bluuebunny/crossref_metadata_2025 huggingface dataset:
Bisthienylethenes Containing a Benzothiadiazole Unit as a Bridge: Photochromic Performance Dependence on Substitution Position
Authors: Zhu Weihong , Meng Xianle , Yang Yuheng , Zhang Qiong , Xie Yongshu , Tian He
Published: November 2009

A conveniently synthesized photochromic compound, BTB‐1, containing an unprecedented six‐membered 2,1,3‐benzothiadiazole unit as the center ethene bridge, possesses good photochromic performance, with a high cyclization quantum yield and moderate fatigue resistance in solution or an organogel system. The fluorescence of BTB‐1 can be modulated by solvato‐ and photochromism. However, the analogue BTB‐2, in which the dimethylthiophene substituents are relocated to the 5,6‐positions of benzothiadiazole, does not show any detectable photochromism. To the best of our knowledge, this is the first example of six‐membered bridge bisthienylethenes (BTEs) in which the photochromism can be controlled by the substitution position. The photochromism difference is elucidated by the analysis of resonance structure, the Woodward–Hoffmann rule, and theoretical calculations on the ground‐state potential‐energy surface. In a well‐ordered single‐crystal state, BTB‐1 adopts a relatively rare parallel conformation, and forms an interesting two‐dimensional structure due to the presence of multiple directional intermolecular interactions, including CH⋅⋅⋅N and CH⋅⋅⋅S hydrogen‐bonding interactions, and π–π stacking interactions. This work contributes to several aspects for developing novel photochromic BTE systems with fluorescence modulation and performances controlled by substitution position in different states (solution, organogel, and single crystal).
Hydroxypyridinechromene and Pyridinechalcone: Two Coupled Photochromic Systems
Authors: Leydet Yoann , Parola A. Jorge , Pina Fernando
Published: November 2009

Substitution of the phenyl group in 2‐hydroxychalcones by a 4‐pyridine unit dramatically changes the network of chemical reactions of this compound: trans‐chalcone‐type (Ct), cis‐chalcone‐type (Cc), and a hemiketal (hydroxy‐4‐pyridinechromene) (B) and their protonated forms are formed, but the presence of a flavylium‐type cation could not be detected even at very acidic pH values. Moreover, whereas in 2‐phenyl‐2‐benzopyrylium compounds B and Cc are generally elusive species whose kinetic processes in aqueous solutions occur on the sub‐second timescale, in the present compound these species equilibrate on a timescale four orders of magnitude lower. Complete characterization of the equilibrium and kinetics of the reaction network could thus be achieved by 1H NMR spectroscopy and UV/Vis spectrophotometry. The network of chemical reactions exhibits cis–trans photoisomerization, as well as photochromism between the hemiketal and the chalcone‐type species. The irradiation of Ct in MeOH/H2O (1:1) at 365 nm produces B almost quantitatively through two consecutive photochemical reactions: Ct→Cc photoisomerization followed by Cc→B photo ring closure with a global quantum yield of 0.02. On the other hand, irradiation of B at 254 nm leads to a photostationary state composed by 80 % Ct and 20 % B, with a quantum yield of 0.21.
Difluorophosphoryl Nitrene F2P(O)N: Matrix Isolation and Unexpected Rearrangement to F2PNO
Authors: Zeng Xiaoqing , Beckers Helmut , Willner Helge , Neuhaus Patrik , Grote Dirk , Sander Wolfram
Published: November 2009

Triplet difluorophosphoryl nitrene F2P(O)N (X3A′′) was generated on ArF excimer laser irradiation (λ=193 nm) of F2P(O)N3 in solid argon matrix at 16 K, and characterized by its matrix IR, UV/Vis, and EPR spectra, in combination with DFT and CBS‐QB3 calculations. On visible light irradiation (λ>420 nm) at 16 K F2P(O)N reacts with molecular nitrogen and some of the azide is regenerated. UV irradiation (λ=255 nm) of F2P(O)N (X3A′′) induced a Curtius‐type rearrangement, but instead of a 1,3‐fluorine shift, nitrogen migration to give F2PON is proposed to be the first step of the photoisomerization of F2P(O)N into F2PNO (difluoronitrosophosphine). Formation of novel F2PNO was confirmed with 15N‐ and 18O‐enriched isotopomers by IR spectroscopy and DFT calculations. Theoretical calculations predict a rather long PN bond of 1.922 Å [B3LYP/6‐311+G(3df)] and low bond‐dissociation energy of 76.3 kJ mol−1 (CBS‐QB3) for F2PNO.
Controlling Helical Chirality in Atrane Structures: Solvent‐Dependent Chirality Sense in Hemicryptophane‐Oxidovanadium(V) Complexes
Authors: Martinez Alexandre , Robert Vincent , Gornitzka Heinz , Dutasta Jean‐Pierre
Published: November 2009

The diastereomeric hemicryptophane oxidovanadium(V) complexes (P)‐(S,S,S)‐3 and (M)‐(S,S,S)‐4 have been synthesized. 1H and 51V NMR spectra in solution are consistent with the formation of Λ and Δ forms of the propeller‐like vanatrane moiety, leading to two diastereomeric conformers for each complex: that is, (P)‐(S,S,S‐Λ)‐3/(P)‐(S,S,S‐Δ)‐3 and (M)‐(S,S,S‐Λ)‐4/(M)‐(S,S,S‐Δ)‐4. The Λ/Δ ratio is rather temperature‐insensitive but strongly dependent on the solvent (the de of (M)‐(S,S,S)‐4 changes from 0 in benzene to 92 % in DMSO). The solvent therefore controls the preferential clockwise or anticlockwise orientation of the propeller‐like atrane unit. The energy barriers for the Λ⇄Δ equilibrium were determined by NMR experiments, and the highest ΔG≠ value (103.7 kJ mol−1) was obtained for (P)‐(S,S,S)‐3, much higher than those reported for other atrane derivatives. This is attributed to the constraints arising from the cage structure. Determination of the activation parameters provides evidence for a concerted, rather than a stepwise, interconversion mechanism with entropies (ΔS≠) of −243 and −272 J mol−1 K−1 for (P)‐(S,S,S)‐3 and (M)‐(S,S,S)‐4, respectively. The molecular structure of the (P)‐(S,S,S‐Λ)‐3 isomer was solved by X‐ray diffraction and shows a distorted structure with one of the linkers located in the CTV cavity. Complementary quantum chemical calculations were carried out to obtain the energy‐minimized structures of (P)‐(S,S,S)‐3 and (M)‐(S,S,S)‐4. Our density functional theory calculations suggest that the (P)‐(S,S,S‐Λ)‐3 is favored, in agreement with experimental data. For the M series, a similar strategy was used to extract molecular structures and relative energies. As in the case of the P diastereomer, the Λ form dominates over the Δ one.
An Interpenetrated Framework Material with Hysteretic CO2 Uptake
Authors: Mulfort Karen L. , Farha Omar K. , Malliakas Christos D. , Kanatzidis Mercouri G. , Hupp Joseph T.
Published: November 2009

A new, twofold interpenetrated metal–organic framework (MOF) material has been synthesized that demonstrates dramatic steps in the adsorption and hysteresis in the desorption of CO2. Measurement of the structure by powder X‐ray diffraction (PXRD) and pair distribution function (PDF) analysis indicates that structural changes upon CO2 sorption most likely involve the interpenetrated frameworks moving with respect to each other.
Variable selection in spatial regression via penalized least squares
Authors: Wang Haonan , Zhu Jun
Published: November 2009

We consider variable selection in linear regression of geostatistical data that arise often in environmental and ecological studies. A penalized least squares procedure is studied for simultaneous variable selection and parameter estimation. Various penalty functions are considered including smoothly clipped absolute deviation. Asymptotic properties of penalized least squares estimates, particularly the oracle properties, are established, under suitable regularity conditions imposed on a random field model for the error process. Moreover, computationally feasible algorithms are proposed for estimating regression coefficients and their standard errors. Finite‐sample properties of the proposed methods are investigated in a simulation study and comparison is made among different penalty functions. The methods are illustrated by an ecological dataset of landcover in Wisconsin. The Canadian Journal of Statistics 37: 607–624; 2009 © 2009 Statistical Society of Canada
Synthesis, Enzymatic Evaluation, and Docking Studies of Fluorogenic Caspase 8 Tetrapeptide Substrates
Authors: Reszka Przemysław , Schulz Riad , Methling Karen , Lalk Michael , Bednarski Patrick J.
Published: November 2009

The synthesis, enzymatic evaluation, and molecular modeling studies of new fluorogenic tetrapeptide‐based substrates selective for caspase 8, having the general structure Ac‐IETD–AXX, are described. Various fluorescent reporter groups (AXX), i.e., 3‐ and 4‐substituted coumarins and quinolin‐2(1H)‐ones were synthesized by von Pechmann condensation. They were subsequently coupled with the caspase‐8‐selective tetrapeptide Ac‐IETD‐OH under newly developed synthetic conditions to give the desired substrates in good yields and in high enantiomeric purity. Based on KM and Vmax values, the new compounds proved to be excellent substrates for recombinant human caspase 8. In contrast, the KM values for the same compounds as substrates for human caspase 3 were approximately 10–20‐fold higher. Molecular modeling studies based on the X‐ray crystal structures of both human caspases 3 and 8 revealed that there is sufficient room within both active sites to accommodate substrates with moderately bulky substituents in the 3‐ and 4‐positions of the fluorogenic coumarins and quinolin‐2(1H)‐ones. Automated docking of the substrates into the active sites of both human caspases 3 and 8 with the program AutoDock 3 gave structures similar to the published crystallographic structures for the same tetrapeptide bound to caspase 8 in the form of an irreversible inhibitor. The calculated binding energies for the new substrates to either caspase 3 or 8 showed little difference between the substrates, consistent with the KM data. In addition, the calculated binding energies (ΔG) to caspase 8 were considerably more negative than those to caspase 3, also consistent with the KM data. A possible molecular interaction that might explain the selectivity of the IETD tetrapeptide motif for caspase 8 over caspase 3 is discussed.
Characteristics associated with early and late melanoma metastases
Authors: Brauer Jeremy A. , Wriston Cooper C. , Troxel Andrea B. , Elenitsas Rosalie , Shin Daniel B. , Guerry DuPont , Ming Michael E.
Published: November 2009

BACKGROUND:

Differences in risk factors for metastases at different time intervals after treatment have been described in several malignancies; however, to the authors' knowledge, no extensive study examining this issue in melanoma has been conducted to date.

METHODS:

The authors performed a nested case‐control study of patients with melanoma who presented with only local disease. Patients in the case group included 549 patients who developed metastases ≥6 months after surgery. Of these, 320 patients developed metastasis within 3 years after undergoing definitive surgery (early metastases [EM]), and 70 patients developed metastasis ≥8 years after undergoing definitive surgery (late metastases [LM]). For each case, a control patient was chosen who had melanoma but who did not develop metastases in the same interval. Univariate and conditional multivariate logistic regression were used in the analysis of 34 clinical and tumor characteristics.

RESULTS:

Multivariate analysis confirmed previously established risk factors for metastases, such as increasing tumor thickness. In addition, the authors discovered that a personal history of nonmelanoma skin cancer (P = .006) and a history of cancer other than skin cancer (P = .020) also were associated with metastasis. In comparing the 320 EM patients with the 70 LM patients, EM patients were more likely to have thicker lesions (P < .001), ulcerated lesions (P = .016), and a history of nonmelanoma skin cancer (P = .024).

CONCLUSIONS:

In this study, 2 potentially novel risk factors for melanoma metastases were identified, and different profiles of risk factors were constructed for EM versus LM. These differences may be important in future risk identification and stratification for clinical trials and for the management and treatment of patients with melanoma. Cancer 2010. © 2010 American Cancer Society.
Phase 2 trial of combination thalidomide plus temozolomide in patients with metastatic malignant melanoma: Southwest Oncology Group S0508
Authors: Clark Joseph I. , Moon James , Hutchins Laura F. , Sosman Jeffrey A. , Kast W. Martin , Da Silva Diane M. , Liu P. Y. , Thompson John A. , Flaherty Lawrence E. , Sondak Vernon K.
Published: November 2009

BACKGROUND:

In limited institution phase 2 studies, thalidomide and temozolomide has yielded response rates (RRs) up to 32% for advanced melanoma, leading to the use of this combination as “standard” by some. We conducted a multicenter phase 2 trial to better define the clinical efficacy of thalidomide and temozolomide and the immune modulatory effects of thalidomide, when combined with temozolomide, in patients with metastatic melanoma.

METHODS:

Patients must have had stage IV cutaneous melanoma, no active brain metastases, Zubrod PS 0‐1, up to 1 prior systemic therapy excluding thalidomide, temozolomide, or dacarbazine, adequate organ function, and given informed consent. The primary endpoint was 6‐month progression‐free survival (PFS). Secondary endpoints included overall survival (OS), RR, toxicities, and assessment of relationships between biomarkers and clinical outcomes. Patients received thalidomide (200 mg/d escalated to 400 mg/d for patients <70, or 100 mg/d escalated to 250 mg/d for patients ≥70) plus temozolomide (75 mg/m2/d × 6 weeks, and then 2 weeks rest).

RESULTS:

Sixty‐four patients were enrolled; 2 refused treatment. The 6‐month PFS was 15% (95% confidence interval [CI], 6%‐23%), the 1‐year OS was 35% (95% CI, 24%‐47%), and the RR was 13% (95% CI, 5%‐25%), all partial. One treatment‐related death occurred from myocardial infarction; 3 other grade 4 events occurred, including pulmonary embolism, neutropenia, and central nervous system (CNS) ischemia. There was no significant correlation between biomarkers and PFS or OS.

CONCLUSIONS:

This combination of thalidomide and temozolomide does not appear to have a clinical benefit that exceeds dacarbazine alone. We would not recommend it further for phase 3 trials or for standard community use. Cancer 2010. © 2010 American Cancer Society.
Evaluation of the breathworks mindfulness‐based pain management programme: effects on well‐being and multiple measures of mindfulness
Authors: Cusens Bryany , Duggan Geoffrey B. , Thorne Kirsty , Burch Vidyamala
Published: November 2009

Two studies of a mindfulness training programme are presented. Study 1 reports on a pilot investigation of the impact on well‐being of the Breathworks mindfulness‐based pain management programme. Significant positive change was found on self‐report measures of depression, outlook, catastrophizing and pain self‐efficacy in the Intervention Group, but not the Comparison Group. Particularly large effects were found for pain acceptance. These results support the short‐term efficacy of the Breathworks programme and reinforce the importance of acceptance for positive outcome with chronic pain patients. Study 2 investigated alterations in mindfulness following participation in the Breathworks programme. Subjective and non‐subjective measures of mindfulness were used. Scores on the Mindful Attention Awareness Scale were significantly higher at Time 2 in the Intervention Group, but not in the Comparison Group. There was no change on a measure of sustained attention. Results from an Implicit Association Test provided some support for an increased awareness of positive stimuli, following the intervention. These results are discussed with reference to the mechanisms of mindfulness. Copyright © 2009 John Wiley & Sons, Ltd.

Key Practitioner Message:

Evidence supporting the efficacy of Breathworks for well‐being.

Mindful Attention Awareness Scale scores improved following mindfulness training.

Mindfulness may increase awareness of pleasant affect.

No change found on a measure of attention.
Shame as a traumatic memory
Authors: Matos Marcela , Pinto‐Gouveia José
Published: November 2009

Background: This study explores the premise that shame episodes can have the properties of traumatic memories, involving intrusions, flashbacks, strong emotional avoidance, hyper arousal, fragmented states of mind and dissociation.

Method: A battery of self‐report questionnaires was used to assess shame, shame traumatic memory and depression in 811 participants from general population (481 undergraduate students and 330 subjects from normal population).

Results: Results show that early shame experiences do indeed reveal traumatic memory characteristics. Moreover, these experiences are associated with current feelings of internal and external shame in adulthood. We also found that current shame and depression are significantly related. Key to our findings is that those individuals whose shame memories display more traumatic characteristics show more depressive symptoms. A moderator analysis suggested an effect of shame traumatic memory on the relationship between shame and depression.

Limitations: The transversal nature of our study design, the use of self‐reports questionnaires, the possibility of selective memories in participants' retrospective reports and the use of a general community sample, are some methodological limitations that should be considered in our investigation.

Conclusion: Our study presents novel perspectives on the nature of shame and its relation to psychopathology, empirically supporting the proposal that shame memories have traumatic memory characteristics, that not only affect shame in adulthood but also seem to moderate the impact of shame on depression. Therefore, these considerations emphasize the importance of assessing and intervening on shame memories in a therapeutic context. Copyright © 2009 John Wiley & Sons, Ltd.

Key Practitioner Message:

Early shame experiences reveal traumatic memory characteristics and are related to current shame and to psychopathology.

Individuals whose shame memories have more traumatic characteristics are those who show more depressive symptoms.

Shame traumatic memories moderate the relationship between shame and depression, hence to the same shame, individuals who experienced shame as more traumatic are the ones who show more depressive symptoms.

Therapy for shame‐based problems needs to incorporate strategies to assess and address individuals shame traumatic memories.
Does illness attribution affect treatment assignment in depression?
Authors: Schweizer Susanne , Peeters Frenk , Huibers Marcus , Roelofs Jeffrey , van Os Jim , Arntz Arnoud
Published: November 2009

Objective: Little is known about depressed individuals' illness attributions and how these influence treatment assignment in clinical practice. The aim of the present study was to examine whether illness attribution across the domains of intraindividual, interpersonal and biological reasons was associated with treatment assignment in a naturalistic treatment setting.

Method: Illness attribution was assessed with the Reasons for Depression Questionnaire in 221 depressed individuals. Participants were assigned to either cognitive–behavioural therapy (CBT), interpersonal therapy (IPT) or psychopharmacological treatment (PHT).

Results: Depressed individuals who strongly attributed their illness to intraindividual factors were more likely to be assigned to CBT, and depressed individuals attributing their depression to biological reasons were more likely to receive in PHT. In contrast, interpersonal illness attribution was not associated with treatment assignment.

Conclusions: Illness attribution influences treatment assignment to CBT and PHT. However, factors other than illness attribution for depression affect a treatment choice of IPT. Copyright © 2009 John Wiley & Sons, Ltd.

Key Practitioner Message:

Intraindividual and biological illness attributions affected depressed individuals' treatment assignment, making these individuals more likely to receive CBT and PHT, respectively.

Interpersonal illness attribution was not found to be associated with treatment assignment.

There were significant gender differences in illness attribution. Men were more likely to endorse in achievement‐related causes, and women attributed their depressive illnesses to more interpersonal reasons (i.e., relationship, childhood and intimacy).
The Green Onion: a corporate environmental strategy framework
Authors: Valentine Scott Victor
Published: November 2009

Since the 1990s, there has been a proliferation of research exploring the benefits of proactive corporate environmental management initiatives. Unfortunately, the absence of a comprehensive, strategic planning framework relegates much of this valuable research to a study of good ideas for making money while operating more sustainably. This paper presents a framework for guiding corporate environmental strategy to bring order to existing observations and allow social scientists to begin the process of ‘orderly control and prediction’. The research is based on modified grounded theory and an extensive literature review pertaining to the benefits of corporate environmental management. The framework has been named the ‘Green Onion’ to highlight the multiple strategic layers of influence uncovered and the importance of retaining resilient outer layers (i.e., stakeholder management) to protect the highly potent core of functional environmental management initiatives (i.e., cost saving initiatives). Copyright © 2009 John Wiley & Sons, Ltd and ERP Environment.
Fusion of uniluminal vascular spheroids: A model for assembly of blood vessels
Authors: Fleming Paul A. , Argraves W. Scott , Gentile Carmine , Neagu Adrian , Forgacs Gabor , Drake Christopher J.
Published: November 2009

We evaluated the self‐assembly properties of uniluminal vascular spheroids having outer layers of vascular smooth muscle cells and a contiguous inner layer of endothelial cells lining a central lumen. We showed that while pairs of uniluminal vascular spheroids suspended in culture medium fused to form a larger diameter spheroidal structure, spheroids in collagen hydrogels formed elongated structures. These findings highlight the potential use of uniluminal vascular spheroids as modules to engineer blood vessels. We also demonstrate that uniluminal vascular spheroid fusion conforms to models describing the coalescence of liquid drops. Furthermore, the fusion of uniluminal vascular spheroids in vitro closely resembled the in vivo process by which the descending aorta forms from the fusion of the paired dorsal aortae during embryonic development. Together, the findings indicate that tissue liquidity underlies uniluminal vascular spheroid fusion and that in vivo anastomosis of blood vessels may involve a similar mechanism. Developmental Dynamics 239:398–406, 2010. © 2009 Wiley‐Liss, Inc.
Sinusoid development and morphogenesis may be stimulated by VEGF‐Flk‐1 signaling during fetal mouse liver development
Authors: Sugiyama Yoshinori , Takabe Yurie , Nakakura Takashi , Tanaka Shigeyasu , Koike Toru , Shiojiri Nobuyoshi
Published: November 2009

Early morphogenesis of hepatic sinusoids was histochemically and experimentally analyzed, and the importance of VEGF‐Flk‐1 signaling in the vascular development was examined during murine liver organogenesis. FITC‐gelatin injection experiments into young murine fetuses demonstrated that all primitive sinusoidal structures were confluent with portal and central veins, suggesting that hepatic vessel development may occur via angiogenesis. At 12.5–14.5 days of gestation, VEGF receptors designated Flk‐1, especially their mature form, were highly expressed in endothelial cells of primitive sinusoidal structures and highly phosphorylated on their tyrosine residues. At the same time, VEGF was also detected in hepatoblasts/hepatocytes, hemopoietic cells, and megakaryocytes of the whole liver parenchyma. Furthermore, the addition of VEGF to E12.5 liver cell cultures significantly induced the growth and branching morphogenesis of sinusoidal endothelial cells. Therefore, VEGF‐Flk‐1 signaling may play an important role in the growth and morphogenesis of primitive sinusoids during fetal liver development. Developmental Dynamics 239:386–397, 2010. © 2009 Wiley‐Liss, Inc.
A migratory role for EphrinB ligands in avian epicardial mesothelial cells
Authors: Wengerhoff Sonia M. , Weiss Amy R. , Dwyer Kathryn L. , Dettman Robert W.
Published: November 2009

Little is known about the molecules that mediate the attachment of proepicardial cells to the heart. Ephrins are cell surface ligands for Eph tyrosine kinase receptors, molecules known to play a role in cell adhesion and migration. Here, we detected EphrinB ligands in proepicardial and epicardial mesothelial cells (EMCs) using reverse transcriptase‐polymerase chain reaction, immunoblotting, immunolocalization, and EphB‐Fc binding. Aggregated EphB‐Fc fragments clustered ephrinB1 ligands on living EMCs indicating that they are cell surface expressed. In vitro assays demonstrated that ephrinB ligands participate in EMC migration but not cell adhesion. Localization studies in hearts at Hamburger and Hamilton stage 30 and older revealed that ephrinB1 is expressed in the epicardium and subepicardial mesenchyme of the atrioventricular sulcus. EMCs treated with platelet‐derived growth factor‐BB expressed smooth muscle markers but not ephrinB1. Our study supports an early role for ephrinB ligands for migration of epicardial cells and a later role in perivascular fibroblasts of coronary vessels in the atrioventricular sulcus. Developmental Dynamics 239:598–609, 2010. © 2009 Wiley‐Liss, Inc.
Spatial (Tbata) expression in mature medullary thymic epithelial cells
Authors: Saade Murielle , Irla Magali , Yammine Miriam , Boulanger Nicolas , Victorero Geneviève , Vincentelli Renaud , Penninger Josef M. , Holländer Georg A. , Chauvet Sophie , Nguyen Catherine
Published: November 2009

The Spatial gene is expressed in highly polarized cell types such as testis germ cells, brain neurons and thymic epithelial cells (TEC). Its expression was documented in testis and brain but poorly characterized in thymus. Here, we characterize for the first time Spatial‐expressing TEC throughout ontogeny and adult mouse thymus. Spatial is expressed in thymic‐fated domain by embryonic day E10.5 and persists in subcapsular, cortical, medullary epithelial cells and in MTS24+ progenitor TEC. Using mouse strains in which thymocyte development is blocked at various stages, we show that Spatial expression is independent of thymocyte‐derived signals during thymus organogenesis. Analyses on purified thymic cell subsets show that Spatial short isoforms are expressed in cortical TEC (cTEC) and mature medullary TEC (mTEC). Spatial long isoforms were detected in the same TEC population. Spatial presents a nuclear distribution specific to mature mTEC expressing UEA1 and Aire. Aire‐ and RANKL‐deficient mice revealed that Spatial expression is drastically reduced in the thymus of these mutants. These findings reveal a critical function of Aire in regulating Spatial expression, which is compatible with promiscuous Spatial gene expression.
hypercloso‐Hexa(amino)hexaboranes: Structurally Related to Known hypercloso‐Dodecaboranes, Metastable with Regard to Their Classical Cycloisomers
Authors: Mesbah Wahid , Soleimani Meisam , Kianfar Elham , Geiseler Gertraud , Massa Werner , Hofmann Matthias , Berndt Armin
Published: November 2009

B6(NMe2)6 (2a) is the first neutral hypercloso‐hexaborane to be characterized by X‐ray structural analysis. The geometry of 2a is in nice agreement with that of the Ci symmetric molecule computed at the B3LYP/6‐311+G** level of theory. Two B3 triangles with long B···B distances in 2a are reminiscent of those in Hawthorne's benzyloxy‐substituted hypercloso‐dodecaboranes 6a,b. Upon heating to 200 °C, 2a transforms into Nöth's classical cyclohexaborane 1a. Computations at the B3LYP/6‐311+G** + ZPE level of theory show 1a to be 21.6 kcal mol–1 lower in energy than 2a, that is, the latter is metastable. hypercloso‐Hexaborane B6(NEt2)6 (2b), which was reported to be thermodynamically more stable than 1b, is computed to be 22.4 kcal mol–1 less stable than 1b. Pure 1b is shown here not to transform into 2b upon standing in solution, which is in contrast to reports in the literature for a mixture containing 1b. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Chiral [Bis(olefin)amine]rhodium(I) Complexes – Transfer Hydrogenation in Ethanol
Authors: Zweifel Theo , Scheschkewitz David , Ott Timo , Vogt Matthias , Grützmacher Hansjörg
Published: November 2009

Bis(olefin)amines (boas) are a new class of ligands for the synthesis of transition metal complexes, which can be used in various homogeneous catalytic reactions. A simple straightforward coupling reaction between 5H‐dibenzo[a,d]cyclohepten‐5‐yl chloride (tropCl) and primary amines allows the synthesis of various chiral boas. Birch reduction of phenylalanine gives (2S)‐2‐amino‐3‐cyclohexa‐1,4‐dien‐1‐yl propanoate, which is used for the synthesis of the bis(olefin)amine methyl (2S)‐3‐(cyclohexa‐1,4‐dienyl)‐2‐(5H‐dibenzo[a,d]cyclohepten‐5‐yl‐amino)propionate. Coupling between cyclohex‐3‐en‐1‐ylamine with tropCl gives N‐(cyclohex‐3′‐en‐1′‐yl)‐5H‐dibenzo[a,d]cyclohepten‐5‐ylamine, which was separated into its enantiomers. Bicyclic cyclohexenylamine derivatives like bicyclo[2.2.2]oct‐5‐en‐2‐ylamine and 2‐(methoxycarbonyl)bicyclo[2.2.1]hept‐5‐en‐3‐ylamine were likewise coupled with tropCl to give chiral bis(olefin)amines. Alternatively, 5H‐dibenzo[a,d]cyclohepten‐5‐ylamine (tropNH2) can react with cyclohexenyl ketones to give prochiral bis(olefin)imines, which were reduced to the corresponding bis(olefin)amines. With [Rh2(μ‐Cl)2(CO)4] or [Rh2(μ‐Cl)2(C2H4)4], a complexation of these compounds was achieved leading to chiral rhodium complexes of the type [Rh(boa)(CO)]OTf or [Rh(boa)(PR3)]OTf. The complexes have a strongly distorted saw‐horse‐type structure (determined by X‐ray diffraction studies) and were tested in transfer hydrogenations with ethanol/2‐propanol as hydrogen donor. Only complexes with tightly bound olefinic binding sites and a pronounced saw‐horse‐type structure give significant activities. Furthermore, a phosphane ligand in trans position to the coordinated amine function has a positive impact of the catalysts performance. None of the investigated catalysts gave an impressive enantiomeric excess (ee < 60 %) in the transfer hydrogenation of acetophenone.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
Mental simulation in language comprehension and social cognition
Authors: Zwaan Rolf A.
Published: November 2009

Current theories in social cognition and cognitive psychology conceptualize understanding of actions and of language describing actions as the performance of sensorimotor simulations. Although there is emerging empirical evidence for these theories, they are currently underspecified and the evidence is correspondingly coarse. Language is a sensitive tool that allows us to construe actions in myriad ways. This paper discusses several challenges that face simulation theories aimed at capturing the subtlety of language. Copyright © 2009 John Wiley & Sons, Ltd.
The scaffolded mind: Higher mental processes are grounded in early experience of the physical world
Authors: Williams Lawrence E. , Huang Julie Y. , Bargh John A.
Published: November 2009

It has long been a staple of psychological theory that early life experiences significantly shape the adult's understanding of and reactions to the social world. Here we consider how early concept development along with evolved motives operating early in life can come to exert a passive, unconscious influence on the human adult's higher‐order goal pursuits, judgments, and actions. In particular, we focus on concepts and goal structures specialized for interacting with the physical environment (e.g., distance cues, temperature, cleanliness, and self‐protection), which emerge early and automatically as a natural part of human development and evolution. It is proposed that via the process ofscaffolding, these early sensorimotor experiences serve as the foundation for the later development of more abstract concepts and goals. Experiments using priming methodologies reveal the extent to which these early concepts serve as the analogical basis for more abstract psychological concepts, such that we come easily and naturally to speak ofcloserelationships,warmpersonalities, moralpurity, and psychologicalpain. Taken together, this research demonstrates the extent to which such foundational concepts are capable of influencing people's information processing, affective judgments, and goal pursuit, oftentimes outside of their intention or awareness. Copyright © 2009 John Wiley & Sons, Ltd.
The hard embodiment of culture
Authors: Cohen Dov , Leung Angela K.‐Y.
Published: November 2009

The way humans move and comport their bodies is one way they (literally) carry their culture. In pre‐wired embodiments, body comportment triggers basic, evolutionarily prepared affective and cognitive reactions that subsequently prime more complex representations. Culture suffuses this process, because (1) cultural artifacts, affordances, and practices make certain body comportments more likely, (2) cultural practices, rituals, schemas, and rules promote the learning of an otherwise underspecified connection between a given body comportment and a particular basic reaction, and (3) cultural meaning systems elaborate basic affective and cognitive reactions into more complex representations. These points are illustrated with three experiments that examine how moral systems can become embodied. We also discuss totem embodiments, in which cultural practices and rituals establish connections between body comportment and complex cultural representations, without the aid of any evolutionarily prepared connection to basic affective and cognitive states. Copyright © 2009 John Wiley & Sons, Ltd.
Becoming a social agent: Developmental foundations of an embodied social psychology
Authors: Daum Moritz M. , Sommerville Jessica A. , Prinz Wolfgang
Published: November 2009

In this paper, we argue that young infants serve as ideal models for disentangling the relative contributions of embodied and symbolic processes to mature social cognition and behavior. Based on evidence suggesting that infants possess a nascent ability to understand others' actions, and to interact and communicate with others in meaningful ways, we argue that the embodiment processes underlying these skills in infancy may also account for a significant portion of adults' social understanding and behavior. Based on evidence suggesting both continuity and change in social understanding and behavior as children encounter a formal language system, and evidence suggesting that manipulating the mode of processing influences social understanding, we argue that embodied and symbolic modes of understanding are potentially dissociable and can yield different construals of the same social behavior. Finally, we suggest that the study of infancy can elucidate outstanding issues in the adult social psychology, and close by providing one illustration of the way in which it might do so. Copyright © 2009 John Wiley & Sons, Ltd.
Culture, psyche, and body make each other up
Authors: Cohen Dov , Leung Angela K.‐Y. , Ijzerman Hans
Published: November 2009

The commentaries make important points, including ones about the purposeful uses of embodiment effects. Research examining such effects needs to look at how such effects play themselves out in people's everyday lives. Research might usefully integrate work on embodiment with work on attribution and work in other disciplines concerned with body–psyche connections (e.g., research on somaticizing versus “psychologizing” illnesses and hypercognizing versus hypocognizing emotions). Such work may help us understand the way positive and negative feedback loops operate as culture, psyche, and body make each other up. Copyright © 2009 John Wiley & Sons, Ltd.
The implications of data selection for regional erosion and sediment yield modelling
Authors: de Vente Joris , Poesen Jean , Govers Gerard , Boix‐Fayos Carolina
Published: November 2009

Regional environmental models often require detailed data on topography, land cover, soil, and climate. Remote sensing derived data form an increasingly important source of information for these models. Yet, it is often not easy to decide what the most feasible source of information is and how different input data affect model outcomes. This paper compares the quality and performance of remote sensing derived data for regional soil erosion and sediment yield modelling with the WATEM‐SEDEM model in south‐east Spain. An ASTER‐derived digital elevation model (DEM) was compared with the DEM obtained from the Shuttle Radar Topography Mission (SRTM), and land cover information from the CORINE database (CLC2000) was compared with classified ASTER satellite images. The SRTM DEM provided more accurate estimates of slope gradient and upslope drainage area than the ASTER DEM. The classified ASTER images provided a high accuracy (90%) land cover map, and due to its higher resolution, it showed a more fragmented landscape than the CORINE land cover data. Notwithstanding the differences in quality and level of detail, CORINE and ASTER land cover data in combination with the SRTM DEM or ASTER DEM allowed accurate predictions of sediment yield at the catchment scale. Although the absolute values of erosion and sediment deposition were different, the qualitative spatial pattern of the major sources and sinks of sediments was comparable, irrespective of the DEM and land cover data used. However, due to its lower accuracy, the quantitative spatial pattern of predictions with the ASTER DEM will be worse than with the SRTM DEM. Therefore, the SRTM DEM in combination with ASTER‐derived land cover data presumably provide most accurate spatially distributed estimates of soil erosion and sediment yield. Nevertheless, model calibration is required for each data set and resolution and validation of the spatial pattern of predictions is urgently needed. Copyright © 2009 John Wiley & Sons, Ltd.
Quantifying the temporal dynamics of wood in large rivers: field trials of wood surveying, dating, tracking, and monitoring techniques
Authors: MacVicar B.J. , Piégay H. , Henderson A. , Comiti F. , Oberlin C. , Pecorari E.
Published: November 2009

Wood plays an important role in stream ecology and geomorphology. Previous studies of wood in rivers have quantified spatial distributions but temporal dynamics remain poorly documented. The lack of such data is related to limitations of existing methods, especially when applied to large rivers. Five techniques are field‐tested to assess their utility for quantifying the temporal dynamics in rivers: repeated high‐resolution aerial surveys, the measurement of wood physical characteristics as proxies for14C dating, passive and active radio frequency identification (RFID) tags, radio transmitters, and video. The spatial distribution of wood is surveyed using aerial imagery with a resolution finer than 0·10 m. The estimation of temporal trends by repeated aerial‐based surveys needs to consider vegetation growth and hiding. Wood residence times can be calculated using14C analysis, but the assessment of wood physical characteristics including decay status and wood density offers a cheaper, if less accurate, alternative. Wood resistance to penetration is tested but results are not significant. Radio transmitters are reliable for multi‐year (∼5 year) surveys and can be detected at 800 m. Passive RFID tags are limited by a read range of 0·30 m but are reliable for longer term (>5 year) studies. Active RFID tags combine a moderate read range (10–300 m) and low cost with in‐flood detection but require more testing. Video monitoring of wood passing on the surface of a river is successfully implemented. For a single flood on the Ain River (France), wood transport rates are an order of magnitude higher on the rising limb of the hydrograph than on the falling limb. Overall, the techniques improve the ability to gather the data needed to understand wood transfer processes and calibrate budgets of wood in rivers. Copyright © 2009 John Wiley & Sons, Ltd.
Hydrological response of abandoned agricultural soils along a climatological gradient on metamorphic parent material in southern Spain
Authors: Ruiz Sinoga J.D. , Martinez Murillo J.F.
Published: November 2009

The hydrological and erosive response of the Mediterranean eco‐geomorphologic system has showed a very variable and complex behaviour depending on several factors: topography, geology, vegetation pattern, soil properties, land use management, etc. Climate is a key factor due to the great spatial and temporal variability. This research was carried out over different micro‐environments representative from five hillslopes localized in the Littoral Bethic Mountains in the south of Spain. The results of 20 experiments with rainfall simulations on micro‐plots (0.24 m2) and the differences of the incidence of some biotic and abiotic factors in the eco‐geomorphologic system from semi‐arid, dry‐Mediterranean and sub‐humid sites are exposed. Runoff, soil moisture and sediment were measured before, during and after the experiments. The results have shown rock fragments disposition on soil surface and vegetation seem to be the main factors that control the hydrological and erosive response at the micro‐plot‐scale of the experiments. Embedded rock fragments are the most important soil surface property because they reduce the infiltration. Whilst vegetation increases it what is more influential on the hydrological and erosive response of micro‐environments at more arid sites. We have also observed that there are micro‐environment particularities which play a more important role than the localization in the climatic gradient at micro‐plot scale. Copyright © 2009 John Wiley & Sons, Ltd.
Using magnetic susceptibility to assess soil degradation in the Eastern Rif, Morocco
Authors: Sadiki A. , Faleh A. , Navas A. , Bouhlassa S.
Published: November 2009

The soil in the Rif, Morocco, is at serious risk because increasing anthropogenic pressures are gradually transforming large natural areas into farmland. The distribution of magnetic minerals within the soil profile can be used to assess soil development and degradation. The soils in the study area are severely eroded because of a combination of highly erodible soils, intense rainstorms and scarce vegetation cover. To sample of representative soil profiles, lithology, slope gradient and land use were considered. The ranges of magnetic susceptibility in the soil profiles distinguished between two primary soil groups. Magnetic susceptibility varied in the soil profile and along the soil toposequence, and the variations were related to the differences in the original magnetic composition and the influence of main erosion factors. Lithology is the main factor contributing to the variation in magnetic susceptibility. The magnetic susceptibility values in soils on Tertiary marls (χ = 13·5 × 10−8 m3 kg−1) differed significantly from those on Quaternary terraces (χ = 122·1 × 10−8 m3 kg−1). Slope affected the distribution of magnetic susceptibility because of the continuous loss of topsoil in some parts of the slope and the deposition of eroded soil in others. Elimination of the natural vegetation cover and a shift to cultivated land for cereals has had a negative impact on soil development and, on similar slopes and substrates, magnetic susceptibility decreased significantly in cultivated soils. The soils on steep slopes that had natural vegetation cover retained the magnetic minerals better than did those on gentler slopes that were under cultivation. Grazing, clearing and, especially, tilling has weakened the soil and made it much more vulnerable to erosion. An analysis of the main factors causing erosion will help to promote rational use of the land and to establish conservation strategies in such fragile agroecosystems. Copyright © 2009 John Wiley & Sons, Ltd.
Soil loss, water ponding and sediment deposition variations as a consequence of rainfall intensity and land use: a multi‐criteria analysis
Authors: Svoray Tal , Ben‐Said Shimon
Published: November 2009

Prediction of areas prone to land degradation in agricultural catchments is a complex task. This is due to the difficulties encountered in data gathering over wide regions and in the translation of existing scientific knowledge to a quantitative and spatially explicit risk assessment system. This paper incorporates the use of remotely sensed data, terrain analysis and a multi‐criteria mechanism for evaluating risks of soil loss, water ponding, and sediment deposition in a mid‐size agricultural Mediterranean catchment, under 80 years of intensive cultivation. The research uses simulations to study the effect of topographic attributes, soil characteristics, vegetation cover, rainfall intensity and human activities on the three above‐mentioned processes. The results show that, from the methodological point of view, the integration of knowledge from several experts yields better predictive results than relying on a single expert, even the one found to be most consistent. Also, the use of a simple weighted linear combination was more useful than the more sophisticated computerized programming technique. From the phenomenological point of view, the increase in rainfall intensity and land‐use transformation from orchard to field‐crops has led to a significant increase in soil loss and sediment yield, while extreme changes in tillage direction have only yielded minor changes in water ponding. The developed system's predictive capabilities also show that the outcomes can be used as a basis for decisions on catchment management in regions of high environmental sensitivity. Copyright © 2009 John Wiley & Sons, Ltd.
Temperature and Impurity Concentration Effects on Degradation of Nickel/Yttria‐stabilised Zirconia Anode in PH3‐Containing Coal Syngas
Authors: Zhi M. , Cayan F. N. , Celik I. , Gemmen R. , Pakalapati S. R. , Wu N. Q.
Published: November 2009

Degradation of the Ni/yttria‐stabilised zirconia (YSZ) anode of the solid oxide fuel cell has been evaluated in the coal syngas containing different PH3 concentrations in the temperature range from 750 to 900 °C. Thermodynamic equilibrium calculations show that PH3 in the coal syngas gas is converted mostly to P2O3 at 750–900 °C. The phosphorous impurity reacts with the Ni‐YSZ anode to form phosphates. The P‐impurity poisoning leads to the deactivation of the Ni catalyst and to the reduction in the electronic conductivity of the anode. The impurity poisoning effect on the anode is exacerbated by increase in the temperature and/or the PH3 concentration.