bluuebunny/crossref_metadata_2025_split huggingface dataset:
Amino‐Substituted Azoxybenzenes as Potential Redox‐Active Catholyte Materials
Authors: Schatz Dominic , Burdenski Chris , Schneider Finn M. , Hansmann Max M. , Wegner Hermann A. 
Published: January 2025

AbstractAryl diazenes, particularly azobenzenes (AB), represent a versatile class of compounds with significant historical and practical relevance, ranging from dyes to molecular machines, solar thermal and electrochemical storage. Their oxygen‐substituted counterparts, azoxybenzenes (AOB), share structural similarities but have been less explored, especially in energy storage applications. This study investigates the redox properties of AOB, comparing them to AB, and evaluates their potential as redox‐active materials for energy storage systems. Through cyclic voltammetry (CV) and spectro‐electrochemical analyses, we demonstrate that AOBs exhibit a distinct redox behaviour, influenced by the solvent and electrolyte environment, with a reversible oxidation process. Despite their promising redox characteristics, AOBs suffer from capacity decay during galvanostatic cycling, likely due to the instability of the radical cation intermediate. These findings suggest that while AOBs offer intriguing redox properties, further investigation into stabilization strategies are needed for their application in energy storage.
Organometallic‐polypeptide Block Copolymers: Synthesis and Crystallization‐driven Self‐assembly in Aqueous Solutions to Rod‐like and Plate‐like Micelles with Polypeptide Coronas
Authors: Wang Yishan , Taek Kim Kyoung , Manners Ian , Winnik Mitchell A. 
Published: January 2025

AbstractThe synthesis of polyferrocenyldimethylsilane‐b‐poly(L‐glutamic acid) block copolymers was systematically explored. Rod‐like and plate‐like micelles were prepared from self‐assembly of the block copolymers in aqueous solution with two different approaches. In a dissolution‐dialysis approach, micelles were prepared by dissolving a block copolymer sample in excess aqueous base followed by the dialysis of the solution against water. The morphology of the resultant micelles showed composition dependence. The block copolymer sample with the lowest soluble block content formed rod‐like micelles, while the other samples with higher soluble block content formed spherical micelles. In a THF‐mediated approach, THF was added into a block copolymer solution, which was first prepared by the dissolution‐dialysis approach, and then the THF was evaporated slowly. Plate‐like micelles were obtained from all the block copolymer samples examined, and these had a broad range of soluble block content. The formation of these plate‐like micelles was attributed to the crystallization of the PFDMS blocks in the presence of THF. A tendency of large platelet micelles evolving to thin filaments over time was observed. This change may have been driven by the increase in the corona‐chain stretching energy as THF evaporated.
Carbene‐Functionalized Bulky‐Cyclopentadiene Rings
Authors: Arumugam Selvakumar , Kushvaha Saroj Kumar , Ravichandran Prathap , Kumar Jayasree , Gorantla Sai Manoj N. V. T. , Mondal Totan , Roesky Herbert W. , Mondal Kartik Chandra 
Published: January 2025

AbstractA series of significantly bulky mono‐ and di‐substituted cyclic alkyl‐amino carbene (cAAC)‐ functionalized cyclopentadiene ring (Cp) compounds were synthesized. The functionalization of the Cp ring with cAAC ligands makes them significantly bulkier, while retaining their ligation properties. These compounds display interesting fluorescence properties. In these compounds, intra‐molecular charge transfer is observed from electron‐rich carbene to electron‐deficient cyclopentadiene unit. These high yielding compounds have been characterized by X‐ray single‐crystal diffraction and their emission properties have been studied. Rotational conformers (via C−C bond rotation) play a pivotal role with possible different extent of intramolecular charge‐transfer (ICT) from carbene to cyclopentadiene ring. Variable temperature‐dependent NMR studies were performed along with NOSY, COSY and different 2D NMR techniques to estimate the energy barriers and 1,5‐Hydrogen shift.
Carbamate‐Functionalized NLOphores via a Formal [2+2] Cycloaddition‐Retroelectrocyclization Strategy
Authors: Savaş İpek , Çelik Mehmet Efe , Barsella Alberto , Dengiz Cagatay 
Published: January 2025

AbstractThis study introduces a new donor group capable of activating click‐type [2+2] cycloaddition‐retroelectrocyclizations, generally known for their limited scope. Target chromophores were synthesized using isocyanate‐free urethane synthesis. The developed synthetic method allows for the tuning of the optical properties of the chromophores by modifying the donor groups, the acceptor units, and the side chains. The charge transfer (CT) bands of the chromophores exhibit λmax values ranging from 363 to 692 nm. The CT bands observed have been supported by solvatochromism and protonation experiments. The synthesized compounds exhibit positive solvatochromism. Due to their potential as NLOphore candidates, the stability of the synthesized compounds have been investigated both experimentally through TGA and theoretically by calculating parameters such as frontier orbital energy differences, electronegativity, and global hardness/softness. TD‐DFT calculations were used to elucidate the nature of the electronic transitions, revealing that the bands correspond to CT arising from HOMO‐to‐LUMO excitations. The NLO properties of the chromophores were investigated theoretically by DFT methods and experimentally by the EFISHG technique. Both results are shown to be in agreement with HOMO‐LUMO energy differences. The experimental μβ values of the selected molecules range from 470×10−48 to 5400×10−48 esu.
Creating Dual Active Sites in Ru‐doped FeMn‐MOF‐74 for Efficient Overall Water Splitting
Authors: Sun Wenting , Hu Jinqi , Lou Yongbin , Chen Jinxi 
Published: January 2025

AbstractThe design of well‐engineered bifunctional electrocatalysts is crucial for achieving durable and efficient performance in overall water splitting. In this study, Ru‐doped FeMn‐MOF‐74 itself has Ru sites and generates FeMnOOH under catalytic conditions, forming dual active sites for overall water splitting. Density functional theory (DFT) calculations demonstrate that the Ru dopants exhibit optimized binding strength for H* and enhanced hydrogen evolution reaction (HER) performance. Moreover, the Mn sites within FeMnOOH lower the energy barrier for the rate‐determining step (from O* to OOH*), serving as the active centre for oxygen evolution reaction (OER). The incorporation of Ru significantly improves the electron transfer properties of FeMn‐MOF‐74 and enhances its water adsorption capacity, synergistically boosting its bifunctional activity. This strategy of designing dual active sites provides new insights into the development of bifunctional metal‐organic frameworks (MOFs) for efficient overall water splitting.
Seeded Growth and Scintillation Properties of Cs3Cu2I5 Perovskite Crystals by the Vertical Bridgman Method
Authors: Gu Yankai , Liu Yongsheng , Li Yang , Huang Yexi , Shen Hui , Xu Jiayue 
Published: January 2025

AbstractCopper halide perovskite Cs3Cu2I5 has attracted great interest due to its excellent scintillation properties, while it is rather challenging to grow large‐size bulk crystals. Herein, the seeded growth of Cs3Cu2I5 crystals are investigated by the vertical Bridgman method. Initially, Cs3Cu2I5 crystal is grown by spontaneous nucleation in a sealed quartz tube. Some Cs3Cu2I5 grains are processed into cylinders for the following seeded growth. Black Cs3Cu2I5 bulk crystal is obtained from the Pt crucible with a seed well in the air, with a dimension of Φ25 mm × 60mm and a <131> preferred growth orientation. The existence of I2 is possibly contributed to the crystal blackening. Using isodiametric seed, transparent Cs3Cu2I5 crystal wafers with dimensions over 20 mm are successfully grown under vacuum. The absorption edge of the Cs3Cu2I5 crystal is located at ≈330 nm. The photoluminescence of the crystal is centered at 445 nm, featuring a primary decay time of 850.88 ns (83.76%). It displays a significant light yield of 37,000 photons per MeV and an energy resolution of 5.1% at 662 keV, when subjected to γ‐ray radiation. The results reveal the feasibility of seeded growth of Cs3Cu2I5 crystals for potential scintillation applications.
Vitamin K‐dependent gamma‐carboxyglutamic acid protein 1 promotes pancreatic ductal adenocarcinoma progression through stabilizing oncoprotein KRAS and tyrosine kinase receptor EGFR
Authors: Wu Zheng , Ye Qing , Zhang Shan , Hu Li‐Peng , Wang Xiao‐Qi , Yao Lin‐Li , Zhu Lei , Xiao Shu‐Yu , Duan Zong‐Hao , Zhang Xue‐Li , Jiang Shu‐Heng , Zhang Zhi‐Gang , Liu De‐Jun , Li Dong‐Xue , Yang Xiao‐Mei 
Published: January 2025

AbstractBackgroundVitamin K‐dependent γ‐glutamic acid carboxylation (Gla) proteins are calcium‐binding and membrane‐associated, participating in coagulation, bone turnover, and cancer biology. The molecular function of transmembrane proline‐rich Gla proteins (PRRGs) remains unexplored.MethodsAnalysis of pancreatic ductal adenocarcinoma (PDAC) datasets, including transcription profiles, clinical data, and tissue microarrays, was conducted to evaluate PRRG1 expression and its clinical relevance. PDAC cell lines with overexpressed, knockdown, and mutated PRRG1 were developed to study biological functions and pathways using RNA‐seq, co‐immunoprecipitation with mass spectrometry, Western blotting, and immunofluorescence. In vivo xenograft and orthotopic models assessed PRRG1's impact on PDAC progression, with and without warfarin treatment.ResultsPRRG1 was significantly upregulated in PDAC compared to normal pancreas, correlating with poorer patient survival. PRRG1 knockdown reduced PDAC cell proliferation, anchorage‐independent growth in vitro, and tumor growth in vivo. PRRG1 localized at the plasma membrane, interacted with the HECT E3 ligase NEDD4 via the C‐terminal PPXY motif, and promoted NEDD4 self‐ubiquitination, reducing its protein levels. PRRG1 knockdown elevated NEDD4, destabilizing the oncoprotein KRAS and receptor EGFR, and attenuating downstream signaling and macropinocytosis under nutrient deprivation. The vitamin K‐dependent Gla modification of PRRG1 was crucial for its membrane localization and pro‐tumorigenic effects, and was inhibited by low‐dose warfarin, a clinical vitamin K antagonist.ConclusionsThis study identifies PRRG1 as a key regulator of pro‐tumorigenic signaling in PDAC, suggesting the potential of repurposing the anticoagulant warfarin as a therapeutic strategy.Key points
PRRG1 is identified as the transmembrane Gla protein mediating PDAC malignancy.
PRRG1 recruits and induces self‐ubiquitination of membrane‐anchoring E3 ligase NEDD4.
PRRG1 exerts a protective role toward KRAS and EGFR by inhibiting NEDD4.
The anticoagulant warfarin can be utilized to inhibit PRRG1 and PDAC advancement.
An Enhanced Heterogeneous Local Directed Acyclic Graph Blockchain With Recalling Enhanced Recurrent Neural Networks for Routing in Secure MANET‐IOT Environments in 6G
Authors: Begum M. Baritha , Suganthi B. , Sivagamasundhari P. , Arunmozhi S. A. , Suhail S. J. Muhamed 
Published: January 2025

ABSTRACTMobile ad hoc networks (MANETs) integrated with the Internet of Things (IoT) form a decentralized communication framework crucial for 6G environments. However, ensuring secure and efficient routing in such networks remains a challenge due to their distributed nature and vulnerability to attacks. This paper introduces a heterogeneous local directed acyclic graph blockchain (HLDAG‐BC) combined with recalling enhanced recurrent neural networks (RERNNs) for secure and efficient routing in MANET‐IoT environments. The HLDAG‐BC offers tamper‐proof communication and identity‐based conditional privacy‐preserving authentication (ICPA) is a lightweight and secure node authentication scheme. Network nodes are grouped using the kernel neutrosophic c‐means (KNCM) algorithm. The optimal cluster heads are chosen using the red piranha optimization (RPO) method. RERNN determines the shortest routing path to increase reliability and minimize latency. Furthermore, an HDLNN is used for intrusion detection to achieve robust network security. The HLDAG‐BC‐RERNN approach proposed shows that the packet delivery ratio improves by 31.35%, throughput by 34.56%, latency by 30.29%, and network lifetime by 28.67% compared to the existing approaches, as shown in the comprehensive evaluations. In conclusion, the proposed framework offers a scalable and secure solution for MANET‐IoT networks, making it a viable approach for future 6G applications.
Putting seedlings on the map: Trade‐offs in demographic rates between ontogenetic size classes in five tropical forests
Authors: Kambach Stephan , Bruelheide Helge , Comita Liza S. , Condit Richard , Wright S. Joseph , Aguilar Salomón , Chang‐Yang Chia‐Hao , Chen Yu‐Yun , Garwood Nancy C. , Hubbell Stephen P. , Luo Pei‐Jen , Metz Margaret R. , Nasardin Musalmah Bt. , Pérez Rolando , Queenborough Simon A. , Sun I‐Fang , Swenson Nathan G. , Thompson Jill , Uriarte María , Valencia Renato , Yao Tze Leong , Zimmerman Jess K. , Rüger Nadja 
Published: January 2025

AbstractAll species must partition resources among the processes that underly growth, survival, and reproduction. The resulting demographic trade‐offs constrain the range of viable life‐history strategies and are hypothesized to promote local coexistence. Tropical forests pose ideal systems to study demographic trade‐offs as they have a high diversity of coexisting tree species whose life‐history strategies tend to align along two orthogonal axes of variation: a growth–survival trade‐off that separates species with fast growth from species with high survival and a stature–recruitment trade‐off that separates species that achieve large stature from species with high recruitment. As these trade‐offs have typically been explored for trees ≥1 cm dbh, it is unclear how species' growth and survival during earliest seedling stages are related to the trade‐offs for trees ≥1 cm dbh. Here, we used principal components and correlation analyses to (1) determine the main demographic trade‐offs among seed‐to‐seedling transition rates and growth and survival rates from the seedling to overstory size classes of 1188 tree species from large‐scale forest dynamics plots in Panama, Puerto Rico, Ecuador, Taiwan, and Malaysia and (2) quantify the predictive power of maximum dbh, wood density, seed mass, and specific leaf area for species' position along these demographic trade‐off gradients. In four out of five forests, the growth–survival trade‐off was the most important demographic trade‐off and encompassed growth and survival of both seedlings and trees ≥1 cm dbh. The second most important trade‐off separated species with relatively fast growth and high survival at the seedling stage from species with relatively fast growth and high survival ≥1 cm dbh. The relationship between seed‐to‐seedling transition rates and these two trade‐off aces differed between sites. All four traits were significant predictors for species' position along the two trade‐off gradients, albeit with varying importance. We concluded that, after accounting for the species' position along the growth–survival trade‐off, tree species tend to trade off growth and survival at the seedling with later life stages. This ontogenetic trade‐off offers a mechanistic explanation for the stature–recruitment trade‐off that constitutes an additional ontogenetic dimension of life‐history variation in species‐rich ecosystems.
Seagrass wasting disease prevalence and lesion area increase with invertebrate grazing across the northeastern Pacific
Authors: Aoki Lillian R. , Ritter Carmen J. , Beatty Deanna S. , Domke Lia K. , Eckert Ginny L. , Graham Olivia J. , Gomes Carla P. , Gross Collin , Hawthorne Timothy L. , Heery Eliza , Hessing‐Lewis Margot , Hovel Kevin , Koehler Karl , Monteith Zachary L. , Mueller Ryan S. , Olson Angeleen M. , Prentice Carolyn , Rappazzo Brendan , Stachowicz John J. , Tomas Fiona , Yang Bo , Harvell C. Drew , Duffy J. Emmett 
Published: January 2025

AbstractDisease is a key driver of community and ecosystem structure, especially when it strikes foundation species. In the widespread marine foundation species eelgrass (Zostera marina), outbreaks of wasting disease have caused large‐scale meadow collapse in the past, and the causative pathogen, Labyrinthula zosterae, is commonly found in meadows globally. Research to date has mainly focused on abiotic environmental drivers of seagrass wasting disease, but there is strong evidence from other systems that biotic interactions such as herbivory can facilitate plant diseases. How biotic interactions influence seagrass wasting disease in the field is unknown but is potentially important for understanding dynamics of this globally valuable and declining habitat. Here, we investigated links between epifaunal grazers and seagrass wasting disease using a latitudinal field study across 32 eelgrass meadows distributed from southeastern Alaska to southern California. From 2019 to 2021, we conducted annual surveys to assess eelgrass shoot density, morphology, epifauna community, and the prevalence and lesion area of wasting disease infections. We integrated field data with satellite measurements of sea surface temperature and used structural equation modeling to test the magnitude and direction of possible drivers of wasting disease. Our results show that grazing by small invertebrates was associated with a 29% increase in prevalence of wasting disease infections and that both the prevalence and lesion area of disease increased with total epifauna abundances. Furthermore, these relationships differed among taxa; disease levels increased with snail (Lacuna spp.) and idoteid isopod abundances but were not related to abundance of ampithoid amphipods. This field study across 23° of latitude suggests a prominent role for invertebrate consumers in facilitating disease outbreaks with potentially large impacts on coastal seagrass ecosystems.
Safety Requirement of Electric Facilities in BESS Fire Accidents Viewpoint
Authors: Tashiro Yoichiro 
Published: January 2025

ABSTRACTBattery Energy Storage Systems (BESS) are compatible with renewable energy, so they are becoming increasingly popular around the world. On the other hand, the number of fire accidents are increasing with the spread of batteries, and as a result of the author's own analysis of these fire accidents, the author found phenomena unique to BESS fires. Therefore, the author will investigate whether Japan domestic laws and regulations are compatible with these unique phenomena and propose necessary safety countermeasures.
Preparation and Physicochemical Characterization of Layered Double Hydroxide MgAl‐LDHs/Celecoxib Hybrid Material
Authors: Chetara Amina , Bahmani Abdellah 
Published: January 2025

AbstractThis study presents the development and characterization of a Mg3Al‐COX hybrid system, designed to enhance the bioavailability of celecoxib (COX), a BCS class II hydrophobic anti‐inflammatory drug. Mg/Al layered double hydroxides (LDHs), with a 3 : 1 ratio, were synthesized via coprecipitation and calcination methods and then used to trap COX through a reconstitution process in a 60/40 v/v ethanol/water mixture. Comprehensive characterization using XRD, FTIR, TGA/DSC, BET, and SEM/EDS techniques confirmed the successful incorporation of COX within the LDHs matrix. Batch loading studies investigated the effects of contact time, initial pH, host material quantity, initial COX concentration, and temperature on the loading capacity Qe (mg/g). Kinetic analyses revealed that COX fixation follows a pseudo‐second‐order model, with intraparticle diffusion occurring in two distinct stages. Thermodynamic analysis detected a spontaneous and exothermic process. The Sips equation best represents the adsorption equilibrium by providing the highest correlation with a maximum loading capacity of 220.10 mg/g. Parameter calculations and error analyses validated the models used for the kinetic, thermodynamic, and equilibrium studies. These results demonstrate the feasibility of using LDHs as inclusion matrices to enhance the release properties of celecoxib, thereby paving the way for the development of controlled‐release dosage forms.
Diethylaluminium Chloride‐Mediated Cycloaddition/Conjugate Reduction Sequence towards Imido‐Substituted Norbornenes
Authors: Kirchhof Manuel , Batman Derman , Nicholas Elliot , Frey Wolfgang , Derdau Volker , Zens Anna , Laschat Sabine 
Published: January 2025

AbstractDiethylaluminium chloride is a known Lewis acid and can undergo 1,2‐ and 1,4‐additions, whereas conjugate reductions are mostly observed as side reactions. By serendipity we found a Et2AlCl‐promoted sequential cycloaddition/conjugate hydrogenation of cyclopentadiene and 4‐isopropyl‐3‐(3‐phenylpropioloyl) oxazolidin‐2‐one resulting in the clean formation of the corresponding norbornene‐oxazolidin‐2‐one. NMR, kinetic and deuteration experiments provided insight into the mechanism of this reaction sequence.
Evaluation of Yeast Alcohol Acetyltransferases for Ethyl Acetate Production in Clostridium ljungdahlii
Authors: Boto Santiago T. , Gerges Kareem , Bardl Bettina , Rosenbaum Miriam A. 
Published: January 2025

ABSTRACTSustainable chemical production from C1 gaseous substrates, such as syngas or CO2/H2, can be achieved through gas fermentation. In gas fermentation, acetogenic bacteria are able to utilize oxidized inorganic carbon sources as the sole carbon source and electron acceptor, while reduced inorganic species are used as the electron donor. Clostridium ljungdahlii, a model acetogen, is only capable of reducing CO2 to acetate and ethanol, with H2 as electron donor. In order to expand the product profile of this bacterium, five alcohol acetyltransferases (AATs) from yeast were heterologously expressed in C. ljungdahlii to evaluate its potential to produce ethyl acetate. When growing on CO2 and H2, up to 7.38 ± 0.43 mg/L of ethyl acetate were produced. Using fructose as the main carbon and energy source, up to 23.15 ± 1.28 mg/L of ethyl acetate were produced. Ethanol and fumarate supplementation were able to boost ethyl acetate titers (up to 37.51 ± 9.44 mg/L). Hence, ethyl acetate production was enabled in C. ljungdahlii at low titers, which could be explained by the high energetic cost of operation of AATs, and their shown promiscuity. However, we also show that this opens the door to more complex esterification reactions of higher added value biomolecules.