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result(s) for
"chiral polymer"
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Synthesis of Main-Chain Chiral Quaternary Ammonium Polymers for Asymmetric Catalysis Using Quaternization Polymerization
by
Parvez, Md. Masud
,
Itsuno, Shinichi
,
Haraguchi, Naoki
in
Catalysis
,
chiral polymer
,
Chromatography
2012
Main-chain chiral quaternary ammonium polymers were successfully synthesized by the quaternization polymerization of cinchonidine dimer with dihalides. The polymerization occurred smoothly under optimized conditions to give novel type of main-chain chiral quaternary ammonium polymers. The catalytic activity of the polymeric chiral organocatalysts was investigated on the asymmetric benzylation of N-(diphenylmethylidene)glycine tert-butyl ester.
Journal Article
Aggregation‐induced emission polymer systems with circularly polarized luminescence
by
He, Youling
,
Han, Ting
,
Wang, Dong
in
aggregation‐induced emission
,
Catalysis
,
chiral polymers
2023
Functional materials with circularly polarized luminescence (CPL) have attracted tremendous attention due to their promising applications in three‐dimensional displays, chiral recognition and catalysis, photoelectronic devices, contrast imaging, information encryption, and other fields. Among various CPL‐active materials, polymeric systems with aggregation‐induced emission (AIE) have emerged as excellent candidates because of their efficient aggregate‐state fluorescence, large solid‐state dissymmetry factor, excellent processibility, diversified self‐assembly behaviors, and readily switchable CPL properties. This review summarizes and discusses the recent progress as well as future perspective of diverse AIE polymer systems with CPL, including CPL‐active covalent AIE polymers, CPL‐active supramolecular AIE polymers, and AIEgen/polymer composites with CPL. According to the location or introduction method of AIEgen in polymer structures, this review further divides CPL‐active covalent AIE polymers into three categories, including polymers with AIEgen in main chains, polymers with AIEgen in side chains, and CPL‐active polymers with clusterization‐triggered emission. CPL‐active supramolecular AIE polymers are discussed based on the driving force for the formation of supramolecular polymers, including host–guest interactions, metal coordination, and other non‐covalent interactions. Moreover, examples on the construction of CPL‐active AIEgen/polymer composites by physically mixing AIEgens with chiral (supra)polymers are also presented. This review is anticipated to provide readers with an overall view on the design strategies of CPL‐active AIE polymers, and facilitate further research on the development of CPL materials and AIE polymers with advanced applications. Aggregation‐induced emission (AIE) polymer systems with circularly polarized luminescence (CPL) have significant advantages in terms of fluorescence quantum yields, dissymmetry factor, and readily tunable CPL activity. This review discusses the recent progress on CPL‐active AIE polymers, including CPL‐active covalent AIE polymers, CPL‐active supramolecular AIE polymers, and AIEgen/polymer composites with CPL.
Journal Article
Synthesis and Characterization of Multilayer 3D Chiral Polymers with Enhanced Optical Properties
by
Li, Guigen
,
Mao, Jialing
,
Zhang, Yue
in
aggregation-induced emission
,
Chromatography
,
Electrodes
2025
This study reports the synthesis of novel multilayer 3D chiral polymers using 2,2′-(2,7-Naphthalenediyl)bis[4,4,5,5-tetramethyl-1,3,2-dioxaborolane] and 1,8-dibronaphthalene along with its derivatives as key precursors. Comprehensive characterization was performed using nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), photoluminescence, ultraviolet (UV) spectroscopy, scanning electron microscopy (SEM), polarimetry, dynamic light scattering (DLS), and thermogravimetric analysis (TGA). Notably, the polymers exhibited remarkable aggregation-induced emission (AIE) and aggregation-induced polarization (AIP) phenomena, revealing enhanced luminescence and optical activity in aggregated states. These findings underscore the potential of these chiral polymers for applications in optoelectronics and advanced sensing technologies, highlighting the intricate relationship between molecular structure and optical behavior.
Journal Article
Chiral polymer micro/nano-objects: evolving preparation strategies in heterogeneous polymerization
2025
Chirality is a fundamental geometric property prevalent in nature, spanning from biomolecules to macroscopic structures. This review explores the rapidly evolving field of chiral polymer micro/nano-objects, which are increasingly applied in chiral recognition, asymmetric catalysis, and circularly polarized luminescence. Conventional heterogeneous polymerization techniques—such as emulsion, precipitation, dispersion, and suspension polymerizations—have emerged as powerful methods for preparing these chiral micro/nano-objects. Additionally, the polymerization-induced chiral self-assembly strategy based on living heterogeneous polymerization has attracted attention for its efficiency and versatility in producing well-defined chiral polymer assemblies with tunable morphologies. This review summarizes recent advances in these preparation strategies, emphasizing the importance of heterogeneous polymerization in developing chiral polymer materials with enhanced optical and functional properties.
Journal Article
Chiral Polymer-Mediated Pd@MOF-808 for Efficient Sequential Asymmetric Reaction
2023
The design and construction of organocatalysts that combined the homogeneous and heterogeneous natures to realize efficient catalysis are highly desired and challenging. Functionalized-polymers, a kind of flexible materials, provide a platform to modulate the states of immobilized catalysts in rigid supports. Herein, a chiral polymer (CP) mediated catalyst containing Pd NPs have been reported (CP@Pd@MOF-808). Chiral active sites were anchored on the polymer, and the chiral polymer threaded within the host pores of MOFs to promise the homogeneousness of chiral sites in a heterogeneous support MOF-808. This strategy kept the flexibility and freedom of chiral sites after immobilization, thus exhibited comparable performances with the corresponding homogeneous catalyst. The well-designed CP@Pd@MOF-808 was applied to sequential asymmetric reactions with excellent reactivity and stereoselectivity (up to 89% yields and 95% ee values), which were even better than that of homogeneous catalyst.A rationally designed Chiral Polymer-Mediated MOF catalyst containing metal NPs was developed for sequential reaction with high efficiency.
Journal Article
Chiral Polymers Based on Vinyl2.2paracyclophane and Their Application as CPL Emitters
by
Zysman-Colman, Eli
,
Crassous, Jeanne
,
Bräse, Stefan
in
Active mirrors
,
Carbon
,
Cationic polymerization
2025
Chiral molecules are integral to various biological and artificial systems, influencing processes from chemical production to optical activities. In this study, we explore the potential of chiral vinyl[2.2]paracyclophane (vinyl-PCP) as a monomer for the synthesis of homopolymers and copolymers with styrene. We achieved polymerization through anionic, cationic, and radical methods. The resulting polymers demonstrated significant chiral properties, even in copolymers with small fractions of the chiral monomer. Further, we developed a polymerizable vinyl emitter from 10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9,9-dimethyl-9,10-dihydroacridine (DMAC-TRZ) through a two-step synthesis with an overall yield of 48%. Copolymerization with chiral vinyl-PCP resulted in emissive polymers that demonstrated circularly polarized luminescence (CPL) properties. The inclusion of the chiral PCP monomer, acting both as a host material and the source of chirality for CPL, enhanced the photoluminescence quantum yield (PLQY) to 47.2% in N2 at 5–10% emitter content, compared to 26.8% for the pure emitter polymer. CPL-active polymers show clear mirror-image Cotton effects at 240 nm and 267 nm and dissymmetry factors around +2 × 10−4 and −1 × 10−4. This self-hosting effect of PCP monomers underscores the potential of chiral vinyl-PCP for advanced functional materials in optical communication and bio-responsive imaging.
Journal Article
New Insights on Solvent-Induced Changes in Refractivity and Specific Rotation of Poly(propylene oxide) Systems Extracted from Channeled Spectra
by
Stoica, Iuliana
,
Albu, Raluca Marinica
,
Dimitriu, Dan Gheorghe
in
Acetates
,
Chemical bonds
,
Density functionals
2024
Investigation of chiroptical polymers in the solution phase is paramount for designing supramolecular architectures for photonic or biomedical devices. This work is devoted to the case study of poly(propylene oxide) (PPO) optical activity in several solvents: benzonitrile, carbon disulfide, chloroform, ethyl acetate, and p-dioxane. To attain information on the interactions in these systems, rheological testing was undertaken, showing distinct variations of the rheological parameters as a function of the solvent type. These aspects are also reflected in the refractive index dispersive behavior, from which linear and non-linear optical properties are extracted. To determine the circular birefringence and specific rotation of the PPO solutions, the alternative method of the channeled spectra was employed. The spectral data were correlated with the molecular modeling of the PPO structural unit in the selected solvents. Density functional theory (DFT) computational data indicated that the torsional potential energy—related to the O1-C2-C3-O4 dihedral angle from the polymer repeating unit—was hindered in solvation environments characterized by high polarity and the ability to interact via hydrogen bonding. This was in agreement with the optical characterization of the samples, which indicated a lower circular birefringence and specific rotation for the solutions of PPO in ethyl acetate and p-dioxane. Also, the shape of optical rotatory dispersion curves was slightly modified for PPO in these solvents compared with the other ones.
Journal Article
Development of chiral functional materials based on natural chiral compounds
2022
Optically active polymers and supramolecules that form well-defined assemblies and architectures are important materials with a wide range of applications. Among the variety of chiral building blocks for the preparation of optically active functional materials, amino acids and sugars stand out because of their versatile structures and functional groups. In these chiral units, intra- and intermolecular noncovalent interactions, such as hydrogen bonding and π-stacking, play significant roles in the generation of smart functions. This review summarizes the fabrication and functions of chiral conjugated polyacetylenes and polyarylene ethynylenes and chiral supramolecules based on these natural chiral compounds.Optically active polymers and supramolecules that form well-defined architectures are important materials with a wide range of applications. Amino acids and sugars are great candidates for the preparation of optically active functional materials because of their versatile structures and functional groups. In these chiral units, intra- and intermolecular noncovalent interactions play significant roles in the generation of smart functions. In this focus review, the author reviews his recent studies related to the fabrication and functions of chiral conjugated polymers and chiral supramolecules based on these natural chiral compounds.
Journal Article
Chiral polymer modified nanoparticles selectively induce autophagy of cancer cells for tumor ablation
2018
Background
Autophagy regulation through exogenous materials has aroused intensive attention to develop treatment protocols according to diverse human diseases. However, to the best of our knowledge, few examples have been reported to selectively control autophagy process and ultimately achieve efficient therapeutic potential.
Results
In this study, monolayers of poly (acryloyl-
l
,
d
and racemic valine) (
l
-PAV-AuNPs,
d
-PAV-AuNPs and
l
/
d
-PAV-AuNPs) chiral molecules were anchored on the surfaces of gold nanoparticles (PAV-AuNPs), and the subsequent chirality-selective effects on autophagy activation were thoroughly studied. The cytotoxicity induced by PAV-AuNPs towards MDA-MB-231 cells (Breast cancer cells) was achieved mainly through autophagy and showed chirality-dependent, with
d
-PAV-AuNPs exhibiting high autophagy-inducing activity in vitro and in vivo. In contrast, the PAV-AuNPs exhibited autophagy inactivation for normal cells, e.g., 3T3 fibroblasts and HBL-100 cells. The chirality-selective autophagy activation effect in MDA-MB-231 cells was likely attributed to the chirality-variant ROS generation, cellular uptake and their continuous autophagy stimulus. Furthermore, the intratumoral injection of
d
-PAV-AuNPs could largely suppress the tumor growth but exhibit negligible toxicity in vivo.
Conclusions
As the first exploration on stereospecific NPs for autophagy induction, this work not only substantiates that chiral polymer coated NPs can selective induce autophagy-specific in cancer cells and achieve a high tumor eradication efficiency in vivo, but also opens up a new direction in discovering unprecedented stereospecific nanoagents for autophagy-associated tumor treatment.
Journal Article
A New Class of Chiral Polyethers and Polyesters Based on the 2.2Paracyclophane Scaffold
2024
Over the past decades, the research on optically active polymers (OAPs) has significantly grown, and extensive studies have been carried out on their syntheses, conformations, and applications. The most commonly used OAPs are based on natural products such as sugars or amino acids, which limits their scope. A broader range of applications can be achieved by synthesizing lab-tailored monomers, which allow precise control over structure and properties. This research developed a four-step synthetic route to a previously unreported chiral [2.2]paracyclophane-based epoxide monomer. An aluminum catalyst and an alkylammonium initiating system were applied and optimized for its polymerization to provide access to a novel class of chiral polyethers. Furthermore, we demonstrated the copolymerization viability of the (4-[2.2]paracyclophanyl)oxirane monomer using phthalic anhydride.
Journal Article