bluuebunny/crossref_metadata_2025_split huggingface dataset:
One‐Pot Synthesis of Tumor‐Microenvironment Responsive Degradable Nanoflower‐Medicine for Multimodal Cancer Therapy with Reinvigorating Antitumor Immunity
Authors: Sun Jiamin , Jiang Kai , Wang Yifan , Liu Yuqing , Wang Ting , Ding Shiyue , Zhang Xianzhi , Xiong Weiwei , Zheng Fenfen , Yang Haitang , Zhu Jun‐Jie 
Published: September 2023

AbstractMultimodal cancer therapies show great promise in synergistically enhancing anticancer efficacy through different mechanisms. However, most current multimodal therapies either rely on complex assemblies of multiple functional nanomaterials and drug molecules or involve the use of nanomedicines with poor in vivo degradability/metabolizability, thus restricting their clinical translatability. Herein, a nanoflower‐medicine using iron ions, thioguanine (TG), and tetracarboxylic porphyrin (TCPP) are synthesized as building blocks through a one‐step hydrothermal method for combined chemo/chemodynamic/photodynamic cancer therapy. The resulting nanoflowers, consisting of low‐density Fe2O3 core and iron complex (Fe‐TG and Fe‐TCPP compounds) shell, exhibit high accumulation at the tumor site, desirable degradability in the tumor microenvironment (TME), robust suppression of tumor growth and metastasis, as well as effective reinvigoration of host antitumor immunity. Triggered by the low pH in tumor microenvironment, the nanoflowers gradually degrade after internalization, contributing to the effective drug release and initiation of high‐efficiency catalytic reactions precisely in tumor sites. Moreover, iron ions can be eliminated from the body through renal clearance after fulfilling their mission. Strikingly, it is also found that the multimodal synergistic therapy effectively elicits the host antitumor immunity without inducing additional toxicity. This easy‐manufactured and degradable multimodal therapeutic nanomedicine is promising for clinical precision oncology.
Leveraging 3D Bioprinting and Photon‐Counting Computed Tomography to Enable Noninvasive Quantitative Tracking of Multifunctional Tissue Engineered Constructs
Authors: Gil Carmen J. , Evans Connor J. , Li Lan , Allphin Alex J. , Tomov Martin L. , Jin Linqi , Vargas Merlyn , Hwang Boeun , Wang Jing , Putaturo Victor , Kabboul Gabriella , Alam Anjum S. , Nandwani Roshni K. , Wu Yuxiao , Sushmit Asif , Fulton Travis , Shen Ming , Kaiser Jarred M. , Ning Liqun , Veneziano Remi , Willet Nick , Wang Ge , Drissi Hicham , Weeks Eric R. , Bauser‐Heaton Holly D. , Badea Cristian T. , Roeder Ryan K. , Serpooshan Vahid 
Published: September 2023

Abstract3D bioprinting is revolutionizing the fields of personalized and precision medicine by enabling the manufacturing of bioartificial implants that recapitulate the structural and functional characteristics of native tissues. However, the lack of quantitative and noninvasive techniques to longitudinally track the function of implants has hampered clinical applications of bioprinted scaffolds. In this study, multimaterial 3D bioprinting, engineered nanoparticles (NPs), and spectral photon‐counting computed tomography (PCCT) technologies are integrated for the aim of developing a new precision medicine approach to custom‐engineer scaffolds with traceability. Multiple CT‐visible hydrogel‐based bioinks, containing distinct molecular (iodine and gadolinium) and NP (iodine‐loaded liposome, gold, methacrylated gold (AuMA), and Gd2O3) contrast agents, are used to bioprint scaffolds with varying geometries at adequate fidelity levels. In vitro release studies, together with printing fidelity, mechanical, and biocompatibility tests identified AuMA and Gd2O3 NPs as optimal reagents to track bioprinted constructs. Spectral PCCT imaging of scaffolds in vitro and subcutaneous implants in mice enabled noninvasive material discrimination and contrast agent quantification. Together, these results establish a novel theranostic platform with high precision, tunability, throughput, and reproducibility and open new prospects for a broad range of applications in the field of precision and personalized regenerative medicine.
A Wearable Touch‐Activated Device Integrated with Hollow Microneedles for Continuous Sampling and Sensing of Dermal Interstitial Fluid
Authors: Abbasiasl Taher , Mirlou Fariborz , Mirzajani Hadi , Bathaei Mohammad Javad , Istif Emin , Shomalizadeh Narges , Cebecioğlu Rümeysa Emine , Özkahraman Ecem Ezgi , Yener Umut Can , Beker Levent 
Published: September 2023

AbstractDermal interstitial fluid (ISF) is emerging as a rich source of biomarkers that complements conventional biofluids such as blood and urine. However, the impact of ISF sampling in clinical applications has been limited owing to the challenges associated with extraction. The implementation of microneedle‐based wearable devices that can extract dermal ISF in a pain‐free and easy‐to‐use manner has attracted growing attention in recent years. Here, a fully integrated touch‐activated wearable device based on a laser‐drilled hollow microneedle (HMN) patch for continuous sampling and sensing of dermal ISF is introduced. The developed platform can produce and maintain the required vacuum pressure (as low as ≈ −53 kPa) to collect adequate volumes of ISF (≈2 µL needle−1 h−1) for medical applications. The vacuum system can be activated through a one‐touch finger operation. A parametric study is performed to investigate the effect of microneedle array size, vacuum pressure, and extraction duration on collected ISF. The capability of the proposed platform for continuous health monitoring is further demonstrated by the electrochemical detection of glucose and pH levels of ISF in animal models. This HMN‐based system provides an alternative tool to the existing invasive techniques for ISF collection and sensing for medical diagnosis and treatment.
Fast Gas‐Adsorption Kinetics in Supraparticle‐Based MOF Packings with Hierarchical Porosity
Authors: Fujiwara Atsushi , Wang Junwei , Hiraide Shotaro , Götz Alexander , Miyahara Minoru T. , Hartmann Martin , Apeleo Zubiri Benjamin , Spiecker Erdmann , Vogel Nicolas , Watanabe Satoshi 
Published: September 2023

AbstractMetal–organic frameworks (MOFs) are microporous adsorbents for high‐throughput gas separation. Such materials exhibit distinct adsorption characteristics owing to the flexibility of the crystal framework in a nanoparticle, which can be different from its bulk crystal. However, for practical applications, such particles need to be compacted into macroscopic pellets, creating mass‐transport limitations. In this work, this problem is addressed by forming materials with structural hierarchy, using a supraparticle‐based approach. Spherical supraparticles composed of nanosized MOF particles are fabricated by emulsion templating and they are used as the structural component forming a macroscopic material. Zeolitic imidazolate framework‐8 (ZIF‐8) particles are used as a model system and the gas‐adsorption kinetics of the hierarchical material are compared with conventional pellets without structural hierarchy. It is demonstrated that a pellet packed with supraparticles exhibits a 30 times faster adsorption rate compared to an unstructured ZIF‐8 powder pellet. These results underline the importance of controlling structural hierarchy to maximize the performance of existing materials. In the hierarchical MOFs, large macropores between the supraparticles, smaller macropores between individual ZIF‐8 primary particles, and micropores inherent to the ZIF‐8 framework collude to combine large surface area, defined adsorption sites, and efficient mass transport to enhance performance.
Spontaneous Vortex‐Antivortex Pairs and Their Topological Transitions in a Chiral‐Lattice Magnet
Authors: Yu Xiuzhen , Kanazawa Naoya , Zhang Xichao , Takahashi Yoshio , Iakoubovskii Konstantin V. , Nakajima Kiyomi , Tanigaki Toshiaki , Mochizuki Masahito , Tokura Yoshinori 
Published: September 2023

AbstractThe spontaneous formation and topological transitions of vortex‐antivortex pairs have implications for a broad range of emergent phenomena, for example, from superconductivity to quantum computing. Unlike magnets exhibiting collinear spin textures, helimagnets with noncollinear spin textures provide unique opportunities to manipulate topological forms such as (anti)merons and (anti)skyrmions. However, it is challenging to achieve multiple topological states and their interconversion in a single helimagnet due to the topological protection for each state. Here, the on‐demand creation of multiple topological states in a helimagnet Fe0.5Co0.5Ge, including a spontaneous vortex pair of meron with topological charge N = −1/2 and antimeron with N = 1/2, and a vortex‐antivortex bundle, that is, a bimeron (meron pair) with N = −1 is reported. The mutual transformation between skyrmions and bimerons with respect to the competitive effects of magnetic field and magnetic shape anisotropy is demonstrated. It is shown that electric currents drive the individual bimerons to form their connecting assembly and then into a skyrmion lattice. These findings signify the feasibility of designing topological states and offer new insights into the manipulation of noncollinear spin textures for potential applications in various fields.
An Enzymatic Electrochemical Biosensing Interface Developed by The Laser‐Induced Graphene Electrode
Authors: Liu Mingyang , Zhao Guangyao , Yang Cheng , Wang Han , Cheng Jing 
Published: September 2023

AbstractLaser‐inducing provides a cost‐effective, easily‐manufacturable, and environment‐friendly approach to directly transfer carbon‐rich polymers into graphene materials, which attracts attention from various fields, such as sensors, electrocatalysts, micro‐supercapacitors, etc. Laser‐induced graphene (LIG) benefits from the intrinsic properties of graphene, for example, high conductivity, high electroactivity, and high specific area. In this work the potential of laser‐induced graphene in constructing an enzymatic electrochemical biosensing interface is evaluated. Here, a laminar‐structured laser‐induced graphene material is fabricated by laser engraving with polyimide. After deposition of the electron mediator ferrocene, a conjugated enzyme complex of bovine serum albumin‐glucose oxidase (BSA‐GOx) is modified on the laser‐induced graphene by cross‐linking. The fabricated glucose oxidase/ferrocene/LIG (GOx/Fc/LIG) biosensor achieves high sensitivity of 11.3 µA mM−1 cm−2), wide linear range of 0–11 mM, and low detection of limit of 0.04 µM. The LIG electrodes exhibit high flexibility with bending angle as high as 60° without observed conductivity change. The repeatability and robustness of the developed LIG biosensor in detection of real serum samples empower it with great potential in clinical implementation in the future.
Asymmetric [4+2]‐Cycloaddition of Anthracene Derivatives via Hydrazone Activation
Authors: Łukasik Beata , Ossowski Jakub , Frankowski Sebastian , Albrecht Łukasz 
Published: September 2023

AbstractEnantio‐ and diastereoselective dearomative [4+2]‐cycloaddition reaction between N,N‐dimethylhydrazone derived from 9‐anthracenecarboxaldehyde and α,β‐unsaturated aldehydes is reported. The developed strategy utilizes HOMO‐rising activation of diene (via hydrazone formation) and aminocatalytic LUMO‐lowering activation of dienophile (via iminium ion formation). High chemical and stereochemical efficiency have been obtained owing to the application of Jørgensen catalyst. Target cycloadducts were subjected to selected transformations aiming at unmasking the hydrazone moiety that proceeded with preservation of optical purity introduced in the organocatalytic step.
Tetrabutylammonium Halides as Selectively Bifunctional Catalysts Enabling the Syntheses of Recyclable High Molecular Weight Salicylic Acid‐Based Copolyesters
Authors: Ren Fangping , Xian Ji , Jia Zhaowei , Chen Zhichun , Fu Hongjun , Wang Rui , Chu Wen‐Dao , Pan Xiaobo , Wu Jincai 
Published: September 2023

AbstractTo synthesize high molecular weight poly(phenolic ester) via a living ring‐opening polymerization (ROP) of cyclic phenolic ester monomers remains a critical challenge due to serious transesterification and back‐biting reactions. Both phenolic ester bonds in monomer and polymer chains are highly active, and it is difficult so far to distinguish them. In this work, an unprecedented selectively bifunctional catalytic system of tetra‐n‐butylammonium chloride (TBACl) was discovered to mediate the syntheses of high molecular weight salicylic acid‐based copolyesters via a living ROP of salicylate cyclic esters (for poly(salicylic methyl glycolide) (PSMG), Mn=361.8 kg/mol, Ð<1.30). Compared to previous catalysis systems, the side reactions were suppressed remarkably in this catalysis system because phenolic ester bond in monomer can be selectively cleaved over that in polymer chains during ROP progress. Mechanistic studies reveal that the halide anion and alkyl‐quaternaryammonium cation work synergistically, where the alkyl‐quaternaryammonium cation moiety interacts with the carbonyl group of substrates via non‐classical hydrogen bonding. Moreover, these salicylic acid‐based copolyesters can be recycled to dimeric monomer under solution condition, and can be recycled to original monomeric monomers without catalyst under sublimation condition.
When Is a Bond Broken? The Polarizability Perspective.
Authors: Hait Diptarka , Head‐Gordon Martin 
Published: September 2023

AbstractThe question of when a chemical bond can be said to be broken is of fundamental chemical interest but has not been widely studied. Herein we propose that the maxima of static polarizability along bond dissociation coordinates naturally define cutoff points for bond rupture, as they represent the onset of localization of shared electron density into constituent fragments. Examples of computed polarizability maxima over the course of bond cleavage in main‐group and transition metal compounds are provided, across covalent, dative and charge‐shift bonds. The behavior along reaction paths is also considered. Overall, the static polarizability is found to be a sensitive reporter of electronic structure reorganization associated with bond stretching, and thus can serve as a metric for describing bond cleavage (or diagnose the absence of a chemical bond).
Dynamic Metal‐ligand Coordination for Fluorescence Color Regulation of Hydrazone‐based Bistable Photoswitches
Authors: Zhang Diankun , Zhao Jufu , Shao Aiwen , Li Jiangang , Zhang Ye , Liu Shujuan , Ma Yun , Zhao Qiang 
Published: September 2023

AbstractAchieving effective manipulation of emission color in photoresponsive materials is crucial for various advanced photonic applications. In this study, we designed and synthesized a hydrazone compound 1, ethyl (Z)‐2‐(2‐([2,2′:6′,2′′‐terpyridin]‐4′‐yl)hydrazineylidene)‐2‐(4‐(diphenylamino)phenyl)acetate, which possesses a push‐pull structure incorporating triphenylamine and terpyridine. The emission intensity of compound 1 can be repeatedly switched “off” and “on” by irradiation with visible light and UV light, which induces the isomerization transition between the Z and E forms. In addition, compound 1 is capable of changing its emission wavelength from 540 nm to 607 nm through coordination with different zinc salts in toluene/CH2Cl2 mixture (v : v=1 : 1). Importantly, we have successfully achieved dynamic manipulation of fluorescence color and intensity by altering the counterions of zinc complexes and switching the isomer from Z to E. Moreover, both compound 1 and its zinc complexes demonstrate remarkable photoswitchable properties with different fluorescence colors in the thin films. Finally, these films with various fluorescence colors were used for the production of luminescent tags.
Cost stickiness behavior and environmental uncertainty in different strategies: Evidence from Southeast Asia
Authors: Restuti Mitha Dwi , Gani Lindawati , Shauki Elvia R. , Leo Lianny 
Published: September 2023

AbstractManagers consider environmental uncertainty in making decisions. Accordingly, this study aims to test the positive effect of environmental uncertainty on cost stickiness. This study also investigates the effects of environmental uncertainty on cost stickiness under different strategies. Further, firms need more able managers to deal with uncertain environments. This study observes the different effects of environmental uncertainty on cost stickiness when managers have varying levels of managerial ability. We run the panel regression analysis of 23,298 firm‐year observations in Southeast Asian countries in 2013–2019. This study documents that environmental uncertainty increases cost stickiness, and the effects are qualitatively similar for prospector and defender strategies. Further, the effect of environmental uncertainty on cost stickiness is stronger in firms with low managerial ability for both the prospector and defender strategies. Greater environmental uncertainty increases cost stickiness (ratio of SG&A to sales). This increase can be interpreted as a negative signal for future profits and a positive signal that firms retain resources to meet future sales expectations. Managerial ability affects cost stickiness. Hence, less managerial ability strengthens the relationship between environmental uncertainty and cost stickiness. This study operationalizes environmental uncertainty using three dimensions: munificence, dynamism, and complexity, which are arguably more comprehensive than prior studies that only use a single uncertainty dimension. This study also adds strategy and managerial ability to the relationship between environmental uncertainty and cost behavior. It demonstrates that firms deal with uncertainty based on their competitive advantage and managerial capabilities. This study documents the cost behavior of Southeast Asian.
Bubble Interfacial Area in a Swirling Contactor: Experiments and Computational Fluid Dynamics Simulations
Authors: Xu Xiao , Gong Chunkai , Wang Shuo , Yang Qiang , Xi Zhenhao 
Published: September 2023

AbstractThe bubble size, gas holdup, and interfacial area in a swirling contactor were investigated through experiments and simulations. The interfacial area was obtained for liquids and gases with Reynolds numbers Rel and Reg, respectively. The contactor was divided into twelve subregions. Rel was negatively related to bubble size, gas holdup, and interfacial area, whereas Reg was positively associated. The maximum bubble interfacial area for the entire swirling contactor was 196.3 m−1 with a gas‐liquid ratio of 0.022. There is a trade‐off between centrifugal acceleration and bubble size for interfacial area.
Dual‐single‐atoms of Pt–Co boost sulfur redox kinetics for ultrafast Li–S batteries
Authors: Wu Hanyan , Gao Xuejie , Chen Xinyang , Li Weihan , Li Junjie , Zhang Lei , Zhao Yang , Jiang Ming , Sun Runcang , Sun Xueliang 
Published: September 2023

AbstractApplications of lithium–sulfur (Li–S) batteries are still limited by the sluggish conversion kinetics from polysulfide to Li2S. Although various single‐atom catalysts are available for improving the conversion kinetics, the sulfur redox kinetics for Li–S batteries is still not ultrafast. Herein, in this work, a catalyst with dual‐single‐atom Pt‐Co embedded in N‐doped carbon nanotubes (Pt&Co@NCNT) was proposed by the atomic layer deposition method to suppress the shuttle effect and synergistically improve the interconversion kinetics from polysulfides to Li2S. The X‐ray absorption near edge curves indicated the reversible conversion of Li2Sx on the S/Pt&Co@NCNT electrode. Meanwhile, density functional theory demonstrated that the Pt&Co@NCNT promoted the free energy of the phase transition of sulfur species and reduced the oxidative decomposition energy of Li2S. As a result, the batteries assembled with S/Pt&Co@NCNT electrodes exhibited a high capacity retention of 80% at 100 cycles at a current density of 1.3 mA cm−2 (S loading: 2.5 mg cm−2). More importantly, an excellent rate performance was achieved with a high capacity of 822.1 mAh g−1 at a high current density of 12.7 mA cm−2. This work opens a new direction to boost the sulfur redox kinetics for ultrafast Li–S batteries.
Polymorphism and Light‐Driven Forward Movement of TPE Derivative Micro‐Crystal due to ArH‐pi Interactions Difference
Authors: Hu Ming , Ye Feng‐Ying , Yu Wei , Sheng Kang , Wang Weizhou , Zheng Yan‐Song 
Published: September 2023

AbstractAggregation‐induced emission (AIE) and aggregation‐caused quenching (ACQ) are two classes of opposite luminescence phenomena. It is almost impossible to show both AIE and ACQ effect simultaneously by the same molecule. However, here we report that a simple TPE derivative TAP‐TPE grows into both AIE crystals and ACQ ones. It is found that equatorial, contact distance‐longer and weak ArH‐π interactions exist in AIE crystals while vertical, contact distance‐shorter and strong ArH‐π interactions appear in ACQ crystals. Theoretical calculation of electron density on the interaction atoms unveils that ACQ crystals have much larger change in electron density than AIE ones, suggesting that the intermolecular electron transfer aroused by the strong ArH‐π hydrogen bonds leads to ACQ phenomenon. This result provides a new insight into the emission mechanism in aggregation state. Interestingly, due to the ArH‐pi interactions difference, only one of five kinds of crystals shows rapid photochromism, and can act as multimode anti‐counterfeiting materials. Very exceptionally, for the first time we find that the photochromic micrometric rod‐like crystal even makes forward rolling movement as it repeatedly bends and straightens by responding to on and off of the ultraviolet light irradiation, displaying potential for photo‐actuator and light‐driven micro‐vehicle.
Deinterpenetration of IRMOF‐9.
Authors: Crom Audrey B. , Strozier Joseph L. , Tatebe Caleb J. , Carey Cassidy A. , Feldblyum Jeremy I. , Genna Douglas T. 
Published: September 2023

AbstractOne of the iconic characteristics of metal‐organic frameworks (MOFs) is the possesssion of guest‐accessible pores. Increasing pore size has a direct and often beneficial impact on a MOF's adsorption and separation properties. However, as pore size increases, the resulting void spaces are often filled by interpenetrated frameworks, where one or more networks crystallize within the pore system of another identical network, reducing the MOF's free volume and pore size. Furthermore, due to the thermodynamic favorability of interpenetration during solvothermal synthesis, techniques to synthetically differentiate interpenetrated from non‐interpenetrated MOFs are paramount. This study reports the synthesis of deinterpenetrated IRMOF‐9 via halide mediated deinterpenetrative conversion of Zn4O‐derived IRMOF‐9. IRMOF‐9, when treated with ethylammonium bromide, is quasi‐selectively etched, revealing the non‐interpenetrated analogue, IRMOF‐10 (deinterpenetrated IRMOF‐9), which can be isolated prior to complete dissolution by the bromide solution. Dye adsorption, surface area and pore size distribution analysis, and powder X‐ray diffraction are consistent with successful deinterpenetration.
One‐Pot Stereoselective Synthesis of Different Fused Multicyclic Iminosugars Based on the Iminium‐Ion Intermediate
Authors: Xie Song , Wu Jilai , Zhou Likai , Wei Chao , Li Xiaoliu , Chen Hua 
Published: September 2023

Comprehensive SummaryDifferent novel fused multicyclic iminosugars were synthesized from D‐ribose tosylate, aniline and vinyl ethyl ether by one‐pot three‐component stereoselective [4+2] reaction at different temperatures. The iminium‐ion is the key intermediate for the reaction. As a result, several complex fused iminosugars 3a were obtained by aza‐Diels‐Alder mechanism at 60 °C, while a series of aza‐C‐glycosides 5a were prepared by Mannich reaction at room temperature accompanied by another tetrahydroquinoline‐fused iminosugars 4a (tricyclic derivatives) through aza‐Diels‐Alder cycloaddition. This strategy will help to construct structurally diverse and bioactive iminosugar analogues.