Review
Biotechnology & Applied Microbiology
Zhongdi Song, Qunfeng Zhang, Wenhui Wu, Zhongji Pu, Haoran Yu
Summary: The strategy of rational design is to predict potential mutants based on the understanding of protein structure-function relationships and introduce mutations using site-directed mutagenesis. Rational design methods are universal, fast, and have the potential for quantitative prediction of designed sequence performance. Designing enzymes with improved activity or selectivity is challenging due to the complexity of enzyme structure and limited understanding of structure-function relationships. However, with computational advancement and deeper understanding of enzyme catalysis, rational design can simplify enzyme engineering and its application is increasing.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Si-Jia Liu, Zhi-Han Chen, Jia-Yi Chen, Shao-Fei Ni, Yu-Chen Zhang, Feng Shi
Summary: A new class of axially chiral styrene-based thiourea tertiary amine catalysts with efficient synthetic route, multiple chiral elements, and multiple activating groups has been designed. These catalysts have proven to be efficient in enabling the cyclization reaction of 2-benzothiazolimines and homophthalic anhydrides with high yields and excellent stereoselectivities. The role of axially chiral styrene moiety in controlling reactivity and enantioselectivity has been elucidated through theoretical calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Danyang Li, Guoqiang Liang, Peiqiang Mu, Jinquan Lin, Jiarun Huang, Chongwen Guo, Yang Li, Ruqin Lin, Jun Jiang, Jun Wu, Yiqun Deng, Jikai Wen
Summary: This study identified sorbose dehydrogenase (SDH) as an effective enzyme for converting deoxynivalenol (DON) to 3keto-DON and a substance that removes four hydrogen atoms. Mutants F103L and F103A showed significantly increased reaction rates. The study also identified catalytic sites W218 and D281. SDH and its mutants have broad application conditions, and F103A showed potential for detoxification of DON.
Article
Chemistry, Physical
Ying Cai, Jin Zhou, Jianan Huang, Wenjuan Zhou, Yuting Wan, Martien A. Cohen Stuart, Junyou Wang
Summary: In this study, a novel bis-ligand (L2) with bipyridine groups connected by a tetra-ethylene oxide (4EO) spacer was used to form coordination complexes with copper ions in phosphate buffer, which could then bind polyacrylic acid (PAA) to produce catalytically active polymeric nanoparticles with well-defined structure and size, referred to as 'nanozymes'. By controlling the L2/Cu mixing ratio and using phosphate as a co-binding motif, cooperative copper centers with promoted oxidation activity were realized. These designed nanozymes demonstrated stable structure and activity even at higher temperatures and multiple application cycles. Increasing ionic strength enhanced their activity, similar to natural tyrosinase. This rational design approach resulted in nanozymes with optimized structure and active sites that outperformed natural enzymes, suggesting the potential application of this class of catalysts.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Chemistry, Physical
Ashish Kumar Kar, Ranjini Sarkar, Arjun K. Manal, Ravi Kumar, Sudip Chakraborty, Rajeev Ahuja, Rajendra Srivastava
Summary: In this study, the catalytic transfer hydrodeoxygenation (CTHDO) of vanillin over a defect-induced UIO-66 MOF was investigated. The unique structural features of the defect-induced UIO-66 MOF significantly enhanced the CTHDO of vanillin. The creation of defects, confirmed by various characterization techniques, resulted in the generation of Lewis acid and dynamic Bronsted acid.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2023)
Article
Chemistry, Multidisciplinary
Hayama Tsutsumi, Yoshitaka Moriwaki, Tohru Terada, Kentaro Shimizu, Kazuo Shin-ya, Yohei Katsuyama, Yasuo Ohnishi
Summary: In this study, we characterized the geranyl pyrophosphate C6-methyltransferase BezA and investigated the molecular basis of its catalytic mechanisms using multiple strategies. The results revealed the important role of E170 as a catalytic base in completing the methylation reaction. Additionally, we successfully altered the substrate specificity by introducing a W210A substitution, resulting in a novel farnesyl pyrophosphate C6-methyltransferase.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biotechnology & Applied Microbiology
Meiqi Chen, Fangwei Song, Yuxi Qin, Shuangyan Han, Yijian Rao, Shuli Liang, Ying Lin
Summary: This study reports the application of a glycosyltransferase PgUGT from Panax ginseng for the biosynthesis of rebaudioside D. By using rational design and site-directed mutagenesis, a mutant Mut8 with improved enzyme activity and thermostability was obtained. Mut8 showed a 3.2-fold increase in enzyme activity compared to the wild type and an increased optimum reaction temperature of 40°C. This study provides a potential novel glycosyltransferase for the industrial production of rebaudioside D and other steviol glycosides.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2022)
Article
Biochemistry & Molecular Biology
Wei Xia, Yingguo Bai, Pengjun Shi
Summary: By analyzing and designing the active center of Bgl3A, this study found that enhancing hydrophobic interactions and hydrogen-bonding networks can strengthen substrate binding, resulting in four dominant mutants with significantly lower K-m values and higher catalytic efficiencies. These findings may serve as a valuable reference for the design of other beta-glucosidases and glycoside hydrolases.
Article
Biochemistry & Molecular Biology
Kenta Arai, Yuumi Sato, Ikumi Nakajima, Manami Saito, Moeka Sasaki, Akiko Kanamori, Michio Iwaoka
Summary: Amphiphilic derivatives of (+/-)-trans-1,2-diselenane-4,5-diol were employed as GPx-like catalysts for the reduction of H2O2 and lipid peroxidation. The compounds with hydrophilic groups showed high antioxidative activities for H2O2 reduction, while lipophilic compounds with long alkyl chains or aromatic substituents were more effective against lipid peroxidation. These compounds exhibited low cytotoxicity and promising anti-lipid peroxidative activities, indicating their potential as selenium-based antioxidative drugs.
BIOORGANIC & MEDICINAL CHEMISTRY
(2021)
Article
Microbiology
Yingting Feng, Shuai Shao, Xueting Zhou, Wan Wei, Xun Liu, Yi Tang, Yuhao Hua, Jianyong Zheng, Yinjun Zhang, Xiangxian Ying
Summary: Glycolate oxidase (CreGO) from Chlamydomonas reinhardtii was selected and its expression was improved through the use of GST, pET22b vector, and optimization of induction conditions. The fusion enzyme GST-Gly-Ser-Gly-CreGO-Y27S/V111G/V212R showed a six-fold increase in catalytic activity compared to the wild type. The oxidation of methyl glycolate was significantly enhanced using crude enzyme GST-Gly-Ser-Gly-CreGO-Y27S/V111G/V212R with catalase.
Article
Biochemistry & Molecular Biology
Alexis J. A. Hennessy, Wenli Huang, Chloe Savary, Dominic J. Campopiano
Summary: The synthesis of amides through acid and amine coupling is common but requires more sustainable and biocatalytic methods. The study identified the potential of nitrile synthetase in amide bond formation and successfully engineered a biocatalyst without the need for coupling agents. This suggests the further development of nitrile synthetases as efficient, coupling agent-free biocatalysts for amide formation.
Article
Chemistry, Physical
Yingang Wang, Jinhui Feng, Wenyue Dong, Xi Chen, Peiyuan Yao, Qiaqing Wu, Dunming Zhu
Summary: The study successfully engineered an omega-transaminase with (S)-selectivity to accept bulky substrates, resulting in several variants that showed activity towards bulky substrates, with the best variant achieving high yield and enantioselectivity in the asymmetric synthesis at a semi-preparative scale. This work will enhance the general understanding of omega-transaminases and inspire further engineering efforts to reverse enantio-specificity.
Article
Chemistry, Physical
Ke Zhang, Tingze Pan, Yangyang Sun, Zhuzhu Tang, Yuhong Ren, Hualei Wang, Dongzhi Wei
Summary: This study developed a rational in silico strategy to accurately identify CP-NLases with significant hydration activity. A key motif, LNCXE, responsible for the catalytic promiscuity in nitrilases was identified by mimicking active site architectural features. Utilizing this strategy, six CP-NLases with significant hydration activity were discovered, and one nitrilase (NitPC) exhibited the highest promiscuous activity ever reported, producing 89.7% mandelamide.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Biotechnology & Applied Microbiology
Ami Takeuchi, Mariko Ohnuma, Hiroshi Teramura, Kenji Asano, Takahiro Noda, Hiroaki Kusano, Koji Tamura, Hiroaki Shimada
Summary: This study successfully created mutants of the potato SBE3 gene using CRISPR/Cas9 technology, with 10 lines containing four mutant SBE3 genes achieving an 8% efficiency of target mutagenesis. These mutants grew normally, yielded sufficient amounts of tubers, and exhibited similar starch properties to the rice BEI mutant, indicating a loss-of-function mutation of SBE3.
PLANT BIOTECHNOLOGY
(2021)
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
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.
Review
Chemistry, Organic
Tadashi Ema
Summary: This study summarizes achievements in solvent-free catalysis, including the development of bifunctional metalloporphyrin catalysts for the synthesis of cyclic carbonates or polycarbonates, and the development of chiral catalysts for the kinetic resolution of epoxides with CO2. The high catalytic activities were attributed to the cooperative action of central metal ions and quaternary ammonium salts.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2021)
Article
Chemistry, Multidisciplinary
Kazuto Takaishi, Sho Murakami, Kazuhiro Iwachido, Tadashi Ema
Summary: A series of axially chiral binaphthyls and quaternaphthyls with alternating aromatic fluorophores were synthesized using a divergent method, leading to the formation of unidirectionally twisted exciplex exhibiting circularly polarized luminescence (CPL). These compounds represent the first examples of monomolecular exciplex CPL dyes and the versatile synthesis method also improved fluorescence intensity. The study confirmed that the excimer chirality rule can be applied to exciplex dyes, with left- and right-handed exciplexes showing (-)- and (+)-CPL, respectively, when the twist angle is less than 90 degrees.
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)