bluuebunny/crossref_metadata_2025 huggingface dataset:
De la capacité, de la compétence, de l’empowerment, repenser l’anthropologie de la participation
Authors: Genard Jean-Louis
Published: October 2013

Le plus souvent étudiée dans le contexte des évolutions du politique et du passage présumé d’une démocratie représentative vers une démocratie davantage participative ou délibérative, la question de la participation est abordée ici sous l’angle d’une transformation de nos coordonnées anthropologiques. Les exigences et les attentes de participation se retrouvent en effet dans de multiples domaines qui excèdent de loin la seule sphère du politique, allant du monde de l’entreprise et de ses cercles de qualité jusqu’à la production de biens en kit sollicitant les capacités de montage des acheteurs. Cette extension du domaine de la participation s’appuie en réalité sur un certain nombre de présupposés anthropologiques. Ceux-ci prêtent aux acteurs descapacitéset descompétencesqu’ils sont censés détenir, à moins qu’ils ne soient appelés à les enrichir par des stratégies d’empowermentsi elles leur font défaut ou sont insuffisantes. Ils leur attribuent aussi un potentiel demotivationindispensable à l’actualisation de ces compétences et capacités. Le texte soutient que l’évaluation des personnes ainsi que la configuration de nombreux dispositifs sociaux récents tendent de plus en plus à s’ajuster à ce nouveau référentiel anthropologique. Il en va ainsi de la participation politique bien sûr, mais aussi des nouvelles politiques sociales, des formations au « pouvoir d’agir », des objectifs éducatifs, des politiques de développement ou de santé. Revenant plus spécifiquement sur la question de la participation politique, le texte montre comment ces nouvelles coordonnées anthropologiques reconfigurent la question de l’expertise en réorganisant les partages entre expertises ordinaire et spécialisée et, du coup, le partage entre les espaces où peut prendre place une démocratie participative et ceux qui demeurent confiés à l’expertise technocratique.
Deux conceptions de l’empowerment
Authors: Cantelli Fabrizio
Published: October 2013

La catégorie d’empowermentdevient omniprésente quand il s’agit de participation. Pourtant, peu de travaux en ont exploré sociologiquement les contours, les propriétés et la portée. Il s’agit de prendre distance avec une approche unidimensionnelle de la catégorie, qui l’appréhende comme une solution démocratique ou une régression liée à un usage managérial. Notre démarche comparative élargie considère plusieurs espaces-temps, ce qui permet de rendre compte de deux manières très différentes de penser le pouvoir et d’agir sur des capacités. Cet article interroge deux conceptions de l’empowerment, soit deux philosophies du pouvoir sous-jacentes : une gestionnaire et une civique. Pour saisir les conceptions gestionnaires de l’empowerment, notre article s’appuie sur un spectre allant du cas spécifique de la Banque mondiale (Empowerment Team) à plusieurs acteurs de la santé en relation avec les institutions européennes. Concernant les conceptions civiques de l’empowerment, l’enquête repose sur le mouvement des droits civiques aux États-Unis et leBlackpowerdans les années 1960, tout en s’interrogeant sur l’héritage contemporain.
L’émancipation coopérative face à la compétence participative
Authors: Boissonade Jérôme
Published: October 2013

Nous souhaitons interroger la pertinence des notions de compétences et de capacités comme concepts critiques pragmatistes opératoires face aux nouveaux processus de domination, notamment ceux exercés par les institutions. Pour ce faire, nous nous appuyons dans ce texte sur l’expérience croisée d’un conseil de quartier et d’une accession sociale à la propriété à gestion coopérative. La démocratie participative exige des capacités spécifiques qui sont en effet perturbées par cette expérience coopérative dont le rapport à la décision repose sur le faire et la dimension capacitaire sur les prises élaborées à cet effet. Il s’agit donc moins pour les accédants concernés d’obtenir une reconnaissance publique de capacités pouvant conduire à un accès à la décision, que de construire de manière coopérative des prises d’émancipation critique vis-à-vis de ces dispositifs participatifs. Ce passage d’une compétence participative à une émancipation coopérative permet à la fois de surmonter l’instrumentalisation capacitaire et de mieux travailler l’articulation entre la constitution des prises et la portée critique des processus d’émancipation.
Critical Shields values in coarse‐bedded steep streams
Authors: Bunte Kristin , Abt Steven R. , Swingle Kurt W. , Cenderelli Dan A. , Schneider Johannes M.
Published: October 2013

Critical Shields values (
) suitable for specific applications are back‐calculated from representative bed load samples in mountain streams and a flow competence/critical flow approach. The general increase of
(for the bed D50 size) as well as
and
(for the bed D16 and D84 sizes) with stream gradient Sx and also the stratification of
by relative flow depth and relative roughness are confirmed. Critical Shields values
are shown to exceed
by about threefold, while those for
are nearly half of
. However, it remains unclear to what extent physical processes or numerical artifacts contribute to determining critical Shields values. Critical bankfull Shields values (
) back‐computed from the average largest particles mobile at bankfull flow DBmax,bf approach
at steep gradients and
at low gradients and therefore increase very steeply with Sx. The relation
is stratified by bed stability (D50/DBmax,bf) and predictable if bed stability can be field categorized. Noncritical Shields values (
) computed from bankfull flow depth and the D50 size differ from
and
. Only in bankfull mobile streams where D50/DBmax = 1 can τ*cbf,
, and
be used interchangeably. In highly mobile streams, substituting
by
overpredicts the DBmax,bf size by up to fivefold and underpredicts DBmax,bf by the same amount in highly stable streams. A value of 0.03 is appropriate for
only on low stability beds with Sx ≅ 0.01, but overpredicts DBmax,bf by 30‐fold on highly stable beds with Sx ≅ 0.1. Differences in field and computational methods also affect critical Shields values.
On the wind mechanical forcing of the ocean general circulation
Authors: Zhai Xiaoming
Published: October 2013

The wind mechanical forcing of the ocean general circulation and its seasonal variations are examined using available observational products, focusing on the role of the mean and fluctuating winds. It is found that including wind fluctuations in the stress calculation produces a qualitative change in the estimates of the mean and seasonal wind stress, particularly at mid and high latitudes where the synoptic wind variability is large. This effect of wind fluctuations on air‐sea momentum exchange has immediate dynamical consequences for the large‐scale ocean circulation. For example, power input to the ocean general circulation and subtropical gyre transport can be underestimated by more than 50% if the fluctuating winds are not taken into account. However, the impact of including wind fluctuations depends strongly on the presence of the mean winds. If the mean winds are ignored in the stress calculation, the net effect of the fluctuating winds is to take energy out of the ocean owing to the skewness of the near‐surface wind field. Furthermore, covariances of wind fluctuations are found to explain most of the effect of the fluctuating winds, while the variable drag coefficient makes a non‐negligible contribution in the Southern Ocean. These results imply that paleo and future climate studies need to take into account the changes of the large‐scale low‐frequency wind field as well as the synoptic weather systems.
Quantifying the transport of subcloud layer reactants by shallow cumulus clouds over the Amazon
Authors: Ouwersloot H. G. , de Arellano J. Vilà‒Guerau , H. van Stratum B. J. , Krol M. C. , Lelieveld J.
Published: October 2013

We investigate the vertical transport of atmospheric chemical reactants from the subcloud layer to the cumulus cloud layer driven by shallow convection over the Amazon during the dry season. The dynamical and chemical assumptions needed for mesoscale and global chemistry transport model parametrizations are systematically analyzed using a Large Eddy Simulation model. We quantify the mass flux transport contribution to the temporal evolution of reactants. Isoprene, a key atmospheric compound over the tropical rain forest, decreases by 8.5% h−1 on average and 15% h−1 at maximum due to mass‒flux‒induced removal. We apply mass flux parametrizations for the transport of chemical reactants and obtain satisfactory agreement with numerically resolved transport, except for some reactants like O3, NO, and NO2. The latter is caused by the local partitioning of reactants, influenced by UV radiation extinction by clouds and small‒scale variability of ambient atmospheric compounds. By considering the longer‒lived NOx (NO + NO2), the transport is well represented by the parametrization. Finally, by considering heterogeneous surface exchange conditions, it is demonstrated that the parametrizations are sensitive to boundary conditions due to changes in the boundary layer dynamics.
Learning Communities as a First Step in an Integrative Learning Curriculum
Authors: Shultz Norah
Published: October 2013

Norah Shultz describes Arcadia University's unique learning communities that support student interactions with each other and the world outside the classroom.
Elevated IgG4 Serum Levels Among Primary Sjögren's Syndrome Patients: Do They Unmask Underlying IgG4‐Related Disease?
Authors: Mavragani Clio P. , Fragoulis George E. , Rontogianni Dimitra , Kanariou Maria , Moutsopoulos Haralampos M.
Published: October 2013

Objective

To determine IgG4 levels in a cohort of consecutive patients with primary Sjögren's syndrome (SS) and other autoimmune diseases and explore whether they associate with distinct clinical, serologic, and histopathologic features.

Methods

Serum IgG4 levels were measured in 133 primary SS patients and 49 healthy donors (HDs). Seventy‐four lupus and 54 rheumatoid arthritis (RA) patients served as disease controls. Immunohistochemical IgG4 analysis was performed in paraffin‐embedded minor salivary gland (MSG) tissues.

Results

Raised IgG4 serum levels (>135 mg/dl) were detected in 10 (7.5%) of 133 primary SS patients (high‐IgG4 group), in 8 (10.8%) of 74 lupus patients, in 7 (12.9%) of 54 RA patients, and in 1 (2%) of 49 HDs. Compared to the normal‐IgG4 (<135 mg/dl) primary SS group, high‐IgG4 patients exhibited increased prevalence of IgG4‐related features (autoimmune cholangitis, autoimmune pancreatitis, and interstitial nephritis), lower rates of antinuclear antibody positivity, and higher IgG2 and IgE levels. Positive staining for IgG4+ plasma cells with an IgG4:IgG ratio ≥40% was detected in 3 of 6 available MSG tissues in the high‐IgG4 group. Criteria of possible or definite IgG4‐related disease (IgG4‐RD) were fulfilled by 10 (7.5%) of 133 of our primary SS cohort.

Conclusion

Raised IgG4 serum levels were detected in 7.5% of primary SS patients in association with IgG4RD–reminiscent clinical, serologic, and histopathologic features. Whether this high‐IgG4 primary SS group represents a misclassified IgG4‐RD group or a distinct primary SS subtype remains to be further explored in future studies.
Price Sensitivity Within and Across Retail Formats
Authors: Widenhorn Andreas , Salhofer Klaus
Published: October 2013

Applying a synthetic demand system approach, we examine if consumers in discount stores reveal different price elasticities of demand than those in conventional supermarkets. Based on a RollAMA dataset containing information on consumption in 12 different retail chains in Austria, we first analyze demand patterns for a scenario in which consumers only frequent either discounters or supermarkets, followed by an investigation of potential cross‐format effects when both types of stores are visited. Our empirical findings suggest that for the three categories of milk products under examination, price elasticities in discount stores are generally higher. Beyond that, demand reactions in supermarkets with respect to price changes in discounters differ from the reverse case, i.e., from demand reactions in discounters when supermarket prices are changed. This is especially true for the case of drinking milk, which confirms the strategic potential of drinking milk as a loss leader product.
The Differential Effects of Food Safety Regulations on Animal Products Trade: The Case of Crustacean Product Trade
Authors: Tran Nhuong , Nguyen Anh , Wilson Norbert L.W.
Published: October 2013

Chloramphenicol is a broad‐spectrum antibiotic that was historically used as a veterinary drug for farm animal disease treatment purposes and it is currently used in human treatment; however, this is a banned substance. This paper investigates the impact of advancing chloramphenicol analytical standards on crustacean imports in the EU15, Japan, and North America. The paper extends the work of Disdier and Marette (2010) by exploring the differential effect of standards on products. We use a Heckman sample selection specification to address zero trade at the product level. We show that submarkets function differently and respond differentially to the standard. Additionally, we show that the level of disaggregation matters in gravity modeling.
Forced convection mass deposition and heat transfer onto a cylinder sheathed by protective garments
Authors: Ambesi Davide , Kleijn Chris R. , den Hartog Emiel A. , Bouma Richard H. B. , Brasser Paul
Published: October 2013

In chemical, biological, radiological, and nuclear protective clothing, a layer of activated carbon material in between two textile layers provides protection against hazardous gases. A cylinder in cross flow, sheathed by such material, is generally used to experimentally test the garment properties. This is, however, complicated and predictive models are needed. We present a computational fluid dynamics model for the initial phase in which the carbon filter material is not yet saturated. The textiles are modeled as chemically inactive porous layers, the carbon filter particles have been resolved explicitly. The model has been validated against experimental data. We demonstrate that (1) computational fluid dynamics simulations can be used for the efficient design and optimization of protective garments, and (2) the addition of a highly porous active carbon layer highly increases the chemical protection capabilities, while having relatively little negative impact on the thermal comfort of protective garments. © 2013 American Institute of Chemical Engineers AIChE J, 60: 353–361, 2014
Too much of a good thing: Evolutionary perspectives on infant formula fortification in the United States and its effects on infant health
Authors: Quinn Elizabeth A.
Published: October 2013

Recently, there has been considerable debate regarding the appropriate amount of iron fortification for commercial infant formula. Globally, there is considerable variation in formula iron content, from 4 to 12 mg iron/L. However, how much fortification is necessary is unclear. Human milk is low in iron (0.2–0.5 mg/L), with the majority of infant iron stores accumulated during gestation. Over the first few months of life, these stores are depleted in breastfeeding infants. This decline has been previously largely perceived as pathological; it may be instead an adaptive mechanism to minimize iron availability to pathogens coinciding with complementary feeding. Many of the pathogens involved in infantile illnesses require iron for growth and replication. By reducing infant iron stores at the onset of complementary feeding, infant physiology may limit its availability to these pathogens, decreasing frequency and severity of infection. This adaptive strategy for iron regulation during development is undermined by the excess dietary iron commonly found in infant formula, both the iron that can be incorporated into the body and the excess iron that will be excreted in feces. Some of this excess iron may promote the growth of pathogenic, iron requiring bacteria disrupting synergistic microflora commonly found in breastfed infants. Evolutionarily, mothers who produced milk with less iron and infants who had decreased iron stores at the time of weaning may have been more likely to survive the transition to solid foods by having limited iron available for pathogens. Contemporary fortification practices may undermine these adaptive mechanisms and increase infant illness risk. Am. J. Hum. Biol. 26:10–17, 2014. © 2013 Wiley Periodicals, Inc.
Temperature‐ and pH‐sensitive IPNs grafted onto polyurethane by gamma radiation for antimicrobial drug‐eluting insertable devices
Authors: Muñoz‐Muñoz Franklin , Bucio Emilio , Magariños Beatriz , Concheiro Angel , Alvarez‐Lorenzo Carmen
Published: October 2013

Temperature‐ and pH‐sensitive interpenetrating polymer networks (IPNs) and semi‐interpenetrating polymer networks (s‐IPNs) were γ‐ray grafted onto polyurethane (Tecoflex®; TFX) to obtain vancomycin‐eluting implantable medical devices with minimized risk of infections. N‐isopropylacrylamide (NIPAAm) was grafted onto TFX catheters and films via a preirradiation oxidative method (method P) or via a direct method (method D). The PNIPAAm network facilitated acrylic acid (AAc) inclusion and subsequent polymerization/crosslinking, under specific reaction conditions. IPNs and s‐IPNs systems were characterized regarding the amount of grafted polymers, surface properties (FTIR‐ATR, ESEM, EDX), thermal behavior (DSC), and their temperature‐ and pH‐responsiveness. Loading and release of vancomycin for preventing in vitro growth of Staphylococcus aureus were also evaluated. Antimicrobial activity tests and hemo‐ (hemolysis, protein adsorption, thrombogenicity) and cyto‐compatibility (cell viability and production of cytokines and NO) assays indicated that the modification of TFX by γ‐radiation may improve the performance of polyurethanes for biomedical applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 39992.
Highly exfoliated nanostructure in trifunctional epoxy/clay nanocomposites using boron trifluoride as initiator
Authors: Hutchinson John M. , Shiravand Fatemeh , Calventus Yolanda , Fernández‐Francos Xavier , Ramis Xavier
Published: October 2013

Epoxy/clay nanocomposites based upon a trifunctional epoxy resin, triglycidyl p‐amino phenol (TGAP), have been prepared by intercalating an initiator of cationic homopolymerization, a boron trifluoride monoethylamine (BF3·MEA) complex, into the montmorillonite clay galleries before the addition of the TGAP and the curing agent, 4,4‐diamino diphenyl sulfone (DDS), and effecting the isothermal curing reaction. The BF3·MEA enhances the intragallery cationic homopolymerization reaction, which occurs before the extragallery cross‐linking reaction of the TGAP with the DDS, and which hence contributes positively to the mechanism of exfoliation of the clay. The effects of isothermal cure temperature and of BF3·MEA content have been studied, in respect of both the reaction kinetics, monitored by differential scanning calorimetry, and the nanostructure, as identified by small‐angle X‐ray scattering and transmission electron microscopy. It is shown that the use of BF3·MEA in this way as an initiator of intragallery homopolymerization significantly improves the degree of exfoliation in the cured nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40020.
Permeability and blood compatibility of nanoporous parylene film‐coated polyethersulfone membrane under long‐term blood diffusion
Authors: Setia Prihandana Gunawan , Ito Hikaru , Sanada Ippei , Nishinaka Yuya , Kanno Yoshihiko , Miki Norihisa
Published: October 2013

Nanoporous polyethersulfone (PES) membranes are widely used in dialysis systems due to their permeability and diffusion characteristics. However, PES membranes lack blood compatibility, which influences their permeability performance when employed in blood contact devices. Parylene film was deposited on a PES membrane surface and the membrane permeability and blood compatibility were investigated by long‐term blood diffusion testing. After 28 days of testing, 90% of a bare PES membrane was covered with platelets, while the parylene film coated PES membrane had improved biocompatibility with a platelet coverage of only 20–30%. The permeability of the bare PES membrane significantly declined during the first 7 days of the blood diffusion and became stable after 8 days. In contrast, the permeability of the parylene film coated PES membrane exhibited more consistent performance during the entire test. Thus, parylene film coating on PES membrane has potential for application in hemodialysis systems. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40024.
Preparation and dielectric properties of sulfonated poly(aryl ether ketone)/acidified graphite nanosheet composites
Authors: Jiang Wenlong , Liu Yu , Wang Jinfeng , Wang Qitong , Zhang Yunhe , Guan Shaowei
Published: October 2013

Percolative dielectric composites of sulfonated poly(aryl ether ketone) (SPAEK) and acidified graphite nanosheets (AGSs) were fabricated by a solution method. The dielectric constant of the as‐prepared composite with 4.01 vol % AGSs was found to be 330 at 1000 Hz; this was a significant increase compared to that of pure SPAEK. Through the calculation, a low percolation threshold of the AGS/SPAEK composite was confirmed at 3.18 vol % (0.0318 volume fraction) AGSs; this was attributed to the large surface area and high conductivity of the AGSs. Additionally, our percolative dielectric composites also exhibited good mechanical performances and good thermostability, with a tensile strength of 71.7 MPa, a tensile modulus of 1.91 GPa, a breaking elongation of 16.4%, and a mass loss temperature at 5% of 336°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40028.
Preparation of vinyl amine‐co‐vinyl alcohol/polysulfone composite membranes and their carbon dioxide facilitated transport properties
Authors: Salih Alsamani A. M. , Yi Chunhai , Hu Jiayang , Yin Lijuan , Yang Bolun
Published: October 2013

A vinyl amine–vinyl alcohol copolymer (VAm–VOH) was synthesized through free‐radical polymerization, basic hydrolysis in methanol, acidic hydrolysis in water, and an anion‐exchange process. In the copolymer, the primary amino groups on the VAm segment acted as the carrier for CO2‐facilitated transport, and the vinyl alcohol segment was used to reduce the crystallinity and increase the gas permeance. VAm–VOH/polysulfone (PS) composite membranes for CO2 separation were prepared with the VAm–VOH copolymer as a selective layer and PS ultrafiltration membrane as a support. The membrane gas permselectivity was investigated with CO2, N2, and CH4 pure gases and their binary mixtures. The results show that the CO2 transport obeyed the facilitated transport mechanism, whereas N2 and CH4 followed the solution–diffusion mechanism. The increase in the VAm fraction in the copolymer resulted in a carrier content increase, a crystallinity increase, and intermolecular hydrogen‐bond formation. Because of these factors, the CO2 permeance and CO2/N2 selectivity had maxima with the VAm fraction. At an optimum applied pressure of 0.14 MPa and at an optimum VAm fraction of 54.8%, the highest CO2 permeance of 189.4 GPU [1 GPU = 1 × 10−6 cm3(STP) cm−2 s−1 cmHg−1] and a CO2/N2 selectivity of 58.9 were obtained for the CO2/N2 mixture. The heat treatment was used to improve the CO2/N2 selectivity. At an applied pressure of 0.8–0.92 MPa, the membrane heat‐treated under 100°C possessed a CO2 permeance of 82 GPU and a CO2/N2 selectivity of 60.4, whereas the non‐heat‐treated membrane exhibited a CO2 permeance of 111 GPU and a CO2/N2 selectivity of 45. After heat treatment, the CO2/N2 selectivity increased obviously, whereas the CO2 permeance decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014, 131, 40043.
Growth Differentiation Factor 15, a Marker of Lung Involvement in Systemic Sclerosis, Is Involved in Fibrosis Development but Is not Indispensable for Fibrosis Development
Authors: Lambrecht Stijn , Smith Vanessa , De Wilde Katelijne , Coudenys Julie , Decuman Saskia , Deforce Dieter , De Keyser Filip , Elewaut Dirk
Published: October 2013

Objective

Transforming growth factor β superfamily members are involved in the pathogenesis of systemic sclerosis (SSc). Growth differentiation factor 15 (GDF‐15) is a distant member of this family. We undertook this study to evaluate the role of GDF‐15 in SSc pathogenesis.

Methods

A longitudinal prospective cohort of SSc patients was screened for serum GDF‐15 levels using enzyme‐linked immunosorbent assay, and associations with clinical data were analyzed. In vitro stimulation experiments were performed on lung fibroblasts. The role of GDF‐15 in fibrosis development in vivo was evaluated in the bleomycin lung fibrosis model in GDF‐15–deficient mice.

Results

GDF‐15 was measured at baseline in serum samples from 119 SSc patients. An increase in GDF‐15 levels was observed in patients classified as having no skin involvement, those with limited cutaneous SSc, and those with diffuse cutaneous SSc. Moreover, baseline serum GDF‐15 levels correlated strongly with disease activity and extent of organ involvement, particularly clinical symptoms of lung fibrosis, including impact on lung function at prospective followup. This was mimicked in the bleomycin model of SSc, in which animals exposed to bleomycin had elevated expression levels of GDF‐15 in lung tissue. Lung fibroblasts isolated from GDF‐15–deficient mice showed reduced induction of interleukin‐6 and CCL2 upon bleomycin stimulation. Surprisingly, no differences in fibrosis development were observed between wild‐type and GDF‐15–deficient animals.

Conclusion

An intriguing profile of serum GDF‐15 levels was found in SSc patients. GDF‐15 expression is induced during fibrosis development and markedly correlates with lung function impairment in this disease. The protein may participate in fibrosis initiation, but is not indispensable in the course of fibrosis development in vivo.
Distributions instead of single numbers: Percentiles and beam plots for the assessment of single researchers
Authors: Bornmann Lutz , Marx Werner
Published: October 2013

Citations measure an aspect of scientific quality: the impact of publications (A.F.J. van Raan, 1996). Percentiles normalize the impact of papers with respect to their publication year and field without using the arithmetic average. They are suitable for visualizing the performance of a single scientist. Beam plots make it possible to present the distributions of percentiles in the different publication years combined with the medians from these percentiles within each year and across all years.
Insensitive Nitrogen‐Rich Materials Incorporating the Nitroguanidyl Functionality
Authors: Zhang Qinghua , He Chunlin , Yin Ping , Shreeve Jean'ne M.
Published: October 2013

A new class of nitroguanidyl‐functionalized nitrogen‐rich materials derived from 1,3,5‐triazine and 1,2,4,5‐tetrazine was synthesized through reactions between N‐nitroso‐N′‐alkylguanidines and the hydrazine derivatives of 1,3,5‐triazine or 1,2,4,5‐tetrazine. These compounds were fully characterized using multinuclear NMR and IR spectroscopies, elemental analysis, and differential scanning calorimetry (DSC). The heats of formation for all compounds were calculated with Gaussian 03 and then combined with experimental densities to determine the detonation pressures (P) and velocities (Dv) of the energetic materials. Interestingly, some of the compounds exhibit an energetic performance (P and Dv) comparable to that of RDX, thus holding promise for application as energetic materials.
On the Design of Observer for Nonlinear Time‐Delay Systems
Authors: Batmani Yazdan , Khaloozadeh Hamid
Published: October 2013

This paper suggests a new method to design observers in a class of nonlinear time‐delay systems with delays in system states. The method is based on an extension of the well‐known state‐dependent Riccati equation (SDRE) technique. The conditions for locally asymptotic stability of the proposed observer are investigated. Some numerical simulations are provided to show the design procedure and the flexibility of the proposed observer.
The anatomy of the clavicle
Authors: Bernat Amit , Huysmans Toon , Van Glabbeek Francis , Sijbers Jan , Gielen Jan , Van Tongel Alexander
Published: October 2013

The clavicle has a complex osteologic structure that makes morphological analysis extremely difficult. A three‐dimensional study was conducted to examine the anatomical variations and characteristics of the bone. Sixty‐eight human cadaver clavicles were dissected, CAT‐scanned, and reconstructed. An automated parameterization and correspondence shape analysis system was developed. A new length, designated as centerline (CL) length, was defined and measured. This length represents the true length of the clavicle. The endpoint length was measured as the distance between two endpoints. The width and curvature were measured in the axial (AX) and frontal (FR) plane and defined along the CL. Next gender and side characteristics and variations were examined. The mean CL length was 159.0 ± 11.0 mm. The mean endpoint length was 149.4 ± 10.3 mm, which was statistically significantly shorter than the CL. The male clavicle was significantly longer (166.8 ± 7.3 mm vs. 151.0 ± 8.2 mm), wider (14.6 ± 1.5 mm vs. 12.7 ± 1.3 mm lateral FR plane, 25.9 ± 4.1 mm vs. 23.5 ± 3.0 mm lateral AX plane and 24.7 ± 2.8 mm vs. 22.8 ± 2.8 mm medial AX plane), and more curved (10.8 ± 2.8 mm vs. 8.6 ± 2.3 mm medial and 10.5 ± 3.3 mm vs. 9.1 ± 2.5 mm lateral) than the female one. Left clavicles were significant longer (159.8 ± 10.9 mm vs. 158.0 ± 11.2 mm) than right clavicles. A novel three‐dimensional system was developed, used and tested in order to explore the anatomical variations and characteristics of the human clavicle. This information, together with the automated system, can be applied to future clavicle populations and to the design of fixation plates for clavicle fractures. Clin. Anat. 27:712–723, 2014. © 2013 Wiley Periodicals, Inc.
Community DSPD pilot services in South London: Rates of reconviction and impact of supported housing on reducing recidivism
Authors: Bruce Matt , Crowley Sarah , Jeffcote Nikki , Coulston Belinda
Published: October 2013

Background

The effectiveness of community services in reducing recidivism by men in the ‘dangerous and severe personality disorder’ framework – with personality disorder and at high risk of recidivism – is unknown.

Aims

To conduct a preliminary examination of the characteristics and reconviction rates of male offenders with personality disorder accessing two South London community dangerous and severe personality disorder pilot outpatient services and to evaluate the role of supported housing for them.

Methods

Reoffending outcomes of 107 high risk offenders with personality disorder were assessed using a cross‐sectional cohort study design. Participants were allocated to outpatient only (non‐residential) or outpatient with supported housing groups. Self‐reported, collateral and criminal justice data and Offender Group Reconviction Scale III predictors of reoffending were used to describe the samples.

Results

The overall reconviction rate over the entire study period was 11%. At 12 months following acceptance to the service, reoffending for the entire sample was significantly lower (5%) than mean Offender Group Reconviction Scale III scores predicted (51%). Multivariate analyses confirmed that those also in receipt of supportive housing were significantly less likely to reoffend than those without. Although there was no difference between groups in violent reconviction specifically, only five men in total reoffended violently.

Conclusions

Although findings appear promising, this was a naturalistic study. The sample size was small, but represented all men accepted into the two pilot services. Further evaluation of the role of supported housing and perhaps other details of community supervision should follow. Copyright © 2013 John Wiley & Sons, Ltd.
Long‐term (8 year) outcomes and predictors of major adverse cardiac events after full metal jacket drug‐eluting stent implantation
Authors: Lee Cheol Whan , Ahn Jung‐Min , Lee Jong‐Young , Kim Won‐Jang , Park Duk‐Woo , Kang Soo‐Jin , Lee Seung‐Whan , Kim Young‐Hak , Park Seong‐Wook , Park Seung‐Jung
Published: October 2013

Objectives

We examined long‐term outcomes and predictors of major adverse cardiac events after the full metal jacket (FMJ) stent implantation.

Background

The FMJ procedure has been used to treat diffuse coronary artery disease (CAD), but long‐term outcomes remain unknown.

Methods

The study population consisted of 347 consecutive patients (352 lesions) who had been treated for de novo diffuse CAD with FMJ stents (stent length ≥ 60 mm).

Results

The mean age was 61.0 ± 10.1 years, and the stent length was 71.9 ± 13.7 mm. The procedural success rate was 97.7%. Major in‐hospital complications (one death and two acute stent thromboses) occurred in three patients (0.7%). The median follow‐up was 101 months (interquartile range, 95–108 months). During follow‐up, there were 60 deaths (33 cardiac), 20 myocardial infarctions, and 94 revascularizations. Definite stent thrombosis occurred in 12 patients. The event‐free survival rate for cardiac death, cardiac death/myocardial infarction, or cardiac death/myocardial infarction/target lesion revascularization was 90.5 ± 1.6, 85.8 ± 1.9, and 71.6 ± 2.5% at 8 years, respectively. Left ventricular dysfunction (ejection fraction < 45%) was an independent predictor of cardiac death (OR: 4.88; 95% CI: 1.81–13.13; P = 0.002). Left ventricular dysfunction and a stent length > 80 mm were significantly related to cardiac death/myocardial infarction. Likewise, a stent length > 80 mm was an independent predictor of cardiac death/myocardial infarction/target lesion revascularization (OR: 2.45; 95% CI: 1.16–5.19; P = 0.019).

Conclusion

Long‐term outcomes appear favorable after FMJ procedures, and left ventricular dysfunction and a stent length > 80 mm are major predictors of major adverse cardiac events. These findings might be useful in identifying the most suitable treatments for patients with very diffuse CAD. © 2013 Wiley Periodicals, Inc.
Blood pressure response to renal artery stenting in 901 patients from five prospective multicenter FDA‐approved trials
Authors: Weinberg Ido , Keyes Michelle J. , Giri Jay , Rogers Kevin R. , Olin Jeffrey W. , White Christopher J. , Jaff Michael R.
Published: October 2013

Background

Renal artery stent revascularization is commonly used for renovascular hypertension. Clinical predictors associated with blood pressure (BP) improvement after renal artery stent revascularization are not well understood.

Methods

Patient‐level data from 901 patients in five prospective multicenter Food and Drug Administration‐approved investigational device exemption studies of renal artery stent revascularization was pooled. BP response was defined as reduction of systolic BP (SBP) by >10 mm Hg. Stent patency was defined within each study. Associations of BP reduction were determined by logistic regression.

Results

Of 901 patients, complete outcome information was available in 527. Of these, 212/527 (40%) were male, mean age was 63 ± 13 years, 196/544 (36%) were diabetic and 504/527 (96%) had a SBP ≥ 140 mm Hg or DBP ≥ 90 mm Hg at baseline. Compared to baseline, 9‐month systolic (164 ± 21 mm Hg vs. 146 ± 22 mm Hg, P < 0.0001) and diastolic (79 ± 13 mm Hg vs. 76 ± 12 mm Hg, P < 0.0001) BP declined significantly. Nine‐month stent patency was 90% (305/339). In a univariate analysis, baseline SBP >150 mm Hg (OR = 4.09, CI = 2.74–6.12, P < 0.0001) was positively associated with BP response following renal artery stent revascularization. In a multivariable analysis, baseline SBP remained associated with a positive BP response (OR = 1.76, CI = 1.53–2.03, P < 0.0001).

Conclusions

In the largest pooled dataset of patients treated with renal artery stent revascularization, SBP and DBP were significantly lower at 9‐months. Elevated baseline SBP (>150 mm Hg) was strongly associated with BP reduction after the procedure. © 2013 Wiley Periodicals, Inc.
Synthesis, Crystal Structure and Photophysical Properties of Pyrene–Helicene Hybrids
Authors: Bédard Anne‐Catherine , Vlassova Anna , Hernandez‐Perez Augusto C. , Bessette André , Hanan Garry S. , Heuft Matthew A. , Collins Shawn K.
Published: October 2013

Synthesis of helically chiral aromatics resulting from fusion of pyrene and [4]‐ or [5]helicene has been accomplished using photoredox catalysis employing a Cu‐based sensitizer as the key step. Photocyclisation experiments for the synthesis of the target compounds were carried out in batch and using continuous flow strategies. The solid‐state structures, UV/Vis absorption spectra and fluorescence spectra of the pyrene–helicene hybrids were investigated and compared to that of the parent [5]helicene to discern the effects of merging a pyrene moiety within a helicene skeleton. The studies demonstrated that pyrene–helicene hybrids adopt co‐planar or stacked arrangements in the solid state, in contrast to the solid‐state structure of the parent [5]helicene. The UV/Vis and fluorescence spectra of the pyrene–helicene hybrids exhibited strong red‐shifts when compared to the parent [5]helicene. DFT calculations suggest that the strategy of extending the π surface in the y axis of the helicenes increased their HOMO levels while also decreasing their LUMO levels, resulting in significantly reduced band gaps.
Chirality Induction by Formation of Assembled Structures Based on Anion‐Responsive π‐Conjugated Molecules
Authors: Maeda Hiromitsu , Hane Wataru , Bando Yuya , Terashima Yoshitaka , Haketa Yohei , Shibaguchi Hiroshi , Kawai Tsuyoshi , Naito Masanobu , Takaishi Kazuto , Uchiyama Masanobu , Muranaka Atsuya
Published: October 2013

Anion‐responsive π‐conjugated compounds having chiral alkyl chains were synthesized. Circular dichroism (CD) and circularly polarized luminescence (CPL) were observed in the solution‐state assemblies of the chiral anion receptors and those of their anion complexes as salts of a planar triazatriangulenium cation. The CD and CPL spectral patterns of the ion‐pair‐based assemblies were completely opposite to those of the anion‐free assemblies, and this suggests that anion binding and subsequent ion pairing change the chirality of the assembly modes.
Rare‐Earth‐Metal Alkylaluminates Supported by N‐Donor‐Functionalized Cyclopentadienyl Ligands: CH Bond Activation and Performance in Isoprene Polymerization
Authors: Jende Lars N. , Maichle‐Mössmer Cäcilia , Anwander Reiner
Published: October 2013

Homoleptic tetramethylaluminate complexes [Ln(AlMe4)3] (Ln=La, Nd, Y) reacted with HCpNMe2 (CpNMe2=1‐[2‐(N,N‐dimethylamino)‐ethyl]‐2,3,4,5‐tetramethyl‐cyclopentadienyl) in pentane at −35 °C to yield half‐sandwich rare‐earth‐metal complexes, [{C5Me4CH2CH2NMe2(AlMe3)}Ln(AlMe4)2]. Removal of the N‐donor‐coordinated trimethylaluminum group through donor displacement by using an equimolar amount of Et2O at ambient temperature only generated the methylene‐bridged complexes [{C5Me4CH2CH2NMe(μ‐CH2)AlMe3}Ln(AlMe4)] with the larger rare‐earth‐metal ions lanthanum and neodymium. X‐ray diffraction analysis revealed the formation of isostructural complexes and the CH bond activation of one aminomethyl group. The formation of Ln(μ‐CH2)Al moieties was further corroborated by 13C and 1H‐13C HSQC NMR spectroscopy. In the case of the largest metal center, lanthanum, this CH bond activation could be suppressed at −35 °C, thereby leading to the isolation of [(CpNMe2)La(AlMe4)2], which contains an intramolecularly coordinated amino group. The protonolysis reaction of [Ln(AlMe4)3] (Ln=La, Nd) with the anilinyl‐substituted cyclopentadiene HCpAMe2 (CpAMe2=1‐[1‐(N,N‐dimethylanilinyl)]‐2,3,4,5‐tetramethylcyclopentadienyl) at −35 °C generated the half‐sandwich complexes [(CpAMe2)Ln(AlMe4)2]. Heating these complexes at 75 °C resulted in the CH bond activation of one of the anilinium methyl groups and the formation of [{C5Me4C6H4NMe(μ‐CH2)AlMe3}Ln(AlMe4)] through the elimination of methane. In contrast, the smaller yttrium metal center already gave the aminomethyl‐activated complex at −35 °C, which is isostructural to those of lanthanum and neodymium. The performance of complexes [{C5Me4CH2CH2NMe(μ‐CH2)AlMe3}‐ Ln(AlMe4)], [(CpAMe2)Ln(AlMe4)2], and [{C5Me4C6H4NMe(μ‐CH2)AlMe3}Ln(AlMe4)] in the polymerization of isoprene was investigated upon activation with [Ph3C][B(C6F5)4], [PhNMe2H][B(C6F5)4], and B(C6F5)3. The highest stereoselectivities were observed with the lanthanum‐based pre‐catalysts, thereby producing polyisoprene with trans‐1,4 contents of up to 95.6 %. Narrow molecular‐weight distributions (Mw/Mn<1.1) and complete consumption of the monomer suggested a living‐polymerization mechanism.
Surfactant Hydrogels for the Dispersion of Carbon‐Nanotube‐Based Catalysts
Authors: Di Crescenzo Antonello , Bardini Luca , Sinjari Bruna , Traini Tonino , Marinelli Lisa , Carraro Mauro , Germani Raimondo , Di Profio Pietro , Caputi Sergio , Di Stefano Antonio , Bonchio Marcella , Paolucci Francesco , Fontana Antonella
Published: October 2013

Novel hydrogel phases based on positively charged and zwitterionic surfactants, namely, N‐[p‐(n‐dodecyloxybenzyl)]‐N,N,N‐trimethylammonium bromide (pDOTABr) and p‐dodecyloxybenzyldimethylamine oxide (pDOAO), which combine pristine carbon nanotubes (CNTs), were obtained, thus leading to stable dispersions and enhanced cross‐linked networks. The composite hydrogel featuring a well‐defined nanostructured morphology and an overall positively charged surface was shown to efficiently immobilise a polyanionic and redox‐active tetraruthenium‐substituted polyoxometalate (Ru4POM) by complementary charge interactions. The resulting hybrid gel has been characterised by electron microscopy techniques, whereas the electrostatic‐directed assembly has been monitored by means of fluorescence spectroscopy and ζ‐potential tests. This protocol offers a straightforward supramolecular strategy for the design of novel aqueous‐based electrocatalytic soft materials, thereby improving the processability of CNTs while tuning their interfacial decoration with multiple catalytic domains. Electrochemical evidence confirms that the activity of the catalyst is preserved within the gel media.
Efficient Access to Enantiopure γ4‐Amino Acids with Proteinogenic Side‐Chains and Structural Investigation of γ4‐Asn and γ4‐Ser in Hybrid Peptide Helices
Authors: Jadhav Sandip V. , Misra Rajkumar , Singh Sumeet K. , Gopi Hosahudya N.
Published: October 2013

Hybrid peptides composed of α‐ and β‐amino acids have recently emerged as new class of peptide foldamers. Comparatively, γ‐ and hybrid γ‐peptides composed of γ4‐amino acids are less studied than their β‐counterparts. However, recent investigations reveal that γ4‐amino acids have a higher propensity to fold into ordered helical structures. As amino acid side‐chain functional groups play a crucial role in the biological context, the objective of this study was to investigate efficient synthesis of γ4‐residues with functional proteinogenic side‐chains and their structural analysis in hybrid‐peptide sequences. Here, the efficient and enantiopure synthesis of various N‐ and C‐terminal free‐γ4‐residues, starting from the benzyl esters (COOBzl) of N‐Cbz‐protected (E)‐α,β‐unsaturated γ‐amino acids through multiple hydrogenolysis and double‐bond reduction in a single‐pot catalytic hydrogenation is reported. The crystal conformations of eight unprotected γ4‐amino acids (γ4‐Val, γ4‐Leu, γ4‐Ile, γ4‐Thr(OtBu), γ4‐Tyr, γ4‐Asp(OtBu), γ4‐Glu(OtBu), and γ‐Aib) reveals that these amino acids adopted a helix favoring gauche conformations along the central CγCβ bond. To study the behavior of γ4‐residues with functional side chains in peptide sequences, two short hybrid γ‐peptides P1 (Ac‐Aib‐γ4‐Asn‐Aib‐γ4‐Leu‐Aib‐γ4‐Leu‐CONH2) and P2 (Ac‐Aib‐γ4‐Ser‐Aib‐γ4‐Val‐Aib‐γ4‐Val‐CONH2) were designed, synthesized on solid phase, and their 12‐helical conformation in single crystals were studied. Remarkably, the γ4‐Asn residue in P1 facilitates the tetrameric helical aggregations through interhelical H bonding between the side‐chain amide groups. Furthermore, the hydroxyl side‐chain of γ4‐Ser in P2 is involved in the interhelical H bonding with the backbone amide group. In addition, the analysis of 87 γ4‐residues in peptide single‐crystals reveal that the γ4‐residues in 12‐helices are more ordered as compared with the 10/12‐ and 12/14‐helices.
Copper‐Catalyzed Aerobic Oxidative CH Functionalization of Substituted Pyridines: Synthesis of Imidazopyridine Derivatives
Authors: Yu Jipan , Jin Yunhe , Zhang Hao , Yang Xiaobo , Fu Hua
Published: October 2013

A novel, efficient, and practical method for the synthesis of imidazopyridine derivatives has been developed through the copper‐catalyzed aerobic oxidative CH functionalization of substituted pyridines with N‐(alkylidene)‐4H‐1,2,4‐triazol‐4‐amines. The procedure occurs by cleavage of the NN bond in the N‐(alkylidene)‐4H‐1,2,4‐triazol‐4‐amines and activation of an aryl CH bond in the substituted pyridines. This is the first example of the preparation of imidazopyridine derivatives by using pyridines as the substrates by transition‐metal‐catalyzed CH functionalization. This method should provide a novel and efficient strategy for the synthesis of other nitrogen heterocycles.
Reactivity of Yttrium Carboxylates Toward Alkylaluminum Hydrides
Authors: Schädle Christoph , Fischbach Andreas , Herdtweck Eberhardt , Törnroos Karl W. , Anwander Reiner
Published: October 2013

Yttrocene‐carboxylate complex [Cp*2Y(OOCArMe)] (Cp*=C5Me5, ArMe=C6H2Me3‐2,4,6) was synthesized as a spectroscopically versatile model system for investigating the reactivity of alkylaluminum hydrides towards rare‐earth‐metal carboxylates. Equimolar reactions with bis‐neosilylaluminum hydride and dimethylaluminum hydride gave adduct complexes of the general formula [Cp*2Y(μ‐OOCArMe)(μ‐H)AlR2] (R=CH2SiMe3, Me). The use of an excess of the respective aluminum hydride led to the formation of product mixtures, from which the yttrium‐aluminum‐hydride complex [{Cp*2Y(μ‐H)AlMe2(μ‐H)AlMe2(μ‐CH3)}2] could be isolated, which features a 12‐membered‐ring structure. The adduct complexes [Cp*2Y(μ‐OOCArMe)(μ‐H)AlR2] display identical 1J(Y,H) coupling constants of 24.5 Hz for the bridging hydrido ligands and similar 89Y NMR shifts of δ=−88.1 ppm (R=CH2SiMe3) and δ=−86.3 ppm (R=Me) in the 89Y DEPT45 NMR experiments.