bluuebunny/crossref_metadata_2025 huggingface dataset:
Phase–Property Diagrams for Multicomponent Oxide Systems toward Materials Libraries
Authors: Velasco Leonardo , Castillo Juan S. , Kante Mohana V. , Olaya Jhon J. , Friederich Pascal , Hahn Horst
Published: September 2021

Exploring the vast compositional space offered by multicomponent systems or high entropy materials using the traditional route of materials discovery, one experiment at a time, is prohibitive in terms of cost and required time. Consequently, the development of high‐throughput experimental methods, aided by machine learning and theoretical predictions will facilitate the search for multicomponent materials in their compositional variety. In this study, high entropy oxides are fabricated and characterized using automated high‐throughput techniques. For intuitive visualization, a graphical phase–property diagram correlating the crystal structure, the chemical composition, and the band gap are introduced. Interpretable machine learning models are trained for automated data analysis and to speed up data comprehension. The establishment of materials libraries of multicomponent systems correlated with their properties (as in the present work), together with machine learning‐based data analysis and theoretical approaches are opening pathways toward virtual development of novel materials for both functional and structural applications.
Design of NiOx/Carbon Heterostructure Interlayer to Improve Hole Extraction Efficiency of Inverted Perovskite Solar Cells
Authors: Yin Xin , Zhai Jifeng , Ingabire Providence Buregeya , Du Pingfan , Chen Wei‐Hsiang , Song Lixin , Xiong Jie , Ko Frank
Published: September 2021

An efficient hole transport layer (HTL) with desirable charge separation and hole extraction efficiency is crucial for inverted perovskite solar cells. However, the interfacial trap recombination loss and mismatched band alignment limit the actual performance of device, especially the open‐circuit voltage (VOC). To address this issue, a unique NiOx/carbon heterostructure is designed as efficient anode interlayer for optimizing the interfacial charge transport dynamics between HTL and perovskite. Such a buffer interlayer can significantly contribute to the improved hole conductivity and hole extraction efficiency at HTL/perovskite interface. Moreover, the more favorable gradient energy level alignment can be formed to increase the interfacial electric field, inhibit the nonradiative recombination, and minimize the VOC loss. Therefore, the champion device achieves 19.51% efficiency with high VOC of 1.13 V, close to the highest power conversion efficiencies of MAPbI3 device. This work suggests that interface design can be an alternative approach to fabricate efficient inverted NiO‐based devices.
Deformable and Robust Core–Shell Protein Microcapsules Templated by Liquid–Liquid Phase‐Separated Microdroplets
Authors: Xu Yufan , Shen Yi , Michaels Thomas C. T. , Baumann Kevin N. , Vigolo Daniele , Peter Quentin , Lu Yuqian , Saar Kadi L. , Vella Dominic , Zhu Hongjia , Li Bing , Yang He , Guttenplan Alexander P. M. , Rodriguez‐Garcia Marc , Klenerman David , Knowles Tuomas P. J.
Published: September 2021

Microcapsules are a key class of microscale materials with applications in areas ranging from personal care to biomedicine, and with increasing potential to act as extracellular matrix (ECM) models of hollow organs, tissues, or biomolecular condensates. Such capsules are conventionally generated from non‐ECM materials including synthetic polymers. Here, robust microcapsules with controllable shell thickness from physically‐ and enzymatically‐crosslinked gelatin are fabricated, and a core–shell architecture is achieved by exploiting a liquid–liquid phase‐separated aqueous system in a one‐step microfluidic process. Microfluidic mechanical testing reveals that the mechanical robustness of thicker‐shell capsules could be controlled through modulation of the shell thickness. Furthermore, the microcapsules demonstrate environmentally‐responsive deformation, including buckling driven by osmosis and external mechanical forces. A sequential release of cargo species is obtained through the degradation of the capsules. Stability measurements show the capsules are stable at 37 °C for more than 2 weeks. Finally, through gel–sol transition, microgels function as precursors for the formation of all‐aqueous liquid–liquid phase‐separated systems that are two‐phase or multiphase. These smart capsules that can undergo phase transition are promising models of hollow biostructures, microscale drug carriers, and building blocks or compartments for active soft materials and robots.
Activation of FGFR2 Signaling Suppresses BRCA1 and Drives Triple‐Negative Mammary Tumorigenesis That is Sensitive to Immunotherapy
Authors: Lei Josh Haipeng , Lee Mi‐Hye , Miao Kai , Huang Zebin , Yao Zhicheng , Zhang Aiping , Xu Jun , Zhao Ming , Huang Zenan , Zhang Xin , Chen Si , Jiaying NG , Feng Yuzhao , Xing Fuqiang , Chen Ping , Sun Heng , Chen Qiang , Xiang Tingxiu , Chen Lin , Xu Xiaoling , Deng Chu‐Xia
Published: September 2021

Fibroblast growth factor receptor 2 (FGFR2) is a membrane‐spanning tyrosine kinase that mediates FGF signaling. Various FGFR2 alterations are detected in breast cancer, yet it remains unclear if activation of FGFR2 signaling initiates tumor formation. In an attempt to answer this question, a mouse model berrying an activation mutation of FGFR2 (FGFR2‐S252W) in the mammary gland is generated. It is found that FGF/FGFR2 signaling drives the development of triple‐negative breast cancer accompanied by epithelial‐mesenchymal transition that is regulated by FGFR2‐STAT3 signaling. It is demonstrated that FGFR2 suppresses BRCA1 via the ERK‐YY1 axis and promotes tumor progression. BRCA1 knockout in the mammary gland of the FGFR2‐S252W mice significantly accelerated tumorigenesis. It is also shown that FGFR2 positively regulates PD‐L1 and that a combination of FGFR2 inhibition and immune checkpoint blockade kills cancer cells. These data suggest that the mouse models mimic human breast cancers and can be used to identify actionable therapeutic targets.
Porous MOFs–Zinc Cobaltite/Carbon Composite Nanofibers for High Lithium Storage
Authors: Dai Zixin , Long Zhiwen , Shi Chu , Wu Caiqin , Qiao Hui , Wang Keliang
Published: September 2021

The zinc cobaltite possesses merit of high theoretical specific capacity. However, issues of low conductivity and volume expansion during lithiation and delithiation lead to severe capacity fading. In this work, a porous zinc cobaltite/carbon composite nanofiber is synthesized with a metal–organic frameworks (MOFs) structure through electrospinning, in situ growth, and hydrothermal reaction. The obtained zinc cobaltite/carbon composite nanofibers have an improved specific surface area (90.61 m2 g‐1), enabling excellent electrochemical performance as anode materials in Li‐ion batteries. Briefly, a high initial discharge capacity of 2468 mAh g‐1 and reversible capacity of 2008 mAh g‐1 after the 200 cycles, and an outstanding rate capability of 937 mAh g‐1 at 2 A g‐1 are achieved. The capacity fading of MOFs–zinc cobaltite/carbon composite nanofibers is significantly improved, which can be attributed to the following reasons: i) the MOFs structure effectively relieve the strain stemming from volume expansion of transition metal; ii) the abundance of mesoporous structure facilitates the electron transport for Li+ diffusion rate by shortening the Li‐ion diffusion path during lithiation/delithiation process; iii) the carbon nanofibers with excellent conductivity enable efficient conduction efficiency of lithium ions and electrons. The proposed strategy offers a new perspective to prepare high‐performance electrode for lithium‐ion batteries.
Frontier luminous strategy of functional silica nanohybrids in sensing and bioimaging: From ACQ to AIE
Authors: Xu Lijie , Jiang Xiaoping , Liang Kang , Gao Meng , Kong Biao
Published: September 2021

Fluorescent silica organic–inorganic nanohybrids which combine designable luminescence performance of organic fluorescent dyes and various outstanding advantages of silica nanomaterials have attracted increasing research interests in these fascinating areas. Optical transparency and facile functional modification properties of silica material provide great opportunities to integrate desired fluorescent molecules for various frontier luminous applications. However, conventional organic dyes are typically subject to aggregation‐caused quenching due to their aggregation in silica matrix, which could be detrimental for their performance in sensing and biomedical applications. The appearance of aggregation‐induced emission luminogens (AIEgens) paves a new way for developing highly efficient fluorescent silica nanohybrids (FSNs). FSNs with intensive luminescence could be obtained due to the formation of aggregates and the restricted intramolecular motion of AIEgens in silica inorganic matrix. In this review, the reported fabrication methodologies of various FSNs based on colloidal silica nanoparticles (SNs) and mesoporous SNs including physical entrapment and covalent strategies are summarized. Especially, the AIEgens‐functionalized silica hybrid nanomaterials are introduced in detail. Furthermore, chemical sensing, biosensing, and bioimaging applications of resultant FSNs are also discussed.
Enhancing magnetic hyperthermia in ferrite nanoparticles through shape anisotropy and surface hybridization
Authors: Jiménez Gloria L. , Thevi Guntnur Rohini , Guiliani Jason , Romero Gabriela
Published: September 2021

Magnetic hyperthermia has been studied for the past two decades in cancer treatments as the local heat generated by magnetic nanoparticles under applied alternating magnetic fields is sufficient to kill cancer cells. More recently, it has been explored for controlling biological signaling through heat‐sensitive transmembrane channels. It is of great interest to produce magnetic nanoparticles with high heat transducing efficiency to minimize potential off‐target heating effects. Here, we describe shape anisotropy and particle hybridization as possible routes to augment magnetic hyperthermia in ferrite nanoparticles. Zinc substituted magnetite core and core‐shell cubic nanoparticles with different sizes were synthetized. It was found that nanoparticles shape and composition are altered from cubic to flower‐like, and to a more franklinite rich phase as size increased. Hybridization with a cobalt shell allowed to enhance nanoparticle magnetic coercivity and specific power loss. The optimized core‐shell nanoparticles were tested to induce cellular activity in hippocampal neurons.

TOPICAL HEADING

Inorganic Materials: Synthesis and Processing.
Rates of longitudinal change in 18F‐flortaucipir PET vary by brain region, cognitive impairment, and age in atypical Alzheimer's disease
Authors: Phillips Jeffrey S. , Nitchie Frederick J. , Da Re Fulvio , Olm Christopher A. , Cook Philip A. , McMillan Corey T. , Irwin David J. , Gee James C. , Dubroff Jacob G. , Grossman Murray , Nasrallah Ilya M. ,   for the Alzheimer's Disease Neuroimaging Initiative
Published: September 2021

Introduction

Longitudinal positron emission tomography (PET) studies of tau accumulation in Alzheimer's disease (AD) have noted reduced increases or frank decreases in tau signal. We investigated how such reductions related to analytical confounds and disease progression markers in atypical AD.

Methods

We assessed regional and interindividual variation in longitudinal change on 18F‐flortaucipir PET imaging in 24 amyloid beta (Aβ)+ patients with atypical, early‐onset amnestic or non‐amnestic AD plus 62 Aβ– and 132 Aβ+ Alzheimer's Disease Neuroimaging Initiative (ADNI) participants.

Results

In atypical AD, 18F‐flortaucipir uptake slowed or declined over time in areas with high baseline signal and older, more impaired individuals. ADNI participants had reduced longitudinal change in early Braak stage regions relative to late‐stage areas.

Discussion

Results suggested radioligand uptake plateaus or declines in advanced neurodegeneration. Further research should investigate whether results generalize to other radioligands and whether they relate to changes of the radioligand binding site structure or accessibility.
Mechanism of the Photodegradation of A‐D‐A Acceptors for Organic Photovoltaics**
Authors: Che Yuxuan , Niazi Muhammad Rizwan , Izquierdo Ricardo , Perepichka Dmitrii F.
Published: September 2021

Herein, we elucidate the photodegradation pathway of A‐D‐A‐type non‐fullerene acceptors for organic photovoltaics. Using IT‐4F as a benchmark example, we isolated the photoproducts and proved them isomers of IT‐4F formed by a 6‐e electrocyclic reaction between the dicyanomethylene unit and the thiophene ring, followed by a 1,5‐sigmatropic hydride shift. This photoisomerization was accelerated under inert conditions, as explained by DFT calculations predicting a triplet‐mediated reaction path (quenchable by oxygen). Adding controlled amounts of the photoproduct P1 to PM6:IT‐4F bulk heterojunction cells led to a progressive decrease in photocurrent and fill factor attributed to its poor absorption and charge transport properties. The reaction is a general photodegradation pathway for a series of A‐D‐A molecules with 1,1‐dicyanomethylene‐3‐indanone termini, and its rate varies with the structure of the donor and acceptor moiety.
Palladium‐Catalyzed Perfluoroalkylative Carbonylation of Unactivated Alkenes: Access to β‐Perfluoroalkyl Esters
Authors: Zhang Youcan , Geng Hui‐Qing , Wu Xiao‐Feng
Published: September 2021

Transition‐metal‐catalyzed multi‐component carbonylation represents an efficient strategy for the preparation of various functionalized carbonyl‐containing compounds. Herein, we report a general palladium‐catalyzed perfluoroalkylative carbonylation of unactivated alkenes using inexpensive and readily available carbon monoxide as the C1 source and perfluoroalkyl halides as the coupling partner. A wide range of phenols and alcohols were transformed into the corresponding β‐perfluoroalkyl esters in high yields with broad functional group tolerance and good chemoselectivity. Additionally, alkyl halides can be utilized as alkoxy source as well to give the desired esters. Moreover, several pharmaceutical and bio‐active molecules were also suitable substrates for this one‐pot multi‐component carbonylation process to give the targeted products in good yields.
Bayesian Optimization of High‐Entropy Alloy Compositions for Electrocatalytic Oxygen Reduction**
Authors: Pedersen Jack K. , Clausen Christian M. , Krysiak Olga A. , Xiao Bin , Batchelor Thomas A. A. , Löffler Tobias , Mints Vladislav A. , Banko Lars , Arenz Matthias , Savan Alan , Schuhmann Wolfgang , Ludwig Alfred , Rossmeisl Jan
Published: September 2021

Active, selective and stable catalysts are imperative for sustainable energy conversion, and engineering materials with such properties are highly desired. High‐entropy alloys (HEAs) offer a vast compositional space for tuning such properties. Too vast, however, to traverse without the proper tools. Here, we report the use of Bayesian optimization on a model based on density functional theory (DFT) to predict the most active compositions for the electrochemical oxygen reduction reaction (ORR) with the least possible number of sampled compositions for the two HEAs Ag‐Ir‐Pd‐Pt‐Ru and Ir‐Pd‐Pt‐Rh‐Ru. The discovered optima are then scrutinized with DFT and subjected to experimental validation where optimal catalytic activities are verified for Ag–Pd, Ir–Pt, and Pd–Ru binary alloys. This study offers insight into the number of experiments needed for optimizing the vast compositional space of multimetallic alloys which has been determined to be on the order of 50 for ORR on these HEAs.
A Phase Inversion‐Based Microfluidic Fabrication of Helical Microfibers towards Versatile Artificial Abdominal Skin
Authors: Liu Ji‐Dong , Du Xiang‐Yun , Chen Su
Published: September 2021

Microfluidic spinning technology (MST), incorporating microfluidics with chemical reactions, has gained considerable interest for constructing anisotropic advanced microfibers, especially helical microfibers. However, these efforts suffer from the limited material choices, restricting their applications. Here, a new phase inversion‐based microfluidic spinning (PIMS) method is proposed for producing helical microfibers. This method undergoes a physicochemical phase inversion process, which is capable of efficiently manufacturing strong (tensile stress of more than 25 MPa), stretchable, flexible and biocompatible helical microfibers. The helical microfibers can be used to fabricate bi‐oriented stretchable artificial abdominal skin, preventing incisional hernia formation and promoting the wound healing without conglutination. This research not only offers a universal approach to design helical microfibers but also provides a new insight into artificial skin.
Stabilization of the Elusive Antimony(I) Cation and Its Coordination Complexes with Transition Metals
Authors: Kumar Vikas , Gonnade Rajesh G. , Yildiz Cem B. , Majumdar Moumita
Published: September 2021

Upon stabilization by 5,6‐bis(diisopropylphosphino)acenaphthene to form compound 1, the fugitive antimony (I) cation exhibited nucleophilic behavior towards coinage metals. Compound 1 was strategically synthesized at room temperature from SbCl3, the bis(phosphine), and trimethylsilyl trifluoromethanesulfonate taken in a 1:2:3 ratio, whereby the bis(phosphine) plays the dual role of a reductant and a supporting ligand. The generation of 1 involves two‐electron oxidation of the ligand to form a P−P bonded diphosphonium dication. Compound 1 was separated from this dication to give both products in pure form in moderate yields. Despite the overall positive charge, the SbI site in 1 was found to bind to metal centers, forming complexes with AuI, AgI and CuI. Compound 1 reduced CuII to CuI and formed a coordination complex with the resulting CuI species. The effects of the electron‐rich bis(phosphine) and the constrained peri geometry in stabilizing and enhancing the nucleophilicity of 1 have been rationalized through computational studies.
Mechanical behavior of 3D‐printed polymeric metamaterials for lightweight applications
Authors: Truszkiewicz Eliza , Thalhamer Andreas , Rossegger Marlene , Vetter Mario , Meier Gerald , Rossegger Elisabeth , Fuchs Peter , Schlögl Sandra , Berer Michael
Published: September 2021

Artificially structured materials, also called metamaterials, can achieve very unique properties due to the fact that their attributes are mainly derived from the design of the structures. This work gives an overview of the mechanical behavior of four differently designed and 3D‐printed metamaterial structures. For each structure, both, the printing technique and the materials used for printing were varied. In total four different polymers were investigated and processed with three different 3D‐printing techniques. Their mechanical behavior was studied by compression tests, which showed the wide range of material properties that can be achieved by utilizing the different materials/3D‐printing techniques. In addition, bending tests of 3D‐printed bending specimens were conducted to provide material data for subsequent finite element simulation of the structures. The comparison of experiments and numerical simulations gave further insight into local deformation mechanisms and allowed for a better understanding of the overall deformation behavior.
Maternal immunization with Group B Streptococcus six‐valent polysaccharide conjugate vaccine supported by lack of toxicity in rat and rabbit fertility and developmental toxicity studies
Authors: Catlin Natasha R. , Cappon Gregg D. , Engel Scott , Rohde Cynthia , Nowland William S. , Buitrago Sandra , Scully Ingrid , Anderson Annaliesa S. , Bowman Christopher J.
Published: September 2021

A maternal Group B Streptococcus (GBS) six‐valent polysaccharide conjugate vaccine (GBS6) is being developed to protect neonates and infants up to 3 months of age through passive transfer of antibodies from the mother to the infant. Fertility and developmental toxicity studies were conducted in female Sprague Dawley rats and New Zealand White rabbits with GBS6 (20 μg capsular polysaccharide/serotype formulated with or without AlPO4, the highest clinical dose). Females were administered the full human dose of the GBS6 formulation intramuscularly twice prior to mating and twice during gestation, to ensure that high antibody levels were maintained throughout gestation and lactation. Approximately, half of the rats and rabbits were evaluated at the end of gestation, and the remainder were evaluated at the end of lactation. Maternal blood for GBS6 serology, to measure antibody titers to the GBS6 antigens, was collected prior to the first dose, prior to mating, and at each necropsy. Blood for serology was also collected from offspring at the end of gestation and lactation. In both species, there was no evidence of vaccine‐related effects on fertility, embryo‐fetal development, or postnatal development of the offspring, supporting regulatory guidance that single‐species evaluation would have been sufficient. Functional serum antibodies to all six serotypes in the vaccine were confirmed in maternal animals and functional serum antibodies to one or more of the six serotypes was also confirmed in some rat offspring and most of the rabbit offspring. The results of these studies supported the safety of GBS6 vaccine administration to pregnant women.
Combined Effects of Low‐Frequency Pulsed Electromagnetic Field and Melatonin on Ovariectomy‐Induced Bone Loss in Mice
Authors: Huang Jinming , Li Yi , Wang Liqiong , He Chengqi
Published: September 2021

Pulsed electromagnetic field (PEMF) therapy and melatonin (MEL) supplementation are expected to be important strategies for the treatment of osteoporosis. The aim of the current study was to investigate the efficacy of PEMF therapy, MEL supplementation, a combination of PEMF therapy, and MEL supplementation (PEMF + MEL) in mice with bilateral ovariectomy (OVX)‐induced osteoporosis. Forty 12‐week‐old female C57/BL mice were randomly assigned to five groups (n = 8/group): OVX, PEMF, MEL, PEMF + MEL, and sham‐operation (sham) groups. All mice in the first four groups were subjected to OVX. The mice in the PEMF and PEMF + MEL groups were exposed to PEMF (75 Hz, 1.6 mT, 1 h/day for 12 weeks), while those in the MEL and PEMF + MEL groups were administered MEL (50 mg/kg, i.p.). Body mass, micro‐computed tomography, histology, immunohistochemistry, and real‐time polymerase chain reaction were performed. PEMF + MEL treatment enhanced bone volume fraction (BV/TV) 2.2‐fold over OVX control (P < 0.001) and increased expression levels of collagen type I (COL1) 1.9‐fold and bone morphogenetic protein 2 (BMP2) 2.5‐fold. PEMF + MEL also reduced the ratio of bone surface/bone volume (BS/BV) by 40% (P < 0.05) and appeared to reduce the number of osteoclasts in the metaphysis area. Preservation of bone value and bone microarchitecture in the combined therapy group were found to be superior to those in the single treatment groups. However, there were no apparent differences between the PEMF and MEL groups. The use of a combination of PEMF therapy and MEL supplementation may be an effective method to treat osteoporosis. © 2021 Bioelectromagnetics Society.
A high cell density perfusion process for Modified Vaccinia virus Ankara production: Process integration with inline DNA digestion and cost analysis
Authors: Gränicher Gwendal , Babakhani Masoud , Göbel Sven , Jordan Ingo , Marichal‐Gallardo Pavel , Genzel Yvonne , Reichl Udo
Published: September 2021

By integrating continuous cell cultures with continuous purification methods, process yields and product quality attributes have been improved over the last 10 years for recombinant protein production. However, for the production of viral vectors such as Modified Vaccinia virus Ankara (MVA), no such studies have been reported although there is an increasing need to meet the requirements for a rising number of clinical trials against infectious or neoplastic diseases. Here, we present for the first time a scalable suspension cell (AGE1.CR.pIX cells) culture‐based perfusion process in bioreactors integrating continuous virus harvesting through an acoustic settler with semi‐continuous chromatographic purification. This allowed obtaining purified MVA particles with a space‐time yield more than 600% higher for the integrated perfusion process (1.05 × 1011 TCID50/Lbioreactor/day) compared to the integrated batch process. Without further optimization, purification by membrane‐based steric exclusion chromatography resulted in an overall product recovery of 50.5%. To decrease the level of host cell DNA before chromatography, a novel inline continuous DNA digestion step was integrated into the process train. A detailed cost analysis comparing integrated production in batch versus production in perfusion mode showed that the cost per dose for MVA was reduced by nearly one‐third using this intensified small‐scale process.
Conditional survival of metastatic clear cell renal cell carcinoma: How prognosis evolves after cytoreductive surgery of primary tumor
Authors: Shen Haixiang , Liu Jin , Liu Wei , Sun Jiazhu , Zheng Xiangyi , Teng Lisong , Wang Xiao , Xie Liping
Published: September 2021

Introduction

Cytoreductive surgery is one of the recommended treatments for metastatic renal cell carcinoma, while the prognostic information of these patients treated with cytoreductive surgery is limited. In this study, we aimed to investigate the survival profiles based on conditional survival (CS) estimates in metastatic clear cell renal cell carcinoma (mccRCC) patients treated with cytoreductive surgery of primary tumor.

Methods and materials

We identified and extracted mccRCC patients from the Surveillance, Epidemiology, and End Results database. We used Kaplan–Meier method to perform CS analyses. A multivariate Cox regression model was applied to explore the changes of well‐known prognostic factors.

Results

Conditional overall survival (COS) and conditional cancer‐specific survival (CCSS) improved increasingly at all periods of survivorships compared to survival estimates at baseline in overall population of mccRCC. The 36‐month COS improved by 3.3%–6.4% given per 12 additional months of survivorships and the CCSS improved significantly from 45.1% (95% CI 42.8–47.3) at 12 months to 67.1% (95% CI 62.0–71.7) at 60 months. Much more survival gain was observed in patients with advanced disease. Furthermore, the prognostic significance of age and pathological factors diminished and even disappeared in a long‐term survivorship.

Conclusions

Conditional overall survival and CCSS improved with time dynamically in mccRCC patients treated with cytoreductive surgery of primary tumor. Patients with advanced disease achieved significant survival gain and even could harvest a better prognosis given that the time of survivorship exceeds a certain period. Our findings could provide valuable and practical data for patient counseling and surveillance strategy making.
Engineering of Silicon Core‐Shell Structures for Li‐ion Anodes
Authors: Rage Bastien , Delbegue Diane , Louvain Nicolas , Lippens Pierre‐Emmanuel
Published: September 2021

The amount of silicon in anode materials for Li‐ion batteries is still limited by the huge volume changes during charge‐discharge cycles. Such changes lead to the loss of electrical contacts, as well as mechanical and surface electrolyte interphase (SEI) instabilities, strongly reducing the cycle life. Core‐shell structures have attracted a vast research interest due to the possibility of modifying some properties with a judicious choice of the shell. It is, for example, possible to improve the electronic conductivity and ionic diffusion, or buffer volume variations. This review gives a comprehensive overview of the recent developments and the different strategies used for the design, synthesis and electrochemical performance of silicon‐based core‐shells. It is based on a selection of the main types of silicon coatings reported in the literature, including carbon, inorganic, organic and double‐layer coatings, Finally, a summary of the advantages and drawbacks of these different types of core‐shells as anode materials for Li‐ion batteries and some insightful suggestions in regards to their use are provided.
Macrocyclic Inorganic Tin‐Containing Oxo Clusters: Heterometallic Strategy for Configuration and Catalytic Activity Modulation
Authors: Wang Di , Chen Guang‐Hui , Yuan Lv‐Bing , Feng Cheng‐Cheng , Zhang Jian , Zhang Lei
Published: September 2021

In this work, the first examples of inorganic macrocyclic tin‐oxo clusters which are stabilized by sulfate ligands are reported. As determined by X‐ray diffraction and photoelectron spectroscopy analyses, the prepared inorganic Sn10‐oxo cluster displays interesting mixed valence behaviors, with 8 Sn4+ located at the cyclic skeleton and two Sn2+ encapsulated in the center. When further introducing Ti4+ and In3+ ions to the synthetic systems, heterometallic Sn2Ti6 and SnIn5Ti6 complexes with Ti6(SO4)9 and SnIn5(SO4)12 macrocyclic skeletons were prepared whose configuration and packing models were affected by the ionic radius of incorporated metals. Moreover, comparative CO2 reduction experiments confirm that such heterometallic composition can significantly improve the catalytic activities of these inorganic macrocyclic oxo clusters. This work represents a milestone in constructing inorganic tin complexes and also macrocyclic metal oxo clusters with tunable configurations and properties.
Somatic intronic TP53 c.375+5G mutations are a recurrent but under‐recognized mode of TP53 inactivation
Authors: Chui M Herman , Yang Ciyu , Mehta Nikita , Rai Vikas , Zehir Ahmet , Momeni Boroujeni Amir , Ladanyi Marc , Mandelker Diana
Published: September 2021

TP53 is one of the most ubiquitously altered genes in human cancer. The biological impact of rare variants, particularly those located within noncoding regions, remains poorly understood. From interrogation of clinical massively parallel sequencing data from over 55,000 tumors, which included 23,330 tumors with known TP53 mutations, TP53 intron 4 nucleotide substitutions at position c.375+5G were identified in 45 tumors (0.2% of TP53‐mutated cancers), comprising cancers of different organ sites. Loss‐of‐heterozygosity or a second‐hit somatic TP53 mutation was observed in 34 of 40 (85%) informative cases. RT‐PCR analysis showed the c.375+5G>T variant to be associated with aberrantly spliced TP53 mRNA transcripts with concomitant loss of the normal transcript. Immunohistochemical staining for p53 was performed on a representative subset of tumors with TP53 c.375+5G variants (n = 14), all of which showed loss of protein expression (100%; n = 13 complete loss, n = 1 subclonal loss). Our data are consistent with classification of TP53 c.375+5G variants as deleterious intronic mutations that interfere with proper mRNA splicing, ultimately resulting in loss of expression of functional p53 protein. The clinical scenario of a tumor with loss of p53 immunohistochemical staining, yet lacking a detectable TP53 exonic mutation, should therefore prompt consideration of splice‐altering intronic variants.
How elemental composition influences the color of igneous and sedimentary rocks: Case of the High Atlas rocks of Morocco
Authors: El Halim Mouhssin , Daoudi Lahcen , El Alaoui El Fels Abdelhafid
Published: September 2021

In spite of color being one of the physicochemical parameters most commonly used to characterize a rock, very limited studies have studied the correlation between the nature, chemical composition, and color of a rock. This study presents a new approach for quantitatively assessing the relationship between these three parameters for specific rocks (example of igneous and sedimentary rocks) collected from the High Atlas of Morocco. A spectrophotometer was used to measure the color of samples, and the measurements were expressed in CIE L*a*b* color system units then converted to Hex color codes. Whereas, the chemical composition of samples was carried out by X‐ray fluorescence. The most abundant oxides in magmatic rock samples are SiO2, Al2O3, Fe2O3, MgO, and CaO, while K2O, Na2O, TiO2, and P2O5 are generally found in trace concentrations. Two categories of clays were studied, non‐calcareous raw materials without carbonate contents (<4% CaO) and calcareous clays or marls (CaO > 10%). Phosphate samples are rich in phosphorus (4.4%‐17.5%) and CaO (11.2%‐42.7%) with relatively low contents of SiO2 (28.5%‐52.2%), Al2O3 (3.1%‐17.5%), and Fe2O3 (1.1%‐6.6%). Results show that the change in the content of these elements from one rock type to another may be indicative of rocks with particular characteristics that do have an impact on color. The main coloration agent of clays was iron, Fe2+, and Fe3+ ions can color clay minerals either red or green or in various shades of orange and brown. However, in marls and phosphates, the high concentration of carbonates inhibits this iron effect by affecting a* (red) and b* (yellow) color parameters, which leads to grayish materials. The same applies to magmatic rocks rich in Fe2O3 and CaO.
Metabolite elucidation of 2‐fluoro‐deschloroketamine (2F‐DCK) using molecular networking across three complementary in vitro and in vivo models
Authors: Gicquel Thomas , Pelletier Romain , Richeval Camille , Gish Alexandr , Hakim Florian , Ferron Pierre‐Jean , Mesli Vadim , Allorge Delphine , Morel Isabelle , Gaulier Jean‐michel
Published: September 2021

This work first aims to investigate metabolites of 2‐fluoro‐deschloroketamine (2F‐DCK), a new arylcyclohexylamine derivatives (a group of dissociative ketamine‐based substances) using two in vitro experimental approaches, and to compare obtained results by means of molecular networking. Metabolites of 2F‐DCK were investigated using both human liver microsomes (HLMs) and hepatic (HepaRG) cell line incubates using molecular networking approach: 2F‐DCK pure substance was incubated with HLMs for up to 1 h at two concentrations (100 and 500 μM) and with HepaRG cells for two time periods (8 and 24 h) at one concentration (20 μM). In vitro obtained results were subsequently applied to a 2F‐DCK‐related fatality case. In vitro‐produced metabolites were investigated using high‐resolution accurate mass spectrometry using Orbitrap mass analyzer technology. Thirteen metabolites were in vitro produced and several metabolic pathways can be postulated. Seven additional metabolites were found in post‐mortem samples (bile and urine) of the case, comprising three Phase II metabolites, which appear to be minor in vivo metabolites. HLMs and HepaRG cell models appear to be complementary and obtained data allowed the identification of several specific 2F‐DCK metabolites in biological samples. In practical terms, observed metabolic ratios suggested that nor‐2F‐DCK (208.1137 m/z) and a hydrogenated metabolite (224.1443 m/z) could be proposed as reliable metabolites to be recorded in HRMS libraries in order to improve detection of 2F‐DCK use.
Intensive multidisciplinary feeding intervention for patients with avoidant/restrictive food intake disorder associated with severe food selectivity: An electronic health record review
Authors: Volkert Valerie M. , Burrell Lindsey , Berry Rashelle C. , Waddle Caitlin , White Lydia , Bottini Summer , Murphy Meredith , Sharp William G.
Published: September 2021

Objective

Expert consensus increasingly recognizes intensive multidisciplinary intervention (IMI) as the standard of care to address chronic and severe feeding problems in pediatric populations. In this study, we examined the clinical presentation, intervention characteristics, and treatment outcomes for young children receiving IMI for avoidant restrictive rood intake disorder (ARFID) involving nutritional insufficiencies associated with severe food selectivity.

Method

We followed the Strengthening the Reporting of Observational Studies in Epidemiology statement to conduct this retrospective chart review. The review focused on consecutive patients (birth to age 21 years) admitted to the IMI program over a 5‐year period (June 2014 to June 2019). Inclusion criteria required micronutrient insufficiencies (vitamins A, B12, C, D, E; folic acid; calcium; iron; and zinc) and chronic mealtime refusal behavior (e.g., turning head away from food/spoon, pushing or throwing spoon, crying, screaming, and leaving the table) associated with severe food selectivity.

Results

Over the 5‐year period, 63 of the patients met study entry requirements. Of these, 60 patients (50 boys and 10 girls; mean age = 72 ± 39 months; range = 23–181) completed intervention (95% treatment completion rate). At discharge, dietary diversity improved by 16 new therapeutic foods (range: 8–22), rapid acceptance and swallowing of new foods exceeded clinical benchmarks (80% or > bites), and risk for nutritional inadequacies declined for this patient cohort.

Discussion

Results of the current study support the benefits of IMI to increase dietary variety, improve mealtime behaviors, and enhance nutritional intake for children with ARFID presenting with severe food selectivity.
Importance of a turbulent river section below a giant waterfall for fish spawning: Indications from drift and dispersion patterns of early life stages
Authors: Makrakis Maristela C. , Refatti Alcione , Keckeis Hubert , da Silva Patrícia S. , de Assumpção Lucileine , Kashiwaqui Elaine A. L. , Gamaro Paulo E. , Makrakis Sergio
Published: September 2021

Seasonal drift patterns of fish eggs and larvae were analysed along the river section downstream the Iguaçu River Falls to the confluence with Paraná River, over three spawning seasons. This river section is situated in a narrow rocky canyon characterized by a steep slope, which leads to highly turbulent and fast flowing conditions in a series of rapids. Water transit time in this river stretch of 20 km was short (5–11 h), the flow‐velocity in rapids can reach values of more than 6 m s−1. Densities of drifting eggs and larvae varied between three spawning seasons, and differences of eggs were more pronounced compared to larvae. Eggs and larvae were observed all along the river section. A spatial, longitudinal distribution pattern of larvae was found, with higher numbers in the upper section. A distinct spatial sequence of different embryonic stages was observed, with the highest abundance of early stages. Larval densities were low in comparison to egg densities, and preflexion and flexion stages predominated. High abundance of buoyant eggs in drift indicates fish spawning in rapid and turbulent waters of the Iguaçu River, particularly downstream from the Iguaçu Falls. Rainfall and turbidity may be the main trigger for spawning. Spawned eggs drifted quickly towards the confluence, most are likely to hatch in the Paraná River, while larvae disperse to nursery habitats even in the river section below the falls. Thus, inshore zones along the whole stretch provide nursery habitats for larval development of fish species exhibiting different reproductive strategies.
Using single visits into integrated occupancy models to make the most of existing monitoring programs
Authors: Lauret Valentin , Labach Hélène , Authier Matthieu , Gimenez Olivier
Published: September 2021

A major challenge in statistical ecology consists of integrating knowledge from different data sets to produce robust ecological indicators. To estimate species distribution, occupancy models are a flexible framework that can accommodate several data sets obtained from different sampling methods. However, repeating visits at sampling sites is a prerequisite for using standard occupancy models. Occupancy models were recently developed to analyze detection/non‐detection data collected during a single visit. To date, single‐visit occupancy models have never been used to integrate several different data sets. Here, we showcase an approach that combines two data sets into an integrated single‐visit occupancy model. As a case study, we estimated the distribution of common bottlenose dolphin (Tursiops truncatus) over the northwestern Mediterranean Sea by combining 24,624 km of aerial surveys and 21,464 km of at‐sea monitoring. We compared the outputs of single‐ vs. repeated‐visit occupancy models into integrated occupancy models. Integrated models allowed a better sampling coverage of the targeted population, which provided a better precision for occupancy estimates than occupancy models using data sets in isolation. Overall, single‐ and repeated‐visit integrated occupancy models produced similar inference about the distribution of bottlenose dolphins. We suggest that single‐visit occupancy models open promising perspectives for the use of existing ecological data sets.
Systematic analysis of CD39, CD103, CD137, and PD‐1 as biomarkers for naturally occurring tumor antigen‐specific TILs
Authors: Eiva Monika A. , Omran Dalia K. , Chacon Jessica A. , Powell Daniel J.
Published: September 2021

The detection of tumor‐specific T cells in solid tumors is integral to interrogate endogenous antitumor responses and to advance downstream therapeutic applications. Multiple biomarkers are reported to identify endogenous tumor‐specific tumor‐infiltrating lymphocytes (TILs), namely CD137, PD‐1, CD103, and CD39; however, a direct comparison of these molecules has yet to be performed. We evaluated these biomarkers in primary human ovarian tumor samples using single‐cell mass cytometry to compare their relative phenotypic profiles, and examined their response to autologous tumor cells ex vivo. PD‐1+, CD103+, and CD39+ TILs all contain a CD137+ cell subset, while CD137+ TILs highly co‐express the aforementioned markers. CD137+ TILs exhibit the highest expression of cytotoxic effector molecules compared to PD‐1+, CD103+, or CD39+ TILs. Removal of CD137+ cells from PD‐1+, CD103+, or CD39+ TILs diminish their IFN‐γ secretion in response to autologous tumor cell stimulation, while CD137+ TILs maintain high HLA‐dependent IFN‐γ secretion. CD137+ TILs exhibited an exhausted phenotype but with CD28 co‐expression, suggesting possible receptiveness to reinvigoration via immune checkpoint blockade. Together, our findings demonstrate that the antitumor abilities of PD‐1+, CD103+, and CD39+ TILs are mainly derived from a subset of CD137‐expressing TILs, implicating CD137 as a more selective biomarker for naturally occurring tumor‐specific TILs.
Polar Lanthanide Anthracene Complexes Exhibiting Magnetic, Luminescent and Dielectric Properties
Authors: Sun Guo‐Bin , Huang Xin‐Da , Shang Tao , Yan Shuo , Bao Song‐Song , Lu Xiao‐Mei , Zhang Yi‐Quan , Zheng Li‐Min
Published: September 2021

Multifunctional molecular materials combining magnetic, luminescent and dielectric properties are attractive for potential applications in spintronics and molecular devices. Herein we report three isostructural mononuclear lanthanide phosphonates, namely, Ln(NO3)3(2‐deap)3 [Ln=Dy (1Dy), Er (2Er), Yb (3Yb), 2‐deap=diethyl anthrancen‐2‐ylphosphonate] which crystallize in polar space group Pna21. Magnetic studies revealed field‐induced slow magnetization relaxation for 1Dy and 3Yb, but not for 2Er down to 1.8 K. Theoretical calculations were conducted to rationalize the magneto‐structural relationship. The photoluminescent properties are also dependent on the lanthanide ion. For 1Dy, luminescence was observed only in the visible region mainly originating from the ligand. For 2Er, luminescence was observed only in the near‐infrared (NIR) region due to a complete energy transfer from the ligand to the ErIII ion. Regarding to 3Yb, luminescence was observed in both visible and NIR regions suggesting a partial energy transfer from the ligand to YbIII ion. Dielectric and piezoelectric measurements were performed on single crystals of 3Yb, which confirmed the presence of high dielectric anisotropy and weak piezoelectric response.
Seismic reliability implied by behavior‐factor‐based design
Authors: Baltzopoulos Georgios , Grella Antonio , Iervolino Iunio
Published: September 2021

Force‐based seismic design involves the reduction of elastic spectra by introducing a behavior factor, q. This approach is widespread in engineering practice; however, recent studies have shown that structures consistently designed at different sites will not share the same level of seismic risk, which can be defined as the annual rate of the structure failing to meet a seismic performance objective, despite seismic actions having the same exceedance return period at all sites. This paper investigates whether the definition of site‐specific q factors can lead to uniform risk across sites characterized by varying levels of seismic hazard, based on the pushover curves of bare frame reinforced concrete buildings. These pushover curves are used to establish the backbones of equivalent single degree of freedom systems with varying lateral resistance. These systems are fictitiously placed at several Italian sites and their seismic failure risk is computed by integrating their fragility, assessed by means of incremental dynamic analysis, with each site's hazard curve. By assuming an arbitrary risk threshold, the same for all sites, the corresponding lateral strength leading to said threshold is determined and the corresponding behavior factor is back calculated. As expected, risk‐targeted q factors tend to increase with decreasing seismic hazard and are highly sensitive to the shape of the hazard curve beyond the design return period. Coupled with the fact that at low hazard sites lateral strength is determined by detailing for gravity‐load design and minimum code requirements, rather than seismic design actions, the results suggest that q factor‐based design is unsuitable for warranting territorially uniform seismic safety, yet it may be suitable for setting an upper‐bound to the annual failure probability.
A Multi–Life Stage Comparison of Silver Nanoparticle Toxicity on the Early Development of Three Canadian Fish Species
Authors: Schultz Dayna R. , Tang Song , Miller Christie , Gagnon Danielle , Shekh Kamran , Alcaraz Alper J. G. , Janz David M. , Hecker Markus
Published: September 2021

Information on the effects of silver nanoparticles (AgNPs) in fish has mostly been generated from standard laboratory species and short-term toxicity tests. However, there is significant uncertainty regarding AgNP toxicity to native species of concern in North America, particularly in northern freshwater ecosystems. We assessed the chronic toxicity of AgNPs in early life stages of three North American fish species: rainbow trout (Oncorhynchus mykiss), lake trout (Salvelinus namaycush), and northern pike (Esox lucius). Newly fertilized embryos were exposed to nominal aqueous concentrations of 0.1, 0.3, 1.0, 3.0, 10.0, or 30.0 nM AgNPs for 126 (rainbow trout), 210 (lake trout), and 25 (northern pike) days. Endpoints included cumulative developmental time (°C × day or degree-days to 50% life-stage transition), mortality, fork length, embryonic malformations, cumulative survival, and histopathology of gill and liver in larvae/alevins. The results showed life stage–specific differences in responses, with endpoints during the embryonic stage occurring more often and at lower concentrations compared to larval/alevin and juvenile stages. Sensitivities among species were highly dependent on the endpoints measured, although developmental time appeared to be the most consistent endpoint across species. At embryonic and larval/alevin stages, northern pike was the most sensitive species (lowest observable effect concentration of 0.1 nM using developmental time). Rainbow trout displayed similar responses to lake trout across multiple endpoints and therefore seems to be an adequate surrogate for trout species in ecotoxicology studies. Moreover, while mortality during individual life stages was not generally affected, the cumulative mortality across life stages was significantly affected, which highlights the importance of chronic, multi-life-stage studies. Environ Toxicol Chem 2021;40:3337–3350. © 2021 SETAC