bluuebunny/crossref_metadata_2025_split huggingface dataset:
CH Bond Activation by f‐Block Complexes
Authors: Arnold Polly L. , McMullon Max W. , Rieb Julia , Kühn Fritz E. 
Published: November 2014

AbstractMost homogeneous catalysis relies on the design of metal complexes to trap and convert substrates or small molecules to value‐added products. Organometallic lanthanide compounds first gave a tantalizing glimpse of their potential for catalytic CH bond transformations with the selective cleavage of one CH bond in methane by bis(permethylcyclopentadienyl)lanthanide methyl [(η5‐C5Me5)2Ln(CH3)] complexes some 25 years ago. Since then, numerous metal complexes from across the periodic table have been shown to selectively activate hydrocarbon CH bonds, but the challenges of closing catalytic cycles still remain; many f‐block complexes show great potential in this important area of chemistry.
Chiroptical Detection of Nonchromophoric, Achiral Guests by Enantiopure Alleno‐Acetylenic Helicages
Authors: Gidron Ori , Ebert Marc‐Olivier , Trapp Nils , Diederich François 
Published: November 2014

AbstractEnantiopure alleno‐acetylenic ligands assemble diastereoselectively upon the addition of a zinc(II) salt to form triple‐stranded helicates, which provide a sufficiently large helical cage (“helicage”) for the encapsulation of guests. The inclusion complexation of heteroalicycles is confirmed by ROESY and DOSY NMR spectroscopy and quantified in 1H NMR binding titrations. The ECD spectra of the helicates, which showed strong Cotton effects and exciton coupling, were found to be extremely sensitive to the nature of the guest molecules. Consequently, a series of nonchromophoric, achiral guests of different sizes as well as regioisomers (1,3‐ and 1,4‐dioxane) became distinguishable on the basis of their induced CD (ICD) spectra. Molecular dynamics (MD) simulations show the adaptability of the cavity size to individual guest molecules and support the selective ICD output. Particularly high affinity towards 1,4‐dioxane allowed its selective detection at parts‐per‐million (ppm) levels in aqueous solutions.
Advancing the Electrochemistry of the Hydrogen‐Evolution Reaction through Combining Experiment and Theory
Authors: Zheng Yao , Jiao Yan , Jaroniec Mietek , Qiao Shi Zhang 
Published: November 2014

AbstractThe electrocatalytic hydrogen‐evolution reaction (HER), as the main step of water splitting and the cornerstone of exploring the mechanism of other multi‐electron transfer electrochemical processes, is the subject of extensive studies. A large number of high‐performance electrocatalysts have been developed for HER accompanied by recent significant advances in exploring its electrochemical nature. Herein we present a critical appraisal of both theoretical and experimental studies of HER electrocatalysts with special emphasis on the electronic structure, surface (electro)chemistry, and molecular design. It addresses the importance of correlating theoretical calculations and electrochemical measurements toward better understanding of HER electrocatalysis at the atomic level. Fundamental concepts in the computational quantum chemistry and its relation to experimental electrochemistry are also presented along with some featured examples.
An Anti CuO2‐type Metal Hydride Square Net Structure in Ln2M2As2Hx (Ln=La or Sm, M=Ti, V, Cr, or Mn)
Authors: Mizoguchi Hiroshi , Park SangWon , Hiraka Haruhiro , Ikeda Kazutaka , Otomo Toshiya , Hosono Hideo 
Published: November 2014

AbstractUsing a high pressure technique and the strong donating nature of H−, a new series of tetragonal La2Fe2Se2O3‐type layered mixed‐anion arsenides, Ln2M2As2Hx, was synthesized (Ln=La or Sm, M=Ti, V, Cr, or Mn; x≈3). In these compounds, an unusual M2H square net, which has anti CuO2 square net structures accompanying two As3− ions, is sandwiched by (LaH)2 fluorite layers. Notably, strong metal–metal bonding with a distance of 2.80 Å was confirmed in La2Ti2As2H2.3, which has metallic properties. In fact, these compounds are situated near the boundary between salt‐like ionic hydrides and transition‐metal hydrides with metallic characters.
Spatial Structuring of a Supramolecular Hydrogel by using a Visible‐Light Triggered Catalyst
Authors: Maity Chandan , Hendriksen Wouter E. , van Esch Jan H. , Eelkema Rienk 
Published: November 2014

AbstractSpatial control over the self‐assembly of synthetic molecular fibers through the use of light‐switchable catalysts can lead to the controlled formation of micropatterns made up of hydrogel structures. A photochromic switch, capable of reversibly releasing a proton upon irradiation, can act as a catalyst for in situ chemical bond formation between otherwise soluble building blocks, thereby leading to fiber formation and gelation in water. The use of a photoswitchable catalyst allows control over the distribution as well as the mechanical properties of the hydrogel material. By using homemade photomasks, spatially structured hydrogels were formed starting from bulk solutions of small molecule gelator precursors through light‐triggered local catalyst activation.
A Randomized, Double‐Blind, Placebo‐Controlled, Twelve‐Week, Dose‐Ranging Study of Decernotinib, an Oral Selective JAK‐3 Inhibitor, as Monotherapy in Patients With Active Rheumatoid Arthritis
Authors: Fleischmann Roy M. , Damjanov Nemanja S. , Kivitz Alan J. , Legedza Anna , Hoock Thomas , Kinnman Nils 
Published: November 2014

ObjectiveTo assess the efficacy and safety of oral decernotinib (VX‐509; Vertex Pharmaceuticals) monotherapy in a 12‐week, randomized, double‐blind, placebo‐controlled, dose‐ranging study of patients with rheumatoid arthritis (RA).MethodsTwo hundred four adults with active RA who had been unsuccessfully treated with ≥1 disease‐modifying antirheumatic drug were administered placebo tablets or decernotinib twice a day at dosages of 25 mg, 50 mg, 100 mg, or 150 mg. Primary measures of efficacy at week 12 were the response rate according to the American College of Rheumatology 20% improvement criteria (ACR20) and mean change from baseline in the Disease Activity Score in 28 joints using the C‐reactive protein level (DAS28‐CRP).ResultsAt week 12, the ACR20 response rates were 39.0%, 61.0%, 65.0%, and 65.9% in the 25‐mg, 50‐mg, 100‐mg, and 150‐mg groups, respectively, and were significantly higher in the 50‐mg group (P = 0.007) and the 100‐mg and 150‐mg groups (P = 0.002) as compared to the response rates in the placebo group (29.3%). The mean change from baseline in DAS28‐CRP was greater in the 50‐mg, 100‐mg, and 150‐mg groups as compared to the placebo group (P < 0.001). Decernotinib treatment resulted in higher ACR50 and ACR70 response rates, more patients with DAS28‐CRP scores <2.6, and improvements in the Health Assessment Questionnaire disability index as compared to placebo. The most common adverse events in any decernotinib group were nausea (6.1%), headache (4.3%), an increase in levels of alanine aminotransferase (4.3%), and hypercholesterolemia (3.7%). In the groups receiving decernotinib, there was an increased risk of infections and increased liver transaminase levels.ConclusionDecernotinib was efficacious in improving clinical signs and symptoms of RA at week 12 at dosages of 50–150 mg twice a day. Infections and increases in liver transaminase and lipid levels were noted as potential safety signals.
BAFF Regulates Follicular Helper T Cells and Affects Their Accumulation and Interferon‐γ Production in Autoimmunity
Authors: Coquery Christine M. , Loo William M. , Wade Nekeithia S. , Bederman Annelise G. , Tung Kenneth S. , Lewis Janet E. , Hess Henry , Erickson Loren D. 
Published: November 2014

ObjectiveFollicular helper T (Tfh) cells are critical for the development of protective antibodies via germinal center (GC) B cell responses; however, uncontrolled Tfh cell expansion activates autoreactive B cells to produce antibodies that cause autoimmunity. The mechanisms that control Tfh cell homeostasis remain largely unknown. The aim of this study was to determine the contribution of BAFF to Tfh cell responses in autoimmunity.MethodsWe analyzed the properties of Tfh cells in lupus‐prone mice sufficient or deficient in BCMA. Adoptive transfer studies and mixed bone marrow chimeras were used to test BCMA signaling in T cells. We assessed BAFF stimulation of Tfh cells through in vitro cell cocultures and in vivo depletion studies using flow cytometry.ResultsIn Nba2 mice, Tfh cells expressed the BAFF receptors BCMA and B lymphocyte stimulator receptor 3 (BR‐3) and accumulated in the spleen when BCMA was absent. BCMA deficiency in T cells promoted the expansion of Tfh cells, GC formation, autoantibody production, and interferon‐γ (IFNγ) production by Tfh cells through BR‐3. IFNγ‐producing Tfh cells increased BAFF expression in dendritic cells. Blocking BAFF or IFNγ in vivo reduced Tfh cell accumulation and reduced autoimmunity in BCMA‐deficient animals. Moreover, circulating Tfh‐like cells that expressed BR‐3 (but not BCMA) were elevated in patients with systemic lupus erythematosus, and this correlated with serum BAFF and IFNγ levels.ConclusionIn Nba2 mice, BCMA negatively regulates Tfh cell expansion, while BAFF signaling through BR‐3 promotes Tfh cell accumulation. Our findings suggest that the balance between BCMA and BR‐3 signaling in Tfh cells serves as a checkpoint of immune tolerance.
MicroRNA‐602 and MicroRNA‐608 Regulate Sonic Hedgehog Expression via Target Sites in the Coding Region in Human Chondrocytes
Authors: Akhtar Nahid , Makki Mohammad S. , Haqqi Tariq M. 
Published: November 2014

ObjectiveHedgehog (HH) signaling has recently been associated with cartilage degradation in osteoarthritis (OA). Because interleukin‐1β (IL‐1β) has been implicated as a principal instigator of OA, we sought to determine whether IL‐1β induces the expression of sonic HH (SHH) and its regulation by microRNAs (miRNAs) in human chondrocytes.MethodsExpression of SHH protein in human OA cartilage and in an animal model of OA was determined by immunohistochemical analysis and immunofluorescence analysis, respectively. Gene and protein expression in IL‐1β– or SHH‐stimulated OA chondrocytes was determined by TaqMan assays and Western blotting, respectively. The effect of overexpression of miRNA‐602 (miR‐602) and miR‐608 or their antagomirs on SHH expression was evaluated by transient transfection of human chondrocytes and HEK 293 cells. The role of signaling pathways was evaluated using small molecule inhibitors. Binding of miRNAs with the putative seed sequence in SHH messenger RNA (mRNA) was validated using a luciferase reporter assay.ResultsExpression of SHH, patched 1, Gli‐1, HH‐interacting protein, matrix metalloproteinase 13 (MMP‐13), and Colα1(X) was high in damaged OA cartilage. In damaged cartilage and in IL‐1β–stimulated OA chondrocytes, expression of SHH was inversely correlated with expression of miR‐608. Cotransfection of OA chondrocytes with miR‐608 or miR‐602 mimic inhibited reporter activity, and mutation of the miRNA seed sequences abolished the repression of reporter activity. Overexpression of miR‐602 or miR‐608 inhibited the expression of SHH mRNA and protein, and this was abrogated by antagomirs. Stimulation with recombinant human SHH protein up‐regulated MMP‐13 expression, and inhibition of HH signaling blocked MMP‐13 expression in OA chondrocytes.ConclusionMiR‐602 and miR‐608 are important posttranscription regulators of SHH expression in OA chondrocytes, and their suppression by IL‐1β may contribute to the enhanced expression of SHH and MMP‐13 in OA.
The Clinical Spectrum and Therapeutic Management of Hypocomplementemic Urticarial Vasculitis: Data From a French Nationwide Study of Fifty‐Seven Patients
Authors: Jachiet Marie , Flageul Béatrice , Deroux Alban , Le Quellec Alain , Maurier François , Cordoliani Florence , Godmer Pascal , Abasq Claire , Astudillo Leonardo , Belenotti Pauline , Bessis Didier , Bigot Adrien , Doutre Marie‐Sylvie , Ebbo Mikaël , Guichard Isabelle , Hachulla Eric , Héron Emmanuel , Jeudy Géraldine , Jourde‐Chiche Noémie , Jullien Denis , Lavigne Christian , Machet Laurent , Macher Marie‐Alice , Martel Clotilde , Melboucy‐Belkhir Sara , Morice Cécile , Petit Antoine , Simorre Bernard , Zenone Thierry , Bouillet Laurence , Bagot Martine , Frémeaux‐Bacchi Véronique , Guillevin Loïc , Mouthon Luc , Dupin Nicolas , Aractingi Selim , Terrier Benjamin ,   for the French Vasculitis Study Group
Published: November 2014

ObjectiveHypocomplementemic urticarial vasculitis (HUV) is an uncommon vasculitis of unknown etiology that is rarely described in the literature. We undertook this study to analyze the clinical spectrum and the therapeutic management of patients with HUV.MethodsWe conducted a French nationwide retrospective study that included 57 patients with chronic urticaria, histologic leukocytoclastic vasculitis, and hypocomplementemia. We assessed clinical and laboratory data and evaluated the patients' cutaneous and immunologic responses to therapy. We evaluated treatment efficacy by measuring the time to treatment failure.ResultsUrticarial lesions were typically more pruritic than painful and were associated with angioedema in 51% of patients, purpura in 35%, and livedo reticularis in 14%. Extracutaneous manifestations included constitutional symptoms (in 56% of patients) as well as musculoskeletal involvement (in 82%), ocular involvement (in 56%), pulmonary involvement (in 19%), gastrointestinal involvement (in 18%), and kidney involvement (in 14%). Patients with HUV typically presented with low C1q levels and normal C1 inhibitor levels, in association with anti‐C1q antibodies in 55% of patients. Hydroxychloroquine or colchicine seemed to be as effective as corticosteroids as first‐line therapy. In patients with relapsing and/or refractory disease, rates of cutaneous and immunologic response to therapy seemed to be higher with conventional immunosuppressive agents, in particular, azathioprine, mycophenolate mofetil, or cyclophosphamide, while a rituximab‐based regimen tended to have higher efficacy. Finally, a cutaneous response to therapy was strongly associated with an immunologic response to therapy.ConclusionHUV represents an uncommon systemic and relapsing vasculitis with various manifestations, mainly, musculoskeletal and ocular involvement associated with anti‐C1q antibodies, which were found in approximately half of the patients. The best strategy for treating HUV has yet to be defined.
Analysis of the Trajectory of Osteoarthritis Development in a Mouse Model by Serial Near‐Infrared Fluorescence Imaging of Matrix Metalloproteinase Activities
Authors: Leahy Averi A. , Esfahani Shadi A. , Foote Andrea T. , Hui Carrie K. , Rainbow Roshni S. , Nakamura Daisy S. , Tracey Brian H. , Mahmood Umar , Zeng Li 
Published: November 2014

ObjectiveA major hurdle in osteoarthritis (OA) research is the lack of sensitive detection and monitoring methods. It is hypothesized that proteases, such as matrix metalloproteinases (MMPs), are up‐regulated in the early stages of OA development. This study was undertaken to investigate if a near‐infrared (NIR) fluorescent probe activated by MMPs could visualize in vivo OA progression beginning in the early stages of the disease.MethodsUsing an MMP‐activatable NIR fluorescent probe (MMPSense 680), we assessed the up‐regulation of MMP activity in vitro by incubating human chondrocytes with the proinflammatory cytokine interleukin‐1β (IL‐1β). MMP activity was then evaluated in vivo serially in a mouse model of chronic, injury‐induced OA. To track MMP activity over time, mice were imaged 1–8 weeks after OA‐inducing surgery. Imaging results were correlated with histologic findings.ResultsIn vitro studies confirmed that NIR fluorescence imaging identified enhanced MMP activity in IL‐1β–treated human chondrocytes. In vivo imaging showed significantly higher fluorescence intensity in OA knees compared to sham‐operated (control) knees of the same mice. Additionally, the total emitted fluorescence intensity steadily increased over the entire course of OA progression that was examined. NIR fluorescence imaging results correlated with histologic findings, which showed an increase in articular cartilage structural damage over time.ConclusionImaging of MMP activity in a mouse model of OA provides sensitive and consistent visualization of OA progression, beginning in the early stages of OA. In addition to facilitating the preclinical study of OA modulators, this approach has the potential for future translation to humans.
Distributed Multi‐Robot Evacuation Incorporating Human Behavior
Authors: Zhang Shubo , Guo Yi 
Published: November 2014

AbstractIt is well known that trained leaders have an important influence on saving human lives in emergency evacuation. In this paper, we present a novel distributed multi‐robot system for guiding people in an emergency evacuation mission. A cooperative exit‐seeking algorithm is designed for the robots to guide evacuees by online estimating the gradient and tracing gradient‐descent while maintaining a predefined formation in movement. To better deal with evacuees' behaviors in emergency situations, two human panic behavior models are taken into account in the evacuation strategies. Guidance algorithms of single robot team and multi‐team are introduced in the evacuation system. We evaluate the proposed method through comparing evacuation time with non‐robot‐assisted procedures in the static and dynamic routing simulations. The results show that our method can significantly shorten the evacuation time.
Methods of biological fluids sample preparation – biogenic amines, methylxanthines, water‐soluble vitamins
Authors: Płonka Joanna 
Published: November 2014

AbstractIn recent years demands on the amount of information that can be obtained from the analysis of a single sample have increased. For time and economic reasons it is necessary to examine at the same time larger number of compounds, and compounds from different groups. This can best be seen in such areas as clinical analysis. In many diseases, the best results for patients are obtained when treatment fits the individual characteristics of the patient. Dosage monitoring is important at the beginning of therapy and in the full process of treatment. In the treatment of many diseases biogenic amines (dopamine, serotonin) and methylxanthines (theophylline, theobromine, caffeine) play an important role. They are used as drugs separately or in combination with others to support and strengthen the action of other drugs – for example, the combination of caffeine and paracetamol. Vitamin supplementation may be also an integral part of the treatment process. Specification of complete sample preparation parameters for extraction of the above compounds from biological matrices has been reviewed. Particular attention was given to the preparation stage and extraction methods. This review provides universal guidance on establishing a common procedures across laboratories to facilitate the preparation and analysis of all discussed compounds. Copyright © 2014 John Wiley & Sons, Ltd.
Centrifugal Separation with Emphasis on the Rotational Particle Separator
Authors: van Kemenade Erik , Brouwers Bert , van Benthum Rob 
Published: November 2014

AbstractA review is given of separation methods based on centrifugation. Attention is focused on separation of mixtures of gases and droplets. More particularly we consider: the method of gas centrifuges or ultra‐centrifuges to separate gases of different molecular weight, and centrifugal separators to separate droplets from gases. Elementary physical principles are used to formulate basic equations. From here on, rules are derived for separation performance, energy consumption and size of the installations. Status of technology of each of the methods is illustrated by presenting actual cases of application.
Oxidative Coupling of Alcohols and Amines over Bimetallic Unsupported Nanoporous Gold: Tailored Activity through Mechanistic Predictability
Authors: Wichmann Andre , Bäumer Marcus , Wittstock Arne 
Published: November 2014

AbstractAn unsupported nanoporous gold catalyst is employed for the direct coupling of primary alcohols and amines to the corresponding amides in the liquid phase. Among others, the reaction of methanol and dimethylamine to the industrially relevant dimethylformamide proceeds smoothly at 40 °C (turnover frequency≈40 h−1). The activation of molecular oxygen is identified as a key parameter. Doping of the unsupported catalyst by an admetal (Ru, Ag) is used to increase the activity of the catalyst considerably for this reaction (turnover frequency≈100 h−1).
Knowledge of the harms of tobacco use among patients with bladder cancer
Authors: Bassett Jeffrey C. , Gore John L. , Kwan Lorna , Ritch Chad R. , Barocas Daniel A. , Penson David F. , McCarthy William J. , Saigal Christopher S. 
Published: November 2014

BACKGROUNDThe objective of this study was to determine tobacco use knowledge and attribution of cause in patients with newly diagnosed bladder cancer.METHODSA stratified, random sample of bladder cancer survivors diagnosed between 2006 and 2009 was obtained from the California Cancer Registry. Respondents were surveyed about tobacco use, risk factors, and sources of information on the causes of bladder cancer. Contingency tables and logistic regression analyses were used to evaluate tobacco use knowledge and beliefs.RESULTSOf 1198 eligible participants, 790 (66%) completed the survey. Sixty‐eight percent of the cohort had a history of tobacco use, and 19% were active smokers at diagnosis. Tobacco use was the most cited risk factor for bladder cancer, with active smokers more knowledgeable than former smokers or never smokers (90% vs 64% vs 61%, respectively; P<.001). Urologists were the predominant source of information and were cited most often by active smokers (82%). In multivariate analyses, active smokers had 6.37 times greater odds (95% confidence interval, 3.35‐12.09) than never smokers of endorsing tobacco use as a risk factor for bladder cancer, and smokers who named the urologist as their information source had 2.80 times greater odds (95% confidence interval, 1.77‐4.43) of believing tobacco use caused their cancer.CONCLUSIONSPatients' smoking status and primary source of information were associated with knowledge of the harms of tobacco use and, in smokers, acknowledgment that tobacco use increased the risk of their own disease. Urologists play a critical role in ensuring patients' knowledge of the connection between smoking and bladder cancer, particularly for active smokers who may be motivated to quit. Cancer 2014;120:3914–3922. © 2014 American Cancer Society.