CN102161886B - Fluorescent molecular machine based on one-dimensional silicon nanowires and using method thereof - Google Patents
Fluorescent molecular machine based on one-dimensional silicon nanowires and using method thereof Download PDFInfo
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Abstract
The invention relates to a fluorescent molecular machine based on one-dimensional silicon nanowires and a using method thereof. The fluorescent molecular machine based on one-dimensional silicon nanowires consists of one-dimensional nanowires modified by 3-aminopropyltriethoxysilane, as well as N,N-bis-(4-p-formylphenylazobenzene-4'-methyl)-dansylamide and alpha-cyclodextrin, wherein the alpha-cyclodextrin is sleeved on the N,N-bis-(4-p-formylphenylazobenzene-4'-methyl)-dansylamide, and the N,N-bis-(4-p-formylphenylazobenzene-4'-methyl)-dansylamide is bonded with the one-dimensional nanowires modified by the 3-aminopropyltriethoxysilane by covalent bonds. In the invention, ultraviolet light and visible light are used as input to control the motion of the fluorescent molecular machine and fluorescence is used as output to demonstrate the motion of the fluorescent molecular machine.
Description
Technical field
The invention belongs to the fluorescence molecule field of machines of one dimension Nano structure, preparation method and the using method of the particularly fluorescence molecule machine based on the One Dimension Silicon nano wire, and this fluorescence molecule machine based on the One Dimension Silicon nano wire.
Background technology
For a long time, scientist wishes to develop the superminiature machine in the nanoscale scope always, wishes to use it for the dredging of blood vessel or the aspects such as reparation of damaged tissue.France and Germany scientist cooperation, successfully develop rotatable " molecular " first, and assemble out First fluorescence molecule machine truly-biological nano fluorescence molecule machine, and this has pulled open the prelude of fluorescence molecule machine research.After this, the investigator prepares again various fluorescence molecule machines, the dumb-bell shape molecule elevator (Science that the motivating force that comprises two chemical compositions drivings is 200pN, 303,1845-1849), can before and after walk about robot (Nature chemistry, 2,96-101), DNA molecular pliers (the Nano letters that controlled by acid-basicity, 9,4510-4514) etc.These fluorescence molecule machinery requirements are controlled as conditions such as pH with chemical reagent, and this just requires the fluorescence molecule machine to operate in solution, and the fluorescence molecule machine in solution is difficult to control, and the development of fluorescence molecule machine is restricted.The fluorescence molecule machine is fixed on solid surface and can solve its uppity problem in solution, and it should be the microcosmic material that the miniaturization of fluorescence molecule machine simultaneously requires carrier.The One Dimension Silicon the fabricate of nanowires is simple, easily finishing, conveniently makes nano-array, by the nano material in pair array, carries out respectively the modification of difference in functionality, and the fluorescence molecule machine array of formation is expected to complete a plurality of operations simultaneously.All these characteristics can make the One Dimension Silicon nano wire become suitable fluorescence molecule machine carrier.In addition, optical signal, as the input operation of fluorescence molecule machine is simple, highly sensitive, the time of response is short, can carry out radio operation at single molecules level, is a kind of desirable input/output signal.In conjunction with above-mentioned, the research of the light-operated fluorescence molecule machine of surface of silicon nanowires is significant to the simulation of following molecular computer and molecular level biological activity.
Summary of the invention
The objective of the invention is to take full advantage of the small size of One Dimension Silicon nano wire and accessibility prepared by the One Dimension Silicon nano-wire array, the nitrogen that combines cyclodextrin that will there is the molecule machine function, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified the surface of silicon nanowires, thereby a kind of molecule machine based on the One Dimension Silicon nano wire is provided, and the preparation method of this molecule machine based on the One Dimension Silicon nano wire.
A further object of the present invention is to provide the using method of the fluorescence molecule machine based on the One Dimension Silicon nano wire.
Fluorescence molecule machine based on the One Dimension Silicon nano wire of the present invention is that the One Dimension Silicon nanowire surface of being modified to the 3-aminopropyl triethoxysilane by the organic functional molecular covalent modification that combines cyclodextrin is built into.Described organic functional molecular is nitrogen, nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, and the One Dimension Silicon nano wire is not only as the substrate of organic functional molecular, and as the building block of light-operated fluorescence molecule machine.
Fluorescence molecule machine based on the One Dimension Silicon nano wire of the present invention is the One Dimension Silicon nano wire of being modified by the 3-aminopropyl triethoxysilane, and nitrogen, nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, and three parts of alpha-cylodextrin form; Wherein, described alpha-cylodextrin is to be enclosed within described nitrogen, on nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, described nitrogen, the One Dimension Silicon nano wire that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified with covalent bonds 3-aminopropyl triethoxysilane again.
The described nitrogen that is enclosed within, alpha-cylodextrin on nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire that can modify at described 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide molecule, move.
The diameter of the One Dimension Silicon nano wire that described 3-aminopropyl triethoxysilane is modified is 8nm～10nm, and length is 1 μ m～10 μ m.
Fluorescence molecule machine based on the One Dimension Silicon nano wire of the present invention is by three parts, nitrogen, the silicon nanowires that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, alpha-cylodextrin and 3-aminopropyl triethoxysilane are modified, at nitrogen, in the mixed solution of nitrogen-diformamide and water, normal-temperature reaction generates.
The preparation method of the fluorescence molecule machine based on the One Dimension Silicon nano wire of the present invention, be that the One Dimension Silicon nano wire to being prepared by vapour deposition process carries out surface treatment, and described surface treatment is to carry out surface active by chemical process; And then the surface of the One Dimension Silicon nano wire of the drying processed of effects on surface is modified, modify the nitrogen that combines alpha-cylodextrin with fluorescence molecule machine function at its surperficial covalent linkage, nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, obtain the fluorescence molecule machine based on the One Dimension Silicon nano wire.
The preparation method of the fluorescence molecule machine based on the One Dimension Silicon nano wire of the present invention is as shown in Figure 1: by nitrogen, the One Dimension Silicon nano wire that nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, alpha-cylodextrin and 3-aminopropyl triethoxysilane are modified is placed in nitrogen, carry out room temperature reaction in the mixed solution of nitrogen-diformamide and water, generate the thick product of target fluorescence molecule machine, then the thick product of the target fluorescence molecule machine that obtains is carried out to ultrasonic cleaning in organic solvent, obtain the described fluorescence molecule machine based on the One Dimension Silicon nano wire; Wherein, nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide: the One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified: the mass ratio of alpha-cylodextrin is 0.5:1:0.1～0.5:10:1; Nitrogen, the nitrogen in the mixed solution of nitrogen-diformamide and water, the volume ratio of nitrogen-diformamide and water is 5:1～10:1.
The described thick product by the target fluorescence molecule machine that obtains carries out ultrasonic cleaning in organic solvent, is successively at toluene, nitrogen, carries out ultrasonic cleaning in nitrogen-dimethyl formamide, methylene dichloride, ethanol.
The One Dimension Silicon nano wire that described 3-aminopropyl triethoxysilane is modified can be prepared by following methods: add the One Dimension Silicon nano wire that oxygen plasma treatment crosses (method of processing 1-3 hour in the oxygen plasma that can to adopt the One Dimension Silicon nano wire be 100-150 ℃ in temperature obtains) and dry toluene (wherein: the mass ratio of One Dimension Silicon nano wire and dry toluene is 1:100～1:200) in container, under rare gas element (as nitrogen) protection, being heated to temperature is 120～140 ℃ of component distillations, after steaming 50～70% dry toluene of added dry toluene volume, be cooled to 70～90 ℃ and add 3-aminopropyl triethoxysilane (wherein: the mass ratio of One Dimension Silicon nano wire and 3-aminopropyl triethoxysilane is 20:1～10:1), in temperature, be to stir (general churning time is 24～36 hours) under 80～100 ℃, be down to room temperature, filtration obtains the thick product of One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified, clean the thick product of One Dimension Silicon nano wire that this 3-aminopropyl triethoxysilane is modified, filter, remove unreacted 3-aminopropyl triethoxysilane, vacuum-drying obtains the One Dimension Silicon nano wire that described 3-aminopropyl triethoxysilane is modified.
The One Dimension Silicon nano wire that described cleaning 3-aminopropyl triethoxysilane is modified is repeatedly to carry out successively ultrasonic cleaning in toluene, methylene dichloride, ethanol.
Described One Dimension Silicon nano wire can prepare with vapour deposition process.
The diameter of described One Dimension Silicon nano wire is 8nm～10nm, and length is 1 μ m～10 μ m.
Described nitrogen, nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide can be prepared by following methods (as shown in Figure 2):
(1) adding 4-2-bromomethylphenyl-4-iodophenyl-azo, Anhydrous potassium carbonate, potassiumiodide, dansyl amide, acetonitrile (4-2-bromomethylphenyl-4-iodophenyl-azo: Anhydrous potassium carbonate: potassiumiodide: dansyl amide: the mol ratio of acetonitrile is 1:2:1:2:520～1:4:1:4:780) in container (as flask), is under 50～90 ℃, to reflux 8～16 hours in temperature; Filtering reacting liquid, obtain nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide;
(2) under rare gas element (as nitrogen) protection; the nitrogen that adds step (1) to obtain in container (as flask), nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide, salt of wormwood, two-triphenyl phosphorus palladium chloride (Pd(PPh
3)
2cl
2) (nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide: salt of wormwood: Pd(PPh
3)
2cl
2mol ratio be 1:2:0.001～1:2:0.006); Inject nitrogen, the mixed solution that the volume ratio of nitrogen-diformamide and water is 5:1～10:1 (mass ratio of the mixed solution of nitrogen-diformamide and water is 1:290～1:780 for nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide and nitrogen); Stir the nitrogen that after 10～20 minutes, injection contains the 4-formylphenylboronic acid, the mixed solution of nitrogen-diformamide and water (4-formylphenylboronic acid and nitrogen, the mass ratio of the mixed solution of nitrogen-diformamide and water is 1:100～1:300, nitrogen, the volume ratio of nitrogen-diformamide and water is 5:1～10:1); Wherein, nitrogen, the mol ratio of nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide and 4-formylphenylboronic acid is 1:2～1:6; Be that 100～150 ℃ of unglazed photographs under condition are reacted 8～24 hours in temperature, obtain described nitrogen, nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide.
The present invention uses UV-light and visible ray as input, described fluorescence molecule machine movement to be controlled, and characterizes the motion of fluorescence molecule machine as output with fluorescence.
Control to the fluorescence molecule machine based on the One Dimension Silicon nano wire of the present invention is used, it is to adopt light to be controlled: the middle suspension liquid (mass ratio of the fluorescence molecule machine based on the One Dimension Silicon nano wire and the mixed solution of second alcohol and water is 1:500～1:2000) that forms of mixed solution (in the mixed solution of second alcohol and water, the quality percentage composition of ethanol is 20%～95%) that the described fluorescence molecule machine based on the One Dimension Silicon nano wire is scattered in to the second alcohol and water, use successively the light that wavelength is 250～260nm, use the light that wavelength is 420～430nm and use the light that wavelength is 365～375nm to carry out the illumination (light of above-mentioned three kinds of wavelength to the above-mentioned suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire, general each light application time is 5～10 minutes), all using wavelength after each illumination is the exciting light of 360～370nm, and the suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after above-mentioned illumination is excited, and to exciting the fluorescent emission wavelength obtained after described fluorescence molecule machine, is tested.The peak value of the fluorescent emission wavelength that test obtains is all between 505～515nm.
Detect the nitrogen of the fluorescence molecule machine surface based on the One Dimension Silicon nano wire by fluorescence spectrophotometer, the enhancing of the fluorescent emission wavelength of nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide or weaken variation.On fluorescence spectrophotometer, use successively light that wavelength is 250～260nm, the suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after using light that wavelength is 420～430nm to above-mentioned illumination carries out the illumination (light of above-mentioned two kinds of wavelength, general each light application time is 5～10 minutes), the fluorescent emission wavelength obtained after the described fluorescence molecule machine of illumination is tested, and the intensity of the fluorescent emission wavelength that test obtains strengthens gradually.And the light that is the suspension that reaches fluorescent emission Wavelength strength peak value 365～375nm with wavelength carries out illumination (general light application time is 5～10 minutes), the strength reduction of fluorescent emission wavelength (as described in Figure 3).The One Dimension Silicon nano wire that above-mentioned explanation alpha-cylodextrin is modified at the 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, move.Because alpha-cylodextrin is near fluorophor nitrogen, can hinder its intramolecular rotatablely moving during nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-position, dansyl amide position, fluorescence is strengthened.
One Dimension Silicon nano wire in the present invention is not only as the substrate of organic functional molecular, and as the building block of light-operated fluorescence molecule machine.By the One Dimension Silicon nano wire is carried out to finishing, realized the fluorescence molecule machine based on the One Dimension Silicon nano wire, it has logic function.And the volume of One Dimension Silicon nano wire is little, easily make array, these provide a kind of new thinking and method for preparing the higher light shutter device of less, the integrated degree of volume.
The accompanying drawing explanation
Fig. 1. the transmission electron microscope figure of One Dimension Silicon nano wire.
Fig. 2. preparation method's schematic diagram of the finishing of One Dimension Silicon nano wire and fluorescence molecule machine in embodiment of the present invention 1-6.
Fig. 3. the schematic diagram of the organic functional molecular building-up process of embodiment of the present invention 1-6.
Fig. 4. the schematic diagram of embodiment of the present invention 1-6 fluorescence molecule machine movement.
Fig. 5. the embodiment of the present invention 2 change in fluorescence figure a and cycle diagram b.
Embodiment
Embodiment 1
1 gram SiO is positioned in the middle of the aluminum oxide boiler tube of horizontal pipe furnace, then the aluminum oxide boiler tube is evacuated to 1 handkerchief, then, to the mixed gas that passes into argon gas and hydrogen in the aluminum oxide boiler tube, wherein hydrogen content accounts for 5% of mixed gas volume.By the stable gas pressure of aluminum oxide boiler tube at 1000 handkerchiefs.Then the tube furnace temperature is elevated to 1350 ℃, and keeps temperature after 6 hours, tube furnace is lowered the temperature naturally.Finally in tube furnace, obtain the One Dimension Silicon nano wire, the diameter of One Dimension Silicon nano wire is 8nm～10nm, and length is 1 μ m～10 μ m.Referring to Fig. 1.
(method of processing 3 hours in the oxygen plasma that can to adopt the One Dimension Silicon nano wire be 50 ℃ in temperature obtains to add the One Dimension Silicon nano wire that oxygen plasma treatment crosses in being connected with the round-bottomed flask of water trap, the diameter of One Dimension Silicon nano wire is 8nm～10nm, length is 1 μ m～10 μ m) and dry toluene (wherein: the mass ratio of One Dimension Silicon nano wire and dry toluene is .1:500), under nitrogen protection, after being heated to 70% the dry toluene that 140 ℃ of component distillations go out added dry toluene volume, be down to 90 ℃ and add 3-aminopropyl triethoxysilane (wherein: the mass ratio of One Dimension Silicon nano wire and 3-aminopropyl triethoxysilane is 20:1), in temperature, be to stir 24 hours under 100 ℃, be down to room temperature, filtration obtains the thick product of One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.This thick product carries out ultrasonic cleaning repeatedly successively in toluene, methylene dichloride, ethanol, filters, and removes unreacted 3-aminopropyl triethoxysilane, and vacuum-drying obtains the One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.Referring to Fig. 2.
Add 260 milligrams of 4-2-bromomethylphenyls-4-iodophenyl-azo (0.65mmol) in round-bottomed flask, 360 milligrams of Anhydrous potassium carbonates, 108 milligrams of potassiumiodides, 650 milligrams of dansyl amides, 27.6 milliliters of acetonitriles, 90 ℃ of lower back flow reaction 16 hours.Filtration obtains nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide.
Under the protection of nitrogen, in 25 milliliters of two-mouth bottles of tinfoil parcel, add 89 milligrams of nitrogen obtained above, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide (0.1mmol), 4.2 milligrams of Pd(PPh
3)
2cl
2, 27.2 milligrams of salt of wormwood.Inject 9 milliliters of nitrogen, the mixed solution of nitrogen-diformamide and water (volume ratio 10:1).Stir 9 milliliters of nitrogen that after 20 minutes, injection contains 90 milligrams of 4-formylphenylboronic acids, the mixed solution of nitrogen-diformamide and water (volume ratio is 10:1).Under 150 ℃, reaction is 24 hours, obtains nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide.Referring to Fig. 3.
At 9 milliliters of nitrogen, add the 50mg alpha-cylodextrin in the mixed solution of nitrogen-diformamide and water (volume ratio 10:1), One Dimension Silicon nano wire and 100mg nitrogen that 1g 3-aminopropyl triethoxysilane obtained above is modified, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, room temperature (25 ℃) stirs 24 hours, reaction generates the thick product of target fluorescence molecule machine, then by the thick product of the target fluorescence molecule machine that obtains successively at toluene, nitrogen, nitrogen-dimethyl formamide, methylene dichloride, carry out ultrasonic cleaning in ethanol, remove unreacted nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, vacuum-drying obtains the fluorescence molecule machine of target based on the One Dimension Silicon nano wire in 24 hours.Alpha-cylodextrin in the described fluorescence molecule machine based on the One Dimension Silicon nano wire is to be enclosed within nitrogen, on nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, nitrogen, the One Dimension Silicon nano wire that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified with covalent bonds 3-aminopropyl triethoxysilane again.
The described nitrogen that is enclosed within, alpha-cylodextrin on nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire that can modify at described 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide molecule, move.Referring to Fig. 4.
Use UV-light and visible ray as input, above-mentioned fluorescence molecule machine movement to be controlled, characterize the motion of fluorescence molecule machine with fluorescence as output.
The described fluorescence molecule machine based on the One Dimension Silicon nano wire is scattered in to the middle suspension liquid (mass ratio of the fluorescence molecule machine based on the One Dimension Silicon nano wire and the mixed solution of second alcohol and water is 1:2000) that forms of mixed solution (in the mixed solution of second alcohol and water, the quality percentage composition of ethanol is 95%) of second alcohol and water, use successively light that wavelength is 260nm, use the light that wavelength is 430nm and use the light that wavelength is 370nm to carry out illumination to the above-mentioned suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire, each light application time is 10 minutes; All using wavelength after each illumination is that the motion of the described fluorescence molecule machine based on the One Dimension Silicon nano wire in the exciting light of the 375nm suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after to above-mentioned illumination is excited, to exciting the fluorescent emission wavelength obtained after described fluorescence molecule machine to be tested, the peak value of the fluorescent emission wavelength that test obtains is all at 515nm.
1 gram SiO is positioned in the middle of the aluminum oxide boiler tube of horizontal pipe furnace, then the aluminum oxide boiler tube is evacuated to 1 handkerchief, then, to the mixed gas that passes into argon gas and hydrogen in the aluminum oxide boiler tube, wherein hydrogen content accounts for 5% of mixed gas volume.By the stable gas pressure of aluminum oxide boiler tube at 1000 handkerchiefs.Then the tube furnace temperature is elevated to 1350 ℃, and keeps temperature after 6 hours, tube furnace is lowered the temperature naturally.Finally in tube furnace, obtain the One Dimension Silicon nano wire, the diameter of One Dimension Silicon nano wire is 8nm～10nm, and length is 1 μ m～10 μ m.Referring to Fig. 1.
(method of processing 1 hour in the oxygen plasma that can to adopt the One Dimension Silicon nano wire be 100 ℃ in temperature obtains to add the One Dimension Silicon nano wire that oxygen plasma treatment crosses in being connected with the round-bottomed flask of water trap, the diameter of One Dimension Silicon nano wire is 8nm～10nm, length is 1 μ m～10 μ m) and dry toluene (wherein: the mass ratio of One Dimension Silicon nano wire and dry toluene is .1:100), under nitrogen protection, after being heated to 50% the dry toluene that 120 ℃ of component distillations go out added dry toluene volume, be down to 70 ℃ and add 3-aminopropyl triethoxysilane (wherein: the mass ratio of One Dimension Silicon nano wire and 3-aminopropyl triethoxysilane is 10:1), in temperature, be to stir 24 hours under 80 ℃, be down to room temperature, filtration obtains the thick product of One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.This thick product carries out ultrasonic cleaning repeatedly successively in toluene, methylene dichloride, ethanol, filters, and removes unreacted 3-aminopropyl triethoxysilane, and vacuum-drying obtains the One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.Referring to Fig. 2.
Add 260 milligrams of 4-2-bromomethylphenyls-4-iodophenyl-azo (0.65mmol) in round-bottomed flask, 180 milligrams of Anhydrous potassium carbonates, 108 milligrams of potassiumiodides, 325 milligrams of dansyl amides, 18.4 milliliters of acetonitriles, 50 ℃ of lower back flow reaction 8 hours.Filtration obtains nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide.
Under the protection of nitrogen, in 25 milliliters of two-mouth bottles of tinfoil parcel, add 89 milligrams of nitrogen obtained above, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide (0.1mmol), 0.7 milligram of Pd(PPh
3)
2cl
2, 27.2 milligrams of salt of wormwood.Inject 3 milliliters of nitrogen, the mixed solution of nitrogen-diformamide and water (volume ratio 5:1).Stir 3 milliliters of nitrogen that after 10 minutes, injection contains 30 milligrams of 4-formylphenylboronic acids, the mixed solution of nitrogen-diformamide and water (volume ratio is 5:1).Under 100 ℃, reaction is 24 hours, obtains nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide.Referring to Fig. 3.
At 3 milliliters of nitrogen, add the 50mg alpha-cylodextrin in the mixed solution of nitrogen-diformamide and water (volume ratio 5:1), One Dimension Silicon nano wire and 10mg nitrogen that 100mg 3-aminopropyl triethoxysilane obtained above is modified, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, room temperature (25 ℃) stirs 24 hours, reaction generates the thick product of target fluorescence molecule machine, then by the thick product of the target fluorescence molecule machine that obtains successively at toluene, nitrogen, nitrogen-dimethyl formamide, methylene dichloride, carry out ultrasonic cleaning in ethanol, remove unreacted nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, vacuum-drying obtains the fluorescence molecule machine of target based on the One Dimension Silicon nano wire in 24 hours.Alpha-cylodextrin in the described fluorescence molecule machine based on the One Dimension Silicon nano wire is to be enclosed within nitrogen, on nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, nitrogen, the One Dimension Silicon nano wire that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified with covalent bonds 3-aminopropyl triethoxysilane again.
The described nitrogen that is enclosed within, alpha-cylodextrin on nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire that can modify at described 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide molecule, move.Referring to Fig. 4.
Use UV-light and visible ray as input, above-mentioned fluorescence molecule machine movement to be controlled, characterize the motion of fluorescence molecule machine with fluorescence as output.
The described fluorescence molecule machine based on the One Dimension Silicon nano wire is scattered in to the middle suspension liquid (mass ratio of the fluorescence molecule machine based on the One Dimension Silicon nano wire and the mixed solution of second alcohol and water is 1:500) that forms of mixed solution (in the mixed solution of second alcohol and water, the quality percentage composition of ethanol is 20%) of second alcohol and water, use successively light that wavelength is 250nm, use the light that wavelength is 420nm and use the light that wavelength is 360nm to carry out illumination to the above-mentioned suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire, each light application time is 5 minutes; All use wavelength after each illumination is fluorometric investigation in the exciting light of the 365nm suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after to above-mentioned illumination, and the peak value of testing the fluorescent emission wavelength obtained is all at 505nm.Referring to Fig. 5.
Embodiment 3
1 gram SiO is positioned in the middle of the aluminum oxide boiler tube of horizontal pipe furnace, then the aluminum oxide boiler tube is evacuated to 1 handkerchief, then, to the mixed gas that passes into argon gas and hydrogen in the aluminum oxide boiler tube, wherein hydrogen content accounts for 5% of mixed gas volume.By the stable gas pressure of aluminum oxide boiler tube at 1000 handkerchiefs.Then the tube furnace temperature is elevated to 1350 ℃, and keeps temperature after 6 hours, tube furnace is lowered the temperature naturally.Finally in tube furnace, obtain the One Dimension Silicon nano wire, the diameter of One Dimension Silicon nano wire is 8nm～10nm, and length is 1 μ m～10 μ m.Referring to Fig. 1.
(method of processing 2 hours in the oxygen plasma that can to adopt the One Dimension Silicon nano wire be 110 ℃ in temperature obtains to add the One Dimension Silicon nano wire that oxygen plasma treatment crosses in being connected with the round-bottomed flask of water trap, the diameter of One Dimension Silicon nano wire is 8nm～10nm, length is 1 μ m～10 μ m) and dry toluene (wherein: the mass ratio of One Dimension Silicon nano wire and dry toluene is .1:200), under nitrogen protection, after being heated to 60% the dry toluene that 130 ℃ of component distillations go out added dry toluene volume, be down to 80 ℃ and add 3-aminopropyl triethoxysilane (wherein: the mass ratio of One Dimension Silicon nano wire and 3-aminopropyl triethoxysilane is 11:1), in temperature, be to stir 24 hours under 80 ℃, be down to room temperature, filtration obtains the thick product of One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.This thick product carries out ultrasonic cleaning repeatedly successively in toluene, methylene dichloride, ethanol, filters, and removes unreacted 3-aminopropyl triethoxysilane, and vacuum-drying obtains the One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.Referring to Fig. 2.
Add 260 milligrams of 4-2-bromomethylphenyls-4-iodophenyl-azo (0.65mmol) in round-bottomed flask, 190 milligrams of Anhydrous potassium carbonates, 108 milligrams of potassiumiodides, 425 milligrams of dansyl amides, 19.4 milliliters of acetonitriles, 60 ℃ of lower back flow reaction 8 hours.Filtration obtains nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide.
Under the protection of nitrogen, in 25 milliliters of two-mouth bottles of tinfoil parcel, add 89 milligrams of nitrogen obtained above, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide (0.1mmol), 3.7 milligrams of Pd(PPh
3)
2cl
2, 27.2 milligrams of salt of wormwood.Inject 5 milliliters of nitrogen, the mixed solution of nitrogen-diformamide and water (volume ratio 7:1).Stir 5 milliliters of nitrogen that after 13 minutes, injection contains 60 milligrams of 4-formylphenylboronic acids, the mixed solution of nitrogen-diformamide and water (volume ratio is 6:1).Under 110 ℃, reaction is 24 hours, obtains nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide.Referring to Fig. 3.
At 8 milliliters of nitrogen, add the 50mg alpha-cylodextrin in the mixed solution of nitrogen-diformamide and water (volume ratio 8:1), One Dimension Silicon nano wire and 20mg nitrogen that 200mg 3-aminopropyl triethoxysilane obtained above is modified, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, room temperature (25 ℃) stirs 24 hours, reaction generates the thick product of target fluorescence molecule machine, then by the thick product of the target fluorescence molecule machine that obtains successively at toluene, nitrogen, nitrogen-dimethyl formamide, methylene dichloride, carry out ultrasonic cleaning in ethanol, remove unreacted nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, vacuum-drying obtains the fluorescence molecule machine of target based on the One Dimension Silicon nano wire in 24 hours.Alpha-cylodextrin in the described fluorescence molecule machine based on the One Dimension Silicon nano wire is to be enclosed within nitrogen, on nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, nitrogen, the One Dimension Silicon nano wire that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified with covalent bonds 3-aminopropyl triethoxysilane again.
The described nitrogen that is enclosed within, alpha-cylodextrin on nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire that can modify at described 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide molecule, move.Referring to Fig. 4
Use UV-light and visible ray as input, above-mentioned fluorescence molecule machine movement to be controlled, characterize the motion of fluorescence molecule machine with fluorescence as output.
The described fluorescence molecule machine based on the One Dimension Silicon nano wire is scattered in to the middle suspension liquid (mass ratio of the fluorescence molecule machine based on the One Dimension Silicon nano wire and the mixed solution of second alcohol and water is 1:600) that forms of mixed solution (in the mixed solution of second alcohol and water, the quality percentage composition of ethanol is 30%) of second alcohol and water, use successively light that wavelength is 251nm, use the light that wavelength is 421nm and use the light that wavelength is 361nm to carry out illumination to the above-mentioned suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire, each light application time is 6 minutes; All use wavelength after each illumination is fluorometric investigation in the exciting light of the 366nm suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after to above-mentioned illumination, and the peak value of testing the fluorescent emission wavelength obtained is all at 508nm.
Embodiment 4
1 gram SiO is positioned in the middle of the aluminum oxide boiler tube of horizontal pipe furnace, then the aluminum oxide boiler tube is evacuated to 1 handkerchief, then, to the mixed gas that passes into argon gas and hydrogen in the aluminum oxide boiler tube, wherein hydrogen content accounts for 5% of mixed gas volume.By the stable gas pressure of aluminum oxide boiler tube at 1000 handkerchiefs.Then the tube furnace temperature is elevated to 1350 ℃, and keeps temperature after 6 hours, tube furnace is lowered the temperature naturally.Finally in tube furnace, obtain the One Dimension Silicon nano wire, the diameter of One Dimension Silicon nano wire is 8nm～10nm, and length is 1 μ m～10 μ m.Referring to Fig. 1.
(method of processing 2 hours in the oxygen plasma that can to adopt the One Dimension Silicon nano wire be 110 ℃ in temperature obtains to add the One Dimension Silicon nano wire that oxygen plasma treatment crosses in being connected with the round-bottomed flask of water trap, the diameter of One Dimension Silicon nano wire is 8nm～10nm, length is 1 μ m～10 μ m) and dry toluene (wherein: the mass ratio of One Dimension Silicon nano wire and dry toluene is .1:300), under nitrogen protection, after being heated to 65% the dry toluene that 130 ℃ of component distillations go out added dry toluene volume, be down to 80 ℃ and add 3-aminopropyl triethoxysilane (wherein: the mass ratio of One Dimension Silicon nano wire and 3-aminopropyl triethoxysilane is 12:1), in temperature, be to stir 24 hours under 85 ℃, be down to room temperature, filtration obtains the thick product of One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.This thick product carries out ultrasonic cleaning repeatedly successively in toluene, methylene dichloride, ethanol, filters, and removes unreacted 3-aminopropyl triethoxysilane, and vacuum-drying obtains the One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.Referring to Fig. 2.
Add 260 milligrams of 4-2-bromomethylphenyls-4-iodophenyl-azo (0.65mmol) in round-bottomed flask, 200 milligrams of Anhydrous potassium carbonates, 108 milligrams of potassiumiodides, 525 milligrams of dansyl amides, 20.4 milliliters of acetonitriles, 65 ℃ of lower back flow reaction 12 hours.Filtration obtains nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide.
Under the protection of nitrogen, in 25 milliliters of two-mouth bottles of tinfoil parcel, add 89 milligrams of nitrogen obtained above, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide (0.1mmol), 2.7 milligrams of Pd(PPh
3)
2cl
2, 27.2 milligrams of salt of wormwood.Inject 6 milliliters of nitrogen, the mixed solution of nitrogen-diformamide and water (volume ratio 9:1).Stir 4 milliliters of nitrogen that after 15 minutes, injection contains 50 milligrams of 4-formylphenylboronic acids, the mixed solution of nitrogen-diformamide and water (volume ratio is 9:1).Under 115 ℃, reaction is 24 hours, obtains nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide.Referring to Fig. 3.
At 6 milliliters of nitrogen, add the 50mg alpha-cylodextrin in the mixed solution of nitrogen-diformamide and water (volume ratio 9:1), One Dimension Silicon nano wire and 30mg nitrogen that 300mg 3-aminopropyl triethoxysilane obtained above is modified, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, stirring at room 24 hours, reaction generates the thick product of target fluorescence molecule machine, then by the thick product of the target fluorescence molecule machine that obtains successively at toluene, nitrogen, nitrogen-dimethyl formamide, methylene dichloride, carry out ultrasonic cleaning in ethanol, remove unreacted nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, vacuum-drying obtains the fluorescence molecule machine of target based on the One Dimension Silicon nano wire in 24 hours.Alpha-cylodextrin in the described fluorescence molecule machine based on the One Dimension Silicon nano wire is to be enclosed within nitrogen, on nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, nitrogen, the One Dimension Silicon nano wire that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified with covalent bonds 3-aminopropyl triethoxysilane again.
The described nitrogen that is enclosed within, alpha-cylodextrin on nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire that can modify at described 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide molecule, move.Referring to Fig. 4.
Use UV-light and visible ray as input, above-mentioned fluorescence molecule machine movement to be controlled, characterize the motion of fluorescence molecule machine with fluorescence as output.
The described fluorescence molecule machine based on the One Dimension Silicon nano wire is scattered in to the middle suspension liquid (mass ratio of the fluorescence molecule machine based on the One Dimension Silicon nano wire and the mixed solution of second alcohol and water is 1:700) that forms of mixed solution (in the mixed solution of second alcohol and water, the quality percentage composition of ethanol is 40%) of second alcohol and water, use successively light that wavelength is 255nm, use the light that wavelength is 425nm and use the light that wavelength is 365nm to carry out illumination to the above-mentioned suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire, each light application time is 6 minutes; All use wavelength after each illumination is fluorometric investigation in the exciting light of the 367nm suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after to above-mentioned illumination, and the peak value of testing the fluorescent emission wavelength obtained is all at 509nm.
Embodiment 5
1 gram SiO is positioned in the middle of the aluminum oxide boiler tube of horizontal pipe furnace, then the aluminum oxide boiler tube is evacuated to 1 handkerchief, then, to the mixed gas that passes into argon gas and hydrogen in the aluminum oxide boiler tube, wherein hydrogen content accounts for 5% of mixed gas volume.By the stable gas pressure of aluminum oxide boiler tube at 1000 handkerchiefs.Then the tube furnace temperature is elevated to 1350 ℃, and keeps temperature after 6 hours, tube furnace is lowered the temperature naturally.Finally in tube furnace, obtain the One Dimension Silicon nano wire, the diameter of One Dimension Silicon nano wire is 8nm～10nm, and length is 1 μ m～10 μ m.Referring to Fig. 1.
(method of processing 2 hours in the oxygen plasma that can to adopt the One Dimension Silicon nano wire be 110 ℃ in temperature obtains to add the One Dimension Silicon nano wire that oxygen plasma treatment crosses in being connected with the round-bottomed flask of water trap, the diameter of One Dimension Silicon nano wire is 8nm～10nm, length is 1 μ m～10 μ m) and dry toluene (wherein: the mass ratio of One Dimension Silicon nano wire and dry toluene is .1:400), under nitrogen protection, after being heated to 55% the dry toluene that 125 ℃ of component distillations go out added dry toluene volume, be down to 85 ℃ and add 3-aminopropyl triethoxysilane (wherein: the mass ratio of One Dimension Silicon nano wire and 3-aminopropyl triethoxysilane is 12:1), in temperature, be to stir 24 hours under 85 ℃, be down to room temperature, filtration obtains the thick product of One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.This thick product carries out ultrasonic cleaning repeatedly successively in toluene, methylene dichloride, ethanol, filters, and removes unreacted 3-aminopropyl triethoxysilane, and vacuum-drying obtains the One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.Referring to Fig. 2.
Add 260 milligrams of 4-2-bromomethylphenyls-4-iodophenyl-azo (0.65mmol) in round-bottomed flask, 300 milligrams of Anhydrous potassium carbonates, 108 milligrams of potassiumiodides, 555 milligrams of dansyl amides, 21.4 milliliters of acetonitriles, 66 ℃ of lower back flow reaction 15 hours.Filtration obtains nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide.
Under the protection of nitrogen, in 25 milliliters of two-mouth bottles of tinfoil parcel, add 89 milligrams of nitrogen obtained above, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide (0.1mmol), 2.5 milligrams of Pd(PPh
3)
2cl
2, 27.2 milligrams of salt of wormwood.Inject 4 milliliters of nitrogen, the mixed solution of nitrogen-diformamide and water (volume ratio 8:1).Stir 5 milliliters of nitrogen that after 12 minutes, injection contains 70 milligrams of 4-formylphenylboronic acids, the mixed solution of nitrogen-diformamide and water (volume ratio is 8:1).Under 125 ℃, reaction is 24 hours, obtains nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide.Referring to Fig. 3.
At 7 milliliters of nitrogen, add the 50mg alpha-cylodextrin in the mixed solution of nitrogen-diformamide and water (volume ratio 7:1), One Dimension Silicon nano wire and 40mg nitrogen that 400mg 3-aminopropyl triethoxysilane obtained above is modified, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, room temperature (25 ℃) stirs 24 hours, reaction generates the thick product of target fluorescence molecule machine, then by the thick product of the target fluorescence molecule machine that obtains successively at toluene, nitrogen, nitrogen-dimethyl formamide, methylene dichloride, carry out ultrasonic cleaning in ethanol, remove unreacted nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, vacuum-drying obtains the fluorescence molecule machine of target based on the One Dimension Silicon nano wire in 24 hours.Alpha-cylodextrin in the described fluorescence molecule machine based on the One Dimension Silicon nano wire is to be enclosed within nitrogen, on nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, nitrogen, the One Dimension Silicon nano wire that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified with covalent bonds 3-aminopropyl triethoxysilane again.
The described nitrogen that is enclosed within, alpha-cylodextrin on nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire that can modify at described 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide molecule, move.Referring to Fig. 4.
Use UV-light and visible ray as input, above-mentioned fluorescence molecule machine movement to be controlled, characterize the motion of fluorescence molecule machine with fluorescence as output.
The described fluorescence molecule machine based on the One Dimension Silicon nano wire is scattered in to the middle suspension liquid (mass ratio of the fluorescence molecule machine based on the One Dimension Silicon nano wire and the mixed solution of second alcohol and water is 1:800) that forms of mixed solution (in the mixed solution of second alcohol and water, the quality percentage composition of ethanol is 50%) of second alcohol and water, use successively light that wavelength is 258nm, use the light that wavelength is 428nm and use the light that wavelength is 368nm to carry out illumination to the above-mentioned suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire, each light application time is 7 minutes; All use wavelength after each illumination is fluorometric investigation in the exciting light of the 368nm suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after to above-mentioned illumination, and the peak value of testing the fluorescent emission wavelength obtained is all at 510nm.
1 gram SiO is positioned in the middle of the aluminum oxide boiler tube of horizontal pipe furnace, then the aluminum oxide boiler tube is evacuated to 1 handkerchief, then, to the mixed gas that passes into argon gas and hydrogen in the aluminum oxide boiler tube, wherein hydrogen content accounts for 5% of mixed gas volume.By the stable gas pressure of aluminum oxide boiler tube at 1000 handkerchiefs.Then the tube furnace temperature is elevated to 1350 ℃, and keeps temperature after 6 hours, tube furnace is lowered the temperature naturally.Finally in tube furnace, obtain the One Dimension Silicon nano wire, the diameter of One Dimension Silicon nano wire is 8nm～10nm, and length is 1 μ m～10 μ m.Referring to Fig. 1.
(method of processing 2 hours in the oxygen plasma that can to adopt the One Dimension Silicon nano wire be 110 ℃ in temperature obtains to add the One Dimension Silicon nano wire that oxygen plasma treatment crosses in being connected with the round-bottomed flask of water trap, the diameter of One Dimension Silicon nano wire is 8nm～10nm, length is 1 μ m～10 μ m) and dry toluene (wherein: the mass ratio of One Dimension Silicon nano wire and dry toluene is .1:450), under nitrogen protection, after being heated to 45% the dry toluene that 125 ℃ of component distillations go out added dry toluene volume, be down to 85 ℃ and add 3-aminopropyl triethoxysilane (wherein: the mass ratio of One Dimension Silicon nano wire and 3-aminopropyl triethoxysilane is 18:1), in temperature, be to stir 24 hours under 85 ℃, be down to room temperature, filtration obtains the thick product of One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.This thick product carries out ultrasonic cleaning repeatedly successively in toluene, methylene dichloride, ethanol, filters, and removes unreacted 3-aminopropyl triethoxysilane, and vacuum-drying obtains the One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified.Referring to Fig. 2.
Add 260 milligrams of 4-2-bromomethylphenyls-4-iodophenyl-azo (0.65mmol) in round-bottomed flask, 320 milligrams of Anhydrous potassium carbonates, 108 milligrams of potassiumiodides, 595 milligrams of dansyl amides, 22.4 milliliters of acetonitriles, 67 ℃ of lower back flow reaction 16 hours.Filtration obtains nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide.
Under the protection of nitrogen, in 25 milliliters of two-mouth bottles of tinfoil parcel, add 89 milligrams of nitrogen obtained above, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide (0.1mmol), 3.5 milligrams of Pd(PPh
3)
2cl
2, 27.2 milligrams of salt of wormwood.Inject 6 milliliters of nitrogen, the mixed solution of nitrogen-diformamide and water (volume ratio 6:1).Stir 6 milliliters of nitrogen that after 18 minutes, injection contains 80 milligrams of 4-formylphenylboronic acids, the mixed solution of nitrogen-diformamide and water (volume ratio is 7:1).Under 124 ℃, reaction is 24 hours, obtains nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide.Referring to Fig. 3.
At 6 milliliters of nitrogen, add the 50mg alpha-cylodextrin in the mixed solution of nitrogen-diformamide and water (volume ratio 6:1), One Dimension Silicon nano wire and 50mg nitrogen that 600mg 3-aminopropyl triethoxysilane obtained above is modified, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, room temperature (25 ℃) stirs 24 hours, reaction generates the thick product of target fluorescence molecule machine, then by the thick product of the target fluorescence molecule machine that obtains successively at toluene, nitrogen, nitrogen-dimethyl formamide, methylene dichloride, carry out ultrasonic cleaning in ethanol, remove unreacted nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, vacuum-drying obtains the fluorescence molecule machine of target based on the One Dimension Silicon nano wire in 24 hours.Alpha-cylodextrin in the described fluorescence molecule machine based on the One Dimension Silicon nano wire is to be enclosed within nitrogen, on nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, nitrogen, the One Dimension Silicon nano wire that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified with covalent bonds 3-aminopropyl triethoxysilane again.
The described nitrogen that is enclosed within, alpha-cylodextrin on nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire that can modify at described 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide molecule, move.Referring to Fig. 4.
Use UV-light and visible ray as input, above-mentioned fluorescence molecule machine movement to be controlled, characterize the motion of fluorescence molecule machine with fluorescence as output.
The described fluorescence molecule machine based on the One Dimension Silicon nano wire is scattered in to the middle suspension liquid (mass ratio of the fluorescence molecule machine based on the One Dimension Silicon nano wire and the mixed solution of second alcohol and water is 1:900) that forms of mixed solution (in the mixed solution of second alcohol and water, the quality percentage composition of ethanol is 70%) of second alcohol and water, use successively light that wavelength is 259nm, use the light that wavelength is 429nm and use the light that wavelength is 369nm to carry out illumination to the above-mentioned suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire, each light application time is 7 minutes; All use wavelength after each illumination is fluorometric investigation in the exciting light of the 369nm suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after to above-mentioned illumination, and the peak value of testing the fluorescent emission wavelength obtained is all at 512nm.
Claims (7)
1. the fluorescence molecule machine based on the One Dimension Silicon nano wire, it is characterized in that: the described fluorescence molecule machine based on the One Dimension Silicon nano wire is the One Dimension Silicon nano wire of being modified by the 3-aminopropyl triethoxysilane, and nitrogen, nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, and three parts of alpha-cylodextrin form; Wherein, described alpha-cylodextrin is to be enclosed within described nitrogen, on nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, described nitrogen, the One Dimension Silicon nano wire that nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is modified with covalent bonds 3-aminopropyl triethoxysilane again;
The described nitrogen that is enclosed within, alpha-cylodextrin on nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire of modifying at described 3-aminopropyl triethoxysilane and with the nitrogen of its covalent bonds, between the end of nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide molecule, move.
2. the preparation method of the fluorescence molecule machine based on the One Dimension Silicon nano wire according to claim 1, it is characterized in that: by nitrogen, nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide, the One Dimension Silicon nano wire that alpha-cylodextrin and 3-aminopropyl triethoxysilane are modified is placed in nitrogen, in the mixed solution of nitrogen-diformamide and water, reacted, generate the thick product of target fluorescence molecule machine, then the thick product of the target fluorescence molecule machine that obtains is carried out to ultrasonic cleaning in organic solvent, obtain the described fluorescence molecule machine based on the One Dimension Silicon nano wire, wherein, nitrogen, nitrogen-bis-(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide: the One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified: the mass ratio of alpha-cylodextrin is 0.5:1:0.1～0.5:10:1.
3. preparation method according to claim 2 is characterized in that: described nitrogen, and the nitrogen in the mixed solution of nitrogen-diformamide and water, the volume ratio of nitrogen-diformamide and water is 5:1～10:1.
4. preparation method according to claim 2, it is characterized in that: the described thick product by the target fluorescence molecule machine that obtains carries out ultrasonic cleaning in organic solvent, be successively at toluene, nitrogen, carry out ultrasonic cleaning in nitrogen-dimethyl formamide, methylene dichloride, ethanol.
5. preparation method according to claim 2, it is characterized in that: the One Dimension Silicon nano wire that described 3-aminopropyl triethoxysilane is modified is to be prepared by following methods: the One Dimension Silicon nano wire and the dry toluene that in container, add oxygen plasma treatment to cross, and wherein: the mass ratio of One Dimension Silicon nano wire and dry toluene is 1:100～1:500; Under protection of inert gas, being heated to temperature is 120～140 ℃ of component distillations, after steaming 50～70% dry toluene of added dry toluene volume, be cooled to 70～90 ℃ and add the 3-aminopropyl triethoxysilane, wherein: the mass ratio of One Dimension Silicon nano wire and 3-aminopropyl triethoxysilane is 20:1～10:1; Be to stir under 80～100 ℃ in temperature, be down to room temperature, filter and obtain the thick product of One Dimension Silicon nano wire that the 3-aminopropyl triethoxysilane is modified; Clean the thick product of One Dimension Silicon nano wire that this 3-aminopropyl triethoxysilane is modified, filter, remove unreacted 3-aminopropyl triethoxysilane, vacuum-drying obtains the One Dimension Silicon nano wire that described 3-aminopropyl triethoxysilane is modified.
6. preparation method according to claim 2 is characterized in that: described nitrogen, and nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide is to be prepared by following methods:
(1) add 4-2-bromomethylphenyl-4-iodophenyl-azo, Anhydrous potassium carbonate, potassiumiodide, dansyl amide, acetonitrile in container, wherein: 4-2-bromomethylphenyl-4-iodophenyl-azo: Anhydrous potassium carbonate: potassiumiodide: dansyl amide: the mol ratio of acetonitrile is 1:2:1:2:520～1:4:1:4:780; In temperature, be under 50～90 ℃, to reflux 8～16 hours; Filtering reacting liquid, obtain nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide;
(2) under protection of inert gas, the nitrogen that adds step (1) to obtain in container, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide, salt of wormwood, two-triphenyl phosphorus palladium chloride, wherein: nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide: salt of wormwood: the mol ratio of two-triphenyl phosphorus palladium chloride is 1:2:0.001～1:2:0.006; Inject nitrogen, the mixed solution that the volume ratio of nitrogen-diformamide and water is 5:1～10:1, wherein: nitrogen, nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide and nitrogen, the mass ratio of the mixed solution of nitrogen-diformamide and water is 1:290～1:780; Stir the nitrogen that after 10～20 minutes, injection contains the 4-formylphenylboronic acid, the mixed solution of nitrogen-diformamide and water, wherein: 4-formylphenylboronic acid and nitrogen, the mass ratio of the mixed solution of nitrogen-diformamide and water is 1:100～1:300, nitrogen, the volume ratio of nitrogen-diformamide and water is 5:1～10:1, nitrogen, and the mol ratio of nitrogen-bis--(4-methylene radical phenyl-4 '-iodophenyl-azo)-dansyl amide and 4-formylphenylboronic acid is 1:2～1:6; Be that 100～150 ℃ of unglazed photographs under condition are reacted 8～24 hours in temperature, obtain described nitrogen, nitrogen-bis--(4-is to formylphenyl nitrogen benzide-4 '-methyl)-dansyl amide.
7. the using method of the fluorescence molecule machine based on the One Dimension Silicon nano wire according to claim 1, it is characterized in that: the described fluorescence molecule machine based on the One Dimension Silicon nano wire is scattered in the mixed solution of second alcohol and water and forms suspension liquid, wherein: in the mixed solution of second alcohol and water, the quality percentage composition of ethanol is 20%～95%, and the mass ratio of the fluorescence molecule machine based on the One Dimension Silicon nano wire and the mixed solution of second alcohol and water is 1:500～1:2000; Use successively the light that wavelength is 250～260nm, the light that wavelength is 420～430nm, the light that wavelength is 365～375nm to carry out illumination to the above-mentioned suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire; All using wavelength after each illumination is the exciting light of 360～370nm, and the suspension that contains the fluorescence molecule machine based on the One Dimension Silicon nano wire after above-mentioned illumination is excited, and to exciting the fluorescent emission wavelength obtained after described fluorescence molecule machine, is tested;
The time of above-mentioned three illumination is respectively all 5～10 minutes.
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