CN106518715A - Preparation method and application for chemical fluorescence sensing material - Google Patents
Preparation method and application for chemical fluorescence sensing material Download PDFInfo
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Abstract
The invention relates to a preparation method and application for a chemical fluorescence sensing material and belongs to the technical field of chemical sensing materials. The preparation method comprises the steps that 4-N,N-dimethyl cinnamyl aldehyde and 4-hydroxy benzoyl hydrazine are put into a round-bottom flask; absolute ethyl alcohol is added and dissolved; an appropriate amount of glacial acetic acid is dropwise added; the materials are put in an oil-bath pan and subjected to stirring and reflux for a reaction; the temperature is reduced to the indoor temperature after the reaction; a crude product is obtained after depressurizing and solvent removing; and a yellow powdered product is obtained after purification. The preparation method only needs the simple one-step reaction, so that reaction time is reduced greatly, the reaction condition is mild, the complicated preparing process is avoided, the relative yield is high, and the cost of raw materials is low. The chemical fluorescence sensing material is accompanied with strong green fluorescence emission due to a conjugated structure of the chemical fluorescence sensing material, the combination with Cu2+ can lead to quenching of fluorescence, and the response time is short; the detection of Cu2+ is not disturbed by other common metal ions; and the limit of the detection of Cu2+ by the chemical fluorescence sensing material is as low as 5.3x10<-9> M.
Description
Technical field
The present invention relates to a kind of preparation method of chemiluminescence sensing material and purposes, more particularly to a kind of to be based on cinnamic aldehyde
The preparation method and purposes of the fluorescence response section bar material of derivant, belongs to chemical sensing material technical field.
Background technology
With the growth developed rapidly with population of Chinese society economy, constantly heavy metal carry out exploiting, smelt, plus
Work and business are manufactured, and cause substantial amounts of heavy metal ion to enter soil and water body environment, and serious have impact on the ecological and mankind's
Health and safety.In recent years, heavy metal pollution event occurs again and again, and relevant report shows that China there are about 12,000,000 ton-grain food every year
Suffer heavy metal pollution, direct economic loss more than 20,000,000,000 yuan, because which has very high dissolubility, heavy metal pair in water environment
The pollution of water body is even more serious.Waste water main source containing heavy metal ion is colliery, metal sulfide mineral, iron mine, metallurgy etc.
Manufacturing enterprise, these production waste water are often the mixing of various wastewater, comprising numerous heavy metal ion, tight to environmental hazard
Weight, the main feature of its environmental pollution have the following aspects：（1）Heavy metal contaminants can not be micro- in natural environment
Biodegradation, the change that form can only occur, and the not basic elimination of its toxicity in the process.（2）Easily by organism
Absorbed, the heavy metal ion of different shape can be migrated by biological, and the mode such as enrichment acts on animals and plants, eventually through food
Thing chain enters human body.（3）Into after human body when heavy metal ion intake has exceeded the Cmax of body permission, will lead
Serious biological disorder is caused, while can also occur to interact with Basic knowledge of analytical reagents, and causes biopolymer to lose work
Property, cause various diseases.So it is accumulated in human body and can causes chronic poisoning, and this accumulation property endangers often short-term and should not send out
It is existing.
As the Cu of one of heavy metal2+Trace element necessary to be animals and plants and the mankind, micro Cu2+Dynamic plant can be promoted
Thing grows, but after certain amount is run up in vivo, just occurs that physiology is obstructed, arrest of development, or even the danger of death
Evil.In order to reduce and avoid which to ecological environment and the harm of the mankind, the important prerequisite for carrying out timely and effective process is to realize ring
Cu in border2+Effective detection analysis.Traditional detection technique such as atomic absorption spectrophotometry, flame atomization and inductance
Coupled plasma-atomic emission spectrometry etc. all needs to carry out sample complicated pretreatment before detection, the interference of testing result because
Element is more, and detecting instrument is expensive in addition, and complex operation limits its universal application.Therefore develop it is a kind of it is quick, convenient,
Sensitive effective detection technique becomes a new challenge.Fluorescent sensing material has high sensitivity due to which, and selectivity is good,
The advantages of being easy to visualization and enjoy favor, in recent years with fluorescent sensing material detecting grinding for heavy metal and transition metal ionss
Study carefully and increasingly receive publicity.Fluorescent sensing material itself has unique optical property, when its combining target ion, in material
Photophysical Behaviors be affected, the output form of fluorescence signal changes, based on sensor before and after combining target ion
Change in fluorescence realizes the quick detection to specific ion as response signal.
In recent years, schiff base compounds are extensively synthesized and the substantial amounts of fluorescence colorimetric detection for zwitterion, are led to
Specific fluorescent chromophore is included in the schiff base compounds for often preparing all for the output of signal, such as common rhodamine
B, coumarin, fluorescein, anthracene etc..And cinnamic aldehyde does not obtain too many concern as a kind of material of low toxicity low cost, its
Not only there is good biological activity and pharmaceutically active, by the food synthesis material as permission addition, but also because of its own
Conjugated structure there is excellent optical property；But report both at home and abroad based on the Schiff bases fluorescent probe of cinnamic aldehyde is simultaneously few
See.
For this purpose, the present invention is successfully prepared a kind of fluorescent sensing material based on cinnamylaldehyde derivatives；Research finds Cortex Cinnamomi
Aldehyde derivatives prepare new schiff base as fluorescent emission group and 4- hydroxybenzoyl hydrazines by simple single step reaction
Compound, in 4- hydroxybenzoyl hydrazines, C=O keys and the C=N double bonds for being formed provide binding site respectively so as to and the combination of object
Ability is higher.The fluorescence quantum yield of itself is also greatly strengthened simultaneously, and the detection sensitivity of sensor is improved.
The content of the invention
The present invention considers the restriction of traditional sensing techniques, it is therefore intended that offer is a kind of stable in properties to be spread out based on cinnamic aldehyde
Biological fluorescent sensing material and its production and use, can be good at realizing trace Cu in environmental water sample2+Effective inspection
Survey, simple with synthesis, selectivity is single and the features such as high detection sensitivity.
The technical solution used in the present invention is：
The present invention provides a kind of fluorescent sensing material based on cinnamylaldehyde derivatives, is by 4-N, N- dimethyl cinnamic aldehyde and 4- hydroxyls
Base benzoyl hydrazine passes through fluorescent sensing material obtained in the simple necleophilic reaction of a step.
The present invention also provides a kind of preparation method of the fluorescent sensing material based on cinnamylaldehyde derivatives, and concrete operations are such as
Under：
Synthesis based on the fluorescent sensing material of cinnamylaldehyde derivatives：By 4-N, N- dimethyl cinnamic aldehyde and 4- hydroxybenzoyl hydrazines
It is placed in round-bottomed flask, adds dehydrated alcohol to dissolve the two, the appropriate glacial acetic acid of Deca is placed in oil bath pan and is stirred at reflux.
Question response is cooled to room temperature after terminating, decompression removes the crude product that solvent obtains fluorescent sensing material.By crude product post layer
Analysis method（Ethyl acetate：Petroleum ether）Carry out purification and obtain pure yellow powder product.
In above-mentioned steps, described 4-N, N- dimethyl cinnamic aldehyde, 4- hydroxybenzoyl hydrazines, glacial acetic acid, dehydrated alcohol are used
Measuring ratio is：0.17 ~0.7g：0.15~0.62g：1 ~ 3 drop：20 ~ 60mL, described back flow reaction temperature are 50～75 DEG C, reaction
Time is 5～10h.Petroleum ether used by chromatography column separating purification is 3 with the volume ratio of ethyl acetate:1.
The present invention also provides a kind of fluorescent sensing material based on cinnamylaldehyde derivatives for Cu in environmental water sample2+Trace
The purposes of detection.
The present invention also provides a kind of fluorescent sensing material based on cinnamylaldehyde derivatives for Cu in biological cell2+'s
Detection.
The present invention technique effect be：
（1）The invention provides a kind of based on the fluorescent sensor material of cinnamylaldehyde derivatives, its preparation method and application, 4-N,
N- dimethyl cinnamic aldehyde prepares schiff base compound with 4- hydroxybenzoyl hydrazines as raw material, only needs simple single step reaction,
Response time is greatly shortened as catalyst using glacial acetic acid, reaction condition is gentle, compared with other fluorescent materials for, it is to avoid
Loaded down with trivial details preparation process, relative productivity are higher, and the cost of raw material is low.
（2）Oxygen and nitrogen difference in fluorescent sensing material structure prepared by the present invention on C=O and C=N groups can be used as knot
Close site and electronics is provided, be which combines Cu2+Lay a good foundation, material due to itself conjugated structure and with strong green fluorescence
Transmitting, with Cu2+Combination can cause fluorescent quenching, response time is fast, and under uviol lamp, the change naked eyes of fluorescence signal are visible, its
His common metal ion is to Cu2+Detection do not result in interference, compare other detection Cu2+Fluorescent material for testing conditions
More gentle, in the present invention fluorescent sensing material detection Cu2+When the dicyandiamide solution that adopted in the composition of water be up to 99%, keep away
The introducing of a large amount of organic solvents, and test limit LOD (L=3 σ/slope, wherein S=6.396 × 10 are exempted from7, σ=0.113)
It is lower, can be low up to 5.3 × 10-9 M。
Description of the drawings
Fig. 1 is the building-up process schematic diagram of the fluorescent sensing material based on cinnamylaldehyde derivatives prepared by embodiment 4.
Fig. 2 is fluorescent sensing material prepared by embodiment 41H NMR scheme.
Fig. 3 is fluorescent sensing material prepared by embodiment 413C NMR scheme.
Fig. 4 is schemed for the ESI-MS of fluorescent sensing material prepared by embodiment 4.
Fluorescence spectras of the Fig. 5 for fluorescent sensing material prepared by embodiment 4.
Fig. 6 is fluorescence spectra of the fluorescent sensing material in the presence of different metal ions prepared by embodiment 4.
Fig. 7 is fluorescent sensing material and Cu prepared by embodiment 42+With reference to Job curve charts；1 expression in figure is this
Fluorescent sensing material prepared by invention.
Fig. 8 is fluorescent sensing material prepared by embodiment 4 in variable concentrations Cu 2+In the presence of fluorescence spectra.
Fig. 9 is the fluorescence intensity of fluorescent sensing material prepared by embodiment 4 and the Cu for existing2+The linear relationship chart of concentration.
Figure 10 is fluorescent sensing material detection Cu prepared by embodiment 42+When other coexistent metallic ions interferogram；In figure
1 expression be the present invention prepare fluorescent sensing material.
Figure 11 is fluorescent sensing material prepared by embodiment 4 to Cu in actual water sample2+Detection.
Figure 12 is that fluorescent sensing material prepared by embodiment 4 is used for Cu in organism living cells2+Image；In figure, a is
Imaging of the cell after fluorescent sensing material culture under light field is added, b is that the cell after adding fluorescent sensing material culture exists
Fluorescence imaging off field, c are 20 μM of Cu of addition2+Imaging of the cell in fluorescence off field afterwards, d are 50 μM of Cu of addition2+Cell exists afterwards
Fluorescence imaging off field.
Specific embodiment
With reference to example is embodied as, the invention will be further described：
Embodiment 1：
Fluorescent sensing material of the synthesis based on cinnamylaldehyde derivatives：By the 4- of the 4-N of 0.17g, N- dimethyl cinnamic aldehyde and 0.15g
Hydroxybenzoyl hydrazine is placed in the round-bottomed flask of 100mL, adds 20 mL dehydrated alcohol to dissolve the two, the ice second of the drop of Deca 1
Acid, is placed in 50 DEG C of oil bath pan and is stirred at reflux 5 h.Question response is cooled to room temperature after terminating, decompression removes solvent and obtains glimmering
The crude product of light sensing material.By crude product column chromatography method（Ethyl acetate：Petroleum ether v/v=1:3）Carry out purification to obtain
（0.255g）Pure yellow powder product.Yield is 82.6%.
Embodiment 2：
Fluorescent sensing material of the synthesis based on cinnamylaldehyde derivatives：By the 4- of the 4-N of 0.35g, N- dimethyl cinnamic aldehyde and 0.31g
Hydroxybenzoyl hydrazine is placed in the round-bottomed flask of 100mL, adds 40 mL dehydrated alcohol to dissolve the two, the ice second of the drop of Deca 2
Acid, is placed in 65 DEG C of oil bath pan and is stirred at reflux 8 h.Question response is cooled to room temperature after terminating, decompression removes solvent and obtains glimmering
The crude product of light sensing material.By crude product column chromatography method（Ethyl acetate：Petroleum ether v/v=1:3）Carry out purification to obtain
（0. 558g）Pure yellow powder product.Yield is 90.3%.
Embodiment 3：
Fluorescent sensing material of the synthesis based on cinnamylaldehyde derivatives：By the 4- of the 4-N of 0.70g, N- dimethyl cinnamic aldehyde and 0.62g
Hydroxybenzoyl hydrazine is placed in the round-bottomed flask of 100mL, adds 60 mL dehydrated alcohol to dissolve the two, the ice second of the drop of Deca 3
Acid, is placed in 75 DEG C of oil bath pan and is stirred at reflux 10 h.Question response is cooled to room temperature after terminating, decompression removes solvent and obtains
The crude product of fluorescent sensing material.By crude product column chromatography method（Ethyl acetate：Petroleum ether v/v=1:3）Carry out purification to obtain
Arrive（1.095g）Pure yellow powder product.Yield is 89.8%.
Embodiment 4：
（1）Fluorescent sensing material of the synthesis based on cinnamylaldehyde derivatives：By the 4-N of 0.35g, N- dimethyl cinnamic aldehyde and 0.31g
4- hydroxybenzoyl hydrazines be placed in the round-bottomed flask of 100mL, add 40 mL dehydrated alcohol dissolve the two, Deca 3 drop ice
Acetic acid, is placed in 65 DEG C of oil bath pan and is stirred at reflux 5 h.Question response is cooled to room temperature after terminating, decompression removes solvent and obtains
The crude product of fluorescent sensing material.By crude product column chromatography method（Ethyl acetate：Petroleum ether v/v=1:3）Carry out purification to obtain
Arrive（0. 555g）Pure yellow powder product.Yield is 89.8%.The material for preparing is characterized using nuclear-magnetism and mass spectrum.
It is the building-up process schematic diagram of the fluorescent sensing material based on cinnamylaldehyde derivatives as shown in Figure 1.
It is fluorescent sensing material as shown in Figures 2 and 3 respectively1H NMR and13C NMR scheme.Nuclear-magnetism figure can determine material
Chemical constitution,1H NMR (400 MHz, DMSO-d6): δ 11.38 (s, 1H), 10.10(s, 1H), 8.14 (d,
1H), 7.76 (d, 2H), 7.43 (d, 2H), 6.86(s, 1H), 6.83(d, 2H), 6.77(d, 1H), 6.70
(d, 2H), 2.95 (s, 6H); 13C NMR(DMSO-d6): δ 162.41, 151.11, 150.88, 140.17,
134.28, 129.16, 123.54, 119.08. 115.41, 112.50, 40.21, 40.00。
It is illustrated in figure 4 fluorescent sensing material (C18H19N3O2, M=309) ESI-MS figure, wherein, 310.20 be [M+H]
Corresponding molecular weight, 330.20 is [M+Na] corresponding molecular weight.Further demonstrate that the structure of the fluorescent sensing material.
（2）Weigh 7.725mg steps（1）The fluorescent sensing material ethanol of middle preparation is dissolved constant volume and is prepared to 25mL
The storing solution of 1mM.The above-mentioned storing solution distilled water constant volumes of 1mL and 2mL are pipetted respectively is configured to 10 μM and 20 μM of second to 100mL
Alcohol/water（v/v=1:99）The stand-by solution of fluorescent sensing material of system, adopts HEPES buffer solution regulation system during being somebody's turn to do
pH=7.4.The stand-by solution of above-mentioned 10 μM of 4mL is pipetted respectively, is separately added into 10 equivalents common metal ion not of the same race（Na+,
Zn2+, Hg2+, Fe2+, Fe3+, Cu2+, Mn2+, Al3+, Cr3+, K+, Ca2+, Sr2+, Cs2+, Mg2+, Pb2+,Co2+,
Li2+And Cd2+）, respectively respective fluorescence spectrum is measured using fluorescence spectrophotometer（Excitation wavelength is 378nm）.
In ethanol/water（v/v=1:99, pH=7.4）Mixed solvent system in, the fluorescence of 10 μM of fluorescent sensing material
Spectrogram（Excitation wavelength is 378nm）As shown in figure 5, it can be seen that fluorescent sensing material is strong from having at 525nm
Emission peak, this is due to its own big conjugated structure.
Fluorescent sensing material is in ethanol/water（v/v=1:99, pH=7.4）Mixed solvent system in, add 10 equivalents not
Same metal ion（Na+, Zn2+, Hg2+, Fe2+, Fe3+, Cu2+, Mn2+, Al3+, Cr3+, K+, Ca2+, Sr2+, Cs2+,
Mg2+, Pb2+, Co2+, Li2+And Cd2+）Rear fluorescence spectrum is as shown in fig. 6, it can be seen that selected common
17 metal ion species in, fluorescent sensing material is to Cu2+With higher selectivity, fluorescent quenching is shown as.Other common gold
The addition of category ion hardly causes to change to the fluorescence of fluorescent sensing material itself.This is due to divalent metal copper ion
Electronics distribution is 3d84s1, 3d orbital electron layer be in underfill state, work as Cu2+After being combined with fluorescent sensing material, as matching somebody with somebody
The fluorescent sensing material of body can be by the electron transfer of excited state to bivalent cupric ion, so as to cause excited state electronics return to base
State track, so as to fluorescence is quenched.
（3）Removing step（2）In 10 μM of stand-by solution, to Cu2+Carry out fluorescence titration experiment, that is, it is separately added into 0～
The Cu of 10 equivalents2+Fluorescence spectrometry is carried out, the copper ion concentration used in the present embodiment is respectively：0、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, additionally, to other common metal ions for coexisting in system to fluorescent sensing material Selective recognition Cu2+Interference feelings
Condition is measured.
In ethanol/water（v/v=1:99, pH=7.4）Mixed solvent system in, fluorescent sensing material is separately added into 0～10
Equivalent Cu2+The fluorescence spectrum of fluorescence titration experiment is carried out as shown in figure 8, it can be seen that with Ni metal2+Concentration
Increase, the fluorescence intensity of system gradually weakens；Fig. 9 shows the corresponding fluorescent quenching degree in certain concentration range（I0-I）
With Cu2+Concentration good linear relationship is presented, illustrate the fluorescent sensing material to the Cu in the range of finite concentration2+Can carry out
Detection by quantitative；It is 0-10 μM of Cu to concentration in Fig. 92+Detected, lowest detectable limit LOD in Fig. 9（L）=3 σ/slope, its
Middle slope s（slope）=6.396×107, standard deviation=0.113 of 20 blank samples, through calculating lowest detectable limit it is reachable
5.3×10-9 M。
Other common metal ions and Cu2+Under ion concurrent conditionses, to fluorescent sensing material recognition detection Cu2+It is dry
Disturb impact as shown in Figure 10, it can be seen that the presence of other common metal ions is recognized to the fluorescent sensing material
Detection Cu2+Impact less.Illustrate the fluorescent sensing material to Cu2+Identification with select unicity, not by other metals from
The interference of son.
（4）Prepare 10 μM of Ni metal2+Solution, respectively by step（2）10 μM of fluorescent sensing materials of middle preparation it is stand-by
The Ni metal of solution and 10 μM2+Solution presses different volumes ratio（0:10～10:0）Mixing so that the total concentration of both mixture is
, fluorescence spectrometry is carried out to a series of mixture, prepare the determination of Job curves and combine ratio by 10 μM.
The Job curves of Fig. 7 further demonstrate that fluorescent sensing material and copper ion with 2:1 stoichiometric proportion is combined, this
Illustrate that prepared fluorescent sensing material can be responded to Ni metal by fluorescence signal2+Carry out single Selective recognition detection.
（5）Collection Yangtze River Water, lake water and tap water, carry out Cu to which respectively2+Mark-on experiment, Cu2+Mark-on amount be 10
μM and 15 μM, take step（2）In 20 μM of stand-by solution 2mL, be separately added into the mark-on water sample of 2mL, to which after mix homogeneously
Fluorescence spectrum is measured.
Fluorescent sensing material is to Cu in actual water sample2+School survey effect as shown in figure 11, from the results, it was seen that fluorescence is passed
Sense material is to the Cu in actual water body2+Detection with very high susceptiveness and good selectivity, Cu in water body2+Concentration is not
Together, the degree of fluorescent quenching is also different, according to corresponding fluorescent quenching degree and Cu2+Linear relationship between concentration can be realized
The qualitative and detection by quantitative of target metal ions in water body.
（6）Culture 24h, cultivation temperature are carried out to Human B lymphoma cell in RPMI-1640 culture fluid (comprising 10%FBS)
For 37 DEG C.Then the cell is cultivated into 30min in PBS with 50 μM of fluorescent sensing material, and washs three times with PBS
The fluorescent sensing material of remnants is removed, 20 μM and 50 μM of Cu are separately added into2+20min is cultivated in continuation in PBS, then
With PBS washed cells again, using inverted fluorescence microscope to adding Cu2+Cell in front and back carries out imaging analysis.
Fluorescent sensing material is to Cu in biological cell2+Imaging results as shown in figure 12, Figure 12-a and Figure 12-b are respectively
Imaging of the cell after fluorescent sensing material culture in light field and fluorescence off field is added, it can be seen that cell is presented from Figure 12-b
Go out green-fluorescent emission, show that fluorescent sensing material has been successfully entered cell interior, this phenomenon also sufficiently illustrates fluorescence
Sensor has good biological permeability.Figure 12-c and Figure 12-d respectively add not commensurability Cu2+Afterwards cell in fluorescence off field
Imaging contexts.It can be seen that not commensurability Cu in cell2+Presence can cause that fluorescence is different degrees of to be quenched.This
As a result also demonstrate that fluorescent sensing material Cu in biological cell2+Context of detection there is certain using value.
Claims (8)
1. a kind of chemiluminescence sensing material based on cinnamylaldehyde derivatives, it is characterised in that the material is by 4-N, N- bis-
Methyl cinnamic aldehyde and 4- hydroxybenzoyl hydrazines pass through fluorescent sensing material obtained in the simple necleophilic reaction of a step.
2. a kind of preparation method of the chemiluminescence sensing material based on cinnamylaldehyde derivatives, it is characterised in that concrete operations are such as
Under：
By 4-N, N- dimethyl cinnamic aldehyde and 4- hydroxybenzoyl hydrazines are placed in round-bottomed flask, add dehydrated alcohol to make the two molten
Solution, the appropriate glacial acetic acid of Deca are placed in oil bath pan and are stirred at reflux reaction；Question response is cooled to room temperature after terminating, decompression
Remove the crude product that solvent obtains fluorescent sensing material；Crude product is carried out into purification with column chromatography method and obtains pure yellow powder
Product.
3. a kind of chemiluminescence sensing material based on cinnamylaldehyde derivatives according to claim 2, it is characterised in that institute
State
4-N, N- dimethyl cinnamic aldehyde, 4- hydroxybenzoyl hydrazines, glacial acetic acid, dehydrated alcohol consumption are：0.17 ~0.7g：0.15~
0.62g：1 ~ 3 drop：20~60mL.
4. a kind of chemiluminescence sensing material based on cinnamylaldehyde derivatives according to claim 2, it is characterised in that institute
The back flow reaction temperature stated is 50～75 DEG C.
5. a kind of chemiluminescence sensing material based on cinnamylaldehyde derivatives according to claim 2, it is characterised in that institute
The reflux time stated is 5～10h.
6. a kind of fluorescent sensing material based on cinnamylaldehyde derivatives is used for Cu in environmental water sample2+Trace detection purposes.
7. purposes according to claim 6, the water sample are Yangtze River Water, lake water or tap water.
8. a kind of fluorescent sensing material based on cinnamylaldehyde derivatives is used for Cu in biological cell2+Detection purposes.
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| CN104829487A (en) * | 2015-03-27 | 2015-08-12 | 福州大学 | Aggregation luminescence enhancement ammonia sensitive metal-organic gel compound soft material and preparation thereof |
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| CN104829487A (en) * | 2015-03-27 | 2015-08-12 | 福州大学 | Aggregation luminescence enhancement ammonia sensitive metal-organic gel compound soft material and preparation thereof |
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