bluuebunny/crossref_metadata_2025_split huggingface dataset:
High‐Quality Gasoline Directly from Syngas by Dual Metal Oxide–Zeolite (OX‐ZEO) Catalysis
Authors: Li Na , Jiao Feng , Pan Xiulian , Chen Yuxiang , Feng Jingyao , Li Gen , Bao Xinhe 
Published: April 2019

AbstractDespite significant efforts towards the direct conversion of syngas into liquid fuels, the selectivity remains a challenge, particularly with regard to high‐quality gasoline with a high octane number and a low content of aromatic compounds. Herein, we show that zeolites with 1D ten‐membered‐ring (10‐MR) channel structures such as SAPO‐11 and ZSM‐22 in combination with zinc‐ and manganese‐based metal oxides (ZnaMnbOx) enable the selective synthesis of gasoline‐range hydrocarbons C5–C11 directly from syngas. The gasoline selectivity reached 76.7 % among hydrocarbons, with only 2.3 % CH4 at 20.3 % CO conversion. The ratio of isoparaffins to n‐paraffins was as high as 15, and the research octane number was estimated to be 92. Furthermore, the content of aromatic compounds in the gasoline was as low as 16 %. The composition and structure of ZnaMnbOx play an important role in determining the overall activity. This process constitutes a potential technology for the one‐step synthesis of environmentally friendly gasoline with a high octane number from a variety of carbon resources via syngas.
Dual‐Targeting Dual‐Action Platinum(IV) Platform for Enhanced Anticancer Activity and Reduced Nephrotoxicity
Authors: Babak Maria V. , Zhi Yang , Czarny Bertrand , Toh Tan Boon , Hooi Lissa , Chow Edward Kai‐Hua , Ang Wee Han , Gibson Dan , Pastorin Giorgia 
Published: April 2019

AbstractA novel and highly efficient dual‐targeting platform was designed to ensure targeted in vivo delivery of dual‐action PtIV prodrugs. The dual targeting was established by liposomal encapsulation of PtIV complexes, thereby utilizing the enhanced permeability and retention (EPR) effect as the first stage of targeting to attain a high accumulation of the drug‐loaded liposomes in the tumor. After the release of the PtIV prodrug inside cancer cells, a second stage of targeting directed a portion of the PtIV prodrugs to the mitochondria. Upon intracellular reduction, these PtIV prodrugs released two bioactive molecules, acting both on the mitochondrial and on the nuclear DNA. Our PtIV system showed excellent activity in vitro and in vivo, characterized by a cytotoxicity in a low micromolar range and complete tumor remission, respectively. Notably, marked in vivo activity was accompanied by reduced kidney toxicity, highlighting the unique therapeutic potential of our novel dual‐targeting dual‐action platform.
19F Magic Angle Spinning Dynamic Nuclear Polarization Enhanced NMR Spectroscopy
Authors: Viger‐Gravel Jasmine , Avalos Claudia E. , Kubicki Dominik J. , Gajan David , Lelli Moreno , Ouari Olivier , Lesage Anne , Emsley Lyndon 
Published: April 2019

AbstractThe introduction of high‐frequency, high‐power microwave sources, tailored biradicals, and low‐temperature magic angle spinning (MAS) probes has led to a rapid development of hyperpolarization strategies for solids and frozen solutions, leading to large gains in NMR sensitivity. Here, we introduce a protocol for efficient hyperpolarization of 19F nuclei in MAS DNP enhanced NMR spectroscopy. We identified trifluoroethanol‐d3 as a versatile glassy matrix and show that 12 mm AMUPol (with microcrystalline KBr) provides direct 19F DNP enhancements of over 100 at 9.4 T. We applied this protocol to obtain DNP‐enhanced 19F and 19F–13C cross‐polarization (CP) spectra for an active pharmaceutical ingredient and a fluorinated mesostructured hybrid material, using incipient wetness impregnation, with enhancements of approximately 25 and 10 in the bulk solid, respectively. This strategy is a general and straightforward method for obtaining enhanced 19F MAS spectra from fluorinated materials.
An Engineered Aryl Acid Adenylation Domain with an Enlarged Substrate Binding Pocket
Authors: Ishikawa Fumihiro , Miyanaga Akimasa , Kitayama Hinano , Nakamura Shinya , Nakanishi Isao , Kudo Fumitaka , Eguchi Tadashi , Tanabe Genzoh 
Published: April 2019

AbstractAdenylation (A) domains act as the gatekeepers of non‐ribosomal peptide synthetases (NRPSs), ensuring the activation and thioesterification of the correct amino acid/aryl acid building blocks. Aryl acid building blocks are most commonly observed in iron‐chelating siderophores, but are not limited to them. Very little is known about the reprogramming of aryl acid A‐domains. We show that a single asparagine‐to‐glycine mutation in an aryl acid A‐domain leads to an enzyme that tolerates a wide range of non‐native aryl acids. The engineered catalyst is capable of activating non‐native aryl acids functionalized with nitro, cyano, bromo, and iodo groups, even though no enzymatic activity of wild‐type enzyme was observed toward these substrates. Co‐crystal structures with non‐hydrolysable aryl‐AMP analogues revealed the origins of this expansion of substrate promiscuity, highlighting an enlargement of the substrate binding pocket of the enzyme. Our findings may be exploited to produce diversified aryl acid containing natural products and serve as a template for further directed evolution in combinatorial biosynthesis.
Tertiary α‐Silyl Alcohols by Diastereoselective Coupling of 1,3‐Dienes and Acylsilanes Initiated by Enantioselective Copper‐Catalyzed Borylation
Authors: Feng Jian‐Jun , Oestreich Martin 
Published: April 2019

AbstractAn efficient synthesis of functionalized tertiary α‐silyl alcohols by an enantio‐ and diastereoselective copper‐catalyzed three‐component coupling of 1,3‐dienes, bis(pinacolato)diboron, and acylsilanes is reported. The reaction proceeds well with different 1,3‐dienes and a broad range of aryl‐ as well as alkenyl‐ but also alkyl‐substituted acylsilanes. The target compounds are formed with high regio‐, diastereo‐, and enantioselectivity (up to 99 % ee and d.r. >20:1) and are highly versatile synthetic building blocks.
A Redox‐Confused Bismuth(I/III) Triamide with a T‐Shaped Planar Ground State
Authors: Kindervater Marcus B. , Marczenko Katherine M. , Werner‐Zwanziger Ulrike , Chitnis Saurabh S. 
Published: April 2019

AbstractReaction of a tethered triamine ligand with Bi(NMe2)3 gives a Bi triamide, for which a BiI electronic structure is shown to be most appropriate. The T‐shaped geometry at bismuth provides the first structural model for edge inversion in bismuthines and the only example of a planar geometry for pnictogen triamides. Analogous phosphorus compounds exhibit a distorted pyramidal geometry because of different Bi−N and P−N bond polarities. Although considerable BiI character is indicated for the title Bi triamide, it exhibits reactivity similar to BiIII electrophiles, and expresses either a vacant or a filled p orbital at Bi, as evidenced by coordination of either pyridine N‐oxide or W(CO)5. The product of the former shows evidence of coordination‐induced oxidation state change at bismuth.
Successful resuscitation after drowning with severe hypernatraemia and prolonged time to return of spontaneous circulation
Authors: Klitgaard T. L. , Kjaergaard B. , Staehr J. B. 
Published: April 2019

SummaryWe describe the successful resuscitation of a 23‐year‐old previously healthy man who had drowned. After prolonged submersion, hypothermia, severe hypernatraemia, a prolonged time to return of spontaneous circulation was possible using a combination of extracorporal life support and early continuous veno‐venous haemofiltration. This combination of clinical circumstances is rarely associated with positive outcomes, but this case demonstrates the utility of extracorporeal life support and haemofiltration in patients drowned in saltwater.
Stabilization of switched neural networks with time‐varying delay via bumpless transfer control
Authors: Liu Chao , Sun Dihua , Yang Zheng , Liu Xiaoyang , Yang Hongyu , Huang Junjian 
Published: April 2019

AbstractThis paper investigates the stabilization of switched neural networks with time‐varying delay. In order to overcome the drawback that the classical switching state feedback controller may generate the bumps at switching time, a new switching feedback controller which can smooth effectively the bumps is proposed. According to mode‐dependent average dwell time, new exponential stabilization results are deduced for switched neural networks under the proposed feedback controller. Based on a simple corollary, the procedures which are used to calculate the feedback control gain matrices are also obtained. Two simple numerical examples are employed to demonstrate the effectiveness of the proposed results.
Fabrication of Self‐Propelled Micro‐ and Nanomotors Based on Janus Structures
Authors: Ye Yicheng , Luan Jiabin , Wang Ming , Chen Yongming , Wilson Daniela A. , Peng Fei , Tu Yingfeng 
Published: April 2019

AbstractDelicate molecular and biological motors are tiny machines capable of achieving numerous vital tasks in biological processes. To gain a deeper understanding of their mechanism of motion, researchers from multiple backgrounds have designed and fabricated artificial micro‐ and nanomotors. These nano‐/microscale motors can self‐propel in solution by exploiting different sources of energy; thus showing tremendous potential in widespread applications. As one of the most common motor systems, Janus motors possess unique asymmetric structures and integrate different functional materials onto two sides. This review mainly focuses on the fabrication of different types of micro‐ and nanomotors based on Janus structures. Furthermore, some challenges still exist in the implementation of Janus motors in the biomedical field. With such common goals in mind, it is expected that the elaborate and multifunctional design of Janus motors will overcome their challenges in the near future.
Diindeno‐Fused Dibenzo[a,h]anthracene and Dibenzo[c,l]chrysene: Syntheses, Structural Analyses, and Properties
Authors: Boominathan Siva Senthil Kumar , Chang Kai‐Hsin , Liu Yu‐Chiao , Wang Chi‐Shin , Wu Cheng‐Feng , Chiang Ming‐Hsi , Chou Pi‐Tai , Wu Yao‐Ting 
Published: April 2019

AbstractDiindeno‐fused dibenzo[a,h]anthracene 6 and diindeno‐fused dibenzo[c,l]chrysene 9 contain the key moieties 1,4‐quinodipropene (1,4‐QDP) and 2,6‐naphthoquinodipropene (2,6‐NQDP), respectively, and they both have an open‐shell singlet ground state. The latter compound exhibits a strong biradical character and interesting properties, including a low ΔET−S (2.44 kcal mol−1), a small HOMO–LUMO gap (1.06 eV), a wide photoabsorption range (250–1172 nm), and a large two‐photon absorption cross‐section (σ=1342±56 GM). This work verifies that 6 has a slightly larger HOMO–LUMO gap and ΔET−S than its helical isomer diindeno[2,1‐f:1′,2′‐j]picene (DIP), but is a much stronger two‐photon absorber, verifying the important effect of geometry on the photophysical properties.
[4]Cyclo‐N‐ethyl‐2,7‐carbazole: Synthesis, Structural, Electronic and Charge Transport Properties
Authors: Lucas Fabien , Sicard Lambert , Jeannin Olivier , Rault‐Berthelot Joëlle , Jacques Emmanuel , Quinton Cassandre , Poriel Cyril 
Published: April 2019

AbstractNanorings, which are macrocycles possessing radially directed π‐orbitals have shown fantastic development in the last ten years. Unravelling their unusual electronic properties has been one of the driving forces of this research field. However, and despite promising properties, their incorporation in organic electronic devices remains very scarce. In this work, we aim to contribute to bridge the gap between organic electronics and nanorings by reporting the synthesis, the structural and electronic properties and the incorporation in an organic field‐effect transistor (OFET) of a cyclic tetracarbazole, namely [4]cyclo‐N‐ethyl‐2,7‐carbazole ([4]C‐Et‐Cbz). The structural, photophysical and electrochemical properties have been compared to those of structurally related analogues [4]cyclo‐9,9‐diethyl‐2,7‐fluorene [4]C‐diEt‐F (with carbon bridges) and [8]‐cycloparaphenylene [8]CPP (without any bridge) in order to shed light on the impact of the bridging in nanorings. This work shows that nanorings can be used as an active layer in an OFET and provides a first benchmark in term of OFET characteristics for this type of molecules.
Prospect of Thiazole‐based γ‐Peptide Foldamers in Enamine Catalysis: Exploration of the Nitro‐Michael Addition
Authors: Aguesseau‐Kondrotas Julie , Simon Matthieu , Legrand Baptiste , Bantigniès Jean‐Louis , Kang Young Kee , Dumitrescu Dan , Van der Lee Arie , Campagne Jean‐Marc , de Figueiredo Renata Marcia , Maillard Ludovic T. 
Published: April 2019

AbstractAs three‐dimensional folding is prerequisite to biopolymer activity, complex functions may also be achieved through foldamer science. Because of the diversity of sizes, shapes and folding available with synthetic monomers, foldamer frameworks enable a numerous opportunities for designing new generations of catalysts. We herein demonstrate that heterocyclic γ‐peptide scaffolds represent a versatile platform for enamine catalysis. One central feature was to determine how the catalytic activity and the transfer of chiral information might be under the control of the conformational behaviours of the oligomer.
1,3‐Diene Polymerization Promoted by Half‐Sandwich Rare‐Earth‐Metal Dimethyl Complexes: Active Species Clustering and Cationization/Deactivation Processes
Authors: Hollfelder Christoph O. , Jende Lars N. , Dietrich Hans‐Martin , Eichele Klaus , Maichle‐Mössmer Cäcilia , Anwander Reiner 
Published: April 2019

AbstractWhen activated with fluorinated borate cocatalysts the trimetallic complexes [Cp*LnMe2]3 (Ln=Y, Lu; Cp*=C5Me5) promote efficiently the formation of high‐cis polybutadiene. Respective polyisoprenes instead bear much less pronounced microstructures, but reveal crosslinked products at lower polymerization temperatures. Varying the amount of cocatalyst, the emerging active species were examined by NMR spectroscopic techniques (incl. 1H DOSY). The occurrence of donor‐solvent and thermally induced degradation products of the highly reactive precatalyst [Cp*YMe2]3 and derived catalyst species was revealed by the elucidation of methylidene clusters [Cp*3Y3Me4(CH2)(thf)2] and [Cp*6Y6Me4(CH2)4], as well as [(Cp*Y)2Me2(N(Me)2(C6H4)]n[B(C6F5)4]n, implying a multimetallic active species.
Structure‐Based Design, Synthesis, and Biological Evaluation of Imidazo[4,5‐b]pyridin‐2‐one‐Based p38 MAP Kinase Inhibitors: Part 1
Authors: Kaieda Akira , Takahashi Masashi , Fukuda Hiromi , Okamoto Rei , Morimoto Shinji , Gotoh Masayuki , Miyazaki Takahiro , Hori Yuri , Unno Satoko , Kawamoto Tomohiro , Tanaka Toshimasa , Itono Sachiko , Takagi Terufumi , Sugimoto Hiroshi , Okada Kengo , Snell Gyorgy , Bertsch Ryan , Nguyen Jasmine , Sang Bi‐Ching , Miwatashi Seiji 
Published: April 2019

AbstractWe identified a lead series of p38 mitogen‐activated protein kinase inhibitors using a structure‐based design strategy from high‐throughput screening of hit compound 1. X‐ray crystallography of 1 with the kinase showed an infrequent flip of the peptide bond between Met109 and Gly110, which was considered to lead to high kinase selectivity. Our structure‐based design strategy was to conduct scaffold transformation of 1 with maintenance of hydrogen bond interactions with the flipped hinge backbone of the enzyme. In accordance with this strategy, we focused on scaffold transformation to identify imidazo[4,5‐b]pyridin‐2‐one derivatives as potent inhibitors of the p38 MAP kinase. Of the compounds evaluated, 21 was found to be a potent inhibitor of the p38 MAP kinase, lipopolysaccharide‐induced tumor necrosis factor‐α (TNF‐α) production in human monocytic leukemia cells, and TNF‐α‐induced production of interleukin‐8 in human whole blood cells. Herein we describe the discovery of potent and orally bioavailable imidazo[4,5‐b]pyridin‐2‐one‐based p38 MAP kinase inhibitors that suppressed cytokine production in a human whole blood cell‐based assay.
A Tough Metal‐Coordinated Elastomer: A Fatigue‐Resistant, Notch‐Insensitive Material with an Excellent Self‐Healing Capacity
Authors: Gai Guangjie , Liu Libin , Li Cheng‐Hui , Bose Ranjita K. , Li Dong , Guo Ning , Kong Biao 
Published: April 2019

AbstractSelf‐healing materials can prolong device life, but their relatively weak mechanical strength limits their applications. Introducing tunable metal‐ligand interactions into self‐healing systems can improve their mechanical strength. However, applying this concept to solid elastomers is a challenge. To address this need, polyurethane‐containing metal complexes were fabricated by introduction of a pyridine‐containing ligand into polyurethane, and subsequent coordination with Fe2+. The strong reversible coordination bond provides mechanical strength and self‐healing ability. By optimizing the monomer ratio and Fe2+ content, the resulting complex possesses a very high tensile strength of 4.6 MPa at strain of around 498 % and a high Young's modulus (3.2 MPa). Importantly, the metal complex exhibits an extremely high self‐healing efficiency of approximately 96 % of tensile strength at room temperature and around 30 % at 5 °C. The complex is notch‐insensitive and the fracture energy is 76186 J/m2, which is among the highest reported values for self‐healing systems.
Tandem Catalysis with Antagonistic Catalysts Compartmentalized in the Dispersed and Continuous Phases of a Pickering Emulsion
Authors: Vis Carolien M. , Smulders Luc C. J. , Bruijnincx Pieter C. A. 
Published: April 2019

AbstractTandem catalysis combines multiple conversion steps, catalysts, and reagents in one reaction medium, offering the potential to reduce waste and time. In this study, Pickering emulsions—emulsions stabilized by solid particles—are used as easy‐to‐prepare and bioinspired, compartmentalized reaction media for tandem catalysis. Making use of simple and inexpensive acid and base catalysts, the strategy of compartmentalization of two noncompatible catalysts in both phases of the emulsion is demonstrated by using the deacetalization–Knoevenagel condensation reaction of benzaldehyde dimethyl acetal as a probe reaction. In contrast to simple biphasic systems, which do not allow for tandem catalysis and show instantaneous quenching of the acid and base catalysts, the Pickering emulsions show efficient antagonistic tandem catalysis and give the desired product in high yield, as a result of an increased interfacial area and suppressed mutual destruction of the acid and base catalysts.
Edge/Defect Sites in α‐Co1−mFem(OH)x Nanoplates Responsible for Water Oxidation Activity
Authors: Liu Yangxing , Wang Miao , Li Yunwei , Yuan Gang , Zhang Xiangwen , Wang Qingfa 
Published: April 2019

AbstractFe‐doped transition metal (oxy)hydroxides are regarded as the most efficient oxygen evolution reaction (OER) electrocatalysts in alkaline conditions. The incorporation of Fe effectively enhances the OER activity of Co‐/Ni‐based materials, but the corresponding role of Fe in Co‐based (oxy)hydroxide materials still remains unresolved. Herein, α‐Co1−mFem(OH)x is synthesized and systematically engineered to study the effect of Fe content on the morphology, crystalline structure, electronic structure, and OER activity. As the Fe content is changed, the basic crystalline phase of α‐Co1−mFem(OH)x is consistent whereas the micromorphology changes. Much smaller and thinner nanoplates with more edge/defect sites are fabricated because of increased Fe incorporation. When the Fe content is more than 0.1, twin nanoparticles emerge at the edge/defect sites of the sister nanoplate. Additionally, the OER activity of α‐Co1−mFem(OH)x against Fe content can be plotted as a volcano curve. These data thus support a hypothesis that the edge/defect sites in α‐Co1−mFem(OH)x are responsible for the OER performance. The incorporation of Fe leads to not only the accelerated intrinsic reactivity of each active site, which is attributed to the strong electronic interaction between Co and Fe but also changes the number of edge/defect sites.
Investigation of the effect of plasma waves excitation on target normal sheath ion acceleration using fs laser‐irradiating hydrogenated structures
Authors: Torrisi L. , Cutroneo M. , Torrisi A. , Rosinski M. , Zaras‐Szydlowska A. , Parys P. 
Published: April 2019

Measurements of ion acceleration in polymethylmethacrylate foils covered by a thin copper film irradiated by fs laser in target normal sheath acceleration regime are presented. The ion acceleration depends on the laser parameters, such as the pulse energy; depends on the irradiation conditions, such as the focal point position of the laser with respect to the target surface; and depends on the target properties, such as the metallic film thickness. The proton acceleration increases in the presence of the metallic film enhancing the plasma electron density, reaching about 1.6 MeV energy for a focal position on the target surface. The plasma diagnostics uses SiC detectors, absorber foils, Faraday cups, and gafchromic films. Employing p‐polarized laser light and a suitable oblique incidence, it is possible to increase the proton acceleration up to about 2.0 MeV thanks to the effects of laser absorption resonance due to plasma waves excitation.
Increased population size of fish in a lowland river following restoration of structural habitat
Authors: Lyon Jarod P. , Bird Tomas J. , Kearns Joanne , Nicol Simon , Tonkin Zeb , Todd Charles R. , O'Mahony Justin , Hackett Graeme , Raymond Scott , Lieschke Jason , Kitchingman Adrian , Bradshaw Corey J. A. 
Published: April 2019

AbstractMost assessments of the effectiveness of river restoration are done at small spatial scales (<10 km) over short time frames (less than three years), potentially failing to capture large‐scale mechanisms such as completion of life‐history processes, changes to system productivity, or time lags of ecosystem responses. To test the hypothesis that populations of two species of large‐bodied, piscivorous, native fishes would increase in response to large‐scale structural habitat restoration (reintroduction of 4,450 pieces of coarse woody habitat into a 110‐km reach of the Murray River, southeastern Australia), we collected annual catch, effort, length, and tagging data over seven years for Murray cod (Maccullochella peelii) and golden perch (Macquaria ambigua) in a restored “intervention” reach and three neighboring “control” reaches. We supplemented mark–recapture data with telemetry and angler phone‐in data to assess the potentially confounding influences of movement among sampled populations, heterogeneous detection rates, and population vital rates. We applied a Bayesian hierarchical model to estimate changes in population parameters including immigration, emigration, and mortality rates. For Murray cod, we observed a threefold increase in abundance in the population within the intervention reach, while populations declined or fluctuated within the control reaches. Golden perch densities also increased twofold in the intervention reach. Our results indicate that restoring habitat heterogeneity by adding coarse woody habitats can increase the abundance of fish at a population scale in a large, lowland river. Successful restoration of poor‐quality “sink” habitats for target species relies on connectivity with high‐quality “source” habitats. We recommend that the analysis of restoration success across appropriately large spatial and temporal scales can help identify mechanisms and success rates of other restoration strategies such as restoring fish passage or delivering water for environmental outcomes.