The interracial assembly of photo-induced dimerization of atypical anthracene-containing amphiphilic dendron and host-vip interaction with γ-cyclodextrin has been investigated. It has been proved that even without ...The interracial assembly of photo-induced dimerization of atypical anthracene-containing amphiphilic dendron and host-vip interaction with γ-cyclodextrin has been investigated. It has been proved that even without long alkyl chain the amphiphilic dendron could still form stable Langmuir monolayer at the air/water interface. Through the host-vip interaction,γ-cyclodextrin can be used to encapsulate two headgroups of amphiphilic dendron in the antiparallel direction. However, the formed host-vip complex was sensitive to the surface pressure. Slight compression of surface pressure led amphiphilic dendron to reassemble into nanofibers through the strong π-π stacking between headgroups. On the other hand, under in situ irradiation, the amphiphilic dendron was stabilized in the cavity of γ- cyclodextrin through headgroup dimerization and the host-vip complex further irregularly aggregated to nanoparticles. Meanwhile, γ-cyclodextrin, as a silencer, blocked the supramolecular chirality transfer. Our conclusion was demonstrated through UV/vis, FT-IR, CD spectrum and AFM images, respectively.展开更多
The [CdCl_4]^（2-） anion as a structure inducer has proved to be useful in the construction of cucurbit[n]urilmetal coordination architectures and materials. In order to better understand the role and influence of th...The [CdCl_4]^（2-） anion as a structure inducer has proved to be useful in the construction of cucurbit[n]urilmetal coordination architectures and materials. In order to better understand the role and influence of the structure inducer in Q[n] systems, we report herein the self-assembly of Q[6] solely in the presence of[CdCl_4]^（2-）anions and in the presence of both a linear cationic organic vip and [CdCl_4]^（2-）anions. X-ray diffraction analysis revealed that 1D Q[6] porous channels were formed by the noncovalent interactions between Q[6] and [CdCl_4]^（2-）anions, but the ＇＇honeycomb effect＇＇ was not observed in the present study.However, it seems that the ＇＇honeycomb effect＇＇ and the self-assembly of Q[6] with [CdCl_4]^（2-）anions can be significantly modified and switched in the presence of a linear cationic dibutylamine vip through some unusual noncovalent interactions.展开更多
Well-defined Si- and Ti-MCM-41 mesoporous molecular sieves were synthesized in high yields through the halogen anion mediated S(+)X(-)I(+) assembly in the presence of cetylpyridinium bromide as template. The spectrosc...Well-defined Si- and Ti-MCM-41 mesoporous molecular sieves were synthesized in high yields through the halogen anion mediated S(+)X(-)I(+) assembly in the presence of cetylpyridinium bromide as template. The spectroscopy characterization of the as-synthesized samples confirmed that Ti (IV) could be isolated in the lattice positions of the MCM-41 mesostructure by this method.展开更多
The assembling of a coating of time-resolved fluorescent chelator BSPDA （ abbreviated for 4, 7-bis （ sulfhydrylphenyl）-1, 10-phenanthroline-2, 9-dicarboxylic acid） onto a nano-gold layer was demonstrated. First, B...The assembling of a coating of time-resolved fluorescent chelator BSPDA （ abbreviated for 4, 7-bis （ sulfhydrylphenyl）-1, 10-phenanthroline-2, 9-dicarboxylic acid） onto a nano-gold layer was demonstrated. First, BSPDA was synthesized by simple procedures, and then an approach was developed to immobilize BSPDA onto the nano-gold layer deposited on a silane modified glass substrate, whereby europium ion （Ⅲ, Eu^3＋ ） was captured and released owing to the interactive process of complexation and dissociation between BSPDA functionalized coating and Eu^3＋ solution. The fluorescence spectra and related lifetimes were determined. Also, the BSPDA functionalized coating＇s specific complexation with Eu^3＋ on the BSPDA assembly layer and the nonspecific adsorption of Eu^3＋ on the nano-gold layer were compared. These results allowed a selective complexation of Eu^3＋ by assembling a BSPDA chelating layer on the nano-gold layer; thus, a tunable time-resolved fluorescent layer was covalently attached, The results of the nanoparticle assembling and probing （or labeling） processes to specific bio-systems were very interesting and had significant implications to time-resolved-fluorescence-based detection on biosensor surfaces such as DNA chip and to arrayed light display devices.展开更多
Macrocycle confinement induced vip near-infrared(NIR)luminescence was research hotspot currently.Here in,we reported a cucurbit[7]uril(CB[7])confined 3,7-bis((E)-2-(pyridin-4-yl)vinyl)-10-Hphenothiazine bridged bis(...Macrocycle confinement induced vip near-infrared(NIR)luminescence was research hotspot currently.Here in,we reported a cucurbit[7]uril(CB[7])confined 3,7-bis((E)-2-(pyridin-4-yl)vinyl)-10-Hphenothiazine bridged bis(4-(4-bromophenyl)pyridine)(G),which not only boosted its NIR luminescence but also realized detection of HClO/ClO^(-)in living cells and lysosome imaging.Fluorescence spectroscopy experiments were performed to calculate the detection ability of probe G to HClO/ClO^(-)up to 147 nmol/L.As compared with G,supramolecular probe G■CB[7]formed after encapsulated by CB[7],the detection ability towards HClO/ClO^(-)was improved to 24 nmol/L which was ascribe to the macrocycle CB[7]confinement increasing the fluorescence intensity to 103 folds.Accompanying the excitation wavelength changing,the fluorescence red-shifted to 820 nm when excited by 570 nm light,which was used to NIR lysosome imaging.Meanwhile,the supramolecular assembly G■CB[7]was also successfully used to highly sense to exogenous HClO/ClO^(-)in RAW 264.7 cells and live animal.展开更多
Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by...Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by using bipyridyl ligands based on biphenyl unit and half-sandwich binuclear rhodium(III)/iridium(III) building blocks.The selective synthesis was realized by adjusting the length of dipyridyl arms.The utilization of curved U-shaped bipyridyl ligand L1 led to tweezer-like molecular assemblies.Subsequently,olefinic bonds were introduced to elongate dipyridyl arms obtaining ligand L2.The ligand L2 has two stable conformations,U-shape and Z-shape,which facilitated the formation of different topologies including the tetranuclear macrocycle and Borromean rings with different building blocks in this work.These structures in solid and solution all have been further confirmed by single-crystal X-ray diffraction,NMR analysis,and mass spectrometry.In addition,as an important driving force,π-π stacking interactions not only played a significant role in the stability of structures but also further triggered photothermal conversion in solution.The experimental results demonstrated that compounds 1a and 2 had good NIR photothermal conversion efficiency (11.83% and 17.76%),and further analysis found the photothermal conversion efficiency had a gradual increase in the trend with the π-π stacking interactions increasing.This research expands the application of topological structures in materials science and provides a new idea for the synthesis of novel photothermal conversion materials.展开更多
Objective:To study several types of ergodicity of the queue length of M/M/c queue with synchronous vacation. Methods: A matrix analytical method is applied to deal with it. Result: It is shown that {L ( t ), J (t) } i...Objective:To study several types of ergodicity of the queue length of M/M/c queue with synchronous vacation. Methods: A matrix analytical method is applied to deal with it. Result: It is shown that {L ( t ), J (t) } is geometrically ergodic if and only if it is ergodic. Conclusion:The criteria for the other types of ergodicity are obtained.展开更多
Recent studies have started to provide initial insights into the aggregation and assembly of two classes of back-rigidified foldamers with flat,curved backbones consisting of aromatic residues.With their persistent sh...Recent studies have started to provide initial insights into the aggregation and assembly of two classes of back-rigidified foldamers with flat,curved backbones consisting of aromatic residues.With their persistent shape that presents large,well-defined aromatic surface areas,these crescent foldamers were found to undergo size-dependent aggregation in solution and pack into 1D assemblies in the solid state.Crescent aromatic oligoamides undergo stacking interactions not only in polar solvents but also in nonpolar ones,a unique property that is not associated with many other molecules that associate via π-π stacking interaction.The stacking of oligo(m-phenylene ethynylenes) is similar to aromatic hydrocarbons,being promoted in polar solvents such as methanol while being discouraged in nonpolar solvents such as halohydrocarbons.The ready synthetic availability of crescent foldamers makes it possible to directly control the intermolecular interaction by tuning surface areas.Besides,the columnar assembly of these cavity-containing molecules provides a new strategy for constructing supramolecular nanotubular structures.展开更多
Current neuromodulation techniques such as optogenetics and deep-brain stimulation are transforming basic and translational neuroscience. These two neuro- modulation approaches are, however, invasive since surgical im...Current neuromodulation techniques such as optogenetics and deep-brain stimulation are transforming basic and translational neuroscience. These two neuro- modulation approaches are, however, invasive since surgical implantation of an optical fiber or wire electrode is required. Here, we have invented a non-invasive magnetogenetics that combines the genetic targeting of a mag- netoreceptor with remote magnetic stimulation. The noninvasive activation of neurons was achieved by neuronal expression of an exogenous magnetoreceptor, an iron-sulfur cluster assembly protein 1 （Iscal）. In HEK-293 cells and cultured hippocampal neurons expressing this magnetoreceptor, application of an external magnetic field resulted in membrane depolarization and calcium influx in a reproducible and reversible manner, as indicated by the ultrasensitive fluorescent calcium indicator GCaMP6s.Moreover, the magnetogenetic control of neuronal activity might be dependent on the direction of the magnetic field and exhibits on-response and off-response patterns for the external magnetic field applied. The activation of this magnetoreceptor can depolarize neurons and elicit trains of action potentials, which can be triggered repetitively with a remote magnetic field in whole-cell patch-clamp recording. In transgenic Caenorhabditis elegans expressing this magnetoreceptor in myo-3-specific muscle cells or mec-4- specific neurons, application of the external magnetic field triggered muscle contraction and withdrawal behavior of the worms, indicative of magnet-dependent activation of muscle cells and touch receptor neurons, respectively. The advantages of magnetogenetics over optogenetics are its exclusive non-invasive, deep penetration, long-term continuous dosing, unlimited accessibility, spatial uniformity and relative safety. Like optogenetics that has gone through decade-long improvements, magnetogenetics, with continuous modification and maturation, will reshape the current landscape of neuromodulation toolboxes and will have a broad range of applications to basic and translational neuroscience as well as other biological sciences. We envision a new age of magnetogenetics is coming.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21021003 and 50673095)the Basic Research Development Program(Nos.2007CB808005 and 2009CB930802)the Fund of the Chinese Academy of Sciences
文摘The interracial assembly of photo-induced dimerization of atypical anthracene-containing amphiphilic dendron and host-vip interaction with γ-cyclodextrin has been investigated. It has been proved that even without long alkyl chain the amphiphilic dendron could still form stable Langmuir monolayer at the air/water interface. Through the host-vip interaction,γ-cyclodextrin can be used to encapsulate two headgroups of amphiphilic dendron in the antiparallel direction. However, the formed host-vip complex was sensitive to the surface pressure. Slight compression of surface pressure led amphiphilic dendron to reassemble into nanofibers through the strong π-π stacking between headgroups. On the other hand, under in situ irradiation, the amphiphilic dendron was stabilized in the cavity of γ- cyclodextrin through headgroup dimerization and the host-vip complex further irregularly aggregated to nanoparticles. Meanwhile, γ-cyclodextrin, as a silencer, blocked the supramolecular chirality transfer. Our conclusion was demonstrated through UV/vis, FT-IR, CD spectrum and AFM images, respectively.
基金supported by the National Natural Science Foundation of China (No. 21361006)‘‘Chun-Hui’’ Fund of Chinese Ministry of Education (No. Z2011037)Guizhou University (No. 20127027)
文摘The [CdCl_4]^（2-） anion as a structure inducer has proved to be useful in the construction of cucurbit[n]urilmetal coordination architectures and materials. In order to better understand the role and influence of the structure inducer in Q[n] systems, we report herein the self-assembly of Q[6] solely in the presence of[CdCl_4]^（2-）anions and in the presence of both a linear cationic organic vip and [CdCl_4]^（2-）anions. X-ray diffraction analysis revealed that 1D Q[6] porous channels were formed by the noncovalent interactions between Q[6] and [CdCl_4]^（2-）anions, but the ＇＇honeycomb effect＇＇ was not observed in the present study.However, it seems that the ＇＇honeycomb effect＇＇ and the self-assembly of Q[6] with [CdCl_4]^（2-）anions can be significantly modified and switched in the presence of a linear cationic dibutylamine vip through some unusual noncovalent interactions.
文摘Well-defined Si- and Ti-MCM-41 mesoporous molecular sieves were synthesized in high yields through the halogen anion mediated S(+)X(-)I(+) assembly in the presence of cetylpyridinium bromide as template. The spectroscopy characterization of the as-synthesized samples confirmed that Ti (IV) could be isolated in the lattice positions of the MCM-41 mesostructure by this method.
基金Project supported by the National Natural Science Foundation of China (20505020) the Natural Science Foundation ofGuangdong Province (06300086) +2 种基金 China Postdoctoral Science Foundation (20060390202) Scientific Research Fund ofHunan Provincial Education Department (05C508) Skeleton Youth Faculty Programof Hunan Higher Educational School
文摘The assembling of a coating of time-resolved fluorescent chelator BSPDA （ abbreviated for 4, 7-bis （ sulfhydrylphenyl）-1, 10-phenanthroline-2, 9-dicarboxylic acid） onto a nano-gold layer was demonstrated. First, BSPDA was synthesized by simple procedures, and then an approach was developed to immobilize BSPDA onto the nano-gold layer deposited on a silane modified glass substrate, whereby europium ion （Ⅲ, Eu^3＋ ） was captured and released owing to the interactive process of complexation and dissociation between BSPDA functionalized coating and Eu^3＋ solution. The fluorescence spectra and related lifetimes were determined. Also, the BSPDA functionalized coating＇s specific complexation with Eu^3＋ on the BSPDA assembly layer and the nonspecific adsorption of Eu^3＋ on the nano-gold layer were compared. These results allowed a selective complexation of Eu^3＋ by assembling a BSPDA chelating layer on the nano-gold layer; thus, a tunable time-resolved fluorescent layer was covalently attached, The results of the nanoparticle assembling and probing （or labeling） processes to specific bio-systems were very interesting and had significant implications to time-resolved-fluorescence-based detection on biosensor surfaces such as DNA chip and to arrayed light display devices.
基金financially supported by the National Natural Science Foundation of China(No.22131008)Liaocheng University Start-up Fund for Doctoral Scientific Research(No.318052327)。
文摘Macrocycle confinement induced vip near-infrared(NIR)luminescence was research hotspot currently.Here in,we reported a cucurbit[7]uril(CB[7])confined 3,7-bis((E)-2-(pyridin-4-yl)vinyl)-10-Hphenothiazine bridged bis(4-(4-bromophenyl)pyridine)(G),which not only boosted its NIR luminescence but also realized detection of HClO/ClO^(-)in living cells and lysosome imaging.Fluorescence spectroscopy experiments were performed to calculate the detection ability of probe G to HClO/ClO^(-)up to 147 nmol/L.As compared with G,supramolecular probe G■CB[7]formed after encapsulated by CB[7],the detection ability towards HClO/ClO^(-)was improved to 24 nmol/L which was ascribe to the macrocycle CB[7]confinement increasing the fluorescence intensity to 103 folds.Accompanying the excitation wavelength changing,the fluorescence red-shifted to 820 nm when excited by 570 nm light,which was used to NIR lysosome imaging.Meanwhile,the supramolecular assembly G■CB[7]was also successfully used to highly sense to exogenous HClO/ClO^(-)in RAW 264.7 cells and live animal.
基金supported by the National Natural Science Foundation of China(Nos.22031003,21720102004)the Shanghai Science Technology Committee(No.19DZ2270100)G.-X.J.thanks the Alexander von Humboldt Foundation for a Humboldt Research Award.
文摘Making full use of coordination-driven self-assembly strategy,we herein described the selective synthesis of a molecular Borromean rings and two cases of “U”-shaped tweezer-like molecular assemblies in high yield by using bipyridyl ligands based on biphenyl unit and half-sandwich binuclear rhodium(III)/iridium(III) building blocks.The selective synthesis was realized by adjusting the length of dipyridyl arms.The utilization of curved U-shaped bipyridyl ligand L1 led to tweezer-like molecular assemblies.Subsequently,olefinic bonds were introduced to elongate dipyridyl arms obtaining ligand L2.The ligand L2 has two stable conformations,U-shape and Z-shape,which facilitated the formation of different topologies including the tetranuclear macrocycle and Borromean rings with different building blocks in this work.These structures in solid and solution all have been further confirmed by single-crystal X-ray diffraction,NMR analysis,and mass spectrometry.In addition,as an important driving force,π-π stacking interactions not only played a significant role in the stability of structures but also further triggered photothermal conversion in solution.The experimental results demonstrated that compounds 1a and 2 had good NIR photothermal conversion efficiency (11.83% and 17.76%),and further analysis found the photothermal conversion efficiency had a gradual increase in the trend with the π-π stacking interactions increasing.This research expands the application of topological structures in materials science and provides a new idea for the synthesis of novel photothermal conversion materials.
基金This work was partially supported by NNSF of China(No.10171009)"211 Project"+1 种基金"985 Project" Research Fund for Ph. D Programs of MOE of China(No.20010533001)
文摘Objective:To study several types of ergodicity of the queue length of M/M/c queue with synchronous vacation. Methods: A matrix analytical method is applied to deal with it. Result: It is shown that {L ( t ), J (t) } is geometrically ergodic if and only if it is ergodic. Conclusion:The criteria for the other types of ergodicity are obtained.
基金supported by the Changjiang Scholar Programthe Cultivation Fund of the Key Scientific and Technical Innovation Project+1 种基金Ministry of Education of China (Grant No. 706009)the US National Science Foundation (CHE-0314577)
文摘Recent studies have started to provide initial insights into the aggregation and assembly of two classes of back-rigidified foldamers with flat,curved backbones consisting of aromatic residues.With their persistent shape that presents large,well-defined aromatic surface areas,these crescent foldamers were found to undergo size-dependent aggregation in solution and pack into 1D assemblies in the solid state.Crescent aromatic oligoamides undergo stacking interactions not only in polar solvents but also in nonpolar ones,a unique property that is not associated with many other molecules that associate via π-π stacking interaction.The stacking of oligo(m-phenylene ethynylenes) is similar to aromatic hydrocarbons,being promoted in polar solvents such as methanol while being discouraged in nonpolar solvents such as halohydrocarbons.The ready synthetic availability of crescent foldamers makes it possible to directly control the intermolecular interaction by tuning surface areas.Besides,the columnar assembly of these cavity-containing molecules provides a new strategy for constructing supramolecular nanotubular structures.
基金supported by Tsinghua-Peking Center for Life SciencesIDG/Mc Govern Foundationthe National Natural Science Foundation of China
文摘Current neuromodulation techniques such as optogenetics and deep-brain stimulation are transforming basic and translational neuroscience. These two neuro- modulation approaches are, however, invasive since surgical implantation of an optical fiber or wire electrode is required. Here, we have invented a non-invasive magnetogenetics that combines the genetic targeting of a mag- netoreceptor with remote magnetic stimulation. The noninvasive activation of neurons was achieved by neuronal expression of an exogenous magnetoreceptor, an iron-sulfur cluster assembly protein 1 （Iscal）. In HEK-293 cells and cultured hippocampal neurons expressing this magnetoreceptor, application of an external magnetic field resulted in membrane depolarization and calcium influx in a reproducible and reversible manner, as indicated by the ultrasensitive fluorescent calcium indicator GCaMP6s.Moreover, the magnetogenetic control of neuronal activity might be dependent on the direction of the magnetic field and exhibits on-response and off-response patterns for the external magnetic field applied. The activation of this magnetoreceptor can depolarize neurons and elicit trains of action potentials, which can be triggered repetitively with a remote magnetic field in whole-cell patch-clamp recording. In transgenic Caenorhabditis elegans expressing this magnetoreceptor in myo-3-specific muscle cells or mec-4- specific neurons, application of the external magnetic field triggered muscle contraction and withdrawal behavior of the worms, indicative of magnet-dependent activation of muscle cells and touch receptor neurons, respectively. The advantages of magnetogenetics over optogenetics are its exclusive non-invasive, deep penetration, long-term continuous dosing, unlimited accessibility, spatial uniformity and relative safety. Like optogenetics that has gone through decade-long improvements, magnetogenetics, with continuous modification and maturation, will reshape the current landscape of neuromodulation toolboxes and will have a broad range of applications to basic and translational neuroscience as well as other biological sciences. We envision a new age of magnetogenetics is coming.
