CN107955156A - One kind enhancing fluorescence probe intermediate and preparation method thereof - Google Patents

One kind enhancing fluorescence probe intermediate and preparation method thereof Download PDF

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CN107955156A
CN107955156A CN201711210192.9A CN201711210192A CN107955156A CN 107955156 A CN107955156 A CN 107955156A CN 201711210192 A CN201711210192 A CN 201711210192A CN 107955156 A CN107955156 A CN 107955156A
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fluorescence probe
preparation
product
peg
enhancing fluorescence
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倪润炎
王伟
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Suzhou Jindian Biotechnology Co Ltd
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Suzhou Jindian Biotechnology Co Ltd
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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    • C09K2211/1408—Carbocyclic compounds
    • C09K2211/1416—Condensed systems

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Abstract

The present invention relates to one kind enhancing fluorescence probe intermediate and preparation method thereof, its chemical structure of general formula is as follows：(1), in formula, Z is PEG the or PEG derivatives groups that molecular weight is 500~10000.It is water-soluble so that water-soluble preferably fluorescence probe is made after grafting fluorophor to improve the detection result to specific molecular (such as singlet oxygen) that it can so be improved；And two fluorophors can be connected so that fluorescence intensity is multiplied；And preparation method is simple, practical, purity and yield are higher.

Description

One kind enhancing fluorescence probe intermediate and preparation method thereof
Technical field
The present invention relates to a kind of fluorescence probe field, is related to a kind of enhancing fluorescence probe intermediate and preparation method thereof, uses Strengthen fluorescence probe in preparation to detect singlet oxygen.
Background technology
Singlet oxygen, the oxygen of the stabilization ground state oxygen molecule from usually breathing is different, is that one kind is in reactive oxygen species Existence form.Compared with ground state, the chemical property of singlet oxygen is more active, more unstable, and oxidisability is very strong, can cause each The oxidation of kind material.Singlet oxygen can participate in a variety of body biochemical reactions and physiology course, for example, signal transduction, enzyme reaction, Cell division, tissue peroxidating, inflammation, aging, Phagocytosis, tumour and chemical poisoning, produce body the double of Various Complex Recast is used.On the one hand, singlet oxygen has stronger toxicity, can cause the damage of body, triggers aging and various diseases；It is and another On the one hand, it is the major antibacterial agent of organism immune system again, it may also be used for the photodynamic therapy of cancer.
At present, a small amount of singlet oxygen is quantitatively detected in aqueous solution in physiological conditions to have difficulties, essentially consist in its longevity Order that short, reactivity is high.The method of existing singlet oxygen detection is broadly divided into (such as the paramagnetic resonance skill of detection method in gas phase Art, emission spectrum, photo-ionisation technology and calorimetry etc.) and liquid phase in detection method (such as phosphorescence detection method, Chemical Trapping inhale Light photometry, chemoluminescence method, fluorescence detection etc.).Above-mentioned detection method or it is of high cost be difficult to apply, or because singlet Oxyluminescence efficiency is low and causes sensitivity low, and detecting signal is weak.
The Chinese invention patent of Application No. 201610093502.2 discloses a kind of dyestuff for being used to detect singlet oxygen With fluorescence probe and preparation method thereof, it is the corresponding fluorescence probe of Material synthesis by using bridged piperazine derivatives, and be fabricated to inspection Test agent box.Obtained fluorescence probe in this application, has high sensitivity and selectivity to singlet oxygen, greatly expands such The application range of fluorescence probe, such as available for the singlet oxygen detection in environment, chemical food and biologic medical field；But It is that the fluorescence intensity of the fluorescence probe still has the space of lifting.It is crucial during the fluorescence probe of synthesis fluorescence intensity lifting The synthesis of intermediate is played and its important effect.
The content of the invention
A kind of enhancing fluorescence probe intermediate is provided the invention aims to overcome the deficiencies in the prior art.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：One kind enhancing fluorescence probe intermediate, its chemistry General structure is as follows：
In formula, Z is PEG the or PEG derivatives groups that molecular weight is 500~10000.
Optimally, Z isR is O, S or NH.
A further object of the present invention is to provide a kind of preparation method of above-mentioned enhancing fluorescence probe intermediate, it include with Lower step：
(a1) willCarry out the substitution reaction of Br free radicals and generate the first product
(a2) first product is carried out substitution reaction with chlorosulfonic acid, generate the second product
(a3) second product and PEG or PEG derivatives are subjected to substitution reaction.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：Present invention enhancing fluorescence Probe intermediate, by using special MOLECULE DESIGN, can so improve its water solubility so that being made after grafting fluorophor Water-soluble preferably fluorescence probe is to improve the detection result to specific molecular (such as singlet oxygen)；And can connect two it is glimmering Light group so that fluorescence intensity is multiplied；And preparation method is simple, practical, purity and yield are higher.
Brief description of the drawings
Attached drawing 1 is the synthetic line figure for strengthening fluorescence probe intermediate in embodiment 1；
Attached drawing 2 is before and after the enhancing fluorescence probe synthesized in the embodiment of the present invention 1 reacts in room temperature DMF with singlet oxygen Fluorescent emission collection of illustrative plates contrast (λ ex=400nm), wherein1O2Produced within 15 minutes by quick dose of phot-luminescence (rose-red)；
Attached drawing 3 is before and after the enhancing fluorescence probe synthesized in the embodiment of the present invention 1 reacts in room temperature water with singlet oxygen Fluorescent emission collection of illustrative plates contrast (λ ex=400nm), wherein1O2Produced within 15 minutes by quick dose of phot-luminescence (rose-red).
Embodiment
Present invention enhancing fluorescence probe intermediate, its chemical structure of general formula are as follows：
In formula, Z is PEG the or PEG derivatives groups that molecular weight is 500~10000.Set by using special molecule Meter, it is water-soluble so that water-soluble preferably fluorescence probe is made after grafting fluorophor to improve to specific can so to improve it The detection result of molecule (such as singlet oxygen)；And two fluorophors can be connected so that fluorescence intensity is multiplied
Z isR is O, S or NH, and fluorescence probe intermediate is optimal is for enhancingThe size of n is determined according to specific molecular weight.
The preparation method of above-mentioned enhancing fluorescence probe intermediate, it comprises the following steps：
(a1) willCarry out the substitution reaction of Br free radicals and generate the first product
(a2) first product is carried out substitution reaction with chlorosulfonic acid, generate the second product
(a3) second product and PEG or PEG derivatives are subjected to substitution reaction.The preparation method process route Simply, practical, product purity and yield are higher.
The present invention is further described below in conjunction with attached drawing embodiment.
Embodiment 1
The present embodiment provides one kind enhancing fluorescence probe intermediate and preparation method thereof, the chemistry knot of the enhancing fluorescence probe Structure formula is as follows：
Its preparation method is as follows, comprises the following steps (such as Fig. 1 institutes Show)：
(a1) in 50mL there-necked flasks, and addition HOCD (1g, 2.43mmol, 1eq, i.e.,), carbon tetrachloride (10mL), NBS (0.95g, 5.36mol, 2.2eq, i.e. N-bromosuccinimide), benzoyl peroxide (5.88mg, 0.0243mmol, 0.01eq), be heated to reflux under nitrogen protection 19 it is small when, be cooled to 0 DEG C, filtering, filter cake is washed with carbon tetrachloride Wash, concentrate, then by column chromatography, obtain compound 1.24g (90%) blue solid (first product).Survey Hydrogen modal data be：1H NMR(300MHz,CDCl3)δ(ppm):8.81 (s, 2H), 8.75 (d, J=6.0Hz, 2H), 8.28 (s, 2H), 8.25 (d, J=6.0Hz, 2H), 7.59-7.56 (m, 4H), the carbon modal data that 2.57 (s, 4H) are measured are：13C NMR (75MHz,CDCl3)d(ppm):1884.73,141.09,136.67,134.96,134.06,132.62,131.58,130.21, 129.10,128.66,128.71,126.38,124.29,26.45.HREI-MS m/z calcd:C30H18Br2O2([M]+)； 567.9674,found:567.9665；
(a2) in 50mL single port bottles, the first product (800mg, 1.38mmol, 1eq) is added, adds chlorosulfonic acid (16mL), Be heated to reflux 24 it is small when, reaction solution is added in 20mL frozen water, is extracted with dichloromethane, concentrated column purification obtains compound 2 652mg (71%) blue solid (second product)。1H NMR(300MHz,CDCl3)δ(ppm): 9.25 (d, J=3.0Hz, 1H), 8.75 (d, J=9.0Hz, 1H), 8.58-6.53 (m, 2H) 8.15 (s, 2H), 7.98-7.89 (m,3H),7.59-7.52(m,2H),2.53(s,2H),2.51(s,2H).13C NMR(75MHz,CDCl3)δ(ppm): 182.94,182.91,142.05,140.67,140.15,134.57,134.14,132.93,132.58,131.40,131.34, 130.80,130.70,130.63,130.00,129.78,129.64,129.54,129.39,129.26,129.17,128.88, 128.39,128.09,126.22,125.36,121.68,21.45ppm.HRESI-MS:m/z cacld.C30H17Br2ClO4S: 665.8903(M+),found:665.8895(weak peak).Cacld:C30H18Br2O5S[M-H]-646.9242 (sulfonate),found:647.9235(strong peak)；
(a3) in 50mL single port bottles, the second product (200mg, 0.3mmol, 1eq) is added, adds dichloromethane (5mL), Et3N (triethylamine, 37mg, 0.36mmol, 1.2eq), methoxy poly (ethylene glycol) (i.e. mPEG-OH, MW=1000) (23mg, 0.36mmol, 1.2eq), when reaction 5 is small at 50 DEG C, room temperature is cooled to, water 1mL on the rocks, concentration, crosses column purification and obtain tertiary industry Thing 144mg is (i.e.68%) blue solid1H NMR(300MHz,CDCl3)δ (ppm):9.27(m,1H),8.79(m,1H),8.68-6.57(m,2H)8.25(m,2H),7.98-7.89(m,3H),7.59- 7.52(m,2H),4.25-4.20(m,2H),3.63-3.60(m,3H),3.45-3.42(m,2H),2.53(m,2H),2.51(m, 2H)。
Embodiment 2
The present embodiment provides one kind enhancing fluorescence probe intermediate and preparation method thereof, the chemistry knot of the enhancing fluorescence probe Structure formula and reactions steps with basically identical in embodiment 1, unlike：(a3) the mPEG-OH molecular weight used in is 10000。
Embodiment 3
The present embodiment provides one kind enhancing fluorescence probe intermediate and preparation method thereof, the chemistry knot of the enhancing fluorescence probe Structure formula and reactions steps with basically identical in embodiment 1, unlike：(a3) the mPEG-OH molecular weight used in is 500.
In three 50mL single port bottles, it is separately added into above-mentioned each enhancing fluorescence probe intermediate, then be separately added into CH3CN(5mL),K2CO3(98mg, 0.705mmol, 5.0eq) and(157mg, 0.31mmol, 2.2eq), when reaction 8 is small at 70 DEG C, room temperature is cooled to, is concentrated, column purification is crossed and obtains 3 parts of enhancing fluorescence probes 150mg (68%) light red solid.Be prepared as：Take piperazine (5.31mg, 0.062mmol) it is dissolved in dry methylene chloride (DCM) (6mL), then adds benzotriazole-N, N, N', N'-15 tetramethyl Urea hexafluorophosphate (HBTU) (34.3mg, 0.091mmol), N, N- diisopropyl ethyl amines (DIPEA) (31 μ L, After 0.184mmol), with(34mg, 0.062mmol) is stirred at room temperature overnight, to obtain the final productCrude product.Product is purified：HCl (1M, 10mL) and NaHCO is used respectively3Aqueous solution (2 times, each 10mL) washing reaction mixture；Collect organic phase and rotary evaporated to dryness is dry.
3 parts of photosensitizer rose bengals (2 μ L, 0.5mg/mL, be dissolved in 10mM PBS buffer, pH=7.4) stock solution is taken, respectively Add the probe mixing in embodiment 1 to embodiment 3；By solution several minutes under the light of fiber luminaire, and with glimmering Photometry records fluorescence intensity change.Wherein, shown in experimental result Fig. 2 in embodiment 1, enhancing fluorescence probe DMF (1 μM) with Fluorescence excitation spectral intensity enhances 148 times respectively after singlet oxygen reaction；And obtained enhancing is glimmering in embodiment 2 and embodiment 3 Fluorescence excitation spectral intensity enhances 146 times to light probe respectively, 145 times (with application number after DMF (1 μM) and singlet oxygen reaction For the IIIa probes in 201610093502.2 Chinese invention patents as a comparison case, measure and add 60 times), it is clear that they are big It is higher than comparative example greatly.In the PBS buffer of simulation biological physiology environment, concentration is 0.1 μM of probe and single line in comparative example 1 Fluorescence excitation spectrum distinguishes intensity 120 times (as shown in Figure 3) after the reaction of state oxygen；And obtained enhancing in embodiment 2 and embodiment 3 Fluorescence excitation spectral intensity enhances 116 times, 115 times respectively after fluorescence probe reacts in PBS buffer with singlet oxygen, about 80% measured in organic solvent DMF, this illustrate the probe it is water-soluble not than oil-soluble reduce how much, have good It is water-soluble.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention, it is all according to the present invention The equivalent change or modification that Spirit Essence is made, should be covered by the protection scope of the present invention.

Claims (3)

1. one kind enhancing fluorescence probe intermediate, it is characterised in that its chemical structure of general formula is as follows：
In formula, Z is PEG the or PEG derivatives groups that molecular weight is 500~10000.
2. enhancing fluorescence probe intermediate according to claim 1, it is characterised in that：Z isR For O, S or NH.
3. in claim 1 to 2 it is any it is described enhancing fluorescence probe intermediate preparation method, it is characterised in that it include with Lower step：
(a1) willCarry out the substitution reaction of Br free radicals and generate the first product
(a2) first product is carried out substitution reaction with chlorosulfonic acid, generate the second product
(a3) second product and PEG or PEG derivatives are subjected to substitution reaction.
CN201711210192.9A 2017-11-28 2017-11-28 One kind enhancing fluorescence probe intermediate and preparation method thereof Withdrawn CN107955156A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721721A (en) * 2018-12-14 2019-05-07 万华化学集团股份有限公司 A kind of polyethers and its synthetic method and application with photoluminescent property

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1953960A (en) * 2004-05-12 2007-04-25 出光兴产株式会社 Aromatic amine derivative, organic electroluminescent device using the same, and method for preparing aromatic amine derivative
CN102300861A (en) * 2009-02-03 2011-12-28 百奥提姆股份有限公司 Xanthene dyes comprising a sulfonamide group
WO2012039685A1 (en) * 2010-09-24 2012-03-29 Agency For Science, Technology And Research A nanoprobe comprising gold colloid nanoparticles for multimodality optical imaging of cancer and targeted drug delivery for cancer
CN107099165A (en) * 2016-02-19 2017-08-29 苏州工业园区新国大研究院 Dyestuff and fluorescence probe for detecting singlet oxygen and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1953960A (en) * 2004-05-12 2007-04-25 出光兴产株式会社 Aromatic amine derivative, organic electroluminescent device using the same, and method for preparing aromatic amine derivative
CN102300861A (en) * 2009-02-03 2011-12-28 百奥提姆股份有限公司 Xanthene dyes comprising a sulfonamide group
WO2012039685A1 (en) * 2010-09-24 2012-03-29 Agency For Science, Technology And Research A nanoprobe comprising gold colloid nanoparticles for multimodality optical imaging of cancer and targeted drug delivery for cancer
CN107099165A (en) * 2016-02-19 2017-08-29 苏州工业园区新国大研究院 Dyestuff and fluorescence probe for detecting singlet oxygen and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721721A (en) * 2018-12-14 2019-05-07 万华化学集团股份有限公司 A kind of polyethers and its synthetic method and application with photoluminescent property
CN109721721B (en) * 2018-12-14 2021-05-14 万华化学集团股份有限公司 Polyether with fluorescence property and synthetic method and application thereof

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Application publication date: 20180424