bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Lutetium Allyl Complex That Bears a Pyridyl‐Functionalized Cyclopentadienyl Ligand: Dual Catalysis on Highly Syndiospecific and cis‐1,4‐Selective (Co)Polymerizations of Styrene and Butadiene
Authors: Jian Zhongbao , Tang Shijia , Cui Dongmei 
Published: October 2010

AbstractA novel linked‐half‐sandwich lutetium–bis(allyl) complex [(C5Me4C5H4N)Lu(η3‐C3H5)2] (1) attached by a pyridyl‐functionalized cyclopentadienyl ligand was synthesized and fully characterized. Complex 1 in combination with [Ph3C][B(C6F5)4] exhibited unprecedented dual catalysis with outstanding activities in highly syndiotactic (rrrr>99 %) styrene polymerization and distinguished cis‐1,4‐selective (99 %) butadiene polymerization, respectively. Strikingly, this catalyst system exhibited remarkable activity (396 kg copolymer (molLu h)−1) for the copolymerization of butadiene and styrene. Irrespective of whether the monomers were fed in concurrent mode or sequential addition of butadiene followed by styrene, diblock copolymers were obtained exclusively, which was confirmed by a kinetics investigation of monomer conversion of copolymerization with time. In the copolymers, the styrene incorporation rate varied from 4.7 to 85.4 mol %, whereas the polybutadiene (PBD) block was highly cis‐1,4‐regulated (95 %) and the polystyrene segment remained purely syndiotactic (rrrr>99 %). Correspondingly, the copolymers exhibited glass transition temperatures (Tg) around −107 °C and melting points (Tm) around 268 °C; typical values for diblock microstructures. Such copolymers cannot be accessed by any other methods known to date. X‐ray powder diffraction analysis of these diblock copolymers showed that the crystallizable syndiotactic polystyrene (syn‐PS) block was in the toluene δ clathrate form. The AFM micrographs of diblock copolymer showed a remarkable phase‐separation morphology of the cis‐1,4‐PBD block and syn‐PS block. This represents the first example of a lutetium‐based catalyst showing both high activity and selectivity for the (co)polymerization of styrene and butadiene.
Silver Pyrazolates as Coordination‐Polymer Luminescent Metallomesogens
Authors: Barberá Joaquín , Lantero Ignacio , Moyano Sandra , Serrano José Luis , Elduque Anabel , Giménez Raquel 
Published: October 2010

AbstractSilver pyrazolates with columnar liquid‐crystal phases that are stable at room temperature have been prepared by reaction of silver nitrate with 3,5‐diarylpyrazolates. The complexes consist of open‐chain oligomers, despite the fact that the most common structural type for homoleptic coinage metal pyrazolates is the trimeric metallacycle [M(μ‐pz)]3. The special characteristics of silver in forming reversible metal–ligand bonds in solution, evidenced experimentally, leads to supramolecular organizations in which the silver cations promote self‐organization of the nonmesomorphic pyrazolates into helical 1D polymers that exhibit columnar mesophases. The materials are readily soluble in common organic solvents and are liquid‐crystalline over a broader temperature range than their gold counterparts, which are known to form discrete cyclic trinuclear species. Thin films of the silver complexes show luminescence at room temperature. The compounds described here are the first examples of luminescent metallomesogens formed by a main‐chain coordination polymer.
Influence of cell‐internalization on relaxometric, optical and compositional properties of targeted paramagnetic quantum dot micelles
Authors: Starmans L.W.E. , Kok M.B. , Sanders H.M.H.F. , Zhao Y. , de Mello Donegá C. , Meijerink A. , Mulder W.J.M. , Grüll H. , Strijkers G.J. , Nicolay K. 
Published: October 2010

AbstractQuantum dot micelles (pQDs) with a paramagnetic coating are promising nanoparticles for bimodal molecular imaging. Their bright fluorescence allows for optical detection, while their Gd payload enables visualization with contrast‐enhanced MRI. A popular approach in molecular MRI is the targeting of abundantly expressed cell surface receptors. Ligand‐receptor binding often results in cell internalization of the targeted contrast agent. The interpretation of molecular imaging with pQDs therefore requires knowledge about the consequences of cellular internalization for their relaxometric, optical and compositional properties. To study these, Cd‐containing core‐shell‐shell QDs coated with a monolayer of lipids, of which 50 mol% was a Gd‐containing lipid, were incubated with human umbilical vein‐derived endothelial cells (HUVECs) for up to 24 h. ανβ3‐integrin targeted (RGD) and non‐targeted (NT) pQDs were compared. pQDs uptake was monitored by fluorescence microscopy, FACS, ICP‐MS, relaxometry and MRI. Cell‐associated pQDs displayed longitudinal relaxation rates and fluorescent intensities which were linear with the cell‐associated Gd and Cd concentrations, implying that the Gd and Cd uptake by HUVECs can be quantified using relaxometric and optical measurements, respectively. However, the Gd‐to‐Cd molar ratio in pellets of pQD‐incubated cells was consistently higher than the Gd‐to‐Cd molar ratio of the pQDs as prepared. It is proposed that this increase in Gd‐to‐Cd molar ratio was due to non‐specific lipid‐transfer between the pQDs and the cellular membranes. These findings show that, in the case of contrast agents that are formed by non‐covalent interactions, experimental procedures are needed with which representative components of the probes can be monitored. Copyright © 2010 John Wiley & Sons, Ltd.
Distribution of Na/K‐ATPase alpha 3 isoform, a sodium‐potassium P‐type pump associated with rapid‐onset of dystonia parkinsonism (RDP) in the adult mouse brain
Authors: Bøttger Pernille , Tracz Zuzanna , Heuck Anders , Nissen Poul , Romero‐Ramos Marina , Lykke‐Hartmann Karin 
Published: October 2010

AbstractThe Na+/K+‐ATPase1 alpha subunit 3 (ATP1α3) is one of many essential components that maintain the sodium and potassium gradients across the plasma membrane in animal cells. Mutations in the ATP1A3 gene cause rapid‐onset of dystonia parkinsonism (RDP), a rare movement disorder characterized by sudden onset of dystonic spasms and slowness of movement. To achieve a better understanding of the pathophysiology of the disease, we used immunohistochemical approaches to describe the regional and cellular distribution of ATP1α3 in the adult mouse brain. Our results show that localization of ATP1α3 is restricted to neurons, and it is expressed mostly in projections (fibers and punctuates), but cell body expression is also observed. We found high expression of ATP1α3 in GABAergic neurons in all nuclei of the basal ganglia (striatum, globus pallidus, subthalamic nucleus, and substantia nigra), which is a key circuitry in the fine movement control. Several thalamic nuclei structures harboring connections to and from the cortex expressed high levels of the ATP1α3 isoform. Other structures with high expression of ATP1α3 included cerebellum, red nucleus, and several areas of the pons (reticulotegmental nucleus of pons). We also found high expression of ATP1α3 in projections and cell bodies in hippocampus; most of these ATP1α3‐positive cell bodies showed colocalization to GABAergic neurons. ATP1α3 expression was not significant in the dopaminergic cells of substantia nigra. In conclusion, and based on our data, ATP1α3 is widely expressed in neuronal populations but mainly in GABAergic neurons in areas and nuclei related to movement control, in agreement with RDP symptoms. J. Comp. Neurol. 519:376‐404, 2011. © 2010 Wiley‐Liss, Inc.
Temperature‐Dependent Prediction of the Liquid Entropy of Ionic Liquids
Authors: Preiss Ulrich , Emel'yanenko Vladimir N. , Verevkin Sergey P. , Himmel Daniel , Paulechka Yauheni U. , Krossing Ingo 
Published: October 2010

AbstractModeling of the temperature‐dependent liquid entropy of ionic liquids (ILs) with great accuracy using COSMO‐RS is demonstrated. The minimum structures of eight IL ion pairs are investigated and the entropy, calculated from ion pairs, is found to differ on average only 2 % from the available experimental values (119 data points). For calculations with single ions, the average error amounts to 2.6 % and stronger‐coordinating ions tend to give higher deviations. Additionally, the first parameterization of the standard liquid entropy for ILs is presented in the context of traditional volume‐based thermodynamics (Sl0=1.585 kJ mol−1 K−1 nm−3⋅rm3+14.09 J mol−1 K−1), which sheds light on the statistical treatment of ionic interactions. The findings provide the first direct access to accurate predictions of liquid entropies of ILs, which are tedious and time‐consuming to measure.
Characterization of in vitro generated metabolites of the selective androgen receptor modulators S‐22 and S‐23 and in vivo comparison to post‐administration canine urine specimens
Authors: Thevis Mario , Gerace Enrico , Thomas Andreas , Beuck Simon , Geyer Hans , Schlörer Nils , Kearbey Jeffrey D. , Dalton James T. , Schänzer Wilhelm 
Published: October 2010

AbstractSelective androgen receptor modulators (SARMs) have great therapeutic potential in various diseases including cancer cachexia, sarcopenia, and osteoporosis, and the number of drug candidates has been growing over the last decade. The SARM drug candidates S‐22 and S‐23 belong to one of the most advanced groups of androgen receptor modulators and are based on an arylpropionamide‐derived core structure. Due to their anabolic effects, SARMs have been prohibited in elite sports and have been a subject of sports drug testing programmes since January 2008. Consequently, the structure of analytically useful urinary metabolites should be elucidated to provide targets for sensitive and retrospective analysis. In the present study, the phase‐I and ‐II metabolism of S‐22 and S‐23 was simulated using hepatic human enzymes, and resulting metabolites were characterized by means of state‐of‐the‐art mass spectrometric approaches employing high resolution/high accuracy Orbitrap mass spectrometry. Subsequently, the newly defined target compounds including the glucuronic acid conjugates of S‐22 and S‐23, their corresponding monohydroxylated and bishydroxylated analogs, as well as their B‐ring depleted counterparts were implemented into an existing routine doping control procedure, which was examined for its specificity for the added substances. In order to obtain proof‐of‐concept data for authentic urine specimens, canine urine samples collected up to 72 h after oral administration of S‐22 to dogs were analyzed using the established approach outlining the capability of the presented assay to detect the glucuronide of S‐22 as well as the B‐ring‐depleted metabolite (M3) in all samples following therapeutic (31.4 µg/kg) dosing. Finally, M3 was chemically synthesized, characterized by nuclear magnetic resonance spectroscopy and high resolution/high accuracy mass spectrometry, and chosen as primary target for future doping control analyses. Copyright © 2010 John Wiley & Sons, Ltd.
Unusually Large Bite Angle of a Distally Diphosphanylated Calix[4]arene Chelator (Eur. J. Inorg. Chem. 31/2010)
Authors: Sameni Soheila , Jeunesse Catherine , Awada Mouhamad , Matt Dominique , Welter Richard 
Published: October 2010

AbstractThe cover picture shows the structure of a calix[4]arene‐based ligand with an unusually large bite angle. Calix[4]arenes constitute versatile macrocyclic compounds, which can be obtained by condensation of phenols with formaldehyde. The so‐called CALDIPs, which are diphosphanes built upon such a skeleton, have recently found applications in a variety of C–C bond‐forming reactions, including polymerisation reactions. In the presence of group 8–10 transition metals, CALDIP ligands form straightforwardly dynamic chelate complexes, in which the ligand bite angle undergoes periodic variation. In the article by C. Jeunesse, D. Matt et al. on p. 4917 ff, a new chelate complex is described in which a CALDIP ligand adopts an unexpectedly large bite angle of 139°, which thus illustrates the great flexibility of the calix[4]arene core. The key ligand is depicted as superimposed over the sky of Strasbourg city (photo courtesy of Dr. R. Ruppert, UdS). Phenol–formaldehyde condensation products were already synthesised in Strasbourg by A. Baeyer in 1872.
Efficient Synthesis of Deazaguanosine‐Derived tRNA Nucleosides PreQ0, PreQ1, and Archaeosine Using the Turbo‐Grignard Method
Authors: Brückl Tobias , Thoma Ines , Wagner Andreas J. , Knochel Paul , Carell Thomas 
Published: October 2010

AbstractThe natural products PreQ1, PreQ0, and archaeosine are deazaguanosine‐derived natural products of immense biological importance. All three are critical components of tRNAs and, as such, are involved in decoding genetic information. We were able to consolidate and shorten the syntheses of all three compounds by using a novel Turbo‐Grignard‐based approach. The reported iodine/magnesium exchange followed by a Grignard reaction with the deazaguanosine skeleton showed a high tolerance towards important functional groups such as esters and amides.
Microwave‐Assisted Diversity‐Oriented Domino Synthesis of Functionalized Nicotinic Acid Derivatives
Authors: Tejedor David , Méndez‐Abt Gabriela , García‐Tellado Fernando 
Published: October 2010

AbstractThe microwave‐assisted diversity‐oriented domino synthesis of functionalized alkyl nicotinates from propargyl vinyl ethers is described. The domino manifold comprises a complex network of reactions involving at least five distinct chemical steps. The obtained alkyl nicotinates incorporate two diversity points at the ring and one ester functionality as convenient handles for further elaboration.
Characterization of particle capture in a sawtooth patterned insulating electrokinetic microfluidic device
Authors: Staton Sarah J. R. , Chen Kang Ping , Taylor Thomas J. , Pacheco Jose Rafael , Hayes Mark A. 
Published: October 2010

AbstractHere we present a scheme to separate particles according to their characteristic physical properties, including size, charge, polarizability, deformability, surface charge mobility, dielectric features, and local capacitance. Separation is accomplished using a microdevice based on direct current insulator gradient dielectrophoresis that can isolate and concentrate multiple analytes simultaneously at different positions. The device is dependent upon dielectrophoretic and electrokinetic forces incorporating a global longitudinal direct current field as well as using shaped insulating features within the channel to induce local gradients. This design allows for the production of strong local field gradients along a global field causing particles to enter, initially transported through the channel by electrophoresis and electroosmosis (electrokinetics), and to be isolatedviarepulsive dielectrophoretic forces that are proportional to an exponent of the field gradient. Sulfate‐capped polystyrene nano and microparticles (20, 200 nm, and 1 μm) were used as probes to demonstrate the influence of channel geometry and applied longitudinal field on separation behavior. These results are consistent with models using similar channel geometry and indicate that specific particulate species can be isolated within a distinct portion of the device, whereas concentrating particles by factors from 103to 106.
Chip‐based CE for rapid separation of 8‐aminopyrene‐1,3,6‐trisulfonic acid (APTS) derivatized glycans
Authors: Smejkal Petr , Szekrényes Ákos , Ryvolová Markéta , Foret František , Guttman András , Bek Fritz , Macka Mirek 
Published: October 2010

AbstractFluorescently labeled carbohydrates released from glycoproteins were separated using a commercially available microfluidic chip electrophoresis system. While the instrumentation was primarily designed for DNA analysis it was found that the application base can be easily expanded using the development software provided by the manufacturer. The carbohydrates were released by enzymatic digestion (PNGase F) from glycoproteins present in human plasma after boronic acid – lectin affinity enrichment. After fluorescent labeling with 8‐aminopyrene‐1,3,6‐trisulfonic acid the carbohydrates were separated based on capillary gel electrophoresis mechanism and detected by a fluorescence detector using a blue (470 nm) LED. The separation was completed in 40 s in a microfluidic channel of 14 mm length. Glucose ladder carbohydrate oligomers differing by one glucose unit were baseline separated up to a 20‐mer with the main limitation being the detection sensitivity. As expected, the observed resolution in these experiments did not approach that of standard CE with 20 times longer separation distance; however, the chip‐based analysis excelled in the speed of the separation. Similar electrophoretic profiles of glycans released from plasma glycoproteins were obtained using a standard CE equipment with 35 cm separation length and microfluidic chips with a separation distance of only 14 mm.
Do verbal interactions with infants during electronic media exposure mitigate adverse impacts on their language development as toddlers?
Authors: Mendelsohn Alan L. , Brockmeyer Carolyn A. , Dreyer Benard P. , Fierman Arthur H. , Berkule‐Silberman Samantha B. , Tomopoulos Suzy 
Published: October 2010

AbstractThe goal of this study was to determine whether verbal interactions between mothers and their 6‐month‐old infants during media exposure (‘media verbal interactions’) might have direct positive impacts, or mitigate any potential adverse impacts of media exposure, on language development at 14 months. For 253 low‐income mother–infant dyads participating in a longitudinal study, media exposure and media verbal interactions were assessed using 24‐hour recall diaries. Additionally, general level of cognitive stimulation in the home [StimQ] was assessed at 6 months and language development [Preschool Language Scale‐4] was assessed at 14 months. Results suggest that media verbal interactions play a role in the language development of infants from low‐income, immigrant families. Evidence showed that media verbal interactions moderated adverse impacts of media exposure found on 14‐month language development, with adverse associations found only in the absence the these interactions. Findings also suggest that media verbal interactions may have some direct positive impacts on language development, in that media verbal interactions during the co‐viewing of media with educational content (but not other content) were predictive of 14‐month language independently of overall level of cognitive stimulation in the home. Copyright © 2010 John Wiley & Sons, Ltd.
A blocking and regularization approach to high‐dimensional realized covariance estimation
Authors: Hautsch Nikolaus , Kyj Lada M. , Oomen Roel C. A. 
Published: October 2010

SUMMARYWe introduce a blocking and regularization approach to estimate high‐dimensional covariances using high‐frequency data. Assets are first grouped according to liquidity. Using the multivariate realized kernel estimator of Barndorff‐Nielsen et al. (2010), the covariance matrix is estimated block‐wise and then regularized. The performance of the resulting blocking and regularization (‘RnB’) estimator is analyzed in an extensive simulation study mimicking the liquidity and market microstructure features of the S&P 1500 universe. The RnB estimator yields efficiency gains for varying liquidity settings, noise‐to‐signal ratios and dimensions. An empirical application of estimating daily covariances of the S&P 500 index confirms the simulation results. Copyright © 2010 John Wiley & Sons, Ltd.
A content analyses of guided imagery scripts: a strategy for the development of cultural adaptations
Authors: La Roche Martin J. , Batista Cynthia , D'Angelo Eugene 
Published: October 2010

AbstractThis paper proposes a first step in deciding whether it is necessary to develop a cultural adaptation by comparing the cultural characteristics of an intervention with the same characteristics of a specific group. Larger cultural differences suggest a greater need to conduct a cultural adaptation. This recommendation stems from the cultural match theory (CMT) which, explains that therapeutic outcomes increase as interventions are more similar to the cultural characteristics of specific treatment groups. However, the CMT has rarely been tested, partly because strategies to effectively measure the cultural characteristics of an intervention are still lacking. This article addresses this gap by assessing two dimensions of the self‐orientation relevant to cultural adaptations, namely, idiocentrism—the tendency to define oneself in isolation from others—and allocentrism—the tendency to define oneself in relationship to others—through a content analysis of guided imagery scripts. Two independent evaluators analyzed 123 guided imagery scripts (published during 1989–2008) using 6 theoretically derived categories to analyze idiocentrism versus allocentrism. Results indicated that idiocentric elements were 1.5 to 52.3 times more frequently used than were allocentric ones. The implications of these findings for the development of culturally adapted interventions are discussed. © 2010 Wiley Periodicals, Inc. J Clin Psychol 00:1–10, 2010.
Generalized anxiety disorder: clinical presentation, diagnostic features, and guidelines for clinical practice
Authors: van der Heiden Colin , Methorst Gerda , Muris Peter , van der Molen Henk T. 
Published: October 2010

AbstractGeneralized anxiety disorder (GAD) is a prevalent and disabling disorder characterised by persistent worrying, anxiety symptoms, and tension. General practitioners and mental healthcare professionals frequently misdiagnose the presenting symptoms. This article addresses the clinical presentation of GAD and provides guidelines for discriminating GAD from other disorders, based on theoretical considerations and clinical experience. Debate relating to the validity of the definition of GAD is discussed, and suggestions are made for improving the criteria for GAD, which may guide future versions of classification systems such as the Diagnostic and Statistical Manual. © 2010 Wiley Periodicals, Inc. J Clin Psychol 00:1–16, 2010.
Antibody formation and mannose‐6‐phosphate receptor expression impact the efficacy of muscle‐specific transgene expression in murine Pompe disease
Authors: Sun Baodong , Li Songtao , Bird Andrew , Yi Haiqing , Kemper Alex , Thurberg Beth L. , Koeberl Dwight D. 
Published: October 2010

AbstractBackgroundLysosomal storage disorders such as Pompe disease can be more effectively treated, if immune tolerance to enzyme or gene replacement therapy can be achieved. Alternatively, immune responses against acid α‐glucosidase (GAA) might be evaded in Pompe disease through muscle‐specific expression of GAA with adeno‐associated virus (AAV) vectors.MethodsAn AAV vector containing the MHCK7 regulatory cassette to drive muscle‐specific GAA expression was administered to GAA knockout (KO) mice, immune tolerant GAA‐KO mice and mannose‐6‐phosphate deficient GAA‐KO mice. GAA activity and glycogen content were analyzed in striated muscle to determine biochemical efficacy.ResultsThe biochemical efficacy from GAA expression was slightly reduced in GAA‐KO mice, as demonstrated by higher residual glycogen content in skeletal muscles. Next, immune tolerance to GAA was induced in GAA‐KO mice by co‐administration of a second AAV vector encoding liver‐specific GAA along with the AAV vector encoding muscle‐specific GAA. Antibody formation was prevented by liver‐specific GAA, and the biochemical efficacy of GAA expression was improved in the absence of antibodies, as demonstrated by significantly reduced glycogen content in the diaphragm. Efficacy was reduced in old GAA‐KO mice despite the absence of antibodies. The greatest impact upon gene therapy was observed in GAA‐KO mice lacking the mannose‐6‐phosphate receptor in muscle. The clearance of stored glycogen was markedly impaired despite high GAA expression in receptor‐deficient Pompe disease mice.ConclusionsOverall, antibody formation had a subtle effect upon efficacy, whereas the absence of mannose‐6‐phosphate receptors markedly impaired muscle‐targeted gene therapy in murine Pompe disease. Copyright © 2010 John Wiley & Sons, Ltd.