bluuebunny/crossref_metadata_2025 huggingface dataset:
Biotechnology and pharmaceutical R&D and licensing trends: You pays your money and takes your chances
Authors: Ratliff Alan
Published: January 2017

R&D costs in the biotechnology and pharmaceutical industries continue to rocket, as do royalty rates for the relatively few new drugs and technology that successfully complete clinical testing. Several of the issues that led to last year's joint Department of Justice/Federal Trade Commission (DOJ/FTC) hearings are significant within those industries, including (1) recent court decisions reaching inconsistent results or at odds with public agency positions; (2) proliferation of new patent filings; (3) efforts to expand the scope of patents; (4) mergers and acquisitions reducing competition and consumer choice; (5) more restrictive, licenser-oriented licences; (6) patent blocking; and (7) patent settlements with reverse payments. This article discusses the results of studies evaluating the rising costs and declining success rates of new biotechnology and pharmaceutical product offerings, the upward trend in royalty rates and litigation awards, and the implications of the DOJ/FTC hearings.
Patentability of inventions involving human stem cells in Europe
Authors: Bouvet Philippe
Published: January 2017

In the last two years, research into stem cells has raised extraordinary therapeutic hopes â€“ such as regenerative medicine â€“ but also strong ethical questions. These questions have been fuelled by announcements, from private companies in particular, of the possibilities for human cloning. One of these questions relates to the patentability of inventions resulting from this area of research. In Europe this question is linked to the general debate surrounding the patentability of biological materials, such as genomic sequences. Although a large number of applications have been filed these last years, a few patents have already been issued. Some of them have been opposed at the European Patent Office. At the request of the European Commission, the European Group on Ethics (EGE) has prepared an opinion on ethical aspects of patenting inventions resulting from human stem cell research.
Legal and regulatory update
Authors: Wilkinson John , Dorey Frederick J
Published: January 2017

The Competitiveness Council of Ministers met last month to discuss the outstanding issues concerning translation of patents in the proposed community patent regime. A year ago, the Council agreed in principle that reliance, in good faith, on an inaccurate translation of a patent would allow the alleged infringer to continue using the invention for up to four years. However, in the recent meeting, the Council was unable to agree on the length of time to be allowed for filing translations into the languages of the other member states.
Bismuth doping effect on crystal structure and photodegradation
activity of Bi–TiO2 nanoparticles
Authors: Wu Ming-Chung , Chang Yin-Hsuan , Lin Ting-Han
Published: January 2017

The bismuth precursor is adopted as dopant to synthesize bismuth doped titanium
dioxide nanoparticles (Bi–TiO2 NPs) with sol–gel method
following by the thermal annealing treatment. We systematically developed a
series of Bi–TiO2 NPs at several calcination temperatures and
discovered the corresponding crystal structure by varying the bismuth doping
concentration. At a certain 650 °C calcination temperature, the crystal
structure of bismuth titanate (Bi2Ti2O7) is
formed when the bismuth doping concentration is as high as 10.0 mol %. The
photocatalytic activity of Bi–TiO2 NPs is increased by varying
the doping concentration at the particular calcination temperature. By the
definition X-ray diffraction (XRD) structural identification, a phase diagram of
Bi–TiO2 NPs in doping concentration versus calcination
temperature is provided. It can be useful for further study in the crystal
structure engineering and the development of photocatalyst.
Mixed‐layer carbon cycling at the Kuroshio Extension Observatory
Authors: Fassbender Andrea J. , Sabine Christopher L. , Cronin Meghan F. , Sutton Adrienne J.
Published: January 2017

Seven years of data from the NOAA Kuroshio Extension Observatory (KEO) surface mooring, located in the North Pacific Ocean carbon sink region, were used to evaluate drivers of mixed‐layer carbon cycling. A time‐dependent mass balance approach relying on two carbon tracers was used to diagnostically evaluate how surface ocean processes influence mixed‐layer carbon concentrations over the annual cycle. Results indicate that the annual physical carbon input is predominantly balanced by biological carbon uptake during the intense spring bloom. Net annual gas exchange that adds carbon to the mixed layer and the opposing influence of net precipitation that dilutes carbon concentrations make up smaller contributions to the annual mixed‐layer carbon budget. Decomposing the biological term into annual net community production (aNCP) and calcium carbonate production (aCaCO3) yields 7 ± 3 mol C m−2 yr−1 aNCP and 0.5 ± 0.3 mol C m−2 yr−1 aCaCO3, giving an annually integrated particulate inorganic carbon to particulate organic carbon production ratio of 0.07 ± 0.05, as a lower limit. Although we find that vertical physical processes dominate carbon input to the mixed layer at KEO, it remains unclear how horizontal features, such as eddies, influence carbon production and export by altering nutrient supply as well as the depth of winter ventilation. Further research evaluating linkages between Kuroshio Extension jet instabilities, eddy activity, and nutrient supply mechanisms is needed to adequately characterize the drivers and sensitivities of carbon cycling near KEO.
Surface imprint of toroidal flow at retreating slab edges: The first geodetic evidence in the Calabrian subduction system
Authors: Palano M. , Piromallo C. , Chiarabba C.
Published: January 2017

Dense GPS observations can help Earth scientists to capture the surface imprint of mantle toroidal flow at slab edges. We document this process in the Calabrian subduction system, where the Ionian slab rollback took place during the past 30 Ma, following a stepwise process driven by migration of lithospheric tearing. We found rotation rates of ~1.29°/Ma (counterclockwise) and ~1.74°/Ma (clockwise), for poles located close to the northern and southern slab edges, respectively. These small‐scale, opposite rotations occur along complex sets of active faults representing the present‐day lithospheric expression of the tearing processes affecting the southeastward retreating Ionian slab at both edges. The observed rotations are likely still young and the process more immature at the northern tear, where it is unable to reorient mantle fabric and therefore is unseen by SKS splitting.
The history and future trends of ocean warming‐induced gas hydrate dissociation in the SW Barents Sea
Authors: Vadakkepuliyambatta Sunil , Chand Shyam , Bünz Stefan
Published: January 2017

The Barents Sea is a major part of the Arctic where the Gulf Stream mixes with the cold Arctic waters. Late Cenozoic uplift and glacial erosion have resulted in hydrocarbon leakage from reservoirs, evolution of fluid flow systems, shallow gas accumulations, and hydrate formation throughout the Barents Sea. Here we integrate seismic data observations of gas hydrate accumulations along with gas hydrate stability modeling to analyze the impact of warming ocean waters in the recent past and future (1960–2060). Seismic observations of bottom‐simulating reflectors (BSRs) indicate significant thermogenic gas input into the hydrate stability zone throughout the SW Barents Sea. The distribution of BSR is controlled primarily by fluid flow focusing features, such as gas chimneys and faults. Warming ocean bottom temperatures over the recent past and in future (1960–2060) can result in hydrate dissociation over an area covering 0.03–38% of the SW Barents Sea.
Observation of suprathermal argon in the exosphere of Mars
Authors: Bhardwaj Anil , Thampi Smitha V. , Das Tirtha Pratim , Dhanya M. B. , Naik Neha , Vajja Dinakar Prasad , Pradeepkumar P. , Sreelatha P. , K. Abhishek J. , Thampi R. Satheesh , Yadav Vipin K. , Sundar B. , Nandi Amarnath , Padmanabhan G. Padma , Aliyas A. V.
Published: January 2017

The altitude profiles of argon‐40 (Ar) in the Martian exosphere are reported using Mars Exospheric Neutral Composition Analyser aboard Indian Mars Orbiter Mission (MOM) from four orbits during December 2014 (Ls = 250°–257°), when MOM's periapsis altitude was the lowest. The upper limit of Ar number density corresponding to this period is ∼5 × 105 cm−3 (∼250 km), and the typical scale height is ∼16 km, corresponding to an exospheric temperature of ∼275 K. However, on two orbits, the scale height over this altitude region is found to increase significantly making the effective temperature >400 K. Neutral Gas and Ion Mass Spectrometer observations on the Mars Atmosphere and Volatile Evolution mission also indicate that the change in slope in Ar density occurs near the upper exosphere (around 230–260 km). These observations indicate significant suprathermal CO2 and Ar populations in the Martian exosphere. Significant wave‐like perturbations are observed but only on certain days when suprathermal population is seen. Pickup ion‐induced heating is discussed as the other viable source.
The geocoronal responses to the geomagnetic disturbances
Authors: Kuwabara M. , Yoshioka K. , Murakami G. , Tsuchiya F. , Kimura T. , Yamazaki A. , Yoshikawa I.
Published: January 2017

Atomic hydrogen atoms in the terrestrial exosphere resonantly scatter solar Lyman alpha (121.6 nm) radiation, observed as the hydrogen geocorona. Measurements of scattered solar photons allow us to probe time‐varying distributions of exospheric hydrogen atoms. The Hisaki satellite with the extreme ultraviolet spectrometer (EXtreme ultraviolet spectrosCope for ExosphEric Dynamics: EXCEED) was launched in September 2013. EXCEED acquires spectral images (52–148 nm) of the atmospheres/magnetospheres of planets from Earth orbit. Due to its low orbital altitude (~1000 km), the images taken by the instrument also contain the geocoronal emissions. In this context, EXCEED has provided quasi‐continuous remote sensing observations of the geocorona with high temporal resolution (~1 min) since 2013. These observations provide a unique database to determine the long‐term behavior of the exospheric density structure. In this paper, we report exospheric structural responses observed by EXCEED to geomagnetic disturbances. Several geomagnetic storms with decreases of Dst index occurred in February 2014 and the Lyman alpha column brightness on the night side of the Earth increased abruptly and temporarily by approximately 10%. Hisaki reveal that the time lag between the peaks of the magnetic activity and the changes in the Lyman alpha column brightness is found to be about 2 to 6 h during storms. In order to interpret the observational results, we evaluate quantitatively the factors causing the increase. On the basis of these results, a coupling effect via charge exchange between the exosphere and plasmasphere causes variations of the exospheric density structure.
Longitudinal structures in Mars' upper atmosphere as observed by MAVEN/NGIMS
Authors: Liu Guiping , England Scott , Lillis Robert J. , Mahaffy Paul R. , Elrod Meredith , Benna Mehdi , Jakosky Bruce
Published: January 2017

Here we report the first comprehensive study of longitudinal structures in Mars' neutral upper atmosphere associated with atmospheric tides in composition, density and temperature using the Mars Atmosphere and Volatile Evolution Mission/Neutral Gas Ion Mass Spectrometer observations during 2015. These are in situ measurements of number densities of atmospheric species (including CO2, Ar, N2, and CO) in the altitude range from 120 to 200 km above the areoid (corresponding to a total density range from ~108–1011 cm−3), providing a data set that is larger than all previous measurements of these waves combined. These observations span from ±70° latitude and cover a wide range of local times and solar longitudes (Ls), allowing for the study of longitudinal structures under various conditions. Furthermore, the data in May and November 2015 are at similar latitudes and local times but different Ls (~340° in May, close to northern spring equinox, and 70° in November, close to northern summer solstice and aphelion), ideal for studying the seasonal effects of tides. Our analysis shows that in each month the Ar density varies with longitude having a large wave structure. It is dominated by wave 2 and 3, accounting for 8–16% of the change of the mean density. Comparison shows that the longitudinal structures at a constant CO2 density level have different amplitudes at different seasons, although their patterns are similar. The temperature structure has a phase difference from the density variation, indicating the dissipation of tides in this altitude region. The longitudinal structure is seen in all species, including major and minor species, consistent with the tidal signatures.
GPS detection of ionospheric Rayleigh wave and its source following the 2012 Haida Gwaii earthquake
Authors: Jin Shuanggen , Jin Rui , Li D.
Published: January 2017

The processes and sources of seismo‐ionospheric disturbances are still not clear. In this paper, coseismic ionospheric disturbances (CIDs) are investigated by dual‐frequency GPS observations following the Mw = 7.8 earthquake as results of the oblique‐thrust fault in the Haida Gwaii region, Canada, on 28 October 2012. Results show that the CIDs with an amplitude of up to 0.15 total electron content units (TECU) are found with spreading out at 2.20 km/s, which agree well with the Rayleigh wave propagation speed at 2.22 km/s detected by the bottom pressure records at about 10 min after the onset. The CIDs are a result of the upward propagation acoustic waves trigged by the Rayleigh wave in sequence from near field to far field. The strong correlation is found between the CIDs and the vertical ground motion recorded by seismometers nearby the epicenter. The total electron content (TEC) series from lower‐elevation angle GPS observations have higher perturbation amplitudes. Furthermore, the simulated ionospheric disturbance following a vertical Gauss pulse on the ground based on the finite difference time domain method confirms the ionospheric Rayleigh wave signature in the near field and the vertical ground motion dependence theoretically. The vertical ground motion is the dominant source of the ionospheric Rayleigh wave and affects the CID waveform directly.
Simulating stick‐slip failure in a sheared granular layer using a physics‐based constitutive model
Authors: Lieou Charles K. C. , Daub Eric G. , Guyer Robert A. , Ecke Robert E. , Marone Chris , Johnson Paul A.
Published: January 2017

We model laboratory earthquakes in a biaxial shear apparatus using the Shear‐Transformation‐Zone (STZ) theory of dense granular flow. The theory is based on the observation that slip events in a granular layer are attributed to grain rearrangement at soft spots called STZs, which can be characterized according to principles of statistical physics. We model lab data on granular shear using STZ theory and document direct connections between the STZ approach and rate‐and‐state friction. We discuss the stability transition from stable shear to stick‐slip failure and show that stick slip is predicted by STZ when the applied shear load exceeds a threshold value that is modulated by elastic stiffness and frictional rheology. We also show that STZ theory mimics fault zone dilation during the stick phase, consistent with lab observations.
Ground validation of GPM IMERG and TRMM 3B42V7 rainfall products over southern Tibetan Plateau based on a high‐density rain gauge network
Authors: Xu Ran , Tian Fuqiang , Yang Long , Hu Hongchang , Lu Hui , Hou Aizhong
Published: January 2017

The objective of this study is to evaluate two satellite rainfall products Global Precipitation Measurement Integrated MultisatellitE Retrievals and Tropical Rainfall Measuring Mission 3B42V7 (GPM IMERG and TRMM 3B42V7) in southern Tibetan Plateau region, with special focus on the dependence of products' performance on topography and rainfall intensity. Over 500 in situ rain gauges constitute an unprecedentedly dense rain gauge network over this region and provide an exceptional resource for ground validation of satellite rainfall estimates. Our evaluation centers on the rainy season from May to October in 2014. Results indicate that (1) GPM product outperforms TRMM at all spatial scales and elevation ranges in detecting daily rainfall accumulation; (2) rainfall accumulation over the entire rainy season is negatively correlated with mean elevation for rain gauges and the two satellite rainfall products, while the performance of TRMM also significantly correlates with topographic variations; (3) in terms of the ability of rainfall detection, false alarming ratio of TRMM (21%) is larger than that of GPM (14%), while missing ratio of GPM (13%) is larger than that of TRMM (9%). GPM tends to underestimate the amount of light rain events of 0–1 mm/d, while the opposite (overestimation) is true for TRMM. GPM shows better detecting ability for light rainfall (0–5 mm/d) events but there is no detection skill for both GPM and TRMM at high‐elevation (>4500 m) regions. Our results not only highlight the superiority of GPM to TRMM in southern Tibetan Plateau region but also recommend that further improvement on the rainfall retrieval algorithm is needed by considering topographical influences for both GPM and TRMM rainfall products.
Climate reconstruction using data assimilation of water isotope ratios from ice cores
Authors: Steiger Nathan J. , Steig Eric J. , Dee Sylvia G. , Roe Gerard H. , Hakim Gregory J.
Published: January 2017

Water isotope data from ice cores, particularly δ18O, have long been used in paleoclimatology. Although δ18O has been primarily interpreted as a proxy for local air temperature, isotope‐enabled climate models have established that there are many nonlocal and nontemperature‐related climatic influences on isotopic signals at coring locations. Moreover, recent observational studies have linked ice core isotopes to nonlocal patterns of climate variability, particularly to midlatitude atmospheric circulation patterns and to variations in tropical climate. Therefore, paleoclimate reconstructions may better utilize ice core isotope proxies by combining them with isotope‐enabled climate models. Here we employ a data assimilation‐based technique that fuses isotopic proxy information with the dynamical constraints of climate models. Through several idealized and real proxy experiments we assess the spatial and temporal extent to which isotope records can reconstruct surface temperature, 500 hPa geopotential height, and precipitation. We find local reconstruction skill to be most robust across the reconstructions, particularly for temperature and geopotential height, as well as limited nonlocal skill in the tropics. These results are in agreement with long‐held views that isotopes in ice cores have clear value as local climate proxies, particularly for temperature and atmospheric circulation. These results also show that in principle nonlocal climate information may also be inferred from ice cores. However, the spatial range of this information is nonuniform and depends on skillful modeling of the proxy data within the reconstruction process.
N‐Acetylgalactosamine‐Targeted Delivery of Dendrimer‐Doxorubicin Conjugates Influences Doxorubicin Cytotoxicity and Metabolic Profile in Hepatic Cancer Cells
Authors: Kuruvilla Sibu P. , Tiruchinapally Gopinath , ElAzzouny Mahmoud , ElSayed Mohamed E. H.
Published: January 2017

This study describes the development of targeted, doxorubicin (DOX)‐loaded generation 5 (G5) polyamidoamine dendrimers able to achieve cell‐specific DOX delivery and release into the cytoplasm of hepatic cancer cells. G5 is functionalized with poly(ethylene glycol) (PEG) brushes displaying N‐acetylgalactosamine (NAcGal) ligands to target hepatic cancer cells. DOX is attached to G5 through one of two aromatic azo‐linkages, L3 or L4, achieving eitherP1((NAcGalβ‐PEGc)16.6‐G5‐(L3‐DOX)11.6) orP2((NAcGalβ‐PEGc)16.6‐G5‐(L4‐DOX)13.4) conjugates. After confirming the conjugates' biocompatibility, flow cytometry studies show P1/P2 achieve 100% uptake into hepatic cancer cells at 30–60 × 10−9mparticle concentration. This internalization correlates with cytotoxicity against HepG2 cells with 50% inhibitory concentration (IC50) values of 24.8, 1414.0, and 237.8 × 10−9mfor free DOX, P1, and P2, respectively. Differences in cytotoxicity prompted metabolomics analysis to identify the intracellular release behavior of DOX. Results show that P1/P2 release alternative DOX metabolites than free DOX. Stable isotope tracer studies show that the different metabolites induce different effects on metabolic cycles. Namely, free DOX reduces glycolysis and increases fatty acid oxidation, while P1/P2 increase glycolysis, likely as a response to high oxidative stress. Overall, P1/P2 conjugates offer a platform drug delivery technology for improving hepatic cancer therapy.
Recent Progress in Metal‐Organic Frameworks for Applications in Electrocatalytic and Photocatalytic Water Splitting
Authors: Wang Wei , Xu Xiaomin , Zhou Wei , Shao Zongping
Published: January 2017

The development of clean and renewable energy materials as alternatives to fossil fuels is foreseen as a potential solution to the crucial problems of environmental pollution and energy shortages. Hydrogen is an ideal energy material for the future, and water splitting using solar/electrical energy is one way to generate hydrogen. Metal‐organic frameworks (MOFs) are a class of porous materials with unique properties that have received rapidly growing attention in recent years for applications in water splitting due to their remarkable design flexibility, ultra‐large surface‐to‐volume ratios and tunable pore channels. This review focuses on recent progress in the application of MOFs in electrocatalytic and photocatalytic water splitting for hydrogen generation, including both oxygen and hydrogen evolution. It starts with the fundamentals of electrocatalytic and photocatalytic water splitting and the related factors to determine the catalytic activity. The recent progress in the exploitation of MOFs for water splitting is then summarized, and strategies for designing MOF‐based catalysts for electrocatalytic and photocatalytic water splitting are presented. Finally, major challenges in the field of water splitting are highlighted, and some perspectives of MOF‐based catalysts for water splitting are proposed.
Extended nonergodic states in disordered many‐body quantum systems
Authors: Torres‐Herrera E. J. , Santos Lea F.
Published: January 2017

This work supports the existence of extended nonergodic states in the intermediate region between the chaotic (thermal) and the many‐body localized phases. These states are identified through an extensive analysis of static and dynamical properties of a finite one‐dimensional system with onsite random disorder. The long‐time dynamics is particularly sensitive to changes in the spectrum and in the structures of the eigenstates. The study of the evolution of the survival probability, Shannon information entropy, and von Neumann entanglement entropy enables the distinction between the chaotic and the intermediate region.

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Biokatalyse mit nicht‐natürlichen Aminosäuren: Enzymologie trifft Xenobiologie
Authors: Agostini Federica , Völler Jan‐Stefan , Koksch Beate , Acevedo‐Rocha Carlos G. , Kubyshkin Vladimir , Budisa Nediljko
Published: January 2017

Das Ziel der Xenobiologie ist das Design von biologischen Systemen, die mit nicht‐natürlichen biochemischen Funktionen ausgestattet sind, während die Enzymologie sich mit dem Verständnis von Enzymen auseinandersetzt, den Routinewerkzeugen der Biokatalyse. In der Biokatalyse werden Enzyme und Organismen dazu verwendet, um nützliche und leistungsfähige Biotransformationen in der synthetischen Chemie und Biotechnologie durchzuführen. In den vergangenen Jahren sind die Auswirkungen des Einbaus von nicht‐kanonischen Aminosäuren (nkAAs) in Enzyme, welche potentiell interessante Anwendung für die Biokatalyse aufweisen, mit gesteigerter Aufmerksamkeit untersucht worden. Mit diesem Aufsatz wollen wir einen Überblick über die Effekte und Auswirkungen neuer chemischer Funktionalitäten geben, mit denen Proteine ausgestattet wurden, um eine Vielzahl von Aspekten der enzymatischen Biokatalyse zu verbessern. Ein weiteres Hauptaugenmerk liegt auf zukünftigen Forschungsperspektiven, welche die nicht‐natürliche Mutagenese durch die Möglichkeiten des herkömmlichen Protein‐Engineerings ergänzen werden, um neue und vielseitige Biokatalysatoren mit Anwendungen in der synthetischen organischen Chemie und Biotechnologie zu generieren.
Reproducibility of tract‐based white matter microstructural measures using the ENIGMA‐DTI protocol
Authors: Acheson Ashley , Wijtenburg S. Andrea , Rowland Laura M. , Winkler Anderson , Mathias Charles W. , Hong L. Elliot , Jahanshad Neda , Patel Binish , Thompson Paul M. , McGuire Stephen A. , Sherman Paul M. , Kochunov Peter , Dougherty Donald M.
Published: January 2017

Background

In preparation for longitudinal analyses of white matter development in youths with family histories of substance use disorders (FH+) or without such histories (FH−), we examined the reproducibility and reliability of global and regional measures of fractional anisotropy (FA) values, measured using the Enhancing Neuro Imaging Genetics Through Meta Analysis (ENIGMA)‐diffusion tensor imaging (DTI) protocol. Highly reliable measures are necessary to detect any subtle differences in brain development.

Methods

First, we analyzed reproducibility data in a sample of 12 healthy young adults (ages 20–28) imaged three times within a week. Next, we calculated the same metrics in data collected 1‐year apart in the sample of 68 FH+ and 21 FH− adolescents. This is a timeframe where within subject changes in white matter microstructure are small compared to between subject variance. Reproducibility was estimated by examining mean coefficients of variation (MCV), mean absolute differences (MAD), and intraclass correlations (ICC) for global and tract‐specific FA values.

Results

We found excellent reproducibility for whole‐brain DTI‐FA values and most of the white matter tracts, except for the corticospinal tract and the fornix in both adults and youths. There was no significant effect of FH‐group on reproducibility (p = .4). Reproducibility metrics were not significantly different between adolescents and adults (all p > .2). In post hoc analyses, the reproducibility metrics for regional FA values showed a strong positive correlation (r = .6) with the regional FA heritability measures previously reported by ENIGMA‐DTI.

Conclusion

Overall, this study demonstrated an excellent reproducibility of ENIGMA‐DTI FA, positing it as viable analysis tools for longitudinal studies and other protocols that repeatedly assess white matter microstructure.
Flexible Graphene Stacks for Sodium‐Ion Storage
Authors: Choe Jun Ho , Kim Na Rae , Lee Min Eui , Yoon Hyeon Ji , Song Min Yeong , Jin Hyoung‐Joon , Yun Young Soo
Published: January 2017

Flexible graphene stacks (FGSs) were prepared as a practically useful anode material for sodium‐ion batteries (SIBs). The FGSs not only exhibited good electrical and mechanical properties, but also showed exceptional sodium‐ion storage capability by utilizing a co‐intercalated charge carrier. In addition, SIBs based on FGSs and a previously reported cathode pair exhibited high specific energy and power of approximately 107.7 Wh kg−1 and 2050 W kg−1, respectively, with stable cycling behavior.
Direct Synthesis of Highly Designable Hybrid Metal Hydroxide Nanosheets by Using Tripodal Ligands as One‐Size‐Fits‐All Modifiers
Authors: Kuroda Yoshiyuki , Koichi Tatsuyuki , Muramatsu Keisuke , Yamaguchi Kazuya , Mizuno Noritaka , Shimojima Atsushi , Wada Hiroaki , Kuroda Kazuyuki
Published: January 2017

Brucite‐type layered metal hydroxides are prepared from diverse metallic elements and have outstanding functions; however, their poor intercalation ability significantly limits their chemical designability and the use of their potentially ultrahigh surface areas and unique properties as two‐dimensional nanosheets. Here, we demonstrate that tripodal ligands (RC(CH2OH)3, R=NH2, CH2OH, or NHC2H4SO3H) are useful as “one‐size‐fits‐all” modifiers for the direct synthesis of hybrid metal hydroxide nanosheets with various constituent metallic elements (M=Mg, Mn, Fe, Co, Ni, or Cu) and surface functional groups. The hybrid nanosheets are formed directly from solution phases, and they are stacked into a turbostratic layered structure. The ligands form tridentate Mg‐O‐C bonds with brucite layers. The hybrid brucite intercalates various molecules and is exfoliated into nanosheets at room temperature, although the non‐modified material does not intercalate any molecules. Consequently, both the constituent metallic elements and surface functional groups are freely designed by the direct synthesis.
Cooperatively Interlocked [2+1]‐Type π‐System–Anion Complexes
Authors: Yamakado Ryohei , Ashida Yukina , Sato Ryuma , Shigeta Yasuteru , Yasuda Nobuhiro , Maeda Hiromitsu
Published: January 2017

As fascinating examples of closely connected multiple π‐electronic systems involving noncovalent interactions, the cooperatively interlocked [2+1]‐type anion complexes of well‐designed π‐electronic molecules are reported. The anion‐responsive π‐electronic molecules investigated in this study are the boron complexes of dipyrrolyldiketones bearing arylethynyl moieties at the pyrrole α‐positions. Diverse substituents were introduced at the terminal aryl moieties, thus controlling the cooperativity to form [2+1]‐type complexes. Theoretical studies showed that this cooperativity was induced by effective interactions between the introduced arylethynyl moieties. The investigations of the anion‐binding processes showed that the first and second bindings to the guest anion were energetically almost equivalent, indicating the fundamental and important features of the electronic states of the halide anions. Furthermore, the interlocked anion complexes, whose geometries were distorted from the orthogonal arrangements, had the racemic states of the chiral conformations, either of which was induced by ion pairing with an appropriate chiral π‐electronic cation, resulting in the chiroptical property as shown by circular dichroism.
Modification of the Onsager Reaction Field and Its Application on Spectral Parameters
Authors: Wang Xinyu , Dao Rina , Yao Jia , Peng De , Li Haoran
Published: January 2017

Solvent polarity is an important solvent property. The Onsager's theory of reaction field was the most classic model to describe solvent effects and was widely used in relating dielectric constant and other solvent polarity parameters. In this study, a modified semi‐empirical reaction field was presented to relate electron transition energies or hyperfine coupling constants with the dielectric constants of solvents. In previous work, this relationship was well established by traditional Onsager reaction field for nonhydrogen‐bonding systems but failed for hydrogen‐bonding systems. In this modified reaction field model, the radius of the field was replaced by that of the primary solvation shell or the molecular fragment rather than that of the probe. In this way, the molecular volume of the solvent which contains information of the molecular size and overall interactions is involved in the reaction field. The 154 sets of electron transition energies and 44 sets of nitrogen isotropic hyperfine coupling constants were used to verify the modified model, indicating it works far better than the traditional model for hydrogen‐bonding systems.
Challenges in detecting substances for equine anti‐doping
Authors: Fragkaki A. G. , Kioukia‐Fougia N. , Kiousi P. , Kioussi M. , Tsivou M.
Published: January 2017

The artificial increase of the physical capability of horses using drugs is well known in racing and other equine sports. Both illicit and therapeutic substances are regarded as prohibited substances in competition in most countries. Some countries make distinctions for a few, specific drugs which are, however, allowed for use in other countries. The primary objective in the case of doping control is the detection of any trace of drug exposure, either parent drug or any of its metabolites, using the most powerful analytical methods which are generally based on chromatographic/mass spectrometric techniques. Of major concern in horseracing is the absence of a single organization regulating the anti‐doping framework; instead of this, individual racing authorities provide rules and regulations often resulting in variations in the applied doping control programmes of different countries. The aim of this paper is to review the recent literature (approximately from 2012 to mid‐2016) to highlight the numerous and diverse challenges faced in doping control of racing and equestrian sports, including the detection of designer drugs (anabolic steroids or stimulants) and of other emerging prohibited substances, such as peptides and noble gases in horse urine and plasma. Moreover, the application of ‘omics’ techniques (especially of metabolomics) deserves attention for establishing possible fingerprints of drug abuse as well as the evolution of instrumental analysis resulting a powerful ally in the fight against doping in equine sports. Copyright © 2017 John Wiley & Sons, Ltd.
Identification of gonadotropin‐releasing hormone metabolites in greyhound urine
Authors: Palmer David , Rademaker Katie , Martin Ingrid , Hessell Joan , Howitt Rob
Published: January 2017

Gonadotropin‐releasing hormone (GnRH) is a 10‐residue peptide hormone that induces secretion of luteinizing hormone (LH) and follicle‐stimulating hormone into the blood from the pituitary gland. In males, LH acts on the testes to produce testosterone. The performance‐enhancing potential of testosterone makes administration of exogenous GnRH a concern in sports doping control. Detection of GnRH abuse is challenging owing to its rapid clearance from the body and its degradation in urine. Following recent investigations of GnRH abuse in racing greyhounds in New Zealand, we carried out a GnRH administration study in greyhounds in an attempt to identify GnRH metabolites that might provide more facile detection of GnRH abuse; little information is available on in vivo metabolites of exogenous GnRH in any species and none in dogs. We identified three C‐terminal GnRH metabolites in urine: GnRH 5–10, GnRH 6–10, and GnRH 7–10. These metabolites and intact GnRH, which was also detected in urine, were all excreted over a 1–3 h period after GnRH administration. Two of the GnRH metabolites – GnRH 5–10 and GnRH 6–10 – were more stable in urine than intact GnRH offering improved potential to detect GnRH administration. Copyright © 2017 John Wiley & Sons, Ltd.
Eggshell coloration and its importance in postmating sexual selection
Authors: Poláček Miroslav , Griggio Matteo , Mikšík Ivan , Bartíková Michaela , Eckenfellner Manfred , Hoi Herbert
Published: January 2017

Avian eggshell color seems to fulfill multiple functions, some of them being structural and others signaling. In this study, we tested whether or not eggshell coloration may play a role in sexual selection of Tree Sparrows (Passer montanus). According to the “Sexually selected eggshell coloration” hypothesis, eggshell coloration signals female, egg or chick quality and males adjust parental investment according to this signal. Eggs of this species are covered with brown spots and patches, and variation between clutches is high. We found that eggshell coloration correlates with both protoporphyrin and biliverdin, but protoporphyrin concentrations are ten times higher. Eggshell coloration reflects egg and offspring quality, but not female quality. Thus, eggshell coloration may signal female postmating investment in offspring rather than female quality. Furthermore, differential allocation in terms of maternal investment is supported by the fact that females lay more pigmented clutches when mated to males with bigger melanin‐based ornaments relative to their own. Moreover, males invested proportionally more to chicks that hatched from more pigmented clutches. Our correlative results thus seem to support a role of sexual selection in the evolution of eggshell coloration in birds laying brown eggs, pigmented mainly by protoporphyrin.
The effect of hydrological and hydrochemical parameters on the microdistribution of aquatic fauna in drip water in the Velika Pasica Cave, Central Slovenia
Authors: Liu Wei , Zhou Cuiying , Ellis Burnet Julia , Brancelj Anton
Published: January 2017

Water quality and quantity significantly affects the aquatic fauna in the epikarst and conversely can also reflect the hydrological environment. Intensive, long‐term studies on hydrological and hydrochemical parameters were monitored at 4 permanent dripping sites (VP1–VP4) in the Velika Pasica Cave (Slovenian) over a period from 2006 to 2013 concurrently with aquatic fauna sampling. Multivariate methods were applied to elucidate the relationship between the environmental conditions and the resident aquatic ecosystem. Seven major aquatic taxa were collected from the drips, with Copepoda being the dominant taxa; however, the spatial distribution and composition of these species varied distinctively at the 4 study sites; the drip water from different sites had distinct hydrological and hydrochemical characteristics. The most significant parameters influencing community composition were drip water discharge volume and NO3− ion content. The results indicate that hydrology and hydrochemistry significantly influence the microdistribution of aquatic fauna within the epikarstic aquifer.
Anionic Bismuth Oxido Clusters with Pendant Silver Cations: Synthesis and Structures of {[Bi4(µ3‐O)2(TFA)9Ag(tol)2]2} and {Bi4(µ3‐O)2(TFA)10(AgPPh3)2}n
Authors: Andleeb Sohaila , Donaldson Samantha L. , Schipper Desmond E. , Loera Fernandez Ismael I. , ud Din Imtiaz , Whitmire Kenton H.
Published: January 2017

BiPh3 and trifluoroacetic acid (TFAH) react in toluene in the presence of Ag2O to form {[Bi4(µ3‐O)2(TFA)9Ag(tol)2]2} (1; tol = PhMe). Similarly, BiPh3, TFAH, PPh3, and Ag2O react in hexane to form [Bi4(µ3‐O)2(TFA)10(AgPPh3)2]n (2). Both contain {Bi4(µ3‐O)2} units, which have been previously observed with a variety of carboxylate ligands in neutral compounds and anionic compounds. In contrast to other anionic [Bi4(µ3‐O)2(TFA)N](N–8)– with metal‐based countercations, the Ag+ ions in 1 and 2 are directly attached to oxygen atoms of the TFA– ligands bonded to the bismuth core. A crystallographic evolution was observed for 1. Solvent‐rich orthorhombic crystals grew initially on standing. However, by three weeks all crystals had converted to a triclinic unit cell that contained no free solvent. The molecular volume decreased from 3146.11 Å3 (orthorhombic) to 2954.06 Å3 (triclinic). The latter had an intermolecular π–π stacking system between silver‐ and bismuth‐bound toluene molecules, which explains the reorganization to a nonsolvated morphology. Compound 2 crystallizes in the triclinic space group P1 as a coordination polymer through bridging carboxylate ligands. The presence of the PPh3 ligands on Ag+ results in a higher Ag/Bi ratio than in 1. The importance of Ag2O in generating the oxido ligands was confirmed by the isolation of {[Bi2(TFA)6(TFAH)(tol)]2}n (3) from the reaction of BiPh3 with TFAH in toluene in the absence of the metal oxide.
Linear Triplatinum Tetrahydride Complex Supported by Triphosphine Ligands, [Pt3(µ‐H)2(H)2(µ‐dpmp)2](BF4)2 {dpmp = bis(diphenylphosphinomethyl)phenylphosphine}
Authors: Tanase Tomoaki , Yamamoto Kana , Hatano Rika , Nakamae Kanako , Kure Bunsho , Ura Yasuyuki , Nakajima Takayuki
Published: January 2017

By treating [Pt6(µ‐H)(H)2(µ‐dpmp)4]BH4 [4, dpmp = bis(diphenylphosphinomethyl)phenylphosphine] with an excess amount of HBF4 in N,N‐dimethylformamide (DMF), a triplatinum tetrahydride complex, [Pt3(µ‐H)2(H)2(µ‐dpmp)2](BF4)2 (5), was obtained in 51 % yield and was characterized by IR, UV/Vis, 1H NMR, and 31P{1H} NMR spectroscopy in addition to ESI mass spectrometry, X‐ray crystallography, and DFT calculations. Complex 5 is composed of linear trinuclear platinum centers supported by two dpmp ligands, {Pt3(µ‐dpmp)2}6+, which accommodate two terminal and two bridging hydrides in a HPtHPtHPtH zigzag structure. The hydride positions were determined by DFT optimization with B3LYP/GD3BJ functionals. Variable‐temperature 1H{31P} NMR spectroscopy in [D7]DMF revealed that the bridging hydrides exhibit fluxional behavior and migrate along the Pt3 chain by switching the bridging site, whereas the terminal hydrides are not exchanged with the bridging ones. The present results suggest that the divalent linear triplatinum unit of {Pt3(µ‐dpmp)2}2+ (Pt3II), which is a building block to construct [Pt6(µ‐H)(H)2(µ‐dpmp)4]+ (4, Pt3IIPt3II), formally acts as a four‐electron source to result in [Pt3(µ‐H)2(H)2(µ‐dpmp)2]2+ (5, Pt3VI) through protonation.
Vector Time Series‐Based Radial Basis Function Neural Network Modeling of Air Quality Inside a Public Transportation Bus Using Available Software
Authors: Kadiyala Akhil , Kumar Ashok
Published: January 2017

This software review article presents a step‐by‐step approach to the development of hybrid indoor air quality (IAQ) models by integrating the use of vector time series and radial basis function neural network (RBFNN) modeling approaches. The RBFNNs are fundamentally supervised machine learning algorithm‐based artificial neural networks that provide a flexible computational platform to integrate the conventional modeling approaches (e.g., time series) and develop hybrid environmental prediction (or forecasting) models. The hybrid vector time series‐based RBFNN IAQ prediction models developed and validated in this study using available software are based on the monitored in‐bus contaminants of carbon dioxide and carbon monoxide. © 2016 American Institute of Chemical Engineers Environ Prog, 36: 4–10, 2017
Theoretical studies on adsorption of Ni(II) from aqueous solution using Citrus limetta peels
Authors: Singh Saurabhkumar , Shukla Sanjeev R.
Published: January 2017

The potential of an agro industrial waste Citrus limetta peels (CLP) for biosorption of Ni(II) ions from aqueous solution was explored in batch system in terms of equilibrium, kinetics and thermodynamics. The peels were characterized by FTIR spectroscopy, TGA analysis, and SEM. The effect of process parameters such as initial pH, metal ion concentration, biosorbent dosage and contact time on metal ion sorption was examined. The optimum values for pH and biosorbent dose for Ni(II) sorption were 6 and 2 g/L, with time for equilibrium adsorption 45 min. Application of the experimental data to several kinetic models and adsorption isotherms showed that the adsorption process follows a pseudo second order and Langmuir isotherm. The maximum adsorption capacity was found to be 27.78 mg/g. Elution efficiency was determined with different concentrations of HCl. Effect of various competing ions on sorption was also evaluated. The study was extended to metal sorption from synthetic wastewater. Results indicate that the CLP can be an effective and environmentally friendly adsorbent to detoxify Ni(II)‐polluted wastewater. The high nickel adsorption capacity of CLP suggests its utility on industrial scale. © 2017 American Institute of Chemical Engineers Environ Prog, 36: 864–872, 2017
Environmental management of tea production using joint of life cycle assessment and data envelopment analysis approaches
Authors: Kouchaki‐Penchah Hamed , Nabavi‐Pelesaraei Ashkan , O'Dwyer Jean , Sharifi Mohammad
Published: January 2017

In this study, two methods including data envelopment analysis (DEA) and life cycle assessment (LCA) were applied in order to determine energy efficiency and aid in the reduction of environmental burdens for tea production in Guilan province, Iran. The initial data were collected from 30 tea producers using a face‐to‐face questionnaire. Two models including constant return to scale (CCR) and variable return to scale (BCC) were used for calculating efficiency scores. Simultaneously, ten impact categories (AD, AC, EP, GW, OLD, FE, ME, HT, TE, and PO) were assessed to identify the main problem areas in the tea farms. The results indicated that the average technical efficiency, pure technical efficiency and scale efficiency were 0.881, 0.979, and 0.897, respectively. Moreover, the total energy saving was computed to be in the range of 7193 MJ ha−1. The highest share of total energy saving potential belonged to nitrogen with 65.93% observed. Based on the results, nitrogen, diesel fuel and machinery were the main hotspots in the majority of impact categories in both of present and DEA farms. Furthermore, in this study, the potential for impact category reduction was investigated and the results illustrated that between 17 and 20% of emissions can be reduced by converting present to DEA farms. In conclusion, the joint DEA + LCA method can improve the energy efficiency and environmental impacts in tea production, significantly. © 2017 American Institute of Chemical Engineers Environ Prog, 36: 1116–1122, 2017
Absence of intestinal microbiota increases ß‐cyclodextrin stimulated reverse cholesterol transport
Authors: Mistry Rima H. , Verkade Henkjan J. , Tietge Uwe J.F.
Published: January 2017

Scope

Non‐digestible oligosaccharides are used as prebiotics for perceived health benefits, among these modulating lipid metabolism. However, the mechanisms of action are incompletely understood. The present study characterized the impact of dietary ß‐cyclodextrin (ßCD, 10%, w/w), a cyclic oligosaccharide, on sterol metabolism and reverse cholesterol transport (RCT) in conventional and also germ‐free mice to establish dependency on metabolism by intestinal bacteria.

Methods and Results

In conventional ßCD‐fed C57BL/6J wild‐type mice plasma cholesterol decreased significantly (−40%, p < 0.05), largely within HDL, while fecal neutral sterol excretion increased (3‐fold, p < 0.01) and fecal bile acid excretion was unchanged. Hepatic cholesterol levels and biliary cholesterol secretion were unaltered. Changes in cholesterol metabolism translated into increased macrophage‐to‐feces RCT in ßCD‐administered mice (1.5‐fold, p < 0.05). In germ‐free C57BL/6J mice ßCD similarly lowered plasma cholesterol (−40%, p < 0.05). However, ßCD increased fecal neutral sterol excretion (7.5‐fold, p < 0.01), bile acid excretion (2‐fold, p < 0.05) and RCT (2.5‐fold, p < 0.01) even more substantially in germ‐free mice compared with the effect in conventional mice.

Conclusion

In summary, this study demonstrates that ßCD lowers plasma cholesterol levels and increases fecal cholesterol excretion from a RCT‐relevant pool. Intestinal bacteria decrease the impact of ßCD on RCT. These data suggest that dietary ßCD might have cardiovascular health benefits.
Bismuth Oxyhalide Induced Growth of Pt Nanoparticles within Mesoporous Alumina Films and their Use as Reusable Catalyst for Chromium(VI) Reduction
Authors: Dandapat Anirban , Huang Youju , Gnayem Hani , Sasson Yoel
Published: January 2017

Green and efficient immobilization of catalytically active metal nanoparticles into porous supporting materials and their successful application in environmental remediation is of important scientific interest in practice. Herein, we established a new role of bismuth oxyhalides (BiOX) to produce Pt NPs inside mesoporous alumina to develop the nanocomposite film (Pt‐ BiOCl0.8Br0.2/Al2O3) using ethanol as reducing agent. Those films were applied as reusable catalysts for the reduction of highly toxic CrVI ions into CrIII by formic acid at room temperature. Different amounts of bismuth oxyhalides were loaded with alumina to generate Pt NPs and found 2 mol% BiOCl0.8Br0.2 loaded film showed optimum activity towards Pt generation and highest catalytic conversion of CrVI with the rate constant 0.177 min−1 which is very high considering any thin film as catalyst.