bluuebunny/crossref_metadata_2025 huggingface dataset:
Direct observation of a deoxyadenosyl radical in an active enzyme environment
Authors: Heidinger Lorenz , Kneuttinger Andrea C. , Kashiwazaki Gengo , Weber Stefan , Carell Thomas , Schleicher Erik
Published: November 2016

5′‐deoxyadenosyl radicals have been proposed as the first common intermediate in the molecular reaction mechanism of the family of radical S‐adenosyl‐l‐methionine (SAM) enzymes. However, this radical species has not yet been directly observed in a catalytically active enzyme environment. In a reduced and SAM‐containing C140A mutant of the spore photoproduct lyase from Geobacillus thermodenitrificans, a mutant with altered catalytic activity, we were able to identify an organic radical with pronounced hyperfine structure using electron paramagnetic resonance spectroscopy. Guided by quantum‐chemical computations at the density functional theory level of theory, this radical could be tentatively assigned to a deoxyadenosyl radical, which provides first experimental evidence for this intermediate in the reaction mechanism of radical SAM enzymes.
Relationships between the El Niño–Southern Oscillation, precipitation, and nitrogen wet deposition rates in the contiguous United States
Authors: Nergui Tsengel , Evans R. David , Adam Jennifer C. , Chung Serena H.
Published: November 2016

Human activities have significantly increased reactive nitrogen (N) in the environment, leading to adverse effects on various ecosystems. We used 1979–2012 seasonal inorganic N wet deposition data from the National Atmospheric Deposition Program to evaluate the relationship between the El Niño–Southern Oscillation (ENSO) and N wet deposition in the contiguous U.S. The correlations between precipitation and inorganic N wet deposition were the strongest and most spatially extensive during winter; up to 62% and 53% of the 2 to 6 year variations of precipitation and N wet deposition rates, respectively, in the Rocky Mountains, along the coast of the Gulf of Mexico and near the Great Lakes, can be explained by variation in the NINO3.4 climate index, which was used as a measure of ENSO activity. During El Niño winters, precipitation and N wet deposition rates were higher than normal in the southern U.S., while La Niña events brought higher precipitation and N wet deposition to the Rocky Mountains and Great Lakes regions. Wintertime N wet deposition correlations held through springtime in the Great Lakes and the northeast; however, correlations between NINO3.4 and precipitation were not significant at most sites, suggesting factors besides precipitation amount contributed to the 2 to 6 year variation of N wet deposition in these regions. As the frequency, strength, and types of ENSO change in the future, interannual variability of N wet deposition will be affected, indirectly affecting spatial distribution of dry N deposition and potentially changing the overall spatial patterns of N deposition.
The influence of declining sea ice on shipping activity in the Canadian Arctic
Authors: Pizzolato Larissa , Howell Stephen E. L. , Dawson Jackie , Laliberté Frédéric , Copland Luke
Published: November 2016

Significant attention has focused on the potential for increased shipping activity driven by recently observed declines in Arctic sea ice cover. In this study, we describe the first coupled spatial analysis between shipping activity and sea ice using observations in the Canadian Arctic over the 1990–2015 period. Shipping activity is measured by using known ship locations enhanced with a least cost path algorithm to generate ship tracks and quantified by computing total distance traveled in kilometers. Statistically significant increases in shipping activity are observed in the Hudson Strait (150–500 km traveled yr−1), the Beaufort Sea (40–450 km traveled yr−1), Baffin Bay (50–350 km traveled yr−1), and regions in the southern route of the Northwest Passage (50–250 km traveled yr−1). Increases in shipping activity are significantly correlated with reductions in sea ice concentration (Kendall's tau up to −0.6) in regions of the Beaufort Sea, Western Parry Channel, Western Baffin Bay, and Foxe Basin. Changes in multiyear ice‐dominant regions in the Canadian Arctic were found to be more influential on changes to shipping activity compared to seasonal sea ice regions.
Performance of a space‐based wavelet compressor for plasma count data on the MMS Fast Plasma Investigation
Authors: Barrie A. C. , Smith S. E. , Dorelli J. C. , Gershman D. J. , Yeh P. , Schiff C. , Avanov L. A.
Published: November 2016

Data compression has been a staple of imaging instruments for years. Recently, plasma measurements have utilized compression with relatively low compression ratios. The Fast Plasma Investigation (FPI) on board the Magnetospheric Multiscale (MMS) mission generates data roughly 100 times faster than previous plasma instruments, requiring a higher compression ratio to fit within the telemetry allocation. This study investigates the performance of a space‐based compression standard employing a Discrete Wavelet Transform and a Bit Plane Encoder (DWT/BPE) in compressing FPI plasma count data. Data from the first 6 months of FPI operation are analyzed to explore the error modes evident in the data and how to adapt to them. While approximately half of the Dual Electron Spectrometer (DES) maps had some level of loss, it was found that there is little effect on the plasma moments and that errors present in individual sky maps are typically minor. The majority of Dual Ion Spectrometer burst sky maps compressed in a lossless fashion, with no error introduced during compression. Because of induced compression error, the size limit for DES burst images has been increased for Phase 1B. Additionally, it was found that the floating point compression mode yielded better results when images have significant compression error, leading to floating point mode being used for the fast survey mode of operation for Phase 1B. Despite the suggested tweaks, it was found that wavelet‐based compression, and a DWT/BPE algorithm in particular, is highly suitable to data compression for plasma measurement instruments and can be recommended for future missions.
Elasticity of ferropericlase and seismic heterogeneity in the Earth's lower mantle
Authors: Yang Jing , Lin Jung‐Fu , Jacobsen Steven D. , Seymour Nikki M. , Tkachev Sergey N. , Prakapenka Vitali B.
Published: November 2016

Deciphering the origin of seismic heterogeneity has been one of the major challenges in understanding the geochemistry and geodynamics of the deep mantle. Fully anisotropic elastic properties of constituent minerals at relevant pressure‐temperature conditions of the lower mantle can be used to calculate seismic heterogeneity parameters in order to better understand chemically and thermally induced seismic heterogeneities. In this study, the single‐crystal elastic properties of ferropericlase (Mg0.94Fe0.06)O were measured using Brillouin spectroscopy and X‐ray diffraction at conditions up to 50 GPa and 900 K. The velocity‐density results were modeled using third‐order finite‐strain theory and thermoelastic equations along a representative geotherm to investigate high pressure‐temperature and compositional effects on the seismic heterogeneity parameters. Our results demonstrate that from 660 to 2000 km, compressional wave anisotropy of ferropericlase increased from 4% to 9.7%, while shear wave anisotropy increased from 9% to as high as 22.5%. The thermally induced lateral heterogeneity ratio (RS/P = ∂lnVS/∂lnVP) of ferropericlase was calculated to be 1.48 at ambient pressure but decreased to 1.43 at 40 GPa along a representative geotherm. The RS/P of a simplified pyrolite model consisting of 80% bridgmanite and 20% ferropericlase was approximately 1.5, consistent with seismic models at depths from 670 to 1500 km, but showed an increased mismatch at lower mantle depths below ~1500 km. This discrepancy below mid‐lower mantle could be due to either a contribution from chemically induced heterogeneity or the effects of the Fe spin transition in the deeper parts of the Earth's lower mantle.
Evaluation of the WRF‐lake model over a highland freshwater lake in southwest China
Authors: Xu Lujun , Liu Huizhi , Du Qun , Wang Lei
Published: November 2016

Evaluation of the Weather Research and Forecasting Model version 3.7.1 lake model performance on lake physical processes and lake‐atmosphere interaction at Erhai Lake was conducted with in situ observation data sets over the lake to verify the model results. The lake model with default parameters presented significant negative bias during the day and positive bias during the night on lake surface temperature. Calibrations of water absorption and extinction coefficients, surface roughness length, and eddy diffusion coefficient were carried out to correct this bias. The added absorption and extinction coefficients increased solar radiation in upper water layer, leading to a little higher surface temperature. Compared to constant surface roughness lengths, parameterization of roughness lengths as functions of friction velocity and fetch length significantly improved simulations of lake surface temperature and sensible heat flux. In Erhai Lake, eddy diffusion coefficient of the Henderson‐Sellers parameterization is smaller than that in deep lakes. The eddy diffusion coefficient was reduced by a factor of 0.05 in dry season and 0.02 in wet season, respectively, to restrict mixing strength, generating a reasonable diurnal range with observed surface temperature. The adjusted parameter simulations matched better with in situ observations in diurnal cycle of temperature and surface heat fluxes but still overestimated wind speed. Topographic correction is effective to correct the bias, indicating that topographic correction over complex terrain was necessary.
Statistical retrieval of thin liquid cloud microphysical properties using ground‐based infrared and microwave observations
Authors: Marke Tobias , Ebell Kerstin , Löhnert Ulrich , Turner David D.
Published: November 2016

In this article, liquid water cloud microphysical properties are retrieved by a combination of microwave and infrared ground‐based observations. Clouds containing liquid water are frequently occurring in most climate regimes and play a significant role in terms of interaction with radiation. Small perturbations in the amount of liquid water contained in the cloud can cause large variations in the radiative fluxes. This effect is enhanced for thin clouds (liquid water path, LWP <100 g/m2), which makes accurate retrieval information of the cloud properties crucial. Due to large relative errors in retrieving low LWP values from observations in the microwave domain and a high sensitivity for infrared methods when the LWP is low, a synergistic retrieval based on a neural network approach is built to estimate both LWP and cloud effective radius (reff). These statistical retrievals can be applied without high computational demand but imply constraints like prior information on cloud phase and cloud layering. The neural network retrievals are able to retrieve LWP and reff for thin clouds with a mean relative error of 9% and 17%, respectively. This is demonstrated using synthetic observations of a microwave radiometer (MWR) and a spectrally highly resolved infrared interferometer. The accuracy and robustness of the synergistic retrievals is confirmed by a low bias in a radiative closure study for the downwelling shortwave flux, even for marginally invalid scenes. Also, broadband infrared radiance observations, in combination with the MWR, have the potential to retrieve LWP with a higher accuracy than a MWR‐only retrieval.
Spatial‐temporal variation of near‐surface temperature lapse rates over the Tianshan Mountains, central Asia
Authors: Shen Yan‐Jun , Shen Yanjun , Goetz Jason , Brenning Alexander
Published: November 2016

Adequate estimates of near‐surface temperature lapse rate (γlocal) are needed to represent air temperature in remote mountain regions with sparse instrumental records such as the mountains of central Asia. To identify the spatial and temporal variations of γlocal in the Tianshan Mountains, long‐term (1961–2011) daily maximum, mean, and minimum temperature (Tmax, Tmean, and Tmin) data from 17 weather stations and 1 year of temperature logger data were analyzed considering three subregions: northern slopes, Kaidu Basin, and southern slopes. Simple linear regression was performed to identify relationships between elevation and temperature, revealing spatial and seasonal variations in γlocal. The γlocal are higher on the southern slopes than the northern slopes due to topography and regional climate conditions. Seasonally, γlocal are more pronounced higher in the summer than in the winter months. The γlocal are generally higher for Tmax than Tmean and Tmin. The Kaidu Basin shows similar seasonal variability but with the highest γlocal for Tmean and Tmin occurring in the spring. Formation of γlocal patterns is associated with the interactions of climate factors in different subregions. Overall, annual mean γlocal for Tmax, Tmean, and Tmin in the study's subregions are lower than the standard atmospheric lapse rate (6.5°C km−1), which would therefore be an inadequate choice for representing the near‐surface temperature conditions in this area. Our findings highlight the importance of spatial and temporal variations of γlocal in hydrometeorological research in the data‐sparse Tianshan Mountains.
Three‐dimensional turbulence‐resolving modeling of the Venusian cloud layer and induced gravity waves
Authors: Lefèvre Maxence , Spiga Aymeric , Lebonnois Sébastien
Published: November 2016

The impact of the cloud convective layer of the atmosphere of Venus on the global circulation remains unclear. The recent observations of gravity waves at the top of the cloud by the Venus Express mission provided some answers. These waves are not resolved at the scale of global circulation models (GCM); therefore, we developed an unprecedented 3‐D turbulence‐resolving large‐eddy simulations (LES) Venusian model using the Weather Research and Forecast terrestrial model. The forcing consists of three different heating rates: two radiative ones for solar and infrared and one associated with the adiabatic cooling/warming of the global circulation. The rates are extracted from the Laboratoire de Météorlogie Dynamique Venus GCM using two different cloud models. Thus, we are able to characterize the convection and associated gravity waves in function of latitude and local time. To assess the impact of the global circulation on the convective layer, we used rates from a 1‐D radiative‐convective model. The resolved layer, taking place between 1.0 × 105 and 3.8 × 104 Pa (48–53 km), is organized as polygonal closed cells of about 10 km wide with vertical wind of several meters per second. The convection emits gravity waves both above and below the convective layer leading to temperature perturbations of several tenths of kelvin with vertical wavelength between 1 and 3 km and horizontal wavelength from 1 to 10 km. The thickness of the convective layer and the amplitudes of waves are consistent with observations, though slightly underestimated. The global dynamics heating greatly modify the convective layer.
Bed conditions of Pine Island Glacier, West Antarctica
Authors: Brisbourne A. M. , Smith A. M. , Vaughan D. G. , King E. C. , Davies D. , Bingham R. G. , Smith E. C. , Nias I. J. , Rosier S. H. R.
Published: November 2016

Although 90% of Antarctica's discharge occurs via its fast‐flowing ice streams, our ability to project future ice sheet response has been limited by poor observational constraints on the ice‐bed conditions used in numerical models to determine basal slip. We have helped address this observational deficit by acquiring and analyzing a series of seismic reflection profiles to determine basal conditions beneath the main trunk and tributaries of Pine Island Glacier (PIG), West Antarctica. Seismic profiles indicate large‐scale sedimentary deposits. Combined with seismic reflection images, measured acoustic impedance values indicate relatively uniform bed conditions directly beneath the main trunk and tributaries, comprising a widespread reworked sediment layer with a dilated sediment lid of minimum thickness 1.5 ± 0.4 m. Beneath a slow‐moving intertributary region, a discrete low‐porosity sediment layer of 7 ± 3 m thickness is imaged. Despite considerable basal topography, seismic observations indicate that a till layer at the ice base is ubiquitous beneath PIG, which requires a highly mobile sediment body to maintain an abundant supply. These results are compatible with existing ice sheet models used to invert for basal shear stress: existing basal conditions upstream will not inhibit further rapid retreat of PIG if the high‐friction region currently restraining flow, directly upstream of the grounding line, is breached. However, small changes in the pressure regime at the bed, as a result of stress reorganization following retreat, may result in a less‐readily deformable bed and conditions which are less likely to maintain high ice‐flow rates.
Improving the lake scheme within a coupled WRF‐lake model in the Laurentian Great Lakes
Authors: Xiao Chuliang , Lofgren Brent M. , Wang Jia , Chu Philip Y.
Published: November 2016

In this study, a one‐dimensional (1‐D) thermal diffusion lake model within the Weather Research and Forecasting (WRF) model was investigated for the Laurentian Great Lakes. In the default 10‐layer lake model, the albedos of water and ice are specified with constant values, 0.08 and 0.6, respectively, ignoring shortwave partitioning and zenith angle, ice melting, and snow effect. Some modifications, including a dynamic lake surface albedo, tuned vertical diffusivities, and a sophisticated treatment of snow cover over lake ice, have been added to the lake model. A set of comparison experiments have been carried out to evaluate the performances of different lake schemes in the coupled WRF‐lake modeling system. Results show that the 1‐D lake model is able to capture the seasonal variability of lake surface temperature (LST) and lake ice coverage (LIC). However, it produces an early warming and quick cooling of LST in deep lakes, and excessive and early persistent LIC in all lakes. Increasing vertical diffusivity can reduce the bias in the 1‐D lake but only in a limited way. After incorporating a sophisticated treatment of lake surface albedo, the new lake model produces a more reasonable LST and LIC than the default lake model, indicating that the processes of ice melting and snow accumulation are important to simulate lake ice in the Great Lakes. Even though substantial efforts have been devoted to improving the 1‐D lake model, it still remains considerably challenging to adequately capture the full dynamics and thermodynamics in deep lakes.
Preparation of Robust CuO/TiO2 Superamphiphobic Steel Surface through Chemical Deposition and Sol–Gel Methods
Authors: Xia Bingbing , Liu Hongtao , Fan Yinan , Zhu Wei , Geng Chao
Published: November 2016

The authors report a novel method of fabricating CuO/TiO2 superamphiphobic surface through chemical deposition and sol–gel on Q235 steel. After modification with FAS‐17, the water, glycerol, and cooking oil contact angles of CuO/TiO2 coating surpass 150° the corresponding sliding angles are all less 10°. Furthermore, the as‐prepared superamphiphobic surfaces can survive 500 times, 400 cm abrasion distance under 2.2 kPa pressure without losing superhydrophobicity. In addition, outstanding corrosion resistance and low adhesion are obtained. The successful fabrication of a robust, good anti‐corrosion superamphiphobic surface can be a prospective applied in metal materials.
A Cooperative Copper Metal–Organic Framework‐Hydrogel System Improves Wound Healing in Diabetes
Authors: Xiao Jisheng , Chen Siyu , Yi Ji , Zhang Hao F. , Ameer Guillermo A.
Published: November 2016

Chronic nonhealing wounds remain a major clinical challenge that would benefit from the development of advanced, regenerative dressings that promote wound closure within a clinically relevant time frame. The use of copper ions has shown promise in wound healing applications, possibly by promoting angiogenesis. However, reported treatments that use copper ions require multiple applications of copper salts or oxides to the wound bed, exposing the patient to potentially toxic levels of copper ions and resulting in variable outcomes. Herein the authors set out to assess whether copper metal organic framework nanoparticles (HKUST‐1 NPs) embedded within an antioxidant thermoresponsive citrate‐based hydrogel would decrease copper ion toxicity and accelerate wound healing in diabetic mice. HKUST‐1 and poly‐(polyethyleneglycol citrate‐co‐N‐isopropylacrylamide) (PPCN) are synthesized and characterized. HKUST‐1 NP stability in a protein solution with and without embedding them in PPCN hydrogel is determined. Copper ion release, cytotoxicity, apoptosis, and in vitro migration processes are measured. Wound closure rates and wound blood perfusion are assessed in vivo using the splinted excisional dermal wound diabetic mouse model. HKUST‐1 NPs disintegrated in protein solution while HKUST‐1 NPs embedded in PPCN (H‐HKUST‐1) are protected from degradation and copper ions are slowly released. Cytotoxicity and apoptosis due to copper ion release are significantly reduced while dermal cell migration in vitro and wound closure rates in vivo are significantly enhanced. In vivo, H‐HKUST‐1 induced angiogenesis, collagen deposition, and re‐epithelialization during wound healing in diabetic mice. These results suggest that a cooperatively stabilized, copper ion‐releasing H‐HKUST‐1 hydrogel is a promising innovative dressing for the treatment of chronic wounds.
“Black” Titania Coatings Composed of Sol–Gel Imprinted Mie Resonators Arrays
Authors: Bottein Thomas , Wood Thomas , David Thomas , Claude Jean Benoît , Favre Luc , Berbézier Isabelle , Ronda Antoine , Abbarchi Marco , Grosso David
Published: November 2016

Optical technologies and devices rely on the controlled manipulation of light propagation through a medium. This is generally governed by the inherent effective refractive index of the material as well as by its structure and dimensionality. Although a precise control over light propagation with sub‐wavelength size objects is a crucial issue for a plethora of applications, the widely used fabrication methods remain cumbersome and expensive. Here, a sol–gel dip‐coating method combined with nanoimprinting lithography on arbitrary glass and silicon substrates is implemented for the fabrication of TiO2‐based dielectric Mie resonators. The technique allows obtaining sub‐micrometric pillars featuring unprecedented vertical aspect ratios (>1) with relatively high fidelity and precision. Spectroscopic characterization at visible and near‐infrared frequencies demonstrate that the resonant properties of these dielectric pillar arrays allow for a drastic reduction of light transmission (cutting more than 50% on glass) and reduced reflection (reflecting less than 3% on glass and 16% on bulk silicon), accounting for an efficient light trapping. These results provide a guideline for the fabrication of Mie resonators using a fast, versatile, low‐cost, low‐temperature technique for efficient light manipulation at the nanoscale.
Gold(I)‐Catalysed Cyclisation of Alkynoic Acids: Towards an Efficient and Eco‐Friendly Synthesis of γ‐, δ‐ and ϵ‐Lactones
Authors: Gasperini Danila , Maggi Lorenzo , Dupuy Stéphanie , Veenboer Richard M. P. , Cordes David B. , Slawin Alexandra M. Z. , Nolan Steven P.
Published: November 2016

The improved synthesis of γ‐, δ‐ and ϵ‐lactones using a dinuclear N‐heterocyclic carbene (NHC)‐gold(I) catalyst is reported. This solvent‐free process provides access to γ‐ and δ‐lactones in high regio‐ and stereoselectivity. Reactions were performed at low catalyst loadings and without the need for any additives. The use of a digold pre‐catalyst provides a new synthetic route to functionalised ϵ‐lactones, poorly accessible using previous methodologies.

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Copper‐Catalyzed Three‐Component One‐Pot Synthesis of Aryl Sulfides with Sulfur Powder under Aqueous Conditions
Authors: Xiao Fuhong , Chen Shuqing , Li Cheng , Huang Huawen , Deng Guo‐Jun
Published: November 2016

A copper‐catalyzed three‐component (arenes, iodohydrocarbon, and sulfur powder) synthesis of substituted aryl sulfides has been developed. Water is used as the green solvent in a simple and environmentally friendly procedure. Various functional groups attached to the substrates were well tolerated in this process to afford the corresponding products in moderate to good yields.

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Air Stable Iron(II) PNP Pincer Complexes as Efficient Catalysts for the Selective Alkylation of Amines with Alcohols
Authors: Mastalir Matthias , Stöger Berthold , Pittenauer Ernst , Puchberger Michael , Allmaier Günter , Kirchner Karl
Published: November 2016

A series of well‐defined iron(II) complexes of the types [Fe(PNP)Br2] and [Fe(PNP)(CO)Br2] with PNP pincer ligands based on triazine and pyridine backbones were prepared and fully characterized. These complexes were tested as catalysts for the alkylation of amines by alcohols. The high‐spin complexes [Fe(PNP)Br2] are catalytically inactive. The low‐spin complexes [Fe(PNP)(CO)Br2] bearing a carbonyl co‐ligand efficiently and selectively convert primary alcohols and aromatic and benzylic amines selectively into mono‐N‐alkylated amines in good to excellent isolated yields. A mechanistic proposal is given.

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Enhanced mechanical properties of styrene–butadiene rubber with low content of bacterial cellulose nanowhiskers
Authors: Yin Biao , Li Geng , Wang Dongni , Wang Liping , Wang Jingyi , Jia Hongbing , Ding Lifeng , Sun Dongping
Published: November 2016

Styrene–butadiene rubber (SBR) nano‐composites were prepared through mixing SBR latex with bacterial cellulose whiskers (BCWs). BCWs were extracted from the residual bacterial cellulose (BC) that was treated with acid hydrolysis. A rod‐like nanofiber structure of BCWs was observed by transmission electron microscopy and atomic force microscopy. BCWs maintained the crystal structure in BCWs/SBR nano‐composites as confirmed by X‐ray diffraction patterns. The dispersion of BCWs in SBR matrix was further detected with field emission scan electron microscope. BCWs acted as a multifunctional physical cross‐linker in the SBR matrix, the combination of BCW reinforcement and increased effective cross‐linking density of the rubber network with incorporating BCWs would cause a more effective transfer of stresses from matrix to filler. Compared with neat SBR, the tensile strength and tear strength of SBR/BCW nano‐composite with 2.5 phr (parts per hundred rubber) BCWs were increased by 319% and 182%, respectively.
Impact of total body irradiation on successful neutrophil engraftment in unrelated bone marrow or cord blood transplantation
Authors: Nakasone Hideki , Shigeo Fuji , Yakushijin Kimikazu , Onizuka Makoto , Shinohara Akihito , Ohashi Kazuteru , Miyamura Koichi , Uchida Naoyuki , Takanashi Minoko , Ichinohe Tatsuo , Atsuta Yoshiko , Fukuda Takahiro , Ogata Masao ,   On Behalf of the Complication Working Group of Japanese Society for Hematopoietic Cell Transplantation
Published: November 2016

Total body irradiation (TBI) has been thought to promote donor cell engraftment in allogeneic hematopoietic cell transplantation (HCT) from alternative donors. However, recent progress in HCT strategies may affect the clinical significance of TBI on neutrophil engraftment. With the use of a Japanese transplant registry database, we analyzed 3933 adult recipients (>15 y.o.) who underwent HCT between 2006 and 2013 from an 8/8 HLA‐matched unrelated bone marrow donor (MUD, n = 1367), an HLA‐mismatched unrelated bone marrow donor (MMUD, n = 1102), or unrelated cord blood (CBT, n = 1464). Conditioning regimens were divided into five groups: High‐TBI‐(>8Gy), Low‐TBI‐ (≤8Gy), and no‐TBI‐myeloablative conditioning (MAC), and Low‐TBI‐ and no‐TBI‐reduced‐intensity conditioning (RIC). In both MUD and MMUD, neutrophil engraftment rate was >90% in each of the five conditioning groups, and TBI was not associated with prompt neutrophil engraftment in multivariate analyses. Conversely, in CBT, TBI regimens had a higher rate of day‐30 neutrophil engraftment than no‐TBI‐regimens: 78% in High‐TBI‐MAC, 83% in Low‐TBI‐MAC, and 76% in Low‐TBI‐RIC versus 65% in No‐TBI‐MAC, and 68% in No‐TBI‐RIC (P < .001). Multivariate analyses in CBT demonstrated that TBI‐regimens were significantly associated with a higher rate of neutrophil engraftment. Subsequently focusing on CBT patients alone, TBI‐regimens were significantly associated with a higher rate of neutrophil engraftment in patients who received CBT with a 4/6 or less HLA allele‐match, or who had anti‐HLA antibodies. In summary, TBI‐regimens had no impact on neutrophil engraftment in the current practice of unrelated bone marrow transplantation. However, in CBT, TBI is still necessary to enhance engraftment.
Template–Framework Interactions in Tetraethylammonium‐Directed Zeolite Synthesis
Authors: Schmidt Joel E. , Fu Donglong , Deem Michael W. , Weckhuysen Bert M.
Published: November 2016

Zeolites, having widespread applications in chemical industries, are often synthesized using organic templates. These can be cost‐prohibitive, motivating investigations into their role in promoting crystallization. Herein, the relationship between framework structure, chemical composition, synthesis conditions and the conformation of the occluded, economical template tetraethylammonium (TEA+) has been systematically examined by experimental and computational means. The results show two distinct regimes of occluded conformer tendencies: 1) In frameworks with a large stabilization energy difference, only a single conformer was found (BEA, LTA and MFI). 2) In the frameworks with small stabilization energy differences (AEI, AFI, CHA and MOR), less than the interconversion of TEA+ in solution, a heteroatom‐dependent (Al, B, Co, Mn, Ti, Zn) distribution of conformers was observed. These findings demonstrate that host–guest chemistry principles, including electrostatic interactions and coordination chemistry, are as important as ideal pore‐filling.
Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion
Authors: Xu Boran , Hartigan Elizabeth M. , Feula Giancarlo , Huang Zheng , Lumb Jean‐Philip , Arndtsen Bruce A.
Published: November 2016

We describe the use of simple copper‐salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations.
On Approaching the Limit of Molecular Magnetic Anisotropy: A Near‐Perfect Pentagonal Bipyramidal Dysprosium(III) Single‐Molecule Magnet
Authors: Ding You‐Song , Chilton Nicholas F. , Winpenny Richard E. P. , Zheng Yan‐Zhen
Published: November 2016

We report a monometallic dysprosium complex, [Dy(OtBu)2(py)5][BPh4] (5), that shows the largest effective energy barrier to magnetic relaxation of Ueff=1815(1) K. The massive magnetic anisotropy is due to bis‐trans‐disposed tert‐butoxide ligands with weak equatorial pyridine donors, approaching proposed schemes for high‐temperature single‐molecule magnets (SMMs). The blocking temperature, TB , is 14 K, defined by zero‐field‐cooled magnetization experiments, and is the largest for any monometallic complex and equal with the current record for [Tb2N2{N(SiMe3)2}4(THF)2].
Characterization and Crystal Structure of a Robust Cyclohexanone Monooxygenase
Authors: Romero Elvira , Castellanos J. Rubén Gómez , Mattevi Andrea , Fraaije Marco W.
Published: November 2016

Cyclohexanone monooxygenase (CHMO) is a promising biocatalyst for industrial reactions owing to its broad substrate spectrum and excellent regio‐, chemo‐, and enantioselectivity. However, the low stability of many Baeyer–Villiger monooxygenases is an obstacle for their exploitation in industry. Characterization and crystal structure determination of a robust CHMO from Thermocrispum municipale is reported. The enzyme efficiently converts a variety of aliphatic, aromatic, and cyclic ketones, as well as prochiral sulfides. A compact substrate‐binding cavity explains its preference for small rather than bulky substrates. Small‐scale conversions with either purified enzyme or whole cells demonstrated the remarkable properties of this newly discovered CHMO. The exceptional solvent tolerance and thermostability make the enzyme very attractive for biotechnology.
Living Cationic Polymerization of Vinyl Ethers through a Photoinduced Radical Oxidation/Addition/Deactivation Sequence
Authors: Ciftci Mustafa , Yoshikawa Yuji , Yagci Yusuf
Published: November 2016

A new photoinitiating system for living cationic polymerization of vinyl ethers is reported. In the current approach, visible‐light irradiation of dimanganese decacarbonyl (Mn2(CO)10) in the presence of an alkyl bromide results in the formation of carbon‐centered radicals. The photochemically generated radicals were then oxidized by diphenyliodonium ions to the corresponding cations. These cations can add vinyl ether monomers, which are then rapidly deactivated by the bromide anions to give α‐halide functional end groups. Poly(vinyl ether) chains are then grown through successive photoinduced radical oxidation/addition/deactivation (PROAD) in a controlled manner. The living nature of the system is evaluated through kinetics studies and block copolymer formation.
Algae fiber polypropylene composites: Modeling of the degradation by solid state kinetics
Authors: Constante Alejandra , Pillay Selvum
Published: November 2016

Knowledge of the mechanisms of degradation in natural fiber composites (NFCs) has great importance for the life cycle assessment of the automotive components based on NFCs. The purpose of this study was to evaluate the solid state kinetic models available to describe the degradation process of algae fiber/grafted polypropylene (AFPPg) composites processed by extrusion compression molding (ECM). Samples of the 0.14 volume fraction (υf) AFPPg composite, algae fiber, and grafted PP were evaluated before and after 576 hours of accelerated UV light weatherization. The weight loss of the specimens was determined by thermogravimetric analysis (TGA) at six isothermal temperatures, and weight loss data were transformed into the conversion fraction α. Curves of the factor α and time were linearized using MATLAB software to find the parameters of the degradation. The best statistical fit to model the degradation was given by the Avrami–Erofe'ev model. The kinetic parameters of PP grafted after UV exposure were frequency factor (A) of 6.26 min−1 and activation energy E0 of 24 kJ/mol. The effect of degradation was characterized by Fourier transformed infrared spectroscopy (FTIR). The characteristic bands of the main products of degradation in the composite were identified as pentane and propane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44622.
Human Digital Meissner Corpuscles Display Immunoreactivity for the Multifunctional Ion Channels Trpc6 and Trpv4
Authors: Alonso‐González Paula , Cabo Roberto , San José Isabel , Gago Angel , Suazo Iván C. , García‐Suárez Olivia , Cobo Juan , Vega José A.
Published: November 2016

Ion channels are at the basis of the sensory processes including mechanosensing. Some members of the transient receptor potential (TRP) ion channel superfamily have been proposed as mechanosensors, but their putative role in mechanotransduction is controversial. Among them there are TRP canonical 6 (TRPC6) and TRP vanilloid 4 (TRPV4) ion channels, which are known to cooperate in mechanical hyperalgesia. Here, we investigated the occurrence, distribution, and possible colocalization of TRPC6 and TRPV4 in human digital Meissner sensory corpuscles using immunohistochemistry and double immunofluorescence (associate with markers for specific corpuscular constituents). TRPC6 immunoreactivity was restricted to the axon of Meissner corpuscles, whereas TRPV4 was detected in the axon but also in the lamellar cells. Moreover, axonal colocalization of TRPV4 and TRPC6 was found in the digital Meissner corpuscles. Present results demonstrate for the first time the occurrence and colocalization of two ion channels candidates to mechanosensors in human cutaneous mechanoreceptors. The functional significance of these ion channels in that place remains to be clarified, but should be related to different properties of mechanosensitivity. Anat Rec, 300:1022–1031, 2017. © 2016 Wiley Periodicals, Inc.
An untold story: The important contributions of Muslim scholars for the understanding of human anatomy
Authors: Alghamdi Malak A. , Ziermann Janine M. , Diogo Rui
Published: November 2016

It is usually assumed that Galen is one of the fathers of anatomy and that between the Corpus Galenicum and the Renaissance there was no major advance in anatomical knowledge. However, it is also consensually accepted that Muslim scholars had the intellectual leadership from the 8th/9th to 13th centuries, and that they made remarkable progresses in numerous scientific fields including medicine. So, how is it possible that they did not contribute to advance human anatomy during that period? According to the dominant view, Muslim scholars exclusively had a passive role: their transmission of knowledge from the Greeks to the West. Here, we summarize, for the first time in a single paper, the studies of major Muslim scholars that published on human anatomy before Vesalius. This summary is based on analyses of original Arabic texts and of more recent publications by anatomists and historians, and on comparisons between the descriptions provided by Galen and by these Muslim scholars. We show that Arabic speakers and Persians made important advances in human anatomy well before Vesalius. The most notable exception concerns the muscular system: strikingly, there were apparently neither advances made by Muslims nor by Westerners for more than 1000 years. Unbiased discussions of these and other related issues, and particularly of the mainly untold story about the major contributions of Muslim scholars to anatomy, are crucial to our knowledge of the history of anatomy, biology and sciences, and also of our way of thinking, biases, and prejudices. Anat Rec, 300:986–1008, 2017. © 2017 Wiley Periodicals, Inc.
Drotaverine – a Concealed Cytostatic!
Authors: Pavel Ioana Z. , Heller Lucie , Sommerwerk Sven , Loesche Anne , Al‐Harrasi Ahmed , Csuk René
Published: November 2016

Drotaverine (also known as dihydroperparine or No‐Spa®) is an antispasmodic drug closely related to papaverin. Drotaverin also acts as a cytostatic compound for several human tumor cell lines and nonmalignant mouse fibroblasts, and EC50 values as low as 3.0 μM were observed in SRB assays for HT‐29 human colorectal carcinoma cells. Small structural changes (e.g., aromatization, benzylic oxidation) led to a reduced activity or a complete loss of cytotoxicity. Staining of the cells with acridine orange showed the cell membrane of the dead cells to be still intact, and a slight G1/G0 arrest in the treated cells was observed after 24 h. Extra annexin V‐FITC/PI assays and flow cytometry revealed drotaverine mainly to act as a cytostatic and only to a minor extent as cytotoxic agent.
Funding Data from Publication Acknowledgments: Coverage, Uses, and Limitations
Authors: Grassano Nicola , Rotolo Daniele , Hutton Joshua , Lang Frédérique , Hopkins Michael M.
Published: November 2016

This article contributes to the development of methods for analysing research funding systems by exploring the robustness and comparability of emerging approaches to generate funding landscapes useful for policy making. We use a novel data set of manually extracted and coded data on the funding acknowledgements of 7,510 publications representing UK cancer research in the year 2011 and compare these “reference data” with funding data provided by Web of Science (WoS) and MEDLINE/PubMed. Findings show high recall (around 93%) of WoS funding data. By contrast, MEDLINE/PubMed data retrieved less than half of the UK cancer publications acknowledging at least one funder. Conversely, both databases have high precision (+90%): That is, few cases of publications with no acknowledgment to funders are identified as having funding data. Nonetheless, funders acknowledged in UK cancer publications were not correctly listed by MEDLINE/PubMed and WoS in around 75% and 32% of the cases, respectively. Reference data on the UK cancer research funding system are used as a case study to demonstrate the utility of funding data for strategic intelligence applications (e.g., mapping of funding landscape and co‐funding activity, comparison of funders' research portfolios).
Robust MPC for Linear Systems with Structured Time‐Varying Uncertainties and Saturating Actuator
Authors: Zhang Langwen , Xie Wei , Wang Jingcheng
Published: November 2016

In this paper, a synthesis of model predictive control (MPC) algorithm is presented for uncertain systems subject to structured time‐varying uncertainties and actuator saturation. The system matrices are not exactly known, but are affine functions of a time varying parameter vector. To deal with the nonlinear actuator saturation, a saturated linear feedback control law is expressed into a convex hull of a group of auxiliary linear feedback laws. At each time instant, a state feedback law is designed to ensure the robust stability of the closed‐loop system. The robust MPC controller design problem is formulated into solving a minimization problem of a worst‐case performance index with respect to model uncertainties. The design of controller is then cast into solving a feasibility of linear matrix inequality (LMI) optimization problem. Then, the result is further extended to saturation dependent robust MPC approach by introducing additional variables. A saturation dependent quadratic function is used to reduce the conservatism of controller design. To show the effectiveness, the proposed robust MPC algorithms are applied to a continuous‐time stirred tank reactor (CSTR) process.
Prenatal toxoplasmosis antibody and childhood autism
Authors: Spann Marisa N. , Sourander Andre , Surcel Heljä‐Marja , Hinkka‐Yli‐Salomäki Susanna , Brown Alan S.
Published: November 2016

There is evidence that some maternal infections during the prenatal period are associated with neurodevelopmental disorders, such as childhood autism. However, the association between autism and Toxoplasma gondii (T. gondii), an intracellular parasite, remains unclear. The authors examined whether serologically confirmed maternal antibodies to T. gondii are associated with odds of childhood autism in offspring. The study is based on a nested case‐control design of a large national birth cohort (N = 1.2 million) and the national psychiatric registries in Finland. There were 874 cases of childhood autism and controls matched 1:1 on date of birth, sex, birthplace and residence in Finland. Maternal sera were prospectively assayed from a national biobank for T. gondii IgM and IgG antibodies; IgG avidity analyses were also performed. High maternal T. gondii IgM antibody was associated with a significantly decreased odds of childhood autism. Low maternal T. gondii IgG antibody was associated with increased offspring odds of autism. In women with high T. gondii IgM antibodies, the IgG avidity was high for both cases and controls, with the exception of three controls. The findings suggest that the relationship between maternal T. gondii antibodies and odds of childhood autism may be related to the immune response to this pathogen or the overall activation of the immune system. Autism Res 2017, 10: 769–777. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Green extraction technologies for high‐value metabolites from algae: a review
Authors: Esquivel‐Hernández Diego A. , Ibarra‐Garza Ingrid P. , Rodríguez‐Rodríguez José , Cuéllar‐Bermúdez Sara P. , Rostro‐Alanis Magdalena de J. , Alemán‐Nava Gibrán S. , García‐Pérez J. Saúl , Parra‐Saldívar Roberto
Published: November 2016

Cultivation of algae (micro and macro) can be used to produce several high‐ value metabolites to supply industries as cosmetics, additives, and pigments, among others. Those metabolites can have physiological and nutritional benefits for human and animal health. However, the availability of high‐value metabolites from algae is still unaffordable due to traditional extraction techniques and their requirements of energy and use of pollutant solvents. Recently, green extraction technologies for the extraction of high‐value metabolites have become more desirable due to their sustainability and environmental benefits. However, the information about green extraction metabolites from algae is limited. Therefore, this review highlights the main green extraction technologies – supercritical fluid extraction (SFE), microwave assisted extraction (MAE), and pressurized liquid extraction (PLE) – and their optimal parameters for the extraction of high‐value metabolites from algae. First, general information is given regarding high‐ value metabolites from algae. Then, the review summarizes the principles, processes, advantages, and disadvantages of each technology. Finally, it presents recommendations and concluding remarks to select the best extraction technology. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd
Congenital malformations in offspring of women with a history of malignancy
Authors: Sabeti Rad Zahra , Friberg Britt , Henic Emir , Rylander Lars , Ståhl Olof , Källén Bengt , Lingman Göran
Published: November 2016

Background

Survival after malignancy has increased and the question of risks, including risk for congenital malformations for the offspring of these women has become important. Data on congenital malformations in such offspring are limited.

Methods

We compared congenital malformation in offspring, born 1994 to 2011 of women with a history of malignancy (at least 1 year before delivery) with all other offspring. Adjustment for confounders was mainly made by Mantel‐Haenszel methodology. Data were obtained by linkage between Swedish national health registers.

Results

We identified 71,954 (4.1%) infants with congenital malformation, of which 47,081 (2.7%) were relatively severe (roughly corresponding to major malformation). Among 7284 infants to women with a history of malignancy 204 relatively severe malformations were found (2.8%; odds ratio [OR] = 1.04; 95% confidence interval [CI], 0.91–1.20). After in vitro fertilization, the risk of a relatively severe malformation was significantly increased in women without a history of malignancy (OR = 1.31; 95% CI, 1.24–1.38) and still more in women with such a history (risk ratio = 1.85; 95% CI, 1.08–2.97). However, there were no significant differences neither, for any malformations (OR = 1.04; 95% CI, 0.92–1.16) nor for relatively severe malformations (OR = 1.04; 95% CI, 0.91–1.20), when comparing offspring only after maternal history of malignancy.

Conclusion

No general increase in malformation rate was found in infants born to women with a history of malignancy. A previously known increased risk after in vitro fertilization was verified and it is possible that this risk is further augmented among infants born of women with a history of malignancy. Birth Defects Research 109:224–233, 2017. © 2016 Wiley Periodicals, Inc.