CN110483513A - Fluorescent molecule, preparation method, its application and luciferase assay reagent - Google Patents
Fluorescent molecule, preparation method, its application and luciferase assay reagent Download PDFInfo
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Abstract
The invention discloses fluorescent molecule, preparation method, its application and luciferase assay reagents.Fluorescent molecule is the compound with formula (1) structure, and formula (1) is as follows:Wherein R1For alkyl or substituted aromatic base, R2For the substituted aroma group containing-HC=N-N=CH- group.- HC=N-N=CH- group in the fluorescent molecule can be acted on specifically with hypochlorite, make it possible to the ability for having naked eye to identify hypochlorite, meanwhile, it is capable to accurately, it is sensitive, specific and efficiently detect hypochlorite ion.
Description
Technical field
The present invention relates to bioassay technique field, in particular to fluorescent molecule, preparation method, its application and
Luciferase assay reagent.
Background technique
The oxidisability of hypochlorite is extremely strong, is a kind of well-known disinfectant, it is deposited as a kind of important active oxygen
It is in organism, is played a crucial role in cell Redox balance, participate in numerous physiology, pathologic process,
Including hepatic injury and cancer, while can also react with multiple proteins, fatty acid, cholesterol and DNA, RNA etc..
Another key property of hypochlorite is antibiotic property, it is mainly realized by enzyme required in haptoreaction this anti-
Bacterium bactericidal effect, and this is reached with the approach for aoxidizing certain virus.And in living organism therein, endogenous by-product
Mainly generated in primary (close) catalysis is reacted by hydrogen peroxide and chloride ion, when internal hypochlorite concentration and pH value not
When in normal physiologic range, all body can be caused to seriously endanger, cause various diseases, for example there are: common cardiovascular diseases
Disease, cancer difficult to treat, the interlink inflammation often sent out and the Alzheimer's disease for influencing intelligence etc..Therefore, it discloses
ClO-It is exploitation for ClO in the occurrence and development of disease-Fluorescence probe critical function, and the intracorporal hypochlorite of biology
Concentration and pH value can be accurately detected, this also has great importance, wherein being the most significantly: can be with studying physiological function
Variation and operating mechanism, solve the problems in pathological process, while the development of the fluorescence probe of practical application is proposed more
High requirement.
The common methods of measurement hypochlorite at present, mainly have: spectrophotometry, fluorimetry, chemiluminescence
Measuring method, phosphorimetric determination, electrochemical determination etc..
Hypochlorous acid (HClO) is used as a kind of high-efficient oxidant, is well known as the key of pathogen in innate immune system
" killer ".More and more evidences show that intracellular HClO plays additional important work in adjusting inflammation and Apoptosis
With.However, the organelle for participating in HClO distribution is still unknown, cause to be difficult to make full use of it in cell signaling pathway and each
Biological function in kind disease.One of them main reason is that, the Strong oxdiative of HClO easily decomposes and unstable, it is caused to lack
Weary effective chemical tools directly detect subcellsular level.Have developed a series of HClO/ClO- fluorescence probes recent years, so
And they the following limitations exist mostly: the detection of big multiprobe is to emit that identification, therefore background interference is strong based on short wavelength,
Identify poor sensitivity；Big multiprobe is all non-Ratiometric fluorescent probe, therefore is single to the identification of signal, in addition, close red
Outer hypochlorous acid is even more few with fluorescence probe.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide fluorescent molecule, can efficiently, sensitively detect hypochlorite, and can be right
ClO-There is apparent naked eye recognition capability.
Luciferase assay reagent provided by the invention, the detection to hypochlorite are sketch-based user interface fluorescence identifying and near-infrared hair
(> the 800nm) of light identification.Therefore, detection method of the invention improves the sensitivity and accuracy of existing hypochlorite detection.
Another object of the present invention is to provide the preparation method of fluorescent molecule, this method is easy to operate, material is easy to get, just
In implementation.
The present invention is implemented as follows:
In a first aspect, the embodiment of the present invention provides a kind of fluorescent molecule, it is the compound with formula (1) structure, formula (1)
It is as follows:
Wherein R1For alkyl or substituted aromatic base, R2For the substituted aroma group containing-HC=N-N=CH- group.
Second aspect, the embodiment of the present invention provide the preparation side such as the described in any item fluorescent molecules of aforementioned embodiments
Method, comprising the following steps:
It reacts bis- substitution -3,4,9,10- tetracarboxylic acid anhydride of 1,7- to form intermediate 1 with amine substance；
And rear center body 1 reacts to form intermediate 2 with compound of benzaldehyde category；
Intermediate 2 reacts to form the fluorescent molecule with aromatic aldehyde condensation hydrazine compound.
The third aspect, the embodiment of the present invention provide a kind of luciferase assay reagent comprising any one of aforementioned embodiments institute
The fluorescent molecule stated；
Preferably, the concentration of fluorescent molecule described in the luciferase assay reagent of unit formulation is 0.1-10 μM.
Fourth aspect, the embodiment of the present invention are provided if the described in any item fluorescent molecules of aforementioned embodiments are in fluorescence detection
In application；
Preferably, hypochlorite ion is detected using for the utilization fluorescent molecule；
Preferably, material concentration >=0.05 μM to be detected when fluorescence detection in detection liquid, preferably 0.1 μM.
The invention has the following advantages: can using-HC=N-N=CH- the group in fluorescent molecule of the invention
Specifically with hypochlorite act on, make it possible to hypochlorite have naked eye identify ability, meanwhile, it is capable to accurately, spirit
It is quick, specific and efficiently detect hypochlorite ion.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the nucleus magnetic hydrogen spectrum figure for the intermediate 2 that the embodiment of the present invention 1 provides；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure for the fluorescent molecule that the embodiment of the present invention 1 provides；
Fig. 3 is the nuclear-magnetism carbon spectrogram for the fluorescent molecule that the embodiment of the present invention 1 provides；
Fig. 4 is the mass spectrogram for the fluorescent molecule that the embodiment of the present invention 1 provides；
Fig. 5 is that the fluorescent molecule that experimental example 1 of the present invention provides takes pictures to the natural light of the Visual retrieval of hypochlorite ion
Result figure；
Fig. 6 is that the fluorescent molecule that experimental example 1 of the present invention provides takes pictures to the ultraviolet lamp of the Visual retrieval of hypochlorite ion
Result figure；
Fig. 7 is ultraviolet spectrogram of the fluorescent molecule that provides of experimental example 2 of the present invention to the spectral response of hypochlorite ion；
Fig. 8 is fluorescence spectra of the fluorescent molecule that provides of experimental example 2 of the present invention to the spectral response of hypochlorite ion；
Fig. 9 is result figure of the fluorescent molecule that provides of experimental example 3 of the present invention to the time response of hypochlorite ion；
Figure 10 is the ultraviolet spectra that the fluorescent molecule that experimental example 4 of the present invention provides responds the concentration gradient of hypochlorite ion
Figure；
Figure 11 is the fluorescence spectrum that the fluorescent molecule that experimental example 4 of the present invention provides responds the concentration gradient of hypochlorite ion
Scheme (359 nanometers)；
Figure 12 is the fluorescence spectrum that the fluorescent molecule that experimental example 4 of the present invention provides responds the concentration gradient of hypochlorite ion
Scheme (740 nanometers)；
Figure 13 is the result that the fluorescent molecule that experimental example 5 of the present invention provides measures the anti-interference of other ions and molecule
Figure.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Feature and performance of the invention are described in further detail with reference to embodiments.
Firstly, being the compound with formula (1) structure, formula (1) is such as the embodiment of the invention provides a kind of fluorescent molecule
Under:
Wherein R1 is alkyl or substituted aromatic base, and R2 is the substituted aroma group containing-HC=N-N=CH- group.The compound
In-HC=N-N=CH- can specifically with hypochlorite act on, can specifically detect hypochlorite, and sensitivity
It is more excellent.Specifically, the fluorescent molecule and hypochlorite can significantly increase the fluorescence intensity at 600nm after acting on, meanwhile,
When being excited with 359nm, fluorescence intensity increases accordingly as time increases, and 800nm or so have one it is apparent
Transmitting, can be effectively detected hypochlorite.
Further, the alkyl of R1 is C1-C10 linear or branched alkyl group, preferably, methyl, ethyl, n-propyl, positive fourth
Any one in base and 3- ethyl hexyl；More preferably normal-butyl；
Preferably, R1Substituted aromatic base be benzyl substituted or unsubstituted；
It is highly preferred that the substituent group of substituted benzyl is alkyl, it is highly preferred that alkyl is C1-C4 alkyl；
Most preferably isopropyl；
Most preferably, R1Any one in following group:
Further, R2For the group with formula (2) structure；-X-R3- HC=N-N=CH-R4Formula (2)；Wherein, X is selected from O
Or sulphur, it is preferable that X O；
R3And R4Separately it is selected from substituted or unsubstituted aromatic group；
Preferably, aromatic group is selected from phenyl or fused aromatic group；More preferably phenyl；
Preferably, substituted aromatic group is mono-substituted aromatic group or polysubstituted aromatic group；
Preferably, the substituent group of substituted aromatic group is any one in hydroxyl, halogen or alkyl；
It is highly preferred that alkyl is C1-C3 alkyl, most preferably methyl；
Preferably, R2With formula (3) structure:
R5For hydroxyl, methyl or halogen；
Most preferably, R2Any one in following group:
It is further preferred that fluorescent molecule is the compound with formula (4) structure, formula (4) is as follows:
R6=OH, Cl, Br, F, CH3；
Preferably, R1For normal-butyl, R6For hydroxyl；
It is highly preferred that any one of the fluorescent molecule in following compounds:
It should be noted that the dotted line and black solid line in structural formula indicate the connection connecting with other groups or parent nucleus
Key.
The embodiment of the present invention also provides a kind of preparation method of above-mentioned fluorescent molecule, comprising the following steps:
S1, synthetic intermediate 1；
It reacts bis- substitution -3,4,9,10- tetracarboxylic acid anhydride of 1,7- to form intermediate 1 with amine substance；Specifically, by 1,
Bis- substitution -3,4,9,10- tetracarboxylic acid anhydride of 7- and amine substance carry out anti-after mixing according to the ratio that molar ratio is 1:2-2.2
It answers；
Preferably, reaction condition are as follows: the reaction time is 12-24 hours, and reaction temperature is 70-100 DEG C；
Preferably, amine substance be n-butylamine, ethamine, n-propylamine, methylamine,
OrIn any one；
Preferably, 1,7- bis- replaces -3,4,9,10- tetracarboxylic acid anhydrides to be 1,7- bis- bromo- 3,4,9,10- tetracarboxylic acid anhydrides.
The intermediate 1 can fast and efficiently be synthesized using above-mentioned synthesis condition, be conducive to the synthesis of fluorescent molecule, energy
Enough guarantee that the fluorescent molecule can be acted on effectively with hypochlorite, hypochlorite is detected.
S2, synthetic intermediate 2；
Intermediate 1 reacts to form intermediate 2 with compound of benzaldehyde category；Specifically, by intermediate 1, benzaldehydes chemical combination
Object and carbonate mixing are reacted；
Preferably, reaction condition are as follows: the molar ratio of intermediate 1 and compound of benzaldehyde category is the 1:2.0-2.5 reaction time
For 8-24h, reaction temperature is 120-140 DEG C；
Preferably, carbonate is potassium carbonate or sodium carbonate；
Preferably, compound of benzaldehyde category is salicylide or o-chlorobenzaldehyde.Intermediate 2 is guaranteed using above-mentioned synthesis condition
Yield and purity, be conducive to the synthesis of subsequent fluorescent molecule.
S3, synthesis aromatic aldehyde are condensed hydrazine compound；
Aromatic aldehyde, hydrazine hydrate and alcoholic solution are mixed and reacted；
It is highly preferred that hydrazine hydrate and aromatic aldehyde and alcoholic solution are separately mixed to form hydrazine hydrate alcoholic solution and fragrance
Hydrazine hydrate alcoholic solution and aromatic aldehyde alcoholic solution are then mixed and are reacted by aldehyde alcohol solution；
It is highly preferred that the concentration of hydrazine hydrate alcoholic solution is 1.1-1.5mol/L, the concentration of aromatic aldehyde alcoholic solution is 1.1-
The molar ratio of 1.6mol/L, the pure and mild fragrant aldehyde alcohol of hydrazine hydrate are 5:1-10:1；
It is reacted 1-8 hours it is highly preferred that hydrazine hydrate alcoholic solution and the reaction of aromatic aldehyde alcoholic solution are included at 20-30 DEG C, and
It is reacted 8-24 hours at a temperature of 70-90 DEG C again afterwards；
Preferably, aromatic aldehyde is selected from salicylide.- HC=N-N=can be guaranteed using above-mentioned aromatic aldehyde condensation hydrazine compound
The formation of CH-, then guarantee fluorescent molecule can it is single, specifically with hypochlorite act on.
S4, synthesis fluorescent molecule；
Intermediate 2 reacts to form the fluorescent molecule with aromatic aldehyde condensation hydrazine compound.Specifically, by intermediate 2, fragrance
Aldehyde condensation hydrazine compound and aprotic solvent mixing are reacted；
Preferably, reaction condition are as follows: the molar ratio of intermediate 2 and aromatic aldehyde condensation hydrazine compound is 1:2.1-2.5, reaction
Time is 8-48 hours, and reaction temperature is 100-140 DEG C；
Preferably, aprotic solvent is tetrahydrofuran solvent；
Preferably, aromatic aldehyde condensation hydrazine compound is any in salicylidene conjunction hydrazine hydrate and o-tolualdehyde contracting hydrazine
It is a kind of.Be conducive to the synthesis of fluorescent molecule using above-mentioned substance and synthesis condition.
Further, the embodiment of the present invention also provides a kind of luciferase assay reagent comprising any one of aforementioned embodiments
The fluorescent molecule；
Preferably, the concentration of fluorescent molecule described in the luciferase assay reagent of unit formulation is 0.1-1 μM.The fluorescence
Detection reagent can efficiently, specifically detect hypochlorite ion, and detection effect is accurate.
Further, the embodiment of the present invention is provided if the described in any item fluorescent molecules of aforementioned embodiments are in fluorescence detection
In application；
Preferably, hypochlorite ion is detected using for the utilization fluorescent molecule；
Preferably, material concentration >=0.05 μM to be detected when fluorescence detection in detection liquid, preferably 0.1 μM.
It should be noted that saying that the room temperature of record is generally referred to as 25 DEG C of temperature in the embodiment of the present invention.
Embodiment 1
The present embodiment provides a kind of fluorescent molecule, structural formula is as follows:
The present embodiment also provides a kind of preparation method of fluorescent molecule, comprising the following steps:
S1, synthetic intermediate 1 (PDI-S)；
PDI-S is synthesized referring to following formula:
Specifically, by two bromo 2g, two equivalents of n-butylamine, 90 DEG C after reaction 24 hours in ethyl alcohol, by reaction solution
It pours into ice water, obtains a brown solid 2.2g, yield: 93%.1HNMR(CDCl3, ppm): δ 8.57-8.56 (d, 3H, J=
3Hz), 8.46-8.44 (d, 3H, J=6Hz), 1.3 (m, 12H), 0.9 (m, 6H) .MALDI-TOF-MS:m/z.Calculated:
[M+H]+=658.01, found:659.01.
S2, synthetic intermediate 2 (PDI-Y)；
PDI-Y is synthesized referring to following formula:
Specifically, first weighed into three-neck flask be added the double acid anhydrides of 1,7- bis- bromo- 3.4.9,10- tetracarboxylic (6.6g,
0.12mol), the excessive salicylide (3.4g, 0.26mol) of addition, potassium carbonate, or so 120 DEG C of three hours, wait react are weighed then
Entirely, make its crystallisation by cooling in ice bath, finally obtain product PDI-Y, black solid, yield: 90%.Referring to Fig. 1,1HNMR
(CDCl3, ppm): δ 10.25 (s, 2H), 7.94 (s, 2H), 7.65-7.63 (d, 3H, J=6.0Hz), 7.53-7.49 (d, 3H, J
=6.0Hz), 6.99-6.9 (t, 6H), 3.82 (q, 2H), 1.24 (m, 10H), 0.83 (m, 6H) .13CNMR (CDCl3, ppm):
δ182.16,160.76,136.86,129.60,122.65,119.74,116.69,36.28,30.26,22.98,
16.32.MALDI-TOF-MS:m/z.Calculated:[M+H]+=742.7780, found:743.7782.
S3, synthesis salicylide contracting hydrazine hydrate；
Salicylide contracting hydrazine hydrate is synthesized referring to following formula:
Specifically, the ethanol solution of 3.5g (1.1mol/L) hydrazine hydrate is added into 250mL round-bottomed flask, at room temperature constantly
It stirs, then the ethanol solution of 12.2g (1mol/L) salicylide is slowly added dropwise thereto with dropping funel, shortly have glassy yellow
Crystal generates, and so that it is reacted 1h or so at room temperature, then be condensed back 1h, and suction filtration is carried out using Buchner funnel, yield 92%.It is molten
Point: 124-126 DEG C.
S4, synthesis fluorescent molecule (PDI-SYQ)；
It is synthesized referring to following formula:
Specifically, PDI-Y (10.3g, 0.12mol/L) is added into three-neck flask, then is added thereto obtained in (2)
Salicylidene hydrazine (3.6g, 0.26mol/L) finally adds a certain amount of THF solvent, makes its mixed dissolution, 120 DEG C of reflux 8h
Left and right filters to obtain a violet solid, and weigh 12.1g, yield 90%, fusing point: 184-186 DEG C.Referring to fig. 2,1HNMR(CDCl3,
Ppm): δ 11.12 (s, 4H), 8.99 (s, 4H), 7.70-7.68 (d, 5H, J=6.0Hz), 7.40-7.38 (t, 5H, J=
6.0Hz), 6.99-6.95 (t, 10H, J=6.0Hz), 3.82 (q, 2H), 1.25 (m, 10H), 0.84 (m, 6H) referring to Fig. 3,13CNMR(CDCl3,ppm):δ192.17,162.78,161.20,136.89,129.65,122.75,119.94,117.69,
36.25,31.24,22.97,14.39. referring to fig. 4, MALDI-TOF-MS:m/z.Calculated:[M+H]+=978.3377,
found:979.3450。
Embodiment 2
The present embodiment provides a kind of fluorescent molecule, structural formula is as follows:
The present embodiment provides a kind of preparation methods of fluorescent molecule:
Condition when synthetic intermediate 1 are as follows: bis- substitution -3,4,9,10- tetracarboxylic acid anhydride of 1,7- and aniline are according to molar ratio
1:2.2, reaction time are 12 hours, and reaction temperature is 70 DEG C.
Condition when synthetic intermediate 2 are as follows: the molar ratio of intermediate 1 and salicylide is 1:2.2, reaction time 8h, reaction
Temperature is 140 DEG C；Carbonate is potassium carbonate.
Condition when synthesizing aromatic aldehyde condensation hydrazine compound are as follows: the concentration of the ethanol solution of hydrazine hydrate is 1.5mol/L, bigcatkin willow
The concentration of the ethanol solution of aldehyde is 1mol/L, and the molar ratio of the pure and mild fragrant aldehyde alcohol of hydrazine hydrate is 5:1, and reaction is: anti-at 20 DEG C
It answers 2 hours, is then reacted 12 hours at a temperature of 80 DEG C again.
Synthesize fluorescent molecule:
Specifically, PDI-B (5.0g, 0.064mol) is added into three-neck flask, then salicylidene hydrazine is added thereto
(1.74g, 0.128mol) finally adds a certain amount of DMSO solvent, makes its mixed dissolution, reflux 2h or so, filter one
Violet solid, weigh 6.4g, yield 95%, fusing point: 196-198 DEG C.1HNMR(CDCl3,ppm):δ10.52(s,4H),10.02
(m, 4H), 8.94-8.66 (m, 6H), 8.62-8.58 (s, 2H), 8.44-8.42 (d, 4H, J=6Hz), 8.02-7.94 (m,
6H),7.86-7.70m,6H),7.68-7.60(m,6H)。
The present embodiment also provides a kind of luciferase assay reagent comprising the concentration of above-mentioned fluorescent molecule, the fluorescent molecule is
10-5mol/L。
Embodiment 3
The present embodiment provides a kind of fluorescent molecule, structural formula is as follows:
The present embodiment provides a kind of preparation methods of fluorescent molecule:
Condition when synthetic intermediate 1 are as follows: bis- substitution -3,4,9,10- tetracarboxylic acid anhydride of 1,7- and aniline are according to molar ratio
1:2.1, reaction time are 18 hours, and reaction temperature is 85 DEG C.
Condition when synthetic intermediate 2 are as follows: the molar ratio of intermediate 1 and salicylide is 1:2.5, and the reaction time is reaction for 24 hours
Temperature is 120 DEG C；Carbonate is potassium carbonate.
Condition when synthesizing aromatic aldehyde condensation hydrazine compound are as follows: the concentration of the ethanol solution of hydrazine hydrate is 1.2mol/L, adjacent first
The concentration of the ethanol solution of benzaldehyde is 1.3mol/L, and the molar ratio of the pure and mild fragrant aldehyde alcohol of hydrazine hydrate is 10:1, and reaction is: In
It reacts at 30 DEG C 1 hour, is then reacted 8 hours at a temperature of 70 DEG C again.
Synthesize fluorescent molecule:
Specifically, into three-neck flask first weigh be added 1,7-, bis- substitution -3.4.9,10- imide derivative (30g,
0.03mol), then the excessive o-tolualdehyde contracting hydrazine (8.2g, 0.0061mol) of addition is weighed, DMF (50ml), reflux 8-12 are a
Hour or so, to fully reacting, make its crystallisation by cooling in ice bath, finally obtains product, black solid, yield: 94%.1HNMR(CDCl3, ppm): δ 10.54 (s, 4H), 8.62-8.58 (s, 2H), 8.46-8.40 (d, 4H, J=6Hz), 8.02-7.94
(m,6H),7.88-7.82(m,6H),7.72-7.64(m,6H),4.82(m,4H),3.64(m,4H),1.28(d,24H),1.32
(s,6H)。
The present embodiment also provides a kind of luciferase assay reagent comprising the concentration of above-mentioned fluorescent molecule, the fluorescent molecule is
10-5mol/L。
Embodiment 4
The present embodiment provides a kind of fluorescent molecule, structural formula is as follows:
The present embodiment provides a kind of preparation methods of fluorescent molecule:
By two bromo 2g, two equivalents of 2,6-DIPA will react in propionic acid after back flow reaction 24 hours
Liquid pours into ice water, obtains a brown solid 3.0g, yield: 95%.1HNMR(CDCl3,ppm):δ8.57-8.56(s,2H),
8.46-8.44 (d, 4H, J=6Hz), 8.10-7.80 (m, 6H), 2.87 (m, 4H), 1.28 (d, 24H).
Specifically, it is first weighed into three-neck flask and the bromo- 3.4.9 of 1,7- bis- is added, 10- acid imide (6.6g,
0.12mol), the excessive salicylide (4g, 0.0046mol) of addition, DMF (50ml), potassium carbonate, three hour left sides of flowing back are weighed then
The right side makes its crystallisation by cooling in ice bath to fully reacting, finally obtains production, black solid, yield: 94%.1HNMR(CDCl3,
Ppm): δ 10.48 (s, 2H), 8.58-8.56 (s, 2H), 8.48-8.46 (d, 4H, J=6Hz), 8.12-7.92 (m, 6H),
7.85-7.69(m,4H),7.68-7.30(m,4H),2.87(m,4H),1.28(d,24H)。
Specifically, into three-neck flask first weigh be added 1,7-, bis- substitution -3.4.9,10- acid imide (6.6g,
0.12mol), the excessive o fluorobenzaldehyde contracting hydrazine (3g, 0.0032mol) of addition, ethyl alcohol (40ml), 12 hour left sides of flowing back are weighed then
The right side makes its crystallisation by cooling in ice bath to fully reacting, finally obtains product, black solid, yield: 92%.1HNMR
(CDCl3, ppm): δ 10.52 (s, 4H), 8.60-8.56 (s, 2H), 8.46-8.44 (d, 4H, J=6Hz), 8.02-7.96 (m,
6H),7.85-7.69(m,6H),7.68-7.30(m,6H),2.87(m,4H),1.28(d,24H)。
The present embodiment also provides a kind of luciferase assay reagent comprising above-mentioned fluorescent molecule, the concentration of the fluorescent molecule are 1
μM。
Embodiment 5
The present embodiment provides a kind of fluorescent molecule, structural formula is as follows:
The present embodiment provides a kind of preparation methods of fluorescent molecule:
Condition when synthetic intermediate 1 are as follows: bis- substitution -3,4,9,10- tetracarboxylic acid anhydride of 1,7- and aniline are according to molar ratio
1:2, reaction time are 18 hours, and reaction temperature is 100 DEG C.
Condition when synthetic intermediate 2 are as follows: the molar ratio of intermediate 1 and salicylide is 1:2, reaction time 12h, reaction temperature
Degree is 130 DEG C；Carbonate is potassium carbonate.
Condition when synthesizing aromatic aldehyde condensation hydrazine compound are as follows: the concentration of the ethanol solution of hydrazine hydrate is 5mol/L, adjacent fluorobenzene
The concentration of the ethanol solution of formaldehyde is 1mol/L, and the molar ratio of the pure and mild aromatic aldehyde of hydrazine hydrate is 5:1, and reaction is: anti-at 25 DEG C
It answers 4 hours, is then reacted 12 hours at a temperature of 80 DEG C again.
Synthesize fluorescent molecule:
Specifically, PDI-N (5.0g, 0.128mol) is added into three-neck flask, then water obtained in (2) is added thereto
Poplar aldehyde contracting hydrazine (3.5g, 0.26mol) finally adds a certain amount of DMSO solvent, makes its mixed dissolution, reflux 3h or so, takes out
A violet solid is filtered to obtain, weigh 12.8g, yield 95%, fusing point: 188-190 DEG C.1HNMR(CDCl3,ppm):δ11.4(s,
4H), 8.96 (s, 4H), 7.74-7.70 (d, 5H, J=6.0Hz), 7.60-7.58 (t, 5H, J=6.0Hz), 6.98-6.94 (t,
10H, J=6.0Hz), 4.52 (q, 2H), 1.25-2.5 (m, 20H), 0.88 (m, 12H).
The present embodiment also provides a kind of luciferase assay reagent comprising the concentration of above-mentioned fluorescent molecule, the fluorescent molecule is
10-5mol/L。
Experimental example 1
Visual retrieval of the fluorescent molecule to hypochlorite ion
Operating method: taking two cuvettes, and the probe solution of two parts of same concentrations is respectively configured, and concentration is controlled 10-5-
10-7Mol/L, the solution 1-2 containing sodium hypochlorite is added dropwise in a cuvette thereto, and (concentration is controlled 10-4-10-5mol/L)
Drop is observed and is taken pictures after being sufficiently mixed and respectively under natural light and under ultraviolet lamp, as a result referring to figs. 5 and 6.
As can be seen from FIG. 5, the luciferase assay reagent that embodiment 1 provides is purple (figure left side), add hypochlorite from
After son, bottom becomes dark green (figure right side) when solution just contacts, and is sufficiently mixed in 3-5 seconds latter, solution colour is thin out, is finally in
Light green.As can be seen from FIG. 6, luciferase assay reagent is put in the UV lamp together with the probe solution that hypochlorite ion is added
Observation finds that the former, substantially without fluorescence phenomenon, and is observed visually solution colour and becomes orange red (figure left side) from purple,
And the latter has apparent absinthe-green fluorescence (figure right side).It therefore, can be to secondary chlorine by near-infrared probe of the invention
Acid group carries out naked eye identification, this is provided convenience for it in the middle application of real life.
Experimental example 2
Spectral response of the fluorescent molecule to hypochlorite ion
Operating method: take 3ml vial several, the probe solution of several pieces same concentrations is respectively configured, concentration is
10-5The solution 1-2 drop containing sodium hypochlorite is added dropwise in mol/L thereto in a cuvette.
As can be seen from FIG. 7, there are two strong absorption peaks at 359nm and 550nm for fluorescent molecule provided by the invention, work as drop
Add hypochlorite (the i.e. 5*10 of 5 equivalents-5Mol/L hypochlorite) after, absorption of the probe molecule at 550nm is decreased obviously,
And there is a new peak to occur at 740nm.
Meanwhile the fluorescence emission spectrum that fluorescent molecule provided by the invention corresponds to its absorption maximum is determined, such as Fig. 8 institute
Show, 359nm excitation, transmitting of the fluorescent molecule provided by the invention at 600nm is remarkably reinforced.Furthermore our also Preliminary Determinations
Probe molecule shows good choosing to hypochlorite to the spectral responses of other common metal ions and small molecule, probe molecule
Selecting property recognition capability.
Experimental example 3
Time response of the fluorescent molecule to hypochlorite ion
Operating method: with the fluorescent molecule PDI-SYQ of liquid-transfering gun difference Example 1 in VH2The mother liquor of O/THF=1:1
Middle 2mL is in 3mL cuvette, [PDI-SYQ]=1 μM, [ClO-]/[PDI-SYQ]=1 equivalent, instill the hypochlorous acid of 1 equivalent
Radical ion stands, and starts timing.Probe molecule is to the fluorescence response time of hypochlorite and its effect picture as shown in figure 9 above.
As can be seen from FIG. 9, with the instillation of hypochlorite, color occurs immediately apparent variation, over time
Probe solution color gradually becomes green from purple.Therefore probe molecule has real-time monitoring effect for hypochlorous acid.
Experimental example 4
Fluorescent molecule responds the concentration gradient of hypochlorite ion
Operating method: the secondary chlorine of different equivalents (0~10equiv) is added in the luciferase assay reagent prepared to embodiment 1
Acid sodium solution is uniformly mixed, and carries out fluorometric investigation and ultraviolet test.Testing result is referring to Figure 10-Figure 12.
As shown in figure 10 above figure -11, fluorescence intensity can be with ClO-The increase of concentration and increase, when being excited with 359nm, most
Height rises to 10-15 times (as shown in figure 11).And ultraviolet absorption peak can also be influenced by hypochlorite concentration, wherein the most aobvious
What is write is the absorption peak in 740nm or so, and absorbance is not obvious when concentration is low at the beginning, but when ultimate density highest, is inhaled
Luminosity also enhances therewith.Meanwhile most particularly, ultraviolet absorption peak is located at 560nm and 740nm, both variation
For trend on the contrary, the former is to increase, the latter then can constantly decline (as shown in Figure 10).In addition, being measured by excitation wave of 740nm
Probe gradually increases (such as Figure 12 institute to (belonging to near-infrared luminous range) at the concentration fluorescent emission intensity 800nm of hypochlorite
Show).As it can be seen that probe molecule has apparent fluorescence intensity and absorbance dependence to hypochlorite, and it is closely red that ratio is presented
Outer emission characteristic.The fluorescence titration curve of spectrum limits equation in conjunction with detection, we obtain as matched curve at 600nm using in Figure 11
0.124 μM is limited to the detection of hypochlorite to probe molecule, therefore probe molecule has good detection spirit to hypochlorite
Sensitivity.
Experimental example 5
Fluorescent molecule measures the anti-interference of other ions and molecule
Liquor natrii hypochloritis's (1 μM) of equimolar amounts will be added in the luciferase assay reagent (1 μM) of embodiment 1, adds 5
Various Competing Species (the Mg of a equivalent2+,Zn2+,Fe3+,Fe2+,Ni2+,Co2+,Mn2+,Cu2+,F-,Cl-,Br-,S2-,SO4 2-,
Ac-,NO2 -,H2O2) then (VTHF:VH is diluted with THF and tap water2O=1:1).Solution after mixing, then vibrates 0-
3min carries out fluorescence intensity test.Testing result is referring to Figure 13.
As can be seen from FIG. 13, relative to skip test liquid (Competing Species are not added), various Competing Species will not be significantly affected
Detection of the probe to sodium hypochlorite shows that probe PDI-SYQ has good anti-interference ability to the identification of sodium hypochlorite.
In conclusion fluorescent molecule provided by the invention is to ClO-There is apparent naked eye recognition capability, with hypochlorite
Purple of the instillation by be changed into light green color, observe in the UV lamp, it is found that fluorescence is by without being changed into light green color fluorescence.
Fluorescent molecule either ultraviolet absorption peak or fluorescence intensity show that ratio fluorescent is responded to hypochlorite；It monitors concentration
Down to 0.1-1 μM, in addition, the probe anti-interference is more excellent, there is excellent Selective recognition ability to hypochlorite.Cause
This, this type probe has application value in terms of industrial wastewater, domestic water and biological monitoring.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of fluorescent molecule, which is characterized in that it is the compound with formula (1) structure, and formula (1) is as follows:
Wherein R1For alkyl or substituted aromatic base, R2For the substituted aroma group containing-HC=N-N=CH- group.
2. fluorescent molecule according to claim 1, which is characterized in that R1Alkyl be C1-C10 linear or branched alkyl group, it is excellent
It is selected as any one in methyl, ethyl, n-propyl, normal-butyl and 3- ethyl hexyl；More preferably normal-butyl；
Preferably, R1Substituted aromatic base be benzyl substituted or unsubstituted；
It is highly preferred that the substituent group of substituted benzyl is alkyl, it is highly preferred that alkyl is C1-C4 alkyl, most preferably isopropyl；
Most preferably, R1Any one in following group:
3. fluorescent molecule according to claim 1 or 2, which is characterized in that R2For the group with formula (2) structure；
-X-R3- HC=N-N=CH-R4Formula (2)；
Wherein, X is selected from O or sulphur, it is preferable that X O；
R3And R4Separately it is selected from substituted or unsubstituted aromatic group；
Preferably, aromatic group is selected from phenyl or fused aromatic group；More preferably phenyl；
Preferably, substituted aromatic group is mono-substituted aromatic group or polysubstituted aromatic group；
Preferably, the substituent group of substituted aromatic group is any one in hydroxyl, halogen or alkyl；
It is highly preferred that alkyl is C1-C3 alkyl, most preferably methyl；
Preferably, R2With formula (3) structure:
R5For hydroxyl, methyl or halogen；
Most preferably, R2Any one in following group:
4. fluorescent molecule according to claim 1 or 2, which is characterized in that it is the compound with formula (4) structure, formula
(4) as follows:
R6=OH, Cl, Br, F, CH3；
Preferably, R1For normal-butyl, R6For hydroxyl；
It is highly preferred that any one of the fluorescent molecule in following compounds:
5. the preparation method of fluorescent molecule according to any one of claims 1-4, which comprises the following steps:
It reacts bis- substitution -3,4,9,10- tetracarboxylic acid anhydride of 1,7- to form intermediate 1 with amine substance；
And rear center body 1 reacts to form intermediate 2 with compound of benzaldehyde category；
Intermediate 2 reacts to form the fluorescent molecule with aromatic aldehyde condensation hydrazine compound.
6. preparation method according to claim 5, which is characterized in that the preparation of intermediate 1 includes: by the substitution of 1,7- bis--
3,4,9,10- tetracarboxylic acid anhydride and amine substance are reacted after mixing according to the ratio that molar ratio is 1:2-2.2；
Preferably, reaction condition are as follows: the reaction time is 12-24 hours, and reaction temperature is 70-100 DEG C；
Preferably, amine substance be n-butylamine, ethamine, n-propylamine, methylamine,OrIn any one；
Preferably, 1,7- bis- replaces -3,4,9,10- tetracarboxylic acid anhydrides to be 1,7- bis- bromo- 3,4,9,10- tetracarboxylic acid anhydrides.
7. preparation method according to claim 5, which is characterized in that the preparation of intermediate 2 includes: by intermediate 1, benzene first
Aldehyde compound and carbonate mixing are reacted,
Preferably, reaction condition are as follows: it is 8- that the molar ratio of intermediate 1 and compound of benzaldehyde category, which is the 1:2.0-2.5 reaction time,
For 24 hours, reaction temperature is 120-140 DEG C；
Preferably, carbonate is potassium carbonate or sodium carbonate；
Preferably, compound of benzaldehyde category is salicylide or o-chlorobenzaldehyde.
8. preparation method according to claim 5, which is characterized in that
Preparation fluorescent molecule includes: that intermediate 2, aromatic aldehyde condensation hydrazine compound and aprotic solvent are mixed and reacted；
Preferably, reaction condition are as follows: the molar ratio of intermediate 2 and aromatic aldehyde condensation hydrazine compound is 1:2.1-2.5, reaction time
It is 8-48 hours, reaction temperature is 100-140 DEG C；
Preferably, aprotic solvent is tetrahydrofuran solvent；
Preferably, aromatic aldehyde condensation hydrazine compound is any one in salicylidene conjunction hydrazine hydrate and o-tolualdehyde contracting hydrazine
Kind；
Preferably, preparing aromatic aldehyde condensation hydrazine compound includes mixing aromatic aldehyde, hydrazine hydrate and alcoholic solution to react；
It is highly preferred that hydrazine hydrate and aromatic aldehyde and alcoholic solution are separately mixed to form hydrazine hydrate alcoholic solution and fragrant aldehyde alcohol
Hydrazine hydrate alcoholic solution and aromatic aldehyde alcoholic solution are then mixed and are reacted by solution；
It is highly preferred that the concentration of hydrazine hydrate alcoholic solution is 1.1-1.5mol/L, the concentration of aromatic aldehyde alcoholic solution is 1.1-1.6mol/
The molar ratio of L, hydrazine hydrate and aromatic aldehyde is 5:1-10:1；
It is highly preferred that hydrazine hydrate alcoholic solution and the reaction of aromatic aldehyde alcoholic solution, which are included at 20-30 DEG C, reacts 1-8 hours, then again
It is reacted 8-24 hours at a temperature of 70-90 DEG C；
Preferably, aromatic aldehyde is selected from salicylide.
9. a kind of luciferase assay reagent comprising the described in any item fluorescent molecules of claim 1-4；
Preferably, the concentration of fluorescent molecule described in the luciferase assay reagent of unit formulation is 0.1-10 μM.
10. application of the fluorescent molecule according to any one of claims 1-4 in fluorescence detection；
Preferably, hypochlorite ion is detected using for the utilization fluorescent molecule；
Preferably, material concentration >=0.05 μM to be detected when fluorescence detection in detection liquid, preferably 0.1 μM.
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