Article
Biochemistry & Molecular Biology
Jieun Choi, Taehwan Yu, Hyun-Joon Ha
Summary: The highly strained three-membered aziridine ring was activated as an aziridinium ion through alkylation of the ring nitrogen and subsequent ring opening with external nucleophiles. This method provides an easy route for synthesizing various N-alkylated amine-containing molecules with the introduction of external nucleophiles at either the alpha or beta position.
Article
Chemistry, Multidisciplinary
Nikhil Srivastava, Hyun-Joon Ha
Summary: Aziridine displays different regioselective ring-opening reactions depending on the functional group of its alkyl substituents. This reaction can efficiently generate various substituted heterocycles.
FRONTIERS IN CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Stefanie Beck, Vanessa Rueck, Lea-Viktoria Pietsch, Christoph Jessen, Andreas J. Kornath
Summary: The reaction of beta-propiolactam in superacidic systems led to the formation of monoprotonated 3-aminopropanoyl fluoride. Diprotonated species beta-alanine was synthesized in the presence of traces of water. Different salts were characterized using low-temperature infrared and Raman spectroscopy, with single-crystal X-ray analyses conducted. Additionally, quantum chemical calculations were carried out to gain a better understanding of the structural properties of protonated beta-propiolactam.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Organic
Du Qingfeng, Zhang Lu, Gao Feng, Wang Le, Zhang Wanbin
Summary: Epoxides and aziridines are important three-membered cyclic compounds and their asymmetric ring-opening reactions catalyzed by transition metals are efficient for constructing chiral molecules. This review focuses on the recent progress in this field, including the influence of catalysts, nucleophiles, and ligands, as well as discussing the possible reaction mechanisms, applications, and future development.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
Linlin Zhu, Qinyong Chen, Ying Wang, Huishan Huang, Wenyi Luo, Zhunxuan Li, Zhen Zhang, Nikos Hadjichristidis
Summary: A facile and effective method involving ring-opening copolymerization of N-sulfonyl aziridines towards cellulose has been developed for efficient oil/water separation. The modified cellulose paper material showed promising properties for efficient oil/water separations, with a grafting ratio ranging from 96 to 150% and a contact angle over 127°.
CARBOHYDRATE POLYMERS
(2021)
Article
Chemistry, Applied
Xavier Marset, Marti Recort-Fornals, Malkaye Kpante, Adam Zielinski, Christopher Golz, Lawrence M. Wolf, Manuel Alcarazo
Summary: A series of strong it-acceptor polyfluorinated and dicationic chelating phosphines were synthesized and evaluated in the Rh-catalysed dimerization of norbornadiene, leading to the selective formation of specific products and site-selective arylation reactions. Theoretical calculations were performed to understand the origin of the observed regioselectivity.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Organic
Xiao-Fei Fu, Qiang Zhao, Wen-Xian Zhao
Summary: A copper-catalyzed three-component tandem reaction involving alkenes, sulfonyl azides, and alcohols has been described for the synthesis of valuable beta-alkoxy amines. This method is practical and cost-effective, showing good yields and tolerance towards various functional groups.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Jan Doubsky, Stanislav Radl, Josef Cinibulk, Robert Klvana
Summary: An efficient and scalable synthesis method for fingolimod hydrochloride has been developed, using the aziridine regioselective ring-opening reaction as a key step. The method is industrially applicable and has been successfully applied to 500 g scales of the target product.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Multidisciplinary
Cameron L. Brown, Brandon H. Bowser, Jan Meisner, Tatiana B. Kouznetsova, Stefan Seritan, Todd J. Martinez, Stephen L. Craig
Summary: Woodward and Hoffman once joked about a Maxwell demon that could open a molecule of cyclobutene in a disrotatory fashion. Nearly 40 years later, this concept was realized in the field of covalent polymer mechanochemistry. By combining single-molecule force spectroscopy and computation, the study explored substituent effects in ring-opening reactions of cyclobutene and benzocyclobutene, revealing differences in the forces required for allowed and forbidden reactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Polymer Science
Peng-Duo Song, Lei Xia, Xuan Nie, Guang Chen, Fei Wang, Ze Zhang, Chun-Yan Hong, Ye-Zi You
Summary: In this study, a ring-opening copolymerization method is reported to synthesize poly(thioester sulfonamide)s with highly alternative structures, high yields, and controlled molecular weights. This method combines the advantages of thioesters and amides, and can also be used to produce novel block copolymers.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Matteo Cavalleri, Caterina Damiano, Gabriele Manca, Emma Gallo
Summary: Protonated commercially available porphyrin ligands can act as bifunctional catalysts for the synthesis of N-alkyl oxazolidinones by CO2 cycloaddition to aziridines. This metal-free methodology is cost effective and eco-compatible, and the protonated porphyrin can be recycled without loss in performance. DFT study provides insights into the mechanism of CO2 cycloaddition to aziridines mediated by protonated porphyrin.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Polymer Science
Rui Chen, Ying Wang, Linlin Zhu, Zhen Zhang
Summary: An ultrafast method for controlled synthesis of polysulfonamides through organocatalytic anionic ring-opening polymerization (ROP) in the melt has been established. Using N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) as catalyst, poly(2-methyl-N-tosylaziridine) with molecular weight over 100 kg/mol can be synthesized in less than 90 s. Various initiators can be applied to achieve molecular weight and end-group controlled polymers under open-flask conditions.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Chemistry, Organic
Stefanie Beck, Christoph Jessen, Andreas J. Kornath
Summary: In binary superacidic systems HF/MF5 (M = Sb, As), transformations of beta-propiolactone were studied at various temperatures. Different salts were obtained depending on the reaction temperature, with monoprotonated products at lower temperatures and cyclic trications at higher temperatures. Protonated species of beta-propiolactone was not observed. The salts were characterized by low temperature Raman and IR spectroscopy, and single-crystal X-ray analyses were performed for selected samples. The formation of acyl cation as a reactive intermediate was proposed based on quantum chemical calculations.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Fang Li, Chao Pei, Calogero Quaranta, Rene M. Koenigs
Summary: This study reports a rhodium-catalyzed reaction of triazoles with acyl selenides, resulting in high yields and stereoselectivity of functionalized compounds. Computational calculations suggest a direct pathway to achieve 1,3-difunctionalization without the formation of ylide intermediates.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Inorganic & Nuclear
Ida Ritacco, Maria Voccia, Salvatore Impemba, Matteo Farnesi Camellone, Stefano Milione, Lucia Caporaso
Summary: The mechanism of L-lactide polymerization promoted by NSSN zirconium complexes was investigated using DFT methods to understand how the electronic and steric features of the ligand affect the reaction energy. The rate determining step was found to be the opening of the L-lactide ring, and increasing steric hindrance or electron-withdrawing properties of the ligand increased the energy barrier. However, introducing small and electron-releasing substituents on the nitrogen atom of the ligand, such as a methyl group, improved the activity of NSSN zirconium catalysts in the ROP of L-lactide.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Jake A. Tan, Jer-Lai Kuo
Summary: Matrix isolation experiments have been used to study the infrared spectra of proton-bound rare gas complexes. However, little attention has been paid to the Fermi resonance interaction between the H+ stretch and bend overtone in asymmetric proton-bound rare gas dimers. This study investigates this interaction in KrH(+)Rg and XeH(+)Rg complexes, providing new assignments for their spectra and calculating binding energies at the CCSD(T)/CBS level.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Dung Van Hoang, Nam Hoang Vu, Nga Thi Do, Anh Tuan Thanh Pham, Truong Huu Nguyen, Jer-Lai Kuo, Thang Bach Phan, Vinh Cao Tran
Summary: This study distinguishes the roles of hydrogen in improving electron mobility and carrier concentration in ZnO and Al doped ZnO sputtered films. The experimental and theoretical results show that hydrogen located at oxygen vacancy sites is the main factor contributing to the simultaneous increase in mobility and carrier concentration. Introducing appropriate hydrogen content during sputtering not only relaxes the crystal structure, but also supports aluminum doping, resulting in increased carrier concentration and electron mobility in the film.
JOURNAL OF MATERIOMICS
(2022)
Article
Chemistry, Multidisciplinary
Jun-Ying Feng, Qian-Rui Huang, Ha-Quyen Nguyen, Jer-Lai Kuo, Takayuki Ebata
Summary: The infrared-vacuum ultraviolet spectroscopy was used to measure the C-H stretching vibrations of pyrimidine and pyrazine, and an anharmonic analysis with evaluation of QP at DFT level was carried out to interpret the F-R mode patterns.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Qian-Rui Huan, Yoshiyuki Matsuda, Riku Eguchi, Asuka Fujii, Jer-Lai Kuo
Summary: The vibrational spectra of methyl groups in different monomers were measured to analyze the complex features resulting from bend/umbrella-stretch Fermi resonance. CH3OH and CH3OCH3 exhibit more complex vibrational features compared to CH3SH and CH3SCH3, with multiple bands recorded and red-shifted C-H stretch fundamentals.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Harender S. Dhattarwal, Jer-Lai Kuo, Hemant K. Kashyap
Summary: Ether-based solvents and their fluorinated derivatives have shown remarkable ability in promoting the formation of a stable solid-electrolyte interphase (SEI) layer in lithium metal batteries. Molecular dynamics simulations reveal that in the Li [FSI]-FDMB system, the dissociation of solvent molecules reduces the stability near the lithium metal anode.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Review
Biochemistry & Molecular Biology
Jake A. Tan, Jer-Lai Kuo
Summary: In this study, the structures and spectral features of protonated noble gas clusters were investigated using a first principles approach. It was found that protonated noble gas monomers and dimers have a linear structure, while the trimers can have a T-shaped or linear structure. Additionally, interesting spectral features such as progression bands and Fermi resonance interactions were observed.
Article
Chemistry, Multidisciplinary
Cheng-chau Chiu, Chung-Yu Wang, Bo-Jie Huang, Jer-Lai Kuo
Summary: We use periodic DFT calculations to study 3d transition metal dihalide monolayers in H- and T-phase. By analyzing the phonon dispersion, we identify possible stable structures and explain trends in the predicted electronic properties. Despite their simple geometric structures, the associated electronic and magnetic properties are not easily understood due to inconsistent results and differences in relative energy between electronic states.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Pei-Kang Tsou, Hai Thi Huynh, Huu Trong Phan, Jer-Lai Kuo
Summary: Understanding the mechanism of collision-induced dissociation in mono-saccharides is challenging due to their high structural diversity. A three-step search scheme with the assistance of neural network potential was proposed to find the transition state from a large number of conformers. The scheme was applied to study the CID reactions in eight types of aldohexose pyranoses and found around 5200 transition states with a mean absolute error of energy less than 4 kJ mol(-1) using the constructed neural network potential.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Huu Trong Phan, Pei-Kang Tsou, Po-Jen Hsu, Jer-Lai Kuo
Summary: Sampling the conformational space of monosaccharides is crucial for interpreting experimental measurements, and a neural network potential (NNP) can improve the accuracy of the computational approach. By training the NNP based on density functional calculations, we obtained a better description of certain aldohexoses. An active learning scheme further enhanced the accuracy of the NNP and enabled the identification of thousands of distinct local minima.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Jun-Ying Feng, Yuan-Pern Lee, Po-Jen Hsu, Jer-Lai Kuo, Takayuki Ebata
Summary: The structures of (pyrazine)2 and (pyrazine)(benzene) hetero-dimer in a supersonic beam were investigated. The most stable structures for both dimers were identified as the cross-displaced K-K stacked structure. The analysis of the infrared spectra and quantum-chemical calculations confirmed the coexistence of multiple isomers in the supersonic jet.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Jake A. A. Tan, Rona F. Barbarona, Jer-Lai Kuo
Summary: In this study, the vibrational structure of N2H+Ng (Ng = {He, Ne, Ar, Kr, Xe, and Rn}) was investigated using reduced-dimensional calculations. It was found that the vibrational coupling in N2H+ can be controlled by tagging it with different noble gases, resulting in interesting anharmonic effects such as Fermi resonance and combination bands. The comparison of the vibrational spectra revealed a transition of .H+ from an Eigen-like to a Zundel-like state. Additionally, the binding energies for the elimination of Ng in N2H+Ng were determined.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Physical
Shweta Jindal, Po-Jen Hsu, Huu Trong Phan, Pei-Kang Tsou, Jer-Lai Kuo
Summary: This study proposes a new method that utilizes a database of stable conformers and borrows the fragmentation concept of many-body expansion (MBE) methods in ab initio methods to train a deep-learning machine learning (ML) model using SchNet. This method allows for accurate exploration of the structure and properties of molecular clusters with the accuracy of first-principles methods and the computational speed of empirical force-fields.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Hai Thi Huynh, Shang-Ting Tsai, Po-Jen Hsu, Anik Biswas, Huu Trong Phan, Jer-Lai Kuo, Chi-Kung Ni, Cheng-chau Chiu
Summary: Collision-induced dissociation tandem mass spectrometry (CID-MSn) and computational investigation were used to study the dissociation pathways of Na+-tagged fructose. Different cyclic isomers of fructose showed distinct mass spectra, indicating the ability of CID-MSn to distinguish them. Kinetic modeling helped explain previous discrepancies and confirmed the assignment of different mass spectra to fructose isomers. The model was able to reproduce most trends observed in the differences between the dissociation pathways of the cyclic fructose isomers.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Chih-Kai Lin, Jer-Lai Kuo
Summary: In this work, the vibrational spectra of ammonium, methylammonium, and dimethylammonium ions solvated by either water molecules or bisulfate anions were analyzed using anharmonic vibrational algorithms. The observed spectral features were attributed to strong Fermi resonance and combination tones. Similarities in band positions and spectral patterns between different solvation environments indicate a common vibrational coupling scheme.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Takahiro Shinkai, Po-Jen Hsu, Asuka Fujii, Jer-Lai Kuo
Summary: This study investigated the impact of fluorination on the hydrogen bond networks of protonated alkylalcohols using infrared spectroscopy and theoretical computations. The results showed that fluorination facilitated the transition of the hydrogen bond networks from linear type to cyclic type in a specific size range for protonated alkylalcohol clusters. Additionally, fluorination effectively inhibited the formation of cyclic hydrogen bond networks in protonated clusters.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
