bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tuning Molecular Packing by Twisting Structure to Facilely Construct Highly Efficient Solid‐State Fluorophores for Two‐Photon Bioimaging and Photodynamic Therapy
Authors: Cao Hui , Gao Ya , Wu Bingshun , Zhang Jianyu , Wang Lianke , Wei Peifa , Liu Lijie , Zou Hang , Zhou Hongping , Zheng Zheng , Tang Ben Zhong 
Published: March 2024

AbstractThe traditional design strategy for constructing highly bright solid‐state luminescent materials relies on incorporating aggregation‐induced emission (AIE) scaffolds, molecular rotors, or bulky substituents to prevent close cofacial packing, which limits the strategy diversity in developing new materials. Herein, a strategy of tuning molecular packing by twisting molecular structure of conventional aggregation‐caused quenching fluorophore is proposed to endow materials with AIE effect and enhance the solid‐state fluorescence. Accordingly, a series of 1,4‐bis(diphenylamino)‐2,5‐disubstituted benzene fluorophores exhibiting AIE characteristics, high solid‐state fluorescence efficiency (up to 0.99), wide emission color tunability, and good near‐infrared (NIR) two‐photon absorption is facilely developed. All these luminogens can specifically stain intracellular lipid droplets with a high signal‐to‐noise ratio, high biocompatibility, and good photostability. Besides, the luminogens exhibit effective reactive oxygen species (ROS) generation capability upon low‐power white light irradiation. Among them, the AIE luminogen, named BDBDC, integrating the NIR emission, good NIR two‐photon absorption and strongest ROS generation demonstrates superior performances in two‐photon fluorescence imaging of various tissues and photodynamic cancer therapy. This molecular design philosophy provides a new way of designing highly bright solid‐state fluorophores for practical applications.
Neural Network‐Inspired Polyurea Ionogel with Mechanical Robustness, Low Hysteresis, and High Transparency for Soft Iontronics
Authors: Zhang Zhipeng , Qian Lu , Cheng Jianfeng , Ma Chunfeng , Zhang Guangzhao 
Published: March 2024

AbstractConcurrently achieving mechanical robustness, low hysteresis, and high transparency are essential for ionogels to enhance their reliability and satisfy the requirements in soft electronics. Fabricating ionogels comprising these characteristics presents a considerable challenge. Herein, inspired by the structure of neural networks, a new strategy for in situ formation of dense urea moieties aggregated domains is proposed to achieve topology‐tailoring polyurea ionogels. Initially, leveraging the pronounced disparity in reactivity of the isocyanate (─NCO) groups between isophorone diisocyanate (IPDI) and NCO‐terminated prepolymer (PPGTD), IPDI preferentially reacts with deblocked trifunctional latent curing agents, resulting in the formation of dense urea moieties aggregated domains. Thereafter, these domains are interconnected via PPGTD to establish polymer networks in which the ionic liquid is uniformly dispersed, forming neural networks like ionogels. Attributed to this unique design strategy, the polyurea ionogel demonstrates remarkable properties, including high strength (0.6–2.4 MPa), excellent toughness (0.9–4.3 MJ m−3), low hysteresis (6.6–11.6%), high transparency (>92%), along with enhanced fatigue and puncture resistance. Furthermore, the polyurea ionogels exhibit outstanding versatility, enabling their in strain sensors, flexible electroluminescence devices, and nanogenerators. This strategy contributes to the design of ionogels with unparalleled combinatory properties, catering to the diverse demands of soft iontronics.
Uplifting Antitumor Immunotherapy with Lymph‐Node‐Targeted and Ratio‐Controlled Codelivery of Tumor Cell Lysate and Adjuvant
Authors: Cui Guanhong , Sun Yinping , Qu Liping , Shen Cui , Sun Yu , Meng Fenghua , Zheng Yiran , Zhong Zhiyuan 
Published: March 2024

AbstractCancer vaccines provide a potential strategy to cure patients. Their clinical utilization and efficacy is, however, limited by incomplete coverage of tumor neoantigens and unspecific and restricted activation of dendritic cells (DCs). Tumor cell lysates (TCLs) containing a broad spectrum of neoantigens, while are considered ideal in formulating personalized vaccines, induce generally poor antigen presentation and transient antitumor immune response. Here, intelligent polymersomal nanovaccines (PNVs) that quantitatively coload, efficiently codeliver, and responsively corelease TCL and CpG adjuvant to lymph node (LN) DCs are developed to boost antigen presentation and to induce specific and robust antitumor immunity. PNVs carrying CpG and ovalbumin (OVA) markedly enhance the maturation, antigen presentation, and downstream T cell activation ability of bone‐marrow‐derived dendritic cells and induce strong systemic immune response after tail base injection. Remarkably, PNVs carrying CpG and TCL cure 85% of B16‐F10 melanoma‐bearing mice and generate long‐lasting anticancer immune memory at a low dose, protecting all cured mice from tumor rechallenge. These LN‐directed PNVs being highly versatile and straightforward opens a new door for personalized cancer vaccines.
Biocompatible 2D Materials via Liquid Phase Exfoliation
Authors: He Yilin , Andrade Andrés Felipe , Ménard‐Moyon Cécilia , Bianco Alberto 
Published: March 2024

Abstract2D materials (2DMs), such as graphene, transition metal dichalcogenides (TMDs), and black phosphorus (BP), have been proposed for different types of bioapplications, owing to their unique physicochemical, electrical, optical, and mechanical properties. Liquid phase exfoliation (LPE), as one of the most effective up‐scalable and size‐controllable methods, is becoming the standard process to produce high quantities of various 2DM types as it can benefit from the use of green and biocompatible conditions. The resulting exfoliated layered materials have garnered significant attention because of their biocompatibility and their potential use in biomedicine as new multimodal therapeutics, antimicrobials, and biosensors. This review focuses on the production of LPE‐assisted 2DMs in aqueous solutions with or without the aid of surfactants, bioactive, or non‐natural molecules, providing insights into the possibilities of applications of such materials in the biological and biomedical fields.
Cutting Edge High‐Throughput Synthesis and Characterization Techniques in Combinatorial Materials Science
Authors: Tan Chao , Wu Haijuan , Yang Lei , Wang Zegao 
Published: March 2024

AbstractThe Materials Genome Initiative is expected to accelerate the materials discovery and design by fundamentally changing the trial‐and‐error research paradigm. However, mass data from high‐throughput experiments is still essential for the revelation of rules and verification of theories. In fact, the development of combinatorial materials science is always on the strength of the upgrade and evolution of high‐throughput techniques in each stage, especially high‐throughput materials synthesis and characterization. Herein, this review summarizes the high‐throughput synthesis methods for combinatorial materials libraries, especially the co‐deposition and masking techniques of thin‐film fabrication; and details the high‐throughput characterization methods for specific material properties and typical material categories, which comes down to the spectroscopy and microscopy techniques. It is considered that high‐throughput concepts will be the predominant lab experimentation in the future, along with advanced experimental techniques and convenient data processing procedures. Before that, more cooperation between multiple researchers from different fields should be conducted to complete the combinatorial materials research, since the high‐throughput technology covers multiple disciplines with a huge span.
Topological Flexible 3D Microwave Perfect Absorber
Authors: Lv Wenjing , Li Mengyao , Wang Feng , Qin Haoye , Song Qinghua , Zhu Pengfei , Li Bo 
Published: March 2024

AbstractIn this work, an approach to achieve perfect absorption and microwave absorption enhancement is proposed by combining traditional wave‐absorbing materials with metamaterials. Specifically, an absorbing basement membrane (BM) is integrated with 3D woodpile (WP) photonic crystals, both of which are composed of flexible silicon materials as matrix and carbonyl iron powder (CIP) as absorbent. Direct ink writing (DIW) is used to fabricate the 3D photonic crystals with either single or coupled concentrations of absorbent. Experiments show that the 10‐dB bandwidth of the integrated absorber can reach 10 GHz with a wide elevation angle of incidence. The absorber composed of BM and WP with coupled concentrations of absorbent leads to perfect absorption with a maximum absorption of over 100 dB at an elevation angle of 30°. By changing the concentration of absorbent in BM, the frequency of perfect absorption can be engineered in the range of 6–16 GHz. Such absorption singularity reveals an experimentally observable topological charge that confirms the robustness of the singularity of perfect absorption. The topologically protected flexible 3D microwave absorber offers exceptional performance for versatile scenarios and enriches the studies on topology arising from scattering singularity.
D‐Band Center Regulation for Durable Catalysts and Constructing a Robust Hybrid Layer on Li Anode Enable Long‐Life Li‐O2 Batteries
Authors: Xiao Fenglong , Bao Qingshan , Sun Chaoyang , Li Yanlu , Cui Deliang , Wang Qilong , Dang Feng , Yu Haohai , Lian Gang 
Published: March 2024

AbstractRechargeable Li‐O2 batteries (LOBs) are regarded as promising candidates for the next generation of energy storage devices. One of the major impediments is the poor cycle stability resulting from unreliable cathode catalysts and serious corrosion of Li anode, hindering the commercial application of LOBs. Herein, a synergetic strategy is proposed, including the design of a stable Co3Ru cathode catalyst via d‐band center modulation and the construction of a robust LiF/Sn/Li5Sn2‐PFDTMS hybrid protective layer on Li anode. Theoretical calculations reveal that the negative shift of the d‐band center provides a dominant descriptor for improving the catalysis activity and stability of Ru‐based catalysts. In situ construction of the PFDTMS‐enhanced LiF/Sn/Li5Sn2 hybrid layer possesses excellent mechanical stability and toughness, which can effectively shield the Li anode from corrosive reaction and ensure good Li+ transport. Consequently, the LOBs exhibit a long cycle life of 990 cycles (≈1980 h). This work confers the concept for high‐performance LOBs via rationally constructing stable catalysts and Li anodes.
Nonlinear effects of conservation reserve program rental rates on land enrollment under varying crop price regimes
Authors: Adjei Eugene , Zhang Jingfang , Sawadgo Wendiam , Li Wenying 
Published: March 2024

AbstractWe use a panel smooth transition regression model to investigate the influence of Conservation Reserve Program (CRP) rental rates on land enrollment under different crop price regimes. We employ a flexible estimation technique, allowing the CRP rental rate incentives to vary with crop prices, and construct a Hausman‐type instrumental variable to address endogeneity. Simulations are conducted to assess the impact of varying crop prices on CRP acreage and its associated environmental effects. Results reveal a nonlinear relationship between rental rates and enrollment, with the impact diminishing as crop prices increase. A 10% rise in CRP rental rates corresponds to a 5.1% expansion in enrollment, reducing to 4.2% when crop prices reach a specific threshold. High crop prices lead to fewer acres enrolled, decreased carbon sequestration, increased phosphorus and nitrogen runoff, and increased sediment loss. Our findings highlight the importance of considering price fluctuations in conservation planning as it has significant implications for environmental conservation policies and programs.
Data stewardship in FTLD research: Investigator and research participant views
Authors: Arias Jalayne J. , Tyler Ana M. , Beskow Laura M. , Carillo Maria C. , Dickinson Susan , Goldman Jill , Majumder Mary A. , Mello Michelle M. , Snyder Heather M. , Yokoyama Jennifer S. 
Published: March 2024

AbstractINTRODUCTIONFederal policies and guidelines have expanded the return of individual results to participants and expectations for data sharing between investigators and through repositories. Here, we report investigators’ and study participants’ views and experiences with data stewardship practices within frontotemporal lobal degeneration (FTLD) research, which reveal unique ethical challenges.METHODSSemi‐structured interviews with (1) investigators conducting FTLD research that includes genetic data collection and/or analysis and (2) participants enrolled in a single site longitudinal FTLD study.RESULTSAnalysis of the interviews identified three meta themes: perspectives on data sharing, experiences with enrollment and participation, and data management and security as mechanisms for participant protections.DISCUSSIONThis study identified a set of preliminary gaps and needs regarding data stewardship within FTLD research. The results offer initial insights on ethical challenges to data stewardship aimed at informing future guidelines and policies.
Asymmetric Total Synthesis and Structural Revision of DAT2, an Antigenic Glycolipid from Mycobacterium tuberculosis
Authors: Lin Zonghao , Kaniraj Jeya Prathap , Holzheimer Mira , Nigou Jérôme , Gilleron Martine , Hekelaar Johan , Minnaard Adriaan J. 
Published: March 2024

AbstractDAT2 is a member of the diacyl trehalose family (DAT) of antigenic glycolipids located in the mycomembrane of Mycobacterium tuberculosis (Mtb). Recently it was shown that the molecular structure of DAT2 had been incorrectly assigned, but the correct structure remained elusive. Herein, the correct molecular structure of DAT2 and its methyl‐branched acyl substituent mycolipanolic acid is determined. For this, four different stereoisomers of mycolipanolic acid were prepared in a stereoselective and unified manner, and incorporated into DAT2. A rigorous comparison of the four isomers to the DAT isolated from Mtb H37Rv by NMR, HPLC, GC, and mass spectrometry allowed a structural revision of mycolipanolic acid and DAT2. Activation of the macrophage inducible Ca2+‐dependent lectin receptor (Mincle) with all four stereoisomers shows that the natural stereochemistry of mycolipanolic acid / DAT2 provides the strongest activation, which indicates its high antigenicity and potential application in serodiagnostics and vaccine adjuvants.
Precise Modulation of Circularly Polarized Luminescence via Polymer Chiral Co‐assembly and Contactless Dynamic Chiral Communication
Authors: Zhang Gong , Bao Yinglong , Ma Haotian , Wang Nianwei , Cheng Xiaoxiao , He Zixiang , Wang Xiang , Miao Tengfei , Zhang Wei 
Published: March 2024

AbstractCircularly polarized luminescence (CPL) plays a pivotal role in cutting‐edge display and information technologies. Currently achieving precise color control and dynamic signal regulation in CPL still remains challenging due to the elusory relationship between fluorescence and chirality. Inspired by the natural mechanisms governing color formation and chiral interaction, we proposed an addition‐subtraction principle theory to address this issue. Three fluorene‐based polymers synthesized by Suzuki polycondensation with different electron‐deficient monomers exhibit similar structures and UV/Vis absorption, but distinct fluorescence emissions due to intramolecular charge transfer. Based on this, precise‐color CPL‐active films are obtained through quantitative supramolecular co‐assembly directed by addition principle. Particularly, an ideal white‐emitting CPL film (CIE coordinates: (0.33, 0.33)) is facilely fabricated with a high quantum yield of 80.8 % and a dissymmetry factor (glum) of 1.4×10−2. Structural analysis reveals that the ordered stacking orientation favors higher glum. Furthermore, to address the dynamically regulated challenge, the comparable subtraction principle is proposed, involving a contactless chiral communication between excited and ground states. The representative system consisting of as‐prepared fluorene‐based polymers and chirality‐selective absorption azobenzene (Azo)‐containing polymers is constructed, achieving CPL weakening, reversal, and enhancement. Finally, a switchable quick response code is realized based on trans‐cis isomerization of Azo moiety.
Lowering Entropic Barriers in Triplex DNA Switches Facilitating Biomedical Applications at Physiological pH
Authors: Lei Yanli , Li Chuangchuang , Ji Xinyue , Sun Haiyan , Liu Xiaowen , Mao Zenghui , Chen Weiju , Qing Zhihe , Liu Juewen 
Published: March 2024

AbstractTriplex DNA switches are attractive allosteric tools for engineering smart nanodevices, but their poor triplex‐forming capacity at physiological conditions limited the practical applications. To address this challenge, we proposed a low‐entropy barrier design to facilitate triplex formation by introducing a hairpin duplex linker into the triplex motif, and the resulting triplex switch was termed as CTNSds. Compared to the conventional clamp‐like triplex switch, CTNSds increased the triplex‐forming ratio from 30 % to 91 % at pH 7.4 and stabilized the triple‐helix structure in FBS and cell lysate. CTNSds was also less sensitive to free‐energy disturbances, such as lengthening linkers or mismatches in the triple‐helix stem. The CTNSds design was utilized to reversibly isolate CTCs from whole blood, achieving high capture efficiencies (>86 %) at pH 7.4 and release efficiencies (>80 %) at pH 8.0. Our approach broadens the potential applications of DNA switches‐based switchable nanodevices, showing great promise in biosensing and biomedicine.
Regulated Dual Defects of Bridging Organic and Terminal Inorganic Ligands in Iron‐based Metal‐Organic Framework Nodes for Efficient Photocatalytic Ammonia Synthesis
Authors: Wang Xiaosong , Fan Guilan , Guo Shoujun , Gao Rong , Guo Yan , Han Chenhui , Gao Yuliang , Zhang Jiangwei , Gu Xiaojun , Wu Limin 
Published: March 2024

AbstractEngineering advantageous defects to construct well‐defined active sites in catalysts is promising but challenging to achieve efficient photocatalytic NH3 synthesis from N2 and H2O due to the chemical inertness of N2 molecule. Here, we report defective Fe‐based metal‐organic framework (MOF) photocatalysts via a non‐thermal plasma‐assisted synthesis strategy, where their NH3 production capability is synergistically regulated by two types of defects, namely, bridging organic ligands and terminal inorganic ligands (OH− and H2O). Specially, the optimized MIL‐100(Fe) catalysts, where there are only terminal inorganic ligand defects and coexistence of dual defects, exhibit the respective 1.7‐ and 7.7‐fold activity enhancement comparable to the pristine catalyst under visible light irradiation. As revealed by experimental and theoretical calculation results, the dual defects in the catalyst induce the formation of abundant and highly accessible coordinatively unsaturated Fe active sites and synergistically optimize their geometric and electronic structures, which favors the injection of more d‐orbital electrons in Fe sites into the N2 π* antibonding orbital to achieve N2 activation and the formation of a key intermediate *NNH in the reaction. This work provides a guidance on the rational design and accurate construction of porous catalysts with precise defective structures for high‐performance activation of catalytic molecules.
Dynamic Chalcogen Squares for Material and Topological Control over Macromolecules
Authors: Bui Aaron H. , Fernando Pulle Anne D. , Micallef Aaron S. , Lessard Jacob J. , Tuten Bryan T. 
Published: March 2024

AbstractHerein we introduce chalcogen squares via selenadiazole motifs as a new class of dynamic supramolecular bonding interactions for the modification and control of soft matter materials. We showcase selenadiazole motifs in supramolecular networks of varying primary chain length prepared through polymerization using tandem step‐growth/Passerini multicomponent reactions (MCRs). Compared to controls lacking the selenadiazole motif, these networks display increased glass transition temperatures and moduli due to the chalcogen bonding linkages formed between chains. These elastomeric networks were shown to autonomously heal at room temperature, retaining up to 83 % of the ultimate tensile strength. Lastly, we use post‐polymerization modification via the Biginelli MCR to add selenadiazole motifs to narrowly dispersed polymers for controlled topology in solution. Chalcogen squares via selenadiazoles introduce an exciting exchange mechanism to the realm of dynamic materials.
Designing Degradable Polymers from Tricycloalkenes via Complete Cascade Metathesis Polymerization
Authors: Yang Yongkang , Cho Yunhyeong , Choi Tae‐Lim 
Published: March 2024

AbstractCascade metathesis polymerization has been developed as a promising method to synthesize complex but well‐defined polymers from monomers containing multiple reactive functional groups. However, this approach has been limited to the monomers involving simple alkene/alkyne moieties or produced mainly non‐degradable polymers. In this study, we demonstrate a complete cascade ring‐opening/ring‐closing metathesis polymerization (RORCMP) using various tricycloalkenes and two strategies for the efficient degradation. Through rational design of tricycloalkene monomers, the structure and reactivity relationship was explored. For example, tricycloalkenes with trans configuration in the central ring enabled faster and better selective cascade RORCMP than the corresponding cis isomers. Also, a 4‐substituted cyclopentene moiety in the monomers significantly enhanced the overall cascade RORCMP performance, with the maximum turnover number (TON) reaching almost 10,000 and molecular weight up to 170 kg/mol using an amide‐containing monomer. Furthermore, we achieved one‐shot cascade multiple olefin metathesis polymerization using tricycloalkenes and a diacrylate, to produce new highly A,B‐alternating copolymers with full degradability. Lastly, we successfully designed xylose‐based tricycloalkenes to give well‐defined polymers that underwent ultra‐fast and complete degradation under mild conditions.
The Cranium I: Neurocranium
Authors: Pantoja‐Pérez Ana , Arsuaga Juan‐Luis 
Published: March 2024

AbstractThe Sima de los Huesos (SH) site has provided a significant collection of hominin remains, including numerous cranial fragments, which have contributed to our understanding of the MP human population. The taxonomic classification of the SH hominins remains a topic of debate, with some studies suggesting a close relationship to Neandertals based on nuclear DNA analysis. The cranial morphology of the SH specimens exhibits a mix of Neandertal‐like features and primitive traits observed in earlier Homo populations, providing insights into the evolutionary pattern of the Neanderthal lineage. This study focuses on the neurocranial traits of the SH population and describes three previously undescribed cranial individuals. The SH cranial collection now comprises 20 nearly complete crania, representing approximately two‐thirds of the estimated population size. The analysis of the SH population reveals variations in robustness, frontal torus development, sagittal keeling, and occipital torus morphology, which may be related to sexual dimorphism and ontogenetic factors. The suprainiac region exhibits notable ontogenetic changes, while suture obliteration patterns do not strictly correlate with dental age. Metric measurements, particularly cranial breadths, highlight significant intrapopulation variation within the SH sample. Compared with other Middle Pleistocene (MP) hominins, the SH cranial vault displays archaic characteristics but differs from Homo erectus and Neandertals. The SH individuals have relatively short and tall cranial vaults, distinguishing them from other MP fossils. These findings contribute to our understanding of the MP human populations and their evolutionary trajectories.