bluuebunny/crossref_metadata_2025 huggingface dataset:
10 - Internet and the Egyptian Public Sphere
Authors: Mehanna Omnia
Published: November 2011

The Internet offers many actors in the society ways to present and raise discussion of ideas that is not possible or easy to engage in, especially in societies with conservative facades such as the Egyptian society. The number of Internet users in Egypt had reached 8.6 million by March 2008. This means that more than 10.per cent of the total Egyptian population had access to the Internet. The number of Internet users in Egypt is the third highest in Africa and represents about 17 per cent of the total number of users in Africa. By taking advantage of the opportunity of having greater access to the Internet and using the security of being anonymous, if one desired, provided by this medium of communication, increasing numbers of Egyptians started using the Internet to gain information and engage in political, social and religious discussions. This new E-public sphere in Egypt is not completely virtual, nor is it completely real.
The Internet facilitated more chances to networking, forming alliances and addressing the public. This has led to the emergence of a kind of alternative media run by professionals, semi-professionals and amateurs. And of equal importance, an increasing number of blogs and websites started addressing highly controversial social and religious issues.
This article, focusing on websites and blogs, explores the new trends which the Internet gave rise to, as well as institutions – such as government and established religious institutions – whose power to monopolise public debates has been challenged by the Internet in Egypt, till 2008. The paper also shows how the state interacts with these trends through recent attempts to increase censorship of the Internet, and in particular its usage for political mobilisation.
Estimation of Absolute Cardiovascular Risk in Individuals with Diabetes Mellitus: Rationale and Approaches
Authors: Echouffo-Tcheugui Justin B. , Ogunniyi Modele O. , Kengne André P.
Published: November 2011

Purpose. To examine the usefulness of cardiovascular risk estimation models in people with diabetes. Methods. Review of published studies that compare the discriminative power of major cardiovascular risk factors single or in combination in individuals with and without diabetes, for major cardiovascular outcomes. Results. In individuals with and without diabetes, major risk factors affect cardiovascular risk similarly, with no evidence of any significant interaction. Accounting for diabetes-specific parameters, cardiopreventative therapies can significantly improve risk estimation in diabetes. General and diabetes-specific cardiovascular risk models have a useful discriminative power, but tend to overestimate risk in individuals with diabetes. Their impact on care delivery, adherence to therapies, and patients' outcome remain poorly understood. Conclusions. The high-risk status conferred by diabetes does not preclude the estimation of absolute cardiovascular risk estimation using global risk tools in individuals with diabetes, as this is useful for the initiation and intensification of preventive measures.
FRACTALS AND SELF-SIMILARITY IN ECONOMICS: THE CASE OF A STOCHASTIC TWO-SECTOR GROWTH MODEL
Authors: La Torre Davide , Marsiglio Simone , Privileggi Fabio
Published: November 2011

We study a stochastic, discrete-time, two-sector optimal growth model in which the production of the homogeneous consumption good uses a Cobb-Douglas technology, combining physical capital and an endogenously determined share of human capital. Education is intensive in human capital as in Lucas (1988), but the marginal returns of the share of human capital employed in education are decreasing, as suggested by Rebelo (1991). Assuming that the exogenous shocks are i.i.d. and affect both physical and human capital, we build specific configurations for the primitives of the model so that the optimal dynamics for the state variables can be converted, through an appropriate log-transformation, into an Iterated Function System converging to an invariant distribution supported on a generalized Sierpinski gasket.
The Marriage of Terpyridines and Inorganic Nanoparticles: Synthetic Aspects, Characterization Techniques, and Potential Applications
Authors: Winter Andreas , Hager Martin D. , Newkome George R. , Schubert Ulrich S.
Published: November 2011

The utilization of supramolecular chemistry, i.e., metal‐to‐ligand coordination, in the field of nanotechnology is evaluated with respect to 2,2′:6′,2″‐terpyridine, as tridentate metal binding site. Stabilization as well as directed self‐assembly of nanometer‐sized materials into ordered arrays are the most widely studied targets of current research. Moreover, energy‐ and/or electron‐transfer processes are enabled when redox‐active terpyridine complexes are bound to (semi)conducting species (e.g., fullerenes, polyoxometalates)–thus, applications in nanoelectronics and catalysis are currently arising from these hybrid materials. Progress made in these fields, resulting from the marriage of terpyridines (as well as their metal complexes) and nanostructures, is summarized in this Review Article.
Deep Energetic Trap States in Organic Photovoltaic Devices
Authors: Shuttle Christopher G. , Treat Neil D. , Douglas Jessica D. , Fréchet Jean M. J. , Chabinyc Michael L.
Published: November 2011

The nature of energetic disorder in organic semiconductors is poorly understood. In photovoltaics, energetic disorder leads to reductions in the open circuit voltage and contributes to other loss processes. In this work, three independent optoelectronic methods were used to determine the long‐lived carrier populations in a high efficiency N‐alkylthieno[3,4‐c]pyrrole‐4,6‐dione (TPD) based polymer: fullerene solar cell. In the TPD co‐polymer, all methods indicate the presence of a long‐lived carrier population of ∼ 1015 cm−3 on timescales ≥ 100 μs. Additionally, the behavior of these photovoltaic devices under optical bias is consistent with deep energetic lying trap states. Comparative measurements were also performed on high efficiency poly‐3‐hexylthiophene (P3HT): fullerene solar cells; however a similar long‐lived carrier population was not observed. This observation is consistent with a higher acceptor concentration (doping) in P3HT than in the TPD‐based copolymer.
Polymeres graphitisches Kohlenstoffnitrid als heterogener Organokatalysator: von der Photochemie über die Vielzweckkatalyse hin zur nachhaltigen Chemie
Authors: Wang Yong , Wang Xinchen , Antonietti Markus
Published: November 2011

Polymere graphitische Kohlenstoffnitrid‐Materialien (vereinfacht g‐C3N4), die nur aus C, N und Spuren von H bestehen, sind in den letzten Jahren wieder verstärkt in das Zentrum des Interesses gerückt, wohl auch wegen der Ähnlichkeit zu Graphit. g‐C3N4ist anders als Graphit ein Halbleiter mit mittlerer Bandlücke und damit ein effektiver (Photo)‐Katalysator für eine ganze Reihe von Reaktionen. In diesem Aufsatz beschreiben wir die “Polymerchemie” des synthetischen Aufbaus, wie die Bandlagen und die Bandlücke durch Copolymerisation und Dotierung verändert werden können und wie Änderungen der Festkörpertextur die Effektivität dieses heterogenen Organokatalysators verbessern können. g‐C3N4und seine Modifikationen zeigen eine sehr hohe thermische und chemische Stabilität und katalysieren eine ganze Reihe von “Traumreaktionen”, wie die photochemische Spaltung von Wasser, milde und selektive Oxidationsreaktionen, oder – als coaktiver Katalysatorträger – superschnelle Hydrierungen. Da Kohlenstoffnitrid metallfrei ist, toleriert es funktionelle Gruppen und ist daher für Vielzweckanwendungen in der Umwandlung von Biomasse und in der nachhaltigen Chemie geeignet.
Synthesis and characterization of diamide–diimide–diamines based on p‐amino benzoic acid and their curing and thermal behavior with epoxy blends containing phosphorus/silicon in the main chain
Authors: Durga Geeta , Narula Anudeep Kumar
Published: November 2011

Diimide–diacid (I) having an imide group in its rigid structure was synthesized by the refluxing of 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride [4,4′‐carbonyldiphthalic anhydride (BTDA)] and p‐amino benzoic acid in a mixture of acetic acid and pyridine (3 : 2 v/v). The chloroderivative of the diacid (I) was synthesized by its reaction with thionyl chloride, this was followed by condensation with different diamines with phenyl, naphthyl, ether, sulfide, and cardo groups to generate a series of diamide–diimide–diamines (DADIDAs). The resultant DADIDAs were characterized by elemental analysis and spectroscopic techniques, namely, Fourier transform infrared spectroscopy and NMR spectroscopy, and were used as epoxy curing agents to impart flame retardancy to the epoxy system. Two epoxy blends (designated as ES and EP) were prepared by the homogeneous mixing of diglycidyl ether of bisphenol A (DGEBA) with 1,3‐bis(3‐glycidyloxypropyl)tetramethyl disiloxane and DGEBA with tris(glycidyloxy)phosphine oxide: each in a ratio of 3 : 2 respectively. The synergistic effect of phosphorus/silicon with nitrogen on the thermal properties of the modified epoxy system was studied. The curing behavior of the epoxy resins formulated by the reaction of stoichiometric amounts of ES/EP with the synthesized DADIDAs were determined by differential scanning calorimetry, and the thermal stabilities of the cured epoxies were evaluated by thermogravimetric analyses (TGAs) under nitrogen and air. TGA indicated that the residual weight percentage of polymers at 800°C was in the range 36.4–60.0 in nitrogen, and in air, it was up to 6.5. However, the major loss in weight in air occurred at elevated temperature; this demonstrated their potential use as flame‐retardant epoxy systems for electronic/electrical encapsulants. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Strontium(II) ion uptake on poly(N‐vinyl imidazole)‐based hydrogels
Authors: Garg Godawari , Chauhan Ghanshyam S. , Ahn J.‐H.
Published: November 2011

In this article, we report on the extraction of Sr(II) ions from aqueous solution with a series of poly(N‐vinyl imidazole)‐based hydrogels. The hydrogels were synthesized by the crosslinking of N‐vinyl imidazole with four different crosslinkers with γ rays as initiators. The well‐characterized hydrogels were used as Sr(II) sorbents. Sr(II) uptake was determined with a colorimetric method with Rose Bengal anionic dye. Scanning electron microscopy–energy‐dispersive spectroscopy analysis of the Sr(II)‐loaded polymers was recorded to ascertain the uptake of Sr(II) ions. The experimental adsorption values were analyzed with the Freundlich and Temkin equations, and the kinetics of adsorption were investigated with a pseudo‐second‐order sorption kinetic model. The results show that the equilibrium data fit well in the Freundlich isotherm and followed a pseudo‐second‐order kinetic model. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Preparation of molecularly imprinted polymers: Diethyl(3‐methylureido)(phenyl)methylphosphonate as a dummy template for the recognition of its organophosphate pesticide analogs
Authors: Kang Shu , Xu Yun , Zhou Li , Pan Canping
Published: November 2011

A novel compound, diethyl(3‐methylureido)(phenyl)methylphosphonate (DEP), possessing an organophosphate skeleton, was synthesized and used as a dummy template to prepare molecularly imprinted polymers (MIPs) for the recognition of organophosphate pesticide analogs. Computational modeling was used to study the primary intermolecular interactions in the prepolymerization mixture. It was found that the interaction force between DEP and the monomers was hydrogen bonding. A series of MIPs were synthesized with different monomers and were evaluated by adsorption experiments, which showed that methacrylic acid was used as an appropriate monomer and a molar ratio of DEP to MAA of 1 : 9 was optimal. Scatchard analysis showed that there might have been two types of binding sites in the MIPs. DEP and several pesticides were used in molecular recognition specificity tests of DEP–MIP, which exhibited better selectivity and reservation ability for organophosphate pesticides, such as methamidophos and orthene, possessing amino or imino groups and a smaller steric hindrance. On the basis of the use of a dummy molecule as template, the problem of template leakage could be avoided; this, thereby, improved the specificity of analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012
Field investigations and multi‐indicators for shallow water lagoon management: perspective for societal benefit
Authors: Brehmer Patrice , Do Chi Thang , Laugier Thierry , GALGANI FRANÇOIS , Laloë Francis , Darnaude Audrey M. , Fiandrino Annie , Mouillot David
Published: November 2011

Abiotic and biotic variables of coastal lagoons are highly heterogeneous in both space and time, and this heterogeneity complicates the assessment of their ecological status. These variables are essential to the monitoring and preservation of these fragile ecotones and the resources and services they sustain.

An integrative approach for evaluating the ecological status of coastal lagoons, based on field investigations of the key parameters driving their functioning and a set of selected ecological indicators matching lagoon management information needs for societal benefits, is investigated. Consistency in lagoon status evaluation from multiple and different variables was estimated, through a case study comparing three adjacent yet contrasting French Mediterranean shallow water lagoons.

French Mediterranean shallow water lagoons are used to demonstrate the potential of such an approach and to underline the need for a multi‐faceted framework, for correctly evaluating lagoon status, and underlining the need for high‐frequency lagoon monitoring to avoid errors in status assessment and resulting management plans.

Based on the results, a continuous monitoring system is proposed that would record high frequency biotic and abiotic data in the lagoons. The use of such an ad hoc observatory system, based on appropriate diagnostic indicators and risk estimators would simplify interactions between scientists and managers and would improve the efficiency of their analyses.

A lagoon management plan based on a holistic approach is proposed to help scientists and local managers to reach a consensus about the set of ecological indicators to monitor in the lagoons needed to assess their ‘global health’ status in accordance with both conservation and/or societal needs.

Copyright © 2011 John Wiley & Sons, Ltd.
Effects of Dye‐Adsorption Solvent on the Performances of the Dye‐Sensitized Solar Cells Based on Black Dye
Authors: Ozawa Hironobu , Awa Megumi , Ono Takahiko , Arakawa Hironori
Published: November 2011

The effects of the dye‐adsorption solvent on the performances of the dye‐sensitized solar cells (DSSCs) based on black dye have been investigated. The highest conversion efficiency (10.6 %) was obtained in the cases for which 1‐PrOH and the mixed solvent of EtOH and tBuOH (3:1 v/v) were employed as dye‐adsorption solvents. The optimized value for the dielectric constant of the dye‐adsorption solvent was found to be around 20. The DSSCs that used MeOH as a dye‐adsorption solvent showed inferior solar‐cell performance relative to the DSSCs that used EtOH, 1‐PrOH, 2‐PrOH, and 1‐BuOH. Photo‐ and electrochemical measurements of black dye both in solution and adsorbed onto the TiO2 surface revealed that black dye aggregates at the TiO2 surface during the adsorption process in the case for MeOH. Both the shorter electron lifetime in the TiO2 photoelectrode and the greater resistance in the TiO2–dye–elecrolyte interface, attributed to the dye aggregation at the TiO2 surface, cause the decrease in the solar‐cell performance of the DSSC that used MeOH as a dye adsorption solvent.
P-selectin mediates neutrophil rolling and recruitment in acute pancreatitis
Authors: Hartman H , Abdulla A , Awla D , Lindkvist B , Jeppsson B , Thorlacius H , Regnér S
Published: November 2011

Background

The adhesive mechanisms regulating leucocyte–endothelium interactions in the pancreas remain elusive, but selectins may play a role. This study examined the molecular mechanisms mediating leucocyte rolling along the endothelium in the pancreas and the therapeutic potential of targeting the rolling adhesive interaction in acute pancreatitis (AP).

Methods

Pancreatitis was induced by retrograde infusion of 5 per cent sodium taurocholate into the pancreatic duct, repeated intraperitoneal administration of caerulein (50 µg/kg) or intraperitoneal administration of l-arginine (4 g/kg) in C57BL/6 mice. A control and a monoclonal antibody against P-selectin were administered before and after induction of AP. Serum and tissue were sampled to assess the severity of pancreatitis, and intravital microscopy was used to study leucocyte rolling.

Results

Taurocholate infusion into the pancreatic duct increased the serum level of trypsinogen, trypsinogen activation, pancreatic neutrophil infiltration, macrophage inflammatory protein (MIP) 2 formation and tissue damage. Immunoneutralization of P-selectin decreased the taurocholate-induced increase in serum trypsinogen (median (range) 17·35 (12·20–30·00) versus 1·55 (0·60–15·70) µg/l; P = 0·017), neutrophil accumulation (4·00 (0·75–4·00) versus 0·63 (0–3·25); P = 0·002) and tissue damage, but had no effect on MIP-2 production (14·08 (1·68–33·38) versus 3·70 (0·55–51·80) pg/mg; P = 0·195) or serum trypsinogen activating peptide level (1·10 (0·60–1·60) versus 0·45 (0–1·80) µg/l; P = 0·069). Intravital fluorescence microscopy revealed that anti-P-selectin antibody inhibited leucocyte rolling completely in postcapillary venules of the inflamed pancreas.

Conclusion

Inhibition of P-selectin protected against pancreatic tissue injury in experimental pancreatitis. Targeting P-selectin may be an effective strategy to ameliorate inflammation in AP.
Histidine affinity chromatography‐based methodology for the simultaneous isolation ofEscherichia colismall and ribosomal RNA
Authors: Martins Rita , Queiroz João António , Sousa Fani
Published: November 2011

Research on RNA has led to many important biological discoveries and the improvement of therapeutic technologies. In particular, there is a great focus on small RNA and ribosomal RNA owing to their key functions in the cell, which make them excellent therapeutic targets. Although the study of these RNA classes is progressing, some limitations have been found regarding the use of suitable techniques that are able to produce and isolate biologically competent and chemically stable RNA. To address this, we have developed a novel histidine affinity chromatography‐based isolation methodology for small and ribosomal RNA molecules. The new procedure involves three main steps: (1) cell lysis with guanidinium buffer, (2) RNA primary isolation with ammonium sulfate precipitation and (3) histidine affinity chromatography to specifically purify small RNA and ribosomal RNA from otherEscherichia coliimpurities (genomic DNA and proteins). The RNA quality assessment revealed that both RNA species were obtained with a high recovery, integrity and purity. The potential of this method to achieve a reproducible RNA isolation with appropriate quality has been demonstrated and it should have broad application in the structural, biophysical and biomedical investigation of systems involving RNA components. Copyright © 2011 John Wiley & Sons, Ltd.
Conformer‐Independent Ureidoimidazole Motifs—Tools to Probe Conformational and Tautomeric Effects on the Molecular Recognition of Triply Hydrogen‐Bonded Heterodimers
Authors: Pellizzaro Maria L. , McGhee Andrea M. , Renton Lisa C. , Nix Michael G. , Fisher Julie , Turnbull W. Bruce , Wilson Andrew J.
Published: November 2011

Linear arrays of hydrogen bonds are useful for the reversible assembly of “stimuli‐responsive” supramolecular materials. There is thus an ongoing requirement for easy‐to‐synthesise motifs that are capable of presenting hydrogen‐bonding functionality in a predictable manner, such that high‐affinity and high‐fidelity recognition occurs. The design of linear arrays is made challenging as a consequence of their ability to adopt multiple conformational and tautomeric configurations; with each additional hydrogen‐bonding heteroatom added to an array, the available tautomeric and conformational space increases and it can be difficult to anticipate where unproductive conformers/tautomers will arise. This paper describes a detailed study on the complementary ureidoimidazole donor–donor–acceptor (DDA) array (1) and amidoisocytosine donor–acceptor–acceptor (DAA) array (2). A specific feature of 1 is that two degenerate, intramolecular hydrogen‐bonded conformations are postulated, both of which present a DDA array that is complementary to appropriate DAA partners. 1D and 2D 1H NMR spectroscopy, isothermal titration calorimetry, and ab initio structure calculations confirm 1 interacts with 2 (Ka≈33000 M−1 in CDCl3) in a conformer‐independent fashion driven by enthalpy. Comparison of the binding behaviour of 1 with hexylamidocytosine (4) and amidonaphthyridine (5) provides insight on the role that intramolecular hydrogen‐bonding plays in mediating affinity towards DAA partners.
3‐Azido‐N‐nitro‐1H‐1,2,4‐triazol‐5‐amine‐Based Energetic Salts
Authors: Wang Kai , Parrish Damon A. , Shreeve Jean'ne M.
Published: November 2011

Twelve energetic nitrogen‐rich salts based on 3‐azido‐N‐nitro‐1H‐1,2,4‐triazol‐5‐amine were prepared and fully characterized by 1H, 13C NMR, and IR spectroscopy, differential scanning calorimetry (DSC), and elemental analysis. The crystal structures of the neutral compound 3‐azido‐N‐nitro‐1H‐1,2,4‐triazole‐5‐amine (1) and its triaminoguanidinium salt (13) were determined by single‐crystal X‐ray diffraction. The density of 1 and its twelve salts ranged from 1.57 to 1.79 g cm−3, and the heat of formation was calculated with the Gaussian 03 suite of programs. Compounds 1–13 exhibit promising detonation performances (pressure: 25.3–39.3 GPa; velocity: 8159–9409 ms−1; EXPLO 5.05). Impact sensitivities were also determined by hammer tests and resulted ranging from 2.5 J (very sensitive) to >40 J (insensitive).
Multi‐scale image segmentation algorithm based on support vector machine approximation criteria
Authors: Wang Liejun , Jia Zhenhong
Published: November 2011

A new multi‐scale image segmentation algorithm based on support vector machine (SVM) approximation criteria has been discussed in this paper. Most current multi‐scale image segmentation algorithms are based on the restricted empirical risk minimization, and the approximation of multi‐scale image segmentation was poor. As the SVM theory was one based on the structural risk minimization, the best approximation results could be reached. So, it was combined with multi‐scale image segmentation algorithms, and one‐image multi‐resolution analysis approximation algorithms based on the SVM theory were presented in this paper, which could obtain more accurate multi‐scale image segmentation. By numerical results, the algorithm was further verified that more accurate image segmentation results were unfolded. Copyright © 2011 John Wiley & Sons, Ltd.
Computation of Hyperfine Tensors for Dinuclear MnIIIMnIV Complexes by Broken‐Symmetry Approaches: Anisotropy Transfer Induced by Local Zero‐Field Splitting
Authors: Schraut Johannes , Arbuznikov Alexei V. , Schinzel Sandra , Kaupp Martin
Published: November 2011

Based on broken‐symmetry density functional calculations, the 55Mn hyperfine tensors of a series of exchange‐coupled, mixed‐valence, dinuclear MnIIIMnIV complexes have been computed. We go beyond previous quantum chemical work by fully including the effects of local zero‐field splitting (ZFS) interactions in the spin projection, following the first‐order perturbation formalism of Sage et al. [J. Am. Chem. Soc. 1989, 111, 7239]. This allows the ZFS‐induced transfer of hyperfine anisotropy from the MnIII site to the MnIV site to be described with full consideration of the orientations of local hyperfine and ZFS tensors. After scaling to correct for systematic deficiencies in the quantum chemically computed local ZFS tensors, good agreement with experimental 55Mn anisotropies at the MnIV site is obtained. The hyperfine coupling anisotropies on the MnIII site depend sensitively on structural distortions for a d4 ion. The latter are neither fully reproduced by using a DFT‐optimized coordination environment nor by using experimental structures. For very small exchange‐coupling constants, the perturbation treatment breaks down and a dramatic sensitivity to the scaling of the local ZFS tensors is observed. These results are discussed with respect to ongoing work to elucidate the structure of the oxygen‐evolving complex of photosystem II by analysis of the EPR spectra.
Polyglycerol‐Derived Amphiphiles for the Solubilization of Single‐Walled Carbon Nanotubes in Water: A Structure–Property Study
Authors: Popeney Chris S. , Setaro Antonio , Mutihac Radu‐Cristian , Bluemmel Pascal , Trappmann Britta , Vonneman Jonathan , Reich Stephanie , Haag Rainer
Published: November 2011

A series of nonionic amphiphiles derived from polyglycerol dendrons were studied for their ability to solubilize and isolate single‐walled carbon nanotubes. The amphiphiles possessed differently sized polar head groups, hydrophobic tail units, and various aromatic and non‐aromatic groups between the head and tail groups. Absorbance analysis revealed that amphiphiles with anchor groups derived from pyrene were far inferior to those that possessed simple linear aliphatic tail groups. Absorbance and near‐infrared fluorescence analyses revealed a weak dependence on the dendron size of the head group, but a strong positive trend in suspended nanotube density and fluorescence intensity for amphiphiles with longer tail units. Variations in the moieties linking the head and tail groups led to a range of effects on the suspensions, with linkers imparting flexibility and a bent shape that gave improved performance overall. This was illustrated most dramatically by a pair of benzamide‐containing amphiphiles, the para isomer of which showed evidence in the fluorescence data of increased nanotube aggregate formation when compared with the meta isomer. In addition, statistical AFM was used to illustrate more directly the microscopic differences between amphiphiles that were effective at nanotube bundle disruption and those that were not.
Benchmarking Density Functional Methods against the S66 and S66x8 Datasets for Non‐Covalent Interactions
Authors: Goerigk Lars , Kruse Holger , Grimme Stefan
Published: November 2011

Dispersion‐corrected density functional theory is assessed on the new S66 and S66x8 benchmark sets for non‐covalent interactions. In total, 17 different density functionals are evaluated. Two flavors of our latest additive London‐dispersion correction DFT‐D3 and DFT‐D3(BJ), which differ in their short‐range damping functions, are tested. In general, dispersion corrections are again shown to be crucial to obtain reliable non‐covalent interaction energies and equilibrium distances. The corrections strongly diminish the performance differences between the functionals, and in summary most dispersion‐corrected methods can be recommended. DFT‐D3 and DFT‐D3(BJ) also yield similar results but for most functionals and intermolecular distances, the rational Becke–Johnson scheme performs slightly better. Particularly, the statistical analysis for S66x8, which covers also non‐equilibrium complex geometries, shows that the Minnesota class of functionals is also improved by the D3 scheme. The best methods on the (meta‐)GGA or hybrid‐ (meta‐)GGA level are B97‐D3, BLYP‐D3(BJ), PW6B95‐D3, MPW1B95‐D3 and LC‐ωPBE‐D3. Double‐hybrid functionals are the most accurate and robust methods, and in particular PWPB95‐D3 and B2‐PLYP‐D3(BJ) can be recommended. The best DFT‐D3 and DFT‐D3(BJ) approaches are competitive to specially adapted perturbation methods and clearly outperform standard MP2. Comparisons between S66, S22 and parts of the GMTKN30 database show that the S66 set provides statistically well‐behaved data and can serve as a valuable tool for, for example, fitting purposes or cross‐validation of other benchmark databases.
Cognitive Analytic Therapy for Borderline Personality Disorder: Therapist Competence and Therapeutic Effectiveness in Routine Practice
Authors: Kellett Stephen , Bennett Dawn , Ryle Tony , Thake Anna
Published: November 2011

This study sought to examine the competency of cognitive analytic therapy (CAT) delivered under routine care conditions and to identify the effectiveness of CAT for patients with borderline personality disorder (BPD). Ten cognitive analytic therapists in six National Health Service Trust sites treated 19 patients with BPD using the standard CAT BPD contract of 24 sessions plus four follow‐ups. The methodology was small N repeated measures deign, with patients interviewed at the third follow‐up session using the Change Interview. Results indicate a high treatment and follow‐up compliance rate (89.47%). Significant reductions in psychological distress, risk and dissociation over the time course of the CAT occurred, with a significant increase in personality integration. Most sessions (92.85%) were delivered in a competent manner. Reductions to psychological distress occurred early in treatment and were sustained, whereas increases in personality integration typically occurred later on in treatment. Patients tended to attribute change to the therapy received. Benchmarking against extant CAT BPD evidence notes a moderate effect size across routine care and trial contexts. The results are discussed in terms of identified methodological shortcomings, clinical implications and the contribution made by the CAT model to the treatment of BPD. Copyright © 2011 John Wiley & Sons, Ltd.

Key Practitioner Message

Narrative and diagrammatic reformulation in CAT offers the opportunity for early and effective engagement and potential symptomatic change in patients with BPD.

It is possible to measure outcomes on a session‐by‐session manner with patients with BPD.

Assessing fidelity to the treatment model is useful in practice‐based studies.
LTE and WiMAX: performance and complexity comparison for possible channel estimation techniques
Authors: Hafez H. , Fahmy Y.A. , Khairy M.M.
Published: November 2011

The similarities between the physical layer of LTE and WiMAX systems trigger the design of a unified hardware platform. As a consequence, there exists a great need to design common blocks that can be adapted to support both of them. In this paper, the choice of the channel estimator is studied where the performance and complexity trade‐off is investigated to seek a unified channel estimation design that can suit both systems under different channel conditions. The performance of different channel estimation techniques when applied to LTE and WiMAX systems is assessed and compared. Two channel profiles with different delay spreads are considered for urban macrocell and bad urban macrocell channels. Three different Doppler frequencies are assumed to illustrate the effect of users’ mobility. The estimators’ computational complexity is also thoroughly studied.Copyright © 2011 John Wiley & Sons, Ltd.
Arbitration Interframe Space‐controlled Medium Access Control: a medium access control protocol guaranteeing absolute priority in wireless local area networks
Authors: Lee Youngsoo , Lee Minsik , Choi Chong‐Ho
Published: November 2011

The demand for multimedia services, such as voice over Internet Protocol, video on demand, information dissemination, and ﬁle sharing, is increasing explosively in wireless local area networks. These multimedia services require a certain level of QoS. Thus, it is important to provide QoS for multimedia applications. IEEE 802.11e tries to meet the QoS requirement of multimedia services by using Enhanced Distributed Channel Access. This gives more weights to high‐priority traﬃc than low‐priority traﬃc in accessing the wireless channel. However, Enhanced Distributed Channel Access suffers from many problems such as low aggregate throughput, high collision rates, and ineffective QoS differentiation among priority classes. In this paper, we propose a new medium access scheme, the Arbitration Interframe Space‐controlled Medium Access Control (AC‐MAC), that guarantees absolute priority in 802.11 wireless networks. In AC‐MAC, the AIFS and contention window values are controlled, so that a higher‐priority traﬃc can preferentially access and effectively utilize the channel. Extensive simulations show that AC‐MAC can perfectly provide absolute priority and good throughput performance regardless of the number of contending nodes. In the simulation of voice over Internet Protocol service, AC‐MAC provides effective QoS differentiation among services and also meets the high level of QoS requirements. AC‐MAC also adapts quickly in a dynamic environment and provides good fairness among the nodes belonging to the same priority class. Copyright © 2011 John Wiley & Sons, Ltd.
Channel estimation for nonlinear MIMO receiver with square envelope detection
Authors: Hao Miin‐Jong , Tsai Yu‐Chi
Published: November 2011

Two practical channel estimation schemes, the moment‐based first‐and‐second moments and the simplified maximum likelihood estimators, are proposed for the MIMO/on–off keying system with square envelope detection applied for wireless sensor networks. Here, both the channel response and noise power are estimated simultaneously in comparison with other approaches in which the noise quantity is assumed to be known at the receiver. Hence, the developed estimators are more practical than those estimators without noise power estimation. Simulation results reveal that the system with both proposed schemes can achieve an excellent BER performance in a wide signal‐to‐noise ratio (SNR) range. More specifically, we observed that the simplified maximum likelihood estimator performed as well as the moment‐based first‐and‐second moments estimator for SNR greater than 7.5 dB, yet had much more decline at low SNRs. This study also investigated the effects of the numbers of receive antennas and transmit antennas on the system performance. Simulation results demonstrated that, at the BER of 10−3, the 5 × 5 system had an improvement of 7 dB in SNR compared with the 3 × 3 system. Copyright © 2011 John Wiley & Sons, Ltd.
Synthesis and Characterization of Nanocrystalline FeSb2 for Thermoelectric Applications
Authors: Datta Anuja , Nolas George S.
Published: November 2011

We report an ethanol‐mediated surfactant‐free solvothermal synthesis of phase‐pure Pnmm FeSb2 nanocrystals with an average size of 40 nm. The capping free growth of the nanocrystals resulted in the formation of inherent orthorhombic shapes. The nanocrystals were densified by spark plasma sintering to prepare a polycrystalline bulk material that consisted of 40–200 nm FeSb2 nanocrystal domains (nanocomposite). Low‐temperature Seebeck coefficient, resisitivity, and thermal conductivity were measured on parallelopipeds cut from the densified specimen and compared to bulk FeSb2 prepared by a solid‐state synthesis process. The FeSb2 nanocomposite showed a large reduction in lattice thermal conductivity relative to the bulk due to significant grain‐boundary phonon scattering. If one notes that the solution‐phase synthesis of Pnnm FeSb2 nanocrystals is accounted here for the first time and the low‐temperature thermoelectric properties indicates a significant reduction in lattice thermal conductivity for this material, this work represents an important step towards optimizing thermoelectric properties for cooling applications.
Photocatalytic H2 Production with a Rhenium/Cobalt System in Water under Acidic Conditions
Authors: Guttentag Miguel , Rodenberg Alexander , Kopelent René , Probst Benjamin , Buchwalder Christian , Brandstätter Marco , Hamm Peter , Alberto Roger
Published: November 2011

In photocatalytic H2 formation, tertiary amines are commonly used as sacrificial electron donors, thereby limiting the pH range for studies in water and the concentration of free protons. We found that ascorbate rapidly reductively quenches the excited state of [Re(CO)3(bipy)(py)]+ (bpy = 2,2′‐bipyridyl; py = pyridine). In combination with the water reduction catalyst (WRC) [Co{(DO)(DOH)pn}Br2] [(DO)(DOH)pn = N2,N2′‐propanediylbis(2,3‐butanedione 2‐imine 3‐oxime)], this system produces H2 upon irradiation with light under acidic conditions (pH range 2–6) and with significantly enhanced turnover numbers. Furthermore, we observed that, in contrast to similar systems with tertiary amines, oxidized ascorbate (dehydroascorbic acid) is slowly re‐reduced during the course of photocatalysis.
Triarylmethanols with Bulky Aryl Groups and the NOESY/EXSY Experimental Observation of a Two‐Ring‐Flip Mechanism for the Helicity Reversal of Molecular Propellers
Authors: Tormyshev Victor M. , Genaev Alexander M. , Sal'nikov Georgy E. , Rogozhnikova Olga Yu. , Troitskaya Tatiana I. , Trukhin Dmitry V. , Mamatyuk Victor I. , Fadeev Dmitry S. , Halpern Howard J.
Published: November 2011

Triarylmethanols – the direct precursors of persistent trityl radicals – are racemic mixtures of chiral three‐bladed molecular propellers. Depending on the bulkiness of the aryl groups, they exhibit various tendencies to interconvert, and the half‐life of room‐temperature racemization varies between 8.4 h and 1.32 years. NOESY/EXSY experiments performed on two representative models strongly support the two‐ring flip mechanism for the configurational interchange.
1‐(Trifluoromethyl)cyclopent‐3‐enecarboxylic Acid Derivatives: Platforms for Bifunctional Cyclic Trifluoromethyl Building Blocks
Authors: Grellepois Fabienne , Kikelj Vincent , Coia Nicolas , Portella Charles
Published: November 2011

We report herein the synthesis and applications of 1‐(trifluoromethyl)cyclopent‐3‐ene‐1‐carboxylic acid and itsesters, promising new trifluoromethylated cyclic building blocks. Initially prepared starting from a pentafluorodithiopropanoic ester, a more convenient and effective approach has been developed starting from commercially available trifluoropropanoic acid or its methyl ester. The interest in these building blocks is exemplified by their use as platforms for a variety of difunctional trifluoromethylcyclopentane derivatives.
Axisymmetric magnetohydrodynamic flow of Jeffrey fluid over a rotating disk
Authors: Hayat T. , Nawaz M. , Awais M. , Obaidat S.
Published: November 2011

This paper examines the magnetohydrodynamic boundary layer flow of Jeffrey fluid due to a rotating disk. The governing partial differential equations are first transformed into the coupled system of ordinary differential equations and then solved by using the homotopy analysis method. The influence of various involved physical parameters on the dimensionless radial and azimuthal velocities is sketched and analyzed. The variation of skin friction coefficients in radial and azimuthal directions is studied for various values of pertinent parameters. Copyright © 2011 John Wiley & Sons, Ltd.
Altered neural activation in ornithine transcarbamylase deficiency during executive cognition: An fMRI study
Authors: Gropman Andrea L. , Shattuck Kyle , Prust Morgan J. , Seltzer Rebecca R. , Breeden Andrew L. , Hailu Ayichew , Rigas Amanda , Hussain Rehan , VanMeter John
Published: November 2011

Background: Ornithine transcarbamylase deficiency (OTCD) is an X‐linked urea cycle disorder characterized by hyperammonemia resulting in white matter injury and impairments in working memory and executive cognition. Objective: To test for differences in BOLD signal activation between subjects with OTCD and healthy controls during a working memory task. Design, setting and patients: Nineteen subjects with OTCD and 21 healthy controls participated in a case‐control, IRB‐approved study at Georgetown University Medical Center. Intervention: An N‐back working memory task was performed in a block design using 3T functional magnetic resonance imaging. Results: In subjects with OTCD we observed increased BOLD signal in the right dorsolateral prefrontal cortex (DLPFC) and anterior cingulate cortex (ACC) relative to healthy age matched controls. Conclusions: Increased neuronal activation in OTCD subjects despite equivalent task performance points to sub‐optimal activation of the working memory network in these subjects, most likely reflecting damage caused by hyperammonemic events. These increases directly relate to our previous finding of reduced frontal white matter integrity in the superior extents of the corpus callosum; key hemispheric connections for these areas. Future studies using higher cognitive load are required to further characterize these effects. Hum Brain Mapp, 2013. © 2011 Wiley Periodicals, Inc.
Assessment of p53 functional activity in tumor cells and histologically normal mucosa from patients with head and neck squamous cell carcinoma
Authors: Van der Vorst Sébastien , Dekairelle Anne–France , Weynand Birgit , Hamoir Marc , Gala Jean–Luc
Published: November 2011

Background

The purpose of this study was to investigate the value of p53 functional analysis of separated alleles in yeast (FASAY) as a witness of p53/p21 pathway alteration in head and neck squamous cell carcinoma (HNSCC).

Methods

The p53 transcriptional activity was prospectively analyzed in 82 newly diagnosed patients with HNSCC. FASAY and p53 immunostaining were carried out on paired tumoral and histologically normal tissues. The predictive value of FASAY for locoregional recurrence was assessed by Cox survival analysis.

Results

Loss of p53/p21 transcriptional activity was encountered in 88% tumoral and 18% histologically normal samples, associated with mutations (79%) and insertions/deletions (21%). The p53 overexpression underestimated p53 transcriptional abnormalities. FASAY‐positive histologically normal mucosa was significantly associated with locoregional recurrence.

Conclusion

FASAY positivity indicates field cancerization in a subgroup of patients with HNSCC, in which nonfunctional p53 was significantly associated with locoregional recurrence. This prompted us to pursue the study on the p53 functional status of normal mucosa in patients with HNSCC. © 2011 Wiley Periodicals, Inc. Head Neck, 2011
Ultrasound‐guided botulinum toxin injection: A simple in‐office technique to improve tracheoesophageal speech in postlaryngectomy patients
Authors: Chaukar Devendra A. , Sayed Suhail I. , Shetty Nitin S. , Kulkarni Aniruddha V. , Kulkarni Suyash S. , Deshmukh Anuja D. , D'Cruz Anil K.
Published: November 2011

Background

Pharyngoesophageal spasm is a known entity to cause hypertonic/failed tracheoesophageal speech and is successfully treated by botulinum toxin A injection. However, success of botulinum toxin treatment is based on the accurate localization of the pharyngoesophageal segment.

Methods

A 65‐year‐old man who had a laryngectomy using voice prosthesis with hypertonic speech underwent ultrasonographic localization of the hypertonic pharyngoesophageal segment. The ultrasound findings were confirmed using videofluoroscopy. Under ultrasound guidance, botulinum toxin was injected into the hypertonic pharyngoesophageal segment and subsequently voice outcomes were evaluated by a speech language pathologist and the pharyngoesophageal segment was assessed by using an ultrasound scan.

Results

The patient had improvement in his postinjection tracheoesophageal puncture speech. Ultrasound scan assessment of the pharyngoesophageal segment showed adequate dilation as compared to the pre–botulinum toxin injection treatment.

Conclusion

Ultrasonographic localization of the hypertonic pharyngoesophageal segment and ultrasound‐guided botulinum toxin injection is a simple, quick, and relatively cheap method to be used in routine practice. © 2011 Wiley Periodicals, Inc. Head Neck, 2013
Predictors of outcome in patients with metastatic cutaneous head and neck squamous cell carcinoma involving cervical lymph nodes: Improved survival with the addition of adjuvant radiotherapy
Authors: Wang Jeffrey T. , Palme Carsten E. , Morgan Gary J. , Gebski Val , Wang Allen Y. , Veness Michael J.
Published: November 2011

Background

The purpose of this study was to compare the outcome of surgery against surgery plus radiotherapy in patients with metastatic cutaneous head and neck squamous cell carcinoma (HNSCC) to cervical nodes.

Methods

We conducted a 28‐year retrospective analysis of 122 patients whom were treated for metastatic cutaneous HNSCC involving the cervical nodes (levels I–V).

Results

After surgery alone, 11 patients (55%) developed recurrence compared with 23 patients (23%) after surgery plus radiotherapy. On multivariate analysis, the following variables were significantly associated with disease‐free survival (DFS): immunosuppression (p = .002), treatment modality (p < .001), extracapsular spread (p = .009), and pathological nodal stage (p = .04). Patients undergoing surgery plus radiotherapy had a significantly better 5‐year DFS (74% vs 34%; p = .001) and 5‐year overall survival (OS; 66% vs 27%; p = .003) compared with surgery alone.

Conclusion

In patients with metastatic cutaneous HNSCC involving cervical nodes, survival was significantly improved with the addition of radiotherapy. © 2011 Wiley Periodicals, Inc. Head Neck, 2011
Quantitative histological-hemodynamic correlations in cirrhosis
Authors: Sethasine Supatsri , Jain Dhanpat , Groszmann Roberto J. , Garcia-Tsao Guadalupe
Published: November 2011

We have previously shown, in a semiquantitative analysis of liver biopsies showing cirrhosis, that thickness of fibrous septa separating cirrhotic nodules and small size of cirrhotic nodules correlated independently with portal pressure (as determined by the hepatic venous pressure gradient; HVPG) and were independent predictors of the presence of clinically significant portal hypertension (PH). This study aimed to confirm these results using quantitative analysis of these biopsies using digital image analysis. Biopsies of 42 patients with cirrhosis and HVPG measurements within 6 months of the biopsy were included in the study. The following parameters were scored quantitatively and without knowledge of HVPG results: total fibrosis area, septal thickness, nodule size, and number of nodules per millimeter of length of liver biopsy. Fibrosis area was the only parameter that independently correlated with HVPG (r = 0.606; P < 0.0001). Correlation was significant, even among patients with clinically significant PH (r = 0.636; P < 0.005). Fibrosis area and nodule size were both independently predictive of the presence of clinically significant PH (r = 0.57; P = 0.003). Conclusions: On quantitative analysis, fibrosis area was the parameter that correlated best with HVPG and the presence of clinically significant PH. Beyond pathophysiological implications, this also has methodological implications that are discussed in this article. (Hepatology 2012)