CN103450486B - Polycationic polymer gelatinous mass of parents' organic poly-fullerene dendrimer crosslinking and preparation method thereof - Google Patents
Polycationic polymer gelatinous mass of parents' organic poly-fullerene dendrimer crosslinking and preparation method thereof Download PDFInfo
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Abstract
The polycationic polymer gelatinous mass of parents' organic poly-fullerene dendrimer crosslinking has following corresponding structural formula,Wherein F is a fullerene core；P1And P2Polycation halogenide for polyamine-containing oligomer or high polymer；E is an affine substituent group；N is 2 50.The invention also discloses a kind of method utilizing the poly-fullerene of nitro or polycyclic sulfonation fullerene to prepare above-mentioned polycationic polymer gelatinous mass as intermediate reaction thing.
Description
Art
The present invention is the polycationic polymer gelatinous mass about the crosslinking of a kind of parents organic poly-fullerene dendrimer and preparation method.
Background technology
One fullerene cage is a nano-sized carbon core texture being made up of 60～92 carbon atoms, i.e. C60、C70、C76、C78、C82、C84Or C92.Having the fullerene cage that the multitube of multiple electron-withdrawing group can roll into a ball and can stand the electrophilic substitution reaction of the affinity interaction with electron rich, this electrophilic substitution reaction causes electrophilic additive group to be substituted by various affine materials.This reaction causes the synthesis of new fullerene derivate.The dynamic response speed of the fullerene that multitube can be rolled into a ball relies on the releasability of additive group and is significantly changed.The most electrophilic functional group is selected to promote the key of the synthesis of fullerene cross-linked polymer gel, because the molecular weight of the increase of polymer trends towards quickly attenuating dynamic response speed progressively, and makes yielding poorly of reaction, and the time is long.In this purposes is invented, general polycyclic sulfonation fullerene derivate, F-(SO4)mFullerene derivate poly-with nitro, F-(NO2)mIt is taken as three-dimensional (3D) cross-linking reagent of the reaction unique, high of polyamines, just as poly-(allylamine), in order to build the parents of polymer gel and hydrophilic supramolecular complex nanometer grid.For example, substantial amounts of polycyclic sulfonation fullerene and the poly-fullerene of nitro can be had on the amido of poly-(allylamine) polymer in the partial cross-linked site of multiple original position by pre-scion grafting to.Remaining a large amount of electrophilic additive group on each fullerene cage keep respective activity and are that next step reaction is ready, with the various nucleopilic reagents one dendritic nano-structure in polymer gel grid.This compounding design strategy is the basis of the present invention.
It is known that such as C60And C70A kind of fullerene cage to such as singlet oxygen (1O2) and free radical (HO, O2-·、NOxDeng) the attack of various reactive oxygen free radical (ROS) the most sensitive.This reactivity by inference can be interrelated with the big electronegativity of the inherence of this molecule.They with prevention and treat free radical relevant disease as the free radical scavenging thing in vector, it is also possible to aging resistance and be added in food with anti-degraded as the antioxidant in cosmetics, it is also possible to as NO in cigarette filterx-remover.Referring specifically to U.S. Patent number 5,648,523.
Antibacterials used in the most active sterilization being provided as in water process and wound healing of polycationic polymer, as the fat in obesity and bile acid binding person (slimming medicine), as the chelating agen removing precious metal ion in Detoxication, as the anticoagulant in hemodilution, and as transgenic and the carrier of gene therapy.Referring specifically to summarizing Adv.Polm.Sci., 2006,192,9-58；Yue, et al., Biomaterials Sci.2013 (DOI:10.1039/c2bm0030j).
Summary of the invention
One aspect of the present invention is the polycationic polymer gelatinous mass about the crosslinking of a kind of parents organic poly-fullerene dendrimer, and this material has a following structural formula:
Wherein, F is a fullerene core；P1And P2The most poly-(N-2-aminoethyl acrylamide), poly-[acrylamide-co-(N-2-aminoethyl acrylamide)], poly-(lysine), poly-(allylamine), poly-(Ethylenimine), polystyrene A-NH2Or polycation halogenide (X) salt of chitosan；
Each E is individually-OH, E1、E2、E3、E4Or E5；Wherein
Each E1It is individually Y1, Y2-amino, (Y1, Y2-alkyl)-amino, Y1, Y2-ethylenediamine, (dihydroxymethyl) alkyl amino, (X1, X3-aromatic radical) amino or X1, X3-aryloxy group；Each E2It is individually Y1, Y2-alkoxyl, (Y1, Y2-amino) alkoxyl, oxo (Y1, Y2, Y3-aromatic radical), (dihydroxyalkyl) aryloxy group, (Y1, Y2, Y3-alkyl) amino, (Y1Y2, Y3-aromatic radical) amino or dihydroxyalkyl amino；Each E3It is individually Y1, Y2, Y3-alkoxyl, (three hydroxyalkyls) alkoxyl, (three hydroxyalkyls) alkyl amino, (dicarboxylic acids alkyl) amino, sulfur generation (Y1, Y2, Y3-alkyl), sulfur generation (X1, X3-aromatic radical), sulfur generation (Y1, Y2-alkyl), sulfur generation (dihydroxyalkyl), Y1, Y2-two contain oxyalkyl；Each E4It is individually ((joining glycosyl) oxygen-containing heteroaryl) amino, ((joining glycosyl) oxygen-containing aromatic radical) amino, (X1, X2, X3-heteroaryl) amino, (X1-two aromatic radical ketone) amino, (X, X1-oxygen-containing aromatic radical) amino, (X, X1-two oxygen-containing aromatic radicals) amino, (Y1-alkyl, Y2The oxygen-containing heteroaryl of-alkyl two) amino, (Y1-alkyl, Y2The oxygen-containing aromatic radical of-alkyl two) amino, (two (Y1, Y2-methyl) two oxygen-containing heteroaryls) amino, (two (Y1, Y2-methyl) two oxygen-containing aromatic radicals) amino, ((joining glycosyl) heteroaryl) amino, ((joining glycosyl) aromatic radical) amino, ((carboxyl acetyl alkyl) oxygen-containing heteroaryl) amino, ((carboxyl acetyl alkyl) oxygen-containing aromatic radical) amino, ((isopropylamino hydroxyl-alkoxy) aromatic radical) amino or (X1, X2, X3-alkylaryl) amino；Each E5It is individually (X1, X2, X3-heteroaryl) epoxide, (isopropylamino hydroxy alkyl) aryloxy group, (X1, X2, X3-oxygen-containing heteroaryl) epoxide, (X1, X2, X3-oxygen-containing aromatic radical) epoxide, (X1, Y1-oxygen-containing heteroaryl) epoxide, (X1-two aromatic radical ketone) epoxide, (X, X1-oxygen-containing aromatic radical) epoxide, (X1, X2-two oxygen-containing aromatic radicals) epoxide, (Y1, Y2, diaminourea dihydroxy) alkyl, (X1, X2-heteroaryl) sulfenyl, ((three carboxyalkyls) ethylenediamine) alkoxyl, (X1, X2-oxygen-containing aromatic radical) sulfenyl, (X1, X2-two oxygen-containing aromatic radicals) sulfenyl, (joining glycosyl heteroaryl) sulfenyl, (joining glycosyl aromatic radical) sulfenyl, Y1-alkyl (thiocarboxyl group) sulfenyl, Y1, Y2-alkyl (thiocarboxyl group) sulfenyl, Y1, Y2, Y3-alkyl (thiocarboxyl group) sulfenyl, (Y1, Y2-aminothio carboxyl) sulfenyl, (pyrans) sulfenyl, cysteine, tyrosine, (phenylalanine) amino, (dicarboxylic acids alkyl) sulfenyl, (amino aryl perfume base)1-20Amino or (pyrans) amino；
Each X is individually halide anions (F-、Cl-、Br-Or I-)；Each X1、X2And X3It is individually-Y1、-O-Y1、-S-Y1、-NH-Y1、-CO-O-Y1、-O-CO-Y1、-CO-NH-Y1、-CO-NY1Y2、-NH-CO-Y1、-SO2-Y1、-CHY1Y2Or-NY1Y2；
Each Y1, Y2And Y3It is individually-B-Z；Each B is individually-Ra-O-[Si(CH3)2-O-]1-100、C1-2000Alkyl, C6-40Aromatic radical, C7-60Alkylaryl, C7-60Arylalkyl group, (C1-30Alkhyl ethers)1-100、(C6-40Aromatic radical ether)1-100、(C7-60Alkylaryl ether)1-100、(C7-60Arylalkyl group ether)1-100、(C1-30Alkylthio ether)1-100、(C6-40Aromatic radical thio-ether)1-100、(C7-60Alkylaryl thio-ether)1-100、(C7-60Arylalkyl group thio-ether)1-100、(C2-50Alkyl ester)1-100、(C7-60Aromatic ester)1-100、(C8-70Alkyl aromatic ester)1-100、(C8-70Aromatic radical alkyl ester)1-100、-R-CO-O-(C1-30Alkhyl ethers)1-100、R-CO-O-(C6-40Aromatic radical ether)1-100、-R-CO-O-(C7-60Alkylaryl ether)1-100、-R-CO-O-(C7-60Arylalkyl group ether)1-100、(C4-50Alkyl urethane)1-100、(C14-60Aromatic radical urethane)1-100、(C10-80Alkylaryl urethane)1-100、(C10-80Arylalkyl group urethane)1-100、(C5-50Alkyl carbamide)1-100、(C14-60Aromatic radical carbamide)1-100、(C10-80Alkylaryl carbamide)1-100、(C10-80Arylalkyl group carbamide)1-100、(C2-50Alkylamide)1-100、(C7-60Aromatic radical amide)1-100、(C8-70Alkylaryl amide)1-100、(C8-70Arylalkyl group amide)1-100、(C3-30Alkyl anhydride)1-100、(C8-50Aromatic radical anhydride)1-100、(C9-60Alkylaryl anhydride)1-100、(C9-60Arylalkyl group anhydride)1-100、(C2-30Alkyl carboxylic acid ester)1-100、(C7-50Aromatic carboxylic ester)1-100、(C8-60Alkylaryl carboxylate)1-100、(C8-60Arylalkyl group carboxylate)1-100、-R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C1-30Alkhyl ethers, C6-40Aromatic radical ether, C7-60Alkylaryl ether or C7-60Arylalkyl group ether)1-100、-R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C2-50Alkyl ester, C7-60Aromatic ester, C8-70Alkyl aromatic ester or C8-70Aromatic radical alkyl ester)1-100、-R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C1-30Alkhyl ethers, C6-40Aromatic radical ether, C7-60Alkylaryl ether or C7-60Arylalkyl group ether)1-100-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-、-R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C2-50Alkyl ester, C7-60Aromatic ester, C8-70Alkyl aromatic ester or C8-70Aromatic radical alkyl ester)1-100-R3-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-、-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C1-30Alkhyl ethers, C6-40Aromatic radical ether, C7-60Alkylaryl ether or C7-60Arylalkyl group ether)1-100、-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-(C2-50Alkyl ester, C7-60Aromatic ester, C8-70Alkyl aromatic ester or C8-70Aromatic radical alkyl ester)1-100、-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C1-30Alkhyl ethers, C6-40Aromatic radical ether, C7-60Alkylaryl ether or C7-60Arylalkyl group ether)1-100-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-、-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C2-50Alkyl ester, C7-60Aromatic ester, C8-70Alkyl aromatic ester or C8-70Aromatic radical alkyl ester)1-100-R3-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-、-R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-NH-(C2-50Alkylamide, C7-60Aromatic radical amide, C8-70Alkylaryl amide or C8-70Arylalkyl group amide)1-100Or-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-NH-(C2-50Alkylamide, C7-60Aromatic radical amide, C8-70Alkylaryl amide or C8-70Arylalkyl group amide)1-100；
Each Z is individually-C-D-, the most each C and is individually-R-,-R-Ar-,-Ar-R-or-Ar-；It is individually-OH ,-SH ,-NH with each D2、-NHOH、-SO3H、-OSO3H、-COOH、-CONH2、-CO-NH-NH2、-CH(NH2)-COOH、-P(OH)3、-PO(OH)2、-O-PO(OH)2、-O-PO(OH)-O-PO(OH)2、-O-PO(O-)-O-CH2CH2NH3,-join sugar ,-OCH3、-O-CH2-(CHOH)4-CH2OH、-O-CH2-(CHOH)2-CH2OH、-C6H3(OH)2、-NH3、-N+H2Rb、-N+HRbRcOr N+HRbRcRd；The most each R, R1、R2、R3、Ra、Rb、RcAnd RdIt is individually C1-30Alkyl, each Ar individually aromatic radical, n are 2-50 and x, y and z are individually 2-200；Or its salt.
Such salt can form (such as: chlorine, bromine and iodide ion are the balance ion of the quaternary ammonium group of this compound) between the balance ion of the compound of an above-mentioned chemical formula and the ionogen of this compound.In disclosure of the invention, fullerene core associates the molecule in a cage, this molecule is made up of carbon atom substantially, such as C60、C60Hx、C70、C70Hx、C76、C76Hx、C78、C78Hx、C82、C82Hx、C84、C84Hx、C92、C92HxIt is 1-30 with analog, wherein x.
The subset of the derivant that the above-mentioned chemical formula quoted is covered is characterised by that each E is respectively E2、E3、E4Or E5。
The subset of the derivant that the above-mentioned chemical formula quoted is covered is characterised by that each E is respectively E3、E4Or E5.Preferably, each X1It is individually-Y1、-O-Y1、-S-Y1、-NH-Y1、-CO-O-Y1、-O-CO-Y1、-CO-NH-Y1、CO-NY1Y2、-NH-CO-Y1、-SO2-Y1、-CHY1Y2Or-NY1Y2；Each B is individually-Ra-O-[Si(CH3)2-O-]1-100、C6-40Aromatic radical, C7-60Alkylaryl, C7-60Arylalkyl group, (C6-40Aromatic radical ether)1-100、(C7-60Alkylaryl ether)1-100、(C7-60Arylalkyl group ether)1-100、(C1-30Alkylthio ether)1-100、 (C6-40Aromatic radical thio-ether)1-100、(C7-60Alkylaryl thio-ether)1-100、(C7-60Arylalkyl group thio-ether)1-100、(C2-50Alkyl ester)1-100、(C7-60Aromatic ester)1-100、(C8-70Alkyl aromatic ester)1-100、(C8-70Aromatic radical alkyl ester)1-100、-R-CO-O-(C1-30Alkhyl ethers)1-100、-R-CO-O-(C6-40Aromatic radical ether)1-100、-R-CO-O-(C7-60Alkylaryl ether)1-100、-R-CO-O-(C7-60Arylalkyl group ether)1-100、(C4-50Alkyl urethane)1-100、(C14-60Aromatic radical urethane)1-100、(C10-80Alkylaryl urethane)1-100、(C10-80Arylalkyl group urethane)1-100、(C5-50Alkyl carbamide)1-100、(C14-60Aromatic radical carbamide)1-100、(C10-80Alkylaryl carbamide)1-100、(C10-80Arylalkyl group carbamide)1-100、(C2-50Alkylamide)1-100、(C7-60Aromatic radical amide)1-100、(C8-70Alkylaryl amide)1-100、(C8-70Arylalkyl group amide)1-100、(C3-30Alkyl anhydride)1-100、(C8-50Aromatic radical anhydride)1-100、(C9-60Alkylaryl anhydride)1-100、(C9-60Arylalkyl group anhydride)1-100、(C2-30Alkyl carboxylic acid ester)1-100、(C7-50Aromatic carboxylic ester)1-100、(C8-60Alkylaryl carboxylate)1-100、(C8-60Arylalkyl group carboxylate)1-100、-R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C1-30Alkhyl ethers, C6-40Aromatic radical ether, C7-60Alkylaryl ether or C7-60Arylalkyl group ether)1-100、-R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C2-50Alkyl ester, C7-60Aromatic ester, C8-70Alkyl aromatic ester or C8-70Aromatic radical alkyl ester)1-100、-R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C1-30Alkhyl ethers, C6-40Aromatic radical ether, C7-60Alkylaryl ether or C7-60Arylalkyl group ether)1-100-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-、R1-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C2-50Alkyl ester, C7-60Aromatic ester, C8-70Alkyl aromatic ester or C8-70Aromatic radical alkyl ester)1-100-R3-OCO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-、-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C1-30Alkhyl ethers, C6-40Aromatic radical ether, C7-60Alkylaryl ether or C7-60Arylalkyl group ether)1-100、-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-(C2-50Alkyl ester, C7-60Aromatic ester, C8-70Alkyl aromatic ester or C8-70Aromatic radical alkyl ester)1-100、-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C1-30Alkhyl ethers, C6-40Aromatic radical ether, C7-60Alkylaryl ether or C7-60Arylalkyl group ether)1-100-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-、-R1-NH-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-(C2-50Alkyl ester, C7-60Aromatic ester, C8-70Alkyl aromatic ester or C8-70Aromatic radical alkyl ester)1-100-R3-O-CO-NH-(R2Or Ar-R2-Ar)-NH-CO-O-、-R1-O-CO-NH-R2Or Ar-R2-Ar)-NH-CO-NH-(C2-50Alkylamide, C7-60Aromatic radical amide, C8-70Alkylaryl amide or C8-70Arylalkyl group amide)1-100Or-R1-NH-CO-NH-R2Or Ar-R2-Ar)-NH-CO-NH-(C2-50Alkylamide, C7-60Aromatic radical amide, C8-70Alkylaryl amide or C8-70Arylalkyl group amide)1-100；The most each R, Ra、R1、R2And R3It is individually C1-20Alkyl, and each Ar is individually aromatic radical；It is individually-SH ,-NHOH ,-SO with each D3H、-OSO3H、-COOH、-CONH2、-CO-NH-NH2、-CH(NH2)-COOH、-P(OH)3、-PO(OH)2、-O-PO(OH)2、-O-PO(OH)-O-PO(OH)2、-O-PO(O-)-O-CH2CH2NH3,-join sugar ,-O-CH2-(CHOH)4-CH2OH、-O-CH2-(CHOH)2-CH2OH、-C6H3(OH)2、-N+H2Rb、-N+HRbRcOr N+HRbRcRd；Wherein, each R, R1、R2、R3、Ra、Rb、RcAnd RdIt is individually C1-30Alkyl and each Ar are individually aromatic radical.
Another subset of the derivant that the above-mentioned chemical formula quoted is covered is characterised by that each E is respectively E4Or E5.Preferably, each X1It is individually-Y1、-O-Y1、-S-Y1、-NH-Y1、-CO-O-Y1、-O-CO-Y1、-CO-NH-Y1、-CO-NY1Y2、-NH-CO-Y1、-SO2-Y1、-CHY1Y2Or-NY1Y2；And each B with D each has above-mentioned identical definition.
Protection scope of the present invention also includes the preparation method of the polycationic polymer gelatinous mass of a kind of crosslinking of the organic poly-fullerene dendrimer of parents with following structural formula:
The method includes obtaining a kind of as general fullerene poly-with the nitro of reactive intermediate or the step of the poly-fullerene derivate of cyclic sulfate with the step contacted with nucleopilic reagent by this intermediate, to obtain the polycationic polymer gel of parents' fullerene dendrimer crosslinking.In this structural formula, F is a fullerene core, each E each-OH, E1、E2、E3、E4Or E5, the most each E1-5There is above-mentioned identical definition.
Method described above can extend further to produce the polycationic polymer gel of a kind of hydrophilic (polyhydroxy) fullerene dendrimer crosslinking by hydrolyzing the polycationic polymer gel of thus obtained parents' fullerene dendrimer crosslinking.
Term " alkyl " the meaning be a straight chain including 1-30 carbon atom or include 3-30 carbon atom branched hydrocarbon chains or include the cyclic hydrocarbon group of 3-30 carbon atom or other.These alkyl groups may also comprise one or more double or triple bonds, and cycloalkyl group can include one or more hetero atom, and above-mentioned hetero atom can be typical nitrogen, oxygen or sulfur.The example of alkyl group includes but not limited to methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, the tert-butyl group, amyl group, pentyl, hexyl, heptyl, octyl group, nonyl, decyl, pentadecyl, Isoeicosane base, acrylic, crotyl, pentenyl, 3-hexenyl, 4-decene, 5-19 thiazolinyl, 2-butyl ester, 3-monooctyl ester, 5-octadecyl ester, cyclopropyl, Pentamethylene. base, cyclohexyl, suberyl, adamantyl, norcamphanyl, different camphyl, methyl cyclopentane, cyclohexyl methyl, 1-or 2-hexamethylene ethyl, cyclopentenyl, cyclohexenyl group, cycloheptenyl, cyclo-octene base, tetrahydrofuran base, THP trtrahydropyranyl, piperidyl, morpholinyl and pyrrole radicals group.
As shown here, term " aromatic radical " refer to C6-40Aromatic rings.These parts can also be condensed ring or aromatic radical defined below or the fusion of heteroaryl.Fusion ring is the ring sharing same carbon-carbon bond.Typical aromatic radical group includes phenyl, naphthyl, biphenyl, indazolyl, phenanthryl and anthryl.
Term disclosed herein " heteroaryl " the meaning be containing the heteroatomic C defined before one or more6-40Aromatic rings.These parts can also is that fusion ring.The example of heteroaryl group includes pyridine radicals, pyrazinyl, pyrimidine radicals, furyl, pyrrole radicals, thienyl, thiazolyl, oxazolyl, imidazole radicals, coumarin base, indyl, benzofuranyl, benzothiazolyl, benzothienyl and diazosulfide base.
As shown here, term " halogenide " is defined as fluorine, chlorine, bromine or iodine.Term " the poly-fullerene of nitro " in the disclosure and " the poly-fullerene of cyclic sulfate " are respectively provided with following structural formula: F-(NO2)mWith F-(SO4)m, wherein m is at least 2.Term " nucleopilic reagent " is defined as providing in the reaction the electron rich class of electronics.The nucleopilic reagent of the polycationic polymer gel that can be used in the crosslinking of parents' fullerene dendrimer includes amine, phenol, alkoxide, organic sulfur alkoxide, carbanion, organic amide anion, mercaptan, aminoacid and sulfhydryl amino formic acid esters anion.It should be noted that the nucleopilic reagent just now mentioned can replace or unsubstituted with other functional groups.Substituted nucleopilic reagent includes Isosorbide-5-Nitrae-naphtho-lamine, tyrosine, dihydroxypropyl mercaptan and the like.For example, the poly-fullerene of nitro is with nucleopilic reagent dihydroxypropyl mercaptan, it is possible to poly-(N-2-aminoethyl acrylamide), poly-[acrylamide-co-(N-2-aminoethyl acrylamide)], poly-(lysine), poly-(allylamine), poly-(Ethylenimine), polystyrene A-NH2Or chitosan reaction, generate the polycationic polymer gel of corresponding parents poly-(dihydroxypropyl sulfydryl) fullerene dendrimer crosslinking, see following embodiment 3～12.The meaning of term " hydrolysis " is that a hydrone attacks the sensitive key of a compound this sensitivity key that ruptures under conditions of alkalescence or acidity.Alkali is here used for preparing the polycationic polymer gel of hydrophilic (polyhydroxy) fullerene dendrimer crosslinking usually used as hydrolysing agent, and preferably hydrolysing agent is sodium hydroxide in the disclosure.
Many structures of part above-mentioned show in the bracket after each part: alkhyl ethers (-R-O-), aromatic radical ether (-Ar-O-), alkylaryl ether (-R-Ar-O-), arylalkyl group ether (-Ar-R-O-), alkylthio ether (-R-S-), aromatic radical thio-ether (-Ar-S-), alkylaryl thio-ether (-R-Ar-S-), arylalkyl group thio-ether (Ar-R-S-), alkyl ester (-R-O-CO-,-R-CO-O-,-R1-CO-O-R2-O-CO-or-R1-O-CO-R2-CO-O-), aromatic ester (-Ar-O-CO-,-Ar-CO-O-,-Ar-CO-O-Ar2-O-CO-or-Ar1-O-CO-Ar2-CO-O-), alkyl aromatic ester (-R-Ar-O-CO-or-R-Ar-CO-O-), aromatic radical alkyl ester (-Ar-R-O-CO-or-Ar-R-CO-O-), alkyl urethane (-R1-O-CO-NH-R2-NH-CO-O-), aromatic radical urethane (-Ar1-O-CO-NH-Ar2-NH-CO-O-), alkylaryl urethane (-R1-Ar-O-CO-NH-R2-NH-CO-O-、-R-Ar1-O-CO-NH-Ar2-NHCO-O-or-R1-O-CO-NH-Ar-R2-Ar-NH-CO-O-), arylalkyl group urethane (-Ar-R1-O-CO-NH-R2-NH-CO-O-、-Ar1-R-O-CO-NH-Ar2-NH-CO-O-or-Ar1-O-CO-NH-Ar2-R-Ar2-NH-CO-O-), alkyl carbamide (-R1-NH-CO-NH-R2-NH-CO-NH-), aromatic radical carbamide (-Ar1-NH-CO-NH-Ar2-NH-CO-NH-), alkylaryl carbamide (-R1-Ar-NH-CO-NH-R2-NH-CO-NH-、-R-Ar-NH-CONH-Ar2-NH-CO-NH-or-R1-NH-CO-NH-Ar-R2-Ar-H-CO-NH-), arylalkyl group carbamide (-Ar-R1-NH-CO-NH-R2-NH-CO-NH-、-Ar1-R-NH-CONH-Ar2-NH-CO-NH-or-Ar1-NH-CO-NH-Ar2-R-Ar2-NH-CO-NH-), alkylamide (-R-NH-CO-,-R-CO-NH-,-R1-CO-NH-R2-NH-CO-or-R1-NH-CO-R2-CO-NH-), aromatic radical amide (-Ar-NH-CO-,-Ar-CO-NH-,-Ar1-CO-NH-Ar2-NH-CO-or-Ar1-NH-CO-Ar2null-CO-NH-)、Alkylaryl amide (-R-Ar-NH-CO-、-R-CO-NH-Ar-NH-CO-or-R-NH-CO-Ar-CONH-)、Arylalkyl group amide (-Ar-R-NH-CO-、-Ar-CO-NH-R-NH-CO-or-Ar-NH-CO-R-CO-NH-)、Alkyl anhydride (-R-CO-O-CO-)、Aromatic radical anhydride (-Ar-CO-O-CO-)、Alkylaryl anhydride (-R-Ar-CO-O-CO-or-R-CO-O-CO-Ar-CO-O-CO-)、Arylalkyl group anhydride (-Ar-R-O-O-CO-or-Ar-CO-O-CO-R-CO-O-CO-)、Alkyl carboxylic acid ester (-R-CO-O-)、Aromatic carboxylic ester (-Ar-O-CO-O-)、Alkylaryl carboxylate (-R-Ar-O-CO-O-or-R-O-CO-O-Ar-O-CO-O-) and arylalkyl group carboxylate (-Ar-R-O-CO-O-or-Ar-O-CO-O-R-O-CO-O-).Notice that the disubstituted form on Ar can be para-position, meta or ortho position.
Term " cross-links " the mutual connection representing between polymer chain.
Term " dendritic " represents the dendritic organometallic alkyl branch in fullerene nanocages.
Term " hydrophilic " refer to that described polymer gel is to the good suction phase interreaction force of water and trend.
Term " hydrophobicity " refers to that described polymer gel is to the good suction phase interreaction force of organic oil material and trend.
Term " parents " refer to that described polymer gel is to water and the good suction phase interreaction force of organic oil material and trend.
Term " additament " refer to the functional group that on a fullerene cage is additional.
Nitro poly-fullerene alkene F-(NO herein2)mOr cyclic sulfate poly-fullerene F-(SO4)mCan be as intermedium in order to prepare the polycationic polymer gel (as shown in following embodiment) of various parents organic poly-fullerene dendrimer crosslinking.Using of these intermediums allows reaction carrying out in a mild condition at high speed to produce organic poly-fullerene derivate.See U.S. Patent number 6,020,523 and 6,046,361.Some of them synthesis can be used for producing fullerene graft polymers from the fullerene derivate of nitro poly-fullerene alkene or the poly-fullerene of cyclic sulfate successively.See U.S. Patent number 5,635,581.Except the starting material as polymer, these derivants are alternatively arranged as useful free radical scavenger.See U.S. Patent number 5,648,523.
Other features and advantages of the present invention will show in ensuing description of preferred embodiments and claim.
Detailed description of the invention
It is described below the various different method of the polycationic polymer gelatinous mass cross-linked via the organic poly-fullerene dendrimer of the poly-fullerene of described nitro or cyclic sulfate poly-fullerenes synthesis parents.Nitro poly-fullerene derivate F-(NO2)m, it is possible to preparing by the one in following method, the poly-fullerene derivate of this nitro is as 3D cross-linking reagent reactive intermediate in the present invention:
A) a kind of production F-(NO2)mMethod relate to fullerene F with originate from sodium nitrite NaNO2With cone nitric acid HNO3Nitrogen dioxide free radical NO2. react.See Chiang etc., Tetrahedron1996,52 (14), 4963.F-(NO2)mStructure be characterised by including at least 4 nitros.
B) with fullerene and the dinitrogen tetroxide N of reaction2O4In Carbon bisulfide solution, the F-(NO that m is 4 is prepared in reaction2)m.See Cataldo etc., Fullerene Sci.&Techno.1997,5 (1), 257.
C) F-(NO is prepared2)mAnother kind of method be that nitrogen dioxide gas produced by fullerene and the mixture of the sodium nitrite in aqueous sulfuric acid and ferrous sulfate with reaction reacts.See Sarkar etc., J.Chem.Soc., Chem.Commum.1994,275.
D) F-(NO is prepared2)mYet another method be with reaction fullerene react with fuming nitric aicd.See Hamwi etc., Fullerene Sci.&Techno.1996,4 (5), 835.
Cyclic sulfate poly-fullerene derivate F-(SO4)m, it is possible to fullerene and solvent-free oleum with reaction are at a kind of oxidant (such as P2O5、V2O5Or SeO2) exist under conditions of prepare.The poly-fullerene derivate of this cyclic sulfate in the present invention can be as one effectively middle 3D cross-linking reaction thing.The structure of this product is characterised by being made up of 4 to 6 cyclic sulfate unit.See Chiang etc., J.Org.Chem.1994,59,3960；JCS Perkin Trans.11998,1171-1173.
Parents gather the application of organic fullerene dendritic crosslinking polycationic polymer gel and relate to their synthesis, and their synthesis is typically the intermedium 3D cross-linking reagent with reaction and poly-(N-2-aminoethyl acrylamide), poly-[acrylamide-co-(N-2-aminoethyl acrylamide)], poly-(lysine), poly-(allylamine), poly-(Ethylenimine), polystyrene A-NH2Or the one in chitosan (as described in following embodiment) reacts, the above-mentioned 3D cross-linking reagent poly-fullerene of such as nitro, F-(NO2)mOr polycyclic sulfonation fullerene, F-(SO4)m.Next react with an affine medium, E-H (main and secondary organic metal amino-compound, alkoxide, organic metal mercaptides, organic metal oxybenzene compound, carbanion, organic metal amide anion, thiocarbamate ion and the like) in just like the non-reactive solvent of oxolane.In some react, (seeing the following examples) needs alkali to produce the nucleophilic anion of enough E-H to carry out substitution reaction.Such alkali includes 1,8-diazabicylo [5.4.0]-ten one carbon-7-ethylene (DBU), 1,5-diazabicylo [4.3.0] nonyl-5-alkene (DBN) and lithium diisopropylamine (LDA).
The polycationic polymer gel of parents' organic poly-fullerene dendrimer crosslinking that a kind of previous reaction prepares further can react the polycationic polymer gel generating hydrophilic hydroxyl poly-fullerene dendrimer crosslinking with hydrolysing agent.For example, sodium hydroxide is a kind of effective hydrolysing agent in disclosure of the invention, and TBAH is here used as phase transfer reagent.It should be noted that the number that the symbol m in each term in the disclosure is not required to represented by the symbol identical with in other terms is identical.
Need not be further elucidated above, those of ordinary skill in the art can make full use of the present invention according to description herein.Therefore, following detailed description of the invention is merely illustrative the present invention, and is not intended to the practical range of the present invention.The public publication of all references herein, including patent, the most complete merging is quoted.
Embodiment 1
The poly-fullerene of nitro, C60(NO2)mPreparation
One neck installing one of one or two neck reaction bulb A (50ml) has the vertical Dropping funnel of piston, another neck installing one connection gas bubble pipe.This gas bubble pipe is upper connects a drying tube (CaCl2) and be inserted into second liang of neck reaction bulb B.Another neck of reaction bulb B connects a bubbling pipe, and this bubbling pipe extends into a capture bottle containing sodium hydrate aqueous solution comprising 2 equivalents.In order to minimize the backflow of the moisture from alkaline solution, between reaction bulb B and capture bottle, a drying tube (CaCl is installed2).Flow from the beginning of the top of Dropping funnel with stable noble gas (nitrogen), flow through reaction bulb A and B successively, finally enter in the alkaline solution of capture bottle.Dropping funnel and reaction bulb A are separately added into the HNO of concentration3(10ml) with copper powder (10g).The benzole soln (50ml is dried) of [60] fullerene (500mg) is loaded with Na in reaction bulb B.C in reactor B60The flow velocity of the noble gas producing bubble in solution is adjusted to 5mL per minute.Fullerene solution the most at least carries out the deoxygenation of 5 minutes.In the sodium nitrite solid that the salpeter solution of concentration is added dropwise in reactor A.Cone nitric acid and sodium nitrite produce the cigarette of brown at a touch.The cigarette of this brown is carried by stable nitrogen stream, and the C in reactor B60Solution produces bubble.In 15 minutes of reaction, C60Purple solution gradually become Chinese red.Mixture is at room temperature stirred for 2 hours with the solution producing the dark brown redness with suspended solid.At the end of reaction, unnecessary nitrogen dioxide is removed by nitrogen bubble and is deteriorated in capture solution.Benzene concentrates out at reduced pressure conditions from product, to obtain the solid of pitchy.Gained solid suspends in anhydrous n-hexane, then is separated from n-hexane by centrifugal, finally carries out being vacuum dried obtaining the brown solid of the poly-fullerene derivate of nitro, C at 40 DEG C60(NO2)m(m=4-6on average) (650mg).Spectroscopic data: IR vmax(KBr) 1572 [s, vas(N-O)], 1328 [s, vs(N-O)], 1085,1038,973,815,760,733,696,545 and 466cm-1.Products obtained therefrom is soluble in ordinary organic solvents, such as THF, DMF, CH2Cl2、CH3OH and DMSO.
Embodiment 2
Polycyclic sulfonation fullerene, C60(SO4)mSynthesis
C is loaded at reaction bulb (50ml)60And C (80%)70(20%) fullerene mixture of (1.0g), a kind of oxidant and oleum (15ml), be stirred at 55-60 DEG C.Logical nitrogen 5 minutes to 3 hours so that produce the float of orange in the solution of light brown.Oxidant is selected from P2O5(6.0g)、V2O5(150mg) or SeO2(700mg).Gained mixture is added dropwise in 200mL mixture of ice and water causing product to precipitate.By centrifugal, precipitation is separated from aqueous solution.Then use mixture of ice and water eccentric cleaning twice, then at a temperature of 40 DEG C, carry out being vacuum dried to obtain the polycyclic sulfonation fullerene solid C of terra-cotta60(SO4)m(1.4g)。C60(SO4)mPhysical data as follows: IR vmax(KBr) 2920 (br), 2400 (br), 1706 (w), 1654 (w), 1598 (w), 1427 (s), 1229 (s), 1168,1046,1002 (s), 981,953 (s), 855,826 (s), 783,641,530,485 (w) and 411 (w) cm-1；13C NMR(DMF-d7, peak center) and δ 148.0,77.0 and 71.0；1H NMR(DMF-d7, peak center) and δ 14.6 (w, the OSO of partial hydrolysate2-OH)。
Embodiment 3
The synthetic method 1 of poly-amino fullerene dendritic crosslinking polycationic polymer gel
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(500mg) tetrahydrofuran solution (10ml), and stirring 1.0 hours at ambient temperature.Within 20 minutes, to produce bubble, the flow velocity of ammonia is that 5mL is per minute to logical ammonia, during dry ice/acetone is full of the cooling grabber being positioned at reactor head simultaneously.At the end of reaction, gained solution adds 100mL methanol to produce the precipitation of brown solid.This solid precipitation of centrifugation.This solid precipitation is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, 30mL every time, and at a temperature of 40 DEG C, carry out the brown solid (560mg) being vacuum dried to obtain the corresponding polycation salt of the poly-dendritic crosslinking of amino fullerene poly-(N-2-aminoethyl acrylamide) gel.The spectroscopic data of the poly-dendritic crosslinking of amino fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3400 (s ,-NH2), 3246 (s), 1668 (s ,-NH-C=O), 1613 (s), 1600,1554,1389,1341,1275,1038 (br, s), 741 and 548cm-1。
Embodiment 4
The synthetic method 2 of poly-amino fullerene dendritic crosslinking polycationic polymer gel
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(520mg) tetrahydrofuran solution (10ml), and stirring 20 minutes at ambient temperature.Within 20 minutes, to produce bubble, the flow velocity of ammonia is that 5ml is per minute to logical ammonia, during dry ice/acetone is full of the cooling grabber being positioned at reactor head simultaneously.At the end of reaction, gained solution adds 100ml methanol to produce the precipitation of brown solid.This solid precipitation of centrifugation.This solid precipitation is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, 30ml every time, and at a temperature of 40 DEG C, carry out the brown solid (610mg) being vacuum dried to obtain the corresponding polycation salt of the poly-dendritic crosslinking of amino fullerene poly-(N-2-aminoethyl acrylamide) gel.The spectroscopic data of the poly-dendritic crosslinking of amino fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3400 (s ,-NH2), 3246 (s), 1670 (s ,-NH-C=O), 1625 (s), 1556,1388,1343,1274,1062 (br, s), 749 and 542cm-1。
Embodiment 5
Poly-(diethanolamine amino) fullerene dendritic crosslinking polycationic polymer gel [E:-N (CH2CH2OH)2] synthesis
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(520mg) tetrahydrofuran solution (10ml), and stirring 20 minutes at ambient temperature.Add diethanolamine (distillation, 700mg) tetrahydrofuran solution (10ml), be stirred for 30 minutes.At the end of reaction, gained solution adds 100ml methanol to produce the precipitation of brown solid.This solid precipitation of centrifugation.This solid precipitation is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, 30ml every time, and at a temperature of 40 DEG C, carry out the brown solid (880mg) being vacuum dried to obtain the corresponding polycation salt of poly-(diethanolamine amino) dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide) gel.The spectroscopic data of poly-(diethanolamine amino) dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3374 (s ,-OH), 2933 (C-H), 1671 (s ,-NH-C=O), 1615 (s), 1561,1455,1392,1272,1074 (br, s), 669 and 534cm-1。
Embodiment 6
Poly-(hydroxyl ethoxy ethyl amino) fullerene dendritic crosslinking polycationic polymer gel (E:-NHCH2CH2OCH2CH2OH) synthesis
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(520mg) tetrahydrofuran solution (10ml), and stirring 20 minutes at ambient temperature.Add the tetrahydrofuran solution (30ml) of three (hydroxymethyl) methyl amine (900mg), be stirred for 30 minutes.At the end of reaction, gained solution adds 100ml methanol to produce the precipitation of brown solid.This solid precipitation of centrifugation.This solid precipitation is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, 30ml every time, and at a temperature of 40 DEG C, carry out the brown solid (895mg) being vacuum dried to obtain the corresponding polycation salt of poly-(hydroxyl ethoxy ethyl amino) dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide) gel.The spectroscopic data of poly-(hydroxyl ethoxy ethyl amino) dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3381 (s ,-OH), 2933 (C-H), 2868 (C-H), 1666 (s,-NH-C=O), 1605 (s), 1565,1455,1349,1248,1117 (s), 1065 (br, s) and 535cm-1。
Embodiment 7
Poly-(TYR halogenide) fullerene dendritic crosslinking polycationic polymer gel [E:-OC6H4CH2CH(NH2)CO2H] synthesis
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(520mg) tetrahydrofuran solution (10ml), and stirring 20 minutes at ambient temperature.Add TYR halogenide (500mg, fine separation) and 1,8-diazabicylo [5.4.0]-ten one carbon-7-ethylene (DBU, 600mg), be stirred for 30 minutes.At the end of reaction, gained solution adds 100ml methanol to produce the precipitation of brown solid.This solid precipitation of centrifugation.This solid precipitation is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, 30ml every time, and at a temperature of 40 DEG C, carry out the brown solid (955mg) being vacuum dried to obtain the corresponding polycation salt of poly-(TYR halogenide) dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide) gel.The spectroscopic data of poly-(TYR halogenide) dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3407 (s), 3260,2925 (C-H), 2575 (br ,-CO2H), 1675 (s ,-NH-C=O), 1602 (s), 1589,1561,1481,1406,1378,1346,1311,1223,1082 (br, s), 825,782,715,644,593 and 534cm-1。
Embodiment 8
Poly-(hexyl sulfydryl) fullerene dendritic crosslinking polycationic polymer gel (E:-SCH2CH2CH2CH2CH2CH3) synthesis
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(520mg) tetrahydrofuran solution (10ml), and stirring 20 minutes at ambient temperature.Add hexyl mercaptan (420mg), be stirred for 30 minutes.At the end of reaction, gained solution adds 100ml methanol to produce the precipitation of brown solid.This solid precipitation of centrifugation.This solid precipitation is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, 30ml every time, and at a temperature of 40 DEG C, carry out the brown solid (930mg) being vacuum dried to obtain the corresponding polycation salt of poly-(hexyl sulfydryl) dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide) gel.The spectroscopic data of poly-(hexyl sulfydryl) dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 2953 (C-H), 2921 (C-H), 2848 (C-H), 1677 (s ,-NH-C=O), 1644,1605 (s), 1459,1428,1384,1183,1075 (br, s), 1045,793,729,577 and 526cm-1。
Embodiment 9
Poly-[double (1,1 '-hydroxyl amino ethyl) methyl] fullerene dendritic crosslinking polycationic polymer gel { E:-CH [C (OH) (NH2)CH3]2Synthesis
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(400mg) tetrahydrofuran solution (25ml), and stirring 20 minutes at ambient temperature.
It is fitted with magnetic stirring apparatus and a cooling capture condenser of a barrier film in another round bottom reaction bulb B (100ml) installing, this reaction bulb B adds 2,4-pentanedione (350mg) and oxolane (20ml).Add the tetrahydrofuran solution (1.1 times of equivalents of 2,4-pentanediones) of diisopropylamine lithium in the mixture, stir 1.0 hours to obtain corresponding acetylacetonate lithium.This solution is joined in reaction bulb A, then is stirred at room temperature 2.0 hours.At the end of reaction, said mixture ammonium iodide (NH4 +I-) merceration, and stir 1.0 hours.Then from solution, oxolane is removed to obtain semi-solid product, this semisolid product dilute hydrochloric acid methanol processes, and repeatedly clean with water acetone, the brown solid (625mg) being vacuum dried to obtain the corresponding polycation salt of poly-[double (1,1 '-hydroxyl amino ethyl) methyl] the dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide) gel is carried out again at a temperature of 40 DEG C.The spectroscopic data of poly-[double (1,1 '-hydroxyl amino ethyl) methyl] dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3400 (s), 3151 (s), 3043,2929 (C-H), 2880 (C-H), 1669 (s,-NH-C=O), 1635,1608 (s), 1403,1222,1068 (br, s), 1035 (s), 775,632 and 548cm-1。
Embodiment 10
Poly-(Isosorbide-5-Nitrae, 7,10-triethylene tetraminos) fullerene dendritic crosslinking polycationic polymer gel (E:-NHCH2CH2NHCH2CH2NHCH2CH2NH2) synthetic method 1
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(520mg) tetrahydrofuran solution (10ml), and stirring 20 minutes at ambient temperature.Add Isosorbide-5-Nitrae, the tetrahydrofuran solution (30ml) of 7,10-triethylene tetramines (1.0g), be stirred for 30 minutes.At the end of reaction, gained solution adds 100ml methanol to produce the precipitation of brown solid.This solid precipitation of centrifugation.This solid precipitation is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, 30ml every time, and carry out being vacuum dried to obtain poly-(1 at a temperature of 40 DEG C, 4,7,10-triethylene tetraminos) brown solid (1.1g) of corresponding polycation salt of the dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide) gel.The spectroscopic data of poly-(Isosorbide-5-Nitrae, 7,10-triethylene tetraminos) the dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3254 (br, s ,-NH), 2935 (C-H), 2871 (C-H), 1669 (s,-NH-C=O), 1608 (s), 1572,1434,1335,1288 (s), 1208 (s), 1062 (br, s) and 533cm-1。
Embodiment 11
Poly-(Isosorbide-5-Nitrae, 7,10-triethylene tetraminos) fullerene dendritic crosslinking polycationic polymer gel (E:-NHCH2CH2NHCH2CH2NHCH2CH2NH2) synthetic method 2
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Poly-(allylamine) or poly-(Ethylenimine) (100mg), double methyl form amide (10ml) and oxolane (40ml) is added in reaction bulb, stirring 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(520mg) tetrahydrofuran solution (10ml), and stirring 20 minutes at ambient temperature.Add Isosorbide-5-Nitrae, the tetrahydrofuran solution (30ml) of 7,10-triethylene tetramines (1.0g), be stirred for 30 minutes.At the end of reaction, gained solution adds 100ml methanol to produce the precipitation of brown solid.This solid precipitation of centrifugation.This solid precipitation is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, 30ml every time, and carry out being vacuum dried to obtain poly-(1 at a temperature of 40 DEG C, 4,7,10-triethylene tetraminos) brown solid (1.0g) of corresponding polycation salt of the dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide) gel.The spectroscopic data of poly-(Isosorbide-5-Nitrae, 7,10-triethylene tetraminos) the dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3232 (br, s ,-NH), 2951 (C-H), 2880 (C-H), 1658,1602,1496,1345,1242 (s), 1178 (br, s), 1075 (br) and 542cm-1。
Embodiment 12
Poly-[methoxyl group oligosaccharide (vinyl alcohol acid)] fullerene dendritic crosslinking polycationic polymer gel [E:-O (CH2CH2O)3 Or 12-13CH3] synthesis
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in round bottom reaction bulb (100ml) installing.Adding poly-(N-2-aminoethyl acrylamide) (100mg) and oxolane (40ml) in round bottom reaction bulb, stir 3 hours, period carries out ultrasonic Treatment frequently.C is added slowly in above-mentioned solution60(NO2)m(400mg) tetrahydrofuran solution (10ml), and stirring 20 minutes at ambient temperature.
Magnetic stirring apparatus and a cooling capture condenser of a barrier film it is fitted with in another round bottom reaction bulb B (100ml) installing.Polyethylene glycol monomethyl ether, HO (CH is added in this reaction bulb B2CH2O)3CH3Or HO (CH2CH2O)12-13CH3(1.3 times of equivalents of the nitro of the poly-fullerene of nitro) and oxolane (20ml).Add sodium (1.2 times of equivalents of-OH) in the mixture, stir 1.0 hours to obtain NaO (CH2CH2O)pCH3.Then this solution is joined in reaction bulb A, stirred at rt for another 2.0 hours.At the end of reaction, add water 0.2ml, and oxolane is evaporated off obtaining from gained solution light brown to the solid of brown.This solid is joined in 100ml hexane so that the good suspension of product is in a solvent.This solid precipitation of centrifugation.Dissolve this solid precipitation with oxolane again, filter and be vacuum dried at 40 DEG C.Gained solid is processed with dilute hydrochloric acid methanol, again with methanol is cleaned twice, every time 30ml, and the light brown carrying out being vacuum dried obtaining the corresponding polycation salt of poly-[methoxyl group oligosaccharide (vinyl alcohol acid)] the dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide) gel is to the solid (670-910mg) of brown.The spectroscopic data of poly-[methoxyl group oligosaccharide (vinyl alcohol acid)] dendritic crosslinking of fullerene poly-(N-2-aminoethyl acrylamide): IR vmax(KBr) 3435 (s), 2920 (C-H), 2874 (C-H), 2835,1672 (s ,-NH-C=O), 1595 (s), 1458,1412,1371,1266,1108 (s), 1045 (br, s), 945,772,629 and 453cm-1。
Other embodiments
Understanding from the description above, those of ordinary skill in the art can know the basic feature of the present invention easily, in the case of without departing from the spirit and scope of the present invention, it is possible to the present invention carries out variations and modifications, adapts to different purposes and condition.Therefore, other embodiments also fall in the scope of the claims of the present invention.
List of references
US5,177,248,10/1991,01/1993, " forming the process of polysubstituted fullerene ".
US5,294,732,12/1992,03/1994, " polysubstituted fullerene and preparation method thereof ".
US5,416,188,02/1994,05/1995, " polysubstituted fullerene and preparation method thereof (C-2608) ".
US5,635,581,11/1994,06/1997, " fullerene polymer ".
US5,648,523,10/1995,07/1997, " as the fullerene derivate of free radical scavenger ".
US6,020,523,03/1999,04/2000, " organic poly-fullerene ".
US6,265,443,06/1997,07/2001, " by the method for carboxyl fullerene treatment neuronal damage ".
US6,380,434,04/2000,04/2002, " fullerene derivate ".
US6,777,445,10/2001,08/2004, " for prevention and the fullerene drug component for the treatment of imbalance ".
US6,790,963,07/2002,09/2004, " E-isomerism fullerene derivate ".
US6,949,660,05/2003,09/2005, " chirality (1-dioxa pyrrolin) fullerene derivate ".
US7,025,840,07/2003,04/2006, " fulminant/activity fullerene ".
US7,163,956,10/2004,01/2007, " the fullerene component of replacement and the application as antioxidant thereof ".
US7,476,375,04/2006,01/2009, " fusion fuel container and system ".
US7,511,075,06/2006,03/2009, " have the malonic acid/acetic acid C of medicative buckminsterfullerence60Three additive compounds and correlation technique ".
US7,588,824,02/2005,09/2009, " comprising the hydrogen cyanogen fullerene of proton-conductive films ".
US7,641,882,09/2003,01/2010, " fullerene structure and this structure being limited in material with carbon element ".
US7,671,230,10/2002,03/2010, " derivatization of insoluble fullerene and solubilising ".
US7,794,682,02/2006,09/2010, " fullerene restoration methods ".
US7,812,190,04/2003,10/2010, " to the derivatization of fullerene and solubilising in treatment and diagnostic application ".
US7,825,161,12/2004,11/2010, " as the high fullerene of free radical scavenger ".
US7,947,262,09/2006,05/2011, " application of the fullerene of the disease for the treatment of mastocyte and basophilic leukocyte mediation ".
US7,956,079,03/2004,07/2011, " anti-hepatitis C virus medicament and AntiHIV1 RT activity medicament ".
US8,048,275,01/2007,11/2011, " solubilization method of the carbon nanomaterial of dissolving ".
US8,058,483,02/2008,11/2011, " comprising the composition of the material coordinating the fullerene species that hydroxyl improves ".
Claims (7)
1. a polycationic polymer gelatinous mass for parents' organic poly-fullerene dendrimer crosslinking, has following knot
Structure formula:
Wherein, F is a fullerene core；P1And P2The most poly-(N-2-aminoethyl acrylamide), poly-[acrylamide-co-(N-2-
Aminoethyl acrylamide)], poly-(lysine), poly-(allylamine), poly-(Ethylenimine) or the polycation halogenide (X) of chitosan
Salt；
Each E is-N (CH2CH2OH)2、-NHCH2CH2OCH2CH2OH、-OC6H4CH2CH(NH2)CO2H、
-SCH2CH2CH2CH2CH2CH3、-CH[C(OH)(NH2)CH3]2、
-NHCH2CH2NHCH2CH2NHCH2CH2NH2、-NHCH2CH2NHCH2CH2NHCH2CH2NH2Or
-O(CH2CH2O)3 or 12-13CH3]；
Each X is individually halide anions F-、Cl-、Br-Or I-。
2. gelatinous mass as claimed in claim 1, it is characterised in that F is a C60、C70、C76、C78、C82、C84
Or C92Fullerene core.
3. gelatinous mass as claimed in claim 1, it is characterised in that n=3 to 40 and x, y and z are individually 3-100.
4. gelatinous mass as claimed in claim 1, it is characterised in that n is 4-30 and x, y and z are individually 4-70.
5. a preparation method for the polycationic polymer gelatinous mass of parents' organic poly-fullerene dendrimer crosslinking,
Wherein, F is a fullerene core；P1And P2The most poly-(N-2-aminoethyl acrylamide), poly-[acrylamide-co-(N-2-
Aminoethyl acrylamide)], poly-(lysine), poly-(allylamine), poly-(Ethylenimine) or the polycation halogenide (X) of chitosan
Salt；
Each E is-N (CH2CH2OH)2、-NHCH2CH2OCH2CH2OH、-OC6H4CH2CH(NH2)CO2H、
-SCH2CH2CH2CH2CH2CH3、-CH[C(OH)(NH2)CH3]2、
-NHCH2CH2NHCH2CH2NHCH2CH2NH2、-NHCH2CH2NHCH2CH2NHCH2CH2NH2Or
-O(CH2CH2O)3 or 12-13CH3]；
Each X is individually halide anions F-、Cl-、Br-Or I-；Described method includes:
With poly-(N-2-aminoethyl acrylamide), poly-[acrylamide-co-(N-2-aminoethyl acrylamide)], poly-(lysine),
Poly-(allylamine), poly-(Ethylenimine) or chitosan with the poly-fullerene of nitro of a nucleopilic reagent or the poly-fowler of cyclic sulfate
The contact of alkene semi-commercial (semiworks) production produces the poly-sun of the corresponding parents' fullerene dendrimer crosslinking shown in the above-mentioned structural formula quoted
Ionic polymer gel material.
6. method as claimed in claim 5, it is characterised in that: described semi-commercial (semiworks) production is a kind of poly-fullerene of nitro.
7. method as claimed in claim 5, it is characterised in that: described semi-commercial (semiworks) production is a kind of poly-fullerene of cyclic sulfate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5177248A (en) * | 1991-10-28 | 1993-01-05 | Exxon Research And Engineering Company | Process of forming polysubstituted fullerenes |
| EP0919520A2 (en) * | 1997-11-20 | 1999-06-02 | Long Y. Chiang | Fullernes substituted by several organic groups |
| JP2008115286A (en) * | 2006-11-06 | 2008-05-22 | Tokyo Institute Of Technology | Polymer membrane comprising fullerene arranged regularly |
| WO2012105872A1 (en) * | 2011-02-01 | 2012-08-09 | Rasnetsov Lev Davidovich | Homo- and hetero-polyamino-acid derivatives of fullerene с60, method for producing same, and pharmaceutical compositions based on said derivatives |
-
2013
- 2013-05-14 CN CN201310177170.2A patent/CN103450486B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5177248A (en) * | 1991-10-28 | 1993-01-05 | Exxon Research And Engineering Company | Process of forming polysubstituted fullerenes |
| US5416188A (en) * | 1991-10-28 | 1995-05-16 | Exxon Research & Engineering Co. | Polysubstituted fullerenes and their preparation (C-2608) |
| US6020523A (en) * | 1995-10-26 | 2000-02-01 | Chiang; Long Y. | Polyorganofullerenes |
| EP0919520A2 (en) * | 1997-11-20 | 1999-06-02 | Long Y. Chiang | Fullernes substituted by several organic groups |
| JP2008115286A (en) * | 2006-11-06 | 2008-05-22 | Tokyo Institute Of Technology | Polymer membrane comprising fullerene arranged regularly |
| WO2012105872A1 (en) * | 2011-02-01 | 2012-08-09 | Rasnetsov Lev Davidovich | Homo- and hetero-polyamino-acid derivatives of fullerene с60, method for producing same, and pharmaceutical compositions based on said derivatives |
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