Article
Chemistry, Multidisciplinary
Pieter J. Gilissen, Annemiek D. Slootbeek, Jiangkun Ouyang, Nicolas Vanthuyne, Rob Bakker, Johannes A. A. W. Elemans, Roeland J. M. Nolte
Summary: The construction of macromolecular hosts capable of threading chiral guests in a stereoselective manner is a challenge. The asymmetric synthesis of two enantiomeric C-2-symmetric porphyrin macrocyclic hosts has been described, showing kinetic selectivity for different viologen guests. The presence or absence of chiral termini in the viologen guests affects the kinetic selectivity of the threading process onto the hosts.
Article
Multidisciplinary Sciences
Song-Meng Wang, Yan-Fang Wang, Liping Huang, Li-Shuo Zheng, Hao Nian, Yu-Tao Zheng, Huan Yao, Wei Jiang, Xiaoping Wang, Liu-Pan Yang
Summary: Developing chiral receptors with an endo-functionalized cavity for chiral recognition is highly significant in the field of molecular recognition. This study introduces chiral naphthotubes containing a bis-thiourea endo-functionalized cavity, which effectively recognize neutral chiral molecules with high enantioselectivity. The chiral recognition mechanism is attributed to differences in multiple non-covalent interactions, where factors such as cavity shape, guest substituents, host flexibility, and binding modes contribute to creating these differences. Enantioselectivity is primarily driven by enthalpic differences, with enthalpy-entropy compensation also influencing the selectivity.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Kenji Yamashita, Yuji Tabata, Katsuya Yamakawa, Takuya Mochizuki, Kai Matsui, Manabu Hatano, Kazuaki Ishihara
Summary: Alkynyl addition to carbonyl compounds is an important synthetic method for the preparation of versatile chiral alcohols. In this study, a catalytic enantioselective addition of lithium acetylide to ketones using macrocyclic lithium binaphtholates as catalysts was reported. The designed macrocyclic structure prevented aggregation and resulted in monomeric and highly active catalysts that can produce enantioenriched tertiary alcohols from various ketones within a short reaction time.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Geunmoo Song, Kyung Mog Kim, Seungwon Lee, Kyu-Sung Jeong
Summary: Aromatic helical receptors P-1 and P-2 were modified slightly by aerobic oxidation to produce new receptors P-7 and P-8 with right-handed helical cavities, which led to significant changes in binding properties for chiral guests. Subtle post-modifications of the synthetic receptors were shown to significantly alter their binding affinities and selectivities, especially for guests with long and flexible chains.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Nanoscience & Nanotechnology
Aya Edagawa, Satoru Matsuda, Hirofumi Kawakubo, Hiroaki Imai, Yuya Oaki
Summary: This study investigates the flexibility of layered polydiacetylene (PDA) by using interlayer polymeric guests with different branching structures. The addition of bulky polymer guests enhances the thermoresponsive color-change properties of PDA. The resulting composite material can be uniformly coated onto substrates and utilized for temperature distribution imaging.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Analytical
Xiaohui Niu, Simeng Yan, Rui Zhao, Sha Han, Kunjie Cao, Hongxia Li, Kunjie Wang
Summary: Chirality is important in natural and life sciences, and chiral materials are widely used for electrochemical chiral recognition. Carbon quantum dots have shown potential as a novel carbon nanomaterial due to their unique properties. Self-assembly of achiral porphyrins induced by chiral carbon quantum dots was demonstrated, and the resulting structure showed good electrochemical chiral recognition properties. This research provides a new approach for synthesizing chiral composites and expanding the applications of electrochemical chiral recognition.
Article
Chemistry, Multidisciplinary
Takashi Komori, Eiji Tsurumaki, Shinji Toyota
Summary: In this study, acridone units were incorporated into the arylene-ethynylene structure as polar arene units. Cyclic trimers consisting of acridone-2,7-diyl units and 1,3-phenylene units were synthesized, and their structures were analyzed using X-ray analysis and H-1 NMR measurements. The trimer formed a 1:1 complex with dihydric phenol guests, and the association constants were determined. The structures of the complexes were supported by DFT calculations, and the spectroscopic data were compared with reference acridone compounds.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Multidisciplinary Sciences
Yusuke Nakakuki, Takashi Hirose, Hikaru Sotome, Min Gao, Daiki Shimizu, Ruiji Li, Jun-Ya Hasegawa, Hiroshi Miyasaka, Kenji Matsuda
Summary: Helically twisted conductive nanocarbon materials are suitable for optoelectronic and electromagnetic molecular devices on the nanometer scale, showing a large effective conjugation length and ultrafast decay dynamics. The extended π-helicenes achieved a large effective conjugation length through helical fusion, leading to an absorption edge in the near-infrared region.
NATURE COMMUNICATIONS
(2022)
Review
Chemistry, Analytical
Pieter De Gauquier, Kenno Vanommeslaeghe, Yvan Vander Heyden, Debby Mangelings
Summary: This article presents an overview of molecular modelling approaches for chiral separations on polysaccharide-based and macrocyclic antibiotic chiral selectors. Both atomistic calculations and empirical fitting procedures are discussed. Atomistic calculations, such as docking and molecular dynamics, can provide insights into the chiral recognition mechanism by modeling the interactions between enantiomers and the chiral stationary phase. On the other hand, empirical fitting procedures involve mathematical models that are fitted to experimental observations using theoretical molecular descriptors. These models can be used to predict a specific response, such as retention, in chiral separations. The article also discusses different regression models, such as multiple linear regression and partial least squares.
ANALYTICA CHIMICA ACTA
(2022)
Article
Chemistry, Organic
Yan-Fang Xue, Jie Liu, Qingmei Ge, Nan Jiang, Wen-Feng Zhao, Mao Liu, Jiang-Lin Zhao, Hang Cong
Summary: In this study, a supramolecular strategy was used for the asymmetric hydrogenation of 4-methylumbelliferone by electrochemical reduction in the presence of a chiral macrocyclic multifarane[3,3]. The reaction afforded a L-7-hydroxy-4-methylchroman-2-one product with a chemical yield of 65% and enantioselectivity up to >99% ee. The developed chiral supramolecular electrode exhibited high stability, allowing for recyclability and repeatability in the electrolysis. The application of this strategy was successfully extended to other coumarin derivatives, providing satisfactory chemical yields and enantioselectivities.
Article
Chemistry, Organic
Yan-Fang Xue, Jie Liu, Qingmei Ge, Nan Jiang, Wen-Feng Zhao, Mao Liu, Hang Cong, Jiang-Lin Zhao
Summary: The supramolecular strategy was successfully used for the asymmetric hydrogenation of 4-methylumbelliferone by electrochemical reduction. A chiral macrocyclic multifarane[3,3] was utilized as the catalyst, leading to a L-7-hydroxy-4-methylchroman-2-one product with a chemical yield of 65% and enantioselectivity up to >99% ee. The developed chiral supramolecular electrode exhibited high stability, allowing for recyclability and repeatability in the electrolysis. Moreover, the strategy was applicable to other coumarin derivatives, providing satisfactory chemical yields and enantioselectivities.
Correction
Chemistry, Multidisciplinary
Davide Ranieri, Fabio Santanni, Alberto Privitera, Andrea Albino, Enrico Salvadori, Mario Chiesa, Federico Totti, Lorenzo Sorace, Roberta Sessoli
Summary: This correction article discusses the application of vanadyl porphyrin dimer in quantum information processing. The authors address some issues and errors in previous works and provide a more accurate understanding of the vanadyl porphyrin dimer.
Article
Chemistry, Multidisciplinary
Dan Qu, Matteo Archimi, Andrea Camposeo, Dario Pisignano, Eyal Zussman
Summary: A method of fabricating circularly polarized lasers using cellulose nanocrystals and a laser dye through evaporation-induced assembly is presented, showing controlled chiral nematic structure and modification of laser polarization state into left-handed, resulting in strong and tailored CP laser emission.
Article
Chemistry, Applied
Zhichao Lin, Zhan Jiang, Yubo Yuan, Huan Li, Hongxuan Wang, Yirong Tang, Chunchen Liu, Yongye Liang
Summary: Metal-N-4 (M-N-4) macrocyclic complexes are interesting electrocatalysts with well-defined structures and molecular tuning. Among them, cobalt phthalocyanine shows high electrocatalytic activity for the carbon dioxide reduction reaction (CO2RR), while cobalt porphyrins and cobalt corroles exhibit inferior performances. The introduction of poly(4-vinylpyridine) enhances the activity of cobalt porphyrin.
CHINESE JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Organic
Fei Yang, Yunong Li, Ran Li, Xiaolin Wang, Xiangkun Cui, Wei Wei, Yanqing Xu
Summary: In this study, a class of organic macrocycles was efficiently synthesized using a new precursor and length-variable linkers. These macrocycles showed evident size-matching effect with different-sized guest molecules. Furthermore, one of the host-guest products exhibited excellent photothermal activity for antibacterial application.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Kazuto Takaishi, Tomoki Matsumoto, Miyu Kawataka, Tadashi Ema
Summary: A series of axially chiral 1,1'-binaphthyls with trialkylsiloxy (OSiR3) groups have been synthesized, with some showing circularly polarized luminescence (CPL) in liquid state at room temperature. Time-dependent DFT calculations revealed a transoid conformation in the excited state is essential for the CPL activity, with a dihedral angle of approximately 110 degrees.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Chihiro Maeda, Shuichi Nomoto, Koki Akiyama, Takayuki Tanaka, Tadashi Ema
Summary: Carbazole-based aza[7]helicenes and hetero[9]helicenes were successfully obtained via intramolecular Scholl reaction. Additionally, a compound with triple helicene structure was discovered through unexpected double aryl rearrangement. The helical dyes exhibited circularly polarized luminescence, and azahepta[8]circulene was further transformed into deeply saddle-distorted dibenzodiaza[8]circulenes as a solution-based synthesis example.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Multidisciplinary Sciences
Kazunori Yoshida, Shun Kawai, Masaya Fujitani, Satoshi Koikeda, Ryuji Kato, Tadashi Ema
Summary: By combining loop-walking method and machine learning, a hot-spot loop crucial for protein thermostability was identified, and an ideal mutant was discovered from 214 variants. Though screening the best mutant remains challenging, a computational discrimination model was successfully constructed to predict thermostability, leading to the selection of 20 promising candidates among 7786 combinations for further evaluation. This approach provides a foundation for improvement and optimization in the future.
SCIENTIFIC REPORTS
(2021)
Article
Chemistry, Multidisciplinary
Kazuto Takaishi, Yusuke Nakatsuka, Hitomi Asano, Yuya Yamada, Tadashi Ema
Summary: A new family of chiral complex dyes was synthesized with ruthenium(II) complexes bearing three axially chiral bipyridyl ligands. The Delta-(S)- and ?-(S)-diastereomers exhibited different circularly polarized phosphorescence properties, with the ?-(S)-isomer showing significant CH/pi interactions to suppress distortion in the excited state T-1.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Takumi Murata, Mahoko Hiyoshi, Shinsuke Maekawa, Yuta Saiki, Manussada Ratanasak, Jun-ya Hasegawa, Tadashi Ema
Summary: BPh3 catalyst enables the N-methylation of secondary amines and C-methylenation of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3 without solvent. Additionally, a cascade reaction from 1-methyl-2-oxindole to 3,3'-methylenebis(1-methylindole) was observed.
Article
Chemistry, Multidisciplinary
Kazuto Takaishi, Sho Murakami, Fumiya Yoshinami, Tadashi Ema
Summary: A series of D-2-symmetric macrocycles composed of alternately linked pyrene and binaphthyl moieties have been synthesized, among which a pyrenophane with ether linkers at the 2,7-positions of pyrenes demonstrated intense circularly polarized luminescence (CPL). The CPL exhibited by this pyrenophane is the highest among excimers and is insensitive to temperature, solvent, or concentration. The CPL originated from a twisting pyrene excimer with left-handed twist produced by (R)-binaphthyl moieties, showing a strong relationship between the electric and magnetic transition dipole moments.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Manussada Ratanasak, Takumi Murata, Taishin Adachi, Jun-ya Hasegawa, Tadashi Ema
Summary: BPh3 catalyzes the N-methylation of secondary amines and the C-methylenation of N,N-dimethylanilines or 1-methylindoles in the presence of CO2 and PhSiH3. The mechanism involves the activation of PhSiH3 by BPh3 to generate key CO2-derived species for the N-methylation reaction. DFT calculations also suggest other mechanisms involving water for the activation of PhSiH3.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Koichi Nakaoka, Chao Guo, Yuta Saiki, Shin Furukawa, Tadashi Ema
Summary: In this study, TBAA and Cu(OAc)(2) were used as a binary catalytic system for the solvent-free N-formylation of amines with CO2 and PhSiH3. This catalysis not only synthesized enamines, aldehydes, and nitriles, but also formed C-H and C-N bonds, achieving a one-pot synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Chihiro Maeda, Hina Inoue, Ayano Ichiki, Takumi Okihara, Tadashi Ema
Summary: Bifunctional aluminum porphyrins can catalyze the conversion of oxetane and CO2 into TMC and PTMC. The catalytic activity is influenced by the Al3+ ion, while the selectivity is controlled by the counteranions. Different TMC compounds can be prepared by using various oxetane derivatives.
Review
Chemistry, Medicinal
Kazuto Takaishi, Chihiro Maeda, Tadashi Ema
Summary: Circularly polarized luminescence (CPL) dyes, recognized as new generation materials, are actively being developed with the help of molecular recognition systems. CPL can be induced through the mixing of different characteristics of host and guest molecules, providing a more efficient alternative to covalent bonding methods in constructing ordered chiral structures.
Article
Chemistry, Multidisciplinary
Chihiro Maeda, Issa Yasutomo, Kazuto Takaishi, Tadashi Ema
Summary: In this article, recent progress in functional dyes showing circularly polarized luminescence (CPL) containing porphyrins or phthalocyanines is summarized. The CPL-active systems are classified into four categories: (i) porphyrins with chiral sources; (ii) axially chiral porphyrin dimers; (iii) self-assembled porphyrins; (iv) porphyrin-sensitized CPL dyes.
JOURNAL OF PORPHYRINS AND PHTHALOCYANINES
(2023)
Article
Chemistry, Applied
Fan Yang, Yuta Saiki, Koichi Nakaoka, Tadashi Ema
Summary: This study reported the solvent-free N-formylation reaction catalyzed by Cu(OAc)(2), which used CO2 and phenylsilane to react with 2-(methylamino)pyridine and produced N-methyl-N-(2-pyridyl)formamide. The improved solubility of copper ion and enhanced nucleophilicity of acetate ion played positive roles in the activation of phenylsilane.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Chihiro Maeda, Koki Akiyama, Tadashi Ema
Summary: Oxidation of dihydroxyhetero[7]-helicenes resulted in the formation of dihetero[8]-circulenesvia simultaneous C-C coupling and dehydrative furan formation. The synthesized pristine dihetero[8]-circulenes were characterized for the first time, with X-ray crystal structures and DFT-optimized structures revealing distorted saddle-like structures. The degree of distortion was found to be correlated with the photophysical properties.
Article
Chemistry, Organic
Kazuto Takaishi, Ritsuki Nishimura, Yuha Toda, Hajime Morishita, Tadashi Ema
Summary: Catalytic CO2 reduction with phenylsilane under solvent-free conditions was utilized to synthesize 3,4-dihydropyrans from beta dicarbonyl compounds and styrenes in a one-pot reaction. The synthesis involves three steps: (1) formation of bis(silyl)acetal from CO2 and phenylsilane, followed by a domino reaction of (2) Knoevenagel condensation and (3) inverse-electron-demand oxa-Diels-Alder reaction. The first step is catalyzed by a pentanuclear ZnII complex (0.07 mol %) to generate bis(silyl)acetals, which are then hydrolyzed into formaldehyde for the second step.
Article
Chemistry, Multidisciplinary
Kazuto Takaishi, Hiroyasu Kosugi, Ritsuki Nishimura, Yuya Yamada, Tadashi Ema
Summary: A pentanuclear zinc complex catalyzed the one-step C-methylenation of anilines and indoles with CO2 and phenylsilane to form diarylmethanes. The zinc-hydride complex generated in situ is proposed as the catalytically active species, with bis(silyl)acetal identified as a key intermediate in the reaction mechanism. Using aniline as a substrate, both C-methylenation and N-methylation were observed.
CHEMICAL COMMUNICATIONS
(2021)
Review
Chemistry, Multidisciplinary
Dan He, Yawen Li, Fuwen Zhao, Yuze Lin
Summary: High trap density in organic solar cells leads to localized charge carriers and reduced carrier lifetime, limiting device efficiency. This feature article summarizes the recent advances of trap suppression by material design and device engineering.
CHEMICAL COMMUNICATIONS
(2024)
Review
Chemistry, Multidisciplinary
Olivier Monfort, Arshitha Madhusudhan, Martin Motola
Summary: This article presents the advantages of coupling photocatalysis and Fenton-based processes for environmental remediation and discusses their synergy. It critically examines the simultaneous triggering of these two processes and provides insights into research approaches. The study aims to enhance understanding of this complex process and highlight the potential integration of new catalysts in current wastewater treatment technology.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Manideepa Dhar, Chittaranjan Mishra, Avijit Das, Uttam Manna
Summary: An approach of 'polymerization of monomers in its aggregated form' has been introduced to tailor the water wettability of fibrous and porous substrates, achieving hydrophobicity to superhydrophobicity transition, as well as patterned wettability. This facile chemical method provides a durable coating with adjustable and patterned wettability for various potential applications.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Saswat Ranjan Bhoi, Chhanda Debnath, Shikha Gandhi
Summary: In this article, a novel catalytic reaction using Pd(0) and Bronsted acid is reported for the synthesis of biologically important imidazolidinone-fused N-heterocycles through redox-neutral intramolecular N-allylation of indoles and pyrroles with alkynes. This atom-economical method is applicable to a wide range of substrates and eliminates the need for leaving groups or oxidizing agents commonly used in traditional allylation reactions.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Longkun Chen, Mingshuai Zhang, Meichen Liu, Zhuoyuan Liu, Yuetong Qiu, Zhilai Zhang, Fuchao Yu, Jiuzhong Huang
Summary: In this study, an efficient Rh(III)-catalyzed selective mono- and dual-C-H bond functionalization/cyclization with iodonium ylide as the sole coupling partner was demonstrated. Fused benzodiazepine skeletons were obtained in excellent yields, providing an improved approach to dual C-H unsymmetrical functionalization.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Alice Kennett, Sven Epple, Gabriella van der Valk, Irene Georgiou, Evelyne Gout, Romain R. Vives, Angela J. Russell
Summary: This study presents the design and synthesis of sulfated disaccharide inhibitors based on IdoA(2S)-GlcNS(6S), which showed potent inhibition of Sulf-2. The results suggest that IdoA(2S)-GlcNS(6S) is the shortest fragment size required for effective inhibition of Sulfs, and a trisulfated disaccharide is identified as the minimal fragment size of heparan sulfate for effective endosulfatase inhibition.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Mauro Garbini, Andrea Brunetti, Riccardo Pedrazzani, Magda Monari, Massimo Marcaccio, Giulio Bertuzzi, Marco Bandini
Summary: The self-adaptability of galvanostatic electrolysis was found to be helpful in a multistage chemo- and diastereoselective electrochemically promoted cyclodimerization of chalcones. Through a series of reductive events, densely functionalized cyclopentanes with five contiguous stereocenters were obtained (25 examples, yields up to 95%, dr values up to >20:1). Further experimental and electrochemical investigations indicated the crucial role of dynamic kinetic resolution of the aldol intermediate in the reaction mechanism.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Dhananjay S. Nipate, Neha Meena, Prakash N. Swami, Krishnan Rangan, Anil Kumar
Summary: In this study, the synthesis of functionalized benzo[a]phenazines and indazolo[2,3-a]quinolines was achieved through Rh(III)-catalyzed oxidative annulation of 2-arylquinoxalines and 2-aryl-2H-indazoles with allyl alcohols. The method showed a wide substrate scope, excellent functional group tolerance, good to high yields of annulated products, and the capability for scaled-up synthesis. A tentative mechanism of the annulation reaction was proposed based on a preliminary mechanistic investigation.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Ruonan Zhang, Abudukadi Tudi, Xia Yang, Xuping Wang, Zhihua Yang, Shujuan Han, Shilie Pan
Summary: A new lead tellurium borate material with a unique fundamental building block [B4O10] was synthesized and found to exhibit high birefringence. The structure-property relationship was discussed using first-principles calculations.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Amresh Kumar Singh, Baishali Thakurta, Anupam Giri, Monalisa Pal
Summary: This study introduces three key concepts for the quick synthesis of large-scale high-quality 2D materials films and their utilization in device fabrication.
CHEMICAL COMMUNICATIONS
(2024)
Article
Chemistry, Multidisciplinary
Reina Hagiwara, Shun Nishimura, Kosuke Okeyoshi
Summary: A copolymer-conjugated nanocatalytic system has been developed to improve electron transfer and enhance photoinduced H2 generation.
CHEMICAL COMMUNICATIONS
(2024)
