bluuebunny/crossref_metadata_2025 huggingface dataset:
Ternary proton exchange membranes with low‐cost raw materials: Solvent type influence on microstructure development, high ionic conductivity, and ionic liquid lixiviation protection
Authors: Rubio Arias Jose Jonathan , Gomes Ailton de Souza
Published: January 2018

A critical stage of solvent evaporation during membrane casting was identified as responsible for significant differences in performance of ternary membranes composed of PEEK with 73% of sulfonation degree. DemaTfO and MmtdemaDMF showed to be the best solvent for casting of membranes prepared through the present study, which is against the observations made through other different studies. Fractal structures are formed regardless of solvent polarity, and interlamellar spacing is found to be higher when DMF is used, which led to higher conductivity and IL leaching protection. Proton relaxometry showed that only the membranes made with DMF and DMAc possess one single mobility domain. Transmission electron microscopy micrographs showed a higher damage in membranes with two different mobility domains and consequent phase separation. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46012.
Looking back to interfacial tension prediction in the compatibilized polymer blends: Discrepancies between theories and experiments
Authors: Hassanpour Asl Farzaneh , Saeb Mohammad Reza , Jafari Seyed Hassan , Khonakdar Hossein Ali , Rastin Hadi , Pötschke Petra , Vogel Roland , Stadler Florian J.
Published: January 2018

Prediction of interfacial tension of compatibilized polymer blends is a challenging open problem, where experiments and theories hardly support each other. In this work, constitutive models proposed for quantifying the interfacial tension of compatibilized polymer blends were revisited and their limitations/capabilities were discussed. In view of available data in the literature, which could provide with possibility of comparison between interfacial tension values obtained in this work and those published before, high‐density polyethylene (HDPE)/polyamide‐6 and HDPE/polyethylene‐co‐vinyl alcohol pairs comprising varying amounts of HDPE‐g‐maleic anhydride compatibilizer precursor were prepared for obtaining model parameters. The inability of theories in monitoring the interfacial tension was accordingly uncovered. However, outcomes from both theoretical and experimental data provided some insights for elucidating the interplay between interfacial tension and rheological characteristics of the studied compatibilized blends. It was also attempted to uncover the relationships between particle size, particle size distribution, and rheological properties of blends compatibilized with different amounts of HDPE‐g‐maleic anhydride precursor. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46144.
Electrochemical and optical properties of dicyclohexylmethyl substituted poly(3,4‐propylenedioxythiophene) analogue
Authors: Çakal Deniz , Cihaner Atilla , Önal Ahmet M.
Published: January 2018

An analogue of disubstituted 3,4‐propylenedioxythiophenes, namely 3,3‐bis(cyclohexylmethyl)‐3,4‐dihydro‐2H‐thieno[3,4‐b][1,4]dioxepin (ProDOT‐CycHex2), was synthesized and its electrochemical polymerization was carried out successfully in an electrolyte solution of 0.1 M tetrabutylammonium hexafluorophosphate dissolved in a mixture of acetonitrile and dichloromethane (3/1: v/v). The corresponding polymer called PProDOT‐CycHex2 has a reduced band gap of 1.85 eV and an electrochromic property: blue/violet when neutralized and highly transparent when oxidized. Also, PProDOT‐CycHex2 film exhibited faster response time (0.7 s) and higher coloration efficiency (769 cm2/C) during oxidation when compared to its benzyl substituted analogue. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46214.
Tunable surface roughness and wettability of a soft magnetoactive elastomer
Authors: Glavan Gašper , Salamon Peter , Belyaeva Inna A. , Shamonin Mikhail , Drevenšek‐Olenik Irena
Published: January 2018

Surface topographical modifications of a soft magnetoactive elastomer (MAE) in response to variable applied magnetic field are investigated. The analysis is performed in situ and is based on optical microscopy, spread optical reflection and optical profilometry measurements. Optical profilometry analysis shows that the responsivity of magnetic field‐induced surface roughness with respect to external magnetic field is in the range of 1 µm/T. A significant hysteresis of surface modifications takes place for increasing and decreasing fields. Investigations of shape of sessile water droplets deposited on the MAE surface reveal that field‐induced topographical modifications affect the contact angle of water at the surface. This effect is reversible and the responsivity to magnetic field is in the range of 20°/T. Despite the increased surface roughness, the apparent contact angle decreases with increasing field, which is attributed to the field‐induced protrusion of hydrophilic microparticles from the surface layer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46221.
Enhanced thermal and mechanical properties of PW‐based HTPB binder using polystyrene (PS) and PS–SiO2 microencapsulated paraffin wax (MePW)
Authors: Gao Xia , Zhao Tianbo , Luo Guan , Zheng Baohui , Huang Hui , Ma Rui , Han Xue , Chai Yuqiao
Published: January 2018

Polystyrene (PS) microencapsulated paraffin wax (MePW) and PS–SiO2 MePW were used to improve the form‐stability of PW in hydroxyl‐terminated polybutadiene‐derived polyurethane (HTPB) binder. HTPB matrix containing different contents of PS MePW, PS–SiO2 MePW, and PW were prepared. The chemical composition, crystallinity, microstructure, heat capacities, thermal stabilities, thermal reliabilities, leakage, and mechanical properties of the composites were compared using Fourier transforms infrared spectroscope, X‐ray diffractometer, scanning electronic microscope, differential scanning calorimeter, thermo‐gravimetric analyzer, thermal cycling test, leaking test, compression, and tensile tests, respectively. The results showed that the MePW/PW/HTPB composites were prepared without chemical reaction. The thermal stability and mechanical properties of PS–SiO2 MePW/PW/HTPB increased more dramatically than that of PS MePW/PW/HTPB. With the increasing contents of MePWs, the PW leakage of the composites decreased, especially for PS MePW/PW/HTPB. Consequently, the MePW/PW/HTPB composites possess a potential application for PW‐based polymer‐bonded explosive system. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46222.
Different Atomic Terminations Affect the Photocatalytic Nitrogen Fixation of Bismuth Oxybromide: A First Principles Study
Authors: Liu Hongxian , Fang Zhenxing , Su Yongfei , Suo Yuanli , Huang Shuping , Zhang Yongfan , Ding Kaining
Published: January 2018

We have systematically investigated the electronic structures and activation capacities of BiOBr {001} facets with different atomic terminations by means of DFT methods. Our calculations reveal that oxygen vacancies (OVs) give a significant boost in band edges of the O‐terminated BiOBr {001} facets, and excess electrons induced by OVs could exceed the reduction potentials of high‐energy N2 intermediates. Interestingly, the Bi‐terminated BiOBr {001} facets may be good candidates for photocatalytic nitrogen fixation due to the stronger activation ability of N2 molecules comparing with O‐terminated BiOBr {001} facets with OVs. Moreover, the Bi‐terminated BiOBr {001} facets may tend to yield NH3 instead of N2H4.
A Survey of Methods Used to Control Piezoelectric Tube Scanners in High‐Speed AFM Imaging
Authors: Rana Md. Sohel , Pota Hemanshu R. , Petersen Ian R.
Published: January 2018

In most nanotechnology applications, speed and precision are important requirements for obtaining good topographical maps of material surfaces using atomic force microscopes (AFMs), many of which use piezoelectric tube scanners (PTSs) for scanning and positioning at nanometric resolutions. For control engineers, the PTS is particularly interesting since its ability to enable the AFM to undertake 3D imaging is entirely dependent upon the use of a feedback loop. However, it suffers from various intrinsic problems that degrade its positioning performance, such as: (i) lightly damped low‐frequency resonant modes due to its mechanical structure; (ii) nonlinear behavior due to hysteresis and creep; (iii) the cross‐coupling effect between its axes (in 3D positioning systems such as AFMs); and (iv) effect of thermal drift. This article presents a survey of the literature on the PTS, an overview of a few existing innovative solutions for its nanopositioning and future research directions. This article will help the reader to walk around the present development of the PTS aimed at meeting the requirements for high‐speed AFM imaging.
LC/MS‐based Intact IgG and Released Glycan Analysis for Bioprocessing Applications
Authors: Wang Tianhua , Hoi Kong Meng , Stöckmann Henning , Wan Corrine , Sim Lyn Chiin , Shi Jie Tay Noor Hayati Bte Kamari , Poo Ce Huang , Woen Susanto , Yang Yuangsheng , Zhang Peiqing , Rudd Pauline M.
Published: January 2018

Robust plate based antibody glycan analysis platforms are urgently needed for biopharmaceutical development and manufacturing as well as for clinical biomarker research. A 96‐well plate based workflow has been developed to analyze both intact IgG antibodies and released N‐glycans using an Orbitrap Fusion Mass Spectrometer and an LC/MS method on the Waters UNIFI platform. Here, such a workflow including protein A purification, PNGaseF digestion, 2‐AB labeling, and SPE clean‐up is described. The measured IgG glycan profile is consistent with that obtained from non‐plate based method and commercial kit and has the advantage of less hands‐on time. Also the application of the workflow in cell culture monitoring and clonal selection work is demonstrated. Apart from checking the major glycan structure changes among clones, post translational modifications (PTMs) such as C‐terminal lysine residue clipping and N‐terminal pyroglutamic acid formation can also be deduced from the workflow.
Genetic analysis of surgical margins in oral cavity cancer
Authors: Liu S A , Wang C C , Jiang R S , Wang W Y , Lin J C
Published: January 2018

Background

A histological, tumour-free surgical margin does not guarantee recurrence-free survival in patients with cancer. This study investigated the association between microsatellite alteration in tumour-free surgical margins and local recurrence in patients with oral cavity squamous cell carcinoma.

Methods

Patients with histologically confirmed oral cavity squamous cell carcinoma were enrolled in this prospective study. Cancerous specimens, corresponding surgical margins and peripheral blood were obtained. Microsatellite alteration was investigated using six dinucleotide microsatellite markers. All samples were amplified by PCR, followed by automatic fragment analysis.

Results

Microsatellite alteration was identified in 100 specimens (69·0 per cent) from 145 patients. Among them, 85 specimens carried loss of heterozygosity, whereas 55 had microsatellite instability (MSI). Patients with MSI at the surgical margin had a higher risk of local recurrence on multivariable analysis (odds ratio 7·17, 95 per cent c.i. 3·49 to 14·73).

Conclusion

Molecular assessment of surgical margins can help identify patients at risk of local recurrence.
Quality-of-life implications of risk-reducing cancer surgery
Authors: Altman A M , Hui J Y C , Tuttle T M
Published: January 2018

Background

Modern advances in genetic sequencing techniques have allowed for increased availability of genetic testing for hereditary cancer syndromes. Consequently, more people are being identified as mutation carriers and becoming aware of their increased risk of malignancy. Testing is commonplace for many inheritable cancer syndromes, and with that comes the knowledge of being a gene carrier for some patients. With increased risk of malignancy, many guidelines recommend that gene carriers partake in risk reduction strategies, including risk-reducing surgery for some syndromes. This review explores the quality-of-life consequences of genetic testing and risk-reducing surgery.

Methods

A narrative review of PubMed/MEDLINE was performed, focusing on the health-related quality-of-life implications of surgery for hereditary breast and ovarian cancer, familial adenomatous polyposis and hereditary diffuse gastric cancer.

Results

Risk-reducing surgery almost uniformly decreases cancer anxiety and affects patients' quality of life.

Conclusion

Although the overwhelming quality-of-life implications of surgery are neutral to positive, risk-reducing surgery is irreversible and can be associated with short- and long-term side-effects.
Clinicopathological, genomic and immunological factors in colorectal cancer prognosis
Authors: Marks K M , West N P , Morris E , Quirke P
Published: January 2018

Background

Numerous factors affect the prognosis of colorectal cancer (CRC), many of which have long been identified, such as patient demographics and the multidisciplinary team. In more recent years, molecular and immunological biomarkers have been shown to have a significant influence on patient outcomes. Whilst some of these biomarkers still require ongoing validation, if proven to be worthwhile they may change our understanding and future management of CRC. The aim of this review was to identify the key prognosticators of CRC, including new molecular and immunological biomarkers, and outline how these might fit into the whole wider context for patients.

Methods

Relevant references were identified through keyword searches of PubMed and Embase Ovid SP databases.

Results

In recent years there have been numerous studies outlining molecular markers of prognosis in CRC. In particular, the Immunoscore® has been shown to hold strong prognostic value. Other molecular biomarkers are useful in guiding treatment decisions, such as mutation testing of genes in the epidermal growth factor receptor pathway. However, epidemiological studies continue to show that patient demographics are fundamental in predicting outcomes.

Conclusion

Current strategies for managing CRC are strongly dependent on clinicopathological staging, although molecular testing is increasingly being implemented into routine clinical practice. As immunological biomarkers are further validated, their testing may also become routine. To obtain clinically useful information from new biomarkers, it is important to implement them into a model that includes all underlying fundamental factors, as this will enable the best possible outcomes and deliver true precision medicine.
Total Syntheses of Biologically Active Pterocarpan, Isoflavan, and Isoflavanone from Dalbergia oliveri
Authors: Singh Dileep Kumar , Kim Jinwoo , Sung Jong‐Hyuk , Kim Ikyon
Published: January 2018

Biological screening of the natural products from Dalbergia oliveri identified that (6aR,11aR)‐3,8‐dihydroxy‐9‐methoxypterocarpan and (3R)‐7,2′‐dihydroxy‐4′,5′‐dimethoxyisoflavanone significantly increased the proliferation of dermal papilla cells and subcutaneous injection of these compounds induced the anagen of hair cycle in animal models. These interesting biological activities led us to design a practical synthetic route to these natural products for further pharmacological evaluation. Here we report the first total syntheses of naturally occurring pterocarpan ((6aR,11aR)‐3,8‐dihydroxy‐9‐methoxypterocarpan), isoflavan ((3R)‐5′‐methoxyvestitol), and isoflavanone ((3R)‐7,2′‐dihydroxy‐4′,5′‐dimethoxyisoflavanone) in a racemic form. A mild ZnCl2‐mediated [3 + 2] annulation method was utilized with chromenes and 2‐methoxy‐1,4‐benzoquinone to construct a pterocarpan framework in a one‐pot manner. O‐methylation and reductive cleavage of the benzylic C─O bond afforded 5′‐methoxyvestitol, which was transformed to isoflavanone, 7,2′‐dihydroxy‐4′,5′‐dimethoxyisoflavanone, via a three‐step sequence including DDQ‐mediated benzylic oxidation.
The mediating role of advertising literacy and the moderating influence of parental mediation on how children of different ages react to brand placements
Authors: Hudders Liselot , Cauberghe Veroline
Published: January 2018

This study investigates the role of advertising literacy in how children of different ages respond to brand placement and how parental advertising mediation strategies can attenuate advertising effects. The results of a cross‐sectional study among 180 children under 12 and their parents show that older children (10 to 11 years) are better able to detect the commercial intent and the source of brand placement compared to the younger children (7 to 8 years). However, parental advertising mediation appears to increase (instead of decrease) brand attitudes for the younger children, whereas it has no significant effect on brand attitudes of the older children. Practical implications of the study are discussed.
Synthesis and Characterization of Photoactivatable Doxycycline Analogues Bearing Two‐Photon‐Sensitive Photoremovable Groups Suitable for Light‐Induced Gene Expression
Authors: Goegan Bastien , Terzi Firat , Bolze Frédéric , Cambridge Sidney , Specht Alexandre
Published: January 2018

We report the synthesis and photolytic properties of caged 9‐aminodoxycycline derivatives modified with 2‐{4′‐bis‐[2‐(2methoxyethoxy)ethyl]‐4‐nitrobiphenyl‐3‐yl}prop‐1‐oxy (EANBP) and PEG7‐ylated (7‐diethylamino‐2‐oxo‐2H‐chromen‐4‐yl)methyl (PEG7‐DEACM) groups. 9‐Aminodoxycycline is a tetracycline analogue capable of activating transcription through the inducible TetOn transgene expression system and can be regioselectively coupled to two‐photon‐sensitive photo‐removable protecting groups by carbamoylation. The EANBP‐based caged 9‐aminodoxycycline showed complex photochemical reactions but did release 10 % of 9‐aminodoxycycline. However, 9‐(PEG7‐DEACMamino)doxycycline exhibited excellent photolysis efficiency at 405 nm with quantitative release of 9‐aminodoxycycline and a 0.21 uncaging quantum yield. Thanks to the good two‐photon sensitivity of the DEACM chromophore, 9‐aminodoxycycline release by two‐photon photolysis is possible, with calculated action cross‐sections of up to 4.0 GM at 740 nm. Therefore, 9‐(PEG7‐DEACMamino)doxycycline represents a very attractive tool for the development of a light‐induced gene expression method in living cells.
Control of Protein Activity and Gene Expression by Cyclofen‐OH Uncaging
Authors: Zhang Weiting , Hamouri Fatima , Feng Zhiping , Aujard Isabelle , Ducos Bertrand , Ye Shixin , Weiss Shimon , Volovitch Michel , Vriz Sophie , Jullien Ludovic , Bensimon David
Published: January 2018

The use of light to control the expression of genes and the activity of proteins is a rapidly expanding field. Whereas many of these approaches use fusion between a light‐activable protein and the protein of interest to control the activity of the latter, it is also possible to control the activity of a protein by uncaging a specific ligand. In that context, controlling the activation of a protein fused to the modified estrogen receptor (ERT) by uncaging its ligand cyclofen‐OH has emerged as a generic and versatile method to control the activation of proteins quantitatively, quickly, and locally in a live organism. We present that approach and its uses in a variety of physiological contexts.
Safe surgical treatment of peripelvic renal cyst combined with renal calculi by percutaneous nephroscopy
Authors: Yang Bowei , Li Jiongming , Liu Jianhe , Bao Yuepan , Mishra Prashant , Guo Haixiang , Li Pei , Jiang Yongming
Published: January 2018

Key Clinical Message

We have tried to establish a safe and effective method to treat the peripelvic renal cyst combined with renal calculi. The key points are as follows: choose the appropriate target calyx; find the gap between cyst and renal pelvic; put a nephrostomy tube to stimulate the closing of cystic cavity.
Microbial Electrochemical Sensors for Anaerobic Digestion Process Control – Performance of Electroactive Biofilms under Real Conditions
Authors: Kretzschmar Jörg , Böhme Paul , Liebetrau Jan , Mertig Michael , Harnisch Falk
Published: January 2018

The autonomous growth of Geobacter sp.‐dominated biofilms on electrodes and their sensitivity on volatile fatty acids (VFAs) allows their application as biosensor. In this study, the implementation of a microbial electrochemical sensor in the anaerobic digestion (AD) process is reported. The amperometric sensor signal follows the acetate concentration profile in the AD process. Yet, the sensor's stability is impaired by the process conditions. Therefore, potential biofilm inhibitors are individually examined, i.e., high salt and NH4+ concentrations as well as fumarate as potential alternative electron acceptor. The results show no influence of high salinity on the signal, whereas ammonia at a concentration ≥ 5 g L−1 NH4+ acts as inhibitor, and fumarate is used as substrate for current generation.
Theoretical Insights into the Switching Off/On of 1O2 Photosensitization in Chemicontrolled Photodynamic Therapy
Authors: Pirillo Jenny , Mazzone Gloria , Russo Nino
Published: January 2018

Density Functional Theory and time‐dependent (TD) DFT calculations were carried out for recently reported 4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY)‐based photosensitizers (PSs) that could be activated by reactive oxygen species (ROS) to generate 1O2 specifically in target tissues. To assess the applicability of the compounds as activatable PSs (a‐PSs) in photodynamic therapy, absorption wavelengths; singlet–triplet energy gaps; and spin–orbit matrix elements for the radiationless transition, Sn→Tm, were investigated. A TD‐DFT qualitative analysis indicated that only a Br‐substituted BODIPY derivative with the chromanol ring of α‐tocopherol linked by methylene functioned as an a‐PS. The chromanol ring promotes photoinduced electron transfer to the BODIPY unit that reduces the probability of intersystem crossing and triplet‐state population, and can turn off 1O2 photosensitization. Therefore, 1O2 photosensitization can be switched on only in target cells in which the chromanol ring is oxidized by ROS. The oxidation reaction pathways of the most promising derivative, by either 1O2 or cumyloxyl radical as typical ROS, have been examined to reveal that oxidation by the cumyloxyl radical is more effective than that by 1O2.
Oxidation of Methylalumoxane Oligomers
Authors: Zijlstra Harmen S. , Collins Scott , McIndoe J. Scott
Published: January 2018

The anions formed from methylalumoxane (MAO) and suitable donors (e.g. octamethyltrisiloxane) are amenable to mass spectrometric (MS) analysis. Their composition as deduced from this data allows direct insight into the chemical transformations of their neutral precursors. One such process is oxidation, which is well‐known to be facile for MAO without any clear idea of what actually occurs at a molecular level. Addition of O2 to MAO results in immediate gelation, but MS analysis reveals no corresponding change to the composition of the principal oligomeric anions. A slow (hours) reaction does occur that involves net incorporation of Me2AlOMe into the oligomeric anions, and the identities of the OMe‐containing anions were confirmed by 1H NMR spectroscopy, MS/MS analysis, and addition of an authentic sample of Me2AlOMe to MAO. The result tallies with the fact that addition of O2 to MAO produces Me2AlOMe from free Me3Al which eventually leads to formation of oxidized MAO oligomers and changes in ion abundance. Aging of the oxygenated MAO results in further growth of the oligomers similar to that of the non‐oxidized species. Mass spectrometric analysis therefore reveals useful insights into the environmental history of a given MAO batch.
Mixed Fluorotryptophan Substitutions at the Same Residue Expand the Versatility of 19F Protein NMR Spectroscopy
Authors: Kenward Calem , Shin Kyungsoo , Rainey Jan K.
Published: January 2018

The strategy of applying fluorine NMR to characterize ligand binding to a membrane protein prepared with mixtures of tryptophans substituted with F at different positions on the indole ring was tested. The 19F NMR behavior of 4‐, 5‐, 6‐, and 7‐fluorotryptophan were directly compared as a function of both micellar environment and fragment size for two overlapping apelin receptor (AR/APJ) segments; one with a single transmembrane (TM) helix and two tryptophan residues, the other with three TM helices and two additional tryptophan residues. Chemical shifts, peak patterns, and nuclear spin relaxation rates were observed to vary as a function of micellar conditions and F substitution position in the indole ring, with the exposure of a given residue to micelle or solvent being the primary differentiating factor. Titration of the 3‐TM AR segment biosynthetically prepared as a mixture of 5‐ and 7‐fluorotryptophan‐containing isoforms by two distinct peptide ligands (apelin‐36 and apela‐32) demonstrated site‐specific 19F peak intensity changes for one ligand but not the other. In contrast, both ligands perturbed 1H–15N HSQC peak patterns to a similar degree. Characterization of multiple fluorotryptophan types for a given set of tryptophan residues, thus, significantly augments the potential to apply 19F NMR to track otherwise obscure modulation of protein conformation and dynamics without an explicit requirement for mutagenesis or chemical modification.
Plasmid‐Templated Control of DNA–Cyclodextrin Nanoparticle Morphology through Molecular Vector Design for Effective Gene Delivery
Authors: Gallego‐Yerga Laura , Benito Juan M. , Blanco‐Fernández Laura , Martínez‐Negro María , Vélaz Itziar , Aicart Emilio , Junquera Elena , Ortiz Mellet Carmen , Tros de Ilarduya Conchita , García Fernández Jose M.
Published: January 2018

Engineering self‐assembled superstructures through complexation of plasmid DNA (pDNA) and single‐isomer nanometric size macromolecules (molecular nanoparticles) is a promising strategy for gene delivery. Notably, the functionality and overall architecture of the vector can be precisely molded at the atomic level by chemical tailoring, thereby enabling unprecedented opportunities for structure/self‐assembling/pDNA delivery relationship studies. Beyond this notion, by judiciously preorganizing the functional elements in cyclodextrin (CD)‐based molecular nanoparticles through covalent dimerization, here we demonstrate that the morphology of the resulting nanocomplexes (CDplexes) can be tuned, from spherical to ellipsoidal, rod‐type, or worm‐like nanoparticles, which makes it possible to gain understanding of their shape‐dependent transfection properties. The experimental findings are in agreement with a shift from chelate to cross‐linking interactions on going from primary‐face‐ to secondary‐face‐linked CD dimers, the pDNA partner acting as an active payload and as a template. Most interestingly, the transfection efficiency in different cells was shown to be differently impacted by modifications of the CDplex morphology, which has led to the identification of an optimal prototype for tissue‐selective DNA delivery to the spleen in vivo.
Synthesis of α‐l‐Fucopyranoside‐Presenting Glycoclusters and Investigation of Their Interaction with Photorhabdus asymbiotica Lectin (PHL)
Authors: Jančaříková Gita , Herczeg Mihály , Fujdiarová Eva , Houser Josef , Kövér Katalin E. , Borbás Anikó , Wimmerová Michaela , Csávás Magdolna
Published: January 2018

Photorhabdus asymbiotica is a gram‐negative bacterium that is not only as effective an insect pathogen as other members of the genus, but it also causes serious diseases in humans. The recently identified lectin PHL from P. asymbiotica verifiably modulates an immune response of humans and insects, which supports the idea that the lectin might play an important role in the host–pathogen interaction. Dimeric PHL contains up to seven l‐fucose‐specific binding sites per monomer, and in order to target multiple binding sites of PHL, α‐l‐fucoside‐containing di‐, tri‐ and tetravalent glycoclusters were synthesized. Methyl gallate and pentaerythritol were chosen as multivalent scaffolds, and the fucoclusters were built from the above‐mentioned cores by coupling with different oligoethylene bridges and propargyl α‐l‐fucosides using 1,3‐dipolar azide‐alkyne cycloaddition. The interaction between fucoside derivates and PHL was investigated by several biophysical and biological methods, ITC and SPR measurements, hemagglutination inhibition assay, and an investigation of bacterial aggregation properties were carried out. Moreover, details of the interaction between PHL and propargyl α‐l‐fucoside as a monomer unit were revealed using X‐ray crystallography. Besides this, the interaction with multivalent compounds was studied by NMR techniques. The newly synthesized multivalent fucoclusters proved to be up to several orders of magnitude better ligands than the natural ligand, l‐fucose.
Circularly Polarized Luminescence from Inorganic Materials: Encapsulating Guest Lanthanide Oxides in Chiral Silica Hosts
Authors: Sugimoto Masumi , Liu Xin‐Ling , Tsunega Seiji , Nakajima Erika , Abe Shunsuke , Nakashima Takuya , Kawai Tsuyoshi , Jin Ren‐Hua
Published: January 2018

Recently, circularly polarized luminescence (CPL)‐active systems have become a very hot and interesting subject in chirality‐ and optics‐related areas. The CPL‐active systems are usually available by two approaches: covalently combining a luminescent centre to chiral motif or associating the guest of luminescent probe to a chiral host. However, all the chiral components in CPL materials were organic, although the luminescent components were alternatively organics or inorganics. Herein, the first totally inorganic CPL‐active system by “luminescent guest–chiral host” strategy is proposed. Luminescent sub‐10 nm lanthanide oxides (Eu2O3 or Tb2O3) nanoparticles (guests) were encapsulated into chiral non‐helical SiO2 nanofibres (host) through calcination of chiral SiO2 hybrid nanofibres, trapping Eu3+ (or Tb3+). These lanthanide oxides display circular dichroism (CD) optical activity in the ultraviolet wavelength and CPL signals around at 615 nm for Eu3+ and 545 nm for Tb3+. This work has implications for inorganic‐based CPL‐active systems by incorporation of various luminescent guests within chiral inorganic hosts.
Twisted Charge‐Transfer Antennae for Ultra‐Bright Terbium(III) and Dysprosium(III) Bioprobes
Authors: Bui Anh Thy , Roux Amandine , Grichine Alexei , Duperray Alain , Andraud Chantal , Maury Olivier
Published: January 2018

The design of original twisted charge transfer antennae in which a non‐planar geometry is enforced thanks to one or two bulky ortho‐Me substituents allows us to prepare the corresponding ultra‐bright TbIII and DyIII bioprobes. The brightness of the TbIII derivative compares well with that of the benchmark Tb‐Lumi4 complex. The first bio‐imaging experiments with a DyIII luminescent bioprobe are also reported.
Ligand‐ and Metal‐Based Reactivity of a Neutral Ruthenium Diolefin Diazadiene Complex: The Innocent, the Guilty and the Suspicious
Authors: Sinha Vivek , Pribanic Bruno , de Bruin Bas , Trincado Monica , Grützmacher Hansjörg
Published: January 2018

Coordination of the diazadiene diolefin ligand (trop2dad) to ruthenium leads to various complexes of composition [Ru(trop2dad)(L)]. DFT studies indicate that the closed‐shell singlet (CSS), open‐shell singlet (OSS), and triplet electronic structures of this species are close in energy, with the OSS spin configuration being the lowest in energy for all tested functionals. Singlet‐state CASSCF calculations revealed a significant multireference character for these complexes. The closed‐shell singlet wavefunction dominates, but these complexes have a significant (≈8–16 %) open‐shell singlet [d7‐RuI(L)(trop2dad.−)] contribution mixed into the ground state. In agreement with their ambivalent electronic structure, these complexes reveal both metal‐ and ligand‐centered reactivity. Most notable are the reactions with AdN3, diazomethane, and a phosphaalkyne leading to scission of the C−C bond of the diazadiene (dad) moiety of the trop2dad ligand, resulting in net (formal) nitrene, carbene, or P≡C insertion in the dad C−C bond, respectively. Supporting DFT studies revealed that several of the ligand‐based reactions proceed via low‐barrier radical‐type pathways, involving the dad.− ligand radical character of the OSS or triplet species.
One‐Pot Synthesis of Functionalized Fused Furans via a BODIPY‐Catalyzed Domino Photooxygenation
Authors: Mauger Audrey , Farjon Jonathan , Nun Pierrick , Coeffard Vincent
Published: January 2018

Six‐membered ring fused furans containing a tetrasubstituted tertiary carbon were prepared in an unprecedented one‐pot BODIPY‐catalyzed domino photooxygenation/reduction process. A series of functionalized furans was synthesized from readily available 2‐alkenylphenols and mechanistic studies were performed to account for the domino photosensitized oxygenation.
Chiral Phosphine–Phosphite Ligands in Asymmetric Gold Catalysis: Highly Enantioselective Synthesis of Furo[3,4‐d]‐Tetrahydropyridazine Derivatives through [3+3]‐Cycloaddition
Authors: Du Qingwei , Neudörfl Jörg‐Martin , Schmalz Hans‐Günther
Published: January 2018

The AuI‐catalyzed reaction of 2‐(1‐alkynyl)‐2‐alken‐1‐ones with azomethine imines regio‐ and diastereoselectively affords furo[3,4‐d]tetrahydropyridazines in a tandem cyclization/intermolecular [3+3]‐cycloaddition process under mild conditions. By employing a chiral gold catalyst (prepared in situ from a Taddol‐derived phosphine‐phosphite ligand, Me2SAuCl, and AgOTf) high yields and enantioselectivities (up to 94 % yield, up to 96 % ee) are obtained. The method provides an efficient modular route to substituted heterotricyclic furan derivatives and can be easily scaled up (using catalyst loads of only 0.15 mol %).
Alternative Liquid Fuels from Renewable Resources
Authors: Niethammer Benjamin , Wodarz Simon , Betz Matthias , Haltenort Philipp , Oestreich Dorian , Hackbarth Kathrin , Arnold Ulrich , Otto Thomas , Sauer Jörg
Published: January 2018

Recent progress regarding the production of alternative liquid fuels is described with a focus on catalyst development. Fuels for spark ignition engines as well as diesel fuels are considered and their potentials regarding the reduction of harmful emissions are addressed. Two main strategies are described. The first implies production of synthesis gas from renewables or CO2 and subsequent synthesis of methanol or dimethyl ether. Both can be further converted to a series of valuable fuels, e.g., high‐quality gasoline or oxymethylene ethers. The second strategy comprises the production of ethanol and its conversion to gasoline.
Phylogeny and distribution of protein kinase C variants in the zebrafish
Authors: Haug Marion F. , Gesemann Matthias , Berger Manuela , Neuhauss Stephan C. F.
Published: January 2018

Conventional protein kinases—consisting of α, β, and γ family members—play key roles in numerous signal transduction events. Phylogenetic analysis demonstrated the existence of five prkcs (the genes representing PKCs) in zebrafish, two paralogous forms of prkca and prkcb and one prkcg variant. mRNA expression analysis showed distinct, mainly nervous system specific expression, for all five prkc genes. For prkca and prkcb paralogs prominent expression can be seen in the telencephalon, in diencephalic regions such as the habenula or the optic tectum, in hypothalamic areas and in distinct cerebellar structures. Each transcript is additionally expressed in distinct areas: prkcaa is highly abundant in cranial sensory ganglia and in dorsal neurons of the hindbrain and the spinal cord, prkcab is strongly expressed in additional cerebellar regions, prkcba shows expression in the pectoral fin, the otic vesicle and in the proximal convoluted tubule of the kidney, and prkcbb shows prominent expression in different hypothalamic areas. Expression of prkcg is most striking in the cerebellum. As zebrafish PKCs are expressed in structures that are equivalent to mammals, the zebrafish model is well suited to study evolutionary conserved functions of PKCs in development and disease.
Excitation Position Sensitive Upconversion Emission of Lanthanide Ions Doped β‐NaYF4 Single Microcrystals
Authors: Wang Bing , Wang Jiao , Huang Gaoshan , Li Shilong , Mei Yongfeng
Published: January 2018

The information about optical propagation properties and the directionality of emission light of individual microcrystal is essential for the applications of lanthanide ions doped (Ln‐doped) upconversion (UC) materials. In this work, we focus on the optical property of UC Yb3+ and Er3+ or Tm3+ doped β‐NaYF4 single crystal microrods and microdisks. Their optical propagation properties and directionality of the UC emission are investigated by the UC photoluminescence (PL) spectra and microarea PL microscopy images. The emission colors, directionality and intensity to the edges of the microcrystals are evidently sensitive to the initial excitation laser position. The waveguide effect and the self‐absorption effect of the doping ions are responsible for such anisotropic emission and emission color changing. And the ray‐dynamical interpretation can give well explanation on the emission light distribution.
Parallel imperialist competitive algorithms
Authors: Majd Amin , Sahebi Golnaz , Daneshtalab Masoud , Plosila Juha , Lotfi Shahriar , Tenhunen Hannu
Published: January 2018

The importance of optimization and NP‐problem solving cannot be overemphasized. The usefulness and popularity of evolutionary computing methods are also well established. There are various types of evolutionary methods; they are mostly sequential but some of them have parallel implementations as well. We propose a multi‐population method to parallelize the Imperialist Competitive Algorithm. The algorithm has been implemented with the Message Passing Interface on 2 computer platforms, and we have tested our method based on shared memory and message passing architectural models. An outstanding performance is obtained, demonstrating that the proposed method is very efficient concerning both speed and accuracy. In addition, compared with a set of existing well‐known parallel algorithms, our approach obtains more accurate results within a shorter time period.
Prospects and challenges of virtual machine migration in HPC
Authors: Pickartz Simon , Clauss Carsten , Breitbart Jens , Lankes Stefan , Monti Antonello
Published: January 2018

The continuous growth of supercomputers is accompanied by increased complexity of the intra‐node level and the interconnection topology. Consequently, the whole software stack ranging from the system software to the applications has to evolve, eg, by means of fault tolerance and support for the rising intra‐node parallelism. Migration techniques are one means to address these challenges. On the one hand, they facilitate the maintenance process by enabling the evacuation of individual nodes during runtime, ie, the implementation of fault avoidance. On the other hand, they enable dynamic load balancing for an improvement of the system's efficiency. However, these prospects come along with certain challenges. On the process level, migration mechanisms have to resolve so‐called residual dependencies to the source node, eg, the communication hardware. On the job level, migrations affect the communication topology, which should be addressed by the communication stack, ie, the optimal communication path between a pair of processes might change after a migration. In this article, we explore migration mechanisms for HPC and discuss their prospects as well as the challenges. Furthermore, we present solutions enabling their efficient usage in this domain. Finally, we evaluate our prototype co‐scheduler leveraging migration for workload optimization.
Design and extensive hardware performance analysis of an efficient pairwise key generation scheme for Smart Grid
Authors: Abbasinezhad‐Mood Dariush , Nikooghadam Morteza
Published: January 2018

Generating pairwise shared keys among different entities of Smart Grid is of great significance because it provides the possibility of subsequent fast and secure communications by means of symmetric key algorithms. Due to the constrained resources of the measurement devices or the smart meters, the shared key generation scheme must not only provide the security features but also put the least possible burden on the measurement devices. Several key generation schemes have been presented thus far. However, many require time and resource consuming operations, some are not suitable for hierarchical data collection in the honest‐but‐curious model, some rely on a third trusted party, and last but not least, most of them have not considered suitable hardware that can be employed for each entity of Smart Grid. Therefore, in this paper, we propose a key generation scheme that not only is free from the aforementioned issues but is also efficient in both communication and computational costs. Additionally, and more importantly, we have implemented the cryptographic elements on (a) an ARM Cortex‐M3 microcontroller, which is a proper candidate for the measurement devices; (b) an Intel Core i7‐4702MQ processor, which can be employed for either the data collectors or the power operator; and (c) 4 ARM processors, three 32‐bit and one 64‐bit. Eventually, we have evaluated the feasibility of using the ARM processors to be employed for the data collectors. We hope that the achieved results be useful for other researches in this field.
Experimental assessment of LNC‐based cooperative communication schemes using commercial off‐the‐shelf wireless sensor network nodes
Authors: Valle Odilson T. , Budke Gerson , Montez Carlos , Moraes Ricardo , Vasques Francisco
Published: January 2018

The use of wireless sensor network nodes to support reliable communication exposes some challenging issues. For instance, the reduced available bandwidth combined with an error‐prone communication medium impairs the provision of reliable communication services. Network coding techniques can be useful to mitigate some of these issues, where multiple message groups can be combined into single messages and retransmitted to their destinations, improving the network reliability and reducing the bandwidth consumption. However, an effective use of network coding requires the availability of wireless sensor network nodes able to encode/decode messages within the required timing constraints. This paper reports an experimental assessment of commercial off‐the‐shelf wireless sensor network nodes, running a set of network coding encoding/decoding tasks. The assessed nodes range from the high‐performance ARM Cortex‐M7 to the low capability Arduino Uno platforms, including some of the most popular ARM Cortex and ATMEL AVR processors. The performed experimental assessment demonstrates that highly complex network coding techniques (with fields as large as
) can be efficiently implemented on a wide range of wireless sensor network nodes, including ARM Cortex, ATMEL AVR, and Arduino Uno platforms, smoothing some relevant reliable communication implementation issues.
Iron pill aspiration: Cytologic and histologic findings of a potential life‐threatening airway injury. A Case report and literature review
Authors: Henriques Vanessa , Santos Diogo Costa , Lérias Graça , Monteiro Lucília Cáceres
Published: January 2018

Iron pill‐induced injury of bronchial mucosa is a complication following accidental aspiration of an iron tablet. Oral iron supplementation is a common therapy, particularly among advanced‐age patients, who are more prone to aspiration. However, iron pill aspiration has been rarely reported in the literature, usually under the format of short case reports, with only 32 cases published in the literature. The cytologic features suspicious for this rare but potentially lethal entity have been seldom described. We report a case of a patient diagnosed with iron pill‐induced bronchial injury, after oral ferrous sulfate has been prescribed during a hospital admission for pneumonia. In the bronchial washing specimen, a background of necrotic cell debris and acute inflammation involving extracellular golden‐brown fibrils positive for iron stains was seen, along with the yeast forms, which, in this clinical context could confirm the iron pill aspiration. Our aim is to highlight the cytology features associated with iron pill aspiration bronchitis, and to review the literature for the histologic, clinical, bronchoscopy, and treatment aspects.
Which egg features predict egg rejection responses in American robins? Replicating Rothstein's (1982) study
Authors: Luro Alec B. , Igic Branislav , Croston Rebecca , López Analía V. , Shawkey Matthew D. , Hauber Mark E.
Published: January 2018

Rothstein (Behavioral Ecology and Sociobiology, 11, 1982, 229) was one of the first comprehensive studies to examine how different egg features influence egg rejection behaviors of avian brood parasite–hosts. The methods and conclusions of Rothstein (1982) laid the foundation for subsequent experimental brood parasitism studies over the past thirty years, but its results have never been evaluated with replication. Here, we partially replicated Rothstein's (1982) experiments using parallel artificial model egg treatments to simulate cowbird (Molothrus ater) parasitism in American robin (Turdus migratorius) nests. We compared our data with those of Rothstein (1982) and confirmed most of its original findings: (1) robins reject model eggs that differ from the appearance of a natural robin egg toward that of a natural cowbird egg in background color, size, and maculation; (2) rejection responses were best predicted by model egg background color; and (3) model eggs differing by two or more features from natural robin eggs were more likely to be rejected than model eggs differing by one feature alone. In contrast with Rothstein's (1982) conclusion that American robin egg recognition is not specifically tuned toward rejection of brown‐headed cowbird eggs, we argue that our results and those of other recent studies of robin egg rejection suggest a discrimination bias toward rejection of cowbird eggs. Future work on egg recognition will benefit from utilizing a range of model eggs varying continuously in background color, maculation patterning, and size in combination with avian visual modeling, rather than using model eggs which vary only discretely.
Impaired phagocytosis directs human monocyte activation in response to fungal derived β‐glucan particles
Authors: Camilli Giorgio , Eren Elif , Williams David L. , Aimanianda Vishukumar , Meunier Etienne , Quintin Jessica
Published: January 2018

Recognition of the fungal cell wall carbohydrate β‐glucan by the host receptor Dectin‐1 elicits broad immunomodulatory responses, such as phagocytosis and activation of oxidative burst. These responses are essential for engulfing and killing fungal pathogens. Phagocytic monocytes are key mediators of these early host inflammatory responses to infection. Remarkably, whether phagocytosis of fungal β‐glucan leads to an inflammatory response in human monocytes remains to be established. Here, we show that phagocytosis of heat‐killed Candida albicans is essential to trigger inflammation and cytokine release. By contrast, inhibition of actin‐dependent phagocytosis of particulate (1‐3,1‐6)‐β‐glucan induces a strong inflammatory signature. Sustained monocyte activation, induced by fungal β‐glucan particles upon actin cytoskeleton disruption, relies on Dectin‐1 and results in the classical caspase‐1 inflammasome formation through NLRP3, generation of an oxidative burst, NF‐κB activation, and increased inflammatory cytokine release. PI3K and NADPH oxidase were crucial for both cytokine secretion and ROS generation, whereas Syk signaling mediated only cytokine production. Our results highlight the mechanism by which phagocytosis tightly controls the activation of phagocytes by fungal pathogens and strongly suggest that actin cytoskeleton dynamics are an essential determinant of the host's susceptibility or resistance to invasive fungal infections.