Review
Chemistry, Inorganic & Nuclear
Le Zhou, Shuai Cao, Chang Liu, Huacheng Zhang, Yanli Zhao
Summary: This review summarizes recent advances in pillar[n]arene-based polymers for biomedical applications, including controlled drug release, chemotherapy, photodynamic therapy, and anti-bacteria. The functional pillar[n]arene-based polymers with intelligent and controllable characteristics offer promising prospects in the field of biomedical materials. The integration of pillar[n]arenes into polymeric architectures endows the supramolecular systems with intriguing properties.
COORDINATION CHEMISTRY REVIEWS
(2023)
Review
Nanoscience & Nanotechnology
Laila E. Khalil-Cruz, Peiren Liu, Feihe Huang, Niveen M. Khashab
Summary: The design and functionalization of smart nanomaterials, particularly using pillar[n]arenes as host macrocycles, have attracted significant attention in recent research. Pillar[n]arenes offer advantages in terms of ease of functionalization and high selectivity in complexing metal ions, resulting in materials with diverse and captivating properties and functions.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Chao Peng, Wenting Liang, Jiecheng Ji, Chunying Fan, Kuppusamy Kanagaraj, Wanhua Wu, Guo Cheng, Dan Su, Zhihui Zhong, Cheng Yang
Summary: A pyrene-tiaraed pillar[5]arene derivative was synthesized, which exhibited concentration-independent intensive excimer emission. Photolysis of the derivative resulted in a switch from excimer to monomer emission, suitable for photo-writing applications.
CHINESE CHEMICAL LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Yang Chao, Tushar Ulhas Thikekar, Wangjian Fang, Rong Chang, Jiong Xu, Nianfeng Ouyang, Jun Xu, Yan Gao, Minjie Guo, Han Zuilhof, Andrew C-H Sue
Summary: A rim-differentiated pillar[6]arene (RD-P[6]) was successfully synthesized and its solid-state conformation can switch upon guest inclusion. It can not only host metal-containing molecules inside its cavity but also form adducts with other molecules. The development of synthetic strategies to desymmetrize pillararenes offers new opportunities for engineering complex molecular architectures and organic electronic materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Materials Science, Multidisciplinary
Li Wang, Guang Li, Lei Yang, Haonan Qu, Jing Cheng, Mohammed Abdallah, Dalia A. Barakat, Haibing Li
Summary: This study successfully prepared MIMs using S-triadimefon as the template molecule and improved the chiral selectivity by adding macrocyclic molecular 1,4-bis(allyloxy)pillar[5]arene. The results showed that the addition of pillar[5]arene significantly improved the separation effect of MIM on triadimefon enantiomers.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Pharmacology & Pharmacy
Yahan Zhang, Mengke Ma, Longming Chen, Xinbei Du, Zhao Meng, Han Zhang, Zhibing Zheng, Junyi Chen, Qingbin Meng
Summary: Advanced external preparations with sustained-release effect and low irritancy are urgently needed for topical administration in clinics. Researchers designed and synthesized liquid pillar[n]arene compounds and constructed a supramolecular liquid reservoir through host-guest complexes with an external antimicrobial agent, regulating drug release and accelerating wound healing.
Article
Chemistry, Multidisciplinary
Kenichi Kato, Katsuto Onishi, Koki Maeda, Masafumi Yagyu, Shixin Fa, Takahiro Ichikawa, Motohiro Mizuno, Takahiro Kakuta, Tada-Aki Yamagishi, Tomoki Ogoshi
Summary: This study demonstrates a method to prepare pseudopolyrotaxanes and polyrotaxanes by threading linear PEOs molecules into pillar[5]arene rings and controlling the number of threaded ring components to tune the mechanical and thermal properties of the materials. Specifically, a polyrotaxane with a high-molecular-weight axle exhibited temperature-dependent shape memory property due to topological confinement and crosslinked hydrogen bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Nanoscience & Nanotechnology
Xin Liu, Ji Liu, Chi Meng, Peng Zhu, Xiao Liu, Jianqiang Qian, Shijia Ling, Yanan Zhang, Yong Ling
Summary: Chemodynamic therapy (CDT) based on the intracellular Fenton reaction is a promising approach for cancer treatment. This study introduces a novel supramolecular nanocatalyst, GOx@T-NPs, which exhibits high efficiency in converting glucose into hydroxyl radicals and enhancing the CDT effect. Furthermore, GOx@T-NPs demonstrate excellent biocompatibility, tumor selectivity, and trimodal synergistic interactions for efficient cancer therapy.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Biochemistry & Molecular Biology
Alan A. Akhmedov, Dmitriy N. Shurpik, Pavel L. Padnya, Alena Khadieva, Rustem R. Gamirov, Yulia Panina, Asiya F. Gazizova, Denis Yu Grishaev, Vitaliy V. Plemenkov, Ivan I. Stoikov
Summary: Research has been conducted on creating supramolecular amphiphiles based on water-soluble pillar[5]arene and synthetic meroterpenoids for universal drug delivery systems; These systems can stably exist without interacting with cell membranes and incorporate the meroterpenoids into the lipid bilayer of model membranes under certain conditions.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2021)
Article
Chemistry, Analytical
Tao Sun, Ruonan Chen, Qiuchen Huang, Mengyi Ba, Zhiqiang Cai, Haipeng Chen, Yueheng Qi, Hong Chen, Xianming Liu, Donatella Nardiello, Maurizio Quinto
Summary: This study investigates the use of pillar [6]arene derivative modified by long alkyl chains (P6A-C10) as a stationary phase for high-resolution gas chromatographic (GC) separations of xylene isomers, addressing the challenge of separating aromatic isomers in chemical and petroleum industries. The P6A-C10 column shows higher resolution and unique advantages compared to commercial HP-5, HP-35, DB-17, and PEG-20M columns. Quantum chemistry calculations reveal differences in non-covalent interactions with the P6A-C10 pillar framework, leading to specific selectivity for xylene isomers. Furthermore, the P6A-C10 column exhibits good repeatability.
ANALYTICA CHIMICA ACTA
(2023)
Review
Chemistry, Multidisciplinary
Roymon Joseph
Summary: Pillar[n]arenes and their derivatives are widely used as host systems for sensing amino acids, with most sensors detecting amino acids using fluorescence techniques and some achieving sensing visually through color changes.
Article
Nanoscience & Nanotechnology
Tao Sun, Ruonan Chen, Qiuchen Huang, Mengyi Ba, Zhiqiang Cai, Shaoqiang Hu, Xianming Liu, Donatella Nardiello, Maurizio Quinto
Summary: This study reported the fabrication, synthesis, and characterization of a new stationary phase based on an amphiphilic pillar[6]arene for gas chromatographic analyses. The column exhibited medium polarity, high efficiency, and unmatched resolving capabilities. The new stationary phase showed excellent repeatability, indicating great potential for applications in separation science.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Nanoscience & Nanotechnology
Yun-Zhe Guo, Fei Gao, Zhuo Wang, Yahu A. Liu, Wei-Bo Hu, Hui Yang, Ke Wen
Summary: The study demonstrated the fabrication of PAF-P5 for efficient adsorption and removal of organic pollutants from water, with a limitation towards aromatic organic dyes. By chemically breaking down the pillar[5]arene rings in PAF-P5, the resultant PAF-DeP5 exhibited altered adsorption capabilities towards different types of organic pollutants.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Multidisciplinary
Helena Butkiewicz, Sandra Kosiorek, Volodymyr Sashuk, Magdalena M. Zimnicka, Oksana Danylyuk
Summary: In this study, the solid state supramolecular chemistry of carboxylated pillar[6]arene was explored, and the structure of carboxylated pillar[6]arene was authenticated for the first time. The successful crystallographic authentication was achieved through the host-guest inclusion complexes of carboxylated pillar[6]arene with methyl viologen and pentamidine. The conformation of pillar[6]arene in the inclusion complex was found to be quasi-pentagonal, deviating from the expected hexagonal shape. These results provide insight into the control of the conformation of flexible pillar[6]arene and the design of advanced supramolecular host-guest structures in the solid state.
CRYSTAL GROWTH & DESIGN
(2023)
Review
Chemistry, Multidisciplinary
Zhaona Liu, Bing Li, Leqian Song, Huacheng Zhang
Summary: Hybrid macrocyclic hosts containing rigid pillar[n]arene and flexible calix[m]arene were designed and prepared to reserve planar chirality, enhance molecular recognition, and build advanced self-assemblies. Different synthetic strategies were summarized and discussed for constructing hybrid macrocyclic structures. These structures exhibited interesting applications in molecular recognition, self-assembly, and catalysis.
Article
Chemistry, Multidisciplinary
Kenichi Kato, Katsuto Onishi, Koki Maeda, Masafumi Yagyu, Shixin Fa, Takahiro Ichikawa, Motohiro Mizuno, Takahiro Kakuta, Tada-Aki Yamagishi, Tomoki Ogoshi
Summary: This study demonstrates a method to prepare pseudopolyrotaxanes and polyrotaxanes by threading linear PEOs molecules into pillar[5]arene rings and controlling the number of threaded ring components to tune the mechanical and thermal properties of the materials. Specifically, a polyrotaxane with a high-molecular-weight axle exhibited temperature-dependent shape memory property due to topological confinement and crosslinked hydrogen bonds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Shixin Fa, Masayuki Mizobata, Shusaku Nagano, Kota Suetsugu, Takahiro Kakuta, Tada-aki Yamagishi, Tomoki Ogoshi
Summary: The study presents chiral assemblies with dual-stimuli responsiveness, consisting of planar-chiral pillar[5]arenes with azobenzene groups that undergo chiral amplification and collapse under thermo- and photostimuli control. The alignment of azobenzenes in the assemblies leads to chiral propagation and amplification, which can be switched on and off through trans to cis photoisomerization and cis to trans thermo-isomerization of the azobenzene groups.
Article
Chemistry, Multidisciplinary
Kenichi Kato, Yuta Kurakake, Shunsuke Ohtani, Shixin Fa, Masayuki Gon, Kazuo Tanaka, Tomoki Ogoshi
Summary: Control of symmetry is crucial in molecular design with desired properties. In this study, a series of chiroptical C-5-symmetric molecules with variable dipolar structures based on pillar[5]arene were reported. Incorporation of electron-withdrawing ester groups led to an explicit two-sided structure, resulting in an increase in response wavelength and luminescence efficiency. Chiroptical measurement of separated enantiomers revealed that the dipolar character reduced the dissymmetry of electronic transitions. By suppressing the dipole, the dissymmetry factor for luminescence was significantly enhanced.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Tan-Hao Shi, Yuuya Nagata, Shigehisa Akine, Shunsuke Ohtani, Kenichi Kato, Tomoki Ogoshi
Summary: This article introduces a method for bottom-up synthesis using chiral seeds and chiral walls to construct twisted chiral cavitands with specific chiralities. By dynamic covalent bonding, thermodynamically stable enantiomeric products are obtained selectively, and selective binding of alkylene dibromides to the twisted cavitand is observed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Keisuke Wada, Misaki Suzuki, Takahiro Kakuta, Tada-aki Yamagishi, Shunsuke Ohtani, Shixin Fa, Kenichi Kato, Shigehisa Akine, Tomoki Ogoshi
Summary: Controlling and memorizing chirality are important in chemistry. Noncovalent interactions have been commonly used for chirality memory, but the memorized chirality can easily be erased by changing conditions. This study successfully transformed dynamic chirality into static chirality in pillar[5]arenes by introducing bulky groups through covalent bonds. The chirality was memorized by the introduction of bulky groups and the diastereomeric excess was amplified by crystallization. The resulting pillar[5]arenes exhibited excellent diastereomeric excess.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Kenichi Kato, Tomoya Kaneda, Shunsuke Ohtani, Tomoki Ogoshi
Summary: Installation of substituents is a useful method to modify macrocyclic molecules, but controlled multifold reactions are often challenging. In this study, we achieved 10- and 12-fold introduction of aryl substituents onto both rims of cylinder-shaped pillar[n]arenes. The arylated pillar[5]arenes displayed unique crystal structures and stereoisomerism. Additionally, pillar[n]arenes with benzofuranyl groups exhibited bright fluorescence and no host-guest complexation with electron-deficient molecules in solution.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Keisuke Adachi, Shixin Fa, Keisuke Wada, Kenichi Kato, Shunsuke Ohtani, Yuuya Nagata, Shigehisa Akine, Tomoki Ogoshi
Summary: Chirality of host molecules can be adapted and inverted by guest molecules, and in this study, a pillar[5]arene-based macrocyclic host, S-Br, was used to adapt its chirality to the length of n-alkanes. Short n-alkanes favored the pS-form of S-Br, while long n-alkanes favored the pR-form. Temperature also played a role in driving the adaptive chirality of S-Br with n-alkanes.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Shin Morioka, Shoko Sato, Naoki Horikoshi, Tomoya Kujirai, Takuya Tomita, Yudai Baba, Takahiro Kakuta, Tomoki Ogoshi, Leonardo Puppulin, Ayumi Sumino, Kenichi Umeda, Noriyuki Kodera, Hitoshi Kurumizaka, Mikihiro Shibata
Summary: This study used high-speed atomic force microscopy to directly observe the subsecond dynamics of human H2A.Z.1-nucleosomes. The results showed that the nucleosomes can slide along 4 nm of DNA within 0.3 s in any direction. The interaction between the N-terminal region of H2A.Z.1 and the DNA was found to be responsible for nucleosome sliding.
Review
Chemistry, Multidisciplinary
Tan-Hao Shi, Shunsuke Ohtani, Kenichi Kato, Shixin Fa, Tomoki Ogoshi
Summary: Pillar[n]arenes typically form 1:1 host-guest complexes with guest molecules, but unique properties arise from the formation of new structures and the crystalline state. Cooperative binding of guest molecules to pillar[n]arene assemblies is crucial to achieve unique host-guest behavior. Moreover, planar chirality of pillar[n]arenes allows for chiral inversion, memory, and erasure, which is coupled with their host-guest properties. In this review, the diversity, functionality, and supramolecular chirality of host-guest pillar[n]arene assemblies are discussed.
TRENDS IN CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Kenichi Kato, Shixin Fa, Tomoki Ogoshi
Summary: Pillar[n]arenes, composed of benzene panels with para-methylene linkages, are symmetrical macrocyclic compounds. The planar chirality of each panel and its preference for chirality-aligned states make pillar[n]arenes attractive scaffolds for chiroptical materials with intense circular dichroism (CD) signals. Additionally, the dynamic nature of the chirality in pillar[n]arenes allows for time- and procedure-dependent alignment phenomena and response to chiral guests, providing molecular sensors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Keisuke Wada, Kiichi Yasuzawa, Shixin Fa, Yuuya Nagata, Kenichi Kato, Shunsuke Ohtani, Tomoki Ogoshi
Summary: Chiral rotaxanes have been receiving much attention due to their unique chirality arising from their interlocked structures, and selective synthesis methods have been developed. The introduction of chiral substituents to produce diastereomers is an effective strategy. This study reports a new method for the diastereoselective synthesis of rotaxanes using solid-phase diastereoselective [3]pseudorotaxane formation and mechanochemical solid-phase end-capping reactions. The co-crystallization of stereodynamic planar chiral pillar[5]arene with suitable end groups and lengths yielded a [3]pseudorotaxane with high diastereomeric excess in the solid state, while maintaining the high diastereomeric excess during the subsequent end-capping reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Polymer Science
Tomoki Ogoshi
Summary: Macrocyclic compounds with highly symmetric structures can be used as building blocks for various supramolecular assemblies. This review presents the diverse and functionalized supramolecular assemblies based on pillar[n]arenes, which have polygonal structures. By functionalizing pillar[n]arenes, one-dimensional channels, two-dimensional sheets, and three-dimensional vesicles with continuous and length-controllable structures have been produced. The review also discusses the bulk-state complexations using liquid and crystalline pillar[n]arenes, as well as the functionalized crystals that show guest-responsive changes and can serve as reaction media.
Article
Multidisciplinary Sciences
Shotaro Tsujioka, Ayumi Sumino, Yutaro Nagasawa, Takashi Sumikama, Holger Flechsig, Leonardo Puppulin, Takuya Tomita, Yudai Baba, Takahiro Kakuta, Tomoki Ogoshi, Kenichi Umeda, Noriyuki Kodera, Hideji Murakoshi, Mikihiro Shibata
Summary: CaMKII plays a crucial role in synaptic plasticity and its molecular behavior has been observed using high-speed atomic force microscopy. The dynamic behavior is dependent on CaM binding and pT286 phosphorylation. Rat CaMKIIa exhibited kinase domain oligomerization, which was not observed in other species. Sensitivity to PP2A also differs between the three species.
Article
Chemistry, Multidisciplinary
Kenichi Kato, Shunsuke Ohtani, Masayuki Gon, Kazuo Tanaka, Tomoki Ogoshi
Summary: The spatial arrangement of multiple planar chromophores is an emerging strategy for molecule-based chiroptical materials, and in this study, five pyrene planes were attached to a chiral macrocycle pillar[5]arene to produce a set of chiroptical molecules. The chiroptical response was found to depend on linker structures and substituted patterns due to variable interactions between pyrene units, leading to enhanced dissymmetry factors and response wavelengths.
Review
Chemistry, Multidisciplinary
Kenichi Kato, Shixin Fa, Shunsuke Ohtani, Tan-hao Shi, Albert M. Brouwer, Tomoki Ogoshi
Summary: Pillar[n]arenes are pillar-shaped macrocyclic compounds with unique structures and excellent properties, such as versatility, substituent-dependent solubility, cavity-size-dependent host-guest properties, and unit rotation. These advantages enable the high-yield synthesis and rational design of pillar[n]arene-based mechanically interlocked molecules (MIMs) that can dynamically convert between interlocked and unlocked states. The highly symmetrical pillar-shaped structures of pillar[n]arenes are also useful for studying the motion of pillar[n]arene wheels in MIMs and creating sophisticated MIMs with higher-order structures.
CHEMICAL SOCIETY REVIEWS
(2022)