bluuebunny/crossref_metadata_2025 huggingface dataset:
Os componentes da identidade de marca de Gramado/Brasil que geram sua imagem de “destino turístico modelo” e os relacionamentos da marca com os stakeholders internos
Authors: Azambuja Vanessa Acosta de , Mecca Marlei Salete
Published: December 2016

Esta pesquisa objetiva descrever os componentes da identidade de marca de Gramado/Brasil que geram sua imagem de “destino turístico modelo”, assim como verificar se há fortes relacionamentos entre a marca e os stakeholders internos dessa destinação. A principal teoria utilizada neste estudo é o modelo “rede relacional da marca” de Hankinson (2004). Sendo um estudo de caso, são realizadas entrevistas e consultadas outras fontes de evidência, como uma dissertação e uma reportagem. Integraram o universo da pesquisa sujeitos do Poder Público, da iniciativa privada, dos trabalhadores e da comunidade local de Gramado, totalizando 21 entrevistados. Os procedimentos organizativos e analíticos dos dados discursivos pautam-se por supostos e técnicas da análise de conteúdo. Dentre os resultados, está que os atributos com maior ocorrência nas respostas dos entrevistados são os simbólicos e os funcionais, destacando-se atrativos/eventos turísticos como aquilo que diferencia Gramado de seus concorrentes. Também, é constatada a falta de um planejamento estratégico com a participação ativa dos stakeholders internos.
Formação de Preço dos Hotéis Turísticos da Cidade de São Luís/Maranhão
Authors: Santos Mauro , Flores Luiz Carlos da Silva
Published: December 2016

O hotel é um estabelecimento comercial com o objetivo de prestação de serviços de hospedagem e alimentação, e para isso, possuem estruturas físicas que satisfaçam as condições específicas e básicas para receber hóspedes, em troca de pagamento. A precificação nesses empreendimentos pode ter enfoque nos custos, mercado, concorrência e na percepção de de valor. Alguns fatores podem ser considerados na formação de preços, tais como, demanda, segmentação, meteorologia, comportamento da concorrência e característica do estabelecimento entre outros. O objetivo deste artigo é analisar as estratégias de formação de preços nos meios de hospedagem em São Luís/Maranhão/Brasil. O estudo justifica-se pela relevância da precificação para a gestão hoteleira, a partir da realidade do setor hoteleiro em São Luís do Maranhão. Foi adotado procedimentos de pesquisa descritiva, predominantemente quantitativa, em uma amostragem de 31 empresas hoteleiras de São Luís, sendo os respondentes os gestores desses estabelecimentos. Os dados foram analisados com apoio software R versão 3.2.1. A pesquisa aponta que a rede hoteleira em São Luís do Maranhão utiliza as ferramentas e estratégias de gestão de preços recomendados pela legislação e outras de apoio para gestão dos preços. Conclui-se que há um esforço da gestão dos hotéis para profissionalizar os métodos de cálculo da diária, utilizando técnicas que lhes deem maior segurança na decisão e formação de preços, abandonando os métodos informais ou empíricos, sem abandonar a pesquisa de mercado.
Monasteries and tourism: interpreting sacred landscape through gastronomy
Authors: Aulet Silvia , Mundet Lluis , Vidal Dolors
Published: December 2016

This article analyses the role of monasteries as a sacred space and how their relationship with tourism depicts a landscape of 'good taste'. Monasteries are examples of both tangible and intangible heritage, and are highly symbolic built spaces that have often become the guardians of tradition. They are strongly embedded within a local cultural landscape, which has determined their historical evolution. Monasteries used to be self-sufficient communities that relied on the resources available in their local environment, e.g. they produced their own wine, which was essential for the celebration of the Eucharist; or they preserved food from their own produce. Gastronomy in monasteries can be a tool to improve tourists' visitor experience, in so far as it respects the values that these sacred spaces represent. This article explores the literature on monasteries as sacred spaces; the relationship between their tangible and intangible heritage attributes; and how monasteries and their heritage are linked to tourism. This is illustrated through examples from Spain.
Calcium Pyrophosphate Deposition Disease and Associated Medical Comorbidities: A National Cross‐Sectional Study of US Veterans
Authors: Kleiber Balderrama Crystal , Rosenthal Ann K. , Lans Daniel , Singh Jasvinder A. , Bartels Christie M.
Published: November 2016

Objective

Calcium pyrophosphate deposition disease (CPDD) is a common cause of acute and chronic arthritis, yet there are few large epidemiologic studies of CPDD. We sought to characterize CPDD in the national Veterans Affairs (VA) population.

Methods

Using data from the Department of VA Corporate Data Warehouse, patients with International Classification of Diseases, Ninth Revision, codes for CPDD seen at any VA medical center from 2010 through 2014 were matched by age and sex with control patients without CPDD. We used multivariate analysis to compare the prevalence and odds ratios (ORs) of various comorbidities, substance use, medication exposures, and arthroplasties among patients with and without CPDD.

Results

We identified 25,157 patients with CPDD, yielding a point prevalence of 5.2 per 1,000. The mean ± SD age was 68.1 ± 12.3 years, and 95% were male. The strongest positive associations with CPDD were hyperparathyroidism (OR 3.35 [95% confidence interval (95% CI) 2.96–3.79]), gout (OR 2.82 [95% CI 2.69–2.95]), osteoarthritis (OR 2.26 [95% CI 2.15–2.37]), rheumatoid arthritis (OR 1.88 [95% CI 1.74–2.03]), and hemochromatosis (OR 1.87 [95% CI 1.57–2.24]). Positive associations were also seen with higher odds for osteoporosis (OR 1.26 [95% CI 1.16–1.36]), hypomagnesemia (OR 1.23 [95% CI 1.16–1.30]), chronic kidney disease (OR 1.12 [95% CI 1.07–1.18]), and calcium supplementation (OR 1.15 [95% CI 1.06–1.24). Negative associations were seen with proton‐pump inhibitors (OR 0.58 [95% CI 0.55–0.60]) and loop diuretics (OR 0.80 [95% CI 0.76–0.84]).

Conclusion

Using a large national data set, we confirmed known associations with CPDD, provided support for positive associations with rheumatoid arthritis, hypomagnesemia, and osteoporosis, and suggested potential novel negative associations with commonly used medications.
Disease Outcomes and Care Fragmentation Among Patients With Systemic Lupus Erythematosus
Authors: Walunas Theresa L. , Jackson Kathryn L. , Chung Anh H. , Mancera‐Cuevas Karen A. , Erickson Daniel L. , Ramsey‐Goldman Rosalind , Kho Abel
Published: November 2016

Objective

To examine the impact of care fragmentation across multiple health care institutions on disease outcomes in patients with systemic lupus erythematosus (SLE).

Methods

Using the Chicago HealthLNK Data Repository, an assembly of electronic health records from 6 institutions, we identified patients with SLE, using International Classification of Diseases, Ninth Revision (ICD‐9) codes, whose care was delivered at more than 1 organization. We examined whether patients had severe infections or comorbidities (ICD‐9 code defined) that indicated SLE‐induced damage. T‐tests and chi‐square tests were used to examine differences between fragmentation groups. Logistic regression was used to assess factors contributing to the occurrence of disease outcomes.

Results

We identified 4,276 patients with SLE. A total of 856 (20%) received care from more than 1 health care institution. African American patients and patients with public insurance were more likely to experience care fragmentation compared to white and private insurance patients (odds ratio [OR] 1.66, 95% confidence interval [95% CI] 1.44–1.97 and OR 1.63, 95% CI 1.42–1.95). We identified increased risk of infections (OR 1.57, 95% CI 1.30–1.88), cardiovascular disease (OR 1.51, 95% CI 1.23–1.86), end‐stage renal disease (OR 1.34, 95% CI 1.05–1.70), nephritis (OR 1.28, 95% CI 1.07–1.54), and stroke (OR 1.28, 95% CI 1.01–1.62) among patients with fragmented care, adjusted for age, sex, race, insurance status, length of followup time, and total visit count.

Conclusion

In this cross‐site cohort of SLE patients, care fragmentation is associated with increased risk of severe infection and comorbidities. These results suggest that improved health information exchange could positively impact outcomes for SLE patients.
Reversible Decomposition of Secondary Phases in BaO Infiltrated LSM Electrodes—Polarization Effects
Authors: Traulsen Marie L. , McIntyre Melissa D. , Norrman Kion , Sanna Simone , Mogensen Mogens B. , Walker Robert A.
Published: November 2016

In operando Raman spectroscopy is used to study ceramic La0.85Sr0.15MnO3±δ electrodes infiltrated with BaO. The aim of this work is to clarify why BaO infiltration reduces the polarization resistance in oxygen containing atmospheres. Prior to the in operando experiments, ex situ X‐ray diffraction and Raman spectroscopy reveal the formation of a secondary phase, Ba3Mn2O8, on the electrode. During the in operando Raman investigation of the BaO‐infiltrated La0.85Sr0.15MnO3±δ electrodes, experiments are performed at 300 and 500 °C with oxygen partial pressure 0.1 atm and with −1 or +1 V applied potential. A changing electrode surface is observed during operation as the Ba3Mn2O8 secondary phase decomposes and manganese oxide accumulates on the electrode surface during cathodic polarization. The observed changes are reversible. These results suggest that the formation of Ba3Mn2O8 is responsible for the reduced polarization resistance observed at open circuit voltage (OCV) in an oxygen containing atmosphere. Furthermore, the results illustrate the dramatic differences between the electrode surface composition at OCV and during cathodic polarization. Overall, the results highlight the dynamic interactions between minor secondary phases and applied potential, a general effect that may be important for the high‐performance frequently observed with ceramic electrodes prepared by infiltration.
Asymmetric Hydroxylation of 4‐Substituted Pyrazolones Catalyzed by Natural Cinchona Alkaloids
Authors: Xue Fuzhao , Bao Xiaoze , Zou Liwei , Qu Jingping , Wang Baomin
Published: November 2016

A natural quinine‐catalyzed, efficient and practical asymmetric α‐hydroxylation of 4‐substituted pyrazolones has been developed, delivering a broad spectrum of pyrazolones bearing an oxygen‐attached carbon stereocenter at C‐4 in high yields and excellent enantioselectivities. The broad substrate scope, ready availability of the catalyst, ease of operation, and valuable transformation of the product highlight the practical utility of this process.

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Transition Metal‐Involved Photon Upconversion
Authors: Ye Shi , Song En‐Hai , Zhang Qin‐Yuan
Published: November 2016

Upconversion (UC) luminescence of lanthanide ions (Ln3+) has been extensively investigated for several decades and is a constant research hotspot owing to its fundamental significance and widespread applications. In contrast to the multiple and fixed UC emissions of Ln3+, transition metal (TM) ions, e.g., Mn2+, usually possess a single broadband emission due to its 3d5 electronic configuration. Wavelength‐tuneable single UC emission can be achieved in some TM ion‐activated systems ascribed to the susceptibility of d electrons to the chemical environment, which is appealing in molecular sensing and lighting. Moreover, the UC emissions of Ln3+ can be modulated by TM ions (specifically d‐block element ions with unfilled d orbitals), which benefits from the specific metastable energy levels of Ln3+ owing to the well‐shielded 4f electrons and tuneable energy levels of the TM ions. The electric versatility of d0 ion‐containing hosts (d0 normally viewed as charged anion groups, such as MoO66‐ and TiO44‐) may also have a strong influence on the electric dipole transition of Ln3+, resulting in multifunctional properties of modulated UC emission and electrical behaviour, such as ferroelectricity and oxide‐ion conductivity. This review focuses on recent advances in the room temperature (RT) UC of TM ions, the UC of Ln3+ tuned by TM or d0 ions, and the UC of d0 ion‐centred groups, as well as their potential applications in bioimaging, solar cells and multifunctional devices.
Development and validation of a septoplasty training model using 3‐dimensional printing technology
Authors: AlReefi Mahmoud A. , Nguyen Lily H.P. , Mongeau Luc G. , Haq Bassam ul , Boyanapalli Siddharth , Hafeez Nauman , Cegarra‐Escolano Francois , Tewfik Marc A.
Published: November 2016

Background

Providing alternative training modalities may improve trainees’ ability to perform septoplasty. Three‐dimensional printing has been shown to be a powerful tool in surgical training. The objectives of this study were to explain the development of our 3‐dimensional (3D) printed septoplasty training model, to assess its face and content validity, and to present evidence supporting its ability to distinguish between levels of surgical proficiency.

Methods

Imaging data of a patient with a nasal septal deviation was selected for printing. Printing materials reproducing the mechanical properties of human tissues were selected based on literature review and prototype testing. Eight expert rhinologists, 6 senior residents, and 6 junior residents performed endoscopic septoplasties on the model and completed a postsimulation survey. Performance metrics in quality (final product analysis), efficiency (time), and safety (eg, perforation length, nares damage) were recorded and analyzed in a study‐blind manner.

Results

The model was judged to be anatomically correct and the steps performed realistic, with scores of 4.05 ± 0.82 and 4.2 ± 1, respectively, on a 5‐point Likert scale. Ninety‐two percent of residents desired the simulator to be integrated into their teaching curriculum. There was a significant difference (p < 0.05) between the expert, intermediate, and novice groups in time taken and nares cuts, whereas other performance metrics showed no significant difference.

Conclusion

To our knowledge, there are no other simulator training models for septoplasty. Our model incorporates 2 different materials mixed into the 3 relevant consistencies necessary to simulate septoplasty. Our findings provide evidence supporting the validity of the model.
Copper‐Catalyzed Bromination of C(sp3)−H Bonds Distal to Functional Groups
Authors: Liu Tao , Myers Michael C. , Yu Jin‐Quan
Published: November 2016

Selective bromination of γ‐methylene C(sp3)−H bonds of aliphatic amides and δ‐methylene C(sp3)−H bonds of nosyl‐protected alkyl amines are developed using NBS as the brominating reagent and catalytic amount of CuII/phenanthroline complexes as the catalyst. Aryl and benzylic C−H bonds at other locations remain intact during this directed radical abstraction reaction.
Unambiguous Determination of Protein Arginine Ionization States in Solution by NMR Spectroscopy
Authors: Yoshimura Yuichi , Oktaviani Nur Alia , Yonezawa Kento , Kamikubo Hironari , Mulder Frans A. A.
Published: November 2016

Because arginine residues in proteins are expected to be in their protonated form almost without exception, reports demonstrating that a protein arginine residue is charge‐neutral are rare and potentially controversial. Herein, we present a 13C‐detected NMR experiment for probing individual arginine residues in proteins notwithstanding the presence of chemical and conformational exchange effects. In the experiment, the 15Nη and 15Nϵ chemical shifts of an arginine head group are correlated with that of the directly attached 13Cζ. In the resulting spectrum, the number of protons in the arginine head group can be obtained directly from the 15N–1H scalar coupling splitting pattern. We applied this method to unambiguously determine the ionization state of the R52 side chain in the photoactive yellow protein from Halorhodospira halophila. Although only three Hη atoms were previously identified by neutron crystallography, we show that R52 is predominantly protonated in solution.
Efficient Overall Water‐Splitting Electrocatalysis Using Lepidocrocite VOOH Hollow Nanospheres
Authors: Shi Huanhuan , Liang Hanfeng , Ming Fangwang , Wang Zhoucheng
Published: November 2016

Herein we report the control synthesis of lepidocrocite VOOH hollow nanospheres and further their applications in electrocatalytic water splitting for the first time. By tuning the surface area of the nanospheres, the optimal performance can be achieved with low overpotentials of 270 mV for the oxygen evolution reaction (OER) and 164 mV for the hydrogen evolution reaction (HER) at 10 mA cm−2 in 1 m KOH, respectively. Furthermore, when used as both the anode and cathode for overall water splitting, a low cell voltage of 1.62 V is required to reach the current density of 10 mA cm−2, making the VOOH hollow nanospheres an efficient alternative to water splitting.
Discrete Silver(I)‐Palladium(II)‐Oxo Nanoclusters, {Ag4Pd13} and {Ag5Pd15}, and the Role of Metal–Metal Bonding Induced by Cation Confinement
Authors: Yang Peng , Xiang Yixian , Lin Zhengguo , Lang Zhongling , Jiménez‐Lozano Pablo , Carbó Jorge J. , Poblet Josep M. , Fan Linyuan , Hu Changwen , Kortz Ulrich
Published: November 2016

We introduce the class of discrete silver(I)‐palladium(II)‐oxo nanoclusters with the preparation of {Ag4Pd13} and {Ag5Pd15}. Both polyanions represent the first examples of noble metal‐capped polyoxo‐noble‐metalates in a fully inorganic assembly, featuring an unprecedented host–guest mode containing hetero‐ and homometallic Ag–Pd and Ag–Ag bonding interactions. Comprehensive theoretical calculations suggest that the Ag–Pd metallic bonds originate partially from surface confinement of AgIguest ions onto the anionic polyoxopalladate host that is induced by strong electrostatic forces. This work opens the field of fully inorganic silver‐palladium‐oxo nanoclusters, which can be considered as discrete mixed noble metal precursors for the formation of monodisperse core–shell nanoparticles, with high relevance for catalysis.
Profiling Functional and Biochemical Phenotypes of Circulating Tumor Cells Using a Two‐Dimensional Sorting Device
Authors: Poudineh Mahla , Labib Mahmoud , Ahmed Sharif , Nguyen L. N. Matthew , Kermanshah Leyla , Mohamadi Reza M. , Sargent Edward H. , Kelley Shana O.
Published: November 2016

During cancer progression, tumors shed circulating tumor cells (CTCs) into the bloodstream. CTCs that originate from the same primary tumor can have heterogeneous phenotypes and, while some CTCs possess benign properties, others have high metastatic potential. Deconstructing the heterogeneity of CTCs is challenging and new methods are needed that can sort small numbers of cancer cells according to their phenotypic properties. Here we describe a new microfluidic approach that profiles, along two independent phenotypic axes, the behavior of heterogeneous cell subpopulations. Cancer cells are first profiled according to expression of a surface marker using a nanoparticle‐enabled approach. Along the second dimension, these subsets are further separated into subpopulations corresponding to migration profiles generated in response to a chemotactic agent. We deploy this new technique and find a strong correlation between the surface expression and migration potential of CTCs present in blood from mice with xenografted tumors. This system provides an important new means to characterize functional diversity in circulating tumor cells.
Gating of Quantum Interference in Molecular Junctions by Heteroatom Substitution
Authors: Liu Xunshan , Sangtarash Sara , Reber David , Zhang Dan , Sadeghi Hatef , Shi Jia , Xiao Zong‐Yuan , Hong Wenjing , Lambert Colin J. , Liu Shi‐Xia
Published: November 2016

To guide the choice of future synthetic targets for single‐molecule electronics, qualitative design rules are needed, which describe the effect of modifying chemical structure. Here the effect of heteroatom substitution on destructive quantum interference (QI) in single‐molecule junctions is, for the first time experimentally addressed by investigating the conductance change when a “parent” meta‐phenylene ethylene‐type oligomer (m‐OPE) is modified to yield a “daughter” by inserting one nitrogen atom into the m‐OPE core. We find that if the substituted nitrogen is in a meta position relative to both acetylene linkers, the daughter conductance remains as low as the parent. However, if the substituted nitrogen is in an ortho position relative to one acetylene linker and a para position relative to the other, destructive QI is alleviated and the daughter conductance is high. This behavior contrasts with that of a para‐connected parent, whose conductance is unaffected by heteroatom substitution. These experimental findings are rationalized by transport calculations and also agree with recent “magic ratio rules”, which capture the role of connectivity in determining the electrical conductance of such parents and daughters.
BCl3‐Induced Annulative Oxo‐ and Thioboration for the Formation of C3‐Borylated Benzofurans and Benzothiophenes
Authors: Warner Andrew J. , Churn Anna , McGough John S. , Ingleson Michael J.
Published: November 2016

BCl3‐induced borylative cyclization of aryl‐alkynes possessing ortho‐EMe (E=S, O) groups represents a simple, metal‐free method for the formation of C3‐borylated benzothiophenes and benzofurans. The dichloro(heteroaryl)borane primary products can be protected to form synthetically ubiquitous pinacol boronate esters or used in situ in Suzuki–Miyaura cross couplings to generate 2,3‐disubstituted heteroarenes from simple alkyne precursors in one pot. In a number of cases alkyne trans‐haloboration occurs alongside, or instead of, borylative cyclization and the factors controlling the reaction outcome are determined.
Rheological investigation of a random copolymer of polyacrylamide and polyacryloyl hydrazide (PAM‐ran‐PAH) for oil recovery applications
Authors: Raman Ujjwal Rewati , Sharma Tushar , Sangwai Jitendra S. , Ojha Umaprasana
Published: November 2016

In this article, we synthesize and investigate the rheological properties of a random copolymer PAM‐ran‐PAH of polyacrylamide (PAM) and polyacryloyl hydrazide (PAH) and compare with the results of PAM at different temperature (30 and 80 °C) and salinity (0 and 1.0 wt %). At 30 °C, both PAM and PAM‐ran‐PAH exhibited non‐Newtonian rheology with both shear thinning and shear thickening responses. The rheological properties such as viscosity and moduli (G′ and G″) of PAM significantly deformed at elevated temperature (80 °C) and salinity (1.0 wt %), resulting no recovery in viscosity and moduli. On the other hand, the effect of temperature and salinity was found to be least on PAM‐ran‐PAH and showed better stability with the possibility of recovering its original rheological properties. The performance of PAM and PAM‐ran‐PAH was also characterized by enhanced oil recovery tests. The use of PAM‐ran‐PAH for polymer flooding, due to its stable rheology, resulted in an increase in the oil recovery than PAM. In general, the rheological behavior of PAM‐ran‐PAH as a chemical agent proved to be thermally stable than PAM, which clearly supports its use for saline environment and high temperature applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44648.
The feasibility of printing polylactic acid–nanohydroxyapatite composites using a low‐cost fused deposition modeling 3D printer
Authors: Esposito Corcione Carola , Gervaso Francesca , Scalera Francesca , Montagna Francesco , Sannino Alessandro , Maffezzoli Alfonso
Published: November 2016

The current “gold standard” to treat bone lesions is allografts and autografts, both presenting important disadvantages such as risk of infection and morbidity. Synthetic grafts and scaffolds for bone regeneration represent a promising solution. Fused deposition modeling is a valid tool for developing synthetic bone grafts of complex shapes, which is a key issue. The possibility of building polylactic acid–nanohydroxyapatite (PLA/nanoHA) composites by 3D printing was systematically evaluated. PLA/nanoHA filaments for low‐cost 3D printers were produced by a multistep solvent‐free procedure and characterized by scanning electron microscopy, energy dispersive X‐ray spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry, and rheometry. TGA analysis confirmed the presence of the nanoHA amounts used in the composites, equal to 5 and 15 wt %. The glass‐transition temperature and degree of crystallinity of PLA are not influenced by presence of nanoHA, which remains substantially amorphous. The morphological analysis and compression testing on printed samples showed that nanoHA was uniformly dispersed within the PLA matrix and improved the PLA mechanical properties without changing the rheological performance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44656.
Double‐Side Co‐Catalytic Activation of Anodic TiO2 Nanotube Membranes with Sputter‐Coated Pt for Photocatalytic H2 Generation from Water/Methanol Mixtures
Authors: Cha Gihoon , Altomare Marco , Truong Nguyen Nhat , Taccardi Nicola , Lee Kiyoung , Schmuki Patrik
Published: November 2016

Self‐standing TiO2 nanotube layers in the form of membranes are fabricated by self‐organizing anodization of Ti metal and a potential shock technique. The membranes are then decorated by sputtering different Pt amounts i) only at the top, ii) only at the bottom or iii) at both top and bottom of the tube layers. The Pt‐decorated membranes are transferred either in tube top‐up or in tube top‐down configuration onto FTO slides and are investigated, after crystallization, as photocatalysts for H2 generation using either front or back‐side light irradiation. Double‐side Pt‐decoration of the tube membranes leads to higher H2 generation rates (independently of tube and light‐irradiation configuration) compared to membranes decorated at only one side with similar overall Pt amounts. The results suggest that this effect cannot be only ascribed to the overall amount of Pt co‐catalyst as such but also to its distribution at both tube extremities. This leads to optimized light absorption and electron diffusion/transfer dynamics: the central part of the membranes acts as light‐harvesting zone and electrons therein generated can diffuse towards the Pt/TiO2 active zones (tube extremities) where they can react with the environment and generate H2.
Stimuli‐Responsive Cucurbit[7]uril‐Mediated BSA Nanoassembly for Uptake and Release of Doxorubicin
Authors: Barooah Nilotpal , Kunwar Amit , Khurana Raman , Bhasikuttan Achikanath C. , Mohanty Jyotirmayee
Published: November 2016

We report the construction of a non‐toxic nanoassembly of bovine serum albumin (BSA) protein and the cucurbit[7]uril macrocycle as well as its stimuli‐responsive breakage with adamantylamine or pH, which restores the protein structure and recognition properties. The assembly showed efficient loading and controlled release of a standard drug, doxorubicin (DOX), and the same was validated in live cells. The cell viability studies documented that the DOX‐loaded assembly mask the cytotoxicity of DOX and the toxicity can be revived at the target on demand, triggering its therapeutic activation. This is found to be more effective in the cancer cells. In addition, such host‐assisted protein assemblies are also highly promising for stabilizing/protecting the native protein structure, a viable approach to prevent/inhibit protein misfolding and aggregation.
Photoswitchable and Water‐Soluble Fluorescent Nano‐Aggregates Based on a Diarylethene–Dansyl Dyad and Liposome
Authors: Cheng Hongbo , Ma Pin , Wang Yanan , Hu Guofei , Fang Shibi , Fang Yanyan , Lin Yuan
Published: November 2016

In this work, a unique approach is developed to generate photoswitchable and water‐soluble fluorescent nano‐aggregates. Initially, a new light‐controlled diarylethene–dansyl dyad DAE 1 is formed by linking two dansyl fluorophores covalently to a symmetrical dithienylethene backbone, whose photophysical properties can be reversibly switched by optical stimuli. Subsequently, the water insolubility of the molecular switch 1 is overcome by incorporating it into the bilayer of liposome DPPC (1,2‐dihexadecanoyl‐sn‐glycero‐3‐phosphocholine) in water. This strategy creates stable fluorescent nano‐aggregates OF‐1@DPPC (≈25 nm diameter) that are soluble in an aqueous medium. The nano‐aggregates OF‐1@DPPC retain and even improve the photoswitchable fluorescence properties of DAE 1. More importantly, OF‐1@DPPC exhibits a remarkable photostability and fatigue resistance after 5 cycles of irradiation with UV and visible light, which is crucial for its practical application.
Self‐calibration strategy for a LOFAR solar radio burst observation
Authors: Vocks C. , Mann G. , Breitling F.
Published: November 2016

The LOw Frequency ARray (LOFAR) is a novel radio interferometer consisting of a central core near Exloo in the Netherlands, remote stations in the Netherlands, and international stations. It observes in two frequency bands, the low band of 10–90 MHz and the high band of 110–250 MHz. The key science project “Solar Physics and Space Weather with LOFAR” aims at studying the solar activity and its influence on interplanetary space. Solar radio radiation in the low and high band emanates from the upper and middle corona, respectively. We present early commissioning observations of the Sun, that serendipitously include a weak radio burst. Since no external calibrator was observed, a self‐calibration approach has tobe used. This works well for the quiet Sun, but not for the burst data. We develop a self‐calibration strategy for radio bursts, and discuss the general properties of such a self‐calibration method. Our results lead to the conclusion that external calibrators with known source structure should generally be preferred. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Reduced modulation of thalamocortical connectivity during exposure to sensory stimuli in ASD
Authors: Green Shulamite A. , Hernandez Leanna , Bookheimer Susan Y. , Dapretto Mirella
Published: November 2016

Recent evidence for abnormal thalamic connectivity in autism spectrum disorders (ASD) and sensory processing disorders suggests the thalamus may play a role in sensory over‐responsivity (SOR), an extreme negative response to sensory stimuli, which is common in ASD. However, there is yet little understanding of changes in thalamic connectivity during exposure to aversive sensory inputs in individuals with ASD. In particular, the pulvinar nucleus of the thalamus is implicated in atypical sensory processing given its role in selective attention, regulation, and sensory integration. This study aimed to examine the role of pulvinar connectivity in ASD during mildly aversive sensory input. Functional magnetic resonance imaging was used to examine connectivity with the pulvinar during exposure to mildly aversive auditory and tactile stimuli in 38 youth (age 9–17; 19 ASD, 19 IQ‐matched typically developing (TD)). Parents rated children's SOR severity on two standard scales. Compared to TD, ASD participants displayed aberrant modulation of connectivity between pulvinar and cortex (including sensory‐motor and prefrontal regions) during sensory stimulation. In ASD participants, pulvinar‐amygdala connectivity was correlated with severity of SOR symptoms. Deficits in modulation of thalamocortical connectivity in youth with ASD may reflect reduced thalamo‐cortical inhibition in response to sensory stimulation, which could lead to difficulty filtering out and/or integrating sensory information. An increase in amygdala connectivity with the pulvinar might be partially responsible for deficits in selective attention as the amygdala signals the brain to attend to distracting sensory stimuli. Autism Res 2017, 10: 801–809. © 2016 International Society for Autism Research, Wiley Periodicals, Inc.
Mid‐childhood outcomes of infant siblings at familial high‐risk of autism spectrum disorder
Authors: Shephard Elizabeth , Milosavljevic Bosiljka , Pasco Greg , Jones Emily J. H. , Gliga Teodora , Happé Francesca , Johnson Mark H. , Charman Tony ,   The BASIS Team
Published: November 2016

Almost 20% of infants with an older sibling with autism spectrum disorder (ASD) exhibit ASD themselves by age 3 years. The longer‐term outcomes of high‐risk infants are less clear. We examined symptoms of ASD, attention‐deficit/hyperactivity disorder (ADHD) and anxiety, language, IQ, and adaptive behaviour at age 7 years in high‐ and low‐risk children prospectively studied since the first year of life. Clinical outcomes were compared between high‐risk children who met diagnostic criteria for ASD at age 7 (HR‐ASD‐7 group, n = 15), high‐risk children without ASD (HR‐Non‐ASD‐7 group, n = 24), and low‐risk control children (LR group, n = 37). Diagnostic stability between age 3 and 7 years was moderate, with five children who did not meet diagnostic criteria for ASD at age 3 years being assigned the diagnosis at age 7, and three children showing the opposite pattern. The HR‐ASD‐7 group showed elevated ADHD and anxiety symptoms and had lower adaptive behaviour scores than LR controls. The HR‐Non‐ASD‐7 group had higher repetitive behaviour, lower adaptive functioning and elevated scores on one anxiety subscale (Separation Anxiety) compared to LR controls, but evidence for subclinical ASD symptoms (the broader autism phenotype, BAP) was limited in the group as a whole, although we identified a subgroup with elevated ASD traits. The difficulties experienced by high‐risk siblings at school‐age extend beyond ASD symptoms. The pattern of difficulties exhibited by the HR‐ASD‐7 group may inform our understanding of developmental trajectories of co‐occurring psychopathology in ASD. Autism Res 2017, 10: 546–557. © The Authors Autism Research published by Wiley Periodicals, Inc. on behalf of International Society for Autism Research
Curcumin as a multifaceted compound against human papilloma virus infection and cervical cancers: A review of chemistry, cellular, molecular, and preclinical features
Authors: Teymouri Manouchehr , Pirro Matteo , Johnston Thomas P. , Sahebkar Amirhosein
Published: November 2016

Curcumin, the bioactive polyphenolic ingredient of turmeric, has been extensively studied for its effects on human papilloma virus (HPV) infection as well as primary and malignant squamous cervical cancers. HPV infections, especially those related to HPV 16 and 18 types, have been established as the leading cause of cervical cancer; however, there are also additional contributory factors involved in the etiopathogenesis of cervical cancers. Curcumin has emerged as having promising chemopreventive and anticancer effects against both HPV‐related and nonrelated cervical cancers. In this review, we first discuss the biological relevance of curcumin and both its pharmacological effects and pharmaceutical considerations from a chemical point of view. Next, the signaling pathways that are modulated by curcumin and are relevant to the elimination of HPV infection and treatment of cervical cancer are discussed. We also present counter arguments regarding the effects of curcumin on signaling pathways and molecular markers dysregulated by benzo(a)pyrene (Bap), a carcinogen found in pathological cervical lesions of women who smoke frequently, and estradiol, as two important risk factors involved in persistent HPV‐infection and cervical cancer. Finally, various strategies to enhance the pharmacological activity and pharmacokinetic characteristics of curcumin are discussed with examples of studies in experimental models of cervical cancer. © 2016 BioFactors, 43(3):331–346, 2017
Reconstruction of biological pathways and metabolic networks from in silico labeled metabolites
Authors: Hadadi Noushin , Hafner Jasmin , Soh Keng Cher , Hatzimanikatis Vassily
Published: November 2016

Reaction atom mappings track the positional changes of all of the atoms between the substrates and the products as they undergo the biochemical transformation. However, information on atom transitions in the context of metabolic pathways is not widely available in the literature. The understanding of metabolic pathways at the atomic level is of great importance as it can deconvolute the overlapping catabolic/anabolic pathways resulting in the observed metabolic phenotype. The automated identification of atom transitions within a metabolic network is a very challenging task since the degree of complexity of metabolic networks dramatically increases when we transit from metabolite‐level studies to atom‐level studies. Despite being studied extensively in various approaches, the field of atom mapping of metabolic networks is lacking an automated approach, which (i) accounts for the information of reaction mechanism for atom mapping and (ii) is extendable from individual atom‐mapped reactions to atom‐mapped reaction networks. Hereby, we introduce a computational framework, iAM.NICE (in silico Atom Mapped Network Integrated Computational Explorer), for the systematic atom‐level reconstruction of metabolic networks from in silico labelled substrates. iAM.NICE is to our knowledge the first automated atom‐mapping algorithm that is based on the underlying enzymatic biotransformation mechanisms, and its application goes beyond individual reactions and it can be used for the reconstruction of atom‐mapped metabolic networks. We illustrate the applicability of our method through the reconstruction of atom‐mapped reactions of the KEGG database and we provide an example of an atom‐level representation of the core metabolic network of E. coli.
Modern Approaches to Discovering New Hydroxynitrile Lyases for Biocatalysis
Authors: Padhi Santosh Kumar
Published: November 2016

Hydroxynitrile lyases (HNLs) have grown in importance from laboratory to industry due to their potential to catalyze stereoselective C−C bond‐formation reactions in the synthesis of several chiral intermediates, such as enantiopure α‐cyanohydrins, β‐nitro alcohols, and their derivatives with multiple functional groups. With these wide applications, the demand for finding new HNLs has increased, and this has led to exploration not only of new HNLs but also of new ways to discover them. An exclusive review article on HNLs by Asano et al. in 2011 described the discovery of HNLs along with their applications. Since then many scientific advancements have been seen in this area. This article aims to highlight the modern HNL discovery approaches, based mainly on 1) genome mining, 2) use of INTMSAlign software, 3) rational design (based on a millipede HNL), 4) evolution of catalytic mechanisms, 5) protein engineering guided by catalytic mechanisms, and 6) screening of plants with cyanogen glycoside (CG) content. This description is followed by future prospects. Overall this review represents the present state and the future potential of HNL discovery approaches, and so might be hoped to be instrumental not only in exploration of new HNLs but also in the invention of methods for potential biotechnological applications.
Bifunctionality of ActIV as a Cyclase‐Thioesterase Revealed by in Vitro Reconstitution of Actinorhodin Biosynthesis in Streptomyces coelicolor A3(2)
Authors: Taguchi Takaaki , Awakawa Takayoshi , Nishihara Yukitaka , Kawamura Michiho , Ohnishi Yasuo , Ichinose Koji
Published: November 2016

Type II polyketide synthases iteratively generate a nascent polyketide thioester of the acyl carrier protein (ACP); this is structurally modified to produce an ACP‐free intermediate towards the final metabolite. However, the timing of ACP off‐loading is not well defined because of the lack of an apparent thioesterase (TE) among relevant biosynthetic enzymes. Here, ActIV, which had been assigned as a second ring cyclase (CYC) in actinorhodin (ACT) biosynthesis, was shown to possess TE activity in vitro with a model substrate, anthraquinone‐2‐carboxylic acid‐N‐acetylcysteamine. In order to investigate its function further, the ACT biosynthetic pathway in Streptomyces coelicolor A3(2) was reconstituted in vitro in a stepwise fashion up to (S)‐DNPA, and the product of ActIV reaction was characterized as an ACP‐free bicyclic intermediate. These findings indicate that ActIV is a bifunctional CYC‐TE and provide clear evidence for the release timing of the intermediate from the ACP anchor.
Roles of Alkaline Earth Ions in Garnet‐Type Superionic Conductors
Authors: Song Shufeng , Kotobuki Masashi , Zheng Feng , Xu Chaohe , Wang Yu , Li Wei Dong Z. , Hu Ning , Lu Li
Published: November 2016

The roles of alkaline earth ions in garnet‐type superionic conductors Li7.1La3Zr1.95M0.05O12 (M=Mg, Sr, Ba) are further investigated. In contrast to previous reports, the alkaline earth ions are specifically allocated to the octahedral sites (Zr4+ sites) instead of dodecahedral sites (La3+ sites) in the present work. The alkaline‐earth‐ion‐doped Li7.1La3Zr1.95M0.05O12 garnets exhibit enhanced room‐temperature conductivities with the increasing ionic radii of alkaline‐earth ions. Ba‐doped Li7.1La3Zr1.95Ba0.05O12 provides the highest conductivity of 1.13×10−3 S cm−1 at room temperature, whereas Mg‐ and Sr‐doped garnets show conductivities of 4.32×10−4 and 8.91×10−4 S cm−1 at room temperature, respectively. The obtained ionic conductivities are comparable to other promising superionic conductors that are already known. Moreover, the alkaline‐earth‐ion‐doped garnets demonstrate a wide electrochemical stability window of 9 V vs. Li/Li+, and stability against metallic lithium by means of symmetric galvanostatic cycling.
Cooperativity in the Self‐Assembly of the Guanine Nucleobase into Quartet and Ribbon Structures on Surfaces
Authors: Paragi Gábor , Fonseca Guerra Célia
Published: November 2016

The guanine nucleobase can self‐assemble into tetrameric or ribbon structures on surfaces or in solution. The origin for the occurrence of different aggregation patterns has not yet been investigated. Herein, a quantum chemical study on the different self‐assembled structures of guanine and xanthine by using dispersion‐corrected DFT is presented. Theoretical investigations can be used to explain, from an electronic point of view, the differences between the experimental findings. With quantitative Kohn–Sham molecular orbital theory and the accompanying energy decomposition analysis, the hydrogen‐bonding mechanism within the guanine ribbons can be disclosed and the preferred self‐assembled structures under different experimental conditions can be explained. An important role of the σ‐electronic system in the guanine self‐assembled structures is revealed as the main factor for the switch between different arrangements on surfaces and in crystals.
Co‐existence of Distinct Supramolecular Assemblies in Solution and in the Solid State
Authors: Reddy G. N. Manjunatha , Huqi Aida , Iuga Dinu , Sakurai Satoshi , Marsh Andrew , Davis Jeffery T. , Masiero Stefano , Brown Steven P.
Published: November 2016

The formation of distinct supramolecular assemblies, including a metastable species, is revealed for a lipophilic guanosine (G) derivative in solution and in the solid state. Structurally different G‐quartet‐based assemblies are formed in chloroform depending on the nature of the cation, anion and the salt concentration, as characterized by circular dichroism and time course diffusion‐ordered NMR spectroscopy data. Intriguingly, even the presence of potassium ions that stabilize G‐quartets in chloroform was insufficient to exclusively retain such assemblies in the solid state, leading to the formation of mixed quartet and ribbon‐like assemblies as revealed by fast magic‐angle spinning (MAS) NMR spectroscopy. Distinct N−H⋅⋅⋅N and N−H⋅⋅⋅O intermolecular hydrogen bonding interactions drive quartet and ribbon‐like self‐assembly resulting in markedly different 2D 1H solid‐state NMR spectra, thus facilitating a direct identification of mixed assemblies. A dissolution NMR experiment confirmed that the quartet and ribbon interconversion is reversible–further demonstrating the changes that occur in the self‐assembly process of a lipophilic nucleoside upon a solid‐state to solution‐state transition and vice versa. A systematic study for complexation with different cations (K+, Sr2+) and anions (picrate, ethanoate and iodide) emphasizes that the existence of a stable solution or solid‐state structure may not reflect the stability of the same supramolecular entity in another phase.
Isomerization of Keggin Al13 Ions Followed by Diffusion Rates
Authors: Oliveri Anna F. , Colla Christopher A. , Perkins Cory K. , Akhavantabib Noushin , Callahan Joseph R. , Pilgrim Corey D. , Smart Scott E. , Cheong Paul H.‐Y. , Pan Long , Casey William H.
Published: November 2016

Invited for the cover of this issue is a group of researchers from the University of California Davis, Colgate–Palmolive Company, and Oregon State University. The image depicts aluminum ions as silver spheres, oxygen atoms as red spheres, carbon as black spheres, and nitrogen as green spheres. Hydrogen atoms were omitted for clarity. Read the full text of the article, which also includes insight on the other aluminum clusters that glycine stabilizes, at 10.1002/chem.201604640.
Color separation for improved perceived image quality in terms of graininess and gamut
Authors: Žitinski Elías Paula , Nyström Daniel , Gooran Sasan
Published: November 2016

Multi‐channel printing employs additional inks to improve the perceived image quality by reducing the graininess and augmenting the printer gamut. It also requires a color separation that deals with the one‐to‐many mapping problem imposed when using more than three inks. The proposed separation model incorporates a multilevel halftoning algorithm, reducing the complexity of the print characterization by grouping inks of similar hues in the same channel. In addition, a cost function is proposed that weights selected factors influencing the print and perceived image quality, namely color accuracy, graininess and ink consumption. The graininess perception is qualitatively assessed using S‐CIELAB, a spatial low‐pass filtering mimicking the human visual system. By applying it to a large set of samples, a generalized prediction quantifying the perceived graininess is carried out and incorporated as a criterion in the color separation. The results of the proposed model are compared with the separation giving the best colorimetric match, showing improvements in the perceived image quality in terms of graininess at a small cost of color accuracy and ink consumption. © 2016 Wiley Periodicals, Inc. Col Res Appl, 42, 486–497, 2017
A Fundamental Tandem Mass Spectrometry Study of the Collision‐Activated Dissociation of Small Deprotonated Molecules Related to Lignin
Authors: Marcum Christopher L. , Jarrell Tiffany M. , Zhu Hanyu , Owen Benjamin C. , Haupert Laura J. , Easton Mckay , Hosseinaei Omid , Bozell Joseph , Nash John J. , Kenttämaa Hilkka I.
Published: November 2016

The collision‐activated fragmentation pathways and reaction mechanisms of 34 deprotonated model compounds representative of lignin degradation products were explored experimentally and computationally. The compounds were evaporated and ionized by using negative‐ion mode electrospray ionization doped with NaOH to produce abundant deprotonated molecules. The ions were isolated and subjected to collision‐activated dissociation (CAD). Their fragment ions were then isolated and also subjected to CAD. This was repeated until no further fragmentation was observed (up to MS6). This approach enabled the identification of characteristic reaction pathways and delineation of reasonable fragmentation mechanisms for deprotonated molecules containing various functional groups. The varying fragmentation patterns observed for different types of compounds allow for the identification of the functionalities in these compounds. This information was utilized to identify the presence of specific functionalities and their combinations in molecules in an organosolv lignin sample.