CN101274935A - Amino acid-containing palisade porphyrin compound, preparation thereof and application thereof - Google Patents
Amino acid-containing palisade porphyrin compound, preparation thereof and application thereof Download PDFInfo
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- CN101274935A CN101274935A CN 200810053134 CN200810053134A CN101274935A CN 101274935 A CN101274935 A CN 101274935A CN 200810053134 CN200810053134 CN 200810053134 CN 200810053134 A CN200810053134 A CN 200810053134A CN 101274935 A CN101274935 A CN 101274935A
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Abstract
The invention discloses palisade porphyrins containing aminoacids and the preparation method and application thereof. The formula of the porphyrins is on the right. The porphyrins of the invention can respectively bond anion, cation and neutral molecule (such as oxygen, carbonic oxide and nitric oxide), simulate ion-channel in living creature, myoglobin and hemoglobin.
Description
Technical field
The present invention relates to a kind of porphyrin compound and Preparation method and use, particularly relate to a kind of palisade porphyrin compound and preparation method thereof and purposes.
Background technology
Porphyrin and derivative thereof extensively are present in interior and relevant with the energy transfer important organelle of organism.Mainly be present in animal body in protoheme (iron porphyrin) and the keyhole limpet hemocyanin (copper porphyrin), mainly being present in plant materials in vitamin B12 (cobalt porphyrin) and the chlorophyll (magnesium porphyrin), is that animal hemocyte oxygen carrier carries out respiration and vegetable cell and carries out key substance in light and the mechanism.As the porphyrin compound of important biomolecule part, because its distinctive fragrant grand-cycle carbon skeleton structure has special advantages as host molecule.Paliform (" picket fence ") porphyrin is owing to be protected the cage cavity configuration that forms hollow all around; when axial ligand is bonded to the porphyrin ring plane; except the axial coordination effect at center; can produce extra interaction between the cage chamber that axial ligand and fence structure constituted, this additional effect can be strengthened the recognition capability of fence porphyrin system.And field such as along with the continuous development of life science, the target that now porphyrins is applied to biological enzyme simulation, phototherapy, tumour kills and wounds, molecular probe and blood substitute.Thereby the biocompatibility of reinforcement porphyrin system, improving its molecular recognition performance can be significant to the application of porphyrin system.Amino acid has good biocompatibility and specific biological function thereby we as the integral part of bioprotein and designs and synthesizes a series of porphyrin compounds with amino acid modified paliform structure, their bonding behaviors have been studied simultaneously, to simulate the function of biological intravital ionic channel and myohaemoglobin, oxyphorase to yin, yang ion and neutral molecule (as: oxygen, carbon monoxide and nitrogen protoxide).
Summary of the invention
The purpose of this invention is to provide a kind of amino acid whose palisade porphyrin compound that contains.
Second purpose of the present invention provides a kind of preparation method who contains amino acid whose palisade porphyrin compound.
The 3rd purpose of the present invention provides the purposes that contains amino acid whose palisade porphyrin compound.
Technical scheme of the present invention is summarized as follows:
A kind ofly contain amino acid whose palisade porphyrin compound, have following general formula (I):
Wherein: M represents zinc, nickel, manganese, lanthanum, cerium, lutetium, thulium, praseodymium, neodymium, samarium, ytterbium, copper, iron, zirconium, europium, cadmium, ruthenium, magnesium, cobalt or hydrogen atom;
R represents the residue of glycine, L-Ala, Xie Ansuan, leucine, Isoleucine, methionine(Met), proline(Pro), phenylalanine, tryptophane, Serine, Threonine, halfcystine, l-asparagine, glutamine, tyrosine, aspartic acid, L-glutamic acid, Methionin, arginine or Histidine.
A kind of preparation method who contains amino acid whose palisade porphyrin compound comprises the steps:
Get the amino acid of tertbutyloxycarbonyl protection; add dimethyl formamide; methylene dichloride; trichloromethane; ethylene dichloride; tetrahydrofuran (THF) or acetic acid ethyl dissolution; add carbodiimide type condensing agent at-10 ℃～5 ℃; add 5; 10; 15; 20-four-(α; α, α, α-adjacent aminophenyl) porphyrin and 4-Dimethylamino pyridine or N-oxy-compound; 10 ℃～40 ℃ were stirred 1～15 day; filter, filtrate is used aqueous hydrochloric acid successively with methylene dichloride or trichloromethane dilution; water; the sodium bicarbonate aqueous solution washing; anhydrous sodium sulphate or dried over mgso; remove by filter siccative, boil off the solid that solvent obtains and carry out separation and purification with the method for column chromatography or high performance liquid chromatography, obtaining M is a kind of palisade porphyrin compound of hydrogen.
Amino acid, the carbodiimide type condensing agent, 5 of described tertbutyloxycarbonyl protection; 10; 15; 20-four-(α; α; α, α-adjacent aminophenyl) mol ratio of porphyrin and 4-Dimethylamino pyridine or N-oxy-compound is 4～12: 4～15: 1: 0.4～1.5, the add-on of described dimethyl formamide, methylene dichloride, trichloromethane, ethylene dichloride, tetrahydrofuran (THF) or ethyl acetate be described tertbutyloxycarbonyl protection amino acid masses 1-10 doubly.
A kind of preparation method who contains amino acid whose palisade porphyrin compound comprises the steps:
(1) gets the amino acid that tertbutyloxycarbonyl is protected, add dimethyl formamide, methylene dichloride, trichloromethane, ethylene dichloride, tetrahydrofuran (THF) or acetic acid ethyl dissolution, add carbodiimide type condensing agent at-10 ℃～5 ℃, add 5,10,15,20-four-(α, α, α, α-adjacent aminophenyl) porphyrin and 4-Dimethylamino pyridine or N-oxy-compound, 10 ℃～40 ℃ were stirred 1～15 day, filter, filtrate is used aqueous hydrochloric acid successively with methylene dichloride or trichloromethane dilution, water, the sodium bicarbonate aqueous solution washing, anhydrous sodium sulphate or dried over mgso, remove by filter siccative, boil off the solid that solvent obtains and carry out separation and purification with the method for column chromatography or high performance liquid chromatography, obtaining M is a kind of palisade porphyrin compound of hydrogen;
(2) get a kind of palisade porphyrin compound that M is a hydrogen; adding M is a kind of palisade porphyrin compound quality 1-10 exsiccant methylene dichloride or trichloromethane or the tetrahydrofuran (THF) or dimethyl formamide dissolving doubly of hydrogen; add metal halide or metal acetate salt and 2; the 6-lutidine; stirring at room or reflux are 1～5 hour under nitrogen protection; the pressure reducing and steaming solvent; adding trichloromethane makes it to dissolve again; wash with water; anhydrous sodium sulfate drying; remove by filter sodium sulfate; after boiling off solvent; obtain the palisade porphyrin compound that a kind of M is a metal, described M is a kind of palisade porphyrin compound of hydrogen; metal halide or metal acetate salt and 2, the mol ratio of 6-lutidine are 1: 5～10: 0～1.
Amino acid, the carbodiimide type condensing agent, 5 of the protection of tertbutyloxycarbonyl described in the described step (1); 10; 15; 20-four-(α; α; α, α-adjacent aminophenyl) porphyrin and-mol ratio of Dimethylamino pyridine or N-oxy-compound is 4～12: 4～15: 1: 0.4～1.5, the add-on of described dimethyl formamide, methylene dichloride, trichloromethane, ethylene dichloride, tetrahydrofuran (THF) or ethyl acetate be described tertbutyloxycarbonyl protection amino acid whose quality 1-10 doubly.
Described carbodiimide type condensing agent is preferred: N, N-dicyclohexylcarbodiimide, DIC or N-dimethylamino-propyl-N-ethyl carbodiimide.
Described N-oxy-compound is preferred: 1-hydroxy benzo triazole, N-hydroxy-succinamide, 1-hydroxyl-7-azo benzotriazole or N-hydroxyl-5-norborneol are rare-2, the 3-imide.
Amino acid in the amino acid of described tertbutyloxycarbonyl protection is glycine, L-Ala, Xie Ansuan, leucine, Isoleucine, methionine(Met), proline(Pro), phenylalanine, tryptophane, Serine, Threonine, halfcystine, l-asparagine, glutamine, tyrosine, aspartic acid, L-glutamic acid, Methionin, arginine, Histidine.
Described metal halide is an iron protochloride, magnesium chloride, Manganous chloride tetrahydrate, zinc chloride, Lanthanum trichloride, Cerium II Chloride, lutecium chloride, praseodymium chloride, Neodymium trichloride, Europium trichloride, cobalt chloride, samarium trichloride, ruthenium chloride, Cadmium chloride fine powder, zirconium chloride, Ytterbium trichloride, thulium chloride, nickelous chloride, ferrous bromide, magnesium bromide, cupric bromide, Manganese dibromide, zinc bromide, lanthanum bromide, comprise cerium bromide, the bromination lutetium, praseodymium bromide, neodymium bromide, the bromination europium, cobaltous bromide, samaric bromide, cadmium bromide, ytterbium bromide, nickelous bromide or bromination thulium.
Described metal acetate salt is Iron diacetate, neutralized verdigris, lanthanum acetate, cerous acetate, acetic acid lutetium, acetic acid ytterbium, praseodymium acetate, acetic acid neodymium, acetic acid europium, acetic acid thulium, acetic acid samarium, manganese acetate, zinc acetate, Cobaltous diacetate, nickel acetate, cadmium acetate or acetic acid zirconium.
What have a general formula (I) a kind ofly contains the purposes that amino acid whose palisade porphyrin compound is simulated biological intravital ionic channel, myohaemoglobin or oxyphorase.
A kind ofly contain the purposes that amino acid whose palisade porphyrin compound is simulated biological intravital ionic channel, myohaemoglobin or oxyphorase.
Advantage of the present invention is:
Compound of the present invention can carry out bonding to yin, yang ion and neutral molecule (as: oxygen, carbon monoxide and nitrogen protoxide) respectively, simulate biological intravital ionic channel and myohaemoglobin, oxyphorase, therefore a kind of amino acid whose paliform (Picket-fence) porphyrin compound that contains of the present invention has remarkable advantages than the porphyrin compound of other models, structure of the present invention is as a kind of novel " picket fence " porphyrin model, because its amino acid fence is a chiral molecules, so have extensive studies and application value.
Description of drawings
Fig. 1 is the mass spectrum of the compound of embodiment 1 preparation;
Fig. 2 is the mass spectrum of the compound of embodiment 2 preparations;
The mass spectrum of the compound of Fig. 3 embodiment 3 preparations;
The mass spectrum of the compound of Fig. 4 embodiment 4 preparations;
The mass spectrum of the compound of Fig. 5 embodiment 5 preparations;
Fig. 6 is the uv absorption spectra of the compound of embodiment 7-embodiment 11 preparations;
Fig. 7 is a kind of amino acid whose palisade porphyrin compound and interactional uv absorption spectra of chlorion of containing of hydrogen for M of the present invention;
Fig. 8 is a kind of amino acid whose palisade porphyrin compound and interactional fluorescence emission spectrogram of chlorion of containing of metal for M of the present invention;
Fig. 9 is that metal a kind of contained amino acid whose palisade porphyrin compound and oxygen, carbon monoxide, the interactional uv absorption spectra of nitric oxide gas body for M of the present invention.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Contain the preparation of the palisade porphyrin compound of glycine:
The glycine of getting the tertbutyloxycarbonyl protection is in a container, and the exsiccant methylene dichloride dissolving that the quality of the glycine of adding tertbutyloxycarbonyl protection is 1 times is at 0 ℃; add N, the N-dicyclohexylcarbodiimide was reacted 0.1 hour; add 5,10,15; 20-four-(α, α, α; α-adjacent aminophenyl) porphyrin and 4-Dimethylamino pyridine; 25 ℃ were stirred 1 day, filtered, and filtrate is diluted with methylene dichloride; use aqueous hydrochloric acid successively; water; the sodium bicarbonate aqueous solution washing; anhydrous sodium sulfate drying removes by filter siccative, boils off solvent; silica gel column chromatography; with volume ratio is 10: 10 methylene dichloride and ether wash-out, collects main colour band, and obtaining black purple solid is that M is a kind of palisade porphyrin compound of hydrogen; the glycine of described tertbutyloxycarbonyl protection; N; the N-dicyclohexylcarbodiimide; 5,10,15; 20-four-(α; α, α, α-adjacent aminophenyl) mol ratio of porphyrin and 4-Dimethylamino pyridine is 4: 4: 1: 0.4.The mass spectrum of present embodiment compound is seen Fig. 1.
To concentration is 1 * 10
-5Dripping concentration in the tetrahydrofuran solution of the compound of the present embodiment preparation of mol/L is 1 * 10
-3The tetrahydrofuran solution of the tetrabutylammonium chloride of mol/L is observed the variation of ultra-violet absorption spectrum, sees Fig. 7.
As can be seen from Figure 7, the compound of present embodiment preparation has recognition reaction to chlorion.
Embodiment 2
Contain the preparation of the palisade porphyrin compound of L-Ala:
The L-Ala of getting the tertbutyloxycarbonyl protection is in a container, and the exsiccant trichloromethane dissolving that the quality of the L-Ala of adding tertbutyloxycarbonyl protection is 3 times adds DIC at 5 ℃; reacted 0.5 hour; add 5,10,15; 20-four-(α; α, α, α-adjacent aminophenyl) porphyrin and 1-hydroxy benzo triazole; 25 ℃ were stirred 2 days; filter, filtrate is diluted with trichloromethane, uses aqueous hydrochloric acid successively; water; the sodium bicarbonate aqueous solution washing; anhydrous magnesium sulfate drying; remove by filter siccative, boil off solvent, silica gel column chromatography; with volume ratio 3: 1 methylene dichloride and ether wash-out; collect main colour band, obtaining black purple solid is that M is a kind of palisade porphyrin compound of hydrogen, the L-Ala of described tertbutyloxycarbonyl protection; DIC; 5; 10; 15,20-four-(α, α; α, α-adjacent aminophenyl) mol ratio of porphyrin and 1-hydroxy benzo triazole is 6: 7: 1: 0.7.The mass spectrum of present embodiment compound is seen Fig. 2.
Contain the preparation of the palisade porphyrin compound of Xie Ansuan:
The Xie Ansuan of getting the tertbutyloxycarbonyl protection is in a container, and the exsiccant tetrahydrofuran (THF) dissolving that the quality of the Xie Ansuan of adding tertbutyloxycarbonyl protection is 5 times adds N-dimethylamino-propyl-N-ethyl carbodiimide down at-2 ℃; react after 0.6 hour; add 5,10,15; 20-four-(α; α, α, α-adjacent aminophenyl) porphyrin and N-hydroxy-succinamide; 30 ℃ were stirred 3 days; filter, filtrate is diluted with trichloromethane, uses aqueous hydrochloric acid successively; water; the sodium bicarbonate aqueous solution washing; anhydrous magnesium sulfate drying; remove by filter siccative, boil off solvent, silica gel column chromatography; with volume ratio 4: 1 methylene dichloride and ether wash-out; collect main colour band, obtaining black purple solid is that M is a kind of palisade porphyrin compound of hydrogen, the Xie Ansuan of described tertbutyloxycarbonyl protection; N-dimethylamino-propyl-N-ethyl carbodiimide; 5; 10; 15,20-four-(α, α; α, α-adjacent aminophenyl) mol ratio of porphyrin and N-hydroxy-succinamide is 6: 7: 1: 0.7.The mass spectrum of present embodiment compound is seen Fig. 3.
Contain the preparation of the palisade porphyrin compound of Isoleucine:
The Isoleucine of getting the tertbutyloxycarbonyl protection is in a container, and the exsiccant dimethyl formamide dissolving that the quality of the Isoleucine of adding tertbutyloxycarbonyl protection is 4 times adds N at-5 ℃; the N-dicyclohexylcarbodiimide was reacted after 0.5 hour, added 5; 10,15,20-four-(α; α; α, α-adjacent aminophenyl) porphyrin and 1-hydroxyl-7-azo benzotriazole, 40 ℃ were stirred 1 day; filter; filtrate is diluted with methylene dichloride, uses aqueous hydrochloric acid successively; water; the sodium bicarbonate aqueous solution washing, anhydrous sodium sulfate drying; remove by filter siccative; boil off solvent, silica gel column chromatography is 5: 1 methylene dichloride and ether wash-out with volume ratio; collect main colour band; obtaining black purple solid is that M is a kind of palisade porphyrin compound of hydrogen, the Isoleucine of described tertbutyloxycarbonyl protection; N, the N-dicyclohexylcarbodiimide; 5; 10; 15,20-four-(α, α; α, α-adjacent aminophenyl) mol ratio of porphyrin and 1-hydroxyl-7-azo benzotriazole is 10: 12: 1: 1.2.The mass spectrum of present embodiment compound is seen Fig. 4.
Contain the preparation of the palisade porphyrin compound of phenylalanine:
The phenylalanine of getting the tertbutyloxycarbonyl protection is in a container, and the exsiccant ethylene dichloride dissolving that the quality of the phenylalanine of adding tertbutyloxycarbonyl protection is 4 times adds N at 0 ℃; the N-dicyclohexylcarbodiimide was reacted after 0.5 hour, added 5; 10,15,20-four-(α; α, α, α-adjacent aminophenyl) porphyrin and N-hydroxyl-5-norborneol rare-2; the 3-imide, 10 ℃ were stirred 15 days, filtered; filtrate is diluted with trichloromethane; use aqueous hydrochloric acid successively; water; the sodium bicarbonate aqueous solution washing, anhydrous magnesium sulfate drying removes by filter siccative; boil off solvent; silica gel column chromatography is 6: 1 methylene dichloride and an ether wash-out with volume ratio, collects main colour band; obtaining black purple solid is that M is a kind of palisade porphyrin compound of hydrogen; the phenylalanine of described tertbutyloxycarbonyl protection; N, the N-dicyclohexylcarbodiimide; 5,10; 15; 20-four-(α, α, α; α-adjacent aminophenyl) porphyrin and N-hydroxyl-5-norborneol are rare-2, and the mol ratio of 3-imide is 12: 15: 1: 1.5.The mass spectrum of present embodiment compound is seen Fig. 5.
Embodiment 6
Contain the preparation of the palisade porphyrin compound of tryptophane:
The tryptophane of getting the tertbutyloxycarbonyl protection is in a container, and the exsiccant acetic acid ethyl dissolution that the quality of the tryptophane of adding tertbutyloxycarbonyl protection is 10 times adds N at-10 ℃; the N-dicyclohexylcarbodiimide; react after 0.5 hour, add 5,10; 15; 20-four-(α, α, α; α-adjacent aminophenyl) porphyrin and 4-Dimethylamino pyridine; 25 ℃ were stirred 13 days, filtered, and filtrate is diluted with methylene dichloride; use aqueous hydrochloric acid successively; water; the sodium bicarbonate aqueous solution washing; anhydrous sodium sulfate drying removes by filter siccative, boils off solvent; use high-efficient liquid phase chromatogram purification; obtaining black purple solid is that M is a kind of palisade porphyrin compound of hydrogen, the tryptophane of described tertbutyloxycarbonyl protection; N, the N-dicyclohexylcarbodiimide; 5; 10; 15,20-four-(α, α; α, α-adjacent aminophenyl) mol ratio of porphyrin and 4-Dimethylamino pyridine is 6: 6: 1: 0.6.
Embodiment 7
A kind of M is the preparation of the palisade porphyrin compound that contains glycine of iron, comprises the steps:
(1) with embodiment 1;
(2) get the compound that step (1) obtains; the exsiccant methylene dichloride dissolving that adds 1 times of this compound quality; add iron protochloride and 2; the 6-lutidine; reflux is 1 hour under nitrogen protection, and the pressure reducing and steaming solvent adds trichloromethane and makes it to dissolve again; wash with water; anhydrous sodium sulfate drying removes by filter sodium sulfate, boil off solvent after; silica gel column chromatography; it with volume ratio 15: 3: 1 chloroform; acetone and methanol-eluted fractions are collected main colour band, and obtaining M is the palisade porphyrin compound that contains glycine of iron; the compound that described step (1) obtains; iron protochloride and 2, the mol ratio of 6-lutidine are 1: 5: 0.5.The uv absorption spectra of present embodiment compound is seen Fig. 6.
A kind of M is the preparation method of the palisade porphyrin compound that contains glycine of zinc, comprises the steps:
(1) with embodiment 1;
(2) get the compound that step (1) obtains, add the exsiccant trichloromethane dissolving of 2 times of this compound qualities, add zinc acetate, stirring at room 2 hours, the pressure reducing and steaming solvent, add chloroform and make it to dissolve again, wash anhydrous sodium sulfate drying with water, remove by filter sodium sulfate, after boiling off solvent, obtaining a kind of M is the palisade porphyrin compound that contains glycine of zinc, and compound and zinc acetate mol ratio that described step (1) obtains are 1: 5.The uv absorption spectra of present embodiment compound is seen Fig. 6.
Embodiment 9
A kind of M is the preparation method of the palisade porphyrin compound that contains glycine of copper, comprises the steps:
(1) with embodiment 1;
(2) get the compound that step (1) obtains; the exsiccant methylene dichloride dissolving that adds 3 times of this compound qualities; add cupric bromide, reflux is 2 hours under nitrogen protection, the pressure reducing and steaming solvent; adding chloroform makes it to dissolve again; wash with water, anhydrous sodium sulfate drying removes by filter sodium sulfate; obtain the palisade porphyrin compound that contains glycine that a kind of M is a copper after boiling off solvent, the compound that described step (1) obtains, the mol ratio of cupric bromide are 1: 10.The uv absorption spectra of present embodiment compound is seen Fig. 6.
A kind of M is the preparation method of the palisade porphyrin compound that contains glycine of manganese, comprises the steps:
(1) with embodiment 1;
(2) get the compound that step (1) obtains, the exsiccant trichloromethane dissolving that adds 5 times of this compound qualities, add manganese acetate, stirring at room 2 hours, pressure reducing and steaming solvent, adding chloroform makes it to dissolve again, wash with water, anhydrous sodium sulfate drying removes by filter sodium sulfate, obtain the palisade porphyrin compound that contains glycine that a kind of M is a manganese after boiling off solvent, the compound that described step (1) obtains and the mol ratio of manganese acetate are 1: 8.The uv absorption spectra of present embodiment compound is seen Fig. 6.
Embodiment 11
A kind of M is the preparation method of the palisade porphyrin compound that contains glycine of nickel, comprises the steps:
(1) with embodiment 1;
(2) get the compound that step (1) obtains, the exsiccant trichloromethane dissolving that adds 5 times of this compound qualities, add nickel acetate, stirring at room 5 hours, pressure reducing and steaming solvent, adding chloroform makes it to dissolve again, wash with water, anhydrous sodium sulfate drying removes by filter sodium sulfate, obtain the palisade porphyrin compound that contains glycine that a kind of M is a nickel after boiling off solvent, the compound that described step (1) obtains is 1: 10 with the mol ratio of, nickel acetate.The uv absorption spectra of present embodiment compound is seen Fig. 6.
Embodiment 12
A kind of M is the preparation method of the palisade porphyrin compound that contains Xie Ansuan of iron, comprises the steps:
(1) with embodiment 3;
(2) get the compound that step (1) obtains; the exsiccant tetrahydrofuran (THF) dissolving that adds 2 times of this compound qualities; add iron protochloride and 2; the 6-lutidine; reflux is 2 hours under nitrogen protection, and the pressure reducing and steaming solvent adds chloroform and makes it to dissolve again; wash with water; anhydrous sodium sulfate drying removes by filter sodium sulfate, boil off solvent after; silica gel column chromatography; it with volume ratio 15: 3: 1 chloroform; acetone and methanol-eluted fractions are collected main colour band, and obtaining M is the palisade porphyrin compound that contains Xie Ansuan of iron; the compound that described step (1) obtains; iron protochloride and 2, the mol ratio of 6-lutidine are 1: 10: 1.
Embodiment 13
A kind of M is the preparation method of the palisade porphyrin compound that contains glycine of cobalt, comprises the steps:
(1) with embodiment 1;
(2) get the compound that step (1) obtains; the exsiccant tetrahydrofuran (THF) dissolving that adds 10 times of this compound qualities; add cobalt chloride and 2; the 6-lutidine; reflux is 5 hours under nitrogen protection, and the pressure reducing and steaming solvent adds chloroform and makes it to dissolve again; wash with water; anhydrous sodium sulfate drying removes by filter sodium sulfate, boil off solvent after; silica gel column chromatography; it with volume ratio 15: 3: 1 chloroform; acetone and methanol-eluted fractions are collected main colour band, and obtaining M is the palisade porphyrin compound that contains glycine of cobalt; the compound that described step (1) obtains; cobalt chloride and 2, the mol ratio of 6-lutidine are 1: 10: 1.
Embodiment 14
A kind of M is the preparation method of the palisade porphyrin compound that contains L-Ala of magnesium, comprises the steps:
(1) with embodiment 2;
(2) get the compound that step (1) obtains; add the exsiccant trichloromethane dissolving of 10 times of this compound qualities, add magnesium chloride, reflux is 5 hours under nitrogen protection; the pressure reducing and steaming solvent; add chloroform and make it to dissolve again, wash anhydrous sodium sulfate drying with water; remove by filter sodium sulfate; after boiling off solvent, obtain the palisade porphyrin compound that M is a magnesium, compound and magnesium chloride mol ratio that described step (1) obtains are 1: 10.
A kind of M is the preparation method of the palisade porphyrin compound that contains proline(Pro) of zirconium, comprises the steps:
(1) gets the proline(Pro) that tertbutyloxycarbonyl is protected, the exsiccant methylene dichloride dissolving that the quality of the proline(Pro) of adding tertbutyloxycarbonyl protection is 10 times, adding N under-10 ℃, the N-dicyclohexylcarbodiimide was reacted 1 hour, added 5,10,15,20-four-(α, α, α, α-adjacent aminophenyl) porphyrin and 4-Dimethylamino pyridine, 40 ℃ were stirred 5 days down, filter, boil off solvent, silica gel column chromatography is 10: 1 methylene dichloride and ether wash-out with volume ratio, collect main colour band, obtaining black purple solid is that M is a kind of palisade porphyrin compound of hydrogen, the proline(Pro) of described tertbutyloxycarbonyl protection, N, the N-dicyclohexylcarbodiimide, 5,10,15,20-four-(α, α, α, α-adjacent aminophenyl) mol ratio of porphyrin and 4-Dimethylamino pyridine is 6: 7: 1: 0.7;
(2) get the compound that step (1) obtains; the exsiccant tetrahydrofuran (THF) dissolving that adds 4 times of this compound qualities; add zirconium chloride and 2; the 6-lutidine; reflux is 5 hours under nitrogen protection; the pressure reducing and steaming solvent; adding chloroform makes it to dissolve again; wash with water, anhydrous sodium sulfate drying removes by filter sodium sulfate; after boiling off solvent; obtaining M is the palisade porphyrin compound that contains proline(Pro) of zirconium, compound, zirconium chloride and 2 that described step (1) obtains, and the mol ratio of 6-lutidine is 1: 10: 0.5.
If can form new embodiment with the zirconium chloride that ferrous bromide, ruthenium chloride, acetic acid zirconium or Iron diacetate substitute in the present embodiment, make corresponding palisade porphyrin compound.
Embodiment 16
A kind of M is the preparation method of the palisade porphyrin compound that contains methionine(Met) of europium, comprises the steps:
(1) gets the methionine(Met) that tertbutyloxycarbonyl is protected, the exsiccant methylene dichloride dissolving that the quality of the methionine(Met) of adding tertbutyloxycarbonyl protection is 5 times, adding N under 5 ℃, the N-dicyclohexylcarbodiimide was reacted 1 hour, added 5,10,15,20-four-(α, α, α, α-adjacent aminophenyl) porphyrin and 4-Dimethylamino pyridine, 25 ℃ were stirred 5 days down, filter, boil off solvent, silica gel column chromatography is 8: 1 methylene dichloride and ether wash-out with volume ratio, collect main colour band, obtaining black purple solid is that M is a kind of palisade porphyrin compound of hydrogen, the methionine(Met) of described tertbutyloxycarbonyl protection, N, the N-dicyclohexylcarbodiimide, 5,10,15,20-four-(α, α, α, α-adjacent aminophenyl) mol ratio of porphyrin and 4-Dimethylamino pyridine is 6: 7: 1: 0.7;
(2) get the compound that step (1) obtains; add the exsiccant tetrahydrofuran (THF) dissolving of 3 times of this compound qualities, add Europium trichloride, reflux is 5 hours under nitrogen protection; the pressure reducing and steaming solvent; add chloroform and make it to dissolve again, wash anhydrous sodium sulfate drying with water; remove by filter sodium sulfate; after boiling off solvent, obtaining M is the palisade porphyrin compound that contains methionine(Met) of europium, and the compound that described step (1) obtains, the mol ratio of Europium trichloride are 1: 10.
If, can make corresponding palisade porphyrin compound with the alternative methionine(Met) in the present embodiment of leucine, tryptophane, Serine, Threonine, halfcystine, l-asparagine, glutamine, tyrosine, aspartic acid, L-glutamic acid, Methionin, arginine or the Histidine of tertbutyloxycarbonyl protection.
If use Lanthanum trichloride, Cerium II Chloride, lutecium chloride, praseodymium chloride, Neodymium trichloride, samarium trichloride, Cadmium chloride fine powder, Ytterbium trichloride, thulium chloride, nickelous chloride, magnesium bromide, Manganese dibromide, zinc bromide, lanthanum bromide, comprise cerium bromide, the bromination lutetium, praseodymium bromide, neodymium bromide, the bromination europium, cobaltous bromide, samaric bromide, cadmium bromide, ytterbium bromide, nickelous bromide, the bromination thulium, neutralized verdigris, lanthanum acetate, cerous acetate, the acetic acid lutetium, the acetic acid ytterbium, praseodymium acetate, the acetic acid neodymium, the acetic acid europium, the acetic acid thulium, the acetic acid samarium, Cobaltous diacetate, Europium trichloride in cadmium acetate or the alternative present embodiment is formed new embodiment, makes corresponding palisade porphyrin compound.
Embodiment 17
To concentration is 1 * 10
-5Dripping concentration in the dichloromethane solution of the compound of embodiment 7 preparations of mol/L is 1 * 10
-3The dichloromethane solution of the tetrabutylammonium chloride of mol/L is observed the variation of fluorescence emission spectrogram, sees Fig. 8.
As can be seen from Figure 8, the compound of the present invention's preparation has recognition reaction to chlorion.
Embodiment 18
To concentration is 1 * 10
-5Add saturated hypo solution in the toluene solution of the compound of embodiment 12 preparations of mol/L, make ferric ion be reduced into ferrous ion, get three parts, respectively aerating oxygen, carbon monoxide and nitric oxide gas, observe the variation of ultra-violet absorption spectrum, see Fig. 9.
As can be seen from Figure 9, the compound of present embodiment preparation has recognition reaction to oxygen and carbon monoxide and nitric oxide gas.Show that compound of the present invention has oxygen carrier, year carbon monoxide of simulation myohaemoglobin and oxyphorase and carries nitric oxide production ability.
Claims (10)
1. one kind contains amino acid whose palisade porphyrin compound, it is characterized in that having following general formula (I):
Wherein: M represents zinc, nickel, manganese, lanthanum, cerium, lutetium, thulium, praseodymium, neodymium, samarium, ytterbium, copper, iron, zirconium, europium, cadmium, ruthenium, magnesium, cobalt or hydrogen atom;
R represents the residue of glycine, L-Ala, Xie Ansuan, leucine, Isoleucine, methionine(Met), proline(Pro), phenylalanine, tryptophane, Serine, Threonine, halfcystine, l-asparagine, glutamine, tyrosine, aspartic acid, L-glutamic acid, Methionin, arginine or Histidine.
2. the described a kind of preparation method who contains amino acid whose palisade porphyrin compound of claim 1, its feature comprises the steps:
Get the amino acid of tertbutyloxycarbonyl protection; add dimethyl formamide; methylene dichloride; trichloromethane; ethylene dichloride; tetrahydrofuran (THF) or acetic acid ethyl dissolution; add carbodiimide type condensing agent at-10 ℃～5 ℃; add 5; 10; 15; 20-four-(α; α, α, α-adjacent aminophenyl) porphyrin and 4-Dimethylamino pyridine or N-oxy-compound; 10 ℃～40 ℃ were stirred 1～15 day; filter, filtrate is used aqueous hydrochloric acid successively with methylene dichloride or trichloromethane dilution; water; the sodium bicarbonate aqueous solution washing; anhydrous sodium sulphate or dried over mgso; remove by filter siccative, boil off the solid that solvent obtains and carry out separation and purification with the method for column chromatography or high performance liquid chromatography, obtaining M is a kind of palisade porphyrin compound of hydrogen.
3. a kind of preparation method who contains amino acid whose palisade porphyrin compound according to claim 2; the amino acid that it is characterized in that described tertbutyloxycarbonyl protection; carbodiimide type condensing agent; 5; 10; 15; 20-four-(α; α; α; α-adjacent aminophenyl) mol ratio of porphyrin and 4-Dimethylamino pyridine or N-oxy-compound is 4～12: 4～15: 1: 0.4～1.5, and described dimethyl formamide; methylene dichloride; trichloromethane; ethylene dichloride; the add-on of tetrahydrofuran (THF) or ethyl acetate be the protection of described tertbutyloxycarbonyl amino acid masses 1-10 doubly.
4. the described a kind of preparation method who contains amino acid whose palisade porphyrin compound of claim 1, its feature comprises the steps:
(1) gets the amino acid that tertbutyloxycarbonyl is protected, add dimethyl formamide, methylene dichloride, trichloromethane, ethylene dichloride, tetrahydrofuran (THF) or acetic acid ethyl dissolution, add carbodiimide type condensing agent at-10 ℃～5 ℃, add 5,10,15,20-four-(α, α, α, α-adjacent aminophenyl) porphyrin and 4-Dimethylamino pyridine or N-oxy-compound, 10 ℃～40 ℃ were stirred 1～15 day, filter, filtrate is used aqueous hydrochloric acid successively with methylene dichloride or trichloromethane dilution, water, the sodium bicarbonate aqueous solution washing, anhydrous sodium sulphate or dried over mgso, remove by filter siccative, boil off the solid that solvent obtains and carry out separation and purification with the method for column chromatography or high performance liquid chromatography, obtaining M is a kind of palisade porphyrin compound of hydrogen;
(2) get a kind of palisade porphyrin compound that M is a hydrogen; adding M is a kind of palisade porphyrin compound quality 1-10 exsiccant methylene dichloride or trichloromethane or the tetrahydrofuran (THF) or dimethyl formamide dissolving doubly of hydrogen; add metal halide or metal acetate salt and 2; the 6-lutidine; stirring at room or reflux are 1～5 hour under nitrogen protection; the pressure reducing and steaming solvent; adding trichloromethane makes it to dissolve again; wash with water; anhydrous sodium sulfate drying; remove by filter sodium sulfate; after boiling off solvent; obtain the palisade porphyrin compound that a kind of M is a metal, described M is a kind of palisade porphyrin compound of hydrogen; metal halide or metal acetate salt and 2, the mol ratio of 6-lutidine are 1: 5～10: 0～1.
5. according to wanting the sharp 4 described a kind of preparation methods that contain amino acid whose palisade porphyrin compound that require; the amino acid that it is characterized in that the protection of tertbutyloxycarbonyl described in the described step (1); carbodiimide type condensing agent; 5; 10; 15; 20-four-(α; α; α; α-adjacent aminophenyl) mol ratio of porphyrin and 4-Dimethylamino pyridine or N-oxy-compound is 4～12: 4～15: 1: 0.4～1.5, and described dimethyl formamide; methylene dichloride; trichloromethane; ethylene dichloride; the add-on of tetrahydrofuran (THF) or ethyl acetate be the protection of described tertbutyloxycarbonyl amino acid whose quality 1-10 doubly.
6. according to a kind of preparation method who contains amino acid whose palisade porphyrin compound of one of claim 2-5, it is characterized in that described carbodiimide type condensing agent is N, N-dicyclohexylcarbodiimide, DIC or N-dimethylamino-propyl-N-ethyl carbodiimide, described N-oxy-compound is that 1-hydroxy benzo triazole, N-hydroxy-succinamide, 1-hydroxyl-7-azo benzotriazole or N-hydroxyl-5-norborneol are rare-2, the 3-imide.
7. according to a kind of preparation method who contains amino acid whose palisade porphyrin compound of one of right 2-5, it is characterized in that the amino acid in the amino acid of described tertbutyloxycarbonyl protection is glycine, L-Ala, Xie Ansuan, leucine, Isoleucine, methionine(Met), proline(Pro), phenylalanine, tryptophane, Serine, Threonine, halfcystine, l-asparagine, glutamine, tyrosine, aspartic acid, L-glutamic acid, Methionin, arginine, Histidine.
8. a kind of preparation method who contains amino acid whose palisade porphyrin compound according to claim 4 is characterized in that described metal halide is an iron protochloride, magnesium chloride, Manganous chloride tetrahydrate, zinc chloride, Lanthanum trichloride, Cerium II Chloride, lutecium chloride, praseodymium chloride, Neodymium trichloride, Europium trichloride, cobalt chloride, samarium trichloride, ruthenium chloride, Cadmium chloride fine powder, zirconium chloride, Ytterbium trichloride, thulium chloride, nickelous chloride, ferrous bromide, magnesium bromide, cupric bromide, Manganese dibromide, zinc bromide, lanthanum bromide, comprise cerium bromide, the bromination lutetium, praseodymium bromide, neodymium bromide, the bromination europium, cobaltous bromide, samaric bromide, cadmium bromide, ytterbium bromide, nickelous bromide or bromination thulium.
9. a kind of preparation method who contains amino acid whose palisade porphyrin compound according to claim 4 is characterized in that described metal acetate salt is Iron diacetate, neutralized verdigris, lanthanum acetate, cerous acetate, acetic acid lutetium, acetic acid ytterbium, praseodymium acetate, acetic acid neodymium, acetic acid europium, acetic acid thulium, acetic acid samarium, manganese acetate, zinc acetate, Cobaltous diacetate, nickel acetate, cadmium acetate or acetic acid zirconium.
10. claim 1 a kind of contained the purposes that amino acid whose palisade porphyrin compound is simulated biological intravital ionic channel, myohaemoglobin or oxyphorase.
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