bluuebunny/crossref_metadata_2025_split huggingface dataset:
Polymer Nanoantidotes
Authors: Yang Jiazhen , Li Hongjie , Zou Haoyang , Ding Jianxun 
Published: June 2023

AbstractIntoxication is one of the most common causes of accidental death globally. Although some antidotes capable of neutralizing the toxicity of certain xenobiotics have become well established, the current reality is that clinicians primarily rely on nonspecific extracorporeal techniques to remove toxins. Nano‐intervention strategies in which nanoantidotes neutralize toxicity in situ via physical interaction, chemical bonding, or biomimetic clearance have begun to show clinical potential. However, most nanoantidotes remain in the proof‐of‐concept stage, and the difficulty of constructing clinical relevance models and the unclear pharmacokinetics of nanoantidotes hinder their translation to clinic. This Concept reviews the detoxification mechanisms of polymer nanoantidotes and predicts the opportunities and challenges associated with their clinical application.
Recent Developments on Photochemical Synthesis of 1,n‐Dicarbonyls
Authors: Mondal Subhashis , Chatterjee Nirbhik , Maity Soumitra 
Published: June 2023

Abstract1,n‐dicarbonyls are one of the most fascinating chemical feedstocks finding abundant usage in the field of pharmaceuticals. Besides, they are utilized in a plethora of synthesis in general synthetic organic chemistry. A number of ‘conventional’ methods are available for their synthesis, such as the Stetter reaction, Baker‐Venkatraman rearrangement, oxidation of vicinal diols, and oxidation of deoxybenzoins, synonymous with unfriendly reagents and conditions. In the last 15 years or so, photocatalysis has taken the world of synthetic organic chemistry by a remarkable renaissance. It is fair to say now that everybody loves the light and photoredox chemistry has opened a new gateway to organic chemists towards milder, more simpler alternatives to the previously available methods, allowing access to many sensitive reactions and products. In this review, we present the readers with the photochemical synthesis of a variety of 1,n‐dicarbonyls. Diverse photocatalytic pathways to these fascinating molecules have been discussed, placing special emphasis on the mechanisms, giving the reader an opportunity to find all these significant developments in one place.
Surface Chemistry and Specific Surface Area Rule the Efficiency of Gold Nanoparticle Sensitizers in Proton Therapy
Authors: Johny Jacob , van Halteren Charlotte E. R. , Cakir Fatih‐Can , Zwiehoff Sandra , Behrends Carina , Bäumer Christian , Timmermann Beate , Rauschenbach Laurèl , Tippelt Stephan , Scheffler Björn , Schramm Alexander , Rehbock Christoph , Barcikowski Stephan 
Published: June 2023

AbstractGold nanoparticles (AuNPs) are currently the most studied radiosensitizers in proton therapy (PT) applicable for the treatment of solid tumors, where they amplify production of reactive oxygen species (ROS). However, it is underexplored how this amplification is correlated with the AuNPs’ surface chemistry. To clarify this issue, we fabricated ligand‐free AuNPs of different mean diameters by laser ablation in liquids (LAL) and laser fragmentation in liquids (LFL) and irradiated them with clinically relevant proton fields by using water phantoms. ROS generation was monitored by the fluorescent dye 7‐OH‐coumarin. Our findings reveal an enhancement of ROS production driven by I) increased total particle surface area, II) utilization of ligand‐free AuNPs avoiding sodium citrate as a radical quencher ligands, and III) a higher density of structural defects generated by LFL synthesis, indicated by surface charge density. Based on these findings it may be concluded that the surface chemistry is a major and underexplored contributor to ROS generation and sensitizing effects of AuNPs in PT. We further highlight the applicability of AuNPs in vitro in human medulloblastoma cells.
Selective Photodynamic Activity of Tetrakis(4‐aminophenyl)porphyrins with and without Acetyl Protecting Groups on Cancer and Normal Cells
Authors: Okuno Masafumi , Yamana Keita , Kawamura Shogo , Nishimura Kotaro , Hino Shodai , Kawasaki Riku , Ikeda Atsushi 
Published: June 2023

AbstractTetrakis(4‐aminophenyl)porphyrin (1) and tetrakis(4‐acetamidophenyl)porphyrin (2) were dissolved in water with the incorporation of a polysaccharide (λ‐carrageenan (CGN)) as a water‐solubilizing agent. Although the photodynamic activity of the CGN‐2 complex was considerably lower than that of the CGN‐1 complex, the selectivity index (SI; IC50 in a normal cell/IC50 in a cancer cell) of the CGN‐2 complex was considerably higher than that of the CGN‐1 complex. This is because the photodynamic activity of the CGN‐2 complex was significantly affected by the intracellular uptakes by the normal and cancer cells. During in vivo experiments, the CGN‐2 complex inhibited tumor growth under light irradiation with high blood retention compared with the CGN‐1 complex and Photofrin, which exhibited lower blood retention. This study showed that the photodynamic activity and SI are influenced by substituent groups of arene in the meso‐positions of porphyrin analogs.
In Situ Formation of CoP/Co3O4 Heterojunction for Efficient Overall Water Splitting
Authors: Tian Guoliang , Liu Xiaolei , Song Shuhong , Zhang Qianqian , Wang Zeyan , Liu Yuanyuan , Zheng Zhaoke , Cheng Hefeng , Dai Ying , Huang Baibiao , Wang Peng 
Published: June 2023

AbstractElectrochemical water splitting is an environmentally friendly and effective energy storage method. However, it is still a huge challenge to prepare non‐noble metal based electrocatalysts that possess high activity and long‐term durability to realize efficient water splitting. Here, we present a novel method of low‐temperature phosphating for preparing CoP/Co3O4 heterojunction nanowires catalyst on titanium mesh (TM) substrate that can be used for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting. CoP/Co3O4@TM heterojunction showed an excellent catalytic performance and long‐term durability in 1.0 M KOH electrolyte. The overpotential of CoP/Co3O4@TM heterojunction was only 257 mV at 20 mA cm−2 during the OER process, and it could work stably more than 40 h at 1.52 V versus reversible hydrogen electrode (vs. RHE). During the HER process, the overpotential of CoP/Co3O4@TM heterojunction was only 98 mV at −10 mA cm−2. More importantly, when used as anodic and cathodic electrocatalyst, they achieved 10 mA cm−2 at 1.59 V. The Faradaic efficiencies of OER and HER were 98.4 % and 99.4 %, respectively, outperforming Ru/Ir‐based noble metal electrocatalysts and other non‐noble metal electrocatalysts for overall water splitting.
Factors Controlling Complex Morphologies of Isomorphous Metal‐Organic Frameworks**
Authors: Singh Vivek , Feldman Yishay , Leitus Gregory , Brumfeld Vlad , Shimon Linda J. W. , Lahav Michal , van der Boom Milko E. 
Published: June 2023

AbstractWe demonstrate here how nitrate salts of bivalent copper, nickel, cobalt, and manganese, along with an achiral organic ligand, assemble into various structures such as symmetrical double‐decker flowers, smooth elongated hexagonal bipyramids, and hexagonal prisms. Large morphological changes occur in these structures because of different metal cations, although they maintain isomorphous hexagonal crystallographic structures. Metal cations with stronger coordination to ligands (Cu and Ni) tend to form uniform crystals with unusual shapes, whereas weaker coordinating metal cations (Mn and Co) produce crystals with more regular hexagonal morphologies. The unusual flower‐like crystals formed with copper nitrate have two pairs of six symmetrical petals with hexagonal convex centers. The texture of the petals indicates dendritic growth. Two different types of morphologies were formed by using different copper nitrate‐to‐ligand ratios. An excess of the metal salt results in uniform and hexagonal crystals having a narrow size distribution, whereas the use of an excess of ligand results in double‐decker morphologies. Mechanistically, an intermediate structure was observed with slightly concave facets and a domed center. Such structures most likely play a key role in the formation of double‐decker crystals that can be formed by fusion processes. The coordination chemistry results in isostructural chiral frameworks consisting of two types of continuous helical channels. Four pyridine units from four separate ligands are coordinated to the metal center in a plane having a chiral (propeller‐type) arrangement. The individual double‐decker flower crystals are homochiral and a batch consists of crystals having both handedness.
Impact of Catalyst Deuteration on the Reactivity of Chiral Phase‐Transfer Organocatalysts
Authors: Murayama Sei , Li Zhurong , Liang Huatai , Liu Yan , Naka Hiroshi , Maruoka Keiji 
Published: June 2023

AbstractSite‐specifically deuterated organocatalysts were prepared and found to show improved reactivity over the non‐deuterated analogs. Two privileged C2‐symmetric chiral binaphthyl‐modified tetraalkylammonium salts were selected for this study. The stability of these phase‐transfer catalysts was generally improved by site‐specific deuteration, though the degree of improvement was structure dependent. In particular, a large secondary kinetic isotope effect was observed for the tetradeuterated phase‐transfer catalyst. The performance of these deuterated catalysts in the asymmetric catalytic alkylation of amino acid derivatives was better than that of non‐deuterated analogs at low catalyst loadings. The results suggest that catalyst deuteration is a promising strategy for enhancing the stability and performance of organocatalysts.
Can we still measure circular dichroism with circular dichroism spectrometers: The dangers of anisotropic artifacts
Authors: Ugras Thomas J. , Yao Yuan , Robinson Richard D. 
Published: June 2023

AbstractChiral materials with strong linear anisotropies are difficult to accurately characterize with circular dichroism (CD) because of artifactual contributions to their spectra from linear dichroism (LD) and birefringence (LB). Historically, researchers have used a second‐order Taylor series expansion on the Mueller matrix to model the LDLB interaction effects on the spectra in conventional materials, but this approach may no longer be sufficient to account for the artifactual CD signals in emergent materials. In this work, we present an expression to model the measured CD using a third‐order expansion, which introduces “pairwise interference” terms that, unlike the LDLB terms, cannot be averaged out of the signal. We find that the third‐order pairwise interference terms can make noticeable contributions to the simulated CD spectra. Using numerical simulations of the measured CD across a broad range of linear and chiral anisotropy parameters, the LDLB interactions are most prominent in samples that have strong linear anisotropies (LD, LB) but negligible chiral anisotropies, where the measured CD strays from the chirality‐induced CD by factors greater than 103. Additionally, the pairwise interactions are most significant in systems with moderate‐to‐strong chiral and linear anisotropies, where the measured CD is inflated twofold, a figure that grows as linear anisotropies approach their maximum. In summary, media with moderate‐to‐strong linear anisotropy are in great danger of having their CD altered by these effects in subtle manners. This work highlights the significance of considering distortions in CD measurements through higher‐order pairwise interference effects in highly anisotropic nanomaterials.
The effects of moral exemplars awareness on common ingroup identification and reconciliation in post‐genocide Rwanda
Authors: Atete Pauline Joy , Bilewicz Michał 
Published: June 2023

AbstractMoral exemplars (Imena) play an important part in commemorative practices and reconciliation in post‐genocide Rwanda. Acknowledging the essential role of moral exemplars in reconciliation and intergroup contact in post‐conflict setting, we aimed at examining the effects of exposure to moral‐exemplars on people's attitudes toward reconciliation and identification with superordinate national category in Rwanda. A study of 168 young Rwandans showed that higher awareness of moral exemplars during genocide was related to stronger ingroup ties with other ingroup members and higher centrality of national identification. Strong ingroup ties significantly mediated the effects of moral exemplars awareness on reconciliation attitudes. This shows that ties with other members of common national ingroup, as well as the centrality of superordinate categories could be effective means for reconciliation after genocide.
Interacting ecological filters influence success and functional composition in restored plant communities over time
Authors: Funk Jennifer L. , Kimball Sarah , Nguyen Monica A. , Lulow Megan , Vose Gregory E. 
Published: June 2023

AbstractA trait‐based community assembly framework has great potential to direct ecological restoration, but uncertainty over how traits and environmental factors interact to influence community composition over time limits the widespread application of this approach. In this study, we examined how the composition of seed mixes and environment (north‐ vs. south‐facing slope aspect) influence functional composition and native plant cover over time in restored grassland and shrubland communities. Variation in native cover over 4 years was primarily driven by species mix, slope aspect, and a species mix by year interaction rather than an interaction between species mix and slope aspect as predicted. Although native cover was higher on wetter, north‐facing slopes for most of the study, south‐facing slopes achieved a similar cover (65%–70%) by year 4. While community‐weighted mean (CWM) values generally became more resource conservative over time, we found shifts in particular traits across community types and habitats. For example, CWM for specific leaf area increased over time in grassland mixes. Belowground, CWM for root mass fraction increased while CWM for specific root length decreased across all seed mixes. Multivariate functional dispersion remained high in shrub‐containing mixes throughout the study, which could enhance invasion resistance and recovery following disturbance. Functional diversity and species richness were initially higher in drier, south‐facing slopes compared to north‐facing slopes, but these metrics were similar across north‐ and south‐facing slopes by the end of the 4‐year study. Our finding that different combinations of traits were favored in south‐ and north‐facing slopes and over time demonstrates that trait‐based approaches can be used to identify good restoration candidate species and, ultimately, enhance native plant cover across community types and microhabitat. Changing the composition of planting mixes based on traits could be a useful strategy for restoration practitioners to match species to specific environmental conditions and may be more informative than using seed mixes based on growth form, as species within functional groups can vary tremendously in leaf and root traits.
Amidyl Radical Directed γ‐C(sp3)−H Functionalization with Silyl Enol Ethers via Photoredox Catalysis
Authors: Xu Kedong , Yang Jiawen , Qin Haitao , Liu Feng 
Published: June 2023

AbstractHerein we reported an efficient photoredox‐catalyzed reaction for site‐selective C(sp3)−H functionalization of carboxamides with silyl enol ethers as radical acceptors. The reaction proceeded through amidyl radical‐directed 1,5‐hydrogen atom transfer (1,5‐HAT) and C(sp3)−C(sp3) bond formation via radical addition of silyl enol ethers. The process features mild conditions and high functional‐group tolerance, allowing the preparation of a series of carboxamides with pendant carbonyl moieties.
Temperature gradient focusing of bio‐analyte in a microfluidic channel dealing with non‐Newtonian electrolyte considering temperature‐dependent zeta potential
Authors: Dutta Amitava , Santra Apurba Kumar , Ganguly Ranjan 
Published: June 2023

AbstractTemperature gradient focusing (TGF) relies on establishing a precise balance between the electrophoretic motility of a target analyte and the advective flow of the background electrolyte (BGE) to locally concentrate the analyte in a microfluidic configuration. This paper presents a finite‐element‐based numerical analysis where the coupled electric field and the transport equations are solved to describe the effects of the shear‐dependent apparent viscosity of a non‐Newtonian BGE on the localized concentration buildup of a charged bio‐sample inside a microchannel by TGF via Joule heating. Effects of the temperature‐dependent nature of the wall zeta potential and the flow behavior index (n) of BGE on the flow, thermal, and species concentration profiles inside the microchannel have been investigated. Study using a fluorescein‐Na analyte sample shows that the maximum normalized analyte concentration (Cmax/C0) reduces as the zeta potential increases linearly with temperature. The maximum concentration enhancement is achieved when the BGE displays the Newtonian rheology. For example, Cmax/C0 increases 134‐ to 280‐fold when n is increased from 0.8 to 1 (pseudoplastic regime) and again reduces to 190‐fold when n increases further from 1 to 1.2 (dilatant regime).
Artificial intelligence driven digital whole slide image for intelligent recognition of different development stages of tongue tumor via a new deep learning framework
Authors: Xu Xiaohong , Peng Xubei , Hou Chunyu , Chen Yanmei , Ren Xuan , Li Zhichen , Li Guancan , Cao Lituo , Li Zhenzhang 
Published: June 2023

AbstractAccurate clinical diagnosis of the stage of tumor development is essential for formulating a treatment plan. However, the stage of tongue tumor development among malignant, benign and leukoplakia is easily misdiagnosed, resulting differing treatment approaches, taking patients in danger and preventing them from receiving the deserved care. This study aimed to establish an automatic recognition system for tongue tumors at different stages of development using artificial intelligence methods along with pathological tissue section images. By improving Swin Transformer framework, a new framework in deep learning, the tissue slice image is used to identify the lesion and non‐lesion areas by the patch‐based method, and then an output is reconstructed by self‐Assembly method that the lesion areas is marked with heat map. Subsequently, an automatic recognition system with a friendly page is designed for the stage of tongue tumor development (malignant, benign, and leukoplakia). The proposed model has a high recognition accuracy (98.45%). The prediction accuracy of each category of the system is higher than that of specialist doctors with 13 years of experience. The Swin Transformer framework was improved in this study to accurately and automatically identify the various stages of tongue tumor development.
The estimation and evolution of hominin body mass
Authors: Ruff Christopher B. , Wood Bernard A. 
Published: June 2023

AbstractBody mass is a critical variable in many hominin evolutionary studies, with implications for reconstructing relative brain size, diet, locomotion, subsistence strategy, and social organization. We review methods that have been proposed for estimating body mass from true and trace fossils, consider their applicability in different contexts, and the appropriateness of different modern reference samples. Recently developed techniques based on a wider range of modern populations hold promise for providing more accurate estimates in earlier hominins, although uncertainties remain, particularly in non‐Homotaxa. When these methods are applied to almost 300 Late Miocene through Late Pleistocene specimens, the resulting body mass estimates fall within a 25–60 kg range for early non‐Homotaxa, increase in earlyHomoto about 50–90 kg, then remain constant until the Terminal Pleistocene, when they decline.
Locally adaptive bubble function enrichment for multiscale finite element methods: Application to convection‐diffusion problems
Authors: Su Yi‐Zhen , Su Syuan‐You , Hwang Feng‐Nan 
Published: June 2023

SummaryWe develop a new class of the multiscale finite element method (MsFEM) to solve the convection‐diffusion problems. In the proposed framework, we decompose the solution function space into two parts in MsFEM with locally adaptive bubble function enrichment (LABFE). The first part is the one that the multiscale basis functions can resolve, and the second part is an unresolved part that is taken care of by a set of bubble functions. These bubble functions are defined similarly to construct multiscale basis functions. We exchange the local‐global information through updated local boundary conditions for these bubble functions. The new multiscale solution recovered from the solution of global numerical formulation provides feedback for updating the local boundary conditions on each coarse element. As the approach iterates, the quality of MsFEM‐LABFE solutions improves since these multiscale basis functions with bubble function enrichment are expected to capture the multiscale feature of the approximate solution more accurately. However, the most expansive part of the algorithm is reconstructing the bubble functions on each coarse element. To reduce the overhead of the bubble function reconstruction, we update the local bubble function only when the intermediate multiscale solution is not well resolved within the region corresponding to the sharp local gradient or the discontinuity of the solution. We illustrate the effectiveness of the proposed method through some numerical examples for convection‐diffusion benchmark problems.
Climate data for Odesa, Ukraine in 2021–2050 based on EURO‐CORDEX simulations
Authors: Borovska Halyna , Khokhlov Valeriy 
Published: June 2023

AbstractClimate change adaptation planning at the municipal level has become mandatory due to the increasing frequency of extreme weather and climate events. The availability of near‐future climate data is the first step towards creating an adaptation plan for a city. We created the CP_OdU (Climate Projections for Odesa, Ukraine) dataset, which contains daily output variables from the 102 model runs and monthly (yearly) indices calculated for 2021–2050 in the closest to Odesa land‐located model grid point. The future data are based on 26 and 76 simulations for the scenarios RCP4.5 and RCP8.5, respectively, of 14 RCMs from the EURO‐CORDEX project. The horizontal resolution of spatial grids in the RCMs is ~0.11° or ~12 km. The CP_OdU dataset contains 76 indices relating to cloudiness, wind parameters, relative humidity, precipitation amount, snow depth and temperature. A very short description of the near‐future climate in Odesa for the RCP8.5 scenario shows its trend towards a Mediterranean climate. The rising temperature supported by the change of intra‐annual variations of precipitation will result in hot, dry summers and mild, moderately wet winters. The CP_OdU dataset can be used by climate scientists, applied science engineers and climate stakeholders in society for the creation of a climate change adaptation plan for Odesa, Ukraine.