Article
Chemistry, Multidisciplinary
Simon Sengupta, Philipp Schueler, Phil Liebing, Matthias Westerhausen
Summary: Magnesium and calcium are too inert to directly deprotonate amines, so alternative strategies are needed for the synthesis of bulky amides. N-bound trialkylsilyl groups have been used to facilitate metalation reactions. In situ Grignard reagent formation in THF with magnesium or calcium, hydryl halide, and imine allows the synthesis of amides with bulky silyl-free substituents. Ball milling protocols may lead to competing side reactions like aza-pinacol coupling reactions. Calcium is a better choice for in situ Grignard reagent formation and subsequent addition to imines, while heavier alkaline-earth metals strontium and barium are less selective, leading to competitive aza-pinacol coupling reactions. Solid-state molecular structures of [(Et2O)Mg(N(Ph)(CHPh2)(2)] and [(Et2O)(2)Ca(N(Ph)(CHPh2)(2)] have been determined.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Engineering, Biomedical
Yihang Weng, Yujia Jian, Wenlong Huang, Zhuojun Xie, Ying Zhou, Xibo Pei
Summary: Regeneration of bone defects is a major challenge, and scaffold materials have potential in treating bone defects, but current materials do not meet expectations. Alkaline earth metals show osteogenic capabilities and their combined use improves properties. This review discusses the characteristics and applications of alkaline earth metals, particularly magnesium, calcium, strontium, and barium, in osteogenesis. It also highlights the potential cross-talk between pathways and addresses current drawbacks and future directions in scaffold materials.
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH PART B-APPLIED BIOMATERIALS
(2023)
Article
Thermodynamics
Xiangyu Fan, Yang Liu, Mingdeng Wang, Chao Li, Yajie Zheng, Yang Liu, Xiangyun Zhong, Guozhong Xu, Yaru Zhang, Yifei Feng, Bin Bai, Jinfeng Bai
Summary: The influence of alkali metals and alkaline earth metals on coke reactivity and coke microstructure was studied, and high-reactivity metallurgical cokes were produced using the mechanical mixing method. The gasification kinetics of coke samples were further investigated to understand the catalytic mechanism of alkali metals and alkaline earth metals on cokes, providing a basis and guidance for hydrogen-rich blast furnace charge production. The addition of alkali metals or alkaline earth metals significantly increased the chemical reactivity index of cokes. Furthermore, it was observed that the microstructure of cokes changed after the addition, with increased contact area and reduced disorder, leading to increased reactivity.
Review
Chemistry, Inorganic & Nuclear
Sangharaj Diyali, Nilankar Diyali, Bhaskar Biswas
Summary: This study discusses the recent progress in the design and development of catalysts, focusing on the factors influencing overpotential, catalytic rate, and stability, as well as the mechanisms of the hydrogen evolution reaction in acidic and alkaline media. Moreover, it outlines the challenges in future design of robust and active electrocatalysts.
COORDINATION CHEMISTRY REVIEWS
(2024)
Review
Chemistry, Multidisciplinary
Xiaoyang Fu, Chengzhang Wan, Yu Huang, Xiangfeng Duan
Summary: This minireview provides a brief introduction to the fundamental challenges associated with anode alcohol oxidation reaction (AOR) in alkaline direct alcohol fuel cells (ADAFCs), as well as the key performance metrics and evaluation protocols for benchmarking AOR electrocatalysts. Recent advances in noble-metal based AOR electrocatalysts, such as Pt, Pd, and Rh, are summarized with a focus on design criteria for improving specific activity and electrochemical surface area to achieve high mass activity and long term durability. Strategies to enhance Faradaic efficiency and reduce overpotential are also discussed. The article concludes with a brief perspective on future challenges and opportunities.
ADVANCED FUNCTIONAL MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Ailijiang Abudurusuli, Junben Huang, Peng Wang, Zhihua Yang, Shilie Pan, Junjie Li
Summary: Li4MgGe2S7 is an infrared NLO material with a large band gap and strong nonlinear optical effect, promising a high laser damage threshold and suitable SHG response. It provides insights into the design of new DL compounds with outstanding IR NLO performances.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Roman G. Belli, Victoria C. Tafuri, Nicholas A. Garcia, Courtney C. Roberts
Summary: Recently, rare earth elements have been utilized in catalyzing alkyl-alkyl cross coupling and other organic transformations. In this study, we synthesized and characterized a tris(amido) Lu complex, 1-Lu, which is similar to the Sc and Y rare earth complexes known to participate in these reactions. While 1-Lu shares similar solid state structural properties as its Group 3 congeners, EPR spectroscopy showed different behavior. Additionally, 1-Lu broke the trend of reaction rates related to oxidation potential and exhibited faster catalysis in alkyl-alkyl cross-coupling reaction compared to Sc and Y analogs. Moreover, complex 1-Lu was also demonstrated to participate in two-electron redox catalysis.
Article
Chemistry, Physical
Pengfei Zhou, Dong Liu, Zhaorui Wen, Mingpeng Chen, Qingju Liu, Ye Ke, Shengwen Li, Shi Chen, Chi Tat Kwok, Shuangpeng Wang, Yuxin Tang, Hui Pan
Summary: The study demonstrated that a multi-metal phosphide FeCoNiNbxP on Ni foam shows high HER activity. The incorporation of Nb significantly improves the catalytic activity, with FeCoNiNb0.3P exhibiting the best performance requiring a low overpotential for high current density.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Engineering, Chemical
Qin Chen, Yanan Chong, Mumin Rao, Ming Su, Yongcai Qiu
Summary: By introducing different alkaline earth metal salt solutions into alpha-Fe2O3 nanorods grown on carbon cloths through quenching, electrodes doped with different alkaline earth metal ions (M-Fe2O3@CC) can be obtained, among which Sr-Fe2O3@CC shows the best electrochemical capacitance of 77.81 mF cm(-2) at a current of 0.5 mA cm(-2), which is 2.5 times that of alpha-Fe2O3@CC. The results demonstrate that quenching is a feasible new idea for improving the electrochemical performances of nanostructured materials.
Article
Materials Science, Multidisciplinary
Zhiqiang Wu, Longwen Jiang, Quan Dong, Qiang Gao, Jingxuan Cai, Xiaowei Cheng
Summary: Active alumina was synthesized via the gel-sol method and the effect of rare Earth and alkaline Earth metal doping modification on its high-temperature stability was investigated. Different contents of La, Ce, and Ba were analyzed using various characterization techniques. The results showed that suitable single doping of La, Ce, and Ba inhibited the phase transition of alumina and improved its high-temperature stability.
FRONTIERS IN MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Zi-Xin You, Chen Wang, Yao Xiao, Qing-Lin Guan, Jin-Xiao Li, Yong-Heng Xing, Hong-Wei Gao, Li-Xian Sun, Feng-Ying Bai
Summary: Photoresponsive materials, particularly alkaline earth metal coordination networks, show promising properties for applications such as secret inks, ultraviolet detectors, and fluorescence sensors for drug molecules. Further research is needed to enhance and optimize these materials for future improvements.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yaprak Subasi, Elif Sena Tekin, Yurii Prots, Franziska Jach, Mehmet Somer, Semih Afyon, Peter Hoehn
Summary: A transparent, dark orange Ba[Au(N-3)(4)](2)·4 H2O compound was synthesized by reacting nitrite and gold salt in aqueous solution. This compound is highly explosive.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Applied
Jiawei Wu, Haotong Liang, Yuxin Wang, Jianzu Zhang, Qijun Zhang, Juan Lv, Enchen Jiang, Yongzhi Ren, Zhifeng Hu
Summary: Alkali metals and alkaline earth metals (AAEMs) have different effects on catalysis and agglomeration at different times during chemical looping gasification (CLG) in biomass. This study investigated the promotion and agglomeration effects of AAEMs on CLG performance at different times. The results showed that K played a major role in promoting CLG before 20 min and inhibiting CLG at 30 min. Na and Mg had obvious catalytic and promotional effects after excitation. Ca significantly promoted the whole CLG process. Mg slightly slowed down the conversion of Fe2O3 to Fe3O4, while Ca delayed the conversion to FeO, resulting in less adhesion and obvious inhibition of agglomeration. The effect of Mg on reducing agglomeration was weaker than that of Ca, but better than that of K and Na.
FUEL PROCESSING TECHNOLOGY
(2023)
Article
Chemistry, Organic
Wen-Jun Han, Jian-Wu Zhang, Chao-Xian Yan, Jia-Wei Wang, Pan-Pan Zhou, Bing Han
Summary: A radical [1,4]-oxygen-atom transfer has been achieved through the reaction of linear alkyne-tethered ketoximes and ethynylbenziodoxolones (EBX) under sequential catalytic conditions. Mechanistic studies reveal a cascade process involving O atom radical cyclization, alkynylation, N-O bond photocleavage, and subsequent N,O-diradical rearrangement. By varying the catalytic sequences, a series of structurally important 3H-pyrrol-3-ones and chlorinated furo[3,2-b]pyrroles were synthesized, accompanied by an O atom shift, using Cu/Ir photosensitization and Cu/Ir photosensitization/AlCl3 catalysis, respectively.
Article
Nanoscience & Nanotechnology
Javaria Naeem, Rehana Bano, Khurshid Ayub, Tariq Mahmood, Sobia Tabassum, Anam Arooj, Mazhar Amjad Gilani
Summary: This study explores the geometric, electronic, and nonlinear optical properties of alkali and alkaline earth metals doped cubane complexes. Doping with these metals enhances the NLO properties by reducing the excitation energy of cubane. The results demonstrate potential applications for these designed complexes in high-performance NLO materials.
JOURNAL OF SCIENCE-ADVANCED MATERIALS AND DEVICES
(2022)
Article
Chemistry, Inorganic & Nuclear
Peter M. Chapple, Thierry Roisnel, Marie Cordier, Jean-Francois Carpentier, Yann Sarazin
Summary: This study reports the synthesis and characterization of two molecular barium-hydroborate complexes obtained through reactions with different precursor materials. The study also reveals the formation of a soluble barium cation and provides insights into its structure. Additionally, the structure of a seven-coordinated cationic complex is determined.
Article
Chemistry, Multidisciplinary
Hui Li, Jerome Ollivier, Sophie M. Guillaume, Jean-Francois Carpentier
Summary: This study reports the first chemical synthesis of poly(3-thiobutyrolactone) (P3TB) through ring-opening polymerization. The reactions proceed rapidly in the presence of various metal-based catalysts, and high selectivity can be achieved by manipulating reaction conditions and catalyst systems. The topology and stereochemistry of the resulting polymer have been characterized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Yutong Han, Zhaohe Liu, Zhongfu Zhao, Bo Liu, Dongmei Cui
Summary: A series of constrained-geometry-configuration rare-earth metal complexes have been synthesized and shown high activity in polymerization reactions. The structures and properties of these complexes provide a basis for further exploration and application of rare-earth metal complexes.
Article
Materials Science, Multidisciplinary
Quentin Beuguel, Evgueni Kirillov, Jean-Francois Carpentier, Sophie M. Guillaume
Summary: By adding SEBS thermoplastic during the preparation process, the ductility and toughness of PDCPD material can be improved, along with an increase in its glass transition temperature. This method offers a simplified approach to adjusting the properties of the material.
ACS APPLIED POLYMER MATERIALS
(2022)
Review
Chemistry, Multidisciplinary
Hui Li, Sophie M. Guillaume, Jean-Francois Carpentier
Summary: This review introduces the synthesis methods and applications of polythioesters (PTEs) in polymer research. With the introduction of sulfur atoms, PTEs have different thermal, optical, and mechanical properties compared to conventional plastics, making them a focus of research. The emphasis is on the synthesis of different cyclic thioesters and thiolactones, as well as the effects of catalysts and initiating systems on the quality, molecular weight, and microstructure of the products.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Polymer Science
Rama. M. M. Shakaroun, Ali Dhaini, Romain Ligny, Ali Alaaeddine, Sophie. M. M. Guillaume, Jean-Francois Carpentier
Summary: Stereoselective ring-opening polymerization (ROP) of cyclic esters is an important strategy to produce stereoregular polyesters, especially in the biomedical and packaging fields. However, the synthesis of synthetic stereo-enriched polyhydroxyalkanoates (PHAs) from racemic ss-lactones by ROP is still challenging. In this study, high molar mass and narrowly dispersed PHAs with syndiotactic enrichment were successfully synthesized using diverse achiral diamino-bis(phenolate) yttrium complexes as catalysts. The steric hindrance of the monomer side-functionality was found to have a significant impact on the ROP kinetics, stereoselectivity, and thermal properties of the resulting PHAs. The results showed that the newly prepared rac-BPLCH2OiPr, rac-BPLCH2OtBu, and rac-BPLCH2OTBDMS monomers all led to syndioenriched polyesters, regardless of the catalyst used.
Article
Chemistry, Physical
Kosuke Higashida, Valentin Smail, Haruki Nagae, Jean-Francois Carpentier, Kazushi Mashima
Summary: We successfully achieved nickel(0)-catalyzed asymmetric allylic alkylation (AAA) of beta-dicarbonyl compounds under ambient conditions by activating unstrained C-C bonds of 2-allylated 2-methylcyclohexane-1,3-dione derivatives. The reaction produced quaternary chiral compounds with high yield and enantioselectivity. The mechanism of the AAA reaction with the Ni(0)-(S)-tol-MeO-BIPHEP catalyst system was elucidated through control experiments and DFT calculations.
Article
Chemistry, Organic
Mohamed Hasyeoui, Peter M. Chapple, Frederic Lassagne, Thierry Roisnel, Marie Cordier, Ali Samarat, Yann Sarazin, Florence Mongin
Summary: The functionalization of methylated azines and diazines has attracted the interest of chemists due to the structural diversity it provides. Hindered lithium dialkylamides have shown chemoselectivity in deprotonating these substrates, while lithium diethylamide has been underutilized for this purpose. This article aims to review the reagents used for deprotonating methylpyridines, -quinolines, and -quinoxalines, and investigates the results obtained by functionalizing various substrates with lithium diethylamide (picolines, 2,4-lutidine, methylquinolines, and 2-methylquinoxaline). The use of an in-situ trap, namely a zinc chloride chelate, in these reactions is also discussed.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Shuqi Dong, Xiaozheng Duan, Tianhao Nan, Chengjiang Lin, Bo Liu, Dongmei Cui
Summary: In this study, a new method for preparing cyclic olefin copolymers based on dicyclopentadiene (DCPD) is reported, and the optimization of their properties by introducing styrene monomers is introduced. The results show that the incorporation of p-fluorostyrene can significantly improve the strength and breakdown voltage of the copolymers while suppressing cross-linking reactions.
Article
Chemistry, Physical
Lars N. Jende, Thierry Roisnel, Virginie Cirriez, Alexandre Welle, Evgueni Kirillov, Jean-Francois Carpentier
Summary: This study presents a synthetic strategy for asymmetric dinuclear bis(ansa-metallocene) pre-catalysts. The strategy involves a Pd-catalyzed Suzuki cross-coupling reaction to generate an asymmetric bifluorene platform. The performance of the resulting pre-catalyst in ethylene, propylene, and ethylene/1-hexene (co-)polymerization has been evaluated and compared to a mononuclear reference pre-catalyst. The resulting (co-)polymers showed slight differences in terms of molecular weights, tacticity, and comonomer incorporation.
Article
Chemistry, Inorganic & Nuclear
Dimitra Theodosopoulou, Miguel Alonso De La Pena, Sary Abou Derhamine, Iskander Douair, Thierry Roisnel, Marie Cordier, Lorenzo Piola, Alvaro Fernandez, Alexandre Welle, Laurent Maron, Jean-Francois Carpentier, Evgueni Kirillov
Summary: A series of new Me2Si-bridged cyclopentadiene/indene proligands were synthesized and characterized. The corresponding C-1-symmetric group 4 ansa-metallocene complexes were also prepared and showed high propylene polymerization activities. DFT calculations allowed rationalizing a polymerization reaction mechanism.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sakshi Mohan, Yahya Al Ayi, Savarithai Jenani Louis Anandaraj, Marie Cordier, Thierry Roisnel, Jean-Francois Carpentier, Yann Sarazin
Summary: Four fluoroarylsilylamides lithium complexes were synthesized and characterized by multinuclear NMR spectroscopy. The role of Li-F and C-F non-covalent interactions in the formation of the molecular structures was investigated. Li-F interatomic distances and |(1) J (C,F)| coupling constants were found to be useful qualitative tools for evaluating the presence and strength of Li center dot center dot center dot F contacts.
MAIN GROUP METAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Kosuke Higashida, Valentin Smail, Haruki Nagae, Jean-Francois Carpentier, Kazushi Mashima
Summary: We achieved a nickel(0)-catalyzed asymmetric allylic alkylation reaction of beta-dicarbonyl compounds under ambient conditions, resulting in high yields of quaternary chiral compounds with high enantioselectivity.
Article
Polymer Science
Yi Wu, Bo Liu, Dongmei Cui
Summary: The ultrafast synthesis of core cross-linked star poly(p-methylstyrene) (s-PMS) with syndiotactic arms was achieved through a coupling reaction between the active species of metal-poly(p-methylstyrene) and the cross-linker of divinylbenzene (DVB). By controlling the molecular weight, DVB loading, and coupling time, narrowly distributed s-PMS with high yield was obtained. Compared to linear PMS, s-PMS with the same molecular weight has lower solution viscosity and smaller hydrodynamic radius.