bluuebunny/crossref_metadata_2025 huggingface dataset:
Assignment of Counsel for Indigents
Authors: Block Lauren M.
Published: January 2014

Provision of legal counsel for indigent defendants is one of the most important rights given to citizens of the United States. It is an essential guarantee of fair and just court proceedings. An indigent defendant is someone who lacks the financial means to hire his/her own counsel to represent him/her in court. After a series of US Supreme Court decisions, the right to counsel for indigent defendants in criminal cases was recognized and applied to defendants charged with felonies at the state level—more specifically, after the landmark decision inGideon v. Wainwright1963. Indigent defendants may be assigned counsel in a variety of ways. These various methods utilize different funding sources and often suffer from inadequate resources and lack accountability, which may compromise the quality of legal representation.
An ethnographic study of participant roles in school bullying
Authors: Gumpel Thomas P. , Zioni‐Koren Vered , Bekerman Zvi
Published: January 2014

An ethnographic study in a 10th grade remedial class was undertaken in order to discern patterns of school bullying. Twenty 10th graders were observed over the course of one academic year as they interacted with their peers and teachers. The observations helped us identify dispositional and situational factors which influenced participant roles. In‐depth interviews of students involved in school bullying showed how participants interpreted and explained their classroom behaviors. The analysis of the data gathered allowed the identification of four main actor roles recognized in the existing literature on bullying—the pure victim, the pure bully, the provocative‐victim, and the bystander—as well as the differentiation between aggressive bullies and the bully managers. Most roles fluctuated according to specific circumstances and often appeared to be moderated by the teacher's management style and contextual variables. Some pupils assumed different roles in different contexts, sometimes changing roles within or between episodes. Teacher personality and style also had an impact on the frequencies and types of aggression and victimization. The use of an ethnographic research paradigm is discussed as an important supplement to positivistic studies of school bullying. Aggr. Behav. 40:214–228, 2014. © 2014 Wiley Periodicals, Inc.
The animal in you: Animalistic descriptions of a violent crime increase punishment of perpetrator
Authors: Vasquez Eduardo A. , Loughnan Steve , Gootjes‐Dreesbach Ellis , Weger Ulrich
Published: January 2014

Criminal acts are sometimes described using animal metaphors. What is the impact of a violent crime being described in an animalistic versus a non‐animalistic way on the subsequent retribution toward the perpetrator? In two studies, we experimentally varied animalistic descriptions of a violent crime and examined its effect on the severity of the punishment for the act. In Study 1, we showed that compared to non‐animalistic descriptions, animalistic descriptions resulted in significantly harsher punishment for the perpetrator. In Study 2, we replicated this effect and further demonstrated that this harsher sentencing is explained by an increase in perceived risk of recidivism. Our findings suggest that animalistic descriptions of crimes lead to more retaliation against the perpetrator by inducing the perception that he is likely to continue engaging in violence. Aggr. Behav. 40:337–344, 2014. © 2014 Wiley Periodicals, Inc.
Safeguarding Youth Interrogation Rights: The Effect of Grade Level and Reading Complexity of Youth Waiver Forms on the Comprehension of Legal Rights
Authors: Freedman Stuart , Eastwood Joseph , Snook Brent , Luther Kirk
Published: January 2014

The extent to which youths understand their interrogation rights was examined. High school students (N = 160) from five different grades were presented with one of two Canadian youth waiver forms—varying widely in reading complexity—and tested on their knowledge of their legal rights. Results showed that comprehension of both waiver forms was equally deficient, and systematic misunderstandings of vital legal rights were discovered (e.g., the right to remain silent). There was also a positive linear relationship between high school grade level and amount of comprehension. Potential ways to enhance youths' understanding of their rights and provide them protection during interrogations are discussed. Copyright © 2014 John Wiley & Sons, Ltd.
Nanoscale Adhesive Properties of Graphene: The Effect of Sliding History
Authors: Liu Xin‐Z. , Li Qunyang , Egberts Philip , Carpick Robert W.
Published: January 2014

Single‐asperity adhesion between nanoscale silicon tips and few‐layer graphene (FLG) sheets, as well as graphite, was measured using atomic force microscopy (AFM). The adhesion mechanism was understood through experiments and finite element method (FEM) simulations by comparing conventional pull‐forces measurements (contact and separation, without sliding) to those obtained after the tip was slid along the surface before separation (“pre‐sliding”). Without pre‐sliding, no variation in the pull‐off force was measured between consecutive measurements, and there was no observable dependence of the mean pull‐off force value on the number of FLG layers. However, when the tip was pre‐slid over a local area, the first pull‐off force was enhanced by 12–17%; subsequent pull‐off forces then relaxed to a lower, constant value. This occurred regardless of the number of layers, and occurred for aged graphite samples as well. Our analysis indicates that this is due to sliding‐induced changes of graphene's interfacial geometry, whereby local delamination of the top graphene layer occurs, provided there is sufficient atmospheric exposure of the surface after cleaving. This effect provides another unique feature of the nanotribological behavior of atomically‐thin sheets and is consequential for designing graphene‐based devices and coatings where adhesive interactions are important.
Resorption of mandibular alveolar bone following loss of molar teeth and its relationship to age at death in a human skeletal population
Authors: Mays Simon
Published: January 2014

Estimating adult age at death in skeletal remains is problematic, particularly in older adults. Molar wear is arguably the most reliable ageing technique for palaeopopulations, but many older adult skeletons have lost their molar teeth ante mortem, precluding its application. Resorption of the alveolar process occurs following tooth loss, and this appears to continue for a prolonged period. The current work investigates the relationship of this process to individual age in a nineteenth century AD European archaeological skeletal series of known age at death (N = 92 individuals), and discusses its potential as an age indicator. Mandibular corpus height was measured at the different molar positions. In females, reduction of corpus height with age was found at molar positions showing ante mortem loss. In both sexes, a relationship was found between age and a simple composite measure of corpus height in the molar region in those showing ante mortem loss of one or more mandibular molars. The correlation was stronger in females (r = −0.74) than in males (r = −0.49), appeared approximately linear, and continued into the ninth decade, the oldest age group in the study material. The results suggest that investigation of height of the posterior part of the mandibular corpus as a skeletal age indicator for individuals that have lost one or more molar teeth is merited in other palaeopopulations. Am J Phys Anthropol 153:643–652, 2014. © 2014 Wiley Periodicals, Inc.
Ecogeographical and phylogenetic effects on craniofacial variation in macaques
Authors: Ito Tsuyoshi , Nishimura Takeshi , Takai Masanaru
Published: January 2014

The widespread and complex ecogeographical diversity of macaques may have caused adaptive morphological convergence among four phylogenetic subgroups, making their phylogenetic relationships unclear. We used geometric morphometrics and multivariate analyses to test the null hypothesis that craniofacial morphology does not vary with ecogeographical and phylogenetic factors. As predicted by Bergmann's rule, size was larger for the fascicularis and sinica groups in colder environments. No clear size cline was observed in the silenus and sylvanus groups. An allometric pattern was observed across macaques, indicating that as size increases, rounded faces become more elongated. However, the elevation was differentiated within each of the former two groups and between the silenus and sylvanus groups, and the slope decreased in each of the two northern species of the fascicularis group. All allometric changes resulted in the similar situation of the face being more rounded in animals inhabiting colder zones and/or in animals having a larger body size than that predicted from the overarching allometric pattern. For non‐allometric components, variations in prognathism were significantly correlated with dietary differences; variations in localized shape components in zygomatics and muzzles were significantly correlated with phylogenetic differences among the subgroups. The common allometric pattern was probably influenced directly or indirectly by climate‐related factors, which are pressures favoring a more rounded face in colder environments and/or a more elongated face in warmer environments. Allometric dissociation could have occurred several times in Macaca even within a subgroup because of their wide latitudinal distributions, critically impairing the taxonomic utility of craniofacial elongation. Am J Phys Anthropol 154:27–41, 2014. © 2014 Wiley Periodicals, Inc.
Die Supersäure HBr/AlBr3: Protonierung von Benzol und ausgeordnete Kristallstruktur von [C6H7]+[Al2Br7]−
Authors: Scholz Franziska , Himmel Daniel , Eisele Lea , Unkrig Wiebke , Krossing Ingo
Published: January 2014

Die Reaktion von festem AlBr3, Benzol und HBr‐Gas führte zur ausgeordneten Kristallstruktur des protonierten Benzols der Zusammensetzung [C6H7]+[Al2Br7]−⋅(C6H6) (1). Die Verbindung konnte mittels Röntgenstrukturanalyse, NMR‐ und Raman‐Spektroskopie zweifelsfrei nachgewiesen werden. Dieser unerwartet einfache und leicht zugängliche Syntheseweg zeigt, dass HBr/AlBr3 eine Supersäure ist, deren Potential bisher unterschätzt wurde und noch weiter untersucht werden sollte.
SF and SC Activation of SF6 and SF5 Derivatives at Rhodium: Conversion of SF6 into H2S
Authors: Zámostná Lada , Braun Thomas , Braun Beatrice
Published: January 2014

The degradation of SF6 and SF5 organyls by SF and SC bond‐activation reactions at [{Rh(μ‐H)(dippp)}2] under mild conditions is reported. Fluorido and thiolato species were identified as products or intermediates, and were characterized by X‐ray diffraction analysis and multinuclear NMR spectroscopy. An unprecedented cyclic process for the conversion of the potent greenhouse gas SF6 into H2S was developed.
Helical Carbon and Graphite Films Prepared from Helical Poly(3,4‐ethylenedioxythiophene) Films Synthesized by Electrochemical Polymerization in Chiral Nematic Liquid Crystals
Authors: Matsushita Satoshi , Yan Bairu , Yamamoto Shinsuke , Jeong Yong Soo , Akagi Kazuo
Published: January 2014

Helical carbon and graphite films from helical poly(3,4‐ethylenedioxythiophene) (H‐PEDOT) films synthesized through electrochemical polymerization in a chiral nematic liquid‐crystal (N*‐LC) field are prepared. The microscope investigations showed that the H‐PEDOT film synthesized in the N*‐LC has large domains of one‐handed spiral morphology consisting of fibril bundles. The H‐PEDOT films exhibited distinct Cotton effects in circular dichroism spectra. The highly twisted N*‐LC with a helical pitch of smaller than 1 μm produced the H‐PEDOT film with a highly ordered morphology. The spiral morphologies with left‐ and right‐handed screws were observed for the carbon films prepared from the H‐PEDOT films at 800 °C and were well correlated with the textures and helical pitches of the N*‐LCs. The spiral morphologies of the precursors were also retained even in the graphite films prepared from the helical carbon films at 2600 °C.
A General Catalytic Hydroamidation of 1,3‐Dienes: Atom‐Efficient Synthesis of N‐Allyl Heterocycles, Amides, and Sulfonamides
Authors: Banerjee Debasis , Junge Kathrin , Beller Matthias
Published: January 2014

Transition‐metal‐catalyzed hydroamination reactions are sustainable and atom‐economical CN bond‐forming processes. Although remarkable progress has been made in the inter‐ and intramolecular amination of olefins and 1,3‐dienes, related intermolecular reactions of amides are still much less known. Control of the regioselectivity without analogous telomerization is the particular challenge in the catalytic hydroamidation of alkenes and 1,3‐dienes. Herein, we report a general protocol for the hydroamidation of electron‐deficient N‐heterocyclic amides and sulfonamides with 1,3‐dienes and vinyl pyridines in the presence of a catalyst derived from [{Pd(π‐cinnamyl)Cl}2] and ligand L7 or L10. The reactions proceeded in good to excellent yield with high regioselectivity. The practical utility of our method is demonstrated by the hydroamidation of functionalized biologically active substrates. The high regioselectivity for linear amide products makes the procedure useful for the synthesis of a variety of allylic amides.
Supramolecular Protein Assemblies in the Nucleus of Human Cells
Authors: Bellapadrona Giuliano , Elbaum Michael
Published: January 2014

Genetically encoded supramolecular protein assemblies (SMPAs) are induced to form in living cells by combination of distinct self‐assembly properties. A single fusion construct contains genes encoding the heavy chain (H) of human ferritin and the citrine fluorescent protein, the latter exposing a weak dimerization interface, as well as a nuclear localization signal. Upon expression in HeLa cells, in vivo confocal fluorescence and differential interference contrast imaging revealed extended SMPA structures exclusively in the nuclei. Assemblies were typically round and took alveolar, shell‐like, or hybrid structure. Transmission electron microscopy revealed a crystalline packing. Site‐specific mutagenesis of the citrine dimerization interface clarified the mechanism of SMPA formation. The constituent proteins retained their activity in iron binding and fluorescence emission, thus suggesting a general strategy for formation of synthetic cellular bodies with specific biochemical function.
Palladium‐Catalyzed Difluoroalkylation of Aryl Boronic Acids: A New Method for the Synthesis of Aryldifluoromethylated Phosphonates and Carboxylic Acid Derivatives
Authors: Feng Zhang , Min Qiao‐Qiao , Xiao Yu‐Lan , Zhang Bo , Zhang Xingang
Published: January 2014

The palladium‐catalyzed difluoroalkylation of aryl boronic acids with bromodifluoromethylphosphonate, bromodifluoroacetate, and further derivatives has been developed. This method provides a facile and useful access to a series of functionalized difluoromethylated arenes (ArCF2PO(OEt)2, ArCF2CO2Et, and ArCF2CONR1R2) that have important applications in drug discovery and development. Preliminary mechanistic studies reveal that a single electron transfer (SET) pathway may be involved in the catalytic cycle.
Chemoselective Polymerization Control: From Mixed‐Monomer Feedstock to Copolymers
Authors: Romain Charles , Williams Charlotte K.
Published: January 2014

A novel chemoselective polymerization control yields predictable (co)polymer compositions from a mixture of monomers. Using a dizinc catalyst and a mixture of caprolactone, cyclohexene oxide, and carbon dioxide enables the selective preparation of either polyesters or polycarbonates or copoly(ester‐carbonates). The selectivity depends on the nature of the zinc–oxygen functionality at the growing polymer chain end, and can be controlled by the addition of exogeneous switch reagents.
Electron Transfer in a Supramolecular Associate of a Fullerene Fragment
Authors: Gallego María , Calbo Joaquín , Aragó Juan , Krick Calderon Rafael M. , Liquido Fernando H. , Iwamoto Takahiro , Greene Allison K. , Jackson Edward A. , Pérez Emilio M. , Ortí Enrique , Guldi Dirk M. , Scott Lawrence T. , Martín Nazario
Published: January 2014

Herein, we investigate the association of a fullerene fragment, hemifullerene C30H12, with an electron‐donating bowl‐shaped tetrathiafulvalene derivative (truxTTF). UV/Vis titrations and DFT calculations support formation of the supramolecular complex, for which an association constant of log Ka=3.6±0.3 in CHCl3 at room temperature is calculated. Remarkably, electron transfer from truxTTF to C30H12 to form the fully charge‐separated species takes place upon irradiation of the associate with light, constituting the first example in which a fullerene fragment mimics the electron‐accepting behavior of fullerenes within a supramolecular complex.
Iron(II)‐Catalyzed Direct Cyanation of Arenes with Aryl(cyano)iodonium Triflates
Authors: Shu Zhibin , Ji Wenzhi , Wang Xi , Zhou Yujing , Zhang Yan , Wang Jianbo
Published: January 2014

A direct oxidative cyanation of arenes under FeII catalysis with 3,5‐di(trifluoromethyl)phenyl(cyano)iodonium triflate (DFCT) as the cyanating agent has been developed. The reaction is applicable to wide range of aromatic substrates, including polycyclic structures and heteroaromatic compounds.
Synthesis of Triangular Tripalladium Cations as Noble‐Metal Analogues of the Cyclopropenyl Cation
Authors: Blanchard Sébastien , Fensterbank Louis , Gontard Geoffrey , Lacôte Emmanuel , Maestri Giovanni , Malacria Max
Published: January 2014

The first C3‐symmetric 44‐core‐valence‐electron triangular palladium clusters, [{(SAr′)(PAr3)Pd}3]+, have been synthesized by activation of the CS bond of isothioureas. Owing to delocalized metal–metal bonding, these stable complexes are the first noble‐metal analogues of the π‐aromatic cyclopropenyl cation [C3H3]+, with their all‐metal aromaticity involving d‐type atomic orbitals.
Aufbau einer B‐C‐Doppelbindung in der Koordinationssphäre des Platins: ein Alkylidenborylligand, der isoelektronisch zu neutralen Aminoborylenen ist
Authors: Brand Johannes , Braunschweig Holger , Hupp Florian , Phukan Ashwini K. , Radacki Krzysztof , Sen Sakya S.
Published: January 2014

Die Reaktion von [Pt(PCy3)2] mit Br2B‐CH(SiMe3)2 lieferte den ersten Alkylidenborylkomplex trans‐[Br(Cy3P)2Pt{BCH(SiMe3)}] unter Eliminierung von Me3SiBr. Der trans‐ständige Bromidligand dieses Alkylidenborylkomplexes konnte durch Umsetzung mit Methyllithium glatt gegen eine Methylgruppe unter Ausbildung eines weiteren Alkylidenborylkomplexes trans‐[Me(Cy3P)2Pt{BCH(SiMe3)}] ausgetauscht werden. Verschiedene spektroskopische Verfahren, Röntgenstrukturanalytik sowie quantenchemische Rechnungen bestätigen das Vorliegen einer Doppelbindung zwischen Bor und Kohlenstoff. Die quantenchemischen Rechnungen lieferten außerdem Belege für einen stärkeren trans‐Einfluss des Alkylidenborylliganden im Vergleich zu Iminoboryl‐ oder Oxoborylliganden.
Gallium Oxide Nanorods: Novel, Template‐Free Synthesis and High Catalytic Activity in Epoxidation Reactions
Authors: Lueangchaichaweng Warunee , Brooks Neil R. , Fiorilli Sonia , Gobechiya Elena , Lin Kaifeng , Li Li , Parres‐Esclapez Sonia , Javon Elsa , Bals Sara , Van Tendeloo Gustaaf , Martens Johan A. , Kirschhock Christine E. A. , Jacobs Pierre A. , Pescarmona Paolo P.
Published: January 2014

Gallium oxide nanorods with unprecedented small dimensions (20–80 nm length and 3–5 nm width) were prepared using a novel, template‐free synthesis method. This nanomaterial is an excellent heterogeneous catalyst for the sustainable epoxidation of alkenes with H2O2, rivaling the industrial benchmark microporous titanosilicate TS‐1 with linear alkenes and being much superior with bulkier substrates. A thorough characterization study elucidated the correlation between the physicochemical properties of the gallium oxide nanorods and their catalytic performance, and underlined the importance of the nanorod morphology for generating a material with high specific surface area and a high number of accessible acid sites.
Highly Efficient Near‐Infrared Organic Light‐Emitting Diode Based on a Butterfly‐Shaped Donor–Acceptor Chromophore with Strong Solid‐State Fluorescence and a Large Proportion of Radiative Excitons
Authors: Yao Liang , Zhang Shitong , Wang Rong , Li Weijun , Shen Fangzhong , Yang Bing , Ma Yuguang
Published: January 2014

The development of near‐infrared (NIR) organic light‐emitting diodes (OLEDs) is of growing interest. Donor–acceptor (D–A) chromophores have served as an important class of NIR materials for NIR OLED applications. However, the external quantum efficiencies (EQEs) of NIR OLEDs based on conventional D–A chromophores are typically below 1 %. Reported herein is a butterfly‐shaped D–A compound, PTZ‐BZP. A PTZ‐BZP film displayed strong NIR fluorescence with an emission peak at 700 nm, and the corresponding quantum efficiency reached 16 %. Remarkably, the EQE of the NIR OLED based on PTZ‐BZP was 1.54 %, and a low efficiency roll‐off was observed, as well as a high radiative exciton ratio of 48 %, which breaks through the limit of 25 % in conventional fluorescent OLEDs. Experimental and theoretical investigations were carried out to understand the excited‐state properties of PTZ‐BZP.
Near‐Infrared‐Light‐Mediated Imaging of Latent Fingerprints based on Molecular Recognition
Authors: Wang Jie , Wei Ting , Li Xinyang , Zhang Binhao , Wang Jiaxi , Huang Chi , Yuan Quan
Published: January 2014

Photoluminescence is one of the most sensitive techniques for fingerprint detection, but it also suffers from background fluorescence and selectivity at the expense of generality. The method described herein integrates the advantages of near‐infrared‐light‐mediated imaging and molecular recognition. In principle, upconversion nanoparticles (UCNPs) functionalized with a lysozyme‐binding aptamer were used to detect fingerprints through recognizing lysozyme in the fingerprint ridges. UCNPs possess the ability to suppress background fluorescence and make it possible for fingerprint imaging on problematic surfaces. Lysozyme, a universal compound in fingerprints, was chosen as the target, thus simultaneously meeting the selectivity and generality criteria in photoluminescence approaches. Fingerprints on different surfaces and from different people were detected successfully. This strategy was used to detect fingerprints with cocaine powder by using UCNPs functionalized with a cocaine‐binding aptamer.
A Double‐Imprinted Diffraction‐Grating Sensor Based on a Virus‐Responsive Super‐Aptamer Hydrogel Derived from an Impure Extract
Authors: Bai Wei , Spivak David A.
Published: January 2014

The detection of viruses is of interest for a number of fields including biomedicine, environmental science, and biosecurity. Of particular interest are methods that do not require expensive equipment or trained personnel, especially if the results can be read by the naked eye. A new “double imprinting” method was developed whereby a virus‐bioimprinted hydrogel is further micromolded into a diffraction grating sensor by using imprint‐lithography techniques to give a “Molecularly Imprinted Polymer Gel Laser Diffraction Sensor” (MIP‐GLaDiS). A simple laser transmission apparatus was used to measure diffraction, and the system can read by the naked eye to detect the Apple Stem Pitting Virus (ASPV) at concentrations as low as 10 ng mL−1, thus setting the limit of detection of these hydrogels as low as other antigen‐binding methods such as ELISA or fluorescence‐tag systems.
Building Nanocomposite Magnets by Coating a Hard Magnetic Core with a Soft Magnetic Shell
Authors: Liu Fei , Zhu Jinghan , Yang Wenlong , Dong Yunhe , Hou Yanglong , Zhang Chenzhen , Yin Han , Sun Shouheng
Published: January 2014

Controlling exchange coupling between hard magnetic and soft magnetic phases is the key to the fabrication of advanced magnets with tunable magnetism and high energy density. Using FePt as an example, control over the magnetism in exchange‐coupled nanocomposites of hard magnetic face‐centered tetragonal (fct) FePt and soft magnetic Co (or Ni, Fe2C) is shown. The dispersible hard magnetic fct‐FePt nanoparticles are first prepared with their coercivity (Hc) reaching 33 kOe. Then core/shell fct‐FePt/Co (or Ni, Fe2C) nanoparticles are synthesized by reductive thermal decomposition of the proper metal precursors in the presence of fct‐FePt nanoparticles. These core/shell nanoparticles are strongly coupled by exchange interactions and their magnetic properties can be rationally tuned by the shell thickness of the soft phase. This work provides an ideal model system for the study of exchange coupling at the nanoscale, which will be essential for building superstrong magnets for various permanent magnet applications in the future.
Ascorbic Acid as an Initiator for the Direct CH Arylation of (Hetero)arenes with Anilines Nitrosated In Situ
Authors: Crisóstomo Fernando Pinacho , Martín Tomás , Carrillo Romen
Published: January 2014

Ascorbic acid (vitamin C) has been used as a radical initiator in a metal‐free direct CH arylation of (hetero)arenes. Starting from an aniline, the corresponding arenediazonium ion is generated in situ and immediately reduced by vitamin C to an aryl radical that undergoes a homolytic aromatic substitution with a (hetero)arene. Notably, neither heating nor irradiation is required. This procedure is mild, operationally simple, and constitutes a greener approach to arylation.
Aqueous polyacrylate/poly(silicone‐co‐acrylate) emulsion coated fertilizers for slow nutrient‐release application
Authors: Shen Yazhen , Du Changwen , Zhou Jianmin
Published: January 2014

Waterborne polyacrylate/poly(silicone‐co‐acrylate) emulsions were synthesized to develop coated fertilizers. The effects of the n‐butyl acrylate (BA)/methyl methacrylate (MMA) ratio, vinyltriethoxysilane, and synthesis method on the water resistance, glass‐transition temperature, mechanical properties, and nutrient‐release profiles were investigated. The results show that miniemulsion polymerization with a BA/MMA ratio of 55:45 was the most suitable for slow nutrient‐release applications. Under these conditions, the preliminary solubility rate of the nutrient was about 3%, and the 30‐day cumulative nutrient release was 15% at 25°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40369.
Cryo‐preservation for the repeated use of a PDMS prepolymer
Authors: Ju Jongil
Published: January 2014

Leftover uncured polydimethylsiloxane (PDMS) polymer is generally discarded. In an effort to minimize this waste, we have developed a method for cryo‐preserving PDMS prepolymer involving a simple storage technique for the preservation and repeated use over 1 month. Aliquots of the uncured PDMS prepolymer were stored at −20 or −80°C, then conveniently and easily thawed at body temperature (37°C). Proposed cryo‐preservation was successfully evaluated using diverse biological and physical tests. This method of cryo‐preserving PDMS reduces both the material waste and labor of soft lithography process and may enable soft lithography to be environmentally friendly relative to previous methods. The method may be popularly accepted for application to a variety of common microdevice fabrication procedures. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40378.
High Level of Construal and Psychological Distance Reduce Melioration
Authors: Pick‐Alony Rotem , Liberman Nira , Trope Yaacov
Published: January 2014

We examined how level of construal and psychological distance affected performance in a task in which value of alternatives depended on frequency of choice. Melioration, a sub‐optimal choice strategy that fails to take into account such value changes, has been found to be prevalent and difficult to change. Participants repeatedly chose between two buttons to earn as many coins as possible. Button A earned N coins, button B earned N + 3 coins, and N was the number of A presses in the last five trials. In this situation, B has a higher immediate payoff, but because choosing A increases the return from both buttons for the next five trials, maximizing A choices is the optimal strategy. We predicted that because a global perspective is needed to appreciate the dependency of value on frequency of choice, frequency of choosing the globally maximizing alternative (A) would increase when participants apply a higher level of construal and assume a more psychologically distal perspective. Study 1 manipulated construal level through segmenting the sequence of trials into segments of different size, with bigger segments representing higher level of construal. In Study 2, participants played a practice game, and we manipulated the probability of playing the actual game. Both a higher level of construal and a lower probability of playing the actual game (higher distance) increased the number of A choices. These results suggest that a broad perspective that is induced by high level of construal or by psychological distancing may reduce sub‐optimal, meliorating choice. Copyright © 2014 John Wiley & Sons, Ltd.
Explaining general anesthesia: A two‐step hypothesis linking sleep circuits and the synaptic release machinery
Authors: van Swinderen Bruno , Kottler Benjamin
Published: January 2014

Several general anesthetics produce their sedative effect by activating endogenous sleep pathways. We propose that general anesthesia is a two‐step process targeting sleep circuits at low doses, and synaptic release mechanisms across the entire brain at the higher doses required for surgery. Our hypothesis synthesizes data from a variety of model systems, some which require sleep (e.g. rodents and adult flies) and others that probably do not sleep (e.g. adult nematodes and cultured cell lines). Non‐sleeping systems can be made insensitive (or hypersensitive) to some anesthetics by modifying a single pre‐synaptic protein, syntaxin1A. This suggests that the synaptic release machinery, centered on the highly conserved SNARE complex, is an important target of general anesthetics in all animals. A careful consideration of SNARE architecture uncovers a potential mechanism for general anesthesia, which may be the primary target in animals that do not sleep, but a secondary target in animals that sleep.
EXAMINING THE EFFECTS OF BRIEF TRAINING ON THE ATTITUDES AND FUTURE USE OF BEHAVIORAL METHODS BY TEACHERS
Authors: Allen Kelly A. , Bowles Terry V.
Published: January 2014

Teachers from government and independent schools anonymously completed a measure of attitudes towards applied behavior analysis (ABA) before and after participation in a short seminar on ABA. A total of 187 primary teachers provided data on professional qualifications, years of teaching, school type, number of students in the classroom, and prior knowledge of ABA. Data were also collected on the number of students with a disability the teacher had instructed. Survey results suggested that, before and after the seminar, teachers held negative attitudes towards ABA. These attitudes, however, significantly and positively shifted after attending the seminar. Neither the number of students taught with a disability over the last 5 years nor teacher type (e.g., specialist or classroom) nor school type (e.g., independent or government) was significantly related to the attitude measure. The findings have implications for ongoing teacher education and professional development, as well as for school psychologists tailoring interventions and framing recommendations for teachers in mainstream primary settings. Copyright © 2014 John Wiley & Sons, Ltd.
ZEBRA cell‐penetrating peptide as an efficient delivery system in Candida albicans
Authors: Marchione Roberta , Daydé David , Lenormand Jean‐Luc , Cornet Muriel
Published: January 2014

There is increasing interest in drug delivery systems, such as nanoparticles, liposomes, and cell‐penetrating peptides, for the development of new antimicrobial treatments. In this study, we investigated the transduction capacity of a carrier peptide derived from the Epstein–Barr virus ZEBRA protein in the pathogenic fungus Candida albicans. ZEBRA‐minimal domain (MD) was able to cross the cell wall and cell membrane, delivering eGFP to the cytoplasm. Uptake into up to 70% of the cells was observed within two hours, without toxicity. This new delivery system could be used in C. albicans as a carrier for different biological molecules including peptides, proteins, and nucleic acids. Thereby, in antifungal therapy, MD may carry promising bioactive fungal inhibitors that otherwise penetrate poorly into the cells. Furthermore, MD will be of interest for deciphering molecular pathways involving cell‐cycle control in yeast or signaling pathways. Short interfering peptides could be internalized using MD, providing new tools for the inhibition of metabolic or signaling cascades essential for the growth and virulence of C. albicans, such as yeast‐to‐hyphae transition, cell wall remodeling, stress signaling and antifungal resistance. These findings create new possibilities for the internalization of cargo molecules, with applications for both treatment and functional analyses.
A column‐switching HPLC‐MS/MS method for mucopolysaccharidosis type I analysis in a multiplex assay for the simultaneous newborn screening of six lysosomal storage disorders
Authors: Gucciardi Antonina , Legnini Elisa , Di Gangi Iole Maria , Corbetta Carlo , Tomanin Rosella , Scarpa Maurizio , Giordano Giuseppe
Published: January 2014

Lysosomal storage disorders comprise a group of rare genetic diseases in which a deficit of specific hydrolases leads to the storage of undegraded substrates in lysosomes. Impaired enzyme activities can be assessed by MS/MS quantification of the reaction products obtained after incubation with specific substrates. In this study, a column‐switching HPLC‐MS/MS method for multiplex screening in dried blood spot of the lysosomal enzymes activities was developed. Mucopolysaccharidosis type I, Fabry, Gaucher, Krabbe, Niemann–Pick A/B and Pompe diseases were simultaneously assayed. Dried blood spots were incubated with substrates and internal standards; thereafter, supernatants were collected with minor manipulations. Samples were injected, trapped into an online perfusion column and, by a six‐port valve, switched online through the C18 analytical column to perform separation of metabolites followed by MS/MS analysis. A total of 1136 de‐identified newborn screening samples were analyzed to determine references for enzymes activity values. As positive controls, we analyzed dried blood spots from three patients with Pompe, one with Fabry, one with Krabbe disease and two with MPS I, and in all cases the enzyme activities were below the cutoff values measured for newborns, except for an MPS I patient after successful hematopoietic stem cell transplantation. Copyright © 2014 John Wiley & Sons, Ltd.
Enhanced cardiac perception predicts impaired performance in the Iowa Gambling Task in patients with panic disorder
Authors: Wölk Julian , Sütterlin Stefan , Koch Stefan , Vögele Claus , Schulz Stefan M.
Published: January 2014

Objective

Somatic marker theory predicts that somatic cues serve intuitive decision making; however, cardiovascular symptoms are threat cues for patients with panic disorder (PD). Therefore, enhanced cardiac perception may aid intuitive decision making only in healthy individuals, but impair intuitive decision making inPDpatients.

Methods

PDpatients and age‐ and sex‐matched volunteers without a psychiatric diagnosis (n = 17, respectively) completed the Iowa Gambling Task (IGT) as a measure of intuitive decision making. Interindividual differences in cardiac perception were assessed with a common mental‐tracking task.

Results

In line with our hypothesis, we found a pattern of opposing associations (Fisher'sZ = 1.78,P = 0.04) of high cardiac perception with improvedIGT‐performance in matched control‐participants (r = 0.36,n = 14) but impairedIGT‐performance inPDpatients (r = −0.38,n = 13).

Conclusion

Interoceptive skills, typically assumed to aid intuitive decision making, can have the opposite effect inPDpatients who experience interoceptive cues as threatening, and tend to avoid them. This may explain whyPDpatients frequently have problems with decision making in everyday life. Screening of cardiac perception may help identifying patients who benefit from specifically tailored interventions.
Single‐step affinity purification of enzyme biotherapeutics: A platform methodology for accelerated process development
Authors: Brower Kevin P. , Ryakala Venkat K. , Bird Ryan , Godawat Rahul , Riske Frank J. , Konstantinov Konstantin , Warikoo Veena , Gamble Jean
Published: January 2014

Downstream sample purification for quality attribute analysis is a significant bottleneck in process development for non‐antibody biologics. Multi‐step chromatography process train purifications are typically required prior to many critical analytical tests. This prerequisite leads to limited throughput, long lead times to obtain purified product, and significant resource requirements. In this work, immunoaffinity purification technology has been leveraged to achieve single‐step affinity purification of two different enzyme biotherapeutics (Fabrazyme® [agalsidase beta] and Enzyme 2) with polyclonal and monoclonal antibodies, respectively, as ligands. Target molecules were rapidly isolated from cell culture harvest in sufficient purity to enable analysis of critical quality attributes (CQAs). Most importantly, this is the first study that demonstrates the application of predictive analytics techniques to predict critical quality attributes of a commercial biologic. The data obtained using the affinity columns were used to generate appropriate models to predict quality attributes that would be obtained after traditional multi‐step purification trains. These models empower process development decision‐making with drug substance‐equivalent product quality information without generation of actual drug substance. Optimization was performed to ensure maximum target recovery and minimal target protein degradation. The methodologies developed for Fabrazyme were successfully reapplied for Enzyme 2, indicating platform opportunities. The impact of the technology is significant, including reductions in time and personnel requirements, rapid product purification, and substantially increased throughput. Applications are discussed, including upstream and downstream process development support to achieve the principles of Quality by Design (QbD) as well as integration with bioprocesses as a process analytical technology (PAT). © 2014 American Institute of Chemical Engineers Biotechnol. Prog., 30:708–717, 2014
An alternate diafiltration strategy to mitigate protein precipitation for low solubility proteins
Authors: Gefroh Eva , Lutz Herbert
Published: January 2014

Application of the minimum diafiltration (DF) time solution for a monoclonal antibody resulted in a 20‐h process time rather than the expected 12 h. Further investigation indicated high turbidity associated with a product solubility issue that caused a flux decline. As a result, the gel flux model and the associated minimum DF time were not predictive. Multiwell plate solubility screening confirmed that the protein passed through a region of low solubility during the ultrafiltration step. Multiple approaches to address this issue were considered and a new strategy involving variable volume diafiltration (VVDF) was developed. Process modeling and simulation were used to predict performance and to select a value of the DF ratio control parameter (buffer flow/permeate flow = 0.65). Feasibility testing at the bench and pilot scales confirmed that the new strategy reduced solubility issues, fit within existing manufacturing tank volume and system area constraints, matched model predictions, and did not present significant implementation issues. Recommendations are made regarding the general value of this strategy, when it should be used, and how to implement it. © 2014 American Institute of Chemical Engineers Biotechnol. Prog., 30:646–655, 2014
Development of an R‐Selective Amine Oxidase with Broad Substrate Specificity and High Enantioselectivity
Authors: Heath Rachel S. , Pontini Marta , Bechi Beatrice , Turner Nicholas J.
Published: January 2014

Amine oxidases are useful bio‐catalysts for the synthesis of enantiomerically pure 1°, 2° and 3° chiral amines. Enzymes in this class (e.g., MAO‐N from Aspergillus niger) reported previously have been shown to be highly S selective. Herein we report the development of an enantiocomplementary R‐selective amine oxidase based on 6‐hydroxy‐D‐nicotine oxidase (6‐HDNO) with broadened substrate scope and high enantioselectivity. The engineered 6‐HDNO enzyme has been applied to the preparative deracemisation of a range of racemic amines to yield S‐configured products, for example, (S)‐nicotine, in high ee.
NOx Reduction at Near Ambient Temperatures and Under Lean‐Burn Conditions on Modified Pd Surfaces
Authors: Roy Kanak , Gopinath Chinnakonda S.
Published: January 2014

Palladium surfaces that are modified with O atoms in the subsurface broaden the NO reduction temperature regime up to 325 K with O2‐rich NO+H2+O2 compositions. Compared to virgin Pd surfaces, up to 150 % higher deNOx catalytic activity was observed with modified Pd surfaces at the reaction maximum. Molecular beam instrument and ambient‐pressure photoelectron spectroscopy were employed to follow the kinetic and surface changes. These results open up a possibility to realize the cold‐start reduction of NOx (deNOx). DeNOx activity reported in the literature with supported Pd catalysts after a simple calcination in air compares well with our present observations. Surface modification is likely to demonstrate a high potential for other catalytic reactions at relatively low temperatures.
First Highly Efficient and Photostable E and C Derivatives of 4,4‐Difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) as Dye Lasers in the Liquid Phase, Thin Films, and Solid‐State Rods
Authors: Duran‐Sampedro Gonzalo , Esnal Ixone , Agarrabeitia Antonia R. , Bañuelos Prieto Jorge , Cerdán Luis , García‐Moreno Inmaculada , Costela Angel , Lopez‐Arbeloa Iñigo , Ortiz María J.
Published: January 2014

A new library of E‐ and C‐4,4‐difluoro‐4‐bora‐3a,4a‐diaza‐s‐indacene (BODIPY) derivatives has been synthesized through a straightforward protocol from commercially available BODIPY complexes, and a systematic study of the photophysical properties and laser behavior related to the electronic properties of the B‐substituent group (alkynyl, cyano, vinyl, aryl, and alkyl) has been carried out. The replacement of fluorine atoms by electron‐withdrawing groups enhances the fluorescence response of the dye, whereas electron‐donor groups diminish the fluorescence efficiency. As a consequence, these compounds exhibit enhanced laser action with respect to their parent dyes, both in liquid solution and in the solid phase, with lasing efficiencies under transversal pumping up to 73 % in liquid solution and 53 % in a solid matrix. The new dyes also showed enhanced photostability. In a solid matrix, the derivative of commercial dye PM597 that incorporated cyano groups at the boron center exhibited a very high lasing stability, with the laser emission remaining at the initial level after 100 000 pump pulses in the same position of the sample at a 10 Hz repetition rate. Distributed feedback laser emission was demonstrated with organic films that incorporated parent dye PM597 and its cyano derivative. The films were deposited onto quartz substrates engraved with appropriate periodical structures. The C derivative exhibited a laser threshold lower than that of the parent dye as well as lasing intensities up to three orders of magnitude higher.
Enantioselective Surface Plasmon Resonance Sensor Based on C60 Fullerene‐Glutathione Self‐Assembled Monolayer (SAM)
Authors: Stefan‐van Staden Raluca‐Ioana
Published: January 2014

A novel enantioselective surface plasmon resonance (SPR) sensor based on a self‐assembled monolayer of C60 fullerene as the chiral selector is proposed. A binding assay, apparent affinity constant, and apparent dissociation binding constant were used to analyze and study the enantioselectivity of C60 fullerene‐glutathione film for L‐histidine, which was chosen as the model analyte. The apparent affinity constant for the complex formed by L‐histidine with C60 fullerene‐glutathione film was 5.2 x 109 M‐1. The proposed SPR sensor can be used for the assay of L‐histidine in the 10‐10 – 10‐7 mol/L concentration range. Chirality 26:129–131, 2014. © 2014 Wiley Periodicals, Inc.
Application of single site catalyst metallocene polyethylenes in extruded films: Effect of molecular structure on sealability, flexural cracking and mechanical properties
Authors: Sadeghi Farhad , Ajji Abdellah
Published: January 2014

Three single site catalysts metallocene polyethylenes (mPE) different in molecular structure were selected and films from them were produced using a semi‐industrial cast film extrusion line. Rheological and gel permeation chromatography tests were performed on the mPE resins to assess their molecular structure. Mechanical, physical and sealability properties of the films were evaluated as well as flexural cracking and particles encapsulation (caulkability) and the results are discussed in relation to the molecular structures of the resins. It was found that molecular weight and distribution of short chain branching (comonomer) on the backbone of the polyethylene chains are the main factors that control sealability, flexural cracking and mechanical properties. The placement of comomoner on medium length chains generated crystals with smaller size that show a lower melting peak. Sealing was controlled by crystal distribution, chain diffusion and entanglement formation at the interface. mPE with lower melting point and linear molecular structure showed greater hot tack and seal strength. Polydispersity along with molecular weight contributed to toughness and puncture resistance. Flexural cracking resistance was revealed to be related to crystallinity, tie chain density and more importantly to fraction of amorphous phase. The amorphous part could absorb flexural energy and hinders crack initiation and propagation. Seal through contamination (caulkability) was found to be related to flowability of the melt. The resin with stronger shear thinning in melt state and lower heat seal initiation temperature showed an improved caulkability.