bluuebunny/crossref_metadata_2025_split huggingface dataset:
Passive Gate‐Tunable Kinetic Photovoltage along Semiconductor‐Water Interfaces
Authors: Li Jidong , Sheng Han , Long Yuyang , Zhu Yinlong , Deng Wei , Li Xuemei , Yin Jun , Guo Wanlin 
Published: March 2023

AbstractMoving boundaries of electric double layer at solid–liquid interface enables unprecedented persistent energy conversion and provokes a kinetic photovoltaic effect by moving an illumination region along the semiconductor‐water interface. Here, we report a transistor‐inspired gate modulation of kinetic photovoltage by applying a bias at the semiconductor‐water interface. The kinetic photovoltage of both p‐type and n‐type silicon samples can be facilely switched on/off, stemming from the electrical‐field‐modulated surface band bending. In contrast to the function of solid‐state transistors relying on external sources, passive gate modulation of the kinetic photovoltage is achieved simply by introducing a counter electrode with materials of desired electrochemical potential. This architecture provides the ability to modulate the kinetic photovoltage over three orders of magnitude and opens up a new way for self‐powered optoelectronic logic devices.
Crystal Structure of an i‐Motif from the HRAS Oncogene Promoter
Authors: Li Kevin S. , Jordan Deondre , Lin Linda Y. , McCarthy Sawyer E. , Schneekloth John S. , Yatsunyk Liliya A. 
Published: March 2023

AbstractAn i‐motif is a non‐canonical DNA structure implicated in gene regulation and linked to cancers. The C‐rich strand of the HRAS oncogene, 5′‐CGCCCGTGCCCTGCGCCCGCAACCCGA‐3′ (herein referred to as iHRAS), forms an i‐motif in vitro but its exact structure was unknown. HRAS is a member of the RAS proto‐oncogene family. About 19 % of US cancer patients carry mutations in RAS genes. We solved the structure of iHRAS at 1.77 Å resolution. The structure reveals that iHRAS folds into a double hairpin. The two double hairpins associate in an antiparallel fashion, forming an i‐motif dimer capped by two loops on each end and linked by a connecting region. Six C−C+ base pairs form each i‐motif core, and the core regions are extended by a G−G base pair and a cytosine stacking. Extensive canonical and non‐canonical base pairing and stacking stabilizes the connecting region and loops. The iHRAS structure is the first atomic resolution structure of an i‐motif from a human oncogene. This structure sheds light on i‐motifs folding and function in the cell.
Ampeln für die Katalyse: Stimulus‐reaktive molekulare und erweiterte katalytische Systeme
Authors: Thaggard Grace C. , Haimerl Johanna , Fischer Roland A. , Park Kyoung Chul , Shustova Natalia B. 
Published: March 2023

AbstractDie Fortschritte, die in den letzten fünf Jahren auf dem Gebiet der Stimuli‐reaktiven Katalyse erzielt wurden, mit dem Schwerpunkt auf neuen, kürzlich erschienenen Richtungen und Anwendungen, werden dargestellt. Diskutiert werden metallfreie Katalysatoren und metallorganische Komplexe sowie biomimetische Systeme und erweiterte Strukturen, die eine schaltbare katalytische Reaktivität für eine Vielzahl von organischen Reaktionen aufweisen. Lichtaktivierte Systeme, die aus photochromen Molekülen bestehen, welche in der Lage sind, Reaktionsgeschwindigkeit, Ausbeute oder Enantioselektivität auf Grundlage der geometrischen und elektronischen Veränderungen im Zusammenhang mit der Photoisomerisierung zu modulieren, stehen im Mittelpunkt der ausführlichen Diskussion. Alternative Stimuli wie pH‐Wert und Temperatur, die entweder allein oder in Kombination mit Licht angewendet werden können, werden ebenfalls behandelt. Die jüngsten Fortschritte zeigen deutlich, dass die Möglichkeit, das Verhalten eines Katalysators durch einen externen Stimulus fein abzustimmen, ein leistungsfähiges Instrument ist, das die Landschaft der nachhaltigen Chemie verändern könnte.
Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization
Authors: Chen Yang‐Bo , Liu Li‐Gao , Chen Can‐Ming , Liu Yi‐Xi , Zhou Bo , Lu Xin , Xu Zhou , Ye Long‐Wu 
Published: March 2023

AbstractAxially chiral biaryls widely exist in natural products and pharmaceuticals and are used as chiral ligands and catalysts in asymmetric synthesis. Compared to the well‐established axially chiral 6‐membered biaryl skeletons, examples of 5‐membered biaryls have been quite scarce, and mono‐substituted 3‐arylpyrrole atropisomers have not been reported. Here, we disclose a copper‐catalyzed atroposelective diyne cyclization for the construction of a range of axially chiral arylpyrrole biaryls in good to excellent yields with generally excellent enantioselectivities via oxidation and X−H insertion of vinyl cations. Importantly, this protocol not only represents the first synthesis of mono‐substituted 3‐arylpyrrole atropisomers, but also constitutes the first example of atroposelective diyne cyclization and the first atropisomer construction via vinyl cations. Theoretical calculations further support the mechanism of vinyl cation‐involved cyclization and elucidate the origin of enantioselectivity.
A Hemilabile NHC‐Gold Complex and its Application to the Redox Neutral 1,2‐Oxyarylation of Feedstock Alkenes
Authors: Scott Samuel C. , Cadge Jamie A. , Boden Grace K. , Bower John F. , Russell Christopher A. 
Published: March 2023

AbstractWe describe a AuI complex of a hemi‐labile (C^N) N‐heterocyclic carbene ligand that is able to mediate oxidative addition of aryl iodides. Detailed computational and experimental investigations have been undertaken to verify and rationalize the oxidative addition process. Application of this initiation mode has resulted in the first examples of “exogenous oxidant‐free” AuI/AuIII catalyzed 1,2‐oxyarylations of ethylene and propylene. These demanding yet powerful processes establish these commodity chemicals as nucleophilic‐electrophilic building blocks in catalytic reaction design.
Longitudinally Grafting of Graphene with Iron Phthalocyanine‐based Porous Organic Polymer to Boost Oxygen Electroreduction
Authors: Li Longbin , Tang Xiannong , Huang Senhe , Lu Chenbao , Lützenkirchen‐Hecht Dirk , Yuan Kai , Zhuang Xiaodong , Chen Yiwang 
Published: March 2023

AbstractIron phthalocyanine‐based polymers (PFePc) are attractive noble‐metal‐free candidates for catalyzing oxygen reduction reaction (ORR). However, the low site‐exposure degree and poor electrical conductivity of bulk PFePc restricted their practical applications. Herein, laminar PFePc nanosheets covalently and longitudinally linked to graphene (3D‐G‐PFePc) was prepared. Such structural engineering qualifies 3D‐G‐PFePc with high site utilization and rapid mass transfer. Thence, 3D‐G‐PFePc demonstrates efficient ORR performance with a high specific activity of 69.31 μA cm−2, a high mass activity of 81.88 A g−1, and a high turnover frequency of 0.93 e s−1 site−1 at 0.90 V vs. reversible hydrogen electrode in O2‐saturated 0.1 M KOH, outperforming the lamellar PFePc wrapped graphene counterpart. Systematic electrochemical analyses integrating variable‐frequency square wave voltammetry and in situ scanning electrochemical microscopy further underline the rapid kinetics of 3D‐G‐PFePc towards ORR.
Diazabicyclic Electroactive Ionenes for Efficient and Stable Organic Solar Cells
Authors: You Zuhao , Song Yanan , Liu Wenxu , Wang Wenlong , Zhu Chenghao , Duan Yuxin , Liu Yao 
Published: March 2023

AbstractElectroactive ionenes combining caged‐shaped diazabicyclic cations and aromatic diimides were developed as interlayers in organic solar cells (OSCs). These ionenes reduce the work‐function of air‐stable metal electrodes (e.g., Ag, Cu and Au) by generating strong interfacial dipoles, and their optoelectronic and morphological characters can be modulated by aromatic diimides, leading to high conductivity and good compatibility with active layers. The optimal ionene exhibits superior charge‐transport, desirable crystallinity, and weak visible‐absorption, boosting the efficiency of benchmark PM6 : Y6‐based OSCs up to 17.44 %. The corresponding normal devices show excellent stability at maximum power point test under one sun illumination for 1000 h. Replacing Y6 with L8‐BO promotes the efficiency to 18.43 %, one of the highest in binary OSCs. Notably, high efficiencies >16 % are maintained as the interlayer thickness increasing to 105 nm, the best result with interlayer‐thickness over 100 nm.
Divergent Total Syntheses of (−)‐Daphnezomines A and B and (+)‐Dapholdhamine B
Authors: Su Shaobin , Lin Chengcheng , Zhai Hongbin 
Published: March 2023

AbstractThe daphnezomine A‐type subfamily of Daphniphyllum alkaloids structurally features a unique aza‐adamantane core skeleton and anticipates efficient strategies for completing their syntheses to thoroughly investigate their biological activities. Herein, divergent total syntheses of (−)‐daphnezomines A and B and (+)‐dapholdhamine B have been accomplished in 16–20 steps from a known epoxide via rapid construction of a common core intermediate. The present work features a Ti‐mediated radical cyclization to establish the azabicyclo[3.3.1]nonane ring system, an intramolecular Heck reaction to install the bridgehead all‐carbon quaternary stereocenter, a tandem deprotection/reduction/keto amine‐carbinolamine tautomerization to furnish the aza‐adamantane backbone, and an NIS‐promoted 6‐endo‐trig aminocyclization to assemble the (+)‐dapholdhamine B backbone.
Freiformbauteile im Stahlbeton‐, Spannbeton‐ und Verbundbau: Berechnung von Querschnittswerten
Authors: Zimmert Florian , Braml Thomas 
Published: March 2023

AbstractEin ressourceneffizienter Einsatz des Baustoffs Beton kann erreicht werden, indem die individuelle Form eines betrachteten Bauteils an die auftretenden Beanspruchungen angepasst wird und Verbundbaustoffe (z. B. Betonstahl, Spannstahl oder Baustahl) in geeigneten Bauteilbereichen angeordnet werden. Durch die fortschreitende Digitalisierung im Bauwesen, beispielsweise im Kontext des Building Information Modeling, finden in der Planung von Bauwerken vermehrt computergestützte 3D‐Modellierungsverfahren Anwendung. Diese ermöglichen es Ingenieurinnen und Ingenieuren, Bauteile in Freiform zu entwerfen. Im Stahlbeton‐, Spannbeton‐ und Verbundbau ist die Bemessung derartiger Bauteile derzeit noch mit einem großen Aufwand verbunden. Im Kontext der Entwicklung eines praxisgerechten Verfahrens zur Berechnung von Freiformbauteilen aus Beton wird in diesem Aufsatz eine CAD‐integrierte Methode zur Berechnung wesentlicher Querschnittswerte vorgestellt. Querschnittswerte werden dann als wesentliche Berechnungsgrundlage benötigt, wenn reale dreidimensionale Bauteile unter Anwendung vereinfachter Berechnungstheorien, wie beispielsweise der Balkentheorie, behandelt werden. In diesem Beitrag werden die mathematischen und numerischen Grundlagen eines Verfahrens vorgestellt, welches es ermöglicht, die Querschnittswerte in Freiform umrandeter Beton‐, Stahlbeton‐, Spannbeton‐ und Verbundbauteile zu berechnen. Dem Verfahren liegen ebene, mittels Non‐uniform rational B‐Spline Tensor‐Produkten beschriebene Flächen zugrunde, welche beispielsweise aus Volumenkörpermodellen extrahiert werden können.
Using Holographic Microscopy To Measure the Effect of Confinement on Crowding Agents in Lipid Vesicles
Authors: Deckel Yaam , Lowe Lauren A. , Rawat Siddharth , Turner Matthew , Luong James , Wang Anna 
Published: March 2023

AbstractThe hydrodynamic effects of macromolecular crowding inside cells are often studied in vitro by using polymers as crowding agents. Confinement of polymers inside cell‐sized droplets has been shown to affect the diffusion of small molecules. Here we develop a method, based on digital holographic microscopy, to measure the diffusion of polystyrene microspheres that are confined within lipid vesicles containing a high concentration of solute. We apply the method to three solutes of varying complexity: sucrose, dextran, and PEG, prepared at ∼7 % (w/w). We find that diffusion inside and outside the vesicles is the same when the solute is sucrose or dextran that is prepared below the critical overlap concentration. For poly(ethylene glycol), which is present at a concentration higher than the critical overlap concentration, the diffusion of microspheres inside vesicles is slower, hinting at the potential effects of confinement on crowding agents.
Detailed overview of incidence and management of cytokine release syndrome observed with teclistamab in the MajesTEC‐1 study of patients with relapsed/refractory multiple myeloma
Authors: Martin Thomas G. , Mateos Maria Victoria , Nooka Ajay , Banerjee Arnob , Kobos Rachel , Pei Lixia , Qi Ming , Verona Raluca , Doyle Margaret , Smit Jennifer , Sun Weili , Trancucci Danielle , Uhlar Clarissa , van de Donk Niels W. C. J. , Rodriguez Cesar 
Published: March 2023

AbstractBackgroundTeclistamab, a B‐cell maturation antigen × CD3 bispecific antibody, demonstrated an overall response rate of 63.0% in 165 heavily pretreated patients with relapsed or refractory multiple myeloma in the phase 1/2 MajesTEC‐1 study. Cytokine release syndrome (CRS), a known manifestation of T‐cell redirection, was observed in 119 of 165 patients (72.1%).MethodsPatients received once‐weekly teclistamab 1.5 mg/kg subcutaneously after two step‐up doses (0.06 and 0.3 mg/kg). CRS was graded according to American Society for Transplantation and Cellular Therapy criteria and managed according to the study protocol, including use of tocilizumab and/or steroids.ResultsMost cases of CRS occurred during the step‐up dosing schedule of teclistamab and were grade 1 (50.3% of patients) or grade 2 (21.2% of patients); a single case of grade 3 CRS was reported in a patient with concurrent grade 3 pneumonia. All CRS cases resolved and none led to treatment discontinuation. Overall, 33.3% of patients had >1 CRS event; CRS recurrence was reduced when tocilizumab was administered for the first CRS event compared with when it was not (20.0% vs. 62.2%, respectively). Baseline characteristics such as tumor burden and cytokine levels did not appear to predict CRS incidence or severity.ConclusionsFindings of this study support the need for preemptive planning and prompt management of CRS in patients treated with T‐cell–engaging bispecific antibodies. Intervention with tocilizumab for CRS appears to decrease the likelihood of patients experiencing subsequent CRS events without compromising response to teclistamab.Plain language summary

Cytokine release syndrome (CRS), observed in 72.1% of patients treated with teclistamab in the MajesTEC‐1 study, was mostly grade 1 or 2 and manageable, without requiring treatment discontinuation.
Most CRS occurred during the step‐up schedule, requiring vigilance during treatment initiation.
Ensure fever is resolved and patients have no signs of infection before initiating the teclistamab step‐up schedule or administering the next teclistamab dose, to avoid exacerbating CRS.
Tocilizumab reduced the risk of subsequent CRS in patients receiving it for their first CRS event (20.0% vs. 62.2% in those not receiving it), without affecting response to teclistamab.
No baseline characteristics, including tumor burden or cytokine levels, appeared to clearly predict for CRS occurrence or severity.
Targeted and untargeted metabolites and antioxidant properties in chili pepper at different maturity stages
Authors: Yap Esther Shiau Ping , Uthairatanakij Apiradee , Laohakunjit Natta , Jitareerat Pongphen , Maier Claudia S. 
Published: March 2023

AbstractChilies (Capsicum sp.) are popular for their pungency and nutrition; however, these parameters vary with harvesting maturity. The effects of maturity stages on secondary compound levels and antioxidant activities in “super hot” chilies were investigated. Seven maturity stages were selected (i.e., 100% green to overripe stage). The differences in overall compounds were examined at each maturity stage, including the capsaicinoid, total phenolic content (TPC), and total flavonoid content (TFC) levels and the antioxidant activities. Untargeted metabolic analysis revealed that the abundance of capsaicin and dihydrocapsaicin, the pungency factors, was the highest among compounds, irrespective of maturity stage. The same was observed for piperidine‐containing compounds (e.g., piperidine propionic acid), which serve as an antidepressant and antioxidant agents. Targeted analysis showed that capsaicinoid levels in chilies increased from 100% green to 70% red stage, followed by a decrease and subsequent increase at the overripe stage. TPC was significantly the highest at the full red stage (13.51 mg GAE/g dry weight [DW]), whereas TFC was the highest at the 90% red stage (223.20 mg RUE/g DW). Regarding antioxidant activities, a decreasing trend was observed until the 90% red stage, followed by an increase thereafter. The capsaicinoid levels, antioxidant properties, and metabolites (e.g., 4‐piperidinol) were highest at the 80% green stage. However, the full red stage had high levels of eugenin, a phenol with antioxidant properties, and was preferred by consumers. Thus, it is recommended that the 80% green stage could be used in pharmaceutical industries, whereas the full 100% red stage could be consumed fresh or cooked.
Special Pore‐Space‐Partition CoFePBA Hollow Framework Realizing High‐Performance Glucose Sensing
Authors: Wang Jiang , Ying Shuanglu , Liu Tian , Kong Yuxuan , Lu Chunxiao , Ma Xinghua , Yi Fei‐Yan 
Published: March 2023

AbstractIn this work for the first time pore‐space‐partition (PSP)‐CoFePBA hollow framework is elaborately designed and successfully obtained via self‐template internal dissolution strategy. As is demonstrated by our previous report, Prussian blue analogue (PBA) with hollow morphology is very beneficial to improve sensing performance. As expected, the PSP‐CoFePBA hollow framework in this work exhibits far superior glucose sensing performance compared with classic CoFePBA nanoparticles and nanoboxes as well as most of reported PBA‐based glucose sensors. Herein, very high sensitivity of 1184.18 μA mM−1 cm−2 and 267.63 μA mM−1 cm−2 in the concentration range of 5–325 μM and 325–1025 μM, respectively, as well as low detection limit of 0.4 μM (S/N=3) and high stability can be observed. In a word, this work proposes and develops a simple and general synthetic strategy for constructing PBA‐based hollow material, that will be very helpful in this field.
Detection of LPS‐induced macrophage activation with single‐cell resolution through DC insulator‐based electrokinetic devices
Authors: Liu Yameng 
Published: March 2023

AbstractMacrophages are considered critical in the initiation, maintenance, and resolution of inflammation. Lipopolysaccharide (LPS)‐induced inflammation is often used as a model to understand the cell inflammation responses. Current techniques identifying the LPS‐induced inflammation are experiencing cell destruction or cell labeling or are based on the whole cell population information with low identification degree. This limits the detection process with time‐consuming cytokine selection, low resolution of population heterogeneity, and unavailability for their next use. Direct current insulator‐based electrokinetics (DC‐iEK) is introduced to achieve an easier and noninvasive identification of inflamed cells with high resolution. A biophysical scale is also established first time for screening medicine in the treatment of inflammation. The new microfluidic design concentrates cells with applied voltages forming streamline providing more stable cell capture conditions and unique biophysical factors at different capture positions. The average electric field of the cell capture positions is recorded to characterize each cell population. The characterization value of macrophage decreases from to 1.61 × 104 V/m when treated with 0.1 mM LPS and to 1.42 × 104 V/m when treated with 1 mM LPS. By treating the inflamed macrophages with representative effective medicines, healing signals could also be detected by a newly established inflammation scale. The cells showed proliferation and functional activity after extraction. DC‐iEK has provided an easy and noninvasive approach to identify inflammation for further fundamental and clinical precision medicine use.
Single‐cell RNA‐sequencing analysis reveals divergent transcriptome events between platinum‐sensitive and platinum‐resistant high‐grade serous ovarian carcinoma
Authors: Wang Zixun , Yang Linlin , Su Xiaoye , Wu Xiaomei , Su Rongjia 
Published: March 2023

AbstractBackgroundTumor resistance is one of the main reasons leading to the failure of ovarian cancer treatment. Overcoming platinum resistance remains the greatest challenge in the management of high‐grade serous ovarian carcinoma (HGSC).MethodsSmall conditional RNA‐sequencing is a powerful method for exploring the complexity of the cellular components and their interactions in the tumor microenvironment. We profiled the transcriptomes of 35,042 cells from two platinum‐sensitive and three platinum resistance HGSC clinical cases downloaded from Gene Expression Omnibus (GSE154600) and annotated tumor cells as platinum‐resistant or sensitive based on the clinical trait. The study systematically investigated the inter‐tumoral (using differential expression analysis, CellChat, and SCENIC) and intra‐tumoral heterogeneity (using enrichment analysis such as gene set enrichment analysis, as well as gene set variation analysis, weighted gene correlation network analysis, and Pseudo‐time analysis) of HGSC.ResultsA cellular map of HGSC generated by profiling 30,780 cells was revisualized using Uniform Manifold Approximation and Projection. The inter‐tumoral heterogeneity was demonstrated with intercellular ligand–receptor interactions of major cell types and regulons networks. FN1, SPP1, and COLLAGEN play important roles in the cross‐talk between tumor cells and the tumor microenvironment. HOXA7, HOXA9_extended, TBL1XR1_extended, KLF5, SOX17, and CTCFL regulons consistent with the distribution of platinum‐resistant HGSC cells were the high activity regions. The intra‐tumoral heterogeneity of HGSC was presented with corresponding functional pathway characteristics, tumor stemness features, and the cellular lineage transition from platinum‐sensitive to resistant condition. Epithelial–mesenchymal transition played an important role in platinum resistance, whereas oxidative phosphorylation was the opposite. There was a small subset of cells in platinum‐sensitive samples that had transcriptomic characteristics similar to platinum‐resistant cells, suggesting that the progression of platinum resistance in ovarian cancer is inevitable.ConclusionsThe present study describes a view of HGSC at single‐cell resolution that reveals the characteristics of the HGSC heterogeneity and provides a useful framework for future investigation of platinum‐resistant.