CN104122222B - Absorption spectrum analytical method for detecting ultraviolet ratio of micro-amount Zn<2+>or F<-> - Google Patents

Absorption spectrum analytical method for detecting ultraviolet ratio of micro-amount Zn<2+>or F<-> Download PDF

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CN104122222B
CN104122222B CN201410385242.7A CN201410385242A CN104122222B CN 104122222 B CN104122222 B CN 104122222B CN 201410385242 A CN201410385242 A CN 201410385242A CN 104122222 B CN104122222 B CN 104122222B
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ratio
reagent
concentration
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absorption
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CN104122222A (en
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李丽
牟兰
曾晞
沈韵
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Guangxi fine chemical products quality technology testing Co., Ltd
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Guizhou University
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Abstract

The invention relates to an absorption spectrum analytical method for detecting the ultraviolet ratio of micro Zn<2+> or F<->, and belongs to the field of analytical chemistry. 1,5-2(7-hydroxyl-8-coumarin methylene)-diamidourea abbreviated into S3 is used as a reagent for detecting the micro-amount Zn<2+> or F<->. Ratio absorption is formed at the positions of 360nm and 310nm in a DMF (dimethylformamide)/H2O(2/3,v/v) solution when Zn<2+> is determined, and an isoabsorptive point exists at the position of 380nm; the ratio absorption is formed at the positions of 400nm and 310nm when F<-> is determined, and an isoabsorptive point exists at the position of 354nm; the linearity range of the concentration of Zn<2+> or F<-> has two magnitude orders, and the detection limit is as low as 10<-7>mol.L<-1>; a preparation method of the S3 comprises the step of connecting 8-formyl group-7-umbelliferone at two ends of carbohydrazide, wherein 7-umbelliferone and the carbohydrazide are used as raw materials. The structural formula is described in the specification.

Description

A kind of detection trace Zn 2+ or the ultraviolet ratio absorption spectroanalysis method of F-
Technical field
The invention belongs to analytical chemistry field, specifically a kind of detection trace Zn2+Or F-Ultraviolet ratio absorption spectrum Analytic approach.
Background technology:Ratio absorption measurement technology is one of ultraviolet absorption spectroscopy important method, refers to adopt There is the probe reagent of the ratio absorbent properties absorbance of maximum absorption wave strong point and after reacting with determinand under separate state To detect a kind of method of material in the ratio of the absorbance of another maximum absorption wave strong point as detection signal.Because ratio is inhaled Receive the ratio of two maximum absorption wave strong point absorbances that probe reagent measures using under same environment as signal parameter, if there being shadow Loud then two at absorbance same change all can occur, error is cancelled out each other, and ratio is substantially unaffected, and result is revised, So can be reduced by the application that ratio absorbs probe reagent losing because of the data that the factors such as concentration and probe concentration, sample and equipment cause Very, obtaining more accurately result is significantly, also improves selectivity, sensitivity, responding range etc. simultaneously. Compared with the change in single wavelength absorption intensity, using different wave length absorb rate of change and possess higher stability and The degree of accuracy.For the probe of single wavelength, probe itself concentration, test condition, the intensity of light source can be subject in actual applications The impact of the factor such as fluctuation and instrument sensitivity, reduces the degree of accuracy of mensure.And the phase with regard to contrast ratio absorption measurement technology It is extremely rare for closing report.
Zinc is the second enriched in metals that life system relays after iron, contains 2~3g zinc in adult human body.People are Recognize that zinc plays a very important role in life process, for example the synthesis of enzyme and neurotransmission, protein structure and The aspects such as function are all closely related with the presence of zinc, and zinc has an effect on immunologic function and ability of learning and memory of people etc..Many raw During reason
Play an important role.Meanwhile, the impact to environment for the zinc ion also result in people's most attention.Therefore, exploitation has The zinc ion detection method of effect, the correlative study for fields such as life science, medical science and environment is of great importance.At present, to the greatest extent Pipe has a lot of reports with regard to detecting zinc ion, but there is also some problems, as relatively low in sensitivity, selective not high defect. And detect that zinc ion has the advantages that high sensitivity, high selectivity using ultraviolet ratio absorption process.
Fluorine ion is one of important trace element in human body, most important to the health of human body, and it can effectively pre- preventing decayed tooth Tooth, improves bone density, is widely used in terms for the treatment of osteoporosis;Meanwhile, clinic study shows, once heavy dose of Absorption or absorption fluorine ion a small amount of for a long time, human stomach, the damage of renal function will be led to and cause bone fluorine poisoning etc..Fluorine To environment, fresh water environment for example for the survival of mankind can produce important impact, no matter from health or ring to the content of ion From the aspect of the protection of border, the detection of fluorine ion is all significant.With traditional fluorine ion detection means such as chromatography of ions Compare, ultraviolet ratio absorption process has the advantages such as easy to detect, sensitivity is high, responding range width.
Content of the invention:It is an object of the invention to study that a kind of energy is highly sensitive, the detection of high selectivity and high stability micro- Amount Zn2+Or F-New method.The purpose of the present invention develops the new colour reagent of synthesis by inventor, using ratio absorbance Method is to Zn2+Or F-Detected.
A kind of present invention detection trace Zn2+Or F-Ultraviolet ratio absorption spectroanalysis method, be with chemical name be 1,5- The compound of two (7- hydroxyl -8- cumarin methylene)-diaminourea, is abbreviated as s3, uses as ultraviolet spectra ratio absorption process In detection trace Zn2+Or F-Reagent;(1)Reagent s3 is in DMF(N,N-dimethylformamide)/H2O(2/3, v/v)Make in solution For ultraviolet spectra ratio absorption detecting trace Zn2+Reagent, measure Zn2+When, form ratio at 360nm and 310nm and absorb, There is isobestic point at 338nm, in Zn2+In the range of finite concentration, absorbance ratio and Zn at 360nm and 310nm2+Concentration becomes Linear relationship, measures Zn with ratio absorbance method2+;(2)Reagent s3 is in DMF solvent as ultraviolet spectroscopy ratio absorption detecting Micro F-Reagent, measure F-When, form ratio at 400nm and 310nm and absorb, have isobestic point at 354nm, in F-One Determine in concentration range, absorbance ratio and F at 400nm and 310nm-Concentration is linear, measures F with ratio absorbance method-.
A kind of above-mentioned detection trace Zn2+Or F-Ultraviolet ratio absorption spectroanalysis method be(1)Measure Zn2+When other altogether Deposit metal ion:Li+, Na+, K+, Mg2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Cd2+, Pb2+, Ag+, Al3+, Fe3+, Cr3+One of, in concentration and Zn2+When concentration is suitable, do not disturb Zn2+Mensure;(2)When measuring F-, other counter anions: Cl-, Br-, I-, HSO4 -, AcO-, NO3 -, ClO4 -, PF6 -, H2PO4 -, PF6 -, in concentration and F-When concentration is suitable, do not disturb F-Survey Fixed.
A kind of above-mentioned detection trace Zn2+Or F-Ultraviolet ratio absorption spectroanalysis method be(1)Reagent s3 is as ultraviolet Spectra ratios absorption process detects trace Zn2+, the concentration range of linearity of detection is 2.0 × 10-7~2.2×10-5mol·L-1, detection Limit as little as 10-7mol·L-1;(2)Reagent s3 detects micro F as ultraviolet spectra ratio absorption process-, the linear model of concentration of detection Enclose for 4.0 × 10-7~1.0 × 10-5mol·L-1, test limit as little as 10-7mol·L-1.
A kind of above-mentioned detection trace Zn2+Or F-Ultraviolet ratio absorption spectroanalysis method, be described reagent s3 chemistry knot Structure formula is:
Molecular formula:C21H14N4O7
Molecular weight:434.09
Fusing point:More than 300 DEG C of C
Dissolubility:It is slightly soluble in chloroform, dimethyl sulfoxide, DMF etc., insoluble in ethanol.
Spectral quality:In N,N-dimethylformamide(DMF)Solution and the mixed solvent of water(V/v, 2/3)In fluorescence swash Sending out wavelength is 310nm, and launch wavelength is 454nm, and UV absorption wavelength is 310nm.
A kind of above-mentioned detection trace Zn2+Or F-Ultraviolet ratio absorption spectroanalysis method, be the preparation of described reagent s3 Method is with umbelliferone as raw material, with dichloromethane as solvent, with the hydroxyl to 7- position in umbelliferone for the acetic anhydride Base carries out after protection obtains AP20am15, with trifluoroacetic acid as catalysts and solvents, reacting with hexamethylenetetramine, Synthesis obtains intermediate 8- formoxyl-umbelliferone;Existed by intermediate 8- formoxyl-umbelliferone and carbohydrazide again The coumarin fluorescent reagent s3 that obtain symmetrical configurations is synthesized in ethanol solution:1,5- bis- (7- hydroxyl -8- cumarin methylene Base)-diaminourea, synthetic route is as follows:
A kind of above-mentioned detection trace Zn2+Or F-Ultraviolet ratio absorption spectroanalysis method, be probe reagent s3 synthesis work Skill condition is:
(1)The synthesis of AP20am15
N2Under protection, add umbelliferone, dichloromethane, acetic anhydride, pyridine in there-necked flask, mol ratio presses 7- hydroxyl Butylcoumariii:Acetic anhydride=1:2 ~ 2.5, reaction is stirred at room temperature, filtrate decompression is distilled off solvent, with using acetic acid second after water dissolves Ester extracts, saturated common salt water washing, and sodium sulphate is dried, and filters, and column chromatography purifies and AP20am15 is obtained:
Reaction temperature:Room temperature
Reaction time:12h
Reaction dissolvent:Dichloromethane
Eluant, eluent:Chloroform
(2)The synthesis of intermediate 8- formoxyl-umbelliferone
N2Under the ice bath of protection, in there-necked flask, add AP20am15, trifluoroacetic acid, stirring, treat that temperature drops During to 0 DEG C, add hexamethylenetetramine, mol ratio presses AP20am15:Hexamethylenetetramine=1:1.5 ~ 1.8, return Stream, vacuum distillation removes solvent, adds water to be warming up to 60 DEG C of stirrings, filters, filtrate chloroform extraction, saturated common salt water washing, It is dried, filters, vacuum distillation removes solvent, all sediment fraction column chromatographies are purified and obtains intermediate 8- formyl -7- hydroxyl perfume Legumin:
Reaction temperature:Backflow
Reaction time:8 h
Reaction dissolvent:Trifluoroacetic acid
Eluant, eluent:Chloroform/methanol(v/v =100/1)
(3)1,5- bis- (7- hydroxyl -8- cumarin methylene)-diaminourea
N2Under protection, add 8- formyl-umbelliferone, absolute ethyl alcohol, carbohydrazide in there-necked flask, mol ratio presses 8- Formyl-umbelliferone:Carbohydrazide=1:0.4 ~ 0.6, backflow, filter, obtain milky with chloroform and recrystallizing methanol solid Body 1,5- bis- (7- hydroxyl -8- cumarin methylene)-diaminourea:
Reaction temperature:Backflow
Reaction time:5 h
Reaction dissolvent:Ethanol
The present invention synthesis reagent s3 with Zn2+Or F-Biabsorption peak and isobestic point, biabsorption peak can be produced during effect Ratio value changes linear with corresponding ion concentration, the change of biabsorption peak ratio is not subject to reagent itself concentration, test The factor impacts such as condition, intensity of light source change and stability of instrument, thus make the stability of mensure, the degree of accuracy higher.
The present invention is to Zn2+Or F-The test limit as little as 10 measuring-7mol·L-1, and many metal ions or anion Not interference measurements, reach selectively good, purpose that sensitivity is high.Because method choice is good, interference is little, saves in detection Many separating steps, make simple to operate, and precision of analysis is high.
The present invention can be used for configuration metal ions Zn2+Detection, can be used for anion F-Detection;Can examine in water-soluble medium Survey, also can detect under the conditions of non-aqueous media DMF.
The structure of the reagent s3 of present invention synthesis is characterized through NMR spectrum, mass spectrum and infrared spectrum.Structure Characterize data is listed in table 1.
Brief description:
The DMF/H of Fig. 1 reagent s32Absorption spectrum in the presence of different metal ions for the O solution.
Concentration is 1.00 × 10-5mol·L-1The DMF/H of reagent s32O(2/3, v/v)Solution, is not added with metal ion respectively Or add 2.00 × 10-4mol·L-1Configuration metal ions Zn2+, Li+, Na+, K+, Mg2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Cd2+, Pb2+, Ag+, Al3+, Fe3+, Cr3+Ultra-violet absorption spectrum afterwards.The DMF/H of reagent s32O mixed solution is at 310nm There are absorption, Zn2+Addition make reagent s3 at the absworption peak red shift at 310nm is to 360nm and absorbance decline, exist simultaneously One isobestic point occurs at 338nm, the addition of other Experiment Metal ions hardly changes the absorption spectrum of reagent s3.
Fig. 2 coexistent metallic ion is to reagent s3 ultraviolet spectroscopy ratio absorption detecting Zn2+Impact.
It is 1.00 × 10 in concentration-5mol·L-1Reagent s3 DMF/H2O(2/3, v/v)In solution, add 2.00 × 10-4mol·L-1Zn2+Measure wavelength afterwards and be respectively the absorbance at 310nm and 360nm.Again respectively to reagent s3-Zn2+Mixed Close other metal ions adding isodose in solution:Li+, Na+, K+, Mg2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2 +, Cd2+, Pb2+, Ag+, Al3+, Fe3+, Cr3+One of after, measure wavelength be respectively 310, the change of absorbance ratio at 360nm. Black bar represents the absorbance ratio being separately added into different metal ions in reagent s3 solution.Red bar represents in reagent s3- Zn2+It is separately added into the change of the absorbance ratio after other metal ions above-mentioned coexist in mixed solution.Show that reagent s3 detects Zn2+Ratio absorb and do not coexisted by other metal ions above-mentioned and affected.Ratio absorbing wavelength is 310,360nm.
The Zn of Fig. 3 variable concentrations2+Spectra for titration figure is absorbed to the ultraviolet spectroscopy ratio of reagent s3.
It is 1.00 × 10 in concentration-5mol·L-1The DMF/H of reagent s32O(2/3, v/v)It is separately added into different dense in solution Degree Zn2+To in reagent s3 solution, with Zn2+Addition, record absorption spectrum curve respectively.Absorption at 310nm for the reagent s3 Gradually, to 360nm, an isobestic point at 338nm simultaneously in red shift at peak.Form ratio at 310nm and 360nm wavelength Absorb.
Ultraviolet absorption spectroscopy ratio absorption detecting Zn of Fig. 4 reagent s32+Calibration curve.Ordinate is absorbing wavelength It is respectively the absorbance ratio at 360nm and 310nm, abscissa is Zn2+Concentration.Zn2+Response the concentration range of linearity be 2.0×10-7~2.2×10-5mol·L-1.
Absorption spectrum in the presence of different anions for the DMF solution of Fig. 5 reagent s3.
Concentration is 1.00 × 10-5mol·L-1The DMF solution of reagent s3, is not added with anion respectively or adds 5.00 × 10-5 mol·L-1Anion F-, Cl-, Br-, I-, HSO4 -, AcO-, NO3 -, ClO4 -, PF6 -, H2PO4 -Ultra-violet absorption spectrum afterwards.F-'s Add make reagent s3 absworption peak 310nm at gradually red shift to 400nm at, simultaneously at 354nm appearance one isobestic point. The addition of other above-mentioned experiment anion hardly changes the absorption spectrum of reagent s3.
Fig. 6 counter anion detects F to reagent s3 ultraviolet absorption spectroscopy-Impact.
It is 1.00 × 10 in concentration-5mol·L-1The DMF solution of reagent s3 in, add 5.00 × 10-5mol·L-1's F-Absworption peak at 310nm after solution gradually red shift to 400 nm.Again respectively to reagent s3-F-Add equal in mixed solution Other anion Cl of amount-, Br-, I-, HSO4 -, AcO-, NO3 -, ClO4 -, PF6 -, H2PO4 -, PF6 -One of after, mensuration absorbance become Change.Black bar represent be separately added into different anions in data s3 solution after absorbance ratio at 400nm and 310nm. Red bar represents in data s3-F-It is separately added into the absorbance ratio after other anion above-mentioned coexist in mixed solution.Show Data s3 detects F-Ratio absorb and do not coexisted by other anion above-mentioned and affected.Ordinate is the suction at 400nm and 310nm Luminosity ratio.
The F of Fig. 7 variable concentrations-Spectra for titration figure is absorbed to data s3 ultraviolet spectroscopy ratio.
It is 1.00 × 10 in concentration-5mol·L-1The DMF solution of data s3 in be separately added into variable concentrations F-To data In s3 solution, with F-Addition, the absorption spectrum curve recording respectively.The gradually red shift of the absworption peak at 310nm of data s3 To 400nm, an isobestic point occurs at 354nm simultaneously.400nm forms ratio absorption with the absorption at 310nm wavelength.
Fig. 8 reagent s3 ultraviolet absorption spectroscopy ratio absorption detecting F-Calibration curve.Ordinate is for absorbing wavelength respectively For the absorbance ratio at 400nm and 310nm, abscissa is F-Concentration.F-The concentration range of linearity of response is 4.0 × 10-7~ 1.0×10-5mol·L-1.
Specific embodiment
Embodiment one:
In analysis method of the present invention, the compound method of each reagent is:
(1)The preparation of reagent s3 solution:Weigh the reagent s3 of 44mg, with DMF dissolving, be configured to 100mL solution, concentration is 1.00×10-3mol·L-1
(2)Zn2+Standard liquid:Weigh 59.5mg and analyze pure Zn (NO3)2, use second distillation water dissolves, and be configured to 100mL solution, Zn2+Concentration be 2.00 × 10-3mol·L-1;Use redistilled water stepwise dilution as needed to suitable Concentration;The preparation of other coexistent metallic ion solution is identical.
(3) F-Storing solution (2.00 × 10-3mol×L-1):Weigh 52.2 mg tetrabutyl ammonium fluoride DMSO dissolvings, join Make 100 mL solution.The preparation of other anion is identical.
Ultraviolet-visible spectrophotometer model UV-1800 used by the present invention, company of Japanese Shimadzu Corporation produces.
Reagent s3 in the inventive method, can be used as trace Zn2+Or F-The ratio absorption reagent of the detection of ion.There is inspection Survey superior performance, detection good stability, ambient interferences are little, selectivity is high, test limit is low, it is to be separated to be not required to, can be in water solubility Or under the conditions of non-aqueous media the advantages of test.Operation and control method are easy, unique properties.
Embodiment two:
(1)To metal ion detection
The DMF storing solution of reagent s3 is added in 10.0 mL volumetric flasks(1.00×10-4mol·L-1, 1mL), metal Ion Zn2+(2.00×10-3mol·L-1, 1 mL), use DMF/H2O(2/3, v/v)Solution is diluted to scale, shakes up and carries out ultraviolet Absorption spectromtry.
The reagent s3 of about 3ml is added in the cuvette of 1cm(1.00×10-5mol·L-1)DMF/H2O(2/3, v/v) Solution carries out ultra-violet absorption spectrum test, adds Zn in reagent s32+(2.00×10-4mol·L-1)Afterwards, reagent s3 is made to exist To 360nm and absorbance have dropped 0.042 for absworption peak red shift at 310nm, occurs one simultaneously and wait absorption at 338nm Point.Under the same terms, in reagent s3 solution, it is separately added into Li+, Na+, K+, Mg2+, Ca2+, Ba2+, Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Ag+, Pb2+, Cd2+, Al3+, Cr3+, Fe3+Metal ion after, hardly change the absorption spectrum of reagent s3 and intensity, Reagent s3 is only to Zn2+Selective ratio absorption detecting response performance, selects the ratio of absorbance at 360nm and 310nm wavelength Quantitative determined(Accompanying drawing 1).
Under above-mentioned ultraviolet spectra test condition, reagent s3 detects Zn2+Ratio absorption value at 360nm and 310nm exists Above-mentioned metal ion is present in reagent s3-Zn respectively as coexisting ion2+In mixed solution, when coexistent metallic ion concentration and survey The Zn of examination2+When ion is suitable, to detection Zn2+Ratio absorbance impact relative deviation within 5%, not interference measurement(Attached Fig. 2).
Under above-mentioned ultraviolet spectra test condition, measure Zn respectively2+Concentration changes the ultra-violet absorption spectrum change with reagent s3 Change and the absorbance ratio at 360nm and 310nm, obtain absorption spectrum titration curve(Accompanying drawing 3)And the calibration of ratio absorption process Curve(Accompanying drawing 4).By slope and the standard deviation measuring 10 blank values of calibration curve, measure and be calculated reagent s3 purple External absorbent method ratio absorption detecting Zn2+The concentration range of linearity and detection limit be listed in table 2.
Table 2 reagent s3 detects Zn2+The analytical parameters of ion
(2)To Anionic recognition
The DMF storing solution (1.00 × 10 of reagent s3 is added in 10.0 mL volumetric flasks-4mol·L-1, 1mL), cloudy from Sub- F-(5.00×10-4mol·L-1, 1 mL).It is diluted to scale with DMF solution, shakes up, the quartz colorimetric utensil moving into 1cm is carried out Ultra-violet absorption spectrum measures.
To reagent s3(1.00×10-5mol·L-1)DMF solution carry out ultra-violet absorption spectrum scanning, add F-(Concentration For 5.00 × 10-5mol·L-1) after, make reagent s3 the absworption peak at 310nm gradually red shift to 400nm at, exist simultaneously One isobestic point occurs at 354nm.Except F-Addition so that reagent s3 is had outside obvious absorption signal, other test anion Cl-, Br-, I-, HSO4 -, NO3 -, AcO-, ClO4 -, PF6 -, H2PO4 -The all no obvious UV response signal to reagent s3(Attached Fig. 5).Show reagent s3 to F-There is UV absorption recognition detection performance.
Under above-mentioned ultraviolet absorption method test condition, reagent s3 detects F-Absorbance in above-mentioned anion respectively as altogether Deposit ion and be present in reagent s3-F-In mixed solution, as the F of coexisting ion concentration and test-When ion is suitable, to detection F-'s Absorbance impact relative deviation within 3%, not interference measurement(Accompanying drawing 6)
In DMF solution, with 310nm as maximum absorption wavelength, measure F-Corresponding reagent s3 solution when concentration changes Ratio Change of absorption, obtains calibration curve(Accompanying drawing 8).Respectively by slope and the standard deviation measuring 10 blank values of calibration curve Difference, measures and is calculated reagent s3 and detect that the concentration range of linearity of specific ion and detection limit are listed in table 3.
Table 3 reagent s3 detects F-The analytical parameters of ion
Embodiment three:In the present invention, reagent s3's is synthetically prepared
(1)The synthesis of 7- acetic anhydride cumarin
N2Under protection, in the round-bottomed flask of 250mL, add umbelliferone(9.3g, 57.3 mmol), dichloromethane Alkane 120 mL, stirring, add acetic anhydride(11.7g, 114.6mmol), pyridine 7-8 drips, and reacts 12h under room temperature, and reaction completes First vacuum distillation removes solvent afterwards, is extracted with ethyl acetate with after water dissolves, saturated common salt water washing, and sodium sulphate is dried, and filters, Vacuum distillation removes solvent, crude product column chromatography for separation(Eluant, eluent:Chloroform)Obtain white products 7- acetic anhydride coumarin 1 1.16g, Yield 95.4%.
(2)The synthesis of intermediate feed 7- hydroxyl -8- aldehyde radical cumarin
N2Under protection, under ice bath, in the round-bottomed flask of 250mL, add 7- acetic anhydride cumarin(15g, 73.51 mmol), trifluoroacetic acid 100 mL, stirring, when temperature is down to 0 DEG C, add hexamethylenetetramine(15g, 106.26mmol), react 1h under ice bath, reaction temperature is gradually increased to room temperature, then return stirring reaction 8h, vacuum distillation removing Solvent, adds water 150mL in surplus solution, mixture is risen to 60 DEG C of stirring 30min, filters, filtrate chloroform extraction, satisfy And brine It, sodium sulphate is dried, and filters, and vacuum distillation removes solvent, and sediment fraction merges, column chromatography for separation(Eluant, eluent: Chloroform/methanol, v/v, 100/1)Obtain milky product 7- hydroxyl -8- aldehyde radical cumarin 2.61g, yield 18.6%.
(3)Fluorometric reagent s3 is the synthesis of 1,5- bis- (7- hydroxyl -8- cumarin methylene)-diaminourea
N2Under protection, in 250ml there-necked flask, add 7- hydroxyl -8- aldehyde radical cumarin(600mg, 3.16mmol)With 70mL absolute ethyl alcohol, stirring, heats up after its dissolving, is down to room temperature.By carbohydrazide(142mg, 1.58mmol)It is dissolved in 20mL no It is added dropwise over after water-ethanol, heating reflux reaction 5h.Filter after the completion of reaction, with chloroform methanol recrystallization, obtain milky white Semu Mark product 470mg, yield is 68.7%.M.p. 300 DEG C of C of >;1H NMR (CDCl3, 400MHz), δ(ppm): 4.349 (s, 1H), 6.282(d, 1H, J=9.6Hz), 6.881(d, 1H, J=8.8Hz), 7.559(d, 1H, J=8.8Hz), 7.969(d, 1H, J=9.2Hz), 8.822(s, 1H), 11.391(s, 1H); ESI-MS: m/z 457.0 [M+Na ]+.

Claims (6)

1. a kind of detection trace Zn2+Or F-Ultraviolet ratio absorption spectroanalysis method, it is characterized in that with chemical name be 1,5- bis- The compound of (7- hydroxyl -8- cumarin methylene)-diaminourea, is abbreviated as s3, is used for as ultraviolet spectra ratio absorption process Detection trace Zn2+Or F-Reagent;(1)Reagent s3 is in DMF(N,N-dimethylformamide)And H2The volume ratio of O is 2:3 solution Middle as ultraviolet spectra ratio absorption detecting trace Zn2+Reagent, measure Zn2+When, form ratio at 360nm and 310nm and inhale Receive, have isobestic point at 338nm, in Zn2+In the range of finite concentration, absorbance ratio and Zn at 360nm and 310nm2+Concentration Linear, measure Zn with ratio absorbance method2+;(2)Reagent s3 absorbs inspection as ultraviolet spectroscopy ratio in DMF solvent Micrometer amount F-Reagent, measure F-When, form ratio at 400nm and 310nm and absorb, have isobestic point at 354nm, in F- In the range of finite concentration, absorbance ratio and F at 400nm and 310nm-Concentration is linear, is measured with ratio absorbance method F-.
2. a kind of detection trace Zn according to claim 12+Or F-Ultraviolet ratio absorption spectroanalysis method, it is characterized in that (1)Measure Zn2+When other coexistent metallic ions:Li+, Na+, K+, Mg2+, Ca2+, Ba2+,Sr2+, Hg2+, Co2+, Ni2+, Cu2+, Cd2 +, Pb2+, Ag+, Al3+, Fe3+, Cr3+One of, in concentration and Zn2+When concentration is suitable, do not disturb Zn2+Mensure;(2)When measuring F-, Other counter anions:Cl-, Br-, I-, HSO4 -, AcO-, NO3 -, ClO4 -, PF6 -, H2PO4 -, PF6 -, in concentration and F-Concentration is suitable When, do not disturb F-Mensure.
3. a kind of detection trace Zn according to claim 12+Or F-Ultraviolet ratio absorption spectroanalysis method, it is characterized in that (1)Reagent s3 detects trace Zn as ultraviolet spectra ratio absorption process2+, the concentration range of linearity of detection is 2.0 × 10-7~2.2 ×10-5mol·L-1, test limit as little as 10-7mol·L-1;(2)Reagent s3 detects micro as ultraviolet spectra ratio absorption process F-, the concentration range of linearity of detection is 4.0 × 10-7~1.0 × 10-5mol·L-1, test limit as little as 10-7mol·L-1.
4. a kind of detection trace Zn according to claim 12+Or F-Ultraviolet ratio absorption spectroanalysis method, it is characterized in that Described reagent s3 chemical structural formula is:
Molecular formula:C21H14N4O7
Molecular weight:434.09
Fusing point:More than 300 DEG C of dissolubilities:It is slightly soluble in chloroform, dimethyl sulfoxide, DMF, insoluble in ethanol, spectrum Property:In N,N-dimethylformamide(DMF)Solution is 2 with the mixed solvent volume ratio of water:3(V/v, 2/3)In fluorescence swash Sending out wavelength is 310nm, and launch wavelength is 454nm, and UV absorption wavelength is 310nm.
5. a kind of detection trace Zn according to claim 42+Or F-Ultraviolet ratio absorption spectroanalysis method, it is characterized in that The preparation method of described reagent s3 is with umbelliferone as raw material, with dichloromethane as solvent, with acetic anhydride to 7- hydroxyl In cumarin, the hydroxyl of 7- position carries out after protection obtains AP20am15, with trifluoroacetic acid as catalysts and solvents, with Hexamethylenetetramine reacts, and synthesis obtains intermediate 8- formoxyl-umbelliferone;Again by intermediate 8- formoxyl -7- hydroxyl Butylcoumariii and carbohydrazide are synthesized the coumarin fluorescent reagent s3 obtaining symmetrical configurations in ethanol solution:1,5- bis- (7- Hydroxyl -8- cumarin methylene)-diaminourea, synthetic route is as follows:
.
6. according to a kind of detection trace Zn described in claim 52+Or F-Ultraviolet ratio absorption spectroanalysis method, it is characterized in that Probe reagent s3 synthetic technological condition is:
(1)The synthesis of AP20am15
N2Under protection, add umbelliferone, dichloromethane, acetic anhydride, pyridine in there-necked flask, it is fragrant that mol ratio presses 7- hydroxyl Legumin:Acetic anhydride=1:2 ~ 2.5, reaction is stirred at room temperature, filtrate decompression is distilled off solvent, with being extracted with ethyl acetate after water dissolves Take, saturated common salt water washing, sodium sulphate is dried, filter, column chromatography purifies and AP20am15 is obtained:
Reaction temperature:Room temperature
Reaction time:12h
Reaction dissolvent:Dichloromethane
Eluant, eluent:Chloroform
(2)The synthesis of intermediate 8- formoxyl-umbelliferone
N2Under the ice bath of protection, add AP20am15, trifluoroacetic acid, stirring in there-necked flask, treat that temperature is down to 0 DEG C When, add hexamethylenetetramine, mol ratio presses AP20am15:Hexamethylenetetramine=1:1.5 ~ 1.8, backflow, subtract Pressure is distilled off solvent, adds water to be warming up to 60 DEG C of stirrings, filters, filtrate chloroform extraction, saturated common salt water washing, is dried, Filter, vacuum distillation removes solvent, all sediment fraction column chromatographies are purified and obtains intermediate 8- formyl-umbelliferone:
Reaction temperature:Backflow
Reaction time:8 h
Reaction dissolvent:Trifluoroacetic acid
Eluant, eluent:Chloroform/methanol(v/v =100/1)
(3)1,5- bis- (7- hydroxyl -8- cumarin methylene)-diaminourea
N2Under protection, in there-necked flask add 8- formyl-umbelliferone, absolute ethyl alcohol, carbohydrazide, mol ratio press 8- formyl- Umbelliferone:Carbohydrazide=1:0.4 ~ 0.6, backflow, filter, obtain Off-white solid 1,5- with chloroform and recrystallizing methanol Two (7- hydroxyl -8- cumarin methylene)-diaminourea:
Reaction temperature:Backflow
Reaction time:5 h
Reaction dissolvent:Ethanol.
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