Article
Chemistry, Multidisciplinary
Ilana B. Stone, Rachel L. Starr, Norah Hoffmann, Xiao Wang, Austin M. Evans, Colin Nuckolls, Tristan H. Lambert, Michael L. Steigerwald, Timothy C. Berkelbach, Xavier Roy, Latha Venkataraman
Summary: This study describes the Ullmann coupling of aryl iodides on rough gold surfaces, investigations of the reaction mechanism using experimental and theoretical methods reveal the influence of surface roughness and local electric fields on the reaction, providing important insights for understanding catalysis.
Article
Chemistry, Physical
Xiang-Yang Liu, Jia-Jia Yang, Wen-Kai Chen, Alexey Akimov, Wei-Hai Fang, Ganglong Cui
Summary: In this study, the interfacial properties of the C-60-Py@MAPbI(3) heterojunction were explored using density functional theory calculations. The results showed that the spin-orbit coupling effects significantly influenced the electron transfer rate, accelerating the transfer of electrons from MAPbI(3) to C-60-Py.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Ding-Rong Deng, Ru-Ming Yuan, Pei-Kai Yu, Fei Xue, Xiao-Xiang Fan, Jie Lei, Jie-Ling Zhang, Xiao-Dong Lin, Qi-Hui Wu, Jing-Min Fan, Jeng-Kuei Chang, Wen-Jing Hong, Ming-Sen Zheng, Quan-Feng Dong
Summary: An electron conductive matrix facilitates electron transport in an electrochemical device by limiting the breadth and depth of electrochemical reactions. By introducing enhanced electrodes coupled with conducting molecules, a new realm of reaction chemistry at the electrode interface is opened up, improving the performance of batteries significantly.
ADVANCED ENERGY MATERIALS
(2021)
Article
Geosciences, Multidisciplinary
Jicai Zeng, Bo Guo
Summary: Per- and polyfluoroalkyl substances (PFAS) are contaminants that are strongly retained in vadose zones due to adsorption. The leaching of PFAS through vadose zones poses a great risk of groundwater contamination. Previous studies have underestimated the impact of preferential flow caused by soil heterogeneities on PFAS transport. Our numerical simulations show that longer-chain PFAS experience accelerated leaching due to reduced accessible air-water interfacial areas along preferential flow pathways. It is critical to characterize soil heterogeneities to accurately predict the leaching of long-chain PFAS in vadose zones.
GEOPHYSICAL RESEARCH LETTERS
(2023)
Article
Multidisciplinary Sciences
Liang Qiao, Zhiyan Zuo, Renhe Zhang, Shilong Piao, Dong Xiao, Kaiwen Zhang
Summary: Soil moisture-atmosphere coupling induces non-linear warming via the 'warmer climate - drier soil' feedback, exerting an accelerating effect on global warming and extreme high temperatures. The projection shows that SA-driven warming will exceed 0.5°C over extratropical landmasses by the end of the 21st Century, increasing the likelihood of extreme high temperatures.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Physical
Payam Ahmadian Koudakan, Xiaobin Hao, Amirabbas Mosallanezhad, Cong Wei, Jinyan Cai, Junxin Xiao, Yuqing Yang, Bo Liu, Jun Liu, Yanyan Fang, Gongming Wang
Summary: Precisely tuning electronic perturbation by interfacial coupling could provide valuable insights into designing highly efficient water splitting catalysts and beyond.
JOURNAL OF MATERIALS CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Cristian Cavedon, Sebastian Gisbertz, Susanne Reischauer, Sarah Vogl, Eric Sperlich, John H. Burke, Rachel F. Wallick, Stefanie Schrottke, Wei-Hsin Hsu, Lucia Anghileri, Yannik Pfeifer, Noah Richter, Christian Teutloff, Henrike Mueller-Werkmeister, Dario Cambie, Peter H. Seeberger, Josh Vura-Weis, Renske M. van der Veen, Arne Thomas, Bartholomaus Pieber
Summary: We demonstrate visible-light-mediated carbon-heteroatom cross-coupling reactions using a photoactive Ni(II) precatalyst. The activation of this precatalyst involves an initial intraligand charge transfer event triggered by visible light irradiation. Additionally, a porous, recyclable organic polymer for heterogeneous nickel catalysis of cross-coupling reactions is obtained through ligand polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qinan Chen, Shuyao Wu, Po Zhang, Xi-Ming Song, Zhining Song
Summary: In this study, a stable hot Pickering emulsion interfacial catalysis (HPEIC) system was constructed to improve the efficiency of catalytic depolymerization of PET. The HPEIC system achieved 100% depolymerization of PET within a short time and maintained a high depolymerization rate under low temperature reaction conditions.
Article
Physics, Fluids & Plasmas
Yechan Noh, N. R. Aluru
Summary: This study reports the influence of atomic-scale vibrational coupling at the solid-fluid interface on interfacial properties such as wettability and fluid slip. Molecular dynamics simulation reveals that the contact angle increases and solid-fluid adsorption weakens when the oscillation frequency of the substrate matches the bending frequency of liquid water. The study also shows that vibrational matching at the interface reduces wall-fluid friction and enhances water transport through nanopores.
Review
Chemistry, Multidisciplinary
Myuto Kashihara, Yoshiaki Nakao
Summary: Cross-coupling reactions using nitroarenes as electrophiles have gained attention due to their ease of accessibility and potential advantages over haloarenes. Recent research has focused on developing new catalyst systems and reaction conditions to improve the efficiency and practicality of these reactions, with promising results in diversifying bond-forming reactions and reducing catalyst loading. Research in this field is expected to continue growing as the utility of nitroarenes in organic synthesis is reevaluated.
ACCOUNTS OF CHEMICAL RESEARCH
(2021)
Article
Chemistry, Multidisciplinary
Cheng-Bin Jin, Nan Yao, Ye Xiao, Jin Xie, Zeheng Li, Xiang Chen, Bo-Quan Li, Xue-Qiang Zhang, Jia-Qi Huang, Qiang Zhang
Summary: Lithium (Li)-metal batteries suffer severe capacity deterioration at extreme temperatures due to increased kinetic barrier of interfacial processes. This study quantitatively probes the interfacial kinetics in three different electrolytes and reveals that desolvation is the limiting step dominating the cell impedance and capacity at low temperature. The use of a 1,3-dioxolane-based electrolyte with tamed solvent-solute interaction facilitates fast desolvation and enables practical Li|LiNi0.5Co0.2Mn0.3O2 cells at -40 degrees C to retain 66% of room-temperature capacity and withstand fast charging rates. The barrier of desolvation dictated by solvent-solute interaction environments is quantitatively uncovered, and regulating this interaction emerges as a promising solution to low-temperature batteries.
ADVANCED MATERIALS
(2023)
Review
Chemistry, Multidisciplinary
Liangliang Song, Lingchao Cai, Lei Gong, Erik V. Van der Eycken
Summary: Copper-catalyzed enantioselective coupling reactions have been extensively studied for the rapid synthesis of chiral molecules. Despite progress in polar and radical mechanisms, the development of general and practical strategies for the regio-, enantio-, and diastereoselective assembly of stereogenic centers remains challenging. The integration of photocatalysis with asymmetric copper catalysis offers new reaction pathways and diverse chiral compounds, expanding the scope of radical chemistry. This review provides a summary of recent advances in photoinduced copper-catalyzed enantioselective coupling reactions, with a discussion on the mechanistic aspects.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Physical
Guang-Yan Xing, Ya-Cheng Zhu, Deng-Yuan Li, Pei-Nian Liu
Summary: On-surface synthesis, a powerful tool for atomically precise fabrication of low-dimensional carbon nanomaterials, has greatly enriched fundamental science and technology. Achieving high selectivity of covalent coupling reactions remains challenging due to the complicated reactivity of organic groups and irreversibility of covalent bonds. Only a few on-surface covalent coupling reactions are frequently used, and this Perspective focuses on the development and synthetic applications of on-surface cross-coupling reactions.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Review
Chemistry, Multidisciplinary
Yaowen Liu, Pengfei Li, Yanwei Wang, Youai Qiu
Summary: Electrochemistry employs electrons as an efficient and sustainable alternative to chemical oxidants or reductants, and has gained popularity for selective organic synthesis. The combination of electrochemistry with readily available electrophiles has emerged as a viable method for constructing challenging C-C and C-heteroatom bonds. This mini-review provides a systematic summary of the recent advances in electroreductive cross-electrophile coupling (eXEC) reactions, focusing on aryl and alkyl organic (pseudo)halides, as well as small molecules such as CO2, SO2, and D2O.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Inorganic & Nuclear
Zhilong Li, Chengyang Li, Yu Ding, Haohua Huo
Summary: The merger of nickel catalysis and photocatalysis has provided a transformative platform for the rapid assembly of molecular complexity. However, the development of enantioselective transformations in nickel photoredox catalysis remains challenging but holds great promise.
COORDINATION CHEMISTRY REVIEWS
(2022)
Article
Chemistry, Medicinal
Sichen Song, Chenguang Wang, Bo Zhang, Changquan Calvin Sun, Timothy P. Lodge, Ronald A. Siegel
Summary: This study reports a method of miscibility determination based on the overlap concentration, c*, which can be conveniently determined from the viscosity-composition diagram. The determined c* values strongly correlate with the physical stability of amorphous solid dispersions (ASDs) of two model drugs, celecoxib and loratadine, with four different grades of polyvinylpyrrolidone (PVP). This suggests the potential application of the c* concept in designing stable high drug loaded ASD formulations and provides a procedure for broader adoption of this methodology, which is easy to apply and widely applicable for thermally stable binary drug/polymer combinations.
JOURNAL OF PHARMACEUTICAL SCIENCES
(2023)
Review
Polymer Science
Saptasree Bose, Victoria Padilla, Alexandra Salinas, Fariha Ahmad, Timothy P. Lodge, Christopher J. Ellison, Karen Lozano
Summary: Nanofibers have unique properties that have attracted significant interest, such as high specific surface area, high aspect ratio, and spatial interconnectivity. Design strategies, including core-sheath, concentric layers, and particle distribution, are being used to prescribe the internal structure of nanofibers. This review provides a comprehensive overview of the design strategies being used to produce the next generation of nanofiber systems, discussing processing methods and their effects on the nano- and microstructure, as well as physico-chemical effects on fiber morphology.
Article
Polymer Science
Claire L. Seitzinger, Timothy P. Lodge
Summary: By incorporating a photoactive moiety into a block polymer, the phase behavior of the polymer can be controlled with light. The positioning of pendant azobenzene groups along the polymer backbone significantly affects the phase transition temperature and the ability to control the behavior with light and temperature. By adjusting the location of the azobenzene units within the polymer solution, the overall behavior of the solution can be changed.
Article
Nanoscience & Nanotechnology
Timothy P. Lodge, Frank S. Bates, Michael B. Sims, Joshua W. Goetze, Gabriela Diaz Gorbea, Zachary M. Gdowski
Summary: We propose an approach to photocrosslink bicontinuous microemulsions derived from ternary blends, enabling detailed structural characterization. This strategy utilizes a photodimerization reaction to covalently crosslink blends, preserving the intricate network structure. The resulting crosslinked microemulsions exhibit rubbery behavior at elevated temperatures and can be imaged by microscopy techniques. The versatile nature of this strategy is demonstrated by achieving a heterogeneous solid electrolyte with high conductivity.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Nicholas J. Van Zee, Amanda S. Peroutka, Marc A. Hillmyer, Timothy P. Lodge
Summary: Poloxamers, also known as Pluronics, have been found to alleviate cellular membrane damage, but the underlying protection mechanism is still unclear. This study investigated the impact of poloxamer molar mass, hydrophobicity, and concentration on the mechanical properties of lipid vesicles, revealing that poloxamers tend to decrease the stretching modulus. The study provides important insights into how poloxamers interact with lipid membranes and protect cells from various stresses.
Article
Polymer Science
Supriya Gupta, Timothy P. Lodge
Summary: This study investigates the fragmentation mechanism of block copolymer micelles in ionic liquids. It is found that the driving force for micelle fragmentation can be enhanced by controlling the amount of low interfacial tension solvent, leading to faster fragmentation.
Article
Polymer Science
Bo Zhang, Shuquan Cui, Timothy P. Lodge, Frank S. Bates
Summary: In this study, the structure and phase behavior of ternary mixtures containing AB bottlebrush diblock copolymer and A and B linear homopolymers were systematically investigated using small-angle X-ray scattering and cloud point measurements. The overall phase behavior of these mixtures closely resembles the linear counterparts, but with a significantly weaker increase in lamellar and microemulsion domain spacing as the homopolymer content increases. This behavior is attributed to an unconventional spatial distribution of the homopolymer within the bottlebrush architecture of the diblock copolymer. These ternary mixtures offer a promising platform for designing cocontinuous materials with an expanded parameter space using bottlebrush polymers.
Article
Materials Science, Multidisciplinary
Bo Zhang, Caini Zheng, Frank S. Bates, Timothy P. Lodge
Summary: Charged block copolymers have potential as next generation battery electrolytes due to their ability to self-assemble into various nanostructures with high ionic conductivity and mechanical strength. This study investigates the impact of ions on the self-assembly of charged block copolymers by employing a nonpolar matrix to enhance electrostatic interactions. The phase behavior was analyzed using small-angle X-ray scattering (SAXS), revealing an asymmetric shape of the phase boundary and comparable composition windows of ordered phases to neutral diblock copolymers. These findings provide insight into the design of nanostructured polymer electrolytes and the influence of ions on charged block copolymer self-assembly.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Nanoscience & Nanotechnology
Ming Liu, Xiao Liu, Hui Liu, Miaomiao Han, Shengxiang Ji
Summary: In this study, a novel antimicrobial cotton fabric was developed by covalently bonding hyperbranched polylysine onto the surface of cotton fabric. The resulting fabric exhibited excellent antimicrobial activity, durability, and safety, highlighting the advantages of using HPL in the antimicrobial finishing of fabrics.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Guohao Chen, Xiao Liu, Rui Zhang, Miaomiao Han, Shengxiang Ji
Summary: In this study, antibacterial plastics were successfully prepared by coating a HPL-DOSS complex onto the surfaces of plastics and demonstrated excellent antibacterial activity and anti-adhesive property against Escherichia coli and MRSA, leading to a reduction in biofilm formation. Furthermore, the antibacterial plastics exhibited excellent biocompatibility, making them a safe option for reducing bacterial infections on plastic surfaces.
JOURNAL OF THE CHINESE CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Joseph F. Hassler, Megan Lawson, Erika Cerna Arroyo, Frank S. Bates, Benjamin J. Hackel, Timothy P. Lodge
Summary: Poloxamers, composed of PEO and PPO blocks, interact with phospholipid bilayers and alter their mechanical and surface properties. This study used NMR spectroscopy to measure the binding affinity of Poloxamers to liposomes at different temperatures and found a significant increase in binding affinity at higher temperatures. Moreover, the polymer chains can penetrate the bilayer and access the interior of liposomes at elevated temperatures, which is not possible at lower temperatures. This research reveals the molecular mechanism of Poloxamer-lipid bilayer interactions and has important implications for modulating the properties of liposomes and cell membranes.
Article
Polymer Science
Timothy P. Lodge, En Wang, Jiahao Zhu, Frank S. Bates
Summary: The self-assembly behavior of four polystyrene and poly(ethylene-alt-propylene) block copolymers in a selective solvent was studied. Spherical micelles were formed by all four polymers, with the symmetric triblock copolymer having the smallest micelle size. However, the asymmetric triblock copolymers did not form any specific packing arrangement. This result suggests that the two-layer corona of the asymmetric triblock copolymers may play a role in their self-assembly behavior. At higher concentrations, all four polymers adopted hexagonal packings before transitioning to lamellar structures.
Article
Polymer Science
Guangcheng Huang, Hanwen Lai, Jun Song, Yizhou Jiang, Shengxiang Ji
Summary: In this work, a universal and fab-compatible approach to fabricating 3D chemical patterns for DSA of BCPs with density multiplication is proposed by combining lithographic patterning and plasma treatment. The wetting behavior of BCP films can be controlled by tuning the surface energy of cross-linked polystyrene (XPS) mat through adjusting oxygen plasma treatment conditions. Non-preferential surfaces for various BCPs are obtained by oxygen plasma treatment, eliminating the use of random copolymer brushes in the LiNe flow.
Article
Chemistry, Physical
Caini Zheng, Bo Zhang, Frank S. Bates, Timothy P. Lodge
Summary: The self-assembly behavior of ternary blends of polystyrene (PS) and poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA(n)) with different lengths of oligo(ethylene glycol) side chains n was investigated in this study. Small-angle X-ray scattering was used to examine the phase behavior at different compositions and temperatures. The results showed that the side chain length impacted the order-to-disorder transition temperature and longer side chains resulted in poorer miscibility of homopolymers in the corresponding block, leading to a more dry-brush like swelling behavior.
Article
Polymer Science
Timothy P. Lodge, Claire L. Seitzinger
Summary: By incorporating a photoactive moiety into a block polymer, the phase behavior of the polymer solution can be controlled with light. The positioning of the pendant azobenzene groups along the polymer backbone significantly affects the order-disorder transition of the polymer in the ionic liquid. Adjusting the location of the azobenzene units within the thermo-and photoresponsive polymer solution changes the overall behavior of the solutions and the ability to control that behavior with light and temperature.