bluuebunny/crossref_metadata_2025 huggingface dataset:
Paysage linguistique dans l’espace public frontalier : entre Brésil et Guyane
française
Authors: Nascimento Day Kelly Cristina , Távora de Mendonça Mileny
Published: May 2023

Cet article s’inscrit dans un projet de recherche sociolinguistique portant sur le
paysage linguistique de la frontière franco-brésilienne. Il présente une étude des pratiques
langagières qui caractérisent le paysage linguistique de cette frontière en tant que
mécanismes de gestion des usages linguistiques entre Oiapoque et Saint-Georges. Les études
menées dans ce domaine ont montré que le paysage linguistique structure l’espace et dicte
les normes de participation et d’exclusion de celui-ci. Dans ce sens, on cherche à
comprendre les relations socioculturelles et linguistiques à partir d’un corpus d’images qui
révèle les pratiques langagières nées des relations socioéconomiques et culturelles
frontalières. La recherche permet de comprendre comment le paysage linguistique reflète les
conflits et les relations de pouvoir entre les unités politiques adjacentes, soit par
rapport à la confrontation des langues majoritaires entre elles (portugais et français),
soit par rapport aux langues les moins prestigieuses (khéuol, créole guyanais, kalinã,
etc.).
A theory of hippocampal theta correlations accounting for extrinsic and intrinsic sequences
Authors: Yiu Yuk-Hoi , Leibold Christian
Published: May 2023

Hippocampal place cell sequences have been hypothesized to serve as diverse purposes as the induction of synaptic plasticity, formation and consolidation of long-term memories, or navigation and planning. During spatial behaviors of rodents, sequential firing of place cells at the theta timescale (known as theta sequences) encodes running trajectories, which can be considered as one-dimensional behavioral sequences of traversed locations. In a two-dimensional space, however, each single location can be visited along arbitrary one-dimensional running trajectories. Thus, a place cell will generally take part in multiple different theta sequences, raising questions about how this two-dimensional topology can be reconciled with the idea of hippocampal sequences underlying memory of (one-dimensional) episodes. Here, we propose a computational model of cornu ammonis 3 (CA3) and dentate gyrus (DG), where sensorimotor input drives the direction-dependent (extrinsic) theta sequences within CA3 reflecting the two-dimensional spatial topology, whereas the intrahippocampal CA3-DG projections concurrently produce intrinsic sequences that are independent of the specific running trajectory. Consistent with experimental data, intrinsic theta sequences are less prominent, but can nevertheless be detected during theta activity, thereby serving as running-direction independent landmark cues. We hypothesize that the intrinsic sequences largely reflect replay and preplay activity during non-theta states.
Histone variants shape the chromatin states in Arabidopsis
Authors: Jamge Bhagyshree , Lorković Zdravko J. , Axelsson Elin , Osakabe Akihisa , Shukla Vikas , Yelagandula Ramesh , Akimcheva Svetlana , Kuehn Annika Luisa , Berger Frédéric
Published: May 2023

How different intrinsic sequence variation or regulatory modifications of histones regulate nucleosome interactions with transcription remain unclear. To clarify this question, we examine how histone variants and histone modifications assemble in the
Arabidopsis thaliana
genome, and show that a limited number of chromatin states divide euchromatin and heterochromatin into biologically significant subdomains. We find that histone variants are as significant as histone modifications in determining the composition of chromatin states. Loss of function of the chromatin remodeler DECREASED IN DNA METHYLATION (DDM1) prevents the exchange of the histone variant H2A.Z to H2A.W and impacts the definition and distribution of chromatin states. In the mutant deprived of DDM1 transposons harbor chromatin states normally found only on proteins coding genes in the wild type. We propose that the dynamics of histone variant exchange control the organization of histone modifications into chromatin states, resulting in molecular landmarks that signify whether genes could be transcribed.
Inhibitory CCK+ basket synapse defects in mouse models of dystroglycanopathy
Authors: Jahncke Jennifer N , Miller Daniel S , Krush Milana , Schnell Eric , Wright Kevin M
Published: May 2023

Dystroglycan (Dag1) is a transmembrane glycoprotein that links the extracellular matrix to the actin cytoskeleton. Mutations in Dag1 or the genes required for its glycosylation result in dystroglycanopathy, a type of congenital muscular dystrophy characterized by a wide range of phenotypes including muscle weakness, brain defects, and cognitive impairment. We investigated interneuron (IN) development, synaptic function, and associated seizure susceptibility in multiple mouse models that reflect the wide phenotypic range of dystroglycanopathy neuropathology. Mice that model severe dystroglycanopathy due to forebrain deletion of Dag1 or Pomt2, which is required for Dystroglycan glycosylation, show significant impairment of CCK+/CB1R+ IN development. CCK+/CB1R+ IN axons failed to properly target the somatodendritic compartment of pyramidal neurons in the hippocampus, resulting in synaptic defects and increased seizure susceptibility. Mice lacking the intracellular domain of Dystroglycan have milder defects in CCK+/CB1R+ IN axon targeting, but exhibit dramatic changes in inhibitory synaptic function, indicating a critical postsynaptic role of this domain. In contrast, CCK+/CB1R+ IN synaptic function and seizure susceptibility was normal in mice that model mild dystroglycanopathy due to partially reduced Dystroglycan glycosylation. Collectively, these data show that inhibitory synaptic defects and elevated seizure susceptibility are hallmarks of severe dystroglycanopathy, and show that Dystroglycan plays an important role in organizing functional inhibitory synapse assembly.
Presión de la regulación ambiental de los negocios de alfarería y su influencia en comportamiento ambiental de los dueños
Authors: Avendaño-Rito María del Carmen , Toledo-López Arcelia , Cruz Dora Lilia Guzmán
Published: May 2023

El objetivo de este estudio es analizar cómo la presión de las normas de regulación ambiental afecta el comportamiento ambiental de los negocios de alfarería. Se utilizó una metodología cuantitativa, para recolectar los datos, se aplicó un cuestionario estructurado a 80 dueños de negocios de alfarería vidriada en Oaxaca y Guadalajara. Mediante una correlación bivariada de Pearson se encontró una relación negativa entre el comportamiento y la regulación ambiental, por medio de un análisis de regresión lineal también se encontró que la regulación ambiental afecta negativa y significativamente el comportamiento ambiental de los dueños de negocios de alfarería. Con este estudio se concluye que la presión coercitiva del gobierno afecta el comportamiento ambiental en negocios de alfarería, ya que las inspecciones frecuentes de las autoridades para dar seguimiento a la implementación de normas ambientales y de salud influyen para que los dueños se nieguen a participar de forma activa en los programas y sólo las cumplen de forma parcial sin conseguir modificar el comportamiento en pro del ambiente.
Referral and resolution of breastfeeding consultancy in a joint accommodation unit / Encaminhamento e resolutividade da consultoria de aleitamento materno em uma unidade de alojamento conjunto
Authors: Betti Thais , Gasparin Vanessa Aparecida , Strada Juliana Karine Rodrigues , Moraes Bruna Alibio , Espírito Santo Lilian Cordova do
Published: May 2023

Objetivo: caracterizar os encaminhamentos e a resolutividade da consultoria em aleitamento materno em uma unidade de alojamento conjunto. Método: estudo transversal descritivo realizado com 231 puérperas e seus recém-nascidos internados em alojamento conjunto no sul do Brasil. A coleta de dados foi realizada no período de agosto de 2016 a maio de 2017. Os dados foram analisados mediante estatística descritiva. Resultados: os motivos prevalentes para o encaminhamento foram dificuldade na técnica de amamentação (81,7%), primiparidade (57,8%), anatomia mamária (28,7%), presença de fissuras mamilares (19,6%) e dor ao amamentar (18,3%). A satisfação com o atendimento foi relatada por 97,8% das puérperas. Quanto a resolutividade, 70,6% considerou o atendimento totalmente resolutivo, 26,4% parcialmente e 3,0% não resolutivo. Conclusão: a consultoria em aleitamento materno foi resolutiva na maioria dos encaminhamentos, motivados por dificuldades que poderiam predispor uma interrupção precoce da amamentação, demonstrando a eficácia da inserção desse profissional nos serviços de saúde.
Incidence of Primary End Point Changes Among Active Cancer Phase 3 Randomized Clinical Trials
Authors: Florez Marcus A. , Jaoude Joseph Abi , Patel Roshal R. , Kouzy Ramez , Lin Timothy A. , De Brian , Beck Esther J. , Taniguchi Cullen M. , Minsky Bruce D. , Fuller Clifton D. , Lee J. Jack , Kupferman Michael , Raghav Kanwal P. , Overman Michael J. , Thomas Charles R. , Ludmir Ethan B.
Published: May 2023

Importance

Primary end point (PEP) changes to an active clinical trial raise questions regarding trial quality and the risk of outcome reporting bias. It is unknown how the frequency and transparency of the reported changes depend on reporting method and whether the PEP changes are associated with trial positivity (ie, the trial met the prespecified statistical threshold for PEP positivity).

Objectives

To assess the frequency of reported PEP changes in oncology randomized clinical trials (RCTs) and whether these changes are associated with trial positivity.

Design, Setting, and Participants

This cross-sectional study used publicly available data for complete oncology phase 3 RCTs registered in ClinicalTrials.gov from inception through February 2020.

Main Outcomes and Measures

The main outcome was change between the initial PEP and the final reported PEP, assessed using 3 methods: (1) history of tracked changes on ClinicalTrials.gov, (2) self-reported changes noted in the article, and (3) changes reported within the protocol, including all available protocol documents. Logistic regression analyses were performed to evaluate whether PEP changes were associated with US Food and Drug Administration approval or trial positivity.

Results

Of 755 included trials, 145 (19.2%) had PEP changes found by at least 1 of the 3 detection methods. Of the 145 trials with PEP changes, 102 (70.3%) did not have PEP changes disclosed within the manuscript. There was significant variability in rates of PEP detection by each method (χ2 = 72.1; P < .001). Across all methods, PEP changes were detected at higher rates when multiple versions of the protocol (47 of 148 [31.8%]) were available compared with 1 version (22 of 134 [16.4%]) or no protocol (76 of 473 [16.1%]) (χ2 = 18.7; P < .001). Multivariable analysis demonstrated that PEP changes were associated with trial positivity (odds ratio, 1.86; 95% CI, 1.25-2.82; P = .003).

Conclusions and Relevance

This cross-sectional study revealed substantial rates of PEP changes among active RCTs; PEP changes were markedly underreported in published articles and mostly occurred after reported study completion dates. Significant discrepancies in the rate of detected PEP changes call into question the role of increased protocol transparency and completeness in identifying key changes occurring in active trials.
Uterus‐Derived Decellularized Extracellular Matrix‐Mediated Endometrial Regeneration and Fertility Enhancement
Authors: Ahn Jungho , Sen Tugce , Lee Danbi , Kim Hyeonji , Lee Jae Yeon , Koo Hwa Seon , Kim Jae Yun , Kim Jisoo , Jang Jinah , Kang Youn‐Jung , Cho Dong‐Woo
Published: May 2023

Tissue‐specific decellularized extracellular matrix recapitulates the complexity of natural ECMs, creating an organ‐specific microenvironment based on its intrinsic characteristics. Here, hydrogels containing uterus‐derived decellularized extracellular matrix (UdECMs) from the endometrium‐specific layer or the entire uterus are developed. UdECMs serve as effective organ‐specific biomaterials, displaying that intrauterine UdECM administration induces endometrial regeneration and fertility enhancement. Moreover, UdECM administration alters the profile of natural killer cell subpopulations to exhibit more mature and less cytotoxic features, providing a favorable uterine environment for successful implantation and decidualization. Interestingly, insulin‐like growth factor 1 and insulin‐like growth factor‐binding protein 3 as key regulatory factors that contribute to UdECM‐mediated endometrial regeneration are discovered. Furthermore, ex vivo culture of human uterine tissues reveals that UdECMs of different origins exhibit distinct therapeutic effects based on the endometrial conditions of patients, suggesting their uses as a therapeutic intervention providing personalized regenerative medicine for infertile patients with a poor uterine environment.
Liquid‐Metal‐Assisted Programmed Galvanic Engineering of Core–shell Nanohybrids for Microwave Absorption
Authors: Zhao Biao , Du Yiqian , Lv Hualiang , Yan Zhikai , Jian Hua , Chen Guanyu , Wu Yuyang , Fan Bingbing , Zhang Jincang , Wu Limin , Zhang David Wei , Che Renchao
Published: May 2023

Core–shell nanostructures have received widespread attention because of their potential usage in various technological and scientific fields. However, they still face significant challenges in terms of fabrication of core–shell nanostructure libraries on a controlled, and even programmed scale. This study proposes a general approach to systematically fabricate core–shell nanohybrids using liquid‐metal Ga alloys as reconfigurable templates, and the initiation of a local galvanic replacement reaction is demonstrated utilizing an ultrasonic system. Under ultrasonic agitation, the hydrated gallium oxides generated on the liquid metal droplets, simultaneously delaminated themselves from the interfaces. Subsequently, single‐metal or bimetallic components are deposited on fresh smooth Ga‐based alloys via galvanic reactions to form unique core–shell metal/metal nanohybrids. Controlled and quantitative regulation of the diversity of the non‐homogeneous nanoparticle shell layer composition is achieved. The obtained core–shell nanostructures are used as efficient microwave absorbers to dissipate unwanted electromagnetic wave pollution. The effective absorption bands (90% absorption) of core–shell GaNi and GaCoNi nanohybrids are 3.92 and 3.8 GHz at a thickness of 1.4 mm, respectively. This general and advanced strategy enables the growth of other oxides or sulfides by spontaneous interfacial redox reactions for the fabrication of functional materials in the future.
Anion Receptor Weakens ClO4− Solvation for High‐Temperature Sodium‐Ion Batteries
Authors: Zhou Xunzhu , Chen Xiaomin , Yang Zhuo , Liu Xiaohao , Hao Zhiqiang , Jin Song , Zhang Longhai , Wang Rui , Zhang Chaofeng , Li Lin , Tan Xin , Chou Shu‐Lei
Published: May 2023

Sodium‐ion batteries (SIBs) with wide operating temperature are regarded as promising candidates for large‐scale energy storage systems. However, SIBs operating under elevated temperature aggravate the electrolyte decomposition with unstable cathode‐electrolyte interphase (CEI), causing a rapid capacity degradation. Herein, anion receptor tris(pentafluorophenyl)borane (TPFPB) is selected as electrolyte additive to construct robust NaF‐rich CEI. The strong interactions between anion and TPFPB via the electron‐deficient boron atoms weaken ClO4− solvation and promote the coordination capability between solvents and Na+ cations, demonstrating greatly improved oxidative stability. Na3V2(PO4)3 cathode in TPFPB‐containing electrolyte delivers long‐term stability with a capacity retention of 86.9% after 100 cycles at a high cut‐off voltage of 4.2 V (vs. Na+/Na) and a high temperature of 60 °C. Besides, TPFPB also works well with enhanced performance over a temperature range from −30 to 60 °C. This study proposes a prospective method by manipulating the solvation chemistry for constructing high‐temperature rechargeable SIBs.
Heterogeneous Nanosized Metal (Metallic Compound)@Metal‐Organic Framework Composites: Recent Advances in the Preparation and Applications
Authors: Cui Yang , Zhao Yujie , Wu Jie , Hou Hongwei
Published: May 2023

Metal‐organic framework (MOF) composites based on MOFs‐wrapped metals or metallic compounds (denoted as M/MC@MOFs) are an important class of materials that integrate M/MCs and MOFs. MOFs can fix and confine M/MCs to regulate their size, prevent uncontrollable aggregation, and enhance the exposure and ordered arrangement of active sites. In turn, M/MCs support the MOFs to enhance their stability and realize more targeted properties. In this review, the features and application scope of different M/MC@MOF synthesis methods are explored, considering the influential factors and regulation modes of the M/MC–MOFs integration. Additionally, the performances of the M/MC@MOF composites are comprehensively discussed, and the underlying mechanisms are clarified. The performance of M/MC@MOFs is dependent on the orderly synergy between the MOFs and M/MCs. MOFs can sieve and transfer specific molecules to the M/MC surface, whereas the robust interface provides new charge/energy‐transfer pathways, which enhance the activity and selectivity of the composites for diverse molecules. Furthermore, the challenges facing this field are analyzed, and the recommendations for advancing the development of M/MC@MOF composites are presented.
Natural Targeting Potent ROS‐Eliminating Tungsten‐Based Polyoxometalate Nanodots for Efficient Treatment of Pulmonary Hypertension
Authors: Liu Hong , Wang Shuya , Chen Qiaohui , Ge Xiaoyue , Ning Huang , Guo Yanzi , Wang Di , Ai Kelong , Hu Changping
Published: May 2023

Pulmonary hypertension (PH) is a disease of pulmonary artery stenosis and blockage caused by abnormal pulmonary artery smooth muscle cells (PASMCs), with high morbidity and mortality. High levels of reactive oxygen species (ROS) in pulmonary arteries play a crucial role in inducing phenotypic switch and abnormal proliferation of PASMCs. However, antioxidants are rarely approved for the treatment of PH because of a lack of targeting and low bioavailability. In this study, the presence of an enhanced permeability and retention effect (EPR)‐like effect in the pulmonary arteries of PH is revealed by tissue transmission electron microscopy (TEM). Subsequently, for the first time, tungsten‐based polyoxometalate nanodots (WNDs) are developed with potent elimination of multiple ROS for efficient treatment of PH thanks to the high proportion of reduced W5+. WNDs are effectively enriched in the pulmonary artery by intravenous injection because of the EPR‐like effect of PH, and significantly prevent the abnormal proliferation of PASMCs, greatly improve the remodeling of pulmonary arteries, and ultimately improve right heart function. In conclusion, this work provides a novel and effective solution to the dilemma of targeting ROS for the treatment of PH.
Lipid Nanoparticle (LNP) Enables mRNA Delivery for Cancer Therapy
Authors: Zong Yan , Lin Yi , Wei Tuo , Cheng Qiang
Published: May 2023

Messenger RNA (mRNA) has received great attention in the prevention and treatment of various diseases due to the success of coronavirus disease 2019 (COVID‐19) mRNA vaccines (Comirnaty and Spikevax). To meet the therapeutic purpose, it is required that mRNA must enter the target cells and express sufficient proteins. Therefore, the development of effective delivery systems is necessary and crucial. Lipid nanoparticle (LNP) represents a remarkable vehicle that has indeed accelerated mRNA applications in humans, as several mRNA‐based therapies have already been approved or are in clinical trials. In this review, the focus is on mRNA‐LNP‐mediated anticancer therapy. It summarizes the main development strategies of mRNA‐LNP formulations, discusses representative therapeutic approaches in cancer, and points out current challenges and possible future directions of this research field. It is hoped that these delivered messages can help further improve the application of mRNA‐LNP technology in cancer therapy.
Designer Adhesives for Tough and Durable Interfaces in High‐Performance Ti‐Carbon PEKK Hybrid Joints
Authors: Kafkopoulos Georgios , Marinosci Vanessa M. , Duvigneau Joost , Grouve Wouter J. B. , Wijskamp Sebastiaan , de Rooij Matthijn B. , Vancso G. Julius , Akkerman Remko
Published: May 2023

Advanced high‐performance structural applications require the right materials in the right place and suitable interface engineering. However, poor adhesion in harsh environmental conditions frequently challenge material interfaces. An example is the moisture sensitivity of titanium‐poly ether ketone ketone (PEKK) interfaces. Here, this work offers a high‐performance composite adhesive system, which combines strong adhesion and high interfacial toughness, particularly when used in metal‐polymer bonding. This system includes aminopropyl triethoxy silane (APTES)–polydopamine (SiPDA) layers, which can be formed on the titanium surface before the joining process with carbon fiber‐reinforced PEKK (C/PEKK). Adhesion between PEKK and titanium is evaluated before and after hot/wet conditioning using mandrel peel tests. This work discovers that applying thin SiPDA layers not only results in a remarkable rise in the interfacial fracture toughness but also provides durable bond stability after hot/wet conditioning. These findings indicate that polydopamine‐based coatings show great potential to achieve stable interfaces for the next generation of high‐performance metal‐polymer hybrid materials.
Suppression of Oxygen Vacancies in Rutile Ruo2 via In Situ Exsolution for Enhanced Water Electrocatalysis
Authors: Zhang Yudi , Wang Yan , Sun Wen , Ma Dandan , Ma Jinfu , Rao Jiancun , Xu Qiunan , Huo Juntao , Liu Jian , Li Guowei
Published: May 2023

Elemental vacancies are proposed as an effective approach to tuning the electronic structure of catalysts that are critical for energy conversion. However, for reactions such as the sluggish oxygen evolution reaction, the excess of oxygen vacancies (VO) is inevitable and detrimental to catalysts’ electrochemical stability and activities, e.g., in the most active RuO2. While significant work is carried out to hinder the formation of VO, the development of a fast and efficient strategy is limited. Herein, a protection SrO layer produced successfully at the surface of RuO2 with the in situ exsolution method with perovskite SrRuO3 as the precatalyst, which could significantly hinder the generation of VO. Benefited from the suppression of VO, the surface‐modified RuO2 requires a low overpotential of 290 mV at 100 mA cm−2, accompanied by remarkably high electrochemical stability (100 h) and Faraday efficiency (≈100%). Theoretical investigation reveals that the formation energy of VO in RuO2 is almost doubled in the exsolved RuO2 phase as a result of the weakened RuO bond covalency. This work not only provides insight into the structural evolution of perovskite oxide catalysts but also demonstrates the feasibility of controlling vacancy formation via in situ exsolution.
Optical Gain Switching by Thermo‐Responsive Light‐Emitting Nanofibers through Moisture Sorption Swelling
Authors: Archimi Matteo , Schoolaert Ella , Becelaere Jana , Hoogenboom Richard , Camposeo Andrea , De Clerck Karen , Pisignano Dario
Published: May 2023

The development of intelligent photonic systems made of stimuli‐responsive materials, i.e., with features tunable and switchable by environmental signals, is gaining increasing attention. Here, the study reports on switchable optical gain based on complex arrays of nanofibers made of thermo‐responsive poly(2‐n‐propyl‐2‐oxazoline), incorporating a blue‐emitting chromophore. The fluorescent component endows the nanofibers with optical gain in addition to the moisture absorption capability of the polymer. Light amplification is found with temperature‐ and humidity‐dependent excitation threshold. The threshold value is halved close to the polymer cloud point temperature, enabling reversible switching of the emission intensity upon temperature change. Waveguiding analysis by back‐focal plane imaging on individual fibers allows the switching mechanisms to be rationalized, in terms of moisture sorption swelling‐induced morphological changes. These responsive light‐emitting nanofibers may find application in a novel class of lasers with dynamically‐controlled properties, environmentally‐switchable optoelectronics, and smart sensors.
Composition‐Dependent High‐Performance Phototransistors Based on Solution Processed CH3NH3PbI3/ZnO Heterostructures
Authors: Haque Farjana , Hasan Md Mehedi , Bestelink Eva , Sporea Radu A. , Mativenga Mallory
Published: May 2023

Recently, hybrid organic−inorganic perovskites have emerged as promising photo‐sensing materials for next‐generation solution‐processed phototransistors, achieving high responsivity, detectivity, and fast response. Here, a phototransistor that can detect visible light using a low‐cost, solution processed methylammonium lead iodide/zinc oxide (CH3NH3PbI3/ZnO) heterostructure is reported. While typical ZnO thin‐film transistors (TFTs) do not show any photocurrent under visible light illumination, CH3NH3PbI3 (MAPbI3) coated ZnO TFTs exhibit substantial photocurrent. Additionally, the optical, morphological, and structural characteristics of the light‐absorbing layers are further controlled by altering the precursor ratio of methylammonium iodide and lead (II) iodide (MAI:PbI2), which in turn affects the photosensitivity. Stoichiometric composition (MAI:PbI2 = 1:1) of MAPbI3 demonstrates optimal characteristics with a responsivity of 234 A/W and a high detectivity of 3.74 × 1013 Jones under white light illumination. The high photo‐responsivity and detectivity result from the combination of the suitable optoelectronic properties of the stoichiometric MAPbI3 film and its smooth interface with the ZnO channel.
Mn2+ as an “Optical Energy Shutter” to Regulate Red‐to‐NIR Luminescence in Rare Earth Doped Layered Quadruple Perovskites
Authors: Yang Wei , Dang Peipei , Zhang Guodong , Lian Hongzhou , Cheng Ziyong , Li Guogang , Lin Jun
Published: May 2023

Metal halide perovskites (MHPs) have shown great application prospects in the field of optoelectronics owing to their superior optical and optoelectronic properties. Bandgap engineering and impurity doping are effective ways to achieve regulation of luminous properties in the visible light region. However, realizing efficient deep red and wide‐range tunable near‐infrared (NIR) emission remains a challenge. Here, a series of rare earth (RE3+) ions (RE = Nd, Dy, Ho, Er, Tm, Yb) doped Cs4Cd1−xMnxSb2Cl12 (0 ≤ x ≤ 1) quadruple perovskites are designed. An efficient tunable luminescence from red to NIR light is achieved based on the energy transfer (ET) from Mn2+ to RE3+ by building the Mn2+ energy bridge, which covers the NIR‐I (650–900 nm) and NIR‐II (900–1700 nm) regions. Moreover, the ET efficiency is availably influenced by the doping concentration of Mn2+. Interestingly, the energy bridge from Mn2+ to RE3+ is cut off because of the increased bandgap when Bi3+ is introduced into the RE3+‐doped Cs4Cd0.4Mn0.6Sb2−yBiyCl12 (0 ≤ y ≤ 2) lattice. Through bandgap engineering, the ET from Mn2+ to RE3+ resembles an “optical energy shutter” which quenches the NIR emission of RE3+ owing to the mismatched energy level but enhances the emission of Mn2+.
Na3SiS3F: A Wide Bandgap Fluorothiosilicate with Unique [SiS3F] Unit and High Laser‐Induced Damage Threshold
Authors: Zhou Jiazheng , Wang Linan , Chu Yu , Wang Hongshan , Pan Shilie , Li Junjie
Published: May 2023

The exploration of antilaser damage wide bandgap infrared (IR) nonlinear optical (NLO) materials is urgent but challenging. Herein, by introducing the idea of fluorination into chalcogenides, a wide bandgap IR NLO material Na3SiS3F with unprecedented [SiS3F] tetrahedra is designed and synthesized. Na3SiS3F shows a wide bandgap of 4.75 eV (the largest one in the reported quaternary metal chalcogenides), resulting in a high laser damage induced threshold of ≈5 × AgGaS2(AGS). Meanwhile, the compound has a moderate NLO response (≈0.3 ×AGS) with phase‐matching behavior, large birefringence (0.15@1064 nm), and wide IR transparent region. The introduction of fluorine breaks the structural symmetry and broadens the highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO‐LUMO) gap, polarizability anisotropy, and hyperpolarizability of the Si–S tetrahedral unit. The results indicate that Na3SiS3F is a promising IR NLO material for the high‐power laser application and open an avenue for the design of new wide bandgap IR NLO materials based on NLO‐active [SiSxF4−x] (x = 1, 2, 3) mixed anionic tetrahedral group.
Towards Automatic Design of Reflective Optical Systems
Authors: Liu Xinyu , Zhu Jun
Published: May 2023

Traditional optical design processes can only obtain a few design solutions after a time‐consuming trial‐and‐error process. During this process, how to select the numbers and sequence of surfaces of different types (spherical, aspherical, and freeform) required by the system remains a difficult problem. Currently, no automatic design method is available for reflective optical systems that contain multiple surface types. Therefore, an automatic design framework for reflective systems is proposed that can output a series of design results with various combinations of surface types automatically after input specifications and constraints. In the first design example, 76 design results with imaging qualities near the diffraction limit are obtained that have 11 different surface type combinations. This framework realizes the automatic design of this type of system, paving the way toward general automatic optical design and significantly improving the efficiency of the optical design process. Using this framework, the numbers and sequence of the surfaces of different types required by the optical system can be determined reasonably, solving a difficult problem that has long puzzled designers. The proposed framework reduces the requirement for design experience and allows more people to participate in optical design processes.
Ultrafast Jahn‐Teller Photoswitching in Cobalt Single‐Ion Magnets
Authors: Canton Sophie E. , Biednov Mykola , Pápai Mátyás , Lima Frederico A. , Choi Tae‐Kyu , Otte Florian , Jiang Yifeng , Frankenberger Paul , Knoll Martin , Zalden Peter , Gawelda Wojciech , Rahaman Ahibur , Møller Klaus B. , Milne Christopher , Gosztola David J. , Zheng Kaibo , Retegan Marius , Khakhulin Dmitry
Published: May 2023

Single‐ion magnets (SIMs) constitute the ultimate size limit in the quest for miniaturizing magnetic materials. Several bottlenecks currently hindering breakthroughs in quantum information and communication technologies could be alleviated by new generations of SIMs displaying multifunctionality. Here, ultrafast optical absorption spectroscopy and X‐ray emission spectroscopy are employed to track the photoinduced spin‐state switching of the prototypical complex [Co(terpy)2]2+ (terpy = 2,2′:6′,2″‐terpyridine) in solution phase. The combined measurements and their analysis supported by density functional theory (DFT), time‐dependent‐DFT (TD‐DFT) and multireference quantum chemistry calculations reveal that the complex undergoes a spin‐state transition from a tetragonally elongated doublet state to a tetragonally compressed quartet state on the femtosecond timescale, i.e., it sustains ultrafast Jahn‐Teller (JT) photoswitching between two different spin multiplicities. Adding new Co‐based complexes as possible contenders in the search for JT photoswitching SIMs will greatly widen the possibilities for implementing magnetic multifunctionality and eventually controlling ultrafast magnetization with optical photons.
A Curcumin‐Modified Coordination Polymers with ROS Scavenging and Macrophage Phenotype Regulating Properties for Efficient Ulcerative Colitis Treatment
Authors: Yao Hang , Wang Feifei , Chong Hui , Wang Jingjing , Bai Yang , Du Meng , Yuan Xiaohui , Yang Xiaofei , Wu Ming , Li Yuping , Pang Huan
Published: May 2023

Overexpression of classically activated macrophages (M1) subtypes and assessed reactive oxygen species (ROS) levels are often observed in patients with ulcerative colitis. At present, the treatment system of these two problems has yet to be established. Here, the chemotherapy drug curcumin (CCM) is decorated with Prussian blue analogs in a straightforward and cost‐saving manner. Modified CCM can be released in inflammatory tissue (acidic environment), eventually causing M1 macrophages to transform into M2 macrophages and inhibiting pro‐inflammatory factors. Co(III) and Fe(II) have abundant valence variations, and the lower REDOX potential in CCM‐CoFe PBA enables ROS clearance through multi‐nanomase activity. In addition, CCM‐CoFe PBA effectively alleviated the symptoms of UC mice induced by DSS and inhibited the progression of the disease. Therefore, the present material may be used as a new therapeutic agent for UC.
Unidirectional Moisture Delivery via a Janus Photothermal Interface for Indoor Dehumidification: A Smart Roof
Authors: Shi Wenbo , Bai Haoyu , Cao Moyuan , Wang Xinsheng , Ning Yuzhen , Li Zhe , Liu Kesong , Jiang Lei
Published: May 2023

Rational control of the humidity in specific environments plays an important role in green building, equipment protection, etc. A smart apparatus that can actively expel inner moisture and largely prevent outer liquid penetration can be highly desirable. Through the integration of the Janus interface with unidirectional liquid manipulation and the solar evaporating layer, here, a Janus solar dehumidifying interface (JSDI) is designed for the switchable moisture management of an indoor environment. By covering with the JSDI roof, the continuous elimination of inner water is achieved via outward condensate delivery and solar evaporation on sunny days. On rainy days, JSDI with a hydrophobic lower surface can largely hamper inward liquid leakage and then spontaneously drain the accumulated water via a siphoning structure. The real‐world water evaporation rate via the JSDI is ≈0.38 kg m−2 h−1 on an autumn day, showing a promising function of in situ moisture expelling. In addition, the JSDI is made of natural materials that are easy to scale up with a cost of four dollars per square meter. It is envisioned that the JSDI may meet the wide requirements of indoor dehumidification and update the understanding of the integration of Janus interfaces and solar steam generation.
A High Utilization and Environmentally Sustainable All‐Organic Aqueous Zinc‐Ion Battery Enabled by a Molecular Architecture Design
Authors: Yang Jin , Hua Haiming , Yang Huiya , Lai Pengbin , Zhang Minghao , Lv Zeheng , Wen Zhipeng , Li Cheng Chao , Zhao Jinbao , Yang Yang
Published: May 2023

Despite their safe and cost‐effective merits, the cycling durability of aqueous zinc–organic batteries is hindered by cathode dissolution and low coulombic efficiency of Zn metal anodes. Herein, a Zn metal‐free all‐organic zinc‐ion battery (ZIB) is proposed by using quinoxalino[2,3‐i]diquinoxalino[2′,3′:6,7]quinoxalino[2,3‐a:2,3‐c] phenazine (QDPA) cathode coupled with a 1,4,5,8‐Naphthalenetetracarboxylic diimide (NPI) anode, rendering excellent electrochemical reversibility with high utilization. Based on the molecular architecture strategy, a QDPA cathode with an enlarged aromatic ring system is designed and synthesized, which not only effectively inhibits structural collapse during cycling but also enhances the working voltage without lowering the active group ratio. Moreover, theoretical calculations and experimental results confirm the rapid H+ storage mechanism in the CN active sites of QDPA, affording ultra‐fast electrochemical kinetics. Thus, it delivers a negligible capacity decay of 0.002% up to 13 000 cycles at 20 A g−1. Moreover, the QDPA//NPI all‐organic aqueous ZIB with a high energy density of 43.1 Wh kg−1 is demonstrated to be easily disassembled and recycled by the incineration treatment after battery failure, ensuring outstanding environmental sustainability.
Tailoring Interfacial Chemistry of Defective Carbon‐Supported Ru Catalyst Toward Efficient and CO‐Tolerant Alkaline Hydrogen Oxidation Reaction
Authors: Yang Zhilong , Lai Wenchuan , He Bingling , Wang Jian , Yu Feifan , Liu Qinghua , Liu Maochang , Zhang Shiguo , Ding Wei , Lin Zhiqun , Huang Hongwen
Published: May 2023

The ability to create highly active and CO‐tolerant platinum‐free catalysts toward alkaline hydrogen oxidation reaction (HOR) represents a significant endeavor to enable commercialization of alkaline fuel cells. This, however, remains a grand challenge. Herein, a robust defective‐carbon‐supported Ru catalyst (denoted as Ru@C) is crafted to achieve efficient and CO‐tolerant HOR in alkaline media via delicately tailoring interfacial chemistry of catalyst. Notably, the degree of defects in the carbon support is the key to tune the interface chemistry. An integrated experimental and density functional theory calculations study demonstrates that the favorable interfacial chemical interaction between Ru and carbon support controlled by the covalently bonded Ru─O─C redistributes the d electrons of Ru and downshiftsits d‐band center, which in turn weakens the hydrogen adsorption and suppresses the Ru 4d→CO 2π* back donation. Consequently, the optimized Ru@C catalyst renders a 6.6‐fold enhancement in mass activity (@25 mV) for alkaline HOR over the conventional Ru/C counterpart, which also outperforms the state‐of‐the‐art catalysts. Intriguingly, the catalyst can tolerate 20 000 ppm CO, far exceeding that of commercial Pt/C and PtRu/C catalysts. This work elucidates the correlation between precisely tailored interfacial chemistry and HOR performance, and is expected to further enlighten the design of advanced catalysts.
Toward More Efficient Organic Solar Cells: A Detailed Study of Loss Pathway and Its Impact on Overall Device Performance in Low‐Offset Organic Solar Cells
Authors: Sun Bowen , Tokmoldin Nurlan , Alqahtani Obaid , Patterson Acacia , De Castro Catherine S. P. , Riley Drew B. , Pranav Manasi , Armin Ardalan , Laquai Frédéric , Collins Brian A. , Neher Dieter , Shoaee Safa
Published: May 2023

Low‐offset organic solar cell systems have attracted great interest since nonfullerene acceptors came into the picture. While numerous studies have focused on the charge generation process in these low‐offset systems, only a few studies have focused on the details of each loss channel in the charge generation process and their impact on the overall device performance. Here, several nonfullerene acceptors are blended with the same polymer donor to form a series of low‐offset organic solar cell systems where significant variation in device performance is observed. Through detailed analyses of loss pathways, it is found that: i) the donor:acceptor interfaces of PM6:Y6 and PM6:TPT10 are close to the optimum energetic condition, ii) energetics at the donor:acceptor interface are the most important factor to the overall device performance, iii) exciton dissociation yield can be field‐dependent owing to the sufficiently small energetic offset at the donor:acceptor interface, and iv) the change in substituents in the terminal group of Y‐series acceptors in this work mainly affects energetics at the donor:acceptor interface instead of the interface density in the active layer. In general, this work presents a path toward more efficient organic solar cells.
Expanding the genetic spectrum of ALKU syndrome: Compound heterozygosity for two deleterious variants in SMG8 gene
Authors: Fernandes André Aires , Grangeia Ana , Dias Leonor , Guimarães Joana
Published: May 2023

Alzahrani–Kuwahara syndrome (ALKUS) is a neurodevelopmental disorder that includes microcephaly, facial dysmorphism, and variable congenital and eye malformations. We present the first case of ALKUS described in the European population caused by two variants in compound heterozygosity of the gene SMG8. We present a patient with two variants in compound heterozygosity in the SMG8 gene identified by in trio whole exome sequencing based in next generation sequencing (xGEN® Exome Research Panel, Nextseq550 platform). International case reporting (CARE) criteria were followed. Patient written consent was obtained through legal responsible persons. We describe a 27‐year‐old male, the second child of a healthy and non‐consanguineous couple, whose genetic analysis showed two variants in compound heterozygosity, c.1159C > T (p.Arg387*) and c.2407del (p.Arg803Glyfs*10), in the SMG8 gene, both classified as likely pathogenic. As described by Fatema Alzahrani et al. in a series of eight patients, our patient had global developmental delay with impaired intellectual development, facial dysmorphism, and limb disproportion. Additionally, our patient had lower limb spastic paraparesis, marked osteotendinous hyperreflexia with extensor plantar response bilaterally and paretic gait. Our patient resembles the phenotype described by Fatema Alzahrani et al., however, he is the first patient with two SMG8 deleterious variants in compound heterozygosity, and the first to exhibit pyramidal signs and gait disorder as part of the phenotype.
Stochastic Simulation of Controlled Radical Polymerization Forming Dendritic Hyperbranched Polymers
Authors: Tosaka Masatoshi , Takeuchi Hinako , Kibune Masato , Tong Tianxiang , Zhu Nanyi , Yamago Shigeru
Published: May 2023

Stochastic simulation of the formation process of hyperbranched polymers (HBPs) based on the reversible deactivation radical polymerization (RDRP) using a branch‐inducing monomer, evolmer, has been carried out. The simulation program successfully reproduced the change of dispersities (Đs) during the polymerization process. Furthermore, the simulation suggested that the observed Đs (=1.5–2) are due to the distribution of the number of branches instead of undesired side reactions, and that the branch structures are well controlled. In addition, the analysis of the polymer structure reveals that the majority of HBPs have structures close to the ideal one. The simulation also suggested the slight dependence of branch density on molecular weight, which was experimentally confirmed by synthesizing HBPs with an evolmer having phenyl group.
Carrier Protein Mediated Formation of the Dihydropyridazinone Ring in Actinopyridazinone Biosynthesis
Authors: Arima Kuga , Akiyama Satoko , Shin‐ya Kazuo , Matsuda Kenichi , Wakimoto Toshiyuki
Published: May 2023

Heterocycles with nitrogen‐nitrogen (N−N) bonds are privileged building blocks of synthetic drugs. They are also found in natural products, although the biosynthetic logic behind them is poorly understood. Actinopyridazinones produced by Streptomyces sp. MSD090630SC‐05 possess unique dihydropyridazinone rings that have been studied as core nuclei in several approved synthetic therapeutics. Herein, we performed gene knockouts and in vitro biochemical experiments to elucidate the major steps in actinopyridazinone biosynthesis, including the unprecedented carrier protein mediated machinery for dihydropyridazinone formation.
Synthesis of Polyethyleneimines from the Manganese‐Catalysed Coupling of Ethylene Glycol and Ethylenediamine
Authors: Brodie Claire N. , Owen Aniekan E. , Kolb Julian S. , Bühl Michael , Kumar Amit
Published: May 2023

Polyethyleneimines find many applications in products such as detergents, adhesives, cosmetics, and for processes such as tissue culture, gene therapy, and CO2 capture. The current state‐of‐the‐art technology for the production of the branched polyethyleneimines involves aziridine feedstock which is a highly toxic, volatile and mutagenic chemical and raises significant concern to human health and environment. We report here a novel method for the synthesis of branched polyethyleneimine derivative from ethylene glycol and ethylenediamine which are much safer, environmentally benign, commercially available and potentially renewable feedstock. The polymerisation reaction is catalysed by a complex of an earth‐abundant metal, manganese and liberates H2O as the only by‐product. Our mechanistic studies using a combination of DFT computation and experiment suggest that the reaction proceeds by the formation and subsequent hydrogenation of imine intermediates.
A Thiazole‐linked Covalent Organic Framework for Lithium‐Sulphur Batteries
Authors: Yan Rui , Mishra Bikash , Traxler Michael , Roeser Jérôme , Chaoui Nicolas , Kumbhakar Bidhan , Schmidt Johannes , Li Shuang , Thomas Arne , Pachfule Pradip
Published: May 2023

Lithium‐sulphur (Li−S) batteries are a promising alternative power source, as they can provide a higher energy density than current lithium‐ion batteries. Porous materials are often used as cathode materials as they can act as a host for sulphur in such batteries. Recently, covalent organic frameworks (COFs) have also been used, however they typically suffer from stability issues, resulting in limited and thus insufficient durability under practical conditions and applications. Herein, we report the synthesis of a crystalline and porous imine‐linked triazine‐based dimethoxybenzo‐dithiophene functionalized COF (TTT‐DMTD) incorporating high‐density redox sites. The imine linkages were further post‐synthetically transformed to yield a robust thiazole‐linked COF (THZ‐DMTD) by utilizing a sulphur‐assisted chemical conversion method, while maintaining the crystallinity. As a synergistic effect of its high crystallinity, porosity and the presence of redox‐active moieties, the thiazole‐linked THZ‐DMTD exhibited a high capacity and long‐term stability (642 mAh g−1 at 1.0 C; 78.9 % capacity retention after 200 cycles) when applied as a cathode material in a Li−S battery.
Reinforcing effect of cross baffles on mass transfer process in raceway photobioreactors
Authors: Fu Shuangcheng , Zhang Xiang , Dou Bin , Zhou Faqi , Dai Chaolei , Ling Jie , Zhang Yue , Yan Shenghu
Published: May 2023

Adding baffles inside raceway photobioreactors is a method to strengthen mixing. In this paper, a new type of staggered baffles are designed and compared with other structural baffles. Computational fluid dynamics was used to analyze the mixing effect of baffles with different structures in the raceway photobioreactors. The light–dark cycle of the staggered baffles was analyzed by coupling the motion trajectories of dynamical proton model particles through the change of outdoor light intensity during the day. The light–dark cycle of the cross baffle was analyzed according to the change of outdoor light intensity during the daytime coupled with the motion curve of dynamical proton model particles. The mixing ability of the staggered baffles was verified by mixing time, mass transfer coefficient, and outdoor cultivation. The results show that when the speed of the paddlewheel reached 20 rpm, compared with the raceway photobioreactors without baffles, vorticity increased by 23.3% respectively; the light–dark cycle period reduced by 18%; the mixing time reduced by 40%, and the mass transfer coefficient increased by 9.67%, the biomass of Chlorella increased by 25.3%. Compared with the other two baffle structures, the light–dark cycle period was reduced by 7.3% and 5.9%, the mixing time was reduced by 15% and 8%, and the mass transfer coefficient was increased by 1.17% and 3.59%. The biomass increased by 8.3% and 4.8%. The staggered baffles have better mass transfer performance, which can provide a reference for the optimal design of raceway photobioreactors.