bluuebunny/crossref_metadata_2025 huggingface dataset:
Eyes on the Prize? Evidence of Diminishing Attention to Experienced and Foregone Outcomes in Repeated Experiential Choice
Authors: Ashby Nathaniel J. S. , Rakow Tim
Published: March 2015

Recently, there has been increased interest in decisions‐from‐experience (where decision makers learn from observing the outcomes of previous choices), which provide valuable insights into the learning and preference construction processes underlying many daily decisions. Several process models have been developed to capture these processes, and while such models often fit the data well, many assume that the decision maker is a vigilant observer, processing each outcome. In two studies, we provide a critical test of this assumption using eye tracking to record directed visual attention when participants choose repeatedly among two options, each time being shown the outcome for their chosen option and for the foregone option. Consistently, we find that the vigilance assumption is not supported, with decision makers often not attending to outcome information. Moreover, (in)attention to outcomes is predictable, with vigilance decreasing as more choices are made, and being greater for obtained than for foregone outcomes, and when options deliver only gains as opposed to losses or a mixture of gains and losses. Furthermore, we find that this variation in attentional allocation plays a central role in the apparent indecisiveness (inconsistency) in choice, with increased attention to foregone outcomes predicting switches to that option on the next choice. Together, these findings highlight the value of eye tracking in investigations of decisions‐from‐experience, providing novel insight into the cognitive processes underlying them. Copyright © 2015 John Wiley & Sons, Ltd.
Experiential response and intention to purchase in the cocreative consumption of music: The Nine Inch Nails experiment
Authors: Aucouturier Jean‐Julien , Fujita Marketa , Sumikura Hiroko
Published: March 2015

Customers allowed to cocreate products are more willing to purchase them eventually because of not only their utilitarian but also their hedonic and experiential value. Experiential responses seem especially relevant in the cocreative consumption of cultural and intangible goods, such as music. To examine how such intangible aspects of cocreation can influence a consumer's intention to purchase, we let two groups of participants rate their experience consuming music in either a traditional or cocreative way, in an experimental situation inspired by the work of American rock band Nine Inch Nails. Participants in the traditional group had to passively watch a series of music videos; participants in the cocreative group were tasked to produce a video montage using the same material. In the traditional group, purchase intention was predicted by music quality, mediated by willingness to reexperience; in the cocreative group, however, purchase intention was only predicted by the consumers' experiential response, with no mediation of either music quality or willingness to reexperience. Additionally, the overall experiential response to music was lower in the cocreative group than in the traditional group, leading to lower intention to purchase. These results suggest that cocreated value for intangible goods is predicted at least as much by the consumers' experiential response as by their evaluation of product quality. It also suggests that there is nothing systematically positive in having consumers participate in the coproduction of intangible goods and that research is needed to identify the factors predicting the perceived quality of a cocreative experience. Copyright © 2015 John Wiley & Sons, Ltd.
Screening for behavioral and emotional problems in primary care
Authors: Fritz Gregory K.
Published: March 2015

Troubled by the fact that psychosocial concerns of children and adolescents are not being consistently identified, the American Academy of Pediatrics (AAP) released a remarkable clinical report in February that should go a long way toward improving things in this area. The report, “Promoting Optimal Development: Screening for Behavioral and Emotional Problems,” is aimed at pediatricians and primary care physicians but is relevant for all professionals working with children, youth, and families.
Coordination Chemistry of N‐Heterocyclic Nitrenium‐Based Ligands
Authors: Tulchinsky Yuri , Kozuch Sebastian , Saha Prasenjit , Mauda Assaf , Nisnevich Gennady , Botoshansky Mark , Shimon Linda J. W. , Gandelman Mark
Published: March 2015

Comprehensive studies on the coordination properties of tridentate nitrenium‐based ligands are presented. N‐heterocyclic nitrenium ions demonstrate general and versatile binding abilities to various transition metals, as exemplified by the synthesis and characterization of RhI, RhIII, Mo0, Ru0, RuII, PdII, PtII, PtIV, and AgI complexes based on these unusual ligands. Formation of nitrenium–metal bonds is unambiguously confirmed both in solution by selective 15N‐labeling experiments and in the solid state by X‐ray crystallography. The generality of N‐heterocyclic nitrenium as a ligand is also validated by a systematic DFT study of its affinity towards all second‐row transition and post‐transition metals (Y–Cd) in terms of the corresponding bond‐dissociation energies.
Redox Communication within Multinuclear Iron–Sulfur Complexes Related to Electronic Interplay in the Active Site of [FeFe]Hydrogenase
Authors: Chu Kai‐Ti , Liu Yu‐Chiao , Huang Yi‐Lan , Lee Gene‐Hsiang , Tseng Mei‐Chun , Chiang Ming‐Hsi
Published: March 2015

The one‐electron oxidations of a Fe2 complex lead to the formation of a persistent metal‐stabilized thiyl radical Fe2 species, mixed‐valent Fe4, and Fe8 complexes. The unpaired spin in the Fe2 radical species delocalizes over the Fe2 and the aromatic dithiolate, mostly on the terminal sulfur. The subsequent dimerization of the singly oxidized Fe2 to the Fe4 retains the partial thiyl radical character. For an analogue with less steric hindrance, the π–π stacking interaction between the dithiolato aromatic rings induces generation of the Fe8, in which process electronic structures of the species are modulated through reducing the thiyl radical to the thiolate. Electronic reorganization repeats when the Fe8 is converted to Fe4. Electronic interplay in the complexes decreases the energy gap of frontier MOs and buffers electronic impacts upon redox events. Easier accessible redox potentials and increased stability of the species are facilitated. The results demonstrate that electronic versatility of the benzenedithiolate exerts pronounced influences on electronic and coordination structure of the metal complexes.
Synthesis of Cu3Sn Alloy Nanocrystals through Sequential Reduction Induced by Gradual Increase of the Reaction Temperature
Authors: Cho Sanghun , Shin Dong‐Hun , Yin Zhenxing , Lee Chaedong , Park Si Yun , Yoo Jeeyoung , Piao Yuanzhe , Kim Youn Sang
Published: March 2015

Cu3Sn alloy nanocrystals are synthesized by sequential reduction of Cu and Sn precursors through a gradual increase of the reaction temperature. By transmission electron microscopy (TEM), energy‐dispersive X‐ray spectroscopy (EDS), UV/Vis spectroscopy, and X‐ray diffraction (XRD) analyses, the alloy formation mechanism of Cu3Sn nanocrystals has been studied. The incremental increase of the reaction temperature sequentially induces the reduction of Sn, the diffusion of Sn into the preformed Cu nanocrystals, resulting in the intermediate phase of Cu–Sn alloy nanocrystals, and then the formation of Cu3Sn alloy nanocrystals. We anticipate that the synthesis of Cu3Sn alloy nanocrystals encourages studies toward the synthesis of various alloy nanomaterials.
Well‐Defined Palladium Nanoparticles Supported on Siliceous Mesocellular Foam as Heterogeneous Catalysts for the Oxidation of Water
Authors: Verho Oscar , Åkermark Torbjörn , Johnston Eric V. , Gustafson Karl P. J. , Tai Cheuk‐W. , Svengren Henrik , Kärkäs Markus D. , Bäckvall Jan‐E. , Åkermark Björn
Published: March 2015

Herein, we describe the use of Pd nanoparticles immobilized on an amino‐functionalized siliceous mesocellular foam for the catalytic oxidation of H2O. The Pd nanocatalyst proved to be capable of mediating the four‐electron oxidation of H2O to O2, both chemically and photochemically. The Pd nanocatalyst is easy to prepare and shows high chemical stability, low leaching, and recyclability. Together with its promising catalytic activity, these features make the Pd nanocatalyst of potential interest for future sustainable solar‐fuel production.
Synthesis of Elusive Chloropnictenium Ions
Authors: Hering‐Junghans Christian , Thomas Max , Villinger Alexander , Schulz Axel
Published: March 2015

This work describes the synthesis and full characterization of elusive chloropnictenium ion salts of the type [RAr*N(SiMe)ECl][A] (RAr*=2,6‐(CHPh2)‐4‐R‐C6H2, R=Me, tBu; E=Sb, Bi; A−=GaCl4, Al(OCH(CF3)2)4). In these species the cation is significantly stabilized by weak arene interactions to flanking phenyl groups of the RAr* moiety. In this context the bonding situation has been studied by computational means and the reactivity towards the Lewis base 4‐dimethylaminopyridine (dmap) was investigated.
Acceleration of Long‐Range Photoinduced Electron Transfer through DNA by Hydroxyquinolines as Artificial Base Pairs
Authors: Bätzner Effi , Liang Yu , Schweigert Caroline , Unterreiner Andreas‐Neil , Wagenknecht Hans‐Achim
Published: March 2015

The C‐nucleoside based on the hydroxyquinoline ligand (Hq) is complementary to itself and forms stable Hq–Hq pairs in double‐stranded DNA. These artificial Hq–Hq pairs may serve as artificial electron carriers for long‐range photoinduced electron transfer in DNA, as elucidated by a combination of gel electrophoretic analysis of irradiated samples and time‐resolved transient absorption spectroscopy. For this study, the Hq–Hq pair was combined with a DNA‐based donor–acceptor system consisting of 6‐N,N‐dimethylaminopyrene conjugated to 2′‐deoxyuridine as photoinducible electron donor, and methyl viologen attached to the 2′‐position of uridine as electron acceptor. The Hq radical anion was identified in the time‐resolved measurements and strand cleavage products support its role as an intermediate charge carrier. Hence, the Hq–Hq pair significantly enhances the electron hopping capability of DNA compared to natural DNA bases over long distances while keeping the self‐assembly properties as the most attractive feature of DNA as a supramolecular architecture.
Sympathetic Preganglionic Neurons: Properties and Inputs
Authors: Deuchars Susan A. , K. Lall Varinder
Published: March 2015

The sympathetic nervous system comprises one half of the autonomic nervous system and participates in maintaining homeostasis and enabling organisms to respond in an appropriate manner to perturbations in their environment, either internal or external. The sympathetic preganglionic neurons (SPNs) lie within the spinal cord and their axons traverse the ventral horn to exit in ventral roots where they form synapses onto postganglionic neurons. Thus, these neurons are the last point at which the central nervous system can exert an effect to enable changes in sympathetic outflow. This review considers the degree of complexity of sympathetic control occurring at the level of the spinal cord. The morphology and targets of SPNs illustrate the diversity within this group, as do their diverse intrinsic properties which reveal some functional significance of these properties. SPNs show high degrees of coupled activity, mediated through gap junctions, that enables rapid and coordinated responses; these gap junctions contribute to the rhythmic activity so critical to sympathetic outflow. The main inputs onto SPNs are considered; these comprise afferent, descending, and interneuronal influences that themselves enable functionally appropriate changes in SPN activity. The complexity of inputs is further demonstrated by the plethora of receptors that mediate the different responses in SPNs; their origins and effects are plentiful and diverse. Together these different inputs and the intrinsic and coupled activity of SPNs result in the rhythmic nature of sympathetic outflow from the spinal cord, which has a variety of frequencies that can be altered in different conditions. © 2015 American Physiological Society.Compr Physiol5:829‐869, 2015.
Endothelial Cell Regulation of Pulmonary Vascular Tone, Inflammation, and Coagulation
Authors: Goldenberg Neil M. , Kuebler Wolfgang M.
Published: March 2015

The pulmonary endothelium represents a heterogeneous cell monolayer covering the luminal surface of the entire lung vasculature. As such, this cell layer lies at a critical interface between the blood, airways, and lung parenchyma, and must act as a selective barrier between these diverse compartments. Lung endothelial cells are able to produce and secrete mediators, display surface receptor, and cellular adhesion molecules, and metabolize circulating hormones to influence vasomotor tone, both local and systemic inflammation, and coagulation functions. In this review, we will explore the role of the pulmonary endothelium in each of these systems, highlighting key regulatory functions of the pulmonary endothelial cell, as well as novel aspects of the pulmonary endothelium in contrast to the systemic cell type. The interactions between pulmonary endothelial cells and both leukocytes and platelets will be discussed in detail, and wherever possible, elements of endothelial control over physiological and pathophysiological processes will be examined. © 2015 American Physiological Society.Compr Physiol5:531‐559, 2015.
Fetal Programming and Cardiovascular Pathology
Authors: Alexander Barbara T. , Dasinger John Henry , Intapad Suttira
Published: March 2015

Low birth weight serves as a crude proxy for impaired growth during fetal life and indicates a failure for the fetus to achieve its full growth potential. Low birth weight can occur in response to numerous etiologies that include complications during pregnancy, poor prenatal care, parental smoking, maternal alcohol consumption, or stress. Numerous epidemiological and experimental studies demonstrate that birth weight is inversely associated with blood pressure and coronary heart disease. Sex and age impact the developmental programming of hypertension. In addition, impaired growth during fetal life also programs enhanced vulnerability to a secondary insult. Macrosomia, which occurs in response to maternal obesity, diabetes, and excessive weight gain during gestation, is also associated with increased cardiovascular risk. Yet, the exact mechanisms that permanently change the structure, physiology, and endocrine health of an individual across their lifespan following altered growth during fetal life are not entirely clear. Transmission of increased risk from one generation to the next in the absence of an additional prenatal insult indicates an important role for epigenetic processes. Experimental studies also indicate that the sympathetic nervous system, the renin angiotensin system, increased production of oxidative stress, and increased endothelin play an important role in the developmental programming of blood pressure in later life. Thus, this review will highlight how adverse influences during fetal life and early development program an increased risk for cardiovascular disease including high blood pressure and provide an overview of the underlying mechanisms that contribute to the fetal origins of cardiovascular pathology. © 2015 American Physiological Society.Compr Physiol5:997‐1025, 2015.
Thioredoxin Superfamily and Its Effects on Cardiac Physiology and Pathology
Authors: Yoshioka Jun
Published: March 2015

A precise control of oxidation/reduction of protein thiols is essential for intact cardiac physiology. Irreversible oxidative modifications have been proposed to play a role in the pathogenesis of cardiovascular diseases. An imbalance of redox homeostasis with diminution of antioxidant capacities predisposes the heart to oxidant injury. There is growing interest in endoplasmic reticulum (ER) stress in the cardiovascular field, since perturbation of redox homeostasis in the ER is sufficient to cause ER stress. Because a number of human diseases are related to altered redox homeostasis and defects in protein folding, many research efforts have been devoted in recent years to understanding the structure and enzymatic properties of the thioredoxin superfamily. The thioredoxin superfamily has been well documented as thiol oxidoreductases to exert a role in various cell signaling pathways. The redox properties of the thioredoxin motif account for the different functions of several members of the thioredoxin superfamily. While thioredoxin and glutaredoxin primarily act as antioxidants by reducing protein disulfides and mixed disulfide, another member of the superfamily, protein disulfide isomerase (PDI), can act as an oxidant by forming intrachain disulfide bonds that contribute to proper protein folding. Increasing evidence suggests a pivotal role of PDI in the survival pathway that promotes cardiomyocyte survival and leads to more favorable cardiac remodeling. Thus, the thiol redox state is important for cellular redox signaling and survival pathway in the heart. This review summarizes the key features of major members of the thioredoxin superfamily directly involved in cardiac physiology and pathology. © 2015 American Physiological Society.Compr Physiol5:513‐530, 2015.
Myocardial Tissue Caveolae
Authors: Sanon Vani P. , Sawaki Daigo , Mjaatvedt Corey H. , Jourdan‐Le Saux Claude
Published: March 2015

Caveolae and their coat proteins, caveolins (Cav), are cave‐like invaginations found in the plasma membrane of a variety of cells. These unique vesicles and their coat proteins, Cavs, have diverse effects on endothelial function, nitric oxide synthesis regulation, signal transduction, cholesterol metabolism, and apoptosis. Animal studies in Cav knockout mice demonstrate the vital role of these structural proteins on endothelial and vascular function. Genetic studies have proposed that beside neoplasia, Cavs may play a role in the development of atherosclerosis, cardiomyopathy, long QT syndrome, pulmonary fibrosis, and muscular dystrophy. The role of Cav expression in atherosclerotic disease is poorly understood and remains controversial. Interestingly, there is emerging evidence between low Cav‐1 levels and the vulnerable plaque, which could potentially identify Cav‐1 as a novel plaque biomarker. Cavs, through intricate biochemical pathways involving endothelial nitric oxide synthase and mitogen‐activated protein kinase, are known to affect the cardiovascular system at multiple levels. In the present review, we aim to highlight the nature and types of caveolae, caveolar signaling mechanisms and regulation, and the pathophysiology of Cavs as it pertains to the cardiovascular system. Ongoing research is needed to clarify the diagnostic and prognostic role of these novel proteins and to determine how the effects of Cavs can translate into clinical medicine. © 2015 American Physiological Society.
Compr Physiol
5:871‐886, 2015.
Nitric Oxide and the Cardiovascular System
Authors: Bohlen Harold Glenn
Published: March 2015

Nitric oxide (NO) generated by endothelial cells to relax vascular smooth muscle is one of the most intensely studied molecules in the past 25 years. Much of what is known about NO regulation of NO is based on blockade of its generation and analysis of changes in vascular regulation. This approach has been useful to demonstrate the importance of NO in large scale forms of regulation but provides less information on the nuances of NO regulation. However, there is a growing body of studies on multiple types ofin vivomeasurement of NO in normal and pathological conditions. This discussion will focus onin vivostudies and how they are reshaping the understanding of NO's role in vascular resistance regulation and the pathologies of hypertension and diabetes mellitus. The role of microelectrode measurements in the measurement of [NO] will be considered because much of the controversy about what NO does and at what concentration depends upon the measurement methodology. For those studies where the technology has been tested and found to be well founded, the concept evolving is that the stresses imposed on the vasculature in the form of flow‐mediated stimulation, chemicals within the tissue, and oxygen tension can cause rapid and large changes in the NO concentration to affect vascular regulation. All these functions are compromised in both animal and human forms of hypertension and diabetes mellitus due to altered regulation of endothelial cells and formation of oxidants that both damage endothelial cells and change the regulation of endothelial nitric oxide synthase. © 2015 American Physiological Society.Compr Physiol5:803‐828, 2015.
Low‐Cost Synthesis of Bimodal Mesoporous Silica‐Based Materials by Pseudomorphic Transformation
Authors: Morales José Manuel , Moragues Alaina , El Haskouri Jamal , Guillem Carmen , Latorre Julio , Murcia‐Mascarós Sonia , Beltrán Aurelio , Beltrán Daniel , Amorós Pedro
Published: March 2015

Nanoparticulate bimodal porous silica‐based materials have been prepared through a surfactant‐assisted procedure by using a simple template and starting from inexpensive sodium silicate as silicon source. Different procedural variables, such as pH or the nature and concentration of the surfactant, have been explored to optimize the preparative protocol, which allows, in turn, improved understanding of the formation process. The final bulk materials (called UVM‐10 or M‐UVM‐10) are formed by pseudomorphic transformation of fresh silica‐based xerogels under mild basic conditions. The UVM‐10 architecture is constructed from small mesoporous nanoparticles, the aggregation of which generates a disordered secondary 3 D pore system (large‐meso/macropores) defined by interparticle voids. Modulation of the intraparticle mesopore size is achieved by using surfactants with variable tail lengths, while maintaining the same head group. Textural porosity has been handled independently by hydrothermally modifying the particle size of the reactive silica‐based xerogel. By simply adding metal alkoxides to the initial reaction mixture, the preparative protocol allows for functionalizing the silica walls by incorporating relatively high proportions of homogeneously dispersed heteroelements, such as Al and Ti.
Controlling Localization and Excretion of Nanoparticles by Click Modification of the Surface Chemical Structures inside Living Cells
Authors: Ito Takeo , Nakamura Takuma , Kusaka Eriko , Kurihara Ryohsuke , Tanabe Kazuhito
Published: March 2015

Surface modification of silica nanoparticles (SiNPs) inside living cells was conducted by using the copper‐free bioorthogonal click reaction to evaluate the effects of surface chemical structures on dynamic behavior and excretion of SiNPs. The results demonstrated the spatial translocation of intracellular SiNPs to the plasma membrane upon surface modification in situ with phospholipids. Moreover, the extent and kinetics of excretion of the SiNPs from inside the cell were enhanced by modification.
Disrupting Deliberative Discourse: Strategic Political Incivility at the Local Level
Authors: Emerson Kirk , Joosse Alexandra P. , Dukes Frank , Willis Wendy , Cowgill Kim Hodge
Published: March 2015

This article focuses on strategic political incivility intended to shut down or disrupt local arenas for public discourse. Professional facilitators who design and manage public discourse and democratic deliberation are the subject of this survey research. Survey questions elicited specific incidences of strategic political incivility and facilitators’ responses to these events. The results from this exploratory study suggest that strategic political incivility at the local level may not be as unmanageable a problem for professional facilitators as media reports purport. Recommendations for improving practice emerge from this study, along with promising avenues for future research on uncivil discourse.
Best practices report from LSAC settlement offers guidance
Authors: Masinter Michael R.
Published: March 2015

In an earlier column, I reported on the settlement of the Department of Justice lawsuit against the Law School Admissions Council. The settlement consent judgment required the creation of a panel of experts tasked with preparing a report with best practices for the LSAC to follow in reviewing test accommodation requests, including requests for extended time. The panel recently released its report.
Binge eating disorder and medical comorbidities in bariatric surgery candidates
Authors: Mitchell James E. , King Wendy C. , Pories Walter , Wolfe Bruce , Flum David R. , Spaniolas Konstatinos , Bessler Mark , Devlin Michael , Marcus Marsha D. , Kalarchian Melissa , Engel Scott , Khandelwal Saurobh , Yanovski Susan
Published: March 2015

Objective

 To determine whether binge eating disorder (BED) status is associated with medical comorbidities in obese adults scheduled for bariatric surgery.

Method

 The study utilized Longitudinal Assessment of Bariatric Surgery‐2 data obtained from six clinical centers around the United States. This is a well‐phenotyped cohort of individuals who were evaluated within 30 days before their scheduled surgery using standardized protocols. In the cohort, 350 participants were classified as having BED and 1,875 as not having BED (non‐BED). Multivariable logistic regression was used to determine whether BED status was independently related to medical comorbidities. As an exploratory analysis, significance was based on nominal p‐values (p < .05). Holm's‐adjusted p‐values were also reported.

Results

 After adjusting for age, sex, education, and body mass index, BED status was found to be independently associated with four of the 15 comorbidities (i.e., impaired glucose levels (odds ratio [OR] = 1.45 (95% confidence interval [CI]: 1.12–1.87)), high triglycerides (OR = 1.28 (95% CI: 1.002–1.63)), and urinary incontinence (OR = 1.30 (95% CI: 1.02–1.66)), all being more common among the BED sample, and severe walking limitations being less common in the BED sample (OR = 0.53 (95% CI: 0.29–0.96)). With further adjustment for psychiatric/emotional health indicators, BED status was independently associated with three comorbidities (impaired glucose levels (OR = 1.36 (95% CI: 1.04–1.79)), cardiovascular disease (OR = 0.50 (95% CI: 0.30–0.86)), and severe walking limitations (OR = 0.38 (95% CI: 0.19–0.77)). However, Holm's‐adjusted p‐values for all variables were greater than .05.

Discussion

 The results suggest the possibility of a contribution of BED to risk of specific medical comorbidities in severely obese adults. © 2015 Wiley Periodicals, Inc. (Int J Eat Disord 2015; 48:471–476)
Natura 2000 Within Discursive Space: The case of the Ria de Aveiro
Authors: Sumares David , Fidelis Teresa
Published: March 2015

The Ria de Aveiro, a Portuguese estuary protected under Natura 2000, has suffered strong development pressures in recent decades which, in combination with the decline of traditional activities, have caused severe environmental problems. To produce a description of the context's discursive dimension and identify obstacles for collaborative and coherent management of this complex socio‐ecological system, we have analysed the consultations related to the environmental assessment of five development projects and a programme for ‘integrated redevelopment and enhancement operations’ in priority coastal areas. The exact meaning of sustainability regarding the estuary is far from consensual among the different participants, and is often in conflict with the vision behind the planned interventions. In this paper, we identify and discuss key themes in local discourses that dialectically interrelate in ways that need to be considered by this territory's environmental governance and argue for the importance of discursive explorations on a case‐by‐case basis. Copyright © 2015 John Wiley & Sons, Ltd and ERP Environment
What Roles are There for Government in Voluntary Environmental Programmes?
Authors: van der Heijden Jeroen
Published: March 2015

This article seeks to understand to a greater extent why and how governments are involved in voluntary environmental programmes (VEPs). A better understanding of the role(s) of government in VEPs is of relevance because the current VEP literature considers such involvement one of the key conditions that may explain VEP performance. Building on the existing VEP literature, the article maps, describes and contrasts the roles of governments in 40 VEPs in the building sector in Australia, the Netherlands, Singapore and the United States. It finds that governments are involved in almost all of these VEPs (95 per cent) and that governments predominantly take up traditional roles (i.e. initiating and leading VEPs and monitoring and enforcing VEPs), sometimes combined with innovative roles (i.e. supporting VEPs or assembling VEPs). This, the article argues, leaves opportunities for other modes of involvement unexplored, particularly those in which governments take up only innovative roles in VEPs. Copyright © 2015 John Wiley & Sons, Ltd and ERP Environment
Modulating Sonogashira Cross‐Coupling Reactivity in Four‐Coordinate Nickel Complexes by Using Geometric Control
Authors: Petuker Anette , Merten Christian , Apfel Ulf‐Peter
Published: March 2015

Herein, we present the synthesis of nickel complexes with tripodal phosphine ligands, CH3Si(CH2PPh2)3 and CH3C(CH2PPh2)3, and their application as catalysts in Sonogashira cross‐coupling reactions in water. Although both types of nickel complexes are based on similar tripodal ligands, the Si‐derived compounds adopt stable tetrahedral coordination geometries, whereas the C‐derived counterparts adopt a square‐planar coordination environment. This structural and electronic difference has an important effect on the catalytic properties of the complexes. Our study demonstrates that C‐derived complexes are catalytically inactive, whereas the complexes [CH3Si(CH2PPh2)3NiX2] (X = Cl–, Br–) are competent catalysts for cross‐coupling reactions of aryl halides with phenylacetylenes. This investigation reveals the importance of structural tuning on catalysis and strongly supports the theory that tetrahedral (PR3)2NiCl2 complexes are the active species in Sonogashira cross‐coupling reactions.
Modular Synthesis of Dihydroxyacetone Monoalkyl Ethers and Isosteric 1‐Hydroxy‐2‐alkanones
Authors: Güclü Deniz , Rale Madhura , Fessner Wolf‐Dieter
Published: March 2015

Straightforward methods for the efficient, systematic preparation of libraries of the title compound classes have been evaluated. A general and efficient modular route to dihydroxyacetone monoethers was developed based on trityl glycidol, which, through epoxide opening, oxidation, and deprotection, provided variously alkylated ethers by three routine operations in good overall yields (eight examples, 24–59 %). The preparation of structurally related 1‐hydroxyalkanones depends on the availability of the most economic starting materials and on their physicochemical properties. Thus, the most practical one‐step approaches consisted of the sec‐selective oxidation of short‐chain 1,2‐diols (≤ C6) using NaOCl, and the direct ketohydroxylation of 1‐alkenes (≥ C6) using buffered stoichiometric KMnO4 or catalytic RuO4 with reoxidation by oxone, for which mostly good overall yields were achieved on a multigram scale (nine examples, 15–78 %).
Synthesis of 3,5,5‐Trisubstituted 4‐Hydroxy‐4H,5H‐1,2,4‐oxadiazoles through the Condensation of N‐Hydroxyamidoximes and Ketones or Aldehydes
Authors: Liu Ning , Zhai Lian‐Jie , Lian Peng , Li Hui , Wang Bo‐Zhou
Published: March 2015

An interesting class of heterocyclic compounds, 1,2,4‐oxadiazoles and their derivatives have attracted the attention of chemists because of their use in the development of new pharmaceuticals and functional materials. Herein, a catalyst‐free reaction of N‐hydroxyamidoxime with various ketones or aldehydes has been investigated. The reaction was carried out in methanol under mild conditions and gave 3,5,5‐trisubstituted 4‐hydroxy‐4H,5H‐1,2,4‐oxadiazole derivatives in excellent yields. The structure of product 3f was confirmed by single‐crystal X‐ray diffraction studies.
A Diels–Alder Approach to a Communesin Model: A/B‐Cyclization Route
Authors: Sanzone Angelo , Somfai Peter
Published: March 2015

Compound 3, a model system for communesin F, was approached by using a Diels–Alder reaction for the introduction of the vicinal quaternary stereocentres. Subsequent introduction of A/B‐ring system followed by D/E‐ring closure gave hexacyclic system 22. All attempts to reduce this material to give compound 3 were, however, unproductive.
Effect of dielectrophoretic force on swimming bacteria
Authors: Tran Ngoc Phu , Marcos
Published: March 2015

Dielectrophoresis (DEP) has been applied widely in bacterial manipulation such as separating, concentrating, and focusing. Previous studies primarily focused on the collective effects of DEP force on the bacterial population. However, the influence of DEP force on the swimming of a single bacterium had not been investigated. In this study, we present a model to analyze the effect of DEP force on a swimming helically flagellated bacterium, particularly on its swimming direction and velocity. We consider a simple DEP force that acts along the X‐direction, and its strength as well as direction varies with the X‐ and Y‐positions. Resistive force theory is employed to compute the hydrodynamic force on the bacterium's flagellar bundle, and the effects of both DEP force and rotational diffusion on the swimming of the bacterium are simultaneously taken into consideration using the Fokker–Planck equation. We show the mechanism of how DEP force alters the orientation and velocity of the bacterium. In most cases, the DEP force dominantly influences the orientation of the swimming bacterium; however, when the DEP force strongly varies along the Y‐direction, the rotational diffusion is also responsible for determining the bacterium's reorientation. More interestingly, the variance of DEP force along the Y‐direction causes the bacterium to experience a translational velocity perpendicular to its primary axis, and this phenomenon could be utilized to focus the bacteria. Finally, we show the feasibility of applying our findings to achieve bacterial focusing.
Development of a capillary electrophoresis method with direct UV detection for the analysis of thiodiglycol and its oxidation products
Authors: Jõul Piia , Lees Heidi , Vaher Merike , Kobrin Eeva‐Gerda , Kaljurand Mihkel , Kuhtinskaja Maria
Published: March 2015

A novel method based on CE with precolumn derivatization and direct UV detection for the determination of thiodiglycol (TDG), TDG sulfoxide, and TDG sulfone in water samples was developed. The lack of a UV chromophore of target analytes was overcome by derivatization with phthalic anhydride. The reactant concentrations, as well as the derivatization dependence on heating temperature and time, were carefully investigated. The baseline separation of three derivatives was achieved in less than 8 min by applying a simple BGE composed of a 30 mM borate buffer at pH 8.5. Several parameters affecting the separation efficiency (buffer pH and concentration, capillary temperature, and applied voltage) were evaluated. Calibration curves of all compounds showed good linear correlations (R2 > 0.9994). The LODs of the TDG and its oxidation products were in the range of 98–154 ng/mL. The precision tests resulted in RSDs for migration times and peak areas of less than 1.2 and 3.6%, respectively. The developed method was successfully applied for the analysis of TDG and oxidation products in seawater, utilizing the carbon aerogel‐based adsorbents for sample purification and concentration. Additionally, the method has the potential to be transformed into a portable CE format.
Orders of magnitude increase in soil erosion associated with land use change from native to cultivated vegetation in a Brazilian savannah environment
Authors: Oliveira Paulo Tarso S. , Nearing Mark A. , Wendland Edson
Published: March 2015

The Brazilian savanna (cerrado) is a large and important economic and environmental region that is experiencing significant loss of its natural landscapes due to pressures of food and energy production, which in turn has caused large increases in soil erosion. However the magnitude of the soil erosion increases in this region is not well understood, in part because scientific studies of surface runoff and soil erosion are scarce or nonexistent in the cerrado as well as in other savannahs of the world. To understand the effects of deforestation we assessed natural rainfall‐driven rates of runoff and soil erosion on an undisturbed tropical woodland classified as ‘cerrado sensu stricto denso’ and bare soil. Results were evaluated and quantified in the context of the cover and management factor (C‐factor) of the Universal Soil Loss Equation (USLE). Replicated data on precipitation, runoff, and soil loss on plots (5 × 20 m) under undisturbed cerrado and bare soil were collected for 77 erosive storms that occurred over 3 years (2012 through 2014). C‐factor was computed annually using values of rainfall erosivity and soil loss rate. We found an average runoff coefficient of ~20% for the plots under bare soil and less than 1% under undisturbed cerrado. The mean annual soil losses in the plots under bare soil and cerrado were 12.4 t ha‐1 yr‐1 and 0.1 t ha‐1 yr‐1, respectively. The erosivity‐weighted C‐factor for the undisturbed cerrado was 0.013. Surface runoff, soil loss and C‐factor were greatest in the summer and fall. Our results suggest that shifts in land use from the native to cultivated vegetation result in orders of magnitude increases in soil loss rates. These results provide benchmark values that will be useful to evaluate past and future land use changes using soil erosion models and have significance for undisturbed savanna regions worldwide. Copyright © 2015 John Wiley & Sons, Ltd.
The Inexorable Historical Press of the Developing Evaluation Profession
Authors: Altschuld James W. , Engle Molly
Published: March 2015

The history of the field of evaluation is described over the past half century to set the context for examining accreditation, certification, and credentialing that are the foci of this New Directions for Evaluation issue. What have been and are the current forces that guide us in regard to thinking about the three concepts? Understanding how evaluation is evolving is crucial for considering actions that might or might not be taken. To the extent possible this is done from a neutral stance without advocating or endorsing what should or could be done next. © Wiley Periodicals, Inc., and the American Evaluation Association.
Accreditation, Certification, Credentialing: Does It Help?
Authors: Shackman Gene
Published: March 2015

The content and discussion of the first six chapters along with some key literature provide the basis upon which the author formulates his views about accreditation, certification, and credentialing. His position is that anything done would have to lead to better evaluations, and at present there is insufficient evidence about whether accreditation, certification, and credentialing would do so. Thus, the main goal now is to gather further evidence. © Wiley Periodicals, Inc., and the American Evaluation Association.
Elevated temperature adhesion testing of spray‐applied fire‐resistive materials
Authors: White Christopher C. , Tan Kar Tean , Hunston Donald L. , Byrd Eric W.
Published: March 2015

Effective fire protection of steel can be fully realized when spray‐applied fire resistive materials (SFRMs) are bonded sufficiently to structural steel during the event of a fire. The adhesion mechanisms and characterization at elevated temperatures, however, have remained elusive, owing to a shortage of quantitative experimental measurements of adhesion between SFRMs and structural steel. In complement with recent efforts aiming to measure the adhesion at ambient temperature, this contribution reports an experimental method based on a fracture mechanics approach to quantify temperature dependent adhesion behaviors of SFRMs adhered to steel substrates.

Using this test method, it is shown that a sharp loss in adhesion occurs at temperatures well below 200 °C, and a less severe rate at higher temperatures. Thermogravimetric analysis and quasi‐state uniaxial compression tests reveal that SFRMs undergo pronounced losses in mass and modulus upon elevated temperature exposures, respectively. Additionally, the dependence of the bulk properties on temperature correlates strongly with that of fracture energy. A mechanism based on mechanical softening and dehydration of SFRMs is proposed to explain the thermally induced adhesion loss. Furthermore, a comparison with the ASTM E736 was made by invoking a fracture mechanics theory. Calculation of bond strengths reveals temperature dependence analogous to the fracture energy data. Also, the residual bond strengths above 150 °C fall below the threshold value (i.e., ≥ 7.2 kPa or 150 lb/ft2) described in the ASTM E736. Importantly, the SFRMs are found to retain appreciable bond strengths greater than their own body masses, permitting them to remain intact in the event of a fire, in the absence of external perturbations. Published 2015. This article is a U.S. Government work and is in the public domain in the USA.
Energy Infrastructure Development Faces Impediments
Authors: Gibbs Kirstin , Johnson Tyler , McCarthy Catherine
Published: March 2015

While political opposition or regulatory agencies themselves may impede natural gas infrastructure projects, it is often the various environmental and citizen groups protesting these projects that create significant challenges. From the Keystone XL oil pipeline to liquefied natural gas (LNG) export terminals, the strategies for derailing or slowing these projects often depend on the statutory and regulatory tools available, which differ by the governing statute—e.g., the Natural Gas Act (NGA) and the Interstate Commerce Act. Of course, other statutes, such as the National Environmental Policy Act (NEPA), influence how the applicable agency reviews a natural gas infrastructure project.
Surveys of Subsurface Utilities Can Reduce Risk in Plant Decommissioning
Authors: Sciulli A. Edward
Published: March 2015

Power‐generating plants are being shut down, decommissioned, and demolished across the United States. This current move away from aging and less efficient power plants is largely being driven by changes in environmental and regulatory requirements, the high cost of modernizing infrastructure to meet new standards, new and more efficient power generation technology, and the current abundance of alternative cleaner fuels. When it is economically infeasible to retool existing plants to take advantage of new technology or alternate fuels, owners are electing to decommission and demolish these facilities.
Opportunities, Risks, and Outlook of US LNG Export Projects
Authors:   Mohanty Galway Group
Published: March 2015

The US natural gas supply growth in recent years has been driven by massive shale gas developments. Natural gas production in the United States is expected to increase by approximately 20 percent by the end of the decade, to approximately 80 billion cubic feet per day. Available gas reserves are estimated to be sufficient for over 100 years of domestic consumption at current consumption levels. As per the US Energy Information Administration's 2014 Annual Energy Outlook projections (Exhibit 1), shale gas production will reach 46.6 billion cubic feet per day by 2040, from 27.3 billion cubic feet per day today.
Renewable Energy Will Force Change in Utilities
Authors: Vlahoplus Chris , Lyons Cristin , Quinlan Paul
Published: March 2015

Renewable generation resources, coupled with the innovation of enabling technology on the distribution grid, are creating the potential for disruptive change for electric utilities. While utility‐scale renewable strategies can be similar to traditional utility‐scale generation (i.e., large‐scale assets with purchase power agreements (PPAs)), the utility business model may face significant changes from customer‐sited distributed resources, especially distributed solar photovoltaics (PV).
Constraining clay hydration state and its role in active fault systems
Authors: Schleicher Anja M. , Hofmann Heiko , van der Pluijm Ben A.
Published: March 2015

To understand the role of hydrated clay minerals in active fault systems, a humidity chamber connected to an X‐ray diffractometer was used to determine the adsorption of water onto and/or into the crystal structure of smectite. This new type of analysis was carried out under specific temperature and humidity conditions, using powdered clay size fractions (< 2 µm) of rock samples from the San Andreas Fault (USA) and the Nankai Trough (Japan). Pressure cannot be controlled, but does not significantly affect clay swelling at shallow conditions. Air‐dried samples show a discrete smectite phase that swells after traditional ethylene glycolation to an interlayer distance of 1.5 and 1.7 nm. Using the humidity chamber, however, the samples show a shorter interlayer distance, between 1.09 and 1.54 nm. Based on our analysis, we show that (i) ethylene glycol overestimates the size of the interlayer space, and therefore water content, so is a crude maximum only; (ii) interlayer swelling occurs in smectite clay minerals at all temperatures between 25 and 95°C; and (iii) particle orientation increases with increasing humidity, indicating a higher mobility of smectite from interlayer hydration. Detailed characterization of the hydration state of smectite under original conditions is critical for understanding of clay‐fluid interaction, the mechanical behavior during fault displacements, and fluid budgets at depth. We propose that humidity chamber experiments should be the new standard procedure to constrain swelling characteristics of natural and synthetic clay minerals.
Glial cell progenitors in the Drosophila embryo
Authors: Altenhein Benjamin
Published: March 2015

Development and general organization of the nervous system is comparable between insects and vertebrates. Our current knowledge on the formation of neurogenic anlagen and the generation of neural stem cells is deeply influenced by work done in invertebrate model organisms such as Drosophila and Caenorhabditis elegans. It is the aim of this review to summarize the most important steps in neurogenesis in the Drosophila embryo with a special emphasis on glial cell progenitors and the specification of glial cells. Induction of neurogenic regions during early embryogenesis and determination of neural stem cells are briefly described. Special attention is given to the formation of neural precursors called neuroblasts (NB) and their lineages. NBs divide in a stem cell mode to generate a cell clone of either neurons and/or glial cells. The latter require the activation of the transcription factor glial cells missing (gcm), thus providing a binary switch between neuronal and glial cell fates. Further aspects of glial cell specification and the resulting heterogeneity of the glial population in Drosophila are discussed. GLIA 2015;63:1291–1302