CN106083993B - Parents' polypeptide amine dendrimer and preparation method thereof - Google Patents
Parents' polypeptide amine dendrimer and preparation method thereof Download PDFInfo
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- 239000000412 dendrimer Substances 0.000 title claims abstract description 57
- 229920000736 dendritic polymer Polymers 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000001412 amines Chemical class 0.000 title abstract description 5
- 102000004196 processed proteins & peptides Human genes 0.000 title description 4
- 108090000765 processed proteins & peptides Proteins 0.000 title description 4
- 229920001184 polypeptide Polymers 0.000 title description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001868 water Inorganic materials 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004472 Lysine Substances 0.000 claims abstract description 13
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 241000219000 Populus Species 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 11
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 238000001338 self-assembly Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 229940125904 compound 1 Drugs 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000012074 organic phase Substances 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 13
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 229940125782 compound 2 Drugs 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 229940125898 compound 5 Drugs 0.000 claims description 5
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- LYUXBTAUKJETMS-KRWDZBQOSA-N (4-nitrophenyl) (2s)-2,6-bis[(2-methylpropan-2-yl)oxycarbonylamino]hexanoate Chemical compound CC(C)(C)OC(=O)NCCCC[C@H](NC(=O)OC(C)(C)C)C(=O)OC1=CC=C([N+]([O-])=O)C=C1 LYUXBTAUKJETMS-KRWDZBQOSA-N 0.000 claims description 3
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical class CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012230 colorless oil Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 3
- -1 methoxyl group Chemical group 0.000 claims description 3
- 230000002572 peristaltic effect Effects 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 claims 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 230000006698 induction Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000008859 change Effects 0.000 abstract description 2
- 238000013270 controlled release Methods 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- 230000008288 physiological mechanism Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- ODHCTXKNWHHXJC-VKHMYHEASA-N 5-oxo-L-proline Chemical compound OC(=O)[C@@H]1CCC(=O)N1 ODHCTXKNWHHXJC-VKHMYHEASA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- 244000291564 Allium cepa Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- NCQXXVRTDHWOSP-UHFFFAOYSA-N CNC1=CN(C=C1)NC Chemical compound CNC1=CN(C=C1)NC NCQXXVRTDHWOSP-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-GSVOUGTGSA-N D-glutamic acid Chemical compound OC(=O)[C@H](N)CCC(O)=O WHUUTDBJXJRKMK-GSVOUGTGSA-N 0.000 description 1
- 102000006395 Globulins Human genes 0.000 description 1
- 108010044091 Globulins Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010353 genetic engineering Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K5/00—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof
- C07K5/02—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link
- C07K5/0215—Peptides containing up to four amino acids in a fully defined sequence; Derivatives thereof containing at least one abnormal peptide link containing natural amino acids, forming a peptide bond via their side chain functional group, e.g. epsilon-Lys, gamma-Glu
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K19/00—Hybrid peptides, i.e. peptides covalently bound to nucleic acids, or non-covalently bound protein-protein complexes
Abstract
The invention discloses the preparation methods of a kind of parents' chirality amine dendrimer.Parents' amine dendrimer is made by lysine dendrimers and alkyloxy-ethers dendrimers by esterification.Parents' dendrimers in the present invention, due to the induction of chiral structure, parents' dendrimers (MeG2-LysG3) that the poplar bundles alkyloxy-ethers in two generations and the poplar bundles lysine of three generations are constituted carry out Supramolecular Assembling in the in the mixed solvent of tetrahydrofuran and water, it can observe the spiral fiber of ordered arrangement under atomic force microscope, and pass through the algebra of the hydrophilic and hydrophobic and poplar bundles primitive that change the molecule periphery group, the assembly of different shape can be obtained, dendrimer in the present invention is not only in drug controlled release, the fields such as catalysis and intellectual material have important application prospect, it has great significance simultaneously to the various physiological mechanisms disclosed in life process.
Description
Technical field
The present invention relates to a kind of parents' chirality dendrimers and preparation method thereof.
Background technique
Parents' dendrimers are a kind of nearest novel organic synthesis high molecular materials, and such molecular structure is regular, molecule
Measure single, unimolecule scale is in Nano grade, and surface has the functional group of very high-density, while also having similar globulin
Structure has many advantages, such as good water-soluble and biodegradability, in drug release, genetic engineering, tissue repair and disease
The fields such as diagnosis play an important role, therefore parents' dendrimers have broad application prospects in field of biomedicine.
Parents' dendrimers have the structure of hydrophilic head and hydrophobic tail, it is vulnerable to hydrogen bond, Van der Waals force, electrostatic interaction, π-π heap
The driving such as product, hydrophobe and surface tension of liquid, carries out self assembly in a solvent or on interface, and obtains a series of microfacies
Structure, such as spherical, rodlike, vesica or biggish composite micelle.Percec et al. (S.Zhang, H.J.Sun,
A.D.Hughes,R.O.Moussodia,A.Bertin,Y.Chen,D.J.Pochan,P.A.Heiney,M.L.Klein,
V.Percec, PNAS., 2014,111,9058-9063) it reports parents' dendrimers injection with adhoc basis structure
Into water or buffer solution, molecule carries out self assembly and obtains the vesica of size uniformity, and the concentration by changing assembling solution, point
Son is scalably self-assembly of more bilayer vesicles of single bilayer vesicle and similar onion structure.
However when chiral primitive is introduced into parents' molecule, due to the induction of chiral structure, parents' molecule can be layered
Ground carries out self assembly to obtain the different forms such as fiber, band-like, spiral, supercoil and tubulose.Ihara and Liu Minghua et al.
A variety of chiral elements are introduced on parents' molecule based on Pidolidone or D-Glu, research finds that the chirality of chiral primitive can
Be transmitted to supermolecule nano structure (M.Takafuji, Y.Kira, H.Tsuji, S.Sawada, H.Hachisako, H.Ihara,
Tetrahedron., 2007,63,7489-7494, C.Liu, Q.Jin, K.Lv, L.Zhang, M.Liu,
.Chem.Commun.2014,50,3702-3705,Q.Jin,L.Zhang,M.Liu,Chem.-Eur.J.2013,19,9234-
9241.) organogel that is formed in DMSO of Pidolidone parents' molecule, such as in pyridine meta position replaced be capable of detecting when compared with
Strong section signal, and clearly observe under transmission electron microscope(TEM) deviously nanobelt (P.Duan, X.Zhu,
M.Liu,.Chem.Commun.2011,47,5569-5571；).
It is more about the self assembly research of parents' chiral molecules at present, and make some progress, but will be chiral
Element is introduced into parents' dendrimers, but rarely has report to study the work of chiral induction parents' dendritic macromole self assembly
Road.
Summary of the invention
One of the object of the invention is to provide a kind of chiral parents' amine dendrimer.
The second object of the present invention is to the preparation method of chirality parents' dendrimer.
The object of the invention third is that the Supramolecular Assembling of such parents' chirality dendrimer.
The present invention obtains two generations and three generations's lysine dendrimer that epipole is hydroxyl using liquid phase synthesizing method, with difference
End group and different algebra alkyloxy-ethers dendrimers carry out esterification, finally obtain parents' dendrimer.
A kind of parents' chirality dendrimers, it is characterised in that the structural formula of the dendrimers is one of following:
1.
2.
3.
4.
A method of preparing above-mentioned parents' dendrimer, it is characterised in that the specific steps of this method are as follows:
A. under ice salt bath and inert atmosphere, in lysine to the tetrahydro furan of nitro-activating ester (Boc-Lys (boc)-ONp)
It mutters in (THF), sequentially adds sodium borohydride (NaBH4) and lithium chloride (LiCl) tetrahydrofuran solution, stirring is to fully reacting；
It adds water into system until no longer bubbling, then reaction solution is washed with saturated salt solution, then organic phase is carried out
Rear solvent evaporated is dried, filtered, obtains colorless oil compound 2, structural formula through separating-purifying are as follows:
Compound 1, LiCl and the NaBH4Molar ratio are as follows: 1:5:8；
B. in ice bath, compound 2 obtained by step a is dissolved in tetrahydrofuran, and the HCl of 25wt% is added, at room temperature
Stirring stops reaction, reaction solution is washed with deionized water and DCM, and water phase liquid nitrogen frozen is finally dried, obtained to fully reacting
To its structural formula of compound as white solid 3 are as follows:
The molar ratio ratio of the HCl of the compound 2 and 25wt% are as follows: 1:20~1:30；；
C. in ice bath, compound 3 obtained by step b is dissolved in H2O and N,N-dimethylformamide (DMF) (V/V=1:2)
Then in the mixed solvent is added n,N-diisopropylethylamine (DIEA) into system, then compound 1 is slowly added dropwise into system
DMF solution, reaction to fully reacting stop reaction, and reaction solution adjusts pH to 5, then anhydrous with saturated common salt water washing 3 times
Organic phase is dried in magnesium sulfate, and solvent is spin-dried for after filtering, obtains white foam product 4, structural formula through separating-purifying
Are as follows:
The molar ratio of the compound 3, DIEA and compound 1 are as follows: 1:10:3；
D. in ice bath, compound 4 obtained by step c is dissolved in THF, the HCl of 25wt%, room are then added into system
The lower stirring of temperature stops reaction, reaction solution deionized water and DCM are washed, water phase liquid nitrogen frozen 10min, most to fully reacting
After dry, obtain compound as white solid 5, structural formula are as follows:
The molar ratio of the HCl of the compound 4 and 25wt% are as follows: 1:20~1:30；
F. in ice bath, compound 5 obtained by step d is dissolved in H2DIEA is added in the mixed solvent of O and DMF (V/V=1:2),
The DMF solution of compound 1 is slowly added dropwise into system again, until fully reacting, stops reaction, reaction solution saturated common salt water washing
3 times, and pH to 5 is adjusted, then organic phase is dried in anhydrous magnesium sulfate, and solvent is spin-dried for after filtering, it is obtained through separating-purifying white
Color solid product 6；Its structural formula are as follows:
The molar ratio of the compound 5, DIEA and compound 1 are as follows: 1:10:6；
G. the synthesis of a generation and two generation alkyloxy-ethers B (MeG1)
It is generation alkyloxy-ethers poplar bundles primitive A (MeG1-COOMe) (the reference literature Li, W. of ester group by core epipole；
Zhang,A.；The synthesis of Schl ü ter, A.D.Chem.Commun.2008,5523-5525) it is dissolved in THF and H2O (V/V=1:1)
In, a water lithium hydride (LiOH.H is then slowly added dropwise into system2O aqueous solution) is stirred at room temperature to fully reacting, reaction
After liquid saturated common salt water washing, with potassium acid sulfate tune PH to 5, after organic phase is dried in anhydrous magnesium sulfate, back spin is filtered
Dry solvent purifies to obtain colourless transparent liquid B, structural formula through column chromatography chromatogram are as follows:
The molar ratio of the compound A and Lithium hydroxide monohydrate is: 1:8~1:10.
H. under ice salt bath and inert atmosphere, in methylene chloride (DCM) solution of the compound 6 obtained by step f, successively plus
Enter compound B, 4-dimethylaminopyridine and 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride, be stirred to react to
Fully reacting, for reaction solution with saturated common salt water washing 3 times, organic phase is spin-dried for solvent after being dried, then obtains through separating-purifying
The molar ratio of white solid C, the compound B and compound 6 is 1:2~1:3, as parents' dendrimer.
The condition of parents' chirality dendrimers self assembly are as follows: by peristaltic pump to the tetrahydro furan of parents' dendrimers
It mutters and fills the water in solution, the final volume ratio of tetrahydrofuran and water is 1:20.
The parents being made of the poplar bundles lysine (MeG2-LysG3) of the poplar bundles alkyloxy-ethers in two generations and three generations
The spiral fiber of ordered arrangement can be obtained in the in the mixed solvent self assembly of water and tetrahydrofuran in chiral dendrimers.
Parents' chirality dendrimers, when the end group on alkyloxy-ethers becomes relative hydrophobic from hydrophilic methoxyl group
Ethyoxyl when, intensive short and Random fiber can be obtained in EtG2-LysG3 self assembly.
Parents' chirality dendrimers reduce the algebra of alkyloxy-ethers, and You Erdai is reduced to a generation, and MeG1-LysG3 is certainly
Assembling is also the same to form relative distribution and short and unordered fiber；
Parents' chirality dendrimers, while the algebra of alkyloxy-ethers and lysine is reduced, MeG1-LysG2 is then obtained
The more uniform nanoparticle of size.
Such macromolecular and is able to carry out supermolecule with the structure and performance of peptides dendrimers and parents' molecule
Self assembly forms the spiral fiber with regular ordered arrangement.Dendrimer in the present invention not only drug controlled release,
The fields such as catalysis and intellectual material have important application prospect, while having to the various physiological mechanisms disclosed in life process
Important meaning.
Parents' chirality dendrimers of the invention change the hydrophilic and hydrophobic and poplar bundles base of parents' dendrimers peripheral groups
The assembly of different shape can be obtained in first algebra.When the end group on alkyloxy-ethers is become from methoxyl group the ethoxy of relative hydrophobic
When base, intensive short and Random fiber is can be obtained in parents' dendrimers (EtG2-LysG3) self assembly；The algebra of alkyloxy-ethers is reduced,
Parents' dendrimers (MeG1-LysG3) self assembly similarly forms relative distribution and short and unordered fiber；But it ought drop simultaneously
The algebra of low alkyloxy-ethers and lysine, parents' dendrimers (MeG1-LysG2) self assembly then obtain diameter dimension 55~
The particle of 100nm.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the present invention is obtaining three generations's branch lysine by liquid phase synthesizing method, opposite conventional solid synthetic method yield is more
It is high；
2. parents' molecule hydrophobic part in the present invention is polypeptide dendrimers, there is good biocompatibility and biology
The advantages that degradability；
3. chiral primitive is introduced into parents' dendrimers by the present invention, chirality can be transmitted to supermolecule from small molecule and received
Rice structure.
Detailed description of the invention
Fig. 1 is the synthesis schematic diagram of LysG3.
Fig. 2 is the synthesis schematic diagram of MeG1.
Fig. 3 is the synthesis schematic diagram of MeG1-LysG3.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram (DMSO) of MeG1-LysG3.
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram (CDCl of MeG1-LysG33)。
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram (DMSO) of MeG1-LysG3.
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram (DMSO) of MeG1-LysG3.
Fig. 8 is the dynamic light scattering data of four kinds of parents' dendrimers.
Fig. 9 is the self assembly AFM figure of four kinds of parents' dendrimers.
Specific embodiment:
Embodiment 1:
The present invention relates to the preparations of MeG1-LysG3.Synthetic route refers to attached drawing Fig. 1, Fig. 2, Fig. 3, other parents' branches point
The preparation of son is referring to this preparation route.
1. the synthesis of three generations's lysine
1) synthesis of compound 2 (Boc-LysG1-OL)
Compound 1 (3.00g, 6.42mmol) is dissolved in dry THF (20mL), uses high-purity N repeatedly2Pumping-inflation
System is placed in ice salt bath cooling 30min by circulation 3 times；Then LiCl (2.18g, 51.33mmol) is sequentially added into system
And NaBH4(1.21g, 32.08mmol), uses high-purity N repeatedly again2Pumping-inflation cycle 3 times, reaction overnight.With the detection of TLC plate
Fully reacting stops reaction, adds water into system and (removes remaining NaBH until no longer bubbling4), then with saturation food
Salt water washs reaction solution, then organic phase is dried with anhydrous magnesium sulfate, and solvent evaporated after filtering chromatographs color through column
Spectrum purification obtains colorless oil compound 2 (1.86g, 87%).
2) synthesis of compound 3 (LL-OL.2HCl)
Compound 2 (1.86g, 5.59mmol) is dissolved in THF (20mL), system is placed in ice bath cooling 30min, then
25% HCl (24.48g, 167.85mmol) is added into system, stirs 1h under ice bath, removes ice bath, stir 3h at room temperature；
Fully reacting is detected with TLC plate, stops reaction, reaction solution is washed with deionized water and DCM, water phase liquid nitrogen frozen 10min, most
It is dried afterwards with freeze drier, obtains compound as white solid 3 (1.04g, 90%).
3) synthesis of compound 4 (Boc-LLG2-OL)
Compound 3 (1.04g, 5.07mmol) is dissolved in H2O (10mL) and DMF (10mL), is put into system cold in ice bath
But 20min, then into system be added DIEA (3.28g, 25.35mmol), freezing stirring 10min, by compound 1 (7.11g,
It 15.21mmol) is dissolved in DMF (30mL), then the compound 1 dissolved is slowly dropped in system, reaction overnight；With TLC
Plate detects fully reacting, stops reaction, and reaction solution is with saturated common salt water washing 3 times, and with potassium acid sulfate tune PH to 5, then it is anhydrous
Organic phase is dried in magnesium sulfate, and solvent is spin-dried for after filtering, purifies to obtain white solid product 4 through column chromatography chromatogram
(3.96g, 90%).
4) synthesis of compound 5 (LL-OL.4HCl)
By compound 4 (1g, 1.27mmol), be dissolved in THF (20mL), system be placed in ice bath cooling 30min, then to
25% HCl (5.56g, 38.02mmol) is added in system, stirs 1h under ice bath, removes ice bath, stir 3h at room temperature, with TLC
Plate detects fully reacting, stops reaction, and reaction solution is washed with deionized water and DCM, and water phase liquid nitrogen frozen 10min is finally used
Freeze drier is dried, and obtains compound as white solid 5 (0.61g, 90%).
5) synthesis of compound 6 (Boc-LysG3)
Compound 5 (0.61g, 1.14mmol) is dissolved in H2O (10mL) and DMF (10mL), is put into system cold in ice bath
But 20min, then into system be added DIEA (1.48g, 11.41mmol), freezing stirring 10min, by compound 1 (2.67g,
It 5.71mmol) is dissolved in DMF (30mL), then the compound 1 dissolved is slowly dropped in system, reaction overnight；With TLC plate
Fully reacting is detected, reaction is stopped, reaction solution is with saturated common salt water washing 3 times, and with potassium acid sulfate tune PH to 5, then anhydrous sulphur
Organic phase is dried in sour magnesium, and solvent is spin-dried for after filtering, through column chromatography chromatogram purify to obtain white solid product 6 (1.82g,
93%).
2. the synthesis of generation alkyloxy-ethers B (MeG1)
It is generation alkyloxy-ethers poplar bundles primitive A (G1-COOMe) (the reference literature Li, W. of ester group by core；Zhang,A.；
The synthesis of Schl ü ter, A.D.Chem.Commun.2008,5523-5525) it weighs 1g and is dissolved in THF (10mL) and H2O(10mL)
In, it then will be dissolved with LiOH.H2The 20mL aqueous solution of O (6.06g) is slowly in above-mentioned solution, stirring two hours to fully reacting,
After reaction solution saturated common salt water washing, with potassium acid sulfate tune PH to 5, after organic phase is dried in anhydrous magnesium sulfate, filtering
After be spin-dried for solvent, purify to obtain colourless transparent liquid A (2.89g, 76%) through column chromatography chromatogram.
3. the synthesis of compound C (MeG1-LysG3)
Weigh Compound 6 (200mg) is dissolved in dry DCM (10mL), uses high-purity N repeatedly2Pumping-inflation cycle 3 times,
System is placed in ice salt bath cooling 20min；Then compound B (214mg), 1,4- dimethylamino pyrrole are sequentially added into system
(DMAP, 4.31mg) and 1- ethyl-(3- dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl 27.36mg), again
High-purity N is used repeatedly2Pumping-inflation cycle 3 times, react 72h；Fully reacting is detected with TLC plate, stops reaction, reaction solution is used full
With brine It 3 times, then with anhydrous MgSO4Organic phase is dried, solvent is spin-dried for after filtering, is mentioned with through column chromatography chromatogram
It is pure to obtain white solid C (110mg, 40%).
Example 2:
The THF solution 100uL for taking 0.5mg/mL MeG2-LysG3, by peristaltic pump with the rate of 1.6uL/s into solution
2mL Watson distilled water is filled the water, stands three days.Solution is dialysed and removes organic solvent THF, to obtain the aqueous solution of assembly,
Solution drop is prepared into atomic force microscope (AFM) sample on mica sheet, assembles volume morphing in observation in AFM.
Claims (7)
1. a kind of parents' chirality dendrimers, it is characterised in that the structural formula of the dendrimers is one of following:
a.
b.
c.
d.
2. a kind of method for preparing parents' dendrimer according to claim 1, which is characterized in that this method it is specific
Step are as follows:
A. under ice salt bath and inert atmosphere, in lysine to the tetrahydrofuran of nitro-activating ester Boc-Lys (Boc)-ONp
(THF) in, the tetrahydrofuran solution of sodium borohydride (NaBH4) and lithium chloride (LiCl), stirring to fully reacting are sequentially added；To
It adds water to until no longer bubbling, then reaction solution is washed with saturated salt solution, then organic phase is done in system
Dry, solvent evaporated after filtering obtains colorless oil compound 2, the molar ratio of compound 1, LiCl and NaBH4 through separating-purifying
Are as follows: 1:5:8；Compound 1 is lysine to nitro-activating ester (Boc-Lys (boc)-ONp)；2 structural formula of compound are as follows:
B. in ice bath, compound 2 obtained by step a is dissolved in tetrahydrofuran, and the HCl of 25wt% is added, is stirred at room temperature
To fully reacting, stop reaction, reaction solution deionized water and methylene chloride DCM are washed, and water phase liquid nitrogen frozen is finally done
It is dry, obtain compound as white solid 3；Its structural formula of compound 3 are as follows:
The molar ratio of the HCl of the compound 2 and 25wt% are as follows: 1:20~1:30；
C. in ice bath, compound 3 obtained by step b is dissolved in water and n,N-Dimethylformamide DMF by the mixing of the volume ratio of 1:2
In solvent, n,N-diisopropylethylamine DIEA is then added into system, then be slowly added dropwise into system compound 1 DMF it is molten
Liquid, reaction to fully reacting stop reaction, and reaction solution adjusts pH to 5, then anhydrous magnesium sulfate with saturated common salt water washing 3 times
Organic phase is dried, solvent is spin-dried for after filtering, obtains white foam product 4, product 4, structural formula through separating-purifying
Are as follows:
The molar ratio of the compound 3, compound 1 and DIEA are as follows: 1:3:10；The product 4 is compound 4；
D. in ice bath, compound 4 obtained by step c is dissolved in THF, the HCl of 25wt% is then added into system, at room temperature
Stirring stops reaction, reaction solution is washed with deionized water and DCM, and water phase liquid nitrogen frozen 10min is finally done to fully reacting
It is dry, obtain compound as white solid 5,5 structural formula of compound are as follows:
The molar ratio of the HCl of the compound 4 and 25wt% are as follows: 1:20~1:30；
F. in ice bath, compound 5 obtained by step d is dissolved in water and DMF by the mixed solvent of the volume ratio of 1:2, N is added,N- bis- is different
Propylethylamine DIEA, then the DMF solution of compound 1 is slowly added dropwise into system, until fully reacting, stops reaction, reaction solution is used
Saturated common salt water washing 3 times, and pH to 5 is adjusted, then organic phase is dried in anhydrous magnesium sulfate, it is spin-dried for solvent after filtering, passes through
Separating-purifying obtains white solid product 6；
6 structural formula of product are as follows:
The product 6 is compound
6；
The molar ratio of the compound 5, DIEA and compound 1 are as follows: 1:10:6；
G. the synthesis of a generation and two generation alkyloxy-ethers B
The generation alkyloxy-ethers poplar bundles primitive A that epipole is ester group is dissolved in the mixed liquor of THF and water by the volume ratio of 1:1, institute
Stating the generation alkyloxy-ethers poplar bundles primitive A that epipole is ester group is G1-COOMe, and a water lithium hydride is then slowly added dropwise into system
Aqueous solution, stirred at room temperature to fully reacting, it is anhydrous with potassium acid sulfate tune PH to 5 after reaction solution saturated common salt water washing
After organic phase is dried in magnesium sulfate, it is spin-dried for solvent after filtering, purifies to obtain colourless transparent liquid B, institute through column chromatography chromatogram
The molar ratio for stating compound A and Lithium hydroxide monohydrate is: 1:8~1:10；
H. it under ice salt bath and inert atmosphere, in methylene chloride (DCM) solution of the compound 6 obtained by step f, sequentially adds
Colourless transparent liquid B, 4-dimethylaminopyridine and 1- ethyl-(3- dimethylaminopropyl) carbodiimide salt are obtained in step g
Hydrochlorate, colourless transparent liquid B are compound B, are stirred to react to fully reacting, reaction solution is organic with saturated common salt water washing 3 times
It is spin-dried for solvent after being mutually dried, then obtains white solid C through separating-purifying, the molar ratio of the compound B and compound 6 is
1:2~1:3, as parents' dendrimer.
3. the method for parents' dendrimer according to claim 2, the item of parents' chirality dendrimers self assembly
Part are as follows: filled the water by peristaltic pump into the tetrahydrofuran solution of parents' dendrimers, the final volume ratio of tetrahydrofuran and water is
1:20。
4. the method for parents' dendrimer according to claim 2, described by the poplar bundles alkyloxy-ethers in two generations and three generations
Parents' chirality dendrimers for constituting of poplar bundles lysine MeG2-LysG3 in the in the mixed solvent of water and tetrahydrofuran from group
Dress, can be obtained the spiral fiber of ordered arrangement.
5. the method for parents' dendrimer according to claim 2, parents' chirality dendrimers, when on alkyloxy-ethers
End group when becoming the ethyoxyl of relative hydrophobic from hydrophilic methoxyl group, EtG2-LysG3 self assembly can be obtained intensive short
And Random fiber.
6. the method for parents' dendrimer according to claim 2, parents' chirality dendrimers reduce alkyloxy-ethers
Algebra, You Erdai is reduced to a generation, and MeG1-LysG3 is self-assembly of relative distribution and short and unordered fiber.
7. the method for parents' dendrimer according to claim 2, parents' chirality dendrimers, while reducing alkane
The algebra of oxygen ether and lysine, MeG1-LysG2 then obtain diameter dimension in the particle of 55~100nm.
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