CN108752265A - Salicylide azine derivatives, its preparation method and the water phase light capture system constructed by it - Google Patents
Salicylide azine derivatives, its preparation method and the water phase light capture system constructed by it Download PDFInfo
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Abstract
The invention belongs to Supramolecular photochemistry fields, and in particular to a kind of salicylide azine derivatives, its preparation method and capture system by the water phase light that it is constructed.Salicylide azine derivatives have the following structure：It is independently filled the present invention also provides a kind of salicylide azine derivatives and is constructed water phase light capture system, the pseudorotaxane self assembly that poplar aldehyde azine derivatives and γ-CD are formed by it and water phase light is constructed by it and capture system；Constructed light capture system has many advantages, such as that stable structure, light capture system construct easy, energy transfer efficiency height and antenna effect is good, has prodigious application potential in Supramolecular self assembly light capture system is constructed.The present invention also provides the preparation method of salicylide azine derivatives, simple synthetic method is efficient, yield is high.
Description
Technical field
The invention belongs to Supramolecular photochemistry fields, and in particular to a kind of salicylide azine derivatives, its preparation method and by it
The water phase light capture system constructed.
Background technology
Light capture system be photosynthesis system important component, it be passed through by a large amount of antenna it is orderly
Assembling is constituted.Photosynthesis originates in absorption of the dye molecule to photon in light capture system, these dye molecules are as energy
Excitation can be efficiently transmitted to the energy acceptor dye molecule of reaction center, induction by energy transfer or energy transmission by donor
A series of redox reaction.Antenna is that photosynthesis realizes that solar energy is converted into chemistry to the efficient capture of photon
The basis of energy is always popular research field in the past few decades manual simulation's light capture system, not only helps people more
The photosynthesis of deep understanding nature, and have promotion directive function to agricultural production and field of environment protection；Simultaneously
People can be inspired to go to research and develop the organic optoelectronic device of highly efficient nanoscale, in photocatalysis, solar-electricity
There is potential application value in the fields such as pond, optical sensing and luminescent material.The core of manual simulation's light capture architectural study is asked
Topic is how to realize efficient light capture, it requires to exist simultaneously the antenna of different absorbing wavelengths in manual simulation's system,
To realize wide absorption bands, while the distance between antenna and spatial orientation are suitable, to ensure that energy transmission is efficient
It carries out.
People are to construct efficient light and capture system to have carried out a large amount of research work, and covalently synthesis and non-total is usually taken
The method of valence assembling captures system to simulate the light of nature.Covalent bonding at system include porphyrin array and dendroid point
The mode of son etc., non-covalent assembling includes organogel, large biological molecule, hybrid inorganic-organic materials etc..These systems
It constructs and helps somewhat to people and go to understand the light acquisition procedure of nature.Although covalently synthesis has efficient energy
Transmission efficiency, but it is limited to the complexity of synthesis, it is difficult to give acceptor ratio with larger；Non-covalent bond assembling can obtain
It is larger to give acceptor ratio, but be difficult to be optimal to receptor distance and relative orientation, therefore energy transfer efficiency is relatively low.
However up to the present, manual simulation's light capture system is often difficult to reach high energy in the case where high energy is to acceptor ratio
Transmission efficiency.Based on this, Development of Novel light capture system has great importance.
Invention content
In view of the deficiencies of the prior art, it is constructed the object of the present invention is to provide a kind of salicylide azine derivatives and by it
Water phase light captures system, and there is constructed light capture system stable structure, light capture system to construct easy, energy transmission effect
The advantages that rate height and good antenna effect, has prodigious application potential, this hair in Supramolecular self assembly light capture system is constructed
The bright preparation method for also providing salicylide azine derivatives, simple synthetic method is efficient, yield is high.
Salicylide azine derivatives of the present invention, have the following structure：
The preparation method of salicylide azine derivatives of the present invention, includes the following steps：
(1) 2,4- 4-dihydroxy benzaldehydes are dissolved in acetonitrile solvent, 1,6- dibromo-hexanes is added dropwise, K is then added2CO3,
Heating reflux reaction obtains 2- hydroxyls -4- (6- bromines hexyloxy) benzaldehyde；
(2) 2- hydroxyls -4- (6- bromines hexyloxy) benzaldehyde, hydrazine hydrate that step (1) obtains and anti-are added in the reactor
Answer etoh solvent, heating reflux reaction；
(3) using the reaction product that step (2) obtains as raw material, using pyridine as the solvent of reaction, by reaction system plus
Hot back flow reaction obtains salicylide azine derivatives.
Wherein：
2,4- 4-dihydroxy benzaldehydes, 1,6- dibromo-hexanes and K in step (1)2CO3Charged material weight ratio be 1.45-1.55:
0.45-0.55:1。
Heating reflux reaction temperature is 80 DEG C -90 DEG C in step (1), and the heating reflux reaction time is 11-13 hours.
2- hydroxyls -4- (6- bromines hexyloxy) benzaldehyde in step (2), hydrazine hydrate rate of charge be 0.5:10-10.5 2- hydroxyls
Benzaldehyde is in terms of g by base -4- (6- bromines hexyloxy), and hydrazine hydrate is in terms of mL.
Heating reflux reaction temperature is 80 DEG C -90 DEG C in step (2), and the heating reflux reaction time is 5-7 hours.
Heating reflux reaction temperature is 110 DEG C -120 DEG C in step (3), and the heating reflux reaction time is 2.5-3.5 hours.
Reaction equation is as follows：
The present invention, which designs, synthesizes a kind of double end base amphiphilic compound-salicylide azine derivatives, and then studying it is having
(1 × 10 in solvent (DMSO) and aqueous solution-4M it is weaker to find that it shines in organic solvent for fluorescence emission spectra), but
It is to be gradually increased with the ratio of Water in Organic Solvents, shines and gradually increase, become light green.
Gamma-cyclodextrin (γ-CD) is added in aqueous solution to salicylide azine derivatives of the present invention, with chemical combination
γ-CD are continuously added in object aqueous solution, are shone and are further enhanced, and bright green is presented.When be added equivalent γ-CD it
Afterwards, fluorescence intensity can enhance about 30 times, and illustrating that salicylide azinium moiety enters in the cavity of γ-CD realizes host and guest
Body wraps up.The package action is further titrated by nuclear-magnetism and is confirmed, while job ' s plot confirm Subjective and Objective most
Excellent proportioning is 1:1.Dynamic light scattering and transmission electron microscope confirm, are added before and after γ-CD, system can be in aqueous solution self assembly
Form the consistent sphere aggregates of size, respectively 30nm and 20nm.
System is captured by the water phase light that salicylide azine derivatives of the present invention are constructed, including following two：
The first is that salicylide azine derivatives of the present invention are self-assembly of sphere aggregates knot in aqueous solution
Structure, using the sphere aggregates as energy donor, Sulforhodamine constructs water phase light capture system as energy acceptor；Second
It is that gamma-cyclodextrin (γ-CD) is added in salicylide azine derivatives aqueous solution of the present invention, forms pseudorotaxane structure,
The pseudorotaxane structure assembles in aqueous solution forms sphere aggregates, and the sphere aggregates are small compared with the sphere aggregates of the first,
Using the sphere aggregates as energy donor, Sulforhodamine constructs water phase light capture system as energy acceptor.Preferably,
The salicylide azine derivatives and gamma-cyclodextrin are equivalents.
The autonomous dress of salicylide azine derivatives of the present invention and the water phase light capture system constructed by it, salicylide
Azine derivatives are shown in figure with the self assembly of the γ-CD pseudorotaxanes formed and the schematic diagram for the water phase light capture system constructed by it
1。
The first and second of water phase light capture system and respectively illustrate 18.2% energy transfer efficiency and 9.5 antenna
Effect and 48.7% energy transfer efficiency and 84.5 antenna effect.By the way that host macrocyclic molecule γ-is simply added
The raising of the luminescence enhancement and energy transfer efficiency and antenna effect of compound in aqueous solution can be realized in CD.
In conclusion the present invention has the following advantages：
(1) there is the light capture system constructed by the present invention stable structure, light capture system to construct easy, energy transmission effect
The advantages that rate height and good antenna effect, has prodigious application potential in Supramolecular self assembly light capture system is constructed.
(2) the present invention also provides the preparation method of salicylide azine derivatives, simple synthetic method is efficient, yield is high.
Description of the drawings
Fig. 1 be salicylide azine derivatives of the present invention autonomous dress and by the water phase light that it is constructed capture system,
Salicylide azine derivatives capture the signal of system with the self assembly of the γ-CD pseudorotaxanes formed and by the water phase light that it is constructed
Figure；
Fig. 2 is fluorograms of the BSA in DMSO aqueous solutions in embodiment 1；
Fig. 3 is the fluorescence emission spectra change schematic diagram that γ-CD are added in embodiment 1 in BSA；
Fig. 4 is α-CD, β-CD, the absorption of γ-CD solution and the fluorogram of BSA and BSA in embodiment 1；
Fig. 5 is job ' s plot curves in embodiment 1；
Fig. 6 is the nuclear magnetic spectrum of BSA, BSA@γ-CD in embodiment 1；
Fig. 7 is the dynamic light scattering and transmission electron microscope picture of BSA and BSA and γ-CD mixed liquors；
Fig. 8 is using BSA, BSA@γ-CD as energy donor in embodiment 1, and Sulforhodamine is constructed by energy acceptor
Light captures the ultra-violet absorption spectrum and fluorescence emission spectra schematic diagram of system；
Fig. 9 is that light captures fluorescence lifetime attenuation curve of the system before and after Sulforhodamine is added.
Specific implementation mode
With reference to embodiment, the present invention will be further described.
Embodiment 1
A kind of salicylide azine derivatives (BSA), have the following structure：
Preparation method includes the following steps：
(1) by 1.5g 2,4- 4-dihydroxy benzaldehydes are dissolved in acetonitrile solvent, dropwise addition 0.5g 1,6- dibromo-hexanes, then
1g K are added2CO3, it is heated to 85 DEG C of back flow reactions 12 hours, obtains 2- hydroxyls -4- (6- bromines hexyloxy) benzaldehyde, yield
30.6%；
(2) 0.5g 2- hydroxyls -4- (6- bromines hexyloxy) benzaldehyde, 10ml water that step (1) obtains are added in the reactor
Hydrazine and reaction dissolvent ethyl alcohol are closed, is heated to 85 DEG C of back flow reactions 6 hours, obtains compound 2, yield 37.8%；
(3) using the compound 2 that step (2) obtains as raw material, using pyridine as the solvent of reaction, reaction system is heated
It flows back 3 hours to 120 DEG C, obtains salicylide azine derivatives (BSA), yield 45.7%, hydrogen spectrum1H NMR(400MHz, D2O)δ
11.48 (s, 2H), 9.12 (s, 4H), 8.86 (s, 2H), 8.61 (t, J=7.5Hz, 2H), 8.17 (t, J=7.0Hz, 4H)
7.53 (d, J=8.7Hz, 2H), 6.55 (d d, J=8.6,2.3Hz, 2H), 6.50 (d, J=2.1J=8.7Hz, 2H), 6.55
(d d, J=8.6,2.3Hz, 2H) 6.50 (d, J=2.1Hz, 2H), 4.62 (d, J=3.4Hz, 4H), 4.01 (t, J=
6.3Hz, 4H), 2.03- 1.89 (m, 4H), 1.79-1.65 (m, 4H), 1.46 (dt, J=14.7,7.3Hz, 4H), 1.40-
1.29(m,4H)；Carbon is composed13C NMR(100MHz,D2), O δ (ppm)=163.1,161.7,157.3,146.0,140.4,
133.0,128.4,110.1,107.1, 103.5,71.9,68.7,30.4,28,25.6。
The BSA being prepared is tested as follows：
1, shining in the assembling of BSA and γ-CD and BSA solvents.
It weighs 0.000378g BSA and is put in the aqueous solution that 1ml is added in the water white transparency bottle of 5ml, it is fully dissolved.
The solution for then therefrom drawing 100ul respectively with micro-injection agent, is placed in the water white transparency bottle of 10 5ml, uses liquid-transfering gun
The aqueous solution of 5ml is added dropwise into each bottle, obtains 10 a concentration of 1 × 10-5BSA solution.
5 5ml water white transparency bottles are taken, according to DMSO:H2O volume ratios are 0:10,3:7,5:5,7:3,10:0 is mixed
It closes, the BSA for then weighing 0.0000378g respectively is added in 5 bottles.Test its fluorescence intensity, collection of illustrative plates is shown in Fig. 2, bent in figure
Line indicates DMSO successively from top to bottom:H2O volume ratios are 0:10,3:7,5:5,7:3,10:0 fluorescence spectrum.With the ratio of dampening
Example constantly increases, and the intensity of fluorescence constantly enhances, and sends out light green fluorescence.
2, the γ-CD for weighing 0.01297g are put in bottle, and the aqueous solution of 2ml is added, and are configured to the γ-of 0.02mol/ml
CD solution is titrated.γ-CD aqueous solutions per 5ul are identical as the amount of substance of solute in the BSA aqueous solutions of 5ml, i.e., 1
Equivalent.Every time to 1 × 10-5BSA solution in be added dropwise 5ul γ-CD aqueous solutions, test fluorescence intensity, as shown in figure 3, in figure
Curve indicates BSA successively from top to bottom:γ-CD equivalent proportions are 1:3,1:2.5,1:2,1:1.5,1:1,1:0.5,1:0 fluorescence
Spectrum.Equivalent with the γ-CD of dropwise addition increases, and the fluorescence intensity of BSA gradually enhances.γ-CD solution in BSA solution from
0ul gradually arrives 30ul, and fluorescence intensity also gradually enhances from 250 or so to 4500 or so.Then compared under ultraviolet light,
BSA solution fluorescence intensity is very weak, and BSA@γ-CD solution has green fluorescence.
3, α-CD and 0.01135g the β-CD for weighing 0.00973g are put in respectively in the clear, colorless bottle of 2 5ml, respectively
The aqueous solution of 2ml is added, is configured to the β-CD solution of the α-CD and 0.02mol/ml of 0.02mol/ml.Take 41 × 10-5BSA
The colourless bottle of solution is separately added into the α-CD, β-CD, γ-CD solution of 15ul, tests UV absorption and fluorescence intensity, collection of illustrative plates
See Fig. 4, curve indicates the UV absorption of BSA- β-CD, BSA- α-CD, BSA- γ-CD successively from top to bottom at 370nm in figure
Spectrum；Curve indicates the fluorescence spectrum of BSA- γ-CD, BSA- α-CD, BSA- β-CD, BSA successively from top to bottom in figure.
The fluorescence intensity that α-CD and β-CD solution is added is similar to the intensity of BSA solution of any substance is not added with, and is 250 left
The right side, and the fluorescence intensity that the BSA solution of γ-CD is added can reach 450 or so.Prove that γ-CD can enhance the fluorescence of BSA
Intensity.
4,0.000378g BSA are weighed to be put in the conical flask of 150ml, the aqueous solution of 100ml is then added, is configured to
The 1 × 10 of 100ml-5BSA solution.It weighs 0.001297g γ-CD to be put in another 150ml conical flasks, the water of 100ml is added
Solution is configured to 100ml 1 × 10-5γ-CD solution.Take 1~11, No. 1 bottle of bottle label of 11 water white transparency 5ml
Middle γ-CD the solution that 5ml is added；0.5ml BSA solution, the γ-CD of 4.5ml are added in No. 2 bottles；It is added in No. 3 bottles
1ml BSA solution, the γ-CD of 4ml；1.5ml BSA solution, the γ-CD of 3.5ml are added in No. 4 bottles；It is added in No. 5 bottles
2ml BSA solution, the γ-CD of 3ml；2.5ml BSA solution, the γ-CD of 2.5ml are added in No. 6 bottles；It is added in No. 7 bottles
3ml BSA solution, the γ-CD of 2ml；3.5ml BSA solution, the γ-CD of 1.5ml are added in No. 8 bottles；It is added in No. 9 bottles
4ml BSA solution, the γ-CD of 1ml；4.5ml BSA solution, the γ-CD of 0.5ml are added in No. 10 bottles；Add in No. 11 bottles
Enter 5ml BSA solution.
The fluorescence intensity for testing solution in 1~No. 11 bottle respectively, takes the maximum value of every test curve fluorescence intensity, horizontal
Coordinate takes 0~1 to make job ' s plot curves, is specifically shown in Fig. 5, and the peak of job ' s plot curves appears in 0.5, it was demonstrated that
BSA and γ-CD are according to 1:1 ratio row are assembled.
5, nuclear-magnetism titration and SEM, TEM, dynamic light scattering test
It weighs 0.0000378g BSA to be put in bottle, with the D of 2ml2O is dissolved；Weigh 0.0000378g BSA with
0.0001297g γ-CD are put in bottle, with the D of 2ml2O is dissolved.Then, two solution are put in two nuclear-magnetisms respectively
Carry out nuclear-magnetism test in pipe, BSA, BSA@γ-CD nuclear magnetic spectrum see Fig. 6, the position at peak is compared with BSA in BSA@γ-CD
It is subjected to displacement, it was demonstrated that BSA has superscribed γ-CD.
6,1 × 10 is configured-5BSA solution 10ml, 1 × 10-5γ-CD solution 5ml.5ml BSA solution is extracted, is put in 1
Label A in a 5ml bottles, extraction 2.5ml BSA solution is mixed with 2.5ml γ-CD solution is put in label in another 1 5ml bottle
B。
A small amount of solution is extracted in A bottles to be put into cuvette, is put into the size that particle is tested in dynamic light scattering；From B bottles
The identical operation of middle repetition.The size of particle is respectively 30nm and 20nm after measuring before assembling.A bottles of dynamic light scattering diagram
It is in Fig. 7 (a), B bottles of dynamic light scattering diagram is in Fig. 7 (b).
A small amount of solution is extracted with disposable dropper smooth silicon chip, copper in surface hydroxylation are added dropwise respectively from A bottles
Net surface；Identical operation is carried out from B bottles.The silicon chip made respectively and copper mesh are subjected to TEM characterizations, it was demonstrated that BSA is being wrapped
It wraps the assembling of the front and back groups of γ-CD and forms sphere aggregates.BSA organizes assembling before and after superscribing γ-CD and forms spherical aggregation
The TEM collection of illustrative plates of body is shown in (c) and (d) in Fig. 7 respectively.
7, light capture energy system construct and the research of energy efficiency.
Configuration 1 × 10-5BSA solution 10ml, 1 × 10-5γ-CD solution 5ml.5ml BSA solution is extracted, is put in 1
Label 01 in 5ml bottles, extraction 2.5ml BSA solution is mixed with 2.5ml γ-CD solution is put in label in another 1 5ml bottle
02。
It weighs Sulforhodamine B (SR101) 0.001044g to be placed in 30ml water white transparency bottles, be added with liquid-transfering gun
The aqueous solution of 30ml is configured to the 1 × 10 of 30ml-5The solution of SR101.
Ultraviolet, fluorometric investigation is carried out to the BSA solution in No. 01 bottle；The SR101 solution of 1ul is drawn with micro-injection agent
No. 01 bottle is added (for acceptor ratio 2500:1) in, ultraviolet, fluorescence test is carried out, corresponding data is obtained；Again with micro note
No. 01 bottle is added (for acceptor ratio 1000 in the SR101 solution that emitter draws 4ul:1) ultraviolet, fluorescence test, is carried out, is obtained
To corresponding data；Then No. 01 bottle is added (for acceptor ratio 625 in the SR101 solution that 4ul is drawn with micro syringe:1) into
Ultraviolet, fluorescence the test of row, obtains corresponding data；The SR101 solution of 2.5ul is injected into No. 01 bottle again (for acceptor ratio
385:1) ultraviolet, fluorescence measurement, is carried out later；The SR101 solution of 4ul is further injected into No. 01 bottle (for receptor ratio
Example 312:1) ultraviolet, fluorescence measurement, is carried out later；Followed by injected into No. 01 bottle SR101 solution 14ul (for by
Body ratio 166:1) ultraviolet, fluorescence test, is carried out later；Then to injected in No. 01 bottle 5ul SR101 solution (for by
Body ratio 142:1) ultraviolet, fluorescence intensity test, is carried out later；Then the SR101 solution of 6ul is added dropwise into No. 01 bottle
(for acceptor ratio 121:1), then ultraviolet, fluorescence test is carried out；The SR101 solution of 7ul is finally added dropwise into No. 01 bottle
(for acceptor ratio 116:1), then ultraviolet, fluorescence test is carried out.Test result is shown in (a) and (b) in Fig. 8, curve in Fig. 8 (a)
Indicate that the ratio of BSA and SR101 is successively from top to bottom at 600nm：1:0(only donor),2500:1,1000:1,
625:1,500:1,385:1,312:1,166:1,156:1,142:1,121:1,116:1 ultra-violet absorption spectrum；In Fig. 8 (b)
Curve indicates that the ratio of BSA and SR101 is successively from top to bottom at 620nm：1:0(only donor), 2500:1,1000:
1,625:1,500:1,385:1,312:1,166:1,156:1,142:1,121:1,116:1 fluorescence spectrum.
In ultraviolet figure, constantly decline with the absorbance for being continuously increased donor of SR101, receptor is then constantly to increase
By force；The fluorescence intensity of donor constantly declines in fluorogram, and the fluorescence intensity of receptor constantly enhances, and improves significantly,
Energy shifts.Under the illumination of 365nm, the luminous intensity of BSA solution is very low, as SR101 is constantly added dropwise, fluorescence
Intensity constantly increases, and increases to 500 or so from 50, sends out yellow fluorescence.
Ultraviolet, fluorometric investigation is carried out to the BSA solution in No. 02 bottle；The SR101 solution of 1ul is drawn with micro-injection agent
No. 02 bottle is added (for acceptor ratio 2500:1) in, ultraviolet, fluorescence test is carried out, corresponding data is obtained；Again with micro note
No. 02 bottle is added (for acceptor ratio 1000 in the SR101 solution that emitter draws 4ul:1) ultraviolet, fluorescence test, is carried out, is obtained
To corresponding data；Then No. 02 bottle is added (for acceptor ratio 625 in the SR101 solution that 4ul is drawn with micro syringe:1) into
Ultraviolet, fluorescence the test of row, obtains corresponding data；The SR101 solution of 2.5ul is injected into No. 02 bottle again (for acceptor ratio
385:1) ultraviolet, fluorescence measurement, is carried out later；The SR101 solution of 4ul is further injected into No. 02 bottle (for receptor ratio
Example 312:1) ultraviolet, fluorescence measurement, is carried out later；Followed by injected into No. 02 bottle SR101 solution 14ul (for by
Body ratio 166:1) ultraviolet, fluorescence test, is carried out later；Then to injected in No. 02 bottle 5ul SR101 solution (for by
Body ratio 142:1) ultraviolet, fluorescence intensity test, is carried out later；Then the SR101 solution of 6ul is added dropwise into No. 02 bottle
(for acceptor ratio 121:1), then ultraviolet, fluorescence test is carried out；The SR101 solution of 7ul is finally added dropwise into No. 02 bottle
(for acceptor ratio 116:1), then ultraviolet, fluorescence test is carried out.Test result is shown in (c) and (d) in Fig. 8, curve in Fig. 8 (c)
Indicate that the ratio of BSA@γ-CD and SR101 are successively from top to bottom at 590nm：1:0(only donor), 2500:1,
1000:1,625:1,500:1,385:1,312:1,166:1,156:1,142:1,121:1,116:1 ultra-violet absorption spectrum；
Curve indicates that the ratio of BSA@γ-CD and SR101 are successively from top to bottom at 620nm in Fig. 8 (d)： 1:0(only
donor),2500:1,1000:1,625:1,500:1,385:1,312:1,166:1,156:1,142:1,121:1, 116:1
Fluorescence spectrum.
In the BSA solution that γ-CD are added, γ-CD are assembled with BSA, and fluorescence intensity significantly improves, with receptor
SR101's is continuously added, and the absorbance of ultraviolet donor site constantly declines, and acceptor site significantly improves；Fluorescence intensity donor
Position fluorescence intensity is remarkably decreased, and acceptor site fluorescence intensity significantly improves.At 365nm, BSA@γ-CD send out yellow green
Fluorescence；With the increase of SR101 in BSA@γ-CD, the fluorescence of pink is sent out.
8, the calculating of energy transfer efficiency and antenna effect.
It is added dropwise in SR101 systems in BSA solution, pure 1 × 10-5The fluorescence intensity of BSA solution is 245, and SR101 is being added dropwise
Afterwards, fluorescence intensity can reach 286 (for acceptor ratio:116:1), according to formula Φ ET=1-IDA/ID,Obtain energy transfer efficiency
It is 18.2%；383nm and 580nm is used to excite 1 × 10 respectively-5The solution of BSA+SR101 obtains receptor fluorescence at 383nm
Intensity can reach 475, and acceptor fluorescence intensity is 50 when 580nm excitations, according to Antenna effect=(IDA,350-ID,350)/
IDA,580It is 9.8 that antenna effect, which can be calculated,.
It is added dropwise in SR101 systems in BSA@γ-CD solution, pure 1 × 10-5The fluorescence intensity of BSA@γ-CD solution is
5094, after SR101 is added dropwise, fluorescence intensity can reach 5927 (for acceptor ratio:116:1), according to formula Φ ET=1-
IDA/ID,It is 41.7% to obtain energy transfer efficiency；383nm and 580nm is used to excite 1 × 10 respectively-5The solution of BSA+SR101, obtains
To receptor, fluorescence intensity can reach 7200 at 383nm, and acceptor fluorescence intensity is 863 when 580nm excitations, according to Antenna
Effect=(IDA,350-ID,350)/IDA,580It is 84.5 that antenna effect, which can be calculated,.
9, the calculating in system service life.
Configuration 1 × 10-5Then the BSA solution of concentration tests this bath life, obtain data and mapped with OringPro；With
It is added dropwise 1 × 10 in backward BSA solution-5The SR101 solution 43ul of concentration, then test this bath life, are made with OringPro
Figure.BSA solution and life span comparison's figure of BSA+SR101 solution are shown in Fig. 9.Curve above in Fig. 9 (a) represents BSA solution
Service life, following curve represent the service life of BSA+SR101 solution.
Configuration 1 × 10-5Then the BSA@γ-CD solution of concentration tests this bath life, obtain data and made with OringPro
Figure；Then to dropwise addition 1 × 10 in BSA@γ-CD solution-5The SR101 solution 43ul of concentration, then test this bath life, use
OringPro maps.Life span comparison's figure of BSA@γ-CD solution and BSA@γ-CD+SR101 solution is shown in Fig. 9, in Fig. 9 (b) on
The curve in face represents the service life of BSA@γ-CD solution, and following curve represents the service life of BSA@γ-CD+SR101 solution.
Claims (9)
1. a kind of salicylide azine derivatives, it is characterised in that：It has the following structure：
2. a kind of preparation method of salicylide azine derivatives described in claim 1, it is characterised in that：Include the following steps：
(1) 2,4- 4-dihydroxy benzaldehydes are dissolved in acetonitrile solvent, 1,6- dibromo-hexanes is added dropwise, K is then added2CO3, heating
Back flow reaction obtains 2- hydroxyls -4- (6- bromines hexyloxy) benzaldehyde；
(2) it is molten that 2- hydroxyls -4- (6- bromines hexyloxy) benzaldehyde, hydrazine hydrate and reaction that step (1) obtains are added in the reactor
Agent ethyl alcohol, heating reflux reaction；
(3) using the reaction product that step (2) obtains as raw material, using pyridine as the solvent of reaction, reaction system is heated back
Stream reaction, obtains salicylide azine derivatives.
3. the preparation method of salicylide azine derivatives according to claim 2, it is characterised in that：2,4- in step (1)
4-dihydroxy benzaldehyde, 1,6- dibromo-hexanes and K2CO3Charged material weight ratio be 1.45-1.55:0.45-0.55:1.
4. the preparation method of salicylide azine derivatives according to claim 2, it is characterised in that：Heating in step (1)
Back flow reaction temperature is 80 DEG C -90 DEG C, and the heating reflux reaction time is 11-13 hours.
5. the preparation method of salicylide azine derivatives according to claim 2, it is characterised in that：2- hydroxyls in step (2)
Base -4- (6- bromines hexyloxy) benzaldehyde, hydrazine hydrate rate of charge be 0.5:10-10.5,2- hydroxyl -4- (6- bromines hexyloxy) benzene first
Aldehyde is in terms of g, and hydrazine hydrate is in terms of mL.
6. the preparation method of salicylide azine derivatives according to claim 2, it is characterised in that：Heating in step (2)
Back flow reaction temperature is 80 DEG C -90 DEG C, and the heating reflux reaction time is 5-7 hours.
7. the preparation method of salicylide azine derivatives according to claim 2, it is characterised in that：Heating in step (3)
Back flow reaction temperature is 110 DEG C -120 DEG C, and the heating reflux reaction time is 2.5-3.5 hours.
8. a kind of water phase light capture system constructed by salicylide azine derivatives described in claim 1, it is characterised in that：Institute
The salicylide azine derivatives stated are self-assembly of sphere aggregates structure in aqueous solution, are given using the sphere aggregates as energy
Body, Sulforhodamine construct water phase light capture system as energy acceptor.
9. a kind of water phase light capture system constructed by salicylide azine derivatives described in claim 1, it is characterised in that：?
Gamma-cyclodextrin is added in the salicylide azine derivatives aqueous solution, forms pseudorotaxane structure, the pseudorotaxane structure is water-soluble
Assembling forms sphere aggregates in liquid, and using the sphere aggregates as energy donor, Sulforhodamine is constructed as energy acceptor
Water phase light captures system.
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| CN106967419A (en) * | 2017-04-14 | 2017-07-21 | 南开大学 | A kind of ternary nano oversubscription sub-light good harvest system of sulfated cyclodextrins phenylenevinylene derivative Nile red and preparation method thereof |
| CN107987291A (en) * | 2017-12-04 | 2018-05-04 | 吉林大学 | A kind of circularly polarized luminescence based on crystalline state nano-cellulose, preparation method and its application on false proof |
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