bluuebunny/crossref_metadata_2025_split huggingface dataset:
Photocatalytic Decontamination of Wastewater Containing Organic Dyes by Metal–Organic Frameworks and their Derivatives
Authors: Wu Zhibin , Yuan Xingzhong , Zhang Jin , Wang Hou , Jiang Longbo , Zeng Guangming 
Published: August 2016

AbstractPhotoactive metal–organic frameworks (MOFs) have lately emerged as a class of crystalline porous materials, which provides an advanced platform to develop catalysts for the photocatalytic decolorization of wastewater. Controllable integration of pure MOFs into other active materials creates fabrication protocols for new multifunctional hybrids with superior photocatalytic properties for dye degradation into individual components, and the calcination of transition‐metal MOF precursors affords a convenient and practical route for preparation of nanosized photocatalysts with novel structures and good purity. Although the application of pure MOFs for organic pollutant decomposition has been reviewed previously, there have been significant advances in diverse MOF‐based composites and their derivatives for dye degradation, which have rarely been reviewed. This review aims to fill this gap and discuss the various influencing factors, the reaction kinetics, and mechanisms of dye degradation, considering the period from 2014 to 2016. Finally, the challenges and outlooks for dye decomposition by MOF‐based materials are suggested.
Carbon Self‐Doping Induced Activation of n–π* Electronic Transitions of g‐C3N4 Nanosheets for Efficient Photocatalytic H2 Evolution
Authors: Su Feng‐Yun , Xu Cheng‐Qun , Yu Yu‐Xiang , Zhang Wei‐De 
Published: August 2016

AbstractThis paper reports a facile one‐pot synthesis strategy to prepare carbon self‐doped g‐C3N4 (C‐g‐C3N4) nanosheets by using supramolecular networks consisting of cyanuric acid, ethylene glycol (EG), and melamine (CEM) bonded through hydrogen bonding as the thermal polycondensation precursor, in which EG serves as a solvent for cyanuric acid and melamine, and as a source of the doped carbon simultaneously. The threedimensional structure of CEM resulted in the distortion of C‐g‐C3N4, which is capable of motivating the n–π* electronic transition involving the N lone pairs to give an additional absorption region from 450 to 600 nm. The hydrogen evolution rate of C‐g‐C3N4 reaches 73.09 μmol h−1, which is about 15 times of that over the g‐C3N4 obtained from direct thermal polycondensation of melamine owing to its extended light harvesting and faster separation of photogenerated electrons and holes.
A Heterogeneous Photocatalytic Hydrogen Evolution Dyad: [(tpy
Authors: Zhao Weiwei , Huang Yi , Liu Yang , Cao Liming , Zhang Fang , Guo Yamei , Zhang Bin 
Published: August 2016

AbstractThe development of an artificial heterogeneous dyad by covalently anchoring a hydrogen‐evolving molecule catalyst to a semiconductor photosensitizer through a bridging ligand is highly challenging. Herein, we adopt the inorganic–organic hybrid CdS–DETA NSs (DETA=diethylenetriamine, NSs=nanosheets) as initial matrix to successfully construct an imine bond (‐CH=N‐) linked heterogeneous dyad [CdS−N=CH−Ni] through the condensation reaction between the amino groups of CdS–DETA and the aldehyde group of the water reduction molecular catalyst, [(tpy‐CHO)2Ni]Cl2 (tpy=terpyridine). The [CdS−N=CH−Ni] enables a turnover number (TON) of about 43 815 versus Ni catalysts and an initial turnover frequency (TOF) of approximately 0.47 s−1 in 26 h under visible‐light irradiation (λ>420 nm). The apparent quantum yield (AQY) reaches (9.9±0.8) % at 420 nm. Under optical conditions, the [CdS−N=CH−Ni] can achieve a considerable amount of hydrogen production, 507.1±27 μmol H2 for 6 h, which is 1.27 times that generated from the mechanically mixed system of CdS–DETA NSs and [(tpy‐CH=NR)2Ni]Cl2 (III) under otherwise identical conditions. Furthermore, its TON value based on Ni species is also higher than that of the mixed system of CdS–DETA and III.
Surface Chemistry of tert‐Butylphosphine (TBP) on Si(001) in the Nucleation Phase of Thin‐Film Growth
Authors: Stegmüller Andreas , Werner Katharina , Reutzel Marcel , Beyer Andreas , Rosenow Phil , Höfer Ulrich , Stolz Wolfgang , Volz Kerstin , Dürr Michael , Tonner Ralf 
Published: August 2016

AbstractWe combine density functional theory calculations and scanning tunneling microscopy investigations to identify the relevant chemical species and reactions in the nucleation phase of chemical vapor deposition. tert‐Butylphosphine (TBP) was deposited on a silicon substrate under conditions typical for surface functionalization and growth of semiconductor materials. On the activated hydrogen‐covered surface H/Si(001) it forms a strong covalent P−Si bond without loss of the tert‐butyl group. Calculations show that site preference for multiple adsorption of TBP is influenced by steric repulsion of the adsorbate's bulky substituent. STM imaging furthermore revealed an anisotropic distribution of TBP with a preference for adsorption perpendicular to the surface dimer rows. The adsorption patterns found can be understood by a mechanism invoking stabilization of surface hydrogen vacancies through electron donation by an adsorbate. The now improved understanding of nucleation in thin‐film growth may help to optimize molecular precursors and experimental conditions and will ultimately lead to higher quality materials.
α‐Aminoxy Oligopeptides: Synthesis, Secondary Structure, and Cytotoxicity of a New Class of Anticancer Foldamers
Authors: Diedrich Daniela , Moita Ana J. Rodrigues , Rüther Anja , Frieg Benedikt , Reiss Guido J. , Hoeppner Astrid , Kurz Thomas , Gohlke Holger , Lüdeke Steffen , Kassack Matthias U. , Hansen Finn K. 
Published: August 2016

Abstractα‐Aminoxy peptides are peptidomimetic foldamers with high proteolytic and conformational stability. To gain an improved synthetic access to α‐aminoxy oligopeptides we used a straightforward combination of solution‐ and solid‐phase‐supported methods and obtained oligomers that showed a remarkable anticancer activity against a panel of cancer cell lines. We solved the first X‐ray crystal structure of an α‐aminoxy peptide with multiple turns around the helical axis. The crystal structure revealed a right‐handed 28‐helical conformation with precisely two residues per turn and a helical pitch of 5.8 Å. By 2D ROESY experiments, molecular dynamics simulations, and CD spectroscopy we were able to identify the 28‐helix as the predominant conformation in organic solvents. In aqueous solution, the α‐aminoxy peptides exist in the 28‐helical conformation at acidic pH, but exhibit remarkable changes in the secondary structure with increasing pH. The most cytotoxic α‐aminoxy peptides have an increased propensity to take up a 28‐helical conformation in the presence of a model membrane. This indicates a correlation between the 28‐helical conformation and the membranolytic activity observed in mode of action studies, thereby providing novel insights in the folding properties and the biological activity of α‐aminoxy peptides.
Oxidation Chemistry of Inorganic Benzene Complexes
Authors: Fleischmann Martin , Dielmann Fabian , Balázs Gábor , Scheer Manfred 
Published: August 2016

AbstractThe oxidation of the 28 VE cyclo‐E6 triple‐decker complexes [(CpRMo)2(μ,η6:η6‐E6)] (E=P, CpR=Cp(2 a), Cp*(2 b), CpBn(2 c)=C5(CH2Ph)5; E=As, CpR=Cp*(3)) by Cu+ or Ag+ leads to cationic 27 VE complexes that retain their general triple‐decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry (CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single‐crystal X‐ray diffraction. The cyclo‐E6 middle decks of the oxidized complexes are distorted to a quinoid (2 a) or bisallylic (2 b, 2 c, 3) geometry. DFT calculations of 2 a, 2 b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ‐system of the cyclo‐E6 ligands in 2 a–3. Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization.
A Photoswitchable Fluorophore for the Real‐Time Monitoring of Dynamic Events in Living Organisms
Authors: Zhang Yang , Tang Sicheng , Sansalone Lorenzo , Baker James D. , Raymo Françisco M. 
Published: August 2016

AbstractThis study reports the synthesis of a photoactivatable fluorophore with optimal photochemical and photophysical properties for the real‐time tracking of motion in vivo. The photoactivation mechanism designed into this particular compound permits the conversion of an emissive reactant into an emissive product with resolved fluorescence, under mild illumination conditions that are impossible to replicate with conventional switching schemes based on bleaching. Indeed, the supramolecular delivery of these photoswitchable probes into the cellular blastoderm of Drosophila melanogaster embryos allows the real‐time visualization of translocating molecules with no detrimental effects on the developing organisms. Thus, this innovative mechanism for fluorescence photoactivation can evolve into a general chemical tool to monitor dynamic processes in living biological specimens.
Rhodium‐Catalyzed Enantioselective Intramolecular Hydroacylation of Trisubstituted Alkenes
Authors: Johnson Kirsten F. , Schneider Eugene A. , Schumacher Brian P. , Ellern Arkady , Scanlon Joseph D. , Stanley Levi M. 
Published: August 2016

AbstractWe report the first examples of transition metal‐catalyzed enantioselective alkene hydroacylations with 1,1,2‐trisubstituted alkenes. DFT and mechanistic studies are consistent with a reaction pathway for these rhodium‐catalyzed processes including intramolecular alkene hydroacylation and α‐epimerization to generate highly enantioenriched, polycyclic architectures. This reaction sequence enables the hydroacylation of 2‐(cyclohex‐1‐en‐1‐yl)benzaldehydes to form hexahydro‐9H‐fluoren‐9‐ones in moderate to high yields (68–91 %) with high enantioselectivities (up to 99 % ee) and diastereoselectivities (typically >20:1).
MgII‐Catalyzed Desymmetrization Reaction of meso‐Aziridines with Hydroxylamines: Synthesis of Novel Chiral 1,2‐Diamine Skeletons
Authors: Li Dan , Yang Dongxu , Wang Linqing , Liu Xihong , Jiang Xianxing , Wang Rui 
Published: August 2016

AbstractA MgII‐catalyzed desymmetrization reaction of meso‐aziridines with hydroxylamines has been disclosed for the first time. A series of novel chiral 1,2‐diamine skeletons were obtained in good yields and enantioselectivities. The reaction employed magnesium catalysis generated in situ from a simple oxazoline‐OH chiral ligand. Obviously, the diverse structures of the obtained chiral 1,2‐diamine compounds could allow them to be potential chiral ligands in future catalytic asymmetric synthesis studies.
Unusual Reactivity of Sodium Tetramesityltetraphosphanediide towards Cyclohexyl Isocyanide
Authors: Adhikari Anup K. , Sárosi Menyhárt B. , Grell Toni , Lönnecke Peter , Hey‐Hawkins Evamarie 
Published: August 2016

AbstractThe reaction of [Na2(thf)4(P4Mes4)] (Mes=2,4,6‐Me3C6H2) with cyclohexyl isocyanide (2:5) resulted in the formation of the heterocyclic N‐(tetramesityltetraphosphacyclopentylidene)cyclohexylamine [cyclo‐{P4Mes4C(NCy)}] (2) (30–35 %), the unusual 1,3,5‐triphospha‐1,4‐pentadiene (3) (40–45 %), and small amounts of the dimeric iminomethylidenephosphane cyclo‐{PMesC(NCy)}2 (4). With catalytic amounts of AgBF4, 2 was the major product. The reaction of 2 with [CuBr(SMe2)] (1:1) produced bromido‐bridged dimeric CuI complex 5. Molecular structures of compounds 3, 4, and 5 were obtained.
Bewertung von Adsorbenzien zur Kraftstoffdampfnachbehandlung in Adsorbern für Personenkraftwagen
Authors: Hedwig Michael , Breitkopf Cornelia 
Published: August 2016

AbstractDie Herausforderungen an die Kraftstoffdampfnachbehandlung in Adsorbern ottomotorisch betriebener PKW steigen infolge zunehmender Emissionsrestriktionen an. Die Arbeitskapazität des Adsorbers ist maßgeblich durch die Sorptionsfähigkeit des darin enthaltenen Adsorbens limitiert und von dem zu adsorbierenden Kraftstoffdampf abhängig. Anhand einer Charakterisierung repräsentativer Kraftstoffe werden hier die dazugehörigen Adsorptivgemische erschlossen. Darauf aufbauend erfolgt in Form einer Gegenüberstellung charakteristischer Stoffeigenschaften eine Bewertung und Auswahl geeigneter Absorbenzien.
Complete identification of four giant interneurons supplying mushroom body calyces in the cockroach Periplaneta americana
Authors: Takahashi Naomi , Katoh Ko , Watanabe Hidehiro , Nakayama Yuta , Iwasaki Masazumi , Mizunami Makoto , Nishino Hiroshi 
Published: August 2016

ABSTRACTGlobal inhibition is a fundamental physiological mechanism that has been proposed to shape odor representation in higher‐order olfactory centers. A pair of mushroom bodies (MBs) in insect brains, an analog of the mammalian olfactory cortex, are implicated in multisensory integration and associative memory formation. With the use of single/multiple intracellular recording and staining in the cockroach Periplaneta americana, we succeeded in unambiguous identification of four tightly bundled GABA‐immunoreactive giant interneurons that are presumably involved in global inhibitory control of the MB. These neurons, including three spiking neurons and one nonspiking neuron, possess dendrites in termination fields of MB output neurons and send axon terminals back to MB input sites, calyces, suggesting feedback roles onto the MB. The largest spiking neuron innervates almost exclusively the basal region of calyces, while the two smaller spiking neurons and the second‐largest nonspiking neuron innervate more profusely the peripheral (lip) region of the calyces than the basal region. This subdivision corresponds well to the calycal zonation made by axon terminals of two populations of uniglomerular projection neurons with dendrites in distinct glomerular groups in the antennal lobe. The four giant neurons exhibited excitatory responses to every odor tested in a neuron‐specific fashion, and two of the neurons also exhibited inhibitory responses in some recording sessions. Our results suggest that two parallel olfactory inputs to the MB undergo different forms of inhibitory control by the giant neurons, which may, in turn, be involved in different aspects of odor discrimination, plasticity, and state‐dependent gain control. J. Comp. Neurol. 525:204–230, 2017. © 2016 Wiley Periodicals, Inc.
Synthesis and Photoinduced Electron‐Transfer Reactions in a La2@Ih‐C80–Phenoxazine Conjugate
Authors: Akasaka Takeshi , Nakata Akira , Rudolf Marc , Wang Wei‐Wei , Yamada Michio , Suzuki Mitsuaki , Maeda Yutaka , Aoyama Ryo , Tsuchiya Takahiro , Nagase Shigeru , Guldi Dirk M. 
Published: August 2016

AbstractA newly designed electron donor–acceptor conjugate consisting of an endohedral dimetallofullerene (La2@Ih‐C80) and phenoxazine (POZ) was successfully synthesized under Prato conditions. Our results document that the 1,3‐dipolar cycloaddition took place across the [5,6] junction to afford exclusively the corresponding [5,6] cycloadduct. The structure of the conjugate was characterized by means of NMR spectroscopy, absorption spectroscopy, and electrochemical studies. Computational calculations suggest that the electron density of the highest occupied molecular orbital (HOMO) is distributed on the POZ moiety, whereas that of the lowest unoccupied molecular orbital (LUMO) is located at the endohedral La atoms, leading to efficient separation of the HOMO and LUMO in the conjugate. Time‐resolved absorption spectroscopic investigations and spectroelectrochemical measurements corroborate the formation of the energetically low‐lying (La2@Ih‐C80).−–(POZ).+ radical‐ion‐pair state by means of ultrafast through‐space electron transfer.
Fe/W Co‐Doped BiVO4 Photoanodes with a Metal–Organic Framework Cocatalyst for Improved Photoelectrochemical Stability and Activity
Authors: Jiao Zhengbo , Zheng Jingjing , Feng Chenchen , Wang Zeli , Wang Xuesen , Lu Gongxuan , Bi Yingpu 
Published: August 2016

AbstractBiVO4 has been identified as one of the excellent visible light responsive photoanodes for use in photoelectrochemical (PEC) water splitting. However, pristine BiVO4 usually exhibits relative low photocatalytic properties owing to insufficient charge separation and transport characteristics. Although the marginal n‐type doping of higher valence ions can obviously raise the photocurrent value, it by no means improves the PEC stability. In this work, we successfully enhanced the PEC stability of BiVO4 by doping Fe ions in substitution of Bi. Density functional theory calculations have illustrated that Fe‐doping would result in an impurity band in the forbidden gap, and thus narrow its energy gap. More importantly, Fe‐doping can synergize with other means to further improve the PEC activities of BiVO4. Therefore, we fabricated a nanoporous Fe/W co‐doped BiVO4 photoelectrode, and then loaded the metal–organic framework (MOF) MIL‐100(Fe) as cocatalyst to further promote the separation of charge carriers. To the best of our knowledge, MOFs have not yet been utilized as a cocatalyst to facilitate the charge separation, which could increase the photocurrent density of Fe/W co‐doped BiVO4.
Thermal sensitivity and the role of behavior in driving an intertidal predator–prey interaction
Authors: Monaco Cristián J. , Wethey David S. , Helmuth Brian 
Published: August 2016

AbstractEnvironmental stress models (ESM) provide a useful framework to study the direct and indirect ecological drivers of community diversity and resilience.ESMs make predictions about the relative importance of structuring processes (e.g., predation) based on the relative stress suffered by consumers and prey. Their practical application, i.e., determining the conditions under which consumers and prey performance is more negatively affected, has been limited because the roles of behavior and physiology are not usually considered. We examined the role of thermal sensitivity and behavior on the thermal performance of the rocky intertidal predatorPisaster ochraceusand its main preyMytilus californianus. We propose a novel framework that merges thermal performance curves (TPC) with observations of microhabitat use to provide a realistic perspective of the relative physiological conditions of predator and prey. First, by deriving aquatic and aerialTPCs for both species and from two sites, we found differences in parameter values that in some cases correspond to the individuals’ origins. Second, we calculated realized thermal performance in the field by combiningTPCs with body temperatures recorded with biomimetic sensors. Notably, thermal performance ofPisasterwas higher than that forMytilus(i.e., prey‐stress model), contrary to previous expectations based on caging experiments. Third, these estimates of thermal performance corresponded loosely with a measured indicator of overall physiological condition (body mass index,BMI) and a marker for extreme thermal stress (heat‐shock proteins 70 kDa), suggesting that environmental drivers other than temperature, such as food supply, must be considered. We found no evidence thatPisastermovement significantly influences thermal performance under typical conditions, suggesting instead that its preference for sheltered microhabitats provides a mechanism for avoiding exposure to extreme environmental conditions. Through the application ofTPCs andESMs, this study provides a unique perspective on the importance of physiology and behavior in driving the sensitivity of species interactions to environmental change. Crucially, this framework allowed clarifying that this system behaves as a prey‐ instead of consumer‐stress model, which may also apply to many other ectotherm species interactions.
Predicting reach‐specific properties of fluvial terraces to guide future fieldwork. A case study for the Late Quaternary River Allier (France) with the FLUVER2 model
Authors: Veldkamp Tom , Schoorl Jeroen M. , Viveen Willem 
Published: August 2016

AbstractNumerical models have not yet systematically been used to predict properties of fluvial terrace records in order to guide fieldwork and sampling. This paper explores the potential of the longitudinal profile model FLUVER2 to predict testable field properties of the relatively well‐studied, Late Quaternary Allier system in France. For the Allier terraces an overlapping 14C and U‐series chronology as well as a record of 10Be erosion rates exist. The FLUVER2 modelling exercise is focused on the last 50 ka of the upper Allier reach because for this location and period the constraints of the available dating techniques are tightest. A systematic calibration based on terrace occurrence and thicknesses was done using three internal parameters related to (1) the sediment erodibility; (2) the sediment transport distance; and (3) the sediment supply derived from the surrounding landscape. As external model inputs, the best available, reconstructed, tectonic, climatic and base‐level data were used. Calibrated model outputs demonstrate a plausible match with the existing fluvial record. Validation of model output was done by comparing the modelled and measured timing of aggradation and incision phases for the three locations. The modelled range of landscape erosion rates showed a reasonably good match with existing erosion rate estimates derived from 10Be measurements of fluvial sands. The quasi‐validated model simulation was subsequently used to make new testable predictions about the timing and location of aggradation and erosion phases for three locations along the Allier river. The validated simulations predict that along the Allier, reach‐specific dynamics of incision and aggradation, related to the variations in sediment supply by major tributaries, cause relevant differences in the local fluvial terrace stratigraphy. Copyright © 2016 John Wiley & Sons, Ltd.
Platinum Nanoparticles Anchored on TiO2/C Nanowires as a High Performance Catalyst for Hydrogen Peroxide Eletroreduction
Authors: Cai Z. , Zhang D. , Cheng K. , Song C. , Li Y. , Ye K. , Yan P. , Cao D. , Wang G. 
Published: August 2016

AbstractIn this paper, we employed the as‐prepared TiO2/C core/shell nanoarrays (TiO2/C) obtained by a facile thermal evaporation method as a three‐dimensional (3D) architecture to support Pt nanoparticles through an optimized electrodeposition process. The morphology and structure of the as‐prepared electrode are characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Its catalytic performance towards H2O2 electroreduction in basic medium is evaluated by linear sweep voltammetry (LSV) and chronoamperometry (CV). Results revealed that the electrode exhibits significantly high catalytic activity. The current density reached –0.172 A cm−2 in 1 mol dm−3 NaOH and 0.5 mol dm−3 H2O2 at –1.1 V (vs. Ag/AgCl). This high performance might be due to the 3D electrode architecture inheriting the high electronic conductivity from carbon shell and providing a short pathway for the ion diffusion, and the using of Pt owning an excellent catalytic activity.