bluuebunny/crossref_metadata_2025_split huggingface dataset:
Retorting Photocorrosion and Enhanced Charge Carrier Separation at CdSe Nanocapsules by Chemically Synthesized TiO2 Shell for Photocatalytic Hydrogen Fuel Generation
Authors: Rao Vempuluru Navakoteswara , Pitchaimuthu Sudhagar , Ravi Parnapalle , Sathish Marappan , Han Hyungkyu , Venkatakrishnan Shankar Muthukonda 
Published: March 2020

AbstractMetal chalcogenide‐based semiconductor nanostructures are promising candidates for photocatalytic or photoelectrocatalytic hydrogen generation. In order to protect CdSe from photocorrosion, a layer of TiO2 wrapped (shell) onto CdSe (core) nanocapsule via the post‐synthesis process. The morphology studies confirm that a thin crystalline TiO2 shell (3–8 nm) wrapped in all the three directions onto CdSe core and thickness of the shell can be controlled through modulating the titania precursor concentration. The feasibility of pristine CdSe nanocapsules and CdSe@TiO2 in transforming visible light to hydrogen conversion was tested through photocatalysis reaction. The CdSe@TiO2 nanocapsules generated a four‐fold high rate of hydrogen gas (21 mmol.h−1.g−1cat) than pristine CdSe. In order to understand the role of shell@core, we have studied the photoelectrochemical and impedance analysis. The CdSe@TiO2 nanocapsules showed higher photoelectric current generation and lower charge transfer resistance at electrode/electrolyte interfaces compared to pristine CdSe. These studies endorse that chemically synthesized crystalline TiO2 shell played a multifunctional role in (a) surface passivation from photocorrosion, (b) promoting photocharge carrier separation via tunneling process between CdSe and TiO2 interface. As a result, CdSe@TiO2 nanocapsules showed a high conversion efficiency of 12.9 % under visible light irradiation (328 mW.cm−2) and a TOF of 0.05018 s−1.
Oligophenyls with Multiple Disulfide Bridges as Higher Homologues of Dibenzo[c,e][1,2]dithiin: Synthesis and Application in Lithium‐Ion Batteries
Authors: Sonnenschein Christoph , Ender Christopher P. , Wang Faxing , Schollmeyer Dieter , Feng Xinliang , Narita Akimitsu , Müllen Klaus 
Published: March 2020

AbstractHigher homologues of dibenzo[c,e][1,2]dithiin were synthesized from oligophenyls bearing multiple methylthio groups. Single‐crystal X‐ray analyses revealed their nonplanar structures and helical enantiomers of higher meta‐congener 6. Such dibenzo[1,2]dithiin homologues are demonstrated to be applicable to lithium‐ion batteries as cathode, displaying a high capacity of 118 mAh g−1 at a current density of 50 mA g−1.
Conformation‐Dependent Response to the Protonation of Diphenanthrioctaphyrin(1.1.1.0.1.1.1.0): A Route to Pseudorotaxane‐Like Structures
Authors: Szyszko Bartosz , Przewoźnik Monika , Białek Michał J. , Białońska Agata , Chmielewski Piotr J. , Latos‐Grażyński Lechosław 
Published: March 2020

AbstractDiphenanthrioctaphyrin(1.1.1.0.1.1.1.0), an expanded carbaporphyrinoid incorporating two phenanthrenylene moieties, exists as two separate, yet interconvertible, locked stereoisomers. These species demonstrate complex dynamic behavior upon protonation, consisting in multiple conformational rearrangements and anion‐binding events. The formation of one of the final dicationic forms is accompanied by the inclusion of a complex anion(s) within the macrocyclic cavity yielding a pseudorotaxane‐like host–guest complex. Protonation with trifluoroacetic or dichloroacetic acids followed by neutralization afforded a conformation‐switching cycle, which involves six structurally different species. Analogous acidification with chiral 10‐camphorsulfonic acid and subsequent neutralization generated one of the free base stereoisomers with enantiomeric excess. Therefore, it was shown that the simple acid‐base chemistry of diphenanthrioctaphyrin can act as stimulus, inducing chirality into the system, allowing for the manipulation of the stereochemical information imprinted into the enantiomers of the macrocycle.
Absolute stereochemical determination of 1,2‐diols via complexation with dinaphthyl borinic acid
Authors: Torabi Kohlbouni Saeedeh , Sarkar Aritra , Zhang Jun , Li Xiaoyong , Borhan Babak 
Published: March 2020

AbstractRapid derivatization of chiral 1,2‐diols with dinaphthyl borinic acid (DBA) leads to a cyclic boronate, enabling the absolute stereochemical prediction via exciton‐coupled circular dichroic (ECCD) of the naphthyl groups. Aryl‐ and alkyl‐substituted 1,2‐diols derivatized with DBA yield a predictable ECCD, which is also in agreement with theoretical predictions derived from computationally minimized structures.
Axially Chiral Aryl‐Alkene‐Indole Framework: A Nascent Member of the Atropisomeric Family and Its Catalytic Asymmetric Construction
Authors: Wang Cong‐Shuai , Li Tian‐Zhen , Liu Si‐Jia , Zhang Yu‐Chen , Deng Shuang , Jiao Yinchun , Shi Feng 
Published: March 2020

Summary of main observation and conclusionA new class of axially chiral aryl‐alkene‐indole frameworks have been designed, and the first catalytic asymmetric construction of such scaffolds has been established by the strategy of organocatalytic (Z/E)‐selective and enantioselective (4+3) cyclization of 3‐alkynyl‐2‐indolylmethanols with 2‐naphthols or phenols (all >95 : 5 E/Z, up to 98% yield, 97% ee). This reaction also represents the first catalytic asymmetric construction of axially chiral alkene‐heteroaryl scaffolds, which will add a new member to the atropisomeric family. This approach has not only confronted the great challenges in constructing axially chiral alkene‐heteroaryl scaffolds but also provided a powerful strategy for the enantioselective construction of axially chiral aryl‐alkene‐indole frameworks.
The Reaction of Sulfur Dioxide Radical Cation with Hydrogen and its Relevance in Solar Geoengineering Models
Authors: Satta Mauro , Cartoni Antonella , Catone Daniele , Castrovilli Mattea Carmen , Bolognesi Paola , Zema Nicola , Avaldi Lorenzo 
Published: March 2020

AbstractSO2 has been proposed in solar geoengineering as a precursor of H2SO4 aerosol, a cooling agent active in the stratosphere to contrast climate change. Atmospheric ionization sources can ionize SO2 into excited states of
, which quickly reacts with trace gases in the stratosphere. In this work we explore the reaction of
with
excited by tunable synchrotron radiation, leading to
(
), where H contributes to O3 depletion and OH formation. Density Functional Theory and Variational Transition State Theory have been used to investigate the dynamics of the title barrierless and exothermic reaction. The present results suggest that solar geoengineering models should test the reactivity of
with major trace gases in the stratosphere, such as H2 since this is a relevant channel for the OH formation during the nighttime when there is not OH production by sunlight. OH oxides SO2, triggering the chemical reactions leading to H2SO4 aerosol.
Hydrogen Evolution Reaction by Atomic Layer‐Deposited MoNx on Porous Carbon Substrates: The Effects of Porosity and Annealing on Catalyst Activity and Stability
Authors: Ramesh Rahul , Sawant Sandesh Y. , Nandi Dip K. , Kim Tae Hyun , Kim Deok Hyun , Han Seung‐Min , Jang Yujin , Ha Myoung Gyu , Cho Moo Hwan , Yoon Taeho , Kim Soo‐Hyun 
Published: March 2020

AbstractMolybdenum‐based compounds are considered as a potential replacement for expensive precious‐metal electrocatalysts for the hydrogen evolution reaction (HER) in acid electrolytes. However, coating of thin films of molybdenum nitride or carbide on a large‐area self‐standing substrate with high precision is still challenging. Here, MoNx is uniformly coated on carbon cloth (CC) and nitrogen‐doped carbon (NC)‐modified CC (NCCC) substrates by atomic layer deposition (ALD). The as‐deposited film has a nanocrystalline character close to amorphous and a composition of approximately Mo2N with significant oxygen contamination, mainly at the surface. Among the as‐prepared ALD‐MoNx electrodes, the MoNx/NCCC has the highest HER activity (overpotential η≈236 mV to achieve 10 mA cm−2) owing to the high surface area and porosity of the NCCC substrate. However, the durability of the electrode is poor, owing to the poor adhesion of NC powder on CC. Annealing MoNx/NCCC in H2 atmosphere at 400 °C improves both the activity and durability of the electrode without significant change in the phase or porosity. Annealing at an elevated temperature of 600 °C results in formation of a Mo2C phase that further enhances the activity (η≈196 mV to achieve 10 mA cm−2), although there is a huge reduction in the porosity of the electrode as a consequence of the annealing. The structure of the electrode is also systematically investigated by electrochemical impedance spectroscopy (EIS). A deviation in the conventional Warburg impedance is observed in EIS of the NCCC‐based electrode and is ascribed to the change in the H+ ion diffusion characteristics, owing to the geometry of the pores. The change in porous nature with annealing and the loss in porosity are reflected in the EIS of H+ ion diffusion observed at high‐frequency. The current work establishes a better understanding of the importance of various parameters for a highly active HER electrode and will help the development of a commercial electrode for HER using the ALD technique.
Short‐Time Hydrothermal Treatment of Poplar Wood for the Production of a Lignin‐Derived Polyphenol Antioxidant
Authors: Zhang Tongtong , Zhou Hao , Fu Yingjuan , Zhao Yingjie , Yuan Zaiwu , Shao Zhiyong , Wang Zhaojiang , Qin Menghua 
Published: March 2020

AbstractArtificial antioxidants are synthesized from fossil sources and are now widely used in the polymer, food, and cosmetics industries. The gradual depletion of fossil resources makes it practically significant and necessary to produce green antioxidants from renewable lignocellulosic resources. Herein, short‐time hydrothermal (STH) treatment was developed for production of lignin‐derived polyphenol antioxidants (LPAs) from poplar wood under conditions of high temperature and high pressure. LPA yields from 21.5 to 37.6 % on the basis of lignin in untreated wood were obtained by STH treatments as result of lignin depolymerization at 190–200 °C and 10 MPa in 5–8 min. Depolymerization reactions were confirmed by the much lower molecular weight of LPA (1076 g mol−1) than that of native lignin (4094 g mol−1). NMR spectroscopy revealed the structural features of lignin in the isolated LPA, namely syringyl and guaiacyl units with well‐preserved interunit linkages. A Folin–Ciocalteu assay indicated that each LPA molecule contained 5.4 phenolic hydroxyl groups on average, much more than other technical lignins. The remarkable antioxidant ability of LPA was verified by the radical‐scavenging index of 53.5–67.3, much higher than 0.2–11.1 of the commercial antioxidants butylated hydroxytoluene (BHT) and butylated hydroxyanisole (BHA). STH treatment only requires water and heat for production of high‐value antioxidant, which provides a green and sustainable method for the utilization of lignocelluloses.
Using the otolith sulcus to aid in prey identification and improve estimates of prey size in diet studies of a piscivorous predator
Authors: Byrd Barbie L. , Hohn Aleta A. , Krause Jacob R. 
Published: March 2020

AbstractDiet studies are fundamental for understanding trophic connections in marine ecosystems. In the southeastern US, the common bottlenose dolphin Tursiops truncatus is the predominant marine mammal in coastal waters, but its role as a top predator has received little attention. Diet studies of piscivorous predators, like bottlenose dolphins, start with assessing prey otoliths recovered from stomachs or feces, but digestive erosion hampers species identification and underestimates fish weight (FW). To compensate, FW is often estimated from the least affected otoliths and scaled to other otoliths, which also introduces bias. The sulcus, an otolith surface feature, has a species‐specific shape of its ostium and caudal extents, which is within the otolith edge for some species. We explored whether the sulcus could improve species identification and estimation of prey size using a case study of four sciaenid species targeted by fisheries and bottlenose dolphins in North Carolina. Methods were assessed first on otoliths from a reference collection (n = 421) and applied to prey otoliths (n = 5,308) recovered from 120 stomachs of dead stranded dolphins. We demonstrated in reference‐collection otoliths that cauda to sulcus length (CL:SL) could discriminate between spotted seatrout (Cynoscion nebulosus) and weakfish (Cynoscion regalis) (classification accuracy = 0.98). This method confirmed for the first time predation of spotted seatrout by bottlenose dolphins in North Carolina. Using predictive models developed from reference‐collection otoliths, we provided evidence that digestion affects otolith length more than sulcus or cauda length, making the latter better predictors. Lastly, we explored scenarios of calculating total consumed biomass across degrees of digestion. A suggested approach was for the least digested otoliths to be scaled to other otoliths iteratively from within the same stomach, month, or season as samples allow. Using the otolith sulcus helped overcome challenges of species identification and fish size estimation, indicating their potential use in other diet studies.
H2O2 Screening from Saliva of Gum Diseased‐patient through CN‐dot Wrapped Cu2O Nano‐frogspawns Ionic Liquid Nanocomposite
Authors: Hayat Khizar , Hassan Akhtar Mahmood , Siddique Saleemi Awais , Badaruddin Ahmad Hafiz , Akhtar Naeem 
Published: March 2020

AbstractHerein, we report the development of a robust, sensitive, and selective non‐enzymatic electrochemical sensor for the detection of hydrogen peroxide (H2O2). The novel BA modified CN‐dot wrapped Cu2O‐nano‐frogspawn (FS@CN‐dot) sensor probe demonstrated a catalytic property towards H2O2 that allowed the highly sensitive electrochemical detection at a low reduction potential. The as prepared CN‐dot wrapped Cu2O hetero‐structured nanocomposite was analyzed using surface analysis methods to confirm the morphology, crystallinity, and oxidation states of various constituents and dopant elements. Further, the morphological analysis of the Cu2O nanoparticles revealed that the Cu2O retains frogspawns‐liked structure. Under the optimized experimental conditions, the sensor showed a wide dynamic range of H2O2 from 0.5 μM to 9 mM with a detection limit (LD) of 1.2±0.1 nM. The designed sensing probe showed good stability, high sensitivity, and selectivity even in the presence of potential interfering molecules. To check the reliability of the fabricated sensor in biomedical applications, the proposed sensing probe was successfully applied to monitor H2O2 in saliva of a gum‐diseased patient. To the best of our knowledge, this report is the first of its kind not only because of its novel construction style in terms of CN source, but also in terms of real sample applicability as well.
Spectral graph theory of brain oscillations
Authors: Raj Ashish , Cai Chang , Xie Xihe , Palacios Eva , Owen Julia , Mukherjee Pratik , Nagarajan Srikantan 
Published: March 2020

AbstractThe relationship between the brain's structural wiring and the functional patterns of neural activity is of fundamental interest in computational neuroscience. We examine a hierarchical, linear graph spectral model of brain activity at mesoscopic and macroscopic scales. The model formulation yields an elegant closed‐form solution for the structure–function problem, specified by the graph spectrum of the structural connectome's Laplacian, with simple, universal rules of dynamics specified by a minimal set of global parameters. The resulting parsimonious and analytical solution stands in contrast to complex numerical simulations of high dimensional coupled nonlinear neural field models. This spectral graph model accurately predicts spatial and spectral features of neural oscillatory activity across the brain and was successful in simultaneously reproducing empirically observed spatial and spectral patterns of alpha‐band (8–12 Hz) and beta‐band (15–30 Hz) activity estimated from source localized magnetoencephalography (MEG). This spectral graph model demonstrates that certain brain oscillations are emergent properties of the graph structure of the structural connectome and provides important insights towards understanding the fundamental relationship between network topology and macroscopic whole‐brain dynamics. .
Palbinone alleviates diabetic retinopathy in STZ‐induced rats by inhibiting NLRP3 inflammatory activity
Authors: Shi Qiang , Wang Jianchao , Cheng Yuhong , Dong Xiaomin , Zhang Ming , Pei Cheng 
Published: March 2020

AbstractDiabetic retinopathy (DR) is the primary cause of blindness and visual impairment in diabetes patients worldwide. However, laser and surgical therapies at DR have short‐term effectiveness and cause side effects. Treatment with natural products is a reasonable alternative treatment for DR. The main objective of this investigation is to explore the efficacy of a bioactive compound such as palbinone (PB) in DR. Experimental rats were injected intraperitoneally with streptozotocin (STZ, 65 mg/kg), and these established experimental rats were treated with PB (20 mg/kg/bw) for 42 days. The observed results showed that PB considerably reduced the proinflammatory cytokine (interleukin‐18 [IL‐18] and IL‐1β) production as well as improved the activities of antioxidant enzymes (superoxide dismutase, catalase, and glutathione peroxidase) particularly in the retinal region of STZ‐induced DR rats. In addition, PB treatment improved nuclear factor erythroid 2‐related factor 2 (Nrf2) accumulation and enhanced the heme oxygenase‐1 expression, and major antioxidants downregulated Nrf2 in the damaged retina. Also, the expression levels of nod‐like receptor family pyrin domain containing 3 (NLRP3), cleaved‐caspase‐1, IL‐1β, and apoptosis‐associated speck‐like protein containing CARD in the retinal region were notably upregulated in STZ‐induced DR, which was eliminated by PB interference. PB administration exerted efficient antioxidant activities, Nrf2 pathway activation, and inhibition of NLRP3 inflammasome. This current investigation concluded that PB considerably reduced the retinal inflammation and oxidative stress stimulated via high glucose, and also activated the antioxidative Nrf2 pathway and inhibited the NLRP3 inflammasome formation in rats.
In the presence of Trypanosoma cruzi antigens, activated peripheral T lymphocytes retained in the liver induce a proinflammatory phenotypic and functional shift in intrahepatic T lymphocyte
Authors: Meuser-Batista Marcelo , Vacani-Martins Natalia , Cascabulho Cynthia Machado , Beghini Daniela Gois , Henriques-Pons Andrea 
Published: March 2020

Abstract
In secondary lymphoid organs, pathogen-derived and endogenous danger molecules are recognized by pattern recognition receptors, leading to adaptive proinflammatory immune responses. This conceptual rule does not apply directly to the liver, as hepatic immune cells tolerate gut-derived bacterial molecules from the flora. Therefore, the recognition of danger and proinflammatory stimuli differs between the periphery and the liver. However, the tolerant nature of the liver must be overcome in the case of infections or cancer, for example. The central paradigm is the basis for danger recognition and the balance between inflammation and tolerance in the liver. Here, we observed functional integration, with activated peripheral T lymphocytes playing a role in the induction of a proinflammatory environment in the liver in the presence of Trypanosoma cruzi antigens. When only parasite extract was orally administered, it led to the up-regulation of hepatic tolerance markers, but oral treatment plus adoptively transferred activated splenic T lymphocytes led to a proinflammatory response. Moreover, treated/recipient mice showed increased levels of TNF, IFN-γ, IL-6, and CCL2 in the liver and increased numbers of effector and/or effector memory T lymphocytes and F4/80+ cells. There was a reduction in FoxP3+ Treg cells, NKT cells, and γδ T lymphocytes with increased liver damage in the presence of activated peripheral T cells. Our results show that the induction of a proinflammatory liver response against T. cruzi danger molecules is at least partially dependent on cooperation with activated peripheral T cells.
Attenuation of allergen-mediated mast cell activation by rosemary extract (Rosmarinus officinalisL.)
Authors: Yousef Michael , Crozier Robert W.E. , Hicks Natalie J. , Watson Colton J.F. , Boyd Tylar , Tsiani Evangelia , MacNeil Adam J. 
Published: March 2020

AbstractMast cells are immune sentinels and a driving force in both normal and pathological contexts of inflammation, with a prominent role in allergic hypersensitivities. Crosslinking of FcεRI by allergen-bound IgE Abs leads to mast cell degranulation, resulting in an early-phase response and release of newly synthesized pro-inflammatory mediators in the late-phase. The MAPK and NF-κB pathways are established as critical intracellular mechanisms directing mast cell-induced inflammation. Rosemary extract (RE) has been shown to modulate the MAPK and NF-κB pathways in other cellular contexts in vitro and in vivo. However, the effect of RE on mast cell activation has not been explored, and thus we aim to evaluate the potential of RE in modulating mast cell activation and FcεRI/c-kit signaling, potentially via these key pathways. Primary murine mast cells were sensitized with anti-TNP IgE and stimulated with cognate allergen (TNP-BSA) under stem cell factor (SCF) potentiation while treated with 0–25 µg/ml RE. RE treatment inhibited phosphorylation of p38 and JNK MAPKs while also impairing NF-кB transcription factor activity. Gene expression and mediator secretion analysis showed that RE treatment decreased IL-6, TNF, IL-13, CCL1, and CCL3, but major component polyphenols do not contribute to these effects. Importantly, RE treatment significantly inhibited early phase mast cell degranulation (down to 15% of control), with carnosic acid and carnosol contributing. These findings indicate that RE is capable of modulating mast cell functional outcomes and that further investigation of the underlying mechanisms and its potential therapeutic properties in allergic inflammatory conditions is warranted.
Autoimmune responses and inflammation in type 2 diabetes
Authors: Prasad Mukul , Chen Elijah W. , Toh Sue-Anne , Gascoigne Nicholas R. J. 
Published: March 2020

Abstract
Obesity-induced insulin resistance is one of the largest noncommunicable disease epidemics that we are facing at the moment. Changes in lifestyle and greater availability of low nutritional value, high caloric food has led to the highest rates of obesity in history. Obesity impacts the immune system and obesity-associated inflammation contributes to metabolic diseases, such as type 2 diabetes. Both the adaptive and the innate immune system play a role in the regulation of glycemic control, and there is a need to understand how metabolic imbalances drive disease pathogenesis. This review discusses the cell types, mediators, and pathways that contribute to immunologic–metabolic crosstalk and explores how the immune system might be targeted as a strategy to treat metabolic disease.