CN102153575A - Dioxane-coordinated rare-earth coordination compound, and preparation method and application thereof - Google Patents

Dioxane-coordinated rare-earth coordination compound, and preparation method and application thereof Download PDF

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CN102153575A
CN102153575A CN2011100318379A CN201110031837A CN102153575A CN 102153575 A CN102153575 A CN 102153575A CN 2011100318379 A CN2011100318379 A CN 2011100318379A CN 201110031837 A CN201110031837 A CN 201110031837A CN 102153575 A CN102153575 A CN 102153575A
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dioxane
ppa
rare earth
rare
earth compounding
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CN102153575B (en
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陶栋梁
崔玉民
徐怡庄
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Fuyang Normal University
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Fuyang Normal University
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Abstract

The invention provides a rare-earth fluorescent coordination compound synthesized by using dioxane micromolecule as a second ligand and pipemidic acid (PPA) as a first ligand, and a preparation method thereof. Due to the existence of dioxane, the fluorescence of the rare-earth coordination compound is obviously enhanced, and the fluorescence lifetime of the rare-earth coordination compound is greatly influenced when the dioxane is used as the second ligand. The novel rare-earth coordination compound provides a new optional reagent for quinolone broad-spectrum antibacterial drugs, and the fluorescence enhanced phenomenon also provides a new method for detecting existence and content of micromolecule dioxane.

Description

Dioxane participates in coordinate rare earth compounding and its production and use
Technical field
The invention provides a kind of dioxane (dioxane) small molecules that utilizes as second part, pipemidic acid (PPA) is as first part institute synthetic rare earth compounding, with and preparation method thereof.
Background technology
At the research and development rare earth compounding, especially seek in the fluorescent rare earth title complex process of excellent property, need find suitable part just can synthesize all gratifying rare earth compounding of stable performance and luminous intensity and fluorescence lifetime.
1, the 4-dioxane claims dioxane Huo diox (dioxide) again, is colourless combustible liquid, and little have an ethereal odor, is a kind of good organic solvent, of many uses, can be used as the solvent of cellulose ethanoate and many resins.Can be used as extraction agent in pharmaceutical industries, used as stabilizers in 1 is produced in Synthetic Leather is produced, substitutes dimethylformamide, tetrahydrofuran (THF) as volatile solvent.In coating, painting technology, make stripper.In dyestuffs industries as solvent and dispersion agent, used as stabilizers aspect printing-ink.And can be used as metal conditioner, also can be used for aspects such as makeup, spices manufacturing, plating.But the method to its detection mainly is confined to gas chromatograph-mass spectrometer and liquid phase chromatography, for example referring to Zhang Zhi-hong, SunXiao-juan (Zhang Zhihong, Sun Xiaojuan).Chinese Journal of Chromatography (chromatogram), 1998,16 (3): 244-246; Ma Jian, Qian Chun-mei, Chen Jian-hua (Ma Jian, Qian Chunmei, Chen Jianhua).Surfactant Industry (tensio-active agent industry), 2000,2:41-43; SCALIA S.J.Pharm.Biomed.Anal., 1990,8:867-870; With Xi Xing-lin, Bao Lun-jun, Chen Jie, et al. (Xi Xinglin, Bao Lunjun, Chen Jie, etc.).China Surfactant Detergent ﹠amp; Cosmetics (daily chemical industry), 2003,33 (6): 390-392.Sample pretreating method has distillation, Solid-Phase Extraction, but the operation of these methods is all more loaded down with trivial details, and more time-consuming.Exploring a kind of novel method detection dioxane has very important significance.
Pipemidic acid is a kind of quinolones extensive pedigree antibiotic, and this molecule has bigger conjugated system, and is sterically hindered very big, during therefore as the part synthetic compound, is difficult to find the second suitable part.It is a kind of approach that develops newtype drug that rare earth ion and pipemidic acid prepare rare earth compounding.Yang Lin etc. had once studied the anti-microbial activity of rare earth ion and the prepared rare earth compounding of pipemidic acid, found to strengthen to some extent than independent pipemidic acid, and the research work of this respect is for example referring to Yang L, TaoD L, Yang X L, et al.Chemical; Pharmaceutical Bulletin, 2003,51 (5): 494-498; With Yang L, Li W, Tao D L, et al.Synthesis And Reactivity InInorganic And Metal-Organic Chemistry, 1999,29 (8): 1485-1494.
The present invention proposes for these needs that satisfy prior art just.
Summary of the invention
The inventor is through discovering with keen determination, the dioxane small molecules can be used as the coordination of second part participation rare earth/pipemidic acid title complex and synthesizes, form the stable novel title complex of rare earth/pipemidic acid/dioxane, this coordination mode has specificity, because other small molecules solvent for example ethanol, acetone, tetrahydrofuran (THF) etc. all is difficult to replace dioxane and rare earth/pipemidic acid to form stable title complex, though and the Norxin similar is difficult to substitute pipemidic acid to form similar title complex in pipemidic acid also; Because the existence of dioxane, the fluorescence of this rare earth compounding is obviously strengthened, and dioxane has a significant impact as the fluorescence lifetime of second part to rare earth compounding; This novel rare earth compounding is not only for the quinolones extensive pedigree antibiotic provides new Gong screening reagent, and this fluorescence enhancing phenomenon also provides a kind of new method for existence and the content thereof that detects the small molecules dioxane; Finish the present invention thus.
Therefore, one of purpose of the present invention is to provide a kind of dioxane small molecules as second part, and pipemidic acid (PPA) is as first part synthetic rare earth compounding, the i.e. rare earth/pipemidic acid/dioxane complex.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned this rare earth compounding.
The inventor finds that after deliberation this novel complex fluorescent intensity has obtained significantly improving, and therefore provides new method for the existence that detects dioxane.The synthetic of this novel title complex also provides new Gong screening reagent for the quinolones extensive pedigree antibiotic.
Therefore, another object of the present invention is to provide a kind of method that detects dioxane, synthesizing rare-earth/pipemidic acid title complex at first, then in the presence of dioxane, as the further synthesizing rare-earth/pipemidic acid of second part/dioxane complex, whether and content the existence that the formation by title complex and the variation of amount thereof detect dioxane with it.
Another purpose of the present invention also is to provide a kind of quinolones extensive pedigree antibiotic, this medicine contains with the dioxane small molecules as second part, with pipemidic acid (PPA) as first part synthetic rare earth compounding, the i.e. rare earth/pipemidic acid/dioxane complex.
The following specifically describes the present invention.
In one embodiment of the invention, provide a kind of dioxane small molecules as second part, pipemidic acid (PPA) is as first part synthetic rare earth compounding, the i.e. rare earth/pipemidic acid/dioxane complex.
In the present invention, the rare earth element Ln in the described rare earth compounding can be can emitting fluorescence any rare earth element, as europium (Eu), terbium (Tb), samarium (Sb) or dysprosium (Dy) etc., preferred europium and terbium, preferred formed title complex is Ln (PPA) 3Dioxane, wherein, Ln=Eu or Tb, PPA are pipemidic acids, dioxane is a dioxane.
In the present invention, measured Eu (PPA) respectively 3NH 2O (n is generally 6), Tb (PPA) 3NH 2O (n is generally 6), Eu (PPA) 3Dioxane and Tb (PPA) 3The infrared spectra of dioxane, as shown in drawings.At Eu (PPA) 3In the infrared spectra of dioxane, at 1625cm -1There is a narrow peak at the place, and at 1547cm -1There is a broad peak at the place.At Tb (PPA) 3In the infrared spectra of dioxane, at 1625cm -1There is a narrow peak at the place, and at 1276cm -1There is a peak at the place.Eu (PPA) 3Dioxane and Tb (PPA) 3The infrared spectrogram of dioxane is closely similar, and the similar of the two is described, Eu (PPA) 3NH 2O and Tb (PPA) 3NH 2The infrared spectra of O is also closely similar, and its structural similitude is described.
In another embodiment of the present invention, a kind of method for preparing above-mentioned this rare earth compounding is provided, at first under alkaline condition, in the presence of organic solvent, with pipemidic acid (PPA) as first part, with the rare earth compounding of the synthetic single part of rare earth ion, choose wantonly then under alkaline condition, in the presence of organic solvent, with the dioxane small molecules as second part, synthesizing rare-earth/pipemidic acid/dioxane complex.
In preparation method of the present invention, the rare earth that is adopted can be can emitting fluorescence any rare earth element, as europium (Eu), terbium (Tb), samarium (Sb) or dysprosium (Dy) etc., preferred europium and terbium, preferred formed title complex is Ln (PPA) 3Dioxane, wherein, Ln=Eu or Tb, PPA are pipemidic acids, dioxane is a dioxane.
In preparation method of the present invention, alkaline condition is meant and has alkaline matter, as mineral alkalis such as sodium hydroxide, potassium hydroxide or ammoniacal liquor, perhaps organic bases such as trolamine, pyridine, preferred mineral alkali such as sodium hydroxide or the potassium hydroxide of using more preferably uses sodium hydroxide.
Described organic solvent be for can dissolving the solvent of PPA and rare-earth salts, preferred alcohols kind solvent, methyl alcohol for example, ethanol, propyl alcohol and butanols, preferred alcohol, more preferably dehydrated alcohol.
Above-mentioned rare-earth salts for example is the inorganic salt of europium or terbium, and the hydrochloride of preferred europium or terbium is as EuCl 3And TbCl 3, perhaps its hydrate is as EuCl 36H 2O and TbCl 36H 2O.
In preferred manufacturing procedure of the present invention, when the rare earth compounding of synthetic single part, at first PPA and mineral alkali are dissolved in the organic solvent, and rare-earth salts is dissolved in separately in this organic solvent, solution with rare-earth salts adds in the solution of PPA and mineral alkali reaction for some time then.
The synthetic and then original position of two ligand rare earth title complexs is carried out, and add dioxane this moment in above-mentioned reaction mixture, then has precipitation to generate, and is the rare earth compounding of two parts; Also can with more than the rare earth compounding solution of single part of making under situation about vacuumizing, solvent evaporation is come out, obtain the rare earth compounding that pressed powder is single part, then it is dissolved in the organic solvent, the optional alkaline matter that adds, and to wherein adding dioxane, generate precipitation, be the rare earth compounding of two parts.
In the preferred preparation method of the present invention, PPA and NaOH are dissolved in the dehydrated alcohol jointly.Then, EuCl 36H 2O or TbCl 36H 2O is dissolved in the dehydrated alcohol, this solution is dropwise added in the ethanol solution of above-mentioned PPA and NaOH.Use Rotary Evaporators under situation about vacuumizing, temperature is controlled at 60 ℃, and etoh solvent is evaporated, and resulting pressed powder is Eu (PPA) 3NH 2O or Tb (PPA) 3NH 2O, wherein n is 1～6, puts into the moisture eliminator drying for standby, the value of n is decided on solvent evaporation situation and degree of drying.When preparing the rare earth compounding of two parts, it is dissolved in the dehydrated alcohol, chooses the adding alkaline matter wantonly, and the precipitation generation is arranged, be Eu (PPA) to wherein adding excessive dioxane, can seeing 3Dioxane or Tb (PPA) 3Dioxane.
Also can be behind the rare earth compounding of the single part of preparation the rare earth compounding of the two parts of in-situ preparing, its step is as follows: under stirring action constantly, PPA and NaOH are dissolved in the dehydrated alcohol jointly.Temperature is controlled at about 80 ℃, keeps reflux state.Then, with EuCl 36H 2O or TbCl 36H 2O is dissolved in the dehydrated alcohol, this solution is dropwise added in the ethanol solution of above-mentioned PPA and NaOH.In solution, add excessive dioxane at last, can see having precipitation to generate, be Eu (PPA) 3Dioxane or Tb (PPA) 3Dioxane, filtering-depositing put into the moisture eliminator drying for standby.
From experimental phenomena, synthesizing rare-earth title complex Eu (PPA) 3Dioxane and Tb (PPA) 3During dioxane, after the second part dioxane adds, have precipitation to generate, this illustrates that second part has participated in coordination.And a spot of dioxane has just added fashionable not a large amount of precipitation generation, and its reason is that the dioxane solvent molecule at first dissolves in and formed hydrogen bond in the dehydrated alcohol.
According to Yang Jun, Xu Yi-zhuang, Weng Shi-fu, et al. (Yang Jun, Xu Yizhuan, Weng Shifu, Deng) Spectroscopy and Spectral Analysis (spectroscopy and spectroscopic analysis), 2002,22 (5): the report of 741-744, the quinolones hapto mainly is the Sauerstoffatom of carboxyl, and carboxyl negative ion after pipemidic acid loses hydrogen under alkaline environment and rare earth ion form the chelating coordinate bond.
In yet another embodiment of the invention, a kind of method that detects dioxane is provided, synthesizing rare-earth/pipemidic acid title complex at first, then in the presence of dioxane, with it as the further synthesizing rare-earth/pipemidic acid of second part/dioxane complex, judge whether to exist dioxane by whether forming described pair of ligand-complexes, and detect the content of dioxane according to the variation of amount before and after the title complex.
In yet another embodiment of the invention, a kind of quinolones extensive pedigree antibiotic is provided, this medicine contains the dioxane small molecules as second part, and pipemidic acid (PPA) is as first part synthetic rare earth compounding, the i.e. rare earth/pipemidic acid/dioxane complex.
Description of drawings
Fig. 1 is the schematic arrangement of pipemidic acid;
Fig. 2 is part PPA, title complex Eu (PPA) 36H 2O and Eu (PPA) 3Dioxane is from 1200cm -1To 1700cm -1Infrared spectrogram;
Fig. 3 is part PPA, title complex Tb (PPA) 36H 2O and Tb (PPA) 3Dioxane is from 1200cm -1To 1700cm -1Infrared spectrogram;
Fig. 4 and Fig. 5 are title complex Eu (PPA) 36H 2O and Eu (PPA) 3The excitation spectrum of dioxane and emmission spectrum figure, the monitoring wavelength of excitation spectrum is 612nm;
Fig. 6 and Fig. 7 are title complex Tb (PPA) 36H 2O and Tb (PPA) 3The excitation spectrum of dioxane and emmission spectrum figure, the monitoring wavelength of excitation spectrum is 546nm;
Fig. 8 and Fig. 9 are title complex Eu (PPA) 36H 2O and Eu (PPA) 3The dioxane fluorescence decay curve;
Figure 10 and Figure 11 are title complex Tb (PPA) 36H 2O and Tb (PPA) 3The fluorescence decay curve of dioxane;
Figure 12 and Figure 13 are title complex Ln (PPA) 3NH 2O and Ln (PPA) 3Dioxane (Ln=Eu, structural formula Tb).
Embodiment
Below with preferred embodiment and further specify the present invention in conjunction with the accompanying drawings.Characteristics of the present invention and advantage will become more clear along with these explanations.But, these embodiments only are illustrative, and it is to protection scope of the present invention and do not constitute any limitation.It will be appreciated by those skilled in the art that under the situation that does not exceed or depart from protection domain of the present invention, technical solutions and their implementation methods of the present invention have multiple modification, improvement or Equivalent, these all should fall within the scope of protection of the present invention.
Reagent
Reagent of the present invention is:
99.9% Eu 2O 3Be dissolved in the dilute hydrochloric acid, slowly crystallization EuCl is separated out in evaporation 36H 2O, suction filtration go out crystal and are positioned over drying for standby in the moisture eliminator.
Under continuous condition of stirring, dropwise add hydrogen peroxide, make 99.9% Tb 4O 7Be dissolved in the dilute hydrochloric acid, slowly crystallization TbCl is separated out in evaporation 36H 2O, suction filtration go out crystal and are positioned over drying for standby in the moisture eliminator.
Pipemidic acid is purchased in Shandong Xinhua Pharmaceutical Factory.
Dehydrated alcohol and dioxane all are analytical reagent.
Embodiment 1: rare earth compounding Eu (PPA) 3NH 2O and Tb (PPA) 3NH 2The preparation of O (n is 1～6)
Under stirring action constantly, the PPA (0.357g) of 3mmol and the NaOH (0.12g) of 3mmol are dissolved in the 30ml dehydrated alcohol jointly.Then, the EuCl of 1mmol 36H 2O is dissolved in the dehydrated alcohol of 10mL, this solution is dropwise added in the solution of above-mentioned PPA and NaOH.Use Rotary Evaporators (RE-52AA) under situation about vacuumizing, temperature is controlled at 60 ℃, and etoh solvent is evaporated, and resulting pressed powder is Eu (PPA) 3NH 2O puts into the moisture eliminator drying for standby, and wherein n is 1～6, decides on evaporation and degree of drying, and general n is 6.
Tb (PPA) 3NH 2The preparation method of O also adopts similar method, and is specific as follows:
Under stirring action constantly, the PPA of 3mmol and the NaOH of 3mmol are dissolved in the 30ml dehydrated alcohol jointly.Then, the TbCl of 1mmol 36H 2O is dissolved in the dehydrated alcohol of 10mL, this solution is dropwise added in the solution of above-mentioned PPA and NaOH.Use Rotary Evaporators under situation about vacuumizing, temperature is controlled at 65 ℃, and etoh solvent is evaporated, and resulting pressed powder is Tb (PPA) 3NH 2O puts into the moisture eliminator drying for standby, and wherein n is 1～6, decides on evaporation and degree of drying, and general n is 6.
Embodiment 2: rare earth compounding Eu (PPA) 3Dioxane and Tb (PPA) 3The preparation of dioxane
The preparation method one:
Under stirring action constantly, the PPA (0.357g) of 3mmol and the NaOH (0.12g) of 3mmol are dissolved in the 30mL dehydrated alcohol jointly.Temperature is controlled at about 80 ℃, keeps reflux state.Then, with the EuCl of 1mmol 36H 2O is dissolved in the dehydrated alcohol of 10mL, this part solution is dropwise added in the solution of above-mentioned PPA and NaOH.In solution, add excessive dioxane (10mL) at last, can see that light-yellow precipitate Eu (PPA) is arranged 3Dioxane generates.Filtering-depositing is put into the moisture eliminator drying for standby.
Tb (PPA) 3Similar method is also adopted in the preparation of dioxane, and is specific as follows:
Under stirring action constantly, the PPA of 3mmol and the NaOH of 3mmol are dissolved in the 30mL dehydrated alcohol jointly.Temperature is controlled at about 80 ℃, keeps reflux state.Then, with the TbCl of 1mmol 36H 2O is dissolved in the dehydrated alcohol of 10mL, this part solution is dropwise added in the solution of above-mentioned PPA and NaOH.In solution, add excessive dioxane (10mL) at last, can see that precipitation Tb (PPA) is arranged 3Dioxane generates.Filtering-depositing is put into the moisture eliminator drying for standby.
The preparation method two:
The pressed powder Eu (PPA) that embodiment 1 is made 3NH 2O or Tb (PPA) 3NH 2O is dissolved in the dehydrated alcohol, optional adding proper amount of sodium hydroxide, and in solution, add excessive dioxane, and can see having precipitation to generate, be Eu (PPA) 3Dioxane or Tb (PPA) 3Dioxane.
From experimental phenomena, synthesizing rare-earth title complex Eu (PPA) 3Dioxane and Tb (PPA) 3In the time of dioxane, add the second part dioxane after, have precipitation to generate, this illustrates that second part has participated in coordination.The quinolones hapto mainly is the Sauerstoffatom of carboxyl.Fig. 1 is the schematic arrangement of pipemidic acid, adds sodium hydroxide is captured carboxyl in the pipemidic acid in ethanolic soln hydrogen, and the carboxyl negative ion then forms the chelating coordinate bond with rare earth ion.
Test implementation example 3: the mensuration of infrared spectra
Part PPA and prepared rare earth compounding adopt on Nicolet Magna-IR 750 Fourier's micro ft-ir spectroscopy instrument to be measured.Spectral resolution 4cm -1, scan scanning area 4000-400cm 64 times -1
Fig. 2 is part PPA, title complex Eu (PPA) 3NH 2O (n=6) and Eu (PPA) 3Dioxane is from 1200cm -1To 1700cm -1Infrared spectrogram.
As we can see from the figure, PPA is by after reacting with rare earth ion, and obvious variation has taken place spectrum.1641cm -1And 1619cm -1Two peaks at place have become a 1627cm -1Broad peak and an acromion.1580cm -1The spike at place disappears, at 1541cm -1One broad peak appears in the place.After the second part dioxane participates in reaction, at 1627cm -1The peak position at place becomes a narrow peak and has moved to 1625cm -1, this may replace crystal water relevant with second part.1541cm -1The peak position generation broadening at place has also moved to 1547cm -1As seen the participation of second part has certain influence for its infrared spectra, illustrates that the adding of dioxane causes the rare earth compounding structure that certain variation has taken place.
Fig. 3 is part PPA, title complex Tb (PPA) 3NH 2O (n=6) and Tb (PPA) 3Dioxane is from 1200cm -1To 1700cm -1Infrared spectrogram.
Form title complex Tb (PPA) 3NH 2Behind the O, 1641cm -1And 1619cm -1Two peaks at place have become a 1618cm -1Broad peak.1580cm -1The spike at place disappears, at 1545cm -1One broad peak appears in the place.After the second part dioxane participates in reaction, at 1618cm -1The peak position at place narrows down slightly and has moved to 1625cm -1, this may replace crystal water relevant with second part.The relative intensity of all peak positions all changes to some extent.In addition, at 1276cm -1A new peak has appearred in the place.As seen the participation of second part has certain influence for its infrared spectra, illustrates that the adding of dioxane causes the rare earth compounding structure that certain variation has taken place.
In addition, owing on the fluorescence emission spectrum of above two kinds of title complexs Eu is arranged all 3+And Tb 3+The feature emission peak, illustrate that coordination reaction has taken place for rare earth ion and PPA, has formed title complex.
Test implementation example 4: the mensuration of fluorescence spectrum.
Fluorescence spectrum is measured on the F-4500 spectrophotofluorometer.
Fig. 4 and Fig. 5 are title complex Eu (PPA) 3NH 2O (n=6) and Eu (PPA) 3The excitation spectrum of dioxane and emmission spectrum figure.The monitoring wavelength of excitation spectrum is 612nm, the intensity of two kinds of title complex excitation spectrums is adjusted to can be compared state.
Can see Eu (PPA) 3The excitation spectrum of dioxane is than Eu (PPA) 3NH 2O (n=6) obviously broadens.As excitation wavelength, can see Eu (PPA) with 351nm 3The fluorescence intensity ratio Eu (PPA) of dioxane 3NH 2The enhancing of O (n=6) nearly one times.This shows that dioxane participates in after the coordination fluorescence to title complex and strengthens and have important contribution.The fluorescence enhanced mechanism may be because replaced water molecules behind two oxygen of dioxane and the rare-earth ion coordination, makes the complex molecule compact construction, thermal vibration minimizing and strengthened fluorescence.
Fig. 6 and Fig. 7 are title complex Tb (PPA) 3NH 2O (n=6) and Tb (PPA) 3The excitation spectrum of dioxane and emmission spectrum figure.The monitoring wavelength of excitation spectrum is 546nm, the intensity of two kinds of title complex excitation spectrums is adjusted to can be compared state.
Can see Tb (PPA) 3The excitation spectrum of dioxane before 400nm than broad, and Tb (PPA) 3NH 2The excitation spectrum of O (n=6) at 400nm later on than broad.As excitation wavelength, can see Tb (PPA) with 351nm 3The fluorescence intensity ratio Tb (PPA) of dioxane 3NH 2The enhancing of O (n=6) nearly 20 times.This shows that dioxane participates in after the coordination fluorescence to title complex and strengthens and have important contribution.The fluorescence enhanced mechanism may be because replaced water molecules behind two oxygen of dioxane and the rare-earth ion coordination, makes the complex molecule compact construction, thermal vibration minimizing and strengthened fluorescence.Simultaneously, with Eu 3+Formed title complex contrast illustrates PPA and rare earth Tb 3+The energy level matching is poor.
Test implementation example 5: the mensuration of time lifetime.
What the mensuration of time lifetime was used is the stable state transient time to differentiate fluorescence spectrophotometer (Britain Edinburgh Instruments Ltd.).
Fig. 8 and Fig. 9 are title complex Eu (PPA) 3NH 2O (n=6) and Eu (PPA) 3The dioxane fluorescence decay curve.Carry out two exponential fittings by extinction curve and obtain its fluorescence lifetime title complex.
Fitting result shows title complex Eu (PPA) 3NH 2O (n=6) and Eu (PPA) 3Dioxane has two life-spans, for Eu (PPA) 3NH 2O (n=6), τ 1=991 μ s (75%), τ 2=478 μ s (25%).For Eu (PPA) 3Dioxane, τ 1=317 μ s (5%), τ 2=897 μ s (95%).As seen very big variation has taken place in the fluorescence decay process of two kinds of title complexs.Eu (PPA) 3Long fluorescence decay process of experience is the fluorescence decay process of a weak point then earlier; And Eu (PPA) 3Dioxane then is the attenuation process that experiences a weak point earlier, is a long attenuation process then.
Figure 10 and Figure 11 are title complex Tb (PPA) 3NH 2O (n=6) and Tb (PPA) 3The fluorescence decay curve of dioxane.
Two exponential fitting results show that the two all has two life-spans.For Tb (PPA) 3NH 2O (n=6), τ 1=21 μ s (39%), τ 2=101 μ s (61%).For Tb (PPA) 3Dioxane, τ 1=161 μ s (28%), τ 2=494 μ s (72%).As seen very big variation has taken place in the fluorescence decay time of the two, and the fluorescence decay time of two processes of the latter all is far longer than the former, and this has just explained that the latter's fluorescence intensity is better than the former reason far away.
Contrast Eu and the formed title complex of Tb, can see that the formed title complex of different rare earth ions adds dioxane after, its fluorescence lifetime changes and is inequality.The formed title complex of Eu has been put upside down the fluorescence decay time of two processes after adding dioxane, and makes the fluorescence decay time of two processes all increase behind the formed title complex adding of the Tb dioxane.This has illustrated for its energy transfer process difference of the formed title complex of different rare earth ions very big, may be relevant with the level structure of rare earth ion itself.
According to above experimental result, Figure 12 and Figure 13 have provided title complex Ln (PPA) 3NH 2O and Ln (PPA) 3Dioxane (Ln=Eu, structural formula Tb).
Abovely describe the present invention in conjunction with specific embodiments.But, these embodiments only are illustrative, and it is to protection scope of the present invention and do not constitute any limitation.It will be appreciated by those skilled in the art that under the situation that does not exceed or depart from protection domain of the present invention, technical solutions and their implementation methods of the present invention have multiple modification, improvement or Equivalent, these all should fall within the scope of protection of the present invention.

Claims (10)

1. rare earth compounding, its be by dioxane as second part, pipemidic acid (PPA) is as the first part synthetic, i.e. rare earth/pipemidic acid/dioxane complex.
2. rare earth compounding according to claim 1 is characterized in that, the rare earth element Ln in the described rare earth compounding be can emitting fluorescence rare earth element, as preferred europium (Eu), terbium (Tb), samarium (Sb) or dysprosium (Dy) etc., preferred europium and terbium; Preferred formed title complex is Ln (PPA) 3Dioxane, wherein, Ln=Eu or Tb, PPA are pipemidic acids, dioxane is a dioxane.
3. rare earth compounding according to claim 2 is characterized in that, at Eu (PPA) 3In the infrared spectra of dioxane, at 1625cm -1There is a narrow peak at the place, and at 1547cm -1There is a broad peak at the place; At Tb (PPA) 3In the infrared spectra of dioxane, at 1625cm -1There is a narrow peak at the place, and at 1276cm -1There is a peak at the place.
4. method for preparing according to the described rare earth compounding of one of claim 1 to 3, at first under alkaline condition, in the presence of organic solvent, with pipemidic acid (PPA) as first part, with the rare earth compounding of the synthetic single part of rare earth ion, choose wantonly then under alkaline condition, in the presence of organic solvent, with dioxane as second part, synthesizing rare-earth/pipemidic acid/dioxane complex.
5. method according to claim 4 is characterized in that, the rare earth that is adopted be can emitting fluorescence rare earth element, as europium (Eu), terbium (Tb), samarium (Sb) or dysprosium (Dy) etc., preferred europium and terbium; Preferred formed title complex is Ln (PPA) 3Dioxane, wherein, Ln=Eu or Tb, PPA are pipemidic acids, dioxane is a dioxane.
6. according to claim 4 or 5 described methods, it is characterized in that, alkaline condition is meant and has alkaline matter, as mineral alkalis such as sodium hydroxide, potassium hydroxide or ammoniacal liquor, perhaps organic bases such as trolamine, pyridine, preferred mineral alkali such as sodium hydroxide or the potassium hydroxide of using more preferably uses sodium hydroxide; Described organic solvent is an alcoholic solvent, methyl alcohol for example, ethanol, propyl alcohol and butanols, preferred alcohol, more preferably dehydrated alcohol; Described rare-earth salts is the inorganic salt of europium or terbium, preferred europium or terbium hydrochloride, as EuCl 3And TbCl 3, perhaps its hydrate is as EuCl 3.6H 2O and TbCl 3.6H 2O.
7. according to the described method of one of claim 4 to 6, it is characterized in that,
When the rare earth compounding of synthetic single part, at first PPA and mineral alkali are dissolved in the organic solvent, and rare-earth salts is dissolved in separately in this organic solvent, the solution with rare-earth salts adds in described PPA and the formed solution of mineral alkali then, react,
When the rare earth compounding of synthetic two parts, perhaps behind the rare earth compounding of synthetic single part and then original position carry out, add dioxane this moment in above-mentioned reaction mixture, then have precipitation to generate, and is the rare earth compounding of two parts; The rare earth compounding solution of the single part that makes more than perhaps inciting somebody to action comes out solvent evaporation under situation about vacuumizing, obtain the rare earth compounding that pressed powder is single part, then it is dissolved in the organic solvent, the optional alkaline matter that adds, and to wherein adding dioxane, generate precipitation, be the rare earth compounding of two parts.
8. according to the described method of one of claim 4 to 7, it is characterized in that,
PPA and NaOH are dissolved in the dehydrated alcohol jointly, then with EuCl 3.6H 2O or TbCl 3.6H 2O is dissolved in the dehydrated alcohol, this solution is dropwise added in the ethanol solution of above-mentioned PPA and NaOH, uses Rotary Evaporators under situation about vacuumizing, and temperature is controlled at 60 ℃, and etoh solvent is evaporated, and resulting pressed powder is Eu (PPA) 3NH 2O or Tb (PPA) 3NH 2O, wherein n is 1～6, puts into the moisture eliminator drying for standby;
When preparing the rare earth compounding of two parts, with Eu (PPA) 3.nH 2O or Tb (PPA) 3.nH 2O is dissolved in the dehydrated alcohol, optional adding alkaline matter, and, have precipitation to generate to wherein adding excessive dioxane, be Eu (PPA) 3Dioxane or Tb (PPA) 3Dioxane,
The perhaps rare earth compounding of the two parts of in-situ preparing behind the rare earth compounding of the single part of preparation, its step is as follows:
Under stirring action constantly, PPA and NaOH are dissolved in the dehydrated alcohol jointly, temperature is controlled at about 80 ℃, keeps reflux state, then, with EuCl 3.6H 2O or TbCl 3.6H 2O is dissolved in the dehydrated alcohol, this solution is dropwise added in the ethanol solution of above-mentioned PPA and NaOH, adds excessive dioxane at last in solution, has precipitation to generate, and is Eu (PPA) 3Dioxane or Tb (PPA) 3Dioxane, filtering-depositing, it is dry to put into moisture eliminator.
9. method that detects dioxane, according to the method for one of claim 4 to 8 synthesizing rare-earth/pipemidic acid title complex at first, then in the presence of dioxane, with it as the further synthesizing rare-earth/pipemidic acid of second part/dioxane complex, judge whether to exist dioxane by whether forming described pair of ligand-complexes, and detect the content of dioxane according to the variation of amount before and after the title complex.
10. quinolones extensive pedigree antibiotic, this medicine contains the rare earth compounding of one of with good grounds claim 1 to 3, promptly by dioxane as second part, pipemidic acid is as the synthetic rare earth/pipemidic acid/dioxane complex that obtains of first part.
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