CN115926083B - Thermochromic covalent organic framework material and application thereof - Google Patents
Thermochromic covalent organic framework material and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 59
- OJUDFURAIYFYBP-UHFFFAOYSA-N (dihydrazinylmethylideneamino)azanium;chloride Chemical compound Cl.NNC(NN)=NN OJUDFURAIYFYBP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000007872 degassing Methods 0.000 claims description 13
- 238000010257 thawing Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- NPQXMTUQLRZKMK-UHFFFAOYSA-N 5-(6-formylpyridin-3-yl)pyridine-2-carbaldehyde Chemical compound C1=NC(C=O)=CC=C1C1=CC=C(C=O)N=C1 NPQXMTUQLRZKMK-UHFFFAOYSA-N 0.000 claims description 3
- NHWCJRHPJLHJPL-UHFFFAOYSA-N 6-(6-formylpyridin-2-yl)pyridine-2-carbaldehyde Chemical group O=CC1=CC=CC(C=2N=C(C=O)C=CC=2)=N1 NHWCJRHPJLHJPL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002262 Schiff base Substances 0.000 claims description 2
- 150000004753 Schiff bases Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 125000000532 dioxanyl group Chemical group 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
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- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000012634 fragment Substances 0.000 abstract 1
- 230000000638 stimulation Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 9
- 238000000944 Soxhlet extraction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
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- 239000012265 solid product Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 239000000370 acceptor Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
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- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
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- 238000009529 body temperature measurement Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
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Landscapes
- Pyridine Compounds (AREA)
Abstract
The invention belongs to the technical field of stimulus response materials, and particularly relates to a thermochromic covalent organic framework material and application thereof. An imine bond linked thermochromic covalent organic framework material is prepared by bridging a molecular module containing a 2-aldehyde pyridine structure with a triaminoguanidine hydrochloride containing an N-H fragment of an abundant proton donor through an imine bond. The covalent organic framework material prepared by the invention has rich intramolecular hydrogen bonds, the unique structure of the covalent organic framework material can generate proton coupling electron transfer process under the stimulation of external temperature, and azo bonds with long wavelength absorption are generated, so that the absorption wavelength of the material has obvious red shift, and ideal temperature response characteristics are shown. The temperature response test result shows that the thermochromic covalent organic framework material provided by the invention has excellent reversibility, stability and quick response, and has good development prospect in the application fields of color-changing pigment, temperature sensing and the like.
Description
Technical Field
The invention belongs to the technical field of stimulus response materials, and particularly relates to a thermochromic covalent organic framework material and application thereof.
Background
Stimulus-responsive materials capable of exhibiting variable changes in physical or chemical properties under external stimuli, such as light, humidity, pH and temperature lamps, are receiving increasing attention in the nanomaterial field. The thermochromic material has wide application prospects in the fields of sensing, green energy sources, intelligent windows, biological medicines and the like. Therefore, development and preparation of nanomaterials with good stimulus response characteristics are a current research hotspot.
The crystalline framework material, because of its high energy transfer properties between external stimuli and active sites, and clear structure-property relationships, is an ideal platform for designing thermochromic systems. The covalent organic framework material is a porous crystal framework material with a two-dimensional or three-dimensional structure, and has wide application prospect in the fields of molecular storage and separation, sensor application, catalysis, energy storage and the like. Covalent organic framework materials, because of all the excellent properties of crystalline framework materials, can be ideal candidates for designing thermochromic systems. At the same time, they may exhibit better stability compared to thermochromic materials based on metal organic frame materials, thanks to their rigid covalent bonds in the backbone.
Theoretically, the thermochromic properties of covalent organic framework materials can be imparted by two strategies. Firstly, adding guest molecules with thermochromic properties into holes of a covalent organic framework material to form a doping system, so as to realize the thermochromic properties of the covalent organic framework material; second, by designing the corresponding backbone structure, the inherent thermochromic properties in the covalent organic framework material are achieved. Compared with a doping system, the inherent thermochromic covalent organic framework material has the advantages of high thermal stability, high response speed, obvious optical signal change and the like, and attracts great research interest.
The low degree of geometric freedom due to strong interlayer stacking, and the lack of suitable building blocks, is still challenging to impart inherent thermochromic properties by designing the backbone structure of covalent organic framework materials. The invention provides a method for designing and preparing thermochromic covalent organic framework materials aiming at the technical problems.
Disclosure of Invention
The low degree of geometric freedom due to strong interlayer stacking, and the lack of suitable building blocks, is still challenging to impart inherent thermochromic properties by designing the backbone structure of covalent organic framework materials. The invention provides a method for designing and preparing thermochromic covalent organic framework materials aiming at the technical problems.
The invention provides a thermochromic covalent organic framework material, which is prepared from triaminoguanidine hydrochloride and a molecular module containing a 2-aldehyde pyridine structure through Schiff base reaction, wherein the chemical structural formula of the thermochromic covalent organic framework material is any one of the following a-d:
the molecular module containing the 2-aldehyde pyridine structure is 2, 6-dialdehyde pyridine, 2, 5-dialdehyde pyridine, 2 '-dipyridine-6, 6' -dicarboxaldehyde or 3,3 '-dipyridine-6, 6' -dicarboxaldehyde.
Preferably, the thermochromic covalent organic framework material is prepared by dissolving triaminoguanidine hydrochloride and a molecular module containing a 2-aldehyde pyridine structure in a mixed solvent, and then performing freeze thawing, degassing and heating reaction.
Specifically, the preparation method of the thermochromic covalent organic framework material comprises the following steps:
(1) Taking a molecular module with a 2-aldehyde pyridine structure and triaminoguanidine hydrochloride as reaction raw materials, adding a reaction solvent into the reaction raw materials to obtain a first mixed solution, and carrying out ultrasonic treatment on the mixed solution to obtain a second mixed solution;
(2) Transferring the second mixed solution into a 5mL Schlenk reaction tube, and performing freeze thawing and degassing treatment for three times to obtain a third mixed solution;
(3) Standing and heating the third mixed solution in a high-temperature oil bath for 72 hours to obtain a final product mixed solution;
(4) And (3) carrying out centrifugal separation operation on the final product mixed solution, retaining a solid product, and carrying out solvent washing, soxhlet extraction and vacuum drying on the obtained solid product to obtain the thermochromic covalent organic framework material.
Further, the molar ratio of the triaminoguanidine hydrochloride to the molecular module containing the 2-aldehyde pyridine structure is 1-3:1-2.
Specifically, the mole ratio of the triaminoguanidine hydrochloride to the molecular module containing the 2-aldehyde pyridine structure is 3:2.
Preferably, when the molecular module containing the 2-aldehyde pyridine structure is 2, 6-dialdehyde pyridine, the mixed solvent is tetrahydrofuran and acetic acid aqueous solution.
Further, the volume ratio of the tetrahydrofuran to the acetic acid aqueous solution is 3-5:1.
Preferably, when the molecular module containing the 2-aldehyde pyridine structure is 2, 5-dialdehyde pyridine, the mixed solvent is acetonitrile and water.
Further, the volume ratio of acetonitrile to water is 6-8:3.
Preferably, when the molecular module containing the 2-aldehyde pyridine structure is 2,2 '-bipyridine-6, 6' -dicarboxaldehyde or 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, the mixed solvent is dioxane, trimethylbenzene and acetic acid aqueous solution.
Further, the volume ratio of the dioxane, the trimethylbenzene and the acetic acid aqueous solution is 6-8:1:1-2.
Further, the concentration of acetic acid in the acetic acid aqueous solution is 2-4mol/L.
Preferably, the number of times of freeze thawing and degassing is 2 to 4.
Preferably, the method of freeze thawing and degassing is to suck negative pressure, defrost and degasify after freezing with liquid nitrogen.
Preferably, the heating reaction is followed by filtration, and the filtration method is centrifugation, washing, soxhlet extraction and vacuum drying.
Further, a mixed solution of 1, 4-dioxane, tetrahydrofuran and water was used for washing.
Specifically, in the step (2), the method of freeze thawing and degassing comprises the following steps: the Schlenk reaction tube filled with the reaction substance is sequentially subjected to 77K liquid nitrogen bath freezing, negative pressure pumping, thawing and degassing, and the process is repeated three times.
Specifically, in the step (4), the solvent washing process specifically includes: the solution was washed with deionized water, 1, 4-dioxane and tetrahydrofuran in this order 2 times each with a washing solvent volume of 5mL each.
Specifically, in the step (4), the soxhlet extraction process specifically includes: the product after washing the solvent was washed with 9:1 tetrahydrofuran/deionized water mixed solvent, and performing Soxhlet extraction for 48 hours.
The invention also provides a temperature sensor which is prepared from the thermochromic covalent organic framework material.
Compared with the prior art, the technical scheme of the invention has the following advantages:
The structure shown in the covalent organic framework material of the stimulus response contains a proton acceptor unit, namely a pyridine group, and a rich proton donor unit, namely N-H, which are bridged by an imine bond. This tight bridging approach enables the covalent organic framework material to form abundant intramolecular hydrogen bonds between the proton donor and proton acceptor. The unique structure enables proton-coupled electron transfer processes to occur under external temperature stimuli, which results in azo bonds (n=n) with long wavelength absorption in covalent organic framework materials, causing significant red shift in the absorption wavelength of the material with concomitant significant color and photoluminescence changes. The thermochromic covalent organic framework material has good thermochromic performance, can realize rapid reversible color and photoluminescence conversion from yellow to red under the regulation and control of external temperature change, has good thermal stability, and can be used in the fields of color-changing pigment, temperature measurement and the like.
Drawings
Fig. 1 is an infrared spectrum of four thermochromic covalent organic framework materials.
Fig. 2 is an optical image of four thermochromic materials at different temperatures.
Fig. 3 is a solid uv-vis absorption spectrum of four thermochromic covalent organic framework materials.
FIG. 4 is a graph of fluorescence spectra of four thermochromic covalent organic framework materials.
Fig. 5 is the switching stability of thermochromic covalent organic framework material TG-mDFP between two temperatures.
FIG. 6 is a powder X-ray diffraction pattern of thermochromic covalent organic framework material TG-mDFP after 10 heating-cooling processes.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for better illustration of the invention, and should not be construed as limiting the invention. In addition, the test methods used in the following examples are all conventional methods unless otherwise specified; the materials and reagents used are all commercially available. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced otherwise than as described herein, and therefore the present invention is not limited to the specific embodiments of the disclosure that follow.
A general combinatorial design strategy of thermochromic covalent organic framework materials is provided, namely, under the premise that pyridine matrix proton acceptors and guanidine matrix proton donors exist in the covalent organic framework materials, an intramolecular proton coupling electron transfer process occurs, and reversible thermochromic properties are generated.
Example 1
The embodiment provides a preparation method of a thermochromic covalent organic framework material TG-mDFP.
The proportion of the triaminoguanidine hydrochloride, the 2, 6-dialdehyde pyridine, the tetrahydrofuran and the acetic acid aqueous solution is respectively as follows: 0.1mmol;0.15mmol;0.8mL;0.2mL. Wherein the concentration of the aqueous acetic acid solution is 3mol/L. The above mixture was sonicated for 10 minutes and transferred to a 5mL schlenk tube. The mixture was subjected to three freeze thawing and degassing treatments, and then the reaction tube was placed in a 90 ℃ high temperature oil bath for heating treatment for 72 hours. After the reaction, the reaction tube was naturally cooled to room temperature, and centrifuged to obtain a yellow powdery solid. The yellow solid product is sequentially subjected to solvent washing, soxhlet extraction and vacuum drying to obtain the covalent organic framework material TG-mDFP, and the infrared spectrum is shown in figure 1.
Example 2
The embodiment provides a preparation method of a thermochromic covalent organic framework material TG-pDFP.
The proportion of the triaminoguanidine hydrochloride, the 2, 5-dialdehyde pyridine, the acetonitrile and the deionized water is respectively as follows: 0.1mmol;0.15mmol;0.7mL;0.3mL. The above mixture was sonicated for 30 minutes and transferred to a 5mL schlenk tube. The mixture was subjected to three freeze thawing and degassing treatments, and the post-reaction tube was placed in an 80 ℃ oil bath for heating treatment for 72 hours. After the reaction, the reaction tube was naturally cooled to room temperature, and centrifuged to obtain an orange powdery solid. The orange solid product is sequentially subjected to solvent washing, soxhlet extraction and vacuum drying to obtain a covalent organic framework material TG-pDFP, and the infrared spectrum is shown in figure 1.
Example 3
The embodiment provides a preparation method of a thermochromic covalent organic framework material TG-oOBPy.
The proportion of the aqueous solution of the triaminoguanidine hydrochloride, the 2,2 '-bipyridine-6, 6' -dicarboxaldehyde, the 1, 4-dioxane, the trimethylbenzene and the acetic acid is respectively as follows: 0.08mmol;0.12mmol;0.7mL;0.1mL;0.2mL. Wherein the concentration of the aqueous acetic acid solution is 3mol/L. The above mixture was sonicated for 30 minutes and transferred to a 5mL schlenk tube. The mixture was subjected to three freeze thawing and degassing treatments, and the post-reaction tube was placed in an oil bath at 120 ℃ and heated for 72 hours. After the reaction, the reaction tube was naturally cooled to room temperature, and centrifuged to obtain a yellow powdery solid. The yellow solid product is sequentially subjected to solvent washing, soxhlet extraction and vacuum drying to obtain the covalent organic framework material TG-oOBPy, and the infrared spectrum is shown in figure 1.
Example 4
The embodiment provides a preparation method of a thermochromic covalent organic framework material TG-oMBPy.
The proportion of the aqueous solution of the triaminoguanidine hydrochloride, the 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, the 1, 4-dioxane, the trimethylbenzene and the acetic acid is respectively as follows: 0.08mmol;0.12mmol;0.7mL;0.1mL;0.2mL. Wherein the concentration of the aqueous acetic acid solution is 3mol/L. The above mixture was sonicated for 30 minutes and transferred to a 5mL schlenk tube. The mixture was subjected to three freeze thawing and degassing treatments, and the post-reaction tube was placed in an oil bath at 120 ℃ and heated for 72 hours. After the reaction, the reaction tube was naturally cooled to room temperature, and centrifuged to obtain a yellow powdery solid. The yellow solid product is sequentially subjected to solvent washing, soxhlet extraction and vacuum drying to obtain the covalent organic framework material TG-oMBPy, and the infrared spectrum is shown in figure 1.
Effect example
Thermochromic properties of the thermochromic covalent organic framework materials obtained in examples 1,2, 3 and 4 were tested. As shown in fig. 2, the different test temperature points were set to 22, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130 ℃, and each temperature point was maintained for 10 seconds after reaching the specified temperature, for optical image acquisition and Kubelka-Munk spectral acquisition. As shown in fig. 2, fig. 3 and fig. 4, the four thermochromic materials each exhibit a rapid temperature response characteristic.
The cycle stability of the thermochromic material is also a key index for evaluating the performance of the thermochromic material, so taking TG-mDFP as an example, 10 heating and cooling cycle stability tests are carried out on the material, and the test results are shown in fig. 5 and 6, and the material can still show the reversibility of nearly 100% after 10 heating and cooling cycles.
The results fully show that the thermochromic covalent organic framework material provided by the invention has excellent reversibility, stability and quick response, and has good development prospect in the application fields of color-changing pigment, temperature sensing and the like.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The thermochromic covalent organic framework material is characterized in that the thermochromic covalent organic framework material is prepared from triaminoguanidine hydrochloride and a molecular module containing a 2-aldehyde pyridine structure through Schiff base reaction, and the chemical structural formula of the thermochromic covalent organic framework material is any one of the following a-d:
The molecular module containing the 2-aldehyde pyridine structure is 2, 6-dialdehyde pyridine, 2, 5-dialdehyde pyridine, 2 '-dipyridine-6, 6' -dicarboxaldehyde or 3,3 '-dipyridine-6, 6' -dicarboxaldehyde.
2. The thermochromic covalent organic framework material according to claim 1, wherein the thermochromic covalent organic framework material is obtained by dissolving a triaminoguanidine hydrochloride and a molecular module containing a 2-aldehyde pyridine structure in a mixed solvent, and then performing freeze thawing and degassing, and performing a heating reaction at 80-120 ℃.
3. Thermochromic covalent organic framework material according to claim 1 or 2, characterized in that the molar ratio of the triaminoguanidine hydrochloride salt to the molecular module comprising a 2-aldehyde pyridine structure is between 1 and 3:1-2.
4. The thermochromic covalent organic framework material of claim 2, wherein when the molecular module containing the 2-aldehyde pyridine structure is 2, 6-dialdehyde pyridine, the mixed solvent is tetrahydrofuran and acetic acid aqueous solution.
5. The thermochromic covalent organic framework material of claim 2, wherein when the molecular module containing a 2-aldehyde pyridine structure is 2, 5-dialdehyde pyridine, the mixed solvent is acetonitrile and water.
6. The thermochromic covalent organic framework material according to claim 2, wherein when the molecular module containing the 2-aldehyde pyridine structure is 2,2 '-bipyridine-6, 6' -dicarboxaldehyde or 3,3 '-bipyridine-6, 6' -dicarboxaldehyde, the mixed solvent is dioxane, trimethylbenzene and acetic acid aqueous solution.
7. The thermochromic covalent organic framework material of claim 2 wherein the number of freeze-thaw deaerations is 2-4.
8. The thermochromic covalent organic framework material of claim 2, wherein the method of freeze-thawing and degassing is vacuum pumping, thawing and degassing after freezing with liquid nitrogen.
9. The thermochromic covalent organic framework material of claim 2, wherein the heating reaction is followed by filtration by centrifugation followed by washing, cable-type extraction and vacuum drying.
10. A temperature sensor, characterized in that it is prepared using a thermochromic covalent organic framework material according to any of claims 1-9.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114752028A (en) * | 2022-05-19 | 2022-07-15 | 广西师范大学 | Solvent-free preparation method and application of covalent organic framework COFs film |
| CN115433367A (en) * | 2022-09-26 | 2022-12-06 | 山西大学 | Porphyrin COF material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114752028A (en) * | 2022-05-19 | 2022-07-15 | 广西师范大学 | Solvent-free preparation method and application of covalent organic framework COFs film |
| CN115433367A (en) * | 2022-09-26 | 2022-12-06 | 山西大学 | Porphyrin COF material and preparation method and application thereof |
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| Title |
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| Redox-Triggered Buoyancy and Size Modulation of a Dynamic Covalent Gel;Gobinda Das等;《American Chemical Society》;20190425;全文 * |
| 几种席夫碱衍生物的室温固相合成及可逆热致变色研究;梁小蕊;张勇;江炎兰;张立春;赵波;;新技术新工艺;20100225(02);全文 * |
| 对硝基苯甲醛缩对氨基乙酰苯胺希夫碱的室温固相合成及其可逆热致变色研究;梁小蕊;张勇;王磊;韩红宾;杨秉东;;新技术新工艺;20111025(10);全文 * |
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