A new alkylpyrrole derivative,fusariumin A(1),was isolated from the culture broth of the fungus Fusarium sp.The absolute configuration of fuasiumin A has been established as(2'R,3'R)using a combination of RDC(...A new alkylpyrrole derivative,fusariumin A(1),was isolated from the culture broth of the fungus Fusarium sp.The absolute configuration of fuasiumin A has been established as(2'R,3'R)using a combination of RDC(residual dipolar coupling)-based NMR and DFT-supported chiroptical spectroscopy.It is worth to note that in this study without the aid of the RDC analysis,an unambiguous determination of configuration and conformation was not feasible due to the excessive conformational possibilities of this open-chain compound.展开更多
Reversible self-assembly of nanoparticles remains challenging due to limited molecular mobility.Moreover,reported successful examples typically rely on inorganic-core nanoparticles that require surface pre-functionali...Reversible self-assembly of nanoparticles remains challenging due to limited molecular mobility.Moreover,reported successful examples typically rely on inorganic-core nanoparticles that require surface pre-functionalization with specific stimuli-responsive ligands.Here,we demonstrate reversible self-assembly of organic nanoparticles through the selective self-modulation of aliphatic chains,without the need for prior modification with external stimuli-responsive ligands.D-glucose 11-octadecylthioundecanoate(D-Glc-C11S18E)self-assembles into microspheres(3-6µm)comprising nanospheres(100-300 nm).Within these nanospheres,octadecylthioundecanoyl(C29)groups form interior crystalline domains(C29 lamella)while octadecyl(C18)chains organize at nanosphere interfaces(C18 lamella).Thermal triggering enables selective reversibility:at 50℃,the C18 lamella dissociates into disordered structures while the C29 lamella remains intact;cooling to 20℃regenerates the C18 lamella.In methanol,this process drives reversible microsphere-nanosphere morphological transitions(validated by scanning electron microscopy/dynamic light scattering),accompanied by a reversible fluorescence modulation.Both structural and optical modulations exhibit no apparent fatigue over 10 consecutive cycles.Energy decomposition analysis reveals stronger C29 binding energy(ΔE_(int)=-29.80 kcal/mol vs.C18’s-19.90 kcal/mol),explaining selective reversibility.Density functional theory calculations confirm the distinct highest occupied molecular orbital-lowest unoccupied molecular orbital gaps correlating with emission wavelengths.Leveraging the temperature/wavelength-dependent fluorescence,we constructed a multi-input logic gate.This work establishes a new insight for reversible assembly and enables smart and fatigue-resistant optoelectronic applications.展开更多
基金Support by the National Natural Science Foundation of China(U1132607)to J.K.L.the DFG(Forschergruppe FOR 934)to C.Gas well as the Chinese/German foundation(GZ1104)to H.S.and C.G.is acknowledged.
文摘A new alkylpyrrole derivative,fusariumin A(1),was isolated from the culture broth of the fungus Fusarium sp.The absolute configuration of fuasiumin A has been established as(2'R,3'R)using a combination of RDC(residual dipolar coupling)-based NMR and DFT-supported chiroptical spectroscopy.It is worth to note that in this study without the aid of the RDC analysis,an unambiguous determination of configuration and conformation was not feasible due to the excessive conformational possibilities of this open-chain compound.
基金supporting the project‘NEuM’(ZW7-85191973)Cheng Li thanks the China Scholarship Council(CSC)for the financial support of his PhD grant.Qiyun Tang acknowledges the financial support from the National Natural Science Foundation of China under Grant Number 12374207the Natural Science Foundation of Jiangsu Province,BK20233001.
文摘Reversible self-assembly of nanoparticles remains challenging due to limited molecular mobility.Moreover,reported successful examples typically rely on inorganic-core nanoparticles that require surface pre-functionalization with specific stimuli-responsive ligands.Here,we demonstrate reversible self-assembly of organic nanoparticles through the selective self-modulation of aliphatic chains,without the need for prior modification with external stimuli-responsive ligands.D-glucose 11-octadecylthioundecanoate(D-Glc-C11S18E)self-assembles into microspheres(3-6µm)comprising nanospheres(100-300 nm).Within these nanospheres,octadecylthioundecanoyl(C29)groups form interior crystalline domains(C29 lamella)while octadecyl(C18)chains organize at nanosphere interfaces(C18 lamella).Thermal triggering enables selective reversibility:at 50℃,the C18 lamella dissociates into disordered structures while the C29 lamella remains intact;cooling to 20℃regenerates the C18 lamella.In methanol,this process drives reversible microsphere-nanosphere morphological transitions(validated by scanning electron microscopy/dynamic light scattering),accompanied by a reversible fluorescence modulation.Both structural and optical modulations exhibit no apparent fatigue over 10 consecutive cycles.Energy decomposition analysis reveals stronger C29 binding energy(ΔE_(int)=-29.80 kcal/mol vs.C18’s-19.90 kcal/mol),explaining selective reversibility.Density functional theory calculations confirm the distinct highest occupied molecular orbital-lowest unoccupied molecular orbital gaps correlating with emission wavelengths.Leveraging the temperature/wavelength-dependent fluorescence,we constructed a multi-input logic gate.This work establishes a new insight for reversible assembly and enables smart and fatigue-resistant optoelectronic applications.
