bluuebunny/crossref_metadata_2025 huggingface dataset:
FeNC Oxygen Reduction Electrocatalyst with High Utilization Penta‐Coordinated Sites
Authors: Barrio Jesús , Pedersen Angus , Sarma Saurav Ch. , Bagger Alexander , Gong Mengjun , Favero Silvia , Zhao Chang‐Xin , Garcia‐Serres Ricardo , Li Alain Y. , Zhang Qiang , Jaouen Frédéric , Maillard Frédéric , Kucernak Anthony , Stephens Ifan E. L. , Titirici Maria‐Magdalena
Published: February 2023

Atomic Fe in N‐doped carbon (FeNC) electrocatalysts for oxygen (O2) reduction at the cathode of proton exchange membrane fuel cells are the most promising alternative to platinum‐group‐metal catalysts. Despite recent progress on atomic FeNC O2 reduction, their controlled synthesis and stability for practical applications remain challenging. A two‐step synthesis approach has recently led to significant advances in terms of Fe‐loading and mass activity; however, the Fe utilization remains low owing to the difficulty of building scaffolds with sufficient porosity that electrochemically exposes the active sites. Herein, this issue is addressed by coordinating Fe in a highly porous nitrogen‐doped carbon support (≈3295 m2 g−1), prepared by pyrolysis of inexpensive 2,4,6‐triaminopyrimidine and a Mg2+ salt active site template and porogen. Upon Fe coordination, a high electrochemical active site density of 2.54 × 1019 sites gFeNC−1 and a record 52% FeNx electrochemical utilization based on in situ nitrite stripping are achieved. The Fe single atoms are characterized pre‐ and post‐electrochemical accelerated stress testing by aberration‐corrected high‐angle annular dark field scanning transmission electron microscopy, showing no Fe clustering. Moreover, ex situ X‐ray absorption spectroscopy and low‐temperature Mössbauer spectroscopy suggest the presence of penta‐coordinated Fe sites, which are further studied by density functional theory calculations.
Butterfly‐Inspired Tri‐State Photonic Crystal Composite Film for Multilevel Information Encryption and Anti‐Counterfeiting
Authors: Huang Hanwen , Li Huateng , Yin Jiamiao , Gu Kai , Guo Jia , Wang Changchun
Published: February 2023

Counterfeiting is a worldwide issue and has long troubled legitimate businesses, while nowadays anti‐counterfeiting materials and technology are still insufficient to combat the escalating counterfeit behaviors. Inspired by hindwing structure of Troides magellanus, a new kind of anti‐counterfeiting material taking advantage of both physical and chemical structures to display multiple optical states is prepared. The chemical units (luminescent lanthanide) are blended with physical units (monodispersed colloidal particles) and mediating molecules, which are then assembled into a photonic crystal structure at room temperature in less than 10 s through a new assembly technique called molecule‐mediated shear‐induced assembly technique (MSAT). The as‐prepared photonic crystal films feature three unique optical states, each displaying structural, fluorescent, and phosphorescent color under different lighting conditions, which integrates colors from both physical and chemical origins. Furthermore, by incorporating different luminescent materials into different parts of the photonic crystal pattern, a high‐level information encryption system is designed to be capable of carrying three distinct types of information. Thanks to this powerful tool of MSAT, it is now possible to assemble different‐sized, even irregular non‐spherical units with monodispersed spherical units into high‐quality photonic crystal films, which provides easy access to incorporating new features into photonic crystal systems.
Dynamic and Reversible Decoration of DNA‐Based Scaffolds
Authors: Farag Nada , Đorđević Milan , Del Grosso Erica , Ricci Francesco
Published: February 2023

An approach to achieving dynamic and reversible decoration of DNA‐based scaffolds is demonstrated here. To do this, rationally engineered DNA tiles containing enzyme‐responsive strands covalently conjugated to different molecular labels are employed. These strands are designed to be recognized and degraded by specific enzymes (i.e., Ribonuclease H, RNase H, or Uracil DNA Glycosylase, UDG) inducing their spontaneous de‐hybridization from the assembled tile and replacement by a new strand conjugated to a different label. Multiple enzyme‐responsive strands that specifically respond to different enzymes allow for dynamic, orthogonal, and reversible decoration of the DNA structures. As a proof‐of‐principle of the strategy, the possibility to orthogonally control the distribution of different labels (i.e., fluorophores and small molecules) on the same scaffold without crosstalk is demonstrated. By doing so, DNA scaffolds that display different antibody recognition patterns are obtained. The approach offers the possibility to control the decoration of higher‐order supramolecular assemblies (including origami) with several functional moieties to achieve functional biomaterials with improved adaptability, precision, and sensing capabilities.
Hexaindium Heptasulfide/Nitrogen and Sulfur Co‐Doped Carbon Hollow Microspindles with Ultrahigh‐Rate Sodium Storage through Stable Conversion and Alloying Reactions
Authors: Zhu Chunyan , Yu Weiqing , Zhang Shuxian , Chen Jianchao , Liu Qingyuan , Li Qingyu , Wang Shijie , Hua Minghao , Lin Xiaohang , Yin Longwei , Wang Rutao
Published: February 2023

Group IIIA–VA metal sulfides (GMSs) have attracted increasing attention because of their unique Na‐storage mechanisms through combined conversion and alloying reactions, thus delivering large theoretical capacities and low working potentials. However, Na+ diffusion within GMSs anodes leads to severe volume change, generally representing a fundamental limitation to rate capability and cycling stability. Here, monodispersed In6S7/nitrogen and sulfur co‐doped carbon hollow microspindles (In6S7/NSC HMS) are produced by morphology‐preserved thermal sulfurization of spindle‐like and porous indium‐based metal organic frameworks. The resulting In6S7/NSC HMS anode exhibits theoretical‐value‐close specific capacity (546.2 mAh g−1 at 0.1 A g−1), ultrahigh rate capability (267.5 mAh g−1 at 30.0 A g−1), high initial coulombic efficiency (≈93.5%), and ≈92.6% capacity retention after 4000 cycles. This kinetically favored In6S7/NSC HMS anode fills up the kinetics gap with a capacitive porous carbon cathode, enabling a sodium‐ion capacitor to deliver an ultrahigh energy density of 136.3 Wh kg−1 and a maximum power density of 47.5 kW kg−1. The in situ/ex situ analytical techniques and theoretical calculation both show that the robust and fast Na+ charge storage of In6S7/NSC HMS arises from the multi‐electron redox mechanism, buffered volume expansion, negligible morphological change, and surface‐controlled solid‐state Na+ transport.
A Nonswelling Hydrogel with Regenerable High Wet Tissue Adhesion for Bioelectronics
Authors: Tian Gongwei , Yang Dan , Liang Cuiyuan , Liu Yan , Chen Jianhui , Zhao Qinyi , Tang Shuanglong , Huang Jianping , Xu Ping , Liu Zhiyuan , Qi Dianpeng
Published: February 2023

Reducing the swelling of tissue‐adhesive hydrogels is crucial for maintaining stable tissue adhesion and inhibiting tissue inflammation. However, reported strategies for reducing swelling always result in a simultaneous decrease in the tissue adhesive strength of the hydrogel. Furthermore, once the covalent bonds break in the currently reported hydrogels, they cannot be rebuilt, and the hydrogel loses its tissue adhesive ability. In this work, a nonswelling hydrogel (named as “PAACP”) possessing regenerable high tissue adhesion is synthesized by copolymerizing and crosslinking poly(vinyl butyral) with acrylic acid, gelatin, and chitosan‐grafted N‐acetyl‐l‐cysteine. The tissue adhesive strength of the obtained PAACP reaches 211.4 kPa, which is approximately ten times higher than that of the reported nonswelling hydrogels, and the hydrogel can be reused for multiple cycles. The as‐prepared hydrogel shows great potential in soft bioelectronics, as muscle fatigue is successfully monitored via the electrode array and strain sensor integrated on PAACP substrates. The success of these bioelectronics offers potential applicability in the long‐term diagnosis of muscle‐related health conditions and prosthetic manipulations.
Therapeutic DNAzymes: From Structure Design to Clinical Applications
Authors: Yan Jiaqi , Ran Meixin , Shen Xian , Zhang Hongbo
Published: February 2023

Therapeutic DNAzymes have unceasingly intrigued the scientific community owing to their prosperous gene regulation capability. The efficacy of DNAzymes against many types of diseases has been extensively studied for over two decades. However, the high expectations for DNAzymes are still not translated to the clinic because of their low effectiveness in vivo. Over the last five years, several aspects have been considered to optimize DNAzyme‐integrated therapeutics, including structural stability, mechanism exploration, cell internalization rate, cofactor activation, and off‐target effects. Hence, this review first discusses the early monotherapy and structural design of DNAzymes. Subsequently, the latest modes of action are reviewed, followed by an elaboration on structural stabilization strategies considering the catalytic core and substrate‐binding arms. DNAzyme‐based synergistic therapy is then examined, highlighting responsive carrier construction, synergistic effects, the latest discovered advanced functions, and off‐target concerns. Beyond this, key clinical advances in DNAzyme‐based therapy are elucidated by showcasing clinical progress. Finally, future trends and development challenges for DNAzyme‐powered therapeutics in the coming years are discussed in detail.
Reliability Improvement from La2O3 Interfaces in Hf0.5Zr0.5O2‐Based Ferroelectric Capacitors
Authors: Mehmood Furqan , Alcala Ruben , Vishnumurthy Pramoda , Xu Bohan , Sachdeva Ridham , Mikolajick Thomas , Schroeder Uwe
Published: February 2023

Further optimization of a typically reported ferroelectric capacitor comprised of a Hf0.5Zr0.5O2 ferroelectric thin film with TiN electrodes is explored by introducing an additional non‐ferroelectric La2O3 interfacial layer evaluated at different positions in the capacitor stack. The role of the interface to the ferroelectric layer is investigated and discussed, with the main focus directed toward the reliability of the device for non‐volatile memory applications. With this investigation, different degradation mechanisms determining electric field cycling and polarization retention are observed, and it is concluded that modifying the bottom interface between the electrode and the ferroelectric layer has the best potential to provide a benefit in device performance.
Monolithic Perovskite/Si Tandem Solar Cells—Silicon Bottom Cell Types and Characterization Methods
Authors: Park Jae Hyun , Ji Su Geun , Yoon Young Seon , Park Min‐Ah , Lee Sun Hwa , Kim Ki Hong , Kim Jin Young
Published: February 2023

As a more efficient alternative to the crystalline Si (c‐Si) cell whose performance is approaching its theoretical limit, perovskite (PVSK)/Si tandem solar cells (TSCs) are attracting attention from academia and industry. The tandem device, which can benefit from the maturity of the c‐Si cells and the high performance of the PVSK solar cell, has undergone tremendous development. The expectation for its commercialization is increasing as the device shows conversion efficiencies surpassing those of single‐junction solar cells. In this perspective article, the recent progress of the PVSK/Si TSC is summarized from a viewpoint balanced between academia and industry, by regrouping reported devices depending on the types of Si bottom cells: passivated emitter rear contact, heterojunction with intrinsic thin layer, and polysilicon‐passivated contact. In addition, opto‐electronic characterization methods of the PVSK/Si TSCs are reviewed, which can provide an in‐depth analysis of the subcells that can facilitate the development.
Advancements in Electronic Materials and Devices for Stretchable Displays
Authors: Lee Yeongjun , Cho Hyeon , Yoon Hyungsoo , Kang Hyunbum , Yoo Hyunjun , Zhou Huanyu , Jeong Sujin , Lee Gae Hwang , Kim Geonhee , Go Gyeong‐Tak , Seo Jiseok , Lee Tae‐Woo , Hong Yongtaek , Yun Youngjun
Published: February 2023

A stretchable display would be the ultimate form factor for the next generation of displays beyond the curved and foldable configurations that have enabled the commercialization of deformable electronic applications. However, because conventional active devices are very brittle and vulnerable to mechanical deformation, appropriate strategies must be developed from the material and structural points of view to achieve the desired mechanical stretchability without compromising electrical properties. In this regard, remarkable findings and achievements in stretchable active materials, geometrical designs, and integration enabling technologies for various types of stretchable electronic elements have been actively reported. This review covers the recent developments in advanced materials and feasible strategies for the realization of stretchable electronic devices for stretchable displays. In particular, representative strain‐engineering technologies for stretchable substrates, electrodes, and active devices are introduced. Various state‐of‐the‐art stretchable active devices such as thin‐film transistors and electroluminescent devices that consist of stretchable matrix displays are also presented. Finally, the future perspectives and challenges for stretchable active displays are discussed.
Wireless and Flexible Optoelectronic System for In Situ Monitoring of Vaginal pH Using a Bioresorbable Fluorescence Sensor
Authors: Paghi Alessandro , Corsi Martina , La Mattina Antonino A. , Egri Gabriella , Dähne Lars , Barillaro Giuseppe
Published: February 2023

Herein, a miniaturized wireless sensing vaginal ring for the in situ continuous monitoring of vaginal pH and real‐time transmission of the pH data to a smartphone is reported, aimed at the diagnosis and management of bacterial vaginosis, a common condition frequently and adversely affecting women. The sensing vaginal ring consists of a bioresorbable pH fluorescence sensor placed on top of a polydimethylsiloxane ring encapsulating a miniaturized driving/readout optoelectronic circuit, data acquisition system, wireless transceiver, and power supply. The pH sensor consists of a micrometer‐thick porous silica scaffold conformably coated with a nanometer‐thick polymer multilayer stack and is intended to be replaced after 4 days. The sensor fully dissolves in biocompatible by‐products eliminating waste management issues; conversely, the ring embedding the circuit is reusable with new sensors. The pH sensor, as well as the sensing vaginal ring, show excellent performance in the continuous measurement of pH in vaginal fluid and can monitor the pH level over the physio‐pathological range of 3–7.5 with high linearity, accuracy, and reliability, transmitting the data to a smartphone in real time. The proposed technology can be immediately translated to other diseases, among which wound healing, intragastric activity, and cancer progression, where continuous monitoring of pH is required, as well as to other markers/analytes by engineering the polymer stack with suitable receptors, such as aptamers and other molecular probes.
3D‐Printed Microinjection Needle Arrays via a Hybrid DLP‐Direct Laser Writing Strategy
Authors: Sarker Sunandita , Colton Adira , Wen Ziteng , Xu Xin , Erdi Metecan , Jones Anthony , Kofinas Peter , Tubaldi Eleonora , Walczak Piotr , Janowski Miroslaw , Liang Yajie , Sochol Ryan D.
Published: February 2023

Microinjection protocols are ubiquitous throughout biomedical fields, with hollow microneedle arrays (MNAs) offering distinctive benefits in both research and clinical settings. Unfortunately, manufacturing‐associated barriers remain a critical impediment to emerging applications that demand high‐density arrays of hollow, high‐aspect‐ratio microneedles. To address such challenges, here, a hybrid additive manufacturing approach that combines digital light processing (DLP) 3D printing with “ex situ direct laser writing (esDLW)” is presented to enable new classes of MNAs for fluidic microinjections. Experimental results for esDLW‐based 3D printing of arrays of high‐aspect‐ratio microneedles—with 30 µm inner diameters, 50 µm outer diameters, and 550 µm heights, and arrayed with 100 µm needle‐to‐needle spacing—directly onto DLP‐printed capillaries reveal uncompromised fluidic integrity at the MNA‐capillary interface during microfluidic cyclic burst‐pressure testing for input pressures in excess of 250 kPa (n = 100 cycles). Ex vivo experiments perform using excised mouse brains reveal that the MNAs not only physically withstand penetration into and retraction from brain tissue but also yield effective and distributed microinjection of surrogate fluids and nanoparticle suspensions directly into the brains. In combination, the results suggest that the presented strategy for fabricating high‐aspect‐ratio, high‐density, hollow MNAs could hold unique promise for biomedical microinjection applications.
Conformal Integration of an Inkjet‐Printed PbS QDs‐Graphene IR Photodetector on a Polymer Optical Fiber
Authors: Kara Gökhan , Bolat Sami , Sharma Khushdeep , Grotevent Matthias J. , Dirin Dmitry N. , Bachmann Dominik , Furrer Roman , Boesel Luciano F. , Romanyuk Yaroslav E. , Rossi René M. , Kovalenko Maksym V. , Calame Michel , Shorubalko Ivan
Published: February 2023

Hybrid graphene‐colloidal PbS quantum dots (QDs) phototransistors are promising to overcome the geometrical restrictions of photodetectors to flat substrates. While compatible with conformal manufacturing, the experimental demonstration of their application to curved surfaces remains elusive. This work demonstrates the seamless integration of an infrared (IR) photodetector to a polymer optical fiber (POF) by wrapping graphene around the POF of 1 mm in diameter and, subsequently, inkjet printing of PbS QDs onto the curved surface. The device acts as a functional coating and detects infrared light propagating through the POF without interrupting the waveguide. The formulated α‐terpineol and hexane co‐solvent ink supports drop‐on‐demand placement with a resolution of 50 µm and is colloidally stable over 7 months. A responsivity map over gate voltage and temperature (300 to 80 K) of a device, fabricated on a common flat substrate, reveals a responsivity of R ≈ 1 × 103AW−1 (irradiance ≈1 µW cm−2) and a detectivity of D* ≈ 1 × 1010 Jones at 1.6 µm wavelength. This work brings the integration of this cost‐effective and adaptable hybrid detector approach closer to multifunctional e‐textiles and will, notably, help to improve the interfacing of the skin as desired for wearable and non‐invasive healthcare applications.
Extreme Metasurfaces Enable Targeted and Protected Wireless Energy Transfer
Authors: Zanganeh Esmaeel , Sayanskiy Andrey , Kosulnikov Sergei , Kapitanova Polina
Published: February 2023

Controlling the electromagnetic properties of materials beyond those achievable with natural substances has become a reality with the advent of metamaterials. The extreme properties that metamaterials provide offer an opportunity to manipulate and tailor electromagnetic waves in an arbitrary manner. Wireless energy transfer demands reliable and stable solutions for charging batteries of electronic devices with high efficiency and no effect on people, animals, plants, etc. Motivated by this challenging problem, a novel approach of using metamaterials with extreme parameters is suggested to enable targeted wireless energy transfer with reduced impact on biological tissues. Epsilon‐near‐zero (ENZ) and epsilon‐and‐mu‐near‐zero (EMNZ) metamaterials are designed and experimentally implemented, providing an energy transmission if and only if both the transmitter and the receiver are equipped with these metamaterials. The nonexistence of these extreme parameter metamaterials in nature protects the system from the presence of other objects with “ordinary” (effective) parameters causing neither noticeable change in operation nor any detrimental effect on foreign objects. The system behind the proposed approach can be realized in virtually any frequency band by appropriate scaling and suitable choice of material. This technology will find applications in targeted wireless energy transfer systems, especially where high power is needed, including electric vehicles.
Highly Efficient Sum‐Frequency Generation in Niobium Oxydichloride NbOCl2 Nanosheets
Authors: Abdelwahab Ibrahim , Tilmann Benjamin , Zhao Xiaoxu , Verzhbitskiy Ivan , Berté Rodrigo , Eda Goki , Wilson William L. , Grinblat Gustavo , de S. Menezes Leonardo , Loh Kian Ping , Maier Stefan A.
Published: February 2023

Parametric infrared (IR) upconversion is a process in which low‐frequency IR photons are upconverted into high‐frequency ultraviolet/visible photons through a nonlinear optical process. It is of paramount importance for a wide range of security, material science, and healthcare applications. However, in general, the efficiencies of upconversion processes are typically extremely low for nanometer‐scale materials due to the short penetration depth of the excitation fields. Here, parametric IR upconversion processes, including frequency doubling and sum‐frequency generation, are studied in layered van der Waals NbOCl2. An upconversion efficiency of up to 0.004% is attained for the NbOCl2 nanosheets, orders of magnitude higher than previously reported values for nonlinear layered materials. The upconverted signal is sensitive to layer numbers, crystal orientation, excitation wavelength, and temperature, and it can be utilized as an optical cross‐correlator for ultrashort pulse characterization.
Impacts of Liquid Level on Microwave Resonance Sensing with a Flexible Microfluidic Channel
Authors: Wang Wan Zhu , Zhang Xuanru , Zhang Long Fei , Cui Tie Jun
Published: February 2023

Permittivity sensing based on resonance tracking lays the fundamental principle for a variety of biochemical sensors, which has found vast applications in cancer biomarker detection, antigen‐antibody analysis, and so on. Driven by continuous promotion of the detection limit, precise environmental control highlights its critical importance. Here, the impacts of liquid level on microwave resonance sensing are investigated, in which a flexible polydimethylsiloxane microfluidic channel and soft tubing are employed to control the liquid under test. The hydraulic pressure affects the effective permittivity of the liquid and the channel material, hence causing extra resonance shift signals. Both contactless and contacting sensing scenarios are studied in numerical simulations and experiments. It is demonstrated that the resonance frequency varies sensitively with the liquid level, and a sensitivity of 343 kHz mm−1 is measured. Meanwhile, a spoof localized surface plasmon resonator and its optimized excitation structure are employed and analyzed for a good figure of merit, addressing the detectability difficulties for high‐permittivity and high‐loss aqueous solutions. These results provide general guidelines for understanding and controlling the resonance sensors in aqueous environments and help to realize further lower detection limits.
Dimeric Cholic Acid Peptide Conjugates Act as Effective Antibiotic Adjuvants against Multidrug Resistance (MDR) Gram‐Negative Bacterial Infections
Authors: Aggarwal Bharti , Saini Varsha , Mehta Devashish , Bajaj Avinash
Published: February 2023

Macrolides, glycopeptides, lipopeptides, and oxazolidinones class of antibiotics are used only for Gram‐positive bacteria, and are ineffective against Gram‐negative bacteria due to inability of these antibiotics to cross the Gram‐negative bacterial membranes. Here, dimeric cholic acid peptide conjugates as effective adjuvants that allow penetration of erythromycin across Gram‐negative bacteria are presented, making it effective antimicrobial. Here, it is shown that synthesized dimers2and3,having tetramethylene and pentamethylene spacers respectively between cholic acid‐triglycine conjugates, in combination with erythromycin cause synergistic antimicrobial effect against Gram‐negative bacteria. Biochemical studies reveal that dimer3causes outer and inner membrane permeabilization by interacting with lipopolysaccharide and displacing Mg2+ions, thereby allowing the erythromycin to cross bacterial membranes. Dimer3in combination with erythromycin can clear the preformed biofilms ofE. coliandP. aeruginosaeffectively. It is further demonstrated that combination of dimer3and erythromycin can clear wound infections ofE. coliandP. aeruginosa. Additionally, activities against multidrug resistant clinical strains ofE. coliandP. aeruginosawitness that combination of dimer3and erythromycin is an ideal combination to mitigate drug‐resistant infections.
Bridging the Binding Sites: Dualsteric Ligands for the Cannabinoid 2 Receptor (CB2R)
Authors: Tutov Anna , Steinmüller Sophie A. M. , Ramírez Yesid A. , Jack Christine E. , Rodríguez‐Soacha Diego A. , Sotriffer Christoph , Hislop James N. , Decker Michael
Published: February 2023

The cannabinoid receptor subtype 2 (CB2R) is rapidly upregulated in neuroinflammatory processes and respective agonists have a high potential to combat several central nervous system disorders related to neuroinflammation and neurodegeneration. As a new strategy for ligand design, dualsteric binding is applied by chemically combining a positive allosteric modulator with an orthosteric ligand. The resulting two sets of potential dualsteric (or bitopic) ligands with different chain lengths of two to five methylene groups are evaluated in [3H]CP55940 binding studies to determine receptor affinity at CB1R and CB2R. Calcium mobilization, receptor endocytosis and BRET assays determine their efficacy and identify compounds of set B to act as agonists with efficacy higher than the reference compound in G protein mediated calcium signaling. Pharmacological evaluation and docking studies support the dualsteric nature of binding of the herein presented compounds.
An IL‐12‐Based Nanocytokine Safely Potentiates Anticancer Immunity through Spatiotemporal Control of Inflammation to Eradicate Advanced Cold Tumors
Authors: Chen Pengwen , Yang Wenqian , Nagaoka Koji , Huang George Lo , Miyazaki Takuya , Hong Taehun , Li Shangwei , Igarashi Kazunori , Takeda Kazuyoshi , Kakimi Kazuhiro , Kataoka Kazunori , Cabral Horacio
Published: February 2023

Treatment of immunologically cold tumors is a major challenge for immune checkpoint inhibitors (ICIs). Interleukin 12 (IL‐12) can invigorate ICIs against cold tumors by establishing a robust antitumor immunity. However, its toxicity and systemic induction of counteracting immunosuppressive signals have hindered translation. Here, IL‐12 activity is spatiotemporally controlled for safely boosting efficacy without the stimulation of interfering immune responses by generating a nanocytokine that remains inactive at physiological pH, but unleashes its full activity at acidic tumor pH. The IL‐12‐based nanocytokine (Nano‐IL‐12) accumulate and release IL‐12 in tumor tissues, eliciting localized antitumoral inflammation, while preventing systemic immune response, counteractive immune reactions, and adverse toxicities even after repeated intravenous administration. The Nano‐IL‐12‐mediated spatiotemporal control of inflammation prompt superior anticancer efficacy, and synergize with ICIs to profoundly inflame the tumor microenvironment and completely eradicate ICI‐resistant primary and metastatic tumors. The strategy could be a promising approach toward safer and more effective immunotherapies.
Near‐Death Cells Cause Chemotherapy‐Induced Metastasis via ATF4‐Mediated NF‐κB Signaling Activation
Authors: Zhu Chenchen , Liu Pei , Li Chuan‐Yuan , Zhang Yuli , Yin Jiang , Hou Linlin , Zheng Guopei , Liu Xinjian
Published: February 2023

Cytotoxic chemotherapy is a primary treatment modality for many patients with advanced cancer. Increasing preclinical and clinical observations indicate that chemotherapy can exacerbate tumor metastasis. However, the underlying mechanism remains unclear. Here, it is attempted to identify the mechanisms underlying chemotherapy‐induced cancer recurrence and metastasis. It is revealed that a small subpopulation of “near‐death cells” (NDCs) with compromised plasma membranes can reverse the death process to enhance survival and repopulation after exposure to lethal doses of cytotoxins. Moreover, these NDCs acquire enhanced tumorigenic and metastatic capabilities, but maintain chemosensitivity in multiple models. Mechanistically, cytotoxin exposure induces activating transcription factor 4 (ATF4)‐dependent nonclassical NF‐κB signaling activation; ultimately, this results in nuclear translocation of p52 and RelB in NDCs. Deletion of ATF4 in parental cancer cells significantly reduces colony formation and metastasis of NDCs, whereas overexpression of ATF4 activates the nonclassical NF‐κB signaling pathway to promote chemotherapy‐induced metastasis of NDCs. Overall, these results provide novel mechanistic insights into the chemotherapy‐induced metastasis and indicate the pivotal role of NDCs in mediating tumor relapse after cytotoxic therapy. This study also suggests that targeting ATF4 may be an effective approach in improving the efficacy of chemotherapy.
Machine Learning Customized Novel Material for Energy‐Efficient 4D Printing
Authors: Tan Chaolin , Li Qian , Yao Xiling , Chen Lequn , Su Jinlong , Ng Fern Lan , Liu Yuchan , Yang Tao , Chew Youxiang , Liu Chain Tsuan , DebRoy Tarasankar
Published: February 2023

Existing commercial powders for laser additive manufacturing (LAM) are designed for traditional manufacturing methods requiring post heat treatments (PHT). LAM's unique cyclic thermal history induces intrinsic heat treatment (IHT) on materials during deposition, which offers an opportunity to develop LAM‐customized new materials. This work customized a novel Fe–Ni–Ti–Al maraging steel assisted by machine learning to leverage the IHT effect for in situ forming massive precipitates during LAM without PHT. Fast precipitation kinetics in steel, tailored intermittent deposition strategy, and the IHT effect facilitate the in situ Ni3Ti precipitation in the martensitic matrix via heterogeneous nucleation on high‐density dislocations. The as‐built steel achieves a tensile strength of 1538 MPa and a uniform elongation of 8.1%, which is superior to a wide range of as‐LAM‐processed high‐strength steel. In the current mainstream ex situ 4D printing, the time‐dependent evolutions (i.e., property or functionality changes) of a 3D printed structure occur after part formation. This work highlights in situ 4D printing via the synchronous integration of time‐dependent precipitation hardening with 3D geometry shaping, which shows high energy efficiency and sustainability. The findings provide insight into developing LAM‐customized materials by understanding and utilizing the IHT‐materials interaction.
Tantalum–Zirconium Co‐Doped Metal–Organic Frameworks Sequentially Sensitize Radio–Radiodynamic–Immunotherapy for Metastatic Osteosarcoma
Authors: Li Tao , Gao Mingquan , Wu Zifei , Yang Junjun , Mo Banghui , Yu Songtao , Gong Xiaoyuan , Liu Jing , Wang Weidong , Luo Shenglin , Li Rong
Published: February 2023

Due to radiation resistance and the immunosuppressive microenvironment of metastatic osteosarcoma, novel radiosensitizers that can sensitize radiotherapy (RT) and antitumor immunity synchronously urgently needed. Here, the authors developed a nanoscale metal–organic framework (MOF, named TZM) by co‐doping high‐atomic elements Ta and Zr as metal nodes and porphyrinic molecules (tetrakis(4‐carboxyphenyl)porphyrin (TCPP)) as a photosensitizing ligand. Given the 3D arrays of ultra‐small heavy metals, porous TZM serves as an efficient attenuator absorbing X‐ray energy and sensitizing hydroxyl radical generation for RT. Ta–Zr co‐doping narrowed the highest occupied molecular orbital‐lowest unoccupied molecular orbital (HOMO–LUMO) energy gap and exhibited close energy levels between the singlet and triplet photoexcited states, facilitating TZM transfer energy to the photosensitizer TCPP to sensitize singlet oxygen (1O2) generation for radiodynamic therapy (RDT). The sensitized RT–RDT effects of TZM elicit a robust antitumor immune response by inducing immunogenic cell death, promoting dendritic cell maturation, and upregulating programmed cell death protein 1 (PD‐L1) expression via the cGAS–STING pathway. Furthermore, a combination of TZM, X‐ray, and anti‐PD‐L1 treatments amplify antitumor immunotherapy and efficiently arrest osteosarcoma growth and metastasis. These results indicate that TZM is a promising radiosensitizer for the synergistic RT and immunotherapy of metastatic osteosarcoma.
Activating One/Two‐Photon Excited Red Fluorescence on Carbon Dots: Emerging n→π Photon Transition Induced by Amino Protonation
Authors: Zhang Qing , Wang Fengqing , Wang Ruoyu , Liu Junlan , Ma Yupengxue , Qin Xiaoru , Zhong Xiaoxia
Published: February 2023

Due to the complicated nature of carbon dots (CDs), fluorescence mechanism of red fluorescent CDs is still unrevealed and features highly controversial. Reliable and effective strategies for manipulating the red fluorescence of CDs are urgently needed. Herein, CDs with one‐photon excited (622 nm, QYs ≈ 17%) and two‐photon (629 nm) excited red fluorescence are prepared by acidifying o‐phenylenediamine‐based reaction sediments. Systematic analysis reveals that the protonation of amino groups increases the particle surface potential, disperse the bulk sediments into nano‐scale CDs. In the meanwhile, amino protonation of pyridinic nitrogen (–N=) structure inserts numerous n orbital energy levels between the π → π* transition, narrows the gap distance for photon transition, and induces red fluorescence emission on CDs. Present research reveals an effective pathway to activate CDs reaction sediments and trigger red emission, thus may open a new avenue for developing CDs with ideal optical properties and promising application prospects.
An Ultrathin Asymmetric Solid Polymer Electrolyte with Intensified Ion Transport Regulated by Biomimetic Channels Enabling Wide‐Temperature High‐Voltage Lithium‐Metal Battery
Authors: Yao Meng , Ruan Qinqin , Pan Shanshan , Zhang Haitao , Zhang Suojiang
Published: February 2023

Solid electrolytes that can be made compatible with high‐voltage cathodes are greatly desired to increase the energy density of solid lithium metal batteries (SLMBs). However, no monophase polymer or ceramic examples can simultaneously exhibit strong electrochemical stability and reasonable lithium compatibility due to their limited internal energy gap. Herein, a novel asymmetric solid polymer electrolyte (AMSE) with tailored Li+ transport mechanisms is proposed. It is composed of a high‐voltage layer (HVL, polyacrylonitrile/ionic liquid [IL]) and lithium‐compatible layer (LCL, poly(vinylidene fluoride‐co‐hexafluoropropylene)/UiO‐66‐SO3Li). The HVL exhibits a vehicular Li+ transport mechanism with the introduction of IL, which achieves exceptional‐electrochemical stability and reduced interfacial resistance. Due to the complexation between anions and UiO‐66‐SO3Li, a structural diffusion mechanism is achieved in LCL, realizing a quasi‐single‐ion migration in biomimetic ionic channels. The as‐proposed asymmetric configuration, combined with the transport mechanisms, leads to a gradient distribution of electric potential and Li+ in the electrolyte, thus realizing a stable Li+ flux, which is proved by COMSOL‐Multiphysics. The AMSE‐based SLMBs and scale‐up pouch cells show remarkable cycling stability at 4.3 V from room temperature (Li/LiNi0.8Mn0.1Co0.1O2, 3.27 mAh cm−2) to 100 °C. The strategy of facilitating the transport mechanism is expected to provide new pathways for designing next‐generation SLMBs with high energy density.
NASICON‐Based Solid State Li‐Fluoride Conversion Batteries Enabled by Constructing a Fluorine‐Rich Trap for Ti4+
Authors: Gu Yuping , Hu Jiulin , Lai Chuanzhong , Li Chilin
Published: February 2023

The application of solid‐state Li metal batteries based on NASICON‐type Li(1+x)AlxTi(2‑x)(PO4)3 (LATP) electrolytes has been hindered by the interface instability, originating from the spontaneous Ti4+ reduction reaction between LATP and Li. Here, a mesoporous fluorination interlayer based on high‐surface‐area AlF3 is proposed to improve the stability and compatibility of the LATP/Li interface and enable the reversible operation of NASICON‐type Li||FeF3 conversion batteries. The high Lewis acidity and porosity in the interlayer can buffer the volume evolution, increase the Li‐ion transference number and promote the formation of LiF domains. Time‐of‐flight secondary‐ion mass spectroscopy (ToF‐SIMS) proves the in situ construction of an F‐rich trap zone for Ti4+, which can pin the easily‐reduced Ti4+ in LATP and retard its conversion to Ti3+ during the electrochemical process. An electro‐fusion process at the LATP/Li interface occurs and successfully welds the solid electrolyte, AlF3 interlayer, and anode into a whole to mitigate the anode resistance, guaranteeing the fast interface migration of Li+. The corresponding Li||Li symmetric cells exhibit a stable cycling performance with small voltage hysteresis for at least 500 h. The ceramic‐type solid‐state Li‐Fe‐F cells modulated by the F‐rich transition layer can deliver a high capacity of 696.7 mAh g−1 and show a good cyclability of the conversion reaction.
Weakly Solvating Effect Spawning Reliable Interfacial Chemistry for Aqueous Zn/Na Hybrid Batteries
Authors: Yang Yihan , Qu Guangmeng , Wei Hua , Wei Zhiquan , Liu Chao , Lin Yilun , Li Xinming , Han Cuiping , Zhi Chunyi , Li Hongfei
Published: February 2023

The insufficient exploration of the interfacial chemistry of Zn anodes and electrolytes in an aqueous environment restricts the application potential of aqueous Zn batteries (AZBs). Herein, a durable anion‐derived solid electrolyte interface (SEI) with high ion conduction properties is constructed by designing an aqueous electrolyte with a weakly solvating effect to manipulate the solvation structure of metal ions (Zn2+/Na+). The constructed SEI significantly restrains the dendrite formation and occurrence of adverse reactions on the surface of the Zn anode, endowing the Zn metal anode with high reversibility of deposition/stripping and ultra‐long lifespan over 5000 h with an exceptional cumulative capacity of over 2.5 Ah cm−2. Significantly, the formation mechanism of the SEI, which is realized by the weakly solvating effect to promote the coordination between anions and metal ions (Zn2+/Na+), and the composition distribution of anion‐derived inorganic‐rich SEI, are clarified in detail. Furthermore, benefiting from the synergy of the elaborate SEI and the regulated electrolyte environment, the Zn//Prussian blue analogue (PBA) full battery can operate with a high voltage platform of 2.1 V and deliver 99.3% capacity retention after 5000 cycles.
Tuning Ion Transport at the Anode‐Electrolyte Interface via a Sulfonate‐Rich Ion‐Exchange Layer for Durable Zinc‐Iodine Batteries
Authors: Zhang Leiqian , Huang Jiajia , Guo Hele , Ge Lingfeng , Tian Zhihong , Zhang Mingjie , Wang Jingtao , He Guanjie , Liu Tianxi , Hofkens Johan , Brett Dan J.L. , Lai Feili
Published: February 2023

Rechargeable aqueous zinc‐iodine batteries (ZIBs) are considered a promising newly‐developing energy‐storage system, but the corrosion and dendritic growth occurring on the anode seriously hinder their future application. Here, the corrosion mechanism of polyiodide is revealed in detail, showing that it can spontaneously react with zinc and cause rapid battery failure. To address this issue, a sulfonate‐rich ion‐exchange layer (SC‐PSS) is purposely constructed to modulate the transport and reaction chemistry of polyiodide and Zn2+at the zinc/electrolyte interface. The resulting ZIBs can work properly over 6000 cycles with high‐capacity retention (90.2%) and reversibility (99.89%). Theoretical calculations and experimental characterization reveal that the SC‐PPS layer blocks polyiodide permeation through electrostatic repulsion, while facilitating desolvation of Zn(H2O)62+and restricting undesirable 2D diffusion of Zn2+by chemisorption.
Effect of Processing on Structure and Ionic Conductivity of Chlorine‐Rich Lithium Argyrodites
Authors: Wang Shuo , Gautam Ajay , Wu Xinbin , Li Shenghao , Zhang Xin , He Hongcai , Lin Yuanhua , Shen Yang , Nan Ce-Wen
Published: February 2023

Lithium argyrodite solid electrolytes have attracted ever‐increasing attention for all‐solid‐state batteries due to their high ionic conductivity and low cost. However, the relation between structure and ionic transport for the halogen‐rich lithium argyrodites under different synthesis routes is still elusive. Herein, the influence of synthesis procedures, such as annealing conditions and balling milling, on the structure, ionic conductivity, and activation energy of the lithium argyrodite (e.g., Li5.5PS4.5Cl1.5, Li5.3PS4.3Cl1.7), is systematically investigated. Compared with high‐energy ball milling followed by annealing, using fast dry mixing followed by annealing can obtain comparable ionic conductivity of the chlorine‐rich lithium argyrodites. Single‐crystal LiNi0.83Co0.11Mn0.06O2‐based solid‐state battery with these electrolytes shows stable cycling performance, demonstrating that chlorine‐rich lithium argyrodite is a promising candidate for all‐solid‐state batteries.
Japanese national survey on declined liver allografts from brain‐dead donors: High decline rate but promising outcomes in allografts with moderate steatosis
Authors: Takemura Yusuke , Shinoda Masahiro , Hasegawa Yasushi , Yamada Yohei , Obara Hideaki , Kitago Minoru , Kasahara Mureo , Umeshita Koji , Eguchi Susumu , Kitagawa Yuko , Ohdan Hideki , Egawa Hiroto
Published: February 2023

Aim

Liver allografts from brain‐dead donors, which were declined and were eventually not transplanted due to accompanying marginal factors, have never been surveyed in Japan. We surveyed the declined allografts and discussed the graft potential focusing on various marginal factors.

Methods

We collected data on brain‐dead donors between 1999 and 2019 from the Japan Organ Transplant Network. We divided their liver allografts into declined (nontransplanted) and transplanted ones, and then characterized declined ones focusing on their timepoints of decline and accompanying marginal factors. For each marginal factor, we calculated the decline rate from the number of declined and transplanted allografts, and assessed the 1‐year graft survival rate from transplanted allografts.

Results

A total of 571 liver allografts were divided into 84 (14.7%) declined and 487 (85.3%) transplanted ones. In the declined allografts, a majority was declined after laparotomy (n = 55, 65.5%), most of which had steatosis and/or fibrosis (n = 52). Out of the moderate steatotic (without F ≥ 2 fibrosis) allografts (n = 33), 21 were declined and 12 were transplanted, leading to a 63.6% decline rate. The latter 12 achieved a 92.9% 1‐year graft survival rate after transplantation. Comparison of donor background showed no significant difference between the declined and transplanted allografts.

Conclusion

Pathological abnormalities of steatosis/fibrosis seem to be the most common donor factor leading to graft decline in Japan. Allografts with moderate steatosis were highly declined; however, transplanted ones achieved promising outcomes. This national survey highlights the potential utility of liver allografts with moderate steatosis.
Habitat and ecological niche characteristics of the elusive Hairy‐eared Dwarf Lemur (Allocebus trichotis) with updated occurrence and geographic range data
Authors: Schüßler Dominik , Rabemananjara Naina R. , Radriarimanga Tahiriniaina , Rafamantanantsoa Stephan M. , Randimbiharinirina Roger D. , Radespiel Ute , Hending Daniel
Published: February 2023

Ecological niche modeling (ENM) is particularly useful in the study of cryptic and elusive species that are only rarely seen, difficult to study in the wild, and simultaneously threatened by a multitude of anthropogenic factors. We collected presence records one such example, the understudied Hairy‐eared Dwarf Lemur (Allocebus trichotis), from the literature and supplemented these with observations from surveys in previously unstudied areas to model its fundamental and realized niche throughout Madagascar. We further evaluated habitat characteristics at each sighting location to judge its conservation status and its adaptability toward habitat degradation. We found 31 presence localities in the literature and directly observed A. trichotis a further 23 times. According to the ENMs, precipitation of the driest quarter and maximum temperature of the warmest month mostly influenced its distribution, restricting it to the higher altitudes of the northeastern humid forests of Madagascar. Its fundamental niche, extent of occurrence, and area of occupancy were estimated as 65,819, 53,054, and 16,967 km² respectively. The latter, however, declined by 29.2% since 1990. On a habitat level, it was most often observed in primary forest habitats of different degradation stages (85.7%, n = 21). The fundamental niche of A. trichotis is most likely restricted by climatic factors. Although it can be found in moderately degraded forests, it is known to depend on the availability of tree holes and therefore old‐growth forest structures. Ongoing deforestation and habitat fragmentation are likely to be the major threats to the survival of this species. Our ENMs provide evidence on where to intensify survey efforts on the elusive Hairy‐eared Dwarf Lemurs of Madagascar.
Blood–Brain Barrier Remodeling in an Organ‐on‐a‐Chip Device Showing Dkk1 to be a Regulator of Early Metastasis
Authors: Westerhof Trisha M. , Yang Benjamin A. , Merrill Nathan M. , Yates Joel A. , Altemus Megan , Russell Liam , Miller Anna J. , Bao Liwei , Wu Zhifen , Ulintz Peter J. , Aguilar Carlos A. , Morikawa Aki , Castro Maria G. , Merajver Sofia D. , Oliver Christopher R.
Published: February 2023

Brain metastases are the most lethal progression events, in part because the biological processes underpinning brain metastases are poorly understood. There is a paucity of realistic models of metastasis, as current in vivo murine models are slow to manifest metastasis. Metabolic and secretory modulators of brain metastases utilizing two models consisting of in vitro microfluidic devices are delineated: 1) a blood–brain niche (BBN) chip that recapitulates the blood–brain‐ barrier and niche; and 2) a migration chip that assesses cell migration. Secretory cues provided by the brain niche that attract metastatic cancer cells to colonize the brain niche region are reported. Astrocytic Dkk‐1 is increased in response to brain‐seeking breast cancer cells and stimulates cancer cell migration. Brain metastatic cancer cells under Dkk‐1 stimulation increase gene expression of FGF‐13 and PLCB1. Further, extracellular Dkk‐1 modulates cancer cell migration upon entering the brain niche.