Stimuli-responsive helical polymeric particles with amplified circularly polarized luminescence

Duan, Huimin; Pan, Hongkun; Li, Jiawei; Qi, Dongming

doi:10.1039/d2tc04292d

Cited by 11 publications

(6 citation statements)

References 61 publications

(74 reference statements)

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“…Inspired by natural helical biomacromolecules, researchers put their enormous efforts toward breaking nature’s monopoly by producing synthetic helical polymers with a diversified helical conformation. In recent years, synthetic polymers with controlled helicity have found significant interest in various potential applications such as chiral resolution and recognition, − asymmetric catalysis, − circularly polarized luminescence, − enantioselective absorption/release, , etc.…”

Section: Introductionmentioning

confidence: 99%

Polymers Bearing Covalently Linked Chiral Proline-Based Pendants: Induction of a Highly Stable Helical Sense that Mimics Double-Stranded Helical Morphology and Their Chiral Resolution Ability

Tilottama,

Vijayakrishna

2024

Macromolecules

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Synthesis of common organic polymers bearing a helical sense in aqueous media is still an inflexible area. Here, we report proline-derived imidazolium-functionalized water-soluble, highly stable chiral polymers/chiral polyelectrolytes whose chiral pendant groups exist at the cation part of the polymer chains with different counteranions. Despite chiral pendants, chiral polymers with chloride counteranions did not respond to circular dichroism (CD) absorption spectroscopy, which suggests that they exist as random coils. Interestingly, hydroxy-containing poly-(L-)-2-OH and poly-(D-)-2-OH showed two intense CD signals (with opposite loops), suggesting that the hydroxyl anion facilitates the noncovalent interactions in the chiral polymers to realize this "random coil to helical" transformation, which failed with the chloride anion. L-Prolinate-substituted polymers (poly-(L-)-2-OH) showed a positive Cotton effect with a double-stranded, right-handed helical sense in the presence of achiral and chiral counteranions. Under identical conditions, D-prolinate-substituted chiral polymers (poly-(D-)-2-OH) showed a negative Cotton effect with a left-handed helical sense, which is exactly opposite to its counterpart. This study discusses the influence of the type of chiral center on a preferred helical sense and tries to establish the influence of chirality at the main chain vs side chain on the type and extent of helicity. The synthesized chiral polymers were successfully used for the chiral resolution of racemic D,L-alanine through enantioselective crystallization. These helical polymers showed good enantio-separation efficiency with an enantiomeric excess (ee) of up to 90%. Here, we demonstrated that by selective choice of the chiral helical polymers, a targeted enantiomer could be recrystallized.

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Section: Introductionmentioning

confidence: 99%

Polymers Bearing Covalently Linked Chiral Proline-Based Pendants: Induction of a Highly Stable Helical Sense that Mimics Double-Stranded Helical Morphology and Their Chiral Resolution Ability

Tilottama,

Vijayakrishna

2024

Macromolecules

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“…These self-assemblies can undergo structural changes in response to temperature variations, thereby altering their chiroptical properties. Additional strategies have involved the design and synthesis of temperature-sensitive chiral molecules [25] , helical polymers [26] , hydrogel [27] , and chiral macrocycles [28] that are covalently linked with emitters. However, the successful implementation of thermo-responsive CPL characteristics in materials is limited, and existing examples often necessitate precise design and complex synthesis, which can be lacking in versatility.…”

Section: Introductionmentioning

confidence: 99%

Thermochromic Circularly Polarized Luminescence via Chiral AIEgen-loaded Microcapsules for Adaptive Camouflage and Security

Chen,

Liu,

Zhang

et al. 2024

Preprint

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Stimuli-responsive circularly polarized luminescence (CPL) materials show great promise for dynamic camouflage, information encryption, and smart sensing. However, synthesis complexity and limited practical versatility hinder current research. This study demonstrates novel thermochromic CPL microcapsules (MCs) that contain chiral aggregation-induced emission luminogens (AIEgens) doped alkane phase change materials (PCMs). The synthesized AIEgens, characterized by a high photoluminescence quantum yield of 73.3% and obvious chiroptical properties, were successfully incorporated into PCMs to form thermochromic CPL materials. Microencapsulation of the AIEgen-doped PCMs effectively addressed practical concerns of leakage and corrosion, yielding stable and thermally reliable MCs. These MCs exhibited versatility across diverse polymeric matrices and substrate surfaces, highlighting their adaptability. Leveraging the thermochromic CPL properties, 2D and 3D information encryption systems based on MC-embedded coatings were developed, ensuring high-level data security. Furthermore, their application in high-end camouflage effectively adapted military vehicle coatings to diverse environmental terrains, improving stealth and survivability. The easy scalable fabrication and multifunctionality of these thermochromic CPL MC-embedded coatings hold transformative potential for security and defense applications, offering innovative solutions for protecting sensitive information and concealing military assets.

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“…This is because noncovalent interactions and dynamic covalent bonds are susceptible to dissociation in response to stimuli, which can lead to detectable macroscopic changes in materials properties. Dynamic covalent bonds such as disulfide bonds, [76‐79] borate ester bonds, [80‐84] Schiff base bonds, [85‐90] and noncovalent interactions such as coordination bonds, [91‐93] ionic bonds, [94‐96] hydrogen bonds, [97‐104] halogen bonds, [105,106] hydrophobic interactions, [107‐109] conjugated π – π stacking interactions, [110] electrostatic interactions, [111‐114] and host–guest interactions [115‐123] have shown to be effective in constructing stimuli‐responsive materials. Among them, coordination bonds, which form between a metal providing an empty orbital and a ligand providing lone pairs, are particularly interesting.…”

Section: Introductionmentioning

confidence: 99%

“…This is because noncovalent interactions and dynamic covalent bonds are susceptible to dissociation in response to stimuli, which can lead to detectable macroscopic changes in materials properties. Dynamic covalent bonds such as disulfide bonds, [76][77][78][79] borate ester bonds, [80][81][82][83][84] Schiff base bonds, [85][86][87][88][89][90] and noncovalent interactions such as coordination bonds, [91][92][93] ionic bonds, [94][95][96] hydrogen bonds, [97][98][99][100][101][102][103][104] halogen bonds, [105,106] hydrophobic interactions, [107][108][109] conjugated π-π stacking interactions, [110] electrostatic interactions, [111][112][113][114] and host-guest interactions [115][116][117][118][119][120][121]…”

Section: Introductionmentioning

confidence: 99%

Responsive materials based on coordination bonds

Chen,

Zhao,

et al. 2023

Responsive Materials

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Responsive materials can respond to different external stimuli by changing their chemical or/and physical properties, thus being useful for various applications such as drug delivery, bioimaging, actuators, and sensors. A common strategy for constructing responsive materials is to introduce dynamic covalent bonds or noncovalent interactions into polymer systems. Compared with noncovalent interactions and other covalent bonds, coordination bonds have the peculiarity that their bond strength and dissociation rate can be tuned to a greater extent. Such tunability makes coordination bonds uniquely advantageous in constructing stimuli‐responsive materials. Herein, we summarize the recent progress of responsive materials based on coordination bonds that are classified into seven categories, that is, thermo‐responsive, photo‐responsive, electro‐responsive, mechano‐responsive, chemo‐responsive, pH‐responsive, and other responsive materials, according to the type of external stimuli. The corresponding mechanism, design strategy, and research status of each category are comprehensively summarized. Finally, the prospects and challenges for the development of stimuli‐responsive materials based on coordination bonds are discussed.

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Stimuli-responsive helical polymeric particles with amplified circularly polarized luminescence

Abstract: The stimuli-responsive circularly polarized luminescence (CPL) property is highly desirable in the development of advanced multifunctional optical materials. However, the fabrication of CPL solid materials showing stimuli-responsive behavior in terms...

Cited by 11 publications

References 61 publications

Polymers Bearing Covalently Linked Chiral Proline-Based Pendants: Induction of a Highly Stable Helical Sense that Mimics Double-Stranded Helical Morphology and Their Chiral Resolution Ability

Polymers Bearing Covalently Linked Chiral Proline-Based Pendants: Induction of a Highly Stable Helical Sense that Mimics Double-Stranded Helical Morphology and Their Chiral Resolution Ability

Thermochromic Circularly Polarized Luminescence via Chiral AIEgen-loaded Microcapsules for Adaptive Camouflage and Security

Responsive materials based on coordination bonds

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