Carbon-rich cycloarene macrocycles can adopt multiple atropisomeric forms due to steric hindrance restrictingσ-bond rotation.These distinct conformations exhibit variations in cavity structure,electronic properties,a...Carbon-rich cycloarene macrocycles can adopt multiple atropisomeric forms due to steric hindrance restrictingσ-bond rotation.These distinct conformations exhibit variations in cavity structure,electronic properties,and functional site distribution,leading to diverse molecular recognition and self-assembly behaviors.In recent years,research on carbon-rich cycloarene macrocyclic compounds has emerged as a cutting-edge and interdisciplinary focus in the fields of carbon-rich functional molecules and macrocyclic chemistry.This review provides a comprehensive overview of the development of atropisomers in carbon-rich cycloarene macrocycles,spanning their design and synthesis,optoelectronic properties,and supramolecular chemistry.展开更多
Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excel...Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excellent stimuli responsiveness,facilitating efficient assembly construction.However,the limited availability of functional groups in conventional macrocycles restricts their ability to meet the demand for fabricating materials with multiple functionalities.To address this limitation,several research groups have introduced tetraphenylethylene(TPE),a well-known building block renowned for its remarkable aggregation-induced emission(AIE)effect,into the macrocycle framework.Herein,this paper summarizes the combination strategies and synergistic approaches that achieve multi-functionality by integrating TPE and macrocyclic architectures.The emission characteristics of TPE-embedded macrocycles are elucidated,and it is anticipated that more AIE-type macrocycles with innovative backbones and broad applications will emerge.展开更多
A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,h...A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,has been synthesized.This multi-stimuli-responsive[3]rotaxane exhibits unique molecular motion,with the macrocycles shuttling along the axle in response to acid-base reactions,temperature changes,solvent variations,and light irradiation.The molecular shuttle and reversibility were investigated by^(1)H NMR,2D NOESY,HRESI-MS,and UV-vis spectroscopy.This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness,highlighting its potential for multi-state control over the motion of interlocked rings on an axle.The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.展开更多
Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydrox...Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydroxybenzaldehyde） with phenylenediamines to prepare a conjugated[2 ＋ 2]Schiff base macrocycle has been investigated and fluorescent[2 ＋ 2]Schiff base macrocycles with N_2O_2 binding pockets has been prepared and characterized by elemental analysis,^1H NMR,IR,fluorescent,UV-visible and MALDI mass spectroscopies.展开更多
Gold nanoparticles （AuNPs） functionalized with supramolecular macrocycles are versatile and diverse hybrid nanomaterials, which combine and enhance the characteristics of the two components. In this mini-review, we ...Gold nanoparticles （AuNPs） functionalized with supramolecular macrocycles are versatile and diverse hybrid nanomaterials, which combine and enhance the characteristics of the two components. In this mini-review, we summarize the recent research progress on the synthesis and assembly of AuNPs functionalized with different supramolecular macrocyclic compounds, i.e., crown ethers, cyclophanes, cyclodextrins （CDs）, cucurbit[n]urils （CB[n]）, calix[n]arenes, and pillar[n]arenes （PIn]A）. Meanwhile, applications of these supramolecular hybrid nanomaterials in the fields of sensors, biomedicine and plasmonic devices are also presented.展开更多
A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b ...A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b = 25.157（2）,c = 8.5489（7） A,β = 104.4760（10）°,V = 2650.7（4） A^3,Z = 4,C26H30N6O10,Mr = 586.56,F（000） = 1232,T = 292（2） K,Dc = 1.470 g/cm^3,μ = 0.115 mm^-1,the final R = 0.0590 and wR = 0.1299 for 4918 observed reflections with I 〉 2σ（I）. In the structure of the title compound,a three-dimensional microporous architecture is formed via intermolecular hydrogen bonding interactions.展开更多
Because the widely used perfluorooctane sulfonate(PFOS) is harmful to both environment and human health, it is of great significance and urgency to develop sensitive and selective sensors for the detection of trace PF...Because the widely used perfluorooctane sulfonate(PFOS) is harmful to both environment and human health, it is of great significance and urgency to develop sensitive and selective sensors for the detection of trace PFOS in water. In this study, a tetraphenylethylene-derived macrocycle Bowtie Cyclophane has been developed as a fluorescent sensor based on aggregation-induced emission enhancement and fluorochromism. Sensitive detection of PFOS has been achieved with a limit of detection(LOD) of47.3 ± 2.0 nmol/L(25.4 ± 1.1 μg/L) accompanied by visual fluorescence color changes.展开更多
The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling ...The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling reaction between the binding site and the reporter. In addition, the formation 1,4-disubstituted1,2,3-triazole linker shows a high binding affinity toward both anions and metal ions. Recently researches revealed this reaction is also an efficient tool to form rigid or shape-persistent, preorganized macrocyclic species. This review summarized the recent advances in click derived macrocyclic receptors for recognition of anion, metal ion and ions pair.展开更多
Supramolecular polymers,which combined of the supramolecular chemistry and polymer science,are constructed from monomers together by reversible noncovalent interactions.Supramolecular polymers in aqueous solution are ...Supramolecular polymers,which combined of the supramolecular chemistry and polymer science,are constructed from monomers together by reversible noncovalent interactions.Supramolecular polymers in aqueous solution are especially important due to their superior biocompatibility and environmental adaptation,which determined they have wide applications in various areas,such as drug delivery,selfhealing,shape memory.Macrocyclic compounds,such as cyclodextrins,calixarenes,cucurbiturils and pillar[n]arenes,are the most used building blocks in the preparation of supramolecular polymers.Macrocycle-based supramolecular polymers,which introduce the host-vip interaction in the system,endow these polymers with interesting and smart physical-chemical properties.In this review,we summarized recent studies about supramolecular polymers in aqueous solution based on macrocyclic compounds.展开更多
The crystal structures of three intramolecularly hydrogen bonded rigid aromatic amide derivatives,which all bear one iodine atom at one end as the donor and one pyridine unit at the other end as the acceptor,have been...The crystal structures of three intramolecularly hydrogen bonded rigid aromatic amide derivatives,which all bear one iodine atom at one end as the donor and one pyridine unit at the other end as the acceptor,have been described to reveal the utility of halogen bonding in inducing the formation of supramolecular macrocycles.All the three compounds formed intermolecular I···N halogen bonding.For short compound 1,halogen bonding induced the formation of an extended supramolecular array.For longer folded compounds 2 and 3,halogen bonding could hold two molecules to form supramolecular macrocycles even by adopting a highly distorted,energetically less favorable conformation(for 3).Depending on the solvent for the growth of crystals,compound 3 could also gave rise to a halogen bonded supramolecular double helix.展开更多
Objective:To develop and validate a radiomics prognostic scoring system(RPSS)for prediction of progressionfree survival(PFS)in patients with stageⅣnon-small cell lung cancer(NSCLC)treated with platinum-based chemothe...Objective:To develop and validate a radiomics prognostic scoring system(RPSS)for prediction of progressionfree survival(PFS)in patients with stageⅣnon-small cell lung cancer(NSCLC)treated with platinum-based chemotherapy.Methods:In this retrospective study,four independent cohorts of stageⅣNSCLC patients treated with platinum-based chemotherapy were included for model construction and validation(Discovery:n=159;Internal validation:n=156;External validation:n=81,Mutation validation:n=64).First,a total of 1,182 three-dimensional radiomics features were extracted from pre-treatment computed tomography(CT)images of each patient.Then,a radiomics signature was constructed using the least absolute shrinkage and selection operator method(LASSO)penalized Cox regression analysis.Finally,an individualized prognostic scoring system incorporating radiomics signature and clinicopathologic risk factors was proposed for PFS prediction.Results:The established radiomics signature consisting of 16 features showed good discrimination for classifying patients with high-risk and low-risk progression to chemotherapy in all cohorts(All P<0.05).On the multivariable analysis,independent factors for PFS were radiomics signature,performance status(PS),and N stage,which were all selected into construction of RPSS.The RPSS showed significant prognostic performance for predicting PFS in discovery[C-index:0.772,95%confidence interval(95%CI):0.765-0.779],internal validation(C-index:0.738,95%CI:0.730-0.746),external validation(C-index:0.750,95%CI:0.734-0.765),and mutation validation(Cindex:0.739,95%CI:0.720-0.758).Decision curve analysis revealed that RPSS significantly outperformed the clinicopathologic-based model in terms of clinical usefulness(All P<0.05).Conclusions:This study established a radiomics prognostic scoring system as RPSS that can be conveniently used to achieve individualized prediction of PFS probability for stageⅣNSCLC patients treated with platinumbased chemotherapy,which holds promise for guiding personalized pre-therapy of stageⅣNSCLC.展开更多
Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors...Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors,magnetic materials,etc.,mainly because of their excellent redox activity.The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials,especially in relation to their electronic properties.Considering the instability of parent TPA radical cation,many efforts have been devoted to the development of stable TPA radical cations and related materials.Among them,TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals,thus endow them with outstanding redox behaviors,multiple resonance structures,and wide application in various optoelectronic devices.In this review,we give a brief introduction of organic radicals and the documented stable TPA radicals.Subsequently,a number of TPA radical cation-based macrocycles are comprehensively surveyed.It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles,but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.展开更多
Background:Platinum-based chemotherapy is the first-line treatment of non-small cell lung cancer(NSCLC);it is therefore important to discover biomarkers that can be used to predict the efficacy and toxicity of this tr...Background:Platinum-based chemotherapy is the first-line treatment of non-small cell lung cancer(NSCLC);it is therefore important to discover biomarkers that can be used to predict the efficacy and toxicity of this treatment.Four important transporter genes are expressed in the kidney,including organic cation transporter 2(OCT2),multidrug and toxin extrusion 1(MATEl),ATP-binding cassette subfamily B member 1 {ABCB1),and ATP-binding cassette subfamily C member 2(ABCC2),and genetic polymorphisms in these genes may alter the efficacy and adverse effects of platinum drugs.This study aimed to evaluate the association of genetic polymorphisms of these transporters with platinumbased chemotherapy response and toxicity in NSCLC patients.Methods:A total of 403 Chinese NSCLC patients were recruited for this study.All patients were newly diagnosed with NSCLC and received at least two cycles of platinum-based chemotherapy.The tumor response and toxicity were evaluated after two cycles of treatment,and the patients' genomic DNA was extracted.Seven single-nucleotide polymorphisms in four transporter genes were selected to investigate their associations with platinum-based chemotherapy toxicity and response.Results:OCT2 rs316019 was associated with hepatotoxicity(P = 0.026) and hematological toxicity(P = 0.039),and MATEl rs2289669 was associated with hematological toxicity induced by platinum(P = 0.016).In addition,ABCC2rs717620 was significantly associated with the platinum-based chemotherapy response(P = 0.031).ABCB1 polymorphisms were associated with neither response nor toxicity.Conclusion:OCT2 rs316019,MATEl rs2289669,and ABCC2 rs717620 might be potential clinical markers for predicting chemotherapy toxicity and response induced by platinum-based treatment in NSCLC patients.Trial registration Chinese Clinical Trial Registry展开更多
The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, ...The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?展开更多
Polyhaloalkanes are broadly useful yet environmentally harmful stock chemicals,therefore the development of adsorbent materials with capacity and selectivity for polyhaloalkane vapors is highly desirable.Here we repor...Polyhaloalkanes are broadly useful yet environmentally harmful stock chemicals,therefore the development of adsorbent materials with capacity and selectivity for polyhaloalkane vapors is highly desirable.Here we report a novel macrocycle WreathArene,a fluorinated C;-symmetrical [1;]-paracyclophane.In the crysalline state,WreathArene features vip-adaptive polymorphism for polyhaloalkanes including chloroform,tribromomethane,1,1,2-trichloroethane,and 1,2-dibromoethane.Non-covalent C-halogen…πinteractions are observed in all of these host-vip structures.Based on these properties,the activated WreathArene crystals can be utilized as a selective and recyclable adsorbent for polyhaloalkane vapors with excellent capacity under user-friendly conditions.展开更多
In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff...In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.展开更多
The synthesis of cyclopolymers upon controlling the degree of macrocyclic polymerization,followed by the discovery of new properties has attracted increasing attention in supramolecular chemistry.Herein,a Schiff-base ...The synthesis of cyclopolymers upon controlling the degree of macrocyclic polymerization,followed by the discovery of new properties has attracted increasing attention in supramolecular chemistry.Herein,a Schiff-base condensation method performed at room temperature was used to control the formation of[1+1]and[2+2]macrocycles.In pure MeOH,the isomer[1+1]macrocycles were synthesized and organic particles such as dendritic,rods,and solid microspheres were directly precipitated from the reaction solution.The[1+1]macrocycles can be efficiently converted into their corresponding[2+2]macrocycles accompanied by the tunable morphology of the organic particles when n-hexane was added to the MeOH solution.Further studies showed that these organic particles have potential application toward the selective removal of Cd^(2+)ions with different adsorption ability in MeOH solution.展开更多
New [1＋1] and 62-membered [2＋2] Schiff base macrocycles containing a 2,6-diamidopyridine subunit have been synthesized by condensation reaction of the precursors pyridine-2,6-dicarboxamide and 1,10- bis（2＇-formylp...New [1＋1] and 62-membered [2＋2] Schiff base macrocycles containing a 2,6-diamidopyridine subunit have been synthesized by condensation reaction of the precursors pyridine-2,6-dicarboxamide and 1,10- bis（2＇-formylphenyloxy）decane in the presence of phosphoric acid via a one-pot process. The cyclo- condensed products were effectively isolated by gel column chromatography and characterized by 1H NMR, FTIR, mass spectrometry and X-ray analysis. The two macrocycles have a twisted structure, and not an open ＇circular＇ conformation in the solid state.展开更多
Supramolecular assemblies constructed through the encapsulation of conductive polymers(CPs)by macrocyclic molecules have attracted increasing interest in the fields of supramolecular chemistry and electrochemistry.In ...Supramolecular assemblies constructed through the encapsulation of conductive polymers(CPs)by macrocyclic molecules have attracted increasing interest in the fields of supramolecular chemistry and electrochemistry.In this work,an effective strategy was reported to improve the stability and conductivity of CPs by electrochemically constructing different supramolecular assemblies composed of macrocycles and CPs.Typically,we uploaded zinc-based MOF(ZIF-8)onto carbon nanotube film(CNTF)and further electrically deposited macrocycles and CPs to gain the flexible conductive electrodes.Herein,five different supramolecular macrocycles,includingα-cyclodextrin(α-CD),sulfato-β-cyclodextrin(SCD),sulfonatocalix[4]arene(SC[4]),cucurbit[6]uril(CB[6])and cucurbit[7]uril(CB[7])were utilized and the electrochemical performances of the assembly electrodes increased in an order ofα-CD<SCD<SC[4]<CB[6]<CB[7],significantly improving the areal capacitance up to 1533 mF/cm^(2).This strategy may provide a new way for the application of macrocyclic supramolecules in electrochemical systems.展开更多
基金H.-Y.Gong is grateful to the National Natural Science Foundation of China(No.92156009)for financial Support.
文摘Carbon-rich cycloarene macrocycles can adopt multiple atropisomeric forms due to steric hindrance restrictingσ-bond rotation.These distinct conformations exhibit variations in cavity structure,electronic properties,and functional site distribution,leading to diverse molecular recognition and self-assembly behaviors.In recent years,research on carbon-rich cycloarene macrocyclic compounds has emerged as a cutting-edge and interdisciplinary focus in the fields of carbon-rich functional molecules and macrocyclic chemistry.This review provides a comprehensive overview of the development of atropisomers in carbon-rich cycloarene macrocycles,spanning their design and synthesis,optoelectronic properties,and supramolecular chemistry.
基金the National Natural Science Foundation of China(No.22271154)the Science Fund for Distinguished Young Scholars of Jiangsu Province(No.BK20240078).
文摘Macrocyclic hosts play a crucial role in supramolecular chemistry and the development of supramolecular functional materials.Their well-defined cavities and diverse host-vip interactions endow macrocycles with excellent stimuli responsiveness,facilitating efficient assembly construction.However,the limited availability of functional groups in conventional macrocycles restricts their ability to meet the demand for fabricating materials with multiple functionalities.To address this limitation,several research groups have introduced tetraphenylethylene(TPE),a well-known building block renowned for its remarkable aggregation-induced emission(AIE)effect,into the macrocycle framework.Herein,this paper summarizes the combination strategies and synergistic approaches that achieve multi-functionality by integrating TPE and macrocyclic architectures.The emission characteristics of TPE-embedded macrocycles are elucidated,and it is anticipated that more AIE-type macrocycles with innovative backbones and broad applications will emerge.
基金supported by the National Natural Science Foundation of China(No.22271202 to L.Yuan,No.22201193 to X.Li)the Sichuan Science and Technology Program(No.2023NSFSC0109 to X.Li)+2 种基金the Fundamental Research Funds for the Central Universities and the Hundred Talent Program of Sichuan University(No.YJ2021158 to X.Li)Sichuan University Interdisciplinary Innovation Fund(X.Li)Open Project of State Key Laboratory of Supramolecular Structure and Materials(No.SKLSSM2024037)。
文摘A novel[3]rotaxane,featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites,a secondary dialkylammonium(AM)unit and a 4,4'-bipyridinium(BP)unit,has been synthesized.This multi-stimuli-responsive[3]rotaxane exhibits unique molecular motion,with the macrocycles shuttling along the axle in response to acid-base reactions,temperature changes,solvent variations,and light irradiation.The molecular shuttle and reversibility were investigated by^(1)H NMR,2D NOESY,HRESI-MS,and UV-vis spectroscopy.This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness,highlighting its potential for multi-state control over the motion of interlocked rings on an axle.The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.
基金sponsored by Isfahan University of technology(IUT)
文摘Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydroxybenzaldehyde） with phenylenediamines to prepare a conjugated[2 ＋ 2]Schiff base macrocycle has been investigated and fluorescent[2 ＋ 2]Schiff base macrocycles with N_2O_2 binding pockets has been prepared and characterized by elemental analysis,^1H NMR,IR,fluorescent,UV-visible and MALDI mass spectroscopies.
基金the National Natural Science Foundation of China(No. 21272093)the Research Fund for the Doctoral Program of Higher Education of China(No.20120061120117)the Independent Innovation Research Program from the State Key Laboratory of Supramolecular Structure and Materials for financial support
文摘Gold nanoparticles （AuNPs） functionalized with supramolecular macrocycles are versatile and diverse hybrid nanomaterials, which combine and enhance the characteristics of the two components. In this mini-review, we summarize the recent research progress on the synthesis and assembly of AuNPs functionalized with different supramolecular macrocyclic compounds, i.e., crown ethers, cyclophanes, cyclodextrins （CDs）, cucurbit[n]urils （CB[n]）, calix[n]arenes, and pillar[n]arenes （PIn]A）. Meanwhile, applications of these supramolecular hybrid nanomaterials in the fields of sensors, biomedicine and plasmonic devices are also presented.
基金supported by Central China Normal University and the National Natural Science Foundation of China (20472022 and 20672042)
文摘A new macrocycle based on diethoxycarbonyl glycoluril 3,C26H30N6O10,has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic,space group P21/c with a = 12.7291（10）,b = 25.157（2）,c = 8.5489（7） A,β = 104.4760（10）°,V = 2650.7（4） A^3,Z = 4,C26H30N6O10,Mr = 586.56,F（000） = 1232,T = 292（2） K,Dc = 1.470 g/cm^3,μ = 0.115 mm^-1,the final R = 0.0590 and wR = 0.1299 for 4918 observed reflections with I 〉 2σ（I）. In the structure of the title compound,a three-dimensional microporous architecture is formed via intermolecular hydrogen bonding interactions.
基金Financial support from the National Natural Science Foundation of China (Nos. 21672227, 21922113, 22071257)the Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB17000000)+2 种基金the National Key Research and Development Program of China (No. 2017YFA0206903)K.C.Wong Education Foundationthe TIPC Director’s Fund。
文摘Because the widely used perfluorooctane sulfonate(PFOS) is harmful to both environment and human health, it is of great significance and urgency to develop sensitive and selective sensors for the detection of trace PFOS in water. In this study, a tetraphenylethylene-derived macrocycle Bowtie Cyclophane has been developed as a fluorescent sensor based on aggregation-induced emission enhancement and fluorochromism. Sensitive detection of PFOS has been achieved with a limit of detection(LOD) of47.3 ± 2.0 nmol/L(25.4 ± 1.1 μg/L) accompanied by visual fluorescence color changes.
基金supported by the National Natural Science Foundation of China (Nos. 21762028 and 21462027)Jiangxi Province Natural Science Foundation (Nos. 20161BAB213065 and 20171BAB203009)
文摘The Cu（I）-catalyzed azide-alkyne 1,3-dipolar cycloaddition（CuAAC） reaction, popularly known as the ＂click reaction＂, have been widely used in chemosensor field. This reaction gives a mild and efficient coupling reaction between the binding site and the reporter. In addition, the formation 1,4-disubstituted1,2,3-triazole linker shows a high binding affinity toward both anions and metal ions. Recently researches revealed this reaction is also an efficient tool to form rigid or shape-persistent, preorganized macrocyclic species. This review summarized the recent advances in click derived macrocyclic receptors for recognition of anion, metal ion and ions pair.
基金supported the National Natural Science Foundation of China(No.21801139)Natural Science Foundation of Jiangsu Province(No.BK20180942)+1 种基金the Natural Science Foundation of Nantong University(No.03083004)the large instruments open foundation of Nantong university(1No.KFJN1814)
文摘Supramolecular polymers,which combined of the supramolecular chemistry and polymer science,are constructed from monomers together by reversible noncovalent interactions.Supramolecular polymers in aqueous solution are especially important due to their superior biocompatibility and environmental adaptation,which determined they have wide applications in various areas,such as drug delivery,selfhealing,shape memory.Macrocyclic compounds,such as cyclodextrins,calixarenes,cucurbiturils and pillar[n]arenes,are the most used building blocks in the preparation of supramolecular polymers.Macrocycle-based supramolecular polymers,which introduce the host-vip interaction in the system,endow these polymers with interesting and smart physical-chemical properties.In this review,we summarized recent studies about supramolecular polymers in aqueous solution based on macrocyclic compounds.
基金the National Natural Science Foundation of China(Nos.21772026 and 21432004)for financial support
文摘The crystal structures of three intramolecularly hydrogen bonded rigid aromatic amide derivatives,which all bear one iodine atom at one end as the donor and one pyridine unit at the other end as the acceptor,have been described to reveal the utility of halogen bonding in inducing the formation of supramolecular macrocycles.All the three compounds formed intermolecular I···N halogen bonding.For short compound 1,halogen bonding induced the formation of an extended supramolecular array.For longer folded compounds 2 and 3,halogen bonding could hold two molecules to form supramolecular macrocycles even by adopting a highly distorted,energetically less favorable conformation(for 3).Depending on the solvent for the growth of crystals,compound 3 could also gave rise to a halogen bonded supramolecular double helix.
基金supported by the National Key Research and Development Plan of China(No.2017YFC1309100)the National Science Fund for Distinguished Young Scholars(No.81925023)the National Natural Scientific Foundation of China(No.81771912,81901910,82072090,and 82001986)。
文摘Objective:To develop and validate a radiomics prognostic scoring system(RPSS)for prediction of progressionfree survival(PFS)in patients with stageⅣnon-small cell lung cancer(NSCLC)treated with platinum-based chemotherapy.Methods:In this retrospective study,four independent cohorts of stageⅣNSCLC patients treated with platinum-based chemotherapy were included for model construction and validation(Discovery:n=159;Internal validation:n=156;External validation:n=81,Mutation validation:n=64).First,a total of 1,182 three-dimensional radiomics features were extracted from pre-treatment computed tomography(CT)images of each patient.Then,a radiomics signature was constructed using the least absolute shrinkage and selection operator method(LASSO)penalized Cox regression analysis.Finally,an individualized prognostic scoring system incorporating radiomics signature and clinicopathologic risk factors was proposed for PFS prediction.Results:The established radiomics signature consisting of 16 features showed good discrimination for classifying patients with high-risk and low-risk progression to chemotherapy in all cohorts(All P<0.05).On the multivariable analysis,independent factors for PFS were radiomics signature,performance status(PS),and N stage,which were all selected into construction of RPSS.The RPSS showed significant prognostic performance for predicting PFS in discovery[C-index:0.772,95%confidence interval(95%CI):0.765-0.779],internal validation(C-index:0.738,95%CI:0.730-0.746),external validation(C-index:0.750,95%CI:0.734-0.765),and mutation validation(Cindex:0.739,95%CI:0.720-0.758).Decision curve analysis revealed that RPSS significantly outperformed the clinicopathologic-based model in terms of clinical usefulness(All P<0.05).Conclusions:This study established a radiomics prognostic scoring system as RPSS that can be conveniently used to achieve individualized prediction of PFS probability for stageⅣNSCLC patients treated with platinumbased chemotherapy,which holds promise for guiding personalized pre-therapy of stageⅣNSCLC.
基金the Innovation Program of Shanghai Municipal Education Commission(No.2019-01-07-00-05-E00012)Program for Changjiang Scholars and Innovative Research Team in University for financial support+2 种基金the financial supports sponsored by NSFC/China(Nos.22071061,52003081)Shanghai Sailing Program(No.19YF1412900)Microscale Magnetic Resonance Platform of ECNU.
文摘Triphenylamine(TPA)derivatives and their radical cation counterparts have successfully demonstrated a great potential for applications in a wide range of fields including organic redox catalysis,organic semiconductors,magnetic materials,etc.,mainly because of their excellent redox activity.The stability of TPA radical cation has significant effect on the properties of the TPA-based functional materials,especially in relation to their electronic properties.Considering the instability of parent TPA radical cation,many efforts have been devoted to the development of stable TPA radical cations and related materials.Among them,TPA radical cation-based macrocycles have attracted particular attention because their large delocalized structures can stabilize the TPA radicals,thus endow them with outstanding redox behaviors,multiple resonance structures,and wide application in various optoelectronic devices.In this review,we give a brief introduction of organic radicals and the documented stable TPA radicals.Subsequently,a number of TPA radical cation-based macrocycles are comprehensively surveyed.It is expected that this minireview will not only summarize the recent development of TPA radical cations and their macrocycles,but also shed new light on the prospect of the design of more sophisticated radical cation-based architectures and related materials.
基金supported by the National High-tech R&D Program of China(863 Program)(2012AA02A517)National Natural Science Foundation of China(81173129,81202595,81373490,81273595)
文摘Background:Platinum-based chemotherapy is the first-line treatment of non-small cell lung cancer(NSCLC);it is therefore important to discover biomarkers that can be used to predict the efficacy and toxicity of this treatment.Four important transporter genes are expressed in the kidney,including organic cation transporter 2(OCT2),multidrug and toxin extrusion 1(MATEl),ATP-binding cassette subfamily B member 1 {ABCB1),and ATP-binding cassette subfamily C member 2(ABCC2),and genetic polymorphisms in these genes may alter the efficacy and adverse effects of platinum drugs.This study aimed to evaluate the association of genetic polymorphisms of these transporters with platinumbased chemotherapy response and toxicity in NSCLC patients.Methods:A total of 403 Chinese NSCLC patients were recruited for this study.All patients were newly diagnosed with NSCLC and received at least two cycles of platinum-based chemotherapy.The tumor response and toxicity were evaluated after two cycles of treatment,and the patients' genomic DNA was extracted.Seven single-nucleotide polymorphisms in four transporter genes were selected to investigate their associations with platinum-based chemotherapy toxicity and response.Results:OCT2 rs316019 was associated with hepatotoxicity(P = 0.026) and hematological toxicity(P = 0.039),and MATEl rs2289669 was associated with hematological toxicity induced by platinum(P = 0.016).In addition,ABCC2rs717620 was significantly associated with the platinum-based chemotherapy response(P = 0.031).ABCB1 polymorphisms were associated with neither response nor toxicity.Conclusion:OCT2 rs316019,MATEl rs2289669,and ABCC2 rs717620 might be potential clinical markers for predicting chemotherapy toxicity and response induced by platinum-based treatment in NSCLC patients.Trial registration Chinese Clinical Trial Registry
文摘The reaction of 4,4?-diaminodiphenylmethane (dadm), malonic acid (H2mal) and Cu(NO3)2 in aqueous solution results in a discrete binuclear Cu(II) macrocycle: [Cu(dadm)(mal)- (H2O)]22H2O. It crystallizes in monoclinic, space group P21/c with a = 15.231(3), b = 11.847(2), c = 9.801(2) ? b = 106.75(3)o, V = 1693.5(6) 3, Z = 2, C32H40Cu2N4O12, Mr = 799.76, Dc = 1.568 g/cm3, ?(MoKa) = 0.71073 ? = 1.325 mm-1, F(000) = 828, the final R = 0.0531 and wR = 0.1244 for 3421 observed reflections with I > 2s(I). Each Cu(II) is coordinated by two oxygen atoms from a mal ligand, two nitrogen atoms from two dadm ligands and a water oxygen atom to form a triangle bipyramidal motif. The title compound possesses a distorted macrocycle enclosed by dadm with approximate dimensions of 8.3 ??5.9 ?
基金Financial support from the National Natural Science Foundation of China (Nos. 21672227, 21922113, 21988102, 22071257)Chinese Academy of Sciences (Nos. XDB17000000)+2 种基金the National Key Research and Development Program (No. 2017YFA0206903)K. C.Wong Education Foundationthe TIPC Director’s Fund。
文摘Polyhaloalkanes are broadly useful yet environmentally harmful stock chemicals,therefore the development of adsorbent materials with capacity and selectivity for polyhaloalkane vapors is highly desirable.Here we report a novel macrocycle WreathArene,a fluorinated C;-symmetrical [1;]-paracyclophane.In the crysalline state,WreathArene features vip-adaptive polymorphism for polyhaloalkanes including chloroform,tribromomethane,1,1,2-trichloroethane,and 1,2-dibromoethane.Non-covalent C-halogen…πinteractions are observed in all of these host-vip structures.Based on these properties,the activated WreathArene crystals can be utilized as a selective and recyclable adsorbent for polyhaloalkane vapors with excellent capacity under user-friendly conditions.
基金Xunta de Galicia for his postdoctoral fellowship(ED481B-2022-068)the Fundación Segundo Gil Dávila for her PhD fellowship。
文摘In this paper,the lanthanoid complexes of N_(5) and N_(6) macrocycle ligands,without pendant arms or additional heteroatoms,are surveyed.This review covers the period from 2015 to the current date,since in 2014 Schiff base macrocyclic ligands incorporating the pyridine moiety,and their complexes,were revised,and in 2015 the chemistry of pentaaza macrocycle ligands with rare earth metals was also summarized.Porphyrin and phthalocyanine ligands are not included in this review,which primarily focuses on complexes with Schiff bases and amines without pendant arms or any additional donor other than nitrogen.The synthetic methods,structural characterization,based on single X-ray crystal data,and properties of the lanthanoid complexes,with special attention to magneto-structural correlations,are presented herein.
基金supported by the National Natural Science Foundation of China(Nos.21961007 and 21871063)the Science and Technology Foundation of Hunan Province(No.2020JJ2021).
文摘The synthesis of cyclopolymers upon controlling the degree of macrocyclic polymerization,followed by the discovery of new properties has attracted increasing attention in supramolecular chemistry.Herein,a Schiff-base condensation method performed at room temperature was used to control the formation of[1+1]and[2+2]macrocycles.In pure MeOH,the isomer[1+1]macrocycles were synthesized and organic particles such as dendritic,rods,and solid microspheres were directly precipitated from the reaction solution.The[1+1]macrocycles can be efficiently converted into their corresponding[2+2]macrocycles accompanied by the tunable morphology of the organic particles when n-hexane was added to the MeOH solution.Further studies showed that these organic particles have potential application toward the selective removal of Cd^(2+)ions with different adsorption ability in MeOH solution.
基金supported by the National Natural Science Foundation of China (No. 21061003)the ‘Chun-Hui’ Fund of Chinese Ministry of Education (No. Z2012054)
文摘New [1＋1] and 62-membered [2＋2] Schiff base macrocycles containing a 2,6-diamidopyridine subunit have been synthesized by condensation reaction of the precursors pyridine-2,6-dicarboxamide and 1,10- bis（2＇-formylphenyloxy）decane in the presence of phosphoric acid via a one-pot process. The cyclo- condensed products were effectively isolated by gel column chromatography and characterized by 1H NMR, FTIR, mass spectrometry and X-ray analysis. The two macrocycles have a twisted structure, and not an open ＇circular＇ conformation in the solid state.
基金National Natural Science Foundation of China(Nos.21971127,21772099 and 21861132001)for financial support。
文摘Supramolecular assemblies constructed through the encapsulation of conductive polymers(CPs)by macrocyclic molecules have attracted increasing interest in the fields of supramolecular chemistry and electrochemistry.In this work,an effective strategy was reported to improve the stability and conductivity of CPs by electrochemically constructing different supramolecular assemblies composed of macrocycles and CPs.Typically,we uploaded zinc-based MOF(ZIF-8)onto carbon nanotube film(CNTF)and further electrically deposited macrocycles and CPs to gain the flexible conductive electrodes.Herein,five different supramolecular macrocycles,includingα-cyclodextrin(α-CD),sulfato-β-cyclodextrin(SCD),sulfonatocalix[4]arene(SC[4]),cucurbit[6]uril(CB[6])and cucurbit[7]uril(CB[7])were utilized and the electrochemical performances of the assembly electrodes increased in an order ofα-CD<SCD<SC[4]<CB[6]<CB[7],significantly improving the areal capacitance up to 1533 mF/cm^(2).This strategy may provide a new way for the application of macrocyclic supramolecules in electrochemical systems.
