Mirror symmetry breaking and restoration within μm-sized polymer particles in optofluidic media by pumping circularly polarised light

Fujiki, Michiya; Yoshida, Kana; Suzuki, Nozomu; Zhang, Jian; Zhang, Wei; Zhu, Xiulin

doi:10.1039/c3ra22709j

Cited by 38 publications

(35 citation statements)

References 77 publications

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“…It should be noted here that high g CD values (10 −3 order) were achieved without a solid support for poly[(9,9‐di‐noctyl‐fluorenyl‐2,7‐diyl)‐alt‐4,4′‐azo‐benzene]3b by CPL and for poly(9,9‐di‐ n ‐decylfluorene)25 through interactions with chiral small molecules. Thus, the chirality induction mechanism may vary depending on chemical structure of a polymer and on the interacting substrate.…”

Section: Methodsmentioning

confidence: 88%

Predicting the Switchable Screw Sense in Fluorene‐Based Polymers

Pietropaolo

Wang

2015

Angewandte Chemie

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A chirality‐switching free‐energy landscape was reconstructed on a 43‐mer of poly(9,9‐dioctylfluoren‐2,7‐diyl) (PDOF). The simulations were conducted on amorphous silica surface as well as in the vacuum phase for a single chain or for a group of sixteen chains. The achiral‐to‐chiral transition occurs only on amorphous silica (activation free‐energy 35 kcal mol−1), where the enantiomeric (homochiral) basins are detected. This was supported by the experiments where effective chirality induction to PDOF using circularly polarized light (CPL) was attained only for a film deposited on a quartz glass and not for a solution or a suspension. These results indicate that interactions of PDOF with amorphous silica play a crucial role in chirality switching. Importance of chain assembling was also indicated. Theoretical ECD spectra of the enantiomeric basins containing a 51 helix reproduce the experimental spectra.

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Section: Methodsmentioning

confidence: 88%

Predicting the Switchable Screw Sense in Fluorene‐Based Polymers

Pietropaolo

Wang

2015

Angewandte Chemie

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“…(ii) Case 2. When 10 < E b < 30 kcal•mol −1 at the S 0 and S 1 states, non-mirror-image CPL and CD spectra are often observed [15,27,90,95,120,122,[125][126][127][128][129][130][131][132][133][134]. Although (+)-and (−)-signs in CPL and CD are primarily determined by atrope and point chirality, the absolute magnitudes and wavelengths at the CPL and CD bands differ considerably from each other.…”

Section: Discussionmentioning

confidence: 99%

Questions of Mirror Symmetry at the Photoexcited and Ground States of Non-Rigid Luminophores Raised by Circularly Polarized Luminescence and Circular Dichroism Spectroscopy. Part 2: Perylenes, BODIPYs, Molecular Scintillators, Coumarins, Rhodamine B, and DCM

2019

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We investigated whether semi-rigid and non-rigid π-conjugated fluorophores in the photoexcited (S1) and ground (S0) states exhibited mirror symmetry by circularly polarized luminescence (CPL) and circular dichroism (CD) spectroscopy using a range of compounds dissolved in achiral liquids. The fluorophores tested were six perylenes, six scintillators, 11 coumarins, two pyrromethene difluoroborates (BODIPYs), rhodamine B (RhB), and 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM). All the fluorophores showed negative-sign CPL signals in the ultraviolet (UV)–visible region, suggesting energetically non-equivalent and non-mirror image structures in the S1 state. The dissymmetry ratio of the CPL (glum) increased discontinuously from approximately −0.2 × 10−3 to −2.0 × 10−3, as the viscosity of the liquids increased. Among these liquids, C2-symmetrical stilbene 420 showed glum ≈ −0.5 × 10−3 at 408 nm in H2O and D2O, while, in a viscous alkanediol, the signal was amplified to glum ≈ −2.0 × 10−3. Moreover, BODIPYs, RhB, and DCM in the S0 states revealed weak (−)-sign CD signals with dissymmetry ratios (gabs) ≈ −1.4 × 10−5 at λmax/λext. The origin of the (−)-sign CPL and the (−)-sign CD signals may arise from an electroweak charge at the polyatomic level. Our CPL and CD spectral analysis could be a possible answer to the molecular parity violation hypothesis based on a weak neutral current of Z0 boson origin that could connect to the origin of biomolecular handedness.

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“…The CPL could trigger the two conformations (P-and M-twists) with asymmetric broken, and the enrichment of one enantiomeric excess could be finally obtained. With continual switching of the CPL handedness, the reversible modulation of chirality in the fluorene-alt-azobenzene copolymer particles could be achieved successfully [83]. This research would be helpful for the design of smart memory devices with the use of the nanosized supramolecular assembly.…”

Section: Enantioselective Photo-modulations Of Fluorene-based Polymersmentioning

confidence: 91%

The Chirality Induction and Modulation of Polymers by Circularly Polarized Light

Yang

Zhang

et al. 2019

Symmetry

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Chirality is a natural attribute nature of living matter and plays an important role in maintaining the metabolism, evolution and functional activities of living organisms. Asymmetric conformation represents the chiral structure of biomacromolecules in living organisms on earth, such as the L-amino acids of proteins and enzymes, and the D-sugars of DNA or RNA, which exist preferentially as one enantiomer. Circularly polarized light (CPL), observed in the formation regions of the Orion constellation, has long been proposed as one of the origins of single chirality. Herein, the CPL triggered asymmetric polymerization, photo-modulation of chirality based on polymers are described. The mechanisms between CPL and polymers (including polydiacetylene, azobenzene polymers, chiral coordination polymers, and polyfluorene) are described in detail. This minireview provides a promising flexible asymmetric synthesis method for the fabrication of chiral polymer via CPL irradiation, with the hope of obtaining a better understanding of the origin of homochirality on earth.

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Mirror symmetry breaking and restoration within μm-sized polymer particles in optofluidic media by pumping circularly polarised light

Abstract: Mirror symmetry breaking and restoration within mmsized polymer particles in optofluidic media by pumping circularly polarised light3

Cited by 38 publications

References 77 publications

Predicting the Switchable Screw Sense in Fluorene‐Based Polymers

Predicting the Switchable Screw Sense in Fluorene‐Based Polymers

Questions of Mirror Symmetry at the Photoexcited and Ground States of Non-Rigid Luminophores Raised by Circularly Polarized Luminescence and Circular Dichroism Spectroscopy. Part 2: Perylenes, BODIPYs, Molecular Scintillators, Coumarins, Rhodamine B, and DCM

The Chirality Induction and Modulation of Polymers by Circularly Polarized Light

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