bluuebunny/crossref_metadata_2025 huggingface dataset:
High‐Performance Doped Silver Films: Overcoming Fundamental Material Limits for Nanophotonic Applications
Authors: Zhang Cheng , Kinsey Nathaniel , Chen Long , Ji Chengang , Xu Mingjie , Ferrera Marcello , Pan Xiaoqing , Shalaev Vladimir M. , Boltasseva Alexandra , Guo L. Jay
Published: March 2017

The field of nanophotonics has ushered in a new paradigm of light manipulation by enabling deep subdiffraction confinement assisted by metallic nanostructures. However, a key limitation which has stunted a full development of high‐performance nanophotonic devices is the typical large losses associated with the constituent metals. Although silver has long been known as the highest quality plasmonic material for visible and near infrared applications, its usage has been limited due to practical issues of continuous thin film formation, stability, adhesion, and surface roughness. Recently, a solution is proposed to the above issues by doping a proper amount of aluminum during silver deposition. In this work, the potential of doped silver for nanophotonic applications is presented by demonstrating several high‐performance key nanophotonic devices. First, long‐range surface plasmon polariton waveguides show propagation distances of a few centimeters. Second, hyperbolic metamaterials consisting of ultrathin Al‐doped Ag films are attained having a homogeneous and low‐loss response, and supporting a broad range of high‐k modes. Finally, transparent conductors based on Al‐doped Ag possess both a high and flat transmittance over the visible and near‐IR range.
Dynamic Thin Films in Controlling the Fabrication of Nanocarbon and Its Composites
Authors: Vimalanathan Kasturi , Raston Colin L.
Published: March 2017

Thin film microfluidics are developed for a wide range of applications, including the synthesis of various types of nanocarbon material, involving both ‘top down’ and ‘bottom up’ continuous flow processing. This type of processing addresses scalability at the inception of the science, and is applicable not just to the synthesis of nanocarbon, but also composites or hybrid material where one or more components is nanocarbon. This review introduces the different types of thin film microfluidics where the liquid is subjected to shear stress (mechanical energy), and then provides a comprehensive treatise of controlling the fabrication of nanocarbon. The shear stress offers scope for controlling the shape, morphology and size of carbon nanomaterial, with the prospect of high green chemistry metrics of the processing. The use of thin film microfluidics has potential where conventional batch processing is limited in terms of practical convenience, and indeed where some novel forms of carbon and composites thereof are not accessible using traditional approaches.
Photosensitizer‐Free, Gold‐Catalyzed C–C Cross‐Coupling of Boronic Acids and Diazonium Salts Enabled by Visible Light
Authors: Witzel Sina , Xie Jin , Rudolph Matthias , Hashmi A. Stephen K.
Published: March 2017

The first photosensitizer‐free visible light‐driven, gold‐catalyzed C–C cross‐couplings of arylboronic acids and aryldiazonium salts are reported. The reactions can be conducted under very mild conditions, using a catalytic amount of tris(4‐trifluoromethyl)phosphinegold(I) chloride [(4‐CF3‐C6H4)3PAuCl] with methanol as the solvent allowing an alternative access to a variety of substituted biaryls in moderate to excellent yields with broad functional group tolerance.

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Numerical simulation and experimental study of filling process of micro prism by isothermal hot embossing in solid‐like state
Authors: Sun Jingyao , Wu Daming , Liu Ying , Dai Le , Jiang Chong
Published: March 2017

Filling process of micro prism array by isothermal hot embossing in solid‐like state (IHESS) with different mold temperature, pressure, and holding time were simulated by DEFORM. Polymethyl methacrylate (PMMA) samples processing by IHESS were tested to validate the numerical simulation results and select the best processing condition. The reliability of simulation was tested quantitatively and qualitatively by comparing the cross‐profile and its developing trend separately. It was found that the cross‐profiles from the simulations and experiments were in high agreement. The simulated and experimental developing trends of cross‐profiles were also the same. These results proved the reliability of simulation and its guidance to the experiments. In order to show the advantages of IHESS, a brief introduction and comparison of IHESS and traditional hot embossing were made.
Structure of Organometal Halide Perovskite Films as Determined with Grazing‐Incidence X‐Ray Scattering Methods
Authors: Schlipf Johannes , Müller‐Buschbaum Peter
Published: March 2017

Grazing‐incidence X‐ray scattering (GIXS) methods have proven to be a valuable asset for investigating the morphology of thin films at different length scales. Consequently, GIXS has been applied to the fast‐progressing field of organometal halide perovskites. This exciting class of materials has propelled research in the areas of cheap and sustainable photovoltaics, light emitting devices, and optoelectronics in general. Especially, perovskite solar cells (PSC) have seen a remarkable rise in power conversion efficiencies, crossing the 20% mark after only five years of research. This research news outlines GIXS studies focusing on the most challenging research topics in the perovskite field today: Current–voltage hysteresis, device reproducibility, and long‐term stability of PSC are inherently linked to perovskite film morphology. On the other hand, film formation depends on the choice of precursors and processing parameters; understanding their interdependence opens possibilities to tailor film morphologies. Owing to their tunability and moisture resistance, 2D perovskites have recently attracted attention. Examples of GIXS studies with different measurement and data analysis techniques are presented, highlighting especially in‐situ investigations on the many kinetic processes involved. Thus, an overview on the toolbox of GIXS techniques is linked to the specific needs of research into organometal halide perovskite optoelectronics.
Formation process of core‐shell microparticles by solute migration during drying of homogenous composite droplets
Authors: Fu Nan , Wu Winston Duo , Wu Zhangxiong , Moo Fei Tzhung , Woo Meng Wai , Selomulya Cordelia , Chen Xiao Dong
Published: March 2017

Particle formation process during spray drying profoundly impacts particle morphology and microstructure. This study experimentally investigated the formation of core‐shell‐structured microparticles by one‐step drying of composite droplets made of Eudragit® RS (a polycationic acrylic polymer in nanoparticle form) and silica sol. The formation of an incipient surface shell was monitored using single droplet drying technique, and the freshly formed shell was recovered for subsequent analyses. Adding silica to RS precursor increased the shell formation time and altered the properties of the incipient shell from water‐dispersible to nondispersible. The incipient shell formed from RS/silica droplets with mass ratios of 1.5%:1.5% and 0.5%:2.5% showed ingredient segregation with a preferential accumulation of RS, similar to the shell region of dried microparticles. After shell formation, excess silica sol in the liquid phase could flow inward, producing a dense core. This mobility‐governed solute migration would be useful for constructing core‐shell microparticles using other precursor systems. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3297–3310, 2017
A superstructure‐based model for multistream heat exchanger design within flow sheet optimization
Authors: Nagesh Rao Harsha , Karimi Iftekhar A.
Published: March 2017

Multistream heat exchangers (MHEXs) are often used in energy‐intensive cryogenic processes. Modeling them within a process optimization formulation has been a challenge due to the needs to accommodate phase changes and ensure temperature approach. In this work, we present a nonlinear model for MHEXs based on a novel single‐stage superstructure of two‐stream exchangers. Our formulation guarantees a minimum temperature approach for all heat exchanges, estimates heat exchange areas for individual stream matches, requires no prior knowledge of phase changes, uses no Boolean variables, and enables seamless optimization of a process with multiple MHEXs. Furthermore, it facilitates dedicated constant‐phase intervals that allow accurate estimation of heat‐transfer parameters for various stream matches. We optimize two natural gas liquefaction processes involving MHEXs, and report better solutions than the existing literature. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3764–3777, 2017
Novel pathogenic variants in FOXP3 in fetuses with echogenic bowel and skin desquamation identified by ultrasound
Authors: Louie Raymond J. , Tan Queenie K.‐G. , Gilner Jennifer B. , Rogers R. Curtis , Younge Noelle , Wechsler Stephanie B. , McDonald Marie T. , Gordon Barbara , Saski Christopher A. , Jones Julie R. , Chapman Shelley J. , Stevenson Roger E. , Sleasman John W. , Friez Michael J.
Published: March 2017

Immunodysregulation, Polyendocrinopathy, Enteropathy, X‐linked (IPEX) syndrome is a rare, X‐linked recessive disease that affects regulatory T cells (Tregs) resulting in diarrhea, enteropathy, eczema, and insulin‐dependent diabetes mellitus. IPEX syndrome is caused by pathogenic alterations in FOXP3 located at Xp11.23. FOXP3 encodes a transcription factor that interacts with several partners, including NFAT and NF‐κB, and is necessary for the proper cellular differentiation of Tregs. Although variable, the vast majority of IPEX syndrome patients have onset of disease during infancy with severe enteropathy. Only five families with prenatal presentation of IPEX syndrome have been reported. Here, we present two additional prenatal onset cases with novel inherited frameshift pathogenic variants in FOXP3 that generate premature stop codons. Ultrasound findings in the first patient identified echogenic bowel, echogenic debris, scalp edema, and hydrops. In the second patient, ultrasound findings included polyhydramnios with echogenic debris, prominent fluid‐filled loops of bowel, and echogenic bowel. These cases further broaden the phenotypic spectrum of IPEX syndrome by describing previously unappreciated prenatal ultrasound findings associated with the disease.
Limb bone allometry in modern Euro‐Americans
Authors: Jantz R. L. , Meadows Jantz L.
Published: March 2017

Objectives

The pattern of static and secular allometry was examined in a time series of limb bone lengths from individuals with birth years ranging from 1840 to 1989. The main hypothesis investigated was that secular changes in limb proportions, as seen in changes in the brachial and crural indices, can be explained by allometric responses to increasing size.

Materials and Methods

Maximum lengths of humerus, radius, femur, and tibia were obtained from 19th and 20th centuries identified skeletons. Allometry was investigated on two levels, static and secular. Static allometry was defined as average allometry within 20‐year birth cohorts, and secular allometry as allometry among birth year cohorts. Allometry was assessed by extracting eigenvectors from covariance matrices of log transformed variables. Departures from allometry were examined using shape variables, and principal components of minor axes.

Results

Static covariance matrices were homogeneous. Eigenvectors extracted from the secular covariance matrix showed important departures from static allometry, particularly a much stronger negative allometry of the humerus and a stronger positive allometry of the tibia. Shape analysis showed that relative humerus length decreased significantly over the time period examined and relative tibia length increased. The last principal component, which combined aspects of the brachial and crural index, showed the highest variation among birth year cohorts.

Discussion

The results demonstrate that the secular changes in limb proportions cannot be explained by allometric responses to increasing size alone. The majority of variation among birth cohorts is found on the last PC and that suggests that canalized development has been disrupted by the unique environment in which modern Americans now live.
Low normal cerebrospinal fluid Aβ42 levels predict clinical progression in nondemented subjects
Authors: Tijms Betty M. , Bertens Daniela , Slot Rosalinde E. , Gouw Alida A. , Teunissen Charlotte E. , Scheltens Philip , van der Flier Wiesje M. , Visser Pieter Jelle
Published: March 2017

We studied whether continuous lower normal cerebrospinal fluid (CSF) amyloid β1‐42 (≥640pg/ml) levels were related with rate of clinical progression in a sample of 393 nondemented memory clinic patients. Lower normal levels were associated with faster clinical progression, and this depended on baseline cognitive status (subjective cognitive decline: hazard ratio [HR] = 0.57, p < 0.05; mild cognitive impairment: HR = 0.19, p < .01), indicating that normal CSF amyloid levels do not exclude incident Alzheimer disease. These findings suggest that research on preclinical markers for Alzheimer disease should take the continuum of CSF amyloid β1‐42 levels within the normal range into account. Ann Neurol 2017;81:749–753
Deoxycytidine and Deoxythymidine Treatment for Thymidine Kinase 2 Deficiency
Authors: Lopez‐Gomez Carlos , Levy Rebecca J. , Sanchez‐Quintero Maria J. , Juanola‐Falgarona Martí , Barca Emanuele , Garcia‐Diaz Beatriz , Tadesse Saba , Garone Caterina , Hirano Michio
Published: March 2017

Objective

Thymidine kinase 2 (TK2), a critical enzyme in the mitochondrial pyrimidine salvage pathway, is essential for mitochondrial DNA (mtDNA) maintenance. Mutations in the nuclear gene, TK2, cause TK2 deficiency, which manifests predominantly in children as myopathy with mtDNA depletion. Molecular bypass therapy with the TK2 products, deoxycytidine monophosphate (dCMP) and deoxythymidine monophosphate (dTMP), prolongs the life span of Tk2‐deficient (Tk2–/–) mice by 2‐ to 3‐fold. Because we observed rapid catabolism of the deoxynucleoside monophosphates to deoxythymidine (dT) and deoxycytidine (dC), we hypothesized that: (1) deoxynucleosides might be the major active agents and (2) inhibition of deoxycytidine deamination might enhance dTMP+dCMP therapy.

Methods

To test these hypotheses, we assessed two therapies in Tk2–/– mice: (1) dT+dC and (2) coadministration of the deaminase inhibitor, tetrahydrouridine (THU), with dTMP+dCMP.

Results

We observed that dC+dT delayed disease onset, prolonged life span of Tk2‐deficient mice and restored mtDNA copy number as well as respiratory chain enzyme activities and levels. In contrast, dCMP+dTMP+THU therapy decreased life span of Tk2–/– animals compared to dCMP+dTMP.

Interpretation

Our studies demonstrate that deoxynucleoside substrate enhancement is a novel therapy, which may ameliorate TK2 deficiency in patients. Ann Neurol 2017;81:641–652
Asymmetric Grignard Synthesis of Tertiary Alcohols through Rational Ligand Design
Authors: Bieszczad Bartosz , Gilheany Declan G.
Published: March 2017

A simple, general and practical method is reported for highly enantioselective construction of tertiary alcohols through the direct addition of organomagnesium reagents to ketones. Discovered by rational ligand design based on a mechanistic hypothesis, it has an unprecedented broad scope. It utilizes a new type of chiral tridentate diamine/phenol ligand that is easily removed from the reaction mixture. It is exemplified by application to a formal asymmetric synthesis (>95:5 d.r.) of vitamin E.
Chemoselective Alteration of Fluorophore Scaffolds as a Strategy for the Development of Ratiometric Chemodosimeters
Authors: Zhou Xinqi , Lesiak Lauren , Lai Rui , Beck Jon R. , Zhao Jia , Elowsky Christian G. , Li Hui , Stains Cliff I.
Published: March 2017

Ratiometric sensors generally couple binding events or chemical reactions at a distal site to changes in the fluorescence of a core fluorophore scaffold. However, such approaches are often hindered by spectral overlap of the product and reactant species. We provide a strategy to design ratiometric sensors that display dramatic spectral shifts by leveraging the chemoselective reactivity of novel functional groups inserted within fluorophore scaffolds. As a proof‐of‐principle, fluorophores containing a borinate (RF620) or silanediol (SiOH2R) functionality at the bridging position of the xanthene ring system are developed as endogenous H2O2 sensors. Both these fluorophores display far‐red to near‐infrared excitation and emission prior to reaction. Upon oxidation by H2O2 both sensors are chemically converted to tetramethylrhodamine, producing significant (≥66 nm) blue‐shifts in excitation and emission maxima. This work provides a new concept for the development of ratiometric probes.
Manganese‐Catalyzed N‐Formylation of Amines by Methanol Liberating H2: A Catalytic and Mechanistic Study
Authors: Chakraborty Subrata , Gellrich Urs , Diskin‐Posner Yael , Leitus Gregory , Avram Liat , Milstein David
Published: March 2017

The first example of a base metal (manganese) catalyzed acceptorless dehydrogenative coupling of methanol and amines to form formamides is reported herein. The novel pincer complex (iPr‐PNHP)Mn(H)(CO)2 catalyzes the reaction under mild conditions in the absence of any additives, bases, or hydrogen acceptors. Mechanistic insight based on the observation of an intermediate and DFT calculations is also provided.
Mesoscale Polarization by Geometric Frustration in Columnar Supramolecular Crystals
Authors: Zehe Christoph S. , Hill Joshua A. , Funnell Nicholas P. , Kreger Klaus , van der Zwan Kasper P. , Goodwin Andrew L. , Schmidt Hans‐Werner , Senker Jürgen
Published: March 2017

Columnar supramolecular phases with polarization along the columnar axis have potential for the development of ultrahigh‐density memories as every single column might function as a memory element. By investigating structure and disorder for four columnar benzene‐1,3,5‐trisamides by total X‐ray scattering and DFT calculations, we demonstrate that the column orientation, and thus the columnar dipole moment, is receptive to geometric frustration if the columns aggregate in a hexagonal rod packing. The frustration suppresses conventional antiferroelectric order and heightens the sensitivity towards collective intercolumnar packing effects. The latter finding allows for the building up of mesoscale domains with spontaneous polarization. Our results suggest how the complex interplay between steric and electrostatic interactions is influenced by a straightforward chemical design of the molecular synthons to create spontaneous polarization and to adjust mesoscale domain size.
Rhodium‐Catalyzed Enantioselective Isomerization of meso‐Oxabenzonorbornadienes to 1,2‐Naphthalene Oxides
Authors: Yen Andy , Choo Ken‐Loon , Yazdi Shabnam K. , Franke Patrick T. , Webster Robert , Franzoni Ivan , Loh Charles C. J. , Poblador‐Bahamonde Amalia I. , Lautens Mark
Published: March 2017

Herein we describe a rhodium‐catalyzed enantioselective isomerization of meso‐oxabicyclic alkenes to 1,2‐naphthalene oxides. These potentially useful building blocks can be accessed in moderate to excellent yields with impressive enantioselectivities. Additionally, experimental findings supported by preliminary computations suggest that ring‐opening reactions of bridgehead disubstituted oxabicyclic alkenes proceed through the intermediacy of these epoxides and may point to a kinetically and thermodynamically favored reductive elimination as the origin for the observed enantioselectivities.
Density functional theory/B3LYP study of nanometric 4‐(2,4‐dihydroxy‐5‐formylphen‐1‐ylazo)‐N‐(4‐methylpyrimidin‐2‐yl)benzenesulfonamide complexes: Quantitative structure–activity relationship, docking, spectral and biological investigations
Authors: Saad Fawaz A. , Elghalban Marwa G. , El‐Metwaly Nashwa M. , El‐Ghamry Hoda , Khedr Abdalla M.
Published: March 2017

New metal ion complexes were isolated after coupling with 4‐(2,4‐dihydroxy‐5‐formylphen‐1‐ylazo)‐N‐(4‐methylpyrimidin‐2‐yl)benzenesulfonamide (H2L) drug ligand. The structural and molecular formulae of drug derivative and its complexes were elucidated using spectral, analytical and theoretical tools. Vibrational spectral data proved that H2L behaves as a monobasic bidentate ligand through one nitrogen from azo group and ionized hydroxyl oxygen towards all metal ions. UV–visible and magnetic moment measurements indicated that Fe(III), Cr(III), Mn(II) and Ni(II) complexes have octahedral configuration whereas Cd(II), Zn(II) and Co(II) complexes are in tetrahedral form. The Cu(II)complex has square planar geometry as verified through electron spin resonance essential parameters. X‐ray diffraction data indicated the amorphous nature of all compounds with no regular arrangement for the solid constituents during the precipitation process. Transmission electron microscopy images showed homogeneous metal ion distribution on the surface of the complexes with nanometric particles. Coats–Redfern equations were applied for calculating thermo‐kinetic parameters for suitable thermal decomposition stages. Gaussian09 and quantitative structure–activity relationship modelling studies were used to verify the structural and biological features. Docking study using microorganism protein receptors was implemented to throw light on the biological behaviour of the proposed drug. The investigated ligand and metal complexes were screened for their in vitro antimicrobial activities against fungal and bacterial strains. The resulting data indicated that the investigated compounds are highly promising bactericides and fungicides. The antitumour activities of all compounds were evaluated towards human liver carcinoma (HEPG2) cell line.
Effect of vapor phase ethylenediamine crosslinking of matrimid on alcohol vapor sorption and diffusion
Authors: Stanford John P. , Pfromm Peter H. , Rezac Mary E.
Published: March 2017

This work examines the sorption, diffusion, and polymer relaxation behavior for water and C1‐C7 alcohol vapors at 30  °C in ethylenediamine vapor‐phase crosslinked Matrimid. Ethylenediamine is sufficiently volatile that crosslinking can occur by exposing the polymeric film to saturated vapor, in contrast to more conventional means of dissolving the crosslinker in a solvent and immersing the polymeric film in the solution. The vapor‐phase exposure method avoids the use of additional solvent and undesired solvent‐induced swelling. Sorption isotherms demonstrate that water and C1‐C5 alcohols do not appreciably differ for unmodified and crosslinked Matrimid; however, an approximate 90% reduction in sorption was determined for hexanol and heptanol. A minor impact on diffusion coefficients for water, methanol, and ethanol was observed, while those of propanol and butanol were reduced over an order of magnitude. Relaxation kinetics were similarly unchanged for water and C1‐C3 alcohols, while being significantly reduced for butanol and higher alcohols. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44771.
Enhanced dielectric properties of poly(vinylidene fluoride)–surface functionalized BiFeO3 composites using sodium dodecyl sulfate as a modulating agent for device applications
Authors: Mishra Mukesh K. , Moharana Srikanta , Mahaling R. N.
Published: March 2017

In this work, we prepared a series of poly(vinylidene fluoride) (PVDF)–surface functionalized BiFeO3 (h‐BFO)–Sodium dodecyl sulfate (SDS) composite films by solvent casting method to investigate the effect of SDS in the composites. The X‐ray diffraction confirmed that the structure of h‐BFO significantly changed in the PVDF‐(h‐BFO)‐SDS composite in comparison with the rhombohedral structure of pure BiFeO3. The microscopic study illustrated that the composite with a higher percentage of SDS content facilitated the dispersion as well as proper distribution of ceramic particles in the polymer matrix. The presence of different functionalities of respective polymer and the modified fillers was confirmed by FTIR Spectrophotometer. The dielectric and electrical study done by Impedance Analyzer revealed that the SDS treated surface functionalized composites showed relatively higher dielectric properties than that of two phase composites and pure polymer. Finally, the ferroelectric properties of the composite films done by P‐E loop tracer revealed that the SDS‐treated composites showed an enhanced remanent polarization. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45040.
Design and Synthesis of Novel Anti‐Plasmodial Histone Deacetylase Inhibitors Containing an Alkoxyamide Connecting Unit
Authors: Alves Avelar Leandro A. , Held Jana , Engel Jessica A. , Sureechatchaiyan Parichat , Hansen Finn K. , Hamacher Alexandra , Kassack Matthias U. , Mordmüller Benjamin , Andrews Katherine T. , Kurz Thomas
Published: March 2017

Despite recent declines in mortality, malaria remains an important global health problem. New therapies are needed, including new drugs with novel modes of action compared to existing agents. Among new potential therapeutic targets for malaria, inhibition of parasitic histone deacetylases (HDACs) is a promising approach. Homology modeling of PfHDAC1, a known target of some anti‐plasmodial HDAC inhibitors, revealed a unique threonine residue at the rim of the active site in close proximity to the location of the cap group of vorinostat‐type HDAC inhibitors. Aiming to obtain HDAC inhibitors with potent and preferential anti‐plasmodial activity, we synthesized a mini‐library of alkoxyamide‐based HDAC inhibitors containing hydrogen bond acceptors in the cap group. Using a 5‐step synthetic route, 12 new inhibitors were synthesized and assayed against Plasmodium falciparum asexual blood stage parasites (clones 3D7 and Dd2) and human cells (HepG2). The most active compound 6h (Pf3D7 IC50: 0.07 µM; PfDd2 IC50: 0.07 µM) was 25‐fold more toxic against the parasite versus human HepG2 cells. Selected compounds were shown to cause hyperacetylation of P. falciparum histone H4, indicating inhibition of one or more PfHDACs.
Surface‐Triggered Tandem Coupling Reactions of Cyclic Azasilanes
Authors: Pan Youlin , Maddox Annalese , Min Taewoo , Gonzaga Ferdinand , Goff Jonathan , Arkles Barry
Published: March 2017

Cyclic azasilanes have been synthesized for the purpose of developing coupling agents appropriate for a variety of nanotechnologies including surface modification of nanoparticles, nanocrystals, mesoporous materials and substrates. N‐Methyl‐aza‐2,2,4‐trimethylsilacyclopentane is representative of this class of compounds. Preliminary data for the treatment of inorganic surfaces, including nanoparticles and oxidized silicon wafers, with cyclic azasilanes suggest high‐density monolayer deposition by a ring‐opening reaction. Cyclic azasilanes contain a cryptic amine functionality that can perform a subsequent tandem coupling reaction with functional molecules after the surface‐triggered ring‐opening reaction, allowing for a one‐pot self‐assembly route on nanostructures. Tandem coupling reactions are demonstrated via addition reactions of the cryptic amine with epoxy and acrylate systems.
Hyper‐Assembly of Self‐Assembled Glycoclusters Mediated by Specific Carbohydrate–Carbohydrate Interactions
Authors: Yan Gengwei , Yamaguchi Takumi , Suzuki Tatsuya , Yanaka Saeko , Sato Sota , Fujita Makoto , Kato Koichi
Published: March 2017

Hybridization of a self‐assembled, spherical complex with oligosaccharides containing Lewis X, a functional trisaccharide displayed on various cell surfaces, yielded well‐defined glycoclusters. The self‐assembled glycoclusters exhibited homophilic hyper‐assembly in aqueous solution in a Ca2+‐dependent manner through specific carbohydrate–carbohydrate interactions, offering a structural scaffold for functional biomimetic systems.
Stabilization of a Heat‐ODE System Cascaded at a Boundary Point and an Intermediate Point
Authors: Zhen Zhiyuan , Tang Shu‐Xia , Zhou Zhongcheng
Published: March 2017

This paper considers the stabilization of a heat‐ODE system cascaded at a boundary point and an intermediate point. The stabilizing feedback control law is designed by the backstepping method. Based on a novel transformation, we prove that all the kernel functions in the forward and inverse transformations are of the class C2. Moreover, the effectiveness of controller design is shown with a numerical simulation. Finally, we show the coherence between the controllability assumption of the main theorem in this paper and the known one for a special case with λ=0.
Hunger and thirst interact to regulate ingestive behavior in flies and mammals
Authors: Jourjine Nicholas
Published: March 2017

In animals, nervous systems regulate the ingestion of food and water in a manner that reflects internal metabolic need. While the coordination of these two ingestive behaviors is essential for homeostasis, it has been unclear how internal signals of hunger and thirst interact to effectively coordinate food and water ingestion. In the last year, work in insects and mammals has begun to elucidate some of these interactions. As reviewed here, these studies have identified novel molecular and neural mechanisms that coordinate the regulation of food and water ingestion behaviors. These mechanisms include peptide signals that modulate neural circuits for both thirst and hunger, neurons that regulate both food and water ingestion, and neurons that integrate sensory information about both food and water in the external world. These studies argue that a deeper understanding of hunger and thirst will require closer examination of how these two biological drives interact.
Correlation between the potency of flavonoids for cytochrome c reduction and inhibition of cardiolipin‐induced peroxidase activity
Authors: Lagoa Ricardo , Samhan‐Arias Alejandro K. , Gutierrez‐Merino Carlos
Published: March 2017

There are large differences between flavonoids to protect against apoptosis, a process in which cytochrome c (Cyt c) plays a key role. In this work, we show that 7 of 13 flavonoids studied have a capacity to reduce Cyt c similar or higher than ascorbate, the flavonols quercetin, kaempferol and myricetin, flavanol epigallocatechin‐gallate, anthocyanidins cyanidin and malvidin, and the flavone luteolin. In contrast, the kaempferol 3(O)‐ and 3,4′(O)‐methylated forms, the flavanone naringenin, and also apigenin and chrysin, had a negligible reducing capacity. Equilibrium dialysis and quenching of 1,6‐diphenyl‐1,3,5‐hexatriene fluorescence experiments showed that flavonoids did not interfere with Cyt c binding to cardiolipin (CL)/phosphatidylcholine (PC) vesicles. However, the CL‐induced loss of Cyt c Soret band intensity was largely attenuated by flavonoids, pointing out a stabilizing action against Cyt c unfolding in the complex. Moreover, flavonoids that behave as Cyt c reductants also inhibited the pro‐apoptotic CL‐induced peroxidase activity of Cyt c, indicating that modulation of Cyt c signaling are probable mechanisms behind the protective biological activities of flavonoids. © 2016 BioFactors, 43(3):451–468, 2017
Differential Cytotoxic Activity of Essential Oil of Lippia citriodora from Different Regions in Morocco
Authors: Oukerrou Moulay Ali , Tilaoui Mounir , Mouse Hassan Ait , Bouchmaa Najat , Zyad Abdelmajid
Published: March 2017

The aim of this work was to investigate the cytotoxic effect of the essential oil of dried leaves of Lippia citriodora (H.B. & K.) harvested in different regions of Morocco. This effect was evaluated against the P815 murine mastocytoma cell line using the MTT assay. Interestingly, this work demonstrated for the first time that these essential oils exhibited a strong cytotoxic activity against the P815 cell line, with IC50 values ranging from 7.75 to 13.25 μg/ml. This cytotoxicity began early and increased in a dose‐ and time‐dependent manner. The chemical profile of these essential oils was analyzed by gas chromatography coupled to mass spectrometry. Importantly, the difference in terms of major components’ contents was not significant suggesting probably that the differential cytotoxicity between these essential oils could be attributed to the difference in the content of these essential oils in minor compounds, which could interact with each other or with the main molecules. Finally, this study demonstrated for the first time that essential oils of L. citriodora from different regions in Morocco induced apoptosis against P815 tumor cell line.
Dienophile‐Modified Mannosamine Derivatives for Metabolic Labeling of Sialic Acids: A Comparative Study
Authors: Dold Jeremias E. G. A. , Pfotzer Jessica , Späte Anne‐Katrin , Wittmann Valentin
Published: March 2017

Sialic acids play an important role in numerous cell adhesion processes, and sialylation levels are known to be altered under certain pathogenic conditions, such as cancer. Metabolic glycoengineering with mannosamine derivatives is a convenient way to introduce non‐natural chemical reporter groups into sialylated glycoconjugates, offering the opportunity to label sialic acids by using bioorthogonal ligation chemistry. The labeling intensity depends not only on the rate of the ligation reaction but also on the extent to which the natural sialic acids are replaced by the modified ones; that is, the incorporation efficiency. Here, we present a comparative study of eight mannosamine derivatives featuring terminal alkenes as chemical reporter groups that can be labeled by an inverse‐electron‐demand Diels–Alder (DAinv) reaction. The derivatives differed in chain length as well as the type of linkage (carbamates, amides, and a urea) that connects the terminal alkene to the sugar. As a general trend, increasing chain lengths resulted in higher DAinv reactivity and, at the same time, reduced incorporation efficiency. Carbamates were better accepted than amides with the same chain length; nevertheless, the latter resulted in more intense cell‐surface staining, visible by live‐cell fluorescence microscopy. A urea derivative was also shown to be accepted.
Silencing of ATF2 inhibits growth of pancreatic cancer cells and enhances sensitivity to chemotherapy
Authors: Li Mu , Wu Xingda , Liu Ning , Li Xiaoying , Meng Fanbin , Song Shaowei
Published: March 2017

Pancreatic cancer is one of the leading causes of cancer‐related death worldwide. Activating transcription factor 2 (ATF2) is a multifunctional transcription factor, and is implicated in tumor progress, yet its role in pancreatic cancer remains unclear. In the present study, the level of ATF2 in pancreatic cancer tissues and the adjacent non‐tumorous tissues was detected by quantitative real‐time PCR and Western blot. The roles of ATF2 in the proliferation, cell cycle, and apoptosis of pancreatic cancer cells were investigated through ATF2 silencing, and the effect of ATF2 shRNA on the sensitivity of pancreatic cancer cells to gemcitabine, an anti‐tumor drug, was explored. The results of our study showed that the ATF2 level in the pancreatic cancer tissues was higher than that in the adjacent non‐tumorous tissues. Silencing of ATF2 was found to inhibit proliferation, arrest cell cycle at G1 phase and induce apoptosis in pancreatic cancer cells. Moreover, ATF2 silencing enhanced gemcitabine‐induced growth‐inhibition and apoptosis‐induction effects in pancreatic cancer cells. In summary, silencing of ATF2 inhibited the growth of pancreatic cancer cells and enhanced the anti‐tumor effects of gemcitabine, suggesting that ATF2 plays a pro‐survival role in pancreatic cancer. Our results also propose that a high level of ATF2 may serve as a potential biomarker of pancreatic cancer, and that ATF2 may become a potential target for anti‐tumor therapy.
Effect of coronary dominance on 2‐year outcomes after percutaneous coronary intervention in patients with acute coronary syndrome
Authors: He Chen , Ma Yuan‐Liang , Wang Chuang‐Shi , Song Ying , Tang Xiao‐Fang , Zhao Xue‐Yan , Gao Run‐Lin , Yang Yue‐Jin , Xu Bo , Yuan Jin‐Qing
Published: March 2017

Objectives

This retrospective, single‐center, observational analysis from prospectively collected database evaluated whether left dominance affected the long‐term outcomes of acute coronary syndrome patients undergoing percutaneous coronary intervention, and whether the effect was independent of SYNTAX score.

Background

Left dominance is believed to be associated with worse prognoses. The anatomical SYNTAX score is a scoring system based on the complexity and severity of coronary lesions and is thought to be a prognostic tool to predict short‐ and long‐term outcomes. There are few studies about whether the effect of left dominance is independent of SYNTAX score.

Methods

Between January 2013 and December 2013, 6255 consecutive acute coronary syndrome patients who were admitted to Fuwai hospital and underwent percutaneous coronary intervention (PCI) were enrolled in this study. Based on coronary dominance and the calculation methods of the SYNTAX score, patients were divided into a left‐dominant group (LD group; 390 patients) and a right‐dominant or co‐dominant group (RD + Co group, 5865 patients).

Result

The 2‐year mortality rate was significantly higher in the LD group than in the RD + Co group (2.58% vs. 1.23%, P = 0.024). In multivariate Cox analysis, the independent predictors of mortality were coronary dominance, IABP support, age, baseline SYNTAX score, and ejection fraction.

Conclusions

LD was an independent predictor of long‐term mortality in ACS patients undergoing PCI. The effect of LD still existed after adjustment for several important variables and was independent of SYNTAX score. © 2017 Wiley Periodicals, Inc.
Biomass‐assisted Zeolite Syntheses as a Tool for Designing New Acid Catalysts
Authors: Louis Benoît , Gomes Elisa S. , Losch Pit , Lutzweiler Gaëtan , Coelho Tiago , Faro Arnaldo , Pinto Joana F. , Cardoso Cristiane S. , Silva Alessandra V. , Pereira Marcelo M.
Published: March 2017

The aim of this Concept article is to highlight different aspects of using biomass residues or extracted molecules in the synthesis of zeolites (mainly), aluminas and layered doubled hydroxides (LDHs). The strategies presented should serve as a basis for rationally preparing those aforementioned materials for catalytic purposes. Indeed, the presence of sugars, lignin, lignocellulosic biomass usually induces morphological/textural changes as well as (in some cases) modified chemical composition and surface properties.
Access to (Hetero)arylated Selenophenes via Palladium‐catalysed Stille, Negishi or Suzuki Couplings or C−H Bond Functionalization Reaction
Authors: Skhiri Aymen , Ben Salem Ridha , Soulé Jean‐François , Doucet Henri
Published: March 2017

(Hetero)aryl‐substituted selenophenes exhibit important physical properties especially for optoelectronics. Palladium‐catalysed coupling reactions currently represent the most efficient methods to prepare such (hetero)arylated selenophene derivatives. Initially, Stille coupling was the most efficient reaction for the synthesis of these compounds; however, over the last decade, Suzuki coupling has become the most commonly employed. Recently, Pd‐catalysed arylation via the C−H bond activation of selenophenes has proved to be a very convenient alternative method for the preparation of several arylated selenophenes as there is no need to prepare organometallic derivatives. In this Review, the progress and substrate scope in the synthesis of both C2‐ and C3‐arylated selenophenes via Pd‐catalysis are summarized.
Optical Sensing of Anions via Supramolecular Recognition with Biimidazole Complexes
Authors: Rommel Sebastian A. , Sorsche Dieter , Fleischmann Maximilian , Rau Sven
Published: March 2017

Phosphorescent metal complexes with peripheral N‐H donor functionalities have attracted great attention as potential molecular sensing units for anionic species lately. In this contribution we discuss the development and potential of anion recognition and sensing features of recent examples of luminescent 2,2′‐biimidazole complexes of ruthenium(II), iridium(III), osmium(II) and cobalt(III). The general dependency of photophysical features in these complexes regarding the acid‐base chemistry of the peripheral N‐H functionalities will be outlined as a basic requirement for optical ion recognition. Systematic strategies for the tuning and specific improvement by synthetic means will be discussed regarding recent reports. With respect to their distinct photophysical features, different transition metals are considered individually to demonstrate particular trends regarding ligand modification within the respective groups. In summary, this review elucidates the current state‐of‐the‐art and future potential of the versatile class of 2,2′‐biimidazole based sensor chromophores.
Ultra‐Narrow Low‐Bandgap Graphene Nanoribbons from Bromoperylenes—Synthesis and Terahertz‐Spectroscopy
Authors: Jänsch Daniel , Ivanov Ivan , Zagranyarski Yulian , Duznovic Ivana , Baumgarten Martin , Turchinovich Dimitry , Li Chen , Bonn Mischa , Müllen Klaus
Published: March 2017

Soluble ultra‐narrow armchair graphene nanoribbons (AGNRs) with length of ≈20 nm and completely fused cores exceeding 5 nm in length, pronounced near‐infrared (NIR) absorption up to 1400 nm, and a low band gap (≈0.9 eV) are synthesized from 3,9(3,10)‐dibromoperylene and 3,4,9,10‐tetrabromoperylene. Since the monomers are obtained from perylene carboxyanhydrides, a remarkable link between dye and graphene chemistry is established. The two‐step protocol for the AGNR synthesis by aryl–aryl coupling and subsequent cyclodehydrogenation is compared with a direct Yamamoto polymerization. Ultrafast photoconductivity analysis by optical pump‐terahertz (THz) probe spectroscopy of the longest AGNRs excited in the NIR regime (800 nm) reveal their high intrinsic charge carrier mobility.
Defective Metal–Organic Frameworks Incorporating Iridium‐Based Metalloligands: Sorption and Dye Degradation Properties
Authors: Fan Kun , Nie Wei‐Xuan , Wang Lu‐Ping , Liao Chwen‐Haw , Bao Song‐Song , Zheng Li‐Min
Published: March 2017

Artificial control and engineering of metal–organic framework (MOF) crystals with defects can endow them with suitable properties for applications in gas storage, separation, and catalysis. A series of defective iridium‐containing MOFs, [Zn4(μ4‐O)(Ir‐A)2(1−x)(Ir‐B)2x] (ZnIr‐MOF‐dx), were synthesized by doping heterostructured linker Ir‐BH3 into the parent [Zn4(μ4‐O)(Ir‐A)2] (ZnIr‐MOF), in which Ir‐AH3 represents [Ir(ppy‐COOH)3] (ppyCOOH=3‐(pyridin‐2‐yl)benzoic acid) and Ir‐BH3 is [Ir(ppy‐COOH)2(2‐pyPO3H)] (2‐pyPO3H2=2‐pyridylphosphonic acid). Samples with different degrees of defects were characterized by SEM, IR and NMR spectroscopy, powder XRD measurements, and thermal and elemental analyses. ZnIr‐MOF‐d0.3 was selected as a representative for gas (N2, CO2) or vapor (H2O, alcohol) sorption studies. The results demonstrate that defective ZnIr‐MOF‐d0.3 possesses multiple pore size distributions, ranging from micro‐ to mesopores, unlike the parent material, which shows a uniform micropore distribution. The hydrophilicity of the interior surface is also increased after defect engineering. As a result, ZnIr‐MOF‐d0.3 shows an enhanced adsorption capability toward n‐butanol, relative to that of the parent compound. Optical studies reveal that both ZnIr‐MOF and ZnIr‐MOF‐d0.3 have low band gaps (2.35 and 2.40 eV), corresponding to semiconductors. ZnIr‐MOF‐d0.3 exhibits dramatically increased photocatalytic efficiency for dye degradation.
Preparation and Reactions of Perfluoroalkanesulfenyl Chlorides
Authors: Xu Ze‐Feng , Jiang Min , Liu Jin‐Tao
Published: March 2017

Several perfluoroalkanesulfenyl chlorides were prepared from the corresponding perfluoroalkanesulfenic acids in high yields, and their reactions with thiol, amine, arene and alkene were studied. A series of perfluoroalkyl‐containing disulfides, sulfonamides, aryl sulfides and α‐chlorosulfides were synthesized under mild conditions.
Cover Picture: Silver‐Catalyzed Cascade Radical Cyclization for Stereoselective Synthesis of Exocyclic Phosphine Oxides (Chin. J. Chem. 3/2017)
Authors: Mao Liuliang , Li Yonghong , Yang Shangdong
Published: March 2017

The cover picture shows a concise and effective protocol for the synthesis of valuable exocyclic phosphine oxides via the process of free radical cascade cyclization. Waterwheel in series shows the implied meaning in the process of phosphorylation/ cascade cyclization of various 1,6‐dienes involving the C—P and C—C bonds formation. More details are discussed in the article by Yang et al. on page 316–322.

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From Trash to Treasure: Turning Air Pollutants into Materials for Energy Storage
Authors: Liang Jiachen , Zhang Chen , Liu Donghai , Zhang Lina , Ling Guowei , Yang Quan‐Hong
Published: March 2017

Environmental and energy issues are hot topics in the sustainable development of our planet. Air pollution, as a vital environmental issue, has puzzled us for decades, and a green and economical approach to control air pollutants is urgently required. New energy‐storage techniques have emerged as fascinating routes to reduce potential environmental problems. Therefore, the combination of air pollutants with energy‐storage devices is an appealing solution for air pollution. Herein, the principles of recovering air pollutants for use in energy‐storage materials are proposed, including their direct use as active materials, their conversion into active materials, and their use as dopants to modify the electrode. Typical air pollutants are selected to demonstrate their potential use in green energy storage. Future prospects of the broad application of air pollutants in energy‐related fields are also commented on.
An Intrinsic Self‐Charging Biosupercapacitor Comprised of a High‐Potential Bioanode and a Low‐Potential Biocathode
Authors: Alsaoub Sabine , Ruff Adrian , Conzuelo Felipe , Ventosa Edgar , Ludwig Roland , Shleev Sergey , Schuhmann Wolfgang
Published: March 2017

An intrinsic self‐charging biosupercapacitor built on a unique concept for the fabrication of biodevices based on redox polymers is presented. The biosupercapacitor consists of a high‐potential redox polymer based bioanode and a low‐potential redox polymer based biocathode in which the potentials of the electrodes in the discharged state show an apparent potential mismatch Eanode>Ecathode and prevent the use of the device as a conventional biofuel cell. Upon charging, the potentials of the electrodes are shifted to more positive (cathode) and more negative (anode) values because of a change in the aox‐to‐ared ratio within the redox polymer matrix. Hence, a potential inversion occurs in the charged state (Eanode0.4 V is achieved and the biodevice acts as a true biosupercapacitor. The bioanode consists of a novel specifically designed high‐potential Os complex modified polymer for the efficient immobilization and electrical wiring of glucose converting enzymes, such as glucose oxidase and flavin adenine dinucleotide (FAD)‐dependent glucose dehydrogenase. The cathodic side is constructed from a low‐potential Os complex modified polymer integrating the O2 reducing enzyme, bilirubin oxidase. The large potential differences between the redox polymers and the prosthetic groups of the biocatalysts ensure fast and efficient charging of the biodevice.
Therapeutic disasters that hastened safety testing of new drugs
Authors: Paine MF
Published: March 2017

New drugs were not required to undergo premarket safety testing in the United States until 1938, when a therapeutic disaster—the Elixir Sulfanilamide tragedy—prompted Congress to pass a bill mandating this now‐routine process. History repeated itself nearly 25 years later, when another therapeutic disaster—the thalidomide tragedy—led to passage of new amendments in 1962 to ensure drug efficacy and greater drug safety. As is typical with historical events, critical information was gained that led to novel approaches for understanding, predicting, diagnosing, and managing drug‐induced toxicities. Continued refinement of current, along with development of new, approaches will mitigate future drug‐related catastrophes, with the goal of avoiding them entirely.