bluuebunny/crossref_metadata_2025_split huggingface dataset:
Recycling of Lithium‐Ion Batteries—Current State of the Art, Circular Economy, and Next Generation Recycling
Authors: Neumann Jonas , Petranikova Martina , Meeus Marcel , Gamarra Jorge D. , Younesi Reza , Winter Martin , Nowak Sascha 
Published: January 2022

AbstractBeing successfully introduced into the market only 30 years ago, lithium‐ion batteries have become state‐of‐the‐art power sources for portable electronic devices and the most promising candidate for energy storage in stationary or electric vehicle applications. This widespread use in a multitude of industrial and private applications leads to the need for recycling and reutilization of their constituent components. Improving the “recycling technology” of lithium ion batteries is a continuous effort and recycling is far from maturity today. The complexity of lithium ion batteries with varying active and inactive material chemistries interferes with the desire to establish one robust recycling procedure for all kinds of lithium ion batteries. Therefore, the current state of the art needs to be analyzed, improved, and adapted for the coming cell chemistries and components. This paper provides an overview of regulations and new battery directive demands. It covers current practices in material collection, sorting, transportation, handling, and recycling. Future generations of batteries will further increase the diversity of cell chemistry and components. Therefore, this paper presents predictions related to the challenges of future battery recycling with regard to battery materials and chemical composition, and discusses future approaches to battery recycling.
Mapping Ambiphile Reactivity Trends in the Anti‐(Hetero)annulation of Non‐Conjugated Alkenes via PdII/PdIV Catalysis
Authors: Ni Hui‐Qi , Cooper Phillippa , Yang Shouliang , Wang Fen , Sach Neal , Bedekar Pranali G. , Donaldson Joyann S. , Tran‐Dubé Michelle , McAlpine Indrawan J. , Engle Keary M. 
Published: January 2022

AbstractIn this study, we systematically evaluate different ambiphilic organohalides for their ability to participate in anti‐selective carbo‐ or heteroannulation with non‐conjugated alkenyl amides under PdII/PdIV catalysis. Detailed optimization of the reaction conditions has led to protocols for synthesizing tetrahydropyridines, tetralins, pyrrolidines, and other carbo/heterocyclic cores via [n+2] (n=3–5) (hetero)annulation. Expansion of scope to otherwise unreactive ambiphilic haloketones through PdII/amine co‐catalysis is also demonstrated. Compared to other annulation processes, this method proceeds via a distinct PdII/PdIV mechanism involving Wacker‐type directed nucleopalladation. This difference results in unique reactivity and selectivity patterns, as revealed through assessment of reaction scope and competition experiments.
Chiral Hybrid Copper(I) Halides for High Efficiency Second Harmonic Generation with a Broadband Transparency Window
Authors: Ge Fei , Li Bo‐Han , Cheng Puxin , Li Geng , Ren Zefeng , Xu Jialiang , Bu Xian‐He 
Published: January 2022

AbstractChiral hybrid organic–inorganic metal halides (HOMHs) with intrinsic noncentrosymmetry have shown great promise for applications in second‐order nonlinear optics (NLO). However, established chiral HOMHs often suffer from their relatively small band gaps, which lead to negative impacts on transparent window and laser‐induced damage thresholds (LDT). Here, we have synthesized two chiral HOMHs based on CuI halides, namely (R‐/S‐MBA)CuBr2, which feature well‐balanced NLO performances with a highly efficient SHG response, outstanding optical transparency, and high LDT. The effective second‐order NLO coefficient of (R‐MBA)CuBr2 has been determined to be ≈24.7 pm V−1, which is two orders of magnitude higher than that of their CuII counterparts. This work shows the promising potential of CuI‐based chiral HOMHs for nonlinear photonic applications in wide wavelength regions.
Orbitale als Ausgangspunkt der Chemischen Bindung in Ge−Sb−Te‐Phasenwechselmaterialien**
Authors: Hempelmann Jan , Müller Peter C. , Ertural Christina , Dronskowski Richard 
Published: January 2022

AbstractSchichtartige Phasenwechselmaterialien des Typs Ge−Sb−Te werden industriell zur Datenspeicherung verwendet und sind auch heute noch Gegenstand intensiver Forschung, um den quantenchemischen Ursprung ihrer Eigenschaften zu verstehen. Zur Analyse der zugrundeliegenden periodischen Wellenfunktion untersuchen wir die wechselwirkenden Atomorbitale einschließlich ihrer Phaseninformation mit Hilfe des Kristallorbitalbindungsindex und der Fragmentkristallorbitalanalyse. In voller Übereinstimmung mit Ergebnissen aus langreichweitigen projizierten Kraftkonstanten untermauern wir die besondere Rolle von Mehrzentrenbindungen entlang geradliniger atomarer Anordnungen. Ebendiese Mehrzentrenbindung ähnelt der bekannten Dreizentren‐Vierelektronenbindung in Molekülen, hat aber im festen Zustand weitreichende Auswirkungen für die üblicherweise als “metavalent” bezeichneten Materialeigenschaften und verdeutlicht die Zusammenhänge. Es liegt nahe, daß diese Mehrzentrenbindung die Ursache für das erstaunliche Bindungsbruch‐ und Phasenwechselverhalten sowie für die zu kleinen “van‐der‐Waals”‐Lücken zwischen den einzelnen Schichten ist.
Passerini–Smiles Reaction of α‐Ketophosphonates: Platform for Phospha‐Brook/Smiles Embedded Cascades
Authors: Cheibas Cristina , Fincias Nicolas , Casaretto Nicolas , Garrec Julian , El Kaïm Laurent 
Published: January 2022

AbstractThe Passerini–Smiles reactions of α‐ketophosphonates with nitrophenols has been used as a platform to observe complex cascades involving multiple Smiles transfers coupled with phospha‐Brook rearrangement. When using 4‐nitrophenols a rare 1,3‐Truce–Smiles rearrangement is observed leading to diarylacetamide derivatives. 2‐Nitro‐derivatives lead to a completely different reactivity pattern that may be explained by a nitro to nitroso conversion followed by a σ–π metathesis. All mechanistic assumptions are confirmed by DFT calculations performed on both families of adducts. The potential of this work has been further demonstrated by the use of N‐aryl α‐ketoamides as alternative starting materials for these cascades as well as the disclosure of new aza‐Nazarov access to hydroxy‐indolones.
A Plausible Prebiotic One‐Pot Synthesis of Orotate and Pyruvate Suggestive of Common Protometabolic Pathways
Authors: Clay Alyssa P. , Cooke Rachel E. , Kumar Ravi , Yadav Mahipal , Krishnamurthy Ramanarayanan , Springsteen Greg 
Published: January 2022

AbstractA reaction between two prebiotically plausible building blocks, hydantoin and glyoxylate, generates both the nucleobase orotate, a precursor of biological pyrimidines, and pyruvate, a core metabolite in the citric acid cycle and amino acid biosynthesis. The reaction proceeds in water to provide significant yields of the two widely divergent chemical motifs. Additionally, the reaction of thiohydantoin and glyoxylate produces thioorotate in high yield under neutral aqueous conditions. The use of an open‐chain thiohydantoin derivative also enables the potential pre‐positioning of a nucleosidic bond prior to the synthesis of an orotate nucleoside. The observation that diverse building blocks of modern metabolism can be produced in a single reaction pot, from common reactants under mild conditions, supports the plausibility of orthogonal chemistries operating at the origins of chemical evolution.
Outstanding Multi‐Photon Absorption at π‐Delocalizable Metallodendrimers
Authors: Zhang Ling , Morshedi Mahbod , Humphrey Mark G. 
Published: January 2022

AbstractMulti‐photon absorption (MPA) has attracted interest for applications exploiting the tight spatial control of interaction volume and long wavelength excitation. However, a deficiency of molecules exhibiting higher‐order nPA (n‐photon absorption, n>2) and a lack of structure–property studies to define the key structural characteristics needed to optimize higher‐order MPA performance have hindered practical development. We herein report the syntheses of second‐ and third‐generation metallodendrimers and assessment of their nonlinear absorption, together with those of zero‐ and first‐generation analogues. We report the first 5PA and 6PA data for an organometallic. The largest dendrimer exhibits exceptional three‐, four‐, five‐ and six‐photon absorption to femtosecond‐pulsed light. The systematically varied compounds highlight the crucial role of metal‐to‐oligo(phenyleneethynylene) charge transfer in promoting outstanding MPA activity.
Rhodium‐Catalyzed Stereoselective Deuteration of Benzylic C–H Bonds via Reversible η6‐Coordination
Authors: Kang Qi‐Kai , Li Yuntong , Chen Kai , Zhu Hui , Wu Wen‐Qiang , Lin Yunzhi , Shi Hang 
Published: January 2022

AbstractWe report a convenient method for benzylic H/D exchange of a wide variety of substrates bearing primary, secondary, or tertiary C−H bonds via a reversible η6‐coordination strategy. A doubly cationic [CpCF3RhIII]2+ catalyst that serves as an arenophile facilitates deprotonation of inert benzylic hydrogen atoms (pKa>40 in DMSO) without affecting other hydrogen atoms, such as those on aromatic rings or in α‐positions of carboxylate groups. Notably, the H/D exchange reactions feature high stereoretention. We demonstrated the potential utility of this method by using it for deuterium labeling of ten pharmaceuticals and their analogues.
Rheumatoid Factor and Anti–Modified Protein Antibody Reactivities Converge on IgG Epitopes
Authors: Mergaert Aisha M. , Zheng Zihao , Denny Michael F. , Amjadi Maya F. , Bashar S. Janna , Newton Michael A. , Malmström Vivianne , Grönwall Caroline , McCoy Sara S. , Shelef Miriam A. 
Published: January 2022

ObjectiveRheumatoid arthritis (RA) patients often develop rheumatoid factors (RFs), antibodies that bind IgG Fc, and anti–modified protein antibodies (AMPAs), multireactive autoantibodies that commonly bind citrullinated, homocitrullinated, and acetylated antigens. Recently, antibodies that bind citrulline‐containing IgG epitopes were discovered in RA, suggesting that additional undiscovered IgG epitopes could exist and that IgG could be a shared antigen for RFs and AMPAs. This study was undertaken to reveal new IgG epitopes in rheumatic disease and to determine if multireactive AMPAs bind IgG.MethodsUsing sera from patients with RA, systemic lupus erythematosus, Sjögren's disease (SjD), or spondyloarthropathy, IgG binding to native, citrulline‐containing, and homocitrulline‐containing linear epitopes of the IgG constant region was evaluated by peptide array, with highly bound epitopes further evaluated by enzyme‐linked immunosorbent assay (ELISA). Binding of monoclonal AMPAs to IgG‐derived peptides and IgG Fc was also evaluated by ELISA.ResultsSeropositive RA sera showed high IgG binding to multiple citrulline‐ and homocitrulline‐containing IgG‐derived peptides, whereas anti‐SSA+ sera from SjD patients showed consistent binding to a single linear native epitope of IgG in the hinge region. Monoclonal AMPAs bound citrulline‐ and homocitrulline‐containing IgG peptides and modified IgG Fc.ConclusionThe repertoire of epitopes bound by AMPAs includes modified IgG epitopes, positioning IgG as a common antigen that connects the otherwise divergent reactivities of RFs and AMPAs.
Central Role of Semaphorin 3B in a Serum‐Induced Arthritis Model and Reduced Levels in Patients With Rheumatoid Arthritis
Authors: Igea Ana , Carvalheiro Tiago , Malvar‐Fernández Beatriz , Martinez‐Ramos Sara , Rafael‐Vidal Carlos , Niemantsverdriet Ellis , Varadé Jezabel , Fernández‐Carrera Andrea , Jimenez Norman , McGarry Trudy , Rodriguez‐Trillo Angela , Veale Douglas , Fearon Ursula , Conde Carmen , Pego‐Reigosa Jose M. , González‐Fernández África , Reedquist Kris A. , Radstake Timothy R. D. J. , van der Helm‐Van Mil Annette , García Samuel 
Published: January 2022

ObjectiveSemaphorin 3B (Sema3B) decreases the migratory and invasive capacities of fibroblast‐like synoviocytes (FLS) in rheumatoid arthritis (RA) and suppresses expression of matrix metalloproteinases. We undertook this study to examine the role of Sema3B in a mouse model of arthritis and its expression in RA patients.MethodsClinical responses, histologic features, and FLS function were examined in wild‐type (WT) and Sema3B−/− mice in a K/BxN serum transfer model of arthritis. Protein and messenger RNA expression of Sema3B in mouse joints and murine FLS, as well as in serum and synovial tissue from patients with arthralgia and patients with RA, was determined using enzyme‐linked immunosorbent assay, immunoblotting, quantitative polymerase chain reaction, and RNA sequencing. FLS migration was determined using a wound closure assay.ResultsThe clinical severity of serum‐induced arthritis was significantly higher in Sema3B−/− mice compared to WT mice. This was associated with increased expression of inflammatory mediators and increased migratory capacity of murine FLS. Administration of recombinant mouse Sema3B reduced the clinical severity of serum‐induced arthritis and the expression of inflammatory mediators. Sema3B expression was significantly lower in the synovial tissue and serum of patients with established RA compared to patients with arthralgia. Serum Sema3B levels were elevated in patients with arthralgia that later progressed to RA, but not in those who did not develop RA; however, these levels drastically decreased 1 and 2 years after RA development.ConclusionSema3B expression plays a protective role in a mouse model of arthritis. In RA patients, expression levels of Sema3B in the serum depend on the disease stage, suggesting different regulatory roles in disease onset and progression.
The ALA5/ALA6/ALA7 repeat polymorphisms of the glutathione peroxidase‐1 (GPx1) gene and autism spectrum disorder
Authors: Carducci Federica , Ardiccioni Chiara , Fiorini Rosamaria , Vignini Arianna , Di Paolo Alice , Alia Sonila , Barucca Marco , Biscotti Maria Assunta 
Published: January 2022

AbstractAutism is a severe neurodevelopmental disorder leading to deficits in social interaction, communication, and several activities. An increasing number of evidence suggests a role of oxidative stress in the etiology of autism spectrum disorder (ASD). Indeed, impaired antioxidant mechanisms may lead to the inadequate removal of H2O2 with a consequent increase in highly active hydroxyl radicals and other reactive oxygen species causing cellular damages. The GPx1 is one of the most important enzymes counteracting oxidative stress. In this work, we investigated a possible correlation between the GCG repeat polymorphism present in the first exon of GPx1 gene encoding a tract of five to seven alanine residues (ALA5, ALA6, and ALA7) and ASD. Our findings highlighted a high frequency of ALA5 allele in ASD subjects. Moreover, proteins corresponding to the three GPx1 variants were produced in vitro, and the evaluation of their activity showed a lower values for GPx1 having ALA5 polymorphism. The comparison of the secondary and tertiary structure predictions revealed an alpha‐helix in correspondence of alanine stretch only in the case of GPx1‐ALA7 variant. Finally, to better investigate protein structure, steady‐state fluorescence measurements of GPx1 intrinsic tryptophan were carried out and the three tested proteins exhibited a different stability under denaturing conditions. This work demonstrates the importance in adopting a multidisciplinary strategy to comprehend the role of GPx1 in ASD.Lay SummaryResults here obtained suggest a possible role of ALA5 GPx1 variant in ASD. However, given the multifactorial nature of autism, this evidence might be a piece of a more complex puzzle being the GPx1 enzyme part of a complex pathway in which several proteins are involved.
Nine‐fold symmetry of centriole: The joint efforts of its core proteins
Authors: Tian Yuan , Yan Yuxuan , Fu Jingyan 
Published: January 2022

AbstractThe centriole is a widely conserved organelle required for the assembly of centrosomes, cilia, and flagella. Its striking feature – the nine‐fold symmetrical structure, was discovered over 70 years ago by transmission electron microscopy, and since elaborated mostly by cryo‐electron microscopy and super‐resolution microscopy. Here, we review the discoveries that led to the current understanding of how the nine‐fold symmetrical structure is built. We focus on the recent findings of the centriole structure in high resolution, its assembly pathways, and its nine‐fold distributed components. We propose a model that the assembly of the nine‐fold symmetrical centriole depends on the concerted efforts of its core proteins. Also see the video abstract here:https://youtu.be/m4h_3II_WJo
Oxidative Stress in Cancer Therapy: Friend or Enemy?
Authors: Azmanova Maria , Pitto‐Barry Anaïs 
Published: January 2022

AbstractExcessive cellular oxidative stress is widely perceived as a key factor in pathophysiological conditions and cancer development. Healthy cells use several mechanisms to maintain intracellular levels of reactive oxygen species (ROS) and overall redox homeostasis to avoid damage to DNA, proteins, and lipids. Cancer cells, in contrast, exhibit elevated ROS levels and upregulated protective antioxidant pathways. Counterintuitively, such elevated oxidative stress and enhanced antioxidant defence mechanisms in cancer cells provide a therapeutic opportunity for the development of drugs with different anticancer mechanisms of action (MoA). In this review, oxidative stress and the role of ROS in cells are described. The tumour‐suppressive and tumour‐promotive functions of ROS are discussed, and these two different therapeutic strategies (increasing or decreasing ROS to fight cancer) are compared. Clinically approved drugs with demonstrated oxidative stress anticancer MoAs are highlighted followed by description of examples of metal‐based anticancer drug candidates causing oxidative stress in cancer cells via novel MoAs.
Molecular Determinants of Carbocation Cyclisation in Bacterial Monoterpene Synthases
Authors: Leferink Nicole G. H. , Escorcia Andrés M. , Ouwersloot Bodi R. , Johanissen Linus O. , Hay Sam , van der Kamp Marc W. , Scrutton Nigel S. 
Published: January 2022

AbstractMonoterpene synthases are often promiscuous enzymes, yielding product mixtures rather than pure compounds due to the nature of the branched reaction mechanism involving reactive carbocations. Two previously identified bacterial monoterpene synthases, a linalool synthase (bLinS) and a cineole synthase (bCinS), produce nearly pure linalool and cineole from geranyl diphosphate, respectively. We used a combined experimental and computational approach to identify critical residues involved in bacterial monoterpenoid synthesis. Phe77 is essential for bCinS activity, guiding the linear carbocation intermediate towards the formation of the cyclic α‐terpinyl intermediate; removal of the aromatic ring results in variants that produce acyclic products only. Computational chemistry confirmed the importance of Phe77 in carbocation stabilisation. Phe74, Phe78 and Phe179 are involved in maintaining the active site shape in bCinS without a specific role for the aromatic ring. Phe295 in bLinS, and the equivalent Ala301 in bCinS, are essential for linalool and cineole formation, respectively. Where Phe295 places steric constraints on the carbocation intermediates, Ala301 is essential for bCinS initial cyclisation and activity. Our multidisciplinary approach gives unique insights into how carefully placed amino acid residues in the active site can direct carbocations down specific paths, by placing steric constraints or offering stabilisation via cation‐π interactions.
Human satellite III long noncoding RNA imparts survival benefits to cancer cells
Authors: Chatterjee Manjima , Sengupta Sonali 
Published: January 2022

AbstractLong noncoding RNAs (lncRNAs) are heterogeneous group of transcripts that lack coding potential and have essential roles in gene regulations. Recent days have seen an increasing association of noncoding RNAs with human diseases, especially cancers. One interesting group of noncoding RNAs strongly linked to cancers are heterochromatic repetitive Satellite RNAs. Satellite RNAs are transcribed from pericentromeric heterochromatic region of the human chromosomes. Satellite II RNA, most extensively studied, is upregulated in wide variety of epithelial cancer. Similarly, alpha satellite is over expressed in BRCA1‐deficient tumors. Though much is known about alpha satellites and SatII repeats, little is known about Satellite III (SatIII) lncRNAs in human cancers. SatIII repeats, though transcriptionally silent in normal conditions is actively transcribed under condition of stress, mainly heat shock. In this study, we show that colon and breast cancer cells aberrantly transcribes SatIII, in a heat shock factor I (HSF1)‐independent manner. Our study also reveals that, the overexpression of SatIII RNA favors cancer cell survival by overriding chemo drug‐induced cell death. Interestingly, knockdown of SatIII sensitizes cells toward chemotherapeutic drugs. This sensitization is possibly mediated by restoration of p53 protein expression that facilitates cell death. Heat shock however helps SatIII to continue with its pro‐cell survival function. Our results, therefore suggest SatIII to be an important regulator of human cancers. Induction of SatIII is not only a response to the oncogenic stress but also facilitates cancer progression by a distinct pathway that is different from heat stress pathway.
Airway malacia in premature infant twins with bronchopulmonary dysplasia: Two case reports
Authors: Yang Wanwan , Zhang Jiuxiang , Lu Dongxue , Zhang Haopeng 
Published: January 2022

AbstractPremature infants who require surgery for retinopathy of prematurity often exhibit bronchopulmonary dysplasia. Reactive airway is a clinical manifestation of bronchopulmonary dysplasia. We describe premature infant twins who had difficulty with positive pressure ventilation during anesthesia. Both cases occurred during induction of anesthesia for binocular anterior chamber puncture and vitreous cavity injection. The most likely cause in each case was airway malacia. We recommend that endotracheal intubation is performed in infant patients with low body weight; the possibility of airway malacia occurrence should be considered, especially for infants with comorbid bronchopulmonary dysplasia.
Evidence for Charge Delocalization in Diazafluorene Ligands Supporting Low‐Valent [Cp*Rh] Complexes**
Authors: Henke Wade C. , Stiel Jonah P. , Day Victor W. , Blakemore James D. 
Published: January 2022

AbstractLigands based upon the 4,5‐diazafluorene core are an important class of emerging ligands in organometallic chemistry, but the structure and electronic properties of these ligands have received less attention than they deserve. Here, we show that 9,9′‐dimethyl‐4,5‐diazafluorene (Me2daf) can stabilize low‐valent complexes through charge delocalization into its conjugated π‐system. Using a new platform of [Cp*Rh] complexes with three accessible formal oxidation states (+III, +II, and +I), we show that the methylation in Me2daf is protective, blocking Brønsted acid‐base chemistry commonly encountered with other daf‐based ligands. Electronic absorption spectroscopy and single‐crystal X‐ray diffraction analysis of a family of eleven new compounds, including the unusual Cp*Rh(Me2daf), reveal features consistent with charge delocalization driven by π‐backbonding into the LUMO of Me2daf, reminiscent of behavior displayed by the workhorse 2,2′‐bipyridyl ligand. Taken together with spectrochemical data demonstrating clean conversion between oxidation states, our findings show that 9,9′‐dialkylated daf‐type ligands are promising building blocks for applications in reductive chemistry and catalysis.