bluuebunny/crossref_metadata_2025 huggingface dataset:
Using Game as an Educational Phenomenon in Foreign Language Education of Adults (Practical Instructions)
Authors: Birova Ilka
Published: March 2019

This review paper is dedicated to the learning game as an educational phenomenon in foreign language education of adults. Gamification becomes one of the main trends in language education not only of children but of adults as well. Game is a central subject of the author’s recent research works, including a monograph about game in foreign language education on the base of Russian language. In the article a general definition of game in language education is given. A conception regarding practical foreign language education with active use of game activities is generally presented. Using game in teaching process is active if it takes an average of 30% learning time. The author gives an explanation about relevance of this proportion. Useful practical instructions for using different game activities at elementary, intermediate and advanced levels of foreign language teaching to adults are presented. Game in the foreign language learning process is a real challenge to the intellect and emotions of adult students. Game activities stimulate not only speaking or writing skills but cognitive, creative, social and intercultural skills as well. The game is a valuable educational phenomenon which has to be actively used in foreign language education of adult students.
Chromatin plates in the interphase nucleus
Authors: Chicano Andrea , Daban Joan‐Ramon
Published: March 2019

Early results showed the emanation of chromatin fibers from mitotic chromosomes and nuclei swollen with water. In contrast, under metaphase ionic conditions, it was found that chromatin from mitotic chromosomes is planar and forms multilayered plates. Here, we show that in buffers containing interphase cation concentrations, the chromatin emanated from disrupted nuclei also has a planar morphology. Furthermore, the chromatin fragments produced by micrococcal nuclease digestion of nuclei form the typical beads‐on‐a‐string fibers in the absence of cations, but they self‐assemble into plate‐like structures in buffers containing magnesium. The plates from interphase nuclei do not form the thick multilayered structures observed in metaphase chromosomes, suggesting that they are more exposed to the medium to facilitate DNA replication and gene expression.
Industrial Wastes and Waste Dumps, Sampling and Analysis
Authors: Rasemann Winfried , Herbst Martin , Seltmann Udo , Kreutzmann Heinrich
Published: March 2019

‘Waste’ is everything that the owner intends to remove, or has to be removed, or has been already removed. This is merely a juridical concept. It is only through a concrete reference that waste becomes a concrete object with a real meaning. The wastes can contain hazardous components that pollute and endanger the environment, but they can also consist of valuable materials, which are a source of secondary raw materials. To assess the environmental risk or to calculate the economic benefit of disposed or dumped material, a reliable knowledge of the waste composition is required. As experience has regularly shown, conflicts and lawsuits result when the waste composition cannot be reliably determined. The problems are created because the wastes are mixtures of particles, pieces, and lumps that vary in size and shape as well as in chemical composition and physical properties. The basis for the evaluation of a waste material are measurement results obtained from samples. The measured values generally differ from the true composition of the waste. These differences, called the measurement deviations, are random and unavoidable. To ensure that the results of investigation and evaluation are comparable, certain regulations must be followed.

The present article takes up this problem on the example of different applications of waste management. The examples confirm that sampling is one of the most important measures for the characterization of waste materials.
Comparative Responsiveness of Outcome Measures for the Assessment of Pain and Function in Osteoarthritis of the First Metatarsophalangeal Joint
Authors: Menz Hylton B. , Auhl Maria , Tan Jade M. , Levinger Pazit , Roddy Edward , Munteanu Shannon E.
Published: March 2019

Objective

The present study was undertaken to assess the comparative responsiveness of outcome measures used for the assessment of pain and function in individuals with osteoarthritis (OA) of the first metatarsophalangeal (MTP) joint.

Methods

Eighty‐eight patients (mean ± SD age 57.2 ± 10.2 years) with OA of the first MTP joint who participated in a randomized trial completed the Foot Health Status Questionnaire (FHSQ), the Foot Function Index Revised Short Form (FFI‐RS), and 100‐mm visual analog scales (VAS) of pain and stiffness at baseline and 12 weeks. Responsiveness of the subscales for each outcome measure was determined using paired t‐tests, Cohen's d coefficient, the standardized response mean (SRM), and the Guyatt index (GI). Sample size estimations were calculated based on minimal important differences (MIDs).

Results

All outcome measures were sensitive to change and demonstrated at least medium effect sizes. Three outcome measures exhibited large or very large effect sizes for Cohen's d coefficient, the SRM, and the GI: the FHSQ pain subscale (d = 1.03; SRM 1.10, GI score 1.30), the FFI‐RS pain subscale (d = 1.09; SRM 1.05, GI score 1.73), and the 100‐mm VAS of pain severity while walking (d = 1.22; SRM 1.07, GI score 1.78). Sample size calculations indicated that between 20 and 33 participants per group would be required to detect MIDs using these measures.

Conclusion

The FHSQ pain subscale, FFI‐RS pain subscale, and the 100‐mm VAS of pain severity while walking are the most responsive outcome measures for the assessment of pain and function in individuals with OA of the first MTP joint. These findings provide useful information to guide researchers in selecting appropriate outcome measures for use in future clinical trials.
Utilizing a Spiro TADF Moiety as a Functional Electron Donor in TADF Molecular Design toward Efficient “Multichannel” Reverse Intersystem Crossing
Authors: Gan Lin , Xu Zhida , Wang Zhiheng , Li Binbin , Li Wei , Cai Xinyi , Liu Kunkun , Liang Qiumin , Su Shi‐Jian
Published: March 2019

Designing thermally activated delayed fluorescence (TADF) materials with an efficient reverse intersystem crossing (RISC) process is regarded as the key to actualize efficient organic light‐emitting diodes (OLEDs) with low efficiency roll‐off. Herein, a novel molecular design strategy is reported where a typical TADF material 10‐phenyl‐10H, 10′H‐spiro[acridine‐9, 9′‐anthracen]‐10′‐one (ACRSA) is utilized as a functional electron donor to design TADF materials of 2,4,6‐triphenyl‐1,3,5‐triazine(TRZ)‐p‐ACRSA and TRZ‐m‐ACRSA. It is unique that the intramolecular charge transfer of the ACRSA moiety and the intramolecular and through‐space intermolecular charge transfer between the TRZ and ACRSA moieties, provide a “multichannel” effect to enhance the rate of the reverse intersystem crossing process (krisc) exceeding 10−6 s−1. TADF OLEDs based on TRZ‐p‐ACRSA as an emitter show a maximum external quantum efficiency (EQE) of 28% with reduced efficiency roll‐off (EQEs of 27.5% and 22.1% at 100 and 1000 cd m−2, respectively). Yellow phosphorescent OLEDs utilizing TRZ‐p‐ACRSA as a host material show record‐high EQE of 25.5% and power efficiency of 115 lm W−1, while phosphorescent OLEDs based on TRZ‐m‐ACRSA show further lower efficiency roll‐off with EQEs of 25.2%, 24.3%, and 21.5% at 100, 1000, and 10 000 cd m−2, respectively.
Tailoring of Silver Nanocubes with Optimized Localized Surface Plasmon in a Gap Mode for a Flexible MoS2 Photodetector
Authors: Sun Bo , Wang Ziyi , Liu Zhiyong , Tan Xianhua , Liu Xingyue , Shi Tielin , Zhou Jianxin , Liao Guanglan
Published: March 2019

Although noble metal nanoparticles as nanoantenna have been applied in 2D material‐based optoelectronic devices, the impact of their morphologies on device performance is still rarely investigated. In this paper, the tailoring of silica‐coated Ag nanocubes with optimized localized surface plasmon in a gap mode for a flexible MoS2 photodetector is demonstrated for the first time. The finite different time domain simulation reveals that the Ag nanocubes with an edge length of 60 nm achieve a maximum electromagnetic field enhancement of 2.8 × 106‐fold under excitation of 520 nm incident light, which is about four orders of magnitude higher than that of Ag nanospheres and nanorods. The Ag nanocube modified devices exhibit excellent performance at low operating potential. External photoresponsivity reaches 7940 A W−1 at 3 V under an incident power of 2.2 pW, achieving a 38‐fold enhancement compared to the pristine MoS2 photodetector, which is more than one order of magnitude higher than most of the reported MoS2 photodetectors. The flexible devices also display a good mechanical endurance during 10 000 bending cycles. These results indicate that Ag nanocubes coupled with Ag films show great prospect for their application in the field of 2D material‐based optoelectronic devices.
Spatially Controlled Transience of Graphene‐Polymer Electronics with Silicon Singulation
Authors: Gund Ved , Ruyack Alexander , Leonardi Amanda , Vinayakumar Kadayra Basavarajappa , Ober Christopher , Lal Amit
Published: March 2019

Transient electronics are an emerging technology for civilian and government applications that require controlled disintegration of an electronic chip into smaller components, by physical or chemical means. Here, a pillar‐on‐polymer architecture is presented for a transient system where the electronic components are partitioned on an array of silicon pillars. The pillars are mechanically tethered by a vaporizable polymer film and electrically routed with atomically thin graphene interconnects. Polymer vaporization is achieved with Joule heating of thin‐film metal heaters associated with each silicon pillar, which singulates the pillar. The pillar singulation breaks the graphene interconnects locally, without collateral damage to other on‐chip components. This process demonstrates a methodology for temporally and spatially controlled transience as any single pillar can be singulated at any time. A novel polymer‐silicon layer transfer fabrication process is used to microfabricate a 3 × 3 array of 200 µm diameter silicon pillars spaced 200 µm apart, with gold heaters and graphene interconnects, and the controlled singulation of individual pillars is demonstrated. As a demonstration of a sensor in this technology, a piezoresistive accelerometer is integrated with this platform, which uses a silicon pillar array suspended from the polymer film as a proof mass.
Efficiency of Light Outcoupling Structures in Organic Light‐Emitting Diodes: 2D TiO2 Array as a Model System
Authors: Will Paul‐Anton , Schmidt Maximilian , Eckhardt Kai , Wisser Florian , Lenk Simone , Grothe Julia , Kaskel Stefan , Reineke Sebastian
Published: March 2019

Organic light‐emitting diodes (OLEDs) are widely used in research and are established in the industry. The building block nature of organic compounds enables a vast variety of materials. On top of that, there exist many strategies to improve the light outcoupling of OLEDs making a direct comparison of outcoupling technologies difficult. Here, a novel approach is introduced for the evaluation of light outcoupling structures. The new defined “efficiency of light outcoupling structures” (ELOS) clearly determines the effectiveness of the light outcoupling structure by weighting the experimental efficiency enhancement over the theoretical outcoupling gain. It neither depends on cavity design nor on the chosen organic material. The methodology is illustrated for red phosphorescent OLEDs comprising internal and external light outcoupling structures. Assumptions and further uses are discussed with respect to experimental and theoretical handling. In addition, the ELOS is calculated for various outcoupling techniques from literature to demonstrate the universality. Finally, most suitable reference OLEDs are discussed for application of light outcoupling structures. The presented approach enables new possibilities for studying light outcoupling structures and improves their comparability in a highly material‐driven research field.
Arbitrarily 3D Configurable Hygroscopic Robots with a Covalent–Noncovalent Interpenetrating Network and Self‐Healing Ability
Authors: Cao Jie , Zhou Changlin , Su Gehong , Zhang Xinxing , Zhou Tao , Zhou Zehang , Yang Yibo
Published: March 2019

Soft materials that can reversibly transform shape in response to moisture have applications in diverse areas such as soft robotics and biomedicine. However, the design of a structurally transformable or mechanically self‐healing version of such a humidity‐responsive material, which can arbitrarily change shape and reconfigure its 3D structures remains challenging. Here, by drawing inspiration from a covalent–noncovalent network, an elaborately designed biopolyester is developed that features a simple hygroscopic actuation mechanism, straightforward manufacturability at low ambient temperature (≤35 °C), fast and stable response, robust mechanical properties, and excellent self‐healing ability. Diverse functions derived from various 3D shapes that can grasp, swing, close–open, lift, or transport an object are further demonstrated. This strategy of easy‐to‐process 3D structured self‐healing actuators is expected to combine with other actuation mechanisms to extend new possibilities in diverse practical applications.
Framework‐Porphyrin‐Derived Single‐Atom Bifunctional Oxygen Electrocatalysts and their Applications in Zn–Air Batteries
Authors: Li Bo‐Quan , Zhao Chang‐Xin , Chen Shuangming , Liu Jia‐Ning , Chen Xiao , Song Li , Zhang Qiang
Published: March 2019

High‐performance bifunctional oxygen electrocatalysis constitutes the key technique for the widespread application of clean and sustainable energy through electrochemical devices such as rechargeable Zn–air batteries. Single‐atom electrocatalysts with maximum atom efficiency are highly considered as an alternative of the present noble‐metal‐based electrocatalysts. However, the fabrication of transition metal single‐atoms is very challenging, requiring extensive attempts of precursors with novel design principles. Herein, an all‐covalently constructed cobalt‐coordinated framework porphyrin with graphene hybridization is innovatively designed and prepared as the pyrolysis precursor to fabricate single‐atom Co–Nx–C electrocatalysts. Excellent electrochemical performances are realized for both bifunctional oxygen electrocatalysis and rechargeable Zn–air batteries with regard to reduced overpotentials, improved kinetics, and prolonged cycling stability comparable with noble‐metal‐based electrocatalysts. Design principles from multiple scales are proposed and rationalized with detailed mechanism investigation. This work not only provides a novel precursor for the fabrication of high‐performance single‐atom electrocatalysts, but also inspires further attempts to develop advanced materials and emerging applications.
Field Effect and Photoconduction in Au25 Nanoclusters Films
Authors: Galchenko Michael , Black Andrés , Heymann Leonard , Klinke Christian
Published: March 2019

Quantum‐confined Au nanoclusters exhibit molecule‐like properties, including atomic precision and discrete energy levels. The electrical conductivity of Au nanocluster films can vary by several orders of magnitude and is determined by the strength of the electronic coupling between the individual nanoclusters in the film. Similar to quantum‐confined, semiconducting quantum dots, the electrical coupling in films is dependent on the size and structure of the Au core and the length and conjugation of the organic ligands surrounding it. Unlike quantum dots, however, semiconducting transport has not been reported in Au nanocluster films. Here, it is demonstrated that through a simple yet careful choice of cluster size and organic ligands, stable Au nanocluster films can electronically couple and become semiconducting, exhibiting electric field effect and photoconductivity. The molecule‐like nature of the Au nanoclusters is evidenced by a hopping transport mechanism reminiscent of doped, disordered organic semiconductor films. These results demonstrate the potential of metal nanoclusters as a solution‐processed material for semiconducting devices.
Structure and Charge Transport Properties of Cycloparaphenylene Monolayers on Graphite
Authors: Pérez‐Guardiola Andrés , Pérez‐Jiménez Ángel José , Muccioli Luca , Sancho‐García Juan Carlos
Published: March 2019

The nanoscale organization of cycloparaphenylene molecules when physisorbed on a graphite surface is theoretically investigated by means of atomistic molecular dynamics simulations employing a tailored and benchmarked force field. The landing of a single molecule is first considered, to progressively deposit more molecules to finally reach the full coverage of the surface. This protocol allows to study, consequently, the mechanism and structural pattern of their self‐aggregation. The interfacial morphologies obtained are then analyzed in terms of the electronic coupling between neighboring molecules, allowing thus to provide information about the associated charge‐transfer phenomena which could take place in these highly organized monomolecular layers.
Highly Sensitive and Ultrafast Responding Array Photodetector Based on a Newly Tailored 2D Lead Iodide Perovskite Crystal
Authors: Xu Zhiyun , Li Yaobin , Liu Xitao , Ji Chengmin , Chen Huaixi , Li Lina , Han Shiguo , Hong Maochun , Luo Junhua , Sun Zhihua
Published: March 2019

2D organic–inorganic hybrid perovskites are emerging as the promising alternatives in photodetection, due to their unique merits stemming from intrinsic quantum‐confined structures. Despite great ongoing effects, highly sensitive and ultrafast responding photodetectors of 2D hybrid perovskites remain a huge blank. Here, the first nanosecond‐responsive array photodetector based on 2D perovskite crystals of (PA)2(G)Pb2I7 (where PA = n‐pentylaminium and G = guanidinium) is fabricated, which features a newly tailored bilayer motif with large‐size G cation as “perovskiter” inside the distorted PbI3 perovskite framework. This motif creates a new branch of the intriguing 2D hybrid perovskite family. Strikingly, both high photodetectivities (6.3 × 1012 Jones) and responsivities (≈47 A W−1), as well as low dark current (≈2.4 × 10−11 A), are achieved in this array photodetector. Further, its ultrafast response time (τ) of 3.1 ns is one of the record‐fast merits for 2D hybrid perovskites. Such attributes originate from its strong in‐plane photoresponse related to perovskite network and low dark current inhibited by the hopping barriers of insulating PA bilayers. All these characteristics make (PA)2(G)Pb2I7 a promising candidate for photodetection, and pave the way to explore new 2D hybrid perovskite candidates for future high‐performance optoelectronic devices.
Organocatalytic Michael/Michael Cycloaddition Enabled Asymmetric Construction of Hexahydroxanthones with Skeletal Diversity
Authors: Liu Xiong‐Li , Wei Qi‐Di , Zuo Xiong , Xu Sheng‐Wen , Yao Zhen , Wang Jun‐Xin , Zhou Ying
Published: March 2019

A highly efficient strategy for stereocontrolled construction of potentially bioactive and structurally rigid isoxazole‐fused spirocyclohexane oxindole‐based hexahydroxanthones via an organocatalytic domino Michael/Michael cycloaddition of multifunctional chromone‐based oxindole as a 4C building block and 3‐methyl‐4‐nitro‐5‐alkenyl‐isoxazole as an activated Michael acceptor is reported. Complex and skeleton‐diversified hexahydroxanthones bearing five continuous stereocenters including one spiro quaternary carton center were smoothly afforded in up to 92% yield, >20:1 d.r. and >99% ee. Further transformation of the product into other potentially bioactive molecules has also been demonstrated. This method could also forge the libraries of medicinally relevant molecules with skeletal diversity, thus to facilitate the search for new bioactive entities.

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Energy Harvesting‐Storage Bracelet Incorporating Electrochemical Microsupercapacitors Self‐Charged from a Single Hand Gesture
Authors: Zhang Steven L. , Jiang Qiu , Wu Zhiyi , Ding Wenbo , Zhang Lei , Alshareef Husam N. , Wang Zhong Lin
Published: March 2019

The development of wearable electronics and sensing networks has increased the demand for wearable power modules that have steady output, high energy density, and long cycle life. Current power modules, such as batteries, suffer from low energy density due to their limited storage capacity. One solution to avoid the issue is to build a hybrid device consisting of both energy harvesting elements that continuously harvest ambient mechanical energy, and electrochemical energy storage units to store the harvested energy. Here, a hybrid energy harvesting bracelet, which combines a dual electromagnetic and triboelectric nanogenerator to harvest wrist motions, is reported. The bracelet is able to charge the RuO2‐based microsupercapacitor to 2 V with a single shake of human wrist, which allows the supercapacitor to power most electronic devices for minutes, such as a calculator, relative humidity, and temperature sensors.
Capture and Catalytic Conversion of Polysulfides by In Situ Built TiO2‐MXene Heterostructures for Lithium–Sulfur Batteries
Authors: Jiao Long , Zhang Chen , Geng Chuannan , Wu Shichao , Li Huan , Lv Wei , Tao Ying , Chen Zijin , Zhou Guangmin , Li Jia , Ling Guowei , Wan Ying , Yang Quan‐Hong
Published: March 2019

The detrimental shuttle effect in lithium–sulfur batteries mainly results from the mobility of soluble polysulfide intermediates and their sluggish conversion kinetics. Herein, presented is a multifunctional catalyst with the merits of strong polysulfides adsorption ability, superior polysulfides conversion activity, high specific surface area, and electron conductivity by in situ crafting of the TiO2‐MXene (Ti3C2Tx) heterostructures. The uniformly distributed TiO2 on MXene sheets act as capturing centers to immobilize polysulfides, the hetero‐interface ensures rapid diffusion of anchored polysulfides from TiO2 to MXene, and the oxygen‐terminated MXene surface is endowed with high catalytic activity toward polysulfide conversion. The improved lithium–sulfur batteries deliver 800 mAh g−1 at 2 C and an ultralow capacity decay of 0.028% per cycle over 1000 cycles at 2 C. Even with a high sulfur loading of 5.1 mg cm−2, the capacity retention of 93% after 200 cycles is still maintained. This work sheds new insights into the design of high‐performance catalysts with manipulated chemical components and tailored surface chemistry to regulate polysulfides in Li–S batteries.
Dual mechanism model for fluid particle breakup in the entire turbulent spectrum
Authors: Karimi Mohsen , Andersson Ronnie
Published: March 2019

This work provides an in‐depth understanding of different breakup mechanisms for fluid particles in turbulent flows. All the disruptive and cohesive stresses are considered for the entire turbulent energy spectrum and their contributions to the breakup are evaluated. A new modeling framework is presented that bridges across turbulent subranges. The model entails different mechanisms for breakup by abandoning the classical limitation of inertial models. The predictions are validated with experiments encompassing both breakup regimes for droplets stabilized by internal viscosity and interfacial tension down to the micrometer length scale, which covers both the inertial and dissipation subranges. The model performance ensures the reliability of the framework, which involves different mechanisms. It retains the breakup rate for inertial models, improves the predictions for the transition region from inertia to dissipation, and bridges seamlessly to Kolmogorov‐sized droplets.
3D‐Printing of Functionally Graded Porous Materials Using On‐Demand Reconfigurable Microfluidics
Authors: Costantini Marco , Jaroszewicz Jakub , Kozoń Łukasz , Szlązak Karol , Święszkowski Wojciech , Garstecki Piotr , Stubenrauch Cosima , Barbetta Andrea , Guzowski Jan
Published: March 2019

Tailoring the morphology of macroporous structures remains one of the biggest challenges in material synthesis. Herein, we present an innovative approach for the fabrication of custom macroporous materials in which pore size varies throughout the structure by up to an order of magnitude. We employed a valve‐based flow‐focusing junction (vFF) in which the size of the orifice can be adjusted in real‐time (within tens of milliseconds) to generate foams with on‐line controlled bubble size. We used the junction to fabricate layered and smoothly graded porous structures with pore size varying in the range of 80–800 μm. Additionally, we mounted the vFF on top of an extrusion printer and 3D‐printed constructs characterized by a predefined 3D geometry and a controlled, spatially varying internal porous architecture, such as a model of a bone. The presented technology opens new possibilities in macroporous material synthesis with potential applications ranging from tissue engineering to aerospace industry and construction.
Continuous‐Flow Electrosynthesis of Benzofused S‐Heterocycles by Dehydrogenative C−S Cross‐Coupling
Authors: Huang Chong , Qian Xiang‐Yang , Xu Hai‐Chao
Published: March 2019

Reported herein is the synthesis of benzofused six‐membered S‐heterocycles by intramolecular dehydrogenative C−S coupling using a modular flow electrolysis cell. The continuous‐flow electrosynthesis not only ensures efficient product formation, but also obviates the need for transition‐metal catalysts, oxidizing reagents, and supporting electrolytes. Reaction scale‐up is conveniently achieved through extended electrolysis without changing the reaction conditions and equipment.
Enantioselective Synthesis of Biaryl Atropisomers by Pd‐Catalyzed C−H Olefination using Chiral Spiro Phosphoric Acid Ligands
Authors: Luo Jun , Zhang Tao , Wang Lei , Liao Gang , Yao Qi‐Jun , Wu Yong‐Jie , Zhan Bei‐Bei , Lan Yu , Lin Xu‐Feng , Shi Bing‐Feng
Published: March 2019

The discovery of proper ligands to simultaneously modulate the reactivity and effectively control the stereoselectivity is a central topic in the field of enantioselective C−H activation. Herein, we reported the synthesis of axially chiral biaryls by Pd‐catalyzed atroposelective C−H olefination. A novel chiral spiro phosphoric acid, STRIP, was identified as a superior ligand for this transformation. A broad range of axially chiral quinoline derivatives were synthesized in good yields with excellent enantioselectivities (up to 98 % ee). Density functional theory was used to gain a theoretical understanding of the enantioselectivities in this reaction.
Polymerization of rac‐Lactide Using Achiral Iron Complexes: Access to Thermally Stable Stereocomplexes
Authors: Marin Paul , Tschan Mathieu J.‐L. , Isnard Florence , Robert Carine , Haquette Pierre , Trivelli Xavier , Chamoreau Lise‐Marie , Guérineau Vincent , del Rosal Iker , Maron Laurent , Venditto Vincenzo , Thomas Christophe M.
Published: March 2019

Enantiopure poly(lactic acid) (PLA) can form stereocomplexes when enantiomeric PLA chains are mixed in equivalent amounts. Such materials provide interesting features that might be suitable for numerous applications. Despite several advantages, the main drawback of PLA is its narrow window of processing, thus limiting its use for industrial applications. Reported herein are achiral iron complexes, that are highly active, productive, and stereoselective under mild reaction conditions for the ring‐opening polymerization of lactide. The corresponding catalytic systems enable the production of stereoblock polymers with high molecular weights, allowing the formation of thermally stable and industrially relevant stereocomplexes.
Building Supramolecular DNA‐Inspired Nanowires on Gold Surfaces: From 2D to 3D
Authors: Gatto Emanuela , Kubitzky Sascha , Schriever Marc , Cesaroni Simona , Mazzuca Claudia , Marafon Giulia , Venanzi Mariano , De Zotti Marta
Published: March 2019

Three building blocks have been designed to chemically link to a gold surface and vertically self‐assemble through thymine–adenine hydrogen bonds. Starting from these building blocks, two different films were engineered on gold surface. Film 1 consists of adenine linked to lipoic acid (Lipo–A) to covalently bind to the gold surface, and ZnTPP linked to a thymine (T–ZnTPP). Film 2 has an additional noncovalently linked layer: a helical undecapeptide analogue of the trichogin GA IV peptide, in which four glycines were replaced by four lysines to favor a helical conformation and reduce flexibility and the two extremities were functionalized with thymine and adenine to enable Lipo–A and T–ZnTPP binding, respectively. These films were characterized by electrochemical and spectroscopic techniques, and were very stable over time and when in contact with solution. Under illumination, they could generate current with higher efficiency than similar previously described systems.
Sulfonium, an Underestimated Moiety for Structural Modification, Alters the Antibacterial Profile of Vancomycin Against Multidrug‐Resistant Bacteria
Authors: Guan Dongliang , Chen Feifei , Qiu Yunguang , Jiang Bofeng , Gong Likun , Lan Lefu , Huang Wei
Published: March 2019

In the antibiotics arsenal, vancomycin is a last resort for the treatment of intractable infections. However, this situation is under threat because of the increasing appearance of vancomycin‐resistant bacteria (VRB). Herein, we report a series of novel vancomycin derivatives carrying a sulfonium moiety. The sulfonium–vancomycin derivatives exhibited enhanced antibacterial activity against VRB both in vitro and in vivo. These derivatives also exhibited activity against some Gram‐negative bacteria. The sulfonium modification enhanced the interaction of vancomycin with the bacterial cell membrane and disrupts membrane integrity. Furthermore, the in vivo pharmacokinetic profile, stability, and toxicity of these derivatives demonstrated good druggability of the sulfonium–vancomycin analogues. This work provides a promising strategy for combating drug‐resistant bacterial infection, and advances the knowledge on sulfonium derivatives for structural optimization and drug development.
Desymmetrization of meso diols using enantiopure zinc (II) dimers: Synthesis and chiroptical properties
Authors: Chinnaraja Eswaran , Arunachalam Rajendran , Samanta Jayanta , Natarajan Ramalingam , Subramanian Palani S.
Published: March 2019

The one‐pot metal templated synthesis of enantiopure binuclear Zn (II) complexes Zn2L1–Zn2L4 were obtained by treating (1R,2R)‐diphenylethylenediamine or (1S,2S)‐diphenylethylenediamine with 2‐hydroxy‐5‐methyl‐1,3‐benzenedicarboxaldehyde or 4‐tert‐butyl‐2,6‐diformylphenol and zinc acetate. The chiroptical properties of the complexes were studied by using circular dichroism spectroscopy. These ΔΔ and ΛΛ complexes were used as enantioselective catalysts for desymmetrization of meso diol to achieve monobenzoylated product with 96% yield and 88% ee.
Robust control of wind turbines based on fractional nonlinear disturbance observer
Authors: Muñoz‐Vázquez Aldo Jonathan , Parra‐Vega Vicente , Sánchez‐Orta Anand , Romero‐Galván Gerardo , Lara‐Alabazares David
Published: March 2019

In order to assure maximum energy conversion, the angular velocity of the wind turbine rotor tracks a nominal profile depending on the wind speed. However, conventionally, wind flows present non‐differentiable components due to turbulence and gust winds, which affect the wind energy management. Thus, a fast and robust controller is required to induce such nominal regime for maximum energy transfer. A fractional‐order nonlinear disturbance‐observer (FNDOB) is proposed in this paper to cancel the non‐differentiable components of the wind speed, as well as dynamic uncertainties and other aerodynamic disturbances. The proposed FNDOB is based on continuous fractional sliding modes, assuring that disturbances and uncertainties are exactly compensated in finite‐time. A representative simulation study for a variable‐speed wind turbine is presented to show the reliability of the proposed scheme, and a comparative analysis with respect to a conventional linear disturbance observer based control is presented.
Why the cellulosic biofuels mandate fell short: a markets and policy perspective
Authors: Brown Tristan R.
Published: March 2019

The revised Renewable Fuel Standard's cellulosic biofuels mandate requires the USA to consume 16 000 million gallons of cellulosic biofuel per year by 2022. The cellulosic biofuels industry has fallen far short of reaching the production targets needed to achieve this volume, and it has even struggled to achieve the greatly reduced revised volumes that were created by the US Environmental Protection Agency despite the subsequent inclusion of landfill gas within the mandate. This article examines the underlying causes of this shortfall from the perspectives of markets and policy. It examines how the cellulosic biofuels production environment has not been conducive to the cost‐competitiveness of pioneer, first‐of‐their‐kind facilities and pathway buildout, and how recent techno‐economic analyses have used uncertainty to quantify the impacts of this environment. It further examines how the cellulosic biofuels mandate has actually hindered commercialization despite being intended to support it. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd
The cellular effects of Pulsed Electromagnetic Fields on osteoblasts: A review
Authors: Galli Carlo , Pedrazzi Giuseppe , Guizzardi Stefano
Published: March 2019

Electromagnetic fields (EMFs) have long been known to interact with living organisms and their cells and to bear the potential for therapeutic use. Among the most extensively investigated applications, the use of Pulsed EMFs (PEMFs) has proven effective to ameliorate bone healing in several studies, although the evidence is still inconclusive. This is due in part to our still‐poor understanding of the mechanisms by which PEMFs act on cells and affect their functions and to an ongoing lack of consensus on the most effective parameters for specific clinical applications. The present review has compared in vitro studies on PEMFs on different osteoblast models, which elucidate potential mechanisms of action for PEMFs, up to the most recent insights into the role of primary cilia, and highlight the critical issues underlying at least some of the inconsistent results in the available literature. Bioelectromagnetics. 2019;9999:XX–XX. © 2019 Bioelectromagnetics Society.
Dynamic prediction: A challenge for biostatisticians, but greatly needed by patients, physicians and the public
Authors: Schumacher Martin , Hieke Stefanie , Ihorst Gabriele , Engelhardt Monika
Published: March 2019

Prognosis is usually expressed in terms of the probability that a patient will or will not have experienced an event of interesttyears after diagnosis of a disease. This quantity, however, is of little informative value for a patient who is still event‐free after a number of years. Such a patient would be much more interested in the conditional probability of being event‐free in the upcomingtyears, given that he/she did not experience the event in thesyears after diagnosis, called “conditional survival.” It is the simplest form of a dynamic prediction and can be dealt with using straightforward extensions of standard time‐to‐event analyses in clinical cohort studies. For a healthy individual, a related problem with further complications is the so‐called “age‐conditional probability of developing cancer” in the nexttyears. Here, the competing risk of dying from other diseases has to be taken into account. For both situations, the hazard function provides the central dynamic concept, which can be further extended in a natural way to build dynamic prediction models that incorporate both baseline and time‐dependent characteristics. Such models are able to exploit the most current information accumulating over time in order to accurately predict the further course or development of a disease. In this article, the biostatistical challenges as well as the relevance and importance of dynamic prediction are illustrated using studies of multiple myeloma, a hematologic malignancy with a formerly rather poor prognosis which has improved over the last few years.
Challenge your stereotypes! Human Library and its impact on prejudice in Poland
Authors: Groyecka Agata , Witkowska Marta , Wróbel Monika , Klamut Olga , Skrodzka Magdalena
Published: March 2019

Human Library is a public event aimed at reducing stereotypes and prejudices, in the form of an interactive, contact‐based intervention. It employs the logic of a regular library yet with readers “borrowing” Living Books, which are real people representing various minority groups. Readers engage in 30‐min conversations, during which they can challenge their stereotypes and widen their scope of knowledge and understanding. This pre‐post intervention study examined the effectiveness of the Human Library (held in Wrocław, Poland) in reducing social distance towards Roma, Muslims, dark‐skinned, and transgender people, as well as in decreasing homonegativity. Also, we measured whether participation in the Human Library changes individual attitudes towards diverse workgroups. We found that the Human Library decreased social distance towards Muslims. Also, the more Living Books that the participants “read,” the bigger the shift in their social distance towards Muslims. Furthermore, we observed an increase in positive affective attitude towards working in diversified groups, as a result of participation in the event. The study serves as partial support for the effectiveness of the Human Library in altering one's attitude towards minority groups and diversity. The intervention is discussed as a promising but not yet entirely understood tool to improve intergroup relations.
Prevention of kidney cell damage in hyperglycaemia condition by adiponectin
Authors: Esmaeili Sajad , Motamedrad Maryam , Hemmati Mina , Mehrpour Omid , Khorashadizadeh Mohsen
Published: March 2019

Adiponectin (APN) is an adipocytokine, secreted from adipose tissue and has anti‐inflammatory, anti‐ageing, and antidiabetic properties. Hyperglycaemia can damage the renal cells, and mammalian target of rapamycin (mTOR), along with Sirtuin 1 (SIRT1), have an important role in kidney cell response to hyperglycaemia. Therefore, understanding the relationship between adiponectin, mTOR, and SIRT1 proteins is beneficial for deciphering the mechanism of adiponectin function. In this study, Human Embryonic Kidney‐293 (HEK‐293) cells were cultured under normal and high‐glucose condition, with and without APN (1, 10, and 100 ng/mL) for 48 hours. mTOR protein expression was evaluated by western blot analysis, and SIRT1 protein was assessed using ELISA method. To evaluate hyperglycaemia‐mediated cytotoxicity, cell viability was determined using MTT assay. Data showed that APN in high dose (100 ng/mL) significantly reduced the expression of mTOR and p‐mTOR, increased SIRT1 protein, and also improved cell viability compared with the control high glucose (p ≤ 0.05). According to this results, APN can be useful in preventing renal cell damage, by affecting on the expression of mTOR and SIRT1 proteins, as well as increasing the survival of kidney cells in hyperglycaemia conditions.

Significance of the study

Adiponectin triggered mTOR/p‐mTOR/SIRT1 pathway and decreased cell death in human kidney cells. Our findings provide preliminary experimental data that support further studies on the potential therapeutic role of adiponectin in diabetes and diabetic‐induced metabolic complications.
Telmisartan protects against high glucose/high lipid‐induced apoptosis and insulin secretion by reducing the oxidative and ER stress
Authors: Wang Yan , Xue Jingjing , Li Yan , Zhou Xin , Qiao Shun , Han Dewu
Published: March 2019

Telmisartan, an angiotensin II receptor blocker, has been widely used for hypertension. It has also been reported to improve insulin sensitivity in animal models of obesity and diabetic patients by targeting to the peroxisome proliferator‐activated receptor (PPAR)‐γ. High glucose/high lipid (HG/HL)‐induced apoptosis of pancreatic β‐cells impairs its function of insulin secretion and is generally believed to be the key factor in the development of diabetes. In this study, we investigated whether telmisartan exerted a protective effect against HG/HL‐induced apoptosis and insulin secretion in vitro as well as in vivo; 10‐μM telmisartan treatment significantly reduced HG (25 mM) or/and HL (0.4 mM palmitic acid) induced‐cell apoptosis and greatly improved insulin secretion in INS‐1 pancreatic β‐cells, which is consistent in an obesity rat model induced by HG/HL diets. Furthermore, telmisartan treatment markedly reduced the protein level of GRP78, CHOP, and caspase 12, while increasing anti‐apoptotic Bcl‐2 protein expression. Moreover, telmisartan treatment significantly reduced intracellular ROS levels. Mechanistically, we demonstrated that PPARγ signaling pathway may be involved in the telmisartan protective effects, which were blocked by a PPARγ blocker, GW9662. In conclusion, the protective effect of telmisartan was mediated by an anti‐ER stress‐induced apoptotic and anti‐oxidative pathway.

Significance of this study

Type 2 diabetes mellitus (T2DM) is a chronic metabolic disorder worldwide pathologically characterized by hyperglycemia and insulin resistance. Long‐term high glucose in the blood has been proposed to induce pancreatic β‐cell loss and is generally believed to be the key factor in the development of diabetes. In the present study, we demonstrated that telmisartan, a common drug used for hypertension treatment, has a protective effect against high glucose/high lipid‐induced cell apoptosis and greatly improves the insulin secretion function by inhibiting the oxidative stress and ER stress. Furthermore, this protective effect of telmisartan is mediated by the PPAR‐γ signal pathway, which may provide a potential strategy against T2DM.
A Bis‐Zn2+‐Pyridyl‐Salen‐Type Complex Conjugated to the ATP Aptamer: An ATPase‐Mimicking Nucleoapzyme
Authors: Biniuri Yonatan , Shpilt Zohar , Albada Bauke , Vázquez‐González Margarita , Wolff Mariusz , Hazan Carina , Golub Eyal , Gelman Dimitri , Willner Itamar
Published: March 2019

Catalytic nucleic acids consisting of a bis‐Zn2+‐pyridyl‐salen‐type ([di‐ZnII 3,5 bis(pyridinylimino) benzoic acid]) complex conjugated to the ATP aptamer act as ATPase‐mimicking catalysts (nucleoapzymes). Direct linking of the Zn2+ complex to the 3′‐ or 5′‐end of the aptamer (nucleoapzymes I and II) or its conjugation to the 3′‐ or 5′‐end of the aptamer through bis‐thymidine spacers (nucleoapzymes III and IV) provided a set of nucleoapzymes exhibiting variable catalytic activities. Whereas the separated bis‐Zn2+‐pyridyl‐salen‐type catalyst and the ATP aptamer do not show any noticeable catalytic activity, the 3′‐catalyst‐modified nucleoapzyme (nucleoapzyme IV) and, specifically, the nucleoapzyme consisting of the catalyst linked to the 3′‐position through the spacer (nucleoapzyme III) reveal enhanced catalytic features in relation to the analogous nucleoapzyme substituted at the 5′‐position (kcat=4.37 and 6.88 min−1, respectively). Evaluation of the binding properties of ATP to the different nucleoapzyme and complementary molecular dynamics simulations suggest that the distance separating the active site from the substrate linked to the aptamer binding site controls the catalytic activities of the different nucleoapzymes.
Postnatal diagnosis of de novo complex der(8) in a boy with prenatal diagnosis of recombinant chromosome 8 syndrome
Authors: Oren Marina S. , Camacho Jenny E. , Xie Hongyan , Lowe Jean , Cushing Tom , Clericuzio Carol , Maxwell Jessie R.
Published: March 2019

Key Clinical Message

Recombinant chromosome 8 syndrome is caused by duplication of 8q and deletion of 8p. A fetus with anomalies was misdiagnosed with this syndrome based on an amniocyte karyotype. Postnatal chromosomal microarray and other studies identified a de novo derivative chromosome 8. For fetal anomalies, detailed genetic studies may be required.
Tuning Zeolite Properties towards CO2 Methanation: An Overview
Authors: Bacariza M. Carmen , Graça Inês , Lopes José M. , Henriques Carlos
Published: March 2019

This work provides a short review of the literature concerning the utilization of zeolites as supports for CO2 methanation catalysts. Indeed, the application of these materials in carbon dioxide hydrogenation into methane has led to considerably relevant performances according to the literature, being zeolite‐based catalysts more active and selective than commercial materials reported. Considering the well‐known zeolite features and the possibility to finely modulate its properties, inducing relevant changes on the adsorbed metal species and in the CO2 activation ability of the catalyst, potentially interesting catalytic properties can be generated also towards this transformation. Possible correlations between the characteristics of these materials, found as relevant for CO2 methanation, and the catalytic properties will be then presented and discussed.
Acid Hydrolysis of Chitosan to Oligomers Using Hydrochloric Acid
Authors: Aljbour Nawzat D. , Beg Mohammad D. H. , Gimbun Jolius
Published: March 2019

The natural polymer chitosan is widely used for medical and drug delivery applications. Low molecular weight chitosan (LMWC) has superior properties compared to high molecular weight chitosan (HMWC), which open new applications of LMWC, especially in the cosmetics, food, and pharmaceutical industries. LMWC is often produced from HMWC by acid, enzymatic, or oxidative hydrolysis. Industrially, hydrolysis with dilute HCl is preferred, since it is simple, practical, and gives a high yield. In this study 2M HCl was used to prepare LMWC. A high average depolymerization yield of 87% was obtained. The LMWCs were characterized by FTIR spectroscopy, and the molecular weight and degree of deacetylation were determined. The prepared LMWCs are fully deacetylated, and their production by this method is reproducible.
Nanopolyaniline Coupled with an Anticorrosive Graphene as a 3D Film Electrocatalyst for Efficient Oxidation of Toluene Methyl C−H Bonds and Hydrogen Production at Low Voltage
Authors: Zhu Yanji , Wang Huaiyuan , Jin Kai , Gong Jinlong
Published: March 2019

A graphene‐wrapped polyaniline nanoparticles film embedded in carbon cloth (CC/PANI/G) was fabricated and used as a 3D anodic electrocatalyst for oxidation of toluene methyl C−H groups. The methyl C−H bonds can be oxidized effectively at the CC/PANI/G anode with 99.9 % toluene conversion at a low applied voltage of only 1.0 V, which implies low energy input. Importantly, 86.6 % of toluene methyl C−H groups were converted to benzoyl groups (C=O), and hydrogen was produced efficiently at the cathode. The electrocatalytic efficiency at the CC/PANI/G anode was higher at lower voltage (1.0 V) than at higher voltage (1.5 V), and more hydrogen was produced at the corresponding cathode. The synergistic effect between the dynamic redox chemistry of nanoPANI and the excellent conductivity and anticorrosive action of graphene determined the high electrocatalytic efficiency of the oxidation of toluene methyl C−H groups at the CC/PANI/G anode. Owing to the chemical bonding between graphene and PANI, the anticorrosive CC/PANI/G anodic electrocatalyst was durable and effective for oxidation of toluene methyl C−H groups in acidic environment. This approach provides advanced electrode materials for transforming stable chemical bonds (C−H) into useful functional groups (C=O), which will be beneficial for the synthesis of organic intermediates with coupled hydrogen production.