bluuebunny/crossref_metadata_2025_split huggingface dataset:
Revealing the Mechanism of sp‐N Doping in Graphdiyne for Developing Site‐Defined Metal‐Free Catalysts
Authors: Liu Baokun , Zhan Shuhui , Du Jiang , Yang Xin , Zhao Yasong , Li Lulu , Wan Jiawei , Zhao Zhi‐Jian , Gong Jinlong , Yang Nailiang , Yu Ranbo , Wang Dan 
Published: October 2022

AbstractDue to the limited reserves of metals, scientists are devoted to exploring high‐performance metal‐free catalysts based on carbon materials to solve environment‐related issues. Doping would build up inhomogeneous charge distribution on surface, which is an efficient approach for boosting the catalytic performance. However, doping sites are difficult to control in traditional carbon materials, thus hindering their development. Taking the advantage of unique sp‐C in graphdiyne (GDY), a new N doping configuration of sp‐hybridized nitrogen (sp‐N), bringing a Pt‐comparable catalytic activity in oxygen reduction reaction is site‐defined introduced. However, the reaction intermediate of this process is never captured, hindering the understanding of the mechanism and the precise synthesis of metal‐free catalysts. After the four‐year study, the fabrication of intermediate‐like molecule is realized, and finally sp‐N doped GDY via the pericyclic reaction is obtained. Compared with GDY doped with other N configurations, the designed sp‐N GDY shows much higher catalytic activity in electroreduction of CO2 toward CH4 production, owing to the unique electronic structure introduced by sp‐N, which is more favorable in stabilizing the intermediate. Thus, besides opening the black‐box for the site‐defined doping, this work reveals the relationship between doping configuration and products of CO2 reduction.
Activating C–H Bonds by Tuning Fe Sites and an Interfacial Effect for Enhanced Methanol Oxidation
Authors: Huang Sheng , Feng Feng , Huang Rong‐Ting , Ouyang Ting , Liu Jinlong , Liu Zhao‐Qing 
Published: October 2022

AbstractThe interaction mechanism between the reacting species and the active site of α‐Fe2O3‐based photoanodes in photoelectrochemical methanol conversion reaction is still ambiguous. Herein, a simple two‐step strategy is demonstrated to fabricate a porous α‐Fe2O3/CoFe2O4 heterojunction for the methanol conversion reaction. The influence of the electronic structure of active site and interfacial effect on the reaction are investigated by constructing two different FeO6 octahedral configurations and heterogeneous structures. The optimal sample ZnFeCo‐2 affords high photocurrent density of 1.17 mA cm−2 at 0.5 V vs Ag/AgCl, which is 3.2 times than that of ZnFe (0.37 mA cm−2). Meanwhile, the ZnFeCo‐2 also exhibits 97.8% Faraday efficiency of CH3OH to HCHO, and long‐term stability over 40 h. Furthermore, density functional theory calculations reveal that the heterostructured α‐Fe2O3/CoFe2O4 with favorable electron transfer effectively lowers methanol adsorption, C–H bond activation, and HCHO desorption energy relative to the pristine α‐Fe2O3, resulting in excellent methanol conversion efficiency.
Fusing ToF‐SIMS Images for Spatial‐Spectral Resolution Enhancement using a Convolutional Neural Network
Authors: Gardner Wil , Winkler David A. , Maliki Ruqaya , Cutts Suzanne M. , Ellis Sarah , Anderson Robin L. , Muir Benjamin W. , Pigram Paul J. 
Published: October 2022

AbstractHyperspectral data sets generated by time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) contain valuable spatial‐spectral information characterizing the distribution of atomic and molecular species across a sample surface. Modern ToF‐SIMS instruments have high spatial resolution (in the order of tens of nanometers) relative to most other mass spectrometry imaging (MSI) techniques. However, there is generally a trade‐off between spatial and mass resolution when using different instrument modes. In this study, a convolutional neural network (CNN) fusion method is used to fuse correlated high spatial and high mass resolution ToF‐SIMS hyperspectral data sets. This process generates resolution‐enhanced data, which exhibit both high spatial and mass resolution. The CNN fusion method is applied to ToF‐SIMS images of a simple, well‐characterized gold mesh sample and a significantly more complex biological (tumor) tissue section. The method is compared to another linear fusion method used in the broader MSI community and a substantial improvement is found. This comparison focuses on both visual quality observations as well as statistical similarity measures. This work demonstrates the utility of the CNN fusion method for ToF‐SIMS data, enabling investigation of the atomic and molecular characteristics of surfaces at high spatial and mass spectral resolution.
Material‐Independent 3D Patterning Via Two‐Photon Lithography and Discontinuous Wetting
Authors: Dong Zheqin , Monti Joël , Cui Haijun , Welle Alexander , Singaraju Surya A. , Blasco Eva , Levkin Pavel. A. 
Published: October 2022

AbstractThe fabrication of complex 3D structures composed of micrometer‐sized features made of different functional materials is an immensely important and yet highly challenging task. Here, a method is developed to fabricate multimaterial 3D structures with micrometer precision by combining macroscopic 3D printing (digital light processing), with two‐photon lithography (2PL) and material‐independent discontinuous dewetting. Specifically, 3D inherently superhydrophobic objects are first printed by DLP, followed by creating hydrophilic micropatterns on their surface using 2PL. By exploiting the effect of discontinuous wetting, the selective deposition of solutions of functional materials into microscopic hydrophilic regions on the surface of 3D structures, with high resolution and great design flexibility is demonstrated. Importantly, the method is material‐independent and enables the micropatterning of a variety of functional materials dispersed in aqueous solutions including polydopamine, silica, or Ag nanoparticles. As an exemplary application, it is shown that conductive Ag electrodes can be created on the curved surface of 3D‐printed objects to construct structural electronics. The flexibility, high resolution, and material diversity in designing multimaterial 3D structures open exciting new functionalities and possibilities in a variety of applications including advanced electronics, soft robotics, and chemical or bioengineering.
Novel Tetradentate Platinum(II) Complexes and Their Use in Blue Phosphorescent Organic Light‐Emitting Diodes
Authors: Ryu Chan Hee , Kim Seung Chan , Kim Mingi , Yi Sanghee , Lee Jun Yeob , Lee Kang Mun 
Published: October 2022

AbstractAlthough the remarkable growth of the organic light‐emitting diode (OLED) industry has occurred via continuous, extensive efforts toward the utilization of various organometallic luminophores as phosphorescent emitters, the development of blue phosphorescent emitters with improved efficiencies and high electrochemical stabilities is essential. To this end, herein the preparation of two novel tetradentate Pt(II) complexes, Pt1 and Pt2, and their application as blue phosphorescent emitters in OLED devices is described. Both complexes exhibit intense bluish emission in the solution and solid states. In addition, these complexes display very high phosphorescent quantum efficiencies (>89%) with host materials and thermal stabilities (>390 °C). Multilayer phosphorescent OLEDs containing Pt1 or Pt2 as emitters with mCBP/CNmCBP‐CN mixed‐host systems are fabricated. The devices exhibit outstanding performances, including high current, power, external efficiencies, and potential device lifetime in addition to sky‐blue (Pt1) or blue (Pt2) electroluminescence. These results clearly suggest that these tetradentate Pt(II) dopants are promising candidates as highly efficient, stable blue phosphorescent emitters in OLEDs.
NIR‐II Excitation Phototheranostic Platform for Synergistic Photothermal Therapy/Chemotherapy/Chemodynamic Therapy of Breast Cancer Bone Metastases
Authors: Sun Pengfei , Qu Fan , Zhang Chi , Cheng Pengfei , Li Xiangyu , Shen Qingming , Li Daifeng , Fan Quli 
Published: October 2022

AbstractTo improve bone metastases treatment efficacy, current strategies are focused on the integration of chemotherapy with phototheranostic. However, the success of phototheranostic approaches is hampered by the limited tissue penetration depth of near‐infrared‐I (NIR‐I) light (700–900 nm). In this study, a NIR‐II (1000–1700 nm) excitation phototheranostic (BTZ/Fe2+@BTF/ALD) is presented for NIR‐II fluorescence imaging and NIR‐II photoacoustic imaging‐guided NIR‐II photothermal therapy (PTT), chemotherapy, and chemodynamic therapy (CDT) of breast cancer bone metastases. This phototheranostic is developed by integrating a dopamine‐modified NIR‐II absorbing donor–acceptor–donor small molecule (BBT‐FT‐DA), the boronate anticancer drug bortezomib (BTZ), and Fe2+ ions, as CDT catalysts, into an amphiphilic PEGylated phospholipid modified with the bone‐targeting ligand alendronate. In acidic and hydrogen peroxide (H2O2) over expression tumor microenvironment, the boronate–catechol linkage is cleaved and BTZ and Fe2+ ions are released to initiate the Fenton reaction, that is, chemotherapy and CDT, respectively, are initialized. It is confirmed using the murine 4T1 bone metastasis model that BTZ/Fe2+@BTF/ALD significantly suppresses the progression of tumor cells in the bone tissue via a synergistic NIR‐II PTT/chemotherapy/CDT effect. Overall, this work provides fresh insights to guide the development of NIR‐II phototheranostics for breast cancer bone metastases.
An exploration into the conversion of dominance to additive genetic variance in contrasting environments
Authors: So Cameron P. , Sibolibane Mia M. , Weis Arthur E. 
Published: October 2022

AbstractPremiseThe evolutionary response of a trait to environmental change depends upon the level of additive genetic variance. It has been long argued that sustained selection will tend to deplete additive genetic variance as favored alleles approach fixation. Non‐additive genetic variance, due to interactions among alleles within and between loci, does not immediately contribute to an evolutionary response. However, shifts in the allele frequencies within and between interacting loci may convert non‐additive variance into additive variance. Here we consider the possibility that an environmental shift may alter allelic interactions in ways that convert dominance into additive genetic variance.MethodsWe grew a pedigreed population of Brassica rapa in greenhouse and field conditions. The field conditions mimicked agricultural conditions from which the base population was drawn, while the greenhouse featured benign conditions. We used Bayesian models to estimate the additive, dominance, and maternal components of quantitative genetic variance. We also estimated genetic correlations across environments using parental breeding values.ResultsAlthough the additive genetic variance was elevated in the greenhouse condition, no consistent pattens emerged that would indicate a conversion of dominance variance. The unusually low genetic variance and broad confidence intervals for the variance estimates obtained through this analysis preclude definitive interpretations.ConclusionsFurther studies are needed to determine whether between‐environment changes in additive genetic variance can be traced to conversion of dominance variance.
The challenges of growing orchids from seeds for conservation: An assessment of asymbiotic techniques
Authors: Jolman Devani , Batalla Martín I. , Hungerford Alexis , Norwood Pryce , Tait Noah , Wallace Lisa E. 
Published: October 2022

AbstractLewis Knudson first successfully germinated orchid seeds asymbiotically on artificial medium in 1922. While many orchid species have since been grown asymbiotically, the tremendous variation in how species respond to artificial medium and growth conditions ex situ has also become apparent in the past century. In this study, we reviewed published journal articles on asymbiotic orchid seed germination to provide a summary of techniques used and to evaluate if these differ between terrestrial and epiphytic species, to identify areas where additional research is needed, and to evaluate whether asymbiotic germination could be used more often in ex situ conservation. We found articles reporting successful asymbiotic germination of 270 species and 20 cultivars across Orchidaceae. Researchers often used different techniques with epiphytic versus terrestrial species, but species‐specific responses to growth media and conditions were common, indicating that individualized protocols will be necessary for most species. The widespread success in generating seedlings on artificial media suggests that asymbiotic techniques should be another tool for the conservation of rare orchid species. Further advances are needed in understanding how to introduce mycorrhizae to axenically grown orchids and to maximize the viability of seedlings reintroduced into natural habitats to fully utilize these methods for conservation.
Iron Catalysis: A New Horizon Towards Organoboron‐mediated C−C Cross‐coupling
Authors: Mondal Suparna , Kanti Das Kanak , Panda Santanu 
Published: October 2022

AbstractTransition metal‐catalyzed cross‐couplings have had a profound impact on chemical synthesis. Among the various transition metals, iron has drawn huge attention due to its cost effectiveness, range of stable oxidation states, Lewis acidic property and releatively less toxicity. Iron complexes have exhibited an efficient catalytic activity towards the cross‐coupling reaction using organomagnesium, organolithium and organozinc reagent. Organoboron compounds are also engaged as a coupling partner for Fe catalysed C−C bond forming reactions. Over the last two decades’ various iron catalysed C−C bond forming reactions have been developed. This review will summarize the chronological development in this research area along with challenges appearing especially in the past decade.
Analysis of Selenoprotein F Binding to UDP‐Glucose:Glycoprotein Glucosyltransferase (UGGT) by a Photoreactive Crosslinker
Authors: Higashi Sayaka , Imamura Yuki , Kikuma Takashi , Matoba Takahiro , Orita Saya , Yamaguchi Yoshiki , Ito Yukishige , Takeda Yoichi 
Published: October 2022

AbstractIn the endoplasmic reticulum glycoprotein quality control system, UDP‐glucose : glycoprotein glucosyltransferase (UGGT) functions as a folding sensor. Although it is known to form a heterodimer with selenoprotein F (SelenoF), the details of the complex formation remain obscure. A pulldown assay using co‐transfected SelenoF and truncated mutants of human UGGT1 (HUGT1) revealed that SelenoF binds to the TRXL2 domain of HUGT1. Additionally, a newly developed photoaffinity crosslinker was selectively introduced into cysteine residues of recombinant SelenoF to determine the spatial orientation of SelenoF to HUGT1. The crosslinking experiments showed that SelenoF formed a covalent bond with amino acids in the TRXL3 region and the interdomain between βS2 and GT24 of HUGT1 via the synthetic crosslinker. SelenoF might play a role in assessing and refining the disulfide bonds of misfolded glycoproteins in the hydrophobic cavity of HUGT1 as it binds to the highly flexible region of HUGT1 to reach its long hydrophobic cavity. Clarification of the SelenoF‐binding domain of UGGT and its relative position will help predict and reveal the function of SelenoF from a structural perspective.
Altering the Regiospecificity of a CatecholO‐methyltransferase through Rational Design: Vanilloid vs. Isovanilloid Motifs in the B‐ring of Flavonoids
Authors: Dippe Martin , Davari Mehdi D. , Weigel Benjamin , Heinke Ramona , Vogt Thomas , Wessjohann Ludger A. 
Published: October 2022

AbstractRational re‐design of the substrate pocket of phenylpropanoid‐flavonoidO‐methyltransferase (PFOMT) fromMesembryanthemum crystallinum, an enzyme that selectively methylates the 3′‐position (=meta‐position) in catechol‐moieties of flavonoids to guiacol‐moieties, provided the basis for the generation of variants with opposite, i. e. 4′‐ (para‐) regioselectivity and enhanced catalytic efficiency. A double variant (Y51R/N202W) identified through a newly developed colorimetric assay efficiently modified thepara‐position in flavanone and flavanonol substrates, providing access to the sweetener molecule hesperetin and other rare plant flavonoids having an isovanilloid motif.
Neutral Boryl Radicals in Mixed‐Valent B(III)Br‐B(II) Adducts
Authors: Liu Tong‐Tong , Chen Jiaxin , Chen Xin‐Lei , Ma Li , Guan Bing‐Tao , Lin Zhenyang , Shi Zhang‐Jie 
Published: October 2022

AbstractThe general strategies to stabilize a boryl radical involve single electron delocalization by π‐system and the steric hinderance from bulky groups. Herein, a new class of boryl radicals is reported, with intramolecular mixed‐valent B(III)Br‐B(II) adducts ligated by a cyclic (alkyl)(amino)carbene (CAAC). The radicals feature a large spin density on the boron center, which is ascertained by EPR spectroscopy and DFT calculations. Structural and computational analyses revealed that the stability of radical species was assisted by the CAAC ligand and a weak but significant B(III)Br‐B(II) interaction, suggesting a cooperative avenue for stabilization of boryl radicals. Two‐electron reduction of these new boryl radicals provides C−H insertion products via a borylene intermediate.
In Situ Synthesis of Cu3P/P‐Doped g‐C3N4 Tight 2D/2D Heterojunction Boosting Photocatalytic H2 Evolution†
Authors: Hou Fangyong , Liu Feng , Wu Haochen , Qasim Muhammad , Chen Yi , Duan Yang , Feng Zhibo , Liu Maochang 
Published: October 2022

Comprehensive SummaryHeterojunction design in a two‐dimensional (2D) fashion has been deemed beneficial for improving the photocatalytic activity of g‐C3N4 because of the promoted interfacial charge transfer, yet still facing challenges. Herein, we construct a novel 2D/2D Cu3P nanosheet/P‐doped g‐C3N4 (PCN) nanosheet heterojunction photocatalyst (PCN/Cu3P) through a simple in‐situ phosphorization treatment of 2D/2D CuS/g‐C3N4 composite for photocatalytic H2 evolution. We demonstrate that the 2D lamellar structure of both CuS and g‐C3N4 could be well reserved in the phosphorization process, while CuS and g‐C3N4 in‐situ transformed into Cu3P and PCN, respectively, leading to the formation of PCN/Cu3P tight 2D/2D heterojunction. Owing to the large contact area provided by intimate face‐to‐face 2D/2D structure, the PCN/Cu3P photocatalyst exhibits significantly enhanced charge separation efficiency, thus achieving a boosted visible‐light‐driven photocatalytic behavior. The highest rate for H2 evolution reaches 5.12 μmol·h–1, nearly 24 times and 368 times higher than that of pristine PCN and g‐C3N4, respectively. This work represents an excellent example in elaborately constructing g‐C3N4‐based 2D/2D heterostructure and could be extended to other photocatalyst/co‐catalyst system.
Vegetation complexity and nesting resource availability predict bee diversity and functional traits in community gardens
Authors: Felderhoff Julia , Gathof Anika K. , Buchholz Sascha , Egerer Monika 
Published: October 2022

AbstractUrban gardens can support diverse bee communities through resource provision in resource poor environments. Yet the effects of local habitat and landscape factors on wild bee communities in cities is still insufficiently understood, nor is how this information could be applied to urban wildlife conservation. Here we investigate how taxonomic and functional diversity of wild bees and their traits in urban community gardens are related to garden factors and surrounding landscape factors (e.g., plant diversity, amount of bare ground, amount of nesting resources, amount of landscape imperviousness). Using active and passive methods in 18 community gardens in Berlin, Germany, we documented 26 genera and 102 species of bees. We found that higher plant species richness and plant diversity as well as higher amounts of deadwood in gardens leads to higher numbers of wild bee species and bee (functional) diversity. Furthermore, higher landscape imperviousness surrounding gardens correlates with more cavity nesting bees, whereas a higher amount of bare ground correlates with more ground‐nesting bees. Pollen specialization was positively associated with plant diversity, but no factors strongly predicted the proportion of endangered bees. Our results suggest that, aside from foraging resources, nesting resources should be implemented in management for more pollinator‐friendly gardens. If designed and managed using such evidence‐based strategies, urban gardens can create valuable foraging and nesting habitats for taxonomically and functionally diverse bee communities in cities.
Phylogenetic risk assessment is robust for forecasting the impact ofEuropean insects onNorthAmerican conifers
Authors: Uden Daniel R. , Mech Angela M. , Havill Nathan P. , Schulz Ashley N. , Ayres Matthew P. , Herms Daniel A. , Hoover Angela M. , Gandhi Kamal J. K. , Hufbauer Ruth A. , Liebhold Andrew M. , Marsico Travis D. , Raffa Kenneth F. , Thomas Kathryn A. , Tobin Patrick C. , Allen Craig R. 
Published: October 2022

AbstractSome introduced species cause severe damage, although the majority have little impact. Robust predictions of which species are most likely to cause substantial impacts could focus efforts to mitigate those impacts or prevent certain invasions entirely. Introduced herbivorous insects can reduce crop yield, fundamentally alter natural and managed forest ecosystems, and are unique among invasive species in that they require certain host plants to succeed. Recent studies have demonstrated that understanding the evolutionary history of introduced herbivores and their host plants can provide robust predictions of impact. Specifically, divergence times between hosts in the native and introduced ranges of a nonnative insect can be used to predict the potential impact of the insect should it establish in a novel ecosystem. However, divergence time estimates vary among published phylogenetic datasets, making it crucial to understand if and how the choice of phylogeny affects prediction of impact. Here, we tested the robustness of impact prediction to variation in host phylogeny by using insects that feed on conifers and predicting the likelihood of high impact using four different published phylogenies. Our analyses ranked 62 insects that are not established in North America and 47 North American conifer species according to overall risk and vulnerability, respectively. We found that results were robust to the choice of phylogeny. Although published vascular plant phylogenies continue to be refined, our analysis indicates that those differences are not substantial enough to alter the predictions of invader impact. Our results can assist in focusing biosecurity programs for conifer pests and can be more generally applied to nonnative insects and their potential hosts by prioritizing surveillance for those insects most likely to be damaging invaders.
Dear old love: Effects of reflecting on nostalgic memories about ex‐partners on current romantic relationship
Authors: Ai Ting , Gillath Omri , Landau Mark 
Published: October 2022

AbstractResearch on the impact of ex‐romantic partners on current romantic relationships is mainly focused on negative aspects. Here instead we focus on the potential positive influence of reflecting on nostalgic memories of one's ex‐partner. In three studies, we found that reflecting on nostalgic memories of one's ex‐partner increased the perception of current relationship quality (Studies 1– 3) and approach motivation towards the current relationship (Study 3), compared to a control condition. We also tested a potential underlying mechanism—perception of self‐growth. We found that perception of self‐growth mediated the positive effects of reflecting on nostalgic memories about an ex‐partner on perceived current relationship quality (Studies 2 and 3) and approach motivation in the current relationship (Study 3). Implications for research and therapy are discussed.