CN1305937C - Prepn process of metal coordinating polymer material in nanometer structure - Google Patents
Prepn process of metal coordinating polymer material in nanometer structure Download PDFInfo
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- CN1305937C CN1305937C CNB2005100240542A CN200510024054A CN1305937C CN 1305937 C CN1305937 C CN 1305937C CN B2005100240542 A CNB2005100240542 A CN B2005100240542A CN 200510024054 A CN200510024054 A CN 200510024054A CN 1305937 C CN1305937 C CN 1305937C
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Abstract
The present invention relates to a preparation method of a novel nanometer structural material of a metallic coordination polymer, which is carried out at an interface formed between water and a water insoluble organic solvent, and a self assembly interface reaction occurs at the liquid-liquid interface between metallic ions or metallic coordination ions in the water solution and an organic ligand in the organic solvent to generate the required nanometer structural material. The conformation of the nanometer structural material can be regulated and controlled by changing the conditions of the kind, the concentration, the reaction time, etc. of the precursor materials (the metallic ions, the metallic coordination ions and the organic ligand) in the two-phase solution. Compared with other preparation methods of nanometer structural materials, the method has the advantages of simple equipment, low environmental requirements, high product purity, etc.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of metal coordinating polymer material in nanometer structure.Self-assembly behavior at the liquid-liquid interface place obtains the nanostructure product to this method based on precursor material, and is simple, equipment, production environment required lower, can realize design and regulation and control to the product pattern simply.Can be applied aspect the production of nano structural material, the preparation.
Technical background
Nanoscale science and technology is to be born in phase late 1980s also obtaining the new science and technology that scientific circles pay much attention in recent years, and nano material technology is the subscience the most dynamic in the nanoscale science and technology field, that research contents is the abundantest, wherein nano structural material then is the research focus and the forward position of present stage nano material, and synthetic based on the control of the molecule self-assembly system of nanostructure, nanostructure pattern then is the development trend of current nano structural material.
Along with the develop rapidly of nanoscale science and technology, the preparation method of nano structural material also emerges in an endless stream.In general, construct the motivating force of process divides according to nano structural material, two kinds of systems of nanostructure self-assembly and artificial nano structure assembling are arranged, according to these two kinds of systems, produced such as utilizing multiple preparation methods such as template, vapour deposition process, sol-gel method, made one dimension, two dimension, three-dimensional nano structural material.Though reached control with comparalive ease to the product pattern based on the method for artificial nano structure assembly system, often production unit, reaction conditions all there are higher requirement, the process of preparation is more complicated also.And self-assembly system passes through intermolecular non-covalent bonding force spontaneously in conjunction with generating nano structural material, is a kind of parallel process, but difficult to the control ratio of product size, pattern, distribution.So, seek equipment, environmental requirement lowlyer, the self-assembling method that can simply control the nano structural material pattern is the development trend of current nano structural material preparation again.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of simple, metal coordinating polymer material in nanometer structure that pattern is controlled.
The metal coordinating polymer material in nanometer structure preparation method that the present invention proposes, at first metal-salt or water-soluble metal coordination ion are dissolved in the water and make the water of metal ion, then with the organosilane precursor material dissolves in the immiscible organic solvent of water in make organic phase, the general proportion of selecting is than the big organic solvent of water such as chloroform, tetracol phenixin, 1,1,2,2-tetrachloroethane etc.Organic phase is added in the reactor earlier, and then slowly add water, self assembly interface reaction promptly takes place at the liquid-liquid interface place that two liquid phases form in metal and organosilane precursor material, and the target product of Sheng Chenging is required nano structural material at the interface.This nano structural material is insoluble to two liquid phases.Preparation method of the present invention all at room temperature carries out.
By the time of control surface reaction, can realize regulation and control to product granularity, pattern; Change the concentration of precursor material, can control the speed of liquid-liquid interface self-assembling reaction, also can realize regulation and control the product pattern.
In the aforesaid method, the metal-salt or the metal coordination ion that are suitable for are very extensive, for example: CdCl
2, AgNO
3, HgCl
2, K
2PdCl
4Deng.The organosilane precursor material that is suitable for is also very extensive, and for example: TPyP (5,10,15,20-Tetra (4-pyridyl)-21H, 23H-porphyrin) (5,10,15,20-four (4-pyridyl)-21 hydrogen, 23 hydrogen-porphyrin), PVP (Poly (4-vinylpyridyl)) (poly-(4-vinylpridine)), ZnDPyDPP (Zn (II) 5,15-di (4-pyridyl) 10,20-diphenyl-porphyrin) (zinc-5,15-two (4-pyridyl)-10,20-phenylbenzene porphyrin) etc.
In the aforesaid method, the reaction times at interface generally is controlled at 1 minute-2 week, and the concentration of aqueous solution of metal-salt or metal coordination ion generally is controlled at 1mM-1M, and the organic solution concentration of organosilane precursor material is 0.1-1mM.
Description of drawings
Fig. 1. the Cd-TPyP metal-many porphyrin arrays nanostructure that makes with the present invention.CdCl
2Concentration of aqueous solution: 0.04M, TPyP chloroformic solution concentration: 0.3mM; Reaction times: (a) 5 days; (b) 2 weeks.
Fig. 2. the Cd-PVP metal-polypyridine array nanostructure that makes with the present invention.CdCl
2Concentration of aqueous solution: 0.04M, PVP chloroformic solution concentration: 0.3mM; Reaction times: (a) 3 hours; (b) 5 hours.
Fig. 3. the Ag-TPyP metal-many porphyrin arrays nanometer rod that makes with the present invention.AgNO
3Concentration of aqueous solution: 0.1M, TPyP chloroformic solution concentration: 0.3mM; Reaction times: (a) 15 minutes; (b) 1 hour.
Fig. 4. the Hg-TPyP metal-many porphyrin arrays nano wire that makes with the present invention.HgCl
2Concentration of aqueous solution: (a) 1mM; (b) 10mM, TPyP chloroformic solution concentration: 0.3mM; Reaction times: 3 minutes.
Fig. 5. the Pd-ZnDPyDPP metal-many porphyrin arrays nano belt that makes with the present invention.K
2PdCl
4Concentration of aqueous solution: 1mM, ZnDPyDPP chloroformic solution concentration: 0.3mM; Reaction times: (a) 6 hours; (b) 1 day.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1:
With 15ml, 5,10,15 of 0.3mM, 20-Tetra (4-pyridyl)-21H, 23H-porphyrin (TPyP) chloroformic solution joins among the beaker, slowly adds 15ml, the CdCl of 0.04M again
2The aqueous solution leaves standstill, and can obtain purple film like nanostructure in water-chloroform surface reaction.By to TPyP chloroformic solution and CdCl
2(the TPyP concentration range is at 0.1mM～1mM, CdCl for the control of the concentration of the aqueous solution
2Concentration range is at 1mM～100mM), and the change in reaction times (1 hour～2 week) can obtain square or orthogonal cadmium-many porphyrin nanos array structures of different sizes.
Embodiment 2:
With 15ml, the Poly of 0.3mM (4-vinylpyridyl) (PVP) chloroformic solution joins among the beaker, slowly adds 15ml, the CdCl of 0.04M again
2The aqueous solution leaves standstill, and can obtain white film shape nanostructure at water-chloroform interface.By to PVP chloroformic solution and CdCl
2(the PVP concentration range is at 0.1mM～1mM, CdCl for the control of the concentration of the aqueous solution
2Concentration range is at 1mM～100mM), and the change in reaction times (1 hour～12 hours) can obtain circular cadmium-polypyridine nanostructure.
Embodiment 3:
With 15ml, 5,10,15 of 0.3mM, 20-Tetra (4-pyridyl)-21H, 23H-porphyrin (TPyP) chloroformic solution joins among the beaker, slowly adds 15ml, the AgNO of 0.1M again
3The aqueous solution, leave standstill some hrs after, can obtain purple film like nanostructure at water-chloroform interface.By to TPyP chloroformic solution and AgNO
3(the TPyP concentration range is at 0.1mM～1mM, AgNO for the control of the concentration of the aqueous solution
3Concentration range is at 0.01M～1M), and the change in reaction times (1 minute～1 hour) can obtain long strip shape Yin-many porphyrin nanos rods of different sizes.
Embodiment 4:
With 15ml, 5,10,15 of 0.3mM, 20-Tetra (4-pyridyl)-21H, 23H-porphyrin (TPyP) chloroformic solution joins among the beaker, slowly adds 15ml, the HgCl of 0.01M again
2The aqueous solution leaves standstill, and can obtain purple film like nanostructure at water-chloroform interface.By to TPyP chloroformic solution and HgCl
2(the TPyP concentration range is at 0.1mM～1mM, HgCl for the control of the concentration of the aqueous solution
2Concentration range is at 10mM～200mM), the change in reaction times (1 minute～1 hour), and the change in reaction times can obtain network-like mercury-many porphyrin nanos line.
Embodiment 5:
With 15ml, 5,10,15 of 0.3mM, 20-Tetra (4-pyridyl)-21H, 23H-porphyrin (TPyP) chloroformic solution joins among the beaker, slowly adds 15ml, the K of 1mM again
2PtCl
4The aqueous solution leaves standstill, and can obtain purple film like nanostructure at water-chloroform interface.By to TPyP chloroformic solution and K
2PtCl
4(the TPyP concentration range is at 0.1mM～1mM, K for the control of the concentration of the aqueous solution
2PtCl
4Concentration range is at 0.1mM～1mM), the change in reaction times (1 hour～1 week), and the change in reaction times can obtain network-like irregular square or unformed platinum-many porphyrin nanos particle.
Embodiment 6:
With 15ml, the Zn of 0.3mM (II) 5,15-di (4-pyridyl) 10,20-diphenyl-porphyrin (ZnDPyDPP) chloroformic solution joins among the beaker, slowly adds 15ml, the K of 1mM again
2PdCl
4The aqueous solution leaves standstill, and can obtain purple film like nanostructure at water-chloroform interface.By to ZnDPyDPP chloroformic solution and K
2PdCl
4(the ZnDPyDPP concentration range is at 0.1mM～1mM, K for the control of the concentration of the aqueous solution
2PdCl
4Concentration range is in that 0.1mM～1mM), the change in reaction times (1 hour～1 week) can obtain palladium-many porphyrin nanos band.
Claims (9)
1, a kind of preparation method of metal coordinating polymer material in nanometer structure, it is characterized in that at first metal-salt or water-soluble metal coordination ion be dissolved in the water makes the water of metal ion, then with the organosilane precursor material dissolves in the immiscible organic solvent of water in make organic phase; Organic phase is added in the reactor earlier, and then add water, self assembly interface reaction promptly takes place at the liquid-liquid interface place that two liquid phases form in metal and organosilane precursor material, and the target product of Sheng Chenging is required nano structural material at the interface; Wherein, said metal-salt or metal coordination ion are CdCl
2, AgNO
3, HgCl
2, K
2PtCl
4Or K
2PdCl
4, said organosilane precursor material is 5,10,15,20-four (4-pyridyl)-21 hydrogen, 23 hydrogen-porphyrin, poly-(4-vinylpridine) or zinc-5,15-two (4-pyridyl)-10,20-phenylbenzene porphyrin.
2, preparation method according to claim 1 is characterized in that said organic solvent is chloroform, tetracol phenixin or sym.-tetrachloroethane.
3, preparation method according to claim 1, it is characterized in that in the self-assembling reaction time at liquid-liquid interface place be 1 minute-2 week, the concentration of aqueous solution of metal-salt or metal coordination ion is controlled at 1mM-1M, and the organic solution concentration of organosilane precursor material is 0.1-1mM.
4, preparation method according to claim 1 is characterized in that metal-salt adopts CdCl
2, organic solvent adopts chloroform, and the organosilane precursor material adopts 5,10,15,20-four (4-pyridyl)-21 hydrogen, 23 hydrogen-porphyrin, CdCl
2Concentration of aqueous solution be 1-100mM, 5,10,15,20-four (4-pyridyl)-21 hydrogen, the chloroformic solution concentration of 23 hydrogen-porphyrin is 0.1-10mM, week 1 minute-2 reaction times.
5, preparation method according to claim 3 is characterized in that metal-salt adopts CdCl
2, organic solvent adopts chloroform, and the organosilane precursor material adopts poly-(4-vinylpridine), CdCl
2Concentration of aqueous solution be 1-100mM, the chloroformic solution concentration of poly-(4-vinylpridine) is 0.1-1mM, 1 hour-12 hours reaction times.
6, preparation method according to claim 3 is characterized in that metal-salt adopts AgNO
3, organic solvent adopts chloroform, and the organosilane precursor material adopts 5,10,15,20-four (4-pyridyl)-21 hydrogen, 23 hydrogen-porphyrin, AgNO
3Concentration of aqueous solution be 0.01-1M, 5,10,15,20-four (4-pyridyl)-21 hydrogen, the concentration of the chloroformic solution of 23 hydrogen-porphyrin is 0.1-1mM, 1 minute-1 hour reaction times.
7, preparation method according to claim 3 is characterized in that metal-salt adopts HgCl
2, organic solvent adopts chloroform, and the organosilane precursor material adopts 5,10,15,20-four (4-pyridyl)-21 hydrogen, 23 hydrogen-porphyrin, HgCl
2Concentration of aqueous solution be 10-200mM, 5,10,15,20-four (4-pyridyl)-21 hydrogen, the concentration of the chloroformic solution of 23 hydrogen-porphyrin is 0.1-1mM, 1 minute-1 hour reaction times.
8, preparation method according to claim 3 is characterized in that metal-salt adopts K
2PtCl
4, organic solvent adopts chloroform, and the organosilane precursor material adopts 5,10,15,20-four (4-pyridyl)-21 hydrogen, 23 hydrogen-porphyrin, K
2PtCl
4Concentration of aqueous solution be 0.1-1mM, 5,10,15,20-four (4-pyridyl)-21 hydrogen, the concentration of the chloroformic solution of 23 hydrogen-porphyrin is 0.1-1mM, week 1 hour-1 reaction times.
9, preparation method according to claim 3 is characterized in that metal-salt adopts K
2PdCl
4, organic solvent adopts chloroform, and the organosilane precursor material adopts zinc-5,15-two (4-pyridyl)-10,20-phenylbenzene porphyrin, K
2PdCl
4Concentration of aqueous solution be 0.1-1mM, zinc-5,15-two (4-pyridyl)-10, the concentration of the chloroformic solution of 20-phenylbenzene porphyrin is 0.1-1mM, week 1 hour-1 reaction times.
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| US20110135571A1 (en) * | 2008-02-22 | 2011-06-09 | Wenbin Lin | Hybrid nanoparticles as anti-cancer therapeutic agents and dual therapeutic/imaging contrast agents |
| CN101649393B (en) * | 2008-08-12 | 2011-05-11 | 兰州大学 | Method for enriching low-concentration valuable metals in mixed solution containing light metals |
| WO2012034379A1 (en) * | 2010-09-17 | 2012-03-22 | 上海交通大学 | Method for preparing ph sensitive metal organic coordination polymer |
| CN102240573A (en) * | 2011-04-09 | 2011-11-16 | 苏州大学 | Method for preparing organic hollow nano-material |
| EP2729180B1 (en) | 2011-07-08 | 2019-01-23 | The University of North Carolina At Chapel Hill | Metal bisphosphonate nanoparticles for anti-cancer therapy and imaging and for treating bone disorders |
| WO2015069926A1 (en) | 2013-11-06 | 2015-05-14 | The University Of Chicago | Nanoscale carriers for the delivery or co-delivery of chemotherapeutics, nucleic acids and photosensitizers |
| CN104232079B (en) * | 2014-09-24 | 2016-06-01 | 西安科技大学 | The preparation method of a kind of argentum nano composite material with fluorescent effect |
| WO2016061256A1 (en) | 2014-10-14 | 2016-04-21 | The University Of Chicago | Nanoparticles for photodynamic therapy, x-ray induced photodynamic therapy, radiotherapy, chemotherapy, immunotherapy, and any combination thereof |
| US10806694B2 (en) | 2014-10-14 | 2020-10-20 | The University Of Chicago | Nanoparticles for photodynamic therapy, X-ray induced photodynamic therapy, radiotherapy, radiodynamic therapy, chemotherapy, immunotherapy, and any combination thereof |
| WO2017201528A1 (en) | 2016-05-20 | 2017-11-23 | The University Of Chicago | Nanoparticles for chemotherapy, targeted therapy, photodynamic therapy, immunotherapy, and any combination thereof |
| EP3638367A4 (en) | 2017-08-02 | 2021-07-21 | The University of Chicago | Nanoscale metal-organic layers and metal-organic nanoplates for x-ray induced photodynamic therapy, radiotherapy, radiodynamic therapy, chemotherapy, immunotherapy, and any combination thereof |
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| WO2003082900A2 (en) * | 2002-03-22 | 2003-10-09 | Emory University | Self-assembling-peptide-based structures and processes for controlling the self-assembly of such structures |
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| CN1569956A (en) * | 2004-04-23 | 2005-01-26 | 中国科学院长春应用化学研究所 | Nano structural material model making method |
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