1
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Duan H, Li S, Wu X, Deng J, Li J, Qi D, Zhao B. Solvent-Free Supramolecular Polymerization for Feather-Like Nanostructured Chiral Fluorescent Polyurethanes with Multimodal Chiroptical Stimuli Responsiveness. ADVANCED SCIENCE (WEINHEIM, BADEN-WURTTEMBERG, GERMANY) 2025; 12:e2417572. [PMID: 40019371 PMCID: PMC12021037 DOI: 10.1002/advs.202417572] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Subscribe] [Scholar Register] [Received: 12/25/2024] [Revised: 02/08/2025] [Indexed: 03/01/2025]
Abstract
Chiral supramolecular polymers with stimuli-responsive circularly polarized luminescence (CPL) are highly desirable for smart flexible optoelectronic devices, but remain rarely reported. Here, a simple solvent-free supramolecular polymerization for preparing chiral polyurethanes is presented by in situ induced self-assembly strategy, using cellulose nanocrystals (CNCs)-based isocyanate prepolymers and macromolecular polyols as precursors, achieving precise control over polymer chain assembly with spot-like arrangement. More importantly, by further incorporating a π-conjugated luminescent dihydroxynaphthalene molecule, CPL-active flexible polyurethane films with feather-like nanostructures are constructed, which promote the ordered arrangement of CNCs-based isocyanate segments due to the increased spatial resistance. The π─H bond network between CNCs and urethane-linked benzene rings drives the self-assembly, enabling higher-level chiral amplification and enhanced fluorescence. Interestingly, the prepared chiral fluorescent polyurethanes display multimodal chiroptical stimuli responsiveness under various stimuli, such as temperature, solvent polarity, pH, and polarized light, due to the sensitivity of the π─H bond network. This work offers new insights into designing solvent-free chiral supramolecular polymers with significant chiroptical potentials.
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Affiliation(s)
- Huimin Duan
- School of Textile Science and Engineering, School of Materials Science and Engineering & School of Chemistry and Chemical EngineeringZhejiang Sci‐Tech UniversityZhejiang310018China
- Zhejiang Provincial Innovation Center of Advanced Textile TechnologyZhejiang312000China
- Shaoxing Keqiao Research Institute of Zhejiang Sci‐Tech UniversityZhejiang312000China
| | - Shuli Li
- School of Textile Science and Engineering, School of Materials Science and Engineering & School of Chemistry and Chemical EngineeringZhejiang Sci‐Tech UniversityZhejiang310018China
| | - Xinlei Wu
- School of Textile Science and Engineering, School of Materials Science and Engineering & School of Chemistry and Chemical EngineeringZhejiang Sci‐Tech UniversityZhejiang310018China
- Zhejiang Provincial Innovation Center of Advanced Textile TechnologyZhejiang312000China
| | - Jianping Deng
- State Key Laboratory of Chemical Resource Engineering, College of Materials Science and EngineeringBeijing University of Chemical TechnologyBeijing100029China
| | - Jiawei Li
- School of Textile Science and Engineering, School of Materials Science and Engineering & School of Chemistry and Chemical EngineeringZhejiang Sci‐Tech UniversityZhejiang310018China
| | - Dongming Qi
- School of Textile Science and Engineering, School of Materials Science and Engineering & School of Chemistry and Chemical EngineeringZhejiang Sci‐Tech UniversityZhejiang310018China
- Zhejiang Provincial Innovation Center of Advanced Textile TechnologyZhejiang312000China
| | - Biao Zhao
- State Key Laboratory of Chemical Resource Engineering, College of Materials Science and EngineeringBeijing University of Chemical TechnologyBeijing100029China
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2
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Fujii N, Hisano N, Hirao T, Kihara SI, Tanabe K, Yoshida M, Tate SI, Haino T. Controlled Helical Organization in Supramolecular Polymers of Pseudo-Macrocyclic Tetrakisporphyrins. Angew Chem Int Ed Engl 2025; 64:e202416770. [PMID: 39445656 DOI: 10.1002/anie.202416770] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 09/01/2024] [Revised: 10/19/2024] [Accepted: 10/21/2024] [Indexed: 10/25/2024]
Abstract
Tetrakisporphyrin monomers with amino acid side chains at each end form intramolecular antiparallel hydrogen-bonds to adopt chirally twisted pseudo-macrocyclic structures that result in right-handed and left-handed (P)- and (M)-conformations. The pseudo-macrocyclic tetrakisporphyrin monomers self-assembled to form supramolecular helical pseudo-polycatenane polymers via head-to-head complementary dimerization of the bisporphyrin cleft units in an isodesmic manner. The formation of one-handed supramolecular helical pseudo-polycatenane polymers was confirmed by circular dichroism (CD) spectroscopy. The methyl and iso-propyl groups at the stereogenic center greatly enhanced the induced circular dichroism in the Soret bands of the supramolecular helical pseudo-polycatenane polymers. The induced CDs were reduced upon the introduction of large iso-butyl and tert-butyl groups. Atomic force microscopy revealed well-grown and long supramolecular helical pseudo-polycatenane polymer chains with chain lengths in the range of 361 to 13.6 nm. The right-handed helical chains were established by the self-assembly of the right-handed (P)-conformation of the pseudo-macrocyclic monomer.
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Affiliation(s)
- Naoka Fujii
- Department of Chemistry Graduate School of Advanced Science and Engineering, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
| | - Naoyuki Hisano
- Department of Chemistry Graduate School of Advanced Science and Engineering, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
| | - Takehiro Hirao
- Department of Chemistry Graduate School of Advanced Science and Engineering, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
| | - Shin-Ichi Kihara
- Department of Chemical Engineering Graduate School of Advanced Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8527, Japan
| | - Kouta Tanabe
- Department of Chemistry Graduate School of Advanced Science and Engineering, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
- International Institute for Sustainability with Knotted Chiral Meta Matter (SKCM2), Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
| | - Masaya Yoshida
- Department of Chemistry Graduate School of Advanced Science and Engineering, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
- International Institute for Sustainability with Knotted Chiral Meta Matter (SKCM2), Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
| | - Shin-Ichi Tate
- International Institute for Sustainability with Knotted Chiral Meta Matter (SKCM2), Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
- Department of Mathematical and Life Sciences, Graduate School of Integrated Sciences for Life, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
| | - Takeharu Haino
- Department of Chemistry Graduate School of Advanced Science and Engineering, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
- International Institute for Sustainability with Knotted Chiral Meta Matter (SKCM2), Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima, 739-8526, Japan
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3
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Li SY, Duan BH, Liu N, Luo J, Chen Z, Wu ZQ. Helical Star-Shaped Bottlebrush Polymers: From Controlled Synthesis to Tunable Photoluminescence and Circularly Polarized Luminescence. ACS Macro Lett 2024; 13:1396-1402. [PMID: 39377270 DOI: 10.1021/acsmacrolett.4c00508] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 10/09/2024]
Abstract
The controlled synthesis of star-shaped bottlebrush polymers with tunable topologies is a challenge. However, such materials may exhibit distinct photoluminescence properties. Bottlebrush polymers have polymerization-induced emission (PIE) properties due to their aggregated side chains, and aggregation-induced emission (AIE) is also a unique luminescent property. In this work, we prepared a variety of highly active alkyne Pd catalysts and polymerized poly(L/D-lactic acid) macromonomers containing polymerizable phenylisocyanide groups as end groups to obtain a variety of topologically structured bottlebrush polymers with controllable molecular weights and narrow molecular weight distributions. Bottlebrush polymers with tetraphenyl ethylene (TPE) units as the core exhibit tunable photoluminescence and circularly polarized luminescence properties. We propose that such properties are due to the unique AIE characteristics of the TPE unit combined with the PIE characteristics of the bottlebrush polymer.
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Affiliation(s)
- Shi-Yi Li
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China
| | - Bing-Hui Duan
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China
| | - Na Liu
- The School of Pharmaceutical Sciences, Jilin University, Changchun, Jilin 130021, China
| | - Jing Luo
- Department of Neurosurgery, The First Affiliated Hospital of Anhui Medical University, 218 Jixi, Hefei, Anhui 230022, China
| | - Zheng Chen
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China
| | - Zong-Quan Wu
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Street, Changchun 130012, China
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4
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Okuda S, Ikai T, Okutsu H, Ando M, Hattori M, Ishidate R, Yashima E. Helix-Sense-Selective Memory Polymerization of Biphenylylacetylenes Bearing Carboxy and Amino Groups in Water. Angew Chem Int Ed Engl 2024; 63:e202412752. [PMID: 39043565 DOI: 10.1002/anie.202412752] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 07/07/2024] [Revised: 07/23/2024] [Accepted: 07/23/2024] [Indexed: 07/25/2024]
Abstract
We report the helix-sense-selective memory polymerization (HSMP) of achiral biphenylylacetylenes bearing carboxy and amino pendant groups in the presence of basic and acidic chiral guests in water, respectively. The HSMP proceeds in a highly helix-sense-selective manner driven by noncovalent chiral ionic interactions between the monomers and guests under kinetic control, producing the one-handed helical polymers with a static memory of helicity in one-pot during the polymerization in a very short time, accompanied by amplification of asymmetry. The carboxy-bound helicity-memorized polymer self-assembles into a cholesteric liquid crystal in concentrated water, in which a variety of basic achiral fluorophores further co-assembles to form supramolecular helical aggregates that exhibit an induced circularly polarized luminescence in a color tunable manner.
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Affiliation(s)
- Shogo Okuda
- Department of Molecular and Macromolecular Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan
| | - Tomoyuki Ikai
- Department of Molecular and Macromolecular Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan
- Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST) Kawaguchi, Saitama, 332-0012, Japan
| | - Hinako Okutsu
- Department of Molecular and Macromolecular Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan
| | - Mitsuka Ando
- Department of Molecular and Macromolecular Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan
| | - Masaki Hattori
- Department of Molecular and Macromolecular Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan
| | - Ryoma Ishidate
- Department of Molecular Design and Engineering Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan
| | - Eiji Yashima
- Department of Molecular and Macromolecular Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan
- Department of Molecular Design and Engineering Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan
- Present address: Department of Chemical Engineering, National Tsing Hua University, 101, Sec. 2, Kuang-Fu Road, Hsinchu, 30013, Taiwan, R.O.C
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5
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Wang Y, Zhang X, Huang CB, Hu L, Wang XQ, Wang W, Yang HB. Inducing and Switching the Handedness of Polyacetylenes with Topologically Chiral [2]Catenane Pendants. Angew Chem Int Ed Engl 2024; 63:e202408271. [PMID: 38837513 DOI: 10.1002/anie.202408271] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 04/30/2024] [Revised: 06/04/2024] [Accepted: 06/04/2024] [Indexed: 06/07/2024]
Abstract
To explore the chirality induction and switching of topological chirality, poly[2]catenanes composed of helical poly(phenylacetylenes) (PPAs) main chain and topologically chiral [2]catenane pendants are described for the first time. These poly[2]catenanes with optically active [2]catenanes on side chains were synthesized by polymerization of enantiomerically pure topologically chiral [2]catenanes with ethynyl polymerization site and/or point chiral moiety. The chirality information of [2]catenane pendants was successfully transferred to the main chain of polyene backbones, leading to preferred-handed helical conformations, while the introduction of point chiral units has negligible effect on the overall helices. More interestingly, attributed to unique dynamic feature of the [2]catenane pendants, these polymers revealed dynamic response behaviors to solvents, temperature, and sodium ions, resulting in the fully reversible switching on/off of the chirality induction. This work provides not only new design strategy for novel chiroptical switches with topologically chiral molecules but also novel platforms for the development of smart chiral materials.
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Affiliation(s)
- Yu Wang
- Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China
| | - Xin Zhang
- Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China
| | - Chang-Bo Huang
- Coatings Applied Research Asia Pacific, BASF Advanced Chemicals Co., Ltd., Shanghai, 200137, China
| | - Lianrui Hu
- Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China
| | - Xu-Qing Wang
- Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China
| | - Wei Wang
- Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China
| | - Hai-Bo Yang
- Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, China
- Shanghai Center of Brain-inspired Intelligent Materials and Devices, East China Normal University, Shanghai, 200241, China
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6
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Song D, Koo B, Kang H, Seo K, Kim C. Chiral Acetal-Based Stereo-Controlled Degradable Polymer Synthesis. Chemistry 2024; 30:e202402064. [PMID: 38923725 DOI: 10.1002/chem.202402064] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 05/27/2024] [Revised: 06/17/2024] [Accepted: 06/25/2024] [Indexed: 06/28/2024]
Abstract
The precise synthesis of chiral polymers remains a significant challenge in polymer chemistry, particularly for applications in advanced biomedical and electronic materials. The development of degradable polymers is important for eco-friendly and advanced materials. Here, we introduce a stereo-controlled degradable polymer via cascade enyne metathesis polymerization and enantioselective acetal synthesis through Pd-catalyzed asymmetric hydroamination. This approach allows for the creation of chiral acetal-based polymers with controlled stereochemistry and degradability, highlighting their potential for use in drug delivery and electronic applications. This concept article reviews the background, development, and potential applications of these stereo-controlled degradable polymers.
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Affiliation(s)
- Dayong Song
- Department of Chemistry, Chungbuk National University, 1 Chungdae-ro, Seowon-gu, Cheongju, 28644, Republic of Korea
| | - Bonwoo Koo
- Department of Chemistry, Chungbuk National University, 1 Chungdae-ro, Seowon-gu, Cheongju, 28644, Republic of Korea
| | - Houng Kang
- Department of Chemistry Education, Chungbuk National University, 1 Chungdae-ro, Seowon-gu, Cheongju, 28644, Republic of Korea
| | - Kyeongdeok Seo
- Infectious Diseases Therapeutic Research Center, Korea Research Institute of Chemical Technology, 141 Gajeong-ro, Yuseong-gu, Daejeon, 34114, Republic of Korea
| | - Choeljae Kim
- Department of Chemistry, Chungbuk National University, 1 Chungdae-ro, Seowon-gu, Cheongju, 28644, Republic of Korea
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7
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Xu XH, Gao RT, Li SY, Zhou L, Liu N, Wu ZQ. Helical polyisocyanide-based macroporous organic catalysts for asymmetric Michael addition with high efficiency and stereoselectivity. Chem Sci 2024; 15:12480-12487. [PMID: 39118633 PMCID: PMC11304732 DOI: 10.1039/d4sc01316f] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Grants] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 02/26/2024] [Accepted: 06/29/2024] [Indexed: 08/10/2024] Open
Abstract
Porous materials have attracted interest due to their high specific surface area and rich functionality. Immobilizing organocatalysts onto porous polymers not only boosts enantioselectivity but also improves the reaction rates. In this work, a series of porous polymers C-poly-3ms with rigid polyisocyanide-carrying secondary amine pendants as building blocks were successfully prepared. And the pore size and optical activity of C-poly-3ms can be controlled by the length of the polyisocyanide blocks due to their rigid and helical backbone. C-poly-3150 demonstrated a preferred left-handed helix with a θ 364 value of -8.21 × 103. The pore size and S BET of C-poly-3150 were 17.52 nm and 7.98 m2 g-1, respectively. The porous C-poly-3150 catalyzes the asymmetric Michael addition reaction efficiently and generates the target products in satisfactory yield and excellent enantioselectivity. For 6ab, an enantiomeric excess (ee) and a diastereomeric ratio (dr) up to 99% and 99/1 could be achieved, respectively. The recovered catalyst can be recycled at least 6 times in the asymmetric Michael addition reaction while maintaining activity and stereoselectivity.
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Affiliation(s)
- Xun-Hui Xu
- Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Province Key Laboratory of Value-Added Catalytic Conversion and Reaction Engineering, Hefei University of Technology Hefei 230009 Anhui Province China
- Beijing National Laboratory for Molecular Sciences, Key Laboratory of Polymer Chemistry and Physics of Ministry of Education, College of Chemistry and Molecular Engineering, Peking University Beijing 100871 China
| | - Run-Tan Gao
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University Changchun Jilin 130012 China
| | - Shi-Yi Li
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University Changchun Jilin 130012 China
| | - Li Zhou
- Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Province Key Laboratory of Value-Added Catalytic Conversion and Reaction Engineering, Hefei University of Technology Hefei 230009 Anhui Province China
| | - Na Liu
- The School of Pharmaceutical Sciences, Jilin University 1266 Fujin Road Changchun Jilin 130021 P. R. China
| | - Zong-Quan Wu
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University Changchun Jilin 130012 China
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8
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Ravikumar AK, Nishimura T, Taniguchi T, Maeda K. Optically active poly(diphenylacetylene)s showing solvent-dependent helix inversion accompanied by modulation of helix inversion barriers. Chem Commun (Camb) 2024; 60:8379-8382. [PMID: 38984457 DOI: 10.1039/d4cc02656j] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 07/11/2024]
Abstract
Symmetrically substituted poly(diphenylacetylene)s bearing optically active 2-octyloxycarbonyl groups at the para-positions of the pendant phenyl rings not only show a unique solvent-dependent helix inversion to afford diastereomeric right- and left-handed helical polymers but also significant unprecedented solvent-dependent changes in the helix inversion barrier of the polymer backbone resulting in switching between static or dynamic behavior of the helical polymers at approximately room temperature depending on the solvents used.
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Affiliation(s)
- Abilesh Kumar Ravikumar
- Division of Nano Life Science, Graduate School of Frontier Science Initiative, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan
| | - Tatsuya Nishimura
- Graduate School of Natural Science & Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
| | - Tsuyoshi Taniguchi
- Graduate School of Natural Science & Technology, Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
- WPI Nano Life Science Institute (WPI-NanoLSI), Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
| | - Katsuhiro Maeda
- WPI Nano Life Science Institute (WPI-NanoLSI), Kanazawa University, Kakuma-machi, Kanazawa 920-1192, Japan.
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9
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Zhu Q, Hsu W, Wang S, Lin F, Wu Y, Fang Y, Chen J, Song L. Synthesis, antimicrobial activity and application of polymers of praseodymium complexes based on pyridine nitrogen oxide. RSC Adv 2024; 14:18519-18527. [PMID: 38860246 PMCID: PMC11164178 DOI: 10.1039/d4ra03003f] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Grants] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 04/22/2024] [Accepted: 05/27/2024] [Indexed: 06/12/2024] Open
Abstract
The traditional pyridine nitrogen oxide-based antimicrobial agents are often associated with health risks due to heavy metal enrichment. To mitigate this concern, we synthesized two novel complexes, Pr2(mpo)6(H2O)2 and Pr(hpo)(mpo)2(H2O)2, and integrated rare-earth salts, Hhpo (2-hydroxypyridine-N-oxide) and Nampo (2-mercapto-pyridine-N-oxide sodium salt). These complexes were characterized through infrared analysis, elemental analysis, thermogravimetric analysis, and X-ray crystallographic analysis. Our comparative analyses demonstrate that the synthesized rare-earth complexes exhibit stronger antimicrobial activity against Staphylococcus aureus (S. aureus ATCC6538) and Escherichia coli (E. coli ATCC25922) compared to the ligands and rare-earth salts alone. Quantitative results revealed the lowest inhibitory concentrations of the two complexes against S. aureus ATCC6538 and E. coli ATCC25922 at 3.125 μg mL-1, 6.25 μg mL-1, 3.125 μg mL-1 and 6.25 μg mL-1, respectively. Preliminary investigations indicated that the antibacterial mechanism of these complexes involved promoting intracellular substance exudation to achieve antibacterial effects. Incorporation of these complexes into polymeric antimicrobial films resulted in a potent antimicrobial effect, achieving a 100% inhibition rate against S. aureus ATCC6538 and E. coli ATCC25922 at a low addition level of 0.6 wt%. Our results suggest that nitrogen oxide-based praseodymium complexes have potential for various antimicrobial applications.
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Affiliation(s)
- Qiuyin Zhu
- JiangXi University of Science and Technology Ganzhou Jiangxi 341000 China
- Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences Xiamen Fujian 361021 China
- CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 China
- Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Fujian 361021 China
| | - Wayne Hsu
- Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences Xiamen Fujian 361021 China
- CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 China
- Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Fujian 361021 China
| | - Shenglong Wang
- Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences Xiamen Fujian 361021 China
- CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 China
- Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Fujian 361021 China
| | - Fenglong Lin
- Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences Xiamen Fujian 361021 China
- CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 China
- Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Fujian 361021 China
| | - Yincai Wu
- Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences Xiamen Fujian 361021 China
- CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 China
- Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Fujian 361021 China
| | - Yimin Fang
- Xiamen AXENT Co. Ltd Xiamen Fujian 361000 China
| | - Jinglin Chen
- JiangXi University of Science and Technology Ganzhou Jiangxi 341000 China
| | - Lijun Song
- Xiamen Institute of Rare Earth Materials, Chinese Academy of Sciences Xiamen Fujian 361021 China
- CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Provincial Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 China
- Xiamen Key Laboratory of Rare Earth Photoelectric Functional Materials Xiamen Fujian 361021 China
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10
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Chen R, Hammoud A, Aoun P, Martínez-Aguirre MA, Vanthuyne N, Maruchenko R, Brocorens P, Bouteiller L, Raynal M. Switchable supramolecular helices for asymmetric stereodivergent catalysis. Nat Commun 2024; 15:4116. [PMID: 38750046 PMCID: PMC11096402 DOI: 10.1038/s41467-024-48412-z] [Citation(s) in RCA: 1] [Impact Index Per Article: 1.0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 12/12/2023] [Accepted: 04/29/2024] [Indexed: 05/18/2024] Open
Abstract
Despite recent developments on the design of dynamic catalysts, none of them have been exploited for the in-situ control of multiple stereogenic centers in a single molecular scaffold. We report herein that it is possible to obtain in majority any amongst the four possible stereoisomers of an amino alcohol by means of a switchable asymmetric catalyst built on supramolecular helices. Hydrogen-bonded assemblies between a benzene-1,3,5-tricarboxamide (BTA) achiral phosphine ligand coordinated to copper and a chiral BTA comonomer are engaged in a copper-hydride catalyzed hydrosilylation and hydroamination cascade process. The nature of the product stereoisomer is related to the handedness of the helices and can thus be directed in a predictable way by changing the nature of the major enantiomer of the BTA comonomer present in the assemblies. The strategy allows all stereoisomers to be obtained one-pot with similar selectivities by conducting the cascade reaction in a concomitant manner, i.e. without inverting the handedness of the helices, or sequentially, i.e. by switching the handedness of the supramolecular helices between the hydrosilylation and hydroamination steps. Supramolecular helical catalysts appear as a unique and versatile platform to control the configuration of molecules or polymers embedding several stereogenic centers.
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Affiliation(s)
- Ran Chen
- Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, 4 Place Jussieu, 75005, Paris, France
| | - Ahmad Hammoud
- Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, 4 Place Jussieu, 75005, Paris, France
| | - Paméla Aoun
- Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, 4 Place Jussieu, 75005, Paris, France
| | - Mayte A Martínez-Aguirre
- Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, 4 Place Jussieu, 75005, Paris, France
| | - Nicolas Vanthuyne
- Aix Marseille Université, Centrale Marseille, CNRS, iSm2, UMR 7313, 13397, Marseille, Cedex 20, France
| | - Régina Maruchenko
- Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, 4 Place Jussieu, 75005, Paris, France
| | - Patrick Brocorens
- Service de Chimie des Matériaux Nouveaux, Institut de Recherche sur les Matériaux, Université de Mons, 20B-7000, 20 B-7000, Mons, Belgium
| | - Laurent Bouteiller
- Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, 4 Place Jussieu, 75005, Paris, France
| | - Matthieu Raynal
- Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, 4 Place Jussieu, 75005, Paris, France.
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11
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Xue M, Zhang L, Wang X, Dong Q, Zhu Z, Wang X, Gu Q, Kang F, Li XX, Zhang Q. A Metal-Free Helical Covalent Inorganic Polymer: Preparation, Crystal Structure and Optical Properties. Angew Chem Int Ed Engl 2024; 63:e202315338. [PMID: 38126955 DOI: 10.1002/anie.202315338] [Citation(s) in RCA: 10] [Impact Index Per Article: 10.0] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 10/11/2023] [Revised: 12/12/2023] [Accepted: 12/21/2023] [Indexed: 12/23/2023]
Abstract
Helical morphologies are widely observed in nature, however, it is very challenging to prepare artificial helical polymers. Especially, precisely understanding the structure information of artificial metal-free helical covalent inorganic polymers via single-crystal X-ray diffraction (SCXRD) analysis is rarely explored. Here, we successfully prepare a novel metal-free helical covalent inorganic polymer ({[Te(C6 H5 )2 ] [PO3 (OH)]}n , named CityU-10) by introducing angular anions (HOPO3 2- ) into traditional tellurium-oxygen chains. The dynamic reversibility of the reaction is realized through the introduction of organic tellurium precursor and the slow hydrolysis of polyphosphoric acid. High-quality and large-size single crystals of CityU-10 have been successfully characterized via SCXRD, where the same-handed helical inorganic polymer chains form a pseudo-two-dimensional layer via multiple hydrogen-bonding interactions. The left-handed layers and right-handed layers alternatively stack together through weak hydrogen bonds to form a three-dimensional supramolecular structure. The single crystals of CityU-10 are found to display promising optical properties with a large birefringence. Our results would offer new guidelines for designing and preparing new crystalline covalent polymers through tellurium-based chemistry.
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Affiliation(s)
- Miaomiao Xue
- Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
| | - Lei Zhang
- Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
| | - Xiang Wang
- Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
| | - Qiang Dong
- Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
| | - Zengkui Zhu
- Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China
| | - Xin Wang
- Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
| | - Qianfeng Gu
- Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
| | - Fangyuan Kang
- Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
| | - Xin-Xiong Li
- Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated-Materials, College of Chemistry, Fuzhou University, Fuzhou, Fujian, 350108, China
| | - Qichun Zhang
- Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
- Department of Chemistry & Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Tat Chee Avenue, Kowloon Tong, Hong Kong SAR, P. R. China
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12
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Lago-Silva M, Fernández-Míguez M, Rodríguez R, Quiñoá E, Freire F. Stimuli-responsive synthetic helical polymers. Chem Soc Rev 2024; 53:793-852. [PMID: 38105704 DOI: 10.1039/d3cs00952a] [Citation(s) in RCA: 24] [Impact Index Per Article: 24.0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/19/2023]
Abstract
Synthetic dynamic helical polymers (supramolecular and covalent) and foldamers share the helix as a structural motif. Although the materials are different, these systems also share many structural properties, such as helix induction or conformational communication mechanisms. The introduction of stimuli responsive building blocks or monomer repeating units in these materials triggers conformational or structural changes, due to the presence/absence of the external stimulus, which are transmitted to the helix resulting in different effects, such as assymetry amplification, helix inversion or even changes in the helical scaffold (elongation, J/H helical aggregates). In this review, we show through selected examples how different stimuli (e.g., temperature, solvents, cations, anions, redox, chiral additives, pH or light) can alter the helical structures of dynamic helical polymers (covalent and supramolecular) and foldamers acting on the conformational composition or molecular structure of their components, which is also transmitted to the macromolecular helical structure.
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Affiliation(s)
- María Lago-Silva
- Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
| | - Manuel Fernández-Míguez
- Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
| | - Rafael Rodríguez
- Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
| | - Emilio Quiñoá
- Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
| | - Félix Freire
- Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares (CiQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
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13
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YASHIMA E. Synthesis and applications of helical polymers with dynamic and static memories of helicity. PROCEEDINGS OF THE JAPAN ACADEMY. SERIES B, PHYSICAL AND BIOLOGICAL SCIENCES 2023; 99:438-459. [PMID: 37853628 PMCID: PMC10822720 DOI: 10.2183/pjab.99.025] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [MESH Headings] [Track Full Text] [Subscribe] [Scholar Register] [Received: 04/03/2023] [Accepted: 09/13/2023] [Indexed: 10/20/2023]
Abstract
This review mainly highlights our studies on the synthesis of one-handed helical polymers with a static memory of helicity based on the noncovalent helicity induction with a helical-sense bias and subsequent memory of the helicity approach that we developed during the past decade. Apart from the previous approaches, an excess one-handed helical conformation, once induced by nonracemic molecules, is immediately retained ("memorized") after the complete removal of the nonracemic molecules, accompanied by a significant amplification of the asymmetry, providing novel switchable chiral materials for chromatographic enantioseparation and asymmetric catalysis as well as a highly sensitive colorimetric and fluorescence chiral sensor. A conceptually new one-handed helix formation in a racemic helical polymer composed of racemic repeating units through the deracemization of the pendants is described.
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Affiliation(s)
- Eiji YASHIMA
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Aichi, Japan
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14
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Rai R, Khazeber R, Sureshan KM. Single-Crystal-to-Single-Crystal Topochemical Synthesis of a Collagen-inspired Covalent Helical Polymer. Angew Chem Int Ed Engl 2023; 62:e202315742. [PMID: 37861464 DOI: 10.1002/anie.202315742] [Citation(s) in RCA: 1] [Impact Index Per Article: 0.5] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 10/18/2023] [Revised: 10/20/2023] [Accepted: 10/20/2023] [Indexed: 10/21/2023]
Abstract
There is much demand for crystalline covalent helical polymers. Inspired by the helical structure of collagen, we synthesized a covalent helical polymer wherein the repeating dipeptide Gly-Pro units are connected by triazole linkages. We synthesized an azide and alkyne-modified dipeptide monomer made up of the repeating amino acid sequence of collagen. In its crystals, the monomer molecules aligned in head-to-tail fashion with proximally placed azide and alkyne forming supramolecular helices. At 60 °C, the monomer underwent single-crystal-to-single-crystal (SCSC) topochemical azide-alkyne cycloaddition polymerization, yielding a covalent helical polymer as confirmed by single-crystal X-ray diffraction (SCXRD) analysis. Compared to the monomer crystals, the polymer single-crystals were very strong and showed three-fold increase in Young's modulus, which is higher than collagen, many synthetic polymers and other materials. The crystals of this covalent helical polymer could bear loads as high as 1.5 million times of their own weight without deformation. These crystals could also withstand high compression force and did not disintegrate even at an applied force of 98 kN. Such light-weight strong materials are in demand for various technological applications.
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Affiliation(s)
- Rishika Rai
- School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram Thiruvananthapuram, Kerala, 695551, India
| | - Ravichandran Khazeber
- School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram Thiruvananthapuram, Kerala, 695551, India
| | - Kana M Sureshan
- School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram Thiruvananthapuram, Kerala, 695551, India
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15
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Ikai T, Morita Y, Majima T, Takeda S, Ishidate R, Oki K, Suzuki N, Ohtani H, Aoi H, Maeda K, Okoshi K, Yashima E. Control of One-Handed Helicity in Polyacetylenes: Impact of an Extremely Small Amount of Chiral Substituents. J Am Chem Soc 2023; 145:24862-24876. [PMID: 37930639 PMCID: PMC10825823 DOI: 10.1021/jacs.3c09308] [Citation(s) in RCA: 6] [Impact Index Per Article: 3.0] [Reference Citation Analysis] [Abstract] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 08/25/2023] [Revised: 10/25/2023] [Accepted: 10/26/2023] [Indexed: 11/07/2023]
Abstract
Controlling the one-handed helicity in synthetic polymers is crucial for developing helical polymer-based advanced chiral materials. We now report that an extremely small amount of chiral biphenylylacetylene (BPA) monomers (ca. 0.3-0.5 mol %) allows complete control of the one-handed helicity throughout the polymer chains mostly composed of achiral BPAs. Chiral substituents introduced at the 2-position of the biphenyl units of BPA positioned in the vicinity of the polymer backbones contribute to a significant amplification of the helical bias, as interpreted by theoretical modeling and simulation. The helical structures, such as the helical pitch and absolute helical handedness (right- or left-handed helix) of the one-handed helical copolymers, were unambiguously determined by high-resolution atomic force microscopy combined with X-ray diffraction. The exceptionally strong helix-biasing power of the chiral BPA provides a highly durable and practically useful chiral material for the separation of enantiomers in chromatography by copolymerization of an achiral functional BPA with a small amount of the chiral BPA (0.5 mol %) due to the robust helical scaffold of the one-handed helical copolymer.
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Affiliation(s)
- Tomoyuki Ikai
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
- Precursory
Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan
| | - Yuki Morita
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
| | - Tsuyoshi Majima
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
| | - Shoki Takeda
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
| | - Ryoma Ishidate
- Department
of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
| | - Kosuke Oki
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
| | - Nozomu Suzuki
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
- Department
of Chemical Science and Engineering, Graduate School of Engineering, Kobe University, Kobe 657-8501, Japan
| | - Hajime Ohtani
- Department
of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan
| | - Hiromi Aoi
- Department
of Life Science and Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya 466-8555, Japan
| | - Katsuhiro Maeda
- Graduate
School of Natural Science and Technology, Kanazawa University, Kanazawa 920-1192, Japan
- Nano
Life Science Institute (WPI-NanoLSI), Kanazawa
University, Kanazawa 920-1192, Japan
| | - Kento Okoshi
- Department
of Applied Chemistry and Bioscience, Chitose
Institute of Science and Technology, Chitose, Hokkaido 066-8655, Japan
| | - Eiji Yashima
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
- Department
of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
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16
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Xu L, Zhou L, Li YX, Gao RT, Chen Z, Liu N, Wu ZQ. Thermo-responsive chiral micelles as recyclable organocatalyst for asymmetric Rauhut-Currier reaction in water. Nat Commun 2023; 14:7287. [PMID: 37949865 PMCID: PMC10638429 DOI: 10.1038/s41467-023-43092-7] [Citation(s) in RCA: 9] [Impact Index Per Article: 4.5] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 11/16/2022] [Accepted: 10/31/2023] [Indexed: 11/12/2023] Open
Abstract
Developing eco-friendly chiral organocatalysts with the combined advantages of homogeneous catalysis and heterogeneous processes is greatly desired. In this work, a family of amphiphilic one-handed helical polyisocyanides bearing phosphine pendants is prepared, which self-assembles into well-defined chiral micelles in water and showed thermo-responsiveness with a cloud point of approximately 38.4 °C. The micelles with abundant phosphine moieties at the interior efficiently catalyze asymmetric cross Rauhut-Currier reaction in water. Various water-insoluble substrates are transferred to target products in high yield with excellent enantioselectivity. The yield and enantiomeric excess (ee) of the product generated in water are up to 90% and 96%, respectively. Meanwhile, the yields of the same R-C reaction catalyzed by the polymer itself in organic solvents is <16%, with an ee < 72%. The homogeneous reaction of the chiral micelles in water turns to heterogeneous at temperatures higher than the cloud point, and the catalyst precipitation facilitates product isolation and catalyst recovery. The polymer catalyst is recycled 10 times while maintaining activity and enantioselectivity.
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Affiliation(s)
- Lei Xu
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 130012, Changchun, China
- Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Huaibei Normal University, 235000, Huaibei, Anhui, China
| | - Li Zhou
- Department of Polymer Science and Engineering, Hefei University of Technology, 230009, Hefei, China
| | - Yan-Xiang Li
- Department of Polymer Science and Engineering, Hefei University of Technology, 230009, Hefei, China
| | - Run-Tan Gao
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 130012, Changchun, China
| | - Zheng Chen
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 130012, Changchun, China
| | - Na Liu
- The School of Pharmaceutical Sciences, Jilin University, 1266 Fujin Road, 130021, Changchun, Jilin, China
| | - Zong-Quan Wu
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 130012, Changchun, China.
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17
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Xu L, Wu YJ, Gao RT, Li SY, Liu N, Wu ZQ. Visible Helicity Induction and Memory in Polyallene toward Circularly Polarized Luminescence, Helicity Discrimination, and Enantiomer Separation. Angew Chem Int Ed Engl 2023; 62:e202217234. [PMID: 36745050 DOI: 10.1002/anie.202217234] [Citation(s) in RCA: 23] [Impact Index Per Article: 11.5] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 11/23/2022] [Revised: 01/31/2023] [Accepted: 02/06/2023] [Indexed: 02/07/2023]
Abstract
Inspired by biological helices (e.g., DNA), artificial helical polymers have attracted intense attention. However, precise synthesis of one-handed helices from achiral materials remains a formidable challenge. Herein, a series of achiral poly(biphenyl allene)s with controlled molar mass and low dispersity were prepared and induced into one-handed helices using chiral amines and alcohols. The induced one-handed helix was simultaneously memorized, even after the chiral inducer was removed. The switchable induction processes were visible to naked eye; the achiral polymers exhibited blue emission (irradiated at 365 nm), whereas the induced one-handed helices exhibited cyan emission with clear circularly polarized luminescence. The induced helices formed stable gels in various solvents with helicity discrimination ability: the same-handed helix gels were self-healing, whereas the gels of opposite-handed helicity were self-sorted. Moreover, the induced helices could separate enantiomers via enantioselective crystallization with high efficiency and switchable enantioselectivity.
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Affiliation(s)
- Lei Xu
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, China.,Key Laboratory of Green and Precise Synthetic Chemistry and Applications, Ministry of Education, Huaibei Normal University, Huaibei, Anhui, 235000, P. R. China
| | - Yong-Jie Wu
- Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Key Laboratory of Advanced Functional Materials and Devices, Hefei University of Technology, Hefei, Anhui Province, 230009, China
| | - Run-Tan Gao
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, China
| | - Shi-Yi Li
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, China
| | - Na Liu
- The School of Pharmaceutical Sciences, Jilin University, 1266 Fujin Road, Changchun, Jilin, 130021, P. R. China
| | - Zong-Quan Wu
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012, China
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18
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Rodríguez R, Rivadulla-Cendal E, Quiñoá E, Freire F. Diastereomeric multi-chiral pendant groups: Their key role in stimuli-responsive polymeric responses. Chirality 2023; 35:172-177. [PMID: 36625726 PMCID: PMC10107841 DOI: 10.1002/chir.23530] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 11/30/2022] [Revised: 12/22/2022] [Accepted: 12/24/2022] [Indexed: 01/11/2023]
Abstract
Chiral information transmission in helical polymers bearing multi-chiral pendant groups is usually determined by the absolute configuration of the first chiral center. The second chiral residue usually has low-to-null influence in the macromolecular handedness of the polymer, due to its remote position respect to the polyene main chain. Here, we demonstrate how the stimuli responsive properties of diastereomeric polymers, obtained by changing the absolute configuration of the second chiral center, are different due to the unlike properties of diastereoisomers.
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Affiliation(s)
- Rafael Rodríguez
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, Spain
| | - Elena Rivadulla-Cendal
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, Spain
| | - Emilio Quiñoá
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, Spain
| | - Félix Freire
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química Orgánica, Universidade de Santiago de Compostela, Santiago de Compostela, Spain
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19
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Visualized thermoresponsive helix-helix switch of polyphenylacetylene with a wide-range tunable transition temperature. Sci China Chem 2023. [DOI: 10.1007/s11426-022-1422-y] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 02/16/2023]
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20
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Fukuda M, Morikawa M, Hirose D, Taniguchi T, Nishimura T, Yashima E, Maeda K. Ultra-fast One-Handed Helix Induction and Its Static Helicity Memory in a Poly(biphenylylacetylene) with a Catalytic Amount of Chiral Ammonium Salts. Angew Chem Int Ed Engl 2023; 62:e202217020. [PMID: 36718497 DOI: 10.1002/anie.202217020] [Citation(s) in RCA: 8] [Impact Index Per Article: 4.0] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 11/18/2022] [Revised: 01/20/2023] [Accepted: 01/30/2023] [Indexed: 02/01/2023]
Abstract
We report an ultra-fast helix induction and subsequent static helicity memory in poly(biphenylylacetylene) (PBPA-A) assisted by a catalytic amount of nonracemic ammonium salts comprised of non-coordinating tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BArF- ) as a counter anion. The remarkable acceleration of the helix-induction rate in PBPA-A accompanied by the significant amplification of the asymmetry relies on the two methoxymethoxy groups of the biphenyl pendants, which can gain access to enfold the chiral ammoniums in a crown-ether manner in specific aromatic solvents, leading to ultra-fast helicity induction, which is completed within 30 s. In aromatic solvents, helicity memory is lost rapidly, but is quite stable in long-chain hydrocarbons. The best use of specific solvents for helicity induction and static helicity memory, respectively, provides a highly sensitive chirality sensing system toward a small amount of chiral amines and amino acids when complexed with BArF- .
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Affiliation(s)
- Mayu Fukuda
- Graduate School of Frontier Science Initiative, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan
| | - Mai Morikawa
- Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan
| | - Daisuke Hirose
- Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan
| | - Tsuyoshi Taniguchi
- Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan
| | - Tatsuya Nishimura
- Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan
| | - Eiji Yashima
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya, 464-8603, Japan
| | - Katsuhiro Maeda
- Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan.,Nano Life Science Institute (WPI-NanoLSI), Kanazawa University, Kakuma-machi, Kanazawa, 920-1192, Japan
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21
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Ikai T, Anzai S, Oki K, Yashima E. Amplification of macromolecular helicity of poly(biphenylylacetylene)s composed of a small amount of chiral [5]helicene units. JOURNAL OF POLYMER SCIENCE 2022. [DOI: 10.1002/pol.20220658] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/12/2022]
Affiliation(s)
- Tomoyuki Ikai
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering Nagoya University Nagoya Japan
- Precursory Research for Embryonic Science and Technology (PRESTO) Japan Science and Technology Agency (JST) Saitama Japan
| | - Shun Anzai
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering Nagoya University Nagoya Japan
| | - Kosuke Oki
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering Nagoya University Nagoya Japan
| | - Eiji Yashima
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering Nagoya University Nagoya Japan
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22
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Rodríguez R, Rivadulla‐Cendal E, Fernández‐Míguez M, Fernández B, Maeda K, Quiñoá E, Freire F. Full Control of the Chiral Overpass Effect in Helical Polymers: P/M Screw Sense Induction by Remote Chiral Centers After Bypassing the First Chiral Residue. Angew Chem Int Ed Engl 2022; 61:e202209953. [PMID: 36121741 PMCID: PMC9828504 DOI: 10.1002/anie.202209953] [Citation(s) in RCA: 3] [Impact Index Per Article: 1.0] [Reference Citation Analysis] [Abstract] [Key Words] [MESH Headings] [Grants] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 07/07/2022] [Indexed: 01/12/2023]
Abstract
In helical polymers, helical sense induction is usually commanded by teleinduction mechanism, where the largest substituent of the chiral residue directly attached to the main chain is the one that commands the helical sense. In this work, different helical structures with different helical senses are induced in a helical polymer [poly-(phenylacetylene)] when the conformational composition of two different dihedral angles of a pendant group with more than two chiral residues is tamed. Thus, while the dihedral angle at chiral residue 1 [(R)- or (S)-alanine], attached to the backbone, produces an extended or bent conformation in the pendant resulting in two scaffolds with different stretching degree, the second dihedral angle at chiral residue 2 [(R)- or (S)-methoxyphenylacetamide] places the substituents of this chiral center in a different spatial orientation, originating opposite helical senses at the polymer that are induced through a total control of the "chiral overpass effect".
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Affiliation(s)
- Rafael Rodríguez
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química OrgánicaUniversidade de Santiago de Compostela15782Santiago de CompostelaSpain
- WPI Nano Life Science Institute (WPI-NanoLSI)Kanazawa UniversityKakuma-machiKanazawa920-1192Japan
| | - Elena Rivadulla‐Cendal
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química OrgánicaUniversidade de Santiago de Compostela15782Santiago de CompostelaSpain
| | - Manuel Fernández‐Míguez
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química OrgánicaUniversidade de Santiago de Compostela15782Santiago de CompostelaSpain
| | - Berta Fernández
- Departamento de Química FísicaUniversidade de Santiago de Compostela15782Santiago de CompostelaSpain
| | - Katsuhiro Maeda
- WPI Nano Life Science Institute (WPI-NanoLSI)Kanazawa UniversityKakuma-machiKanazawa920-1192Japan
- Graduate School of Natural Science and TechnologyKanazawa UniversityKakuma-machiKanazawa920-1192Japan
| | - Emilio Quiñoá
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química OrgánicaUniversidade de Santiago de Compostela15782Santiago de CompostelaSpain
| | - Félix Freire
- Centro Singular de investigación en Química Biolóxica e Materiais Moleculares (CiQUS) e Departamento de Química OrgánicaUniversidade de Santiago de Compostela15782Santiago de CompostelaSpain
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23
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Ikai T, Okuda S, Aizawa M, Yashima E. Chiral and Achiral Pendant-Bound Poly(biphenylylacetylene)s Bearing Amide and/or Carbamate Groups: One-Handed Helix Formations and Chiral Recognition Abilities. Macromolecules 2022. [DOI: 10.1021/acs.macromol.2c01362] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/29/2022]
Affiliation(s)
- Tomoyuki Ikai
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
- Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan
| | - Shogo Okuda
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
| | - Motoki Aizawa
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
| | - Eiji Yashima
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
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24
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Khazeber R, Sureshan KM. Single-crystal-to-single-crystal translation of a helical supramolecular polymer to a helical covalent polymer. Proc Natl Acad Sci U S A 2022; 119:e2205320119. [PMID: 35858342 PMCID: PMC9303982 DOI: 10.1073/pnas.2205320119] [Citation(s) in RCA: 13] [Impact Index Per Article: 4.3] [Reference Citation Analysis] [Abstract] [Key Words] [Grants] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 03/29/2022] [Accepted: 05/30/2022] [Indexed: 01/16/2023] Open
Abstract
Polymers possessing helical conformation in the solid state are in high demand. We report a helical peptide-polymer via the topochemical ene-azide cycloaddition (TEAC) polymerization. The molecules of the designed Gly-Phe-based dipeptide, decorated with ene and azide, assemble in its crystals as β-sheets and as supramolecular helices in two mutually perpendicular directions. While the NH…O H-bonding facilitates β-sheet-like stacking along one direction, weak CH…N H-bonding between the azide-nitrogen and vinylic-hydrogen of molecules belonging to the adjacent stacks arranges them in a head-to-tail manner as supramolecular helices. In the crystal lattice, the azide and alkene of adjacent molecules in the supramolecular helix are suitably preorganized for their TEAC reaction. The dipeptide underwent regio- and stereospecific polymerization upon mild heating in a single-crystal-to-single-crystal fashion, yielding a triazoline-linked helical covalent polymer that could be characterized by single-crystal X-ray diffraction studies. Upon heating, the triazoline-linked polymer undergoes denitrogenation to aziridine-linked polymer, as evidenced by differential scanning calorimetry, thermogravimetric analysis, and solid-state NMR analyses.
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Affiliation(s)
- Ravichandran Khazeber
- School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Kerala-695551, India
| | - Kana M. Sureshan
- School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Kerala-695551, India
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25
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Ikai T, Takeda S, Yashima E. Catalytic One-Handed Helix Induction and Subsequent Static Memory of Poly(biphenylylacetylene)s Assisted by a Small Amount of Carboxy Groups Introduced at the Pendants. ACS Macro Lett 2022; 11:525-531. [PMID: 35575344 PMCID: PMC9022430 DOI: 10.1021/acsmacrolett.2c00136] [Citation(s) in RCA: 6] [Impact Index Per Article: 2.0] [Reference Citation Analysis] [Abstract] [MESH Headings] [Grants] [Track Full Text] [Download PDF] [Figures] [Journal Information] [Subscribe] [Scholar Register] [Received: 03/01/2022] [Accepted: 03/25/2022] [Indexed: 12/04/2022]
Abstract
A dynamically racemic helical copolymer composed of an achiral biphenylylacetylene (BPA) bearing methoxymethoxy groups at the 2,2'-positions and 1 mol % of an achiral BPA carrying 2-carboxy-2'-methoxymethoxy groups at the biphenyl pendants was found to fold into an excess one-handed helix with significant amplification of the helicity in the presence of a small amount of optically active amines. The induced macromolecular helicity was retained ("memorized") after removal of the chiral amines. The copolymer had a significant sensitivity for detecting the chirality of chiral amines with a sensitivity more than 10000-fold higher than that of the corresponding homopolymers with no carboxy group, thus showing Cotton effects even in the presence of a 0.01 equiv of an optically active amine. The effects of the substituents at the 4'-position of the biphenyl pendants of the copolymers and the structures of the chiral amines on the macromolecular helicity induction were also investigated.
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Affiliation(s)
- Tomoyuki Ikai
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
- Precursory
Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST), Kawaguchi, Saitama 332-0012, Japan
| | - Shoki Takeda
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
| | - Eiji Yashima
- Department
of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan
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26
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Aoun P, Hammoud A, Martínez-Aguirre MA, Bouteiller L, Raynal M. Asymmetric hydroamination with far fewer chiral species than copper centers achieved by tuning the structure of supramolecular helical catalysts. Catal Sci Technol 2022. [DOI: 10.1039/d1cy02168k] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/21/2022]
Abstract
Mixing a BTA ligand (in black), a “sergeant” (in blue) and an achiral BTA additive (in orange) affords the amination product in 75% e.e. even though only one “sergeant” for ca. 10 copper centers are present in the supramolecular helical catalyst.
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Affiliation(s)
- Paméla Aoun
- CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, Sorbonne Université, 4 Place Jussieu, 75005 Paris, France
| | - Ahmad Hammoud
- CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, Sorbonne Université, 4 Place Jussieu, 75005 Paris, France
| | - Mayte A. Martínez-Aguirre
- CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, Sorbonne Université, 4 Place Jussieu, 75005 Paris, France
| | - Laurent Bouteiller
- CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, Sorbonne Université, 4 Place Jussieu, 75005 Paris, France
| | - Matthieu Raynal
- CNRS, Institut Parisien de Chimie Moléculaire, Equipe Chimie des Polymères, Sorbonne Université, 4 Place Jussieu, 75005 Paris, France
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27
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Zhou L, He K, Liu N, Wu ZQ. Recent advances in asymmetric organocatalysis based on helical polymers. Polym Chem 2022. [DOI: 10.1039/d2py00483f] [Citation(s) in RCA: 3] [Impact Index Per Article: 1.0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 12/21/2022]
Abstract
The significant research progress (from 2011 to 2021) in artificial helical polymers, such as polyacetylenes, polyisocyanides, polycarbenes, etc., in the fields of asymmetric organocatalysis is described.
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Affiliation(s)
- Li Zhou
- Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei 230009, Anhui Province, China
| | - Kai He
- Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei 230009, Anhui Province, China
| | - Na Liu
- Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei 230009, Anhui Province, China
| | - Zong-Quan Wu
- Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, and Anhui Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, Hefei University of Technology, Hefei 230009, Anhui Province, China
- State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China
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28
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Ikai T, Okuda S, Yashima E. Macromolecular helicity induction and static helicity memory of poly(biphenylylacetylene)s bearing aromatic pendant groups and their use as chiral stationary phases for high-performance liquid chromatography. Chirality 2021; 34:306-316. [PMID: 34839544 DOI: 10.1002/chir.23399] [Citation(s) in RCA: 6] [Impact Index Per Article: 1.5] [Reference Citation Analysis] [Abstract] [Key Words] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Received: 10/06/2021] [Revised: 11/08/2021] [Accepted: 11/10/2021] [Indexed: 12/28/2022]
Abstract
Two novel poly(biphenylylacetylene)s (PBPAs) bearing achiral alkylphenyl groups at the 4'-position of the biphenyl pendant through ester linkers with different sequences were synthesized by the rhodium-catalyzed polymerization of the corresponding monomers. The influence of the alkylphenyl pendants and the ester sequences on the macromolecular helicity induction and subsequent static helicity memory was investigated. In addition, the chiral recognition ability as chiral stationary phases for high-performance liquid chromatography of the helicity-memorized PBPAs was also examined. Both polymers formed almost perfect right- and left-handed helical conformations through noncovalent chiral interactions with enantiomeric alcohols, and their induced macromolecular helicities were completely retained ("memorized") after removal of the helix inducer. A PBPA bearing a 4-n-butylphenoxycarbonyl pendant group with a static helicity memory showed a remarkably high chiral recognition ability toward a wide variety of chiral aromatics, including simple point chiral compounds, axially chiral biaryls, a chiral spiro compound, helicenes, and planar chiral cyclophanes, particularly under the reversed-phase conditions.
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Affiliation(s)
- Tomoyuki Ikai
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan
| | - Shogo Okuda
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan
| | - Eiji Yashima
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Nagoya, Japan
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29
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Yashima E, Maeda K. Helical Polymers with Dynamic and Static Macromolecular Helicity Memory: The Power of Helicity Memory for Helical Polymer Synthesis and Applications. BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 2021. [DOI: 10.1246/bcsj.20210282] [Citation(s) in RCA: 18] [Impact Index Per Article: 4.5] [Reference Citation Analysis] [Track Full Text] [Subscribe] [Scholar Register] [Indexed: 12/28/2022]
Affiliation(s)
- Eiji Yashima
- Department of Molecular and Macromolecular Chemistry, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya, Aichi 464-8603, Japan
| | - Katsuhiro Maeda
- Nano Life Science Institute (WPI-NanoLSI), Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192, Japan
- Graduate School of Natural Science and Technology, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192, Japan
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30
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Helical Polycarbenes Bearing D-Prolinol Ester Pendants: An Efficient Catalyst for Asymmetric Michael Addition Reaction. Catalysts 2021. [DOI: 10.3390/catal11111369] [Citation(s) in RCA: 0] [Impact Index Per Article: 0] [Reference Citation Analysis] [Abstract] [Track Full Text] [Journal Information] [Subscribe] [Scholar Register] [Indexed: 11/16/2022] Open
Abstract
A novel diazoacetate monomer (1) carrying tert-butyloxycarboryl (Boc) protected D-prolinol ester was designed and synthesized successfully. Molecular weight-controlled polymerization of 1 using the complex of π-allylPdCl coordinated Wei-phos (LR) ligand gives a series of helical polycarbenes (poly-1ms) with well-defined molecular weights (Mns) and low polydispersity (Mw/Mns). Removing the protecting Boc groups on the D-prolinol ester pendants leads to the formation of helical poly-1m-As, which showed high optical activity. Furthermore, the poly-1m-As showed high catalytic ability on asymmetric Michael addition reaction (up to 76% ee and 94/6 dr). Both the enantioselectivity and diastereoselectivity of the Michael addition reaction were increased comparing to D-prolinol as catalyst. Moreover, the helical polycarbene catalyst can be easily recovered and reused at least four times without significant loss of its enantioselectivity and diastereoselectivity.
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