CN105001666B - A kind of asymmetric near-infrared squaraine dye and preparation method and application - Google Patents
A kind of asymmetric near-infrared squaraine dye and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of asymmetric near-infrared squaraine dye and preparation method and application, be by m-aminophenol derivatives and side's acid mixing, be dissolved in appropriate solvent, and reflux water-dividing processes under nitrogen protection；Then gained reactant mixture is cooled to room temperature, removal of solvent under reduced pressure, through silica gel column chromatography purification after the washing of gained thick product dichloromethane, obtains described asymmetric near-infrared squaraine dye.The present invention can be effectively improved squaraine dye dissolubility in aqueous by the introducing of oxygen ether chain, gained asymmetric near-infrared squaraine dye good stability, excellent in optical properties, the protein marker can answered as fluorescence and colorimetric double-bang firecracker, for biomolecular labeling, analyze and multiple fields such as separation.
Description
Technical field
The invention belongs to technical field of analytical chemistry, be specifically related to a kind of asymmetric near-infrared squaraine dye and preparation side thereof
Method and application.
Background technology
The transmitting wavelength of near infrared fluorescent dye is between 650-900 nm, and biomolecule autofluorescence is relatively within the range
Weak, biological context interference can be avoided to obtain higher sensitivity for analysis (Shi Feng;Li Hongyang;Peng Xiaojun. bioanalysis is used
Near infrared fluorescent dye progress.Fine chemistry industry2003, 20 (5), 268-272.), and wavelength > HONGGUANG of 650 nm can
To penetrate animal skin and tissue, therefore, nir dye is applied in bioanalysis and cell imaging as fluorescent probe
Attract wide attention.
Squaraine dye is 1,3-bis-replacement generated with electron rich aryl compound or amino benzenes compounds condensation by side's acid
Derivant.This compounds is noteworthy characterized by has narrow and strong absorption band and higher amount at visible ray to near-infrared region
Sub-productivity.This photoelectric characteristic is mainly derived from the strong Donor-Acceptor-Donor of intramolecular (donor-acceptor-donor)
Between charge transfer interaction.In recent years, squaraine dye receives much concern with optical property, the good light stability of its excellence, becomes
One of focus for functional dye research.The planar structure having due to squaraine dye makes it easily assemble in polar solvent,
Thus cause absorption band broadening and fluorescent quenching；And fluorescence signal would generally occur to recover or strengthen in disaggregation process,
This provides a kind of interesting new way for design " Fluorescence Increasing type " probe.Buncel and McKerrow et al. is by inhaling in early days
Receive the state of aggregation absworption peak that optical spectroscopy squaraine dye is formed in the different proportion organic solvent mixed phase with water, subsequently
Research in point out that again chromophoric structure can affect dye molecule accumulation mode (Buncel, E. in the solution;
McKerrow, A. J.; Kazmaier, P. M. Solvent-controlled aggregation of a
photoconductive dye. J. Chem. Soc., Chem. Commun.1992, (17), 1242-1243;
McKerrow, A. J.; Buncel, E.; Kazmaier, P. M. Aggregation of squaraine dyes:
structure-property relationships and solvent effects. Can. J. Chem.1995, 73 (10), 1605-1615.).2010, Pang et al., by the small change of molecular structure, made squaraine dye containing trace table
The solution of face activating agent assembles and obtains H-aggregation and J-aggregation.Formed state of aggregation and biomacromolecule albumen between non-
Covalent effect power makes dyestuff disaggregation, discharges fluorescence signal, it is achieved that Selective recognition (Xu, the Y. of albumen; Li, Z.;
Malkovskiy, A.; Sun, S.; Pang, Y. Aggregation control of squaraines and their
use as near-infrared fluorescent sensors for protein. J. Phys. Chem. B2010,114 (25), 8574-8580.).This seminar utilizes part dithiocarbamate (dithiocarbamate, DTC) right
The affinity that heavy metal ion is good, devising mercury ion coordination induction disaggregation type squaraine dye colorimetric fluorescence double-bang firecracker should visit
Pin.Hg2+Combination with dye molecule side chain DTC is formed sterically hindered, causes dyestuff disaggregation, and makes solution colour by purplish red
Complexion changed is blue, solution fluorescence intensity enhancing 700 times, and the detection limit of mercury ion be can reach 7.1 nM(Chen, C.; Wang,
R.; Guo, L.; Fu, N.; Dong, H.; Yuan, Y. A squaraine-based colorimetric and
“turn on” fluorescent sensor for selective detection of Hg2+ in an aqueous
medium. Org. Lett.2011, 13 (5), 1162-1165.).But it is water miscible due to biomacromolecule mostly, institute
Good spectrum property is not needed only have in the application of biomedical sector with squaraine dye, good water-soluble with greater need for having
Property.But the water solublity of current most of squaraine dye is poor, limit its application at biomedical aspect.
Serum albumin is one of component of buffer system of blood, has Nutrition, is to maintain blood colloid osmotic pressure
Main component and transport endogenous and the important carrier of exogenous material.Bovine serum albumin (Bovine Serum
Albumin, BSA) as the main component albumen (0.38 g/mL) of blood plasma, owing to its molecular weight is little, low cost, Stability Analysis of Structures,
Excellent binding ability and with the structural homology of human serum albumin (Human Serum Albumin) and cause widely
Research.The present invention introduces hydrophilic radical oxygen ether chain by the side chain at squaraine dye, and to strengthen its water solublity, gained is asymmetric
Near-infrared squaraine dye purity is high, good stability, and the protein marker can answered as fluorescence and colorimetric double-bang firecracker, for serum albumin
Deng detection.
Summary of the invention
It is an object of the invention to provide a kind of asymmetric near-infrared squaraine dye and preparation method and application, by
The side chain of squaraine dye introduces hydrophilic radical oxygen ether chain, and to strengthen its water solublity, gained dye stability is good, and optical property is excellent
Different, and synthetic method is simple, easy control of reaction conditions, product purity is high, the albumen mark can answered as fluorescence and colorimetric double-bang firecracker
Note thing, for the detection of serum albumin etc..
For achieving the above object, the present invention adopts the following technical scheme that
A kind of asymmetric near-infrared squaraine dye, its structural formula is:
。
The preparation method of described asymmetric near-infrared squaraine dye comprises the following steps:
1) general side's acidAdd after dissolving in solventWith
, and carry out reflux water-dividing process under nitrogen protection；
2), after reaction terminates, gained reactant mixture is cooled to room temperature, removal of solvent under reduced pressure, obtains thick product；
3) the thick product of gained is after dichloromethane washs, and uses silica gel column chromatography to carry out gradient elution, obtains described asymmetric
Near-infrared squaraine dye.
Above-mentioned steps 1) in used、With square acidRub
That ratio is 2:4:3；Solvent for use is n-butyl alcohol and benzene 2:1 by volume mixes.
Gradient elution described in step 3) is first to carry out eluting with dichloromethane, then by dichloromethane with methanol by volume
Eluting is carried out after 100:1 mixing.
Wherein, describedSynthetic method comprise the steps:
1) by m-aminophenol,Mix with sodium carbonate, be dissolved in isopropanol with water by volume
In the solution of 1:1 mixing, it is heated with stirring to 85 DEG C under nitrogen protection, is then refluxed for reacting 48 hours, reacts complete and be cooled to
Room temperature；
2) after adding saturated aqueous common salt mixing, extracting with dichloromethane, gained organic facies is dried with anhydrous magnesium sulfate, rotation
Solvent is evaporated off and obtains crude product；
3) gained crude on silica gel column chromatography purification is got product.
DescribedSynthetic method comprise the steps:
1) m-aminophenol, bromoethane and sodium carbonate are mixed, be dissolved in the solution that isopropanol mixes with water 1:1 by volume
In, it is heated with stirring to 85 DEG C under nitrogen protection, is then refluxed for reacting 24 hours, reacts complete and be cooled to room temperature；
2) after adding saturated aqueous common salt mixing, extracting with dichloromethane, gained organic facies is dried with anhydrous magnesium sulfate, rotation
Solvent is evaporated off and obtains crude product；
3) gained crude on silica gel column chromatography purification is got product.
The protein marker that acid dye in gained asymmetric near-infrared side can be answered as fluorescence and colorimetric double-bang firecracker is for serum albumin
Deng detection.
The remarkable advantage of the present invention is: the present invention, by accessing oxygen ether chain to aniline side chain, have adjusted the dissolving of dyestuff
Performance and Assembling Behavior, improve its dissolubility in water, thus have impact on the photophysical property of dyestuff.Gained is asymmetric closely
Infrared squaraine dye good stability, excellent in optical properties, the protein marker can answered as fluorescence and colorimetric double-bang firecracker, for biology
Molecular marker, analyze and multiple fields such as separation.
Accompanying drawing explanation
Fig. 1 is the present invention asymmetric near-infrared squaraine dye absorption spectrum variation diagram in different solvents.
Fig. 2 is that the present invention asymmetric near-infrared squaraine dye absorption spectrum in the ethanol-water solution of different proportion becomes
Change figure.
Fig. 3 be the present invention asymmetric near-infrared squaraine dye in the PB buffer (10 mM) of pH 7.0 to variable concentrations
The abosrption spectrogram (A) of BSA and fluorescence spectrum figure (B) (λex=620 nm, PMT=650 V, slit=5 nm/5 nm).
Fig. 4 is the grain after the present invention asymmetric near-infrared squaraine dye grain size distribution (A) in pure water and dropping BSA
Footpath scattergram (B).
Fig. 5 is that the response of BSA is become by the present invention asymmetric near-infrared squaraine dye fluorescence intensity at 660 nm with pH value
Change trendgram (λex=620 nm, PMT=650 V, slit=5 nm/5 nm).
Fig. 6 dropping BSA that is the present invention asymmetric near-infrared squaraine dye in the PB buffer (10 mM) of pH 7.0 and
Fluorescence spectrum figure (λ during its bioturbation thingex=620 nm, PMT=650 V, slit=5 nm/5 nm).
Detailed description of the invention
In order to make content of the present invention easily facilitate understanding, below in conjunction with detailed description of the invention to of the present invention
Technical scheme is described further, but the present invention is not limited only to this.
Embodiment 1
The concrete steps of synthesis:
M-aminophenol (0.196 g, 1.80 mmol) is added in the clean there-necked flask of 50 mL,(0.988 g, 3.60 mmol), sodium carbonate (0.267 g, 2.52 mmol), add 30 mL
Isopropanol-water mixed liquor (1:1, v/v) dissolves, mixes, and is heated with stirring to 85 DEG C under nitrogen protection, is then refluxed for reacting 48 little
Time, TLC tracks to raw material point and is wholly absent, is reaction end.After reaction terminates, the isopropyl that rotation is evaporated off in dereaction mixed liquor
Alcohol.Then product is transferred in the separatory funnel of 100 mL, adds a small amount of saturated aqueous common salt, then with the two of 30 mL
Chloromethanes extracts three times, merges organic layer.Being dried organic layer with anhydrous magnesium sulfate, stand, be filtered to remove magnesium sulfate, mother solution is through rotation
Unnecessary dichloromethane is evaporated off.Gained material silicagel column purifies, first with petroleum ether: ethyl acetate (1.5:1, v/v) is for washing
De-agent remove impurity and monosubstituted between hydroxyanilines derivant, then eluant polarity is increased to petroleum ether: ethyl acetate (1:1,
V/v), obtain flaxen grease 0.200 g, be disubstituted hydroxyanilines derivant of target, productivity 35 %.1H
NMR(400 MHz, CDCl3): δ 7.01(t,J=8.4 Hz, 1H), 6.23(d,J=6.3 Hz, 2H), 6.17(d,J=8.1 Hz,
1H), 3.60(t,J=6.3 Hz, 8H), 3.53(dd,J=13.4,6.4 Hz, 8H), 3.39(s, 6H).13C NMR(100 MHz,
CDCl3): δ 157.43,149.29,130.21,104.02,103.42,99.02,72.02,70.48,68.44,58.92,
50.99。
Embodiment 2
The concrete steps of synthesis:
M-aminophenol (1.96 g, 18.0 mmol), sodium carbonate (2.76 is added in the clean there-necked flask of 100 mL
G, 26.0 mmol), bromoethane (3.92 g, 36.0 mmol), add 60 mL isopropanol-water mixed liquor (1:1, v/v) molten
Solving, mix, be heated with stirring to 85 DEG C under nitrogen protection, be then refluxed for reacting 24 hours, TLC tracks to raw material point and disappears completely
Lose, be reaction end.After reaction terminates, the isopropanol that rotation is evaporated off in dereaction mixed liquor.Then product is transferred to 250
In the separatory funnel of mL, add a small amount of saturated aqueous common salt, then extract three times with the dichloromethane of 30 mL, merge organic layer.
Being dried organic layer with anhydrous magnesium sulfate, stand, be filtered to remove magnesium sulfate, then rotation is evaporated off unnecessary dichloromethane.Gains
Matter silicagel column purifies, and eluant is petroleum ether: ethyl acetate (10:1, v/v), obtains mauve grease 1.81 g, produces
Rate 61%.1H NMR(400 MHz, CDCl3): δ 7.11(t,J=8.1 Hz, 1H), 6.36(d,J=8.3 Hz, 1H), 6.28(s,
1H), 6.24(d,J=7.9 Hz, 1H), 5.67(s, 1H), 3.34(q,J=7.0 Hz, 4H), 1.18(t,J=7.0 Hz, 6H).13C
NMR(100 MHz, CDCl3): δ 156.95,149.53,130.25,105.58,103.67,100.20,44.62,12.43.
Embodiment 3
Asymmetric near-infrared squaraine dyeConcrete preparation
Method is as follows:
The side's of being separately added into acid in the there-necked flask of 100 mL(43.3 mg, 0.38 mmol), 30 mL are just
Butanol and the benzene of 15 mL, be heated to reflux about 1 hour under nitrogen protection, when water knockout drum not having obvious water separate,
Start to be slowly added to a small amount of n-Butanol soluble(81.5 mg, 0.26 mmol), reacts 20 minutes
Add a small amount of n-Butanol soluble afterwards(84.3 mg, 0.51 mmol), lower point of water backflow 2 of stirring condition
Hour, stopped reaction, reactant mixture is cooled to room temperature, after removal of solvent under reduced pressure, obtained product uses silicagel column pure
Change, be first that eluant carries out eluting with dichloromethane, then with dichloromethane: the eluent of methanol (100:1, v/v) is washed
De-, obtain target product 57.5 mg, productivity 40%, fusing point: 154-156 DEG C.1H NMR(400 MHz, CDCl3): δ 12.13
(s, 1H), 11.43(s, 1H), 7.89(s, 2H), 6.41(dd,J=9.2,2.4 Hz, 1H), 6.38(dd,J=9.3,2.3 Hz,
1H), 6.17(d,J=2.4 Hz, 1H), 6.16(d,J=2.2 Hz, 1H), 3.70(dd,J=9.7,4.3 Hz, 8H), 3.60(dd,J=5.6,3.2 Hz, 4H), 3.52(dd, J=6.2,3.0 Hz, 4H), 3.48(q,J=7.1 Hz, 4H), 3.38(s, 6H), 1.26
(t,J=7.1 Hz, 6H).13C NMR(100 MHz, CDCl3): δ 182.91,173.45,172.10,164.95,164.22,
156.47,156.43,132.78,132.23,110.13,110.04,107.76,107.58,98.91,98.38,71.93,
70.77,68.54,59.10,51.61,45.47,12.97.ESI-MS:m/z579.5([M+Na]+).
By accessing oxygen ether chain to aniline side chain, solubility property and the Assembling Behavior of dyestuff can be regulated, improve it at water
In dissolubility, thus affect the photophysical property of dyestuff.This dyestuff is in state of aggregation, fluorescent quenching, place in pure aquatic system
Noncovalent interaction power between the dyestuff and BSA of state of aggregation makes dyestuff disaggregation, discharges fluorescence signal, it is achieved that fluorescence and ratio
The protein labeling that color double-bang firecracker is answered.
Fig. 1 is the present invention asymmetric near-infrared squaraine dye (concentration is 1.0 μMs) absorption spectrum in different solvents.
From figure 1 it appears that in the range of the absorption maximum that this dyestuff is in different organic solvents is positioned at 638-654 nm, with solvent
Polarity strengthens, and the red shift of the maximum absorption wavelength of dyestuff shows less forward solvation effect.In formic acid solution,
Label occurs mountain peak shape absworption peak at 450-600 nm, is the absworption peak after squaraine dye protonation.In pure aquatic system,
There is significantly reduction at monomer absorption peak, the obvious broad peak of appearance wavelength 500 nm at, this show in pure aquatic system dyestuff with
State of aggregation form exists.
Fig. 2 is the present invention asymmetric near-infrared squaraine dye (concentration the is 1.0 μMs) ethanol-water solution at different proportion
In absorption spectrum.From figure 2 it can be seen that when water content is 90%, monomer absorption peak begins with significantly reduction, at ripple
Obvious broad peak occur at long 500 nm, this shows that in system, dyestuff is assembled, and thus may determine that connecing of oxygen ether chain simultaneously
Enter to be effectively improved squaraine dye dissolubility in aqueous and stop the generation of aggregation.
Fig. 3 is respectively the present invention asymmetric near-infrared squaraine dye (concentration is 1.0 μMs) the PB buffer at pH 7.0
Absorption and fluorescence spectrum variation diagram to variable concentrations BSA aqueous solution in (10 mM).It can be seen that to test
After adding BSA in system, the uv absorption at 650 nm gradually strengthens, and the uv absorption at 500 nm gradually weakens, table
Bright squaraine dye is morphon from state of aggregation gradually depolymerization, and the color of dyestuff is after the aubergine of state of aggregation is changed into depolymerization
Cyanic colours.Simultaneously along with the dropping of BSA, the fluorescence of system gradually strengthens, and therefore this dyestuff can be as fluorescence and colorimetric double-bang firecracker
The protein marker answered.Change according to surveyed fluorescence intensity (λ ex=630 nm, slit:5 nm/5 nm, PMT Volts:
750), draw the relation curve of BSA concentration and fluorescence intensity, and obtain matched curve (k=2.68 × 107Au/M, R2=
0.9982), thus calculating detection limit (LOD) is 1.5 μ g mL-1(3 σ/k).
Fig. 4 be respectively the present invention asymmetric near-infrared squaraine dye (concentration is 1.0 μMs) in pure water with add after BSA
The grain size distribution of solution.Test result indicate that, this squaraine dye exists with aggregate form in pure water, and mean diameter is about
581 nm, after adding BSA, mean diameter reduces to 338 nm, it was demonstrated that dyestuff occurs to understand under the effect of BSA to be assembled.
Fig. 5 is that the present invention asymmetric near-infrared squaraine dye (concentration is 1.0 μMs) is strong to the fluorescence of BSA at 660 nm
Spend the trendgram with pH value change.As seen from Figure 5, in the case of pH=7.0, fluorescence intensity is the strongest, and effect is best, says
This dyestuff bright can be effectively combined with BSA and improve fluorescence intensity under conditions of neutrality, is expected in living things system realize
Mark to albumen.
Fig. 6 is the present invention asymmetric near-infrared squaraine dye (concentration is 1.0 μMs) the PB buffer (10 at pH 7.0
MM) to dropping BSA and the protease such as trypsin, lipase in, proline, histidine, cysteine, arginine, serine,
Fluorescence light during other chaff interferences such as the little molecule aminoacid such as lysine, glutamic acid, aspartic acid, tyrosine and glutathion
Spectrum variation diagram.It will be appreciated from fig. 6 that this dyestuff can cause the disaggregation of dyestuff with BSA by noncovalent interaction, thus cause absorbing
The red shift of spectrum and the release of fluorescence, and this protein marker only has spectral response to BSA, and to trypsin, lipase etc.
Protease, proline, histidine, cysteine, arginine, serine, lysine, glutamic acid, aspartic acid, tyrosine etc.
The multiple chaff interferences such as little molecule aminoacid and glutathion are without response, it is possible to achieve the specific recognition to BSA.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (7)
1. an asymmetric near-infrared squaraine dye, it is characterised in that: its structural formula is:
。
2. the preparation method of an asymmetric near-infrared squaraine dye as claimed in claim 1, it is characterised in that: include following step
Rapid:
1) general side's acidAdd after dissolving in solventWith, and
Carry out reflux water-dividing process under nitrogen protection；
2), after reaction terminates, gained reactant mixture is cooled to room temperature, removal of solvent under reduced pressure, obtains thick product；
3) the thick product of gained is after dichloromethane washs, and uses silica gel column chromatography to carry out gradient elution, obtains described asymmetric the reddest
Outer squaraine dye.
The preparation method of the most asymmetric near-infrared squaraine dye, it is characterised in that: describedSynthetic method comprise the steps:
1) by m-aminophenol,Mix with sodium carbonate, be dissolved in isopropanol and mix with water 1:1 by volume
In the solution closed, it is heated with stirring to 85 DEG C under nitrogen protection, is then refluxed for reacting 48 hours, reacts complete and be cooled to room temperature；
2) after adding saturated aqueous common salt mixing, extracting with dichloromethane, gained organic facies is dried with anhydrous magnesium sulfate, and rotation is evaporated off
Solvent is gone to obtain crude product；
3) gained crude on silica gel column chromatography purification is got product.
The preparation method of the most asymmetric near-infrared squaraine dye, it is characterised in that: describedSynthetic method comprise the steps:
1) m-aminophenol, bromoethane and sodium carbonate are mixed, are dissolved in the solution that isopropanol mixes with water 1:1 by volume,
It is heated with stirring to 85 DEG C under nitrogen protection, is then refluxed for reacting 24 hours, reacts complete and be cooled to room temperature；
2) after adding saturated aqueous common salt mixing, extracting with dichloromethane, gained organic facies is dried with anhydrous magnesium sulfate, and rotation is evaporated off
Solvent is gone to obtain crude product；
3) gained crude on silica gel column chromatography purification is got product.
The preparation method of the most asymmetric near-infrared squaraine dye, it is characterised in that: used in step 1)、It is 2:4:3 with the mol ratio of side's acid；Solvent for use be n-butyl alcohol and benzene by
Volume ratio 2:1 mixes.
The preparation method of the most asymmetric near-infrared squaraine dye, it is characterised in that: described in step 3)
Gradient elution is first to carry out eluting with dichloromethane, then dichloromethane and methanol are carried out eluting after 100:1 mixes by volume.
7. the application of an asymmetric near-infrared squaraine dye as claimed in claim 1, it is characterised in that: as fluorescence and colorimetric
The protein marker that double-bang firecracker is answered.
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