bluuebunny/crossref_metadata_2025_split huggingface dataset:
In Situ Nitric Oxide Gas Nanogenerator Reprograms Glioma Immunosuppressive Microenvironment
Authors: Liu Yang , Cui Lin , Wang Xiao , Miao Weiling , Ju Yongxu , Chen Tiandong , Xu Huiting , Gu Ning , Yang Fang 
Published: April 2023

AbstractUniversal chemotherapy in glioblastoma patients causes chemoresistance and further limits immune cells by creating an immunosuppressive tumor microenvironment that are difficult to solve by single‐drug therapeutic approaches. Here, this work designs hybrid drug‐loaded nanoliposomes by co‐loading the chemotherapeutic drug temozolomide (TMZ) and nitric oxide (NO) prodrug JS‐K with sphingosine‐1‐phosphate molecules (S1P) on the surface. The S1P‐S1P receptors axis endows nanoliposomes with rapid targeting and lysosomal escaping capability. Then, fine‐tuned TMZ release and NO gas production following JS‐K release in glioma microenvironment decrease chemoresistance and increase tumor immunogenicity through inhibiting the cellular autophagy as well as inducing mitochondrial dysfunction. RNA sequencing analysis demonstrates that the NO gas generation reprograms glioma microenvironment immune and inflammation‐related pathways. The positive immune response in turn effectively activates the enhanced efficacy of chemotherapy. NO gas generated nanoliposomes thus have attractive paradigm‐shifting applications in the treatment of “cold” tumors across a range of immunosuppressive indications.
Molecularly Resonant Metamaterials for Broad‐Band Electromagnetic Stealth
Authors: Wang Yifan , Niu Jiarong , Jin Xin , Qian Xiaoming , Xiao Changfa , Wang Wenyu 
Published: April 2023

AbstractElectromagnetic (EM) metamaterial is a composite material with EM stealth properties, which is constructed by artificially reverse engineering metal split resonance rings (SRR). However, the greatest limitation of EM metamaterials is that they can only stealth at a fixed and lower frequency of EM waves, and modern processing techniques still cannot meet the accuracy requirements to fabric nano‐size structural unit. Nano‐sized and even ultra‐small SRR at molecular level are promising arrays to realize the ability of EM stealth function at a higher frequency, although it has proven challenging to synthesize long, straight, connected molecular SRR, and also difficult to arrange those molecular SRR into a strict array. Here, the study overcomes this challenge and demonstrates that the fabric of polypyrrole molecular SRR achieves an ultra‐small inner diameter of 2.49 Å and realizes the arrays arrangement at molecular level. Furthermore, the study exploits the EM stealth function and verifies that such arrays of molecular SRR with 2.49 Å have the ability to reach high‐performance EM stealth in the range of 106–1016 Hz. This design concept opens a pathway for developing new metamaterials with broadband EM wave stealth and also serves the wider range of new applications.
A Smart Nano‐Theranostic Platform Based on Dual‐microRNAs Guided Self‐Feedback Tetrahedral Entropy‐Driven DNA Circuit
Authors: Yang Sha , Luo Jie , Zhang Ligai , Feng Liu , He Yuan , Gao Xueping , Xie Shuang , Gao Mingxuan , Luo Dan , Chang Kai , Chen Ming 
Published: April 2023

AbstractMicroRNAs (miRNAs) can act as oncogenes or tumor suppressors, capable of up or down‐regulating gene expression during tumorigenesis; they are diagnostic biomarkers or therapeutic targets for tumors. To detect low abundance of intracellular oncogenic miRNAs (onco‐miRNAs) and realize synergistic gene therapy of onco‐miRNAs and tumor suppressors, a smart nano‐theranostic platform based on dual‐miRNAs guided self‐feedback tetrahedral entropy‐driven DNA circuit is created. The platform as a delivery vehicle is a DNA tetrahedral framework, in which the entropy‐driven DNA circuit achieves a dual‐miRNAs guided self‐feedback, between an in situ amplification of the onco‐miRNAs and activation of suppressor miRNAs release. To test this platform, dual‐miRNAs are selected, miRNA‐155, an up‐regulated miRNA, as cancer indicators, and miRNA‐122, a down‐regulated miRNA as therapy targets in hepatocellular carcinoma, respectively. Through the circuit, the platform to detect onco‐miRNAs at femtomolar level as well as visualized miRNAs inside cells, fixed tissues, and mice is programmed. Furthermore, triggered by miRNA‐155, preloaded miRNA‐122 is amplified via the self‐feedback and released into target cells; the sudden increase of miRNA‐122 and simultaneous decrease of miRNA‐155 synergistically served as therapeutic drugs for gene regulation with enhanced antitumor efficacy and superior biosafety. It is envisioned that this nano‐theranostic platform will initiate an essential step toward tumor theranostics in personalized/precise medicine.
Ultrathin Carbon Coating and Defect Engineering Promote RuO2 as an Efficient Catalyst for Acidic Oxygen Evolution Reaction with Super‐High Durability
Authors: Yan Haohao , Jiang Zhongqing , Deng Binglu , Wang Yongjie , Jiang Zhong‐Jie 
Published: April 2023

AbstractDeveloping acid‐stable electrocatalysts with high activity for the oxygen evolution reaction (OER) is of paramount importance for many energy‐related technologies. This work reports that ultrathin nitrogen‐doped carbon coated oxygen‐vacancy (Vo·) rich RuO2 nanoparticles on carbon nanotubes (CNTs) (NC@Vo·‐RuO2/CNTs‐350), synthesized through the controlled calcination in air, is an efficient acid‐stable electrocatalyst for the OER. It only needs an overpotential of 170.0 mV to drive 10.0 mA cm−2 and shows excellent stability with no distinguishable activity loss observed for >900 h. Its mass activity is >110 times higher than the commercial RuO2. In particular, an electrolyzer assembled with this catalyst shows a record‐low cell voltage of 1.45 V to deliver 10.0 mA cm−2 and exhibits a low performance drop for >1000 h. The NC@Vo·‐RuO2/CNTs‐350 also shows super‐high catalytic activities and excellent stabilities for OER in neutral and alkaline media. DFT calculations indicate that its high catalytic activity mainly arises from the strong electronic coupling between RuO2 and NC/CNTs, which increases the oxidation state and catalytic activity of Ru at the active site and improves the stabilities of lattice oxygen and surface Ru during the OER processes. The presence of Vo· can strengthen the electronic coupling between RuO2 and NC/CNTs.
A Stable Imide‐Linked Metalphthalocyanine Framework with Atomically Dispersed Fe‐N4 Sites and Ultrafine Nickel Oxide Nanoparticles to Boost Reversible Oxygen Electrocatalysis with a Record‐Low ΔE of 0.59 V
Authors: Zhang Zhen , Wang Tianping , Wang Weiwen , Wang Xiangnan , Luo Xianglin , Cheng Chong , Liu Xikui 
Published: April 2023

AbstractMetallophthalocyanines (MPcs) hold great promise in the electrochemical reduction of oxygen; however, their practical applications in energy storage and conversion are still limited by their low stability and poor water oxidation activity. Herein, a novel stable 2D imide‐linked metalphthalocyanine framework (denoted as FePc‐PI) is reported, that has atomically dispersed Fe‐N4 sites deposited on the KB substrate via in situ growth, followed by incorporation of ultrafine nickel oxide nanoparticles (NiOx@FePc‐PI/KB) to induce bifunctional electrocatalytic activities for the oxygen reduction reaction and oxygen evolution reaction. Benefitting from the robust aromatic backbone, the engineered catalytic centers, and the unique electronic structures owing to the interaction between the Fe‐N4 sites and NiOx species, the newly developed NiOx@FePc‐PI/KB catalyst exhibits excellent reversible oxygen bifunctional activity (E1/2 = 0.926 V, η10 = 285 mV), delivering a record‐low overpotential difference (ΔE) of 0.59 V, which far exceeds the noble‐metal‐based Pt/C+RuO2 benchmark (ΔE = 0.77 V) and represents the highest level for reported bifunctional electrocatalysts. Furthermore, the rechargeable aqueous Zn‐air batteries assembled with the NiOx@FePc‐PI/KB catalyst deliver a high peak power density of 232.9 mW cm−2 and long‐term cycling durability over 1400 cycles. Flexible all‐solid‐state Zn‐air batteries exhibit stable cycling at various flat/bent/flat states, thus demonstrating their excellent prospects in realistic implementations.
Hafnium Diboride Spherical Superstructure Born of 5d‐Metal Hf‐MOF‐Induced p Orbital Activity of B Atom and Enhanced Kinetics of Sulfur Cathode Reaction
Authors: Wang Bin , Wang Lu , Kong Yueyue , Wang Fengbo , Jing Zhongxin , Yang Xiaofan , Qian Yitai , Chen Ming , Xu Liqiang 
Published: April 2023

AbstractImproving the intrinsic catalytic activity of electrocatalysts is considered to be the “gold standard” to inhibit the shuttle effect in Li–S batteries. The question of how to expose active sites for anchoring and catalytic conversion of the polysulfides represents the direction of this research. The assembly of 0D nanoparticles or 2D nanosheets into 3D spherical superstructure is one of the problems of materials synthesis. Here, a spherical superstructure hafnium diboride derived from metal‐organic framework (MOF) nanoparticles is synthesized by one‐step borification. Benefiting from its unique superstructure, the obtained HfB2 exhibits excellent catalytic activity for the conversion of polysulfide. Theoretical calculations indicate that the strong spin–orbital coupling property of electron configuration of 5d Hf induces p orbitals of nonmetallic atoms closer to the Fermi level, thus endowing the anions with redox activity and unconventional superconductivity. These merits enable the HfB2‐based sulfur cathode to deliver a high initial discharge capacity of 1433 mAh g−1 at 0.2 C and 580 mAh g−1 at 5 C. With sulfur loading of 12.8 mg cm−2 and electrolyte dosage of 4 µL mg−1, the areal capacity can reach 15.5 mAh cm−2. This work provides a new understanding for designing superstructure borides involving 5d metals in Li–S batteries.
Employment effects of an emergency assistance package for migrants displaced by COVID‐19 in India
Authors: Varshney Deepak , Meenakshi J. V. 
Published: April 2023

AbstractThis paper examines the employment effects of an emergency assistance package by the Indian government, the Garib Kalyan Rozgar Abhiyaan that had the sole objective of providing employment to returning migrants. It was targeted to 116 districts that had seen returning migrants in excess of 25,000, was limited in duration to 4 months, and was directed at top‐up funding to public works and 25 other target sectors in rural areas. Using a sharp RD approach, we find that the intervention had substantive impacts on employment and in reducing rationing in public works and that it did so in a cost‐effective manner. In contrast to the widespread impression of a slow‐moving bureaucracy, these results point to an administrative machinery that was able to successfully implement this project within a relatively short period of time.
“Just because I have a medical degree does not mean I have the answers”: Using CBPR to enhance patient‐centered care within a primary care setting
Authors: Siegal Rachel , Nance Andrew , Johnson Atalaya , Case Andrew 
Published: April 2023

AbstractPatient‐centered care (PCC) is a health care delivery model that is considered a means to reduce inequities in the healthcare system, specifically through its prioritization of patient voice and preference in treatment planning. Yet, there are documented challenges to its implementation. Community‐based participatory research (CBPR) is seemingly well‐positioned to address such challenges, but there has been limited discussion of utilizing CBPR in this way. This article begins to address this gap. In it, we present three diverse stakeholders' perspectives on a CBPR project to enhance PCC within a primary care clinic serving low‐income patients. These perspectives provide insights into benefits, challenges, and lessons learned in using CBPR to implement PCC. Key benefits of using CBPR to implement PCC include increasing the acceptability and feasibility of data collection tools and process, and the generating of high‐quality actionable feedback. Important CBPR facilitators of PCC implementation include intentional power‐sharing between patients and providers and having invested stakeholders who “champion” CBPR within an organization with empowering practices.
Synthesis and Application of Amino‐1H‐1,2,3‐triazolium Salts
Authors: Kase Daiya , Takada Tsuyoshi , Tsuji Nanami , Mitsuhashi Takuya , Haraguchi Ryosuke 
Published: April 2023

AbstractHerein, we developed a fluoride‐mediated nucleophilic aromatic amination of chloro‐1H‐1,2,3‐triazolium salts. Various functional groups were tolerated in this reaction, which enabled the synthesis of functionalized amino‐1H‐1,2,3‐triazolium salts. In addition, we investigated the catalytic properties of triazolium‐based N‐heterocyclic imines (NHIs) for cyanosilylation of ketones. The substituent was found to play a crucial role for inducing high catalytic activity.
Modification of Landau Levels in a 2D Ring Due to Rotation Effects and Edge States
Authors: Pereira Luís Fernando C. , Silva Edilberto O. 
Published: April 2023

AbstractThe properties of a 2D quantum ring under rotating and external magnetic field effects are investigated. The Landau levels and their inertial effects on them are initially analyzed. Among the results obtained, it is emphasized that the rotation lifted the degeneracy of Landau levels. The second part deals with the electronic confinement in a 2D ring modeled by a hard wall potential. The eigenstates are described by Landau states as long as they are not too close to the ring edges. On the other hand, near the ring edges, the energies increase monotonically. These states are known as edge states. Edge states have a significant role in the physical properties of the ring. Thus, the Fermi energy and magnetization are analyzed. In the specific case of magnetization, two approaches are considered. In the first approach, an analytical result for magnetization is obtained but without considering rotation. Numerical results show the de Haas‐Van Alphen (dHvA) oscillations. In the second approach, rotating effects are considered. In addition to the dHvA oscillations, the Aharonov–Bohm‐type (AB) oscillations are verified, which are associated with the presence of edge states. The effects of rotation on the results are discussed and it is found that rotation is responsible for inducing AB oscillations.
Enhancement of the Quantum Coherence in a Hierarchical Environment System by Weak Measurement and Weak Measurement Reversal
Authors: Bai Xue‐Min , Chen Xin‐Yu , Shi Jun‐Jie , Bai Xue‐Yun , Li Jun‐Qi , Liang Jiu‐Qing 
Published: April 2023

AbstractThe quantum coherence of a two‐qubit system in which each qubit is coupled to its own hierarchical environment is studied. The effect of the hierarchical environment is explored in order to improve the coherence effectively. It is discovered that the dynamics of coherence can be manipulated by the number N of the second‐layer cavities (), the coupling strengths Ω0, Ω, κ, respectively for the qubit‐cavity (m0), nearest‐neighbor, and m0‐ cavities. It depends also on the decay rate Γ of second‐layer cavities. Furthermore, an effective scheme for enhancing coherence is proposed by using weak measurement and weak measurement reversal. The explicit conditions of the optimal measurement strengths to improve the coherence comparatively are derived. It is seen that the final stable value of the coherence is independent of the number N of second‐layer cavities but is related to the weak measurement strength m when the coupling strength between two nearest‐neighbor cavities is taken into account.
Anomalous Spin Textures in a 2D Topological Superconductor Induced by Point Impurities
Authors: Martínez Dunkan , Díaz‐Fernández Álvaro , Orellana Pedro A. , Domínguez‐Adame Francisco 
Published: April 2023

AbstractTopological superconductors are foreseen as good candidates for the search of Majorana zero modes, where they appear as edge states and can be used for quantum computation. In this context, it becomes necessary to study the robustness and behavior of electron states in topological superconductors when a magnetic or non‐magnetic impurity is present. The focus is on scattering resonances in the bands and on spin texture to know what the spin behavior of the electrons in the system will be. It is found that the scattering resonances appear outside the superconducting gap, thus providing evidence of topological robustness. Non‐trivial and anisotropic spin textures related to the Dzyaloshinskii–Moriya interaction are also found. The spin textures show a Ruderman–Kittel–Kasuya–Yosida interaction governed by Friedel oscillations. It is believed that the results are useful for further studies which consider many‐point‐impurity scattering or a more structured impurity potential with a finite range.
Copper(I)‐Catalyzed Conjugate Addition/Enantioselective Protonation with Selenols and α‐Substituted α,β‐Unsaturated Thioamides
Authors: Tian Hu , Zhang Hong‐Ming , Yin Liang 
Published: April 2023

AbstractHerein, a copper(I)‐catalyzed asymmetric conjugate addition/protonation with selenols and α‐substituted α,β‐unsaturated thioamides is disclosed, which affords a series of chiral selenides in high to excellent enantioselectivity. As for both selenols and α‐substituted α,β‐unsaturated thioamides, the reaction enjoys broad substrate scopes. The present catalytic system is also successfully applied to asymmetric selenation of β‐substituted α,β‐unsaturated thioamides. A [Cu‐(R,RP)‐TANIAPHOS]‐SePh species is characterized by its 77Se NMR spectra, which gives a chemical shift at δ 462 ppm. Moreover, a {[Cu‐(R)‐TOL‐BINAP]‐SePh}2 species is characterized by X‐ray analysis, which confirms the formation of Cu−Se bond in the reaction. Finally, the transformations of the thioamide group to amine and thioester are demonstrated to be straightforward.
Elucidation of a Dearomatization Route in the Biosynthesis of Oxysporidinone Involving a TenA‐like Cytochrome P450 Enzyme
Authors: Li Dan , Wang Wenxuan , Xu Kangping , Li Jing , Long Bi , Li Zhansheng , Tan Guishan , Yu Xia 
Published: April 2023

AbstractOxidative dearomatization of phenols is an important transformation for synthesis of complex molecules. Oxysporidinone and related 2‐pyridones feature a hydroxy‐substituted cyclohexanone ring, which has been proposed to form by phenol dearomatization, although the details of the biochemical process are still unknown. In this study, we identified the oxysporidinone biosynthetic gene cluster in Fusarium oxysporum by regulator activation and gene knockout studies. Through in vivo and in vitro studies, we confirmed that the phenol dearomatization process involves two enzymes. OsdM, a TenA‐like cytochrome P450 with expected ring‐expansion activity, converts the phenol ring and the 4‐hydroxy‐2‐pyridone core into an unexpected fused [6‐5‐6] ring system. OsdN, on the other hand, catalyzes two successive ene reduction reactions, followed by hydroxylation by OsdM. This new route enriches current knowledge on enzymatic phenol dearomatization and the mechanism of TenA‐like P450s.
Design of a Bilateral Disulfurating Reagent for Unsymmetrical Polysulfidation
Authors: Tian Qingqiang , Li Yahui 
Published: April 2023

AbstractIn this study, we designed a bilateral disulfurating reagent via S−S motif “snip and stitch” processes, allowing diverse functional groups to be bridged via S−S bonds. The reagent is readily synthesized in high yield using a one‐step reaction from easily available starting materials and is air‐stable. With this reagent, diverse electrophiles including inactivated alkyl Cl/Br/I/OMs and benzyl chloride were sequentially installed on either side of the S−S motif. Natural products, agrochemicals, and pharmaceuticals can be successively cross‐linked with S−S bonds. Notably, the disulfurating reagent can be used in cyclic disulfide synthesis. At last, some desired products of this work showed good antibacterial activities, which could be employed as novel candidates to control plant pathogenic bacteria.
Photo‐Driven Iron‐Induced Non‐Oxidative Coupling of Methane to Ethane
Authors: Zhang Huizhen , Zhong Wanfu , Gong Qiaobin , Sun Pengfei , Fei Xiaozhen , Wu Xuejiao , Xu Sha , Zhang Qinghong , Fu Gang , Xie Shunji , Wang Ye 
Published: April 2023

AbstractPhoto‐driven CH4 conversion to multi‐carbon products and H2 is attractive but challenging, and the development of efficient catalytic systems is critical. Herein, we construct a solar‐energy‐driven redox cycle for combining CH4 conversion and H2 production using iron ions. A photo‐driven iron‐induced reaction system was developed, which is efficient at selective coupling of CH4 as well as conversion of benzene and cyclohexane under mild conditions. For CH4 conversion, 94 % C2 selectivity and a C2H6 formation rate of 8.4 μmol h−1 is achieved. Mechanistic studies reveal that CH4 coupling is induced by hydroxyl radical, which is generated by photo‐driven intermolecular charge migration of an Fe3+ complex. The delicate coordination structure of the [Fe(H2O)5OH]2+ complex ensures selective C−H bond activation and C−C coupling of CH4. The produced Fe2+ can be used to reduce the potential for electrolytic H2 production, and then turns back into Fe3+, forming an energy‐saving and sustainable recyclable system.
Exploring Synthetic Strategies for 1H‐Indazoles and Their N‐Oxides: Electrochemical Synthesis of 1H‐Indazole N‐Oxides and Their Divergent C−H Functionalizations
Authors: Arepally Sagar , Kim Taehoon , Kim Gyeongho , Yang Haesik , Park Jin Kyoon 
Published: April 2023

AbstractThe selective electrochemical synthesis of 1H‐indazoles and their N‐oxides and the subsequent C−H functionalization of the 1H‐indazole N‐oxides are described. The electrochemical outcomes were determined by the nature of the cathode material. When a reticulated vitreous carbon cathode was used, a wide range of 1H‐indazole N‐oxides were selectively synthesized, and the electrosynthesis products were deoxygenated to N‐heteroaromatics, owing to cathodic cleavage of the N−O bond via paired electrolysis, when a Zn cathode was used. The scope of this electrochemical protocol is broad, as both electron‐rich and electron‐poor substrates were tolerated. The potency of this electrochemical strategy was demonstrated through the late‐stage functionalization of various bioactive molecules, making this reaction attractive for the synthesis of 1H‐indazole derivatives for pharmaceutical research and development. Detailed mechanistic investigations involving electron paramagnetic resonance spectroscopy and cyclic voltammetry suggested a radical pathway featuring iminoxyl radicals. Owing to the rich reactivity of 1H‐indazole N‐oxides, diverse C−H functionalization reactions were performed. We demonstrated the synthetic utility of 1H‐indazole N‐oxides by synthesizing the pharmaceutical molecules lificiguat and YD (3); key intermediates for bendazac, benzydamine, norepinephrine/serotonin reuptake inhibitors, SAM‐531, and gamendazole analogues; and a precursor for organic light‐emitting diodes.