bluuebunny/crossref_metadata_2025_split huggingface dataset:
Socioecologic Factors and Racial Differences in Breast Cancer Multigene Prognostic Scores in US Women
Authors: Parab Ashwini Z. , Kong Angela , Lee Todd A. , Kim Kibum , Nutescu Edith A. , Malecki Kristen C. , Hoskins Kent F. , Calip Gregory S. 
Published: April 2024

ImportanceDisproportionately aggressive tumor biology among non-Hispanic Black women with early-stage, estrogen receptor (ER)–positive breast cancer contributes to racial disparities in breast cancer mortality. It is unclear whether socioecologic factors underlie racial differences in breast tumor biology.ObjectiveTo examine individual-level (insurance status) and contextual (area-level socioeconomic position and rural or urban residence) factors as possible mediators of racial and ethnic differences in the prevalence of ER-positive breast tumors with aggressive biology, as indicated by a high-risk gene expression profile.Design, Setting, and ParticipantsThis retrospective cohort study included women 18 years or older diagnosed with stage I to II, ER-positive breast cancer between January 1, 2007, and December 31, 2015. All data analyses were conducted between December 2022 and April 2023.Main Outcomes and MeasuresThe primary outcome was the likelihood of a high-risk recurrence score (RS) (≥26) on the Oncotype DX 21-gene breast tumor prognostic genomic biomarker.ResultsAmong 69 139 women (mean [SD] age, 57.7 [10.5] years; 6310 Hispanic [9.1%], 274 non-Hispanic American Indian and Alaskan Native [0.4%], 6017 non-Hispanic Asian and Pacific Islander [8.7%], 5380 non-Hispanic Black [7.8%], and 51 158 non-Hispanic White [74.0%]) included in our analysis, non-Hispanic Black (odds ratio [OR], 1.33; 95% CI, 1.23-1.43) and non-Hispanic American Indian and Alaska Native women (OR, 1.38; 95% CI, 1.01-1.86) had greater likelihood of a high-risk RS compared with non-Hispanic White women. There were no significant differences among other racial and ethnic groups. Compared with non-Hispanic White patients, there were greater odds of a high-risk RS for non-Hispanic Black women residing in urban areas (OR, 1.35; 95% CI, 1.24-1.46), but not among rural residents (OR, 1.05; 95% CI, 0.77-1.41). Mediation analysis demonstrated that lack of insurance, county-level disadvantage, and urban vs rural residence partially explained the greater odds of a high-risk RS among non-Hispanic Black women (proportion mediated, 17%; P &amp;lt; .001).Conclusions and RelevanceThe findings of this cohort study suggest that the consequences of structural racism extend beyond inequities in health care to drive disparities in breast cancer outcome. Additional research is needed with more comprehensive social and environmental measures to better understand the influence of social determinants on aggressive ER-positive tumor biology among racial and ethnic minoritized women from disadvantaged and historically marginalized communities.
RheumMadness Over Two Years: Engaging Participants in Active Learning and Connecting Early Trainees to the Rheumatology Community
Authors: He Lauren , Katz Guy , Garren Akrithi , Kellogg Ben , Macklin Michael , Bair Courtney , Qaiser Iman , Usmani Sabahat , Balbach Meridith , Lueck Benjamin , Sparks Matthew , Criscione‐Schreiber Lisa , Leverenz David 
Published: April 2024

ObjectiveRheumMadness is an online learning collaborative that seeks to actively engage the rheumatology community. The objective of this manuscript is to analyze the educational experience of RheumMadness over two years.MethodsDirect measures of participant engagement were obtained using web‐based analytics. An electronic survey was created after the tournament to capture self‐reported engagement and educational experience using the Community of Inquiry framework. Data were analyzed according to the following objectives: (1) compare demographics, engagement, and educational experience of participants between 2021 and 2022; (2) describe the educational experience of those who created scouting reports; (3) explore the impact of RheumMadness on early learners (medical students and residents).ResultsCompared with 2021, the 2022 tournament had more participants who submitted a bracket, more early learners, and more scouting report creators. Self‐reported engagement and educational experience was high in both years of the tournament among all participants. Over 85% of scouting report creators reported that making a report was a fun and valuable learning experience. Early learners reported significantly higher levels of knowledge integration, sense of belonging in the rheumatology community, social connection, and overall learning experience compared with more advanced participants. Eighty‐five percent of early learners reported that RheumMadness increased their interest in rheumatology.ConclusionRheumMadness expanded from 2021 to 2022, engaging more participants in collaborative learning. Our results demonstrate that RheumMadness is particularly impactful among medical students and residents by helping them explore rheumatology topics and connect with the rheumatology community.
A TLR4‐Targeting Bioactive Peptide Hydrogel to Regulate Immune‐Microenvironment for Diabetic Wound Repair
Authors: Jian Chuanjiang , Wang Minjia , Qian Yunyun , Song Xuejiao , Wang Li , Li Ling , Huang Lulu , Wang Guan , Shi Xianjie , Dong Jinqiao , Li Hao , Lin Ang , Shi Leilei 
Published: April 2024

AbstractPersistent inflammation and disrupted immunoregulation are critical factors in impeding diabetic wound healing. While immunoregulatory hydrogel dressings hold significant promise for clinical applications in diabetic wound healing, the current application often demands intricate interventions and high‐cost treatments involving cytokines and cell therapies. The development of single component immunoregulatory hydrogels remains a complex challenge. To address this issue, an active peptide hydrogel with immunoregulatory properties targeting the TLR4/NF‐kB pathway, aiming to promote rapid diabetic wound healing, is engineered. The hydrogel sequence comprises naphthalene derivative, phenylalanine, and glycine to modulate hydrophilic/hydrophobic characteristics. The amino group on arginine contributes to tissue adhesion and regulation of intermolecular forces, ultimately yielding stable gels. The results underscore the formation of the peptide hydrogel (NFA) via the physical crosslinking of self‐assembled nanofibers in water, thereby affording both excellent injectability and tissue adhesion. Notably, NFA demonstrates significant potential in promoting wound healing in a mouse model with full‐thickness wounds by regulating macrophage responses in the inflammatory microenvironment through the TLR4/NF‐kB pathway.
Beyond Conventional Charge Density Wave for Strongly Enhanced 2D Superconductivity in 1H‐TaS2 Superlattices
Authors: Li Zejun , Lyu Pin , Chen Zhaolong , Guan Dandan , Yu Shuang , Zhao Jinpei , Huang Pengru , Zhou Xin , Qiu Zhizhan , Fang Hanyan , Hashimoto Makoto , Lu Donghui , Song Fei , Loh Kian Ping , Zheng Yi , Shen Zhi‐Xun , Novoselov Kostya S. , Lu Jiong 
Published: April 2024

AbstractNoncentrosymmetric transition metal dichalcogenide (TMD) monolayers offer a fertile platform for exploring unconventional Ising superconductivity (SC) and charge density waves (CDWs). However, the vulnerability of isolated monolayers to structural disorder and environmental oxidation often degrade their electronic coherence. Herein, an alternative approach is reported for fabricating stable and intrinsic monolayers of 1H‐TaS2 sandwiched between SnS blocks in a (SnS)1.15TaS2 van der Waals (vdW) superlattice. The SnS block layers not only decouple individual 1H‐TaS2 sublayers to endow them with monolayer‐like electronic characteristics, but also protect the 1H‐TaS2 layers from electronic degradation. The results reveal the characteristic 3 × 3 CDW order in 1H‐TaS2 sublayers associated with electronic rearrangement in the low‐lying sulfur p band, which uncovers a previously undiscovered CDW mechanism rather than the conventional Fermi surface‐related framework. Additionally, the (SnS)1.15TaS2 superlattice exhibits a strongly enhanced Ising‐like SC with a layer‐independent Tc of ≈3.0 K, comparable to that of the isolated monolayer 1H‐TaS2 sample, presumably attributed to their monolayer‐like characteristics and retained Fermi states. These results provide new insights into the long‐debated CDW order and enhanced SC of monolayer 1H‐TaS2, establishing bulk vdW superlattices as promising platforms for investigating exotic collective quantum phases in the 2D limit.
Electronic Spin Alignment within Homologous NiS2/NiSe2 Heterostructures to Promote Sulfur Redox Kinetics in Lithium‐Sulfur Batteries
Authors: Huang Chen , Yu Jing , Zhang Chao Yue , Cui Zhibiao , Chen Jiakun , Lai Wei‐Hong , Lei Yao‐Jie , Nan Bingfei , Lu Xuan , He Ren , Gong Li , Li Junshan , Li Canhuang , Qi Xuede , Xue Qian , Zhou Jin Yuan , Qi Xueqiang , Balcells Lluís , Arbiol Jordi , Cabot Andreu 
Published: April 2024

AbstractThe catalytic activation of the Li‐S reaction is fundamental to maximize the capacity and stability of Li‐S batteries (LSBs). Current research on Li‐S catalysts mainly focuses on optimizing the energy levels to promote adsorption and catalytic conversion, while frequently overlooking the electronic spin state influence on charge transfer and orbital interactions. Here, hollow NiS2/NiSe2 heterostructures encapsulated in a nitrogen‐doped carbon matrix (NiS2/NiSe2@NC) are synthesized and used as a catalytic additive in sulfur cathodes. The NiS2/NiSe2 heterostructure promotes the spin splitting of the 3d orbital, driving the Ni3+ transformation from low to high spin. This high spin configuration raises the electronic energy level and activates the electronic state. This accelerates the charge transfer and optimizes the adsorption energy, lowering the reaction energy barrier of the polysulfides conversion. Benefiting from these characteristics, LSBs based on NiS2/NiSe2@NC/S cathodes exhibit high initial capacity (1458 mAh·g⁻1 at 0.1C), excellent rate capability (572 mAh·g⁻1 at 5C), and stable cycling with an average capacity decay rate of only 0.025% per cycle at 1C during 500 cycles. Even at high sulfur loadings (6.2 mg·cm⁻2), high initial capacities of 1173 mAh·g⁻1 (7.27 mAh·cm⁻2) are measured at 0.1C, and 1058 mAh·g⁻1 is retained after 300 cycles.
Photochemical Design for Diverse Controllable Patterns in Self‐Wrinkling Films
Authors: Yuan Wenqiang , Deng Xinlu , Wang Zehong , Ma Tianjiao , Yan Shuzhen , Gao Xiaxin , Li Jin , Ma Xiaodong , Yin Jie , Hu Kaiming , Zhang Wenming , Jiang Xuesong 
Published: April 2024

AbstractHarnessing the spontaneous surface instability of pliable substances to create intricate, well‐ordered, and on‐demand controlled surface patterns holds great potential for advancing applications in optical, electrical, and biological processes. However, the current limitations stem from challenges in modulating multidirectional stress fields and diverse boundary environments. Herein, this work proposes a universal strategy to achieve arbitrarily controllable wrinkle patterns via the spatiotemporal photochemical boundaries. Utilizing constraints and inductive effects of the photochemical boundaries, the multiple coupling relationship is accomplished among the light fields, stress fields, and morphology of wrinkles in photosensitive polyurethane (PSPU) film. Moreover, employing sequential light‐irradiation with photomask enables the attainment of a diverse array of controllable patterns, ranging from highly ordered 2D patterns to periodic or intricate designs. The fundamental mechanics of underlying buckling and the formation of surface features are comprehensively elucidated through theoretical stimulation and finite element analysis. The results reveal the evolution laws of wrinkles under photochemical boundaries and represent a new effective toolkit for fabricating intricate and captivating patterns in single‐layer films.
Pan‐Cancer Single‐Cell and Spatial‐Resolved Profiling Reveals the Immunosuppressive Role of APOE+ Macrophages in Immune Checkpoint Inhibitor Therapy
Authors: Liu Chuan , Xie Jindong , Lin Bo , Tian Weihong , Wu Yifan , Xin Shan , Hong Libing , Li Xin , Liu Lulu , Jin Yuzhi , Tang Hailin , Deng Xinpei , Zou Yutian , Zheng Shaoquan , Fang Weijia , Cheng Jinlin , Dai Xiaomeng , Bao Xuanwen , Zhao Peng 
Published: April 2024

AbstractThe heterogeneity of macrophages influences the response to immune checkpoint inhibitor (ICI) therapy. However, few studies explore the impact of APOE+ macrophages on ICI therapy using single‐cell RNA sequencing (scRNA‐seq) and machine learning methods. The scRNA‐seq and bulk RNA‐seq data are Integrated to construct an M.Sig model for predicting ICI response based on the distinct molecular signatures of macrophage and machine learning algorithms. Comprehensive single‐cell analysis as well as in vivo and in vitro experiments are applied to explore the potential mechanisms of the APOE+ macrophage in affecting ICI response. The M.Sig model shows clear advantages in predicting the efficacy and prognosis of ICI therapy in pan‐cancer patients. The proportion of APOE+ macrophages is higher in ICI non‐responders of triple‐negative breast cancer compared with responders, and the interaction and longer distance between APOE+ macrophages and CD8+ exhausted T (Tex) cells affecting ICI response is confirmed by multiplex immunohistochemistry. In a 4T1 tumor‐bearing mice model, the APOE inhibitor combined with ICI treatment shows the best efficacy. The M.Sig model using real‐world immunotherapy data accurately predicts the ICI response of pan‐cancer, which may be associated with the interaction between APOE+ macrophages and CD8+ Tex cells.
Torsion Effects Beyond the δ Bond and the Role of π Metal‐Ligand Interactions
Authors: Inchausti Almudena , Mollfulleda Rosa , Swart Marcel , Perles Josefina , Herrero Santiago , Baonza Valentín G. , Taravillo Mercedes , Lobato Álvaro 
Published: April 2024

AbstractPrevious studies on bimetallic paddlewheel compounds have established a direct correlation between metal–metal distance and ligand torsion angles, leading to the rule that higher torsion results in longer metal‐metal bond distances. Here, the new discovery based on diarylformamidinate Ru₂⁵⁺ paddlewheel compounds [Ru2Cl(DArF)4] that show an opposite behavior is reported: higher torsions lead to shorter metal–metal distances. This discovery challenges the assumption that internal rotation solely impacts the δ bond. By combining experimental and theoretical techniques, it is demostrated that this trend is associated with previously overlooked π metal‐ligand interactions. These π metal‐ligand interactions are a direct consequence of the paddlewheel structure and the conjugated nature of the bidentate ligands. This findings offer far‐reaching insights into the influence of equatorial ligands and their π‐conjugation characteristics on the electronic properties of paddlewheel complexes. That this effect is not exclusive of diruthenium compounds but also occurs in other bimetallic cores such as ditungsten or dirhodium is demonstrated, and with other ligands showing allyl type conjugation. These results provide a novel approach for fine‐tuning the properties of these compounds with significant implications for materials design.
Programmable Racetrack for Magnetic Domain Wall Motion via Local Tuning of Exchange Biased Field
Authors: Kim Hyun‐Joong , Moon Kyoung‐Woong , Yoon Seongsoo , An Kyongmo , Kim Changsoo , Yang Seungmo , Ju Tae‐Seong , Son Jong Wan , Hong Jung‐Il , Hwang Chanyong 
Published: April 2024

AbstractTo overcome memory bottleneck issues in memory‐centric chip technologies, in‐memory computing has been considered an alternative route involving simultaneous data storage and computing in a memory network. In the context of spintronics, a memory‐in‐logic device based on spin‐transfer‐torque or spin‐orbit‐torque magnetoresistive random‐access memory, and a magnetic domain wall (DW) racetrack has been studied. To expand the functionalities of a conventional magnetic DW racetrack, the study devises a reprogrammable exchange‐biased DW racetrack with local engineering of the exchange bias field (HE) in continuous magnetic films without requiring a lithography process for specific patterning of the films. Furthermore, current‐driven and field‐driven DW motion along the exchange‐biased racetrack is demonstrated. Additionally, within the route of the locally different exchange‐biased racetrack, a gate function can be performed to guide or stop DW motion by locally tuning HE. The complex maze racetrack is rewritable, and multiple input channels can be controlled.
Direct Access to Carbamates through Palladium‐Catalyzed Carbonylation of Nitroarenes and Siloxanes
Authors: Yuan Weiheng , An Tongshun , Liu Chenwei , Qin Xiaowen , Yin Zhiping 
Published: April 2024

AbstractA novel and applicable method for the preparation of various carbamates via a palladium‐catalyzed carbonylation reaction was developed. In the absence of fluorine sources, a wide range of nitroarenes and siloxanes are readily reacted to give the corresponding carbamates in yields ranging from 23 % to 97 % using Mo(CO)6 as both the reducing agent and the carbonyl source. Mechanistic experiments indicated that isocyanate was found to be a critical intermediate in the overall reaction.
Electronic Metal‐Support Interactions Boost *OOH Intermediate Generation in Cu/In2Se3 for Electrochemical H2O2 Production
Authors: Liu Yuepeng , Wang Pengfei , Xie Liangbo , Xia Yuguo , Zhan Sihui , Hu Wenping , Li Yi 
Published: April 2024

AbstractTwo‐electron oxygen reduction reaction (2e− ORR) is a promising method for the synthesis of hydrogen peroxide (H2O2). However, high energy barriers for the generation of key *OOH intermediates hinder the process of 2e− ORR. Herein, we prepared a copper‐supported indium selenide catalyst (Cu/In2Se3) to enhance the selectivity and yield of 2e− ORR by employing an electronic metal–support interactions (EMSIs) strategy. EMSIs‐induced charge rearrangement between metallic Cu and In2Se3 is conducive to *OOH intermediate generation, promoting H2O2 production. Theoretical investigations reveal that the inclusion of Cu significantly lowers the energy barrier of the 2e− ORR intermediate and impedes the 4e− ORR pathway, thus favoring the formation of H2O2. The concentration of H2O2 produced by Cu/In2Se3 is ~2 times than In2Se3, and Cu/In2Se3 shows promising applications in antibiotic degradation. This research presents a valuable approach for the future utilization of EMSIs in 2e− ORR.
Aerobic Oxidative Synthesis of Formamides from Amines and Bioderived Formyl Surrogates
Authors: Dai Xingchao , Han Yunyan , Jiao Haijun , Shi Feng , Rabeah Jabor , Brückner Angelika 
Published: April 2024

AbstractHerein we present a new strategy for the oxidative synthesis of formamides from various types of amines and bioderived formyl sources (DHA, GLA and GLCA) and molecular oxygen (O2) as oxidant on g‐C3N4 supported Cu catalysts. Combined characterization data from EPR, XAFS, XRD and XPS revealed the formation of single CuN4 sites on supported Cuphen/C3N4 catalysts. EPR spin trapping experiments disclosed ⋅OOH radicals as reactive oxygen species and ⋅NR1R2 radicals being responsible for the initial C−C bond cleavage. Control experiments and DFT calculations showed that the successive C−C bond cleavage in DHA proceeds via a reaction mechanism co‐mediated by ⋅NR1R2 and ⋅OOH radicals based on the well‐equilibrated CuII and CuI cycle. Our catalyst has much higher activity (TOF) than those based on noble metals.
Strong Interactions between Au Nanoparticles and BiVO4 Photoanode Boosts Hole Extraction for Photoelectrochemical Water Splitting
Authors: He Bing , Cao Yu , Lin Kaijie , Wang Yang , Li Zhen , Yang Yingkui , Zhao Yanli , Liu Xueqin 
Published: April 2024

AbstractStrong metal‐support interaction (SMSI) is widely proposed as a key factor in tuning catalytic performances. Herein, the classical SMSI between Au nanoparticles (NPs) and BiVO4 (BVO) supports (Au/BVO‐SMSI) is discovered and used innovatively for photoelectrochemical (PEC) water splitting. Owing to the SMSI, the electrons transfer from V4+ to Au NPs, leading to the formation of electron‐rich Au species (Auδ−) and strong electronic interaction (i.e., Auδ−‐Ov‐V4+), which readily contributes to extract photogenerated holes and promote charge separation. Benefitted from the SMSI effect, the as‐prepared Au/BVO‐SMSI photoanode exhibits a superior photocurrent density of 6.25 mA cm−2 at 1.23 V versus the reversible hydrogen electrode after the deposition of FeOOH/NiOOH cocatalysts. This work provides a pioneering view for extending SMSI effect to bimetal oxide supports for PEC water splitting, and guides the interfacial electronic and geometric structure modulation of photoanodes consisting of metal NPs and reducible oxides for improved solar energy conversion efficiency.
Confinement of Sustainable Carbon Dots Results in Long Afterglow Emitters and Photocatalyst for Radical Photopolymerization
Authors: Wang Ping , Ge Min , Luo Xiongfei , Zhai Yingxiang , Meckbach Nicolai , Strehmel Veronika , Li Shujun , Chen Zhijun , Strehmel Bernd 
Published: April 2024

AbstractSustainable carbon dots based on cellulose, particularly carboxymethyl cellulose carbon dots (CMCCDs), were confined in an inorganic network resulting in CMCCDs@SiO2. This resulted in a material exhibiting long afterglow covering a time frame of several seconds also under air. Temperature‐dependent emission spectra gave information on thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) while photocurrent experiments provided a deeper understanding of charge availability in the dark period, and therefore, its availability on the photocatalyst surface. The photo‐ATRP initiator, ethyl α‐bromophenylacetate (EBPA), quenched the emission from the millisecond to the nanosecond time frame indicating participation of the triplet state in photoinduced electron transfer (PET). Both free radical and controlled radical polymerization based on photo‐ATRP protocol worked successfully. Metal‐free photo‐ATRP resulted in chain extendable macroinitiators based on a reductive mechanism with either MMA or in combination with styrene. Addition of 9 ppm Cu2+ resulted in Mw/Mn of 1.4 while an increase to 72 ppm improved uniformity of the polymers; that is Mw/Mn=1.03. Complementary experiments with kerria laca carbon dots confined materials, namely KCDs@SiO2, provided similar results. Deposition of Cu2+ (9 ppm) on the photocatalyst surface explains better uniformity of the polymers formed in the ATRP protocol.
Hydrogen Source Tuned Regiodivergent Asymmetric Hydroalkylations of 2‐Substituted 1,3‐Dienes with Aldehydes by Cobalt‐Catalysis
Authors: Zeng Xian‐Wang , Lin Jia‐Ni , Shu Wei 
Published: April 2024

AbstractCatalytic methods allowing for the reliable prediction and control of diverse regioselectivity along with the control of enantioselectivity to access different regio‐ and enantiomers by switching the least reaction parameters are one of the most attractive ways in organic synthesis, which provide access to diverse enantioenriched architectures from identical starting materials. Herein, a Co‐catalyzed regiodivergent and enantioselective reductive hydroalkylation of 1,3‐dienes with aldehydes has been achieved, furnishing different enantioenriched homoallylic alcohol architectures in good levels of enantioselectivity. The reaction features the switch of regioselectivity tuned by the selection of proton source. The use of an acid as proton source provided asymmetric 1,2‐hydroalkylation products under reductive conditions, yet asymmetric 4,3‐hydroalkylation products were obtained with silane as hydride source. This catalytic protocol allows for the access of homoallylic alcohols with two continuous saturated carbon centers in good levels of regio‐, diastereo‐, and enantioselectivity.