bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractMicroinjection 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

AbstractHybrid 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

AbstractControlling 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

AbstractParametric 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

AbstractPermittivity 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

AbstractMacrolides, 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

AbstractThe 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

AbstractTreatment 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

AbstractCytotoxic 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

AbstractExisting 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

AbstractDue 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

AbstractDue 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

AbstractSolid 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

AbstractThe 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

AbstractThe 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.