bluuebunny/crossref_metadata_2025 huggingface dataset:
Horizontal circulation and jumps in Hamiltonian wave models
Authors: Gagarina E. , van der Vegt J. , Bokhove O.
Published: July 2013

Abstract. We are interested in the modelling of wave-current interactions around surf zones at beaches. Any model that aims to predict the onset of wave breaking at the breaker line needs to capture both the nonlinearity of the wave and its dispersion. We have therefore formulated the Hamiltonian dynamics of a new water wave model, incorporating both the shallow water and pure potential flow water wave models as limiting systems. It is based on a Hamiltonian reformulation of the variational principle derived by Cotter and Bokhove (2010) by using more convenient variables. Our new model has a three-dimensional velocity field consisting of the full three-dimensional potential velocity field plus extra horizontal velocity components. This implies that only the vertical vorticity component is nonzero. Variational Boussinesq models and Green–Naghdi equations, and extensions thereof, follow directly from the new Hamiltonian formulation after using simplifications of the vertical flow profile. Since the full water wave dispersion is retained in the new model, waves can break. We therefore explore a variational approach to derive jump conditions for the new model and its Boussinesq simplifications.
Mobile Robot for Life Science Automation
Authors: Liu Hui , Stoll Norbert , Junginger Steffen , Thurow Kerstin
Published: July 2013

The paper presents a control system for mobile robots in distributed life science laboratories. The system covers all technical aspects of laboratory mobile robotics. In this system: (a) to get an accurate and low-cost robot localization, a method using a StarGazer module with a number of ceiling landmarks is utilized; (b) to have an expansible communication network, a standard IEEE 802.11g wireless network is adopted and a XML-based command protocol is designed for the communication between the remote side and the robot board side; (c) to realize a function of dynamic obstacle measurement and collision avoidance, an artificial potential field method based on a Microsoft Kinect sensor is used; and (d) to determine the shortest paths for transportation tasks, a hybrid planning strategy based on a Floyd algorithm and a Genetic Algorithm (GA) is proposed. Additionally, to make the traditional GA method suitable for the laboratory robot's routing, a series of optimized works are also provided in detail. Two experiments show that the proposed system and its control strategy are effective for a complex life science laboratory.
Dimensional Analysis of Acid Etching Effects on Vertically Grown Carbon Nanofibers Using Atomic Force Microscopy
Authors: Wejinya Uchechukwu C. , Chalamalasetty Siva Naga Sandeep , Dong Zhuxin , Meyyappan Meyya , Iyuke Sunny E.
Published: July 2013

This paper presents a discrete-time decentralized control scheme for trajectory tracking of a two degrees of freedom (DOF) robot manipulator. A high order neural network (HONN) is used to approximate a decentralized control law designed by the backstepping technique as applied to a block strict feedback form (BSFF). The weights for each neural network are adapted online by an extended Kalman filter training algorithm. The motion for each joint is controlled independently using only local angular position and velocity measurements. The stability analysis for the closed-loop system via the Lyapunov approach is included. Finally, the real-time results show the feasibility of the proposed control scheme robot manipulator.
Cultural Contexts of Domestic and Juvenile Violence: A Cross-Cultural Perspective from Germany, Turkey and Norway
Authors: Uslucan Haci-Halil
Published: July 2013

The use of violence by parents in child rearing and acts of juvenile violence, which are often intertwined, up to the present day represent serious developmental, cultural and practical challenges, although the rates of domestic violence show a slight decrease in many European countries. This study examines three selected countries, Norway, Germany and Turkey, on the extent to which experiences of domestic violence and harsh parenting are associated with juvenile violence. For this purpose, 386 German, 386 Turkish and 322 Norwegian juveniles (aged 13 to 20 years) were interviewed at schools in Magdeburg, Germany (in the former GDR), Kayseri (Turkey), and Oslo and Tönsberg (Norway) from June 2001 to April 2002, using a standardised questionnaire with 5-point Likert-rating scales. The scales measured maternal violence within the home, family climate, personal and familial risks and variables of juvenile violence (e.g., acceptance of violence, perpetrating violence, and victimisation). The results of this cross-cultural study show significant differences between the three countries examined here regarding both active juvenile violence and the acceptance of violence. Furthermore, both the experience of domestic violence as well as the climate within the family unit points out remarkable differences. Lastly, the results of multiple regression analyses reveals that the proposed model, in which maternal domestic violence, irritability and gender were the predictors of juvenile violence, could explain a great range of variance, especially among German juveniles.
Des dialectiques relatives aux médias et à la culture dans la francophonie canadienne
Authors: Laflamme Simon
Published: July 2013

La culture, dans son sens sociologique, est le résultat d’une dialectique toujours en cours entre des symboliques et des ensembles d’individus, d’une part, et entre des individus entre eux et des collectifs entre eux, d’autre part; elle est information et communication. Dans les sociétés hautement définies par les moyens de communication de masse, cette dialectique non seulement est-elle mouvement continu, mais elle est encore pluralité. Cette pluralité remet en cause la possibilité même de l’identité sociale. S’opère ainsi une autre dialectique, celle-ci entre homogénéisation et différenciation. Les médias constituent l’un des facteurs les plus déterminants des symboliques, et donc des identités. Les messages qu’ils émettent sont soumis aux diverses contraintes de la concurrence, notamment à celles de l’économie et de la démographie, mais aussi à celles de la représentation et de la dialectique entre les producteurs de message et leurs destinataires. Une collectivité, dans la contemporanéité, ne peut se reproduire que dans la mesure où elle évolue dans ce complexe. C’est ce dont nous tenterons de rendre compte en mettant l’accent sur la francophonie canadienne.
Récit de Soi médiatique et identitaire. La Liberté entre francisation, rentrée scolaire, discipline et éloge
Authors: Valenti Jean
Published: July 2013

Cet article porte sur la rubrique « Dans nos écoles » du journal franco-manitobain La Liberté (2006-2008). L’auteur vise à montrer que le récit de soi y explore certaines stratégies de reconnaissance identitaires au croisement de l’individuel et du social. Il insiste sur les figures de la francisation, de la rentrée scolaire et de la discipline en milieu scolaire, tout en montrant que la dialectique de soi et de l’autre y ouvre un parcours symbolique à la faveur duquel l’autre de la culture franco-manitobaine (le monde anglophone) s’énonce implicitement. À ce titre, le récit de soi, comme forme narrative, constitue un lieu de médiations et de mémoire. Afin de mieux préciser son objet de recherche, l’auteur propose d’entrée de jeu une synthèse des travaux menés sur l’identité dans quelques champs disciplinaires en sciences humaines et sociales. Cette synthèse permet non seulement de mettre en relief la complexité du concept d’identité, mais aussi quelques idées directrices sans lesquelles celui-ci demeure perméable à tous les abus conceptuels.
Influence of TiCl4Treatment on Structure and Performance of Dye-Sensitized Solar Cells
Authors: Sedghi Arman , Miankushki Hoda Nourmohammadi
Published: July 2013

Titanium dioxide (TiO2) electrodes are vital components for the fabrication of dye-sensitized solar cells (DSSC). Titanium tetrachloride (TiCl4) treatment is usually adopted as a pre- or post-treatment for the improvement of TiO2electrodes in DSSCs. Previous reports associated these treatments with the improvement of bonding strength between the fluorinated tin oxide (FTO) substrate and the porous TiO2layer, blocking the charge recombination at the interface between the FTO and electrolyte, but pre- and post-treatment effects were not studied simultaneously. In this study, three types of TiO2electrode, untreated, post-treated, and pre- and post-treated, were fabricated. After the TiCl4treatment of TiO2electrodes, they were immersed in a dye solution and cells were assembled. Cell performance was measured using a solar light simulator at an intensity of 1000 W·m-2. The best result was achieved by the pre- and post-treated TiO2electrode. The performance of the cell was improved by increasing the thickness of electrodes and this would raise the overall conversion efficiency up to 7.5%.
Genotype Imputation in Genome‐Wide Association Studies
Authors: Porcu Eleonora , Sanna Serena , Fuchsberger Christian , Fritsche Lars G.
Published: July 2013

Imputation is an in silico method that can increase the power of association studies by inferring missing genotypes, harmonizing data sets for meta‐analyses, and increasing the overall number of markers available for association testing. This unit provides an introductory overview of the imputation method and describes a two‐step imputation approach that consists of the phasing of the study genotypes and the imputation of reference panel genotypes into the study haplotypes. Detailed steps for data preparation and quality control illustrate how to run the computationally intensive two‐step imputation with the high‐density reference panels of the 1000 Genomes Project, which currently integrates more than 39 million variants. Additionally, the influence of reference panel selection, input marker density, and imputation settings on imputation quality are demonstrated with a simulated data set to give insight into crucial points of successful genotype imputation. Curr. Protoc. Hum. Genet. 78:1.25.1‐1.25.14. © 2013 by John Wiley & Sons, Inc.
Single Nucleotide Polymorphism Genotyping Using BeadChip Microarrays
Authors: Lambert Gilliam , Tsinajinnie Darwin , Duggan David
Published: July 2013

The genotyping of single nucleotide polymorphisms (SNPs) has successfully contributed to the study of complex diseases more than any other technology to date. Genome‐wide association studies (GWAS) using 10,000s to >1,000,000 SNPs have identified 1000s of statistically significant SNPs pertaining to 17 different human disease and trait categories. Post‐GWAS fine‐mapping studies using 10,000s to 100,000s SNPs on a microarray have narrowed the region of interest for many of these GWAS findings; in addition, independent signals within the original GWAS region have been identified. Focused content, SNP‐based microarrays such as the human exome, for example, have too been used successfully to identify novel disease associations. Success has come to studies where 100s to 10,000s (mostly) to >100,000 samples were genotyped. For the time being, SNP‐based microarrays remain cost‐effective especially when studying large numbers of samples compared to other “genotyping” technologies including next generation sequencing. In this unit, protocols for manual (LIMS‐free), semi‐manual, and automated processing of BeadChip microarrays are presented. Lower throughput studies will find value in the manual and semi‐manual protocols, while all types of studies‐‐‐low‐, medium‐, and high‐throughput‐‐‐will find value in the semi‐manual and automated protocols. Curr. Protoc. Hum. Genet. 78:2.9.1‐2.9.34. © 2013 by John Wiley & Sons, Inc.
Superhydrophobic Polymers
Authors: Wolfs Mélanie , Darmanin Thierry , Guittard Frédéric
Published: July 2013

Antiwetting materials have been widely studied because of their potential applications in several fields. Polymeric materials are of special interest because they provide advantages including ease of processability and cost. This article introduces basic wetting theories and overviews the main techniques to produce superhydrophobic polymers, such as templating, molding, self‐assembly, soft lithography, layer‐by‐layer deposition, precipitation and crystallization, electrospinning, and electrochemical polymerization. For each method, representative examples as well as practical advantages and disadvantages are also presented.
Variation and Distribution: Forest Patterns as a Model for Urban Morphologies
Authors: Greenberg Evan , Jeronimidis George
Published: July 2013

What can we learn from the spatial logic of collections of trees in the rainforest? Evan Greenberg of the EmTech programme at the Architectural Association (AA) School of Architecture in London and George Jeronimidis of the Centre for Biomimetics at the University of Reading combine forces to analyse the rainforest's morphology and its potential as an urban model. They suggest how the sectional height differentiation of trees could present a new way of thinking about urban organisation, accommodating varied microclimates, programmes and the city's infrastructural flows.
A History of Territories, Movements and Borders: Politics of Inhabitation
Authors: Lathouri Marina
Published: July 2013

If the city is as much about culture as nature, then a cultural understanding of the shaping of the urban is as essential as a scientific one. Here, architect and critic Marina Lathouri, who directs the graduate programme in History and Critical Thinking at the Architectural Association (AA) School of Architecture in London, describes how the concept of planning in the 19th century became intrinsically linked to notions of territory, borders and spatial organisation. She questions whether this might now be tested, and new design technologies used, to expose underlying emerging patterns of disruptive flows beckoning the possibility of the logic of a new social disposition.
Cities and Grids: In Search of New Paradigms
Authors: Busquets Joan
Published: July 2013

The wider global influences of expanded populations, new technologies and economies in both Europe and the Far East are having a direct impact on the pattern and planning of urban form. Joan Busquets, the principal of B Arquitectura I Urbanisme (BAU) in Barcelona, and Professor in Practice of Urban Planning and Design at Harvard Graduate School of Design (GSD), describes how the urban grid is continuing to evolve with these changes, becoming ‘a matrix for innovation within urban development, allowing the creation of sustainable and compact cities’, enabling the forming of ‘new networks and innovative city systems’.
The Grounds of a Renewed Practice: Groundlab's Approach Towards Landscape and Infrastructure
Authors: Castro Eva , Ramírez José Alfredo , Rico Eduardo
Published: July 2013

Based in London and Beijing, Groundlab is an emerging international practice that specialises in landscape urbanism. Eva Castro, José Alfredo Ramírez and Eduardo Rico of Groundlab describe the potential that the ground itself provides for a new urbanism, which is able to integrate multiple fields and scales while also engaging with greater territorial systems. They explain how landscape architect Frederick Law Olmsted was influential in establishing an approach that uses ecological infrastructure as the basis for design. They proceed in describing two Groundlab projects that integrate ground remediation and water infrastructure techniques: Paisajes Latentes urban design masterplan for Valle De Chalco Solidaridad in Mexico City (2011) and the Ground Ecologies masterplan for the redevelopment of the Jiading District in Shanghai (2010).
Networks and the City
Authors: Valverde Sergi , Solé Ricard V
Published: July 2013

‘Cities need to change to survive. As living beings that are constantly replacing their cells, rebuilding their veins and arteries, and pumping energy and matter or producing waste, cities are also growing and evolving as they age.’ Just how complex, though, are cities? Sergi Valverde and Ricard V Solé of the ICREA‐Complex Systems Lab at the Universitat Pompeu Fabra in Barcelona look at how network theory and emergent dynamics might be bringing us closer to an overarching theory of urban organisation.
Atomic‐Scale Visualization of Polarization Pinning and Relaxation at Coherent BiFeO3/LaAlO3 Interfaces
Authors: Huang Rong , Ding Hang‐Chen , Liang Wen‐I , Gao Yong‐Chao , Tang Xiao‐Dong , He Qing , Duan Chun‐Gang , Zhu Ziqiang , Chu Junhao , Fisher Craig A. J. , Hirayama Tsukasa , Ikuhara Yuichi , Chu Ying‐Hao
Published: July 2013

Complex oxide heterointerfaces, which play host to an incredible variety of interface physical phenomena, are of great current interest in introducing new functionalities to systems. Here, coherent super‐tetragonal BiFeO3/LaAlO3 and rhombohedral BiFeO3/LaAlO3 heterointerfaces are investigated by using a combination of high‐angle annular dark‐field (HAADF) imaging and annular bright‐field (ABF) imaging in a spherical aberration (Cs) corrected scanning transmission electron microscope (STEM), and first‐principles calculations. The complicated ferroelectric polarization pinning and relaxation that occurs at both interfaces is revealed with atomic resolution, with a dramatic change in structure of BiFeO3, from cubic to super‐tetragonal‐like. The results enable a detailed explanation to be given of how non‐bulk phase structures are stabilized in thin films of this material.
Cyclometallated Gold(III) Complexes as Effective Catalysts for Synthesis of Propargylic Amines, Chiral Allenes and Isoxazoles
Authors: Kung Karen Ka‐Yan , Lo Vanessa Kar‐Yan , Ko Hok‐Ming , Li Gai‐Li , Chan Pui‐Ying , Leung King‐Chi , Zhou Zhongyuan , Wang Ming‐Zhong , Che Chi‐Ming , Wong Man‐Kin
Published: July 2013

A series of cyclometallated gold(III) complexes [Au($\widehat{CN}$)Cl2] 1a–l (H$\widehat{CN}$=arylpyridines) and a PEG‐linked complex 1m were synthesized. Complexes 1a–m are effective in catalyzing the synthesis of propargylic amines, chiral allenes and isoxazoles. Six‐membered ring cyclometallated gold(III) complexes 1f–l exhibited higher catalytic activity than five‐membered ring cyclometallated gold(III) complexes 1a–e. The diastereoselectivity of propargylic amines could be tuned by using chiral aldehyde and/or amine substrates. Excellent enantioselectivities (90–98% ee) were achieved in chiral allene synthesis. Chiral allene racemization could be minimized by using 1f as catalyst. The PEG‐linked catalyst 1m is the most catalytically active towards synthesis of propargylic amines, in which case a product turnover of 900 was achieved. Moreover, 1m could be repeatedly used for 12 reaction cycles, leading to an overall turnover number of 872.
Polystyrene‐Supported N‐Heterocyclic Carbene–Silver Complexes as Robust and Efficient Catalysts for the Reaction of Carbon Dioxide and Propargylic Alcohols
Authors: Tang Xiaodong , Qi Chaorong , He Haitao , Jiang Huanfeng , Ren Yanwei , Yuan Gaoqing
Published: July 2013

Three polystyrene‐supported N‐heterocyclic carbene–silver complexes [PS‐NHC‐Ag(I)] and a polystyrene‐supported N‐heterocyclic carbene–copper complex [PS‐NHC‐Cu(I)] catalyst were synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy, inductively coupled plasma‐atom emission spectrometer, thermogravimetric analysis and scanning electron micrographs. The catalytic activity of the supported catalysts was investigated for the reaction of propargylic alcohols and carbon dioxide. PS‐NHC‐Cu(I) showed no catalytic activity to the reaction, while PS‐NHC‐Ag(I) showed a considerable high activity and selectivity for the reaction, yielding the corresponding α‐alkylidene cyclic carbonates in high to excellent yields under mild conditions. Most importantly, the supported catalysts could be separated easily from the products and reused up to 15 times without loss of their high catalytic activity, showing excellent stability. The effect of various reaction parameters such as carbon dioxide pressure, temperature, time, and catalyst loading on the reaction was also investigated.
Diastereoselective and Enantioselective Epoxidation of Acyclic β‐Trifluoromethyl‐β,β‐Disubstituted Enones by Hydrogen Peroxide with a Pentafluorinated Quinidine‐Derived Phase‐Transfer Catalyst
Authors: Wu Shaoxiang , Pan Dong , Cao Chengyao , Wang Qi , Chen Fu‐Xue
Published: July 2013

An efficient catalytic asymmetric epoxidation of β‐trifluoromethyl‐β,β‐disubstituted unsaturated ketones has been achieved by a pentafluorine‐substituted phase‐transfer catalyst with hydrogen peroxide (30%). Thus, the β‐trifluoromethyl‐α,β‐epoxy ketones with a quaternary carbon centre were obtained in excellent diastereoselectivities (up to 100:1 dr) and excellent enantioselectivities (up to 99.7% ee). Low catalyst loading, recycle of catalyst, environmentally benign oxidant and easy transformation of the epoxides into medicinally important trifluoromethylated intermediate make our protocol much more practical.
Calcium‐Catalyzed Cycloisomerization of Enynes
Authors: Meyer Vera J. , Fu Liang , Marquardt Fabian , Niggemann Meike
Published: July 2013

A cycloisomerization of enynes with a benign calcium catalyst is presented exploring a complementary reactivity to that usually found in transition and noble metal‐catalyzed reactions. Thereby, a systematic investigation of the π‐activation of alkynes with reactive carbocations has been realized and ketones of various ring sizes were easily accessed. We are certain that these basic investigations will pave the way for the elaboration of further reactions based on the reaction principles discovered in the area of noble metal catalysis.
Room Temperature Ambient Pressure (RTAP)‐Hydroformylation in Water Using a Self‐Assembling Ligand
Authors: Straub Alexander T. , Otto Marina , Usui Ippei , Breit Bernhard
Published: July 2013

We herein demonstrate a hydroformylation at room temperature and ambient pressure (RTAP) using our Rh/6‐DPPon (1) system in aqueous media. The hydrogen bonding network of the ligand backbone stays intact, exemplified by the excellent regioselectivity for the linear aldehyde. Various substrates with different functional groups (with some prone to hydrolysis) are stable under the applied conditions and can undergo hydroformylation resulting in good yields.
Gold(III) Chloride‐Catalyzed 6‐endo‐trig Oxa‐Michael Addition Reactions for Diastereoselective Synthesis of Fused Tetrahydropyranones
Authors: Ciesielski Jennifer , Lebœuf David , Stern Harry A. , Frontier Alison J.
Published: July 2013

Alkynones were treated with boron trifluoride diethyl etherate to generate β‐iodoallenolates, which underwent intramolecular aldol reactions to produce cycloalkenyl alcohols. Diastereoselective oxa‐Michael ring closure could then be induced by treatment with a catalytic amount of gold(III) chloride, affording highly functionalized tetrahydropyranone‐containing ring systems.
Triarylaminium Salt‐Initiated Aerobic Double Friedel–Crafts Reaction of Glycine Derivatives with Indoles
Authors: Huo Congde , Wang Cheng , Sun Chougu , Jia Xiaodong , Wang Xicun , Chang Wenju , Wu Mingxia
Published: July 2013

A novel and efficient stable radical cation triarylaminium salt‐catalyzed aerobic double Friedel–Crafts alkylation reaction of glycine derivatives with indoles has been developed. The reaction was performed in the absence of any other additives under mild conditions and only requires an air atmosphere (or oxygen, 1 atm) as co‐oxidant.
A Catalytic Michael/Horner–Wadsworth–Emmons Cascade Reaction for Enantioselective Synthesis of Thiochromenes
Authors: Choudhury Abhijnan Ray , Mukherjee Santanu
Published: July 2013

A catalytic enantioselective sulfa‐Michael/Horner–Wadsworth–Emmons reaction cascade has been developed, taking advantage of phosphonate as an electrophilic activator and a traceless binding site. Using a chiral bifunctional urea derivative as the catalyst, a variety of aryl and heteroaryl substituted thiochromenes was obtained in excellent yield with a high level of enantioselectivity.
Synthesis of 3,4‐Disubstituted Quinolin‐2‐(1H)‐ones via Palladium‐Catalyzed Decarboxylative Arylation Reactions
Authors: Carrër Amandine , Brion Jean‐Daniel , Messaoudi Samir , Alami Mouad
Published: July 2013

The Pd‐catalyzed decarboxylative cross‐coupling reaction of 4‐substituted quinolin‐2(1H)‐one‐3‐carboxylic acids with (hetero)aryl halides is described. With palladium(II) bromide and triphenylarsine ligand as the catalyst system, a variety of 4‐substituted 3‐(hetero)aryl quinolin‐2(1 H)‐ones and related heterocycles, such as 4‐substituted 3‐arylcoumarins can be prepared in good to excellent yields.
Synthesis of Well‐Defined Diphenylvinyl(cyclopropyl)phosphine‐Palladium Complexes for the Suzuki–Miyaura Reaction and Buchwald–Hartwig Amination
Authors: Yokoyama Naota , Nakayama Yuji , Nara Hideki , Sayo Noboru
Published: July 2013

The well‐defined diphenylvinylphosphine‐palladium complex 1 and the diphenylcyclopropylphosphine‐palladium complex 2 were successfully synthesized. The crystal structures of these complexes were obtained by X‐ray crystallographic analysis. Both complexes were air‐ and moisture‐stable, and could be prepared on a gram scale. These palladium complexes catalyzed the Suzuki–Miyaura reaction of aryl bromides [turnover numbers (TON) up to 196,000] and aryl chlorides (TON up to 50,000). Furthermore, complex 2 catalyzed the Buchwald–Hartwig amination of aryl chlorides and aromatic/aliphatic amines with a low catalyst loading. These complexes showed different reactivities for the coupling of 2‐chloropyridine, and the origin of this difference is discussed.
Adaptive deep brain stimulation in advanced Parkinson disease
Authors: Little Simon , Pogosyan Alex , Neal Spencer , Zavala Baltazar , Zrinzo Ludvic , Hariz Marwan , Foltynie Thomas , Limousin Patricia , Ashkan Keyoumars , FitzGerald James , Green Alexander L. , Aziz Tipu Z. , Brown Peter
Published: July 2013

Objective

Brain–computer interfaces (BCIs) could potentially be used to interact with pathological brain signals to intervene and ameliorate their effects in disease states. Here, we provide proof‐of‐principle of this approach by using a BCI to interpret pathological brain activity in patients with advanced Parkinson disease (PD) and to use this feedback to control when therapeutic deep brain stimulation (DBS) is delivered. Our goal was to demonstrate that by personalizing and optimizing stimulation in real time, we could improve on both the efficacy and efficiency of conventional continuous DBS.

Methods

We tested BCI‐controlled adaptive DBS (aDBS) of the subthalamic nucleus in 8 PD patients. Feedback was provided by processing of the local field potentials recorded directly from the stimulation electrodes. The results were compared to no stimulation, conventional continuous stimulation (cDBS), and random intermittent stimulation. Both unblinded and blinded clinical assessments of motor effect were performed using the Unified Parkinson's Disease Rating Scale.

Results

Motor scores improved by 66% (unblinded) and 50% (blinded) during aDBS, which were 29% (p = 0.03) and 27% (p = 0.005) better than cDBS, respectively. These improvements were achieved with a 56% reduction in stimulation time compared to cDBS, and a corresponding reduction in energy requirements (p < 0.001). aDBS was also more effective than no stimulation and random intermittent stimulation.

Interpretation

BCI‐controlled DBS is tractable and can be more efficient and efficacious than conventional continuous neuromodulation for PD. Ann Neurol 2013;74:449–457
Effect of drug loading and laser surface melting on drug release profile from biodegradable polymer
Authors: Hsu Shan‐Ting , Yao Y. Lawrence
Published: July 2013

The biodegradable polymer such as poly(l‐lactic acid) is promising in drug delivery applications because it allows for drug release in a controlled manner. In a polymer‐based drug delivery system, drug release is controlled by polymer degradation and drug loading concentration. In this study, effect of drug concentration on drug release profile is investigated through polymer crystallinity, chain mobility, and polymer degradation, as characterized by the wide‐angle X‐ray diffraction, differential scanning calorimetry, and gel permeation chromatography, respectively. The addition of drug has been shown to accelerate polymer degradation and drug release rate. With a low drug concentration, the slow polymer degradation kinetics results in an induction period of drug release, during which a limited amount of drug is released. The induction period is undesirable because it delays drug release and effectiveness. Since drug release is controlled by polymer degradation, which is a function of polymer crystallinity, laser surface melting is conducted to reduce polymer surface crystallinity and modify its degradation. The effect of laser crystallinity modification on drug release is investigated. A numerical model is also implemented based on hydrolysis and diffusion mechanisms to investigate the effects of drug loading and laser surface melting on polymer degradation and drug release process. It has been demonstrated that laser treatment shortens the induction period of drug release while keeps the release rate unmodified, as desired in drug delivery applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4147–4156, 2013
The thematic and conceptual flow of disciplinary research: A citation context analysis of the journal of informetrics, 2007
Authors: Halevi Gali , Moed Henk F.
Published: July 2013

This article analyzes the context of citations within the full text of research articles. It studies articles published in a single journal: the Journal of Informetrics (JOI), in the first year the journal was published, 2007. The analysis classified the citations into in‐ and out‐disciplinary content and looked at their use within the articles' sections such as introduction, literature review, methodology, findings, discussion, and conclusions. In addition, it took into account the age of cited articles. A thematic analysis of these citations was performed in order to identify the evolution of topics within the articles sections and the journal's content. A matrix describing the relationships between the citations' use, and their in‐ and out‐disciplinary focus within the articles' sections is presented. The findings show that an analysis of citations based on their in‐ and out‐disciplinary orientation within the context of the articles' sections can be an indication of the manner by which cross‐disciplinary science works, and reveals the connections between the issues, methods, analysis, and conclusions coming from different research disciplines.
Purpurides B and C, Two New Sesquiterpene Esters from the Aciduric Fungus Penicillium purpurogenum JS03‐21
Authors: Wang Hui , Wang Yi , Liu Peipei , Wang Wei , Fan Yaqin , Zhu Weiming
Published: July 2013

Purpurides B and C (1 and 2, resp.), two new sesquiterpene alcohol esters generated from a drimane‐type sesquiterpenoid lactone and an amino acid, together with two known analogs, berkedrimane B (3) and purpuride (4), were isolated from the aciduric fungus Penicillium purpurogenum JS03‐21. Their structures were elucidated by spectroscopic analysis, X‐ray single‐crystal diffraction, and application of Marfey's method. Compounds 1–4 showed modest antifungal activities against Candida albicans with MIC values in the range of 1.2–3.3 μM. Compounds 1 and 2 showed moderate antimicrobial activities against Enterobacter aerogenes and Pseudomonas aeruginosa with MIC values in the range of 1.2–2.6 μM.
Phytochemical Fingerprints of Copaiba Oils (Copaifera multijugaHayne) Determined by Multivariate Analysis
Authors: Souza Barbosa Paula Cristina , Moreira Wiedemann Larissa Silveira , da Silva Medeiros Raquel , de Tarso Barbosa Sampaio Paulo , Vieira Gil , Florêncio da Veiga‐Junior Valdir
Published: July 2013

Oils of various species of Copaifera are commonly found in pharmacies and on popular markets and are widely sold for their medicinal properties. However, the chemical variability between and within species and the lack of standardization of these oils have presented barriers to their wider commercialization. With the aim to recognize patterns for the chemical composition of copaiba oils, 22 oil samples of C. multijuga Hayne species were collected, esterified with CH2N2, and characterized by GC‐FID and GC/MS analyses. The chromatographic data were processed using hierarchical cluster analysis (HCA) and principal component analysis (PCA). In total, 35 components were identified in the oils, and the multivariate analyses (MVA) allowed the samples to be divided into three groups, with the sesquiterpenes β‐caryophyllene and caryophyllene oxide as the main components. These sesquiterpenes, which were detected in all the samples analyzed in different concentrations, were the most important constituents in the differentiation of the groups. There was a prevalence of sesquiterpenes in all the oils studied. In conclusion, GC‐FID and GC/MS analyses combined with MVA can be used to determine the chemical composition and to recognize chemical patterns of copaiba oils.
A Novel MonoterpeneStilbene Adduct with a 4,4‐Dimethyl‐2,3‐diphenylchromane Skeleton from Artocarpus xanthocarpus
Authors: Ko Horng‐Huey , Jin Yu‐Jing , Lu Tzy‐Ming , Chen Ih‐Sheng
Published: July 2013

Artoxanthochromane (1), a DielsAlder‐type conjugation product of 4‐isopropenylresorcinol and oxyresveratrol, was isolated from the heartwood of Artocarpus xanthocarpus and characterized. The structure of 1 was elucidated as 2‐(2,4‐dihydroxyphenyl)‐3‐(3,5‐dihydroxyphenyl)‐7‐hydroxy‐4,4‐dimethylchromane by 1D‐ and 2D‐NMR spectroscopy, and other spectral evidences. A plausible metabolic mechanism was proposed to illustrate the biosynthetic pathway of artoxanthochromane. This compound exhibited mild mushroom tyrosinase inhibitory, and weak free radical‐scavenging activities on ABTS+. and superoxide anion (O$\rm{{_{2}^{-{^\cdot} }}}$) free radicals.
Diastereoselective Synthesis of a Lilac Aldehyde Isomer and Its Electrophysiological Detection by a Moth
Authors: Schneider Marc‐André , Dötterl Stefan , Seifert Karlheinz
Published: July 2013

The monoterpene lilac aldehyde (=2‐(5‐ethenyl‐5‐methyloxolan‐2‐yl)propanal) is a widespread flower scent. Lilac aldehyde is emitted in high amounts from nocturnal plant species, and it is highly attractive to nocturnal moth pollinators, such as Hadena bicruris, the pollinating seed predator of Silene latifolia. Lilac aldehyde possesses three stereogenic centers and can occur in eight stereoisomers which induce different antennal responses in H. bicruris. The distribution pattern of stereoisomers differs among plant species, and if H. bicruris has different receptors for detecting different isomers, it may use these differences to discriminate flowers of S. latifolia hosts from flowers of non‐host plants. To investigate the question whether the moths have in their antennae one olfactory receptor or several different receptors for the detection of the single lilac aldehyde isomers, (2S,2′S,5′S)‐lilac aldehyde was diastereoselectively synthesized. (2S,2′S,5′S)‐Lilac aldehyde and its isomeric mixture were tested electrophysiologically on antennae of H. bicruris. The results displayed antennal responses, which are characteristic for a single receptor that detects the different lilac aldehyde isomers.
A New Cytotoxic Carbazole Alkaloid and Two New Other Alkaloids from Clausena excavata
Authors: Peng Wen‐Wen , Zeng Guang‐Zhi , Song Wei‐Wu , Tan Ning‐Hua
Published: July 2013

One new carbazole alkaloid, excavatine A (1), and two additional new alkaloids, excavatine B (2) and excavatine C (3), were isolated from the stems and leaves of Clausena excavata Burm.f. (Rutaceae). Their structures were determined on the basis of detailed spectroscopic analyses, especially 2D‐NMR and HR‐EI‐MS data. Compounds 1–3 were tested for their cytotoxic activities against A549, HeLa, and BGC‐823 cancer cell lines, and for their antimicrobial activities against Candida albicans and Staphylococcus aureus. Only 1 exhibited cytotoxicity against A549 and HeLa cell lines with the IC50 values of 5.25 and 1.91 μg/ml, respectively.
Unusual Secondary Metabolites from Astragalus halicacabusLam.
Authors: Djimtombaye Basile‐Jimmy , Alankuş‐Çalışkan Özgen , Gülcemal Derya , Khan Ikhlas A. , Anıl Hüseyin , Bedir Erdal
Published: July 2013

From the whole plant of Astragalus halicacabus (Sect. Halicacabus), a new cycloartane‐type glycoside, (20R,24S)‐3‐O‐[α‐L‐arabinopyranosyl‐(1→2)‐β‐D‐xylopyranosyl]‐20,24‐epoxy‐16‐O‐β‐D‐glucopyranosyl‐3β,6α,16β,25‐tetrahydroxycycloartane, and a new glycoside, 3‐O‐[β‐D‐apiofuranosyl‐(1→2)‐β‐D‐glucopyranosyl]maltol were isolated together with seven known cycloartane‐type glycosides, i.e., cyclocanthoside D, askendosides D, F, and G, cyclosieversioside G, cyclostipuloside A, elongatoside, and a known maltol glucoside, 3‐O‐β‐D‐glucopyranosylmaltol. The structures were elucidated by means of high‐resolution mass spectrometry, and extensive 1D‐ and 2D‐NMR spectroscopic analysis. This is the first phytochemical work on A. halicacabus, and a maltol glycoside was encountered for the first time in the Leguminosae family.
Cytotoxic Activities of Amino Acid‐Conjugate Derivatives of Abietane‐Type Diterpenoids against Human Cancer Cell Lines
Authors: Ukiya Motohiko , Kawaguchi Takuma , Ishii Kenta , Ogihara Eri , Tachi Yosuke , Kurita Masahiro , Ezaki Yoichiro , Fukatsu Makoto , Kushi Yasunori , Akihisa Toshihiro
Published: July 2013

Nine amino acid conjugate derivatives, each 2–10 and 12–20, were prepared from abietic acid (1) and dehydroabietic acid (11), respectively, and they were evaluated for their cytotoxicities against four human cancer cell lines, i.e., leukemia (HL60), lung (A549), stomach (AZ521), and breast (SK‐BR‐3). All compounds showed cytotoxicities against HL60 with IC50 values in the range of 2.3–37.3 μM. In addition, most of the derivatives exhibited moderate cytotoxicities against the other cancer cell lines. Among the derivatives, methyl N‐[18‐oxoabieta‐8,11,13‐trien‐18‐yl]‐L‐tyrosinate (19) exhibited potent cytotoxic activities against four cancer cell lines with IC50 values of 2.3 (HL60), 7.1 (A549), 3.9 (AZ521), and 8.1 μM (SK‐BR‐3). Furthermore, all derivatives were shown to possess high selective cytotoxic activities for leukemia cells, since they exhibited only weak cytotoxicities against normal lymphocyte cell line RPMI1788.
A Silyliumylidene Cation Stabilized by an Amidinate Ligand and 4‐Dimethylaminopyridine
Authors: Yeong Hui‐Xian , Xi Hong‐Wei , Li Yongxin , Lim Kok Hwa , So Cheuk‐Wai
Published: July 2013

The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [LSi:]2 (1; L=PhC(NtBu)2) with one equivalent of N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe2C5H4NSiMe3]OTf and two equivalents of DMAP in THF afforded [LSi(DMAP)]OTf (2). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [L′2(L)Si]OTf (3; L′=LSi:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)3}] and elemental sulfur in THF afforded the silylsilylene [LSiSi(H){(NtBu)2C(H)Ph}] (4) and the base‐stabilized silanethionium triflate [LSi(S)DMAP]OTf (5), respectively. Compounds 2, 3, and 5 have been characterized by X‐ray crystallography.
Fluorescent Hydroxylamine Derived from the Fragmentation of PAMAM Dendrimers for Intracellular Hypochlorite Recognition
Authors: Wu Te‐Haw , Liu Ching‐Ping , Chien Chih‐Te , Lin Shu‐Yi
Published: July 2013

Herein, a promising sensing approach based on the structure fragmentation of poly(amidoamine) (PAMAM) dendrimers for the selective detection of intracellular hypochlorite (OCl−) is reported. PAMAM dendrimers were easily disrupted by a cascade of oxidations in the tertiary amines of the dendritic core to produce an unsaturated hydroxylamine with blue fluorescence. Specially, the novel fluorophore was only sensitive to OCl−, one of reactive oxygen species (ROS), resulting in an irreversible fluorescence turn‐off. The fluorescent hydroxylamine was selectively oxidised by OCl− to form a labile oxoammonium cation that underwent further degradation. Without using any troublesomely synthetic steps, the novel sensing platform based on the fragmentation of PAMAM dendrimers, can be applied to detect OCl− in macrophage cells. The results suggest that the sensing approach may be useful for the detection of intracellular OCl− with minimal interference from biological matrixes.
Enantio‐ and Regioselective Conjugate Addition of Organometallic Reagents to Linear Polyconjugated Nitroolefins
Authors: Tissot Matthieu , Alexakis Alexandre
Published: July 2013

The copper‐catalysed conjugate addition of trialkylaluminium and dialkylzinc reagents to polyconjugated nitroolefins (nitrodiene and nitroenyne derivatives) is reported. A reversed Josiphos ligand L7 allows for the selective 1,4‐ or 1,6‐addition with high enantioselectivities.
Super‐Hydrated Zeolites: Pressure‐Induced Hydration in Natrolites
Authors: Seoung Donghoon , Lee Yongmoon , Kao Chi‐Chang , Vogt Thomas , Lee Yongjae
Published: July 2013

High‐pressure synchrotron X‐ray powder diffraction studies of a series of alkali‐metal‐exchanged natrolites, A16Al16Si24O80⋅n H2O (A=Li, K, Na, Rb, and Cs and n=14, 16, 22, 24, 32), in the presence of water, reveal structural changes that far exceed what can be achieved by varying temperature and chemical composition. The degree of volume expansion caused by pressure‐induced hydration (PIH) is inversely proportional to the non‐framework cation radius. The expansion of the unit‐cell volume through PIH is as large as 20.6 % in Li‐natrolite at 1.0 GPa and decreases to 6.7, 3.8, and 0.3 % in Na‐, K‐, and Rb‐natrolites, respectively. On the other hand, the onset pressure of PIH appears to increase with non‐framework cation radius up to 2.0 GPa in Rb‐natrolite. In Cs‐natrolite, no PIH is observed but a new phase forms at 0.3 GPa with a 4.8 % contracted unit cell and different cation–water configuration in the pores. In K‐natrolite, the elliptical channel undergoes a unique overturn upon the formation of super‐hydrated natrolite K16Al16Si24O80⋅32 H2O at 1.0 GPa, a species that reverts back above 2.5 GPa as the potassium ions interchange their locations with those of water and migrate from the hinge to the center of the pores. Super‐hydrated zeolites are new materials that offer numerous opportunities to expand and modify known chemical and physical properties by reversibly changing the composition and structure using pressure in the presence of water.
Synthesis of Polycyclic Aminocyclobutane Systems by the Rearrangement of N‐(ortho‐Vinylphenyl) 2‐Azabicyclo[3.1.0]hexane Derivatives
Authors: Wasilewska Agnieszka , Woźniak Bartosz A. , Doridot Gabriel , Piotrowska Kamila , Witkowska Natalia , Retailleau Pascal , Six Yvan
Published: July 2013

The acid‐catalysed thermal rearrangements of a family of N‐aryl 2‐azabicyclo[3.1.0]hexanes is described. These substrates, designed in such a way that the aromatic system is conjugated with an alkene group located at the ortho position relative to the nitrogen atom, have been prepared by using an intramolecular Kulinkovich–de Meijere reaction. The rearrangements can then be conducted either under standard thermal conditions or with microwave activation. Depending on the conditions applied and the substitution pattern, dihydroquinoline or polycyclic aminocyclobutane derivatives can be obtained. A mechanistic discussion is provided, with the proposition of the initial protonation of the aminocyclopropane moiety to give an iminium intermediate. By analogy with related intermolecular reactions, the involvement of electrocyclic reactions among the series of elementary steps that follow is put forward.
Redox‐Switchable Ring‐Closing Metathesis: Catalyst Design, Synthesis, and Study
Authors: Arumugam Kuppuswamy , Varnado C. Daniel , Sproules Stephen , Lynch Vincent M. , Bielawski Christopher W.
Published: July 2013

High yielding syntheses of 1‐(ferrocenylmethyl)‐3‐mesitylimidazolium iodide (1) and 1‐(ferrocenylmethyl)‐3‐mesitylimidazol‐2‐ylidene (2) were developed. Complexation of 2 to [{Ir(cod)Cl}2] (cod=cis,cis‐1,5‐cyclooctadiene) or [Ru(PCy3)Cl2(CH‐o‐O‐iPrC6H4)] (Cy=cyclohexyl) afforded 3 ([Ir(2)(cod)Cl]) and 5 ([Ru(2)Cl2(CH‐o‐O‐iPrC6H4)]), respectively. Complex 4 ([Ir(2)(CO)2Cl]) was obtained by bubbling carbon monoxide through a solution of 3 in CH2Cl2. Spectroelectrochemical IR analysis of 4 revealed that the oxidation of the ferrocene moiety in 2 significantly reduced the electron‐donating ability of the N‐heterocyclic carbene ligand (ΔTEP=9 cm−1; TEP=Tolman electronic parameter). The oxidation of 5 with [Fe(η5‐C5H4COMe)Cp][BF4] as well as the subsequent reduction of the corresponding product [5][BF4] with decamethylferrocene (Fc*) each proceeded in greater than 95 % yield. Mössbauer, UV/Vis and EPR spectroscopy analysis confirmed that [5][BF4] contained a ferrocenium species, indicating that the iron center was selectively oxidized over the ruthenium center. Complexes 5 and [5][BF4] were found to catalyze the ring‐closing metathesis (RCM) of diethyl diallylmalonate with observed pseudo‐first‐order rate constants (kobs) of 3.1×10−4 and 1.2×10−5 s−1, respectively. By adding suitable oxidants or reductants over the course of a RCM reaction, complex 5 was switched between different states of catalytic activity. A second‐generation N‐heterocyclic carbene that featured a 1′,2′,3′,4′,5′‐ pentamethylferrocenyl moiety (10) was also prepared and metal complexes containing this ligand were found to undergo iron‐centered oxidations at lower potentials than analogous complexes supported by 2 (0.30–0.36 V vs. 0.56–0.62 V, respectively). Redox switching experiments using [Ru(10)Cl2(CH‐o‐O‐iPrC6H4)] revealed that greater than 94 % of the initial catalytic activity was restored after an oxidation–reduction cycle.