bluuebunny/crossref_metadata_2025 huggingface dataset:
Doctoral Symposium Submission
Authors: Roberto K R
Published: June 2013

How successful are controlled vocabularies at describing transgender topics? This work explores the use of hierarchical taxonomic structures to describe people's often-fluid gender and sexuality identities, particularly the lack of accurate and appropriate language in most commonly used subject thesauri, and how the lack of this accurate and appropriate language can affect potential users. Specifically, I am referring to individuals who identify as gender-nonconforming. This term, as defined by the Sylvia Rivera Law Project, refers to “people who do not follow other people's ideas or stereotypes about how they should look or act based on the female or male sex they were assigned at birth.” The phrase is frequently used as an umbrella term that encompasses a wide variety of gender identities, including transsexual, drag queen, genderqueer, and butch.

Many standard vocabularies, including the Library of Congress Subject Headings, have a long and thorny history with regards to prescriptive access points about marginalized groups and sexualities. This work offers a historical overview of the ways in which authorized vocabularies have differed from vernacular language commonly used by community members and LGBTQ scholars to describe their own lives, and explores well- and lesser-known subject vocabularies such as LCSH, MeSH, IHLIA's Homosaurus, and tags assigned by LGBTQ people when describing their personal collections.

 
Participation financière et climat social : une analyse des perceptions comparées dirigeants/salariés
Authors: Stévenot Anne , Guery Loris
Published: June 2013

L’article s’interroge, dans la perspective de l’institutionnalisme économique de Commons, sur la relation unissant les dispositifs de participation financière au climat social, appréhendé par le biais de la perception qu’en ont les dirigeants et les salariés, d’une part, et par des indicateurs de dysfonctionnements sociaux, tels que l’absentéisme et les conflits sociaux, d’autre part. La question des caractéristiques de ces pratiques (modalités de négociation présidant à leur mise en oeuvre, types de dispositifs, mode de calcul) est également posée. L’étude empirique est fondée sur l’exploitation de l’enquête REPONSE qui représente un échantillon de 3 000 établissements français et de 8 000 salariés. Au-delà des différences de perception entre dirigeants et salariés, les résultats, obtenus à l’aide de modèles de régressions logistiques, mettent tout d’abord en évidence que plus que le montant versé, c’est l’existence même d’un dispositif de participation financière qui influence le climat social. Par ailleurs plus les dispositifs apparaissent comme désintéressés de la part de l’entreprise et meilleur est le climat social du point de vue des salariés. Les modalités de conclusion de l’accord de participation financière, notamment l’intervention des syndicats, ont également une influence sur le climat social. Compte tenu des différences de résultats pouvant exister selon que l’on s’intéresse à la perception des dirigeants, à celle des salariés ou aux indicateurs de dysfonctionnements sociaux, l’article met également en lumière l’importance pour les recherches sur le climat social de prendre en compte à la fois les dimensions objectives du climat social et la perception qu’en ont les acteurs.
Antiretroviral treatment, management challenges and outcomes in perinatally HIV‐infected adolescents
Authors: Agwu Allison L , Fairlie Lee
Published: June 2013

Three decades into the HIV/AIDS epidemic there is a growing cohort of perinatally HIV‐infected adolescents globally. Their survival into adolescence and beyond represent one of the major successes in the battle against the disease that has claimed the lives of millions of children. This population is diverse and there are unique issues related to antiretroviral treatment and management. Drawing from the literature and experience, this paper discusses several broad areas related to antiretroviral management, including: 1) diverse presentation of HIV, (2) use of combination antiretroviral therapy including in the setting of co‐morbidities and rapid growth and development, (3) challenges of cART, including nonadherence, resistance, and management of the highly treatment‐experienced adolescent patient, (4) additional unique concerns and management issues related to PHIV‐infected adolescents, including the consequences of longterm inflammation, risk of transmission, and transitions to adult care. In each section, the experience in both resource‐rich and limited settings are discussed with the aim of highlighting the differences and importantly the similarities, to share lessons learnt and provide insight into the multi‐faceted approaches that may be needed to address the challenges faced by this unique and resilient population.
Neurodevelopment in perinatally HIV‐infected children: a concern for adolescence
Authors: Laughton Barbara , Cornell Morna , Boivin Michael , Van Rie Annelies
Published: June 2013

Globally, an estimated 3.4 million children are living with HIV, yet little is known about the effects of HIV and antiretroviral treatment (ART) on the developing brain, and the neurodevelopmental and behavioural outcomes of perinatally HIV‐infected (PHIV+) adolescents.

We reviewed the literature on neurodevelopmental outcomes in PHIV+ children and adolescents, and summarized the current evidence on behaviour, general cognition, specific domains, hearing and language, school performance and physical disabilities due to neurological problems.

Evidence suggests that PHIV+ children do not perform as well as controls on general cognitive tests, processing speed and visual–spatial tasks, and are at much higher risk for psychiatric and mental health problems. Children with AIDS‐defining diagnoses are particularly at risk for poorer outcomes.

A striking finding is the lack of published data specific to the adolescent age group (10–25 years), particularly from resource‐constrained countries, which have the highest HIV prevalence. In addition, extreme heterogeneity in terms of timing and source of infection, and antiretroviral experience limits our ability to summarize findings of studies and generalize results to other settings.

Due to the complex nature of the developing adolescent brain, environmental influences and variation in access to ART, there is an urgent need for research on the longitudinal trajectory of neurodevelopment among children and adolescents perinatally infected with HIV, especially in high burden resource‐constrained settings.
Preparation of Oligodeoxyribonucleotides Containing the Pyrimidine(6–4)pyrimidone Photoproduct by Using a Dinucleotide Building Block
Authors: Iwai Shigenori
Published: June 2013

This unit describes procedures for the synthesis of a dinucleotide‐type building block of the pyrimidine(6–4)pyrimidone photoproduct [(6–4) photoproduct], which is one of the major DNA lesions induced by ultraviolet (UV) light, and its incorporation into oligodeoxyribonucleotides. Although this type of lesion is frequently found at thymine‐cytosine sites, the building block of the (6–4) photoproduct formed at thymine‐thymine sites can be synthesized much more easily. The problem in the oligonucleotide synthesis is that the (6–4) photoproduct is labile under alkaline conditions. Therefore, building blocks with an amino‐protecting group that can be removed by a brief treatment with ammonia water at room temperature must be used for the incorporation of the normal bases. Byproduct formation by the coupling of phosphoramidites with the N3 of the 5′ component should also be considered. This side reaction can be avoided by using benzimidazolium triflate as an activator. Curr. Protoc. Nucleic Acid Chem. 53:4.56.1‐4.56.18. © 2013 by John Wiley & Sons, Inc.
Synthesis of Phosphoramidate Prodrugs: ProTide Approach
Authors: Serpi Michaela , Madela Karolina , Pertusati Fabrizio , Slusarczyk Magdalena
Published: June 2013

The ProTide (pronucleotide) approach is a prodrug strategy elaborated to deliver nucleoside monophosphate into the cell, circumventing the first and inefficient rate‐limiting phosphorylation step of nucleosides and improving the cellular penetration of nucleotides. The ProTide of a nucleoside phosphate is a phosphoramidate prodrug consisting of an amino acid ester promoiety linked via P‐N bond to a nucleoside aryl phosphate. Such prodrugs have increased lipophilicity and thus are capable of altering cell and tissue distribution. The ProTide technology was successfully and extensively applied to a wide variety of nucleoside phosphates, endowed with antiviral and anticancer activity. This unit describes two different synthetic strategies allowing the preparation of phosphoramidates of 6‐O‐methyl‐2′−β‐C‐methylguanosine as model compounds for nucleosides having only the 5′‐OH as reactive hydroxyl group, and phosphoramidates of 2′−β‐D‐arabinouridine (AraU) as model compounds for nucleosides containing two or more reactive hydroxyl groups. Curr. Protoc. Nucleic Acid Chem. 53:15.5.1‐15.5.15. © 2013 by John Wiley & Sons, Inc.
Seismic Arrays to Study African Rift Initiation
Authors: Gao Stephen S. , Liu Kelly H. , Reed Cory A. , Yu Youqiang , Massinque Belarmino , Mdala Hassan , Moidaki Moikwathai , Mutamina Daniel , Atekwana Estella A. , Ingate Shane , Reusch Angela M.
Published: June 2013

Rifting of stable continents is a key element of plate tectonic cycles. In spite of numerous studies, the mechanism responsible for the initiation and evolution of rift valleys such as the East African Rift System (EARS) is still poorly understood, partly because most previous investigations focused on rift segments that were in the mature stage. Geodynamic modeling [Huismans et al., 2001] suggests that upwelling of the asthenosphere ubiquitously observed beneath mature rifts can either originate from thermal or dynamic anomalies in the deep mantle (active rifting) or be induced by thinning of the lithosphere from far‐field stresses (passive rifting) [Sengor and Burke, 1978].
Science academies issue statement about science and sustainable development
Authors: Showstack Randy
Published: June 2013

In advance of the Group of 8's (G8) 17–18 June meeting of some of the world's leading industrialized nations, 14 science academies have issued a joint statement about how science, technology, and innovation can play a role in driving sustainable development. The statement, issued on 29 May, highlights a number of challenges for bringing an estimated 1.3 billion people out of poverty while also meeting the needs of a soaring world population that is expected to be approximately 9 billion by 2050.
Report ranks U.S. coastal state protection of marine areas
Authors: Showstack Randy
Published: June 2013

Most U.S. coastal states are not doing enough to safeguard nearby marine areas, according to a 29 May report by two environmental groups, the Marine Conservation Institute (MCI) and Mission Blue. The groups ranked U.S. coastal states and territories based on the percentage of state marine waters classified as no‐take marine protected areas (MPAs) where fishing, mining, and oil and gas development are not allowed.
Coupled model boosts reproduction of inner magnetosphere ring current
Authors: Schultz Colin
Published: June 2013

The inner magnetosphere ring current, which circles the Earth a few Earth radii above the surface, consists of energetic ions and electrons and plays an important role in the space environment. During geomagnetic storms the flow in the ring current rises dramatically. The behavior of the ring current and other features of the inner magnetosphere depend strongly on conditions in other regions of the magnetosphere. The small scale of the particle dynamics that drive the ring current, compared to the vast spatial scale of the entire magnetosphere, makes it difficult to represent both the nuance of the inner magnetosphere and the full scope of the magnetospheric system.
Drug‐Impaired Driving
Authors: Verstraete Alain G. , Legrand Sara‐Ann
Published: June 2013

Driving is a complex task, requiring the cooperation of several different cognitive and psychomotor functions. Experimental studies have shown that drugs can have a detrimental influence on capacities that are essential for driving. Epidemiological studies have shown that drugs (not including alcohol) are found in 1–11% of the general driving population, in 6–53% of drivers who are injured or killed in traffic crashes, and in 55–99% of drivers who are suspected of driving under the influence of drugs (DUID). Drivers who are under the influence of drugs have a higher risk of being involved in, or being responsible for, a crash. Responsibility analyses show that driving under the influence of several drugs increases the risk of being responsible for a crash. Three types of DUID legislation exist: “impairment” legislation, “
per se
” legislation, and the “two‐tier” approach. In impairment legislation, the prosecution must demonstrate that the driver was impaired or “under the influence”. A “
per se
” law prohibits driving if drugs are present in blood, serum, plasma, or oral fluid (OF) above a certain threshold concentration. In the two‐tier approach, the
per se
and impairment approach are combined. In recent years, OF has been used more and more as biological matrix for roadside drug screening. Recent multi‐analyte methods developed for confirmation analysis, either on blood or on OF, use liquid chromatography (tandem) mass spectrometry.
Deception Detection
Authors: Honts Charles R.
Published: June 2013

Deception detection is an important task in forensics and security. Criminals and terrorists are highly motivated to deceive, and people are not good in detecting deception without technological assistance. Traditional approaches to assist in the deception detection task have made use of physiological cues measured from the suspect in a controlled environment. To date, only the polygraph has achieved widespread application in forensics. Although there is controversy, research suggests that in forensic settings the polygraph is about 90% accurate in discriminating truth‐tellers from deceivers. This is a considerable improvement over naïve deception detection. Research has examined other physiological measures. Voice stress analysis, although used in forensics, is without demonstrated scientific validity. Recent research suggests that ocular‐motor measures may be able to provide high validity deception detection even in screening settings.
Coordination Chemistry ofo‐Semiquinones
Authors: Pierpont Cortlandt G. , Kelly Joseph K.
Published: June 2013

o‐Semiquinone (SQ) radicals are ideally suited to chelate with transition metal ions. Ligand paramagnetism results in spin‐coupling interactions with paramagnetic metal ions, and complexes containing multiple SQ ligands have magnetic properties resulting from inter‐ligand coupling. The unpaired SQ electron resides in a ligand‐localized π orbital close in energy with the valence d orbitals of many transition metal ions. Electron transfer between ligand and metal may be observed under equilibrium conditions by monitoring the temperature‐dependence of spectral and magnetic properties in a process known as valence tautomerism. The redox potentials of common SQ ligands overlap with the redox potentials of metal ions contributing to redox series that may involve reversible electron transfer steps at both the metal and SQ ligands. Multielectron redox reactions involving SQ ligands are useful in small molecule transformations that involve substrate oxidation or reduction over a narrow range in electrochemical potential. These properties are unique to complexes containing ligands capable of changing their charged state by either intramolecular electron transfer within the complex molecule or by an exchange of charge with an external redox component. Reactions and processes of this type will be the focus of this review on the coordination chemistry ofo‐semiquinonate ligands.
The Chemistry of Iron–Alkyl Complexes
Authors: Alberch Eduardo , Ulicki Joseph S. , Asad MD. Sharif , Hossain M. Mahmun
Published: June 2013

Iron‐alkyl complexes are found as intermediates in a variety of homogenous organometallic reactions. The chapter deals with the synthesis, stability and reactions of iron‐alkyl complexes. Wilkinson and Piper in 1956 were the first to report an iron‐alkyl complex, and these investigations lead to the discovery of a whole range of reactions involving these complexes. This chapter will firstly cover the preparation of iron‐alkyl complexes, followed by the main categories of reactions in which these complexes take part, mainly CO insertion reactions and electrophilic cleavage reactions. A brief account of the role of FpMe (Fp = CpFe(CO)2) complexes in catalytic processes are also included in this chapter.
A Summary of Functional Groups Containing Selenium and Tellurium: A Catalog of the Many Groups that are Known and Some that are Not
Authors: Hack Janet E. , Liebman Joel F.
Published: June 2013

In the current chapter we provide a catalog of functional groups containing the chalcogens selenium and tellurium where by functional group we mean the central atom, Se or Te, and its local arrangement of atoms bonded to it by single or multiple bonds (its neighborhood). We will do so by cataloging examples of compounds containing the groups. The atoms that define the local neighborhood are limited here to H, C, N, the chalcogens O, S, Se, Te, and the halogens F, Cl, Br and I. As such we avoid Se‐ and Te‐bonding to metals and metalloids and so we will ignore all salts, and we also ignore all groups with formal charges. However arbitrarily, we did include complexes involving species wherein, with appropriate bond‐shifting, we can draw the compound of interest without any formal charges. We have also avoided mention of free radicals and other species with unpaired electrons. All of the groups were explicitly chosen, and have at least one carbon attached to the selenium or tellurium. For each group we generally give one compound as an example (admittedly our choice of name is often unsystematic), a reference to the primary literature (again chosen unsystematically), and the CAS RN for the example compound (when available). Where there is no example we will generally explicitly say so, occasionally with due annotation as NO CAS RN or “no compounds identified” to encourage their study.
Organic Selenocyanates, Tellurocyanates and Related Compounds
Authors: Toshimitsu Akio
Published: June 2013

Preparations, physical properties and reactions of organic selenocyanates, isoselenocyanates, and tellurocyanates are described. The preparations of organic selenocyanates include synthetic procedures (1) by substitution of halogen and related group, (2) from diazonium salts, (3) from organometallic compounds, (4) by selenocyanation, and (5) by formation of an SeCN bond. The preparations of organic isoselenocyanates include synthetic procedures (1) by formation of a CSe bond, (2) by substitution of halogen atom and (3) by [3.3]sigmatropic rearrangement. The reactions of organic selenocyanates include (1) additions to the CN bond, (2) substitution of the CN group, (3) elimination of the CN group, and (4) isomerization to isoselenocyanates. The reactions of organic isoselenocyanates include (1) addition of nitrogen nucleophile, (2) addition of oxygen nucleophile, (3) addition of sulfur, selenium or tellurium nucleophile, and (4) reaction of carbon nucleophile. Coverage of the literature is nearly complete from 1986 to 2011.
Advances in the Photochemistry of Organoselenium and Organotellurium Compounds
Authors: Ouchi Akihiko , Ando Wataru , Oba Makoto
Published: June 2013

Review on the photochemistry of organoselenium and tellurium compounds. The reactions were classified to photofragmentation and photoelimination, photosubstitution, photoaddition, photoisomerization and photorearrangement, photooxidation, photoreduction, photochemical reaction of organometallic complexes, and miscellaneous reactions.
Ultrasonic Welding of Aluminum Alloys to Fiber Reinforced Polymers
Authors: Wagner Guntram , Balle Frank , Eifler Dietmar
Published: June 2013

To realize multi‐material structures, e.g., out of light metals and fiber reinforced polymer (FRP) composites suitable joining methods are required. The ultrasonic metal welding technology was applied to produce high strength joints between different aluminum alloys and carbon fiber reinforced polymers (CFRPs) in the framework of research unit 524 of the German Research Foundation. The bonding mechanisms were characterized by light optical and scanning electron microscopy (SEM). The performed analysis have shown a bonding zone with an intensive contact between the metallic surface and the load bearing carbon fibers of the CFRP as a result of the ultrasonic welding process. Using precipitation hardening aluminum alloy AA2024 tensile shear strengths of up to 58 MPa could be achieved. In comparison to established joining techniques ultrasonic metal welding can be an interesting alternative to realize dissimilar joints for the automotive or aircraft industry.
Aligned Chitosan‐Polycaprolactone Polyblend Nanofibers Promote the Migration of Glioblastoma Cells
Authors: Kievit Forrest M. , Cooper Ashleigh , Jana Soumen , Leung Matthew C. , Wang Kui , Edmondson Dennis , Wood David , Lee Jerry S. H. , Ellenbogen Richard G. , Zhang Miqin
Published: June 2013

In vitro models that accurately mimic the microenvironment of invading glioblastoma multiform (GBM) cells will provide a high‐throughput system for testing potential anti‐invasion therapies. Here, the ability of chitosan‐polycaprolactone polyblend nanofibers to promote a migratory phenotype in human GBM cells by altering the nanotopography of the nanofiber membranes is investigated. Fibers are prepared with diameters of 200 nm, 400 nm, and 1.1 μm, and are either randomly oriented or aligned to produce six distinct nanotopographies. Human U‐87 MG GBM cells, a model cell line commonly used for invasion assays, are cultured on the various nanofibrous substrates. Cells show elongation and alignment along the orientation of aligned fibers as early as 24 h and up to 120 h of culture. After 24 h of culture, human GBM cells cultured on aligned 200 nm and 400 nm fibers show marked upregulation of invasion‐related genes including β‐catenin, Snail, STAT3, TGF‐β, and Twist, suggesting a mesenchymal change in these migrating cells. Additionally, cells cultured on 400 nm aligned fibers show similar migration profiles as those reported in vivo, and thus these nanofibers should provide a unique high‐throughput in vitro culture substrate for developing anti‐migration therapies for the treatment of GBM.
Precision spectroscopy of the 2S‐4P transition in atomic hydrogen on a cryogenic beam of optically excited 2S atoms
Authors: Beyer Axel , Alnis Janis , Khabarova Ksenia , Matveev Arthur , Parthey Christian G. , Yost Dylan C. , Pohl Randolf , Udem Thomas , Hänsch Theodor W. , Kolachevsky Nikolai
Published: June 2013

Precision spectroscopy of the 2S − 4P1/2 and 2S − 4P3/2 transitions in atomic hydrogen is performed with a reproducibility of a few parts in 1012. A cryogenic beam of metastable 2S atoms is obtained by optical excitation, avoiding excessive heating of electron impact excitation used in all previous experiments of this kind. Despite the low temperature of 5.8 K, the first‐order Doppler effect is the dominating systematic shift, which is suppressed to a very high degree. The effectiveness of this suppression is verified by employing a time‐resolved detection scheme. This experiment should contribute to an improved determination of the Rydberg constant and the proton r.m.s. charge radius.
Anticancer metallopharmaceutical agents based on mixed‐ligand palladium(II) complexes with dithiocarbamates and tertiary organophosphine ligands
Authors: Khan Hizbullah , Badshah Amin , Said Muhammad , Murtaza Ghulam , Ahmad Jamil , Jean‐Claude Bertrand J. , Todorova Margarita , Butler Ian S.
Published: June 2013

Mixed‐ligand palladium(II) complexes of the type [(DT)Pd(PR3)Cl], where DT = diethyldithiocarbamate (1), dibutyldithiocarbamate (2,3), dipropyldithiocarbamate (4,5), bis(2‐methoxyethyl)dithiocarbamate; PR3 = benzyldiphenylphosphine (1,4), diphenyl‐o‐tolylphosphine (2), diphenyl‐t‐butylphosphine (3), P‐chlorodiphenylphosphine (5) and triphenylphosphine (6), have been synthesized and characterized by elemental analyses and FT‐IR, Raman and multinuclear NMR spectroscopy. The structures of compounds 1 and 2 were determined by single‐crystal X‐ray diffraction (XRD) measurements and these analyses showed that the complexes have pseudo square‐planar geometry around the Pd(II) and that the dithiocarbamate ligand is bound in a bidentate fashion, while the remaining two positions are occupied by a tertiary organophosphine and a chloride ligand. The anticancer studies showed that the Pd(II) complexes are highly active against cisplatin‐resistant DU145 human prostate carcinoma (HTB‐81) cells with the highest activity shown by compound 6 (IC50 = 2.12 µm). The redox behavior and ds‐DNA‐denaturing ability of the complexes were studied by cyclic voltammetry and two reduction and one oxidation waves were observed. The decrease in the reduction peak currents illustrated the consumption of the mixed‐ligand drug by the DNA molecule. Copyright © 2013 John Wiley & Sons, Ltd.
Synthesis and characterization of salep sulfate and its utilization in preparation of heavy metal ion adsorbent
Authors: Pourjavadi Ali , Doulabi Malihe , Alamolhoda Ali Asghar , Tavakkoli Elham , Amirshekari Shokoufe
Published: June 2013

A multicomponent polysaccharide obtained from dried tubers of certain natural terrestrial orchids was chemically modified by sulfonation using chlorosulfonic acid–dimethylformamide (HClSO3–DMF) complex as a reagent. For a structural characterization of salep sulfate 1H nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectra, and Thermogravimetric analysis (TGA) curves were recorded. The sulfate content of modified salep was determined using elemental analysis. This modified biopolymer was used to prepare a new environment‐friendly heavy metal ion adsorbent, salep sulfate‐graft‐polyacrylic acid hydrogel (SS‐g‐PAA). Swelling rate and equilibrium water absorbency in various pH and saline solutions were investigated to study the effect of salep sulfate on swelling behavior of the hydrogel. In addition, the effect of sulfate content on heavy metal ion adsorption from aqueous solution was investigated. The results show that SS‐g‐PAA can effectively remove heavy metal ions (Co2+, Zn2+, Cu2+) from aqueous solution and swelling behavior of the hydrogels highly dependent on the amount of sulfate group on corresponding modified polysaccharide. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3001–3008, 2013
Synthesis and characterization of elastomeric polyurethane and PU/clay nanocomposites based on an aliphatic diisocyanate
Authors: Saha Chinmoy , Chaki Tapan K. , Singha Nikhil K.
Published: June 2013

This investigation reports preparation of polyurethane and polyurethane/clay nanocomposites based on polyethylene glycol, isophorone diisocyanate (IPDI), an aliphatic diisocyanate and 1,4‐ Butanediol as chain extender by solution polymerization. In this case PU/clay nanocomposites were prepared viaex‐situmethod using 1, 3, and 5 wt % of Cloisite 30B. Thermogravimetric analysis showed that the maximum decomposition temperature (Tmax) of the PU/clay nanocomposite is much higher than the pristine PU. The tensile properties improved upon increasing the organoclay (Cloisite 30B) content upto 3 wt %, and then decreased to some extent upon further increasing the nanoparticle loading to 5 wt %. Optical properties of the nanocomposites were studied by UV‐vis spectrophotometer. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the morphology of the nanocomposites. It was observed that with the incorporation of 3 wt % nanoclay the crystallinity in PU nanocomposite increases, then diminishes with further loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3328–3334, 2013
Free volume as an internal material parameter to probe interfaces in ternary polymer blends: A positron lifetime study
Authors: Dinesh Meghala , Chikkakuntappa Ranganathaiah
Published: June 2013

A new method to characterize individual interfaces in ternary polymer blends from experimentally measured fractional free volume from Positron Annihilation Lifetime Spectroscopy (PALS) has been developed. By this, we derive the composition dependent miscibility level in ternary polymer blends. This method has its genesis in KRZ (Kirkwood–Risemann–Zimm) theory which introduces hydrodynamic interaction parameter as a measure of excess friction generated at the interface between dissimilar polymer chains resulting in energy dissipation. The method successfully applied for binary blends has been theoretically modified to suit ternary blends in the present work. The efficacy of this method has been tested for two ternary blends namely polycaprolactone/poly(styrene‐co‐acrylonitrile)/poly(vinyl chloride) (PCL/SAN/PVC) and polycaprolactone/poly(vinyl chloride)/poly(vinyl acetate) (PCL/PVC/PVAc) in different compositions. We obtained a maximum effective hydrodynamic interaction (αeff) of −12.60 at composition 80/10/10 of PCL/PVC/PVAc while PCL/SAN/PVC showed −1.60 at 68/16/16 composition. These results suggest that these compositions produce high miscibility level as compared to other compositions. DSC measurements have also been used to supplement positron results. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3335–3344, 2013
Geometrical dependence of viscosity of polymethylmethacrylate melt in capillary flow
Authors: Lin Xiang , Kelly Adrian , Ren Dongyun , Woodhead Mike , Coates Phil , Wang Kuisheng
Published: June 2013

The shear viscosity of polymethylmethacrylate (PMMA) melt is particularly investigated by using a twin‐bore capillary rheometer at four temperatures of 210, 225, 240, and 255°C with different capillary dies. Experimental results show that the geometrical dependence of shear viscosity is significantly dependent on melt pressure as well as melt temperature. The measured shear viscosity increases with the decrease of die diameter at lower temperatures (210 and 225°C) but decreases with the decrease of die diameter at higher temperatures (240 and 255°C). Based on the deviation of shear viscosity curves and Mooney method, negative slip velocity is obtained at low temperatures and positive slip velocity is obtained at high temperatures, respectively. Geometrical dependence and pressure sensitivity of shear viscosity as well as temperature effect are emphasized for this viscosity deviation. Moreover, shear viscosity curve at 210°C deviates from the power law model above a critical pressure and then becomes less thinning. Mechanisms of the negative slip velocity at low temperatures are explored through Doolittle viscosity model and Barus equation, in which the pressure drop is used to obtain the pressure coefficient by curve fitting. Dependence of pressure coefficient on melt temperature suggests that the pressure sensitivity of shear viscosity is significantly affected by temperature. Geometrical dependence of shear viscosity can be somewhat weakened by increasing melt temperature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3384–3394, 2013
Synthesis and Antibacterial Activity of 4‐Aryl‐2‐(1‐substituted ethylidene)thiazoles
Authors: Hassan Alaa A. , Ibrahim Yusria R. , El‐Sheref Essmat M. , Abdel‐Aziz Mohamed , Bräse Stefan , Nieger Martin
Published: June 2013

(E)‐4‐Aryl‐2‐[2‐(1‐substituted ethylidene)hydrazinyl]thiazoles and (Z)‐3‐substituted‐4‐aryl‐2‐[(E)‐(1‐phenylethylidene)hydrazono]‐2,3‐dihydrothiazoles were synthesized by the reaction of (substituted ethylidene)hydrazinecarbothioamides with ω‐bromoacetophenones. The characterization of this new class of compounds was performed using different spectroscopic tools. The structure of (Z)‐3‐benzyl‐4‐(4‐bromophenyl)‐2‐[(E)‐(1‐phenylethylidene)hydrazono]‐2,3‐dihydrothiazole 6e was unambiguously confirmed by single‐crystal X‐ray crystallography. Compounds 5a–e, 5i, 6e, 6g, and 6i were screened for their in vitro antibacterial activity against different strains of microorganisms; most of the tested compounds exhibited promising antibacterial activity against some organisms compared to ciprofloxacin and sulbactam penicillin. Compounds 5e, 5i, 6e, 6g, and 6i exhibited several‐fold significant antibacterial activity against the Gram‐positive bacteria Staphylococcus aureus, better than ciprofloxacin, with minimum inhibitory concentration values ranging from 0.05 to 0.4 µg/mL. The rest of the tested compounds gave significant antibacterial activities against different Gram‐negative bacterial strains.
Highly Efficient Synthesis of Heterocyclic and Alicyclic β2‐Amino Acid Derivatives by Catalytic Asymmetric Hydrogenation
Authors: Li Lanning , Chen Bin , Ke Yuanyuan , Li Qing , Zhuang Yue , Duan Kun , Huang Yichun , Pang Jiyan , Qiu Liqin
Published: June 2013

A valuable class of new heterocyclic and alicyclic prochiral α‐aminomethylacrylates has been conveniently synthesized through a three‐step transformation involving a Baylis–Hillman reaction, O‐acetylation, and a subsequent allylic amination. The corresponding novel β2‐amino acid derivatives were prepared with excellent enantioselectivities and high yields by catalytic asymmetric hydrogenation using the catalyst rhodium(Et‐Duphos) (Et‐Duphos=2′,5′,2′′,5′′‐tetraethyl‐1,2‐bis(phospholanyl)benzene)) under mild reaction conditions (up to 99 % ee and S/C=1000). The influence of the substrate on the enantioselectivity and reactivity is investigated, and the most suitable substrate configuration for the highly efficient enantioselective hydrogenation of β‐substituted α‐aminomethylacrylates under the Rh–Duphos system is reported. The current protocol provides a very practical, facile, and scalable method for the preparation of heterocyclic and alicyclic β2‐amino acids and their derivatives.
Allylation Reactions of Aldehydes with Allylboronates in Aqueous Media: Unique Reactivity and Selectivity that are Only Observed in the Presence of Water
Authors: Kobayashi Shū , Endo Toshimitsu , Yoshino Takumi , Schneider Uwe , Ueno Masaharu
Published: June 2013

Zn(OH)2‐catalyzed allylation reactions of aldehydes with allylboronates in aqueous media have been developed. In contrast to conventional allylboration reactions of aldehydes in organic solvents, the α‐addition products were obtained exclusively. A catalytic cycle in which the allylzinc species was generated through a B‐to‐Zn exchange process is proposed and kinetic studies were performed. The key intermediate, an allylzinc species, was detected by HRMS (ESI) analysis and by online continuous MS (ESI) analysis. This analysis revealed that, in aqueous media, the allylzinc species competitively reacted with the aldehydes and water. An investigation of the reactivity and selectivity of the allylzinc species by using several typical allylboronates (6a, 6b, 6c, 6d) clarified several important roles of water in this allylation reaction. The allylation reactions of aldehydes with allylboronic acid 2,2‐dimethyl‐1,3‐propanediol esters proceeded smoothly in the presence of catalytic amounts of Zn(OH)2 and achiral ligand 4d in aqueous media to afford the corresponding syn‐adducts in high yields with high diastereoselectivities. In all cases, the α‐addition products were obtained and a wide substrate scope was tolerated. Furthermore, this reaction was applied to asymmetric catalysis by using chiral ligand 9. Based on the X‐ray structure of the Zn‐9 complex, several nonsymmetrical chiral ligands were also found to be effective. This reaction was further applied to catalytic asymmetric alkylallylation, chloroallylation, and alkoxyallylation processes and the synthetic utility of these reactions has been demonstrated.
Systematic review and meta-analysis of liver resection for metastatic melanoma
Authors: Aubin J-M , Rekman J , Vandenbroucke-Menu F , Lapointe R , Fairfull-Smith R J , Mimeault R , Balaa F K , Martel G
Published: June 2013

Background

The multidisciplinary management of metastatic melanoma now occasionally includes major hepatic resection. The objective of this work was to conduct a systematic review of the literature on liver resection for metastatic melanoma.

Methods

MEDLINE, Embase, the Cochrane Library and Scopus were searched (1990 to December 2012). Studies with at least ten patients undergoing liver resection for metastatic melanoma were included. Data on the outcomes of overall survival (OS) and/or disease-free survival (DFS) were abstracted and synthesized. Hazard ratios (HRs) were derived from survival curves and subjected to meta-analysis using random-effects models.

Results

Twenty-two studies involving 579 patients (13 per cent weighted resection rate) who underwent liver resection were included. Study quality was poor to moderate. Median follow-up ranged from 9 to 59 months. Median DFS ranged from 8 to 23 months, and median OS ranged from 14 to 41 months (R0, 22–66 months, R2, 10–16 months; R0versus R1/R2: HR 0.52, 95 per cent confidence interval (c.i.) 0.37 to 0.73). The OS rate was 56–100 per cent at 1 year, 34–53 per cent at 3 years and 11–36 per cent at 5 years. Median OS with non-operative management ranged from 4 to 12 months. Comparison of OS with resection and non-operative management favoured resection (HR 0.32, 95 per cent c.i. 0.22 to 0.46).

Conclusion

Radical resection of liver metastases from melanoma appears to improve overall survival compared with non-operative management or incomplete resection, but this observation requires future confirmation as selection bias may have confounded the results.
Sustained and transient attentional processes modulate neural predictors of memory encoding in consecutive time periods
Authors: Padovani Tullia , Koenig Thomas , Eckstein Doris , Perrig Walter J.
Published: June 2013

Memory formation is commonly thought to rely on brain activity following an event. Yet, recent research has shown that even brain activity previous to an event can predict later recollection (subsequent memory effect, SME). In order to investigate the attentional sources of the SME, event‐related potentials (ERPs) elicited by task cues preceding target words were recorded in a switched task paradigm that was followed by a surprise recognition test. Stay trials, that is, those with the same task as the previous trial, were contrasted with switch trials, which included a task switch compared to the previous trial. The underlying assumption was that sustained attention would be dominant in stay trials and that transient attentional reconfiguration processes would be dominant in switch trials. To determine the SME, local and global statistics of scalp electric fields were used to identify differences between subsequently remembered and forgotten items. Results showed that the SME in stay trials occurred in a time window from 2 to 1 sec before target onset, whereas the SME in switch trials occurred subsequently, in a time window from 1 to 0 sec before target onset. Both SMEs showed a frontal negativity resembling the topography of previously reported effects, which suggests that sustained and transient attentional processes contribute to the prestimulus SME in consecutive time periods.
Bifunctional Iron Complexes: Efficient Catalysts for CO and CN Reduction in Water
Authors: Mérel Delphine S. , Elie Margaux , Lohier Jean‐François , Gaillard Sylvain , Renaud Jean‐Luc
Published: June 2013

The application of bifunctional iron complexes for the hydrogenation of polarized CX bonds is reported. Two modified Knölker complexes bearing ionic fragments were synthesized and fully characterized. With these well‐defined complexes, the reaction proceeded under mild conditions in pure water, and various alcohols and amines were isolated in good yields. Compared with hydrogenation in organic solvents, better reactivities were observed.
Exploiting Multivalent Nanoparticles for the Supramolecular Functionalization of Graphene with a Nonplanar Recognition Motif
Authors: Brunetti Fulvio G. , Isla Helena , Aragó Juan , Ortí Enrique , Pérez Emilio M. , Martín Nazario
Published: June 2013

The supramolecular modification of planar graphene with the geometrically mismatched, curved 9,10‐di(1,3‐dithiole‐2‐ylidene)‐9,10‐dihydroanthracene (exTTF) molecule is demonstrated. The exTTF–graphene interaction is governed by π–π and CH–π interactions, with a negligible contribution from charge transfer. We amplified these weak forces through multivalent gold nanoparticles. Our results show that planarity is not a prerequisite for recognition motifs for graphene.
Asymmetric Synthesis of 2,4,5‐Trisubstituted Δ2‐Thiazolines
Authors: Bengtsson Christoffer , Nelander Hanna , Almqvist Fredrik
Published: June 2013

Δ2‐Thiazolines are interesting heterocycles that display a wide variety of biological characteristics. They are also common in chiral ligands used for asymmetric syntheses and as synthetic intermediates. Herein, we present asymmetric routes to 2,4,5‐trisubstituted Δ2‐thiazolines. These Δ2‐thiazolines were synthesized from readily accessible/commercially available α,β‐unsaturated methyl esters through a Sharpless asymmetric dihydroxylation and an O→N acyl migration reaction as key steps. The final products were obtained in good yields with up to 97 % enantiomeric excess.
Predictability of Enantiomeric Chromatographic Behavior on Various Chiral Stationary Phases Using Typical Reversed Phase Modeling Software
Authors: Wagdy Hebatallah A. , Hanafi Rasha S. , El‐Nashar Rasha M. , Aboul‐Enein Hassan Y.
Published: June 2013

Pharmaceutical companies worldwide tend to apply chiral chromatographic separation techniques in their mass production strategy rather than asymmetric synthesis. The present work aims to investigate the predictability of chromatographic behavior of enantiomers using DryLab HPLC method development software, which is typically used to predict the effect of changing various chromatographic parameters on resolution in the reversed phase mode. Three different types of chiral stationary phases were tested for predictability: macrocyclic antibiotics‐based columns (Chirobiotic V and T), polysaccharide‐based chiral column (Chiralpak AD‐RH), and protein‐based chiral column (Ultron ES‐OVM). Preliminary basic runs were implemented, then exported to DryLab after peak tracking was accomplished. Prediction of the effect of % organic mobile phase on separation was possible for separations on Chirobiotic V for several probes: racemic propranolol with 97.80% accuracy; mixture of racemates of propranolol and terbutaline sulphate, as well as, racemates of propranolol and salbutamol sulphate with average 90.46% accuracy for the effect of percent organic mobile phase and average 98.39% for the effect of pH; and racemic warfarin with 93.45% accuracy for the effect of percent organic mobile phase and average 99.64% for the effect of pH. It can be concluded that Chirobiotic V reversed phase retention mechanism follows the solvophobic theory. Chirality 25:506–513, 2013. © 2013 Wiley Periodicals, Inc.
A Highly Diastereoselective Three‐component Domino Reaction in Water Yielding Poly‐substituted 4,5‐Dihydropyrroles
Authors: Tong Guangjing , Xu Haiwei , Fan Wei , Jiang Bo , Wang Shuliang , Tu Shujiang
Published: June 2013

An efficient methodology for highly diastereoselective synthesis of poly‐substituted 4,5‐dihydropyrrole derivatives from readily available common reactants in water has been developed. During domino processes, the formation of pyrrole skeleton and its C2‐hydroxylation and C3‐arylamination were readily achieved via metal‐free [3+2] heterocyclization in a one‐pot operation.
Synthesis of Guanidines from Amines and Carbodiimides Catalyzed by Mono‐Indenyl‐Ligated Rare Earth Metal Bis(silylamide) Complexes
Authors: Chen Jue , Wang Yibin , Luo Yunjie
Published: June 2013

Nucleophilic addition of primary aromatic amines to carbodiimides in the presence of catalytic amount of the mono‐indenyl‐ligated rare earth metal bis(silylamide) complexes (C9H6CMe2CH2C5H4N‐α)Ln[N(SiHMe2)2]2 at room temperature afforded efficiently a series of guanidines with a wide spectrum of substituents on the nitrogen atoms.
Assessing the potential cost‐effectiveness of retesting IHC0, IHC1+, or FISH‐negative early stage breast cancer patients for HER2 status
Authors: Garrison Louis P. , Lalla Deepa , Brammer Melissa , Babigumira Joseph B. , Wang Bruce , Perez Edith A.
Published: June 2013

BACKGROUND

Fluorescence in situ hybridization (FISH) and immunohistochemistry (IHC) tests are commonly used to assess human epidermal growth factor 2 (HER2) status of tumors in patients with breast cancer. This analysis evaluates the likely cost‐effectiveness of expanded retesting to assess HER2 tumor status in women with early stage breast cancer.

METHODS

We developed a decision‐analytic model to estimate the incremental cost‐effectiveness ratio (ICER) of expanded reflex testing from a US payer perspective. Expanded reflex testing is defined as retesting tumor specimens from patients whose tumors are IHC0, IHC1+, or FISH‐negative on their first test. In the base case, we assumed that 80% of patient tumors are initially IHC‐tested and 20% are FISH‐tested. Testing outcomes for IHC and FISH with and without retesting were based on published meta‐analyses. The cost of tests and treatment and the long‐term health outcomes were obtained from the literature.

RESULTS

In the base case, we estimated that 2.27% of women who received expanded reflex testing would be HER2‐positive and receive trastuzumab treatment: the projected ICER was $36,721 per life year or $39,745 per quality‐adjusted life year (QALY). This varied between $47,100 per QALY and $35,500 per QALY if we assumed that 1%‐8% of patients retested were then HER2+, respectively. The results of deterministic and probabilistic sensitivity analysis were robust. This strategy would result in 4700 (2000‐17,000) patients being eligible to receive trastuzumab treatment annually.

CONCLUSIONS

Retesting patients who are IHC0, IHC1+, or FISH‐negative is projected to be a cost‐effective clinical strategy. Cancer 2013;119:3113–3122. © 2013 American Cancer Society.
Contactless magnetic gear for robot control application
Authors: Komiyama Hiroki , Uchimura Yutaka
Published: June 2013

This paper describes the application of a magnetic gear to a robot by fulfilling the essential requirements for a robot control, which are velocity control, position control, and force control. A magnetic gear is a transmission device that realizes contactless torque transmission by applying a magnetic force. When using a magnetic gear, cogging torque and spring characteristics need to be considered. In this paper, we introduce an approximate model of cogging torque. This model is used for velocity control to attenuate the disturbance due to cogging torque. In the case of position control, the oscillations due to the spring effect of the magnetic attractive force become a problem. To reduce the adverse effect due to these oscillations, resonance ratio control is applied. We also propose to use a magnetic gear for realizing force sensorless bilateral control of teleoperation. Because of the frictionless transmission of a magnetic gear, the force sensorless estimation of a reaction force can be realized using a reaction force observer. © 2013 Wiley Periodicals, Inc. Electr Eng Jpn, 184(4): 32–41, 2013; Published online in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/eej.22414