bluuebunny/crossref_metadata_2025_split huggingface dataset:
Asymmetric Synthesis of Trisubstituted Piperidines via Biocatalytic Transamination and Diastereoselective Enamine or Imine Reduction
Authors: Petermeier Philipp , Kohlfuerst Christoph , Torvisco Ana , Fischer Roland C. , Mata Alejandro , Dallinger Doris , Kappe C. Oliver , Schrittwieser Joerg H. , Kroutil Wolfgang 
Published: February 2023

AbstractSubstituted piperidine rings are a common motif in natural products and pharmaceutical drugs. The asymmetric synthesis of piperidines bearing multiple stereocentres remains a challenge, and current approaches often rely on lengthy reaction sequences and ‘chiral pool’ strategies. Herein, we report multi‐enzymatic and chemo‐enzymatic methods that allow the preparation of piperidines with three chirality centres in only two steps from achiral diketoester precursors. Stereocontrol is achieved by a highly enantioselective transamination leading to optically pure (ee >99%) enamine or imine intermediates, followed by diastereoselective reduction of these unsaturated N‐heterocycles using either platinum(0)‐catalysed flow hydrogenation or enzymatic imine reduction. In the latter case, coupling of the two biocatalytic reactions in a concurrent one‐pot process is possible, thus reducing the synthetic sequence to a single biotransformation. In total, nine trisubstituted piperidines were prepared in high stereoisomeric purities (dr ≥98:2) and isolated yields of up to 73%. Lead‐likeness analysis of five representative products using an open‐source webtool suggests that these compounds possess considerable application potential as building blocks in drug discovery.
Liquid Nitrogen Sources Assisting Gram‐Scale Production of Single‐Atom Catalysts for Electrochemical Carbon Dioxide Reduction
Authors: An Beibei , Zhou Jingsheng , Duan Liangjing , Liu Xiao , Yu Guanyao , Ren Tiegang , Guo Xugeng , Li Yuanyuan , Ågren Hans , Wang Li , Zhang Jinglai 
Published: February 2023

AbstractDeveloping metal‐nitrogen‐carbon (M‐N‐C)‐based single‐atom electrocatalysts for carbon dioxide reduction reaction (CO2RR) have captured widespread interest because of their outstanding activity and selectivity. Yet, the loss of nitrogen sources during the synthetic process hinders their further development. Herein, an effective strategy using 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIM][BF4]) as a liquid nitrogen source to construct a nickel single‐atom electrocatalyst (Ni‐SA) with well‐defined Ni‐N4 sites on a carbon support (denoted as Ni‐SA‐BB/C) is reported. This is shown to deliver a carbon monoxide faradaic efficiency of >95% over a potential of −0.7 to −1.1 V (vs reversible hydrogen electrode) with excellent durability. Furthermore, the obtained Ni‐SA‐BB/C catalyst possesses higher nitrogen content than the Ni‐SA catalyst prepared by conventional nitrogen sources. Importantly, only thimbleful Ni nanoparticles (Ni‐NP) are contained in the large‐scale‐prepared Ni‐SA‐BB/C catalyst without acid leaching, and with only a slight decrease in the catalytic activity. Density functional theory calculations indicate a salient difference between Ni‐SA and Ni‐NP in the catalytic performance toward CO2RR. This work introduces a simple and amenable manufacturing strategy to large‐scale fabrication of nickel single‐atom electrocatalysts for CO2‐to‐CO conversion.
New Interpretation of Glass Formation in Isomeric Substances: Shifting from Melting‐Point to Melting‐Entropy
Authors: Ren Baokang , Li Zijing , Zhang Yanhui , Feng Shidong , Wang Li‐Min 
Published: February 2023

AbstractRevealing the critical thermodynamic parameters determining the glass formation of substances is of great significance for understanding the glass transition and guiding the composition design of glass‐forming materials. Nevertheless, the direct access to glass‐forming ability (GFA) by thermodynamics for various substances remains to be substantiated. The strategy to seek the fundamental properties of glass formation is explored several decades ago, as pioneered by Angell, arguing that the GFA in isomeric xylenes depends on the low lattice energy manifested by the low melting point. Here, an in‐depth study is advanced using two more isomeric systems. Surprisingly, the results do not constantly support the reported relationship between the melting point and glass formation among isomeric molecules. Instead, molecules with enhanced glass formability are featured by the properties of low melting entropy without exception. Comprehensive studies of isomeric molecules find that the low melting entropy is roughly accompanied by the low melting point, explaining the apparent link between melting point and glass formation. Progressively, the viscosity measurements of the isomers uncover a strong dependence of the melting viscosity on melting entropy. These results emphasize the significance of the melting entropy in governing the glass formability of substances.
Ultrahigh Nitrogen Content Carbon Nanosheets for High Stable Sodium Metal Anodes
Authors: Huang Bicheng , Sun Shixiong , Wan Jing , Zhang Wen , Liu Siying , Zhang Jingwen , Yan Feiyang , Liu Yi , Xu Jia , Cheng Fangyuan , Xu Yue , Lin Yaqing , Fang Chun , Han Jiantao , Huang Yunhui 
Published: February 2023

AbstractSodium metal, with a high theoretical specific capacity of 1165 mAh g−1, is the ultimate anode for sodium batteries, yet how to deal with the inhomogeneous and dendritic sodium deposition and the infinite relative dimension change of sodium metal anodes during sodium depositing/stripping is still challenging. Here, a facile fabricated sodiuphilic 2D N‐doped carbon nanosheets (N‐CSs) are proposed as sodium host material for sodium metal batteries (SMBs) to prevent dendrite formation and eliminate volume change during cycling. Revealing from combined in situ characterization analyses and theoretical simulations, the high nitrogen content and porous nanoscale interlayer gaps of the 2D N‐CSs can not only concede dendrite‐free sodium stripping/depositing but also accommodate the infinite relative dimension change. Furthermore, N‐CSs can be easily process into N‐CSs/Cu electrode via traditional commercial battery electrode coating equipment that pave the way for large‐scale industrial applications. On account of the abundant nucleation sites and sufficient deposition space, N‐CSs/Cu electrodes demonstrate a superior cycle stability of more than 1500 h at a current density of 2 mA cm−2 with a high coulomb efficiency of more than 99.9% and ultralow nucleation overpotential, which enable reversible and dendrites‐free SMBs and shed light on further development of SMBs with even higher performance.
X‐Ray Activatable Au/Ag Nanorods for Tumor Radioimmunotherapy Sensitization and Monitoring of the Therapeutic Response Using NIR‐II Photoacoustic Imaging
Authors: Zheng Si , Gao Duyang , Wu Yayun , Hu Dehong , Li Ziyue , Wang Yuenan , Zheng Hairong , Li Yingjia , Sheng Zonghai 
Published: February 2023

AbstractRadioimmunotherapy (RIT) is an advanced physical therapy used to kill primary cancer cells and inhibit the growth of distant metastatic cancer cells. However, challenges remain because RIT generally has low efficacy and serious side effects, and its effects are difficult to monitor in vivo. This work reports that Au/Ag nanorods (NRs) enhance the effectiveness of RIT against cancer while allowing the therapeutic response to be monitored using activatable photoacoustic (PA) imaging in the second near‐infrared region (NIR‐II, 1000–1700 nm). The Au/Ag NRs can be etched using high‐energy X‐ray to release silver ions (Ag+), which promotes dendritic cell (DC) maturation, enhances T‐cell activation and infiltration, and effectively inhibits primary and distant metastatic tumor growth. The survival time of metastatic tumor‐bearing mice treated with Au/Ag NR‐enhanced RIT is 39 days compared with 23 days in the PBS control group. Furthermore, the surface plasmon absorption intensity at 1040 nm increases fourfold after Ag+ are released from the Au/Ag NRs, allowing X‐ray activatable NIR‐II PA imaging to monitor the RIT response with a high signal‐to‐background ratio of 24.4. Au/Ag NR‐based RIT has minimal side effects and shows great promise for precise cancer RIT.
Understanding the Configurational Entropy Evolution in Metal‐Phosphorus Solid Solution for Highly Reversible Li‐Ion Batteries
Authors: Wei Yaqing , Yao Runzhe , Liu Xuhao , Chen Wen , Qian Jiayao , Yin Yiyi , Li De , Chen Yong 
Published: February 2023

AbstractThe high‐entropy materials (HEM) have attracted increasing attention in catalysis and energy storage due to their large configurational entropy and multiunique properties. However, it is failed in alloying‐type anode due to their Li‐inactive transition‐metal compositions. Herein, inspired by high‐entropy concept, the Li‐active elements instead of transition‐metal ones are introduced for metal‐phosphorus synthesis. Interestingly, a new ZnxGeyCuzSiwP2 solid solution is successfully synthesized as proof of concept, which is first verified to cubic system in F‐43m. More specially, such ZnxGeyCuzSiwP2 possesses wide‐range tunable region from 9911 to 4466, in which the Zn0.5Ge0.5Cu0.5Si0.5P2 accounts for the highest configurational entropy. When served as anode, ZnxGeyCuzSiwP2 delivers large capacity (>1500 mAh g−1) and suitable plateau (≈0.5 V) for energy storage, breaking the conventional view that HEM is helpless for alloying anode due to its transition‐metal compositions. Among them, the Zn0.5Ge0.5Cu0.5Si0.5P2 exhibits the highest initial coulombic efficiency (ICE) (93%), Li‐diffusivity (1.11 × 10−10), lowest volume‐expansion (34.5%), and best rate performances (551 mAh g−1 at 6400 mA g−1) owing to its largest configurational entropy. Possible mechanism reveals the high entropy stabilization enables good accommodation of volume change and fast electronic transportation, thus supporting superior cyclability and rate performances. This large configurational entropy strategy in metal‐phosphorus solid solution may open new avenues to develop other high‐entropy materials for advanced energy storage.
Challenges and Perspectives toward Future Wide‐Bandgap Mixed‐Halide Perovskite Photovoltaics
Authors: Xu Fan , Zhang Meng , Li Zikun , Yang Xiaoyu , Zhu Rui 
Published: February 2023

AbstractWide‐bandgap (WBG) perovskite solar cells (PSCs) are acknowledged as promising candidates for multijunction tandem and building photovoltaics, which attract broad research interest in related research communities. However, the performance of WBG PSCs based on the mixed‐halide perovskites still lags far behind their pure‐iodide counterparts because of the complex compositional evolution, huge photovoltage deficits, and intrinsic spectral losses. Here, by comprehensively understanding the representative WBG PSCs, the main “WBG drawbacks” from the device point of view are discussed in‐depth and three intrinsic critical issues for the growth of high‐quality WBG perovskites are proposed. The prospects for WBG PSCs toward future advancements and commercialization are also presented to guide the coming research hot spots.
Controlling Electrolyte Properties and Redox Reactions Using Solvation and Implications in Battery Functions: A Mini‐Review
Authors: Leverick Graham , Shao‐Horn Yang 
Published: February 2023

AbstractElectrolytes will play a central role in the development of next‐generation batteries with increased energy density and cycle life and reduced cost. While molecular designs can enable electrolytes with favorable properties like increased (electro)chemical stability, such properties can be manipulated additionally through the intermolecular interactions among species within the electrolyte. In this mini‐review, a number of intermolecular interactions in the electrolyte that can give rise to significant enhancement in battery functions are highlighted. The critical role of reactant and product solubility is shown in battery reactions, where increasing solubility can enable a dissolution–precipitation reaction pathway, decrease overpotential, and increase capacity. Through the intermolecular interactions among solvent, additives, and ions, the reactivity of electrolyte species can be altered significantly by either enhancing solvent (electro)chemical stability or facilitating water deprotonation in Li–O2 reactions. It is shown that incorporating redox active species in the electrolyte can reduce the reaction overpotential and enhance cycle life. Moreover, intermolecular interactions that can increase the ionic conductivity and transference number of electrolytes are identified. Finally, future opportunities are highlighted to exploit these intermolecular interactions to gain unprecedented molecular control over the electrolyte and enable next‐generation batteries.
A performance indicator for the screening of adsorbent/desorbent pairs for gas‐phase simulated moving bed applications
Authors: Dias Rafael O. M. , Nogueira Idelfonso B. R. , Ferreira Alexandre F. P. , Rodrigues Alírio E. , Ribeiro Ana M. 
Published: February 2023

AbstractIn a simulated moving bed, the regeneration is accomplished by the introduction of a third species, the desorbent, which is later recovered by two downstream separations. As such, the choice of a proper adsorbent/desorbent pair is critical to ensure the effectiveness of the SMB process. While this can be done by comparing the separation region for each system, the computational effort required is extremely high. By developing a parameter that uses readily available literature data, the selection process is sped up and can be easily accomplished. In this work, an SMB performance indicator (SPI) is suggested. This indicator involves the trade‐off between the adsorption selectivity in the presence of the desorbent, the adsorption capacity of the most retained species, and the ratio of the most and less retained species' enthalpies. The developed metric can select the most suitable adsorbent/pair for a specific gas separation by SMB through simple calculations.
CSF biomarker concordance with amyloid PET in Phase 3 studies of aducanumab
Authors: Nisenbaum Laura , Martone Robert , Chen Tianle , Rajagovindan Rajasimhan , Dent Gersham , Beaver John , Rubel Carrie , Racine Annie , He Ping , Harrison Katie , Dean Robert , Vandijck Manu , Haeberlein Samantha Budd 
Published: February 2023

AbstractIntroductionWe assessed the use of cerebrospinal fluid (CSF) biomarkers as an alternative to positron emission tomography (PET) for brain amyloid beta (Aβ) pathology confirmation in the EMERGE and ENGAGE clinical trials.MethodsEMERGE and ENGAGE were randomized, placebo‐controlled, Phase 3 trials of aducanumab in participants with early Alzheimer's disease. Concordance between CSF biomarkers (Aβ42, Aβ40, phosphorylated tau 181, and total tau) and amyloid PET status (visual read) at screening was examined.ResultsRobust concordance between CSF biomarkers and amyloid PET visual status was observed (for Aβ42/Aβ40, AUC: 0.90; 95% CI: 0.83‐0.97; p < 0.0001), confirming CSF biomarkers as a reliable alternative to amyloid PET in these studies. Compared with single CSF biomarkers, CSF biomarker ratios showed better agreement with amyloid PET visual reads, demonstrating high diagnostic accuracy.DiscussionThese analyses add to the growing body of evidence supporting CSF biomarkers as reliable alternatives to amyloid PET imaging for brain Aβ pathology confirmation.Highlights
CSF biomarkers and amyloid PET concordance were assessed in Ph3 aducanumab trials.
Robust concordance between CSF biomarkers and amyloid PET was observed.
CSF biomarker ratios increased diagnostic accuracy over single CSF biomarkers.
CSF Aβ42/Aβ40 demonstrated high concordance with amyloid PET.
Results support CSF biomarker testing as a reliable alternative to amyloid PET.
Neuropathology‐based APOE genetic risk score better quantifies Alzheimer's risk
Authors: Deming Yuetiva , Vasiljevic Eva , Morrow Autumn , Miao Jiacheng , Van Hulle Carol , Jonaitis Erin , Ma Yue , Whitenack Vanessa , Kollmorgen Gwendlyn , Wild Norbert , Suridjan Ivonne , Shaw Leslie M. , Asthana Sanjay , Carlsson Cynthia M. , Johnson Sterling C. , Zetterberg Henrik , Blennow Kaj , Bendlin Barbara B. , Lu Qiongshi , Engelman Corinne D. ,   the Alzheimer's Disease Neuroimaging Initiative
Published: February 2023

AbstractINTRODUCTIONApolipoprotein E (APOE) ε4‐carrier status or ε4 allele count are included in analyses to account for the APOE genetic effect on Alzheimer's disease (AD); however, this does not account for protective effects of APOE ε2 or heterogeneous effect of ε2, ε3, and ε4 haplotypes.METHODSWe leveraged results from an autopsy‐confirmed AD study to generate a weighted risk score for APOE (APOE‐npscore). We regressed cerebrospinal fluid (CSF) amyloid and tau biomarkers on APOE variables from the Wisconsin Registry for Alzheimer's Prevention (WRAP), Wisconsin Alzheimer's Disease Research Center (WADRC), and Alzheimer's Disease Neuroimaging Initiative (ADNI).RESULTSThe APOE‐npscore explained more variance and provided a better model fit for all three CSF measures than APOE ε4‐carrier status and ε4 allele count. These findings were replicated in ADNI and observed in subsets of cognitively unimpaired (CU) participants.DISCUSSIONThe APOE‐npscore reflects the genetic effect on neuropathology and provides an improved method to account for APOE in AD‐related analyses.
ARMOR: Auto‐Assembled Resilient Biomimetic Calcified Ornaments for Selective Cell Protection by Dual‐Aptamer‐Driven Hybridization Chain Reaction
Authors: Yu Xiyuan , Lin Wei , Lai Qian , Song Juan , Liu Yilong , Su Rui , Niu Qi , Yang Liu , Yang Chaoyong , Zhang Huimin , Zhu Zhi 
Published: February 2023

AbstractUnlike plant and microbial cells having cell walls, the outermost layer of mammalian cell is a delicate, two‐layered structure of phospholipids with proteins embedded, which is susceptible to environmental changes. It is necessary to create an “armor” on cell surface to protect cell integrity. Here, we propose an Auto‐assembled Resilient bioMimetic calcified ORnaments (ARMOR) strategy driven by dual‐aptamer‐based hybridization chain reaction (HCR) and Ca2+ assisted calcification for selective cell protection. This co‐recognition design enhances the selectivity and leverages robust in situ signal amplification by HCR to improve the sensitivity. The calcified shell is cogenerated by crosslinking the alginate‐HCR product with Ca2+ ion. ARMOR has high efficiency for shielding cells from environmental assaults, which can be applied to circulating tumor cell (CTC) protection, isolation, and identification, maintaining the native state and intact genetic information for downstream analysis.
Metal‐Organic Frameworks for C6 Alkane Separation
Authors: Xie Feng , Yu Liang , Wang Hao , Li Jing 
Published: February 2023

AbstractThe separation of alkane isomers is an important yet challenging process in the petrochemical industry. Being a crucial step to produce premium gasoline components as well as optimum ethylene feed, the current industrial separation by distillation is extremely energy intensive. Adsorptive separation based on zeolite is limited by insufficient adsorption capacity. Metal‐organic frameworks (MOFs) hold enormous promise as alternative adsorbents due to their diverse structural tunability and exceptional porosity. Precise control of their pore geometry/dimensions has led to superior performance. In this minireview, we highlight the recent progresses in developing MOFs for the separation of C6 alkane isomers. Representative MOFs are reviewed based on their separation mechanisms. Emphasis is put on the material design rationale for achieving optimal separation capability. Finally, we briefly discuss the existing challenges, possible solutions, and future directions of this important field.
Equations of state for dense matter and astrophysical constraints
Authors: Jacobsen Rafael Bán , Dexheimer Verônica , Farias Ricardo Luciano Sonego 
Published: February 2023

AbstractThis conference proceeding presents an overview of the modern approaches in the study of baryonic matter at high densities, focusing on the use of online repositories such as CompOSE and MUSES for the calculation of neutron star properties. In this context, relevant astrophysical constraints for the equations of state (mass‐radius relation, speed of sound, tidal deformability) are discussed.
Effects of the protonation and the polar solvation on the molecular properties of methyl orange: A density functional theory study
Authors: You Kanghyeon , Kwon O‐Pil , Kim Dongwook 
Published: February 2023

AbstractMethyl orange (MO) and its protonated derivatives were investigated at the density functional theory (DFT) level using CAM‐B3LYP functional and 6‐311 + G(d,p) basis sets; their absorption spectra in aqueous solution were simulated, their relative stabilities in both the gas phase and the polar solutions were calculated, and the activation energy barrier for the cis‐to‐trans isomerization in both phases were computed. Except the protonation at the amino group, all the protonated isomers show a bathochromic shift of the most intense absorption peak. In the gas phase, the sulfonate unit turns out to be the most favorable proton acceptor. In the polar solutions, however, azo groups are more effective to accept the proton. The protonation at the azo N atom next to the phenyl‐sulfonate group significantly reduces the energy barrier for the cis‐to‐trans conversion in the aqueous solution, which suggests a swift conversion in the ground state.
The tissue distribution of Jinzhen oral liquid in healthy and influenza mice
Authors: Chen Xialin , Gao Xia , Cao Liang , Wang Shanli , Qian Mengyu , Tong Xiaoyu , Wang Jiajia , Gao Huifang , Wang Zhenzhong , Li Jifeng , Xiao Wei 
Published: February 2023

AbstractJinzhen oral liquid (JZOL) is widely used in China. However, its tissue distribution, a vital part of the efficacy substances research, has not been reported yet. This study characterized its chemical components and its prototypes and metabolites in mice, and investigated its tissue distribution in pathological and healthy mice. Several constituents were characterized, including 55 constituents in JZOL, 11 absorbed prototypes and six metabolites in plasma and tissues. The metabolic pathways were demethylation, dehydration and acetylation. A sensitive, accurate and stable quantitative method was established and applied to the tissue distribution. After administration of JZOL, these seven components were rapidly distributed to various tissues, mainly staying in the small intestine, and less distributed to lung, liver and kidney. Compared with healthy mice, the absorption of baicalin, wogonoside, rhein, glycyrrhizic acid and liquiritin apioside was reduced in influenza mice, but their elimination was slow. However, influenza infection had no obvious effect on the overall distribution of the most important components (baicalin, glycyrrhizic acid and wogonoside) in the plasma or small intestine, but obviously affected the distribution of baicalin in liver. In summary, seven components are rapidly distributed to various tissues, and influenza infection has certain influence on the tissue distribution of JZOL.