bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photoelectrocatalytic C–H halogenation over an oxygen vacancy-rich TiO2 photoanode
Authors: Li Zhenhua , Luo Lan , Li Min , Chen Wangsong , Liu Yuguang , Yang Jiangrong , Xu Si-Min , Zhou Hua , Ma Lina , Xu Ming , Kong Xianggui , Duan Haohong 
Published: November 2021

AbstractPhotoelectrochemical cells are emerging as powerful tools for organic synthesis. However, they have rarely been explored for C–H halogenation to produce organic halides of industrial and medicinal importance. Here we report a photoelectrocatalytic strategy for C–H halogenation using an oxygen-vacancy-rich TiO2 photoanode with NaX (X=Cl−, Br−, I−). Under illumination, the photogenerated holes in TiO2 oxidize the halide ions to corresponding radicals or X2, which then react with the substrates to yield organic halides. The PEC C–H halogenation strategy exhibits broad substrate scope, including arenes, heteroarenes, nonpolar cycloalkanes, and aliphatic hydrocarbons. Experimental and theoretical data reveal that the oxygen vacancy on TiO2 facilitates the photo-induced carriers separation efficiency and more importantly, promotes halide ions adsorption with intermediary strength and hence increases the activity. Moreover, we designed a self-powered PEC system and directly utilised seawater as both the electrolyte and chloride ions source, attaining chlorocyclohexane productivity of 412 µmol h−1 coupled with H2 productivity of 9.2 mL h−1, thus achieving a promising way to use solar for upcycling halogen in ocean resource into valuable organic halides.
Strong metal-support interactions induced by an ultrafast laser
Authors: Zhang Jian , Zhu Dezhi , Yan Jianfeng , Wang Chang-An 
Published: November 2021

AbstractSupported metal catalysts play a crucial role in the modern industry. Constructing strong metal-support interactions (SMSI) is an effective means of regulating the interfacial properties of noble metal-based supported catalysts. Here, we propose a new strategy of ultrafast laser-induced SMSI that can be constructed on a CeO2-supported Pt system by confining electric field in localized interface. The nanoconfined field essentially boosts the formation of surface defects and metastable CeOx migration. The SMSI is evidenced by covering Pt nanoparticles with the CeOx thin overlayer and suppression of CO adsorption. The overlayer is permeable to the reactant molecules. Owing to the SMSI, the resulting Pt/CeO2 catalyst exhibits enhanced activity and stability for CO oxidation. This strategy of constructing SMSI can be extended not only to other noble metal systems (such as Au/TiO2, Pd/TiO2, and Pt/TiO2) but also on non-reducible oxide supports (such as Pt/Al2O3, Au/MgO, and Pt/SiO2), providing a universal way to engineer and develop high-performance supported noble metal catalysts.
Osseosurface electronics—thin, wireless, battery-free and multimodal musculoskeletal biointerfaces
Authors: Cai Le , Burton Alex , Gonzales David A. , Kasper Kevin Albert , Azami Amirhossein , Peralta Roberto , Johnson Megan , Bakall Jakob A. , Barron Villalobos Efren , Ross Ethan C. , Szivek John A. , Margolis David S. , Gutruf Philipp 
Published: November 2021

AbstractBioelectronic interfaces have been extensively investigated in recent years and advances in technology derived from these tools, such as soft and ultrathin sensors, now offer the opportunity to interface with parts of the body that were largely unexplored due to the lack of suitable tools. The musculoskeletal system is an understudied area where these new technologies can result in advanced capabilities. Bones as a sensor and stimulation location offer tremendous advantages for chronic biointerfaces because devices can be permanently bonded and provide stable optical, electromagnetic, and mechanical impedance over the course of years. Here we introduce a new class of wireless battery-free devices, named osseosurface electronics, which feature soft mechanics, ultra-thin form factor and miniaturized multimodal biointerfaces comprised of sensors and optoelectronics directly adhered to the surface of the bone. Potential of this fully implanted device class is demonstrated via real-time recording of bone strain, millikelvin resolution thermography and delivery of optical stimulation in freely-moving small animal models. Battery-free device architecture, direct growth to the bone via surface engineered calcium phosphate ceramic particles, demonstration of operation in deep tissue in large animal models and readout with a smartphone highlight suitable characteristics for exploratory research and utility as a diagnostic and therapeutic platform.
Direct observation of one-dimensional disordered diffusion channel in a chain-like thermoelectric with ultralow thermal conductivity
Authors: Zhang Jiawei , Roth Nikolaj , Tolborg Kasper , Takahashi Seiya , Song Lirong , Bondesgaard Martin , Nishibori Eiji , Iversen Bo B. 
Published: November 2021

AbstractStructural disorder, highly effective in reducing thermal conductivity, is important in technological applications such as thermal barrier coatings and thermoelectrics. In particular, interstitial, disordered, diffusive atoms are common in complex crystal structures with ultralow thermal conductivity, but are rarely found in simple crystalline solids. Combining single-crystal synchrotron X-ray diffraction, the maximum entropy method, diffuse scattering, and theoretical calculations, here we report the direct observation of one-dimensional disordered In1+ chains in a simple chain-like thermoelectric InTe, which contains a significant In1+ vacancy along with interstitial indium sites. Intriguingly, the disordered In1+ chains undergo a static-dynamic transition with increasing temperature to form a one-dimensional diffusion channel, which is attributed to a low In1+-ion migration energy barrier along the c direction, a general feature in many other TlSe-type compounds. Our work provides a basis towards understanding ultralow thermal conductivity with weak temperature dependence in TlSe-type chain-like materials.
Micronutrient supplements can promote disruptive protozoan and fungal communities in the developing infant gut
Authors: Popovic Ana , Bourdon Celine , Wang Pauline W. , Guttman David S. , Soofi Sajid , Bhutta Zulfiqar A. , Bandsma Robert H. J. , Parkinson John , Pell Lisa G. 
Published: November 2021

AbstractSupplementation with micronutrients, including vitamins, iron and zinc, is a key strategy to alleviate child malnutrition. However, association of gastrointestinal disorders with iron has led to ongoing debate over their administration. To better understand their impact on gut microbiota, we analyse the bacterial, protozoal, fungal and helminth communities of stool samples collected from a subset of 80 children at 12 and 24 months of age, previously enrolled into a large cluster randomized controlled trial of micronutrient supplementation in Pakistan (ClinicalTrials.gov identifier NCT00705445). We show that while bacterial diversity is reduced in supplemented children, vitamins and iron (as well as residence in a rural setting) may promote colonization with distinct protozoa and mucormycetes, whereas the addition of zinc appears to ameliorate this effect. We suggest that the risks and benefits of micronutrient interventions may depend on eukaryotic communities, potentially exacerbated by exposure to a rural setting. Larger studies are needed to evaluate the clinical significance of these findings and their impact on health outcomes.
Impact damping and vibration attenuation in nematic liquid crystal elastomers
Authors: Saed Mohand O. , Elmadih Waiel , Terentjev Andrew , Chronopoulos Dimitrios , Williamson David , Terentjev Eugene M. 
Published: November 2021

AbstractNematic liquid crystal elastomers (LCE) exhibit unique mechanical properties, placing them in a category distinct from other viscoelastic systems. One of their most celebrated properties is the ‘soft elasticity’, leading to a wide plateau of low, nearly-constant stress upon stretching, a characteristically slow stress relaxation, enhanced surface adhesion, and other remarkable effects. The dynamic soft response of LCE to shear deformations leads to the extremely large loss behaviour with the loss factor tanδ approaching unity over a wide temperature and frequency ranges, with clear implications for damping applications. Here we investigate this effect of anomalous damping, optimising the impact and vibration geometries to reach the greatest benefits in vibration isolation and impact damping by accessing internal shear deformation modes. We compare impact energy dissipation in shaped samples and projectiles, with elastic wave transmission and resonance, finding a good correlation between the results of such diverse tests. By comparing with ordinary elastomers used for industrial damping, we demonstrate that the nematic LCE is an exceptional damping material and propose directions that should be explored for further improvements in practical damping applications.
Machine learning of genomic features in organotropic metastases stratifies progression risk of primary tumors
Authors: Jiang Biaobin , Mu Quanhua , Qiu Fufang , Li Xuefeng , Xu Weiqi , Yu Jun , Fu Weilun , Cao Yong , Wang Jiguang 
Published: November 2021

AbstractMetastatic cancer is associated with poor patient prognosis but its spatiotemporal behavior remains unpredictable at early stage. Here we develop MetaNet, a computational framework that integrates clinical and sequencing data from 32,176 primary and metastatic cancer cases, to assess metastatic risks of primary tumors. MetaNet achieves high accuracy in distinguishing the metastasis from the primary in breast and prostate cancers. From the prediction, we identify Metastasis-Featuring Primary (MFP) tumors, a subset of primary tumors with genomic features enriched in metastasis and demonstrate their higher metastatic risk and shorter disease-free survival. In addition, we identify genomic alterations associated with organ-specific metastases and employ them to stratify patients into various risk groups with propensities toward different metastatic organs. This organotropic stratification method achieves better prognostic value than the standard histological grading system in prostate cancer, especially in the identification of Bone-MFP and Liver-MFP subtypes, with potential in informing organ-specific examinations in follow-ups.
Bioorthogonal labeling of transmembrane proteins with non-canonical amino acids unveils masked epitopes in live neurons
Authors: Bessa-Neto Diogo , Beliu Gerti , Kuhlemann Alexander , Pecoraro Valeria , Doose Sören , Retailleau Natacha , Chevrier Nicolas , Perrais David , Sauer Markus , Choquet Daniel 
Published: November 2021

AbstractProgress in biological imaging is intrinsically linked to advances in labeling methods. The explosion in the development of high-resolution and super-resolution imaging calls for new approaches to label targets with small probes. These should allow to faithfully report the localization of the target within the imaging resolution – typically nowadays a few nanometers - and allow access to any epitope of the target, in the native cellular and tissue environment. We report here the development of a complete labeling and imaging pipeline using genetic code expansion and non-canonical amino acids in neurons that allows to fluorescently label masked epitopes in target transmembrane proteins in live neurons, both in dissociated culture and organotypic brain slices. This allows us to image the differential localization of two AMPA receptor (AMPAR) auxiliary subunits of the transmembrane AMPAR regulatory protein family in complex with their partner with a variety of methods including widefield, confocal, and dSTORM super-resolution microscopy.
Single-cell analysis of diverse immune phenotypes in malignant pleural effusion
Authors: Huang Zhong-Yin , Shao Ming-Ming , Zhang Jian-Chu , Yi Feng-Shuang , Du Juan , Zhou Qiong , Wu Feng-Yao , Li Sha , Li Wei , Huang Xian-Zhen , Zhai Kan , Shi Huan-Zhong 
Published: November 2021

AbstractThe complex interactions among different immune cells have important functions in the development of malignant pleural effusion (MPE). Here we perform single-cell RNA sequencing on 62,382 cells from MPE patients induced by non-small cell lung cancer to describe the composition, lineage, and functional states of infiltrating immune cells in MPE. Immune cells in MPE display a number of transcriptional signatures enriched for regulatory T cells, B cells, macrophages, and dendritic cells compared to corresponding counterparts in blood. Helper T, cytotoxic T, regulatory T, and T follicular helper cells express multiple immune checkpoints or costimulatory molecules. Cell-cell interaction analysis identifies regulatory B cells with more interactions with CD4+ T cells compared to CD8+ T cells. Macrophages are transcriptionally heterogeneous and conform to M2 polarization characteristics. In addition, immune cells in MPE show the general up-regulation of glycolytic pathways associated with the hypoxic microenvironment. These findings show a detailed atlas of immune cells in human MPE and enhance the understanding of potential diagnostic and therapeutic targets in advanced non-small cell lung cancer.
Visual prototypes in the ventral stream are attuned to complexity and gaze behavior
Authors: Rose Olivia , Johnson James , Wang Binxu , Ponce Carlos R. 
Published: November 2021

AbstractEarly theories of efficient coding suggested the visual system could compress the world by learning to represent features where information was concentrated, such as contours. This view was validated by the discovery that neurons in posterior visual cortex respond to edges and curvature. Still, it remains unclear what other information-rich features are encoded by neurons in more anterior cortical regions (e.g., inferotemporal cortex). Here, we use a generative deep neural network to synthesize images guided by neuronal responses from across the visuocortical hierarchy, using floating microelectrode arrays in areas V1, V4 and inferotemporal cortex of two macaque monkeys. We hypothesize these images (“prototypes”) represent such predicted information-rich features. Prototypes vary across areas, show moderate complexity, and resemble salient visual attributes and semantic content of natural images, as indicated by the animals’ gaze behavior. This suggests the code for object recognition represents compressed features of behavioral relevance, an underexplored aspect of efficient coding.
Asymmetric construction of acyclic quaternary stereocenters via direct enantioselective additions of α-alkynyl ketones to allenamides
Authors: Wang Jiawen , He Faqian , Yang Xiaoyu 
Published: November 2021

AbstractAcyclic quaternary stereocenters are widely present in a series of biologically active natural products and pharmaceuticals. However, development of highly efficient asymmetric catalytic methods for the construction of these privileged motifs represents a longstanding challenge in organic synthesis. Herein, an efficient chiral phosphoric acid catalyzed direct asymmetric addition of α-alkynyl acyclic ketones with allenamides has been developed, furnishing the acyclic all-carbon quaternary stereocenters with excellent regioselectivities and high enantioselectivities. Extensive and detailed experimental mechanistic studies were performed to investigate the mechanism of this reaction. Despite a novel covalent allyl phosphate intermediate was found in these reactions, further studies indicated that a SN2-type mechanism with the ketone nucleophiles is not very possible. Instead, a more plausible mechanism involving the elimination of the allyl phosphate to give the α,β-unsaturated iminium intermediate, which underwent the asymmetric conjugate addition with the enol form of ketone nucleophiles under chiral anion catalysis, was proposed. In virtue of the fruitful functional groups bearing in the chiral products, the diverse derivatizations of the chiral products provided access to a wide array of chiral scaffolds with quaternary stereocenters.
Inflammasome-mediated GSDMD activation facilitates escape of Candida albicans from macrophages
Authors: Ding Xionghui , Kambara Hiroto , Guo Rongxia , Kanneganti Apurva , Acosta-Zaldívar Maikel , Li Jiajia , Liu Fei , Bei Ting , Qi Wanjun , Xie Xuemei , Han Wenli , Liu Ningning , Zhang Cunling , Zhang Xiaoyu , Yu Hongbo , Zhao Li , Ma Fengxia , Köhler Julia R. , Luo Hongbo R. 
Published: November 2021

AbstractCandida albicansis the most common cause of fungal sepsis. Inhibition of inflammasome activity confers resistance to polymicrobial and LPS-induced sepsis; however, inflammasome signaling appears to protect againstC. albicansinfection, so inflammasome inhibitors are not clinically useful for candidiasis. Here we show disruption of GSDMD, a known inflammasome target and key pyroptotic cell death mediator, paradoxically alleviates candidiasis, improving outcomes and survival ofCandida-infected mice. Mechanistically,C. albicanshijacked the canonical inflammasome-GSDMD axis-mediated pyroptosis to promote their escape from macrophages, deploying hyphae and candidalysin, a pore-forming toxin expressed by hyphae. GSDMD inhibition alleviated candidiasis by preventingC. albicansescape from macrophages while maintaining inflammasome-dependent but GSDMD-independent IL-1β production for anti-fungal host defenses. This study demonstrates key functions for GSDMD inCandida’s escape from host immunity in vitro and in vivo and suggests that GSDMD may be a potential therapeutic target inC. albicans-induced sepsis.
Evidence for anisotropic spin-triplet Andreev reflection at the 2D van der Waals ferromagnet/superconductor interface
Authors: Cai Ranran , Yao Yunyan , Lv Peng , Ma Yang , Xing Wenyu , Li Boning , Ji Yuan , Zhou Huibin , Shen Chenghao , Jia Shuang , Xie X. C. , Žutić Igor , Sun Qing-Feng , Han Wei 
Published: November 2021

AbstractFundamental symmetry breaking and relativistic spin–orbit coupling give rise to fascinating phenomena in quantum materials. Of particular interest are the interfaces between ferromagnets and common s-wave superconductors, where the emergent spin-orbit fields support elusive spin-triplet superconductivity, crucial for superconducting spintronics and topologically-protected Majorana bound states. Here, we report the observation of large magnetoresistances at the interface between a quasi-two-dimensional van der Waals ferromagnet Fe0.29TaS2 and a conventional s-wave superconductor NbN, which provides the possible experimental evidence for the spin-triplet Andreev reflection and induced spin-triplet superconductivity at ferromagnet/superconductor interface arising from Rashba spin-orbit coupling. The temperature, voltage, and interfacial barrier dependences of the magnetoresistance further support the induced spin-triplet superconductivity and spin-triplet Andreev reflection. This discovery, together with the impressive advances in two-dimensional van der Waals ferromagnets, opens an important opportunity to design and probe superconducting interfaces with exotic properties.
Pre-existing immunity and vaccine history determine hemagglutinin-specific CD4 T cell and IgG response following seasonal influenza vaccination
Authors: Wild Katharina , Smits Maike , Killmer Saskia , Strohmeier Shirin , Neumann-Haefelin Christoph , Bengsch Bertram , Krammer Florian , Schwemmle Martin , Hofmann Maike , Thimme Robert , Zoldan Katharina , Boettler Tobias 
Published: November 2021

AbstractEffectiveness of seasonal influenza vaccination varies between individuals and might be affected by vaccination history among other factors. Here we show, by monitoring frequencies of CD4 T cells specific to the conserved hemagglutinin epitope HA118-132 and titres of IgG against the corresponding recombinant hemagglutinin protein, that antigen-specific CD4 T cell and antibody responses are closely linked to pre-existing immunity and vaccine history. Upon immunization, a strong early reaction is observed in all vaccine naïve participants and also in vaccine experienced individuals who have not received the respective seasonal vaccine in the previous year. This response is characterized by HA118-132 specific CD4 T cells with a follicular helper T cell phenotype and by ascending titers of hemagglutinin-specific antibodies from baseline to day 28 following vaccination. This trend was observed in only a proportion of those participants who received the seasonal vaccine the year preceding the study. Regardless of history, levels of pre-existing antibodies and CD127 expression on CD4 T cells at baseline were the strongest predictors of robust early response. Thus, both pre-existing immunity and vaccine history contribute to the response to seasonal influenza vaccines.
Proofreading experimentally assigned stereochemistry through Q2MM predictions in Pd-catalyzed allylic aminations
Authors: Wahlers Jessica , Margalef Jèssica , Hansen Eric , Bayesteh Armita , Helquist Paul , Diéguez Montserrat , Pàmies Oscar , Wiest Olaf , Norrby Per-Ola 
Published: November 2021

AbstractThe palladium-catalyzed enantioselective allylic substitution by carbon or nitrogen nucleophiles is a key transformation that is particularly useful for the synthesis of bioactive compounds. Unfortunately, the selection of a suitable ligand/substrate combination often requires significant screening effort. Here, we show that a transition state force field (TSFF) derived by the quantum-guided molecular mechanics (Q2MM) method can be used to rapidly screen ligand/substrate combinations. Testing of this method on 77 literature reactions revealed several cases where the computationally predicted major enantiomer differed from the one reported. Interestingly, experimental follow-up led to a reassignment of the experimentally observed configuration. This result demonstrates the power of mechanistically based methods to predict and, where necessary, correct the stereochemical outcome.
Combination of epigenetic regulation with gene therapy-mediated immune checkpoint blockade induces anti-tumour effects and immune response in vivo
Authors: Fang Huapan , Guo Zhaopei , Chen Jie , Lin Lin , Hu Yingying , Li Yanhui , Tian Huayu , Chen Xuesi 
Published: November 2021

AbstractImmunotherapy has become a powerful cancer treatment, but only a small fraction of patients have achieved durable benefits due to the immune escape mechanism. In this study, epigenetic regulation is combined with gene therapy-mediated immune checkpoint blockade to relieve this immune escape mechanism. PPD (i.e., mPEG-b-PLG/PEI-RT3/DNA) is developed to mediate plasmid-encoding shPD-L1 delivery by introducing multiple interactions (i.e., electrostatic, hydrogen bonding, and hydrophobic interactions) and polyproline II (PPII)-helix conformation, which downregulates PD-L1 expression on tumour cells to relieve the immunosuppression of T cells. Zebularine (abbreviated as Zeb), a DNA methyltransferase inhibitor (DNMTi), is used for the epigenetic regulation of the tumour immune microenvironment, thus inducing DC maturation and MHC I molecule expression to enhance antigen presentation. PPD plus Zeb combination therapy initiates a systemic anti-tumour immune response and effectively prevents tumour relapse and metastasis by generating durable immune memory. This strategy provides a scheme for tumour treatment and the inhibition of relapse and metastasis.