bluuebunny/crossref_metadata_2025_split huggingface dataset:
Oxygen Vacancies Engineering in Thick Semiconductor Films via Deep Ultraviolet Photoactivation for Selective and Sensitive Gas Sensing
Authors: Abideen Zain Ul , Choi Jun‐Gyu , Yuwono Jodie A. , Kiy Alexander , Kumar Priyank Vijaya , Murugappan Krishnan , Lee Won‐June , Kluth Patrick , Nisbet David R. , Tran‐Phu Thanh , Yoon Myung‐Han , Tricoli Antonio 
Published: February 2023

AbstractRoom‐temperature detection of volatile organic compounds in particle‐per‐billion concentrations is critical for the development of wearable and distributed sensor networks. However, sensitivity and selectivity are limited at low operating temperatures. Here, a strategy is proposed to substantially improve the performance of semiconductor sensors. Tunable oxygen vacancies in thick 3D networks of metal oxide nanoparticles are engineered using deep ultraviolet photoactivation. High selectivity and sensitivity are achieved by optimizing the electronic structure and surface activity while preserving the 3D morphology. Cross‐sectional depth analysis reveals oxygen vacancies present at various depths (≈24% at a depth of 1.13 µm), with a uniform distribution throughout the thick films. This results in ≈58% increase in the sensitivity of ZnO to 20‐ppb ethanol at room temperature while ≈51% and 64% decrease in the response and recovery times, respectively. At an operating temperature of 150 °C, oxygen‐vacant nanostructures achieve a lower limit of detection of 2 ppb. Density functional theory analysis shows that inducing oxygen vacancies reduces activation energy for ethanol adsorption and dissociation, leading to improved sensing performance. This scalable approach has the potential for designing low‐power wearable chemical and bio‐sensors and tuning the activity and band structure of porous, thick oxide films for multiple applications.
Enhancement of Light Extraction Efficiency and Suppression of Roll‐Off Characteristics of Thermally Activated Delayed Fluorescence Organic Light‐Emitting Diodes by Inserting Nanoscale Pixel‐Defining Layer
Authors: Lee Seungwon , Park Jun‐Young , Park Jaewon , Bi Jian Cheng , Kang Byeongwoo , Hwang Young Hyun , Seok Jiwon , Park Young Wook , Ju Byeong‐Kwon 
Published: February 2023

AbstractThermally activated delayed fluorescence (TADF) organic molecules are considered the most suitable for blue organic light‐emitting diodes (OLEDs) after extensive research; however, they are plagued by issues of internally guided light and the roll‐off characteristics contributed by triplet exciton‐utilized emission. Thus, this study leverages exciton diffusion guidance and energy extraction to simultaneously achieve optical efficiency enhancement and roll‐off characteristic suppression of mixed‐host blue TADF OLEDs. The array of nanopixels, defined by the inserted nanoscale pixel‐defining layer (nPDL), spatially separates the excitons and polarons, resulting in the exacerbation of triplet quenching by securing exciton diffusion. Furthermore, through the formation of a metal cathode with a corrugated profile, nonradiative energy transfer to the surface plasmon polaritons is capitalized via Bragg diffraction, thereby boosting the emission efficiency. The structure of the nPDL is judiciously determined by finite‐difference time‐domain computational analysis. Consequently, the device with the optimized nPDL demonstrates 88.4%, 118.8%, and 108.8% improvements in external quantum, current, and power efficiencies, respectively, compared to the reference. Moreover, the critical luminance, which quantifies the degree of roll‐off, is improved by 83.7%. This pioneering demonstration of hybridizing the material combination and nanopatterning techniques is expected to provide new insights for designing high‐performance OLEDs.
Understanding of Low‐Porosity Sulfur Electrode for High‐Energy Lithium–Sulfur Batteries
Authors: Fu Yucheng , Singh Rajesh K , Feng Shuo , Liu Jun , Xiao Jie , Bao Jie , Xu Zhijie , Lu Dongping 
Published: February 2023

AbstractThe lithium–sulfur (Li–S) battery is a promising technology for large‐scale energy storage and vehicle electrification due to its high theoretical energy density and low cost. Reducing the sulfur cathode porosity has been identified recently as a viable strategy for improving the cell practical energy density and minimizing pore‐filling electrolytes to extend cell life at lean electrolyte conditions. Direct use of a low‐porosity cathode for Li–S battery results in poor electrode wetting, nonuniform electrode reactions, and thus early cell failure. To understand and mitigate the barriers associated with the use of low‐porosity electrodes, multiscale modeling is performed to predict electrode wetting, electrolyte diffusion, and their impacts on sulfur reactions in Li–S cells by explicitly considering the electrode wettability impacts and electrode morphologies. The study elucidates the critical impact of low tortuosity and large channel pore design for promoting electrode wetting and species diffusion. It is suggested that the secondary particle size should be comparable with the electrode thickness to effectively promote electrolyte wettability and sulfur reactivity. This study provides new insights into the low‐porosity electrode material and designs and is expected to accelerate the development of practical high‐energy Li–S batteries.
Multifunctional Doping Strategy to Develop High‐Performance Ni‐Rich Cathode Material
Authors: Park Nam‐Yung , Cho Gyeil , Kim Su‐Bin , Sun Yang‐Kook 
Published: February 2023

AbstractA high fraction of reactive Ni4+ ions at the cathode–electrolyte interfaces lead to capacity fading of Ni‐rich cathodes. Therefore, a core–shell (CS) design encapsulating the Ni‐rich region by a Ni‐less shell is an effective approach for improving the cycling stability of the cathodes. However, with increasing average Ni content to increase the capacity, the thickness of the shell should be reduced or the Ni fraction of the shell will be inevitably higher, making it susceptible to interdiffusion, which flattens the concentration gradient during the lithiation process. Herein, the limit of the average Ni composition in the CS‐type cathode is pushed to 94% via Ta doping, which suppresses interdiffusion by segregating the Ta‐rich phases at the particle boundaries. Ta doping allows the maintenance of the highly aligned microstructure and the ordered intermixing structure of Li and transition metal ions, as well as the concentration gradient, over a wide lithiation temperature range. The Ta‐doped CS‐type cathode retains 92.6% of its initial capacity after 1000 cycles and exhibits resistance to damage from fast charging. Multifunctional Ta doping in the CS‐type cathode provides a simple and all‐around solution to maximize the electrochemical performance of Ni‐rich cathodes, providing flexibility in the lithiation process.
Probing the electrostatic aggregation of nanoparticles with oppositely charged molecular ions
Authors: Huang Jianxiang , Buratto Damiano , Zhou Ruhong 
Published: February 2023

AbstractThe co‐assembly of charged nanoparticles with oppositely charged molecular ions has emerged as a promising technique in the fabrication of nanoparticle superstructures. However, the underlying mechanism behind these molecular ions in mediating the repulsion between these charged nanoparticles remains elusive. Herein, coarse‐grained molecular dynamics simulations are used to elucidate the effects of valency, shape, and size of molecular anions on their co‐assembly with gold nanoparticles coated with positively charged ligands. The findings suggest that the valency, shape, and size of molecular anions significantly influence the repulsion and aggregating dynamics among these positively charged nanoparticles. Moreover, the free energy calculations reveal that ring‐shaped molecular anions with higher valences and larger sizes are more effective at reducing the repulsion between these gold nanoparticles and thus enhance the stability of the aggregate. This study contributes to a better understanding of the critical roles of valence, shape, and size of ions in mediating the electrostatic co‐assembly of nanoparticles with oppositely charged ions, and it also guides the future design of DNA templates and DNA origami in co‐assembly with oppositely charged nanoparticles.
Photo‐responsive Single‐Molecule Magnet Showing 0D to 1D Single‐Crystal‐to‐Single‐Crystal Structural Transition and Hysteresis Modulation
Authors: Huang Xin‐Da , Ma Xiu‐Fang , Zheng Li‐Min 
Published: February 2023

AbstractPhoto‐responsive lanthanide‐based single‐molecule magnets (SMM) hold great promise for future switching and memory devices. Herein, we report a dysprosium phosphonate [DyIII(SCN)2(NO3)(depma)2(4‐hpy)2] (1Dy), which features a supramolecular framework containing layers of hydrogen‐bonding network and pillars of π–π interacted anthracene units. The photocycloaddition reaction of anthracene pairs led to a rapid and reversible single‐crystal‐to‐single‐crystal (SC–SC) structural transition to form the 1D coordination polymer [DyIII(SCN)2(NO3)(depma2)(4‐hpy)2]n(2Dy), accompanied by photoswitchable SMM properties with the reduction of effective energy barrier by half and the narrowing of the butterfly‐like hysteresis loop. The diluted sample showed a photo‐induced switch of the blocking temperature (TB) from 3.8 K for1Dy@Yto 2.6 K for2Dy@Y. This work may inspire the construction of lanthanide‐based molecular materials with targeted photo‐responsive magnetic properties.
Impact of mechanochemical treatment on surface chemistry and flocculation of kaolinite dispersion
Authors: Bhatti Qaisar Abbas , Baloch Musa Kaleem , Schwarz Simona , Ishaq Muhammad 
Published: February 2023

AbstractFor many industrial applications, an extensive research of the stabilization and destabilization mechanisms of aqueous suspensions of fine particles is crucial. The flocculation of charged particles from their aqueous suspensions is greatly influenced by the surface characteristics of the particles. For the purpose of improving the flocculation efficiency of kaolin suspensions, the impact of the proposed mechanochemical treatment, which includes homogenization and/or ultrasonication followed by the addition of polycation such as poly (diallyl dimethyl‐ammonium chloride) (PDADMAC), was examined under standard conditions. It was demonstrated that parameters including kaolin's specific surface area, surface charge density, and particle size reduction are all affected by the duration of the ultrasonication. While ultrasonication (10 min) has a significant impact on particle size distributions, 300 and 200 nm‐sized particles were also seen. A narrow flocculation window was obtained by PDADMAC at a Cp/Cs ratio of 0.1 mg/g (Cp/Cs means the ratio of mass polymer/mass substrate), while the mechanical treatment via homogenization with magnetic stirring (60 min) resulted in a larger flocculation window of kaolin caused by the polyelectrolyte used. However, mechanochemical treatment via ultrasonication followed by the addition of aforementioned polyelectrolyte played a significant role in achieving the highest turbidity removal. Hence, the settling behavior of kaolin suspension depends upon the pH, ultra‐sonication time, and the concentration of polyelectrolyte. The combination of ultra‐sonication, PDADMAC dosage, and pH (mechanic‐chemical treatment) played an excellent role in the maximum removal of turbidity, and the broadest flocculation window comprising of 0.4 to 1.6 mg/g was observed at pH 8.
Chiral Self‐Sorting in Pd6L12 Metal‐Organic Cages
Authors: Ghorai Sandipan , Maji Suman , Paul Bhaswati , Samanta Krishanu , Kumar Sen Shovan , Natarajan Ramalingam 
Published: February 2023

AbstractChiral self‐sorting during the formation of cage‐like molecules continues to fascinate and advance our understanding of the phenomenon in general. Herein, we report the chiral self‐sorting in the Pd6L12‐type metal‐organic cages. When a racemic mixture of axially chiral bis‐pyridyl ligands undergo coordination‐driven self‐assembly with Pd(II) ions to form Pd6L12‐type cages, the system has the option of chiral self‐sorting to afford any of at least 70 pairs of (one homochiral and 69 heterochiral) enantiomers and 5 meso isomers or a statistical mixture of everything. However, the system resulted in diastereoselective self‐assembly through a high‐fidelity chiral social self‐sorting to form a racemic mixture of D3 symmetric heterochiral [Pd6(L6R/6S)12]12+/[Pd6(L6S/6R)12]12+ cages.
Universally Exhaustive Generation of Molecular Structures and Prediction of Their Electronic States Using Machine Learning for N‐type Organic Transistor Materials
Authors: Ohno Akira , Hanna Jun‐ichi , Iino Hiroaki , Nakago Kosuke , Yamaguchi Taiki , Abe Motoki , Akita Hirotaka , Takemoto Mizuki 
Published: February 2023

AbstractWe have proposed a new method for the exploration of organic functional molecules, using an exhaustive molecular generator combined without combinatorial explosion and electronic state predicted by machine learning and adapted for developing n‐type organic semiconductor molecules for field‐effect transistors. Our method first enumerates skeletal structures as much as possible and next generates fused ring structures using substitution operations for atomic nodes and bond edges. We have succeeded in generating more than 4.8 million molecules. We calculated the electron affinity (EA) of about 51 thousand molecules with DFT calculation and trained the graph neural networks to estimate EA values of generated molecules. Finally, we obtained the 727 thousand molecules as candidates that satisfy EA values over 3 eV. The number of these possible candidate molecules is far beyond what we have been able to propose based on our knowledge and experience in synthetic chemistry, indicating a wide diversity of organic molecules.
Halogen Bond‐Involving Supramolecular Assembly Utilizing Carbon as a Nucleophilic Partner of I⋅⋅⋅C Non‐covalent Interaction
Authors: Smirnov Andrey S. , Mikherdov Alexander S. , Rozhkov Anton V. , Gomila Rosa M. , Frontera Antonio , Kukushkin Vadim Yu. , Bokach Nadezhda A. 
Published: February 2023

AbstractCo‐crystallization of 180°‐orienting σ‐hole‐accepting tectons, namely, 1,4‐diisocyanobenzene (1) and 1,4‐diisocyanotetramethylbenzene (2), with such homoditopic halogen bond donors as 1,4‐diiodotetrafluorobenzene (1,4‐FIB) and 4,4’‐diiodoperfluorobiphenyl (4,4’‐FIBP) afforded co‐crystals 1 ⋅ 1,4‐FIB, 1 ⋅ 4,4’‐FIBP, and 2 ⋅ 1,4‐FIB. Their solid‐state structures exhibit 1D‐supramolecular arrangements, which are based on poorly explored I⋅⋅⋅C halogen bonding; this study is the first in which the supramolecular assembly utilizing halogen bonding with a terminal C atom was performed. The use of the potentially tetrafunctional σ‐hole accepting tetraiodoethylene (TIE) leads to supramolecular architecture of a higher dimension, 3D‐framework, observed in the structure of 1 ⋅ TIE. DFT calculations, used to characterize the halogen bonding situation, revealed that the I⋅⋅⋅C non‐covalent interactions are moderately strong, ranging from −4.07 in 1 ⋅ TIE to −5.45 kcal/mol in 2 ⋅ 1,4‐FIB. The NBO analysis disclosed that LP(C)→σ* charge transfer effects are relevant in all co‐crystals.
Few‐layer Graphene Lithiophilic and Sodiophilic Diffusion Layer on Porous Stainless Steel as Lithium and Sodium Metal Anodes
Authors: Patrike Apurva , Wasnik Kundan , Shelke Manjusha V. 
Published: February 2023

AbstractIn order to subdue the obvious problem of uneven electric field distribution on regularly used copper/aluminum current collectors for alkali metal batteries, graphene on porous stainless steel (pSS_Gr) was fabricated using the ion etching technique that is employed as an effective host for lithium and sodium metal anodes. The binder‐free pSS_Gr demonstrated stable Li plating and stripping at areal current and capacity of 6 mA cm−2 and 2.54 mAh cm−2, respectively, for over 1000 cycles with 98% coulombic efficiency (C.E.). Also, in the case of Na metal anode, the host has shown stable performance at 4 mA cm−2 and 1 mAh cm−2 over 1000 cycles with ∼100% C.E.. Further, a full cell composed of Li‐plated pSS_Gr as an anode and LiFePO4 as a cathode is electrochemically tested at 50 mA g−1 current density with stable 100 cycles.
Event‐triggered state estimation for nonlinear systems aid by machine learning
Authors: Huong D. C. , Nguyen T. N. , Le H. T. , Trinh H. 
Published: February 2023

AbstractThe event‐triggered state estimation problem with the aid of machine learning for nonlinear systems is considered in this paper. First, we develop a recurrent neural network (RNN) model to predict the nonlinear systems. Second, we design a discrete‐time dynamic event‐triggered mechanism (ETM) and a state observer based on this ETM for the prediction model. This discrete‐time dynamic event‐triggered state observer significantly reduces the utilization of communication resources. Third, we establish a sufficient condition to ensure that the state observer can robustly estimate the state vector of the RNN model. Finally, we provide an illustrative example to verify the merit of the obtained results.
Black holes as “time capsules”: A cosmological graviton background and the Hubble tension
Authors: Piran Tsvi , Jimenez Raul 
Published: February 2023

AbstractMinuscule primordial black holes (BHs) before the end and after inflation can serve as “time capsules” bringing back energy from the past to a later epoch when they evaporate. As these BHs behave like matter, while the rest of the universe's content behaves like radiation, the mass fraction of these BHs, which is tiny at formation, becomes significant later. If sufficiently small, these BHs will evaporate while the Universe is still radiation dominated. We revisit this process and point out that gravitons produced during evaporation behave as “dark radiation.” If the initial BHs are uniformly distributed so will the gravitons and in this case, they will be free of Silk damping and avoid current limits on “dark radiation” scenarios. Seeds for such BHs can arise during the last phases of inflation. We show here that with suitable parameters, this background graviton field can resolve the Hubble tension. We present current observational constraints on this scenario and suggest upcoming observational tests to prove or refute it. Finally, we also elaborate on the graviton background produced by particle annihilation during the Planck era or shortly after inflation.
Integrated UPLC–Q‐TOF–MS and network pharmacology approach‐driven quality marker discovery of Danggui Shaoyao San for primary dysmenorrhea
Authors: Li Zhe , Xiong Hui , Li Na , Zhao Lanqingqing , Liu Zi , Yu Yongzhou , Zhao Chunying 
Published: February 2023

AbstractDanggui Shaoyao San (DSS), a famous prescription, has been clinically proved to be effective in treating primary dysmenorrhea (PD). Currently there is no valid quality control data available for DSS. The main aim of the current research was to explore quality markers (Q‐markers) of DSS. The chemical constituents of DSS were qualitatively identified using ultra‐performance liquid chromatography tandem quadrupole time of flight mass spectrometry (UPLC–Q‐TOF–MS) technology. On this basis, the targets of DSS and PD were predicted and screened using the TCMSP, SwissTargetPrediction, GeneCards, OMIM and TTD databases. Gene Ontology and Kyoto Encyclopedia of Genes and Genomes pathway analysis was performed on the core intersection targets using string and Cytoscape 3.7.1 software. Then molecular docking was conducted to screen the Q‐markers of DSS in PD. A total of 126 chemical constituents, including 22 organic acids, 14 phthalides, 24 monoterpenoids, five sesquiterpene lactones, 22 triterpenoids, four phenylpropanoids and 35 other compounds were preliminarily characterized. According to network pharmacology prediction analysis, six compounds containing polyporenic acid C, senkyunolide P, alisol B 23‐acetate, naringenin, gallic acid, ferulic acid and albiflorin were regarded as Q‐markers of DSS. The present research established an integrative UPLC–Q‐TOF–MS and network pharmacology method to discover the latent Q‐markers of DSS and provided a theoretical data for the follow‐up quality control of DSS.
Engineering strategies of metal‐organic frameworks toward advanced batteries
Authors: Sun Ruimin , Dou Mingyue , Chen Ziliang , Wang Ruirui , Zheng Xiangyi , Zhang Yuxiang , Zhou Chenggang , Menezes Prashanth W. 
Published: February 2023

AbstractMetal‐organic frameworks (MOFs) integrate several advantages such as adjustable pore sizes, large specific surface areas, controllable geometrical morphology, and feasible surface modification. Benefiting from these appealing merits, MOFs have recently been extensively explored in the field of advanced secondary batteries. However, a systematic summarization of the specific functional units that these materials can act as in batteries as well as their related design strategies to underline their functions has not been perceived to date. Motivated by this point, this review dedicates to the elucidation of diverse functions of MOFs for batteries, which involve the electrodes, separators, interface modifiers, and electrolytes. Particularly, the main engineering strategies based on the physical and chemical features to enable their enhanced performance have been highlighted for the individual functions. In addition, perspectives and possible research questions in the future development of these materials have also been outlined. This review captures such progress ranging from fundamental understanding and optimized protocols to multidirectional applications of MOF‐based materials in advanced secondary batteries.
Promoting the application of pediatric radiomics via an integrated medical engineering approach
Authors: Zheng Haige , Wang Fang , Li Yang , Li Zhicheng , Zhang Xiaochun , Yin Xuntao 
Published: February 2023

AbstractRadiomics is widely used in adult tumors but has been rarely applied to the field of pediatrics. Promoting the application of radiomics in pediatric diseases, especially in the early diagnosis and stratified treatment of tumors, is of great value to the realization of the WHO 2030 “Global Initiative for Childhood Cancer.” This paper discusses the general characteristics of radiomics, the particularity of its application to pediatric diseases, and the current status and prospects of pediatric radiomics. Radiomics is a data‐driven science, and the combination of medicine and engineering plays a decisive role in improving data quality, data diversity, and sample size. Compared with adult radiomics, pediatric radiomics is significantly different in data type, disease spectrum, disease staging, and progression. Some progress has been made in the identification, classification, stratification, survival prediction, and prognosis of tumor diseases. In the future, big data applications from multiple centers and cross‐talent training should be strengthened to improve the benefits for clinical workers and children.