bluuebunny/crossref_metadata_2025 huggingface dataset:
Moho depth model for the Central Asian Orogenic Belt from satellite gravity gradients
Authors: Guy Alexandra , Holzrichter Nils , Ebbing Jörg
Published: August 2017

The main purpose of this study is to construct a new 3‐D model of the Central Asian Orogenic Belt (CAOB) crust, which can be used as a starting point for future lithospheric studies. The CAOB is a Paleozoic accretionary orogen surrounded by the Siberian Craton to the north and the North China and Tarim Cratons to the south. This area is of great interest due to its enigmatic and still not completely understood geodynamic evolution. First, we estimate an initial crustal thickness by inversion of the vertical gravity component of the Gravity Field and Steady‐State Ocean Circulation Explorer (GOCE) and DTU10 models. Second, 3‐D forward modeling of the GOCE gravity gradients is performed, which determines the topography of the Moho, the geometry, and the density distribution of the deeper parts of the CAOB and its surroundings, taking into account the lateral and vertical density variations of the crust. The model is constrained by seismic refraction, reflection, and receiver function studies and geological studies. In addition, we discuss the isostatic implications of the differences between the seismic Moho and the resulting 3‐D gravity Moho, complemented by the analysis of the lithostatic load distribution at the upper mantle level. Finally, the correlation between the contrasting tectonic domains and the thickness of the crust reveals the inheritance of Paleozoic and Mesozoic geodynamics, particularly the magmatic provinces and the orocline which preserve their crustal features.
Single Component Organic Solar Cells Based on Oligothiophene‐Fullerene Conjugate
Authors: Nguyen Thanh Luan , Lee Tack Ho , Gautam Bhoj , Park Song Yi , Gundogdu Kenan , Kim Jin Young , Woo Han Young
Published: August 2017

A new donor (D)–acceptor (A) conjugate, benzodithiophene‐rhodanine–[6,6]‐phenyl‐C61 butyric acid methyl ester (BDTRh–PCBM) comprising three covalently linked blocks, one of p‐type oligothiophene containing BDTRh moieties and two of n‐type PCBM, is designed and synthesized. A single component organic solar cell (SCOSC) fabricated from BDTRh–PCBM exhibits the power conversion efficiency (PCE) of 2.44% and maximum external quantum efficiency of 46%, which are the highest among the reported efficiencies so far. The SCOSC device shows efficient charge transfer (CT, ≈300 fs) and smaller CT energy loss, resulting in the higher open‐circuit voltage of 0.97 V, compared to the binary blend (BDTRh:PCBM). Because of the integration of the donor and acceptor in a single molecule, BDTRh‐PCBM has a specific D–A arrangement with less energetic disorder and reorganization energy than blend systems. In addition, the SCOSC device shows excellent device and morphological stabilities, showing no degradation of PCE at 80 °C for 100 h. The SCOSC approach may suggest a great way to suppress the large phase segregation of donor and acceptor domains with better morphological stability compared to the blend device.
Graded Heterojunction Engineering for Hole‐Conductor‐Free Perovskite Solar Cells with High Hole Extraction Efficiency and Conductivity
Authors: Li Bo , Zhang Yanan , Zhang Luyuan , Yin Longwei
Published: August 2017

Despite great progress in the photovoltaic conversion efficiency (PCE) of inorganic–organic hybrid perovskite solar cells (PSCs), the large‐scale application of PSCs still faces serious challenges due to the poor‐stability and high‐cost of the spiro‐OMeTAD hole transport layer (HTL). It is of great fundamental importance to rationally address the issues of hole extraction and transfer arising from HTL‐free PSCs. Herein, a brand‐new PSC architecture is designed by introducing multigraded‐heterojunction (GHJ) inorganic perovskite CsPbBrxI3−x layers as an efficient HTL. The grade adjustment can be achieved by precisely tuning the halide proportion and distribution in the CsPbBrxI3−x film to reach an optimal energy alignment of the valance and conduction band between MAPbI3 and CsPbBrxI3−x. The CsPbBrxI3−x GHJ as an efficient HTL can induce an electric field where a valance/conduction band edge is leveraged to bend at the heterojunction interface, boosting the interfacial electron–hole splitting and photoelectron extraction. The GHJ architecture enhances the hole extraction and conduction efficiency from the MAPbI3 to the counter electrode, decreases the recombination loss during the hole transfer, and benefits in increasing the open‐circuit voltage. The optimized HTL‐free PCS based on the GHJ architecture demonstrates an outstanding thermal stability and a significantly improved PCE of 11.33%, nearly 40% increase compared with 8.16% for pure HTL‐free devices.
Scalable, “Dip‐and‐Dry” Fabrication of a Wide‐Angle Plasmonic Selective Absorber for High‐Efficiency Solar–Thermal Energy Conversion
Authors: Mandal Jyotirmoy , Wang Derek , Overvig Adam C. , Shi Norman N. , Paley Daniel , Zangiabadi Amirali , Cheng Qian , Barmak Katayun , Yu Nanfang , Yang Yuan
Published: August 2017

A galvanic‐displacement‐reaction‐based, room‐temperature “dip‐and‐dry” technique is demonstrated for fabricating selectively solar‐absorbing plasmonic‐nanoparticle‐coated foils (PNFs). The technique, which allows for facile tuning of the PNFs' spectral reflectance to suit different radiative and thermal environments, yields PNFs which exhibit excellent, wide‐angle solar absorptance (0.96 at 15°, to 0.97 at 35°, to 0.79 at 80°), and low hemispherical thermal emittance (0.10) without the aid of antireflection coatings. The thermal emittance is on par with those of notable selective solar absorbers (SSAs) in the literature, while the wide‐angle solar absorptance surpasses those of previously reported SSAs with comparable optical selectivities. In addition, the PNFs show promising mechanical and thermal stabilities at temperatures of up to 200 °C. Along with the performance of the PNFs, the simplicity, inexpensiveness, and environmental friendliness of the “dip‐and‐dry” technique makes it an appealing alternative to current methods for fabricating selective solar absorbers.
Exploring the Charge Transport in Conjugated Polymers
Authors: Xu Yong , Sun Huabin , Li Wenwu , Lin Yen‐Fu , Balestra Francis , Ghibaudo Gerard , Noh Yong‐Young
Published: August 2017

Conjugated polymers came to an unprecedented epoch that the charge transport is limited only by small disorder within aggregated domains. Accurate evaluation of transport performance is thus vital to optimizing further molecule design. Yet, the routine method by means of the conventional field‐effect transistors may not satisfy such a requirement. Here, it is shown that the extrinsic effects of Schottky barrier, access transport through semiconductor bulk, and concurrent ambipolar conduction seriously influence transport analysis. The planar transistors incorporating ohmic contacts free of access and ambipolar conduction afford an ideal access to charge transport. It is found, however, that only the planar transistors operating in low‐field regime are reliable to explore the inherent transport properties due to the energetic disorder lowering by the lateral field induced by high drain voltage. This work opens up a robust approach to comprehend the delicate charge transport in conjugated polymers so as to develop high‐performance semiconducting polymers for promising plastic electronics.
Recent Progress in Bionic Condensate Microdrop Self‐Propelling Surfaces
Authors: Gong Xiaojing , Gao Xuefeng , Jiang Lei
Published: August 2017

Bionic condensate microdrop self‐propelling (CMDSP) surfaces are attracting increased attention as novel, low‐adhesivity superhydrophobic surfaces due to their value in fundamental research and technological innovation, e.g., for enhancing heat transfer, energy‐effective antifreezing, and electrostatic energy harvesting. Here, the focus is on recent progress in bionic CMDSP surfaces. Metal‐based CMDSP surfaces, which are the most promising in their respective fields, are highlighted for use in future applications. The selected topics are divided into four sections: biological prototypes, mechanism and construction rules, fabrication, and applications of metal‐based CMDSP surfaces. Finally, the challenges and future development trends in bionic CMDSP surfaces are envisioned, especially the utilization of potential bionic inspiration in the design of more advanced CMDSP surfaces.
Water‐Enabled Healing of Conducting Polymer Films
Authors: Zhang Shiming , Cicoira Fabio
Published: August 2017

The conducting polymer polyethylenedioxythiophene doped with polystyrene sulfonate (PEDOT:PSS) has become one of the most successful organic conductive materials due to its high air stability, high electrical conductivity, and biocompatibility. In recent years, a great deal of attention has been paid to its fundamental physicochemical properties, but its healability has not been explored in depth. This communication reports the first observation of mechanical and electrical healability of PEDOT:PSS thin films. Upon reaching a certain thickness (about 1 µm), PEDOT:PSS thin films damaged with a sharp blade can be electrically healed by simply wetting the damaged area with water. The process is rapid, with a response time on the order of 150 ms. Significantly, after being wetted the films are transformed into autonomic self‐healing materials without the need of external stimulation. This work reveals a new property of PEDOT:PSS and enables its immediate use in flexible and biocompatible electronics, such as electronic skin and bioimplanted electronics, placing conducting polymers on the front line for healing applications in electronics.
Kinetics of Photoinduced Wettability Switching on Nanoporous Titania Surfaces under Oil
Authors: Panchanathan Divya , Kwon Gibum , Qahtan Talal F. , Gondal Mohammad A. , Varanasi Kripa K. , McKinley Gareth H.
Published: August 2017

Titanium dioxide (titania or TiO2) is well known for its photocatalytic properties and its ability to remove organic contaminants under UV light illumination. It is also known to switch its surface wetting characteristics from being hydrophilic to superhydrophilic under exposure to UV light in air. However, less is known about the switching of the hydrophilicity of TiO2 surfaces immersed in an oil medium. In this work, self‐assembled TiO2 nanoparticle surfaces are immersed in an oil environment, and the kinetics of contamination‐induced hydrophobicity and photoinduced hydrophilicity are studied using in situ contact angle measurements. A simple model is developed to relate the evolution in the measured contact angle to photocatalytically induced changes on the surface of nanoporous titania by integrating the Langmuir–Hinshelwood adsorption isotherm with the Cassie–Baxter analysis of the effective contact angle of a drop sitting on a composite surface. The resulting model can be used to predict and control wetting kinetics in drop coalescence applications. Moreover, it is shown that immersed oil–water separation membranes which have been fouled by low surface tension contaminants can be rapidly recovered in situ using this underwater photocatalytic reaction without the need for backwashing or harsh chemical reagents.
Cellular Architecture‐Based All‐Polymer Flexible Thin‐Film Photodetectors with High Performance and Stability in Harsh Environment
Authors: Wang Qian , Jin Zhiwen , Zhang Xisheng , Gao Zhenfei , Xu Hua , Bin Haijun , Zhang Zhi‐Guo , Li Yongfang , Liu Shengzhong (Frank)
Published: August 2017

Here, a cellular architecture consisting of hundreds of blend cylinders embedded into P‐type film is designed for all‐polymer (donor J51 and acceptor N2200) flexibility thin‐film photodetectors for the first time. The blend cylinders provide more blend/P‐type interfaces, which is beneficial for excitons to efficiently dissociate, while the high mobility P‐type film guarantees high mobility and free carriers to fast transport. Moreover, each individual cylinder exhibits high resistance to the interdiffusion from the cylinders into the P‐layer, thus it effectively prevents formation of nanoscale network even under stressed conditions. As a result, the photocurrent of cellular device enhances about two orders of magnitude and the rise/decay times decrease to 0.50/1.01 s compared with the blend one. Meanwhile, the all polymer J51:N2200‐based cellular photodetectors show very high stability when heated to 200 °C or bended 1000 times, which is due to the low diffusion rate of the very‐long‐chain polymer and the nature of the cellular structure. These results demonstrate that the cellular structure‐based all‐polymer thin‐film photodetectors might be promising candidates for further applications.
Widely Tunable Infrared Plasmonic Nanoantennas Using Directed Assembly
Authors: Fontana Jake , Nita Rafaela , Charipar Nicholas , Naciri Jawad , Park Kyoungweon , Dunkelberger Adam , Owrutsky Jeff , Piqué Alberto , Vaia Richard , Ratna Banahalli
Published: August 2017

Infrared plasmonic nanoantennas are key building blocks in nanotechnology. By coupling and confining light into spatial volumes below the diffraction limit, infrared plasmonic nanoantennas provide unique opportunities to sense and signal at nanometer length scales for energy harvesting, as light sources, and in nanomedicine applications. However, in contrast to their radio‐ and microwave counterparts, widespread use of plasmonic nanoantennas has been limited, due in part to the inability to synthesize these structures maintaining nanoscale precision in large batches with uniform yields. This communication describes a directed assembly approach to generate large quantities of infrared plasmonic nanoantennas with sharp and widely tunable absorption peaks from 1 to 3 µm. It is experimentally demonstrated that the nanoantenna absorption peak depends linearly on the chain length, in agreement with simulations, providing a straightforward means to understand and predict the infrared response of these materials.
Nanostructuring Noble Metals as Unsupported Electrocatalysts for Polymer Electrolyte Fuel Cells
Authors: Cai Bin , Henning Sebastian , Herranz Juan , Schmidt Thomas J. , Eychmüller Alexander
Published: August 2017

Two major challenges that impede fuel cell technology breakthrough are the insufficient activity of the electrocatalysts for the oxygen reduction reaction and their degradation during operation, caused by the potential‐induced corrosion of their carbon‐support upon fuel cell operation. Unsupported electrocatalysts derived from tailored noble‐metal nanostructures are superior to the conventional carbon‐supported Pt nanoparticle catalysts and address these barriers by fine‐tuning the surface composition and eliminating the support. Herein, recent efforts and achievements in the design, synthesis and characterization of unsupported electrocatalysts are reviewed, paying special attention to noble‐metal aerogels, nano/meso‐structured thin films and template‐derived metal nanoarchitectures. Their electrocatalytic performances for oxygen reduction are compared and discussed, and examples of successful catalyst transfer to polymer electrolyte fuel cells are highlighted. This report aims to demonstrate the potential and challenges of implementing unsupported catalysts in fuel cells, thereby providing a perspective on the further development of these materials.
Post Iron Decoration of Mesoporous Nitrogen‐Doped Carbon Spheres for Efficient Electrochemical Oxygen Reduction
Authors: Liu Zhuang , Sun Fei , Gu Lin , Chen Gen , Shang Tongtong , Liu Jing , Le Zaiyuan , Li Xianyang , Wu Hao Bin , Lu Yunfeng
Published: August 2017

Iron–nitrogen–carbon (Fe–N–C) catalysts are considered as the most promising nonprecious metal catalysts for oxygen reduction reactions (ORRs). Their synthesis generally involves complex pyrolysis reactions at high temperature, making it difficult to optimize their composition, pore structure, and active sites. This study reports a simple synthesis strategy by reacting preformed nitrogen‐doped carbon scaffolds with iron pentacarbonyl, a liquid precursor that can effectively form active sites with the nitrogen sites, enabling more effective control of the catalyst. The resultant catalyst possesses a well‐defined mesoporous structure, a high surface area, and optimized active sites. The catalysts exhibit high ORR activity comparable to that of Pt/C catalyst (40% Pt loading) in alkaline media, with excellent stability and methanol tolerance. The synthetic strategy can be extended to synthesize other metal–N–C catalysts.
Surface Free Energy‐Induced Assembly to the Synthesis of Grid‐Like Multicavity Carbon Spheres with High Level In‐Cavity Encapsulation for Lithium–Sulfur Cathode
Authors: Zhang Lu‐Hua , He Bin , Li Wen‐Cui , Lu An‐Hui
Published: August 2017

Carbon microcapsules with a large interior cavity and porous shell are ideal hosts for guest species, while to maximize in‐cavity volume has always been a challenge. Herein, a surface free energy‐induced assembly approach is proposed for synthesis of multicavity carbon spheres (MCC). When used as a host for lithium–sulfur cathodes, MCC are fully accessible for sulfur—with high level in‐cavity encapsulation ability of grid‐like cavities. The crucial point for this assembly approach is the employment of small sized nanoemulsions with high homogeneity as primary building blocks. Spontaneous aggregation and assembly of substructural units are processing in following hydrothermal synthesis induced by reduction of surface free energy of system. As a result, multicavity structure is formed, where the size and number of cavities can be modulated by changing size of nanoemulsion and concentration of polymer. Confined pyrolysis enables to further enlarge cavity size compared to regular pyrolysis. The carbon–sulfur cathode exhibits excellent cycling stability and rate performance, i.e., high capacity of 943 and 869 mA h g−1 after 200 cycles at current density of 0.5 and 2.0 C. The strategy has paved the way for custom‐ordered synthesis of nanostructured carbon with keen demands in high loading capacity of guest species.
Using video and theater to increase knowledge and change attitudes—Why are gorillas important to the world and to Congo?
Authors: Breuer Thomas , Mavinga Franck Barrel , Evans Ron , Lukas Kristen E.
Published: August 2017

Applying environmental education in primate range countries is an important long‐term activity to stimulate pro‐conservation behavior. Within captive settings, mega‐charismatic species, such as great apes are often used to increase knowledge and positively influence attitudes of visitors. Here, we evaluate the effectiveness of a short‐term video and theater program developed for a Western audience and adapted to rural people living in two villages around Nouabalé‐Ndoki National Park, Republic of Congo. We assessed the knowledge gain and attitude change using oral evaluation in the local language (N = 111). Overall pre‐program knowledge about Western gorillas (Gorilla gorilla) was high. Detailed multivariate analysis of pre‐program knowledge revealed differences in knowledge between two villages and people with different jobs while attitudes largely were similar between groups. The short‐term education program was successful in raising knowledge, particularly of those people with less pre‐program knowledge. We also noted an overall significant attitude improvement. Our data indicate short‐term education programs are useful in quickly raising knowledge as well improving attitudes. Furthermore, education messages need to be clearly adapted to the daily livelihood realities of the audience, and multi‐variate analysis can help to identify potential target groups for education programs.
Two‐Dimensional Calix[4]arene‐based Metal–Organic Coordination Networks of Tunable Crystallinity
Authors: Moradi Mina , Tulli Ludovico G. , Nowakowski Jan , Baljozovic Milos , Jung Thomas A. , Shahgaldian Patrick
Published: August 2017

A flexible and versatile method to fabricate two‐dimensional metal–organic coordination networks (MOCNs) by bottom‐up self‐assembly is described. 2D crystalline layers were formed at the air–water interface, coordinated by ions from the liquid phase, and transferred onto a solid substrate with their crystallinity preserved. By using an inherently three‐dimensional amphiphile, namely 25,26,27,28‐tetrapropoxycalix[4]arene‐5,11,17,23‐tetracarboxylic acid, and a copper metal node, large and monocrystalline dendritic MOCN domains were formed. The method described allows for the fabrication of monolayers of tunable crystallinity on liquid and solid substrates. It can be applied to a large range of differently functionalized organic building blocks, also beyond macrocycles, which can be interconnected by diverse metal nodes.
Malonic Acid Diazoesters for C−H Insertion Crosslinking (CHic) Reactions: A Versatile Method for the Generation of Tailor‐Made Surfaces
Authors: Kotrade Philip F. , Rühe Jürgen
Published: August 2017

A simple and versatile method for the modification of a broad spectrum of surfaces with thin polymer films through the thermally or photochemically induced generation of surface‐attached polymer networks is reported. The system is based on copolymers containing diazomalonate groups, which can be activated by heat or light. To this end, the copolymers are deposited from solution onto solid substrates by standard techniques of thin‐film deposition (spin coating, dip coating). Upon activation the diazomalonate group decomposes and forms a carbene, which induces C−H insertion crosslinking (CHic) reactions. In the course of this process network formation and covalent surface attachment occur at the same time. The crosslinking process proceeds very rapidly, especially when the carbenes generated in the activation process cannot undergo Wolff‐rearrangement. The presented system can be used for the generation of a wide range of polymer layers and microstructures on a broad spectrum of surfaces.
HKOH‐1: A Highly Sensitive and Selective Fluorescent Probe for Detecting Endogenous Hydroxyl Radicals in Living Cells
Authors: Bai Xiaoyu , Huang Yueyang , Lu Mingyang , Yang Dan
Published: August 2017

The hydroxyl radical (.OH), one of the most reactive and deleterious reactive oxygen species (ROS), has been suggested to play an essential role in many physiological and pathological scenarios. However, a reliable and robust method to detect endogenous .OH is currently lacking owing to its extremely high reactivity and short lifetime. Herein we report a fluorescent probe HKOH‐1 with superior in vitro selectivity and sensitivity towards .OH. With this probe, we have calibrated and quantified the scavenging capacities of a wide range of reported .OH scavengers. Furthermore, HKOH‐1r, which was designed for better cellular uptake and retention, has performed robustly in detection of endogenous .OH generation by both confocal imaging and flow cytometry. Furthermore, this probe has been applied to monitor .OH generation in HeLa cells in response to UV light irradiation. Therefore, HKOH‐1 could be used for elucidating .OH related biological functions.
Iron‐Catalyzed anti‐Selective Carbosilylation of Internal Alkynes
Authors: Iwamoto Takahiro , Nishikori Tatsushi , Nakagawa Naohisa , Takaya Hikaru , Nakamura Masaharu
Published: August 2017

Reported is the anti‐selective carbosilylation of internal alkynes with silylborane and alkyl halides using a FeBr2/DPPE catalyst system. The iron catalyst allows simultaneous introduction of a carbon electrophile and a silicon nucleophile to simple internal alkynes, including diaryl‐, dialkyl‐, and aryl/alkyl‐substituted alkynes, in a highly stereoselective manner. Alkyl halides are applicable as the electrophiles, thereby enabling the synthesis of a variety of tetrasubstituted alkenylsilanes. In addition, syn‐selective carbosilylation was achieved through stereoswitching, by using a silylborane having oxygen functionality on the silyl group. This novel iron‐catalyzed carbosilylation is a useful tool for expedient synthesis of stereodefined multisubstituted olefins, a fundamental structural motif in organic chemistry.
Fluorine Pseudocontact Shifts Used for Characterizing the Protein–Ligand Interaction Mode in the Limit of NMR Intermediate Exchange
Authors: Gao Jia , Liang E , Ma Rongsheng , Li Fudong , Liu Yixiang , Liu Jiuyang , Jiang Ling , Li Conggang , Dai Haiming , Wu Jihui , Su Xuncheng , He Wei , Ruan Ke
Published: August 2017

The characterization of protein–ligand interaction modes becomes recalcitrant in the NMR intermediate exchange regime as the interface resonances are broadened beyond detection. Here, we determined the 19F low‐populated bound‐state pseudocontact shifts (PCSs) of mono‐ and di‐fluorinated inhibitors of the BRM bromodomain using a highly skewed protein/ligand ratio. The bound‐state 19F PCSs were retrieved from 19F chemical exchange saturation transfer (CEST) in the presence of the lanthanide‐labeled protein, which was termed the 19F PCS‐CEST approach. These PCSs enriched in spatial information enabled the identification of best‐fitting poses, which agree well with the crystal structure of a more soluble analog in complex with the BRM bromodomain. This approach fills the gap of the NMR structural characterization of lead‐like inhibitors with moderate affinities to target proteins, which are essential for structure‐guided hit‐to‐lead evolution.
Efficient Aryl Migration from an Aryl Ether to a Carboxylic Acid Group To Form an Ester by Visible‐Light Photoredox Catalysis
Authors: Wang Shao‐Feng , Cao Xiao‐Ping , Li Yang
Published: August 2017

We have developed a highly efficient aryl migration from an aryl ether to a carboxylic acid group through retro‐Smiles rearrangement by visible‐light photoredox catalysis at ambient temperature. Transition metals and a stoichiometric oxidant and base are avoided in the transformation. Inspired by the high efficiency of this transformation and the fundamental importance of C−O bond cleavage, we developed a novel approach to the C−O cleavage of a biaryl ether to form two phenolic compounds, as demonstrated by a one‐pot, two‐step gram‐scale reaction under mild conditions. The aryl migration exhibits broad scope and can be applied to the synthesis of pharmaceutical compounds, such as guacetisal. Primary mechanistic studies indicate that the catalytic cycle occurs by a reductive quenching pathway.
Valence Interconversion of Octahedral Nickel(II/III/IV) Centers
Authors: Kouno Masahiro , Yoshinari Nobuto , Kuwamura Naoto , Yamagami Kohei , Sekiyama Akira , Okumura Mitsutaka , Konno Takumi
Published: August 2017

Three oxidation states (+2, +3, +4) of an octahedral nickel center were stabilized in a newly prepared RhNiRh trinuclear complex, [Ni{Rh(apt)3}2]n+ (apt=3‐ aminopropanethiolate), in which the nickel center was bound by six thiolato donors sourced from two redox‐inert fac‐[RhIII(apt)3] octahedral units. The three oxidation states of the octahedral nickel center were fully characterized by single‐crystal X‐ray crystallography, as well as spectroscopic, electrochemical, and magnetic measurements; all three were interconvertible, and the conversion was accompanied by changes in color, magnetism, and Jahn–Teller distortion.
The Effect of Carboxamide/Sulfonamide Replacement in Arylpiperazinylalkyl Derivatives on Activity to Serotonin and Dopamine Receptors
Authors: Kowalski Piotr , Śliwa Paweł , Satała Grzegorz , Kurczab Rafał , Bartos Ilona , Zuchowicz Karol
Published: August 2017

A series of carboxamide and sulfonamide alkyl (p‐xylyl and benzyl) 1‐(2‐methoxyphenyl)piperazine (o‐OMe‐PhP) and 1‐(2,3‐dichlorophenyl)piperazine (2,3‐DCPP) analogs were prepared and tested for their affinity to bind to serotonin 5‐HT1A/5‐HT6/5‐HT7 and dopamine D2 receptors. This chemical modification let us explore the impact of the replacement of the carboxamide by the sulfonamide group on the affinity changes. In both the o‐OMe‐PhP and 2,3‐DCPP series, the relative activities of the carboxamides versus sulfonamides toward the 5‐HT1A/5‐HT6/5‐HT7 and D2 receptors show similar trends. Varied or similar activities for particular receptors were found for the carboxamides/sulfonamides with p‐xylyl spacer, while of the two classes of carboxamides and sulfonamides examined, benzyl derivatives of the sulfonamides displayed the highest serotoninergic affinity, in particular to the 5‐HT7 receptors (Ki 8–85 nM). The Ki values revealed that, irrespective of the carboxamide/sulfonamide zone, both p‐xylyl and benzyl derivatives had the highest affinity for the dopamine D2 receptor (i.e., 16 out of 24 compounds investigated have an affinity below 100 nM). A molecular modeling study of carboxamide 9a and sulfonamide 9b showed that their binding effects to each of 5‐HT1AR and D2R created binding modes interaction with different conserved receptors residues. Structural similarities of carboxamide 9a in complexes with a 5‐HT1AR (9aI) and D2R (9aII) are over 83%, while the respective similarities of sulfonamide 9b structures (9bI/9bII) are only about 40%.
The Safety and Immunogenicity of Live Zoster Vaccination in Patients With Rheumatoid Arthritis Before Starting Tofacitinib: A Randomized Phase II Trial
Authors: Winthrop Kevin L. , Wouters Ann G. , Choy Ernest H. , Soma Koshika , Hodge Jennifer A. , Nduaka Chudy I. , Biswas Pinaki , Needle Elie , Passador Sherry , Mojcik Christopher F. , Rigby William F.
Published: August 2017

Objective

Patients with rheumatoid arthritis (RA) are at increased risk of herpes zoster, and vaccination is recommended for patients ages 50 years and older, prior to starting treatment with biologic agents or tofacitinib. Tofacitinib is an oral JAK inhibitor for the treatment of RA. We evaluated its effect on the immune response and safety of live zoster vaccine (LZV).

Methods

In this phase II, 14‐week, placebo‐controlled trial, patients ages 50 years and older who had active RA and were receiving background methotrexate were given LZV and randomized to receive tofacitinib 5 mg twice daily or placebo 2–3 weeks postvaccination. We measured humoral responses (varicella zoster virus [VZV]–specific IgG level as determined by glycoprotein enzyme‐linked immunosorbent assay) and cell‐mediated responses (VZV‐specific T cell enumeration, as determined by enzyme‐linked immunospot assay) at baseline and 2 weeks, 6 weeks, and 14 weeks postvaccination. End points included the geometric mean fold rise (GMFR) in VZV‐specific IgG levels (primary end point) and T cells (number of spot‐forming cells/106 peripheral blood mononuclear cells) at 6 weeks postvaccination.

Results

One hundred twelve patients were randomized to receive tofacitinib (n = 55) or placebo (n = 57). Six weeks postvaccination, the GMFR in VZV‐specific IgG levels was 2.11 in the tofacitinib group and 1.74 in the placebo group, and the VZV‐specific T cell GMFR was similar in the tofacitinib group and the placebo group (1.50 and 1.29, respectively). Serious adverse events occurred in 3 patients in the tofacitinib group (5.5%) and 0 patients (0.0%) in the placebo group. One patient, who lacked preexisting VZV immunity, developed cutaneous vaccine dissemination 2 days after starting tofacitinib (16 days postvaccination). This resolved after tofacitinib was discontinued and the patient received antiviral treatment.

Conclusion

Patients who began treatment with tofacitinib 2–3 weeks after receiving LZV had VZV‐specific humoral and cell‐mediated immune responses to LZV similar to those in placebo‐treated patients. Vaccination appeared to be safe in all of the patients except 1 patient who lacked preexisting VZV immunity.
Anschlüsse für den Holzbau mit Polymerverguss
Authors: Jahreis Markus , Oppel Mike , Rautenstrauch Karl
Published: August 2017

Mit dem zunehmenden Einsatz von Holz für Ingenieurbauwerke steigen die Ansprüche an eine montagefreundliche und materialgerechte Ausbildung effektiver Anschlüsse mit hoher Tragfähigkeit auch unter mehrachsig interagierenden Beanspruchungen. Dieser Beitrag stellt baustellengerechte Varianten für Zug‐, Druck‐ sowie Biegeanschlüsse im Holzbau auf der Basis polymergebundener Vergussmassen vor. Hierbei werden typisierte frei geformte Einbauteile, z. B. aus Stahl mit metrischem Gewinde als Muffen‐ oder Gewindeanschluss, bereits vom Hersteller mittels „Vergusskleben“ in nahezu beliebig geformten, auch größer dimensionierten Ausnehmungen im Holzbauteil verankert. Damit ermöglichen derartige Vergusslösungen dem Holzbau nicht nur einen optimalen Kraftschluss, sondern auch das effiziente direkte Zusammenspiel mit typisierten Anschlüssen anderer Bauweisen, wie sie z. B. im Stahl‐ oder Stahlbetonbau üblich sind. In diesem Kontext können daher die als Stütze oder Biegeträger optimierten Holzbauteile effektiver als bisher eingesetzt werden. Darüber hinaus eignet sich der Polymerverguss hervorragend für die Ein‐ sowie Durchleitung lokaler hoher Druckbeanspruchungen quer zur Holzfaserrichtung. Der vorliegende Artikel zeigt zudem, dass mittels geeigneter numerischer 3‐D‐FE‐Modelle der vorhandene komplexe Beanspruchungszustand dieser Vergussanschlüsse zuverlässig beurteilt werden kann.
Bio‐Based Production of Dimethyl Itaconate From Rice Wine Waste‐Derived Itaconic Acid
Authors: Joo Young‐Chul , You Seung Kyou , Shin Sang Kyu , Ko Young Jin , Jung Ki Ho , Sim Sang A. , Han Sung Ok
Published: August 2017

Dimethyl itaconate is an important raw material for copolymerization, but it is not synthesized from itaconic acid by organisms. Moreover, Corynebacterium glutamicum is used as an important industrial host for the production of organic acids, but it does not metabolize itaconic acid. Therefore, the biosynthetic route toward dimethyl itaconate from itaconic acid is highly needed. In this study, a biological procedure for dimethyl itaconate production is developed from rice wine waste‐derived itaconic acid using the engineered C. glutamicum strain. The first step is to investigate the effect of the co‐overexpression of the codon‐optimized cis‐aconitic acid decarboxylase (CadA*) and a transcriptional regulator of genes involved in acetic acid metabolism (RamA) on itaconic acid production. The second step is to convert itaconic acid into dimethyl itaconate by lipase‐catalyzed esterification. The CadA* and RamA‐overexpressing CG4 strain increases the itaconic acid concentration under N‐starvation with glucose and acetic acid compared with the concentration produced in the base mCGXII medium with glucose. Furthermore, the rice wine waste‐derived itaconic acid is successfully converted into dimethyl itaconate using lipase from Rhizomucor miehei and a methanol substrate. This study is the first trial for bio‐based production of dimethyl itaconate from rice wine waste‐derived itaconic acid.
Sorbus aucuparia and Sorbus aria as a Source of Antioxidant Phenolics, Tocopherols, and Pigments
Authors: Šavikin Katarina P. , Zdunić Gordana M. , Krstić‐Milošević Dijana B. , Šircelj Helena J. , Stešević Danijela D. , Pljevljakušić Dejan S.
Published: August 2017

Due to its nutritive and medicinal properties, berries of some Sorbus species are used for the preparation of jams and jelly as well as in traditional medicine. On the other hand, their chemical composition is not much studied especially of those grown in Balkan Peninsula. We have analyzed individual phenolics, tocopherols, carotenoids and chlorophylls using HPLC in berries from Sorbus aucuparia and Sorbus aria collected in different localities in Serbia and Montenegro together with the amounts of total phenolics and proanthocyanidins as well as their radical scavenging activity against DPPH radical. Berries of S. aucuparia were richer source of polyphenolics in comparision with S. aria and, regardless the species and locality, caffeoylquinic acids such as neochlorogenic and chlorogenic acid were the most abundant compounds. Among analyzed tocopherols the most abundant in all samples was α‐tocopherol (0.48 – 19.85 μg/g dw) as it was β‐carotene among carotenoids (mean concentration of 0.98 μg/g dw in S. aucuparia and 0.40 μg/g dw in S. aria, respectively). Correlation between total phenolics and DPPH radical scavenging activity was noticed. Our study represents comprehensive report on chemical composition of S. aucuparia and S. aria which could contribute to a better understanding of their quality.
Efficient Biocatalytic Reductive Aminations by Extending the Imine Reductase Toolbox
Authors: Roiban Gheorghe‐Doru , Kern Marcelo , Liu Zhi , Hyslop Julia , Tey Pei Lyn , Levine Matthew S. , Jordan Lydia S. , Brown Kristin K. , Hadi Timin , Ihnken Leigh Anne F. , Brown Murray J. B.
Published: August 2017

Chiral secondary and tertiary amines are ubiquitous in pharmaceutical, fine, and specialty chemicals, but their synthesis typically suffers from significant sustainability and selectivity challenges. Biocatalytic alternatives, such as enzyme‐catalyzed reductive amination, offer several advantages over traditional chemistry, but industrial applicability has not yet been demonstrated. Herein, we report the use of cell lysates expressing imine reductases operating at 1:1 stoichiometry for a variety of amines and carbonyls. A collection of biocatalysts with diversity in coverage of small molecules and direct industrial applicability is presented.
Reaction Engineering for Continuous Production of Silver Nanoparticles
Authors: Deshpande Javdeep B. , Kulkarni Amol A.
Published: August 2017

A scalable process for the production of silver nanoparticles that allows for complete conversion of the limiting reactant is analyzed in detail. The kinetics of silver nanoparticle synthesis using citrate reduction are investigated and used for development of a reaction engineering model to facilitate the reactor design. The effect of temperature, pH, concentration and mixing (axial dispersion) on the rates of nucleation and growth are analyzed quantitatively. An approach that considers reaction kinetics coupled with quality of dispersion is developed for reactor design as well as selection of reactor configurations for the synthesis of specific particle sizes. The developed approach has been applied for continuous production of 10‐L suspension silver nanoparticles with very narrow particle size distribution.
Ligand Noninnocence in Iron Corroles: Insights from Optical and X‐ray Absorption Spectroscopies and Electrochemical Redox Potentials
Authors: Ganguly Sumit , Giles Logan J. , Thomas Kolle E. , Sarangi Ritimukta , Ghosh Abhik
Published: August 2017

Two new series of iron meso‐tris(para‐X‐phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF3, H, Me, and OMe, and Tol=p‐methylphenyl (p‐tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe2(μ‐O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]}2O, and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity‐weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe‐K pre‐edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected FeIV‐like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be FeIII‐like. These results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.
Catalytic Asymmetric Formal [3+2] Cycloaddition of 2‐Isocyanatomalonate Esters and Unsaturated Imines: Synthesis of Highly Substituted Chiral γ‐Lactams
Authors: Espinosa Miguel , Blay Gonzalo , Cardona Luz , Muñoz M. Carmen , Pedro José R.
Published: August 2017

Unlike their isocyano and isothiocyanato analogues, isocyanato esters remain almost unexplored as formal 1,3‐dipoles in asymmetric catalytic reactions. The first asymmetric formal [3+2] cycloaddition involving isocyanato esters and electrophilic alkenes is reported. Diisopropyl 2‐isocyanatomalonate reacts with α,β‐unsaturated N‐(o‐anisidyl) imines in the presence of a Mg(OTf)2–BOX complex to give highly substituted chiral pyrrolidinones featuring a conjugate exocyclic double bond with excellent yields and enantiomeric excesses up to 99 %. Several transformations of the resulting heterocycles, including the synthesis of a pyroglutamic acid derivative, have been carried out.
Synergistic Effects in PtII–Porphyrinoid Dyes as Candidates for a Dual‐Action Anticancer Therapy: A Theoretical Exploration
Authors: Alberto Marta Erminia , Adamo Carlo
Published: August 2017

The combination of a photosensitizer (PS) with a cisplatin‐like unit represents a challenging strategy to increase the effectiveness of photodynamic therapy and to afford a dual‐action anticancer treatment. Recently, new tetra‐PtII–porphyrin conjugates have been proposed as promising multitarget agents. To reveal the effect of the PtII center on the chemical and physical properties of the PS and to explore the effect of the PS on the activation mechanism of PtII ligand before reaching its biological target, we carried out a first‐principle investigation on these tetra‐PtII–porphyrin conjugates. To propose a further advance in this novel field and to gain useful insights for the design of new, more efficient PtII–PS conjugates, we introduced structural modifications into the porphyrin dye, which involved the synthesis of the tetra‐PtII–chlorin and tetra‐PtII–bacteriochlorin derivatives. Results showed that the designed dyes better met the criteria to be successful in a dual‐action therapy, as they displayed improved optical properties and reduced the hydrolysis rate of the PtII moiety, the latter being a desirable feature to avoid many side reactions of the conjugate during their transport to the biological target.
DNA methylation dysregulations in valvular atrial fibrillation
Authors: Shen Kangjun , Tu Tao , Yuan Zhaoshun , Yi Jiangfeng , Zhou Yangzhao , Liao Xiaobo , Liu Qiming , Zhou Xinmin
Published: August 2017

Background

The epigenetic changes underlying the development of atrial fibrillation (AF) remain incompletely understood. Limited evidence suggests that abnormal DNA methylation might be involved in the pathogenesis of AF. In the present study, we evaluated the methylation status of genomic DNA from myocardial tissue in AF patients and sinus rhythm (SR) patients systematically.

Hypothesis

DNA methylation dysregulations will be associated with valvular AF.

Methods

Right atrial myocardial tissue was obtained from rheumatic valvular patients who had undergone valve replacement surgery (SR group, n = 10; AF group, n = 10). The global DNA methylation level, the promoter methylation level of the natriuretic peptide receptor‐A gene (NPRA), and its correlation with the mRNA expression level of DNA methyltransferase genes were detected.

Results

The global DNA methylation level was significantly higher in the AF group than in the SR group (P < 0.05). The NPRA mRNA expression was decreased and the NPRA gene was hypermethylated in the AF group (P < 0.05). Meanwhile, the NPRA mRNA expression level has a negative correlation with the mean methylation level in the promoter region of the NPRA gene.

Conclusions

DNA methylation dysregulations may be relevant in the pathogenesis of AF. DNA methyltransferase 3B likely plays an essential role in the DNA methylation dysregulations in AF.
Comprehensive primary prevention of cardiovascular disease in women
Authors: Lee Suegene K. , Khambhati Jay , Varghese Tina , Stahl Eric P. , Kumar Sonali , Sandesara Pratik B. , Wenger Nanette K. , Sperling Laurence S.
Published: August 2017

Atherosclerotic cardiovascular disease (ASCVD) remains the leading cause of mortality in women. Historically, medical research has focused on male patients, and subsequently, there has been decreased awareness of the burden of ASCVD in females until recent years. The biological differences between sexes and differences in societal expectations defined by gender roles contribute to gender differences in ASCVD risk factors. With these differing risk profiles, risk assessment, risk stratification, and primary preventive measures of ASCVD are different in women and men. In this review article, clinicians will understand the risk factors unique to women, such as preeclampsia, gestational diabetes, and those that disproportionately affect them such as autoimmune disorders. With these conditions in mind, the approach to ASCVD risk assessment and stratification in women will be discussed. Furthermore, the literature behind the effects of primary preventive measures in women, including lifestyle modifications, aspirin, statins, and anticoagulation, will be reviewed. The aim of this review article was to ultimately improve ASCVD primary prevention by reducing gender disparities through education of physicians.
An exploration of the association between ischemic etiology and the likelihood of heart failure hospitalization following cardiac resynchronization therapy
Authors: Powell Adam C. , Rogstad Teresa L. , Deshmukh Uday U. , Price Stephen E. , Simmons Jeffrey D.
Published: August 2017

Background

Myocardial scarring resulting from cardiomyopathy with ischemic etiology may interfere with effective lead placement during implantation of multi‐lead cardioverter‐defibrillators for cardiac resynchronization therapy (CRT‐D). Extensive scarring is known to be associated with poorer physiological and survival outcomes in patients who undergo CRT‐D.

Hypothesis

Ischemic CRT‐D recipients respond as well as nonischemic recipients, using hospital admission for heart failure (HF) as a measure of response.

Methods

Patients who underwent CRT‐D between February 1, 2013, and February 1, 2014, were identified in an insurer's claims. Inclusion required 1 year of enrollment pre– and post–CRT‐D. The sample was divided into nonischemic and ischemic groups, and a subset of the ischemic group with a history of ST‐segment elevation myocardial infarction (STEMI) was identified. The likelihood of HF hospital admissions in the year before and after CRT‐D was computed for each group, as well as for the subset of patients with HF admissions prior to CRT‐D.

Results

A significant (P = 0.02) association was found between ischemic etiology and the post–CRT‐D HF admission likelihood. No association was found between history of STEMI vs nonischemic status and likelihood of post–CRT‐D HF admission. All groups had significantly lower risk of HF admissions after CRT‐D. None of the comparisons involving only patients with a HF hospitalization in the year prior to CRT‐D were significant.

Conclusions

Patients with nonischemic etiology were significantly less likely to experience a HF admission after CRT‐D, but the risk of HF admission improved significantly in all groups after CRT‐D.