bluuebunny/crossref_metadata_2025 huggingface dataset:
Self‐Assembly of Therapeutic Peptide into Stimuli‐Responsive Clustered Nanohybrids for Cancer‐Targeted Therapy
Authors: He Wangxiao , Wang Simeng , Yan Jin , Qu Yiping , Jin Liang , Sui Fang , Li Yujun , You Weiming , Yang Guang , Yang Qi , Ji Meiju , Shao Yongping , Ma Peter X. , Lu Wuyuan , Hou Peng
Published: January 2019

Clinical translation of therapeutic peptides, particularly those targeting intracellular protein–protein interactions (PPIs), has been hampered by their inefficacious cellular internalization in diseased tissue. Therapeutic peptides engineered into nanostructures with stable spatial architectures and smart disease targeting ability may provide a viable strategy to overcome the pharmaceutical obstacles of peptides. This study describes a strategy to assemble therapeutic peptides into a stable peptide–Au nanohybrid, followed by further self‐assembling into higher‐order nanoclusters with responsiveness to tumor microenvironment. As a proof of concept, an anticancer peptide termed β‐catenin/Bcl9 inhibitors is copolymerized with gold ion and assembled into a cluster of nanohybrids (pCluster). Through a battery of in vitro and in vivo tests, it is demonstrated that pClusters potently inhibit tumor growth and metastasis in several animal models through the impairment of the Wnt/β‐catenin pathway, while maintaining a highly favorable biosafety profile. In addition, it is also found that pClusters synergize with the PD1/PD‐L1 checkpoint blockade immunotherapy. This new strategy of peptide delivery will likely have a broad impact on the development of peptide‐derived therapeutic nanomedicine and reinvigorate efforts to discover peptide drugs that target intracellular PPIs in a great variety of human diseases, including cancer.
Long‐Term Prevention of Bacterial Infection and Enhanced Osteoinductivity of a Hybrid Coating with Selective Silver Toxicity
Authors: Xie Kai , Zhou Ziao , Guo Yu , Wang Lei , Li Guoyuan , Zhao Shuang , Liu Xiangmei , Li Jun , Jiang Wenbo , Wu Shuilin , Hao Yongqiang
Published: January 2019

Antibacterial and osteogenic design is required for ideal orthopedic implants. The excellent antimicrobial performance of silver nanoparticles (AgNPs) has attracted interest for the treatment of implant‐related infections. However, the dose‐dependent cytotoxicity of silver and its negative impact on bone implants restrict the further use of AgNPs coatings. Therefore, a hybrid coating containing polydopamine (PDA), hydroxyapatite (HA), AgNPs, and chitosan (CS) is prepared. Organic chelators CS and PDA that have promising biocompatibility are used to prevent the rapid release of silver ions from the AgNPs coating. The double chelating effect of PDA and CS significantly reduces silver ion release from the hybrid coating. The coating exhibits excellent anti‐biofilm efficiency of 91.7%, 89.5%, and 92.0% for Staphylococcus aureus, Staphylococcus epidermidis, and Escherichia coli, respectively. In addition, the coating can significantly stimulate osteogenic differentiation of MC3T3‐E1 cells and promote bone‐implant osseointegration in vivo as compared to that in the control group. The longitudinal biosafety of the coating is confirmed in vivo by histological evaluation and blood tests. The results of this study indicate that the hybrid coating exhibits antibacterial properties as well as allow bone‐implant osseointegration, thereby providing insight into the design of multifunctional implants for long‐term orthopedic applications.
Anode Interface Engineering and Architecture Design for High‐Performance Lithium–Sulfur Batteries
Authors: Zhao Yuanyuan , Ye Yusheng , Wu Feng , Li Yuejiao , Li Li , Chen Renjie
Published: January 2019

Lithium–sulfur (Li–S) batteries are considered as one of the most promising options to realize rechargeable batteries with high energy capacity. Previously, research has mainly focused on solving the polysulfides' shuttle, cathode volume changes, and sulfur conductivity problems. However, the instability of anodes in Li–S batteries has become a bottleneck to achieving high performance. Herein, the main efforts to develop highly stable anodes for Li–S batteries, mainly including lithium metal anodes, carbon‐based anodes, and alloy‐based anodes, are considered. Based on these anodes, their interfacial engineering and structure design are identified as the two most important directions to achieve ideal anodes. Because of high reactivity and large volume change during cycling, Li anodes suffer from severe side reactions and structure collapse. The solid electrolyte interphase formed in situ by modified electrolytes and ex situ artificial coating layers can enhance the interfacial stability of anodes. Replacing common Li foil with rationally designed anodes not only suppresses the formation of dendritic Li but also delays the failure of Li anodes. Manipulating the anode interface engineering and rationally designing anode architecture represents an attractive path to develop high‐performance Li–S batteries.
Advances in Alternating Current Electroluminescent Devices
Authors: Wang Lin , Xiao Lian , Gu Haoshuang , Sun Handong
Published: January 2019

Alternating current (AC)‐driven electroluminescent (EL) devices have recently attracted attention as potential alternatives to direct current (DC)‐driven organic light‐emitting diodes (OLEDs), as they have the great advantage of easy integration into the AC power system of 110/220 V at 50/60 Hz without complicated back‐end electronics. However, the high driving voltage and low power efficiency inherent to AC‐driven EL devices limit their widespread application. While researchers have made some remarkable progress in this field, the underlying causes during the development process remain to be explored. The strategies for improving the performance of AC‐driven EL devices with different configurations, such as the conventional sandwiched structure and multilayer‐based light‐emitting devices, are summarized in this review. For example, it is crucial to enhance the effective electric field around the emitters for AC‐driven thin film electroluminescent (AC‐TFEL) devices, while the unbalanced generation/injection of charge carriers is the main limiting factor for the performance of AC‐driven light‐emitting devices (AC‐LEDs). The recent advances in AC‐driven EL devices, with some new configurations or new‐type emitting materials, are presented by category. The challenges and opportunities for the further development of AC‐driven EL devices are also discussed.
High‐Efficiency Green InP Quantum Dot‐Based Electroluminescent Device Comprising Thick‐Shell Quantum Dots
Authors: Zhang Han , Hu Ning , Zeng Zaiping , Lin Qingli , Zhang Fengjuan , Tang Aiwei , Jia Yu , Li Lin Song , Shen Huaibin , Teng Feng , Du Zuliang
Published: January 2019

Indium phosphide (InP) core/shell quantum dots (QDs) without intrinsic toxicity have shown great potential to replace the widely applied cadmium‐containing QDs in next‐generation commercial display and lighting applications. However, it remains challenging to synthesize InP core/shell QDs with high quantum yields (QYs), uniform particle size, and simultaneously thicker shell thickness to reduce nonradiative Förster resonant energy transfer (FRET). Here, thick InP‐Based QLEDs shell InP/GaP/ZnS//ZnS core/shell QDs with high stability, high QY (≈70%), and large particle size (7.2 ± 1.3 nm) are successfully synthesized through extending the growth time of shell materials along with the timely replenishment of shelling precursor. The existence of GaP interface layer minimizes the lattice mismatch and reduces interfacial defects. While thick ZnS shell, which suppresses the FRET between closely packed QDs, ensures high PL QY and stability. The robustness of such properties is demonstrated by the fabrication of green electroluminescent LEDs based on InP core/shell QDs with the peak external quantum efficiency and current efficiency of 6.3% and 13.7 cd A−1, respectively, which are the most‐efficient InP‐based green quantum dot light‐emitting diodes (QLEDs) till now. This work provides an effective strategy to further improve heavy‐metal‐free QLED performance and moves a significant step toward the commercial application of InP‐based electroluminescent device.
Modeling Gas Adsorption in Flexible Metal–Organic Frameworks via Hybrid Monte Carlo/Molecular Dynamics Schemes
Authors: Rogge Sven M. J. , Goeminne Ruben , Demuynck Ruben , Gutiérrez‐Sevillano Juan José , Vandenbrande Steven , Vanduyfhuys Louis , Waroquier Michel , Verstraelen Toon , Van Speybroeck Veronique
Published: January 2019

Herein, a hybrid Monte Carlo (MC)/molecular dynamics (MD) simulation protocol that properly accounts for the extraordinary structural flexibility of metal–organic frameworks (MOFs) is developed and validated. This is vital to accurately predict gas adsorption isotherms and guest‐induced flexibility of these materials. First, the performance of three recent models to predict adsorption isotherms and flexibility in MOFs is critically investigated. While these methods succeed in providing qualitative insight in the gas adsorption process in MOFs, their accuracy remains limited as the intrinsic flexibility of these materials is very hard to account for. To overcome this challenge, a hybrid MC/MD simulation protocol that is specifically designed to handle the flexibility of the adsorbent, including the shape flexibility, is introduced, thereby unifying the strengths of the previous models. It is demonstrated that the application of this new protocol to the adsorption of neon, argon, xenon, methane, and carbon dioxide in MIL‐53(Al), a prototypical flexible MOF, substantially decreases the inaccuracy of the obtained adsorption isotherms and predicted guest‐induced flexibility. As a result, this method is ideally suited to rationalize the adsorption performance of flexible nanoporous materials at the molecular level, paving the way for the conscious design of MOFs as industrial adsorbents.
Programmable Collective Behavior in Dynamically Self‐Assembled Mobile Microrobotic Swarms
Authors: Yigit Berk , Alapan Yunus , Sitti Metin
Published: January 2019

Collective control of mobile microrobotic swarms is indispensable for their potential high‐impact applications in targeted drug delivery, medical diagnostics, parallel micromanipulation, and environmental sensing and remediation. Without integrated electronics for sensing and actuation, current microrobotic systems should rely on physical interactions among individual microrobots for local communication and cooperation. Here, it is shown that mobile microrobotic swarms with well‐defined collective behavior can be designed by engineering magnetic interactions among individual units. Microrobots, dynamically self‐assembled from magnetic microparticles into linear chains, locomote on surfaces in response to a precessing magnetic field. Control over precessing magnetic field allows engineering attractive and repulsive interactions among microrobots and, thus, collective order with well‐defined spatial organization and stable parallel operation over macroscale distances (≈1 cm) and through confining obstacles. The design approach described here addresses programmable assembly, propulsion, and collective behavior of dense mobile microrobot swarms simultaneously by engineering magnetic interactions and dynamic actuation of microrobots. The presented approach will advance swarm microrobotics by enabling facile and rapid formation of self‐organized and reconfigurable microrobotic swarms with programmable collective order and stability.
Mortality among United States aerospace materials manufacturing workers
Authors: Marsh Gary M. , Buchanich Jeanine M. , Graves Jessica , Zimmerman Sarah , Liu Yimeng
Published: January 2019

Objectives

To evaluate long‐term mortality rates among aerospace material manufacturing workers as follow‐up to an earlier observed excess of nephritis/nephrosis.

Methods

Subjects were 2020 workers ever employed in the facility during 1963‐2014. Vital status through 2014 was determined for all subjects and cause of death for 99.2% of 492 deaths. We computed standard mortality ratios (SMR) and internal relative risks.

Results

SMRs for nephritis/nephrosis were unremarkable. We observed statistically significant elevated SMRs for kidney cancer among all workers and for the category “other lymphatic hematopoietic tissue cancer” (4/5 deaths from multiple myeloma) among long‐term workers with potential plant exposure.

Conclusions

We found no evidence of elevated mortality rates for nephritis/nephrosis. Study limitations precluded robust evaluation of whether the elevated rates for kidney cancer and other lymphatic hematopoietic tissue cancer were related to occupational factors at the study site. Our findings for these two cancers warrant continued mortality follow‐up.
Congenital central hypoventilation syndrome: Severe disease caused by co‐occurrence of two PHOX2B variants inherited separately from asymptomatic family members
Authors: Sivan Yakov , Zhou Amy , Jennings Lawrence J. , Berry‐Kravis Elizabeth M. , Yu Min , Zhou Lili , Rand Casey M. , Weese‐Mayer Debra E.
Published: January 2019

Congenital Central Hypoventilation Syndrome (CCHS) is a rare disease characterized by autonomic nervous system dysregulation. Central hypoventilation is the most prominent and clinically important presentation. CCHS is caused by mutations in paired‐like homeobox 2b (PHOX2B) and is inherited in an autosomal dominant pattern. A co‐occurrence of two asymptomatic PHOX2B variants with a classical CCHS presentation highlights the importance of clinical PHOX2B testing in parents and family members of all CCHS probands. Despite being an autosomal dominant disease, once a polyalanine repeat expansion mutation has been identified, sequencing of the other allele should also be considered.
Development of the clinical assessment scale in autoimmune encephalitis
Authors: Lim Jung‐Ah , Lee Soon‐Tae , Moon Jangsup , Jun Jin‐Sun , Kim Tae‐Joon , Shin Yong‐Won , Abdullah Suhailah , Byun Jung‐Ick , Sunwoo Jun‐Sang , Kim Keun Tae , Yang Tae‐Won , Lee Woo‐Jin , Moon Hye‐Jin , Kim Dong Wook , Lim Byung Chan , Cho Yong Won , Yang Tae‐Ho , Kim Hee Jin , Kim Young‐Soo , Koo Yong Seo , Park Byeongsu , Jung Keun‐Hwa , Kim Manho , Park Kyung‐Il , Jung Ki‐Young , Chu Kon , Lee Sang Kun
Published: January 2019

Objective

There is no scale for rating the severity of autoimmune encephalitis (AE). In this study, we aimed to develop a novel scale for rating severity in patients with diverse AE syndromes and to verify the reliability and validity of the developed scale.

Methods

The key items were generated by a panel of experts and selected according to content validity ratios. The developed scale was initially applied to 50 patients with AE (development cohort) to evaluate its acceptability, reproducibility, internal consistency, and construct validity. Then, the scale was applied to another independent cohort (validation cohort, n = 38).

Results

A new scale consisting of 9 items (seizure, memory dysfunction, psychiatric symptoms, consciousness, language problems, dyskinesia/dystonia, gait instability and ataxia, brainstem dysfunction, and weakness) was developed. Each item was assigned a value of up to 3 points. The total score could therefore range from 0 to 27. We named the scale the Clinical Assessment Scale in Autoimmune Encephalitis (CASE). The new scale showed excellent interobserver (intraclass correlation coefficient [ICC] = 0.97) and intraobserver (ICC = 0.96) reliability for total scores, was highly correlated with modified Rankin scale (r = 0.86, p < 0.001), and had acceptable internal consistency (Cronbach α = 0.88). Additionally, in the validation cohort, the scale showed high interobserver reliability (ICC = 0.99) and internal consistency (Cronbach α = 0.92).

Interpretation

CASE is a novel clinical scale for AE with a high level of clinimetric properties. It would be suitable for application in clinical practice and might help overcome the limitations of current outcome scales for AE. ANN NEUROL 2019;85:352–358.
Quantitative Mapping of Endosomal DNA Processing by Single Molecule Counting
Authors: Prakash Ved , Tsekouras Konstantinos , Venkatachalapathy Muthukumaran , Heinicke Laurie , Pressé Steve , Walter Nils G. , Krishnan Yamuna
Published: January 2019

Extracellular DNA is engulfed by innate immune cells and digested by endosomal DNase II to generate an immune response. Quantitative information on endosomal stage‐specific cargo processing is a critical parameter to predict and model the innate immune response. Biochemical assays quantify endosomal processing but lack organelle‐specific information, while fluorescence microscopy has provided the latter without the former. Herein, we report a single molecule counting method based on fluorescence imaging that quantitatively maps endosomal processing of cargo DNA in innate immune cells with organelle‐specific resolution. Our studies reveal that endosomal DNA degradation occurs mainly in lysosomes and is negligible in late endosomes. This method can be used to study cargo processing in diverse endocytic pathways and measure stage‐specific activity of processing factors in endosomes.
An N‐Heterocyclic Boryloxy Ligand Isoelectronic with N‐Heterocyclic Imines: Access to an Acyclic Dioxysilylene and its Heavier Congeners
Authors: Loh Ying Kai , Ying Lu , Ángeles Fuentes M. , Do Dinh Cao Huan , Aldridge Simon
Published: January 2019

Introduced here is a new type of strongly donating N‐heterocyclic boryloxy (NHBO) ligand, [(HCDippN)2BO]− (Dipp=2,6‐diisopropylphenyl), which is isoelectronic with the well‐known N‐heterocyclic iminato (NHI) donor class. This 1,3,2‐diazaborole functionalized oxy ligand has been used to stabilize the first acyclic two‐coordinate dioxysilylene and its Ge, Sn, and Pb congeners, thereby presenting the first complete series of heavier group 14 dioxycarbene analogues. All four compounds have been characterized by X‐ray crystallography and density‐functional theory, enabling analysis of periodic trends: the potential for the [(HCDippN)2BO]− ligand to subtly vary its electronic‐donor capabilities is revealed by snapshots showing the gradual evolution of arene π coordination on going from Si to Pb.
2,2′‐Diamino‐6,6′‐diboryl‐1,1′‐binaphthyl: A Versatile Building Block for Temperature‐Dependent Dual Fluorescence and Switchable Circularly Polarized Luminescence
Authors: Sun Zuo‐Bang , Liu Jun‐Kai , Yuan Da‐Fei , Zhao Zheng‐Hua , Zhu Xiao‐Zhang , Liu Di‐Hong , Peng Qian , Zhao Cui‐Hua
Published: January 2019

Temperature‐dependent dual fluorescence and switchable circularly polarized luminescence (CPL) are two highly pursued but challenging properties for small organic molecules (SOMs). We herein disclose a triarylborane π‐system based on a 2,2′‐diamino‐6,6′‐diboryl‐1,1′‐binaphthyl scaffold that can serve as a versatile building block for achieving these two properties by simply choosing different amino groups. BNMe2‐BNaph with less bulky dimethylamino groups displays temperature‐dependent dual fluorescence, and can thus be used as a highly sensitive ratiometric fluorescence thermometer. On the other hand, BNPh2‐BNaph with bulky diphenylamino groups exhibits intense fluorescence in both solution and in the solid state. A change of solvent from nonpolar cyclohexane to highly polar MeCN not only shifts the CPL position to much longer wavelength but also inverts the CPL sign. In addition, the complexation of BNPh2‐BNaph with fluoride greatly enhances the CPL intensity.
Selective Ion Exchange in Supramolecular Channels in the Crystalline State
Authors: Ichihashi Katsuya , Konno Daisuke , Maryunina Kseniya Yu. , Inoue Katsuya , Toyoda Kazuhiro , Kawaguchi Shogo , Kubota Yoshiki , Tatewaki Yoko , Akutagawa Tomoyuki , Nakamura Takayoshi , Nishihara Sadafumi
Published: January 2019

Artificial ion channels are of increasing interest because of potential applications in biomimetics, for example, for realizing selective ion permeability through the transport and/or exchange of selected ions. However, selective ion transport and/or exchange in the crystalline state is rare, and to the best of our knowledge, such a process has not been successfully combined with changes in the physical properties of a material. Herein, by soaking single crystals of Li2([18]crown‐6)3[Ni(dmit)2]2(H2O)4 (1) in an aqueous solution containing K+, we succeeded in complete ion exchange of the Li+ ions in 1 with K+ ions in the solution, while maintaining the crystalline state of the material. This ion exchange with K+ was selectively conducted even in mixed solutions containing K+ as well as Na+/Li+. Furthermore, remarkable changes in the physical properties of 1 resulted from the ion exchange. Our finding enables not only the realization of selective ion permeability but also the development of highly sensitive biosensors and futuristic ion exchange agents, for example.
Super‐Bulky Penta‐arylcyclopentadienyl Ligands: Isolation of the Full Range of Half‐Sandwich Heavy Alkaline‐Earth Metal Hydrides
Authors: Shi Xianghui , Qin Guorui , Wang Yang , Zhao Lanxiao , Liu Zhizhou , Cheng Jianhua
Published: January 2019

Hydrogenolysis of the half‐sandwich penta‐arylcyclopentadienyl‐supported heavy alkaline‐earth‐metal alkyl complexes (CpAr)Ae[CH(SiMe3)2](S) (CpAr=C5Ar5, Ar=3,5‐iPr2‐C6H3; S=THF or DABCO) in hexane afforded the calcium, strontium, and barium metal–hydride complexes as the same dimers [(CpAr)Ae(μ‐H)(S)]2 (Ae=Ca, S=THF, 2‐Ca; Ae=Sr, Ba, S=DABCO, 4‐Ae), which were characterized by NMR spectroscopy and single‐crystal X‐ray analysis. 2‐Ca, 4‐Sr, and 4‐Ba catalyzed alkene hydrogenation under mild conditions (30 °C, 6 atm, 5 mol % cat.), with the activity increasing with the metal size. A variety of activated alkenes including tri‐ and tetra‐substituted olefins, semi‐activated alkene (Me3SiCH=CH2), and unactivated terminal alkene (1‐hexene) were evaluated.
Copper‐Catalyzed C(sp3)−H Amidation: Sterically Driven Primary and Secondary C−H Site‐Selectivity
Authors: Bakhoda Abolghasem (Gus) , Jiang Quan , Badiei Yosra M. , Bertke Jeffery A. , Cundari Thomas R. , Warren Timothy H.
Published: January 2019

Undirected C(sp3)−H functionalization reactions often follow site‐selectivity patterns that mirror the corresponding C−H bond dissociation energies (BDEs). This often results in the functionalization of weaker tertiary C−H bonds in the presence of stronger secondary and primary bonds. An important, contemporary challenge is the development of catalyst systems capable of selectively functionalizing stronger primary and secondary C−H bonds over tertiary and benzylic C−H sites. Herein, we report a Cu catalyst that exhibits a high degree of primary and secondary over tertiary C−H bond selectivity in the amidation of linear and cyclic hydrocarbons with aroyl azides ArC(O)N3. Mechanistic and DFT studies indicate that C−H amidation involves H‐atom abstraction from R‐H substrates by nitrene intermediates [Cu](κ2‐N,O‐NC(O)Ar) to provide carbon‐based radicals R. and copper(II)amide intermediates [CuII]‐NHC(O)Ar that subsequently capture radicals R. to form products R‐NHC(O)Ar. These studies reveal important catalyst features required to achieve primary and secondary C−H amidation selectivity in the absence of directing groups.
NMR Crystallography: Evaluation of Hydrogen Positions in Hydromagnesite by 13C{1H} REDOR Solid‐State NMR and Density Functional Theory Calculation of Chemical Shielding Tensors
Authors: Cui Jinlei , Olmsted David L. , Mehta Anil K. , Asta Mark , Hayes Sophia E.
Published: January 2019

Solid‐state NMR measurements coupled with density functional theory (DFT) calculations demonstrate how hydrogen positions can be refined in a crystalline system. The precision afforded by rotational‐echo double‐resonance (REDOR) NMR to interrogate 13C–1H distances is exploited along with DFT determinations of the 13C tensor of carbonates (CO32−). Nearby 1H nuclei perturb the axial symmetry of the carbonate sites in the hydrated carbonate mineral, hydromagnesite [4 MgCO3⋅Mg(OH)2⋅4 H2O]. A match between the calculated structure and solid‐state NMR was found by testing multiple semi‐local and dispersion‐corrected DFT functionals and applying them to optimize atom positions, starting from X‐ray diffraction (XRD)‐determined atomic coordinates. This was validated by comparing calculated to experimental 13C{1H} REDOR and 13C chemical shift anisotropy (CSA) tensor values. The results show that the combination of solid‐state NMR, XRD, and DFT can improve structure refinement for hydrated materials.
A Dissolution/Precipitation Equilibrium on the Surface of Iridium‐Based Perovskites Controls Their Activity as Oxygen Evolution Reaction Catalysts in Acidic Media
Authors: Zhang Ronghuan , Dubouis Nicolas , Ben Osman Manel , Yin Wei , Sougrati Moulay T. , Corte Daniel A. D. , Giaume Domitille , Grimaud Alexis
Published: January 2019

Recently, IrV‐based perovskite‐like materials were proposed as oxygen evolution reaction (OER) catalysts in acidic media with promising performance. However, iridium dissolution and surface reconstruction were observed, questioning the real active sites on the surface of these catalysts. In this work, Sr2MIr(V)O6(M=Fe, Co) and Sr2Fe0.5Ir0.5(V)O4were explored as OER catalysts in acidic media. Their activities were observed to be roughly equal to those previously reported for La2LiIrO6or Ba2PrIrO6. Coupling electrochemical measurements with iridium dissolution studies under chemical or electrochemical conditions, we show that the deposition of an IrOxlayer on the surface of these perovskites is responsible for their OER activity. Furthermore, we experimentally reconstruct the iridium Pourbaix diagram, which will help guide future research in controlling the dissolution/precipitation equilibrium of iridium species for the design of better Ir‐based OER catalysts.
Spatially Controlled Occlusion of Polymer‐Stabilized Gold Nanoparticles within ZnO
Authors: Ning Yin , Fielding Lee A. , Nutter John , Kulak Alexander N. , Meldrum Fiona C. , Armes Steven P.
Published: January 2019

In principle, incorporating nanoparticles into growing crystals offers an attractive and highly convenient route for the production of a wide range of novel nanocomposites. Herein we describe an efficient aqueous route that enables the spatially controlled occlusion of gold nanoparticles (AuNPs) within ZnO crystals at up to 20 % by mass. Depending on the precise synthesis protocol, these AuNPs can be (i) solely located within a central region, (ii) uniformly distributed throughout the ZnO host crystal or (iii) confined to a surface layer. Remarkably, such efficient occlusion is mediated by a non‐ionic water‐soluble polymer, poly(glycerol monomethacrylate)70(G70), which is chemically grafted to the AuNPs; pendentcis‐diol side groups on this steric stabilizer bind Zn2+cations, which promotes nanoparticle interaction with the growing ZnO crystals. Finally, uniform occlusion of G70‐AuNPs within this inorganic host leads to faster UV‐induced photodegradation of a model dye.
Chiral Heterobimetallic Bismuth–Rhodium Paddlewheel Catalysts: A Conceptually New Approach to Asymmetric Cyclopropanation
Authors: Collins Lee R. , Auris Sebastian , Goddard Richard , Fürstner Alois
Published: January 2019

Cyclopropanation reactions of styrene derivatives with donor–acceptor carbenes formed in situ are significantly more enantioselective when catalyzed by the heterobimetallic bismuth–rhodium complex 5 a endowed with N‐phthalimido tert‐leucine paddlewheel ligands rather than by its homobimetallic dirhodium analogue 1 a. This virtue is likely the result of two synergizing factors: the conical shape of 5 a translates into a narrower calyx‐like chiral binding site about the catalytically active Rh center; the Bi atom, although fully solvent exposed, does not decompose aryl diazoacetates and is hence incapable of promoting a racemic background reaction. Moreover, ligand variation proved that successful catalyst design mandates that the anisotropy of the conical heterobimetallic core be matched by proper directionality of the ligand sphere.
Structure Switching and Modulation of the Magnetic Properties in Diarylethene‐Bridged Metallosupramolecular Compounds by Controlled Coordination‐Driven Self‐Assembly
Authors: Li Zhao‐Yang , Dai Jing‐Wei , Damjanović Marko , Shiga Takuya , Wang Jin‐Hua , Zhao Jia , Oshio Hiroki , Yamashita Masahiro , Bu Xian‐He
Published: January 2019

We report three self‐assembled iron complexes that comprised an anti‐parallel open form (o‐Lanti), a parallel open form (o‐Lsyn), and a closed form (c‐L) of diarylethene conformers. Under kinetic control, FeII2(o‐Lanti)3 was isolated, which exhibited a dinuclear structure with diamagnetic properties. Under light‐irradiation control, FeII2(c‐L)3 was prepared and exhibited paramagnetism and spin‐crossover behaviour. Under thermodynamic control and in the presence of indispensable [FeIII(Tp*)(CN)3]−, FeII2(o‐Lanti)3 and FeII2(c‐L)3 transformed into tetranuclear FeIII2FeII2(o‐Lsyn)2, which exhibited complete spin‐crossover behaviour at T1/2=353 K.
Matrix–particle interactions in catalyzed and uncatalyzed copper‐filled epoxy matrix composites
Authors: Tognana Sebastián , Salgueiro Walter , Valcarce Beatriz , Schreiner Wido , Montecinos Susana
Published: January 2019

Epoxy composites filled with copper particles with sizes of the order of 100 μm are studied with the aim of analyzing the particle–matrix interphase. Two matrixes are used: diglycidyl ether of bisphenol A resin (DGEBA)–anhydride catalyzed using a tertiary amine, and uncatalyzed DGEBA–anhydride. The surface of both types of composites was analyzed using scanning electron microscopy, X‐ray photoelectron spectroscopy, and instrumented nanoindentation. The formation of Cu(I) and Cu(II) complexes is revealed using X‐ray photoelectron spectroscopy, while instrumented nanoindentation measurements allow us to determine regions with different mechanical properties in the uncatalyzed composite. The influence of anhydride and the type of curing reaction on the formation of copper complexes is analyzed. The main results point out that copper particles can interact strongly with the epoxy, depending on the chemistry and kinetics of the curing reaction, to modify the composite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47511.
Documentation and access to knowledge in online communities: Know your audience and write appropriately?
Authors: Østerlund Carsten , Crowston Kevin
Published: January 2019

Virtual collaborations bring together people who must work together despite having varied access to and understanding of the work at hand. In many cases, the collaborations are technology supported, meaning that the work is done through shared documents. We develop a framework articulating the characteristics of documents supporting collaborators with access to asymmetric knowledge versus those with access to symmetric knowledge. Drawing on theories about document genre, boundary objects, and provenance, we hypothesize that documents supporting asymmetric collaborators are likely to articulate or prescribe their own (a) purpose, (b) context of use, (c) content and form, and (d) provenance in greater detail than documents supporting symmetric collaborators. We explore these hypotheses through content analysis of documents and instructions for documents from a variety of free/libre open‐source projects (FLOSS). We present findings consistent with the hypotheses developed as well as results extending beyond our theory‐derived assumptions. When participants have access to the same knowledge, the study suggests that prescriptions about the content of documents become less important compared with prescriptions about the context, provenance, and process of work. The study contributes with a dynamic perspective on communicative practices that consider an often‐uneven distribution of knowledge in virtual collaborations.
Ionothermal Synthesis of Germanosilicate Zeolites Constructed with Double‐Four‐Ring Structure‐Building Units in the Presence of Organic Base
Authors: Wang Miao , Zhang Ling , Guo Ke , Lin Yutong , Meng Xiangzhi , Huang Pengfei , Wei Ying , Zhang Runduo
Published: January 2019

The crystallization chemistry of silica‐based zeolites in ionic liquids remains highly puzzling and interesting in the field of zeolite science. Herein, we report the successful ionothermal synthesis of germanosilicate zeolites. The ionothermal templating effect with respect to the structure, alkalinity and concentration of organic additives was comparatively studied. The results showed that a small amount of organic base could effectively aid the dissolution of silica source and facilitate the crystallization of germanosilicate zeolites with ionic liquid as template. Remarkably, STW and IRR structures constructed with double‐four‐ring (D4R) structure‐building units were ionothermally prepared using 1‐ethyl/butyl‐3‐methyl imidazolium and 1‐benzyl‐3‐methyl imidazolium ionic liquids as template, respectively. Ionothermal synthesis tailored with organic base showed suitable chemistry for the formation of germanium‐containing siliceous D4R units. This finding will be helpful for the rational exploration of novel extra‐large‐pore zeolitic structures.
An Advanced NiCoFeO/Polyaniline Composite for High‐Performance Supercapacitors
Authors: Hu Xi , Liu Lu , Zeng Hong‐Yan , Xu Sheng , Cao Xi , Cao Xiao‐Ju
Published: January 2019

To reduce the charge‐transfer resistance of supercapacitors and achieve faster reversible redox reactions, ternary Ni‐Co‐Fe layered double hydroxide was prepared by using the urea method and then calcined to give NiCoFe oxide (NiCoFeO). To enhance conductivity, a polyaniline (PANI) conductive layer was assembled on the surface of the NiCoFeO particles by in situ oxidative polymerization of aniline monomers. The as‐prepared NiCoFeO/PANI composite was successful employed as a supercapacitor electrode. It was found that the NiCoFeO/PANI composite displayed good cycling stability, with a capacity loss of only 29.54 % after 5000 cycles. Furthermore, the NiCoFeO/PANI composite also exhibited excellent supercapacitor performance, with a high specific capacity of 843 F g−1 at a current density of 2 A g−1, whereas NiCoFeO showed a specific capacity of only 478 F g−1. This result was attributed to the synergistic effect between NiCoFeO and PANI. The facile synthesis strategy and excellent electrochemical performance suggest that NiCoFeO/PANI is a promising economical electrode material for applications in supercapacitors.
Biomass‐Derived Carbon Materials as Prospective Electrodes for High‐Energy Lithium‐ and Sodium‐Ion Capacitors
Authors: Natarajan Subramanian , Lee Yun‐Sung , Aravindan Vanchiappan
Published: January 2019

Biomass‐derived carbon materials have received special attention as efficient, low‐cost, active materials for charge‐storage devices, regardless of the power system, such as supercapacitors and rechargeable batteries. In this Minireview, we discuss the influence of biomass‐derived carbonaceous materials as positive or negative electrodes (or both) in high‐energy hybrid lithium‐ion configurations with an organic electrolyte. In such hybrid configurations, the electrochemical activity is completely different to conventional electrical double‐layer capacitors; that is, one of the electrodes undergoes a Faradaic reaction, whilst the counter electrode undergoes a non‐Faradaic reaction, to achieve high energy density. The use of a variety of biomass precursors with different properties, such as surface functionality, the presence of inherent heteroatoms, tailored meso‐/microporosity, high specific surface area, various degrees of crystallization, calcination temperature, and atmosphere, are described in detail. Sodium‐ion capacitors are also discussed, because they are an important alternative to lithium‐ion capacitors, owing to the low abundance and high cost of lithium. The electrochemical performance of carbonaceous electrodes in supercapacitors and rechargeable batteries are not discussed.
Robust PID controller for flexible satellite attitude control under angular velocity and control torque constraint
Authors: Li You , Ye Dong
Published: January 2019

A PID controller for flexible satellite attitude control with unknown perturbation is proposed in this paper. System inertia uncertainty, stochastic disturbance torque, and perturbation of flexible deformation are discussed, and the controller proposed in this paper is robust to these perturbations. A novel integral term is designed; hence the Lyapunov function structure is modified and the stability proof is simplified. The angular velocity constraint is discussed and a novel method to solve the angular velocity saturation issue is given. The control torque saturation issue is also taken into consideration. Stability for all conditions considered in this paper is proved by the Lyapunov method. The performance of the controller is demonstrated by numerical simulation.
Profiles of vocalization change in children with autism receiving early intervention
Authors: Trembath David , Westerveld Marleen F. , Teppala Srinivas , Thirumanickam Abirami , Sulek Rhylee , Rose Veronica , Tucker Madonna , Paynter Jessica , Hetzroni Orit , Keen Deb , Vivanti Giacomo
Published: January 2019

Children with autism spectrum disorder (ASD) commonly present with comorbid language impairment, negatively impacting their learning and participation across settings. Addressing these needs requires a detailed understanding of their communication trajectories. In this study, we used the language environment and analysis (LENA) system to examine possible changes in children's (a) vocalizations and (b) ratio of speech to nonspeech vocalizations over a 10‐month period. Data for 23 children with ASD (17M, 6F; ages 32–67 months) were analyzed, including monthly 3‐hr in‐class recordings and standardized measures of language, cognition, and ASD characteristics. Using hierarchical generalized linear models, we found significant time‐trends for child vocalizations (P ≤ 0.001) and the vocalization ratio (P = 0.02), reflecting a waxing and waning pattern. Children with higher expressive language scores (Mullen scales of early learning, Vineland adaptive behavior scales – 2nd Ed.) and nonverbal cognition (Mullen scales of early learning), and fewer ASD characteristics (social communication questionnaire) demonstrated greater increases in the vocalization ratio over time (P values 0.04–0.01). Children with greater language and cognition difficulties were the most vocal, but produced a higher proportion of nonspeech vocalizations. The results demonstrate that significant fluctuations, as opposed to linear increases, may be observed in children with ASD receiving intervention, highlighting the value of assessment at multiple time‐points. In addition, the findings highlight the need to consider both the quantity (vocalization counts) and quality (ratio of speech to nonspeech vocalizations) when interpreting LENA data, with the latter appearing to provide a more robust measure of communication. Autism Research 2019, 12: 830–842. © 2019 International Society for Autism Research, Wiley Periodicals, Inc.

Lay Abstract

In this study, we examined possible changes in speech and nonspeech vocalizations in 23 children with autism attending a comprehensive early intervention program over a 10‐month period. Contrary to our expectation, we observed a waxing and waning pattern of change in children's vocalizations over time, rather than a steady increase. We also found evidence to suggest that looking at the quality of children's vocalizations (i.e., the ratio of speech to nonspeech vocalizations) provides a more accurate picture of children's development than simply looking at the quantity (i.e., how frequently they vocalize).
Zur Gestaltung von Fertigteilbrücken
Authors: Gabler Markus , Fakhouri Abdalla , Baumann Katrin
Published: January 2019

Fertigteilbrücken können in bis zu 75 % kürzerer Bauzeit gegenüber herkömmlicher Bauweise errichtet werden, was sie besonders für den Ersatz baufälliger Überführungsbauwerke attraktiv macht. Denn dadurch kann die Sperrung der überführten Straße auf ein Minimum reduziert werden. In Deutschland spielt die Fertigteilweise bislang jedoch eine untergeordnete Rolle. Allenfalls kommen nur Halbfertigteile zur Anwendung. Es empfiehlt sich daher, den Blick zunächst auf die Praxis in anderen Ländern zu richten. In diesem Artikel werden Erfahrungen aus den Niederlanden, Irland und den USA kurz analysiert, welche auch in deutschen Projekten einfließen könnten.

Ein wichtiger Punkt bei der Entwicklung neuer Systeme für Fertigteilbrücken ist die Feststellung, dass die Gestaltung häufig unter der Prämisse leidet, auf wenige einheitliche Bauteile zurückgreifen zu müssen. Dabei kommt meist ein streng rechtwinkliger Grundriss und ein orthogonaler Kreuzungswinkel der Unterbauten zur Anwendung, was solche Bauwerke häufig besonders groß und plump werden lässt.

Arup hat zusammen mit Straßen.NRW auf Grundlage dieser Erkenntnisse eine neue Fertigteilbauweise entwickelt, welche im Jahr 2018 anhand von zwei Pilotprojekten erstmals umgesetzt wurde. Neben der Sicherstellung einer kurzen Bauzeit lag dabei ein wesentlicher Fokus auf der Gestaltung der Brücken. Die entwickelte Bauweise und die beiden Überführungsbauwerke bei Werne werden in diesem Beitrag eingehend beschrieben. Zuletzt wird die Frage diskutiert, wie die Fertigteilindustrie in Deutschland reagieren könnte, um diese neue Bauweise hierzulande auch salonfähig zu machen.
Suicide risk in adolescents with fetal alcohol spectrum disorders
Authors: O'Connor Mary J. , Portnoff Larissa C. , Lebsack‐Coleman Michael , Dipple Katrina M.
Published: January 2019

Background

The teratogenic effects of prenatal alcohol exposure (PAE) have been extensively documented over the course of 45 years of research and psychiatric problems are pervasive in this population. In adults with PAE, suicidal risk is high but less is known about the suicidal risk in adolescents with fetal alcohol spectrum disorders (FASD). This study describes the prevalence of suicidal ideation and serious suicide attempts in a sample of 54 adolescents between the ages of 13 and 18 years with FASD.

Methods

Adolescents were diagnosed with FASD using the Updated Clinical Guidelines for Diagnosing Fetal Alcohol Spectrum Disorders. The Children's Interview for Psychiatric Syndromes was used to identify those adolescents who experienced suicidal ideation and/or who had made a serious suicide attempt in the last 12 months.

Results

The prevalence of suicidal behaviors in this sample was high with 35.2% of teens reporting incidences of suicidal ideation and 13.0% reporting at least one serious suicide attempt in the past year. This finding is in contrast to the 17.2% and 2.4% for ideation and serious attempts, respectively, reported in the general U.S. adolescent population. Alarmingly, 29.2% of males with FASD reported a serious suicide attempt which was 19½ times higher than national norms for males. No females reported attempts. Number of home placements and the presence of a depressive disorder contributed to study outcomes.

Conclusions

Findings demonstrate the significant risk for suicidality in this population, particularly adolescent males, and the need to assess and treat this life threatening behavior.
Mutational signatures and the genomic landscape of betel quid chewing‐associated tongue carcinoma
Authors: Zhang Weilong , Wang Mu , Wu Qifeng , Zhu Qing , Jiao Yuchen , Zhu Yiming , Yang Beibei , Ni Song , Yu Jianjun , Sun Hong , Zeng Yi‐Xin
Published: January 2019

Our study presents the genetic landscape betel quid chewing‐associated tongue carcinomas (BQ‐TCs). We compared the genetic landscape and mutational signatures of 15 BQ‐TCs, five nonbetel quid chewing‐associated tongue carcinomas (nBQ‐TCs), and 82 tongue carcinomas in general population from the TCGA (TCGA‐TCs) project. The highlights of this research mainly include: (a) The genetic landscape of BQ‐TC was characterized with frequent mutations in RASA1 gene and in CpG islands throughout the genome. (b) The BQ‐TC had a distinct mutational signature from that of nBQ‐TC and tongue carcinomas in the general population, and this signature was associated with the mutations in RASA1 and in CpG islands. (c) Our study indicates that betel quid (BQ) chewing classifies a distinct group of tongue carcinoma. The BQ chewing might not contribute to the tumorigenesis of tongue carcinomas as a mutagen.
Brexit and emergent politics: In search of a social psychology
Authors: Andreouli Eleni , Kaposi David , Stenner Paul
Published: January 2019

In this paper, we develop a conceptual and methodological approach that psychologists and other social scientists can employ to study emergence. We consider relevant social psychological approaches and conclude that, for the most part, social psychology has tended to focus on processes of normalisation following disruptions, rather than examining emergence in itself. An exception to this is G. H. Mead, whose work we draw on to theorise emergence with a focus on contemporary “affective politics.” In the second part of the paper, we use focus group data on the European Union referendum in the UK to empirically illustrate our theoretical points. We discuss in particular three axes for exploring the emergent politics of Brexit: political values, political authority, and the authority of affect. We conclude our discussion by reflecting on some of the theoretical and political implications of our analysis.
Chemical Characterization, Antioxidant Capacity and Antimicrobial Potential of Essential Oil from the Leaves of Baccharis oreophilaMalme
Authors: Terezinha de Oliveira Cledes , Lameiro de Noronha Sales Maia Beatriz Helena , Portes Ferriani Aurea , Aparecida Queiroz Santos Vidiany , Antônio Alves da Cunha Mário , Dias Teixeira Sirlei
Published: January 2019

This is the first time that composition, antimicrobial potential and antioxidant ability of essential oil from the leaves of Baccharis oreophila are reported. Essential oil was obtained by hydrodistillation and analyzed by GC/MS. Antimicrobial potential was evaluated by diffusion disk and broth microdilution methods. ABTS.+, DPPH. and FRAP methods were employed for antioxidant activity evaluation. Essential oil yield was 0.47 %. Sixty‐five compounds were identified, representing 88.53 % of the total essential oil, which showed to be rich in oxygenated (37.88 %) and hydrocarbons sesquiterpenes (34.84 %). The main constituents were khusimone (16.37 %) and spathulenol (16.12 %). Antimicrobial activity was verified against S. aureus (10.33±0.5 mm, MIC: 1250 μg mL−1) and C. albicans (8.66±0.5 mm, MIC: >2500 μg mL.1). Antioxidant ability was evidenced by FRAP (4.09 μmol FeSO4 E mL−1), ABTS.+ (1.45 μmol TE mL−1) and DPPH. (1.04 μmol TE mL−1) scavenging capacity. Results showed that this essential oil has interesting biological potential, encouraging further investigations especially in relation to action mechanisms of antimicrobial and antioxidant activity.
Reversible hand tremors, downbeat nystagmus, and an unsteady gait with nontoxic lithium level
Authors: Peng Yen‐Yi
Published: January 2019

Key Clinical Message

Patients with nontoxic lithium levels can still develop hand tremors, downbeat nystagmus, and an unsteady gait.
P450 Monooxygenases Enable Rapid Late‐Stage Diversification of Natural Products via C−H Bond Activation
Authors: Fessner Nico D.
Published: January 2019

The biological potency of natural products has been exploited for decades. Their inherent structural complexity and natural diversity might hold the key to efficiently address the urgent need for the development of novel pharmaceuticals. At the same time, it is that very complexity, which impedes necessary chemical modifications such as structural diversification, to improve the effectiveness of the drug. For this purpose, Cytochrome P450 enzymes, which possess unique abilities to activate inert sp3‐hybridised C−H bonds in a late‐stage fashion, offer an attractive synthetic tool. In this review the potential of cytochrome P450 enzymes in chemoenzymatic lead diversification is illustrated discussing studies reporting late‐stage functionalisations of natural products and other high‐value compounds. These enzymes were proven to extend the synthetic toolbox significantly by adding to the flexibility and efficacy of synthetic strategies of natural product chemists, and scientists of other related disciplines.