bluuebunny/crossref_metadata_2025 huggingface dataset:
Self‐Assembly of Molecular Metal Oxide Nanoclusters
Authors: Vilà‐Nadal Laia , Cronin Leroy
Published: August 2017

The aim to both understand and control molecular self‐assembly from the molecule up to the material has been an important goal. This is because the ability to manipulate the formation of building blocks at small scales lies at the very foundations of nanotechnology and is vital if we are to access the room available at the bottom. Molecular metal oxides or polyoxometalates (POMs) offer a route to achieve this control at a molecular level. In fact,POMsare an archetypal family of self‐assembled molecular clusters that display a vast range of physical properties, structural features, and sizes. Over the last twenty years, the community of researchers in the area of polyoxometalate cluster science has developed synthetic methodologies, theoretical approaches, and analytical techniques allowing understanding their complex self‐assembly mechanisms and reactions. In the present chapter, we will introduce the basic principles that rule POM self‐assembly, discussing their building blocks and recent advances toward the understanding of their complex chemical transformations, leading to the design of reactivity by structural control. Finally, we discuss how the flow of material and energy, coupled with control of local rules, allows control of intricate assemblies via manipulation of the dissipative dynamics leading to the self‐organization of architectures formed far from equilibrium.
Inorganic Nanotubes and Fullerene–Like Nanoparticles from Layered (2D) Compounds
Authors: Yadgarov L. , Popovitz‐Biro R. , Tenne R.
Published: August 2017

Soon after carbon nanotubes were discovered by Iijima (Nature, 1991), we proposed (Nature, 1992) that inorganic layered compounds, likeWS2, are unstable in the planar form in the nanorange. Under proper chemical conditions, this inherent instability leads to folding of the layers and formation of hollow closed‐cage structures, that is, nanotubes (INT) and fullerene‐like (IF) nanoparticles. Given the elastic energy of the bending, formation of these closed‐cage nanostructures is pending on providing enough energy, that is, high temperature reactions. In the following years, we and others have preparedIF/INTfrom numerous layered compounds and studied their properties. Numerousab initiostudies were also dedicated to the study of nanotubes from different layered compounds. Recent developments in this field will be described, including the study of nanotubes from “misfit” compounds; doping of theIF/INT; ultrahigh temperature synthesis ofIF/INT; their optical and electrical properties, and so on. The mechanical properties of individual nanotubes were studied experimentally and usingab initiocalculations.

Studying in detail the growth‐mechanism ofIF/INTof several compounds, mostlyWS2andMoS2we were able to scale‐up their synthesis to mass production. Several applications for theseIF/INT, especially as superior solid lubricants and for reinforcing polymer nanocomposites, were put forward. The successful commercialization of products based on these ideas will be briefly described.
Layered Materials: Oxides and Hydroxides
Authors: Shintaro Ida
Published: August 2017

Layered compounds exhibit various properties based on their layered structures. The most typical chemical property is the intercalation reaction, which most layered oxides and hydroxides possess and which is important for the charge–discharge of secondary batteries and the preparation of new layered compounds. Layered materials have been a focus in the fields of superconductors, ferromagnetics, thermoelectrics, cosmetics, and photocatalytic materials, where investigations have been conducted for a wide range of applications. Therefore, although it is not possible to introduce all of the layered oxides and hydroxides here, their fundamental properties and reactions are often dependent on the transition metal elements in the layered structure. In this chapter, the fundamental structures and properties of layered perovskite oxides, layered oxides (cobalt, manganese, copper, titanium, niobium), and layered double hydroxides are described. In addition, exfoliation of the layered structures and the formation of layered structures using nanosheets are introduced.
Ordered Mesoporous Materials
Authors: Kruk Michal
Published: August 2017

Mesoporous materials are classified as materials with pores of widths between 2 and 50 nm. These materials are important in separations, heterogeneous catalysis, and many other applications. Mesoporous materials are usually disordered at nanoscale, but their structurally well‐defined families emerged in 1990s and have gained prominence. Herein, ordered materials with mesopores templated by surfactant micelles are discussed, with the primary focus on those with silica‐based frameworks. Structures of representative ordered mesoporous silicas, including those with cylindrical and spherical mesopores, are presented in the context of families of surfactants (primarily cationic surfactants and poly(ethylene oxide)‐based nonionic surfactants) that are suitable for their synthesis. Selected mechanisms of formation of the materials are outlined. Different achievable framework compositions are briefly noted. Basic principles of the pore shape control based on surfactant packing considerations are introduced. Mechanisms of pore size control are discussed. In particular, the pore size adjustability through the selection of surfactants of different molecular sizes and the addition of micelle swelling agents (expanders) is reviewed, and ranges of achievable pore diameters are outlined. The pore size tuning based on the framework shrinkage upon surfactant removal is also noted. The pore accessibility and connectivity are delineated for both spherical and cylindrical mesopores, and the means of their control are outlined, noting also limitations in their applicability. While this chapter provides only a glimpse of a vast field of ordered mesoporous solids, it is meant to reflect some of the most important characteristics of the remarkable family of materials.
Macroporous Materials Synthesized by Colloidal Crystal Templating
Authors: Hu Jinbo , Stein Andreas
Published: August 2017

Colloidal crystal templating is a versatile approach to synthesize nanostructured porous materials with a wide variety of compositions. The resulting three‐dimensionally ordered macroporous (3
DOM
) or mesoporous (3
DOm
) materials exhibit periodic pore structure with pore diameters that can be tuned via the template from a few nanometers to hundreds of micrometers. This architecture endows the materials with unique properties that can benefit a variety of applications, including optical, catalytic, electrochemical, and tissue engineering applications. This chapter describes synthesis–structure–property relationships of porous materials prepared by colloidal crystal templating and provides specific examples from the literature. Emphasis is placed on understanding the structural features of these materials, how to obtain these structural features from a synthetic point of view, and how the unique structures benefit specific applications. Most of the discussions are focused on 3
DOM
materials, but also apply to similar mesoporous or hierarchically structured materials prepared by colloidal crystal templating. The chapter ends with our perspectives on the field.
Predicting the Structure and Chemistry of Low‐Dimensional Materials
Authors: Yu Xiaohu , Oganov Artem R. , Wang Zhenhai , Saleh Gabriele , Sharma Vinit , Zhu Qiang , Wang Qinggao , Zhou Xiang‐Feng , Popov Ivan A. , Boldyrev Alexander I. , Baturin Vladimir S. , Lepeshkin Sergey V.
Published: August 2017

In this chapter, we focus on evolutionary algorithms for predicting structures of low‐dimensional systems and their applications to clusters, polymers, surfaces, and 2
D
crystals. The principles of evolutionary algorithms in application to such systems are systematically reviewed, and a number of applications are discussed, with emphasis on the structure, functionality, and chemical bonding.
Electrical Energy Storage: Batteries
Authors: McCalla Eric
Published: August 2017

Secondary batteries have become the dominant source of energy for personal electronics and are the most promising technology for widespread implementation of electric vehicles. Much of the innovations that have taken place in the last 20 years in the field of Li‐ion batteries (and other battery technologies) relate to the design of new materials allowing for greater energy density without compromising long‐term performance. This chapter is devoted to components of modern batteries where solid‐state chemistry has played and will continue to play a significant role. The batteries of particular interest will be Li‐ion (nearing maturity) and all solid‐state batteries (currently used for niche applications only). In metal–ion battery systems, the stoichiometry and synthesis conditions of the electrode materials have dramatic effects on the battery properties and solid‐state chemistry has therefore played a vital role in developing these technologies. Here, the topics covered will be the operation of state‐of‐the‐art batteries, the structures of typical materials used in batteries as well as their synthesis, and finally an overview of ways in which solid‐state chemistry has contributed to battery research, including a discussion of combinatorial chemistry. The prospects for all solid batteries will also be critically examined.
Dye‐Sensitized Solar Cells
Authors: Nikolskaia Anna , Shevaleevskiy Oleg
Published: August 2017

The dye‐sensitized nanocrystalline solar cells (DSSCs), considered as third‐ or next‐generation solar cells, attracted a significant interest as a possible cost‐attractive alternative to the conventional silicon‐based counterparts. DSSCs can achieve up to nearly 13% of certified power conversion efficiency and show great potential for large‐scale production due to using cheap materials and an economically friendly and easy fabrication process. This chapter schematically illustrates the structure and the energy level diagram of a dye‐sensitized solar cell. A variety of wide‐bandgap metal oxides, such as TiO2, ZnO, SnO2, and Nb2O5, can be used as n‐type semiconductor materials for fabricating photoanodes for DSSCs. DSSCs have a number of attractive features and advantages as compared to the conventional solid‐state silicon‐based solar cells. One of the main advantages is their high power conversion efficiency under low solar radiation and in cloudy weather conditions.
Designing Thermoelectric Materials Using 2DLayers
Authors: Bauers Sage R. , Johnson David C.
Published: August 2017

Research efforts over the past few decades have resulted in significant progress in the discovery of new thermoelectric materials. This includes advances in traditional bulk compounds and the introduction of new paradigms to the field, such as composite compounds, correlated electron systems, and low‐dimensional materials. Several of these results are presented, with a particular emphasis on composite structures comprised of 2D building blocks.
Functional Materials: For Sensing/Diagnostics
Authors: Munje Rujuta D. , Prasad Shalini , Graef Edward
Published: August 2017

There has been a tremendous growth in the field of diagnostic sensors and environmental gas sensors in the past 10 years. The global market for commercial sensors was estimated to be aroundUS$12 billion in 2015. A diagnostic sensor or a biosensor is used for recognition of molecules such as proteins, enzymes, or metabolites from body fluids. Gas sensing has become an active field of research that has far reaching implication into the future. From the viewpoint of global climate change, air quality, and toxic gas detection, gas sensors are being researched both on the industrial and on the university levels to provide tools to better understand these applications and more. The environmental gas sensors can be used for detection of gas,VOCs, or trace elements from environment. Both biosensors and environmental sensors have evolved through multiple generations based on the advancements of the functional materials that are being used for detection of the biomolecule or environmental gas of interest. Functional materials can be characterized as materials possessing special properties such as magnetic, piezoelectric, high tensile strength, capacitive energy storage, and so on. The enrichment in the field of nanotechnology in terms of growth, fabrication, and integration of nanomaterials into a sensor device has set a new paradigm for the form and function of sensor devices. This chapter reviews the current state‐of‐the‐art nanomaterial technology leveraged both for the development of protein, hormone, and enzyme biosensors and for the development of environmental gas sensors.
Catalysis/Selective Oxidation by Metal Oxides
Authors: Ueda Wataru
Published: August 2017

Selective oxidation catalysts based on metal oxides are categorically summarized in terms of their functions derived from high dimensionality in crystalline catalytic materials, which are titanosilicate, divanadyl pyrophosphate, heteropoly compounds, molybdenum–vanadium mixed oxides, and multicomponentBi–Mooxides.
Combinatorial Approaches for Bulk Solid‐State Synthesis of Oxides
Authors: McGinn Paul J.
Published: August 2017

Combinatorial approaches have been developed to accelerate and improve the repetitive serial synthesis and analysis of individual samples. This chapter focuses on techniques that have been utilized to process inorganic solid‐state materials, particularly in bulk or particulate form. Combinatorial powder synthesis from liquid precursors is a commonly used route in bulk high‐throughput materials studies. Liquid deposition routes are attractive to researchers because implementation is usually straightforward and relatively inexpensive. Combinatorial processing from dry powders is appealing because it scales directly to common industrial practice. A significant advantage compared to some liquid routes is that one can realize a high yield from inexpensive reagents, and it can be easily scaled to large quantities. Polymer complex methods have also been used for combinatorial powder synthesis. These methods are widely used in the synthesis of complex oxides because they are simple to utilize and synthesis occurs at lower temperature and shorter reaction times than solid‐state routes.
Construction of Pyridazine Analogues via Rhodium‐mediated C‐H Activation
Authors: Yang Chao , Song Feifei , Chen Jiean , Huang Yong
Published: August 2017

Herein a rhodium (III)‐mediated catalysis was demonstrated for approaching the structurally divergent N,N‐bicyclic pyridazine analogues. The pyrazolidinone moiety was used to direct the ortho C−H activation and this led to a general synthesis of benzopyridazine analogues with satisfactory yields. The crucial effect of the base was illustrated in the sequential dehydration process. For mechanistic insight, control experiments were performed for illustration of the catalytic circle. Gram scale synthesis and several practical transformations were conducted for further applications.

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A Biobased Flame‐Retardant Resin Based on Lignin
Authors: Matsushita Yasuyuki , Hirano Daisuke , Aoki Dan , Yagami Sachie , Takagi Yasuo , Fukushima Kazuhiko
Published: August 2017

This study focuses on the development of biobased flame‐retardant resins. Lignin and α,ω‐alkanediols are used, which can be obtained from biomass. To introduce intumescent properties, phosphoryl chloride and 3‐amino‐1,2,4‐triazole are introduced into kraft lignin prior to it being resinified with the α,ω‐alkanediols. In simple combustion tests using a gas burner at 1300 °C, the resins prepared exhibit nonburnable properties, producing only a swollen char. According to dynamic mechanical analysis, the glass transition temperature decreases with an increase in the carbon number and amount of the alkanediols introduced. The mechanical loss tangent (tan δ) value of the prepared resins is below 1, indicating that the resins would not drip flaming particles during burning. Indeed, the specimens do not generate particles in the simple combustion tests. According to the results of cone calorimeter testing, the total heat release and the peak heat release rate are significantly smaller than those of a commercial phenol‐formaldehyde‐resin‐containing flame retardant.
Efficient Red‐Emissive Organic Crystals with Amplified Spontaneous Emissions Based on a Single Benzene Framework
Authors: Tang Baolei , Wang Chenguang , Wang Yue , Zhang Hongyu
Published: August 2017

Red‐emissive fluorophores generally consist of large π‐extended systems and thus encounter the problem of serious fluorescence quenching in the solid state. A series of structurally simple compounds 2,5‐bis(alkylamino)terephthalates 1 a–c are reported that consist of a very small π‐system (only a single benzene) but display efficient red emission in crystals. Crystal 1 a having a molecular weight of only 252 g mol−1 shows red emission with the maximum of 620 nm and a fluorescence quantum yield of 0.40. The unique emission property of crystal 1 a is mainly because of the planarization of skeleton dominated by the strong intramolecular hydrogen bonds and the packing structure with negligible π–π interactions contributed by the mini π‐system. Moreover, besides efficient red emission, high crystallinity with co‐planar facets endows crystal 1 a with significant amplified spontaneous emission.
Relationship between structure and physical strength of silk fibroin nanofiber sheet depending on insolubilization treatment
Authors: Fukuda Yasuhiro , Aytemiz Derya , Higuchi Akira , Ichida Yuya , Asakura Tetsuo , Kameda Tsunenori , Nakazawa Yasumoto
Published: August 2017

Materials such as expanded polytetrafluoroethylene and glutaraldehyde‐fixed bovine pericardium are currently used for cardiac tissue regeneration. However, patches made from these materials remain permanently without being absorbed by the body and must be replaced overtime because of degeneration or lack of growth. To improve the long‐term outcomes for cardiac tissue regeneration, biocompatible and biodegradable materials must be used. In this study, we used two biocompatible polymers, silk fibroin (SF), which is biodegradable and segmented polyurethane, to prepare nonwoven sheets that were then insolubilized by water vapor or methanol treatment. The tensile stress increased significantly on adding segmented polyurethane to pure SF and the water vapor processed sheets showed higher extension on strain than the methanol‐processed sheets. The different insolubilization treatments also resulted in different SF structures. Our results show that it is possible to obtain the physical properties required for cardiac tissue repair patch by varying the insolubilization treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45560.
Effect of solvent quality and humidity on the porous formation and oil absorbency of SAN electrospun nanofibers
Authors: Bandegi Alireza , Moghbeli Mohammad Reza
Published: August 2017

In this study, nanofibrous mat with high oil sorption capability was prepared via one‐step electrospinning process without any further post‐treatments. For this purpose, the fabrication of styrene/acrylonitrile copolymer nanofibers was carried out using various dimethylformamide (DMF)/tetrahydrofuran and DMF/ethanol (DMF/EtOH) binary mixture ratios in an electrospining atmosphere with various relative humidity (RH) levels. Scanning electron microscope micrographs showed that DMF/tetrahydrofuran and DMF/EtOH ratio and RH value could considerably affect the diameter, surface, and interior morphology of the resultant nanofibers. The nanofiber morphology was dependent upon the polymer/solvent(s)/water ternary phase diagram behavior. In overall, the partial hydrophilicity of styrene/acrylonitrile copolymer resulted in electrospun nanofibers with wrinkled surface. In addition, the incorporation of nonsolvent in the spinning solution and using high RH atmosphere forced the polymeric solution jet to intensively phase separate and, therefore, produce the nanofibers with highly interior porous structure during drying process. The maximal capacity and rate of oil sorption (170 g/g) was observed for the nanofibrous mat prepared using EtOH/DMF (2/3: vol/vol) and RH value of 60% showing the highest internal porosity. The results showed that the oil sorption capability and mechanical strength of the fibrous mat are strongly dependent on nanofibers diameter and porous structure, which can be controlled through adjusting the RH and spinning solvent quality. The electrospun mat with highest Young's modulus (7.68 MPa) was prepared using EtOH/DMF (2/3) binary mixture and RH value of 45%. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45586.
Diffusion and desorption of CO2 in foamed polystyrene film
Authors: Qian Ying‐Hui , Cao Jun‐Ming , Li Xue‐Kun , Cao Gui‐Ping , Wang Chang‐Chun , Shi Yun‐Hai
Published: August 2017

Based on the existence of the pores in foamed polystyrene (PS), foamed‐non‐Fickian diffusion (FNFD) model was proposed, for the first time, to regress the desorption data obtained by gravimetric method. Results showed that FNFD model could accurately describe the diffusion behavior of CO2 out of foamed PS, and well predict the solubility of CO2 in foamed PS. The characterization of scanning electron microscopy indicated that there were abundant pores in the foamed PS, and the pores store most of CO2, which would diffuse in the pores, adsorb to the wall of the pores, penetrate across walls of the pores, diffuse in the matrix of PS, and desorb out of PS. The mass of CO2 in the pores of foamed PS was expressed as a function of foaming pressure and temperature according to foaming kinetics. Results showed that the values calculated by this function agreed well with the values obtained from the FNFD model. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45645.
Random walk designs for selecting pool sizes in group testing estimation with small samples
Authors: Haber Gregory , Malinovsky Yaakov
Published: August 2017

Group testing estimation, which utilizes pooled rather than individual units for testing, has been an ongoing area of research for over six decades. While it is often argued that such methods can yield large savings in terms of resources and/or time, these benefits depend very much on the initial choice of pool sizes. In fact, when poor group sizes are used, the results can be much worse than those obtained using standard techniques. Tools for addressing this problem in the literature have been based on either large sample results or prior knowledge of the parameter being estimated, with little guidance when these assumptions are not met. In this paper, we introduce and study random walk designs for choosing pool sizes when only a small number of tests can be run and prior knowledge is vague. To illustrate these methods, application is made to the estimation of prevalence for two diseases among Australian chrysanthemum crops.
Novel Benzamide Derivatives: Synthesis and Bioactivity as Potent PARP‐1 Inhibitors
Authors: Ryu Hwani , Ahn Jiyeon , Choi Hyun Kyung
Published: August 2017

The poly(ADP‐ribose) polymerases (PARPs) are located in the nuclei of cells and involved in DNA damage repair. PARP inhibitors have been used to target BRCA1/2‐defective cells that experience increases in DNA single‐strand breaks (SSBs). In the presence of PAPR inhibitors, these SSBs are converted into irreparable and toxic double‐strand breaks (DSBs) during replication, eventually leading to cell death due to genome instability caused by the impaired homologous‐mediated repair system. We designed and synthesized several novel benzamide derivatives based on the previously reported PARP‐1‐inhibitory activities of benzoxazole and benzamide moieties. Next, we used an in vitro assay to quantify their PARP‐1 inhibitory activity and evaluate their potential as possible anti‐cancer therapeutics. Compound 28d contains a hydroxamate group and showed a significant inhibitory capacity (IC50 value of 3.2 μM; 2.8‐ and 4.2‐fold decrease in SNU‐251 and MDA‐MB‐231 cells, respectively, compared with the DMSO‐treated controls). Based on these results, we suggest that we have identified a novel hydroxybenzamide derivative of a benzamide moiety which is known as a key pharmacophore in existing PARP inhibitors.
Single Cell Fabrication Towards the Realistic Evaluation of a CNT‐Strung ZIF‐Derived Electrocatalyst as a Cathode Material in Alkaline Fuel Cells and Metal−Air Batteries
Authors: Aiyappa Harshitha Barike , Bhange Siddheshwar N. , Sivasankaran Vijitha P. , Kurungot Sreekumar
Published: August 2017

The development of an electrocatalyst possessing all the vital requisites of an ideal electrode material, such as high porosity, high conductivity, and high intrinsic electrochemical activity, holds a decisive key in determining the activity of the triple‐phase boundary in many energy devices like fuel cells and metal−air battery systems. In the present work, highly porous cobalt‐based ZIFs are strung along the highly conducive CNT backbone by using a simple one‐pot technique at room temperature, which is then utilized to derive a porous, corrosion‐resistant, Co nanoparticle‐embedded electrocatalyst. Herein, for the first time, the single cell performance of the Co‐ZIF‐67‐derived electrocatalyst has been evaluated by fabricating membrane electrode assemblies of alkaline exchange membrane fuel cell (AEMFC) and zinc–air battery (ZAB) systems. A maximum power density of 296 mW/cm2 (vs. 317 mW/cm2 for 40 wt.% Pt/C) and 60 mW/cm2 (vs. 64 mW/cm2 for 40 wt.% Pt/C) in the single cells of ZAB and AEMFC systems, respectively, establishes the practical proficiency of the homemade electrocatalyst for cathode applications during realistic system‐level validations.
Aryl Transfer Selectivity in Metal‐Free Reactions of Unsymmetrical Diaryliodonium Salts
Authors: Stuart David R.
Published: August 2017

Aromatic rings are found in a wide variety of products, including pharmaceuticals, agrochemicals, and functional materials. Diaryliodonium salts are new reagents used to transfer aryl groups under both metal‐free and metal‐catalyzed reactions and thereby synthesize arene‐containing compounds. This minireview focuses on recent studies in selective aryl transfer reactions from unsymmetrical diaryliodonium salts under metal‐free conditions. Reactions reported from 2007 to 2017, which represents a period of significant growth in diaryliodonium salt chemistry, are presented and organized by the type of reactive intermediate formed in the reaction. Specifically, reactions involving λ3‐iodane, λ3‐iodane radical anions, aryl radicals, and arynes are discussed. Chemoselectivity trends in aryl transfer are compared and contrasted across reaction intermediates and translation to potential auxiliaries are posited.
Competing Pathways in O‐Arylations with Diaryliodonium Salts: Mechanistic Insights
Authors: Stridfeldt Elin , Lindstedt Erik , Reitti Marcus , Blid Jan , Norrby Per‐Ola , Olofsson Berit
Published: August 2017

A mechanistic study of arylations of aliphatic alcohols and hydroxide with diaryliodonium salts, to give alkyl aryl ethers and diaryl ethers, has been performed using experimental techniques and DFT calculations. Aryne intermediates have been trapped, and additives to avoid by‐product formation originating from arynes have been found. An alcohol oxidation pathway was observed in parallel to arylation; this is suggested to proceed by an intramolecular mechanism. Product formation pathways via ligand coupling and arynes have been compared, and 4‐coordinated transition states were found to be favored in reactions with alcohols. Furthermore, a novel, direct nucleophilic substitution pathway has been identified in reactions with electron‐deficient diaryliodonium salts.
Reducing the Flexibility of Type II Dehydroquinase for Inhibition: A Fragment‐Based Approach and Molecular Dynamics Study
Authors: Peón Antonio , Robles Adrián , Blanco Beatriz , Convertino Marino , Thompson Paul , Hawkins Alastair R. , Caflisch Amedeo , González‐Bello Concepción
Published: August 2017

A multidisciplinary approach was used to identify and optimize a quinazolinedione‐based ligand that would decrease the flexibility of the substrate‐covering loop (catalytic loop) of the type II dehydroquinase from Helicobacter pylori. This enzyme, which is essential for the survival of this bacterium, is involved in the biosynthesis of aromatic amino acids. A computer‐aided fragment‐based protocol (ALTA) was first used to identify the aromatic fragments able to block the interface pocket that separates two neighboring enzyme subunits and is located at the active site entrance. Chemical modification of its non‐aromatic moiety through an olefin cross‐metathesis and Seebach's self‐reproduction of chirality synthetic principle allowed the development of a quinazolinedione derivative that disables the catalytic loop plasticity, which is essential for the enzyme′s catalytic cycle. Molecular dynamics simulations revealed that the ligand would force the catalytic loop into an inappropriate arrangement for catalysis by strong interactions with the catalytic tyrosine and by expelling the essential arginine out of the active site.
The Impact of Corporate Social Responsibility on Consumer Preference: A Structural Equation Analysis
Authors: Boccia Flavio , Sarnacchiaro Pasquale
Published: August 2017

Nowadays, environmental and social problems are very important for modern consumers and firms, which cannot operate only in accordance with the logic of profit. In this paper, by administering a questionnaire to consumers, we have tried to assess the impact of the solidarity of responsible initiatives on consumer preferences: the conclusions are also a matter for thought for further discussion. The investigation was conducted through a sample size survey. The analysis was carried out considering a representative sample of more than 300 families, selected on a functional relation to the objectives of the work in one of the most important and representative Italian cities. This study has two main aims: to investigate consumer preferences regarding responsible initiatives of a company; and to develop and validate a structural equation model, in order to formalize the origins of behaviours regarding consumer preferences towards responsible initiatives and detect the drivers of their purchase. Copyright © 2017 John Wiley & Sons, Ltd and ERP Environment
Gene network underlying the glial regenerative response to central nervous system injury
Authors: Kato Kentaro , Losada‐Perez Maria , Hidalgo Alicia
Published: August 2017

Although the central nervous system does not regenerate, injury induces repair and regenerative responses in glial cells. In mammals, activated microglia clear up apoptotic cells and debris resulting from the injury, astrocytes form a scar that contains the lesion, and NG2‐glia elicit a prominent regenerative response. NG2‐glia regenerate themselves and differentiate into oligodendrocytes, which remyelinate axons leading to some recovery of locomotion. The regenerative response of glial cells is evolutionarily conserved across the animals and Drosophila genetics revealed an underlying gene network. This involves the genes Notch, kon‐tiki, eiger, dorsal, and prospero, homologues of mammalian Notch1, ng2, TNF, NFκB, and prox1, respectively. Feedback loops between these genes enable a surge in proliferation in response to injury and ensuing differentiation. Negative feedback sets a timer for proliferation, and prevents uncontrolled growth that could lead to glioma. Remarkable parallels are found in these genetic relationships between fruit flies and mammals. Drosophila findings provide insights into gene functions that could be manipulated in stem cells and progenitors for therapeutic repair. Developmental Dynamics 247:85–93, 2018. © 2017 Wiley Periodicals, Inc.
One‐Pot Synthesis of Butadiyne‐Bridged Bipyrrole Derivatives and Bisporphyrin
Authors: Kishore M. V. Nanda , Panda Pradeepta K.
Published: August 2017

Butadiyne‐bridged bipyrroles were prepared from 2‐iodopyrroles and trimethylsilylacetylene through a facile one‐pot synthesis involving a modified Sonogashira coupling reaction and in situ aerobic oxidative coupling of the acetylenic pyrroles; the products were obtained in yields of 31–72 % depending on the substituents on the pyrrole. The acetylene‐bridged diacids obtained from the hydrolysis of the corresponding ester derivatives are highly stable, unlike most reported oligopyrrolic diacids. This protocol could be easily extended towards the synthesis of butadiyne‐bridged bisporphyrins.
The association of genetic variations in DNA repair pathways with severe toxicities in NSCLC patients undergoing platinum‐based chemotherapy
Authors: Zheng Yi , Deng Zheng , Yin Jiye , Wang Shiming , Lu Daru , Wen Xiaoke , Li Xiangping , Xiao Di , Hu Chengping , Chen Xiang , Zhang Wei , Zhou Honghao , Liu Zhaoqian
Published: August 2017

Genetic variations in genes involved in repairing platinum‐induced DNA lesions may contribute to the toxicity of platinum‐based chemotherapy. The role of single‐nucleotide polymorphisms (SNPs) within DNA repair pathways in the occurrence of severe toxicity is not yet understood. Current studies prefer to do original works rather than analyze previously published data. Our study aimed to replicate associations between previously investigated SNPs and toxicities and to identify new genetic makers. We systematically examined the relevance of 97 SNPs in 54 candidate genes responsible for repairing DNA interstrand and intrastrand cross‐links to severe toxicity in a discovery cohort of 437 NSCLC patients receiving platinum‐based chemotherapy. Statistically significant SNPs were then assessed for replication in an independent validation cohort of 781 NSCLC patients. We found that 7 SNPs were significant at p < 0.01 (RRM1 rs12806698, XPC rs2228000, XPF rs1799801, hMLH1 rs1800734, PMS2 rs1062372, REV3L rs462779 and FANCC rs4647554) in the discovery cohort. Among them, two SNPs (RRM1 rs12806698 and hMLH1 rs1800734) remained significant after Bonferroni correction. XPC rs2228000 showed a significant relationship with severe gastrointestinal toxicity in the validation cohort. When the two cohorts were combined, XPC rs2228000 presented better tolerance of severe hematologic toxicity, gastrointestinal toxicity and leukopenia (OR = 0.677, 95% CI: 0.510–0.899, p = 0.007; OR = 0.565, 95% CI: 0.368–0.869, p = 0.009; OR = 0.628, 95% CI: 0.439–0.899, p = 0.011, respectively). Our findings can offer comprehensive pharmacogenetic information for platinum‐induced toxicities.
Work addiction and presenteeism: The buffering role of managerial support
Authors: Mazzetti Greta , Vignoli Michela , Schaufeli Wilmar B. , Guglielmi Dina
Published: August 2017

The current study examined the mediating effect of presenteeism and moderating effect of managerial support in the relation between workaholism and work–family conflict. A sample of 1065 white‐collar employees from an Italian company filled in an online survey and hypotheses were tested using a bootstrapping procedure. Results showed that presenteeism mediated the association between workaholism and work–family conflict. Moreover, the mediating effect of presenteeism was moderated by managerial support: for employees reporting lower levels of support workaholism was stronger related to presenteeism than for those experiencing higher support. Presenteeism, in turn, was related to greater levels of work–family conflict. The present study sheds light into the protective role played by managerial support in preventing workaholic employees from forcing themselves to attend work also when feeling sick. Accordingly, early intervention aimed at buffering the negative association between workaholism and work–family conflict should focus on training managers to develop supportive leadership skills.
Assessment of the imprinting efficiency of an imide with a “stoichiometric” pyridine‐based functional monomer in precipitation polymerisation
Authors: Lim K. Fremielle , Hall Andrew J. , Lettieri Stefania , Holdsworth Clovia I.
Published: August 2017

The efficiency of the stoichiometric non‐covalent imprinting of the imide 2,3,5‐tri‐O‐acetyluridine (TAU) with 2,6‐bis(acrylamido)pyridine (BAAPy) as functional monomer due to their strong donor‐acceptor‐donor/acceptor‐donor‐acceptor (DAD/ADA) hydrogen bond array interaction has been evaluated by bulk imprinting. This study is the first to investigate the imprinting and template rebinding efficiencies of the TAU/BAAPy molecularly imprinted polymeric (MIP) system prepared by precipitation polymerisation. We found that the stoichiometric 1:1 T:FM ratio has not been maintained in precipitation polymerisation and an optimal TAU:BAAPy ratio of 1:2.5 was obtained in acetonitrile without agitation affording an affinity constant (1.7 × 104 M−1) and a binding capacity (3.69 μmol/g) higher than its bulk counterpart. Molecular modelling, NMR studies, and selectivity assays against analogues uridine and 2,3,5‐tri‐O‐acetyl cytidine (TAC) indicate that, aside from the DAD/ADA hydrogen bond interaction, BAAPy also interacts with the acetyl groups of TAU. Template incorporation and rebinding in precipitation MIPs are favoured by a moderate initiator concentration, ie, initiator:total monomer (I:TM) ratio of 1:131, while low I:TM ratio (ie, 1:200) drastically reduced template incorporation and binding capacity. Vigorous agitation by stirring showed higher template incorporation but significantly lower template rebinding compared to that prepared without agitation. While the imprinting efficiencies for the best performing bulk and precipitation TAU MIPs generated in this study were moderate, 41% and 60%, respectively, their rebinding capacities were only between 3 and 4% of the incorporated template. We also present quantitative nuclear magnetic resonance spectroscopy as an efficient method for MIP characterisation.
Rotator cuff healing using demineralized cancellous bone matrix sponge interposition compared to standard repair in a preclinical canine model
Authors: Smith Matthew J. , Pfeiffer Ferris M. , Cook Cristi R. , Kuroki Keiichi , Cook James L.
Published: August 2017

This Level II study assessed clinically relevant outcomes for repair of large, retracted infraspinatus tendons (ISTs) using a demineralized bone matrix (DBM) sponge (FlexiGraft) hydrated in platelet‐rich plasma (PRP) versus direct repair in a validated canine model. Adult research dogs (n = 10) were used. The IST was transected in each shoulder (n = 20) and randomized to direct repair or repair with DBM‐PRP interposition at 4 weeks posttransection. At 12 weeks postrepair, dogs were sacrificed, and the repair evaluated by magnetic resonance imaging (MRI), histology, and biomechanical testing. MRI and histology scores were significantly (p < 0.05) better in the DBM‐PRP shoulders. Biomechanical testing revealed significantly improved strength of the DBM‐PRP repairs at 5 and 10 mm of displacement, as well as for ultimate failure load. In this canine model of retracted IST repair, DBM‐PRP sponge hydrated in PRP was considered safe and effective. In addition, use of DBM‐PRP was associated with improved MRI and histologic appearance, and improved strength compared to direct repair. Clinical significance: Based on reported failure rates for repair of large, retracted rotator cuff tears, improving tendon‐to‐bone healing is critical. Use of DBM combined with PRP shows potential for addressing this critical clinical need. © 2017 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 36:906–912, 2018.
Resilience by diversity: Large intraspecific differences in climate change responses of an Arctic diatom
Authors: Wolf Klara K. E. , Hoppe Clara J. M. , Rost Björn
Published: August 2017

The potential for adaptation of phytoplankton to future climate is often extrapolated based on single strain responses of a representative species, ignoring variability within and between species. The aim of this study was to approximate the range of strain‐specific reaction patterns within an Arctic diatom population, which selection can act upon. In a laboratory experiment, we first incubated natural communities from an Arctic fjord under present and future conditions. In a second step, single strains of the diatom Thalassiosira hyalina were isolated from these selection environments and exposed to a matrix of temperature (3°C and 6°C) and pCO2 levels (180 μatm, 370 μatm, 1000 μatm, 1400 μatm) to establish reaction norms for growth, production rates, and elemental quotas. The results revealed interactive effects of temperature and pCO2 as well as wide tolerance ranges. Between strains, however, sensitivities and optima differed greatly. These strain‐specific responses corresponded well with their respective selection environments of the previous community incubation. We therefore hypothesize that intraspecific variability and the selection between coexisting strains may pose an underestimated source of species' plasticity. Thus, adaptation of phytoplankton assemblages may also occur by selection within rather than only between species, and species‐wide inferences from single strain experiments should be treated with caution.
Synthesis of π‐Conjugated Polymer Thin Films by Electropolymerization of Benzodithiophene Derivatives
Authors: Wakana Sho , Nishiyama Hiroki , Inagi Shinsuke , Tomita Ikuyoshi
Published: August 2017

π‐conjugated polymer thin films are successfully prepared by the electropolymerization of 4,5‐diaryl benzodithiophenes, which are readily obtained by the three‐component coupling reactions of aryl iodides, 1,2‐di(thiophen‐2‐yl)ethyne, and phenylboronic acid, followed by the photochemical annulation. The resulting polymer films exhibit π‐conjugated properties as convinced from their UV–vis absorption spectra and cyclic voltammetric analyses. The electronic properties such as highest occupied molecular orbital (HOMO) energy levels of the resulting polymer films are affected by the 4‐aryl substituents. The π‐conjugated polymer thin films exhibit electrochromism, where the color of the polymer film turns from yellow to blue by oxidation.
Periodically Grafted Linear–Hyperbranched Copolymers Based on Polyethylene and Polyglycidol: Importance of the Architecture on Properties
Authors: Wu Xuanhong , Yang Fei , Liu Zhongsu , Li Wei , Gong Dirong , Mu Jingshan
Published: August 2017

Here, the periodically grafted linear–hyperbranched copolymers (LHGCs) based on polyethylene (PE) and hyperbranched polyglycidol is synthesized via acyclic diene metathesis polymerization and anionic ring‐opening multibranching polymerization. The chemical composition of LHGCs can be controlled by changing the amount of the initial monomer. For the first time this allows to control the architecture (composition and sequence distribution), in which the run length between adjacent hyperbranched pendants is exact along PE backbone. By comparing with aperiodically grafted analogues, the results clearly show the composition and the sequence distribution of LHGCs is identified as the major factor to influence the thermal stability, crystallinity as well as hydrophilicity.
“Breathing” CO2‐, O2‐, and Light‐Responsive Vesicles from a Triblock Copolymer for Rate‐Tunable Controlled Release
Authors: Lin Shaojian , Shang Jiaojiao , Zhang Xiaoxiao , Theato Patrick
Published: August 2017

A well‐defined amphiphilic triblock copolymer, poly[(ethylene glycol)methyl ether]‐block‐poly(N,N‐dimethylamino ethyl methacrylate‐co‐2,2,2‐trifluoroethyl methacrylate)‐block‐poly(4‐(4‐methoxy‐phenylazo)phenoxy methacrylate) (PEG‐b‐P(DMAEMA‐co‐TFEMA)‐b‐PMEPPMA), is successfully synthesized by stepwise atom transfer radical polymerization. Owing to its amphiphilic nature, PEG‐b‐P(DMAEMA‐co‐TFEMA)‐b‐PMEPPMA can self‐assemble into vesicles in aqueous solution and exhibits a reversible triple‐responsive behavior toward CO2, O2, and light stimuli. More importantly, such vesicles can exhibit a controlled “breathing” behavior via external stimuli due to their suitable chemical structure and stimuli responsiveness. Consequently, these vesicles can be employed as nanocarriers for rate‐tunable controlled release via adjustment of their membrane permeability by a single stimulus or various stimuli combinations.
The effect of full dose composite tissue allotransplantation immunosuppression on allograft motor nerve regeneration in a rat sciatic nerve model
Authors: Kim Jong Pil , Hundepool Caroline A. , Friedrich Patricia F. , Moran Steven L. , Bishop Allen T. , Shin Alexander Y.
Published: August 2017

Background

The purpose of this study was to identify which triple immunosuppressive protocols, currently used for vascularized composite allotransplantation in the clinic, will have the best effect on motor function recovery following nerve allograft reconstruction.

Methods

Eighty‐eight Lewis rats underwent a 1‐cm sciatic nerve allograft transplantation and skin graft from 44 Brown‐Norway rats. Group I received 0.9% isotonic saline (control); Group II, 2 mg/kg FK506; Group III, 1 mg/kg FK506 with 15 mg/kg mycophenolate mofetil (MMF); and Group IV, 2 mg/kg FK506 with 30 mg/kg MMF and prednisone. Each group consisted of 11 rats. After 12 weeks, motor function recovery was evaluated with isometric tetanic force, muscle mass, ankle contracture angle, electrophysiology, and nerve histomorphometry. Adequacy of immunosuppression was monitored with the transplanted skin graft. All data are expressed as a percentage of the contralateral side.

Results

Isometric tetanic force showed significantly better functional recovery in all groups treated with immunosuppression compared to control. Within the immunosuppression groups no significant difference was found: 42.1 ± 6.4% (Group I), 56.1 ± 12.4% (Group II), 58.4 ± 10.7% (Group III), and 61.3 ± 11.2% (Group IV). Group IV was superior to all other groups regarding ankle contracture (P < .05) and electrophysiology (P < .001). Skin graft rejection occurred in 41 and 0% (Groups III and IV, respectively).

Conclusions

FK506 significantly enhanced motor recovery after allograft reconstruction. This effect was comparable between combination treatment (low‐dose FK506 and MMF) and triple therapy (high‐dose FK506 and MMF plus prednisolone). However, triple therapy was more effective in suppressing skin rejection.
Evaluation and management of tethered cord syndrome in occult spinal dysraphism: Recommendations from the international children's continence society
Authors: Tuite Gerald F. , Thompson Dominic N.P. , Austin Paul F. , Bauer Stuart B.
Published: August 2017

Aims

As awareness and frequency of tethered spinal cord (TSC) related to occult spinal dysraphism (OSD) has increased with magnetic resonance imaging (MRI), variability exists in its evaluation and management. Due to no published level I data, we summarize the current International Children's Continence Society (ICCS) recommendations for diagnosis and treatment of OSD.

Methods

Guidelines were formulated based on analysis of pertinent literature and consensus among authors. This document was vetted by the multidisciplinary members of the ICCS via its website before submission for peer review publication.

Results

The more frequent diagnosis of OSD is associated with increased operative intervention. Spinal cord untethering (SCU) has a highly variable risk profile, largely dependent on the specific form of OSD. Progressive neurological deterioration attributed to “tethered cord” may occur, with or without surgery, in selected forms of OSD whereas other cohorts do well.

Conclusion

Infants with classic cutaneous markers of OSD, with progressive neurologic, skeletal, and/or urologic findings, present no diagnostic or therapeutic dilemma: they routinely undergo MRI and SCU. Conversely, in asymptomatic patients or those with fixed, minor abnormalities, the risk profile of these OSD cohorts should be carefully considered before SCU is performed. Irrespective of whether or not SCU is performed, patients at risk for progression should be followed carefully throughout childhood and adolescence by a multidisciplinary team.