bluuebunny/crossref_metadata_2025_split huggingface dataset:
Alkoxythiophene‐Directed Fibrillization of Polymer Donor for Efficient Organic Solar Cells
Authors: Liu Chenhao , Fu Yiwei , Zhou Jinpeng , Wang Liang , Guo Chuanhang , Cheng Jingchao , Sun Wei , Chen Chen , Zhou Jing , Liu Dan , Li Wei , Wang Tao 
Published: November 2023

AbstractRealizing fibrillar molecular framework is highly encouraged in organic solar cells (OSCs) due to the merit of efficient charge carrier transport. This is however mainly achieved via the chemical structural design of photovoltaic semiconductors. In this work, through the utilization of three alkoxythiophene additives, T‐2OMe, T‐OEH, and T‐2OEH, the intermolecular interactions among a series of BDT‐type polymer donors, i.e., PM6, D18, PBDB‐T, and PTB7‐Th, are tuned to self‐assemble into nanofibrils during solution casting. X‐ray technique and molecular dynamics simulation reveal that the alkoxythiophene with (2‐ethylhexyl)oxy (─OEH) chains can attach on the 2‐ethylhexyl (EH) chains of these polymer donors and promote their self‐assembly into 1D nanofibrils, in their neat films as well as photovoltaic blends with L8‐BO. By adapting these fibrillar polymer donors to construct pseudo‐bulk heterojunction (P‐BHJ) OSCs via layer‐by‐layer deposition, generally improved device performance is seen, with power conversion efficiencies enhanced from 18.2% to 19.2% (certified 18.96%) and from 17.9% to 18.7% for the PM6/L8‐BO and D18/L8‐BO devices, respectively. This work provides a physical approach to promote the fibrillar charge transport channels for efficient photovoltaics.
Non‐Polaritonic Effects in Cavity‐Modified Photochemistry
Authors: Thomas Philip A. , Tan Wai Jue , Kravets Vasyl G. , Grigorenko Alexander N. , Barnes William L. 
Published: November 2023

AbstractStrong coupling of molecules to vacuum fields is widely reported to lead to modified chemical properties such as reaction rates. However, some recent attempts to reproduce infrared strong coupling results have not been successful, suggesting that factors other than strong coupling may sometimes be involved. In the first vacuum‐modified chemistry experiment, changes to a molecular photoisomerization process in the ultraviolet‐visible spectral range are attributed to strong coupling of the molecules to visible light. Here, this process is re‐examined, finding significant variations in photoisomerization rates consistent with the original work. However, there is no evidence that these changes need to be attributed to strong coupling. Instead, it is suggested that the photoisomerization rates involved are most strongly influenced by the absorption of ultraviolet radiation in the cavity. These results indicate that care must be taken to rule out non‐polaritonic effects before invoking strong coupling to explain any changes of properties arising in cavity‐based experiments.
The Synergetic Ionic and Electronic Features of MAPbI3 Perovskite Films Revealed by Electrochemical Impedance Spectroscopy
Authors: Jha Sauraj , Haroldson Ross , Zakhidov Anvar A. , Slinker Jason D. 
Published: November 2023

AbstractPerovskites have emerged as a forerunner of electronics research due to their vast potential for optoelectronic applications. The numerous combinations of constituent ions and the potential for doping of perovskites lead to a high demand to track the underlying electronic properties. Solution‐based electrochemistry is particularly promising for detailed and facile assessment of perovskites. Here, electrochemical impedance spectroscopy (EIS) of methylammonium lead iodide (MAPbI3) thin films is performed and model them with an equivalent circuit that accounts for solvent, ionic, and thin film effects. A dielectric constant consistent with prior AC studies and a diffusion constant harmonious with cation motion in MAPbI3 are extracted. An electrical double layer thickness in the perovskite film of 54 nm is obtained, consistent with lithium doping in perovskite films. Comparing the EIS and equivalent circuit model of perovskite films to control ITO‐only data enabled the assignment of the ions at each interface. This comparison implied a double layer of primarily lithium ions inside the perovskite film at the solution interface with significant recombination of ions on the solution side of the interface. This demonstrates EIS as a powerful tool for studying the fundamental charge accumulation and transport processes in perovskite thin films.
Spiro[Acridine‐Indoloacridine] Donor Based TADF Emitter with Near‐Unity PLQY and Horizontal Dipole Orientation toward High‐Efficiency OLEDs with Low Efficiency Roll‐Off
Authors: Wu Yaxun , Li Nengquan , Ni Fan , Ning Weimin , Ying Ao , Zhang He , Gao Xiang , Gong Shaolong , Yang Chuluo 
Published: November 2023

AbstractDesigning thermally activated delayed fluorescence (TADF) emitters with excellent photoluminescence quantum yield (PLQY), preferential horizontal emitting dipole orientation (𝛩//), and fascinating ability to rapidly utilize both singlet and triplet excitons for radiation is crucial for high‐performance organic light‐emitting diodes (OLEDs) with both high efficiency and relieved efficiency roll‐off. Integrating these advantages into a single TADF emitter is a formidable challenge. In this work, a spiro[acridine‐indoloacridine]‐based rigid donor, named AIA, is designed to establish a cooperatively long‐axis extended and conjugation expanded donor–acceptor type TADF emitter (AIA‐TRZ). The proof‐of‐the‐concept emitter simultaneously achieves an excellent PLQY of 99%, a near‐unity 𝛩// of 99%, and balanced excited state dynamic parameters. OLEDs based on AIA‐TRZ realize remarkable performance with an emission peak at around 480 nm, including doping concentration insensitivity, a maximum external quantum efficiency (EQEmax) of 37.3%, extremely low efficiency roll‐off, and over 20% EQE even at 14000 cd m−2.
Extremely Thin Perfect Absorber by Generalized Multipole Bianisotropic Effect
Authors: Ma Hao , Evlyukhin Andrey B. , Miroshnichenko Andrey E. , Zhu Fengjie , Duan Siyu , Wu Jingbo , Zhang Caihong , Chen Jian , Jin Biaobing , Padilla Willie J. , Fan Kebin 
Published: November 2023

AbstractSymmetry breaking plays a crucial role in understanding the fundamental physics underlying numerous physical phenomena, including the electromagnetic response in resonators, giving rise to intriguing effects such as directional light scattering, supercavity lasing, and topologically protected states. This work demonstrates that adding a small fraction of lossy metal (as low as 1 × 10−6 in volume) to a lossless dielectric resonator breaks inversion symmetry (IS), thereby lifting its degeneracy, leading to a strong bianisotropic response. In the case of the metasurface composed of such resonators, this effect leads to unidirectional perfect absorption while maintaining nearly perfect reflection from the opposite direction. It has developed more general Onsager‐Casimir relations for the polarizabilities of particle arrays, taking into account the contributions of quadrupoles, which shows that bianisotropy is not solely due to dipoles, but also involves high‐order multipoles. The experimental validation demonstrates an extremely thin terahertz‐perfect absorber with a wavelength‐to‐thickness ratio of up to 25,000, where the material thickness is only 2% of the theoretical minimum thickness dictated by the fundamental limit. The findings can pave a new route to design devices for applications involving optical‐to‐heat conversion processes.
Metal‐Free Electrochemical [3+2] Cycloaddition between α‐Amino Carbonyls and Tosylmethyl Isocyanide en route to Substituted Imidazoles
Authors: Mallick Samrat , Baidya Mrinmay , De Sarkar Suman 
Published: November 2023

AbstractThe established strategy unveils a metal and mediator‐free electrochemical [3+2] cycloaddition approach among α‐amino carbonyls and tosylmethyl isocyanide (TosMIC) fabricating substituted imidazole scaffolds. Implementation of electro‐redox conditions on this cycloaddition approach eliminates the essential requirement of transition metal catalysts and chemical oxidants. A wide variety of different functionalities are well tolerated under this reaction condition, contributing to the substrate scope and applicability. Several control experiments and cyclic voltammetry studies suggest an electro‐oxidation triggered successive C−C and C−N bond formations followed by rapid aromatization for constructing the five‐membered core structure.
Recent Advances in Synthetic Methods for 2H‐Pyrroles
Authors: Choi Seoung‐Mi , Kim Ju Hyun 
Published: November 2023

AbstractThe compound, 2H‐pyrrole, is a key scaffold contained in natural products, bioactive compounds, pharmaceuticals, and organic functional materials. However, the development of efficient synthetic strategies for 2H‐pyrroles is challenging. This is because 2H‐pyrroles, owing to their nonaromatic nature, are easily converted into the thermodynamically more stable 1H‐pyrroles. Recently, efficient and straightforward synthetic strategies for 2H‐pyrroles have been developed, including the dearomatization of 1H‐pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H‐pyrroles. In this review, we summarize the progress in the research on 2H‐pyrrole synthesis since 2000 and briefly discuss the synthesis reaction mechanisms.
Recent Advances in the 3 d‐Transition‐Metal‐Catalyzed Synthesis of Isoquinolines and its Derivatives
Authors: Maikhuri Vipin K. , Rawat Manish , Rawat Diwan S. 
Published: November 2023

AbstractThe preservation of scarce rare earth metals, such as palladium, rhodium, iridium, and others, poses a significant challenge for humanity due to their limited availability. These rare earth metals might be replaced by earth‐abundant 3d‐transition metals such as cobalt, manganese, iron, nickel, copper, etc. Isoquinolines have acquired an important position in synthetic organic chemistry as well as medicinal chemistry. They manifest in a diverse range of natural and synthetic molecules, serving as pivotal synthons for the synthesis of numerous bioactive compounds with notable medicinal significance. Numerous reports on the synthesis of isoquinoline derivatives via transition metal catalysis have been published worldwide. In this review, we summarize recent approaches for synthesizing various isoquinoline derivatives using 3d‐transition‐metal catalysts since 2020. The review has been divided into different 3d‐transition‐metal‐based catalysis. We expect that this review will bring a better overview of the present status of the significant progress made in the 3d‐transition‐metal‐based synthesis of isoquinolines and persuade more advancements and research in this area in the near future.
Cover crops, farm economics, and policy
Authors: Schnitkey Gary D. , Sellars Sarah C. , Gentry Laura F. 
Published: November 2023

AbstractCover crops have many environmental benefits, including nutrient sequestering, soil health improvements, carbon dioxide removal, and biodiversity increases. Yet, farmers often do not receive enough benefits to warrant planting cover crops, particularly when they have no prior experience with managing cover crops. Therefore, public policies supporting cover crop use may be justified because of the positive externalities of cover crops are greater than the social cost of cover crop programs. Current Federal programs do not provide enough funding to elicit large cover crop use. We present a Federal program designed to increase cover crop use.
Copper‐Catalyzed Aminoazidation of Alkenes with NFC: One‐step Vicinal Functionalization for CuAAC and SuFEx Reactions
Authors: Kimura Hiroto , Aikawa Kohsuke , Hashimoto Takuya 
Published: November 2023

AbstractCuAAC and SuFEx reactions are two major tools to connect molecules in click chemistry. An azide plays the pivotal role in the former, and a fluorosulfonyl group is the key functionality in the latter. While there are various synthetic methods to attach one of these two functionalities, the simultaneous attachment of both an azide and a fluorosulfonyl group to one molecule remains unexplored. We report the copper‐catalyzed aminoazidation of alkenes using neopentyl N‐fluoro‐N‐(fluorosulfonyl)carbamate (NFC), which incorporates an azide and a (fluorosulfonyl)amino group to an alkene in one step. Derivatization of a product via consecutive CuAAC and SuFEx reactions is also demonstrated, enabling rapid diversification of molecular structure.
In Situ Scattering Studies of Superconducting Vacancy‐Ordered Monoclinic TiO Thin Films
Authors: Baksi Merve , Hong Hawoong , Kumah Divine P. 
Published: November 2023

AbstractThe structural and transport properties of vacancy‐ordered monoclinic superconducting titanium oxide (TiO) thin films grown by molecular beam epitaxy are investigated. The evolution of the crystal structure during growth is monitored by in situ synchrotron X‐ray diffraction. Long‐range ordering of Ti and O vacancies in the disordered cubic phase stabilizes the vacancy‐ordered monoclinic TiO phase. The reduced structural disorder arising from vacancy‐ordering is correlated with a superconductor‐metal transition (SMT) in contrast to the superconductor‐insulator transition (SIT) observed in cubic TiO, orthorhombic Ti2O3, and the Magneli γ − Ti3O5 and γ − Ti4O7 phase. Magnetoresistance measurements for the SIT phases indicate superconducting fluctuations persisting in the normal phase. These results confirm the role of disorder related to Ti and O vacancies and structural inhomogeneity in determining the electronic properties of the normal state of titanium oxide‐based superconductors.
Quinoline‐based thiazolyl‐hydrazones target cancer cells through autophagy inhibition
Authors: Ćurčić Vladimir , Olszewski Mateusz , Maciejewska Natalia , Višnjevac Aleksandar , Srdić‐Rajić Tatjana , Dobričić Vladimir , García‐Sosa Alfonso T. , Kokanov Sanja B. , Araškov Jovana B. , Silvestri Romano , Schüle Roland , Jung Manfred , Nikolić Milan , Filipović Nenad R. 
Published: November 2023

AbstractHeterocyclic pharmacophores such as thiazole and quinoline rings have a significant role in medicinal chemistry. They are considered privileged structures since they constitute several Food and Drug Administration (FDA)‐approved drugs for cancer treatment. Herein, we report the synthesis, in silico evaluation of the ADMET profiles, and in vitro investigation of the anticancer activity of a series of novel thiazolyl‐hydrazones based on the 8‐quinoline (1a–c), 2‐quinoline (2a–c), and 8‐hydroxy‐2‐quinolyl moiety (3a–c). The panel of several human cancer cell lines and the nontumorigenic human embryonic kidney cell line HEK‐293 were used to evaluate the compound‐mediated in vitro anticancer activities, leading to [2‐(2‐(quinolyl‐8‐ol‐2‐ylmethylene)hydrazinyl)]‐4‐(4‐methoxyphenyl)‐1,3‐thiazole (3c) as the most promising compound. The study revealed that 3c blocks the cell‐cycle progression of a human colon cancer cell line (HCT‐116) in the S phase and induces DNA double‐strand breaks. Also, our findings demonstrate that 3c accumulates in lysosomes, ultimately leading to the cell death of the hepatocellular carcinoma cell line (Hep‐G2) and HCT‐116 cells, by the mechanism of autophagy inhibition.
Programmed Death Ligand 1–Expressing Macrophages and Their Protective Role in the Joint During Arthritis
Authors: Wood Megan Kay , Daoud Abdel , Talor Monica Vladut , Kalinoski Hannah Maryam , Hughes David Matthew , Jaime Camille Marie , Hooper Jody Elizabeth , Won Taejoon , Čiháková Daniela 
Published: November 2023

ObjectiveArthritis associated with immune checkpoint inhibitor therapies highlights the importance of immune checkpoint expression for joint homeostasis. We investigated the role of programmed death ligand (PD‐L) 1 in the synovium using a collagen‐induced arthritis (CIA) mouse model.MethodsWe blocked PD‐L1 using blocking antibodies during CIA and assessed the arthritis severity by clinical and histologic scoring. PD‐L1 expression and the origin of synovial macrophages were investigated using flow cytometry and parabiosis. We used Cre‐Lox mice to ascertain the protective role of PD‐L1–expressing macrophages in arthritis. The immune profile of human and murine synovial PD‐L1+ macrophages was determined by reverse transcriptase–polymerase chain reaction, flow cytometry, and single‐cell RNA sequencing.ResultsAnti–PD‐L1 antibody treatment during CIA worsened arthritis with increased immune cell infiltration compared with isotype control, supporting the regulatory role of PD‐L1 in the joint. The main cells expressing PD‐L1 in the synovium were macrophages. Using parabiosis, we showed that synovial PD‐L1+ macrophages were both locally proliferating and partially replaced by the circulation. PD‐L1+ macrophages had increased levels of MER proto‐oncogene tyrosine kinase (MerTK) and interleukin (IL)‐10 expression during acute CIA. Genetic depletion of PD‐L1 on macrophages in LyzcrePD‐L1fl/fl mice resulted in worsened CIA compared with controls. We found that human PD‐L1+ macrophages in the synovium of healthy individuals and patients with rheumatoid arthritis express MerTK and IL‐10.ConclusionPD‐L1+ macrophages with efferocytotic and anti‐inflammatory characteristics protect the synovium from severe arthritis in the CIA mouse model. Tissue‐protective, PD‐L1–expressing macrophages are also present in the human synovium at homeostasis and during rheumatoid arthritis.
Neuroanatomy in virtual reality: Development and pedagogical evaluation of photogrammetry‐based 3D brain models
Authors: Aridan Nadav , Bernstein‐Eliav Michal , Gamzo Dana , Schmeidler Maya , Tik Niv , Tavor Ido 
Published: November 2023

AbstractAnatomy studies are an essential part of medical training. The study of neuroanatomy in particular presents students with a unique challenge of three‐dimensional spatial understanding. Virtual Reality (VR) has been suggested to address this challenge, yet the majority of previous reports have implemented computer‐generated or imaging‐based models rather than models of real brain specimens. Using photogrammetry of real human bodies and advanced editing software, we developed 3D models of a real human brain at different stages of dissection. Models were placed in a custom‐built virtual laboratory, where students can walk around freely, explore, and manipulate (i.e., lift the models, rotate them for different viewpoints, etc.). Sixty participants were randomly assigned to one of three learning groups: VR, 3D printed models or read‐only, and given 1 h to study the white matter tracts of the cerebrum, followed by theoretical and practical exams and a learning experience questionnaire. We show that following self‐guided learning in virtual reality, students demonstrate a gain in spatial understanding and an increased satisfaction with the learning experience, compared with traditional learning approaches. We conclude that the models and virtual lab described in this work may enhance learning experience and improve learning outcomes.
Lithium‐Sulfur Batteries with Triethylsulfonium Bis(trifluoromethane sulfonyl)imide Ionic Liquid During First Charge‐Discharge Cycling: EIS & DFT Study
Authors: Pushpa Selvi M. , Nimma Elizabeth R. , Sinthika S. , Arockia Shyamala Paniyarasi S. , Padmaja S. , Susanna Victoria Backiyaleela S. 
Published: November 2023

AbstractWith high theoretical capacity and energy density, lithium‐sulfur batteries (Li−S) have the potential to meet future energy demands including electric vehicles. Various strategies have been developed to address the challenges of Li−S batteries such as polysulfide shuttling, capacity fading, and lithium dendrite formation. By using suitable electrolyte additives, it is possible to enhance the interfacial properties of Li−S batteries and mitigate polysulfide shuttling. In the present work, an aprotic ionic liquid Triethylsulfonium bis(trifluoromethane sulfonyl)imide ([S222][TFSI]) has been used as an electrolyte additive, and the physico‐electrochemical and interfacial properties are investigated. The Li||Li cell with hybrid electrolyte shows stable interfacial resistance and the EIS study during the first discharge and charge of Li−S cell demonstrates stable charge transfer and bulk resistances which indicate the enhanced interfacial properties and the inhibition of polysulfide shuttling. The first‐principles calculations were conducted to investigate the nature of the interaction between the lithium polysulfides (LiPSs) and the [S222][TFSI] molecule. Long chain LiPSs (Li2Sx, 4<x<8) interact with [S222][TFSI] molecule via Li‐bond and hyperconjugation effect. [S222][TFSI] shows the ability to dissolve Li2S and Li2S2 precipitation at the cathode surface which can result in increased utilization of active sulfur and reduced capacity fading.
Immobilizing white‐rot fungi laccase: Toward bio‐derived supports as a circular economy approach in organochlorine removal
Authors: Serbent Maria Pilar , Magario Ivana , Saux Clara 
Published: November 2023

AbstractDespite their high persistence in the environment, organochlorines (OC) are widely used in the pharmaceutical industry, in plastics, and in the manufacture of pesticides, among other applications. These compounds and the byproducts of their decomposition deserve attention and efficient proposals for their treatment. Among sustainable alternatives, the use of ligninolytic enzymes (LEs) from fungi stands out, as these molecules can catalyze the transformation of a wide range of pollutants. Among LEs, laccases (Lac) are known for their efficiency as biocatalysts in the conversion of organic pollutants. Their application in biotechnological processes is possible, but the enzymes are often unstable and difficult to recover after use, driving up costs. Immobilization of enzymes on a matrix (support or solid carrier) allows recovery and stabilization of this catalytic capacity. Agricultural residual biomass is a passive environmental asset. Although underestimated and still treated as an undesirable component, residual biomass can be used as a low‐cost adsorbent and as a support for the immobilization of enzymes. In this review, the adsorption capacity and immobilization of fungal Lac on supports made from residual biomass, including compounds such as biochar, for the removal of OC compounds are analyzed and compared with the use of synthetic supports. A qualitative and quantitative comparison of the reported results was made. In this context, the use of peanut shells is highlighted in view of the increasing peanut production worldwide. The linkage of methods with circular economy approaches that can be applied in practice is discussed.
Exploring how attorneys address grooming in criminal trials of child sexual abuse
Authors: Denne Emily , Stolzenberg Stacia N. 
Published: November 2023

AbstractGrooming is a common tactic among perpetrators of child sexual abuse (CSA). It is important that grooming is addressed in court to explain the unintuitive ways a child may act when they have been victims of abuse. The present study draws upon 134 transcripts of CSA criminal trials to establish how attorneys talk about grooming in court. Only 1.8% of attorney's questions addressed grooming behaviors. The majority of these focusing on exposure to pornography (27%) or boundary pushing (19%). Invitations elicited the most productive reports of grooming from children. There was a statistically significant difference in the proportion with which defense and prosecuting attorney's raised grooming issues, with prosecutors raising grooming issues more often than defense attorneys. We suggest that attorneys consider devoting proportionally more time to addressing grooming in court, to help jurors demystify common myths surrounding CSA.