bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intracellular Construction of Cathepsin B‐Guided Gadolinium Nanoparticles for Enhanced T2‐Weighted MR Tumor Imaging
Authors: Wei Mengxing , Wang Lulu , Wang Yanfang , Zhang Tong , Wang Chenchen , Wu Chengfan , Tian Changlin , Liang Gaolin , Yuan Yue 
Published: April 2023

AbstractMagnetic resonance imaging (MRI) is a superior and noninvasive imaging technique with unlimited tissue penetration depth and superb spatiotemporal resolution, however, using intracellular self‐assembly of Gd‐containing nanoparticles to enhance the T2‐weighted MR contrast of cancer cells in vivo for precise tumor MRI is rarely reported. The lysosomal cysteine protease cathepsin B (CTSB) is regarded as an attractive biomarker for the early diagnosis of cancers and metastasis. Herein, taking advantage of a biocompatible condensation reaction, a “smart” Gd‐based CTSB‐responsive small molecular contrast agent VC‐Gd‐CBT is developed, which can self‐assemble into large intracellular Gd‐containing nanoparticles by glutathione reduction and CTSB cleavage to enhance the T2‐weighted MR contrast of CTSB‐overexpressing MDA‐MB‐231 cells at 9.4 T. In vivo T2‐weighted MRI studies using MDA‐MB‐231 murine xenografts show that the T2‐weighted MR contrast change of tumors in VC‐Gd‐CBT‐injected mice is distinctly larger than the mice injected with the commercial agent gadopentetate dimeglumine, or co‐injected with CTSB inhibitor and VC‐Gd‐CBT, indicating that the accumulation of self‐assembled Gd‐containing nanoparticles at tumor sites effectively enhances the T2‐weighted MR tumor imaging. Hence, this CTSB‐targeted small molecule VC‐Gd‐CBT has the potential to be employed as a T2 contrast agent for the clinical diagnosis of cancers at an early stage.
Metastable Polymorphic Phases in Monolayer TaTe2
Authors: Di Bernardo Iolanda , Ripoll‐Sau Joan , Silva‐Guillén Jose Angel , Calleja Fabian , Ayani Cosme G. , Miranda Rodolfo , Canadell Enric , Garnica Manuela , Vázquez de Parga Amadeo L. 
Published: April 2023

AbstractPolymorphic phases and collective phenomena—such as charge density waves (CDWs)—in transition metal dichalcogenides (TMDs) dictate the physical and electronic properties of the material. Most TMDs naturally occur in a single given phase, but the fine‐tuning of growth conditions via methods such as molecular beam epitaxy (MBE) allows to unlock otherwise inaccessible polymorphic structures. Exploring and understanding the morphological and electronic properties of new phases of TMDs is an essential step to enable their exploitation in technological applications. Here, scanning tunneling microscopy (STM) is used to map MBE‐grown monolayer (ML) TaTe2. This work reports the first observation of the 1H polymorphic phase, coexisting with the 1T, and demonstrates that their relative coverage can be controlled by adjusting synthesis parameters. Several superperiodic structures, compatible with CDWs, are observed to coexist on the 1T phase. Finally, this work provides theoretical insight on the delicate balance between Te…Te and Ta–Ta interactions that dictates the stability of the different phases. The findings demonstrate that TaTe2 is an ideal platform to investigate competing interactions, and indicate that accurate tuning of growth conditions is key to accessing metastable states in TMDs.
Spatial Specific Janus S‐Scheme Photocatalyst with Enhanced H2O2 Production Performance
Authors: Xia Chunhong , Yuan Ling , Song Hao , Zhang Chaoqi , Li Zimeng , Zou Yingying , Li Jiaxin , Bao Tong , Yu Chengzhong , Liu Chao 
Published: April 2023

AbstractPhotocatalytic oxygen reduction reaction (ORR) for H2O2 production in the absence of sacrificing agents is a green approach and of great significance, where the design of photocatalysts with high performance is the central task. Herein, a spatial specific S‐scheme heterojunction design by introducing a novel semiconducting pair with a S‐scheme mechanism in a purpose‐designed Janus core–shell‐structured hollow morphology is reported. In this design, TiO2 nanocrystals are grown inside the inner wall of resorcinol‐formaldehyde (RF) resin hollow nanocakes with a reverse bumpy ball morphology (TiO2@RF). The S‐scheme heterojunction preserves the high redox ability of the TiO2 and RF pair, the spatial specific Janus design enhances the charge separation, promotes active site exposure, and reduces the H2O2 decomposition to a large extent. The TiO2@RF photocatalyst shows a high H2O2 yield of 66.6 mM g−1 h−1 and solar‐to‐chemical conversion efficiency of 1.11%, superior to another Janus structure (RF@TiO2) with the same heterojunction but a reversed Janus spatial arrangement, and most reported photocatalysts under similar reaction conditions. The work has paved the way toward the design of next‐generation photocatalysts for green synthesis of H2O2 production.
Harnessing Hafnium‐Based Nanomaterials for Cancer Diagnosis and Therapy
Authors: Ding Shuaishuai , Chen Lei , Liao Jing , Huo Qing , Wang Qiang , Tian Gan , Yin Wenyan 
Published: April 2023

AbstractWith the rapid development of nanotechnology and nanomedicine, there are great interests in employing nanomaterials to improve the efficiency of disease diagnosis and treatment. The clinical translation of hafnium oxide (HfO2), commercially namedas NBTXR3, as a new kind of nanoradiosensitizer for radiotherapy (RT) of cancers has aroused extensive interest in researches on Hf‐based nanomaterials for biomedical application. In the past 20 years, Hf‐based nanomaterials have emerged as potential and important nanomedicine for computed tomography (CT)‐involved bioimaging and RT‐associated cancer treatment due to their excellent electronic structures and intrinsic physiochemical properties. In this review, a bibliometric analysis method is employed to summarize the progress on the synthesis technology of various Hf‐based nanomaterials, including HfO2, HfO2‐based compounds, and Hf‐organic ligand coordination hybrids, such as metal‐organic frameworks or nanoscaled coordination polymers. Moreover, current states in the application of Hf‐based CT‐involved contrasts for tissue imaging or cancer diagnosis are reviewed in detail. Importantly, the recent advances in Hf‐based nanomaterials‐mediated radiosensitization and synergistic RT with other current mainstream treatments are also generalized. Finally, current challenges and future perspectives of Hf‐based nanomaterials with a view to maximize their great potential in the research of translational medicine are also discussed.
Boosting Thermal and Mechanical Properties: Achieving High‐Safety Separator Chemically Bonded with Nano TiN Particles for High Performance Lithium‐Ion Batteries
Authors: Zhao Qian , Wu Xiulong , Li Shenghu , Zheng Qiaotian , Jiang Shuai , Xu Ye , He Bin , Ma Ling , Luo Yangtong , Wang Yujue , Cen Wanglai , Meng Yan , Xiao Dan 
Published: April 2023

AbstractCurrently, the commercial separator (Celgard2500) of lithium‐ion batteries (LIBs) suffers from poor electrolyte affinity, mechanical property and thermal stability, which seriously affect the electrochemical performances and safety of LIBs. Here, the composite separators named PVDF‐HFP/TiN for high‐safety LIBs are synthesized. The integration of PVDF‐HFP and TiN forms porous structure with a uniform and rich organic framework. TiN significantly improves the adsorption between PVDF‐HFP and electrolyte, causing a higher electrolyte absorption rate (192%). Meanwhile, XPS results further demonstrate the tight link between PVDF‐HFP and TiN due to the existence of TiF bond in PVDF‐HFP/TiN, resulting in a strong impediment for the puncture of lithium dendrites as a result of the improved mechanical strengths. And PVDF‐HFP/TiN can effectively suppress the growth of lithium dendrites by means of uniform lithium flux. In addition, the excellent heat resistance of TiN improves the thermal stability of PVDF‐HFP/TiN. As a result, the LiFePO4||Li cells assembled PVDF‐HFP/TiN‐12 exhibit excellent specific capacity, rate performance, and capacity retention rate. Even the high specific capacity of 153 mAh g−1 can be obtained at the high temperature of 80 °C. Meaningfully, a reliable modification strategy for the preparation of separators with high safety and electrochemical performance in LIBs is provided.
Calcium Phosphate‐Based Nanoformulation Selectively Abolishes Phenytoin Resistance in Epileptic Neurons for Ceasing Seizures
Authors: Guan Qiwen , Wang Xuan , Cao Danfeng , Li Menghuan , Luo Zhong , Mao Xiaoyuan 
Published: April 2023

AbstractPhenytoin (PHT) is a first‐line antiepileptic drug in clinics, which could decrease neuronal bioelectric activity by blocking the voltage‐operated sodium channels. However, the intrinsically low blood–brain‐barrier (BBB)‐crossing capability of PHT and upregulated expression level of the efflux transporter p‐glycoprotein (P‐gp) coded by the gene Abcb1 in epileptic neurons limit its efficacy in vivo. Herein, a nanointegrated strategy to overcome PHT resistance mechanisms for enhanced antiepileptic efficacy is reported. Specifically, PHT is first incorporated into calcium phosphate (CaP) nanoparticles through biomineralization, followed by the surface modification of the PEGylated BBB‐penetrating TAT peptide. The CaP@PHT‐PEG‐TAT nanoformulation could effectively cross the BBB to be taken in by epileptic neurons. Afterward, the acidic lysosomal environment would trigger their complete degradation to release Ca2+ and PHT into the cytosol. Ca2+ ions would inhibit mitochondrial oxidative phosphorylation to reverse cellular hypoxia to block hypoxia‐inducible factor‐1α (Hif1α)‐Abcb1‐axis, as well as disrupt adenosine triphosphate generation, leading to simultaneous suppression of the expression and drug efflux capacity of P‐gp to enhance PHT retention. This study offers an approach for effective therapeutic intervention against drug‐resistant epilepsy.
Optimized Solid Electrolyte Interphase and Solvation Structure of Potassium Ions in Carbonate Electrolytes for High‐Performance Potassium Metal Batteries
Authors: Jiang Yong , Lu Shangying , Jiang Jinlong , Li Meng , Liao Yalan , Xu Yi , Huang Shoushuang , Zhao Bing , Zhang Jiujun 
Published: April 2023

AbstractThe introduction of electrolyte additives is one of the most potential strategies to improve the performance of potassium metal batteries (PMBs). However, designing an additive that can alter the K+ solvation shell and essentially inhibit K dendrite remains a challenge. Herein, the amyl‐triphenyl‐phosphonium bromide was introduced as an additive to build a stable solid electrolyte interphase layer. The amyl‐TPP cations can form a cation shielding layer on the metal surface during the nucleation stage, preventing K+ from gathering at the tip to form K dendrites. Besides, the cations can be preferentially reduced to form KxPy with fast K+ transport kinetics. The Br− anions, as Lewis bases with strong electronegativity, can not only coordinate the Lewis acid pentafluoride to inhibit the formation of HF, but also change the K+ solvation structure to reduce solvent molecules in the first solvation structure. Therefore, the symmetrical battery exhibits a low deposition overpotential of 123 mV at 0.1 mA cm−2 over 4200 h cycle life. The full battery, paried with a perylene‐tetracarboxylic dianhydride (PTCDA) cathode, possesses a cycle life of 250 cycles at 2 C and 81.9% capacity retention. This work offers a reasonable electrolyte design to obtain PMBs with long‐term stablity and safety.
Carbon Nanotube‐Reinforced Dual Carbon Stress‐Buffering for Highly Stable Silicon Anode Material in Lithium‐Ion Battery
Authors: Fan Xiaoming , Cai Ting , Wang Shuying , Yang Zeheng , Zhang Weixin 
Published: April 2023

AbstractSilicon (Si) anode suffers from huge volume expansion which causes poor structural stability in terms of electrode material, solid electrolyte interface, and electrode, limiting its practical application in high‐energy‐density lithium‐ion batteries. Rationally designing architectures to optimize the stress distribution of Si/carbon (Si/C) composites has been proven to be effective in enhancing their structural stability and cycling stability, but this remains a big challenge. Here, metal‐organic frameworks (ZIF‐67)‐derived carbon nanotube‐reinforced carbon framework is employed as an outer protective layer to encapsulate the inner carbon‐coated Si nanoparticles (Si@C@CNTs), which features dual carbon stress‐buffering to enhance the structural stability of Si/C composite and prolong their cycling lifetime. Finite element simulation proves the structural advantage of dual carbon stress‐buffering through significantly relieving stress concentration when Si lithiation. The outer carbon framework also accelerates the charge transfer efficiency during charging/discharging by the improvement of lithium‐ion diffusion and electron transport. As a result, the Si@C@CNTs electrode exhibits excellent long‐term lifetime and good rate capability, showing a specific capacity of 680 mAh g−1 even at a high rate of 1 A g−1 after 1000 cycles. This work provides insight into the design of robust architectures for Si/C composites by stress optimization.
Size‐Defined Ru Nanoclusters Supported by TiO2 Nanotubes Enable Low‐Concentration Nitrate Electroreduction to Ammonia with Suppressed Hydrogen Evolution
Authors: Qiu Wenxi , Xie Minghao , Wang Pengfei , Gao Taotao , Li Ran , Xiao Dan , Jin Zhaoyu , Li Panpan 
Published: April 2023

AbstractAnthropogenic nitrate pollution has an adverse impact on the environment and human health. As part of a sustainable nitrate management strategy, electrochemical denitrification is studied as an innovative strategy for nutrients recycling and recovering. It is, however, challenging to selectively electro‐reduce nitrate with low‐concentration for ammonia. Herein, the photo‐deposition of size‐defined Ru nanoclusters (NCs, average size: ≈1.66 nm) on TiO2 nanotubes (NTs) is demonstrated, which show improved performance for nitrate‐to‐ammonia electroreduction with a maximum yield rate of ≈600 µg h−1 cm−2 and a faradic efficiency (FE) of > 90.0% across a broad range of potentials in comparison with electrodeposited Ru nanoparticles (NPs, average size: ≈23.78 nm) on TiO2 NTs. Experimental and theoretical evidence further suggests the small‐size Ru NCs with the intrinsically enhanced selectivity and activity because of the strong metal/substrate interaction and unsaturated coordination state. The findings highlight the size effect on Ru‐based catalyst supported on metal oxides, a versatile catalytic model, which allows the regulation of hydrogen adsorption to favor ammonia production over the competing hydrogen evolution reaction.
A Bipyridyl Covalent Organic Framework with Coordinated Cu(I) for Membrane C3H6/C3H8 Separation
Authors: Cheng Zeliang , Zhang Pinyue , Wang Ziyang , Jiang Haicheng , Wang Wenjian , Liu Dandan , Wang Lina , Zhu Guangshan , Zou Xiaoqin 
Published: April 2023

AbstractCovalent organic frameworks (COFs) mixed matrix membranes (MMMs) combining individual attributes of COFs and polymers are promising for gas separation. However, applying COF MMMs for propylene/propane (C3H6/C3H8) separation remains a big challenge due to COF inert pores and C3H6/C3H8 similar molecular sizes. Herein, the designed synthesis of a Cu(I) coordinated COF for membrane C3H6/C3H8 separation is reported. A platform COF is synthesized from 5,5′‐diamino‐2,2′‐bipyridine and 2‐hydroxybenzene‐1,3,5‐tricarbaldehyde. This COF possesses a porous 2D structure with high crystallinity. Cu(I) is coordinated to bipyridyl moieties in the COF framework, acting as recognizable sites for C3H6 gas, as shown by the adsorption measurements. Cu(I) COF is blended with 6FDA‐DAM polymer to yield MMMs. This COF MMM exhibits selective and permeable separation of C3H6 from C3H8 (C3H6 permeability of 44.7 barrer, C3H6/C3H8 selectivity of 28.1). The high porosity and Cu(I) species contribute to the great improvement of separation performance by virtue of 2.3‐fold increase in permeability and 2.2‐fold increase in selectivity compared to pure 6FDA‐DAM. The superior performance to those of most relevant reported MMMs demonstrates that the Cu(I) coordinated COF is an excellent candidate material for C3H6 separation membranes.
Asymmetric Swelling Behaviors of High‐Energy‐Density Lithium‐Ion Batteries with a SiOx/Graphite Composite Anode
Authors: Zhen Huijuan , Meng Fanhui , Gao Jinhui , Liu Yibo , Liu Xizheng 
Published: April 2023

AbstractThe battery swelling originated from the electrode swelling is a big obstacle for the practical application of high‐energy‐density lithium‐ion batteries (HED‐LIBs). Herein, the HED‐LIBs are constructed by SiOx/graphite composite anode and LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode and their swelling behaviors are investigated at the cell, electrode, and particle scales. there are three expansion stages during the charging while one expansion followed by two contraction stages during the discharging process. The expansion ratio is in direct proportion to the ratio of SiOx content and about 10 times larger than that of the cathode. A 100 nm thick double‐layer solid electrolyte interface, comprises LiF, Li2O, and Li2CO3, forms on the surface of the SiOx particles, and evolves into a 300 nm thick triple‐layer after cycling. The performance degradation of HED‐LIBs is associated with the expansion of anodes, increase in resistance, and consumption of Li in the anodes during cycling. This study is expected to guide the future selection and design of HED‐LIBs and battery packs.
Structural Transformation by Crystal Engineering Endows Aqueous Zinc‐Ion Batteries with Ultra‐long Cyclability
Authors: Wang Kangning , Wang Jianwei , Chen Peiming , Qin Mengran , Yang Chunming , Zhang Wenlin , Zhang Zhuangzhuang , Zhen Yanzhong , Fu Feng , Xu Bin 
Published: April 2023

AbstractManganese oxide is a promising cathode material for aqueous zinc batteries. However, its weak structural stability, low electrical conductivity, and sluggish reaction kinetics lead to rapid capacity fading. Herein, a crystal engineering strategy is proposed to construct a novel MnO2 cathode material. Both experimental results and theoretical calculations demonstrate that Al‐doping plays a crucial role in phase transition and doping‐superlattice structure construction, which stabilizes the structure of MnO2 cathode materials, improves conductivity, and accelerates ion diffusion dynamics. As a result, 1.98% Al‐doping MnO2 (AlMO) cathode shows an incredible 15 000 cycle stability with a low capacity decay rate of 0.0014% per cycle at 4 A g−1. Additionally, it provides superior specific capacity of 311.2 mAh g−1 at 0.1 A g−1 and excellent rate performance (145.2 mAh g−1 at 5.0 A g−1). To illustrate the potential of 1.98%AlMO to be applied in actual practice, flexible energy storage devices are fabricated and measured. These discoveries provide a new insight for structural transformation via crystal engineering, as well as a new avenue for the rational design of electrode material in other battery systems.
Watermelon Flesh‐Like Ni3S2@C Composite Separator with Polysulfide Shuttle Inhibition for High‐Performance Lithium‐Sulfur Batteries
Authors: Zhang Bo , Qie Jiaxin , Liu Xuefei , Wang Wenju , Li Yuqian , Cao Yongan , Mao Yangyang , Zou Jiaxuan , You Jiyuan 
Published: April 2023

AbstractThe shuttle effect limits the practical application of lithium‐sulfur (Li‐S) batteries with high specific capacity and cheap price. Herein, a three‐dimensional carbon substrate containing Ni3S2nanoparticles is created to modify the separator. The in situ optical visualization battery proves that the material can realize the rapid conversion of Li2S6. Moreover, the impact of lithium‐ion diffusion on the reactions in the cell is investigated, and the mechanism of Ni3S2@C in the cell is proposed based on the “adsorption‐diffusion‐conversion” mechanism. The “adsorption‐diffusion‐conversion” process of polysulfide is carried out on the surface of the composite separator, showing positive effects on the inhibition of polysulfide shuttle and the promotion of conversion. The separator is modified to improve sulfur utilization and reduce dead sulfur accumulation through a strategy of chemical immobilization and physical blocking. This helps to bridge the existing gaps of Li‐S batteries.
Formation of Size‐Controllable Tetragonal Nanoprisms by Crystallization‐Directed Ionic Self‐Assembly of Anionic Porphyrin and PEO‐Containing Triblock Cationic Copolymer
Authors: Jin Hongjun , Wu Ziyan , Lin Weilin , Chen Yinye , Zhang Jingran , Zheng Ruyi , Wei Haibing , Chen Qinghua , Qian Qingrong , Huang Jianbin , Zhang Jie , Yan Yun 
Published: April 2023

AbstractThe creation of anisotropic nanostructures with precise size control is desirable for new properties and functions, but it is challenging for ionic self‐assembly (ISA) because of the non‐directional electrostatic interactions. Herein, the formation of size‐controllable tetragonal nanoprisms is reported via crystallization‐directed ionic self‐assembly (CDISA) through evaporating a micellar solution on solid substrates. First, ISA is designed with a crystalline polyethylene oxide (PEO) containing cationic polymer poly(2‐(2‐guanidinoethoxy)ethyl methacrylate)‐b‐poly(ethyleneoxide)‐b‐poly(2‐(2‐guanidinoethoxy)‐ethylmethacrylate) (PGn‐PEO230‐PGn) and an anionic 5,10,15,20‐Tetrakis(4‐sulfonatophenyl) porphyrin (TPPS) to form micelles in aqueous solution. The PG segments binds excessive TPPS with amplenet chargeto form hydrophilic corona, while the PEO segments are unprecedentedly dehydrated and tightly packed into cores. Upon naturally drying the micellar solution on a silicon wafer, PEO crystallizationdirects the micelles to aggregate into square nanoplates, which are further connected to nanoprisms. Length and width of the nanoprisms can be facilely tuned by varying the initial concentration. In this hierarchical process, the aqueous self‐assembly is prerequisite and the water evaporation rate is crucial for the formation of nanostructures, which provides multiple factors for morphology regulating. Such precise size‐control strategy is highly expected to provide a new vision for the design of advanced materials with size controllable anisotropic nanostructures.
The Key Effect of Carboxyl Group and CuN2O2 Coordinate Structure for Cu, N Co‐Doped Carbon Dots with Peroxidase‐Like Property
Authors: Ma Yurong , Zhang Mengling , Wu Jie , Zhao Yajie , Du Xin , Huang Hui , Zhou Yunjie , Liu Yang , Kang Zhenhui 
Published: April 2023

AbstractCarbon dots (CDs) with good water solubility and biocompatibility have become a research hotspot in the nano‐enzyme and biomedical field. However, the problems of low catalytic activity and ambiguous catalytic site of CDs as nanozymes still need to be addressed. In this work, CDs loaded with Cu single atoms are obtained through pyrolysis, and the coordination structure and surface functional groups are regulated by adjusting the pyrolysis temperature. CDs obtained at 300 °C (named Cu‐CDs‐300) have the most carboxyl content and Cu is coordinated in the form of CuN2O2, which can better decompose H2O2 to produce free radical and is beneficial to catalyze the oxidation of 3,3′,5,5′‐tetramethylbenzidine (TMB). The vmax is 6.56*10−7 m s−1, 6.56 times higher than that of horseradish peroxidase (HRP). Moreover, Cu‐CDs‐300 can effectively lead to CT26 apoptosis by generating much free radicals. This work demonstrates the synergistic effect of oxygen‐containing functional groups and metal coordination structures on peroxide‐like activity of CDs and provides new ideas for the design of clear active structure and high efficiency peroxide‐like single atom CDs catalyst.