Article
Chemistry, Organic
Guang-Qi Hu, Jing-Wen Bai, En-Ci Li, Kai-Hui Liu, Fei-Fei Sheng, Hong-Hai Zhang
Summary: A new method for deuterating (hetero)aryl bromides using Ag2CO3 as catalyst and D2O as deuterium source is disclosed in this study, which is highly efficient and easy to manipulate. In comparison to traditional multistep syntheses, this method allows for one-step deuterium labeling of various bioactive druglike molecules and key intermediates of functional materials. Additionally, this method demonstrates unique site-selectivity in comparison to existing transition-metal-catalyzed processes, leading to multideuterated (hetero)aryl bromides in one step.
Article
Engineering, Environmental
Xuteng Zhao, Dejun Xu, Yinan Wang, Zuwei Zheng, Ke Li, Yiran Zhang, Reggie Zhan, He Lin
Summary: This study demonstrates that the combination of electric field with 1% Pt/Ce0.75Zr0.25O2 catalyst can improve the catalytic performance of benzene oxidation at low temperature, increase the adsorbed oxygen content on the catalyst surface, accelerate the generation and consumption of intermediate products, and produce new intermediate products.
JOURNAL OF HAZARDOUS MATERIALS
(2021)
Article
Chemistry, Physical
Jie Feng, Qiaoyun Liu, Haojie Li, Zhongxian Song, Lin Dong, Shufang Zhao, Young Dok Kim, Zhongyi Liu, Zhikun Peng
Summary: In this study, the lattice contraction and electron-rich surface of Pd were successfully regulated by doping low electronegative metal M (M = Zn, Ni, Co, or Cu), leading to an enhanced selectivity for the conversion of benzene to cyclohexylbenzene. Mechanistic investigation revealed that PdZn promoted the asymmetric adsorption and activation of benzene to cyclohexene, and regulated its moderate adsorption. This work provides new insights into the intrinsic regulation of tandem reactions with one key intermediate.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Chemistry, Analytical
Tatsuya Sakamoto, Keiko Odera, Mayu Onozato, Hiroshi Sugasawa, Ryoya Takahashi, Yasuto Fujimaki, Takeshi Fukushima
Summary: D-Amino acid oxidase (DAO) has been suggested to be associated with central nervous system diseases. A nonfluorescent substrate, MeS-D-KYN, was synthesized and showed potential for evaluating DAO activity by converting to blue-fluorescent MeS-KYNA. Fluorescence imaging confirmed the overlap of MeS-KYNA fluorescence with the distribution of DAO in cells, indicating the direct evaluation of cellular DAO activity using MeS-D-KYN as a substrate.
ANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Physical
Aaron Sattler, Michele Paccagnini, Lichen Liu, Elaine Gomez, Henry Klutse, Allen W. Burton, Avelino Corma
Summary: The study showed that increasing the reduction time of PtSn-K/MFI can enhance the catalyst's selectivity towards propylene, reduce catalyst deactivation and dehydrogenation rates. It also slows down hydrogenolysis and C-H activation rates on the catalyst.
JOURNAL OF CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Christopher J. Koch, Vicente Galvan, Alain Goeppert, G. K. Surya Prakash
Summary: The direct conversion of inorganic carbonate salts into methane using Ni/Al2O3 and Ni/CaAl2O4 catalysts under 50 bar of hydrogen at a temperature of 225 degrees C is reported. Water improved the conversion rate and the Ni/Al2O3 catalyst retained 99% of its activity after five hydrogenation cycles. The metal hydroxide was regenerated and reused to capture CO2 for subsequent reactions. Compared to the sequential approach, this integrated route offers energetic and economic benefits for carbon capture and conversion.
Article
Biochemistry & Molecular Biology
Jingwen Li, Jingfei Chen, Yefei Wang, Lishan Yao
Summary: The hydrogen bond cooperativity in the beta-sheet of GB3 protein is investigated using a NMR hydrogen/deuterium exchange method. It is found that weakening one hydrogen bond perturbs other neighboring hydrogen bonds, with three being cooperative and one being anticooperative. This hydrogen bond cooperativity plays a significant role in the stability and conformational coupling of the beta-sheet.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Inorganic & Nuclear
Tatiana S. Bogomolova, Alexander S. Lisitsyn, Artem B. Ayupov, Evgeny Yu. Gerasimov, Oleg V. Klimov, Alexander S. Noskov, Marina Yu. Smirnova
Summary: This study investigates the effect of Mg on the acidic and metal functions in Pt/ZSM-23 catalysts. The results show that Mg loading can tune the surface acidity and selectivity of the catalyst, but the addition of Mg through ion-exchange has an opposite effect.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yi Li, Hemanth Somarajan Pillai, Teng Wang, Sooyeon Hwang, Yun Zhao, Zhi Qiao, Qingmin Mu, Stavros Karakalos, Mengjie Chen, Juan Yang, Dong Su, Hongliang Xin, Yushan Yan, Gang Wu
Summary: Low-temperature direct ammonia fuel cells (DAFCs) are promising with PtIrZn/CeO2-ZIF-8 as a catalyst for efficient ammonia oxidation reaction, improving the performance of the fuel cells.
ENERGY & ENVIRONMENTAL SCIENCE
(2021)
Article
Chemistry, Applied
Tatinaidu Kella, Debaprasad Shee
Summary: This study investigates the direct conversion of n-butanol to aromatics using Zn-deposited HZSM5 catalysts, showing that the presence of Zn enhances the selectivities of aromatics and BTEX. Increasing temperature and decreasing WHSV also contribute to higher selectivities, but high pressure has a adverse effect on the aromatics selectivity.
MICROPOROUS AND MESOPOROUS MATERIALS
(2021)
Article
Chemistry, Physical
Yutao Hu, Xiaolong Liu, Yang Zou, Haijiao Xie, Tingyu Zhu
Summary: Pt nanoparticle catalysts supported on a series of TiO2-SiO2 composites were prepared and their CO oxidation activities were evaluated under dry and humid conditions. The catalyst Pt/1Ti-3Si showed the best performance under both conditions and has potential for future industrial applications. The promotion effect of H2O was studied and found to be correlated with H2O concentration and Ti-Si ratio. Defects on the supports inhibited phase transformation and lattice growth for TiO2. The formation of metallic Pt0 particles was beneficial for CO oxidation. The H2O promotion effect could be controlled by regulating the nature of the support. The proposed mechanism of H2O promotion confirmed the carboxyl intermediate pathway.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Tongxin Han, Yuanyuan Li, Yueqiang Cao, Ilkeun Lee, Xinggui Zhou, Anatoly I. Frenkel, Francisco Zaera
Summary: The effect of gases on the surface composition of Cu-Pt bimetallic catalysts has been investigated through in situ infrared and x-ray absorption spectroscopies. The results showed that Pt atoms can diffuse within the Cu-Pt nanoparticles in both vacuum and gaseous atmospheres. Reversible segregation and diffusion of Pt on the surface were observed when varying the temperature and gas environment. The surface composition of the catalysts is highly dependent on temperature.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Organic
Yue Dong, Xiangmin Li, Peng Ji, Feng Gao, Xiang Meng, Wei Wang
Summary: A direct formylation method using cost-effective deuterated glyoxylic acid as the formylation agent has been developed. This method allows for the synthesis of structurally diverse C1-deuterated 3-formylindoles with high D-incorporation using visible light and air as the terminal oxidant.
Article
Chemistry, Multidisciplinary
Kwihwan Park, Naoya Ito, Tsuyoshi Yamada, Hironao Sajiki
Summary: A continuous-flow deuteration methodology for various aromatic compounds is developed based on heterogeneous platinum-catalyzed hydrogen-deuterium exchange. The use of Pt/CB as catalyst support allows for continuous operation for at least 24 hours without significant deterioration of catalyst activity. Deuteration of substrate solutions through the Pt/CB layer in the cartridge packed with Pt/CB can be completed within 60 seconds.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2021)
Article
Chemistry, Multidisciplinary
Richard J. Lewis, Maximilian Koy, Margherita Macino, Mowpriya Das, James H. Carter, David J. Morgan, Thomas E. Davies, Johannes B. Ernst, Simon J. Freakley, Frank Glorius, Graham J. Hutchings
Summary: Heterogeneous palladium catalysts modified by N-heterocyclic carbenes (NHCs) have shown high effectiveness in the direct synthesis of hydrogen peroxide (H2O2) without the need for promoters. By carefully selecting the N-substituent of the NHC, catalytic performance can be greatly improved, reaching concentrations of H2O2 rivaling that obtained by state-of-the-art catalysts.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Dukhan Kim, Melanie S. Sanford, Thomas P. Vaid, Anne J. McNeil
Summary: The nonaqueous redox-matched flow battery (RMFB) stores charge on redox-active moieties tethered to insoluble polymer beads, transferring charge between electrodes and beads via soluble mediators with matching redox potentials. This approach enables high energy density and prevents crossover of active material.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Liam S. Sharninghausen, Sean Preshlock, Stephen T. Joy, Mami Horikawa, Xia Shao, Wade P. Winton, Jenelle Stauff, Tanpreet Kaur, Robert A. Koeppe, Anna K. Mapp, Peter J. H. Scott, Melanie S. Sanford
Summary: This report presents a copper-mediated radiocyanation method for aryl halides that can be applied to complex molecules. The reaction demonstrates a broad tolerance to various functional groups, including unprotected amino acids, making it possible to introduce [C-11]CN into specific sites of peptides. The use of a diamine-ligated copper(I) mediator is essential for achieving high radiochemical yield under mild conditions, while minimizing unwanted side reactions. The method has been successfully scaled and automated for the synthesis of radiolabeled peptides, and has been applied to the preparation of [C-11]cyano-NOP for biodistribution studies using positron emission tomography.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Matthew R. Lasky, Tolani K. Salvador, Sukrit Mukhopadhyay, Matthew S. Remy, Thomas P. Vaid, Melanie S. Sanford
Summary: This report describes the development of a photochemical method for C(sp(2))-H pyridination that leverages the photoexcitation of electron donor-acceptor (EDA) complexes. The reaction results in aryl radical cation intermediates that can be trapped with pyridine nucleophiles under aerobic conditions. This approach eliminates the need for an exogenous photocatalyst and is cost-effective.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Thomas P. Vaid, Monique E. Cook, Jessica D. Scott, Marino Borjesson Carazo, Jonathan Ruchti, Shelley D. Minteer, Matthew S. Sigman, Anne J. McNeil, Melanie S. Sanford
Summary: Cyanopyridines and cyanophenylpyridines were investigated as anolytes for nonaqueous redox flow batteries. Adding a phenyl group can improve the stability of the radical anions and voltage efficiency, with 3-CN-6-PhPy and 3-CN-4-PhPy showing the most promising results.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Review
Chemistry, Multidisciplinary
Naish Lalloo, Conor E. Brigham, Melanie S. Sanford
Summary: Transition-metal-catalyzed decarbonylative coupling reactions using carboxylic acid derivatives as electrophiles have the advantages of abundant and inexpensive reactants. This Account highlights the development of base-free decarbonylative coupling reactions catalyzed by group 10 metals and discusses the catalyst design guided by stoichiometric organometallic studies. The article also discusses the challenges and future directions in this field.
ACCOUNTS OF CHEMICAL RESEARCH
(2022)
Article
Chemistry, Physical
Yichao Yan, Leyuan Zhang, Ryan Walser-Kuntz, David B. Vogt, Matthew S. Sigman, Guihua Yu, Melanie S. Sanford
Summary: This report addresses the challenge of limited redox active molecules for non-aqueous redox flow batteries through the development of an organic storage material based on the benzotriazole scaffold. The developed derivative exhibits a low redox potential, high solubility, and stable electrochemical cycling in a prototype flow battery.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Michael W. Milbauer, Jeff W. Kampf, Melanie S. Sanford
Summary: In this study, we successfully isolated a cyclometalated nickel(IV) complex that is similar to a key intermediate proposed in aminoquinoline-directed C-H functionalization catalysis. The complex undergoes bond-forming reaction under mild conditions and demonstrates the importance of LX-type ligands in stabilizing these nickel(IV) species.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Review
Chemistry, Multidisciplinary
Ryan Walser-Kuntz, Yichao Yan, MatthewS. Sigman, Melanie S. Sanford
Summary: Redox flow batteries are a promising technology for energy storage, and the design of optimal molecules as energy storage materials is crucial. These molecules should undergo reversible redox reactions at high or low potentials for oxidation and reduction, respectively, in addition to being highly soluble and stable during electrochemical cycling. The Account describes the design and optimization process of organic molecules, using aminocyclopropenium-based catholytes as an example.
ACCOUNTS OF CHEMICAL RESEARCH
(2023)
Article
Chemistry, Multidisciplinary
E. William Webb, Kevin Cheng, Jay S. Wright, Jocelyn Cha, Xia Shao, Melanie S. Sanford, Peter J. H. Scott
Summary: Radiocyanation is an attractive and complementary strategy for incorporating carbon-11 into radiotracer targets. This approach utilizes a Cu-11CN complex to capture aryl radical intermediates, enabling rapid and mild radiocyanation. Examples include the reaction of CuI with aryldiazonium salt and visible-light photocatalysis of aryl iodides, both followed by coupling with Cu-11CN to access challenging radiocyanated products.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Applied
Tanpreet Kaur, Xia Shao, Mami Horikawa, Liam S. Sharninghausen, Sean Preshlock, Allen F. Brooks, Bradford D. Henderson, Robert A. Koeppe, Alexandre F. DaSilva, Melanie S. Sanford, Peter J. H. Scott
Summary: This report compares four different routes for the clinical-scale radiosynthesis of the kappa-opioid receptor antagonist [11C]LY2795050. Palladium-mediated radiocyanation and radiocarbonylation of an aryl iodide precursor, as well as copper-mediated radiocyanation of an aryl iodide and an aryl boronate ester, have been investigated. Full automation of all four methods is reported, each of which provides [11C]LY2795050 in sufficient radiochemical yield, molar activity, and radiochemical purity for clinical use. The advantages and disadvantages of each radiosynthesis method are compared and contrasted.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2023)
Article
Chemistry, Inorganic & Nuclear
Jonathan R. Hall, Isaac M. Blythe, Liam S. Sharninghausen, Melanie S. Sanford
Summary: This report describes the Cu-catalyzed directed fluoroalkylation of aryl bromide substrates using N heterocyclic carbene copper(I) fluoroalkyl complexes and aryl halides bearing ortho-directing groups such as pyridine, pyrazole, oxazoline, imine, and ester. These directing groups significantly enhance the reactivity of aryl bromides and chlorides with (IPr)CuI-fluoroalkyl complexes, leading to the formation of aryl-fluoroalkyl coupling products.
Article
Chemistry, Inorganic & Nuclear
Abebu A. Kassie, Ila Y. Castro De la Torre, Matthew S. Remy, Sukrit Mukhopadhyay, Jeff Kampf, Fengrui Qu, Melanie S. Sanford
Summary: This manuscript investigates the impact of different metals (ruthenium, iron, and manganese) on the PNP pincer complex-catalyzed dehydrogenative coupling reaction. The study reveals that the structures and reactivities of the intermediates vary depending on the metal used. It is found that the manganese pincer complex is an effective catalyst for the conversion of formamides and alcohols to carbamates under specific conditions.
Article
Chemistry, Inorganic & Nuclear
Ellen Y. Aguilera, En-Chih Liu, Scott M. Thullen, Melanie S. Sanford
Summary: This study describes the Pd-catalyzed C(sp3)-H functionalization of a tropane derivative, resulting in functionalization at two (beta/gamma) or three (beta/gamma/beta) different positions on the alicyclic amine core. The reaction involves initial dehydrogenation to generate alkene products, which can further react to form a Pd(I) alkene-bridged dimer. Functionalization of this dimer leads to beta/gamma/beta-functionalized allylic arylation and allylic acetoxylation products.
Article
Chemistry, Inorganic & Nuclear
Ellen Y. Aguilera, En-Chih Liu, Scott M. Thullen, Melanie S. Sanford
Summary: This study describes the Pd-catalyzed C(sp(3))-H functionalization of a tropane derivative, resulting in products with functionalization at two or three different sites on the alicyclic amine core. The reaction involves dehydrogenation to generate an alkene product, which can further react to form a Pd(I) alkene-bridged dimer. Functionalization of this dimer produces ss/./ss-functionalized allylic arylation and allylic acetoxylation products.
Article
Materials Science, Multidisciplinary
Yichao Yan, Ryan Walser-Kuntz, Melanie S. Sanford
Summary: In this study, phenoxazine derivatives with N-methyl, N-isopropyl, and N-cyclopropenium substituents were synthesized and studied as catholytes for nonaqueous redox flow batteries. The derivatives showed high redox potentials and stable electrochemical cycling.
ACS MATERIALS LETTERS
(2022)