A series of full-color circularly polarized luminescence (CPL)-active materials are fabricated by judiciously combining multifarious chiral nanoarchitectures with achiral fluorescence dyes. The investigated nanoarchitectures include organic polymer nanofibers, organic−inorganic hybrid nanoflowers, and inorganic nanoflowers. The as-prepared chiral nanoarchitectures all can act as handed-selective fluorescence filters to powerfully transform unpolarized fluorescent light into circularly polarized luminescence. Also notable, no interaction is required between chiral and fluorescent components for achieving CPL emission. The present study provides a convenient and universal approach for preparing full-color CPL materials. Following the strategy, numerous chiroptical materials with CPL performance can be expected due to the abundant chiral matters and achiral fluorophores.
To
take advantage of the chirality of cellulose nanocrystals (CNCs) and
to develop novel chiral polymer materials, alkynylated CNCs (alkynyl-CNCs)
were prepared and copolymerized with an achiral acetylenic monomer
through suspension polymerization in aqueous media. The chirality
of the alkynyl-CNCs was efficiently transferred to racemic helical
polymer chains, by which inducing predominantly one-handed polymer
helicity. Moreover, alkynyl-CNCs simultaneously acted as a comonomer
and stabilizing agent, directly providing optically active microparticles
(400–800 μm) constructed by chirally helical polymer
chains. So the alkynylated CNCs played triple roles in our strategy:
chiral source, comonomer, and stabilizing agent for performing suspension
polymerizations. SEM images showed the successful formation of microparticles
with regular spherical morphology, while circular dichroism spectra
demonstrated the formation of one-handed helical polymer chains and
optical activity of the microparticles thereof. The present study
opens new opportunities for using CNCs and for preparing novel optically
active helical polymer materials.
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.
The
importance of chiral compounds has been widely recognized.
Enantioselectively controlled release of the desired enantiomer from
a racemate while retarding the other isomer provides a novel route
toward practical applications of biologically chiral molecules. Such
processes may maximize the efficacy while minimizing the dosage and
frequency of chiral compounds. So far, exciting achievements have
been made in enantioselective release (ESR), which can be classified
into two main groups according to the essential strategy: (1) chiral
interactions occurring between chiral compounds and chiral matrices
(“enantioselective interaction” strategy); and (2) recognizing
sites inside molecular-imprinting polymers (MIPs; “key-to-lock”
strategy). The chiral compounds of interest are not limited to chiral
drugs, but also include other biologically important chiral compounds
(e.g., amino acids). Based on our studies, this article reviews the
state-of-the-art techniques and materials systems toward ESR. The
emphasis is placed on the materials and material systems established
for the ESR purpose.
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