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WO2004085442A2 - Nouveaux composes calix arenes, leur procede de preparation et leur utilisation, en particulier comme mimes de sites enzymatiques - Google Patents

Nouveaux composes calix arenes, leur procede de preparation et leur utilisation, en particulier comme mimes de sites enzymatiques Download PDF

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WO2004085442A2
WO2004085442A2 PCT/EP2004/003140 EP2004003140W WO2004085442A2 WO 2004085442 A2 WO2004085442 A2 WO 2004085442A2 EP 2004003140 W EP2004003140 W EP 2004003140W WO 2004085442 A2 WO2004085442 A2 WO 2004085442A2
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WO2004085442A3 (fr
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Olivia Reinaud
Ivan Jabin
Ulrich Darbost
Yun Xu-Li
Sophie Redon
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Centre National de la Recherche Scientifique CNRS
Universite Paris Descartes
UNIVERSITE DU HAVRE
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Centre National de la Recherche Scientifique CNRS
Universite Paris Descartes
UNIVERSITE DU HAVRE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents

Definitions

  • the present invention relates to new calix arene compounds, their process of preparation and their use, particularly as enzymatic mimes.
  • Calix[4]arenes have been extensively studied for host-guest chemistry. However, because of their small size, they have mostly been used as a platform for the preorganization of a binding site.
  • the larger calix[6]arenes appear more suitable to play the role of a molecular receptor, yet their higher conformational flexibility, due to facile ring inversion, represents an obstacle (C. D. Gutsche, Calixarenes Revisited, Monographs in Supramolecular Chemistry, 1998, J. F. Stoddart, Ed. The Royal Society of Chemistry, Cambridge, U.K.). It has been recently shown that rigidification of the calix[6] arene core could be achieved through the use of coordination chemistry
  • the binding of a metal ion to three amino groups that are covalently linked to the calix[6]arene small rim can constrain the macrocycle into a cone conformation.
  • the so-called funnel complexes present a biomimetic environment for Cu or Zn, which can coordinate a neutral guest inside the hydrophobic cavity (Seneque, O. et al. Chem. Commun. (2001) 984-985; Seneque, O. et al. J. Am. Chem. Soc. (2001) 123, 8442-8443;
  • the aim of the present invention is to provide new compounds calix[6](aza)crown, and their process of preparation.
  • the aim of the present invention is to describe the synthesis of the first C 3v - symmetrical calix[6](aza)crown, where the small rim is capped with the tris(2- aminoethyl)amine tripodal unit.
  • Such caped calix[6](aza)crown compounds present the following advantages: A metal ion is not required anymore to constrain the calixarene in a cone conformation.
  • the covalent aza-links at the small rim prevent the cone-cone inversion of the calixarene structure and maintain it in a conformation suitable for playing the role of a good and selective host for organic guests.
  • the aza crown can bind a protic guest through hydrogen bonding for example but also a cationic species such as a metal ion.
  • the coordinated metal is then strongly complexed by the aza crown and is highly resistant to decoordinating processes.
  • Coordination of an organic molecule or inorganic ligand such as an anion will be highly controlled by the design of the calixarene host, thanks to its caping at the small rim.
  • these compounds can be transformed into water-soluble hosts that will display selective coordinating abilities of small molecules or ions in biological media.
  • the present invention relates to compounds of the following formula (I):
  • R and R l5 identical or different, represent: H, a halogen atom such as F, Cl, Br, I, an ester or a thioester group of 2 to 20 carbon atoms, a carboxylic group, an amide or a thioamide group, a sulfonamide group, SO 3 " .
  • R 3 represents: H, an alkyl group or an alkyl chain , of 1 to 20 carbon atoms possibly substituted by any other functional group, such as defined for R and R 1 ⁇ and is particularly a methyl group;
  • R 5 representing an H, NO 2 , OH or an alkyl group being possibly substituted with a halogen atom, an ester, a carboxylic group, an amide or a thioamide group, a sulfonamide group, SO 3 " , a phosphate, a carboxylate, NO 2 , a primary, secondary or tertiary amine group, a nitrilo, an alcohol, an ether, a thiol, a thiother derivative; and being preferably a methyl group;
  • * or X represents a group of formula (A): or a corresponding ammonium salt of said formula (A), wherein at least one of the three nitrogen atoms bears a R 6 substituent, R 6 having the same definition as R 5 ;
  • the present invention consists in a calix[6]arene capped with a C 3v - symmetrical azacrown bridge.
  • a rigidified ligand should possess a reinforced complexation ability since the cap should prevent decomplexation processes by protecting the metal ion from the external medium, while maintaining a large degree of flexibility essential for; the system in order to act as a biomimetic receptor.
  • the present invention also relates to compounds having the following formula (II):
  • R, R l5 R 3 and p are such as defined above.
  • the present invention also relates to compounds having the following formula
  • R, Ri, R 3 , R 6 and p are such as defined above.
  • the compounds of the invention are characterised in that R and Ri are tBu groups and R 3 represents a methyl group, and in that p is equal to 2.
  • the present invention also relates to compounds having the following formula
  • m, n, R, Ri, R 2 and R 3 are such as defined above, and wherein X represents a nitrogen atom, an ammonium I T ⁇ Rs, or CR 5 group, R 5 being such as defined above.
  • the present invention also relates to compounds having the following formula
  • the present invention also relates to compounds having the following formula
  • n, R, Ri, R , R 3 and R 5 are such as defined above.
  • the present invention also relates to compounds having the following formula
  • the present invention also relates to compounds having the following formula
  • the present invention also relates to compounds having the following formula
  • n, R, Ri, R 2 , and R 3 are such as defined above.
  • the present invention also relates to compounds having the following formula
  • the present invention also relates to compounds having the following formula
  • the compounds of the invention are characterised in that R 3 represents a methyl group and R 2 , R4 and R 5 represent a hydrogen atom.
  • the compounds of the invention are characterized in that R and Ri represent tBu groups.
  • the compounds of the invention are characterised in that R represents SO 3 Na and Ri represents NO 2 .
  • the present invention also relates to compounds such as defined above, characterised in that they are linked to: - a function liable to bind, if necessary via a binding site, to molecules, such as antibodies, haptens or peptides, which are able to bind specifically with epitopes located at the surface of the cells of the organism, or to chemical or biological compounds located at the surface of a solid carrier, or
  • the present invention also relates to complexes between a compound such as defined above, and an element chosen among:
  • a metal such as zinc, cadmium, mercury, copper, silver, gold, iron, cobalt, cesium
  • - an actinide such as uranium, americium, plutonium or a lanthanide such as lanthanum, europium, gadolinium, ytterbium;
  • radioelement more particularly chosen among ⁇ , ⁇ or ⁇ emitter radiometals, such as Tc, Re;
  • a cationic guest such as an ammonium
  • an anionic guest such as a phosphate, a phosphonate, a sulfonate, a sulfate, a carboxylate, CIST, F " , CT " , Br ⁇ T
  • said complexes resulting from the insertion of said element into the calix arene group and from interactions between said element and the coordination sites Ai, A 2 , A 3 , and X, of the calix arene group of said compound.
  • Ai, A 2 , A 3 , and X, of the calix arene group of said compound are preferably ionic interactions.
  • the present invention also relates to pharmaceutical compositions comprising a compound such as defined above, or a complex such as defmed above, in association with a pharmaceutically acceptable carrier.
  • the present invention also relates to the use of compounds such as defmed above: - for the preparation of selective metal extractants such as radioactive or precious metals;
  • depolluting agents in aquatic media captors of molecules in gas phase, ligands in medical imaging, biological probes, carriers of therapeutic molecules, stationary phases for gas chromatography, or stabilizers of compounds sensitive to the presence of metals.
  • the present invention also relates to the use of a complex such as defined above, between a compound such as defined above and a radioelement for the manufacture of a medicament for radioimmunotherapy, in particular for the treatment of cancers, or for the treatment against metastase proliferation.
  • the present invention also relates to a process of preparation of compounds such as defined above, characterized in that it comprises the following steps:
  • R 3 Y a selective 1,3,5-trialkylation with alkyl halide R 3 Y, R 3 being such as defined above and Y representing a leaving group, and particularly a halogen atom, such as Cl, Br and I, of compound 2 of following formula:
  • R, R ls R 3 and p being such as defined above,
  • the process of preparation of compounds of formula (2b) from compounds of formula (2a) comprises eventually a step of treatment with an electrophile, which can be:
  • RZ a step of treatment with RZ, wherein R is such as defmed above and is different from H and Z is a halogen atom, RZ being preferably HSO 3 Cl or HNO 3 , or
  • the present invention also relates to compounds having the following formula
  • the present invention also relates to compounds having one of the following
  • R, Ri, R3 and p are such as defined above, said compounds being liable to be used as synthesis intermediaries for the preparation of compounds of formula (II) such as defined above, provided that the compounds wherein R and Ri represent tBu, R 3 represents a methyl group and p is 2, are excluded.
  • the present invention also relates to a process of preparation of water-soluble compounds, characterized in that it comprises the following steps:
  • - x and y are integers different from 0, x + y varying from 4 to 8,
  • R, Ri and R3 are such as defined for formula (I), R and Ri being different from SO 3 " and NO 2 ,
  • - W represents an alkyl group comprising 1 to 5 carbon atoms, said alkyl group being substituted with a protonable element chosen among: a heterocycle such as
  • R 7 represents a primary, secondary or tertiary amine group, particularly a NH 2 group, or heterocycles, particularly such as_ N , or a -OR 8 group, wherein Rg represents H or an alkyl group comprising from 1 to 10 carbon atoms, or
  • the present invention also relates to a process of preparation of water-soluble compounds, characterized in that it comprises the following steps:
  • the process of the invention is a process wherein the reaction of sulfonation is carried out with the chlorosulfonic acid, and the reaction of nitration is carried out with the nitric acid.
  • the process of the invention is characterized in that it comprises the possible step of transformation of the functions N0 and S0 2 Y, in one of the following respective functions:
  • a catalytic hydrogenation is carried out with the NO 2 function in order to obtain a NH 2 function, which can then alkylated in order to obtain a primary, secondary or tertiary amine group, or an ammonium group.
  • the function NO 2 is treated with an acyl chloride or a sulfonyl chloride, in order to obtain a sulfonamide function, or is treated with a thioacid chloride in order to obtain a thioamide function.
  • the transformation of the SO 2 Y group into a sulfonamide function is carried out by the reaction with an amine; the transformation of the SO 2 Y group into a sulfothioester function is carried out by the reaction with a thiol and the transformation of the SO 2 Y group into a sulfonic ester function is carried out by the reaction with an alcohol.
  • the process of the invention is characterized in that it comprises the following steps:
  • the process of the invention is characterized in that R and K ⁇ represent tBu groups.
  • the present invention also relates to compounds having one of the following i formulas:
  • R and R3 are such as defined above for formula (I), R being different from NO 2 and SO 3 " ,
  • - x and y are integers different from 0, x + y varying from 4 to 8,
  • - W represents an alkyl group comprising 1 to 5 carbon atoms, said alkyl group being substituted with a protonable element chosen among:
  • R represents a primary, secondary or tertiary amine group, particularly a NH 2 group, or heterocycles, particularly such as_ N r , or a -OR 8 group, wherein R 8 represents H or an alkyl group com vprising from 1 to 10 carbon atoms, or * a -OR 8 or -SR 8 group, wherein R 8 is such as defined above, - Y represents OH, or an alkoxy group, or a primary or secondary amine group, or a halogen atom or a thioalkyl group.
  • the present invention also relates to compounds having one of the following formulas:
  • the compounds of the invention are characterized in that R 3 represents a methyl group.
  • the present invention also relates to the process of preparation of compound of formula (IV) corresponding to the reaction of the compound of formula (12) such as defined above with formaldehyde.
  • the present invention also relates to the process of preparation of compound of formula (V) corresponding to the reaction of the compound of formula (12) such as defined above with tris(2-carboxaldehyde)triphenylphosphine of formula ⁇ , followed by the reaction with NaBH 4 .
  • the present invention also relates to the process of preparation of compound of formula (VI) to (X) corresponding to the reaction of the compound of formula (12) such as defined above with an appropriate tris-aldehyde, followed by the reaction with NaBH DESCRIPTION OF THE FIGURES
  • Figure 3-a 1H NMR spectrum of compound 7-a in CDC1 3 at 298K.
  • Figure 3-b 1H NMR spectrum of compound 8-a in CDC1 3 at 298K. +: residual water or solvent peaks (CHC1 3 and CH 3 CN; this latter was present in elemental analysis characterization of compound 8-a).
  • Figure 4-a 1H NMR spectrum of compound 10-a in CDC1 3 at 298K.
  • Figure 4-b 1H NMR spectrum of complex 10-a/MeNH 3 + Cl " in CDCI 3 at 298K. Solvent, water and reference are labelled S, W and R, respectively.
  • the required tris-tosyl calix[6]arene was prepared from the known X 6 H 3 M ⁇ 3 3-a (Scheme 2)(Janssen, R. G. et al. Synthesis (1993) 380-385)[obtained by selective 1,3,5- trimethylation of -ffiu-calix[6]arene (X 6 H 6 )(Gutsche, C. D. et al. Org. Syn. (1990) 68, 238-242] in an efficient three step sequence (54 % overall yield).
  • 8-a has a more straight and regular cone conformation. As in the case of compound 5-a, these features might well be due to the establishment of hydrogen bonds between the anisole units and their neighboring phenoxy protic substituents, namely the tren-NH groups in the case of 8-a. Indeed, addition of CD 3 OD induced a split of the tBu resonances attesting to a conformational change. Finally, a variable temperature 1H
  • the present invention describes the synthesis of the first C 3V - symmetrical calix[6](aza)crown 8-a.
  • a 1H NMR study has shown that the alternate 1,3,5-azabridge at the small rim rigidifies the whole edifice preventing ring inversion and constraining the calixarene core in a straight cone conformation.
  • THF and ether were distilled over sodium/benzophenone under argon. Pyridine was distilled over KOH under argon. (Chloroform was distilled over P 2 O 5 under argon. DMF was distilled over MgSO 4 and stored over 4 A° molecular sieves under argon. TsCl was recristallized (dichloromethane/pentane) before use. 1H and 13 C NMR spectra were recorded respectively at 200 and 50 MHz. Thin-layer chromatographies (TLC) were performed with aluminum plates (0.20 mm) precoated with fluorescent silica gel. Reaction components were then visualized under UV light and dipped in a Dragendorff solution.
  • TLC Thin-layer chromatographies
  • This compound is prepared from compound 8-a (Calixtren).
  • butyraldehyde (0.020 mL, 0.099 mmol) was added to a solution of calixtren (8-a)(20.5 mg, 0.017 mmol) in 1 mL of anhydrous dichloromethane. After lh at room temperature, the reaction mixture was cooled at 0°C and NaBH(OAc) 3 (54 mg, 0.255 mmol) was added. After 15 h at room temperature, 5 mL of dichloromethane and then 5 mL of a saturated aqueous solution of NaHCO 3 were added. The reaction mixture was stirred 15 min and the aqueous layer was extracted twice with 10 mL of dichloromethane.
  • These new compounds can be used as ligands to coordinate a metal ion. They also have host- guest properties (neutral or charged molecules recognition).
  • the goal of the invention is to design new receptors based on a calix[6]arene core larger enough for the inclusion of small molecules and possessing a cage structure through rigidification by an aza-crown cap. It was observed that the tripodal aza-crown cap prevents ring inversion, constraining the calixarene core in a straight cone conformation ideal for host-guest chemistry.
  • the new compounds of the invention C 3v -symmetrical calix[6](aza)crown are useful for the complexation of ammoniums through cation- ⁇ interactions. Host behavior of receptor 10-a toward ammoniums. !
  • the upfield shifts measured for the proton resonances of the included ammoniums can indicate its spatial position in the aromatic cavity.
  • the protons at the ⁇ -and ⁇ - position of the nitrogen atom display the higher shift values suggesting that they sit in the centre of the cavity.
  • the complex 13 is in equilibrium with its acid form 14 and the equilibrium can be moved according to the p ⁇ .
  • an acid s ⁇ ch as tiifluoroacetic acid (TFA) moves the equilibrium towards species 14 and the subsequent addition of a base such as triethylamine (TEA) moves again the equilibrium towards the initial form 13.
  • TFA triethylamine
  • the complexes 13 and 16 are particularly interesting as they can be used in catalysis. Thus, these complexes are very good biomimetic models for enzymes such as peptidases or esterases. These complexes can be used for the catalysis of hydrolysis reactions or of enantioselective transfer of hydrides.
  • the ligand 10-a can complex ammoniums derived from amine I such as MeNH 3 + , PrNH 3 + , BuNH 3 + , but also derived from amine II such as Me 2 NH 2 + , but also derived from amine III such as Mes H " or bis-ammoniums such as H B ⁇ CHJC ⁇ NH S ⁇
  • amine I such as MeNH 3 + , PrNH 3 + , BuNH 3 +
  • amine II such as Me 2 NH 2 +
  • amine III such as Mes H " or bis-ammoniums
  • H B ⁇ CHJC ⁇ NH S ⁇ bis-ammoniums
  • the nitrogen atomes of the cap of the ligands of tire invention can readily protonated or alkylated (by Mel) to obtain the corresponding ammoniums. These polyammoniums are very good candidates for the anion complexation.
  • calix[6]arenes functionalized in alternate position by methoxy groups (as in J) and primary amines (J-2), tertiary amines (J-3), amides (J-4 and J-5), acids (3-6), esters (J-7), alcohols (J-8) or alkyl groups of similar bulkiness (J-9). All these compounds were submitted to the exact same experimental procedure as that described for the selective nitration of J (Scheme 6, Table 1). The results are collected in Table 1.
  • R ⁇ groups plays a key role in . directing the nitration positions.
  • a possible explanation might well be related to the presence of a protonable site in ⁇ -position of the phenolic oxygen atom.
  • compounds J and J-l to J-3 due to their basic character, all nitrogeneous arms must be protonated under the strongly acidic reaction conditions. This protonated nitrogen group is in an ideal position for hydrogen-bonding to the phenolic oxygen atom, thereby deactivating the whole aromatic cycle towards electrophilic attack by removing electron density.
  • a protonable oxygen atom is situated in ⁇ -position.
  • J-4 (COCl) 2 (1 mL, 11.45 mmols, 27.2 eq.). was added to a solution of J-6 (500 mg, 0.42 mmol) in anhydrous CH 2 C1 2 (40 mL) under argon. After 4 h at reflux, the mixture was evaporated under vacuum to dryness.
  • Boc deprotection TFA (0.1 mL) was added to a solution of Boc-J-2 (N02)3 (30 mg) in CHCI 3 (0.9 mL). After 1 h at room temperature, NaOH (1 M, 1 mL) was added and the mixture was extracted with CH 2 C1 2 (2 5 mL). The organic layer was dried
  • J-4 (N02)3 from J-4 (55 mg, 0.041 mmol); the crude product was purified by chromatography on silica gel using MeOH/CH 2 Cl 2 /conc. aq. NH 3 (5:95:0.25) as eluant to yield J-4 (N02)3 as a pale-yellow solid (30 mg, 56%).
  • the sililated products were suspended in a 9/1 TF A/water mixture and stirred a room temperature overnight. The solvents were then evaporated and toluene was added and evaporated twice, giving a brownish oil. The products were then neutralized and purified.
  • the present inventors have also synthesized a compound J-ll having the formula of compound J wherein W is a -CH 2 CH 2 CH 2 NMe 2 group.
  • THF was distilled over sodium/benzophenone under argon.
  • CH 2 C1 was distilled over CaH 2 under argon.
  • Ethanol was distilled over sodium/diethylphtalate under argon. All reactions were performed under an inert atmosphere.
  • Silica gel (230- 400 mesh) was used for flash chromatography separations.
  • Calixtrisimine 3 Calixtriamine 1 (230 mg, 0.201 mmol) was dissolved in CH 2 C1 2 (400 mL). To this solution was added a solution of tris(2- carboxaldehyde)triphenylphosphine (70 mg, 0.202 mmol) in CH 2 C1 2 (100 mL). The resulting yellow solution was stirred overnight at room temperature. The solvent was removed under reduced pressure. The residue was dissolved , ! in ethanol (500 mL) and refluxed for 2 h. The solvent was condensed to about 5 mL. The resulting white precipitate was collected by centrifugation and washed twice with ethanol (3 mL x 2). After drying on vacuum pump, 262 mg (0.182 mmol) of the desired product 3 was obtained as a white powder in 91 % yield.

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Abstract

La présente invention porte sur de nouveaux composés calix arènes de formule (1), et sur leur procédé de préparation, ainsi que sur des complexes entre un composé de formule (1) et un élément choisi parmi un métal, un actinide, un radioélément, un hôte cationique ou un hôte anionique. La présente invention porte également sur une composition pharmaceutique comprenant un composé de formule (I) en association avec un excipient acceptable d'un point de vue pharmaceutique. La présente invention porte également sur un procédé de préparation de composés solubles dans l'eau, ce procédé comprenant une réaction de nitration ou sulfonation, et éventuellement une réaction de sulfonation ou nitration, en particulier des composés de formule (1), et sur les composés ainsi obtenus.
PCT/EP2004/003140 2003-03-24 2004-03-24 Nouveaux composes calix arenes, leur procede de preparation et leur utilisation, en particulier comme mimes de sites enzymatiques Ceased WO2004085442A2 (fr)

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EPPCT/EP03/03045 2003-03-24

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Cited By (5)

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FR2939666A1 (fr) * 2008-12-17 2010-06-18 Inst Radioprot Et De Surete Nu Formulations cosmetiques et pharmaceutiques de molecules de calix[6]arenes
CN104017417A (zh) * 2014-06-19 2014-09-03 安徽师范大学 一种粉末涂料用流平剂及其制备方法、一种粉末涂料
CN109627437A (zh) * 2018-12-26 2019-04-16 上海应用技术大学 三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用
CN110982086A (zh) * 2019-12-18 2020-04-10 西北师范大学 一种主客体组装的超分子聚合物及其制备和识别汞离子的应用
CN111116933A (zh) * 2020-01-03 2020-05-08 西北师范大学 一种超分子聚合物及其在汞离子检测中的应用

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US8557020B2 (en) * 2010-04-13 2013-10-15 Dowa Holdings Co., Ltd. Compound, metal extractant, and application of the same
CN109608636B (zh) * 2018-12-13 2021-05-11 上海应用技术大学 富含杂原子的三嗪基杯[4]芳烃聚合物、制备方法及其应用

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IE68312B1 (en) * 1989-12-13 1996-06-12 Loctite Ireland Ltd Calixarene and oxacalixarene derivatives and use thereof for sequestration of metals
AU1545395A (en) * 1994-01-24 1995-08-08 Stephen J. Harris Calixarene-based compounds having antibacterial, antifungal, anticancer-hiv activity

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2939666A1 (fr) * 2008-12-17 2010-06-18 Inst Radioprot Et De Surete Nu Formulations cosmetiques et pharmaceutiques de molecules de calix[6]arenes
WO2010070049A1 (fr) * 2008-12-17 2010-06-24 Institut De Radioprotection Et De Surete Nucleaire Formulations cosmetiques et pharmaceutiques de molecules de calixarenes
RU2493818C2 (ru) * 2008-12-17 2013-09-27 Энститю Де Радиопротексион Э Де Сюрте Нюклеер Косметические и фармацевтические композиции молекул каликсарена
US8987334B2 (en) 2008-12-17 2015-03-24 Institut De Radioprotection Et De Surete Nucleaire Cosmetic and pharmaceutical formulations of calixarene molecules
CN104017417A (zh) * 2014-06-19 2014-09-03 安徽师范大学 一种粉末涂料用流平剂及其制备方法、一种粉末涂料
CN109627437A (zh) * 2018-12-26 2019-04-16 上海应用技术大学 三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用
CN109627437B (zh) * 2018-12-26 2021-05-11 上海应用技术大学 三嗪基杯[4]芳烃多孔聚合物、制备方法及其应用
CN110982086A (zh) * 2019-12-18 2020-04-10 西北师范大学 一种主客体组装的超分子聚合物及其制备和识别汞离子的应用
CN110982086B (zh) * 2019-12-18 2021-07-23 西北师范大学 一种主客体组装的超分子聚合物及其制备和识别汞离子的应用
CN111116933A (zh) * 2020-01-03 2020-05-08 西北师范大学 一种超分子聚合物及其在汞离子检测中的应用
CN111116933B (zh) * 2020-01-03 2021-09-24 西北师范大学 一种超分子聚合物及其在汞离子检测中的应用

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