bluuebunny/crossref_metadata_2025_split huggingface dataset:
Efficient Palladium‐Catalyzed CO Hydrogenolysis of Benzylic Alcohols and Aromatic Ketones with Polymethylhydrosiloxane
Authors: Wang Hu , Li Li , Bai Xing‐Feng , Shang Jun‐Yan , Yang Ke‐Fang , Xu Li‐Wen 
Published: February 2013

AbstractA simple method has been developed for the reductive deoxygenation of aromatic ketones and benzylic alcohols in the presence of polymethylhydrosiloxane (PMHS). The reductive deoxygenation of aromatic ketones and benzylic alcohols, including secondary alcohols, to the corresponding methylene hydrocarbons has been achieved in good to excellent yields using palladium chloride (PdCl2) as catalyst and PMHS as hydride source. Such deoxygenations were successfully with aryl alkyl ketones and diaryl ketones, as exemplified by the reductive deoxygenation of acetophenone and benzopheneone, respectively. The corresponding benzylic alcohols and secondary alcohol analogues could also be converted into their respective methylene hydrocarbons by the PdCl2/PMHS system.
Rhodium(III)‐Catalyzed Annulation of Azomethine Ylides with Alkynes via CH Activation
Authors: Chen Yuye , Wang Fen , Zhen Wencui , Li Xingwei 
Published: February 2013

AbstractThe rhodium(III)‐catalyzed coupling of azomethine ylides with alkynes via CH activation has been developed for the synthesis of indenamines in moderate to high yields. The coupled products can be further oxidized to indenones and derivatives.
A Deacetylation–Diazotation–Coupling Sequence: Palladium‐ Catalyzed CC Bond Formation with Acetanilides as Formal Leaving Groups
Authors: Schmidt Bernd , Berger René 
Published: February 2013

AbstractAcetanilides can be deacetylated and diazotized in situ, and subsequently used in Pd‐catalyzed coupling reactions without isolation of the diazonium intermediate. Heck reactions, Suzuki cross‐coupling reactions, and a Pd‐catalyzed [2+2+1] cycloaddition have been investigated as terminating CC bond‐forming steps of this one‐flask sequence. The sequence does not require the exchange of solvents or removal of by‐products between the individual steps, but proceeds by addition of reagents and catalysts in due course.
Synthesis of N,N′‐Disulfonylamidines from Sulfonamides and Alkynes by a Two‐Step, One‐Pot Reaction with Nonafluorobutanesulfonyl Azide
Authors: Suárez José Ramón , Kwiczak Joanna , Grenda Katarzyna , Jimeno M. Luisa , Chiara Jose Luis 
Published: February 2013

AbstractNonafluorobutanesulfonyl azide is an advantageous alternative to triflyl azide for the efficient synthesis of sulfonyl azides from sulfonamides in terms of its higher reactivity, lower cost, and non‐hazardous nature. The reagent has proven its utility in a novel synthesis of N,N′‐disulfonylamidines from available sulfonamides by a copper‐catalyzed two‐step, one‐pot sequential process with added terminal alkynes.
Synthesis of Functionalized Bicyclic Imines via Intramolecular Azide‐Alkene 1,3‐Dipolar Cycloaddition/Intramolecular Stork Alkylation Cascade Reaction
Authors: de Miguel Irene , Velado Marina , Herradón Bernardo , Mann Enrique 
Published: February 2013

AbstractA cascade intramolecular azide‐alkene 1,3‐dipolar cycloaddition/Stork alkylation reaction has been developed for the synthesis of functionalized cyclic imines with a pyrroline and piperideine structures, employing readily available ω‐azidodienes.
Cu2‐xS Surface Phases and Their Impact on the Electronic Structure of CuInS2 Thin Films – A Hidden Parameter in Solar Cell Optimization
Authors: Bär Marcus , Klaer Joachim , Weinhardt Lothar , Wilks Regan G. , Krause Stefan , Blum Monika , Yang Wanli , Heske Clemens , Schock Hans‐Werner 
Published: February 2013

AbstractThe surface properties of CuInS2 (CIS) thin‐film solar cell absorbers are investigated by a combination of electron and soft X‐ray spectroscopies. Spatially separated regions of varying colors are observed and identified to be dominated by either CuS or Cu2S surface phases. After their removal by KCN etching, the samples cannot be distinguished by eye and the CIS surface is found to be Cu‐deficient in both regions. However, a significantly more pronounced off‐stoichiometry in the region initially covered by Cu2S can be identified. In this region, the resulting surface band gap is also significantly larger than the EgSurf of the initially CuS‐terminated region. Such variations may represent a hidden parameter which, if overlooked, induces irreproducibility and thus prevents systematic optimization efforts.
Band Gap Control in Diketopyrrolopyrrole‐Based Polymer Solar Cells Using Electron Donating Side Chains
Authors: Hendriks Koen H. , Li Weiwei , Wienk Martijn M. , Janssen René A. J. 
Published: February 2013

AbstractWe compare the opto‐electronic and photovoltaic properties of two diketopyrrolopyrrole (DPP) based semiconducting polymers in which the DPP unit alternates along the chain with a conjugated bis(dithienyl)phenylene (4TP) unit. The two polymers differ only in the solubilizing substituents on the thiophene rings which are either alkyl (PDPP4TP) or alkoxy (PDPP4TOP) groups. We show that alkoxy groups lower the optical band gap and increase the ionization potential compared to the alkyl groups. As a result, PDDP4TOP provides a significantly higher charge generation efficiency and concomitant higher short‐circuit current, 18.0 mA cm−2 vs. 12.4 mA cm−2, compared to PDPP4TP in optimized devices with [6,6]phenyl‐C71‐butyric acid methyl ester ([70]PCBM) as acceptor, but a simultaneous decrease in open circuit voltage, 0.51 vs. 0.67 V. The increased current arises from a higher external quantum efficiency and a wider spectral coverage. The net result is a small increase in power conversion efficiency from 5.8% for PDPP4TP to 6.0% for the PDPP4TOP in optimized devices. The optimized processing conditions and bulk heterojunction morphology are virtually identical for both photoactive layers. The study demonstrates that the side chains enable effective method for rationally designing new photoactive semiconducting polymers.
Talocalcaneal coalition in Muenke syndrome: Report of a patient, review of the literature in FGFR‐related craniosynostoses, and consideration of mechanism
Authors: Agochukwu Nneamaka B. , Solomon Benjamin D. , Benson Laurel J. , Muenke Maximilian 
Published: February 2013

AbstractMuenke syndrome is an autosomal dominant craniosynostosis syndrome resulting from a defining point mutation in the Fibroblast Growth Factor Receptor3 (FGFR3) gene. Muenke syndrome is characterized by coronal craniosynostosis (bilateral more often than unilateral), hearing loss, developmental delay, and carpal and/or tarsal bone coalition. Tarsal coalition is a distinct feature of Muenke syndrome and has been reported since the initial description of the disorder in the 1990s. Although talocalcaneal coalition is the most common tarsal coalition in the general population, it has never previously been reported in a patient with Muenke syndrome. We present a 7‐year‐old female patient with Muenke syndrome and symptomatic talocalcaneal coalition. She presented at the age of 7 with limping, tenderness and pain in her right foot following a fall and strain of her right foot. She was treated with ibuprofen, shoe inserts, a CAM walker boot, and stretching exercises without much improvement in symptoms. A computed tomography (CT) scan revealed bilateral talocalcaneal coalitions involving the middle facet. She underwent resection of the talocalcaneal coalitions, remaining pain‐free post‐operatively with an improvement in her range of motion, gait, and mobility. This report expands the phenotype of tarsal coalition in Muenke syndrome to include talocalcaneal coalition. A literature review revealed a high incidence of tarsal coalition in all FGFR related craniosynostosis syndromes when compared to the general population, a difference that is statistically significant. The most common articulation involved in all syndromic craniosynostoses associated with FGFR mutations is the calcaneocuboid articulation. © 2013 Wiley Periodicals, Inc.
Microwave curing of epoxy polymers reinforced with carbon nanotubes
Authors: Fotiou Ignatios , Baltopoulos Athanasios , Vavouliotis Antonios , Kostopoulos Vassilis 
Published: February 2013

AbstractThe driver for this study is the observation that heating of carbon nanotubes (CNTs) with electromagnetic field can offer a more efficient and cost‐effective alternative in heat transfer for the production of composites. The idea of this study is twofold; CNT can work as microwave (MW) radiation susceptors and they can act as nanoreinforcements in the final system. To test these assumptions, a household oven was modified to control the curing schedule. Polymers with different CNT concentrations were prepared (0.5 and 1.0 wt %). The dispersion of the CNTs in the epoxy was achieved using shear‐mixing dissolver technique. MW and conventionally cured specimens were also produced in a convection oven for reference. Thermal and mechanical tests were used as control point. A curing schedule investigation was further performed to quantify the energy and time‐saving capabilities using CNT and MWs. The presence of CNTs into epoxy matrix has been proven beneficial for the shortening of the curing time. MW‐cured composites showed the same degree of polymerization with the conventionally cured composites in a shorter time period and this time was reduced as the CNT concentration was increased. A good distribution of the CNT is required to avoid hot spot effects and local degradation. Mechanical performance was, in some cases, favored by the use of CNT. The benefit from the use of MWs and CNT could reach at least 40% in terms of energy needed and time without sacrificing mechanical performance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Description of a Bivalent Cannabinoid Ligand with Hypophagic Properties
Authors: Fernández‐Fernández Cristina , Decara Juan , Bermúdez‐Silva Francisco J. , Sánchez Eva , Morales Paula , Gómez‐Cañas María , Gómez‐Ruíz María , Callado Luis F. , Goya Pilar , Rodríguez de Fonseca Fernando , Martín M. Isabel , Fernández‐Ruíz Javier , Meana J. Javier , Jagerovic Nadine 
Published: February 2013

AbstractA series of bivalent cannabinoid ligands is proposed. The synthesis of double amides based on the rimonabant structure separated by an alkyl chain and the evaluation of their affinities for cannabinoid receptors are reported. The data of 4d confirmed that a bivalent structure is a suitable scaffold for CB1 cannabinoid receptor binding. The compound 4d was selected for in vitro and in vivo pharmacological evaluations. Moreover, intraperitoneal administration of 4d to food‐deprived rats resulted in a dose‐dependent inhibition of feeding that was maintained up to 240 min.
One‐Pot Stereoselective Synthesis of 2‐Acylaziridines and 2‐Acylpyrrolidines from N‐(Propargylic)hydroxylamines
Authors: Miyamoto Yoshiaki , Wada Norihiro , Soeta Takahiro , Fujinami Shuhei , Inomata Katsuhiko , Ukaji Yutaka 
Published: February 2013

AbstractThe stereoselective direct transformation of N‐(propargylic)hydroxylamines into cis‐2‐acylaziridines was achieved by the combined use of AgBF4 and CuCl. Copper salts were found to promote the transformation of the intermediary 4‐isoxazolines into 2‐acylaziridines and both 3‐aryl‐ and 3‐alkyl‐substituted 2‐acylaziridines could be prepared by using this method. Furthermore, subsequent 1,3‐dipolar cycloaddition of azomethine ylides that were generated in situ from the intermediary 2‐acylaziridines with maleimides was achieved in a stereoselective one‐pot procedure to afford the corresponding 2‐acylpyrrolidines, which consisted of an octahydropyrrolo[3,4‐c]pyrrole skeleton.
Descriptive epidemiology of cleft lip and cleft palate in Western Australia
Authors: Bell Jane C. , Raynes‐Greenow Camille , Bower Carol , Turner Robin M. , Roberts Christine L. , Nassar Natasha 
Published: February 2013

AbstractBackgroundThe reported birth prevalence of orofacial clefts (OFCs) varies considerably. This study describes the epidemiology of OFCs in an Australian population.MethodsWe studied infants diagnosed with cleft lip, with or without cleft palate (CL±P), and cleft palate only (CPO) since 1980 and reported to the population based Western Australian Register of Developmental Anomalies. We calculated prevalence rates by sex, Aboriginal status, geographic location, and socio‐economic status. Associations between clefts and folate availability, pregnancy characteristics, pregnancy outcomes, other congenital anomalies, and age at diagnosis were also investigated.ResultsFrom 1980 to 2009, 917 infants with CL±P (12.05 per 10,000) and from 1980 to 2004, 621 infants with CPO (10.12 per 10,000) were registered. Prevalence rates for CL±P and CPO were 1.9 and 1.3 times higher, respectively, for Aboriginal Australians. Additional anomalies were reported for 31% of infants with CL±P and for 61% with CPO; chromosomal anomalies and other specific diagnoses accounted for 46% and 66%, respectively, of those with CL±P and CPO with additional anomalies. Almost all (99.7%) children with CL±P were diagnosed before 1 year of age, but 12% of CPO diagnoses were made after 1 year of age; 94% of these diagnoses were of submucous clefts and bifid uvula.ConclusionsThese data provide a picture of the prevalence of OFCs in WA since 1980, and provide a useful reference for OFC data in Australia and internationally. The quality and completeness of the WARDA data are high, reflected in high prevalence rates, and proportions of clefts occurring with other anomalies. Birth Defects Research (Part A), 2013 © 2013 Wiley Periodicals, Inc.
Re‐offending in forensic patients released from secure care: The role of antisocial/borderline personality disorder co‐morbidity, substance dependence and severe childhood conduct disorder
Authors: Howard Rick , McCarthy Lucy , Huband Nick , Duggan Conor 
Published: February 2013

ABSTRACTBackgroundResearch suggests that a particular externalising phenotype, manifested in a developmental trajectory from severe childhood conduct disorder through early‐onset substance abuse to adult antisocial/borderline personality disorder co‐morbidity, may increase risk of antisocial behaviour in general and criminal recidivism in particular.AimThis study aims to test the hypothesis that antisocial/borderline co‐morbidity together with the triad of substance dependence, severe conduct disorder and borderline pathology would result in an increased risk of criminal recidivism.MethodsFifty‐three men who had been assessed and treated in a secure hospital unit were followed up after they had returned to the community. They were assessed for severity of the following: (i) antisocial personality disorder; (ii) borderline personality disorder; (iii) drug/alcohol dependence; and (iv) high Psychopathy Checklist Revised scores (factors 1 and 2).ResultsPatients with antisocial/borderline co‐morbidity took significantly less time to re‐offend compared with those without such co‐morbidity. Both Psychopathy Checklist Revised factor 2 and the tripartite risk measure significantly predicted time to re‐offence; the former largely accounted for the predictive accuracy of the latter.ConclusionRisk of criminal recidivism can be adequately assessed without recourse to the pejorative term ‘psychopath’. It is sufficient to assess the presence of the three elements of our risk measure: borderline and antisocial personality disorders in the context of drug/alcohol dependence and severe childhood conduct disorder.Practical implications of the study are as follows. (i) Sound assessment of personality, inclusive of a detailed history of childhood conduct disorder as well as adolescent and adult substance misuse, yields good enough information about risk of recidivism without recourse to the pejorative concept of ‘psychopathy’. (ii) Given the high risk of alcohol‐related violence in individuals with antisocial/borderline co‐morbidity, there is a need for specific alcohol‐directed interventions to help such men retain control of their substance use. Copyright © 2013 John Wiley & Sons, Ltd.
Development of a Stepwise Reductive Deoxygenation Process by Ru‐Catalysed Homogeneous Ketone Reduction and Pd‐Catalysed Hydrogenolysis in the Presence of Cu Salts
Authors: Grainger Damian M. , Zanotti‐Gerosa Antonio , Cole Kevin P. , Mitchell David , May Scott A. , Pollock Patrick M. , Calvin Joel R. 
Published: February 2013

AbstractA stepwise catalytic reduction of ketone 1 to alcohol 2 and subsequently to aryl(imidazo[1,2‐b]pyridazinyl)methane 3 is described, which provides synthetically useful chemoselectivity at acceptably low catalyst loadings. Undesired reactive sites include an aryl chloride, heteroarylchloride and benzylic amine group. The presence of these functional groups presents a significant challenge to chemoselectivity for both reduction steps. For selective CO reduction of highly functionalised 1, high chemoselectivity was observed at low catalyst loading by using Wills’ tethered Ru transfer‐hydrogenation catalyst 13. The selective hydrogenolysis of 2 was then accomplished under acidic hydrogenation conditions by using a Pd/C catalyst in the presence of Cu salts. This procedure has been demonstrated on a multi‐gram scale, which makes this approach a viable method to use a combination of homogeneous and heterogeneous catalysis.
Dendron to Central Core S1–S1 and S2–Sn (n>1) Energy Transfers in Artificial Special Pairs Containing Dendrimers with Limited Numbers of Conformations
Authors: Harvey Pierre D. , Brégier Frédérique , Aly Shawkat M. , Szmytkowski Jędrzej , Paige Matthew F. , Steer Ronald P. 
Published: February 2013

AbstractTwo dendrimers consisting of a cofacial free‐base bisporphyrin held by a biphenylene spacer and functionalized with 4‐benzeneoxomethane (5‐(4‐benzene)tri‐10,15,20‐(4‐n‐octylbenzene)zinc(II)porphyrin) using either five or six of the six available meso‐positions, have been synthesized and characterized as models for the antenna effect in Photosystems I and II. The presence of the short linkers, ‐CH2O‐, and long C8H17 soluble side chains substantially reduces the number of conformers (foldamers) compared with classic dendrimers built with longer flexible chains. This simplification assists in their spectroscopic and photophysical analysis, notably with respect to fluorescence resonance energy transfer (FRET). Both steady‐state and time‐resolved spectroscopic measurements indicate that the cofacial free bases and the flanking zinc(II)–porphyrin antennas act as energy acceptor and donor, respectively, following excitation in either the Q or Soret bands of the dendrimers. The rate constants for singlet electronic energy transfer (kEET) extracted from the S1 and S2 fluorescence lifetimes of the donor in the presence and absence of the acceptor are ≤ (0.1–0.3)×109 and ∼2×109 s−1 for S1→S1 (range from a bi‐exponential decay model) and about 1.5×1012 s−1 for S2→Sn (n>1). Comparisons of these experimental data with those calculated from Förster theory using orientation factors and donor–acceptor distances extracted from computer modeling suggest that a highly restricted number of the many foldamers facilitate energy transfer. These foldamers have the lowest energy by molecular modeling and consist of one or at most two of the flanking zinc porphyrin antennas folded so they lie near the central artificial special pair core with the remaining antennas located almost parallel to and far from it.
A New Class of Remote N‐Heterocyclic Carbenes with Exceptionally Strong σ‐Donor Properties: Introducing Benzo[c]quinolin‐6‐ylidene
Authors: Mayer Ulrich F. J. , Murphy Elliot , Haddow Mairi F. , Green Michael , Alder Roger W. , Wass Duncan F. 
Published: February 2013

AbstractWe make the case for benzo[c]quinolin‐6‐ylidene (1) as a strongly electron‐donating carbene ligand. The facile synthesis of 6‐trifluoromethanesulfonylbenzo[c]quinolizinium trifluoromethanesulfonate (2) gives straightforward access to a useful precursor for oxidative addition to low‐valent metals, to yield the desired carbene complexes. This concept has been achieved in the case of [Mn(benzo[c]quinolin‐6‐ylidene)(CO)5]+ (15) and [Pd(benzo[c]quinolin‐6‐ylidene)(PPh3)2(L)]2+ L=THF (21), OTf (22) or pyridine (23). Attempts to coordinate to nickel result in coupling products from two carbene precursor fragments. The CO IR‐stretching‐frequency data for the manganese compound suggests benzo[c]quinolin‐6‐ylidene is at least as strong a donor as any heteroatom‐stabilised carbene ligand reported.
[Pd(Fmes)2(tmeda)]: A Case of Intermittent CH⋅⋅⋅FC Hydrogen‐Bond Interaction in Solution
Authors: Bartolomé Camino , Villafañe Fernando , Martín‐Alvarez Jose M. , Martínez‐Ilarduya Jesús M. , Espinet Pablo 
Published: February 2013

AbstractThe X‐ray structure of the title compound [Pd(Fmes)2(tmeda)] (Fmes=2,4,6‐tris(trifluoromethyl)phenyl; tmeda=N,N,N′,N′‐tetramethylethylenediamine) shows the existence of uncommon CH⋅⋅⋅FC hydrogen‐bond interactions between methyl groups of the TMEDA ligand and ortho‐CF3 groups of the Fmes ligand. The 19F NMR spectra in CD2Cl2 at very low temperature (157 K) detect restricted rotation for the two ortho‐CF3 groups involved in hydrogen bonding, which might suggest that the hydrogen bond is responsible for this hindrance to rotation. However, a theoretical study of the hydrogen‐bond energy shows that it is too weak (about 7 kJ mol−1) to account for the rotational barrier observed (ΔH≠=26.8 kJ mol−1), and it is the steric hindrance associated with the puckering of the TMEDA ligand that should be held responsible for most of the rotational barrier. At higher temperatures the rotation becomes fast, which requires that the hydrogen bond is continuously being split up and restored and exists only intermittently, following the pulse of the conformational changes of TMEDA.
Kinetics and Reactor Design for N2O Decomposition in the EnviNOx® Process
Authors: Perbandt Christian , Bacher Vanessa , Groves Michael , Schwefer Meinhard , Siefert Rolf , Turek Thomas 
Published: February 2013

AbstractThe kinetics of N2O decomposition over a commercial iron zeolite catalyst was determined in an integral laboratory reactor. The formal kinetic equation developed permits a very good description of the observed rate as a function of temperature and the concentrations of N2O, NO and H2O. The influence of mass transfer phenomena on the reaction rate was investigated experimentally by using different catalyst particle sizes. A reactor model taking into account internal and external mass transfer resistances, axial dispersion and pressure drop was developed. Reactor simulations for different configurations revealed that random packings of catalyst extrudates must be placed in radial‐flow reactors to limit the pressure drop. Honeycomb monolith catalysts are attractive alternative geometries because they allow both better utilization of active material and the design of more compact reactors.
Screening of Catalysts for the Catalytic Cracking of Lignite
Authors: Seitz Mathias , Nowak Sascha , Welscher Julia , Zimmermann Jens , Nägler Thomas , Stam‐Creutz Timo , Frank Willy , Schwieger Wilhelm 
Published: February 2013

AbstractFür die stoffliche Verwertung von Braunkohle sind in der Vergangenheit unterschiedliche Verfahren entwickelt worden. Eines davon ist die thermische Pyrolyse. In dieser Arbeit wird ein neuer Ansatz aufgezeigt, der den Einsatz von heterogenen Katalysatoren im direkten Kontakt mit der Einsatzkohle verfolgt. Dabei können aliphatische Bestandteile der Braunkohle gespalten und Olefine sowie Aromate erzeugt werden. Ein Katalysatorscreening zeigt, dass zeolithische Materialien für diesen Zweck geeignet sind. Diese können mit vergleichbaren Eigenschaften zur besseren Abtrennung von den Koksrückständen auf Trägermaterialien aufgebracht werden.