bluuebunny/crossref_metadata_2025_split huggingface dataset:
Neutral Zn‐Air Battery Assembled with Single‐Atom Iridium Catalysts for Sensitive Self‐Powered Sensing System
Authors: Luo Xin , Yang Min , Song Weiyu , Fang Qie , Wei Xiaoqian , Jiao Lei , Xu Weiqing , Kang Yikun , Wang Hengjia , Wu Nannan , Gu Wenling , Zheng Lirong , Hu Liuyong , Zhu Chengzhou 
Published: April 2021

AbstractSelf‐powered sensing systems (SPSSs) are critical components in smart portable electronic devices. Zinc‐air batteries (ZABs) as promising energy devices provide a great opportunity to develop novel SPSS for sensing applications owing to the merit of high open‐circuit potential. Herein, hierarchically porous single‐atom iridium embedded nitrogen‐doped carbon (SA‐Ir/NC) is reported as an efficient catalyst for the oxygen reduction reaction (ORR) in the neutral ZABs, enabling the SPSSs towards glucose detection with a high sensitivity and stable output signal. The resultant SA‐Ir/NC shows superior ORR activity and stability to commercial Pt/C in neutral electrolytes. According to the theoretical calculations, IrN5 active sites in SA‐Ir/NC exhibit moderate adsorption free energy to reaction intermediates, giving SA‐Ir/NC excellent four‐electron ORR activity and well‐enhanced H2O2 tolerance. When SA‐Ir/NC is applied as an air cathode, the as‐prepared ZABs display a large open‐circuit voltage of 1.42 V, a remarkable power density of 90.4 mW cm−2, and excellent long‐term stability. After being integrated with glucose oxidase, the SPSSs are successfully established for sensitive detection of glucose based on a competitive model, holding great promise in biosensing applications.
Functionalized Polyurethane‐Coated Fabric with High Breathability, Durability, Reusability, and Protection Ability
Authors: Choi Moonhyun , Kim Youna , Park Sohyeon , Ka Dongwon , Kim Taihyun , Lee Sangmin , Sohn Eun‐Ho , Jin Youngho , Hong Jinkee 
Published: April 2021

AbstractTransmission of pathogens via respiratory droplets can spread infections such as COVID‐19. Wearing a mask hinders the spread of COVID‐19 infection and has become mandatory in some cases. Although most masks are affordable and disposable, continual daily replacement is required due to their performance deterioration caused by washing and contamination. Hence, a urethane‐reactive coating material comprising perfluoro‐tert‐butanol‐hexamethylene diisocyanate is developed with highly hydrophobic and oleophobic properties to functionalize a polyurethane‐coated fabric to bestow high breathability, durability, reusability, and protection ability. Its functions are maintained after scratch and wash testing, and its air permeability and water vapor transmittance rate (necessary for respiration) are unaffected. Its filtration efficiency of water droplets containing 100 nm polystyrene particles (similar in size to SARS‐CoV‐2) is increased due to its highly hydrophobic properties. In addition, it inhibits the adsorption of bovine serum albumin, the spike protein of COVID‐19, and Staphylococcus aureus and Pseudomonas aeruginosa.
Environment Tolerant Conductive Nanocomposite Organohydrogels as Flexible Strain Sensors and Power Sources for Sustainable Electronics
Authors: Sun Hongling , Zhao Yi , Jiao Sulin , Wang Chunfeng , Jia Yunpeng , Dai Kun , Zheng Guoqiang , Liu Chuntai , Wan Pengbo , Shen Changyu 
Published: April 2021

AbstractConductive hydrogels (CHs) have been highlighted in the design of flexible strain sensors and stretchable triboelectric nanogenerators (TENGs) on the basis of their excellent physicochemical properties such as large stretchability and high conductivity. Nevertheless, the incident freezing and drying behaviors of CHs by using water solvent as the dispersion medium limit their application scopes significantly. Herein, an environment tolerant and ultrastretchable organohydrogel is demonstrated by a simple solvent‐replacement strategy, in which the partial water in the as‐synthesized polyacrylamide/montmorillonite/carbon nanotubes hydrogel is replaced with the glycerol, leading to excellent temperature toleration (−60 to 60 °C) and good stability (30 days under normal environment) without sacrificing the stretchability and conductivity. The organohydrogel exhibits an ultrawide strain sensing range (0–4196%) with a high sensitivity of 8.5, enabling effective detection and discrimination of human activities that are gentle or drastic under various conditions. Furthermore, the organohydrogel is assembled in a single‐electrode TENG, which displays excellent energy harvesting ability even under a stretchability of 500% and robustness to directly power wearable electronics in harsh cold conditions. This work inspires a simple route for multifunctional organohydrogel and promises the practical application of flexible and self‐powered wearable devices in extreme environments.
Large‐eddy simulation of coal combustion in 15 MW pilot‐scale boiler‐simulation facility
Authors: Zhou Minmin , Parra‐Álvarez John , Wu Yuxin , Smith Sean T. , Smith Philip J. 
Published: April 2021

AbstractHigh‐fidelity modeling provides a useful approach to investigate the multiscale multiphysics mechanism in the pulverized coal combustion. This research focuses on understanding the pulverized coal combustion in a pilot‐up facility: General electric (GE) 15 MW pilot‐scale boiler simulation facility (BSF). The heat flux to the boiler water wall, O2 concentration, and gas temperature are the quality of interest (QoI's) for this research, as they are the most important parameters for designing a full‐scale pulverized coal boiler. Even the heat flux in boiler is largely determined by the heat transfer mechanism, and other detailed multiphysics mechanisms, including multiphase turbulent flow, radiation heat transfer, ash deposition, coal devolatilization, and oxidation, also need to be accounted. This work applies large‐eddy simulation (LES) code on high‐performance computing facility to simulate pulverized coal combustion in BSF. The physics‐based submodel that contains the significant sensitivity for QoI's has been identified using the detailed impact factor analysis on this high‐fidelity modeling. Results indicate that the most sensitive submodel on QoI's is the wall‐heat‐transfer coupling with the ash‐deposition model, which allows us to prioritize to improve this submodel in the LES simulation. Thus, ash deposition and wall‐heat‐transfer processes have been modeled and integrated into coal combustion numerical simulation. The simulation results show quantitative agreement between the simulation with experimental data regarding gas temperature, O2 concentration, and heat‐flux profile across the exposed boiler walls. Another implication of this research is to demonstrate a positive societal impact of extreme computing and accelerate the development of new combustion technology using a capable exascale computing technique.
Hyperbaric oxygen management of recurrent cellulitis in poikiloderma with neutropenia
Authors: Roebke Logan J. , Vander Maten Josh W. , Alkhoury Ghattas 
Published: April 2021

AbstractPoikiloderma with neutropenia (PN), is a rare autosomal recessive condition with many associated complications and manifestations. Here we present a patient with confirmed PN who is of one‐quarter Chucktaw or Cherokee heritage with no known descent from the Navajo tribe. The patient's condition was complicated by chronic bilateral lower limb cellulitis and associated osteomyelitis which was unresponsive to extensive antibiotic regimens. Subsequent treatment with hyperbaric oxygen therapy (HBOT) was successful. To date, no author has reported on the treatment of recurrent cellulitis using HBOT in this patient population. Based on our experience, HBOT should be considered in patients with PN.
In Vivo X‐ray Triggered Catalysis of H2 Generation for Cancer Synergistic Gas Radiotherapy
Authors: Wu Ying , Su Lichao , Yuan Meng , Chen Tao , Ye Jiamin , Jiang Yifan , Song Jibin , Yang Huanghao 
Published: April 2021

AbstractTo date, hydrogen (H2) therapy has received widespread attention. However, X‐ray triggered sustainable H2‐producing materials with controlled release for cancer treatment have not been reported. Herein, an X‐ray triggered sustainable in situ H2 producing platform, Au NR‐TiO2@ZnS:Cu,Co‐A(Au‐TiO2@ZnS), composed of Au‐amorphous TiO2 nano‐dumbbell‐shaped heterostructure coated with long afterglow particles, was developed for cancer synergistic H2‐radiotherapy. The mechanism of H2 production was verified by theoretical calculations and in vitro experiments. Changes in the apoptosis pathway caused by the synergistic effect of H2 and radiotherapy were reported. Guided by its excellent photoacoustic imaging capabilities, mice with orthotopic liver cancer achieved excellent therapeutic effects and low inflammatory side effects, suggesting that Au‐TiO2@ZnS has promising application potential for cancer treatment and prognosis.
Exploiting Supramolecular Dynamics in Metal–Phenolic Networks to Generate Metal–Oxide and Metal–Carbon Networks
Authors: Pan Shuaijun , Goudeli Eirini , Chen Jingqu , Lin Zhixing , Zhong Qi‐Zhi , Zhang Wenjie , Yu Haitao , Guo Rui , Richardson Joseph J. , Caruso Frank 
Published: April 2021

AbstractSupramolecular complexation is a powerful strategy for engineering materials in bulk and at interfaces. Metal–phenolic networks (MPNs), which are assembled through supramolecular complexes, have emerged as suitable candidates for surface and particle engineering owing to their diverse properties. Herein, we examine the supramolecular dynamics of MPNs during thermal transformation processes. Changes in the local supramolecular network including enlarged pores, ordered aromatic packing, and metal relocation arise from thermal treatment in air or an inert atmosphere, enabling the engineering of metal–oxide networks (MONs) and metal–carbon networks, respectively. Furthermore, by integrating photo‐responsive motifs (i.e., TiO2) and silanization, the MONs are endowed with reversible superhydrophobic (>150°) and superhydrophilic (≈0°) properties. By highlighting the thermodynamics of MPNs and their transformation into diverse materials, this work offers a versatile pathway for advanced materials engineering.
Wearable Tin‐Based Perovskite Solar Cells Achieved by a Crystallographic Size Effect
Authors: Rao Li , Meng Xiangchuan , Xiao Shuqin , Xing Zhi , Fu Qingxia , Wang Hongyu , Gong Chenxiang , Hu Ting , Hu Xiaotian , Guo Rui , Chen Yiwang 
Published: April 2021

AbstractTin‐based perovskite solar cells (PSCs) demonstrate a potential application in wearable electronics due to its hypotoxicity. However, poor crystal quality is still the bottleneck for achieving high‐performance flexible devices. In this work, graphite phase‐C3N4(g‐C3N4) is applied into tin‐based perovskite as a crystalline template, which delays crystallization via a size‐effect and passivates defects simultaneously. The double hydrogen bond between g‐C3N4and formamidine cation can optimize lattice matching and passivation. Moreover, the two‐dimensional network structure of g‐C3N4can fit on the crystals, resulting an enhanced hydrophobicity and oxidation resistance. Therefore, the flexible tin‐based PSCs with g‐C3N4realize a stabilized power conversion efficiency (PCE) of 8.56 % with negligible hysteresis. In addition, the PSCs can maintain 91 % of the initial PCE after 1000 h under N2environment and keep 92 % of their original PCE after 600 cycles at a curvature radius of 3 mm.
Structural Transformative Antioxidants for Dual‐Responsive Anti‐Inflammatory Delivery and Photoacoustic Inflammation Imaging
Authors: Zhao Caiyan , Chen Jingxiao , Ye Jiamin , Li Zhi , Su Lichao , Wang Junqing , Zhang Ye , Chen Jinghua , Yang Huanghao , Shi Jinjun , Song Jibin 
Published: April 2021

AbstractWe have synthesized a PEGylated, phenylboronic acid modified L‐DOPA pro‐antioxidant (pPAD) that can self‐assemble into nanoparticles (pPADN) for the loading of a model glucocorticoid dexamethasone (Dex) through 1,3‐diol/phenylboronic acid chemistry and hydrophobic interactions for more effective treatment of inflammation. Upon exposure to ROS, pPADN convert into the active form of L‐DOPA, and a cascade of oxidative reactions transform it into antioxidative melanin‐like materials. Concomitantly, the structural transformation of pPADN triggers the specific release of Dex, along with the acidic pH of inflammatory tissue. In a rat model of osteoarthritis, Dex‐loaded pPADN markedly mitigate synovial inflammation, suppress joint destruction and cartilage matrix degradation, with negligible in vivo toxicity. Moreover, in situ structural transformation makes pPADN suitable for noninvasive monitoring of therapeutic effects as a photoacoustic imaging contrast agent.
Effect of the Ligand Backbone on the Reactivity and Mechanistic Paradigm of Non‐Heme Iron(IV)‐Oxo during Olefin Epoxidation
Authors: Biswas Jyoti Prasad , Ansari Mursaleem , Paik Aniruddha , Sasmal Sheuli , Paul Sabarni , Rana Sujoy , Rajaraman Gopalan , Maiti Debabrata 
Published: April 2021

AbstractThe oxygen atom transfer (OAT) reactivity of the non‐heme [FeIV(2PyN2Q)(O)]2+ (2) containing the sterically bulky quinoline‐pyridine pentadentate ligand (2PyN2Q) has been thoroughly studied with different olefins. The ferryl‐oxo complex 2 shows excellent OAT reactivity during epoxidations. The steric encumbrance and electronic effect of the ligand influence the mechanistic shuttle between OAT pathway I and isomerization pathway II (during the reaction stereo pure olefins), resulting in a mixture of cis‐trans epoxide products. In contrast, the sterically less hindered and electronically different [FeIV(N4Py)(O)]2+ (1) provides only cis‐stilbene epoxide. A Hammett study suggests the role of dominant inductive electronic along with minor resonance effect during electron transfer from olefin to 2 in the rate‐limiting step. Additionally, a computational study supports the involvement of stepwise pathways during olefin epoxidation. The ferryl bend due to the bulkier ligand incorporation leads to destabilization of both
and
orbitals, leading to a very small quintet–triplet gap and enhanced reactivity for 2 compared to 1. Thus, the present study unveils the role of steric and electronic effects of the ligand towards mechanistic modification during olefin epoxidation
Carbon dioxide adducts from DOPO‐grafted polyethylenimines as both blowing agents and flame retardants for polyurethanes
Authors: Zeng Jianming , Luo Wenli , An Jianing , Xie Xingyi 
Published: April 2021

AbstractThe high risk of flammability of polyurethane foams (PUFs) and the high global warming potentials of polyurethane (PU) blowing agents rank key problems to be solved in PUF industry. Herein, 9,10‐dihydro‐9‐oxa‐10‐phosphenanthrene‐10‐oxide (DOPO)‐grafted polyethylenimines (PEIs) are synthesized via Atherton–Todd reaction, with grafting rate ranging from 13.3% to 28.3%. The grafted PEIs further react with CO2 to obtain corresponding CO2 adducts (DOPO‐PEI‐CO2s). On the one hand, these CO2 adducts can disperse into PU foaming mixture to release CO2 as a climate‐friendly blowing agent. The resultant PUFs possess a density about 56 kg m−3 and a compressive strength over 200 kPa, suitable for some industrial applications. On the other hand, the DOPO grafting endows the PUFs with moderate flame retardancy, increasing the PUFs' limiting oxygen index value from 19.7 to 25 vol%, and decreasing the horizontal burning speed from about 360 mm min−1 down to 130 mm min−1. This study for the first time provides a type of polyurethane (PU) raw material that can serve as both blowing agents and flame retardants.
Brandschutztechnischer Nachweis von historischen Stahlstützen am praktischen Beispiel
Authors: Sothmann Jörg , Winkler Michael , Molochnikova Olga 
Published: April 2021

AbstractDie Historie des Gewerbehofs Wiesendamm 22–30 in Hamburg geht auf das Jahr 1917 zurück. Das Gebäude wurde für die Maschinenfabrik Heidenreich & Harbeck errichtet und in den Folgejahren erweitert, umgebaut, ausgebaut, aufgestockt, tw. rückgebaut und umgenutzt. Bezüglich des Tragwerks wurde es 1937 wesentlich erweitert. Nun wurde das Gebäude einer neuen Nutzung als Theater zugeführt. Im Zuge des Brandschutzkonzepts und der Abstimmungen mit der Bauaufsicht wurde die Anforderung feuerbeständig für das Tragwerk, insbesondere für die Stahlstützen festgelegt. Im Rahmen der Ausführungsplanung wurde mit allen Beteiligten abgestimmt, dass eine brandschutztechnische Bemessung der Stützen mit einem Naturbrandszenario und einer gleichwertigen Sicherheit zu feuerbeständigen Stützen umgesetzt werden soll. Die Herausforderung dabei liegt insbesondere in der Tatsache, dass über 70 Stützen im Brandfall zu betrachten sind. Dabei liegen zehn unterschiedliche Querschnitte, sechs unterschiedliche Knicklängen und sechs verschiedene Belastungen vor. Weiterhin sind diese Stützen über das ganze Gebäude verteilt und weisen unterschiedlichste thermische Einwirkungen im Brandfall auf. Erschwerend kommt hinzu, dass die Anwendbarkeit der Spannungs‐Dehnungsbeziehung sowie der thermischen Materialkennwerte im Brandfall aus DIN EN 1993‐1‐2 bei dem Stahl aus 1917 fraglich ist. Im Zuge einer wirtschaftlichen und einfachen Bemessung im Brandfall wurden die Stützen bez. der thermischen Einwirkung gruppiert und entsprechende Brandsimulationen mit dem Feldmodell FDS durchgeführt. Hinsichtlich der mechanischen Beanspruchung wurden die ungünstigen Stützen ermittelt, den Gruppen aus der thermischen Einwirkung zugeordnet und im Brandfall bemessen. Zur Absicherung der Bemessung im Brandfall wurden Proben aus den Stützen entnommen und sowohl bei Normaltemperatur als auch bei hohen Temperaturen bez. der Festigkeiten und der Spannungs‐Dehnungsbeziehungen untersucht. Begleitend von Literaturrecherchen konnten die Grundlagen für die mechanischen Simulationen festgestellt werden. In dem Beitrag werden das Vorgehen, die Berechnungen und auch die Versuchsergebnisse beschrieben.
A case report of pneumomediastinum in a COVID‐19 patient treated with high‐flow nasal cannula and review of the literature: Is this a “spontaneous” complication?
Authors: Cancelliere Anna , Procopio Giada , Mazzitelli Maria , Lio Elena , Petullà Maria , Serapide Francesca , Pelle Maria Chiara , Davoli Chiara , Trecarichi Enrico Maria , Torti Carlo ,   The IDTM UMG COVID‐19 Group
Published: April 2021

AbstractOxygen support with high‐flow nasal cannula (HFNC) is gentler than mechanical ventilation and may provide significant benefits, but more studies are needed to investigate the efficacy and safety of different respiratory supports in patients with COVID‐19 pneumonia.
On the Structural Assignments Underlying R. B. Woodward's Most Personal Data That Led to the Woodward–Hoffmann Rules: Subramania Ranganathan's Key Role and Related Research by E. J. Corey and A. G. Hortmann
Authors: Tantillo Dean J. , Seeman Jeffrey I. 
Published: April 2021

AbstractIn the early 1960s, as part of R. B. Woodward's isoxazole route to vitamin B12, Subramania Ranganathan uncovered two coupled sets of stereospecific reactions, a thermal set and a photochemical set. These four reactions illustrated the alternating configurations that were the major data points that prompted the solution of the no‐mechanism problem. Though Ranganathan's reactions played a major role, according to Woodward, in the development of the Woodward–Hoffmann rules, they were published only as part of the documentation of a lecture given by Woodward in 1966. The authors of this paper have uncovered Subramania Ranganathan's 1964 postdoctoral report and have used modern quantum chemical theory to predict the 1H NMR spectra for Ranganathan's key compounds, providing support for the structure assignments made by Woodward and Ranganathan. A similar set of alternating, stereospecific reactions was observed by E. J. Corey and Alfred Hortmann in their 1963 total synthesis of dihydrocostunolide. We also have applied the computational process used for Ranganathan's compounds to Hortmann's compounds, now also including the calculation of coupling constants, and find computational support for Corey and Hortmann's structure assignments.
A Cyclometalated IrIII Complex Conjugated to a Coumarin Derivative Is a Potent Photodynamic Agent against Prostate Differentiated and Tumorigenic Cancer Stem Cells
Authors: Novohradsky Vojtech , Markova Lenka , Kostrhunova Hana , Kasparkova Jana , Ruiz José , Marchán Vicente , Brabec Viktor 
Published: April 2021

AbstractA cyclometalated IrIII complex conjugated to a far‐red‐emitting coumarin, IrIII‐COUPY (3), was recently shown as a very promising photosensitizer suitable for photodynamic therapy of cancer. Therefore, the primary goal of this work was to deepen knowledge on the mechanism of its photoactivated antitumor action so that this information could be used to propose a new class of compounds as drug candidates for curing very hardly treatable human tumors, such as androgen resistant prostatic tumors of metastatic origin. Conventional anticancer chemotherapies exhibit several disadvantages, such as limited efficiency to target cancer stem cells (CSCs), which are considered the main reason for chemotherapy resistance, relapse, and metastasis. Herein, we show, using DU145 tumor cells, taken as the model of hormone‐refractory and aggressive prostate cancer cells resistant to conventional antineoplastic drugs, that the photoactivated conjugate 3 very efficiently eliminates both prostate bulk (differentiated) and prostate hardly treatable CSCs simultaneously and with a similar efficiency. Notably, the very low toxicity of IrIII‐COUPY conjugate in the prostate DU145 cells in the dark and its pronounced selectivity for tumor cells compared with noncancerous cells could result in low side effects and reduced damage of healthy cells during the photoactivated therapy by this agent. Moreover, the experiments performed with the 3D spheroids formed from DU145 CSCs showed that conjugate 3 can penetrate the inner layers of tumor spheres, which might markedly increase its therapeutic effect. Also interestingly, this conjugate induces apoptotic cell death in prostate cancer DU145 cells associated with calcium signaling flux in these cells and autophagy. To the best of our knowledge, this is the first study demonstrating that a photoactivatable metal‐based compound is an efficient agent capable of killing even hardly treatable CSCs.
Reactions on a 1,2‐Dicarbonyl Moiety of a Fullerene Skeleton
Authors: Hashikawa Yoshifumi , Li Jiayue , Okamoto Shu , Murata Yasujiro 
Published: April 2021

AbstractA 1,2‐dicarbonyl moiety on a cage‐opened fullerene skeleton is one of suitable building blocks for the further derivatization. Herein, we discuss the chemical transformation of a 1,2‐dicarbonyl compound into β‐oxo‐phosphorus ylide, acid anhydride, and α‐methylene carbonyl derivatives. Despite possessing a sterically small methylene unit in the last one, the release of an encapsulated water molecule was significantly supressed whereas the β‐oxo‐phosphorus ylide bearing three bulky p‐tolyl groups on the P‐atom enabled the faster insertion/release dynamics, implying the flexibility of the phosphonium substituent. The replacement of the carbonyl group with phosphorus ylide and methylene units largely varied electrochemical properties of the fullerene skeleton, likely arising from the anionic charge delocalized over the entire molecule and removal of an electron‐withdrawable carbonyl group, respectively.
Isolation of an Antiaromatic 9‐Hydroxy Fluorenyl Cation
Authors: Duvinage Daniel , Mebs Stefan , Beckmann Jens 
Published: April 2021

AbstractFluorenyl cations are textbook examples of 4π electron antiaromatic five‐membered ring systems. So far, they were reported only as short‐lived intermediates generated under superacidic conditions or by flash photolysis. Attempts to prepare am‐terphenyl acylium cation by fluoride abstraction from a benzoyl fluoride gave rise to an isolable 9‐hydroxy fluorenyl cation that formed by an intramolecular electrophilic attack at a flanking mesityl group prior to a 1,2‐methyl shift and proton transfer to oxygen.