bluuebunny/crossref_metadata_2025_split huggingface dataset:
Carbene‐Catalyzed and Pnictogen Bond‐Assisted Access to PIII‐Stereogenic Compounds
Authors: Liu Jianjian , Deng Rui , Liang Xuyang , Zhou Mali , Zheng Pengcheng , Chi Yonggui Robin 
Published: April 2024

AbstractIntermolecular pnictogen bonding (PnB) catalysis has received increased interest in non‐covalent organocatalysis. It has been demonstrated that organic electron‐deficient pnictogen atoms can act as prospective Lewis acids. Here, we present a catalytic approach for the asymmetric synthesis of chiral PIII compounds by combining intramolecular PnB interactions and carbene catalysis. Our design features a pre‐chiral phosphorus molecule bearing two electron‐withdrawing benzoyl groups, resulting in the formation of a σ‐hole at the P atom. X‐ray and non‐covalent interaction (NCI) analysis indicate that the model substrates exhibit intrinsic PnB interaction between the oxygen atom of the formyl group and the phosphorus atom. This induces a conformational locking effect, leading to the crystallization of the phosphorus substrate in a preferred conformation (P212121 chiral group). Under the catalysis of N–heterocyclic carbene, the aldehyde moiety activated by the pnictogen bond selectively reacts with an alcohol to yield the corresponding chiral monoester/phosphorus product with excellent enantioselectivity. This Lewis acidic phosphorus center, aroused by the non‐polarized intramolecular pnictogen bond interaction, assists in conformational and selective regulations, providing unique opportunities for catalysis and beyond.
Chiral Ligand‐Concentration Mediating Asymmetric Transformations of Silver Nanoclusters: NIR‐II Circularly Polarized Phosphorescence Lighting
Authors: Zhang Chengkai , Si Wei‐Dan , Wang Zhi , Tung Chen‐Ho , Sun Di 
Published: April 2024

AbstractNear infrared (NIR) emitter with circularly polarized phosphorescence (CPP), known as NIR CPP, has emerged as a key part in the research of cutting‐edge luminescent materials. However, it remains a challenge to obtain nanoclusters with NIR CPP activity. Here, we propose an asymmetric transformation approach to efficiently synthesize two pairs of chiral silver nanoclusters (R/S‐Ag29 and R/S‐Ag16) using an achiral Ag10 nanocluster as starting material in the presence of different concentration chiral inducer (R/S)‐1,1′‐binaphthyl‐2,2′‐diyl hydrogenphosphate (R/S‐BNP). R/S‐Ag29, formed in the low‐concentration R/S‐BNP, exhibits a unique kernel‐shell structure consisting of a distorted Ag13 icosahedron and an integrated cage‐like organometallic shell with a C3 symmetry, and possesses a superatomic 6‐electron configuration (1S2|1P4). By contrast, R/S‐Ag16, formed in the high‐concentration R/S‐BNP, features a sandwich‐like pentagram with AgI‐pure kernel. Profiting from the hierarchically chiral structures and superatomic kernel‐dominated phosphorescence, R/S‐Ag29 exhibits infrequent CPP activity in the second near‐infrared (975 nm) region, being the first instance of NIR‐II CPP observed among CPL‐active metal nanoclusters. This study presents a new approach to reduce the difficulty of de novo synthesis for chiral silver nanomaterials, and facilitates the design of CPP‐active superatomic nanoclusters in NIR region.
Triaryl Carbenium Ion Pair Mediated Electrocatalytic Benzylic C−H Oxygenation in Air
Authors: Zhang Zhenguo , Lv Yongheng , Ji Liang , Chen Peng , Han Shuyan , Zhu Yufei , Li Lanyang , Jia Zhenhua , Loh Teck‐Peng 
Published: April 2024

AbstractThe selective oxidation of benzylic C−H bonds is a pivotal transformation in organic synthesis. Undoubtedly, achieving efficient and highly selective aerobic oxidation of methylarenes to benzaldehydes has been highly challenging due to the propensity of benzaldehyde to undergo overoxidation under typical aerobic conditions. Herein, we propose an innovative approach to address this issue by leveraging electrocatalytic processes, facilitated by ion‐pair mediators [Ph3C]+[B(C6F5)4]−. By harnessing the power of electrochemistry, we successfully demonstrated the effectiveness of our strategy, which enables the selective oxidation of benzylic C−H bonds in benzylic molecules and toluene derivatives. Notably, our approach exhibited high efficiency, excellent selectivity, and compatibility with various functional groups, underscoring the broad applicability of our methodology.
Enhanced Electrochemical CO2 Reduction to Formate over Phosphate‐Modified In: Water Activation and Active Site Tuning
Authors: Wei Zhiming , Ding Jie , Wang Ziyi , Wang Anyang , Zhang Li , Liu Yuhang , Guo Yuzheng , Yang Xuan , Zhai Yueming , Liu Bin 
Published: April 2024

AbstractElectrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P−O)δ− modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P−O)δ− has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface‐enhanced infrared absorption spectroscopy (ATR‐SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P−O)δ− modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P−O)δ− modified oxide‐derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm−2 and a cathodic potential of −1.2 V vs. RHE in an alkaline electrolyte.
Molecular Wiring of Electrocatalytic Nitrate reduction to Ammonia and Water Oxidation by Iron‐Coordinated Macroporous Conductive Networks
Authors: Li Mengjie , Wen Yingke , Fang Yanjie , Shan Bing 
Published: April 2024

AbstractDeveloping stable electrocatalysts with accessible isolated sites is desirable but highly challenging due to metal agglomeration and low surface stability of host materials. Here we report a general approach for synthesis of single‐site Fe electrocatalysts by integrating a solvated Fe complex in conductive macroporous organic networks through redox‐active coordination linkages. Electrochemical activation of the electrode exposes high‐density coordinately unsaturated Fe sites for efficient adsorption and conversion of reaction substrates such as NO3− and H2O. Using the electrode with isolated active Fe sites, electrocatalytic NO3− reduction and H2O oxidation can be coupled in a single cell to produce NH3 and O2 at Faradaic efficiencies of 97 % and 100 %, respectively. The electrode exhibits excellent robustness in electrocatalysis for 200 hours with small decrease in catalytic efficiencies. Both the maximized Fe‐site efficiency and the microscopic localization effect of the conductive organic matrix contribute to the high catalytic performances, which provides new understandings in tuning the efficiencies of metal catalysts for high‐performance electrocatalytic cells.
The distribution of the juvenile stages and eggcases of skates (Rajidae) around the British Isles
Authors: Ellis Jim R. , Gordon Cat A. , Allen Harriet L. , Silva Joana F. , Bird Christopher , Johnston Graham , O'Connor Bríd , McCully Phillips Sophy R. , Hood Ali 
Published: April 2024

Abstract

Skates (Rajidae) include species of conservation and commercial importance, but there is limited information regarding their ecologically important habitats, including spawning and nursery areas, in northern European seas.
Data on the distribution, relative abundance and length composition of skates were collated from scientific trawl surveys, and based on length‐frequency information, length‐at‐hatching and length‐at‐maturity, skates were allocated to length‐based categories representing early‐juvenile stages (EJS) and mid‐juvenile stages (MJS).
Citizen science data were used to inform on the occurrence of eggcases. The Great Eggcase Hunt (starting in 2003) citizen science recording project collects georeferenced data for elasmobranch eggcases, primarily from around the British Isles. This provided verified species‐specific data for a total of 227,407 specimens from 11 skate species. Purse Search Ireland (starting in 2005) provided a further 2491 records of 10 skate species from around Ireland.
The most frequently observed skate eggcases were from the genus Raja and occurred around much of the British Isles. The EJS and MJS of such species were observed most frequently in inshore waters. Data for EJS were more limited for Raja microocellata and Raja undulata, indicating that the EJS of these species occur in shallower (<20 m) waters.
Juveniles of the genus Leucoraja occurred further offshore. Only the eggcases of Leucoraja naevus were recorded regularly, with the eggcase of Leucoraja fullonica described here.
The data collated here provide an overview of skate spawning and nursery areas, thus informing fisheries management and marine spatial planning, including the identification and delineation of Important Shark and Ray Areas (ISRAs).
Adaptive neural network finite‐time control for fractional‐order nonlinear systems with external disturbance
Authors: Shang Zhendong , Lin Siyu , Xu Jinglan , Zhang Weiwei , You Xingxing , Dian Songyi 
Published: April 2024

AbstractThis paper is concerned with the finite‐time tracking control problem of fractional‐order nonlinear systems (FONSs) with uncertainty and external disturbance. A novel design scheme of the adaptive neural network finite‐time controller (ANNFTC) is developed by utilizing the theory of finite‐time stability and fractional‐order dynamic surface control (DSC) scheme combined with backstepping method. Radial basis function neural networks (RBF NNs) are employed to estimate the unknown nonlinear function. Furthermore, an auxiliary function is introduced to approximate the unknown upper bounds of the approximation error in RBF NNs and external disturbance. The ANNFTC ensures the finite‐time boundedness of all signals in FONSs and enhances the system output's tracking performance. The effectiveness of the proposed approach is demonstrated through a simulation example, providing empirical evidence to support the theoretical framework presented in this paper.
Algae to HEFA: Economics and potential deployment in the United States
Authors: Atnoorkar Swaroop , Wiatrowski Matthew , Newes Emily , Davis Ryan , Peterson Steve 
Published: April 2024

AbstractTo reach the goals set by the US Department of Energy's Sustainable Aviation Fuel (SAF) Grand Challenge, currently available feedstocks may be insufficient. Giving priority to developing, prototyping and reducing the cost of algal feedstock before investing and lining up locations is important. As the production of algal feedstocks advances, a simplified conversion approach using more mature technologies can help reduce the investment risk for algae‐based fuels. Reducing process complexity to the steps described here [namely, conversion of lipids to HEFA (hydroprocessed esters and fatty acids) fuels and relegating the remainder of the biomass to anaerobic digestion or food/feed production] enables the near‐term production of algal SAF but presents challenging economics depending on achievable cultivation costs and compositional quality. However, these economics can be improved by present‐day policy incentives. With these incentives, the modeled algae‐to‐HEFA pathway could reach a minimum fuel selling price as low as $4.7 per gasoline gallon equivalent depending on the carbon intensity reduction that can be achieved compared with petroleum. Uncertainty about algal feedstock production maturity in the current state of technology and the future will play a large role in determining the economic feasibility of building algae‐to‐HEFA facilities. For example, if immaturity increases the feedstock price by even 10%, SAF production in 2050 is about 58% of the production which could have been achieved with mature feedstock. Additionally, growth in this conversion pathway can be notably boosted through the inclusion of subsidies, and also through higher‐value coproducts or higher lipid yields beyond the scope of the process considered here.
Identification of key mRNAs and signaling pathways in obsessive compulsive disorder based on weighted gene co‐expression network analysis and cytoHubba plugin
Authors: Zhang Xiaoming , Liu Yanru , Guo Bin , Li Binbin , Liu Huaqing , Wang Zhiren 
Published: April 2024

AbstractPurposeObsessive‐compulsive disorder (OCD) is a complex psychiatric disorder. Genetic and broad environmental factors are common risk factors for OCD. The purpose of this study is to explore the molecular mechanism of OCD and to find new molecular targets for the diagnosis and management of OCD.MethodsAll data were downloaded from public dataset. Key modules and candidate key mRNAs were identified based on weighted gene co‐expression network analysis (WGCNA). The “limma” R package was used for differential expression analysis of mRNAs. Subsequently, functional enrichment analysis of differentially expressed mRNAs (DEmRNAs) was also carried out. In addition, a diagnostic model was constructed. Finally, the infiltration level of immune cells in OCD and its correlation with multicentric key DEmRNAs were analyzed.ResultsGreen and red modules were selected as the hub modules. A total of 447 mRNAs were considered candidate key mRNAs according to GS > 0.2 and MM > 0.3. A total of 26 DEmRNAs in the same direction were identified in the GSE60190 and GSE78104 datasets. A total of 26 DEmRNAs were intersected with candidate key mRNAs in WGCNA to obtain 10 intersection DEmRNAs (HSPB1, ITPK1, CBX7, PPP1R10, TAOK1, PISD, MKNK2, RWDD1, PPA1, and RELN). However, only four DEmRNAs (HSPB1, TAOK1, MKNK2, and PPA1) predicted related drugs. Subsequently, receiver operating characteristic analysis shows that the diagnostic model has high diagnostic value. Moreover, six multicentric key DEmRNAs (SNRPF, SNRNP70, PRPF8, NOP56, EPRS, and CCT2) were screened by UpSet package. Finally, six multicentric key DEmRNAs were found to be associated with immune cells.ConclusionThe key molecules obtained in this study lay a foundation for further research on the molecular mechanism of OCD.
The impact of sestrin2 on reactive oxygen species in diabetic retinopathy
Authors: Yang Xueli , Wu Xiaoli 
Published: April 2024

AbstractDiabetic retinopathy (DR) is a significant complication of diabetes that often leads to blindness, impacting Müller cells, the primary retinal macroglia involved in DR pathogenesis. Reactive oxygen species (ROS) play a crucial role in the development of DR. The objective of this study was to investigate the involvement of sestrin2 in DR using a high‐glucose (HG)‐induced Müller cell model and assessing cell proliferation with 5‐ethynyl‐2‐deoxyuridine (EdU) labeling. Following this, sestrin2 was upregulated in Müller cells to investigate its effects on ROS, tube formation, and inflammation both in vitro and in vivo, as well as its interaction with the nuclear factor erythroid2‐related factor 2 (Nrf2) signaling pathway. The findings demonstrated a gradual increase in the number of EdU‐positive cells over time, with a subsequent decrease after 72 h of exposure to high glucose levels. Additionally, the expression of sestrin2 exhibited a progressive increase over time, followed by a decrease at 72 h. The rh‐sestrin2 treatment suppressed the injury of Müller cells, decreased ROS level, and inhibited the tube formation. Rh‐sestrin2 treatment enhanced the expression of sestrin2, Nrf2, heme oxygenase‐1 (HO‐1), and glutamine synthetase (GS); however, the ML385 treatment reversed the protective effect of rh‐sestrin2. Finally, we evaluated the effect of sestrin2 in a DR rat model. Sestrin2 overexpression treatment improved the pathological injury of retina and attenuated the oxidative damage and inflammatory reaction. Our results highlighted the inhibitory effect of sestrin2 in the damage of retina, thus presenting a novel therapeutic sight for DR.
Pd‐Pt Bimetallic Catalysts for Enhanced Low‐Temperature Hydrodeoxygenation of Vanillin
Authors: Govoni Simone , Ventimiglia Alessia , Ferraz Camila P. , Itabaiana Ivaldo , Dufour Anthony , Pasc Andreea , Wojcieszak Robert , Dimitratos Nikolaos 
Published: April 2024

AbstractTo make pyrolytic bio‐oil useful as a transportation fuel, the oxygen content must be reduced, and this can be carried out by using catalytic hydrodeoxygenation (HDO) reaction. The greatest challenge is associated with the removal of strongly bound oxygenated groups without saturating the aromatic ring while preserving the number of carbons. However, the development of a stable catalyst that can selectively remove such oxygenated groups with low hydrogen consumption is still challenging. In this context, a systematic study on HDO of vanillin on bimetallic Pd−Pt catalysts was carried out. It aims to study the effect of bimetallic synergy in terms of activity and selectivity to creosol. Metallic nanoparticles of Pd and Pt were synthesized by sol immobilization technique and deposited on TiO2. The conversion of vanillin was correlated to the Pd−Pt atomic ratio, while the production of the creosol was correlated to the Pd(0)/(Pd+Pt) ratio at the surface. Full conversion of vanillin was obtained at low reaction temperature (20 °C) achieving nearly 100 % selectivity to creosol. These results represent a step forward in advancing the development of more efficient and sustainable processes for bio‐oil upgrading.
Alles unter Kontrolle
Authors: Hupach Sascha 
Published: April 2024

AbstractWasser wird in der chemischen Industrie in verschiedenen Prozessen eingesetzt. Zur Kontrolle hat sich der Summenparameter TOC durchgesetzt. Online‐ oder Prozessanalytik erlauben eine möglichst engmaschige Kontrolle der Wasserströme in unterschiedlichen Einsatzgebieten in der chemischen Industrie.
Die richtige Mischung für klare Verhältnisse
Authors: Tigges Bastian 
Published: April 2024

AbstractUm den Betrieb von Kläranlagen zukunftsfähig und effizient zu gestalten, wird der entstehende Klärschlamm thermisch verwertet. Für die erforderlichen Prozessbedingungen in einer der größten Kläranlagen Europas in Bottrrop sorgen Pflugscharmischer, die den Klärschlamm konditionieren und stets gleichbleibende Qualität sicherstellen, damit die Trocknung möglichst energieeffizient betrieben werden kann.
Removal performance of leonardite toward volatile organic compounds and toxic metals from landfill leachates
Authors: Kocaman Ayhan , Turan Metin , Vakili Amir Hossein , Savas Burak Feyyaz , Aydemir Özlem Ete , Çakici Avni 
Published: April 2024

AbstractLeachate from municipal waste contains volatile organic compounds and potentially toxic metals. The leaching of which into water sources also jeopardizes access to clean water. Therefore, reducing the concentration of pollutants in leachate is important to reduce health risks and environmental pollution. In this study, the efficacy of granulated organic leonardite added to leachate from municipal waste in reducing the toxic concentrations of the leachate for different time points (30, 60, 90, and 120 min) at a shaking speed of 200 rpm was investigated. Results demonstrated that leonardite significantly removed various contaminants, including organic acids (71.16%), alcohols (74.31%), aldehydes (68.01%), esters (78.28%), ethers (81.03%), ketones (68.52%), hydrocarbons (84.25%), N compounds (78.56%), S compounds (80.67%), organic N (86.01%), total Kjeldahl nitrogen (93.26%), NH4‐N (84.83%), NO3‐N (89.30%), SO4 (76.62%), PO4 (73.85%), organic C (50.07%), Hg (96.80%), Pb (95.99%), Cu (82.68%), Al (65.56%), total Cr (98.11%), Cd (99.28%), Li (96.31%), Ni (97.27%), and As (67.79%). The leonardite granules used in this study showed high adsorption and removal performance for organic/inorganic and volatile compounds in landfill leachate. These results indicate that leonardite can be a suitable adsorption material for leachate pretreatment. However, it is necessary to perform a durability test to use the material in the long term as a covering on landfills.
A spiral modeling based on manta ray foraging optimization for wireless networks resource allocation
Authors: Luo Qifang , Wang Meiyan , Zhou Yongquan 
Published: April 2024

SummaryThe wireless network resource allocation is a NP‐hard combinatorial optimization problem. This paper proposes a new optimization method using the manta ray foraging optimization (MRFO) based on spiral modeling to solve the wireless network resource problem. In order to reduce the computational complexity and ensure the optimal performance of the allocation scheme, a MRFO algorithm based on spiral modeling and mutation strategy is proposed. In the first stage, spiral modeling is introduced to narrow the exploration area, while the mutation strategy of the genetic algorithm enhances the ability of the algorithm to jump out of the local optimal. In the second stage, a binary MRFO algorithm for using different transfer functions is proposed to solve the mixed integer programming problem. The experimental results show that IMRFO and BIMRFO have high comprehensive performance advantages, achieve better effects than the other optimization algorithms, which lead to faster convergence, faster accuracy, and lower complexity.
Quantification of GTPase Cycling Rates of GTPases and GTPase:Effector Mixtures Using GTPase Glo Assays
Authors: Tschirpke Sophie , Daalman Werner K.‐G. , Laan Liedewij 
Published: April 2024

AbstractIn different cellular activities such as signal transduction, cell division, and intracellular transportation, small guanosine triphosphatases (GTPases) take on a vital role. Their function involves hydrolysis of guanosine triphosphate (GTP) to guanosine diphosphate (GDP). In this article, we explain the application of a commercially available GTPase assay—the GTPase Glo assay by Promega—for investigation of GTPase‐effector interactions. We provide experimental protocols together with an analysis model and software to obtain GTPase cycling rates of GTPases and GTPase:effector mixtures. GTPase cycling rates refer to the rates by which a GTPase completes an entire GTPase cycle. These rates enable quantification of the strength of GTPase effectors in a concentration‐dependent fashion, as well as quantification of the combined effect of two effectors, independent of which GTPase cycle step they are affecting. © 2024 The Authors. Current Protocols published by Wiley Periodicals LLC.Basic Protocol: Conducting GTPase Glo assaysSupport Protocol 1: Analyzing GTPase assays to correlate luminescence with remaining GTPSupport Protocol 2: Fitting GTPase assay data to obtain GTPase cycling rates