CN107129425A - A kind of calixarenes fluorescent chemicals and its application - Google Patents
A kind of calixarenes fluorescent chemicals and its application Download PDFInfo
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- CN107129425A CN107129425A CN201710514919.6A CN201710514919A CN107129425A CN 107129425 A CN107129425 A CN 107129425A CN 201710514919 A CN201710514919 A CN 201710514919A CN 107129425 A CN107129425 A CN 107129425A
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- fluorescent chemicals
- calixarenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- 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"
- G01N2021/6432—Quenching
Abstract
The invention discloses a kind of calixarenes fluorescent chemicals, with structure shown in formula I.The present invention is to Fe3+And Cu2+With good recognition performance, and to Fe3+Detectable limit reaches 6.48ppm；The preparation method of the calixarenes fluorescent chemicals is simple, and raw material is cheap and easy to get, to cell without overt toxicity, the Fe in environment, organism3+Or Cu2+Context of detection there is wide application prospect.
Description
Technical field
The present invention relates to type fluorescent chemicals technical field, more particularly, to a kind of calixarenes fluorescent chemicals and its should
With.
Background technology
Fluorescence analysis is the analysis method that a kind of sensitivity is high, selectivity is strong, easy to use, is widely used in analysisization
, bioanalysis, environmental project, material science, medicine and other fields.Fluorescent chemicals is a kind of thing with special optical performance
Matter, after the energy such as ultraviolet, visible ray are absorbed, then electron transition to excitation state occurs radiative decay and is returned to ground state, release
Photon, produces fluorescence.In recent years, people are with calixarenes --- the new hole that a class is formed by methylene-bridged phenol units
Shape compound is molecule platform, develops various fluorescent probe compounds, has in medical domains such as clinical diagnosis, molecular biology
Wide potential using value.For example, Calixarene Derivatives can determine human plasma as metal-ion fluorescent identification agent
Interior Na+、K+、Ca2+And Mg2+Deng metal ion.
Iron, is one of the essential trace elements of the human body, abundant to be present in organism.In many biochemical reactions, Fe3+Play the part of
Very important role is drilled, its shortage and excess all can make the function of body get muddled, for example, alzheimer's disease,
Exception of the generation development of the disease such as parkinson's syndrome and anaemia all with internal iron concentration has substantial connection.Therefore, open
Hair is in Fe in quantitative detection human body3+Selective fluorescence probe, for ensure life and health it is significant.Current iron from
Sub- fluorescence probe has metal-organic framework materials (such as Tb-MOF), rhodamine, nano material (such as S-GQDs, GSH@AgNC)
Deng, but these fluorescence probe synthetic methods are cumbersome, toxic side effect is poor.
The content of the invention
It is an object of the invention to provide a kind of calixarenes fluorescent chemicals, it is readily synthesized, and selectivity is high, without substantially thin
Cellular toxicity, can detect internal Fe according to the change of fluorescence intensity3+Content.
To realize the above-mentioned purpose of the present invention, the present invention is adopted the following technical scheme that：
A kind of calixarenes fluorescent chemicals, with structure shown in formula I.
As a kind of preferred scheme, the calixarenes fluorescent chemicals with structure shown in formula I is to Li+、Na+、K+、Ca2+、
Al3+、Zn2+、Cd2+、Cu2+And Fe3+It is respectively provided with selectivity.
As a kind of preferred scheme, the calixarenes fluorescent chemicals with structure shown in formula I is to Fe3+Detectable limit reach
To 6.48ppm.
A kind of preparation method of calixarenes fluorescent chemicals, comprises the following steps,
1) pyrogallol is substantially soluble in ethanol and hydrochloric acid by, forms mixture A；
2) freezes mixture A, and propionic aldehyde is added dropwise on the mixture A after frost dropwise, forms mixture B；
3) warms to room temperature mixture B, then is heated to reflux 22-26 hours under argon gas protection；
4) is cooled to after room temperature, mixture B is placed 22-26 hours under conditions of temperature is -20 DEG C, through suction filtration
Afterwards, solid is obtained；
5) with frost ethanol repeatedly to as step 4) made from solid wash, until waste liquid become clarification；
6) solid after will be scrubbed is placed on temperature to be dried in vacuo 14-18 hours under conditions of 80 DEG C -120 DEG C, obtains
It is calixarenes fluorescent chemicals to pale pink powder.
It is used as a kind of preferred scheme, step 1) mass ratio of pyrogallol in mixture A, ethanol and hydrochloric acid is 10:40-
50:3-8, the volumetric concentration of the ethanol is 95%, and the mass fraction of the hydrochloric acid is 36%.
Be used as a kind of preferred scheme, step 2) in propionic aldehyde and mixture A mass ratio be 1:9-11.
Be used as a kind of preferred scheme, step 3) and 4) in room temperature temperature range be 18 DEG C -25 DEG C.
Be used as a kind of preferred scheme, step 5) in ethanol volumetric concentration be 95%.
Be used as a kind of preferred scheme, step 6) in vacuum be 0.1MPa.
As a kind of preferred scheme, the calixarenes fluorescent chemicals with the structure as described in Formulas I is in environment or organism
Fe3+Or Cu2+Detection is identified.
Calixarenes fluorescent chemicals of the present invention is according to its own fluorescence excitation peak intensity to the recognition capability of metal ion
Change carry out analyzing judgement.Fluorescence titration by various different metal ions to calixarenes fluorescent chemicals of the present invention
Experiment, finding the presence of metal ion can make fluorescence intensity change, especially Fe3+Or Cu2+Fluorescence can occurs sudden
Go out, and to Fe3+Detectable limit reaches 6.48ppm.Therefore, calixarenes fluorescent chemicals of the present invention can be used as fluorescence probe pair
Fe3+Or Cu2+Detection is identified.
By using various concentrations calixarenes fluorescent chemicals of the present invention the cells of HEK 293 (human embryonic kidney cells) are grown into
Row is intervened, and detects influence of the calixarenes fluorescent chemicals of the present invention to normal human cells.Specifically used MTT methods：It is exogenous
Butanedioic acid dehydrogenations of the MTT (3- (4,5- dimethylthiazoles -2) -2,5- diphenyltetrazolium bromide bromides) in living cells mitochondria
Water insoluble bluish violet crystallization first a ceremonial jade-ladle, used in libation can be reduced in the presence of enzyme and is deposited in cell, and dead cell is acted on without this.
DMSO (dimethyl sulfoxide (DMSO)) can dissolve the first a ceremonial jade-ladle, used in libation in cell, and absorbance value is determined at 490nm wavelength with enzyme-linked immunosorbent assay instrument,
Living cells quantity can be reflected indirectly.MTT experiment shows that the calixarenes fluorescent chemicals of the present invention in the range of finite concentration is to normal
Living cells is without overt toxicity.
Beneficial effects of the present invention are：Calixarenes fluorescent chemicals of the present invention is to Fe3+With good recognition performance, the cup
Aromatic hydrocarbons fluorescent chemicals is to Fe3+Detectable limit reaches 6.48ppm, and preparation method is simple, and raw material is cheap and easy to get, to cell without bright
Aobvious toxicity, the Fe in environment, organism3+Context of detection there is wide application prospect.
Brief description of the drawings
Fig. 1 is the carbon-13 nmr spectra of calixarenes fluorescent chemicals of the present invention；
Fig. 2 is the proton nmr spectra of calixarenes fluorescent chemicals of the present invention；
Fig. 3 is fluorescence identifying spectrum of the calixarenes fluorescent chemicals of the present invention to each metal ion species；
Fig. 4 is fluorescence identifying spectrum of the calixarenes fluorescent chemicals of the present invention to the iron ion of various concentrations；
Fig. 5 is the cell after intervening HEK293 cells 24,48 and 72h through various concentrations calixarenes fluorescent chemicals of the present invention
Activity figure.
Embodiment
Embodiment 1
1) it is 36% that 20g pyrogallols are substantially soluble in ethanol and 38mL mass fractions that 107mL volumetric concentrations are 95% by
Hydrochloric acid in, form mixture A；
2) freezes mixture A, and 16mL propionic aldehyde is added dropwise on the mixture A after frost dropwise, forms mixture B；
3) mixture B is warmed to 25 DEG C by, then is heated to reflux 22 hours under argon gas protection；
4) is cooled to after 25 DEG C, mixture B is placed 22 hours under conditions of temperature is -20 DEG C, after suction filtration,
Obtain solid；
5) with 5mL volumetric concentrations for 95% frost ethanol repeatedly to as step 4) made from solid wash, directly
Become to waste liquid and clarify；
6) solid after will be scrubbed be placed on temperature be 120 DEG C, vacuum be to be dried in vacuo 14 under conditions of 0.1MPa
Hour, obtain pale pink powder i.e. calixarenes fluorescent chemicals.
Embodiment 2
1) it is 36% that 20g pyrogallols are substantially soluble in ethanol and 14mL mass fractions that 133mL volumetric concentrations are 95% by
Hydrochloric acid in, form mixture A；
2) freezes mixture A, and 14mL propionic aldehyde is added dropwise on the mixture A after frost dropwise, forms mixture B；
3) mixture B is warmed to 18 DEG C by, then is heated to reflux 26 hours under argon gas protection；
4) is cooled to after 18 DEG C, mixture B is placed 26 hours under conditions of temperature is -20 DEG C, after suction filtration,
Obtain solid；
5) with 5mL volumetric concentrations for 95% frost ethanol repeatedly to as step 4) made from solid wash, directly
Become to waste liquid and clarify；
6) solid after will be scrubbed be placed on temperature be 80 DEG C, vacuum be to be dried in vacuo 16 under conditions of 0.1MPa
Hour, obtain pale pink powder i.e. calixarenes fluorescent chemicals.
Embodiment 3
1) it is 36% that 20g pyrogallols are substantially soluble in ethanol and 24mL mass fractions that 120mL volumetric concentrations are 95% by
Hydrochloric acid in, form mixture A；
2) freezes mixture A, and 15mL propionic aldehyde is added dropwise on the mixture A after frost dropwise, forms mixture B；
3) mixture B is warmed to 20 DEG C by, then is heated to reflux 24 hours under argon gas protection；
4) is cooled to after 20 DEG C, mixture B is placed 24 hours under conditions of temperature is -20 DEG C, after suction filtration,
Obtain solid；
5) with 5mL volumetric concentrations for 95% frost ethanol solution repeatedly to as step 4) made from solid wash
Wash, until waste liquid becomes clarification；
6) solid after will be scrubbed be placed on temperature be 100 DEG C, vacuum be to be dried in vacuo 18 under conditions of 0.1MPa
Hour, obtain pale pink powder i.e. calixarenes fluorescent chemicals.
In summary, the preparation method of calixarenes fluorescent chemicals of the present invention is simple, and preparing raw material is cheap and easy to get, is easy to
Industrial production.
In above example, embodiment 3 is that the calixarenes fluorescent chemicals used in optimal case, embodiment 4-8 is equal
It is made by embodiment 3.
Embodiment 4
Nuclear magnetic resonance is carried out to the carbon in calixarenes fluorescent chemicals of the present invention, carbon-13 nmr spectra is obtained, as a result such as Fig. 1
It is shown.
Embodiment 5
Nuclear magnetic resonance is carried out to the hydrogen in calixarenes fluorescent chemicals of the present invention, proton nmr spectra is obtained, as a result such as Fig. 2
It is shown.
Embodiment 6
Calixarenes fluorescent chemicals of the present invention is tested to the fluorescence identifying of each metal ion species
Description of test：The metallic compound for participating in fluorescence identifying is LiNO3、NaNO3、KNO3、Ca(NO3)2、Al(NO3)3、
Zn(NO3)2、Cd(NO3)2、Cu(NO3)2With Fe (NO3)3.All metal compound concentrations are 0.01M.
Experimental procedure：5mg calixarenes fluorescent chemicalses of the present invention are added in several 5mL volumetric flasks, are then distinguished again
Above metallic solution is added, finally solvent DMF (DMF) constant volume is determined with through 5A molecular sieve dryings, in ultrasound
Frequency is ultrasound 20 minutes under conditions of 10K Hz, is tested after placing 12 hours at room temperature, record data, obtains experiment knot
Really.
Experimental result：
From the figure 3, it may be seen that NO3-Do not interfere with the fluorescence intensity of the compounds of this invention, and the change of fluorescence intensity be strictly by
Metal ion is caused in itself.Calixarenes fluorescent chemicals of the present invention has most strong when any metal is not added at 356nm
Excitation peak, with the addition of metallic compound, the fluorescence intensity of most strong excitation peak occurs in that change.That especially pronounced is Fe
(NO3)3With Cu (NO3)2Fluorescent quenching can be made, therefore calixarenes fluorescent chemicals of the present invention can be used as Fe3+Or Cu2+Fluorescence
Probe.In addition, except KNO3With Cd (NO3)2Fluorescence intensity of the calixarenes fluorescent chemicals of the present invention at 356nm can be made
Enhancing is outer, LiNO3、NaNO3、Ca(NO3)2、Al(NO3)3With Zn (NO3)2This most strong excitation peak can be strengthened to a certain extent
Fluorescence.
Embodiment 7
Calixarenes fluorescent chemicals of the present invention is by Fe (NO3)3The experiment being gradually quenched
Experimental procedure：Weigh 5mg calixarenes fluorescent chemicalses of the present invention be dissolved in 5mL Jing Guo 5A molecular sieve dryings DMF (N,
Dinethylformamide) in solution, ultrasonically treated 20 minutes under conditions of supersonic frequency is 10K Hz, after standing 12 hours again
Ultrasonically treated 20 minutes under conditions of supersonic frequency is 10K Hz, then tests, Fe (NO are added dropwise dropwise3)3(1000ppm), note
Data are recorded, drafting obtains experimental result.
Experimental result：
As shown in Figure 4, with Fe (NO3)3The gradually increase of concentration, fluorescence intensity gradually weakens, is finally quenched.
Embodiment 8
Calixarenes fluorescent chemicals of the present invention is used for MTT cytotoxicity experiments
Experimental procedure：
(1) preparation of various concentrations calixarenes fluorescent chemicals of the present invention
The cells of HEK 293 (human embryonic kidney cells) are put into 96 orifice plates and cultivated.It incite somebody to action this with DMSO (dimethyl sulfoxide (DMSO))
Invention calixarenes fluorescent chemicals is made into 40mg/mL, then distinguishes 40mg/mL calixarenes fluorescent chemicals solution of the present invention
Be diluted to the DMEM in high glucose nutrient solution without serum 25 μ g/mL, 50 μ g/mL, 100 μ g/mL, 200 μ g/mL, 300 μ g/mL and
400 μ g/mL solution, and be placed on temperature to preserve under conditions of 4 DEG C.After after the cell attachment in 96 orifice plates, taking 10 μ L respectively
The above-mentioned solution prepared is put in culture (calixarenes fluorescence chemical combination of the present invention in 96 orifice plates containing 90 μ L serum-containing mediums
The concentration of thing is diluted 10 times, and the calixarenes fluorescent chemicals concentration of the present invention in hole is respectively 2.5 μ g/mL, 5 μ g/mL, 10
μ g/mL, 20 μ g/mL, 30 μ g/mL and 40 μ g/mL).
(2) cell culture --- counting --- fishplate bar
The cells of HEK 293 (human embryonic kidney cells) adherent growth can be passed on to 90-95%.In superclean bench, suction is abandoned
Nutrient solution in above-mentioned 96 orifice plate, then with 2mL through PBS (phosphate buffer) of the high pressure after degerming to adherent thin in 96 orifice plates
Born of the same parents carry out rinse, then add 1mL trypsase (0.25%Trypsin-EDTA of gibco companies production) in 96 orifice plates
Attached cell is digested, and observes after circle, be added immediately the termination of 2mL nutrient solutions to most cells diminution change under the microscope
Digestion, then with centrifuge tube absorption, 15mL is through postdigestive cell liquid and puts it into centrifuge, with 1000r/min rotating speed
Carry out centrifugation 5 minutes.Remove after supernatant, add 1mL nutrient solutions, then the cell of bottom precipitation is broken up and is formed uniformly cell
Suspension.Draw 400 μ L cell suspensions and be put into another culture vessel and cultivated, draw 100 μ L cell suspensions again in addition and be put in
Cell counting count board number number, then remaining 500 μ L cell suspensions, which are diluted, makes its density reach 5.6*104/ mL, and will dilution
Cell suspension inoculation afterwards continues to cultivate in 3 piece of 96 orifice plate (adding 90 μ L cell suspensions per hole).
(3) MTT is tested
Next day observes the cell growth condition in 96 orifice plates, after after cell attachment, being separately added into 10 μ L (25 μ g/mL), 10 μ
L (50 μ g/mL), 10 μ L (100 μ g/mL), 10 μ L (200 μ g/mL), 10 μ L (300 μ g/mL) and 10 μ L (400 μ g/mL) this hair
Bright compound and DMEM in high glucose nutrient solution without serum are in hole.MTT (3- (4,5- dimethylthiazoles -2) -2,5- diphenyl
Tetrazole bromide) it is dissolved in formation MTT solution in PBS (phosphate buffer).Culture 1,2, after 3 days, be separately added into hole
10 MTT solution of the μ L (5mg/mL) through filtration sterilization, continue after cultivating 4 hours, waste liquid in hole is abandoned in suction, 150 μ L are added per hole
DMSO (dimethyl sulfoxide (DMSO)) solution, places shaking table (the TS-2 shaking tables of its woods Bel's instrument manufacturing Co., Ltd production) in shimmy width
Spend to be rocked under conditions of 70Rpm 20 minutes, finally with enzyme-linked immunosorbent assay instrument (the Epoch series that Bai Teng instrument companies produce)
Measure absorbance value, record data at 490nm wavelength, the concentration using calixarenes fluorescent chemicals of the present invention is abscissa, carefully
Born of the same parents' vigor is that ordinate draws block diagram, as shown in Figure 5.
Experimental result：
As shown in Figure 5, the calixarenes fluorescent chemicals of the present invention in the range of finite concentration to normal live cells without obvious
Toxicity.
Above-described is only the preferred embodiment of the present invention, it is noted that for one of ordinary skill in the art
For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention
Protection domain.
Claims (10)
1. a kind of calixarenes fluorescent chemicals, it is characterised in that：With structure shown in formula I.
2. calixarenes fluorescent chemicals according to claim 1, it is characterised in that：Fluorescence with structure shown in formula I
Compound is to Li+、Na+、K+、Ca2+、Al3+、Zn2+、Cd2+、Cu2+And Fe3+It is respectively provided with selectivity.
3. calixarenes fluorescent chemicals according to claim 2, it is characterised in that：Fluorescence with structure shown in formula I
Compound is to Fe3+Detectable limit reach 6.48ppm.
4. a kind of preparation method of calixarenes fluorescent chemicals, it is characterised in that：Comprise the following steps,
1) pyrogallol is substantially soluble in ethanol and hydrochloric acid by, forms mixture A；
2) freezes mixture A, and propionic aldehyde is added dropwise on the mixture A after frost dropwise, forms mixture B；
3) warms to room temperature mixture B, then is heated to reflux 22-26 hours under argon gas protection；
4) is cooled to after room temperature, mixture B is placed 22-26 hours under conditions of temperature is -20 DEG C, after suction filtration, is obtained
To solid；
5) with frost ethanol repeatedly to as step 4) made from solid wash, until waste liquid become clarification；
6) solid after will be scrubbed is placed on temperature to be dried in vacuo 14-18 hours under conditions of 80 DEG C -120 DEG C, obtains light
Pink powder is calixarenes fluorescent chemicals.
5. the preparation method of calixarenes fluorescent chemicals according to claim 4, it is characterised in that：Step 1) mixture A
In pyrogallol, the mass ratio of ethanol and hydrochloric acid be 10:40-50:3-8, the volumetric concentration of the ethanol is 95%, the salt
The mass fraction of acid is 36%.
6. the preparation method of calixarenes fluorescent chemicals according to claim 4, it is characterised in that：Step 2) in propionic aldehyde
Mass ratio with mixture A is 1:9-11.
7. the preparation method of calixarenes fluorescent chemicals according to claim 4, it is characterised in that：Step 3) and 4) in
The temperature range of room temperature is 18 DEG C -25 DEG C.
8. the preparation method of calixarenes fluorescent chemicals according to claim 4, it is characterised in that：Step 5) in ethanol
Volumetric concentration is 95%.
9. the preparation method of calixarenes fluorescent chemicals according to claim 4, it is characterised in that：Step 6) in vacuum
Spend for 0.1MPa.
10. the application of the calixarenes fluorescent chemicals according to any one of claim 1-3, it is characterised in that：Have
The fluorescent chemicals of structure is to the Fe in environment or organism as described in Formulas I3+Or Cu2+Detection is identified.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169991A (en) * | 1989-03-16 | 1992-12-08 | Imperial Chemicals Industries Plc | Compound |
| WO2003033649A2 (en) * | 2001-10-16 | 2003-04-24 | The Curators Of The University Of Missouri | Hexameric complexes and their preparation |
-
2017
- 2017-06-29 CN CN201710514919.6A patent/CN107129425A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5169991A (en) * | 1989-03-16 | 1992-12-08 | Imperial Chemicals Industries Plc | Compound |
| WO2003033649A2 (en) * | 2001-10-16 | 2003-04-24 | The Curators Of The University Of Missouri | Hexameric complexes and their preparation |
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