CN106512004B - A kind of nano-graphene/porphyrin nano supermolecule assembly of Permethylated β-cyclodextrin modification - Google Patents
A kind of nano-graphene/porphyrin nano supermolecule assembly of Permethylated β-cyclodextrin modification Download PDFInfo
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Abstract
A kind of nano-graphene/porphyrin nano supermolecule assembly of Permethylated β-cyclodextrin modification, the chemical formula of construction unit are as follows: C252H375N9O114And C44H26N4Na4O12S4, chemical structural formula is as follows:The strong noncovalent interaction of nano-graphene and tetrasulfonic acid sodium porphyrin that the super-molecule assembling body is modified by Permethylated β-cyclodextrin is constructed, and pattern scale is nanoscale, netted aggregation.The invention has the advantages that nano-graphene/tetrasulfonic acid sodium porphyrin Supramolecular Assembling preparation of the Permethylated β-cyclodextrin modification is easy, has good aqueous solubility;Under illumination condition, which shows good cutting performance to DNA, which has broad application prospects in field of photodynamic.
Description
Technical field
The invention belongs to Nanosized Supramolecular Materials Composed of Host technical field, especially a kind of nanometer of Permethylated β-cyclodextrin modification
Graphene/porphyrin super-molecule assembling body.
Background technique
In recent years, artificial synthesized the having of " bottom-up " strategy is taken to determine the nano-graphene of structure due to its spy
Different property and possible practical application receive more and more attention, referring to: (1) M.Ball, Y.Zhong, Y.Wu,
C.Schenck,F.Ng,M.Steigerwald,S.Xiao and C.Nuckolls,Acc.Chem.Res.,2015,48,267-
276.(2)M.Kastler,J.Schmidt,W.Pisula,D.Sebastiani and K.Müllen,J.Am.Chem.Soc.,
2006,128,9526-9534.However in many nano-graphenes, the cool analog derivative of six benzos, and it is known as most brief summary
The nano-graphene of structure, the hot spot even more studied.Using the pi-pi accumulation performance of the cool analog derivative of six benzos, unique transmitting electricity
The characteristic of son and the ability of easy self assembly, are widely used in photovoltaic device, bio-imaging, the fields such as chemical sensitisation, referring to:
(3)L.Chen,K.S.Mali,S.R.Puniredd,M.Baumgarten,K.Parvez,W.Pisula,S.De Feyter
and K.Müllen,J.Am.Chem.Soc.,2013,135,13531-13537.(4)C.Zhang,Y.Liu,X.-Q.Xiong,
L.-H.Peng,L.Gan,C.-F.Chen and H.-B.Xu,Org.Lett.,2012,14,5912-5915.(5)V.Vij,
V.Bhalla and M.Kumar,ACSAppl.Mater.Interfaces,2013,5,5373-5380.(6)P.-C.Zhu,
L.-N.Luo,P.-Q.Cen,J.-T.Li and C.Zhang,Tetrahedron Lett.,2014,55,6277-6280.Separately
On the one hand, the dye molecule that porphyrin is studied extensively as one kind has unique performance and is widely applied.Recently there are also
Nano-graphene and porphyrin are passed through into the report being covalently keyed.It is cool that Wong et al. has synthesized porphyrin modified six benzo for the first time
Derivative, and inquired into it in the possible application of field of photovoltaic devices, referring to: (7) W.W.H.Wong, T.Khoury, D.Vak,
C.Yan,D.J.Jones,M.J.Crossley and A.B.Holmes,J.Mater.Chem.,2010,20,7005-7014。
Englert et al. synthesis report porphyrin repair conjugation connection six benzos it is cool, referring to (8) J.M.Englert, J.Malig,
V.A.Zamolo,A.Hirsch andN.Jux,Chem.Commun.,2013,49,4827-4829.Lungerich et al. synthesis
Report two porphyrins repair conjugation connection six benzos it is cool, and have studied the ultraviolet of these compounds, fluorescence spectrum variation, ginseng
See: (9) D.Lungerich, J.F.Hitzenberger, M.Marcia, F.Hampel, T.Drewello and N.Jux,
Angew.Chem.Int.Ed.,2014,53,12231-12235。
It is various each so as to easily construct since there are strong bonding effects between Permethylated β-cyclodextrin and porphyrin
The super-molecule assembling body of sample.Liu Yu seminar reports cyclodextrin modified derivatives of porphyrin with water-soluble porphyrin Bu Tong molten
Bonding behavior in agent, referring to: (10) Y.Liu, C.-F.Ke, H.-Y.Zhang, J.Cui and F.Ding,
J.Am.Chem.Soc.,2008,130,600-605.Thereafter it has registered the oversubscription subgroup based on cyclodextrin porphyrin covalent effect again
Dress body is simultaneously applied to drug delivery field, referring to: (11) J.Zhao, H.-Y.Zhang, H.-L.Sun andY.Liu,
Chem.-Eur.J.,2015,21,4457-4464。
Since the cool analog derivative of six benzos is generally dissolved only in organic solvent (such as methylene chloride, chloroform, toluene etc.), so
In terms of relevant application report is confined to nano electron device mostly, six benzo cool derivatives are limited in other research fields
Using.Especially in biomedicine field, such as: photo-thermal, optical dynamic therapy etc., the report in relation to nano-graphene porphyrin are even more few
See.
Summary of the invention
The purpose of the present invention is a kind of nano-graphite of Permethylated β-cyclodextrin modification there are problem, is provided for above-mentioned
Alkene porphyrin super-molecule assembling body and its preparation method and application, the super-molecule assembling body have good water solubility, and in illumination
Under to DNA have good cutting performance, have broad application prospects in photo-thermal and field of photodynamic.
Technical solution of the present invention:
A kind of nano-graphene/porphyrin nano supermolecule assembly of Permethylated β-cyclodextrin modification, constructs list
The chemical formula of member are as follows: C252H375N9O114And C44H26N4Na4O12S4, chemical structural formula is as follows:
The super-molecule assembling body is constructed by Permethylated β-cyclodextrin and the interaction of tetrasulfonic acid sodium porphyrin, pattern ruler
Degree is nanoscale, netted aggregation.
A kind of preparation side of nano-graphene/porphyrin nano supermolecule assembly of Permethylated β-cyclodextrin modification
Method, steps are as follows:
1) by three propinyls modify six benzos are cool and 6- deoxidation -6- nitrine-permethylated-beta-cyclodextrin is dissolved in N, N-
Dimethylformamide, is added cuprous iodide, the modification of three propinyls six benzos are cool, 6- deoxidation -6- nitrine-permethylated-β -
The amount ratio of cyclodextrin, n,N-Dimethylformamide and cuprous iodide is 200mg:1.12g:100mL:146mg, then in nitrogen
It is heated to 120 DEG C under protection to react 72 hours, filters, be spin-dried for, the mixing for 40:1 with the volume ratio of methylene chloride and methanol
It closes solution and carries out column chromatography, obtain permethylated β-ring paste modification nano-graphene of yellow;
2) nano-graphene and tetrasulfonic acid sodium porphyrin that the Permethylated β-cyclodextrin of above-mentioned yellow is modified are dissolved in water
In, the amount ratio of nano-graphene, tetrasulfonic acid sodium porphyrin and water that Permethylated β-cyclodextrin is modified is 5.35mg:1.86mg:
100mL obtains nano supermolecule assembly.
A kind of nano-graphene/porphyrin super-molecule assembling body application of the Permethylated β-cyclodextrin modification, is used for
The cutting of DNA, method are: nano-graphene/porphyrin super-molecule assembling body that above-mentioned gained Permethylated β-cyclodextrin is modified
It is added in DNA, after light irradiates 30 minutes, carries out gel electrophoresis experiment, assembly is judged according to the brightness of gel electrophoresis swimming band
To the light cutting power of DNA.
The invention has the advantages that
The nano-graphene and tetrasulfonic acid sodium porphyrin of Permethylated β-cyclodextrin modification all have preferable water solubility, the two
It is added to obtain Permethylated β-cyclodextrin modification nano-graphene/porphyrin super-molecule assembling body with can be convenient in water;It constructs
Super-molecule assembling body there is good DNA cutting performance, the nano-graphene modified than single methylated β-cyclodextrin or
The cutting power of person's tetrasulfonic acid sodium porphyrin is strong, which has broad application prospects in field of photodynamic.
Detailed description of the invention
Fig. 1 is the synthetic method schematic diagram of the nano-graphite ene derivative of Permethylated β-cyclodextrin modification.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of the nano-graphite ene derivative of Permethylated β-cyclodextrin modification.
Fig. 3 is the mass spectrogram of the nano-graphite ene derivative of Permethylated β-cyclodextrin modification.
Fig. 4 is the ultraviolet titration spectrogram of the nano-graphite ene derivative of Permethylated β-cyclodextrin modification.
Fig. 5 is nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body two dimension of Permethylated β-cyclodextrin modification
Nuclear magnetic spectrogram.
Fig. 6 is that nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body fourth of Permethylated β-cyclodextrin modification reaches
That phenomenon figure.
Fig. 7 is nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body transmission of Permethylated β-cyclodextrin modification
Electronic Speculum pattern.
Fig. 8 is nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body scanning of Permethylated β-cyclodextrin modification
Electronic Speculum pattern.
Fig. 9 is nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body of Permethylated β-cyclodextrin modification to DNA
Cutting performance test chart.
Specific embodiment
Embodiment:
A kind of nano-graphene/porphyrin nano supermolecule assembly of Permethylated β-cyclodextrin modification, constructs list
The chemical formula of member are as follows: C252H375N9O114And C44H26N4Na4O12S4, chemical structural formula is as follows:
The super-molecule assembling body is constructed by Permethylated β-cyclodextrin and the interaction of tetrasulfonic acid sodium porphyrin, pattern ruler
Degree is nanoscale, netted aggregation;Preparation methods steps are as follows:
1) the cool 6- deoxidation -6- nitrine-permethylated-β-with 1.12g of six benzos modified three propinyls of 200mg
Cyclodextrin is dissolved in the n,N-Dimethylformamide of 100mL, and the cuprous iodide of 146mg is added, and then heating rises under nitrogen protection
Temperature to 120 DEG C react 72 hours, filter, be spin-dried for, with the volume ratio of methylene chloride and methanol for 40:1 mixed solution carry out column
Chromatography obtains permethylated β-ring paste modification nano-graphene of yellow;
2) tetrasulfonic acid of the nano-graphene and 1.86mg modified the yellow Permethylated β-cyclodextrin of above-mentioned 5.35mg
Sodium porphyrin is dissolved in 100mL water, obtains nano supermolecule assembly.
Fig. 1 is the synthetic method schematic diagram of the nano-graphite ene derivative of Permethylated β-cyclodextrin modification.
Fig. 2 is the nucleus magnetic hydrogen spectrum spectrogram of the nano-graphite ene derivative of Permethylated β-cyclodextrin modification.Show in figure: complete
The structure of the nano-graphene of methylated β-cyclodextrin modification is correct.
Fig. 3 is the mass spectrogram of the nano-graphite ene derivative of Permethylated β-cyclodextrin modification.Show in figure: Quan Jiaji
The molecular weight for changing the nano-graphene of beta-cyclodextrin modified is correct.
Fig. 4 is the ultraviolet titration spectrogram of the nano-graphite ene derivative of Permethylated β-cyclodextrin modification.Show in figure: complete
The nano-graphene and tetrasulfonic acid sodium porphyrin of methylated β-cyclodextrin modification form the super-molecule assembling body of 1:1.5 in water.
Fig. 5 is nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body two dimension of Permethylated β-cyclodextrin modification
Nuclear magnetic spectrogram.Show in figure: the nano-graphene and tetrasulfonic acid sodium porphyrin of Permethylated β-cyclodextrin modification form in water
Super-molecule assembling body.
Fig. 6 is that nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body fourth of Permethylated β-cyclodextrin modification reaches
That phenomenon figure.Show in figure: the nano-graphene and tetrasulfonic acid sodium porphyrin of Permethylated β-cyclodextrin modification form in water
Super-molecule assembling body.The nano-graphene or tetrasulfonic acid sodium porphyrin of individual Permethylated β-cyclodextrin modification are in water not
Super-molecule assembling body can be formed
Fig. 7 is nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body transmission of Permethylated β-cyclodextrin modification
Electronic Speculum pattern.Show in figure: the nano-graphene and tetrasulfonic acid sodium porphyrin of Permethylated β-cyclodextrin modification form in water
Network-like super-molecule assembling body.
Fig. 8 is nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body scanning of Permethylated β-cyclodextrin modification
Electronic Speculum pattern.Show in figure: the nano-graphene and tetrasulfonic acid sodium porphyrin of Permethylated β-cyclodextrin modification form in water
Network-like super-molecule assembling body.
Fig. 9 is nano-graphene/tetrasulfonic acid sodium porphyrin super-molecule assembling body of Permethylated β-cyclodextrin modification to DNA
Cutting performance test chart.Show in figure: under illumination condition, nano-graphene/porphyrin of Permethylated β-cyclodextrin modification is super
Molecular assembly shows good cutting power to DNA.
Claims (2)
1. a kind of nano-graphene/porphyrin nano supermolecule assembly of Permethylated β-cyclodextrin modification, construction unit
Chemical formula are as follows: C252H375N9O114And C44H26N4Na4O12S4, chemical structural formula is as follows:
The super-molecule assembling body is constructed by Permethylated β-cyclodextrin and the interaction of tetrasulfonic acid sodium porphyrin, and pattern scale is
Nanoscale, netted aggregation.
2. a kind of nano-graphene/porphyrin nano-supermolecule group of Permethylated β-cyclodextrin modification as described in claim 1
Fill the preparation method of body, it is characterised in that steps are as follows:
1) by three propinyls modify six benzos are cool and 6- deoxidation -6- nitrine-permethylated-beta-cyclodextrin is dissolved in N, N- diformazan
Cuprous iodide is added in base formamide, and six benzos of three propinyls modification are cool, 6- deoxidation -6- nitrine-permethylated-β-ring is pasted
The amount ratio of essence, n,N-Dimethylformamide and cuprous iodide is 200mg:1.12g:100mL:146mg, then in nitrogen protection
Under be heated to 120 DEG C react 72 hours, filter, be spin-dried for, is molten for the mixing of 40:1 with the volume ratio of methylene chloride and methanol
Liquid carries out column chromatography, obtains the nano-graphene of the Permethylated β-cyclodextrin modification of yellow;
2) nano-graphene of above-mentioned yellow Permethylated β-cyclodextrin modification and tetrasulfonic acid sodium porphyrin are dissolved in water, full first
The amount ratio of the nano-graphene of base beta-cyclodextrin modified, tetrasulfonic acid sodium porphyrin and water is 5.35mg:1.86mg:100mL, is obtained
To nano supermolecule assembly.
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CN113816974B (en) * | 2021-09-22 | 2022-09-06 | 同济大学 | Porphyrin covalent connection sym-triazacyclonium compound and preparation and application thereof |
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CN102258788A (en) * | 2011-06-13 | 2011-11-30 | 南开大学 | Targeted transmission assembly of adriamycin anticancer medicine and preparation method thereof |
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CN102258788A (en) * | 2011-06-13 | 2011-11-30 | 南开大学 | Targeted transmission assembly of adriamycin anticancer medicine and preparation method thereof |
CN103920160A (en) * | 2014-04-25 | 2014-07-16 | 南开大学 | Graphene/hyaluronic acid assembly taking cyclodextrin as medium and preparation method thereof |
CN104127882A (en) * | 2014-08-11 | 2014-11-05 | 南开大学 | Supermolecular assembly for targeted conduction of anticancer taxol prodrug and preparation method thereof |
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