bluuebunny/crossref_metadata_2025_split huggingface dataset:
[LiCl2]− Superhalide: A New Charge Carrier for Graphite Cathode of Dual‐Ion Batteries
Authors: Kim Keun‐il , Tang Longteng , Mirabedini Pegah , Yokoi Amika , Muratli Jesse M. , Guo Qiubo , Lerner Michael M. , Gotoh Kazuma , Greaney Peter Alex , Fang Chong , Ji Xiulei 
Published: March 2022

AbstractNew acceptor‐type graphite intercalation compounds (GICs) offer candidates of cathode materials for dual‐ion batteries (DIBs), where superhalides represent the emerging anion charge carriers for such batteries. Here, the reversible insertion of [LiCl2]− into graphite from an aqueous deep eutectic solvent electrolyte of 20 m LiCl + 20 m choline chloride is reported. [LiCl2]− is the primary anion species in this electrolyte as revealed by the femtosecond stimulated Raman spectroscopy results, particularly through the rarely observed H–O–H bending mode. The insertion of Li–Cl anionic species is suggested by 7Li magic angle spinning nuclear magnetic resonance results that describe a unique chemical environment of Li+ ions with electron donors around. 2H nuclear magnetic resonance results suggest that water molecules are co‐inserted into graphite. Density functional theory calculations reveal that the anionic insertion of hydrated [LiCl2]− takes place at a lower potential, being more favorable. X‐ray diffraction and the Raman results show that the insertion of [LiCl2]− creates turbostratic structure in graphite instead of forming long‐range ordered GICs. The storage of [LiCl2]− in graphite as a cathode for DIBs offers a capacity of 114 mAh g−1 that is stable over 440 cycles.
The Fluorine‐Rich Electrolyte as an Interface Modifier to Stabilize Lithium Metal Battery at Ultra‐Low Temperature
Authors: Zhang Da , Zhu DaWei , Guo WenYao , Deng ChenWei , Xu QunJie , Li HeXing , Min YuLin 
Published: March 2022

AbstractLithium (Li) metal batteries (LMBs) are still limited by lithium dendrite growth and solvated structure at low temperatures. A stable solid electrolyte interface (SEI) and solvent sheath structure are the future directions of liquid metal battery development. However, most artificial SEIs and electrolytes cannot meet the original objective of high conductivity and low nucleation potential multifunctional design. To address this challenge, an electrolyte with excellent high current density and low‐temperature performance is reported here. In this electrolyte environment, the thickness and microstructure of the “Chain Link Ships” SEI are formed. Moreover, the additives improve the desolvation ability of Li+ in the ester electrolytes. Under the harsh environment (−30 °C), the average coulombic efficiency (CE) of the Li||copper (Cu) battery reaches 98% after 200 cycles. Even at −40 °C, the Li||LiFePO4 (LFP) battery shows 90% capacity retention after 100 cycles at the cathode‐limited areal capacity (5 mAh cm−2). Furthermore, at 30 °C, the Li||LFP battery can cycle stably for 1200 cycles at 5 C, and the capacity retention reaches 93.5%. This addition strategy provides insights into the commercial application of new solvated structure electrolytes and a new approach for commercial low‐temperature LMBs.
Comment on “Wide‐Range‐Tunable p‐Type Conductivity of Transparent CuI1‐xBrx Alloy”
Authors: Wang Zhi‐Hao , Wei Su‐Huai , Zhang Xie 
Published: March 2022

AbstractIn a recent article, Yamada et al. proposed to utilize CuI‐CuBr alloys (CuI1‐xBrx) as a hole‐density‐tunable p‐type transparent semiconductor. Employing first‐principles calculations, they attributed the acceptor state to Cu vacancies (VCu). Despite the interesting experimental demonstration, it is found that the first‐principles results in the paper are unphysical and misleading due to the adoption of an incorrect level of theory and the lack of a rigorous methodology for computing defect formation energies. Below are the specific concerns.
Hierarchical Therapeutic Ion‐Based Microspheres with Precise Ratio‐Controlled Delivery as Microscaffolds for In Situ Vascularized Bone Regeneration
Authors: Wan Zhuo , Yuan Zuoying , Li Yechen , Zhang Yanling , Wang Yue , Yu Yingjie , Mao Jianping , Cai Qing , Yang Xiaoping 
Published: March 2022

AbstractTherapeutic ions, such as Si and Mg, play vital roles in regulating metabolism and promoting tissue repair, hence providing an efficient strategy in tissue engineering. The regenerative outcome is strongly dependent on the targeted delivery and controlled release of therapeutic ions. Nevertheless, it remains challenging to deliver multiple ions at controlled manners and ratios. Herein, hierarchical therapeutic ion‐based microspheres are fabricated. The coordinated release of Mg and Si ions at pre‐set ratios is achieved, based on which, Mg favors osteogenesis by inducing highly efficient cell recruitment and angiogenesis, and Si promotes massive collagen secretion and biomineralization to accelerate the bone maturation process. These therapeutic ion‐based microspheres (namely PNM2) can steadily release Mg and Si ions at an optimized ratio of 2:1, which shows the most significant synergistic effect on angiogenesis and osteogenesis. Furthermore, in a rat calvarial defects model, the volume and maturity of the vascularized neo‐bone tissue regenerated with PNM2 microspheres are comparable with or even surpassing those defects regenerated with growth factors and/or cell‐laden scaffolds. Overall, this platform provides a controllable strategy for the coordinated delivery of Mg/Si ions, opening a new avenue for developing therapeutic ion‐based microscaffold for tissue engineering.
Toward the Rational Design of Mid‐Infrared Nonlinear Optical Materials with Targeted Properties via a Multi‐Level Data‐Driven Approach
Authors: Cai Wenbing , Abudurusuli Ailijiang , Xie Congwei , Tikhonov Evgenii , Li Junjie , Pan Shilie , Yang Zhihua 
Published: March 2022

AbstractDesign and exploratory synthesis of new mid‐infrared (mid‐IR) nonlinear optical (NLO) materials are urgently needed for modern laser science and technology because the widely used IR NLO crystals still suffer from their inextricable drawbacks. Herein, a multi‐level data‐driven approach to realize fast and efficient structure prediction for the exploration of promising mid‐IR NLO materials is proposed. Techniques based on machine learning, crystal structure prediction, high‐throughput calculation and screening, database building, and experimental verification are tightly combined for creating pathways from chemical compositions, crystal structures to rational synthesis. Through this data‐driven approach, not only are all known structures successfully predicted but also five thermodynamically stable and 50 metastable new selenides in AIBIIISe2 systems (AI = Li, Na, K, Rb, and Cs; BIII = Al and Ga) are found, among which eight outstanding compounds with wide bandgaps (> 2.70 eV) and large SHG responses (>10 pm V−1) are suggested. Moreover, the predicted compounds I2d‐LiGaSe2 and I4/mcm‐KAlSe2 are successfully obtained experimentally. In particular, LiGaSe2 exhibits a robust SHG response (≈2 × AGS) and long IR absorption edge that can cover two atmospheric windows (3–5, 8–12 µm). Simultaneously, this new research paradigm is also applicative for discovering new materials in other fields.
Dendrites‐Free Lithium Metal Anode Enabled by Synergistic Surface Structural Engineering
Authors: Di Jie , Yang Jin‐Lin , Tian Han , Ren Pengfei , Deng Yirui , Tang Wenhao , Yan Wenqi , Liu Ruiping , Ma Jianmin 
Published: March 2022

AbstractLithium (Li) metal with high specific capacity and low redox potential is widely considered as a potential anode for lithium‐ion batteries (LIBs) with high energy density. However, the catastrophic dendrites growth, “dead Li” formation, and surface passivation hinder its practical application. Herein, a selective artificial solid electrolyte interphase (SEI) layer (Li2Sx, x = 1, 2) protection strategy is adopted, where the tip sites passivation and the uniform Li nucleation in grooves are well combined, which enables reversible Li stripping/plating with high storage capacity and robust electrode framework. The grooves derived patterned array Li with selective Li2Sx artificial SEI (LS@A‐Li) exhibit over 1800 h cycling life at 1.0 mA cm–2/1.0 mAh cm–2 and over 600 h even under 5.0 mA cm–2/10.0 mAh cm–2. The application feasibility of such LS@A‐Li is also confirmed by coupling with commercial LiFePO4 and LiNi0.5Co0.2Mn0.3O2 (NCM523) in the full batteries. This work paves way for the large‐scale application of Li metal anode in lithium‐metal batteries with a facile and efficient fabrication process.
DNA‐Based Nanoarchitectures as Eminent Vehicles for Smart Drug Delivery Systems
Authors: Komiyama Makoto , Shigi Narumi , Ariga Katsuhiko 
Published: March 2022

AbstractIn order to cure diseases efficiently with minimal side effects in sophisticated medicine, eminent drugs must be selectively delivered to diseased parts and allow to work only there. However, most of drug delivery systems (DDSs) previously proposed are not yet sufficiently selective and effective. This review covers recent developments of DDS in which DNA nanoarchitectures are employed as drug carriers. From short DNA fragments, a variety of complicated nanomedicines are fabricated to show unprecedentedly smart DDS functions. Encapsulated drugs are released mostly through controlled disassembly of DNA nanoarchitectures. Recent attention has been focusing to the use of appropriate stimuli to regulate each process in the DDS (delivery of drug, its release, and others) for further improved therapy. As intracellular stimuli for the regulation, various endogenous compounds (e.g., mRNA and enzymes), which are specifically abundant in target cells, are employed. Alternatively, physical perturbation (e.g., light irradiation) is provided from outside of tissues to control DDS. By combining multiple strategies in terms of new concepts, enormously smart DDSs are being achieved. Further progresses of these approaches in the future are guaranteed by complete freedom of molecular design in DNA nanoarchitectonics.
Nontrivial Doping Evolution of Electronic Properties in Ising‐Superconducting Alloys
Authors: Wan Wen , Wickramaratne Darshana , Dreher Paul , Harsh Rishav , Mazin Igor I. , Ugeda Miguel M. 
Published: March 2022

AbstractTransition metal dichalcogenides offer unprecedented versatility to engineer 2D materials with tailored properties to explore novel structural and electronic phase transitions. In this work, the atomic‐scale evolution of the electronic ground state of a monolayer of Nb1−δMoδSe2 across the entire alloy composition range (0 < δ < 1) is investigated using low‐temperature (300 mK) scanning tunneling microscopy and spectroscopy (STM/STS). In particular, the atomic and electronic structure of this 2D alloy throughout the metal to semiconductor transition (monolayer NbSe2 to MoSe2) is studied. The measurements enable extraction of the effective doping of Mo atoms, the bandgap evolution and the band shifts, which are monotonic with δ. Furthermore, it is demonstrated that collective electronic phases (charge density wave and superconductivity) are remarkably robust against disorder and further shown that the superconducting TC changes non‐monotonically with doping. This contrasting behavior in the normal and superconducting state is explained using first‐principles calculations. Mo doping is shown to decrease the density of states at the Fermi level and the magnitude of pair‐breaking spin fluctuations as a function of Mo content. These results paint a detailed picture of the electronic structure evolution in 2D TMD alloys, which is of utmost relevance for future 2D materials design.
Metallaphotoredox‐Enabled Intermolecular Carbobromination of Alkynes with Alkenyl Bromides
Authors: Yu Wei , Jiao Xiaorui , Fan Yanmin , Zhu Shengqing , Chu Lingling 
Published: March 2022

AbstractA regioselective intermolecular carbohalogenation of alkynes with alkenyl bromides enabled by dual photoredox and nickel catalysis is described. This dual protocol enables an atom‐economic access to a wide array of brominated 1,3‐dienes from simple starting materials. Broad substrate scope and high regioselectivity are observed. The synthetic utility has been demonstrated and preliminary mechanistic studies have been performed to elucidate the reaction pathway.magnified image
Prevention of Tumor Growth and Dissemination by In Situ Vaccination with Mitochondria‐Targeted Atovaquone
Authors: Huang Mofei , Xiong Donghai , Pan Jing , Zhang Qi , Wang Yian , Myers Charles R. , Johnson Bryon D. , Hardy Micael , Kalyanaraman Balaraman , You Ming 
Published: March 2022

AbstractAtovaquone, an FDA‐approved drug for malaria, is known to inhibit mitochondrial electron transport. A recently synthesized mitochondria‐targeted atovaquone increased mitochondrial accumulation and antitumor activity in vitro. Using an in situ vaccination approach, local injection of mitochondria‐targeted atovaquone into primary tumors triggered potent T cell immune responses locally and in distant tumor sites. Mitochondria‐targeted atovaquone treatment led to significant reductions of both granulocytic myeloid‐derived suppressor cells and regulatory T cells in the tumor microenvironment. Mitochondria‐targeted atovaquone treatment blocks the expression of genes involved in oxidative phosphorylation and glycolysis in granulocytic‐myeloid‐derived suppressor cells and regulatory T cells, which may lead to death of granulocytic‐myeloid‐derived suppressor cells and regulatory T cells. Mitochondria‐targeted atovaquone inhibits expression of genes for mitochondrial complex components, oxidative phosphorylation, and glycolysis in both granulocytic‐myeloid‐derived suppressor cells and regulatory T cells. The resulting decreases in intratumoral granulocytic‐myeloid‐derived suppressor cells and regulatory T cells could facilitate the observed increase in tumor‐infiltrating CD4+ T cells. Mitochondria‐targeted atovaquone also improves the anti‐tumor activity of PD‐1 blockade immunotherapy. The results implicate granulocytic‐myeloid‐derived suppressor cells and regulatory T cells as novel targets of mitochondria‐targeted atovaquone that facilitate its antitumor efficacy.
Observation of Anomalously Large Magnetoelectric Coupling in the Hexagonal Z‐Type Ferrite Films
Authors: Shin Kwang Woo , Soroka Miroslav , Shahee Aga , Kim Kee Hoon , Buršík Josef , Kužel Radomír , Vronka Marek , Aguirre Myriam Haydee 
Published: March 2022

AbstractAlthough the bulk hexaferrites are known to exhibit strong magnetoelectric (ME) effects near room temperature, the same effects are not realized in a thin film form. Herein, the growth of nearly epitaxial Co2Z‐type hexaferrite Ba0.3Sr2.7Co2Fe24O41 (BSCFO) thin films on a SrTiO3 (111) substrate by a chemical solution deposition method is reported. The reciprocal space mapping on the annealed BSCFO films reveals broadening along the qx directions in the (0014) and (0018) peaks, indicating that the oxygen planes belonging to the off‐centered octahedra have randomly distributed out‐of‐plane tilt to indicate significant disorder in the crystallographic orientation. Quantitative investigations reveal that both ME susceptibility and modulated electric polarization (ΔP) by magnetic field up to 370 K in the BSCFO films are always larger than those of the Co2Z‐type single crystal by ≈2–15 times and further increase upon having enhanced qx broadening in the (0014) and (0018) peaks. As the off‐centered octahedral sites can be a primary source of ΔP as predicted by the p–d hybridization mechanism, these results indicate that effective off‐centering could be further enhanced by the orientational disorder. This study identifies the potential of applying the ME hexaferrite films for multifunctional devices.
Microwave Flexible Electronics Directly Transformed from Foundry‐Produced, Multilayered Monolithic Integrated Circuits
Authors: Qin Guoxuan , Jung Yei Hwan , Zhang Huilong , Jiang Ningyue , Ma Pingxi , Stetson Scott , Racanelli Marco , Ma Zhenqiang 
Published: March 2022

AbstractMonolithic microwave integrated circuits hold a dominant position in telecom applications, especially in mobile devices with capabilities for wireless connectivity, due to high and repeatable performance, compact form factor, and low cost. With flexible electronic technologies forming the foundation for a rapidly growing wearable and implantable device segment, the need for flexible microwave electronics with levels of performance that match those of rigid counterparts has increased to unprecedented levels. Here, the fabrication processes for transforming a rigid form of foundry‐produced, multilayered monolithic microwave integrated circuit into a flexible format for amplification of radio frequency signals in the gigahertz level are described. The strategy involves a complete replacement of all rigid materials in the integrated circuit that do not provide any active electronic functionality with a soft, silicone elastomer to yield an overall structure that is mechanically compliant. Experimental studies indicate that the transformation process leads to a flexible silicon‐germanium‐based heterojunction bipolar transistor with a maximum oscillation frequency of 49 GHz and a 24 GHz amplifier with a small‐signal gain of 13.2 dB. This approach has potential uses across a diverse set of microwave devices and circuits, in a manner that could enable wireless connectivity using entirely flexible electronics.
Cantù syndrome: Report of a patient with a novel variant in KCNJ8 and revision of literature
Authors: Apuril Velgara Erika Solansh , Mariani Milena , Torella Annalaura , Musacchia Francesco ,   Telethon Undiagnosed Diseases Program (TUDP) consortium, Nigro Vincenzo , Selicorni Angelo 
Published: March 2022

AbstractCantù syndrome (CS) is a rare multisystemic disorder, characterized by congenital hypertrichosis, macrocephaly, facial dysmorphisms, cardiomegaly, vascular, and skeletal anomalies. From the cognitive point of view, most of the patients show a mild speech delay and a few of them present intellectual disability and learning difficulties. To date, most CS‐reported cases are caused by heterozygous ABCC9 gene mutations. Only three patients with CS and heterozygous KCNJ8 gene variants have been reported. The authors here present the fourth case of CS with a variant in KCNJ8 in a 6‐month‐old baby. Diagnosis was reached through Trio‐Whole Exome analysis that revealed a de novo missense variant in KCNJ8.
Challenges, Prospects, and Emerging Applications of Inkjet‐Printed Electronics: A Chemist's Point of View
Authors: Lemarchand Justin , Bridonneau Nathalie , Battaglini Nicolas , Carn Florent , Mattana Giorgio , Piro Benoit , Zrig Samia , Noël Vincent 
Published: March 2022

AbstractDriven by the development of new functional inks, inkjet‐printed electronics has achieved several milestones upon moving from the integration of simple electronic elements (e.g., temperature and pressure sensors, RFID antennas, etc.) to high‐tech applications (e.g. in optoelectronics, energy storage and harvesting, medical diagnosis). Currently, inkjet printing techniques are limited by spatial resolution higher than several micrometers, which sets a redhibitorythreshold for miniaturization and for many applications that require the controlled organization of constituents at the nanometer scale. In this Review, we present the physico‐chemical concepts and the equipment constraints underpinning the resolution limit of inkjet printing and describe the contributions from molecular, supramolecular, and nanomaterials‐based approaches for their circumvention. Based on these considerations, we propose future trajectories for improving inkjet‐printing resolution that will be driven and supported by breakthroughs coming from chemistry.
Demonstrating and Unraveling a Controlled Nanometer‐Scale Expansion of the Vacancy Defects in Graphene by CO2
Authors: Rezaei Mojtaba , Villalobos Luis Francisco , Hsu Kuang‐Jung , Agrawal Kumar Varoon 
Published: March 2022

AbstractA controlled manipulation of graphene edges and vacancies is desired for molecular separation, sensing and electronics applications. Unfortunately, available etching methods always lead to vacancy nucleation making it challenging to control etching. Herein, we report CO2‐led controlled etching down to 2–3 Å per minute while completely avoiding vacancy nucleation. This makes CO2 a unique etchant for decoupling pore nucleation and expansion. We show that CO2 expands the steric‐hindrance‐free edges with an activation energy of 2.71 eV, corresponding to the energy barrier for the dissociative chemisorption of CO2. We demonstrate the presence of an additional configurational energy barrier for nanometer‐sized vacancies resulting in a significantly slower rate of expansion. Finally, CO2 etching is applied to map the location of the intrinsic vacancies in the polycrystalline graphene film where we show that the intrinsic vacancy defects manifest mainly as grain boundary defects where intragrain defects from oxidative etching constitute a minor population.
Temperature‐Reliable Low‐Dimensional Perovskites Passivated Black‐Phase CsPbI3 toward Stable and Efficient Photovoltaics
Authors: Tan Shan , Yu Bingcheng , Cui Yuqi , Meng Fanqi , Huang Chunjie , Li Yiming , Chen Zijing , Wu Huijue , Shi Jiangjian , Luo Yanhong , Li Dongmei , Meng Qingbo 
Published: March 2022

AbstractLow‐dimensional (LD) perovskites can effectively passivate and stabilize 3D perovskites for high‐performance perovskite solar cells (PSCs). Regards CsPbI3‐based PSCs, the influence of high‐temperature annealing on the LD perovskite passivation effect has to be taken into account due to fact the black‐phase CsPbI3 crystallization requires high‐temperature treatment, however, which has been rarely concerned so far. Here, the thermal stability of LD perovskites based on three hydrophobic organic ammonium salts and their passivation effect toward CsPbI3 and the whole device performance, have been investigated. It is found that, phenyltrimethylammonium iodide (PTAI) and its corresponding LD perovskites exhibit excellent thermal stability. Further investigation reveals that PTAI‐based LD perovskites are mainly distributed at grain boundaries, which not only enhances the phase stability of CsPbI3 but also effectively suppresses non‐radiative recombination. As a consequence, the champion PSC device based on CsPbI3 exhibits a record efficiency of 21.0 % with high stability.
Identifying Performance Descriptors in CO2 Hydrogenation over Iron‐Based Catalysts Promoted with Alkali Metals
Authors: Yang Qingxin , Kondratenko Vita A. , Petrov Sergey A. , Doronkin Dmitry E. , Saraçi Erisa , Lund Henrik , Arinchtein Aleks , Kraehnert Ralph , Skrypnik Andrey S. , Matvienko Alexander A. , Kondratenko Evgenii V. 
Published: March 2022

AbstractAlkali metal promoters have been widely employed for preparation of heterogeneous catalysts used in many industrially important reactions. However, the fundamentals of their effects are usually difficult to access. Herein, we unravel mechanistic and kinetic aspects of the role of alkali metals in CO2 hydrogenation over Fe‐based catalysts through state‐of‐the‐art characterization techniques, spatially resolved steady‐state and transient kinetic analyses. The promoters affect electronic properties of iron in iron carbides. These carbide characteristics determine catalyst ability to activate H2, CO and CO2. The Allen scale electronegativity of alkali metal promoter was successfully correlated with the rates of CO2 hydrogenation to higher hydrocarbons and CH4 as well as with the rate constants of individual steps of CO or CO2 activation. The derived knowledge can be valuable for designing and preparing catalysts applied in other reactions where such promoters are also used.