bluuebunny/crossref_metadata_2025_split huggingface dataset:
The 7-Item Generalized Anxiety Disorder Scale as a Tool for Measuring Generalized Anxiety in Multiple Sclerosis
Authors: Terrill Alexandra L. , Hartoonian Narineh , Beier Meghan , Salem Rana , Alschuler Kevin 
Published: September 2014

Background: Generalized anxiety disorder (GAD) is common in multiple sclerosis (MS) but understudied. Reliable and valid measures are needed to advance clinical care and expand research in this area. The objectives of this study were to examine the psychometric properties of the 7-item Generalized Anxiety Disorder Scale (GAD-7) in individuals with MS and to analyze correlates of GAD.Methods: Participants (N = 513) completed the anxiety module of the Patient Health Questionnaire (GAD-7). To evaluate psychometric properties of the GAD-7, the sample was randomly split to conduct exploratory and confirmatory factor analyses.Results: Based on the exploratory factor analysis, a one-factor structure was specified for the confirmatory factor analysis, which showed excellent global fit to the data (χ212 = 15.17, P = .23, comparative fit index = 0.99, root mean square error of approximation = 0.03, standardized root mean square residual = 0.03). The Cronbach alpha (0.75) indicated acceptable internal consistency for the scale. Furthermore, the GAD-7 was highly correlated with the Hospital Anxiety and Depression Scale–Anxiety (r = 0.70). Age and duration of MS were both negatively associated with GAD. Higher GAD-7 scores were observed in women and individuals with secondary progressive MS. Individuals with higher GAD-7 scores also endorsed more depressive symptoms.Conclusions: These findings support the reliability and internal validity of the GAD-7 for use in MS. Correlational analyses revealed important relationships with demographics, disease course, and depressive symptoms, which suggest the need for further anxiety research.
Hourly, daily, and seasonal variability in the absorption spectra of chromophoric dissolved organic matter in a eutrophic, humic lake
Authors: Müller R. A. , Kothawala D. N. , Podgrajsek E. , Sahlée E. , Koehler B. , Tranvik L. J. , Weyhenmeyer G. A. 
Published: September 2014

AbstractThe short‐term (hourly and daily) variation in chromophoric dissolved organic matter (CDOM) in lakes is largely unknown. We assessed the spectral characteristics of light absorption by CDOM in a eutrophic, humic shallow mixed lake of temperate Sweden at a high‐frequency (30 min) interval and during a full growing season (May to October). Physical time series, such as solar radiation, temperature, wind, and partial pressures of carbon dioxide in water and air, were measured synchronously. We identified a strong radiation‐induced summer CDOM loss (25 to 50%) that developed over 4 months, which was accompanied by strong changes in CDOM absorption spectral shape. The magnitude of the CDOM loss exceeded subhourly to daily variability by an order of magnitude. Applying Fourier analysis, we demonstrate that variation in CDOM remained largely unaffected by rapid shifts in weather, and no apparent response to in‐lake dissolved organic carbon production was found. In autumn, CDOM occasionally showed variation at hourly to daily time scales, reaching a maximum daily coefficient of variation of 15%. We suggest that lake‐internal effects on CDOM are quenched in humic lake waters by dominating effects associated with imported CDOM and solar exposure. Since humic lake waters belong to one of the most abundant lake types on Earth, our results have important implications for the understanding of global CDOM cycling.
Extension of the tuning constant in the Huber's function for robust modeling of piezoelectric systems
Authors: Corbier C. , Carmona J.‐C. 
Published: September 2014

SummaryThis paper proposes a new modeling approach that is experimentally validated on piezoelectric systems in order to provide a black‐box pseudolinear model for complex systems control. Most of the time, one uses physical based approaches. However, sometimes complex phenomena occur in the system due to atypical changes of the process behavior, output noise or some hard nonlinearities. Therefore, we adopt identification methods to achieve the modeling task. The microdisplacements of the piezoelectric systems generate atypical data named outliers, leading to large estimated prediction errors. Since these errors disturb the classical normal probability density function, we choose here, as corrupted distribution model, the gross error model (GEM). In order to deal more efficiently with the outliers, we use the Huber's function, as mixed L2/L1 norms in which the tuning threshold named scaling factor is extended. From this function, a cost function also named PREC as parameterized robust estimation criterion is established. The identification is performed by choosing an Output Error model structure. In order to express the asymptotic covariance matrix of the robust estimator, we present a L finite Taylor's expansion to linearize the gradient and the hessian of the PREC. Experimental results are presented and discussed. Copyright © 2014 John Wiley & Sons, Ltd.
Immediate postoperative imaging after uncomplicated endoscopic approach to the anterior skull base: is it necessary?
Authors: Nadimi Sahar , Caballero Nadieska , Carpenter Patrick , Sowa Lauren , Cunningham Ryan , Welch Kevin C. 
Published: September 2014

BackgroundPostoperative imaging is frequently performed to assess for intracranial complications following anterior skull base (ASB) surgery. However, there is little data to suggest that radiologic studies change the management of complications. In this study, the utility of postoperative imaging within 72 hours after uncomplicated ASB surgery was examined.MethodsA retrospective review was conducted of 143 patients who underwent endoscopic ASB surgery between 2007 and 2013 at Loyola University Medical Center. The main outcomes measures included the ability of head computed tomography (CT) scan to identify postoperative complications and hallmark symptoms associated with complications.ResultsSeventy‐nine patients underwent postoperative imaging within 72 hours of the initial surgery. The most common finding was pneumocephalus (35/79; 44%). Expanding pneumocephalus requiring surgical intervention developed in 3 cases. Cerebrospinal fluid (CSF) leak was the most common complication, occurring in 22 of 143 (15%) of the patients. Of the 24 patients who developed a postoperative complication, all had clinical signs or symptoms indicative of the need for surgical or medical intervention. The positive predictive value for a head CT scan to detect a complication was 12%, negative predictive value was 92%, and sensitivity and specificity were 63% and 48%, respectively.ConclusionRoutine postoperative imaging may be unnecessary after uncomplicated endoscopic ASB surgery because (1) it may not alter patient management; (2) it may not detect the most common complication (CSF leak); and (3) when imaging is positive, the patient has clinical symptoms suggesting a need for intervention.
A Trifluorinated Thiazoline Scaffold Leading to Pro‐apoptotic Agents Targeting Prohibitins
Authors: Pérez‐Perarnau Alba , Preciado Sara , Palmeri Claudia Mariela , Moncunill‐Massaguer Cristina , Iglesias‐Serret Daniel , González‐Gironès Diana M. , Miguel Miriam , Karasawa Satoki , Sakamoto Satoshi , Cosialls Ana M. , Rubio‐Patiño Camila , Saura‐Esteller José , Ramón Rosario , Caja Laia , Fabregat Isabel , Pons Gabriel , Handa Hiroshi , Albericio Fernando , Gil Joan , Lavilla Rodolfo 
Published: September 2014

AbstractA new class of small molecules, with an unprecedented trifluorothiazoline scaffold, were synthesized and their pro‐apoptotic activity was evaluated. With an EC50 in the low micromolar range, these compounds proved to be potent inducers of apoptosis in a broad spectrum of tumor cell lines, regardless of the functional status of p53. Fast structure–activity relationship studies allowed the preparation of the strongest apoptosis‐inducing candidate. Using a high performance affinity purification approach, we identified prohibitins 1 and 2, key proteins involved in the maintenance of cell viability, as the targets for these compounds.
Anion Complexation and The Hofmeister Effect
Authors: Carnegie Ryan S. , Gibb Corinne L. D. , Gibb Bruce C. 
Published: September 2014

AbstractThe 1H NMR spectroscopic analysis of the binding of the ClO4− anion to the hydrophobic, concave binding site of a deep‐cavity cavitand is presented. The strength of association between the host and the ClO4− anion is controlled by both the nature and concentration of co‐salts in a manner that follows the Hofmeister series. A model that partitions this trend into the competitive binding of the co‐salt anion to the hydrophobic pocket of the host and counterion binding to its external carboxylate groups successfully accounts for the observed changes in ClO4− affinity.
Hochaufgelöste spektroskopische Untersuchungen des chiralen Metallkomplexes [CpRe(CH3)(CO)(NO)] – ein möglicher Kandidat für die Untersuchung der Paritätsverletzung
Authors: Medcraft Chris , Wolf Robert , Schnell Melanie 
Published: September 2014

AbstractChirale Moleküle mit Schwermetallatomen wurden als vielversprechende Kandidaten für die Untersuchung von Paritätsverletzungseffekten vorgeschlagen. Hier stellen wir eine spektroskopische Untersuchung des chiralen Komplexes [CpRe(CH3)(CO)(NO)] mittels Breitband‐Rotationsspektroskopie in der Gasphase vor. Die hochaufgelösten Molekülspektren sind aufgrund der beiden Rhenium‐Isotopologe (185Re und 187Re), der Hyperfeinstruktur durch die Rhenium‐ und Stickstoffkerne sowie durch die Asymmetrie der chiralen Spezies sehr komplex. Da sich das Rheniumatom sehr nah am Molekülmassenschwerpunkt befindet, sind die Rotationskonstanten der beiden Rhenium‐Isotopologe einander sehr ähnlich, ihre eindeutige Unterscheidung ist allerdings über die charakteristische Kernquadrupolhyperfeinaufspaltung möglich. Der Vergleich mit berechneten Kernquadrupolkopplungskonstanten zeigt, dass relativistische Basissätze, die die Gesamtzahl der Elektronen berücksichtigen, notwendig sind, um das Rheniumatom in dieser Art von Komplexen korrekt zu beschreiben.
An Above‐Room‐Temperature Ferroelectric Organo–Metal Halide Perovskite: (3‐Pyrrolinium)(CdCl3)
Authors: Ye Heng‐Yun , Zhang Yi , Fu Da‐Wei , Xiong Ren‐Gen 
Published: September 2014

AbstractHybrid organo–metal halide perovskite materials, such as CH3NH3PbI3, have been shown to be some of the most competitive candidates for absorber materials in photovoltaic (PV) applications. However, their potential has not been completely developed, because a photovoltaic effect with an anomalously large voltage can be achieved only in a ferroelectric phase, while these materials are probably ferroelectric only at temperatures below 180 K. A new hexagonal stacking perovskite‐type complex (3‐pyrrolinium)(CdCl3) exhibits above‐room‐temperature ferroelectricity with a Curie temperature Tc=316 K and a spontaneous polarization Ps=5.1 μC cm−2. The material also exhibits antiparallel 180° domains which are related to the anomalous photovoltaic effect. The open‐circuit photovoltage for a 1 mm‐thick bulky crystal reaches 32 V. This finding could provide a new approach to develop solar cells based on organo–metal halide perovskites in photovoltaic research.
Lignin‐polyethylene glycol matrices and ethylcellulose to encapsulate highly soluble herbicides
Authors: Fernández‐Pérez Manuel , Villafranca‐Sánchez Matilde , Flores‐Céspedes Francisco , Daza‐Fernández Isabel 
Published: September 2014

ABSTRACTThe blending of lignin with polyethylene glycol (PEG) allowed us to obtain formulations with controlled release properties in which metribuzin have been successfully trapped with encapsulation efficiency higher than 85%. Moreover, the modification of the lignin's viscoelastic properties by the addition of PEG led to obtain herbicide formulations with active ingredient contents lower than 15%, suitable for its application in soil. Fourier transformed infrared spectroscopy and differential scanning calorimetry studies indicated the compatibility between polymers and metribuzin in lignin‐based controlled release formulations (CRFs). Lignin‐based formulations were coated in a Wurster‐type fluidized‐bed equipment using ethylcellulose and dibutylsebacate. Scanning electron microscope pictures showed a homogeneous film in ethylcellulose‐coated CRFs. The kinetic release studies showed that the release rate of metribuzin was mainly controlled either by selecting the granule size of controlled release lignin‐PEG matrixes, or by changing the thickness of coating film for ethylcellulose coated CRFs. These results could help to increase the efficiency of delivery of the highly soluble herbicide metribuzin and prevent the environmental pollution derived from its use. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41422.
In vitro and in vivo evaluations of three‐dimensional hydroxyapatite/silk fibroin nanocomposite scaffolds
Authors: Gholipourmalekabadi Mazaher , Mozafari Masoud , Gholipourmalekabadi Mahdieh , Nazm Bojnordi Maryam , Hashemi‐soteh Mohamad B. , Salimi Maryam , Rezaei Nourollah , Sameni Marzieh , Samadikuchaksaraei Ali , Ghasemi Hamidabadi Hatef 
Published: September 2014

AbstractIn this study, three‐dimensional hydroxyapatite/silk fibroin (HAp/SF) nanocomposite scaffolds were successfully prepared through layer solvent casting combined with the freeze‐drying technique for tissue engineering applications. Various SF aqueous concentrations, ranging from 2.5% to 10%, were used to control the physicochemical properties of the prepared scaffolds. Biologic responses of the rat bone marrow stromal cells (rBMSCs) to the HAp/SF scaffolds were examined by culturing the cells within them. In addition, biodegradation and biocompatibility of the scaffolds were evaluated in vitro and in vivo, respectively. Among the prepared scaffolds, HAp/SF‐2.5% was the most brittle sample and showed porous structure with lowest mechanical properties. The average pore diameters were 350 ± 67 and 112 ± 89 µm and decreased with the increase in the SF concentration from 5% to 10%, respectively. The pores formed in the scaffolds, made up of the 5% SF, were more uniform and regular than those of the scaffolds made up of 5% and 10% SF. The HAp/SF scaffolds did not change the rBMSCs viability and were not cytotoxic compared with the control sample. The scanning electron microscopy micrographs showed that the cells migrated into the pores and well attached to the scaffolds and their cytoplasm was extended in all directions, indicating a promising cell adhesion, high biocompatibility, and no cytotoxicity of the HAp/SF‐5% nanocomposite scaffolds. Subcutaneous implantation of the HAp/SF‐5% scaffolds in rat models suggested an excellent biocompatibility. All data obtained from this study suggest the potential use of the HAp/SF‐5% for hard tissue engineering.
Reversible covalent immobilization of Trametes villosa laccase onto thiolsulfinate‐agarose: An insoluble biocatalyst with potential for decoloring recalcitrant dyes
Authors: Gioia Larissa , Rodríguez‐Couto Susana , Menéndez María del Pilar , Manta Carmen , Ovsejevi Karen 
Published: September 2014

AbstractThe development of a solid‐phase biocatalyst based on the reversible covalent immobilization of laccase onto thiol‐reactive supports (thiolsulfinate‐agarose [TSI‐agarose]) was performed. To achieve this goal, laccase‐producing strains isolated from Eucalyptus globulus were screened and white rot fungus Trametes villosa was selected as the best strain for enzyme production. Reduction of disulfide bonds and introduction of “de novo” thiol groups in partially purified laccase were assessed to perform its reversible covalent immobilization onto thiol‐reactive supports (TSI‐agarose). Only the thiolation process dramatically improved the immobilization yield, from 0% for the native and reduced enzyme to 60% for the thiolated enzyme. Mild conditions for the immobilization process (pH 7.5 and 4°C) allowed the achievement of nearly 100% of coupling efficiency when low loads were applied. The kinetic parameters, pH, and thermal stabilities for the immobilized biocatalyst were similar to those for the native enzyme. After the first use and three consecutives reuses, the insoluble derivative kept more than 80% of its initial capacity for decolorizing Remazol Brilliant Blue R, showing its suitability for color removal from textile industrial effluents. The possibility of reusing the support was demonstrated by the reversibility of enzyme‐support binding.
Asymmetric Contribution of Aromatic Interactions Stems from Spatial Positioning of the Interacting Aryl Pairs in β‐Hairpins
Authors: Makwana Kamlesh Madhusudan , Mahalakshmi Radhakrishnan 
Published: September 2014

AbstractIsolated aromatic interactions in designed octapeptide β‐hairpin scaffolds display a near‐universal T‐shaped face‐to‐edge geometry in all positional permutations, with the exception of aryl‐Trp interactions. The heterogeneous asymmetric indole ring of Trp competes for a “shielding” face geometry, which lowers the scaffold stability in FtE aryl‐Trp pairs. Assessment of the contributions of aryl pairs (in the absence of solvent‐driven interactions) to the overall β‐hairpin structure reveals the superiority of Trp‐Phe and Trp‐Tyr contributions over the well‐established scaffold stabilization by Trp‐Trp.
Masked Rhodamine Dyes of Five Principal Colors Revealed by Photolysis of a 2‐Diazo‐1‐Indanone Caging Group: Synthesis, Photophysics, and Light Microscopy Applications
Authors: Belov Vladimir N. , Mitronova Gyuzel Yu. , Bossi Mariano L. , Boyarskiy Vadim P. , Hebisch Elke , Geisler Claudia , Kolmakov Kirill , Wurm Christian A. , Willig Katrin I. , Hell Stefan W. 
Published: September 2014

AbstractCaged rhodamine dyes (Rhodamines NN) of five basic colors were synthesized and used as “hidden” markers in subdiffractional and conventional light microscopy. These masked fluorophores with a 2‐diazo‐1‐indanone group can be irreversibly photoactivated, either by irradiation with UV‐ or violet light (one‐photon process), or by exposure to intense red light (λ∼750 nm; two‐photon mode). All dyes possess a very small 2‐diazoketone caging group incorporated into the 2‐diazo‐1‐indanone residue with a quaternary carbon atom (C‐3) and a spiro‐9H‐xanthene fragment. Initially they are non‐colored (pale yellow), non‐fluorescent, and absorb at λ=330–350 nm (molar extinction coefficient (ε)≈104 M−1 cm−1) with a band edge that extends to about λ=440 nm. The absorption and emission bands of the uncaged derivatives are tunable over a wide range (λ=511–633 and 525–653 nm, respectively). The unmasked dyes are highly colored and fluorescent (ε= 3–8×104 M−1 cm−1 and fluorescence quantum yields (ϕ)=40–85 % in the unbound state and in methanol). By stepwise and orthogonal protection of carboxylic and sulfonic acid groups a highly water‐soluble caged red‐emitting dye with two sulfonic acid residues was prepared. Rhodamines NN were decorated with amino‐reactive N‐hydroxysuccinimidyl ester groups, applied in aqueous buffers, easily conjugated with proteins, and readily photoactivated (uncaged) with λ=375–420 nm light or intense red light (λ=775 nm). Protein conjugates with optimal degrees of labeling (3–6) were prepared and uncaged with λ=405 nm light in aqueous buffer solutions (ϕ=20–38 %). The photochemical cleavage of the masking group generates only molecular nitrogen. Some 10–40 % of the non‐fluorescent (dark) byproducts are also formed. However, they have low absorbance and do not quench the fluorescence of the uncaged dyes. Photoactivation of the individual molecules of Rhodamines NN (e.g., due to reversible or irreversible transition to a “dark” non‐emitting state or photobleaching) provides multicolor images with subdiffractional optical resolution. The applicability of these novel caged fluorophores in super‐resolution optical microscopy is exemplified.
Essential Factors for Control of the Equilibrium in the Reversible Rearrangement of M3N@Ih‐C80 Fulleropyrrolidines: Exohedral Functional Groups versus Endohedral Metal Clusters
Authors: Aroua Safwan , Garcia‐Borràs Marc , Osuna Sílvia , Yamakoshi Yoko 
Published: September 2014

AbstractThe effects of exohedral moieties and endohedral metal clusters on the isomerization of M3N@Ih‐C80 products from the Prato reaction through [1,5]‐sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C80 was the single essential factor in determining the equilibrium between the [6,6]‐isomer (kinetic product) and the [5,6]‐isomer. In all the derivatives, the [6,6]‐ and [5,6]‐Prato adducts with larger metal clusters, such as Y3N and Gd3N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal‐cluster size. Further DFT calculations and 13C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]‐ and [5,6]‐fulleropyrrolidines.
Enhancement of Spin Relaxation in an FeDy2Fe Coordination Cluster by Magnetic Fields
Authors: Peng Guo , Mereacre Valeriu , Kostakis George E. , Wolny Juliusz A. , Schünemann Volker , Powell Annie K. 
Published: September 2014

AbstractTwo [FeLn2Fe(μ3‐OH)2(teg)2(N3)2(C6H5COO)4] compounds (where Ln=YIII and DyIII; teg=triethylene glycol anion) have been synthesized and studied using SQUID and Mössbauer spectroscopy. The magnetic measurements on both compounds indicate dominant antiferromagnetic interactions between the metal centers. Analysis of the 57Fe Mössbauer spectra complement the ac magnetic susceptibility measurements, which show how a static magnetic field can quench the slow relaxation of magnetization generated by the anisotropic DyIII ions.
Copper‐Catalyzed Aerobic Oxidations of 3‐N‐Hydoxyaminoprop‐1‐ynes to Form 3‐Substituted 3‐Amino‐2‐en‐1‐ones: Oxidative Mannich Reactions with a Skeletal Rearrangement
Authors: Kawade Rahul Kisan , Tseng Chang‐Chin , Liu Rai‐Shung 
Published: September 2014

AbstractCu‐catalyzed aerobic oxidations of readily available 3‐N‐hydroxyaminopro‐1‐ynes with water, alcohols, or thiols to form diverse 3‐substituted 3‐amino‐2‐en‐1‐ones are described. The utility of this catalysis is manifested by a wide scope of applicable N‐hydroxyl propargylamines and nucleophiles, thus enabling the design of one‐pot cascade or two‐step sequential reactions. Besides synthetic significances, such oxidative Mannich reactions are mechanistically interesting because structurally reorganized products were obtained. Our mechanistic studies reveal that the aerobic oxidations involve initial formation of nitrone intermediates, followed by the attack of nucleophiles. Herein, water and MeOH implement the conversion of nitrone intermediates to reaction products in two distinct pathways.