CN106700087A - Triple hydrogen-bond supramolecular polymer and preparation method thereof - Google Patents
Triple hydrogen-bond supramolecular polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a triple hydrogen-bond supramolecular polymer and a preparation method thereof. A repeat unit comprises a hydrogen bond receptor and a hydrogen bond donor which are connected through a triple hydrogen bond, wherein the hydrogen bond receptor and the hydrogen bond donor are of a specific structure. The triple hydrogen-bond supramolecular polymer disclosed by the invention has high viscosity and can be biologically degraded. The triple hydrogen-bond supramolecular polymer is prepared by a self-assembly reaction of the hydrogen bond receptor and hydrogen bond donor in an organic solvent, and the hydrogen bond receptor and the hydrogen bond donor both can be synthesized from the easily available and economical and cheap raw materials through simple steps, so that the triple hydrogen-bond supramolecular polymer has strong practicability.
Description
Technical field
The present invention relates to supermolecule polymer field, more particularly to a kind of three deuterium bonds supermolecule polymer and its preparation side
Method.
Background technology
Supermolecule polymer be it is a kind of connected by reversible, directionality non-covalent interaction by repeat unit and
Into new polymers, the mostly monomer with double-functional group spontaneously formed by molecular self-assembling in a solvent, it is not necessary to
Initiator.The difference of supermolecule polymer and traditional polymer is that the connecting key between monomer is become with direction by covalent bond
Property and reversible non-covalent bond.The polymer phase ratio formed with traditional covalent bond, the supermolecule of non-covalent bond induced synthesis
Polymer has the characteristics such as environment-responsive and self-healing, and it is in degradation material, drug delivery and sustained release and functional material
Deng being had broad application prospects in field.And because the supramolecular system that non-covalent bond is constructed has certain invertibity,
Selfreparing mechanism can be utilized it as.The selfreparing supermolecule polymer type based on non-covalent bond studied at present is main
Have：1. using the Polymer Systems of hydrogen bond；2. the macromolecule being coordinated based on metal ligand；3. Subjective and Objective macromolecule；4. ion gathers
Compound；5. the reversible non-covalent bound complex system of reversible covalent bonds one.
Hydrogen bond has the non-covalent bond of invertibity and directionality while being a kind of common.It is multiple when having on polymer chain
When can form the group of hydrogen bond, the supramolecular structure of reversible crosslink state can be gathered under certain condition.On macromolecular chain
Hydrogen bond is easy to be formed at low temperature.And hydrogen bond can be broken in liter high-temperature, the fine fisssure that so can be used to heal in macromolecule
Line.Although single hydrogen bond energy is smaller, binding constant is relatively low, and being overlapped mutually between multiple hydrogen bonding and cooperateing with can but obtain
Extensive concern is obtained and has ground to the relatively strong effect for combining energy, thus the supermolecule polymer system that multiple hydrogen bonding is combined
Study carefully.
Than two deuterium bond systems it is more likely to form stronger network, its linear arrangement mode has DAD- to three deuterium bond systems
Tri- kinds of (A of ADA, AAD-DDA, AAA-DDD:Acceptor, hydrogen bond donor；D:Doner, hydrogen bond receptor).For complementary type hydrogen bond
For compound system, when hydrogen bond receptor and hydrogen bond donor are respectively at the both sides of hydrogen bond assembly system, all secondary hydrogen bonds are equal
Adelphotaxy is produced, the compound of now hydrogen bond assembling has high stability.Therefore in all triple hydrogen bonding arrangements
In combination, AAA-DDD hydrogen bonding arrangements systems are considered to have highest stability.But the existing deuterium bond of AAA-DDD types three surpasses
The general synthesis step of Molecularly Imprinted Polymer is cumbersome, relatively costly.
The content of the invention
In order to solve problem of the prior art, goal of the invention of the invention is to provide a kind of three deuterium bonds supermolecule polymerization
Thing, the three deuterium bonds supermolecule polymer viscosity is high, and can be with biodegradation.Another goal of the invention of the invention is to provide
The preparation method of above-mentioned three deuterium bonds supermolecule polymer.The technical scheme is as follows：
A kind of three deuterium bond supermolecule polymers, its repeat unit includes the hydrogen bond receptor being connected with each other by three deuterium bonds
And hydrogen bond donor, shown in the structure such as formula (1) of the hydrogen bond receptor：
Shown in the structure of the hydrogen bond donor such as formula (2)：
Wherein, R1、R2And R3The group based on hydrocarbon of respective independent expression saturation or undersaturated straight or branched, or
Person's alkyl chain of each independent expression containing aromatic ring, the alkyl chain containing aromatic ring can optionally include one or more miscellaneous originals
Son.
Preferably, the hetero atom is one or more in N, O, S, Si, P and halogen.
Preferably, the alkyl chain in the alkyl chain containing aromatic ring contains 2 to 10 C atoms.
Preferably, the group based on hydrocarbon contains 1 to 10 C atom.
It is furthermore preferred that R1、R2And R3Each independent expression is containing 1 to 5 saturated straight chain or branched paraffin of C atoms, or
The each independent alkyl chain containing aromatic ring for representing hetero atom substitution of person, the alkyl chain in the alkyl chain containing aromatic ring contains
There are 2 to 5 C atoms.It is further preferred that R1、R2And R3Respective independent expression methyl, ethyl, propyl group, isopropyl, acetyl
Base, phenethyl or a chlorobenzene ethyl, still more preferably, R1、R2And R3The each independent 1-3 alkyl of carbon atom of expression,
Most preferably, R1、R2And R3Represent ethyl.
It is a further object to provide the preparation method of above-mentioned three deuterium bonds supermolecule polymer, its step bag
Include：
S1. hydrogen bond receptor of the composite structure as shown in formula (1)：
S2. hydrogen bond donor of the composite structure as shown in formula (2)：
S3. hydrogen bond donor of the hydrogen bond receptor and structure by structure as shown in formula (1) as shown in formula (2) in chloroform and
Self-assembling reaction is carried out in the mixed solvent of methyl alcohol, the three deuterium bonds supermolecule polymer is obtained after removing mixed solvent；
The above S1 and S2 step are in no particular order.
Preferably, the step S1 is that compound first by structure as shown in formula (3) is carried out with 2- amino -3- pyridine carboxaldehydes
Cyclization reaction obtains 7-naphthyridine derivatives of the structure as shown in formula (4),
Then the 7-naphthyridine derivatives by structure as shown in formula (4) enter with DMFDMA (N,N-dimethylformamide dimethylacetal)
Row cyclization reaction obtains compound of the structure as shown in formula (5),
Finally isocyanates reaction of the compound by structure as shown in formula (5) with structure as shown in formula (6) is i.e. available
The hydrogen bond receptor,
Hydrogen bond receptor of the invention can preferably be prepared using the above method, and those skilled in the art can also basis
Structure design others reaction scheme.7-naphthyridine derivatives of the composite structure as shown in formula (4) can be with the preferred synthetic route
Using existing reaction method, the present invention is preferably in ethanol as solvent, by compound of the structure as shown in formula (3) and 2- ammonia
Base -3- pyridine carboxaldehydes, piperidines mixing, react what is obtained within 4~6 hours at 70 DEG C~80 DEG C.Wherein 2- amino -3- pyridine carboxaldehydes with
The mol ratio for feeding intake of compound of the structure as shown in formula (3) is 1：(1~1.2), compound of the structure as shown in formula (3) is skipped over
Amount, suction filtration and solid is washed after the completion of reaction, and preferred mode of washing is respectively with ethyl acetate and absolute ethyl alcohol flushing.
It is furthermore preferred that by 7-naphthyridine derivatives of the structure as shown in formula (4) and DMFDMA in 70W~80W, 100 DEG C~120
DEG C, carry out cyclization reaction under 100PSI~150PSI microwave conditions and obtain compound of the structure as shown in formula (5).In reaction,
DMFDMA both as raw material or made solvent, and inventory can significantly be in excess in 7-naphthyridine derivatives of the structure as shown in formula (4).During reaction
Between be preferably 40 minutes~1 hour, using TLC (thin layer chromatography board) monitoring reactions completely after, stand 16h~24h, then carry out pure
Change.Purifying refers to carry out suction filtration after completion of the reaction and wash solid, preferably uses ethyl acetate rinse.
The reaction condition of the isocyanates reaction by compound of the structure as shown in formula (5) with structure as shown in formula (6) is excellent
The compound by structure as shown in formula (5) is elected as with isocyanates of the structure as shown in formula (6) according to mol ratio 2:1 anhydrous
Mixing in DCM (dichloromethane), DBTDL (dibutyl tin laurate), then after reaction completely at 60 DEG C purify
The hydrogen bond receptor for arriving.Those skilled in the art can also carry out the reaction of isocyanates and hydroxyl using other known methods.Instead
Using silica gel column chromatography purify obtaining hydrogen bond receptor after the completion of answering.
Preferably, the step S2 is compound and chemical combination of the structure as shown in formula (8) first by structure as shown in formula (7)
Thing carries out substitution reaction and obtains compound of the structure as shown in formula (9),
Then the compound by structure as shown in formula (9) carries out cyclization reaction with compound of the structure as shown in (10), obtains
To the hydrogen bond donor,
Hydrogen bond donor of the invention can be prepared using the above method, and those skilled in the art can also be according to structure
The other reaction schemes of design.In the preferred synthetic route, compound of the composite structure as shown in formula (9) can be by structure such as
Compound shown in formula (7) with compound of the structure as shown in formula (8) with EA (ethyl acetate) as solvent, with Et3N (triethylamine)
Mixing, reacts at 0 DEG C~10 DEG C and obtains.Compound of the structure as shown in formula (7) and compound of the structure as shown in formula (8)
Mol ratio is (3~3.6):1, reaction carries out suction filtration after terminating, and filtrate with silica gel column chromatography purify and obtains structure such as formula
(9) compound shown in.
It is furthermore preferred that compound of the structure as shown in formula (9) and compound of the structure as shown in formula (10) are in alkalescence
Under the conditions of, in DMF solvent, being heated to 80 DEG C~90 DEG C carries out cyclization reaction.Wherein described alkalescence condition can be anhydrous by adding
Potassium carbonate obtain, compound and potassium carbonate of compound, structure of the structure as shown in formula (9) as shown in formula (10) mole
Amount ratio is：1：15：15.Reaction carries out a point liquid extraction with water and EA after terminating, then (organic phase washing is preferably used into saturated common salt
Water washing), dry (preferably with anhydrous sodium sulfate drying) after with silica gel column chromatography purify obtaining hydrogen bond donor.
Preferably, the step S3 is after first adding hydrogen bond receptor and mixed solvent, according to hydrogen bond receptor and hydrogen bond donor
Mol ratio is 3:2 add hydrogen bond donor, carry out self-assembling reaction to removing mixed solvent by transparent and obtain three heavy hydrogen
Key supermolecule polymer.Mixed solvent is preferably chloroform and methyl alcohol according to volume ratio 10:The mixed solvent of 1 mixing, self assembly is anti-
After should terminating, the mixed solvent directly can be removed by volatilizing at room temperature.
Shown in the reaction scheme such as formula (10) of hydrogen bond receptor of the composite structure of the present invention as shown in formula (1)：
Shown in the reaction scheme such as formula (11) of hydrogen bond donor of the composite structure of the present invention as shown in formula (2)：
The linear arrangement mode of the three deuterium bond supermolecule polymers according to obtained by above-mentioned preparation method is AAA-DDD types,
As shown in formula (12)：
The beneficial effect that technical scheme provided in an embodiment of the present invention is brought is：
The characteristics of three deuterium bonds supermolecule polymer of the present invention not only has general hydrogen bond supermolecule polymer, can be with
Network-like structure is formed in space, with invertibity and stronger binding ability, makes it have supermolecule polymer to temperature
Sensitive the characteristics of, can be used for the multiple uses such as the micro-crack healed in macromolecule, it is important that also high with viscosity, and can
The characteristics of to carry out biodegradation.The three deuterium bonds supermolecule polymer can be by hydrogen bond receptor and hydrogen bond donor organic molten
Carry out self-assembling reaction in agent to obtain, the hydrogen bond donor and hydrogen bond receptor can be by being readily available and economical cheap
Raw material synthesizes by simple step, with very strong practicality.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with reaction scheme to of the invention real
The mode of applying is described in further detail.
Embodiment 1 synthesizes 7-naphthyridine derivatives (1-4)
Difference Weigh Compound(1250mg, 8.8mmol), 2- amino -3- pyridines
Formaldehyde (976mg, 8.0mmol) pours into 20mL absolute ethyl alcohol and stirrings to being completely dissolved in the single necked round bottom flask of 100mL.With
Afterwards, add 7mL piperidines that 5h is reacted at being placed in 80 DEG C, TLC (using thin-layer chromatography chromatography) detections are complete to reaction.Locate after carrying out
Reason：System is carried out into suction filtration, suction filtration obtains faint yellow solid powder, and uses ethyl acetate and absolute ethyl alcohol to rinse respectively to obtain twice
To pure compound (1-4), yield：70%.
7-naphthyridine derivatives (1-4) are after tested:
1H NMR (400MHz, DMSO) δ 8.84-8.72 (m, 2H), 8.43 (s, 1H), 8.14 (dd, J=7.9,2.0Hz,
1H), 7.45 (s, 2H), 7.23 (dd, J=7.8,4.4Hz, 1H), 4.53 (s, 1H), 3.51 (dd, J=11.5,6.2Hz, 2H),
1.73 (p, J=6.5Hz, 2H)
Embodiment is 2-in-1 into compound (1-5)
Weigh Compound (1-4) (800mg, 3.25mmol) in 35mL microwave reaction pipes, add 10mL DMFFMA (N,
Dinethylformamide dimethylacetal) be placed in 80W, 110 DEG C, 45min is reacted under the conditions of 150PSI, TLC detections reaction is completely simultaneously
Stand overnight.Post-processed：Reaction system is carried out into suction filtration and obtains khaki solid powder, with ethyl acetate rinse 2 times, very
Sky is dried to obtain khaki solid powder as compound (1-5), yield：75%.
Compound (1-5) is after tested:
1H NMR (400MHz, DMSO) δ 10.92 (s, 1H), 8.46-8.36 (m, 2H), 8.10 (dd, J=7.7,1.6Hz,
1H), 7.22 (dd, J=7.6,4.8Hz, 1H), 4.68 (t, J=5.0Hz, 1H), 4.02 (dq, J=15.7,6.5Hz, 2H),
3.48 (d, J=5.2Hz, 2H), 1.90-1.81 (m, 2H)
Embodiment 3 synthesizes hydrogen bond receptor (1-1)
Weigh Compound (1-5) (740mg, 2.75mmol) and 1, hexamethylene-diisocyanate (210mg, 1.25mmol) in
In 100mL round-bottomed flasks, add the anhydrous DCM of 50mL (chloroform), DBTDL (dibutyl tin laurate) 10 to drip, be placed in 60 DEG C of oil
Heating response in bath.Reaction is post-processed after terminating：Organic solvent is removed under reduced pressure, with silica gel column chromatography separating purification [V (second
Acetoacetic ester)：V (methyl alcohol)=8:1], hydrogen bond receptor (1-1) is obtained.
Hydrogen bond receptor (1-1) is after tested:
1H NMR (400MHz, DMSO) δ 9.43 (s, 2H), 9.30-9.24 (m, 2H), 8.76 (dd, J=8.3,2.0Hz,
2H), 8.69 (s, 2H), 7.70 (dd, J=8.2,4.1Hz, 2H), 7.09 (d, J=5.3Hz, 2H), 4.07 (dt, J=12.2,
6.4Hz, 8H), 2.92 (dd, J=12.5,6.2Hz, 4H), 2.19-1.94 (m, 4H), 1.31 (s, 4H), 1.23-1.14 (m,
4H).
mp 211.4℃。
Embodiment 4 synthesizes compound (1-9)
Weigh Compound (1-7)(547.8mg, 3.3mmol) and triethylamine (404mg, 4.0mmol) are in 25mL
In round-bottomed flask, add the EA (ethyl acetate) of 8mL to be dissolved to clarification and be placed in ice-water bath.After temperature stabilization after 0~5 DEG C,
The EA solution 3mL of 1,3,5- tri-benzoyls chlorine (265.2mg, 1mmol) is added dropwise.Occur a large amount of white opacity things in reaction system,
Post-processed after reaction completely：Suction filtration, taking filtrate carries out silica gel column chromatography separating purification [V (petroleum ether)：V (ethyl acetate)
=4:1], that is, neat compounds (1-9), yellow solid powder, yield 85% are obtained.
Compound (1-9) is after tested：
1H NMR (400MHz, DMSO) δ 9.87 (s, 3H), 8.70-8.60 (m, 3H), 7.85 (dd, J=9.1,2.2Hz,
6H), (dd, J=5.1,3.5Hz, the 6H) of 7.18 (d, J=8.7Hz, 6H), 4.72 (dd, J=5.2,3.3Hz, 6H), 4.51
Embodiment 5 synthesizes hydrogen bond donor (1-2)
Weigh Compound (1-9) (327mg, 0.5mmol), compound
(1.25g, 7.5mmol) and anhydrous K2CO3(1.035g, 7.5mmol) adds DMF (N, the N- of 8mL in the single-necked flask of 50mL
Dimethylformamide) it is placed in reaction under 85 DEG C of oil baths.Reaction is post-processed after terminating：Reaction system is poured into 20mL originally
(20mL × 5) are extracted with EA after being mixed in water, organic phase saturated common salt water washing 3 times is collected, then by the anhydrous sulphur of organic phase
Sour sodium is dried.Decompression suction filtration, carries out silica gel column chromatography [V (ethyl acetate)：V (methyl alcohol)=10:1], that is, the confession of purified hydrogen key is obtained
Body (1-2), yield 40%.
Hydrogen bond donor (1-2) is after testing：
1H NMR (400MHz, DMSO) δ 8.68 (s, 3H), 7.03 (d, J=7.6Hz, 6H), 6.98-6.82 (m, 9H),
6.76 (d, J=7.8Hz, 3H), 4.65 (s, 6H), 4.28 (d, J=13.1Hz, 6H), 4.11 (dd, J=17.5,7.1Hz,
3H), 3.90 (d, J=6.9Hz, 9H), 1.34-0.89 (m, 18H)
mp 74.4℃。
Embodiment 6 synthesizes three deuterium bond supermolecule polymers
Hydrogen bond receptor (1-1) (50mg, 0.0376mmol) is weighed in 4mL sample bottles, 300 μ L chloroforms and 30 μ L first are added
Alcohol, hydrogen bond receptor (1-1) component is not completely dissolved.Hydrogen bond donor (1-2) (38.34mg, 0.0564mmol) is added immediately, and is mended
Plus 400 μ L chloroforms and 40 μ L methyl alcohol, two components are completely dissolved to form transparent red solution.Treat that solvent volatilizees at ambient temperature
The larger viscoid of viscosity is formd in bottle afterwards, is three deuterium bond supermolecule polymers, its linear repeating units such as formula (12) institute
Show：
The three deuterium bonds supermolecule polymer is carried out into fluorescence titration and Identification On Crystal, specific authentication method such as document
Described in Chemistry-A European Journal 2014,20,16980.Crystal structure shows that the three deuterium bonds supermolecule gathers
Compound only has three hydrogen bonding sites.Fluorescence titration experiment shows that 1 can be formed：The compound knot of the AAA-DDD of 1 mol ratio
Structure, therefore qualification result illustrates that the three deuterium bonds supermolecule polymer has the structure of three deuterium bonds, its linear repeating units is such as
Shown in formula (12).
The three deuterium bonds supermolecule polymer is rufous, and viscosity is big, can be hung upside down maintained above up to 5 minutes in test tube wall
Do not flow.Meanwhile, by three deuterium bonds supermolecule polymer of the invention according to document Biomed.Chromatogr.2011；25:
1360-1363 method carries out zoopery, to experiment mice according to mice weights 5mg/KG injection concentrations for 10 μ g/L are triple
The normal saline solution of hydrogen bond supermolecule polymer, the three deuterium bonds supermolecule polymer can in rat liver 30 minutes it is complete
Into degraded.
It should be noted that：The preparation method of the three deuterium bond supermolecule polymers that above-described embodiment is provided, only with above-mentioned
A kind of obtained three deuterium bonds supermolecule polymer is illustrated, in practical application, can be in the base of linear repeating units
On plinth, Material synthesis other three similar deuterium bond supermolecule polymers, its specific preparation method and this hair are selected as needed
Bright specific embodiment is similar, and those skilled in the art can carry out the adjustment of reaction condition according to general knowledge, repeat no more here.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all it is of the invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (10)
1. a kind of three deuterium bonds supermolecule polymer, its repeat unit comprising the hydrogen bond receptor being connected with each other by three deuterium bonds and
Hydrogen bond donor, it is characterised in that：Shown in the structure of the hydrogen bond receptor such as formula (1)：
Shown in the structure of the hydrogen bond donor such as formula (2)：
Wherein, R1、R2And R3The group based on hydrocarbon of respective independent expression saturation or undersaturated straight or branched, or respectively
From alkyl chain of the independent expression containing aromatic ring, the alkyl chain containing aromatic ring can optionally include one or more hetero atoms.
2. three deuterium bonds supermolecule polymer according to claim 1, it is characterised in that：The hetero atom be N, O, S,
One or more in Si, P and halogen.
3. three deuterium bonds supermolecule polymer according to claim 1, it is characterised in that：The group based on hydrocarbon contains
1 to 10 C atom.
4. three deuterium bonds supermolecule polymer according to claim 1, it is characterised in that：The alkyl chain containing aromatic ring
In alkyl chain contain 2 to 10 C atoms.
5. the preparation method of three deuterium bond supermolecule polymers any one of a kind of claim 1-4, it is characterised in that：Its
Step includes：
S1. hydrogen bond receptor of the composite structure as shown in formula (1)：
S2. hydrogen bond donor of the composite structure as shown in formula (2)：
S3. hydrogen bond donor of the hydrogen bond receptor and structure by structure as shown in formula (1) as shown in formula (2) is in chloroform and methyl alcohol
Mixed solvent in carry out self-assembling reaction, obtain the three deuterium bonds supermolecule polymer after removing mixed solvent；
The above S1 and S2 step are in no particular order.
6. the preparation method of three deuterium bond supermolecule polymers according to claim 5, it is characterised in that：The step S1 is
First the compound by structure as shown in formula (3) and 2- amino -3- pyridine carboxaldehydes carry out cyclization reaction and obtain shown in structure such as formula (4)
7-naphthyridine derivatives,
Then the 7-naphthyridine derivatives by structure as shown in formula (4) and N,N-dimethylformamide dimethylacetal carry out cyclization and react
To compound of the structure as shown in formula (5),
Finally isocyanates reaction of the compound by structure as shown in formula (5) with structure as shown in formula (6) can obtain described
Hydrogen bond receptor,
7. the preparation method of three deuterium bond supermolecule polymers according to claim 6, it is characterised in that：By structure such as formula
(4) 7-naphthyridine derivatives shown in enter with DMFDMA under 70W~80W, 100 DEG C~120 DEG C, 100PSI~150PSI microwave conditions
Row cyclization reaction obtains compound of the structure as shown in formula (5).
8. the preparation method of three deuterium bond supermolecule polymers according to claim 5, it is characterised in that：The step S2 is
First the compound by structure as shown in formula (7) carries out substitution reaction and obtains structure such as formula with compound of the structure as shown in formula (8)
(9) compound shown in,
Then the compound by structure as shown in formula (9) carries out cyclization reaction with compound of the structure as shown in (10), obtains institute
State hydrogen bond donor,
9. the preparation method of three deuterium bond supermolecule polymers according to claim 8, it is characterised in that：The structure such as formula
(9) compound shown in compound of the structure as shown in formula (10) in the basic conditions, in DMF solvent, be heated to 80 DEG C~
90 DEG C carry out cyclization reaction.
10. the preparation method of three deuterium bond supermolecule polymers according to claim 5, it is characterised in that：The step S3
It is 3 according to hydrogen bond receptor and hydrogen bond donor mol ratio after first adding hydrogen bond receptor and mixed solvent to be:2 add hydrogen bond donor,
Carry out self-assembling reaction and obtain the three deuterium bonds supermolecule polymer to removing solvent by transparent.
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| CN108641092B (en) * | 2018-04-25 | 2021-06-18 | 辽宁大学 | Preparation method of supramolecular polymer composite micelle based on hydrogen bond |
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| CN109400900B (en) * | 2018-10-30 | 2021-02-05 | 西北师范大学 | Supermolecule gel assembled based on column [5] arene main-object and application thereof in detection and adsorption of iron ions |
| CN110591140A (en) * | 2019-08-27 | 2019-12-20 | 北京大学 | Nano-porous polymer film material constructed by utilizing hydrogen bonds |
| CN110627993A (en) * | 2019-10-22 | 2019-12-31 | 华南理工大学 | Waterborne polyurethane dispersion containing quadruple hydrogen bonds and preparation method thereof |
| CN110627993B (en) * | 2019-10-22 | 2021-09-21 | 华南理工大学 | Waterborne polyurethane dispersion containing quadruple hydrogen bonds and preparation method thereof |
| CN114105986A (en) * | 2021-12-06 | 2022-03-01 | 华东理工大学 | Aromatic condensed ring diketone compound and preparation method and application thereof |
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