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Control on Dimensions and Supramolecular Chirality of Self-Assemblies through Light and Metal Ions
摘要： Precise control over helical chirality and dimensions of molecular self-assemblies, a remaining challenge for both chemists and materials scientists, is the key to manipulate the property and performance of supramolecular materials. Herein, we report that a cholesterol-azopyridine conjugate could self-assemble into organogels with photo-controllable dimensional transition from 2D microbelts to 1D nanotubes and finally to 0D nanoparticles. The E/Z-Photoisomerization of the 4-azopyridine unit is the major driving force for the dimensional transformation. Furthermore, the self-assembled structures were observed to exhibit metal ion-mediated helicity inversion through the metal coordination. These observations were collectively confirmed by several techniques including scanning electron microscopy, atomic force microscope, circular dichroism, and X-ray crystallography. The rational design of building blocks for the construction of dimension and chirality controllable self-assembly systems may lead to versatile applications in smart display, advanced optoelectronic device, and supramolecular asymmetric catalysis.
关键词： photoisomerization,dimensional transition,supramolecular chirality,metal coordination,self-assembly
更新于2025-09-23 15:21:21
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A self-assembly/disassembly two-photo ratiometric fluorogenic probe for bacteria imaging
摘要： A fluorogenic probe for bacteria imaging was reported. The binding with anionic bacterial surfaces disassembled the self-assembly probe to turn-on the fluorescence and shift pyrene monomer/excimer ratiometric signals.
关键词： Self-assembly,Pyrene,Bacteria,Fluorogenic probe,Imidazolium
更新于2025-09-23 15:21:21
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Preparing Semiconducting Nanoribbons with Tunable Length and Width via Crystallization-Driven Self-Assembly of a Simple Conjugated Homopolymer
摘要： Precise control of width and length of one-dimensional (1D) semiconducting nanostructures has attracted much attention owing to its potential for optoelectronic applications. However, regulating both their length and width using conjugated polymers or even block copolymers is a huge challenge. To solve this problem, we synthesized a unique conjugated polyacetylene homopolymer by living cyclopolymerization, which spontaneously formed 1D nanoribbons via in situ nanoparticlization. Interestingly, their widths could be controlled from 8 to 41 nm, which were directly proportional to their degree of polymerization. Furthermore, a self-seeding technique via crystallization-driven self-assembly (CDSA) was used to control the length of the nanoribbons up to 5.2 μm with narrow distributions less than 1.1. Interestingly, adding a block copolymer unimer to these nanoribbons produced triblock comicelles by the living CDSA mechanism. Finally, these nanoribbons were visualized directly by super-resolution optical fluorescence microscopy. Now, one can modulate both length and width of 1D nanoribbons simultaneously.
关键词： semiconducting nanostructures,crystallization-driven self-assembly,nanoribbons,optoelectronic applications,conjugated polymers
更新于2025-09-23 15:21:21
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Self-Assembly of a Carboxyl-Functionalized BODIPY Dye via Hydrogen Bonding
摘要： We report the synthesis, characterization, and self-assembly behavior of a 4,4-Difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dye functionalized at the meso-position with a butyric acid group. Various spectroscopic investigations (UV-Vis, emission, and Fourier-transform infrared spectroscopy (FTIR) studies) supported by X-ray analysis revealed the formation of self-assembled structures in the solid state with translationally stacked BODIPY units driven by hydrogen bonding between the carboxyl groups.
关键词： hydrogen bonding,Self-Assembly,weak non-covalent interactions,BODIPY dyes
更新于2025-09-23 15:21:21
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Supramolecular Photothermal Nanomaterials as an Emerging Paradigm toward Precision Cancer Therapy
摘要： The concept of the “supramolecular photothermal effects” refers to the collection property and photothermal conversion efficiency resulting from the supramolecular assembly of molecular photothermal sensitizers. This review considers organic supramolecular photothermal materials assembled at the nanoscale via various molecular self-assembly strategies and associated with the organization of multiple noncovalent interactions. In these materials, the individual photosensitizer molecules are typically aggregated through self-assembly in a certain form that exhibits enhanced biostability, increased photothermal conversion efficiency with photoluminescence quenching, and improved photothermal therapeutic effects in comparison with those of the monomeric photosensitizer molecules. These supramolecular photothermal effects are controlled or influenced by intermolecular noncovalent interactions, especially the hydrophobic effects, which are distinct from the mechanisms of conventional sensitizer molecules and polymers and inorganic photothermal agents. A focus lies on how self-assembly strategies give rise to supramolecular photothermal effects, including polymer and protein fabrication, small molecule self-assembly, and the construction of donor–acceptor binary systems. Emphases are placed on the rational design of supramolecular photothermal nanomaterials, drug delivery, and in vivo photothermal therapeutic effects. Finally, the key challenges and promising prospects of these supramolecular photothermal nanomaterials in terms of both technical advances and clinical translation are discussed.
关键词： photothermal therapy,nanomaterials,cancer therapy,supramolecular photothermal effects,self-assembly
更新于2025-09-23 15:21:21
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3D graphene aerogels/Sb2WO6 hybrid with enhanced photocatalytic activity under UV- and visible-light irradiation
摘要： A novel ultraviolet (UV)- and visible-light-active 3D graphene aerogels (3DGA)/Sb2WO6 hybrid photocatalyst was prepared by electrostatic self-assembly (ESSA) method. The photocatalytic activity of the 3DGA/Sb2WO6 hybrid was studied by monitoring the change in the concentration of methyl orange (MO) under UV-light and visible-light irradiation. The results demonstrated that the as-prepared hybrid exhibited significantly enhanced efficiency for the photodegradation of MO in comparison with pure Sb2WO6. This was ascribed to the efficient separation of the photogenerated electrons (e–) and holes (h+) with the aid of 3DGA as well as the generated reactive superoxide radical anions (O2(cid:129)–). Moreover, the 3DGA/Sb2WO6 hybrid exhibited high recyclability, because the highly hydrophobic 3DGA in the hybrid was very advantageous to the separation of the hybrid photocatalyst from the MO solutions.
关键词： 3D graphene aerogels,Sb2WO6,Electrostatic self-assembly,Hybrid photocatalyst,Visible-light irradiation
更新于2025-09-23 15:21:21
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Semiconducting Langmuir-Blodgett Films of Porphyrin Paddle-Wheel Frameworks for Photoelectric Conversion
摘要： Understanding the photocurrent transportation within porphyrin-containing metal-organic frameworks (PMOFs) will be a critical step for applying these materials in light-harvesting molecular devices in the future. Two copper porphyrin paddle-wheel frameworks (Cu-PPFs) were employed to study the influence of metal ions coordinated into the porphyrin ligands on conductivity and photoelectron transfer capability. To compare the electronic and optical properties of both materials, we prepared an ultra-thin film of each PPF via a Langmuir-Blodgett method. The resulting films exhibited uniform morphology and single-crystalline domains, in addition to photoelectric conversion capabilities. We confirmed both Cu-PPFs have semiconducting properties with an optical bandgap around 2.7 eV. The current density generated by both Cu-PPFs were studied through a mercury drop junction approach. We observed a slightly higher conductivity from the Cu-PPF film consisting of metalloporphyrins than the one without copper doping in the porphyrin centers. In addition, the copper ions coordinated porphyrins were found to be more favorable for facilitating photo-induced electron transfer from the Cu-PPF film to a conductive glass substrate. This work presents a new approach of combining thin film fabrication and electro-heterojunction measurement to study electron transfer within an ultra-thin film.
关键词： Metal-Organic Framework (MOF),2D Material,Langmuir-Blodgett Film,Self-Assembly,Semiconductor,Porphyrin Thin Film,Photoelectric Conversion
更新于2025-09-23 15:21:21
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p-Doping Poly(3-hexylthiophene) in Solvent Mixtures
摘要： One method to improve the conductivity of conjugated polymers, like poly(3-hexylthiophene) (P3HT), is to “chemically dope” them analogous to inorganic materials. One electron acceptor that has been used in tandem to p-doped P3HT is 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), and recently there has been much interest in the nature of the interactions between F4TCNQ and P3HT in the solution phase. To date, however, there are few reports that investigate the behavior of F4TCNQ-doped P3HT in binary solvent mixtures. The study reported herein is an investigation of F4TCNQ-doped P3HT in mixtures of chloroform (CF) with dichloromethane (DCM) or acetonitrile (AcN), wherein variations in the doping efficiency in these mixtures are observed using UV–vis absorption, Raman, and electron paramagnetic resonance spectroscopic techniques. The contrasting solubility and charge transfer behavior of F4TCNQ-doped P3HT in CF:DCM and CF:AcN show that judicious selection of solvent mixtures may be exploited to improve the doping efficiency and solution processability of p-doped P3HT dispersions.
关键词： dispersions,charge transfer,conjugated polymers,self-assembly
更新于2025-09-23 15:21:21
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A Novel Nanorod Self-Assembled WO <sub/>3</sub> ?· H <sub/>2</sub> O Spherical Structure: Preparation and Flexible Gas Sensor
摘要： In this work, a novel WO3·H2O spherical structure which was self-assembled by nanorods was achieved by using hydrothermal method. A comprehensive growth mechanism was proposed to explain the formation of three different type nanostructures. Flexible gas sensors were successfully fabricated based on such unique nanostructures. We found that these nanorods and nanoparticle’s self-assembled spherical structure showed excellent gas response to ammonia. This result may provide great benefit potential to further study for the preparation and gas performance of such self-assembled structure of WO3·H2O.
关键词： WO3·H2O,Nanostructures,Self-Assembly,Hydrothermal Process,Gas-Sensing
更新于2025-09-23 15:21:01
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Photophysical Properties of Fluorescent Self-Assembled Peptide Nanostructures for Singlet Oxygen Generation
摘要： In this work, a drug delivery system for perillyl alcohol based on the peptide self-assembly containing 3-(2-benzothiazolyl)-7-(diethylamino)coumarin (C6) as a fluorescent additive is obtained, and its photophysical characteristics as well as its release dynamics were studied by steady-state and time-resolved fluorescence spectroscopy. Results proved the dynamics of drug release from the peptide nanostructures and showed that the system formed by the self-assembled peptide and C6, along with perillyl alcohol, presents unique photophysical properties that can be exploited to generate singlet oxygen (1O2) upon irradiation, which is not achieved by the sole components. Through epifluorescence microscopy combined with time-correlated single photon counting fluorescence spectroscopy, the release mechanism was proven to occur upon peptide structure interconversion, which is controlled by environmental changes.
关键词： photophysical properties,perillyl alcohol,drug delivery system,time-resolved fluorescence spectroscopy,fluorescent additive,peptide self-assembly,epifluorescence microscopy,singlet oxygen generation
更新于2025-09-23 15:21:01