bluuebunny/crossref_metadata_2025 huggingface dataset:
Délitement sociétal et appartenances
Authors: Martin Marcienne
Published: November 2012

Évoquer le délitement sociétal renvoie à la notion de structures organisationnelles, lesquelles s’inscrivent dans les appartenances au sein desquelles se construit l’identité du sujet. Force est de constater que la première inscription dans la société humaine prend sa source dans l’anthroponymie. À ce système d’appartenances, s’ajoutent ceux liés à la nationalité et à la langue ou aux langues, pour ne citer que ces derniers. Si les appartenances fédèrent le groupe, qu’en est-il quand plusieurs groupes appartiennent à un territoire commun (réel ou symbolique), mais construisent leur identité dans le cadre de valeurs antinomiques ? Peut-on alors parler d’un projet sociétal commun ? Dans ce présent article, il sera mis en perspective structures organisationnelles et construction identitaire du groupe et de l’individu et, à partir d’exemples, il sera interrogé comment l’adhésion à un système d’appartenances données peut faire évoluer une structure sociale soit vers la néguentropie ou, encore, soit vers l’entropie.
John Adams, Cicero and the Traditions of Republicanism
Authors: CORNISH PAUL JOSEPH
Published: November 2012

John Adams' approach to republican politics emphasizes the need to check and balance powers in a republican constitution, but also the need to check the power of the ‘aristocracies' that arise in society. The need for checks on power is explained in terms of the weakness of human reason relative to the passions, and in terms of the need for harmony and justice to promote happiness in society. Adams retains a Ciceronian view of the origins of human society and of republican government, and relies on Cicero's definitions of ‘people' and ‘republic' to help frame his Defense of the Constitutions of the United States of America. His approach is conservative in that part of his defense is to stress that the colonial governments that existed before Independence were republican, and that the institutions of the colonial governments were the primary models for the new state constitutions after Independence. The study suggests that historical interpretations of the ‘republican tradition' are better understood in terms of a ‘traditions of republicanism.’
Medical Progress and the Influenza Pandemic of 1918
Authors: VANNESTE SARAH FRANCES
Published: November 2012

The influenza outbreak of 1918 spread around the world and left millions of people dead. This pandemic was both a crisis for human life and a crisis for medical professionals attempting to combat the disease. During a period when medicine had become thoroughly professionalized and had made numerous advances in medical treatment, medical professionals perceived their field to be rapidly and consistently progressing, and many believed that there was little medicine could not overcome. Success against such diseases as yellow fever fed the idea that science and rational thought could conquer society's ills drove medical professionals' efforts. However, these modern ideas of progress, perfectibility, and medicine's pending triumph over disease adversely affected the medical profession's ability to deal effectively with the influenza pandemic of 1918. Physicians' efforts had not prevented a serious outbreak, and once it had exploded, they could not control it. Looking specifically at the British medical profession's struggle with the pandemic, as it coursed through both Britain and Britain's armies abroad, this paper examines physicians' own writings and investigates both their initial confidence in the face of disease and their disappointment, fear, and lack of clear direction as the pandemic exploded. In the aftermath of the pandemic, their confusion, dearth of understanding, and pressure to fill the void in knowledge are evident. This paper, then, discusses how confidence affected their mindset when they confronted the pandemic, and how the pandemic, in turn, affected their concept of progress, the ability of medicine, and their duty thereafter.
The Bricolage Approach of Teaching in a Blended Learning Environment
Authors: Aguinaldo Betchie E.
Published: November 2012

The proliferation of technology in various areas in our society can be compare to flowing water that supplies energy to each part of its system. In the field of education, technology pours its strength not only to the process of teaching and learning but also to the continuous improvement of delivery of education. Unfortunately, not all academic institutions are enjoying the benefits provided by technological innovations in education. Various academic institutions have been suffering for several years since the advent of technological innovations in education. Poor academic institutions are far left behind in this educational innovation. This study presented the development of Bricolage Approach of teaching using four types of ICT sustainability. Technology Acceptance Model (TAM) of Davis (1989) was adapted in this study using a customized blended learning environment tool to gauge the students’ acceptability of the Bricolage Approach of Teaching in a blended learning environment. The findings of the study resulted to the increase of students’ knowledge in e-learning tool. Furthermore, result demonstrated concrete evidence of students’ favorable acceptability of Bricolage Approach of teaching in a blended learning environment using TAM’s factor perceived usefulness, perceived ease of use, attitude towards usage and behavior intention to use.   Keywords: Bricolage approach; Bricola; Blended learning; Technology Acceptance Model (TAM)
Surface‐Activated Nanoparticles for Controlled Light‐Responsiveness
Authors: Ahn Sungsook , Jung Sung Yong , Lee Sang Joon
Published: November 2012

Most of the optical properties of nanoparticles (NPs) depend on a nonadditive effect, where there is a maximum (or optimum) value at a specific distance from the NP surface (proximity length). However, knowledge on the relation between the specific surface layer and light responsiveness of NPs is limited. In this study, surface properties of NPs are modulated by electron beam (e‐beam) treatment together with ionic control of the NP surface and dispersing media. The surface modification in terms of the proximity length is found to be critical to the selective enhancement of light absorbance in the ultraviolet‐visible (UV‐vis) and terahertz (THz) regions. In particular, the non‐temporarily electron‐activated NPs absorb short wavelength UV‐vis light, rendering them particulary advantageous for solar energy use. The control over the physical properties of general light‐responsive NPs is a new approach to designing solar‐energy‐based technologies.
Near‐Infrared Fluorescent Silica‐Coated Gold Nanoparticle Clusters for X‐Ray Computed Tomography/Optical Dual Modal Imaging of the Lymphatic System
Authors: Hayashi Koichiro , Nakamura Michihiro , Ishimura Kazunori
Published: November 2012

Lymph nodes (LNs) are often removed to prevent the spread of cancer because they are frequently the first site of metastases. However, the enucleation of LNs requires difficult operative techniques and lymphedema can result as a complication. Although lymphedema can be cured by anastomosis of a lymph vessel (LV) to a vein, the operative procedure is extremely difficult because LNs and LVs are too small and indistinct to be identified. Therefore, visualization of LNs and LVs is important. The combination of X‐ray computed tomography (CT) and fluorescence imaging, CT/fluorescence dual modal imaging, enables the visualization of LNs and LVs before and during surgery. To accomplish this, near‐infrared fluorescent silica‐coated gold nanoparticle clusters (Au@SiO2) with a high X‐ray absorption coefficient are synthesized. Both fluorescence imaging and CT show that the Au@SiO2 nanoparticles gradually accumulate in LNs through LVs. CT determines the location and size of the LNs and LVs without dissection, and fluorescence imaging facilitates their identification. The Au@SiO2 nanoparticles have neither hepatotoxicity nor nephrotoxicity. The results demonstrate that CT/fluorescence dual modal imaging using Au@SiO2 nanoparticles provides anatomical information, including the location and size of LNs and LVs for determining a surgery plan, and provides intraoperative visualization of LNs and LVs to facilitate the operation.
No association of genetic variants in BDNF with major depression: A meta‐ and gene‐based analysis
Authors: Gyekis Joseph P. , Yu Weihong , Dong Shuqian , Wang Haina , Qian Jun , Kota Pravina , Yang Jingyun
Published: November 2012

Major depressive disorder (MDD) is a complex psychiatric condition with strong genetic predisposition. The association of MDD with genetic polymorphisms, such as Val66Met (rs6265), in the brain derived neurotrophic factor (BDNF), have been reported in many studies and the results were conflicting. In this study, we performed a systematic literature search and conducted random‐effects meta‐analysis to evaluate genetic variants in BDNF with MDD. A gene‐based analysis was also conducted to investigate the cumulative effects of genetic polymorphisms in BDNF. A total of 28 studies from 26 published articles were included in our analysis. Meta‐analysis yielded an estimated odds ratio (OR) of 0.96 (95% CI: 0.89–1.05; P = 0.402) for Val66Met (rs6265), 0.83 (95% CI: 0.67–1.04; P = 0.103) for 11757C/G, 1.16 (95% CI: 0.74–1.82; P = 0.527) for 270T/C, 1.03 (95% CI: 0.18–5.75; P = 0.974) for 712A/G and 0.98 (95% CI: 0.85–1.14; P = 0.831) for rs988748. The gene‐based analysis indicated that BDNF is not associated with MDD (P > 0.21). Our updated meta‐ and novel gene‐based analyses provide no evidence of the association of BDNF with major depression. © 2012 Wiley Periodicals, Inc.
Rethinking Primate Origins Again
Authors: SUSSMAN ROBERT W. , TAB RASMUSSEN D. , RAVEN PETER H.
Published: November 2012

In 1974, Cartmill introduced the theory that the earliest primate adaptations were related to their being visually oriented predators active on slender branches. Given more recent data on primate‐like marsupials, nocturnal prosimians, and early fossil primates, and the context in which these primates first appeared, this theory has been modified. We hypothesize that our earliest primate relatives were likely exploiting the products of co‐evolving angiosperms, along with insects attracted to fruits and flowers, in the slender supports of the terminal branch milieu. This has been referred to as the primate/angiosperm co‐evolution theory. Cartmill subsequently posited that: “If the first euprimates had grasping feet and blunt teeth adapted for eating fruit, but retained small divergent orbits…” then the angiosperm coevolution theory would have support. The recent discovery ofCarpolestes simpsoniprovides this support. In addition, new field data on small primate diets, and a new theory concerning the visual adaptations of primates, have provided further evidence supporting the angiosperm coevolution theory.Am. J. Primatol. 75:95‐106, 2013. © 2012 Wiley Periodicals, Inc.
Excessive sleep duration and quality of life
Authors: Ohayon Maurice M. , Reynolds Charles F. , Dauvilliers Yves
Published: November 2012

Objective

Using population‐based data, we document the comorbidities (medical, neurologic, and psychiatric) and consequences for daily functioning of excessive quantity of sleep (EQS), defined as a main sleep period or 24‐hour sleep duration ≥9 hours accompanied by complaints of impaired functioning or distress due to excessive sleep, and its links to excessive sleepiness.

Methods

A cross‐sectional telephone study using a representative sample of 19,136 noninstitutionalized individuals living in the United States, aged ≥18 years (participation rate = 83.2%). The Sleep‐EVAL expert system administered questions on life and sleeping habits; health; and sleep, mental, and organic disorders (Diagnostic and Statistical Manual of Mental Disorders, 4th edition, text revision; International Classification of Sleep Disorders: Diagnostic and Coding Manual II, International Classification of Diseases and Related Health Problems, 10th edition).

Results

Sleeping at least 9 hours per 24‐hour period was reported by 8.4% (95% confidence interval = 8.0–8.8%) of participants; EQS (prolonged sleep episode with distress/impairment) was observed in 1.6% (1.4–1.8%) of the sample. The likelihood of EQS was 3 to 12× higher among individuals with a mood disorder. EQS individuals were 2 to 4× more likely to report poor quality of life than non‐EQS individuals as well as interference with socioprofessional activities and relationships. Although between 33 and 66% of individuals with prolonged sleep perceived it as a major problem, only 6.3 to 27.5% of them reported having sought medical attention.

Interpretation

EQS is widespread in the general population, co‐occurring with a broad spectrum of sleep, medical, neurologic, and psychiatric disorders. Therefore, physicians must recognize EQS as a mixed clinical entity indicating careful assessment and specific treatment planning. ANN NEUROL 2013;73:785–794
Asymmetric Catalysis with Bis(hydroxyphenyl)diamides/Rare‐Earth Metal Complexes
Authors: Kumagai Naoya , Shibasaki Masakatsu
Published: November 2012

A series of asymmetric catalysts composed of conformationally flexible amide‐based chiral ligands and rare‐earth metals was developed for proton‐transfer catalysis. These ligands derived from amino acids provide an intriguing chiral platform for the formation of asymmetric catalysts upon complexation with rare‐earth metals. The scope of this arsenal of catalysts was further broadened by the development of heterobimetallic catalytic systems. The cooperative function of hydrogen bonding and metal coordination resulted in intriguing substrate specificity and stereocontrol, and the dynamic nature of the catalysts led to a switch of their function. Herein, we summarize our recent exploration of this class of catalysts.
Effects of radio frequency and heat on wood bonding with a poly(vinyl acetate) dispersion adhesive
Authors: Chiozza Fabio , Toniolo Fabrizio , Pizzo Benedetto
Published: November 2012

Water‐based poly(vinyl acetate) dispersions are widely used as wood adhesives with dielectric heating systems. However, little is known about the effects of radio frequency (RF) exposure or heat on the adhesive characteristics and on the performances of bonded joints. In this study, the properties of bonded joints exposed to RF were compared with hot pressing and with standard drying, and the observed behavior was explained. Joint characteristics were evaluated by means of both conventional (e.g., shear strength in both dry and wet conditions, etc.) and unconventional (e.g., bondline temperature, moisture content at interface, etc.) procedures, and also selected properties of polymeric film were measured (e.g., water absorption, analysis of the fraction dissolved in water, glass transition temperature [Tg], etc.) to explicate the observed differences. Results evidenced that the effect of both RF and heating was to appreciably speed up the drying process. However, when high values of energetic impulse (owing to both hot pressing and RF) were given to the assemblies, permanent changes were induced into the polymeric glueline. This occurrence was a time‐driven process and reflected mainly on the mechanical performance in wet conditions, which improved appreciably in comparison to the standard reference series. The reason of such behavior was connected to the poly(vinyl alcohol) phase present inside the polymer, and a role was also assigned to AlCl3, used as complexing agent of the polymeric protective colloid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
SVD‐Based Accurate Identification and Compensation of the Coupling Hysteresis and Creep Dynamics in Piezoelectric Actuators
Authors: Liu Lei , Tan Kok Kiong , Lee Tong Heng
Published: November 2012

In this paper, the coupling hysteresis and creep in piezoelectric actuators are identified and compensated for accurate tracking. First, we present the coupling hysteresis and creep model in smart actuators. Next, a complete identification strategy is designed according to the properties of the Preisach model. Then, an approach for parameter updating of the coupling model is provided. With the identified hysteresis and creep, the model‐based inversion compensation is designed. Finally, we apply the model identification and compensation to a piezoelectric stage to demonstrate the effectiveness of the proposed approaches. Significant reduction of the tracking error is achieved with the model‐based inversion feedforward compensator in which the relative errors at 10 Hz and 50 Hz are reduced to 1.85% and 4.53%, respectively. In addition, the model‐based feedforward is augmented with an integral feedback controller. With the composite controller, the relative errors at 10 Hz and 50 Hz are reduced to 0.42% and 3.04%, respectively.
Length‐dependent stability of α‐helical peptide upon adsorption to single‐walled carbon nanotube
Authors: Balamurugan Kanagasabai , Subramanian Venkatesan
Published: November 2012

Earlier studies have shown that the helical content of α‐helical peptide decreases upon its interaction with carbon nanotube (CNT). Further, the length of the α‐helix varies from few residues in the small globular protein to several number of residues in structural and membrane proteins. In structural and membrane proteins, helices are widely present as the supercoil i.e., helical bundles. Thus, in this study, the length‐dependent interaction pattern of α‐helical peptides with CNT and the stability of isolated α‐helical fragment versus supercoiled helical bundle upon interaction with CNT have been investigated using classical molecular dynamics (MD) simulation. Results reveal that the disruption in the helical motif on interaction with CNT is directly proportional to the length of the helix. Also it is found that the shorter helix does not undergo noticeable changes in the helicity upon adsorption with CNT. On the other hand, helicity of longer peptides is considerably affected by its interaction with CNT. In contrast to the known fact that the stability of the helix increases with its length, the disruption in the helical peptide increases with its length upon its interaction with CNT. Comparison of results shows that structural changes in the isolated helical fragment are higher than that in supercoiled helix. In fact, helical chain in supercoiled bundle does not undergo significant changes in the helicity upon interaction with CNT. Both the length of the helical peptide and the inherent stability of the helical unit in the supercoiled helix influence the interaction pattern with the CNT. © 2012 Wiley Periodicals, Inc. Biopolymers 99: 357–369, 2013.
Differences in outcomes of oesophageal and gastric cancer surgery across Europe
Authors: Dikken J L , van Sandick J W , Allum W H , Johansson J , Jensen L S , Putter H , Coupland V H , Wouters M W J M , Lemmens V E P , van de Velde C J H
Published: November 2012

Background

In several European countries, centralization of oesophagogastric cancer surgery has been realized and clinical audits initiated. The present study was designed to evaluate differences in resection rates, outcomes and annual hospital volumes between these countries, and to analyse the relationship between hospital volume and outcomes.

Methods

National data were obtained from cancer registries or clinical audits in the Netherlands, Sweden, Denmark and England. Differences in outcomes were analysed between countries and between hospital volume categories, adjusting for available case-mix factors.

Results

Between 2004 and 2009, 10 854 oesophagectomies and 9010 gastrectomies were registered. Resection rates in England were 18·2 and 21·6 per cent for oesophageal and gastric cancer respectively, compared with 28·5–29·9 and 41·4–41·9 per cent in the Netherlands and Denmark (P < 0·001). The adjusted 30-day mortality rate after oesophagectomy was lowest in Sweden (1·9 per cent). After gastrectomy, the adjusted 30-day mortality rate was significantly higher in the Netherlands (6·9 per cent) than in Sweden (3·5 per cent; P = 0·017) and Denmark (4·3 per cent; P = 0·029). Increasing hospital volume was associated with a lower 30-day mortality rate after oesophagectomy (odds ratio 0·55 (95 per cent confidence interval 0·42 to 0·72) for at least 41 versus 1–10 procedures per year) and gastrectomy (odds ratio 0·64 (0·41 to 0·99) for at least 21 versus 1–10 procedures per year).

Conclusion

Hospitals performing larger numbers of oesophagogastric cancer resections had a lower 30-day mortality rate. Differences in outcomes between several European countries could not be explained by differences in hospital volumes. To understand these differences in outcomes and resection rates, with reliable case-mix adjustments, a uniform European upper gastrointestinal cancer audit with recording of standardized data is warranted.
Elucidation of Nitrate Reduction Mechanisms on a Pd‐In Bimetallic Catalyst using Isotope Labeled Nitrogen Species
Authors: Zhang Rui , Shuai Danmeng , Guy Kathryn A. , Shapley John R. , Strathmann Timothy J. , Werth Charles J.
Published: November 2012

To understand nitrate reduction pathway and to improve selectivity towards dinitrogen (N2) over toxic ammonia species (NH4+, NH3), aqueous reduction experiments with an Al2O3‐supported Pd‐In bimetallic catalyst were conducted by using isotope‐labeled nitrite (15NO2−). Nitrite is the first reduction intermediate of nitrate. Experiments were performed using nitrite alone and in combination with unlabeled proposed reduction intermediates (N2O, NO), and using only N2O and NO alone, each as a starting reactant. Use of 15N‐labeled species eliminates interference from ambient N2 when assessing mass balances and product distributions. Simultaneous catalytic reduction of 15NO2− and 14N2O shows no isotope mixing in the final N2 product, demonstrating that N2O does not react with other NO2− reduction intermediates; N2O reduction alone yielded only N2. In contrast, simultaneous catalytic reduction of 15NO2− and 14NO yielded mixed‐labeled 15/14N2 (MW: 29), whereas reduction of 15NO alone yields a mixture N2 and NH4+, the ratio of which varies with initial 15NO concentration. These findings, along with those from a new kinetic model we propose, indicate that highly reactive adsorbed NO (NO*), or other unspecified adsorbed N species (Nads), is a key intermediate involved in determining final product selectivity.
Application of modified particle swarm optimization as an efficient variable selection strategy in QSAR/QSPR studies
Authors: Khajeh Aboozar , Modarress Hamid , Zeinoddini‐Meymand Hamed
Published: November 2012

In this work, we present a novel method combining modified particle swarm optimization (MPSO) and partial least squares (PLS) for selecting a subset of relevant descriptors and building the optimal linear model for quantitative structure–activity relationship (QSAR)/quantitative structure–property relationship (QSPR) studies. The proposed method is applied to the QSPR modeling of the entropy of formation for 1133 different organic compounds. By using the MPSO–PLS approach, three descriptors are selected from a large set of molecular descriptors, and a linear model is developed. Analysis of the results indicates the squared correlation coefficient of 0.9691 for MPSO–PLS model. Thus, MPSO–PLS is a promising technique, which is helpful for developing the QSAR/QSPR models with high accuracy. Copyright © 2012 John Wiley & Sons, Ltd.
Expanding the Applications of the Ilmenite Mineral to the Preparation of Nanostructures: TiO2 Nanorods and their Photocatalytic Properties in the Degradation of Oxalic Acid
Authors: Tao Tao , Chen Ying , Zhou Dan , Zhang Hongzhou , Liu Sanly , Amal Rose , Sharma Neeraj , Glushenkov Alexey M.
Published: November 2012

The mineral ilmenite is one of the most abundant ores in the Earth′s crust and it is the main source for the industrial production of bulk titanium oxide. At the same time, methods to convert ilmenite into nanostructures of TiO2 (which are required for new advanced applications, such as solar cells, batteries, and photocatalysts) have not been explored to any significant extent. Herein, we describe a simple and effective method for the preparation of rutile TiO2 nanorods from ball‐milled ilmenite. These nanorods have small dimensions (width: 5–20 nm, length: 50–100 nm, thickness: 2–5 nm) and possess large specific surface areas (up to 97 m2 g−1). Dissolution/hydrolysis/precipitation is proposed as a growth mechanism. The nanorods were found to have attractive photocatalytic properties in the degradation of oxalic acid. Their photocatalytic activity is close to that of the benchmark Degussa P25 material and better than that of a commercial high‐surface‐area rutile powder.
Remarkable Solvent, Porphyrin Ligand, and Substrate Effects on Participation of Multiple Active Oxidants in Manganese(III) Porphyrin Catalyzed Oxidation Reactions
Authors: Hyun Min Young , Jo Young Dan , Lee Jun Ho , Lee Hong Gyu , Park Hyun Min , Hwang In Hong , Kim Kyeong Beom , Lee Suk Joong , Kim Cheal
Published: November 2012

The participation of multiple active oxidants generated from the reactions of two manganese(III) porphyrin complexes containing electron‐withdrawing and ‐donating substituents with peroxyphenylacetic acid (PPAA) as a mechanistic probe was studied by carrying out catalytic oxidations of cyclohexene, 1‐octene, and ethylbenzene in various solvent systems, namely, toluene, CH2Cl2, CH3CN, and H2O/CH3CN (1:4). With an increase in the concentration of the easy‐to‐oxidize substrate cyclohexene in the presence of [(TMP)MnCl] (1 a) with electron‐donating substituents, the ratio of heterolysis to homolysis increased gradually in all solvent systems, suggesting that [(TMP)MnOOC(O)R] species 2 a is the major active species. When the substrate was changed from the easy‐to‐oxidize one (cyclohexene) to difficult‐to‐oxidize ones (1‐octene and ethylbenzene), the ratio of heterolysis to homolysis increased a little or did not change. [(F20TPP)MnOOC(O)R] species 2 b generated from the reaction of [(F20TPP)MnCl] (1 b) with electron‐withdrawing substituents and PPAA also gradually becomes involved in olefin epoxidation (although to a much lesser degree than with [(TMP)MnOOR] 2 a) depending on the concentration of the easy‐to‐oxidize substrate cyclohexene in all aprotic solvent systems except for CH3CN, whereas MnVO species is the major active oxidant in the protic solvent system. With difficult‐to‐oxidize substrates, the ratio of heterolysis to homolysis did not vary except for 1‐octene in toluene, indicating that a MnVO intermediate generated from the heterolytic cleavage of 2 b becomes a major reactive species. We also studied the competitive epoxidations of cis‐2‐octene and trans‐2‐octene with two manganese(III) porphyrin complexes by meta‐chloroperbenzoic acid (MCPBA) in various solvents under catalytic reaction conditions. The ratios of cis‐ to trans‐2‐octene oxide formed in the reactions of MCPBA varied depending on the substrate concentration, further supporting the contention that the reactions of manganese porphyrin complexes with peracids generate multiple reactive oxidizing intermediates.
Comparative Electrochemical and Photophysical Studies of Tetrathiafulvalene‐Annulated Porphyrins and Their ZnII Complexes: The Effect of Metalation and Structural Variation
Authors: Jana Atanu , Ishida Masatoshi , Kwak Kyuju , Sung Young Mo , Kim Dong Sub , Lynch Vincent M. , Lee Dongil , Kim Dongho , Sessler Jonathan L.
Published: November 2012

A series of tetrathiafulvalene (TTF)‐annulated porphyrins, and their corresponding ZnII complexes, have been synthesized. Detailed electrochemical, photophysical, and theoretical studies reveal the effects of intramolecular charge‐transfer transitions that originate from the TTF fragments to the macrocyclic core. The incremental synthetic addition of TTF moieties to the porphyrin core makes the species more susceptible to these charge‐transfer (CT) effects as evidenced by spectroscopic studies. On the other hand, regular positive shifts in the reduction signals are seen in the square‐wave voltammograms as the number of TTF subunits increases. Structural studies that involve the tetrakis‐substituted TTF–porphyrin (both free‐base and ZnII complex) reveal only modest deviations from planarity. The effect of TTF substitution is thus ascribed to electronic overlap between annulated TTF subunits rather than steric effects. The directly linked thiafulvalene subunits function as both π acceptors as well as σ donors. Whereas σ donation accounts for the substituent‐dependent charge‐transfer transitions, it is the π‐acceptor nature of the appended tetrathiafulvalene groups that dominates the redox chemistry. Interactions between the subunits are also reflected in the square‐wave voltammograms. In the case of the free‐base derivatives that bear multiple TTF subunits, the neighboring TTF units, as well as the TTF⋅+ generated through one‐electron oxidation, can interact with each other; this gives rise to multiple signals in the square‐wave voltammograms. On the other hand, after metalation, the electronic communication between the separate TTF moieties becomes restricted and they act as separate redox centers under conditions of oxidation. Thus only two signals, which correspond to TTF.+ and TTF2+, are observed. The reduction potentials are also seen to shift towards more negative values after metalation, a finding that is considered to reflect an increased HOMO–LUMO gap. To probe the excited‐state dynamics and internal CT character, transient absorption spectral studies were performed. These analyses revealed that all the TTF–porphyrins of this study display relatively short excited‐state lifetimes, which range from 1 to 20 ps. This reflects a very fast decay to the ground state and is consistent with the proposed intramolecular charge‐transfer effects inferred from the ground‐state studies. Complementary DFT calculations provide a mechanistic rationale for the electron flow within the TTF–porphyrins and support the proposed intramolecular charge‐transfer interactions and π‐acceptor effects.
Rapid, General Synthesis of PdPt Bimetallic Alloy Nanosponges and Their Enhanced Catalytic Performance for Ethanol/Methanol Electrooxidation in an Alkaline Medium
Authors: Zhu Chengzhou , Guo Shaojun , Dong Shaojun
Published: November 2012

We have demonstrated a rapid and general strategy to synthesize novel three‐dimensional PdPt bimetallic alloy nanosponges in the absence of a capping agent. Significantly, the as‐prepared PdPt bimetallic alloy nanosponges exhibited greatly enhanced activity and stability towards ethanol/methanol electrooxidation in an alkaline medium, which demonstrates the potential of applying these PdPt bimetallic alloy nanosponges as effective electrocatalysts for direct alcohol fuel cells. In addition, this simple method has also been applied for the synthesis of AuPt, AuPd bimetallic, and AuPtPd trimetallic alloy nanosponges. The as‐synthesized three‐dimensional bimetallic/trimetallic alloy nanosponges, because of their convenient preparation, well‐defined sponge‐like network, large‐scale production, and high electrocatalytic performance for ethanol/methanol electrooxidation, may find promising potential applications in various fields, such as formic acid oxidation or oxygen reduction reactions, electrochemical sensors, and hydrogen‐gas sensors.
Using Two Simple Methods of ArArF Self‐Assembly and Isolation Chromophores to Further Improve the Comprehensive Performance of NLO Dendrimers
Authors: Wu Wenbo , Yu Gui , Liu Yunqi , Ye Cheng , Qin Jingui , Li Zhen
Published: November 2012

Herein, through a combination of divergent and convergent approaches, coupled with the utilization of the powerful Sharpless “click chemistry” reaction, two series of high‐generation nonlinear optical (NLO) dendrimers have been conveniently prepared in high purity and satisfactory yields. Perfluoroaromatic rings and isolation chromophores were introduced to further improve their comprehensive performance. Thanks to the effects of ArArF self‐assembly and the isolation chromophores, coupled with perfect 3D spatial isolation from the highly branched structure of the dendrimer, G5‐PFPh‐NS displayed very large NLO efficiency (up to 257 pm V−1), which is, to the best of our knowledge, the new record highest value reported so far for simple azo chromophore moieties. High‐quality wide optical transparency and good stability were also achieved.
Chemical Adaptability: The Integration of Different Kinds of Matter into Giant Molecular Metal Oxides
Authors: Müller Achim , Merca Alice , Al‐Karawi Ahmed Jasim M. , Garai Somenath , Bögge Hartmut , Hou Guangfeng , Wu Lixin , Haupt Erhard T. K. , Rehder Dieter , Haso Fadi , Liu Tianbo
Published: November 2012

Unique properties of the two giant wheel‐shaped molybdenum‐oxides of the type {Mo154}≡[{Mo2}{Mo8}{Mo1}]14 (1) and {Mo176}≡[{Mo2}{Mo8}{Mo1}]16 (2) that have the same building blocks either 14 or 16 times, respectively, are considered and show a “chemical adaptability” as a new phenomenon regarding the integration of a large number of appropriate cations and anions, for example, in form of the large “salt‐like” {M(SO4)}16 rings (M=K+, NH4+), while the two resulting {Mo146 (K(SO4))16} (3) and {Mo146 (NH4(SO4))16} (4) type hybrid compounds have the same shape as the parent ring structures. The chemical adaptability, which also allows the integration of anions and cations even at the same positions in the {Mo4O6}‐type units of 1 and 2, is caused by easy changes in constitution by reorganisation and simultaneous release of (some) building blocks (one example: two opposite orientations of the same functional groups, that is, of H2O{MoO} (I) and O{Mo(H2O)} (II) are possible). Whereas Cu2+ in [(H4CuII5)MoV28MoVI114O432(H2O)58]26− (5 a) is simply coordinated to two parent O2− ions of {Mo4O6} and to two fragments of type II, the SO42− integration in 3 and 4 occurs through the substitution of two oxo ligands of {Mo4O6} as well as two H2O ligands of fragment I. Complexes 3 and now 4 were characterised by different physical methods, for example, solutions of 4 in DMSO with sophisticated NMR spectroscopy (EXSY, DOSY and HSQC). The NH4+ ions integrated in the cluster anion of 4 “communicate” with those in solution in the sense that the related H+ ion exchange is in equilibrium. The important message: the reported “chemical adaptability” has its formal counterpart in solutions of “molybdates”, which can form unique dynamic libraries containing constituents/building blocks that may form and break reversibly and can lead to the isolation of a variety of giant clusters with unusual properties.
Superacidic or Not…︁? Synthesis, Characterisation, and Acidity of the Room‐Temperature Ionic Liquid [C(CH3)3]+ [Al2Br7]−
Authors: Scholz Franziska , Himmel Daniel , Scherer Harald , Krossing Ingo
Published: November 2012

The room‐temperature ionic liquid (RT‐IL) [C(CH3)3]+ [Al2Br7]− (m.p. 2 °C) was generated by bromide abstraction from tert‐butyl bromide with the Lewis acid aluminum bromide in the absence of solvent. The crystal structure of the tert‐butyl cation salt was determined by X‐ray diffraction. NMR, IR, and Raman spectroscopy, as well as quantum‐chemical and thermodynamic calculations, confirm the composition of this RT‐IL. Thus, one may consider this RT‐IL to be a readily accessible (and on a large scale) cationic Brønsted acid (protonated isobutene) with the potential for further reactivity. Based on the new absolute Brønsted acidity scale, we calculated an absolute pHabs value of 171 for liquid bulk [C(CH3)3]+ [Al2Br7]−. This value is about as acidic as 100 % sulfuric acid (pHabs=171) and, thus, on the edge of superacidity.
Heteroleptic [n]Chromoarenophanes: ansa Complexes Derived from [Cr(η5‐C5H5)(η6‐C6H6)]
Authors: Braunschweig Holger , Breher Frank , Capper Sabrina , Dück Klaus , Fuß Marco , Jimenez‐Halla J. Oscar C. , Krummenacher Ivo , Kupfer Thomas , Nied Dominik , Radacki Krzysztof
Published: November 2012

The synthesis of ansa complexes has been studied intensively owing to their importance as homogeneous catalysts and as precursors of metal‐containing polymers. However, paramagnetic non‐metallocene derivatives are rare and have been limited to examples with vanadium and titanium. Herein, we report an efficient procedure for the selective dilithiation of paramagnetic sandwich complex [Cr(η5‐C5H5)(η6‐C6H6)], which allows the preparation of a series of [n]chromoarenophanes (n=1, 2, 3) that feature silicon, germanium, and tin atoms at the bridging positions. The electronic and structural properties of these complexes were probed by X‐ray diffraction analysis, cyclic voltammetry, and by UV/Vis and EPR spectroscopy. The spectroscopic parameters for the strained and less strained complexes (i.e., with multiple‐atom linkers) indicate that the unpaired electron resides primarily in a d orbital on chromium(I); this result was also supported by density functional theory (DFT) calculations. We did not observe a correlation between the experimental UV/Vis and EPR data and the degree of molecular distortion in these ansa complexes. The treatment of tin‐bridged complex [Cr(η5‐C5H4)(η6‐C6H5)SntBu2] with [Pt(PEt3)3] results in the non‐regioselective insertion of the low‐valent Pt0 fragment into the CipsoSn bonds in both the five‐ and six‐membered rings, thereby furnishing a bimetallic complex. This observed reactivity suggests that ansa complexes of this type are promising starting materials for the synthesis of bimetallic complexes in general and also underline their potential to undergo ring‐opening processes to yield new metal‐containing polymers.
Novel Electrochemical Method for the Characterization of the Degree of Chirality in Chiral Polyaniline
Authors: Feng Zhang , Li Ma , Yan Yang , Jihai Tang , Xiao Li , Wanglin Li
Published: November 2012

A novel method to indicate the degree of chirality in polyaniline (PANI) was developed. The ( d‐camphorsulfonic acid)‐ and (HCl)‐PANI‐based electrodes exhibited significantly different electrochemical performances in d‐ and l‐Alanine (Ala) aqueous solution, respectively, which can be used for the characterization the optical activity of chiral PANI. Cyclic voltammogram, tafel, and open circuit potential of PANI‐based electrodes were measured within d‐ and l‐Ala electrolyte solution, respectively. The open circuit potentials under different reacting conditions were analyzed by Doblhofer model formula, in which [C+]poly1/[C+]poly2 was used as a parameter to characterize the degree of chirality in chiral PANI. The results showed that [C+]poly1/[C+]poly2 can be increased with increasing concentrations of (1S)‐(+)‐ and (1R)‐(−)‐10‐camphorsulfonic acid. In addition, we detected that appropriate response time and lower temperature are necessary to improve the degree of chirality. Chirality 25:39‐42, 2013.© 2012 Wiley Periodicals, Inc.
Coupling of Azomethine Ylides with Nitrilium Derivatives of closo‐Decaborate Clusters: A Synthetic and Theoretical Study
Authors: Mindich Aleksey L. , Bokach Nadezhda A. , Kuznetsov Maxim L. , Haukka Matti , Zhdanov Andrey P. , Zhizhin Konstantin Yu. , Miltsov Serguei A. , Kuznetsov Nikolay T. , Kukushkin Vadim Yu.
Published: November 2012

The azomethine ylides p‐R3C5H4N+CH−COC6H4R2‐p (3 a: R3=H, R2=H, X=Br; 3 b: R3=H, R2=Me, X=I; 3 c: R3=H, R2=OMe, X=I; 3 d: R3=H, R2=F, X=I; 3 e: R3=Me, R2=Me, X=Br) react with the nitrile functionality of the closo‐decaborate clusters [Bun4N][B10H9(NCR1)] (1 a: R1=Me; 1 b: R1=Et; 1 c: R1=Ph) in a CH3NO2 solution under mild conditions (20–25 °C, 2 min) to afford selectively products of the nucleophilic addition (ca. quantitative yields based on NMR analysis in [D6]DMSO, 71–87 % yield of isolated products). These products are the borylated enamino ketones as the salts bearing exclusively a tetrabutylammonium cation [Bun4N][B10H9{NCR1=C(N+C5H4R3‐p)COC6H4R2‐p}] (4 a–h,k–n) or the mixed salts [Bun4N]1‐x[p‐R3C5H4N+CH2COC6H4R2‐p]x[B10H9{NCR1=C(N+C5H4R3‐p)COC6H4R2‐p}] (4 i, 4 j, and 4 o). This reaction represents the first example of the selective nucleophilic addition of pyridinium azomethine ylides to the nitrile group and the first example of new CC bond formation in the reaction of nitrilium derivatives of boron clusters with any nucleophiles so far tested. Compounds 4 a–h,k–n were characterized by ICP‐MS, high resolution ESI‐MS, molar conductivity, and IR, 1H, 13C{1H}, and 11B{1H} NMR spectroscopy. The structures of 4 a and 4 b were determined by a single‐crystal X‐ray analysis. Theoretical calculations at the DFT level allowed the interpretation of the observed reaction selectivity, which is driven mostly by thermodynamic rather than kinetic factors, and steric repulsion between the boron cluster and the azomethine ylide molecule plays a crucial role. The activation of the nitrile group upon binding to the boron cluster is explained in terms of the electrostatic arguments. The mechanisms of the nucleophilic addition and the hypothetical cycloaddition between the azomethine ylide and nitriles were investigated in detail.
The challenges of statistical patterns of language: The case of Menzerath's law in genomes
Authors: Ferrer‐I‐Cancho Ramon , Forns Núria , Hernández‐Fernández Antoni , Bel‐enguix Gemma , Baixeries Jaume
Published: November 2012

The importance of statistical patterns of language has been debated over decades. Although Zipf's law is perhaps the most popular case, recently, Menzerath's law has begun to be involved. Menzerath's law manifests in language, music and genomes as a tendency of the mean size of the parts to decrease as the number of parts increases in many situations. This statistical regularity emerges also in the context of genomes, for instance, as a tendency of species with more chromosomes to have a smaller mean chromosome size. It has been argued that the instantiation of this law in genomes is not indicative of any parallel between language and genomes because (a) the law is inevitable and (b) noncoding DNA dominates genomes. Here mathematical, statistical, and conceptual challenges of these criticisms are discussed. Two major conclusions are drawn: the law is not inevitable and languages also have a correlate of noncoding DNA. However, the wide range of manifestations of the law in and outside genomes suggests that the striking similarities between noncoding DNA and certain linguistics units could be anecdotal for understanding the recurrence of that statistical law. © 2012 Wiley Periodicals, Inc. Complexity, 2012
A genetic‐based cognitive link decision algorithm for OFDM system
Authors: Tan Xiaobo , Zhang Hang , Liu Zhiwen , Hu Jian
Published: November 2012

To solve the problem of cognitive link decision for OFDM system in a time‐varying environment, an improved genetic algorithm‐based decision‐making module is proposed. At first, the decision‐making module collects the environmental information and QoS requirements of the radio and then produces link configuration for the radio on the basis of the improved genetic algorithm. New crossover and mutation strategies are introduced to accelerate convergence rate of the genetic algorithm. A novel population initialization method is also proposed to reduce the time of achieving the optimal decision by the decision‐making module when the radio is operated in a slow changeable environment. Simulations and discussions demonstrate the effectiveness of the decision‐making module, and this research work exhibits its importance of enhancing the decision speed that is of crucial demand in cognitive decision‐making applications. Copyright © 2012 John Wiley & Sons, Ltd.
Multiple evolutionary processes drive the patterns of genetic differentiation in a forest tree species complex
Authors: Jones Rebecca C. , Steane Dorothy A. , Lavery Martyn , Vaillancourt René E. , Potts Brad M.
Published: November 2012

Forest trees frequently form species complexes, complicating taxonomic classification and gene pool management. This is certainly the case in Eucalyptus, and well exemplified by the Eucalyptus globulus complex. This ecologically and economically significant complex comprises four taxa (sspp. bicostata, globulus, maidenii, pseudoglobulus) that are geographically and morphologically distinct, but linked by extensive “intergrade” populations. To resolve their genetic affinities, nine microsatellites were used to genotype 1200 trees from throughout the natural range of the complex in Australia, representing 33 morphological core and intergrade populations. There was significant spatial genetic structure (FST = 0.10), but variation was continuous. High genetic diversity in southern ssp. maidenii indicates that this region is the center of origin. Genetic diversity decreases and population differentiation increases with distance from this area, suggesting that drift is a major evolutionary process. Many of the intergrade populations, along with other populations morphologically classified as ssp. pseudoglobulus or ssp. globulus, belong to a “cryptic genetic entity” that is genetically and geographically intermediate between core ssp. bicostata, ssp. maidenii, and ssp. globulus. Geography, rather than morphology, therefore, is the best predictor of overall genetic affinities within the complex and should be used to classify germplasm into management units for conservation and breeding purposes.
IL‐2 promotes the function of memory‐like autoregulatory CD8+T cells but suppresses their development via FoxP3+Treg cells
Authors: Shameli Afshin , Yamanouchi Jun , Tsai Sue , Yang Yang , Clemente‐Casares Xavier , Moore Anna , Serra Pau , Santamaria Pere
Published: November 2012

IL‐2 plays a critical role in both effector T‐cell development and FoxP3+CD4+ Treg‐cell homeostasis. A reduction in Il2 transcription results in impaired FoxP3+CD4+ Treg‐cell recruitment and function, and accounts for the association between murine Il2 and type 1 diabetes (T1D). The progression of T1D elicits a disease‐countering negative feedback regulatory loop that involves the differentiation of low‐avidity autoreactive CD8+ T cells into memory‐like autoregulatory T cells in a CD4+ Th‐dependent manner. Since these auto‐regulatory T cells express IL‐2Rβ (CD122), we hypothesized that their development might also be regulated by IL‐2. Here, we investigate the effects of differences in IL‐2 expression on this autoregulatory subset. We show that decreased IL‐2 production impairs the regulatory capacity of memory‐like autoregulatory CD8+CD122+ T cells. Surprisingly, we also find that a reduction in IL‐2 production capacity increases memory autoregulatory CD8+ T‐cell formation indirectly, by decreasing the development and function of FoxP3+ Treg cells in nonobese diabetic mice. These results illustrate a complex homeostatic interplay between IL‐2, CD4+ Th cells, FoxP3+CD4+ Treg cells and autoregulatory CD8+ T‐cell memory whereby IL‐2 controls the function of both Treg‐cell subsets, but IL‐2‐potentiation of FoxP3+CD4+ Treg‐cell function results in the suppression of CD4+ Th‐cell activation and autoregulatory memory CD8+ T‐cell formation.