Article
Chemistry, Inorganic & Nuclear
Zhen-Li Yang, Yue-Mei Wu, Piao He, Wen-li Cao, Saira Manzoor, Jian-Guo Zhang
Summary: The study has successfully synthesized a series of 3-amino-5-hydrazinopyrazole energetic salts with excellent performance, which opens up more prospects for the design of insensitive and novel high-energy green materials.
DALTON TRANSACTIONS
(2021)
Article
Engineering, Chemical
Yan Xu, Lu Wang, Junwei Wu, Guanzhong Zhai, Daohua Sun
Summary: Acceptorless alcohol dehydrogenation is a promising strategy in hydrogen storage technologies. Cost-effective molecular catalysts using phosphine-free ligands have gained attention, but the challenge is to overcome the one-electron pathway of non-precious metals.
FRONTIERS OF CHEMICAL SCIENCE AND ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Ke Zhao, Philip Kohnke, Ziguang Yang, Xinpeng Cheng, Shu-Li You, Liming Zhang
Summary: A gold(I)-catalyzed enantioselective dearomatization is achieved through metal-chiral ligand cooperation. A new and divergent synthesis of chiral bifunctional binaphthyl-2-ylphosphines is developed for rapid access to these ligands, enabling broad substrate scope. The selective acceleration of one enantiomer formation is achieved through hydrogen bonding between substrate and ligand remote basic group, leading to enantiomeric excesses up to 98%.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Yongliang Zhang, Ke Zhao, Xinyi Li, Carlos D. Quintanilla, Liming Zhang
Summary: By using a chiral bifunctional phosphine ligand, a highly efficient and enantioselective dearomatization of phenols is achieved through metal-ligand cooperation. The reaction shows great generality by allowing substitutions at various positions of benzene, including electron-withdrawing groups and carbon-based groups. Spirocyclohexadienone-pyrrol-2-ones, spirocyclohexadienone-butenolides, and spirocyclohexadenone-cyclopentenones are formed in high yields and with high enantioselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Zhen Fu, Chengming Wang, Cong-Ying Zhou
Summary: In this study, an alkylcarbene-mediated intramolecular alkene cyclopropanation was developed for the synthesis of azabicyclo[3.1.0]hexanes. With the catalyst Rh2(esp)2, alkyl diazomethanes generated in situ from 2,4,6-triisopropylbenzenesulfonylhydrazones underwent intramolecular cyclopropanation with alkenes, leading to the formation of azabicyclo[3.1.0]hexanes in good to high yields under mild reaction conditions. This method has important synthetic applications.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Materials Science, Multidisciplinary
Huadong Yuan, Xufen Ding, Tiefeng Liu, Jianwei Nai, Yao Wang, Yujing Liu, Chuntai Liu, Xinyong Tao
Summary: This review presents a historical framework of important concepts and breakthroughs in enabling lithium metal anodes to be practically applied. It also discusses and summarizes the major contributions from different institutions, journals, authors, and highly cited papers. The goal of this review is to motivate more researchers to pave the way for high-energy lithium metal batteries in the future.
Article
Chemistry, Organic
Hong Hou, Yue Sun, Yingjie Pan, Huaguang Yu, Ying Han, Yaocheng Shi, Chaoguo Yan, Shaoqun Zhu
Summary: This study describes a selenylative cyclization reaction using diselenides as radical sources, with visible light irradiation generating selenium atom radical to trigger radical addition/cyclization/selenation sequences. Both terminal alkyne and internal alkyne derived 1,6-enynes were suitable for the synthetic protocol, leading to good yields of various selenium-containing cycles.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Nanoscience & Nanotechnology
Yangfan Liu, Xinghan Liu, Jun Gong, Yejun Li, Xiaoming Yuan, Gufei Zhang, Qing Wu, Zhou Li
Summary: In this study, FeM-N6 configuration catalysts (M = Fe, Co, Ni, Cu, Ag, and Au) were constructed by embedding M dopants on Fe-N4 systems for the oxygen evolution reaction (OER). The Fe-M metal interactions play a dominant role in regulating the d orbital distributions of Fe sites and altering the OER performance. The effects of axial ligands on the OER activity were also considered, revealing a competitive relationship between the axial ligand and the adsorbed intermediate species during the reaction.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Physics, Applied
Andrew C. Antony, Dean Thelen, Nikolay Zhelev, Kaveh Adib, Robert G. Manley
Summary: The study reveals that contact charging between metals and hydroxylated SiO2 induces electronic states at the SiO2 surface, with the magnitude of these states varying with the type of metal and the density of surface defect states.
JOURNAL OF APPLIED PHYSICS
(2021)
Article
Chemistry, Organic
Rong Liang, Qinghai Zhou, Xin Li, Ming Wah Wong, Lung Wa Chung
Summary: The macrocycle effect of [2]rotaxane on the highly trans-stereoselective cyclization reaction of N-benzylfumaramide has been extensively studied. Computational results suggest that the most favorable mechanism involves deprotonation of a N-benzyl group of the fumaramide substrate by CsOH, followed by C-C bond formation and protonation by an amide functional group of the macrocycle. The trans-selective cyclization within the rotaxane is attributed to higher distortion energy caused by the twisted cis-fumaramide conformation enforced by the rotaxane.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Ruben Mirzoyan, Nathanael P. Kazmierczak, Ryan G. Hadt
Summary: Transition metal complexes have become prominent candidates for quantum bit applications in the past decade due to their tunability and long coherence times. However, decoherence limits their use in quantum information technologies. Recent developments have proposed various chemical design principles to extend coherence in molecular transition metal qubits, outlining different decoherence regimes and design principles for each. Dynamic ligand field models can provide insights into the intramolecular vibrational contributions in the spin-phonon decoherence regime. This minireview aims to inform the development of molecular quantum technologies tailored for different environments and conditions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Nanoscience & Nanotechnology
Guoying Yao, Liang Zhao, Tao Zeng, Zhenyu Yang
Summary: Reduced-dimensional (RD) perovskites have attractive properties for optoelectronic applications. However, the coexistence of different organic ligands commonly inhibits the formation of more complex crystal structures. In this study, a mixed-dimensional (MD) perovskite single crystal containing two types of sulfide-containing ligands was reported. X-ray diffraction confirmed the structure contains layered and isolated inorganic components. The MD perovskite showed an enlarged bandgap and isotropic optical features.
Article
Chemistry, Physical
Rabi Khanal, Stephan Irle
Summary: We studied the electron transport within the MXene layers as a function of composition and found a linear relationship between current and voltage at lower potentials in all MXene compositions, indicating their metallic character. However, the conductivity varies among different compositions, with MXenes without surface terminations exhibiting higher conductivity compared to MXenes with surface functionalization. The conductivity also changes with the ratio of -O and -OH on the MXene surface. The surface composition-dependent conductivity of MXenes provides a way to enhance the pseudocapacitive performance.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Engineering, Environmental
Jeongyeon Ahn, Yongkwon Song, Ye Ji Kim, Donghyeon Nam, Taewoo Kim, Kyungwon Kwak, Cheong Hoon Kwon, Yongmin Ko, Suk Joong Lee, Jinhan Cho
Summary: The important issues in preparing transition metal oxide nanoparticle-based energy storage electrodes are to minimize electrochemically inactive organics and increase the amount of high-energy nanoparticles. A redox-active ligand-mediated layer-by-layer assembly approach is introduced to enhance the energy storage performance of these electrodes.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Qin Zhu, Shuoqi Zhang, Jing Ma, Jun Zhu, Shuhua Li, Guixiang Zeng
Summary: The transfer hydrogenation of azobenzene with ammonia borane mediated by pincer bismuth complex 1 was studied using density functional theory calculations. The study revealed an unusual metal-ligand cooperation mechanism involving the saturation/regeneration of the C=N functional group on the pincer ligand. The reaction proceeds through the hydrogenation of the C=N bond, followed by the conversion of 3(CN) to a Bi-H intermediate, and eventually results in the production of N,N'-diphenylhydrazine and regeneration of the catalyst. The substitution of the phenyl group with a tert-butyl group on the pincer ligand improves the catalyst's performance.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Nanoscience & Nanotechnology
Srikanth Nayak, Raju R. Kumal, Zhu Liu, Baofu Qiao, Aurora E. Clark, Ahmet Uysal
Summary: Liquid-liquid extraction is an effective technique for separating precious and rare metals, with the organizational structure of the organic phase being correlated with different local hydration effects that are independent of metal concentration.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Chemistry, Physical
Joshua Mirth, Yanqin Zhai, Johnathan Bush, Enrique G. Alvarado, Howie Jordan, Mark Heim, Bala Krishnamoorthy, Markus Pflaum, Aurora Clark, Y. Z, Henry Adams
Summary: Encoding complex energy landscape features is challenging, with chemists focusing on minima and barriers. Tools like sublevelset persistent homology are used to explore the topology of these landscapes and make comparisons between analytical and simulated data. This work lays the foundation for future studies on quantifying differences in topological features of high-dimensional energy landscapes.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Michael J. Servis, Aurora E. Clark
Summary: Structural heterogeneity in solutions and liquids requires multimodal experimental measurement and the application of new techniques to identify and characterize variability. This study utilizes graph theory to partition chemical networks, demonstrating the ability to identify multiple scale features.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Multidisciplinary
Nitesh Kumar, Michael J. Servis, Aurora E. Clark
Summary: This study examines the speciation of uranyl at the liquid/liquid interface using classical molecular dynamics simulations. The interactions of uranyl with nitrate exhibit variability that prevents dehydration at the interface, while Li+ loses solvation water in the interfacial region. Despite significant perturbations in ion-ion interactions and solvation dynamics, the association constants of uranyl with nitrate remain unchanged, allowing for the prediction of the distribution of interfacial uranyl nitrate complexes.
SOLVENT EXTRACTION AND ION EXCHANGE
(2022)
Editorial Material
Chemistry, Multidisciplinary
Aurora E. Clark, Henry Adams, Rigoberto Hernandez, Anna I. Krylov, Anders M. N. Niklasson, Sapna Sarupria, Yusu Wang, Stefan M. Wild, Qian Yang
Summary: The theory and simulation of systems with realistic complexity and size, evolving across massive time scales, pose a critical challenge that requires an accurate description of many-body interactions. Building upon small-scale science, a new Middle Science integrates modern math and data science with chemical theories, as proposed in this article.
ACS CENTRAL SCIENCE
(2021)
Article
Chemistry, Inorganic & Nuclear
Micah P. Prange, Trent R. Graham, Rafal Gorniak, Maxime Pouvreau, Mateusz Dembowski, Hsiu-Wen Wang, Luke L. Daemen, Gregory K. Schenter, Mark E. Bowden, Emily T. Nienhuis, Kevin M. Rosso, Aurora E. Clark, Carolyn Pearce
Summary: Aluminate salts precipitated from caustic alkaline solutions show a correlation between the anionic speciation and the identity of the alkali cation in the precipitate. The use of inelastic neutron scattering and Raman spectroscopy reveals the anion structures and solution speciation characteristics.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Ernest R. Davidson, Aurora E. Clark
Summary: Population analyses are crucial for computational chemists, particularly when dealing with partitioning electron density into atomic contributions, which involves interesting philosophical choices. Historical context significantly influences common conceptions of chemical bonding and reactivity. This work reviews aspects of orbital and spatial decomposition schemes of the density matrix.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2022)
Article
Chemistry, Physical
Michael J. Servis, Biswajit Sadhu, L. Soderholm, Aurora E. Clark
Summary: This study investigates the impact of dipole-dipole interactions and molecular structure on the morphology of amphiphile assemblies. The research demonstrates that appropriate conformational sampling significantly influences the self-assembly of malonamide-based amphiphiles. Quantitative analysis reveals that dipole alignment and alkyl tail sterics play crucial roles in determining the structure of aggregates, with dipole alignment promoting linear patterns of intermolecular interactions within aggregates.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Physical
Hung M. Le, Sushant Kumar, Nathan May, Ernesto Martinez-Baez, Ravishankar Sundararaman, Bala Krishnamoorthy, Aurora E. Clark
Summary: Identifying collective variables (CVs) for chemical reactions is crucial but challenging due to the nonmeaningful motions of bulk solvent. This work proposes a distance-attenuated projection method that enables both PCA and UMAP to accurately identify CVs in the presence of explicit solvent and determine the specific importance of solvent molecules in chemical reactions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Biswajit Sadhu, Aurora E. Clark
Summary: In non-polar media, polar co-solutes enhance the self-assembly of amphiphiles. This study investigates the individual effects of water and nitric acid on the self-assembly of TODGA and reveals that water promotes local aggregation while inhibiting the formation of large water clusters, while nitric acid disrupts the water hydrogen bond network and encourages local aggregation.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Physical
William Smith, Maxime Pouvreau, Kevin Rosso, Aurora E. Clark
Summary: pH dependent interfacial chemistry is influenced by the distribution and pK(a) values of different surface active sites. Recent advancements in synthesizing nanoparticles of various minerals offer an opportunity to reinterpret interfacial properties and reactivity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Nitesh Kumar, Aurora E. Clark
Summary: Liquid/liquid extraction is a widely used separation and purification method, and current research focuses on the transport mechanisms of solute partitioning and its relationship to solution structure at the phase boundary. Recent studies have shown that a metal salt like LiNO3 can be transported through a protrusion mechanism similar to that of H2O, highlighting the competition and complexity of solute transport mechanisms.
Article
Chemistry, Physical
Lance E. Edens, Enrique G. Alvarado, Abhinendra Singh, Jeffrey F. Morris, Gregory K. Schenter, Jaehun Chun, Aurora E. Clark
Summary: A study using simulations shows that there are significant rearrangements in the balance of attractive, lubrication, and contact forces as 3D dense suspensions transition across shear thinning and shear thickening regimes. Attractive forces dominate in shear thinning regions, while lubrication forces grow as shear thickening is approached. Contact forces become dominant in shear thickening and are an order of magnitude higher than in shear-thinning regimes.
Article
Chemistry, Inorganic & Nuclear
Hung M. Le, Mariano Guagliardo, Anne E. V. Gorden, Aurora E. Clark
Summary: Umbrella-sampling density functional theory molecular dynamics (DFT-MD) was used to investigate the full catalytic cycle of allylic oxidation of cyclohexene using a Cu(ii) complex in acetonitrile, revealing two distinct reaction pathways involving dehydrogenation and re-hydrogenation of the -NH2 group. The energy span was estimated to be approximately 22.7 kcal mol(-1) to 26.2 kcal mol(-1) for the different pathways, both consistent with the equilibrium between Cu(ii) and Cu(iii). The ensemble sampling of configurations provided a more comprehensive understanding of radical reactions and catalysis recovery compared to prior static DFT calculations.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Zhu Liu, Aurora E. Clark
Summary: Using molecular dynamics and other methods, this study reveals an elegant mechanism for the transport of water across water/octanol phase boundaries. The mechanism involves the formation of a semi-organized bilayer island and is driven by the differential free energies of solvation of H2O across the interface.