bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemically Defined Culture and Cardiomyocyte Differentiation of Human Pluripotent Stem Cells
Authors: Burridge Paul W. , Holmström Alexandra , Wu Joseph C.
Published: October 2015

Since the first discovery that human pluripotent stem cells (hPS cells) can differentiate to cardiomyocytes, efforts have been made to optimize the conditions under which this process occurs. One of the most effective methodologies to optimize this process is reductionist simplification of the medium formula, which eliminates complex animal‐derived components to help reveal the precise underlying mechanisms. Here we describe our latest, cost‐effective and efficient methodology for the culture of hPS cells in the pluripotent state using a modified variant of chemically defined E8 medium. We provide exact guidelines for cell handling under these conditions, including non‐enzymatic EDTA passaging, which have been optimized for subsequent cardiomyocyte differentiation. We describe in depth the latest version of our monolayer chemically defined small molecule differentiation protocol, including metabolic selection–based cardiomyocyte purification and the addition of triiodothyronine to enhance cardiomyocyte maturation. Finally, we describe a method for the dissociation of hPS cell–derived cardiomyocytes, cryopreservation, and thawing. © 2015 by John Wiley & Sons, Inc.
Foehn winds link climate‐driven warming to ice shelf evolution in Antarctica
Authors: Cape M. R. , Vernet Maria , Skvarca Pedro , Marinsek Sebastián , Scambos Ted , Domack Eugene
Published: October 2015

Rapid warming of the Antarctic Peninsula over the past several decades has led to extensive surface melting on its eastern side, and the disintegration of the Prince Gustav, Larsen A, and Larsen B ice shelves. The warming trend has been attributed to strengthening of circumpolar westerlies resulting from a positive trend in the Southern Annular Mode (SAM), which is thought to promote more frequent warm, dry, downsloping foehn winds along the lee, or eastern side, of the peninsula. We examined variability in foehn frequency and its relationship to temperature and patterns of synoptic‐scale circulation using a multidecadal meteorological record from the Argentine station Matienzo, located between the Larsen A and B embayments. This record was further augmented with a network of six weather stations installed under the U.S. NSF LARsen Ice Shelf System, Antarctica, project. Significant warming was observed in all seasons at Matienzo, with the largest seasonal increase occurring in austral winter (+3.71°C between 1962–1972 and 1999–2010). Frequency and duration of foehn events were found to strongly influence regional temperature variability over hourly to seasonal time scales. Surface temperature and foehn winds were also sensitive to climate variability, with both variables exhibiting strong, positive correlations with the SAM index. Concomitant positive trends in foehn frequency, temperature, and SAM are present during austral summer, with sustained foehn events consistently associated with surface melting across the ice sheet and ice shelves. These observations support the notion that increased foehn frequency played a critical role in precipitating the collapse of the Larsen B ice shelf.
Intercomparison of methods of coupling between convection and large‐scale circulation: 1. Comparison over uniform surface conditions
Authors: Daleu C. L. , Plant R. S. , Woolnough S. J. , Sessions S. , Herman M. J. , Sobel A. , Wang S. , Kim D. , Cheng A. , Bellon G. , Peyrille P. , Ferry F. , Siebesma P. , van Ulft L.
Published: October 2015

As part of an international intercomparison project, a set of single‐column models (SCMs) and cloud‐resolving models (CRMs) are run under the weak‐temperature gradient (WTG) method and the damped gravity wave (DGW) method. For each model, the implementation of the WTG or DGW method involves a simulated column which is coupled to a reference state defined with profiles obtained from the same model in radiative‐convective equilibrium. The simulated column has the same surface conditions as the reference state and is initialized with profiles from the reference state. We performed systematic comparison of the behavior of different models under a consistent implementation of the WTG method and the DGW method and systematic comparison of the WTG and DGW methods in models with different physics and numerics. CRMs and SCMs produce a variety of behaviors under both WTG and DGW methods. Some of the models reproduce the reference state while others sustain a large‐scale circulation which results in either substantially lower or higher precipitation compared to the value of the reference state. CRMs show a fairly linear relationship between precipitation and circulation strength. SCMs display a wider range of behaviors than CRMs. Some SCMs under the WTG method produce zero precipitation. Within an individual SCM, a DGW simulation and a corresponding WTG simulation can produce different signed circulation. When initialized with a dry troposphere, DGW simulations always result in a precipitating equilibrium state. The greatest sensitivities to the initial moisture conditions occur for multiple stable equilibria in some WTG simulations, corresponding to either a dry equilibrium state when initialized as dry or a precipitating equilibrium state when initialized as moist. Multiple equilibria are seen in more WTG simulations for higher SST. In some models, the existence of multiple equilibria is sensitive to some parameters in the WTG calculations.
Mixed norm regularized recursive total least squares for group sparse system identification
Authors: Lim Jun‐seok , Pang Hee‐Suk
Published: October 2015

A mixed lp,0‐regularized recursive total least squares (RTLS) algorithm is considered for group sparse system identification. Regularized recursive least squares (RLS) has been successfully applied to group sparse system identification; however, the estimation performance in regularized RLS‐based algorithms deteriorates when both input and output are contaminated by noise (the error‐in‐variables problem). We propose an lp,0‐RTLS algorithm to handle group sparse system identification with errors‐in‐variables. The proposed algorithm is an RLS‐like solution that utilizes lp,0‐regularization. The proposed algorithm provides excellent performance as well as reduces the required complexity by effective inversion matrix handling. Simulations demonstrate the superiority of the proposed lp,0‐regularized RTLS for a group sparse system identification setting. Copyright © 2015 John Wiley & Sons, Ltd.
Microneedles for Transdermal Biosensing: Current Picture and Future Direction
Authors: Ventrelli Letizia , Marsilio Strambini Lucanos , Barillaro Giuseppe
Published: October 2015

A novel trend is rapidly emerging in the use of microneedles, which are a miniaturized replica of hypodermic needles with length‐scales of hundreds of micrometers, aimed at the transdermal biosensing of analytes of clinical interest, e.g., glucose, biomarkers, and others. Transdermal biosensing via microneedles offers remarkable opportunities for moving biosensing technologies and biochips from research laboratories to real‐field applications, and envisages easy‐to‐use point‐of‐care microdevices with pain‐free, minimally invasive, and minimal‐training features that are very attractive for both developed and emerging countries. In addition to this, microneedles for transdermal biosensing offer a unique possibility for the development of biochips provided with end‐effectors for their interaction with the biological system under investigation. Direct and efficient collection of the biological sample to be analyzed will then become feasible in situ at the same length‐scale of the other biochip components by minimally trained personnel and in a minimally invasive fashion. This would eliminate the need for blood extraction using hypodermic needles and reduce, in turn, related problems, such as patient infections, sample contaminations, analysis artifacts, etc.

The aim here is to provide a thorough and critical analysis of state‐of‐the‐art developments in this novel research trend, and to bridge the gap between microneedles and biosensors.
Inhibition of phagocytic recognition of anti‐D opsonized Rh D+ RBC by polymer‐mediated immunocamouflage
Authors: Li Li , Noumsi Ghislain T. , Kwok Yin Yu Eunice , Moulds Joann M. , Scott Mark D.
Published: October 2015

The Rh D antigen posed both a significant clinical risk and inventory supply issue in transfusion medicine. The successful development of the immunocamouflaged RBC has the potential to address both the risk of acute anti‐D transfusion reactions and to improve D− blood inventory in geographic locations where D− blood is rare (e.g., China). The immunocamouflage of RBC was mediated by the covalent grafting of methoxy(polyethylene glycol) to the cell membrane thereby obscuring the D protein from the immune system. To determine the potential efficacy of mPEG‐D+ RBC in D− recipients, anti‐D alloantibodies from previously alloimmunized individuals were utilized. The effects of polymer chain size (2–30 kDa) and grafting concentration (0–4 mM) on antibody binding and erythrophagocytosis were determined using the clinically validated monocyte monolayer assay (MMA) and flow cytometry. The immunocamouflage of D was polymer size and grafting concentration dependent as determined using human anti‐D alloantibodies (both pooled [RhoGAM] and single donors). Importantly, the 20 kDa polymer provided excellent immunocamouflage of D and reached a clinically significant level of protection, as measured by the MMA, at grafting concentrations of ≥1.5 mM. These findings further support the potential use of immunocamouflaged RBC to reduce the risk of acute transfusion reactions following administration of D+ blood to D− recipients in situations where D− units are unavailable or supply is geographically constrained. Am. J. Hematol. 90:1165–1170, 2015. © 2015 Wiley Periodicals, Inc.
Epilepsy is a possible feature in Williams‐Beuren syndrome patients harboring typical deletions of the 7q11.23 critical region
Authors: Nicita Francesco , Garone Giacomo , Spalice Alberto , Savasta Salvatore , Striano Pasquale , Pantaleoni Chiara , Spartà Maria Valentina , Kluger Gerhard , Capovilla Giuseppe , Pruna Dario , Freri Elena , D'Arrigo Stefano , Verrotti Alberto
Published: October 2015

Seizures are rarely reported in Williams‐Beuren syndrome (WBS)—a contiguous‐gene‐deletion disorder caused by a 7q11.23 heterozygous deletion of 1.5–1.8 Mb—and no previous study evaluated electro‐clinical features of epilepsy in this syndrome. Furthermore, it has been hypothesized that atypical deletion (e.g., larger than 1.8 Mb) may be responsible for a more pronounced neurological phenotypes, especially including seizures. Our objectives are to describe the electro‐clinical features in WBS and to correlate the epileptic phenotype with deletion of the 7q11.23 critical region. We evaluate the electro‐clinical features in one case of distal 7q11.23 deletion syndrome and in eight epileptic WBS (eWBS) patients. Additionally, we compare the deletion size—and deleted genes—of four epileptic WBS (eWBS) with that of four non‐epileptic WBS (neWBS) patients. Infantile spasms, focal (e.g., motor and dyscognitive with autonomic features) and generalized (e.g., tonic‐clonic, tonic, clonic, myoclonic) seizures were encountered. Drug‐resistance was observed in one patient. Neuroimaging discovered one case of focal cortical dysplasia, one case of fronto‐temporal cortical atrophy and one case of periventricular nodular heterotopia. Comparison of deletion size between eWBS and neWBS patients did not reveal candidate genes potentially underlying epilepsy. This is the largest series describing electro‐clinical features of epilepsy in WBS. In WBS, epilepsy should be considered both in case of typical and atypical deletions, which do not involve HIP1, YWHAG or MAGI2. © 2015 Wiley Periodicals, Inc.
A novel missense mutation in the gene EDARADD associated with an unusual phenotype of hypohidrotic ectodermal dysplasia
Authors: Wohlfart Sigrun , Söder Stephan , Smahi Asma , Schneider Holm
Published: October 2015

Hypohidrotic ectodermal dysplasia (HED) is a rare disorder characterized by deficient development of structures derived from the ectoderm including hair, nails, eccrine glands, and teeth. HED forms that are caused by mutations in the genes EDA, EDAR, or EDARADD may show almost identical phenotypes, explained by a common signaling pathway. Proper interaction of the proteins encoded by these three genes is important for the activation of the NF‐κB signaling pathway and subsequent transcription of the target genes. Mutations in the gene EDARADD are most rarely implicated in HED. Here we describe a novel missense mutation, c.367G>A (p.Asp123Asn), in this gene which did not appear to influence the interaction between EDAR and EDARADD proteins, but led to an impaired ability to activate NF‐κB signaling. Female members of the affected family showed either unilateral or bilateral amazia. In addition, an affected girl developed bilateral ovarian teratomas, possibly associated with her genetic condition. © 2015 Wiley Periodicals, Inc.
Regulatory Mechanism of the Enantioselective Intramolecular Enone [2+2] Photocycloaddition Reaction Mediated by a Chiral Lewis Acid Catalyst Containing Heavy Atoms
Authors: Wang Hongjuan , Cao Xiaoyan , Chen Xuebo , Fang Weihai , Dolg Michael
Published: October 2015

The asymmetric catalysis of the intramolecular enone [2+2] photocycloaddition has been subject of extensive experimental studies, however theoretical insight to its regulatory mechanism is still sparse. Accurate quantum chemical calculations at the CASPT2//CASSCF level of theory associated with energy‐consistent relativistic pseudopotentials provide a basis for the first regulation theory that the enantioselective reaction is predominantly controlled by the presence of relativistic effects, that is, spin–orbit coupling resulting from heavy atoms in the chiral Lewis acid catalyst.
Metallic Co4N Porous Nanowire Arrays Activated by Surface Oxidation as Electrocatalysts for the Oxygen Evolution Reaction
Authors: Chen Pengzuo , Xu Kun , Fang Zhiwei , Tong Yun , Wu Junchi , Lu Xiuli , Peng Xu , Ding Hui , Wu Changzheng , Xie Yi
Published: October 2015

Designing highly efficient electrocatalysts for oxygen evolution reaction (OER) plays a key role in the development of various renewable energy storage and conversion devices. In this work, we developed metallic Co4N porous nanowire arrays directly grown on flexible substrates as highly active OER electrocatalysts for the first time. Benefiting from the collaborative advantages of metallic character, 1D porous nanowire arrays, and unique 3D electrode configuration, surface oxidation activated Co4N porous nanowire arrays/carbon cloth achieved an extremely small overpotential of 257 mV at a current density of 10 mA cm−2, and a low Tafel slope of 44 mV dec−1 in an alkaline medium, which is the best OER performance among reported Co‐based electrocatalysts to date. Moreover, in‐depth mechanistic investigations demonstrate the active phases are the metallic Co4N core inside with a thin cobalt oxides/hydroxides shell during the OER process. Our finding introduces a new concept to explore the design of high‐efficiency OER electrocatalysts.
Nitrene Insertion into CC and CH Bonds of Diamide Diimine Ligands Ligated to Chromium and Iron
Authors: Heins Spencer P. , Morris Wesley D. , Wolczanski Peter T. , Lobkovsky Emil B. , Cundari Thomas R.
Published: October 2015

The impact of redox non‐innocence (RNI) on chemical reactivity is a forefront theme in coordination chemistry. A diamide diimine ligand, [{‐CHN(1,2‐C6H4)NH(2,6‐iPr2C6H3)}2]n (n=0 to −4), (dadi)n, chelates Cr and Fe to give [(dadi)M] ([1Cr(thf)] and [1Fe]). Calculations show [1Cr(thf)] (and [1Cr]) to have a d4 Cr configuration antiferromagnetically coupled to (dadi)2−*, and [1Fe] to be S=2. Treatment with RN3 provides products where RN is formally inserted into the CC bond of the diimine or into a CH bond of the diimine. Calculations on the process support a mechanism in which a transient imide (imidyl) aziridinates the diimine, which subsequently ring opens.
Palladium immobilized on amidoxime‐functionalized magnetic Fe3O4 nanoparticles: a highly stable and efficient magnetically recoverable nanocatalyst for sonogashira coupling reaction
Authors: Veisi Hojat , Sedrpoushan Alireza , Maleki Behrooz , Hekmati Malak , Heidari Masoud , Hemmati Saba
Published: October 2015

We describe the synthesis of a novel Fe3O4/amidoxime (AO)/Pd nanocatalyst by grafting of AO groups on Fe3O4 nanoparticles and subsequent deposition of Pd nanoparticles. Prior to grafting of AO, the 2‐cyanoethyl‐functionalized Fe3O4 nanoparticles prepared through combining 2‐cyanoethyltriethoxysilane and Fe3O4 were treated with hydroxylamine. The AO‐grafted Fe3O4 nanoparticles were then used as a platform for the deposition of Pd nanoparticles. The catalyst was characterized using Fourier transform infrared spectroscopy, X‐ray diffraction, scanning and transmission electron microscopies, vibrating sample magnetometry, wavelength‐ and energy‐dispersive X‐ray spectroscopies and inductively coupled plasma analysis. Fe3O4/AO/Pd is novel phosphine‐free recyclable heterogeneous catalyst for Sonogashira reactions. Interestingly, the novel catalyst could be recovered in a facile manner from the reaction mixture by applying an external magnet device and recycled seven times without any significant loss in activity. Copyright © 2015 John Wiley & Sons, Ltd.
Particle number and size of polystyrene‐dependent micellar crosslinking polymerization of acrylic acid
Authors: Kim Byungsoo , Hong Daesun , Chang Wenji V.
Published: October 2015

The effect of the number and size of polystyrene particles and the concentration of ammonium persulfate used as the initiator on the micellar crosslinking polymerization of acrylic acid was studied by real‐time monitoring of the storage modulus (G ′), the damping factor (tanδ), and the ratio of the complex modulus (G*) to the maximumG* (G*max) during 1 h of polymerization. The molar ratio (5.83 × 10−4) ofN,N′‐methylenebis‐acrylamide to acrylic acid was fixed. Polystyrene particles were prepared by emulsifier‐free emulsion polymerization. The diameter of the particles ranged from 233 to 696 nm. The results show that crosslinking polymerization was most effective when 1.31 × 1012particles were incorporated into the system, while crosslinking polymerization was less effective in the particle‐filled system than in the unfilled polymerization system if the particle number was 50% lower or higher. Crosslinking was also more effective with the use of uncrosslinked firmer and larger particles at the fixed particle number, except for the anomalous behavior observed with 696 nm polystyrene particles. Increasing the feed concentration of the initiator resulted in more efficient crosslinking up to a limiting concentration of 0.765 mg mL−1(the molar ratio of initiator to monomer was 8.52 × 10−4). When this initiator concentration was doubled, the rate of increase ofG ′ in the deceleration phase was slower after the network was formed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 42851.
Mechanical behavior and failure analysis of recycled polymers by use of miniature punch specimens
Authors: Cuesta Isidro Ivan , Alegre Jesus Manuel , Rodríguez Cristina
Published: October 2015

In today's society, recycling is a priority, and using recycled materials to obtain new 100% reusable materials is an important aspect of some manufacturing sectors. Clearly, the mechanical properties of these new materials can vary considerably from the original material, so it is necessary to carry out a complete mechanical characterization to know its behavior for both standard specimens and final components. One of the common drawbacks is the inability to extract standard size specimens from a final component with a reduced size. In this paper, the use of the small punch test is proposed as a means of solving this problem. At present, this test is used for estimating mechanical properties in those cases when there is not a sufficient amount of material to perform standard tests. The main purpose of this paper is to analyse the feasibility of using miniature punch specimens for the mechanical characterization of recycled polymers. The results are compared with those obtained from standard uniaxial tensile specimens, and a corresponding correlation between the two tests is established. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 42911.
Influence of the coupling agent and graphene oxide on the thermal and mechanical behavior of tea dust–polypropylene composites
Authors: Bari Pravin , Lanjewar Shital , Hansora Dharmesh Parshottam , Mishra Satyendra
Published: October 2015

In this study, the effects of a coupling agent and additive on the physicomechanical (morphological, mechanical, thermal, and swelling) properties of tea dust (TD)–polypropylene (PP) composites were studied. TD–PP composites were prepared with untreated tea dust (UTD) and tetraethylsilane (TES)‐treated TD or silanated tea dust (STD) particles at ratios of 0:100, 10:90, 20:80, 30:70, and 40:60 w/w. Initially, TD particles were grafted by TES as a coupling agent, and these STD particles were then modified with graphene oxide (GO) as an additive to study their effects on the STD–PP composites; these were compared to the STD–PP and UTD–PP composites in accordance with a study of improvements in the mechanical properties. All of the TD–PP composites were analyzed with Fourier transform infrared spectroscopy, scanning electron microscopy, and mechanical, thermal, and physical tests. The thermal and mechanical properties of both the STD–PP and GO‐modified STD–PP composites were found to be improved as compared to those of the UTD–PP composites. So, the recycling of a large amount of TD as a waste material could be useful in the preparation of TD–PP composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42927.
CLONING AND EXPRESSING TRYPSIN MODULATING OOSTATIC FACTOR IN Chlorella desiccata TO CONTROL MOSQUITO LARVAE
Authors: Borovsky Dov , Sterner Andeas , Powell Charles A.
Published: October 2015

The insect peptide hormone trypsin modulating oostatic factor (TMOF), a decapeptide that is synthesized by the mosquito ovary and controls the translation of the gut's trypsin mRNA was cloned and expressed in the marine alga Chlorella desiccata. To express Aedes aegypti TMOF gene (tmfA) in C. desiccata cells, two plasmids (pYES2/TMOF and pYDB4‐tmfA) were engineered with pKYLX71 DNA (5 Kb) carrying the cauliflower mosaic virus (CaMV) promoter 35S2 and the kanamycin resistant gene (neo), as well as, a 8 Kb nitrate reductase gene (nit) from Chlorella vulgaris. Transforming C. desiccata with pYES2/TMOF and pYDB4‐tmfA show that the engineered algal cells express TMOF (20 ± 4 μg ± SEM and 17 ± 3 μg ± SEM, respectively in 3 × 108 cells) and feeding the cells to mosquito larvae kill 75 and 60% of Ae. aegypti larvae in 4 days, respectively. Southern and Northern blots analyses show that tmfA integrated into the genome of C. desiccata by homologous recombination using the yeast 2 μ circle of replication and the nit in pYES2/TMOF and pYDB4‐tmfA, respectively, and the transformed algal cells express tmfA transcript. Using these algal cells it will be possible in the future to control mosquito larvae in the marsh.
Effect of Age, Duration of Exposure, and Dose of Atrazine on Sexual Maturation and the Luteinizing Hormone Surge in the Female Sprague–Dawley Rat
Authors: Breckenridge Charles B. , Sawhney Coder Pragati , Tisdel Merrill O. , Simpkins James W. , Yi Kun Don , Foradori Chad D. , Handa Robert J.
Published: October 2015

Atrazine (ATZ) was administered daily by gavage to pregnant female Sprague Dawley rats at doses of 0, 6.25, 25 or 50 mg/kg/day, either during gestation, lactation and post‐weaning (G/L/PW cohort) to F1 generation female offspring or only from postnatal day (PND 21) until five days after sexual maturation (vaginal opening) when the estrogen‐primed, luteinizing hormone (LH) surge was evaluated (PW cohort). Additional subgroups of F1 females received the vehicle or ATZ from PND 21–133 or from PND 120–133. Slight reductions in fertility and the percentage of F1 generation pups surviving to PND 21 in the gestationally exposed 50 mg/kg dose group were accompanied by decreased food intake and body weight of dams and F1 generation offspring. The onset of puberty was delayed in of the F1 generation G/L/PW females at doses of 25 and 50 mg/kg/day. F1 generation females in the PW high‐dose ATZ group also experienced a delay in the onset of puberty. ATZ had no effect on peak LH or LH AUC in ovariectomized rats 5 days after sexual maturation, irrespective of whether the F1 generation females were treated from gestation onward or only peripubertally. There was no effect of ATZ treatment on the estrous cycle, peak LH or LH AUC of F1 generation females exposed from gestation through to PND 133 or only for two weeks from PND 120–133. These results indicate that developing females exposed to ATZ are not more sensitive compared to animals exposed to ATZ as young adults
Combining mechanistic and data‐driven approaches to gain process knowledge on the control of the metabolic shift to lactate uptake in a fed‐batch CHO process
Authors: Zalai Dénes , Koczka Krisztina , Párta László , Wechselberger Patrick , Klein Tobias , Herwig Christoph
Published: October 2015

A growing body of knowledge is available on the cellular regulation of overflow metabolism in mammalian hosts of recombinant protein production. However, to develop strategies to control the regulation of overflow metabolism in cell culture processes, the effect of process parameters on metabolism has to be well understood. In this study, we investigated the effect of pH and temperature shift timing on lactate metabolism in a fed‐batch Chinese hamster ovary (CHO) process by using a Design of Experiments (DoE) approach. The metabolic switch to lactate consumption was controlled in a broad range by the proper timing of pH and temperature shifts. To extract process knowledge from the large experimental dataset, we proposed a novel methodological concept and demonstrated its usefulness with the analysis of lactate metabolism. Time‐resolved metabolic flux analysis and PLS‐R VIP were combined to assess the correlation of lactate metabolism and the activity of the major intracellular pathways. Whereas the switch to lactate uptake was mainly triggered by the decrease in the glycolytic flux, lactate uptake was correlated to TCA activity in the last days of the cultivation. These metabolic interactions were visualized on simple mechanistic plots to facilitate the interpretation of the results. Taken together, the combination of knowledge‐based mechanistic modeling and data‐driven multivariate analysis delivered valuable insights into the metabolic control of lactate production and has proven to be a powerful tool for the analysis of large metabolic datasets. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:1657–1668, 2015
Enhanced Electrochemical Performance of Zr‐Modified Layered LiNi1/3Co1/3Mn1/3O2 Cathode Material for Lithium‐Ion Batteries
Authors: Li Xing , Peng Hui , Wang Ming‐Shan , Zhao Xing , Huang Peng‐Xiao , Yang Wei , Xu Jun , Wang Zhi‐Qiang , Qu Mei‐Zhen , Yu Zuo‐Long
Published: October 2015

Zr‐modified LiNi1/3Co1/3Mn1/3−xZrxO2 samples were prepared through a rheological‐phase method. The results indicate that there is only partial Zr doping into the bulk phase of the LiNi1/3Co1/3Mn1/3O2 particles, whereas the rest of the Zr remained on the surface to form a Li2ZrO3 coating layer during the Zr‐modification process. The Zr‐modified LiNi1/3Co1/3Mn1/3−xZrxO2 samples show lower discharge specific capacities at low rates, however, which exhibit clearly improved rate capabilities than that of pristine LiNi1/3Co1/3Mn1/3O2. Among the Zr‐modified LiNi1/3Co1/3Mn1/3−xZrxO2 samples, LiNi1/3Co1/3Mn1/3−0.01Zr0.01O2 (x=0.01) shows the best rate capability, which exhibts158, 142, and 132 mAh g−1 at 1.0, 2.0, and 3.0 C, respectively. The related results indicate that the doped Zr in pristine LiNi1/3Co1/3Mn1/3O2 could improve the structure stability and the formation of an inactive Li2ZrO3 coating layer which could suppress the interfacial side reaction of LiNi1/3Co1/3Mn1/3O2.
Ruthenium‐Grafted Vinylhelicenes: Chiroptical Properties and Redox Switching
Authors: Srebro Monika , Anger Emmanuel , Moore II Barry , Vanthuyne Nicolas , Roussel Christian , Réau Régis , Autschbach Jochen , Crassous Jeanne
Published: October 2015

The properties of mono‐ and bis‐Ru–vinyl[6]helicene complexes (2 a and 2 b, respectively), recently synthesized by using molecular engineering of helicenes based on the grafting of lateral organometallic substituents on the π‐helical backbone through a vinyl bridge, are presented. These helicene derivatives are thoroughly characterized, with special attention given to their chiroptical properties and redox switching activity. The UV/Vis and electronic circular dichroism (ECD) spectra of P and M enantiopure species, both in the neutral and oxidized states ([2 a].+, [2 b].+, and [2 b]2+), are analyzed with the aid of quantum‐chemical calculations. The extended π‐conjugation facilitated by the vinyl moiety, clearly visible in the electronic structures of 2 a,b, introduces new active bands in the ECD spectra that consequently lead to a significant increase in optical rotation of Ru–vinylhelicenes compared with the organic precursors. The vibrational circular dichroism (VCD) spectra were measured and calculated for both the organic and organometallic species and constitute the first examples of VCD for metal‐based helicene derivatives. Finally, the redox‐triggered chiroptical switching activity of 2 a,b is examined in detail by using ECD spectroscopy. The modifications of the ECD spectra in the UV/Vis and NIR region are well reproduced and rationalized by calculations.
2‐Aminoethanol Extraction as a Method for Purifying Sc3N@C80 and for Differentiating Classes of Endohedral Fullerenes on the Basis of Reactivity
Authors: Sarina Evan A. , Mercado Brandon Q. , Franco Jimmy U. , Thompson Christopher J. , Easterling Michael L. , Olmstead Marilyn M. , Balch Alan L.
Published: October 2015

Extraction with 2‐aminoethanol is an inexpensive method for removing empty cage fullerenes from the soluble extract from electric‐arc‐generated fullerene soot that contains endohedral metallofullerenes of the type Sc3N@C2n (n=34, 39, 40). Our method of separation exploits the fact that C60, C70, and other larger, empty cage fullerenes are more susceptible to nucleophilic attack than endohedral fullerenes and that these adducts can be readily extracted into 2‐aminoethanol. This methodology has also been employed to examine the reactivity of the mixture of soluble endohedral fullerenes that result from doping graphite rods used in the Krätschmer–Huffman electric‐arc generator with the oxides of Y, Lu, Dy, Tb, and Gd. For example, with Y2O3, we were able to detect by mass spectrometry several new families of endohedral fullerenes, namely Y3C108 to Y3C126, Y3C107 to Y3C125, Y4C128 to Y4C146, that resisted reactivity with 2‐aminoethanol more than the empty cage fullerenes and the mono‐ and dimetallo fullerenes. The discovery of the family Y3C107 to Y3C125 with odd numbers of carbon atoms is remarkable, since fullerene cages must involve even numbers of carbon atoms. The newly discovered families of endohedral fullerenes with the composition M4C2n (M=Y, Lu, Dy, Tb, and Gd) are unusually resistant to reaction with 2‐aminoethanol. Additionally, the individual endohedrals, Y3C112 and M3C102 (M=Lu, Dy, Tb and Gd), were remarkably less reactive toward 2‐aminoethanol.
A Straightforward Route to Potent Phenolic Chain‐Breaking Antioxidants by Acid‐Promoted Transposition of 1,4‐Benzo[b]oxathiines to Dihydrobenzo[b]thiophenes
Authors: Viglianisi Caterina , Amorati Riccardo , Di Pietro Leonardo , Menichetti Stefano
Published: October 2015

The transformation of simple phenols with limited antioxidant activity into potent chain‐breaking antioxidants was achieved by a three‐step protocol, consisting of the conversion of phenols into 1,4‐benzo[b]oxathiines followed by an unprecedented acid‐promoted transposition to o‐hydroxydihydrobenzo[b]thiophenes, or dihydrobenzo[de]thiochromenes, starting from phenols or naphthols, respectively. These derivatives, bearing a benzo‐fused heterocycle with a sulfide sulfur ortho to the phenolic OH, have a rate constant of reaction with alkylperoxyl radicals (kinh) comparable to that of α‐tocopherol. A solid rationale for the transposition mechanism as well as for the structure‐antioxidant activity relationship is presented.
Efficient Chemical Modification of Carbon Nanotubes with Metallacarboranes
Authors: Cabana Laura , González‐Campo Arántzazu , Ke Xiaoxing , Van Tendeloo Gustaaf , Núñez Rosario , Tobias Gerard
Published: October 2015

As‐produced single‐walled carbon nanotubes (SWCNTs) tend to aggregate in bundles due to π–π interactions. Several approaches are nowadays available to debundle, at least partially, the nanotubes through surface modification by both covalent and noncovalent approaches. Herein, we explore different strategies to afford an efficient covalent functionalization of SWCNTs with cobaltabisdicarbollide anions. Aberration‐corrected HRTEM analysis reveals the presence of metallacarboranes along the walls of the SWCNTs. This new family of materials presents an outstanding water dispersibility that facilitates its processability for potential applications.
Electrochemically Exfoliated Graphene and Graphene Oxide for Energy Storage and Electrochemistry Applications
Authors: Ambrosi Adriano , Pumera Martin
Published: October 2015

Top‐down methods are of key importance for large‐scale graphene and graphene oxide preparation. Electrochemical exfoliation of graphite has lately gained much interest because of the simplicity of execution, the short process time, and the good quality of graphene that can be obtained. Here, we test three different electrolytes, that is, H2SO4, Na2SO4, and LiClO4, with a common exfoliation procedure to evaluate the difference in structural and chemical properties that result for the graphene. The properties are analyzed by means of scanning transmission electron microscopy (STEM), Raman spectroscopy, and X‐ray photoelectron spectroscopy. We then tested the graphene materials for electrochemical applications, measuring the heterogeneous electron transfer (HET) rates with a Fe(CN)63−/4− redox probe, and their capacitive behavior in alkaline solutions. We correlate the electrochemical features with the presence of structural defects and oxygen functionalities on the graphene materials. In particular, the use of LiClO4 during the electrochemical exfoliation of graphite allowed the formation of highly oxidized graphene with a C/O ratio close to 4.0 and represents a possible avenue for the mass production of graphene oxide as valid alternative to the current laborious and dangerous chemical procedures, which also have limited scalability.
Pd(II)‐Catalyzed CH Activation of Styrylindoles: Short, Efficient, and Regioselective Synthesis of Functionalized Carbazoles
Authors: Saunthwal Rakesh K. , Patel Monika , Kumar Sonu , Danodia Abhinandan K. , Verma Akhilesh K.
Published: October 2015

A novel PdII‐catalyzed approach for the direct synthesis of highly functionalized carbazoles from unprotected styrylindoles has been developed. The reaction features a variety of olefin substrates, which are readily switchable by subtle tuning of the reaction conditions. Investigations of the mechanism suggest that the CH activation proceeds via enamine formation.
Study on Multiphase Discrete Random Medium Model and its GPR Wave Field Characteristics
Authors: Shi‐Li GUO , Meng‐En JI , Pei‐Min ZHU , Xiu‐Zhong LI
Published: October 2015

Asphalt concrete is a typical multiphase discrete random medium, which is composed of aggregate, asphalt mortar and air with different volume fraction. Aggregate, asphalt mortar and air usually have different sizes, shapes, dielectric properties, and distribute randomly in space. This paper is based on random medium theory, (1) we measured the dielectric constants of the asphalt concrete samples, and computed the statistical characteristics (such as mean values, standard deviations) of spatial random distribution of dielectric constants and the volume fraction of each component; (2) we calculated the autocorrelation function of asphalt concrete based on Wiener‐Khintchine theorem, and extracted its characteristic parameters (such as autocorrelation length, autocorrelation angle), and then classified the type of random media; (3) we developed the modeling algorithm of multiphase discrete random medium under quantization constrain, and constructed multiphase discrete random medium model based on intermixed elliptic autocorrelation function. Additionally, we studied the propagation characteristics of ground penetrating radar wave in multiphase discrete random medium model and compared the model with homogeneous medium model and continuous random medium model using numerical simulation. The calculated results show that the autocorrelation functions of a large number of asphalt concrete sections are approximate to ellipsoidal autocorrelation functions, which provide the foundation for using random medium theory to describe asphalt concrete. The multiphase discrete random medium model not only describes the statistical characteristics of spatial random distribution of asphalt concrete, but also describe the volume fractions of its compositions. For multiphase discrete random medium model and continuous random medium model, ground penetrating radar wave has strong scattering phenomenon. Random and disorderly scattering waves overlie and interfere with each other, which resulting random perturbations and noise in received waves. The reflected waves from anomalous body are with distortion and discontinuity and reduce the signal to noise ratio and resolution of ground penetrating radar data. When multiphase discrete random medium model and continuous random medium model have the same given model parameters, ground penetrating radar waves have stronger scattering in continuous random medium model. The study reveals that the multiphase discrete random medium model can describe asphalt concrete more comprehensive and precise than homogeneous medium model and continuous random medium model. The multiphase discrete random medium model also provides a new way for studying similar media or materials. The radar profile is more consistent with the field measured data, and more conducive to guide the interpretation of the ground penetrating radar profile data.
The molecular landscape of extraskeletal osteosarcoma: A clinicopathological and molecular biomarker study
Authors: Jour George , Wang Lu , Middha Sumit , Zehir Ahmet , Chen Wen , Sadowska Justyna , Healey John , Agaram Narasimhan P , Choi Lisa , Nafa Khedoudja , Hameed Meera
Published: October 2015

Extraskeletal osteosarcoma (ESOSA) is a rare soft tissue neoplasm representing <5% of osteosarcomas and <1% of all soft‐tissue sarcomas. Herein, we investigate the clinicopathological and molecular features of ESOSA and explore potential parameters that may affect outcome. Thirty‐two cases were retrieved and histomorphology was reviewed. Clinical history and follow‐up were obtained through electronic record review. DNA from formalin‐fixed paraffin‐embedded (FFPE) tissue was extracted and processed from 27 cases. Genome‐wide DNA copy number (CN) alterations and allelic imbalances were analyzed by single nucleotide polymorphism array using Affymetrix OncoScan FFPE Assay. Massive high‐throughput deep parallel sequencing was performed using a customized panel targeting 410 cancer genes. Log rank, Fisher's exact test and Cox proportional hazards were used for statistical analysis. In this series of 32 patients (male n = 12, female n = 20), the average age was 66 years (19–93) and median follow up was 24 months (range 6–120 months). Frequent genomic alterations included CN losses in tumour suppressor genes including CDKN2A (70%), TP53 (56%) and RB1 (49%). Mutations affecting methylation/demethylation, chromatin remodeling and WNT/SHH pathways were identified in 40%, 27%, and 27%, respectively. PIK3CA and TERT promoter variant mutations were identified in 11% of the cases. Cases harbouring simultaneous TP53 and RB1 biallelic CN losses were associated with worse overall survival and local recurrence (p = 0.04, p = 0.02, respectively). CDKN2A losses and positive margins were also associated with worse overall survival (p = 0.002; p = 0.03, respectively). Our findings suggest that age above 60, positive margin status, simultaneous biallelic TP53 and RB1 losses and CDKN2A loss are associated with a worse outcome in ESOSA. Comparison between conventional paediatric osteosarcoma and ESOSA shows that, while both share genetic similarities, there are notable dissimilarities and mechanistic differences in the molecular pathways involved in ESOSA.
Identification of germline genetic mutations in patients with pancreatic cancer
Authors: Salo‐Mullen Erin E. , O'Reilly Eileen M. , Kelsen David P. , Ashraf Asad M. , Lowery Maeve A. , Yu Kenneth H. , Reidy Diane L. , Epstein Andrew S. , Lincoln Anne , Saldia Amethyst , Jacobs Lauren M. , Rau‐Murthy Rohini , Zhang Liying , Kurtz Robert C. , Saltz Leonard , Offit Kenneth , Robson Mark E. , Stadler Zsofia K.
Published: October 2015

BACKGROUND

Pancreatic adenocarcinoma (PAC) is part of several cancer predisposition syndromes; however, indications for genetic counseling/testing are not well‐defined. In the current study, the authors sought to determine mutation prevalence and characteristics that are predictive of an inherited predisposition for PAC.

METHODS

A total of 175 consecutive patients with PAC who underwent clinical genetics assessment at Memorial Sloan Kettering Cancer Center between 2011 and 2014 were identified. Clinical data, family history, and germline results were evaluated.

RESULTS

Among 159 patients with PAC who pursued genetic testing, 24 pathogenic mutations were identified (15.1%; 95% confidence interval, 9.5%‐20.7%), including BRCA2 (13 mutations), BRCA1 (4 mutations), p16 (2 mutations), PALB2 (1 mutation), and Lynch syndrome (4 mutations). BRCA1/BRCA2 prevalence was 13.7% in Ashkenazi Jewish (AJ) patients (95 patients) and 7.1% in non‐AJ patients (56 patients). In AJ patients with a strong, weak, or absent family history of BRCA‐associated cancers, the mutation prevalence was 16.7%, 15.8%, and 7.4%, respectively. The mean age at the time of diagnosis in all mutation carriers was 58.5 years (range, 45‐75 years) compared with 64 years (range, 27‐87 years) in those not carrying a mutation (P = .02). Although BRCA2 was the most common mutation identified, no patients with early‐onset PAC (diagnosed at age ≤ 50 years) harbored a BRCA2 mutation and the mean age at diagnosis in BRCA2 carriers was equivalent to that of individuals who were not mutation carriers (P = .34). Mutation prevalence in patients with early‐onset disease (21 patients) was 28.6%, including BRCA1 (2 mutations), p16 (2 mutations), MSH2 (1 mutation), and MLH1 (1 mutation).

CONCLUSIONS

Mutations in BRCA2 account for > 50% of patients with PAC with an identified susceptibility syndrome. AJ patients were found to have high BRCA1/BRCA2 prevalence regardless of personal/family history, suggesting that ancestry alone indicates a need for genetic evaluation. With the exception of BRCA2‐associated PAC, an inherited predisposition for PAC is associated with an earlier age at PAC diagnosis, suggesting that this subset of patients may also represent a population warranting further evaluation. Cancer 2015;121:4382–8. © 2015 American Cancer Society.
Cardiovascular toxicity after antiangiogenic therapy in persons older than 65 years with advanced renal cell carcinoma
Authors: Jang Sekwon , Zheng Chaoyi , Tsai Huei‐Ting , Fu Alex Z. , Barac Ana , Atkins Michael B. , Freedman Andrew N. , Minasian Lori , Potosky Arnold L.
Published: October 2015

BACKGROUND

Sorafenib and sunitinib are oral vascular endothelial growth factor receptor (VEGFR) tyrosine kinase inhibitors (TKIs) approved in 2005 and 2006, respectively, for the treatment of patients with renal cell carcinoma (RCC). A population‐based, observational cohort study of the cardiovascular risk of VEGFR TKI therapy in elderly RCC patients was conducted.

METHODS

Using the Surveillance, Epidemiology, and End Results–Medicare database, this study analyzed patients who were 66 years old or older and were diagnosed with RCC from 2000 to 2009. The incidence of cardiovascular adverse events, including congestive heart failure and cardiomyopathy (CHF/CM), acute myocardial infarction (AMI), stroke, and cardiovascular deaths, was examined through December 2010. A Cox proportional hazards model was created to calculate the hazard ratio (HR), and adjustments were made for age, sex, comorbidity, and the use of other systemic therapy.

RESULTS

A total of 171 of 670 patients who received sunitinib or sorafenib had cardiovascular events. The incidence rates for CHF/CM, AMI, and stroke were 0.87, 0.14, and 0.14 per 1000 person‐days, respectively. Sunitinib or sorafenib use was associated with an increased risk of cardiovascular events (HR, 1.38; 95% confidence interval [CI], 1.02‐1.87) and especially stroke (HR, 2.84; 95% CI, 1.52‐5.31) in comparison with 788 patients diagnosed with advanced RCC from 2007 to 2009 who were eligible for Part D but did not receive either agent. In subgroup analyses, patients who were 66 to 74 years old at diagnosis had the highest increased risk of stroke associated with the use of either or both drugs.

CONCLUSIONS

Sunitinib and sorafenib might be associated with an increased risk of cardiovascular events and particularly stroke. Cancer 2016;122:124–130. © 2015 American Cancer Society.
The neuropeptide SIFamide in the brain of three cockroach species
Authors: Arendt Andreas , Neupert Susanne , Schendzielorz Julia , Predel Reinhard , Stengl Monika
Published: October 2015

The sequence as well as the distribution pattern of SIFamide in the brain of different insects is highly conserved. As a general rule, at least four prominent SIFamide‐immunoreactive somata occur in the pars intercerebralis. They arborize throughout the brain and the ventral nerve cord. Whereas SIFamide is implicated in mating and sleep regulation in Drosophila, other functions of this peptide remain largely unknown. To determine whether SIFamide plays a role in the circadian system of cockroaches, we studied SIFamide in Rhyparobia (= Leucophaea) maderae (Blaberidae), Periplaneta americana (Blattidae), and Therea petiveriana (Polyphagidae). Matrix‐assisted laser desorption/ionization–time of flight (MALDI–TOF) mass spectrometry revealed identical SIFamide sequences (TYRKPPFNGSIFamide) in the three species. In addition to four large immunoreactive cells in the pars intercerebralis (group 1), smaller SIFamide‐immunoreactive somata were detected in the pars intercerebralis (group 2), in the superior median protocerebrum (group 3), and in the lateral protocerebrum (group 4). Additional cells in the optic lobe (group 5) and posterior protocerebrum (group 6) were stained only in P. americana. Almost the entire protocerebrum was filled with a beaded network of SIFamide‐immunoreactive processes that especially strongly invaded the upper unit of the central body. Double‐label experiments did not confirm colocalizations with γ‐aminobutyric acid (GABA) or the circadian coupling peptide pigment‐dispersing factor (PDF). In contrast to locusts, colocalization of SIFamide and histamine immunoreactivity occurred not in group 1, but in group 4 cells. Because the accessory medulla displayed SIFamide immunoreactivity and injections of SIFamide delayed locomotor activity rhythms circadian time‐dependently, SIFamide plays a role in the circadian system of cockroaches. J. Comp. Neurol. 524:1337–1360, 2016. © 2015 Wiley Periodicals, Inc.