT
4-GGT
3-GGT
2-GGT
1-Ala is an example
According to the preparation method of embodiment 7, as base T
5Synthetic completion after, according to embodiment 7 circulation 1 identical operations process, continue next circulation (promptly with 2mL TFA processing 3 times; Each 3 minutes; Use the 2mL mol ratio to wash 3 times as the DMF/DCM (methylene dichloride) of 1:1 then respectively, the 2mL pyridine washes twice, adds the PBI perylene diimides for preparing through dehydration catalyst (HBTU) and DIEA activatory embodiment 19) DMF solution (about 125 μ L); React after 20 minutes; Use the DMF washed twice, handle and the washing back with capping reagent (diacetyl oxide)), accomplish this loop ends of PBI.Then, use 5mL TFA and 5mL TFMSA solution-treated 2～3 times respectively, and, obtain unpurified pna molecule with the ETHYLE ACETATE deposition.
(approximately 100mg) is dissolved among the 2mL DMF with above-mentioned unpurified pna molecule, is injected in the high pressure liquid chromatograph (HPLC), uses TFA/H
2O (volume ratio 0.5%) and CH
3CN/H
2The mixed solvent wash-out of O (volume ratio 0.5%) is collected elutriant, confirm required product with mass spectrum (TOF-MS) after, lyophilize, the solid that obtains is confirmed as target P NA molecule (pna molecule of coupling You perylene diimides) with HPLC and TOF-MS again.
This pna molecule (4mmol) is dissolved in DMF (5mL), under dewatering agent (HBTU) and triethylamine effect, and presses document (J.B.Liu; F.Q.Zhao, Y.Zhao, ActaPhys.-Chim.Sin.; 1996,12,491) synthetic (1mmol) condensation of tetramino phthalocyanine (structure is following) that obtains; After 3 hours,, obtain having the functionalization pna molecule (pna molecule of coupling You perylene diimides and tetramino phthalocyanine) of photoelectric functional with the HPLC/TOF-MS separation and purification at room temperature reaction with the ETHYLE ACETATE deposition.
With the above-mentioned functionalization pna molecule that obtains with the DNA that the sequence complementary relationship is arranged, PNA, LNA or HNA; Be dissolved in the solution of 50 μ L water and 50 μ L NaCl (200mM/L) for the ratio of 1:1 in molar ratio; Place 37 ℃ incubator to cultivate 3 hours, obtain having the opto-electronic conversion nano material of the unidirectional stalling characteristic of quantity of photogenerated charge based on DNA/PNA, PNA/PNA, LNA/PNA or HNA/PNA system.
Embodiment 22.
Opto-electronic conversion nano material with the unidirectional transfer characteristics of electric charge.
The pna molecule that embodiment 21 is prepared into: PBI-Ala-T
5-GGT
4-GGT
3-GGT
2-GGT
1-Ala (1mmol) is dissolved in DMF (5mL), under dewatering agent (HBTU) and triethylamine effect; With the synthetic OPV condensation (1mmol) that obtains among the embodiment 20; After 3 hours,, obtain having the functionalization pna molecule of photoelectric functional with the HPLC/TOF-MS separation and purification at room temperature reaction with the ETHYLE ACETATE deposition.
With the above-mentioned functionalization pna molecule that obtains with the DNA that the sequence complementary relationship is arranged, PNA, LNA or HNA; Be dissolved in the solution of 50 μ L water and 50 μ LNaCl (200mM/L) for the ratio of 1:1 in molar ratio; Place 37 ℃ incubator to cultivate 10 hours, obtain having the opto-electronic conversion nano material of the unidirectional stalling characteristic of quantity of photogenerated charge based on DNA/PNA, PNA/PNA, LNA/PNA or HNA/PNA system.
Claims (7)
1. nucleic acid bionic nano material with electric potential gradient; It is characterized in that: the verivate of natural base T, C, A or the G of different electric performance is along nucleic acid and/or nucleic acid model molecule chain; Press reduction potential or oxidizing potential from high or low; The interval number that passes through is that 0～5 natural base is arranged in an orderly manner, forms the electric potential gradient that has along the duplex chain of nucleic acid and/or nucleic acid model molecule formation;
The verivate of described natural base T is:
Wherein X is O or S;
The verivate of described natural base C is:
Wherein X is O or S;
The verivate of described natural base A is:
Wherein X is Cl, Br, I, OH, NH
2Or N (CH
3)
2
The verivate of described natural bases G is:
Wherein X is Cl, Br, I, OH, NH
2Or N (CH
3)
2
Described nucleic acid model molecule is PNAG3, lock nucleic acid or own carbon alcohol nucleic acid.
2. material according to claim 1 is characterized in that: the number of the verivate of the natural base T of described different electric performance, C, A, G is 2～20.
3. material according to claim 1 is characterized in that: described natural base is to be selected among base T, C, A, the G more than one.
4. one kind according to each described preparation methods of claim 1～3, it is characterized in that:
Utilize solid phase synthesis process; Sequence according to the verivate of the natural base T, C, A or the G that design; Nucleic acid or nucleic acid model molecule monomer with the verivate of natural base T, C, A or the G of different electric performance; Press reduction potential or oxidizing potential from high or low; Along nucleic acid or nucleic acid model molecule chain; The number that passes through at interval is that 0～5 natural base is arranged in an orderly manner and formed nucleic acid or nucleic acid model molecule, and the nucleic acid or the nucleic acid model molecule that the complementary sequence relation are arranged with this nucleic acid or nucleic acid model molecule be 1: 1 ratio hydridization with mol ratio, and separation and purification obtains having the nucleic acid bionic nano material of the electric potential gradient of the duplex chain that constitutes along nucleic acid and/or nucleic acid model molecule after the hydridization;
The verivate of described natural base T is:
Wherein X is O or S;
The verivate of described natural base C is:
Wherein X is O or S;
The verivate of described natural base A is:
Wherein X is Cl, Br, I, OH, NH
2Or N (CH
3)
2
The verivate of described natural bases G is:
Wherein X is Cl, Br, I, OH, NH
2Or N (CH
3)
2
Described nucleic acid model molecule is PNAG3, lock nucleic acid or own carbon alcohol nucleic acid.
5. purposes according to each described material of claim 1～3, it is characterized in that: described nucleic acid bionic nano material is to be used to prepare the opto-electronic conversion nano material with the unidirectional transfer characteristics of electric charge.
6. purposes according to claim 5; It is characterized in that: described opto-electronic conversion nano material be at the two ends of nucleic acid bionic nano material respectively with organic electronic donor and the coupling of organic electronic acceptor, obtain having the opto-electronic conversion nano material of the unidirectional transfer characteristics of electric charge;
Described organic electronic donor is phthalocyanine, phthalocyanine derivates or oligomerization styrene derivatives; Organic electronic acceptor Shi perylene diimides verivate;
The structural formula of described phthalocyanine or phthalocyanine derivates is:
Wherein: R is alkyl chain or ether chain or 0～3 benzene of 1～20 atomicity or the oligomer that thiophene unit is formed;
The structural formula of described oligomerization styrene derivatives is:
Wherein: R
1, R
2, R
3Be alkyl chain or ether chain or 0～3 benzene of 1～20 atomicity or the oligomer that thiophene unit is formed independently;
The structural formula of Suo Shu De perylene diimides is:
Wherein: R
1, R
2, R
3, R
4Be alkyl chain or ether chain or 0～3 benzene of 1～20 atomicity or the oligomer that thiophene unit is formed independently.
7. purposes according to claim 6 is characterized in that, described two ends at nucleic acid bionic nano material respectively with organic electronic donor and the coupling of organic electronic acceptor, the opto-electronic conversion nano material that obtains having the unidirectional transfer characteristics of electric charge is:
(1). the intermediate product---nucleic acid or the nucleic acid model molecule that obtain when preparation is had the nucleic acid bionic nano material along the electric potential gradient of duplex chain; 3 of nucleic acid or nucleic acid model molecule ' or C end or 5 ' or the N end pass through the bridged bond coupling with organic electronic acceptor and organic electronic donor; And, obtain nucleic acid or nucleic acid model molecule that coupling has the photoelectric functional group through HPLC and mass spectrum separation and purification;
(2). the synthetic coupling that obtains of step (1) there are the nucleic acid or the nucleic acid model molecule of photoelectric functional group; With this nucleic acid or nucleic acid model molecule sequence complementary nucleic acid or nucleic acid model molecule being arranged is 1: 1 ratio hydridization in molar ratio, obtains having the opto-electronic conversion nano material of the unidirectional stalling characteristic of quantity of photogenerated charge after the hydridization;
Described bridged bond is alkyl chain or ether chain or 0～3 benzene of 1～20 atomicity or the oligomer that thiophene unit is formed;
Described nucleic acid model molecule is PNAG3, lock nucleic acid or own carbon alcohol nucleic acid.
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| Title |
|---|
| Chu-Sheng Liu,et al.Base Sequence Effects in Radical Cation Migration in Duplex DNA: Support for the Polaron-Like Hopping Model.<journal of American Chemical Society>.2003,第125卷(第20期),6098-6102. * |
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