bluuebunny/crossref_metadata_2025_split huggingface dataset:
Conformation‐Determined Through‐Bond versus Through‐Space Electronic Communication in Mixed‐Valence Systems with a Cross‐Conjugated Urea Bridge
Authors: Gong Zhong‐Liang , Zhong Yu‐Wu , Yao Jiannian 
Published: November 2014

AbstractBis‐triarylamine 2 and cyclometalated diruthenium 6(PF6)2 with a linear trans,trans‐urea bridge have been prepared, together with the bis‐triarylamine 3 and cyclometalated diruthenium 8(PF6)2 with a folded cis,cis‐N,N‐dimethylurea bridge. The linear or folded conformations of these molecules are supported by single‐crystal X‐ray structures of 2, 3, and other related compounds. These compounds display two consecutive anodic redox waves (N.+/0 or RuIII/II processes) with a potential separation of 110–170 mV. This suggests that an efficient electronic coupling is present between two redox termini through the cross‐conjugated urea bridge. The degree of electronic coupling has been investigated by using spectroelectrochemical measurements. Distinct intervalence charge‐transfer (IVCT) transitions have been observed for mixed‐valent (MV) compounds with a linear conformation. The IVCT transitions can also be identified for the folded MV compounds, albeit with a much weaker intensity. DFT results support that the electronic communication occurs by a through‐bond and through‐space pathway for the linear and folded compounds, respectively. The IVCT transitions of the MV compounds have been reproduced by TDDFT calculations. For the purpose of comparison, a bistriarylamine and a diruthenium complex with an imidazolidin‐2‐one bridge and a urea‐containing mono‐triarylamine and monoruthenium complex have been synthesized and studied.
Multicomponent Synthesis of Chiral Bidentate Unsymmetrical Unsaturated N‐Heterocyclic Carbenes: Copper‐Catalyzed Asymmetric CC Bond Formation
Authors: Jahier‐Diallo Claire , Morin Marie S. T. , Queval Pierre , Rouen Mathieu , Artur Isabelle , Querard Pierre , Toupet Loic , Crévisy Christophe , Baslé Olivier , Mauduit Marc 
Published: November 2014

AbstractA multicomponent strategy was applied to the synthesis of chiral bidentate unsaturated hydroxyalkyl‐ and carboxyalkyl‐N‐heterocyclic carbene (NHC) precursors. The newly developed low‐cost chiral ligands derived from amino alcohols and amino acids were evaluated in copper‐catalyzed asymmetric conjugated addition and asymmetric allylic alkylation, which afforded the desired tertiary and quaternary carbon stereocenters with excellent regio‐ and enantioselectivities (up to 99:1 e.r.).
Vibrational Circular Dichroism and Theoretical Study of the Conformational Equilibrium in (−)‐S‐Nicotine
Authors: Ortega Pilar Gema Rodríguez , Montejo Manuel , González Juan Jesus López 
Published: November 2014

AbstractWe report an extensive study of the molecular and electronic structure of (−)‐S‐nicotine, to deduce the phenomenon that controls its conformational equilibrium and to solve its solution‐state conformer population. Density functional theory, ab initio, and molecular mechanics calculations were used together with vibrational circular dichroism (VCD) and Fourier transform infrared spectroscopies. Calculations and experiments in solution show that the structure and the conformational energy profile of (−)‐S‐nicotine are not strongly dependent on the medium, thus suggesting that the conformational equilibrium is dominated by hyperconjugative interactions rather than repulsive electronic effects. The analysis of the first recorded VCD spectra of (−)‐S‐nicotine confirmed the presence of two main conformers at room temperature. Our results provide further evidence of the hypersensitivity of vibrational optical activity spectroscopies to the three‐dimensional structure of chiral samples and prove their suitability for the elucidation of solution‐state conformer distribution.
Testing the Mediating Effects of Obsessive Beliefs in Internet‐Based Cognitive Behaviour Therapy for Obsessive‐Compulsive Disorder: Results from a Randomized Controlled Trial
Authors: Andersson Erik , Ljótsson Brjánn , Hedman Erik , Hesser Hugo , Enander Jesper , Kaldo Viktor , Andersson Gerhard , Lindefors Nils , Rück Christian 
Published: November 2014

Although cognitive interventions for obsessive–compulsive disorder (OCD) have been tested in randomized trials, there are few trials that have tested the specific mechanisms of cognitive interventions, i.e. how they achieve their effects. In this study, we aimed to investigate the mediating effects of a short cognitive intervention in the treatment of OCD and used data from a recently conducted randomized controlled trial where 101 participants were allocated to either Internet‐based CBT (ICBT) or to a control condition. Obsessive beliefs were measured at pre‐treatment, at the time they had received the cognitive intervention, and also at post‐treatment. Weekly OCD symptoms were measured throughout the 10 weeks of treatment. We hypothesized that (1) the ICBT group would have greater reductions in obsessive beliefs (controlling for change in OCD symptoms) after completing the cognitive intervention, and that (2) this reduction would, in turn, predict greater OCD symptom reduction throughout the rest of the treatment period. Contrary to our expectations, the longitudinal mediation analysis indicated that (1) being randomized to ICBT actually increased the degree of obsessive beliefs after receiving the cognitive intervention at weeks 1–3, and (2) increase in obsessive beliefs predicted better outcome later in treatment. However, when repeating the analysis using cross‐sectional data at post‐treatment, the results were in line with the initial hypotheses. Results were replicated when the control condition received ICBT. We conclude that, although obsessive beliefs were significantly reduced at post‐treatment for the ICBT group, early increase rather than decrease in obsessive beliefs predicted favourable outcome. Copyright © 2014 John Wiley & Sons, Ltd.Key Practitioner Message

This study investigated the impact of cognitive interventions on obsessive beliefs for patients with obsessive–compulsive disorder.
Results showed that a sudden increase in obsessive beliefs is not an indicator of worse treatment response. On the contrary, it is more likely that the patient is better off when having this sudden increase.
Clinicians should not be alarmed if the patient has a sudden increase in obsessive beliefs, but we do recommend the clinician to investigate the reasons for this further.
The Effect of Alkaline Pretreatment Methods on Cellulose Structure and Accessibility
Authors: Bali Garima , Meng Xianzhi , Deneff Jacob I. , Sun Qining , Ragauskas Arthur J. 
Published: November 2014

AbstractThe effects of different alkaline pretreatments on cellulose structural features and accessibility are compared and correlated with the enzymatic hydrolysis of Populus. The pretreatments are shown to modify polysaccharides and lignin content to enhance the accessibility for cellulase enzymes. The highest increase in the cellulose accessibility was observed in dilute sodium hydroxide, followed by methods using ammonia soaking and lime (Ca(OH)2). The biggest increase of cellulose accessibility occurs during the first 10 min of pretreatment, with further increases at a slower rate as severity increases. Low temperature ammonia soaking at longer residence times dissolved a major portion of hemicellulose and exhibited higher cellulose accessibility than high temperature soaking. Moreover, the most significant reduction of degree of polymerization (DP) occurred for dilute sodium hydroxide (NaOH) and ammonia pretreated Populus samples. The study thus identifies important cellulose structural features and relevant parameters related to biomass recalcitrance.
Galectin‐3 in patients with heart failure with preserved ejection fraction: results from the Aldo‐DHF trial
Authors: Edelmann Frank , Holzendorf Volker , Wachter Rolf , Nolte Kathleen , Schmidt Albrecht G. , Kraigher‐Krainer Elisabeth , Duvinage André , Unkelbach Ines , Düngen Hans‐Dirk , Tschöpe Carsten , Herrmann‐Lingen Christoph , Halle Martin , Hasenfuss Gerd , Gelbrich Götz , Stough Wendy Gattis , Pieske Burkert M. 
Published: November 2014

AimsGalectin‐3 is a marker of myocardial fibrosis and mediates aldosterone‐induced cardiovascular inflammation and fibrosis. Characteristics of galectin‐3 and its response to spironolactone have not been evaluated in heart failure with preserved ejection fraction (HFpEF). The aim of this study was to determine the association between galectin‐3 levels and patient characteristics in HFpEF; to evaluate the interaction between spironolactone and galectin‐3 levels; and to assess the association between galectin‐3 and clinical outcomes.Methods and resultsAldo‐DHF investigated spironolactone 25 mg once daily vs. placebo for 12 months in patients with NYHA class II–III, LVEF ≥50%, grade ≥ I diastolic dysfunction, and peakVO2 ≤ 25 mL/kg/min. Galectin‐3 levels were obtained at baseline, and at 6 and 12 months. The association between baseline galectin‐3, change in galectin‐3, and all‐cause death or hospitalization was evaluated, and the interaction between galectin‐3 and treatment was assessed. Median baseline galectin‐3 was 12.1 ng/mL. After multivariable adjustment, baseline galectin‐3 inversely correlated with peak VO2 (P = 0.021), 6 min walk distance (P = 0.002), and Short Form 36 (SF‐36) physical functioning (P = 0.001), and directly correlated with NYHA class (P = 0.007). Baseline NT‐proBNP correlated with E/e' velocity ratio (P ≤ 0.001), left atrial volume index (P < 0.001), and LV mass index (P = 0.009). Increasing galectin‐3 at 6 or 12 months was associated with all‐cause death or hospitalization independent of treatment arm [hazard ratio (HR) 3.319, 95% confidence interval (CI) 1.214–9.07, P = 0.019] and NT‐proBNP (HR 3.127, 95% CI 1.144–8.549, P = 0.026). Spironolactone did not influence galectin‐3 levels.ConclusionGalectin‐3 levels are modestly elevated in patients with stable HFpEF and relate to functional performance and quality of life. Increasing galectin‐3 was associated with worse outcome, independent of treatment or NT‐proBNP.
Platinum Diolefin Complexes – Synthesis, Structures, and Cytotoxicity
Authors: Lüning Anna , Neugebauer Michael , Lingen Verena , Krest Alexander , Stirnat Kathrin , Deacon Glen B. , Drago Penny R. , Ott Ingo , Schur Julia , Pantenburg Ingo , Meyer Gerd , Klein Axel 
Published: November 2014

AbstractThe synthesis, spectroscopy, structures and chemical reactivity of platinum(II) diolefin complexescis‐[(∥∧∥)PtCl2],cis‐[(∥∧∥)PtCl(R)] andcis‐[(∥∧∥)Pt(R)2] [∥∧∥ = chelate diolefin ligand: 1,5‐cyclooctadiene (COD), 1,5‐dimethylocta‐1,5‐diene (Me2COD), norbornadiene (NBD), 1,5‐hexadiene (HEX), 3‐allyloxypropene (All2O, diallyl ether), diallylamine (All2NH); R = Me, Bn, C6F5, C6F4H‐4 (or ‐5), or C≡C(4‐Me)Ph] have been explored. The relative exchange rates of thecis‐[(∥∧∥)PtCl2] complexes towards the diimine ligand diisopropyl‐1,4‐diazabutadiene (iPr‐DAB) increased along the series COD < Me2COD < NBD < HEX < All2O by a factor of 4. The presumably dimeric complex [(All2NH)PtCl2]2undergoes a unique rearrangement process in dimethyl sulfoxide (DMSO) solution to yield the dimeric piperazine complex [PtCl(dmso)(C6H10N)]2, which has been characterised by single‐crystal XRD. For selected platinum complexes, cytotoxic effects in HT‐29 colon carcinoma and MCF‐7 breast cancer cell lines were evaluated. For comparison, the dicationic complexes [(COD)Pt(Bn)(L)][PF6]2with the very labile coligandsN‐methyl‐4,4′‐bipyridinium (MQ+) andN‐methyl‐1,4‐pyrazinium (Mpz+) were added to the study. Although the hexadiene complexes [(HEX)Pt(C6F4H‐4)2] and [(HEX)Pt(C6F4H‐5)2] show strong cytotoxicity, the introduction of labile diolefin ligands or the labile cationic MQ+or Mpz+coligands does not generally lead to markedly increased cytotoxicity.
Cyclic behaviour of interior beam–column joints reinforced with plain bars
Authors: Melo José , Varum Humberto , Rossetto Tiziana 
Published: November 2014

SummaryThe seismic damages commonly observed on beam–column joints of old reinforced concrete structures, built with plain bars and without proper detailing, justifies the need to further study the behaviour of this type of structures. The response of these structures when loaded cyclically, as occurs during the earthquakes, is partially controlled by the bond properties between the reinforcing bars and the surrounding concrete. This paper presents the results of an experimental campaign of unidirectional cyclic tests carried out on six full‐scale beam–column joints built with plain bars. These joint specimens are representative of existing reinforced concrete structures, that is, built without adequate reinforcement detailing for seismic demands. For comparison, an additional specimen is built with deformed bars and tested. The seven specimens are designed and detailed to allow the investigation of the influence of bond properties, lapping of the longitudinal bars in columns and beams, bent‐up bars in the beams, slab contribution and concrete strength. The lateral force–drift relationships, global dissipated energy evolution, contribution of the joint, beams and columns to the global dissipated energy, ductility, equivalent damping, final damage observed, homogenized reinforced concrete damage index, displacement components, curvature evolutions and Eurocode requirements are presented and discussed. Copyright © 2014 John Wiley & Sons, Ltd.
Grammatical analysis as a distributed neurobiological function
Authors: Bozic Mirjana , Fonteneau Elisabeth , Su Li , Marslen‐Wilson William D 
Published: November 2014

AbstractLanguage processing engages large‐scale functional networks in both hemispheres. Although it is widely accepted that left perisylvian regions have a key role in supporting complex grammatical computations, patient data suggest that some aspects of grammatical processing could be supported bilaterally. We investigated the distribution and the nature of grammatical computations across language processing networks by comparing two types of combinatorial grammatical sequences—inflectionally complex words and minimal phrases—and contrasting them with grammatically simple words. Novel multivariate analyses revealed that they engage a coalition of separable subsystems: inflected forms triggered left‐lateralized activation, dissociable into dorsal processes supporting morphophonological parsing and ventral, lexically driven morphosyntactic processes. In contrast, simple phrases activated a consistently bilateral pattern of temporal regions, overlapping with inflectional activations in L middle temporal gyrus. These data confirm the role of the left‐lateralized frontotemporal network in supporting complex grammatical computations. Critically, they also point to the capacity of bilateral temporal regions to support simple, linear grammatical computations. This is consistent with a dual neurobiological framework where phylogenetically older bihemispheric systems form part of the network that supports language function in the modern human, and where significant capacities for language comprehension remain intact even following severe left hemisphere damage. Hum Brain Mapp 36:1190–1201, 2015. © 2014 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc.
Dynamic shifts in brain network activation during supracapacity working memory task performance
Authors: Van Snellenberg Jared X. , Slifstein Mark , Read Christina , Weber Jochen , Thompson Judy L. , Wager Tor D. , Shohamy Daphna , Abi‐Dargham Anissa , Smith Edward E. 
Published: November 2014

AbstractDespite significant advances in understanding how brain networks support working memory (WM) and cognitive control, relatively little is known about how these networks respond when cognitive capabilities are overtaxed. We used a fine‐grained manipulation of memory load within a single trial to exceed WM capacity during functional magnetic resonance imaging to investigate how these networks respond to support task performance when WM capacity is exceeded. Analyzing correct trials only, we observed a nonmonotonic (inverted‐U) response to WM load throughout the classic WM network (including bilateral dorsolateral prefrontal cortex, posterior parietal cortex, and presupplementary motor areas) that peaked later in individuals with greater WM capacity. We also observed a relative increase in activity in medial anterior prefrontal cortex, posterior cingulate/precuneus, and lateral temporal and parietal regions at the highest WM loads, and a set of predominantly subcortical and prefrontal regions whose activation was greatest at the lowest WM loads. At the individual subject level, the inverted‐U pattern was associated with poorer performance while expression of the early and late activating patterns was predictive of better performance. In addition, greater activation in bilateral fusiform gyrus and right occipital lobe at the highest WM loads predicted better performance. These results demonstrate dynamic and behaviorally relevant changes in the level of activation of multiple brain networks in response to increasing WM load that are not well accounted for by present models of how the brain subserves the cognitive ability to hold and manipulate information on‐line. Hum Brain Mapp 36:1245–1264, 2015. © 2014 Wiley Periodicals, Inc.
The Water Use of Sweet Sorghum and Development of Crop Coefficients
Authors: Martínez‐Cruz Tania E. , Slack Donald C. , Ogden Kimberly L. , Ottman Michael 
Published: November 2014

AbstractReliable estimates of crop water use are essential to economic production of sweet sorghum under irrigated conditions. In Tucson, Arizona, USA, two planting dates, May 5th and June 15th, and four sweet sorghum varieties (M81E, ST, SM and A4) were evaluated to estimate crop coefficients (kc) based on the heat unit accumulation concept (GDD). One irrigation level at 50% depletion of available water capacity prior to irrigation and its effect on juice, biomass and ethanol yields was evaluated. Results show that it was possible to develop heat unit based kc´s for two day‐neutral varieties (ST and SM) and that they required 25% less water than the photo‐sensitive varieties. Peak crop coefficients were determined as 1.13, 1.05, 1.16 and 1.22 for M81E, ST, SM and A4. Results also showed that growing degree days accumulated to flowering were 2226 and 1759 GDD for ST and SM respectively. At a P‐value of 5% there were differences in crop water use, juice yields and bagasse production among treatments. For the May planting there was a slight effect on ethanol yields but no effect for the June planting, showing that regardless of the planting date and variety they are more likely to be similar. Copyright © 2015 John Wiley & Sons, Ltd.
Biodegradation of p‐cresol and sulfide removal by a marine‐denitrifying consortium
Authors: Meza‐Escalante Edna R. , Alvarez Luis H. , Serrano Denisse , Mendoza Erika , Bonola Ramsés 
Published: November 2014

AbstractThe simultaneous removal of sulfide and p‐cresol was carried out by using a marine‐denitrifying consortium collected in the coastal zone of Sonora, Mexico. Different experimental conditions were used to evaluate the capacity of the consortium to simultaneously eliminate nitrate, sulfide, and p‐cresol. For instance, the first set of assays was conducted at different sulfide concentrations (20, 50, and 100 mg S2− L−1), with a fixed concentration of p‐cresol (45 mg C L−1). The second set of assays was developed at different concentrations of p‐cresol (45, 75, and 100 mg C L−1), in the presence of 20 mg S2− L−1. In all cases, the concentration of nitrate was stoichiometrically added for the complete oxidization of the substrates. The results showed removal efficiencies up to 92% for p‐cresol and nitrate at 20 and 50 mg S2− L−1; whereas at 100 mg S2− L−1 removal efficiencies were 77% and 59% for p‐cresol and nitrate, respectively. On the other hand, sulfide (20 mg L−1) was completely removed under different concentrations of p‐cresol tested, with a partial accumulation of nitrite according to the increment of p‐cresol concentration. The results obtained indicate that the marine consortium was able to simultaneously remove the pollutants studied.
The place of the osteoplastic flap in the endoscopic era: Indications and pitfalls
Authors: Ochsner Matthew C. , DelGaudio John M. 
Published: November 2014

Objectives/HypothesisTo evaluate the osteoplastic flap (OPF) procedure for frontal sinus pathology at our institution, including indications, revisions, obliteration vs. nonobliteration, and obliteration materials.Study DesignSingle‐institution retrospective review from 1998 to 2013.MethodsCurrent Procedural Terminology codes identified all OPF procedures. Demographic data, diagnoses, previous frontal procedures, obliteration materials, and outcomes were evaluated. Diagnoses were divided into two groups: inflammatory (refractory sinusitis, mucoceles, surgical material infections) and noninflammatory (tumors, cerebrospinal fluid leaks).ResultsFifty‐seven patients underwent 73 OPF procedures: 36 obliterative and 37 nonobliterative/unobliterative. Inflammatory indications accounted for 76% of obliterated patients, but only 38% of nonobliterative procedures. Ten patients (17.5%) required revision, 90% of whom had an OPF for inflammatory indications. Only one patient who underwent an OPF procedure for noninflammatory pathology required revision. Twenty‐four percent of patients obliterated with bone cement ultimately required complete removal to resolve infection.ConclusionsThe OPF approach is still valuable for pathology refractory to or inaccessible to endoscopic approaches. Infectious etiologies have a much higher revision rate. Careful selection of pathologies can reduce revision rates, but in some cases a repeated OPF procedure is the only viable alternative. When bone cement becomes infected the only resolution is complete removal.Level of Evidence4. Laryngoscope, 125:801–806, 2015
Primary soft tissue reconstruction after transoral laryngeal tumor resection
Authors: Woo Peak 
Published: November 2014

Objectives/HypothesisPrimary reconstruction by endoscopic buccal mucosal grafting can be considered in cancer patients with large defects and in patients with bilateral disease. We present our case series of primary endoscopic buccal grafting after cancer surgery.Study DesignSeventeen cases in 16 patients treated with buccal primary reconstruction (PR) are compared to 26 subjects without reconstruction (SO) and to 18 radiation patients (RO). The Voice Handicap Index, voice grade, and acoustic analysis were used to compare voice outcomes between groups.MethodsCase–control study.ResultsThere were more European Laryngological Association type II, III, and type Va resections in the PR group. Acoustic analysis, Voice Handicap Index short form, and perceptual ratings by three expert listeners showed no differences in voice outcomes between groups. There were voice‐related differences between surgical patients, with the European Laryngological Association type I patients having better voices than European Laryngological Association type II, III, and Va groups combined. Voice outcomes showed mild to moderate dysphonia in all three groups. The presence of the buccal graft did not hinder tumor surveillance.ConclusionsPrimary reconstruction appears to be safe in patients with large soft tissue defects. There were no detectable functional differences between the PR, SO, and RO groups.Level of Evidence3b Laryngoscope, 125:1144–1148, 2015