bluuebunny/crossref_metadata_2025_split huggingface dataset:
Organic Binary and Ternary Cocrystal Engineering Based on Halogen Bonding Aimed at Room‐Temperature Phosphorescence
Authors: Abe Ayano , Goushi Kenichi , Mamada Masashi , Adachi Chihaya 
Published: March 2023

AbstractRecently, there has been intense interest in pure organic room‐temperature phosphorescence (ORTP) from cocrystals composed of 1,4‐diiodotetrafluorobenzene (DITFB) and a variety of polycyclic aromatic hydrocarbons (PAHs) or their derivatives. To expand the possibility of halogen bonding‐based cocrystals, the relationship between the crystal packing motifs and ORTP characteristics in binary cocrystals composed of DITFB and PAHs of phenanthrene (Phen), chrysene (Chry), and pyrene (Pyr), respectively, is investigated. The σ‐hole···π and π‐hole···π interactions determine not only the crystal packing motifs but also photoluminescence quantum yields (PLQYs). The Phen‐DITFB and Chry‐DITFB binary cocrystals with σ‐hole···π interactions show higher PLQY compared with the Pyr‐DITFB binary cocrystal with π‐hole···π interaction. Further, to clarify the effect of crystal structures on PLQY, ternary cocrystals are prepared by partially doping Pyr into Phen‐DITFB. The crystal packing motif of the ternary cocrystal originates from a Phen‐DITFB cocrystal with σ‐hole···π interaction, and some of the Phen sites are randomly replaced with Pyr molecules. The ORTP emission is derived from Pyr. The maximum PLQY is >20% due to suppressing nonradiative decay by changing the crystal packing motif.
Repeatedly Recyclable 3D Printing Catalyst‐Free Dynamic Thermosetting Photopolymers
Authors: Cui Jingjing , Liu Fukang , Lu Zhe , Feng Shiwei , Liang Chen , Sun Yongding , Cui Jin , Zhang Biao 
Published: March 2023

AbstractPhoto‐curing 3D printing technology has promoted the advanced manufacturing in various fields, but has exacerbated the environmental crisis by the demand for the chemically cross‐linked thermosetting photopolymers. Here, the authors report a generic strategy to develop catalyst‐free dynamic thermosetting photopolymers, based on photopolymerization and transesterification, that can enable users to realize repeatable 3D printing, providing a practical solution to the environmental challenges. That the β‐carbonyl group adjacent to the ester group greatly accelerates the rate of transesterification is demonstrated. The generated resins from the immobilization of the catalyst‐free reversible bonds into the photopolymers leads to a dynamic covalently crosslinked network structure upon UV based 3D printing, which exhibit controllable mechanical properties with elastomeric behaviors to thermadapt shape memory polymers. Furthermore, the resulting network can be reverted into an acrylate‐functioned photopolymer that is suitable for 3D printing again, presenting an on‐demand, repeatedly recyclable thermosetting photopolymer platform for sustainable 3D printing.
A Mechanistic Insight into the Oxygen Redox of Li‐Rich Layered Cathodes and their Related Electronic/Atomic Behaviors Upon Cycling
Authors: Kang Seongkoo , Choi Dayeon , Lee Hakwoo , Choi Byungjin , Kang Yong‐Mook 
Published: March 2023

AbstractLi‐rich cathodes are extensively investigated as their energy density is superior to Li stoichiometric cathode materials. In addition to the transition metal redox, this intriguing electrochemical performance originates from the redox reaction of the anionic sublattice. This new redox process, the so‐called anionic redox or, more directly, oxygen redox in the case of oxides, almost doubles the energy density of Li‐rich cathodes compared to conventional cathodes. Numerous theoretical and experimental investigations have thoroughly established the current understanding of the oxygen redox of Li‐rich cathodes. However, different reports are occasionally contradictory, indicating that current knowledge remains incomplete. Moreover, several practical issues still hinder the real‐world application of Li‐rich cathodes. As these issues are related to phenomena resulting from the electronic to atomic evolution induced by unstable oxygen redox, a fundamental multiscale understanding is essential for solving the problem. In this review, the current mechanistic understanding of oxygen redox, the origin of the practical problems, and how current studies tackle the issues are summarized.
Pyroptosis‐Mediated Synergistic Photodynamic and Photothermal Immunotherapy Enabled by a Tumor‐Membrane‐Targeted Photosensitive Dimer
Authors: Tang Yuqi , Bisoyi Hari Krishna , Chen Xu‐Man , Liu Zhiyang , Chen Xiao , Zhang Shu , Li Quan 
Published: March 2023

AbstractOvercoming the resistance to apoptosis and immunosuppression of tumor cells is a significant challenge in augmenting the effect of cancer immunotherapy. Pyroptosis, a lytic programmed cell‐death pathway unlike apoptosis, is considered a type of immunogenic cell death (ICD) that can intensify the ICD process in tumor cells, releasing dramatically increased tumor‐associated antigens and damage‐associated molecular patterns to promote cancer immunotherapy. Herein, a tumor cell membrane‐targeted aggregation‐induced emission photosensitive dimer is found to be able to achieve highly efficient ICD under the synergistic effect of photodynamic and photothermal therapy. The photosensitive dimer can efficiently produce type‐I reactive oxygen species (ROS) by photodynamic therapy in hypoxic tumor tissue, leading to pyroptosis by direct cell membrane damage, which is further reinforced by its photothermal effect. Furthermore, the enhanced ICD effect based on the dimer can completely eliminate the primary tumor on the seventh day of treatment and can also boost systemic antitumor immunity by generating immune memory, which is demonstrated by the superior antitumor therapeutic effects on both solid tumors and metastatic tumors when healing 4T1 tumor mouse models with poor immunogenicity.
GIWAXS Characterization of Metal–Organic Framework Thin Films and Heterostructures: Quantifying Structure and Orientation
Authors: Fischer Jan C. , Li Chun , Hamer Sebastian , Heinke Lars , Herges Rainer , Richards Bryce S. , Howard Ian A. 
Published: March 2023

AbstractFor optoelectronic applications of metal–organic framework (MOF) thin films, it is important to be able to fabricate films and heterostructures that are highly oriented relative to the substrate's surface normal. However, process optimization to achieve this is difficult without sufficiently detailed structural characterization of the deposited films. It is demonstrated that 2D grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) data from a laboratory system go a long way to providing such characterization and can 1) better test structural models than 1D scans, 2) provide a quantitative estimate—useful for process optimization—of the fraction of the deposited film that has the desired surface‐oriented texture (2D powder), and 3) deliver such information as a function of depth into the film—useful for heterostructure characterization. Herein, GIWAXS data collection and analysis are introduced in the context of understanding MOF thin films, then it is shown how the desired oriented fraction (2D powder fraction) of UiO‐66 fabricated by vapor‐assisted conversion can be increased from 4% to over 95% by minimizing nucleation in solution. Finally, it is demonstrated that heterostructures of UiO‐66 and UiO‐67 can be grown wherein both layers are highly ordered (UiO‐66 83%, UiO‐67 >94%) once synthetic protocols are optimized.
Synthesis of Fluoroalkylated Pyrrolidines through Neat Reaction of Fluoroalkyl Iodides with N, N‐Diallylamines
Authors: Mao Ting , Li Weipiao , Liu Xiao‐Xiao , Wang Haoyang , Han Wen‐Yong , Tong Jie , Xiao Shi‐Ji , Zhao Liang , He Chun‐Yang 
Published: March 2023

AbstractWe presented a cascade transformation of N, N‐diallylamines and fluoroalkyl iodides into various functionalized fluoroalkylated pyrrolidines through a visible light‐induced synthetic process in the solvent‐free conditions. In this reaction system, the substrate N, N‐diallylamine acted both as the base and the electron donor. We further demonstrated the practicality of this protocol by the direct modification of amino acids and pharmaceutical molecules.
Fat Extract Modulates Calcium Signaling and Protects against Hyperactive Osteoclastogenesis in Bone Remodeling with Antioxidant Capacity
Authors: Yang Yiqi , Xu Mingming , Kan Tianyou , Wang Yao , Zhang Shuhong , Deng Mingwu , Zhang Wenjie , Li Hanjun , Yu Zhifeng 
Published: March 2023

AbstractOsteoclasts are cells primarily involved in bone remodeling. Hyperactive osteoclastogenesis leads to pathological bone loss and microarchitectural deterioration. However, given the limitations of current osteoclast inhibitors, there is an urgent need for a novel antiresorptive agent with higher efficiency and fewer side effects. Cell‐free fat extract (CEFFE) is the liquid fraction obtained from adipose tissues, which are enriched with a variety of adipokines. This study aims to explore its pharmacologic effect on hyperactive osteoclastogenesis. CEFFE exhibits excellent potentials to attenuate osteoclast‐associated bone loss in ovariectomy mice and to inhibit osteoclastogenesis in primary monocytes. Furthermore, the cationic protein fraction of CEFFE (CEFFE‐Cation) is identified as the main inhibitory component in osteoclast formation assay. According to liquid chromatography with tandem mass spectrometry analysis, the CEFFE‐Cation fraction mainly consists of various antioxidant enzymes and cytokines, which endow it with a superior antioxidant capacity. Meanwhile, CEFFE‐Cation is also capable of mitigating Ca2+ oscillation and subsequent nuclear factor of activated T‐cells 1 nuclear translocation during osteoclastogenesis. Overall, this study elucidates the promising translational potential of CEFFE as a next‐generation personalized antiresorptive agent for osteolytic bone disease treatment.
Battling bots: Experiences and strategies to mitigate fraudulent responses in online surveys
Authors: Goodrich Brittney , Fenton Marieke , Penn Jerrod , Bovay John , Mountain Travis 
Published: March 2023

AbstractDeclining survey response rates have driven many researchers to seek out cost‐effective methods of increasing participation, such as conducting surveys online, paying incentives, and using social media to engage hard‐to‐reach populations. Malicious actors can exploit the monetary incentives and anonymity of online surveys, threatening the integrity of survey data. We share two recent experiences conducting online surveys that were inundated with fraudulent responses. Our objective is to increase awareness of this emerging issue and offer guidance for others to mitigate the effects of fraudulent responders in their own research.
Impact of modernization on oxidative stress among indigenous populations in northern Laos
Authors: Mizuno Yuki , Inaba Yohei , Masuoka Hiroaki , Kibe Mihoko , Kosaka Satoko , Natsuhara Kazumi , Hirayama Kazuhiro , Inthavong Nouhak , Kounnavong Sengchanh , Tomita Shinsuke , Umezaki Masahiro 
Published: March 2023

AbstractObjectivesTo explore the impact of modernization on oxidative stress during a momentous health transition process, we investigated differences in oxidative stress among the indigenous populations of villages in northern Laos with different levels of modernization.MethodsWe conducted a cross‐sectional study of 380 adults in three villages with different levels of modernization. Three biomarkers related to oxidative stress were measured: urinary 8‐hydroxy‐2′‐deoxyguanosine (8‐OHdG) and 8‐isoprostane concentrations (both measured by liquid chromatography–tandem mass spectrometry), and blood telomere length (measured with qPCR). We examined associations between village‐level modernization and oxidative stress‐related biomarkers in a multilevel analysis including a random effect and covariates.ResultsThe geometric means of urinary 8‐OHdG and 8‐isoprostane concentrations were 2.92 and 0.700 μg/g creatinine, respectively, in our study population. Higher urinary 8‐OHdG concentrations and shorter telomeres were observed in participants from the more modernized villages, whereas urinary 8‐isoprostane concentrations did not differ significantly among villages.ConclusionsOur findings imply that modernization‐induced changes in lifestyle may increase oxidative DNA damage. Baseline levels of oxidative lipid damage are expected to be high in the indigenous populations of northern Laos. Assessments of oxidative stress may provide valuable insights into the mechanisms of health transition in specific populations.
Proton Tunneling Distances for Metal Hydrides Formation Manage the Selectivity of Electrochemical CO2 Reduction Reaction
Authors: He Shuanglin , Qing Yuhang , Zhang Ping , Xiong Ying , Wu Qianqian , Zhang Yaping , Chen Lin , Huang Fang , Li Fei 
Published: March 2023

AbstractA series of manganese polypyridine complexes were prepared as CO2 reduction electrocatalysts. Among these catalysts, the intramolecular proton tunneling distance for metal hydride formation (PTD‐MH) vary from 2.400 to 2.696 Å while the structural, energetic, and electronic factors remain essentially similar to each other. The experimental and theoretical results revealed that the selectivity of CO2 reduction reaction (CO2RR) is dominated by the intramolecular PTD‐MH within a difference of ca. 0.3 Å. Specifically, the catalyst functionalized with a pendent phenol group featuring a slightly longer PTD‐MH favors the binding of proton to the [Mn−CO2] adduct rather than the Mn center and results in ca. 100 % selectivity for CO product. In contrast, decreasing the PTD‐MH by attaching a dangling tertiary amine in the same catalyst skeleton facilitates the proton binding on the Mn center and switches the product from CO to HCOOH with a selectivity of 86 %.
Laser Writing of Block‐Copolymer Images into Mesopores Using SBDC‐Initiated Visible‐Light‐Induced Polymerization
Authors: Förster Claire , Lehn Robert , Saritas Enis Musa , Andrieu‐Brunsen Annette 
Published: March 2023

AbstractFor miniaturization, as well as for improving artificial nanopore performance, precise local polymer functionalization and the combination of different functionalities are required. Imagining data driven nanopore design automated nanopore functionalization would be beneficial. Using direct laser writing as one option of automated nanopore polymer functionalization visible light induced polymerizations are beneficial. Here, we demonstrate the functionalization of mesoporous silicafilms with two different polymers using automated laser writing. For this we developed a visible light (400–700 nm and 405 nm) N,N(diethylamino)dithiocarbamoylbenzyl(trimethoxy)silane (SBDC) inifierter initiated polymerization. While transferring this visible light induced polymerization using SBDC to a commercially available microscope, direct, automated laser writing, as well as polymer re‐initiation was demonstrated. Thereby, polymer spots of 37 and 40 μm in diameter were achieved using 1–5 seconds for each irradiated spot.
Hydrogen Evolution on Electrode‐Supported Ptn Clusters: Ensemble of Hydride States Governs the Size Dependent Reactivity
Authors: Zhang Zisheng , Masubuchi Tsugunosuke , Sautet Philippe , Anderson Scott L. , Alexandrova Anastassia N. 
Published: March 2023

AbstractWe report the size‐dependent activity and stability of supported Pt1,4,7,8 for electrocatalytic hydrogen evolution reaction, and show that clusters outperform polycrystalline Pt in activity, with size‐dependent stability. To understand the size effects, we use DFT calculations to study the structural fluxionality under varying potentials. We show that the clusters can reshape under H coverage and populate an ensemble of states with diverse stoichiometry, structure, and thus reactivity. Both experiment and theory suggest that electrocatalytic species are hydridic states of the clusters (≈2 H/Pt). An ensemble‐based kinetic model reproduces the experimental activity trend and reveals the role of metastable states. The stability trend is rationalized by chemical bonding analysis. Our joint study demonstrates the potential‐ and adsorbate‐coverage‐dependent fluxionality of subnano clusters of different sizes and offers a systematic modeling strategy to tackle the complexities.
Single‐Atom Catalysis in Organic Synthesis
Authors: Saptal Vitthal B. , Ruta Vincenzo , Bajada Mark A. , Vilé Gianvito 
Published: March 2023

AbstractSingle‐atom catalysts hold the potential to significantly impact the chemical sector, pushing the boundaries of catalysis in new, uncharted directions. These materials, featuring isolated metal species ligated on solid supports, can exist in many coordination environments, all of which have shown important functions in specific transformations. Their emergence has also provided exciting opportunities for mimicking metalloenzymes and bridging the gap between homogeneous and heterogeneous catalysis. This Review outlines the impressive progress made in recent years regarding the use of single‐atom catalysts in organic synthesis. We also illustrate potential knowledge gaps in the search for more sustainable, earth‐abundant single‐atom catalysts for synthetic applications.
Mosaic CuI−CuII−InIII2D Perovskites: Pressure‐Dependence of the Intervalence Charge Transfer and a Mechanochemical Alloying Method
Authors: Li Jiayi , Matheu Roc , Ke Feng , Liu Zhenxian , Lin Yu , Karunadasa Hemamala I. 
Published: March 2023

AbstractThe perovskite (BA)4[CuII(CuIInIII)0.5]Cl8(1BA; BA+=butylammonium) allows us to study the high‐pressure structural, optical, and transport properties of a mixed‐valence 2D perovskite. Compressing1BAreduces the onset energy of CuI/IIintervalence charge transfer from 1.2 eV at ambient pressure to 0.2 eV at 21 GPa. The electronic conductivity of1BAincreases by 4 orders of magnitude upon compression to 20 GPa, when the activation energy for conduction decreases to 0.16 eV. In contrast, CuIIperovskites achieve similar conductivity at ≈50 GPa. The solution‐state synthesis of these perovskites is complicated, with more undesirable side products likely from the precursor mixtures containing three different metal ions. To circumvent this problem, we demonstrate an efficient mechanochemical synthesis to expand this family of halide perovskites with complex composition by simply pulverizing together powders of 2D CuIIsingle perovskites and CuIInIIIdouble perovskites.
A Remotely Controlled Nanosystem for Spatiotemporally Specific Gene Regulation and Combinational Tumor Therapy
Authors: Chai Xin , Yi Deyu , Sheng Chuangui , Zhao Jian , Li Lele 
Published: March 2023

AbstractThe dearth of technologies that allow gene modulation and therapy with high spatiotemporal precision remains a bottleneck in biomedical research and applications. Here we present a near‐infrared (NIR) light‐controlled nanosystem that allows spatiotemporally controlled regulation of gene expression and thus combinational tumor therapy. The nanosystem is built by engineering of an enzyme‐activatable antisense oligonucleotide and further combination with an upconversion nanoparticle‐based photodynamic system and a mitochondria localization signal. The system relies on photodynamic effect‐induced translocation of a DNA repair enzyme from nucleus into mitochondria, which enables spatially selective gene regulation via enzymatic reactions. We demonstrate that the NIR light‐induced mitochondrial photodamage and gene regulation enable enhanced antitumor effect. Our approach may enable the specific gene regulation and tumor treatment with high precision both spatially and temporally.
Low‐Dimensional Phase Regulation to Restrain Non‐Radiative Recombination for Sky‐Blue Perovskite LEDs with EQE Exceeding 15 %
Authors: Wang Bin , Zhou Yu‐Hang , Yuan Shuai , Lou Yan‐Hui , Wang Kai‐Li , Xia Yu , Chen Chun‐Hao , Chen Jing , Shi Yi‐Ran , Wang Zhao‐Kui , Liao Liang‐Sheng 
Published: March 2023

AbstractAchieving efficient blue electroluminescence (EL) remains the fundamental challenge that impedes perovskite light‐emitting diodes (PeLEDs) towards commercial applications. The bottleneck accounting for the inefficient blue PeLEDs is broadly attributed to the poor‐emissive blue perovskite emitters based on either mixed halide engineering or reduced‐dimensional strategy. Herein, we report the high‐performing sky‐blue PeLEDs (490 nm) with the maximum EQE exceeding 15 % by incorporating a molecular modifier, namely 4,4′‐Difluorophenone, for significantly suppressing the non‐radiative recombination and tuning of the low‐dimensional phase distribution of quasi‐2D blue perovskites, which represents a remarkable paradigm for developing the new generation of blue lighting sources.
A Simple Molecular Design Strategy for Pure‐Red Multiple Resonance Emitters
Authors: Chen Haowen , Fan Tianjiao , Zhao Guimin , Zhang Dongdong , Li Guomeng , Jiang Wei , Duan Lian , Zhang Yuewei 
Published: March 2023

AbstractThough the flourishment of materials with multiple resonance (MR) in blue to green regions, red‐emissive MR emitters are still rare in literatures, which definitely should be resolved for further applications. Herein, we report a simple molecular design strategy for the construction of pure‐red MR emitters by conjugate charge transfer, which could greatly enhance the π‐conjugation degree and charge‐transfer property of the target molecule while maintaining the basic feature of MR, leading to a significant redshift of more than 128 nm compared to the selected parent MR core. The proof‐of‐concept emitter PPZ‐BN exhibited a pure‐red emission with a dominant peak at 613 nm and a small full‐width‐at‐half‐maximum of 0.16 eV (48 nm). The optimized organic light‐emitting diode showed a high external quantum efficiency of 26.9 %, a small efficiency roll‐off, and an excellent operation stability (LT99) of more than 43 hours at an initial luminance of 10 000 cd m−2.
An Electron‐Deficient CpE Iridium(III) Catalyst: Synthesis, Characterization, and Application to Ether‐Directed C−H Amidation
Authors: Tomita Eiki , Kojima Masahiro , Nagashima Yuki , Tanaka Ken , Sugiyama Haruki , Segawa Yasutomo , Furukawa Atsushi , Maenaka Katsumi , Maeda Satoshi , Yoshino Tatsuhiko , Matsunaga Shigeki 
Published: March 2023

AbstractThe synthesis, characterization, and catalytic performance of an iridium(III) catalyst with an electron‐deficient cyclopentadienyl ligand ([CpEIrI2]2) are reported. The [CpEIrI2]2 catalyst was synthesized by complexation of a precursor of the CpE ligand with [Ir(cod)OAc]2, followed by oxidation, desilylation, and removal of the COD ligand. The electron‐deficient [CpEIrI2]2 catalyst enabled C−H amidation reactions assisted by a weakly coordinating ether directing group. Experimental mechanistic studies and DFT calculations suggested that the high catalytic performance of [CpEIrI2]2 is due to its electron‐deficient nature, which accelerates both C−H activation and IrV‐nitrenoid formation.
Stereospecific Photoredox‐Catalyzed Vinylations to Functionalized Alkenes and C‐Glycosides**
Authors: Bhaskar Pal Kumar , Di Tommaso Ester Maria , Inge A. Ken , Olofsson Berit 
Published: March 2023

AbstractWe report an efficient radical‐mediated C−C coupling through photoredox‐catalyzed reactions of 4‐alkyl‐dihydropyridines (DHPs) and vinylbenziodoxol(on)es (VBX, VBO). This transition‐metal‐free and mild photocatalytic method has excellent functional group tolerance and affords vinylated products in good yields, with complete retention of the alkene configuration. The utility of the methodology is demonstrated by the diastereoselective synthesis of C‐vinyl glycosides. Preliminary mechanistic studies suggest that the C−C bond formation is stereospecific and proceeds through a concerted radical coupling transition state.