bluuebunny/crossref_metadata_2025 huggingface dataset:
Introduction to special section on The U.S. IOOS Coastal and Ocean Modeling Testbed
Authors: Luettich Richard A , Wright L. Donelson , Signell Richard , Friedrichs Carl , Friedrichs Marjy , Harding John , Fennel Katja , Howlett Eoin , Graves Sara , Smith Elizabeth , Crane Gary , Baltes Rebecca
Published: November 2013

Strong and strategic collaborations among experts from academia, federal operational centers, and industry have been forged to create a U.S. IOOS Coastal and Ocean Modeling Testbed (COMT). The COMT mission is to accelerate the transition of scientific and technical advances from the coastal and ocean modeling research community to improved operational ocean products and services. This is achieved via the evaluation of existing technology or the development of new technology depending on the status of technology within the research community. The initial phase of the COMT has addressed three coastal and ocean prediction challenges of great societal importance: estuarine hypoxia, shelf hypoxia, and coastal inundation. A fourth effort concentrated on providing and refining the cyberinfrastructure and cyber tools to support the modeling work and to advance interoperability and community access to the COMT archive. This paper presents an overview of the initiation of the COMT, the findings of each team and a discussion of the role of the COMT in research to operations and its interface with the coastal and ocean modeling community in general. Detailed technical results are presented in the accompanying series of 16 technical papers in this special issue.
Skill testing a three‐dimensional global tide model to historical current meter records
Authors: Timko Patrick G. , Arbic Brian K. , Richman James G. , Scott Robert B. , Metzger E. Joseph , Wallcraft Alan J.
Published: November 2013

We apply several skill tests to assess tidal currents within a three‐dimensional, eddy resolving, global ocean circulation model compared to over 5000 observational velocity records spanning 40 years. We examine the skill of the HYbrid Coordinate Ocean Model (HYCOM) on a regional, basin, and global scale and in deep versus shallow water. On a global scale, we examine the model tidal kinetic energy (KE) compared to the tidal KE estimated from the observational velocity records. We examine the vertical structure of the model tidal KE by averaging over predetermined depth bins. We also investigate the ability of the model to satisfy the 95% confidence intervals of the individual tidal ellipse parameters. On a basin scale, we determine if any bias exists in model performance with regards to a particular part of the global ocean and further investigate if any variability of model skill exists within the ocean basins by testing the model against smaller subsets of the observations. Our results show that the skill of the nondata assimilative HYCOM is comparable to the skill of the altimetric‐constrained model TPXO7.2. HYCOM is shown to have up to 20% higher skill in resolving the Greenwich phase of the tides on a global basis and demonstrates moderate skill in replicating the vertical structure of the tidal currents as represented by the current meters. HYCOM demonstrates up to 20% higher skill than TPXO7.2 for some ocean basins and some ocean regions but exhibits up to 20% weaker skill in the Southern Ocean.
The atmospheric HCHO budget at Dumont d'Urville (East Antarctica): Contribution of photochemical gas‐phase production versus snow emissions
Authors: Preunkert Susanne , Legrand Michel , Pépy Guillaume , Gallée Hubert , Jones Anna , Jourdain Bruno
Published: November 2013

HCHO was monitored throughout the year 2009 at the coastal East Antarctic site of Dumont d'Urville (DDU) using Aerolaser AL‐4021 analyzers. The accurate determination of less than 100 pptv required optimization of the analyzers, in particular, to minimize effects of changing ambient temperatures. The impact of station activities and of the presence of large penguin colonies at the site in summer was scrutinized. The obtained contamination‐free record indicates monthly means close to 50 pptv from May to September and a maximum of 200 pptv in January. Zero‐dimensional and 2‐D calculations suggest that in summer, the largest HCHO source is the gas‐phase photochemistry (80%) mainly driven by methane oxidation, which is considerably greater than from snow emissions (20%). The influence of light alkenes, dimethyl sulfide, and halogens remains weak. In winter, snow emissions represent the main HCHO source (70%). These findings are compared to previous studies conducted at the West Antarctic coast. It is shown that in summer the HCHO production from methane chemistry is 3 times more efficient at DDU than at the west coast due to more frequent arrival of oxidant‐rich air masses from inland Antarctica. Halogen chemistry is found to represent a weak HCHO sink at both West and East Antarctica. Compared to DDU, the shallower atmospheric boundary layer and the less efficient gas‐phase production at the west coast make the snow pack the dominant HCHO source (85%) compared to gas‐phase photochemistry (15%) there in summer.
Analysis of ATMS striping noise from its Earth scene observations
Authors: Qin Zhengkun , Zou Xiaolei , Weng Fuzhong
Published: November 2013

The differences between brightness temperature observations and simulated observations based on numerical weather predictions, i.e., O‐B, for Advanced Technology Microwave Sounder (ATMS) temperature sounding channels exhibit a clear striping pattern [Bormann et al., 2013]. We propose to first use the principal component analysis to isolate scan‐dependent features such as the cross‐track striping from the atmospheric signal and then to use an Ensemble Empirical Mode Decomposition (EEMD) to extract the striping noise in ATMS Earth scene brightness temperature observations for both temperature and water vapor sounding channels. It is shown that the Principal Component (PC) coefficient of the first PC mode, which mainly describes a scan‐dependent feature of cross‐track radiometer measurements, captures the striping noise. The EEMD is then applied to the PC coefficient to extract the first three high‐frequency intrinsic mode functions (IMFs), which are denoted as the PC1/IMF3 noise. When the PC1/IMF3 noise is removed from the data, the striping noise is imperceptible in the global distribution of O‐B for ATMS temperature sounding channels 1–16. Using the same method, it is demonstrated that the striping noise is also present in ATMS water vapor sounding channels 17–22. The magnitude of the ATMS striping noise is about ±0.3 K for the temperature sounding channels and ±1.0 K for the moisture sounding channels. The same technique is also applied to Advanced Microwave Sounding Unit‐A (AMSU‐A), AMSU‐B, and Microwave Humidity Sounder (MHS). The striping noise is undetectable for AMSU‐A but present in AMSU‐B and MHS data.
Noise performance of the CrIS instrument
Authors: Zavyalov Vladimir , Esplin Mark , Scott Deron , Esplin Benjamin , Bingham Gail , Hoffman Erik , Lietzke Christopher , Predina Joseph , Frain Rebecca , Suwinski Lawrence , Han Yong , Major Charles , Graham Brandon , Phillips Lee
Published: November 2013

The Cross‐track Infrared Sounder (CrIS) is a spaceborne Fourier transform spectrometer (FTS) that was launched into orbit on 28 October 2011 onboard the Suomi National Polar‐orbiting Partnership satellite. CrIS is a sophisticated sounding sensor that accurately measures upwelling infrared radiance at high spectral resolution. Data obtained from this sensor are used for atmospheric profiles retrieval and assimilation by numerical weather prediction models. Optimum vertical sounding resolution is achieved with high spectral resolution and multiple spectral channels; however, this can lead to increased noise. The CrIS instrument is designed to overcome this problem. Noise Equivalent Differential Radiance (NEdN) is one of the key parameters of the Sensor Data Record product. The CrIS on‐orbit NEdN surpasses mission requirements with margin and has comparable or better performance when compared to heritage hyperspectral sensors currently on orbit. This paper describes CrIS noise performance through the characterization of the sensor's NEdN and compares it to calibration data obtained during ground test. In addition, since FTS sensors can be affected by vibration that leads to spectrally correlated noise on top of the random noise inherent to infrared detectors, this paper also characterizes the CrIS NEdN with respect to the correlated noise contribution to the total NEdN. Lastly, the noise estimated from the imaginary part of the complex FTS spectra is extremely useful to assess and monitor in‐flight FTS sensor health. Preliminary results on the imaginary spectra noise analysis are also presented.
Cell Culture Processes in Monoclonal Antibody Production
Authors: Li Feng , Shen Amy , Amanullah Ashraf
Published: November 2013

This chapter outlines cell culture processes in monoclonal antibody production. Cell culture process development starts with cell line generation and selection, followed by media and culture condition optimization in small‐scale systems, including 96‐well plate, shaker flasks, and bench‐scale bioreactors, for high throughput screening purposes. Once the process conditions are defined, the process is often transferred to the pilot scale to get scale‐up information and to produce toxicology materials and later to cGMP manufacturing for production of clinical material. As development of a commercial cell culture process for production of a biological product is completed at the laboratory and pilot scales, the commercialization process begins with process characterization, scale‐up, technology transfer, and validation for the manufacturing process. The strong demand of therapeutic antibody production, relatively modest titers, and reduction of cost of goods has resulted in a trend toward large‐scale manufacturing. Today, the largest biotech companies are using several hundred to 2,000 L scale bioreactors for early clinical production and 10,000‐25,000 L stirred tank bioreactors to produce commercial products.
Regulatory Strategies and Lessons in the Development of Biosimilars
Authors: Shah Umang S.
Published: November 2013

The objective of this chapter is to understand the scientific challenges and the main elements of the EU pathway and the proposed US FDA regulatory pathway for biosimilars while considering potential strategies in the development of a successful biosimilar. In summary, the European Union has a well‐established and well‐documented legal and regulatory pathway for the review and approval of biosimilars. With a biosimilar registration pathway in place in the US, it is expected to pave the way for the market entry of biosimilars beginning in 2013. The FDA may commit to publishing class‐specific guidelines that discuss the approval standards and other key implementation issues for particular product classes. As discussed, class‐specific guidance will be the most meaningful for manufacturers and will foster the confidence in biosimilars needed for physician and patient acceptance of this new class of product.
Control of Rabinovich chaotic system using sliding mode control
Authors: Kocamaz Uğur Erkin , Uyaroğlu Yılmaz , Kizmaz Hakan
Published: November 2013

This paper investigates the control of the continuous time Rabinovich chaotic system with the sliding mode control method. Based on the properties of the sliding mode theory, the controllers are designed and added to the nonlinear Rabinovich system. Numerical simulations show that the Rabinovich chaotic system can be regulated to its equilibrium points in the state space by using the sliding mode controllers, which verifies all the theoretical analyses. Simulation results of the proposed sliding mode control strategy have been also compared with the passive control method, and their performances are discussed. Copyright © 2013 John Wiley & Sons, Ltd.
Sites of extranodal involvement are prognostic in patients with diffuse large B‐cell lymphoma in the rituximab era: An analysis of the Surveillance, Epidemiology and End Results database
Authors: Castillo Jorge J. , Winer Eric S. , Olszewski Adam J.
Published: November 2013

Approximately a third of the patients with diffuse large B‐cell lymphoma present with extranodal involvement. Our study aims to identify primary extranodal sites of disease associated with prognosis in patients with diffuse large B‐cell lymphoma (DLBCL) in the rituximab era. A secondary objective is to describe epidemiological and clinical characteristics of patients with extranodal DLBCL. We included adult patients from the Surveillance, Epidemiology and End Results (SEER) database (2004–2009) in whom DLBCL was the first malignancy diagnosed. Extranodal primary sites were divided into 12 groups according to the topography code reported by SEER. Multivariate overall survival (OS) analyses were performed using Cox proportional‐hazard regression models adjusted for age, sex, race, and stage. From a total of 25,992 adult DLBCL patients included in our analysis, 32% presented with extranodal primary sites. Gastrointestinal tract (34%), head/neck (H&N; 14%), and skin/soft tissue (11%) were the most common. In comparison with nodal DLBCL, patients with extranodal involvement were older (with exception of skeletal sites) and presented with earlier stages. In the multivariate analysis, sites associated with worse OS rates were gastrointestinal (Hazard ratio (HR) 1.24, 95% confidence interval (CI) 1.15–1.33; P <0.001), pulmonary (HR 1.59, 95% CI 1.38–1.83; P <0.001), and liver/pancreas (HR 1.58, 95% CI 1.35–1.85; P <0.001), whereas H&N was associated with better survival (HR 0.79, 95% CI 0.70–0.89; P <0.001). In this population‐based study, primary extranodal sites of involvement are associated with distinct outcomes in patients with DLBCL. Gastrointestinal, pulmonary, and liver/pancreas sites had a significant worse outcome than nodal sites. Am. J. Hematol. 89:310–314, 2014. © 2013 Wiley Periodicals, Inc.
Novel interstitial 2.6 Mb deletion on 9q21 associated with multiple congenital anomalies
Authors: Pua Heather H. , Krishnamurthi Swetha , Farrell Jessica , Margeta Marta , Ursell Philip C. , Powers Martin , Slavotinek Anne M. , Jeng Linda J.B.
Published: November 2013

Array comparative genomic hybridization (aCGH) is now commonly used to identify copy number changes in individuals with developmental delay, intellectual disabilities, autism spectrum disorders, and/or multiple congenital anomalies. We report on an infant with multiple congenital anomalies and a novel 2.6 Mb interstitial deletion within 9q21.32q21.33 detected by aCGH. Her clinical presentation included dysmorphic craniofacial features, cleft palate, atrial septal defect, bicornuate uterus, bilateral hip dislocation, hypotonia, and recurrent pneumonia. Parental aCGH studies were negative for copy loss in this region. To our knowledge, no similar deletions have been reported in available databases or published literature. This deletion encompasses 12 genes, and prediction algorithms as well as experimental data suggest that a subset is likely to be haploinsufficient. Included are a neurotrophin receptor (NKG2D), a gene implicated in cilia function (KIF27), an adaptor protein important for ubiquitin‐dependent protein quality control (UBQLN1), a gene important for transcription and signaling (HNRNPK), and a gene involved in maintaining genomic stability (RMI1). Identifying additional patients with similar copy losses and further study of these genes will contribute to a better understanding of the pathophysiology of multiple congenital anomalies. © 2013 Wiley Periodicals, Inc.
Anxiety, attention problems, hyperactivity, and the Aberrant Behavior Checklist in fragile X syndrome
Authors: Wheeler Anne , Raspa Melissa , Bann Carla , Bishop Ellen , Hessl David , Sacco Pat , Bailey Donald B.
Published: November 2013

Behavior problems are a common challenge for individuals with fragile X syndrome (FXS) and constitute the primary clinical outcome domain in trials testing new FXS medications. However, little is known about the relationship between caregiver‐reported behavior problems and co‐occurring conditions such as anxiety and attention problems. In this study, 350 caregivers, each with at least one son or daughter with full‐mutation FXS, rated one of their children with FXS using the Aberrant Behavior Checklist—Community Version (ABC‐C); the Anxiety subscale of the Anxiety, Depression, and Mood Scale; and the Attention/Hyperactivity Items from the Symptom Inventories. In addition to examining family consequences of these behaviors, this study also sought to replicate psychometric findings for the ABC‐C in FXS, to provide greater confidence for its use in clinical trials with this population. Psychometric properties and baseline ratings of problem behavior were consistent with other recent studies, further establishing the profile of problem behavior in FXS. Cross‐sectional analyses suggest that selected dimensions of problem behavior, anxiety, and hyperactivity are age related; thus, age should serve as an important control in any studies of problem behavior in FXS. Measures of anxiety, attention, and hyperactivity were highly associated with behavior problems, suggesting that these factors at least coincide with problem behavior. However, these problems generally did not add substantially to variance in caregiver burden predicted by elevated behavior problems. The results provide further evidence of the incidence of problem behaviors and co‐occurring conditions in FXS and the impact of these behaviors on the family. © 2013 Wiley Periodicals, Inc.
Contribution of congenital heart disease to neuropsychiatric outcome in school‐age children with 22q11.2 deletion syndrome
Authors: Yi James J. , Tang Sunny X. , McDonald‐McGinn Donna M. , Calkins Monica E. , Whinna Daneen A. , Souders Margaret C. , Zackai Elaine H. , Goldmuntz Elizabeth , Gaynor James W. , Gur Ruben C. , Emanuel Beverly S. , Gur Raquel E.
Published: November 2013

Children with 22q11.2 deletion syndrome (22q11DS) present with congenital heart disease (CHD) and high prevalence of psychiatric disorders and neurocognitive deficits. Although CHD has been implicated in neurodevelopment, its role in the neuropsychiatric outcome in 22q11DS is poorly understood. We investigated whether CHD contributes to the high prevalence of psychiatric disorders and neurocognitive impairments in 22q11DS. Fifty‐four children ages 8–14 years with 22q11DS and 16 age‐matched non‐deleted children with CHD participated. They were assessed using semi‐structured interviews and a Computerized Neurocognitive Battery. CHD status was assessed using available medical records. Prevalence of psychiatric disorders and cognitive profiles were compared among the groups. There were no significant differences between the prevalence of psychiatric disorders in the 22q11DS with and without CHD. In 22q11DS with CHD, the prevalence rates were 41% anxiety disorders, 37% ADHD and 71% psychosis spectrum. In 22q11DS without CHD, the rates were 33% anxiety disorders, 41% ADHD and 64% psychosis spectrum. In comparison, the non‐deleted CHD group had lower rates of psychopathology (25% anxiety disorders, 6% ADHD, and 13% psychosis spectrum). Similarly, the 22q11DS groups, regardless of CHD status, had significantly greater neurocognitive deficits across multiple domains, compared to the CHD‐only group. We conclude that CHD in this sample of children with 22q11.2DS does not have a major impact on the prevalence of psychiatric disorders and is not associated with increased neurocognitive deficits. These findings suggest that the 22q11.2 deletion status itself may confer significant neuropsychiatric vulnerability in this population. © 2013 Wiley Periodicals, Inc.
Synthesis of 3,5‐Disubstituted Cyclohex‐2‐en‐1‐one via a Five‐Step Domino Reaction Catalyzed by Secondary Amines: Formation of (E)‐α,β‐Unsaturated Methyl Ketones
Authors: Ghorai Manas K. , Samanta Sauvik , Das Subhomoy
Published: November 2013

A simple strategy for the synthesis of 5‐substituted‐3‐methylcyclohex‐2‐en‐1‐ones by proline‐catalyzed five‐step domino reactions of acetone and aromatic aldehydes is reported. The starting materials are stirred in the presence of L‐proline for 24 h then heated to 45 °C for a further 4‐6 h. The method can also be changed to exclusively form α,β‐unsaturated methyl ketones with >99 % E‐selectivity by heating the mixture to 80 °C in the second stage.
Organocatalytic Enantioselective Friedel–Crafts Reaction of 1‐Naphthols with Isatins and an Unexpected Spontaneous Dehydration Process
Authors: Wu Deyan , Zhang Xuwen , Xu Yong , Xue Yingfei , Li Jian , Wang Wei , Zhu Jin
Published: November 2013

An organocatalytic enantioselective Friedel–Crafts alkylation of 1‐naphthols with isatins has been developed. The process is catalyzed by a simple cinchona alkaloid derived thiourea and gives biologically interesting, enantioenriched 3‐(naphthalen‐2‐yl)‐3‐hydroxy‐2‐oxindoles in moderate to good yields of 42–83 % and with good to high enantioselectivity of up to 94 % ee. Furthermore, an unexpected intramolecular dehydration reaction proceeds spontaneously with 4‐substituted 1‐naphthols to offer structurally different ketone oxindoles.
Nutzung natürlicher Proteinsymmetrie zum Design lichtschaltbarer Enzyminhibitoren
Authors: Reisinger Bernd , Kuzmanovic Natascha , Löffler Patrick , Merkl Rainer , König Burkhard , Sterner Reinhard
Published: November 2013

Die Aktivität des metabolischen Schlüsselenzyms PriA aus Mycobacterium tuberculosis (mtPriA) kann reversibel durch Licht kontrolliert werden. Auf der Grundlage des Dithienylethen‐Gerüsts wurden entsprechend der zweifachen Rotationssymmetrie des Proteins symmetrische Inhibitoren mit terminalen Ankern entworfen. Durch Schalten vom flexiblen, offenen Isomer zur starren, geschlossenen Form wurde die Inhibitionsaktivität um eine Größenordnung reduziert.
Simple and Compelling Biomimetic Metal–Organic Framework Catalyst for the Degradation of Nerve Agent Simulants
Authors: Katz Michael J. , Mondloch Joseph E. , Totten Ryan K. , Park Jin K. , Nguyen SonBinh T. , Farha Omar K. , Hupp Joseph T.
Published: November 2013

Inspired by biology, in which a bimetallic hydroxide‐bridged zinc(II)‐containing enzyme is utilized to catalytically hydrolyze phosphate ester bonds, the utility of a zirconium(IV)‐cluster‐containing metal–organic framework as a catalyst for the methanolysis and hydrolysis of phosphate‐based nerve agent simulants was examined. The combination of the strong Lewis‐acidic ZrIV and bridging hydroxide anions led to ultrafast half‐lives for these solvolysis reactions. This is especially remarkable considering that the actual catalyst loading was a mere 0.045 % as a result of the surface‐only catalysis observed.
Umkodierung des genetischen Codes mit Selenocystein
Authors: Bröcker Markus J. , Ho Joanne M. L. , Church George M. , Söll Dieter , O'Donoghue Patrick
Published: November 2013

Der Selenocystein(Sec)‐Einbau in Proteine erfolgt in der Natur durch die kotranslationale Umkodierung eines UGA‐Stopp‐Codons. Diese Studie zeigt nun, dass Sec nicht ausschließlich durch UGA, sondern vielmehr durch 58 aller 64 möglichen Codons kodiert werden kann. Hierbei erlauben 15 Codons nicht nur die vollständige Umkodierung von ihrer ursprünglichen Bedeutung als kanonische Aminosäure zu Selenocystein, sondern sie führen zu Proteinausbeuten, die um mehr als das Zehnfache gesteigert sind. Der hoch effiziente Mechanismus zur Selenocystein‐Rekodierung wird anhand zweier Reporterenzyme, der Escherichia‐coli‐Formiatdehydrogenase und der humanen Thioredoxinreduktase, beschrieben. Da der Selenocysteineinbau an der Position eines UGA‐Stopp‐Codons zwangsläufig mit translationaler Termination konkurriert, war es umso erstaunlicher, dass die Selenocystein‐Einbaumaschinerie während der Umkodierung von Sense‐Codons erfolgreich mit den im Überfluss vorhandenen regulären Aminoacyl‐tRNAs konkurriert.
Furan/imide Diels–Alder polymers as dielectric materials
Authors: Lorenzini Robert G. , Sotzing Gregory A.
Published: November 2013

Herein, the synthesis and characterization of a series of Diels–Alder (DA) polymers made with various bis‐furans and 1,3‐bis(maleimide)propane are described. Due to the fact that these syntheses produce no byproducts inherent to their mechanism, as well as the relative ease at which highly functionalized monomers can be made, these polymers are identified as candidates for dielectric materials with high dielectric constants. The dielectric spectra of these polymers are reported, with an emphasis placed on describing observed structure–property trends. Dielectric constants for these materials range from 4.31 to 6.75 at room temperature, with dielectric losses in the 1–2% regime. These polymers are thermally stable to ∼130°C, where the retro DA reaction was confirmed with multiple analytical methods, including thermogravimetric analysis, differential scanning calorimetry, and gas chromatography/mass spectrometry thermal desorption spectroscopy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40179.
Microtextured polystyrene surfaces for three‐dimensional cell culture made by a simple solvent treatment method
Authors: DeRosa Michael E. , Hong Yulong , Faris Ronald A. , Rao Hongwei
Published: November 2013

This article describes a solvent treatment process for transforming standard flat polystyrene surfaces into textured microenvironments for three‐dimensional (3D) cell culture. The process can be used with off‐the‐shelf microplates having 6, 12, 96, or even 384‐well formats and completed in a few steps. The surface microtexture resembles tightly packed, non‐interconnected micropores having a median pore size of either 115 or 19 μm depending on the strength of the solvent mixture. Hansen solubility parameter analysis was used to map out the polymer–solvent interaction conditions necessary for creating the surface texture. Primary human hepatocytes cultured on two‐dimensional control surfaces attached with a flat monolayer morphology while those cultured on surfaces having 115 μm‐sized pores exhibited a round 3D morphology. The cells also showed more in‐vivo like behavior on the porous surface by exhibiting significantly higher basal enzymatic activity and expressing higher levels of several drug metabolism‐related genes. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40181.
Acrylate–vinylidene chloride copolymers derived from corresponding water‐borne latexes: Influence of acrylate units on their potential as heavy‐duty anticorrosive coating materials
Authors: Fu Ce , Qin Hong‐Wei , Ben Hai‐Jie , Han Jing , Cui Wen‐Zhu , Cheng Fa , Chen Yu
Published: November 2013

A series of aqueous latexes with solid contents of 56%–59% were synthesized by binary emulsion copolymerization of vinylidene chloride (VDC) with an acrylate, namely methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), hexyl acrylate (HA), or 2‐ethylhexyl acrylate (EHA). Differential scanning calorimetry (DSC) and Fourier‐transform infrared (FTIR) spectroscopy showed that the acrylate units with short ester side‐chains, such as MA and EA, made the copolymers hard and the crystallization tendency of their PVDC segments was reduced. Hydrophobic acrylates with relatively long ester groups, such as HA and EHA, gave flexible copolymers, and favored the crystallization of their PVDC segments. BA endowed the copolymers with medium flexibility and crystallization tendency. As coating materials, the copolymers bearing MA and EA adhered poorly to the tinplate before or after 100 hr of salt‐spray corrosion, whereas those bearing BA, HA, or EHA showed good adhesion to tinplate when they had little or no crystallinity. After 100 hr of salt‐spray corrosion, only BA–VDC80, containing 80% VDC, retained both excellent adhesion to metal and excellent barrier performance. Further study demonstrated that BA–VDC80 could protect tinplate from rusting for at least 250 hr under harsh salt‐spray corrosion. Scanning electron microscopy, FTIR‐attenuated total reflectance spectroscopy and DSC were used to evaluate the corroded BA–VDC80 film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40192.
Enantiomerization Pathway and Atropochiral Stability of the BINAP Ligand: A Density Functional Theory Study
Authors: Sanz García Juan , Lepetit Christine , Canac Yves , Chauvin Remi , Boggio‐Pasqua Martial
Published: November 2013

A theoretical study of the enantiomerization pathway of BINAP, the paradigm of atropochiral ligands in asymmetric organometallic catalysis, is reported. Density functional theory was used with the B3PW91 functional and the 6‐31G(d,p) basis set. The calculation level was validated through the study of the syn and anti enantiomerization pathways of the 1,1′‐binaphthyl reference for which the enantiomerization barrier was calculated to be in good agreement with experimental data. Calculations were then performed on BINAP itself using the same level of theory, and showed that its enantiomerization mechanism follows the syn route through a concerted, yet highly asynchronous, all‐chiral process. The enantiomerization barrier was computed at 213 kJ mol−1 and proved little sensitive to the functional or to the basis set used, with values always larger than 200 kJ mol−1. The configurational stability of BINAP was finally characterized by a computed Oki’s racemization temperature of 491 °C.
Olfaction: Anatomy, physiology, and disease
Authors: Patel Riddhi M. , Pinto Jayant M.
Published: November 2013

The olfactory system is an essential part of human physiology, with a rich evolutionary history. Although humans are less dependent on chemosensory input than are other mammals (Niimura 2009, Hum. Genomics 4:107–118), olfactory function still plays a critical role in health and behavior. The detection of hazards in the environment, generating feelings of pleasure, promoting adequate nutrition, influencing sexuality, and maintenance of mood are described roles of the olfactory system, while other novel functions are being elucidated. A growing body of evidence has implicated a role for olfaction in such diverse physiologic processes as kin recognition and mating (Jacob et al. 2002a, Nat. Genet. 30:175–179; Horth 2007, Genomics 90:159–175; Havlicek and Roberts 2009, Psychoneuroendocrinology 34:497–512), pheromone detection (Jacob et al. 200b, Horm. Behav. 42:274–283; Wyart et al. 2007, J. Neurosci. 27:1261–1265), mother–infant bonding (Doucet et al. 2009, PLoS One 4:e7579), food preferences (Mennella et al. 2001, Pediatrics 107:E88), central nervous system physiology (Welge‐Lüssen 2009, B‐ENT 5:129–132), and even longevity (Murphy 2009, JAMA 288:2307–2312). The olfactory system, although phylogenetically ancient, has historically received less attention than other special senses, perhaps due to challenges related to its study in humans. In this article, we review the anatomic pathways of olfaction, from peripheral nasal airflow leading to odorant detection, to epithelial recognition of these odorants and related signal transduction, and finally to central processing. Olfactory dysfunction, which can be defined as conductive, sensorineural, or central (typically related to neurodegenerative disorders), is a clinically significant problem, with a high burden on quality of life that is likely to grow in prevalence due to demographic shifts and increased environmental exposures. Clin. Anat. 27:54–60, 2014. © 2013 Wiley Periodicals, Inc.
Dehydrogenative Lactonization of Diols in Aqueous Media Catalyzed by a Water‐Soluble Iridium Complex Bearing a Functional Bipyridine Ligand
Authors: Fujita Ken‐ichi , Ito Wataru , Yamaguchi Ryohei
Published: November 2013

A new catalytic system for the dehydrogenative lactonization of a variety of benzylic and aliphatic diols in aqueous media was developed. By using a water‐soluble, dicationic iridium catalyst bearing 6,6′‐dihydroxy‐2,2′‐bipyridine as a functional ligand, highly atom economical and environmentally benign synthesis of various lactones was achieved in good to excellent yields. Recovery and reuse of the catalyst were also accomplished by a simple phase separation and the recovered catalyst maintained its high activity at least until the fifth run.
Resistance‐Switchable Graphene Oxide–Polymer Nanocomposites for Molecular Electronics
Authors: Liu Gang , Chen Yu , Li Run‐Wei , Zhang Bin , Kang En‐Tang , Wang Cheng , Zhuang Xiaodong
Published: November 2013

As the thinnest material ever known in the universe, graphene has attracted a tremendous amount of attention in recent years. To switch graphene ON and OFF for memory devices, electroactive polymers, including polyaniline (PANI), polyvinylcarbazole (PVK), triphenylamine‐based polyazomethine (TPAPAM), polythiophene (PTh), and others, have been covalently bonded to graphene oxide (GO) to manipulate the processability and to engineer the molecular bandgap of the atomic carbon nanosheets. GO–PANI, GO–PVK, and GO–TPAPAM demonstrate promising bi‐stable resistive switching behaviors with small turn‐on voltages of less than 2.0 V, low power consumptions of 6.7 nW–221.4 μW, and large ON/OFF ratios exceeding 103. With advantages including miniaturized dimensions, mechanical flexibility, and the non‐exotic nature of the raw carbon material, GO–polymer nanocomposites promise to have great potential for next‐generation information‐storage applications.
Atom‐Efficient Gold(I)‐Chloride‐Catalyzed Synthesis of α‐Sulfenylated Carbonyl Compounds from Propargylic Alcohols and Aryl Thiols: Substrate Scope and Experimental and Theoretical Mechanistic Investigation
Authors: Biswas Srijit , Dahlstrand Christian , Watile Rahul A. , Kalek Marcin , Himo Fahmi , Samec Joseph S. M.
Published: November 2013

Gold(I)‐chloride‐catalyzed synthesis of α‐sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols showed a wide substrate scope with respect to both propargylic alcohols and aryl thiols. Primary and secondary aromatic propargylic alcohols generated α‐sulfenylated aldehydes and ketones in 60–97 % yield. Secondary aliphatic propargylic alcohols generated α‐sulfenylated ketones in yields of 47–71 %. Different gold sources and ligand effects were studied, and it was shown that gold(I) chloride gave the highest product yields. Experimental and theoretical studies demonstrated that the reaction proceeds in two separate steps. A sulfenylated allylic alcohol, generated by initial regioselective attack of the aryl thiol on the triple bond of the propargylic alcohol, was isolated, evaluated, and found to be an intermediate in the reaction. Deuterium labeling experiments showed that the protons from the propargylic alcohol and aryl thiol were transferred to the 3‐position, and that the hydride from the alcohol was transferred to the 2‐position of the product. Density functional theory (DFT) calculations showed that the observed regioselectivity of the aryl thiol attack towards the 2‐position of propargylic alcohol was determined by a low‐energy, five‐membered cyclic protodeauration transition state instead of the strained, four‐membered cyclic transition state found for attack at the 3‐position. Experimental data and DFT calculations supported that the second step of the reaction is initiated by protonation of the double bond of the sulfenylated allylic alcohol with a proton donor coordinated to gold(I) chloride. This in turn allows for a 1,2‐hydride shift, generating the final product of the reaction.
Synthesis of Cyclobakuchiols A, B, and C by Using Conformation‐Controlled Stereoselective Reactions
Authors: Kawashima Hidehisa , Kaneko Yuki , Sakai Masahiro , Kobayashi Yuichi
Published: November 2013

Cyclohexanone with the pMeOC6H4 and CH2C(Me) substituents at the C3 and C4‐positions was prepared from (+)‐β‐pinene and converted to the allylic picolinate by a Masamune–Wittig reaction followed by reduction and esterification. Allylic substitution of this picolinate with Me2CuMgBr⋅MgBr2 in the presence of ZnI2 proceeded with γ regio‐ and stereoselectively to afford the quaternary carbon center on the cyclohexane ring with the CH2CH and Me groups in axial and equatorial positions, respectively. This product was converted to cyclobakuchiol A by demethylation and to cyclobakuchiol C by epoxidation of the CH2C(Me) group. For the synthesis of cyclobakuchiol B, the enantiomer of the above cyclohexanone derived from (−)‐β‐pinene was converted to the cyclohexane‐carboxylate, and the derived enolate was subjected to the reaction with CH2CHSOPh followed by sulfoxide elimination to afford the intermediate with the quaternary carbon center with MeOC(O) and CH2CH groups in axial and equatorial positions. The MeOC(O) group was transformed to the Me group to complete the synthesis of cyclobakuchiol B.
The awesome power of dikaryons for studying flagella and basal bodies in Chlamydomonas reinhardtii
Authors: Dutcher Susan K.
Published: November 2013

Cilia/flagella and basal bodies/centrioles play key roles in human health and homeostasis. Among the organisms used to study these microtubule‐based organelles, the green alga Chlamydomonas reinhardtii has several advantages. One is the existence of a temporary phase of the life cycle, termed the dikaryon. These cells are formed during mating when the cells fuse and the behavior of flagella from two genetically distinguishable parents can be observed. During this stage, the cytoplasms mix allowing for a defect in the flagella of one parent to be rescued by proteins from the other parent. This offers the unique advantage of adding back wild‐type gene product or labeled protein at endogenous levels that can used to monitor various flagellar and basal body phenotypes. Mutants that show rescue and ones that fail to show rescue are both informative about the nature of the flagella and basal body defects. When rescue occurs, it can be used to determine the mutant gene product and to follow the temporal and spatial patterns of flagellar assembly. This review describes many examples of insights into basal body and flagellar proteins' function and assembly that have been discovered using dikaryons and discusses the potential for further analyses. © 2013 Wiley Periodicals, Inc.
Distribution of neuronal KCC2a and KCC2b isoforms in mouse CNS
Authors: Markkanen Marika , Karhunen Tuula , Llano Olaya , Ludwig Anastasia , Rivera Claudio , Uvarov Pavel , Airaksinen Matti S.
Published: November 2013

The neuronal K‐Cl cotransporter KCC2 maintains the low intracellular chloride concentration required for the fast hyperpolarizing actions of inhibitory neurotransmitters in mature central nervous system (CNS). The KCC2 gene produces two isoforms, KCC2a and KCC2b, that differ in their N‐termini. Increase of KCC2b in the cortex underlies the developmental shift in γ‐aminobutyric acid (GABA)ergic responses, whereas the physiological role of KCC2a is still poorly characterized. The two KCC2 isoforms show equal distribution in mouse brainstem neurons at birth; however their postnatal expression patterns, and the subcellular localization of KCC2a, have not yet been described. Here, we compared the pattern of KCC2a and KCC2b expression in different regions of postnatal mouse CNS by immunohistochemistry by using isoform‐specific antibodies. Tissue from KCC2a isoform‐specific knockout mice was used as a negative control. KCC2b expression increased postnatally and was widely expressed in adult brain. KCC2a immunoreactivity was low or absent in most parts of the adult cortex, hippocampus, thalamus, and cerebellar cortex. Both isoforms were widely present in the developing and mature hypothalamus, a large part of the brainstem, and the spinal cord. A notable exception was the lack of KCC2a staining in the brainstem auditory system. At the subcellular level, the isoforms were only partially colocalized. In neuronal somas, KCC2b immunoreactivity was concentrated at the plasma membrane, whereas KCC2a signal was not. Moreover, although both isoforms were expressed in microtubule‐associated protein (MAP)2‐positive dendrites, they appeared in non‐overlapping dendritic compartments. The results, together with those of previous studies, suggest that KCC2a and KCC2b have overlapping roles in neonatal neurons but presumably different roles in mature neurons. J. Comp. Neurol. 522:1897–1914, 2014. © 2013 Wiley Periodicals, Inc.
A novel method of network function analysis based on the Andreani–Mattisson extension to the Cochrun–Grabel algorithm
Authors: Fontana Giuseppe
Published: November 2013

Knowing the Network Function (NF) pertaining to a certain input–output couple individuated inside a linear electrical network (LEN) is crucial, as it provides a synthetic and effective description of the input–output relationship and allows one to derive several key features of the subject system as well as to devise proper strategies to modify them.

From a mathematical point of view, an NF may be expressed as the product of a real number, called the gain constant (GC), by a real rational function of the complex variables, whose numerator and denominator are called the zero polynomial (ZP) and the characteristic polynomial (CP), respectively, and may be obtained by calculating the determinants of proper matrices. However, when a design‐oriented symbolic hand analysis is needed, calculating the said polynomials in this manner may turn out to be tediously cumbersome; and above all, such a route may fail to illuminate the way that their coefficients depend on the circuit elements. The same may be said of numerical computer methods, which are suited to providing a global description of the NF in the frequency domain rather than analytical expressions of its coefficients. In this paper, a method is proposed that permits one to obtain the ZP without calculating any determinants. With respect to other methods that achieve the same goal, the present one does not require prior calculation of the CP or a nullator‐norator pair (NNP) to be compulsorily inserted in the subject circuit. Instead, it is based on applying the Andreani‐Mattisson extension (AME) of the Cochrun–Grabel algorithm (CGA) for the calculation of the CP to a circuit obtained from the assigned one by inserting in the latter a proper dependent source. The nature of such new circuit allows the worker to employ the classical tools of LEN theory so as to make the analysis as simple as possible and often performable by straightforward inspection, without the need for possibly involved equilibrium equations. Moreover, it is shown how the same technique can be applied to a properly modified version of the original network in order to calculate the CP as well. In this case (not compulsorily but if judged convenient for simplifying the calculations), a NNP may be employed in conjunction with the dependent source. The proposed method once again allows one to exploit the classic tools of LEN theory so as to considerably, if not drastically, simplify the analysis associated with the direct application of the AME to the original network. Finally, the calculation of the GC (that completes the knowledge of the whole NF under study) as well as circuit degeneracy are discussed and practical examples of application of the proposed techniques are given. Copyright © 2013 John Wiley & Sons, Ltd.
Neural crest‐derived cells sustain their multipotency even after entry into their target tissues
Authors: Motohashi Tsutomu , Kitagawa Daisuke , Watanabe Natsuki , Wakaoka Takanori , Kunisada Takahiro
Published: November 2013

Background: Neural crest cells (NC cells) are highly migratory multipotent cells. Their multipotency is transient at the early stage of their generation; soon after emerging from the neural tube, these cells turn into lineage‐restricted precursors. However, recent studies have disputed this conventionally believed paradigm. In this study, we analyzed the differentiation potency of NC‐derived cells after their arrival at target tissues. Results: Using Sox10‐IRES‐Venus mice, we found that the NC‐derived cells in the skin, DRG, and inner ear could be divided into two populations: Sox10‐positive/Kit‐negative cells (Sox10+/Kit‐ cells) and Sox10‐ and Kit‐positive cells (Sox10+/Kit+ cells). Only the Sox10+/Kit‐ cells were detected in the intestines. Unexpectedly, the Sox10+/Kit+ cells differentiated into neurons, glial cells, and melanocytes, showing that they had maintained their multipotency even after having entered the target tissues. The Sox10+/Kit+ cells in the DRG maintained their multipotency for a restricted period during the earlier embryonic stages, whereas those in the skin and inner ear were multipotent yet even in later embryonic stages. Conclusions: We showed that NC‐derived Sox10+/Kit+ cells maintained their multipotency even after entry into the target tissues. This unexpected differentiation potency of these cells in tissues seems to have been strictly restricted by the tissue microenvironment. Developmental Dynamics 243:368–380, 2014. © 2013 Wiley Periodicals, Inc.
Rhodamine‐Based Chromo‐/Fluorogenic Dual Signalling Probe for Selective Recognition of HgII with Potential Applications for INHIBIT Logic Devices and Cell‐Imaging Studies
Authors: Mistri Tarun , Alam Rabiul , Dolai Malay , Kumar Mandal Sushil , Guha Pratik , Rahman Khuda‐Bukhsh Anisur , Ali Mahammad
Published: November 2013

A new rhodamine‐based dual signaling probe (L3) has been found to display quick responses through visible colorimetric changes as well as fluorogenic properties on selective 1:1 binding to Hg2+, as delineated by absorption and fluorescence titrations as well as by Job′s method and ESI‐MS+ studies. The fluorescent probe L3 displays a 252‐fold fluorescence enhancement on binding to Hg2+. A Benesi–Hilderband fit of the absorption titration data gives Kd = (32.01 ± 0.74) μM and a 1:1 binding stoichiometry. Owing to its solubility in mixed organic/aqueous solvents as well as its cell permeability, L3 could be used for in vitro/in vivo cell imaging of Hg2+ with no or negligible cytotoxicity. The detection limit of Hg2+ was calculated by the 3σ method to be 9.28 ng L–1. Moreover, the fluorescence of the L3–Hg2+ system was turned off and its red colour disappeared when KI was added. Thus, the “OFF–ON–OFF” fluorescence sensing behaviour of L3 observed in the presence of Hg2+ and I– may find applications in devices with logic gate functions.