bluuebunny/crossref_metadata_2025 huggingface dataset:
Oxygen‐Deficient BiOBr as a Highly Stable Photocatalyst for Efficient CO2 Reduction into Renewable Carbon‐Neutral Fuels
Authors: Kong Xin Ying , Lee W. P. Cathie , Ong Wee‐Jun , Chai Siang‐Piao , Mohamed Abdul Rahman
Published: September 2016

A highly facile one‐pot ethylene glycol‐assisted solvothermal process was employed to fabricate bismuth oxybromide (BiOBr) with oxygen‐deficient defects. These defects played an indispensable role for superior photocatalytic CO2 reduction, in which the as‐prepared sample demonstrated a remarkable improvement of 3.3 and 5.7‐fold for CH4 production over pristine BiOBr and P25, respectively. The enhancement could be attributed to the presence of oxygen vacancies, which acted as the active sites for CO2 adsorption and activation. In addition, the oxygen–deficiency–induced defect states could effectively trap photogenerated electrons, thus improving the separation of the electron–hole pairs and significantly slow down the recombination rate of charge carriers. On top of that, oxygen‐deficient BiOBr exhibited long term stability (>50 hours of catalytic reaction) for CO2 photoreduction under simulated solar light, where no reducing agent or any post‐treatment was needed to regenerate the oxygen vacancies.
Mechanochemical Immobilisation of Metathesis Catalysts in a Metal–Organic Framework
Authors: Spekreijse Jurjen , Öhrström Lars , Sanders Johan P. M. , Bitter Johannes H. , Scott Elinor L.
Published: September 2016

A simple, one‐step mechanochemical procedure for immobilisation of homogeneous metathesis catalysts in metal–organic frameworks was developed. Grinding MIL‐101‐NH2(Al) with a Hoveyda–Grubbs second‐generation catalyst resulted in a heterogeneous catalyst that is active for metathesis and one of the most stable immobilised metathesis catalysts. During the mechanochemical immobilisation the MIL‐101‐NH2(Al) structure was partially converted to MIL‐53‐NH2(Al). The Hoveyda–Grubbs catalyst entrapped in MIL‐101‐NH2(Al) is responsible for the observed catalytic activity. The developed synthetic procedure was also successful for the immobilisation of a Zhan catalyst.
Air‐Stable Spirofluorene‐Containing Ladder‐Type Bis(alkynyl)borane Compounds with Readily Tunable Full Color Emission Properties
Authors: Wong Ben Yiu‐Wing , Wong Hok‐Lai , Wong Yi‐Chun , Chan Mei‐Yee , Yam Vivian Wing‐Wah
Published: September 2016

A series of air‐stable spiro‐fused ladder‐type boron(III) compounds has been designed, synthesized, and the electrochemistry and photophysical behavior have been characterized. By simply varying the substituents on the pyridine ring and extending the π‐conjugation of the spiro framework, the emission color of these compounds can be easily fine‐tuned spanning the visible spectrum from blue to red. All compounds exhibit a broad and structureless emission band across the entire visible region, assigned as an intramolecular charge‐transfer transition originating from the thiophene of the spiro framework to the pyridine‐borane moieties. In addition, these compounds demonstrate high photoluminescence quantum yields of up to 0.81 in dichloromethane solution and 0.86 in doped thin films. Some of the compounds have also been employed as emissive materials, in which solution‐processed organic light‐emitting devices (OLEDs) with tunable emission colors spanning the visible spectrum from blue, green to red have been realized, demonstrating the potential applications of these boron compounds in OLEDs.
A Porous Zirconium‐Based Metal‐Organic Framework with the Potential for the Separation of Butene Isomers
Authors: Liu Huimin , He Yabing , Jiao Jingjing , Bai Dongjie , Chen De‐li , Krishna Rajamani , Chen Banglin
Published: September 2016

By using a novel C3‐symmetrical tricarboxylate (4,4′,4′′‐benzene‐1,3,5‐triyl‐1,1′,1′′‐trinaphthoic acid), a novel zirconium‐based metal‐organic framework ZJNU‐30 was solvothermally synthesized and structurally characterized. Single‐crystal X‐ray structural analyses show that ZJNU‐30 consists of Zr6‐based nodes connected by the organic linkers to form a (3,8)‐connected network featuring the coexistence of two different polyhedral cages: octahedral and cuboctahedral cages with the dimensions of about 14 and 22 Å, respectively. Remarkably, ZJNU‐30 is very stable when exposed to air for one month. More importantly, with a moderately high surface area, hierarchical pore structures, and an aromatic‐rich pore surface in the framework, ZJNU‐30, after activation, exhibits a promising potential for the selective adsorptive separation of industrially important butene isomers consisting of cis‐2‐butene, trans‐2‐butene, 1‐butene, and iso‐butene at ambient temperature. This separation was established exclusively by gas adsorption isotherms and simulated breakthrough experiments. To the best of our knowledge, this is the first study investigating porous metal‐organic frameworks for butene‐isomer separation.
Axially Substituted Silicon Phthalocyanine as Electron Donor in a Dyad and Triad with Azafullerene as Electron Acceptor for Photoinduced Charge Separation
Authors: Rotas Georgios , Martín‐Gomis Luis , Ohkubo Kei , Fernández‐Lázaro Fernando , Fukuzumi Shunichi , Tagmatarchis Nikos , Sastre‐Santos Ángela
Published: September 2016

The synthesis of a donor–acceptor silicon phthalocyanine (SiPc)‐azafullerene (C59N) dyad 1 and of the first acceptor–donor–acceptor C59N‐SiPc‐C59N dumbbell triad 2 was accomplished. The two C59N‐based materials were comprehensively characterized with the aid of NMR spectroscopy, MALDI‐MS as well as DFT calculations and their redox and photophysical properties were evaluated with CV and steady‐state and time‐resolved absorption and photoluminescence spectroscopy measurements. Notably, femtosecond transient absorption spectroscopy assays revealed that both dyad 1 and triad 2 undergo, after selective photoexcitation of the SiPc moiety, photoinduced electron transfer from the singlet excited state of the SiPc moiety to the azafullerene counterpart to produce the charge‐separated state, with lifetimes of 660 ps, in the case of dyad 1, and 810 ps, in the case of triad 2. The current results are expected to have significant implications en route to the design of advanced C59N‐based donor–acceptor systems targeting energy conversion applications.
Multi‐Metal‐Substituted‐Goethite as an Effective Catalyst for Azo Dye Wastewater Oxidation
Authors: Schlichter Sofía , Diez Alejandra S. , Zenobi María C. , Dennehy Mariana , Alvarez Mariana
Published: September 2016

Different samples of goethite modified with cobalt, manganese, or aluminum were synthesized and characterized by means of X‐ray diffraction, chemical analysis, scanning electron microscopy, zeta potential measurements, and N2 adsorption–desorption isotherm analysis. The goethite oxides were tested as efficient catalysts for the degradation of methyl orange (MO, sodium 4‐[(4‐dimethylamino)phenylazo]benzenesulfonate), a sulfonated azo dye indicator, employing potassium persulfate (PS) in water, at pH 3. The Mn, Co, and Al substitution in goethite gave rise to active sites for PS activation. The most effective catalyst reached 93% of degradation at 120 min of reaction. The increase of temperature led to an expected conversion enhancement, and kinetic parameters were calculated for one of the evaluated catalysts. MO degradation curves best fitted to pseudo‐second order kinetics. The extent of mineralization, measured as total removed organic carbon (TOC), was also monitored. A significant degree of mineralization was achieved and confirmed by TOC analysis. A mechanism for MO oxidation with radicals was discarded and a pathway involving peroxymonosulfate species was proposed. The results indicate that the goethite‐substituted oxides are effective catalysts for the studied azo dye degradation in aqueous solution.
Molecular Dissociation on the SiC(0001) 3×3 Surface
Authors: Sonnet Philippe , Stauffer Louise , Gille Marie , Bléger David , Hecht Stefan , Cejas Cesare , Dujardin Gérald , Mayne Andrew J.
Published: September 2016

In the framework of density functional theory, the adsorption of the halogenated polycyclic aromatic hydrocarbon 2,11‐diiodohexabenzocoronene (HBC‐I2) on the SiC(0001) 3×3 surface has been investigated. Nondissociative and dissociative molecular adsorption is considered, and simulated scanning tunneling microscopy (STM) images are compared with the corresponding experimental observations. Calculations show that dissociative adsorption is favorable and reveal the crucial importance of the extended flat carbon core on molecule–surface interactions in dissociative adsorption; the iodine atom–surface interaction is of minor importance. Indeed, removing iodine atoms does not significantly affect the STM images of the central part of the molecule. This study shows that the dissociation of large halogenated polycyclic aromatic hydrocarbon molecules can occur on the SiC surface. This opens up interesting perspectives in the chemical reactivity and functionalization of wide band gap semiconductors.
Structural and Theoretical Study of Salts of the [B9H14]− Ion: Isolation of Multiple Isomers and Implications for Energy Storage
Authors: Kelley Steven P. , McCrary Parker D. , Flores Luis , Garner Edward B. , Dixon David A. , Rogers Robin D.
Published: September 2016

Invited for this month's cover are the research groups of Prof. Robin Rogers, based at McGill University, and Prof. David Dixon, based at The University of Alabama. The cover picture shows two isomers of [B9H14]− which coexist in a crystalline salt, the mirror symmetric form on the left and the unsymmetrical form on the right. Read the full text of the article at 10.1002/cplu.201600270.
The Conversion of Starch and Sugars into Branched C10 and C11 Hydrocarbons
Authors: Sutton Andrew D. , Kim Jin K. , Wu Ruilian , Hoyt Caroline B. , Kimball David B. , Silks Louis A. , Gordon John C.
Published: September 2016

Invited for this month′s cover are Andrew Sutton and John Gordon and their co‐workers at Los Alamos National Laboratory. The image illustrates a concept of using biomass to derived fuel and fuel molecules through simple catalytic transformations. The Communication itself is available at 10.1002/cssc.201600669.
Diagnostic screening of paroxysmal nocturnal hemoglobinuria: Prospective multicentric evaluation of the current medical indications
Authors: Morado Marta , Freire Sandes Alex , Colado Enrique , Subirá Dolores , Isusi Paloma , Soledad Noya María , Belén Vidriales María , Sempere Amparo , Ángel Díaz José , Minguela Alfredo , Álvarez Beatriz , Serrano Cristina , Caballero Teresa , Rey Mercedes , Pérez Corral Ana , Cristina Fernández Jiménez María , Magro Elena , Lemes Angelina , Benavente Celina , Bañas Helena , Merino Juana , Castejon Celine , Gutierrez Olivier , Rabasa Pilar , Vescosi Gonçalves Matheus , Perez‐Andres Martin , Orfao Alberto ,   on behalf of the PNH working group of the Iberian Society of Cytometry (SIC)
Published: September 2016

Background

Although consensus guidelines have been proposed in 2010 for the diagnostic screening of paroxysmal nocturnal hemoglobinuria (PNH) by flow cytometry (FCM), so far no study has investigated the efficiency of such medical indications in multicentric vs. reference laboratory settings.

Methods

Here we evaluate the efficiency of consensus medical indications for PNH testing in 3,938 peripheral blood samples submitted to FCM testing in 24 laboratories in Spain and one reference center in Brazil.

Results

Overall, diagnostic screening based on consensus medical indications was highly efficient (14% of PNH+ samples) both in the multicenter setting in Spain (10%) and the reference laboratory in Brazil (16%). The highest frequency of PNH+ cases was observed among patients screened because of bone marrow (BM) failure syndrome (33%), particularly among those with aplastic anemia (AA; 45%) and to a less extent also a myelodysplastic syndrome (MDS; 10%). Among the other individuals studied, the most efficient medical indications for PNH screening included: hemolytic anemia (19%), hemoglobinuria (48%) and unexplained cytopenias (9%). In contrast, only a minor fraction of the patients who had been submitted for PNH testing because of unexplained thrombosis in the absence of cytopenia, were positive (0.4%).

Conclusions

In summary, our results demonstrate that the current medical indications for PNH screening by FCM are highly efficient, although improved screening algorithms are needed for patients presenting with thrombosis and normal blood cell counts. © 2016 International Clinical Cytometry Society
The potential for deep groundwater use by Acacia papyrocarpa (Western myall) in a water‐limited environment
Authors: Steggles Emma K. , Holland Kate L. , Chittleborough David J. , Doudle Samantha L. , Clarke Laurence J. , Watling Jennifer R. , Facelli José M.
Published: September 2016

Knowledge regarding the use of groundwater by plants has implications for successful mine rehabilitation and revegetation programs in water‐limited environments. In this study, we combined several approaches to investigate water sources used by Acacia papyrocarpa (Western myall) in the far west of South Australia, including stable isotopes, water potential, groundwater and soil chemistry, and root mapping techniques. Plant δ18O signatures and water potentials were compared against a range of possible sources: rainwater, surface soil water (≤1 m depth), and deep groundwater (>20 m depth). Our aim was to determine whether groundwater contributed to the mix of waters used by A. papyrocarpa.

Overall, we found that trees did not source surface soil water (≤1 m), and probably sourced deep soil water (i.e. >1 m) rather than deep groundwater. Groundwater, however, could not be dismissed as a potential source, as root mapping showed tree roots were capable of reaching groundwater at depths >20 m, and isotope results indicated a potential contribution by groundwater to tree water use. However, low osmotic potentials and/or high acidity levels were shown to pose likely barriers to groundwater uptake, at least at the time of sampling. We conclude that because groundwater salinity and acidity are spatially variable in this region, plants with extensive root systems may be able to utilize zones of groundwater with lower salinity and pH levels. Overall, this study contributes to our limited understanding of groundwater use by trees occurring in water‐limited environments where groundwater is extremely deep (>20 m depth).
Cascade SN2′–SNAr, Elimination, and 1,5‐Hydride Shift Reactions by Acetylacetone/Acetoacetic Esters: Synthesis of 9,10‐Dihydroacridines
Authors: Gupta Tanu , Bharadwaj Kishor Chandra , Singh Radhey M.
Published: September 2016

A reaction involving the use of acetylacetone/methyl acetoacetate and Morita–Baylis–Hillman acetates for the efficient, one‐pot, metal‐free synthesis of 9,10‐dihydroacridines at room temperature was developed. The cascade of reactions involved sequential SN2′–SNAr reactions, elimination, and reduction through ketene generation and hydride transfer. Evidence for hydride shift via a ketene intermediate was also discussed.
Biofuel and Methyl Levulinate from Biomass‐Derived Fractional Condensed Pyrolysis Oil and Alcohol
Authors: Westerhof Roel. J. M. , Oudenhoven Stijn R G. , Hu Xun , Heeres Hero J. , Li Chun‐Zhu , Garcia‐Perez Manuel , Kersten Sascha R. A.
Published: September 2016

The aim of this research was to evaluate the potential for the stabilization of biomass‐derived pyrolysis oils by using acid‐catalyzed (Amberlyst 70) reactions with alcohol (T=140–170 °C, P≈20 bar (1 bar=105 Pa)). The alcohol‐stabilized oils were further upgraded by catalytic hydrotreatment (T=400 °C, non‐sulfided NiMo/Al2O3 catalyst) to give a biofuel. The concept was evaluated experimentally in terms of overall mass and energy balances and biofuel properties. The pyrolysis oil used in this study was obtained by fractional condensation of pyrolysis vapors and had a very low water content that favored the equilibrium conversion of the stabilization reactions. The energy efficiency was between 44 and 48 %. Preliminary results with acid‐leached biomass showed that 43 % of levoglucosan in the pyrolysis oil was converted into methyl levulinate after the pyrolysis oil was purified. The proposed integrated concept of alcoholysis can be applied locally at the pyrolysis oil production site.
Using UAV acquired photography and structure from motion techniques for studying glacier landforms: application to the glacial flutes at Isfallsglaciären
Authors: Ely Jeremy C. , Graham Conor , Barr Iestyn D. , Rea Brice R. , Spagnolo Matteo , Evans Jeff
Published: September 2016

Glacier and ice sheet retreat exposes freshly deglaciated terrain which often contains small‐scale fragile geomorphological features which could provide insight into subglacial or submarginal processes. Subaerial exposure results in potentially rapid landscape modification or even disappearance of the minor‐relief landforms as wind, weather, water and vegetation impact on the newly exposed surface. Ongoing retreat of many ice masses means there is a growing opportunity to obtain high resolution geospatial data from glacier forelands to aid in the understanding of recent subglacial and submarginal processes. Here we used an unmanned aerial vehicle to capture close‐range aerial photography of the foreland of Isfallsglaciären, a small polythermal glacier situated in Swedish Lapland. An orthophoto and a digital elevation model with ~2 cm horizontal resolution were created from this photography using structure from motion software. These geospatial data was used to create a geomorphological map of the foreland, documenting moraines, fans, channels and flutes. The unprecedented resolution of the data enabled us to derive morphological metrics (length, width and relief) of the smallest flutes, which is not possible with other data products normally used for glacial landform metrics mapping. The map and flute metrics compare well with previous studies, highlighting the potential of this technique for rapidly documenting glacier foreland geomorphology at an unprecedented scale and resolution. The vast majority of flutes were found to have an associated stoss‐side boulder, with the remainder having a likely explanation for boulder absence (burial or erosion). Furthermore, the size of this boulder was found to strongly correlate with the width and relief of the lee‐side flute. This is consistent with the lee‐side cavity infill model of flute formation. Whether this model is applicable to all flutes, or multiple mechanisms are required, awaits further study. © 2016 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.
Bioturbation by gophers and marmots and its effects on conifer germination
Authors: Whitesides Clayton J. , Butler David R.
Published: September 2016

Although climate has been shown to have a considerable influence on alpine forest dynamics, many fine‐scale processes contribute to observable forest patterns. Disturbances created by burrowing mammals may provide conifer seedlings with refuge in previously inhospitable environments and may result in conifer invasion that is not directly associated with climate change. In Olympic National Park, Washington, USA, Olympic marmot (Marmota olympus) populations have declined. Abandoned marmot burrows, which may provide ideal sites for conifer establishment, now dot the alpine landscape. Similarly, in Glacier National Park, Montana, USA, pocket gophers (Thomomys talpoides) have disturbed large areas of alpine meadows at treeline. Field and laboratory analysis of gopher eskers and spoil mounds of abandoned marmot burrows illustrated that such sites are less compacted than soils in adjacent, undisturbed locations. Additionally, disturbed soils contained higher amounts of phosphorus and lower amounts of potassium and organic matter. Soils disturbed by gophers were cooler at the surface and warmer at depth than undisturbed soils, whereas marmot‐disturbed soils were warmer at the surface and cooler at depth. Experimental seed germination of subalpine fir (Abies lasiocarpa) was higher on mammal‐disturbed soils, and this was statistically significant for marmot‐disturbed soils. These findings suggest that fossorial mammal disturbances have the potential to affect conifer germination and establishment. Furthermore, this research initiates the dialogue for future research on the distinct morphological and behavioral influences of different fossorial mammals as zoogeomorphic agents and ecosystem engineers. Copyright © 2016 John Wiley & Sons, Ltd.
Predictive value of molecular remissions postconsolidation chemotherapy in patients with Core Binding Factor Acute Myeloid Leukemia (CBF‐AML) – a single center analysis
Authors: Deotare Uday , Shaheen Marwan , Brandwein Joseph M. , Pitcher Bethany , Kamel‐Reid Suzanne , Yee Karen W.L. , Schimmer Aaron , Minden Mark D. , Gupta Vikas , Schuh Andre C.
Published: September 2016

We analyzed the outcome of 80 sequential patients with core binding factor acute myeloid leukemia and evaluated the influence of molecular monitoring by quantitative reverse transcriptase polymerase chain reaction. With a median follow‐up of 5 years, the estimated 5‐year relapse‐free survival and overall survival were 58% and 66%, respectively. Patients who were in molecular remission at the completion of consolidation chemotherapy had a 21% risk of relapse, while the relapse risk for those in molecular remission at the end of 2 years was 5.5%. Our data indicate that postconsolidation molecular remission does not necessarily preclude disease relapse and further monitoring is required. In contrast, molecular negativity by quantitative reverse transcriptase polymerase chain reaction at the end of 2 years is associated with a low risk of relapse.
BRAFV600E and MAP2K1 mutations in Langerhans cell histiocytosis occur predominantly in children
Authors: Zeng Kaixuan , Ohshima Koichi , Liu Yixiong , Zhang Weichen , Wang Lu , Fan Linni , Li Mingyang , Li Xia , Wang Zhe , Guo Shuangping , Yan Qingguo , Guo Ying
Published: September 2016

Langerhans cell histiocytosis (LCH) is a proliferative disease of CD1a+/CD207+ dendritic cells. Recurrent BRAFV600E and MAP2K1 mutations have been reported in LCH. To investigate the relationship among the mutation, clinical findings, and differentiation status of LCH, respectively, we studied 97 cases of LCH by using Sanger sequencing and immunohistochemistry. The mutually exclusive BRAFV600E and MAP2K1 mutation rates were 32% and 17.5%, respectively. All MAP2K1 mutations were missense mutations without any in‐frame deletions; 2 new recurrent missense mutations (ie, p.E38K and p.P105S) were also found. More BRAFV600E and MAP2K1 mutations occurred in children compared with those in adult patients (P = .001), and BRAF mutation was correlated with relapse (P = .009). To the differentiation‐related markers, the BRAF/MAP2K1‐mut LCH expressed CD14 but rarely expressed CD83 or CD86 (P < .001). On the contrary, BRAF/MAP2K1‐wt LCH cells rarely expressed CD14 but expressed CD86, and some also expressed CD83 (P < .001). This indicated that the BRAF/MAP2K1‐mut LCH cells had a more immature state than BRAF/MAP2K1‐wt LCH cells. Moreover, we also found the BRAFV600E and MAP2K1 mutations were significantly associated with pERK expression (P < .001). Therefore, the RAS/RAF/MEK/ERK pathway might play a more important role in children than in adult patients with LCH.
Collecting and Using Postgraduate Outcomes Data at a Private College
Authors: Laguilles Jerold S.
Published: September 2016

This chapter describes the background and process for collecting postgraduation outcomes data at a 4‐year not‐for‐profit private college. The strategies, analyses, and reporting of this data‐collection effort are highlighted with the use of a case study.
First‐Destination Outcomes at a Public Research University: Aligning Our Survey With a Set of Standards
Authors: Kelly Heather A. , Walters Allison M.
Published: September 2016

Comprehensive data are essential to answer questions from prospective students, parents, and private and public entities about the cost of college and students’ return on investment, as well as to demonstrate how colleges and universities are helping to prepare the future workforce. An evolutionary data‐collection process, efforts to improve the distribution of results, and implications will be discussed to inform public research universities hoping to begin or refine a first‐destination survey.
Community Colleges: Preparing Students for Diverse Careers
Authors: Guthrie Lou A.
Published: September 2016

Postgraduation outcomes for community college students are complex. In addition to traditional job placement and earnings information, transferring to a 4‐year institution is a positive first‐destination outcome. Furthermore, community college students may have education and career goals that do not include earning a degree. Community college measures of success, two case studies, and how community colleges use outcomes data will be discussed.
Magnesium alloys: A stony pathway from intensive research to clinical reality. Different test methods and approval‐related considerations
Authors: Willbold Elmar , Weizbauer Andreas , Loos Anneke , Seitz Jan‐Marten , Angrisani Nina , Windhagen Henning , Reifenrath Janin
Published: September 2016

The first degradable implant made of a magnesium alloy, a compression screw, was launched to the clinical market in March 2013. Many different complex considerations are required for the marketing authorization of degradable implant materials. This review gives an overview of existing and proposed standards for implant testing for marketing approval. Furthermore, different commonin vitroandin vivotesting methods are discussed. In some cases, animal tests are inevitable to investigate the biological safety of a novel medical material. The choice of an appropriate animal model is as important as subsequent histological examination. Furthermore, this review focuses on the results of various mechanical tests to investigate the stability of implants for temporary use. All the above aspects are examined in the context of development and testing of magnesium‐based biomaterials and their progress them from bench to bedside. A brief history of the first market launch of a magnesium‐based degradable implant is given. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 329–347, 2017.
Harmonization Study Between LC‐MS/MS and Diasorin RIA for Measurement of 25‐Hydroxyvitamin D Concentrations in a Large Population Survey
Authors: Berry Diane J. , Dutton John , Fraser William D. , Järvelin Marjo‐Riitta , Hyppönen Elina
Published: September 2016

Background

Population‐based research on vitamin D has increased dramatically in recent years. Such studies are typically reliant on assay procedures to measure reliable and comparable levels of 25‐hydroxyvitamin D [25(OH)D] concentrations.

Methods

Concentrations of 25(OH)D3 and 25(OH)D2 were measured using LC‐MS/MS in 5,915 participants (aged 31 years) of Northern Finland Birth Cohort 1966. Blood samples were assayed in batches over a course of 18 months. As anomalies were present in the measurements, 200 samples were reassayed using Diasorin RIA. Agreement between measurements was assessed by Passing–Bablok regression and limits of agreement (LoA). To harmonize LC‐MS/MS with Diasorin RIA measurements, formulae were derived from the LoA.

Results

Concentrations measured by LC‐MS/MS were much higher than those measured by Diasorin RIA, with a mean difference of 12.9 ng/ml. Constant variation was evident between batch measurements after log transformation. Statistical formula was applied separately for each batch of LC‐MS/MS measurements, enabling us to remove both the constant and proportional bias that was evident prior to the transformation.

Conclusion

Despite the introduction of schemes/programs to improve accuracy of assays to measure 25(OH)D, significant differences can still happen. In these instances, methods to harmonize measurements based on a relatively small number of replicates can be successfully applied to establish confidence and to enable between‐study comparisons.
Determination of Fetal RHD Genotype Including the RHD Pseudogene in Maternal Plasma
Authors: Ziza Karen Chinoca , Liao Adolfo Wenjaw , Dezan Marcia , Dinardo Carla Luana , Jens Eduardo , Francisco Rossana Pulcineli Vieira , Junior Alfredo Mendrone , Zugaib Marcelo , Levi José Eduardo
Published: September 2016

Objective

To examine the accuracy of fetal RHD genotype and RHD pseudogene determination in a multiethnical population.

Methods

Prospective study involving D‐negative pregnant women. Cell‐free DNA was extracted from 1 ml of maternal plasma by an automated system (MagNA Pure Compact, Roche) and real‐time PCR was performed in triplicate targeting the RHD gene exons 5 and 7. Inconclusive samples underwent RHD pseudogene testing by real‐time PCR analysis employing novel primers and probe.

Results

A positive result was observed in 128/185 (69.2%) samples and negative in 50 (27.0%). Umbilical cord blood phenotype confirmed all cases with a positive or negative PCR result. Seven (3.8%) cases were found inconclusive (exon 7 amplification only) and RHD pseudogene testing with both conventional and real‐time PCR demonstrated a positive result in five of them, while two samples were also RHD pseudogene negative.

Conclusion

Real‐time PCR targeting RHD exons 5 and 7 simultaneously in maternal plasma is an accurate method for the diagnosis of fetal D genotype in our population. The RHD pseudogene real‐time PCR assay is feasible and is particularly useful in populations with a high prevalence of this allele.
Suitability of Watershed Models to Predict Distributed Hydrologic Response in the Awramba Watershed in Lake Tana Basin
Authors: Moges Mamaru A. , Schmitter Petra , Tilahun Seifu A. , Langan Simon , Dagnew Dessalegn C. , Akale Adugnaw T. , Steenhuis Tammo S.
Published: September 2016

Planning effective landscape interventions is an important tool to fight against land degradation and requires knowledge on spatial distribution of runoff. The objective of this paper was to test models that predict temporal and spatial distribution of runoff. The selected models were parameter‐efficient semi‐distributed watershed model (PED‐WM), Hydrologiska Byrans Vattenbalansavdelning integrated hydrological modeling system (HBV‐IHMS), and Soil and Water Assessment Tool (SWAT). We choose 7‐km2 Awramba watershed in the Lake Tana basin with detailed hydrological information for testing these models. Discharge at the outlet, rainfall, and distributed information on infiltration rates, water table, and extent of the saturated area were collected from 2013 to 2015. The maximum saturated area was 6·5% of the watershed. Infiltration rates exceeded rainfall intensities 91% of the time. Hence, saturation excess runoff was the main runoff mechanism. Models were calibrated for the rainy seasons in 2013 and 2014 and validated for 2015. For daily flow validation, the PED‐WM model (Nash–Sutcliff efficiency, NSE = 0·61) outperformed HBV‐IHMS (NSE = 0·51) and SWAT (NSE = 0·48). Performance on monthly time step was similar. Difference in model behavior depended on runoff mechanism. In PED‐WM, saturation excess is the main direct runoff process and could predict the maximum extent of the saturated area closely at 6·9%. HBV‐IHMS model runoff simulation depended on soil moisture status and evapotranspiration, and hence was able to simulate saturation excess flow but not the extent of the saturated area. SWAT, where infiltration excess is the main runoff mechanism, could only predict the monthly discharges well. This study shows that prevailing runoff mechanisms and distribution of runoff source areas should be used for proper model selection. Copyright © 2016 John Wiley & Sons, Ltd.
Optical absorbers based on strong interference in ultra‐thin films
Authors: Kats Mikhail A. , Capasso Federico
Published: September 2016

Optical absorbers find uses in a wide array of applications across the electromagnetic spectrum, including photovoltaic and photochemical cells, photodetectors, optical filters, stealth technology, and thermal light sources. Recent efforts have sought to reduce the footprint of optical absorbers, conventionally based on graded structures or Fabry‐Perot‐type cavities, by using emerging concepts in plasmonics, metamaterials, and metasurfaces. Unfortunately, these new absorber designs require patterning on subwavelength length scales, and are therefore impractical for many large‐scale optical and optoelectronic devices.

In this article, we summarize recent progress in the development of optical absorbers based on lossy films with thicknesses significantly smaller than the incident optical wavelength. These structures have a small footprint and require no nanoscale patterning. We outline the theoretical foundation of these absorbers based on “ultra‐thin‐film interference”, including the concepts of loss‐induced phase shifts and critical coupling, and then review several applications, including ultra‐thin color coatings, decorative photovoltaics, high‐efficiency photochemical cells, and infrared scene generators.

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Plasma membrane‐bound G protein–coupled bile acid receptor attenuates liver ischemia/reperfusion injury via the inhibition of toll‐like receptor 4 signaling in mice
Authors: Yang Haojun , Zhou Haoming , Zhuang Lin , Auwerx Johan , Schoonjans Kristina , Wang Xuehao , Feng Cheng , Lu Ling
Published: September 2016

The plasma membrane‐bound G protein–coupled bile acid receptor (TGR5) displays varied levels of expression in different tissues. TGR5‐induced liver protection has been demonstrated during several liver diseases, except during ischemia/reperfusion injury (IRI). Male adult wild‐type and TGR5 knockout (KO) mice were subjected to liver partial warm ischemia/reperfusion. Hepatic injury was evaluated based on serum alanine aminotransferase and serum aspartate aminotransferase. Liver histological injury and inflammatory cell infiltration were evaluated in tissue sections using liver immunohistochemical analysis. We used quantitative real‐time polymerase chain reaction to analyze the liver expression of inflammatory cytokines. The toll‐like receptor 4 (TLR4) signaling pathway and its related apoptotic molecules were investigated after reperfusion. Moreover, the effect of TGR5 on inflammation was determined with TGR5+/+ or TGR5−/− primary bone marrow–derived macrophages in vitro. TGR5 significantly attenuated liver damage after IRI. As demonstrated by in vivo experiments, TGR5 significantly reduced the up‐regulation of the TLR4–nuclear factor kappa B (NF‐κB) pathway and inhibited caspase 8 activation after IRI. Later experiments showed that TGR5 KO significantly increased the expression of TLR4–NF‐κB signaling molecules and promoted hepatocellular apoptosis. In addition, in vitro experiments showed that overexpression of 6alpha‐ethyl‐23(S)‐methylcholic acid (INT‐777)–activated TGR5 directly down‐regulated tumor necrosis factor α (TNF‐α) and interleukin (IL) 6 expression but up‐regulated IL10 expression in hypoxia/reoxygenation–induced primary TGR5+/+ macrophages. Moreover, the expression of TLR4–NF‐κB signaling molecules was significantly inhibited by the activation of TGR5. Importantly, these results were completely reversed in primary TGR5−/− macrophages. This work is the first to provide evidence for a TGR5‐inhibited inflammatory response in IRI through suppression of the TLR4–NF‐κB pathway, which may be critical in reducing related inflammatory molecules and modulating innate inflammation. Liver Transplantation 23:63–74 2017 AASLD.
Lifetime of environmental/thermal barrier coatings deposited on a niobium silicide composite with boron containing M7Si6‐based bond coat
Authors: Braun R. , Lange A. , Schulz U. , Portebois L. , Mathieu S. , Vilasi M. , Drawin S.
Published: September 2016

Environmental/thermal barrier coatings (E/TBCs) of yttria partially stabilised zirconia (YSZ), gadolinium zirconate (GZO) and a combination of Y2SiO5 and GZO were applied on a Nb/Nb5Si3‐based alloy with the nominal composition of Nb‐25Ti‐8Hf‐2Cr‐2Al‐16Si (at%). A B‐containing M7Si6‐based (M = Ti, Nb, Fe, Cr) layer produced by pack cementation was used as bond coat. The ceramic topcoats were manufactured by electron‐beam physical vapour deposition (YSZ and GZO) and magnetron sputtering (Y2SiO5). The different E/TBC systems were tested under cyclic oxidation conditions in air at 1100 and 1200 °C. Lifetimes exceeding 1000 cycles of 1 h dwell time at 1100 °C were determined. The YSZ, GZO and combined Y2SiO5 + GZO topcoats did not spall off during the maximum exposure time, exhibiting good adherence to the thermally grown oxide scale which consisted of mixed oxides of Fe, Ti, Cr and Nb embedded in silica. For the E/TBC systems with YSZ and GZO which were thermally cycled at 1200 °C, lifetimes up to 850 cycles were measured; that of the system with a combined Y2SiO5 + GZO topcoat exceeded again 1000 cycles.
S100A6 promotes cell proliferation in human nasopharyngeal carcinoma via the p38/MAPK signaling pathway
Authors: Li Anchuan , Shi Dingbo , Xu Benhua , Wang Jingshu , Tang Yan‐Lai , Xiao WeiWei , Shen Guanzhu , Deng Wuguo , Zhao Chong
Published: September 2016

An elevated level of S100A6 is associated with poor outcomes of many tumor types, but, how S100A6 contributes to nasopharyngeal carcinoma (NPC) progression remains unknown. Here, we investigated the expression and prognostic significance of S100A6 in NPC and explored the molecular mechanisms under­lying the role of S100A6 in NPC development. The results showed that S100A6 was markedly up‐regulated in NPC tissues and cell lines compared to paired peritumoral normal tissues and a normal nasopharyngeal epithelial cell line, respectively. In tissues from 92 NPC patients, high S100A6 expression was associated with advanced N stage, locoregional failure and disease progression and was predictive of poor locoregional recurrence‐free survival (LRRFS, P = 0.001) and progression‐free survival (PFS, P = 0.001). Multivariate analysis showed that S100A6 is an independent prognostic factor for LRRFS and PFS. Silencing S100A6 using siRNA or shRNA significantly suppressed NPC cell proliferation, colony formation and p38/mitogen‐activated protein kinase (MAPK) activity in vitro and inhibited tumor growth in a xenograft mouse model of NPC. In contrast, overexpressing S100A6 via plasmid transfection resulted in increased NPC cell proliferation and p38/MAPK activation. S100A6‐induced proliferation was abolished by a p38 inhibitor. In summary, S100A6 may be a new prognostic marker of NPC and may promote NPC development via the activation of p38/MAPK signaling pathways. These findings suggest S100A6/p38/MAPK signaling as a potential therapeutic target for NPC. © 2016 Wiley Periodicals, Inc.
p16INK4A induces senescence and inhibits EMT through microRNA‐141/microRNA‐146b‐5p‐dependent repression of AUF1
Authors: Al‐Khalaf Huda H. , Aboussekhra Abdelilah
Published: September 2016

Senescence and epithelial‐to‐mesenchymal transition (EMT) processes are under the control of common tumor suppressor proteins, EMT transcription factors, and microRNAs. However, the molecular mechanisms that coordinate the functional link between senescence and EMT are still elusive. We have shown here that p16INK4A‐related induction of senescence is mediated through miR‐141 and miR‐146b‐5p. These two microRNAs are up‐regulated in aging human fibroblast and epithelial cells. Furthermore, miR‐141 and miR146b‐5p trigger cell cycle arrest at G1 phase and induce senescence in primary human fibroblasts and breast cancer cells in the presence and absence of p16INK4A. Like p16INK4A‐induced senescence, miR‐141/miR146b‐5p‐related senescence is not associated with secretory phenotype, and is mediated through the RNA binding protein AUF1. We have further demonstrated that p16INK4A and its downstream miRNA targets inhibit EMT through suppressing the EMT inducer ZEB1 in an AUF1‐dependent manner. Indeed, AUF1 binds the mRNA of this gene leading to increase in its level. These results indicate that p16INK4A controls both senescence and EMT through repressing EMT‐related transcription factor via miR‐141/miR146b‐5p and their target AUF1. This sheds more light on the molecular basis of the tumor suppressive functions of p16INK4A, which represses both the proliferative and the migratory/invasive capacities of cells. © 2016 Wiley Periodicals, Inc.
Detection and evaluation of estrogen DNA‐adducts and their carcinogenic effects in cultured human cells using biotinylated estradiol
Authors: Tripathi Kaushlendra , Mani Chinnadurai , Somasagara Ranganatha R. , Clark David W. , Ananthapur Venkateshwari , Vinaya Kambappa , Palle Komaraiah
Published: September 2016

The normal female reproductive hormone estrogen has been linked with increased risk of breast and many other forms of cancer. This is largely due to metabolic conversion of estrogens into highly reactive catechol estrogen quinones which can interact with DNA and cause a variety of DNA adducts and lesions. Detection and analysis of these adducts and their associated cellular responses involve complex chemical, enzymatic, and LC‐MS based methods, which are both laborious and require specialized expertise and instrumentation. Herein, we show that using a biotin‐labeled estradiol allows immunodetection of estrogen‐induced DNA adducts by slot blot and single‐cell molecular combing and proximity ligation assays. The biotinylated and unlabeled estradiols induced similar levels of DNA single and double strand breaks as measured by comet assays. Using biotinylated estrogen, we further show that estrogens are able to activate the Fanconi anemia‐BRCA tumor suppressor pathway and cause DNA strand breaks and oxidatively modified DNA bases as well as gross chromosomal aberrations. Utilization of biotin‐labeled estrogens could be a powerful tool to detect estrogen adducts and associated DNA damage, and to track estrogen adduct‐induced cellular responses and carcinogenic mechanisms in cultured cells. The techniques presented here allow simple and rapid detection and quantitation of estrogen adducts by slot blot as well as direct visualization on the DNA strand and could pave the way for developing new treatments to protect the genome from the effects of reactive estrogen metabolites. © 2016 Wiley Periodicals, Inc.
A singular reaction‐diffusion equation associated with brain lactate kinetics
Authors: Miranville Alain
Published: September 2016

Our aim in this paper is to study the well‐posedness of a singular reaction‐diffusion equation which is related with brain lactate kinetics, when spatial diffusion is taken into account. Copyright © 2016 John Wiley & Sons, Ltd.
Tensile versus AFM testing of electrospun PVA nanofibers: Bridging the gap from Microscale to nanoscale
Authors: Neugirg Benedikt R. , Burgard Matthias , Greiner Andreas , Fery Andreas
Published: September 2016

Design and application of mechanically extraordinary nanofibers requires their full comprehension, based on conclusive testing methods. Electrospun polymer nanofibers, for instance, show a progressive and pronounced increase in their Young's moduli when diameters decrease below the µm scale. Measurement of mechanical properties in this diameter range is challenging and in the vast majority of reports, two classes of methods are commonly used: highly sensitive tensile testing and atomic force microscopy three‐point deformation testing. Despite the methods' inherent dissimilarity, we resolve their conformity for the first time, with respect to the determination of Young's moduli. Here, we benchmark them against each other for electrospun polyvinyl‐alcohol nanofibers, a well‐defined model system. Our results provide an experimental basis for a comprehensive understanding of nanofiber structures and its implications on their mechanical properties. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2418–2424
The intervening removable affinity tag (iRAT) production system facilitates Fv antibody fragment‐mediated crystallography
Authors: Nomura Yayoi , Sato Yumi , Suno Ryoji , Horita Shoichiro , Iwata So , Nomura Norimichi
Published: September 2016

Fv antibody fragments have been used as co‐crystallization partners in structural biology, particularly in membrane protein crystallography. However, there are inherent technical issues associated with the large‐scale production of soluble, functional Fv fragments through conventional methods in various expression systems. To circumvent these problems, we developed a new method, in which a single synthetic polyprotein consisting of a variable light (VL) domain, an intervening removable affinity tag (iRAT), and a variable heavy (VH) domain is expressed by a Gram‐positive bacterial secretion system. This method ensures stoichiometric expression of VL and VH from the monocistronic construct followed by proper folding and assembly of the two variable domains. The iRAT segment can be removed by a site‐specific protease during the purification process to yield tag‐free Fv fragments suitable for crystallization trials. In vitro refolding step is not required to obtain correctly folded Fv fragments. As a proof of concept, we tested the iRAT‐based production of multiple Fv fragments, including a crystallization chaperone for a mammalian membrane protein as well as FDA‐approved therapeutic antibodies. The resulting Fv fragments were functionally active and crystallized in complex with the target proteins. The iRAT system is a reliable, rapid and broadly applicable means of producing milligram quantities of Fv fragments for structural and biochemical studies.
Effects of ligand binding on the stability of aldo–keto reductases: Implications for stabilizer or destabilizer chaperones
Authors: Kabir Aurangazeb , Honda Ryo P. , Kamatari Yuji O. , Endo Satoshi , Fukuoka Mayuko , Kuwata Kazuo
Published: September 2016

Ligands such as enzyme inhibitors stabilize the native conformation of a protein upon binding to the native state, but some compounds destabilize the native conformation upon binding to the non‐native state. The former ligands are termed “stabilizer chaperones” and the latter ones “destabilizer chaperones.” Because the stabilization effects are essential for the medical chaperone (MC) hypothesis, here we have formulated a thermodynamic system consisting of a ligand and a protein in its native‐ and non‐native state. Using the differential scanning fluorimetry and the circular dichroism varying the urea concentration and temperature, we found that when the coenzyme NADP+ was absent, inhibitors such as isolithocholic acid stabilized the aldo–keto reductase AKR1A1 upon binding, which showed actually the three‐state folding, but destabilized AKR1B10. In contrast, in the presence of NADP+, they destabilized AKR1A1 and stabilized AKR1B10. To explain these phenomena, we decomposed the free energy of stabilization (ΔΔG) into its enthalpy (ΔΔH) and entropy (ΔΔS) components. Then we found that in a relatively unstable protein showing the three‐state folding, native conformation was stabilized by the negative ΔΔH in association with the negative ΔΔS, suggesting that the stabilizer chaperon decreases the conformational fluctuation of the target protein or increase its hydration. However, in other cases, ΔΔG was essentially determined by the delicate balance between ΔΔH and ΔΔS. The proposed thermodynamic formalism is applicable to the system including multiple ligands with allosteric interactions. These findings would promote the development of screening strategies for MCs to regulate the target conformations.
Wide area network discrete feedback control on FastADR of a cluster of building air‐conditioning facilities
Authors: Kiyota Akihisa , Takahama Morio , Ninagawa Chuzo
Published: September 2016

Building air‐conditioning facilities are promising resources of the fast automated demand response (FastADR) aggregation. However, designing a closed‐loop control includes problems of strong nonlinear dynamic properties of the facility and large sampling period due to building facility communications. This paper proposes an original aggregated transfer function that approximates hundreds of air‐conditioners with large wide area network communication delays. © 2016 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.