CN103509042B - A kind of preparation method of new terbium complex probe and the purposes as potassium ion identification agent thereof - Google Patents
A kind of preparation method of new terbium complex probe and the purposes as potassium ion identification agent thereof Download PDFInfo
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- CN103509042B CN103509042B CN201210204303.6A CN201210204303A CN103509042B CN 103509042 B CN103509042 B CN 103509042B CN 201210204303 A CN201210204303 A CN 201210204303A CN 103509042 B CN103509042 B CN 103509042B
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- 0 CCC(*)(CN(CCNC)CC[N+](CCN(C)CC)CC([O+])=O)O Chemical compound CCC(*)(CN(CCNC)CC[N+](CCN(C)CC)CC([O+])=O)O 0.000 description 2
- UMUVMLVJQYSOKA-UHFFFAOYSA-N CC(C)(C)OC(N1CCOCCOCCN(CCc(cc2)ccc2O)CCOCCOCC1)=O Chemical compound CC(C)(C)OC(N1CCOCCOCCN(CCc(cc2)ccc2O)CCOCCOCC1)=O UMUVMLVJQYSOKA-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention relates to a kind of terbium coordination compound of general formula I, its preparation method and the purposes as potassium ion identification agent thereof.Terbium coordination compound of the present invention optionally can identify K
+, and can as K
+ion probe and not by other metallic cation Na
+, Li
+, Cd
2+, Mn
2+, Fe
2+, Mg
2+, Co
2+, Ca
2+, Hg
2+, Pb
2+, Ni
2+, Cu
2+, Zn
2+interference.
Description
Technical field
The present invention relates to a kind of novel cpd, the Its Preparation Method And Use that can be used as metal ion identification agent.More particularly, the present invention relates to a kind of terbium coordination compound, its preparation method and the purposes as potassium ion identification agent thereof.
Background technology
Molecular recognition occupies very important status in modern development in science and technology, and in molecular recognition to the Study of recognition of ion object maximum be identification to alkali and alkaline earth metal ions ion.Potassium ion, as a kind of common alkalimetal ion, is indispensable major element in human body, maintains the physiological function that body weight for humans is wanted, as maintained cell metabolism, regulate osmotic pressure, maintain acid base equilibrium, the concentration of other ions in control agent and the generation etc. of neural system electrical signal.In addition, potassium ion also has an important function to be exactly the coordination maintaining normal myocardium contractile motion in human body.When the concentration of potassium ion occurs abnormal, the generation of numerous disease will be caused, such as hypertension, apoplexy, epilepsy etc.So the content measuring potassium ion in human body has great importance.
Although the measuring method of potassium ion is varied, such as ion specific electrode method, flame photometric analysis method, enzyme process etc., the large multioperation more complicated of these methods, ion interference is comparatively large, and influence factor is more, and accuracy is also good not.In recent years, engendered that the time resolved fluorescence detection technique based on rare earth compounding carries out the method for ion identification.This technology judges that measured matter is to certain the even complex performance of some ion and selectivity according to the change of fluorescence intensity.The maximum advantage of time resolved fluorescence detection technique is exactly the interference can eliminated from the short life such as reagent, sample background fluorescence and light at random, only detects the distinctive long-life phosphors of target compound, thus greatly improves the sensitivity that target compound measures.
Rare earth compounding has that fluorescence lifetime is long, emission peak is narrow and the Stokes shift superior characteristics of luminescence such as large, and just because of this, this kind of title complex has been applied to the every field of life science.With the derivative of Azacrown ether containing for part, metal ion centered by lanthanide ion and the rare earth compounding that formed as identifying that the probe of individual metal ion is also taken seriously gradually, and develop the research becoming metal-ion fluorescent probe gradually.One optionally fluorescent probe should have can with the unit of target detect molecule or ion generation selective reaction, and Azacrown ether containing is exactly the main unit of inclusion alkalimetal ion in this kind of rare earth compounding probe.Because Azacrown ether containing has certain cavity size, and its structure is easy to modify, if introduce suitable functional group on the nitrogen-atoms of ring, aza-crown ether derivative after modifying like this can identify metal ion, so greatly can improve the Selective recognition effect to alkalimetal ion by means of non covalent bond synergies such as hydrogen bond, electrostatic interaction, Van der Waals force, hydrophobic interaction, positively charged ion-π effect, pi-pi accumulation effect and induction wedgings.
Summary of the invention
The object of this invention is to provide a kind of novel cpd that can be used for identifying potassium ion.
Object more specifically of the present invention is to provide a kind of terbium coordination compound probe, and it can be used as the identification agent of K+, and has highly selective and sensitivity.
Another object of the present invention is to provide a kind of method preparing above-mentioned terbium coordination compound.
Another object of the present invention is the purposes of above-mentioned terbium coordination compound as potassium ion identification agent.
One aspect of the present invention provides a kind of terbium coordination compound of general formula I, and it has structure as shown below.
The present invention provides a kind of method preparing the terbium coordination compound of general formula I on the other hand, and it comprises step 1-9 as shown below.
Further aspect of the present invention provides the terbium coordination compound of general formula I as the purposes of potassium ion identification agent.
These and other objects of the present invention, feature and advantage will become more clear after reading this specification sheets by reference to the accompanying drawings.
Accompanying drawing explanation
Fig. 1 is that the compound Tb-L obtained in embodiment 2 identifies K
+principle schematic.
Fig. 2 is that the compound Tb-L that obtains in embodiment 2 is at different concns K
+titration curve under existing.
Fig. 3 is that the compound Tb-L that obtains in embodiment 2 is to K
+the test result of Selective recognition.
Embodiment
Terbium coordination compound of the present invention has no bibliographical information and is represented by following general formula I:
Wherein R
1, R
2and R
3be hydrogen or be selected from C independently of each other
1-C
6alkyl and C
1-C
6the electron-donating group of alkyl oxy, preferred hydrogen or be selected from C
1-C
4alkyl and C
1-C
4the electron-donating group of alkyl oxy.
For term C herein
1-C
6alkyl refers to the saturated straight chain or branched hydrocarbyl radical with 1-6 carbon atom, such as C
1-C
4alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl and the tertiary butyl.
The invention still further relates to compound 11:
Wherein R
1, R
2and R
3as defined above.
Formula I of the present invention can be obtained by hereafter described preparation method.
Preparation process can be divided into nine steps to carry out, shown in the following scheme II of total synthetic route.
Step 1:
Step 2:
Step 3:
Step 4:
Step 5:
Step 6:
Step 7:
Step 8:
Step 9:
Scheme II
Step 1 is usually carried out at room temperature to 40 DEG C.Boc
2the mol ratio of O and compound 1 is generally 1.Reaction times can be 10-30 hour.In addition, step 1 is carried out usually in the solvent being selected from dioxane, methylene dichloride and trichloromethane.Typically, every g compound 1 uses 10-1000ml solvent, preferred 20-100ml solvent.
Step 2 is carried out usually under nitrogen protection.Temperature of reaction is generally 40-70 DEG C.Reaction times is generally 10-30 hour.Compound 3 is generally 1-2 with the mol ratio of compound 2.In addition, step 2 is carried out usually in the solvent being selected from MeCN, DMF and DMSO.Typically, every g compound 2 uses 10-1000ml solvent, preferred 20-300ml solvent.In addition, step 2 is being selected from Cs usually
2cO
3and Na
2cO
3alkali exist under carry out.Typically, every mol compound 2 uses 1-5mol alkali.
Step 3 is carried out usually under nitrogen protection.Temperature of reaction is generally 20-50 DEG C.Reaction times is generally 0.5-2 hour.Compound 5 is generally 1-1.5 with the mol ratio of compound 4.In addition, step 3 is carried out usually in the solvent being selected from DMF, acetonitrile and DMSO.Typically, every g compound 4 uses 10-1000ml solvent, preferred 20-300ml solvent.In addition, step 3 is being selected from Cs usually
2cO
3and Na
2cO
3alkali exist under carry out.Typically, every mol compound 4 uses 1-5mol alkali.
Compound 5 in step 3 can be commercial, or by making corresponding 4-methyl benzophenone compound and bromine react and obtain.Such as by under backflow and high voltage mercury lamp radiation, bromine is added in the carbon tetrachloride solution of corresponding 4-methyl benzophenone compound, add rear continuation stirring and refluxing reaction 1-5 hour and prepare compound 5.Bromine and corresponding 4-methyl benzophenone compound are usually with the molar ratio reaction of 1:1.
Step 4 is usually carried out under the ethyl acetate solution of trifluoroacetic acid or hydrogenchloride exists.The amount of trifluoroacetic acid or hydrogenchloride is usually excessive, as used with the mol ratio of the trifluoroacetic acid of 2-100 or hydrogenchloride and compound 6.Temperature of reaction is 20-50 DEG C, and the reaction times is 1-2 hour.In addition, step 4 is carried out usually under the solvent being selected from methylene dichloride, trichloromethane and dioxane exists.Typically, every g compound 6 uses 10-1000ml solvent, preferred 20-300ml solvent.
Step 5 by first at a lower temperature, as added in compound 7 by chloroacetyl chloride at-5 DEG C to 5 DEG C, can be increased to room temperature after adding and carrying out.Reaction carries out 2-5 hour usually.The mol ratio of chloroacetyl chloride and compound 7 can be 1.5-4 usually.In addition, step 5 is carried out usually in the solvent being selected from methylene dichloride, trichloromethane and DMF.Typically, every g compound 7 uses 10-1000ml solvent, preferred 20-300ml solvent.In addition, step 5 is being selected from triethylamine, pyridine, Na usually
2cO
3and Cs
2cO
3alkali exist under carry out.Typically, every mol compound 7 uses 1-5mol alkali.
Step 6, usually by room temperature compound 8 being added dropwise to Isosorbide-5-Nitrae, in 7,10-tetraazacyclododecanand, is warming up to 50-70 DEG C and carry out after adding.Reaction times is generally 6-10 hour.Isosorbide-5-Nitrae, the mol ratio of 7,10-tetraazacyclododecanand and compound 8 is generally 1.5-5.In addition, step 6 is carried out usually in the solvent being selected from acetonitrile, DMF and DMSO.Typically, every g compound 8 uses 10-1000ml solvent, preferred 20-300ml solvent.In addition, step 6 is being selected from Cs usually
2cO
3, Na
2cO
3carry out under existing with the alkali of triethylamine.Typically, every mol compound 8 uses 1-5mol alkali.
Step 7 is carried out usually at 20-50 DEG C.Reaction times is generally 10-20 hour.The mol ratio of bromo-acetic acid tert-butyl and compound 9 is generally 3-6.In addition, step 7 is carried out usually in the solvent being selected from acetonitrile, trichloromethane, DMF and DMSO.Typically, every g compound 9 uses 10-1000ml solvent, preferred 20-300ml solvent.In addition, step 7 is being selected from Cs usually
2cO
3, Na
2cO
3, triethylamine alkali exist under carry out.Typically, every mol compound 9 uses 2-10mol alkali.
Step 8, being usually used in carrying out under esterolytic condition, is carried out usually under room temperature and nitrogen protection.For this reason, ethyl acetate solution or the sulfuric acid of TFA, hydrogenchloride is usually used.Reaction times is not particularly limited, and is generally 10-24 hour.The amount of above-mentioned acid is usually excessive, as used with the mol ratio of the acid of 4-500 and compound 10.In addition, step 8 is carried out usually in the solvent being selected from methylene dichloride, trichloromethane, acetonitrile and DMF.Typically, every g compound 10 uses 5-100ml solvent.
Step 9 is passed through with sodium hydroxide usually by TbCl
36H
2it is 6-8 that the aqueous solution of O and compound 11 is adjusted to pH, then at elevated temperature, carries out to the lower reaction of backflow as 70 DEG C.Reaction times is generally 10-30 hour.TbCl
36H
2the mol ratio of O and compound 11 can be 1.5-5.The concentration of the aqueous solution of compound 11 can be 2-10mmol/L.
The compounds of this invention comprises the crown ether unit with certain cavity size, the cavity size of this unit can inclusion metal ion, form the induction of cation-π interaction at phenyl ring under, the compounds of this invention is made to have very strong selective complexation effect to potassium metal ion, and can as K
+ion probe and not by other metallic cation Na
+, Li
+, Cd
2+, Mn
2+, Fe
2+, Mg
2+, Co
2+, Ca
2+, Hg
2+, Pb
2+, Ni
2+, Cu
2+, Zn
2+interference.
The ion identification effect of the compounds of this invention is judged by the change of the luminous intensity to this compound.The compounds of this invention self has the performance be excited, and therefore can adopt titration experiments, judges that it is to the identification of object potassium ion and complexing action by the change of self luminous intensity of this compound.Pass through K
+to the titration experiments of the compounds of this invention, find the K of different concns
+the enhancing of the different amplitudes of this compound light-emitting intensity can be caused.Confirm that the compounds of this invention can be used for K by this titration experiments
+selective recognition.
Embodiment 1
The preparation of 4-brooethyl benzophenone
In reaction flask, add 19.6g (0.1mol) 4-methyl benzophenone, then add 100mLCCl
4, stirring and dissolving, reflux, under then remaining at high voltage mercury lamp radiation, drips bromine 16g (0.1mol) in 30min, after adding, continues stirring and refluxing 2h.Then stopped reaction, after rotary evaporation remove portion solvent to about 20-30mL, pours in 50mL dehydrated alcohol, recrystallization by mixture, filter, obtain 13.6g white crystal 4-brooethyl benzophenone, productive rate 49.4%, m.p.111 ~ 113 DEG C.
1HNMR(400MHz，CDCl
3)δ(ppm)=4.54(s，2H)，7.49(t，2H，J=8Hz)，7.51(d，2H，J=8Hz)，7.60(t，1H，J=8Hz)，7.79(d，2H，J=8Hz)，7.80(d，2H，J=8Hz)。
Embodiment 2
The preparation of the compounds of this invention Tb-L
Step 1: prepare compound S 2
By 3.72g (13.59mmol) 1,10-diaza 18 be preced with that 6 are dissolved in 78mL 1, in 4-dioxane, separately 3.06g (13.59mmol) tert-Butyl dicarbonate (BOC acid anhydrides) is dissolved in 1 of 42mL, in 4-dioxane, be added dropwise in crown ether solution by BOC anhydride solution in 1.5h, after stirring 30min at 40 DEG C, stirring at room temperature reacts 16h.Then rotary evaporation is except desolventizing, and the thick product obtained crosses purification by silica gel column chromatography, and (elutriant is CH
2cl
2: CH
3oH=80:20, TLC monitor, and iodine cylinder develops the color), obtain the liquid S2 of 1946mg colorless oil, productive rate 39.5%.
1HNMR(400MHz，CDCl
3)δ(ppm)=1.44(s，9H)，2.83(t，4H，J=5Hz)，3.51(t，4H，J=6Hz)，3.60(bs，12H)，3.64(t，4H，J=5Hz)。
Step 2: prepare compound S 3
By 1946mg (5.37mmol) S2 and 2627mg (8.05mmol) Cs
2cO
3be dissolved in 240mL acetonitrile; separately p-for 1693mg (8.42mmol) (2-bromotrifluoromethane) phenol is dissolved in 36mL acetonitrile; in 3h, p-(2-bromotrifluoromethane) phenol solution is added dropwise in S2 solution, then under the protection of nitrogen, is heated to 65 DEG C of stirring reaction 18h.After the mixture obtained filters, filtrate rotary evaporation is removed desolventizing, the thick product obtained crosses purification by silica gel column chromatography, and (elutriant is CH
2cl
2: CH
3oH=90:10, TLC monitor, and UV develops the color, and iodine cylinder develops the color), obtain the liquid S3 of 626.7mg pale yellowish oil, productive rate 24.2%.
1HNMR(400MHz，CDCl
3)δ(ppm)=1.45(s，9H)，2.75(b，2H)，2.81(b，2H)，2.94(b，4H)，3.49(b，4H)，3.60(bs，12H)，3.67(b，4H)，6.75(d，2H，J=8Hz)，7.04(d，2H，J=8Hz)。
Step 3: prepare compound S 4
By 626.7mg (1.30mmol) S3 and 1272mg (3.90mmol) Cs
2cO
3be dissolved in 21mL dry DMF, then add 429mg (1.56mmol) 4-brooethyl benzophenone wherein, stirring at room temperature reaction 1h under the protection of nitrogen.After the mixture obtained filters, filtrate rotary evaporation is removed desolventizing, the thick product obtained crosses purification by silica gel column chromatography (CH
2cl
2: CH
3oH=90:10, TLC monitor, and UV develops the color), obtain the liquid S4 of 512mg safran oily, productive rate 58.2%.
1HNMR(400MHz，CDCl
3)δ(ppm)=1.45(s，9H)，2.75(bs，4H)，2.88(bs，4H)，3.49(t，4H，J=6Hz)，3.61(bs，16H)，5.13(s，2H)，6.90(d，2H，J=8Hz)，7.12(d，2H，J=8Hz)，7.49(t，2H，J=8Hz)，7.54(d，2H，J=8Hz)，7.60(t，1H，J=8Hz)，7.81(t，4H，J=8Hz)。
Step 4: prepare compound S 5
512mg (0.75mmol) S4 is dissolved in 14mL anhydrous methylene chloride, then drips 4mL trifluoroacetic acid wherein, add rear stirring at room temperature reaction 1h.The mixture rotary evaporation obtained is except desolventizing, and the thick product obtained is dissolved in 40mL methylene dichloride, uses 2MCs
2cO
3washing (3 × 30mL) uses anhydrous magnesium sulfate drying afterwards, and rotary evaporation removes the liquid S5 that desolventizing obtains 377mg brown oil, productive rate 87.3%.
1HNMR(400MHz，CDCl
3)δ(ppm)=2.70(bs，2H)，2.76(bs，2H)，2.83(t，4H，J=5Hz)，2.93(bs，4H)，3.62(bs，12H)，3.71(bs，4H)，5.14(s，2H)，6.91(d，2H，J=8Hz)，7.11(d，2H，J=8Hz)，7.49(t，2H，J=8Hz)，7.55(d，2H，J=8Hz)，7.60(t，1H，J=8Hz)，7.82(t，4H，J=8Hz)。
Step 5: prepare compound s 6
377mg (0.65mmol) S5 and 270 μ L (1.94mmol) triethylamines are dissolved in 18mL anhydrous methylene chloride, separately the chloroacetyl chloride of 110 μ L (1.38mmol) is dissolved in 5.4mL anhydrous methylene chloride, then at 0 DEG C, chloroacetyl chloride solution is joined in S5 solution, after adding, rise to stirring at room temperature reaction 2.5h.The mixture rotary evaporation obtained is except desolventizing, and the thick product obtained is dissolved in 40mL methylene dichloride, uses 2MCs
2cO
3washing (3 × 30mL) uses anhydrous magnesium sulfate drying afterwards, and the thick product that rotary evaporation obtains except desolventizing crosses purification by silica gel column chromatography (CH
2cl
2: CH
3oH=95:5, TLC monitor, and UV develops the color), obtain the liquid S6 of 167mg yellow oily, productive rate 39.4%.
1HNMR(400MHz，CDCl
3)δ(ppm)=2.88(bs，4H)，3.03(bs，4H)，3.62(m，16H)，3.71(bs，4H)，4.16(s，2H)，5.14(s，2H)，6.91(d，2H，J=8Hz)，7.14(d，2H，J=8Hz)，7.49(t，2H，J=8Hz)，7.55(d，2H，J=8Hz)，7.60(t，1H，J=8Hz)，7.82(t，4H，J=8Hz)。
Step 6: prepare compound S 7
By 108mg (0.63mmol) Isosorbide-5-Nitrae, 7,10-tetraazacyclododecanand and 245mg (0.75mmol) Cs
2cO
3be dissolved in 35mL anhydrous acetonitrile, separately 167mg (0.25mmol) S6 be dissolved in 8mL anhydrous acetonitrile, in 50min, S6 solution be added dropwise to Isosorbide-5-Nitrae, in 7,10-tetraazacyclododecanand solution, after adding, rise to 60 DEG C of stirring reaction 8h.After the mixture obtained filters, filtrate rotary evaporation is removed desolventizing, the thick product obtained crosses purification by silica gel column chromatography (CH
2cl
2: CH
3oH:NH
4oH=80:17:3, TLC monitor, and UV develops the color, and iodine cylinder is painted), obtain the liquid S7 of 162mg yellow oily, productive rate 82.2%.
1HNMR(400MHz，CDCl
3)δ(ppm)=2.70(m，8H)，2.78(m，4H)，2.84(m，12H)，3.51(bs，4H)，3.60(bs，18H)，5.14(s，2H)，6.91(d，2H，J=8Hz)，7.14(d，2H，J=8Hz)，7.49(t，2H，J=8Hz)，7.55(d，2H，J=8Hz)，7.60(t，1H，J=8Hz)，7.82(t，4H，J=8Hz)。
Step 7: prepare compound S 8
By 162mg (0.20mmol) S7 and 326mg (1.0mmol) Cs
2cO
3be dissolved in 14mL anhydrous acetonitrile, then add 95 μ L (0.654mmol) bromo-acetic acid tert-butyls wherein, add rear stirring at room temperature reaction 16h.After the mixture obtained filters, filtrate rotary evaporation is removed desolventizing, the thick product obtained crosses purification by silica gel column chromatography (CH
2cl
2: CH
3oH=80:20, TLC monitor, and UV develops the color), obtain the liquid S8 of 130mg yellow oily, productive rate 57.5%.
1HNMR(400MHz，CDCl
3)δ(ppm)=1.45(s，27H)，2.58(b，6H)，2.90(b，10H)，3.09(b，8H)，3.39(s，2H)，3.46(s，4H)，3.60(b，18H)，3.76(bs，4H)，5.14(s，2H)，6.91(d，2H，J=8Hz)，7.16(d，2H，J=8Hz)，7.49(t，2H，J=8Hz)，7.55(d，2H，J=8Hz)，7.61(t，1H，J=8Hz)，7.81(t，4H，J=8Hz)。
Step 8: prepare compound L
130mg (115 μm of ol) S8 and 3.0mL (39mmol) trifluoroacetic acid is dissolved in 1.5mL anhydrous methylene chloride, stirred overnight at room temperature under nitrogen protection.The mixture rotary evaporation obtained is except desolventizing, and thick product is dissolved in 10mL tri-water, and after dichloromethane extraction (3 × 10mL), rotary evaporation removes desolventizing and obtains 40mg colourless powder L, productive rate 36.1%.
1HNMR(400MHz，D
2O)δ(ppm)=2.5–3.5(m，52H)，4.09(s，2H)，6.67(b，2H)，6.97(b，2H)，7.14(b，5H)，7.31(b，4H)。
Step 9: prepare compound Tb-L
By 15.2mg (40 μm of ol) TbCl
36H
2the L of O and 20mg (20 μm of ol) is dissolved in 4mL tri-water, by the pH value to 7 of 1MNaOH regulator solution, is then warming up to 80 DEG C of stirrings and spends the night.The mixture rotary evaporation obtained is removed desolventizing, then uses CHCl
3washing (6 × 10mL), rotary evaporation washings obtains 2.8mg colourless powder Tb-L, productive rate 12.5%.
1hNMR (400MHz, CDCl
3) δ (ppm)=0.87 (b, 10H), 1.25 (b, 24H), 1.40 (bm; 2H), 1.94 (bs, 8H), 3.13 (s, 2H); 3.62 (b, 6H), 7.15 (b, 2H); 7.51 (d, 2H, J=8Hz), 7.62 (d; 2H, J=8Hz), 7.82 (d, 5H; J=8Hz), 8.20 (d, 4H, J=8Hz); ES-MSm/z=1118.8 (M+H
+) (calculated value 1119.2), 1140.7 (M+Na
+) (calculated value 1141.2).
Embodiment 3
From the compounds of this invention Tb-L of embodiment 2 to K
+sensitivity experiments
In experiment below, unless specifically indicated and point out, solvent for use is tested in all identifications is all three water.The concentration of the compounds of this invention Tb-L is 8.0 × 10
-4mol/L, the concentration of potassium ion is 0-30mM.
Specific practice is: in some the graduated tool plug test tubes of band, add 8.0 × 10 of 0.5mL respectively
-4the compounds of this invention of mol/L, 0 μ L, 5 μ L, 10.5 μ L, 16 μ L, 21 μ L, 26.5 μ L, 32 μ L, 37.5 μ L, 44 μ L, 51 μ L, 60.5 μ L, 72 μ L, 84 μ L, 95 μ L, 105 μ L, 115 μ L, 125 μ L, 137.5 μ L, the KCl solution of the 1.0mol/L of 150 μ L, constant volume is to 5mL.Be excitation wavelength with 232nm, time of lag is set to 0.2ms, uses CaryEclipse spectrophotofluorometer to obtain the luminous intensity of system at 545nm place.Utilize in the luminous intensity in system under different potassium concentration condition and system the ratio (I/I of luminous intensity when not having potassium ion
0) to K
+concentration map, obtain Fig. 2, as can be seen from Figure 2, the compounds of this invention after adding metal-salt KCl, along with K
+the increase of concentration, luminous intensity strengthens gradually.Work as K
+when concentration is 12mM, luminous intensity strengthens as not add K
+time 19 times of luminous intensity.
Embodiment 4
From the compounds of this invention Tb-L of embodiment 2 to K
+selectivity experiment
In experiment below, unless specifically indicated and point out, solvent for use is tested in all identifications is all three water.The concentration of the compounds of this invention Tb-L is 5.0 × 10
-4mol/L, the concentration of potassium ion is 20mM.Metal-salt NaCl, LiCl, CdCl in test system
2, MnCl
2, FeCl
2, Mg (NO
3)
2, Co (NO
3)
2, Ca (NO
3)
2, Hg (NO
3)
2, Pb (NO
3)
2, Ni (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2concentration be 20mM.
Specific practice is: in some the graduated tool plug test tubes of band, add 5.0 × 10 of 0.5mL respectively
-4the compounds of this invention of mol/L, NaCl, LiCl, CdCl of 100 μ L1.0mol/L
2, MnCl
2, FeCl
2, Mg (NO
3)
2, Co (NO
3)
2, Ca (NO
3)
2, Hg (NO
3)
2, Pb (NO
3)
2, Ni (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2, last constant volume is to 5mL.Be excitation wavelength with 232nm, time delay is set to 0.2ms, the luminous intensity at test 545nm place.In the system identical with above-mentioned condition, add the KCl solution of 100 μ L1.0mol/L, constant volume is to 5mL.Same is excitation wavelength with 232nm, and time of lag is set to 0.2ms, and test system is in the maximum emission intensity at 545nm place.Exist with potassium ion and map with the luminous intensity of system at 545nm place when not existing, containing the potassium ion of 20mM and the corresponding metal ion of equivalent in dark expression system, corresponding metal ion only containing 20mM in light color expression system, does not have potassium ion, sees Fig. 3.Experimental result shows: when having KCl to exist, and high 21 times when the luminous strength ratio of system does not have a KCl, the luminous intensity variations that other metal ions cause is no more than K
+3% of the luminous intensity variations caused, therefore on other physiology, coexisting of significant metal ion does not affect the compounds of this invention to K
+selectivity.Therefore, the compounds of this invention is to K
+there is good recognition reaction and selectivity, can as K
+probe in living things system.
Claims (16)
1. the terbium coordination compound of general formula I:
Wherein R
1, R
2and R
3be hydrogen or be selected from C independently of each other
1-C
6alkyl and C
1-C
6the electron-donating group of alkyl oxy.
2. the terbium coordination compound of general formula I according to claim 1, wherein R
1, R
2and R
3be hydrogen or be selected from C independently of each other
1-C
4alkyl and C
1-C
4the electron-donating group of alkyl oxy.
3. prepare a method for the terbium coordination compound of the general formula I according to claim 1 or 2, it comprises the steps:
Step 1:
Step 2:
Step 3:
Step 4:
Step 5:
Step 6:
Step 7:
Step 8:
Step 9:
Wherein R
1, R
2and R
3as claim 1 or 2 define.
4. method according to claim 3, wherein step 1 is carried out at room temperature to 40 DEG C, the mol ratio of tert-Butyl dicarbonate and compound 1 is 1, reaction times is 10-30 hour and step 1 is carried out in the solvent being selected from dioxane, methylene dichloride and trichloromethane, and every g compound 1 uses 10-1000ml solvent.
5. method according to claim 3; wherein step 2 is carried out under nitrogen protection, and temperature of reaction is 40-70 DEG C, and the reaction times is 10-30 hour; compound 3 is 1-2 with the mol ratio of compound 2, and step 2 is being selected from Cs in the solvent being selected from MeCN, DMF and DMSO
2cO
3and Na
2cO
3alkali exist under carry out, every g compound 2 uses 10-1000ml solvent and every mol compound 2 uses 1-5mol alkali.
6. method according to claim 4; wherein step 2 is carried out under nitrogen protection, and temperature of reaction is 40-70 DEG C, and the reaction times is 10-30 hour; compound 3 is 1-2 with the mol ratio of compound 2, and step 2 is being selected from Cs in the solvent being selected from MeCN, DMF and DMSO
2cO
3and Na
2cO
3alkali exist under carry out, every g compound 2 uses 10-1000ml solvent and every mol compound 2 uses 1-5mol alkali.
7. the method any one of claim 3-6; wherein step 3 is carried out under nitrogen protection, and temperature of reaction is 20-50 DEG C, and the reaction times is 0.5-2 hour; compound 5 is 1-1.5 with the mol ratio of compound 4, and step 3 is being selected from Cs in the solvent being selected from DMF, acetonitrile and DMSO
2cO
3and Na
2cO
3alkali exist under carry out, every g compound 4 uses 10-1000ml solvent and every mol compound 4 uses 1-5mol alkali.
8. method according to claim 7, the compound 5 wherein in step 3 reacts by making corresponding 4-methyl benzophenone compound and bromine and obtains.
9. the method any one of claim 3-6, wherein step 4 is carried out under the ethyl acetate solution of trifluoroacetic acid or hydrogenchloride exists, the mol ratio of trifluoroacetic acid or hydrogenchloride and compound 6 is 2-100, temperature of reaction is 20-50 DEG C, reaction times is 1-2 hour, and step 4 is carried out under the solvent being selected from methylene dichloride, trichloromethane and dioxane exists and every g compound 6 uses 10-1000ml solvent.
10. the method any one of claim 3-6, wherein first step 5 by adding chloroacetyl chloride in compound 7 at-5 DEG C to 5 DEG C, be increased to room temperature after adding and carry out, wherein the reaction times is 2-5 hour, the mol ratio of chloroacetyl chloride and compound 7 is 1.5-4, and step 5 is being selected from triethylamine, pyridine, Na in the solvent being selected from methylene dichloride, trichloromethane and DMF
2cO
3and Cs
2cO
3alkali exist under carry out, every g compound 7 uses 10-1000ml solvent and every mol compound 7 uses 1-5mol alkali.
11. methods any one of claim 3-6, wherein step 6 is by being at room temperature added dropwise to Isosorbide-5-Nitrae by compound 8,7, in 10-tetraazacyclododecanand, be warming up to 50-70 DEG C after adding and carry out, wherein the reaction times is 6-10 hour, 1,4, the mol ratio of 7,10-tetraazacyclododecanand and compound 8 is 1.5-5, and step 6 is being selected from Cs in the solvent being selected from acetonitrile, DMF and DMSO
2cO
3, Na
2cO
3carry out under existing with the alkali of triethylamine, every g compound 8 uses 10-1000ml solvent and every mol compound 8 uses 1-5mol alkali.
12. methods any one of claim 3-6, wherein step 7 is carried out at 20-50 DEG C, reaction times is 10-20 hour, and the mol ratio of bromo-acetic acid tert-butyl and compound 9 is 3-6, and step 7 is being selected from Cs in the solvent being selected from acetonitrile, trichloromethane, DMF and DMSO
2cO
3, Na
2cO
3, triethylamine alkali exist under carry out, every g compound 9 uses 10-1000ml solvent and every mol compound 9 uses 2-10mol alkali.
13. methods any one of claim 3-6, wherein step 8 is carried out under room temperature and nitrogen protection, and step 8 is carried out in the solvent being selected from methylene dichloride, trichloromethane, acetonitrile and DMF and every g compound 10 uses 5-100ml solvent.
14. methods any one of claim 3-6, wherein step 9 by with sodium hydroxide by TbCl
36H
2it is 6-8 that the aqueous solution of O and compound 11 is adjusted to pH, and then react under 70 DEG C to backflow and carry out, wherein the concentration of the aqueous solution of compound 11 is 2-10mmol/L, and the reaction times is 10-30 hour and TbCl
36H
2the mol ratio of O and compound 11 is 1.5-5.
15. compounds 11:
Wherein R
1, R
2and R
3as claim 1 or 2 define.
16. according to the terbium coordination compound of the general formula I of claim 1 or 2 purposes as potassium ion identification agent.
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| JP2007238650A (en) * | 2006-03-03 | 2007-09-20 | Kyoto Univ | Rare earth metal complex and fluorescent material using the same |
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| JP2009215238A (en) * | 2008-03-11 | 2009-09-24 | Osaka Univ | Rare earth luminescent probe |
| CN101705084A (en) * | 2009-11-09 | 2010-05-12 | 东南大学 | Multicolour rare earth nano particle and preparation method thereof |
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| CN101348468A (en) * | 2007-07-16 | 2009-01-21 | 中国医学科学院放射医学研究所 | P-isosulfhydryl phenyl five-membered nitrogen heterocyclic ring tetraacethyl chelate and preparation thereof |
| JP2009215238A (en) * | 2008-03-11 | 2009-09-24 | Osaka Univ | Rare earth luminescent probe |
| CN101705084A (en) * | 2009-11-09 | 2010-05-12 | 东南大学 | Multicolour rare earth nano particle and preparation method thereof |
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| 《Luminescent Tb3+ Complex with Pendant Crown Ether Showing Dual-Component Recognition of H+ and K+ at Multiple pH Windows》;Cong Li等;《ORGANIC LETTERS》;20041120;第6卷(第26期);4841-4844 * |
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