CN108752265B - Salicylaldehyde azine derivative, preparation method thereof and aqueous phase light capture system constructed by salicylaldehyde azine derivative - Google Patents
Salicylaldehyde azine derivative, preparation method thereof and aqueous phase light capture system constructed by salicylaldehyde azine derivative Download PDFInfo
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Abstract
The invention belongs to the field of supermolecule photochemistry, and particularly relates to a salicylaldehyde azine derivative, a preparation method thereof and an aqueous phase light capture system constructed by the salicylaldehyde azine derivative.Salicylaldehyde azine derivatives have the following structure:
the invention also provides a salicylaldehyde azine derivative self-assembly and a water-phase light capture system constructed by the salicylaldehyde azine derivative self-assembly, a pseudo-rotaxane self-assembly formed by the salicylaldehyde azine derivative and gamma-CD and a water-phase light capture system constructed by the salicylaldehyde azine derivative self-assembly; the constructed light capture system has the advantages of stable structure, simple and convenient construction of the light capture system, high energy transfer efficiency, good antenna effect and the like, and has great application potential in the construction of the supermolecule self-assembly light capture system. The invention also provides a preparation method of the salicylaldehyde azine derivative, and the synthesis method is simple, convenient and efficient and has high yield.
Description
Technical Field
The invention belongs to the field of supermolecule photochemistry, and particularly relates to a salicylaldehyde azine derivative, a preparation method thereof and an aqueous phase light capture system constructed by the salicylaldehyde azine derivative.
Background
The light harvesting system is an important component of the photosynthesis system and is composed of a large number of antenna molecules assembled in an orderly manner. The photosynthesis starts from the absorption of photons by dye molecules in a light trapping system, these dye molecules act as energy donors and efficiently transfer excitation energy to energy acceptor dye molecules in a reaction center by energy transfer or energy transfer, inducing a series of redox reactions. The efficient capture of photons by antenna molecules is the basis for realizing the conversion of solar energy into chemical energy through photosynthesis, and the artificial simulation light capture system is always the hot research field in the past decades, so that the artificial simulation light capture system not only is beneficial to people to understand the photosynthesis process in the nature more deeply, but also has a promotion and guidance effect on the fields of agricultural production and environmental protection; meanwhile, people can be inspired to research and develop more efficient nanoscale organic optoelectronic devices, and the organic optoelectronic devices have potential application values in the fields of photocatalysis, solar cells, optical sensing, luminescent materials and the like. The core problem of the research of the artificial simulation light capture system is how to realize high-efficiency light capture, which requires that antenna molecules with different absorption wavelengths exist in the artificial simulation system at the same time to realize a wide absorption waveband, and the distance and the spatial orientation between the antenna molecules are proper to ensure that the energy transfer is carried out efficiently.
A great deal of research work is carried out to construct efficient light capture systems, and covalent synthesis and non-covalent assembly methods are generally adopted to simulate the light capture systems in the nature. The system synthesized by covalent bonds comprises a porphyrin array, dendritic molecules and the like, and the noncovalent assembly mode comprises organogel, biomacromolecules, organic-inorganic hybrid materials and the like. The construction of these systems is somewhat helpful to people in understanding the light trapping process in nature. Although the covalent synthesis has high energy transfer efficiency, the covalent synthesis is limited by the complexity of the synthesis and is difficult to have a large donor-acceptor ratio; non-covalent assembly can result in a large donor-acceptor ratio, but optimal donor-acceptor distance and relative orientation is difficult to achieve, and thus energy transfer efficiency is low. However, to date, it has often been difficult to achieve high energy transfer efficiency at high energy to receptor ratios with artificial analog light harvesting systems. Based on this, the development of novel light trapping systems is of great significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the salicylaldehyde azine derivative and a water-phase light capture system constructed by the salicylaldehyde azine derivative, wherein the constructed light capture system has the advantages of stable structure, simplicity and convenience in construction of the light capture system, high energy transfer efficiency, good antenna effect and the like, and has great application potential in construction of a supermolecule self-assembly light capture system.
The salicylaldehyde azine derivative has the following structure:
the preparation method of the salicylaldehyde azine derivative comprises the following steps:
(1) dissolving 2, 4-dihydroxybenzaldehyde in acetonitrile solvent, dropwise adding 1, 6-dibromohexane, and adding K2CO3Heating and refluxing for reaction to obtain 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde;
(2) adding the 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde obtained in the step (1), hydrazine hydrate and a reaction solvent ethanol into a reactor, and heating and refluxing for reaction;
(3) and (3) taking the reaction product obtained in the step (2) as a raw material, taking pyridine as a reaction solvent, and heating and refluxing the reaction system for reaction to obtain the salicylaldehyde azine derivative.
Wherein:
2, 4-dihydroxybenzaldehyde, 1, 6-dibromohexane and K in the step (1)2CO3The feeding weight ratio of (A) is 1.45-1.55:0.45-0.55: 1.
In the step (1), the heating reflux reaction temperature is 80-90 ℃, and the heating reflux reaction time is 11-13 hours.
In the step (2), the feeding ratio of the 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde to the hydrazine hydrate is 0.5:10-10.5, wherein the 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde is counted by g, and the hydrazine hydrate is counted by mL.
In the step (2), the heating reflux reaction temperature is 80-90 ℃, and the heating reflux reaction time is 5-7 hours.
In the step (3), the heating reflux reaction temperature is 110-120 ℃, and the heating reflux reaction time is 2.5-3.5 hours.
The reaction equation is as follows:
the invention designs and synthesizes a double-headed amphiphilic compound-salicylaldehyde azine derivative, and then researches the double-headed amphiphilic compound-salicylaldehyde azine derivative in an organic solvent (DMSO) and an aqueous solution (1 x 10)-4M) was found to emit light weakly in an organic solvent,however, as the proportion of water in the organic solvent is gradually increased, the light emission thereof is gradually increased to turn into light green.
The salicylaldehyde azine derivative provided by the invention is added with gamma-cyclodextrin (gamma-CD) in an aqueous solution, and the luminescence of the salicylaldehyde azine derivative is further enhanced along with the continuous addition of the gamma-CD in the aqueous solution of the compound, so that the salicylaldehyde azine derivative is bright green. When an equivalent amount of gamma-CD is added, the fluorescence intensity can be enhanced by about 30 times, which indicates that the salicylaldehyde azine part enters the cavity of the gamma-CD to realize the host-guest encapsulation. The wrapping effect is further verified by nuclear magnetic titration, and the jobs's plot confirms that the optimal ratio of the subject to the object is 1:1. Dynamic light scattering and transmission electron microscopy confirm that the system can form spherical aggregates with consistent sizes respectively of 30nm and 20nm in aqueous solution through self-assembly before and after the gamma-CD is added.
The aqueous phase light trapping system constructed by the salicylaldehyde azine derivative comprises the following two types:
the first is that the salicylaldehyde azine derivative is self-assembled in a water solution to form a spherical aggregate structure, the spherical aggregate is used as an energy donor, sulforhodamine is used as an energy acceptor, and a water-phase light capture system is constructed; and secondly, adding gamma-cyclodextrin (gamma-CD) into the aqueous solution of the salicylaldehyde azine derivative to form a pseudo-rotaxane structure, assembling the pseudo-rotaxane structure in the aqueous solution to form a spherical aggregate, wherein the spherical aggregate is smaller than the first spherical aggregate, and the spherical aggregate is used as an energy donor and sulforhodamine is used as an energy acceptor to construct an aqueous phase light capture system. Preferably, the salicylaldehyde azine derivative is equivalent to gamma-cyclodextrin.
The self-assembly of the salicylaldehyde azine derivative and the aqueous phase light capture system constructed by the salicylaldehyde azine derivative, the self-assembly of the pseudorotaxane formed by the salicylaldehyde azine derivative and gamma-CD and the schematic diagram of the aqueous phase light capture system constructed by the salicylaldehyde azine derivative are shown in figure 1.
The first and second aqueous phase light harvesting systems showed an energy transfer efficiency of 18.2% and an antenna effect of 9.5, and an energy transfer efficiency of 48.7% and an antenna effect of 84.5, respectively. The enhancement of the luminescence of the compound in aqueous solution and the improvement of the energy transfer efficiency and the antenna effect can be realized by simply adding the main macrocyclic molecule gamma-CD.
In summary, the invention has the following advantages:
(1) the light capture system constructed by the invention has the advantages of stable structure, simple and convenient construction of the light capture system, high energy transfer efficiency, good antenna effect and the like, and has great application potential in the construction of the supermolecule self-assembly light capture system.
(2) The invention also provides a preparation method of the salicylaldehyde azine derivative, and the synthesis method is simple, convenient and efficient and has high yield.
Drawings
FIG. 1 is a schematic diagram of the self-assembly of salicylaldehyde azine derivative and an aqueous phase light trapping system constructed by the same, the self-assembly of pseudorotaxane formed by salicylaldehyde azine derivative and gamma-CD, and the aqueous phase light trapping system constructed by the same;
FIG. 2 is a fluorescence diagram of BSA in DMSO aqueous solution in example 1;
FIG. 3 is a graph showing the change of fluorescence spectrum of BSA with gamma-CD added in example 1;
FIG. 4 is a graph of the absorbance and fluorescence of solutions of BSA and BSA in α -CD, β -CD, and γ -CD in example 1;
FIG. 5 is a plot of jobs's plot in example 1;
FIG. 6 is a nuclear magnetic spectrum of BSA, BSA @ gamma-CD in example 1;
FIG. 7 is a dynamic light scattering and transmission electron micrograph of BSA and a mixture of BSA and γ -CD;
FIG. 8 is a schematic diagram of an ultraviolet absorption spectrum and a fluorescence emission spectrum of a light trapping system constructed by using BSA, BSA @ gamma-CD as energy donors and sulforhodamine as energy acceptors in example 1;
FIG. 9 is a plot of the decay of fluorescence lifetime of a light trapping system before and after sulforhodamine addition.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
A salicylaldehyde azine derivative (BSA) having the structure:
the preparation method comprises the following steps:
(1) 1.5g of 2, 4-dihydroxybenzaldehyde was dissolved in acetonitrile solvent, 0.5g of 1, 6-dibromohexane was added dropwise, followed by addition of 1g K2CO3Heating to 85 ℃ for reflux reaction for 12 hours to obtain 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde with the yield of 30.6 percent;
(2) adding 0.5g of 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde obtained in the step (1), 10ml of hydrazine hydrate and reaction solvent ethanol into a reactor, heating to 85 ℃, and carrying out reflux reaction for 6 hours to obtain a compound 2, wherein the yield is 37.8%;
(3) heating the reaction system to 120 ℃ by taking the compound 2 obtained in the step (2) as a raw material and pyridine as a reaction solvent and refluxing for 3 hours to obtain the salicylaldehyde azine derivative (BSA), wherein the yield is 45.7 percent, and the hydrogen spectrum is shown1H 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 ═ 6.3, 4H), 2.89-1.89 (m), 1.65(m, 1.65, 1.7H), 1.79 (t, 1.7H), 1.7H, 1H), 1.46 (1H), 7H, 1H); carbon spectrum13C NMR(100MHz,D2O),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 prepared was tested as follows:
1. assembly of BSA with γ -CD and luminescence in BSA solvent.
0.000378g of BSA were weighed into a 5ml colorless clear vial, and 1ml of an aqueous solution was added to dissolve it sufficiently. Then, 100ul of each solution was aspirated from the solution using a microinjection, and the solution was placed in 10 colorless transparent vials of 5ml, and 5ml of an aqueous solution was added dropwise to each vial using a pipette gun to obtain 10 solutions of 1X 10 concentration-5BSA solution (1).
5 clear, colorless vials were taken, according to DMSO: H2O volume ratios of 0:10, 3:7, 5:5, 7:3, 10:0 were mixed, and then 0.0000378g of BSA was weighed into 5 vials, respectively. The fluorescence intensity is measured, the graph is shown in figure 2, and the curve in the graph sequentially represents DMSO: H from top to bottom2Fluorescence spectra with O volume ratios of 0:10, 3:7, 5:5, 7:3, 10: 0. As the proportion of water is increased, the intensity of fluorescence is increased continuously, and light green fluorescence is emitted.
2. 0.01297g of gamma-CD were weighed into a vial, and 2ml of an aqueous solution was added to prepare a 0.02mol/ml gamma-CD solution for titration. The amount of solute species in 5ul of aqueous gamma-CD solution was the same as 5ml of aqueous BSA solution, i.e., 1 equivalent. Each time to 1 × 10-55ul of an aqueous solution of gamma-CD was dropped into the BSA solution to measure the fluorescence intensity, as shown in FIG. 3, wherein the curve in the figure shows the fluorescence spectra of BSA to gamma-CD equivalent ratios of 1:3, 1:2.5, 1:2, 1:1.5, 1:1, 1:0.5, and 1:0 in order from top to bottom. The fluorescence intensity of BSA increased gradually as the equivalent of added gamma-CD increased. The gamma-CD solution in the BSA solution is gradually increased from 0ul to 30ul, and the fluorescence intensity is also gradually increased from about 250 to about 4500. Subsequent comparison under UV light showed very weak fluorescence intensity for the BSA solution and green fluorescence for the BSA @ gamma-CD solution.
3. 0.00973g of α -CD and 0.01135g of β -CD are weighed and respectively placed in 2 transparent colorless vials of 5ml, 2ml of aqueous solution is respectively added to prepare 0.02mol/ml of α -CD and 0.02mol/ml of β -CD solution, 4 are taken, and the concentration of the α -CD solution and the β -CD solution is 1X 10-515ul of α -CD, β -CD, gamma-CD solutions were added to the colorless vial of BSA solution and the UV absorption and fluorescence intensity were measured, as shown in FIG. 4, which is a graph in which the curves are plottedThe ultraviolet absorption spectra of BSA- β -CD, BSA- α -CD and BSA-gamma-CD are shown in the sequence from top to bottom at 370nm, and the curves in the figure sequentially show the fluorescence spectra of BSA-gamma-CD, BSA- α -CD, BSA- β -CD and BSA from top to bottom.
The fluorescence intensity of the solutions with α -CD and β -CD is similar to that of the BSA solution without any substance and is about 250, while the fluorescence intensity of the BSA solution with gamma-CD can reach about 450.
4. 0.000378g BSA were weighed into a 150ml Erlenmeyer flask, and 100ml aqueous solution was added to prepare 100ml 1X 10-5BSA solution (1). 0.001297g of gamma-CD were weighed and placed in another 150ml Erlenmeyer flask, and 100ml of aqueous solution was added to prepare 100ml of 1X 10-5The gamma-CD solution of (1). Taking 11 colorless and transparent 5ml vials with the label of 1-11, and adding 5ml of gamma-CD solution into the vial No. 1; vial No. 2 was charged with 0.5ml BSA solution, 4.5ml gamma-CD; vial No. 3 was charged with 1ml BSA solution, 4ml gamma-CD; vial No. 4 was charged with 1.5ml BSA solution, 3.5ml gamma-CD; vial No. 5 was charged with 2ml BSA solution, 3ml gamma-CD; vial No. 6 was charged with 2.5ml BSA solution, 2.5ml gamma-CD; vial 7 was filled with 3ml of BSA solution, 2ml of gamma-CD; vial No. 8 was charged with 3.5ml BSA solution, 1.5ml gamma-CD; vial No. 9 was charged with 4ml BSA solution, 1ml gamma-CD; vial No. 10 was charged with 4.5ml BSA solution, 0.5ml gamma-CD; vial 11 was charged with 5ml of BSA solution.
And (3) respectively testing the fluorescence intensity of the solution in the vials 1-11, taking the maximum value of the fluorescence intensity of each test curve, taking 0-1 on the abscissa to make a joba's plot curve, specifically referring to FIG. 5, wherein the highest point of the joba's plot curve appears at 0.5, and the combination of BSA and gamma-CD according to the ratio of 1:1 is proved.
5. Nuclear magnetic titration and SEM, TEM, dynamic light scattering testing
0.0000378g BSA were weighed into a vial and 2ml D was used2Dissolving O; 0.0000378g BSA and 0.0001297g gamma-CD were weighed into a vial and 2ml D was added2And dissolving the O. Subsequently, the two solutions were placed in two nuclear magnetic tubes for nuclear magnetic testing, and the nuclear magnetic spectra of BSA, BSA @ gamma-CD are shown in FIG. 6, and the position of the peak in BSA @ gamma-CD and BSThe phase ratio of A is shifted, and the encapsulation of BSA by gamma-CD is proved.
6. Configuration 1 × 10-510ml of BSA solution (1X 10)-55ml of gamma-CD solution. 5ml of BSA solution was taken and placed in 15 ml vial labeled A, 2.5ml of BSA solution was taken mixed with 2.5ml of gamma-CD solution and placed in another 1ml vial labeled B.
A small amount of solution is extracted from the bottle A and is put into a cuvette, and the cuvette is put into a dynamic light scattering instrument to test the size of particles; the same operation was repeated from bottle B. The particle sizes before and after assembly were measured to be 30nm and 20nm, respectively. The dynamic light scattering pattern of the A bottle is shown in FIG. 7 (a), and the dynamic light scattering pattern of the B bottle is shown in FIG. 7 (B).
A small amount of solution is extracted from a bottle A by a disposable dropper and is respectively dripped on the surfaces of the smooth silicon chip and the copper mesh with hydroxylated surfaces; the same operation was performed from bottle B. And performing TEM (transmission electron microscope) characterization on the respectively prepared silicon wafer and the copper mesh, and proving that BSA (bovine serum albumin) is assembled into spherical aggregates before and after the gamma-CD is wrapped. TEM patterns of BSA assembled into spherical aggregates before and after coating with gamma-CD are shown in FIG. 7 (c) and (d), respectively.
7. The construction of a light capture energy system and the study of energy efficiency.
Weighing 0.001044g of sulforhodamine B (SR101) in a 30ml colorless transparent vial, adding 30ml of aqueous solution by using a pipette to prepare 30ml of 1 × 10-5A solution of SR 101.
Carrying out ultraviolet and fluorescence tests on the BSA solution in a No. 01 small bottle; sucking 1ul of SR101 solution by using a micro-injection, adding the solution into a No. 01 small bottle (with a donor ratio of 2500:1), and carrying out ultraviolet and fluorescence tests to obtain corresponding data; then a micro-syringe is used for sucking 4ul of SR101 solution, the solution is added into a No. 01 small bottle (the ratio of the donor to the acceptor is 1000:1), and ultraviolet and fluorescence tests are carried out to obtain corresponding data; then, a micro-syringe is used for sucking 4ul of SR101 solution, and the solution is added into a No. 01 small bottle (donor-acceptor ratio is 625:1) for ultraviolet and fluorescence tests to obtain corresponding data; then 2.5ul of SR101 solution (acceptor supply ratio 385:1) is injected into a No. 01 small bottle, and then ultraviolet and fluorescence are measured; further 4ul of SR101 solution (donor to acceptor ratio 312:1) was injected into vial No. 01, followed by UV and fluorescence measurements; then, 14ul of SR101 solution (donor-acceptor ratio 166:1) is injected into a No. 01 vial, and then ultraviolet and fluorescence tests are carried out; then 5ul of SR101 solution (donor-acceptor ratio: 142:1) was injected into No. 01 flask, and then UV and fluorescence intensity were measured; then 6ul of SR101 solution (the ratio of donor to acceptor is 121:1) is dripped into a No. 01 small bottle, and then ultraviolet and fluorescence tests are carried out; finally, 7ul of SR101 solution (donor to acceptor ratio 116:1) was added dropwise to vial No. 01, and then UV and fluorescence measurements were performed. The test results are shown in fig. 8(a) and (b), and the curve in fig. 8(a) shows the ratio of BSA to SR101 at 600nm from bottom to top in sequence: ultraviolet absorption spectra of 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; the curve in FIG. 8(b) shows, at 620nm, the ratio of BSA to SR101 in order from bottom to top: fluorescence spectra of 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.
In the ultraviolet diagram, the absorbance of the donor is continuously reduced with the increase of SR101, and the absorbance of the acceptor is continuously increased; in the fluorescence image, the fluorescence intensity of the donor is continuously reduced, the fluorescence intensity of the acceptor is continuously enhanced, the enhancement is obvious, and the energy is transferred. Under 365nm illumination, the BSA solution has low luminous intensity, and as SR101 is continuously added dropwise, the fluorescence intensity is continuously increased from 50 to about 500, and yellow fluorescence is emitted.
Carrying out ultraviolet and fluorescence tests on the BSA solution in a No. 02 small bottle; sucking 1ul of SR101 solution by using a micro-injection, adding the solution into a No. 02 vial (with a donor ratio of 2500:1), and carrying out ultraviolet and fluorescence tests to obtain corresponding data; then a micro-syringe is used for sucking 4ul of SR101 solution, the solution is added into a No. 02 vial (the ratio of the donor to the acceptor is 1000:1), and ultraviolet and fluorescence tests are carried out to obtain corresponding data; then, 4ul of SR101 solution is absorbed by a micro-syringe and added into a No. 02 vial (donor-acceptor ratio 625:1) for ultraviolet and fluorescence tests, and corresponding data are obtained; 2.5ul of SR101 solution (acceptor supply ratio 385:1) is injected into a No. 02 vial, and then ultraviolet and fluorescence are measured; further 4ul of SR101 solution (donor to acceptor ratio 312:1) was injected into a No. 02 vial, followed by UV and fluorescence measurements; then 14ul of SR101 solution (donor to acceptor ratio 166:1) was injected into a 02 # vial, followed by uv, fluorescence tests; then 5ul of SR101 solution (donor to acceptor ratio 142:1) was injected into No. 02 flask, and then UV and fluorescence intensity were measured; then 6ul of SR101 solution (the ratio of donor to acceptor is 121:1) is dripped into a No. 02 small bottle, and then ultraviolet and fluorescence tests are carried out; finally, 7ul of SR101 solution (donor to acceptor ratio 116:1) was added dropwise to vial No. 02 and subjected to UV irradiation. And (4) testing fluorescence. The results of the tests are shown in FIGS. 8(c) and (d), and the curves in FIG. 8(c) indicate the ratio of BSA @ gamma-CD to SR101 at 590nm from bottom to top in sequence: ultraviolet absorption spectra of 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; the curve in FIG. 8(d) shows, from bottom to top at 620nm, the ratio of BSA @ γ -CD to SR101 in order: fluorescence spectra of 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.
In a BSA solution added with gamma-CD, the gamma-CD is assembled with the BSA, the fluorescence intensity is obviously improved, the absorbance of the ultraviolet donor position is continuously reduced along with the continuous addition of the receptor SR101, and the receptor position is obviously improved; fluorescence intensity at donor site is significantly reduced and fluorescence intensity at acceptor site is significantly increased. At 365nm, BSA @ gamma-CD emits yellow green fluorescence; with increasing SR101, the BSA @ γ -CD fluoresces pink.
8. Energy transfer efficiency and antenna effect calculation.
In a system of adding SR101 dropwise in BSA solution, pure 1X 10-5The fluorescence intensity of the BSA solution was 245, and after addition of SR101, the fluorescence intensity reached 286 (donor-acceptor ratio: 116:1), according to the formula Φ ET ═ 1-IDA/IDThe energy transfer efficiency is 18.2 percent; exciting by 1X 10 at 383nm and 580nm respectively-5Solubilization of BSA + SR101The fluorescence intensity of the obtained acceptor at 383nm can reach 475, the fluorescence intensity of the acceptor when the acceptor is excited at 580nm is 50, and the fluorescence intensity of the acceptor is expressed according to the Antenna effect ═ IDA,350-ID,350)/IDA,580The antenna effect can be calculated to be 9.8.
In a system of adding SR101 dropwise into BSA @ gamma-CD solution, pure 1X 10-5The fluorescence intensity of the BSA @ gamma-CD solution is 5094, and after SR101 is added, the fluorescence intensity can reach 5927 (donor-acceptor ratio: 116:1), and the formula phi ET is 1-IDA/IDThe energy transfer efficiency is 41.7 percent; exciting by 1X 10 at 383nm and 580nm respectively-5BSA + SR101 gave a solution with an acceptor fluorescence intensity of 7200 at 383nm and 863 at 580nm, according to the Antennaeffect ═ IDA,350-ID,350)/IDA,580The antenna effect can be calculated to be 84.5.
9. And calculating the service life of the system.
Claims (7)
1. An aqueous phase light trapping system constructed by salicylaldehyde azine derivatives, which is characterized in that: adding gamma-cyclodextrin into a salicylaldehyde azine derivative aqueous solution to form a pseudo-rotaxane structure, assembling the pseudo-rotaxane structure in the aqueous solution to form a spherical aggregate, and constructing a water-phase light capture system by using the spherical aggregate as an energy donor and sulforhodamine as an energy acceptor;
a process for the preparation of salicylaldehyde azine derivatives comprising the steps of:
(1) dissolving 2, 4-dihydroxybenzaldehyde in acetonitrile solvent, dropwise adding 1, 6-dibromohexane, and adding K2CO3Heating and refluxing for reaction to obtain 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde;
(2) adding the 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde obtained in the step (1), hydrazine hydrate and a reaction solvent ethanol into a reactor, and heating and refluxing for reaction;
(3) taking the reaction product obtained in the step (2) as a raw material, taking pyridine as a reaction solvent, and heating and refluxing the reaction system for reaction to obtain a salicylaldehyde azine derivative;
a salicylaldehyde azine derivative having the structure:
2. the aqueous phase light trapping system constructed from salicylaldehyde azine derivatives as claimed in claim 1, wherein: 2, 4-dihydroxybenzaldehyde, 1, 6-dibromohexane and K in the step (1)2CO3The feeding weight ratio of (A) is 1.45-1.55:0.45-0.55: 1.
3. The aqueous phase light trapping system constructed from salicylaldehyde azine derivatives as claimed in claim 1, wherein: in the step (1), the heating reflux reaction temperature is 80-90 ℃, and the heating reflux reaction time is 11-13 hours.
4. The aqueous phase light trapping system constructed from salicylaldehyde azine derivatives as claimed in claim 1, wherein: in the step (2), the feeding ratio of the 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde to the hydrazine hydrate is 0.5:10-10.5, wherein the 2-hydroxy-4- (6-bromohexyloxy) benzaldehyde is counted by g, and the hydrazine hydrate is counted by mL.
5. The aqueous phase light trapping system constructed from salicylaldehyde azine derivatives as claimed in claim 1, wherein: in the step (2), the heating reflux reaction temperature is 80-90 ℃, and the heating reflux reaction time is 5-7 hours.
6. The aqueous phase light trapping system constructed from salicylaldehyde azine derivatives as claimed in claim 1, wherein: in the step (3), the heating reflux reaction temperature is 110-120 ℃, and the heating reflux reaction time is 2.5-3.5 hours.
7. An aqueous phase light trapping system constructed from the salicylaldehyde azine derivative of claim 1, wherein: the salicylaldehyde azine derivative forms a spherical aggregate structure in a self-assembly manner in an aqueous solution, the spherical aggregate is used as an energy donor, sulforhodamine is used as an energy acceptor, and a water-phase light capture system is constructed.
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