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Enhanced Ordering and Efficient Photoalignment of Nanostructures in Block Copolymers Enabled by Halogen Bond
摘要： Fabrication and manipulation of macroscopically ordered nanostructures in polymer ?lms via supramolecular self-organization are fascinating from the viewpoints of science and technology. Here, a halogen bond (XB) was introduced into a block copolymer to facilitate its microphase separation process upon XB-driven supramolecular self-assembly. To the best of our knowledge, this is an extremely rare example to elegantly maneuver nanostructures of polymers by the emerging supramolecular interaction, XB. The nonmesogenic block copolymer composed of poly(ethylene oxide) and azopyridine-containing polymethacrylate was transformed into a supramolecular liquid-crystalline polymer through the halogen-bonded interaction between 1,2-diiodo-3,4,5,6-tetra?uorobenzene and the azopyridine group with the optimal molar ratio of 1:1. For comparison, one hydrogen-bonded liquid-crystalline polymer was also fabricated but no such ordering enhancement was acquired, indicating that both the high directionality of XB and the resulting supramolecular mesogenic ordering played key roles in the enhanced ordering of nanostructures in polymer ?lms. In addition, e?cient photoalignment and photoreorientation of nanostructures coinciding with the oriented direction of the supramolecular mesogens were also obtained by manipulating photoirradiation of linearly polarized light for the present XB-involved liquid-crystalline block copolymer, which is promising for the development of a novel generation of advanced composite liquid crystal (LC) materials.
关键词： halogen bond,supramolecular self-assembly,photoalignment,block copolymer,nanostructures
更新于2025-09-23 15:19:57
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Physicala??Chemical Properties of Self-Assembled Structures in Solution of Zinc Phthalocyanine and Bis-3-pentyl-PTCDI Derivative
摘要： For the first time, in this work, we succeed in synthesizing in solution a novel supramolecular self-assembled zinc phthalocyanine (ZnPc) and N,N′-bis(3-pentyl)-perylene-3,4,9,10-bis(dicarboximide) (bis-3-pentyl-PTCDI) system with improved light absorption and phosphorescence lifetime of the charge separated states up to 2.5 ms. Moreover, the structural and optical properties of undoped and doped with iodine ZnPc thin films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman analysis, and UV?vis spectroscopy. Analysis of ZnPc:I2:bis-3-pentyl-PTCDI blend in a 2:1 ratio shows that sandwich complexes between them result in improved bulk properties as compared to those of the single-component systems.
关键词： light absorption,Fourier transform infrared spectroscopy,UV?vis spectroscopy,bis-3-pentyl-PTCDI,X-ray diffraction,supramolecular self-assembly,X-ray photoelectron spectroscopy,zinc phthalocyanine,phosphorescence lifetime,Raman analysis
更新于2025-09-23 15:19:57
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CO2 and photo-controlled reversible conversion of supramolecular assemblies based on water soluble pillar[5]arene and coumarin-containing guest
摘要： In this communication, a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO2 responsive tertiary amine unit and a UV responsive coumarin group. When guest molecule 1 dispersed in water, it self-assembled into sheet-like structures. Upon bubbling CO2, 1 transformed into 1H due to the tertiary amine unit was protonated, accompany the nano-sheets transformed into vesicles. Further irradiation of 1H with 365 nm light for 3 h, the coumarin group reacted with each other to form bola-type amphiphie 2H. In this case, vesicles collapsed and re-assembled into nano-tubes. However, when addition of WP5 into the solution of 1H, the vesicles transformed into micelles, this is due to the formation of supramolecular amphiphile WP5&1H. Upon irradiation of WP5&1H with 365 nm light for 3 h, nano-ribbons observed instead of micelles in the solution. Notably, nanotubes from 2H could also transform into nano-ribbons after adding WP5. The self-assembly process and the resultant assemblies were characterized by TEM, SEM, DLS, SAXS and NMR technologies. Due to both CO2 and light are "green" for living organisms, we anticipated our system can offer the possibilities in "on demand" drug absorption and release.
关键词： Reversible conversion,Coumarin,Supramolecular assemblies,Amphiphiles,Pillar[5]arene
更新于2025-09-23 15:19:57
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Enhancing the performance of pollution degradation through secondary self-assembled composite supramolecular heterojunction photocatalyst BiOCl/PDI under visible light irradiation
摘要： A novel n-n type inorganic/organic heterojunction of flaky-like BiOCl/PDI photocatalyst was constructed by water bath heating method. Meanwhile, a simple method - secondary self-assembly was used to prepare the BiOCl/PDI with a special band structure. The photocatalytic activities were evaluated by degrading aqueous organic pollutants under visible light (λ > 420 nm). The removal rates of 5 mg L?1 phenol (non-ionic type), methyl orange (MO, anionic type), rhodamine B (RhB, cationic type) and 10 mg L?1 RhB by secondary self-assembly BiOCl/PDI (BiOCl/PDI-2) were 8.0%, 3.4%, 27.8% and 78.9% higher than self-assembly BiOCl/PDI (BiOCl/PDI-1) under visible light (λ > 420 nm). The better photocatalytic activity for BiOCl/PDI-2 was attributed to the optimization of energy-band structures, which arose from different exposed surfaces, narrower interplanar spacing and stronger visible light absorption performance. Under acidic condition, BiOCl/PDI-2 showed a good photocatalytic activity, which was not affected by neutral ionic intensity and had good recycling properties. Moreover, the photocatalytic mechanism was explored by free radical capture test and electron paramagnetic resonance (EPR), and contribution of active species was calculated. The main active species of BiOCl/PDI-2 were ?O2?, 1O2 and h+. Our work may provide a route to design efficient inorganic/organic heterojunctions for organic pollutants degradation.
关键词： Supramolecular,Visible light photocatalysts,Perylene diimide,BiOCl,Heterojunction
更新于2025-09-23 15:19:57
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Reply to Comment on a??Photo-Controlled Reversible Microtubule Assembly Mediated by Paclitaxel-Modified Cyclodextrina??
摘要： In a Correspondence on our previous study “Photo-Controlled Reversible Microtubule Assembly Mediated by Paclitaxel-Modified Cyclodextrin” published in this journal in 2018,[1a] Thorn-Seshold comments on our results.[1b] First of all, we would like to appreciate his comments and interest in our work. The aggregation behavior of microtubules (MTs) in our work has been demonstrated from the viewpoint of macrocycle-based host–guest complexation at the supramolecular level and subsequently, the MT stabilizers based on azobenzene-modified paclitaxel (PTX) derivatives as photoswitchable small molecules have been investigated by Thorn-Seshold and co-workers in 2019.[2] In our case, the microscopy results showed that the MT morphology was dramatically affected by the photoisomeric complexation between cyclodextrin (CD) and arylazopyrazole (AAP). No fibrous assembly as free MT could be observed in the presence of free PTX-CD, PTX-AAP, or their inclusion complex in the cis/trans states. Therefore, the introduction of CD and AAP definitely influenced the self-assembling behavior between PTX and MT. Moreover, fluorescent-dye-staining assays demonstrated that the PTX-derived host and guest compounds still possessed MT-targeting ability to some extent, because MT could be co-labeled by FITC-tagged antibodies and adamantane-containing RhB. Thus, the microtubular aggregation was proposed as one of the possible assembling modes in Scheme 1 (cartoon presentation). The binding mode of MT with CD and AAP was directly deduced from our microscopy images and cellular confocal experiments. The biological effect in our work may be jointly attributed to both the PTX-dependent pathway (PTX-induced microtubular stabilization) and the PTX-independent pathway (complexation-induced multivalent supramolecular cross-linkage) at the nanometer scale.[3] Under these circumstances, one reasonable explanation is that the latter (independent) effect may become comparable to the former (dependent) one when the MT affinity is reduced by chemical modification at the 2’-OH position of PTX. Moreover, as a widely studied macrocyclic receptor in supramolecular chemistry, CD can form a diversity of supramolecular assemblies.[4] To determine the precise binding mode, in addition to the viewpoint of structural biology for evaluating the original PTX–MT interaction at the single-molecule level, many other factors and multiple supramolecular noncovalent interactions (e.g., self-inclusion, self-exclusion, amphiphilicity, extensive hydrogen bonding, and supramolecular multivalency/cooperativity) between PTX-CD and PTX-AAP should also be taken into account. For example, the multivalent inclusion complexation between multiple CD and PTX molecules may confer high stability to the nano-assembly.[5] Therefore, in our opinion, no binding mode can be exclusively confirmed at the present time until the hyperfine structures of such multicomponent CD–protein assemblies have been obtained both in solution and in the solid state (e.g., in a single crystal). Moreover, azobenzene/CD is one of the most frequently used host–guest pairs in adjusting the assembling/disassembling behavior of proteins and other biomacromolecules.[6] Meanwhile, AAP is a new type of azo compound, which possesses quite distinct photophysical behavior compared to conventional azobenzenes, such as enhanced photostability and photoconversion efficiency. The biological effect of pristine AAP on pure MT may deserve further attention, but this aspect was outside the scope of our previous study. Overall, based on NMR, TEM, UV/Vis transmittance, and confocal microscopy experiments, we clearly demonstrated in our previous study that 1) the MT self-assembling morphology can be strongly affected by the host–guest complexation between CD and AAP, and that 2) complexation-induced MT aggregation can be realized in a cellular environment. Thus, our work provides an alternative supramolecular chemistry method to modulate a biomacromolecular assembling process. Finally, we would like to thank Dr. Thorn-Seshold for his constructive suggestions and express our hope that we can improve the chemical simulation and gain further insight into the biological mechanism in further work.
关键词： molecular recognition,photo-responsiveness,cyclodextrin,supramolecular assembly,microtubules
更新于2025-09-23 15:19:57
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Self-assembled Ln(III) cyclen-based micelles and AuNPs conjugates as candidates for luminescent and magnetic resonance imaging (MRI) agents
摘要： The tetra-substituted heptadentate cyclen (1,4,7,10-tetraazacyclododecane) based Eu(III)/Tb(III)/Gd(III)-complexes 1.Ln and 2.Ln were developed. 1.Eu/Tb and 2.Eu/Tb were employed in the formation of luminescent self-assembling ternary structures, and we demonstrate that only in the presence of appropriate sensitizing antennae, was the lanthanide-emission of 1.Eu/Tb and 2.Eu/Tb ‘switched on’. 1.Gd/2.Gd were developed as potential MIR contrast agents, and employed in NMRD-measurements, where their relaxivity was investigated, and their (relatively high) r1 values determined. The formation of a self-assembled micelle-type structure was clearly observed for 2.Gd. The functionalised gold nanoparticles 1.Ln-AuNP were also synthesized from 1.Ln. As for the free complexes, the Ln-emission was ‘switched on’ for 1.Eu/Tb-AuNP in the presence of the antennae. NMRD measurements indicated that the relaxivity for the 1.Gd-AuNP systems was very high, with a value of 445 s-1mM-1 (at 400 MHz), demonstrating the cumulative effect of the relatively high number of 1.Gd complexes on the surface of the AuNP.
关键词： gold nanoparticles,lanthanides,Supramolecular chemistry,luminescence,MRI contrast agents,cyclen complexes
更新于2025-09-23 15:19:57
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Reply to Comment on a??Photo-Controlled Reversible Microtubule Assembly Mediated by Paclitaxel-Modified Cyclodextrina??
摘要： In a Correspondence on our previous study ?Photo-Controlled Reversible Microtubule Assembly Mediated by Paclitaxel-Modified Cyclodextrin“ published in this journal in 2018,[1a] Thorn-Seshold comments on our results.[1b] First of all, we would like to appreciate his comments and interest in our work. The aggregation behavior of microtubules (MTs) in our work has been demonstrated from the viewpoint of macrocycle-based host–guest complexation at the supramolecular level and subsequently, the MT stabilizers based on azobenzene-modified paclitaxel (PTX) derivatives as photoswitchable small molecules have been investigated by Thorn-Seshold and co-workers in 2019.[2] In our case, the microscopy results showed that the MT morphology was dramatically affected by the photoisomeric complexation between cyclodextrin (CD) and arylazopyrazole (AAP). No fibrous assembly as free MT could be observed in the presence of free PTX-CD, PTX-AAP, or their inclusion complex in the cis/trans states. Therefore, the introduction of CD and AAP definitely influenced the self-assembling behavior between PTX and MT. Moreover, fluorescent-dye-staining assays demonstrated that the PTX-derived host and guest compounds still possessed MT-targeting ability to some extent, because MT could be co-labeled by FITC-tagged antibodies and adamantane-containing RhB. Thus, the microtubular aggregation was proposed as one of the possible assembling modes in Scheme 1 (cartoon presentation). The binding mode of MT with CD and AAP was directly deduced from our microscopy images and cellular confocal experiments. The biological effect in our work may be jointly attributed to both the PTX-dependent pathway (PTX-induced microtubular stabilization) and the PTX-independent pathway (complexation-induced multivalent supramolecular cross-linkage) at the nanometer scale.[3] Under these circumstances, one reasonable explanation is that the latter (independent) effect may become comparable to the former (dependent) one when the MT affinity is reduced by chemical modification at the 2’-OH position of PTX.
关键词： molecular recognition,photo-responsiveness,cyclodextrin,supramolecular assembly,microtubules
更新于2025-09-23 15:19:57
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Luminescent switch of polysaccharide-peptide-quantum dot nanostructures for targeted-intracellular imaging of glioblastoma cells
摘要： Glioblastoma multiforme (or GBM) remains one of the deadliest types of brain cancers. Nanomedicine can offer new strategies for fighting against GBM by combining the earliest possible diagnosis with multiple options of therapy. Hence, in this work, cysteine (Cys) and Poly-L-Arginine (PA) moieties were grafted to carboxymethyl cellulose (CMC) to produce biofunctional hybridized macromolecules (CMC_Cys and CMC_PA). These polymer-peptide conjugates were used simultaneously as surface capping ligands and biofunctional modifiers for the synthesis of ternary Ag-In-S (AIS) quantum dots (AIS QDs) via a green chemical process in aqueous medium and room temperature. These core-shell supramolecular nanostructures (AIS@CMC, AIS@CMC_Cys, and AIS@CMC_PA) were tested as fluorescent nanoprobes (“OFF-ON”) for targeted bioimaging and in vitro intracellular tracking of glioblastoma cells (GBM, U-87 MG). The nanosystems were characterized for physicochemical, structural, and morphological properties by NMR, UV–Vis, PL, FTIR, TEM/EDX/SAED, zeta potential, and DLS. Cytocompatibility was evaluated by mitochondrial activity assay, and confocal laser scanning microscopy was performed for investigating the kinetics of cellular uptake. The grafting caused a noticeable reduction of surface charges, associated with a drastic photoluminescence quenching (i.e., “OFF-state”) of AIS@CMC_Cys and AIS@CMC_PA compared to unmodified AIS@CMC. This effect was smartly applied for bioimaging GBM cells and for monitoring the internalization process by intracellular tracking, which underwent strong “de-quenching” at very early incubation times (~5 min). Thus, these novel hybrid nanocolloids produced via eco-friendly scalable aqueous process show potential as responsive fluorescent bioprobes for bioimaging and tracking intracellular pathways and mechanisms as a powerful weapon for fighting against brain cancer cells.
关键词： nanoconjugates,nanomaterials,colloids,polymer-semiconductor nanoprobes,supramolecular nanoparticles,fluorescent nanoparticles
更新于2025-09-23 15:19:57
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Nanohybrid Structures Based on Plasmonic or Fluorescent Nanoparticles and Retinal-Containing Proteins
摘要： Rhodopsins are light-sensitive membrane proteins enabling transmembrane charge separation (proton pump) on absorption of a light quantum. Bacteriorhodopsin (BR) is a transmembrane protein from halophilic bacteria that belongs to the rhodopsin family. Potential applications of BR are considered so promising that the number of studies devoted to the use of BR itself, its mutant variants, as well as hybrid materials containing BR, in various areas grows steadily. Formation of hybrid structures combining BR with nanoparticles is an essential step in promotion of BR-based devices. However, rapid progress, continuous emergence of new data, as well as challenges of analyzing the entire data require regular reviews of the achievements in this area. This review is devoted to the issues of formation of materials based on hybrids of BR with fluorescent semiconductor nanocrystals (quantum dots) and with noble metal (silver, gold) plasmonic nanoparticles. Recent data on formation of thin (mono-) and thick (multi-) layers from materials containing BR and BR/nanoparticle hybrids are presented.
关键词： hybrid structures,quantum dots,bacteriorhodopsin,supramolecular systems,SERS,plasmon nanoparticles,Raman scattering
更新于2025-09-23 15:19:57
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Supramolecular Design of Donor-Acceptor Complexes via Heteroatom Replacement towards Structure and Electrical Transporting Property Tailoring
摘要： A feasible strategy relies on using heteroatom replacement which is namely chemical modification to the organic compound. Here we present this design concept for donor-acceptor complexes, which involves introducing nitrogen atoms to the middle ring of donor molecules to promote short contacts and reduce steric effect of the mixed framework. These nitrogen modified complexes are able to possess shorter molecular distance besides the mixed stacking pathway, enlarged π–π interactions or even a scarce 1:2.5 molar ratio through extra acceptor insertion. As a result, the unique 1:2 complex with nitrogen atoms on the different sides demonstrated stable electron field-effect mobility performance, while the binary system with no nitrogen replacement or N atoms on the identical side displayed poor ambipolar properties. These results confirmed that the heteroatom replacement is a powerful molecular design tool to fine tune the molecular packing of organic donor-acceptor complexes and their corresponding electronic properties.
关键词： Theoretical Calculation,Electron Transport,Heteroatom Replacement,Supramolecular Design,Short Contacts,Stoichiometry Varying
更新于2025-09-23 15:19:57