bluuebunny/crossref_metadata_2025_split huggingface dataset:
CH Oxidative Functionalization Enabled Transformations of the Alkenes
Authors: Li Yang , Han Ya‐Fei , Li Jin‐Heng 
Published: October 2022

Abstract

Both the CH bonds and alkenes are abundant, readily available feedstocks, and have attracted much ongoing attention on the development of efficient methods for their ideal transformations. Methods that merge their transformations in a single reaction are particularly appealing due to their highest atom‐/step‐economy for constructing complex molecules. Here, recent advances in the CH oxidative functionalization enabled transformations of the alkenes are summarized. To date, a variety of CH bonds, including C(sp
3
)H and C(sp
2
)H bonds, underwent the functionalization across the CC bonds in alkene to enable the transformation of alkenes, such as difunctionalization of alkenes and alkylation/arylation of alkenes. These transformations of alkenes are achieved using two strategies, including the radical‐mediated oxidative strategy or transition‐metal oxidative catalysis.
Hypervalent Iodine and Sulfur‐Mediated CH Functionalization
Authors: Xu Zhenchuang , Cai Yanyao , Zhao Yanchuan 
Published: October 2022

Abstract
Hypervalent main group nonmetallic elements, such as iodine and sulfur, have attracted increasing attention owing to their unique reactivities. The facilely interconvertible valencies sometimes render these nonmetallic elements chemical behaviors analogs to transition metals, allowing diverse CH functionalizations to proceed in a green manner. Since their discovery, hypervalent iodine reagents have played a pivotal role in synthetic organic chemistry. Besides their usage as selective oxidants, hypervalent iodine reagents readily participate in single‐electron transfer processes to produce radical cation intermediates, enabling a variety of oxidative carbon–carbon and carbon–heteroatom bond formations. Direct CH functionalization of arenes, alkenes, and alkynes gives rapid access to aryl iodonium salts, which are easily transformed into other functionalities. Similarly, site‐selective CH thianthrenation proceeds smoothly upon suitable activation of sulfoxide reagents. The superior leaving ability and redox properties make the thianthrene moiety an ideal synthetic handle for structural diversifications via transition‐metal and photoredox catalysis. In this article, we focus on the hypervalent iodine and sulfur‐mediated CH functionalizations and describe their applications in carbon–carbon and carbon–heteroatom bond‐forming reactions. The rearrangement‐based CH functionalization will be briefly introduced where possible.
Sequential CH Functionalization in Complex Molecular Synthesis
Authors: Ma Hao‐Ran , Tang Can , Peng Xiao‐Shui 
Published: October 2022

AbstractCH functionalization is a fundamentally important topic in organic synthesis. Sequentially, application of CH functionalization protocols in the complex molecular synthesis has already been proved to be a practical strategy. In this article, selected significant synthesis of complex molecules involving sequential CH functionalization approaches will be presented and classified into sp2and sp3carbon systems, demonstrating the advantages of the sequential CH functionalization protocol.
Manganese‐Catalyzed CH Bond Activation and Functionalization, From Mechanism to Applications
Authors: Burden Thomas J. , Eastwood Jonathan B. , Fairlamb Ian J.S. , Lynam Jason M. 
Published: October 2022

AbstractStoichiometric Mn(I) CH activation and functionalization reactions have seen a steady growth over the last 50 years, with particular interest in catalytic breakthroughs seen in the last 10 years. CH bond functionalization can take place in suitably activated unsaturated aromatic/heteroaromatic ring systems, containing a directing group for Mn(I), with activation typically occurring proximal (ortho) to the directing group. A range of Mn(I) carbonyl complexes can be used as precatalysts for a raft of transformations involving cyclomanganted intermediates and appropriate acceptor molecules, which brings about the formation of a plethora of organic and organometallic products. One of the limitations in Mn(I) carbonyl catalysis is the requirement for typically high catalyst loadings (10 mol% being common). Thus we have focused on mechanistic work that might help solve this problem, particularly if the promising reported synthetic chemistry of Mn(I) carbonyls is to be used more widely, particularly in industry. Finally, we showcase how time‐resolved IR spectroscopic methods are particularly useful for probing the mechanistic steps involved in CH bond activation catalysis, from picosecond to second timescale. The approaches used might be amenable to the study of other metal‐catalyzed processes.
CH Activation for the Synthesis of Organic Redox‐Active Compounds
Authors: Joo Jung Min 
Published: October 2022

Abstract
Organic redox‐active materials are used in several electrochemical applications; however, their application has expanded from conventional optoelectronic devices to new energy storage systems in recent years. Therefore, the design and synthesis of redox‐active organic compounds are critical for modulating their redox potentials, stability, solubility, and related properties to achieve optimal performance. Through a variety of CH functionalization reactions, the CH bonds of representative redox‐active cores, such as quinones, diimides, and ferrocenes, can be directly replaced to form new CC and C–heteroatom bonds. In addition to increasing the atom‐ and step‐economy, this late‐stage modification strategy allows for the preparation of structural analogs that are not readily accessible by conventional methods. This article reviews the position and type of substituents that can be added to these redox‐active cores, thus providing a perspective on CH functionalization and molecular engineering strategies that can be applied to fine‐tune redox‐active compounds.
Photocatalytic Hydrogen Atom Transfer Enabled Ni‐ and Cu‐Catalyzed C(sp
3
)H Functionalization
Authors: Zhu Shengqing , Qin Jian , Huo Liping , Zhang Yanyan , Chu Lingling 
Published: October 2022

Abstract

Transition metal‐catalyzed CH functionalization represents one of the most viably pursuing research areas in modern synthetic chemistry. Significant attention has been drawn to addressing the challenging functionalization of C(sp
3
)H bonds, particularly un‐activated C(sp
3
)H bonds. Among various strategies, hydrogen atom transfer (HAT) represents a distinct yet attractive approach for the direct and selective functionalization of C(sp
3
)H bonds. This article highlights the recent development of photochemical HAT‐enabled nickel and copper‐catalyzed selective functionalization of C(sp
3
)H bonds, with a particular emphasis on reaction development and mechanistic discussions.
CH Functionalization by Weak Interactions
Authors: Bera Shyamal K. , Bose Anima , Mal Prasenjit 
Published: October 2022

Abstract
Transition metal‐catalyzed CH functionalization or activation reactions of organic compounds have witnessed a broad avenue in the synthesis. However, the metal‐free CH functionalization reactions are relatively less explored. In addition, the research area to control the chemical reactions by various cooperative noncovalent or weak interactions has also appeared to be one of the widespread research topics in supramolecular catalysis. In this article, attempts have been made to collect the literature which utilizes hydrogen bonding (H‐bonding) and halogen bonding (XB) interactions toward CH functionalization reactions.
CS Bonds via CH Functionalization
Authors: Pramanik Milan , Mal Prasenjit 
Published: October 2022

TOC Graphic

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Abstract
The development of CS bonds‐making methodology is mainly explored by condensing metal thiolate with prefunctionalized organic substrates. However, the synthesis of CS bonds via CH functionalization reactions has a significant impact on organic chemistry. Herein, we have collected the literature based on various CS bond formation reactions via CH functionalizations. This article has been subdivided into four categories: (i) metal‐catalysis, (ii) metal‐free reagent, (iii) photoredox catalysis, and (iv) electrochemical‐based.
Recent Advances in Multicomponent Reaction Through CH Bond Functionalization
Authors: Nanda Tanmayee , Mohanty Smruti R. , Ravikumar Ponneri C. 
Published: October 2022

Abstract
Multicomponent reactions (MCRs) serve as a strategic tool for the synthesis of complex molecular architecture in just one step, and hence, it has been an attractive area of research for the synthetic community. In recent years, transition metal‐catalyzed CH bond activation/functionalization has taken the center stage of organic synthesis on account of step and atom economy. The combination of these two enabling methodologies provides a wide opportunity to diversify and enrich the known molecular library. In this regard, MCRs involving transition metal‐catalyzed CH bond activation strategy have been studied in the past few years, which led to many pathbreaking discoveries. This article aims to provide comprehensive knowledge to the reader about MCRs involving the CH bond activation strategy as a key threshold step.
Heterogenous Palladium‐Catalyzed CH Functionalization Reactions
Authors: Liu Dan , Bao Yong‐Sheng 
Published: October 2022

Abstract
Direct CH bond functionalization to construct carbon–carbon bonds has been known as a chemical economic strategy for sustainable syntheses. Especially, palladium‐catalyzed CH functionalization has been extensively studied and proved to be the most efficient and powerful protocol to assemble complex compounds, but this approach was limited by the high price and heavy metal pollution of homogeneous Pd catalysts. To improve the chemical economic and environmentally benign Pd‐catalyzed CH functionalization, heterogeneous Pd nanoparticles were used as catalysts, which can be recovered and reused. This article presented the advances in the heterogeneous Pd nanoparticles with a variety of supporting materials that was applied to catalyze CH functionalization reaction. The common characteristics of the heterogeneous Pd catalyst are recommended, after which methods of Pd nanoparticle catalyst preparation and reactions catalyzed by them are also described.
Design and Synthesis of Carbazole‐Cyclopentathiophene Alternating Copolymers for Inhibiting Phase Separation of Cs0.15FA0.85PbI3
Authors: Tan Yulin , Wan Li , Zhao Yang , Lou Lingyun , Wang Zhong‐Sheng 
Published: October 2022

AbstractTo inhibit phase separation of CsxFA1−xPbI3 perovskite into optically inactive δ‐CsPbI3 and δ‐FAPbI3 under high humidity and light conditions, herein two polymers, poly[3‐methyl‐6‐(2‐methylspiro[cyclopenta[1,2‐b:5,4‐b′]dithiophene‐4,2′‐[1,3]dithiolan]‐6‐yl)‐9‐octyl‐9H‐carbazole] (TM3) and poly[3‐methyl‐6‐(2‐methylspiro[cyclopenta[1,2‐b:5,4‐b′]dithiophene‐4,2′‐[1,3]dioxolan]‐6‐yl)‐9‐octyl‐9H‐carbazole] (TM4), are designed and synthesized to dope the Cs0.15FA0.85PbI3 perovskite film for perovskite solar cells (PSCs). The results of X‐ray photoelectron spectroscopy and nuclear magnetic resonance confirm the existence of coordination and hydrogen bonds between the polymer and Cs0.15FA0.85PbI3 perovskite. Ion migration in the perovskite film is thus markedly suppressed by the TM doping, as verified by the electrical poling measurement. Benefiting from these interactions, the TM doping is able to inhibit phase separation of Cs0.15FA0.85PbI3 markedly at a relative humidity of 55–65% and under light. Furthermore, the TM doping has other positive effects such as enhancing perovskite crystallinity, improving crystal growth orientation, reducing trap density, increasing hole extraction, and suppressing charge recombination. Consequently, the TM3‐ and TM4‐doped PSCs achieve a power conversion efficiency of 21.96% and 20.01%, respectively, against 17.82% for the undoped PSC. The humidity, environmental, illumination, and thermal stabilities of unencapsulated devices are also improved significantly by the TM3‐ and TM4‐doping, respectively. By comparison, TM3 with the S substitution shows abetter effect than TM4 with the O substation on photovoltaic performance and device stability.
Engineering Interfacial Effects in Electron and Phonon Transport of Sb2Te3/MoS2 Multilayer for Thermoelectric ZT Above 2.0
Authors: Ahmad Mujeeb , Agarwal Khushboo , Munoz Sergio Gonzalez , Ghosh Abhishek , Kodan Nisha , Kolosov Oleg Victor , Mehta Bodh Raj 
Published: October 2022

AbstractEfficient thermoelectric (TE) conversion of waste heat to usable energy is a holy grail promising to address major societal issues related to energy crisis and global heat management. For these to be economical, synthesis of a solid‐state material with a high figure‐of‐merit (ZT) values is the key, with characterization methods quantifying TE and heat transport properties being indispensable for guiding the development of such materials. In the present study, a large enhancement of the TE power factor in Sb2Te3/MoS2 multilayer structures is reported. A new approach is used to simultaneously experimentally determine the values of in‐plane (kxy) and out‐of‐pane (kz) thermal conductivities for multilayer samples with characteristic layer thickness of few nanometres, essential for the quantification of the ZT, the key parameter for the TE material. Combining simultaneous enhancement in the value of in‐plane power factor (to (4.9 ± 0.4) × mWm−1 K−2) and reduction of the in‐plane value of the thermal conductivity (to 0.7 ± 0.1 Wm−1 K−1) for Sb2Te3/MoS2 multilayer sample led to high values of ZT of 2.08 ± 0.37 at room temperature. The present study, therefore, sets the foundation for a new methodology of exploiting the properties of 2D/3D interfaces for the development of novel fully viable thermoelectric materials.
Solution Plasma Processing Single‐Atom Au1 on CeO2 Nanosheet for Low Temperature Photo‐Enhanced Mars–van Krevelen CO Oxidation
Authors: Xing Yanmei , Wang Changhua , Li Dashuai , Wang Rui , Liang Shuang , Li Yuanyuan , Liu Yichun , Zhang Xintong 
Published: October 2022

AbstractCreating oxygen vacancies in metal oxide support holds promise in anchoring and stabilizing single atom metals, activating the lattice oxygen of metal oxide and accelerating Mars–van Krevelen (MvK) catalytic oxidation. However, it is challenging to achieve nearly 100% trapping of single atom metal in solution by oxygen vacancy typed metal oxide, resulting from the difficulty in synchronized formation of oxygen vacancies and capture of the single atom metal. In this study, a solution plasma process (SPP) is developed, enabling ≈99% trapping of single atom Au by using oxygen vacancy typed CeO2 nanosheet in 2 min. Owing to the large number of electrons and free radicals present in the plasma region, the SPP can simultaneously reduce HAuCl4 to single‐atom Au and bring oxygen vacancies as anchoring sites onto CeO2. The catalytic test of CO oxidation assisted by solar light can reach a conversion of 91.7% with a high turnover frequency of 1.3 s−1 at room temperature, far exceeding the requirements for the “150 °C challenge.” A photo‐enhanced MvK pathway is proposed for the superior performance of Au1/CeO2. This study not only explores a novel solution approach to prepare single‐atom metal catalysts, but also provides an effective strategy for efficient low‐temperature catalytic oxidation.
Self‐Passivated Metal Klein Edge of 1T‐Phase Transition Metal Dichalcogenides and the Induced High‐Efficient Hydrogen Evolution Reaction Activity
Authors: Liu Yue , Li Da , Cui Tian 
Published: October 2022

AbstractThe pristine edge of a 2D material generally undergoes an edge self‐passivation into its ground‐state configuration. To date, several self‐passivated edges of 1H‐phase transition metal dichalcogenides (TMDCs) have been reported in theories and experiments. However, no self‐passivated edges of its sister material 1T‐phase TMDCs are found. Here, taking 1T‐VS2 as an example, a self‐passivated V2 dimer‐like metal Klein (DM‐Klein) edge of 1T‐TMDCs is reported. It exhibits high thermodynamic stability and can spontaneously form at V‐rich chemical potential conditions. Unexpected intermetallic d–d orbital interaction of edge metal atoms results in metal dimerization. This edge self‐passivation mode is universal in group IV and V 1T‐TMDCs. Furthermore, strong intermetallic interaction and appropriate edge sulfur saturation make DM‐Klein edges of 1T‐TMDCs show excellent catalytic activity in the hydrogen evolution reaction compared to that of well‐known Pt(111) surface. This study provides opportunities for the further practical application of 1T‐TMDCs in catalysts.
Hierarchically Designed Super‐Elastic Metafabric for Thermal‐Wet Comfortable and Antibacterial Epidermal Electrode
Authors: Dong Jiancheng , Peng Yidong , Nie Xiaolin , Li Le , Zhang Chao , Lai Feili , He Guanjie , Ma Piming , Wei Qufu , Huang Yunpeng , Liu Tianxi 
Published: October 2022

AbstractOn‐skin electronic systems represent a burgeoning technology that develops wearable devices capable of adapting to the dynamic surfaces of the human body. Present film‐based electronics are constrained to single‐layered constructions on impermeable substrates that severely inhibit their wearing comfort and multi‐functionality. Herein, a thermal‐wet comfortable and antibacterial epidermal electrode is hierarchically designed on an ultra‐stretchable metafabric. Via the layer‐by‐layer assembly of trilayered elastomeric fibers with multi‐scale sizes and varied compositions, porosity and wettability asymmetries are established across the nonwoven fabric, rendering it with unidirectional liquid conduction and sweat self‐pumping performance. The successful printing of stretchable liquid‐metal (EGaIn) circuits on ZnO NPs anchored microfibers simultaneously equips the trilayered metafabric with robust antibacterial capability, low‐watt heating ability, and high‐fidelity detectability for surface electromyography signals of various physical activities. Moreover, the incorporation of thermochromic microcapsules in the outmost fibers also enables the fabric Joule heater with visual indicating ability via reversible color‐switching. Thus, this hierarchically engineered epidermal electrode with thermal‐wet comfort and antibacterial ability holds great promise in daily applicable healthcare and sports monitoring electronics.
Enhanced Triboelectric Nanogenerator Performance Based on Mechanical Imprinting PDMS Microstructures
Authors: Zhou Hui , Wang Xiutong , Wang Youqiang , Nan Youbo , Xu Hui , Wu Yan , Niu Jianmin , Duan Jizhou , Huang Yanliang , Hou Baorong 
Published: October 2022

AbstractA vertical contact‐separated mode triboelectric nanogenerator (TENG) is fabricated by imprinting the nylon mesh to obtain the polydimethylsiloxane (PDMS) film with micro‐nano structure, and it is used to provide electric energy for the impressed current cathodic protection. The output of PDMS film obtained by 200 mesh nylon mesh imprinting is significantly improved, with an open circuit potential of 1120 V and a charge transfer of 63 nC, which is about twice that of a smooth PDMS film. It also performs well for cathodic protection, and electrochemical test results show that the open circuit potential of the protected metal in artificial seawater can decrease by 275 mV. Experiments show that the output of TENG can make calculators, flame alarms, and other electronic equipment work normally after being stored by capacitors. In addition, this work has the advantages of having simple operation, low equipment demands, and low cost.
Ultrathin Poly(Ionic Liquid) Nanomembranes for High Performance Mg2+/Li+ Separation
Authors: Ni Yunxia , Peng Huawen , Zhao Qiang 
Published: October 2022

AbstractThe fragility and brittleness of glassy poly(ionic liquid)s (PILs) hinders the processing of ultrathin PILs membranes. This work is reported the interfacial polymerization of PILs, which enables the first preparation of defect‐free PIL nanomembranes for high flux separation of lithium (Li+, 3.8 Å) and magnesium (Mg2+, 4.3 Å) ions mixture. Aqueous solution of an amine‐functionalized PIL is brought in contact with trimesoyl chloride (TMC) hexane solution. The “amine ≈ acyl chloride” condensation reaction occurs at the “water ≈ hexane” interface to form ≈50 nm thin PILNH2‐TMC nanomembranes consisting of water‐stable nanoaggregates (≈20 nm in size). Water permeance of the PIL nanomembrane is 3 times as high as the state‐of‐the‐art polyamide nanofiltration membranes, while its MgCl2 rejection is as high as 95%. Both the structures and separation performance of PIL nanomembranes are stable versus operation time and pressure. This work opens a new avenue to process fragile PILs, such as into functional nanomembranes for ion separation.
A Predictive Oxygen Durability Model to Analyze Oxygen Consumption of Insulin Producing Cells Encapsulated Within a Highly Oxygenated Hydrogel
Authors: Domingo‐Lopez Daniel A. , Levey Ruth E. , Brennan Benjamin , Carroll Oliver , Gale Sarah E. , Millman Jeffrey R. , McDonough Liam , Kelly Helena M. , Ronan William , Duffy Garry P. 
Published: October 2022

AbstractCell transplantation aims to regenerate damaged tissues and cure currently incurable diseases, such as Type 1 diabetes. Post‐transplantation cell survival is highly limited by the lack of suitable support matrix (anoikis) and insufficient oxygen supply (hypoxia), which is aggravated when using macroencapsulation devices. Graft failure can be overcome by encapsulation in extracellular matrix (ECM)‐based hydrogels with high oxygen capacity. Estimation of the oxygen durability in these systems is critical for the design of hydrogel loaded macroencapsulation devices aimed to increase graft survival. In this study, a novel hyaluronic acid/perfluorocarbon biomaterial (Oxygel) is formulated, oxygenated, and characterized. Oxygel exhibits shear thinning and self‐healing properties while it can carry high oxygen payloads and slowly release them for 90 h, exhibiting a 14.5 times smaller oxygen diffusivity than PBS. In parallel, a model able to predict the oxygen durability within Oxygel upon cell encapsulation is developed and experimentally validated in vitro. Correlations between model estimations and experimental results are found, demonstrating the validity of the model to analyze oxygen durability. The application of this mathematical model to oxygenated cell scaffolds (such as Oxygel) holds great promise to improve cell transplantation success.
Birefringence in the Polarized Raman Scattering of Biaxial van der Waals α‐MoO3
Authors: Zhao Yanyu , Gong Youning , Zhu Jiaqi , Li Delong , Mao Hu , Bao Qiaoliang , Zhang Yupeng , Wang Guo Ping 
Published: October 2022

AbstractThe effect of birefringence in anisotropic materials has been a long‐term issue for polarized Raman scattering. In this work, the polarization‐dependent Raman scattering in anisotropically birefringent materials is modeled with birefringence considered in the fundamental polarization selection rule. The birefringence‐induced polarization transformation is treated as a tensor in the calculation of Raman scattering intensity. The validity of this theory is further demonstrated in experiments by taking angle‐resolved polarized Raman measurements on the basal and cross planes of α‐MoO3—a typical biaxial van der Waals crystal with strong in‐plane and out‐of‐plane anisotropy. The anomalous angular dependency of polarized Raman scattering intensity can be well reproduced by the modified theoretical model with fitted real‐valued Raman tensors and birefringence‐related parameters. It can be concluded that this work can provide a valuable reference and guidance for quantitative analyses of anisotropic materials by using polarization‐resolved Raman scattering spectroscopy.