bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Clonal Invariant NKT Cell Repertoire in People with Type 1 Diabetes Is Characterized by a Loss of Clones Expressing High-Affinity TCRs
Authors: Tocheva Anna S. , Mansour Salah , Holt Tristan G. H. , Jones Samuel , Chancellor Andrew , Sanderson Joseph P. , Eren Efrem , Elliott Tim J. , Holt Richard I. G. , Gadola Stephan D. 
Published: January 2017

Abstract
Invariant NKT (iNKT) cells in healthy people express iNKT-TCRs with widely varying affinities for CD1d, suggesting different roles for high- and low-affinity iNKT clones in immune regulation. However, the functional implications of this heterogeneity have not yet been determined. Functionally aberrant iNKT responses have been previously demonstrated in different autoimmune diseases, including human type 1 diabetes, but their relationship to changes in the iNKT clonal repertoire have not been addressed. In this study, we directly compared the clonal iNKT repertoire of people with recent onset type 1 diabetes and age- and gender-matched healthy controls with regard to iNKT-TCR affinity and cytokine production. Our results demonstrate a selective loss of clones expressing high-affinity iNKT-TCRs from the iNKT repertoire of people with type 1 diabetes. Furthermore, this bias in the clonal iNKT repertoire in type 1 diabetes was associated with increased GM-CSF, IL-4, and IL-13 cytokine secretion among Ag-stimulated low-affinity iNKT clones. Thus, qualitative changes of the clonal iNKT repertoire with the potential to affect the regulatory function of this highly conserved T cell population are already established at the early stages in type 1 diabetes. These findings may inform future rationales for the development of iNKT-based therapies aiming to restore immune tolerance in type 1 diabetes.
Prostaglandin E2 Inhibition of IL-27 Production in Murine Dendritic Cells: A Novel Mechanism That Involves IRF1
Authors: Hooper Kirsten M. , Yen Jui-Hung , Kong Weimin , Rahbari Kate M. , Kuo Ping-Chang , Gamero Ana M. , Ganea Doina 
Published: January 2017

Abstract
IL-27, a multifunctional cytokine produced by APCs, antagonizes inflammation by affecting conventional dendritic cells (cDC), inducing IL-10, and promoting development of regulatory Tr1 cells. Although the mechanisms involved in IL-27 induction are well studied, much less is known about the factors that negatively impact IL-27 expression. PGE2, a major immunomodulatory prostanoid, acts as a proinflammatory agent in several models of inflammatory/autoimmune disease, promoting primarily Th17 development and function. In this study, we report on a novel mechanism that promotes the proinflammatory function of PGE2. We showed previously that PGE2 inhibits IL-27 production in murine bone marrow–derived DCs. In this study, we show that, in addition to bone marrow–derived DCs, PGE2 inhibits IL-27 production in macrophages and in splenic cDC, and we identify a novel pathway consisting of signaling through EP2/EP4→induction of cAMP→downregulation of IFN regulatory factor 1 expression and binding to the p28 IFN-stimulated response element site. The inhibitory effect of PGE2 on p28 and irf1 expression does not involve endogenous IFN-β, STAT1, or STAT2, and inhibition of IL-27 does not appear to be mediated through PKA, exchange protein activated by cAMP, PI3K, or MAPKs. We observed similar inhibition of il27p28 expression in vivo in splenic DC following administration of dimethyl PGE2 in conjunction with LPS. Based on the anti-inflammatory role of IL-27 in cDC and through the generation of Tr1 cells, we propose that the PGE2-induced inhibition of IL-27 in activated cDC represents an important additional mechanism for its in vivo proinflammatory functions.
Monoclonal Antibodies against Epidermal Growth Factor Receptor Acquire an Ability To Kill Tumor Cells through Complement Activation by Mutations That Selectively Facilitate the Hexamerization of IgG on Opsonized Cells
Authors: Tammen Annalina , Derer Stefanie , Schwanbeck Ralf , Rösner Thies , Kretschmer Anna , Beurskens Frank J. , Schuurman Janine , Parren Paul W. H. I. , Valerius Thomas 
Published: January 2017

Abstract
Triggering of the complement cascade induces tumor cell lysis via complement-dependent cytotoxicity (CDC) and attracts and activates cytotoxic cells. It therefore represents an attractive mechanism for mAb in cancer immunotherapy development. The classical complement pathway is initiated by IgG molecules that have assembled into ordered hexamers after binding their Ag on the tumor cell surface. The requirements for CDC are further impacted by factors such as Ab epitope, valency, and affinity. Thus, mAb against well-validated solid tumor targets, such as the epidermal growth factor receptor (EGFR) that effectively induces complement activation and CDC, are highly sought after. The potency of complement activation by IgG Abs can be increased via several strategies. We identified single-point mutations in the Fc domain (e.g., E345K or E430G) enhancing Fc:Fc interactions, hexamer formation, and CDC after Ab binds cell-surface Ag. We show that EGFR Abs directed against clinically relevant epitopes can be converted into mAb with unprecedented CDC activity. Alternative strategies rely on increasing the affinity of monomeric IgG for C1q by introduction of a quadruple mutation at the C1q binding site or via generation of an IgG1/IgG3 chimera. In this study we show that selective enhancement of C1q binding via avidity modulation is superior to the unattended increase in C1q binding via affinity approaches, particularly for target cells with reduced EGFR expression levels. Improving Fc:Fc interactions of Ag-bound IgG therefore represents a highly promising and novel approach for potentiating the anti-tumor activity of therapeutic mAb against EGFR and potentially other tumor targets.
Subclinical Herpes Simplex Virus Type 1 Infections Provide Site-Specific Resistance to an Unrelated Pathogen
Authors: Rowe Alexander M. , Yun Hongming , Treat Benjamin R. , Kinchington Paul R. , Hendricks Robert L. 
Published: January 2017

Abstract
HSV-1 infections of the cornea range in severity from minor transient discomfort to the blinding disease herpes stromal keratitis, yet most patients experience a single episode of epithelial keratitis followed by re-establishment of a clear cornea. We asked whether a single transient episode of HSV-1 epithelial keratitis causes long-term changes in the corneal microenvironment that influence immune responses to subsequent corneal infection or trauma. We showed that C57BL/6 mouse corneas infected with HSV-1 KOS, which induces transient herpes epithelial keratitis without herpes stromal keratitis sequelae, possessed a significant leukocytic infiltrate composed primarily of CD4+ T cells and macrophages along with elevated chemokines and cytokines that persisted without loss of corneal clarity (subclinical inflammation). Chemokine and cytokine expression was CD4+ T cell dependent, in that their production was significantly reduced by systemic CD4+ T cell depletion starting before infection, although short-term (3-d) local CD4+ T cell depletion postinfection did not influence chemokine levels in cornea. Corneas with subclinical inflammation developed significantly greater trauma-induced inflammation when they were recipients of syngeneic corneal transplants but also exhibited significantly increased resistance to infections by unrelated pathogens, such as pseudorabies virus. The resistance to pseudorabies virus was CD4+ T cell dependent, because it was eliminated by local CD4+ T cell depletion from the cornea. We conclude that transient HSV-1 corneal infections cause long-term alterations of the corneal microenvironment that provide CD4-dependent innate resistance to subsequent infections by antigenically unrelated pathogens.
A Landscape Never Goes Out of Style. Diachronic Lexical Variation in Exhibition Press Announcements
Authors: Lazzeretti Cecilia 
Published: January 2017

The paper focuses on diachronic lexical variation in a professional textual genre which has gained growing importance over time in the fi eld of museum public relations and art discourse: exhibition press announcements (EPAs). The aim of the analysis is to investigate the language of EPAs from a diachronic perspective in order to identify word frequencies showing large increases or decreases, or stability in word frequencies. Baker’s (2011) method to distinguish variation over time across multiple corpora was applied and particular attention was placed on the presence of “lockwords”, i.e. words “relatively static in terms of frequency” (Baker 2011: 66). The analysis is carried out on a corpus of EPAs dating from 1950 to 2009 issued by American and British museums. The study reports on a number of trends relating to linguistic and cultural change of EPAs, including the emergence of new criteria in assessing the value of artists and artworks despite a certain consistency in terms of subjects, the shift from one-item to multi-item exhibitions and the preference for more vivid and straight-forward descriptions. For instance, the frequency of the noun landscape has remained stable over time, suggesting that this subject is particularly consistent in art displays, quite a sort of classic, that never grows old, while the artist's career – a word showing a clear pattern of growth – has become particularly valuable over time for museum professionals in charge of exhibitions.
Harnessing Multi‐Asymmetric Engineering: A New Horizon in Bifunctional Oxygen Electrocatalysis with Iron‐Group Atom‐Cluster Nanohybrid
Authors: Xu Qiaoling , Zhang Lei , Li Luhan , Zhang Shijing , Zhou Yingtang , Hu Guangzhi 
Published: September 2024

AbstractIntegrating active sites for oxygen reduction and evolution reactions (ORR and OER) is pivotal for advancing bifunctional oxygen electrodes. Addressing the geometric/electronic properties of these sites is essential to disrupt the linear scaling relationship between the adsorption and desorption of complex intermediates. Herein, a proof‐of‐concept is presented for constructing asymmetric trinuclear sites employing both composition‐ and size‐based asymmetric coupling strategies. These sites comprise ORR‐active Fe single atom (FeSA), OER‐active atomically clustered Fe species (FeAC), and NiSA sites as modulators. This FeAC‐SA‐NiSA@N‐doped carbon exhibits excellent bifunctional catalytic activities, with a narrow potential gap of 0.661 V between an ORR half‐wave potential of 0.931 V and an OER potential of 1.592 V at 10 mA cm−2. The Zn‐air battery employing this material achieves a peak power density of 293 mW cm−2, a specific capacity of 748 mAh gZn−1, and remarkable stability. Experimental findings and theoretical simulations reveal that NiSA sites induced strong electronic coupling among the trinuclear centers, facilitating charge redistribution and optimizing the adsorption and desorption barriers for intermediates. This enhances the rapid release of *OH during ORR and the efficient transformation from *O to *OOH during OER. This study presents a novel strategy for developing robust bifunctional oxygen electrodes.
Thiourea Suppressing Iodide Oxidation and Passivating Perovskite Surface to Achieve High‐Efficiency Stable Solar Cells
Authors: Hua Guoxin , Lin Xinyue , Lai Yiliang , Huo Le , Wang Wanhai , Tang Weihua 
Published: September 2024

AbstractMetal halide perovskite solar cells (PSCs) have witnessed their power conversion efficiency (PCE) record continuously refreshed over the last two decades. The device long‐term stability however remains as the critical consideration for their industrialization. In particular, the redox‐sensitive ions and precursors can easily initiate reaction, leading to perovskite lattice segregation and defect formation and thus instability of PSCs. In this work, a versatile perovskite film stabilizing method is reported here using 1‐(3‐(trifluoromethyl)phenyl) thiourea (TPT) as a redox modifier to achieve high‐efficiency and stable PSCs. Featuring large dipole moments, TPT performs excellent antioxidation for iodides and constructs multiple interactions with FA+ and Pb2+ cations to dramatically reduce defect state density as well as modulate surface potential in perovskite film. The TPT‐modified perovskite films readily endow the inverted PSCs with a highest PCE of 24.71% in 0.12 cm2 device area and a superior fill factor of 84.59%, together with an excellent device stability against moisture and oxygen. Over 88% retention of initial PCE has been achieved after 2000 h aging in ambient air with 30%–40% relative humidity. This thiourea stabilizing perovskite strategy is expected to benefit large‐area fabrication of PSCs for simultaneously achieving high performance in both power output and long‐term stability.
Dual Active Intermediates Induced LiOH Formation via the OH‐Rich Proton Donor in Li−O2 Batteries
Authors: Song Li‐Na , Wang Xiao‐Xue , Wang Huan‐Feng , Wang Yue , Wu Jia‐Yi , Sun Yu , Xu Ji‐Jing 
Published: September 2024

AbstractGenerally, water displays a dominated impact on the solution growth mechanism of the aprotic lithium−oxygen (Li−O2) batteries, however, the high reaction activity and laborious secondary chemistry transformation process are associated with the irreversible utilization of water. In this paper, a substituted proton‐containing, highly dispersed and hydroxyl group (−OH)‐rich contained catalyst is employed in the Li−O2 battery chemistry, and lithium hydroxide (LiOH) is identified as the primary discharge product. Intriguingly, the hydrogen (H) in LiOH comes solely from the added −OH‐rich onion carbon (OLC), which is capable of building a high‐speed proton transfer bridge between the generated moieties of dual active intermediates superoxide species (O2−) and the moderate hydroperoxide (HO2−) over the platinum (Pt) active sites. The new mechanism involving the HO2− intermediate realizes a hydrogen transfer process via O2− nucleophilic attack toward OLC, which significantly suppresses the O2−‐related side reactions. Thereby, the batteries with Pt/OLC attain a high specific capacity of 12 500 mAh g−1 at a current density of 100 mA g−1, exceptional energy efficiency (100%), and remarkable rechargeability. In addition, the strong OLC‐DMSO interaction inhibits the lithium metal corrosion caused by the shuttle reactions and ensures favorable battery cycling stability. The promising results open up a new reaction pathway for Li−O2 battery electrochemistry.
Low‐Symmetry Van der Waals Dielectric GaInS3 Triggered 2D MoS2 Giant Anisotropy via Symmetry Engineering
Authors: Sun Zongdong , Liu Jie , Xu Yongshan , Xiong Xiong , Li Yuan , Wang Meihui , Liu Kailang , Li Huiqiao , Wu Yanqing , Zhai Tianyou 
Published: September 2024

AbstractLow‐symmetry structures in van der Waals materials have facilitated the advancement of anisotropic electronic and optoelectronic devices. However, the intrinsic low symmetry structure exhibits a small adjustable anisotropy ratio (1–10), which hinders its further assembly and processing into high‐performance devices. Here, a novel 2D anisotropic dielectric, GaInS3 (GIS), which induces isotropic MoS2 to exhibit significant anisotropic optical and electrical responses is demonstrated. With the excellent gate modulation ability of 2D GIS (dielectric constant k ∼12), MoS2 field effect transistor (FET) shows an adjustable conductance ratio from isotropic to anisotropic under dual‐gate modulation, up to 106. Theoretical calculations indicate that anisotropy originates from lattice mismatch‐induced charge density deformation at the interface. Moreover, the MoS2/GIS photodetector demonstrates high responsivity (≈4750 A W−1) and a large dichroic ratio (≈167). The anisotropic van der Waals dielectric GIS paves the way for the development of 2D transition metal dichalcogenides (TMDCs) in the fields of anisotropic photonics, electronics, and optoelectronics.
Morphological and Interfacial Engineering with a Surfactant Additive Toward High‐Performance Blade‐Coated Quantum Dot Light‐Emitting Diodes
Authors: Liu Wei‐Zhi , Duan Hong‐Wei , Meng Shu‐Guang , Zhou Dong‐Ying , Liao Liang‐Sheng 
Published: September 2024

AbstractThe development of scalable and cost‐effective solution processes for large‐area quantum light‐emitting diodes (QLEDs) remains a pressing challenge. In this work, the blade‐coating process is explored for fabricating bottom‐emitting QLEDs using a poly(3,4‐ ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) layer modified with methanol (MeOH) and polyethylene glycol (PEG). By incorporating MeOH into the PEDOT:PSS solution, a significant reduction in surface tension is achieved, resulting in thinner and more uniform films. The addition of PEG further enhanced the film quality by suppressing PEDOT aggregation and improving phase separation, which is confirmed via atomic force microscopy (AFM). These modifications not only enhanced the conductivity of the PEDOT:PSS film due to the conformation changes, but also improved energy level alignment, leading to improved hole‐injecting properties and reduced driving voltages in QLED devices. Small‐area QLEDs with the optimized PEDOT:PSS/MeOH/PEG layer demonstrated peak current efficiencies (CE) and external quantum efficiencies (EQE) comparable to those of spin‐coated devices. The best performance is observed at a PEG concentration of 0.1 mg mL−1, yielding a CE of 33.1 cd A−1 and an EQE of 26.0%. Additionally, large‐area QLEDs (25 × 25 mm) fabricated with this approach showed uniform emission and high efficiencies, underscoring the potential of the blade‐coating method for scalable production of high‐performance QLEDs.
Understanding the Size‐Dependent Photostability and Photoluminescence Intermittency of Blue‐Emitting Core/Graded Alloy/Shell “giant”‐Quantum Dots
Authors: Singh Rahul , Praneeth NVS , Biswas Subarna , Palabathuni Manoj , Muralidharan Anandu , Mishra Nimai , Khatua Saumyakanti 
Published: September 2024

AbstractRecently, giant quantum dots (g‐QDs) with a core/interface graded alloy shell/shell structure have shown promise in reducing photoluminescence (PL) intermittency and improving photostability. However, this approach has been mainly demonstrated with red and green emitting g‐QDs but the blue‐emitting graded alloy QDs has remained less explored. To tackle this challenge, a composition gradient method is employed to create three blue‐emitting CdZnS/CdxZn1–xS/ZnS core/interface graded alloy shell/shell (C/A/S) quantum dots (QDs) with different diameters. The sample with the largest diameter (gQD‐3) exhibits superior optical characteristics, with a photoluminescence quantum yield (PLQY) of approximately 62% and around 80% ON/radiative events at the single‐particle level. Conversely, the smallest diameter (gQD‐1) sample shows lower PLQY and only 30% radiative events with longer OFF/nonradiative events. Probability distribution analysis of PL trajectories, fitted with a truncated power law, reveals a significantly higher carrier de‐trapping rate in gQD‐3 compared to gQD‐1, attributed to its proximity to band edge trap states. Additionally, the largest diameter sample retains remarkable optical performance during 48 h of continuous UV irradiation in colloidal suspension and single‐particle levels. These findings show optimized core/shell structures, gradual alloy interfaces, and outer shell coatings can stabilize blue‐emitting quantum dots, advancing next‐gen optoelectronics.
Multilevel Supramolecular Assembly with Three‐Step Sequential Energy Transfer for Selective Generation of Sulfides and Sulfoxides by Photoredox Thiol‐Ene Cross‐Coupling Reactions
Authors: Zhang Rong‐Zhen , Bi Yu‐Song , Niu Kai‐Kai , Yu Shengsheng , Liu Hui , Xing Ling‐Bao 
Published: September 2024

AbstractPhotosynthesis in natural systems involves a series of steps for energy transfer, but replicating this process in artificial light‐harvesting systems (ALHS) with three or more steps is still difficult. This work presents a set of ALHS that exhibit an intricate three‐step energy transfer mechanism. The ALHS are meticulously fabricated by utilizing cyano‐substituted diphenyl ethylene derivative (DCMI), cucurbit[7]uril (CB[7]), and sulfobutylether‐β‐cyclodextrin (SBE‐βCD) through host–guest and electrostatic interactions in water to create a multilevel molecular assembly serving as energy donors. Three distinct types of fluorescent dyes, namely rhodamine B (RhB), sulforhodamine 101 (SR101), and cyanine 5 (Cy5), are employed as energy acceptors. The DCMI‐2CB[7]@SBE‐βCD+RhB+SR101+Cy5 system demonstrates an effective three‐step sequential energy transfer process, which involves the transfer of energy from DCMI‐2CB[7]@SBE‐βCD to RhB, SR101, and Cy5 in a consecutive manner, resulting in a substantial energy transfer efficiency. Remarkably, within the multi‐step energy transfer system, the generation of reactive oxygen species (ROS) exhibit a progressive augmentation. Furthermore, to fully utilize the harvested energy and obtained ROS, the ALHS with multistep sequential energy transfer further promotes the visible‐light induced photoredox thiol‐ene cross‐coupling reaction between thiophenol and styrene to selectively obtain sulfides and sulfoxides in water with high yields.
One‐Pot Synthesis of 2‐Substituted‐4,5‐dimethyloxazoles from Amides and Acetylene Gas in the KOH/MeOH/DMSO Catalytic Triad
Authors: Schmidt Elena Yu. , Semenova Nadezhda V. , Ivanova Evgeniya E. , Ushakov Igor A. , Bidusenko Ivan A. , Bobkov Alexander S. , Vitkovskaya Nadezhda M. , Trofimov Boris A. 
Published: September 2024

AbstractPharmaceutically prospective 2‐substituted‐4,5‐dimethyloxazoles are synthesized in 16–58% yield via cascade assembly of one molecule of primary amide with two molecules of acetylene gas in the KOH/MeOH/DMSO catalytic triad (90 °C, 2 h). This self‐organization of oxazoles demonstrates unexpected successful competition with the alkaline hydrolysis of amides. The mechanism involving amide N‐vinylation, enamine‐imine isomerization, imine ethynylation and intramolecular O‐vinylation cascade sequence has been deduced and supported by quantum‐chemical calculations using the B2PLYP−D3/6‐311+G**//B3LYP/6‐31+G*+IEF PCM (B3LYP/6‐31+G*) approach.
Precise Regulation of Interlayer Stacking Modes in Trinuclear Copper Organic Frameworks for Efficient Photocatalytic Reduction of Uranium(VI)
Authors: Gao Zhi , Lv Sijia , Wang Yue , Xu Zhenzhen , Zong Yingtong , Tao Yuan , Zhao Yingji , Liu Xingyu , Yu Shuhui , Luo Mingbiao , Khaorapapong Nithima , Zhang Ruikang , Yamauchi Yusuke 
Published: September 2024

AbstractThe interlayer stacking modes of 2D covalent‐organic frameworks (COFs) directly influence their structural features, ultimately determining their functional output. However, controllably modulating the interlayer stacking structure in traditional 2D metal‐free COFs, based on the same building blocks, remains challenging. Here, two trinuclear copper organic frameworks are synthesized successfully with different interlayer stacking structures: eclipsed AA stacking in Cu3‐PA‐COF‐AA and staggered ABC stacking in Cu3‐PA‐COF‐ABC, using the same monomers. Remarkably, various functionalities, including porosity and electronic and optical properties, can be effectively regulated by interlayer stacking. As a result, Cu3‐PA‐COF‐AA and Cu3‐PA‐COF‐ABC exhibit significantly different activities toward the photoreduction of U(VI), presenting a promising strategy for removing radioactive uranium pollution. Due to its broader visible‐light absorption range and superior photogenerated carrier migration and separation efficiency, Cu3‐PA‐COF‐AA achieves a U(VI) removal ratio of 93.6% without additional sacrificial agents in an air atmosphere—≈2.2 times higher than that of Cu3‐PA‐COF‐ABC (42.0%). To the best of the knowledge, this is the first study to elucidate the effect of interlayer stacking in COFs on the photocatalytic activity of U(VI) reduction. This finding may inspire further exploration of the structure‐function relationship in COFs as photocatalysts and their potential for photoinduced removal of radionuclides.