bluuebunny/crossref_metadata_2025 huggingface dataset:
Solution‐Processed Extremely Efficient Multicolor Perovskite Light‐Emitting Diodes Utilizing Doped Electron Transport Layer
Authors: Qasim Khan , Wang Baoping , Zhang Yupeng , Li Pengfei , Wang Yusheng , Li Shaojuan , Lee Shuit‐Tong , Liao Liang‐Sheng , Lei Wei , Bao Qiaoliang
Published: March 2017

A specially designed n‐type semiconductor consisting of Ca‐doped ZnO (CZO) nanoparticles is used as the electron transport layer (ETL) in high‐performance multicolor perovskite light‐emitting diodes (PeLEDs) fabricated using an all‐solution process. The band structure of the ZnO is tailored via Ca doping to create a cascade of conduction energy levels from the cathode to the perovskite. This energy band alignment significantly enhances conductivity and carrier mobility in the CZO ETL and enables controlled electron injection, giving rise to sub‐bandgap turn‐on voltages of 1.65 V for red emission, 1.8 V for yellow, and 2.2 V for green. The devices exhibit significantly improved luminance yields and external quantum efficiencies of, respectively, 19 cd A−1 and 5.8% for red emission, 16 cd A−1 and 4.2% for yellow, and 21 cd A−1 and 6.2% for green. The power efficiencies of these multicolor devices demonstrated in this study, 30 lm W−1 for green light‐emitting PeLED, 28 lm W−1 for yellow, and 36 lm W−1 for red are the highest to date reported. In addition, the perovskite layers are fabricated using a two‐step hot‐casting technique that affords highly continuous (>95% coverage) and pinhole‐free thin films. By virtue of the efficiency of the ETL and the uniformity of the perovskite film, high brightnesses of 10 100, 4200, and 16,060 cd m−2 are demonstrated for red, yellow, and green PeLEDs, respectively. The strategy of using a tunable ETL in combination with a solution process pushes perovskite‐based materials a step closer to practical application in multicolor light‐emitting devices.
Simple Protein Modification Using Zwitterionic Polymer to Mitigate the Bioactivity Loss of Conjugated Insulin
Authors: Xie Jinbing , Lu Yang , Wang Wei , Zhu Hui , Wang Zhigang , Cao Zhiqiang
Published: March 2017

Polymer–protein conjugation has been extensively explored toward a better protein drug with improved pharmacokinetics. However, a major problem with polymer–protein conjugation is that the polymers drastically reduce the bioactivity of the modified protein. There is no perfect solution to prevent the bioactivity loss, no matter the polymer is conjugated in a non‐site specific way, or a more complex site‐specific procedure. Here the authors report for the first time that when zwitterionic carboxybetaine polymer (PCB) is conjugated to insulin through simple conventional coupling chemistry. The resulting PCB–insulin does not show a significant reduction of in vitro bioactivity. The obtained PCB–insulin shows two significant advantages as a novel pharmaceutical agent. First, its therapeutic performance is remarkable. For PCB–insulin, there is a 24% increase of in vivo pharmacological activity of lowering blood glucose compared with native insulin. Such uncommonly seen increase has rarely been reported and is expected to be due to both the improved pharmacokinetics and retained bioactivity of PCB–insulin. Second, the production is simple from manufacturing standpoints. Conjugation procedure involves only one‐step coupling reaction without complex site‐specific linkage technique. The synthesized PCB–insulin conjugates do not require chromatographic separation to purify and obtain particular isoforms.
Versatile Polymer Nanoparticles as Two‐Photon‐Triggered Photosensitizers for Simultaneous Cellular, Deep‐Tissue Imaging, and Photodynamic Therapy
Authors: Guo Liang , Ge Jiechao , Liu Qian , Jia Qingyan , Zhang Hongyan , Liu Weimin , Niu Guangle , Liu Sha , Gong Jianru , Hackbarth Steffen , Wang Pengfei
Published: March 2017

Clinical applications of current photodynamic therapy (PDT) photosensitizers (PSs) are often limited by their absorption in the UV–vis range that possesses limited tissue penetration ability, leading to ineffective therapeutic response for deep‐seated tumors. Alternatively, two‐photon excited PS (TPE‐PS) using NIR light triggered is one the most promising candidates for PDT improvement. Herein, multimodal polymer nanoparticles (PNPs) from polythiophene derivative as two‐photon fluorescence imaging as well as two‐photon‐excited PDT agent are developed. The prepared PNPs exhibit excellent water dispersibility, high photostability and pH stability, strong fluorescence brightness, and low dark toxicity. More importantly, the PNPs also possess other outstanding features including: (1) the high 1O2 quantum yield; (2) the strong two‐photon‐induced fluorescence and efficient 1O2 generation; (3) the specific accumulation in lysosomes of HeLa cells; and (4) the imaging detection depth up to 2100 µm in the mock tissue under two‐photon. The multifunctional PNPs are promising candidates as TPE‐PDT agent for simultaneous cellular, deep‐tissue imaging, and highly efficient in vivo PDT of cancer.
Effects of Interlayer Coupling on Hot‐Carrier Dynamics in Graphene‐Derived van der Waals Heterostructures
Authors: Narang Prineha , Zhao Litao , Claybrook Steven , Sundararaman Ravishankar
Published: March 2017

Graphene exhibits promise as a plasmonic material with high mode confinement that could enable efficient hot carrier extraction. The lifetimes and mean free paths of energetic carriers have been investigated in free‐standing graphene, graphite, and a heterostructure consisting of alternating graphene and hexagonal boron nitride layers using ab initio calculations of electron–electron and electron–phonon scattering in these materials. It is found that the extremely high lifetimes (3 ps) of low‐energy carriers near the Dirac point in graphene, which are a 100 times larger than that in noble metals, are reduced by an order of magnitude due to interlayer coupling in graphite, but enhanced in the heterostructure due to phonon mode clamping. However, these lifetimes drop precipitously with increasing carrier energy and are smaller than those in noble metals at energies exceeding 0.5 eV. By analyzing the contribution of different scattering mechanisms and interlayer interactions, desirable spacer layer characteristics—high dielectric constant and heavy atoms—that could pave the way for plasmonic heterostructures with improved hot carrier transport have been identified.
Hydrophilic films: How hydrophilicity affects blood compatibility and cellular compatibility
Authors: Kuo Zong‐Keng , Fang Mei‐Yen , Wu Tu‐Yi , Yang Ted , Tseng Hsiang‐Wen , Chen Chih‐Chen , Cheng Chao‐Min
Published: March 2017

Hydrophilic materials have been used in many fields, but have recently garnered growing attention in biomedicine. To promote the development and use of suitable hydrophilic materials for biomedical applications, we used three hydrophilic films of varying hydrophilicity and examined the effects of their hydrophilicity on blood compatibility, protein adsorption, blood clotting time, hemolytic activity, biocompatibility, and cell attachment. Across the spectrum of hydrophilicity examined, no obvious differences in biocompatibility were observed. While high material hydrophilicity was associated with higher hemolytic activity, it still fit the nonhemolytic criteria. Further, higher hydrophilicity decreased protein adsorption and cell attachment, but increased thromboresistance in our blood clotting time assay (~30% higher blood clotting index at 10 min). These results indicate that hydrophilicity increases blood compatibility with regard to thromboresistance, but reduces cellular compatibility (i.e., cell attachment), characteristics that could be exploited for a wide range of potential applications in various fields, such as glucose electrode test strips.
Mechanical, interfacial, and fracture characteristics of poly (lactic acid) and Moringa oleifera fiber composites
Authors: Islam Muhammad R. , Isa Nadia , Yahaya Ahmad N. , Beg Mohammad Dalour Hossen , Yunus Rosli M.
Published: March 2017

Three different processing techniques, extrusion, injection, and compression, were followed to fabricate poly (lactic acid) (PLA) and Moringa oleifera fiber (MOF) based composites. Chopped fibers of length 3–5 mm were used for the extrusion followed by injection molding, whereas long‐length fibers (~100 mm) were used for compression molding process. For compression molding, long‐length fibers were spread in single and double layers. The interfacial shear strength of the composites was evaluated by fiber pull‐out testing. Composites were characterized for fracture behavior and mechanical properties. Additionally, surface morphology was also observed by scanning electron microscopy, whereas crystalline properties were evaluated by X‐ray diffraction analysis. Analyses revealed that compression molding with double layers of long‐length fibers reinforcement showed better properties than other samples. Tensile strengths of extruded and compression processed samples (double‐layered) were 75.5 and 81.1 MPa, which are approximately 33% and 44% higher respectively than neat PLA (56.5 MPa). The crack generation of PLA during applied load was observed and found eliminated for the double‐layered sample processed via compression molding. It was found that compression molding with double layer can be considered as easy and less time‐consuming method for composite preparation, with nearly 8 wt.% of less fiber consumption compared with extrusion/injection molding.
Selection of oxygen permeation models for different mixed ionic‐electronic conducting membranes
Authors: Zhu Yue , Li Wenping , Liu Yan , Zhu Xuefeng , Yang Weishen
Published: March 2017

Permeation data of several mixed ionic‐electronic conducting (MIEC) membranes were analyzed by two oxygen permeation models (i.e., Zhu's model and Xu–Thomson's model), respectively, to find a concise method to guide the choice of permeation models. We found that Zhu's model can well fit the permeation data of perovskite‐type membranes, like Ba0.5Sr0.5Co0.8Fe0.2O3‐δ (BSCF) and BaCe0.05Fe0.95O3‐δ (BCF), and dual‐phase membranes, like 75 wt % Ce0.85Sm0.15O1.925–25 wt % Sm0.6Sr0.4Al0.3Fe0.7O3‐δ (SDC‐SSAF), whose oxygen vacancy concentrations are almost independent of the oxygen partial pressure at elevated temperatures. However, Zhu's model was not appropriate for membranes whose oxygen vacancy concentration changed obviously with oxygen partial pressure at elevated temperatures, such as La0.6Sr0.4Co0.2Fe0.8O3‐δ (LSCF) and La0.7Sr0.3CoO3‐δ (LSC). On the contrary, Xu–Thomson's model can fit the data of LSCF and LSC well, but it is inapplicable for BSCF, BCF, and SDC‐SSAF. Therefore, the dependence of oxygen vacancy concentration on oxygen partial pressure was suggested as an index for the selection of the permeation models. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4043–4053, 2017
BCAP31‐associated encephalopathy and complex movement disorder mimicking mitochondrial encephalopathy
Authors: Albanyan Saleh , Al Teneiji Amal , Monfared Nasim , Mercimek‐Mahmutoglu Saadet
Published: March 2017

BCAP31, encoded by BCAP31, is involved in the export of transmembrane proteins from the endoplasmic reticulum. Pathogenic variants in BCAP31 results in global developmental delay, dystonia, deafness and dysmorphic features in males, called deafness, dystonia, and cerebral hypomyelination (DDCH) syndrome. We report a new patient with BCAP3‐associated encephalopathy, DDCH syndrome, sensorineural hearing loss, generalized dystonia, and choreoathetosis. This 3.5‐year‐old boy had microcephaly and failure to thrive within the first 3 months of life. His brain MRI showed bilateral increased signal intensity in globus pallidus at age 3 months raising the suspicion of mitochondrial encephalopathy. His muscle biopsy revealed pleomorphic subsarcolemmal mitochondria collection in electron microscopy. Respiratory chain enzyme activities were normal in muscle. He was enrolled to a whole exome sequencing research study, which identified a hemizygous likely pathogenic truncating variant (c.533_536dup; p.Ser180AlafsX6) in BCAP31, inherited from his mother, who had sensorineural hearing loss and normal cognitive functions. We report a new patient with BCAP31‐associated encephalopathy, DDCH syndrome, mimicking mitochondrial encephalopathy. We also report a heterozygous mother who has bilateral sensorineural hearing loss. This patient's clinical features, muscle histopathology, brain MRI features, and family history were suggestive of mitochondrial encephalopathy. Whole exome sequencing research study confirmed the diagnosis of BCAP31‐associated encephalopathy, DDCH syndrome.
Advanced cardiovascular imaging in Williams syndrome: Abnormalities, usefulness, and strategy for use
Authors: Hills Jordan A. , Zarate Yuri A. , Danylchuk Noelle R. , Lepard Tiffany , Chen Jean Chi‐Jen , Collins Ronnie Thomas
Published: March 2017

Extracardiac arterial stenoses are not uncommon in Williams syndrome (WS); however, data on the utility of advanced cardiovascular imaging (CVI) to assess these stenoses are lacking. We retrospectively reviewed the frequency, indication, and diagnostic outcomes of CVI modalities performed in patients with WS evaluated at a single institution between 2001 and 2014. Data were collected and analyzed from 34 patients (56% female) who underwent CVI during the study period. The median age was 10 years (range 1.8–33 years). Excluding echocardiograms, 78 CVI studies “advanced” were performed in the 34 patients (mean 2.3 studies/patient). The most common advanced CVI was renal ultrasound with Doppler (29/34, 85%), followed by computed tomographic angiography (13/34, 38%) and magnetic resonance angiography in (9/34, 26%). Abnormalities were detected in 62% of patients (21/34). For the 20 patients in whom advanced CVI were performed for defined clinical indications, the rate of abnormalities were 73, 70, 57, and 100% when performed for anatomic delineation (15 patients), hypertension (10 patients), bruits (7 patients), and/or decreased peripheral pulses (2 patients), respectively. Advanced CVI in patients with WS reveals abnormalities in the majority of cases, and physical exam findings frequently indicate abnormalities on advanced CVI.
Intrafamilial phenotypic variability in a Polish family with Sensenbrenner syndrome and biallelic WDR35 mutations
Authors: Walczak‐Sztulpa Joanna , Wawrocka Anna , Sobierajewicz Agata , Kuszel Lukasz , Zawadzki Jan , Grenda Ryszard , Swiader‐Lesniak Anna , Kocyla‐Karczmarewicz Beata , Wnuk Anna , Latos‐Bielenska Anna , Chrzanowska Krystyna H.
Published: March 2017

Sensenbrenner syndrome (cranioectodermal dysplasia, CED) is a very rare autosomal recessive ciliopathy. Cranioectodermal dysplasia is characterized by craniofacial, skeletal, and ectodermal abnormalities. About 50 patients have been described to date. Sensenbrenner syndrome belongs to a group of ciliary chondrodysplasias and is a genetically heterogeneous disorder. Mutations in five genes: IFT122, WDR35, IFT43, WDR19, and IFT52 have been associated with CED. All known genes encode proteins that are part of the intraflagellar transport complex, which plays an important role in the assembly and maintenance of cilia. Here, we report a family with two children affected by Sensenbrenner syndrome, a 9‐year‐old girl and her older sister who died in infancy due to respiratory, liver, and renal insufficiency. Dysmorphic features included short stature with rhizomelic shortening of limbs, short fingers, preaxial polydactyly of left hand, narrow chest, craniosynostosis, dolichocephaly, high anterior hairline, epicanthal folds and telecanthus, depressed nasal bridge, low‐set ears, and additional ectodermal abnormalities. The patient presented with chronic tubulointerstitial renal disease. She had abnormal echogenicity on renal ultrasound, reduced glomerular filtration, albuminuria and tubular proteinuria, hypocalciuria and hypocitraturia, accompanied by pre‐hypertensive state. This pattern of renal abnormality was regarded as nephronophthisis. Psychomotor development was apparently normal. Molecular analysis in one of the affected individuals identified compound heterozygosity for a nonsense (c.1922T>G, p.(Leu641*)) and missense (c.2522A>T, p.(Asp841Val)) variants in WDR35. We present a detailed clinical descriptions of two female siblings showing an intrafamilial phenotypic variability of the disease, and illustrating the potential lethality of CED.
Thyroid dysfunction in patients with Down syndrome: Results from a multi‐institutional registry study
Authors: Lavigne Jenifer , Sharr Christianne , Elsharkawi Ibrahim , Ozonoff Al , Baumer Nicole , Brasington Campbell , Cannon Sheila , Crissman Blythe , Davidson Emily , Florez Jose C. , Kishnani Priya , Lombardo Angela , Lyerly Jordan , McDonough Mary Ellen , Schwartz Alison , Berrier Kathryn , Sparks Susan , Stock‐Guild Kara , Toler Tomi L. , Vellody Kishore , Voelz Lauren , Skotko Brian G.
Published: March 2017

The goals of this undertaking were to assess the outcomes of thyroid screening tests and adherence to thyroid screening guidelines across five Down syndrome (DS) specialty clinics in various states. Data related to thyroid screening were collected for 663 individuals across five clinics specializing in the comprehensive care of individuals with DS for a period of 1 year. Of the 663 participants, 47.7% of participants had a TSH and free T4 ordered at their DS specialty clinic visit. Approximately 19.0% (60/316) had a new thyroid disorder diagnosis made. We conclude that a sizable proportion of the patients with DS are not up‐to‐date on current guidelines when they present to a DS specialty clinic, while adherence to thyroid screening guidelines helps facilitate early diagnoses. Hypothyroidism is prevalent in the population, consistent with reported literature. DS specialty clinics can help patients stay current on screening guidelines.
Regioselective Synthesis of Thiocyanate‐Containing Isoxazolines via FeIII/K2S2O8‐Mediated Radical Thiocyanation/Cyclization Cascade Reaction of β,γ‐Unsaturated Oximes
Authors: Ji Fei , Fan Yun , Yang Run , Yang Yueyan , Yu Dianwen , Wang Minyu , Li Zhiyu
Published: March 2017

A simple approach for the synthesis of thiocyanate‐containing isoxazolines by FeIII/K2S2O8 mediated radical thiocyanation/cyclization cascade reaction of accessible β,γ‐unsaturated oximes has been developed. The high selectivity, mild reaction conditions and absence of harmful heavy‐metal reagents render this reaction attractive. Additionally, the thiocyanate group from isoxazolines could be easily converted to various important functional groups, which could make these compounds important building blocks in organic synthesis.
Localization properties of the disordered XY spin chain
Authors: Abdul‐Rahman Houssam , Nachtergaele Bruno , Sims Robert , Stolz Günter
Published: March 2017

We review several aspects of Many‐Body Localization‐like properties exhibited by the disordered XY chains: localization properties of the energy eigenstates and thermal states, propagation bounds of Lieb‐Robinson type, decay of correlation functions, absence of particle transport, bounds on the bipartite entanglement, and bounded entanglement growth under the dynamics. We also prove new results on the absence of energy transport and Fock space localization. All these properties are made accessible to mathematical analysis due to the exact mapping of the XY chain to a system of quasi‐free fermions given by the Jordan‐Wigner transformation. Motivated by these results we discuss conjectured properties of more general disordered quantum spin and other systems as possible directions for future mathematical research.
Surface plasmon polariton amplification in semiconductor–graphene–dielectric structure
Authors: Dadoenkova Yuliya S. , Moiseev Sergey G. , Abramov Aleksei S. , Kadochkin Aleksei S. , Fotiadi Andrei A. , Zolotovskii Igor O.
Published: March 2017

A mechanism of amplification of surface plasmon polaritons due to the transfer of electromagnetic energy from a drift current wave into a far‐infrared surface wave propagating along a semiconductor‐dielectric boundary in waveguide geometry is proposed. A necessary condition of the interaction of these waves is phase matching condition, i. e., when the phase velocity of the surface wave approaches the drift velocity of charge carriers. It is shown that in the spectral region of the surface plasmon polariton slowing‐down its amplification coefficient can reach values substantially exceeding the ohmic loss coefficient of the surface wave in the structure.

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Zirconacyclopentadiene‐Annulated Polycyclic Aromatic Hydrocarbons
Authors: Kiel Gavin R. , Ziegler Micah S. , Tilley T. Don
Published: March 2017

Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low‐valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high‐yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X‐ray crystallography) of PAHs containing one or more appended dienes with the ortho‐quinodimethane (o‐QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels–Alder reactions.
Signal‐Induced Release of Guests from a Photolatent Metal–Phenolic Supramolecular Cage and Its Hybrid Assemblies
Authors: Park Chiyoung , Yang Beom Joo , Jeong Ki Beom , Kim Chae Bin , Lee Seunghyun , Ku Bon‐Cheol
Published: March 2017

The coordination chemistry of plant polyphenols and metal ions can be used for coating various substrates and for creating modular superstructures. We herein explored this chemistry for the controlled release of guests from mesoporous silica nanoparticles (MSNs). The selective adsorption of tannic acids (TAs) on MSN silica walls opens the MSN mesoporous channels without disturbing mass transport. The channel may be closed by the coordination of TA with CuII ions. Upon exposure to light, photolysis of Trojan horse guests (photoacid generators, PAGs) leads to acid generation, which enables the release of payloads by decomposing the outer coordination shell consisting of TA and CuII. We also fabricated a modular assembly of MSNs on glass substrates. The photoresponsive release characteristics of the resulting film are similar to those of the individual MSNs. This method is a fast and facile strategy for producing photoresponsive nanocontainers by non‐covalent engineering of MSN surfaces that should be suitable for various applications in materials science.
Iridium‐Catalyzed Asymmetric Hydrogenation of Benzo[b]thiophene 1,1‐Dioxides
Authors: Tosatti Paolo , Pfaltz Andreas
Published: March 2017

An efficient iridium‐catalyzed asymmetric hydrogenation of substituted benzothiophene 1,1‐dioxides is described. The use of iridium complexes with chiral pyridyl phosphinite ligands provides access to highly enantiomerically enriched sulfones with substituents at the 2‐ and 3‐position. Sulfones of this type are of interest as core structures of agrochemicals and pharmaceuticals. Moreover, they can be further reduced to chiral 2,3‐dihydrobenzothiophenes.
Palladium‐Catalyzed Enantioselective Synthesis of 2‐Aryl Cyclohex‐2‐enone Atropisomers: Platform Molecules for the Divergent Synthesis of Axially Chiral Biaryl Compounds
Authors: Pan Chongqing , Zhu Zixi , Zhang Mingkai , Gu Zhenhua
Published: March 2017

The palladium‐catalyzed asymmetric synthesis of enone‐based atropisomers from 2‐iodo‐3‐methylcyclohex‐2‐enones and aryl boronic acid is reported. BoPhoz‐type phosphine–aminophosphine ligands showed superior enantioselectivity over other ligands. These cyclohexenone‐based atropisomers are useful compounds for further elaboration. The divergent synthesis of biaryl atropisomers with different ortho substituents was demonstrated.
Engineering High‐Energy Interfacial Structures for High‐Performance Oxygen‐Involving Electrocatalysis
Authors: Guo Chunxian , Zheng Yao , Ran Jingrun , Xie Fangxi , Jaroniec Mietek , Qiao Shi‐Zhang
Published: March 2017

Engineering high‐energy interfacial structures for high‐performance electrocatalysis is achieved by chemical coupling of active CoO nanoclusters and high‐index facet Mn3O4 nano‐octahedrons (hi‐Mn3O4). A thorough characterization, including synchrotron‐based near edge X‐ray absorption fine structure, reveals that strong interactions between both components promote the formation of high‐energy interfacial Mn‐O‐Co species and high oxidation state CoO, from which electrons are drawn by MnIII‐O present in hi‐Mn3O4. The CoO/hi‐Mn3O4 demonstrates an excellent catalytic performance over the conventional metal oxide‐based electrocatalysts, which is reflected by 1.2 times higher oxygen evolution reaction (OER) activity than that of Ru/C and a comparable oxygen reduction reaction (ORR) activity to that of Pt/C as well as a better stability than that of Ru/C (95 % vs. 81 % retained OER activity) and Pt/C (92 % vs. 78 % retained ORR activity after 10 h running) in alkaline electrolyte.
A Sodium‐Ion‐Conducting Direct Formate Fuel Cell: Generating Electricity and Producing Base
Authors: Li Yinshi , Feng Ying , Sun Xianda , He Yaling
Published: March 2017

A barrier that limits the development of the conventional cation‐exchange membrane direct liquid fuel cells (CEM‐DLFCs) is that the CEM‐DLFCs need additional base to offer both alkaline environment and charge carriers. Herein, we propose a Na+‐conducting direct formate fuel cell (Na‐DFFC) that is operated in the absence of added base. A proof‐of‐concept Na‐DFFC yields a peak power density of 33 mW cm−2 at 60 °C, mainly because the hydrolysis of sodium formate provides enough OH− and Na+ ions, proving the conceptual feasibility. Moreover, contrary to the conventional chlor‐alkali process, this Na‐DFFC enables to generate electricity and produce NaOH simultaneously without polluting the environment. The Na‐DFFC runs stably during 13 hours of continuous operation at a constant current of 10 mA, along with a theoretical production of 195 mg NaOH. This work presents a new type of electrochemical conversion device that possesses a wide range of potential applications.
Novel phase change materials based on fatty acid eutectics and triallyl isocyanurate composites for thermal energy storage
Authors: Huang Xuelin , Guo Jing , He Jing , Gong Yumei , Wang Di , Song Zhaoyang
Published: March 2017

In this study, a series of dimension‐stabilized fatty acid eutectics and triallyl isocyanurate (TAIC) composite phase change materials were prepared via in situ reaction by blending the fatty acids and TAIC, in which the fatty acids were introduced as a phase change material (PCM), and TAIC performed as a supporting material by self‐crosslinking. Fourier transform infrared spectroscopy, X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy (SEM), and thermogravimetric analysis were applied to investigate the chemical structure, crystalline properties, phase transition behavior, microstructure, and thermal stability of the composites. The results indicated that the composite possessed excellent thermal reliability and heat storage durability even after 300 heating–cooling cycles. Moreover, the composites had applicable phase transition temperatures in the range of 26–40 °C and satisfying latent heat storage capacities of higher than 110 J/g. The SEM images showed that the particle size of the nanoparticles of the composites was about 200 nm after treatment. The dimensional measurement of the composites proved a high service temperature of 100 °C, indicating that the composites were promising for thermal energy storage materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44866.
Aging of anhydride‐hardened epoxies in lubricants at elevated temperatures
Authors: Reuscher Vivien , Haag Sabine , Patzelt Gesa , Mayer Bernd
Published: March 2017

In automotive under‐the‐hood applications, electronics respectively their packaging materials come in contact with automotive fluids. The effect of automatic transmission fluid (ATF) on an anhydride‐cured epoxy was investigated at temperatures up to 180 °C for up to 1000 h. This study has shown that ATF retards the oxidative aging of the epoxy, presumably due to oxygen consumption. Whereas in air the material underwent a thermo‐oxidative aging with a mass loss of up to 4% and a strong broadening of Tg to higher temperatures, in ATF a temperature dependent distinctive drop of Tg from 142 to 126 °C after 1000 h aging at 180 °C, and a mass loss of maximum 1% was observed which might be a thermal decomposition of the epoxy material. A slight broadening of the damping factors might indicate an intrusion of ATF components. A color change of the samples could be observed after aging in air and ATF, with the discoloration in air being more intense. An explanation for the color change might be either a minor amount of oxygen causing an oxidative discoloration reaction or the intrusion of colored ATF degradation products. While the oxidation‐kinetics in air exhibited Arrhenius temperature‐dependence the mechanism in ATF changed above 165 °C. An acceleration of aging tests at temperatures beyond 150 °C is, therefore, not possible. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44877.
Industrial polyethylene melt index prediction using ensemble manifold learning–based local model
Authors: Liu Yi , Liang Yu , Gao Zengliang
Published: March 2017

For online melt index prediction in multiple‐grade polyethylene polymerization processes, using only a fixed model is insufficient. Additionally, without enough process knowledge, it is difficult to select suitable input variables to accurately construct prediction models. A novel manifold learning based local probabilistic modeling method named ensemble just‐in‐time Gaussian process regression (EJGPR) is developed. By utilizing output variables, an optimization framework is proposed to preserve the local structure of both input and output variables. Then the output information is integrated into construction of a JGPR‐based local model. Additionally, some new extracted variables in the projection space can be obtained. Moreover, using the probabilistic prediction information, the uncertainty of each JGPR‐based local candidate model can be simply described. Consequently, using an efficient ensemble strategy, a more accurate EJGPR prediction model can be constructed online. The melt index prediction results in an industrial polyethylene process show it has better performance than conventional methods. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45094.
Regulated in Development and DNA Damage Response 1 Deficiency Impairs Autophagy and Mitochondrial Biogenesis in Articular Cartilage and Increases the Severity of Experimental Osteoarthritis
Authors: Alvarez‐Garcia Oscar , Matsuzaki Tokio , Olmer Merissa , Plate Lars , Kelly Jeffery W. , Lotz Martin K.
Published: March 2017

Objective

Regulated in development and DNA damage response 1 (REDD1) is an endogenous inhibitor of mechanistic target of rapamycin (mTOR) that regulates cellular stress responses. REDD1 expression is decreased in aged and osteoarthritic (OA) cartilage, and it regulates mTOR signaling and autophagy in articular chondrocytes in vitro. This study was undertaken to investigate the effects of REDD1 deletion in vivo using a mouse model of experimental OA.

Methods

OA severity was histologically assessed in 4‐month‐old wild‐type and REDD1−/− mice subjected to surgical destabilization of the medial meniscus (DMM). Chondrocyte autophagy, apoptosis, mitochondrial content, and expression of mitochondrial biogenesis markers were determined in cartilage and cultured chondrocytes from wild‐type and REDD1−/− mice.

Results

REDD1 deficiency increased the severity of changes in cartilage, menisci, subchondral bone, and synovium in the DMM model of OA. Chondrocyte death was increased in the cartilage of REDD1−/− mice and in cultured REDD1−/− mouse chondrocytes under oxidative stress conditions. Expression of key autophagy markers (microtubule‐associated protein 1A/1B light chain 3 and autophagy protein 5) was markedly reduced in cartilage from REDD1−/− mice and in cultured human and mouse chondrocytes with REDD1 depletion. Mitochondrial content, ATP levels, and expression of the mitochondrial biogenesis markers peroxisome proliferator–activated receptor γ coactivator 1α (PGC‐1α) and transcription factor A, mitochondrial (TFAM) were also decreased in REDD1‐deficient chondrocytes. REDD1 was required for AMP‐activated protein kinase–induced PGC‐1α in chondrocytes.

Conclusion

Our findings suggest that REDD1 is a key mediator of cartilage homeostasis through regulation of autophagy and mitochondrial biogenesis and that REDD1 deficiency exacerbates the severity of injury‐induced OA.
Simple and Versatile Preparation of Luminescent Amphiphilic Platinum(II)‐containing Polystyrene Complexes With Transformable Nanostructures Assisted by Pt⋅⋅⋅Pt and π–π Interactions
Authors: Cheng Heung‐Kiu , Chung Clive Yik‐Sham , Zhang Kaka , Yam Vivian Wing‐Wah
Published: March 2017

Platinum(II)‐containing polystyrene (PS) complexes have been synthesized by dehydrohalogenation of α‐alkyne‐PS and chloroplatinum(II) precursors with different functionalities on the terpyridine ligands. Through modulation of the hydrophilicity/hydrophobicity of the terpyridine ligands and hence the overall amphiphilicity of the complexes, the complexes can undergo self‐assembly into various superstructures with remarkable luminescence properties in different solution mixtures, as revealed by electron microscopy, UV/Vis absorption and emission spectroscopy. Pt⋅⋅⋅Pt and/or π–π interactions among the platinum(II) terpyridine moieties are found to play substantial roles in the stabilization of the superstructures and the turn‐on/off of the triplet metal–metal‐to‐ligand charge transfer (3MMLCT) emission of the complexes.
Self‐Healable Supramolecular Hydrogel Formed by Nor‐Seco‐Cucurbit[10]uril as a Supramolecular Crosslinker
Authors: Park Kyeng Min , Roh Joon Ho , Sung Gihyun , Murray James , Kim Kimoon
Published: March 2017

A supramolecular hydrogel was formed by a simple mixing of solutions of nor‐seco‐cucurbit[10]uril (NS‐CB[10]) and adamantylamine‐terminated 4‐armed polyethylene glycol (AdA‐4‐arm‐PEG). In the formation of the hydrogel, NS‐CB[10] acted as a noncovalent crosslinker to form a ternary complex with two AdA moieties. The dynamic and selective nature of the host–guest interaction between NS‐CB[10] and AdA enabled the supramolecular hydrogel to rapidly recover its physical properties after it was damaged. In addition, the recovered hydrogel retained its physical properties with negligible differences from those of the pristine material, even after multiple self‐healing cycles. The NS‐CB[10]‐based hydrogel with the self‐healing property may be useful for various biological applications such as drug delivery, cell therapy and tissue engineering.
BIM‐Anwendungen im Tunnelbau
Authors: König Markus , Rahm Tobias , Nagel Felix , Speier Ludger
Published: March 2017

Die Anwendung von Building Information Modeling (BIM) im Infrastrukturbau soll bis zum Jahr 2020 in Deutschland eingeführt und anschließend etabliert werden. Dies schließt auch die Planung, die Herstellung und den Betrieb von Tunnelbauwerken ein. Im Rahmen von Forschungs‐ und Praxisprojekten wurden in den letzten Jahren bereits Erfahrungen zur Verwendung der BIM‐Methodik gesammelt. Es hat sich gezeigt, dass die ganzheitliche Einführung von BIM eine genaue Analyse der einzelnen Prozesse und eine projektspezifische Definition von sinnvollen Anwendungsfällen erfordert. Im Rahmen des Beitrags werden aktuelle Erfahrungen und einzelne BIM‐Anwendungsfälle im Tunnelbau erläutert. Es wird exemplarisch gezeigt, wie die geometrische und semantische Informationstiefe anwendungsfallorientiert festgelegt werden kann. Anschließend wird auf die Umsetzung einer gemeinsamen Datenumgebung sowie die Verknüpfung und den Austausch von Fachmodellen eingegangen. Hierbei haben sich insbesondere Ansätze auf Basis von Linked Data bzw. Multimodell‐Containern als besonders geeignet herausgestellt. Anhand von praxisnahen Beispielen werden verschiedene Anwendungsfälle und damit verbundene Ziele für den Einsatz von BIM präsentiert.
The impact of emotions on recall: An empirical study on social ads
Authors: Missaglia Anna Laura , Oppo Annalisa , Mauri Maurizio , Ghiringhelli Barbara , Ciceri Andrea , Russo Vincenzo
Published: March 2017

Emotions are a complex phenomenon that entails a tricky problem regarding the measurement. To partially overcome this question, we assess emotions both using self‐report and measures commonly used in neuromarketing. This study assesses the accuracy of the recall after 4 months regarding two social advertising videos about female genital mutilation. Forty female participants were recruited. The skin conductance trend of the participants is different when viewing the two videos. The majority of participants (94.9%) reported that the two videos elicited different emotions (sadness for the first video and anger for the second one). Furthermore, according to arousal and valence model, these data are consistent with the literature that underlines the importance of psychophysiological indexes in measuring emotions and their associations with memory performances.
Cytotoxic Essential Oils from Eryngium campestre and Eryngium amethystinum (Apiaceae) Growing in Central Italy
Authors: Cianfaglione Kevin , Blomme Evy E. , Quassinti Luana , Bramucci Massimo , Lupidi Giulio , Dall'Acqua Stefano , Maggi Filippo
Published: March 2017

Eryngium campestre and E. amethystinum are thorny herbs belonging to the Apiaceae family and spontaneously growing in stony pastures and dry meadows, preferentially on calcareous substrates. In the Mediterranean countries, these plants have been used as a food or traditional remedies to treat various ailments. In the present work, we have analyzed the chemical composition of the essential oils distilled from the aerial parts by GC‐FID and GC/MS, and evaluated their cytotoxic effects on a panel of human cancer cells, namely A375 (human malignant melanoma), MDA‐MB 231 cells (human breast adenocarcinoma), and HCT116 cells (human colon carcinoma), by the MTT assay. Furthermore, the Eryngium essential oils were evaluated for antioxidant and acetylcholinesterase (AChE) activities. The two essential oils were rich in sesquiterpene hydrocarbons, with germacrene D as the major compound, accompanied by allo‐aromadendrene, β‐elemene, spathulenol, and ledol. They turned out to be highly cytotoxic on the tumor cells, with IC50 values (1.65 – 5.32 and 1.57 – 2.99 μg/ml for E. amethystinum and E. campestre, respectively) comparable or close to those of the anticancer drug cisplatin. The E. amethystinum essential oil exhibited a moderate antioxidant activity, whereas that of E. campestre a weak AChE inhibition.
Amine Transaminase Engineering for Spatially Bulky Substrate Acceptance
Authors: Weiß Martin S. , Pavlidis Ioannis V. , Spurr Paul , Hanlon Steven P. , Wirz Beat , Iding Hans , Bornscheuer Uwe T.
Published: March 2017

Amine transaminase (ATA) catalyzing stereoselective amination of prochiral ketones is an attractive alternative to transition metal catalysis. As wild‐type ATAs do not accept sterically hindered ketones, efforts to widen the substrate scope to more challenging targets are of general interest. We recently designed ATAs to accept aromatic and thus planar bulky amines, with a sequence‐based motif that supports the identification of novel enzymes. However, these variants were not active against 2,2‐dimethyl‐1‐phenyl‐propan‐1‐one, which carries a bulky tert‐butyl substituent adjacent to the carbonyl function. Here, we report a solution for this type of substrate. The evolved ATAs perform asymmetric synthesis of the respective R amine with high conversions by using either alanine or isopropylamine as amine donor.
Mental Health First Aid: A course and a movement
Authors: Paccione‐Dyszlewski Margaret R.
Published: March 2017

We are on Main Street and a middle‐aged man clutches his chest in cardiac crisis. A member of the community trained in medical first aid administers cardiopulmonary resuscitation (CPR) until paramedics arrive. A life is saved.
Staged management of giant bilateral perinephric adipocytic neoplasms
Authors: Arriola Aileen Grace P. , Bartlett Edmund K. , Zhang Paul J. , Cooper Kumarasen , Naji Ali , Roses Robert E.
Published: March 2017

Key Clinical Message

We present a patient with giant bilateral perinephric masses favored to represent liposarcoma preoperatively. Bilateral renal involvement posed a clinical challenge; careful histologic assessment and surgical planning allowed preservation of renal function.
FMR1 premutation with Prader–Willi phenotype and fragile X‐associated tremor/ataxia syndrome
Authors: Martínez‐Cerdeño Verónica , Lechpammer Mirna , Noctor Stephen , Ariza Jeanelle , Hagerman Paul , Hagerman Randi
Published: March 2017

Key Clinical Message

This is a report of FMR1 premutation with Prader–Willi phenotype (PWP) and FXTAS. Although the PWP is common in fragile X syndrome (FXS), it has never been described in someone with the premutation. The patient presented intranuclear inclusions, severe obesity, hyperphagia, and ADHD symptoms, typical of the PWP in FXS. In addition, the autopsy revealed multiple architectural cortical abnormalities.
Peptide‐FlgA3‐Based Gold Palladium Bimetallic Nanoparticles That Catalyze the Oxygen Reduction Reaction in Alkaline Solution
Authors: Li Dongliang , Tang Zhenghua , Chen Shaowei , Tian Yong , Wang Xiufang
Published: March 2017

Given the synergetic properties of different metal species, bimetallic nanoparticles are of immense scientific interest and technological importance in the field of catalysis. A peptide‐based method represents a new avenue to fabricate bimetallic nanocatalysts with a controllable size, shape, composition, and subtle surface microstructure. However, the electrocatalytic abilities of these peptide‐based bimetallic nanoparticles remain largely unexplored. Herein, we employed the peptide sequence FlgA3 to fabricate a series of AuPd alloys that were used as catalysts for the oxygen reduction reaction (ORR). Among the samples tested, Au33Pd67 exhibited the best activity, evidenced by the most positive onset potential and the largest diffusion‐limited current. Notably, the ORR activity of Au33Pd67 was comparable with that of commercial Pt/C, and the long‐term durability was significantly superior to that of Pt/C. A peptide‐enabled approach might pave the way for the fabrication of bimetallic nanomaterials with enhanced electrocatalytic properties under mild conditions.
Role of Composition and Size of Cobalt Ferrite Nanocrystals in the Oxygen Evolution Reaction
Authors: Chakrapani Kalapu , Bendt Georg , Hajiyani Hamidreza , Schwarzrock Ingo , Lunkenbein Thomas , Salamon Soma , Landers Joachim , Wende Heiko , Schlögl Robert , Pentcheva Rossitza , Behrens Malte , Schulz Stephan
Published: March 2017

Sub‐10 nm CoFe2O4 nanoparticles with different sizes and various compositions obtained by (partial) substitution of Co with Ni cations have been synthesized by using a one‐pot method from organic solutions by the decomposition of metal acetylacetonates in the presence of oleylamine. The electrocatalytic activity of CoFe2O4 towards the oxygen evolution reaction (OER) is clearly enhanced with a smaller size (3.1 nm) of the CoFe2O4 nanoparticles (compared with 4.5 and 5.9 nm). In addition, the catalytic activity is improved by partial substitution of Co with Ni, which also leads to a higher degree of inversion of the spinel structure. Theoretical calculations attribute the positive catalytic effect of Ni owing to the lower binding energy differences between adsorbed O and OH compared with pure cobalt or nickel ferrites, resulting in higher OER activity. Co0.5Ni0.5Fe2O4 exhibited a low overpotential of approximately 340 mV at 10 mA cm−2, a smaller Tafel slope of 51 mV dec−1, and stability over 30 h. The unique tunability of these CoFe2O4 nanocrystals provides great potential for their application as an efficient and competitive anode material in the field of electrochemical water splitting as well as for systematic fundamental studies aiming at understanding the correlation of composition and structure with performance in electrocatalysis.
Highly Active Gold and Gold–Palladium Catalysts Prepared by Colloidal Methods in the Absence of Polymer Stabilizers
Authors: Abis Laura , Freakley Simon J. , Dodekatos Georgios , Morgan David J. , Sankar Meenakshisundaram , Dimitratos Nikolaos , He Qian , Kiely Christopher J. , Hutchings Graham J.
Published: March 2017

Supported gold and gold–palladium nanoparticles were found to be effective catalysts for the selective oxidation of glycerol and benzyl alcohol. The properties and stabilities of catalysts are often sensitive to factors such as the dimensions, shape, and composition of the metal nanoparticles. Although colloidal methods provide an easy and quick way to synthesize supported metal catalysts, they typically involve the use of polymers such as polyvinyl alcohol and polyvinylpyrrolidone as steric stabilizers, which can sometimes be detrimental in subsequent catalytic reactions. Herein, we report the synthesis of supported gold and gold–palladium nanoparticles without the addition of stabilizing polymers. The catalysts prepared with and without the addition of polymers performed very similarly in the selective oxidation of glycerol and benzyl alcohol, which suggests that polymers are not essential to make active catalysts for these reactions. Thus, this new stabilizer‐free method provides a facile and highly effective way of circumventing the inherent problems of polymer stabilizers in the preparation of gold and gold–palladium catalysts.
Cobalt‐Porphyrin‐Catalysed Intramolecular Ring‐Closing C−H Amination of Aliphatic Azides: A Nitrene‐Radical Approach to Saturated Heterocycles
Authors: Kuijpers Petrus F. , Tiekink Martijn J. , Breukelaar Willem B. , Broere Daniël L. J. , van Leest Nicolaas P. , van der Vlugt Jarl Ivar , Reek Joost N. H. , de Bruin Bas
Published: March 2017

Cobalt‐porphyrin‐catalysed intramolecular ring‐closing C−H bond amination enables direct synthesis of various N‐heterocycles from aliphatic azides. Pyrrolidines, oxazolidines, imidazolidines, isoindolines and tetrahydroisoquinoline can be obtained in good to excellent yields in a single reaction step with an air‐ and moisture‐stable catalyst. Kinetic studies of the reaction in combination with DFT calculations reveal a metallo‐radical‐type mechanism involving rate‐limiting azide activation to form the key cobalt(III)‐nitrene radical intermediate. A subsequent low barrier intramolecular hydrogen‐atom transfer from a benzylic C−H bond to the nitrene‐radical intermediate followed by a radical rebound step leads to formation of the desired N‐heterocyclic ring products. Kinetic isotope competition experiments are in agreement with a radical‐type C−H bond‐activation step (intramolecular KIE=7), which occurs after the rate‐limiting azide activation step. The use of di‐tert‐butyldicarbonate (Boc2O) significantly enhances the reaction rate by preventing competitive binding of the formed amine product. Under these conditions, the reaction shows clean first‐order kinetics in both the [catalyst] and the [azide substrate], and is zero‐order in [Boc2O]. Modest enantioselectivities (29–46 % ee in the temperature range of 100–80 °C) could be achieved in the ring closure of (4‐azidobutyl)benzene using a new chiral cobalt‐porphyrin catalyst equipped with four (1S)‐(−)‐camphanic‐ester groups.