bluuebunny/crossref_metadata_2025_split huggingface dataset:
Atom‐Specific Mutagenesis Reveals Structural and Catalytic Roles for an Active‐Site Adenosine and Hydrated Mg2+ in Pistol Ribozymes
Authors: Neuner Sandro , Falschlunger Christoph , Fuchs Elisabeth , Himmelstoss Maximilian , Ren Aiming , Patel Dinshaw J. , Micura Ronald 
Published: November 2017

AbstractThe pistol RNA motif represents a new class of self‐cleaving ribozymes of yet unknown biological function. Our recent crystal structure of a pre‐catalytic state of this RNA shows guanosine G40 and adenosine A32 close to the G53–U54 cleavage site. While the N1 of G40 is within 3.4 Å of the modeled G53 2′‐OH group that attacks the scissile phosphate, thus suggesting a direct role in general acid–base catalysis, the function of A32 is less clear. We present evidence from atom‐specific mutagenesis that neither the N1 nor N3 base positions of A32 are involved in catalysis. By contrast, the ribose 2′‐OH of A32 seems crucial for the proper positioning of G40 through a H‐bond network that involves G42 as a bridging unit between A32 and G40. We also found that disruption of the inner‐sphere coordination of the active‐site Mg2+ cation to N7 of G33 makes the ribozyme drastically slower. A mechanistic proposal is suggested, with A32 playing a structural role and hydrated Mg2+ playing a catalytic role in cleavage.
Ligand‐Directed Divergent Synthesis of Carbo‐ and Heterocyclic Ring Systems
Authors: Lee Yen‐Chun , Kumar Kamal , Waldmann Herbert 
Published: November 2017

AbstractChemical tools that enable a catalytic reaction to selectively and efficiently yield different products will allow charting of wider chemical space. In ligand‐directed divergent synthesis, a common mode of catalysis is modulated by employing different ligands for catalytic organometallic complexes to transform either common substrates or common reactive intermediates into distinct molecular scaffolds. The strategy has the potential to create important and diverse scaffolds and to unveil novel modes of catalytic transformations for wider synthetic applications. This strategy is described and recent efforts in this emerging field of catalysis, focusing on transition‐metal catalysis for the synthesis of carbo‐ and heterocyclic ring systems, are reviewed.
Effect of adding a reactive plasticizer on the mechanical, thermal, and morphology properties of nylon toughened wheat gluten materials
Authors: Langstraat Thomas , Van Puyvelde Peter , Delcour Jan , Verpoest Ignaas , Goderis Bart 
Published: November 2017

ABSTRACTBlends of wheat gluten (WG) with up to 30% aliphatic nylon were prepared by mixing in 70% aqueous ethanol solution at 110 °C in a sealed reactor. After solvent removal and mechanical milling, rigid plaques were compression molded from the powdered blends. The microstructure of the molded plaques was studied via scanning electron microscopy. All compositions showed a phase separated morphology with seemingly poor compatibility between the two components. Up to 10% addition, the nylon was dispersed within the gluten matrix as discrete particles with an average diameter >10 μm. At higher nylon volume fractions there was evidence for the presence of gluten sub‐inclusions within the nylon phases. The dispersion of particles in a blend containing 10% nylon was improved and the particle size was decreased to roughly 5 μm by addition of an epoxy functionalized ethylene glycol oligomer. The additive simultaneously lowered the modulus of the WG matrix and appeared to improve the interfacial bonding between the gluten and the nylon. In cross‐sections of the ternary blends, fine filaments were observed spanning the gluten/nylon phases at the phase boundary. The compression molded plaques continued to exhibit brittle failure in mechanical bending tests characteristic of glassy gluten materials, however, the mechanical toughness was boosted to almost three times that of reference gluten plaques by the combined addition of the nylon and reactive plasticizer. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45931.
Evolution of morphology, ferroelectric, and mechanical properties in poly(vinylidene fluoride)–poly(vinylidene fluoride‐trifluoroethylene) blends
Authors: Suresh G. , Mallikarjunachari G. , Jatav Sanjay , Thirmal Ch. , Ramachandra Rao M. S. , Satapathy Dillip K. 
Published: November 2017

ABSTRACTConsidering the complementary properties of poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride‐trifluoroethylene) [P(VDF‐TrFE)], it appears that their blends have the potential to be promising candidates for device applications. We report the evolution of morphology, ferroelectric, and mechanical properties (modulus and hardness) and their dependence on preparation temperature for PVDF–P(VDF‐TrFE) blends. From ferroelectric hysteresis measurements it was found that P(VDF‐TrFE) rich blends treated at higher temperature show significant values of remanent polarization. Remanent polarization values show a fourfold increase in these P(VDF‐TrFE) rich blends treated at higher temperature. Interestingly, blends prepared from high temperature showed greater value of remanent polarization even though they were found to consist of smaller amount of electroactive phase as compared to their low temperature treated counterpart. Nanoindentation experiments revealed that high temperature treatment improves the modulus of blends by at least 100%. This report attempts to tie these findings to the morphology and crystallinity of these blends. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45955.
Genetic Variants inERAP1andERAP2Associated With Immune‐Mediated Diseases Influence Protein Expression and the Isoform Profile
Authors: Hanson Aimee L. , Cuddihy Thomas , Haynes Katelin , Loo Dorothy , Morton Craig J. , Oppermann Udo , Leo Paul , Thomas Gethin P. , Lê Cao Kim‐Anh , Kenna Tony J. , Brown Matthew A. 
Published: November 2017

ObjectiveEndoplasmic reticulum aminopeptidase 1 (ERAP‐1) andERAP‐2,encoded on chromosome 5q15, trim endogenous peptides forHLA‐mediated presentation to the immune system. Polymorphisms inERAP1and/orERAP2are strongly associated with several immune‐mediated diseases with specificHLAbackgrounds, implicating altered peptide handling and presentation as prerequisites for autoreactivity against an arthritogenic peptide. Given the thorough characterization of disease risk–associated polymorphisms that alterERAPactivity, this study aimed instead to interrogate the expression effect of chromosome 5q15 polymorphisms to determine their effect onERAPisoform and protein expression.MethodsRNAsequencing and genotyping across chromosome 5q15 were performed to detect genetic variants inERAP1andERAP2associated with altered total gene and isoform‐specific expression. The functional implication of a putative messengerRNAsplice‐altering variant onERAP‐1 protein levels was validated using mass spectrometry.ResultsPolymorphisms associated with ankylosing spondylitis (AS) significantly influenced the transcript and protein expression of ERAP‐1 and ERAP‐2. Disease risk–associated polymorphisms in and around both genes were also associated with increased gene expression. Furthermore, key risk‐associatedERAP1variants were associated with altered transcript splicing, leading to allele‐dependent alternate expression of 2 distinct isoforms and significant differences in the type ofERAP‐1 protein produced.ConclusionIn accordance with studies demonstrating that polymorphisms that increase aminopeptidase activity predispose to immune disease, the increased risk also attributed to increased expression ofERAP1andERAP2supports the notion of using aminopeptidase inhibition to treatASand otherERAP‐associated conditions.
Semi‐Global Robust Output Regulation for A Class of Singular Nonlinear Systems with Unknown Algebraic Equations
Authors: Huang Bomin , Lan Weiyao 
Published: November 2017

AbstractThis paper considers semi‐global robust output regulation problem for a class of singular nonlinear systems whose algebraic equations are not precisely known. Since the algebraic equations are not known, the output regulation problem of singular nonlinear systems cannot be solved by directly reducing the singular nonlinear system into a normal nonlinear system. Based on internal model principle, we convert the robust output regulation problem of singular nonlinear systems into a robust stabilization problem of an augmented singular nonlinear system. The augmented singular nonlinear system is also with unknown algebraic equations. However, without transforming the singular nonlinear system into a normal nonlinear system, it is shown that the augmented singular nonlinear system can be semi‐globally stabilized by a high gain output feedback control law under some reasonable assumptions. Moreover, the semi‐global stabilization control law of the augmented singular nonlinear systems also solves the semi‐global robust output regulation problem of the original singular nonlinear system.
Dynamic Output Feedback Control for Systems Subject to Actuator Saturation via Event‐Triggered Scheme
Authors: Li Hongchao , Zuo Zhiqiang , Wang Yijing 
Published: November 2017

AbstractIn this paper, the event‐triggered dynamic output feedback control problem for linear systems with actuator saturation is investigated. Event‐triggered scheme only transmits the corresponding signal when the event‐triggered condition is violated. Due to its advantage of saving communication resources, it is utilized to design the dynamic output feedback controller. A criterion is established to guarantee the stability of the closed‐loop system by introducing an exponential term for the Lyapunov function, which corresponds to the exponential term in the event‐triggered condition. The explicit design of the coefficient matrices of the controller is presented. Furthermore, a lower bound of the inter‐event time is calculated to avoid Zeno behavior. An optimization algorithm is then formulated to maximize the estimation of the domain of attraction. Finally, a numerical example is given to illustrate the effectiveness of our methods and to show the trade‐off between the size of the domain of attraction and communication resources saving.
Preferential capture of EpCAM‐expressing extracellular vesicles on solid surfaces coated with an aptamer‐conjugated zwitterionic polymer
Authors: Yoshida Mitsutaka , Hibino Kazuhiro , Yamamoto Satoshi , Matsumura Sachiko , Yajima Yasutomo , Shiba Kiyotaka 
Published: November 2017

AbstractExtracellular vesicles (EVs) collectively represent small vesicles that are secreted from cells and carry biomolecules (e.g., miRNA, lncRNA, mRNA, proteins, lipids, metabolites, etc.) that originate in those cells. Body fluids, such as blood and saliva, include large numbers of EVs, making them potentially a rich source of diagnostic information. However, these EVs are mixtures of vesicles released from diseased tissues as well as from normal cells. This heterogeneous nature therefore blurs the clinical information obtainable from EV‐based diagnosis. Here, we synthesized an EpCAM‐affinity coating agent, which consists of a peptide aptamer for EpCAM and a zwitterionic MPC polymer, and have shown that this conjugate endowed the surfaces of inorganic materials with the preferential affinity to EpCAM‐expressing EVs. This coating agent, designated as EpiVeta, could be useful as a coating for various diagnostic devices to allow concentration of cancer‐related EVs from heterogeneous EV mixtures.
Pharmacokinetics of pidotimod in broiler chickens by UHPLC–MS/MS after oral and intravenous administration
Authors: Zhang Ruili , Qiu Mei , Zhao Li , Cui Liangliang , Wang Chunyuan , Zhu Jiajia , Hao Zhihui 
Published: November 2017

AbstractPidotimod is widely used in children as an immune promoter but it has not been fully evaluated in animals. The pharmacokinetics of pidotimod and its oral bioavailability have not been described in broiler chickens. We developed a simple and sensitive UHPLC–MS/MS assay for rapid determination of pidotimod levels in chicken blood. Recoveries were nearly 100% and the coefficients of accuracy and precision were minimal. Healthy broiler chickens were given 10 mg/kg pidotimod either orally or intravenously. The oral pidotimod was rapidly absorbed (time to reach maximum concentration, 1.25 h) and rapidly eliminated (the mean residence time was 3.2 h). A noncompartmental analysis of the intravenous route indicated a mean plasma clearance of 2.2 L (h kg)−1 with an estimated mean volume of distribution at steady state of 12.69 L/kg. The bioavailability of pidotimod after oral dosing was 27%.
Does the end justify the means? The contemporary role of dissection/re‐entry strategies for recanalization of coronary chronic total occlusions
Authors: Karatasakis Aris , Brilakis Emmanouil S. 
Published: November 2017

Key Points

Antegrade and retrograde dissection/re‐entry techniques are frequently utilized in contemporary CTO PCI, especially for complex lesions.
One‐year outcomes with modern dissection/re‐entry techniques appear favorable and comparable with those achieved after intraplaque crossing, supporting their increased use.
Randomized data on the procedural safety, efficiency, and long‐term outcomes of subadventitial CTO PCI techniques are needed.
Comparison of self‐expanding and balloon‐expandable transcatheter aortic valves morphology and association with paravalvular regurgitation: Evaluation using multidetector computed tomography
Authors: Almeida João G. , Ferreira Sara M. , Fonseca Paulo , Dias Tiago , Guerreiro Cláudio , Barbosa Ana , Teixeira Pedro , Carvalho Mónica , Ferreira Wilson , Ferreira Nuno D. , Braga Pedro , Ribeiro José , Ribeiro Vasco G. 
Published: November 2017

ObjectivesCompare final morphology of self‐expanding and balloon‐expandable prosthesis and association with paravalvular regurgitation (PVR).BackgroundPVR after transcatheter aortic valve replacement (TAVR) remains a frequent complication. A better understanding of the prosthesis geometry may be important to improve selection of the best device for each case and possibly reduce the rates of PVR.MethodsRetrospective study including patients consecutively submitted to transcatheter aortic valve replacement: August/2007‐October/2016. Three months after the procedure a multidetector computed tomography (MDCT) was performed to assess prosthesis geometry: dimensions, eccentricity, and expansion.ResultsA total of 147 individuals were included (mean age of 78.8 ± 6.7 and 50.3% males), 57% treated with a self‐expanding prosthesis. On the postprocedure MDCT, the self‐expanding group had higher eccentricity index (15.0 vs. 7.1%, p < .001) and lower expansion (68.3 vs. 82.8%, p < .001). In that group, the volume of calcium of landing zone had a significant correlation with eccentricity index and under‐expansion. Patients with ≥mild PVR presented higher eccentricity (12.6 vs. 7.9%, p < .001) and lower expansion (68 vs. 75%, p = .012). Eccentricity index and landing zone calcium volume were independent predictors of PVR.ConclusionsSelf‐expanding prosthesis have greater eccentricity and under‐expansion. Calcium burden exerts more influence in the final morphology of that type of valve. Calcification and eccentricity are associated with the development of PVR. These factors should be considered in the selection of the most appropriate type of prosthesis for each scenario.
Fabricating Sulfur/Oxygen Co‐Doped Crumpled Graphene for High‐Performance Oxygen Reduction Reaction Electrocatalysis
Authors: Guo Mei , Qiu Chaochao , Li Yu , Jin Xiuyan , Zhang Guoxin , Sun Xiaoming 
Published: November 2017

AbstractHerein, defect‐rich graphene oxide with a crumpled form was fabricated through the fast thermal expansion of H2SO4‐intercalated graphite oxide. The fast removal of intercalated H2SO4 molecules and by‐product gases result in the formation of crumpled edges, whereas the partial reduction of H2SO4 leads to a large amount of defects and minor S doping (ca. 0.55 at%). The expanded graphene oxide with a crumpled form and rich defects was used as electrode materials for the oxygen reduction reaction (ORR), and a very high ORR performance was observed in 0.1 mol L−1 KOH, exhibiting an onset potential of 0.92 V, a half‐wave potential of 0.83 V, and a roughly 5.68 mA cm−2 limiting current density with catalyst loading of 0.1274 mg cm−2. Our work provides reliable GO‐based catalyst materials for the ORR; moreover, it will expand the knowledge one type of high‐activity site for the ORR: defects on crumpled edges.
A Critical Check for the Role of Resonance in Intramolecular Hydrogen Bonding
Authors: Jiang Xiaoyu , Zhang Huaiyu , Wu Wei , Mo Yirong 
Published: November 2017

AbstractAlthough resonance‐assisted H‐bonds (RAHBs) are well recognized, the role of π resonance in RAHBs is controversial, as the seemingly enhanced H‐bonds in unsaturated compounds may result from the constraints imposed by the σ skeleton. Herein the block‐localized wave function (BLW) method, which can derive optimal yet resonance‐quenched structures with related physiochemical properties, was employed to examine the correlation between π resonance and the strength of intramolecular RAHBs. Examination of a series of paradigmatic molecules with RAHBs and their saturated analogues showed that it is inappropriate to compare a conjugated system with its saturated counterpart, as they may have quite different σ frameworks. Nevertheless, comparison between a conjugated system and its resonance‐quenched (i.e., electron‐localized) state, which have identical σ skeletons, shows that in all studied cases, π resonance unanimously reduces the bonding distance by 0.111–0.477 Å, strengthens the bonding by 40–56 %, and redshifts the D−H vibrational frequency by 104–628 cm−1. Furthermore, there is an excellent correlation between hydrogen‐bonding strength and the classical Coulomb attraction between the hydrogen‐bond donor and the acceptor, which suggests that the dominant role of the electrostatic interaction in H‐bonds and RAHBs originates from the charge flow from H‐bond donors to acceptors through π conjugation.
Inserting Porphyrin Quantum Dots in Bottom‐Up Synthesized Graphene Nanoribbons
Authors: Perkins Wade , Fischer Felix R. 
Published: November 2017

AbstractDiels–Alder copolymerization of tetraphenylcyclopentadienone, a precursor for cove graphene nanoribbons (cGNRs), with bifunctional porphyrins yields defined nanostructures comprised of a single cGNR‐porphyrin‐cGNR heterojunction within each ribbon. 13C NMR labeling and high‐resolution mass spectrometry of solubilized polymer intermediates indicates that every porphyrin is covalently linked to two extended segments of cGNRs. UV/Vis absorption and fluorescence emission spectroscopy reveal a strong electronic correlation between the porphyrin and the adjacent cGNR segments that can be attenuated through reversible metalation of the porphyrin core. This versatile bottom‐up synthetic strategy provides access to structurally well‐defined, functional GNR‐quantum dot‐GNR heterostructures within a single graphene nanoribbon.
Inversion of Bicyclic Decanes: Rotational Spectra of the Trans and Double Cis Conformations of 2‐Decalone
Authors: Wachsmuth Dennis , Jahn Michaela K. , Blanco Susana , Gigosos Marco A. , Lesarri Alberto , Grabow Jens‐Uwe 
Published: November 2017

AbstractThe conformational landscape of the bicyclic molecule 2‐decalone has been studied in a jet‐cooled expansion by using rotational spectroscopy. The investigation covered the frequency region 7–19 GHz using broadband fast‐passage IMPACT Fourier‐transform microwave techniques. The introduction of the asymmetric carbonyl substituent in the double‐chair decalin skeleton originates two distinct inverting conformers with cis ring junction, which were independently identified and characterized in the gas phase. Additionally, a single trans conformer was detected, as expected for the non‐inverting equatorial ring junction. Accurate rotational parameters and quartic centrifugal distortion constants have been determined for the three observed species. A population estimation is given for the observed conformations based on relative intensities. Supporting ab initio calculations up to MP2/cc‐pVTZ complement the experimental work.
A Two‐Photon Luminescent Dye‐Loaded Metal–Organic Framework for Physiological Temperature Sensing within Biological Windows
Authors: Wan Yating , Xia Tifeng , Cui Yuanjing , Yang Yu , Qian Guodong 
Published: November 2017

AbstractLuminescent temperature sensing in biological windows is uniquely superior compared to traditional temperature sensing methods because the scattering and absorption by skin, tissue and blood is minimal. In this study, the two‐photon luminescence from dyes loaded into a metal–organic framework was utilised to achieve physiological temperature sensing within two biological windows. A composite was prepared that can be excited at 1064 nm to emit at 650 nm, well within the two biological windows. The two‐photon luminescence intensity at 650 nm has a linear relationship with temperature over the range 20 to 60 °C. In addition, the stability and quantum efficiency were significantly improved after loading into the MOF and, with high temperature resolution, excellent repeatability and low biological toxicity, measurements with this composite has great potential to be applied to physiological temperature sensing in cells or tissues.
Electrolyte Engineering towards Efficient Water Splitting at Mild pH
Authors: Shinagawa Tatsuya , Ng Marcus Tze‐Kiat , Takanabe Kazuhiro 
Published: November 2017

AbstractInvited for this month′s cover is the group of Takanabe Kazuhiro at King Abdullah University of Science and Technology (KAUST). The image shows how buffer species plays a crucial role for efficient water electrolysis at near‐neutral pH. The Full Paper itself is available at 10.1002/cssc.201701266.
High sensitivity of the Hematoflow™ solution for chronic myelomonocytic leukemia screening
Authors: Vazquez Romain , Roussel Mikael , Badaoui Bouchra , Freynet Nicolas , Tarfi Sihem , Solary Eric , Selimoglu‐Buet Dorothée , Wagner‐Ballon Orianne ,   on behalf of the Groupe Francophone des Myélodysplasies (GFM)
Published: November 2017

BackgroundAccumulation of classical monocytes CD14++CD16– (also called MO1) ≥ 94% can accurately distinguish chronic myelomonocytic leukemia (CMML) from reactive monocytosis. The HematoFlow™ solution, able to quantify CD16 negative monocytes, could be a useful tool to manage monocytosis which remains a common issue in routine laboratories.MethodsClassical monocytes were quantified from 153 whole blood samples collected on EDTA using both flow cytometry methods, either MO1 percentage determination by the multiparameter assay previously published and regarded here as the reference method, or CD16 negative monocyte percentage determination by the means of HematoFlow™.ResultsBoth methods of classical monocyte percentage determination were highly and significantly correlated (r = 0.87, P < 0.0001). The HematoFlow™ solution leant toward an overestimation of the genuine classical monocyte percentages obtained by the reference method. Percentages of CD16 negative monocytes provided by HematoFlow were higher than 94% for all the 73 patients displaying classical monocytes MO1 found ≥94% by the reference method, indicating a sensitivity of 100%. Furthermore, the calculation of CD16 negative monocyte percentage can be easily computerized and integrated to the middleware.ConclusionsWe propose a new application of the Hematoflow™ solution that can be used as a flag system for monocytosis management and CMML detection. © 2017 International Clinical Cytometry Society