bluuebunny/crossref_metadata_2025 huggingface dataset:
Increasing Thyromimetic Potency through Halogen Substitution
Authors: Devereaux Jordan , Ferrara Skylar J. , Banerji Tania , Placzek Andrew T. , Scanlan Thomas S.
Published: October 2016

Sobetirome is one of the most studied thyroid hormone receptor β (TRβ)‐selective thyromimetics in the field due to its excellent selectivity and potency. A small structural change—replacing the 3,5‐dimethyl groups of sobetirome with either chlorine or bromine—produces significantly more potent compounds, both in vitro and in vivo. These halogenated compounds induce transactivation of a TRβ‐mediated cell‐based reporter with an EC50 value comparable to that of T3, access the central nervous system (CNS) at levels similar to their parent, and activate an endogenous TR‐regulated gene in the brain with an EC50 value roughly five‐fold lower than that of sobetirome. Previous studies suggest that this apparent increase in affinity can be explained by halogen bonding between the ligand and a backbone carbonyl group in the receptor. This makes the new analogues potential candidates for treating CNS disorders that may respond favorably to thyroid‐hormone‐stimulated pathways.
Organofluorine Isoselenocyanate Analogues of Sulforaphane: Synthesis and Anticancer Activity
Authors: Cierpiał Tomasz , Łuczak Jerzy , Kwiatkowska Małgorzata , Kiełbasiński Piotr , Mielczarek Lidia , Wiktorska Katarzyna , Chilmonczyk Zdzisław , Milczarek Małgorzata , Karwowska Katarzyna
Published: October 2016

A series of previously unknown sulforaphane analogues with organofluorine substituents bonded to the sulfinyl sulfur atom, an isoselenocyanate moiety in place of the isothiocyanate group, the central sulfur atom in various oxidation states, and different numbers of methylene groups in the central alkyl chain were synthesized and fully characterized. All new compounds were tested for their biological properties in vitro and demonstrated much higher anticancer activity against two breast cancer cell lines than that shown by native sulforaphane; at the same time, the compounds were less toxic for normal cells. The influence of the particular structural changes in the molecules on the cytotoxicity is discussed.
Effects of age and ambient illuminance on visual comfort for reading on a mobile device
Authors: Huang Hsin‐Pou , Ou Li‐Chen , Yuan Yinqiu
Published: October 2016

A psychophysical experiment was carried out to investigate visual comfort for reading on an iPad under various illuminance levels, ranging from 50 lx to 1200 lx, in order to see whether and how the following variables can influence the visual comfort: observer's age, gender, the illuminance of ambient lighting, and the background colour in a document layout. A panel of 21 young and 22 older Taiwanese observers participated in the study. The paired comparison method was used for data collection and analysis. The experimental results show that for all lighting conditions, young observers tended to prefer reading documents that had a moderate CIELAB lightness difference between text and background, while older observers tended to prefer reading those with an extremely large lightness difference. The results also show that female observers tended to feel less comfortable than male observers when reading documents with an extremely large lightness difference. These findings were found not to be affected by the ambient illuminance. Regarding the influence of document background colour on visual comfort, the observers tended to feel more comfortable reading documents that had a gray background than reading those with a background colour of either white or black. It was also found that the visual comfort was slightly higher for positive polarity than for negative polarity, but the difference between the two settings was insignificant. © 2016 Wiley Periodicals, Inc. Col Res Appl, 42, 352–361, 2017
Variable message encryption through blockcipher compression function
Authors: Chen Jiageng , Mazumder Rashed , Miyaji Atsuko , Su Chunhua
Published: October 2016

A constrained device is an emerging technology that has enormous applications in our daily life such as access control, inventory control, luggage tracking, bar‐code reader, and IoT. However, it has certain drawbacks of low memory and less computing power. Thus, one of the cracking challenges is to provide efficient and secure cryptographic solution for the constrained device in the aspect of security issue. An (n,n) blockcipher‐based cryptographic compression function is applicable to provide provable security to the constrained device. Though, there are many constructions of (n,n) blockcipher such as MDC‐2, MDC‐4, MJH, Bart‐12, and SKS‐15. However, most of the familiar schemes are not suitable for short and variable message encryption without padding because of their internal structures. Furthermore, the security margin is provided based on blocklength rather than the flexible size of message. In this paper, we present two different (n,n) blockcipher compression function schemes. The first scheme (FS) satisfies better efficiency such as less call of blockcipher, less key scheduling, and higher efficiency rate. On the contrary, the second scheme (SS) has upper security bound. Moreover, both of the schemes are suitable for small and variable message encryption (message size =   tn|t < 1,n:blocklength), which is handy for the constrained device. The collision and preimage security bound of the FS are O(2tn/2) and O(2tn). In addition, the SS's collision resistance and preimage resistance are bounded by O(2tn) and O(22tn). Moreover, the efficiency rate of the proposed two schemes are respectively t and t/3. The numbers of key scheduling are 2 for the constructions of FS and SS. We use two calls of blockcipher in the FS. On the contrary, three calls of blockcipher are used in the SS. Copyright © 2016 John Wiley & Sons, Ltd.
Synthesis and Thermophysical Properties of Ether‐Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications
Authors: Coadou Erwan , Goodrich Peter , Neale Alex R. , Timperman Laure , Hardacre Christopher , Jacquemin Johan , Anouti Mérièm
Published: October 2016

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis{(trifluoromethyl)sulfonyl}imide, [NTf2]− anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window, along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity, and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.
SERS Enhancement on the Basis of Temperature‐Dependent Chemisorption: Microcalorimetric Evidence
Authors: Roy Chandra Nath , Ghosh Debasmita , Mondal Somrita , Kundu Somashree , Maiti Susmita , Saha Abhijit
Published: October 2016

The mechanism of surface‐enhanced Raman spectroscopy (SERS) is not very clear in view of the magnitude of the contribution of electromagnetic factor as well as the chemical mechanism. This report presents the extent of adsorption at different temperatures in terms of signal enhancements in SERS employing silver nanoparticles (AgNPs) of various shapes as substrate and dye molecules, crystal violet or Rhodamine 6G, as model Raman probes. Initially, the SERS signal increases with increasing temperature until a maximum intensity is reached, before it gradually decreases with increasing temperature. This trend is independent of the shape of the Raman substrates and probes. However, the temperature at which maximum intensity is obtained may depend upon the nature of the Raman probe. The energetics involved in the chemisorption process between dye molecules and AgNPs were determined through isothermal titration calorimetry and their implications for the observed SERS signals were assessed. The maximum heat change occurred at the temperature at which the maximum signal enhancement in SERS was obtained and the enhanced interaction at optimum temperature was confirmed by absorption spectroscopy.
Theoretical Investigation and Design of Highly Efficient Blue Phosphorescent Iridium(III) Complexes Bearing Fluorinated Aromatic Sulfonyl Groups
Authors: Zhang Wenting , Luo Yafei , Xu Yanyan , Li Wenqian , Shen Wei
Published: October 2016

Aromatic sulfonyl groups have attracted increasing interest due to their unique electronic features. In this article, a series of IrIII complexes bearing fluorinated phenylsulfonyl groups were evaluated by density functional theory and time‐dependent density functional theory methods. To explore their phosphorescence efficiencies, factors that determine the radiative decay rate constant, kr, and the nonradiative decay rate constant, knr, were computed. As demonstrated by the results, complex 4, which has fluorinated phenylsulfonyl groups at the 5‐positions of the phenyl rings for all three C^N ligands, was found to have the highest phosphorescence efficiencies with the largest kr and smallest knr values among these complexes. Moreover, it was found to exhibit significantly blueshifted behavior relative to complex 1 and emits in the blue region, and thus, it can serve as a highly efficient blue emitter for application in organic light‐emitting diodes. These findings successfully illustrated the structure–properties relationship and provided valuable information for the development of future highly efficient blue‐emitting phosphors.
On the Versatility of BH2X (X=F, Cl, Br, and I) Compounds as Halogen‐, Hydrogen‐, and Triel‐Bond Donors: An Ab Initio Study
Authors: Bauzá Antonio , Frontera Antonio
Published: October 2016

The front cover artwork is provided by the group of Prof. Antonio Frontera (Universitat de les Illes Balears). The image shows the versatility of boron halides in establishing σ‐ and π‐hole interactions. Read the full text of the article at 10.1002/cphc.201600683.
Covalent and Non‐Covalent DNA–Gold‐Nanoparticle Interactions: New Avenues of Research
Authors: Carnerero Jose M. , Jimenez‐Ruiz Aila , Castillo Paula M. , Prado‐Gotor Rafael
Published: October 2016

The interactions of DNA, whether long, hundred base pair chains or short‐chained oligonucleotides, with ligands play a key role in the field of structural biology. Its biological activity not only depends on the thermodynamic properties of DNA–ligand complexes, but can and often is conditioned by the formation kinetics of those complexes. On the other hand, gold nanoparticles have long been known to present excellent biocompatibility with biomolecules and are themselves remarkable for their structural, electronic, magnetic, optical and catalytic properties, radically different from those of their counterpart bulk materials, and which make them an important asset in multiple applications. Therefore, thermodynamic and kinetic studies of the interactions of DNA with nanoparticles acting as small ligands are key for a better understanding of those interactions to allow for their control and modulation and for the opening of new venues of research in nanomedicine, analytic and biologic fields. The interactions of gold nanoparticles with both DNA polymers and their smaller subunits; special focus is placed on those interactions taking place with nonfunctionalized gold nanoparticles are reviewed in the present work.
Molecular Diagnosis of Myotonic Dystrophy
Authors: Chakraborty Sujata , Vatta Matteo , Bachinski Linda L. , Krahe Ralf , Dlouhy Stephen , Bai Shaochun
Published: October 2016

Myotonic dystrophy types 1 (DM1) and 2 (DM2) are autosomal dominant, microsatellite repeat expansion disorders that affect muscle function. Myotonic dystrophy type 1 is caused by CTG repeat expansion in the 3′ UTR region of the DMPK gene. Patients with DM2 have expansion of CCTG repeats in intron 1 of the CNBP gene. In this unit, we review and discuss the clinical phenotypes, genetic mutations causing the diseases, and the molecular diagnostic approaches and tools that are used to determine repeat sizes in DM1/2. In summary, the goal of this chapter is to provide the reader with a basic understanding of the clinical, genetic and diagnostic aspects of these disorders. © 2016 by John Wiley & Sons, Inc.
Light‐Induced Cell‐Sheet Harvest on TiO2 Films Sensitized with Carbon Quantum Dots
Authors: Wang Xiaozhao , Cheng Kui , Weng Wenjian , Wang Huiming , Lin Jun
Published: October 2016

Invited for this month's cover is the interdisciplinary research group of Prof. Kui Cheng from Zhejiang University, China. The cover picture shows a schematic figure of carbon quantum dots incorporated as a sensitizer into TiO2 films to regulate the light‐induced cell‐detachment performance. Read the full text of the article at 10.1002/cplu.201600202.
Development of carbon transport and modeling in Czochralski silicon crystal growth
Authors: Liu Xin , Nakano Satoshi , Kakimoto Koichi
Published: October 2016

In Czochralski silicon (CZ‐Si) crystal growth, species generated from high temperature reactions and transported by Si melt and argon (Ar) gas strongly affect the purity and quality of the grown crystals. The reduction of carbon (C) contamination in crystal is required for producing Si wafers with long carrier lifetimes. Advances in the modeling of C contamination in CZ‐Si growth are reviewed on the basis of the mass transport phenomena in the Ar gas and Si domains. The generation, incorporation, and accumulation of C were investigated by the transient global simulations of heat and mass transport during the melting process of CZ‐Si growth. In addition to graphite etching, two additional sources of carbon monoxide (CO) were analyzed according to their contributions to the accumulation of C in the Si melt. The effect of gas flow control on the back diffusion of the generated CO was examined via a parametric study of the furnace pressure and the Ar gas flow rate. Strategies for C content reduction are discussed on the basis of the mechanisms of C accumulation, which indicate that the final C content depends on both the growth duration as well as the flux of contaminants at the gas/melt interface.
Synthesis of Terephthalic Acid by p‐Cymene Oxidation using Oxygen: Toward a More Sustainable Production of Bio‐Polyethylene Terephthalate
Authors: Neaţu Florentina , Culică Geanina , Florea Mihaela , Parvulescu Vasile I. , Cavani Fabrizio
Published: October 2016

The synthesis of terephthalic acid from biomass remains an unsolved challenge. In this study, we conducted the selective oxidation of p‐cymene (synthesized from biodegradable terpenes, limonene, or eucalyptol) into terephthalic acid over a Mn–Fe mixed‐oxide heterogeneous catalyst. The impact of various process parameters (oxidant, temperature, reaction time, catalyst amount, oxygen pressure) on the selectivity to terephthalic acid was evaluated, and some mechanistic aspects were elucidated. An unprecedented synthesis of biobased terephthalic acid (51 % yield) in the presence of O2 is reported.
Management of atypical squamous cells of undetermined significance or low‐grade squamous intraepithelial lesions of the uterine cervix with human papilloma virus infection among young women aged less than 25 years
Authors: Ryu Ki‐Jin , Lee Sanghoon , Min Kyung‐Jin , Hong Jin Hwa , Song Jae Yun , Lee Jae Kwan , Lee Nak Woo
Published: October 2016

Current ASCCP guidelines recommend repeat cytology 12 months after HPV‐positive results in women aged 21–24 years with either atypical squamous cells of undetermined significance (ASCUS) or a low‐grade squamous intraepithelial lesion (LSIL). The purpose of this study was to validate an algorithm in such women with ASCUS or LSIL.

A multicenter cross‐sectional study was carried out at three academic hospitals involving 40,847 Korean women who underwent cervical cancer screening with cytology and HPV testing with or without subsequent colposcopic biopsies between January 2007 and December 2013.

Among a total of 3,193 women with available histopathology data, 762 women with ASCUS and 758 with LSIL were HPV‐positive. Among HPV‐positive women with ASCUS, 38.5% of women aged 21–24 years had ≥CIN2, compared to 20.8% of women aged 30–65 years and 21.1% of the total women. Among HPV‐positive women with LSIL, 25.8% aged 21–24 years had ≥CIN2, compared to 21.2% of women aged 30–65 years and 21.9% of the total women. In HPV‐positive women with ASCUS/LSIL aged less than 25 years, the prevalence of ≥CIN2 lesions was 34.5%, which was significantly higher than that (21.0%) in women aged ≥25 years.

The risk of ≥CIN2 lesions in HPV‐positive Korean women aged 21–24 years with ASCUS or LSIL was not lower than that in older women. Colposcopic examination should be considered for management of HPV‐positive young women with ASCUS or LSIL. Diagn. Cytopathol. 2016;44:959–963. © 2016 Wiley Periodicals, Inc.
Behavioral development in embryonic and early juvenile cuttlefish (Sepia officinalis)
Authors: O'Brien Caitlin E. , Mezrai Nawel , Darmaillacq Anne‐Sophie , Dickel Ludovic
Published: October 2016

Though a mollusc, the cuttlefishSepia officinalispossesses a sophisticated brain, advanced sensory systems, and a large behavioral repertoire. Cuttlefish provide a unique perspective on animal behavior due to their phylogenic distance from more traditional (vertebrate) models.S. officinalisis well‐suited to addressing questions of behavioral ontogeny. As embryos, they can perceive and learn from their environment and experience no direct parental care. A marked progression in learning and behavior is observed during late embryonic and early juvenile development. This improvement is concomitant with expansion and maturation of the vertical lobe, the cephalopod analog of the mammalian hippocampus. This review synthesizes existing knowledge regarding embryonic and juvenile development in this species in an effort to better understand cuttlefish behavior and animal behavior in general. It will serve as a guide to future researchers and encourage greater awareness of the utility of this species to behavioral science.
Intranasal delivery of Natesto® testosterone gel and its effects on doping markers
Authors: Miller Geoffrey D. , Nair Vinod , Morrison M. Scott , Summers Maggie , Willick Stuart E. , Eichner Daniel
Published: October 2016

The laboratory profile of intranasal testosterone gel has not been previously reported from an anti‐doping perspective. Because intranasal testosterone gel is newly available as a commercial product, we sought to examine the laboratory parameters following administration of this formulation, with particular attention to anti‐doping guidelines. Five healthy and active male subjects were administered testosterone intranasal gel three times daily for four weeks, using a pattern of five consecutive days on, two days off. Urine was collected after each five‐day round of drug administration and analyzed using a full steroid screen and isotope ratio mass spectrometry (IRMS). Windows of detection for elevated testosterone/epitestosterone (T/E) and other steroid ratios, World Anti‐Doping Agency (WADA) athlete biological passport (ABP) findings, and IRMS results were analyzed in this study. In the 0–24 h window post‐administration, 70% of samples were flagged with a suspicious steroid profile and 85% were flagged as atypical passport findings according to the WADA ABP steroid module. In the 24–48 h window, 0% of samples displayed suspicious steroid profiles while 40% resulted in atypical passport findings. IRMS testing confirmed the presence of exogenous testosterone in 90% and 40% of samples in the 0–24 h and 24–48 h windows post‐administration, respectively. Additionally, IRMS data were analyzed to determine commonalities in the population changes in δ13C values of testosterone, androsterone, etiocholanolone, 5αAdiol, and 5βAdiol. Though no discernible metabolic trend of the route of administration was identified, we discovered that intranasal gel testosterone is detectable using conventional anti‐doping tests. Copyright © 2016 John Wiley & Sons, Ltd.
Potential detection of low‐dose transdermal testosterone administration in blood, urine, and saliva
Authors: Schönfelder M. , Hofmann H. , Schulz T. , Engl T. , Kemper D. , Mayr B. , Rautenberg C. , Oberhoffer R. , Thieme D.
Published: October 2016

Administration of low amounts of endogenous hormones – so‐called micro‐dosages – are supposed to represent a major challenge in doping analysis. To model such a situation, we have studied transdermal administrations of 2.4 mg/24 h testosterone patches and examined various steroid concentrations in blood, urine, and saliva of 11 volunteers. Multiple samples were collected at t = 0, 3, 6, 9, 24, 48, and 72 h in four different phases, i.e., all combinations with/without physical exercise and with/without testosterone. Testosterone was analyzed by enzyme‐linked‐immuno‐assay as well as by mass spectrometry and validated in an accredited anti‐doping laboratory. Circadian controls with and without exercise did not provoke prominent alterations of whole, free, and salivary testosterone. Testosterone application for 24 h led to a significant (all p < 0.001) mean increase above controls: total testosterone (median: 5.2 vs. 8.0 ng/mL), free testosterone (median: 11.3 vs. 15.6 pg/mL), and salivary testosterone (median: 62.4 vs. 99.9 pg/mL). Additionally, all three testosterone measurements indicated significant correlations to each other (all r > 0.538, all p < .001). Circadian‐matching showed peaking testosterone values after 6 h and 9 h, reaching highest augmentation up to 252.6 ± 123.5% in saliva after 9 h. After removal of the testosterone patch, all testosterone levels in blood, saliva, and urine returned to baseline within 24 h. Different techniques of hormone detection (enzyme‐linked immunosorbent assay (ELISA), gas chromatography‐tandem mass spectrometry (GC‐MS/MS), liquid chromatography‐tandem mass spectrometry (LC‐MS/MS)) indicated significant correlations. Results indicate that saliva, blood, and urine exhibit comparable hormone augmentation during micro‐dose testosterone application, indicating a possible consideration in future doping analysis. The inter‐individual variability was high in all biofluids, requiring the use of an individual biological passport rather than statistical values. Copyright © 2016 John Wiley & Sons, Ltd.
A review of designer anabolic steroids in equine sports
Authors: Waller Christopher C. , McLeod Malcolm D.
Published: October 2016

In recent years, the potential for anabolic steroid abuse in equine sports has increased due to the growing availability of designer steroids. These compounds are readily accessible online in ‘dietary’ or ‘nutritional’ supplements and contain steroidal compounds which have never been tested or approved as veterinary agents. They typically have unusual structures or substitution and as a result may pass undetected through current anti‐doping screening protocols, making them a significant concern for the integrity of the industry. Despite considerable focus in human sports, until recently there has been limited investigation into these compounds in equine systems. To effectively respond to the threat of designer steroids, a detailed understanding of their metabolism is needed to identify markers and metabolites arising from their misuse. A summary of the literature detailing the metabolism of these compounds in equine systems is presented with an aim to identify metabolites suitable for incorporation into screening protocols by anti‐doping laboratories. The future of equine anti‐doping research is likely to be guided by the incorporation of alternate testing matrices into routine screening, the improvement ofin vitrotechnologies that can mimicin vivoequine metabolism, and the improvement of instrumentation or analytical methods that allow for the development of untargeted screening, and metabolomics approaches for use in anti‐doping screening protocols. Copyright © 2016 John Wiley & Sons, Ltd.
A hyperspectral image can predict tropical tree growth rates in single‐species stands
Authors: Caughlin T. Trevor , Graves Sarah J. , Asner Gregory P. , van Breugel Michiel , Hall Jefferson S. , Martin Roberta E. , Ashton Mark S. , Bohlman Stephanie A.
Published: October 2016

Remote sensing is increasingly needed to meet the critical demand for estimates of forest structure and composition at landscape to continental scales. Hyperspectral images can detect tree canopy properties, including species identity, leaf chemistry and disease. Tree growth rates are related to these measurable canopy properties but whether growth can be directly predicted from hyperspectral data remains unknown. We used a single hyperspectral image and light detection and ranging‐derived elevation to predict growth rates for 20 tropical tree species planted in experimental plots. We asked whether a consistent relationship between spectral data and growth rates exists across all species and which spectral regions, associated with different canopy chemical and structural properties, are important for predicting growth rates. We found that a linear combination of narrowband indices and elevation is correlated with standardized growth rates across all 20 tree species (R2 = 53.70%). Although wavelengths from the entire visible‐to‐shortwave infrared spectrum were involved in our analysis, results point to relatively greater importance of visible and near‐infrared regions for relating canopy reflectance to tree growth data. Overall, we demonstrate the potential for hyperspectral data to quantify tree demography over a much larger area than possible with field‐based methods in forest inventory plots.
Cryptic diversity and multiple origins of the widespread mayfly species groupBaetis rhodani(Ephemeroptera: Baetidae) on northwestern Mediterranean islands
Authors: Bisconti Roberta , Canestrelli Daniele , Tenchini Roberta , Belfiore Carlo , Buffagni Andrea , Nascetti Giuseppe
Published: October 2016

How the often highly endemic biodiversity of islands originated has been debated for decades, and it remains a fervid research ground. Here, using mitochondrial and nuclear gene sequence analyses, we investigate the diversity, phylogenetic relationships, and evolutionary history of the mayflyBaetis gr. rhodanion the three largest northwestern Mediterranean islands (Sardinia, Corsica, Elba). We identify three distinct, largely co‐distributed, and deeply differentiated lineages, with divergences tentatively dated back to the Eocene–Oligocene transition. Bayesian population structure analyses reveal a lack of gene exchange between them, even at sites where they are syntopic, indicating that these lineages belong to three putative species. Their phylogenetic relationships with continental relatives, together with the dating estimates, support a role for three processes contributing to this diversity: (1) vicariance, primed by microplate disjunction and oceanic transgression; (2) dispersal from the continent; and (3) speciation within the island group. Thus, our results do not point toward a prevailing role for any of the previously invoked processes. Rather, they suggest that a variety of processes equally contributed to shape the diverse and endemic biota of this group of islands.
Flies evolved small bodies and cells at high or fluctuating temperatures
Authors: Adrian Gregory J. , Czarnoleski Marcin , Angilletta Michael J.
Published: October 2016

Recent theory predicts that the sizes of cells will evolve according to fluctuations in body temperature. Smaller cells speed metabolism during periods of warming but require more energy to maintain and repair. To evaluate this theory, we studied the evolution of cell size in populations of Drosophila melanogaster held at either a constant temperature (16°C or 25°C) or fluctuating temperatures (16 and 25°C). Populations that evolved at fluctuating temperatures or a constant 25°C developed smaller thoraxes, wings, and cells than did flies exposed to a constant 16°C. The cells of flies from fluctuating environments were intermediate in size to those of flies from constant environments. Most genetic variation in cell size was independent of variation in wing size, suggesting that cell size was a target of selection. These evolutionary patterns accord with patterns of developmental plasticity documented previously. Future studies should focus on the mechanisms that underlie the selective advantage of small cells at high or fluctuating temperatures.
Critical loads and exceedances for nitrogen and sulfur atmospheric deposition in Great Smoky Mountains National Park, United States
Authors: Fakhraei Habibollah , Driscoll Charles T. , Renfro James R. , Kulp Matt A. , Blett Tamara F. , Brewer Patricia F. , Schwartz John S.
Published: October 2016

Acid deposition has impacted sensitive streams, reducing the amount of habitat available for fish survival in the Great Smoky Mountains National Park (GRSM) and portions of the surrounding Southern Appalachian Mountains by decreasing pH and acid neutralizing capacity (ANC) and mobilizing aluminum dissolved from soil. Land managers need to understand whether streams can recover from the elevated acid deposition and sustain the healthy aquatic biota, and if so, how long it would take to achieve this condition. We used a dynamic biogeochemical model, PnET‐BGC, to evaluate past, current, and potential future changes in soil and water chemistry of watersheds of the GRSM in response to the projected changes in acid deposition. The model was parameterized with soil, vegetation, and stream observations for 30 stream watersheds in the GRSM. Using model results, the level of atmospheric deposition (known as a “critical load”) above which harmful ecosystem effects (defined here as modeled stream ANC below a defined target) occur was determined for the 30 study watersheds. In spite of the recent marked decreases in atmospheric sulfur and nitrate deposition, our results suggest that stream recovery has been limited and delayed due to the high sulfate adsorption capacity of soils in the park resulting in a long lag time for recovery of soil chemistry to occur. Model simulations suggest that over the long term, increases in modeled stream ANC per unit decrease in NH4+ deposition are greater than unit decreases in SO42− or NO3− deposition, due to high SO42− adsorption capacity and the limited N retention of the watersheds. Watershed simulations were used to extrapolate the critical load results to 387 monitored stream sites throughout the park and depict the spatial pattern of atmospheric deposition exceedances. These types of model simulations inform park managers on the amount of air quality improvement needed to meet the stream restoration goals.
Can coyote predation risk induce reproduction suppression in white‐tailed deer?
Authors: Cherry Michael J. , Morgan Keri E. , Rutledge Brandon T. , Conner L. Mike , Warren Robert J.
Published: October 2016

Predators can have powerful nonconsumptive effects on their prey by inducing behavioral, physiological, and morphological responses. These nonconsumptive effects may influence prey demography if they decrease birthrates or increase susceptibility to other sources of mortality. The Reproductive Suppression Model suggests that iteroparous species may maximize their lifetime reproductive success by suppressing their reproduction until a future time, when conditions may be more favorable. Coyote (Canis latrans) range expansion in the United States has exposed white‐tailed deer (Odocoileus virginianus) populations to increased predation risk, and coyote predation can have profound effects on white‐tailed deer reproductive success. We evaluated effects of temporal variation in predation risk (i.e., coyote–deer ratios) on fecundity and reproductive success of white‐tailed deer on the Joseph W. Jones Ecological Research Center in southwestern Georgia, United States, by exploiting a rapid decline in coyote abundance to establish a natural experiment. We measured fecundity by examining ovaries for evidence of ovulation, and measured reproductive success using evidence of lactation from deer harvested before and after the decline in coyote abundance. We found that incidence of ovulation and lactation increased following the decline in predation risk. Our results suggest coyotes may be able to influence deer recruitment, independent of direct predation, through interactions that result in reduced fecundity. More broadly, our study suggests that in order to understand the totality of the effect of predators on prey population dynamics, studies should incorporate measures of direct and indirect predator effects.
S1P1 downregulation tailors CD8+ T‐cell residence time in lymph nodes to the strength of the antigenic stimulation
Authors: Breart Béatrice , Bousso Philippe
Published: October 2016

T cells are sequestered for several days in lymph nodes following antigen recognition but the precise mechanism regulating their timing of egress is not fully understood. In particular, whether interactions with antigen‐presenting cells (APCs) and/or strength of the TCR stimulation shape T‐cell residence time is unclear. We report here that the probability of T‐cell egress decreases upon stimulation with high affinity TCR ligands. In contrast, low affinity peptides favor early egress, a phenomenon that could be reversed by sustaining antigen availability. The delayed egress of high affinity T cells could not be accounted by physical sequestration by APCs. Instead, we found that the sphingosine‐1‐phosphate receptor (S1P1) downregulation mirrors the strength and persistence of the TCR stimulation, limiting egress of high affinity T cells. We propose that S1P1 acts as a rheostat to tailor T‐cell residence time in the lymph node to the local availability of antigen and to optimize the expansion of high affinity T cells.
Irreversible splenic atrophy following chronic LCMV infection is associated with compromised immunity in mice
Authors: Mbanwi Achire N. , Wang Chao , Geddes Kaoru , Philpott Dana J. , Watts Tania H.
Published: October 2016

Lymphocytic choriomeningitis virus clone 13 (LCMV13) infection of mice is a widely used model for investigating the mechanisms driving persistent viral infection in humans. LCMV13 disrupts splenic architecture early during infection, but this returns to normal within a few weeks. However, the long‐term effects of LCMV13 infection on splenic structure have not been reported. Here, we report that persistent infection with LCMV13 results in sustained splenic atrophy that persists for at least 500 days following infection, whereas infection with the acutely infecting LCMV Armstrong is associated with a return to preinfection spleen weights. Splenic atrophy is associated with loss of T, B, and non‐B non‐T cells, with B cells most significantly affected. These effects were partly ameliorated by anti‐NK1.1 or anti‐CD8 antibody treatment. Antigen presentation was detectable at the time of contraction of the spleen, but no longer detected at late time points, suggesting that continued antigen presentation is not required to maintain splenic atrophy. Immunity to Salmonella infection and influenza vaccination were decreased after the virus was no longer detected. Thus splenic atrophy following LCMV13 infection is irreversible and may contribute to impaired immunity following clearance of LCMV13.
Universal Approach to the Synthesis of Silver Sulfide in the Forms of Nanopowders, Quantum Dots, Core‐Shell Nanoparticles, and Heteronanostructures
Authors: Sadovnikov Stanislav I. , Gusev Aleksandr I.
Published: October 2016

Nanostructured silver sulfide is one of the semiconducting chalcogenides most in demand, due to its unique combination of structure, physical, and chemical properties, and its potential applications in optoelectronics, biosensing, and catalysis. Much research has been carried out in the last decade, with the goals of producing silver sulfide in the form of nanopowders, stable colloidal solutions, quantum dots with protective shells, and heteronanostructures by different chemical and physical methods. This review considers the main challenges in the synthesis of all these forms of nanostructured silver sulfide by a universal, simple, and environmentally friendly method without the use or generation of any hazardous substances. Recent experimental studies have revealed that such universal synthesis can be carried out by hydrochemical bath deposition.
Zinc(II) and Copper(II) Metal–Organic Frameworks Constructed from a Terphenyl‐4,4′′‐dicarboxylic Acid Derivative: Synthesis, Structure, and Catalytic Application in the Cyanosilylation of Aldehydes
Authors: Karmakar Anirban , Paul Anup , Rúbio Guilherme M. D. M. , Guedes da Silva M. Fátima C. , Pombeiro Armando J. L.
Published: October 2016

Solvothermal reaction of zinc(II) and copper(II) salts with 3,3′′‐dipropoxy‐[1,1′:4′,1′′‐terphenyl]‐4,4′′‐dicarboxylic acid (H2L) gave rise to the 1D and 2D metal–organic frameworks (MOFs) [Zn(L)(dmf)2]n (1), [Zn2(L)(NO3)2(4,4′‐bipyridine)2]n·n(DMF) (2), [Cu(L)(H2O)2]n·2n(H2O) (3), and [Cu3(OH)2(L)2]n·n(H2O) (4), which were characterized by elemental analysis, FTIR spectroscopy, and X‐ray single‐crystal diffraction. MOFs 1 and 3 have zigzag‐ and linear‐type 1D structures, respectively, whereas 2 and 4 possess rectangular grid‐ and layer‐type 2D structures. In 2 and in 4, a dinuclear ZnII cluster (C2O4Zn2) and a trinuclear µ3‐hydroxo‐bridged CuII cluster [Cu3(OH)2]n, respectively, act as building block units. These frameworks act as heterogeneous catalysts (the Zn‐MOFs are more active than Cu‐MOFs, and 1 is the most efficient) for the cyanosilylation of aldehydes with trimethylsilyl cyanide at room temperature. These MOF‐based heterogeneous catalysts can be easily recovered and reused, at least over a few consecutive cycles, without losing activity.
Aggregation‐Induced Orange‐to‐Red Fluorescence of 2,5‐Bis(diarylamino)terephthalic Acid Dithioesters
Authors: Shimizu Masaki , Fukui Hiroki , Natakani Masaki , Sakaguchi Hiroshi
Published: October 2016

π‐conjugated systems substituted by electron donors (D) or acceptors (A) are useful platforms for various kinds of organic optoelectronic materials. The exploration and development of new donors and acceptors can expand the possible molecular designs of D–π–A‐type electronic structures. Herein we report 2,5‐bis(diarylamino)terephthalic acid dithioesters, in which organosulfanylcarbonyl groups serve as electron acceptors, as new fluorophores exhibiting efficient solid‐state emission. The absorption spectra of the thioesters in toluene show two bands, with the smaller band located at the longer wavelength corresponding to the intramolecular charge‐transfer transition from the diarylamino to organosulfanylcarbonyl groups. The dithioesters are faintly fluorescent in toluene, but exhibit efficient orange‐to‐red emission in the powder form; therefore, aggregation‐induced emission was observed. Compared with the corresponding terephthalic acid diesters, the fluorescence spectra of the dithioesters in the powder form are significantly redshifted.
1‐Hydrosilatrane: A Locomotive for Efficient Ketone Reductions
Authors: Varjosaari Sami E. , Skrypai Vladislav , Suating Paolo , Hurley Joseph J. M. , Gilbert Thomas M. , Adler Marc J.
Published: October 2016

An efficient method for the reduction of ketones with 1‐hydrosilatrane is described. In the presence of a Lewis base activator, the resulting secondary alcohols are rapidly formed in good to excellent yields (20 examples, 71–99 % yields). The relative bulkiness of 1‐hydrosilatrane also enables the diastereoselective reduction of (–)‐menthone to (+)‐neomenthol, and the use of a chiral alkoxide activator can lead to the enantioselective reduction of prochiral ketones.
Temperature Compensation by Calibration Transfer for an AC Voltammetric Analyzer of Electroplating Baths
Authors: Jaworski Aleksander , Wikiel Hanna , Wikiel Kazimierz
Published: October 2016

The application of methods for mitigating the effects of temperature fluctuations on the analytical performance of an in‐situ DC‐ and AC‐voltammetric sensor employed for electroplating process control in semiconductor manufacturing is presented. This sensor is a part of an automated analytical system capable of predicting concentration values of deliberately‐added bath constituents based on the component‐specific multivariate voltammetric responses. However, these responses include physicochemical phenomena, some of which are strongly dependent on temperature; therefore temperature fluctuations can produce an additional source of variance in the voltammetric responses adversely affecting the accuracy of analyte concentration predictions. Several calibration‐transfer‐based techniques, both discrete and continuous, using Piecewise Direct Standardization and Direct Standardization combined with PCR and PLS analytical models are comparatively validated for temperature compensation using AC voltammetric data for the example of accelerator additive. An extension of implementation of continuous methods for Direct Standardization is proposed along with an introduction of a new hybrid method of Standardization Models.
The Osmium Tetroxide Bipyridine‐labeled DNA Probe: Hairpin Conformations and Characterization of Redox‐label Behavior
Authors: Joda Hamdi , Sedova Ada , Awan Waqas , Flechsig Gerd‐Uwe
Published: October 2016

Osmium tetroxide bipyridine ([OsO4(bpy)]) is a versatile label for DNA electrochemistry. Here we report our efforts to create an osmium tetroxide‐labeled immobilized DNA probe for use in biosensing experiments. Our label is applied in‐house, as opposed to many other covalent redox labels used with DNA. We developed an on‐electrode labeling method that was able to avoid attack of our disulfide‐based linker by the [OsO4(bpy)]. Our results include two different hairpin‐based signal‐off hybridization detection assays, each with robust, reproducible signal decrease on binding to complementary target. We also found that 6‐mercapto‐1‐hexanol was able to interact with [OsO4(bpy)] in a stable manner when assembled at the surface, but was able to remove excess [OsO4(bpy)], which was found to adsorb strongly to the gold surface, and avoid MCH transformation, when applied after the labeling process. Furthermore, we found an increased adsorption affinity of [OsO4(bpy)]‐labeled DNA onto gold, characterized the redox behavior of adsorbed [OsO4(bpy)], and determined voltammetric signals on the HMDE of our intact disulfide linker while verifying that this linker is attacked by [OsO4(bpy)] when in solution.
Global mapping of rat plasma proteins with a native proteomic approach using nondenaturing micro 2DE and quantitative LC‐MS/MS
Authors: Chen Shumin , Wen Meiling , Bu Shujie , Wang Ahui , Jin Ya , Tan Wen
Published: October 2016

Plasma samples from adult male rats were separated by nondenaturing micro 2DE and a reference gel was selected, on which 136 CBB‐stained spots were numbered and subjected to in‐gel digestion and quantitative LC‐MS/MS. The analysis provided the assignment of 1–25 (average eight) non‐redundant proteins in each spot and totally 199 proteins were assigned in the 136 spots. About 40% of the proteins were detected in more than one spot and 15% in more than ten spots. We speculate this complexity arose from multiple causes, including protein heterogeneity, overlapping of protein locations and formation of protein complexes. Consequently, such results could not be appropriately presented as a conventional 2DE map, i.e. a list or a gel pattern with one or a few proteins annotated to each spot. Therefore, the LC‐MS/MS quantity data was used to reconstruct the gel distribution of each protein and a library containing 199 native protein maps was established for rat plasma. Since proteins that formed a complex would migrate together during the nondenaturing 2DE and thus show similar gel distributions, correlation analysis was attempted for similarity comparison between the maps. The protein pairs showing high correlation coefficients included some well‐known complexes, suggesting the promising application of native protein mapping for interaction analysis. With the importance of rat as the most commonly used laboratory animal in biomedical research, we expect this work would facilitate relevant studies by providing not only a reference library of rat plasma protein maps but a means for functional and interaction analysis.
How to Control the Discharge Product in Sodium–Oxygen Batteries: Proposing New Pathways for Sodium Peroxide Formation
Authors: Schröder Daniel , Bender Conrad L. , Pinedo Ricardo , Bartuli Waldemar , Schwab Matthias G. , Tomović Željko , Janek Jürgen
Published: October 2016

It is an unsolved problem how to steer between sodium superoxide and sodium peroxide as discharge products in sodium–oxygen batteries. Sodium peroxide yields a higher theoretical energy density; thus, it is preferred in view of maximized energy density. Three novel approaches to form sodium peroxide are presented: First, cells loaded with sodium superoxide are further discharged in argon, with the aim of reducing sodium superoxide to peroxide. Second, carbon nanotube electrodes preloaded with sodium peroxide are utilized. Third, sodium peroxide is dissolved in the electrolyte to enhance precipitation of solid sodium peroxide. Interestingly, all approaches yield sodium superoxide as a discharge product. Thus, it might not be possible to have high energy density sodium–oxygen batteries with sodium peroxide as the discharge product. However, potential pathways for peroxide formation during discharge have been excluded to help to find the true factors that govern the competition between superoxide and peroxide formation.
Optimized design of a hybrid PV‐wind‐diesel energy system for sustainable development at coastal areas in Bangladesh
Authors: Rashid Sumon , Rana S. , Shezan S.K.A. , A.B. Karim Sayuti , Anower Shamim
Published: October 2016

Power generation capacity of Bangladesh needs to be enhanced to support the rising electricity demand. Bangladesh has predominantly used fossil fuel generators for the past decades. Saint Martin's Island and Kuakata are two significant areas that lie at or near the coast of Bangladesh with an average annual solar radiation of 4.81 and 4.65 kWh m−2 day−1, respectively. The monthly average wind speeds at a height of 25 meters are 4.79 and 4.54 m s−1, respectively. Considering this data and the benefits of the optimized hybrid systems, HOMER (Hybrid Optimization Model for Electric Renewable) is used to optimize a system for each of these areas. The costs of energy found from the proposed optimized PV‐wind‐diesel hybrid Energy system for Saint Martin's island and Kuakata are 0.393 and 0.392 USD kW−1 h−1, respectively, the net present cost (NPC) also has been evaluated as 168767.831 USD which are quite reasonable with respect to the present situation in Bangladesh. The major objective of this proposed optimized design is to supply the maximum load demand using renewable sources with the minimum cost of energy (COE) and reduce the burning of fuel and also reduce the emission of CO2. The proposed energy system is able to meet 67.3 and 62.3% load demand using renewable sources, which helps to reduce the GHG (Green Houses Gas) emission by 67 and 64% for Saint Martin's island and Kuakata, respectively when compared to a diesel system. Total load served throughout the year is 33,611 kWh, which is 16% higher than the previously designed system with approximately equivalent COE. © 2016 American Institute of Chemical Engineers Environ Prog, 36: 297–304, 2017