In recent years, cancer has become the number two cause of death around the world, and scientists have exploited various treatment maps. Calixarenes, with diversified features, have been widely applied into drug deliv...In recent years, cancer has become the number two cause of death around the world, and scientists have exploited various treatment maps. Calixarenes, with diversified features, have been widely applied into drug delivery systems, which can respond to multi-stimuli and exhibit excellent performance. In this mini-review, we summarize the recent advances on controlled drug delivery systems based on calixarenes, in the form of inclusion complexes, amphiphilic self-assembly nanocarriers including micelles, hydrogels, vesicles and liposomes, and supramolecular nanovalves on mesoporous silica nanomaterials.展开更多
The equilibrium molecular geometry of 25, 26, 27. 28-tetrahydroxycalix[4]arene in cone cowtrmation was calculated by a CNDO/2 method based on the standard geometrical models. The results are in good agreement with tho...The equilibrium molecular geometry of 25, 26, 27. 28-tetrahydroxycalix[4]arene in cone cowtrmation was calculated by a CNDO/2 method based on the standard geometrical models. The results are in good agreement with those obtained from X-ray analysis.展开更多
A kind of photosensitive ultra-thin film was fabricated from diazoresin (DR) and various calixarenes by using theself-assembly technique. Under UV irradiation both the ionic- and hydrogen bonds between the layers of t...A kind of photosensitive ultra-thin film was fabricated from diazoresin (DR) and various calixarenes by using theself-assembly technique. Under UV irradiation both the ionic- and hydrogen bonds between the layers of the film will convert into covalent bonds. As a result, the stability of the film toward polar solvents increases dramatically.展开更多
A series of extractants （tert-butylcalix[6]arene, tert-butylcalix[8]arene and octeacetate of tert-butylcalix[8]arene） were synthesized, and their structures were identified by IR and JH-NMR. The distribution behavio...A series of extractants （tert-butylcalix[6]arene, tert-butylcalix[8]arene and octeacetate of tert-butylcalix[8]arene） were synthesized, and their structures were identified by IR and JH-NMR. The distribution behavior of ester catechins monomer in the aqueous and chloroform two-phase system containing one of calixarene was studied. The influences of different extractants, concentration of tert-butylcalix[8]arene and extraction temperature on the partition coefficients and the separation factors were investigated. The experiment results show that tert-butylcalix[8]arene is the best extractant that forms a more stable supramolecular compound with gallocatechin gallate （GCG） than with epigallocathechin gallate （EGCG） or epicatechin gallate （ECG）. When the concentration ofp-tert-butylcalix[8]arene is 3.79 mmol/L, the extraction temperature is 4 ℃, the partition coefficients ofKGCG, KECG, KEGCG are 0.987, 0.629, 0.449, the separation factors of al and a2 are 1.450 and 1.596, respectively. The important factors influencing the extraction properties of calixarene are discovered to be its cavity size and hydrogen bonding.展开更多
A new bridging reagent,N,N′-bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p-tert-buty lcalix\arene,p-tert-buty lcalix\arene and butylcalix\arene.It was found that...A new bridging reagent,N,N′-bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p-tert-buty lcalix\arene,p-tert-buty lcalix\arene and butylcalix\arene.It was found that the bridging reaction is selectively,at least,preferably at 1,3-position for p-tert-butylcalix\arene and p-tert-b utylcalix\arene,1,5-position for p-tert-butylcalix\arene.Taking the yield of bridged calixarene as a comparsion standard,the activity decreases with the increasing of the number of phenolic units in calixarene.展开更多
Excipients are important components of pharmaceutical preparations that affect their quality, safety, and efficacy. Macrocyclic receptors are a family of supramolecular excipients with several advantages, including mo...Excipients are important components of pharmaceutical preparations that affect their quality, safety, and efficacy. Macrocyclic receptors are a family of supramolecular excipients with several advantages, including molecular-level protection, small sizes,fast kinetics of host-vip recognition, and modular construction. With the continuous advances in the medical field, personalized and precision medicine requires the development of excipients with low dosages, integrated modifying effects, universality,and controlled release. To meet these requirements, we have developed a new family of macrocyclic excipients based on calixarenes by integrating their covalent(broad chemical design space) and noncovalent(wide range of substrates) advantages.Accordingly, azocalixarenes(Azo CAs) were designed, showing high binding affinities to a broad spectrum of active pharmaceutical ingredients(APIs), selectivity to interferents, and responsiveness to hypoxic microenvironments. Due to their highly efficient and controllable recognition, Azo CAs serve as low-dose excipients for 30 APIs. Molecular encapsulation by Azo CAs results in the integrated modification of the physicochemical properties of APIs, including solubility, stability, bioavailability,and biocompatibility. Moreover, Azo CAs can be reduced by azoreductases overexpressed in hypoxic microenvironments,leading to the controlled release of APIs. Collectively, Azo CA excipients have broad application prospects for a series of diseases such as enteritis, arthritis, stroke, cancer, bacterial infection and kidney injury, with diverse therapeutic modalities,including chemotherapy, photodynamic therapy, photothermal therapy, immunotherapy, boron neutron capture therapy, radiotherapy, fluorescence imaging, and their combinations.展开更多
Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation,fast response,high spatial resolution,and so on,for which the luminescent thermometers are the key.Here,a...Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation,fast response,high spatial resolution,and so on,for which the luminescent thermometers are the key.Here,a 1D complex[Tb_(4)(HTC4A)(TC4A)(OBBA)_(2)(CH_(3)OH)_(4)(μ4-OH)]n(1)was obtained by solvothermal synthesis,where H 4TC4A=p-tert-butylthiacalix[4]arene,and H_(2)OBBA=4,4'-oxybisbenzoic acid.This complex is featured with a chain-like polymer constructed by bridging some sandwich-like Tb_(4)-(TC4A)_(2)entities through OBBA2-ligands.It exhibited the characteristic emission of the Tb^(3+)ion.Both fluorescence intensity and lifetime decreased with increasing temperature.The relative sensitivity was up to 8.743%·K^(-1)at 473 K,indicating it is a good ratiometric luminescent thermometer.This complex had good stability under different pH values and in common solvents.CCDC:2392643.展开更多
Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific rele...Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific release and biological distribution.Herein,sulfonated azocalix[4]arene(SAC4A)with enhanced water solubility,recognition capacity,and designed responsiveness was used to improve the efficiency of icariin for OA therapy.SAC4A,a macrocycle with well-defined molecular weight and structure,could encapsulate and enhance water solubility of various drugs.In addition,SAC4A enables hypoxia-responsive release of loaded drug.Compared with icariin treatment,supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats,including more regular bone morphology and structure,and lower degree of cartilage damage.Moreover,the supramolecular formulation demonstrated various advantages,including easy preparation,hypoxia-triggered release,and small size that conducive to drug penetration.展开更多
Compared with organic solar cells(OSCs) adopting conventional architecture,inverted OSCs have offered generally better stability,where Zn O is the most widely used electron transporting layer(ETL) material.For ZnO-bas...Compared with organic solar cells(OSCs) adopting conventional architecture,inverted OSCs have offered generally better stability,where Zn O is the most widely used electron transporting layer(ETL) material.For ZnO-based inverted OSCs,a welltuned interface of organic(active layer)-inorganic(Zn O film) with matched surface energy(γS) is critical for both high performance and high stability.In this work,two typical calixarenes,C4A and Bu C4A,were employed as the tuning agents to adjust this organic-inorganic interface for ZnO-based inverted OSCs.As a result,with PM6:L8-BO as the active layer,significantly promoted power conversion efficiencies(PCEs) from 17.14%(for ZnO) to 18.25%(for ZnO/C4A) and 17.80%(for ZnO/Bu C4A) were achieved.Photodynamic studies indicate that the enhanced performance is due to the faster charge extraction process,the suppressed recombination and more ideal internal electric field in ZnO/calixarene-based devices.In addition,wellmatched interface energy and more ordered molecular aggregation in active layer effectively improved photostability and thermal stability for ZnO/calixarene-based devices.These results indicate that calixarenes could act as effective modifying agents of ZnO to improve inverted OSCs’ performance and stability simultaneously,and likely also stimulate calixarenes’ and other macromolecules’ broader studies in other organic electronic devices.展开更多
The extraction of copper with calixarenes was researched by comparing the results from calix[4]-, calix[6]- and calix[8]-arenes. The extraction ability increased as the order: calix [4]? calix[8]? calix[6]-arenes, wit...The extraction of copper with calixarenes was researched by comparing the results from calix[4]-, calix[6]- and calix[8]-arenes. The extraction ability increased as the order: calix [4]? calix[8]? calix[6]-arenes, with the binding ratio being 1:1. The extraction mechanism was also discussed, and its equation Cu(NH3)42+ +H2L(0)→KexCu(NH3)4L(0) +2H+ and the extraction equilbrium constants (Kex) for calix[6]- and calix[8]-arenes were obtained respectively.展开更多
Several new calixcrowns were synthesized and characterized. The transport of Ca 2+ ion was investigated through a bubbling pseudo emulsion liquid membrane with these calixcrowns, the parent calixarenes ( n ...Several new calixcrowns were synthesized and characterized. The transport of Ca 2+ ion was investigated through a bubbling pseudo emulsion liquid membrane with these calixcrowns, the parent calixarenes ( n =4, 6, 8) and the ester, acid derivatives of calixarene as mobile carriers. The effects of the initial concentrations of Ca 2+ ion in the source phase and the initial pH difference (ΔpH) between the receiving phase and the source phase were studied. The results suggest that there are two different transport mechanisms. The transports using calixarenes and their ester, acid derivatives as carriers represent a proton coupled co transport with a flow of protons in the opposite direction, while the transports using the calixcrowns as carriers exhibit the characteristics of an anion coupled co transport with a flow of anion in the same direction.展开更多
Macrocycle-induced formation of pure organic supramolecular aggregates is a challenge that has attracted considerable attention from researchers in the fields of chemistry,biology,and materials science.In particular,a...Macrocycle-induced formation of pure organic supramolecular aggregates is a challenge that has attracted considerable attention from researchers in the fields of chemistry,biology,and materials science.In particular,aggregation induced by water-soluble cyclodextrins and calixarenes,which are two classic of macrocycles with a hydrophobic cavity and a hydrophilic external surface,has attracted interest because these host molecules can form aggregates with vip molecules via various noncovalent interactions,including hydrophobic interactions,van der Waals forces,hydrogen bonds,and electrostatic interactions.In this review,we focus mainly on some impressive recent progress,both by our group and other groups,on the construction of cyclodextrin-and calixarene-based organic supramolecular aggregates,control of their topological morphology,and their use for biological applications such as molecular recognition and bioimaging,photodynamic therapy,light-harvesting energy transfer,and targeted drug delivery.We also discuss shortcomings of the current reported results and future prospects for the development of multifunctional organic supramolecular aggregates for use in various fields.展开更多
Study of host-vip interaction with the aid of proper model system is helpful to the understanding of complicated chemical reactions in biological processes on the molecular level. Cyclodextrins and crown ethers are ...Study of host-vip interaction with the aid of proper model system is helpful to the understanding of complicated chemical reactions in biological processes on the molecular level. Cyclodextrins and crown ethers are two kinds of the most extensively studied host molecules and enzyme mimics. The cyclodextrins are very hydrophilic on their out rims but lipophilic on the inner remainder; the crown ethers are highly lipophilic on the outside and hydrophilic on the inside. In recent years, calixarene has been found a new kind of host compounds, which can form host-vip inclusion complexes with many kinds of展开更多
A series of monobridged calixarenes 3a-f, cyclic biscalix arenes 4a-f, diametrically bridged at the upper rim with saturated aliphatic diester chains, have been synthesized. The results at dilute conditions show tha...A series of monobridged calixarenes 3a-f, cyclic biscalix arenes 4a-f, diametrically bridged at the upper rim with saturated aliphatic diester chains, have been synthesized. The results at dilute conditions show that the percentage of yields of mono , bis and oligo calixarenes are related to the length of the chains. With the shortening of the chains, the percentage of monocalixarenes decreased. All the calixarene moieties are in a cone conformation according to the AB quartet pattern of the methylene protons between the phenolic rings in the 1H NMR spectra.展开更多
Two functionalized calixarenes in cone conformation L 2-3 have been synthesized and their intramolecular inclusion complexes (1∶1) with organic neutral molecules CH 3CN and CH 3NO 2 have been prepared and c...Two functionalized calixarenes in cone conformation L 2-3 have been synthesized and their intramolecular inclusion complexes (1∶1) with organic neutral molecules CH 3CN and CH 3NO 2 have been prepared and characterized, respectively. The X-ray crystallographic analysis shows that L 2 in L 2·CH 3CN·C 2H 5OH has C 4 symmestry and L 3 in L 3·CH 3NO 2 exhibits C 2 symmestry. The CH-π aromatic interactions between the CH group of the vip and the phenyl rings of the calix backbond have been proved to be able to stabilize the intramolecular inclusion complexes formed. The interaction is directional, but it is independent of the acidity of the vip. To gain information on CH-π interactions, suitable geometrical parameters have been calculated from the crystal data of intramolecular inclusion complexes. The results show that L 3·CH 3NO 2 with L 3 in C 2 symmestry can also be bound stably in the intramolecular inclusion complex, being consistent with the thermal analysis. The geometrical parameters and the results of the thermal analysis of L 1·CH 3CN and L 1·CH 3NO 2 were also given and discussed.展开更多
Currently a technique widely used for gold extraction is mercury by amalgamation technique, the tailing produced pollutes water of all kinds, so it is necessary to develop a form of selective mitigation, for which it ...Currently a technique widely used for gold extraction is mercury by amalgamation technique, the tailing produced pollutes water of all kinds, so it is necessary to develop a form of selective mitigation, for which it is necessary to use complexing agents based on calixarene functionalized with mercury sequestering agents. These are immobilized by adding supports based on natural silica to form polymers and make them insoluble in all types of solvents, so that they can be used as an extractor and at the same time regenerate to their original properties for continuous reuse.展开更多
A novel fluorescent sensor was prepared from sulfonated calix[4]arene(SC4A)by the host-vip com-plexation method using the fluorescent dye rhodamine B(RB)as a structure-directing agent.The crystal structure of the ho...A novel fluorescent sensor was prepared from sulfonated calix[4]arene(SC4A)by the host-vip com-plexation method using the fluorescent dye rhodamine B(RB)as a structure-directing agent.The crystal structure of the host-vip complex(RB@(SC4A)_(3))was confirmed by X-ray diffraction studies while its performance and sensing mechanism for metal ion pollutants were characterized using fluorescence and nuclear magnetic resonance spectroscopies.The results showed that RB@(SC4A)_(3) had a triangular branch structure resulting from host-vip mediation of the interactions between the three SC4A host molecules and the three terminal groups of the vip molecule RB.The host-vip complex exhibited sensitive and selective sensing towards Fe^(3+)ions via a fluorescence quenching mechanism.The results indicated that RB@(SC4A)_(3) could be a promising sensitive and selective fluorescent sensor for metal ion pollutants mon-itoring.It also provided new insights into the synthesis of calixarene-based host-vip complex.展开更多
Two novel fluorescent calix[4]arene derivatives la and lb with benzoxazole or benzothiazole units in 1,3-alternate conformation have been synthesized and characterized by IR, ^1H NMR, ^13C NMR and MS. Their complexati...Two novel fluorescent calix[4]arene derivatives la and lb with benzoxazole or benzothiazole units in 1,3-alternate conformation have been synthesized and characterized by IR, ^1H NMR, ^13C NMR and MS. Their complexation properties to different heavy and transition metal ions have been studied by UV-vis spectroscopy and fluorescence spectrometer. Compounds 1a and 1b show selective recognition to Fe^3＋ and Cr^3＋.展开更多
基金the National Natural Science Foundation of China (Nos. 21272093 and 51473061)the Fundamental Research Funds for the Central Universities (No. JCKY-QKJC05) for financial support
文摘In recent years, cancer has become the number two cause of death around the world, and scientists have exploited various treatment maps. Calixarenes, with diversified features, have been widely applied into drug delivery systems, which can respond to multi-stimuli and exhibit excellent performance. In this mini-review, we summarize the recent advances on controlled drug delivery systems based on calixarenes, in the form of inclusion complexes, amphiphilic self-assembly nanocarriers including micelles, hydrogels, vesicles and liposomes, and supramolecular nanovalves on mesoporous silica nanomaterials.
文摘The equilibrium molecular geometry of 25, 26, 27. 28-tetrahydroxycalix[4]arene in cone cowtrmation was calculated by a CNDO/2 method based on the standard geometrical models. The results are in good agreement with those obtained from X-ray analysis.
基金This work was supported by the National Natural Science Foundation of China (No. 50173002 and 20274002).
文摘A kind of photosensitive ultra-thin film was fabricated from diazoresin (DR) and various calixarenes by using theself-assembly technique. Under UV irradiation both the ionic- and hydrogen bonds between the layers of the film will convert into covalent bonds. As a result, the stability of the film toward polar solvents increases dramatically.
基金Project (20576029) supported by the National Natural Science Foundation of China
文摘A series of extractants （tert-butylcalix[6]arene, tert-butylcalix[8]arene and octeacetate of tert-butylcalix[8]arene） were synthesized, and their structures were identified by IR and JH-NMR. The distribution behavior of ester catechins monomer in the aqueous and chloroform two-phase system containing one of calixarene was studied. The influences of different extractants, concentration of tert-butylcalix[8]arene and extraction temperature on the partition coefficients and the separation factors were investigated. The experiment results show that tert-butylcalix[8]arene is the best extractant that forms a more stable supramolecular compound with gallocatechin gallate （GCG） than with epigallocathechin gallate （EGCG） or epicatechin gallate （ECG）. When the concentration ofp-tert-butylcalix[8]arene is 3.79 mmol/L, the extraction temperature is 4 ℃, the partition coefficients ofKGCG, KECG, KEGCG are 0.987, 0.629, 0.449, the separation factors of al and a2 are 1.450 and 1.596, respectively. The important factors influencing the extraction properties of calixarene are discovered to be its cavity size and hydrogen bonding.
基金Supported by the National Natural Science Foundation of China(20272044)
文摘A new bridging reagent,N,N′-bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p-tert-buty lcalix\arene,p-tert-buty lcalix\arene and butylcalix\arene.It was found that the bridging reaction is selectively,at least,preferably at 1,3-position for p-tert-butylcalix\arene and p-tert-b utylcalix\arene,1,5-position for p-tert-butylcalix\arene.Taking the yield of bridged calixarene as a comparsion standard,the activity decreases with the increasing of the number of phenolic units in calixarene.
基金supported by the National Natural Science Foundation of China (U20A20259, 22201141)the Fundamental Research Funds for the Central Universities+1 种基金the NCC Fund(NCC2020FH04)the China Postdoctoral Science Foundation(2022M711697)。
文摘Excipients are important components of pharmaceutical preparations that affect their quality, safety, and efficacy. Macrocyclic receptors are a family of supramolecular excipients with several advantages, including molecular-level protection, small sizes,fast kinetics of host-vip recognition, and modular construction. With the continuous advances in the medical field, personalized and precision medicine requires the development of excipients with low dosages, integrated modifying effects, universality,and controlled release. To meet these requirements, we have developed a new family of macrocyclic excipients based on calixarenes by integrating their covalent(broad chemical design space) and noncovalent(wide range of substrates) advantages.Accordingly, azocalixarenes(Azo CAs) were designed, showing high binding affinities to a broad spectrum of active pharmaceutical ingredients(APIs), selectivity to interferents, and responsiveness to hypoxic microenvironments. Due to their highly efficient and controllable recognition, Azo CAs serve as low-dose excipients for 30 APIs. Molecular encapsulation by Azo CAs results in the integrated modification of the physicochemical properties of APIs, including solubility, stability, bioavailability,and biocompatibility. Moreover, Azo CAs can be reduced by azoreductases overexpressed in hypoxic microenvironments,leading to the controlled release of APIs. Collectively, Azo CA excipients have broad application prospects for a series of diseases such as enteritis, arthritis, stroke, cancer, bacterial infection and kidney injury, with diverse therapeutic modalities,including chemotherapy, photodynamic therapy, photothermal therapy, immunotherapy, boron neutron capture therapy, radiotherapy, fluorescence imaging, and their combinations.
文摘Luminescence thermometry has attracted more and more attention due to its non-contact and noninvasive operation,fast response,high spatial resolution,and so on,for which the luminescent thermometers are the key.Here,a 1D complex[Tb_(4)(HTC4A)(TC4A)(OBBA)_(2)(CH_(3)OH)_(4)(μ4-OH)]n(1)was obtained by solvothermal synthesis,where H 4TC4A=p-tert-butylthiacalix[4]arene,and H_(2)OBBA=4,4'-oxybisbenzoic acid.This complex is featured with a chain-like polymer constructed by bridging some sandwich-like Tb_(4)-(TC4A)_(2)entities through OBBA2-ligands.It exhibited the characteristic emission of the Tb^(3+)ion.Both fluorescence intensity and lifetime decreased with increasing temperature.The relative sensitivity was up to 8.743%·K^(-1)at 473 K,indicating it is a good ratiometric luminescent thermometer.This complex had good stability under different pH values and in common solvents.CCDC:2392643.
基金supported by grants from the National Natural Science Foundation of China(Nos.82374489,U20A20259 and 22201299)the Scientific Research Program of the Tianjin Municipal Education Commission(No.2021ZD013)。
文摘Osteoarthritis(OA)is the most prevalent joint disease and icariin is a promising drug for its treatment.However,the clinical use of icariin is hindered by poor water solubility,low bioavailability,and nonspecific release and biological distribution.Herein,sulfonated azocalix[4]arene(SAC4A)with enhanced water solubility,recognition capacity,and designed responsiveness was used to improve the efficiency of icariin for OA therapy.SAC4A,a macrocycle with well-defined molecular weight and structure,could encapsulate and enhance water solubility of various drugs.In addition,SAC4A enables hypoxia-responsive release of loaded drug.Compared with icariin treatment,supramolecular complex icariin@SAC4A significantly relieved OA symptoms of rats,including more regular bone morphology and structure,and lower degree of cartilage damage.Moreover,the supramolecular formulation demonstrated various advantages,including easy preparation,hypoxia-triggered release,and small size that conducive to drug penetration.
基金supported by the Ministry of Science and Technology of China(MoST,2019YFA0705900)the National Natural Science Foundation of China(21935007,52025033,51873089)+1 种基金Tianjin city(20JCZDJC00740)111 Project(B12015)。
文摘Compared with organic solar cells(OSCs) adopting conventional architecture,inverted OSCs have offered generally better stability,where Zn O is the most widely used electron transporting layer(ETL) material.For ZnO-based inverted OSCs,a welltuned interface of organic(active layer)-inorganic(Zn O film) with matched surface energy(γS) is critical for both high performance and high stability.In this work,two typical calixarenes,C4A and Bu C4A,were employed as the tuning agents to adjust this organic-inorganic interface for ZnO-based inverted OSCs.As a result,with PM6:L8-BO as the active layer,significantly promoted power conversion efficiencies(PCEs) from 17.14%(for ZnO) to 18.25%(for ZnO/C4A) and 17.80%(for ZnO/Bu C4A) were achieved.Photodynamic studies indicate that the enhanced performance is due to the faster charge extraction process,the suppressed recombination and more ideal internal electric field in ZnO/calixarene-based devices.In addition,wellmatched interface energy and more ordered molecular aggregation in active layer effectively improved photostability and thermal stability for ZnO/calixarene-based devices.These results indicate that calixarenes could act as effective modifying agents of ZnO to improve inverted OSCs’ performance and stability simultaneously,and likely also stimulate calixarenes’ and other macromolecules’ broader studies in other organic electronic devices.
基金Project (No. 29201004) supported by the National Natural Science Foundation of China
文摘The extraction of copper with calixarenes was researched by comparing the results from calix[4]-, calix[6]- and calix[8]-arenes. The extraction ability increased as the order: calix [4]? calix[8]? calix[6]-arenes, with the binding ratio being 1:1. The extraction mechanism was also discussed, and its equation Cu(NH3)42+ +H2L(0)→KexCu(NH3)4L(0) +2H+ and the extraction equilbrium constants (Kex) for calix[6]- and calix[8]-arenes were obtained respectively.
文摘Several new calixcrowns were synthesized and characterized. The transport of Ca 2+ ion was investigated through a bubbling pseudo emulsion liquid membrane with these calixcrowns, the parent calixarenes ( n =4, 6, 8) and the ester, acid derivatives of calixarene as mobile carriers. The effects of the initial concentrations of Ca 2+ ion in the source phase and the initial pH difference (ΔpH) between the receiving phase and the source phase were studied. The results suggest that there are two different transport mechanisms. The transports using calixarenes and their ester, acid derivatives as carriers represent a proton coupled co transport with a flow of protons in the opposite direction, while the transports using the calixcrowns as carriers exhibit the characteristics of an anion coupled co transport with a flow of anion in the same direction.
基金National Natural Science Foundation of China,Grant/Award Numbers:21807038,21772099,21861132001China Postdoctoral Science Foundation,Grant/Award Number:2019M651006。
文摘Macrocycle-induced formation of pure organic supramolecular aggregates is a challenge that has attracted considerable attention from researchers in the fields of chemistry,biology,and materials science.In particular,aggregation induced by water-soluble cyclodextrins and calixarenes,which are two classic of macrocycles with a hydrophobic cavity and a hydrophilic external surface,has attracted interest because these host molecules can form aggregates with vip molecules via various noncovalent interactions,including hydrophobic interactions,van der Waals forces,hydrogen bonds,and electrostatic interactions.In this review,we focus mainly on some impressive recent progress,both by our group and other groups,on the construction of cyclodextrin-and calixarene-based organic supramolecular aggregates,control of their topological morphology,and their use for biological applications such as molecular recognition and bioimaging,photodynamic therapy,light-harvesting energy transfer,and targeted drug delivery.We also discuss shortcomings of the current reported results and future prospects for the development of multifunctional organic supramolecular aggregates for use in various fields.
文摘Study of host-vip interaction with the aid of proper model system is helpful to the understanding of complicated chemical reactions in biological processes on the molecular level. Cyclodextrins and crown ethers are two kinds of the most extensively studied host molecules and enzyme mimics. The cyclodextrins are very hydrophilic on their out rims but lipophilic on the inner remainder; the crown ethers are highly lipophilic on the outside and hydrophilic on the inside. In recent years, calixarene has been found a new kind of host compounds, which can form host-vip inclusion complexes with many kinds of
文摘A series of monobridged calixarenes 3a-f, cyclic biscalix arenes 4a-f, diametrically bridged at the upper rim with saturated aliphatic diester chains, have been synthesized. The results at dilute conditions show that the percentage of yields of mono , bis and oligo calixarenes are related to the length of the chains. With the shortening of the chains, the percentage of monocalixarenes decreased. All the calixarene moieties are in a cone conformation according to the AB quartet pattern of the methylene protons between the phenolic rings in the 1H NMR spectra.
基金theNationalNaturalScienceFoundationofChina (No .2 9872 0 34 )andtheNaturalScienceFoundationofHenan ,China
文摘Two functionalized calixarenes in cone conformation L 2-3 have been synthesized and their intramolecular inclusion complexes (1∶1) with organic neutral molecules CH 3CN and CH 3NO 2 have been prepared and characterized, respectively. The X-ray crystallographic analysis shows that L 2 in L 2·CH 3CN·C 2H 5OH has C 4 symmestry and L 3 in L 3·CH 3NO 2 exhibits C 2 symmestry. The CH-π aromatic interactions between the CH group of the vip and the phenyl rings of the calix backbond have been proved to be able to stabilize the intramolecular inclusion complexes formed. The interaction is directional, but it is independent of the acidity of the vip. To gain information on CH-π interactions, suitable geometrical parameters have been calculated from the crystal data of intramolecular inclusion complexes. The results show that L 3·CH 3NO 2 with L 3 in C 2 symmestry can also be bound stably in the intramolecular inclusion complex, being consistent with the thermal analysis. The geometrical parameters and the results of the thermal analysis of L 1·CH 3CN and L 1·CH 3NO 2 were also given and discussed.
文摘Currently a technique widely used for gold extraction is mercury by amalgamation technique, the tailing produced pollutes water of all kinds, so it is necessary to develop a form of selective mitigation, for which it is necessary to use complexing agents based on calixarene functionalized with mercury sequestering agents. These are immobilized by adding supports based on natural silica to form polymers and make them insoluble in all types of solvents, so that they can be used as an extractor and at the same time regenerate to their original properties for continuous reuse.
基金the National Natural Science Foundation of China (NSFC, No. 21861011)the Innovation Program for High-level Talents of Guizhou Province (No. 2016–5657) are gratefully acknowledged for financial support
文摘A novel fluorescent sensor was prepared from sulfonated calix[4]arene(SC4A)by the host-vip com-plexation method using the fluorescent dye rhodamine B(RB)as a structure-directing agent.The crystal structure of the host-vip complex(RB@(SC4A)_(3))was confirmed by X-ray diffraction studies while its performance and sensing mechanism for metal ion pollutants were characterized using fluorescence and nuclear magnetic resonance spectroscopies.The results showed that RB@(SC4A)_(3) had a triangular branch structure resulting from host-vip mediation of the interactions between the three SC4A host molecules and the three terminal groups of the vip molecule RB.The host-vip complex exhibited sensitive and selective sensing towards Fe^(3+)ions via a fluorescence quenching mechanism.The results indicated that RB@(SC4A)_(3) could be a promising sensitive and selective fluorescent sensor for metal ion pollutants mon-itoring.It also provided new insights into the synthesis of calixarene-based host-vip complex.
基金Natural Science Foundation of Tianjin(No.07JCZDJC00300)Tianjin International Coorperation Program of Science and Technology(No.08ZCGHHZ00400)
文摘Two novel fluorescent calix[4]arene derivatives la and lb with benzoxazole or benzothiazole units in 1,3-alternate conformation have been synthesized and characterized by IR, ^1H NMR, ^13C NMR and MS. Their complexation properties to different heavy and transition metal ions have been studied by UV-vis spectroscopy and fluorescence spectrometer. Compounds 1a and 1b show selective recognition to Fe^3＋ and Cr^3＋.
