bluuebunny/crossref_metadata_2025 huggingface dataset:
Theories of Pragmatics Learning
Authors: Li Shuai
Published: March 2023

This entry provides an overview of two major theoretical approaches to second language (L2) pragmatic development: cognitive and socially oriented approaches. The cognitive theories include the noticing hypothesis, the two‐dimensional model, and the skill acquisition theory (ACT‐R). The socially oriented theories include the Vygotskian sociocultural theory and language socialization. It is argued that the cognitive and socially oriented approaches differ in their views toward the nature of L2 pragmatic development (i.e., intrapersonal vs. interpersonal), which has important implications for conceptualizing pragmatic knowledge and for understanding the mechanisms underlying pragmatic development.
Literacy in Multilingual Classrooms
Authors: Cervantes‐Soon Claudia G. , García Ofelia
Published: March 2023

Literacy instruction that provides opportunities for learners from diverse language backgrounds to access their entire meaning‐making repertoire is essential in multilingual classrooms. This requires shifting conceptions of language/multilingualism and literacy/biliteracy that are prevalent in schools today by considering minoritized and racialized multi/bilingual learners as legitimate meaning makers themselves, with valid linguistic knowledge rather than as inadequate or incomplete language users. This discussion redefines conceptions of language and literacy in multilingual classrooms by situating them in more expansive sociocultural and critical perspectives. It then outlines five principles for literacy instruction in multilingual classrooms that leverage students' entire meaning‐making repertoire to enact social and cognitive justice for multi/bilingual learners.
English for Specific and Academic Purposes as Pedagogical Frameworks
Authors: Basturkmen Helen
Published: March 2023

This entry examines ways English for specific purposes (ESP) and English for academic purposes (EAP) support teachers in their endeavors to devise instruction to prepare English as a second language (ESL) learners for the demands of working or studying in English. EAP grew out of ESP and shares similar, pedagogical features with ESP. The entry describes a range of contexts in which specialized (ESP and EAP) language instructions typically occur and ways in which ESP and EAP are distinctive pedagogical frameworks. For learners, the provision of specialized language instruction that is based on identification of their work or study needs is widely understood to be motivating, effective, and efficient. However, for teachers of specialized English, working in this area can present considerable challenges in terms of developing their own knowledge of the specialist linguistic register, devising in‐house materials, and developing new courses or revising others, to meet the precise needs of their groups of learners. The entry describes ways the ESP and EAP research supports the work of teachers. It highlights the important role of linguistic inquiry into specialist language use and case reports of ESP and EAP teaching practices in particular contexts as major forms of support. It identifies lacunae in the literature and suggests future research directions.
Achieving Thermodynamic Stability of Single‐Crystal Co‐Free Ni‐Rich Cathode Material for High Voltage Lithium‐Ion Batteries
Authors: Shen Jixue , Zhang Bao , Huang Weiyuan , Li Xiao , Xiao Zhiming , Wang Jing , Zhou Tao , Wen Jianguo , Liu Tongchao , Amine Khalil , Ou Xing
Published: March 2023

Ni‐rich layered cathode materials are progressively considered as the standard configuration of high‐energy electric vehicles by virtues of their high capacity and eliminated “range anxiety.” However, the poor cyclic stability and severe cobalt supply crisis would restrain their wide commercial applicability. Here, a cost‐effective single‐crystal Co‐free Ni‐rich cathode material LiNi0.8Mn0.18Fe0.02O2 (NMF), which outperforms widely commercial polycrystalline LiNi0.83Co0.11Mn0.06O2 (MNCM) and single‐crystal LiNi0.83Co0.11Mn0.06O2 (SNCM) is reported. Surprisingly, NMF can compensate for the reversible capacity loss under the designed conditions of high‐temperature and elevated‐voltage, achieving a competitive energy density compared with conventional MNCM or SNCM. Combining operando characterizations and density functional theory calculation, it is revealed that NMF cathode with improved dynamic structure evolution largely alleviates the mechanical strain issue commonly found in Ni‐rich cathode, which can reduce the formation of intragranular cracks and improve the safety performance. Consequently, this new Co‐free NMF cathode can achieve a perfect equilibrium between material cost and electrochemical performance, which not only reduces the production cost by >15%, but also demonstrates excellent thermal stability and cycling performance..
Progress and Insight of Van der Waals Heterostructures Containing Interlayer Transition for Near Infrared Photodetectors
Authors: Ahmad Waqas , Pan Liang , Khan Karim , Jia Lingpu , Zhuang Qiandong , Wang Zhiming
Published: March 2023

Van der Waals (vdWs) heterostructures enable bandgap engineering of different 2D materials to realize the interlayer transition via type‐II band alignment leading to broaden spectrum that is beyond the cut‐off wavelength of individual 2D materials. Interlayer transition has a significant effect on the optoelectronic performance of vdWs heterostructure devices, and strong interlayer transition in 2D vdWs heterojunction is always demandable for sufficient charge transfer and rapid speed response. Herein, a state‐of‐the‐art review is presented on recent progress on interlayer transition in vdWs heterostructures for near‐infrared (NIR) photodetectors. First, the general synthesis techniques for vdWs heterostructures, band alignments in the vdWs heterostructures are provided. Then, the mechanism of interlayer transition in vdWs heterostructure and recent progress on interlayer transition in vdWs heterostructures for NIR photodetectors are summarized. Afterward, some worthy applications of NIR photodetectors are reviewed in related areas of this topic. At the last, an outlook, challenges, and future research directions of vdWs heterostructures for photodetectors at broaden response spectrum are presented.
Highly Improved Photocurrent Density and Efficiency of Perovskite Solar Cells via Inclined Fluorine Sputtering Process
Authors: Cho Eunmi , Son Jung Geon , Park Chan Beom , Kim In , Yuk Dohun , Park Jin‐Seong , Kim Jin Young , Lee Sang‐Jin
Published: March 2023

Increase in incident light and surface modification of the charge transport layer are powerful routes to achieve high‐performance efficiency of perovskite solar cells (PSCs) by improving the short‐circuit current density (JSC) and charge transport characteristics, respectively. However, few techniques are studied to reduce reflection loss and simultaneously improve the electrical performance of the electron transport layer (ETL). Herein, an inclined fluorine (F) sputtering process to fabricate high‐performance PSCs is proposed. The proposed process simultaneously implements the antireflection effect of F coating and the effect of F doping on a TiO2 ETL, which increases the amount of light transmitted into the PSC due to the extremely low refractive index (≈1.39) and drastically improves the electrical properties of TiO2. Consequently, the JSC of the F coating and doping perovskite solar cell (F‐PSC) increased from 25.05 to 26.01 mA cm−2, and the power conversion efficiency increased from 24.17% to 25.30%. The unencapsulated F‐PSC exhibits enhanced air stability after 900 h of exposure to ambient environment atmosphere (30% relative humidity, 25 °C under dark condition). The inclined F sputtering process in this study can become a universal method for PSCs from the development stage to commercialization in the future.
Deciphering Structural Origins of Highly Reversible Lithium Storage in High Entropy Oxides with In Situ Transmission Electron Microscopy
Authors: Su Lin , Ren Jingke , Lu Tao , Chen Kexuan , Ouyang Jianwei , Zhang Yue , Zhu Xingyu , Wang Luyang , Min Huihua , Luo Wen , Sun Zhefei , Zhang Qiaobao , Wu Yi , Sun Litao , Mai Liqiang , Xu Feng
Published: March 2023

Configurational entropy‐stabilized single‐phase high‐entropy oxides (HEOs) have been considered revolutionary electrode materials with both reversible lithium storage and high specific capacity that are difficult to fulfill simultaneously by conventional electrodes. However, precise understanding of lithium storage mechanisms in such HEOs remains controversial due to complex multi‐cationic oxide systems. Here, distinct reaction dynamics and structural evolutions in rocksalt‐type HEOs upon cycling are carefully studied by in situ transmission electron microscopy (TEM) including imaging, electron diffraction, and electron energy loss spectroscopy at atomic scale. The mechanisms of composition‐dependent conversion/alloying reaction kinetics along with spatiotemporal variations of valence states upon lithiation are revealed, characterized by disappearance of the original rocksalt phase. Unexpectedly, it is found from the first visualization evidence that the post‐lithiation polyphase state can be recovered to the original rocksalt‐structured HEOs via reversible and symmetrical delithiation reactions, which is unavailable for monometallic oxide systems. Rigorous electrochemical tests coupled with postmortem ex situ TEM and bulk‐level phase analyses further validate the crucial role of structural recovery capability in ensuring the reversible high‐capacity Li‐storage in HEOs. These findings can provide valuable guidelines to design compositionally engineer HEOs for almighty electrodes of next‐generation long‐life energy storage devices.
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

Recently, 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

Photo‐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

Li‐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

Overcoming 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

For 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

We 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

Osteoclasts 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

Declining 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

Objectives

To 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.

Methods

We 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.

Results

The 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.

Conclusions

Our 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

A 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

For 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

We 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

Single‐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

The 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

The 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

Achieving 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

Though 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

The 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

We 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.
Alcohol‐Induced Strong Metal‐Support Interactions in a Supported Copper/ZnO Catalyst
Authors: Jin Shiqing , Zhang Zekai , Li Didi , Wang Yiming , Lian Cheng , Zhu Minghui
Published: March 2023

Tuning the strong metal‐support interaction (SMSI) in metal catalysts is a promising strategy to improve their catalytic performance. In this article, we systematically investigated the influences of different alcohol/water mixtures on the evolution of the interfacial structure of Cu/ZnO catalysts in the reduction stage. A series of in situ characterization and theoretical simulation studies were performed to elucidate the various mechanisms of alcohol induced SMSI. It was found that when methanol/water is added to H2 during the reduction pretreatment, more oxygen vacancies are formed on the ZnO support, which facilitates the dissociation of H2O and the hydroxylation of ZnO species. Such promotion eventually favors the SMSI between Cu and ZnO and increases the catalytic activity for the methanol steam reforming reaction. In contrast, the addition of ethanol/water and 1‐propanol/water during reduction leads to a physical blockage of the catalyst by alcohol molecules, poisoning the active Cu sites and limiting the migration of ZnO species.
Csp3−PIII Bond Formation via Cross‐Coupling of Umpolung Carbonyls with Phosphine Halides Catalyzed by Nickel
Authors: Cheng Ruofei , Li Chao‐Jun
Published: March 2023

A novel method for the formation of Csp3−PIII bonds via the nickel‐catalyzed cross‐coupling of Umpolung carbonyls and phosphine chlorides is reported herein. This process leads to a series of alkylphosphines, which are characterized as sulfides or borane‐phosphine complexes after undergoing further transformation with moderate to good yields. Invaluable free alkylphosphines can be easily obtained by desulfurization or deboration of the products. A possible mechanistic pathway is also discussed. This report represents the first example of using renewable carbonyls as latent organometallic reagent surrogates for cross‐coupling with heteroatom electrophiles.
Defect‐Free Synthesis of a Fully π‐Conjugated Helical Ladder Polymer and Resolution into a Pair of Enantiomeric Helical Ladders**
Authors: Ikai Tomoyuki , Miyoshi Sayaka , Oki Kosuke , Saha Ranajit , Hijikata Yuh , Yashima Eiji
Published: March 2023

Fully π‐conjugated ladder polymers with a spiral geometry represent a new class of helical polymers with great potential for organic nanodevices, but there is no precedent for an optically active helical ladder polymer totally composed of achiral units. We now report the defect‐free synthesis and resolution of a fully π‐conjugated helical ladder polymer with a rigid helical cavity, which has been achieved by quantitative and chemoselective acid‐promoted alkyne benzannulations of a rationally designed, random‐coil achiral polymer followed by chromatographic enantioseparation. Because of a sufficiently high helix‐inversion barrier, the isolated excess one‐handed helical ladder polymer with a degree of polymerization of more than 15 showed a strong circular dichroism with a dissymmetry factor of up to 1.7×10−2 and is thermally stable, maintaining its optical activity in solution even at 100 °C, as well‐supported by molecular dynamics simulation.
Photopolymerization‐Driven Macroscopic Mechanical Motions of a Composite Film Containing a Vinyl Coordination Polymer
Authors: Yang Zhan‐Yong , Sang Xiao , Liu Dong , Li Qiu‐Yi , Lang Feifan , Abrahams Brendan F. , Hou Hongwei , Braunstein Pierre , Lang Jian‐Ping
Published: March 2023

We report a unique vinyl coordination polymer (CP), [Zn(4‐Fb)2(tkpvb)]n (1, 4‐HFb=4‐fluorobenzoic acid, tkpvb=1,2,4,5‐tetrakis(4‐pyridylvinyl)benzene) that undergoes a rare photopolymerization reaction to form a two‐dimensional CP integrated with a one‐dimensional linear organic polymer. Upon light irradiation at different wavelengths, 1 exhibits an unprecedented phenomenon of photoinduced nonlinear lattice expansion. 1 can be uniformly dispersed in polyvinyl alcohol (PVA) to form the composite film of 1‐PVA. When this film is exposed to UV light, internal minute stresses within crystallites are released by lattice expansion, resulting in a variety of photopolymerization‐driven macroscopic mechanical motions. The findings provide new insights into the conversion of small lattice expansions of CPs into macroscopic mechanical motions based on photopolymerization reactions, which can promote the development of CPs‐based smart photoactuators in the burgeoning field of microrobotics.
3D Co‐culturing of human neuroblastoma and human oligodendrocytes, emulating native tissue using 3D porous biodegradable liquid crystal elastomers
Authors: Ustunel Senay , Sternbach Sarah , Prévôt Marianne E. , Freeman Ernie J. , McDonough Jennifer A. , Clements Robert J. , Hegmann Elda
Published: March 2023

Biomaterials cover and are an integral part of tissue engineering and regenerative medicine fields. They are crucial to mimic endogenous tissue responses and help to eliminate high research costs and ethical concerns that come with 2D systems and animal models. In this study, we present a co‐culturing system wherein neuroblastoma (SH‐SY5Y) and oligodendrocyte (MO3.13) cell lines grow within both a caprolactone‐based 3D elastomer and liquid crystal elastomer (LCE) scaffolding. We also demonstrate that LCE scaffolds promote maturation and differentiation of both cell lines alone, and in co‐culturing fashion as they provide a suitable 3D in vitro environment to study myelination. Additionally, we validate that these scaffolds are suitable for primary cell growth and proliferation using neurons, oligodendrocyte progenitor cells (OPCs) and astrocytes. Our data suggest that responsive LCE scaffolds can effectively impact cellular function, differentiation, and myelination of co‐cultured cell lines, allowing the mimicry of a more endogenous environment and providing support for long term studies to manipulate cellular crosstalk.
Thiourea‐Based Tritopic Halogen‐Bonding Acceptors
Authors: Happonen Lauri , Mattila Milla , Peshev Ivan , Lehikoinen Arttu , Valkonen Arto
Published: March 2023

A series of thiourea‐based tritopic receptor molecules were synthesized to be used as building blocks for halogen‐bonded assemblies. Here, 16 new receptor molecules were synthesized from two different 2,4,6‐trialkyl‐1,3,5‐tris(bromomethyl)benzene starting materials via tris(isothiocyanatomethyl)benzene intermediates. The alkyl substituents in the benzene ring proved to be important for isothiocyanate group formation instead of competing thiocyanate group. The synthesis route allowed us to synthesize the isothiocyanate intermediates and further the receptor molecules without the typically used and highly toxic thiophosgene. The synthesized receptor molecules were used to study their halogen‐bond acceptor properties with diiodotetrafluorobenzene donors by single‐crystal X‐ray diffraction method. We were able to obtain five new crystal structures of halogen‐bonded complexes, in which all receptors showed two to four accepted C−I⋅⋅⋅S halogen bonds. The observed halogen bonds were highly directional and showed large variation in C=S⋅⋅⋅I acceptor angles, indicating flexible acceptor properties of sulfur.
Entwicklung von Prototypen für Balkone und Loggien aus Infraleichtbeton (ILC) unter Berücksichtigung bauphysikalischer Aspekte und der Anforderungen aus der Fertigung
Authors: Mendgen Anna
Published: March 2023

Im Rahmen des von der DBU (Deutsche Bundesstiftung Umwelt) geförderten Forschungsprojekts ILVO (Vorfabrikation von Fertigteilen aus Infraleichtbeton) wurden 2019–2021 Fertigteile aus ILC für den Geschosswohnungsbau an der TU Berlin entwickelt. Die daraus resultierenden Protoypen wurden 2022–2023 in Form von Modellen in der Ausstellung „Technoscape: The Architecture of Engineers“ (Kuratoren: Maristella Casciato, Pippo Ciorra) im MAXXI Museum in Rom ausgestellt. Das Bauen mit großformatigen Elementen aus Infraleichtbeton (ILC) bietet eine Reihe an Vorteilen gegenüber dem herkömmlichen Bauen mit Wärmedämmverbundsystemen (WDVS). Dies wird im Geschosswohnungsbau insbesondere bei der Konstruktion von Fenstern, Balkonen und Loggien deutlich. Details, die sonst kompliziert und aufwendig sind und gerade im Bereich von Wärmebrücken Probleme aufweisen, können mit Infraleichtbeton neu gedacht werden. Im Folgenden sollen die Vorteile des Bauens mit großformatigen Elementen aus Infraleichtbeton im Geschosswohnungsbau aufgezeigt werden. Darauf aufbauend werden die Grundlagen des Entwurfs, der Konstruktion sowie der Fertigung von großformatigen Elementen aus Infraleichtbeton erklärt und die Entwicklung von drei exemplarischen Prototypen (französischer Balkon, Balkon, Loggia) für den Geschosswohnungsbau erläutert. Weiter wird ein Bezug zum seriellen Bauen im Hochbau und Ingenieurbau hergestellt.
The hydrogen bond between tryptophan and the host molecule induced fluorescence enhancement
Authors: Yang Xi , Xue Ting , Zhao Ran , Liang Han‐Ning , Chen De‐Jun , Yuan Bin , Gu Xun‐Gang , Shen Yong‐Hui , Qin Ling
Published: March 2023

Tryptophan is one of important amino acids in the human body, therefore its detection is particularly important. The 3,5‐bis(4‐pyridyl)‐4‐amino‐1,2,4‐triazole (BPAT) organic molecule was designed to be used as fluorescence detectors to detect tryptophan molecules for the interaction between the host and the guest. BPAT shows good sensitivity and selectivity towards tryptophan compared with other amino acid molecules. The limit of detection obtained from formula 3δ/KSV is considered to be 5.43 × 10−7 mol/L. We speculated that this change is mainly caused by the hydrogen bond between tryptophan and the host molecule BPAT. This conjecture was verified by the controlled experiments with other host molecules.
Leveraging mathematical models for optimizing filter utility at manufacturing scale
Authors: Rose Steven , Dhingra Ashna , Joseph Adrian , Coffman Jon
Published: March 2023

In the production of biopharmaceuticals depth filters followed by sterile filters are often employed to remove residual cell debris present in the feed stream. In the back drop of a global pandemic, supply chains associated with the production of biopharmaceuticals have been constrained. These constraints have limited the available amount of depth filters for the manufacture of biologics. This has placed manufacturing facilities in a difficult position having to choose between running processes with reduced number of depth filters and risking a failed batch or the prospect of plants going into temporary shutdown until the depth filter resources are replenished. This communication describes a modeling based method that leverages manufacturing scale filtration data to predict the depth filter performance with a reduced number of filters and an increased operational flux. This method can be used to quantify the acceptable level of area reduction before which the filtration process performance is affected. This enables facilities to manage their filter inventory avoiding potential plant shutdowns and reduces the risks of negative depth filter performance.
Design, Synthesis and Antitumor Activity of FAK/PLK1 Dual Inhibitors with Quinazolinone as the Skeleton
Authors: Sun Juan , Fang Ze‐Yu , Tao Yi‐Nuo , Zhang Yi‐Heng , Zhang Yao , Sun Hai‐Ya , Zhou Yang , Wu Yuan‐Feng
Published: March 2023

Febrifugine is a kind of quinazolinone compound with high biological activity from a Chinese herb called Chang Shan (Dichroa febrifuga). Febrifugine and its derivatives possess extensive biological activities, some of which exhibited anti‐tumor activities as FAK inhibitors. However, they are not very effective at inhibiting tumor metastasis, perhaps because tumors gain energy through compensatory activation of other signaling pathways that promote cell migration and invasion. Therefore, seventeen novel febrifugine derivatives with quinazolinone skeleton were designed, synthesized and acted as potential FAK/PLK1 dual inhibitors. These compounds were determined by 1H‐NMR, 13C‐NMR and MS. Most of the compounds exhibited good inhibitory activity against cancer cell lines by computer‐assisted screening, antitumor activity test and FAK/PLK1 inhibitory activity test, wherein compound 3b was screened as a high‐efficiency lead compound.
Aqueous Rosa damascena extract: Antibacterial activity and its role of adhesion to human epithelial cells in vitro
Authors: Alsafi Alaa , AlKaabi Siham Jasim
Published: March 2023

The current study aimed to investigate the inhibitory activity of aqueous extracts of different plant parts of Rosa damascena, represented by the whole rose, petals, and calyces, against clinical isolates of Staphylococcus spp., Escherichia coli, and Klebsiella pneumoniae, and the inhibition of the bacterial cell. The isolates were obtained from the advanced microbiology laboratory for postgraduate studies in the Department of Biology, Faculty of Education for Girls. They were isolated from urinary tract infections, which were subsequently subjected to diagnosis by the Vitek‐2 compact system to confirm the type of bacteria as well as their sensitivity to antibiotics. The results obtained included Staphylococcus aureus, Staphylococcus haemolyticus, Staphylococcus lentus, Staphylococcus saprophyticus, E. coli, and K. pneumoniae. A test was conducted to investigate the microbiological inhibitory activity of aqueous plant extracts of the whole rose, petals, and calyces using the well diffusion method and three concentrations of each aqueous extract (25, 50, and 100 mg/ml). The results showed the inhibitory ability of all concentrations of the different extracts toward Staphylococcus spp., and E. coli and K. pneumoniae bacteria were not affected by the different concentrations of the plant extract. The concentration of (100 mg/ml) for the aqueous extract was the most efficient in inhibiting growth compared to the other concentrations. The synergistic effect of three antibiotics was examined (Amoxicillin‐clavulanate 10/20 μg, Piperacillin 100 μg, Trimethoprim‐sulfamethoxazole 23.75/1.25 μg) and for all concentrations of the aqueous plant extract was investigated in both E. coli and K. pneumoniae, as it found a synergistic action between some of the antibiotics and extracts towards inhibiting the growth of the two bacterial isolates Resistance to the plant extract alone. Bacterial isolates showed a significant decrease in the rate of adhesion to epithelial cells isolated from urine samples of healthy women in the presence of the aqueous extract of whole rose, petals, and calyces at their three concentrations compared with the control treatment.