bluuebunny/crossref_metadata_2025 huggingface dataset:
Hybrid Transverse–Longitudinal Modes for High Figure‐of‐Merit Localized Plasmonic Refractometric Sensing in the Visible Spectrum
Authors: Soehartono Alana M. , Tobing Landobasa Y. M. , Mueller Aaron D. , Zhang Dao Hua , Yong Ken‐Tye
Published: February 2020

The nanoscale confinement of plasmonic fields, coupled with their high susceptibility to refractive index changes, makes localized surface plasmons (LSPs) an excellent platform for rapid and label‐free sensing. However, the small spatial overlap of the LSP fields with the adsorbed analyte dictates the sensitivity and figure of merit (FOM) of LSP‐based sensing. The linear dependence of sensitivity on resonance wavelength, coupled with the dependence of FOM on the achievable resonance Q factor, leads to a sensitivity of ≈100–300 nm per RIU and FOM < 5 for gold‐based LSP resonance in the visible range. This presents a dilemma for the realization of a practical sensing platform that requires high sensitivity and high FOM in the visible spectrum. Higher sensitivity and resonance Q factor can be achieved with a larger interaction volume between the plasmonic field and the analyte. This work explores a hybrid mode resulting from an interaction between transverse LSP and longitudinal Fabry–Perot (FP) modes, capable of improving the sensitivity and FOM simultaneously. This hybrid mode is demonstrated in tall v‐shaped split ring resonator structures, fabricated via seedless pulsed gold electrodeposition, with FOM of ≈24 in the visible range.
Recent Progress of Nanomedicine in the Treatment of Central Nervous System Diseases
Authors: Feng Leyan , Wang Heping , Xue Xue
Published: February 2020

Central nervous system (CNS) diseases, mainly including neurodegenerative diseases and psychiatric diseases, have become the leading cause of death and disability in the world today, which bring huge suffering to both patients and their families. Nanomedicine is an emerging and rapidly evolving discipline that mainly involves the application of nanoparticles in the diagnosis and treatment of various diseases. Although many challenges in the clinical application of nanomedicine still exist, the prospects for development cannot be ignored. Furthermore, better outcomes for patients with CNS diseases can be expected with the rapid development of nanotechnology in diagnosis and treatment. In the present review, an overview is given of the outstanding recent progress of nanomedicine from three aspects: drug delivery, imaging, and therapy in CNS diseases.
Molecular Entrapment in Thermophilic Ferritin for Nanoformulation in Photodynamic Therapy
Authors: Pasula Rupali Reddy , Kuniyil Ambili , Lim Sierin
Published: February 2020

Nanoformulation of therapeutic and diagnostic agents is beneficial as they accumulate at tumor sites due to enhanced permeability and retention effects. However, many in vitro studies performed on 2D cultures lack the realistic dimension of in vivo systems. In this work, a photosensitizer, acridine orange (AO), used in photodynamic therapy of cancer, is nanoformulated by entrapment in thermophilic ferritin. The efficacy is tested on 2D and 3D in vitro models and complemented with studies on the cellular uptake routes. Ferritin from the archaeon Archaeoglobus fulgidus (AfFtn) exhibits the unique property of divalent metal ion or ionic strength mediated assembly, making it an interesting nanocarrier for the entrapment of small molecules. The photosensitization and toxicity studies on 2D monolayers and 3D spheroid models of colorectal cancer cells show that AO loaded in AfFtn is functional. The killing efficiency in 2D monolayers reaches 50% while the growth of 3D spheroids is arrested after the first day with a subsequent 10% reduction of tumor diameter over the next 2 days. Results show that AO loaded AfFtn has better penetration ability than free AO alone in 3D spheroid models indicating that nanocage formulation provides for an efficient delivery vehicle into the tumor tissue.
Light Absorption and Recycling in Hybrid Metal Halide Perovskite Photovoltaic Devices
Authors: Patel Jay B. , Wright Adam D. , Lohmann Kilian B. , Peng Kun , Xia Chelsea Q. , Ball James M. , Noel Nakita K. , Crothers Timothy W. , Wong‐Leung Jenny , Snaith Henry J. , Herz Laura M. , Johnston Michael B.
Published: February 2020

The production of highly efficient single‐ and multijunction metal halide perovskite (MHP) solar cells requires careful optimization of the optical and electrical properties of these devices. Here, precise control of CH3NH3PbI3 perovskite layers is demonstrated in solar cell devices through the use of dual source coevaporation. Light absorption and device performance are tracked for incorporated MHP films ranging from ≈67 nm to ≈1.4 µm thickness and transfer‐matrix optical modeling is utilized to quantify optical losses that arise from interference effects. Based on these results, a device with 19.2% steady‐state power conversion efficiency is achieved through incorporation of a perovskite film with near‐optimum predicted thickness (≈709 nm). Significantly, a clear signature of photon reabsorption is observed in perovskite films that have the same thickness (≈709 nm) as in the optimized device. Despite the positive effect of photon recycling associated with photon reabsorption, devices with thicker (>750 nm) MHP layers exhibit poor performance owing to competing nonradiative charge recombination in a “dead‐volume” of MHP. Overall, these findings demonstrate the need for fine control over MHP thickness to achieve the highest efficiency cells, and accurate consideration of photon reabsorption, optical interference, and charge transport properties.
Biomechanical Energy‐Driven Hybridized Generator as a Universal Portable Power Source for Smart/Wearable Electronics
Authors: Rahman Muhammad Toyabur , Rana SM Sohel , Salauddin Md , Maharjan Pukar , Bhatta Trilochan , Park Jae Yeong
Published: February 2020

The fast growth of smart electronics requires novel solutions to power them sustainably. Portable power sources capable of harvesting biomechanical energy are a promising modern approach to reduce battery dependency. Herein, a novel elastic impact‐based nonresonant hybridized generator (EINR‐HG) is reported to effectively harvest biomechanical energy from diverse human activities outdoors. Through the rational integration of a nonlinear electromagnetic generator with two contact‐mode triboelectric nanogenerators, the proposed EINR‐HG generates hybrid electrical output simultaneously under the same mechanical excitations. By introducing a flux‐concentrator with a nanowire‐nanofiber surface modification, significant improvement in the energy harvesting efficiency of the EINR‐HG is achieved. After optimizing using simulations and vibration tests, the as‐fabricated EINR‐HG delivers an outstanding normalized power density of 3.13 mW cm−3 g−2 across a matching resistance of 1.5 kΩ at 6 Hz under 1 g acceleration. Under human motion testing, the EINR‐HG generates an optimal output power of 131.4 mW with horizontal handshaking. With a customized power management circuit, the EINR‐HG serves as a universal power source that successfully drives commercial smart electronics, including smart bands and smartphones. This work shows the massive potential of biomechanical energy‐driven hybridized generators for powering personal electronics and portable healthcare monitoring devices.
The Impacts of Biofuel Policies on Spatial and Vertical Price Relationships in the US Fertilizer Industry
Authors: Bekkerman Anton , Gumbley Thomas , Brester Gary W.
Published: February 2020

Biofuel policies and concomitant market forces in the mid‐2000s systemically altered US corn markets. Because corn production requires large nitrogen fertilizer inputs, those policies may have also impacted US fertilizer markets. We model fertilizer price relationships across US regions and leverage the natural experiment of biofuel policy intervention to show the secondary impacts on fertilizer markets. Long‐run fertilizer price adjustments became faster and short‐run price dynamics became more responsive to corn markets and less affected by natural gas prices. Additionally, regions where corn production significantly increased after the policies had a 10–20% increase in influencing the fertilizer price discovery process.
Amelioration of high temperature stress by exogenously applied salicylic acid: Genotype‐specific response of physiological traits
Authors: Pirnajmedin Fatemeh , Majidi Mohammad Mahdi , Taleb Hadi , Maibody Sayed Ali Mohammad Mirmohammady , Saeidi Ghodratollah
Published: February 2020

In arid and semi‐arid regions of the world, high temperature stress adversely affects growth and development of cool‐season grasses during late spring and summer. Salicylic acid (SA) is one of the endogenous plant growth regulators that plays an important role in the regulation of plant growth and development in response to high temperature stress. The aim of the present study was to assess the effectiveness of SA in alleviating the negative effects of high temperature during the summer in different tall fescue (Festuca arundinacea Schreb.) genotypes under field conditions. Twenty genotypes of tall fescue (selected from a broad native and exotic germplasm) were assessed at field condition for morphological and physiological characteristics during 2016 and 2017 under normal irrigation in the presence of two SA concentrations (0 and 1 mM). High temperature during the summer led to induction of incomplete summer dormancy and depression in summer forage yield. Application of SA decreased the adverse effects of high temperature stress by elevation of photosynthetic pigments, proline accumulation, and increasing nonenzyme and enzymatic antioxidant activities, and could therefore be used to enhance forage yield and heat tolerance in tall fescue genotypes. The genotypes exhibited obvious differences in their response to SA application under the semiarid climate conditions of central Iran. Among the studied genotypes, 3L and 1E were recognized as heat tolerant and stable genotypes that would be preferable for regions with high temperature.
On the fast modeling of species transport in fluidized beds using recurrence computational fluid dynamics
Authors: Dabbagh Firas , Pirker Stefan , Schneiderbauer Simon
Published: February 2020

Due to variety of scale dynamics evolved in gas–solid flows, most of its numerical description is limited to expensive short durations. This has made the slow processes therein, such as the chemical species conversion, to be out of an appropriate reach. In this work, an application of the transport‐based recurrence computational fluid dynamics (CFD) has been introduced for the fast modeling of passive scalar transport, which is considered as species conversion and heat transfer in fluidized beds. The methodology discloses the recurrent dynamics during a short‐term full CFD simulation as Lagrangian shift operations upon which a passive scalar can infinitely be traced. Apart from convecting, a proper approach based on the turbulent kinetic energy of tracked dynamics is introduced for modeling the physical diffusion of the scalar transported. Our outcomes have revealed a subtle chasing to the full CFD species simulation with a speed‐up up to 1,600.
A molecular model for ion dehydration in confined water
Authors: Qing Leying , Tao Jiabo , Yu Hongping , Jiang Peng , Qiao Chongzhi , Zhao Shuangliang , Liu Honglai
Published: February 2020

Although ion dehydration in confined water is ubiquitous in many important processes concerning ion adsorption, transport and separation, and so forth, few theoretical models have been developed to unravel the mechanism of dehydration in confined space. Herein, a molecular model is proposed by weighing the molecular orientation of surrounding water within the first hydration shell, and then this model is applied to predict the hydration numbers and hydrated radii of simple ions with the help of molecular density functional theory. The predictions are rationalized not only with parallel simulations but also with relevant experimental measurements. We find that the ion hydration in confined water is depressed owing to the confinement, and thus the multilayer hydration shell is disturbed, which results in the decline of hydration number and hydrated radius, favoring the ion dehydration. This work provides an insightful route toward the quantitative understanding and prediction of ion dehydration in confined water.
Recent Progress in the Development of Solid‐State Luminescent o‐Carboranes with Stimuli Responsivity
Authors: Ochi Junki , Tanaka Kazuo , Chujo Yoshiki
Published: February 2020

o‐Carborane, a cluster compound containing boron and adjacent carbon atoms, displays intriguing luminescent properties. Recently, compounds containing o‐carborane units were found to show suppressed aggregation‐induced quenching and intense solid‐state emission; they also show potential for the development of stimuli‐responsive luminochromic materials. In this Minireview, we introduce three kinds of fundamental photochemical properties: aggregation‐induced emission, twisted intramolecular charge transfer in crystals, and environment‐sensitive excimer formation in solids. Based on these properties, several types of luminochromism, such as thermos‐, vapo‐, and mechanochromism, have been discovered. Based mainly on results from recent studies, we illustrate these mechanisms as well as unique luminescent behaviors of o‐carborane derivatives.
Synthesis of Nitrogen‐Containing Polyaromatics by Aza‐Annulative π‐Extension of Unfunctionalized Aromatics
Authors: Kawahara Kou P. , Matsuoka Wataru , Ito Hideto , Itami Kenichiro
Published: February 2020

Nitrogen‐containing polycyclic aromatic compounds (N‐PACs) are an important class of compounds in materials science. Reported here is a new aza‐annulative π‐extension (aza‐APEX) reaction that allows rapid access to a range of N‐PACs in 11–84 % yields from readily available unfunctionalized aromatics and imidoyl chlorides. In the presence of silver hexafluorophosphate, arenes and imidoyl chlorides couple in a regioselective fashion. The follow‐up oxidative treatment with p‐chloranil affords structurally diverse N‐PACs, which are very difficult to synthesize. DFT calculations reveal that the aza‐APEX reaction proceeds through the formal [4+2] cycloaddition of an arene and an in situ generated diarylnitrilium salt, with sequential aromatizations having relatively low activation energies. Transformation of N‐PACs into nitrogen‐doped nanographenes and their photophysical properties are also described.
Cove‐Edged Nanographenes with Localized Double Bonds
Authors: Gu Yanwei , Muñoz‐Mármol Rafael , Wu Shaofei , Han Yi , Ni Yong , Díaz‐García María A. , Casado Juan , Wu Jishan
Published: February 2020

The efficient synthesis and electronic properties of two large‐size cove‐edged nanographenes (NGs), CN1 and CN2, are presented. X‐ray crystallographic analysis reveals a contorted backbone for both molecules owing to the steric repulsion at the inner cove position. Noticeably, the dominant structures of these molecules contain four (for CN1) or six (for CN2) localized C=C double bonds embedded in nine (for CN1) or twelve (for CN2) aromatic sextet rings according to Clar's formula, which is supported by bond length analysis and theoretical (NICS, ACID) calculations. Furthermore, Raman spectra exhibit a band associated with the longitudinal CC stretching mode of olefinic double bonds. Owing to the existence of the additional olefinic bonds, both compounds show a small band gap (1.84 eV for CN1 and 1.37 eV for CN2). They also display moderate fluorescence quantum yield (35 % for CN1 and 50 % for CN2) owing to the contorted geometry, which can suppress aggregation in solution.
Clarification of Decomposition Pathways in a State‐of‐the‐Art Lithium Ion Battery Electrolyte through 13C‐Labeling of Electrolyte Components
Authors: Henschel Jonas , Peschel Christoph , Klein Sven , Horsthemke Fabian , Winter Martin , Nowak Sascha
Published: February 2020

The decomposition of state‐of‐the‐art lithium ion battery (LIB) electrolytes leads to a highly complex mixture during battery cell operation. Furthermore, thermal strain by e.g., fast charging can initiate the degradation and generate various compounds. The correlation of electrolyte decomposition products and LIB performance fading over life‐time is mainly unknown. The thermal and electrochemical degradation in electrolytes comprising 1 m LiPF6 dissolved in 13C3‐labeled ethylene carbonate (EC) and unlabeled diethyl carbonate is investigated and the corresponding reaction pathways are postulated. Furthermore, a fragmentation mechanism assumption for oligomeric compounds is depicted. Soluble decomposition products classes are examined and evaluated with liquid chromatography‐high resolution mass spectrometry. This study proposes a formation scheme for oligo phosphates as well as contradictory findings regarding phosphate‐carbonates, disproving monoglycolate methyl/ethyl carbonate as the central reactive species.
A series of Salen‐type homodinuclear lanthanide complexes and their slow magnetic relaxation in Dy2 and Ho2
Authors: Zhang Lun , Yang Pei‐Pei , Li Ling‐Fei , Hu Yi‐Ye , Gao Yu , Tao Jin
Published: February 2020

A series of homodinuclear lanthanide complexes, namely, [Ln2(L)2(MeOH)2(NO3)2] [Ln = Gd (1), Tb (2), Dy (3), and Ho (4)], were synthesized by the reaction of Salen‐type ligand, namely N, N′‐bis(5‐bromosalicylidene)ethane‐1,2‐diamine (H2L), with lanthanide salts in methanol and acetonitrile solution. The two LnIII ions in 1–4 are linked by two Ophenoxo atoms of two L2− ligands to build a dinuclear skeleton. The eight‐coordinate LnIII center adopts a triangular dodecahedron geometry of D2d symmetry. Theoretical calculations revealed that antiferromagnetic interactions exist in those complexes. Dynamic magnetic properties studies indicate that the Dy2 complex behaves as a single‐molecule magnet with an anisotropy barrier of Ueff ≈ 47.68 K and a pre‐exponential factor τ0 = 3.17 × 10−6 s under a zero applied field, whereas the Ho2 complex exhibits a fast tunneling relaxation process that is rationalized through ab initio calculations.
Characterization of bis‐Schiff bases synthesized using ZnFe2O4 nanoparticles as catalyst, and examination of their antibacterial and in vitro cytotoxic properties
Authors: Maaref Hamed , Sheikhhosseini Enayatollah , Foroughi Mohammad Mehdi , Akhgar Mohammad Reza , Jahani Shohreh
Published: February 2020

In this study, ZnFe2O4 nanoparticles (NPs) were prepared by a hydro/solvothermal method, and their structures were characterized by infrared, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy and X‐ray diffraction analyses. These ZnFe2O4 NPs were used in the synthesis of new bis‐Schiff bases by condensation of hydroxyl‐substituted aldehydes with various aromatic diamines in aqueous media. The antimicrobial activities of the synthesized bis‐Schiff bases were tested against gram‐negative as well as gram‐positive bacteria. The MTT method was used to assess the anticancer activity of the bis‐Schiff bases towards human lung and breast cancer cell lines. The results indicated that these compounds could be considered as new anti‐tumor candidates.
The performance of epoxy coatings containing polyaniline (PANI) nanowires in neutral salt, alkaline, and acidic aqueous media
Authors: Gao Min , Wang Jixiao , Zhou Yu , He Pei , Wang Zhi , Zhao Song
Published: February 2020

PANI/epoxy coatings have great promise applications in the industry as the metal corrosion protection coating, and their performance directly determines the life span of the coating and equipment durability. In this study, the performance of epoxy coatings with and without PANI nanowires immersed in 12 wt% NaCl, 5 wt% HCl, and 5 wt% NaOH solutions at different temperature were investigated for the first time. The performance and the degradation reactions of the coating cooperated with PANI nanowires were characterized by the variety of techniques and methods, including ultraviolet–visible spectrophotometry (UV–vis), field emission scanning electron microscopy (SEM), Attenuated Total Reflectance‐Fourier transform Infrared spectroscopy (ATR‐FTIR), and thermogravimetric analysis (TGA). The experiment results indicated that the failure mechanism of the different coatings varied with the different temperatures and solutions. Electrochemical impedance spectra (EIS) results showed that an appropriate content of PANI nanowires improve the protection performance of epoxy coatings in 12 wt% NaCl, 5 wt% HCl, and 5 wt% NaOH solutions, which is attributed to the passivation ability and shielding effect of PANI nanowires.
Muscle Weakness in Myositis: MicroRNA‐Mediated Dystrophin Reduction in a Myositis Mouse Model and Human Muscle Biopsies
Authors: Kinder Travis B. , Heier Christopher R. , Tully Christopher B. , Van der Muelen Jack H. , Hoffman Eric P. , Nagaraju Kanneboyina , Fiorillo Alyson A.
Published: February 2020

Objective

Muscle inflammation is a feature in myositis and Duchenne muscular dystrophy (DMD). Autoimmune mechanisms are thought to contribute to muscle weakness in patients with myositis. However, a lack of correlation between the extent of inflammatory cell infiltration and muscle weakness indicates that nonimmune pathologic mechanisms may play a role. The present study focused on 2 microRNA (miRNA) sets previously identified as being elevated in the muscle of patients with DMD—an “inflammatory” miRNA set that is dampened with glucocorticoids, and a “dystrophin‐targeting” miRNA set that inhibits dystrophin translation—to test the hypothesis that these miRNAs are similarly dysregulated in the muscle of patients with myositis, and could contribute to muscle weakness and disease severity.

Methods

A major histocompatibility complex class I–transgenic mouse model of myositis was utilized to study gene and miRNA expression and histologic features in the muscle tissue, with the findings validated in human muscle biopsy tissue from 6 patients with myositis. Mice were classified as having mild or severe myositis based on transgene expression, body weight, histologic disease severity, and muscle strength/weakness.

Results

In mice with severe myositis, muscle tissue showed mononuclear cell infiltration along with elevated expression of type I interferon and NF‐κB–regulated genes, including Tlr7 (3.8‐fold increase, P < 0.05). Furthermore, mice with severe myositis showed elevated expression of inflammatory miRNAs (miR‐146a, miR‐142‐3p, miR‐142‐5p, miR‐455‐3p, and miR‐455‐5p; ~3–40‐fold increase, P < 0.05) and dystrophin‐targeting miRNAs (miR‐146a, miR‐146b, miR‐31, and miR‐223; ~3–38‐fold increase, P < 0.05). Bioinformatics analyses of chromatin immunoprecipitation sequencing (ChIP‐seq) data identified at least one NF‐κB consensus element within the promoter/enhancer regions of these miRNAs. Western blotting and immunofluorescence analyses of the muscle tissue from mice with severe myositis demonstrated reduced levels of dystrophin. In addition, elevated levels of NF‐κB–regulated genes, TLR7, and miRNAs along with reduced dystrophin levels were observed in muscle biopsy tissue from patients with histologically severe myositis.

Conclusion

These data demonstrate that an acquired dystrophin deficiency may occur through NF‐κB–regulated miRNAs in myositis, thereby suggesting a unifying theme in which muscle injury, inflammation, and weakness are perpetuated both in myositis and in DMD.
Constructing Co3O4 Nanowires on Carbon Fiber Film as a Lithiophilic Host for Stable Lithium Metal Anodes
Authors: Liu Fanfan , Jin Zongzi , Hu Zexun , Zhang Zhiwen , Liu Wei , Yu Yan
Published: February 2020

Lithium metal has been considered as the most promising anode electrode for substantially improving the energy density of next‐generation energy storage devices. However, uncontrollable lithium dendrite growth, an unstable solid electrolyte interface (SEI), and infinite volume variation severely shortens its service lifespan and causes safety hazards, thus hindering the practical application of lithium metal electrodes. Here, carbon fiber film (CFF) modified by lithiophilic Co3O4 nanowires (denoted as Co3O4 Nws) was proposed as a matrix for prestoring lithium metal through a thermal infusion method. The homogeneous needle‐like Co3O4 nanowires can effectively promote molten lithium to infiltrate into the CFF skeleton. The post‐formed Co−Li2O nanowires produced by the reaction of Co3O4 Nws and molten lithium can homogeneously distribute lithium ions flux and efficaciously increase the adsorption energy with lithium ions proved by density functional theory (DFT) calculation, boosting a uniform lithium deposition without dendrite growth. Therefore, the obtained composite anode (denoted as CFF/Co−Li2O@Li) exhibits superior electrochemical performance with high stripping/plating capacities of 3 mAh cm−2 and 5 mAh cm−2 over long‐term cycles in symmetrical batteries. Moreover, in comparison with bare lithium anode, superior Coulombic efficiencies coupled with copper collector and full battery behaviors paired with LiFePO4 cathode are achieved when CFF/Co−Li2O@Li composite anode was employed.
Carbometalation and Heterometalation of Carbon‐Carbon Multiple‐Bonds Using Group‐13 Heavy Metals: Carbogallation, Carboindation, Heterogallation, and Heteroindation
Authors: Nishimoto Yoshihiro , Yasuda Makoto
Published: February 2020

Organogallium and ‐indium compounds are useful reagents in organic synthesis because of their moderate stability, efficient reactivity and high chemoselectivity. Carbogallation and ‐indation of a carbon‐carbon multiple bond achieves the simultaneous formation of carbon‐carbon and carbon‐metal bonds. Heterogallation and ‐indation construct carbon‐heteroatom and carbon‐metal bonds. Therefore, these reaction systems represent a significant synthetic method for organogalliums and ‐indiums. Many chemists have attempted to apply various types of unsaturated compounds such as alkynes, alkenes, and allenes to these reaction systems. This minireview provides an overview of carboindation and ‐gallation as well as heteroindation and ‐gallation.
Enhanced Charge Transport in a Conjugated Polymer Blended with an Insulating Polymer
Authors: Kim Hyung Do , Iriguchi Ryo , Fukuhara Tomohiro , Benten Hiroaki , Ohkita Hideo
Published: February 2020

Herein, the hole transport in a quinoxaline–thiophene based conjugated polymer (PTQ1) mixed with an insulating polystyrene (PS) was studied by macroscopic and local current density−voltage characteristics measurements. As a result, we found that the hole conductivity in PTQ1 : PS blends increases as the weight ratio of PTQ1 is reduced down to 20 wt%. This is mainly ascribed to increases in mobility because the charge carrier density would be constant in the insulating PS matrix. With decreasing PTQ1 weight ratio in the blends, the absorption bandwidth of PTQ1 and additional emission due to excimer decreased, suggesting that interchain interactions are suppressed. By measuring the temperature‐dependent conductivity, we also found that the activation energy for the hole conductivity is smaller in PTQ1 : PS blends than in PTQ1 neat films. These findings suggest that trap sites decrease because of the suppressed interaction between PTQ1 chains in blend films. We also measured conductive atomic force microscope images of the blend films to clarify the local conductive property. For PTQ1 neat films, a low conductive image was observed over the entire film. For PTQ1 : PS blends, on the other hand, many highly conductive spots were locally found. We thus conclude that the dilution of PTQ1 chains in the PS matrix leads to a lower formation of trap sites, resulting in more conductive transport in PTQ1 : PS blends than in PTQ1 neat films.
A Tale of Biphenyl and Terphenyl Substituents for Structurally Diverse Ketiminato Magnesium, Calcium and Germanium Complexes
Authors: Kumar Rohit , Yadav Sandeep , Gour Kritika , Sangtani Ekta , Ranjan Dash Soumya , Raja Abhishekram , Vanka Kumar , Gonnade Rajesh G. , Sen Sakya S.
Published: February 2020

In this paper, we have used two N,O‐ketiminato ligands (L1 and L2) with biphenyl and terphenyl substituent on the nitrogen atom. Deprotonation of L1 with KN(SiMe3)2 and subsequent reaction with MgI2 led to a homoleptic dinuclear magnesium complex (1) with a Mg2O2 four‐membered ring. Deprotonation with nBuLi and subsequent reaction with MgI2 afforded a unusual dinuclear magnesium complex (2) with a Mg2O2 ring. Extension of the ligand for calcium resulted in a trinuclear calcium complex (3) with six four‐membered Ca2O2 rings. We could not isolate any chelating complex when L2 was used as a ligand, and only oxygen bound magnesium (4) and calcium (5) adducts were isolated. DFT studies were performed to understand this dissimilar behavior. More diverse results were obtained when lithiated L1 and L2 were treated with germanium dichloride. We were able to stabilize a monomeric germylene monochloride (7) with L1. However, with L2, an unusual ligand scrambling, and a C−C coupling take place, leading to the formation of a secondary carbocation with GeCl3‐ as a counter‐anion (8). Besides, a germanium dichloride adduct (9) bound to the oxygen center of the ligand was obtained as the minor product.
A Low‐Temperature Molecular Precursor Approach to Copper‐Based Nano‐Sized Digenite Mineral for Efficient Electrocatalytic Oxygen Evolution Reaction
Authors: Chakraborty Biswarup , Kalra Shweta , Beltrán‐Suito Rodrigo , Das Chittaranjan , Hellmann Tim , Menezes Prashanth W. , Driess Matthias
Published: February 2020

In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu9S5 has been prepared from a molecular copper(I) precursor, [{(PyHS)2CuI(PyHS)}2](OTf)2 (1), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu9S5, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu9S5/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm−2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO2 and IrO2 electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu9S5/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu9S5 can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu9S5 that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals.
High‐Voltage Electrolytes for Aqueous Energy Storage Devices
Authors: Wan Fang , Zhu Jiacai , Huang Shuo , Niu Zhiqiang
Published: February 2020

Aqueous energy storage devices have been considered as one of the most promising candidates for large‐scale energy storage owing to their high safety and low cost. However, the narrow stability voltage window of electrolytes originating from the decomposition of water limits their energy density. In this Minireview, we discuss the limited energy density of aqueous energy storage devices in detail, and then the water decomposition mechanism and corresponding key factors. Furthermore, we present the comprehensive overview of the strategies for increasing the stability of aqueous electrolytes, including redox‐active additives, pH regulation of electrolytes, utilization of water‐in‐salt electrolytes, and selection of highly stable electrolyte salts. Finally, this Minireview also offers insights in the design of high‐voltage aqueous electrolytes.
Clinical features of right‐to‐left shunt in the different subgroups of migraine
Authors: Ling Yanyan , Wang Min , Pan Xudong , Zhao Hongqin
Published: February 2020

Objective

Several investigations have documented an association between migraine and right‐to‐left shunt (RLS). However, whether there are specific clinical features that can distinguish between migraine patients with and without RLS is unclear. This study aims to explore whether there are specific clinical features that can distinguish between migraine patients with and without RLS, and to investigate the relationship between the degree of shunt and clinical parameters of headache.

Methods

In this study, we enrolled consecutive migraineurs who underwent a structured, standardized questionnaire for family and personal history and for detailed migraine features. RLS was diagnosed based on a contrast enhancement transcranial Doppler (c‐TCD) examination.

Results

Overall, 113 migraine with aura (MA) and 192 migraine without aura (MO) patients were included. Patients with MA and RLS (MARLS+) had a higher frequency for sensory aura symptoms than those with MA without RLS (MARLS−) (27.4% vs. 10.0%, p = .03). Patients with MO and RLS (MORLS+) presented with significantly younger initial age of migraine onset and experienced more severe pain intensity than those with MO without RLS (MORLS−) (mean ± SD, 25.6 ± 8.9 vs. 29.8 ± 12.7 years, p = .008 and 5.9 ± 1.4 vs. 5.3 ± 1.3, p = .006, respectively). There was no relationship between the degree of shunt and the clinical parameters of headache.

Conclusions

Our results indicate that MO patients presented with a younger initial age of migraine onset and that sensory aura symptoms in MA patients may predict the presence of RLS. However, we did not find support for relationship between the degree of shunt and clinical parameters of headache.
The correlation between serum apolipoprotein B/apolipoprotein A1 ratio and brain necrosis in patients underwent radiotherapy for nasopharyngeal carcinoma
Authors: Li Honghong , Zheng Dong , Xie Fukang , Huang Xiaolong , Zhuo Xiaohuang , Lin Jinpeng , Li Yi , Tang Yamei
Published: February 2020

Introduction

The apolipoprotein B/apolipoprotein A1 (ApoB/ApoA1) ratio is recognized as a clinical indicator of cardiovascular disease and ischemic cerebral disease. Cerebrovascular dysfunction is also involved in head and neck radiotherapy. The aim of this study was to investigate the correlation between ApoB/ApoA1 ratio and the severity of radiation‐induced brain necrosis (RN) in patients who underwent radiotherapy after nasopharyngeal carcinoma (NPC).

Methods

In this retrospective study, 191 NPC patients diagnosed with RN were evaluated. Clinical characteristics, serum lipid, apolipoproteins, and brain magnetic resonance imaging findings were collected. Serum lipid and apolipoproteins were quantified using standard diagnostic assays, and the quality of life (QOL) was assessed by the World Health Organization quality of life abbreviated instrument (WHOQOL‐BREF).

Results

ApoB/ApoA1 ratio was positively correlated with lesion volume (r = .18, p = .03) and negatively correlated with WHOQOL‐BREF scores (r = −.28, p < .01). The ApoB/ApoA1 ratio and intensity‐modulated radiation therapy (IMRT) were independent risk factor of RN volume. Moreover, ApoB/ApoA1 ratio was significantly negatively correlated with physical health (r = −.29, p < .01), psychological (r = −.27, p < .01), social relationships (r = −.17, p = .02), and environment (r = −.27, p < .01) domains of WHOQOL‐BREF.

Conclusions

Serum ApoB/ApoA1 ratio is positively correlated with RN volume, which indicated serum ApoB/ApoA1 ratio as an independent risk factor for lesion volume in patients with RN after radiotherapy for NPC, suggesting a bright intervention target in RN treatment.
Crisis spillover of corporate environmental misconducts: The roles of perceived similarity, familiarity, and corporate environmental responsibility in determining the impact on oppositional behavioral intention
Authors: Ouyang Zhe , Yao Chris Nengzhi , Hu Xi
Published: February 2020

Negative impact of a firm's environmental misconduct can spread to other firms under the same category due to stakeholders' categorization. Such problem implies a sociocognitive process that has yet to be explored. Therefore, this study extends the current literature by exploring how interfirm similarity affects the spillover effects through stakeholders' engagement. We propose that interfirm similarity can be perceived by stakeholders as a categorization standard, which can lead to their opposition to other firms. Spillover of misconduct is caused by the decreasing stakeholders' trust, wherein the negative effect is contingent upon stakeholders' perceptions. A questionnaire study is conducted to investigate how people resist an innocent firm in China when a chemistry firm experienced an explosion accident. Our findings confirm that interfirm similarity increases stakeholders' opposition to the innocent firm by decreasing their trust. However, the negative effect is alleviated when the innocent firm is perceived as highly environmentally responsible. Our work contributes to the crisis spillover literature and carries important implications for the management of innocent firms that may lose from an industry peer's misconduct.
Computational analysis of morphological and molecular features in gastric cancer tissues
Authors: Yasuda Yoko , Tokunaga Kazuaki , Koga Tomoaki , Sakamoto Chiyomi , Goldberg Ilya G. , Saitoh Noriko , Nakao Mitsuyoshi
Published: February 2020

Biological morphologies of cells and tissues represent their physiological and pathological conditions. The importance of quantitative assessment of morphological information has been highly recognized in clinical diagnosis and therapeutic strategies. In this study, we used a supervised machine learning algorithm wndchrm to classify hematoxylin and eosin (H&E)‐stained images of human gastric cancer tissues. This analysis distinguished between noncancer and cancer tissues with different histological grades. We then classified the H&E‐stained images by expression levels of cancer‐associated nuclear ATF7IP/MCAF1 and membranous PD‐L1 proteins using immunohistochemistry of serial sections. Interestingly, classes with low and high expressions of each protein exhibited significant morphological dissimilarity in H&E images. These results indicated that morphological features in cancer tissues are correlated with expression of specific cancer‐associated proteins, suggesting the usefulness of biomolecular‐based morphological classification.
Site‐Specific Protein Labeling with Fluorophores as a Tool To Monitor Protein Turnover
Authors: Mideksa Yonatan G. , Fottner Maximilian , Braus Sebastian , Weiß Caroline A. M. , Nguyen Tuan‐Anh , Meier Susanne , Lang Kathrin , Feige Matthias J.
Published: February 2020

Proteins that terminally fail to acquire their native structure are detected and degraded by cellular quality control systems. Insights into cellular protein quality control are key to a better understanding of how cells establish and maintain the integrity of their proteome and of how failures in these processes cause human disease. Here we have used genetic code expansion and fast bio‐orthogonal reactions to monitor protein turnover in mammalian cells through a fluorescence‐based assay. We have used immune signaling molecules (interleukins) as model substrates and shown that our approach preserves normal cellular quality control, assembly processes, and protein functionality and works for different proteins and fluorophores. We have further extended our approach to a pulse‐chase type of assay that can provide kinetic insights into cellular protein behavior. Taken together, this study establishes a minimally invasive method to investigate protein turnover in cells as a key determinant of cellular homeostasis.
Exploring Opportunities for Platinum Nanoparticles Encapsulated in Porous Liquids as Hydrogenation Catalysts
Authors: Hemming Ellen B. , Masters Anthony F. , Maschmeyer Thomas
Published: February 2020

The unusual combination of characteristics observed for porous liquids, which are typically associated with either porous solids or liquids, has led to considerable interest in this new class of materials. However, these porous liquids have so far only been investigated for their ability to separate and store gases. Herein, the catalytic capability of Pt nanoparticles encapsulated within a Type I porous liquid (Pt@HS‐SiO2PL) is explored for the hydrogenation of several alkenes and nitroarenes under mild conditions (T=40 °C,PH2=1 atm). The different intermediates in the porous liquid synthesis (i.e., the initial Pt@HS‐SiO2, the organosilane‐functionalized intermediate, and the final porous liquid) are employed as catalysts in order to understand the effect of each component of the porous liquid on the catalysis. For the hydrogenation of 1‐decene, the Pt@HS‐SiO2PL catalyst in ethanol has the fastest reaction rate if normalized with respect to the concentration of Pt. The reaction rate slows if the reaction is completed in a “neat” porous liquid system, probably because of the high viscosity of the system. These systems may find application in cascade reactions, in particular, for those with mutually incompatible catalysts.
Rational Design of a Cocktail of Inhibitors against Aβ Aggregation
Authors: Li Gao , Yang Wu‐Yue , Li Wen‐Hao , Luo Yun‐Yi , Lim Yeh‐Jun , Li Yang , Paul Ashim , Segal Daniel , Hong Liu , Li Yan‐Mei
Published: February 2020

It has been reported that many molecules could inhibit the aggregation of Aβ (amyloid‐β) through suppressing either primary nucleation, secondary nucleation, or elongation processes. In order to suppress multiple pathways of Aβ aggregation, we screened 23 small molecules and found two types of inhibitors with different inhibiting mechanisms based on chemical kinetics analysis. Trp‐glucose conjugates (AS2) could bind with fibril ends while natural products (D3 and D4) could associate with monomers. A cocktail of these two kinds of molecules achieved co‐inhibition of various fibrillar species and avoid unwanted interference.
Iron‐Catalyzed Cleavage Reaction of Keto Acids with Aliphatic Aldehydes for the Synthesis of Ketones and Ketone Esters
Authors: Zhou Fangyuan , Li Lesong , Lin Kao , Zhang Feng , Deng Guo‐Jun , Gong Hang
Published: February 2020

The radical–radical coupling reaction is an important synthetic strategy. In this study, the iron‐catalyzed radical–radical cross‐coupling reaction based on the decarboxylation of keto acids and decarbonylation of aliphatic aldehydes to obtain valuable aryl ketones is reported for the first time. Remarkably, when tertiary aldehydes were used as carbonyl sources, ketone esters were selectively obtained instead of ketones. The gram‐scale preparation of aryl ketone through this strategy was easily achieved by using only 3 mol % of the iron catalyst. As a proof‐of‐concept, the bioactive molecule flurprimidol was synthesized in two steps by using this strategy.
Amino Alcohol Acrylonitriles as Activators of the Aryl Hydrocarbon Receptor Pathway: An Unexpected MTT Phenotypic Screening Outcome
Authors: Baker Jennifer R. , Russell Cecilia C. , Gilbert Jayne , Sakoff Jennette A. , McCluskey Adam
Published: February 2020

Lead (Z)‐N‐(4‐(2‐cyano‐2‐(3,4‐dichlorophenyl)vinyl)phenyl)acetamide, 1 showed MCF‐7 GI50=30 nM and 400‐fold selective c.f. MCF10A (normal breast tissue). Acetamide moiety modification (13 a‐g) to introduce additional hydrophobicity was favoured with MCF‐7 breast cancer cell activity enhanced at 1.3 nM. Other analogues were potent against the HT29 colon cancer cell line at 23 nM. Textbook SAR data was observed in the MCF‐7 cell line, in an MTT assay, via the ortho (17 a), meta (17 b) and para (13 f). The amino alcohol ‐OH moiety was pivotal, but no stereochemical preference noted. But, these data did not fit our homology modelling expectations. Aberrant MTT ((3‐[4,5‐dimethylthiazol‐2‐yl]‐2,5‐diphenyl‐tetrazolium bromide) screening results and metabolic interference confirmed by sulforhodamine B (SRB) screening. Interfering analogues resulted in 120 and 80‐fold CYP1A1 and CYP1A2 amplification, with no upregulation of SULT1A1. This is consistent with activation of the AhR pathway. Piperidine per‐deuteration reduced metabolic inactivation. 3‐OH / 4‐OH piperidine analogues showed differential MTT and SRB activity supporting MTT assay metabolic inactivation. Data supports piperidine 3‐OH, but not the 4‐OH, as a CYP substrate. This family of β‐amino alcohol substituted 3,4‐dichlorophenylacetonitriles show broad activity modulated via the AhR pathway. By SRB analysis the most potent analogue was 23 b, (Z)‐3‐(4‐(3‐(4‐phenylpiperidin‐1‐yl)‐2‐hydroxypropoxy)phenyl)‐2‐(3,4‐dichlorophenyl)‐acrylonitrile.
Application of a machine learning algorithm to predict malignancy in thyroid cytopathology
Authors: Elliott Range Danielle D. , Dov David , Kovalsky Shahar Z. , Henao Ricardo , Carin Lawrence , Cohen Jonathan
Published: February 2020

Background

The Bethesda System for Reporting Thyroid Cytopathology (TBSRTC) comprises 6 categories used for the diagnosis of thyroid fine‐needle aspiration biopsy (FNAB). Each category has an associated risk of malignancy, which is important in the management of a thyroid nodule. More accurate predictions of malignancy may help to reduce unnecessary surgery. A machine learning algorithm (MLA) was developed to evaluate thyroid FNAB via whole slide images (WSIs) to predict malignancy.

Methods

Files were searched for all thyroidectomy specimens with preceding FNAB over 8 years. All cytologic and surgical pathology diagnoses were recorded and correlated for each nodule. One representative slide from each case was scanned to create a WSI. An MLA was designed to identify follicular cells and predict the malignancy of the final pathology. The test set comprised cases blindly reviewed by a cytopathologist who assigned a TBSRTC category. The area under the receiver operating characteristic curve was used to assess the MLA performance.

Results

Nine hundred eight FNABs met the criteria. The MLA predicted malignancy with a sensitivity and specificity of 92.0% and 90.5%, respectively. The areas under the curve for the prediction of malignancy by the cytopathologist and the MLA were 0.931 and 0.932, respectively.

Conclusions

The performance of the MLA in predicting thyroid malignancy from FNAB WSIs is comparable to the performance of an expert cytopathologist. When the MLA and electronic medical record diagnoses are combined, the performance is superior to the performance of either alone. An MLA may be used as an adjunct to FNAB to assist in refining the indeterminate categories.
Nanocellulose‐Mediated Transition of Lithium‐Rich Pseudo‐Quaternary Metal Oxide Nanoparticles into Lithium Nickel Cobalt Manganese Oxide (NCM) Nanostructures
Authors: Zehetmaier Peter M. , Zoller Florian , Beetz Michael , Plaß Maximilian A. , Häringer Sebastian , Böller Bernhard , Döblinger Markus , Bein Thomas , Fattakhova‐Rohlfing Dina
Published: February 2020

We report the syntheses of various compounds within the pseudo‐quaternary system of the type LiwNixCoyMnzOδ (δ≤1) (pre‐NCMs). Four different compositions of this compound were realized as ultrasmall crystalline nanoparticles of 1–4 nm diameter using low‐temperature solvothermal reaction conditions in tert‐butanol at only 170 °C. All of the pre‐NCMs crystallize in the rock‐salt structure and their lithium content is between 20% and 30% with respect to the complete metal content. By adjusting the lithium content to 105% stoichiometry in the solvothermal reaction, the pre‐NCMs can easily react to the respective Li(NixCoyMnz)O2 (NCM) nanoparticles. Furthermore, nanosized desert‐rose structured NCMs were obtained after addition of nanocellulose during the synthesis. By using the mixed metal monoxides as precursor for the NCMs, cation mixing between lithium and nickel is favored and gets more pronounced with increasing nickel content. The cation mixing effect compromises good electrochemical capacity retention, but the desert‐rose structure nevertheless enables enhanced stability at high power conditions, especially for NCM333.