CN106432366A - Preparation and application of nano metal-organic framework material PCN-223 based on porphyrin ligand - Google Patents
Preparation and application of nano metal-organic framework material PCN-223 based on porphyrin ligand Download PDFInfo
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- CN106432366A CN106432366A CN201610825376.5A CN201610825376A CN106432366A CN 106432366 A CN106432366 A CN 106432366A CN 201610825376 A CN201610825376 A CN 201610825376A CN 106432366 A CN106432366 A CN 106432366A
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- porphyrin
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- organic framework
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- 239000000463 material Substances 0.000 title claims abstract description 113
- 239000013105 nano metal-organic framework Substances 0.000 title claims abstract description 55
- 239000013289 nano-metal-organic framework Substances 0.000 title claims abstract description 55
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003446 ligand Substances 0.000 title abstract 2
- 239000003814 drug Substances 0.000 claims abstract description 49
- 239000013110 organic ligand Substances 0.000 claims abstract description 29
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 26
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229960002949 fluorouracil Drugs 0.000 claims abstract description 19
- 238000011068 loading method Methods 0.000 claims abstract description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 96
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 54
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- -1 4- methoxycarbonyl-phenyl Chemical group 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 24
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 229910007926 ZrCl Inorganic materials 0.000 claims description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 14
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 14
- 235000019260 propionic acid Nutrition 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 150000003233 pyrroles Chemical class 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- IARNVKSBRPYBMQ-UHFFFAOYSA-N COC(=O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound COC(=O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 IARNVKSBRPYBMQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000013384 organic framework Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229940079593 drug Drugs 0.000 abstract description 17
- 239000012621 metal-organic framework Substances 0.000 abstract description 16
- 239000012876 carrier material Substances 0.000 abstract description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000003937 drug carrier Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229960004756 ethanol Drugs 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZOSVFAIIFHTUEG-UHFFFAOYSA-L dipotassium;dihydroxide Chemical compound [OH-].[OH-].[K+].[K+] ZOSVFAIIFHTUEG-UHFFFAOYSA-L 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/33—Heterocyclic compounds
- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
- A61K31/505—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim
- A61K31/513—Pyrimidines; Hydrogenated pyrimidines, e.g. trimethoprim having oxo groups directly attached to the heterocyclic ring, e.g. cytosine
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
- A61K47/24—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing atoms other than carbon, hydrogen, oxygen, halogen, nitrogen or sulfur, e.g. cyclomethicone or phospholipids
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Organic Chemistry (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Epidemiology (AREA)
- Medicinal Chemistry (AREA)
- Biophysics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- Catalysts (AREA)
Abstract
The invention provides preparation and application of nano metal-organic framework material PCN-223 based on porphyrin ligand. The invention relates to a preparation method and application of a metal-organic framework material. The invention aims at solving the problems that an existing carrier material used for loading a medicine 5-fluorouracil is poor in drug carrying performance and drug release performance. The preparation comprises the following steps of I, the synthesis of 5,10,15,20-tetra(4-methoxycarbonylphenyl)porphyrin; II, the synthesis of [5,10,15,20-tetra(4-methoxycarbonylphenyl)porphyrin] ferric chloride; III, the synthesis of organic ligand Fe(III)-TCPPCl; IV, the synthesis of the nano metal-organic framework material PCN-223. The maximum drug carrying amount of the nano metal-organic framework material PCN-223 prepared by the invention can reach 0.344g/g. The release performance of the medicine is also higher; the release rate can reach 90 percent. The convenience is provided for loading different medicines.
Description
Technical field
The present invention relates to a kind of preparation method and application of metal-organic framework materials.
Background technology
The fast development of metal-organic framework materials is the important breakthrough that recent two decades carry out domain of inorganic chemistry.MOFs material
Material be by metal center or metal cluster as central point.It is formed by connecting by coordinate bond self assembly with organic ligand, with height
Periodic network crystalline complex, also referred to as metal coordinating polymer.
The unique texture feature of this hybrid inorganic-organic of MOFs and the bore hole size of its Nano grade, make it one
One or more catalytic site are provided in individual cavity, this is that other materials institute is irrealizable.Therefore MOFs material has many
Tempting feature：First, MOFs material has component multiformity, by selecting different metal ions and different parts, just
Miscellaneous MOFs material can be synthesized.The structure of second, MOFs material has performance-adjustable, with designed, designed and can close
Become wanted structure, and the functionalization of MOF material can be realized by the modification of functional material.3rd, MOFs material
With loose structure of uniform size, larger specific surface area.4th, MOFs material has good heat stability and chemistry is steady
Qualitative.5th, simple synthetic method, simple to operate.
In the research of nearly 30 years, MOFs material develops with surprising rapidity.In many chemical periodicals, with regard to MOFs
Paper or summary exponentially growth, so fast development speed also illustrate that this material has in field of scientific study that to lift foot light
The status of weight.So far, researchers oneself through having synthesized novel, the of good performance MOFs material of substantial amounts of structure, obtain
Numerous scientific research effects highly visible.
MOFs booming two during the decade, the researchers from countries in the world join in this field, constantly
The various structures of synthesis and expand its application in every field.The Many researchers of recent year are in the field
Certain achievement is achieved, also there is far-reaching influence in the world.
Pharmaceutical carrier to the transmission of medicine it is critical that, traditional pharmaceutical carrier is uncontrollable to the release of medicine
, cause medicine in vivo within a certain period of time medication amount reach very big concentration change, and medicine is released quickly, is embodied
The therapeutic effect that medicine can't have.And the uncertain release of medicine also can cause the secondary work of poison to body in many cases
With.Therefore seek a kind of dynamical, the carrier material of controllability is extremely urgent.
Content of the invention
The invention aims to the carrier material for solving to be currently used for loading medicine 5-fluorouracil carries the property of medicine and drug release
Property difference problem, and provide a kind of preparation of the nano metal organic framework material PCN-223 based on porphyrin part and application.
A kind of preparation method of the nano metal organic framework material PCN-223 based on porphyrin part of the present invention be by with
Lower step is completed：
First, the synthesis of 5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin：Low whipping speed be 1000r/min～
To in propanoic acid, add pyrroles and methyl to benzoyl under conditions of 1500r/min, then heat under conditions of without light irradiation
It is 140～160 DEG C to temperature, and back flow reaction 10h～14h under conditions of temperature is 140～160 DEG C, after the completion of reaction certainly
So be cooled to room temperature, the suspension for obtaining is carried out sucking filtration, solid matter vacuum drying obtains purple and precipitates, i.e., 5,10,15,
20- tetra- (4- methoxycarbonyl-phenyl) porphyrin；
The volume of propanoic acid described in step one is 100mL with the amount of the material of pyrroles:(0.04～0.05) mol；
The volume of propanoic acid described in step one and methyl are 100mL to the amount ratio of the material of benzoyl:(0.04～0.05)
mol；
2nd, the synthesis of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride：By 5,10,15,20- tetra-
(4- methoxycarbonyl-phenyl) porphyrin and FeCl2·4H2It is 150～170 DEG C that O is placed in N,N-dimethylformamide in temperature
Under the conditions of back flow reaction 5h～7h, naturally cool to room temperature after the completion of reaction, be washed with water and wash 2～3 times after the filtration that adds water, filter
The solid for obtaining afterwards first with the salt acid elution 2～3 times of 1mol/L, is washed with water and washs 2～3 times with after chloroform dissolving, after layering
The organic layer for arriving is dry with anhydrous magnesium sulfate, obtains brown precipitate, i.e. [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphin
Quinoline] iron chloride；
(4- methoxycarbonyl-phenyl) porphyrin of 5,10,15,20- tetra- described in step 2 and FeCl2·4H2The amount of the material of O
Than for 1:(12～13)；
The amount of the material of 5,10,15,20- tetra- described in step 2 (4- methoxycarbonyl-phenyl) porphyrin and N, N- dimethyl
The ratio of the volume of Methanamide is 1mmol:(80～120) mL；
3rd, the synthesis of organic ligand Fe (III)-TCPPCl：By [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphin
Quinoline] iron chloride is dissolved in the mixed solvent of methanol and tetrahydrofuran, is subsequently adding the aqueous solution of potassium hydroxide, temperature be
Back flow reaction 10h～14h under conditions of～110 DEG C, naturally cools to room temperature after the completion of reaction, then by methanol and tetrahydrofuran
Steaming, add water and solid matter is dissolved, solution ph is then adjusted to pH=3, obtain brown suspension, wash after filtration,
Then it is vacuum dried, obtains organic ligand Fe (III)-TCPPCl；
The quality of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride described in step 3 and methanol and
The ratio of the volume of the mixed solvent of tetrahydrofuran is 0.75g:(40～60) mL；
In the mixed solvent of methanol described in step 3 and tetrahydrofuran, methanol is 1 with the ratio of the volume of tetrahydrofuran:1；
Quality and the hydroxide of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride described in step 3
The ratio of the volume of the aqueous solution of potassium is 0.75g:(20～30) mL；Wherein in the aqueous solution of the potassium hydroxide, potassium hydroxide is dense
Spend for 1.5mol/L～2mol/L；
4th, the synthesis of nano metal organic framework material PCN-223：To ZrCl4·4H2N, N- dimethyl formyl is added in O
Amine and glacial acetic acid, under conditions of supersonic frequency is for 30KHz～50KHz, supersound process is clarified to solution, is subsequently adding organic joining
Body Fe (III)-TCPPCl, ultrasonic to organic ligand Fe (III)-TCPPCl under conditions of supersonic frequency is for 30KHz～50KHz
All dissolving, temperature is then heated to for 110～130 DEG C, and the 0.5h that flows back under conditions of temperature is 110～130 DEG C～
10h, is centrifuged after reaction completely under conditions of rotating speed is for 7000r/min～9000r/min, then first uses N, N- dimethyl
Methanamide is washed, and again with methanol is washed, and is finally dry under the vacuum condition that temperature is 70～80 DEG C, is obtained brown solid, i.e.,
Nano metal organic framework material PCN-223；
ZrCl described in step 44·4H2The ratio of the quality of O and N,N-dimethylformamide volume for (0.007～
0.028)g:15mL；
ZrCl described in step 44·4H2The ratio of the quality of O and glacial acetic acid volume is 0.007g:(0.5～0.7) mL；
ZrCl described in step 44·4H2The mass ratio of O and organic ligand Fe (III)-TCPPCl is (0.06～0.08):
0.1.
A kind of application of the nano metal organic framework material PCN-223 based on porphyrin part of the present invention：By nanometer gold
Category organic framework material PCN-223 soaks 36h～40h in methanol solution carries out the exchange of solvent, changes a first every 12h
Alcoholic solution, filters after having soaked, and the solid being filtrated to get is placed in vacuum drying oven vacuum at temperature is 60～70 DEG C
Dry, the nanometer PCN-223 material for activating is obtained, the nanometer PCN-223 material of activation is used for loading medicine 5-fluorouracil.
Beneficial effects of the present invention
Nanometer PCN-223 material use synthesized by the present invention is refluxed method synthesis, than ever hydro-thermal method and diffusion
Method is compared, and is more convenient, and fast, and nanometer particle size is less, and chooses different concentration and the response time can control its hole
Footpath size, nano metal organic framework material PCN-223 highest drug loading prepared by the present invention is up to 0.344g/g.The releasing of medicine
Putting property is also higher, and release rate can reach 90%.For loading the convenience that different medicines are provided.
Description of the drawings
Fig. 1 is the infrared spectrogram for testing organic ligand Fe (the III)-TCPPCl that a step 3 is obtained；
Fig. 2 is the infrared spectrogram for testing a nano metal organic framework material PCN-223 for obtaining；
Fig. 3 is the X-ray powder diffraction characterization result for testing a nano metal organic framework material PCN-223 for obtaining
With its monocrystalline analytic simulation figure；
Fig. 4 is the SEM figure for testing a nano metal organic framework material PCN-223 for obtaining；
Fig. 5 is the SEM figure for testing the two nano metal organic framework material PCN-223 for obtaining；
Fig. 6 is the uv-visible absorption spectrum figure of 5-fluorouracil；
Fig. 7 is the canonical plotting of 5-fluorouracil；
Fig. 8 is the drug loading of the nanometer PCN-223 material for testing three activation for obtaining and load medicine time plot；
Fig. 9 is medicine realeasing rate and load medicine time plot after the nanometer PCN-223 material drug carrier for testing three activation for obtaining.
Specific embodiment
Specific embodiment one：A kind of nano metal organic framework material PCN- based on porphyrin part of present embodiment
223 preparation method is completed according to the following steps：
First, the synthesis of 5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin：Low whipping speed be 1000r/min～
To in propanoic acid, add pyrroles and methyl to benzoyl under conditions of 1500r/min, then heat under conditions of without light irradiation
It is 140～160 DEG C to temperature, and back flow reaction 10h～14h under conditions of temperature is 140～160 DEG C, after the completion of reaction certainly
So be cooled to room temperature, the suspension for obtaining is carried out sucking filtration, solid matter vacuum drying obtains purple and precipitates, i.e., 5,10,15,
20- tetra- (4- methoxycarbonyl-phenyl) porphyrin；
The volume of propanoic acid described in step one is 100mL with the amount of the material of pyrroles:(0.04～0.05) mol；
The volume of propanoic acid described in step one and methyl are 100mL to the amount ratio of the material of benzoyl:(0.04～0.05)
mol；
2nd, the synthesis of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride：By 5,10,15,20- tetra-
(4- methoxycarbonyl-phenyl) porphyrin and FeCl2·4H2It is 150～170 DEG C that O is placed in N,N-dimethylformamide in temperature
Under the conditions of back flow reaction 5h～7h, naturally cool to room temperature after the completion of reaction, be washed with water and wash 2～3 times after the filtration that adds water, filter
The solid for obtaining afterwards first with the salt acid elution 2～3 times of 1mol/L, is washed with water and washs 2～3 times with after chloroform dissolving, after layering
The organic layer for arriving is dry with anhydrous magnesium sulfate, obtains brown precipitate, i.e. [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphin
Quinoline] iron chloride；
(4- methoxycarbonyl-phenyl) porphyrin of 5,10,15,20- tetra- described in step 2 and FeCl2·4H2The amount of the material of O
Than for 1:(12～13)；
The amount of the material of 5,10,15,20- tetra- described in step 2 (4- methoxycarbonyl-phenyl) porphyrin and N, N- dimethyl
The ratio of the volume of Methanamide is 1mmol:(80～120) mL；
3rd, the synthesis of organic ligand Fe (III)-TCPPCl：By [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphin
Quinoline] iron chloride is dissolved in the mixed solvent of methanol and tetrahydrofuran, is subsequently adding the aqueous solution of potassium hydroxide, temperature be
Back flow reaction 10h～14h under conditions of～110 DEG C, naturally cools to room temperature after the completion of reaction, then by methanol and tetrahydrofuran
Steaming, add water and solid matter is dissolved, solution ph is then adjusted to pH=3, obtain brown suspension, wash after filtration,
Then it is vacuum dried, obtains organic ligand Fe (III)-TCPPCl；
The quality of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride described in step 3 and methanol and
The ratio of the volume of the mixed solvent of tetrahydrofuran is 0.75g:(40～60) mL；
In the mixed solvent of methanol described in step 3 and tetrahydrofuran, methanol is 1 with the ratio of the volume of tetrahydrofuran:1；
Quality and the hydroxide of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride described in step 3
The ratio of the volume of the aqueous solution of potassium is 0.75g:(20～30) mL；Wherein in the aqueous solution of the potassium hydroxide, potassium hydroxide is dense
Spend for 1.5mol/L～2mol/L；
4th, the synthesis of nano metal organic framework material PCN-223：To ZrCl4·4H2N, N- dimethyl formyl is added in O
Amine and glacial acetic acid, under conditions of supersonic frequency is for 30KHz～50KHz, supersound process is clarified to solution, is subsequently adding organic joining
Body Fe (III)-TCPPCl, ultrasonic to organic ligand Fe (III)-TCPPCl under conditions of supersonic frequency is for 30KHz～50KHz
All dissolving, temperature is then heated to for 110～130 DEG C, and the 0.5h that flows back under conditions of temperature is 110～130 DEG C～
10h, is centrifuged after reaction completely under conditions of rotating speed is for 7000r/min～9000r/min, then first uses N, N- dimethyl
Methanamide is washed, and again with methanol is washed, and is finally dry under the vacuum condition that temperature is 70～80 DEG C, is obtained brown solid, i.e.,
Nano metal organic framework material PCN-223；
ZrCl described in step 44·4H2The ratio of the quality of O and N,N-dimethylformamide volume for (0.007～
0.028)g:15mL；
ZrCl described in step 44·4H2The ratio of the quality of O and glacial acetic acid volume is 0.007g:(0.5～0.7) mL；
ZrCl described in step 44·4H2The mass ratio of O and organic ligand Fe (III)-TCPPCl is (0.06～0.08):
0.1.
Specific embodiment two：Present embodiment from unlike specific embodiment one：Propanoic acid described in step one
Volume is 100mL with the amount ratio of the material of pyrroles:0.043mol.Other steps and parameter are identical with specific embodiment one.
Specific embodiment three：Present embodiment from unlike specific embodiment one or two：Third described in step one
Volume and the methyl of acid is 100mL to the amount ratio of the material of benzoyl:0.042mol.Other steps and parameter and specific embodiment party
Formula one or two is identical.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Institute in step 2
State tetra- (4- methoxycarbonyl-phenyl) porphyrin of 5,10,15,20- and FeCl2·4H2The amount ratio of the material of O is 1:12.8.Other steps
One of rapid and parameter and specific embodiment one to three are identical.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Institute in step 2
State the amount of material of 5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin and the ratio of the volume of N,N-dimethylformamide is
1mmol:100mL.One of other steps and parameter and specific embodiment one to four are identical.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Institute in step 3
State quality and methanol and the mixed solvent of tetrahydrofuran of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride
Volume ratio be 0.75g:50mL.One of other steps and parameter and specific embodiment one to five are identical.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Institute in step 3
State quality and the volume of the aqueous solution of potassium hydroxide of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride
Than for 0.75g:25mL.One of other steps and parameter and specific embodiment one to six are identical.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：Institute in step 3
The concentration for stating potassium hydroxide in the aqueous solution of potassium hydroxide is 1.5mol/L～2mol/L.Other steps and parameter be embodied as
Mode one is identical to one of the Seventh Five-Year Plan.
Specific embodiment nine：Unlike one of present embodiment and specific embodiment one to eight：Institute in step 3
The concentration for stating potassium hydroxide in the aqueous solution of potassium hydroxide is 1.878mol/L.Other steps and parameter and specific embodiment one
Identical to one of eight.
Specific embodiment ten：Unlike one of present embodiment and specific embodiment one to nine：Institute in step 4
State ZrCl4·4H2The ratio of the quality of O and N,N-dimethylformamide volume is (0.007～0.014) g:15mL.Other steps and
One of parameter and specific embodiment one to nine are identical.
Specific embodiment 11：Unlike one of present embodiment and specific embodiment one to ten：In step 4
The ZrCl4·4H2The ratio of the quality of O and glacial acetic acid volume is 0.007g:0.6mL.Other steps and parameter and specific embodiment party
One of formula one to ten is identical.
Specific embodiment 12：Unlike one of present embodiment and specific embodiment one to ten one：Step 4
Described in ZrCl4·4H2The mass ratio of O and organic ligand Fe (III)-TCPPCl is 0.07:0.1.Other steps and parameter and tool
One of body embodiment one to ten one is identical.
Specific embodiment 13：A kind of nano metal organic framework material based on porphyrin part of present embodiment
The application of PCN-223, it is characterised in that nano metal organic framework material PCN-223 is soaked 36h～40h in methanol solution
The exchange of solvent is carried out, is filtered after 12h changes a methanol solution, soaked, the solid being filtrated to get is placed in very
It is vacuum dried at temperature is 60～70 DEG C in empty drying baker, the nanometer PCN-223 material for activating is obtained, by the nanometer of activation
PCN-223 material is used for loading medicine 5-fluorouracil.
Beneficial effects of the present invention are verified with tests below
A kind of test one, nano metal organic framework material PCN-223 method based on porphyrin part of this experiment by with
Lower step is carried out：
First, the synthesis of 5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin：Low whipping speed is for 1200r/min's
Under the conditions of add the methyl of the pyrroles of 3g and 6.9g in the propanoic acid of 100mL to benzoyl, then in the condition without light irradiation
Under be heated to temperature for 150 DEG C, and back flow reaction 12h under conditions of temperature is 150 DEG C, naturally cool to room after the completion of reaction
Temperature, the suspension for obtaining is carried out sucking filtration, and solid matter vacuum drying obtains purple precipitation, i.e., 5,10,15,20- tetra- (4- methoxies
Base carbonyl phenyl) porphyrin；
2nd, the synthesis of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride：By the 5,10 of 0.854g,
Tetra- (4- methoxycarbonyl-phenyl) porphyrin of 15,20- and the FeCl of 2.5g2·4H2O is placed in the N,N-dimethylformamide of 100mL
Back flow reaction 6h under conditions of temperature is 160 DEG C, naturally cools to room temperature after the completion of reaction, is washed with water and washs after the filtration that adds water
2 times, the solid for obtaining after filtration first with the salt acid elution 2 times of 1mol/L, is washed with water and washs 2 times, after layering with after chloroform dissolving
The organic layer for obtaining is dry with anhydrous magnesium sulfate, obtains brown precipitate, i.e. [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl)
Porphyrin] iron chloride；
3rd, the synthesis of organic ligand Fe (III)-TCPPCl：[tetra- (4- methoxycarbonyl of 5,10,15,20- by 0.75g
Phenyl) porphyrin] iron chloride is dissolved in the mixed solvent of the methanol of 25mL and the tetrahydrofuran of 25mL, is subsequently adding the hydrogen of 25mL
The aqueous solution of potassium oxide, back flow reaction 12h under conditions of temperature is 100 DEG C, room temperature is naturally cooled to after the completion of reaction, then
Methanol and tetrahydrofuran being steamed, is added water and solid matter is dissolved, solution ph is then adjusted to pH=3, obtains brown and hang
Supernatant liquid, washes after filtration, is then vacuum dried, obtains organic ligand Fe (III)-TCPPCl；
Wherein in the aqueous solution of the potassium hydroxide potassium hydroxide, the concentration of potassium hydroxide is 1.878mol/L；
4th, the synthesis of nano metal organic framework material PCN-223：ZrCl to 0.007g4·4H2Add 15mL's in O
DMF and the glacial acetic acid of 0.6mL, under conditions of supersonic frequency is for 40KHz, supersound process is clarified to solution,
Organic ligand Fe (the III)-TCPPCl of 0.01g is subsequently adding, ultrasound is to organic ligand under conditions of supersonic frequency is for 40KHz
Fe (III)-TCPPCl all dissolves, and is then heated to temperature for 120 DEG C, and the 0.5h that flows back under conditions of temperature is 120 DEG C,
It is centrifuged under conditions of rotating speed is for 8000r/min after reaction completely, is then first washed with DMF, then use
Methanol is washed, and is finally dry under the vacuum condition that temperature is 75 DEG C, is obtained brown solid, i.e. nano metal organic framework material
PCN-223.
A kind of test two, nano metal organic framework material PCN-223 method based on porphyrin part of this experiment by with
Lower step is carried out：
First, the synthesis of 5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin：Low whipping speed is for 1200r/min's
Under the conditions of add the methyl of the pyrroles of 3g and 6.9g in the propanoic acid of 100mL to benzoyl, then in the condition without light irradiation
Under be heated to temperature for 150 DEG C, and back flow reaction 12h under conditions of temperature is 150 DEG C, naturally cool to room after the completion of reaction
Temperature, the suspension for obtaining is carried out sucking filtration, and solid matter vacuum drying obtains purple precipitation, i.e., 5,10,15,20- tetra- (4- methoxies
Base carbonyl phenyl) porphyrin；
2nd, the synthesis of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride：By the 5,10 of 0.854g,
Tetra- (4- methoxycarbonyl-phenyl) porphyrin of 15,20- and the FeCl of 2.5g2·4H2O is placed in the N,N-dimethylformamide of 100mL
Back flow reaction 6h under conditions of temperature is 160 DEG C, naturally cools to room temperature after the completion of reaction, is washed with water and washs after the filtration that adds water
2 times, the solid for obtaining after filtration first with the salt acid elution 2 times of 1mol/L, is washed with water and washs 2 times, after layering with after chloroform dissolving
The organic layer for obtaining is dry with anhydrous magnesium sulfate, obtains brown precipitate, i.e. [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl)
Porphyrin] iron chloride；
3rd, the synthesis of organic ligand Fe (III)-TCPPCl：[tetra- (4- methoxycarbonyl of 5,10,15,20- by 0.75g
Phenyl) porphyrin] iron chloride is dissolved in the mixed solvent of the methanol of 25mL and the tetrahydrofuran of 25mL, is subsequently adding the hydrogen of 25mL
The aqueous solution of potassium oxide, back flow reaction 12h under conditions of temperature is 100 DEG C, room temperature is naturally cooled to after the completion of reaction, then
Methanol and tetrahydrofuran being steamed, is added water and solid matter is dissolved, solution ph is then adjusted to pH=3, obtains brown and hang
Supernatant liquid, washes after filtration, is then vacuum dried, obtains organic ligand Fe (III)-TCPPCl；
Wherein in the aqueous solution of the potassium hydroxide potassium hydroxide, the concentration of potassium hydroxide is 1.878mol/L；
4th, the synthesis of nano metal organic framework material PCN-223：ZrCl to 0.014g4·4H2Add 15mL's in O
DMF and the glacial acetic acid of 1.2mL, under conditions of supersonic frequency is for 40KHz, supersound process is clarified to solution,
Organic ligand Fe (the III)-TCPPCl of 0.02g is subsequently adding, ultrasound is to organic ligand under conditions of supersonic frequency is for 40KHz
Fe (III)-TCPPCl all dissolves, and is then heated to temperature for 120 DEG C, and the 1h that flows back under conditions of temperature is 120 DEG C, instead
It is centrifuged under conditions of rotating speed is for 8000r/min after answering completely, is then first washed with DMF, then use first
Alcohol is washed, and is finally dry under the vacuum condition that temperature is 75 DEG C, is obtained brown solid, i.e. nano metal organic framework material
PCN-223.
First, the performance detection of nano metal organic framework material PCN-223：
(1) carry out infrared spectrum detection to testing organic ligand Fe (the III)-TCPPCl that obtains of a step 3, obtain as
The infrared spectrogram of organic ligand Fe (the III)-TCPPCl that one step 3 of test shown in Fig. 1 is obtained, FTIR (KBr)：ν=
3444 (m), 2922 (w), 1701 (s), 1605 (s), 1274 (s), 799 (m) cm-1.
(2) infrared spectrum detection is carried out to the one nano metal organic framework material PCN-223 that obtains of test, obtain as
The infrared spectrogram of the nano metal organic framework material PCN-223 that the test one shown in Fig. 2 is obtained；Wherein 1 obtains for test one
The nano metal organic framework material PCN-223 for arriving, 2 organic ligand Fe (the III)-TCPPCl for obtaining for one step 3 of test,
As seen from Figure 2, carbonyl (C-O) stretching vibration peak there occurs obvious red shift after the completion of the reaction, illustrate Fe (III)-
TCPPCl there occurs complexation reaction with metal ion.
(3) the nano metal organic framework material PCN-223 obtained by test one carries out X-ray powder diffraction detection,
The X-ray powder diffraction for obtaining the nano metal organic framework material PCN-223 that test one as shown in Figure 3 is obtained characterizes knot
Fruit and its monocrystalline analytic simulation figure；The wherein 1 nano metal organic framework material PCN-223 for obtaining for test one, 2 is its simulation
Crystal, as seen from Figure 3, the crystal XRD data for going out peak position and intensity with simulating of XRD are basically identical, and free from admixture peak,
Show that the coordination compound synthesized by the method has higher purity.
(4) Electronic Speculum detection is scanned to the one nano metal organic framework material PCN-223 that obtains of test, obtain as
The SEM figure of the nano metal organic framework material PCN-223 that the test one shown in Fig. 4 is obtained, as seen from Figure 4, test one
The size of the nano metal organic framework material PCN-223 for obtaining is 500nm × 150nm (long × wide).
(5) Electronic Speculum detection is scanned to the two nano metal organic framework material PCN-223 that obtain of test, obtain as
The SEM figure of the nano metal organic framework material PCN-223 that the test two shown in Fig. 5 is obtained, as seen from Figure 5, test two
The size of the nano metal organic framework material PCN-223 for obtaining is 490nm × 145nm (long × wide).
2nd, the load medicine of nano metal organic framework material PCN-223-drug release property detection：
(1) maximum absorption wavelength of the 5-fluorouracil in dehydrated alcohol is found by ultra-violet absorption spectrum, obtains as figure
The uv-visible absorption spectrum figure of the 5-fluorouracil shown in 6；In figure curve represents 5-fluorouracil from top to bottom successively no
Concentration in water-ethanol be 0.020mg/mL, 0.018mg/mL, 0.016mg/mL, 0.014mg/mL, 0.012mg/mL,
0.010mg/mL, 0.008mg/mL, 0.006mg/mL, 0.004mg/mL and 0.002mg/mL, it will be appreciated from fig. 6 that 5-fluorouracil
The a length of 262nm of maximum absorption wave.
(2) absorbance of 5-fluorouracil under variable concentrations is measured according to the maximum absorption wavelength of 5-fluorouracil, due to
Detectable concentration of the 5-fluorouracil in ethanol solution in the range of 0.5-50ug/mL, absorbance (A) and concentration (c)
Just there is good linear relationship.Therefore the canonical plotting of 5-fluorouracil as shown in Figure 7 is obtained；Can be drawn by Fig. 7,
Regression equation is A=0.0660c+0.009 (R2=0.9975).
Nano metal organic framework material PCN-223 prepared by test three, test one is used as loading medicine 5-fluorouracil
Application, detailed process is as follows：
Nano metal organic framework material PCN-223 prepared by test one soaks 36h in methanol solution carries out solvent
Exchange, every 12h change a methanol solution, has soaked after filtration, the solid being filtrated to get is placed in vacuum drying oven
In temperature be 65 DEG C at be vacuum dried, obtain activate nanometer PCN-223 material, by activation nanometer PCN-223 material use
In loading medicine 5-fluorouracil.
(3) using the nanometer PCN-223 material of three activation for obtaining is tested for loading medicine 5-fluorouracil, then
With nanometer PCN-223 material of the ultraviolet spectrophotometer (Co., Ltd. stock power make institute U3270) to activation that test three is obtained
Carry out carrying medicine test, detailed process is as follows：
First the 5-fluorouracil of 20mg is dissolved in the ethanol solution of 20mL, stirring makes which all dissolve, backward
The nanometer PCN-223 material of the activation for adding the test three of 5mg to obtain in solution is used as pharmaceutical carrier so as to be loaded.Per
The ultraviolet absorptivity of a sample is surveyed every 2h, the standard curve according to above-mentioned gained calculates its concentration and drug loading.
Obtain drug loading and carry medicine time plot as shown in figure 8, as can be seen from Figure 8, when the time more than 58h it
Afterwards, PCN-223 carries substantially medicine and completes, and as 60-80h, drug loading has fluctuation slightly, this is because medicine is in solvent soaking mistake
Long, cause nanometer some drugs of PCN-223 material surface to split away off and cause.Subsequently drug loading is tended towards stability substantially.Most
High drug load is up to 0.344g/g.
(4) and then with ultraviolet spectrophotometer (Co., Ltd.'s stock power makes institute U3270) to testing three activation for obtaining
Material after nanometer PCN-223 material drug carrier carries out drug release test, and detailed process is as follows：
The nanometer PCN-223 material of the activation that the test three for loading medicine in (three) is obtained is filtered, and 70 DEG C true
Empty dry, to be dried after dissolve it in the ethanol solution of 20mL, be put in shaking table and vibrated that (concussion frequency is
100rpm/min), starting surveys its uv absorption situation every 1-2 hour, after 12 hours, extends minute.And according to its mark
Directrix curve calculates the burst size of medicine.
Obtaining medicine realeasing rate and medicine time plot is carried as shown in figure 9, it can be seen in figure 9 that ought be basic after 20 hours
No longer medicine is discharged, this shows medicine from slow release the hole of nanometer PCN-223 material out.And the release of medicine
Property is also higher, and release rate can reach 90%.
Claims (10)
1. a kind of preparation method of the nano metal organic framework material PCN-223 based on porphyrin part, it is characterised in that a kind of
Carried out based on the nano metal organic framework material PCN-223 method of porphyrin part according to the following steps：
First, the synthesis of 5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin：Low whipping speed be 1000r/min～
To in propanoic acid, add pyrroles and methyl to benzoyl under conditions of 1500r/min, then heat under conditions of without light irradiation
It is 140～160 DEG C to temperature, and back flow reaction 10h～14h under conditions of temperature is 140～160 DEG C, after the completion of reaction certainly
So be cooled to room temperature, the suspension for obtaining is carried out sucking filtration, solid matter vacuum drying obtains purple and precipitates, i.e., 5,10,15,
20- tetra- (4- methoxycarbonyl-phenyl) porphyrin；
The volume of propanoic acid described in step one is 100mL with the amount of the material of pyrroles:(0.04～0.05) mol；
The volume of propanoic acid described in step one and methyl are 100mL to the amount ratio of the material of benzoyl:(0.04～0.05) mol；
2nd, the synthesis of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride：By tetra- (4- first of 5,10,15,20-
Epoxide carbonyl phenyl) porphyrin and FeCl2·4H2O is placed in N,N-dimethylformamide under conditions of temperature is 150～170 DEG C
Back flow reaction 5h～7h, naturally cools to room temperature after the completion of reaction, is washed with water and washs 2～3 times, obtain after filtration after the filtration that adds water
Solid with after chloroform dissolving, first with the salt acid elution 2～3 times of 1mol/L, be washed with water and wash 2～3 times, obtained after layering has
Machine layer is dry with anhydrous magnesium sulfate, obtains brown precipitate, i.e. [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] chlorination
Ferrum；
(4- methoxycarbonyl-phenyl) porphyrin of 5,10,15,20- tetra- described in step 2 and FeCl2·4H2The amount ratio of the material of O is
1:(12～13)；
The amount of the material of 5,10,15,20- tetra- described in step 2 (4- methoxycarbonyl-phenyl) porphyrin and N, N- dimethyl formyl
The ratio of the volume of amine is 1mmol:(80～120) mL；
3rd, the synthesis of organic ligand Fe (III)-TCPPCl：By [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] chlorine
Change dissolved ferric iron in the mixed solvent of methanol and tetrahydrofuran, the aqueous solution of potassium hydroxide is subsequently adding, be 90～110 in temperature
Back flow reaction 10h～14h under conditions of DEG C, naturally cools to room temperature after the completion of reaction, then steam methanol and tetrahydrofuran,
Adding water and solid matter is dissolved, solution ph is then adjusted to pH=3, obtain brown suspension, wash, Ran Houzhen after filtration
Empty dry, obtain organic ligand Fe (III)-TCPPCl；
Quality and methanol and the tetrahydrochysene of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride described in step 3
The ratio of the volume of the mixed solvent of furan is 0.75g:(40～60) mL；
In the mixed solvent of methanol described in step 3 and tetrahydrofuran, methanol is 1 with the ratio of the volume of tetrahydrofuran:1；
Quality and the potassium hydroxide of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride described in step 3
The ratio of the volume of aqueous solution is 0.75g:(20～30) mL；Wherein in the aqueous solution of the potassium hydroxide, the concentration of potassium hydroxide is
1.5mol/L～2mol/L；
4th, the synthesis of nano metal organic framework material PCN-223：To ZrCl4·4H2In O add N,N-dimethylformamide and
Glacial acetic acid, under conditions of supersonic frequency is for 30KHz～50KHz, supersound process is clarified to solution, is subsequently adding organic ligand Fe
(III)-TCPPCl, under conditions of supersonic frequency is for 30KHz～50KHz, ultrasound is whole to organic ligand Fe (III)-TCPPCl
Dissolving, is then heated to temperature for 110～130 DEG C, and the 0.5h～10h that flows back under conditions of temperature is 110～130 DEG C, instead
It is centrifuged under conditions of rotating speed is for 7000r/min～9000r/min after answering completely, is then first used DMF
Washing, again with methanol is washed, and is finally dry under the vacuum condition that temperature is 70～80 DEG C, is obtained brown solid, i.e. nanometer gold
Category organic framework material PCN-223；
ZrCl described in step 44·4H2The ratio of the quality of O and N,N-dimethylformamide volume is (0.007～0.028) g:
15mL；
ZrCl described in step 44·4H2The ratio of the quality of O and glacial acetic acid volume is 0.007g:(0.5～0.7) mL；
ZrCl described in step 44·4H2The mass ratio of O and organic ligand Fe (III)-TCPPCl is (0.06～0.08):0.1.
2. the preparation of a kind of nano metal organic framework material PCN-223 based on porphyrin part according to claim 1
Method, it is characterised in that the volume of propanoic acid described in step one is 100mL with the amount ratio of the material of pyrroles:0.043mol；Step
The volume of propanoic acid described in one and methyl are 100mL to the amount ratio of the material of benzoyl:0.042mol.
3. the preparation of a kind of nano metal organic framework material PCN-223 based on porphyrin part according to claim 1
Method, it is characterised in that 5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrins and FeCl described in step 22·4H2O's
The amount ratio of material is 1:12.8.
4. the preparation of a kind of nano metal organic framework material PCN-223 based on porphyrin part according to claim 1
Method, it is characterised in that the amount of the material of 5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin described in step 2 and N,
The ratio of the volume of dinethylformamide is 1mmol:100mL.
5. the preparation of a kind of nano metal organic framework material PCN-223 based on porphyrin part according to claim 1
Method, it is characterised in that the quality of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride described in step 3
Ratio with the volume of methanol and the mixed solvent of tetrahydrofuran is 0.75g:50mL.
6. the preparation of a kind of nano metal organic framework material PCN-223 based on porphyrin part according to claim 1
Method, it is characterised in that the quality of [5,10,15,20- tetra- (4- methoxycarbonyl-phenyl) porphyrin] iron chloride described in step 3
Ratio with the volume of the aqueous solution of potassium hydroxide is 0.75g:25mL.
7. the preparation of a kind of nano metal organic framework material PCN-223 based on porphyrin part according to claim 1
Method, it is characterised in that ZrCl described in step 44·4H2The ratio of the quality of O and N,N-dimethylformamide volume is (0.007
～0.014) g:15mL.
8. the preparation of a kind of nano metal organic framework material PCN-223 based on porphyrin part according to claim 1
Method, it is characterised in that ZrCl described in step 44·4H2The ratio of the quality of O and glacial acetic acid volume is 0.007g:0.6mL.
9. the preparation of a kind of nano metal organic framework material PCN-223 based on porphyrin part according to claim 1
Method, it is characterised in that ZrCl described in step 44·4H2The mass ratio of O and organic ligand Fe (III)-TCPPCl is 0.07:
0.1.
10. a kind of application of the nano metal organic framework material PCN-223 based on porphyrin part as claimed in claim 1,
It is characterized in that nano metal organic framework material PCN-223 is soaked 36h～40h in methanol solution carry out the friendship of solvent
Change, filter after 12h changes a methanol solution, soaked, the solid being filtrated to get is placed in vacuum drying oven
Temperature is vacuum dried at being 60～70 DEG C, obtains the nanometer PCN-223 material for activating, the nanometer PCN-223 material of activation is used
In loading medicine 5-fluorouracil.
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| CN109970985A (en) * | 2019-03-15 | 2019-07-05 | 中国石油大学(华东) | A kind of method of room temperature synthesis metal-organic framework material PCN-224 |
| CN110327984A (en) * | 2019-07-12 | 2019-10-15 | 西北工业大学 | A kind of Pt@PCN-224 photochemical catalyst and preparation method thereof preparing qinghaosu for double hydrogen Arteannuic acids |
| CN110713603A (en) * | 2019-09-18 | 2020-01-21 | 山东大学 | Polymer, preparation method thereof and application of polymer as bacteria detection and antibacterial material |
| CN112587661A (en) * | 2020-12-08 | 2021-04-02 | 中国科学院高能物理研究所 | Boric acid-loaded zirconium-based metalloporphyrin MOFs material as well as preparation method and application thereof |
| CN114196030A (en) * | 2020-09-02 | 2022-03-18 | 南京大学 | Preparation method and application of water-soluble macroporous zirconium porphyrin structure compound |
| KR20220155000A (en) * | 2021-05-14 | 2022-11-22 | 울산과학기술원 | Large scale manufacturing method for porphyrinic zirconium metal-organic frameworks |
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| CN109970985A (en) * | 2019-03-15 | 2019-07-05 | 中国石油大学(华东) | A kind of method of room temperature synthesis metal-organic framework material PCN-224 |
| CN110327984A (en) * | 2019-07-12 | 2019-10-15 | 西北工业大学 | A kind of Pt@PCN-224 photochemical catalyst and preparation method thereof preparing qinghaosu for double hydrogen Arteannuic acids |
| CN110327984B (en) * | 2019-07-12 | 2022-04-22 | 西北工业大学 | Pt @ PCN-224 photocatalyst for preparing artemisinin from dihydroarteannuic acid and preparation method thereof |
| CN110713603A (en) * | 2019-09-18 | 2020-01-21 | 山东大学 | Polymer, preparation method thereof and application of polymer as bacteria detection and antibacterial material |
| CN110713603B (en) * | 2019-09-18 | 2020-12-01 | 山东大学 | Polymer, preparation method thereof and application of polymer as bacteria detection and antibacterial material |
| CN114196030A (en) * | 2020-09-02 | 2022-03-18 | 南京大学 | Preparation method and application of water-soluble macroporous zirconium porphyrin structure compound |
| CN114196030B (en) * | 2020-09-02 | 2022-09-23 | 南京大学 | Preparation method and application of water-soluble macroporous zirconium porphyrin structure compound |
| CN112587661A (en) * | 2020-12-08 | 2021-04-02 | 中国科学院高能物理研究所 | Boric acid-loaded zirconium-based metalloporphyrin MOFs material as well as preparation method and application thereof |
| KR20220155000A (en) * | 2021-05-14 | 2022-11-22 | 울산과학기술원 | Large scale manufacturing method for porphyrinic zirconium metal-organic frameworks |
| KR102594252B1 (en) * | 2021-05-14 | 2023-10-30 | 울산과학기술원 | Large scale manufacturing method for porphyrinic zirconium metal-organic frameworks |
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