bluuebunny/crossref_metadata_2025 huggingface dataset:
Stress and Damage Mitigation from Oriented Nanostructures within the Radular Teeth of Cryptochiton stelleri
Authors: Grunenfelder Lessa Kay , de Obaldia Enrique Escobar , Wang Qianqian , Li Dongsheng , Weden Brian , Salinas Christopher , Wuhrer Richard , Zavattieri Pablo , Kisailus David
Published: August 2014

Chiton are marine mollusks who use heavily mineralized and ultrahard teeth to feed on epilithic and endolithic algae on intertidal rocks. To fulfill this function, chiton teeth must be tough and wear‐resistant. Impressive mechanical properties are achieved in the chiton tooth through a hierarchically arranged composite structure consisting of a hard shell of organic‐encased and highly oriented nanostructured magnetite rods that surround a soft core of organic‐rich iron phosphate. Microscopic and spectroscopic analyses combined with finite element simulations are used to probe the ultrastructural features and uncover structure–mechanical property relationships in the fully mineralized teeth of the gumboot chiton Cryptochiton stelleri. By understanding the effects of the nanostructured architecture within the chiton tooth, abrasion‐resistant materials can be developed for tooling and machining applications, as well as coatings for equipment and medical implants.
Revisiting the Saito Photochemical Reduction and the Development of a One‐Pot Deoxygenation of Alcohols
Authors: Matsubara Ryosuke , Shin Yong‐Soon , Shimada Toshiyuki , Hayashi Masahiko
Published: August 2014

We have revisited the Saito photochemical reduction and established practical reaction conditions, under which the reduction of m‐(trifluoromethyl)benzoates, derived from secondary and tertiary alcohols, proceeds selectively at high concentration to afford the corresponding alkane products in good yields without formation of alkenes. A one‐pot deoxygenation of alcohols to alkanes has also been developed.
Transition‐metal dichalcogenides for spintronic applications
Authors: Zibouche Nourdine , Kuc Agnieszka , Musfeldt Janice , Heine Thomas
Published: August 2014

Spin‐orbit splitting in transition‐metal dichalcogenide monolayers is investigated on the basis of density‐functional theory within explicit two‐dimensional periodic boundary conditions. The spin‐orbit splitting reaches few hundred meV and increases with the size of the metal and chalcogen atoms, resulting in nearly 500 meV for WTe2. Furthermore, we find that similar to the band gap, spin‐orbit splitting changes drastically under tensile strain. In centrosymmetric transition metal dichalcogenide bilayers, spin‐orbit splitting is suppressed by the inversion symmetry. However, it could be induced if the inversion symmetry is explicitly broken, e.g. by a potential gradient normal to the plane, as it is present in heterobilayers (Rashba‐splitting). In such systems, the spin‐orbit splitting could be as large as for the heavier monolayer that forms heterobilayer. These properties of transition metal dichalcogenide materials suggest them for potential applications in opto‐, spin‐ and straintronics.
A Metal‐Free Strategy to Release Chemisorbed H2 from Hydrogenated Boron Nitride Nanotubes
Authors: Roy Lisa , Bhunya Sourav , Paul Ankan
Published: August 2014

Chemisorbed hydrogen on boron nitride nanotubes (BNNT) can only be released thermally at very high temperatures above 350 °C. However, no catalyst has been identified that could liberate H2 from hydrogenated BN nanotubes under moderate conditions. Using different density functional methods we predict that the desorption of chemisorbed hydrogen from hydrogenated BN nanotubes can be facilitated catalytically by triflic acid at low free‐energy activation barriers and appreciable rates under metal free conditions and mildly elevated temperatures (40–50 °C). Our proposed mechanism shows that the acid is regenerated in the process and can further facilitate similar catalytic release of H2, thus suggesting all the chemisorbed hydrogen on the surface of the hydrogenated nanotube can be released in the form of H2. These findings essentially raise hope for the development of a sustainable chemical hydrogen storage strategy in BN nanomaterials.
A First‐Cycle Coulombic Efficiency Higher than 100 % Observed for a Li2MO3 (M=Mo or Ru) Electrode
Authors: Jang Jihyun , Kim Youngjin , Chae Oh B. , Yoon Taeho , Kim Sang‐Mo , Kim Hyun‐seung , Park Hosang , Ryu Ji Heon , Oh Seung M.
Published: August 2014

The lithiation/de‐lithiation behavior of a ternary oxide (Li2MO3, where M=Mo or Ru) is examined. In the first lithiation, the metal oxide (MO2) component in Li2MO3 is lithiated by a conversion reaction to generate nano‐sized metal (M) particles and two equivalents of Li2O. As a result, one idling Li2O equivalent is generated from Li2MO3. In the de‐lithiation period, three equivalents of Li2O react with M to generate MO3. The first‐cycle Coulombic efficiency is theoretically 150 % since the initial Li2MO3 takes four Li+ ions and four electrons per formula unit, whereas the M component is oxidized to MO3 by releasing six Li+ ions and six electrons. In practice, the first‐cycle Coulombic efficiency is less than 150 % owing to an irreversible charge consumption for electrolyte decomposition. The as‐generated MO3 is lithiated/de‐lithiated from the second cycle with excellent cycle performance and rate capability.
Fabrication of Ultralong Hybrid Microfibers from Nanosheets of Reduced Graphene Oxide and Transition‐Metal Dichalcogenides and their Application as Supercapacitors
Authors: Sun Gengzhi , Liu Juqing , Zhang Xiao , Wang Xuewan , Li Hai , Yu Yang , Huang Wei , Zhang Hua , Chen Peng
Published: August 2014

Two‐dimensional materials have attracted increasing research interest owing to their unique electronic, physical, optical, and mechanical properties. We thus developed a general strategy for the fabrication of ultralong hybrid microfibers from a mixture of reduced graphene oxide and transition‐metal dichalcogenides (TMDs), including MoS2, TiS2, TaS2, and NbSe2. Furthermore, we prepared fiber‐based solid‐state supercapacitors as a proof‐of‐concept application. The performance of thus‐prepared supercapacitors was greatly improved by the introduction of the TMDs.
Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex
Authors: Konnick Michael M. , Hashiguchi Brian G. , Devarajan Deepa , Boaz Nicholas C. , Gunnoe T. Brent , Groves John T. , Gunsalus Niles , Ess Daniel H. , Periana Roy A.
Published: August 2014

Direct partial oxidation of methane, ethane, and propane to their respective trifluoroacetate esters is achieved by a homogeneous hypervalent iodine(III) complex in non‐superacidic (trifluoroacetic acid) solvent. The reaction is highly selective for ester formation (>99 %). In the case of ethane, greater than 0.5 M EtTFA can be achieved. Preliminary kinetic analysis and density functional calculations support a nonradical electrophilic CH activation and iodine alkyl functionalization mechanism.
Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry
Authors: Dong Jiajia , Krasnova Larissa , Finn M. G. , Sharpless K. Barry
Published: August 2014

Aryl sulfonyl chlorides (e.g. Ts‐Cl) are beloved of organic chemists as the most commonly used SVI electrophiles, and the parent sulfuryl chloride, O2SVICl2, has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the SVICl bond is exceedingly sensitive to reductive collapse yielding SIV species and Cl−. Fortunately, the use of sulfur(VI) fluorides (e.g., R‐SO2‐F and SO2F2) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid‐20th century. Here we seek to revive it, along with John Hyatt’s unnoticed 1979 full paper exposition on CH2CH‐SO2‐F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.
Synthesis of Nitrogen‐Doped ZigZag‐Edge Peripheries: Dibenzo‐9a‐azaphenalene as Repeating Unit
Authors: Berger Reinhard , Giannakopoulos Angelos , Ravat Prince , Wagner Manfred , Beljonne David , Feng Xinliang , Müllen Klaus
Published: August 2014

A bottom‐up approach toward stable and monodisperse segments of graphenes with a nitrogen‐doped zigzag edge is introduced. Exemplified by the so far unprecedented dibenzo‐9a‐azaphenalene (DBAPhen) as the core unit, a versatile synthetic concept is introduced that leads to nitrogen‐doped zigzag nanographenes and graphene nanoribbons.
Dissolution‐Enhanced Luminescent Bioassay Based on Inorganic Lanthanide Nanoparticles
Authors: Zhou Shanyong , Zheng Wei , Chen Zhuo , Tu Datao , Liu Yongsheng , Ma En , Li Renfu , Zhu Haomiao , Huang Mingdong , Chen Xueyuan
Published: August 2014

Conventional dissociation‐enhanced lanthanide fluoroimmunoassays (DELFIA) using molecular probes suffer from a low labeling ratio of lanthanide ions (Ln3+) per biomolecule. Herein, we develop a unique bioassay based on the dissolution‐enhanced luminescence of inorganic lanthanide nanoparticles (NPs). As a result of the highly concentrated Ln3+ ions in a single Ln3+ NP, an extremely high Ln3+ labeling ratio can be achieved, which amplifies significantly the luminescence signal and thus improves the detection sensitivity compared to DELFIA. Utilizing sub‐10 nm NaEuF4 NPs as dissolution‐enhanced luminescent nanoprobes, we demonstrate the successful in vitro detection of carcinoembryonic antigen (CEA, an important tumor marker) in human serum samples with a record‐low detection limit of 0.1 pg mL−1 (0.5 fM). This value is an improvement of approximately 3 orders of magnitude relative to that of DELFIA. The dissolution‐enhanced luminescent bioassay shows great promise in versatile bioapplications, such as ultrasensitive and multiplexed in vitro detection of disease markers in clinical diagnosis.
Efficient Solar Cells Sensitized by Porphyrins with an Extended Conjugation Framework and a Carbazole Donor: From Molecular Design to Cosensitization
Authors: Wang Yueqiang , Chen Bin , Wu Wenjun , Li Xin , Zhu Weihong , Tian He , Xie Yongshu
Published: August 2014

Porphyrin dyes containing the carbazole electron donor have been designed and optimized by wrapping the porphyrin framework, introducing an additional ethynylene bridge to extend the wavelength range of light absorption, and further suppression of the dye aggregation by introducing additional alkoxy chains. Application of a cosensitization approach results in improved current density (Jsc) and open‐circuit voltage (Voc) values, thus achieving the highest cell efficiency of 10.45 %. This work provides an effective combined strategy of molecular design and cosensitization for developing efficient dye‐sensitized solar cells (DSSCs). In addition, carbazole has been demonstrated to be a promising donor for porphyrin sensitizers.
Interconvertible Living Radical and Cationic Polymerization through Reversible Activation of Dormant Species with Dual Activity
Authors: Aoshima Hiroshi , Uchiyama Mineto , Satoh Kotaro , Kamigaito Masami
Published: August 2014

The polymerization of vinyl monomers generally requires the selection of an appropriate single intermediate, whereas in copolymerization, the selection of the comonomer is limited by the intermediate. Herein, we propose interconvertible dual active species that can connect comonomers through different mechanisms to produce specific comonomer sequences in a single polymer chain. More specifically, two different stimuli, that is, a radical initiator and a Lewis acid, are used to activate the common dormant CSC(S)Z group into radical and cationic species, thereby inducing interconvertible radical and cationic copolymerization of acrylate and vinyl ether to produce a copolymer chain that consists of radically and cationically polymerized segments. The dual reversible activation provides control over molecular weights and multiblock copolymers with tunable segment lengths.
Numerical simulation study of the T‐peel behavior of coated fabric films used in inflatable structures
Authors: Yang Yabin , Zeng Pan , Lei Liping
Published: August 2014

A simple and reliable finite element method was developed to analyze the T‐peel behavior of fabric coated with thin films. The material model was constructed simply by a tensile test of the coating and the coated fabric. In addition, the influence of the welding parameters on the mechanical properties of the welded zone was considered. Although some material characters were neglected, the material model was found to be convenient for engineering applications. The reliability was examined by a comparison of the numerical results with the experiments. A T‐peel test was conducted, and a camera configured with an optical microscope lens was used to observe the material flow from the thickness view. The load–displacement curve predicted by the simulation agreed well with the experimental results. Small voids were detected when the sample was near fracture. These places were consistent with the simulation results and showed where the maximum stress–strain was located. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41299.
Synthesis of polyimides with low viscosity and good thermal properties via copolymerization
Authors: Zhang Chunhong , Su Guangdong , Chen Hui , Sun Ying , Song Hairui , Tong Lili
Published: August 2014

Novel polyimides were successfully synthesized through copolymerization of diamine monomers p‐phenylenediamine (p‐PDA) and 4,4'‐diaminodiphenylmethane (MDA) with different proportions and 2,3,3',4'‐biphenyltetracarboxylic dianhydride (a‐BPDA) using 4‐phenylethynylphthalic anhydride (4‐PEPA) as an end‐capping agent. The melt rheological properties, thermal properties, and crystallinity of PI oligomers were investigated via rheometer, dynamic mechanical analysis (DMA), thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and X‐ray diffraction (XRD). The results indicate that melt viscosity and solubility of the PI oligomers were improved, but the glass transition temperature (Tg) and crystallinity decreased with the increasing molar ratio of MDA. PI oligomer 3 with the molar ratio of MDA/p‐PDA = 2/1 shows a lower minimum melt viscosity (66 Pa.s) at 313°C and better solubility in aprotic solvents. The corresponding PI‐3 exhibits a high glass transition temperature of 406°C and excellent thermal stability. This copolyimide shows good processability and thermal properties, and could become a good candidate of matrix resins for high performance composites in aerospace field. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41303.
Polyurethanes derived from carbohydrates and cystine‐based monomers
Authors: Begines Belén , Zamora Francisca , de Paz M. Violante , Hakkou Khalid , Galbis Juan A.
Published: August 2014

Linear [m,n]‐type polyurethanes (PUs) fully based on renewable materials are synthesized by interfacial polycondensation reaction of diamines derived from the amino‐acid cystine with (bis)chloroformates derived from alditols having L‐arabino or xylo configuration. The degradability of the new PUs has been enhanced by the introduction of disulfide linkages into the polymer backbone leading to a new group of stimulus‐responsive sugar‐based polyurethanes able to be degraded by glutathione under physiological conditions. All these polyurethanes are stable up to around 245°C, decomposing at higher temperatures through a one‐stage mechanism. The new materials display high chemical homogeneity and degradability in both hydrolytic and reductive environments, with reductions of above 90% in Mw. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41304.
Study on the preparation and thermal shrinkage properties of nano‐SiO2/UHMWPE/HDPE blend microporous membranes
Authors: Wu Yin‐Cai , Cui Yi‐Hua , Jin Huai‐Long , Ning Chong‐Chong
Published: August 2014

Nano‐SiO2/UHMWPE/HDPE blend microporous membranes (NBMs) with different content of nano‐SiO2 particles were prepared via thermally induced phase separation process. Thermogravimetric analysis was used to investigation of the amount of nano‐SiO2 particles reserved in NBMs. This approach showed that about 59% of total content of nano‐SiO2 particles reserved in NBMs. The formation and development of the interface pores were studied by scanning electron microscopy. NBMs performance was characterized by a variety of metrics including thermal shrinkage, melting and crystallization behavior, porosity and pore diameter, and permeability. The results indicated that nano‐SiO2 particles served as nucleating agent increasing the crystalline of NBMs. The comprehensive properties of NBMs were optimum when the content of nano‐SiO2 particles was 1%. Compared with pure HDPE separators, NBMs exhibit higher porosity and lower thermal shrinkage due to its high crystalline and the enrichment of UHMWPE chains. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41321.
Biodiversity values of remnant freshwater floodplain lagoons in agricultural catchments: evidence for fish of the Wet Tropics bioregion, northern Australia
Authors: Arthington Angela H. , Godfrey Paul C. , Pearson Richard G. , Karim Fazlul , Wallace Jim
Published: August 2014

Tropical floodplain wetlands are among the world's most threatened and poorly documented freshwater ecosystems. This paper describes patterns of fish diversity in remnant freshwater lagoons in relation to natural environmental gradients and impacts of agriculture in the Tully–Murray catchment, Queensland Wet Tropics bioregion (QWT), in north‐eastern Australia.

Floodplain lagoons supported 21 of 29 native fish species recorded from freshwater habitats of these rivers, including three species not typically found in main river channels or tributaries, and six that require access to saline areas for spawning or larval development. Eight species favoured lagoons during their early life history, highlighting the vital role of these water bodies in providing nursery habitat.

Assemblage composition differed with distance from the coast, position on the floodplain, water quality and habitat. Aquatic vegetation discriminated lagoons and habitat patches within lagoons, and fish species richness was lower in patches of exotic ponded‐pasture grasses.

Although the lagoons are surrounded by intensive agriculture, especially sugarcane plantations, they are in good ecological condition, largely because of retention of some riparian vegetation, and frequent flushing by high stream flows. They offer opportunities to conserve taxonomic and functional biodiversity that is at present poorly protected by terrestrial reserves focused mainly on forested uplands. Of the 21 native species recorded, only one has >20% of its QWT distribution protected in IUCN category II protected areas (National Parks), and nine species have <10% of their QWT distribution in protected areas.

Opportunities to protect tropical freshwater fish diversity may be lost if threatening processes are not held in check through maintenance of natural flow regimes and floodplain connectivity, protection of riparian vegetation and aquatic habitat structure, continued application of best management farming practices and off‐reserve protection of freshwater habitats on public and private lands.

Copyright © 2014 John Wiley & Sons, Ltd.
Synthesis and In Vitro Pharmacological Evaluation of Novel 2‐Hydroxypropyl‐4‐arylpiperazine Derivatives as Serotoninergic Ligands
Authors: Fiorino Ferdinando , Magli Elisa , Severino Beatrice , Corvino Angela , Ciano Antonio , Perissutti Elisa , Frecentese Francesco , Massarelli Paola , Nencini Cristina , Santagada Vincenzo , Caliendo Giuseppe
Published: August 2014

This paper reports the synthesis of new norbornene and exo‐N‐hydroxy‐7‐oxabicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboximide derivatives and their binding to the 5‐HT1A, 5‐HT2A, and 5‐HT2C receptors, in order to identify selective ligands for these 5‐hydroxytryptamine (5‐HT, serotonine) receptor subtypes. The combination of structural elements (heterocyclic nucleus, hydroxyalkyl chain, and 4‐substituted piperazine) known to be critical for affinity to 5‐HT1A receptors and the proper selection of substituents led to compounds with high specificity and affinity toward serotoninergic receptors. The most active compounds were selected and further evaluated for their binding affinities to D1, D2 dopaminergic and α1, α2 adrenergic receptors. 4‐[3‐[4‐(2‐Furoyl)piperazin‐1‐yl]propoxy‐2‐ol]‐4‐aza‐tricyclo[5.2.1.02,6]dec‐8‐ene‐3,5‐dione 3e with Ki = 5.04 ± 0.227 nM was the most active and selective derivative for the 5‐HT2C receptor with respect to other serotonin receptors, and the most selective derivative versus dopaminergic and adrenergic receptors.
Cisplatin/gemcitabine or oxaliplatin/gemcitabine in the treatment of advanced biliary tract cancer: a systematic review
Authors: Fiteni Frédéric , Nguyen Thierry , Vernerey Dewi , Paillard Marie‐Justine , Kim Stefano , Demarchi Martin , Fein Francine , Borg Christophe , Bonnetain Franck , Pivot Xavier
Published: August 2014

Cisplatin/gemcitabine association has been a standard of care for first‐line regimen in advanced biliary tract cancer nevertheless oxaliplatin/gemcitabine regimen is frequently preferred. Because comparative effectiveness in clinical outcomes of cisplatin‐ versus oxaliplatin‐containing chemotherapy is not available, a systematic review of studies assessing cisplatin/gemcitabine or oxaliplatin/gemcitabine chemotherapies in advanced biliary tract cancer was performed. Published studies evaluating cisplatin/gemcitabine or oxaliplatin/gemcitabine in advanced biliary tract cancer were included. Each study was weighted according to the number of patients included. The primary objective was to assess weighted median of medians overall survival (mOS) reported for both regimens. Secondary goals were to assess weighted median of medians progression‐free survival (mPFS) and toxic effects were pooled and compared within each arm. Thirty‐three studies involving 1470 patients were analyzed. In total, 771 and 699 patients were treated by cisplatin/gemcitabine and oxaliplatin/gemcitabine, respectively. Weighted median of mOS was 9.7 months in cisplatin group and 9.5 months in oxaliplatin group. Cisplatin‐based chemotherapy was significantly associated with more grade 3 and 4 asthenia, diarrhea, liver toxicity, and hematological toxicity. Sensitivity analysis including only the studies with the standard regimen of cisplatin (25–35 mg/m2 administered on days 1 and 8) showed that the weighted median of mOS increased from 9.7 to 11.7 months but Gem/CDDP regimen remained more toxic than Gemox regimen. These results suggest that the Gem/CDDP regimen with cisplatin (25–35 mg/m2) administered on days 1 and 8 is associated with survival advantage than Gemox regimen but with addition of toxicity.
Biofuel‐Cell Cathodes Based on Bilirubin Oxidase Immobilized through Organic Linkers on 3D Hierarchically Structured Carbon Electrodes
Authors: Vivekananthan Jeevanthi , Rincón Rosalba A. , Kuznetsov Volodymyr , Pöller Sascha , Schuhmann Wolfgang
Published: August 2014

Different modification procedures to stabilize and control the orientation of Myrothecium verrucaria bilirubin oxidase (MvBOD) on 3D carbon nanotube/carbon microfiber‐modified graphite electrode surfaces were evaluated for the development of biofuel‐cell cathodes. The surface properties of different linkers for covalent binding of BOD were investigated by using atomic force microscopy‐based techniques. For all immobilization strategies, the maximal current response was obtained at a pH value of 6.5 with temperatures between 20 and 35 °C. The biocathode based on MvBOD immobilized through an imino bond to the electrode showed the highest current density (1600 μA cm−2) and was resistant to the presence of chloride ions. A biofuel cell was constructed, and it exhibited a maximal power of 54 μW cm−2 at 350 mV with an open‐circuit voltage of about 600 mV by using a cellobiose dehydrogenase based bioanode and glucose as the fuel.
A Monosaccharide‐Based Coin‐Cell Biobattery
Authors: Giroud Fabien , Hickey David P. , Schmidtke David W. , Glatzhofer Daniel T. , Minteer Shelley D.
Published: August 2014

The utilization of carbon felt as the conductive material for the construction of a monosaccharide‐based coin‐cell biobattery is explored. Anthracene‐modified carbon nanotubes were used at the positive electrode to preferentially orientate laccase for direct electron transfer during O2 reduction. A ferrocene‐modified poly(ethylenimine) redox polymer was used to electrically communicate with either glucose oxidase or fructose dehydrogenase at the negative electrode. The use of carbon felt helped in the immobilization of a larger quantity of enzyme. Cathodic and anodic currents with carbon felt electrodes showed a three‐fold and twofold increase, respectively, relative to the currents obtained with Toray paper materials. Bioelectrodes were assembled in a commercial coin‐cell battery casing and were tested as possible biobatteries. This work presents the first time in which a traditional battery design is used for the performance evaluation of different biobatteries.
Control of the Single‐Molecule Magnet Behavior of Lanthanide‐Diarylethene Photochromic Assemblies by Irradiation with Light
Authors: Pinkowicz Dawid , Ren Min , Zheng Li‐Min , Sato Saki , Hasegawa Miki , Morimoto Masakazu , Irie Masahiro , Breedlove Brian K. , Cosquer Goulven , Katoh Keiichi , Yamashita Masahiro
Published: August 2014

Lanthanide‐based extended coordination frameworks showing photocontrolled single‐molecule magnet (SMM) behavior were prepared by combining highly anisotropic DyIII and HoIII ions with the carboxylato‐functionalized photochromic molecule 1,2‐bis(5‐carboxyl‐2‐methyl‐3‐thienyl)perfluorocyclopentene (H2dae), which acts as a bridging ligand. As a result, two new compounds of the general formula [{LnIII2(dae)3(DMSO)3(MeOH)}⋅10 MeOH]n (M=Dy for 1 a and Ho for 2) and two additional pseudo‐polymorphs [{DyIII2(dae)3(DMSO)3(H2O)}⋅x MeOH]n (1 b) and [{DyIII2(dae)3(DMSO)3(DMSO)}⋅x MeOH]n (1 c) were obtained. All four compounds have 2D coordination‐layer topologies, in which carboxylate‐bridged Ln2 units are linked together by dae2− anions into grid‐like frameworks. All four compounds exhibited a strong reversible photochromic response to UV/Vis light. Moreover, both 1 a and 2 show field‐induced SMM behavior. The slow magnetic relaxation of 1 a is influenced by the photoisomerization reaction leading to the observation of the cross‐effect: photocontrolled SMM behavior.
A Fast Way to Fluorescence: A Fourfold Domino Reaction to Condensed Polycyclic Compounds
Authors: Tietze Lutz F. , Eichhorst Christoph , Hungerland Tim , Steinert Markus
Published: August 2014

A fast and efficient palladium‐catalyzed fourfold domino Sonogashira/double‐carbopalladation/CH‐activation reaction that converts simple aromatic systems into complex polycyclic hydrocarbons has been developed. A number of substituted products has thus been prepared in yields up to 89 %. The structural assignment has been confirmed by using single‐crystal X‐ray crystallography. The products show intriguing fluorescence activity and thus might serve as chemical sensors or fluorescent imaging dyes.
Synthesis and Evaluation of Novel Analogues of Ripostatins
Authors: Tang Wufeng , Liu Shuang , Degen David , Ebright Richard H. , Prusov Evgeny V.
Published: August 2014

Ripostatins are polyene macrolactones isolated from the myxobacterium Sorangium cellulosum. They exhibit antibiotic activity by inhibiting bacterial RNA polymerase (RNAP) through a binding site and mechanism that are different from those of current antibacterial drugs. Thus, the ripostatins serve as starting points for the development of new anti‐infective agents with a novel mode of action. In this work, several derivatives of ripostatins were produced. 15‐Desoxyripostatin A was synthesized by using a one‐pot carboalumination/cross‐coupling. 5,6‐Dihydroripostatin A was constructed by utilizing an intramolecular Suzuki cross‐coupling macrolactonization approach. 14,14′‐Difluororipostatin A and both epimeric 14,14′‐difluororipostatins B were synthesized by using a Reformatsky type aldol addition of a haloketone, Stille cross‐coupling, and ring‐closing metathesis. The RNAP‐inhibitory and antibacterial activities are presented. Structure–activity relationships indicate that the monocyclic keto‐ol form of ripostatin A is the active form of ripostatin A, that the ripostatin C5–C6 unsaturation is important for activity, and that C14 geminal difluorination of ripostatin B results in no loss of activity.
Bis[N,N′‐diisopropylbenzamidinato(−)]silicon(II): Lewis Acid/Base Reactions with Triorganylboranes
Authors: Junold Konstantin , Baus Johannes A. , Burschka Christian , Fonseca Guerra Célia , Bickelhaupt F. Matthias , Tacke Reinhold
Published: August 2014

Reaction of the donor‐stabilized silylene 1 (which is three‐coordinate in the solid state and four‐coordinate in solution) with BEt3 and BPh3 leads to the formation of the Lewis acid/base complexes 2 and 3, respectively, which are the first five‐coordinate silicon compounds with an SiB bond. These compounds were structurally characterized by crystal structure analyses and by multinuclear NMR spectroscopic studies in the solid state and in solution. Additionally, the bonding situation in 2 and 3 was analyzed by quantum chemical studies.
Oxygenation by Ruthenium Monosubstituted Polyoxotungstates in Aqueous Solution: Experimental and Computational Dissection of a Ru(III)–Ru(V) Catalytic Cycle
Authors: Sartorel Andrea , Miró Pere , Carraro Mauro , Berardi Serena , Bortolini Olga , Bagno Alessandro , Bo Carles , Bonchio Marcella
Published: August 2014

Molecular polyoxometalates with one embedded ruthenium center, with general formula [RuII/III(DMSO)XW11O39]n− (X=P, Si; n=4–6), are readily synthesized in gram scale under microwave irradiation by a flash hydrothermal protocol. These nanodimensional and polyanionic complexes enable aerobic oxygenation in water. Catalytic oxygen transfer to dimethylsulfoxide (DMSO) yielding the corresponding sulfone (DMSO2) has been investigated with a combined kinetic, spectroscopic and computational approach addressing: (i ) the RuIII catalyst resting state; (ii ) the bimolecular event dictating its transformation in the rate‐determining step; (iii ) its aerobic evolution to a high‐valent ruthenium oxene species; (iv ) the terminal fate to diamagnetic dimers. This pathway is reminiscent of natural heme systems and of bioinspired artificial porphyrins. The in silico characterization of a key bis‐Ru(IV)‐μ‐peroxo‐POM dimeric intermediate has been accessed by density functional theory. This observation indicates a new landmark for tracing POM‐based manifolds for multiredox oxygen reduction/activation, where metal‐centered oxygenated species play a pivotal role.
ChemInform Abstract: A Novel Tunable Na2Ba6(Si2O7) (SiO4)2:Ce3+,Mn2+ Phosphor with Excellent Thermal Stability for White Light Emitting Diodes.
Authors: Lv Wenzhen , Jia Yongchao , Zhao Qi , Jiao Mengmeng , Shao Baiqi , Lv Wei , You Hongpeng
Published: August 2014

The title phosphor is synthesized by solid state reaction of NaNO3, BaCO3, SiO2, CeO2, and MnCO3 (5% H2—95% N2, 1050 °C, 8 h) and characterized by XRD and photoluminescence spectroscopy.
ChemInform Abstract: A Novel Tunnel Na0.61Ti0.48Mn0.52O2 Cathode Material for Sodium‐Ion Batteries.
Authors: Guo Shaohua , Yu Haijun , Liu Dequan , Tian Wei , Liu Xizheng , Hanada Nobuko , Ishida Masayoshi , Zhou Haoshen
Published: August 2014

The title material is synthesized by solid state reaction of Na2CO3, Mn2O5, and TiO2 (Ar, 900 °C, 20 h).
ChemInform Abstract: Lithium Cycling in a Self‐Assembled Copper Chloride—Polyether Hybrid Electrode.
Authors: Jaffe Adam , Karunadasa Hemamala I.
Published: August 2014

Addition of a HCl solution to a mixture of 2,2′‐(ethylenedioxy)bis(ethylamine) (edbe) and CuCl2 in EtOH leads to the precipitation of (H2edbe)[CuCl4] crystals with a yield of 87%.
ChemInform Abstract: Iodine Mediated Deprotection of N‐tert‐Butanesulfinyl Amines: A Functional Group Compatible Method.
Authors: Chen Wen , Ren Jian , Wang Minshou , Dang Lingjing , Shen Xianfu , Yang Xiaodong , Zhang Hongbin
Published: August 2014

Tert‐butanesulfinyl and p‐toluenesulfinyl amines are cleaved by iodine.
ChemInform Abstract: Acetals: A New Organocatalysis Chemotype for One‐Pot Enantioselective α‐Amination.
Authors: Msutu Ath'enkosi , Hunter Roger
Published: August 2014

Conditions for the enantioselective α‐amination of acetals with azodicarboxylate (II) are elaborated.
ChemInform Abstract: A Homologation Approach to the Synthesis of Difluorinated Cycloalkynes.
Authors: Sletten Ellen M. , de Almeida Gabriela , Bertozzi Carolyn R.
Published: August 2014

The starting material (I) is synthesized beginning with the difluorination of cycloheptane‐1,3‐dione using Selectfluor, mono‐Wittig olefination and hydrogenation of the olefin moiety.
ChemInform Abstract: Asymmetric Henry Reaction Catalyzed by L‐Proline Derivatives in the Presence of Cu(OAc)2: Isolation and Characterization of an in situ Formed Cu(II) Complex.
Authors: Atoholi Sema H. , Bez Ghanashyam , Karmakar Sanjib
Published: August 2014

In addition to the synthesis of the ligand PRO, the preparation of five proline‐derived chiral ligands is described all showing inferior catalytic activity compared to PRO under the investigated conditions.
ChemInform Abstract: Boronic Acid‐Catalyzed Selective Oxidation of 1,2‐Diols to α‐Hydroxy Ketones in Water.
Authors: William Julius M. , Kuriyama Masami , Onomura Osamu
Published: August 2014

Various 1,2‐diols are selectively oxidized to α‐hydroxyketones via their boronate esters using dibromoisocyanuric acid as the terminal oxidant or an electrochemical oxidation.
ChemInform Abstract: RhIII‐Catalyzed Hydroacylation Reactions Between N‐Sulfonyl 2‐Aminobenzaldehydes and Olefins.
Authors: Zhang Tao , Qi Zisong , Zhang Xueyun , Wu Lamei , Li Xingwei
Published: August 2014

A facile procedure allows the coupling of aminobenzaldehydes with olefins.
ChemInform Abstract: PdCl2 Catalyzed Efficient Assembly of Organic Azides, CO, and Alcohols under Mild Conditions: A Direct Approach to Synthesize Carbamates.
Authors: Ren Long , Jiao Ning
Published: August 2014

Phenols are ineffective for intermolecular reactions.
ChemInform Abstract: Heck—Matsuda Arylation of Olefins Through a Bicatalytic Approach: Improved Procedures and Rationalization.
Authors: Oger Nicolas , Le Callonnec Francois , Jacquemin Denis , Fouquet Eric , Le Grognec Erwan , Felpin Francois‐Xavier
Published: August 2014

The reaction yields dramatically depend on the experimental procedure requiring the addition of most of the anisole derivative over 24 h to a mixture of a small amount of the anisole derivative and all other reagents.
ChemInform Abstract: N‐Heterocyclic Carbene‐Catalyzed Formal Cross‐Coupling Reaction of α‐Haloenals with Thiols: Organocatalytic Construction of sp2 Carbon—Sulfur Bonds.
Authors: He Lin , Guo Hao , Li Yuan‐Zhen , Du Guang‐Fen , Dai Bin
Published: August 2014

Inter‐ and intramolecular competition reactions between an alcohol and a thiol revealed that the α‐bromoenal (I) preferentially reacts with thiols.
ChemInform Abstract: Active Palladium Catalyst Supported by Bulky Diimine Ligand Catalyzed Suzuki—Miyaura Coupling Reaction in Water under Phosphane‐Free and Low Catalyst Loading Conditions.
Authors: Gholinejad Mohammad , Karimkhani Vahid , Kim Il
Published: August 2014

The synthesis of the catalyst is described.
ChemInform Abstract: 4‐(Dimethylamino)pyridine as a Catalyst for the Lactonization of 4‐Hydroxy‐2‐methylenebutanoate Esters.
Authors: Nicponski Daniel R.
Published: August 2014

The starting compounds for these lactonization reactions are prepared in a three step procedure from methyl acrylate.
ChemInform Abstract: Palladium‐Catalyzed One‐Pot Three‐ or Four‐Component Coupling of Aryl Iodides, Alkynes, and Amines Through C—N Bond Cleavage: Efficient Synthesis of Indole Derivatives.
Authors: Hao Wei , Geng Weizhi , Zhang Wen‐Xiong , Xi Zhenfeng
Published: August 2014

A variety of aryl iodides and substituted 1‐bromo‐2‐iodobenzene derivatives [e.g. (XIV) in four‐component reaction], and symmetric and unsymmetric alkynes can be used for the title synthesis.
ChemInform Abstract: Synthesis of Substituted Tetrahydron‐1H‐carbazol‐1‐one and Analogues via PhI(OCOCF3)2‐Mediated Oxidative C—C Bond Formation.
Authors: Shi Hao , Guo Tianjian , Zhang‐Negrerie Daisy , Du Yunfei , Zhao Kang
Published: August 2014

The title compounds are conveniently synthesized through direct intramolecular oxidative cyclization of 2‐(phenylamine)cyclohex‐2‐enones.
ChemInform Abstract: Synthesis of Substituted 2,4,5,6‐Tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6‐Tetrahydropyrrolo[3,4‐c]pyrazoles by Intramolecular Nitrilimine Cycloaddition.
Authors: Winters Michael P. , Teleha Christopher A. , Sui Zhihua
Published: August 2014

Treatment of sensitive hydrazonyl chlorides with triethylamine results in the formation of nitrilimine intermediates.
ChemInform Abstract: Copper(II)‐Catalyzed Aerobic Oxidative Coupling Between Chalcone and 2‐Aminopyridine via C—H Amination: An Expedient Synthesis of 3‐Aroylimidazo[1,2‐a]pyridines.
Authors: Monir Kamarul , Kumar Bagdi Avik , Mishra Subhajit , Majee Adinath , Hajra Alakananda
Published: August 2014

The α,β‐unsaturated ketones trans‐3‐nonen‐2‐one and 2‐cyclohexen‐1‐one as well as acrylonitrile, vinyl phosphate and ethyl acrylate do not afford the desired imidazopyridine derivatives.
ChemInform Abstract: Straightforward Synthesis of Orthogonally Protected Piperidin‐3‐ylmethanamine and Piperidin‐4‐ylmethanamine Derivatives.
Authors: Kosak Urban , Brus Boris , Gobec Stanislav
Published: August 2014

Two convenient procedures are developed for the synthesis of protected piperidin‐4‐ylmethanamine derivatives from isonipecotamide (I) and isonipecotic acid (VI).
ChemInform Abstract: Rhodium(III)‐Catalyzed Oxidative Olefination of Picolinamides: Convenient Synthesis of 3‐Alkenylpicolinamides.
Authors: Zhou Jun , Li Bo , Qian Zhen‐Chao , Shi Bing‐Feng
Published: August 2014

The olefination is advantageous with regards to high yields, excellent regioselectivity, and good functional group tolerance.
ChemInform Abstract: Enantioselective Synthesis of Azaflavanones Using Organocatalytic 6‐endo Aza‐Michael Addition.
Authors: Cheng Shuanghua , Zhao Lili , Yu Shouyun
Published: August 2014

The optimized conditions allow the highly enantioselective conversion of 2‐aminochalcones into 2‐substituted azaflavanones via intramolecular 6‐endo aza‐Michael addition.
ChemInform Abstract: Direct sp3 C—H Acroleination of N‐Aryl‐tetrahydroisoquinolines by Merging Photoredox Catalysis with Nucleophilic Catalysis.
Authors: Feng Zhu‐Jia , Xuan Jun , Xia Xu‐Dong , Ding Wei , Guo Wei , Chen Jia‐Rong , Zou You‐Quan , Lu Liang‐Qiu , Xiao Wen‐Jing
Published: August 2014

The first example of sequence catalysis by merging visible light photoredox catalysis and nucleophilic catalysis is reported.
ChemInform Abstract: Organocatalytic Enantioselective Multicomponent Synthesis of Pyrrolopiperazines.
Authors: Du Haiying , Rodriguez Jean , Bugaut Xavier , Constantieux Thierry
Published: August 2014

Original and biologically relevant fused tricyclic piperazines are synthesized via this new organocatalytic multicomponent reaction.
ChemInform Abstract: Sesquiterpenoids from the Fruits of Alpinia oxyphylla and Their anti‐Acetylcholinesterase Activity
Authors: Chen Ping , Wang Pei‐Pei , Jiao Ze‐Zhao , Xiang Lan
Published: August 2014

isolation and structure elucidation of fourteen sesquiterpenoids including the novel terpenoids (I) and (II) and in vitro effects of twenty sesquiterpenoids on AChE activity
ChemInform Abstract: Cinanthrenol A, an Estrogenic Steroid Containing Phenanthrene Nucleus, from a Marine Sponge Cinachyrella sp.
Authors: Machida Koshi , Abe Takahiro , Arai Daisuke , Okamoto Mayumi , Shimizu Isao , de Voogd Nicole J. , Fusetani Nobuhiro , Nakao Yoichi
Published: August 2014

The isolation, structure elucidation and determination of the absolute configuration of the title compound (I) is described.
ChemInform Abstract: Stereoisomers of Ieodoglucomides A and B: Synthesis and Evaluation of Anticancer Activity.
Authors: Reddy Chada Raji , Jithender Enukonda , Singh Ashita , Ummanni Ramesh
Published: August 2014

The alpha‐isomers (Ia) and (Ib) of ieodoglucosamides A and B as well as their C14‐epimers (II) are prepared from glucose and tested on their anticancer activity (prostate cancer DU145, human lung carcinoma A549, breast cancer MCF‐7, human epithelial cervical cancer HeLa cells).
ChemInform Abstract: Expanding the Synthetic Portfolio of Organolithiums: Direct Use in Catalytic Cross‐Coupling Reactions
Authors: Pace Vittorio , Luisi Renzo
Published: August 2014

Review: 23 refs.
ChemInform Abstract: Sonochemistry: Synthesis of Bioactive Heterocycles
Authors: Hussein Essam M. , Khairou Khalid S.
Published: August 2014

Review: 113 refs.
ChemInform Abstract: Recent Developments of Metal N‐Heterocyclic Carbenes as Anticancer Agents
Authors: Aher Sainath Babaji , Muskawar Prashant Narayan , Thenmozhi K. , Bhagat Pundlik Rambhau
Published: August 2014

Review: 68 refs.
ChemInform Abstract: Recent Advances in Biocompatible Nanocarriers for Delivery of Chemotherapeutic Cargoes Towards Cancer Therapy
Authors: Ang Chung Yen , Tan Si Yu , Zhao Yanli
Published: August 2014

Review: 270 refs.
ChemInform Abstract: Smart Drug Delivery Systems: From Fundamentals to the Clinic
Authors: Alvarez‐Lorenzo Carmen , Concheiro Angel
Published: August 2014

Review: 244 refs.
ChemInform Abstract: Understanding Low Bandgap Polymer PTB7 and Optimizing Polymer Solar Cells Based on It
Authors: Lu Luyao , Yu Luping
Published: August 2014

Review: 88 refs.
ChemInform Abstract: The Evolution of Life Cycle Assessment in Pharmaceutical and Chemical Applications — A Perspective
Authors: Jimenez‐Gonzalez Concepcion , Overcash Michael R.
Published: August 2014

Review: 56 refs.
ChemInform Abstract: Short Review: Mitigation of Current Environmental Concerns from Methanol Synthesis
Authors: Young Andrew , Lesmana Donny , Dai Der‐Jong , Wu Ho‐Shing
Published: August 2014

Review: 66 refs.
CFD modelling of continuous protein extraction process using liquid‐solid circulating fluidized beds
Authors: Dadashi Abbas , Zhu Jingxu , Zhang Chao
Published: August 2014

A computational fluid dynamics (CFD) model was developed to describe the hydrodynamics and mass transfer in the process of continuous protein extraction from broth using a liquid‐solid circulating fluidized bed (LSCFB) ion exchange system. The CFD model took into account both the adsorption and desorption processes. The quantitative predictions for the protein concentration were compared favourably with the experimental data from a lab‐scale system. The model was used to investigate the effects of hydrodynamic and kinetic parameters on the performance of the LSCFB ion exchange system. It was demonstrated that the model is a robust tool to simulate, scale up, and optimize the LSCFB ion exchange systems for protein extraction process.
Aptamers as Drug Delivery Vehicles
Authors: Kruspe Sven , Mittelberger Florian , Szameit Kristina , Hahn Ulrich
Published: August 2014

The benefits of directed and selective therapy for systemic treatment are reasons for increased interest in exploiting aptamers for cell‐specific drug delivery. Nucleic acid based pharmaceuticals represent an interesting and novel tool to counter human diseases. Combining inhibitory potential and cargo transfer upon internalization, nanocarriers as well as various therapeutics including siRNAs, chemotherapeutics, photosensitizers, or proteins can be imported via these synthetic nucleic acids. However, widespread clinical application is still hampered by obstacles that must be overcome. In this review, we give an overview of applications and recent advances in aptamer‐mediated drug delivery. We also introduce prominent selection methods as well as useful approaches in choice of drug and conjugation method. We discuss the challenges that need to be considered and present strategies that have been applied to achieve intracellular delivery of effectors transported by readily internalized aptamers.
Design and Characterization of a Twin Ribozyme for Potential Repair of a Deletion Mutation within the Oncogenic CTNNB1‐ΔS45 mRNA
Authors: Balke Darko , Zieten Irene , Strahl Anne , Müller Oliver , Müller Sabine
Published: August 2014

RNA repair is an emerging strategy for gene therapy. Conventional gene therapy typically relies on the addition of the corrected DNA sequence of a defective gene to restore gene function. As an additional option, RNA repair allows alteration of the sequence of endogenous messenger RNAs (mRNAs). mRNA sequence alteration is either facilitated by intracellular spliceosome machinery or by the intrinsic catalytic activity of trans‐acting ribozymes. Previously we developed twin ribozymes, derived from the hairpin ribozyme, by tandem duplication and demonstrated their potential for patchwise RNA repair. Herein we describe the development of such a twin ribozyme for potential repair of a deletion mutation in the oncogenic CTNNB1‐ΔS45 mRNA. We demonstrate that hairpin ribozyme units within the twin ribozyme can be adapted to efficiently cleave/ligate non‐consensus substrates by introduction of compensatory mutations in the ribozyme. Thus, we show the twin ribozyme mediated repair of truncated CTNNB1 transcripts (up to 1000 nt length). Repair of the entire CTNNB1‐ΔS45 mRNA, although apparently possible in general, is hampered in vitro by the secondary structure of the transcript.
Poor outcome and death among youth, young adults, and midlife adults with eating disorders: An investigation of risk factors by age at assessment
Authors: Ackard Diann M. , Richter Sara , Egan Amber , Cronemeyer Catherine
Published: August 2014

Objective

Eating disorders (EDs) present across a broad age range, yet little is known about the characteristics and outcome of midlife patients compared to younger patients. Among patients seeking ED treatment who were stratified by age at initial assessment (IA), this study aimed to (1) discern sociodemographic and clinical differences, (2) determine outcome rates, and (3) identify predictors of poor outcome including death.

Method

Participants [219 females (12 years or older, 94.1% Caucasian) who completed outcome assessment and 31 known decedents] were stratified by age at IA (<18 as youth, 18–39 as young adult, and ≥40 years as midlife adult). Analyses of variance and chi‐square tests identified group differences; ordered logistic regression with stepwise selection identified factors predicting outcome.

Results

Midlife adults were more significantly compromised at follow‐up compared to youths and young adults, including psychological and physical quality of life, ineffectiveness, interpersonal concerns, and general psychological maladjustment. Midlife adults had the highest rates of poor outcome or death; good outcome was achieved by only 5.9% of midlife adult compared to 14.0% of young adult and 27.5% of youth patients. Older age at IA, alcohol and/or drug misuse, endocrine concerns, and absence of family ED history predicted poor outcome or death.

Discussion

Midlife adults seeking ED treatment have more complex medical and psychological concerns and poorer outcomes than youths and young adults; further exploration is needed to improve treatment outcome. Specialized treatment focusing on quality of life, comorbid medical concerns, interpersonal connection, and emotion regulation is encouraged. © 2014 Wiley Periodicals, Inc. Int J Eat Disord 2014; 47:825–835