bluuebunny/crossref_metadata_2025 huggingface dataset:
Reconstitution of a Type II Polyketide Synthase that Catalyzes Polyene Formation
Authors: Du Danyao , Katsuyama Yohei , Shin‐ya Kazuo , Ohnishi Yasuo
Published: December 2017

While type II polyketide synthases (PKSs) are known for producing aromatic compounds, a phylogenetically new subfamily of type II PKSs have been recently proposed to synthesize polyene structures. Here we report in vitro analysis of such a type II PKS, IgaPKS for ishigamide biosynthesis. The ketoreductase (Iga13) and dehydratase (Iga16) were shown to catalyze the reduction of a β‐keto group and dehydration of a β‐hydroxy group, respectively, to form a trans double bond. Incubation of the acyl carrier protein (Iga10), the ketosynthase/chain length factor complex (Iga11–Iga12), Iga13 and Iga16 with malonyl and hexanoyl‐CoAs and NADPH followed by KOH hydrolysis resulted in the formation of four unsaturated carboxylic acids (C8, C10, C12, and C14), indicating that IgaPKS catalyzes tetraene formation by repeating the cycle of condensation, keto‐reduction and dehydration with strict stereo‐specificity. We propose “highly reducing type II PKS subfamily” for the polyene‐producing type II PKSs.
Highly Regio‐ and Stereodivergent Access to 1,2‐Amino Alcohols or 1,4‐Fluoro Alcohols by NHC‐Catalyzed Ring Opening of Epoxy enals
Authors: Poh Si Bei , Ong Jun‐Yang , Lu Shenci , Zhao Yu
Published: December 2017

Described is an unprecedented NHC‐catalyzed (NHC=N‐heterocyclic carbene), stereoselective ring opening of epoxy and cyclopropyl enals to deliver valuable compounds bearing multiple stereocenters. A straightforward three‐step procedure involving two catalytic enantioselective transformations has been developed and leads to a regio‐ and stereodivergent synthesis of either 1,2‐amino alcohols/diamines or 1,4‐fluoro alcohols with excellent diastereo‐ and enantiopurity.
In‐Plane Black Phosphorus/Dicobalt Phosphide Heterostructure for Efficient Electrocatalysis
Authors: Wang Jiahong , Liu Danni , Huang Hao , Yang Na , Yu Bo , Wen Min , Wang Xin , Chu Paul K. , Yu Xue‐Feng
Published: December 2017

Heterostructures composed of two‐dimensional black phosphorus (2D BP) with unique physical/chemical properties are of great interest. Herein, we report a simple solvothermal method to synthesize in‐plane BP/Co2P heterostructures for electrocatalysis. By using the reactive edge defects of the BP nanosheets as the initial sites, Co2P nanocrystals are selectively grown on the BP edges to form the in‐plane BP/Co2P heterostructures. Owing to disposition on the original defects of BP, Co2P improves the conductivity and offers more active electrocatalytic sites, so that the BP/Co2P nanosheets exhibit better and more stable electrocatalytic activities in the hydrogen evolution and oxygen evolution reactions. Our work not only extends the application of BP to electrochemistry, but also provides a new idea to improve the performance of BP by utilization of defects. Furthermore, this strategy can be extended to produce other BP heterostructures to expand the corresponding applications.
Auf sichtbares Licht ansprechende Photoanoden für hochaktive, dauerhafte Wasseroxidation
Authors: Seo Jeongsuk , Nishiyama Hiroshi , Yamada Taro , Domen Kazunari
Published: December 2017

Solarenergie ist eine natürliche und ständig verfügbare Ressource, sodass die Umwandlung von Sonnenstrahlung in chemische oder elektrische Energie eine attraktive Möglichkeit, wenngleich auch eine anspruchsvolle Herausforderung, darstellt. Die photoelektrochemische (PEC‐)Wasserspaltung spielt eine Schlüsselrolle bei der Herstellung von Wasserstoff aus Solarenergie als Energiequelle der Zukunft. Allerdings ist die praktische Wasseroxidation an Photoanoden (in Kombination mit der Wasserreduktion an einer Photokathode) für PEC‐Zellen aufgrund hoher Überspannungen und geringer Photoaktivität der Halbleiter derzeit nur schwer realisierbar. Für eine effiziente und dauerhafte Wasseroxidation wird die Entwicklung von Halbleitern notwendig sein, die hohe Wirkungsgrade bei der Umwandlung von Solarenergie in Wasserstoff ermöglichen und in Photoanoden nutzbar sind. In diesem Aufsatz werden Fortschritte in der Wasseroxidationsaktivität von Photoanoden aus (Oxy)Nitriden und Oxiden vom n‐Typ beschrieben.
Direkte Umwandlung von Estern in heterocyclische Fluorophore
Authors: Fischer Christian , Sparr Christof
Published: December 2017

Obwohl heterocyclische Fluorophore vielseitig eingesetzt werden, kann mit den derzeitigen Synthesemethoden nur ein Bruchteil der erwünschten Farbstoffdiversität zugänglich gemacht werden. Hier beschreiben wir eine modulare Methode, welche verschiedenste Carbonsäureester direkt in ein breites Spektrum an Heteroanthrylium‐Fluorophore umwandelt. Die doppelte Addition von Heteroatom‐verknüpften 1,5‐difunktionellen Organomagnesium‐Reagenzien an Ester führt nach dehydratisierender saurer Aufarbeitung zur Bildung von Acridinium‐, Xanthylium‐ und SiR‐Fluorophoren. Diese einstufige Synthesemethode liefert organische Photoredoxkatalysatoren für die duale Katalyse mit Nickel und Fluorophore, welche Fluoreszenzverstärkungsreaktionen zulassen.
Pd‐Catalyzed Enantioselective [6+4] Cycloaddition of Vinyl Oxetanes with Azadienes to Access Ten‐Membered Heterocycles
Authors: Wang Ya‐Nong , Yang Li‐Cheng , Rong Zi‐Qiang , Liu Tang‐Lin , Liu Ruoyang , Zhao Yu
Published: December 2017

We report herein the first enantioselective cycloaddition of vinyl oxetanes, the reaction of which with azadienes provided unprecedented access to ten‐membered heterocycles through a [6+4] cycloaddition. By using a commercially available chiral Pd‐SIPHOX catalyst, a wide range of benzofuran‐ as well as indole‐fused heterocycles could be accessed in excellent yield and enantioselectivity. A unique Lewis acid induced fragmentation of these ten‐membered heterocycles was also discovered.
Direct Transformation of Esters into Heterocyclic Fluorophores
Authors: Fischer Christian , Sparr Christof
Published: December 2017

Despite the manifold use of heterocyclic fluorophores, only a fraction of the desired dye diversity can be accessed by contemporary synthetic approaches. Herein, we describe a modular method that converts various carboxylic acid esters directly into a broad spectrum of heteroanthrylium fluorophores. The double addition of heteroatom‐bridged 1,5‐bifunctional organomagnesium reagents to esters leads to the formation of acridinium, xanthylium, and SiR fluorophores after dehydrative acidic work‐up. This one‐step synthetic method provides access to organophotoredox catalysts for dual catalysis with nickel and dyes amenable to fluorescence enhancement.
Synthesis, spectral, DFT calculations and antibacterial studies of Fe(III) complexes of new fluorescent Schiff bases derived from imidazo[4',5':3,4]benzo[1,2‐c]isoxazole
Authors: Ramezani Shirin , Pordel Mehdi , Davoodnia Abolghasem
Published: December 2017

New fluorescent heterocyclic ligands were synthesized by the reaction of 8‐(4‐chlorophenyl)‐3‐alkyl‐3H‐imidazo[4',5':3,4]benzo [1,2‐c]isoxazol‐5‐amine with p‐hydroxybenzaldehyde and p‐chlorobenzaldehyde in good yields. The coordination ability of the ligands with Fe3+ ion was examined in an aqueous metanolic solution. Schiff base ligands and their metal complexes were characterized by elemental analyses, IR, UV–vis, mass, and NMR spectra. The optical properties of the compounds were investigated and the results showed that the fluorescence of all compounds is intense and their obtained emission quantum yields are around 0.15 – 0.53. Optimized geometries and assignment of the IR bands and NMR chemical shifts of the new complexes were also computed by using density functional theory (DFT) methods. The DFT‐calculated vibrational wavenumbers and NMR chemical shifts are in good agreement with the experimental values, confirming suitability of the optimized geometries for Fe(III) complexes. Also, the 3D‐distribution map for HOMO and LUMO of the compounds were obtained. The new compounds showed potent antibacterial activity and their antibacterial activity (MIC) against Gram‐positive and Gram‐negative bacterial species were also determined. Results of antibacterial test revealed that coordination of ligands to Fe(III) leads to improvement in the antibacterial activity.
Can satellite ponds buffer the impact of introduced fish on newts in a mountain pond network?
Authors: Tiberti Rocco
Published: December 2017

Fish introductions into originally fishless mountain lentic habitats can affect native amphibians at different spatial scales. Introductions are often associated with local extinctions, but they can also affect amphibian metapopulations at a landscape level, intercepting amphibians when they move into reproductive and overwintering sites, preventing these movements, or reducing the overall metapopulation abundance and diversity.

Freshwater habitat networks are considered more resistant to biological invasions than isolated habitats, because they usually provide safe alternative sites that can buffer the impact of introduced fish. However, few studies have attempted to understand whether fish stocking also affects amphibians in surrounding fishless habitats.

This general hypothesis was tested using distribution data of Italian crested newt (Triturus carnifex Laurenti 1768) in a mountain pond network collected over a 13‐year‐long study (2005–2017), encompassing the periods before (pre‐2011) and after (post‐2012) fish (Salmo trutta L. 1758) were introduced in the pond where most of the newts were initially observed.

After fish introduction, visual counts dropped down close to zero in the invaded pond, but they increased in satellite ponds. This was a progressive increase not related to population size and should be regarded as a short‐term consequence of the slow colonization of satellite ponds.

These results confirm the dramatic impact of fish introductions on native amphibians at a local scale, but suggest that some amphibians can counteract their impact by moving to alternative sites, when available.

Halting fish stocking, lake and pond recovery, and the construction of alternative sites are proposed as management and conservation actions to preserve amphibian diversity.
Attitude certainty: Antecedents, consequences, and new directions
Authors: Tormala Zakary L. , Rucker Derek D.
Published: December 2017

Psychological certainty has been the subject of a great deal of research across a number of different literatures. This review focuses on prior and ongoing research on attitude certainty—the subjective sense of confidence of conviction a person has about an attitude—to provide a general overview of the role of certainty in attitudes and persuasion. First, we describe the antecedents, or origins, of attitude certainty, with particular attention to the metacognitive appraisals that drive people's feelings of certainty or uncertainty about their own attitudes. Second, we review the known consequences of attitude certainty, emphasizing the role of certainty in shaping information processing, attitude strength, and attitudinal advocacy. Third, we discuss recent developments that point to an upside for uncertainty in persuasion, whereby uncertainty experienced during message processing can increase message engagement and, thus, enhance message impact. Finally, we highlight several promising directions for future research. Our hope is that this review helps organize classic and contemporary research on attitude certainty and, in so doing, sparks new interest and continuing progress in the years to come.
Relating Decision‐Making Styles to Social Orientation and Time Approach
Authors: Geisler Martin , Allwood Carl Martin
Published: December 2017

Research on decision‐making styles has shown that stylistic differences matter for real‐life outcomes, but less research has explored how styles relate to other differences between individuals. Heeding a call for a more systematic and theoretically sound understanding of decision‐making styles, we investigated the relation between decision‐making styles and specific aspects of social orientation and approach to time in two samples (students, n = 118, and police investigators, n = 90). The results of regression analyses showed that decision‐making styles are related to specific differences in social orientation and time approach. Furthermore, results of structural equation model analyses suggested possible adjustments to the proposed two‐factor model for decision‐making styles (Dewberry, Juanchich, & Narendran, ). © 2017 The Authors Journal of Behavioral Decision Making Published by John Wiley & Sons Ltd.
Functional communication training and noncontingent reinforcement in treatment of stereotypy
Authors: Boyle Megan A. , Ortman Mary E. , Beckman Alexandra C. , Aholt Stephanie L. , Keenan Ginny L.
Published: December 2017

A 6‐year‐old boy with autism spectrum disorder engaged in automatically maintained stereotypy in the form of opening and closing doors. A functional analysis confirmed that he also emitted problem behavior that was maintained by access to stereotypy. We evaluated the separate and combined effects of functional communication training and arbitrary noncontingent reinforcement on both response classes. Results showed that the combination of functional communication training and noncontingent reinforcement was more effective at reducing stereotypy than either intervention on its own, although effects on problem behavior were unclear. These results suggest that combinations of interventions may be useful in the treatment of automatically maintained problem behavior.
3D stromal tissue equivalent affects intestinal epithelium morphogenesis in vitro
Authors: De Gregorio Vincenza , Imparato Giorgia , Urciuolo Francesco , Netti Paolo A.
Published: December 2017

Current in vitro models of human intestine commonly fail to mimic the complex intestinal functions and features required for drug development and disease research. Here, we deeply investigate the interaction existing between epithelium and the underneath stroma, and its role in the epithelium morphogenesis. We cultured human intestinal subepithelial myofibroblasts (ISEMFs) in two different 3D configurations: 3D‐collagen gel equivalent (3D‐CGE) and 3D cell‐synthetized stromal equivalent (3D‐CSSE). The 3D‐CGEs were obtained by means of the traditional collagen‐based cell technique and the 3D‐CSSE were obtained by bottom‐up tissue engineering strategy. The biophysical properties of both 3D models with regard to cell growth and composition (via histological analysis, immunofluorescence, and multiphoton imaging) were assessed. Then, human colorectal adenocarcinoma cell line (CaCo‐2) was cultured on both the 3D constructs in order to produce the intestinal model. We identified higher levels of matrix‐associated proteins from ISEMFs cultured in 3D‐CSSE compared to 3D‐CGE. Furthermore, multiphoton investigation revealed differences in the collagen network architecture in both models. At last, the more physiologically relevant stromal environment of the 3D‐CSSE drove the CaCo‐2 cell differentiation toward the four different type of intestinal epithelial cells (absorptive, mucus‐secretory, enteroendocrine, and Paneth) phenotype and promotes, in contrast to the 3D‐CGE, the production of the basement membrane. Taken together, these results highlight a fundamental role of the 3D stromal environment in addressing a correct epithelium morphogenesis as well as epithelial–stromal interface establishment.
New approach for determination of the degradation products of fenspiride hydrochloride found in oral liquid formulations
Authors: Cioroiu Bogdan I. , Caba Ioana C. , Prisăcaru Irina , Cioroiu Mona E. , Lazar Mihai I. , Niculaua Marius
Published: December 2017

Fenspiride hydrochloride (FNS) is used in treating chronic inflammatory diseases, most commonly as a liquid oral solution. FNS produces degradation products along with fenspiride N‐oxide (FNO) and 1‐phenylethyl‐4‐hydroxy‐4‐aminomethyl piperidine hydrochloride (PHAP). We aimed to develop and validate a chromatographic method in order to identify the main degradation products in the presence of other compounds from a liquid preparation. The method used a dual gradient using two buffer solutions: the first with pH 4.5 (buffer 1, pH 4.5–MeOH 90:10%, v/v) and the second with pH 2.9 (buffer 2, pH 2.9–acetronitrile–methanol, 65:15:10%, v/v/v). As mentioned, there was a modification of the organic mixture, starting with 10% methanol and ending with a mixture of acetonitrile–methanol (15:10%, v/v). The flow‐rate was 1.5 mL/min. According to the elution program, experimental conditions started with 100% solution S1, which decreased to 0% and, simultaneously, solution S2 increased to 100% during the first 10 min and was maintained for a further 5 min. After 15 min, initial conditions were re‐established. The linearity interval was 0.5–2 μg/mL and the minimum correlation coefficient was 0.999. The recovery factor was 100.47–103.17% and the limit of quantification was 0.19–0.332 μg/mL. Intra‐day maximum precision was 4.08% for FNS and 2.65% for PHAP. This double‐gradient mobile phase produced good specificity in relation to the degradation products of FNS and other constituents of the oral liquid formulation. Forced degradation studies revealed other related substances that were confirmed in mass balance analyses. Degradation products were confirmed in acidic, basic and oxidative media.
Transthyretin familial amyloid polyneuropathy (TTR‐FAP): Parameters for early diagnosis
Authors: Escolano‐Lozano Fabiola , Barreiros Ana Paula , Birklein Frank , Geber Christian
Published: December 2017

Background

Familial transthyretin amyloidosis is a life‐threatening disease presenting with sensorimotor and autonomic polyneuropathy. Delayed diagnosis has a detrimental effect on treatment and prognosis. To facilitate diagnosis, we analyzed data patterns of patients with transthyretin familial amyloid polyneuropathy (TTR‐FAP) and compared them to polyneuropathies of different etiology for clinical and electrophysiological discriminators.

Methods

Twenty‐four patients with TTR‐FAP and 48 patients with diabetic polyneuropathy (dPNP) were investigated (neurological impairment score NIS; neurological disability score NDS) in a cross‐sectional design. Both groups were matched for gender and presence of pain. Quantitative sensory testing (QST), sympathetic skin response (SSR), heart rate variability (HRV), and nerve conduction studies (NCV) were performed. Both groups were compared using univariate analysis. In a stepwise discriminant analysis, discriminators between both neuropathies were identified. These discriminators were validated comparing TTR‐FAP patients with a cohort of patients with chemotherapy‐induced polyneuropathy (CIN) and chronic inflammatory demyelinating neuropathy (CIDP).

Results

TTR‐FAP patients scored higher in NDS and NIS and had impaired cold detection (CDT, p = .024), cold–warm discrimination (TSL, p = .019) and mechanical hyperalgesia (MPT, p = .029) at the hands, SSR (upper limb, p = .022) HRV and ulnar and sural NCS (all p < .05) were more affected in TTR‐FAP. Ulnar nerve sensory NCV, CDT, and the MPT but not the other parameters discriminated TTR‐FAP from dPNP (82% of cases), from CIN (86.7%) and from CIDP (68%; only ulnar sNCV).

Conclusion

Low ulnar SNCV, impaired cold perception, and mechanical hyperalgesia at the hands seem to characterize TTR‐FAP and might help to differentiate from other polyneuropathies.
Familial multiple sclerosis and association with other autoimmune diseases
Authors: Pytel Vanesa , Matías‐Guiu Jordi A. , Torre‐Fuentes Laura , Montero Paloma , Gómez‐Graña Álvaro , García‐Ramos Rocío , Moreno‐Ramos Teresa , Oreja‐Guevara Celia , Fernández‐Arquero Miguel , Gómez‐Pinedo Ulises , Matías‐Guiu Jorge
Published: December 2017

Objectives

Autoimmune diseases (AID) follow a complex, probably polygenic, pattern of inheritance and often cluster in families of patients with multiple sclerosis (MS). Our objective was to analyze family patterns and characteristics in families including more than one patient with MS.

Materials and Methods

We analyzed personal and family history of neurological, systemic, and autoimmune diseases in 84 MS patients from 40 different families. Families were classified in two groups: families with cases of MS in at least two different generations (15 families) and families in which cases of MS belonged to only one generation (25 families).

Results

The two previously established groups presented different clinical patterns and frequency of association with another AID. In one group, the second generation displayed a higher annual relapse rate than the first generation, higher frequency of progressive forms of MS, and more patients with another AID in addition to MS. Relapsing‐remitting forms of MS (RRMS) were more frequent in the other group.

Conclusions

Families that include more than one MS patient may show two distinct patterns. This finding seems important for the compression and analysis of genetic information on MS.
Assessment of Consumer Behavior Towards Environmental Responsibility: A Structural Equations Modeling Approach
Authors: Pawaskar Uttam Shankar , Raut Rakesh D , Gardas Bhaskar B
Published: December 2017

This paper analyses the factors impacting consumer environmental responsibility using a structural equation modeling approach. Consumer environmental responsibility is the intention of a person to act towards remediation of environmental problems not as an individual user with economic interests but as a responsible citizen having concerns about the social and environmental wellbeing of society. Therefore, awareness of environmental problems and knowledge of remedial alternatives will help individuals to pursue their chosen action and bolster a genuine desire to act and determine the measures for alleviation of environmental challenges. The four dimensions of an environmentally responsible consumer – opinion and beliefs, willingness, awareness, and an ability to act – are analysed. During the analysis, the dimension of ‘ability to move’ is found to be critical, because it has a direct influence on the capacity of the consumer to act. This research is intended to guide policy‐ and decision‐makers of regulatory bodies in understanding consumer behavior towards improving environmental performance index. It also helps organizational managers to make their supply chains green, and competitive, which in turn improves brand image and overall organizational performance. Copyright © 2017 John Wiley & Sons, Ltd and ERP Environment
Development of structural analysis virtual modules for iPad application
Authors: Pena Nicolas , Chen An
Published: December 2017

Structural Analysis is a course to study structures subjected to different loading conditions, which employs engineering mechanics, material science, and applied mathematics to determine structural deformation, internal forces, and structural support reactions. Without any lab demonstrations, students taking the course miss the opportunity to observe key visual concepts of structural analysis. To address this issue, this paper aims to develop an iPad application, iStructure, which will illustrate and teach key concepts of structural analysis and can be used as an instructional tool for instructors and learning tool for students. iStructure covers three main structural modules: beam, truss, and frame. This paper reports structural analysis methods and computer algorithms used to develop iStructure and its applications. The structural characteristics, such as structural deformation, internal force diagrams, stress and strain diagrams, and influence line are illustrated and simulated within each module using Objective‐C programming. The Frame and Truss Modules employ Matrix Structural Analysis methods for determining the conditions of the structure. The modules incorporate a modified and efficient matrix structural analysis procedure through the use of pointer addresses, which avoid developing multiple large matrices for structural analysis by using the DOF indices to develop the global partition matrix directly. This procedure provides faster computation and less memory demands, while making instant structural analysis of relatively complicated structural configurations possible. The Beam Module utilizes a predefined beam formulas method for determining the conditions of the structure. This method significantly reduces the structural analysis computation demand and is necessary for the development of the Influence Line, which requires multiple structural analyses iteration.
Biochemical Characterization and Mechanistic Analysis of the Levoglucosan Kinase from Lipomyces starkeyi
Authors: Rother Christina , Gutmann Alexander , Gudiminchi Ramakrishna , Weber Hansjörg , Lepak Alexander , Nidetzky Bernd
Published: December 2017

Levoglucosan kinase (LGK) catalyzes the simultaneous hydrolysis and phosphorylation of levoglucosan (1,6‐anhydro‐β‐d‐glucopyranose) in the presence of Mg2+–ATP. For the Lipomyces starkeyi LGK, we show here with real‐time in situ NMR spectroscopy at 10 °C and pH 7.0 that the enzymatic reaction proceeds with inversion of anomeric stereochemistry, resulting in the formation of α‐d‐glucose‐6‐phosphate in a manner reminiscent of an inverting β‐glycoside hydrolase. Kinetic characterization revealed the Mg2+ concentration for optimum activity (20–50 mm), the apparent binding of levoglucosan (Km=180 mm) and ATP (Km=1.0 mm), as well as the inhibition by ADP (Ki=0.45 mm) and d‐glucose‐6‐phosphate (IC50=56 mm). The enzyme was highly specific for levoglucosan and exhibited weak ATPase activity in the absence of substrate. The equilibrium conversion of levoglucosan and ATP lay far on the product side, and no enzymatic back reaction from d‐glucose‐6‐phosphate and ADP was observed under a broad range of conditions. 6‐Phospho‐α‐d‐glucopyranosyl fluoride and 6‐phospho‐1,5‐anhydro‐2‐deoxy‐d‐arabino‐hex‐1‐enitol (6‐phospho‐d‐glucal) were synthesized as probes for the enzymatic mechanism but proved inactive with the enzyme in the presence of ADP. The pyranose ring flip 4C1→1C4 required for 1,6‐anhydro‐product synthesis from d‐glucose‐6‐phosphate probably presents a major thermodynamic restriction to the back reaction of the enzyme.
Green Synthesis of Rhodium Nanoparticles that are Catalytically Active in Benzene Hydrogenation and 1‐Hexene Hydroformylation
Authors: Alsalahi Waleed , Tylus Wlodzimierz , Trzeciak Anna M.
Published: December 2017

Rhodium nanoparticles (Rh NPs) were prepared according to a green method based on the reduction of (acetylacetonato)dicarbonylrhodium(I), Rh(acac)(CO)2, in water at 80 °C. The nanoparticles, which were obtained without the addition of a reducing agent, were stabilized by polyvinylpyrrolidone (PVP) or polyvinyl alcohol (PVA) polymers and characterized by TEM (transmission electron microscopy), XPS (X‐ray photoelectron spectroscopy), and XRD (X‐ray powder diffraction) methods. The excellent catalytic activity of these Rh NPs was evidenced in the hydrogenation of benzene to cyclohexane. In the presence of PPh3, Rh NPs formed a highly active system in the hydroformylation of 1‐hexene. In this system, they acted as a source of soluble rhodium species. Rh NPs were also synthesized in water using rhodium(II) acetate, Rh2(OAc)4, and rhodium(III) chloride, RhCl3, as rhodium sources, and their catalytic activity was compared with that of the rhodium precursors.
Graphene Quantum‐Dot‐Modified Hexagonal Tubular Carbon Nitride for Visible‐Light Photocatalytic Hydrogen Evolution
Authors: Gao Yanting , Hou Feng , Hu Shan , Wu Baogang , Wang Ying , Zhang Haiqiu , Jiang Baojiang , Fu Honggang
Published: December 2017

Graphene quantum dots were modified on hexagonal tubular carbon nitride to form a composite photocatalyst by freeze‐drying technology. With an optimum loading amount of 0.15 wt % GQDs, the composite photocatalyst exhibits an improved visible‐light photocatalytic performance for hydrogen evolution (112.1 μmol h−1) that is about 9 times higher than that of bulk carbon nitride. During the photocatalytic reaction, graphene quantum dots play a photosensitizer role and an electron reservoir, which can extend the visible‐light response of the photocatalyst, decrease its band gap, and improve the separation efficiency of photoinduced electron–hole pairs. The graphene quantum dots can also absorb the long‐wavelength light and then emit the shorter wavelength light based on its upper transfer luminescence properties, which also contribute to the utilization of visible light. This finding demonstrates that the graphene quantum‐dot modification is a promising method to improve visible‐light photocatalytic activities for traditional photocatalysts.
Using Mg‐Al Mixed Oxide and Reconstructed Hydrotalcite as Basic Catalysts for Aldol Condensation of Furfural and Cyclohexanone
Authors: Kikhtyanin Oleg , Kadlec David , Velvarská Romana , Kubička David
Published: December 2017

This study presents results on aldol condensation of furfural and cyclohexanone in presence of Mg‐Al hydrotalcite‐derived materials as solid basic catalysts at reaction temperatures from 25 to 90 °C and a cyclohexanone to furfural molar ratio of 1–10. Mg‐Al mixed oxide exhibited reasonable activity with furfural conversion of ca. 50 % after 180 min of the reaction at T=90 °C. The activity of reconstructed hydrotalcite was much higher with furfural conversion close to 100 % at short reaction times. In comparison with Mg‐Al mixed oxide, the initial reaction rate has increased 30–50 times. Under similar reaction conditions, cyclohexanone self‐condensation on HTC‐derived catalysts could not compete with aldol condensation because the former reaction was inhibited by produced water. The change in CH/F molar ratio influenced both furfural conversion and product selectivity; higher furfural content in the reaction mixture favored the second condensation step.
Some Attributes of Mn3+ Sites in Nickel‐Based Layered Double Hydroxides during Methanol Electro‐oxidation in Alkaline Media
Authors: Oliver‐Tolentino Miguel A. , Ramos‐Sánchez Guadalupe , Manzo‐Robledo Arturo , Ramírez‐Rosales Daniel , Flores‐Moreno Jorge L. , Lima Enrique , Guzmán‐Vargas Ariel
Published: December 2017

Ni‐based layered double hydroxides (LDHs), or hydrotalcite‐like materials (HTs), were synthetized through co‐precipitation at constant pH (NiAl and NiMg) and urea hydrolysis (NiMn) methods, and they were tested in the electrochemical methanol oxidation (MOR). The physicochemical properties were explored by using techniques such as X‐ray diffraction, FT‐IR spectroscopy, as well as electron paramagnetic resonance. In addition, correlation between active site arrangements and electrocatalytic activity was evidenced by density functional calculations. Specific site μ(Ni2Mn‐OH) showed the lowest proton energy removal at approximately 3.6 eV and the NiMn LDH sample containing a higher proportion of this site exhibited the best performance for the MOR process, with an enhancement factor of 5.16, which is attributed to limited deactivation of Ni during the reaction. CO2 production was detected by differential electrochemical mass spectrometry to be on the order of ten times greater than O2.
MOF‐Derived Cobalt Phosphide/Carbon Nanocubes for Selective Hydrogenation of Nitroarenes to Anilines
Authors: Yang Shuliang , Peng Li , Oveisi Emad , Bulut Safak , Sun Daniel T. , Asgari Mehrdad , Trukhina Olga , Queen Wendy L.
Published: December 2017

Transition‐metal phosphides have received tremendous attention during the past few years because they are earth‐abundant, cost‐effective, and show outstanding catalytic performance in several electrochemically driven conversions including hydrogen evolution, oxygen evolution, and water splitting. As one member of the transition‐metal phosphides, CoxP‐based materials have been widely explored as electrocatalyts; however, their application in the traditional thermal catalysis are rarely reported. In this work, cobalt phosphide/carbon nanocubes are designed and their catalytic activity for the selective hydrogenation of nitroarenes to anilines is studied. A high surface area metal‐organic framework (MOF), ZIF‐67, is infused with red phosphorous, and then pyrolysis promotes the facile production of the phosphide‐based catalysts. The resulting composite, consisting of Co2P/CNx nanocubes, is shown to exhibit excellent catalytic performance in the selective hydrogenation of nitroarenes to anilines. To the best of our knowledge, this is the first report showing catalytic activity of a cobalt phosphide in nitroarenes hydrogenation.
Enhanced adsorption of xylenol orange from aqueous solutions by polyethylenimine‐grafted chitosan microspheres
Authors: Yu Xueqing , Jing Yingjun , Gao Hui
Published: December 2017

To enhance the adsorption performance, chitosan microspheres (CS–MSs) were grafted with polyethylenimine (PEI), a cationic compound with abundant amine groups. The resulting PEI‐grafted CS–MSs (PEI–CS–MSs) were used for the adsorption of xylenol orange (XO), an anionic dye. The results show that PEI–CS–MSs were in regular spherical shape without porous structure. XO molecules were adsorbed onto the amine groups of PEI–CS–MSs through electrostatic interaction. The maximum adsorption capacity of XO onto PEI–CS–MSs was 816.33 mg/g at 303 K, being much higher than that onto CS–MSs. The adsorption process could be properly described by the pseudo‐second‐order kinetic and Langmuir models. The adsorption of XO was a spontaneous process with exothermic nature. In addition, the adsorption capacity only decreased by 0.52 % after seven cycles of adsorption‐desorption, indicating the excellent reusability of PEI–CS–MSs.
Genomic profiling identifies GPC5 amplification in association with sarcomatous transformation in a subset of uterine carcinosarcomas
Authors: Chui M Herman , Have Cherry , Hoang Lien N , Shaw Patricia , Lee Cheng‐Han , Clarke Blaise A
Published: December 2017

Uterine carcinosarcoma, also known as Malignant Mixed Müllerian Tumour, is a high‐grade biphasic neoplasm composed of sarcomatous elements thought to originate via transdifferentiation from high‐grade endometrial carcinoma. To identify molecular factors contributing to the histogenesis of this tumour, we analyzed DNA extracted from matched carcinoma and sarcoma components from 12 cases of carcinosarcoma by a molecular inversion probe microarray to assess genomic copy number alterations (CNAs) and allelic imbalances. Widespread CNAs were identified in tumours with serous histology in the carcinoma component (9/12), while the remaining three cases with endometrioid carcinoma were near‐diploid. Quantification of the extent of genomic aberrations revealed a significant increase in sarcoma relative to carcinoma in tumours with well‐delineated histologic components. Focal amplification of 13q31.3 was identified in 6/12 profiled tumours, of which four harboured the aberration exclusively in the sarcoma component. This result was verified by fluorescence in situ hybridization against GPC5, the only gene situated within the minimal region of amplification. In a validation cohort composed of 97 carcinosarcomas and other uterine sarcomas, amplification of GPC5 (GPC5/CEP13 ratio ≥ 2.2) was identified in 11/97 (11.3%) cases (9/64 carcinosarcoma, 1/3 rhabdomyosarcoma, 1/21 leiomyosarcoma, 0/8 adenosarcoma, 0/1 undifferentiated endometrial sarcoma) and an additional 4 (2.8%) cases had low level gains (GPC5/CEP13 ratio ≥1.5 but <2.2). The functional relevance of Glypican‐5, the gene product of GPC5, in regulating differentiation and lineage commitment was demonstrated in an endometrial carcinoma cell line in vitro. In conclusion, we identified GPC5 amplification as a molecular event mediating epithelial‐mesenchymal transdifferentiation in a subset of uterine carcinosarcomas.
Rapid amplification of prions from variant Creutzfeldt–Jakob disease cerebrospinal fluid
Authors: Barria Marcelo A , Lee Andrew , Green Alison JE , Knight Richard , Head Mark W
Published: December 2017

Human prion diseases constitute a group of infectious and invariably fatal neurodegenerative disorders associated with misfolding of the prion protein. Variant Creutzfeldt–Jakob disease (vCJD) is a zoonotic prion disease linked to oral exposure to the infectious agent that causes bovine spongiform encephalopathy (BSE) in cattle. The most recent case of definite vCJD was heterozygous (MV) at polymorphic codon 129 of the prion protein gene PRNP while all of the previous 177 definite or probable vCJD cases who underwent genetic analysis were methionine homozygous (MM). Retrospective prevalence studies conducted on lympho‐reticular tissue suggest that the number of asymptomatic vCJD carriers in the United Kingdom might be around 1 in 2000 people. In addition, there have been four known cases of the transmission of vCJD infection via blood transfusion. For these reasons, a sensitive, reliable, and fast diagnostic test is currently needed. We describe a rapid and highly sensitive seeding conversion assay that detects disease‐associated prion protein in the brain and cerebrospinal fluid in vCJD after 48–96 h of amplification, with 100% sensitivity and specificity. This method can amplify prions from definite, probable, and possible vCJD cases from patients who are either MM or MV at PRNP‐codon 129.
Co‐administration of Antimicrobial Peptides Enhances Toll‐like Receptor 4 Antagonist Activity of a Synthetic Glycolipid
Authors: Facchini Fabio A. , Coelho Helena , Sestito Stefania E. , Delgado Sandra , Minotti Alberto , Andreu David , Jiménez‐Barbero Jesús , Peri Francesco
Published: December 2017

This study examines the effect of co‐administration of antimicrobial peptides and the synthetic glycolipid FP7, which is active in inhibiting inflammatory cytokine production caused by TLR4 activation and signaling. The co‐administration of two lipopolysaccharide (LPS)‐neutralizing peptides (a cecropin A–melittin hybrid peptide and a human cathelicidin) enhances by an order of magnitude the potency of FP7 in blocking the TLR4 signal. Interestingly, this is not an additional effect of LPS neutralization by peptides, because it also occurs if cells are stimulated by the plant lectin phytohemagglutinin, a non‐LPS TLR4 agonist. Our data suggest a dual mechanism of action for the peptides, not exclusively based on LPS binding and neutralization, but also on a direct effect on the LPS‐binding proteins of the TLR4 receptor complex. NMR experiments in solution show that peptide addition changes the aggregation state of FP7, promoting the formation of larger micelles. These results suggest a relationship between the aggregation state of lipid A‐like ligands and the type and intensity of the TLR4 response.
Surgery versus stereotactic body radiation therapy for stage I non–small cell lung cancer: A comprehensive review
Authors: Tandberg Daniel J. , Tong Betty C. , Ackerson Bradley G. , Kelsey Chris R.
Published: December 2017

Non–small cell lung cancer (NSCLC) is the leading cause of cancer‐related death in the United States. With the implementation of lung cancer screening, the number and proportion of patients diagnosed with early‐stage disease are anticipated to increase. Surgery is currently the standard of care for patients with operable stage I NSCLC. However, promising outcomes with stereotactic body radiation therapy (SBRT) in patients with inoperable disease has led to interest in directly comparing SBRT and surgery in operable patients. Unfortunately, early randomized trials comparing surgery and SBRT closed early because of poor accrual. In this article, the nuances of surgery and SBRT for early‐stage NSCLC are reviewed. Furthermore, retrospective and prospective analyses of SBRT in early‐stage NSCLC are discussed, and active randomized trials comparing these 2 approaches are described. Cancer 2018;124:667‐78. © 2017 American Cancer Society.
Method Evaluations for Adsorption Free Energy Calculations at the Solid/Water Interface through Metadynamics, Umbrella Sampling, and Jarzynski's Equality
Authors: Wei Qichao , Zhao Weilong , Yang Yang , Cui Beiliang , Xu Zhijun , Yang Xiaoning
Published: December 2017

Considerable interest in characterizing protein/peptide–surface interactions has prompted extensive computational studies on calculations of adsorption free energy. However, in many cases, each individual study has focused on the application of free energy calculations to a specific system; therefore, it is difficult to combine the results into a general picture for choosing an appropriate strategy for the system of interest. Herein, three well‐established computational algorithms are systemically compared and evaluated to compute the adsorption free energy of small molecules on two representative surfaces. The results clearly demonstrate that the characteristics of studied interfacial systems have crucial effects on the accuracy and efficiency of the adsorption free energy calculations. For the hydrophobic surface, steered molecular dynamics exhibits the highest efficiency, which appears to be a favorable method of choice for enhanced sampling simulations. However, for the charged surface, only the umbrella sampling method has the ability to accurately explore the adsorption free energy surface. The affinity of the water layer to the surface significantly affects the performance of free energy calculation methods, especially at the region close to the surface. Therefore, a general principle of how to discriminate between methodological and sampling issues based on the interfacial characteristics of the system under investigation is proposed.
The role of shame and self‐compassion in psychotherapy for narcissistic personality disorder: An exploratory study
Authors: Kramer Ueli , Pascual‐Leone Antonio , Rohde Kristina B. , Sachse Rainer
Published: December 2017

This process‐outcome study aims at exploring the role of shame, self‐compassion, and specific therapeutic interventions in psychotherapy for patients with narcissistic personality disorder (NPD). This exploratory study included a total of N = 17 patients with NPD undergoing long‐term clarification‐oriented psychotherapy. Their mean age was 39 years, and 10 were male. On average, treatments were 64 sessions long (range between 45 and 99). Sessions 25 and 36 were rated using the Classification of Affective Meaning States and the Process‐Content‐Relationship Scale. Outcome was assessed using the Symptom Check List‐90 and Beck Depression Inventory‐II. Between Sessions 25 and 36, a small decrease in the frequency of shame was found (d = .30). In Session 36, the presence of self‐compassion was linked with a set of specific therapist interventions (process‐guidance and treatment of behaviour‐underlying assumptions; 51% of variance explained and adjusted). This study points to the possible central role of shame in the therapeutic process of patients with NPD. Hypothetically, one way of resolving shame is, for the patient, to access underlying self‐compassion.
Environmentally Responsible Consumption: Construct Definition, Scale Development, and Validation
Authors: Gupta Sudhanshu , Agrawal Richa
Published: December 2017

Most environmental problems are rooted in human behaviour, especially consumption. While not consuming is not an option, it would help if all consumption could be measured for environmental responsibility. This study conceptualizes and operationalizes environmentally responsible consumption (ERC), and develops a standardized scale for measuring the same. Depth interviews, blog data analysis, and customer surveys were conducted to develop a standardized 38‐item ERC scale that captures ten unique behaviours pertaining to acquisition, use, and disposal. The scale is an improvement over available measures and compares favourably on several key parameters. The ERC scale could be potentially used by governmental and non‐governmental bodies, policymakers, and environmental groups, for gaining insights into current consumption behaviours of the general public or specific target groups, identifying specific behaviour/s that need improvement, and targeting and tracking such behaviours over time. It could also be used by businesses for identifying opportunities in green products and/or services. Copyright © 2017 John Wiley & Sons, Ltd and ERP Environment
Classical ion–grain scattering in plasmas: Image force correction
Authors: Bastykova N.Kh. , Kodanova S.K. , Ramazanov T.S. , Moldabekov Zh.A.
Published: December 2017

Corrections to the classical ion–grain scattering and capture cross‐sections due to polarization charges on the dust particle, which acts as an image charge, have been obtained for a low‐charged grain (with the charge number Z = 10). The trajectory of the ion around the dust particle is used for visual illustration of the influence of the grain polarization on scattering. The correction to the scattering cross‐section due to the image force can be as large as 25% in the strong ion–grain coupling regime and up to 10% in the moderately coupled case. The correction to the capture cross‐section turns out to be nearly constant (∼14%) for moderate as well as strong ion–grain coupling.
Deconvolution model to resolve cytometric microbial community patterns in flowing waters
Authors: Amalfitano Stefano , Fazi Stefano , Ejarque Elisabet , Freixa Anna , Romaní Anna M. , Butturini Andrea
Published: December 2017

Flow cytometry is suitable to discriminate and quantify aquatic microbial cells within a spectrum of fluorescence and light scatter signals. Using fixed gating and operational settings, we developed a finite distribution mixture model, followed by the Voronoi tessellation, to resolve bivariate cytometric profiles into cohesive subgroups of events. This procedure was applied to outline recurrent patterns and quantitative changes of the aquatic microbial community along a river hydrologic continuum. We found five major subgroups within each of the commonly retrieved populations of cells with Low and High content of Nucleic Acids (namely, LNA, and HNA cells). Moreover, the advanced analysis allowed assessing changes of community patterns perturbed by a wastewater feed. Our approach for cytometric data deconvolution confirmed that flow cytometry could represent a prime candidate technology for assessing microbial community patterns in flowing waters. © 2017 International Society for Advancement of Cytometry
Optimal deployment of femtocells using cost function
Authors: Akindeji Akinlabi , Joseph Meera
Published: December 2017

In fact, the demand for mobile data has turned out to be one of the most pressing needs of the human race. In more details, the researcher deals with the voice calling performance and good network signal, which are needed to achieve the above. The femtocells are mostly designed for indoor environments. It enables voice calling and traffic loading, where it improves network coverage. Thus, a femtocell is deployed for signal improvement in the indoor setting. Interference occurs among femtocells. The optimisation of femtocells depends on system factors that require performance and capacity of the network for indoor users. In the above circumstance, the authors considered using the cost function to optimise the mobile coverage, whereby reducing the interference within the users. Adequate MATLAB simulation was utilised for this study. The simulated results were satisfactory since they illustrate the benefits of the methods for the service performance.