bluuebunny/crossref_metadata_2025 huggingface dataset:
Pongo's ecological diversity from dental macrowear analysis
Authors: Fiorenza Luca , Mitchell D. Rex , Kullmer Ottmar
Published: September 2024

Objectives

Orangutans are found in tropical rainforests of Borneo (Pongo pygmaeus) and Sumatra (Pongo abelii and Pongo tapanuliensis), and they are primarily considered frugivorous species. However, ecological studies reported differences in feeding behavior between these species. P. pygmaeus spend more time feeding on low‐quality foods, such as bark and tough vegetation than do P. abelii. The aim of this study is to investigate if there is any geographic variation in molar macrowear pattern between the two species.

Methods

We analyzed the macrowear pattern of second mandibular molars of 58 orangutan specimens combining dental topographic measurements (occlusal relief index, percentage of dentine exposure, and percentage of enamel wear) with the occlusal fingerprint analysis method.

Results

The molar macrowear patterns of P. abelii and P. pygmaeus show no significant differences in most of the variables examined in this study. While P. pygmaeus molars are generally characterized by flatter occlusal morphology with slightly larger crushing and grinding areas than those of P. abelii, these differences are not statistically significant. However, we do observe a more variable wear in P. pygmaeus.

Conclusions

Similarities in molar macrowear patterns between the two species could be linked to overlapping long‐term diets, primarily composed of ripe and pulpy fruits. Dental macrowear is a cumulative process that occurs during the individual's lifetime, and it may be difficult to detect seasonal changes through its examination. Future studies could integrate tooth micro‐ and macrowear data for a better understanding of primate dental ecology.
Beyond administrative burden: Activation and administrative harm
Authors: McGann Michael , Ball Sarah
Published: September 2024

Within recent public policy and administration scholarship, there has been a growing focus on the concept of “administrative burden” to describe the learning, compliance and psychological costs incurred by citizens when trying to access services and exercise social and political rights. Specifically, in the context of activation and welfare‐to‐work programmes, scholars have highlighted the effects of administrative burdens on claimants' autonomy, dignity and well‐being. We bring critical social policy scholarship on administrative harm into conversation with Adam and Balfour's concept of “administrative evil” to highlight the underlying dynamics of masking, moral inversion and dehumanisation that facilitate street‐level workers to adopt dispositions of enforcement of administrative burdens. To illustrate the applicability of Adam and Balfour's work to understanding how experiences of administrative burden can be intensified by the practices and dispositions of street‐level workers, we draw on examples of from an ethnographic study of the delivery of welfare‐to‐work in Australia.
Pentagon‐Rich Caged Carbon Catalyst for the Oxygen Reduction Reaction in Acidic Electrolytes
Authors: Chen Guoping , Isegawa Miho , Koide Taro , Yoshida Yasuo , Harano Koji , Hayashida Kenji , Fujita Shusaku , Takeyasu Kotaro , Ariga Katsuhiko , Nakamura Junji
Published: September 2024

The interaction between electron spin and oxygen molecules in non‐platinum catalysts, particularly carbon catalysts, significantly influences the catalytic performance of the oxygen reduction reaction (ORR). A promising approach to developing high‐performance catalysts involves introducing five‐membered ring structures with spin into graphitic carbons. In this study, we present the successful synthesis of cage‐like cubic carbon catalysts enriched with pentagon structures using pentagon ring‐containing C60 and a NaCl template. The number of pentagons contained in the structure was increased by doping with nitrogen and annealing, and the number of electron spins also increased, thereby improving catalytic activity. The prepared catalyst exhibits remarkable activity in ORR under acidic electrolytes. Furthermore, we elucidate the correlation between the pentagon structure, the number of spin, and catalytic activity, demonstrating that enhanced activity is contingent upon the presence of spin. Density functional theory (DFT) calculations support the role of spin in improving activity. The concept of spin and the introduction of pentagon structures provide new design principles for carbon catalysts.
As Aggregation‐Induced Emission Meets with Noncovalent Conformational Locks: Subtly Regulating NIR‐II Molecules for Multimodal Imaging‐Navigated Synergistic Therapies
Authors: Li Jiangao , Niu Niu , Wang Deliang , Zhu Jun , Li Xue , Kong Qiyu , Zhong Tang Ben , Wang Dong
Published: September 2024

Phototheranostics is growing into a sparking frontier in disease treatment. Developing single molecular species synchronously featured by powerful absorption capacity, superior second near‐infrared (NIR‐II) fluorescence and prominent photothermal conversion ability is highly desirable for phototheranostics, yet remains formidably challenging. In this work, we propose a molecular design philosophy that the integration of noncovalent conformational locks (NoCLs) with aggregation‐induced emission (AIE) in a single formulation is able to boost multiple photophysical properties for efficient phototheranostics. The introduction of NoCLs skeleton with conformation‐locking feature in the center of molecular architecture indeed elevates the structural planarity and rigidity, which simultaneously promotes the absorption capacity and bathochromic‐shifts the emission wavelength centered in NIR‐II region. Meanwhile, the AIE tendency mainly originated from flexibly propeller‐like geometry at the ends of molecular architecture eventually endows the molecule with satisfactory emission intensity and photothermal conversion in aggregates. Consequently, by utilizing the optimized molecule, unprecedented performance on NIR‐II fluorescence‐photoacoustic‐photothermal trimodal imaging‐guided photothermal‐chemo synergistic therapy is demonstrated by the precise tumor diagnosis and complete tumor ablation.
Disilicon‐Mediated Carbon Monoxide Activation: From a 1,2,3‐Trisila‐ to 1,3‐Disilacyclopentadienes with Hypercoordinate λ4Si‐λ3C Double Bonds
Authors: Yao Shenglai , Budde Markus Stefan , Yang Xing , Xiong Yun , Zhao Lili , Driess Matthias
Published: September 2024

The facile reaction of the SiPh2‐bridged bis‐silylene (LSi:)2SiPh2 (L=PhC(NBut)2) with diphenylacetylene affords the unprecedented 1,2,3‐trisilacyclopentadiene (LSi)2(PhC)2SiPh2 1 with a hypercoordinate λ4Si−λ3Si double bond. Compound 1 is very oxophilic and consumes three molar equivalents of inert N2O to form the bicyclic oxygenation product 2 through O‐atom insertion in the Si=Si and Si−Si bonds. Strikingly, 1 can completely split the C≡O bonds of carbon monoxide under ambient conditions (1 atm, room temperature), yielding the 1,3‐disilacyclopentadiene 3, representing the first hypercoordinate example of a cyclosilene with a λ4Si‐λ3C double bond. Likewise, reaction of Xyl‐NC (Xyl=2,6‐dimethylphenyl), an isocyanide isoelectronic with CO, with 1 furnishes the related 1,3‐disilacyclopentadiene 4 but with an amidinato silylene pendent attached to the Si=C carbon ring atom.
LiLnGeS4 (Ln=La−Nd): Designing High Performance Infrared Nonlinear Optical Sulfides through “Band Reformation of AGS”
Authors: Liu Qian‐Qian , Liu Xin , Li Mei‐Ze , Wang Rui‐Xi , Li Bingxuan , Wu Li‐Ming , Chen Ling
Published: September 2024

AgGaS2 (AGS) is the most commonly used commercial infrared nonlinear optical (IR NLO) material. However, AGS has a narrow band gap (Eg=2.58 eV) and a low laser‐induced damage threshold (LIDT), primarily attributed to its mobile liquid‐like Ag+ constituent and the unstable Ag−S chemical bond. Herein, we propose a “band reformation of AGS” strategy, which leads to the successful syntheses of four lanthanide sulfides, LiLnGeS4 (Ln=La−Nd), crystalizing in an asymmetric Ama2 structure. LiLaGeS4 demonstrates that eliminating the presence of Ag‐4d band increases the Eg to 3.32 eV and enhances the LIDT (14–29×AGS, measured by both powder and single crystal); while increasing the nonbonding density of states of the S‐3p band enhances the 2nd‐nonlinear optical coefficient (1.06×AGS). Besides, the bond length discrepancy between [LiS4], [GeS4] and [LaS8] units leads to a moderate birefringence (Δn=0.052). Such a unique structure further results in extremely small thermal expansion with αL=0.41–1.74×10−5 K−1, along different crystallographic axes. Our theoretical studies indicate that the synergy of the structure building units contribute to the second harmonic generation performance. These results suggest that the “band reformation of AGS” strategy provides effective guidance to discover new NLO crystals with optimized performance.
Solution‐processing induced H‐aggregate of Perylene‐Diimide Zwitterion Exhibiting Compact Molecular Stacking toward Efficient Cathode Modification in Organic Solar Cells
Authors: Li Zhe , Xiang Yanhe , Li Jiayu , Feng Luxin , Zhang Ming , Zhang Zhiguo , Yan Shouke , Xu Bowei
Published: September 2024

High‐performance organic cathode interlayers (CILs) play a crucial role in the advance of organic solar cells (OSCs). However, organic CILs have exhibited inferior performances to their inorganic counterparts over a long time, due to the inherent shortcoming of poor charge transporting capability. Here, we designed and synthesized a perylene‐diimide (PDI) zwitterion PDI‐B as high‐performance organic CIL for OSCs. We revealed that an obvious H‐aggregate of PDI‐B was formed during the solution processing, thereby significantly enhancing the charge transporting capability of the CIL. Compared to the classic PDINN, the π–π stacking distance of PDI‐B was reduced from 4.2 Å to 3.9 Å, which further facilitated the charge transport. Consequently, PDI‐B showed a high conductivity of 1.81×10−3S/m; this is comparable to that of inorganic CILs. The binary OSC showed an elevated PCE of 19.23 %, which is among the highest PCE values for binary OSCs. Benefitting from improved solvent resistance and good compatibility with large‐area processing method of PDI‐B, the photovoltaic performances of inverted and 1‐cm2 OSC were significantly improved. The results from this work provide a new approach of optimizing the condensed structure of PDI film to boost the charge conductivity, opening an avenue to develop high‐performance PDI‐based CILs.
Concise and Modular Chemoenzymatic Total Synthesis of Bisbenzylisoquinoline Alkaloids
Authors: Wang Jin , Zhao Jianxiong , Yu Zhenyang , Wang Siyuan , Guo Fusheng , Yang Jun , Gao Lei , Lei Xiaoguang
Published: September 2024

The bisbenzylisoquinoline alkaloids (bisBIAs) have attracted tremendous attention from the synthetic community due to their diverse and intriguing biological activities. Herein, we report the convergent and modular chemoenzymatic syntheses of eight bisBIAs bearing various substitutes and linkages in 5–7 steps. The gram‐scale synthesis of various well‐designed enantiopure benzylisoquinoline monomers was accomplished through an enzymatic stereoselective Pictet–Spengler reaction, followed by regioselective enzymatic methylation or chemical functionalization in a sequential one‐pot process. A modified intermolecular copper‐mediated Ullmann coupling enabled the concise and efficient total synthesis of five different linear bisBIAs with either head‐to‐tail or tail‐to‐tail linkage. A biomimetic oxidative phenol dimerization selectively formed the sterically hindered, electron‐rich diaryl ether bond, and subsequent intramolecular Suzuki–Miyaura domino reaction or Ullmann coupling facilitated the first enantioselective total synthesis of three macrocyclic bisBIAs, including ent‐isogranjine, tetrandrine and O‐methylrepandine. This study highlights the great potential of chemoenzymatic strategies in the total synthesis of diverse bisBIAs and paves the way to further explore the biological functions of these natural products.
Flavin‐Catalyzed, Photochemical Conversion of Dehydroalanine into 4,5‐Dihydroxynorvaline
Authors: Langschwager Tim , Storch Golo
Published: September 2024

The chemical synthesis of unnatural amino acids (UAA) is a key strategy for preparing designed peptides, including pharmaceutically active compounds. Alterations of existing amino acid residues such as dehydroalanine (Dha) are particularly important since selected positions can be addressed without the necessity of a complete de novo synthesis. The intriguing UAA 4,5‐dihydroxynorvaline (Dnv) is found in a variety of naturally occurring peptides and biologically active compounds. However, no method is currently available to modify an existing peptide with this residue. We report the use of flavin catalysts and visible light irradiation for this challenge, which serves as a versatile strategy for converting Dha into Dnv. Our study shows that excited flavins are competent hydrogen atom abstraction catalysts for ethers and acetals, which allows masked 1,2‐dihydroxyethylene functionalization from 2,2‐dimethyl‐1,3‐dioxolane. The masked diol was successfully coupled to Dha residues, and a series of Dnv‐containing products is reported. A mild and orthogonal protocol for deprotection of the acetal group was also identified, allowing free Dnv‐modified peptides to be obtained. This method provides a straightforward strategy for Dnv functionalization, which is envisioned to be crucial for accessing natural products and synthetic analogues with pharmaceutical activity.
Metal‐N Coordination in Lithium‐Sulfur Batteries: Inhibiting Catalyst Passivation
Authors: Ao Xin , Kong Yang , Zhao Shangquan , Chen Zhongxin , Li Yong , Liao Xingyu , Tian Bingbing
Published: September 2024

Lithium‐sulfur (Li−S) batteries exhibit great potential as the next‐generation energy storage techniques. Application of catalyst is widely adopted to accelerate the redox kinetics of polysulfide conversion reactions and improve battery performance. Although significant attention has been devoted to seeking new catalysts, the problem of catalyst passivation remains underexplored. Herein, we find that metal‐N coordination has a previously overlooked role in preventing the catalyst passivation. In the case of nickel, the Ni catalyst reacts with S8 to produce NiSx compounds on the surface, leading to catalyst passivation and slow the kinetics of LiPSs conversion. In contrast, when Ni is coordinated with N (typically Ni−N4), S8 remains stable on the surface. The Ni−N4 exhibits excellent resistance to passivation and rapid kinetics of LiPSs conversion. Consequently, the sulfur cathode with Ni−N4 exhibits a high rate capability of 604.11 mAh g−1 at 3 C and maintains a low capacity decay rate of 0.046 % per cycle over 1000 cycles at 2 C. Furthermore, preventing S passivation in M−N coordination applies not only to Ni−N4 but also to various coordination numbers and transition metals. This study reveals a new aspect of metal‐N coordination in inhibiting catalyst passivation, improving our understanding of catalysts in Li−S batteries.
Non‐Fused Star‐Shape Giant Trimer Electron Acceptors for Organic Solar Cells with Efficiency over 19 %
Authors: Zhou Wen , Liu Jiabin , Xie Jiaping , You Shiyong , Deng Jiawei , Yu Fan , Jeong Sang Young , Woo Han Young , Wu Feiyan , Chen Lie
Published: September 2024

Organic solar cells (OSCs) based on giant molecular acceptors (GMAs) have attracted extensive attention due to their excellent power conversion efficiency (PCE) and operation stability. However, the large conjugated plane of GMAs poses great challenges in regulating the solubility, over‐size aggregation and yield, which in turn further constrains their development in commercial products. Herein, we employ a non‐fused skeleton strategy to develop novel non‐fused star‐shape trimers (3BTT6F and 3BTT6Cl) for improving device performance. Single‐bond linkage can break the rigid planarity to form a 3D architecture, generating multidimensional charge transfer pathways. Importantly, the non‐fused skeleton strategy can not only significantly improve solubility and synthesis yield, but also effectively suppress molecular excessive aggregation. Consequently, due to the optimized film‐forming process and charge dynamics, 3BTT6F‐based binary device obtains a high PCE of 17.52 %, which is significantly higher than the reported fully fused trimers. Excitingly, 3BTT6F‐based ternary device even obtains a top‐level PCE of 19.26 %. Furthermore, the non‐fused star‐shape configuration also endows these acceptors with enhanced intermolecular interaction in the active layer, demonstrating excellent operational stability. Our work emphasizes the potential of non‐fused star‐shape trimers, providing a new pathway for achieving highly efficient and stable OSCs.
Exploring Cu(triNHC) as a Bifunctional Catalyst for Carbonate Synthesis From CO2 and Epoxy Amines/Sulfides/Ethers
Authors: Ha Changsu , Lee Jong Hyeok , Sokolova Ekaterina , Sung Kihyuk , Jang Hye‐Young
Published: September 2024

This study highlights the synergistic interplay between a Lewis acidic copper ion and a dissociated ligand from Cu(triNHC) complexes in the synthesis of cyclic carbonates from CO2 and epoxy compounds. The reactions were found to proceed efficiently under Cu(triNHC)‐catalyzed conditions, yielding significant quantities of cyclic carbonates across various epoxy substrates encompassing amine, sulfide, and ether functionalities. Stereochemical analyses underscore a pronounced propensity for retaining the stereochemistry of epoxy compounds in the resultant carbonates. This suggests a mechanism involving double inversion of stereochemistry during the reaction, which comprises catalyst‐mediated epoxide ring opening, subsequent CO2 addition, and carbonate ring closing. These findings align with established mechanisms for CO2 fixation reactions, shedding light on the intricate pathways underlying this catalytic process.
A new Co‐based cathode with high performance for intermediate‐temperature solid oxide fuel cells
Authors: Zhou Chaoran , Liang Zhixian , Qiu Hao , Jiang Shanshan , Wang Wei , Su Chao
Published: September 2024

Solid oxide fuel cells (SOFCs) as highly effective energy conversation devices have gained substantial recognition and research interest. The electrochemical properties of the traditional SOFCs are restricted by the sluggish reaction kinetics for the cathode material when lowering the operation temperature to below 600°C. In addition, the stability of the cathode at reduced temperatures is also a big challenge for the widely popularization of SOFC technology. Achieving high activities and stable ORR in the cathode is crucial for the development of SOFCs. The doping active metal method has been demonstrated as an effective approach to optimize the phase structure and improve the ORR activity of the cathode. Herein, we successfully develop an Ir‐doped SrCoO3 − δ (SrCo0.98Ir0.02O3 − δ, SCI) cathode for SOFCs. SCI exhibits a low area‐specific resistance (ASR) of 0.057 Ω cm2 at 650°C, ~ 44% lower than 0.102 Ω cm2 of Ir‐free SrCoO3 − δ. The Ni–Sm0.2Ce0.8O1.90 (SDC) anode‐supported fuel cell with SDC electrolyte and SCI cathode obtains an excellent output performance (e.g., 1,128 mW cm−2 at 650°C). The desired results underscore the feasibility of the Ir‐doping strategy as an optimized method for the exploitation of advancing cathode in SOFCs.
Plasma treatment and annealing conditions on mechanical and electrical properties of thermoplastic composites
Authors: Keerthiveettil Ramakrishnan Sumesh , Vackova Tatana , Jenikova Zdenka , Krum Stanislav , Spatenka Petr
Published: September 2024

In this research carbon fibers (CFs) with plasma polyethylene (PPE) was utilized for enhancing the properties. The 10 wt% CF with PPE (CF/PPE) exhibited favorable electrical conductivity (34 Ω cm), with better tensile strength (22.7 MPa), flexural strength (26.89 MPa) compared with the other CF combinations. In the positive temperature coefficient (PTC) test, after the initial trial, the CF/PPE combination exhibited a change in path at higher temperatures (125 and 128°C) due to temperature fluctuations, which altered the properties of composites. It is evident that the resistivity (R) ratio exhibits higher values (CF/PPE) for annealing samples (90°C for 5 h). The annealing process resulted in a PTC intensity of 2.53, which was higher than nonannealing (1.94). Scanning electron microscopy (SEM) analysis without annealing procedure revealed a greater number of deformations in the combination, which resulted in decrease in repeatability. The majority of combinations exhibited enthalpy of melting between 114.3 and 116.4 J/g. The annealed combination, which was heated to 128°C, exhibited an increase in enthalpy up to 122.4 J/g. The melting point of both the annealing and nonannealing samples increased from 131 to 134.1°C following the R–T test, while the crystallization temperature remained unaffected.
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

Rhodolith 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

The 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

Objectives

To 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.

Methods

This 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.

Results

The 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.

Conclusions

Elective 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

Homogeneous, 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

Nucleic 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

Epoxides 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

A 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

The 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

The 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

para‐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

In 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

Multivariate 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

Two 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

The 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

Perfluorooctanoic 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

Graphitic 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

Super 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.
Intelligent Solar Grid Integration: Advancements in Control Strategies and Power Quality Enhancement
Authors: Shambhu Choudhary Shiv , Nath Gupta Tripurari , Hussain Ikhlaq
Published: September 2024

This study delves into the advancements, challenges, and opportunities in the solar grid technology, emphasizing its integration into the existing power infrastructure. The proposed ML‐FOGI (multilayer fourth‐order generalized integrator) algorithm presents a promising solution for modern grid synchronization requirements, addressing challenges posed by the integration of renewable energy into the distributed generation. This technology enhances system robustness and dynamic response, particularly in weak distribution grids characterized by voltage distortions and imbalances. This innovative approach enhances system stability and performance, particularly in polluted grid conditions. Through MATLAB/Simulink modelling and experimental validation, the effectiveness of the proposed control strategy is investigated across diverse testing conditions. Emphasizing the significant role of the control strategy in enhancing power quality and grid stability in the solar photovoltaic systems, this research underscores the importance of robust and adaptive control mechanisms for optimizing performance and ensuring grid reliability in modern microgrid. This study delves into this complex issue of working of the grid connected photovoltaic (GCPV) system, emphasizing the importance of balanced unit templates and a stable DC link voltage with unpredictable grid harmonics. This research aims to enhance the resilience of solar PV systems against grid disturbances by drawing inspiration from the adaptable nature of ADALINE filters and adhering to the IEEE519 requirements. This study employs OPAL‐RT's resilient experimental configuration.
IFIT3 mediates TBK1 phosphorylation to promote activation of pDCs and exacerbate systemic sclerosis in mice
Authors: Huang Xiangyang , Liu Yi , Rong Xia , Zhao Yiheng , Feng Dan , Wang Jun , Xing Wanhong
Published: September 2024

Objective

To assess the impact of the IFIT3/TBK1 signalling pathway in activating plasmacytoid dendritic cells (pDCs) and its role in the development of SSc.

Methods

Utilized single‐cell RNA sequencing (scRNA‐seq) and high‐throughput transcriptome RNA sequencing to reveal the differential abundance of pDCs and the role of the key gene IFIT3 in SSc. Conducted in vitro cell experiments to evaluate the effect of IFIT3/TBK1 signalling pathway intervention on pDC activation cytokine release and fibroblast function. Constructed an IFIT3−/− mouse model using clustered regularly interspaced short palindromic repeats (CRISPR)/CRISPR‐associated protein 9 (Cas9) gene editing to assess the potential benefits of intervening in the IFIT3/TBK1 signalling pathway on skin and lung fibrosis in the SSc mouse model.

Results

The IFIT3/TBK1 signalling pathway plays a crucial role in activating pDCs, with IFIT3 acting as an upstream regulator of TBK1. Intervention in the IFIT3/TBK1 signalling pathway can inhibit pDC activation cytokine release and impact fibroblast function. The IFIT3−/− mouse model shows potential benefits of targeting the IFIT3/TBK1 signalling pathway in reducing skin and lung fibrosis in the SSc mouse model.

Conclusion

This study provides new insights into potential therapeutic targets for SSc, highlighting the critical role of the IFIT3/TBK1 signalling pathway in SSc development.

Highlights

This study elucidates the pivotal role of plasmacytoid dendritic cells (pDCs) in systemic sclerosis (SSc).

This study identified the key regulatory gene involved in systemic sclerosis (SSc) as IFIT3.

This study has found that IFIT3 functions as an upstream regulatory factor, activating TBK1.

This study provides Evidence of the regulatory effects of the IFIT3/TBK1 pathway on plasmacytoid dendritic cells (pDCs).

This study validated the therapeutic potential using the IFIT3−/− mouse model.