bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structural, Photophysical, and Magnetic Circular Dichroism Studies of Three Rigidified meso‐Pentafluorophenyl‐Substituted Hexaphyrin Analogues
Authors: Ishida Masatoshi , Furuyama Taniyuki , Lim Jong Min , Lee Sangsu , Zhang Zhan , Ghosh Sudip K. , Lynch Vincent M. , Lee Chang‐Hee , Kobayashi Nagao , Kim Dongho , Sessler Jonathan L. 
Published: March 2017

AbstractDetailed electronic, structural, photophysical, and redox studies of a series of meso‐pentafluorophenyl‐substituted hexaphyrins, namely amethyrin (1), rosarin (2), and rubyrin (3), are described. In prior work, it was found that the electronic states of the antiaromatic hexapyrrolic macrocycle, [24]rosarin 2, could be modified by exposure to several Brønsted acids (e.g., HCl, HBr and HI) to produce either one‐ and two‐electron reduced species, or both. In an effort to gain further insights into the reactivity of hexaphyrins possessing different π‐conjugation pathways, the β‐dodecamethyl‐substituted [24]amethyrin 1 was prepared and its electronic structure was analyzed along with that of the o‐phenylene‐bridged [26]rubyrin 3 and rosarin 2 The [4n] and [4n+2] π‐conjugated formulations of 2 and 3, respectively, were inferred from steady‐state, fs‐transient absorption and two photon absorption measurements. Similar photophysical analyses lead to the conclusion that 1 is best considered as nonaromatic or weakly antiaromatic. Magnetic circular dichroism (MCD) spectroscopic analyses of hexaphyrins 1 and 3, as well as comparisons to 2, and theoretical perimeter MO diagram analyses provided support for the electronic assignments. In contrast to what was found for 2, simple protonation of 1 and 3 by halohydric acids did not induce an evident, redox‐based change in the electronic structure of the macrocycle.
Anionic Derivatives of Perfluorinated Trimethylgold
Authors: Pérez‐Bitrián Alberto , Martínez‐Salvador Sonia , Baya Miguel , Casas José M. , Martín Antonio , Menjón Babil , Orduna Jesús 
Published: March 2017

AbstractThe homoleptic compound [PPh4][CF3AuCF3] cleanly undergoes photoinduced oxidative addition of CF3I to afford the organogold(III) derivative [PPh4][(CF3)3AuI] in good yield and under mild conditions. This compound provides a convenient entry to the chemistry of the perfluorinated (CF3)3Au fragment, the properties of which were analyzed with the aid of DFT methods and compared with those of the homologous non‐fluorinated (CH3)3Au moiety. It was found that reductive elimination of CX3−CX3 in the former (X=F) requires a much higher energy barrier than in the latter (X=H) and is therefore considerably less favored. This can be considered as one of the main features underlying the significantly higher stability associated to the (CF3)3Au fragment and its derivatives. This unsaturated, 14‐electron species can be stabilized by coordination of any of the halide ligands, including fluoride. In fact, the whole series of anionic [PPh4][(CF3)3AuX] complexes (X=F, Cl, Br, I, CN) has now been isolated and conveniently characterized. Evidence for intermolecular decomposition pathways upon thermolysis in the condensed phase is presented.
Cancer‐Specific, Intracellular, Reductive Activation of Anticancer PtIV Prodrugs
Authors: Reshetnikov Viktor , Daum Steffen , Mokhir Andriy 
Published: March 2017

AbstractBecause cellular uptake of anticancer PtII and PtIV drugs occurs by different mechanisms, the latter ones can exhibit substantial activity towards cells, which have either intrinsic or acquired resistance towards PtII drugs. However, this positive effect is diminished due to reductive activation of PtIV drugs in extracellular space that can be one of the reasons why they have not yet been approved for clinical use despite over 60 clinical trials conducted worldwide. Herein, we suggest a solution to this problem by achieving highly specific intracellular versus extracellular prodrug reduction. In particular, we prepared a hybrid PtIV prodrug containing two pro‐reductants. This hybrid was uptaken by cells, the pro‐reductants were activated in the cancer‐specific microenvironment (high H2O2), and reduced PtIV by two one‐electron transfers. The drug formed in this way induced cell death both in cisplatin‐sensitive and resistant cell lines, but remained nontoxic to normal cells.
Design, Synthesis, Biological Evaluation and SARs of Novel Anthranilic Diamides Derivatives Containing Amide, Carbamate, Urea, and Thiourea Moieties
Authors: Liu Jingbo , Li Yuxin , Zhang Xiulan , Cheng Dandan , Wei Wei , Wu Changchun , Xie Yongtao , Xiong Lixia , Li Zhengming 
Published: March 2017

AbstractIn order to discover potential ryanodine receptor insecticides, 21 novel anthranilic diamides analogues (C, D, E, and F) containing amide, carbamate, urea, and thiourea moieties were designed and synthesized based on bioisosteric approach. The biological assays against oriental armyworm (Mythimna separata) and diamondback moth (Plutella xylostella) indicated that these compounds displayed moderate to excellent activities. Especially, compound D1 showed 100% larvicidal activities against oriental armyworm at 1.0 mg•L−1, equivalent to the standard chlorantraniliprole (100%, 1.0 mg•L−1). Moreover, the larvicidal activity of D1 against diamondback moth was 100% at 0.1 mg•L−1, more effective than that of chlorantraniliprole (90%, 0.1 mg•L−1). Therefore, D1 can be used as a new lead structure for the development of insecticidal agents. The preliminary structure‐activity relationship showed that the introduction od carbamate groups into 4‐position on the benzene ring of the N‐phenylpyrazole moiety has a positive effect on the larvicidal activities.
Synthesis of β‐tubulin occurs within chromatoid body of round spermatids
Authors: Fujii Yuki , Fujita Hideaki , Yokota Sadaki 
Published: March 2017

AbstractmRNAs for proteins required in elongated spermatids are considered to be transcribed at an early stage and stored in cytoplasm, presumably in chromatoid body (CB), one type of nuage component (a unique structure that appears and disappears during spermatogenesis), because transcription of genes does not occur at late stages. In elongated spermatids, a large amount of tubulin molecules is required to form microtubules of manchette and flagellum. To investigate the possible role of CB in translation of tubulin mRNA, we performed immunofluorescence and immunoelectron microscopic localization studies of α‐ and β‐tubulin in rat spermatogenic cells. β‐tubulin was detected in CB, but α‐tubulin was not. Other nuage components present in pachytene spermatocytes (ISPG, IMC, SB) were negative for both α‐ and β‐tubulin. Our findings suggest that: (i) β‐tubulin in round spermatids is translated within the CB, whereas α‐tubulin is not; (ii) αβ‐heterodimers are formed outside CB and incorporated into microtubules of manchette and flagellum.
Improving Nonspecific Binding and Solubility: Bicycloalkyl Groups and Cubanes as para‐Phenyl Bioisosteres
Authors: Auberson Yves P. , Brocklehurst Cara , Furegati Markus , Fessard Thomas C. , Koch Guido , Decker Andrea , La Vecchia Luigi , Briard Emmanuelle 
Published: March 2017

AbstractBicycloalkyl groups have been previously described as phenyl group bioisosteres. This article describes the synthesis of new building blocks allowing their introduction into complex molecules, and explores their use as a means to modify the physicochemical properties of drug candidates and improve the quality of imaging agents. In particular, the replacement of an aromatic ring with a bicyclo[1.1.1]pentane‐1,3‐diyl (BCP) group improves aqueous solubility by at least 50‐fold, and markedly decreases nonspecific binding (NSB) as measured by CHI(IAM), the chromatographic hydrophobicity index on immobilized artificial membranes. Structural variations with the bicyclo[2.2.2]octane‐1,4‐diyl group led to more lipophilic molecules and did not show the same benefits regarding NSB or solubility, whereas substitutions with cubane‐1,4‐diyl showed improvements for both parameters. These results confirm the potential advantages of both BCP and cubane motifs as bioisosteric replacements for optimizing para‐phenyl‐substituted molecules.
Nanostructured Multilayer Films Assembled from Poly(dopamine)‐Coated Carbon Nanotubes for Controlling Cell Behavior
Authors: Li Bo‐chao , Ren Ke‐feng , Zhang He , Jia Fan , Wang Jin‐lei , Chang Hao , Wang Yun‐bing , Ji Jian 
Published: March 2017

AbstractNano‐topographic surfaces have been used as an effective tool to control cell behavior such as adhesion and proliferation. In this study, multilayer films with nano‐topographic features were fabricated by alternatively assembling poly(l‐lysine) (PLL) and poly(dopamine)‐coated carbon nanotubes (CNTs@PDA) layers. The growth of PLL/CNTs@PDA film presented a perfect linear relationship with the number of bilayers. A nanostructured morphology with interpenetrating CNT networks was observed by scanning electron microscopy (SEM). Adhesion and proliferation of endothelial cells (ECs) and smooth muscle cells (SMCs) on the PLL/CNTs@PDA multilayer films have been evaluated. The films support initial adhesion of both ECs and SMCs. Interestingly, the PLL/CNTs@PDA multilayer films were found to promote proliferation of SMCs and inhibited proliferation of ECs. Further, pheochromocytoma (PC12) cells were employed to evaluate the influence of PLL/CNTs@PDA multilayer films on the outgrowth of synapses. We found that the nanostructured surface significantly promoted the synapses of PC12 cell growth and formation. Our findings suggest that cytophilic surfaces with the nanostructured morphology have diverse effects on different cells, which sheds light on new design of biomaterial surfaces in cell‐based applications.
Application of Azulene in Constructing Organic Optoelectronic Materials: New Tricks for an Old Dog
Authors: Xin Hanshen , Gao Xike 
Published: March 2017

AbstractAzulene, as an isomer of naphthalene, has received increasing interest due to its unique chemical structure and unusual photophysical properties, including a large dipole moment of 1.08 D, a narrow energy gap between the HOMO and LUMO, and abnormal fluorescence (anti‐Kasha's rule) from the second excited state to the ground state. In this Minireview, the general strategies and representative synthetic methods for the preparation and functionalization of azulene and its derivatives are presented, and then the application of azulene‐based optoelectronic materials in organic field‐effect transistors and solar cells is discussed. Finally, the challenges and outlook on developing azulene‐based optoelectronic materials are discussed, together with several key points on molecular design and synthesis.
Understanding the Changes to Biomass Surface Characteristics after Ammonia and Organosolv Pretreatments by Using Time‐of‐Flight Secondary‐Ion Mass Spectrometry (TOF‐SIMS)
Authors: Tolbert Allison K. , Yoo Chang Geun , Ragauskas Arthur J. 
Published: March 2017

AbstractSurface characteristic changes to poplar after ammonia and organosolv pretreatments were investigated by means of time‐of‐flight secondary‐ion mass spectrometry (TOF‐SIMS) analysis. Whereas normalized total polysaccharides and lignin contents on the surface differed from bulk chemical compositions, the surface cellulose ions detected by TOF‐SIMS showed the same value trend as the cellulose content in the biomass. In addition, the lignin syringyl/guaiacyl ratio according to TOF‐SIMS results showed the same trend as the ratio measured by means of NMR spectroscopic analysis, even though the ratio scales for each method were different. A similar correlation was determined between the surface cellulose and glucose release after enzymatic hydrolysis. These results demonstrate that surface characterization using TOF‐SIMS can provide important information about the effects of pretreatment on biomass properties and its hydrolysis.
Decarboxylative Alkynylation of Biomass‐Derived Compounds by Metal‐Free Visible Light Photocatalysis
Authors: Schwarz Johanna , König Burkhard 
Published: March 2017

AbstractA mild method for decarboxylative C−C bond formation between natural carboxylic acids and alkynes is reported. Activation of a very broad scope of carboxylic acids derived from renewable resources is achieved by esterification to N‐(acyloxy)phthalimides. The cross‐coupling with acetylenic sulfones proceeds under irradiation with green light (528 nm) in the presence of the organic photocatalyst eosin Y and provides a metal‐free, environmentally friendly and inexpensive alternative to known decarboxylative alkynylations.
Integrating Eco‐Innovations and Stakeholder Engagement for Sustainable Development and a Social License to Operate
Authors: Provasnek Anna Katharina , Sentic Anton , Schmid Erwin 
Published: March 2017

AbstractEco‐innovations of corporations are seen to contribute to the mitigation of negative impacts on the natural environment. However, despite environmental gains, some eco‐innovations fail in the marketplace while others succeed. We propose a framework that reflects the connection between eco‐innovations and their social license to operate. Corporations can increase the market success of eco‐innovations if they can gain a social license to operate based on fair and trustworthy stakeholder engagement shaped by the context of their societal environment. Eco‐innovations can be transformed following management steps of an internal and external evaluation, the analysis of companies' interactional status, and conformation activities for the introduction of sustainability‐oriented innovations. We conclude that the successful transformation of eco‐innovations requires the inclusion of social factors, such as stakeholders' multiple claims, to secure a social license to operate and thereby even reduce costs by avoiding sketchy corporate social responsibility measures. Copyright © 2017 John Wiley & Sons, Ltd and ERP Environment
Eco‐Efficient Synthesis of Highly Porous CoCO3 Anodes from Supercritical CO2 for Li+ and Na+ Storage
Authors: Li Hui‐Ying , Tseng Chuan‐Ming , Yang Cheng‐Hsien , Lee Tai‐Chou , Su Ching‐Yuan , Hsieh Chien‐Te , Chang Jeng‐Kuei 
Published: March 2017

AbstractAn eco‐efficient synthetic route for the preparation of high‐performance carbonate anodes for Li+ and Na+ batteries is developed. With supercritical CO2 (scCO2) as the precursor, which has gas‐like diffusivity, extremely low viscosity, and near‐zero surface tension, CoCO3 particles are uniformly formed and tightly connected on graphene nanosheets (GNSs). This synthesis can be conducted at 50 °C, which is considerably lower than the temperature required for conventional preparation methods, minimizing energy consumption. The obtained CoCO3 particles (ca. 20 nm in diameter), which have a unique interpenetrating porous structure, can increase the number of electroactive sites, promote electrolyte accessibility, shorten ion diffusion length, and readily accommodate the strain generated upon charging/discharging. With a reversible capacity of 1105 mAh g−1, the proposed CoCO3/GNS anode shows an excellent rate capability, as it can deliver 745 mAh g−1 in 7.5 min. More than 98 % of the initial capacity is retained after 200 cycles. These properties are clearly superior to those of previously reported CoCO3‐based electrodes for Li+ storage, indicating the merit of our scCO2‐based synthesis, which is facile, green, and can be easily scaled up for mass production.
Ghost of invasion past: legacy effects on community disassembly following eradication of an invasive ecosystem engineer
Authors: Reynolds Pamela L. , Glanz Jess , Yang Sylvia , Hann Courtney , Couture Jessica , Grosholz Edwin 
Published: March 2017

AbstractBy changing ecosystem processes and altering the physical landscape, invasive ecosystem engineers can have substantial impacts on ecosystem functions and human economies and may facilitate other non‐native species. Eradication programs in terrestrial and aquatic systems aim to reverse the impacts of invasive species and return the system to its pre‐invasion conditions. Despite an extensive focus on the impacts of both native and non‐native ecosystem engineers, the consequences of removing invasive ecosystem engineers, particularly in coastal ecosystems, are largely unknown. In this study, we quantified changes in a benthic community following the eradication of the invasive ecosystem engineer, hybrid cordgrassSpartina, in San Francisco Bay, California. We used field experimental manipulations to test for persistent effects of both aboveground and belowground structural modifications of the invasive plant on the benthic community. We found significant effects of the invasive plant more than four years following eradication. Experimental modification of the above‐ vs. belowground structure of this ecosystem engineer revealed taxonomic specific effects resulting in hysteresis in the recovery of the benthic food webs. We found that these “legacy effects” resulted from two specific mechanisms: (1) delayed breakdown of belowground structures (stems, roots) and (2) persistence of other invasive species whose invasion was facilitated by the ecosystem engineer. Both of these mechanisms are likely to occur in similar systems where belowground structures breakdown more slowly or where other associated long‐lived invaders persist. Our work is among the first to quantify the slow rate of change in food web and community processes and the persistent legacy effects of an invasive ecosystem engineer in a coastal ecosystem. We suggest that this delayed transition to pre‐invasion conditions could resemble an alternate state that would be misidentified without a sufficient monitoring interval or recovery duration, with consequences for future management and restoration activity planning.
Atlantic frugivory: a plant–frugivore interaction data set for the Atlantic Forest
Authors: Bello Carolina , Galetti Mauro , Montan Denise , Pizo Marco A. , Mariguela Tatiane C. , Culot Laurence , Bufalo Felipe , Labecca Fabio , Pedrosa Felipe , Constantini Rafaela , Emer Carine , Silva Wesley R. , da Silva Fernanda R. , Ovaskainen Otso , Jordano Pedro 
Published: March 2017

AbstractThe data set provided here includes 8,320 frugivory interactions (records of pairwise interactions between plant and frugivore species) reported for the Atlantic Forest. The data set includes interactions between 331 vertebrate species (232 birds, 90 mammals, 5 fishes, 1 amphibian, and 3 reptiles) and 788 plant species. We also present information on traits directly related to the frugivory process (endozoochory), such as the size of fruits and seeds and the body mass and gape size of frugivores. Data were extracted from 166 published and unpublished sources spanning from 1961 to 2016. While this is probably the most comprehensive data set available for a tropical ecosystem, it is arguably taxonomically and geographically biased. The plant families better represented are Melastomataceae, Myrtaceae, Moraceae, Urticaceae, and Solanaceae. Myrsine coriacea, Alchornea glandulosa, Cecropia pachystachya, and Trema micrantha are the plant species with the most animal dispersers (83, 76, 76, and 74 species, respectively). Among the animal taxa, the highest number of interactions is reported for birds (3,883) followed by mammals (1,315). The woolly spider monkey or muriqui, Brachyteles arachnoides, and Rufous‐bellied Thrush, Turdus rufiventris, are the frugivores with the most diverse fruit diets (137 and 121 plants species, respectively). The most important general patterns that we note are that larger seeded plant species (>12 mm) are mainly eaten by terrestrial mammals (rodents, ungulates, primates, and carnivores) and that birds are the main consumers of fruits with a high concentration of lipids. Our data set is geographically biased, with most interactions recorded for the southeast Atlantic Forest.
An experimental test of the habitat‐amount hypothesis for saproxylic beetles in a forested region
Authors: Seibold Sebastian , Bässler Claus , Brandl Roland , Fahrig Lenore , Förster Bernhard , Heurich Marco , Hothorn Torsten , Scheipl Fabian , Thorn Simon , Müller Jörg 
Published: March 2017

AbstractThe habitat‐amount hypothesis challenges traditional concepts that explain species richness within habitats, such as the habitat‐patch hypothesis, where species number is a function of patch size and patch isolation. It posits that effects of patch size and patch isolation are driven by effects of sample area, and thus that the number of species at a site is basically a function of the total habitat amount surrounding this site. We tested the habitat‐amount hypothesis for saproxylic beetles and their habitat of dead wood by using an experiment comprising 190 plots with manipulated patch sizes situated in a forested region with a high variation in habitat amount (i.e., density of dead trees in the surrounding landscape). Although dead wood is a spatio‐temporally dynamic habitat, saproxylic insects have life cycles shorter than the time needed for habitat turnover and they closely track their resource. Patch size was manipulated by adding various amounts of downed dead wood to the plots (~800 m³ in total); dead trees in the surrounding landscape (~240 km2) were identified using airborne laser scanning (light detection and ranging). Over 3 yr, 477 saproxylic species (101,416 individuals) were recorded. Considering 20–1,000 m radii around the patches, local landscapes were identified as having a radius of 40–120 m. Both patch size and habitat amount in the local landscapes independently affected species numbers without a significant interaction effect, hence refuting the island effect. Species accumulation curves relative to cumulative patch size were not consistent with either the habitat‐patch hypothesis or the habitat‐amount hypothesis: several small dead‐wood patches held more species than a single large patch with an amount of dead wood equal to the sum of that of the small patches. Our results indicate that conservation of saproxylic beetles in forested regions should primarily focus on increasing the overall amount of dead wood without considering its spatial arrangement. This means dead wood should be added wherever possible including in local landscapes with low or high dead‐wood amounts. For species that have disappeared from most forests owing to anthropogenic habitat degradation, this should, however, be complemented by specific conservation measures pursued within their extant distributional ranges.