CN101531683B - Bipyridine ruthenium/osmium ECL marker with phenothiazine power supplying groups in molecules - Google Patents

Bipyridine ruthenium/osmium ECL marker with phenothiazine power supplying groups in molecules Download PDF

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CN101531683B
CN101531683B CN 200910011139 CN200910011139A CN101531683B CN 101531683 B CN101531683 B CN 101531683B CN 200910011139 CN200910011139 CN 200910011139 CN 200910011139 A CN200910011139 A CN 200910011139A CN 101531683 B CN101531683 B CN 101531683B
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ecl
phenothiazine
osmium
bpy
ptz
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CN101531683A (en
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孙世国
孙立成
杨洋
彭孝军
樊江莉
刘凤玉
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

The invention belongs to the field of fine chemistry industry, and in particular relates to a bipyridine ruthenium/osmium ECL marker with phenothiazine power supplying groups in molecules. The bipyridine ruthenium/osmium ECL marker with the phenothiazine power supplying groups in the molecules has the following structurale general formula: M(L)2L', wherein M is Ru or Os; L is selected from any one of 2,2'-bipyridine and derivatives thereof, or 1,10-phenanthroline (naphthisodiazine) and derivatives thereof, and L' is selected from ligands of the compounds; in the formula, B is -(CH2)n-, wherein n is an integer from 1 to 10 or an alkyl chain -(CH2)n- of an amide group and exists at any positions, and the total carbon number n of the alkyl chain is an integer from 1 to 10; and P is phenothiazine (PTZ) or H. The invention introduces an electron donor phenothiazine (PTZ) which has reversible redox activity to the structure of the bipyridine ruthenium/osmium ECL marker to modify the structure of bipyridine ruthenium/osmium ligands, and with the intramolecular and intermolecular synergic actions, the dosage of amine co-reactants is reduced, the background interference is reduced, and the ECL is greatly enhanced.

Description

Intramolecularly has the bipyridyl ruthenium/osmium ECL affinity tag of phenothiazine power supplying groups
Technical field
The invention belongs to field of fine chemical, be specifically related to the bipyridyl ruthenium/osmium ECL affinity tag that a kind of intramolecularly has phenothiazine power supplying groups.
Background technology
Tris (bipyridine) ruthenium Ru (bpy) 3 2+Electrochemiluminescence (Electrochemiluminescence; Be called for short ECL) have the original position response, advantage such as detection sensitivity is high, linearity range is wide and instrument is simple, obtained widespread use in pharmaceutical analysis, amino acid analysis, dna probe analysis, enzyme biologic sensor field.Particularly IGEN Inc. and GaithersburgMD company are at first with Ru (bpy) 3 2+After being applied to immunoassay, polymerase chain and transcribing the mensuration and gene order research of (PCR) product, Ru (bpy) 3 2+ECL has obtained common concern in the application in fields such as clinical medicine, electroanalytical chemistry, life science.(Massey?R.J.，Powell?M.J.，Mied?P.A.，et?al.WO?87?06?706，1987)
Ru (bpy) 3 2+The most extensive with the ECL application of tripropyl amine (TPrA) co-blended system, detectability has reached the fm level at present, the irreversible TPrA that has determined must use in the detection excessive greatly (100mM) of intermolecular interaction in this mixed system and TPrA oxidation.And the autoxidation of TPrA can produce the ECL stray light, and the existence of this background interference light must have influence on SNR, sensitivity and the LDL etc. that ECL detects, thereby is fundamentally restricting further developing of this mixed system ECL detection application.Along with science and technology development, the sensitivity of ECL is had higher requirement at a lot of detection ranges.For this reason, each study group has carried out many fruitful researchs both at home and abroad:
(1) through changing co-reactant composition optimizes electrochemiluminescence reaction process.Tripropyl amine (TPrA) is to study fullest over nearly 20 years, most widely used Ru (bpy) 3 2+ECL coreaction reagent.And as the new coreaction reagent N of reporting in 2007, N-dibutyl thanomin (DBAE) then showed the most outstanding illumination effect.Use gold electrode and platinum electrode as working electrode, Ru (bpy) 3 2+-DBAE system ECL is respectively than Ru (bpy) 3 2+-TPrA strengthens 10 times and 100 times.But the discovery of DBAE can't thoroughly change the present situation that in ECL detects, must use a large amount of reductive agents.
(2) set up double-core and multinuclear ruthenium metal complex system, the divalence Ru that forms excited state is the basis of whole ECL process, so increase the intensity that the quantity of central metal will certainly improve ECL.Double-core and multinuclear ruthenium metal complex system become a focus of correlative study.
(3) electron transport mechanism design new E CL affinity tag in the applied molecular.TPrA is introduced in the bipyridine ligand through covalent linkage, relies on the effect of intramolecularly transfer transport to realize that ECL detects, in the practical implementation process, can observe the ECL phenomenon, but compare the intermolecular ECL of existing co-blended system, luminous intensity relatively a little less than.
Summary of the invention
The objective of the invention is to improve in the existing co-blended system tris (bipyridine) ruthenium and have that effect causes the system electronic transfer efficiency low between reactant molecule altogether; Must use the shortcoming of excessive greatly amine co-reactant; Provide a kind of and can when reducing amine co-reactant consumption, strengthen the bipyridyl ruthenium/osmium ECL affinity tag of ECL intensity.
For achieving the above object, the present invention adopts following technical scheme: the bipyridyl ruthenium/osmium ECL affinity tag that intramolecularly has phenothiazine power supplying groups has the structure general formula:
M(L) 2L′
In the general formula: M is Ru or Os; L is selected from arbitrarily 2,2 '-dipyridyl and verivate or 1,10-o-phenanthroline (phenanthroline) and verivate thereof, L ' is selected from following part:
Figure G2009100111395D00021
In the formula: B is-(CH 2) n-, wherein n is integer 1-10 or the alkyl chain-(CH that has the amido linkage group at an arbitrary position 2) n-, the total carbon number n of alkyl chain is integer 1-10; P is thiodiphenylamine (PTZ) or H.
The compound method of bipyridyl ruthenium/osmium ECL affinity tag that intramolecularly has phenothiazine power supplying groups is following:
With 4,4 '-dimethyl-dipyridyl is a raw material, experience monomethyl lithiumation, the synthetic ECL affinity tag Ru-PTZ that connects with the different chain length carbochain such as the prolongation of dipyridyl side chain and thiodiphenylamine (PTZ) nucleophilic substitution reaction; Simultaneously, be that raw material adopts the synthetic substituted thiodiphenylamine of propyl group amine (PTZ) of Gabrial synthesis method with the phthalic imidine; With the 2-acetylpyridine is that raw material adopts the synthetic 4-methyl dipyridyl of Krohnke pyridine synthesis method, experiences methyl oxidation afterwards, the last and synthetic ECL affinity tag Ru-A-PTZ that has amido linkage of the substituted thiodiphenylamine of propyl group amine (PTZ) reaction.
The invention has the beneficial effects as follows: will have the active electron donor thiodiphenylamine of reversible redox (PTZ) and be incorporated in the bipyridyl ruthenium/osmium ECL tag structure; The bipyridyl ruthenium/osmium ligand structure is modified; Utilize intramolecularly and intermolecular synergy; Reduce the consumption of amine co-reactant, reduce background interference, ECL is strengthened greatly.
Description of drawings
Fig. 1 adopts platinum (Pt) to be working electrode, the ECL affinity tag Ru-PTZ and the reference compound tris (bipyridine) ruthenium Ru (bpy) of embodiment 1 preparation 3 2+Electrochemiluminescence intensity contrast figure under tripropyl amine (TPrA) effect respectively.
Fig. 2 adopts gold (Au) to be working electrode, the ECL affinity tag Ru-PTZ and the reference compound tris (bipyridine) ruthenium Ru (bpy) of embodiment 1 preparation 3 2+Electrochemiluminescence intensity contrast figure under tripropyl amine (TPrA) effect respectively.
Fig. 3 adopts platinum (Pt) to be working electrode, the ECL affinity tag Ru-A-PTZ and the reference compound tris (bipyridine) ruthenium Ru (bpy) of embodiment 2 preparations 3 2+Electrochemiluminescence intensity contrast figure under tripropyl amine (TPrA) effect respectively.
Fig. 4 adopts gold (Au) to be working electrode, the ECL affinity tag Ru-A-PTZ and the reference compound tris (bipyridine) ruthenium Ru (bpy) of embodiment 2 preparations 3 2+Electrochemiluminescence intensity contrast figure under tripropyl amine (TPrA) effect respectively.
Fig. 5 is ECL affinity tag Ru-PTZ and the reference compound tris (bipyridine) ruthenium Ru (bpy) of the concentration of tripropyl amine (TPrA) to embodiment 1 preparation 3 2+Electrochemiluminescence intensity influence synoptic diagram.
Embodiment
Below in conjunction with specific embodiment the present invention is done further elaboration, but do not influence protection scope of the present invention.
Embodiment 1
ECL affinity tag Ru-PTZ's is synthetic:
Reaction formula is as follows:
Figure G2009100111395D00041
(1) midbody 1 is synthetic:
25ml single port bottle, syringe (1ml * 2,10ml * 1) are put into baking oven, thoroughly dry moisture after, 1ml THF and the 0.82ml Diisopropylamine (5.88mmol) that dewaters that dewaters is injected 25ml single port bottle through syringe, and places ice-water bath with rubber stopper seal.The syringe needle that is connected in oil pump is inserted the single port bottle vacuumize, and displacement N 2, 3 times repeatedly, the hexane solution 2.4ml (5.43mmol) with syringe extraction 2.2mol/L n-Butyl Lithium injects N afterwards 2In the single port bottle of atmosphere, stir subsequent use.
With 1g 4,4 '-dimethyl--2,2 '-dipyridyl (5.43mmol), the 40ml THF that dewaters adds in the 100ml single port bottle, and places ice-water bath with rubber stopper seal, vacuumizes displacement N 2, 3 times repeatedly.All extract the solution in the 25ml single port bottle out slowly injection 100ml there-necked flask with syringe, colourless solution becomes brown, and ice-water bath stirs 1h.
With syringe with 1.6ml, 1,3-dibromopropane (16.29mmol) injects there-necked flask; Remove ice-water bath, solution becomes yellow behind the reaction 3h, adds 50ml phosphoric acid buffer (PH=7); And with methylene dichloride (3 * 50ml) extractions, anhydrous sodium sulfate drying organic phase, silica gel column chromatography separation (methylene dichloride-ETHYLE ACETATE behind the rotation evaporate to dryness; 4: 1) get faint yellow transparent oily matter 0.97g, yield is 85%.
(2) midbody 2 is synthetic:
Add thiodiphenylamine (PTZ) 0.5g (2.5mmol) in the 25ml single necked round bottom flask, sodium hydride 0.06g (2.5mmol) is dissolved in 10mL DMF, N 2Protection adds 1.5g midbody 1 (5mmol) behind the room temperature reaction 1h down.12 hours postcooling of reflux are to room temperature, the evaporated under reduced pressure solvent, and silicagel column separates (sherwood oil/CH 2Cl 2=5: 1), obtain pale brown look oily matter 0.6g.Yield is 80%.
(3) Ru (bpy) 2Cl 22H 2O's is synthetic:
With RuCl 33H 2O (3.9g, 19.9mmol) with 2,2 '-dipyridyl (4.68g 30mmol) is dissolved in 50mL and dewaters among the DMF, nitrogen add down anhydrous LiCl (4.2g, 1mmol).Mixed solution lucifuge back flow reaction 8h is cooled to room temperature under nitrogen, adds 250mL acetone, and the suspension liquid that obtains is placed spend the night (about 16h) at 0-3 ℃ of refrigerator.Filter, the blackish green solid that obtains is used the 25mL water washing respectively 3 times, and then respectively with 25mL ether washing 3 times, vacuum-drying gets bright black crystalline particles product 5.46g.Yield is 35%.
(4) ECL affinity tag Ru-PTZ's is synthetic:
Under magnetic agitation, in the mixing solutions of 40mL ethanol that is dissolved with 200mg midbody 2 (0.472mmol) and 5ml water, add 207mg Ru (bpy) 2Cl 22H 2O (0.4mmol) obtains the black mixed solution.Under nitrogen protection, behind the lucifuge heating reflux reaction 24h, solution becomes redness with this mixed solution.Utilize the rotatory evaporator solvent evaporated, be dissolved in the red oil that obtains in the ethanol.Utilize silica gel column chromatography to separate purification, developping agent: CH 3CN: H 2O: KNO 3Saturated aqueous solution=10: 1: 1 (V/V/V) is collected red component, behind the evaporate to dryness developping agent it is dissolved in an amount of acetonitrile solvent, removes by filter insoluble saltpetre, again with the acetonitrile evaporate to dryness, is dissolved in minute quantity methyl alcohol, then it is added saturated NH 4PF 6The aqueous solution is with displacement NO 3 -To ion,, get red solid powdery product 686mg after the drying with the sedimentation and filtration of separating out, fully washing.Yield is 76%.
1H-NMR(δppm，CD 3COCD 3)：1.84-1.89(m，4H，C 2H 2，C 3H 2)，2.58(s，3H，bpy-CH 3)，2.88(t，J＝7.0Hz，2H，NCH 2)，4.00(t，J＝5.8Hz，2H，bpy-CH 2)，6.93(t，J＝7.4Hz，2H，PTZ-H)，7.00(d，J＝8.0Hz，2H，PTZ-H)，7.08-7.17(m，4H，PTZ-H)，7.32-7.34(d，J＝5.8Hz，1H，bpy′-H)，7.38-7.40(d，J＝5.8Hz，1H，bpy′-H)，7.52-7.58(m，4H，bpy-H，bpy′-H)，7.78-8.00(d，J＝5.8Hz，1H，bpy′-H)，7.82-7.84(d，J＝5.8Hz，1H，bpy′-H)，7.96-8.04(m，4H，bpy-H，bpy′-H)，8.17-8.20(m，4H，bpy-H，bpy′-H)，8.64(s，2H，bpy′-H)，8.79-8.80(m，4H，bpy-H，bpy′-H)。HRMS?calculated?for?C 47H 41N 7RuS[M-2PF 6 -] 2+837.2188，found?837.2180。
(5) testing method of ECL affinity tag Ru-PTZ electrochemiluminescence:
Adopt cyclic voltammetric electrochemical method test ECL affinity tag Ru-PTZ and reference compound tris (bipyridine) ruthenium Ru (bpy) 3 2+Electrochemiluminescence intensity under tripropyl amine (TPrA) effect respectively, ECL affinity tag Ru-PTZ and reference compound tris (bipyridine) ruthenium Ru (bpy) 3 2+Concentration be 1 μ M, the concentration range of coreaction reagent tripropyl amine (TPrA) is 5mM, test electrode is platinum (Pt) electrode, test result is seen Fig. 1; Other conditions are constant, and test electrode changes gold (Au) electrode into, and test result is seen Fig. 2.
Embodiment 2
ECL affinity tag Ru-A-PTZ's is synthetic:
Reaction formula is as follows:
Figure G2009100111395D00061
Figure G2009100111395D00071
(1) midbody 3 is synthetic:
In the 200ml single necked round bottom flask of straight cold finger is housed, add the 80ml absolute ethyl alcohol, to stir, gradation adds phthalic imidine 10g (68mmol), heating 1h.(3.8g behind methanol solution 60ml 68mmol), has the oyster white flocks at once, continues to stir 3h to add 8% Pottasium Hydroxide.Cooled and filtered, drying obtains white plates crystal 12.7g, and yield is 92%.
(2) midbody 4 is synthetic:
In the 50ml single necked round bottom flask, add 5g (25mmol) thiodiphenylamine (PTZ), 0.6g (25mmol) sodium hydride is dissolved in 20mL DMF, N 2Protection add behind the room temperature reaction 1h down 1,3 dibromopropane (15g, 75mmol), reflux 12h postcooling to room temperature, the evaporated under reduced pressure solvent, silicagel column separates (sherwood oil: CH 2Cl 2=20: 1), obtain faint yellow oily thing 3.6g.Yield is 45%.
(3) midbody 5 is synthetic:
3.5g (18.9mmol) midbody 3 and 3g (9.4mmol) midbody 4 are mixed, and the cetomacrogol 1000 that adds midbody 4 quality 3% is a phase-transfer catalyst, and acetone is solvent; Reflux 3h; Cooled and filtered, steam solvent after underpressure distillation go out excessive glycol dibromide and polyoxyethylene glycol.Residuum adds less water, and dichloromethane extraction is used for removing does not have the sylvite that reacted.Merge organic phase, steam CH 2Cl 2, the absolute ethyl alcohol recrystallization.Obtain the faint yellow midbody 5 of 2.7g.Yield is 75%.
(4) midbody 6 is synthetic:
1.5g midbody 5 is dissolved in the 20ml ethanol, adds the 10ml Hydrazine Hydrate 80, reflux 5h.After the solvent evaporated, add 2M hydrochloric acid soln 60ml, add 12M hydrochloric acid 3ml again.Suspension-s is stirred 2h down at 50 ℃, at room temperature stir 24h again, filter, concentrate.Enriched material is dissolved in the 5ml water.Add 15% sodium hydroxide solution, with dichloromethane extraction 3 times, consumption 30ml at every turn.Merge organic phase, solvent evaporated gets faint yellow oily thing 0.84g, and yield is 85%.
(5) midbody 7 is synthetic:
(40.8g 0.148mol) is dissolved in the pyridine (120ml), and (16.56ml 0.148mol) is dissolved in dropwise adding in the pyridine (40ml) to the 2-acetylpyridine with iodine.Solution backflow 2.5h leaves standstill 12h then.Collect black precipitate, black precipitate is dissolved in the ethanol (500ml), add gac 5-8g, reflux 10min.With the gac filtered while hot, the filtrating cooling is separated out and is obtained product, and yield is 85%.
(6) midbody 8 is synthetic:
With midbody 7 (15g, 46mmol) and ammonium acetate (15g 195mmol) is dissolved in the 150ml methyl alcohol; The adding crotonic aldehyde (3.8ml, 46mmol), solution is heated to 65 ℃ of reaction overnight; Reaction back evaporate to dryness solution, (6 * 50ml) extract, and the gained organic phase is used the saturated common salt water washing with normal hexane to obtain the dark oil thing; And use dried over mgso, product application column chromatography for separation (Al 2O 3: normal hexane-acetone=9: 1).With sherwood oil recrystallization at low temperatures, obtain the 3.1g powder-product midbody 8 that is white in color, yield is 40%.
(7) midbody 9 is synthetic:
Under the magnetic agitation, 2.0g (11.7mmol) midbody 8 is joined in the 30mL vitriol oil, treat that it dissolves fully after, reaction solution is cooled to 0 ℃, in 1h, in this reaction solution, add 6.5g (65.1mmol) CrO in batches 3Particle.Then this blue-green solution is warming up to 75 ℃, behind the constant temperature 4h, is cooled to room temperature, continue to stir 10h.Reaction solution is poured in the ice-water bath, filters, fully after the washing filter cake is suspended in the water, add the KOH particle under the violent stirring to pH=9-10.Cross the blue-greenish colour insolubles that filters out wherein, will filtrate and to pH=1-2, separate out milky white precipitate with hcl acidifying.Filter, washing, ethanol is washed, and ether is washed, and obtains product 2.1g after the drying, and yield is 90%.
(8) ECL affinity tag Ru-A-PTZ's is synthetic:
Under magnetic agitation, in the mixing solutions of 40mL ethanol that is dissolved with 200mg midbody 9 (1mmol) and 5ml water, add 518mg Ru (bpy) 2Cl 22H 2O (1mmol) obtains the black mixed solution.Under nitrogen protection, behind the lucifuge heating reflux reaction 24h, solution becomes redness with this mixed solution.Utilize the rotatory evaporator solvent evaporated, be dissolved in the red oil that obtains in the ethanol.Utilize silica gel column chromatography to separate purification, developping agent: CH 3CN: H 2O: KNO 3Saturated aqueous solution=4: 1: 1 (V/V/V) is collected red component, behind the evaporate to dryness developping agent it is dissolved in an amount of acetonitrile solvent, removes by filter insoluble saltpetre, again with the acetonitrile evaporate to dryness, is dissolved in minute quantity methyl alcohol, then it is added saturated NH 4PF 6The aqueous solution is with displacement NO 3 -To ion, with the sedimentation and filtration of separating out, fully washing, get red solid powdery product 542mg after the drying, yield is 60%.
At N 2Protection down, will go up step gained compound (452mg, 0.5mmol) and SOCl 2(4mL 20mmol) mixes back backflow 6h.Excessive SOCl is removed in air distillation 2Be cooled to room temperature, the solid that obtains be dissolved in MeCN (10mL) solvent that dewaters, this drips of solution is added to is dissolved with midbody 6 (256mg then; 1.0mmol) and triethylamine (0.6mL; 4.3mmol) MeCN (20mL) solution in, dropwise back stirring reaction 1h, reheat continues reaction 4h to refluxing.After reaction solution is cooled to room temperature,, use CHCl to wherein adding 20mL water 3Extract 3 times, each consumption is 20mL, and the aqueous hydrochloric acid with 0.1N washs organic phase 2 times again, and each consumption 20ml tells organic phase, and behind anhydrous magnesium sulfate drying, rotary evaporation is removed solvent.Separate purification with silica gel column chromatography, developping agent: CH 3CN: H 2O: KNO 3Saturated aqueous solution=10: 1: 1 (V/V/V) is collected red component, behind the evaporate to dryness developping agent it is dissolved in an amount of acetonitrile solvent, removes by filter insoluble saltpetre, again with the acetonitrile evaporate to dryness, is dissolved in minute quantity methyl alcohol, then it is added saturated NH 4PF 6The aqueous solution is with displacement NO 3 -To ion, with the sedimentation and filtration of separating out, fully washing, get red solid powdery product Ru-A-PTZ 240mg after the drying, yield is 42%.
1H-NMR(δppm，CD 3COCD 3)：2.1-2.17(m，2H，C 2H 2)，3.59(t，J＝6.4Hz，2H，NCH 2)，4.09(t，J＝6.4Hz，2H，CONH-H)，6.88-6.93(m，2H，PTZ-H)，7.01-7.06(m，4H，PTZ-H)，7.16-7.20(m，2H，PTZ-H)，7.54-7.63(m，5H，bpy-H，bpy′-H)，7.75-7.77(m，1H，bpy′-H)，8.04-8.10(m，5H，bpy-H，bpy′-H)，8.15-8.17(m，1H，bpy′-H)，8.19-8.26(m，5H，bpy-H，bpy′-H)，8.81-8.86(m，5H，bpy-H，bpy′-H)，8.96-8.97(m，1H，bpy′-H)。HRMS?calculated?for?C 46H 38N 8ORuS[M-2PF 6 -] 2+852.1933，found?852.1922。
(9) testing method of ECL affinity tag Ru-A-PTZ electrochemiluminescence:
Adopt cyclic voltammetric electrochemical method test ECL affinity tag Ru-A-PTZ and reference compound tris (bipyridine) ruthenium Ru (bpy) 3 2+Electrochemiluminescence intensity under tripropyl amine (TPrA) effect respectively, ECL affinity tag Ru-A-PTZ and reference compound tris (bipyridine) ruthenium Ru (bpy) 3 2+Concentration be respectively 1 μ M, the concentration range of coreaction reagent tripropyl amine (TPrA) is 5mM, test electrode is platinum (Pt) electrode, test result is seen Fig. 3; Other conditions are constant, and test electrode changes gold (Au) electrode into, and test result is seen Fig. 4.

Claims (1)

1. intramolecularly has the bipyridyl ruthenium ECL affinity tag of phenothiazine power supplying groups, it is characterized in that, the bipyridyl ruthenium ECL tag structure formula that described intramolecularly has phenothiazine power supplying groups is following:
Figure FSB00000728591600011
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