CN107739604A - A kind of fluorescent sensing material and its preparation and application based on rhodamine B and cyanobiphenyl phenol - Google Patents

A kind of fluorescent sensing material and its preparation and application based on rhodamine B and cyanobiphenyl phenol Download PDF

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CN107739604A
CN107739604A CN201710699751.0A CN201710699751A CN107739604A CN 107739604 A CN107739604 A CN 107739604A CN 201710699751 A CN201710699751 A CN 201710699751A CN 107739604 A CN107739604 A CN 107739604A
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sensing material
rhodamine
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CN107739604B (en
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唐旭
王赟
李静
韩娟
李程
王蕾
倪良
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Jiangsu University
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Abstract

The present invention relates to a kind of fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol and its preparation method and application, belongs to fluorescence chemical sensing material and chemical analysis detection technique field；Rhodamine acyl ethylenediamine and the xenyl cyanogen of 3 formoxyl, 4 hydroxyl 4 are dissolved in absolute ethyl alcohol by the present invention; appropriate glacial acetic acid is added, oil bath pan is stirred at reflux, and question response is cooled to room temperature after terminating; decompression removes solvent and draws crude product, recrystallizes to obtain fluorescent sensing material in ethanol；Fluorescent sensing material prepared by the present invention is to Zn2+, Al3+, Fe3+And Cr3+Four metal ion species have multiple response, the effective detection of the trace of target metal ions in environmental water sample can be realized well by the different fluorescence signals of presentation, it is easy to get with raw material, the features such as preparation technology is simple, and product stability is good and detection sensitivity is high.

Description

A kind of fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol and its prepare and Using
Technical field
It is more particularly to a kind of based on rhodamine B and cyanobiphenyl phenol the present invention relates to a kind of chemiluminescence sensing material Fluorescent sensing material and its preparation method and application, belong to fluorescence chemical sensing material and chemical analysis detection technique field.
Background technology
With the fast development of social economy, thing followed problem of environmental pollution is all heat of concern all the time Point.Heavy metal ion as one of pollutant is extremely serious to environmental hazard, is mainly shown as that heavy metal contaminants exist It can not be degraded in natural environment by Institute of Micro-biology, the change of form can only occur, and its toxicity does not have root in the process This elimination；Easily absorbed by organism, the heavy metal ion of different shape can be migrated by biological, and the mode such as enrichment acts on In animals and plants, enter human body eventually through food chain；Although some metal ions are trace elements necessary to human body, when gold When category ion intake has exceeded the Cmax of body permission, serious biological disorder is also resulted in, while can also be with life Thing polymer substance interacts, and causes boiomacromolecule to lose activity, and causes various diseases.Such as common A Er Ci Haimo diseases, Parkinson's are caused by precisely due to iron ion and aluminium ion intake are excessive；Diabetes, cardiovascular and cerebrovascular disease, swell Knurl and paraplasm all with to take in excessive chromium ion closely bound up；Slow poisoning can be caused by being so accumulated in human body, and this Kind accumulation property harm should not often be found in short term.
In order to reduce and avoid harm of the heavy metal ion to ecological environment and the mankind, the effective monitoring in real time of progress is must Indispensable.Traditional detection technique such as atomic absorption spectrophotometry, flame atomization and inductively coupled plasma Atomic emission spectrometry etc. all needs to carry out complicated pretreatment to sample before detection, and the disturbing factor of testing result is more, in addition Detecting instrument is expensive, and complex operation limits its universal application.Comparatively speaking, fluorescence detection has sensitivity Height, selectivity is strong, and the response time is short, simple to operate, and dosage is few and low cost and other advantages, trace and micro inspection available for ion Survey, be widely used in the various fields such as environmental monitoring, clinical medicine, biomolecule detection.Fluorescent sensing material is certainly Body has unique optical property, when its combining target ion, in material Photophysical Behaviors be affected, fluorescence signal Output form changes, and is realized based on the change in fluorescence of sensor before and after combining target ion as response signal to specific The quick detection of ion.The fluorescent sensing material for being directed to metal ion in recent years has been achieved for certain progress.Report Most of sensing materials in road are all based on the Schiff base material of the fluorophors such as rhodamine B, cumarin, quinoline, anthraquinone.But The sensor of wherein most is all corresponding to specific simple target metal ion.Therefore the ion fluorescence with multiple response Sensing material is the frontier studied at present, and during discriminance analysis, for different target metal ions, it can be with The change of different, measurable output optical signal is produced, therefore there are more potential using values.
The content of the invention
Present invention aims to overcome that the limitation of traditional sensing techniques, there is provided one kind is based on rhodamine B and cyanobiphenyl phenol The fluorescent sensing material with multiple response property and its production and use, the fluorescence of described multiple response property passes Sense material can realize trace Fe in environmental water sample well by the different fluorescence signals of presentation3+, Cr3+, Al3+And Zn2+Four kinds The effective detection of metal ion, is easy to get with raw material, and preparation technology is simple, and product stability is good and the spy such as detection sensitivity height Point.
The technical solution adopted by the present invention is：
Present invention firstly provides a kind of multiple response type fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol, the material Material dissolves the material in methanol/HEPES cushioning liquid (v/v=9 originally as yellowish orange pulverulent solids:1, pH=7.4) system In, yellow is presented in solution, and obvious fluorescent emission is had no under 365nm ultraviolet light.
The present invention also provides a kind of preparation of the multiple response type fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol Method, it is characterised in that comprise the following steps：
S1. the synthesis of rhodamine acyl ethylenediamine：
Bibliography Dong L, Zeng X, Mu L, et al. The synthesis of a rhodamine B schiff-base chemosensor and recognition properties for Fe3+ in neutral ethanol aqueous solution[J]. Sensors and Actuators B: Chemical, 2010, 145(1): 433- 437. are prepared.
Rhodamine B is placed in 100mL round-bottomed flask, is completely dissolved with absolute ethyl alcohol, second is added dropwise while stirring Diamines, it is placed in oil bath pan and is stirred at reflux.Question response is cooled to room temperature after terminating, decompression removes solvent and obtains rhodamine acyl second Diamines crude product, recrystallization purifying is carried out to crude product with absolute ethyl alcohol and obtains pale pink solid.
Rhodamine B, ethylenediamine in above-mentioned synthetic method, absolute ethyl alcohol：1~2.4 g（2~5mmol）：0.18~0.36 g （3~6mmol）：20 ~ 40 mL, described back flow reaction temperature are 60~70 DEG C, and the reaction time is 8~12 h.
S2. the preparation of 3- formoxyls -4- hydroxyls -4- xenyl cyanogen：
Bibliography Alici O, Erdemir S. A cyanobiphenyl containing fluorescence " turn on” sensor for Al3+ ion in CH 3CN–water [J]. Sensors and Actuators B: Chemical, 2015, 208:It is prepared by 159-163.
Cyanobiphenyl phenol and methenamine will be dissolved in glacial acetic acid, will be placed in 100 mL round-bottomed flask in oil bath pan It is stirred at reflux.Question response is cooled to room temperature after terminating, 10 M of addition hydrochloric acid solution, which is stirred at room temperature, carries out acidifying 1h, then Extracted with dichloromethane, collected organic layer, and with water washing is distilled 3 times, saturated aqueous common salt 1 time, dried with anhydrous magnesium sulfate, mistake Filter decompression removes solvent, obtains faint yellow solid.
4- hydroxyl -4- xenyls cyanogen, methenamine, glacial acetic acid, hydrochloric acid solution amount ratio in above-mentioned synthetic method are： 0.39~0.78g（2~ 4mmol): 1.41~2.82 g (10~20mmol) :30~70 mL, 80~120mL, it is described Back flow reaction temperature is 90~110 DEG C, and the reaction time is 8-12 h.
S3. the synthesis of the multiple response type fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol：
Rhodamine acyl ethylenediamine and 3- formoxyl -4- hydroxyl -4- xenyl cyanogen are dissolved in absolute ethyl alcohol, add appropriate ice second Acid, oil bath pan are stirred at reflux, and question response is cooled to room temperature after terminating, and decompression removes solvent and draws crude product, ties again in ethanol It is brilliant to obtain fluorescent sensing material.
Rhodamine acyl ethylenediamine, 3- formoxyl -4- hydroxyl -4- xenyls cyanogen described in step S3, absolute ethyl alcohol, ice second Sour amount ratio is：0.52~1.56g (1 ~ 3 mmol)：0.22g~0.67g (1 ~ 3mmol)：20~40mL：1 ~ 3 drop, it is described Back flow reaction temperature be 65~75 DEG C, the reaction time is 8~12 h.
The multiple response type fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol is used for Zn in environmental water sample2+、 Al3+、Fe3+Or Cr3+The trace analysis detection of four metal ion species.
The present invention compared with prior art, has the beneficial effect that：
（1）The invention provides a kind of multiple response type fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol, its preparation Method and application.Rhodamine B has unique lactam ring structure, the fluorescence of its solution system in itself as a kind of fluorescent dye It can be changed with color because of the opening of lactam nucleus, there is good optical property.To also having in cyanobiphenyl phenol structure Aromatic rings conjugated system, and phenolic hydroxyl group ortho position is easy to modify aldehyde radical in structure.Both are entered as connecting bridge using ethylenediamine Row combines to form the compound of a double fluorophors, and obtained material self structure is stable, and placing will not also occur for a long time Decompose.Because the lactam nucleus of rhodamine B derivative group in the compound-material is in closure state, to cyano group neighbour's phenylol The fluorescence of regiment headquarters point is not also launched, so integral system does not show fluorescence.This is also to realize switching mode fluorescence probe Provide premise.In addition the nitrogen-atoms on the carbonylic oxygen atom in compound structure, hydroxyl oxygen atom and C=N groups can all carry Binding site of the supplied for electronic as metal ion, for the material compares in general small molecule metalfluorescent sensing material, have More binding sites, it is stronger with target metal ions binding ability.
（2）The synthesis condition of fluorescent sensing material in the present invention is gently easily controllable, and post processing uses recrystallization purifying It is simple and easy, prepare that cost is cheap, and the feeding quantity in preparation process is based on lot of experiments and the optimal reaction that determines Mol ratio.Reaction temperature and time are determined based on reaction rate and yield.In optimal parameter area, synthetic yield Up to more than 75%.
（3）Fluorescent sensing material prepared by the present invention has multiple response, in fluorescent sensing material solution system, adds Zn2+Afterwards, strong blue fluorescent emissions can be observed under ultra violet lamp；Add Al3+Afterwards, the fluorescence hair of yellow can be observed Penetrate；Add Fe3+And Cr3+Afterwards, red fluorescence can be presented in system.This is because the sensing material has two different fluorescent emissions Group, when different target metal ions（Zn2+, Al3+, Fe3+, Cr3+）Difference during addition due to complexing mode can be formed The complex structure of various configuration, cause different fluorescent emissions, utilize the difference of this optical property between complex The Mutiple Choice of metal ion is realized, compared to the detection technique of traditional metal ion, the fluorescence point prepared using the present invention Son is to Zn2+, Al3+, Fe3+And Cr3+Four metal ion species are detected, selectivity and high sensitivity, it is only necessary to fluorescence spectrophotometry Meter carries out auxiliary detection, and the change naked eyes of fluorescence signal are visible under uviol lamp, and other common metal ion interference are small, greatly Big adds value.
Brief description of the drawings
Fig. 1 is the multiple response type fluorescence sense based on rhodamine B derivative and cyanobiphenyl phenol prepared by embodiment 3 The building-up process schematic diagram of material；
Fig. 2 is the fluorescent sensing material prepared by embodiment 31H NMR, wherein solvent are DMSO-D6。
Fig. 3 is the fluorescent sensing material prepared by embodiment 313C NMR scheme, and wherein solvent is DMSO-D6。
Fig. 4 is that the MS of fluorescent sensing material prepared by embodiment 3 schemes；
Fig. 5 is fluorescence spectra of the fluorescent sensing material to different metal ions prepared by embodiment 3；A is in excitation wave in figure Fluorescence spectrum under long 360nm, figure b are the fluorescence spectrum under excitation wavelength 520nm.
Fig. 6 is that fluorescent sensing material prepared by embodiment 3 is presented after different metal ions are added under ultra violet lamp The macroscopic different fluorescent emissions gone out；1 in figure represent is the fluorescent sensing material for preparing of the present invention.
Fig. 7 is ultraviolet-visible absorption spectroscopy of the fluorescent sensing material to different metal ions prepared by embodiment 3.
Fig. 8 is fluorescent sensing material prepared by embodiment 3 respectively in various concentrations Zn2+（Fig. 8 a）, Al3+（Fig. 8 b）, Fe3+ （Fig. 8 c）And Cr3+（Fig. 8 d）Fluorescence spectra in the presence of four metal ion species；Wherein illustration is respectively corresponding Fluorescence Increasing Degree（I-I0）Linear relationship between the concentration of metal ion.
Fig. 9 is fluorescent sensing material prepared by embodiment 3 in identification Zn2+（Fig. 9 a）, Al3+（Fig. 9 b）, Fe3+（Fig. 9 c）With Cr3+（Fig. 9 d）Interference experiment result figure of other common metal ions to object ion during four kinds of target metal ions；1 in figure What is represented is fluorescent sensing material prepared by the present invention.
Figure 10 is that fluorescent sensing material prepared by embodiment 3 is used for Fe in environmental water sample3+Detection fluorogram.
Embodiment
To make those skilled in the art be better understood from technical scheme, below in conjunction with brief description of the drawings to this hair Technical scheme in bright embodiment is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented Example, rather than whole embodiments, based on the embodiment in the present invention, those of ordinary skill in the art are not making creativeness The every other embodiment obtained on the premise of work, belongs to the scope of protection of the invention.
Embodiment 1：
S1. the synthesis of rhodamine acyl ethylenediamine：1g (2mmol) rhodamine B is placed in 100mL round-bottomed flask, with 20mL without Water-ethanol is completely dissolved, and 0.18g (3mmol) ethylenediamine is added dropwise while stirring, is placed in 60 DEG C of oil bath pans and is stirred at reflux 8h.Question response is cooled to room temperature after terminating, decompression removes solvent and obtains rhodamine acyl ethylenediamine crude product, with absolute ethyl alcohol pair Crude product carries out recrystallization purifying and obtains pale pink product.
S2. the preparation of 3- formoxyls -4- hydroxyls -4- xenyl cyanogen：By 0.39g（2mmol）4- hydroxyl -4- xenyl cyanogen, 1.41g (10mmol) methenamine is dissolved in 30 mL glacial acetic acids, is placed in 100mL round-bottomed flask and is stirred in 90 DEG C of oil bath pans Mix backflow.Question response is cooled to room temperature after terminating, addition 80mL 10M hydrochloric acid solution, which is stirred at room temperature, carries out acidifying 1h, so Extracted with dichloromethane, collected organic layer, and with water washing is distilled 3 times, saturated aqueous common salt 1 time, dried with anhydrous magnesium sulfate afterwards Filtering decompression removes solvent and obtains faint yellow solid afterwards.
S3. the synthesis of the multiple response type fluorescent sensing material based on rhodamine B derivative and cyanobiphenyl phenol：Will 0.52g（1mmol）Rhodamine acyl ethylenediamine and 0.23g（1mmol）3- formoxyl -4- hydroxyl -4- xenyl cyanogen be dissolved in 20mL without In water-ethanol, the glacial acetic acid of 1 drop is added, 8h is stirred at reflux in 65 DEG C of oil bath pans, question response is cooled to room temperature after terminating, decompression moves Except solvent obtains crude product, orange/yellow solid, yield 78.2% are recrystallized to obtain in ethanol.
Embodiment 2：
S1. the synthesis of rhodamine acyl ethylenediamine：By 1.44g（3mmol）Rhodamine B is placed in 100mL round-bottomed flask, uses 30mL Absolute ethyl alcohol is completely dissolved, and 0.27g (4.5mmol) ethylenediamine is added dropwise while stirring, is placed in 65 DEG C of oil bath pans and stirs back Flow 10h.Question response is cooled to room temperature after terminating, decompression removes solvent and obtains rhodamine acid diamide crude product, uses absolute ethyl alcohol Recrystallization purifying is carried out to crude product and obtains pale pink product.
S2. the preparation of 3- formoxyls -4- hydroxyls -4- xenyl cyanogen：By 0.59g (3mmol) 4- hydroxyl -4- xenyls Cyanogen, 2.11g (15mmol) methenamine are dissolved in 50 mL glacial acetic acids, are placed in 100mL round-bottomed flask in 100 DEG C of oil bath pans In be stirred at reflux.Question response is cooled to room temperature after terminating, addition 100mL 10M hydrochloric acid solution, which is stirred at room temperature, to be acidified 1h, then extracted with dichloromethane, collected organic layer, and with water washing is distilled 3 times, saturated aqueous common salt 1 time, use anhydrous magnesium sulfate Filtering decompression removes solvent and obtains faint yellow solid after drying.
S3. the synthesis of the multiple response type fluorescent sensing material based on rhodamine B derivative and cyanobiphenyl phenol：Will 1.04g rhodamine acyl ethylenediamines are dissolved in 30mL absolute ethyl alcohols with 0.45g 3- formoxyl -4- hydroxyl -4- xenyl cyanogen, add 2 The glacial acetic acid of drop, is stirred at reflux 10h in 70 DEG C of oil bath pans, and question response is cooled to room temperature after terminating, and decompression, which removes solvent and obtained, slightly produces Product, orange/yellow solid, yield 79.7% are recrystallized to obtain in ethanol
Embodiment 3：
S1. the synthesis of rhodamine acyl ethylenediamine：By 2.4g（5mmol））Rhodamine B is placed in 100mL round-bottomed flask, uses 40mL Absolute ethyl alcohol is completely dissolved, and 0.36g is added dropwise while stirring（6mmol）Ethylenediamine, it is placed in 70 DEG C of oil bath pans and is stirred at reflux 12h.Question response is cooled to room temperature after terminating, decompression removes solvent and obtains rhodamine acid diamide crude product, with absolute ethyl alcohol pair Crude product carries out recrystallization purifying and obtains pale pink product.
S2. the preparation of 3- formoxyls -4- hydroxyls -4- xenyl cyanogen：By 0.78g (4mmol) 4- hydroxyl -4- xenyls Cyanogen, 2.82g (20mmol) methenamine are dissolved in 70 mL glacial acetic acids, are placed in 100mL round-bottomed flask in 110 DEG C of oil bath pans In be stirred at reflux.Question response is cooled to room temperature after terminating, addition 120mL 10M hydrochloric acid solution, which is stirred at room temperature, to be acidified 1h, then extracted with dichloromethane, collected organic layer, and with water washing is distilled 3 times, saturated aqueous common salt 1 time, use anhydrous magnesium sulfate Filtering decompression removes solvent and obtains faint yellow solid after drying.
S3. the synthesis of the multiple response type fluorescent sensing material based on rhodamine B derivative and cyanobiphenyl phenol：Will 1.56g (3mmol) rhodamine acyl ethylenediamine and 0.67g（3mmol）3- formoxyl -4- hydroxyl -4- xenyl cyanogen be dissolved in 40mL without In water-ethanol, the glacial acetic acid of 3 drops is added, 12h is stirred at reflux in 75 DEG C of oil bath pans, question response is cooled to room temperature after terminating, decompression Remove solvent and obtain crude product, recrystallize to obtain orange/yellow solid, yield 81.5% in ethanol
It is the synthesis of the multiple response type fluorescent sensing material based on rhodamine B derivative and cyanobiphenyl phenol as shown in Figure 1 Journey schematic diagram.
It is illustrated in figure 2 the multiple response type fluorescent sensing material based on rhodamine B derivative and cyanobiphenyl phenol1H NMR schemes, and wherein solvent is CDCl3.Spectrum resolution： 1H NMR (400MHz CDCl3 ) 8.15(1H, s), 7.94(1H, dd), 7.71(2H, d), 7.71(2H, d), 7.62(2H, d), 7.53(1H, dd), 7.47(2H, dd) 7.39 (1H, d), 7.11(1H, dd), 7.02(1H, d), 6.44(4H, t), 6.28( 1H, d), 6.25(1H, d), 3.51(2H, dd), 3.44(2H, m), 3.34(8H, dd), 1.18(12H, t);It is illustrated in figure 3 and is based on rhodamine B The multiple response type fluorescent sensing material of derivative and cyanobiphenyl phenol13C NMR scheme, and wherein solvent is CDCl3.Spectrum solution Analysis：13C NMR (101 MHz, CDCl3) δ 168.40 (s, 1H), 165.65 (s, 1H), 162.15 (s, 1H), 153.47 (d, J = 17.7 Hz, 4H), 148.89 (s, 3H), 144.85 (s, 1H), 132.58 (d, J = 7.3 Hz, 9H), 130.98 (s, 2H), 130.78 (s, 2H), 129.86 (s, 2H), 129.18 (s, 2H), 128.84 (s, 5H), 128.10 (s, 4H), 126.87 (s, 5H), 123.84 (s, 5H), 122.88 (s, 3H), 119.01 (s, 3H), 118.11 (s, 3H), 110.14 (s, 2H), 108.17 (s, 7H), 105.49 (s, 5H), 97.87 (s, 8H), 77.36 (s, 35H), 77.04 (s, 33H), 76.73 (s, 34H), 65.00 (s, 5H), 56.98 (s, 6H), 44.35 (s, 12H), 40.86 (s, 9H), 12.62 (s, 13H).
It can determine that prepare the fluorescent sensing material molecular structure synthesized is with expected structure in Fig. 1 by nuclear magnetic spectrogram parsing Consistent.
It is illustrated in figure 4 fluorescent sensing material (C44H43N5O3, Mn=689) mass spectrogram, wherein, 712.13 be [M+ Na] corresponding to fluorescent sensing material molecular weight.
Embodiment 4：Fluorescent sensing material prepared by the present invention is to Zn2+, Al3+, Fe3+And Cr3+The specificity verification of detection
Weigh the fluorescent sensing material methanol prepared in 6.89 mg embodiments 3 and dissolved constant volume and prepare 10mM's to 10mL Storing solution.Pipette the above-mentioned storing solution constant volumes of 0.1mL and be configured to 10 μM to 100mL（Methanol/HEPES cushioning liquid, v/v:9:1, pH=7.2）The stand-by solution of fluorescent sensing material.Above-mentioned 10 μM of 4mL stand-by solution is pipetted respectively, is separately added into 10 equivalents not Common metal ion of the same race（Ni2+, Ca2+, Co2+, Zn2+, Cr3+, Al3+, Fe3+, Na+, Cd2+, K+, Mg2+, Li+, Fe2+, Cu2+, Mn2+, Sr2+, Cs2+, Pb2+And Hg2+）, respective fluorescence spectrum is entered respectively using XRF Row measure.
Fluorescent sensing material solution has extremely faint fluorescent emission at 465nm certainly（Excitation wavelength is 360nm）, when The fluorescence spectrum added after 10 equivalent different metal ions is as shown in figure 5, wherein Fig. 5 a and Fig. 5 b excitation wavelength is respectively 360nm and 520nm, it can be seen that Zn2+, Al3+, Fe3+And Cr3+Addition can cause different fluorescence light respectively The change of spectrum.Work as Zn2+In the presence of, occur a strong fluorescence emission peak at 465nm；Al3+Presence can cause 490nm With fluorescence emission peak at 580nm two；Fe3+And Cr3+Add and trigger strong fluorescent emission at 580nm respectively.Fig. 6 is uviol lamp The macroscopic different fluorescence signals showed under irradiation.Fig. 7 is corresponding ultraviolet-visible absorption spectroscopy.From spectrum and fluorescence Figure is not it has also been discovered that the presence of other metal ions has the change for causing sensing material system fluorescence.This result shows this The fluorescent sensing material prepared is invented to Zn2+, Al3+, Fe3+And Cr3+With multiple response, it is possible to achieve to Zn2+, Al3 +, Fe3+And Cr3+Selective recognition detection.
Embodiment 5：Fluorescent sensing material prepared by the present invention is to Zn2+, Al3+, Fe3+ And Cr3+The sensitivity checking of detection
10 μM of stand-by solution of the preparation in embodiment 4 is pipetted, respectively to Zn2+, Al3+, Fe3+And Cr3+Carry out fluorescence drop Fixed experiment, that is, it is separately added into the Zn of 0~10 equivalent2+, Al3+, Fe3+And Cr3+Carry out fluorescence spectrometry.Used in the present embodiment To concentration of metal ions be respectively：0.05×10-5M、0.1×10-5M、0.2×10-5M、0.3×10-5M、0.4×10-5M、 0.5×10-5M、0.6×10-5M、0.7×10-5M、0.8×10-5M、0.9×10-5M、1.0×10-5M、2.0×10-5M、3.0× 10-5M、4.0×10-5M、6.0×10-5M、8.0×10-5M、10.0×10-5M.Wherein for Zn2+And Al3+Treat that test sample excites Wavelength is 365nm, for Fe3+And Cr3+Treat that test sample excitation wavelength is 520nm.
The fluorescence emission spectrum of fluorescence titration experiment is as shown in figure 8, it can be seen that increasing with metal concentration Add, corresponding fluorescence emission peak gradually strengthens, and corresponding fluorescence intensity also becomes after saturation state is reached with metal ion combination It is not further added by stable.Furthermore it should be noted that with Al3+The increase of concentration, its corresponding fluorescence spectrum not only show The increase of fluorescence intensity, also shows the Red Shift Phenomena of spectrum, i.e., one of emission peak with concentration of metal ions increase from Gradual red shift is to 490nm at 460nm.Corresponding illustration shows in certain concentration range (0 ~ 1 × 10 in Fig. 8-5M it is corresponding in) Fluorescence Increasing degree（I-I0）Good linear relationship is showed with the concentration of metal ion.This shows the fluorescent sensing material pair Four kinds of target metal ions in the range of finite concentration can carry out quantitative detection.According to the slope of linear equation（slope）And inspection Rising limit calculation formula LOD=3 σ/slope（Wherein σ is that the corresponding value of standard deviation of 20 blank samples is 1.462）Calculate most Low detection limits respectively can be low up to 1.61 × 10-7 M (Zn2+), 8.94×10-8 M (Al3+), 8.61×10-8 M (Fe3+) With 8.42 × 10-8 M (Cr3+).As a result it is high to illustrate that detection of the fluorescent sensing material to four kinds of target metal ions has Sensitivity.
Embodiment 6：Fluorescent sensing material prepared by the present invention is to Zn2+, Al3+, Fe3+ And Cr3+To other metals during detection Ion anti-interference is verified
10 μM of the stand-by solution prepared in embodiment 4 is pipetted, is separately added into the Zn of 10 equivalents2+, Al3+, Fe3+And Cr3+Gold Category solion prepares multigroup Duplicate Samples, adds 10 equivalents other common metal ions after 10min in every group of Duplicate Samples （Ni2+, Ca2+, Co2+, Na+, Cd2+, K+, Mg2+, Li+, Fe2+, Cu2+, Mn2+, Sr2+, Cs2+, Pb2+And Hg2 +）, and respective fluorescence spectrum is measured respectively using XRF, wherein containing Zn2+And Al3+Treat that test sample excites Wavelength is 365nm, contains Fe3+And Cr3+Treat that test sample excitation wavelength is 520 nm.
Fig. 9 is sensing material system detection Zn in the presence of other metal ions2+, Al3+, Fe3+And Cr3+When interference feelings Condition, it can be seen that in addition to four kinds of object ions have a little interference between each other, other coexistent metallic ions are to this Sensing material recognition detection Zn2+, Al3+, Fe3+ And Cr3+Almost without influence.Can for interfering between four metal ion species Reduce and avoid by the concentration of fluorescent sensing material during increase detection.
Embodiment 7：Fluorescent sensing material prepared by the present invention is to Zn in water sample2+, Al3+, Fe3+And Cr3+The mark-on of progress Experiment
Gather actual environment water sample（Yangtze River Water and lake water）, to Zn2+, Al3+, Fe3+And Cr3+Four kinds of target metal ions are carried out Mark-on is tested, and is configured to 0.5mM, 1mM, 2mM Zn respectively2+, Al3+, Fe3+And Cr3+The aqueous solution is as water sample to be measured.Pipette The stand-by solution for the 10 μM of fluorescent sensing materials prepared in 5mL embodiments 4, it is separately added into the above-mentioned various concentrations prepared of 50 μ L Zn2+, Al3+, Fe3+And Cr3+Water sample, and the fluorescence spectrum of measurement system.
Fluorescent sensing material is to Zn in actual water sample2+, Al3+, Fe3+And Cr3+Detection results it is as shown in Figure 10, from knot Fruit can be seen that fluorescent sensing material to the Zn in actual water body2+, Al3+, Fe3+And Cr3+Recognition detection it is equally applicable, still With very high sensitivity, for the Zn of various concentrations2+, Al3+, Fe3+And Cr3+For, detect the obtained journey of Fluorescence Increasing Degree meets the linear relationship between Fluorescence Increasing degree and concentration of metal ions in embodiment 5, and this also illustrates using the present invention The fluorescent sensing material of preparation can realize the qualitative and quantitative detection of target metal ions in water body.

Claims (7)

  1. A kind of 1. multiple response type fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol, it is characterised in that the material For yellowish orange pulverulent solids, methanol/HEPES cushioning liquid (v/v=9 are dissolved in:1, pH=7.4) in system, solution is presented Yellow, obvious fluorescent emission is had no under 365nm ultraviolet light.
  2. 2. a kind of preparation method of the multiple response type fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol, its feature exist In comprising the following steps：
    S1. the synthesis of rhodamine acyl ethylenediamine：
    S2. the preparation of 3- formoxyls -4- hydroxyls -4- xenyl cyanogen：
    S3. the synthesis of the multiple response type fluorescent sensing material based on rhodamine B and cyanobiphenyl phenol：
    Rhodamine acyl ethylenediamine and 3- formoxyl -4- hydroxyl -4- xenyl cyanogen are dissolved in absolute ethyl alcohol, add appropriate ice second Acid, oil bath pan are stirred at reflux, and question response is cooled to room temperature after terminating, and decompression removes solvent and draws crude product, ties again in ethanol It is brilliant to obtain fluorescent sensing material.
  3. 3. preparation method according to claim 4, it is characterised in that rhodamine acyl ethylenediamine and 3- the formoxyls -4- The mass ratio of hydroxyl -4- xenyls is 0.52~1.56g：0.22g~0.67g.
  4. 4. preparation method according to claim 3, it is characterised in that absolute ethyl alcohol dosage described in step S3 for 20~ 40mL。
  5. 5. preparation method according to claim 3, it is characterised in that the back flow reaction temperature is 65~75 DEG C.
  6. 6. preparation method according to claim 3, it is characterised in that the reflux time is 8~12 h.
  7. A kind of 7. multiple response type fluorescent sensing material Zn in environmental water sample based on rhodamine B derivative and cyanobiphenyl phenol2 +、Al3+、Fe3+Or Cr3+Trace detection in application.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110526946A (en) * 2019-07-25 2019-12-03 山东师范大学 The Model multiple response acceptor molecule and its synthetic method of a kind of pyridine bridging and application
CN113698499A (en) * 2021-08-24 2021-11-26 华南理工大学 Iron ion response nanocellulose-based fluorescent material and preparation method and application thereof

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CN101550234A (en) * 2009-05-13 2009-10-07 中国科学院上海微系统与信息技术研究所 Fluorescent sensing material with sensing function to phenyl amine compounds, method and application thereof
CN104371709A (en) * 2014-11-18 2015-02-25 苏州大学 Fluorescent sensing material as well as preparation method and application thereof

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CN101550234A (en) * 2009-05-13 2009-10-07 中国科学院上海微系统与信息技术研究所 Fluorescent sensing material with sensing function to phenyl amine compounds, method and application thereof
CN104371709A (en) * 2014-11-18 2015-02-25 苏州大学 Fluorescent sensing material as well as preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN110526946A (en) * 2019-07-25 2019-12-03 山东师范大学 The Model multiple response acceptor molecule and its synthetic method of a kind of pyridine bridging and application
CN110526946B (en) * 2019-07-25 2022-02-08 山东师范大学 Pyridine-bridged multiple-response receptor molecule and synthesis method and application thereof
CN113698499A (en) * 2021-08-24 2021-11-26 华南理工大学 Iron ion response nanocellulose-based fluorescent material and preparation method and application thereof
CN113698499B (en) * 2021-08-24 2022-05-24 华南理工大学 Iron ion response nanocellulose-based fluorescent material and preparation method and application thereof

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