bluuebunny/crossref_metadata_2025_split huggingface dataset:
Predicting DNAPL mass discharge and contaminated site longevity probabilities: Conceptual model and high‐resolution stochastic simulation
Authors: Koch J. , Nowak W. 
Published: January 2015

AbstractImproper storage and disposal of nonaqueous‐phase liquids (NAPLs) has resulted in widespread contamination of the subsurface, threatening the quality of groundwater as a freshwater resource. The high frequency of contaminated sites and the difficulties of remediation efforts demand rational decisions based on a sound risk assessment. Due to sparse data and natural heterogeneities, this risk assessment needs to be supported by appropriate predictive models with quantified uncertainty. This study proposes a physically and stochastically coherent model concept to simulate and predict crucial impact metrics for DNAPL contaminated sites, such as contaminant mass discharge and DNAPL source longevity. To this end, aquifer parameters and the contaminant source architecture are conceptualized as random space functions. The governing processes are simulated in a three‐dimensional, highly resolved, stochastic, and coupled model that can predict probability density functions of mass discharge and source depletion times. While it is not possible to determine whether the presented model framework is sufficiently complex or not, we can investigate whether and to which degree the desired model predictions are sensitive to simplifications often found in the literature. By testing four commonly made simplifications, we identified aquifer heterogeneity, groundwater flow irregularity, uncertain and physically based contaminant source zones, and their mutual interlinkages as indispensable components of a sound model framework.
On the upscaling of mass transfer rate expressions for interpretation of source zone partitioning tracer tests
Authors: Boroumand Ali , Abriola Linda M. 
Published: January 2015

AbstractAnalysis of partitioning tracer tests conducted in dense nonaqueous phase liquid (DNAPL) source zones relies on conceptual models that describe mass exchange between the DNAPL and aqueous phases. Such analysis, however, is complicated by the complex distribution of entrapped DNAPL mass and formation heterogeneity. Due to parameter uncertainty in heterogeneous regions and the desire to reduce model complexity, the effect of mass transfer limitations is often neglected, and an equilibrium‐based model is typically used to interpret test results. This work explores the consequences of that simplifying assumption on test data interpretation and develops an alternative upscaled modeling approach to quantify effective mass transfer rates. To this end, a series of partitioning tracer tests is numerically simulated in heterogeneous two‐dimensional PCE‐DNAPL source zones, representative of a range of hydraulic conductivity and DNAPL mass distribution characteristics. The effective mass transfer coefficient corresponding to each test is determined by fitting an upscaled model to the simulated data, and regression analysis is performed to explore the correlation between various source zone metrics and the effective mass transfer coefficient. Results suggest that vertical DNAPL spreading, Reynolds number, pool fraction, and the effective organic phase saturation are the most significant parameters controlling tracer partitioning rates. Finally, a correlation for prediction of the effective (upscaled) mass transfer coefficient is proposed and verified using existing experimental data. The developed upscaled model incorporates the influence of physical heterogeneity on the rate of tracer partitioning and, thus, can be used for the estimation of source zone mass distribution characteristics from tracer test results.
Projected changes in snowfall extremes and interannual variability of snowfall in the western United States
Authors: Lute A. C. , Abatzoglou J. T. , Hegewisch K. C. 
Published: January 2015

AbstractProjected warming will have significant impacts on snowfall accumulation and melt, with implications for water availability and management in snow‐dominated regions. Changes in snowfall extremes are confounded by projected increases in precipitation extremes. Downscaled climate projections from 20 global climate models were bias‐corrected to montane Snowpack Telemetry stations across the western United States to assess mid‐21st century changes in the mean and variability of annual snowfall water equivalent (SFE) and extreme snowfall events, defined by the 90th percentile of cumulative 3 day SFE amounts. Declines in annual SFE and number of snowfall days were projected for all stations. Changes in the magnitude of snowfall event quantiles were sensitive to historical winter temperature. At climatologically cooler locations, such as in the Rocky Mountains, changes in the magnitude of snowfall events mirrored changes in the distribution of precipitation events, with increases in extremes and less change in more moderate events. By contrast, declines in snowfall event magnitudes were found for all quantiles in warmer locations. Common to both warmer and colder sites was a relative increase in the magnitude of snowfall extremes compared to annual SFE and a larger fraction of annual SFE from snowfall extremes. The coefficient of variation of annual SFE increased up to 80% in warmer montane regions due to projected declines in snowfall days and the increased contribution of snowfall extremes to annual SFE. In addition to declines in mean annual SFE, more frequent low‐snowfall years and less frequent high‐snowfall years were projected for every station.
Cardiovascular Risk Profile at the Onset of Psoriatic Arthritis: A Population‐Based Cohort Study
Authors: Ernste F. C. , Sánchez‐Menéndez M. , Wilton K. M. , Crowson C. S. , Matteson E. L. , Maradit Kremers H. 
Published: January 2015

ObjectiveThe role of cardiovascular disease (CVD) risk factors in psoriatic arthritis (PsA) is poorly understood. We examined the prevalence of CVD risk factors at initial onset of PsA and compared the observed incidence of CVD events with that predicted by the Framingham Risk Score (FRS) to determine its applicability in this patient population.MethodsA population‐based incidence cohort of 158 patients with PsA who fulfilled Classification of Psoriatic Arthritis criteria for PsA in 1989–2008 was assembled. Medical records were reviewed to ascertain CVD risk factors and CVD events. Future risk of CVD was estimated using the FRS algorithm.ResultsMean age was 43.4 years (range 19–74 years), 61% were men, and 44% were obese (body mass index ≥30 kg/m2). Fifty‐four patients (34%) presented with ≥2 CVD risk factors at PsA incidence. Among 126 patients ages ≥30 years at PsA incidence with no prior history of CVD, 33% had an FRS ≥10%, with 11% having an FRS ≥20%, and 18 experienced a CVD event in the first 10 years of disease duration. The 10‐year cumulative incidence of CVD events was 17% (95% confidence interval [95% CI] 10%–24%), almost twice as high as the predicted incidence based on the FRS (standardized incidence ratio 1.80, 95% CI 1.14–2.86; P = 0.012).ConclusionThe majority of newly diagnosed PsA patients have a >10% risk of CVD within 10 years of PsA incidence. The CVD risk in these patients is higher than expected and underestimated by the FRS.
Comprehensive Appraisal of Magnetic Resonance Imaging Findings in Sustained Rheumatoid Arthritis Remission: A Substudy
Authors: Ranganath Veena K. , Motamedi Kambiz , Haavardsholm Espen A. , Maranian Paul , Elashoff David , McQueen Fiona , Duffy Erin L. , Bathon Joan M. , Curtis Jeffrey R. , Chen Weiling , Moreland Larry , Louie James , Amjadi Sogol , O'Dell James , Cofield Stacey S. , St.Clair E. William , Bridges S. Louis , Paulus Harold E. 
Published: January 2015

ObjectiveTo evaluate the effect of sustained American College of Rheumatology (ACR)/European League Against Rheumatism (EULAR) Boolean remission on residual joint inflammation assessed by magnetic resonance imaging (MRI) and to secondarily evaluate other clinical definitions of remission, within an early seropositive rheumatoid arthritis (RA) cohort.MethodsA subcohort of 118 RA patients was enrolled from patients who completed the 2‐year, double‐blind randomized Treatment of Early Aggressive Rheumatoid Arthritis (TEAR) trial. Patients received a single contrast‐enhanced 1.5T MRI of their most involved wrist. Two readers scored MRIs for synovitis, osteitis, tenosynovitis, and erosions. Clinical assessments were performed every 3 months during the trial and at time of MRI.ResultsThe subcohort was 92% seropositive with mean age 51 years, duration 4.1 months, and Disease Activity Score in 28 joints using the erythrocyte sedimentation rate 5.8 at TEAR entry. Total MRI inflammatory scores (tenosynovitis + synovitis + osteitis) were lower among patients in clinical remission. Lower MRI scores were correlated with longer duration of Clinical Disease Activity Index (CDAI) remission (ρ = 0.22, P = 0.03). At the time of MRI, 89 patients had no wrist pain/tenderness/swelling; however, all 118 patients had MRI evidence of residual joint inflammation after 2 years. No statistically significant differences in damage or MRI inflammatory scores were observed across treatment groups.ConclusionThis is the first detailed appraisal describing the relationship between clinical remission cut points and MRI inflammatory scores within an RA randomized controlled trial. The most stringent remission criteria (2011 ACR/EULAR and CDAI) best differentiate the total MRI inflammatory scores. These results document that 2 years of triple therapy or tumor necrosis factor plus methotrexate treatment in early RA does not eliminate MRI evidence of joint inflammation.
Association of Socioeconomic Status With Treatment Delays, Disease Activity, Joint Damage, and Disability in Rheumatoid Arthritis
Authors: Molina Emily , del Rincon Inmaculada , Restrepo Jose Felix , Battafarano Daniel F. , Escalante Agustin 
Published: January 2015

ObjectiveTo examine the association of socioeconomic status (SES) and delays in disease‐modifying antirheumatic drug (DMARD) treatment with clinical measures in rheumatoid arthritis (RA) patients.MethodsRA patients were recruited from rheumatology practices. We assessed SES based on education, occupation, and income, and divided patients into tertiles. The time from RA symptom onset to DMARD initiation (DMARD lag) was determined by self‐report of the 2 dates, and distance to the rheumatologist (Distance) was obtained from Google Maps. We examined disease activity, determined by the Disease Activity Score in 28 joints using the erythrocyte sedimentation rate (DAS28‐ESR); joint damage, determined from hand radiographs by Sharp scores; and physical disability, determined by the modified Health Assessment Questionnaire (M‐HAQ). We used linear regression models to examine the relationship between clinical measures and SES, Distance, and DMARD lag.ResultsWe recruited 1,209 RA patients, 1,159 of whom had received DMARD treatment. Mean ± SD DMARD lag was 6.9 ± 9.0 years. On average, patients with lower SES waited 8.5 ± 10.2 years after onset of RA symptoms to begin DMARD treatment, compared to those in the middle and upper SES tertiles who waited 6.1 ± 7.9 years (P = 0.002) and 6.1 ± 8.6 years (P = 0.009), respectively. Each year of delayed treatment was associated with a DAS28‐ESR increase of 0.02 (P ≤ 0.001), a Sharp score increase of 1.33 (P ≤ 0.001), and an M‐HAQ score increase of 0.01 (P ≤ 0.001).ConclusionLow SES was associated with delay in DMARD initiation, and both were independently associated with worse clinical measures in RA. Strategies to reduce treatment delay in low‐SES RA patients are needed.
Expert Panel Consensus on Assessment Checklists for a Rheumatology Objective Structured Clinical Examination
Authors: Criscione‐Schreiber Lisa G. , Sloane Richard J. , Hawley Jeffrey , Jonas Beth L. , O'Rourke Kenneth S. , Bolster Marcy B. 
Published: January 2015

ObjectiveWhile several regional fellowship groups conduct rheumatology objective structured clinical examinations (ROSCEs), none have been validated for use across programs. We aimed to establish agreement among subspecialty experts regarding checklist items for several ROSCE stations.MethodsWe administered a 1‐round survey to assess the importance of 173 assessment checklist items for 11 possible ROSCE stations. We e‐mailed the survey to 127 rheumatology educators from across the US. Participants rated each item's importance on a 5‐point Likert scale (1 = not important to 5 = very important). Consensus for high importance was predefined as a lower bound of the 95% confidence interval ≥4.0.ResultsTwenty‐five individuals (20%) completed the expert panel survey. A total of 133 of the 173 items (77%) met statistical cutoff for consensus to retain. Several items that had population means of ≥4.0 but did not meet the predetermined definition for consensus were rejected. The percentage of retained items for individual stations ranged from 24% to 100%; all items were retained for core elements of patient counseling and radiograph interpretation tasks. Only 24% of items were retained for a rehabilitation medicine station and 60% for a microscope use/synovial fluid analysis station.ConclusionThis single‐round expert panel survey established consensus on 133 items to assess on 11 proposed ROSCE stations. The method used in this study, which can engage a diverse geographic representation and employs rigorous statistical methods to establish checklist content agreement, can be used in any medical field.
Characterizing Pain Flares From the Perspective of Individuals With Symptomatic Knee Osteoarthritis
Authors: Murphy Susan L. , Lyden Angela K. , Kratz Anna L. , Fritz Heather , Williams David A. , Clauw Daniel J. , Gammaitoni Arnold R. , Phillips Kristine 
Published: January 2015

ObjectiveAlthough pain in knee osteoarthritis (OA) commonly affects activity engagement, the daily pain experience has not been fully characterized. Specifically, the nature and impact of pain flares is not well understood. This study characterized pain flares as defined by participants with knee OA. Pain flare occurrence and experience were measured over 7 days.MethodsThis was a multiple methods study; qualitative methods were dominant. Data were collected during the baseline portion of a randomized controlled trial. Participants met criteria for knee OA and had moderate to severe pain. They completed questionnaires and a 7‐day home monitoring period that captured momentary symptom reports simultaneously with physical activity via accelerometry (n = 45). Participants also provided individual definitions of pain flare that were used throughout the home monitoring period to indicate whether a pain flare occurred.ResultsPain flares were described most often by quality (often sharp), followed by timing (seconds, minutes) and by antecedents and consequences. When asked if their definition of a flare agreed with a supplied definition, 49% of the sample reported only “somewhat,” “a little,” or “not at all.” Using individual definitions, 78% experienced at least 1 daily pain flare over the home monitoring period; 24% had a flare on more than 50% of the monitored days.ConclusionPain flares were common, fleeting, and often experienced in the context of activity engagement. Participants’ views on what constitutes a pain flare differ from commonly accepted definitions. Pain flares are an understudied aspect of the knee OA pain experience and require further characterization.
Thermodynamic Studies on Polyvinylpyrrolidone Solution Systems Used for Fabrication of Electrospun Nanostructures: Effects of the Solvent
Authors: Nasouri Komeil , Shoushtari Ahmad Mousavi , Mojtahedi Mohammad Reza Mohaddes 
Published: January 2015

ABSTRACTIn this research, we investigate the influence of polyvinylpyrrolidone (PVP) solution systems on the morphology of the PVP nanofibers fabricated by electrospinning of PVP solutions prepared in different organic solvents, including ethanol (EtOH), propanol (PrOH), chloroform, N‐methyl‐2‐pyrrolidone (NMP), and N,N‐dimethylformamide (DMF) and then compared with the experimental results. First, by considering the electrospun solutions behavior, the thermodynamic studies were evaluated then Hansen solubility theory was applied to select the desirable solvent systems. The dissolving power of the solvents for PVP was obtained in the following order: DMF > NMP >> chloroform > PrOH > EtOH. It seems that every solvent, which is able to dissolve PVP polymer, shows different spinning characteristics under identical conditions of processing parameters. By using PrOH, chloroform, and NMP solvents, electrospun nanofibers’ average diameter was decreased intensively but at the same time beads formation was observed. We investigated that EtOH was a desirable solvent for PVP to fabricate fibers with z micrometer diameter distribution, but because of its low dissolving power it is suitable for microfiber synthesis with the electrospinning process. Based on the Hansen theory and experimental results, the PVP/DMF solutions showed desirable characteristics for the electrospinning system. Furthermore, the PVP nanofiber's uniformity of the PVP/DMF solution was higher than other solvent systems, which mean that fiber diameter distribution is scanty than others. Finally, it has been demonstrated that with an appropriate solvent the nanofiber diameter distribution and formation of beads can be controlled by Hansen theory.
Lipid‐specific immunoglobulin M bands in cerebrospinal fluid are associated with a reduced risk of developing progressive multifocal leukoencephalopathy during treatment with natalizumab
Authors: Villar Luisa M. , Costa‐Frossard Lucienne , Masterman Thomas , Fernandez Oscar , Montalban Xavier , Casanova Bonaventura , Izquierdo Guillermo , Coret Francisco , Tumani Hayrettin , Saiz Albert , Arroyo Rafael , Fink Katharina , Leyva Laura , Espejo Carmen , Simó‐Castelló María , García‐Sánchez María I. , Lauda Florian , Llufriú Sara , Álvarez‐Lafuente Roberto , Olascoaga Javier , Prada Alvaro , Oterino Agustín , de Andrés Clara , Tintoré Mar , Ramió‐Torrentà Lluis , Rodríguez‐Martín Eulalia , Picón Carmen , Comabella Manuel , Quintana Ester , Agüera Eduardo , Díaz Santiago , Fernandez‐Bolaños Ricardo , García‐Merino Juan A. , Landete Lamberto , Menéndez‐González Manuel , Navarro Laura , Pérez Domingo , Sánchez‐López Fernando , Serrano‐Castro Pedro J. , Tuñón Alberto , Espiño Mercedes , Muriel Alfonso , Bar‐Or Amit , Álvarez‐Cermeño José C. 
Published: January 2015

ObjectiveProgressive multifocal leukoencephalopathy (PML) is a serious side effect associated with natalizumab treatment in multiple sclerosis (MS). PML risk increases in individuals seropositive for anti–John Cunningham virus (JC) antibodies, with prolonged duration of natalizumab treatment, and with prior exposure to immunosuppressants. We explored whether the presence of lipid‐specific immunoglobulin M oligoclonal bands in cerebrospinal fluid (CSF; IgM bands), a recognized marker of highly inflammatory MS, may identify individuals better able to counteract the potential immunosuppressive effect of natalizumab and hence be associated with a reduced risk of developing PML.MethodsWe studied 24 MS patients who developed PML and another 343 who did not suffer this opportunistic infection during natalizumab treatment. Patients were recruited at 25 university hospitals. IgM bands were studied by isoelectric focusing and immunodetection. CSF lymphocyte counts were explored in 151 MS patients recruited at Ramon y Cajal Hospital in Madrid, Spain.ResultsIgM bands were independently associated with decreased PML risk (odds ratio [OR] = 45.9, 95% confidence interval [CI] = 5.9–339.3, p < 0.0001) in patients treated with natalizumab. They were also associated with significantly higher CSF CD4, CD8, and B‐cell numbers. Patients positive for IgM bands and anti‐JC antibodies had similar levels of reduced PML risk to those who were anti‐JC negative (OR = 1.55, 95% CI = 0.09–25.2, p = 1.0). Higher risk was observed in patients positive for anti‐JC antibodies and negative for IgM bands (19% of the total cohort, OR = 59.71, 95% CI = 13.6–262.2).InterpretationThe presence of IgM bands reflects a process that may diminish the risk of PML by counteracting the excess of immunosuppression that may occur during natalizumab therapy. Ann Neurol 2015;77:447–457
Ligand‐Controlled Regiodivergent Palladium‐Catalyzed Decarboxylative Allylation Reaction to Access α,α‐Difluoroketones
Authors: Yang Ming‐Hsiu , Orsi Douglas L. , Altman Ryan A. 
Published: January 2015

Abstractα,α‐Difluoroketones possess unique physicochemical properties that are useful for developing therapeutics and probes for chemical biology. To access the α‐allyl‐α,α‐difluoroketone substructure, complementary palladium‐catalyzed decarboxylative allylation reactions were developed to provide linear and branched α‐allyl‐α,α‐difluoroketones. For these orthogonal processes, the fluorination pattern of the substrate enabled the ligands to dictate the regioselectivity of the transformations.
Indolo‐Phakelline als β5‐spezifische nichtkovalente Proteasom‐Inhibitoren
Authors: Beck Philipp , Lansdell Theresa A. , Hewlett Nicole M. , Tepe Jetze J. , Groll Michael 
Published: January 2015

AbstractDas Proteasom ist ein etabliertes Angriffsziel zur Behandlung von Krebs und Autoimmunerkrankungen. Die Anwendung von Proteasominhibitoren ist jedoch auf Blutkrebs beschränkt, da ihre peptidischen Grundgerüste und reaktiven Kopfgruppen ungünstige pharmakodynamische Eigenschaften mit sich bringen. Die Entdeckung neuer Leitstrukturen ist somit von grundlegender Bedeuteutung. Hier stellen wir die erste Kristallstruktur des Proteasoms im Komplex mit einem Indolo‐Phakellin vor, das sich strukturell von allen bisheringen Inhibitoren signifikant unterscheidet und einen einzigartigen, nichtkovalenten Bindemodus aufweist. Das pentacyclische Alkaloid bindet ausschließlich und spezifisch in die S3‐sub‐Tasche des proteasomalen β5‐Substratbindekanals und wird durch eine Halogenbrücke mit dem Proteinrückgrat stabilisiert. Der Ligand bietet ein ideales Grundgerüst für die strukturbasierte Entwicklung von Untereinheit‐spezifischen nichtpeptidischen Proteasomhemmstoffen.
Die Reaktion von Pentelidenkomplexen mit Carbodiimiden und Alkylaziden – ein direkter Weg zu viergliedrigen Heterocyclen
Authors: Seidl Michael , Kuntz Christian , Bodensteiner Michael , Timoshkin Alexey Y. , Scheer Manfred 
Published: January 2015

AbstractDie Reaktion der Pentelidenkomplexe [Cp*E{W(CO)5}2] (E=P (1 a), As (1 b); Cp*=C5Me5) mit Carbodiimiden führt zu den neuen viergliedrigen Heterocyclen des Typs [Cp*C(NR)2E{W(CO)5}2] (E=P: R=iPr (2 a), Cy (3 a); E=As: R=iPr (2 b), Cy (3 b)). Die Reaktion des Phosphinidenkomplexes 1 a mit Alkylaziden ergibt die Triazaphosphetderivate [Cp*P{W(CO)5}N(R)NN{W(CO)5}] (R=Hex, Cy; 4). Diese beispiellosen viergliedrigen Triazaphosphetkomplexe können als stabilisierte Intermediate der Staudinger‐Reaktion betrachtet werden, die bisher noch nicht isoliert werden konnten. Alle erhaltenen Produkte wurden durch NMR‐ und IR‐Spektroskopie, Massenspektrometrie und durch Röntgenstrukturanalyse an Einkristallen charakterisiert.
Catalytic Asymmetric Hydrogenation of Pyrimidines
Authors: Kuwano Ryoichi , Hashiguchi Yuta , Ikeda Ryuhei , Ishizuka Kentaro 
Published: January 2015

AbstractThe asymmetric hydrogenation of pyrimidines proceeded with high enantioselectivity (up to 99 % ee) using an iridium catalyst composed of [IrCl(cod)]2, a ferrocene‐containing chiral diphosphine ligand (Josiphos), iodine, and Yb(OTf)3 (cod=1,5‐cyclooctadiene). The chiral catalyst converted various 4‐substituted pyrimidines into chiral 1,4,5,6‐tetrahydropyrimidines in high yield. The lanthanide triflate is crucial for achieving the high enantioselectivity as well as for activating the heteroarene substrate.