bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rotational Molding of Poly(lactic acid): Effect of Polymer Grade and Granulometry
Authors: Greco Antonio , Maffezzoli Alfonso 
Published: November 2015

ABSTRACTThis paper is aimed at studying the effect of the grade and the granulometry of poly(lactic acid) (PLA) on its processability by rotational molding. Two PLA grades were considered: a low melt flow rate (MFR), high viscosity, material, characterized by an excellent quenchability, leading to a completely amorphous structure of rotomolded samples; a high MFR, low viscosity, material, characterized by a lower quenchability, leading to a semicrystalline structure of rotomolded samples. Three different granulometries were considered: a coarser one, that is, the pellets as received, intermediate size pellets produced by extrusion followed by pelletizing, and a powder obtained by grinding of as received pellets. Besides the different dimensions, the intermediate size pellets also experienced a supplementary extrusion step, which induced some degradation in the material. For both grades and three granulometries, void‐free prototypes were obtained, which indicate a very efficient sintering process, attributed to the low viscosity of all PLA grades. As a consequence, the modulus of the rotomolded samples was found to be unaffected by the PLA grade or granulometry. In contrast, the strength was shown to be more significantly dependent on quenchability than on the grade. To obtain an adequately high strength, an amorphous structure must be developed during cooling. Finally, the supplementary extrusion step experienced by the intermediate size pellets was shown to significantly decrease the strength of prototypes, as a consequence of the thermal degradation induced by this additional processing step.
Primary Progressive Multiple Sclerosis Evolving From Radiologically Isolated Syndrome
Authors: Kantarci Orhun H. , Lebrun Christine , Siva Aksel , Keegan Mark B. , Azevedo Christina J. , Inglese Matilde , Tintoré Mar , Newton Braeden D. , Durand‐Dubief Francoise , Amato Maria Pia , De Stefano Nicola , Sormani Maria Pia , Pelletier Daniel , Okuda Darin T. 
Published: November 2015

ObjectiveThe aim of this work was to evaluate the preprogressive phase in subjects with radiologically isolated syndrome (RIS) who evolve to primary progressive multiple sclerosis (PPMS).MethodsA multicenter RIS cohort was previously established. Demographic, clinical, and radiological characteristics of subjects with RIS that evolved directly to PPMS were compared to those that developed a relapsing disease course from onset (clinically isolated syndrome [CIS] or relapsing‐remitting MS) and were also compared to two other population‐ and clinic‐based PPMS cohorts.ResultsOf the 453 subjects with RIS, 128 evolved to symptomatic MS during the follow‐up (113 developed a first acute clinical event consistent with CIS/MS, 15 evolved to PPMS). PPMS prevalence (11.7%) and onset age (mean ± standard deviation; 49.1 ± 12.1) in the RIS group were comparable to other PPMS populations (p > 0.05). Median time to PPMS was 3.5 years (range, 1.6–5.4). RIS evolved to PPMS more commonly in men (p = 0.005) and at an older age (p < 0.001) when compared to CIS/MS, independent of follow‐up duration. Subjects who evolved to PPMS had more spinal cord lesions (100%) before symptomatic evolution than those that developed CIS/MS (64%) and those that remained asymptomatic (23%) within the follow‐up period (P = 0.005). Other MRI characteristics in the preprogressive phase of PPMS were indistinguishable from CIS/MS.InterpretationSubjects with RIS evolve to PPMS at the same frequency as expected from general MS populations in an age‐dependent manner. Besides age, unequivocal presence of spinal cord lesions and being male predicted evolution to PPMS. Our findings further suggest that RIS is biologically part of the MS spectrum. Ann Neurol 2016;79:288–294
Free fatty acid as an outcome predictor of atrial fibrillation–associated stroke
Authors: Choi Jeong‐Yoon , Jung Jin‐Man , Kwon Do‐Young , Park Moon Ho , Kim Ji Hyun , Oh Kyungmi , Koh Seong‐Beom , Seo Woo‐Keun 
Published: November 2015

ObjectiveWe investigated whether baseline plasma free fatty acid (FFA) concentration is associated with any (ischemic/hemorrhagic) stroke, ischemic stroke/systemic embolism (ISSE), or ischemic stroke among stroke survivors with atrial fibrillation (A‐fib). Moreover, we compared the outcome predictability of FFA with previously adopted models, including the CHADS2 and CHA2DS2‐VASc scoring systems.MethodsWe analyzed data from 279 stroke patients with A‐fib and investigated the association between plasma FFA concentration and outcomes using Cox regression models with competing risk analyses.ResultsMedian follow‐up period was 17.5 months. During the study period, any stroke, ISSE, and ischemic stroke occurred in 22, 21, and 17 patients, respectively. The cumulative risk for any stroke, ISSE, and ischemic stroke were 5.1%, 4.7%, and 4.2% at the end of the first year and 14.8%, 12.1%, and 10.8% at the end of the third year, respectively. After adjusting covariates (model 1), baseline FFA concentration was associated with recurrence of any stroke (hazard ratio [HR] = 1.774, 95% confidence interval [CI] = 1.124–2.801, per 1mEq/l increment of FFA). FFA showed a trend association with ISSE (HR = 1.569, 95% CI = 0.950–2.592) and ischemic stroke (HR = 1.630, 95% CI = 0.967–2.746). In adjusted models including CHADS2 or CHA2DS2‐VASc score as a covariate, (models 2 and 3) FFA was still shown to be an independent predictor of any stroke and ischemic stroke. There was a significant or trend association between FFA and ISSE.InterpretationFFA may be a potential biomarker that predicts outcome events in stroke with A‐fib along with the CHADS2 and CHA2DS2‐VASc scoring systems. Ann Neurol 2016;79:317–325
A Catalyst Designed for the Enantioselective Construction of Methyl‐ and Alkyl‐Substituted Tertiary Stereocenters
Authors: Claraz Aurélie , Sahoo Gokarneswar , Berta Dénes , Madarász Ádám , Pápai Imre , Pihko Petri M. 
Published: November 2015

AbstractTertiary methyl‐substituted stereocenters are present in numerous biologically active natural products. Reported herein is a catalytic enantioselective method for accessing these chiral building blocks using the Mukaiyama–Michael reaction between silyl ketene thioacetals and acrolein. To enable remote enantioface control on the nucleophile, a new iminium catalyst, optimized by three‐parameter tuning and by identifying substituent effects on enantioselectivity, was designed. The catalytic process allows rapid access to chiral thioesters, amides, aldehydes, and ketones bearing an α‐methyl stereocenter with excellent enantioselectivities, and allowed rapid access to the C4–C13 segment of (−)‐bistramide A. DFT calculations rationalized the observed sense and level of enantioselectivity.
Enantioselective Synthesis of 3a‐Amino‐Pyrroloindolines by Copper‐Catalyzed Direct Asymmetric Dearomative Amination of Tryptamines
Authors: Liu Chuan , Yi Ji‐Cheng , Zheng Zhong‐Bo , Tang Yong , Dai Li‐Xin , You Shu‐Li 
Published: November 2015

AbstractA direct asymmetric dearomative amination of tryptamines with O‐(2,4‐dinitrophenyl)hydroxylamine (DPH) was achieved using CuBr‐bisoxazoline complex as a catalyst, affording 3a‐amino‐pyrroloindolines in good to excellent enantioselectivity under mild reaction conditions. Furthermore, the synthetic value of this method was demonstrated in the total synthesis of (−)‐psychotriasine in a highly concise manner.
Nociceptive Sensitizers Are Regulated in Damaged Joint Tissues, Including Articular Cartilage, When Osteoarthritic Mice Display Pain Behavior
Authors: Driscoll Clare , Chanalaris Anastasios , Knights Chancie , Ismail Heba , Sacitharan Pradeep K. , Gentry Clive , Bevan Stuart , Vincent Tonia L. 
Published: November 2015

ObjectivePain is the most common symptom of osteoarthritis (OA), yet where it originates in the joint and how it is driven are unknown. The aim of this study was to identify pain‐sensitizing molecules that are regulated in the joint when mice subjected to surgical joint destabilization develop OA‐related pain behavior, the tissues in which these molecules are being regulated, and the factors that control their regulation.MethodsTen‐week‐old mice underwent sham surgery, partial meniscectomy, or surgical destabilization of the medial meniscus (DMM). Pain‐related behavior as determined by a variety of methods (testing of responses to von Frey filaments, cold plate testing for cold sensitivity, analgesiometry, incapacitance testing, and forced flexion testing) was assessed weekly. Once pain‐related behavior was established, RNA was extracted from either whole joints or microdissected tissue samples (articular cartilage, meniscus, and bone). Reverse transcription–polymerase chain reaction analysis was performed to analyze the expression of 54 genes known to regulate pain sensitization. Cartilage injury assays were performed using avulsed immature hips from wild‐type or genetically modified mice or by explanting articular cartilage from porcine joints preinjected with pharmacologic inhibitors. Levels of nerve growth factor (NGF) protein were measured by enzyme‐linked immunosorbent assay.ResultsMice developed pain‐related behavior 8 weeks after undergoing partial meniscectomy or 12 weeks after undergoing DMM. NGF, bradykinin receptors B1 and B2, tachykinin, and tachykinin receptor 1 were significantly regulated in the joints of mice displaying pain‐related behavior. Little regulation of inflammatory cytokines, leukocyte activation markers, or chemokines was observed. When tissue samples from articular cartilage, meniscus, and bone were analyzed separately, NGF was consistently regulated in the articular cartilage. The other pain sensitizers were also largely regulated in the articular cartilage, although there were some differences between the 2 models. NGF and tachykinin were strongly regulated by simple mechanical injury of cartilage in vitro in a transforming growth factor β–activated kinase 1–, fibroblast growth factor 2–, and Src kinase–dependent manner.ConclusionDamaged joint tissues produce proalgesic molecules, including NGF, in murine OA.
RETRACTION: Long noncoding RNA linc‐ITGB1 promotes cell migration and invasion in human breast cancer
Authors: Yan Meidi , Zhang Lina , Li Guoqing , Xiao Shengwen , Dai Ji , Cen Xueying 
Published: November 2015

AbstractRETRACTION: Breast cancer is the most commonly diagnosed cancer and the leading cause of cancer‐related death in women globally. Its high morbidity and mortality, as well as its elevated tendency to metastasize to other organs, warrant the urgency to find new biomarkers for breast cancer diagnosis and treatment. The specific roles of long noncoding RNA linc‐ITGB1 on cell proliferation and metastasis in breast cancer were explored in this study. The expression of linc‐ITGB1 was significantly upregulated in both clinical breast cancer tissues and cultured breast cancer cell lines. The linc‐ITGB1 knockdown with specific short hairpin RNA (shRNA) decreased cell proliferation and colony formation in vitro. Tumor growth in vivo was also inhibited by linc‐ITGB1 depletion. In addition, linc‐ITGB1 depletion caused cell accumulation in the G0/G1 phase. Breast cancer cell lines with linc‐ITGB1 depletion exhibited decreased migration and invasion abilities compared with the control cells. Furthermore, the linc‐ITGB1 knockdown decreased the expression of mesenchymal markers N‐cadherin and vimentin while increasing the expression of the epithelial marker E‐cadherin. Key cell cycle regulators Cdc25C and Cyclin B1 were also decreased by the linc‐ITGB1 knockdown. These data suggest that linc‐ITGB1 promotes breast cancer progression by inducing cell cycle arrest and interrupting the epithelial‐to‐mesenchymal transition process.
Cell‐Like Nanostructured Environments Alter Diffusion and Reaction Kinetics in Cell‐Free Gene Expression
Authors: Hansen Maike M. K. , Paffenholz Sabine , Foschepoth David , Heus Hans A. , Thiele Julian , Huck Wilhelm T. S. 
Published: November 2015

AbstractIn highly crowded and viscous intracellular environments, the kinetics of complex enzymatic reactions are determined by both reaction and diffusion rates. However in vitro studies on transcription and translation often fail to take into account the density of the prokaryotic cytoplasm. Here we mimic the cellular environment by using a porous hydrogel matrix, to study the effects of macromolecular crowding on gene expression. We found that within microgels gene expression is localized, transcription is enhanced up to fivefold, and translation is enhanced up to fourfold. Our results highlight the need to consider the role of the physical environment on complex biochemical reactions, in this case macromolecular crowding, nanoscale spatial organization, and confinement.
Subtypes of firesetters
Authors: Dalhuisen Lydia , Koenraadt Frans , Liem Marieke 
Published: November 2015

AbstractBackgroundPrior research has classified firesetters by motive. The multi‐trajectory theory of adult firesetting (M‐TTAF) takes a more aetiological perspective, differentiating between five hypothesised trajectories towards firesetting: antisocial cognition, grievance, fire interest, emotionally expressive/need for recognition and multifaceted trajectories.AimThe objective of this study was to validate the five routes to firesetting as proposed in the M‐TTAF.MethodsAll 389 adult firesetters referred for forensic mental health assessment to one central clinic in the Netherlands between 1950 and 2012 were rated on variables linked to the M‐TTAF. Cluster analysis was then applied.ResultsA reliable cluster solution emerged revealing five subtypes of firesetters – labelled instrumental, reward, multi‐problem, disturbed relationship and disordered. Significant differences were observed regarding both offender and offence characteristics.DiscussionOur five‐cluster solution with five subtypes of firesetters partially validates the proposed M‐TTAF trajectories and suggests that for offenders with and without mental disorder, this classification may be useful. If further validated with larger and more diverse samples, the M‐TTAF could provide guidance on staging evidence‐based treatment. Copyright © 2015 John Wiley & Sons, Ltd.
Organocatalytic Asymmetric Conjugate Additions to Cyclopent‐1‐enecarbaldehyde: A Critical Assessment of Organocatalytic Approaches towards the Telaprevir Bicyclic Core
Authors: Bernardi Luca , Fochi Mariafrancesca , Carbone Riccardo , Martinelli Ada , Fox Martin E. , Cobley Christopher J. , Kandagatla Bhaskar , Oruganti Srinivas , Dahanukar Vilas H. , Carlone Armando 
Published: November 2015

AbstractIn the context of a programme directed at the manufacture of telaprevir, eight possible approaches to its bicyclic α‐amino acid core, based on organocatalytic enantioselective conjugate additions to cyclopent‐1‐enecarbaldehyde, were identified and preliminarily explored. Four reactions, delivering advanced intermediates en route to the target amino acid, were selected for a thorough optimisation. Three of this reactions involved iminium ion catalysis with a prolinol catalyst (addition of nitromethane, nitroacetate and acetamidomalonate) and one was based on a Cinchona‐derived phase‐transfer catalyst (addition of glycine imines). A careful choice of additives allowed lowering of the catalyst loading to 0.5 mol % in some cases. The preparation of intermediates that would give access to the core of telaprevir in good yields and enantioselectivities by exploiting readily available substrates and catalysts, highlights the potential of organocatalytic technology for a cost‐effective preparation of pharmaceuticals.
Metal‐Directed Self‐Assembly of a Polyoxometalate‐Based Molecular Triangle: Using Powerful Analytical Tools to Probe the Chemical Structure of Complex Supramolecular Assemblies
Authors: Izzet Guillaume , Macdonell Andrew , Rinfray Corentin , Piot Madeleine , Renaudineau Séverine , Derat Etienne , Abécassis Benjamin , Afonso Carlos , Proust Anna 
Published: November 2015

AbstractA polyoxometalate‐based molecular triangle has been synthesized through the metal‐driven self‐assembly of covalent organic/inorganic hybrid oxo‐clusters with remote pyridyl binding sites. The new metallomacrocycle was unambiguously characterized by using a combination of 1H NMR spectroscopy, 2D diffusion NMR spectroscopy (DOSY), electrospray ionization travelling wave ion mobility mass spectrometry (ESI‐TWIM‐MS), small‐angle X‐ray scattering (SAXS) and molecular modelling. The collision cross‐sections obtained from TWIM‐MS and the hydrodynamic radii derived from DOSY are in good agreement with the geometry‐optimized structures obtained by using theoretical calculations. Furthermore, SAXS was successfully employed and proved to be a powerful technique for characterizing such large supramolecular assemblies.
Diazo Strategy for the Synthesis of Pyridazines: Pivotal Impact of the Configuration of the Diazo Precursor on the Process
Authors: Nikolaev Valerij A. , Cantillo David , Kappe C. Oliver , Medvedev Jury J. , Prakash G. K. Surya. , Supurgibekov Murat B. 
Published: November 2015

AbstractPhosphazenes of vinyldiazocarbonyl compounds having cis stereochemistry of the functional groups on the vinyl bond readily produce pyridazines by a diaza‐Wittig process, whereas their counterparts with trans configuration remain intact under similar reaction conditions. Upon UV irradiation trans‐phosphazenes furnish pyridazines through a tandem trans‐to‐cis isomerization followed by intramolecular cyclization. At elevated temperatures trans‐(triphenyl)phosphazenes dissociate to give the initial vinyldiazo compounds, which produce pyrazoles in high yields. The first theoretical study on the mechanism of the diaza‐Wittig process by DFT calculations at the M06‐2X/6‐31G(d) level of theory suggest that for the cis‐phosphazenes a rapid tandem [2+2] cycloaddition/cycloelimination process with low energy barriers is preferred over trans isomers.
Carboranes as a Tool to Tune Phosphorescence
Authors: Li Xiang , Yan Hong , Zhao Qiang 
Published: November 2015

AbstractPhosphorescent transition‐metal complexes (PTMCs) have attracted great interest because of their excellent properties which may lead to promising applications in optoelectronics. In recent years, carboranes have been demonstrated to be a novel and effective tool to tune phosphorescence of PTMCs. This Concept article deals with the advances of carborane‐functionalized PTMCs for potential optical applications. The discussions are focused on the design strategies and synthetic procedures leading to carborane‐functionalized PTMCs, the influence of carboranes on the optical properties of PTMCs, and the promising optical applications of this interesting class of phosphorescent materials.
Scalable Synthesis of Efficient Water Oxidation Catalysts: Insights into the Activity of Flame‐Made Manganese Oxide Nanocrystals
Authors: Liu Guanyu , Hall Jeremy , Nasiri Noushin , Gengenbach Thomas , Spiccia Leone , Cheah Mun Hon , Tricoli Antonio 
Published: November 2015

AbstractChemical energy storage by water splitting is a promising solution for the utilization of renewable energy in numerous currently impracticable needs, such as transportation and high temperature processing. Here, the synthesis of efficient ultra‐fine Mn3O4 water oxidation catalysts with tunable specific surface area is demonstrated by a scalable one‐step flame‐synthesis process. The water oxidation performance of these flame‐made structures is compared with pure Mn2O3 and Mn5O8, obtained by post‐calcination of as‐prepared Mn3O4 (115 m2 g−1), and commercial iso‐structural polymorphs, probing the effect of the manganese oxidation state and synthetic route. The structural properties of the manganese oxide nanoparticles were investigated by XRD, FTIR, high‐resolution TEM, and XPS. It is found that these flame‐made nanostructures have substantially higher activity, reaching up to 350 % higher surface‐specific turnover frequency (0.07 μmol
m−2 s−1) than commercial nanocrystals (0.02 μmol
m−2 s−1), and production of up to 0.33 mmol
molMn−1 s−1. Electrochemical characterization confirmed the high water oxidation activity of these catalysts with an initial current density of 10 mA cm−2 achieved with overpotentials between 0.35 and 0.50 V in 1 m NaOH electrolyte.
Reactions of Li/Cl Phosphinidenoid Complexes with 1,3,4,5‐Tetramethylimidazol‐2‐ylidene: A New Route to N‐Heterocyclic Carbene Adducts of Terminal Phosphin­idene Complexes and an Unprecedented Transformation of an Oxaphosphirane Complex
Authors: Klein Melina , Schnakenburg Gregor , Espinosa Ferao Arturo , Tokitoh Norihiro , Streubel Rainer 
Published: November 2015

AbstractThe reaction of Li/Cl phosphinidenoid tungsten(0) complex 2 [R = CH(SiMe3)2] with 1,3,4,5‐tetramethylimidazol‐2‐ylidene (3) yielded the zwitterionic phosphaalkene complex 4. A comparative study on chloro‐ (5) or dichloro(organo)phosphane complexes 1 [R = CH(SiMe3)2] and NHC 3 revealed the formation of 4 at ambient temperature. First evidence for the formation of phosphinidenoid complex 7, having a C‐Cl imidazolium cation, and its reaction with benzaldehyde to give oxaphosphirane complex 9 are presented. Furthermore, the first example of a formal exchange at the phosphorus center of an oxaphosphirane complex to give zwitterion 4 is demonstrated.
Practical Synthesis of Phenanthrid­inones by Palladium‐Catalyzed One‐Pot C–C and C–N Coupling Reaction: Extending the Substrate Scope to o‐Chlorobenzamides
Authors: Liu Hailong , Han Weibiao , Li Chun , Ma Zhiyong , Li Ruixiang , Zheng Xueli , Fu Haiyan , Chen Hua 
Published: November 2015

AbstractA highly efficient construction of phenanthridinone derivatives from o‐halobenzamides was developed by using a phosphine‐free palladium catalyst in N,N‐dimethylacetamide. The domino reaction proceeds through a sequential C–C and C–N bond‐formation process in one pot. This protocol exhibits broad substrate scope and affords a series of phenanthridinones in up to 93 % yield. Importantly, the protocol could also be applied for the less reactive o‐chlorobenzamides. The approach constitutes the first example of the synthesis of phenanthridinones from this kind of substrate. Moreover, the success of a gram‐scale reaction demonstrated that this operationally simple process is scalable.
Quality of Life, Body Image and Sexual Functioning in Bariatric Surgery Patients
Authors: Sarwer David B. , Steffen Kristine J. 
Published: November 2015

AbstractThis article provides an overview of the literature on quality of life, body image and sexual behaviour in individuals with extreme obesity and who undergo bariatric surgery. Quality of life is a psychosocial construct that includes multiple domains, including health‐related quality of life, weight‐related quality of life, as well as other psychological constructs such as body image and sexual functioning. A large literature has documented the impairments in quality of life and these other domains in persons with obesity and extreme obesity in particular. These impairments are believed to play an influential role in the decision to undergo bariatric surgery. Individuals who undergo bariatric surgery typically report significant improvements in these and other areas of psychosocial functioning, often before they reach their maximum weight loss. The durability of these changes as patients maintain or regain weight, however, is largely unknown. Copyright © 2015 John Wiley & Sons, Ltd and Eating Disorders Association.