Article
Chemistry, Applied
Xuerui Ma, Robert P. Davies
Summary: Readily accessible tartramide ligands have been shown to promote copper-catalysed N-arylation under mild conditions. The coupling protocol overcomes limitations of Ullmann coupling and is cost-effective, operating at low catalyst loadings and room temperature with improved tolerance to air and moisture. Detailed kinetic studies provide insights into the factors influencing the reaction rate and have been used for further optimization of the reaction protocol. The reaction scope includes a wide range of substituted aryl iodides with both primary and secondary amines.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Man Li, Rong-Zhen Liao
Summary: Density functional theory calculations were used to elucidate the water oxidation mechanism catalyzed by polyanionic tetramanganese complex. Theoretical results showed that sequential proton-coupled electron transfer oxidations led to the formation of an oxygen radical, facilitating the formation of O-O bond. Subsequent oxidation reactions enabled the release of oxygen.
Article
Chemistry, Physical
Linette Ronn Barsoe, Shunmugavel Saravanamurugan, Esben Taarning, Juan Salvador Martinez Espin, Sebastian Meier
Summary: Recent advances in sustainable materials and energy production have led to a renewed focus on the study and utilization of carbohydrates. A promising approach involves cracking C6 carbohydrates into C2 fragments and then combining them to produce C4 carbohydrates. Under suitable reaction conditions, rare aldrotetroses THR and ERY can be stabilized kinetically and selectively produced using commercial resins with tertiary amine groups as catalysts.
Article
Biochemistry & Molecular Biology
Baichuan Mo, Zhanyu Li, Jinsong Peng, Chunxia Chen
Summary: In this study, polyhydroxylated lignin was prepared by demethylation and hydroxylation of lignin, followed by grafting of phosphorus-containing groups through nucleophilic substitution reaction. The resulting material, PHL-CuI-OPR2, could be used as a carrier for the preparation of heterogeneous Cu-based catalysts. The optimal PHL-CuI-OPtBu2 catalyst was characterized and its catalytic performance in the Ullmann C-N coupling reaction was evaluated, showing high product yields. Furthermore, the catalyst could be easily recovered from the reaction medium.
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
(2023)
Review
Biochemistry & Molecular Biology
Agnes Mastalir, Arpad Molnar
Summary: The Ullmann reaction is the first cross-coupling reaction using a transition metal catalyst. It involves the copper-catalyzed homocoupling of aryl halides, leading to the formation of symmetrical biaryl compounds through the generation of novel C-C bonds. Despite extensive research and valuable results, there is still a focus on developing novel catalytic systems, mild reaction conditions, and expanded substrate scope. The use of recyclable heterogeneous catalysts and alternative metal catalysts has shown promising results in overcoming limitations.
Article
Chemistry, Applied
Neil K. Adlington, Paul S. Siedlecki, Ian Derrick, Simon D. Yates, Andrew D. Campbell, Paula Tomlin, Thomas Langer
Summary: The plant-scale manufacture of AZD5069 faced challenges in removing palladium residues and dealing with the increasing costs of metal, ligand, and scavenger. An alternative copper-catalyzed reaction was developed and successfully operated.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Green & Sustainable Science & Technology
Jun Zhang, Chengyu Li, Sheng Hu, Jing Gu, Haoran Yuan, Yong Chen
Summary: In this study, CuO and Cu2O were used as catalysts for the transformation of bio-based furfural in methanol, serving as both the solvent and an in-situ hydrogen source. The catalytic mechanism of copper oxides (CuOx, x = 0.5, 1) during the reaction was clearly elucidated. The results showed that the conversion of furfural into furfuryl alcohol and 2-methylfuran largely depended on the hydrogen production capability from methanol reforming and furfural adsorption strength over CuOx.
Article
Nanoscience & Nanotechnology
Mei Zhang, Lin Cui, Qiqi Mao, Ziqiang Wang, Hongjie Yu, You Xu, Xiaonian Li, Liang Wang, Hongjing Wang
Summary: In this study, a self-supported mesoporous Pd film catalyst with superior performance for nitrogen reduction reaction (NRR) was successfully synthesized. It was discovered that the coexistence of metallic Pd and its oxide domains with a phase boundary between them can enhance the NRR performance.
Article
Multidisciplinary Sciences
Sandip B. Jadhav, Soumya Ranjan Dash, Sundaram Maurya, Jagadeesh Babu Nanubolu, Kumar Vanka, Rambabu Chegondi
Summary: The authors present a tandem copper-catalyzed reaction for the synthesis of bicyclic borylated compounds with high yield and enantioselectivity. This method combines beta-borylation and Michael addition reactions on specific prochiral enone-tethered compounds. The asymmetric desymmetrization strategy used in this reaction allows for the synthesis of densely functionalized bicyclic enones with multiple stereocenters.
NATURE COMMUNICATIONS
(2022)
Article
Green & Sustainable Science & Technology
Pak-Chung Lau, Tsz-Lung Kwong, Ka-Fu Yung
Summary: This study employed various characterizations to investigate the manganese glycerolate catalyst. The catalyst exhibited a mixed-valence compound with a ratio of Mn2+ to Mn3+ that supports the surface analysis. The catalytic system demonstrated efficient biodiesel synthesis and compatibility with higher alcohols.
Article
Chemistry, Organic
Lingyu Zhang, Songlin Zhang
Summary: An efficient method for the synthesis of 1,4-benzothiazinone-3-one derivatives via a potassium carbonate and copper-mediated C-S and C-N Ullmann coupling reaction between 2-bromothiophenol and 2-haloacetanilide is reported. This approach eliminates the need for noble metals and expensive ligands, making it a simple and cost-effective strategy.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Organic
Kaustubh U. Jagushte, Rohit N. Ketkar, Chinmay Thakkar, Sharmistha Dutta Choudhury, Nabanita Sadhukhan
Summary: In this study, a strategic approach was used to synthesize 6-amino-2-naphthol with high efficiency and consistent yield. Two protocols, direct amination and a cascade synthetic approach, were explored. Through extensive method optimization, a superior catalyst combination was discovered, making the synthesis of 6-amino-2-naphthol simple, sustainable, efficient, and with consistent yield.
TETRAHEDRON LETTERS
(2023)
Article
Chemistry, Physical
Wenyan Jia, Maoshuai Li, Mingchan Chen, Jing Lv, Mei-Yan Wang, Xiaojun Bao, Xinbin Ma
Summary: In this study, the detailed mechanism pathways for ethylene oxide methoxycarbonylation over Co-based complexes were established, along with the reaction pathway of the main by-product acetaldehyde. The effect of nitrogen-containing heterocycles on the pathways was examined using DFT calculation and experimental study. The addition of pyrazole as a ligand generated the highest conversion and selectively inhibited by-product formation, leading to the highest selectivity of methyl 3-hydroxypropionate.
MOLECULAR CATALYSIS
(2023)
Article
Chemistry, Physical
Seongmin Jin, Yongha Park, Gina Bang, Nguyen Dat Vo, Chang-Ha Lee
Summary: This study presents the use of a MgCeOx-supported Cu catalyst with a unique bead structure to enhance the water-gas shift reaction. The introduction of MgO led to unprecedented improvements in activity, promoting water dissociation and participating in redox mechanisms. The use of MgCuCe resulted in a lower hydrogen production cost compared to commercial and CeO2-supported catalysts, paving the way for the development of efficient catalysts utilizing earth-abundant MgO and contributing to cost reduction in H-2 production.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Chemistry, Multidisciplinary
Christian Biermaier, Carolin Gleissner, Thomas Bechtold, Tung Pham
Summary: Researchers investigated the basic mechanism of using citrate anion to fix silver species and form metal catalyst directly on textile substrates. During the particle formation process and subsequent electroless copper deposition, silver undergoes multiple oxidation state changes. Under reducing conditions, silver ions are converted to silver metal. Additionally, the thermal decomposition of silver citrate generates CO2 and hexane-2,5-dione.
ARABIAN JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Steven L. Suib, Jan Prech, Ewelina Szaniawska, Jiri Cejka
Summary: Metal substitution in molecular sieve systems is a driving force for developing novel catalytic processes in green chemistry and achieving sustainability in the chemical industry and our everyday life. Metal-substituted molecular sieves provide advantages such as high surface areas, molecular sieving effects, confinement effects, and variability and stability in active site and morphology.
Article
Engineering, Chemical
Shubham Jamdade, Rishi Gurnani, Hanjun Fang, Salah Eddine Boulfelfel, Rampi Ramprasad, David S. Sholl
Summary: We developed a computational approach to screen MOFs for oxygen-helium separation at low temperatures. Through molecular simulations and stability evaluation, we identified high-performance materials for this separation process. This method can also be applied to selecting adsorbents for other gas separations.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Physical
Huan Tran, Kuan-Hsuan Shen, Shivank Shukla, Ha-Kyung Kwon, Rampi Ramprasad
Summary: Modern fuel cell technologies use Nafion for proton-exchange membrane and as the binding material for the catalyst layers. This study proposes an informatics-based scheme to search large polymer chemical spaces and identifies 60 new polymer candidates for various applications in fuel cells.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
D. Randil K. Weerasuriya, Keshani Hiniduma, Snehasis Bhakta, Lisa M. Nigro, Luisa F. Posada, Haiyan Tan, Steven L. Suib, Richard Kremer, James F. Rusling
Summary: This study reports a low-cost, mix-and-read COVID-19 assay using a synthetic SARS-CoV-2 sensor, imaged and processed using a smartphone. The assay was optimized for saliva and demonstrated a detection limit of 200 TCID50/mL in artificial saliva.
Article
Chemistry, Physical
Samson O. Owalude, Isaac T. Olowookere, Inosh Perera, Harshul S. Khanna, Elsa Njeri, Xueni Huang, Andrew G. Meguerdichian, Hamad-Tijani O. Ayilara, Steven L. Suib
Summary: A series of mixed-phase Zr-doped TiO2 photocatalysts were synthesized using a sol-gel technique and their performance in the photocatalytic degradation of orange II dye was investigated. Characterization methods including XRD, TEM, XRF, Raman spectroscopy, TGA, and XPS revealed the composition and structure of the materials. The results showed that the photocatalysts consisted of zirconium, titanium, and oxygen, with anatase and rutile phases of TiO2 present. The undoped TiO2 exhibited the highest stability, and the materials successfully degraded orange II dye solution up to 7 cycles through asymmetric cleavage of the azo bond.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Rishi Gurnani, Christopher Kuenneth, Aubrey Toland, Rampi Ramprasad
Summary: Artificial intelligence-based methods are effective in screening polymer libraries for experimental inquiry. Our approach uses machine learning to extract important features from polymer repeat units, speeding up feature extraction by 1-2 orders of magnitude without compromising model accuracy. This approach will enable more sophisticated and large-scale screening technologies in polymer informatics.
CHEMISTRY OF MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Yong-Liang Su, Liang Yue, Huan Tran, Mizhi Xu, Anthony Engler, Rampi Ramprasad, H. Jerry Qi, Will R. R. Gutekunst
Summary: In this study, a chemically recyclable polythioether system based on nucleophilic aromatic substitution (SNAr) was developed. The system demonstrated chain-growth ring-opening polymerization through SNAr reactions, with fast reaction rates and efficient polymerization and depolymerization cycles. The resulting polythioether materials showed comparable performance to commercial thermoplastics, and could be depolymerized to the original monomers in high yields.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Biochemistry & Molecular Biology
Caroline Donaghy, Jose Gabriel Javellana, Young-Jin Hong, Karrera Djoko, Alfredo M. Angeles-Boza
Summary: Antimicrobial peptides (AMPs) are being studied as an alternative to antibiotics due to their broad-spectrum antimicrobial activity and ability to avoid resistance development. In this review, the focus is on metalloAMPs that interact with the essential metal ion zinc(II) to enhance their antimicrobial efficacy. By understanding the synergistic interactions between AMPs and zinc(II), researchers can develop new antimicrobial agents and accelerate their therapeutic use.
Article
Chemistry, Multidisciplinary
Shanka Dissanayake, Noah Leonard, Shubhashish Shubhashish, Isaac T. Olowookere, Inosh Prabasha Perera, Luisa F. Posada, Mohammad Khairul Islam, Steven L. Suib, Partha Nandi
Summary: This study introduces a novel method for the production of allyl acrylate from allyl alcohol as the starting substrate. The reaction employs a reusable catalyst based on Li-ion-promoted mesoporous manganese oxide, offering mild reaction conditions. The catalytic activity, selectivity, and substrate scope of the reaction are reported to have a yield of 60%. The proposed system consists of an allylic alcohol substrate, O2 as the oxidant, N-hydroxyphthalimide (NHPI) as the promoter, trichloro acetonitrile (CCl3CN) as the solvent, and Li-promoted manganese oxide as the catalyst (surface area >150 m2/g).
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Physical
Pranav Shetty, Arunkumar Chitteth Rajan, Chris Kuenneth, Sonakshi Gupta, Lakshmi Prerana Panchumarti, Lauren Holm, Chao Zhang, Rampi Ramprasad
Summary: This study used natural language processing methods to extract material property data from polymer literature abstracts. By training the MaterialsBERT language model, we obtained around 300,000 material property records for analysis in various applications such as fuel cells, supercapacitors, and polymer solar cells.
NPJ COMPUTATIONAL MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Alireza Shirazi Amin, Wen Zhao, Panteha Toloueinia, Inosh Prabasha Perera, Jared Fee, Yue Su, Luisa F. Posada, Steven L. Suib
Summary: This research reports the synthesis and characterization of an artificially layered LiTaO3 electrode material for lithium-ion batteries. The designed layered anode shows high specific capacity and cycling-induced capacity increase. Various characterization techniques were used to understand the mechanisms behind the improved performance of the electrode.
Article
Chemistry, Multidisciplinary
Hanlin Chen, Gaoling Wei, Zijuan You, Xiaoliang Liang, Peng Liu, Yiping Yang, Fuding Tan, Suhua Wang, Jieqi Xing, Steven L. Suib
Summary: For perovskite La1-xCaxCoO3 (Ca-x, x = 0-0.3), Ca-0.2 with the closest O p band center to the Fermi level, exhibits the highest catalytic activity for toluene oxidation. The O p band center plays a crucial role in determining reducibility and active oxygen content. This discovery is beneficial for designing highly active perovskite catalysts.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Qiang Luo, Hanyi Duan, Michael C. McLaughlin, Kecheng Wei, Joseph Tapia, Joseph A. Adewuyi, Seth Shuster, Maham Liaqat, Steven Suib, Gael Ung, Peng Bai, Shouheng Sun, Jie He
Summary: We used polymer N-heterocyclic carbenes (NHCs) to control the microenvironment surrounding metal nanocatalysts, enhancing their catalytic performance in CO2 electroreduction. Three polymer NHC ligands were designed with different hydrophobicity: hydrophilic poly(ethylene oxide) (PEO-NHC), hydrophobic polystyrene (PS-NHC), and amphiphilic block copolymer (PEO-b-PS-NHC). The introduction of hydrophobic PS segments led to a twofold increase in the partial current density for CO formation. The hydrophobic polymers altered the hydrogen bonding structures of water, improving CO2 diffusion and subsequent reduction.
Article
Chemistry, Multidisciplinary
Zichao Wei, Chung-Hao Liu, Qiang Luo, Srinivas Thanneeru, Alfredo M. Angeles-Boza, Mu-Ping Nieh, Jie He
Summary: We investigated the hydrophobicity-enhanced reactivity of Cu2+ ions as an ester hydrolase. By varying the synthetic sequence of amphiphilic block copolymers, we controlled the location of the Cu2+ binding motif in polymer micelles. The hydrophobicity of Cu2+ sites significantly impacted their catalytic efficiency, with as much as 60 times more activity. Our findings highlight the importance of hydrophobic microenvironments in the design of bioinspired catalysts.
MATERIALS CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Murphy Jennings, Elena Cuellar, Ariadna Rojo, Sergio Ferrero, Gabriel Garcia-Herbosa, John Nganga, Alfredo M. Angeles-Boza, Jose M. Martin-Alvarez, Daniel Miguel, Fernando Villafane
Summary: New 1,2-azolylamidino complexes were synthesized and characterized. The compounds showed catalytic activity in CO2 electrocatalytic reduction and photocatalytic CO2 reduction, producing CO and formate.
DALTON TRANSACTIONS
(2023)