bluuebunny/crossref_metadata_2025 huggingface dataset:
Physical Activity and Features of Knee Osteoarthritis on Magnetic Resonance Imaging in Individuals Without Osteoarthritis: A Systematic Review
Authors: Xu Dawei , Van Middelkoop Marienke , Bierma‐Zeinstra Sebastia M. A. , Runhaar Jos
Published: December 2022

Objective

To systematically review all studies that have evaluated the association between physical activity (PA) levels and features of knee osteoarthritis (OA) on magnetic resonance imaging (MRI) for subjects without OA.

Methods

The inclusion criteria for prospective studies were as follows: 1) subjects without OA; 2) average age 35–80 years; and 3) any self‐reported PA or objective measurement of PA. The eligible MRI outcomes were OA‐related measures of intraarticular knee joint structures. Exclusion criteria were evaluations of instant associations with transient structural changes after PA.

Results

Two randomized controlled trials and 16 observational studies were included. One of 11 studies found that PA was harmfully related to cartilage volume or thickness, but 4 studies found a significant protective association. Four of 10 studies found that PA was harmfully related to cartilage defects, while others showed no significant associations. Two of 3 studies reported a significantly increased cartilage T2 value in individuals with more PA. All 3 studies reported no significant association between PA and bone marrow lesions. Two studies assessed the association between PA and meniscus pathology, in which only occupational PA involving knee bending was associated with a greater risk of progression.

Conclusion

Within the sparse and diverse evidence available, no strong evidence was found for the presence or absence of an association between PA and the presence or progression of features of OA on MRI among subjects without OA. Therefore, more research is required before PA in general and also specific forms of PA can be deemed safe for knee joint structures.
Air‐Stable Li2S Cathode for Quasi‐Solid‐State Anode‐Free Batteries with High Volumetric Energy
Authors: Meng Xiangyu , Liu Yuzhao , Yu Le , Qiu Jieshan , Wang Zhiyu
Published: December 2022

Anode‐free batteries can maximize the energy density but their development is hindered by a lack of Li‐rich cathodes for compensating the irreversible Li loss. Li2S cathode is particularly appealing to this desire due to 2.6–4.7 folds more Li content and 4.2–6.8 times higher capacity than conventional intercalation cathodes. But its practical application is hindered by poor stability against moisture attacking in the air. Herein, a facile expendable polymer sheathing strategy toward air‐stable Li2S cathodes with high capacities for developing high‐performance quasi‐solid‐state anode‐free batteries without risk of cell leakage is reported. Tight protection by dense polymer barrier dramatically prolongs the lifetime of Li2S cathode by 2,000 times at least in the air. Such air‐stable Li2S cathode allows for high compatibility of anode‐free battery production with commercial schemes. More attractively, the polymer protective layer can in situ transform to multifunctional gel polymer electrolyte for releasing ionic pathways and enhancing cell performance by inhibiting LiPS loss and smoothing Li plating. With air‐stable Li2S cathode, the quasi‐solid‐state anode‐free cells are assembled in ambient environment to deliver superb volumetric energy density of 1093 Wh L−1. This study may shed new light to push the commercialization of high‐energy and reliable anode‐free batteries forward.
Vacancy Manipulation Induced Optimal Carrier Concentration, Band Convergence and Low Lattice Thermal Conductivity in Nano‐Crystalline SnTe Yielding Superior Thermoelectric Performance
Authors: Zhang Tingdong , Pan Wenfeng , Ning Suiting , Qi Ning , Chen Zhiquan , Su Xianli , Tang Xinfeng
Published: December 2022

Synergetic optimization of electrical and thermal transport properties is achieved for SnTe‐based nano‐crystalline materials. Gd doping is able to suppress the Sn vacancy, which is confirmed by positron annihilation measurements and corresponding theoretical calculations. Hence, the optimal hole carrier concentration is obtained, leading to the improvement of electrical transport performance and simultaneous decrease of electronic thermal conductivity. In addition, the incremental density of states effective mass m* in SnTe is realized by the promotion of the band convergence via Gd doping, which is further confirmed by the band structure calculation. Hence, the enhancement of the Seebeck coefficient is also achieved, leading to a high power factor of 2922 µW m−1 K−2 for Sn0.96Gd0.04Te at 900 K. Meanwhile, substantial suppression of the lattice thermal conductivity is observed in Gd‐doped SnTe, which is originated from enhanced phonon scattering by multiple processes including mass and strain fluctuations due to the Gd doping, scattering of grain boundaries, nano‐pores, and secondary phases induced by Gd doping. With the decreased phonon mean free path and reduced average phonon group velocity, a rather low lattice thermal conductivity is achieved. As a result, the synergetic optimization of the electric and thermal transport properties contributes to a rather high ZT value of ≈1.5 at 900 K, leading to the superior thermoelectric performance of SnTe‐based nanoscale polycrystalline materials.
In Situ Structure Transformation of a Sprayed Gel for pH‐Ultrasensitive Nano‐Catalytic Antibacterial Therapy
Authors: Niu Zhihui , Xie Mingxiao , Wei Zicheng , Guo Yang , Han Mengxuan , Ding Yingying , Huang Jianyu , Zheng Kang , Zhang Yao , Song Yuanda , Niu Dechao , Li Yongsheng , Wen Guangwu , Li Xiaowei , Shi Jianlin
Published: December 2022

Nano‐catalytic bacterial killing provides new opportunities to address ever‐increasing antibiotic resistance. However, the intrinsic catalytic activity usually depends on a much lower pH conditions (pH = 2–5) than that in the weakly acidic bacterial microenvironments (pH = 6–7) for reactive oxygen species production by Fenton reactions. Herein, a MnSiO3‐based pH‐ultrasensitive “in situ structure transformation” is first reported to significantly promote the adhesion between material and bacteria, and shorten the diffusion distance (<20 nm) to compensate ultra‐short life (<200 ns) of ·OH generated by Mn2+‐mediated Fenton‐like reaction, finally enhancing its nano‐catalytic antibacterial performance in weakly acidic conditions. A separated spray bottle is further designed to achieve in situ gelation at the wound site, which demonstrates excellent shape adaptability to complicated and rough surfaces of wounds, allowing for long‐term nano‐catalyst release. As a result, bacterial‐infected wound healing is efficiently promoted. Herein, the in situ sprayed nano‐catalytic antibacterial gel presents a promising paradigm for bacterial infection treatment.
Multicolor and 3D Holography Generated by Inverse‐Designed Single‐Cell Metasurfaces
Authors: So Sunae , Kim Joohoon , Badloe Trevon , Lee Chihun , Yang Younghwan , Kang Hyunjung , Rho Junsuk
Published: December 2022

Metasurface‐generated holography has emerged as a promising route for fully reproducing vivid scenes by manipulating the optical properties of light using ultra‐compact devices. However, achieving multiple holographic images using a single metasurface is still difficult due to the capacity limit of a single meta‐atom. In this work, an inverse design method based on gradient‐descent optimization is presented to encode multiple pieces of holographic information into a single metasurface. The proposed method allows the inverse design of single‐cell metasurfaces without the need for complex meta‐atom design strategies, facilitating high‐throughput fabrication using broadband low‐loss materials. By exploiting the proposed design method, both multiplane red‐green‐blue (RGB) color and three‐dimensional (3D) holograms are designed and experimentally demonstrated. Multiplane RGB color holograms with nine distinct holograms are achieved, which demonstrate the state‐of‐the‐art data capacity of a phase‐only metasurface. The first experimental demonstration of metasurface‐generated 3D holograms with completely independent and distinct images in each plane is also presented. The current research findings provide a viable route for practical metasurface‐generated holography by demonstrating the high‐density holography produced by a single metasurface. It is expected to ultimately lead to optical storage, display, and full‐color imaging applications.
A Multifunctional Interphase Layer Enabling Superior Sodium‐Metal Batteries under Ambient Temperature and −40 °C
Authors: Xia Xianming , Xu Shitan , Tang Fang , Yao Yu , Wang Lifeng , Liu Lin , He Shengnan , Yang Yaxiong , Sun Wenping , Xu Chen , Feng Yuezhan , Pan Hongge , Rui Xianhong , Yu Yan
Published: December 2022

The sodium (Na)‐metal anode with high theoretical capacity and low cost is promising for construction of high‐energy‐density metal batteries. However, the unsatisfactory interface between Na and the liquid electrolyte induces tardy ion transfer kinetics and dendritic Na growth, especially at ultralow temperature (−40 °C). Herein, an artificial heterogeneous interphase consisting of disodium selenide (Na2Se) and metal vanadium (V) is produced on the surface of Na (Na@Na2Se/V) via an in situ spontaneous chemical reaction. Such interphase layer possesses high sodiophilicity, excellent ionic conductivity, and high Young's modulus, which can promote Na‐ion adsorption and transport, realizing homogenous Na deposition without dendrites. The symmetric Na@Na2Se/V cell exhibits outstanding cycling life span of over 1790 h (0.5 mA cm−2/1 mAh cm−2) in carbonate‐based electrolyte. More remarkably, ab initio molecular dynamics simulations reveal that the artificial Na2Se/V hybrid interphase can accelerate the desolvation of solvated Na+ at −40 °C. The Na@Na2Se/V electrode thus exhibits exceptional electrochemical performance in symmetric cell (over 1500 h at 0.5 mA cm−2/0.5 mAh cm−2) and full cell (over 700 cycles at 0.5 C) at −40 °C. This work provides an avenue to design artificial heterogeneous interphase layers for superior high‐energy‐density metal batteries at ambient and ultralow temperatures.
Semi‐Transparent, Chiral Organic Photodiodes with Incident Direction‐Dependent Selectivity for Circularly Polarized Light
Authors: Liu Lixuan , Wei Zhixiang , Meskers Stefan C. J.
Published: December 2022

Detection of the circular polarization of light is possible using chiral semiconductors, yet the mechanisms remain poorly understood. Semi‐transparent chiral photodiodes allow for a simple experiment to investigate the basis of their selectivity: changing the side from which the diode is illuminated. A reversal of circular selectivity is observed in photocurrent generation when changing the direction of illumination on organic, bulk‐heterojunction cells. The change in selectivity can be explained by a space‐charge limitation on the collection of photocarriers in combination with preferential absorption of one of the circular polarizations of near‐infrared light by the chiral non‐fullerene acceptor. The space‐charge limitation is supported by detailed measurements of frequency and intensity dependence of dc and ac photocurrents.
Trojan Horse Nanocapsule Enabled In Situ Modulation of the Phenotypic Conversion of Th17 Cells to Treg Cells for the Treatment of Multiple Sclerosis in Mice
Authors: Shi Chongdeng , Zhang Jing , Wang Huijun , Chen Chen , Han Maosen , Gao Lin , Tang Chunwei , Sun Peng , Zhao Xiaotian , Guo Feiyue , Wang Zhaozhong , Abdalla Mohnad , Yang Zhenmei , Liu Ying , Li Anning , Zhang Cai , Jiang Xinyi
Published: December 2022

Th17/Treg imbalance is closely related to the occurrence and development of multiple sclerosis (MS), and the transdifferentiation of Th17 cells into Treg cells may contribute to the resolution of inflammation, presenting a therapeutic strategy for MS. To modulate this phenotypic shift in situ, a “Trojan horse”‐like hybrid system, nanocapsule‐coupled Th17 cells, is reported for MS treatment. Following intravenous injection into MS mice, the hybrid system efficiently transmigrates across the blood–brain barrier and homes to the inflamed MS niche. (Aminooxy)‐acetic acid, a transdifferentiation inducer, is locally released upon the production of ROS and in turn taken up by Th17 cells. It is demonstrated that the Trojan horse hybrid system enables in situ phenotypic transdifferentiation of Th17 cells into anti‐inflammatory Treg cells. This phenotypic conversion leads to a domino‐like immune response that is conducive to MS therapy. Overall, this work highlights a new pathway for accurate modulation of the phenotypes of adoptively transferred cells in situ, from proinflammatory to anti‐inflammatory for MS therapy, and may be broadly applicable for patients suffering from other autoimmune diseases.
Organocatalytic Asymmetric Synthesis of α‐Trifluoromethyl Homoallylic Amine Derivatives from Trifluoromethyl‐Containing Ketoimines and Isatin‐Derived Morita‐Baylis‐Hillman Carbonates
Authors: Chen Danna , Deng Yabo , Sun Shuo , Jia Pengfei , Huang Jinqi , Yan Wenjin
Published: December 2022

The asymmetric γ‐regioselective‐alkylation reaction which is catalyzed by a chiral tertiary amine ((DHQ)2PHAL) and takes advantage of isatin‐derived Morita‐Baylis‐Hillman carbonates and CF3‐contained ketoimines, delivered chiral α‐trifluoromethylamine derivatives and incorporated an oxindole motif in yields of 65–98%, diastereoselectivities (>20:1 in most cases) and enantioselectivities of 73–99%. The subsequent deprotection gave α‐ trifluoromethyl amines in a stereoselective manner. Furthermore, fused polycyclic frameworks can be furnished by subsequent derivatization of the product without eroding its stereoselectivity.

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Surface Lattice Resonances in 3D Chiral Metacrystals for Plasmonic Sensing
Authors: Manoccio Mariachiara , Tasco Vittorianna , Todisco Francesco , Passaseo Adriana , Cuscuna Massimo , Tarantini Iolena , Gigli Giuseppe , Esposito Marco
Published: December 2022

Chiral lattice modes are hybrid states arising from the chiral plasmonic particles assembled in ordered arrays with opportune periodicity. These resonances exhibit dependence on excitation handedness, and their observation in plasmonic lattices is strictly related to the chiroptical features of the fundamental plasmonic unit. Here, the emergence of chiral surface lattice resonances (c‐SLRs) is shown in properly engineered arrays of nanohelices (NHs), fully three dimensional (3D) chiral nano‐objects fabricated by focused ion beam processing. By tuning the relative weight of plasmonic and photonic components in the hybrid mode, the physical mechanism of strong diffractive coupling leading to the emergence of the lattice modes is analyzed, opening the way to the engineering of chiral plasmonic systems for sensing applications. In particular, a coupling regime is identified where the combination of a large intrinsic circular dichroism (CD) of the plasmonic resonance with a well‐defined balance between the photonic quality factor (Q factor) and the plasmonic field enhancement (M) maximizes the capability of the system to discriminate refractive index (RI) changes in the surrounding medium. The results lay the foundation for exploiting CD in plasmonic lattices to high performance refractometric sensing.
Mechanisms and Synthetic Strategies in Visible Light‐Driven [2+2]‐Heterocycloadditions
Authors: Franceschi Pietro , Cuadros Sara , Goti Giulio , Dell'Amico Luca
Published: December 2022

The synthesis of four membered heterocycles usually requires multi‐step procedures and prefunctionalized reactants. A straightforward alternative is the photochemical [2+2]‐heterocycloaddition between an alkene and a carbonyl derivative, conventionally based on the photoexcitation of this latter. However, this approach is limited by the absorption profile of the carbonyl, requiring in most of the cases the use of high‐energy UV‐light, that often results in undesired side reactions and/or the degradation of the reaction components. The development of new and milder visible light‐driven [2+2]‐heterocycloadditions is, therefore, highly desirable. In this Review, we highlight the most relevant achievements in the development of [2+2]‐heterocycloadditions promoted by visible light, with a particular emphasis on the involved reaction mechanisms. The open challenges will also be discussed, suggesting new possible evolutions, and stimulating new methodological developments in the field.
A General Synthetic Route to High‐Quality Perovskite Oxide Nanoparticles and Their Enhanced Solar Photocatalytic Activity
Authors: Amdouni Wafa , Otoničar Mojca , Gemeiner Pascale , Butin Vincent , Guiblin Nicolas , Maghraoui‐Meherzi Hager , Dkhil Brahim
Published: December 2022

The main limitations of current methods for synthesizing perovskite oxide (ABO3) nanoparticles (NPs), e.g., the high reagent costs and sophisticated equipment, the long time and high‐temperature processing, or multiple post‐processing and thermal treatment steps, hamper their full study and potential application. Here, we use a facile low temperature (50 °C) chemical bath synthesis and only one annealing step to successfully produce high phase purity and crystalline quality nano‐shaped rare‐earth‐based REMO3 NPs (RE=La, Nd, Sm, Gd; M=Fe, Mn, Al). We also show the versatility of this approach by fabricating La0.7Sr0.3MnO3 solid solution and non‐RE‐based BiFeO3 perovskite. To assess the potential of the as‐prepared REFeO3 and REMnO3 NPs, they are used for photocatalytic degradation of the norfloxacin antibiotic and show high efficiency. We believe this easy, robust, versatile, and general route for synthesizing ABO3‐based NPs can be further explored in the vast perovskite family and beyond.
Selective Formal Carbene Insertion into Carbon‐Boron Bonds of Diboronates by N‐Trisylhydrazones
Authors: Bao Zhicheng , Huang Meirong , Xu Yan , Zhang Xinhao , Wu Yun‐Dong , Wang Jianbo
Published: December 2022

Bisborylalkanes play important roles in organic synthesis as versatile bifunctional reagents. The two boron moieties in these compounds can be selectively converted into other functional groups through cross‐coupling, oxidation or radical reactions. Thus, the development of efficient methods for synthesizing bisborylalkanes is highly demanded. Herein we report a new strategy to access bisborylalkanes through the reaction of N‐trisylhydrazones with diboronate, in which the bis(boryl) methane is transformed into 1,2‐bis(boronates) via formal carbene insertion. Since the N‐trisylhydrazones can be readily derived from the corresponding aldehydes, this strategy represents a practical synthesis of 1,2‐diboronates with broad substrate scope. Mechanistic studies reveal an unusual neighboring group effect of 1,1‐bis(boronates), which accounts for the observed regioselectivity when unsymmetric 1,1‐diboronates are applied.
Imaginal disc growth factor is involved in melanin synthesis and energy metabolism in Bombyx mori
Authors: Tian Huan , Liu Shuai‐Qi , Jing Wen‐Hui , Hao Zhi‐Hua , Li Ying‐Hui , Lu Zhe‐Hao , Ding Ze‐Kai , Huang Shao‐Li , Xu Yu‐Song , Wang Hua‐Bing
Published: December 2022

The imaginal disc growth factor (IDGF), belonging to the glycoside hydrolase 18 family, plays an important role in various physiological processes in insects. However, the detail physiological function of IDGF is still unclear. In this study, transcriptome analysis was performed on the fatbody isolated from staged control and BmIDGF mutant silkworm larvae. Transcriptional profiling revealed that the absence of BmIDGF significantly affected differentially expressed genes involved in tyrosine and purine metabolism, as well as multiple energy metabolism pathways, including glycolysis, galactose, starch, and sucrose metabolism. The interruption of BmIDGF caused similar and specific gene expression changes to male and female fatbody. Furthermore, a genome‐scale metabolic network integrating metabolomic and transcriptomic datasets revealed 11 pathways significantly altered at the transcriptional and metabolic levels, including amino acid, carbohydrate, uric acid metabolism pathways, insect hormone biosynthesis, and ABC transporters. In conclusion, this multiomics analysis suggests that IDGF is involved in gene‐metabolism interactions, revealing its unique role in melanin synthesis and energy metabolism. This study provides new insights into the physiological function of IDGF in insects.
Down‐Regulation–Resistant STAT4 Risk Haplotype Contributes to Lupus Nephritis Through CD4+ T Cell Interferon‐γ Production
Authors: Madera‐Salcedo Iris K. , Ramírez‐Sánchez Ada L. , Rodríguez‐Rodríguez Noé , García‐Quintero Roberto , Rubio Rosa M. , Morales‐Montes de Oca Gabriela , Dávalos Emmanuel , Cuervo Rogelio , Furuzawa‐Carballeda Janette , Alcocer‐Varela Jorge , Gómez‐Martín Diana , González‐Yáñez Marysol , de la Cruz Abigail , Albarrán‐Godínez Adrián , Suárez‐Rojas Gerardo , Romero‐Díaz Juanita , Uribe‐Uribe Norma O. , Alarcón‐Riquelme Marta , Furlan‐Magaril Mayra , Mejía‐Vilet Juan Manuel , Crispín José C. , Rosetti Florencia
Published: December 2022

Objective

Variants in STAT4 are associated with systemic lupus erythematosus (SLE) and other autoimmune diseases. We undertook this study to investigate how disease‐associated variants affect STAT4 expression, in particular in CD4+ T cells where STAT4 plays an essential role.

Methods

We compared Th1 differentiation between naive CD4+ T cells from healthy donors homozygous for the risk (R/R) or nonrisk (NR/NR) alleles. We analyzed epigenetic marks in STAT4 and evaluated the relevance of its third intron, assessed the consequences of Stat4 overexpression in vivo in mice, and analyzed the effects of the STAT4 genotype in patients with lupus nephritis.

Results

Naive CD4+ T cells from NR/NR healthy donors down‐regulated STAT4 in response to interleukin‐12 (IL‐12). In contrast, cells from R/R healthy donors maintained high levels. R/R cells exhibited a higher abundance of transcriptionally active STAT4 and increased interferon‐γ production. Accordingly, R/R healthy donors exhibited a stronger induction of local active enhancer marks. Genetic editing confirmed the presence of a negative regulatory region in the STAT4 third intron, where most of the SLE‐associated STAT4 single‐nucleotide polymorphisms (SNPs) are located. In vivo forced expression demonstrated that increases in Stat4 levels in T cells enhanced glomerulonephritis in mice. Accordingly, the R/R genotype was associated with suboptimal response to treatment and with worse clinical outcomes in patients with proliferative lupus nephritis.

Conclusion

The SLE‐associated STAT4 haplotype correlates with an abnormal IL‐12–mediated STAT4 transcriptional regulation. Carriers of the risk variant exhibit exaggerated CD4+ proinflammatory capacities that, in the context of SLE, contribute to more severe disease. R/R patients may benefit from blockade of the IL‐12/STAT4 pathway.

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Metabolic engineering of Aspergillus niger to enhance production of ethanol
Authors: de los Santos Mondragón Ara Itzel , Barragan Brisia Alejandra Aguilar , Sánchez Uriel Rojas , Calleja Cristian Alberto López , Millán‐Chiu Blanca E. , Loske Achim M. , Lim Miguel Angel Gómez
Published: December 2022

This work describes the genetic transformation of a strain of Aspergillus niger with five different constructs containing 16 different heterologous genes, coding for four oxidoreductases, two cellobiohydrolases, one endoglucanase, one β‐glucosidase, six enzymes involved in xylose metabolism, and two enzymes involved in fermentation. The aim was to try and engineer a consolidated bioprocessing in A. niger. The fungus already contains most of these enzymes and we only enhanced endogenous activities. We recovered nine transformants containing all genes, as indicated by polymerase chain reaction (PCR). To confirm that the products of the genes were functional, we measured the activity of five different enzymes in all the strains, and they all showed enhanced activity over the wild‐type (wt) strain. The strains were grown on carboxymethyl cellulose (CMC) and xylan as substrates, and they produced considerably more ethanol than the wt. The levels of ethanol production were comparable to those reported in the literature.
Design of a multi‐epitope‐based vaccine consisted of immunodominant epitopes of structural proteins of SARS‐CoV‐2 using immunoinformatics approach
Authors: Mahmoudvand Shahab , Esmaeili Gouvarchin Ghaleh Hadi , Jalilian Farid Azizi , Farzanehpour Mahdieh , Dorostkar Ruhollah
Published: December 2022

Severe acute respiratory syndrome coronavirus 2 (SARS‐CoV‐2) has shown rapid global spread and has resulted in a significant death toll worldwide. In this study, we aimed to design a multi‐epitope vaccine against SARS‐CoV‐2 based on structural proteins S, M, N, and E. We identified B‐ and T‐cell epitopes and then the antigenicity, toxicity, allergenicity, and similarity of predicted epitopes were analyzed. T‐cell epitopes were docked with corresponding HLA alleles. Consequently, the selected T‐ and B‐cell epitopes were included in the final construct. All selected epitopes were connected with different linkers and flagellin and pan‐HLA DR binding epitopes (PADRE) as an adjuvant were used in the vaccine construct. Furthermore, molecular docking was used to evaluate the complex between the final vaccine construct and two alleles, HLA‐A*02:01 and HLA‐DRB1*01:01. Finally, codons were optimized for in silico cloning into pET28a(+) vector using SnapGene. The final vaccine construct comprised 11 CTL, HTL, and B‐cell epitopes corresponding to 394 amino acid residues. In silico evaluation showed that the designed vaccine might potentially promote an immune response. Further in vivo preclinical and clinical testing is required to determine the safety and efficacy of the designed vaccine.
Synthesis, molecular docking, and antioxidant activity of new fluorescent tetrafluoroterphenyl analogues
Authors: Al‐Anazi Menier
Published: December 2022

Nucleophilic aromatic substitution (SNAr) chemistry has been applied to develop many functionalized pentafluorobenzene derivatives. Those compounds are highly specific at the para position of the fluorinated ring. Therefore, they are typical adducts for the preparation of antioxidant molecular systems. In this context, we report the use of SNAr chemistry as a suitable and simple approach for the synthesis of fluorescent antioxidant perfluorinated materials bearing ether bonds in various para‐substituted alkoxy chains and with high purity and excellent yields. The fluoroterphenyl core was prepared via alkylation, Cu(I)‐assisted decarboxylation, and cross‐coupling using the potassium salt of fluorobenzoate, followed by the reaction with different alcohols. The structures of the synthesized fluoroterphenyl adducts were investigated using FT‐IR, 1H NMR, 13C NMR, and 19F NMR spectroscopy. The emission spectra and absorption spectra showed solvatochromism. The newly prepared tetrafluoroterphenyl analogues were investigated by antioxidant examination using the 2,2‐diphenyl‐1‐picrylhydrazyl assay. Results were compared with ascorbic acid and butylated hydroxytoluene as references, and revealed that the tetrafluoroterphenyl analogues containing a decyl chain had the highest activity, with an IC50 value of 22.36 ± 0.19 g/ml. The produced tetrafluoroterphenyl analogues were used in molecular docking strategies with a Protein Data Bank protein ID 5IKQ. The antioxidant investigations and docking results were convergent.
SLAM‐seq reveals early transcriptomic response mechanisms upon glutamine deprivation in Chinese hamster ovary cells
Authors: Papež Maja , Jiménez Lancho Víctor , Eisenhut Peter , Motheramgari Krishna , Borth Nicole
Published: December 2022

Mammalian cells frequently encounter subtle perturbations during recombinant protein production. Identifying the genetic factors that govern the cellular stress response can facilitate targeted genetic engineering to obtain production cell lines that demonstrate a higher stress tolerance. To simulate nutrient stress, Chinese hamster ovary (CHO) cells were transferred into a glutamine(Q)‐free medium and transcriptional dynamics using thiol(SH)‐linked alkylation for the metabolic sequencing of RNA (SLAM‐seq) along with standard RNA‐seq of stressed and unstressed cells were investigated. The SLAM‐seq method allows differentiation between actively transcribed, nascent mRNA, and total (previously present) mRNA in the sample, adding an additional, time‐resolved layer to classic RNA‐sequencing. The cells tackle amino acid (AA) limitation by inducing the integrated stress response (ISR) signaling pathway, reflected in Atf4 overexpression in the early hours post Q deprivation, leading to subsequent activation of its targets, Asns, Atf3, Ddit3, Eif4ebp1, Gpt2, Herpud1, Slc7a1, Slc7a11, Slc38a2, Trib3, and Vegfa. The GCN2‐eIF2α‐ATF4 pathway is confirmed by a significant halt in transcription of translation‐related genes at 24 h post Q deprivation. The downregulation of lipid synthesis indicates the inhibition of the mTOR pathway, further confirmed by overexpression of Sesn2. Furthermore, SLAM‐seq detects short‐lived transcription factors, such as Egr1, that would have been missed in standard experimental designs with RNA‐seq. Our results describe the successful establishment of SLAM‐seq in CHO cells and therefore facilitate its future use in other scenarios where dynamic transcriptome profiling in CHO cells is essential.
Responses in left inferior frontal gyrus are altered for speech‐in‐noise processing, but not for clear speech in autism
Authors: Schelinski Stefanie , von Kriegstein Katharina
Published: December 2022

Introduction

Autistic individuals often have difficulties with recognizing what another person is saying in noisy conditions such as in a crowded classroom or a restaurant. The underlying neural mechanisms of this speech perception difficulty are unclear. In typically developed individuals, three cerebral cortex regions are particularly related to speech‐in‐noise perception: the left inferior frontal gyrus (IFG), the right insula, and the left inferior parietal lobule (IPL). Here, we tested whether responses in these cerebral cortex regions are altered in speech‐in‐noise perception in autism.

Methods

Seventeen autistic adults and 17 typically developed controls (matched pairwise on age, sex, and IQ) performed an auditory‐only speech recognition task during functional magnetic resonance imaging (fMRI). Speech was presented either with noise (noise condition) or without noise (no noise condition, i.e., clear speech).

Results

In the left IFG, blood‐oxygenation‐level‐dependent (BOLD) responses were higher in the control compared to the autism group for recognizing speech‐in‐noise compared to clear speech. For this contrast, both groups had similar response magnitudes in the right insula and left IPL. Additionally, we replicated previous findings that BOLD responses in speech‐related and auditory brain regions (including bilateral superior temporal sulcus and Heschl's gyrus) for clear speech were similar in both groups and that voice identity recognition was impaired for clear and noisy speech in autism.

Discussion

Our findings show that in autism, the processing of speech is particularly reduced under noisy conditions in the left IFG—a dysfunction that might be important in explaining restricted speech comprehension in noisy environments.
Climate risk disclosures and global sustainability initiatives: A conceptual analysis and agenda for future research
Authors: Ngo Thanh , Le Tu , Ullah Subhan , Trinh Hai Hong
Published: December 2022

Climate change impacts, risks and sustainability disclosures have attracted increasing attention from scholars in various streams of the economics and finance literature towards achieving the UN's Sustainable Development Goals (SDGs). Within the stream of climate finance, the global initiatives for corporate social responsibility (CSR) and environment, social and governance (ESG) practices have had important roles in leveraging firms to become more actively involved in environment‐related disclosure, in which climate risk reporting is central to evaluating whether and to what extent a firm and its operations are friendly to the environment. Along with the growth of the UN Principles for Responsible Investing in 2005, one of the most recent global initiatives that has been formed is the Taskforce on Climate‐Related Financial Disclosures (TCFD), which has considered the climate‐related financial disclosure recommendations of G20 finance ministers. Given that TCFD recommendations have recently been released for a broad domain of players (such as banks, investors, insurers and governments) in various countries (e.g., New Zealand, the United States and Japan), we surveyed the most recent studies on the TCFD by using a conceptual framework for climate‐related disclosures focusing on studies published worldwide. On the basis of a thorough review, we highlight the essential functions of financial markets and also provide the critical implications for different market players ranging from providers to supporters of the TCFD. Our study offers a timely conceptual review of the TCFD which is critical for stimulating sustainable investments, climate finance and enhanced corporate reporting.
Hydrogel viscoelasticity modulates migration and fusion of mesenchymal stem cell spheroids
Authors: Wu David T. , Diba Mani , Yang Stephanie , Freedman Benjamin R. , Elosegui‐Artola Alberto , Mooney David J.
Published: December 2022

Multicellular spheroids made of stem cells can act as building blocks that fuse to capture complex aspects of native in vivo environments, but the effect of hydrogel viscoelasticity on cell migration from spheroids and their fusion remains largely unknown. Here, we investigated the effect of viscoelasticity on migration and fusion behavior of mesenchymal stem cell (MSC) spheroids using hydrogels with a similar elasticity but different stress relaxation profiles. Fast relaxing (FR) matrices were found to be significantly more permissive to cell migration and consequent fusion of MSC spheroids. Mechanistically, inhibition of ROCK and Rac1 pathways prevented cell migration. Moreover, the combination of biophysical and biochemical cues provided by fast relaxing hydrogels and platelet‐derived growth factor (PDGF) supplementation, respectively, resulted in a synergistic enhancement of migration and fusion. Overall, these findings emphasize the important role of matrix viscoelasticity in tissue engineering and regenerative medicine strategies based on spheroids.
Clients' experiences of online therapy in the early stages of a COVID‐19 world: A scoping review
Authors: van Kessel Kirsten , de Pont Sarita , Gasteiger Chiara , Goedeke Sonja
Published: December 2022

The emergence of the COVID‐19 pandemic in 2019 forced an abrupt shift in the modality through which psychotherapy was delivered and online therapy became the only viable option for clients. Research regarding experiences of online therapy during the early stages of the COVID‐19 pandemic is minimal, however, and has largely focussed on therapists' experiences of delivering online treatment, as opposed to clients' experiences of receiving it. A scoping review was undertaken to establish what is known from the existing literature about clients' experiences of online therapy during the initial stages of the COVID‐19 pandemic and identify gaps in the current knowledge. Searches were conducted across four academic databases: Scopus, EBSCO CINAHL Complete, EBSCO MEDLINE and OVID PsycInfo; the literature was excluded based on established PICOS criteria. Data were summarised through data charting and synthesised by way of inductive content analysis. A total of five articles were identified. All articles focussed on online therapy using video or audio conferencing, and four of the five studies examined clients with eating disorders. Inductive content analysis identified seven categories, as follows: preference for face‐to‐face therapy; appreciation of accessibility and convenience; online format hindered connection; positive experience of online therapy; individual client differences impacted experience; strong therapeutic alliance indicative of positive experience; and gratitude for continuation of treatment. Future research could explore clients' experiences of online therapy in a “post‐pandemic” world and include a broader range of client populations and online therapy approaches in the COVID‐19 context.
Chemical Composition and Antimicrobial Effect of Western Ethiopian Propolis
Authors: Afata Tariku Neme , Dekebo Aman
Published: December 2022

Propolis or bee glue is commonly named as a natural resinous mixture produced by honeybees (Apis mellifera) from substances collected from parts of plants, buds, and exudate. The result of the ethyl acetate ‐ methanol (3 : 2) volume by volume fraction yielded a total of two compounds namely betulinic acid and β‐amyrin isolated from Bodji Dirmaji and Fincha'a district propolis, respectively. The crude ethanolic extract was portioned with the different solvent systems by increasing the polarities in the following order of hexane, ethyl acetate, and methanol. Column chromatographic method on normal silica gel was used to isolate the compounds. The structures of the compounds were characterized using 1D NMR techniques. The study revealed that western Ethiopian propolis was rich in saponins, tannins, flavonoids, steroids, triterpenes, and glycosides. The antibacterial activity for the isolated compound (betulinic acid) showed the highest inhibition for S. aureus (11.2±1.6), E. coli (17.7±1.1), and A. niger (12.6±1.2) mm.
COVID‐associated non‐vasculitic thrombotic retiform purpura of the face and extremities: A case report
Authors: Bunch Connor M. , Zackariya Nuha , Thomas Anthony V. , Langford Jack H. , Aboukhaled Michael , Thomas Samuel J. , Ansari Aida , Patel Shivani S. , Buckner Hallie , Miller Joseph B. , Annis Christy L. , Quate‐Operacz Margaret A. , Schmitz Leslie A. , Pulvirenti Joseph J. , Konopinski Jonathan C. , Kelley Kathleen M. , Hassna Samer , Nelligan Luke G. , Walsh Mark M.
Published: December 2022

SARS‐CoV‐2 infection can manifest many rashes. However, thrombotic retiform purpura rarely occurs during COVID‐19 illness. Aggressive anti‐COVID‐19 therapy with a high‐dose steroid regimen led to rapid recovery. This immunothrombotic phenomenon likely represents a poor type 1 interferon response and complement activation on the endothelial surface in response to acute infection.
Chronic myelogenous leukemia presenting with Morel Lavallée lesion: A case report of a rare presentation
Authors: Mohamed Sara S. I. , Qasim Hana Mahmoud , Mahfouz Ahmed , Osman Maab A. , Ahmed Ashraf O. E. , Al‐Azewi Safa H. , Yassin Mohamad A. , Fareed Shehab
Published: December 2022

Chronic myelogenous leukemia is a myeloproliferative neoplasm characterized by the BCR‐ABL1 fusion gene and the development of the Philadelphia chromosome, which leads to an increase in granulocytes and bone marrow myeloid precursors in the blood, it can lead to many possible complications depending on the disease stage at the time of diagnosis. The Morel‐Lavallée lesion (MLL) is a closed traumatic soft‐tissue degloving injury, that results from the separation of the hypodermis from the underlying fascia, with resultant hemo‐lymphatic fluid collection between the tissue layers. We report a case of a 48‐year‐old male patient, with no chronic illnesses, who presented with 2 weeks history of posterior chest wall pain and swelling. Initial investigation showed a white blood cell count of 364.4 × 103/μl. Bone marrow pathology report findings were consistent with chronic myeloid leukemia (CML), and the BCR‐ABL test came positive. CT chest with contrast showed a large chest wall lesion, suggestive of a Morel‐Lavallee lesion. Ultrasound‐guided aspiration of the lesion yielded 20 mm of fluid from the thick hematoma. Histopathology of the fluid showed Necrotic debris with mixed inflammation. Patient's condition improved, and he was discharged on Dasatinib with follow‐up in hematology and surgery clinics.
Essential Role of Pulping Route on Thermal Stability Performance of Rice Straw‐Based Nanocelluloses
Authors: Basta Altaf H. , Lotfy Vivian F.
Published: December 2022

There is a strong interest in production of thermally stable nanocelluloses for further applications. Despite the enormous success achieved in preparing cellulose nanocrystals (CNCs) by acid catalyst technique, these products remain a major challenge due to the lack of thermal stability which till now could not be solved. This work deals with assessing the role of alkali, neutral, acid, and organosolvent pulping agents on thermal stability performances of produced rice straw (RS)‐based CNCs. This property was estimated by thermogravimetric analysis. The data obtained indicated that employing a pulping to RS > 4.75 mm with sodium hydroxide in the presence of anthraquinone‐sodium borohydride can help address these challenges by providing CNCs with highest activation energy as well as a lower aspect length‐to‐width ratio according to transmission electron microscopy images.
A Nitrogen‐Doped Porous Carbon Supported Copper Catalyst from a Scalable One‐Step Method for Efficient Carbon Dioxide Electroreduction
Authors: Vijayakumar Amruthalakshmi , Zhao Yong , Wang Kezhong , Chao Yunfeng , Chen Haiqun , Wang Caiyun , Wallace Gordon G.
Published: December 2022

In this work, a scalable one‐step glucose blowing method has been used to prepare a porous N‐doped carbon supported Cu nanoparticles (Cu‐NC) composite catalyst for CO2 electroreduction. This Cu‐NC catalyst demonstrates efficient catalytic activity for CO2‐to‐C1 product (CO and formate) conversion, with a high efficiency of 69 % at an overpotential of 590 mV. The excellent catalytic activity is correlated to the structure of this composite and the N‐species (pyridinic and graphitic nitrogen) in the carbonaceous matrix that may promote the CO2 adsorption and subsequent formation of reduction reaction intermediates and products.
Electrochemical Synthesis of 5‐Benzylidenebarbiturate Derivatives and Their Application as Colorimetric Cyanide Probe
Authors: El‐Dash Yara S. , Mahmoud Amr M. , El‐Mosallamy Sally S. , El‐Nassan Hala B.
Published: December 2022

A highly efficient, fast, catalyst‐free, and atom economical method was developed for the synthesis of 5‐benzylidenebarbiturates. Thus, reacting barbituric acid and aldehydes in water as a green solvent under electrochemical conditions afforded the synthesis of the target compounds in six minutes and in highly pure forms. The effects of solvent, reaction time, temperature, electrolyte, and electrode material were studied to optimize the reaction conditions. The scope of the reaction was broadened by the synthesis of 5‐(arylidene)barbiturate derivatives 3 a–3 q using different aldehydes. Calculation of the green chemistry metrics proved the efficiency of the reaction in terms of E‐factor, mass intensity, mass productivity, and reaction mass efficiency. Compound 3 g [5‐(4‐(dimethylamino)benzylidene) barbiturate] was used for the colorimetric detection of cyanide ion over dynamic linear range 1–25 μM with limit of detection (LOD) of 0.86 μM.
LiNi0.5Mn1.5O4 Thin Films Grown by Magnetron Sputtering under Inert Gas Flow Mixtures as High‐Voltage Cathode Materials for Lithium‐Ion Batteries
Authors: Darjazi Hamideh , Madinabeitia Iñaki , Zarrabeitia Maider , Gonzalo Elena , Acebedo Begoña , Javad Rezvani S. , Fernández‐Carretero Francisco José , Nobili Francesco , García‐Luis Alberto , Muñoz‐Márquez Miguel Ángel
Published: December 2022

Delivering a commercial high‐voltage spinel LiNi0.5Mn1.5O4 (LNMO) cathode electrode for Li‐ion batteries would result in a significant step forward in terms of energy density. However, the structural ordering of the spinel and particle size have considerable effects on the cathode material's cyclability and rate capability, which are crucial challenges to address. Here, a novel mid‐frequency alternating current dual magnetron sputtering method was presented, using different Ar‐N2 gas mixtures ratios for the process gas to prepare various LNMO thin films with highly controlled morphology and particle size; as determined from X‐ray diffraction, Raman spectroscopy and electron microscopy. It resulted in enhanced cycling and rate performance. This processing method delivered N‐containing LNMO thin film electrodes with up to 15 % increased discharge capacity at 1 C (120 mAh g−1) with respect to standard LNMO (grown under only Ar gas flow) thin film electrodes, along with outstanding rate performance up to 10 C (99 mAh g−1) in the operating voltage window 3.5–4.85 V vs. Li+/Li. Besides, electrochemical impedance spectroscopy results showed that the intricate phase transitions present in standard LNMO electrodes were almost suppressed in N‐containing LNMO thin films grown under different Ar‐N2 gas flow mixtures.
Understanding PFOS Adsorption on a Pt Electrode for Electrochemical Sensing Applications
Authors: Gogoi Pratahdeep , Yao Yu , Li Yuguang C.
Published: December 2022

Per‐ and polyfluroalkyl substances (PFAS) are drawing increasing attention in the research community due to their wide spread applications and their toxicity to animals and humans. Effective early detection method of PFAS chemicals in aqueous environment is important to reduce exposure and mitigate the potential toxic effects. This study focuses on the electrochemical detection of per‐fluoro octane sulfonate (PFOS) with differential pulse voltammetry and electrochemical impedance spectroscopy on a bare platinum electrode. We observe three distinct regions of adsorption behaviors with respect to PFOS concentration from 0–1000 nM, reflecting changes in the modes of adsorption due to different adsorbate‐adsorbate interactions on a bare electrode. The adsorption isotherm constant for PFOS adsorption on a Pt electrode is calculated to be 1.6×1012 cm3 mol−1 from fitting the electrochemical data with a modified Langmuir isotherm model.
Ni3Se4 Nanostructure as a Battery‐type Positive Electrode for Hybrid Capacitors
Authors: Reddy Inta Harish , Koppisetti Heramba V. S. R. M. , Ghosh Sourav , Roy Avishek , Mahalingam Venkataramanan
Published: December 2022

Battery‐type supercapacitors have drawn significant attention due to their high charge storage ability resulted from the combined surface and intercalation redox phenomenon. In this regard, nickel chalcogenides are expected to deliver high specific capacity accompanied by their dominant battery‐type supercapacitor features. Herein, we have developed a facile one step solvothermal route to prepare pure phase Ni3Se4 nanostructures and attempted to understand the synthetic factors such as solvent and Ni/Se ratio on the formation of Ni3Se4 phase. The obtained Ni3Se4 nanostructures were subjected to the supercapacitor performance evaluation by loading them onto carbon paper and found that the electrode materials are able to store the charge through dominant intercalation redox process (battery‐type storage mechanism). Among them, Ni3Se4 (NS‐15E(1)) synthesized in water/ethanol (2 : 3) mixture with Ni/Se (1 : 1) ratio has displayed a high specific capacity of 376 C g−1 (104 mA hg−1) at a current density of 1 A g−1 in 2 m KOH. The superior charge storage of NS‐15E(1) could be attributed to the improved redox process facilitated by the easier diffusion of electrolyte ions into the bulk of the material. Furthermore, a hybrid device fabricated by using Activated charcoal (AC) and NS‐15E(1) as negative and positive electrodes, respectively has showed an extended voltage window of 1.6 V and achieved a high energy density ∼20 Wh Kg−1 at a power density of 329 W kg−1.