bluuebunny/crossref_metadata_2025_split huggingface dataset:
Stacking of Metal Chelates with Benzene: Can Dispersion‐Corrected DFT Be Used to Calculate Organic–Inorganic Stacking?
Authors: Malenov Dušan P. , Ninković Dragan B. , Zarić Snežana D. 
Published: January 2015

AbstractCCSD(T)/CBS energies for stacking of nickel and copper chelates are calculated and used as benchmark data for evaluating the performance of dispersion‐corrected density functionals for calculating the interaction energies. The best functionals for modeling the stacking of benzene with the nickel chelate are M06HF‐D3 with the def2‐TZVP basis set, and B3LYP‐D3 with either def2‐TZVP or aug‐cc‐pVDZ basis set, whereas for copper chelate the PBE0‐D3 with def2‐TZVP basis set yielded the best results. M06L‐D3 with aug‐cc‐pVDZ gives satisfying results for both chelates. Most of the tested dispersion‐corrected density functionals do not reproduce the benchmark data for stacking of benzene with both nickel (no unpaired electrons) and copper chelate (one unpaired electron), whereas a number of these functionals perform well for interactions of organic molecules.
Mechanism for the Nonadiabatic Photooxidation of Benzene to Phenol: Orientation‐Dependent Proton‐Coupled Electron Transfer
Authors: Chang Xue‐Ping , Cui Ganglong , Fang Wei‐Hai , Thiel Walter 
Published: January 2015

AbstractAn efficient catalytic one‐step conversion of benzene to phenol was achieved recently by selective photooxidation under mild conditions with 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ) as the photocatalyst. Herein, high‐level electronic structure calculations in the gas phase and in acetonitrile solution are reported to explore the underlying mechanism. The initially populated 1ππ* state of DDQ can relax efficiently through a nearby dark 1nπ* doorway state to the 3ππ* state of DDQ, which is found to be the precursor state involved in the initial intermolecular electron transfer from benzene to DDQ. The subsequent triplet‐state reaction between DDQ radical anions, benzene radical cations, and water is computed to be facile. The formed DDQH and benzene‐OH radicals can undergo T1→S0 intersystem crossing and concomitant proton‐coupled electron transfer (PCET) to generate the products DDQH2 and phenol. Two of the four considered nonadiabatic pathways involve an orientation‐dependent triplet PCET process, followed by intersystem crossing to the ground state (S0). The other two first undergo a nonadiabatic T1→S0 transition to produce a zwitterionic S0 complex, followed by a barrierless proton transfer. The present theoretical study identifies novel types of nonadiabatic PCET processes and provides detailed mechanistic insight into DDQ‐catalyzed photooxidation.
A New Self‐Report Inventory of Dyslexia for Students: Criterion and Construct Validity
Authors: Tamboer Peter , Vorst Harrie C. M. 
Published: January 2015

The validity of a Dutch self‐report inventory of dyslexia was ascertained in two samples of students. Six biographical questions, 20 general language statements and 56 specific language statements were based on dyslexia as a multi‐dimensional deficit.Dyslexia and non‐dyslexia were assessed with two criteria: identification with test results (Sample 1) and classification using biographical information (both samples). Using discriminant analyses, these criteria were predicted with various groups of statements. All together, 11 discriminant functions were used to estimate classification accuracy of the inventory. In Sample 1, 15 statements predicted the test criterion with classification accuracy of 98%, and 18 statements predicted the biographical criterion with classification accuracy of 97%. In Sample 2, 16 statements predicted the biographical criterion with classification accuracy of 94%. Estimations of positive and negative predictive value were 89% and 99%.Items of various discriminant functions were factor analysed to find characteristic difficulties of students with dyslexia, resulting in a five‐factor structure in Sample 1 and a four‐factor structure in Sample 2. Answer bias was investigated with measures of internal consistency reliability.Less than 20 self‐report items are sufficient to accurately classify students with and without dyslexia. This supports the usefulness of self‐assessment of dyslexia as a valid alternative to diagnostic test batteries. Copyright © 2015 John Wiley & Sons, Ltd.
Range of Validity of a Simplified Model for Diffuse Charge Dynamics
Authors: Li Mengying , Hu Howard H. , Bau Haim H. 
Published: January 2015

AbstractThe modelling of electrochemical processes often requires the solution of the Poisson‐Nernst‐Planck (PNP) equations. In complex geometries, such as porous electrodes, that is challenging due to the presence of disparate length scales, ranging from the Debye screening length (∼nm) to the device length scale (∼cm). To overcome this difficulty, one often assumes that the electric double layer (EDL) is at quasi‐equilibrium to construct a simplified model that accounts for ion diffusion in the electro‐neutral bulk of the electrolyte while replacing the EDLs with appropriate boundary conditions. Various researchers have demonstrated that such an approach is valid in the asymptotic limit of a thin EDL and moderate electrode potentials. In this note, we explore the range of validity of this approximation by considering a one‐dimensional electrolytic cell with blocking electrodes subjected to a step change and time‐periodic alternations in the electrodes’ potentials by calculating the errors associated with the approximate approach as functions of the EDL thickness and electric field frequency and intensity. Additionally, we delineate numerical instabilities associated with the numerical solutions of the bulk equations with the nonlinear boundary condition peculiar to this problem.
Unraveling the relationship between regional gray matter atrophy and pathology in connected white matter tracts in long‐standing multiple sclerosis
Authors: Steenwijk Martijn D. , Daams Marita , Pouwels Petra J.W. , J. Balk Lisanne , Tewarie Prejaas K. , Geurts Jeroen J. G. , Barkhof Frederik , Vrenken Hugo 
Published: January 2015

AbstractIntroductionGray matter (GM) atrophy is common in multiple sclerosis (MS), but the relationship with white matter (WM) pathology is largely unknown. Some studies found a co‐occurrence in specific systems, but a regional analysis across the brain in different clinical phenotypes is necessary to further understand the disease mechanism underlying GM atrophy in MS. Therefore, we investigated the association between regional GM atrophy and pathology in anatomically connected WM tracts.MethodsConventional and diffusion tensor imaging was performed at 3T in 208 patients with long‐standing MS and 60 healthy controls. Deep and cortical GM regions were segmented and quantified, and both lesion volumes and average normal appearing WM fractional anisotropy of their associated tracts were derived using an atlas obtained by probabilistic tractography in the controls. Linear regression was then performed to quantify the amount of regional GM atrophy that can be explained by WM pathology in the connected tract.ResultsMS patients showed extensive deep and cortical GM atrophy. Cortical atrophy was particularly present in frontal and temporal regions. Pathology in connected WM tracts statistically explained both regional deep and cortical GM atrophy in relapsing‐remitting (RR) patients, but only deep GM atrophy in secondary‐progressive (SP) patients.ConclusionIn RRMS patients, both deep and cortical GM atrophy were associated with pathology in connected WM tracts. In SPMS patients, only regional deep GM atrophy could be explained by pathology in connected WM tracts. This suggests that in SPMS patients cortical GM atrophy and WM damage are (at least partly) independent disease processes. Hum Brain Mapp, 36:1796–1807, 2015. © 2015 Wiley Periodicals, Inc.
Making sense: Dopamine activates conscious self‐monitoring through medial prefrontal cortex
Authors: Joensson Morten , Thomsen Kristine Rømer , Andersen Lau M. , Gross Joachim , Mouridsen Kim , Sandberg Kristian , Østergaard Leif , Lou Hans C. 
Published: January 2015

AbstractWhen experiences become meaningful to the self, they are linked to synchronous activity in a paralimbic network of self‐awareness and dopaminergic activity. This network includes medial prefrontal and medial parietal/posterior cingulate cortices, where transcranial magnetic stimulation may transiently impair self‐awareness. Conversely, we hypothesize that dopaminergic stimulation may improve self‐awareness and metacognition (i.e., the ability of the brain to consciously monitor its own cognitive processes). Here, we demonstrate improved noetic (conscious) metacognition by oral administration of 100 mg dopamine in minimal self‐awareness. In a separate experiment with extended self‐awareness dopamine improved the retrieval accuracy of memories of self‐judgment (autonoetic, i.e., explicitly self‐conscious) metacognition. Concomitantly, magnetoencephalography (MEG) showed increased amplitudes of oscillations (power) preferentially in the medial prefrontal cortex. Given that electromagnetic activity in this region is instrumental in self‐awareness, this explains the specific effect of dopamine on explicit self‐awareness and autonoetic metacognition. Hum Brain Mapp 36:1866–1877, 2015. © 2015 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc..
The intrinsic resting state voice network in Parkinson's disease
Authors: New Anneliese B. , Robin Donald A. , Parkinson Amy L. , Eickhoff Claudia R. , Reetz Kathrin , Hoffstaedter Felix , Mathys Christian , Sudmeyer Martin , Michely Jochen , Caspers Julian , Grefkes Christian , Larson Charles R. , Ramig Loraine O. , Fox Peter T. , Eickhoff Simon B. 
Published: January 2015

AbstractOver 90 percent of patients with Parkinson's disease experience speech‐motor impairment, namely, hypokinetic dysarthria characterized by reduced pitch and loudness. Resting‐state functional connectivity analysis of blood oxygen level‐dependent functional magnetic resonance imaging is a useful measure of intrinsic neural functioning. We utilized resting‐state functional connectivity modeling to analyze the intrinsic connectivity in patients with Parkinson's disease within a vocalization network defined by a previous meta‐analysis of speech (Brown et al., 2009). Functional connectivity of this network was assessed in 56 patients with Parkinson's disease and 56 gender‐, age‐, and movement‐matched healthy controls. We also had item 5 and 18 of the UPDRS, and the PDQ‐39 Communication subscale available for correlation with the voice network connectivity strength in patients. The within‐group analyses of connectivity patterns demonstrated a lack of subcortical–cortical connectivity in patients with Parkinson's disease. At the cortical level, we found robust (homotopic) interhemispheric connectivity but only inconsistent evidence for many intrahemispheric connections. When directly contrasted to the control group, we found a significant reduction of connections between the left thalamus and putamen, and cortical motor areas, as well as reduced right superior temporal gyrus connectivity. Furthermore, most symptom measures correlated with right putamen, left cerebellum, left superior temporal gyrus, right premotor, and left Rolandic operculum connectivity in the voice network. The results reflect the importance of (right) subcortical nodes and the superior temporal gyrus in Parkinson's disease, enhancing our understanding of the neurobiological underpinnings of vocalization impairment in Parkinson's disease. Hum Brain Mapp 36:1951–1962, 2015. © 2015 The Authors Human Brain Mapping Published by Wiley Periodicals, Inc.
Climate warming causes intensification of the hydrological cycle, resulting in changes to the vernal and autumnal windows in a northern temperate forest
Authors: Creed I. F. , Hwang T. , Lutz B. , Way D. 
Published: January 2015

AbstractClimate warming is likely to lead to complex effects on northern forests of the temperate forest biome. We investigated whether rising temperatures altered the timing of snowmelt and snowpack accumulation or extended the forest growing season length in the Turkey Lakes Watershed in central Ontario. Archived satellite imagery was used to track changes in timing of snowpack loss/gain and canopy leaf on/off; the periods between these events were defined as the vernal (spring) and autumnal (fall) windows. We found only a slight extension of the growing season into the autumn period and no increase in the width of the vernal or autumnal windows, indicating that forest growth is not responding significantly to temperature increases during these windows. Archived time series of temperature, precipitation and discharge data for a nested set of catchments ranging in size from headwater (<10 ha) to regional (103 ha) catchments were used to track changes in the magnitude, timing and partitioning of precipitation into evapotranspiration and discharge. We found an intensification of hydrological cycling, with (1) a higher dryness index (PET/P) during the summer growing season and (2) earlier spring snowmelt discharges, and later more concentrated autumn storm discharges during the shoulder seasons. This intensification of the hydrological cycle during the summer growth season and the vernal and autumnal windows may not only limit opportunities for enhanced forest growth, but may be contributing to the recent observations of forest decline within this biome. Copyright © 2015 John Wiley & Sons, Ltd.
Adhesion and activation of platelets from subjects with coronary artery disease and apparently healthy individuals on biomaterials
Authors: Braune S. , Groß M. , Walter M. , Zhou S. , Dietze S. , Rutschow S. , Lendlein A. , Tschöpe C. , Jung F. 
Published: January 2015

AbstractOn the basis of the clinical studies in patients with coronary artery disease (CAD) presenting an increased percentage of activated platelets, we hypothesized that hemocompatibility testing utilizing platelets from healthy individuals may result in an underestimation of the materials' thrombogenicity. Therefore, we investigated the interaction of polymer‐based biomaterials with platelets from CAD patients in comparison to platelets from apparently healthy individuals. In vitro static thrombogenicity tests revealed that adherent platelet densities and total platelet covered areas were significantly increased for the low (polydimethylsiloxane, PDMS) and medium (Collagen) thrombogenic surfaces in the CAD group compared to the healthy subjects group. The area per single platelet—indicating the spreading and activation of the platelets—was markedly increased on PDMS treated with PRP from CAD subjects. This could not be observed for collagen or polytetrafluoroethylene (PTFE). For the latter material, platelet adhesion and surface coverage did not differ between the two groups. Irrespective of the substrate, the variability of these parameters was increased for CAD patients compared to healthy subjects. This indicates a higher reactivity of platelets from CAD patients compared to the healthy individuals. Our results revealed, for the first time, that utilizing platelets from apparently healthy donors bears the risk of underestimating the thrombogenicity of polymer‐based biomaterials. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 210–217, 2016.
Binding of Paeonol to Human Serum Albumin: A Hybrid Spectroscopic Approach and Conformational Study
Authors: Wang Juan 
Published: January 2015

ABSTRACTThe purpose of this study was to elucidate the binding of paeonol to human serum albumin (HSA) through spectroscopic methods. The fluorescence quenching of HSA by paeonol was a result of the formation of the HSA–paeonol complex with low binding affinity (K = 4.45 × 103 M−1 at 298 K). Thermodynamic parameters (ΔG○ = –2.08 × 104 J·mol−1, ΔS○ = 77.9 J·mol−1·K−1, ΔH○ = 2.41 × 103 J·mol−1, kq = 9.67 × 1012 M−1·s−1) revealed that paeonol mainly binds HSA through hydrophobic force following a static quenching mode. The binding distance was estimated to be 1.91 nm by fluorescence resonant energy transfer. The conformation of HSA was changed and aggregates were formed in the presence of paeonol, revealed by synchronous fluorescence, circular dichroism, Fourier transform infrared spectroscopy, three‐dimensional fluorescence spectroscopy, and resonance light scattering results.
Hospital course and discharge criteria for children hospitalized with bronchiolitis
Authors: Mansbach Jonathan M. , Clark Sunday , Piedra Pedro A. , Macias Charles G. , Schroeder Alan R. , Pate Brian M. , Sullivan Ashley F. , Espinola Janice A. , Camargo Carlos A. ,   for the MARC‐30 Investigators
Published: January 2015

BACKGROUNDFor children hospitalized with bronchiolitis, there is uncertainty about the expected inpatient clinical course and when children are safe for discharge.OBJECTIVESExamine the time to clinical improvement, risk of clinical worsening after improvement, and develop discharge criteria.DESIGNProspective multiyear cohort study.SETTINGSixteen US hospitals.PARTICIPANTSConsecutive hospitalized children age <2 years with bronchiolitis.MEASUREMENTWe defined clinical improvement using: (1) retraction severity, (2) respiratory rate, (3) room air oxygen saturation, and (4) hydration status. After meeting improvement criteria, children were considered clinically worse based on the inverse of ≥1 of these criteria or need for intensive care.RESULTSAmong 1916 children, the median number of days from onset of difficulty breathing until clinical improvement was 4 (interquartile range, 3–7.5 days). Of the total, 1702 (88%) met clinical improvement criteria, with 4% worsening (3% required intensive care). Children who worsened were age <2 months (adjusted odds ratio [AOR]: 3.51; 95% confidence interval [CI]: 2.07‐5.94), gestational age <37 weeks (AOR: 1.94; 95% CI: 1.13‐3.32), and presented with severe retractions (AOR: 5.55; 95% CI: 2.12‐14.50), inadequate oral intake (AOR: 2.54; 95% CI: 1.39‐4.62), or apnea (AOR: 2.87; 95% CI: 1.45‐5.68). Readmissions were similar for children who did and did not worsen.CONCLUSIONSAlthough children hospitalized with bronchiolitis had wide‐ranging recovery times, only 4% worsened after initial improvement. Children who worsened were more likely to be younger, premature infants presenting in more severe distress. For children hospitalized with bronchiolitis, these data may help establish more evidence‐based discharge criteria, reduce practice variability, and safely shorten hospital length‐of‐stay. Journal of Hospital Medicine 2015;10:205–211. © 2015 Society of Hospital Medicine
Creating Capabilities through Maternal Mental Health Interventions: A Case Study at Hanover Park, Cape Town
Authors: Meintjes Ingrid , Field Sally , Van Heyningen Thandi , Honikman Simone 
Published: January 2015

AbstractIn South Africa, approximately one third of resource‐poor women experience mental illness during pregnancy. Prevalence is higher in low‐resource settings than in developed countries. The poverty–mental illness cycle is well documented. Through the capabilities approach, this paper locates maternal mental illness in a development framework and explores the deprivational impacts of mental illness. It describes a counselling intervention in South Africa as a case study and applies a qualitative content analysis to descriptive data of a sample of five typical clients. Findings suggest that integrated maternal mental health care may act as a strategic intervention for capability formation and sustainable development. Copyright © 2015 John Wiley & Sons, Ltd.
Nitrate content in a collection of higher mushrooms
Authors: Bóbics Renáta , Krüzselyi Dániel , Vetter János 
Published: January 2015

AbstractBACKGROUNDData of mushroom nitrate content from scientific studies is limited. There have been two such recent investigations (mainly regarding certain cultivated species). To obtain comparable analytical data, we analyzed 134 samples of 54 taxa gathered and prepared by our department.RESULTSThe mushroom species were evaluated according to their nutritional types: saprotrophic, mycorrhizal and wood‐decaying groups. Low and relatively invariable contents were found in the mycorrhizal (216.5 mg kg−1 dry matter (DM) and wood‐decaying groups (228.6 mg kg−1 DM), but in the saprotrophic group we observed a wide variability (151.4–12 715 mg kg−1 DM).CONCLUSIONA considerable nitrate content was found in samples of seven ‘accumulator’ species (Clitocybe nebularis, C. odora, Lepista nuda, L. personata, L. irina, Macrolepiota rachodes and M. procera). The toxicological relevance of daily uptake of acceptable nitrate content via mushrooms only is not presumable, but the ‘accumulator’ saprotrophic species can be ‘contributors’ to our nitrate intake in foods. © 2015 Society of Chemical Industry
Sleep Variability in Military‐Related PTSD: A Comparison to Primary Insomnia and Healthy Controls
Authors: Straus Laura D. , Drummond Sean P. A. , Nappi Carla M. , Jenkins Melissa M. , Norman Sonya B. 
Published: January 2015

AbstractSleep disturbances are prevalent in posttraumatic stress disorder (PTSD) and are associated with a number of adverse health consequences. Few studies have used comprehensive assessment methods to characterize sleep in Operation Iraqi Freedom/Operation Enduring Freedom/Operation New Dawn (OEF/OIF/OND) veterans with PTSD. OEF/OIF/OND veterans with PTSD and sleep disturbance (n = 45) were compared to patients with primary insomnia (n = 25) and healthy control subjects (n = 27). Participants were assessed using questionnaire‐based measures as well as daily subjective and objective measures of sleep. The 3 groups were compared with regard to (a) group means, (b) intraindividual (i.e., night‐to‐night) variability of sleep, and (c) interindividual (i.e., within‐group) variability of sleep. In terms of group means, only objective sleep efficiency was significantly worse with PTSD than with primary insomnia (d = 0.54). Those with PTSD differed from those with primary insomnia on measures of intraindividual as well as interindividual variability (d = 0.48–0.73). These results suggested sleep symptoms in OEF/OIF/OND veterans with PTSD are more variable across nights and less consistent across patients relative to sleep symptoms in insomnia patients without PTSD. These findings have implications for research, as well as for personalizing treatment for individuals with PTSD.
A widespread allergic reaction to black tattoo ink caused by laser treatment
Authors: Bernstein Eric F. 
Published: January 2015

Background and ObjectiveThis is the first reported case of a local and widespread reaction in a 39 year old woman, to black tattoo ink, induced by Q‐switched laser treatment.Study Design/Patients and MethodsA 39 year old woman was treated with the Q‐switched Nd:YAG laser for removal of a decorative tattoo of her lower back.ResultsSubsequent to laser treatment, a severe, widespread allergic reaction developed within and surrounding the treated tattoo.ConclusionsTattoo reactions subsequent to laser treatment should be considered in addition to reactions to topical antibiotics or wound dressings, following laser treatment of tattoos. Lasers Surg. Med. 47:180–182, 2015. © 2015 Wiley Periodicals, Inc.