CN104237194B - Fluorescent spectrometry for detecting micro-Mg2+, Zn2+ or F- - Google Patents
Fluorescent spectrometry for detecting micro-Mg2+, Zn2+ or F- Download PDFInfo
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- CN104237194B CN104237194B CN201410565802.7A CN201410565802A CN104237194B CN 104237194 B CN104237194 B CN 104237194B CN 201410565802 A CN201410565802 A CN 201410565802A CN 104237194 B CN104237194 B CN 104237194B
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Abstract
The invention discloses a fluorescent spectrometry for detecting micro-Mg2+, Zn2+ or F- and belongs to the technical field of analytic chemistry. The fluorescent spectrometry for detecting micro-Mg2+, Zn2+ or F- uses di-(7-hydroxy-coumarin-8-aldehyde) disalicylidene as fluorescent reagent and uses the fluorescent spectrometry to detect micro-Mg2+, Zn2+ or F-. The fluorescent spectrometry for detecting micro-Mg2+, Zn2+ or F- includes that measuring Mg2+ in DMF (N,N-dimethyl formamide) solution, using 350 nanometers as fluorescence excitation wavelength, measuring the fluorescence intensity at the 430 nanometers part, wherein the linear concentration range of detection comprises two magnitude orders, and the limit of detection can as low as 10-8 mol.L-1; measuring Zn2+ in DMF/H2O (1/4, v/v) solution, using 360 nanometers as fluorescence excitation wavelength, measuring the fluorescence intensity at the 457 nanometers part, wherein the linear concentration range of detection comprises two magnitude orders, and the limit of detection can as low as 10-8 mol.L-1; measuring F- in DMF solution, using 360 nanometers as fluorescence excitation wavelength, measuring the fluorescence intensity at the 460 nanometers part, wherein the linear concentration range of detection comprises two magnitude orders, and the limit of detection can as low as 10-8 mol.L-1. Fluorescent reagent is researched by the inventor, and the structure formula is FORMULA (shown in the description).
Description
Technical field
The invention belongs to analytical chemistry field, specifically a kind of detection micro Mg2+、Zn2+Or F-Fluorescent spectrometry.
Background technology
Fluorescent probe technique, as selection highly sensitive, high, detection ion quick, convenient and the important means of molecule, is being given birth to
Life science, environmental science are widely used.Set up the fluorescent probe technique on the basis of molecular recognition, by specific
Target molecule, the selective binding of ion, be converted to identification information be prone to the spectral signal of detection, thus realize at molecular water
Original position on Ping, detect in real time.Screening novel structure, possess the luciferase assay reagent of more excellent selectivity and sensitivity, it is achieved
The recognition detection method of special metal ion and anion had Research Significance and using value.
Magnesium ion is the bivalent metal ion that in cell, content is the highest.Magnesium ion is clinical medicine, threpsology and physiology
In effect caused the extensive concern of people.Develop high selectivity, the sensor of high-sensitivity detection magnesium ion has and grinds
Study carefully meaning.But, with it has been reported that other metal-ion fluorescent probes a large amount of compared with, the magnesium ion fluorescent probe of excellent performance
The most less.Many magnesium ion fluorescent probes reported are all based on familiar crown ether, polyether or carboxylic acid structure, due to
This kind of probe has higher complexing power to calcium ion comparison magnesium ion, causes major part magnesium ion probe can be subject to when detection
The interference of calcium ion.
Zinc ion is the deputy transition metal ions of the human body amount of including, and plays an important role in many physiological process,
Such as the important cofactor etc. in brain function and pathology, genetic transcription, immunologic function and mammalian reproduction.Meanwhile, zinc
The impact of ion pair environment also result in the concern of people.To zinc ion in the association areas such as research life, medical science and environment
Detection method is all significant.In the method for all detection zinc ioies, fluorescent ion probe owing to it is at selectivity,
Sensitivity, the advantage of the aspect such as real-time and in situ detection, it is widely used in this field.Therefore, high selectivity, height are developed
The sensor of sensitivity technique zinc ion has Research Significance.
As important anion, fluorion is widely present in environment and organism.Realize easy to fluorion, quickly
Detection in clinical medicine, show the most important effect.Development structure is simple, simple synthetic method, cheap,
Sensitivity and the superior fluorion fluorometric reagent of selectivity have using value in a lot of association areas.Most fluorometric reagent
It is only used for the detection of metal ion, the Multifunction fluorescent reagent of special metal ion and anion can be detected for number very simultaneously
Few.
Coumarin kind compound has important application at pharmaceutical chemistry and optical material field, in recent years, and many novel tonkabeans
Synthesis and the applied research of element derivant are reported in succession.The one of document report is based on 7-lignocaine-3-aldehyde radical coumarin base
The fluorescent probe of group, to Cu2+There is preferable Selective recognition effect；The one of document report is based on 7-lignocaine-3-aldehyde
The fluorescent probe of butylcoumariii group, to CN-There is preferable Selective recognition effect, face can be observed directly by naked eyes
The change of color, and this probe is to CN-Detection limit can as little as 3.0 μm ol L-1；A kind of coumarin derivative of document report is glimmering
Light probe can be used for detection by quantitative sulfite ion in aqueous solution.But have no and reported that a kind of coumarin fluorescent reagent can be distinguished
Detection different metal ion or the method for anion.
Summary of the invention: it is an object of the invention to study that a kind of energy is highly sensitive, the detection micro Mg of high selection2+、Zn2+Or F-
Spectrofluorimetry new method.Developed the new fluorometric reagent of synthesis by inventor, use fluorescent spectrometry, control difference
Solvent, it is achieved to Mg2+、Zn2+Or F-Highly sensitive, high selection detection.
One of the present invention detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry, with chemical name be double-(7-hydroxyl-
Coumarin-8-aldehyde) compound of contracting ethylenediamine, it is abbreviated as s1, is used for detecting micro Mg as fluorescence method2+、Zn2+Or F-Fluorescence
Reagent；(1) reagent s1 measures Mg in N,N-dimethylformamide (DMF) solution2+Time, with 350nm as fluorescence exciting wavelength, survey
Determine the fluorescence intensity at 430nm, at Mg2+In the range of finite concentration, fluorescence intensity and Mg2+Concentration is linear, increases with fluorescence
Strong method measures Mg2+；(2) reagent s1 is at DMF/H2O(1/4, v/v) solution measures Zn2+Time, with 360nm as fluorescence exciting wavelength,
Measure the fluorescence intensity at 457nm, at Zn2+In the range of finite concentration, fluorescence intensity and Zn2+Concentration is linear, uses fluorescence
Enhancing method measures Zn2+；(3) reagent s1 measures F in DMF solution-Time, with 360nm as fluorescence exciting wavelength, measure at 460nm
Fluorescence intensity, at F-In the range of finite concentration, fluorescence intensity and F-Concentration is linear, measures F with catalytic fluorescence method-。
Above-mentioned one detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry be (1) measure Mg2+Time, other gold that coexists
Belong to ion: Zn2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Cd2+, Pb2+, Li+, Na+, K+, Ag+, Al3+, Fe3+, Cr3+
One of, it is Mg in concentration2+During concentration 10 times amount, except Co2+, Cu2+, Pb2+, Cd2+, Zn2+Ion coexists outside impact, other metal
Ion does not disturb Mg2+Mensuration；(2) Zn is measured2+Time, other coexistent metallic ion: Mg2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+,
Ni2+, Cu2+, Cd2+, Pb2+, Li+, Na+, K+, Ag+, Al3+, Fe3+, Cr3+One of, it is Zn in concentration2+During concentration 10 times amount, except Hg2 +, Co2+, Cu2+, Cr3+, Ni2+Ion coexists outside impact, and other metal ion does not disturb Zn2+Mensuration；(3) F is measured-Time, its
Its counter anion: Cl-, Br-, I-, HSO4 -, AcO-, NO3 -, ClO4 -, PF6 -, H2PO4 -, PF6 -One of, it is F in concentration-Concentration 10
During times amount, do not disturb F-Mensuration.
Above-mentioned one detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry be (1) fluorometric reagent s1 detect micro Mg2 +The concentration range of linearity be 8.0 × 10-7~1.0×10-5 mol·L-1, detection limit as little as 10-8 mol·L-1；(2) fluorometric reagent
S1 detects trace Zn2+The concentration range of linearity be 9.0 × 10-7~1.2×10-5 mol·L-1, detection limit as little as 10-8 mol·L-1；(3) fluorometric reagent s1 detects trace F-The concentration range of linearity be 8.0 × 10-7~1.2×10-5 mol·L-1, detection limit is all
As little as 10-8 mol·L-1。
Above-mentioned one detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry described in fluorometric reagent s1 chemical structural formula
For:
S1
Molecular formula: C22H16N2O6
Molecular weight: 404.10
Fusing point: more than 300 DEG C
Dissolubility: be slightly soluble in chloroform, dimethyl sulfoxide, DMF etc., insoluble in ethanol.
Spectral quality: with Mg in DMF solution2+After forming coordination compound, with 350nm as fluorescence exciting wavelength, launch 430nm
The fluorescence of wavelength；At DMF/H2O(1/4, v/v) in solution with Zn2+After forming coordination compound, with 360nm as fluorescence exciting wavelength, send out
Penetrate the fluorescence of 457nm wavelength；With F in DMF solution-After forming coordination compound, with 360nm as fluorescence exciting wavelength, launch 460nm
The fluorescence of wavelength.
Above-mentioned one detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry, fluorometric reagent used is double-(7-hydroxyl-perfume
Legumin-8-aldehyde) to it is characterized in that synthetic method is be former with umbelliferone, hexamethylenetetramine and ethylenediamine to contracting ethylenediamine
Material, is solvent at dichloromethane, ethanol, with trifluoroacetic acid as solvent with catalyst, through acetylation, formylated, condensation reaction
And obtain.
Accompanying drawing explanation
Fig. 1. the DMF solution of reagent s1 fluorescence spectrum in the presence of different metal ion.
It is 1.00 × 10 in concentration-4 mol·L-1In the DMF solution of reagent s1, it is not added with metal ion respectively or adds 2.00
×10-3 mol·L-1Metal ion Li+, Na+, K+, Mg2+, Zn2+, Ca2+, Hg2+, Ba2+, Pb2+, Cd2+, Co2+, Ni2+, Sr2+,
Cr3+, Cu2+, Ag+, Al3+, Fe3+After fluorescence spectrum.Mg2+Addition make reagent s1 fluorescence intensity at 430nm strengthen.And
The addition of other above-mentioned Experiment Metal ions, except Zn2+Outside being increased slightly, do not change the fluorescence intensity of reagent s1.Exciting of test
Wavelength is 350nm.
Fig. 2. the DMF/H of reagent s12O(1/4, v/v) solution fluorescence spectrum in the presence of different metal ion.
It is 1.00 × 10 in concentration-4 mol·L-1The DMF(N of reagent s1, dinethylformamide)/H2O(1/4, v/v) molten
In liquid, it is not added with metal ion respectively or adds 2.00 × 10-3 mol·L-1Metal ion Li+, Na+, K+, Mg2+, Zn2+, Ca2+,
Hg2+, Ba2+, Pb2+, Cd2+, Co2+, Ni2+, Sr2+, Cr3+, Cu2+, Ag+, Al3+, Fe3+After fluorescence spectrum.Zn2+Addition make examination
Agent s1 fluorescence intensity at 457nm strengthens.And the addition of other above-mentioned Experiment Metal ions, the fluorescence not changing reagent s1 is strong
Degree.The excitation wavelength of test is 360nm.
Fig. 3. reagent s1 is detected Mg by coexistent metallic ion2+Fluorescence intensity impact.
It is 1.00 × 10 in concentration-4 mol·L-1In the DMF solution of reagent s1, add 2.00 × 10-3 mol·L-1's
Mg2+Rear mensuration reagent s1 is the fluorescence intensity level at 430nm at wavelength.The most respectively to reagent s1-Mg2+Mixed solution adds
Concentration is Mg2+Other metal ions of concentration 10 times amount: Li+, Na+, K+, Zn2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2 +, Cd2+, Pb2+, Ag+, Al3+, Fe3+, Cr3+After the change of fluorescence intensity level.Black bar represents and adds respectively in reagent s1 solution
Enter the fluorescence intensity of different metal ion.White bars represents at reagent s1-Mg2+Solution is separately added into again other metals above-mentioned from
Son coexist after the change of fluorescence intensity level at 430nm.Reagent s1 detects Mg2+Fluorescence intensity except slightly by Hg2+, Pb2+, Cd2 +, Co2+And Cu2+Outside the impact that ion coexists, other Experiment Metal ion coexists and will not cause reagent s1-Mg2+Solution fluorescence is strong
The change of degree.Show that reagent s1 detects Mg2+Fluorescence intensity by other Experiment Metal ions in addition to above-mentioned metal ion not altogether
The impact deposited.The excitation wavelength of test is 350nm, and fluorescence emission wavelengths is 430nm.
Fig. 4. reagent s1 is detected Zn by coexistent metallic ion2+Fluorescence intensity impact.
It is 1.00 × 10 in concentration-4 mol·L-1The DMF/H of s12O(1/4, v/v) in solution, add 2.00 × 10-3
mol·L-1Zn2+Rear mensuration reagent s1 is the fluorescence intensity level at 457nm at wavelength.The most respectively to reagent s1-Zn2+In solution
Addition concentration is Zn2+Other metal ions of concentration 10 times amount: Li+, Na+, K+, Mg2+, Ca2+, Ba2+, Sr2+, Hg2+, Co2+, Ni2 +, Cu2+, Cd2+, Pb2+, Ag+, Al3+, Fe3+, Cr3+After the change of fluorescence intensity level.Black bar represents and divides in reagent s1 solution
Jia Ru the fluorescence intensity of different metal ion.White bars represents at reagent s1-Zn2+Solution is separately added into other metals above-mentioned again
Ion coexist after the change of fluorescence intensity level at 457nm.Reagent s1 detects Zn2+Fluorescence intensity except slightly by Co2+, Cr3+,
Ni2+, Cu2+And Hg2+Impact outside, other Experiment Metal ion coexists and will not cause reagent s1-Zn2+The change of solution fluorescence intensity
Change.Show that reagent s1 detects Zn2+Fluorescence intensity do not coexisted by other metal ions in addition to above-mentioned metal ion and affected.Survey
The excitation wavelength of examination is 360nm, and fluorescence emission wavelengths is 457nm.
Fig. 5. the Mg of variable concentrations2+Fluorescence titration spectrogram to reagent s1.
It is 1.00 × 10 in concentration-4 mol·L-1The DMF solution of reagent s1 is separately added into variable concentrations Mg2+To reagent
In s1 solution, along with Mg2+Addition, the fluorescence spectrum recorded respectively.Emission peak at 430nm gradually rises.Swashing of test
Sending out wavelength is 350nm.
Fig. 6. the Zn of variable concentrations2+Fluorescence titration spectrogram to reagent s1.
It is 1.00 × 10 in concentration-4 mol·L-1The DMF/H of reagent s12O(1/4, v/v) solution is separately added into different dense
Degree Zn2+In s1 solution, along with Zn2+Addition, the fluorescence spectrum recorded respectively.Emission peak at 457nm gradually rises.
The excitation wavelength of test is 360nm.
Fig. 7. reagent s1 fluorescent spectrometry detection Mg2+Calibration curve.
Vertical coordinate is the fluorescence intensity level at a length of 430nm of transmitted wave, and abscissa is Mg2+Concentration.Excitation wavelength is
350nm。Mg2+The concentration range of linearity of response is 8.0 × 10-7~1.0×10-5 mol·L-1。
Fig. 8. reagent s1 fluorescent spectrometry detection Zn2+Calibration curve.
Vertical coordinate is the fluorescence intensity level at a length of 457nm of transmitted wave, and abscissa is Zn2+Concentration.Excitation wavelength is
360nm。Zn2+The concentration range of linearity of response is 9.0 × 10-7~1.2×10-5 mol·L-1。
Fig. 9. the DMF solution of reagent s1 fluorescence spectrum in the presence of different anions.
Concentration is 1.00 × 10-4 mol·L-1The DMF solution of reagent s1, is not added with anion respectively or adds 2.00 × 10-3
mol·L-1Anion F-, Cl-, Br-, I-, HSO4 -, AcO-, NO3 -, ClO4 -, PF6 -, H2PO4 -After fluorescence spectrum.F-Addition
S1 fluorescence at 460nm is made to be obviously enhanced.And fluorescence that the addition of other above-mentioned experiment aniones will not change reagent s1 is strong
Degree.Maximum excitation and transmitting wavelength are respectively 360nm and 460nm.
Figure 10 counter anion is to reagent s1 Fluorometric assay F-Impact.
It is 1.00 × 10 in concentration-4 mol·L-1In the DMF solution of reagent s1, add 2.00 × 10-3 mol·L-1F-
Rear fluorescence is obviously enhanced.The most respectively to reagent s1-F-Adding concentration in solution is F-Other aniones Cl of concentration 10 times amount-,
Br-, I-, HSO4 -, AcO-, NO3 -, ClO4 -, PF6 -, H2PO4 -After fluorescence intensity change.Black bar represents in reagent s1 solution
It is separately added into the fluorescence intensity of different anions.White bars represents at reagent s1-F-Solution is separately added into other the moon above-mentioned from
Son coexist after fluorescence intensity change.Show that reagent s1 detects F-The shadow that do not coexisted by other aniones above-mentioned of fluorescence intensity
Ring.Maximum excitation and transmitting wavelength are respectively 360nm and 460 nm.
Figure 11. the F of variable concentrations-Fluorescence method spectra for titration figure to reagent s1.
It is 1.00 × 10 in concentration-4 mol·L-1 The DMF solution of reagent s1 is separately added into variable concentrations F-To reagent s1
In solution, along with F-Addition, the fluorescence spectrum recorded respectively.Emission peak at 460nm gradually rises.The excitation wave of test
A length of 360nm.
Figure 12. reagent s1 fluorescent spectrometry detection F-Calibration curve.
Vertical coordinate is the fluorescence intensity at a length of 460nm of transmitted wave, and abscissa is F-Concentration.Excitation wavelength is 360nm.
The range of linearity is 8.0 × 10-7~1.2×10-5 mol·L-1。
Detailed description of the invention
Embodiment one:
In analysis method of the present invention, the compound method of each reagent is:
(1) preparation of reagent s1 solution: weigh the reagent s1 of 21.5 mg, dissolves with DMF, is configured to 500mL solution, dense
Degree is 1.00 × 10-4 mol·L-1。
(2) Mg2+Standard solution: weigh 25.6mg analytical pure Mg (NO3)2, use second distillation water dissolution, and be configured to
100mL solution, Mg2+Concentration be 2.00 × 10-3 mol·L-1；As required with redistilled water stepwise dilution to suitable
Concentration；Other experiment metal ion compound methods are identical.
(3) Zn2+Standard solution: weigh 29.7mg analytical pure Zn (NO3)2, use second distillation water dissolution, and be configured to
100mL solution, Zn2+Concentration be 2.00 × 10-3 mol·L-1；As required with redistilled water stepwise dilution to suitable
Concentration；Other experiment metal ion compound methods are identical.
(4) F-Standard solution: weigh 52.2 mg tetrabutyl ammonium fluoride DMSO and dissolve, be configured to 100 mL solution, concentration
It is 2.00 × 10-3 mol×L-1.The preparation of other aniones is identical.
Spectrofluorophotometer model used by the present invention is Cary Eclipse spectrofluorophotometer, U.S. VARIAN
Company produces.
The present invention utilizes a kind of fluorometric reagent s1, can be used not only for metal ions M g2+And Zn2+Detection, but also also can
For anion F-Detection, by control aqueous medium condition, under the conditions of water solublity and non-aqueous media, realize difference respectively
The high selection of ion, high-sensitive detection.The present invention is to Mg2+、Zn2+Or F-Detection limit as little as 10-8 mol·L-1, detection limit
Low, selectivity is good, highly sensitive.Without separating step, simple to operate, operation and control method are easy, unique properties.
Embodiment two:
(1) to Mg2+Ion detection
The DMF storing solution (1.00 × 10 of reagent s1 is added in 10.0 mL volumetric flasks-4 mol·L-1, 1mL), metal
ION Mg2+(2.00 × 10-3 mol·L-1, 1 mL), it is diluted to scale with DMF solution, shakes up and carry out fluorescence spectrometry.
Arranging fluorescence exciting wavelength is 350nm, adds reagent s1(1.00 × 10 of about 3ml in the cuvette of 1cm-4
mol·L-1) DMF solution carry out fluorescence spectrum test, reagent s1 has hypofluorescence to launch at 430nm wavelength, under uviol lamp
Substantially fluorescence is not observed.Add Mg2+(2.00 × 10-3 mol·L-1After), the fluorescence at 430nm of reagent s1 solution is strong
Degree is obviously enhanced (increasing by 13.7 times), under the same terms, is separately added into Li in reagent s1 solution+, Na+, K+, Zn2+, Ca2+, Ba2 +,Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Ag+, Pb2+, Cd2+, Al3+, Cr3+, Fe3+After metal ion, change reagent s1 hardly
Fluorescence spectrum and intensity.Reagent s1 is only to Mg2+Selective fluoroscopic examination response performance, selecting wavelength is at 430nm wavelength
Fluorescence intensity level carry out quantitative determining (accompanying drawing 1).
Under the conditions of above-mentioned fluorescence method same test, reagent s1 detects Mg2+Fluorescent value at 430nm wavelength above-mentioned its
He is present in reagent s1-Mg respectively as coexisting ion by metal ion2+In mixed solution, when coexistent metallic ion concentration is test
Mg2+During 10 times of ion, other metal ion does not the most affect reagent s1 to Mg2+Fluoremetry (accompanying drawing 3).
Under the conditions of above-mentioned fluorometric investigation, measure Mg respectively2+Concentration changes the fluorescence spectrum change with reagent s1, it is thus achieved that glimmering
Light spectra for titration curve (accompanying drawing 5) and calibration curve (accompanying drawing 7).By the slope of calibration curve and the standard of 10 blank values of mensuration
Deviation, measures and is calculated reagent s1 Fluorometric assay Mg2+The concentration range of linearity and detection limit be listed in table 1.
The analytical parameters of table 1 reagent s1 detection Mg2+ ion2+
| The calibration curve range of linearity | Correlation coefficient | Detection limit |
| 8.0×10-7~1.0×10-5 mol·L-1 | 0.9934(n=11) | 3.25×10-8 mol·L-1 |
(2) to Zn2+Ion detection
The DMF/H of reagent s1 is added in 10.0 mL volumetric flasks2O(1/4, v/v) storing solution (1.00 × 10-4 mol·
L-1, 1mL), configuration metal ions Zn2+(2.00 × 10-3 mol·L-1, 1 mL), use DMF/H2O(1/4, v/v) solution be diluted to carve
Degree, shakes up and carries out fluorescence spectrometry.
Arranging fluorescence exciting wavelength is 360nm, adds reagent s1(1.00 × 10 of about 3ml in the cuvette of 1cm-4
mol·L-1) DMF/H2O(1/4, v/v) solution carries out fluorescence spectrum test, and reagent s1 has hypofluorescence to send out at 457nm wavelength
Penetrate, under uviol lamp, substantially do not observe fluorescence.Add Zn2+(2.00 × 10-3 mol·L-1After), reagent s1 solution
Fluorescence intensity at 457nm is obviously enhanced (increasing by 13.1 times), under the same terms, is separately added into Li in reagent s1 solution+, Na+, K+, Mg2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Ag+, Pb2+, Cd2+, Al3+, Cr3+, Fe3+After metal ion, several
Fluorescence spectrum and the intensity of reagent s1 will not be changed.Reagent s1 is only to Zn2+Selective fluoroscopic examination response performance, selects ripple
Fluorescence intensity level at a length of 457nm wavelength carries out quantitative determining (accompanying drawing 2).
Under the conditions of above-mentioned fluorescence method same test, reagent s1 detects Zn2+Fluorescent value at 457nm wavelength above-mentioned its
He is present in reagent s1-Zn respectively as coexisting ion by metal ion2+In mixed solution, when coexistent metallic ion concentration is test
Zn2+During 10 times of ion, other metal ion does not the most affect reagent s1 to Zn2+Fluoremetry (accompanying drawing 4).
Under the conditions of above-mentioned fluorometric investigation, measure Zn respectively2+Concentration changes the fluorescence spectrum change with reagent s1, it is thus achieved that glimmering
Light spectra for titration curve (accompanying drawing 6) and calibration curve (accompanying drawing 8).By the slope of calibration curve and the standard of 10 blank values of mensuration
Deviation, measures and is calculated reagent s1 Fluorometric assay Zn2+The concentration range of linearity and detection limit be listed in table 2.
The analytical parameters of table 2 reagent s1 detection Zn2+ ion2+
| The calibration curve range of linearity | Correlation coefficient | Detection limit |
| 9.0×10-7~1.2×10-5 mol·L-1 | 0.9965(n=11) | 5.32×10-8 mol·L-1 |
(3) to F-Ion detection
The DMF storing solution (1.00 × 10 of reagent s1 is added in 10.0 mL volumetric flasks-4 mol·L-1, 1mL), cloudy from
Sub-F-(2.00 × 10-3 mol·L-1, 1 mL).Being diluted to scale with DMF solution, shake up, the quartz colorimetric utensil moving into 1cm is carried out
Fluorescence spectrometry.The spectrometric excitation wavelength of reagent s1 solution fluorescence is 360nm.
Agents useful for same, test water and spectrofluorophotometer model and manufacturing firm are the most ibid.
In DMF solution, reagent s1(1.00 × 10-4 mol·L-1) itself there is the most weak fluorescent emission, at uviol lamp
Under substantially do not observe fluorescence.It is separately added into F-(2.00 × 10-3 mol·L-1Reagent s1 solution fluorescence at 460nm is made after)
It is obviously enhanced (strengthening 22.4 times), except F-There was added outside significant Fluorescence Increasing, other test anion Cl-, Br-, I-,
AcO-, HSO4 -, NO3 -, ClO4 -, PF6 -, H2PO4 -Reagent s1 solution is all responded without obvious signal, shows that reagent s1 is only to F-
Selective Fluorescence Increasing detection response performance (accompanying drawing 9).
Under above-mentioned fluorescence method test condition, reagent s1 detects F-Fluorescence intensity in above-mentioned anion respectively as coexisting
Ion is present in reagent s1-F-In mixed solution, as the F that coexisting ion concentration is test-During 10 times of ion, all above-mentioned common
Deposit ion-pairing agent s1 and detect F-Fluorescence intensity impact relative deviation within 5%, not interference measurement (accompanying drawing 10).
In DMF solution, for fluorescence excitation and launch wavelength with 360/460nm, measure F-Concentration is tried when changing accordingly
The fluorescence intensity change (accompanying drawing 11) of agent s1 solution, it is thus achieved that calibration curve (accompanying drawing 12).Respectively by slope and the survey of calibration trace
The standard deviation of fixed 10 blank values, measures and is calculated the concentration range of linearity and the detection limit of reagent s1 detection specific ion
It is listed in table 3.
The analytical parameters of table 3 reagent s1 detection F-ion-
| Calibration curve range of linearity mol L-1 | Correlation coefficient | Detection limit mol L-1 |
| 8.0×10-7~1.2×10-5 | 0.9917(n=11) | 1.65×10-8 |
Claims (5)
1. one kind is detected micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry, it is characterized in that with chemical name for double-(7-hydroxyl-
Coumarin-8-aldehyde) compound of contracting ethylenediamine, it is abbreviated as s1, is used for detecting micro Mg as fluorescence method2+、Zn2+Or F-Fluorescence
Reagent；(1) reagent s1 measures Mg in N,N-dimethylformamide (DMF) solution2+Time, with 350nm as fluorescence exciting wavelength, survey
Determine the fluorescence intensity at 430nm, at Mg2+In the range of finite concentration, fluorescence intensity and Mg2+Concentration is linear, increases with fluorescence
Strong method measures Mg2+；(2) reagent s1 is at DMF/H2O:1/4, v/v solution measures Zn2+Time, with 360nm as fluorescence exciting wavelength,
Measure the fluorescence intensity at 457nm, at Zn2+In the range of finite concentration, fluorescence intensity and Zn2+Concentration is linear, uses fluorescence
Enhancing method measures Zn2+；(3) reagent s1 measures F in DMF solution-Time, with 360nm as fluorescence exciting wavelength, measure at 460nm
Fluorescence intensity, at F-In the range of finite concentration, fluorescence intensity and F-Concentration is linear, measures F with catalytic fluorescence method-。
One the most according to claim 1 detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry, it is characterized in that (1)
Measure Mg2+Time, other coexistent metallic ion: Zn2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Cd2+, Pb2+, Li+, Na+, K+, Ag+, Al3+, Fe3+, Cr3+One of, it is Mg in concentration2+During concentration 10 times amount, except Co2+, Cu2+, Pb2+, Cd2+, Zn2+Ion
Coexisting outside impact, other metal ion does not disturb Mg2+Mensuration；(2) Zn is measured2+Time, other coexistent metallic ion: Mg2+,
Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Cd2+, Pb2+, Li+, Na+, K+, Ag+, Al3+, Fe3+, Cr3+One of, in concentration
For Zn2+During concentration 10 times amount, except Hg2+, Co2+, Cu2+, Cr3+, Ni2+Ion coexists outside impact, and other metal ion does not disturbs
Zn2+Mensuration；(3) F is measured-Time, other counter anion: Cl-, Br-, I-, HSO4 -, AcO-, NO3 -, ClO4 -, PF6 -, H2PO4 -,
PF6 -One of, it is F in concentration-During concentration 10 times amount, do not disturb F-Mensuration.
One the most according to claim 1 detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry, it is characterized in that (1)
Fluorometric reagent s1 detects micro Mg2+The concentration range of linearity be 8.0 × 10-7~1.0×10-5 mol·L-1, detection limit as little as 10-8 mol·L-1；(2) fluorometric reagent s1 detects trace Zn2+The concentration range of linearity be 9.0 × 10-7~1.2×10-5 mol·L-1, detection limit as little as 10-8 mol·L-1；(3) fluorometric reagent s1 detects trace F-The concentration range of linearity be 8.0 × 10-7~1.2
×10-5 mol·L-1, detection limit the most as little as 10-8 mol·L-1。
One the most according to claim 1 detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry, it is characterized in that described
Fluorometric reagent s1 chemical structural formula is:
S1
Molecular formula: C22H16N2O6
Molecular weight: 404.10
Fusing point: more than 300 DEG C
Dissolubility: be slightly soluble in chloroform, dimethyl sulfoxide, DMF etc., insoluble in ethanol
Spectral quality: with Mg in DMF solution2+After forming coordination compound, with 350nm as fluorescence exciting wavelength, launch 430nm wavelength
Fluorescence；At DMF/H2With Zn in O:1/4, v/v solution2+After forming coordination compound, with 360nm as fluorescence exciting wavelength, launch
The fluorescence of 457nm wavelength；With F in DMF solution-After forming coordination compound, with 360nm as fluorescence exciting wavelength, launch 460nm ripple
Long fluorescence.
One the most according to claim 1 detects micro Mg respectively2+、Zn2+Or F-Fluorescent spectrometry, fluorometric reagent used
Double-(7-hydroxyl-coumarin-8-aldehyde) contracting ethylenediamine is characterized in that synthetic method is with umbelliferone, hexamethylenetetramine
It is raw material with ethylenediamine, with dichloromethane, ethanol as solvent, with trifluoroacetic acid as solvent with catalyst, through acetylation, formyl
Change, condensation reaction and obtain.
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| US4007188A (en) * | 1973-01-02 | 1977-02-08 | Sandoz Ltd. | Coumarin and coumarinimide derivatives |
| JP3720520B2 (en) * | 1997-03-27 | 2005-11-30 | タカラバイオ株式会社 | Method for measuring the interaction between sugar and target |
| CN1111190C (en) * | 2000-01-21 | 2003-06-11 | 大连理工大学 | Fluorescent coumarin dye |
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