bluuebunny/crossref_metadata_2025_split huggingface dataset:
Methanolierung von Olefinen: Niederdruck‐Synthese von Alkoholen durch die formale Addition von Methanol an Olefine
Authors: Stahl Sebastian , Vossen Jeroen T. , Popp Stephan , Leitner Walter , Vorholt Andreas J. 
Published: November 2024

AbstractIn dieser Arbeit wird die Methanolierung von Olefinen als neue Niederdruck Synthese von C1‐verlängerten Alkoholen eingeführt. Formal wird H3COH an die C=C‐Bindung mit einer 100 %igen Atomeffizienz hinzugefügt. Mechanistisch gesehen, läuft die gesamte Umwandlung als Tandemreaktion ab, wobei Methanol zu Synthesegas in einem CO : H2 Verhältnis von 1 : 2 dehydriert wird, welches anschließend in der Hydroformylierung vom Olefin zum Aldehyd und der Hydrierung zum Alkohol umgesetzt wird. Die Dehydrierung von Methanol und die Hydrierung des Aldehyds werden durch einen Mn/Pincer‐Komplex katalysiert, während die Hydroformylierung mit einen Rh/Phosphin‐Katalysator erfolgt. Mit 1‐Octen als Modellsubstrat wurde eine Ausbeute von 80 % Nonanol mit einer n : iso‐Selektivität von 93 : 7 von linearen zu verzweigten Alkoholen erreicht, und es konnte eine Turn Over Number (TONRh ) von mehr als 17 000 in Bezug auf Rhodium erzielt werden. Das integrierte katalytische System ermöglicht den direkten Zugang zu Alkoholen aus Olefinen und “grünem” Methanol, wobei keine Handhabung von CO und H2 unter Druck oder spezielle Hochdruckanlagen notwendig sind, da die Prozessbedingungen 10 bar nicht überschreiten und die Partialdrücke des Synthesegases nur im Bereich von1–2 bar liegen.
Formally Zerovalent Bis(arene) Germylene Complexes of Zirconium and Hafnium
Authors: Eberhardt Max J. , Baum Mira , Clewing Stefan F. , Schubert Hartmut , Wesemann Lars 
Published: November 2024

AbstractTetrachlorides of zirconium and hafnium form adducts (2, 3) with an intramolecular germylene phosphine Lewis pair. Two electron reduction treating the adducts with [MesNacnacMg]2 gives the low‐valent metal complexes (4, 5) featuring η6‐Trip coordination at the Zr(II) and Hf(II) metal atom. Reduction of the M(II)‐complexes gives the zerovalent metal complexes of zirconium (6) and hafnium (7), which have been structurally characterized. Two arene moieties and the germylene exhibit metal coordination. Puckered coordination of a P‐phenyl unit was observed for both derivatives 6 and 7. Four electron reduction of a reaction mixture of metal tetrachloride with the germylene phosphine Lewis pair also gives the zerovalent complexes in good yield. Carbonyl complexes were synthesized treating the reduced metal complexes with carbon monoxide. Dimethylbutadiene shows a reaction with an arene moiety and the coordinated germylene ligand of the zerovalent complexes. A cyclohexadienyl and a triorganogermate ligand are formed. For zirconium this reaction is reversible at room temperature.
Molecular Components and Molecular Modelling for Asphalt: A Review
Authors: Wang Zhijin , Zhou Yuanbin , Zhang Jiandong , Ji Xinlv , Zhan Haifei 
Published: November 2024

AbstractAsphalt is a complex, heterogeneous organic mixture increasingly used in modern pavement. With the rising traffic load and sustainable strategies, developing high‐performance asphalt materials becomes crucial, which relies on the understanding of the relationship between the physical chemical properties of asphalt and its constituent molecular components. This work aims to review the progress on the identification of asphalt molecular components, as well as different types of molecules being employed in various molecular dynamics simulations to assess the physical properties of asphalt. The state‐of‐the‐art techniques for the separation of molecular components for asphalt materials are first introduced, followed by common characterization techniques for asphalt molecules and microstructural features, which serve as the foundations for molecular modeling for asphalt materials. Various asphalt molecular models being employed in molecular dynamics simulations are summarised, covering pristine asphalt, modified asphalt, and aged asphalt. Different factors that impact the physical properties of asphalt as uncovered from these simulations are also discussed. This work provides a comprehensive overview on the molecular components of asphalt and the corresponding modeling as atomistic scale, which can guide the preparation of asphalt materials with on‐demand properties for sustainable development.
Pre‐Procedural Virtual Reality Guiding Catheter Simulation Navigating Successful Percutaneous Coronary Intervention of a Chronic Total Occlusion of an Anomalous Origin of the Right Coronary Artery
Authors: Yoshinaga Masataka , Muramatsu Takashi , Higami Hiroki , Nasu Kenya 
Published: November 2024

ABSTRACTWe report two cases of successful percutaneous coronary intervention (PCI) of a chronic total occlusion (CTO) lesion with an anomalous origin of the right coronary artery (AORCA) and challenging guiding catheter engagement using a new 3D virtual reality (VR) guiding catheter simulation system. Appropriate guiding catheter selection is critical for a successful complex PCI. A more suitable guiding catheter size, shape, and position with a robust backup force often leads to the successful completion of more accessible and safer procedures. The present case report highlights that VR simulation provides a greater possibility than usual of pre‐procedural planning when selecting appropriate guiding catheters and vascular access. The present VR simulation system is based on three‐dimensional volume rendering reconstructions of the computed tomography (CT) imaging data; thus, another strength of this technology is that it does not require radiation or radiocontrast exposure to patients. Therefore, transcatheter interventionalists who usually perform complex PCI should be familiar with this innovative system.
Manganese‐Modified Metal Nanoparticle Catalysts for Syngas to C2+‐Oxygenates
Authors: Xiao Jiale , Meng Haotian , Wang Chengtao , Xiao Feng‐Shou 
Published: November 2024

AbstractSyngas to oxygenates, in particular to alcohols containing two or more carbon atoms (i.e., C2+‐oxygenates), is one of the important research subjects in syngas conversion. The key to this process is the design and synthesis of efficient catalysts. Metal nanoparticle catalysts such as Rh‐based and Co‐based catalysts in the presence of Mn promoter are popular candidates for the syngas to C2+‐oxygenates, where the Mn effectively optimizes the dispersion of metal species and significantly influences the C─O dissociation and *CO insertion activity, thereby enhancing the yield of C2+‐oxygenates. In this review, the mechanism on the formation of C2+‐oxygenates from syngas was briefly discussed, typical examples were highlighted, design of efficient RhMn‐based and CoMn‐based catalysts for enhancing the C2+‐oxygenates yields was summarized, and the perspectives and challenges for catalyst design in this area were suggested.
The Emissive and Electrochemical Properties of Hypervalent Pyridine‐Dipyrrolide Bismuth Complexes
Authors: Deuter Katharina L. , Kather Felix , Linseis Michael , Bodensteiner Michael , Winter Rainer F. 
Published: November 2024

AbstractWe present a series of six hypervalent bismuth complexes Bi(R1PDPR2)X bearing ligands characterized by the pyridine‐2,6‐bis(pyrrolide) (PDP) structural motif. While bismuth holds considerable potential for facilitating efficient intersystem crossing (ISC), reports on phosphorescent molecular bismuth complexes are still scarce and mostly based on systems that exhibit inter‐ or intraligand charge transfer character of their optical excitations. Herein, the UV/vis absorptive, luminescent, and electrochemical properties of complexes Bi(R1PDPR2)X are explored, where the substituents R1 and R2, as well as the halide ligand X are varied. These compounds are characterized by an intense HOMO→LUMO transition of mixed ligand‐to‐metal charge transfer (LMCT) and interligand charge transfer (LL'CT) character, as shown by time‐dependent density functional theory (TD‐DFT) calculations. At 77 K in a 2‐MeTHF matrix, these compounds exhibit red, long‐lived phosphorescence with lifetimes ranging from 479 to 14 μs. Cyclic voltammetry measurements and TD‐DFT calculations show that the substituents influence HOMO and LUMO energies to almost equal extent, resulting in nearly constant emission wavelengths throughout this series. Single‐crystal X‐ray diffraction studies of four of the six complexes exemplify the inherent Lewis acidity of the coordinated Bi3+ ion, in spite of its hypervalency.
In‐situ Reduced Cu3N Nanocrystals Enable High‐Efficiency Ammonia Synthesis and Zinc‐nitrate Batteries
Authors: Chen Shanshan , Wang Zhiwei , Zhang Quan , Qiu Shiming , Liu Yifan , Hu Guangzhi , Luo Jun , Liu Xijun 
Published: November 2024

AbstractNitrate reduction reaction (NO3RR) involves an 8‐electron transfer process and competes with the hydrogen evolution reaction process, resulting in lower yields and Faraday efficiency (FE) in the process of NH3 synthesis. Especially, Cu‐based catalysts (Cu0 and Cu+) have been investigated in the field of NO3RR due to the energy levels of d‐orbital and the least unoccupied molecular orbital (LUMO) π* of nitrate's orbital. Based on the above, we synthesized a Cu‐based compound containing Cu3N (Cu+) through a simple one‐step pyrolysis method, applied it to electrocatalytic NO3RR, and tested the performance of the Zn‐NO3− battery. Through various characterization analyses, Cu‐based catalysts (Cu+) are the key active sites in reduction reactions, making Cu3N a potential catalyst for ammonia synthesis. The research results indicate the application of Cu3N catalyst in NO3RR shows the best NH3 yield of 173.7 μmol h−1 cm−2 with FENH3 reaching 91.0 % at −0.3 V vs. RHE, which is much higher than that of Cu catalyst without N. In addition, the Zn‐NO3− battery based on Cu3N electrode also exhibits an NH3 yield of 39.8 μmol h−1 cm−2 63.0 % FENH3, and a power density of 2.7 mW cm−2 as well as stable cycling charge‐discharge stability for 5 hours. This work guides the application of Cu3N enhanced regulation of the active site in the electrocatalytic synthesis of NH3 from NO3RR.
Divergent Synthesis of Novel 3(5)‐Aminoazole–Benzopyrone Hybrids and their Evaluation as α‐Glucosidase Inhibitors
Authors: Myshko Andrii S. , Mrug Galyna P. , Bondarenko Svitlana P. , Demydchuk Bohdan A. , Kobzar Oleksandr L. , Buldenko Vladyslav M. , Vovk Andriy I. , Frasinyuk Mykhaylo S. 
Published: November 2024

AbstractAn efficient approach has been developed for the trapping in situ generated benzopyrone‐based ortho‐quinone methide intermediates by 3‐ and 5‐amino pyrazoles or isoxazoles. In cases of naturally occurring phenolic Mannich bases, hybrid compounds between the azole and flavonoid, namely, coumarin, chromone, isoflavone, and aurone were synthesized in moderate to good yields. It is remarkable that depending on 3‐ or 5‐position of the amino group, the reaction led to the formation of C‐4 or 3‐NH substituted azole derivatives, respectively. In vitro studies showed that some of the obtained compounds bearing 5‐aminoisoxazole part exhibit inhibitory activity towards α‐glucosidase with IC50 values in the micromolar range.
American Society of Clinical Oncology guideline update on palliative care for patients with cancer: Addressing the reality gap
Authors: Crowley Fionnuala , Smith Cardinale B. , Arnold Robert M. , Afezolli Debora 
Published: November 2024

Plain Language Summary

We commend the American Society of Clinical Oncology for their sweeping recommendations and advocacy for integrated palliative care as part of oncologic care. The literature that exists is heterogeneous and at times difficult to interpret, and the panel has clearly described their systemic review process and subsequent rationale for their recommendations.
Although we agree with the overall recommendations, there are significant practical limitations to their application that renders them aspirational. We worry that the guidelines may be impossible for most programs to fully achieve due to a variety of factors including specialty palliative care workforce shortages, limited health care system resource allocation to integrate palliative care widely in cancer care, and lack of financial support for the research necessary to better answer outstanding clinical and implementation questions.
We outline briefly some practical ways in which these recommendations can be applied by existing cancer centers and health care systems. Ultimately, both financial and quality incentives will be necessary to push forward the expansion and integration of palliative care within our national health care system as a whole.
Yield determination of temperate maize hybrids with different end‐uses: An ecophysiological analysis
Authors: Chazarreta Yésica D. , Alvarez Prado Santiago , Giménez Víctor D. , Carcedo Ana J. P. , López César G. , Ciampitti Ignacio A. , Otegui Maria E. 
Published: November 2024

AbstractMaize (Zea mays L.) production in Argentina changed markedly during the last decade due to the widespread adoption of late sowing dates, expanding its productive area, and diversifying crop end‐uses. This study was conducted to assess how the sowing date and nitrogen (N) availability affect grain yield, its physiological determinants (biomass and its partitioning), and numeric components (kernel number and kernel weight) of maize hybrids marketed for different end‐uses. Field experiments were conducted in two growing seasons (2019–2020 and 2020–2021) and two sowing dates within each season (early and late) at a site in the main maize‐producing region of Argentina. Within each season × sowing date combination, eight commercial maize hybrids (commercialized as grain, dual‐purpose, or silage) were tested under two N levels (N0: no N applied; N250: fertilized with 250 kg N ha−1). The greatest grain yield, biomass, kernel number, and harvest index corresponded to the grain hybrids. Dual‐purpose hybrids showed an intermediate grain yield, the highest kernel weight, and a more “silage” than “graniferous” behavior. Silage hybrids had improved light interception up to silking + 15 days (R2) but exhibited the lowest grain yield. Differences in end‐use steered crop breeding efforts toward different physiological strategies. The improved understanding of the physiological mechanisms underlying the productivity among maize hybrids with varying end‐uses will assist in the selection and management of suitable cultivars to be grown under different systems and environmental variations associated with an extended sowing date period.
PuraStat as secondary therapy for hemostasis in Mallory−Weiss syndrome with oral antithrombotic medication
Authors: Higashino Makoto , Murakami Hidehiro , Hirata Tetsu , Miyaoka Hiroaki 
Published: November 2024

AbstractMallory−Weiss syndrome (MWS) is a common cause of gastroesophageal bleeding. Vomiting increases intra‐abdominal and intra‐esophageal pressures, causing hyperextension of the esophagogastric junction and laceration. Most affected patients respond well to conservative treatment; however, those with active bleeding require endoscopic intervention. Upon contacting blood, PuraStat gels and coats the bleeding point to achieve hemostasis. PuraStat is reportedly effective for non‐variceal bleeding and bleeding associated with endoscopic procedures. However, there have been no reports on the use of PuraStat in MWS. Here we report a case in which PuraStat was useful for achieving hemostasis in a patient with MWS and difficult‐to‐achieve hemostasis. The patient was a 67‐year‐old man who had undergone coronary artery bypass grafting 1 month earlier and was taking an antithrombotic drug. He visited our hospital with bloody vomiting and melena in the evening and was diagnosed with upper gastrointestinal bleeding for which he underwent endoscopy. MWS with active bleeding was observed in the lower esophagus extending to the esophagogastric junction. We treated the patient with clipping; however, the oozing did not stop because of the large laceration. We applied PuraStat to the bleeding site and confirmed that the oozing had resolved; therefore, the procedure was terminated. The endoscope was reinserted the next day and confirmed the hemostasis. The patient was discharged without further deterioration. In patients with MWS with active bleeding, endoscopic hemostasis is commonly achieved using clips or endoscopic band ligation. However, PuraStat can achieve complete hemostasis when these techniques fail.
Endoscopic features of the duodenal pyloric gland adenoma: A case series of 14 patients
Authors: Uozumi Takeshi , Nonaka Satoru , Mizuguchi Yasuhiko , Suzuki Haruhisa , Abe Seiichiro , Yoshinaga Shigetaka , Sekine Shigeki , Saito Yutaka 
Published: November 2024

AbstractBackgroundPyloric gland adenoma (PGA) is a distinct subtype of duodenal adenoma. PGA has been increasingly recognized as a histologically and molecularly distinct entity; however, its endoscopic features have not been precisely described. This study aims to investigate the endoscopic characteristics of duodenal PGA, including the association of their putative precursors, Brunner's gland hyperplasia (BGH), and gastric epithelial heterotopia/metaplasia (GEM/H).MethodsThis study was a single‐center, retrospective case series. Fourteen consecutive patients with duodenal PGA were retrieved from the pathological database. PGA was diagnosed according to the World Health Organization classification.ResultsThe median tumor size was 22.5 mm (range: 12–40 mm), and 79% of cases were located in the first part of the duodenum. Six PGAs demonstrated high‐grade dysplasia. PGA could be classified into two subtypes based on their appearance: villous lobulated type and smoothly protruding type. BGH and GEM/H were identified in the background mucosa in 28% and 7% of the cases, respectively. BGH was more abundant in the background mucosa of the PGA group than in the control group (p < 0.05). Six PGAs (43%) exhibited high‐grade dysplasia, and no significant difference was observed in the endoscopic findings between low‐ and high‐grade dysplasia.ConclusionsThe 14 patients with PGA demonstrated characteristic endoscopic findings. BGH and GEM/H might be precursors of PGA.
ARHGAP29 promotes keratinocyte proliferation and migration in vitro and is dispensable for in vivo wound healing
Authors: Rhea Lindsey , Reeb Tanner , Adelizzi Emily , Garnica Bailey , Stein Allison , Kollash Alexis , Dunnwald Elliot , Dunnwald Martine 
Published: November 2024

AbstractBackgroundRhoA GTPases play critical roles in actin cytoskeletal remodeling required for controlling a diverse range of cellular functions including cell proliferation, adhesion, migration and changes in cell shape, all required for cutaneous wound healing. RhoA cycles between an active GTP‐bound and an inactive GDP‐bound form, a process regulated by guanine nucleotide exchange factors (GEFs) and GTPase‐activating proteins (GAPs). ARHGAP29 is a GAP expressed in skin keratinocytes and is decreased in the absence of interferon regulator factor 6, a critical regulator of cell proliferation, migration, and wound healing. However, the role for ARHGAP29 in keratinocyte biology is unknown.ResultsWe generated ARHGAP29 knockdown keratinocyte cell lines and show they displayed increased filamentous actin, phospho‐myosin regulatory light chain, cell area and population doubling time. Furthermore, we found that ARHGAP29 knockdown keratinocytes displayed significant delays in scratch wound closure in both single and collective cell migration conditions; these delays were rescued by both adding back ARHGAP29 or adding a ROCK inhibitor to ARHGAP29 knockdown cells. In vivo, however, Arhgap29 heterozygotes or keratinocyte‐specific knockouts showed on‐time wound healing.ConclusionsThese data demonstrate that ARHGAP29 is required for keratinocyte morphology, proliferation and migration in vitro but is dispensable during wound healing in vivo.
Evolution of Duplicated Glutathione Metabolic Pathway in Gossypium hirsutum and Its Response to UV‐B Stress
Authors: Song Xiaolin , Yin Xiaoyu , Zhu Yingjie , Su Qi , Bao Ying 
Published: November 2024

ABSTRACTIncreasing levels of UV‐B radiation caused by the greenhouse effect has become an emerging threat to crop health and yield. The glutathione (GSH) metabolic pathway is generally involved in plant stress responses through scavenging accumulated reactive oxygen species, and is therefore believed to play an essential role in enhancing plant tolerance to UV‐B stress. However, the complex evolutionary details of this pathway in polyploid plants, especially under UV‐B stress, remain largely unknown. Here, using the important allotetraploid crop, Gossypium hirsutum, as an example, we comprehensively investigated the composition and phylogenetic relationships of genes encoding 12 key structural enzymes in this pathway, and compared the expression changes of all the relevant genes under UV‐B stress (16 kJ m−2 d−1) based on six leaf transcriptomes. Consequently, we identified 205 structural genes by genome‐wide searching and predicted 98 potential regulatory genes under multiple stress conditions by co‐expression network analysis. Furthermore, we revealed that 19 structural genes including 5 homoeologous pairs and 96 regulatory genes possessing 25 homoeologous pairs were reticulately correlated without homoeologous selection preference under UV‐B stress. This result suggests a complex rewiring and reassignment between structural genes and their regulatory networks in the duplicated metabolic pathways of polyploid cotton. This study extends our understanding of the molecular dynamics of the GSH metabolic pathway in response to UV‐B stress in G. hirsutum and, more broadly, in polyploid plants.
Why Are Widely Distributed Species Widely Distributed? Understanding From a Quantified Investment Acquisition Strategy
Authors: Liu Xiao , Yi Shijie , Wu Pan , Wang Ning , Li Qiang 
Published: November 2024

ABSTRACTResearch on plant functional traits have advanced our understanding of plant investment acquisition strategies. However, it is still unknown how a plant investment acquisition strategy varies or how the relative position of plants on the leaf economic spectrum changes across different habitats. Therefore, we conducted the field experiments at two long‐term ecological research sites in Shandong and Xinjiang, China, in August 2023. Twenty‐two common species in both sites and four endemics in each site were selected for leaf gas exchange traits, leaf growth traits, and leaf nutrient trait measurements. We used two different methods to quantify the leaf economic spectrum, PCA quantification and functional area quantification. We found that the 22 common species had a significantly faster investment acquisition strategy than local endemics on the leaf economic spectrum. Besides, the plasticity of the 22 common species was not coupled with the plasticity of their investment acquisition strategy. According to our results, we quantified and constructed the leaf economic spectrum of the 30 woody plant species in Shandong and Xinjiang and discussed that high plasticity and fast investment acquisition strategy may be an ecological adaptation and distribution strategy for widely distributed species.