CN101451954A - Phosphorescent chemical sensor for qualitatively detecting contrast of aminothiopropionic acid and homocysteine and use thereof - Google Patents
Phosphorescent chemical sensor for qualitatively detecting contrast of aminothiopropionic acid and homocysteine and use thereof Download PDFInfo
- Publication number
- CN101451954A CN101451954A CNA2008102044206A CN200810204420A CN101451954A CN 101451954 A CN101451954 A CN 101451954A CN A2008102044206 A CNA2008102044206 A CN A2008102044206A CN 200810204420 A CN200810204420 A CN 200810204420A CN 101451954 A CN101451954 A CN 101451954A
- Authority
- CN
- China
- Prior art keywords
- homocysteine
- iridium
- chemical sensor
- complex
- phosphorescence
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to the field of phosphorescence chemical sensor technology, specifically to a scale phosphorescence chemical sensor for qualitatively detecting cysteine and homocysteine and application thereof, characterized by relating to an iridium complex containing aldehyde group. The aldehyde group of the iridium complex generates cyclization reaction with amido and sulfhydryl of homocysteine and cysteine to convert to heterocycle, aldehyde group and benzene ring contained in original iridium complex conjugate, then conjugation of aldehyde group and benzene ring disappears after reacting with cysteine or homocysteine, thereby affecting spectroscopic properties of the generated products, and detecting cysteine and homocysteine through using the property. The inventive iridium complex solution emits yellow phosphorescence when being excitated by 365 nm ultraviolet light, and emits red phosphorescence reacting with mercaptoamino acid, without being interrupted by other amino acid.
Description
Technical field
The present invention relates to technical field of phosphorescent chemical sensor, be specifically related to a kind of qualitative detection of cysteine and homocysteine than degree phosphorescence chemical sensor and application thereof.
Background technology
Mercaptoamino acid comprises homocysteine and halfcystine, and this two seed amino acid all has the important physical function.Homocysteine application clinically is mainly as angiocardiopathy, the dangerous index of sclerosis of coronary artery congee and miocardial infarction especially, and its concentration rising degree is directly proportional with the danger of disease.Halfcystine participates in the reduction process of cell and the phospholipid metabolism in the liver, and it has the protection liver cell to be without prejudice, to impel the vigorous effect of liver function.Because these important physical functions, the detection that contains mercaptoamino acid has been subjected to very big concern.Present detection method mainly contains chromatographic resolution and immunoassay, but these two kinds of methods all need expensive complicated instrument, operate also very loaded down with trivial details.
Fluorescent technique since its intrinsic highly sensitive and simple operation and other advantages be widely used among design and the development of Optochemical sensor of various types of, various detected objects.Over the past two years, people began to pay close attention to that design is synthetic that homocysteine (Hcy) and halfcystine (Cys) thereof are had the fluorescent optical sensor of response, but most sensors concentrate on organic fluorescent dye, and kind is single.
In recent years, be the great interest that chemical sensor has caused people with the phosphorescence heavy metal complex, this is because the phosphorescence heavy metal complex has following characteristics: emission wavelength changes with the variation of environment of living in; Compare with organic phosphorescent material, the phosphorescence heavy metal complex has bigger (Stokes) Stokes displacement and long emission lifetime, and long emission lifetime helps the service time resolution techniques makes phosphorescent signal distinguish mutually with the phosphorescent signal of background.At present more existing phosphorescence heavy metal complexes as platinum, rhenium and ruthenium complex, are used as the phosphorescence chemical sensor that detects negative ion, oxygen concentration and metallic ion.Yet as the best phosphor material of performance, complex of iridium but seldom is used as chemical sensor.Under this class complex room temperature very strong phosphorescence is just arranged, its phosphorescent lifetime (microsecond level) is than the long several magnitude of common phosphorescent lifetime (nanosecond).Up to the present, have only the minority complex of iridium to be used as and detect oxygen concentration and calcium ion, also not about detecting amino acid whose complex of iridium report.
Summary of the invention
The objective of the invention is to a kind of complex of iridium as the mercaptoamino acid in more semi-aqueous than degree phosphorescence chemical sensor qualitative detection, to solve the technical matters that detects in real time fast of mercaptoamino acid.
Mercaptoamino acid was meant that than degree phosphorescence chemical sensor part contains the complex of iridium of aldehyde radical during a kind of qualitative detection that the present invention proposes was semi-aqueous, and the concrete structure formula is:
The complex of iridium chemical sensor its preparation method that contains aldehyde radical proposed by the invention is:
(1) at first prepares the complex (pba) of iridium dichloro bridge
2Ir (μ-Cl)
2Ir (pba), pba are 4-(2-pyridine)-benzaldehyde.Take by weighing IrCl
33H
2O and corresponding Cyclometalated C^N part 4-(2-pyridine)-benzaldehyde join in the two-neck bottle, and the mol ratio of the two is 2～0.2:1, and optimum mole ratio is 0.5:1.On biexhaust pipe, vacuumize-inflated with nitrogen or argon gas-vacuumize, circulate three times, at last with nitrogen or argon shield reaction system.With the potpourri of syringe injection cellosolvo and water, the two volume ratio is 1～5:1, and optimum volume ratio is 3:1.Then reaction mixture is heated to 80 ℃-140 ℃, optimal reaction temperature is 10 ℃.Stirring reaction 1-24 hours has precipitation to generate.After reaction stops reaction mixture being reduced to room temperature, filter and obtain precipitation.Gained precipitates respectively water, ethanol to be washed, and obtains red solid iridium dichloro endo compound (pba)
2Ir (μ-Cl)
2Ir (pba)
2
(2) then iridium dichloro endo compound and the bipyridine ligand that makes in the step (1) joined in the two-neck bottle, mol ratio is 1:1～5, and optimum mole ratio is 1:2; On biexhaust pipe, vacuumize-inflated with nitrogen or argon gas-vacuumize, circulate three times, at last with nitrogen or argon shield reaction system.Inject methylene chloride and methyl alcohol mixed solvent with syringe, volume ratio 1～3:1, optimum volume ratio are 2:1; With the reaction mixture reflux, stirring reaction 0.5-4 hour, cool off the back and add excessive Potassium Hexafluorophosphate, continue to stir 0.5-2 hour, (methylene chloride/acetone=15:1) separation makes the pure product of described phosphorescence chemical sensor complex of iridium to column chromatography.
As above shown in the reaction equation, the aldehyde radical of the complex of iridium among the present invention can change hydridization into the amino and the sulfydryl generation cyclization of homocysteine and halfcystine, there are aldehyde radical and phenyl ring conjugation in the former complex of iridium, and with the reaction of halfcystine or homocysteine after the conjugation disappearance of aldehyde radical and phenyl ring, thereby influenced the spectral quality of the product that generates, utilized the change of this character to detect halfcystine and homocysteine.Complex of iridium solution among the present invention sends yellow phosphorescence when the 365nm ultraviolet excitation, and with the mercaptoamino acid effect after send red phosphorescent, other amino acid to do not disturb.
Complex of iridium is tested the ultraviolet spectrum of mercaptoamino acid response: the mensuration of ultraviolet spectrum is to carry out in the buffer solution of DMSO (dimethyl sulfoxide) and HEPES (4-hydroxyethyl piperazine ethanesulfonic acid), complex of iridium is dissolved in the mixed solution of buffer solution of DMSO and HEPES, adds the homocysteine and the halfcystine solution with the HEPES preparation of variable concentrations again.Test after reaching balance.
Complex of iridium is tested the phosphorescence spectrum of mercaptoamino acid response: the mensuration of phosphorescence spectrum is to carry out in the buffer solution of DMSO and HEPES, complex of iridium is dissolved in the buffer solution of DMSO and HEPES, adds the homocysteine and the halfcystine solution with the HEPES preparation of variable concentrations again.Test after reaching balance.
Advantage of the present invention: the luminescent lifetime of complex of iridium can reach microsecond, can eliminate the interference of background fluorescence effectively by the time-resolved fluorescence technology, obtains high detection sensitivity.Complex of iridium can detect halfcystine and homocysteine among the present invention, and other amino acid does not disturb.
Description of drawings
Fig. 1 is the ultraviolet spectrum variation of complex of iridium to homocysteine and halfcystine response.Maximum absorption band descends.Horizontal ordinate is represented absorbing wavelength, and ordinate is represented absorbance.Fig. 1 a is a homocysteine, and 1b is a halfcystine.
Fig. 2 is the phosphorescence spectrum variation of complex of iridium to homocysteine and halfcystine response.The general 40nm of maximum emission wavelength red shift, fluorescence intensity descends to some extent.Horizontal ordinate is represented emission wavelength, and ordinate is represented emissive porwer.Fig. 2 a is a homocysteine, and 2b is a halfcystine.
Fig. 3 is a complex of iridium to the phosphorescence spectrum selectivity test of 21 seed amino acids and a kind of little peptide response, only contains mercaptoamino acid and makes the ratio degree phosphorescence generation obvious variation of system.The ordinate representative is at the ratio of wavelength 586nm and 547nm emissive porwer, and horizontal ordinate is represented different aminoacids, and 1-22 amino acid are the L-serine respectively, L-glutaminate, L-glutamic acid, L-isoleucine, L-threonine, the L-glycocoll, L-valine, L-methionine, L-arginine, L-lysine, L-histidine, L-aspartic acid, L-tryptophane, the L-proline, L-phenylalanine, L-tyrosine, L-leucine, the L-alanine, glutathione, L-halfcystine and homocysteine.
Fig. 4 tests the interference that contains mercaptoamino acid for other amino acid.The result shows that other amino acid do not disturb the test of this two seed amino acid.Ordinate is represented the ratio in wavelength 586nm and 547nm emissive porwer, a, and the horizontal ordinate 1-20 of b is represented different aminoacids, and amino acid is respectively the L-histidine, the L-leucine, L-arginine, L-tryptophane, L-threonine, the L-proline, L-isoleucine, L-methionine, L-aspartic acid, the L-valine, L-alanine, L-phenylalanine, L-glutaminate, L-glutamic acid, L-serine, L-hydroxyproline, L-lysine, L-glycocoll and L-tyrosine.Fig. 4 a is a homocysteine, and 4b is a halfcystine.
Embodiment
The preparation of complex of iridium: take by weighing IrCl
33H
2O (5.52mmol) and corresponding Cyclometalated C^N part 4-(2-pyridine)-benzaldehyde (1.04mmol) join in the two-neck bottle, vacuumize on biexhaust pipe-inflated with nitrogen-vacuumize, and circulate three times, use the nitrogen protection reaction system at last.With syringe inject cellosolvo and water potpourri (3:1, v/v) after, reaction mixture is heated to 10 ℃, about 24 hours of stirring reaction has precipitation to generate.After reaction stops reaction mixture being reduced to room temperature, filter and obtain precipitation.Gained precipitates respectively water, ethanol to be washed, and obtains red solid iridium dichloro endo compound (pba)
2Ir (μ-Cl)
2Ir (pba)
2Take by weighing iridium dichloro endo compound (0.16mmol) and bipyridine ligand (0.32mmol) joins in the two-neck bottle, on biexhaust pipe, vacuumize-inflated with nitrogen-vacuumize, circulate three times, use the nitrogen protection reaction system at last.With syringe inject methylene chloride and methyl alcohol mixed solvent (2:1, v/v), with the reaction mixture reflux, about 4 hours of stirring reaction, cool off the back and add excessive Potassium Hexafluorophosphate, continue to stir 2 hours, (methylene chloride/acetone=15:1) separation obtains pure product to column chromatography.
1H?NMR(400MHz，DMSO，25℃)：δ＝9.72(s，2H，13-H)，8.90(d，
3J
H，H＝8.0Hz，2H，9-H)，8.48(d，
3J
H，H＝8.0Hz，2H，1-H)，8.29(d，
3J
H，H＝8.0Hz，2H，12-H)，8.19(d，
3J
H，H＝7.6Hz，2H，4-H)，8.09(dd，
3J
H，H＝7.6Hz?2H，3-H)，7.86(d，
3J
H，H＝4.2Hz，2H，5-H)，7.75(d，
3J
H，H＝4.2Hz，2H，6-H)，7.68(t，
3J
H，H＝8.0Hz，2H，10-H)，7.59(t，
3J
H，H＝8.0Hz，2H，11-H)，7.32(d，
3J
H，H＝8.0Hz，2H，2-H)，6.66(s，2H，8-H).MS(ESI-MS)：m/z?713(M
+).
Complex is tested the ultraviolet spectrum of mercaptoamino acid response: complex of iridium is dissolved in the middle of the buffer solution of DMSO and HEPES, the pH value is 7.2, the two volume ratio is 9:1, the concentration of HEPES is 50mmol/L, the concentration of complex is 20 μ mol/L, then adds the homocysteine and the halfcystine solution of the HEPES damping fluid configuration of equal-volume 0-120eq.After the ready to balance, measure ultraviolet spectrum, see Fig. 1.
Complex is tested the phosphorescence spectrum of mercaptoamino acid response: complex of iridium is dissolved in the middle of the buffer solution of DMSO and HEPES, the pH value is 7.2, the two volume ratio is 9:1, the concentration of HEPES is 50mmol/L, the concentration of complex is 20 μ mol/L, then adds the homocysteine and the halfcystine solution of the HEPES damping fluid configuration of equal-volume 0-120eq.After the ready to balance, measure phosphorescence spectrum, see Fig. 2.
Complex of iridium is dissolved in that concentration is 20 μ mol/L among the DMSO, adds the different aminoacids of 120 times of equivalents, and amino acid is respectively homocysteine, the L-halfcystine, glutathione, L-alanine, L-glycocoll, L-tyrosine, the L-phenylalanine, L-proline, L-tryptophane, L-aspartic acid, the L-histidine, L-lysine, L-arginine, L-methionine, the L-valine, L-threonine, L-leucine, L-isoleucine, L-glutamic acid, L-glutaminate and L-serine.Test after reaching balance, test result is seen Fig. 3.
The interference test.Complex of iridium is dissolved in that concentration is 20 μ mol/L among the DMSO, adds the different aminoacids of 120 times of equivalents respectively, and amino acid is respectively the L-histidine, the L-leucine, L-arginine, L-tryptophane, the L-threonine, L-proline, L-isoleucine, the L-methionine, L-aspartic acid, L-valine, the L-alanine, the L-phenylalanine, L-glutaminate, L-glutamic acid, the L-serine, the L-hydroxyproline, L-lysine, L-glycocoll and L-tyrosine, fully reaction is after 12 hours, add respectively again homocysteine (Fig. 4 a) and halfcystine (Fig. 4 b), test after reaching balance, test result is seen Fig. 4.
Claims (3)
- Qualitative detection of cysteine and homocysteine than degree phosphorescence chemical sensor, be a kind of complex of iridium that contains aldehyde radical specifically, it is characterized in that structural formula is as follows:
- 2. the preparation method of a phosphorescence chemical sensor as claimed in claim 1 is characterized in that preparation process is as follows:(1) at first prepares the complex (pba) of iridium dichloro bridge 2Ir (μ-Cl) 2Ir (pba) takes by weighing IrCl 33H 2O and corresponding Cyclometalated C^N part 4-(2-pyridine)-benzaldehyde join in the two-neck bottle; the mol ratio of the two is 0.2～2:1; with nitrogen or argon shield reaction system; the potpourri of cellosolvo and water reinjects; the two volume ratio is 1～5:1; reaction mixture is heated to 80～140 ℃; stirring reaction 1-24 hour; there is precipitation to generate; after reaction stops reaction mixture being reduced to room temperature; filtration obtains precipitation, will precipitate respectively water, ethanol and wash, and obtains red solid iridium dichloro endo compound (pba) 2Ir (μ-Cl) 2Ir (pba) 2, wherein pba is 4-(2-pyridine)-benzaldehyde;(2) prepare the target complex of iridium then; taking by weighing iridium dichloro endo compound and the acetyl acetone ligands that step (1) makes joins in the two-neck bottle; mol ratio is 1:1～5; with nitrogen or argon shield reaction system; in system, inject methylene chloride and methyl alcohol mixed solvent; volume ratio 1～3:1; with the reaction mixture reflux; stirring reaction 0.5-4 hour; the cooling back adds excessive Potassium Hexafluorophosphate; continue to stir 0.5-2 hour, make described pure product as the eluant, eluent column chromatography for separation than degree phosphorescence chemical sensor complex of iridium with methylene chloride/acetone=15:1.
- 3. the application of phosphorescence chemical sensor as claimed in claim 1 in detecting halfcystine and homocysteine, it is characterized in that detecting halfcystine and homocysteine is to carry out in the buffer solution of dimethyl sulfoxide DMSO and HEPES.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102044206A CN101451954A (en) | 2008-12-11 | 2008-12-11 | Phosphorescent chemical sensor for qualitatively detecting contrast of aminothiopropionic acid and homocysteine and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102044206A CN101451954A (en) | 2008-12-11 | 2008-12-11 | Phosphorescent chemical sensor for qualitatively detecting contrast of aminothiopropionic acid and homocysteine and use thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101451954A true CN101451954A (en) | 2009-06-10 |
Family
ID=40734319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008102044206A Pending CN101451954A (en) | 2008-12-11 | 2008-12-11 | Phosphorescent chemical sensor for qualitatively detecting contrast of aminothiopropionic acid and homocysteine and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101451954A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206235A (en) * | 2011-03-18 | 2011-10-05 | 南京邮电大学 | Phosphorescent iridium complex capable of dissolving in water system, and preparation method thereof |
| CN102516282A (en) * | 2011-11-19 | 2012-06-27 | 浙江大学 | Aldehyde-substituted active silole, and preparation method and application thereof |
| CN103347888A (en) * | 2011-02-09 | 2013-10-09 | 霍夫曼-拉罗奇有限公司 | New iridium-based complexes for ECL |
| CN103555321A (en) * | 2013-10-30 | 2014-02-05 | 南京邮电大学 | Phosphorescent ionic type iridium complex probe and preparation method and application thereof |
| CN105223171A (en) * | 2015-08-31 | 2016-01-06 | 赣南师范学院 | A kind of synthesis of near infrared phosphorescent iridium complex and fluoroscopic examination imaging applications thereof |
| CN107629088A (en) * | 2017-09-22 | 2018-01-26 | 福州大学 | Metal iridium complex containing aldehyde radical and its application on detection differentiation homocysteine and cysteine |
| CN108997439A (en) * | 2018-09-11 | 2018-12-14 | 福州大学 | A kind of metal iridium complex and its application based on the preparation of 5- aldehyde radical -1,10- phenanthroline |
-
2008
- 2008-12-11 CN CNA2008102044206A patent/CN101451954A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103347888B (en) * | 2011-02-09 | 2016-12-21 | 霍夫曼-拉罗奇有限公司 | New complex based on iridium for ECL |
| CN103347888A (en) * | 2011-02-09 | 2013-10-09 | 霍夫曼-拉罗奇有限公司 | New iridium-based complexes for ECL |
| CN102206235A (en) * | 2011-03-18 | 2011-10-05 | 南京邮电大学 | Phosphorescent iridium complex capable of dissolving in water system, and preparation method thereof |
| CN102516282A (en) * | 2011-11-19 | 2012-06-27 | 浙江大学 | Aldehyde-substituted active silole, and preparation method and application thereof |
| CN102516282B (en) * | 2011-11-19 | 2014-09-17 | 浙江大学 | Aldehyde-substituted active silole, and preparation method and application thereof |
| CN103555321A (en) * | 2013-10-30 | 2014-02-05 | 南京邮电大学 | Phosphorescent ionic type iridium complex probe and preparation method and application thereof |
| CN103555321B (en) * | 2013-10-30 | 2015-12-30 | 南京邮电大学 | A kind of Phosphorescent ionic type iridium complex probe and its preparation method and application |
| CN105223171A (en) * | 2015-08-31 | 2016-01-06 | 赣南师范学院 | A kind of synthesis of near infrared phosphorescent iridium complex and fluoroscopic examination imaging applications thereof |
| CN105223171B (en) * | 2015-08-31 | 2018-03-27 | 赣南师范大学 | A kind of synthesis of near-infrared phosphorescent iridium complex and its fluoroscopic examination imaging applications |
| CN107629088A (en) * | 2017-09-22 | 2018-01-26 | 福州大学 | Metal iridium complex containing aldehyde radical and its application on detection differentiation homocysteine and cysteine |
| CN107629088B (en) * | 2017-09-22 | 2019-06-07 | 福州大学 | Metal iridium complex containing aldehyde radical and its application on detection differentiation homocysteine and cysteine |
| CN108997439A (en) * | 2018-09-11 | 2018-12-14 | 福州大学 | A kind of metal iridium complex and its application based on the preparation of 5- aldehyde radical -1,10- phenanthroline |
| CN108997439B (en) * | 2018-09-11 | 2020-09-01 | 福州大学 | Metal iridium complex prepared based on 5-aldehyde-1, 10-phenanthroline and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101451954A (en) | Phosphorescent chemical sensor for qualitatively detecting contrast of aminothiopropionic acid and homocysteine and use thereof | |
| CN101430280A (en) | Phosphorescence chemical sensor for qualitative homocysteine detection and use thereof | |
| Liu et al. | Flavone-based ESIPT ratiometric chemodosimeter for detection of cysteine in living cells | |
| Liu et al. | A ratiometric fluorescent chemosensor for fluoride ions based on a proton transfer signaling mechanism | |
| Yang et al. | An ‘OFF–ON’fluorescent probe for specially recognize on Cys and its application in bioimaging | |
| Gong et al. | A fluorescence enhancement probe based on BODIPY for the discrimination of cysteine from homocysteine and glutathione | |
| Wang et al. | A novel colorimetric and ratiometric fluorescent Cu2+ sensor based on hydrazone bearing 1, 8-naphthalimide and pyrrole moieties | |
| Zhang et al. | A selectively fluorescein-based colorimetric probe for detecting copper (II) ion | |
| Wang et al. | A colorimetric and fluorescent chemodosimeter for discriminative and simultaneous quantification of cysteine and homocysteine | |
| Lee et al. | Quantification of small molecule–protein interactions using FRET between tryptophan and the pacific blue fluorophore | |
| Yu et al. | A neutral pH probe of rhodamine derivatives inspired by effect of hydrogen bond on pKa and its organelle-targetable fluorescent imaging | |
| Wang et al. | A ratiometric fluorescent probe for rapid and sensitive detection of biothiols in fetal bovine serum | |
| Wang et al. | Two-isophorone fluorophore-based design of a ratiometric fluorescent probe and its application in the sensing of biothiols | |
| Liu et al. | A benzoxazine–hemicyanine based probe for the colorimetric and ratiometric detection of biothiols | |
| Li et al. | An effective “turn-on” rodamine-based fluorescent chemosensor for Cu (II) in living cells | |
| Liu et al. | A phthalimide-based fluorescent probe for thiol detection with a large Stokes shift | |
| Zhang et al. | A 4, 5-quinolimide-based fluorescent sensor for sequential detection of Cu2+ and cysteine in water and living cells with application in a memorized device | |
| Guo et al. | A visible-near-infrared fluorescent probe for peroxynitrite with large pseudo-Stokes and emission shift via through-bond energy and charge transfers controlled by energy matching | |
| Zheng et al. | A highly selective colorimetric sensor for cysteine and homocysteine based on a new photochromic diarylethene | |
| Liu et al. | A squaraine-based red emission off–on chemosensor for biothiols and its application in living cells imaging | |
| Hou et al. | The first ratiometric probe for lysine in water | |
| Yang et al. | Fluorescent probe for Cu 2+ and the secondary application of the resultant complex to detect cysteine | |
| Zeng et al. | A significant fluorescent “turn-on” chemosensor for Al3+ detection and application in real sample, logic gate and bioimaging | |
| Gao et al. | Aldehyde bearing bis-cyclometalated Ir (III) complex as selective photoluminescence turn-on probe for imaging intracellular homocysteine | |
| Wang et al. | A rhodamine derivative as selective fluorescent and colorimetric chemosensor for mercury (II) in buffer solution, test strips and living cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090610 |