bluuebunny/crossref_metadata_2025 huggingface dataset:
Reactive Oxygen Species Release, Alkylating Ability, and DNA Interactions of a Pterocarpanquinone: A Test Case for Electrochemistry
Authors: Silva Thaissa L. , Ferreira Fabricia R. , de Vasconcelos Camila C. , da Silva Rosanny Christhinny , Lima Dimas José da P. , Costa Paulo R. R. , Netto Chaquip D. , Goulart Marília O. F.
Published: October 2016

The electrochemistry of a redox‐based bioactive pterocarpanquinone, designated as LQB‐118, and its precursor chromenquinone (CQ) was investigated in protic and aprotic media with a focus on the reduction mechanism in both media, the reactivity with oxygen, and the interaction with biological targets, such as DNA. UV/Vis spectroelectrochemistry clarified the proposed mechanism. The appearance of bands at λ=331, 400, and 600 nm suggests the generation of transient quinonemethides (QM). Electrochemical experiments revealed homogeneous electron transfer to oxygen. LQB‐118 itself interacts with calf‐thymus DNA and ssDNA in solution. It, and its electrogenerated intermediates, have been shown to decrease the diagnostic oxidation peaks of guanosine and adenosine residues. These results, together with electrochemical evidence for the formation of QMs and the reductive addition of thiols, partly explain the reported cytotoxic and parasiticidal effects of this quinone. Overall, the electrochemical methods do well to predict the molecular mechanism of the biological activity of the present class of compounds. As an additional competitive advantage, electrochemistry allows reductive cleavage in situ, the characterization of the generated intermediate, the calculation of the number of transferred electrons, and positively mimics in vitro and in vivo experiments.
ROSA—a fast extension of partial least squares regression for multiblock data analysis
Authors: Liland Kristian Hovde , Næs Tormod , Indahl Ulf G.
Published: October 2016

We present the response‐oriented sequential alternation (ROSA) method for multiblock data analysis. ROSA is a novel and transparent multiblock extension of the partial least squares regression (PLSR). According to a “winner takes all” approach, each component of the model is calculated from the block of predictors that most reduces the current residual error. The suggested algorithm is computationally fast compared with other multiblock methods because orthogonal scores and loading weights are calculated without deflation of the predictor blocks. Therefore, it can work effectively even with a large number of blocks included. The ROSA method is invariant to block scaling and ordering. The ROSA model has the same attributes (vectors of scores, loadings, and loading weights) as PLSR and is identical to PLSR modeling for the case with only one block of predictors.
Improved superresolution microscopy imaging by sparse deconvolution with an interframe penalty
Authors: Hugelier S. , Eilers P. H. C. , Devos O. , Ruckebusch C.
Published: October 2016

Penalized regression with a combination of sparseness and an interframe penalty is explored for image deconvolution in wide‐field single‐molecule fluorescence microscopy. The aim is to reconstruct superresolution images, which can be achieved by averaging the positions and intensities of individual fluorophores obtained from the analysis of successive frames. Sparsity of the fluorophore distribution in the spatial domain is obtained with an L0‐norm penalty on estimated fluorophore intensities, effectively constraining the number of fluorophores per frame. Simultaneously, continuity of the fluorophore localizations in the time mode is obtained by penalizing the total numbers of pixel status changes between successive frames. We implemented the interframe penalty in a sparse deconvolution algorithm (sparse image deconvolution and reconstruction) for improved imaging of densely labeled biological samples. For simulated and real biological data, we show that more accurate estimates of the final superresolution images of cellular structures can be obtained.
Optimal Bicelle Size q for Solution NMR Studies of the Protein Transmembrane Partition
Authors: Piai Alessandro , Fu Qingshan , Dev Jyoti , Chou James J.
Published: October 2016

Structural characterization of transmembrane proteins in isotropic bicelles has become an increasingly popular application of solution NMR spectroscopy, as the fast‐tumbling bicelles are membrane‐like, yet can often yield spectral quality comparable to those of detergent micelles. While larger bicelles are closer to the true lipid bilayer, it remains unclear how large the bicelles need to be to allow accurate assessment of the protein transmembrane partition in the lipid bilayer. Here, we address the above question from the perspective of the protein residing in the bicelles, through systematic measurement of the protein chemical shift and transmembrane partition at different lipid/detergent ratios (q), ranging from 0.3 to 0.7, using the transmembrane domain of the human Fas receptor as model system. We found that the lipid environment of the bicelles, as reflected by the protein chemical shift, begins to be perturbed when q is reduced to below 0.6. We also implemented a solvent paramagnetic relaxation enhancement (PRE) approach for bicelles to show that the protein transmembrane partition in bicelles with q=0.5 and 0.7 are very similar, but at q=0.3 the solvent PRE profile is significantly different. Our data indicate that q values between 0.5 and 0.6 are a good compromise between high resolution NMR and closeness to the membrane environment, and allow accurate characterization of the protein position in the lipid bilayer.
The Brønsted Acid‐Catalyzed, Enantioselective Aza‐Diels–Alder Reaction for the Direct Synthesis of Chiral Piperidones
Authors: Weilbeer Claudia , Sickert Marcel , Naumov Sergei , Schneider Christoph
Published: October 2016

We disclose herein the first enantioselective aza‐Diels–Alder reaction of β‐alkyl‐substituted vinylketene silyl‐O,O‐acetals and imines furnishing a broad range of optically highly enriched 4‐alkyl‐substituted 2‐piperidones. As a catalyst for this one‐pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring‐closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds.
Total Synthesis of Gelsedilam by Means of a Thiol‐Mediated Diastereoselective Conjugate Addition–Aldol Reaction
Authors: Huang You‐Ming , Liu Yang , Zheng Chang‐Wu , Jin Qiao‐Wen , Pan Lu , Pan Ren‐Ming , Liu Jun , Zhao Gang
Published: October 2016

The total synthesis of gelsedilam, which features a highly diastereoselective thiol conjugate addition–intramolecular aldol reaction to install the strained and caged [3.2.2] bridged ring system and highly efficient NiCl2/NaBH4‐mediated four‐step transformation in one‐pot to construct its five‐membered lactam ring is reported. The synthesis requires only 18 linear steps from the known compounds, providing useful strategies for the construction of the intricate ring system in the synthesis of related gelsedine‐type alkaloids.
Influence of the Thiol Anchor on the Orientation of Surface‐Grafted dsDNA Assemblies
Authors: Su Qiang , Nöll Gilbert
Published: October 2016

The orientation of surface‐grafted dsDNA assemblies relative to the surface depends strongly on the nature of the employed thiol anchor. This was shown by ssDNA capture probe strands of 20 bases grafted to a gold surface by three dithiane rings or a single mercaptohexyl group. The capture probe strands were hybridized to one end of complementary ssDNA strands (target) comprising 40, 60, or 80 bases (T40, T60, and T80). At the other end of the targets a fluorophore‐labeled reporter probe ssDNA strand of 20 bases was hybridized. To stiffen the DNA assemblies, the targets T60 and T80 were further hybridized to ssDNA patches of 20 or 40 bases. Whether the fluorescence intensity, and thus the distance between surface and fluorophore, increases or decreases with increasing target length depends on the thiol anchor. Attempts were made to heal the nicks that are present in the formed dsDNA assemblies by ligation. For enzymatic ligation, the presence of a phosphate at the 5′‐end of the reporter probe and a patch is required, which may also influence the fluorescence intensity.
Syntheses and Photophysical Properties of meso‐Phenylene ridged Boron Dipyrromethene Monomers, Dimers and Trimer
Authors: Li Tingting , Gu Wei , Yu Changjiang , Lv Xiaokang , Wang Hua , Hao Erhong , Jiao Lijuan
Published: October 2016

Multichromophoric boron dipyrromethene (BODIPY) dyes have been efficiently synthesized from a one‐pot condensation of acyl chloride with 2,4‐dimethylpyrrole and have been converted to energy transfer cassettes through a one‐pot Knoevenagel condensation. Various BODIPYs containing 2‐ketopyrrole unit were also isolated as the side products and one of their BF2 complex was also isolated from these condensation reactions. The fluorescence quantum yields of these phenylene bridged dimers and trimer are much lower than those of their corresponding monomers. A significant decrease of the fluorescence quantum yield was observed in most polar solvents for these dimers and trimer, which may be due to a possible symmetry breaking resulted intramolecular charge transfer (ICT) in the excited state. Efficient energy transfer between the donor and acceptor was observed in these energy transfer cassettes, which could be useful as large pseudo‐Stokes shift fluorescent dyes with potential applications in diverse fields.
Sudden death and its risk factors after atrioventricular junction ablation and pacemaker implantation in patients with atrial fibrillation
Authors: Wang Ru‐Xing , Lee Hon‐Chi , Li Jia‐Ping , Hodge David O. , Cha Yong‐Mei , Friedman Paul A. , Munger Thomas M. , Srivathsan Komandoor , Pavri Behzad B. , Shen Win‐Kuang
Published: October 2016

Background

Although sudden death (SD) is a rare complication after atrioventricular junction (AVJ) ablation and permanent pacemaker implantation, the risk factors leading to this SD remain unknown. The purpose of this study was to investigate SD and its risk factors after ablate‐and‐pace strategy for rate control in atrial fibrillation (AF) patients during long‐term follow‐up.

Hypothesis

Methods

From January 2005 to December 2009, we enrolled into this study 517 AF patients with AVJ ablation and right ventricular pacemaker implantation. Patients were divided into 2 groups, SD and non‐SD. Cox proportional hazards models were used to assess potential risk factors for overall mortality and SD.

Results

During a mean follow‐up of 25.8 ± 18.6 months (range, 3 days to 63.8 months), 53 patients died (15 with SD). Cox proportional hazards models showed that the presence of congestive heart failure, New York Heart Association functional class, chronic renal failure, and nonsustained ventricular tachycardia were risk factors that predicted overall mortality. For SD, the presence of dilated cardiomyopathy and mitral stenosis were associated risk factors. SD was exclusively seen in patients who had narrow QRS complex or right bundle branch block prior to AVJ ablation and pacemaker implantation; SD was not seen in any patient with preexisting complete left bundle branch block.

Conclusions

Dilated cardiomyopathy, mitral stenosis, and baseline QRS morphology should be examined as potential risk factors for SD after AVJ ablation and pacemaker implantation.
Performance and energy efficiency analysis of HPC physics simulation applications in a cluster of ARM processors
Authors: Bez Jean Luca , Bernart Eliezer E. , dos Santos Fernando F. , Schnorr Lucas Mello , Navaux Philippe Olivier Alexandre
Published: October 2016

We analyze the feasibility and energy efficiency of using an unconventional cluster of low‐power Advanced RISC Machines processors to execute two scientific parallel applications. For this purpose, we have selected two applications that present high computational and communication cost: the Ondes3D that simulates geophysical events, and the all‐pairs N‐Body that simulates astrophysical events. We compare and discuss the impact of different compilation directives and processor frequency and how they interfere in Time‐to‐Solution and Energy‐to‐Solution. Our results demonstrate that by correctly tuning the application at compile time, for the Advanced RISC Machines architecture, we can considerably reduce the execution time and the energy spent by computing simulations. Furthermore, we observe reductions of up to 54.14% in Time‐to‐Solution and gains of up to 53.65% in Energy‐to‐Solution with two cores. Additionally, we consider the impact of two processor frequency governors on these metrics. Results indicate that the powersave governor presents a smaller instantaneous power consumption. However, it spends more time executing tasks, increasing the energy needed to achieve the solution. Finally, we correlate the energy consumption with the execution time in the experimental results using Pareto. These findings suggest that it is possible to explore low‐powered clusters for high‐performance computing applications by tuning application and hardware configuration to achieve energy efficiency. Copyright © 2016 John Wiley & Sons, Ltd.
Correlation between the O 2p Orbital and Redox Reaction in LiMn0.6Fe0.4PO4 Nanowires Studied by Soft X‐ray Absorption
Authors: Asakura Daisuke , Hosono Eiji , Okubo Masashi , Nanba Yusuke , Zhou Haoshen , Glans Per‐Anders , Guo Jinghua
Published: October 2016

The changes in the electronic structure of LiMn0.6Fe0.4PO4 nanowires during discharge processes were investigated by using ex situ soft X‐ray absorption spectroscopy. The Fe L‐edge X‐ray absorption spectrum attributes the potential plateau at 3.45 V versus Li/Li+ of the discharge curve to a reduction of Fe3+ to Fe2+. The Mn L‐edge X‐ray absorption spectra exhibit the Mn2+ multiplet structure throughout the discharge process, and the crystal‐field splitting was slightly enhanced upon full discharge. The configuration‐interaction full‐multiplet calculation for the X‐ray absorption spectra reveals that the charge‐transfer effect from O 2p to Mn 3d orbitals should be considerably small, unlike that from the O 2p to Fe 3d orbitals. Instead, the O K‐edge X‐ray absorption spectrum shows a clear spectral change during the discharge process, suggesting that the hybridization of O 2p orbitals with Fe 3d orbitals contributes essentially to the reduction.
Targeted and non‐targeted drug screening in whole blood by UHPLC‐TOF‐MS with data‐independent acquisition
Authors: Mollerup Christian Brinch , Dalsgaard Petur Weihe , Mardal Marie , Linnet Kristian
Published: October 2016

High‐resolution mass spectrometry (HRMS) is widely used for the drug screening of biological samples in clinical and forensic laboratories. With the continuous addition of new psychoactive substances (NPS), keeping such methods updated is challenging. HRMS allows for combined targeted and non‐targeted screening. First, peaks are identified by software algorithms, and identifications are based on reference standard data. Attempts are made to identify the remaining unknown peaks with in silico and literature data. However, several thousand peaks remain where most are unidentifiable or uninteresting in drug screening. The aims of the study were to apply a combined targeted and non‐targeted screening approach to authentic driving‐under‐the‐influence‐of‐drugs (DUID) samples (n = 44) and further validate the approach using whole‐blood samples spiked with 11 low‐dose synthetic benzodiazepine analogues (SBAs). Analytical data were acquired using ultra‐high‐performance liquid chromatography coupled with a time‐of‐flight mass spectrometer (UHPLC‐TOF‐MS) with data‐independent acquisition (DIA). We present a combined targeted and non‐targeted screening, where peak deconvolution and filtering reduced the number of peaks to inspect by three orders of magnitude, down to four peaks per DUID sample. The screening allowed for tentative identification of metabolites and drugs not included in the initial screening; 3 drugs and 14 metabolites were tentatively identified in the authentic DUID samples. Running targeted‐screening true‐positive identifications through the filters retained 73% of identifications. In the non‐targeted screening, nine of the spiked SBAs were identified in the concentration range of 0.005–0.1 mg/kg, of which three were tentatively identified at concentrations below those reported in the literature. Copyright © 2016 John Wiley & Sons, Ltd.
A review of subtropical community resistance and resilience to extreme cold spells
Authors: Boucek R. E. , Gaiser E. E. , Liu H. , Rehage J. S.
Published: October 2016

Forecasted changes in global climate predict not only shifts in average conditions but also changes in the frequency and intensity of climate extremes. In the subtropics, the passage of extreme cold spells functions as a major structuring force for ecological communities, and can incur substantial losses to biodiversity, agriculture, and infrastructure. If these events persist in the future, it is likely that their effects on subtropical communities and ecosystems will become more pronounced, as tropical species migrate poleward. Recent extreme cold spells in subtropical China (2008) and United States (2010) occurred in ecosystems that are the subject of long‐term ecological study, enabling key questions about cold spell affects to be addressed. In this study, we (1) discuss the meteorological drivers that resulted in these two extreme cold spells, and (2) use findings from case studies published in theEcosphereSpecial Feature on effects of extreme cold spells on the dynamics of subtropical communities, and on poleward expansion of tropical species and other previously published works to identify consistencies of subtropical community resilience and resistance to extreme cold spells. In this review, we highlight three consistent findings related to this particularly type of extreme climate event: (1) cold spells drive predictable community change in the subtropics by altering ratios of coexisting tropical and temperate species; (2) certain landscape features consistently affect subtropical resistance and resilience to extreme cold spells; and (3) native tropical species are more resistant and resilient to extreme cold spells than tropical nonnative taxa. Our review should improve forecasts of the response of subtropical community dynamics in scenarios where extreme cold spells either increase or decrease in frequency and intensity.
Structural Arrangement of 4‐[4‐(Dimethylamino)phenylazo]pyridine Push–Pull Molecules in Acidic Layered Hosts Solved by Experimental and Calculation Methods
Authors: Melánová Klára , Kovář Petr , Gamba Martina , Pospíšil Miroslav , Beneš Ludvík , Zima Vítězslav , Svoboda Jan , Miklík David , Bureš Filip , Knotek Petr
Published: October 2016

4‐[4‐(dimethylamino)phenylazo]pyridine (further denoted as G) representing a type of push–pull molecules can be intercalated into α‐ and γ‐modifications of zirconium phosphate (α‐ZrP and γ‐ZrP) and into zirconium (4‐sulfophenyl)phosphonate (ZrSPP). The obtained intercalates form single phases with interlayer distances of 12.75, 16.31, and 24.11 Å for α‐ZrP·0.2G·1.5H2O, γ‐ZrP·0.2G·1.5H2O, and ZrSPP·0.5G·1H2O, respectively. The increase of the interlayer distance upon intercalation suggests that the molecules of the intercalated guest lie parallel to the host layers. All intercalates were further characterized by IR and UV/Vis spectroscopy. The arrangement of the guests in the interlayer space was determined by molecular simulation methods. The calculations were performed separately for protonated and unprotonated forms of the guest in the models of hydrated and dehydrated α‐ZrP and γ‐ZrP intercalates. In the case of the α‐ZrP intercalate, the presence of interlayer water stabilizes the head‐to‐tail arrangement of the guest molecules. Dehydration of this intercalate disturbs their arrangement, mainly in the case of protonated guest molecules. In the case of dehydrated γ‐ZrP, the guest molecules are head‐to‐tail ordered, and the guest molecules in the hydrated form of γ‐ZrP are more disordered than in the dehydrated intercalate. The simulations also describe a layer shift present in the dehydrated γ‐ZrP intercalate, which explains why the rehydration of this intercalate is not possible.
Reducing polycyclic aromatic hydrocarbons (PAHs) formation in olive pomace oil using microwave pre‐heating of olive pomace
Authors: Kiralan Sündüz Sezer , Erdogdu Ferruh , Tekin Aziz
Published: October 2016

High temperature application during drying of olive pomace before solvent extraction leads to formation of polycyclic aromatic hydrocarbons (PAHs) and their eventual presence in the oil. Therefore, the objective of this study was to investigate a mitigation possibility of PAHs in olive pomace oil. For this purpose, microwave pre‐treatment was applied to the olive pomace before drying at 200°C to final moisture content of less than 5%. Effect of pre‐drying microwave process was carried out against drying at 200°C and vacuum drying. PAH content analysis of the solvent extracted oil was completed using a HPLC method with fluorescence detection (HPLC‐FLD). The results demonstrated that the pre‐microwave application led to 75% reduction of total PAHs content in olive pomace oil. This study highlighted the possibility of an alternative innovative strategy to apply in a process to suggest a simple solution for a significant industrial problem.

Practical applications: PAHs are serious problem in olive pomace oil. Removal of PAHs in olive pomace oil has a great importance because of their carcinogenic potential. Results show that PAHs are formed during drying of olive pomace at high temperature (200°C). This study reveals that microwave application was effective strategy to reduce PAHs in olive pomace oil. Therefore, drying process was modified with microwave pre‐heating application to produce high quality olive pomace oil.

In this study, the effect of microwave pre‐heating application before drying to reduce PAH formation in olive pomace oil is demonstrated. The eventual reduction of total PAH concentration in olive pomace oil indicated the effectiveness of this pre‐heating application.
Organic Superbases in Annulation with Propargylic Alcohols: Straightforward Synthesis of the Functionalized Oxazolopyrrolohexahydropyrimidine and Oxazolohexahydropyrimidoazepine Scaffolds
Authors: Trofimov Boris A. , Shemyakina Olesya A. , Mal'kina Anastasiya G. , Stepanov Anton V. , Volostnykh Ol'ga G. , Ushakov Igor' A. , Vashchenko Alexander V.
Published: October 2016

The popular organic superbases 1,5‐diazabicyclo[4.3.0]non‐5‐ene (DBN) and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) underwent annulation with electron‐deficient propargylic alcohols [EWG = CN, C(O)Ph, CO2Me] to afford functionalized condensed hexahydropyrimidine systems, [1,3]oxazolo[3,2‐a]pyrrolo[2,1‐b]hexahydropyrimidines and [1,3]oxazolo[3′,2′:3,4] hexahydropyrimido[1,2‐a]azepines, in good to high yields. The reactions proceeded regioselectively and, in most cases, stereoselectively under mild conditions (without catalyst, 20–25 °C). The synthesized compounds, owing to their potential rich chemistry, are novel promising precursors for pyrimidine‐based pharmaceuticals.
Specific ion effects on the particle size distributions of cell culture–derived influenza A virus particles within the Hofmeister series
Authors: Pieler Michael Martin , Heyse Anja , Wolff Michael Werner , Reichl Udo
Published: October 2016

Virus particle (VP) aggregation can have serious implications on clinical safety and efficacy of virus‐based therapeutics. Typically, VP are suspended in buffers to establish defined product properties. Salts used to achieve these properties show specific effects in chemical and biological systems in a reoccurring trend known as Hofmeister series (HS). Hofmeister series effects are ubiquitous and can affect colloidal particle systems. In this study, influences of different ions (anions: SO42−, HPO42−, Cl−, Br−, NO3−, I−; cations: K+, Na+, Li+, Mg2+, Ca2+) on particle size distributions of cell culture‐derived influenza VP were investigated. For the experimental setup, influenza virus A/Puerto Rico/8/34 (H1N1) VP produced in adherent and suspension Madin Darby canine kidney cells were used. Inactivated and concentrated virus harvests were dialyzed against buffers containing the ions of interest, followed by differential centrifugal sedimentation to measure particle size distributions. VP from both cell lines showed no aggregation over a wide range of buffers containing different salts in concentrations ≥60 mM. However, when dialyzed to low salt or Ca2+ buffers, VP produced in adherent cells showed increased aggregation compared to VP produced in suspension cells. Additionally, changes in VP diameters depending on specific ion concentrations were observed that partially reflected the HS trend.
Bioscrubber treatment of exhaust air from intensive pig production: Case study in northern Germany at mild climate condition
Authors: Liu Fang , Fiencke Claudia , Guo Jianbin , Rieth Robert , Cuhls Carsten , Dong Renjie , Pfeiffer Eva‐Maria
Published: October 2016

Treatment by field‐scale bioscrubber of exhaust air, including ammonia (NH3) and the greenhouse gases methane (CH4), nitrous oxide (N2O), and carbon dioxide (CO2), from 13 intensive pig production houses located in northern Germany were investigated in 2013 and 2015. NH3 removal efficiencies varied between 35 and 100% with an overall average value of 79% under the NH3 inlet fluctuations from 34 to 755 g d−1 m−3 in both 2013 and 2015. Results of the electron microscopic analyses demonstrated that the bacteria Nitrosomonas sp. and methanotrophs type I were the dominant NH3 and CH4 oxidizers, respectively. However, overall average removal efficiencies of CH4 was approximately zero, which means CH4 is hard to remove in bioscrubbers under normal operation. The pH of recirculation water in the bioscrubber varied from 6.1 to 8.1, and the bioscrubbers with low pH values (<7.0) had high NH3 removal efficiencies (>79%). Electrical conductivity was commonly used to diagnose the bioscrubbers’ performance; in the present study, electrical conductivity presented a significant linear relationship with dissolved inorganic nitrogen, which indicates the performance stability of the 13 selected bioscrubbers.
Immunophenotypic, cytogenetic, and mutational characterization of cell lines derived from myelodysplastic syndrome patients after progression to acute myeloid leukemia
Authors: Palau Anna , Mallo Mar , Palomo Laura , Rodríguez‐Hernández Ines , Diesch Jeannine , Campos Diana , Granada Isabel , Juncà Jordi , Drexler Hans G. , Solé Francesc , Buschbeck Marcus
Published: October 2016

Leukemia cell lines have been widely used in the hematology field to unravel mechanistic insights and to test new therapeutic strategies. Myelodysplastic syndromes (MDS) comprise a heterogeneous group of diseases that are characterized by ineffective hematopoiesis and frequent progress to acute myeloid leukemia (AML). A few cell lines have been established from MDS patients after progression to AML but their characterization is incomplete. Here we provide a detailed description of the immunophenotypic profile of the MDS‐derived cell lines SKK‐1, SKM‐1, F‐36P; and MOLM‐13. Specifically, we analyzed a comprehensive panel of markers that are currently applied in the diagnostic routine for myeloid disorders. To provide high‐resolution genetic data comprising copy number alterations and losses of heterozygosity we performed whole genome single nucleotide polymorphism‐based arrays and included the cell line OHN‐GM that harbors the frequent chromosome arm 5q deletion. Furthermore, we assessed the mutational status of 83 disease‐relevant genes. Our results provide a resource to the MDS and AML field that allows researchers to choose the best‐matching cell line for their functional studies. © 2016 Wiley Periodicals, Inc.
The Effect of Widowhood on Mental Health ‐ an Analysis of Anticipation Patterns Surrounding the Death of a Spouse
Authors: Siflinger Bettina
Published: October 2016

This study explores the effects of widowhood on mental health by taking into account the anticipation and adaptation to the partner's death. The empirical analysis uses representative panel data from the USA that are linked to administrative death records of the National Death Index. I estimate static and dynamic specifications of the panel probit model in which unobserved heterogeneity is modeled with correlated random effects. I find strong anticipation effects of the partner's death on the probability of depression, implying that the partner's death event cannot be assumed to be exogenous in econometric models. In the absence of any anticipation effects, the partner's death has long‐lasting mental health consequences, leading to a significantly slower adaptation to widowhood. The results suggest that both anticipation effects and adaptation effects can be attributed to a caregiver burden and to the cause of death. The findings of this study have important implications for designing adequate social policies for the elderly US population that alleviate the negative consequences of bereavement. Copyright © 2016 John Wiley & Sons, Ltd.
Processing and strengthening of 58S bioactive glass‐infiltrated titania scaffolds
Authors: Mesquita‐Guimarães J. , Leite M. A. , Souza J. C. M. , Henriques B. , Silva F. S. , Hotza D. , Boccaccini A. R. , Fredel M. C.
Published: October 2016

In this work, TiO2 ceramic scaffolds were fabricated by the replica method using polyurethane (PU) sponges. Suspensions with high solid content were used to achieve scaffolds with improved mechanical behavior. TiO2 ceramic suspensions were optimized by rheological studies using different additives. It was found that the composition with 0.5 wt % Darvan enhanced the covering of the sponge struts. PU sponges of 45 to 80 ppi (pore per inch) were well coated without clogging pores. A thermal treatment with varying holding times, temperatures and heating rates was adjusted. The influence of different pore sizes on mechanical strength was evaluated. It was possible to obtain TiO2 scaffolds with 90% porosity and high pore interconnectivity, having compressive strength exceeding 0.6 MPa. TiO2 scaffolds were filled up with a 58S bioactive glass suspension to impart bioactive character to the scaffolds. These hybrid structures presented mechanical strengthening of about 26–213% depending on their sponge porosity. The prediction for cells viability via zeta potential measures indicated that this hybrid material is very promising for scaffold application with −19 to −25 mV between pH of 7.35–7.45. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 590–600, 2017.
Immunogenicity of antigen‐conjugated biodegradable polydiacetylene liposomes administered mucosally
Authors: Abrams Jasmyn S. , Howe Savannah E. , Becerra Nathalie , Kohli Punit , Konjufca Vjollca
Published: October 2016

In this work, we report a protocol for synthesizing nanosize ovalbumin‐functionalized polydiacetylene (PDA) liposomes (LP‐Ova). We show that LP‐Ova administered per‐orally (p.o.) and subcutaneously (s.c.), without the use of adjuvants, induces high serum IgG1 titers. As reported previously using polystyrene nanoparticles (NPs), p.o.‐primed mice developed high titers of IgG2c and intestinal IgA following s.c. boosting immunization with LP‐Ova. Mice that received a single s.c. immunization with LP‐Ova did not develop serum IgG2c or intestinal IgA antibodies. Additionally, in s.c.‐immunized mice serum IgG1 titers decreased significantly by 3 months after immunization. In contrast, in mice primed p.o. and boosted s.c. with LP‐Ova, serum IgG1/IgG2c, and intestinal IgA antibody titers remained stable. Administration of LPs exerted no adverse effects on immunized mice as no morbidity or signs of toxicity were observed for the duration of the studies. These results indicate that antigen‐conjugated liposomes are immunogenic and confirm a previous report that mucosal priming followed by a s.c. boosting immunization is the most effective strategy for inducing long‐lasting mucosal IgA, as well as a polarized Th1/Th2 systemic response. In addition to being biodegradable and easily functionalized by conjugation, liposomes have a hollow core which can also be loaded with cargo, allowing for a targeted delivery of multiple antigens (or drugs) simultaneously. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 557–565, 2017.
p62 Promotes Amino Acid Sensitivity of mTOR Pathway and Hepatic Differentiation in Adult Liver Stem/Progenitor Cells
Authors: Sugiyama Masakazu , Yoshizumi Tomoharu , Yoshida Yoshihiro , Bekki Yuki , Matsumoto Yoshihiro , Yoshiya Shohei , Toshima Takeo , Ikegami Toru , Itoh Shinji , Harimoto Norifumi , Okano Shinji , Soejima Yuji , Shirabe Ken , Maehara Yoshihiko
Published: October 2016

Autophagy is a homeostatic process regulating turnover of impaired proteins and organelles, and p62 (sequestosome‐1, SQSTM1) functions as the autophagic receptor in this process. p62 also functions as a hub for intracellular signaling such as that in the mammalian target of rapamycin (mTOR) pathway. Liver stem/progenitor cells have the potential to differentiate to form hepatocytes or cholangiocytes. In this study, we examined effects of autophagy, p62, and associated signaling on hepatic differentiation. Adult stem/progenitor cells were isolated from the liver of mice with chemically induced liver injury. Effects of autophagy, p62, and related signaling pathways on hepatic differentiation were investigated by silencing the genes for autophagy protein 5 (ATG5) and/or SQSTM1/p62 using small interfering RNAs. Hepatic differentiation was assessed based on increased albumin and hepatocyte nuclear factor 4α, as hepatocyte markers, and decreased cytokeratin 19 and SOX9, as stem/progenitor cell markers. These markers were measured using quantitative RT‐PCR, immunofluorescence, and Western blotting. ATG5 silencing decreased active LC3 and increased p62, indicating inhibition of autophagy. Inhibition of autophagy promoted hepatic differentiation in the stem/progenitor cells. Conversely, SQSTM1/p62 silencing impaired hepatic differentiation. A suggested mechanism for p62‐dependent hepatic differentiation in our study was activation of the mTOR pathway by amino acids. Amino acid activation of mTOR signaling was enhanced by ATG5 silencing and suppressed by SQSTM1/p62 silencing. Our findings indicated that promoting amino acid sensitivity of the mTOR pathway is dependent on p62 accumulated by inhibition of autophagy and that this process plays an important role in the hepatic differentiation of stem/progenitor cells. J. Cell. Physiol. 232: 2112–2124, 2017. © 2016 Wiley Periodicals, Inc.
Micro‐Raman and SER spectroscopy to unfold Lefranc's early organic pigment formulations
Authors: Gabrieli F. , Doherty B. , Miliani C. , Degano I. , Modugno F. , Uldank D. , Kunzelman D. , Buzzegoli E. , Patti M. , Rosi F.
Published: October 2016

The introduction of synthetic dyes and pigments into commerce in the late 19th century was a stimulating time for experimental scientists in their laboratory formulations and for artists in their usage. Nowadays, the period of pioneering syntheses and employment of synthetic organic colouring materials is highly intriguing for scientific research and for conservation purposes in heritage science. In this work, a combination of spectroscopic and chromatographic methods has permitted the elucidation of the chemical composition of 16 early synthetic organic pigment powders from the Lefranc experimental laboratory collection dating 1890–1914. It can be hypothesized that the most successful of these formulations could have been finalized in paint tubes and released onto the market, meaning that they may even be found in artworks from the same period.

Specifically, information from this crucial period of transition from the exclusive use of natural dyes/colourants (such as neoflavonoids and plant and insect anthraquinones) to the introduction of their synthetic counterparts (such as synthetic alizarin and purpurin, and acid stable cochineal, together with monoazo and diazo pigments) is confirmed through Raman/surface‐enhanced Raman spectroscopy and high‐performance liquid chromatography with diode array detection. By means of X‐ray fluorescence and mid‐Fourier transform infrared spectroscopy, a combination of traditional and modern inorganic substrates has been identified (alum, kaolin, barium sulfate and metallic salts), while Raman has provided additional data regarding the possible complexation of these pigments in the form of lakes. Copyright © 2016 John Wiley & Sons, Ltd.
Kinetics of enzyme‐catalysed oxygen isotope exchange between phosphate and water revealed by Raman spectroscopy
Authors: von Sperber Christian , Lewandowski Hans , Tamburini Federica , Bernasconi Stefano M. , Amelung Wulf , Frossard Emmanuel
Published: October 2016

Pyrophosphatases (EC 3.6.1.1) are ubiquitous enzymes that catalyse the hydrolysis of pyrophosphate, a byproduct of many biochemical reactions. The hydrolysis leads to an oxygen isotope exchange between the newly formed phosphate molecules and water. Here, we applied Raman spectroscopy to monitor the oxygen isotope exchange reaction in presence of pyrophosphatase from baker's yeast. For this purpose, enzymatic assays consisting of 0.8 m 18O‐enriched phosphate were prepared under pH‐buffered conditions. Upon addition of pyrophosphatase, the Raman spectrum of the solution immediately started to shift to higher wavenumbers, indicating the progressive substitution of 18O in phosphate by 16O from water. The analytical results were quantified by fitting a Voigt function to the measured Raman spectra that allowed to determine the relative contribution of each phosphate isotopologue in solution over time. Based on the relative contribution of the different phosphate species, the apparent overall oxygen exchange rate could be calculated assuming a first‐order kinetic. The progressive formation and disappearance of the different phosphate isotopologues were then modelled by applying a consecutive reaction scheme with first‐order steps. The results of our experiments show that Raman spectroscopy can be used to study the kinetics of enzyme‐catalysed oxygen isotope exchange in the phosphate–water system. Copyright © 2016 John Wiley & Sons, Ltd.
High‐intensity ultrasound enhances the immunoglobulin (Ig)G and IgE binding of ovalbumin
Authors: Yang Wen‐Hua , Tu Zong‐Cai , Wang Hui , Li Xue , Tian Ming
Published: October 2016

BACKGROUND

Hen eggs are widely used in food industry as a result of their excellent nutritional and processing properties and ovalbumin (OVA) is the major allergen of hen egg whites. Ultrasound has been widely used in the food processing industry, although the effect of high‐intensity ultrasound on the immunoglobulin (Ig)G binding, IgE binding and conformational structure of OVA remains unclear.

RESULTS

Ultrasound treatment at 600–800 W dramatically increased the IgG and IgE binding of OVA, with the highest values observed at 600 W. The free sulfhydryl content, surface hydrophobicity and ultraviolet absorption were gradually increased when the power was increased from 200 to 600 W, implying the occurrence of molecule unfolding. When the power was 800 W, the binding ability was slightly decreased and was associated with the aggregation of OVA molecules. Polyacrylamide gel electrophoresis analysis implied that ultrasound treatment at 800 W could induce the aggregation of OVA molecules via disulfide bonds and/or hydrophobic interactions.

CONCLUSION

High‐intensity ultrasound can increase the potential allergenicity of OVA. Therefore, high‐intensity ultrasound processing of some egg products alone may improve the risk of an allergenic reaction in egg allergy patients to some extent. © 2016 Society of Chemical Industry
Gas chromatography analysis of major free mono‐ and disaccharides in milk: Method assessment, validation, and application to real samples
Authors: Idda Ilenia , Spano Nadia , Ciulu Marco , Nurchi Valeria M. , Panzanelli Angelo , Pilo Maria I. , Sanna Gavino
Published: October 2016

Saccharides are functional constituents of milk. Although d‐lactose represents almost the totality of the saccharides in the milk, minor species, like d‐glucose, d‐galactose, myo‐inositol and, as a result of severe thermal treatments, monosaccharides like d‐tagatose, are also detectable. Although chromatography has been the main analytical approach used for accomplishing this task, quite surprisingly a validated gas chromatographic method aimed at the simultaneous determination of these compounds is still needed. Hence, our contribution is devoted to fill this gap. After the optimization of clean‐up and derivatization (conversion of saccharides in their trimethyl silyl ethers) steps, the adoption of a highly cross‐linked silphenylene stationary phase permitted to obtain high resolution and a fast chromatographic run. Validation was accomplished in terms of limit of detection, limit of quantification, linearity, precision, and trueness. The accuracy of the method was successfully tested on a number of partially skimmed milk samples. Excellent limits of detection for all analytes make this method eligible, also with respect to a gas chromatographic/mass spectrometry approach, for routine analysis and quality control in the dairy industries.
Inorganic–organic hybrid coating material for the online in‐tube solid‐phase microextraction of monohydroxy polycyclic aromatic hydrocarbons in urine
Authors: Wang ShuLing , Xu Hui
Published: October 2016

An inorganic–organic hybrid nanocomposite (zinc oxide/polypyrrole) that represents a novel kind of coating for in‐tube solid‐phase microextraction is reported. The composite coating was prepared by a facile electrochemical polymerization strategy on the inner surface of a stainless‐steel tube. Based on the coated tube, a novel online in‐tube solid‐phase microextraction with liquid chromatography and mass spectrometry method was developed and applied for the extraction of three monohydroxy polycyclic aromatic hydrocarbons in human urine. The coating displayed good extraction ability toward monohydroxy polycyclic aromatic hydrocarbons. In addition, long lifespan, excellent stability, and good compression resistance were also obtained for the coating. The experimental conditions affecting the extraction were optimized systematically. Under the optimal conditions, the limits of detection and quantification were in the range of 0.039–0.050 and 0.130–0.167 ng/mL, respectively. Good linearity (0.2–100 ng/mL) was obtained with correlation coefficients larger than 0.9967. The repeatability, expressed as relative standard deviation, ranged between 2.5% and 9.4%. The method offered the advantage of process simplicity, rapidity, automation, and sensitivity in the analysis of human urinary monohydroxy polycyclic aromatic hydrocarbons in two different cities of Hubei province. An acceptable recovery of monohydroxy polycyclic aromatic hydrocarbons (64–122%) represented the additional attractive features of the method in real urine analysis.
Recovery of lakes and coastal marine ecosystems from eutrophication: A global meta‐analysis
Authors: McCrackin Michelle L. , Jones Holly P. , Jones Peter C. , Moreno‐Mateos David
Published: October 2016

In order to inform policies aimed at reducing nutrient emissions to surface waters, it is essential to understand how aquatic ecosystems respond to eutrophication management. Using data from 89 studies worldwide, we examined responses to the reduction or cessation of anthropogenic nutrient inputs relative to baseline conditions. Baseline conditions were pre‐disturbance conditions, undisturbed reference sites, restoration targets, or experimental controls. We estimated recovery completeness (% baseline conditions reached) and recovery rate (annual % change relative to baseline conditions) for plant and animal abundance and diversity and for ecosystem functions. Categories were considered fully recovered if the 95% confidence interval (CI) of recovery completeness overlapped 100% and partially recovered if the CI did not overlap either 100% or zero. Cessation of nutrient inputs did not result in more complete or faster recovery than partial nutrient reductions, due likely to insufficient passage of time, nutrients from other sources, or shifting baselines. Together, lakes and coastal marine areas achieved 34% (±16% CI) and 24% (±15% CI) of baseline conditions decades after the cessation or partial reduction of nutrients, respectively. One third of individual response variables showed no change or worsened conditions, suggesting that achieving baseline conditions may not be possible in all cases. Implied recovery times after cessation of nutrient inputs varied widely, from < 1 yr to nearly a century, depending on response. Our results suggest that long‐term monitoring is needed to better understand recovery timescales and trajectories and that policy measures must consider the potential for slow and partial recovery.
The oxidation behaviour of the pulse plasma sintered β‐NiAl intermetallic compound under thermal cycling conditions at 1150 °C
Authors: Jedliński J. , Dąbek J. , Prażuch J. , Michalski A. , Rosiński M. , Grosseau‐Poussard J.‐L. , Takashima D. , Wołczyk W. , Żurek Z.
Published: October 2016

The effect of microstructure engineering using a new manufacturing route (pulse plasma sintering (PPS)) on the high temperature oxidation behaviour of β‐NiAl coating material with and without small amounts of Hf was determined at 1150 °C under thermal cycling conditions in air. Vacuum melted β‐NiAl compounds with and without Hf were used as reference materials and tested under the same conditions. The oxide scales were observed using SEM and analysed using EDX. The results showed that the Hf‐containing materials behaved better than Hf‐free ones and among the Hf‐containing materials, the vacuum melted one exhibited significantly better cyclic oxidation resistance than the PPS material. Thus, no improvement of the oxidation resistance was achieved using the applied manufacturing procedure. The scales prone to spallation were at considerably later stages of the scale evolution and less intact with the substrate than the scale resistant to spallation.
Effect of powder size on the long‐term corrosion performance of pure aluminium coatings on mild steel by cold spraying
Authors: Li N. , Li W. Y. , Yang X. W. , Alexopoulos N. D. , Niu P. L.
Published: October 2016

To achieve the long‐term corrosion protection of mild steel under corrosive environment, pure aluminium coatings were cold sprayed (CS) on mild steel with three different powder sizes, namely within the three following classes 85–100, 60–75 and 40–50 µm. The as‐sprayed samples were exposed to the atmosphere for 11 years. The long‐term corrosion behaviour of the sprayed steels was studied by atmospheric exposure, immersion tests as well as electrochemical measurements in 3.5 wt% sodium chloride (NaCl) solution. It was found that the coatings with coarse powder reduced the long‐term corrosion resistance of the samples. The deteriorated corrosion resistance of the sprayed samples was ascribed to the penetration of the corrosive medium (oxygen, water and electrolyte) through the porosity defects of coatings and with coarse powder. These results provide a guide for the design of cold sprayed corrosion‐resistance pure Al coatings for engineering applications.