bluuebunny/crossref_metadata_2025_split huggingface dataset:
Ligand Displacement Reaction Paths in a Diiron Hydrogenase Active Site Model Complex
Authors: Blank Jan H. , Moncho Salvador , Lunsford Allen M. , Brothers Edward N. , Darensbourg Marcetta Y. , Bengali Ashfaq A. 
Published: August 2016

AbstractThe mechanism and energetics of CO, 1‐hexene, and 1‐hexyne substitution from the complexes (SBenz)2[Fe2(CO)6] (SBenz=SCH2Ph) (1‐CO), (SBenz)2[Fe2(CO)5(η2‐1‐hexene)] (1‐(η2‐1‐hexene)), and (SBenz)2[Fe2(CO)5(η2‐1‐hexyne)] (1‐(η2‐1‐hexyne)) were studied by using time‐resolved infrared spectroscopy. Exchange of both CO and 1‐hexyne by P(OEt)3 and pyridine, respectively, proceeds by a bimolecular mechanism. As similar activation enthalpies are obtained for both reactions, the rate‐determining step in both cases is assumed to be the rotation of the Fe(CO)2L (L=CO or 1‐hexyne) unit to accommodate the incoming ligand. The kinetic profile for the displacement of 1‐hexene is quite different than that for the alkyne and, in this case, both reaction channels, that is, dissociative (SN1) and associative (SN2), were found to be competitive. Because DFT calculations predict similar binding enthalpies of alkene and alkyne to the iron center, the results indicate that the bimolecular pathway in the case of the alkyne is lower in free energy than that of the alkene. In complexes of this type, subtle changes in the departing ligand characteristics and the nature of the mercapto bridge can influence the exchange mechanism, such that more than one reaction pathway is available for ligand substitution. The difference between this and the analogous study of (μ‐pdt)[Fe(CO)3]2 (pdt=S(CH2)3S) underscores the unique characteristics of a three‐atom S−S linker in the active site of diiron hydrogenases.
Vapor‐Phase Deposition and Modification of Metal–Organic Frameworks: State‐of‐the‐Art and Future Directions
Authors: Stassen Ivo , De Vos Dirk , Ameloot Rob 
Published: August 2016

AbstractMaterials processing, and thin‐film deposition in particular, is decisive in the implementation of functional materials in industry and real‐world applications. Vapor processing of materials plays a central role in manufacturing, especially in electronics. Metal–organic frameworks (MOFs) are a class of nanoporous crystalline materials on the brink of breakthrough in many application areas. Vapor deposition of MOF thin films will facilitate their implementation in micro‐ and nanofabrication research and industries. In addition, vapor–solid modification can be used for postsynthetic tailoring of MOF properties. In this context, we review the recent progress in vapor processing of MOFs, summarize the underpinning chemistry and principles, and highlight promising directions for future research.
Enhancement of TbIII–CuII Single‐Molecule Magnet Performance through Structural Modification
Authors: Heras Ojea María José , Milway Victoria A. , Velmurugan Gunasekaran , Thomas Lynne H. , Coles Simon J. , Wilson Claire , Wernsdorfer Wolfgang , Rajaraman Gopalan , Murrie Mark 
Published: August 2016

AbstractWe report a series of 3d–4f complexes {Ln2Cu3(H3L)2Xn} (X=OAc−, Ln=Gd, Tb or X=NO3−, Ln=Gd, Tb, Dy, Ho, Er) using the 2,2′‐(propane‐1,3‐diyldiimino)bis[2‐(hydroxylmethyl)propane‐1,3‐diol] (H6L) pro‐ligand. All complexes, except that in which Ln=Gd, show slow magnetic relaxation in zero applied dc field. A remarkable improvement of the energy barrier to reorientation of the magnetisation in the {Tb2Cu3(H3L)2Xn} complexes is seen by changing the auxiliary ligands (X=OAc− for NO3−). This leads to the largest reported relaxation barrier in zero applied dc field for a Tb/Cu‐based single‐molecule magnet. Ab initio CASSCF calculations performed on mononuclear TbIII models are employed to understand the increase in energy barrier and the calculations suggest that the difference stems from a change in the TbIII coordination environment (C4v versus Cs).
6‐Azido‐6‐deoxy‐l‐idose as a Hetero‐Bifunctional Spacer for the Synthesis of Azido‐Containing Chemical Probes
Authors: Hamagami Hiroki , Kumazoe Motofumi , Yamaguchi Yoshiki , Fuse Shinichiro , Tachibana Hirofumi , Tanaka Hiroshi 
Published: August 2016

AbstractThe design of 6‐azido‐6‐deoxy‐l‐idose for use as a hetero‐bifunctional spacer is reported. The hemiacetal at one terminus is an equivalent of an aldehyde and can react with nucleophiles, such as amino groups and electron‐rich aromatics. The azido group at the other terminus bio‐orthogonally undergoes a Hüisgen [3+2] cycloaddition with an acetylene. The idose derivative exhibited a higher level of reactivity towards oxime formation than a corresponding glucose derivative. The 13C NMR spectrum of the uniformly 13C‐labeled 6‐azido‐idose indicated that the acyclic forms of the sugar totaled 0.3 % of all the isomers, whereas those of glucose totaled 0.01 %. The larger population of the acyclic forms of the idose derivative would result in higher reactivity towards electrophilic addition in comparison with glucose derivatives. Finally, we prepared a C‐idosyl epigallocatechin gallate (EGCG) that bears an azido group through C‐glycosylation of EGCG with 6‐azido‐idose. This glycosyl form of the C‐idosyl EGCG exhibited a cytotoxicity against U266 cells that was comparable to that of EGCG. These results suggested that the EGCG derivative could be used as an effective chemical probe for the elucidation of EGCG biological functions.
Mesoporous Carbon Materials with Functional Compositions
Authors: Zhang Pengfei , Zhang Jinshui , Dai Sheng 
Published: August 2016

AbstractSince the 1990s, there has been rapidly expanding development of solid materials with mesoporous structure, of which mesoporous carbons are an important family. Toward the design of functional materials, mesoporous carbons with various compositions have been prepared for specific uses, such as catalysts, adsorbents, and electrode materials. Some of those novel materials indeed show promising performance in several fields, such as nitrogen‐doped mesoporous carbon for oxygen reduction reactions in fuel cells and mesoporous carbon nitride for photocatalysis. This Minireview summarizes recent advances in the design, synthesis, characterization, and application of mesoporous carbons with functional compositions and briefly discusses next‐generation mesoporous carbons.
Engineering safety into the design
Authors: Scantlebury Peter 
Published: August 2016

AbstractSafety by design is Amec Foster Wheeler's systematic approach to engineering safety into the design. It is a five‐step approach to engineering design which results in the ability to demonstrate that hazards to people, the environment, assets, and reputation have been systematically and comprehensively identified, and eliminated or controlled during the design phase of the facility/system or equipment.As a result of the safety by design process, the overall risks of a design are minimized by eliminating hazards or applying the right hazards controls to minimize the right hazards. Furthermore, the design elements to control or eliminate the hazards are identified and designed early in the design process when the implementation cost is at a minimum.
A Semantic Corpus Comparison Analysis of Couple‐Focused Interventions for Problematic Alcohol Use
Authors: Soriano Emily C. , Rentscher Kelly E. , Rohrbaugh Michael J. , Mehl Matthias R. 
Published: August 2016

Incorporating spouses into interventions for problematic alcohol use is associated with increased efficacy; yet, little is known about the therapeutic processes that may explain these effects. In a study of partner language use during couple‐focused alcohol interventions, we utilized a linguistic corpus comparison tool, Wmatrix, to identify semantic themes that differentiated couples with successful and unsuccessful treatment outcomes and may therefore also reflect potential change processes. Thirty‐three couples participated in a randomized control trial of Family Systems Therapy (FST) or Cognitive Behavioural Therapy (CBT). Linguistic comparisons of partners' speech during the therapy sessions suggested that drinks and alcohol was a significant differentiating semantic theme. Specifically, patients and spouses in FST with successful outcomes used more language related to drinks and alcohol than patients and spouses in FST with unsuccessful outcomes. Post‐hoc analyses of context suggested that, in FST, successful spouses spoke less about the patient's drinking and more about alcohol in general (without reference to an individual) than unsuccessful spouses. Conversely, spouses in CBT with successful outcomes used less language related to drinks and alcohol than spouses in CBT with unsuccessful outcomes. In CBT, successful spouses spoke more about the patient's and couple's drinking and less about the spouse's and other people's drinking than unsuccessful spouses. Results emphasize the role of spouse behaviour—in this case indexed via language use—in alcohol treatment outcomes. Findings also suggest potentially distinct therapeutic processes in FST and CBT and highlight the utility of linguistic corpus comparison methods in couple‐focused intervention research. Copyright © 2016 John Wiley & Sons, Ltd.Key Practitioner Message

Incorporating spouses into interventions for problematic alcohol use is associated with increased efficacy; yet, little is known about the specific therapeutic processes that may explain these effects.
Findings from this study suggest that semantic themes such as drinks and alcohol in partner speech during therapy sessions differentiate successful and unsuccessful treatment outcomes among couples participating in two couple‐focused interventions for problematic alcohol use.
In addition, the context in which partners used alcohol‐related language differed by intervention type and treatment outcome, which suggests potential therapeutic processes that are unique to the two interventions (Family Systems versus Cognitive Behavioural Therapy).
The converse to Bergmann's rule in bumblebees, a phylogenetic approach
Authors: Ramírez‐Delgado Víctor Hugo , Sanabria‐Urbán Salomón , Serrano‐Meneses Martin A. , Cueva del Castillo Raúl 
Published: August 2016

AbstractTwo patterns commonly emerge when animal body size is analyzed as a function of latitudinal distribution. First, body size increases with latitude, a temperature effect known as Bergmann's rule, and second, the converse to Bergmann's rule, a pattern in which body size decreases with latitude. However, other geographic patterns can emerge when the mechanisms that generate Bergmann's and the converse to Bergmann's clines operate together. Here, we use phylogenetic comparative analysis in order to control for phylogenetic inertia, and we show that bumblebees exhibit the converse to Bergmann's rule. Bumblebee taxa are distributed worldwide in temperate and tropical regions. The largest species are found in places with high water availability during the driest time of the year. Nonetheless, large body size is constrained by extreme temperatures. Bumblebees’ body size could be related to a higher extent to the size of food rewards to be harvested than to the energetic advantages of thermoregulation. Moreover, we found that the body size of eusocial and cuckoo species responded in the same way to environmental variables, suggesting that they have not diverged due to different selective pressures.
Population attenuation in zooplankton communities during transoceanic transfer in ballast water
Authors: Ghabooli Sara , Zhan Aibin , Paolucci Esteban , Hernandez Marco R. , Briski Elizabeta , Cristescu Melania E. , MacIsaac Hugh J. 
Published: August 2016

AbstractSuccessful biological invasion requires introduction of a viable population of a nonindigenous species (NIS). Rarely have ecologists assessed changes in populations while entrained in invasion pathways. Here, we investigate how zooplankton communities resident in ballast water change during transoceanic voyages. We used next‐generation sequencing technology to sequence a nuclear small subunit ribosomal DNA fragment of zooplankton from ballast water during initial, middle, and final segments as a vessel transited between Canada and Brazil. Operational taxonomic unit (OTU) diversity decreased as voyage duration increased, indicating loss of community‐based genetic diversity and development of bottlenecks for zooplankton taxa prior to discharge of ballast water. On average, we observed 47, 26, and 24 OTUs in initial, middle, and final samples, respectively. Moreover, a comparison of genetic diversity within taxa indicated likely attenuation of OTUs in final relative to initial samples. Abundance of the most common taxa (copepods) declined in all final relative to initial samples. Some taxa (e.g., Copepoda) were represented by a high number of OTUs throughout the voyage, and thus had a high level of intraspecific genetic variation. It is not clear whether genotypes that were most successful in surviving transit in ballast water will be the most successful upon introduction to novel environments. This study highlights that population bottlenecks may be common prior to introduction of NIS to new ecosystems.
Genetic connectivity across marginal habitats: the elephants of the Namib Desert
Authors: Ishida Yasuko , Van Coeverden de Groot Peter J. , Leggett Keith E. A. , Putnam Andrea S. , Fox Virginia E. , Lai Jesse , Boag Peter T. , Georgiadis Nicholas J. , Roca Alfred L. 
Published: August 2016

AbstractLocally isolated populations in marginal habitats may be genetically distinctive and of heightened conservation concern. Elephants inhabiting the Namib Desert have been reported to show distinctive behavioral and phenotypic adaptations in that severely arid environment. The genetic distinctiveness of Namibian desert elephants relative to other African savanna elephant (Loxodonta africana) populations has not been established. To investigate the genetic structure of elephants in Namibia, we determined the mitochondrial (mt) DNA control region sequences and genotyped 17 microsatellite loci in desert elephants (n = 8) from the Hoanib River catchment and the Hoarusib River catchment. We compared these to the genotypes of elephants (n = 77) from other localities in Namibia. The mtDNA haplotype sequences and frequencies among desert elephants were similar to those of elephants in Etosha National Park, the Huab River catchment, the Ugab River catchment, and central Kunene, although the geographically distant Caprivi Strip had different mtDNA haplotypes. Likewise, analysis of the microsatellite genotypes of desert‐dwelling elephants revealed that they were not genetically distinctive from Etosha elephants, and there was no evidence for isolation by distance across the Etosha region. These results, and a review of the historical record, suggest that a high learning capacity and long‐distance migrations allowed Namibian elephants to regularly shift their ranges to survive in the face of high variability in climate and in hunting pressure.
Integrated foundation–structure seismic assessment through non‐linear dynamic analyses
Authors: Figini R. , Paolucci R. 
Published: August 2016

SummaryThis paper aims at clarifying the role of dynamic soil–structure interaction in the seismic assessment of structure and foundation, when the non‐linear coupling of both subsystems is accounted for. For this purpose, the seismic assessment of an ideal set of bridge piers on shallow foundations is considered. After an initial standard assessment, based on capacity design principles, the evaluation of the seismic response of the piers is carried out by dynamic simulations, where both the non‐linear responses of the superstructure and of the foundation are accounted for, in the latter case through the macro‐element modeling of the soil–foundation system. The results of the dynamic simulations point out the beneficial effects of the non‐linear response of the foundation, which provides a substantial contribution to the overall energy dissipation during seismic excitation, thus allowing the structural ductility demand to decrease significantly with respect to a standard fixed‐base or linear‐elastic base assessment. Permanent deformations at the foundation level, such as rotation and settlement, turn out to be of limited amount. Therefore, an advanced assessment approach of the integrated non‐linear system, consisting of the interacting foundation and superstructure, is expected to provide more rationale and economic results than the standard uncoupled approach, which, neglecting any energy dissipation at the foundation level, generally overestimates the ductility demand on the superstructure. Copyright © 2016 John Wiley & Sons, Ltd.
Marginal abatement cost curve for wind power in China: a provincial‐level analysis
Authors: Xiong Weiming , Yang Yuanzhe , Wang Yu , Zhang Xiliang 
Published: August 2016

AbstractWind power has seen a remarkable growth in China since the Renewable Energy Law came into force in the beginning of 2006. However, the contribution and the economic cost of wind power development to reduce carbon emission at the provincial level are still unclear. This research combined geographic information system analysis and levelized production cost calculation to provide provincial‐level supply curve of carbon dioxide (CO2) mitigation by wind power in China. The results showed that wind power could be a very competitive mitigation option in China, with a potential to contribute 500 million tons of CO2 emission mitigation at an average abatement cost of 75 RMB/t of CO2 mitigation. The emission abatement cost and the potential to reduce carbon emission in different provinces may be used for national planning as well as for the allocation of investments.
Co‐optimization of CO2‐EOR and storage processes in mature oil reservoirs
Authors: Ampomah William , Balch Robert S. , Grigg Reid B. , McPherson Brian , Will Robert A. , Lee Si‐Yong , Dai Zhenxue , Pan Feng 
Published: August 2016

AbstractThis paper presents an optimization methodology for CO2enhanced oil recovery in partially depleted reservoirs. A field‐scale compositional reservoir flow model was developed for assessing the performance history of an active CO2flood and for optimizing both oil production and CO2storage in the Farnsworth Unit (FWU), Ochiltree County, Texas. A geological framework model constructed from geophysical, geological, and engineering data acquired from the FWU was the basis for all reservoir simulations and the optimization method. An equation of state was calibrated with laboratory fluid analyses and subsequently used to predict the thermodynamic minimum miscible pressure (MMP). Initial history calibrations of primary, secondary and tertiary recovery were conducted as the basis for the study. After a good match was achieved, an optimization approach consisting of a proxy or surrogate model was constructed with a polynomial response surface method (PRSM). The PRSM utilized an objective function that maximized both oil recovery and CO2storage. Experimental design was used to link uncertain parameters to the objective function. Control variables considered in this study included: water alternating gas cycle and ratio, production rates and bottom‐hole pressure of injectors and producers. Other key parameters considered in the modeling process were CO2purchase, gas recycle and addition of infill wells and/or patterns. The PRSM proxy model was ‘trained’ or calibrated with a series of training simulations. This involved an iterative process until the surrogate model reached a specific validation criterion. A sensitivity analysis was first conducted to ascertain which of these control variables to retain in the surrogate model. A genetic algorithm with a mixed‐integer capability optimization approach was employed to determine the optimum developmental strategy to maximize both oil recovery and CO2storage. The proxy model reduced the computational cost significantly. The validation criteria of the reduced order model ensured accuracy in the dynamic modeling results. The prediction outcome suggested robustness and reliability of the genetic algorithm for optimizing both oil recovery and CO2storage. The reservoir modeling approach used in this study illustrates an improved approach to optimizing oil production and CO2storage within partially depleted oil reservoirs such as FWU. This study may serve as a benchmark for potential CO2–EOR projects in the Anadarko basin and/or geologically similar basins throughout the world. © 2016 Society of Chemical Industry and John Wiley & Sons, Ltd.
Effects of Romosozumab Compared With Teriparatide on Bone Density and Mass at the Spine and Hip in Postmenopausal Women With Low Bone Mass
Authors: Genant Harry K , Engelke Klaus , Bolognese Michael A , Mautalen Carlos , Brown Jacques P , Recknor Chris , Goemaere Stefan , Fuerst Thomas , Yang Yu-Ching , Grauer Andreas , Libanati Cesar 
Published: August 2016

ABSTRACT

Romosozumab, a monoclonal antibody that binds sclerostin, has a dual effect on bone by increasing bone formation and reducing bone resorption, and thus has favorable effects in both aspects of bone volume regulation. In a phase 2 study, romosozumab increased areal BMD at the lumbar spine and total hip as measured by DXA compared with placebo, alendronate, and teriparatide in postmenopausal women with low bone mass. In additional analyses from this international, randomized study, we now describe the effect of romosozumab on lumbar spine and hip volumetric BMD (vBMD) and BMC at month 12 as assessed by QCT in the subset of participants receiving placebo, s.c. teriparatide (20 µg once daily), and s.c. romosozumab (210 mg once monthly). QCT measurements were performed at the lumbar spine (mean of L1 and L2 entire vertebral bodies, excluding posterior processes) and hip. One year of treatment with romosozumab significantly increased integral vBMD and BMC at the lumbar spine and total hip from baseline, and compared with placebo and teriparatide (all p &lt; 0.05). Trabecular vertebral vBMD improved significantly and similarly from baseline (p &lt; 0.05) with both romosozumab (18.3%) and teriparatide (20.1%), whereas cortical vertebral vBMD gains were larger with romosozumab compared with teriparatide (13.7% versus 5.7%, p &lt; 0.0001). Trabecular hip vBMD gains were significantly larger with romosozumab than with teriparatide (10.8% versus 4.2%, p = 0.01), but were similar for cortical vBMD (1.1% versus –0.9%, p = 0.12). Cortical BMC gains were larger with romosozumab compared with teriparatide at both the spine (23.3% versus 10.9%, p &lt; 0.0001) and hip (3.4% versus 0.0%, p = 0.03). These improvements are expected to result in strength gains and support the continued clinical investigation of romosozumab as a potential therapy to rapidly reduce fracture risk in ongoing phase 3 studies. © 2016 American Society for Bone and Mineral Research.
The Application of Positive Psychotherapy in Mental Health Care: A Systematic Review
Authors: Walsh Sophie , Cassidy Megan , Priebe Stefan 
Published: August 2016

ObjectivePositive psychotherapy (PPT) stems from the positive psychology movement and is a multicomponent model promoting therapeutic change by developing engagement, pleasure, and meaning. There is some evidence it is effective for depression. PPT is recommended as a flexible model that can be applied to other patient groups alongside other treatments approaches. However, it remains unclear which of the many components are applied. The study aimed to identify how PPT is applied in mental health care.MethodWe systematically searched online databases, including Medline, Embase, PsycINFO, British Nursing Index, Cumulative Index of Nursing and Applied Health, and Cochrane registers (CENTRAL), and completed complementary hand and citation searches. Narrative synthesis was used for analysis.ResultsA total of 12 papers (from 9 studies) widely applied some PPT components (e.g., blessings journal, character strengths) and scarcely applied others (e.g., satisficing plan or family strengths tree). However, papers poorly described the intervention and rationale for applying components.ConclusionGiven the lack of rationale for applying PPT, further research is needed to establish which components are acceptable and feasible for use in different patient groups and settings.