P450 enzymes-catalyzed aromatic hydroxylation plays an important role in detoxification,biosynthesis,and potential carcinogenic effect of aromatic compounds.Though it has been explored for decades,the actual process o...P450 enzymes-catalyzed aromatic hydroxylation plays an important role in detoxification,biosynthesis,and potential carcinogenic effect of aromatic compounds.Though it has been explored for decades,the actual process of aromatic hydroxylation and mechanism of regioselectivity catalyzed by cytochrome P450 monooxygenases remained ambiguous.Here,we have resolved these issues.With a stable chiral organofluorine probe,and especially with X-ray data of two isolated arene oxides derivatives,we demonstrate that an arene oxide pathway is definitely involved in P450-catalyzed aromatic hydroxylation.By the capture,isolation,identification and reactivity exploration of the arene 1,2-oxide and arene 2,3-oxide intermediates,together with advanced QM calculations,the mechanism of how two intermediates go to the same product has been elucidated.In addition to the model substrate,we also confirmed that an arene oxide intermediate is involved in the P450-catalyzed hydroxylation pathway of a natural product derivative methyl cinnamate,which indicates that this intermediate appears to be universal in P450-catalyzed aromatic hydroxylation.Our work not only provides the most direct evidence for the arene oxide pathway and new insights into the regioselectivity involved in P450-catalyzed aromatic hydroxylation,but also supplies a new synthetic approach to achieve the dearomatization of aromatic compounds.展开更多
In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due t...In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due to the rich host-vip recognition in their rigid electron-rich cavities.However,most reported pillararenes are functionalized by alkoxy modification,which results in poor charge transfer nature and weak fluorescence response.A π-conjugated charge-transfer system P5BN was obtained by introducing electron-donating triarylamine(Ar_(3)N)and electron-deficient triarylborane(Ar_(3)B)into pillar[5]arene skeleton,which significantly improved its luminescence behavior and was further used for fluorescence detection applications.The molecular structure showed that P5BN provided a good macrocyclic cavity to encapsulate amino acids molecules of suitable size.It was found that P5BN,as a fluorescent sensor,showed a highly sensitive and selective response to L-arginine(L-Arg),resulting in a significant enhancement of the fluorescence at 408 nm of P5BN with the lowest detection concentration being 2.21×10^(-8) mol/L.The recognition mechanism was demonstrated through experiments and DFT theoretical calculations.展开更多
Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin de...Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin depolymerization.Herein,we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%.Particularly,high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin.The process begins with the reductive depolymerization of formaldehyde-stabilized lignin,followed by transmethylation between lignin monomers over Au/Nb_(2)O_(5) catalyst,and the Ru/Nb2O5-catalyzed hydrodeoxygenation.This work demonstrates the potential of value-added arenes production directly from lignin.展开更多
Intracellular protein delivery is vital for the development of therapeutic proteins that act on intracellular targets.Although numerous carriers based on polymers and nanomaterials have been reported to facilitate cel...Intracellular protein delivery is vital for the development of therapeutic proteins that act on intracellular targets.Although numerous carriers based on polymers and nanomaterials have been reported to facilitate cellular internalization of membrane impermeable proteins,it is still a great challenge to intracellularly deliver proteins with different sizes and isoelectric points through small molecule-based protein carrier.Herein,amidinium functionalized pillar[5]arene(AP5)was used as a small molecular carrier to facilitate intracellular delivery of proteins with different sizes and isoelectric points.The densely preorganized amidinium groups on pillar[5]arene skeleton could not only glue proteins together to form AP5@protein complex through multiple salt-bridges,but also promote cellular internalization AP5@protein complex.The bioactivities of the internalized proteins were well-maintained.This study provides a novel,versatile and macrocyclic-molecule based intracellular protein delivery carrier through the preorganization of amidiniums on pillar[5]arene.展开更多
Herein we report an environmentally friendly and energy-efficient method for the adsorptive separation of toluene from toluene-alcohol azeotropes using porous crystalline fluorinated leaning pillar[6]arene(FLP6α),ach...Herein we report an environmentally friendly and energy-efficient method for the adsorptive separation of toluene from toluene-alcohol azeotropes using porous crystalline fluorinated leaning pillar[6]arene(FLP6α),achieving up to 100%purity.Moreover,FLP6αdemonstrates rapid adsorption and excellent recyclability.展开更多
Chiral anticancer drugs are the subject of ongoing research due to their optical characterization and pharmacological effects.Achieving a single enantiomer of a chiral anticancer drug is arduous,but it can significant...Chiral anticancer drugs are the subject of ongoing research due to their optical characterization and pharmacological effects.Achieving a single enantiomer of a chiral anticancer drug is arduous,but it can significantly improve its pharmacokinetics for tumor therapy.Here,the chiral nanocatchers,known as Dbiotin-P5■MCC NCs,were designed and prepared based on host-vip self-assembly between D-biotin anchored pillar[5]arene(D-biotin-P5)and myristoyl chloride choline(MCC).D-Biotin-P5■MCC NCs featuring the chiral separation and enzyme-induced disassemble were evaluated for their ability to selectively capture and subsequently target the release of(R,R)-OXA enantiomers into tumor cells.Furthermore,the use of D-biotin-P5■MCC NCs has demonstrated a significant enhancement in the intracellular uptake of OXA,with the drug being efficiently released to MCF-7 breast cancer cells.This has led to a superior inhibitory effect on MCF-7 cells when compared to free OXA,while also reducing the cytotoxicity of the drug in HEK 293 human embryonic kidney cells.This research not only paves a promising way for the fabrication of chiral supramolecular nanocarriers but also holds the potential to improve the processes of chiral drug separation and targeted therapy.展开更多
Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequenc...Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequency of the carbon-deuterium(C-D)bond,leading to lower ground state energy and higher bond dis-sociation energy compared to the carbon-hydrogen(C–H)bond.展开更多
Sulfur dioxide(SO_(2)),being one of the therapeutic gaseous molecules,has been widely utilized in cancer therapy because of its high therapeutic efficacy and biosafety.Nevertheless,the in situ-triggered and efficient ...Sulfur dioxide(SO_(2)),being one of the therapeutic gaseous molecules,has been widely utilized in cancer therapy because of its high therapeutic efficacy and biosafety.Nevertheless,the in situ-triggered and efficient transportation of SO_(2)to tumors are the main obstacles that restrict its clinical application.To overcome this impediment,we functionalized pillar[5]arene with 2,4-dinitrobenzene sulfonic acid(DNSB)and then self-assembled it with tetraphenyl-PEG(TPE-PEG)in aqueous media to form fluorescent nanoparticles(PSTPE NPs).Meanwhile,the target vip(NH_(2)-PEG-FA)was encapsulated within the spacious cavity of pillar[5]arene via host-vip interaction.The resulting nanoparticles possess distinctive characteristics:(Ⅰ)dual GSH recognition motifs for enhanced SO_(2)release kinetics;(Ⅱ)incorporation of targeting ligands for selective cytotoxicity towards tumor cells while sparing normal tissues and cells;and(Ⅲ)surface modification of pillar[5]arene with TPE-PEG conferring excellent dispersibility,biocompatibility,and fluorescence properties in aqueous environments.Collectively,this novel nanoparticle represents an innovative approach that utilizes macrocyclics as SO_(2)gas donors to induce cellular apoptosis and provides new insights into gas-based therapy.展开更多
Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of lum...Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.展开更多
Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes.The method of metal co...Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes.The method of metal coordination has emerged as a robust methodology for chirality induction in many systems.In this work,we engineered two rigid and flexible chiral organic ligands(L_(1) and L_(2))by synergizing the inherent planar chirality of pillar[5]arenes with tailored metal-coordination moieties.They demonstrate versatile coordination capabilities toward both 3d-and 4f-block metals,enabling modulation of luminescent characteristics with blue,green and red emissions.Four planar chiral complexes exhibiting CPL activity were synthesized through systematic coordination of L_(1)/L_(2) with Zn^(2+),Eu^(3+),and Tb^(3+).The coordination processes effectively rigidify molecular conformations,leading to an enhanced CPL performance.Particularly,the Tb-L_(2) complex displays superior lanthanide-centered emission with a fluorescence quantum yield of~55%and an emission dissymmetry factor glum=5.5×10^(-3).By engineering the substitution on pillar[5]arene scaffolds,we have established a metal-coordination platform with CPL characteristics,which paves the way in the design of new metal-based luminescent materials.展开更多
The separation of alicyclic ketones and alicyclic alcohols is one of the challenges in the field of petrochemical industry. However, traditional separation methods suffer from excessive energy consumption,complicated ...The separation of alicyclic ketones and alicyclic alcohols is one of the challenges in the field of petrochemical industry. However, traditional separation methods suffer from excessive energy consumption,complicated operation, and unsatisfactory separation efficiency for substances with similar boiling points.Herein, we offer an innovative method for the separation of alicyclic ketones and alicyclic alcohols employing nonporous adaptive crystals(NACs) of perethylated pillar[5]arene(EtP5) and perethylated pillar[6]arene(Et P6). NACs of EtP5 cannot adsorb either alicyclic ketones or alicyclic alcohols because of the small cavity size of Et P5. By contrast, NACs of Et P6 can separate cyclopentanone from the vapor mixture of cyclopentanone/cyclopentanol(v:v = 1:1) and cyclohexanone from the vapor mixture of cyclohexanone/cyclohexanol(v:v = 1:1) with purities of 99.1% and 100%, respectively. Density functional theory calculations show that the selectivity comes from the thermodynamic stability of the newly formed crystal structure after adsorption of the preferred vip molecule. Moreover, NACs of Et P6 can be reused without losing selectivity and performance.展开更多
Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active...Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.展开更多
Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for...Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for these compounds serves a dual-purpose:enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation.This study investigated the host–vip recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules,1-chloro-2,4-dinitrobenzene and picric acid.Various techniques including^(1)H NMR,2D NOESY NMR,and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro vips in solution.Moreover,valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these vips with different pillararenes.The assembled solid-state supramolecular structures observed encompassed a 1:1 host–vip inclusion complex,an external binding complex,and an exo-wall tessellation complex.Furthermore,based on the findings from these systems,a pillararene-based test paper was developed for efficient picric acid detection,and the removal of picric acid from solution was also achieved using pillararenes powder.This research provides novel insights into the development of diverse host–vip systems toward hazardous compounds,offering potential applications in environmental protection and explosive detection domains.展开更多
Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-vip properties and ease of modifications, pillar[n]arenes ...Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-vip properties and ease of modifications, pillar[n]arenes have been developed rapidly in the field of functional materials and biomedicine. The modifications of pillar[n]arenes at different positions can give them varied characteristics. Functional groups can be introduced into one position of pillar[n]arenes without changing host-vip properties of pillar[n]arenes. A series of pillar[n]arene dimers, trimers, tetramers and metallacycles can be constructed by mono-functionalized pillar[n]arenes. In this review, two synthetic methods of mono-functionalized pillar[n]arenes are summarized and structures containing mono-functionalized pillar[n]arenes are described. Furthermore, the applications of mono-functionalized pillar[n]arenes in different fields (e.g., supramolecular polymers, sensors, molecular machines, catalysis, biological applications and light-harvesting systems) are also introduced. Hopefully, this article will be useful for researchers studying pillar[n]arenes, especially the mono-functionalized pillar[n]arenes.展开更多
Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene...Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.展开更多
Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules.In this study,a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ)metallacycle...Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules.In this study,a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ)metallacycle and pillar[5]arene-based host–vip interactions in an orthogonal way.The supramolecular oligo[2]rotaxane is further applied in fabricating a light harvesting system.展开更多
Macrocyclic materials have attracted much attention due to their particular chemical and physical properties.Herein we report the precise synthesis and characterization of a new bismacrocycle structure base on cyclopa...Macrocyclic materials have attracted much attention due to their particular chemical and physical properties.Herein we report the precise synthesis and characterization of a new bismacrocycle structure base on cycloparaphenylene(CPP)and pillar[5]arene,named cycloparaphenylene-pillar[5]arenes(CPPn[5]).The bismacrocycle was fully characterized by NMR and HR-MS.The photophysical properties of CPPn[5]were investigated by UV–vis,and the maximum absorption peak was located at 331 nm,which was consistent with density functional theory(DFT)calculations.The fluorescence spectrum was further studied and the emission peak was maximized at 458 nm.The computational results indicate the strain energy of CPPn[5]is 27.80 kcal/mol and the HOMO-LUMO gap is 3.39 eV Notably,CPPn[5]showed interesting supramolecular properties.展开更多
Early diagnosis and treatment of cancer requires the development of tools that are both sensitive and selective in detecting spermine.In this study,we presented a"supramolecular cyclization-induced emission enhan...Early diagnosis and treatment of cancer requires the development of tools that are both sensitive and selective in detecting spermine.In this study,we presented a"supramolecular cyclization-induced emission enhancement"strategy for the sensitive and selective detection of spermine.A new pillar[5]arene probe(P1)demonstrated excellent solution/solid dual-state emission properties,and the addition of certain spermine(Spm)resulted in fluorescence enhancement due to the synergy of multiple weak interactions that restricted the free motion of P1 in the P1⊃Spm complex.This mechanism was further confirmed by time-resolved spectroscopy,DFT calculations,and IGM analysis.With its low limit of detection and high selectivity,P1 is a promising tool for measuring spermine in artificial urine samples.展开更多
Multicharged supramolecular assemblies based on luminescent macrocycle play an important role in extending their optical properties and functions.Herein,we reported macrocyclic supramolecular assemblies based on lumin...Multicharged supramolecular assemblies based on luminescent macrocycle play an important role in extending their optical properties and functions.Herein,we reported macrocyclic supramolecular assemblies based on luminescent terphen[3]arene sulfate(TP[3]AS)and tetraphenylethylene pyridinium(TPE-4Py)through electrostatic interactions,host-vip encapsulation andπ-πstacking interactions.F?rster resonance energy transfer(FRET)process from TP[3]AS to TPE-4Py was achieved with the energy transfer efficiency of 99.9%,accompanied by TPE-4Py fluorescence emission bathochromic shifted of 15 nm and enhanced by 1.68 times in PBS solution.In contrast,other non-luminescent sulfato-β-cyclodextrin and sulfobutylether-β-cyclodextrin only can enhance the fluorescence intensity of TPE-4Py without bathochromic shift.Due to the strong fluorescence and good stability of TPE-4Py@TP[3]AS,it can be used for optical imaging in living cells,which provided an effective approach for the construction of assembling-confined luminescent biomaterials.展开更多
Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiropti...Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiroptical molecular devices.The structure of MUJ was confirmed by 1H NMR spectra and single-crystal X-ray diffraction analysis,and their planar-chiral enantiomers were successfully separated.Chiroptical inversion behaviors from in to out configurations triggered by temperature,solvent,and vip complexation were investigated by circular dichroism spectra.Chiroptical inversion could be realized in the presence of adiponitrile in certain solvents due to the solvation effects on the side ring and the threading of the vip into the pillar[5]arene cavity.However,the stronger self-included interactions between the cavity and the inside ring of certain MUJs led to inhibition of the switching.展开更多
文摘P450 enzymes-catalyzed aromatic hydroxylation plays an important role in detoxification,biosynthesis,and potential carcinogenic effect of aromatic compounds.Though it has been explored for decades,the actual process of aromatic hydroxylation and mechanism of regioselectivity catalyzed by cytochrome P450 monooxygenases remained ambiguous.Here,we have resolved these issues.With a stable chiral organofluorine probe,and especially with X-ray data of two isolated arene oxides derivatives,we demonstrate that an arene oxide pathway is definitely involved in P450-catalyzed aromatic hydroxylation.By the capture,isolation,identification and reactivity exploration of the arene 1,2-oxide and arene 2,3-oxide intermediates,together with advanced QM calculations,the mechanism of how two intermediates go to the same product has been elucidated.In addition to the model substrate,we also confirmed that an arene oxide intermediate is involved in the P450-catalyzed hydroxylation pathway of a natural product derivative methyl cinnamate,which indicates that this intermediate appears to be universal in P450-catalyzed aromatic hydroxylation.Our work not only provides the most direct evidence for the arene oxide pathway and new insights into the regioselectivity involved in P450-catalyzed aromatic hydroxylation,but also supplies a new synthetic approach to achieve the dearomatization of aromatic compounds.
文摘In the past decade,people have conducted extensive research on the synthesis and application properties of various functionalized pillararenes.Pillararenes show good application prospects in the field of sensors due to the rich host-vip recognition in their rigid electron-rich cavities.However,most reported pillararenes are functionalized by alkoxy modification,which results in poor charge transfer nature and weak fluorescence response.A π-conjugated charge-transfer system P5BN was obtained by introducing electron-donating triarylamine(Ar_(3)N)and electron-deficient triarylborane(Ar_(3)B)into pillar[5]arene skeleton,which significantly improved its luminescence behavior and was further used for fluorescence detection applications.The molecular structure showed that P5BN provided a good macrocyclic cavity to encapsulate amino acids molecules of suitable size.It was found that P5BN,as a fluorescent sensor,showed a highly sensitive and selective response to L-arginine(L-Arg),resulting in a significant enhancement of the fluorescence at 408 nm of P5BN with the lowest detection concentration being 2.21×10^(-8) mol/L.The recognition mechanism was demonstrated through experiments and DFT theoretical calculations.
文摘Many strategies have been proposed to produce arenes from lignin as liquid fuel additives.However,the development of these methods is limited by the low yield of products,low atom utilization,and inefficient lignin depolymerization.Herein,we develop an energy-efficient synthetic method for the production of high-carbon-number arenes from sustainable lignin with a total yield of 23.1 wt%.Particularly,high carbon number arenes are obtained by fully utilizing the formaldehyde stabilizing additive and the methoxy group in lignin.The process begins with the reductive depolymerization of formaldehyde-stabilized lignin,followed by transmethylation between lignin monomers over Au/Nb_(2)O_(5) catalyst,and the Ru/Nb2O5-catalyzed hydrodeoxygenation.This work demonstrates the potential of value-added arenes production directly from lignin.
基金the financial support from the National Natural Science Foundation of China(No.22101310)Fundamental Research Funds for the Central Universities(No.GK202207013)NJU International Fellowship program。
文摘Intracellular protein delivery is vital for the development of therapeutic proteins that act on intracellular targets.Although numerous carriers based on polymers and nanomaterials have been reported to facilitate cellular internalization of membrane impermeable proteins,it is still a great challenge to intracellularly deliver proteins with different sizes and isoelectric points through small molecule-based protein carrier.Herein,amidinium functionalized pillar[5]arene(AP5)was used as a small molecular carrier to facilitate intracellular delivery of proteins with different sizes and isoelectric points.The densely preorganized amidinium groups on pillar[5]arene skeleton could not only glue proteins together to form AP5@protein complex through multiple salt-bridges,but also promote cellular internalization AP5@protein complex.The bioactivities of the internalized proteins were well-maintained.This study provides a novel,versatile and macrocyclic-molecule based intracellular protein delivery carrier through the preorganization of amidiniums on pillar[5]arene.
基金financially supported by the National Natural Science Foundation of China(Nos.22001214,21662031,21661028 and 22061039)the Science Fund for Distinguished Young Scholars of Gansu Province(No.22JR5RA131)+4 种基金the Longyuan Innovation and Entrepreneurship Talent Project of Gansu Provincethe Major Project Cultivation Program of Northwest Normal Universitythe Top Leading Talents Project of Gansu Provincethe Key R&D program of Gansu Province(No.21YF5GA066)College Industry Support Plan Project of Gansu Province(No.2022CYZC-18)。
文摘Herein we report an environmentally friendly and energy-efficient method for the adsorptive separation of toluene from toluene-alcohol azeotropes using porous crystalline fluorinated leaning pillar[6]arene(FLP6α),achieving up to 100%purity.Moreover,FLP6αdemonstrates rapid adsorption and excellent recyclability.
基金supported by the National Natural Science Foundations of China(Nos.22464022,22461048,and 22364023)Scientific Research Fund Project of Yunnan Education Department(No.2023j0204)+3 种基金Yunnan Normal University Doctoral Research Initiation Program(No.01100205020503180)Xing Dian Talent Support Program Foundations(No.01100208019916016)Yunnan Normal University Graduate Research Innovation Fund Project(No.YJSJJ23-B87)Yunnan Basic Research Funding Program(Nos.202401AT070128,202301AT070074,and 202201AU070056)。
文摘Chiral anticancer drugs are the subject of ongoing research due to their optical characterization and pharmacological effects.Achieving a single enantiomer of a chiral anticancer drug is arduous,but it can significantly improve its pharmacokinetics for tumor therapy.Here,the chiral nanocatchers,known as Dbiotin-P5■MCC NCs,were designed and prepared based on host-vip self-assembly between D-biotin anchored pillar[5]arene(D-biotin-P5)and myristoyl chloride choline(MCC).D-Biotin-P5■MCC NCs featuring the chiral separation and enzyme-induced disassemble were evaluated for their ability to selectively capture and subsequently target the release of(R,R)-OXA enantiomers into tumor cells.Furthermore,the use of D-biotin-P5■MCC NCs has demonstrated a significant enhancement in the intracellular uptake of OXA,with the drug being efficiently released to MCF-7 breast cancer cells.This has led to a superior inhibitory effect on MCF-7 cells when compared to free OXA,while also reducing the cytotoxicity of the drug in HEK 293 human embryonic kidney cells.This research not only paves a promising way for the fabrication of chiral supramolecular nanocarriers but also holds the potential to improve the processes of chiral drug separation and targeted therapy.
基金Financial support from Science and Technology Innovation Program of Hunan Province(No.2022RC4044)。
文摘Deuterium(D),a stable and non-radioactive isotope of hydro-gen,is naturally present in the environment and is distinguishedfrom hydrogen by its greater mass.This mass difference resultsin a reduced stretching frequency of the carbon-deuterium(C-D)bond,leading to lower ground state energy and higher bond dis-sociation energy compared to the carbon-hydrogen(C–H)bond.
基金supported by the High-level Talent Cultivation Project of Nantong University。
文摘Sulfur dioxide(SO_(2)),being one of the therapeutic gaseous molecules,has been widely utilized in cancer therapy because of its high therapeutic efficacy and biosafety.Nevertheless,the in situ-triggered and efficient transportation of SO_(2)to tumors are the main obstacles that restrict its clinical application.To overcome this impediment,we functionalized pillar[5]arene with 2,4-dinitrobenzene sulfonic acid(DNSB)and then self-assembled it with tetraphenyl-PEG(TPE-PEG)in aqueous media to form fluorescent nanoparticles(PSTPE NPs).Meanwhile,the target vip(NH_(2)-PEG-FA)was encapsulated within the spacious cavity of pillar[5]arene via host-vip interaction.The resulting nanoparticles possess distinctive characteristics:(Ⅰ)dual GSH recognition motifs for enhanced SO_(2)release kinetics;(Ⅱ)incorporation of targeting ligands for selective cytotoxicity towards tumor cells while sparing normal tissues and cells;and(Ⅲ)surface modification of pillar[5]arene with TPE-PEG conferring excellent dispersibility,biocompatibility,and fluorescence properties in aqueous environments.Collectively,this novel nanoparticle represents an innovative approach that utilizes macrocyclics as SO_(2)gas donors to induce cellular apoptosis and provides new insights into gas-based therapy.
基金the National Natural Science Foundation of China(Nos.22171272,22031010)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0520302)the Youth Innovation Promotion Association CAS(No.2021035)for financial support。
文摘Supramolecular luminescent materials(SLMs)exhibit exceptional luminescence properties and the ability to be intelligently regulated through diverse assembly approaches,making them highly attractive in the field of luminescent materials.In recent years,the novel macrocyclic arenes characterized by unique electron-rich structures,ease of derivatization,tunable conformations and even inherent luminescence properties afford much opportunities to create such dynamic smart luminescent materials.The incorporation of macrocyclic arenes into SLMs leads to simple preparation process,diverse photophysical phenomena and sophisticated regulatory mechanisms,which is also currently one of the most frontier and hot topics in macrocyclic and supramolecular chemistry and even luminescent materials.In this review,the research advances in construction and applications of SLMs based on macrocyclic arenes in the last several years will be presented from the different assembly strategies,including host-vip complexes,supramolecular polymers,nanoparticles,and other assemblies.Moreover,some insights into future directions for this research area will also be offered.
基金supported by the Beijing Natural Science Foundation(No.2232024)the Analysis&Testing Centre at Beijing Institute of Technology for advanced facilities.
文摘Metal-complexed chiral macrocyclic architectures have attracted increasing research interests in circularly polarized luminescence owing to their distinctive structural and functional attributes.The method of metal coordination has emerged as a robust methodology for chirality induction in many systems.In this work,we engineered two rigid and flexible chiral organic ligands(L_(1) and L_(2))by synergizing the inherent planar chirality of pillar[5]arenes with tailored metal-coordination moieties.They demonstrate versatile coordination capabilities toward both 3d-and 4f-block metals,enabling modulation of luminescent characteristics with blue,green and red emissions.Four planar chiral complexes exhibiting CPL activity were synthesized through systematic coordination of L_(1)/L_(2) with Zn^(2+),Eu^(3+),and Tb^(3+).The coordination processes effectively rigidify molecular conformations,leading to an enhanced CPL performance.Particularly,the Tb-L_(2) complex displays superior lanthanide-centered emission with a fluorescence quantum yield of~55%and an emission dissymmetry factor glum=5.5×10^(-3).By engineering the substitution on pillar[5]arene scaffolds,we have established a metal-coordination platform with CPL characteristics,which paves the way in the design of new metal-based luminescent materials.
基金supported by the National Natural Science Foundation of China (No. 22101043)the Fundamental Research Funds for the Central Universities (Nos. N2205013, N232410019, N2405013)+2 种基金Natural Science Foundation of Liaoning Province (No. 2023-MSBA-068)the Opening Fund of State Key Laboratory of Heavy Oil Processing (No. SKLHOP202203006)Northeastern University。
文摘The separation of alicyclic ketones and alicyclic alcohols is one of the challenges in the field of petrochemical industry. However, traditional separation methods suffer from excessive energy consumption,complicated operation, and unsatisfactory separation efficiency for substances with similar boiling points.Herein, we offer an innovative method for the separation of alicyclic ketones and alicyclic alcohols employing nonporous adaptive crystals(NACs) of perethylated pillar[5]arene(EtP5) and perethylated pillar[6]arene(Et P6). NACs of EtP5 cannot adsorb either alicyclic ketones or alicyclic alcohols because of the small cavity size of Et P5. By contrast, NACs of Et P6 can separate cyclopentanone from the vapor mixture of cyclopentanone/cyclopentanol(v:v = 1:1) and cyclohexanone from the vapor mixture of cyclohexanone/cyclohexanol(v:v = 1:1) with purities of 99.1% and 100%, respectively. Density functional theory calculations show that the selectivity comes from the thermodynamic stability of the newly formed crystal structure after adsorption of the preferred vip molecule. Moreover, NACs of Et P6 can be reused without losing selectivity and performance.
文摘Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.
基金supported by the fundamental research funds of Zhejiang Sci-Tech University(No.22212286-Y)the Natural Science Foundation of Zhejiang Province(No.LQ24B040003)。
文摘Aromatic nitro compounds present substantial health and environmental concerns due to their toxic nature and potential explosive properties.Consequently,the development of host–vip molecular recognition systems for these compounds serves a dual-purpose:enabling the fabrication of high-performance sensors for detection and guiding the design of efficient adsorbents for environmental remediation.This study investigated the host–vip recognition behavior of perethylated pillar[n]arenes toward two aromatic nitro molecules,1-chloro-2,4-dinitrobenzene and picric acid.Various techniques including^(1)H NMR,2D NOESY NMR,and UV-vis spectroscopy were employed to explore the binding behavior between pillararenes and aromatic nitro vips in solution.Moreover,valuable single crystal structures were obtained to elucidate the distinct solid-state assembly behaviors of these vips with different pillararenes.The assembled solid-state supramolecular structures observed encompassed a 1:1 host–vip inclusion complex,an external binding complex,and an exo-wall tessellation complex.Furthermore,based on the findings from these systems,a pillararene-based test paper was developed for efficient picric acid detection,and the removal of picric acid from solution was also achieved using pillararenes powder.This research provides novel insights into the development of diverse host–vip systems toward hazardous compounds,offering potential applications in environmental protection and explosive detection domains.
基金the National Natural Science Foundation of China(No.22101043)the Fundamental Research Funds for the Central Universities(No.N2205013)and Northeastern University for financial support.
文摘Pillar[n]arenes are a novel class of macrocyclic hosts reported by Ogoshi and co-workers in 2008. Because of their rigid pillar structures, interesting host-vip properties and ease of modifications, pillar[n]arenes have been developed rapidly in the field of functional materials and biomedicine. The modifications of pillar[n]arenes at different positions can give them varied characteristics. Functional groups can be introduced into one position of pillar[n]arenes without changing host-vip properties of pillar[n]arenes. A series of pillar[n]arene dimers, trimers, tetramers and metallacycles can be constructed by mono-functionalized pillar[n]arenes. In this review, two synthetic methods of mono-functionalized pillar[n]arenes are summarized and structures containing mono-functionalized pillar[n]arenes are described. Furthermore, the applications of mono-functionalized pillar[n]arenes in different fields (e.g., supramolecular polymers, sensors, molecular machines, catalysis, biological applications and light-harvesting systems) are also introduced. Hopefully, this article will be useful for researchers studying pillar[n]arenes, especially the mono-functionalized pillar[n]arenes.
基金supported by the National Natural Science Foundation of China(U20A20268)Natural Science Foundation of Hunan Province(2020JJ1004)Hunan Provincial Innovation Foundation for Postgraduate(CX20211190)。
文摘Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.
基金financially supported by the National Natural Science Foundation of China(Nos.22001214,21662031,21661028,22061039)the Science Fund for Distinguished Young Scholars of Gansu Province(No.22JR5RA131)+3 种基金the Longyuan Innovation and Entrepreneurship Talent Project of Gansu Provincethe Major Project Cultivation Program of Northwest Normal University(No.NWNU-LKZD2022-01)the Top Leading Talents Project of Gansu Province,the Key R&D Program of Gansu Province(No.21YF5GA066)Gansu Province College Industry Support Plan Project(No.2022CYZC-18)。
文摘Oligo[n]rotaxanes are one of the most extensively studied categories of mechanically bonded macromolecules.In this study,a supramolecular oligo[2]rotaxane is successfully constructed driven by platinum(Ⅱ)metallacycle and pillar[5]arene-based host–vip interactions in an orthogonal way.The supramolecular oligo[2]rotaxane is further applied in fabricating a light harvesting system.
基金financially supported by the National Natural Science Foundation of China(Nos.22225108,21971229,U1932214)Hefei National Research Center for Physical Sciences at the Microscale。
文摘Macrocyclic materials have attracted much attention due to their particular chemical and physical properties.Herein we report the precise synthesis and characterization of a new bismacrocycle structure base on cycloparaphenylene(CPP)and pillar[5]arene,named cycloparaphenylene-pillar[5]arenes(CPPn[5]).The bismacrocycle was fully characterized by NMR and HR-MS.The photophysical properties of CPPn[5]were investigated by UV–vis,and the maximum absorption peak was located at 331 nm,which was consistent with density functional theory(DFT)calculations.The fluorescence spectrum was further studied and the emission peak was maximized at 458 nm.The computational results indicate the strain energy of CPPn[5]is 27.80 kcal/mol and the HOMO-LUMO gap is 3.39 eV Notably,CPPn[5]showed interesting supramolecular properties.
基金the National Natural Science Foundation of China(Nos.22071066,22071065)the National Key Research and Development Program of China(No.2016YFA0602900)+1 种基金the Guangdong Natural Science Foundation,China(No.2018B030311008)the Guangzhou Science and Technology Project,China(No.202102020802).
文摘Early diagnosis and treatment of cancer requires the development of tools that are both sensitive and selective in detecting spermine.In this study,we presented a"supramolecular cyclization-induced emission enhancement"strategy for the sensitive and selective detection of spermine.A new pillar[5]arene probe(P1)demonstrated excellent solution/solid dual-state emission properties,and the addition of certain spermine(Spm)resulted in fluorescence enhancement due to the synergy of multiple weak interactions that restricted the free motion of P1 in the P1⊃Spm complex.This mechanism was further confirmed by time-resolved spectroscopy,DFT calculations,and IGM analysis.With its low limit of detection and high selectivity,P1 is a promising tool for measuring spermine in artificial urine samples.
基金the National Natural Science Foundation of China(Nos.21971192,21807038)the Tianjin Municipal Education Commission(No.2021KJ188)the China Postdoctoral Science Foundation(No.2021T140343)。
文摘Multicharged supramolecular assemblies based on luminescent macrocycle play an important role in extending their optical properties and functions.Herein,we reported macrocyclic supramolecular assemblies based on luminescent terphen[3]arene sulfate(TP[3]AS)and tetraphenylethylene pyridinium(TPE-4Py)through electrostatic interactions,host-vip encapsulation andπ-πstacking interactions.F?rster resonance energy transfer(FRET)process from TP[3]AS to TPE-4Py was achieved with the energy transfer efficiency of 99.9%,accompanied by TPE-4Py fluorescence emission bathochromic shifted of 15 nm and enhanced by 1.68 times in PBS solution.In contrast,other non-luminescent sulfato-β-cyclodextrin and sulfobutylether-β-cyclodextrin only can enhance the fluorescence intensity of TPE-4Py without bathochromic shift.Due to the strong fluorescence and good stability of TPE-4Py@TP[3]AS,it can be used for optical imaging in living cells,which provided an effective approach for the construction of assembling-confined luminescent biomaterials.
基金the National Natural Science Foundation of China(Nos.92056116,21871194,21971169)National Key Research and Development Program of China(No.2017YFA0505903).
文摘Four pillar[5]arene-based bicyclic compounds,so-called molecular universal joint(MUJ),were synthesized by incorporating a bisamide ring containing N,O,or S-heteroatom groups,which served as stimuli-responsive chiroptical molecular devices.The structure of MUJ was confirmed by 1H NMR spectra and single-crystal X-ray diffraction analysis,and their planar-chiral enantiomers were successfully separated.Chiroptical inversion behaviors from in to out configurations triggered by temperature,solvent,and vip complexation were investigated by circular dichroism spectra.Chiroptical inversion could be realized in the presence of adiponitrile in certain solvents due to the solvation effects on the side ring and the threading of the vip into the pillar[5]arene cavity.However,the stronger self-included interactions between the cavity and the inside ring of certain MUJs led to inhibition of the switching.
