Constructing circularly polarized luminescence (CPL) materials that exhibit dynamic handedness inversion and emissive color modulation for multimodal information encryption presents both a significant challenge and a compelling opportunity. Here, we have developed a pyridinethiazole acrylonitrile-cholesterol derivative (Z-PTC) that exhibits wavelength-dependent photoisomerization and photocyclization, enabling dynamic handedness inversion and emissive color modulation in supramolecular assemblies with decent CPL activity. Coordination with Ag ions form the Z-PTC Ag supramolecular polymer (SP), which assembles into nanotubes displaying enhanced positive yellow-green CPL.
View Article and Find Full Text PDFIt remains challenging to elucidate the fundamental mechanisms behind the dynamic chirality inversion of supramolecular assemblies with pathway complexity. Herein, metal coordination driven assembly systems based on pyridyl-conjugated cholesterol (PVPCC) and metal ions (Ag or Al) are established to demonstrate pathway-directed, recyclable chirality inversion and assembly polymorphism. In the Ag(I)/PVPCC system, a competitive pathway leads Ag-Complex to form either kinetically controlled supramolecular polymer (Ag-SP I) or thermodynamically favored Ag-SP II, accompanied by reversible chiroptical inversion.
View Article and Find Full Text PDFConstructing full-color circularly polarized luminescence (CPL) materials with switchable handedness in the solid state is an appealing yet considerably challenging task, especially for supramolecular polymer films assembled from homochiral monomers. Herein, supramolecular polymers with full-color CPL and inverted handedness are realized through the coassembly of a homochiral cholesterol derivative (PVPCC), metal ions (Zn), and achiral fluorescent dyes. The obtained coassembled systems show anion-directed supramolecular chirality inversion by exchanging the anions of NO, ClO, BF, and Cl.
View Article and Find Full Text PDFChem Commun (Camb)
November 2023
Metal-organic supramolecular polymers (MOSPs) with multicolor circularly polarized luminescence (CPL) and handedness inversion were constructed from the coordination-driven assembly of pyridine-cyanostilbene-cholesterol and metal salts by modulating the treatment modes, solvents, and metal ions.
View Article and Find Full Text PDFACS Appl Mater Interfaces
August 2023
It is important to identify the effect of assembly and aggregation on the chirality transfer and energy transmission in supramolecular polymer system, since the unordered aggregation is insufficient to promote luminescence enhancement and chirality transfer, even causing the negative effect. Another key issue is to identify the solvent effect on hierarchically chiral self-assembly. Herein, we designed an AIE-core based building block, tetraphenylpyrazine-cholesterol (TPP-Chol), to explore how the solvent component influences chirality transfer and energy transmission of its aggregates and/or assemblies.
View Article and Find Full Text PDFThe study of dynamic supramolecular chirality inversion (SMCI) not only helps to deepen the understanding of chiral transfer and amplification in both living organizations and artificially chemical self-assembly systems but also is useful for the development of smart chiral nanomaterials. However, it is still challenging to achieve the dynamic SMCI of the self-aggregation of metal-organic supramolecular polymers with great potential in asymmetric synthesis, chiroptical switches, and circular polarized luminescence. Here, we successfully developed a hierarchical coassembly system based on the PAzPCC and various metal ions with effective chirality transfer and temporal-controlled SMCI.
View Article and Find Full Text PDFBased on a metal coordination driven co-assembly strategy, a metal-organic supramolecular polymer system of pyridine Schiff-base cholesterol and metal ions with multiple supramolecular chirality inversion was successfully achieved by the stoichiometry and exchange of metal ions (such as Co, Ni, Cu, Zn, and Ag), as well as the solvent polarity.
View Article and Find Full Text PDFLight is essential to all life on the earth. Thus, highly efficient light-harvesting systems with the sequential energy transfer process are significant for using solar energy in photosynthesis. For developing an efficient light-harvesting system, a liquid aggregation-induced emission (AIE) dye TPE-EA is obtained, as a donor and solvent, which can light up the aggregation caused quenching (ACQ) Nile Red (NiR, acceptor) to construct a quantitative Förster resonance energy transfer (FRET) system in NiR⊂TPE-EA.
View Article and Find Full Text PDFBalancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal-optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system.
View Article and Find Full Text PDFThe development of circularly polarized luminescent materials with a large luminescence dissymmetry factor (g) is continuing to be a big challenge. Here, we present a general approach for amplifying circular polarization of circularly polarized luminescence (CPL) through intergrating molecular self-assembly and surface plasmon resonance (SPR). Molecular self-assembly could amplify the CPL performance.
View Article and Find Full Text PDFHighly expressed in cancer 1 (Hec1) plays an essential role in mitosis and is correlated with cancer formation, progression, and survival. Phosphorylation of Hec1 by Nek2 kinase is essential for its mitotic function, thus any disruption of Hec1/Nek2 protein-protein interaction has potential for cancer therapy. We have developed T-1101 tosylate (9j tosylate, 9j formerly known as TAI-95), optimized from 4-aryl-N-pyridinylcarbonyl-2-aminothiazole of scaffold 9 by introducing various C-4' substituents to enhance potency and water solubility, as a first-in-class oral clinical candidate for Hec1 inhibition with potential for cancer therapy.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2019
A luminescent liquid crystal molecule (TPEMes) with efficient solid-state emission is rationally constructed via the chemical conjugation of blue-emitting tetraphenylethene cores and luminescent mesogenic tolane moieties, which are both featured with aggregation-induced emission properties. As for this fluorophore, aggregation-induced energy transfer from the emissive tolane mesogens to the lighting-up tetraphenylethene units endows the molecule pure blue emission in the suspension and bulk state. Combining differential scanning calorimetry, polarized optical microscope, and one-dimensional X-ray diffraction (1D XRD) experiments, the compound TPEMes is deduced to adapt thermodynamically more stable layered crystalline phase and can be "frozen" into a monotropic smectic mesophase due to kinetic reasons.
View Article and Find Full Text PDFThis study examined the moderation of classroom ethnic composition and the mediation of group identification in the relationships between upward comparisons, depression, and self-efficacy in a sample of 359 Taiwanese aboriginal students. A stronger negative effect was found in highly ethnically concentrated classes. Upward comparisons were found to reinforce depression, decrease self-esteem, and reduce school belonging in aborigines-only classes but not in mainstream classes.
View Article and Find Full Text PDFThis study aimed to elucidate whether the interaction of classroom composition and the need to belong influences belongingness seeking and, if so, to investigate how upward comparison mediates the effects. The analyses were conducted with a cross-sectional sample of 383 Taiwanese aboriginal adolescents (39.7% male) recruited from schools with mixed-sex/ethnicity (n = 113), single-sex (n = 122), and minority-only (n = 148) classrooms.
View Article and Find Full Text PDFA series of 3-O-acylated (-)-epigallocatechins were synthesized and their inhibition of steroid 5α-reductase was studied. They were prepared from the reaction of EGCG with tert-butyldimethylsilyl chloride followed by reductive cleavage of the ester bond. The resultant (-)-epigallocatechins penta-O-tert-butyldimethylsilyl ether was esterified with different fatty acids then desilylated to provide the corresponding products.
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