bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ligand effect on switching the rate-determining step of water oxidation in atomically precise metal nanoclusters
Authors: Liu Zhihe , Tan Hua , Li Bo , Hu Zehua , Jiang De-en , Yao Qiaofeng , Wang Lei , Xie Jianping 
Published: June 2023

AbstractThe ligand effects of atomically precise metal nanoclusters on electrocatalysis kinetics have been rarely revealed. Herein, we employ atomically precise Au25nanoclusters with different ligands (i.e., para-mercaptobenzoic acid, 6-mercaptohexanoic acid, and homocysteine) as paradigm electrocatalysts to demonstrate oxygen evolution reaction rate-determining step switching through ligand engineering. Au25nanoclusters capped by para-mercaptobenzoic acid exhibit a better performance with nearly 4 times higher than that of Au25NCs capped by other two ligands. We deduce that para-mercaptobenzoic acid with a stronger electron-withdrawing ability establishes more partial positive charges on Au(I) (i.e., active sites) for facilitating feasible adsorption of OH–in alkaline media. X-ray photo-electron spectroscopy and theoretical study indicate a profound electron transfer from Au(I) to para-mercaptobenzoic acid. The Tafel slope and in situ Raman spectroscopy suggest different ligands trigger different rate-determining step for these Au25nanoclusters. The mechanistic insights reported here can add to the acceptance of atomically precise metal nanoclusters as effective electrocatalysts.
Direct determination of high-order transverse ligand field parameters via µSQUID-EPR in a Et4N[160GdPc2] SMM
Authors: Taran Gheorghe , Moreno-Pineda Eufemio , Schulze Michael , Bonet Edgar , Ruben Mario , Wernsdorfer Wolfgang 
Published: June 2023

AbstractThe development of quantum technologies requires a thorough understanding of systems possessing quantum effects that can ultimately be manipulated. In the field of molecular magnetism, one of the main challenges is to measure high-order ligand field parameters, which play an essential role in the relaxation properties of SMMs. The development of highly advanced theoretical calculations has allowed the ab-initio determination of such parameters; however, currently, there is a lack of quantitative assessment of how good the ab-initio parameters are. In our quest for technologies that can allow the extraction of such elusive parameters, we develop an experimental technique that combines the EPR spectroscopy and µSQUID magnetometry. We demonstrate the power of the technique by performing EPR-µSQUID measurement of a magnetically diluted single crystal of Et4N[GdPc2], by sweeping the magnetic field and applying a range of multifrequency microwave pulses. As a result, we were able to directly determine the high-order ligand field parameters of the system, enabling us to test theoretical predictions made by state-of-the-art ab-initio methods.
Multi-chiral materials comprising metallosupramolecular and covalent helical polymers containing five axial motifs within a helix
Authors: Rey- Tarrío Francisco , Quiñoá Emilio , Fernández Gustavo , Freire Félix 
Published: June 2023

AbstractSupramolecular and covalent polymers share multiple structural effects such as communication mechanisms among monomer repeating units, which are related to their axial helical structure. Herein, a unique multi-helical material combining information from both metallosupramolecular and covalent helical polymers is presented. In this system, the helical structure described by the poly(acetylene) (PA) backbone (cis-cisoidal,cis-transoidal) guides the pendant groups in a fashion where a tilting degree emerges between a pendant and the adjacent ones. As a result, a multi-chiral material is formed comprising four or five axial motifs when the polyene skeleton adopts either acis-transoidalorcis-cisoidalconfiguration: the two coaxial helices—internal and external—and the two or three chiral axial motifs described by the bispyridyldichlorido PtIIcomplex array. These results show that complex multi-chiral materials can be obtained by polymerizing appropriate monomers that combine both point chirality and the ability to generate chiral supramolecular assemblies.
B cell profiles, antibody repertoire and reactivity reveal dysregulated responses with autoimmune features in melanoma
Authors: Crescioli Silvia , Correa Isabel , Ng Joseph , Willsmore Zena N. , Laddach Roman , Chenoweth Alicia , Chauhan Jitesh , Di Meo Ashley , Stewart Alexander , Kalliolia Eleni , Alberts Elena , Adams Rebecca , Harris Robert J. , Mele Silvia , Pellizzari Giulia , Black Anna B. M. , Bax Heather J. , Cheung Anthony , Nakamura Mano , Hoffmann Ricarda M. , Terranova-Barberio Manuela , Ali Niwa , Batruch Ihor , Soosaipillai Antoninus , Prassas Ioannis , Ulndreaj Antigona , Chatanaka Miyo K. , Nuamah Rosamund , Kannambath Shichina , Dhami Pawan , Geh Jenny L. C. , MacKenzie Ross Alastair D. , Healy Ciaran , Grigoriadis Anita , Kipling David , Karagiannis Panagiotis , Dunn-Walters Deborah K. , Diamandis Eleftherios P. , Tsoka Sophia , Spicer James , Lacy Katie E. , Fraternali Franca , Karagiannis Sophia N. 
Published: June 2023

AbstractB cells are known to contribute to the anti-tumor immune response, especially in immunogenic tumors such as melanoma, yet humoral immunity has not been characterized in these cancers to detail. Here we show comprehensive phenotyping in samples of circulating and tumor-resident B cells as well as serum antibodies in melanoma patients. Memory B cells are enriched in tumors compared to blood in paired samples and feature distinct antibody repertoires, linked to specific isotypes. Tumor-associated B cells undergo clonal expansion, class switch recombination, somatic hypermutation and receptor revision. Compared with blood, tumor-associated B cells produce antibodies with proportionally higher levels of unproductive sequences and distinct complementarity determining region 3 properties. The observed features are signs of affinity maturation and polyreactivity and suggest an active and aberrant autoimmune-like reaction in the tumor microenvironment. Consistent with this, tumor-derived antibodies are polyreactive and characterized by autoantigen recognition. Serum antibodies show reactivity to antigens attributed to autoimmune diseases and cancer, and their levels are higher in patients with active disease compared to post-resection state. Our findings thus reveal B cell lineage dysregulation with distinct antibody repertoire and specificity, alongside clonally-expanded tumor-infiltrating B cells with autoimmune-like features, shaping the humoral immune response in melanoma.
Astrocyte-oligodendrocyte interaction regulates central nervous system regeneration
Authors: Molina-Gonzalez Irene , Holloway Rebecca K. , Jiwaji Zoeb , Dando Owen , Kent Sarah A. , Emelianova Katie , Lloyd Amy F. , Forbes Lindsey H. , Mahmood Ayisha , Skripuletz Thomas , Gudi Viktoria , Febery James A. , Johnson Jeffrey A. , Fowler Jill H. , Kuhlmann Tanja , Williams Anna , Chandran Siddharthan , Stangel Martin , Howden Andrew J. M. , Hardingham Giles E. , Miron Veronique E. 
Published: June 2023

AbstractFailed regeneration of myelin around neuronal axons following central nervous system damage contributes to nerve dysfunction and clinical decline in various neurological conditions, for which there is an unmet therapeutic demand. Here, we show that interaction between glial cells – astrocytes and mature myelin-forming oligodendrocytes – is a determinant of remyelination. Using in vivo/ ex vivo/ in vitro rodent models, unbiased RNA sequencing, functional manipulation, and human brain lesion analyses, we discover that astrocytes support the survival of regenerating oligodendrocytes, via downregulation of the Nrf2 pathway associated with increased astrocytic cholesterol biosynthesis pathway activation. Remyelination fails following sustained astrocytic Nrf2 activation in focally-lesioned male mice yet is restored by either cholesterol biosynthesis/efflux stimulation, or Nrf2 inhibition using the existing therapeutic Luteolin. We identify that astrocyte-oligodendrocyte interaction regulates remyelination, and reveal a drug strategy for central nervous system regeneration centred on targeting this interaction.
TRIM5α recruits HDAC1 to p50 and Sp1 and promotes H3K9 deacetylation at the HIV-1 LTR
Authors: Ran Xiang-Hong , Zhu Jia-Wu , Ni Run-Ze , Zheng Yong-Tang , Chen Ya-Yun , Zheng Wei-Hua , Mu Dan 
Published: June 2023

AbstractTripartite motif-containing protein 5α (TRIM5α) is generally known to block the postentry events of HIV-1. Here, we report an uncharacterized role for TRIM5α in the maintenance of viral latency. Knockdown of TRIM5α potentiates the transcription of HIV-1 in multiple latency models, which is reversed by shRNA-resistant TRIM5α. TRIM5α suppresses TNFα-activated HIV-1 LTR-driven as well as NF-κB- and Sp1-driven gene expression, with the RING and B-box 2 domains being the essential determinants. Mechanistically, TRIM5α binds to and enhances the recruitment of histone deacetylase 1 (HDAC1) to NF-κB p50 and Sp1. ChIP‒qPCR analyses further reveal that the association of TRIM5α with HIV-1 LTR induces HDAC1 recruitment and local H3K9 deacetylation. Conserved suppression effects of TRIM5α orthologs from multiple species on both HIV-1 and endo-retroelement HERV-K LTR activities have also been demonstrated. These findings provide new insights into the molecular mechanisms by which proviral latency is initially established and activatable proviruses are resilenced by histone deacetylase recruitment.
THRONCAT: metabolic labeling of newly synthesized proteins using a bioorthogonal threonine analog
Authors: Ignacio Bob J. , Dijkstra Jelmer , Mora Natalia , Slot Erik F. J. , van Weijsten Margot J. , Storkebaum Erik , Vermeulen Michiel , Bonger Kimberly M. 
Published: June 2023

AbstractProfiling the nascent cellular proteome and capturing early proteomic changes in response to external stimuli provides valuable insights into cellular physiology. Existing metabolic protein labeling approaches based on bioorthogonal methionine- or puromycin analogs allow for the selective visualization and enrichment of newly synthesized proteins. However, their applications are limited as they often require methionine-free conditions, auxotrophic cells and/or are toxic to cells. Here, we introduce THRONCAT, a threonine-derived non-canonical amino acid tagging method based on the bioorthogonal threonine analog β-ethynylserine (βES) that enables efficient labeling of the nascent proteome in complete growth media within minutes. We use THRONCAT for the visualization and enrichment of nascent proteins in bacteria, mammalian cells and Drosophila melanogaster. We profile immediate proteome dynamics of B-cells in response to B-cell receptor activation simply by adding βES to the culture medium, demonstrating the ease-of-use of the method and its potential to address diverse biological questions. In addition, using a Drosophila model of Charcot-Marie-Tooth peripheral neuropathy, we show that THRONCAT enables visualization and quantification of relative protein synthesis rates in specific cell types in vivo.
NO at low concentration can enhance the formation of highly oxygenated biogenic molecules in the atmosphere
Authors: Nie Wei , Yan Chao , Yang Liwen , Roldin Pontus , Liu Yuliang , Vogel Alexander L. , Molteni Ugo , Stolzenburg Dominik , Finkenzeller Henning , Amorim Antonio , Bianchi Federico , Curtius Joachim , Dada Lubna , Draper Danielle C. , Duplissy Jonathan , Hansel Armin , He Xu-Cheng , Hofbauer Victoria , Jokinen Tuija , Kim Changhyuk , Lehtipalo Katrianne , Nichman Leonid , Mauldin Roy L. , Makhmutov Vladimir , Mentler Bernhard , Mizelli-Ojdanic Andrea , Petäjä Tuukka , Quéléver Lauriane L. J. , Schallhart Simon , Simon Mario , Tauber Christian , Tomé António , Volkamer Rainer , Wagner Andrea C. , Wagner Robert , Wang Mingyi , Ye Penglin , Li Haiyan , Huang Wei , Qi Ximeng , Lou Sijia , Liu Tengyu , Chi Xuguang , Dommen Josef , Baltensperger Urs , El Haddad Imad , Kirkby Jasper , Worsnop Douglas , Kulmala Markku , Donahue Neil M. , Ehn Mikael , Ding Aijun 
Published: June 2023

AbstractThe interaction between nitrogen monoxide (NO) and organic peroxy radicals (RO2) greatly impacts the formation of highly oxygenated organic molecules (HOM), the key precursors of secondary organic aerosols. It has been thought that HOM production can be significantly suppressed by NO even at low concentrations. Here, we perform dedicated experiments focusing on HOM formation from monoterpenes at low NO concentrations (0 – 82 pptv). We demonstrate that such low NO can enhance HOM production by modulating the RO2loss and favoring the formation of alkoxy radicals that can continue to autoxidize through isomerization. These insights suggest that HOM yields from typical boreal forest emissions can vary between 2.5%-6.5%, and HOM formation will not be completely inhibited even at high NO concentrations. Our findings challenge the notion that NO monotonically reduces HOM yields by extending the knowledge of RO2-NO interactions to the low-NO regime. This represents a major advance towards an accurate assessment of HOM budgets, especially in low-NO environments, which prevails in the pre-industrial atmosphere, pristine areas, and the upper boundary layer.
Northern expansion is not compensating for southern declines in North American boreal forests
Authors: Rotbarth Ronny , Van Nes Egbert H. , Scheffer Marten , Jepsen Jane Uhd , Vindstad Ole Petter Laksforsmo , Xu Chi , Holmgren Milena 
Published: June 2023

AbstractClimate change is expected to shift the boreal biome northward through expansion at the northern and contraction at the southern boundary respectively. However, biome-scale evidence of such a shift is rare. Here, we used remotely-sensed tree cover data to quantify temporal changes across the North American boreal biome from 2000 to 2019. We reveal a strong north-south asymmetry in tree cover change, coupled with a range shrinkage of tree cover distributions. We found no evidence for tree cover expansion in the northern biome, while tree cover increased markedly in the core of the biome range. By contrast, tree cover declined along the southern biome boundary, where losses were related largely to wildfires and timber logging. We show that these contrasting trends are structural indicators for a possible onset of a biome contraction which may lead to long-term carbon declines.
Single-gene resolution of diversity-driven overyielding in plant genotype mixtures
Authors: Wuest Samuel E. , Schulz Lukas , Rana Surbhi , Frommelt Julia , Ehmig Merten , Pires Nuno D. , Grossniklaus Ueli , Hardtke Christian S. , Hammes Ulrich Z. , Schmid Bernhard , Niklaus Pascal A. 
Published: June 2023

AbstractIn plant communities, diversity often increases productivity and functioning, but the specific underlying drivers are difficult to identify. Most ecological theories attribute positive diversity effects to complementary niches occupied by different species or genotypes. However, the specific nature of niche complementarity often remains unclear, including how it is expressed in terms of trait differences between plants. Here, we use a gene-centred approach to study positive diversity effects in mixtures of natural Arabidopsis thaliana genotypes. Using two orthogonal genetic mapping approaches, we find that between-plant allelic differences at the AtSUC8 locus are strongly associated with mixture overyielding. AtSUC8 encodes a proton-sucrose symporter and is expressed in root tissues. Genetic variation in AtSUC8 affects the biochemical activities of protein variants and natural variation at this locus is associated with different sensitivities of root growth to changes in substrate pH. We thus speculate that - in the particular case studied here - evolutionary divergence along an edaphic gradient resulted in the niche complementarity between genotypes that now drives overyielding in mixtures. Identifying genes important for ecosystem functioning may ultimately allow linking ecological processes to evolutionary drivers, help identify traits underlying positive diversity effects, and facilitate the development of high-performance crop variety mixtures.
Sensitive near-infrared circularly polarized light detection via non-fullerene acceptor blends
Authors: Wan Li , Zhang Rui , Cho Eunkyung , Li Hongxiang , Coropceanu Veaceslav , Brédas Jean-Luc , Gao Feng 
Published: June 2023

AbstractCircularly polarized light (CPL) is widely used for various applications in sensing and imaging1–3. An ongoing challenge is to realize high-quality CPL detection using chiral organic semiconductors, especially in the near-infrared (NIR) region4. Chiral molecules tend to rely on twisted stereogenic moieties; however, conventional approaches to reduce the bandgap of organic semiconductors are based on the use of co-planar backbones that commonly lead to molecular symmetries preventing chirality. Here we report a widely applicable strategy to directly induce chiroptical activity in planar non-fullerene acceptors5–7, which are widely used for high-performance organic photovoltaics and provide a wealth of opportunities to fill the spectral gap of CPL detection in the NIR regime. We demonstrate proof-of-concept circularly polarized organic photodiodes using chiroptically active non-fullerene acceptor blends, which exhibit strong circular dichroism and hence great sensitivity to CPL in the NIR region. Importantly, this strategy is found to be effective in a wide series of state-of-the-art non-fullerene acceptor families including ITIC5, o-IDTBR6 and Y6 analogues7, which substantially broadens the range of materials applicable to NIR CPL detection.
Population, land use and economic exposure estimates for Europe at 100 m resolution from 1870 to 2020
Authors: Paprotny Dominik , Mengel Matthias 
Published: June 2023

AbstractUnderstanding the influence of climate change on past extreme weather impacts is a vital research task. However, the effects of climate change are obscured in the observed impact data series due to the rapid evolution of the social and economic circumstances in which the events occurred. The HANZE v2.0 (Historical Analysis of Natural HaZards in Europe) dataset presented in this study quantifies the evolution of key socioeconomic drivers in Europe since 1870, namely land use, population, economic activity and assets. It consists of algorithms to reallocate baseline (2011) land use and population for any given year based on a large collection of historical subnational- and national-level statistics, and then disaggregate data on production and tangible assets by economic sector into a high-resolution grid. Raster datasets generated by the model enable reconstructing exposure within the footprint of any extreme event both at the time of occurrence and anytime between 1870 and 2020. This allows the separation of the effects of climate change from the effects of exposure change.
Impacts of spaceflight experience on human brain structure
Authors: McGregor Heather R. , Hupfeld Kathleen E. , Pasternak Ofer , Beltran Nichole E. , De Dios Yiri E. , Bloomberg Jacob J. , Wood Scott J. , Mulavara Ajitkumar P. , Riascos Roy F. , Reuter-Lorenz Patricia A. , Seidler Rachael D. 
Published: June 2023

AbstractSpaceflight induces widespread changes in human brain morphology. It is unclear if these brain changes differ with varying mission duration or spaceflight experience history (i.e., novice or experienced, number of prior missions, time between missions). Here we addressed this issue by quantifying regional voxelwise changes in brain gray matter volume, white matter microstructure, extracellular free water (FW) distribution, and ventricular volume from pre- to post-flight in a sample of 30 astronauts. We found that longer missions were associated with greater expansion of the right lateral and third ventricles, with the majority of expansion occurring during the first 6 months in space then appearing to taper off for longer missions. Longer inter-mission intervals were associated with greater expansion of the ventricles following flight; crew with less than 3 years of time to recover between successive flights showed little to no enlargement of the lateral and third ventricles. These findings demonstrate that ventricle expansion continues with spaceflight with increasing mission duration, and inter-mission intervals less than 3 years may not allow sufficient time for the ventricles to fully recover their compensatory capacity. These findings illustrate some potential plateaus in and boundaries of human brain changes with spaceflight.
Underpinning the use of indium as a neutron absorbing additive in zirconolite by X-ray absorption spectroscopy
Authors: Blackburn Lewis R. , Townsend Luke T. , Dixon Wilkins Malin C. , Ina Toshiaki , Kuman Merve , Sun Shi-Kuan , Mason Amber R. , Gardner Laura J. , Stennett Martin C. , Corkhill Claire L. , Hyatt Neil C. 
Published: June 2023

AbstractIndium (In) is a neutron absorbing additive that could feasibly be used to mitigate criticality in ceramic wasteforms containing Pu in the immobilised form, for which zirconolite (nominally CaZrTi2O7) is a candidate host phase. Herein, the solid solutions Ca1-xZr1-xIn2xTi2O7 (0.10 ≤ x ≤ 1.00; air synthesis) and Ca1-xUxZrTi2-2xIn2xO7 (x = 0.05, 0.10; air and argon synthesis) were investigated by conventional solid state sintering at a temperature of 1350 °C maintained for 20 h, with a view to characterise In3+ substitution behaviour in the zirconolite phase across the Ca2+, Zr4+ and Ti4+ sites. When targeting Ca1-xZr1-xIn2xTi2O7, single phase zirconolite-2M was formed at In concentrations of 0.10 ≤ x ≤ 0.20; beyond x ≥ 0.20, a number of secondary In-containing phases were stabilised. Zirconolite-2M remained a constituent of the phase assemblage up to a concentration of x = 0.80, albeit at relatively low concentration beyond x ≥ 0.40. It was not possible to synthesise the In2Ti2O7 end member compound using a solid state route. Analysis of the In K-edge XANES spectra in the single phase zirconolite-2M compounds confirmed that the In inventory was speciated as trivalent In3+, consistent with targeted oxidation state. However, fitting of the EXAFS region using the zirconolite-2M structural model was consistent with In3+ cations accommodated within the Ti4+ site, contrary to the targeted substitution scheme. When deploying U as a surrogate for immobilised Pu in the Ca1-xUxZrTi2-2xIn2xO7 solid solution, it was demonstrated that, for both x = 0.05 and 0.10, In3+ was successfully able to stabilise zirconolite-2M when U was distributed predominantly as both U4+ and average U5+, when synthesised under argon and air, respectively, determined by U L3-edge XANES analysis.