CN106518715B - A kind of preparation method and purposes of chemiluminescence sensing material - Google Patents
A kind of preparation method and purposes of chemiluminescence sensing material Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods and purposes of chemiluminescence sensing material, belong to chemical sensing material technical field；4 N, N dimethyl cinnamic acid and 4 hydroxybenzoyl hydrazines are placed in round-bottomed flask by the present invention, add in absolute ethyl alcohol dissolving, appropriate glacial acetic acid is added dropwise, is placed in oil bath pan and is stirred at reflux reaction；It treats to be cooled to room temperature after reaction, decompression removes solvent and obtains crude product, obtains yellow powder product after purification；The method of the present invention only needs simple single step reaction, substantially reduces the reaction time, reaction condition is mild, avoids cumbersome preparation process, and relative productivity is higher, and the cost of raw material is low；The present invention material due to itself conjugated structure and with strong green-fluorescent emission, with Cu2+Combination can cause fluorescent quenching, the response time is fast, for other common metal ions, to Cu2+Detection will not interfere, resulting materials of the present invention are to Cu2+Detection limit is down to 5.3 × 10‑9 M。
Description
Technical field
It is more particularly to a kind of to be based on cinnamic acid the present invention relates to a kind of preparation method and purposes of chemiluminescence sensing material
The preparation method and purposes of the fluorescence response section bar material of derivative, belong to chemical sensing material technical field.
Background technology
With the rapid development of Chinese society economy and the growth of population, constantly heavy metal is exploited, is smelted, is added
Work and business manufacture, and substantial amounts of heavy metal ion is caused to enter soil and water body environment, serious to affect ecology and the mankind's
Health and safety.In recent years, heavy metal pollution event occurs again and again, and relevant report shows that there are about 12,000,000 ton-grain foods every year in China
By heavy metal pollution, direct economic loss is more than 20,000,000,000 yuan, because it has very high solubility, 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 ore, metallurgy etc.
Manufacturing enterprise, these production waste water are often the mixing of various wastewater, tight to environmental hazard comprising numerous heavy metal ion
Weight, the main feature of environmental pollution have the following aspects：（1）Heavy metal contaminants can not be micro- in natural environment
The change of form can only occur for biodegradation, and its toxicity is eliminated there is no basic in the process.（2）Easily by organism
It is absorbed, the heavy metal ion of different shape can be migrated by biological, and the modes such as enrichment act on animals and plants, eventually by food
Object chain enters human body.（3）After into human body when heavy metal ion intake has been more than the maximum concentration that body allows, it will lead
Serious biological disorder is caused, while can also be interacted with Basic knowledge of analytical reagents, and boiomacromolecule is caused to lose work
Property, cause various diseases.Slow poisoning can be caused by being so accumulated in human body, and this accumulation property harm should not often be sent out in short term
It is existing.
Cu as one of heavy metal2+Cu micro- necessary to be animals and plants and the mankind, micro2+It can promote dynamic plant
Object is grown, but after certain amount is run up in vivo, is just present with physiology and is obstructed, the danger of arrest of development or even death
Evil.In order to reduce and avoid its harm to ecological environment and the mankind, the important prerequisite for carrying out timely and effective processing is to realize ring
Cu in border2+Effective detection and 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, complicated for operation to limit its universal application.Therefore develop it is a kind of it is quick, convenient,
Sensitive effective detection technique becomes a new challenge.For fluorescent sensing material since it has high sensitivity, selectivity is good,
The advantages that being easy to visualization and receive favor, detect grinding for heavy metal and transition metal ions with fluorescent sensing material in recent years
Study carefully and increasingly attract attention.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
Signal realizes the quick detection to specific ion to change in fluorescence in response.
In recent years, schiff base compounds are synthesized and by extensive largely for the fluorescence colorimetric detection of zwitterion, logical
The output of signal, such as common rhodamine are all used in the schiff base compounds often prepared comprising specific fluorescent chromophore
B, cumarin, fluorescein, anthracene Kun etc..And cinnamic acid does not obtain too many concern as a kind of material of low toxicity low cost,
Not only there is good bioactivity and pharmaceutical activity, by as the food synthesis material for allowing addition, but also because of its own
Conjugated structure have excellent optical property；But the report of the Schiff bases fluorescence probe based on cinnamic acid and few both at home and abroad
See.
For this purpose, the present invention is successfully prepared a kind of fluorescent sensing material based on cinnamylaldehyde derivatives；Research finds Chinese cassia tree
Aldehyde derivatives prepare new schiff base by simple single step reaction as fluorescent emission group and 4- hydroxybenzoyl hydrazines
Object is closed, C=O keys provide binding site respectively with the C=N double bonds formed in 4- hydroxybenzoyl hydrazines, make the combination of itself and object
Ability is stronger.The fluorescence quantum yield of itself is also greatly enhanced simultaneously, and the detection sensitivity of sensor is improved.
The content of the invention
The present invention considers the limitation of traditional sensing techniques, and it is an object of the present invention to provide a kind of being spread out based on cinnamic acid for property stabilization
Fluorescent sensing material of biology and its preparation method and application can be good at realizing trace Cu in environmental water sample2+Effective inspection
It surveys, there is the features such as synthesis is simple, and selectivity is single and detection sensitivity is high.
The technical solution adopted by the present invention is：
The present invention provides a kind of fluorescent sensing material based on cinnamylaldehyde derivatives, be by 4-N, N- dimethyl cinnamic acid and
4- hydroxybenzoyl hydrazines pass through fluorescent sensing material made from the simple necleophilic reaction of a step.
The present invention also provides a kind of preparation methods of the fluorescent sensing material based on cinnamylaldehyde derivatives, and concrete operations are such as
Under：
The synthesis of fluorescent sensing material based on cinnamylaldehyde derivatives：By 4-N, N- dimethyl cinnamic acid and 4- hydroxy benzenes first
Hydrazides is placed in round-bottomed flask, and adding in absolute ethyl alcohol dissolves the two, and suitable glacial acetic acid is added dropwise, is placed in oil bath pan and stirs back
Stream.It treats to be cooled to room temperature after reaction, decompression removes the crude product that solvent obtains fluorescent sensing material.By crude product column
Chromatography method（Ethyl acetate：Petroleum ether）It is purified to obtain pure yellow powder product.
In above-mentioned steps, the 4-N, N- dimethyl cinnamic acid, 4- hydroxybenzoyl hydrazines, glacial acetic acid, absolute ethyl alcohol are used
Measuring ratio is：0.17 ~0.7g：0.15~0.62g：1 ~ 3 drop：20 ~ 60mL, the back flow reaction temperature are 50~75 DEG C, reaction
Time is 5~10h.The volume ratio for chromatographing the petroleum ether used in column separating purification and ethyl acetate is 3:1.
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 present invention provides a kind of fluorescent sensor material based on cinnamylaldehyde derivatives, its preparation method and application,
4-N, N- dimethyl cinnamic acid prepare schiff base compound with 4- hydroxybenzoyl hydrazines as raw material, only need a simple step anti-
Should, the reaction time is greatly shortened as catalyst using glacial acetic acid, reaction condition is mild, for other fluorescent materials,
Cumbersome preparation process is avoided, relative productivity is higher, and the cost of raw material is low.
（2）C=O and oxygen on C=N groups and nitrogen can be used as knot respectively in fluorescent sensing material structure prepared by the present invention
It closes site and electronics is provided, Cu is combined for it2+Lay a good foundation, material due to itself conjugated structure and with strong green fluorescence
Transmitting, with Cu2+Combination can cause fluorescent quenching, the response time is fast, in the UV lamp fluorescence signal variation naked eyes as it can be seen that its
His common metal ion is to Cu2+Detection will not interfere, compared to other detection Cu2+Fluorescent material for testing conditions
It is more mild, the fluorescent sensing material detection Cu in the present invention2+When used dicyandiamide solution in the ingredient of water be up to 99%, keep away
Exempt from the introducing of a large amount of organic solvents, and detect limit LOD (L=3 σ/slope, wherein S=6.396 × 107, σ=0.113)
It is lower, it can be down 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 that the ESI-MS of fluorescent sensing material prepared by embodiment 4 schemes.
Fig. 5 is the fluorescence spectra of 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 graphs；1 in figure represent is this
Invent the fluorescent sensing material prepared.
Fig. 8 is fluorescent sensing material prepared by embodiment 4 in various concentration Cu 2+In the presence of fluorescence spectra.
Fig. 9 is the fluorescence intensity of fluorescent sensing material prepared by embodiment 4 and existing Cu2+The linear relationship chart of concentration.
Figure 10 is that fluorescent sensing material prepared by embodiment 4 detects Cu2+When other coexistent metallic ions interference figure；In figure
1 represent is the fluorescent sensing material for preparing of the present invention.
Figure 11 is fluorescent sensing material prepared by embodiment 4 to Cu in actual water sample2+Detection.
Figure 12 is fluorescent sensing material prepared by embodiment 4 for Cu in organism living cells2+Image；A is in figure
Imaging of the cell after fluorescent sensing material culture under light field is added in, b is that the cell after addition fluorescent sensing material culture exists
The imaging of fluorescence 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
The imaging of fluorescence off field.
Specific embodiment
With reference to specific implementation example, the invention will be further described：
Embodiment 1：
Synthesize the fluorescent sensing material based on cinnamylaldehyde derivatives：By the 4-N of 0.17g, N- dimethyl cinnamic acid and 0.15g
4- hydroxybenzoyl hydrazines be placed in the round-bottomed flask of 100mL, adding in 20 mL absolute ethyl alcohols both makes to dissolve, and the ice of 1 drop is added dropwise
Acetic acid is placed in 50 DEG C of oil bath pan and is stirred at reflux 5 h.It treats to be cooled to room temperature after reaction, 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）Purify
It arrives（0.255g）Pure yellow powder product.Yield is 82.6%.
Embodiment 2：
Synthesize the fluorescent sensing material based on cinnamylaldehyde derivatives：By the 4-N of 0.35g, N- dimethyl cinnamic acid and 0.31g
4- hydroxybenzoyl hydrazines be placed in the round-bottomed flask of 100mL, adding in 40 mL absolute ethyl alcohols both makes to dissolve, and the ice of 2 drops are added dropwise
Acetic acid is placed in 65 DEG C of oil bath pan and is stirred at reflux 8 h.It treats to be cooled to room temperature after reaction, 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）Purify
It arrives（0. 558g）Pure yellow powder product.Yield is 90.3%.
Embodiment 3：
Synthesize the fluorescent sensing material based on cinnamylaldehyde derivatives：By the 4-N of 0.70g, N- dimethyl cinnamic acid and 0.62g
4- hydroxybenzoyl hydrazines be placed in the round-bottomed flask of 100mL, adding in 60 mL absolute ethyl alcohols both makes to dissolve, and the ice of 3 drops are added dropwise
Acetic acid is placed in 75 DEG C of oil bath pan and is stirred at reflux 10 h.It treats to be cooled to room temperature after reaction, decompression removes solvent
Obtain the crude product of fluorescent sensing material.By crude product column chromatography method（Ethyl acetate：Petroleum ether v/v=1:3）It is purified
It obtains（1.095g）Pure yellow powder product.Yield is 89.8%.
Embodiment 4：
（1）Synthesize the fluorescent sensing material based on cinnamylaldehyde derivatives：By the 4-N of 0.35g, N- dimethyl cinnamic acid and
The 4- hydroxybenzoyl hydrazines of 0.31g are placed in the round-bottomed flask of 100mL, and adding in 40 mL absolute ethyl alcohols dissolves the two, is added dropwise 3
The glacial acetic acid of drop is placed in 65 DEG C of oil bath pan and is stirred at reflux 5 h.It treats to be cooled to room temperature after reaction, decompression removes
Solvent obtains the crude product of fluorescent sensing material.By crude product column chromatography method（Ethyl acetate：Petroleum ether v/v=1:3）It carries out
Purifying obtains（0. 555g）Pure yellow powder product.Yield is 89.8%.Using nuclear-magnetism and mass spectrum to the material of preparation into
Row characterization.
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 respectively as shown in Figures 2 and 31H 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 be [M+Na] corresponding molecular weight.Further demonstrate the structure of the fluorescent sensing material.
（2）Weigh 7.725mg steps（1）The fluorescent sensing material ethyl alcohol of middle preparation is dissolved constant volume and is prepared to 25mL
The storing solution of 1mM.The above-mentioned storing solutions of 1mL and 2mL are pipetted respectively is configured to 10 μM and 20 μM of second with distilled water constant volume to 100mL
Alcohol/water（v/v=1:99）The for use solution of fluorescent sensing material of system should use HEPES buffer solution regulation systems in the process
pH=7.4.The for use 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+）, respective fluorescence spectrum is measured respectively using Fluorescence Spectrometer（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 from the figure that fluorescent sensing material is strong from having at 525nm
Emission peak, this is because caused by its own big conjugated structure.
Fluorescent sensing material is in ethanol/water（v/v=1:99, pH=7.4）Mixed solvent system in, add in 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 from the figure 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 for belonging to ion hardly causes to change to the fluorescence of fluorescent sensing material itself.This is because divalent metal copper ion
Electronics distribution is 3d84s1, 3d orbital electron layer is in underfill state, works as Cu2+After being combined with fluorescent sensing material, as with
The electronics of excitation state can be transferred to bivalent cupric ion by the fluorescent sensing material of body, and base can not be returned to so as to cause excitation state electronics
State track, so as to which fluorescence is quenched.
（3）Removing step（2）In 10 μM of for use 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, in addition, to other common metal ions for being coexisted 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 from the figure 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 a certain concentration2+Can carry out
Quantitative detection；It is 0-10 μM of Cu to concentration in Fig. 92+It is detected, minimum detection limit LOD in Fig. 9（L）=3 σ/slope,
Middle slope s（slope）=6.396×107, standard deviation=0.113 of 20 blank samples, through calculating minimum detection limit it is reachable
5.3×10-9 M。
Other common metal ions and Cu2+Under ion concurrent conditions, to fluorescent sensing material recognition detection Cu2+It is dry
It is as shown in Figure 10 to disturb influence, it can be seen from the figure that the presence of other common metal ions identifies the fluorescent sensing material
Detect Cu2+Influence and little.Illustrate the fluorescent sensing material to Cu2+Identification have selection unicity, from 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 for use
Solution and 10 μM of Ni metal2+Solution presses different volumes ratio（0:10~10:0）Mixing so that the total concentration of the two mixture is
10 μM, fluorescence spectrometry is carried out to a series of mixture, Job curves is prepared and determines to combine ratio.
The Job curves of Fig. 7 further demonstrate that fluorescent sensing material with copper ion with 2:1 stoichiometric ratio is combined, this
Illustrate that prepared fluorescent sensing material can be responded by fluorescence signal to Ni metal2+Carry out single Selective recognition detection.
（5）Yangtze River Water, lake water and tap water are gathered, Cu is carried out to it respectively2+Mark-on experiment, Cu2+Mark-on amount be 10
μM and 15 μM, take step（2）In 20 μM of for use solution 2mL, the mark-on water sample of 2mL is separately added into, after mixing to it
Fluorescence spectrum is measured.
Fluorescent sensing material is to Cu in actual water sample2+School survey effect it is as shown in figure 11, from the results, it was seen that fluorescence pass
Material is felt to the Cu in actual water body2+Detection there is very high sensitivity and well 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 quantitative detection of target metal ions in water body.
（6）Human B lymphoma cell is cultivated for 24 hours in RPMI-1640 culture solutions (including 10%FBS), cultivation temperature
For 37 DEG C.Then the cell in PBS buffer solution is cultivated into 30min with 50 μM of fluorescent sensing material, and is washed three times with PBS
Remaining fluorescent sensing material is removed, is separately added into 20 μM and 50 μM of Cu2+20min is cultivated in continuation in PBS buffer solution, then
Cell is washed again with PBS, using inverted fluorescence microscope to adding in Cu2+Front and rear cell carries out imaging analysis.
Fluorescent sensing material is to Cu in biological cell2+Imaging results it is 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 in, 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 are respectively to add in not same amount Cu2+Afterwards cell in fluorescence off field
Imaging contexts.It can be seen from the figure that not same amount Cu in cell2+Presence can cause fluorescence is different degrees of to be quenched.This
As a result fluorescent sensing material Cu in biological cell is also demonstrated2+Context of detection have certain application value.
Claims (6)
1. a kind of preparation method of the chemiluminescence sensing material based on cinnamylaldehyde derivatives, which is characterized in that the material is
By 4-N, N- dimethyl cinnamic acid and 4- hydroxybenzoyl hydrazines pass through fluorescent sensing material made from the simple necleophilic reaction of a step；
Concrete operations are as follows：
By 4-N, N- dimethyl cinnamic acid and 4- hydroxybenzoyl hydrazines are placed in round-bottomed flask, and adding in absolute ethyl alcohol makes the two molten
Solution, is added dropwise suitable glacial acetic acid, is placed in oil bath pan and is stirred at reflux reaction；It treats to be cooled to room temperature after reaction, depressurize
Remove the crude product that solvent obtains fluorescent sensing material；Crude product is purified with column chromatography method to obtain pure yellow powder
Product；The back flow reaction temperature is 50~75 DEG C.
2. a kind of preparation method of chemiluminescence sensing material based on cinnamylaldehyde derivatives according to claim 1,
It is characterized in that, the 4-N, N- dimethyl cinnamic acid, 4- hydroxybenzoyl hydrazines, glacial acetic acid, absolute ethyl alcohol dosage are：0.17 ~
0.7g：0.15~0.62g：1 ~ 3 drop：20~60mL.
3. a kind of preparation method of chemiluminescence sensing material based on cinnamylaldehyde derivatives according to claim 1,
It is characterized in that, the reflux time is 5~10h.
4. a kind of fluorescent sensing material based on cinnamylaldehyde derivatives prepared by claim 1 the method is in environmental water sample
Cu2+Trace detection purposes.
5. purposes according to claim 4, the water sample is Yangtze River Water, lake water or tap water.
6. a kind of fluorescent sensing material based on cinnamylaldehyde derivatives prepared by claim 1 the method is used for Human B lymphoma
Cu in cell2+Detection non-disease diagnostic and therapeutic method purposes.
Priority Applications (1)
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| CN103409134A (en) * | 2013-08-08 | 2013-11-27 | 泰山学院 | Bifluorescence-emission organic light-emitting material and preparation method thereof |
| 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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| CN103409134A (en) * | 2013-08-08 | 2013-11-27 | 泰山学院 | Bifluorescence-emission organic light-emitting material and preparation method thereof |
| 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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| A fluorescent chemosensor for Cu2+ ions and its application in cell imaging;Xu Tang et al.;《Tetrahedron》;20170118;第73卷;第1367-1373页 * |
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