The benzoin group caged compound has received strong interests due to its excellent photo- deprotection properties and wide use in chemical and biological studies. We used timeresolved infrared spectroscopy to investi...The benzoin group caged compound has received strong interests due to its excellent photo- deprotection properties and wide use in chemical and biological studies. We used timeresolved infrared spectroscopy to investigate the photochemical reaction of the benzoin caged compound, o-（2-methylbenzoyl）-DL-benzoin under 266 nm laser irradiation. Taking advantage of the specific vibrational marker bands and the IR discerning capability, we have detected and identified the uncaging product 2-methylbenzoic acid, and two intermediate radicals of benzoyl and 2-methylbenzoate benzyl in the transient infrared spectra. Our results provide spectral evidence to support the homolytic cleavage reaction of C-C=O bond in competition with the deprotection reaction. Moreover, the product yields of 2-methylbenzoic acid and benzoyl radical were observed to be affected by solvents and a largely water contalning solvent can be in favor of the deprotection reaction.展开更多
Two new cage compounds,4-trinitroethyl-10-nitro-2,6,8,12-tetraacetylhexaazaisowurtzitane（3） and 4-trinitroethyl- 2,6,8,10,12-pentanitrohexaazaisowurtzitane（4）,containing trinitromethyl group were synthesized by a ...Two new cage compounds,4-trinitroethyl-10-nitro-2,6,8,12-tetraacetylhexaazaisowurtzitane（3） and 4-trinitroethyl- 2,6,8,10,12-pentanitrohexaazaisowurtzitane（4）,containing trinitromethyl group were synthesized by a novel method,and their structures were confirmed by IR,;H NMR,MS and single crystal X-ray.DSC result shows that compound 4 has surprising thermal stability and could be a potential energetic compound.展开更多
A mathematical model has been built up for compound cage rotor induction machine with the rotor resistance and leakage inductance in the model identified through Kalman filtering method. Using the identified parameter...A mathematical model has been built up for compound cage rotor induction machine with the rotor resistance and leakage inductance in the model identified through Kalman filtering method. Using the identified parameters, simulation studies are performed, and simulation results are compared with testing results.展开更多
The photocaging strategy has been widely used for activating biomolecules and hence regulating the underlying biological processes with high temporal and spatial resolution.Herein,we integrate this strategy into metab...The photocaging strategy has been widely used for activating biomolecules and hence regulating the underlying biological processes with high temporal and spatial resolution.Herein,we integrate this strategy into metabolic glycan labeling,which enables optical-ly-controlled metabolic labeling of cell-surface sialoglycans with azides.N-Azidoacetylmannosamine(ManNAz)is caged with a 4,5-dimethoxy-2-nitrobenzyl(DMNB)group at the anomeric hydroxyl group to block its cellular metabolism.After feeding to the cells,irradiation with 365 nm UV light or 405 nm visible light cleaves the photocage and generates ManNAz within the cells.ManNAz is metabolically converted to azido sialic acid,which is then incorporated into cell-surface sialoglycans.We demonstrated spatial and temporal control of this strategy by specifically labeling sialoglycans on a single cell and tracking the metabolism of ManNAz based on light-triggered pulse-chase labeling,respectively.The light-controlled metabolic glycan labeling strategy should facilitate probing of glycosylation in complex biological systems with high spatiotemporal precision.展开更多
Comprehensive Summary Triple interlocked systems represent highly intricate topological structures,formed by entwining two mechanically interlocked cages.Achieving controlled and straightforward construction of these ...Comprehensive Summary Triple interlocked systems represent highly intricate topological structures,formed by entwining two mechanically interlocked cages.Achieving controlled and straightforward construction of these aesthetic topologies continues to pose an enduring challenge.Herein,we employ a coordination-driven self-assembly strategy,capitalizing on non-covalent interactions in conjunction with half-sandwich metal units and meticulously designed isoquinoline-based ligands,to achieve the effective construction of organometallic interlocked cages 1 and 2.The resulting triple interlocked system's formation and architecture were validated by single-crystal X-ray diffraction,electrospray ionization mass spectroscopy,and comprehensive NMR tests.The Independent Gradient Model(IGM)more intuitively demonstrates the multiple stacking interactions within cage compounds,while planarity analysis elucidates the self-adaptability of the ligands and their tunable conformations.展开更多
Research into controlling the self-assembly of discrete porous organic cages(POCs)with specific geometries and functions is difficult,but important for understanding their structure-property relationship,as well as se...Research into controlling the self-assembly of discrete porous organic cages(POCs)with specific geometries and functions is difficult,but important for understanding their structure-property relationship,as well as self-assembly behavior in supramolecular chemistry.Herein,we report the self-assembly of two POCs based on the same tetraformyl-functionalized calix[4]resorcinarene(C4RACHO)and 2,4-diaminophenol dihydrochloride(DAP)organic building blocks,including a[3+6]triangular prism(CPOC-201-OH)and a[4+8]square prism(CPOC-401-OH),as determined by single X-ray crystallographic analysis.Both POCs exhibit large intrinsic cavities,rich oxygen sites,and high porosity with Brunauer-Emmett-Teller(BET)specific surface areas up to 966 m^(2)·g^(-1).Owing to such virtues,both cages can effectively capture iodine in aqueous media with removal rate>99%within 2 min.展开更多
Photodynamic therapy(PDT)is a promising noninvasive method for targeted cancer cell destruction.Still,its effectiveness is often hindered by the aggregation-caused quenching effect of organic photosensitizer(PS)in aqu...Photodynamic therapy(PDT)is a promising noninvasive method for targeted cancer cell destruction.Still,its effectiveness is often hindered by the aggregation-caused quenching effect of organic photosensitizer(PS)in aqueous environments.Here,we have employed a combination of covalent and noncovalent restricted-intramolecularrotation strategies to develop supramolecular PSs with aggregation-induced emission(AIE)characteristics.Firstly,a water-soluble octacationic molecular cage(1)with a bilayer tetraphenylethene(TPE)structure has been designed and synthesized,which minimizes intramolecular rotation of TPE moieties and achieves the single-molecule-level aggregation by the covalent restriction of intramolecular rotation(RIR)via molecular engineering synthesis.Compared with its single-layer TPE analog,1 exhibits superior efficiency in generating reactive oxygen species(ROS)including superoxide radical(O2−•)and singlet oxygen(1O2)upon whitelight irradiation.Subsequently,by forming a 1:4 host–vip complex(1@CB[8]4)between 1 and cucurbit[8]uril(CB[8]),O2−•generation can be further enhanced by the noncovalent RIR via the host–vip assembly.Additionally,1@CB[8]4 as a photocatalyst promotes rapid oxidation of nicotinamide adenine dinucleotide(NADH)in water.Given its Type-I ROS generation and catalytic activity for NADH oxidation,1@CB[8]4 acts as a supramolecular AIE-type PS to exhibit strong photo-induced cytotoxicity upon white-light irradiation under hypoxic conditions,showcasing its potential for synergistic PDT.展开更多
Main observation and conclusion Important progress has been made in the development of energetic molecules with high performance by computer-aided molecular design in recent years,but structural novelty of organic sca...Main observation and conclusion Important progress has been made in the development of energetic molecules with high performance by computer-aided molecular design in recent years,but structural novelty of organic scaffolds is insufficient.In this work,we propose an intra-ring bridging strategy inspired by the known energetic nitramines to design novel polycyclic and cage energetic molecules.More than 100 energetic structures were designed by introducing the C—C bridges and increasing the ring size.The synthesis difficulty is considered besides the two most concerned properties of EMs,energy and safety.After a comprehensive estimation,a symmetric cage molecule labeled as 8U-30 was finally selected because of its relatively high detonation performance,and comparable impact sensitivity as well as synthetic accessibility with CL-20.Hopefully,the proposed strategy could be utilized in further molecular design to gain various scaffolds,especially cage structures,for different demands.展开更多
Many emerging strategies in chemo-,gene-,and immunotherapy require the accumulation of reagents in the cell nucleus.However,their delivery into the nucleus is often limited.Nuclear delivery could be enhanced with a ra...Many emerging strategies in chemo-,gene-,and immunotherapy require the accumulation of reagents in the cell nucleus.However,their delivery into the nucleus is often limited.Nuclear delivery could be enhanced with a rationally designed cargo-delivery scaffold,but this approach has rarely been successfully implemented.Herein,a stable,biocompatible molecular capsule that encapsulates and delivers camptothecin,a DNA topoisomerase I inhibitor,into the nucleus of living cells was reported.Nuclear delivery is facilitated by the ultra-small diameter,zero net charge,and hydrophobicity of the capsule.The encapsulated drug complex displays superior toxicity towards multiple cancer cells over the free drug,the Food and Drug Administration(FDA)approved drugs,as well as conventionally reported drug vectors.Additionally,it inhibits liver cancer tumor growth in a xenograft mouse model.Modification of the properties of such molecular capsules may make it possible to design therapeutic strategies that target specific cell organelles.展开更多
Comprehensive Summary 2,4,6,8-Tetraazanoradamantane skeleton is a unique rigid cage-like organic structure that has not been established.In this article,a facile protocol to build all-bridge-position-functionalized 2,...Comprehensive Summary 2,4,6,8-Tetraazanoradamantane skeleton is a unique rigid cage-like organic structure that has not been established.In this article,a facile protocol to build all-bridge-position-functionalized 2,4,6,8-tetraazanoradamantane skeleton by condensation of glyoxal,primary amines and disubstituted malondialdehydes,which were in situ generated from 2,2-dipropenyl-1,3-dioxolane or 4,4-dimethoxyhepta-2,5-diene via ozonation,is reported for the first time.A variety of primary amines are compatible with this process,and the corresponding 2,4,6,8-tetraalkyl-2,4,6,8-tetraazanoradamantane-9-one ethylene or methyl ketals were achieved in 16%—58%yields.N-Benzyl group could be converted to other functionalities such as acetyl and nitro,which indicates the structural diversity of this scaffold.展开更多
The sequestration of organic luminescent molecules(OLMs)within cage-based metal-organic frameworks(MOFs)as a dispersion platform has been developed to impede aggregation-caused quenching(ACQ).The homogenous encapsulat...The sequestration of organic luminescent molecules(OLMs)within cage-based metal-organic frameworks(MOFs)as a dispersion platform has been developed to impede aggregation-caused quenching(ACQ).The homogenous encapsulation of distinct luminescent vips of different sizes and emissive behaviors in the cage structure of a MOF resulted in high fluorescent quantum yields of 44.8%for DAPI@NKU-110(DAPI=4',6-diamidino-2-phenylindole),65.4%for TPPA@NKU-110(TPPA=tris(4-(pyridin-4-yl)phenyl)amine),31.3%for R6G@NKU-110(R6G=Rhodamine 6G),and 58.3%for PY@NKU-110(PY=Pyronin Y),attributable to the confinement effect caused by the rigid cages of NKU-110.More significantly,a positive correlation of the encapsulated quantity of OLMs with their concentration in the in-situ solvothermal reaction was unveiled by spectral analysis and utilized to facilely fabricate a white-light-emitting crystal material TPPA+R6G@NKU-110.This material features a large crystal size on the millimeter-scale,broadband white emission,ideal CIE coordinates(0.33,0.34),and a high quantum yield(49.1%)when excited at 365 nm.Moreover,such a strategy can be easily generalized to an abundance of other cage-based MOFs and a plentiful volume of OLMs for the future development of colorful,high performance luminescent materials.展开更多
Herein,we demonstrate a very useful strategy to construct cage-based metal-organic frameworks(MOFs)with third-order nonlinear-optical properties.More specifically,by employing the Zr_(4)L_(6)(L=embonate)cages to assem...Herein,we demonstrate a very useful strategy to construct cage-based metal-organic frameworks(MOFs)with third-order nonlinear-optical properties.More specifically,by employing the Zr_(4)L_(6)(L=embonate)cages to assembly with N-contained ligands and Mn^(2+)/Zn^(2+) ions,four Zr_(4)L_(6)-cage-based MOFs have been synthesized and structurally characterized.Among them,a 3D framework with strong aromatic π−πstacking force exhibits a good optical limiting effect.展开更多
Porous organic cages(POCs)as an innovative type of porous molecular materials enable multifunctional applications.Herein,a fluorescence POC(denoted as 1)has been constructed by means of 5/5'-((2/5-dimethoxy-l/4-ph...Porous organic cages(POCs)as an innovative type of porous molecular materials enable multifunctional applications.Herein,a fluorescence POC(denoted as 1)has been constructed by means of 5/5'-((2/5-dimethoxy-l/4-phenylene)bis(ethyne-2/1-diyl))diiso-phthalaldehyde condensing with cyclohexanediamine enantiomer with the aid of trifluoroacetic acid.1 exhibits the permanent void and prominent fluorescence with relative quantum yield of 73%confirmed by gas sorption and emission experiments,respectively.Moreover,this organic cage is capable of sensing diavalent Pd2+according to the fluorescence response to the addition of various metal ions.The dispersion of 1 in methanol containing palladium acetate was stirred at 25℃and then 80℃to reduce Pd2+ions into nanoparticles(NPs),leading to the composite(Pd@l)composed of fine Pd NPs with the size of co.1.8 nm.The catalytic nature of Pd@l over NaBH4 promoted the degeneration of nitrobenzene and congo red.This work introduces one new case of POCs with versatile properties and functions,including ion fluorescence recognition,fine Pd NPs stabilizer,and gas adsorption,enriching the family of POC-based materials.展开更多
The reasons for facile double desilylation of 13-vertex carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)(2)are discussed in this article.New 13-and 14-vertex ruthenacarboranes bearing the same-CH_(2)SiMe_(2)CH...The reasons for facile double desilylation of 13-vertex carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)(2)are discussed in this article.New 13-and 14-vertex ruthenacarboranes bearing the same-CH_(2)SiMe_(2)CH_(2)-linkage have been prepared and structurally characterized for comparison.Structural analyses of 13-and 14-vertex heteroboranes as well as control experiments suggest that the facile double desilylation of 2 on silica gel can be attributed to the joint actions of several factors involving the high ring-strain of exo five-membered C_(4)Si ring,Lewis acidity of Si atom and Brønsted acidity of silica surface.展开更多
Oxidation of hexabenzylhexaazaisowurtzitane by different Cr(VI) reagents has been studied, and a very stable amide product, hexabenzoylhexaazaisowurtzitane, has been obtained.
The additive reactivity of 2,6,8,12-tetraacetyl-4, 10-dibenzyl-2,4,6,8,10,12-hexazatetracyclo [5.5.0.05.9. 03.11] dodecane (3) in several conditions was studied. It was found that the N-benzyl groups in compound 3 cou...The additive reactivity of 2,6,8,12-tetraacetyl-4, 10-dibenzyl-2,4,6,8,10,12-hexazatetracyclo [5.5.0.05.9. 03.11] dodecane (3) in several conditions was studied. It was found that the N-benzyl groups in compound 3 could be oxidized to benzoyl groups by Cr(VI) reagents, and could be removed by cerium ammonium nitrate (CAN), meanwhile nitroamine products were given.展开更多
Reticular chemistry enables the precise design and synthesis of crystalline extended materials,however,its application in hierarchical self-assembly of superstructures remains challenging due to the limited control ov...Reticular chemistry enables the precise design and synthesis of crystalline extended materials,however,its application in hierarchical self-assembly of superstructures remains challenging due to the limited control over weak interactions between synthons,in contrast to the stronger coordination or covalent bonds typically involved.Herein,we introduce an anion-competitive strategy to control the topology and structural diversity of superstructures.Cationic tetrahedral Zr-based metal–organic polyhedra were used as cage-like synthons,which were charge-balanced by Cl^(-)ions and interconnected via hydrogen bonds to form hierarchical superstructures.Introducing trigonal planar NO_(3)^(-)ions to compete with spherical Cl^(-)ions produced three new superstructures featuring different hydrogen bond-based linkages and distinct topologies(dia,bnn,and xhy),diverging from the previously reported flu topology.Furthermore,the superstructures with dia and bnn topologies exhibit high porosities and record iodine adsorption capacities in solution(4.31 and 4.19 g·g^(-1),respectively).This work demonstrates the potential of reticular chemistry for the versatile design and construction of diversified hierarchical superstructures.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.21333012 and No.21425313） and the National Basic Research Program of China （No.2013CB834602）.
文摘The benzoin group caged compound has received strong interests due to its excellent photo- deprotection properties and wide use in chemical and biological studies. We used timeresolved infrared spectroscopy to investigate the photochemical reaction of the benzoin caged compound, o-（2-methylbenzoyl）-DL-benzoin under 266 nm laser irradiation. Taking advantage of the specific vibrational marker bands and the IR discerning capability, we have detected and identified the uncaging product 2-methylbenzoic acid, and two intermediate radicals of benzoyl and 2-methylbenzoate benzyl in the transient infrared spectra. Our results provide spectral evidence to support the homolytic cleavage reaction of C-C=O bond in competition with the deprotection reaction. Moreover, the product yields of 2-methylbenzoic acid and benzoyl radical were observed to be affected by solvents and a largely water contalning solvent can be in favor of the deprotection reaction.
基金the National Natural Science Foundation of China(No.20772011)the Basic Research Foundation of Beijing Institute of Technology(No.3090050320906) for financial support for this work.
文摘Two new cage compounds,4-trinitroethyl-10-nitro-2,6,8,12-tetraacetylhexaazaisowurtzitane（3） and 4-trinitroethyl- 2,6,8,10,12-pentanitrohexaazaisowurtzitane（4）,containing trinitromethyl group were synthesized by a novel method,and their structures were confirmed by IR,;H NMR,MS and single crystal X-ray.DSC result shows that compound 4 has surprising thermal stability and could be a potential energetic compound.
文摘A mathematical model has been built up for compound cage rotor induction machine with the rotor resistance and leakage inductance in the model identified through Kalman filtering method. Using the identified parameters, simulation studies are performed, and simulation results are compared with testing results.
基金supported by the National Key R&D Program of China(No.2018YFA0507600)the National Natural Science Foundation of China(Nos.91753206 and 21521003)。
文摘The photocaging strategy has been widely used for activating biomolecules and hence regulating the underlying biological processes with high temporal and spatial resolution.Herein,we integrate this strategy into metabolic glycan labeling,which enables optical-ly-controlled metabolic labeling of cell-surface sialoglycans with azides.N-Azidoacetylmannosamine(ManNAz)is caged with a 4,5-dimethoxy-2-nitrobenzyl(DMNB)group at the anomeric hydroxyl group to block its cellular metabolism.After feeding to the cells,irradiation with 365 nm UV light or 405 nm visible light cleaves the photocage and generates ManNAz within the cells.ManNAz is metabolically converted to azido sialic acid,which is then incorporated into cell-surface sialoglycans.We demonstrated spatial and temporal control of this strategy by specifically labeling sialoglycans on a single cell and tracking the metabolism of ManNAz based on light-triggered pulse-chase labeling,respectively.The light-controlled metabolic glycan labeling strategy should facilitate probing of glycosylation in complex biological systems with high spatiotemporal precision.
基金supported by the National Science Foundation of China(22031003,21720102004,and 22301040)the Shanghai Science Technology Committee(19DZ2270100).
文摘Comprehensive Summary Triple interlocked systems represent highly intricate topological structures,formed by entwining two mechanically interlocked cages.Achieving controlled and straightforward construction of these aesthetic topologies continues to pose an enduring challenge.Herein,we employ a coordination-driven self-assembly strategy,capitalizing on non-covalent interactions in conjunction with half-sandwich metal units and meticulously designed isoquinoline-based ligands,to achieve the effective construction of organometallic interlocked cages 1 and 2.The resulting triple interlocked system's formation and architecture were validated by single-crystal X-ray diffraction,electrospray ionization mass spectroscopy,and comprehensive NMR tests.The Independent Gradient Model(IGM)more intuitively demonstrates the multiple stacking interactions within cage compounds,while planarity analysis elucidates the self-adaptability of the ligands and their tunable conformations.
基金supported by the National Nature Science Foundation of China(22071244,22275191)Youth Innovation Promotion Association CAS(2022305)+1 种基金Natural Science Foundation of Fujian Province of China(2022J01503,2020J05087)Self-deployment Project Research Program of Haixi Institutes,Chinese Academy of Sciences(CXZX-2022-GH01).
文摘Research into controlling the self-assembly of discrete porous organic cages(POCs)with specific geometries and functions is difficult,but important for understanding their structure-property relationship,as well as self-assembly behavior in supramolecular chemistry.Herein,we report the self-assembly of two POCs based on the same tetraformyl-functionalized calix[4]resorcinarene(C4RACHO)and 2,4-diaminophenol dihydrochloride(DAP)organic building blocks,including a[3+6]triangular prism(CPOC-201-OH)and a[4+8]square prism(CPOC-401-OH),as determined by single X-ray crystallographic analysis.Both POCs exhibit large intrinsic cavities,rich oxygen sites,and high porosity with Brunauer-Emmett-Teller(BET)specific surface areas up to 966 m^(2)·g^(-1).Owing to such virtues,both cages can effectively capture iodine in aqueous media with removal rate>99%within 2 min.
基金Fok Ying Tong Education Foundation,Grant/Award Number:171010Natural Science Basic Research Plan for Distinguished Young Scholars in Shaanxi Province of China,Grant/Award Number:2021JC-37+1 种基金Northwestern University 2024 Excellent Doctoral Dissertation Cultivation Project,Grant/Award Number:YB2024011National Natural Science Foundation of China,Grant/Award Numbers:22122108,22371229,21975197。
文摘Photodynamic therapy(PDT)is a promising noninvasive method for targeted cancer cell destruction.Still,its effectiveness is often hindered by the aggregation-caused quenching effect of organic photosensitizer(PS)in aqueous environments.Here,we have employed a combination of covalent and noncovalent restricted-intramolecularrotation strategies to develop supramolecular PSs with aggregation-induced emission(AIE)characteristics.Firstly,a water-soluble octacationic molecular cage(1)with a bilayer tetraphenylethene(TPE)structure has been designed and synthesized,which minimizes intramolecular rotation of TPE moieties and achieves the single-molecule-level aggregation by the covalent restriction of intramolecular rotation(RIR)via molecular engineering synthesis.Compared with its single-layer TPE analog,1 exhibits superior efficiency in generating reactive oxygen species(ROS)including superoxide radical(O2−•)and singlet oxygen(1O2)upon whitelight irradiation.Subsequently,by forming a 1:4 host–vip complex(1@CB[8]4)between 1 and cucurbit[8]uril(CB[8]),O2−•generation can be further enhanced by the noncovalent RIR via the host–vip assembly.Additionally,1@CB[8]4 as a photocatalyst promotes rapid oxidation of nicotinamide adenine dinucleotide(NADH)in water.Given its Type-I ROS generation and catalytic activity for NADH oxidation,1@CB[8]4 acts as a supramolecular AIE-type PS to exhibit strong photo-induced cytotoxicity upon white-light irradiation under hypoxic conditions,showcasing its potential for synergistic PDT.
基金support from the National Natural Science Foundation of China(Nos.21875184,21978311)the Youth Talent of Shaanxi"TeZhi"Programproject sponsored by Xi’an Modern Chemistry Research Institute(WDZCKYXM20190101).
文摘Main observation and conclusion Important progress has been made in the development of energetic molecules with high performance by computer-aided molecular design in recent years,but structural novelty of organic scaffolds is insufficient.In this work,we propose an intra-ring bridging strategy inspired by the known energetic nitramines to design novel polycyclic and cage energetic molecules.More than 100 energetic structures were designed by introducing the C—C bridges and increasing the ring size.The synthesis difficulty is considered besides the two most concerned properties of EMs,energy and safety.After a comprehensive estimation,a symmetric cage molecule labeled as 8U-30 was finally selected because of its relatively high detonation performance,and comparable impact sensitivity as well as synthetic accessibility with CL-20.Hopefully,the proposed strategy could be utilized in further molecular design to gain various scaffolds,especially cage structures,for different demands.
基金the National Natural Science Foundation of China(No.22071049)the fund from China Hunan Provincial Science&Technology Department(No.2020RC3020)。
文摘Many emerging strategies in chemo-,gene-,and immunotherapy require the accumulation of reagents in the cell nucleus.However,their delivery into the nucleus is often limited.Nuclear delivery could be enhanced with a rationally designed cargo-delivery scaffold,but this approach has rarely been successfully implemented.Herein,a stable,biocompatible molecular capsule that encapsulates and delivers camptothecin,a DNA topoisomerase I inhibitor,into the nucleus of living cells was reported.Nuclear delivery is facilitated by the ultra-small diameter,zero net charge,and hydrophobicity of the capsule.The encapsulated drug complex displays superior toxicity towards multiple cancer cells over the free drug,the Food and Drug Administration(FDA)approved drugs,as well as conventionally reported drug vectors.Additionally,it inhibits liver cancer tumor growth in a xenograft mouse model.Modification of the properties of such molecular capsules may make it possible to design therapeutic strategies that target specific cell organelles.
基金financial support from the National Natural Science Foundation of China(22075144)the Natural ScienceFoundationof Jiangsu Province(BK20200459).
文摘Comprehensive Summary 2,4,6,8-Tetraazanoradamantane skeleton is a unique rigid cage-like organic structure that has not been established.In this article,a facile protocol to build all-bridge-position-functionalized 2,4,6,8-tetraazanoradamantane skeleton by condensation of glyoxal,primary amines and disubstituted malondialdehydes,which were in situ generated from 2,2-dipropenyl-1,3-dioxolane or 4,4-dimethoxyhepta-2,5-diene via ozonation,is reported for the first time.A variety of primary amines are compatible with this process,and the corresponding 2,4,6,8-tetraalkyl-2,4,6,8-tetraazanoradamantane-9-one ethylene or methyl ketals were achieved in 16%—58%yields.N-Benzyl group could be converted to other functionalities such as acetyl and nitro,which indicates the structural diversity of this scaffold.
基金This work was supported by NSFC(Nos.21531005,91856124,and 21905142)the Programme of Introducing Talents of Dis-[9]cipline to Universities(B18030).
文摘The sequestration of organic luminescent molecules(OLMs)within cage-based metal-organic frameworks(MOFs)as a dispersion platform has been developed to impede aggregation-caused quenching(ACQ).The homogenous encapsulation of distinct luminescent vips of different sizes and emissive behaviors in the cage structure of a MOF resulted in high fluorescent quantum yields of 44.8%for DAPI@NKU-110(DAPI=4',6-diamidino-2-phenylindole),65.4%for TPPA@NKU-110(TPPA=tris(4-(pyridin-4-yl)phenyl)amine),31.3%for R6G@NKU-110(R6G=Rhodamine 6G),and 58.3%for PY@NKU-110(PY=Pyronin Y),attributable to the confinement effect caused by the rigid cages of NKU-110.More significantly,a positive correlation of the encapsulated quantity of OLMs with their concentration in the in-situ solvothermal reaction was unveiled by spectral analysis and utilized to facilely fabricate a white-light-emitting crystal material TPPA+R6G@NKU-110.This material features a large crystal size on the millimeter-scale,broadband white emission,ideal CIE coordinates(0.33,0.34),and a high quantum yield(49.1%)when excited at 365 nm.Moreover,such a strategy can be easily generalized to an abundance of other cage-based MOFs and a plentiful volume of OLMs for the future development of colorful,high performance luminescent materials.
基金supported by the National Natural Science Foundation of China(21922111,21871050 and 21975288)the Natural Science Foundation of Fujian Province(2017J06009).
文摘Herein,we demonstrate a very useful strategy to construct cage-based metal-organic frameworks(MOFs)with third-order nonlinear-optical properties.More specifically,by employing the Zr_(4)L_(6)(L=embonate)cages to assembly with N-contained ligands and Mn^(2+)/Zn^(2+) ions,four Zr_(4)L_(6)-cage-based MOFs have been synthesized and structurally characterized.Among them,a 3D framework with strong aromatic π−πstacking force exhibits a good optical limiting effect.
基金the National Natural Science Foundation of China(Nos.21631003,21805005 and 22175020)the Fundamental Research Funds for the Central Universities(No.FRF-BD-20-14A)University of Science and Technology Beijing is gratefully acknowledged.
文摘Porous organic cages(POCs)as an innovative type of porous molecular materials enable multifunctional applications.Herein,a fluorescence POC(denoted as 1)has been constructed by means of 5/5'-((2/5-dimethoxy-l/4-phenylene)bis(ethyne-2/1-diyl))diiso-phthalaldehyde condensing with cyclohexanediamine enantiomer with the aid of trifluoroacetic acid.1 exhibits the permanent void and prominent fluorescence with relative quantum yield of 73%confirmed by gas sorption and emission experiments,respectively.Moreover,this organic cage is capable of sensing diavalent Pd2+according to the fluorescence response to the addition of various metal ions.The dispersion of 1 in methanol containing palladium acetate was stirred at 25℃and then 80℃to reduce Pd2+ions into nanoparticles(NPs),leading to the composite(Pd@l)composed of fine Pd NPs with the size of co.1.8 nm.The catalytic nature of Pd@l over NaBH4 promoted the degeneration of nitrobenzene and congo red.This work introduces one new case of POCs with versatile properties and functions,including ion fluorescence recognition,fine Pd NPs stabilizer,and gas adsorption,enriching the family of POC-based materials.
基金The work described in this paper was supported by grants from the Research Grants Council of the Hong Kong Special Administration Region(Nos.404610 and CUHK7/CRF/12G).
文摘The reasons for facile double desilylation of 13-vertex carborane 1,2-Me_(2)Si(CH_(2))_(2)-1,2-C_(2)B_(11)H_(11)(2)are discussed in this article.New 13-and 14-vertex ruthenacarboranes bearing the same-CH_(2)SiMe_(2)CH_(2)-linkage have been prepared and structurally characterized for comparison.Structural analyses of 13-and 14-vertex heteroboranes as well as control experiments suggest that the facile double desilylation of 2 on silica gel can be attributed to the joint actions of several factors involving the high ring-strain of exo five-membered C_(4)Si ring,Lewis acidity of Si atom and Brønsted acidity of silica surface.
文摘Oxidation of hexabenzylhexaazaisowurtzitane by different Cr(VI) reagents has been studied, and a very stable amide product, hexabenzoylhexaazaisowurtzitane, has been obtained.
文摘The additive reactivity of 2,6,8,12-tetraacetyl-4, 10-dibenzyl-2,4,6,8,10,12-hexazatetracyclo [5.5.0.05.9. 03.11] dodecane (3) in several conditions was studied. It was found that the N-benzyl groups in compound 3 could be oxidized to benzoyl groups by Cr(VI) reagents, and could be removed by cerium ammonium nitrate (CAN), meanwhile nitroamine products were given.
基金supported by National Natural Science Foundation of China(grant no.22101093)Natural Science Foundation of Hubei Province,China(grant no.2022CFB163)Knowledge Innovation Program of Wuhan-Shuguang Project,and Fundamental Research Funds for the Central Universities(grant no.CCNU22QN008,CCNU24JCPT017).
文摘Reticular chemistry enables the precise design and synthesis of crystalline extended materials,however,its application in hierarchical self-assembly of superstructures remains challenging due to the limited control over weak interactions between synthons,in contrast to the stronger coordination or covalent bonds typically involved.Herein,we introduce an anion-competitive strategy to control the topology and structural diversity of superstructures.Cationic tetrahedral Zr-based metal–organic polyhedra were used as cage-like synthons,which were charge-balanced by Cl^(-)ions and interconnected via hydrogen bonds to form hierarchical superstructures.Introducing trigonal planar NO_(3)^(-)ions to compete with spherical Cl^(-)ions produced three new superstructures featuring different hydrogen bond-based linkages and distinct topologies(dia,bnn,and xhy),diverging from the previously reported flu topology.Furthermore,the superstructures with dia and bnn topologies exhibit high porosities and record iodine adsorption capacities in solution(4.31 and 4.19 g·g^(-1),respectively).This work demonstrates the potential of reticular chemistry for the versatile design and construction of diversified hierarchical superstructures.
