bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multi‐layer 3D Chirality and Double‐Helical Assembly in a Copper Nanocluster with a Triple‐Helical Cu15 Core
Authors: Dong Guanglei , Pan Zhonghua , Han Baoliang , Tao Yunwen , Chen Xin , Luo Geng‐Geng , Sun Panpan , Sun Cunfa , Sun Di 
Published: April 2023

AbstractConceptually mimicking biomolecules’ ability to construct multiple‐helical aggregates with emergent properties and functions remains a long‐standing challenge. Here we report an atom‐precise 18‐copper nanocluster (NC), Cu18H(PET)14(TPP)6(NCS)3 (Cu18H) which contains a pseudo D3‐symmetrical triple‐helical Cu15 core. Structurally, Cu18H may be also viewed as sandwich type of sulfur‐bridged chiral copper cluster units [Cu6−Cu6−Cu6], endowing three‐layered 3D chirality. More importantly, the chiral NCs are aggregated into an infinite double‐stranded helix supported by intra‐strand homonuclear C−H⋅⋅⋅H−C dihydrogen contacts and inter‐strand C−H/π and C−H/S interactions. The unique multi‐layered 3D chirality and the double‐helical assembly of Cu18H are evocative of DNA. Moreover, the collective behaviours of the aggregated NCs not only exhibit crystallization‐induced emission enhancement (CIEE) and aggregation‐induced emission enhancement (AIEE) effects in the deep‐red region, but also efficiently catalyze electron transfer (ET) reaction. This study thus presents that hierarchical assemblies of atomically defined copper NCs could be intricate as observed for important biomolecules like DNA with emergent properties arising from aggregated behaviours.
Formal γ−C−H Functionalization of Cyclobutyl Ketones: Synthesis of cis‐1,3‐Difunctionalized Cyclobutanes
Authors: Fan Zhoulong , Strassfeld Daniel A. , Park Han Seul , Wu Kevin , Yu Jin‐Quan 
Published: April 2023

Abstract1,3‐Difunctionalized cyclobutanes are an emerging scaffold in medicinal chemistry that can confer beneficial pharmacological properties to small‐molecule drug candidates. However, the diastereocontrolled synthesis of these compounds typically requires complicated synthetic routes, indicating a need for novel methods. Here, we report a sequential C−H/C−C functionalization strategy for the stereospecific synthesis of cis‐γ‐functionalized cyclobutyl ketones from readily available cyclobutyl aryl ketones. Specifically, a bicyclo[1.1.1]pentan‐2‐ol intermediate is generated from the parent cyclobutyl ketone via an optimized Norrish‐Yang procedure. This intermediate then undergoes a ligand‐enabled, palladium‐catalyzed C−C cleavage/functionalization to produce valuable cis‐γ‐(hetero)arylated, alkenylated, and alkynylated cyclobutyl aryl ketones, the benzoyl moiety of which can subsequently be converted to a wide range of functional groups including amides and esters.
Combining MN6 Octahedra and PN5 Trigonal Bipyramids in the Mica‐like Nitridophosphates MP6N11 (M=Al, In)
Authors: Ambach Sebastian J. , Pointner Monika , Falkai Sophie , Paulmann Carsten , Oeckler Oliver , Schnick Wolfgang 
Published: April 2023

AbstractLayered silicates are a very versatile class of materials with high importance to humanity. The new nitridophosphates MP6N11 (M=Al, In), synthesized from MCl3, P3N5 and NH4N3 in a high‐pressure high‐temperature reaction at 1100 °C and 8 GPa, show a mica‐like layer setup and feature rare nitrogen coordination motifs. The crystal structure of AlP6N11 was elucidated from synchrotron single‐crystal diffraction data (space group Cm (no. 8), a=4.9354(10), b=8.1608(16), c=9.0401(18) Å, β=98.63(3)°), enabling Rietveld refinement of isotypic InP6N11. It is built up from layers of PN4 tetrahedra, PN5 trigonal bipyramids and MN6 octahedra. PN5 trigonal bipyramids have been reported only once and MN6 octahedra are sparsely found in the literature. AlP6N11 was further characterized by energy‐dispersive X‐ray (EDX), IR and NMR spectroscopy. Despite the vast amount of known layered silicates, there is no isostructural compound to MP6N11 as yet.
Electrode‐Potential‐Driven Dissociation of N‐Heterocycle/BF3 Adducts: A Possible Manifestation of the Electro‐Inductive Effect
Authors: Hossain Md. Sazzad , Romo Adolfo I. B. , Putnam Seth T. , Dawlaty Jahan , Augustyn Veronica , Rodríguez‐López Joaquín 
Published: April 2023

AbstractRecently, non‐Faradaic effects were used to modify the electronic structure and reactivity of electrode‐bound species. We hypothesize that these electrostatic perturbations could influence the chemical reactivity of electrolyte species near an electrode in the absence of Faradaic electron transfer. A prime example of non‐Faradaic effects is acid‐base dissociation near an interface. Here, we probed the near‐electrode dissociation of N‐heterocycle‐BF3 Lewis adducts upon electrode polarization, well outside of the redox potential window of the adducts. Using scanning electrochemical microscopy and confocal fluorescence spectroscopy, we detected a potential‐dependent depletion of the adduct near the electrode. We propose an electro‐inductive effect where a more positive potential leads to electron withdrawal on the N‐heterocycle. This study takes a step forward in the use of electrostatics at electrochemical interfaces for field‐driven electrocatalytic and electro‐synthetic processes.
Gradientenbeton 2.0 – Ressourcenoptimierung durch Kombination von Hohlkörperbauweise und Trajektorienbewehrung
Authors: Sobek Werner , Schmeer Daniel 
Published: April 2023

AbstractMit Ausnahme der sog. Schubbügel folgt die Bewehrungsführung in Bauteilen aus Stahlbeton in der Regel der Geometrie der Bauteile, d. h., die Bewehrung wird entweder parallel zu den berandenden Oberflächen oder, seltener, senkrecht dazu verlegt. Obwohl bekannt ist, dass diese Art der Bewehrungsführung zu einem signifikanten Mehrverbrauch an Betonstahl führt, gilt sie auch heute noch als weltweiter Standard. Begründet wird dies mit der Einfachheit der Verlegung der Bewehrung, der hierdurch möglichen geringeren Fehlerquote auf der Baustelle und den durch beides erzielbaren Einsparungen an Lohnkosten. Aufgrund der weltweit erforderlichen Reduktion der Ressourcenverbräuche, des Energiebedarfs und der klimaschädlichen Emissionen gerade bei der Herstellung von Bauwerken kann davon ausgegangen werden, dass die Menge an eingebauter Bewehrung pro Bauteil zukünftig abnehmen wird. Aus den vorgenannten Gründen werden auch die Mengen an dem pro Bauteil eingebauten Beton abnehmen. Neben einer stärkeren Gliederung der Bauteiloberflächen werden dabei Hohlräume innerhalb der Bauteile sowie die Verwendung unterschiedlicher Betongüten innerhalb eines Bauteils zunehmend Verwendung finden. Im vorliegenden Beitrag wird eine Technologie vorgestellt, mit der im Stahlbetonbau deutliche Materialeinsparungen erzielt werden können. Sie besteht aus einer Hohlkörperbauweise in Kombination mit einer lastpfadgerechten Bewehrungsführung. Diese Technologie erlaubt die Umsetzung von gewichtsminimierten, materialeffizienten, emissionsreduzierten und sortenrein trennbaren Stahlbetonbauteilen.
A quantitative analysis method for a new glycogen synthase kinase‐3 inhibitor and its pharmacokinetics in rats
Authors: Wu Dan , Bai Xue , Yu Jiasi , Guo Linli , Zhao Yanan , Liu Ping 
Published: April 2023

AbstractAlzheimer's disease (AD), as a chronic and frequent neurodegenerative disease in the elderly population, has caused a huge economic burden to society, family, and other aspects. (E)‐N‐(4‐(((2‐amino‐5‐phenylpyridin‐3‐yl) imino) methyl) pyridine‐2‐yl) cyclopropanecarboxamide (PIMPC), a new glycogen synthase kinase‐3 (GSK‐3) inhibitor, has been designed and synthesized as a potential anti‐AD compound with antioxidant and metal chelating properties. In this study, we established an HPLC method for the determination of PIMPC, which has high accuracy, good sensitivity, and repeatability. This method determined the PIMPC content in rat plasma at different time points after intragastric administration to understand the pharmacokinetics (PK) process of PIMPC in rats. In addition, we preliminarily evaluated the effect of PIMPC on the liver and kidney in rats at pharmacodynamic doses. In conclusion, we have established a quantitative analysis method for PIMPC with excellent performance. And the PK process of PIMPC in rats, which was characterized by fast absorption, rapid distribution, and rapid elimination, conformed to the characteristics of the two‐compartment model. In addition, long‐term administration of PIMPC at therapeutic doses would not affect liver and kidney function. These studies have a certain reference for the development and research of PIMPC as a potential anti‐AD drug.
Metabolite profiles of Gansuibanxia decoction in rat plasma and urine by UHPLC‐Q‐TOF/MS analysis
Authors: Cui Yue , Tang Xinmiao , Feng Bo 
Published: April 2023

AbstractGansuibanxia decoction (GSBXD), a traditional Chinese medicine (TCM) formula with 2000 years of history, has good efficacies on treating cancerous ascites, pleural effusion, etc. However, little is known about its metabolite profiles owing to the lack of in vivo studies. In this study, we explored the prototypes and metabolites of GSBXD in rat plasma and urine using UHPLC–Q‐TOF/MS technology. A total of 82 GSBXD‐related xenobiotic bioactive components (38 prototypes and 44 metabolites) were confirmed or tentatively characterized, including 32 prototypes and 29 metabolites in plasma, and 25 prototypes and 29 metabolites in urine. The results showed that the bioactive components absorbed in vivo mainly contained diterpenoids, triterpenoids, flavonoids and monoterpene glycosides. Both phase I reactions (methylation, reduction, demethylation, hydrolysis, hydroxylation and oxidation) and phase II reactions (glucuronidation and sulfation) were involved in the metabolism of GSBXD in vivo. This study will provide a foundation for the quality control, pharmacological study and clinical application of GSBXD.
A rare case of perforated jejunal diverticula of an uncommon origin
Authors: Jawed Aleeza , Jawed Areesha , Kumari Sandhya , Shaikh Omer Ahmed , Nashwan Abdulqadir J. 
Published: April 2023

AbstractJejunal diverticula are often asymptomatic and rare, so they can go unnoticed until serious complications like obstruction, bleeding, perforation, volvulus, or diverticulitis occur. Elderly people over 60 are more likely to have this condition.
Methane Oxidation over PdO: Towards a Better Understanding of the Influence of the Support Material
Authors: Keller Kevin , Lott Patrick , Tischer Steffen , Casapu Maria , Grunwaldt Jan‐Dierk , Deutschmann Olaf 
Published: April 2023

AbstractThe presence of water vapor during the oxidation of the strong greenhouse gas methane over PdO‐based catalysts is known to result in severe inhibition and catalyst deactivation. In this context, our current study elucidates the role of the support material for different water concentrations in the reaction gas mixture. Compared to a reference PdO/Al2O3 catalyst, the catalytic activity can be significantly enhanced when using SnO2 and ZrO2 as support materials and remains stable during 24 h of operation at 823 K in the presence of 12 % H2O, whereas under identical conditions CH4 conversion drops by 68 % over PdO/Al2O3. The interplay between Pd species and catalyst support was systematically characterized by thermogravimetric analysis, temperature‐programmed reduction experiments and TEM measurements. Finally, a kinetic scheme was derived based on the experimental data.
Concentration‐, Temperature‐ and Solvent‐Dependent Self‐Assembly: Merocyanine Dimerization as a Showcase Example for Obtaining Reliable Thermodynamic Data
Authors: Vonhausen Yvonne , Würthner Frank 
Published: April 2023

AbstractMathematical models for the concentration‐, temperature‐ and solvent‐dependent analysis of self‐assembly equilibria are derived for the most simple case of dimer formation, to highlight the assumptions these models and the thus determined thermodynamic parameters are based on. The three models were applied to UV/Vis absorption data for the dimerization of a highly dipolar merocyanine dye in 1,4‐dioxane. Isothermal titration calorimetry (ITC) dilution experiments were performed as an independent reference technique. While the concentration‐dependent analysis is according to our studies the most reliable method, also the less time‐consuming temperature‐dependent evaluation can give accurate results in the present example, despite small thermochromic effects. In contrast, the strong negative solvatochromism of the merocyanine tampers with the results from the solvent‐dependent evaluation. Even though the studies presented in this work are limited to the monomer‐dimer equilibrium of a dipolar dye, the basic principles can be transferred to other chromophores and different self‐assembly models, including those for supramolecular polymerization.
Latent Pronucleophiles in Lewis Base Catalysis: Enantioselective Allylation of Silyl Enol Ethers with Allylic Fluorides
Authors: Kumar Suresh , Lange Markus , Zi You , Görls Helmar , Vilotijevic Ivan 
Published: April 2023

AbstractLewis base catalyzed allylations of C‐centered nucleophiles have been largely limited to the niche substrates with acidic C−H substituted for C−F bonds at the stabilized carbanionic carbon. Herein we report that the concept of latent pronucleophiles serves to overcome these limitations and allow for a variety of common stabilized C‐nucleophiles, when they are introduced as the corresponding silylated compounds, to undergo enantioselective allylations using allylic fluorides. The reactions of silyl enol ethers afford the allylation products in good yields and with high degree of regio/stereoselectivity as well as diastereoselectivity when cyclic silyl enol ethers are used. Further examples of silylated stabilized carbon nucleophiles that undergo efficient allylation speak in favor of the general applicability of this concept to C‐centered nucleophiles.
Dynamically Visualized Mechano‐Responsive Supramolecular Self‐Assembly System for Small Molecule Release
Authors: Wu Shihong , Qi Jiajia , Xia Xin , Zhou Ronghui , Zhao Hang 
Published: April 2023

AbstractThe mechano‐responsiverelease of small molecules has received extensive attention in ultrasound (US)‐controlled drug release in recent years because it can achieve non‐invasive, spatiotemporally controlled precise drug release. However, the vast majority of small molecules mechano‐release reported so far are based on polymer systems, which suffer from complex preparations and single mechano‐response. Here, an isoguanosine (isoG) visualized mechano‐responsive supramolecular self‐assembly (isoG‐VMRSS) system was successfully constructed by a one‐pot reaction. It is completely composed of small molecules, which allows for multiple mechano‐responsive releases of isoG (at least 9 times) and ultimately has potential for application in US drug release. A combined experimental‐computational approach reveals the supramolecular network structure (formed by the joint action of related metal coordination bonds, boronate ester bonds and hydrogen bonds mediated by isoG) gradually formed inside the system is the underlying internal mechanism. Therefore, it provides a new and effective idea of small molecule release in the field of mechanochemistry.
Using the Reactome Database
Authors: Rothfels Karen , Milacic Marija , Matthews Lisa , Haw Robin , Sevilla Cristoffer , Gillespie Marc , Stephan Ralf , Gong Chuqiao , Ragueneau Eliot , May Bruce , Shamovsky Veronica , Wright Adam , Weiser Joel , Beavers Deidre , Conley Patrick , Tiwari Krishna , Jassal Bijay , Griss Johannes , Senff‐Ribeiro Andrea , Brunson Timothy , Petryszak Robert , Hermjakob Henning , D'Eustachio Peter , Wu Guanming , Stein Lincoln 
Published: April 2023

AbstractPathway databases provide descriptions of the roles of proteins, nucleic acids, lipids, carbohydrates, and other molecular entities within their biological cellular contexts. Pathway‐centric views of these roles may allow for the discovery of unexpected functional relationships in data such as gene expression profiles and somatic mutation catalogues from tumor cells. For this reason, there is a high demand for high‐quality pathway databases and their associated tools. The Reactome project (a collaboration between the Ontario Institute for Cancer Research, New York University Langone Health, the European Bioinformatics Institute, and Oregon Health & Science University) is one such pathway database. Reactome collects detailed information on biological pathways and processes in humans from the primary literature. Reactome content is manually curated, expert‐authored, and peer‐reviewed and spans the gamut from simple intermediate metabolism to signaling pathways and complex cellular events. This information is supplemented with likely orthologous molecular reactions in mouse, rat, zebrafish, worm, and other model organisms. © 2023 The Authors. Current Protocols published by Wiley Periodicals LLC.Basic Protocol 1: Browsing a Reactome pathwayBasic Protocol 2: Exploring Reactome annotations of disease and drugsBasic Protocol 3: Finding the pathways involving a gene or proteinAlternate Protocol 1: Finding the pathways involving a gene or protein using UniProtKB (SwissProt), Ensembl, or Entrez gene identifierAlternate Protocol 2: Using advanced searchBasic Protocol 4: Using the Reactome pathway analysis tool to identify statistically overrepresented pathwaysBasic Protocol 5: Using the Reactome pathway analysis tool to overlay expression data onto Reactome pathway diagramsBasic Protocol 6: Comparing inferred model organism and human pathways using the Species Comparison toolBasic Protocol 7: Comparing tissue‐specific expression using the Tissue Distribution tool
Changes in water flow alter community dynamics in oyster reefs
Authors: Powers Sean P. , Grabowski Jonathan H. 
Published: April 2023

AbstractFluid (air or water) movements are key determinants of living systems from cellular to community levels of organization. Water flow can influence individual fitness and local population dynamics, but less is known about the collective response of natural communities to alteration in water flow because parameter responses to flow may be additive, juxtaposed, or interactive. To examine how changes in water flow affected initial larval settlement patterns of epifaunal and infaunal animals, colonization of larger individuals, and prey survival, we manipulated water flow (−50% or +47%) in situ using large wooden channels over small experimental oyster reefs. To test whether initial settlement patterns were additive or influenced by early post‐settlement processes (i.e., predation or competition reduced the densities), we compared patterns in short‐duration trials (two weeks) to those in longer duration deployments (six weeks). We found that minor changes in water flow (5–10 cm s−1) resulted in large changes in settlement of many species, predation levels, and the modification of initial settlement patterns. Settlement (two‐week intervals) and subsequent recruitment (six‐week intervals) increased for several species as flow rate increased. For most species, this relationship peaked at mid‐level flows (mud crabs, barnacles, and bivalves), whereas others (oysters) continued to increase with higher flow rates. Settlement patterns were best preserved in recruitment under high flow conditions where post‐settlement mortality was lower. Collectively, our results demonstrate how biological and physical processes are coupled in oyster reef systems, with relatively minor changes in water flow affecting pre‐ and post‐settlement processes.
Immunomodulation under the lens of real‐time in vivo imaging
Authors: Bousso Philippe , Grandjean Capucine L. 
Published: April 2023

AbstractModulation of cells and molecules of the immune system not only represents a major opportunity to treat a variety of diseases including infections, cancer, autoimmune, and inflammatory disorders but could also help understand the intricacies of immune responses. A detailed mechanistic understanding of how a specific immune intervention may provide clinical benefit is essential for the rational design of efficient immunomodulators. Visualizing the impact of immunomodulation in real‐time and in vivo has emerged as an important approach to achieve this goal. In this review, we aim to illustrate how multiphoton intravital imaging has helped clarify the mode of action of immunomodulatory strategies such as antibodies or cell therapies. We also discuss how optogenetics combined with imaging will further help manipulate and precisely understand immunomodulatory pathways. Combined with other single‐cell technologies, in vivo dynamic imaging has therefore a major potential for guiding preclinical development of immunomodulatory drugs.
The assessment of suture spacing on the esthetic and functional outcomes of skin closures in different age groups
Authors: Pazyar Nader , Movahedyan Maryam , Yaghoobi Reza , Haghighizadeh Mohammad Hosein 
Published: April 2023

AbstractBackground and AimsDermatological surgeons must master the factors affecting wound healing. Suturing is the most common method of wound closure. One of the significant factors in suturing that affects wound healing and cosmetic results is the distance between sutures, which has been studied very little to date. The aim of the current study was to investigate the effect of simple interrupted suture with a distance of 2 and 5 mm on the esthetic and functional results of suture closure in different age groups.MethodsIn patients with two skin lesions, one wound was sutured with a distance of 2 mm and the other with a distance of 5 mm, and the wounds were evaluated 1 and 3 months after the operation using the POSAS scale.ResultsPatients' opinions indicate that, in the suture intervals of 2‐ and 5‐mm and at 1 and 3 months, the average was lower in the younger group than it was in the older group and also, as per the physician's opinion, the average in the age group under 50 years was significantly lower than that in the age group over 50 years.ConclusionsAccording to the results of the present study, a suture of 2‐mm and a suture of 5‐mm would result in different esthetic and functional outcomes depending on the patient's age. The average in the age group less than 50 years was significantly lower than that of the age group greater than 50 years.