bluuebunny/crossref_metadata_2025 huggingface dataset:
Electrochemically Induced Crystalline‐to‐Amorphous Transition of Dinuclear Polyoxovanadate for High‐Rate Lithium‐Ion Batteries
Authors: Li Xiaolei , Lin Zifeng , Jin Na , Sun Lei , Yang Xiaojiao , Liu Ying
Published: January 2023

Polyoxometalates are intriguing high‐capacity anode materials for alkali‐metal‐ion storage due to their multi‐electron redox capabilities and flexible structure. However, their poor electrical conductivity and high working voltage severely restrict their practical application. Herein, the dinuclear polyoxovanadate Sr2V2O7·H2O with unusually high electrical conductivity is reported as a promising anode material for lithium‐ion batteries. During the initial lithiation process, the Sr2V2O7·H2O anode experiences an electrochemically induced crystalline‐to‐amorphous transition. The resulting amorphous structure provides high redox activity and fast reaction kinetics via reversible V4.9+/V2.8+ redox couple through the intercalation mechanism. Furthermore, when coupled with the LiFePO4 cathode, the strong VO bonds of the amorphous anode provide excellent structural stability, with the full‐cell capable of performing >12 000 cycles with a capacity retention of 72%. Another advantage of Sr2xV2O7‐δ·yH2O (0.5 ≤ x ≤ 1.0) is its composition adjustability, which enables delicately regulating the Sr vacancy content without destroying the structure. The defect Sr2xV2O7‐δ·yH2O (x = 0.5) electrodes show significantly improved specific capacity and rate capability without sacrificing other key properties, delivering a high specific capacity of 479 mAh g‐1 at 0.1 mA cm‐2 and 41.9% of its capacity in 2 min. Overall, the preliminary study points the way forward for the facile preparation of high‐quality polyoxometalates for advanced energy storage applications and beyond.
Machine‐Learning‐Assisted Nanozyme Design: Lessons from Materials and Engineered Enzymes
Authors: Zhuang Jie , Midgley Adam C. , Wei Yonghua , Liu Qiqi , Kong Deling , Huang Xinglu
Published: January 2023

Nanozymes are nanomaterials that exhibit enzyme‐like biomimicry. In combination with intrinsic characteristics of nanomaterials, nanozymes have broad applicability in materials science, chemical engineering, bioengineering, biochemistry, and disease theranostics. Recently, the heterogeneity of published results has highlighted the complexity and diversity of nanozymes in terms of consistency of catalytic capacity. Machine learning (ML) shows promising potential for discovering new materials, yet it remains challenging for the design of new nanozymes based on ML approaches. Alternatively, ML is employed to promote optimization of intelligent design and application of catalytic materials and engineered enzymes. Incorporation of the successful ML algorithms used in the intelligent design of catalytic materials and engineered enzymes can concomitantly facilitate the guided development of next‐generation nanozymes with desirable properties. Here, recent progress in ML, its utilization in the design of catalytic materials and enzymes, and how emergent ML applications serve as promising strategies to circumvent challenges associated with time‐expensive and laborious testing in nanozyme research and development are summarized. The potential applications of successful examples of ML‐aided catalytic materials and engineered enzymes in nanozyme design are also highlighted, with special focus on the unified aims in enhancing design and recapitulation of substrate selectivity and catalytic activity.
Cell Therapy Biomanufacturing: Integrating Biomaterial and Flow‐Based Membrane Technologies for Production of Engineered T‐Cells
Authors: Bomb Kartik , LeValley Paige J. , Woodward Ian R. , Cassel Samantha E. , Sutherland Bryan P. , Bhattacharjee Arnab , Yun Zaining , Steen Jonathan , Kurdzo Emily , McCoskey Jacob , Burris David , Levine Kara , Carbrello Christina , Lenhoff Abraham M. , Fromen Catherine A. , Kloxin April M.
Published: January 2023

Adoptive T‐cell therapies (ATCTs) are increasingly important for the treatment of cancer, where patient immune cells are engineered to target and eradicate diseased cells. The biomanufacturing of ATCTs involves a series of time‐intensive, lab‐scale steps, including isolation, activation, genetic modification, and expansion of a patient's T‐cells prior to achieving a final product. Innovative modular technologies are needed to produce cell therapies at improved scale and enhanced efficacy. In this work, well‐defined, bioinspired soft materials are integrated within flow‐based membrane devices for improving the activation and transduction of T‐cells. Hydrogel coated membranes (HCM) functionalized with cell‐activating antibodies are produced as a tunable biomaterial for the activation of primary human T‐cells. T‐cell activation utilizing HCMs lead to highly proliferative T‐cells that express a memory phenotype. Further, transduction efficiency is improved by several folds over static conditions by using a tangential flow filtration (TFF) flow‐cell, commonly used in the production of protein therapeutics, to transduce T‐cells under flow. The combination of HCMs and TFF technology leads to increased cell activation, proliferation, and transduction compared to current industrial biomanufacturing processes. The combined power of biomaterials with scalable flow‐through transduction techniques provides future opportunities for improving the biomanufacturing of ATCTs.
Aerosol Jet Printing of Multi‐Dimensional OECT Force Sensor with High Sensitivity and Large Measuring Range
Authors: Zhou Xinzhao , Zhang Liwen , Wang Yan , Zhao Song , Zhou Yu , Guo Yurun , Wang Yamei , Liang Jing , Chen Huawei
Published: January 2023

Multi‐dimensional tactile force sensors with high sensitivity, large measuring range, and direction recognition are essential for human‐machine interaction, medical rehabilitation, and humanoid robotics. Current tactile force sensors mainly make use of bump structure or 3D patterned composite layers to achieve multi‐dimensional force sensing, which not only results in thick sensors with unadjustable measuring performance, but brings about significant difficulties in fabrication. Here, an organic electrochemical transistor (OECT) based thin multi‐dimensional force sensor with tunable range/sensitivity has been designed with unilateral conductive micro‐riblets array, and aerosol jet printing was developed to build the unilateral conductive structure and multi‐material layers. Such unilateral conductive micro‐riblets array's directional dependent deformation endows the sensor with the capacities of lateral force response and force direction recognition. With the profound contact area sensitivity from super capacitance effect and signal amplifying of OECT, the aerosol jet printing OECT force sensor shows an adjustable sensing performance with high sensitivity of ≈1.45 kPa−1 at low‐pressure range of 0–500 Pa and a large measuring range even up to as high as 50 kPa. Finally, several tactile sensing applications have been demonstrated for the sensor's multifunctional performance.
An Effective Methodology for Achieving Highly Reliable Physical Sensors with High Sensitivity and Low Hysteresis through Parallel‐Structured Piezoresistors
Authors: Li Shuangying , Hwang Taehoon , Seo Jungyoon , Ko Eun , Tsogbayar Dashdendev , Khan Md. Rajibur Rahaman , Lee Hwa Sung
Published: January 2023

The representatively chronic problems of the piezoresistive‐type sensing media containing conductive fillers such as carbon nanotubes are dispersion problem when conductive fillers are composited with a high content for securing a certain conductivity and are low reliable sensor performance owing to the hysteresis of the sensing signals. Therefore, this study introduces a piezoresistive sensing medium with a multilayered parallel structure of resistors which effectively reduces the resistance and stabilizes the sensing signal. The multiparallel resistor (MPR) sensing medium with parallel‐connected structure shows an initial resistance ≈2.5 times lower compared to that of the typical single‐resistive type. When the proposed MPR sensing medium is applied as a strain sensor, GF value is 0.103 ± 0.009%−1 showing a remarkable improvement over 0.030 ± 0.018%−1 of the single type. The MPR strain sensor exhibits approximately the same GF values with no hysteresis and high linearity of the sensing signals in the forward and reverse strain directions. Finally, the developed MPR sensing medium is applied both as a strain sensor as well as a pressure sensor with excellent performance, thereby suggesting a new methodology to develop the high‐performance piezoresistive physical sensors.
Enhanced Supercontinuum Generation in Integrated Waveguides Incorporated with Graphene Oxide Films
Authors: Zhang Yuning , Wu Jiayang , Yang Yunyi , Qu Yang , Jia Linnan , Dirani Houssein El , Kerdiles Sébastien , Sciancalepore Corrado , Demongodin Pierre , Grillet Christian , Monat Christelle , Jia Baohua , Moss David J.
Published: January 2023

Enhanced supercontinuum generation (SCG) is experimentally demonstrated in integrated silicon nitride (Si3N4) waveguides incorporating highly nonlinear graphene oxide (GO) in the form of 2D films. On‐chip integration of the 2D GO films with precise control of their thickness is realized by using a transfer‐free and layer‐by‐layer coating method. The control of the film length and coating position is achieved via window opening in the upper silica cladding of the photonic integrated chips. Detailed SCG measurements are performed using the fabricated devices with different waveguide geometries and GO film thicknesses, and the results are compared with devices without GO. Significantly improved spectral broadening of ultrashort optical pulses with ultrahigh peak powers exceeding 1000 W is observed for the hybrid devices, achieving up to 2.4 times improvement in the spectral bandwidth relative to devices without GO. Theoretical analyses for the influence of GO film thickness, coating length, coating position, and waveguide geometry are also provided by fitting the experimental results with theory, showing that there is still significant room for further improvement. This work opens up a new avenue toward improving the SCG performance of photonic integrated devices by incorporating functional 2D materials.
A Magnetically Driven Amoeba‐Like Nanorobot for Whole‐Process Active Drug Transport
Authors: Zhu Yueqiang , Song Yonghong , Cao Ziyang , Dong Liang , Shen Song , Lu Yang , Yang Xianzhu
Published: January 2023

The passive diffusion performance of nanocarriers results in inefficient drug transport across multiple biological barriers and consequently cancer therapy failure. Here, a magnetically driven amoeba‐like nanorobot (amNR) is presented for whole‐process active drug transport. The amNR is actively extravasated from blood vessels and penetrated into deep tumor tissue through a magnetically driven deformation effect. Moreover, the acidic microenvironment of deep tumor tissue uncovers the masked targeting ligand of amNR to achieve active tumor cell uptake. Furthermore, the amNR rapidly releases the encapsulated doxorubicin (DOX) after alternating magnetic field application. The amNRs eventually deliver DOX into ≈92.3% of tumor cells and completely delay tumor growth with an inhibition rate of 96.1%. The deformable amNRs, with the assistance of magnetic field application, provide a facile strategy for whole‐process active drug transport.
From Free‐Radical to Radical‐Free: A Paradigm Shift in Light‐Mediated Biofabrication
Authors: Rizzo Riccardo , Petelinšek Nika , Bonato Angela , Zenobi‐Wong Marcy
Published: January 2023

In recent years, the development of novel photocrosslinking strategies and photoactivatable materials has stimulated widespread use of light‐mediated biofabrication techniques. However, despite great progress toward more efficient and biocompatible photochemical strategies, current photoresins still rely on photoinitiators (PIs) producing radical‐initiating species to trigger the so‐called free‐radical crosslinking/polymerization. In the context of bioprinting, where cells are encapsulated in the bioink, the presence of radicals raises concerns of potential cytotoxicity. In this work, a universal, radical‐free (RF) photocrosslinking strategy to be used for light‐based technologies is presented. Leveraging RF uncaging mechanisms and Michael addition, cell‐laden constructs are photocrosslinked by means of one‐ and two‐photon excitation with high biocompatibility. A hydrophilic coumarin‐based group is used to cage a universal RF photocrosslinker based on 4‐arm‐PEG‐thiol (PEG4SH). Upon light exposure, thiols are uncaged and react with an alkene counterpart to form a hydrogel. RF photocrosslinker is shown to be highly stable, enabling potential for off‐the‐shelf products. While PI‐based systems cause a strong upregulation of reactive oxygen species (ROS)‐associated genes, ROS are not detected in RF photoresins. Finally, optimized RF photoresin is successfully exploited for high resolution two‐photon stereolithography (2P‐SL) using remarkably low polymer concentration (<1.5%), paving the way for a shift toward radical‐free light‐based bioprinting.
Borophene Embedded Cellulose Paper for Enhanced Photothermal Water Evaporation and Prompt Bacterial Killing
Authors: Guan Xinwei , Kumar Prashant , Li Zhixuan , Tran Thi Kim Anh , Chahal Sumit , Lei Zhihao , Huang Chien‐Yu , Lin Chun‐Ho , Huang Jing‐Kai , Hu Long , Chang Yuan‐Chih , Wang Li , Britto Jolitta S. J. , Panneerselvan Logeshwaran , Chu Dewei , Wu Tom , Karakoti Ajay , Yi Jiabao , Vinu Ajayan
Published: January 2023

Solar‐driven photothermal water evaporation is considered an elegant and sustainable technology for freshwater production. The existing systems, however, often suffer from poor stability and biofouling issues, which severely hamper their prospects in practical applications. Conventionally, photothermal materials are deposited on the membrane supports via vacuum‐assisted filtration or dip‐coating methods. Nevertheless, the weak inherent material‐membrane interactions frequently lead to poor durability, and the photothermal material layer can be easily peeled off from the hosting substrates or partially dissolved when immersed in water. In the present article, the discovery of the incorporation of borophene into cellulose nanofibers (CNF), enabling excellent environmental stability with a high light‐to‐heat conversion efficiency of 91.5% and water evaporation rate of 1.45 kg m−2 h−1 under simulated sunlight is reported. It is also demonstrated that borophene papers can be employed as an excellent active photothermal material for eliminating almost 100% of both gram‐positive and gram‐negative bacteria within 20 min under three sun irradiations. The result opens a new direction for the design of borophene‐based papers with unique photothermal properties which can be used for the effective treatment of a wide range of wastewaters.
Oxygen Anion Redox Chemistry Correlated with Spin State in Ni‐Rich Layered Cathodes
Authors: Lu Zhihua , Zhang Jicheng , Zhang Qinghua , Wong Deniz , Yin Wen , Zhang Nian , Chen Zhongjun , Gu Lin , Hu Zhongbo , Liu Xiangfeng
Published: January 2023

Despite the low cost and high capacity of Ni‐rich layered oxides (NRLOs), their widespread implementation in electric vehicles is hindered by capacity decay and O release. These issues originate from chemo‐mechanical heterogeneity, which is mainly related to oxygen anion redox (OAR). However, what to tune regarding OAR in NRLOs and how to tune it remains unknown. In this study, a close correlation between the OAR chemistry and Li/Ni antisite defects is revealed. Experiments and calculations show the opposite effects of aggregative and dispersive Li/Ni antisite defects on the NiO6 configuration and Ni spin state in NRLOs. The resulting broad or narrow spans for the energy bands caused by spin states lead to different OAR chemistries. By tuning the Li/Ni antisite defects to be dispersive rather than aggregative, the threshold voltage for triggering OAR is obviously elevated, and the generation of bulk‐O2‐like species and O2 release at phase transition nodes is fundamentally restrained. The OAR is regulated from irreversible to reversible, fundamentally addressing structural degradation and heterogeneity. This study reveals the interaction of the Li/Ni antisite defect/OAR chemistry/chemo‐mechanical heterogeneity and presents some insights into the design of high‐performance NRLO cathodes.
Site‐Specific Antibody Assembly on Nanoparticles via a Versatile Coating Method for Improved Cell Targeting
Authors: Zhang Qianyi , Liang Jieying , Bongers Andre , Richardson Joseph J. , Liang Kang , Gu Zi
Published: January 2023

Antibody‐nanoparticle conjugates are promising candidates for precision medicine. However, developing a controllable method for conjugating antibodies to nanoparticles without compromising the antibody activity represents a critical challenge. Here, a facile and generalizable film‐coating method is presented using zeolitic imidazole framework‐8 (ZIF‐8) to immobilize antibodies on various nanoparticles in a favorable orientation for enhanced cell targeting. Different model and therapeutic antibodies (e.g., Herceptin) are assembled on nanoparticles via a biomineralized film‐coating method and exhibited high antibody loading and targeting efficiencies. Importantly, the antibodies selectively bind to ZIF‐8 via their Fc regions, which favorably exposes the functional Fab regions to the biological target, thus improving the cell targeting ability of antibody‐coated nanoparticles. In combination, molecular dynamics simulations and experimental studies on antibody immobilization, orientation efficiency, and biofunctionality collectively demonstrate that this versatile site‐specific antibody conjugation method provides effective control over antibody orientation and leads to improved cell targeting for a variety of nanoparticles.
A Flexible Corn Starch‐Based Biomaterial Device Integrated with Capacitive‐Coupled Memristive Memory, Mechanical Stress Sensing, Synapse, and Logic Operation Functions
Authors: Sun Bai , Chen Yuanzheng , Zhou Guangdong , Zhou Yongzan , Guo Tao , Zhu Shouhui , Mao Shuangsuo , Zhao Yong , Shao Jinyou , Li Yuning
Published: January 2023

Biomaterials‐based electronic devices (BEDs) have remarkable advantages such as biocompatibility and biodegradability, which are expected to have promising prospects in the development of green electronics such as wearable smart sensors and brain‐like synaptic devices. However, the development of BEDs is still in its infancy, and much work remains to be done before this technology can be widely used. Here, a novel corn starch‐based BED with a sandwiched structure of Ag/Corn starch:PVDF/ITO is developed, which has integrated multifunctional performance of capacitive‐coupled memristive memory, flexible mechanical stress sensing, synaptic application, and logic operation. Specifically, this device exhibits a wide memristive voltage operating range (1–16 V), a high bending response current (3.5–4.5 µA), long‐term durability synaptic performance, and logic operation capability. These advantageous characteristics endow this device has a good potential to be used in flexible wearable electronics and artificial intelligence.
Insights into the Enhanced Interfacial Stability Enabled by Electronic Conductor Layers in Solid‐State Li Batteries
Authors: Luo Linshan , Sun Zhefei , Gao Haowen , Lan Chaofei , Huang Xiaojuan , Han Xiang , Su Pengfei , Zhang Zhiyong , Li Cheng , Huang Wei , Wei Qiulong , Zhang Qiaobao , Wang Ming‐Sheng , Chen Songyan
Published: January 2023

The (electro)chemical reactions between Li1.3Al0.3Ti1.7(PO4)3 (LATP) solid‐state electrolyte and lithium metal plague the practical applications of LATP. A commonly used strategy to tackle this issue is to construct an ionic conductor layer to stabilize Li/LATP interface. Herein, it is demonstrated that an electronic conductor interlayer (Al or Ag) can also greatly enhance the interfacial stability of Li/LATP. To unveil the origin of the enhanced interfacial stability, a series of techniques, including in situ electron and optical microscopies, kelvin probe force microscopy, and finite element analysis, is exploited. Control experiments show clearly that Al layer can effectively homogenize the electric field distribution, which enables the uniform growth of interphases and thus prevents stress concentration and crack propagation. Moreover, when coupled with solid polymer electrolyte (SPE) to form Al‐SPE bilayer, it can effectively protect LATP from electron attack and interphase formation. Remarkably, Li symmetrical cells with an Al‐SPE bilayer exhibit superior stability of more than 5000 h at 0.2 mA cm−2, among the best cycling performances to date. This work presents an in‐depth understanding of the mechanism of the enhanced interfacial stability enabled by electronic conductor interlayers, as well as a universal interface architecture to boost the cyclability of solid‐state batteries.
Quantitative Understanding of Lithium Deposition‐Stripping Process on Graphite Anodes of Lithium‐Ion Batteries
Authors: Duan Xudong , Li Binqi , Li Jiani , Gao Xiang , Wang Lubing , Xu Jun
Published: January 2023

Metallic Lithium deposited on graphite particles is the major phenomenon responsible for the degradation of cell capacity, triggering of internal short circuit (ISC), and exacerbating thermal runaway (TR) in lithium‐ion batteries (LIBs). However, currently, no available physics‐based model can provide an accurate quantitative description of lithium‐plating behavior. Herein, this work establishes a mechanism model to characterize the Li deposition‐stripping process, especially the formation of dead Li and the reversibility of deposited Li. By the combination of the battery model and 3D particle model with the Li deposition‐stripping model, this work enables the quantitative prediction of Li deposition during charging–discharging cycles at various charging rates. Based on the revealed understanding of the Li deposition‐stripping process, a smart charging strategy with the optimization of the minimized Li‐deposition and expedited charging time is proposed. Furthermore, this work also quantifies the influence of anode heterogeneity on Li plating. The results highlight the promise of physics‐based mechanistic modeling for the quantification of the Li disposition‐stripping process and provide fundamental guidance on battery design and charging protocols for next‐generation long cycle life Li‐ion cells.
Sowing Single Atom Seeds: A Versatile Strategy for Hyper‐Low Noble Metal Loading to Boost Hydrogen Evolution Reaction
Authors: Li Qiqi , Zhang Qin , Xu Wenli , Zhao Rong , Jiang Min , Gao Yinhong , Zhong Wenda , Chen Kai , Chen Yongting , Li Xuanke , Yang Nianjun
Published: January 2023

The universal preparation of noble metal single‐atom catalysts (NMSACs) is critical for efficient sustainable energy conversion. In this study, a versatile sowing strategy is proposed to prepare the NMSACs with hyper‐low loading. A metal‐organic framework derived Ni(OH)x with Ni2+ vacancies serves as fertile soil with plentiful trapping holes, where the Pt atom seeds can be inserted. The Pt atoms tend to form tetradentate Pt‐O4 as the roots, confining the loading concentration to a hyper‐low range (≈0.17 wt%). This Pt‐Ni(OH)x catalyst exhibits an overpotential of 58 mV at a current density of 10 mA cm−2 in 1 m KOH for hydrogen evolution reaction and needs only 1.47 V to achieve η10 for water splitting. This approach is extended to the formation of other NMSACs such as Ir and Ru. The versatile sowing strategy thus provides guidance to prepare different NMSACs with excellent catalytic performance.
Engineering Self‐Supported Hydrophobic–Aerophilic Air Cathode with CoS/Fe3S4 Nanoparticles Embedded in S, N Co‐Doped Carbon Plate Arrays for Long‐Life Rechargeable Zn–Air Batteries
Authors: Yan Lei , Xie Binbin , Yang Chen , Wang Yahao , Ning Jiqiang , Zhong Yijun , Hu Yong
Published: January 2023

The highly sluggish kinetics of oxygen reduction/evolution reactions (ORR/OER) at air cathodes lead to problems such as low power density and unsatisfactory cycling life with rechargeable Zn–air batteries (RZABs). To engineer the reaction kinetics at the air cathodes, a hydrophobic–aerophilic strategy is developed to fabricate a self‐supported air cathode based on CoS/Fe3S4 nanoparticles encapsulated in S, N co‐doped carbon plate arrays (CoS/Fe3S4@SNCP). It is experimentally shown that the in situ growth of bimetallic sulfides nanoparticles on the carbon plate arrays improves the intrinsic electrocatalytic activity and electron conduction of the air cathode. Meanwhile, the ab initio molecular dynamics simulations reveal that the hydrophobic–aerophilic surface can repel water molecules to create abundant solid–liquid–gas three‐phase reaction interfaces as well as to expose Fe‐sites, which consequently promote the diffusion of reactive molecules/ions across the interface and the oxygen adsorption. As a result, the CoS/Fe3S4@SNCP electrode exhibits excellent OER and ORR activities with a smaller potential gap of 0.65 V. For the engineered hydrophobicity of the catalyst, the RZAB demonstrates a high power density of 272 mW cm−2, a narrow discharge/charge gap of 0.75 V at 10 mA cm−2, and long‐term cycling stability over 1400 h, outperforming its hydrophilic CoS@SNCP counterparts.
Fast and Facile Microwave Synthesis of Cubic CuFe2O4 Nanoparticles for Electrochemical CO2 Reduction
Authors: Zander Judith , Weiss Morten , Marschall Roland
Published: January 2023

Nanoparticles of cubic CuFe2O4 are obtained in a fast microwave‐assisted hydrothermal synthesis. By adjusting the pH value and solvent ratio (ethylene glycol to water), phase purity and high crystallinity is achieved at very short reaction times of 1 min, or low temperatures of 120 °C, without the need for subsequent heat treatment steps. The influence of the synthesis time or temperature on material properties and performance in electrochemical CO2 reduction to CO are investigated. While particle size and crystallinity are not changed significantly with longer synthesis times at 175 °C, prolonged heating results in a decrease of the degree of inversion, which leads to a decrease in the CO2 reduction ability. The best performance is observed for CuFe2O4 with an intermediate degree of inversion of approx. 0.75, together with the largest crystallite size and micro‐strain, as revealed by Rietveld refinement. For CuFe2O4 synthesized under these conditions, a CO evolution rate of 0.2 μmol h−1 g−1 is obtained at a Faradaic efficiency of 20%. The CO to H2 ratio is 1:3, which makes it a promising candidate for a sustainable production of syngas.
A Symmetry‐Broken Charge‐Separated State in the Marcus Inverted Region
Authors: Sebastian Ebin , Hariharan Mahesh
Published: January 2023

We report a long‐lived charge‐separated state in a chromophoric pair (DC‐PDI2) that uniquely integrates the advantages of fundamental processes of photosynthetic reaction centers: i) Symmetry‐breaking charge‐separation (SB‐CS) and ii) Marcus‐inverted‐region dependence. The near‐orthogonal bichromophoric DC‐PDI2 manifests an ultrafast evolution of the SB‐CS state with a time constant of
=0.35±0.02 ps and a slow charge recombination (CR) kinetics with
=4.09±0.01 ns in ACN. The rate constant of CR of DC‐PDI2 is 11 686 times slower than SB‐CS in ACN, as the CR of the PDI radical ion‐pair occurs in the deep inverted region of the Marcus parabola (
>λ). In contrast, an analogous benzyloxy (BnO)‐substituted DC‐BPDI2 showcases a ≈10‐fold accelerated CR kinetics with
lowering to ≈1536 in ACN, by virtue of a decreased CR driving force. The present investigation demonstrates a control of molecular engineering to tune the energetics and kinetics of the SB‐CS material, which is essential for next‐generation optoelectronic devices.
Enantioselective Intramolecular α‐Arylation of Benzylamine Derivatives: Synthesis of a Precursor to Levocetirizine
Authors: Saunthwal Rakesh K. , Schwarz Maria , Mallick Rajendra K. , Terry‐Wright William , Clayden Jonathan
Published: January 2023

A practical, transition metal‐free method allows the enantioselective synthesis of α,α‐diarylmethylamines by asymmetric α‐arylation of benzylamines. Enantioselective lithiation of N′‐aryl‐N‐benzyl‐N‐isopropyl ureas using a chiral lithium amide base generates a benzyllithium that undergoes an unactivated stereospecific intramolecular nucleophilic aromatic substitution to generate an α,α‐diarylmethylamine in the form of its urea derivative, in up to >99 % ee. Treatment with acid induces an “azatropic shift” with retention of configuration, the product of which may be hydrolysed to the target amine.
Halide Layer Cathodes for Compatible and Fast‐Charged Halides‐Based All‐Solid‐State Li Metal Batteries
Authors: Liang Jianwen , Li Xiaona , Kim Jung Tae , Hao Xiaoge , Duan Hui , Li Ruying , Sun Xueliang
Published: January 2023

Insertion‐type compounds based on oxides and sulfides have been widely identified and well‐studied as cathode materials in lithium‐ion batteries. However, halides have rarely been used due to their high solubility in organic liquid electrolytes. Here, we reveal the insertion electrochemistry of VX3 (X=Cl, Br, I) by introducing a compatible halide solid‐state electrolyte with a wide electrochemical stability window. X‐ray absorption near‐edge structure analyses reveal a two‐step lithiation process and the structural transition of typical VCl3. Fast Li+ insertion/extraction in the layered VX3 active materials and favorable interface guaranteed by the compatible electrode‐electrolyte design enables high rate capability and stable operation of all‐solid‐state Li‐VX3 batteries. The findings from this study will contribute to developing intercalation insertion electrochemistry of halide materials and exploring novel electrode materials in viable energy storage systems.
A Metabolic‐Tag‐Based Method for Assessing the Permeation of Small Molecules Across the Mycomembrane in Live Mycobacteria**
Authors: Liu Zichen , Lepori Irene , Chordia Mahendra D. , Dalesandro Brianna E. , Guo Taijie , Dong Jiajia , Siegrist M. Sloan , Pires Marcos M.
Published: January 2023

The general lack of permeability of small molecules observed for Mycobacterium tuberculosis (Mtb) is most ascribed to its unique cell envelope. More specifically, the outer mycomembrane is hypothesized to be the principal determinant for access of antibiotics to their molecular targets. We describe a novel assay that combines metabolic tagging of the peptidoglycan, which sits directly beneath the mycomembrane, click chemistry of test molecules, and a fluorescent labeling chase step, to measure the permeation of small molecules. We showed that the assay workflow was robust and compatible with high‐throughput analysis in mycobacteria by testing a small panel of azide‐tagged molecules. The general trend is similar across the two types of mycobacteria with some notable exceptions. We anticipate that this assay platform will lay the foundation for medicinal chemistry efforts to understand and improve uptake of both existing drugs and newly‐discovered compounds into mycobacteria.
Fluorescent Probes Based on AIEgen‐Mediated Polyelectrolyte Assemblies for Manipulating Intramolecular Motion and Magnetic Relaxivity
Authors: Yao Yongkang , Ding Peng , Yan Chenxu , Tao Yining , Peng Bo , Liu Weimin , Wang Junyou , Cohen Stuart Martien A. , Guo Zhiqian
Published: January 2023

Uniting photothermal therapy (PTT) with magnetic resonance imaging (MRI) holds great potential in nanotheranostics. However, the extensively utilized hydrophobicity‐driven assembling strategy not only restricts the intramolecular motion‐induced PTT, but also blocks the interactions between MR agents and water. Herein, we report an aggregation‐induced emission luminogen (AIEgen)‐mediated polyelectrolyte nanoassemblies (APN) strategy, which bestows a unique “soft” inner microenvironment with good water permeability. Femtosecond transient spectra verify that APN well activates intramolecular motion from the twisted intramolecular charge transfer process. This de novo APN strategy uniting synergistically three factors (rotational motion, local motion, and hydration number) brings out high MR relaxivity. For the first time, APN strategy has successfully modulated both intramolecular motion and magnetic relaxivity, achieving fluorescence lifetime imaging of tumor spheroids and spatio‐temporal MRI‐guided high‐efficient PTT.
CNTs‐coated TPU/ANF composite fiber with flexible conductive performance for joule heating, photothermal, and strain sensing
Authors: He Pengxin , Pu Haihong , Li Xinfeng , Hao Xiaoqiong , Ma Jianhua
Published: January 2023

Flexible and highly conductive fiber has attracted considerable attention with its massive potential in functional fabric, stretchable circuits, and wearable electronic devices. Herein, we prepared a novel secondary structure composite fiber based on aramid nanofibers (ANF)‐reinforced thermoplastic polyurethane (TPU) fiber accompanied by carbon nanotube (CNT)‐coated on its surface. The composite fibers' dispersibility, micromorphology, and application were systematically investigated. The TPU/ANF‐0.5 wt% sample showed a robust reinforcing effect, as Young's modulus and tensile strength reached 17.2 and 20.2 MPa, respectively. Meanwhile, the conductive coating layer in the outer frame was formed via a TPU solution with 10 wt% CNT content, which gives the fiber excellent flexible electrical conductivity. Such a unique structural design enables the fiber to be closely attached to human skin and monitor human movement. In addition, this TPU/ANF@CNT composite fiber can also be used for light and electric heating. The photothermal equilibrium temperature can reach 120°C in 50 s, and the electrothermal equilibrium temperature increases to 62°C under 30 V. In summary, this secondary structure composite fiber with excellent electrical and mechanical properties might have great practical application potential in wearable electronic devices.
Three‐dimensional culture of rat ovarian granulosa cells shows increased SPP1 and FGF7 expression through the PI3K/Akt pathway
Authors: Zhang Yaping , Zhu Huasu , Liu Linghong , Ma Huixian , Shi Qing , Li Dong , Ju Xiuli
Published: January 2023

Ovarian granulosa cells (OGCs) play an essential role in the regulation of follicular growth and development. However, previous studies of OGCs have concentrated on traditional 2D cultures. In the present study, we used the hanging drop culture method to culture rat OGCs (rOGCs) and assessed the effects of 3D conditions on their proliferation and gene expression profiles. Compared with those grown in 2D conditions, rOGCs grown in 3D cultures showed a significantly different spatial cell distribution and cell alignment under electron microscopy. In particular, rOGCs in 3D cultures showed abundant rough and microvilli‐like structures on their cell surface. Here, we showed that these cells grew slowly following 3D culture; the G0/G1‐phase increased and the S‐ and G2/M‐phases decreased. Using whole‐transcriptome sequencing analysis, 501 genes were shown to have been significantly upregulated and 502 were shown to have been downregulated. Differentially expressed genes were most enriched in pathways involved in focal adhesion, MAPK, and PI3K/Akt signaling according to Kyoto Encyclopedia of Genes and Genomes pathway enrichment analysis. Western blotting revealed that SPP1 and FGF7 in the PI3K/Akt pathway were significantly upregulated following 3D culture. These findings improve our understanding of OGCs in real 3D environments in vivo and provide possible avenues for future research on OGCs.
Preparation of Ropivacaine Encapsulated by Zeolite Imidazole Framework Microspheres as Sustained‐Release System and Efficacy Evaluation
Authors: Wang Peng , Wang Guangyu , Tang Hongwen , Feng Siwen , Tan Lichuan , Zhang Pu , Wei Guihua , Wang Cuijuan
Published: January 2023

The management of persistent postoperative pain still remains a clinical challenge currently. Although ropivacaine (RVC) is widely used for postoperative analgesia as a local anesthetic, the short half‐life makes it difficult to achieve the desired duration of analgesia. Herein, a RVC sustained‐release microspheres encapsulated by zeolite imidazole framework‐8 (RVC@ZIF‐8) was synthesized for the first time, which prolonged the sustained‐release of RVC and decreased the resulting drug toxicity. RVC can continuously release in vitro for at least 96 h with high drug loading of 30.6 % and RVC@ZIF‐8 had excellent biocompatibility and low cytotoxicity. In sciatic nerve block model, the sensory block time of RVC@ZIF‐8 was significantly prolonged compared with RVC, achieving more than 72 h post injection and no inflammation or lesion were found. Based on high drug loading, ideal sustained‐release and superior biological safety, RVC@ZIF‐8 will be a novel delivery material for local anesthetic with potential application.
Evaluation by Experimentation and Simulation of a FRET Pair Comprising Fluorescent Nucleobase Analogs in Nucleosomes
Authors: Hirashima Shingo , Park Soyoung , Sugiyama Hiroshi
Published: January 2023

Förster resonance energy transfer (FRET) is an attractive tool for understanding biomolecular dynamics. FRET‐based analysis of nucleosomes has the potential to fill the knowledge gaps between static structures and dynamic cellular behaviors. Compared with typical FRET pairs using bulky fluorophores introduced by flexible linkers, fluorescent nucleoside‐based FRET pair has great potential since it can be fitted within the helical structures of nucleic acids. Herein we report on the construction of nucleosomes containing a nucleobase FRET pair and the investigation of experimental and theoretical FRET efficiencies through steady‐state fluorescence spectroscopy and calculation based on molecular dynamics simulations, respectively. Distinguishable experimental FRET efficiencies were observed depending on the positions of FRET pairs in nucleosomal DNA. The tendency could be supported by theoretical study. This work suggests the possibility of our approach to analyze structural changes of nucleosomes by epigenetic modifications or internucleosomal interactions.
The survival of childhood leukemia: An 8‐year single‐center experience
Authors: Bordbar Mohammadreza , Jam Nazila , Karimi Mehran , Shahriari Mahdi , Zareifar Soheila , Zekavat Omid Reza , Haghpanah Sezaneh , Mottaghipisheh Hadi
Published: January 2023

Background

The survival of childhood leukemia has improved. We aimed to report the survival rate and the associated factors in children with acute leukemia during an 8‐year follow‐up.

Aims

This study investigates the 8‐year survival rates of children with acute myeloid leukemia (AML) and acute lymphoblastic leukemia (ALL) in Shiraz, the largest oncology center in Southern Iran. We also aimed to assess the independent factors associated with higher mortality in childhood leukemia.

Methods

Children 0–18 years with acute leukemia were followed from 2013 to 2021 in Shiraz, Iran. The 8‐year overall survival (OS) and event‐free survival (EFS) rates were estimated by the Kaplan–Meier method. Independent factors associated with survival were assessed by the Cox regression hazard modeling.

Results

We included 786 children, with 43.5% female, and a mean age of 6.32 ± 4.62 years. Patients with AML compared to ALL experienced more relapse (34.6% vs. 22.5%,p = .01) and death (31.7% vs. 11.3%,p < .001). The cumulative 8‐year OS and EFS were 81% (95% confidence interval (CI), 74.3% to 86.1%) and 68.3% (95% CI, 63.5% to 72.7%) in ALL patients and 63.5% (95% CI, 52.1% to 72.9%) and 43% (95% CI, 33.1% to 52.6%) in AML patients. Multivariable analysis revealed that hepatomegaly (hazard ratio = 4, 95% CI, 1.0 to 22.3,p = .05) was the main independent risk factor of death in ALL patients. No definite risk factor was defined for AML patients.

Conclusion

The survival of childhood leukemia has recently increased dramatically in low‐middle income countries. Hepatomegaly was introduced as a potential risk factor for lower survival in ALL patients. Further multicenter studies are needed to confirm the validity of this association.
The Helmholtz‐Kohlrausch effect on display‐based light colors and simulated substrate colors
Authors: High Gregory , Green Phil , Nussbaum Peter
Published: January 2023

The Helmholtz‐Kohlrausch (H‐K) effect is investigated in relation to light colors of every hue, including those typical of print substrate colors that might be simulated on a graphic arts display. A method of adjustment is used in conjunction with a soft‐proof setup, in which an achromatic stimulus is adjusted until it has the same lightness appearance as a set of test colors. Higher chroma colors are found to appear lighter than their metric would indicate. The H‐K effect is found to be quite strong in bluish colors, but negligible in yellowish colors, consistent with several previous studies. However, qualitative analysis reveals a peak H‐K effect in red‐magenta hues. We propose a modification to Fairchild and Pirrotta's existing H‐K lightness appearance function1 which addresses the peak in red hues, and which may prove beneficial in hue‐dependent applications.
Stochastic modeling for energy efficiency in modified directional discontinuous reception for LTE‐5G networks
Authors: Kalita Priyanka , Selvamuthu Dharmaraja
Published: January 2023

Fifth‐generation (5G) networks deal with high‐frequency data rates, ultra‐low latency, more reliability, massive network capacity, more availability, and a more uniform user experience. To validate the high‐frequency rates, 5G networks engage beam searching operation. By adopting a beam searching state between the short and long sleep, one can reduce the system's delay. The energy consumption of user equipment (UE) in 5G networks is much higher than in the 4G networks. To reduce the energy consumption and increase the energy saving in UE, Long‐Term Evolution (LTE)‐5G networks adopt the discontinuous reception (DRX) scheme with a fixed number of short sleep. LTE‐DRX without beam search operation (i.e., beam alignment) cannot work in 5G networks. Hence, keeping this scenario in mind, we have modeled a new modified directional discontinuous reception (MD‐DRX) mechanism for LTE‐5G networks. The MD‐DRX mechanism captures the behavior of a beam searching, an inactive, an active, a long sleep, an ON, and a short sleep states. The short sleep state consists of a maximum short sleep. To get the optimal energy saving and energy consumption (i.e., energy efficiency) from the MD‐DRX mechanism, it is required to check the system's throughput. The trade‐off between energy saving/energy consumption and throughput will provide the system's optimal energy saving and optimal energy consumption. In this paper, we have obtained the system's optimal energy saving and throughput by optimizing the maximum short sleep and short sleep duration. To get the energy efficiency for LTE‐5G networks, the trade‐off between average energy consumption/energy saving and throughput is shown.
Does Milan affect management? A retrospective analysis of resection rate and time to surgery among Milan categories
Authors: Tenney Troy B. , Mullane Patrick C. , Viswanathan Kartik , Shi Qiuying , Lui Shu K. , Lubin Daniel J.
Published: January 2023

Introduction

The Milan System for Reporting Salivary Gland Cytopathology (MSRSGC) is an established system with reproducible risk of malignancies (ROM) for salivary gland fine needle aspiration (SGFNA). No studies have reviewed the relationship between Milan categories and the resection rate (RR) and time to resection (TTR).

Methods

We searched our database (January 1, 2011 to January 4, 2021) for non‐lymphoma SGFNAs and assigned appropriate MSRSGC categories. RR and TTR were calculated and compared for each category. A literature search was performed; RRs and TTRs were compared.

Results

Seven hundred and eighty SGFNAs were identified, 333 with follow‐up. RR was highest in suspicious for malignancy (SUS, V; 70.6%, n = 12/17), followed by the salivary gland neoplasm of uncertain malignant potential (SUMP, IVb; 69.6%, n = 80/115) and malignant (M, VI; 55.6%, n = 75/135). Among M, primary tumors had a higher RR (65.1%, n = 41/63) than metastases (47.2%, n = 34/72, p = .36). In literature review, SUS had the highest RR (69.3%, n = 233/336) followed by M (61.6%, n = 821/1332) and SUMP (60.2%, n = 632/1050). TTR was shorter in SUS (mean = 32.3 days, median = 25 days). Within the benign neoplasms (BN, IVa), Pleomorphic adenomas (PAs) had a higher RR than Warthin tumors (WTs) (66.3% vs. 37.2%, p < .00001), and a shorter TTR (median = 63 days vs. 90 days).

Conclusions

Tumors classified as SUS had higher RR and at shorter intervals than those classified as SUMP. PAs have higher RRs and more expedient surgery than WTs. Cases classified as M are less likely to undergo follow‐up than SUS, perhaps due to a lower RR for metastases.
Metabolites identification of anabolic steroid bolasterone in vitro and in rats by high resolution liquid chromatography mass spectrometry
Authors: Muresan Anca Raluca , Rahaman Khandoker Asiqur , Son Junghyun , Kang Min‐Jung , Kwon Oh‐Seung
Published: January 2023

Bolasterone (7α,17α–dimethyltestosterone) and anabolic androgenic steroids are included in the World Anti‐Doping Agency's Prohibited list of substances. This study aimed to evaluate the metabolism of bolasterone through in vitro experiments using rat liver microsomes and in vivo experiments using rat urine after oral administration. Urine samples were collected over a 168‐h period. Bolasterone and its metabolites were detected by liquid chromatography coupled with a Q‐Exactive Obitrap mass spectrometry (LC‐HRMS). Ultimately 16 hydroxylated metabolites (M1–M16), one metabolite from the reduction of the 3‐keto function and 4‐ene (M17), and one glucuronic acid conjugated metabolite (M18) were detected. Metabolites M17 and M18 were confirmed by comparison with available reference or authentic standards. Metabolic modifications in the structure of the parent bolasterone result in different fragmentation patterns. Based on the sensitivity of the HRMS data, characteristic ions such as m/z 121.064 (C8H9O) generated from ring A of the mono‐hydroxylated metabolites and 121.101 (C9H13) generated from ring D of the di‐hydroxylated metabolites were observed that helped differentiate between the obtained metabolites. The structures of fragment ions were tentatively proposed based on their fragmentation pathways, where the significant ions were correlated to the possible structural fragments. In conclusion, new metabolites of bolasterone were detected and characterized by the use of the full‐scan and dd‐MS/MS using LC‐HRMS, and this data can be useful for providing metabolite information for the interpretation of mass spectra of anabolic bolasterone analogues for doping screening tests.
Simultaneous voltammetric determination of acetylsalicylic acid, caffeine and paracetamol in pharmaceutical formulations using screen‐printed carbon electrode
Authors: Cortés Karla , Triviño Juan José , Arancibia Verónica
Published: January 2023

Electrochemical oxidation of Paracetamol (PAR), Acetylsalicylic acid (ASA) and Caffeine (CAF) was investigated employing square wave stripping voltammetry (SWSV) using screen–printed carbon electrodes (SPCE). Determinations were performed in 0.1 mol L−1 BR buffer (pH 2.0) without accumulation step. SWV were obtained by scanning the potential from 0.00 to 1.40 V employing a scan increment of 4 mV, pulse amplitude 25 mV and frequency of 25 Hz. PAR, ASA and CAF presents oxidation signals at 0.45, 1.03 and 1.32 V. The detection limits were 1.2, 1.7 and 1.7 mg L−1, respectively. The method was applied in the PAR‐ASA‐CAF determination on pharmaceutical formulations.