bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Intelligent, User‐Inclusive Pipeline for Organic Semiconductor Design
Authors: Packwood Daniel M. , Kaneko Yu , Ikeda Daiji , Ohno Mitsuru 
Published: May 2023

AbstractData‐guided methodologies for designing new materials are developing apace, yet advances for organic crystals have been infrequent. For the case of organic crystals, data‐guided design platforms involve two problems: the need to construct regression models that can predict solid‐state properties from molecular structures alone and the vast number of molecular structures that satisfy a targeted solid‐state property. In this paper, a new pipeline is presented for designing molecules with targeted solid‐state electronic properties. Here, the first problem is overcome by means of a novel visualization method for band structure data, which allows the user to specify their design preferences and simplify the creation of the required regression models. The second problem is overcome by allowing for user intervention in the selection of the final molecule for subsequent synthesis. The effectiveness of this pipeline is demonstrated by using it to design a simple new molecule with a targeted bandgap and impressive band dispersion. This pipeline is the first data‐guided method that can design new molecules on the basis of genuine solid‐state electronic properties, and with its emphasis on user‐inclusivity, it can easily be applied in collaborative or industry settings.
Molecular Dipoles as a Surface Flattening and Interface Stabilizing Agent for Lithium‐Metal Batteries
Authors: Jun Seo‐Young , Shin Kihyun , Lee Jun‐Seo , Kim Suji , Chun Jinyoung , Ryu Won‐Hee 
Published: May 2023

AbstractReaching the border of the capable energy limit in existing battery technology has turned research attention away from the rebirth of unstable Li‐metal anode chemistry in order to achieve exceptional performance. Strict regulation of the dendritic Li surface reaction, which results in a short circuit and safety issues, should be achieved to realize Li‐metal batteries. Herein, this study reports a surface‐flattening and interface product stabilizing agent employing methyl pyrrolidone (MP) molecular dipoles in the electrolyte for cyclable Li‐metal batteries. The excellent stability of the Li‐metal electrode over 600 cycles at a high current density of 5 mA cm−2 has been demonstrated using an optimal concentration of the MP additive. This study has identified the flattening surface reconstruction and crystal rearrangement behavior along the stable (110) plane assisted by the MP molecular dipoles. The stabilization of the Li‐metal anodes using molecular dipole agents has helped develop next‐generation energy storage devices using Li‐metal anodes, such as Li–air, Li–S, and semi‐solid‐state batteries.
Synthesis of Triazatriphenylene Derivative Through Multi‐Component Reaction of Aryl‐amine, Aldehyde, and Alkyne
Authors: Yamamoto Sachie , Ishida Naruki , Yasuda Takeshi , Kanbara Takaki , Kuwabara Junpei 
Published: May 2023

AbstractThe Povarov reaction is a representative multicomponent reaction used for synthesizing nitrogen‐containing aromatic compounds from aromatic amines, aldehydes, and dienophiles, such as electron‐rich alkenes and alkynes. In this study, we investigated a triple Povarov reaction of 1,3,5‐triaminobenzne with aromatic aldehydes and phenylacetylene to obtain triazatriphenylene derivatives. Reactions with arylaldehydes containing electron‐donating groups proceeded smoothly to provide triazatriphenylene derivatives. In contrast, reactions with arylaldehydes containing electron‐withdrawing groups resulted in low yields. Reactions with electron‐rich arylaldehydes are probably more favorable in terms of high stability of imine intermediates and smooth electrophilic cyclization. Single‐crystal X‐ray structure analysis revealed that the aryl groups derived from the aldehydes had small dihedral angles between with the triazatriphenylene core. The derivative with tertiary butyl groups (tBu‐TaT) had a high glass transition temperature, while that without tertiary butyl groups (H‐TaT) had a lower highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) level and served as an efficient hole‐blocking material with better electron transport properties than those of tBu‐TaT. This study provides insights into the scope and limitations of the multicomponent reactions based on the Povarov reaction, substituent dependence on the crystal structures, and physical properties of π‐extended nitrogen‐containing aromatic compounds.
Synthesis and Resolution of an Axially Chiral Spirocyclic Quaternary Ammonium Ion‐Based Phase‐Transfer Catalyst
Authors: Li Shen , Zhou Hui , List Benjamin 
Published: May 2023

AbstractWe report the synthesis of a novel spirocyclic quaternary ammonium salt that possesses axial chirality. Enantiopure material was obtained by fractional crystallization of the corresponding (R,R)‐tartrate salt. Application of this chiral quaternary ammonium salt in phase‐transfer catalytic asymmetric alkylation of glycinate Schiff base was examined.
Large‐scale proteome and metabolome analysis of CSF implicates altered glucose and carbon metabolism and succinylcarnitine in Alzheimer's disease
Authors: Panyard Daniel J. , McKetney Justin , Deming Yuetiva K. , Morrow Autumn R. , Ennis Gilda E. , Jonaitis Erin M. , Van Hulle Carol A. , Yang Chengran , Sung Yun Ju , Ali Muhammad , Kollmorgen Gwendlyn , Suridjan Ivonne , Bayfield Anna , Bendlin Barbara B. , Zetterberg Henrik , Blennow Kaj , Cruchaga Carlos , Carlsson Cynthia M. , Johnson Sterling C. , Asthana Sanjay , Coon Joshua J. , Engelman Corinne D. 
Published: May 2023

AbstractINTRODUCTIONA hallmark of Alzheimer's disease (AD) is the aggregation of proteins (amyloid beta [A] and hyperphosphorylated tau [T]) in the brain, making cerebrospinal fluid (CSF) proteins of particular interest.METHODSWe conducted a CSF proteome‐wide analysis among participants of varying AT pathology (n = 137 participants; 915 proteins) with nine CSF biomarkers of neurodegeneration and neuroinflammation.RESULTSWe identified 61 proteins significantly associated with the AT category (P < 5.46 × 10−5) and 636 significant protein‐biomarker associations (P < 6.07 × 10−6). Proteins from glucose and carbon metabolism pathways were enriched among amyloid‐ and tau‐associated proteins, including malate dehydrogenase and aldolase A, whose associations with tau were replicated in an independent cohort (n = 717). CSF metabolomics identified and replicated an association of succinylcarnitine with phosphorylated tau and other biomarkers.DISCUSSIONThese results implicate glucose and carbon metabolic dysregulation and increased CSF succinylcarnitine levels with amyloid and tau pathology in AD.HighlightsCerebrospinal fluid (CSF) proteome enriched for extracellular, neuronal, immune, and protein processing.Glucose/carbon metabolic pathways enriched among amyloid/tau‐associated proteins.Key glucose/carbon metabolism protein associations independently replicated.CSF proteome outperformed other omics data in predicting amyloid/tau positivity.CSF metabolomics identified and replicated a succinylcarnitine–phosphorylated tau association.
Subjective cognitive decline across ethnoracial groups in the A4 study
Authors: Robinson Talia , Klinger Hannah , Buckley Rachel , Deters Kacie D. , Quiroz Yakeel T. , Rentz Dorene , Rabin Jennifer S. , Sperling Reisa A. , Amariglio Rebecca E. 
Published: May 2023

AbstractINTRODUCTIONThe associations between subjective cognitive decline (SCD), cognition, and amyloid were explored across diverse participants in the A4 study.METHODSFive thousand one hundred and fifty‐one non‐Hispanic White, 262 non‐Hispanic Black, 179 Hispanic‐White, and 225 Asian participants completed the Preclinical Alzheimer Cognitive Composite (PACC), self‐ and study partner‐reported Cognitive Function Index (CFI). A subsample underwent amyloid positron emission tomography (18F‐florbetapir) (N = 4384). We examined self‐reported CFI, PACC, amyloid, and study partner‐reported CFI by ethnoracial group.RESULTSThe associations between PACC‐CFI and amyloid‐CFI were moderated by race. The relationships were weaker or non‐significant in non‐Hispanic Black and Hispanic White groups. Depression and anxiety scores were stronger predictors of CFI in these groups. Despite group differences in the types of study partners, self‐ and study partner‐CFI were congruent across groups.DISCUSSIONSCD may not uniformly relate to cognition or AD biomarkers in different ethnoracial groups. Nonetheless, self‐ and study partner‐SCD were congruent despite differences in study partner type.Highlights
Association between SCD and objective cognition was moderated by ethnoracial group.
Association between SCD and amyloid was moderated by ethnoracial group.
Depression and anxiety were stronger predictors of SCD in Black and Hispanic groups.
Study‐partner and self‐reported SCD are congruent across groups.
Study‐partner report was consistent despite difference in study partner types.
Insights into Electrochemical CO2 Reduction on SnS2: Main Product Switch from Hydrogen to Formate by Pulsed Potential Electrolysis
Authors: Woldu Abebe R. , Talebi Pooya , Yohannes Asfaw G. , Xu Jianyin , Wu Xu‐Dong , Siahrostami Samira , Hu Liangsheng , Huang Xiao‐Chun 
Published: May 2023

AbstractTin disulfide (SnS2) is a promising candidate for electrosynthesis of CO2‐to‐formate while the low activity and selectivity remain a great challenge. Herein, we report the potentiostatic and pulsed potential CO2RR performance of SnS2 nanosheets (NSs) with tunable S‐vacancy and exposure of Sn‐atoms or S‐atoms prepared controllably by calcination of SnS2 at different temperatures under the H2/Ar atmosphere. The catalytic activity of S‐vacancy SnS2 (Vs‐SnS2) is improved 1.8 times, but it exhibits an exclusive hydrogen evolution with about 100 % FE under all potentials investigated in the static conditions. The theoretical calculations reveal that the adsorption of *H on the Vs‐SnS2 surface is energetically more favorable than the carbonaceous intermediates, resulting in active site coverage that hinders the carbon intermediates from being adsorbed. Fortunately, the main product can be switched from hydrogen to formate by applying pulsed potential electrolysis benefiting from in situ formed partially oxidized SnS2−x with the oxide phase selective to formate and the S‐vacancy to hydrogen. This work highlights not only the Vs‐SnS2 NSs lead to exclusively H2 formation, but also provides insights into the systematic design of highly selective CO2 reduction catalysts reconstructed by pulsed potential electrolysis.
Phase Transition Engineering of Host Perovskite toward Optimal Exsolution‐facilitated Catalysts for Carbon Dioxide Electrolysis
Authors: Zhang Bo‐Wen , Zhu Meng‐Nan , Gao Min‐Rui , Chen Jian , Xi Xiuan , Shen Jing , Feng Ren‐Fei , Semagina Natalia , Duan Nanqi , Zeng Hongbo , Luo Jing‐Li 
Published: May 2023

AbstractThe in situ exsolution technique of nanoparticles has brought new opportunities for the utilization of perovskite‐based catalysts in solid oxide cells. However, the lack of control over the structural evolution of host perovskites during the promotion of exsolution has restricted the architectural exploitation of exsolution‐facilitated perovskites. In this study, we strategically broke the long‐standing trade‐off phenomenon between promoted exsolution and suppressed phase transition via B‐site supplement, thus broadening the scope of exsolution‐facilitated perovskite materials. Using carbon dioxide electrolysis as an illustrative case study, we demonstrate that the catalytic activity and stability of perovskites with exsolved nanoparticles (P‐eNs) can be selectively enhanced by regulating the explicit phase of host perovskites, accentuating the critical role of the architectures of perovskite scaffold in catalytic reactions occurring on P‐eNs. The concept demonstrated could potentially pave the way for designing the advanced exsolution‐facilitated P‐eNs materials and unveiling a wide range of catalytic chemistry taking place on P‐eNs.
Dimerization of a Reactive Azaacene Diradical: Synthesis of a Covalent Azaacene Cage
Authors: Fuchs Kathleen , Medina Rivero Samara , Weidlich Anna , Rominger Frank , Israel Noel , Popov Alexey A. , Dreuw Andreas , Freudenberg Jan , Casado Juan , Bunz Uwe H. F. 
Published: May 2023

AbstractTwo series of regioisomeric dicyanomethylene substituted dithienodiazatetracenes with formal para‐ or ortho‐quinodimethane subunits were synthesized and characterized. Whereas the para‐isomers (p‐n, diradical index y0=0.01) are stable and isolable, the ortho‐isomer (y0=0.98) dimerizes into a covalent azaacene cage. Four elongated σ‐CC bonds are formed and the former triisopropylsilyl(TIPS) ‐ethynylene groups transformed into cumulene units. The azaacene cage dimer (o‐1)2 was characterized by X‐ray single crystal structure analysis and temperature‐dependent infrared (IR), electron paramagnetic resonance (EPR, solid‐state), nuclear magnetic resonance (NMR) and ultraviolet‐visible (UV/Vis) spectroscopies (solution) indicating reformation of o‐1.
Reversible Electrodeposition of Potassium‐bridged Molecular Vanadium Oxides: A New Approach Towards Multi‐Electron Storage
Authors: Arya Nikhil , Philipp Tom , Greiner Simon , Steiner Michael , Kranz Christine , Anjass Montaha 
Published: May 2023

AbstractMolecular metal oxides, so‐called polyoxometalates (POMs), have shown outstanding performance as catalysts and lately attracted interest as materials in energy conversion and storage systems due to their capability of storing and exchanging multiple electrons. Here, we report the first example of redox‐driven reversible electrodeposition of molecular vanadium oxide clusters, leading to the formation of thin films. The detailed investigation of the deposition mechanism reveals that the reversibility is dependent on the reduction potential. Correlating electrochemical quartz microbalance studies with X‐ray photoelectron spectroscopy (XPS) data gave insight into the redox chemistry and oxidation states of vanadium in the deposited films in dependence on the potential window. A multi‐electron reduction of the polyoxovanadate cluster, which facilitates the potassium (K+) cation‐assisted reversible formation of potassium vanadium oxide thin films was confirmed. At anodic potentials, re‐oxidation of the polyoxovanadate and complete stripping of the thin film is observed for films deposited at potentials more positive than −500 mV vs. Ag/Ag+, while electrodeposition at more negative cathodic potential reduces the electrochemical reversibility of the process and increases the stripping overpotential. As proof of principle, we demonstrate the electrochemical performance of the deposited films for potential use in potassium‐ion batteries.
Alteration of Gut Microbiota in Individuals at High‐Risk for Rheumatoid Arthritis Associated With Disturbed Metabolome and the Initiation of Arthritis Through the Triggering of Mucosal Immunity Imbalance
Authors: Luo Yubin , Tong Yanli , Wu Liang , Niu Haitao , Li Yanhong , Su Lin Chong , Wu Yuxi , Bozec Aline , Zaiss Mario M. , Qing Pingying , Zhao Hua , Tan Chunyu , Zhang Qiuping , Zhao Yi , Tang Huairong , Liu Yi 
Published: May 2023

ObjectiveIn this study, we aimed to decipher the gut microbiome (GM) and serum metabolic characteristic of individuals at high risk for rheumatoid arthritis (RA) and to investigate the causative effect of GM on the mucosal immune system and its involvement in the pathogenesis of arthritis.MethodsFecal samples were collected from 38 healthy individuals and 53 high‐risk RA individuals with anti–citrullinated protein antibody (ACPA) positivity (Pre‐RA), 12 of 53 Pre‐RA individuals developed RA within 5 years of follow‐up. The differences in intestinal microbial composition between the healthy controls and Pre‐RA individuals or among Pre‐RA subgroups were identified by 16S ribosomal RNA sequencing. The serum metabolite profile and its correlation with GM were also explored. Moreover, antibiotic‐pretreated mice that received GM from the healthy control or Pre‐RA groups were then evaluated for intestinal permeability, inflammatory cytokines, and immune cell populations. Collagen‐induced arthritis (CIA) was also applied to test the effect of fecal microbiota transplantation (FMT) from Pre‐RA individuals on arthritis severity in mice.ResultsStool microbial diversity was lower in Pre‐RA individuals than in healthy controls. The bacterial community structure and function significantly differed between healthy controls and Pre‐RA individuals. Although there were differences to some extent in the bacterial abundance among the Pre‐RA subgroups, no robust functional differences were observed. The metabolites in the serum of the Pre‐RA group were dramatically different from those in the healthy controls group, with KEGG pathway enrichment of amino acid and lipid metabolism. Moreover, intestinal bacteria from the Pre‐RA group increased intestinal permeability in FMT mice and zonula occludens‐1 expression in the small intestine and Caco‐2 cells. Moreover, Th17 cells in the mesenteric lymph nodes and Peyer's patches were also increased in mice receiving Pre‐RA feces compared to healthy controls. The changes in intestinal permeability and Th17‐cell activation prior to arthritis induction enhanced CIA severity in PreRA‐FMT mice compared with HC‐FMT mice.ConclusionGut microbial dysbiosis and metabolome alterations already occur in individuals at high risk for RA. FMT from preclinical individuals triggers intestinal barrier dysfunction and changes mucosal immunity, further contributing to the development of arthritis.
Torpor‐responsive microRNAs in the heart of the Monito del monte, Dromiciops gliroides
Authors: Breedon Sarah A. , Varma Anchal , Quintero‐Galvis Julian F. , Gaitán‐Espitia Juan Diego , Mejías Carlos , Nespolo Roberto F. , Storey Kenneth B. 
Published: May 2023

AbstractThe marsupial Monito del monte (Dromiciops gliroides) utilizes both daily and seasonal bouts of torpor to preserve energy and prolong survival during periods of cold and unpredictable food availability. Torpor involves changes in cellular metabolism, including specific changes to gene expression that is coordinated in part, by the posttranscriptional gene silencing activity of microRNAs (miRNA). Previously, differential miRNA expression has been identified in D. gliroides liver and skeletal muscle; however, miRNAs in the heart of Monito del monte remained unstudied. In this study, the expression of 82 miRNAs was assessed in the hearts of active and torpid D. gliroides, finding that 14 were significantly differentially expressed during torpor. These 14 miRNAs were then used in bioinformatic analyses to identify Kyoto Encyclopedia of Genes and Genomes (KEGG) pathways that were predicted to be most affected by these differentially expressed miRNAs. Overexpressed miRNAs were predicted to primarily regulate glycosaminoglycan biosynthesis, along with various signaling pathways such as Phosphoinositide‐3‐kinase/protein kinase B and transforming growth factor‐β. Similarly, signaling pathways including phosphatidylinositol and Hippo were predicted to be regulated by the underexpression of miRNAs during torpor. Together, these results suggest potential molecular adaptations that protect against irreversible tissue damage and enable continued cardiac and vascular function despite hypothermia and limited organ perfusion during torpor.
Serial virus filtration: A case study evaluating the product‐dependent impact of control strategies on process efficiency
Authors: Kozaili Julie , Shah Aesha , Robbins Donna , Brinkman Nathan , Burdick Michael , Strauss Daniel 
Published: May 2023

AbstractThe production of biopharmaceutical products carries an inherent risk of contamination by adventitious viruses. Historically, these manufacturing processes have incorporated a dedicated virus filtration step to ensure product safety. However, challenging process conditions can lead to passage of small viruses to the permeate pool and an overall decrease in the desired virus logarithmic reduction value (LRV) for the process. The implementation of serial virus filtration has improved the robustness of such processes, albeit concerns about increased operating times and process complexity have limited its implementation. This work focused on optimizing a serial filtration process and identifying process control strategies to provide maximum efficiency while ensuring proper controls for process complexity. Constant TMP was identified as the optimal control strategy, which combined with the optimal filter ratio, resulted in a robust and faster virus filtration process. To demonstrate this hypothesis, data with two filters connected in series (1:1 filter ratio) are presented for a representative non‐fouling molecule. Similarly, for a fouling product, the optimal setup was a combination of a filter connected in series to two filters operated in parallel (2:1 filter ratio). The optimized filter ratios bring cost‐ and time‐savings benefits to the virus filtration step, thereby offering improved productivity. The results of risk and cost analyses performed as part of this study combined with the control strategy, offer companies a toolbox of strategies to accommodate products with different filterability profiles in their downstream processes. This work demonstrates that the safety advantages of performing filters in series can be achieved with minimal increases in time, cost, and risk.
Medium composition overturns the widely accepted sulfate‐dependent repression of desulfurization phenotype in Rhodococcus qingshengii IGTS8
Authors: Martzoukou Olga , Mamma Diomi , Hatzinikolaou Dimitris G. 
Published: May 2023

AbstractMicrobial desulfurization has been extensively studied as a promising alternative to the widely applied chemical desulfurization process. Sulfur removal from petroleum and its products becomes essential, as the environmental regulations become increasingly stringent. Rhodococcus qingshengii IGTS8 has gained ground as a naturally occurring model biocatalyst, due to its superior specific activity for desulfurization of dibenzothiophene (DBT). Recalcitrant organic sulfur compounds—DBT included—are preferentially removed by selective carbon‐sulfur bond cleavage to avoid a reduction in the calorific value of the fuel. The process, however, still has not reached economically sustainable levels, as certain limitations have been identified. One of those bottlenecks is the repression of catalytic activity caused by ubiquitous sulfur sources such as inorganic sulfate, methionine, or cysteine. Herein, we report an optimized culture medium for wild‐type stain IGTS8 that completely alleviates the sulfate‐mediated repression of biodesulfurization activity without modification of the natural biocatalyst. Medium C not only promotes growth in the presence of several sulfur sources, including DBT, but also enhances biodesulfurization of resting cells grown in the presence of up to 5 mM sulfate. Based on the above, the present work can be considered as a step towards the development of a more viable commercial biodesulfurization process.