bluuebunny/crossref_metadata_2025 huggingface dataset:
Efficient Reversible Conversion between MoS2 and Mo/Na2S Enabled by Graphene‐Supported Single Atom Catalysts
Authors: Chen Biao , Wang Tianshuai , Zhao Shiyong , Tan Junyang , Zhao Naiqin , Jiang San Ping , Zhang Qianfan , Zhou Guangmin , Cheng Hui‐Ming
Published: February 2021

Sodium‐ion batteries (SIBs) based on conversion‐type metal sulfide (MS) anodes have attracted extraordinary attention due to relatively high capacity and intrinsic safety. The highly reversible conversion of M/Na2S to pristine MS in charge plays a vital role with regard to the electrochemical performance. Here, taking conventional MoS2 as an example, guided by theoretical simulations, a catalyst of iron single atoms on nitrogen‐doped graphene (SAFe@NG) is selected and first used as a substrate to facilitate the reaction kinetics of MoS2 in the discharging process. In the following charging process, using a combination of spectroscopy and microscopy, it is demonstrated that the SAFe@NG catalyst enables an efficient reversible conversion reaction of Mo/Na2S→NaMoS2→MoS2. Moreover, theoretical simulations reveal that the reversible conversion mechanism shows favorable formation energy barrier and reaction kinetics, in which SAFe@NG with the Fe–N4 coordination center facilitates the uniform dispersion of Na2S/Mo and the decomposition of Na2S and NaMoS2. Therefore, efficient reversible conversion reaction MoS2↔NaMoS2↔Mo/Na2S is enabled by the SAFe@NG catalyst. This work contributes new avenues for designing conversion‐type materials with an efficient reversible mechanism.
Toward Practical High‐Areal‐Capacity Aqueous Zinc‐Metal Batteries: Quantifying Hydrogen Evolution and a Solid‐Ion Conductor for Stable Zinc Anodes
Authors: Ma Longtao , Li Qing , Ying Yiran , Ma Feixiang , Chen Shengmei , Li Yangyang , Huang Haitao , Zhi Chunyi
Published: February 2021

The hydrogen evolution in Zn metal battery is accurately quantified by in situ battery–gas chromatography–mass analysis. The hydrogen fluxes reach 3.76 mmol h−1 cm−2 in a Zn//Zn symmetric cell in each segment, and 7.70 mmol h−1 cm−2 in a Zn//MnO2 full cell. Then, a highly electronically insulating (0.11 mS cm−1) but highly Zn2+ ion conductive (80.2 mS cm−1) ZnF2 solid ion conductor with high Zn2+ transfer number (0.65) is constructed to isolate Zn metal from liquid electrolyte, which not only prohibits over 99.2% parasitic hydrogen evolution but also guides uniform Zn electrodeposition. Precisely quantitated, the Zn@ZnF2//Zn@ZnF2 cell only produces 0.02 mmol h−1 cm−2 of hydrogen (0.53% of the Zn//Zn cell). Encouragingly, a high‐areal‐capacity Zn@ZnF2//MnO2 (≈3.2 mAh cm−2) full cell only produces maximum hydrogen flux of 0.06 mmol h−1 cm−2 (0.78% of the Zn//Zn cell) at the fully charging state. Meanwhile, Zn@ZnF2//Zn@ZnF2 symmetric cell exhibits excellent stability under ultrahigh current density and areal capacity (10 mA cm−2, 10 mAh cm−2) over 590 h (285 cycles), which far outperforms all reported Zn metal anodes in aqueous systems. In light of the superior Zn@ZnF2 anode, the high‐areal‐capacity aqueous Zn@ZnF2//MnO2 batteries (≈3.2 mAh cm−2) shows remarkable cycling stability over 1000 cycles with 93.63% capacity retained at ≈100% Coulombic efficiency.
Capturing Mobile Lithium Ions in a Molecular Hole Transporter Enhances the Thermal Stability of Perovskite Solar Cells
Authors: Kim Seul‐Gi , Le Thi Huong , de Monfreid Thybault , Goubard Fabrice , Bui Thanh‐Tuân , Park Nam‐Gyu
Published: February 2021

A thermally stable perovskite solar cell (PSC) based on a new molecular hole transporter (MHT) of 1,3‐bis(5‐(4‐(bis(4‐methoxyphenyl) amino)phenyl)thieno[3,2‐b]thiophen‐2‐yl)‐5‐octyl‐4H‐thieno[3,4‐c]pyrrole‐4,6(5H)‐dione (coded HL38) is reported. Hole mobility of 1.36 × 10−3 cm2 V−1 s−1 and glass transition temperature of 92.2 °C are determined for the HL38 doped with lithium bis(trifluoromethanesulfonyl)imide and 4‐tert‐butylpyridine as additives. Interface engineering with 2‐(2‐aminoethyl)thiophene hydroiodide (2‐TEAI) between the perovskite and the HL38 improves the power conversion efficiency (PCE) from 19.60% (untreated) to 21.98%, and this champion PCE is even higher than that of the additive‐containing 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐MeOTAD)‐based device (21.15%). Thermal stability testing at 85 °C for over 1000 h shows that the HL38‐based PSC retains 85.9% of the initial PCE, while the spiro‐MeOTAD‐based PSC degrades unrecoverably from 21.1% to 5.8%. Time‐of‐flight secondary‐ion mass spectrometry studies combined with Fourier transform infrared spectroscopy reveal that HL38 shows lower lithium ion diffusivity than spiro‐MeOTAD due to a strong complexation of the Li+ with HL38, which is responsible for the higher degree of thermal stability. This work delivers an important message that capturing mobile Li+ in a hole‐transporting layer is critical in designing novel MHTs for improving the thermal stability of PSCs. In addition, it also highlights the impact of interface design on non‐conventional MHTs.
Targeted Dual Small Interfering Ribonucleic Acid Delivery via Non‐Viral Polymeric Vectors for Pulmonary Fibrosis Therapy
Authors: Ji Qijian , Hou Jiwei , Yong Xueqing , Gong Guangming , Muddassir Mohd. , Tang Tianyu , Xie Jinbing , Fan Wenpei , Chen Xiaoyuan
Published: February 2021

Inhibiting the myofibroblast differentiation of lung‐resident mesenchymal stem cells (LR‐MSCs) is a promising yet challenging approach for pulmonary fibrosis (PF) therapy. Here, micelles formed by a graft copolymer of multiple PEGs modified branched polyethylenimine are used for delivering runt‐related transcription factor‐1 (RUNX1) small interfering RNA (siRNA) (siRUNX1) to the lung, aiming to inhibit the myofibroblast differentiation of LR‐MSCs. LR‐MSC targeting is achieved by functionalizing the micelle surface with an anti‐stem‐cell antigen‐1 antibody fragment (Fab′). Consequently, therapeutic benefits are obtained by successful suppression of myofibroblast differentiation of LR‐MSCs in bleomycin‐induced PF model mice treated with siRUNX1‐loaded micelles. Furthermore, an excellent synergistic effect of PF therapy is achieved for this micelle system loaded siRUNX1 and glioma‐associated oncogene homolog‐1 (Gli1) small interfering RNA (siGli1), a traditional anti‐PF siRNA of glioma‐associated oncogene homolog‐1. Hence, this work not only provides RUNX1 as a novel PF therapeutic target, but also as a promising dual siRNA‐loaded nanocarrier system for the therapy of PF.
Understanding Oxygen Bubble‐Triggered Exfoliation of Graphite Toward the Low‐Defect Graphene
Authors: Yang Juan , Zhang Xiaqing , Liu Yajie , Tai Zhixin , Yan Xingbin , Ma Jiantai
Published: February 2021

Although graphene has been developed and widely used in many fields over the past decades, the effect of oxygen (O2) on the exfoliation of graphite is still unclear. Here, a simple bubble‐triggered exfoliation method is employed for controllable synthesis of graphene nanoplatelets (GNPs) with low‐oxidation level and high electrical conductivity. The exfoliation process is studied and a formation mechanism for the synthesis of the low‐defect GNPs is proposed. The results show that the synergistic effect of H2SO4 and H2O2 plays an important role in the procession of exfoliation of graphite. Moreover, density functional theory (DFT) simulations exhibit that H2O2 would preferentially adsorb on the edge of graphite, indicating the possibility to initiate the exfoliation by O2. In the whole process, some oxygen free radicals can be released from H2O2, resulting in some O2 and oxygen functional groups formed on the graphite edge, and which can finally lead to the fast exfoliation of graphite. In addition, a time‐dependent temperature profile under an applied voltage of 5 V exhibits a steady‐state with temperature up to 275 °C. Overall, this work elucidates the selectivity of gas bubble absorbed on the side edge of graphite and presents a potential application for high‐electrical conductivity graphene.
Excited‐State Intramolecular Proton Transfer (ESIPT) for Optical Sensing in Solid State
Authors: Chen Ling , Fu Peng‐Yan , Wang Hai‐Ping , Pan Mei
Published: February 2021

Excited‐state intramolecular proton transfer (ESIPT) process brings about ultrafast keto‐enol tautomerism, which simultaneously induces the unique four‐leveled energy state cycle and concomitant multi‐emissions. Such transformation is easily affected by the environmental conditions, leading to intricate spectral responses. In contrast with the widely reported researches that inclined to the solution systems dissolved with ESIPT molecules, ESIPT materials including small organic molecules, metal‐organic materials, covalent‐organic frameworks, and so on, which can be formed in solid state are emerging in recent years, bringing more scientific information and novel applications for the family of ESIPT materials. In this short review, the progress for the different types of these materials will be introduced, especially their optical sensing performances and mechanisms, like responses to external physical stimulations (pressure, temperature, light), solvent polarities, pH, ions, and small molecule compounds. And the potential photophysical and photochemical applications will also be surveyed.
Modulating the Electrical and Mechanical Microenvironment to Guide Neuronal Stem Cell Differentiation
Authors: Oh Byeongtaek , Wu Yu‐Wei , Swaminathan Vishal , Lam Vivek , Ding Jun , George Paul M.
Published: February 2021

The application of induced pluripotent stem cells (iPSCs) in disease modeling and regenerative medicine can be limited by the prolonged times required for functional human neuronal differentiation and traditional 2D culture techniques. Here, a conductive graphene scaffold (CGS) to modulate mechanical and electrical signals to promote human iPSC‐derived neurons is presented. The soft CGS with cortex‐like stiffness (≈3 kPa) and electrical stimulation (±800 mV/100 Hz for 1 h) incurs a fivefold improvement in the rate (14d) of generating iPSC‐derived neurons over some traditional protocols, with an increase in mature cellular markers and electrophysiological characteristics. Consistent with other culture conditions, it is found that the pro‐neurogenic effects of mechanical and electrical stimuli rely on RhoA/ROCK signaling and de novo ciliary neurotrophic factor (CNTF) production respectively. Thus, the CGS system creates a combined physical and continuously modifiable, electrical niche to efficiently and quickly generate iPSC‐derived neurons.
Inter‐ and Transgenerational Effects of Paternal Exposure to Inorganic Arsenic
Authors: Gong Yingyun , Xue Yanfeng , Li Xin , Zhang Zhao , Zhou Wenjun , Marcolongo Paola , Benedetti Angiolo , Mao Shengyong , Han Leng , Ding Guolian , Sun Zheng
Published: February 2021

The rise of metabolic disorders in modern times is mainly attributed to the environment. However, heritable effects of environmental chemicals on mammalian offsprings' metabolic health are unclear. Inorganic arsenic (iAs) is the top chemical on the Agency for Toxic Substances and Disease Registry priority list of hazardous substances. Here, we assess cross‐generational effects of iAs in an exclusive male‐lineage transmission paradigm. The exposure of male mice to 250 ppb iAs causes glucose intolerance and hepatic insulin resistance in F1 females, but not males, without affecting body weight. Hepatic expression of glucose metabolic genes, glucose output, and insulin signaling are disrupted in F1 females. Inhibition of the glucose 6‐phosphatase complex masks the intergenerational effect of iAs, demonstrating a causative role of hepatic glucose production. F2 offspring from grandpaternal iAs exposure show temporary growth retardation at an early age, which diminishes in adults. However, reduced adiposity persists into middle age and is associated with altered gut microbiome and increased brown adipose thermogenesis. In contrast, F3 offspring of the male‐lineage iAs exposure show increased adiposity, especially on a high‐calorie diet. These findings have unveiled sex‐ and generation‐specific heritable effects of iAs on metabolic physiology, which has broad implications in understanding gene‐environment interactions.
Wearable and Implantable Electroceuticals for Therapeutic Electrostimulations
Authors: Long Yin , Li Jun , Yang Fan , Wang Jingyu , Wang Xudong
Published: February 2021

Wearable and implantable electroceuticals (WIEs) for therapeutic electrostimulation (ES) have become indispensable medical devices in modern healthcare. In addition to functionality, device miniaturization, conformability, biocompatibility, and/or biodegradability are the main engineering targets for the development and clinical translation of WIEs. Recent innovations are mainly focused on wearable/implantable power sources, advanced conformable electrodes, and efficient ES on targeted organs and tissues. Herein, nanogenerators as a hotspot wearable/implantable energy‐harvesting technique suitable for powering WIEs are reviewed. Then, electrodes for comfortable attachment and efficient delivery of electrical signals to targeted tissue/organ are introduced and compared. A few promising application directions of ES are discussed, including heart stimulation, nerve modulation, skin regeneration, muscle activation, and assistance to other therapeutic modalities.
A Study of Model‐Based Protective Fast‐Charging and Associated Degradation in Commercial Smartphone Cells: Insights on Cathode Degradation as a Result of Lithium Depositions on the Anode
Authors: Besli Münir M. , Subbaraman Anantharaman , Pour Safaei Farshad R. , Johnston Christina , Schneider Gerhard , Ravi Nikhil , Christensen Jake , Liu Yijin , Doeff Marca M. , Metzger Michael , Kuppan Saravanan
Published: February 2021

The ever expanding mobile consumer electronic market has accelerated the need for safe and efficient fast‐charging approaches that improve the overall speed of battery charging without hastened deterioration of the battery performance. Herein, the impact of a resource inexpensive, physics‐based, electrochemically optimized fast‐charging algorithm (charging time < 2 h) for mobile devices is investigated. A critical difference in the amount and morphology of lithium deposits on the anode for cells fast‐charged without an optimized algorithm is observed and found to be the main cause of capacity decay. An in‐depth study of the LiCoO2 cathode regions opposite to pronounced lithium deposits on the anode reveals a “mirroring” phenomenon, i.e., a frozen monoclinic phase, and inactivity to relithiation. In operando hard X‐ray absorption spectroscopy reveals that degraded spots on harvested cathodes seem to be activated again and participate in the intercalation process when lithiated at low rates from lithium foil counter electrodes. On the other hand, tests at higher C‐rates, closer to the actual fast‐charging rate, reveal only negligible oxidation state changes and therefore poor performance.
Interface Aspects in All‐Solid‐State Li‐Based Batteries Reviewed
Authors: Chen Chunguang , Jiang Ming , Zhou Tao , Raijmakers Luc , Vezhlev Egor , Wu Baolin , Schülli Tobias U. , Danilov Dmitri L. , Wei Yujie , Eichel Rüdiger‐A. , Notten Peter H. L.
Published: February 2021

Extensive efforts have been made to improve the Li‐ionic conductivity of solid electrolytes (SE) for developing promising all‐solid‐state Li‐based batteries (ASSB). Recent studies suggest that minimizing the existing interface problems is even more important than maximizing the conductivity of SE. Interfaces are essential in ASSB, and their properties significantly influence the battery performance. Interface problems, arising from both physical and (electro)chemical material properties, can significantly inhibit the transport of electrons and Li‐ions in ASSB. Consequently, interface problems may result in interlayer formation, high impedances, immobilization of moveable Li‐ions, loss of active host sites available to accommodate Li‐ions, and Li‐dendrite formation, all causing significant storage capacity losses and ultimately battery failures. The characteristic differences of interfaces between liquid‐ and solid‐type Li‐based batteries are presented here. Interface types, interlayer origin, physical and chemical structures, properties, time evolution, complex interrelations between various factors, and promising interfacial tailoring approaches are reviewed. Furthermore, recent advances in the interface‐sensitive or depth‐resolved analytical tools that can provide mechanistic insights into the interlayer formation and strategies to tailor the interlayer formation, composition, and properties are discussed.
Pleistocene aridification underlies the evolutionary history of the Caribbean endemic, insular, giantConsolea(Opuntioideae)
Authors: Majure Lucas C. , Barrios Duniel , Díaz Edgardo , Zumwalde Bethany A. , Testo Weston , Negrón‐Ortíz Vivian
Published: February 2021

Premise

The Caribbean islands are in the top five biodiversity hotspots on the planet; however, the biogeographic history of the seasonally dry tropical forest (SDTF) there is poorly studied.Consoleaconsists of nine species of dioecious, hummingbird‐pollinated tree cacti endemic to the West Indies, which form a conspicuous element of the SDTF. Several species are threatened by anthropogenic disturbance, disease, sea‐level rise, and invasive species and are of conservation concern. However, no comprehensive phylogeny yet exists for the clade.

Methods

We reconstructed the phylogeny ofConsolea, sampling all species using plastomic data to determine relationships, understand the evolution of key morphological characters, and test their biogeographic history. We estimated divergence times to determine the role climate change may have played in shaping the current diversity of the clade.

Results

Consoleaappears to have evolved very recently during the latter part of the Pleistocene on Cuba/Hispaniola likely from a South American ancestor and, from there, moved into the Bahamas, Jamaica, Puerto Rico, Florida, and the Lesser Antilles. The tree growth form is a synapomorphy ofConsoleaand likely aided in the establishment and diversification of the clade.

Conclusions

Pleistocene aridification associated with glaciation likely played a role in shaping the current diversity ofConsolea, and insular gigantism may have been a key innovation leading to the success of these species to invade the often‐dense SDTF. This in‐situ Caribbean radiation provides a window into the generation of species diversity and the complexity of the SDTF community within the Antilles.
Scales of Practices and Outcomes for Community‐Engaged Research
Authors: Boursaw Blake , Oetzel John G. , Dickson Elizabeth , Thein Thomas S. , Sanchez‐Youngman Shannon , Peña Juan , Parker Myra , Magarati Maya , Littledeer Lenora , Duran Bonnie , Wallerstein Nina
Published: February 2021

Despite the growth of research on community‐engaged research (CEnR), recent reviews suggest there has been limited development of validated scales to measure key contexts, mechanisms, and outcomes, impairing testing and refinement of theoretical models. The purpose of this study is to present the psychometric properties of scales from the Engage for Equity (E2) project, stemming from a long‐term research partnership examining community‐engaged research projects. This study used a three‐stage, cross‐sectional format: (a) a sampling frame of 413 CEnR projects was identified; (b) 210 principal investigators completed a project‐level survey and nominated partners for another survey; (c) 457 investigators and partners completed a survey about project contexts, processes, interventions, and outcomes. Factorial validity was established through confirmatory factor analysis supporting seven scales: contextual capacity, commitment to collective empowerment, relationships, community engagement in research actions, synergy, partner and partnership transformation, and projected outcomes. Convergent validity was established through examining covariances among the scales. This study largely yielded results consistent with a previous psychometric study of related measures, while demonstrating improved ceiling effects of the items and refined conceptualization of core theoretical constructs.
Language in young females with fragile X syndrome: Influence on the neurocognitive profile and adaptive behavior
Authors: Joga‐Elvira Lorena , Roche‐Martínez Ana , Joga María‐Luisa , Jacas‐Escarcelle Carlos , Brun‐Gasca Carme
Published: February 2021

Fragile X syndrome (FXS) is the leading cause of inherited intellectual disability. The objective of this research is to analyze the relationship between linguistic functions and performance of the following neuropsychological functions: executive, quantitative reasoning, social perception, behavior, social skills, and adaptive behavior. A neuropsychological and behavioral evaluations were carried out with a group of 26 girls with FXS, and 14 girls without FXS as a control group, using standardized tests. The two groups were homogeneous in age and IQ. Significant differences were found between groups in the relationship between some language processes: inhibition, auditory working memory, cognitive flexibility, level of social adaptation, self‐direction, conceptual adaptation, academic skills, leadership ability, theory of mind, and arithmetic. In the group of girls with FXS, it was found that different aspects of language influence some of the executive functions evaluated, in addition to some specific aspects of social perception, adaptive behavior, and quantitative reasoning, in different ways. Future research should incorporate the study of the influence of other cognitive variables such as visual perception and executive function on behavioral, social, and adaptive aspects to know the real influence of all the cognitive variables on the behavior of girls with FXS.
Understanding the Origin of the Chiral Recognition of Esters with Octahedral Chiral Cobalt Complexes
Authors: Jang Sumin , Kim Hyunwoo
Published: February 2021

Here, we report a combined experimental and computational study to understand the chiral recognition of cationic cobalt complexes with esters. The cationic cobalt complexes were synthesized by stereoselective assembly of ligands to the cobalt center. The tetradentate N2O2 ligand was used to control the metal‐centered chirality, and the bidentate diamine ligand played an important role in the chiral discrimination of esters by 1H NMR spectroscopy. The phenyl rings of the cobalt complexes additively enhanced the chiral discrimination. The opposite chiralities of the N2O2 ligand and bidentate diamine ligand constituted a well‐matched combination, which was further demonstrated by computational analysis of 1 : 2 binding models of the cationic cobalt complex and 1‐phenylethyl acetate.
Sex differences in the behavioral variant of frontotemporal dementia: A new window to executive and behavioral reserve
Authors: Illán‐Gala Ignacio , Casaletto Kaitlin B. , Borrego‐Écija Sergi , Arenaza‐Urquijo Eider M. , Wolf Amy , Cobigo Yann , Goh Sheng Yang M. , Staffaroni Adam M. , Alcolea Daniel , Fortea Juan , Blesa Rafael , Clarimon Jordi , Iulita Maria Florencia , Brugulat‐Serrat Anna , Lladó Albert , Grinberg Lea T. , Possin Katherine , Rankin Katherine P. , Kramer Joel H. , Rabinovici Gil D. , Boxer Adam , Seeley William W. , Sturm Virginia E. , Gorno‐Tempini Maria Luisa , Miller Bruce L. , Sánchez‐Valle Raquel , Perry David C. , Lleó Alberto , Rosen Howard J.
Published: February 2021

Introduction

Biological sex is an increasingly recognized factor driving clinical and structural heterogeneity in Alzheimer's disease, but its role in the behavioral variant of frontotemporal dementia (bvFTD) is unknown.

Methods

We included 216 patients with bvFTD and 235 controls with magnetic resonance imaging (MRI) from a large multicenter cohort. We compared the clinical characteristics and cortical thickness between men and women with bvFTD and controls. We followed the residuals approach to study behavioral and cognitive reserve.

Results

At diagnosis, women with bvFTD showed greater atrophy burden in the frontotemporal regions compared to men despite similar clinical characteristics. For a similar amount of atrophy, women demonstrated better‐than‐expected scores on executive function and fewer changes in apathy, sleep, and appetite than men.

Discussion

Our findings suggest that women might have greater behavioral and executive reserve than men, and neurodegeneration must be more severe in women to produce symptoms similar in severity to those in men.
Copper(II) complexes with a benzimidazole functionalized Schiff base: Synthesis, crystal structures, and role of ancillary ions in phenoxazinone synthase activity
Authors: Mudi Prafullya Kumar , Mahato Rajani Kanta , Joshi Mayank , Shit Madhusudan , Choudhury Angshuman Roy , Das Hari Sankar , Biswas Bhaskar
Published: February 2021

This research study reports the synthesis, structural characterization and phenoxazinone synthase‐like activity of two structurally similar copper(II) complexes developed with a benzimidazole functionalized Schiff base (L). The ligand, L, was designed and synthesized in high yield by the reaction of p‐methoxy benzaldehyde with o‐phenylenediamine. The reaction of L with CuCl2 and Cu(NO3)2 leads to the formation of two isostructural complexes, [Cu(L)2Cl2]2 (1) and [Cu(L)2(NO3)2]2 (2). Single crystal X‐ray structural study reveals that both the Cu(II) centre in 1 and 2 adopts a square planar geometry. An attempt has also been made to understand the role of coordinated co‐ligands on the catalytic oxidation of 2‐aminophenol (2‐AP) to 2‐amino‐3H‐phenoxazine‐3‐one (2‐APX) in methanol. The presence of coordinated nitrate to Cu(II) ions imparts a more labile character to complex 2, and the catalytic efficiency (kcat/KM) for complex 2 (1.50 × 107) was determined almost double compared with that of complex 1 (8.78 × 106). Electro‐chemical and electrospray ionization mass spectrometry studies of 1 and 2 with 2‐AP suggests that the square planar geometries of the Cu(II) centres remain the driving force to develop enzyme‐substrate adducts and excellent catalytic performance of the complexes. Electrochemical and EPR spectral analysis of the reaction mixture confirm the presence of active 2‐AP−/2‐AP•− redox species in the course of catalytic oxidation and suggest the radical driven oxidative coupling of 2‐AP in an aerobic environment. Temperature‐dependent kinetic measurements were carried out to evaluate the activation parameters (Ea, ΔH‡, ΔS‡), which favours the higher rate of catalytic oxidation of 2‐AP for complex 2 than complex 1.
Chemical Compositions and Oxidative Stabilities of Ginkgo biloba Kernel Oils from Four Cultivated Regions in China
Authors: Xie Liangliang , Zhang Tao , Zheng Liyou , Xie Dan , Jin Jun , Wang Xingguo , Jin Qingzhe
Published: February 2021

Ginkgo biloba is a living fossil and traditionally known as a source of pharmaceuticals and cosmetics, largely because of the lipids in the kernels. In the present study, fatty acids, triacylglycerols, micronutrients, and oxidative stabilities of G. biloba kernel oils from four major different cultivated regions in China were systematically analyzed. The results showed that the kernel oils contained more than 26 triacylglycerol species with high contents of linoleic acid (42.04–43.01%), oleic acid (14.33–18.00%), and trans‐vaccenic acid (15.13–16.86%). Functional fatty acids such as trans‐vaccenic acid, palmitoleic acid, and podocarpic acid were particularly enriched in the oils. In addition, high levels of tocopherols (173.41–272.18 mg/100 g) and 304.09–673.26 mg/100 g of phytosterols in the oils contributed to significantly improve their oxidative stabilities. In particular, α‐tocopherol (106.63–127.35 mg/100 g), γ‐tocopherol (41.41–133.65 mg/100 g), campesterol (53.22–139.88 mg/100 g), and β‐sitosterol (245.50–522.62 mg/100 g) were the dominant micronutrients; while γ‐tocopherol significantly affected oxidative stabilities of the four oils from different regions. It is suggested that the G. biloba kernel oils are ideal sources for high‐valued usages in skin care purpose, physical therapy, functional food, and nutritional supplements.
Geophysical investigation, in a regional and local mode, at Thorikos Valley, Attica, Greece, trying to answer archaeological questions
Authors: Apostolopoulos George , Kapetanios Andreas
Published: February 2021

The area known today as Lavreotiki corresponds roughly to the ancient mining district of Lavrion, located in the south‐easternmost part of Attica in Greece. In Classical times, the 5000 hectares of mines and metallurgical workshops provided the wealth to enable the Polis of Athens (the Athenian city‐state) to become the leading hegemonic political power in the Greek world. During this time, Thorikos was one of 10 Attic Demes in the mining district, extending over a complex system of alluvial valleys and across the slopes of the surrounding hills. Archaeological research in this area has previously revealed a theatre, a double doric stoa, mines and metallurgical workshops, dispersed or in clusters. The geoarchaeological investigation presented in this paper attempts to shed light on the spatial organization of the ancient Attic Deme of Thorikos through developing an understanding of the contemporaneous palaeoenvironment. It is designed to test the hypothesis that the ‘Double Doric Stoa’ building was originally part of the Thorician community centre, that is, its Agora, and to suggest possible locations for the Deme's harbour. A geophysical survey of the Thorikos Valley was conducted in regional mode utilizing frequency electromagnetic method (FEM) measurements in order to accommodate a local salinization phenomenon and in local mode, around a ‘Double Doric Stoa’ building, with FEM and ground‐penetrating radar (GPR) measurements. The survey used electrical resistivity tomography (ERT) profiles for deep investigation. This multi‐proxy survey generated a stratigraphy for the palaeoenvironment around the ‘Double Doric Stoa’ building and revealed outlines of anthropogenic, probably ancient, structures. The results suggest that the surveyed area and its features lay on a peninsula‐like land formation, close to the palaeo‐coastline (thus providing clues to the location of the ancient harbour), and that the dispersion and outlines of the buried anthropogenic structures corroborate the interpretation of the site as the Thorician Agora.
A Proinflammatory Cytokine Network Profile in Th1/Type 1 Effector B Cells Delineates a Common Group of Patients in Four Systemic Autoimmune Diseases
Authors: Simon Quentin , Grasseau Alexis , Boudigou Marina , Le Pottier Laëtitia , Bettachioli Eléonore , Cornec Divi , Rouvière Bénédicte , Jamin Christophe , Le Lann Lucas ,   PRECISESADS Clinical Consortium,   PRECISESADS Flow Cytometry Study Group, Borghi Maria Orietta , Aguilar‐Quesada Rocio , Renaudineau Yves , Alarcón‐Riquelme Marta E. , Pers Jacques‐Olivier , Hillion Sophie
Published: February 2021

Objective

The effector T cell and B cell cytokine networks have been implicated in the pathogenesis of systemic autoimmune diseases, but the association of these cytokine networks with the heterogeneity of clinical manifestations and immune profiles has not been carefully examined. This study was undertaken to examine whether cytokine profiles can delineate distinct groups of patients in 4 systemic autoimmune diseases (systemic lupus erythematosus, Sjögren’s syndrome, rheumatoid arthritis, and systemic sclerosis).

Methods

A total of 179 patients and 48 healthy volunteers were enrolled in the multicenter cross‐sectional PRECISE Systemic Autoimmune Diseases (PRECISESADS) study. Multi‐low‐dimensional omics data (cytokines, autoantibodies, circulating immune cells) were examined. Coculture experiments were performed to test the impact of the cytokine microenvironment on T cell/B cell cross‐talk.

Results

A proinflammatory cytokine profile defined by high levels of CXCL10, interleukin‐6 (IL‐6), IL‐2, and tumor necrosis factor characterized a distinct group of patients in the 4 systemic autoimmune diseases. In each disease, this proinflammatory cluster was associated with a specific circulating immune cell signature, more severe disease, and higher levels of autoantibodies, suggesting an uncontrolled proinflammatory Th1 immune response. We observed in vitro that B cells reinforce Th1 differentiation and naive T cell proliferation, leading to the induction of type 1 effector B cells and IgG production. This process was associated with an increase in CXCL10, IL‐6, IL‐2, and interferon‐γ production.

Conclusion

This composite analysis brings new insights into human B cell functional heterogeneity based on T cell/B cell cross‐talk, and proposes a better stratification of patients with systemic autoimmune diseases, suggesting that combined biomarkers would be of great value for the design of personalized treatments.
A Randomized, Phase II Study Evaluating the Efficacy and Safety of Anakinra in the Treatment of Gout Flares
Authors: Saag Kenneth G. , Khanna Puja P. , Keenan Robert T. , Ohlman Sven , Osterling Koskinen Lisa , Sparve Erik , Åkerblad Ann‐Charlotte , Wikén Margareta , So Alexander , Pillinger Michael H. , Terkeltaub Robert
Published: February 2021

Objective

To evaluate the efficacy and safety of anakinra compared to triamcinolone in the treatment of gout flares.

Methods

Patients for whom nonsteroidal antiinflammatory drugs and colchicine were not suitable treatments were enrolled in this multicenter, randomized, double‐blind study with follow‐up for up to 2 years. The study was designed to assess superiority of anakinra (100 or 200 mg/day for 5 days) over triamcinolone (40 mg in a single injection) for the primary end point of changed patient‐assessed pain intensity in the most affected joint (scored on a visual analog scale of 0–100) from baseline to 24–72 hours. Secondary outcome measures included: safety, immunogenicity, and patient‐ and physician‐assessed global response.

Results

One hundred sixty‐five patients were randomized to receive anakinra (n = 110) or triamcinolone (n = 55). The median age was 55 years (range 25–83), 87% were men, the mean disease duration was 8.7 years, and the mean number of self‐reported flares during the prior year was 4.5. A total of 301 flares were treated (214 with anakinra; 87 with triamcinolone). Anakinra in both doses and triamcinolone provided clinically meaningful reduction in patient‐assessed pain intensity in the first and subsequent flares. For the first flare, the mean decline in pain intensity from baseline to 24–72 hours for total anakinra and triamcinolone was −41.2 and −39.4, respectively (P = 0.688). Anakinra performed better than triamcinolone for most secondary end points. There were no unexpected safety findings. The presence of antidrug antibodies was not associated with adverse events or altered pain reduction.

Conclusion

Anakinra was not superior to triamcinolone for the primary end point, but had comparable efficacy in pain reduction and was favored for most secondary end points. Anakinra is an effective option for gout flares when conventional therapy is unsuitable.
Spallationsversuche von Faserbetonprobekörpern im Split‐Hopkinson‐Bar
Authors: Mosig Oliver , Zohrabyan Vahan , Curbach Manfred , Braml Thomas , Keuser Manfred , Gebbeken Norbert
Published: February 2021

Auf Basis von Spallationsversuchen an faserbewehrten Betonproben im Split‐Hopkinson‐Bar wurden die dynamischen Kennwerte Elastizitätsmodul, Zugfestigkeit und Bruchenergie ermittelt. Untersucht wurden Betonproben der Festigkeitsklassen C20/25, C40/50 und C80/95 mit Stahlfasergehalten von 0 bis 2,0 Vol.‐ % sowie mit Carbon‐ und PP‐Fasern im Dehnratenbereich von etwa 15 bis 25 1/s. Die Ergebnisse zeigen eine Zunahme der dynamischen Zugfestigkeit und des dynamischen Elastizitätsmoduls des Faserbetons mit steigendem Fasergehalt. Durch die Zugabe von Fasern ist zudem eine enorme Steigerung der Bruchenergie des Faserbetons gegenüber unbewehrten Proben festzustellen, welche für den Stahlfaserbeton im Vergleich zu dem untersuchten Carbon‐ und PP‐Faserbeton höher ausfällt. Mit 1,0 Vol.‐ % Stahlfasern konnte etwa eine Verzehnfachung der Bruchenergie des Stahlfaserbetons ermittelt werden. Weiter wurde festgestellt, dass der Anteil der Einzelfaser an der Verbundtragfähigkeit des Faserbetons mit steigendem Faservolumengehalt abnimmt, da aus der schwierigeren Verarbeitbarkeit eine inhomogene Faserverteilung mit schlechteren Verbundeigenschaften resultiert.
D‐optimal designs of mean‐covariance models for longitudinal data
Authors: Yi Siyu , Zhou Yongdao , Pan Jianxin
Published: February 2021

Longitudinal data analysis has been very common in various fields. It is important in longitudinal studies to choose appropriate numbers of subjects and repeated measurements and allocation of time points as well. Therefore, existing studies proposed many criteria to select the optimal designs. However, most of them focused on the precision of the mean estimation based on some specific models and certain structures of the covariance matrix. In this paper, we focus on both the mean and the marginal covariance matrix. Based on the mean–covariance models, it is shown that the trick of symmetrization can generate better designs under a Bayesian D‐optimality criterion over a given prior parameter space. Then, we propose a novel criterion to select the optimal designs. The goal of the proposed criterion is to make the estimates of both the mean vector and the covariance matrix more accurate, and the total cost is as low as possible. Further, we develop an algorithm to solve the corresponding optimization problem. Based on the algorithm, the criterion is illustrated by an application to a real dataset and some simulation studies. We show the superiority of the symmetric optimal design and the symmetrized optimal design in terms of the relative efficiency and parameter estimation. Moreover, we also demonstrate that the proposed criterion is more effective than the previous criteria, and it is suitable for both maximum likelihood estimation and restricted maximum likelihood estimation procedures.
Restoration of NRF2 attenuates myocardial ischemia reperfusion injury through mediating microRNA‐29a‐3p/CCNT2 axis
Authors: Tian Ran , Guan Xin , Qian Hao , Wang Liang , Shen Zhujun , Fang Ligang , Liu Zhenyu
Published: February 2021

Accumulated studies have been implemented for comprehending the mechanism of myocardial ischemia reperfusion injury (MI/RI). Nuclear factor erythroid‐2 related factor 2 (NRF2)‐mediated transcription activity in MI/RI has not been completely interpreted from the perspective of microRNA‐29a‐3p (miR‐29a‐3p) and cyclin T2 (CCNT2). Therein, this study intends to decode the mechanism of NRF2/miR‐29a‐3p/CCNT2 axis in MI/RI. Rat MI/RI models were established by left anterior descending artery ligation. Rats were injected with NRF2 or CCNT2 overexpression plasmids or miR‐29a‐3p agomir to explore their effects on MI/RI. Hypoxia/reoxygenation (H/R) cardiomyocytes were established and transfected with restored NRF2 or miR‐29a‐3p or CCNT2 for further exploration of their roles. NRF2, miR‐29a‐3p, and CCNT2 expression in myocardial tissues in rats with MI/RI and in cardiomyocytes in H/R injury were detected. ChIP assay verified the relationship between miR‐29a‐3p and NRF2, and the bioinformatics software and dual‐luciferase reporter experiment verified the interaction between miR‐29a‐3p and CCNT2. NRF2 and miR‐29a‐3p were down‐regulated while CCNT2 was up‐regulated in myocardial tissues in rats with MI/RI and in H/R‐treated cardiomyocytes. Restoration of NRF2 or miR‐29a‐3p improved hemodynamics and myocardial injury and suppressed serum inflammation and cardiomyocyte apoptosis via CCNT2 in rats with MI/RI. Upregulation of NRF2 or miR‐29a‐3p inhibited LDH and CK‐MB activities, oxidative stress, and apoptosis and promoted viability of cardiomyocytes with H/R injury. NRF2 bound to the promoter of miR‐29a‐3p and CCNT2 was targeted by miR‐29a‐3p. This study elucidates that up‐regulating NRF2 or miR‐29a‐3p attenuates MI/RI via inhibiting CCNT2, which may renew the existed knowledge of MI/RI‐related mechanism and provide a novel guidance toward MI/RI treatment.
Parcellation‐based anatomic model of the semantic network
Authors: Milton Camille K. , Dhanaraj Vukshitha , Young Isabella M. , Taylor Hugh M. , Nicholas Peter J. , Briggs Robert G. , Bai Michael Y. , Fonseka Rannulu D. , Hormovas Jorge , Lin Yueh‐Hsin , Tanglay Onur , Conner Andrew K. , Glenn Chad A. , Teo Charles , Doyen Stéphane , Sughrue Michael E.
Published: February 2021

Introduction

The semantic network is an important mediator of language, enabling both speech production and the comprehension of multimodal stimuli. A major challenge in the field of neurosurgery is preventing semantic deficits. Multiple cortical areas have been linked to semantic processing, though knowledge of network connectivity has lacked anatomic specificity. Using attentional task‐based fMRI studies, we built a neuroanatomical model of this network.

Methods

One hundred and fifty‐five task‐based fMRI studies related to categorization of visual words and objects, and auditory words and stories were used to generate an activation likelihood estimation (ALE). Cortical parcellations overlapping the ALE were used to construct a preliminary model of the semantic network based on the cortical parcellation scheme previously published under the Human Connectome Project. Deterministic fiber tractography was performed on 25 randomly chosen subjects from the Human Connectome Project, to determine the connectivity of the cortical parcellations comprising the network.

Results

The ALE analysis demonstrated fourteen left hemisphere cortical regions to be a part of the semantic network: 44, 45, 55b, IFJa, 8C, p32pr, SFL, SCEF, 8BM, STSdp, STSvp, TE1p, PHT, and PBelt. These regions showed consistent interconnections between parcellations. Notably, the anterior temporal pole, a region often implicated in semantic function, was absent from our model.

Conclusions

We describe a preliminary cortical model for the underlying structural connectivity of the semantic network. Future studies will further characterize the neurotractographic details of the semantic network in the context of medical application.
Should we be less reactive about contrast reaction prophylaxis?
Authors: Grines Cindy L. , Marshall J Jeffrey
Published: February 2021

Key Points

The risk of anaphylaxis from contrast allergy is very low, and there is little evidence to support the use of steroids for premedication.

Use of oral steroids prior to cardiac catheterization in diabetics is associated with more hyperglycemia and hypertension.

The long‐term consequences of steroid induced transient hyperglycemia is unknown.
Linking the right education to right heart catheterization
Authors: Lange Richard A. , Mukherjee Debabrata
Published: February 2021

Key Points

Simulation based education (SBE) allows novice cardiology fellows to achieve a right heart catheterization skill level similar to that of a senior cardiology fellow in a short period of time.

With SBE, novice fellows acquire knowledge of hemodynamic waveform interpretation and the confidence of a senior level trainee.

SBE (i.e., during the first month of training) prepares fellows before patient contact.
The incidence, natural history, and predictive factors for tissue protrusion after drug‐eluting stent implantation
Authors: Otagaki Munemitsu , Fujii Kenichi , Matsumura Koichiro , Noda Teppei , Shibutani Hiroki , Hashimoto Kenta , Morishita Shun , Tsujimoto Satoshi , Yamamoto Yoshihiro , Park Haengnam , Yoshioka Kei , Shiojima Ichiro
Published: February 2021

Objectives and background

Although tissue protrusion (TP) between the stent struts after stent implantation has been implicate as a potential factor of stent failure, the incidence, natural history, and predictive factor of TP after stent implantation remains unclear. This prospective study evaluated the fate of TP after drug‐eluting stent (DES) deployment using optical coherence tomography (OCT).

Method and result

This study analyzed TP for 42 lesions after DES in which three serial OCTs, including preprocedure, postprocedure, and 1‐month after the procedure were performed. TP was classified into the five groups: (a) persistent, (b) progressive, (c) healed, (d) regressive, and (e) late‐acquired. Immediately after the procedure, 100 TPs in 37 lesions (88%) were identified. Of those, 53 (53%) were persistent, 3 (3%) were progressive, 20 (20%) were healed, and 24 (24%) were regressed at 1‐month follow‐up. Seven TPs in five patients (13%) were observed only at 1‐month follow‐up (late‐acquired).

Conclusion

In lesions with late‐acquired TP, calcified nodule was identified as an underlying plaque morphology on preprocedural OCT. A serial OCT analysis found TP occurred not only immediately after DES implantation, but also 1‐month after DES implantation.
Superselective adrenal arterial embolization for idiopathic hyperaldosteronism: 12‐month results from a proof‐of‐principle trial
Authors: Dong Hui , Zou Yubao , He Jining , Deng Yu , Chen Yang , Song Lei , Xu Bo , Gao Runlin , Jiang Xiongjing
Published: February 2021

Objectives

This study aimed to assess the safety, blood pressure changes, and biochemical responses of superselective adrenal artery embolization (SAAE) in hypertensive patients with idiopathic hyperaldosteronism (IHA).

Background

SAAE is a minimally invasive procedure that has been used to successfully treat aldosterone‐producing adenoma. However, its effect for patients with IHA is unevaluated.

Methods

A total of 41 hypertensive patients who were diagnosed with IHA and underwent SAAE at the Fuwai Hospital between December 2010 and June 2016 were prospectively enrolled. The blood pressure, antihypertensive medications, plasma aldosterone and potassium levels, and adverse events were assessed. The primary endpoint was the change in home blood pressure at 12 months, compared with baseline.

Results

SAAE was technically successful in 39 patients. Postoperatively, home and 24‐hr mean blood pressures were reduced by 14/9 and 10/7 mmHg at 1 month, respectively, and by 13/7 and 11/7 mmHg at 12 months, respectively. The number of antihypertensive agents used reduced by 1.0 and 1.1 at 1 month and 12 months, respectively (all p < .001). Compared with baseline (524.0 pmol/L), the standing plasma aldosterone reduced to 293.4 pmol/L at 12 months (p < .001). Serum potassium increased from 3.0 to 4.1 mmol/L while the rate of potassium supplement and mineralocorticoid receptor antagonist use reduced from 87.1 and 89.7%, respectively, to 28.2 and 17.9%, respectively, at 12 months (all p < .001). There were no serious complications in the perioperative and 12‐month follow‐up periods.

Conclusions

SAAE was effective and feasible for IHA treatment, without serious complications, therefore, maybe a potential treatment.