bluuebunny/crossref_metadata_2025 huggingface dataset:
Fabrication of Hierarchical Micro Patterns on PET Substrates Using Direct Laser Interference Patterning
Authors: Rößler Florian , Günther Denise , Lasagni Andrés Fabián
Published: July 2016

Hierarchical microstructures offer improved surface functionalities or a combination of surface properties compared to single‐scale patterns, e.g., low reflectivity and hydrophobicity. The fabrication of three‐level length‐scales microstructures on polyethylene terephthalate (PET) substrates is demonstrated using UV nanosecond‐pulsed direct laser interference patterning. The 1st level is created by an array with 10 µm spatial period. The 2nd level results from the interference within a holographic pixel (1–2 µm spatial periods), while the 3rd level is related to the pixel distance (35 µm). The effect of the laser fluence on the structure quality and depth is investigated. Finally, optical properties of the produced multiscale patterns are determined and compared to numerical calculations.
Hierarchical Directed Self‐Assembly of Diblock Copolymers for Modified Pattern Symmetry
Authors: Choi Young Joo , Kim Ju Young , Kim Ji Eun , Mun Jeong Ho , Cha Seung Keun , Kim Sang Ouk
Published: July 2016

Block copolymer lithography exploiting diblock copolymer thin films is promising for scalable manufacture of device‐oriented nanostructures. Nonetheless, its intrinsic limitation in the degree of freedom for pattern symmetry within hexagonal dot or parallel line array greatly diminishes the potential application fields. Here, we report multi‐level hierarchical self‐assembled nanopatterning of diblock copolymers for modified pattern symmetry. Sequential hierarchical integration of two layers of diblock copolymer films with judiciously chosen molecular weights and chemical composition creates nanopatterned morphology with modified pattern symmetry, including sparse linear cylinder or lamellar arrays. Internal structure of the hierarchically patterned morphology is characterized by grazing‐incidence small‐angle X‐ray scattering throughout the film thickness. Pattern transfer of the modified nanopattern generates linear metal nanodot array with uniform size and regular spacing as a typical example of functional nanopatterned structures.
Patterned Growth of P‐Type MoS2 Atomic Layers Using Sol–Gel as Precursor
Authors: Zheng Wei , Lin Junhao , Feng Wei , Xiao Kai , Qiu Yunfeng , Chen XiaoShuang , Liu Guangbo , Cao Wenwu , Pantelides Sokrates T. , Zhou Wu , Hu PingAn
Published: July 2016

2D layered MoS2 has drawn intense attention for its applications in flexible electronic, optoelectronic, and spintronic devices. Most of the MoS2 atomic layers grown by conventional chemical vapor deposition techniques are n‐type due to the abundant sulfur vacancies. Facile production of MoS2 atomic layers with p‐type behavior, however, remains challenging. Here, a novel one‐step growth has been developed to attain p‐type MoS2 layers in large scale by using Mo‐containing sol–gel, including 1% tungsten (W). Atomic‐resolution electron microscopy characterization reveals that small tungsten oxide clusters are commonly present on the as‐grown MoS2 film due to the incomplete reduction of W precursor at the reaction temperature. These omnipresent small tungsten oxide clusters contribute to the p‐type behavior, as verified by density functional theory calculations, while preserving the crystallinity of the MoS2 atomic layers. The Mo containing sol–gel precursor is compatible with the soft‐lithography techniques, which enables patterned growth of p‐type MoS2 atomic layers into regular arrays with different shapes, holding great promise for highly integrated device applications. Furthermore, an atomically thin p–n junction is fabricated by the as‐prepared MoS2, which shows strong rectifying behavior.
Biodegradable Photothermal and pH Responsive Calcium Carbonate@Phospholipid@Acetalated Dextran Hybrid Platform for Advancing Biomedical Applications
Authors: Kong Feng , Zhang Hongbo , Zhang Xu , Liu Dongfei , Chen Dong , Zhang Weixia , Zhang Liyuan , Santos Hélder A. , Hai Mingtan
Published: July 2016

A biodegradable multifunctional carrier for combination therapy with high efficiency and low side effect is essential for effective cancer treatment and for advancing biomedical applications. Therapeutics combination could reduce multidrug resistance and minimize doses through synergism. This study develops biodegradable gold nanorods@calcium carbonate particles coated with pH‐responsive acetalated dextran and phospholipid as an advanced platform for the incorporation of versatile molecular targeted therapeutics, including hydrophilic and hydrophobic drugs, as well as the model enzyme, green fluorescent protein, or antibody. The developed calcium carbonate based hybrid particles show good biocompatibility, stability with photothermal, and pH responsiveness, which protect the payloads from premature release, and maintain the enzyme activity. The therapeutics co‐loaded CaCO3 based hybrid particles efficiently induce cancer cell death and reduce the multidrug resistance and HER2 expression with synergism. The photothermal effects promote ultrafast therapeutics release and induce significant cytotoxicity. Importantly, Anti‐HER2 antibody or HER2 targeted therapeutic is more effective in reducing HER2 expression when combined with drug or drugs via synergism. Overall, the cheap and simply manufactured biodegradable hybrid platform has great potential for advancing biomedical applications, including targeted photothermal combination therapy by co‐delivery of different types of therapeutics, including molecular targeted drugs, antibodies, and enzymes.
Egg‐Derived Mesoporous Carbon Microspheres as Bifunctional Oxygen Evolution and Oxygen Reduction Electrocatalysts
Authors: Wu Hao , Geng Jing , Ge Hongtao , Guo Ziyang , Wang Yonggang , Zheng Gengfeng
Published: July 2016

A bifunctional evolution reaction (OER) and oxygen reduction reaction (ORR) electrocatalysts are developed, based on codoped mesoporous carbon microspheres from ecofriendly biomass of eggs without the introduction of extrinsic dopants, via a facile and high‐throughput spray‐drying process. The obtained egg‐derived mesoporous carbon microspheres (egg‐CMS) present large specific surface area and high pore volume, as well as abundant dopant types including nitrogen, phosphorous, and iron that are originated from the innate protein and small organic molecule contents. When fabricated as OER or ORR catalysts, these egg‐CMS exhibit low onset potentials, high current densities, small Tafel slopes, and excellent stabilities. As a proof‐of‐concept, a rechargeable Zn‐air battery is demonstrated using the high‐active egg‐CMS as a bifunctional OER and ORR catalyst, suggesting the capability of utilizing full biomass materials for efficient energy storage and utilization.
Moisture‐Assisted Preparation of Compact GaN:ZnO Photoanode Toward Efficient Photoelectrochemical Water Oxidation
Authors: Wang Zhiliang , Han Jingfeng , Li Zheng , Li Mingrun , Wang Hong , Zong Xu , Li Can
Published: July 2016

Developing strategies that can promote charge transportation in photodevices is crucial for achieving high solar energy conversion efficiency. Herein a moisture‐assisted nitridation approach is presented for the fabrication of efficient gallium‐zinc oxynitride (GaN:ZnO) photoanode with compact structure to facilitate the charge transportation. With moisture‐assisted nitridation, the charge separation efficiency and injection efficiency obtained on GaN:ZnO photoanode are significantly enhanced. Correspondingly, the photocurrent at 1.23 V vs reversible hydrogen electrode (RHE) has 18 folds improvement compared with that prepared without moisture assistance. Furthermore, via treating with HCl acid and modification with cobalt phosphate (CoPi) as a cocatalyst, state‐of‐the‐art photocurrent over 2.0 mA cm−2 is achieved on independent GaN:ZnO photoanode when bias is higher than 1.4 V vs RHE. To the best of our knowledge, this is the first paradigm of moisture‐assisted preparing oxynitride‐based photoanode. The participation of moisture is found to improve the interconnection between adjacent GaN:ZnO nanoparticles as well as that between the GaN:ZnO film and the underlying substrate. Moreover, the volatilization of Zn can be substantially suppressed due to the modulation of reaction pathway by moisture. These two factors are confirmed to be the main reasons for the enhanced charge transportation and PEC performance obtained on GaN:ZnO photoanode.
Covalent Chemical 5′‐Functionalization of RNA with Diazo Reagents
Authors: Gampe Christian M. , Hollis‐Symynkywicz Micah , Zécri Frédéric
Published: July 2016

Functionalization of RNA at the 5′‐terminus is important for analytical and therapeutic purposes. Currently, these RNAs are synthesized de novo starting with a chemically functionalized 5′‐nucleotide, which is incorporated into RNA using chemical synthesis or biochemical techniques. Methods for direct chemical modification of native RNA would provide an attractive alternative but are currently underexplored. Herein, we report that diazo compounds can be used to selectively alkylate the 5′‐phosphate of ribo(oligo)nucleotides to give RNA labelled through a native phosphate ester bond. We applied this method to functionalize oligonucleotides with biotin and an orthosteric inhibitor of the eukaryotic initiation factor 4E (eIF4E), an enzyme involved in mRNA recognition. The modified RNA binds to eIF4E, demonstrating the utility of this labelling technique to modulate biological activity of RNA. This method complements existing techniques and may be used to chemically introduce a broad range of functional handles at the 5′‐end of RNA.
Cyclodextrins 3‐Functionalized with 8‐Hydroxyquinolines: Copper‐Binding Ability and Inhibition of Synuclein Aggregation
Authors: Oliveri Valentina , Sgarlata Carmelo , Vecchio Graziella
Published: July 2016

Neurodegenerative diseases such as Parkinson's and Alzheimer's diseases are multifactorial disorders related to protein aggregation, metal dyshomeostasis, and oxidative stress. To advance understanding in this area and to contribute to therapeutic development, many efforts have been directed at devising suitable agents that can target metal ions associated with relevant biomolecules such as α‐synuclein. This paper presents a new cyclodextrin–8‐hydroxyquinoline conjugate and discusses the properties of four cyclodextrins 3‐functionalized with 8‐hydroxyquinoline as copper(II) chelators and inhibitors of copper‐induced synuclein aggregation. The encouraging results establish the potential of cyclodextrin–8‐hydroxyquinoline conjugates as chelators for the control of copper toxicity.
Assessment of pharmacokinetics, bioavailability and protein binding of anacetrapib in rats by a simple high‐performance liquid chromatography–tandem mass spectrometry method
Authors: Kim Sang‐Bum , Kim Ki Taek , Joo Jeongmin , Seo Kyung‐Ah , Hwang Hayoung , Kim Soong‐Hyun , Song Minsoo , Lee Sungwoo , Jahn Alexander , Cho Hyun‐Jong , Kim Dae‐Duk , Yoon In‐Soo
Published: July 2016

Anacetrapib is a potent and selective CETP inhibitor and is undergoing phase III clinical trials for the treatment of dyslipidemia. A simple and sensitive high‐performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) method for the quantification of anacetrapib in rat plasma was developed and validated using an easily purchasable compound, chlorpropamide, as an internal standard (IS). A minimal volume of rat plasma sample (20 μL) was prepared by a single‐step deproteinization procedure with 80 μL of acetonitrile. Chromatographic separation was performed using Kinetex C18 column with a gradient mobile phase consisting of water and acetonitrile containing 0.1% formic acid at a flow rate of 0.3 mL/min. Mass spectrometric detection was performed using selected reaction monitoring modes at the mass/charge transitions m/z 638 → 283 for anacetrapib and m/z 277 → 175 for IS. The assay was validated to demonstrate the selectivity, linearity, precision, accuracy, recovery, matrix effect and stability. The lower limit of quantification was 5 ng/mL. This LC‐MS/MS assay was successfully applied in the rat plasma protein binding and pharmacokinetic studies of anacetrapib. The fraction of unbound anacetrapib was determined to be low (ranging from 5.66 to 12.3%), and the absolute oral bioavailability of anacetrapib was 32.7%.
An Fc–Small Molecule Conjugate for Targeted Inhibition of the Adenosine 2A Receptor
Authors: Hsiao Po‐Yuan , Kalin Jay H. , Sun Im‐Hong , Amin Mohammed N. , Lo Ying‐Chun , Chiang Meng‐Jung , Giddens John , Sysa‐Shah Polina , Gabrielson Kathleen , Wang Lai‐Xi , Powell Jonathan D. , Cole Philip A.
Published: July 2016

The adenosine A2A receptor (A2AR) is expressed in immune cells, as well as brain and heart tissue, and has been intensively studied as a therapeutic target for multiple disease indications. Inhibitors of the A2AR have the potential for stimulating immune response, which could be valuable for cancer immune surveillance and mounting a response against pathogens. One well‐established potent and selective small molecule A2AR antagonist, ZM‐241385 (ZM), has a short pharmacokinetic half‐life and the potential for systemic toxicity due to A2AR effects in the brain and the heart. In this study, we designed an analogue of ZM and tethered it to the Fc domain of the immunoglobulin IgG3 by using expressed protein ligation. The resulting protein–small molecule conjugate, Fc–ZM, retained high affinity for two Fc receptors: FcγRI and the neonatal Fc receptor, FcRn. In addition, Fc–ZM was a potent A2AR antagonist, as measured by a cell‐based cAMP assay. Cell‐based assays also revealed that Fc–ZM could stimulate interferon γ production in splenocytes in a fashion that was dependent on the presence of A2AR. We found that Fc–ZM, compared with the small molecule ZM, was a superior A2AR antagonist in mice, consistent with the possibility that Fc attachment can improve pharmacokinetic and/or pharmacodynamic properties of the small molecule.
Selective Deposition of Silver Oxide on Single‐Domain Ferroelectric Nanoplates and Their Efficient Visible‐Light Photoactivity
Authors: Chen Fang , Ren Zhaohui , Gong Siyu , Li Xiang , Shen Ge , Han Gaorong
Published: July 2016

In this work, single‐crystal and single‐domain PbTiO3 nanoplates are employed as substrates to prepare Ag2O/PbTiO3 composite materials through a photodeposition method. It is revealed that silver oxide nanocrystals with an average size of 63 nm are selectively deposited on the positive polar surface of the ferroelectric substrate. The possible mechanism leading to the formation of silver oxide is that silver ions are first reduced to silver and then oxidized by oxygen generation. The composite shows an efficient photodegradation performance towards rhodamine B (RhB) and methyl orange (MO) under visible‐light irradiation. Such highly efficient photoactivity can be attributed to the ferroelectric polarization effect of the substrate, which promotes the separation of photogenerated electrons and holes at the interface.
Visible‐Light‐Induced Trifluoromethylation of Isonitrile‐Substituted Methylenecyclopropanes: Facile Access to 6‐(Trifluoromethyl)‐7,8‐Dihydrobenzo[k]phenanthridine Derivatives
Authors: Yuan Yu‐Chao , Liu Hou‐Lu , Hu Xu‐Bo , Wei Yin , Shi Min
Published: July 2016

A new visible‐light‐induced trifluoromethylation of isonitrile‐substituted methylenecyclopropanes is developed. A range of substituted 6‐(trifluoromethyl)‐7,8‐dihydrobenzo[k]phenanthridine derivatives are readily furnished by this newly developed tandem reaction with moderate to good yields. This reaction allows the direct formation of two six‐membered rings and three new C−C bonds, including the C−CF3 bond, under visible light irradiation.
TBAI‐Catalyzed/Water‐Assisted Double C−S Bond Formations: An Efficient Approach to Sulfides through Metal‐Free Three‐Component Reactions
Authors: Chu Xue‐Qiang , Xu Xiao‐Ping , Ji Shun‐Jun
Published: July 2016

An aqueous catalytic method for double C−S bond formations that involves alcohol derivatives, organic halides, and sodium thiosulfate has been developed. A diverse range of functionalized sulfides, including pharmaceutical and biological derivatives, can be obtained in an efficient and eco‐friendly manner under air. The mechanistic studies revealed that this tetrabutylammonium‐iodide‐catalyzed/water‐assisted reaction generated a mercaptan species as the key intermediate.
A phase 1 dose‐escalation study of filanesib plus bortezomib and dexamethasone in patients with recurrent/refractory multiple myeloma
Authors: Chari Ajai , Htut Myo , Zonder Jeffrey A. , Fay Joseph W. , Jakubowiak Andrzej J. , Levy Joan B. , Lau Kenneth , Burt Steven M. , Tunquist Brian J. , Hilder Brandi W. , Rush Selena A. , Walker Duncan H. , Ptaszynski Mieke , Kaufman Jonathan L.
Published: July 2016

BACKGROUND

Filanesib is a kinesin spindle protein inhibitor that has demonstrated encouraging activity in patients with recurrent/refractory multiple myeloma. Preclinical synergy with bortezomib was the rationale for the current phase 1 study.

METHODS

The current study was a multicenter study with an initial dose‐escalation phase to determine the maximum tolerated dose of 2 schedules of filanesib plus bortezomib with and without dexamethasone, followed by a dose‐expansion phase.

RESULTS

With the addition of prophylactic filgastrim, the maximum planned dose was attained: 1.3 mg/m2/day of bortezomib plus 40 mg of dexamethasone on days 1, 8, and 15 of a 28‐day cycle, with filanesib given intravenously either at a dose of 1.5 mg/m2/day (schedule 1: days 1, 2, 15, and 16) or 3 mg/m2/day (schedule 2: days 1 and 15). The most common adverse events (assessed for severity using version 4.0 of the National Cancer Institute Common Terminology Criteria for Adverse Events) were transient, noncumulative neutropenia and thrombocytopenia with grade 3/4 events reported in 44% (16% in cycle 1 with filgastrim) and 29% of patients, respectively. A low (≤11%) overall rate of nonhematological grade 3/4 toxicity was observed. With a median of 3 prior lines of therapy and 56% of patients with disease that was refractory to proteasome inhibitors, the overall response rate was 20% (55 patients), and was 29% in 14 patients with proteasome inhibitors‐refractory disease receiving filanesib at a dose of ≥1.25 mg/m2 (duration of response, 5.2 to ≥21.2 months).

CONCLUSIONS

The current phase 1 study established a dosing schedule for the combination of these agents that demonstrated a favorable safety profile with a low incidence of nonhematologic toxicity and manageable hematologic toxicity. The combination of filanesib, bortezomib, and dexamethasone appears to have durable activity in patients with recurrent/refractory multiple myeloma. Cancer 2016;122:3327–3335. © 2016 American Cancer Society.
A novel relay nucleus between the inferior colliculus and the optic tectum in the chicken (Gallus gallus)
Authors: Niederleitner Bertram , Gutierrez‐Ibanez Cristian , Krabichler Quirin , Weigel Stefan , Luksch Harald
Published: July 2016

Processing multimodal sensory information is vital for behaving animals in many contexts. The barn owl, an auditory specialist, is a classic model for studying multisensory integration. In the barn owl, spatial auditory information is conveyed to the optic tectum (TeO) by a direct projection from the external nucleus of the inferior colliculus (ICX). In contrast, evidence of an integration of visual and auditory information in auditory generalist avian species is completely lacking. In particular, it is not known whether in auditory generalist species the ICX projects to the TeO at all. Here we use various retrograde and anterograde tracing techniques both in vivo and in vitro, intracellular fillings of neurons in vitro, and whole‐cell patch recordings to characterize the connectivity between ICX and TeO in the chicken. We found that there is a direct projection from ICX to the TeO in the chicken, although this is small and only to the deeper layers (layers 13–15) of the TeO. However, we found a relay area interposed among the IC, the TeO, and the isthmic complex that receives strong synaptic input from the ICX and projects broadly upon the intermediate and deep layers of the TeO. This area is an external portion of the formatio reticularis lateralis (FRLx). In addition to the projection to the TeO, cells in FRLx send, via collaterals, descending projections through tectopontine‐tectoreticular pathways. This newly described connection from the inferior colliculus to the TeO provides a solid basis for visual‐auditory integration in an auditory generalist bird. J. Comp. Neurol. 525:513–534, 2017. © 2016 Wiley Periodicals, Inc.
Tuning Colloidal Stability of Layered Double Hydroxides: From Monovalent Ions to Polyelectrolytes
Authors: Pavlovic Marko , Rouster Paul , Oncsik Tamas , Szilagyi Istvan
Published: July 2016

The growing number of applications of layered double hydroxide (LDH) colloids demands for detailed understanding of particle aggregation processes in such samples. Tuning the colloidal stability in aqueous suspensions is essential to design stable systems or to induce controlled aggregation of these elongated particles. In this review, recent progress in this field is summarized; in particular, the charging and aggregation of LDHs of various compositions and sizes in the presence of different aggregating agents are discussed. The review focuses on the effect of monovalent salts, multivalent ions, and polyelectrolytes on the suspension stability of LDHs. The provided information will help to better understand the origin of interparticle forces responsible for the colloidal stability and to design highly stable or aggregating LDH colloids according to the desired goals in certain applications. Moreover, potential future research directions to obtain a broader picture of LDH aggregation are also suggested.
The New Brazilian Cooperation and Facilitation Investment Agreement: An Analysis of the Conflict Resolution Mechanism in Light of the Theory of the Shadow of the Law
Authors: Gabriel Vivian
Published: July 2016

This article focuses on the changes that have occurred in Brazil's position in the regulatory regime of investments. My main interest is the dispute settlement method adopted in the new Cooperation and Facilitation Investment Agreement, which consists of a preventive mechanism and a jurisdictional method. Using the metaphor of the “shadow of the law” and relying on a comparative data analysis of the South Korean model of investment protection, I explore whether this dispute settlement method represents a stimulus or an obstacle to negotiations.
Superficial CD34‐positive fibroblastic tumor: Cytologic features, tissue correlation, ancillary studies, and differential diagnosis of a recently described soft tissue neoplasm
Authors: Li Weihong , Molnar Stacy L. , Mott Michael , White Erik , De Las Casas Luis E.
Published: July 2016

Superficial CD34‐positive fibroblastic tumor is a low‐grade mesenchymal neoplasm of superficial soft tissues characterized by fascicles of spindle to epithelioid cells displaying nuclear pleomorphism and strong diffuse CD34 immunoreactivity. The intraoperative imprint cytology preparations (ICP) of a superficial CD34‐positive fibroblastic tumor from a 50‐year‐old female are described. To the best of our knowledge, there is no report of the cytologic findings of superficial CD34‐positive fibroblastic tumor in the English medical literature. The ICP, differential diagnosis, tissue correlation, and ancillary studies of this fascinating entity are discussed. Diagn. Cytopathol. 2016;44:926–930. © 2016 Wiley Periodicals, Inc.
Metastatic urinary tract cancers in pap test: Cytomorphologic findings and differential diagnosis
Authors: Allison Derek B. , Olson Matthew T. , Maleki Zahra , Ali Syed Z.
Published: July 2016

Although the cervical Pap test was devised for the detection of primary cervical neoplasia, it can provide additional diagnostic information, and in some cases, be diagnostic for noncervical processes. The diagnosis of metastatic extrauterine cervical cancers on the Pap test is extremely rare; and in most cases, it is the result of an ovarian or fallopian tube primary. Further, urinary tract cancers, including renal and urinary primaries are exceedingly rare. To our knowledge, six surgical cases of metastatic clear cell renal cell carcinoma (RCC) have been described. We report the first case of metastatic clear cell RCC detected on the cervical Pap test. Additionally, to our knowledge, we report the second case of metastatic high‐grade urothelial carcinoma detected on the cervical Pap test. Both patients had a history of malignancy, which underscore the importance of broadening the differential diagnosis to rule out cytomorphologic features consistent with a patient's primary diagnosis when interpreting the cervical Pap test. Diagn. Cytopathol. 2016;44:1078–1081. © 2016 Wiley Periodicals, Inc.
Quantifying the human influence on fire ignition across the westernUSA
Authors: Fusco Emily J. , Abatzoglou John T. , Balch Jennifer K. , Finn John T. , Bradley Bethany A.
Published: July 2016

Humans have a profound effect on fire regimes by increasing the frequency of ignitions. Although ignition is an integral component of understanding and predicting fire, to date fire models have not been able to isolate the ignition location, leading to inconsistent use of anthropogenic ignition proxies. Here, we identified fire ignitions from the Moderate Resolution Imaging Spectrometer (MODIS) Burned Area Product (2000–2012) to create the first remotely sensed, consistently derived, and regionally comprehensive fire ignition data set for the western United States. We quantified the spatial relationships between several anthropogenic land‐use/disturbance features and ignition for ecoregions within the study area and used hierarchical partitioning to test how the anthropogenic predictors of fire ignition vary among ecoregions. The degree to which anthropogenic features predicted ignition varied considerably by ecoregion, with the strongest relationships found in the Marine West Coast Forest and North American Desert ecoregions. Similarly, the contribution of individual anthropogenic predictors varied greatly among ecoregions. Railroad corridors and agricultural presence tended to be the most important predictors of anthropogenic ignition, while population density and roads were generally poor predictors. Although human population has often been used as a proxy for ignitions at global scales, it is less important at regional scales when more specific land uses (e.g., agriculture) can be identified. The variability of ignition predictors among ecoregions suggests that human activities have heterogeneous impacts in altering fire regimes within different vegetation types and geographies.
Acetylation impacts Fli‐1‐driven regulation of granulocyte colony stimulating factor
Authors: Lennard Richard Mara L. , Brandon Danielle , Lou Ning , Sato Shuzo , Caldwell Tomika , Nowling Tamara K. , Gilkeson Gary , Zhang Xian K.
Published: July 2016

Fli‐1 has emerged as a critical regulator of inflammatory mediators, including MCP‐1, CCL5, and IL‐6. The cytokine, granulocyte colony stimulating factor (G‐CSF) regulates neutrophil precursor maturation and survival, and activates mature neutrophils. Previously, a significant decrease in neutrophil infiltration into the kidneys of Fli‐1+/‐ lupus‐prone mice was observed. In this study, a significant decrease in G‐CSF protein expression was detected in stimulated murine and human endothelial cells when expression of Fli‐1 was inhibited. The murine G‐CSF promoter contains numerous putative Fli‐1 binding sites and several regions within the proximal promoter are significantly enriched for Fli‐1 binding. Transient transfection assays indicate that Fli‐1 drives transcription from the G‐CSF promoter and mutation of the Fli‐1 DNA binding domain resulted in a 94% loss of transcriptional activation. Mutation of a known acetylation site, led to a significant increase in G‐CSF promoter activation. The histone acetyltransferases p300/CBP and p300/CBP associated factor (PCAF) significantly decrease Fli‐1 specific activation of the G‐CSF promoter. Thus, acetylation appears to be an important mechanism behind Fli‐1 driven activation of the G‐CSF promoter. These results further support the theory that Fli‐1 plays a major role in the regulation of several inflammatory mediators, ultimately affecting inflammatory disease pathogenesis.
Ruthenium‐Catalyzed C–H Amidation and Alkenylation of Cyclic N‐Sulfonyl Ketimines
Authors: Manoharan Ramasamy , Jeganmohan Masilamani
Published: July 2016

A highly regioselective ruthenium‐catalyzed C–H amidation of cyclic N‐sulfonyl ketimines with organic sulfonyl azides is described. An alkenylation at the C–H bond of cyclic N‐sulfonyl ketimines with various alkenes was also carried out. Only a catalytic amount of the oxidant Cu(OAc)2 was used in the reaction; the remainder of the required amount of oxidant was formed by regeneration of Cu(OAc)2 under an air atmosphere.
Synthesis of 1,2,3,4,5,6,7‐Heptasubstituted Cycloheptatrienes through Cycloaddition Reactions of Substituted Cyclopentadienones
Authors: Platonov Dmitry N. , Belyy Aleksandr Yu. , Ananyev Ivan V. , Tomilov Yury V.
Published: July 2016

Two schemes for synthesizing heptasubstituted cycloheptatrienes with various substituents in the ring are suggested. The first method is based on cycloaddition of 2,5‐dimethoxycarbonyl‐3,4‐diphenylcyclopentadienone with substituted cyclopropenes and allows cycloheptatrienes containing two or three electron‐withdrawing substituents in the molecule to be obtained. The second method employs a cascade reaction between a substituted cyclopentadienone and appropriate vinyldiazoacetates. It allows the number of electron‐withdrawing substituents to be increased to five. In all cases, heptasubstituted cycloheptatrienes are formed as just one of the possible isomers.
Consecutive Pictet–Spengler Condensations toward Bioactive 8‐Benzylprotoberberines: Highly Selective Total Syntheses of (+)‐Javaberine A, (+)‐Javaberine B, and (–)‐Latifolian A
Authors: Kayhan Jenifer , Wanner Martin J. , Ingemann Steen , van Maarseveen Jan H. , Hiemstra Henk
Published: July 2016

Enantiopure 8‐benzylprotoberberines were synthesized by two consecutive Pictet–Spengler (PS) condensations with protected 3,4‐dihydroxyphenylacetaldehydes. The first PS to (+)‐(R)‐norprotosinomenine was optimized to 90 % ee with 5 mol‐% of (R)‐TRIP as chiral Brønsted acid (> 99 % ee after trituration). The second PS did not require any catalyst, and its regioselectivity was strongly dependent on the solvent: 99:1 para selectivity was obtained in trifluoroethanol leading to (+)‐javaberine A; 81:19 ortho selectivity was reached in apolar aprotic solvents for the synthesis of (+)‐javaberine B. Complete, natural diastereoselectivity was observed in the second PS. Through selective catechol oxidation the spirocyclic alkaloid (–)‐latifolian A was prepared from protected (+)‐javaberine A.
Conducting Polyaniline Nanowire Arrays Modified Electrode for High Performance Supercapacitor and Enhanced Catalysis of Nitrite Reduction
Authors: Hui Ni , Wang Jiasheng , Liang Aiqin , Jiang Meilin
Published: July 2016

Vertically aligned conducting polymer nanowire arrays had great potential applications in supercapacitor electrode material and exhibited enhanced electrocatalytic behavior towards the reduction of nitrite. In this paper, a facial template‐free approach to synthesize large arrays of vertically aligned polyaniline (PANI) nanowires on electrochemically pretreated glassy carbon electrodes was reported by using a galvanostatic current method. The as‐prepared large arrays of PANI nanowires had very narrow diameters and were oriented perpendicular to the substrate, which was a benefit to the ion diffusion when being used as the supercapacitor electrode. The highest specific capacitance of PANI nanowire arrays was measured and kept high at a large charge‐discharge current density. Furthermore, it also can detect nitrite with ultrahigh sensitivity of 62.99 µA mM−1 cm−2 and a remarkable fast response time of less 1 s. The results indicated that the vertically aligned PANI nanowires could dramatically enhance the electrochemical performance.
Diffusion, Adsorption and Electrode Kinetics of Electro‐oxidatons on a Stationary Solid Electrode
Authors: Bozal‐Palabiyik Burcin , Kurbanoglu Sevinc , Uslu Bengi , Ozkan Sibel A. , Zuman Petr
Published: July 2016

The i‐E oxidation curves, obtained using a boron doped diamond electrode, for studies of oxidations of two piperazine derivatives ARIP (I) and PIRI (II), resulted in a sharp increase of current in the range of the oxidation potentials. After reaching a value, depending on concentration of I or II, the current remains practically constant up to +1.6 V. Such limiting currents i1 are a linear function of concentrations and depend on the v1/2. Hence it is diffusion controlled, shifts of the oxidation potentials indicate, that the monoprotonated forms are oxidized. At more negative potentials a limiting current i2 occurs, due to the oxidation of the diprotonated form. Current i2 increases with decreasing pH in a shape of a part of a dissociation curve. Diffusion control reflects the large size of molecules I and II. The two‐electron oxidations yield a C=N bond in the piperazine ring. It seems to be the first reported diffusion controlled oxidation curves obtained on a stationary solid electrode.
Approaches for enantioselective resolution of pharmaceuticals by miniaturised separation techniques with new chiral phases based on nanoparticles and monolithis
Authors: Sierra Isabel , Marina Maria Luisa , Pérez‐Quintanilla Damián , Morante‐Zarcero Sonia , Silva Mariana
Published: July 2016

This article discusses new developments in the preparation of nanoparticles and monoliths with emphasis upon their application as the stationary and pseudo‐stationary phases for miniaturised liquid phase separation techniques, which have occurred in the last 10 years (from 2006 to the actuality). References included in this review represent current trends and state of the art in the application of these materials to the analysis, by EKC, CEC and miniaturised chromatography, of chiral compounds with environmental interest such as pharmaceuticals. Due to their extraordinary properties, columns prepared with these new chiral stationary or pseudo‐stationary phases, based on materials such as gold nanoparticles, metal‐organic frameworks, ordered mesoporous silicas, carbonaceous materials, polymeric‐based and silica‐based monoliths or molecularly imprinted materials, can usually show some improvements in the separation selectivity, column efficiency and chemical stability in comparison with conventional chiral columns available commercially.
MEKC‐UV as an effective tool for the separation and identification of explosives, high explosives, and their degradation products in environmental samples
Authors: Copper Christine , Brensinger Karen , Rollman Christopher , Clark Alexis , Perez Marlene , Genzman Ashton , Rine Jacqueline , Moini Mehdi
Published: July 2016

MEKC has been used in conjunction with UV detection for identification and quantitation of high explosives in environmental samples. To ensure the compatibility of the technique with ESI‐MS, perfluorooctanoic acid (PFOA), a volatile micelle, was used. Separation of EPA Method 8330 Mixes A and B using various concentrations of the micelle showed that the 80 mM solution of PFOA was the optimum concentration for the separation of the explosives. MEKC analysis of explosives with ESI‐MS under optimum micelle concentration provided excellent results indicating the compatibility of the method with ESI‐MS. Finally, the MEKC‐UV method was applied to the detection and quantitation of explosives in various environmental samples including water, sand, and soil. The results demonstrate that the MEKC method described herein is a viable technique for detection of explosives in environmental samples using UV detection, while maintaining the compatibility of the technique with MS detection without any modification to the separation method, if laboratories decided to pursue this route in the future.
Research on the effect of additives on mercury speciation in coal‐fired derived flue gas
Authors: Gao Zhengyang , Sun Liwei , Lv Shaokun , Yang Pengfei
Published: July 2016

In order to study the effect of additives on mercury speciation in coal‐fired derived flue gases, the additives experiment was conducted in one 110MW coal‐fired power plant, the additives including calcium bromide and iron oxide. Taking advantage of the Ontario Water Act (OHM) and sorbent tube method, mercury at the denitration (SCR) entrance and export and desulfurization (WFGD) entrance was sampled and the variation of mercury before and during adding the additives was analyzed. The results show that the additives of calcium bromide can oxidize elemental mercury and contribute to increasing the proportion of divalent mercury, and in denitration device, the ratio of divalent mercury in flue gas shows an increasing trend along with the increasing of calcium bromide. However, there is no such trend appearing at desulfurization entrance. In addition, the additives of iron oxide have no obvious effect on the oxidation of elemental mercury in flue gas. Adding a small amount of iron oxide has little effect on the form of mercury, and may even reduce the proportion of divalent mercury. © 2016 American Institute of Chemical Engineers Environ Prog, 35: 1566–1574, 2016
Novel separation and immobilization of heavy metals in municipal solid waste fly ash by grinding with nano‐Fe/Ca/CaO/[PO4] mixture
Authors: Mallampati Srinivasa Reddy , Simion Cristian , Mitoma Yoshiharu
Published: July 2016

This study was conducted to examine the dry synthesis and application of novel nano‐size calcium/iron‐based composite material as a separation/immobilization treatment of heavy metals (As, Cd, Cr, and Pb) in fly ash from municipal solid waste incinerator. After grinding with nano‐Fe/Ca/CaO and with nano‐Fe/Ca/CaO/[PO4], approximately 30 wt % and 25 wt % of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lighter, magnetically‐separated fly ash fraction (i.e. 91% heavy metals in 25% treated fly ash). Immobilization rate of heavy metals in the magnetic or non‐magnetic fly ash fractions were about 98% and 100%, respectively. SEM‐EDS observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO4‐associated crystalline complexes. After nano‐Fe/Ca/CaO/[PO4] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. The addition of a nano‐Fe/Ca/CaO/PO4mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals. © 2016 American Institute of Chemical Engineers Environ Prog, 35: 1693–1698, 2016
Controls on the occurrence and prevalence of floodplain channels in meandering rivers
Authors: David Scott R. , Edmonds Douglas A. , Letsinger Sally L.
Published: July 2016

The process of channelization on river floodplains plays an essential role in regulating river sinuosity and creating river avulsions. Most channelization occurs within the channel belt (e.g. chute channels), but growing evidence suggests some channels originate outside of the channel‐belt in the floodplain. To understand the occurrence and prevalence of these floodplain channels we mapped 3064 km2 of floodplain in Indiana, USA using 1.5 m resolution digital elevation models (DEMs) derived from airborne light detection and ranging (LiDAR) data. We find the following range of channelization types on floodplains in Indiana: 6.8% of floodplain area has no evidence of channelization, 55.9% of floodplains show evidence (e.g. oxbow lakes) of chute‐channel activity in the channel belt, and 37.3% of floodplains contain floodplain channels that form long, coherent down‐valley pathways with bifurcations and confluences, and they are active only during overbank discharge. Whereas the first two types of floodplains are relatively well studied, only a few studies have recognized the existence of floodplain channels. To understand why floodplain channels occur, we compared the presence of channelization types with measured floodplain width, floodplain slope, river width, river meander rate, sinuosity, flooding frequency, soil composition, and land cover. Results show floodplain channels occur when the fluvial systems are characterized by large floodplain‐to‐river widths, relatively higher meandering rates, and are dominantly used for agriculture. More detailed reach‐scale mapping reveals that up to 75% of channel reaches within floodplain channels are likely paleo‐meander cutoffs. The meander cutoffs are connected by secondary channels to form floodplain channels. We suggest that secondary channels within floodplains form by differential erosion across the floodplain, linking together pre‐existing topographic lows, such as meander cutoffs. Copyright © 2016 John Wiley & Sons, Ltd.
The morphological response of foredunes at a breached barrier system to winter 2013/2014 storms on the southwest coast of Ireland
Authors: Kandrot Sarah , Farrell Eugene , Devoy Robert
Published: July 2016

The level of storminess in Ireland during the winter of 2013/2014 was exceptional, the effects of which cost the Irish state in excess of €260 million in infrastructure repair and insurance claims. In Ireland, a lack of coastal process data from monitoring programmes means that the response of protective barrier coasts to such events remains largely un‐investigated. This study addresses this issue through an examination of the geomorphic impacts of recent storms, including those that occurred during the winter 2013/2014, on a breached barrier on the southwest coast of Ireland. Data from a two‐year terrestrial laser scanning (TLS) monitoring campaign shows that the winter 2013/2014 events caused a major (>50 m) dune recession at Rossbehy, County Kerry. Results from a simple linear regression analysis indicate storm duration plays an important role in the removal of foredunes at the study site. Given the fact that the frequency of intense storms in the vicinity of Ireland is forecast to increase within the next century, a scientific understanding of barrier response to such events is critical to inform sound management practices. Copyright © 2016 John Wiley & Sons, Ltd.
Human–Landscape Interactions during the Early and High Medieval Period in Central Spain Based on New Estimates of Sediment Yield from the Melque Agricultural Complex
Authors: Ortega Raúl , Vanacker Veerle , Sanjurjo‐Sánchez Jorge , Miralles Isabel
Published: July 2016

An agrosilvopastoral system and millennium of human occupation make Santa Maria de Melque an important archaeological site in Europe. Previous archaeological work mainly focused on ceramics and wooden structural elements of a church and anthracological, palynological, and paleocarpological analyses of sediments around a rural monastery. In this paper, we extend the geoarchaeological work to dams that were constructed nearby, applying innovative techniques such as optically stimulated luminescence (OSL) dating and seismic refraction to help understand human–landscape interactions. Our OSL dating of dams and reservoir sediments provide a first detailed chronological framework for historical water storage in Central Spain. In Melque, the four dams were built consecutively during phases of Christian occupation, thereby assuring water availability to support agrosilvopastoral activities. The maximum splendor of the rural complex occurred during Phase III (Christian occupation, 12th–16th centuries A.D.). Dam construction was an integral part of the agricultural production system, and the reservoirs were effective as water harvesting systems in support of irrigated agriculture from the 7th to 16th centuries A.D. during the Early and High Medieval occupation of the site.
Cigarette use, comorbidities, and prognosis in a prospective head and neck squamous cell carcinoma population
Authors: Peterson Lisa A. , Bellile Emily L. , Wolf Gregory T. , Virani Shama , Shuman Andrew G. , Taylor Jeremy M. G. , Rozek Laura S. ,   The University of Michigan Head and Neck Specialized Program of Research Excellence Program
Published: July 2016

Background

To better understand the associations between a history of tobacco use and survival outcomes, cigarette use was prospectively surveyed in 687 previously untreated patients with cancer of the oral cavity (n = 271), oropharynx (n = 257), larynx (n = 135), or hypopharynx (n = 24).

Methods

Kaplan–Meier and Cox models explored the associations of tobacco use intensity (packs/day), duration (years of use), and timing before diagnosis with overall survival (OS), disease‐specific survival (DSS), and recurrence‐free survival (RFS).

Results

Cigarette use duration, timing, and intensity were significant predictors for all outcomes in univariate analysis. Never smoking and pack‐years were not significantly associated with outcomes after adjustment for prognostic factors, such as stage, comorbidities, and human papillomavirus (HPV) status, which were strongly associated with clinical outcomes.

Conclusion

The findings confirm the association between smoking history and survival and the importance of clinical variables in evaluating smoking as a prognostic factor. Timing, intensity, and duration of cigarette use should be considered with other prognostic factors when considering risk stratification for treatment planning. © 2016 Wiley Periodicals, Inc. Head Neck 38: 1810–1820, 2016
Tissue Inhibitor of Metalloproteinase 1 Influences Vascular Adaptations to Chronic Alterations in Blood Flow
Authors: Mandel Erin R. , Uchida Cassandra , Nwadozi Emmanuel , Makki Armin , Haas Tara L.
Published: July 2016

Remodeling of the skeletal muscle microvasculature involves the coordinated actions of matrix metalloproteinases (MMPs) and their endogenous inhibitors, tissue inhibitor of metalloproteinases (TIMPs). We hypothesized that the loss of TIMP1 would enhance both ischemia and flow‐induced vascular remodeling by increasing MMP activity. TIMP1 deficient (Timp1−/−) and wild‐type (WT) C57BL/6 mice underwent unilateral femoral artery (FA) ligation or were treated with prazosin, an alpha‐1 adrenergic receptor antagonist, in order to investigate vascular remodeling to altered flow. Under basal conditions, Timp1−/− mice had reduced microvascular content as compared to WT mice. Furthermore, vascular remodeling was impaired in Timp1−/− mice. Timp1−/− mice displayed reduced blood flow recovery in response to FA ligation and no arteriogenic response to prazosin treatment. Timp1−/− mice failed to undergo angiogenesis in response to ischemia or prazosin, despite maintaining the capacity to increase VEGF‐A and eNOS mRNA. Vascular permeability was increased in muscles of Timp1−/− mice in response to both prazosin treatment and FA ligation, but this was not accompanied by greater MMP activity. This study highlights a previously undescribed integral role for TIMP1 in both vascular network maturation and adaptations to ischemia or alterations in flow. J. Cell. Physiol. 232: 831–841, 2017. © 2016 Wiley Periodicals, Inc.