MACROMOLECULES
·
2018
·
IF 5.914
Huli Yu,Kai Pan,Jianping Deng
Alkynylated carboxymethylcellulose (A-CMC) was used to construct optically active helical polymer microparticles (spherical and spindle-like) through suspension polymerization of achiral acetylic monomer. Taking advantage of the “sergeant and soldiers rule”, the chirality of A-CMC effectively transferred to the resulting helical polymers, thus inducing the latter to form predominantly one-handed screw sense and endowing the microparticles with optical activity. Simply adjusting the stirring speed in suspension polymerizations provided spherical and spindle-like microparticles. The microparticles were assembled by small spheres, under the guidance of oriented A-CMC macromolecular chains depending on stirring rate. The spherical and spindle microparticles demonstrated different enantio-differentiating release process due to their varied shape. A-CMC concurrently plays three roles in the present study: as stabilizing agent and chiral source for fabricating chiral helical polymer particles and as template for adjusting the particles’ shape. The study provides new approaches to utilize biomacromolecules as chiral source for developing novel chiral bioconjugated materials.
研究领域:
材料科学
·
高分子化学
·
生物材料
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2023
·
IF 17.1
Shuo Ma,Huanyu Ma,Kai Yang,Zhan’ao Tan,Biao Zhao,Jianping Deng
Chiral carbon dots (C-dots) with a circularly polarized fluorescence (CPF) property have attracted tremendous attention due to their significant applications in chiral optoelectronics and theranostics. However, constructing circularly polarized room-temperature phosphorescent (CPRTP) C-dots remains a great challenge. Herein, a strategy is established to achieve efficient CPF and CPRTP emissions in C-dots/chiral helical polymer bilayer composite film. Taking advantage of the chiral filter effect of chiral helical polymer, intense CPF and CPRTP emissions with large dissymmetric factors up to 1.4 × 10–1 and 1.2 × 10–2 are respectively obtained, even though there is only a simple interface contact between the C-dots layer and the chiral helical polymer layer. More importantly, white-color CPF emission and multiple information display and encryption are further realized based on the prepared chiral luminescent composite films.
研究领域:
材料科学
·
光学
·
化学
✓ 已验证
DOI
高影响因子
Advanced Fiber Materials
·
2022
·Vol. 4
·期 6
·1632-1644
·
IF 12.958
Li Pengpeng,Gao Xiaobin,Zhao Biao,Pan Kai,Deng Jianping
Circularly polarized luminescence (CPL)-active nanomaterials have attracted tremendous attention. However, it is still a big challenge to conveniently fabricate multi-color and white CPL-active nanomaterials on a large scale. Herein, a simple and scalable approach to achieve the above goals is presented. Multicolor CPL-active nanofibers are fabricated from chiral helical substituted polyacetylene, achiral fluorescent dyes and polyacrylonitrile via uniaxial electrospinning; the highest luminescence dissymmetry factor ( g lum ) of the resulting nanofibers can reach 10 − 2 . Furthermore, white CPL-active nanofibers are obtained by coaxial electrospinning, in which the resulting core-shell structure has excellent adjustability and can be utilized to physically isolate different fluorescent dyes to reduce energy transfer efficiency; therefore, stable white CPL emissions can be achieved with high g lum values up to 10 − 3 . Notably, the prepared white-emission CPL nanofibrous films show bright white circularly polarized light when coated on UV chips, demonstrating their future application in constructing low-cost and flexible light-emitting devices such as circularly polarized light-emitting diodes. Graphical Abstract
Multi-color tunable and white circularly polarized luminescence (CPL)-active nanofibers are prepared from chiral helical polymers and commercial fluorescence dyes via electrospinning process. The obtained composite nanofibers exhibit considerable luminescence dissymmetry factor ( g lum ), with the highest g lum up to 10 −2 . White circularly polarized light-emitting diodes are further fabricated by packaging the white CPL nanofiber film on UV chip.
研究领域:
材料科学
·
光学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Yanan Wang,Hai Zhong,Biao Zhao,Jianping Deng
Polymerized high internal phase emulsions (polyHIPEs) with circularly polarized luminescence (CPL), as an interesting class of porous materials, are of great significance for the development of CPL porous materials but have not been reported so far. Herein, we report the construction of polyHIPE-based CPL porous materials, taking advantage of an adsorption strategy. The pristine polyHIPEs constructed by chiral helical polymers, which acted as a chiral microenvironment, were fabricated by coordination polymerization of chiral acetylene monomers (R/S-SA) using HIPEs as templates. Achiral fluorescent small molecules were dispersed in the pores of the 3D porous organic chiral polymer matrix provided by polyHIPEs through the adsorption strategy, and CPL-active porous materials with blue, cyan, and green emissions were constructed using a fluorescence-selective absorption mechanism that does not rely on chirality transfer at the molecular level. The maximum luminescence dissymmetry factor (glum) value was −2.6 × 10–2. This work establishes a new and simple way for developing CPL porous materials.
研究领域:
材料科学
·
光学
·
化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ANALYTICA CHIMICA ACTA
·
2022
·
IF 6.911
Datong Wu,Cong Ma,Ting Wan,Pengfen Zhu,Yong Kong
In most cases, the recognition efficiency of chiral electroanalysis relies on the chiral carbon center, whereas its medium is just used to transfer the electron. Differently, in this study, an ionic helical polymer with right- or left-handed configuration was prepared via an acid-base interaction between the ionic polymer and enantiopure 1,2-diphenylethane-1,2-diamine. The structure and absolute handedness of the helical polymers were well characterized by the circular dichroism spectrum, gel permeation chromatography , and Fourier transform infrared spectroscopy . The pyridinium moiety of the helical polymer contributes to the electron transfer when it was directly modified on the surface of the glassy carbon electrode as an electrochemical enantioselector for chiral electroanalysis. Results indicated that different configurations of amino acids can be recognized in the responses of different electric signals, namely peak current or peak potential. The peak current ratio between L- and d -isomer can be up to 7.5 and 23.2 for tryptophan and tyrosine , respectively. Most importantly, the reversal of the electric signal can be observed toward L- and d -isomer under the different testing conditions such as pH and metal ion content, because of two stereogenic centers (the chiral inducer and the stereogenic axis) in the helical polymer. Overall, we believe that the present study offers a great promise for the synthesis and application of the ionic helical polymers accompanying with multiple stereogenic centers.
研究领域:
化学
·
材料科学
·
分析化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2011
·Vol. 21
·期 12
·2345-2350
·
IF 8.508
Bo Chen,Jianping Deng,Wantai Yang
This article reports for the first time a novel category of hollow organic@inorganic hybrid two-layered nanoparticles (NPs), in which the inner layer is formed by optically active helical polyacetylene, and the outer layer by silica. Such NPs show remarkable optical activity and are successfully used for enantioselective crystallization. To prepare such NPs, n -butyl acrylate undergoes radical polymerization to first form poly(n-butyl acrylate) (PBA) cores two shells by catalytic polymerization of substituted acetylene and sol–gel approach of TEOS (tetraethyl orthosilicate), respectively. Removal of the PBA cores provides the expected hollow core/shell NPs. The intense dircular dichroism (CD) effects demonstrate that the hollow chiral NPs possess considerable optical activity, arising from the helical substituted polyacetylenes forming the inner layer. The hollow NPs are further used as chiral templates to induce enantioselective crystallization of racemic alanines, demonstrating the significant potential applications of the hollow chiral NPs in chiral technologies. Also of particular significance is the detailed process of the induced crystallization observed by TEM. The strategy for preparing the hollow hybrid chiral NPs should be highlighted since it combines free radical polymerization and catalytic polymerization with sol–gel process in a single system, by which numerous advanced materials will be accessible.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULES
·
2016
·
IF 5.554
Junjiang Li,Min Du,Zhongqiang Zhao,Hewen Liu
Synthetic polymers mimicking the stimuli-responsive coiled-coil structures of naturally occurring macromolecules such as motor proteins remain challenging. Here we report that chirality switchable quasi-double helical polymers can be synthesized by the free radical cyclopolymerization of the tetramethyldisiloxane-tethered divinyl monomers. Two cyclopolymers (pbSt and pbMA) are obtained in this work, which in solid state are helical polymers investigated by both ECD and VCD. According to VCD analysis, the C–H deformation modes including C–H bending (mode I) and C–H rocking (mode II) in the main-chain helix show strong signals in VCD spectra and the plots of the division of VCD by IR, which have different responses to solvation histories or thermal treatment compared with other vibrational signals arising from side rings (especially signals from tetramethyldisiloxane groups). After thermal treatment, all the side-ring VCD signals of both pbSt and pbMA are inverted, while the VCD signals from mode II of the main chain are unchanged. In cast films from chloroform solutions, pbSt shows only and inverted VCD signals arising from mode I and mode II of the main-chain helix, but not any VCD signals from side rings. Ab initio quantum calculation reveals that the change in the orientation of side-ring distortion against the main chain may account for the inversion of side-ring VCD signals. The responses of the experimental VCD spectra of the cyclopolymers can thus be rationalized based on the quantum calculation results. The main-chain helices of the cyclopolymers remained unchanged, while the side rings changed their distortion orientation during thermal treatment. In cast films from chloroform solutions, the polymer main-chain helix was inverted, hence inverted main-chain VCD; while the side rings might be randomly distorted, causing loss of VCD from side rings. Overall, the main-chain helices and side-ring pseudohelices can be switched independently. This work presents the first example that a single macromolecule can display such (quasi-)double-helical conformation. Besides the theoretical value, this kind of chirality switchable quasi-double-helical polymer may find application in asymmetric catalyst, smart molecular devices, etc.
研究领域:
高分子化学
·
物理化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULES
·
2023
·
IF 5.5
Xueting Lu,Yunli Liu,Dongxu Lu,Anqiu Xu,Yuexin Cao,Xiacong Zhang,Wen Li,Afang Zhang
Helical polymers with dynamic chirality are interesting not only for understanding the relationship between polymer structure and chiral conformation but also for developing responsive chiral polymeric materials. We report here the synthesis and characterization of a homologous series of dendronized poly(phenylacetylene)s (PPAs) via both macromonomer and grafting-to routes. These copolymers consist of achiral units carrying dendritic oligoethylene glycol (OEG) pendants and chiral units of dynamic imines formed from aldehydes and amino acids, which combine the constitutional dynamic chemistry (Schiff base) in the pendants with the conformational dynamic PPA backbones. Dendritic OEG pendants endow these copolymers with characteristic thermoresponsive behavior. The principles for modulating the helicity of these dendronized copolymers were examined, and factors including molecular structures (copolymer compositions and pendant linkage via ester or amide), solution pH, and thermally induced phase transitions have been investigated. These copolymers adopt tailored helicities in the presence of additional amino acids through multiple interaction balances between the copolymers and the amino acids. We believe that the methodology developed in this work will pave a convenient way to afford optically inactive copolymers or active polymers with featured dynamic helicity.
研究领域:
高分子化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Photonics Research
·
2021
·Vol. 2
·期 8
·2100018
·
IF 0
Ning Shen,Mengting Hu,Xiao-Qian Wang,Pei-Zhi Sun,Cong-Long Yuan,Binghui Liu,Dong Shen,Zhi-Gang Zheng,Quan Li
Volatility monitoring of a tiny amount of organic solvent, which reflects the profound understanding of the micro-environmental chemical physics effect, plays a significant role in chemical reactions. Common approaches, such as microfluidic technology, undeniably encounter the issue of complicated fabrication or high cost, impeding their large-scale application for monitoring the processes of chemical physics in micro-reactions. Herein, a helical polymer film (HPF) molded by a cholesteric liquid crystal (CLC) is reported to record the helical arrangement. By infiltrating less than 1.0 μL volatile solvent into the HPF and monitoring the corresponding reflection spectral behaviors, an intrinsic dynamic chemical physics process, solvent properties, and molecular interactions between the solvent and the polymer network are quantitatively evaluated. Furthermore, to further explore the underlying interaction mechanism that results in spectral band shift, a dynamical model is established and elucidated, providing remarkable information and understanding of the dynamic chemical physics processes and interfacial molecular interactions between the solvent and the polymer. This work has tied a close bond among chemical engineering, photonics, and soft condensed physics, which can provide an avenue for the new field of application of LC photonics beyond display and optics.
研究领域:
化学工程
·
光子学
·
软凝聚态物理
✓ 已验证
产品关联
DOI
POLYMER
·
2018
·
IF 3.483
Huajun Huang,Huilei Wang,Youping Wu,Yan Shi,Jianping Deng
Owing to the ever-rising importance of chirality , chiral polymeric spheres are becoming especially attractive for both chirality and material scientists. The microspheres consisting of helical polymers , e.g. substituted polyacetylenes , are particularly intriguing because their chirality not only originates in pendant chiral groups, but also originates in one-handed helical polymer backbones. Unfortunately, the size of such spheres is limited, and their crosslinking is a huge challenge; specifically, preparing chiral crosslinked microspheres ( CCMs ) of substituted polyacetylenes with diameter of 1–50 μm remains as an intractable task. In this work, such CCMs (with diameters of 1.3–2.3 μm) were successfully prepared for the first time through precipitation polymerization. Circular dichroism and UV-vis absorption spectra demonstrate that the chirality of CCMs not only simply originates in the monomer units, but also originates in the chirally helical structures of the polymer. The CCMs thus have the potential to be applied as chiral stationary phase for high-performance liquid chromatography. Based on macroscopic and microscopic observations, a mechanism for the precipitation polymerization of acetylenic monomers in the presence of crosslinker is proposed. The present study provides new opportunities for designing and synthesizing functional CCMs constructed from helical polymers.
研究领域:
材料科学
·
聚合物化学
·
分析化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）