bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rhodolith Beds Along the Southwest Atlantic Ocean: From Shallow to Mesophotic Habitats. Review of a Singular Ecosystem
Authors: Curbelo‐Fernandez Maria Patricia , Yoneshigue‐Valentin Yocie , Valentin Jean Louis , Lavrado Helena Passeri 
Published: September 2024

ABSTRACTRhodolith beds are one of the major marine coastal ecosystems. Knowing the spatial distribution, environmental characteristics and composition is not only scientifically pertinent but also crucial to allow comparisons in case of changes due to local and global anthropogenic pressures. With slow algal growth rates, high associated diversity and potential importance as nursery grounds, rhodolith beds are present along the Brazilian coast of the Southwest Atlantic Ocean. This study provides an updated map of shallow and mesophotic rhodolith distribution after a systematic literature review. The prevailing oceanographic conditions along most parts of the Brazilian coast render the environment suitable for the developing rhodolith beds (a total of 68 taxa in this review), with 63 taxa along the East Brazilian Shelf, seven taxa for the North Brazilian Shelf and 10 taxa in the South Brazilian Shelf. According to composition, shallow and mesophotic communities were more similar in each large marine ecosystem than among them. In addition to gaps in terms of distribution, there are uncertainties about the taxonomic composition of the rhodoliths, associated fauna and flora and oceanographic and geological characteristics of the bottoms, which call attention to the importance of further studies, mainly in the mesophotic. This review provides a more precise distribution of these habitats along the Brazilian coast of the Southwest Atlantic Ocean. It contributes to a more detailed taxonomic composition of calcareous algae in an extremely relevant marine ecosystem, which is crucial for many species, including the endemic kelp, Laminaria abyssalis.
Microporous Polyethylene and Cellulose Composite Separators for Reversible Lithium Electrode in Lithium Rechargeable Batteries
Authors: Hirai Yuna , Ohnishi Rio , Taminato Sou , Mori Daisuke , Eimura Hiroki , Ikoma Kei , Sawamoto Atsushi , Yamamoto Osamu , Takeda Yasuo , Imanishi Nobuyuki 
Published: September 2024

AbstractThe lithium metal anode is the best candidate for high energy density batteries because of its high specific capacity and low negative potential. Rechargeable lithium metal batteries (RLMB) have not yet been commercialized. The key factors that limit the practical use of RLMB are the formation and growth of lithium dendrites during the lithium deposition process and the reaction of the lithium anode with the organic solvent of the electrolyte, quantified by the Columbic efficiency (CE). To suppress the lithium dendrite formation and to improve CE, many approaches such as the formation of a protective layer on the lithium electrode and the use of additives to the electrolyte have been proposed. In this study, the effect of a thin cellulose film to improve CE of lithium deposition and stripping on the lithium electrode was examined. The cycle performance of a Li/Li symmetrical cell with a cellulose and polyethylene composite separator was examined for a carbonate electrolyte and an ether electrolyte. The improvements of CE were observed for both electrolytes with the cellulose film separator. The improvement could be explained by the good wettability of the cellulose film separator with the electrolyte.
Bilateral orchidopexy for intermittent testicular torsion
Authors: Hegarty Paul K. , Kalantar Mona , Hegarty Penelope A. , Zafirakis Helen , Monahan Jack E. 
Published: September 2024

AbstractObjectivesTo assess the effect of bilateral orchidopexy in preventing future torsion and testicular loss in patients with intermittent testicular torsion. Secondarily, this study aims to assess the rate of pain improvement following orchidopexy.MethodsThis is a prospective cohort of patients. Participants were men who underwent elective bilateral orchidopexy for intermittent testicular torsion. All consecutive cases were treated by a single surgeon in a single centre between 2015 and 2023. The primary outcomes were prevention of torsion and testicular loss. The secondary outcome was the resolution or improvement in pain.ResultsThe success rate of bilateral orchidopexy in preventing testicular loss due to torsion was 100%, at a follow‐up of mean 33.5 months. Of the 50 patients, 88% were pain‐free following orchidopexy, and 12% had an improvement in their pain. There were no cases of hydrocoele or haematoma in this series. To our knowledge, this is the largest series reported in the literature.ConclusionsElective bilateral orchidopexy prevents torsion and preserves testicular viability. Pain is resolved in most but not all cases. This is important in counselling men who are considering surgical management of intermittent torsion of the testicle.
Site‐Specific Modification of Native IgGs with Flexible Drug‐Load
Authors: Wehrmüller Jöri E. , Frei Julia C. , Hechler Torsten , Kulke Michael , Pahl Andreas , Béhé Martin , Schibli Roger , Spycher Philipp R. 
Published: September 2024

AbstractHomogeneous, site‐specifically conjugated antibodies have shown to result in antibody‐drug conjugates (ADCs) with improved efficacy and tolerability compared to stochastically conjugated ADCs. However, precisely controlling the drug load as well as attaching multiple payload moieties to the antibody remains challenging. Here, we demonstrate the simple and direct modification of native IgG‐antibodies at the residue glutamine 295 (Q295) without the need for any protein engineering with flexible drug‐to‐antibody ratios of one or multiple payloads. The conjugation is enabled through short, positively charged lysine containing peptides and native, commercially available microbial transglutaminase. In proof‐of‐concept studies, HER2‐targeting ADCs based on trastuzumab were generated with drug‐to‐antibody ratios (DARs) of 2 and 4 of the same or different payloads using orthogonal conjugation chemistries. Quantitative biodistribution studies performed with 111In‐radiolabeled conjugates showed high tumour uptake and low accumulation of radioactivity in non‐targeted tissues. A single dose study of trastuzumab conjugated to the highly potent payload α‐Amanitin demonstrated complete and long‐lasting tumour remission and was well‐tolerated at all dose levels tested.
Genetically Expressed RNA Strand Displacement for Cellular Manipulation
Authors: Wu Chao‐Qun , Feng Hui‐Ye , Liu Yan , Xu Liang 
Published: September 2024

AbstractNucleic acid strand displacement is a pivotal concept in dynamic nucleic acid nanotechnologies, which has been extensively investigated and applied across various fields. Compared with DNA systems, the genetically expressed RNA strand displacement technology offers unique advantages for construction of genetic circuits in living cells, where RNA expression and modulation may be seamlessly integrated into the genomic network for long‐term and stable regulations of diversified biological functionalities. This Concept paper provides an overview of previous efforts on developments of synthetic gene circuits through utilization of RNA strand displacement, including our endeavors in this field. Moreover, future prospects, potential applications and challenges of the genetically expressed RNA strand displacement technology are also discussed.
Constructing Highly Efficient Catalysts for the 1‐Butene Epoxidation
Authors: Dong Yaqi , Yuan Juncong , He Sheng , Ma Zhe , Chen De , Yang Chaohe , Feng Xiang 
Published: September 2024

AbstractEpoxides are high‐valued intermediates in the production of chemicals, pharmaceuticals, perfumes, and polymers. Given the growing demand for epoxides, it is imperative to develop more environmental friendly and sustainable routes instead of the chlorohydrin process. Notably, the direct utilization of hydrogen peroxide (H2O2) for the epoxidation reaction presents significant advantages from both environmental and economic perspectives. The review provides insights into both homogeneous and heterogeneous catalysts employed in the 1‐butene epoxidation using the green oxidant H2O2. Among the diverse range of catalysts, titanosilicate‐1 (TS‐1) has garnered extensive attention due to its exceptional selectivity and high oxygen atom utilization. The aim of this review is to illustrate various strategies for TS‐1 catalysts preparation that can lead to more versatile, higher‐performance, and greener epoxidation processes. Additionally, various potential approaches to enhance the catalyst performance of TS‐1 are highlighted, including (i) constructing specific coordination modes of Ti sites, (ii) regulating the microenvironment around Ti sites, and (iii) improving the accessibility of Ti sites. Furthermore, advances in molding TS‐1 catalysts are also introduced from the perspective of the industrialization. Finally, future research directions are discussed with emphasis on the application scope of TS‐1 to gain deeper insights into epoxidation process.
Synthesis, Structure, and Optical Property of [6]Cyclo‐1,2‐naphthylene
Authors: Hara Masaki , Toriumi Naoyuki , Uchiyama Masanobu , Nozaki Kyoko 
Published: September 2024

AbstractA one‐pot procedure with cobalt‐mediated oxidation of 2,2’‐dilithio‐1,1’‐binaphthyl by ferrocenium salts afforded the chiral cyclic hexamer of naphthylene, [6]cyclo‐1,2‐naphthylene (1). The molecular structure of 1 was determined by single crystal X‐ray crystallography and NMR analyses, revealing its cyclic structure with an approximate D3 symmetry. Compound 1 exhibits blue emission at 383 nm with high photoluminescence quantum yield of 97 %, which can be attributed to its rigid twelve‐membered ring structure. Optical resolution of 1 by chiral HPLC allowed for the evaluation of its chiroptical properties. Each enantiomer exhibits circular dichroism with complex Cotton effects, which are grouped into three positive or three negative couplets. Circularly polarized luminescence is observed at 383 nm with an anisotropy factor |glum| on the order of 10−4. The high photoluminescence quantum yield and the CPL properties of 1 indicate its potential application as a CPL emitter.
Asymmetric Synthesis of Axially Chiral N, N‐1,2‐Pentatomic Heterobiaryl Diamines by an Organocatalytic Arylation Reaction
Authors: Zhao Shi‐Na , Li Qian , Qiao Xiu‐Xiu , He Yonghui , Li Ganpeng , Zhao Xiao‐Jing 
Published: September 2024

AbstractThe utilization of axially chiral biaryl diamines has been widely acknowledged as highly advantageous structures for the advancement of chiral catalysts and ligands. This highlights their extensive range of applications in asymmetric catalysis and synthesis. Herein, we devised a direct arylation reactions of 5‐aminopyrazoles with azonaphthalenes, utilizing chiral phosphoric acid as the catalyst. This method delivers structurally novel atroposelective N, N‐1,2‐azole heteroaryl diamines with high yields (up to >98 %) and good to excellent enantiomeric ratios while exhibiting a wide range of substrate compatibility.
Photo‐Induced Three‐Component Reaction for the Construction Of α‐Tertiary Amino Acid Derivatives
Authors: He Yuhang , Zhao Qianyi , Yuan Wei , Gong Lei 
Published: September 2024

AbstractThe synthesis of α‐tertiary amino acids (ATAAs), which are pivotal components in natural metabolism and pharmaceutical innovation, continues to attract significant research interest. Despite substantial advancements, the pursuit of a facile, versatile, and resource‐efficient methodology remains an area of active development. In this work, we introduce a visible light‐triggered three‐component reaction involving readily available nitrosoarenes, N‐acyl pyrazoles, and allyl or (bromomethyl)benzenes under mild conditions. This approach enables the straightforward assembly of a wide array of ATAA derivatives (42 examples) in commendably high yields (up to 89 %). Mechanistic investigations elucidate that the reaction proceeds through a dehydration condensation between nitrosoarenes and N‐acyl pyrazoles to generate ketimine intermediates. This is followed by a light‐driven halogen atom transfer (XAT) process and a radical addition, culminating in the formation of the desired products. The approach showcases excellent functional group compatibility and late‐stage derivatization potential, offering new insights and avenues for the synthesis of ATAA analogs.
Migration of para‐Nitrophenyl Groups in Methyl Pyranosides: Configuration and Conformation Determine the Kinetics
Authors: Friedrich Leon M. , Lütjohann Clemens , Hartke Bernd , Lindhorst Thisbe K. 
Published: September 2024

Abstractpara‐Nitrophenyl (PNP) ethers of glycosides are important building blocks en route to functional carbohydrates. They are stable in neutral media, however, under basic conditions such as during the Zemplén deacylation of sugars, aryl migration is frequently observed. We have employed a library of O‐PNP‐substituted methyl glycosides of the manno‐, galacto‐, gluco‐ and altro‐series to study the kinetics of aryl migration in MeOH/sodium methoxide using NMR spectroscopy revealing that migration between cis‐oriented OH groups is faster than between trans‐oriented ones. The rate constants of migration decrease in the order of Alt>Man>Gal>Glc and are related to the energy barriers of chair conformation inversion. The energy profile of the 3 to 4‐PNP migration in methyl mannoside was calculated using DFT methods suggesting the Meisenheimer complex is an intermediate of PNP migration and that coordination of the sodium cation has a major impact on the energy profile.
First‐Principles Molecular Dynamics Study on Reductive Stability of High Concentration Electrolyte on Zn Doped Cu Current Collector Surface
Authors: Nachimuthu Santhanamoorthi , Wang Yuan‐Yu , Pan Shih‐Huang , Jiang Jyh‐Chiang 
Published: September 2024

AbstractIn enhancing the lifespan of anode‐free Li metal batteries (AFLMBs), current collector (CC) engineering is crucial for achieving uniform and dendrite‐free lithium deposition. The commonly used copper (Cu) CC is unsatisfactory because of its poor lithiophilicity. Here, we consider Zn doping on the Cu CC surface (Zn−Cu) and explore the reductive stability of a high‐concentration electrolyte (HCE), consisting of 3.6 M Lithium Hexafluorophosphate (LiPF6) salt in a mixture of ethylene carbonate (EC) and diethylcarbonate (DEC), on the Zn−Cu (111) surface (HCE|Zn−Cu) using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. The interfacial reactions in the HCE|Zn−Cu system are compared to those on the pristine Cu (111) surface (HCE|Cu). We have also studied the effect of electron‐rich environments on the decomposition mechanism of the HCE mixture on both the CC surfaces. It is found that the HCE mixture is electrochemically stable on both Cu and Zn−Cu surfaces in a neutral environment. However, under electron‐rich conditions, only one DEC molecule has decomposed upon contact with the Cu CC surface, while the two PF6− anion groups from Li salts have decomposed much faster (within 100 fs) when the HCE mixture interacts with the Zn−Cu surface. Our results indicate that Zn doping suppresses undesirable solvent decomposition and improves the quality of the solid electrolyte interphase (SEI) layer.
Multiscale spatial‐temporal transformer with consistency representation learning for multivariate time series classification
Authors: Wu Wei , Qiu Feiyue , Wang Liping , Liu Yanxiu 
Published: September 2024

SummaryMultivariate time series classification holds significant importance in fields such as healthcare, energy management, and industrial manufacturing. Existing research focuses on capturing temporal changes or calculating time similarities to accomplish classification tasks. However, as the state of the system changes, capturing spatial‐temporal consistency within multivariate time series is key to the ability of the model to classify accurately. This paper proposes the MSTformer model, specifically designed for multivariate time series classification tasks. Based on the Transformer architecture, this model uniquely focuses on multiscale information across both time and feature dimensions. The encoder, through a designed learnable multiscale attention mechanism, divides data into sequences of varying temporal scales to learn multiscale temporal features. The decoder, which receives the spatial view of the data, utilizes a dynamic scale attention mechanism to learn spatial‐temporal consistency in a one‐dimensional space. In addition, this paper proposes an adaptive aggregation mechanism to synchronize and combine the outputs of the encoder and decoder. It also introduces a multiscale 2D separable convolution designed to learn spatial‐temporal consistency in two‐dimensional space, enhancing the ability of the model to learn spatial‐temporal consistency representation. Extensive experiments were conducted on 30 datasets, where the MSTformer outperformed other models with an average accuracy rate of 85.6%. Ablation studies further demonstrate the reliability and stability of MSTformer.
Synthesis and Spectroscopic Properties of Diarylethene‐Subporphyrinoid Hybrids
Authors: Muto Taichi , Tamiya Nanari , Takagi Akuto , Mizutani Tadashi , Bourissou Didier , Rapenne Gwénaël , Yamada Mihoko , Kawai Tsuyoshi 
Published: September 2024

AbstractTwo novel diarylethene‐fused subporphyrinoids were prepared and characterized. A mono diarylethene derivative was obtained via a statistical condensation reaction with 2 eq. of 1,2‐dicyanobenzene and 1 eq. of thiophene‐disubstituted butenedinitrile. The symmetric triply diarylethene‐fused subporphyrazine was synthesized via a cyclotrimerization reaction of the thiophene‐disubstituted butenedinitrile derivative. These compounds were characterized by NMR spectroscopy and high‐resolution mass spectrometry. The spectroscopic properties have been measured in hexane and in chloroform. The mono diarylethene‐fused‐type compound showed photochromism at 580 nm and >700 nm wavelength, accompanied by degradation. According to DFT calculations, photoreactivity likely depends on the contribution of aromatic feature of pyrrole ring bonded to two thiophene rings.
How Flexible Is the Hydrogen Sulfide Molecule Structure? Influence of Hydrogen Sulfide Molecule Geometry on Its Hydrogen Bonds.
Authors: Milovavnović Milan R. , Zarić Snežana D. 
Published: September 2024

AbstractThe geometry of hydrogen sulfide was studied by calculating potential energy surface (PES) with over 1800 configurations. The calculations were performed at very accurate CCSD(T)/aug‐cc‐pvz5 level. The most stable geometry on the PES has bond angle (H−S−H) of 92.40° and bond length (S−H) of 1.338 Å. The PES shows that hydrogen sulfide is a quite flexible molecule. Namely, it can change the bonding angle (H−S−H) in the range of 15.6° (from 84.6° to 100.2°) and the bond lengths (S−H) in the range of 0.082 Å (from 1.299 Å to 1.381 Å) with an energy increase of only 1.0 kcal/mol. An influence of hydrogen sulfide geometry on its hydrogen bonds was studied on several hydrogen sulfide/hydrogen sulfide and water/hydrogen sulfide dimers. It showed that the change of hydrogen sulfide geometry does not influence the strength of hydrogen bond. Fully optimized geometries in gas and water solution phases revealed structural differences of both monomers and dimers in gas phase and water phase. SAPT analysis of the optimized dimer geometries showed that in all the dimers electrostatic is the most dominant contribution, while, in the dimers with hydrogen sulfide, the influence of dispersion contribution becomes quite pronounced.
Pillar[5]arene‐based Polymer Network for Efficiently Removing Perfluorooctanoic Acid through Synergistic Binding Interactions
Authors: Zhang Qian , Yue Tian‐Jiao , Sun Si‐Yuan , Jiang Shi‐Jie , Feng Jing‐Lan , Guo Hai‐Ming 
Published: September 2024

AbstractPerfluorooctanoic acid (PFOA) is currently one of the most important chemicals posing environmental risks, and there is an urgent need to find methods to efficiently remove PFOA from environmental media. Here, two decaamino‐pillar[5]arene‐based fluorine‐rich polymer networks, called FA2P‐P and FA6P‐P, were constructed using a convenient method. FA6P‐P had an excellent ability to take up PFOA, and had a capacity of 1423 (mg PFOA) (g FA6P‐P)−1, which is the second highest adsorption capacity reported for any PFOA sorbent. FA6P‐P removed >99 % of the PFOA from a solution and decreased the PFOA concentration from 1000 μg L−1 in 5 min at an exceedingly low adsorbent loading of 0.7 mg L−1, giving a final PFOA concentration <4 ng L−1, which is lower than the most recent enforceable maximum concentration set by the United States Environmental Protection Agency. A high rate constant (kobs) of 55.8 g mg−1 h−1 was observed. Pillar[5]arene gives the material hydrophobic properties and also amino sites and hydrophobic chains, which are synergistic PFOA binding sites. The polymer was very stable and readily regenerated. The results indicated that pillar[5]arene‐based porous organic polymer sorbents are excellent candidates for capturing PFOA.
Self‐Assembly Synthesis of Oxygen and Sulfur Co‐Doped Porous Graphitic Carbon Nitride Nanosheets for Boosting CO2 Photoreduction
Authors: Cao Shihai , Yang Haocheng , Zeng Fan , Lu Yao , Chen Huan , Jiang Fang 
Published: September 2024

AbstractGraphitic carbon nitride (CN) has garnered considerable attention in the field of visible‐light CO2 photoreduction, but its efficiency remains limited by the intrinsic π‐conjugated skeleton. Here, O and S were co‐doped CN (O, S/CN) by a facile “hydrolysis + calcination” approach to modulate the physicochemical and electronic structure. Distinctive from S doped CN (SCN), O, S/CN owned porous layer structure with several nanosheets and less SO42− groups on the surface. The amount of heteroatom‐doping was achieved by changing the hydrothermal temperature. The optimum O, S/CN‐80 achieved moderate CO production rate of 1.29 μmol g−1 h−1, which was 3.79 times as much as SCN (0.34 μmol g−1 h−1). The O and most S atoms were substitutionally doped and the effect of S doped state on the improved efficiency of CO generation in O, S/CN was also explored based on the theoretical calculations. This work provides an inspiration to develop efficient dual‐doped CN photocatalysts for photocatalytic CO2 reduction.
Facile Depolymerization of Thermally Stable Polyetherethersulfone and Polyetheretherketone Using Hydroquinone and Bases
Authors: Minami Yasunori , Honobe Rena , Tsuyuki Shunsuke , Sato Kazuhiko , Yoshida Masaru 
Published: September 2024

AbstractSuper engineering plastics such as polyetheretherketone (PEEK) and polyetherethersulfone (PEES) exhibit thermal stability, chemical resistance, and mechanical strength. Such characteristics are attributed to their robust chemical structures composed of stable aryl ethers. These features make chemical recycling difficult. This is because it is necessary to overcome through the stability of the material and then precisely cleave the stable bonds. This study demonstrates the depolymerization of PEES and PEEK by hydroquinone in the presence of sodium hydroxide in 1,3‐dimethyl‐2‐imidazolidinone (DMI) solvent at 150 °C. This method effectively provides monomeric products, diphenylsulfone and benzophenone having two 4‐hydroxyphenoxy groups at both para positions. DMI solvent was the crucial factor for this transformation, since it enhanced the reactivity of hydroquinone to cleave the aryl ether bonds.