bluuebunny/crossref_metadata_2025_split huggingface dataset:
Advances in Asymmetric Hydrogenation of Unfunctionalized Enol Ethers
Authors: Zhang Jian , Song Yuxi , Zhang Zhenfeng , Zhang Wanbin 
Published: November 2024

AbstractAsymmetric hydrogenation of enol ethers has emerged as a valuable and environmentally friendly method for the preparation of optically active cyclic and acyclic ethers, some of which have demonstrated substantial potential for application in the synthesis of valuable compounds and total synthesis of natural products. Over the past few decades, significant attention has been devoted to the use of transition‐metal catalysts, particularly those containing chiral phosphine‐phosphine, phosphine‐amine, or carbene ligands, in the hydrogenation of unfunctionalized enol ethers. In parallel, frustrated Lewis pair catalysts have also been successfully applied in this transformation, enabling the efficient production of various chiral ethers. This review highlights the momentum and most notable advances in enantioselective hydrogenation of unfunctionalized enol ethers (with only alkyl and aryl substituents on the vinyl group). Owing to ubiquitous industrial interest, the utility in the synthesis of chiral ethers and related derivatives is included.
Cationic Ring‐Opening Polymerization‐Induced Self‐Assembly (CROPISA) of 2‐Oxazolines: From Block Copolymers to One‐Step Gradient Copolymer Nanoparticles
Authors: Lusiani Niccolò , Pavlova Ewa , Hoogenboom Richard , Sedlacek Ondrej 
Published: November 2024

AbstractIn recent years, polymerization‐induced self‐assembly (PISA) has emerged as a powerful method for the straightforward synthesis of polymer nanoparticles at high concentration. In this study, we describe for the first time the synthesis of poly(2‐oxazoline) nanoparticles by dispersion cationic ring‐opening polymerization‐induced self‐assembly (CROPISA) in n‐dodecane. Specifically, a n‐dodecane‐soluble aliphatic poly(2‐(3‐ethylheptyl)‐2‐oxazoline) (PEHOx) block was chain‐extended with poly(2‐phenyl‐2‐oxazoline) (PPhOx). While the PhOx monomer is soluble in n‐dodecane, its polymerization leads to n‐dodecane‐insoluble PPhOx, which leads to in situ self‐assembly of the formed PEHOx‐b‐PPhOx copolymers. The polymerization kinetics and micellization upon second block formation were studied, and diverse nanoparticle dispersions were prepared, featuring varying block lengths and polymer concentrations, leading to dispersions with distinctive morphologies and physical properties. Finally, we developed a single‐step protocol for the synthesis of polymer nanoparticles directly from monomers via gradient copolymerization CROPISA, which exploits the significantly greater reactivity of EHOx compared to that of PhOx during the statistical copolymerization of both monomers. Notably, this approach provides access to formulations with monomer compositions otherwise unattainable through the block copolymerization method. Given the synthetic versatility and application potential of poly(2‐oxazolines), the developed CROPISA method can pave the way for advanced nanomaterials with favorable properties as demonstrated by using the obtained nanoparticles for stabilization of Pickering emulsions.
Restraining Planar Gliding in Single‐Crystalline LiNi0.9Co0.05Mn0.05O2 Cathodes by Combining Bulk and Surface Modification Strategies
Authors: Tan Zhouliang , Chen Xiaoxuan , Lin Jing , Huang Yudai , Cheng Wenhua , Liu Qingcui , Zhang Han , Ren Fucheng , Huang Yingde , Liu Zhenjie , Brezesinski Torsten , Yang Yong , Zhao Wengao 
Published: November 2024

AbstractThe delamination cracking from planar gliding along the (003) facets and anisotropic lattice strain perpendicular to the (003) facets inevitable lead to degradation of Ni‐rich single‐crystal cathode materials, adversely affecting their cyclability. Herein, we rationally design a single‐crystal LiNi0.9Co0.05Mn0.05O2 (SC90) cathode with robust chemo‐mechanical properties, in which coherently grown MgO6 octahedra and BO4 tetrahedra are incorporated into the lattice, and a stabilizing Mg3(BO3)2 layer is concurrently formed on the particle surface. Multiscale in/ex situ characterizations and theoretical calculations indicate that introducing the MgO6 and BO4 units leads to a “pinning effect” within the layered structure. This in turn strongly mitigates mechanical degradation by reducing planar gliding and delamination cracking over extended cycling. Moreover, the Mg3(BO3)2 coating maintains fast lithium diffusion by suppressing parasitic reactions at the cathode|electrolyte interface. The tailored SC90 cathode exhibits a capacity retention of ~88 % after 300 cycles at 5 C rate, significantly outperforming the pristine counterpart (~60 %). Additionally, a pouch‐type full cell with a graphite anode sustains a specific discharge capacity of 177 mAh g−1 after 500 cycles, with 90 % capacity retention. This work highlights the “pining effect” in preventing unfavorable slab sliding and structural deterioration, offering new insights for designing advanced ultrahigh Ni single‐crystal cathodes.
Benzothiadiazole‐Fused Cyanoindone: A Superior Building Block for Designing Ultra‐Narrow Bandgap Electron Acceptor with Long‐Range Ordered Stacking
Authors: Zhang Nuo , Chen Tianyi , Li Yaokai , Li Shuixing , Yu Jinyang , Liu Heng , Wang Mengting , Ye Xiu‐Kun , Ding Xueyan , Lu Xinhui , Li Chang‐Zhi , Zhu Haiming , Shi Minmin , Chen Hongzheng 
Published: November 2024

AbstractThere are great demands of developing ultra‐narrow bandgap electron acceptors for multifunctional electronic devices, particularly semi‐transparent organic photovoltaics (OPVs) for building‐integrated applications. However, current ultra‐narrow bandgap materials applied in OPVs, primarily based on electron‐rich cores, exhibit defects of high‐lying energy levels and inferior performance. We herein proposed a novel strategy by designing the benzothiazole‐fused cyanoindone (BTC) unit with ultra‐strong electron‐withdrawing ability as the terminal to synthesize the acceptor BTC‐2. The BTC unit imparts red‐shifted absorption up to 1000 nm to BTC‐2, attributed to enhanced intramolecular charge transfer and the quinoid resonance effect. Additionally, BTC‐2 features deep‐lying energy levels with the highest occupied molecular orbital level of −5.81 eV, due to the ultra‐strong electron‐withdrawing ability of BTC. Furthermore, BTC‐2 exhibits long‐range ordering in both molecular packing and macroscopic blend morphology, resulting from shoulder‐to‐shoulder packing of two BTC units, leading to an ultra‐long exciton lifetime over 1.1 ns. These superiorities facilitated a 17.17 % efficiency in the binary OPV device with an extremely high photocurrent of 30.34 mA cm−2, representing the best performance for ultra‐narrow bandgap electron acceptors, and a record light utilization efficiency of 4.88 % in binary semi‐transparent systems. Overall, BTC is a superior building block for designing ultra‐narrow bandgap electron acceptors.
Property Prediction of Bio‐Derived Block Copolymer Thermoplastic Elastomers Using Graph Kernel Methods
Authors: Petersen Shannon R. , Kohan Marzagão David , Gregory Georgina L. , Huang Yichen , Clifton David A. , Williams Charlotte K. , Siviour Clive R. 
Published: November 2024

AbstractIncreasing the diversity of bio‐based polymers is needed to address the combined problems of plastic pollution and greenhouse gas emissions. The magnitude of the problems necessitates rapid discovery of new materials; however, identification of appropriate chemistries maybe slow using current iterative methods. Machine learning (ML) methods could significantly expedite new material discovery and property identification. Here, PolyAGM, a ML algorithm using graph kernel methods, is introduced and used to predict the properties of block copolymers and identify the responsible structural ‘motifs’. It applies a “fingerprinting” method to convert Graph representations of polymers into numerical vectors. The Graphs explicitly encode the entire copolymer of atoms and bonds such that the sequencing of chemical features and polymer chain length are included, alongside relevant stereochemical information. PolyAGM gives predictions for both thermal and mechanical properties that are in good agreement with experimental measurements. This work focuses on predicting the properties of bio‐derived ABA‐block polymer thermoplastic elastomers, but the general fingerprinting technique of PolyAGM should be relevant to other application fields.
Phenyl Propyl Polysiloxane‐Modified Epoxy Resin III: The Reaction Condition, Phase Structures, and Macroproperties
Authors: Ji Yundong , Feng Jitao , Wang Changzeng , Li Shuxin , Cao Dongfeng , Huang Duanping 
Published: November 2024

ABSTRACTPolysiloxanes are known to significantly enhance the toughness and thermal stability of epoxy resins. However, unsatisfactory grafting or copolymerization often occurs due to compatibility issues between the two materials, resulting in noticeable phase separation and a significant reduction in strength. In this paper, the copolymerization extent of epoxy resin with polysiloxanes was enhanced through solution polymerization by refining the synthesis process. The investigation explored the impact of polymerization process parameters on the reaction extent, phase structure, and mechanical properties. The results of refractive index and epoxy value showed that the extent of copolymerization ceased to increase after a 3‐h reaction duration at 15°C, 25°C, and 40°C. The results of FTIR and NMR showed that the lower the reaction temperature, the higher the extent of copolymerization. The toughness and strength of the resins copolymerized at 15°C increased simultaneously, while the strength of the resins copolymerized at 40°C decreased. The SEM results showed that the higher the extent of copolymerization, the finer the size of the second phase of the resins and that controlling the size of the second phase to an average of about 600 nm is the key to the strengthening of the resins. It is found that a low temperature is more favorable for the occurrence of a copolymerization reaction between polysiloxanes and epoxy resin, and it is pointed out that the relationship between the extent of reaction, phase structure, and macroscopic properties is an important guide for the work on siloxane‐modified epoxy resins.
Quinoline Endoperoxides for Mitochondria Targeted Singlet Oxygen Delivery
Authors: Si Yu , Wang Lei , Wu Hao , Yan Shoucai , Wang Yang , Qian Xiao , Liu Ziang , Akkaya Engin U. 
Published: November 2024

AbstractControlled release of singlet oxygen from chemical sources is becoming an interesting path for eliciting apoptotic death of cancer cells. In this work, we present the synthesis and characterization of hitherto unknown class of aromatic endoperoxides, namely quinoline endoperoxides. Quinolines, especially after quaternization, show significant targeting of mitochondria. This leads to more effective cytotoxicity in cancer cell cultures suggesting a potential utility in cancer therapy.
Construction of Alkaloid‐Type Bis Carbazoles via Pd(II)‐Catalyzed C‐H Functionalization
Authors: Kaur Ramandeep , Babu Srinivasarao Arulananda 
Published: November 2024

AbstractWe report the construction of unsymmetrical dimeric carbazoles and π‐extended bis carbazoles (having an aryl ring spacer) via the C−H functionalization route. Generally, oxidative coupling and traditional cross‐coupling reactions have been used to construct bis‐ and π‐extended carbazoles. Natural bis carbazole alkaloids and synthetic dimeric carbazoles are important molecules in medicinal, materials chemistry research. There is scope for developing new synthetic transformations leading to structurally appealing bis carbazoles. The synthesis of symmetrical bis carbazoles via cross‐coupling and C−H functionalization is well known in the literature and it is noted that there exist limited reports on the construction of unsymmetrical bis carbazoles via the C−H functionalization route. Accordingly, this paper reveals the Pd(II)‐catalyzed bidentate directing group‐assisted C−H functionalization as a progressive route for the synthesis of a library of unsymmetrical dimeric carbazoles and π‐extended bis carbazoles (connected through an aryl ring spacer).
Analysis of mitochondrial DNA replisome in autism spectrum disorder: Exploring the role of replisome genes
Authors: Rojas Valentina , Carrasco‐Gallardo Carlos , Tenorio Lidia , Olesen Margrethe A. , Tapia Victor , Carrasco Manuel , Araos Patricio , Quintanilla Rodrigo A. , Ruiz Lina M. 
Published: November 2024

AbstractAutism spectrum disorder (ASD) is a neurodevelopmental condition often associated with mitochondrial dysfunction, including increased mitochondrial DNA (mtDNA) copy number and impaired energy production. This study investigates the role of the mitochondrial replisome—specifically, the genes TFAM, TWNK, POLG, and TOP1MT—in mtDNA replication and its potential contribution to ASD pathophysiology. We analyzed samples from the oral mucosa of children with ASD and typically developing (TD) controls, assessing mtDNA copy number, gene expression, and protein levels. Our findings revealed a significant increase in mtDNA copy number in the oral mucosa of ASD children, along with partially deleted mtDNA molecules. However, there were no significant changes in the expression of TFAM, TWNK, POLG, or MT‐TL1 genes between ASD and TD samples. Additionally, TFAM protein levels, including monomeric, dimeric, and trimeric forms, did not differ significantly. We also observed increased oxidative stress and inflammatory markers in the oral mucosa of ASD children, suggesting that mitochondrial alterations may be linked to inflammation and oxidative damage in ASD. To further investigate the functional impact of TFAM, we overexpressed it in human HEK293 cells and cortical neurons (CN1.4). TFAM overexpression led to increased mtDNA copy number, cell proliferation, and ATP production in HEK293 cells, but did not significantly alter mitochondrial gene expression, protein oxidation, or mtDNA integrity. In CN1.4 neurons, TFAM overexpression increased mitochondrial membrane potential and length, indicating potential changes in mitochondrial dynamics. Overall, our study suggests that while mtDNA alterations are present in ASD, they are not directly driven by changes in mitochondrial replisome gene expression. These findings highlight the complexity of mitochondrial dysfunction in ASD and suggest the need for further investigation into the underlying molecular mechanisms.
Enhanced Oxygen Redox Kinetics and Stability in Li−O2 Batteries Using Trimetallic MnCo2‐xCuxO₄ Spinel Catalysts
Authors: Kannan Pavithra , Guddehalli Chandrappa Shivaraju , Kumar Gupta Raju , Prakash Annigere S. 
Published: November 2024

AbstractHigh energy density rechargeable Li−O2 batteries (LOBs) have garnered significant attention as a promising energy storage device. However, the sluggish oxygen redox kinetics impeded the efficiency and cycling performance during both the charge and discharge processes. To address this issue, we introduce a non‐noble‐trimetallic MnCo2‐xCuxO4 (X=0 to 1) spinel interface as a bifunctional catalyst, to improve the reaction kinetics and cycle stability of LOBs. The half‐filled eg orbital improves the synergistic interaction between Cu+/Cu2+, Co2+/Co3+, and Mn3+/Mn4+ redox pairs in the lattice, which enhances catalytic performance. In the series of MnCo2‐xCuxO4 (X=0 to 1) spinel catalyst MnCo1.75Cu0.25O4 (MCU25) emerged as a standout performer. This exhibited notable half‐cell performance, featuring superior ORR/OER bifunctional electrocatalytic activity with a ΔE of 1.15 V (vs RHE). Notably, the MCU25 cathode exhibited remarkable stability for over 1250 hours, enduring 225 cycles at 500 mA h g−1 and stable up to 70 cycles at a capacity limit of 1000 mA h g−1 in LOBs. Furthermore, it demonstrated an exceptional discharge‐specific capacity of 11272 mA h g−1 at a current density of 175 mA g−1, exceeding the performance achieved by state‐of‐the‐art RuO2 around 10180 mA h g−1.
Sustainable entrepreneurship support programs in nature‐protected areas: How universities third mission aids sustainability transitions
Authors: Buzzao Giacomo , Long Thomas B. , Argade Padmaja 
Published: November 2024

AbstractThis research examines the role of universities in supporting sustainability transitions in the context of nature‐protected areas through the leveraging of sustainable entrepreneurship. Universities are legitimate agents of change embedded within a territory and can play a pivotal role by initiating and supporting sustainable entrepreneurship ‐ a means of replacing unsustainable ventures with regenerative solutions linked to the success of sustainability transitions. However, the context of nature‐protected areas is unique on account of fragile ecosystems and cultural heritage sites – sustainable entrepreneurship can thus face a variety of challenges. This study focuses on a university‐led sustainable entrepreneurship program in North Sea nature‐protected areas, employing a multi‐level perspective framework for studying sustainability transitions. Through qualitative analysis of interviews, the study explores how such programs contribute to sustainability transitions by facilitating support to new sustainable entrepreneurs, creating coordination across actors and sustainability concerns, and creating a narrative for sustainability transition. The research contributes by spotlighting the role of universities in enhancing legitimacy and embeddedness in these areas, and in doing so, identifies new ‘third mission’ roles for universities. The research also provides one of the first attempts to synthesize ‘third mission’ concepts with sustainability transitions literature.
‘Therapy Through the Lens of Autism’: Qualitative exploration of autistic adults' therapy experiences
Authors: Pappagianopoulos Jessica , Brunt Sophie , Smith Jessica V. , Menezes Michelle , Howard Mya , Sadikova Eleonora , Burroughs Christina , Mazurek Micah O. 
Published: November 2024

AbstractBackgroundAutistic adults are at increased risk for mental health (MH) conditions. As such, there is a need for effective MH care services that meet the unique needs of autistic clients. However, a deeper understanding of the therapy experiences and preferences of autistic adults is necessary to inform future enhancements to clinical practice for this population.AimThis study aimed to qualitatively examine the perspectives of autistic adults regarding past MH therapy experiences through semi‐structured interviews.Method: Autistic adults (N = 19, ages 21–51 years) completed a demographics survey and participated in individual interviews to share experiences and recommendations.FindingsReflexive thematic analysis revealed three over‐arching themes and eight sub‐themes. Overall, findings highlight therapeutic approaches that are important to autistic adults. Specifically, participants emphasised the value of the following strategies: (1) cultivating a safe space informed by an understanding of autism; (2) demonstrating a flexible and collaborative approach to therapy that is responsive to clients' needs; and (3) considering clients' preferences regarding talking in session when supporting personal growth and skill development.LimitationsThe study was limited by a relatively non‐diverse sample in terms of racial and ethnic identity and potential recall bias due to the retrospective nature of the investigation.
Progress in the Functionalization of Purines and Purine Nucleosides by Minisci Reactions Over the Past 50 Years
Authors: Li Yangyan , Butt Madiha , Bao Wenhu , Xie Ruoqian , Chen Gang 
Published: November 2024

AbstractOver the past decade, significant progress has been witnessed in the functionalization of purines and purine nucleosides via Minisci reactions. This review primarily focuses on the latest advancements in applying Minisci reactions to purine bases, while also including some notable early examples, with an emphasis on the late‐stage functionalization of purine nucleosides. The Minisci reaction, a radical‐based method, enables direct C─H functionalization of purines, facilitating the incorporation of a wide range of functional groups under mild conditions. Key developments discussed in this review include the regioselective functionalizations at the C6, C8, and C2 positions, which have greatly expanded the toolkit for nucleoside modification. Additionally, this review also explores mechanistic insights, as well as the role of catalysts and reaction conditions that enhance the selectivity and efficiency of these transformations. The progress in Minisci‐type reactions offers valuable strategies for the synthesis of novel purine‐based compounds with promising applications in drug discovery and development.
Synthesis of Bis(diimino)palladium Nanosheets as Highly Active Electrocatalysts for Hydrogen Evolution
Authors: Maeda Hiroaki , Jia Han Phua Eunice , Sudo Yuta , Nagashima Sayoko , Chen Wentai , Fujino Mayumi , Takada Kenji , Fukui Naoya , Masunaga Hiroyasu , Sasaki Sono , Tsukagoshi Kazuhito , Nishihara Hiroshi 
Published: November 2024

AbstractDevelopment of efficient electrocatalysts for hydrogen evolution reactions (HERs) is necessary to achieve environmentally friendly and sustainable hydrogen production. To reduce cost and to circumvent the scarcity of platinum, the most efficient catalyst for HER, it is essential to develop catalysts using ubiquitous base metals or minimal amounts of precious metals. Bis(diimino)metal (MDI) coordination nanosheets are potential HER catalysts because their electric conductivities, two‐dimensionality, and porous structures provide large surface areas and efficient mass and electron transfer. In addition, with sparse metal arrangements in their chemical structures, nanosheets can reduce the amount of metal needed. We synthesized bis(diimino)palladium coordination nanosheets (PdDI) as a coordination polymer composed of bis(diimino)palladium, with semiconducting characteristics, using gas‐liquid interfacial synthesis and electrochemical oxidation. These electrochemically synthesized PdDIs exhibit remarkable catalytic performance with overpotential reaching 10 mA cm−2 of 34 mV, a Tafel slope of 47 mV dec−1, and an exchange current density of 2.1 mA cm−2 after appropriate activation. This performance is closely comparable to that of metallic platinum. An ex‐situ investigation of the activation process revealed that reduction of the divalent Pd center in bis(diimino)palladium produced a composite of Pd(0) species and PdDI, combining high catalytic activity with smooth electron transfer.