bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Air‐ and Water‐Tolerant Zinc Hydride Cluster That Reacts Selectively With CO2
Authors: Ermert David M. , Ghiviriga Ion , Catalano Vincent J. , Shearer Jason , Murray Leslie J. 
Published: April 2015

AbstractThe reaction of [Zn3Cl3L], in which L3− is a tris(β‐diketiminate) cyclophane, with K(sBu)3BH afforded [Zn3(μ‐H)3L] (2), as confirmed by NMR spectroscopy, NOESY, and X‐ray crystallography. The complex 2 was air‐stable and unreactive towards water, methanol, and other substrates (e.g., nitriles) at room temperature over 24 h but reacted with CO2 (ca. 1 atm) to generate [Zn3(μ‐H)2(μ‐1,1‐O2CH)] (3). In contrast, [Zn3(OH)3L] (4) was found to be unreactive toward CO2 over the course of several days at 90 °C.
Trifluoromethylthiolation of Aryl Iodides and Bromides Enabled by a Bench‐Stable and Easy‐To‐Recover Dinuclear Palladium(I) Catalyst
Authors: Yin Guoyin , Kalvet Indrek , Schoenebeck Franziska 
Published: April 2015

AbstractWhile palladium catalysis is ubiquitous in modern chemical research, the recovery of the active transition‐metal complex under routine laboratory applications is frequently challenging. Described herein is the concept of alternative cross‐coupling cycles with a more robust (air‐, moisture‐, and thermally‐stable) dinuclear PdI complex, thus avoiding the handling of sensitive Pd0 species or ligands. Highly efficient CSCF3 coupling of a range of aryl iodides and bromides was achieved, and the recovery of the PdI complex was accomplished via simple open‐atmosphere column chromatography. Kinetic and computational data support the feasibility of dinuclear PdI catalysis. A novel SCF3‐bridged PdI dimer was isolated, characterized by X‐ray crystallography, and verified to be a competent catalytic intermediate.
Enzymatic Chemoselective Aldehyde–Ketone Cross‐Couplings through the Polarity Reversal of Methylacetoin
Authors: Bernacchia Giovanni , Bortolini Olga , De Bastiani Morena , Lerin Lindomar Alberto , Loschonsky Sabrina , Massi Alessandro , Müller Michael , Giovannini Pier Paolo 
Published: April 2015

AbstractThe thiamine diphosphate (ThDP) dependent enzyme acetoin:dichlorophenolindophenol oxidoreductase (Ao:DCPIP OR) from Bacillus licheniformis was cloned and overexpressed in Escherichia coli. The recombinant enzyme shared close similarities with the acetylacetoin synthase (AAS) partially purified from Bacillus licheniformis suggesting that they could be the same enzyme. The product scope of the recombinant Ao:DCPIP OR was expanded to chiral tertiary α‐hydroxy ketones through the rare aldehyde–ketone cross‐carboligation reaction. Unprecedented is the use of methylacetoin as the acetyl anion donor in combination with a range of strongly to weakly activated ketones. In some cases, Ao:DCPIP OR produced the desired tertiary alcohols with stereochemistry opposite to that obtained with other ThDP‐dependent enzymes. The combination of methylacetoin as acyl anion synthon and novel ThDP‐dependent enzymes considerably expands the available range of CC bond formations in asymmetric synthesis.
Benzene‐Fused Azacorannulene Bearing an Internal Nitrogen Atom
Authors: Ito Shingo , Tokimaru Yuki , Nozaki Kyoko 
Published: April 2015

AbstractA novel nitrogen‐doped corannulene derivative, 8‐tert‐butyl‐6b2‐azapentabenzo[bc,ef,hi,kl,no]corannulene, was synthesized by 1,3‐dipolar cycloaddition of a polycyclic aromatic azomethine ylide with a diarylethyne and subsequent palladium‐catalyzed intramolecular cyclization. This molecule represents the first example of a corannulene derivative bearing an internal heteroatom, and exhibits unique structural and physical properties caused by the introduction of the nitrogen atom and extended π‐conjugation, as compared to the parent corannulene.
Multiformat T‐Cell‐Engaging Bispecific Antibodies Targeting Human Breast Cancers
Authors: Cao Yu , Axup Jun Y. , Ma Jennifer S. Y. , Wang Rongsheng E. , Choi Seihyun , Tardif Virginie , Lim Reyna K. V. , Pugh Holly M. , Lawson Brian R. , Welzel Gus , Kazane Stephanie A. , Sun Ying , Tian Feng , Srinagesh Shailaja , Javahishvili Tsotne , Schultz Peter G. , Kim Chan Hyuk 
Published: April 2015

AbstractFour different formats of bispecific antibodies (bsAbs) were generated that consist of anti‐Her2 IgG or Fab site‐specifically conjugated to anti‐CD3 Fab using the genetically encoded noncanonical amino acid. These bsAbs varied in valency or in the presence or absence of an Fc domain. Different valencies did not significantly affect antitumor efficacy, whereas the presence of an Fc domain enhanced cytotoxic activity, but triggered antigen‐independent T‐cell activation. We show that the bsAbs can efficiently redirect T cells to kill all Her2 expressing cancer cells, including Her2 1+ cancers, both in vitro and in rodent xenograft models. This work increases our understanding of the structural features that affect bsAb activity, and underscores the potential of bsAbs as a promising therapeutic option for breast cancer patients with low or heterogeneous Her2 expression.
The Synthesis and Biological Evaluation of Desepoxyisotedanolide and a Comparison with Desepoxytedanolide
Authors: Naini Arun , Muthukumar Yazh , Raja Aruna , Franke Raimo , Harrier Ian , Smith Amos B. , Lee Dongjoo , Taylor Richard E. , Sasse Florenz , Kalesse Markus 
Published: April 2015

AbstractThe tedanolides are biologically active polyketides that exhibit a macrolactone constructed from a primary alcohol. Since polyketidal transformations only generate secondary alcohols, it has been hypothesized by Taylor that this unique lactone could arise from a postketidal transesterification. In order to probe this hypothesis and to investigate the biological profile of the putative precursor of all members of the tedanolide family, we embarked on the synthesis of desepoxyisotedanolide and its biological evaluation in comparison to desepoxytedanolide. The biological experiments unraveled a second target for desepoxytedanolide and provided evidence that the proposed transesterification indeed provides a survival advantage for the producing microorganism.
Potential‐Dependent Adlayer Structure and Dynamics at the Ionic Liquid/Au(111) Interface: A Molecular‐Scale In Situ Video‐STM Study
Authors: Wen Rui , Rahn Björn , Magnussen Olaf M. 
Published: April 2015

AbstractRoom‐temperature ionic liquids are of great current interest for electrochemical applications in material and energy science. Essential for understanding the electrochemical reactivity of these systems are detailed data on the structure and dynamics of the interfaces between these compounds and metal electrodes, which distinctly differ from those in traditional electrolytes. In situ studies are presented of Au(111) electrodes in 1‐butyl‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([BMP][TFSA]) by high‐speed scanning tunneling microscopy (video‐STM). [BMP][TFSA] is one of the best‐understood air and water stable ionic liquids. The measurements provide direct insights into the potential‐dependent molecular arrangement and surface dynamics of adsorbed [BMP]+ cations in the innermost layer on the negatively charged Au electrode surface. In particular, two distinct subsequent transitions in the adlayer structure and lateral mobility are observed with decreasing potential.
Effects of surfactants on rheological properties of a dispersed viscoelastic microsphere
Authors: Yang Hongbin , Kang Wanli , Yu Yang , Lu Yao , Li Zhe , Wang Manying , Liu Tongjing 
Published: April 2015

ABSTRACTThe swelling ratio is an important performance for the application of viscoelastic microsphere. The reduction of swelling ratio can affect the particle size. The compatibility between particle size and formation pore can affect the plugging performance and EOR capability. Adsorption characteristics of cationic surfactant cetyltriethylammnonium bromide (CTAB), anionic surfactant petroleum sulfonate applied in GangXi oilfield (GXPS), and nonionic surfactant nonylphenol ether (TX‐10) onto viscoelastic microspheres and the effect of the three types of surfactant on swelling ratio of viscoelastic microspheres were investigated. Effects of surfactants on rheological properties of viscoelastic microspheres were researched in two different modes referring to steady shear and dynamic shear, respectively, using Physica MCR301 Rheometer. The results showed that the interactions between viscoelastic microsphere and surfactants CTAB were electrostatic attraction and hydrophobic association, that the interaction between viscoelastic microsphere and surfactants TX‐10 was just hydrophobic association, and that the interactions between viscoelastic microsphere and GXPS were electrostatic repulsion and hydrophobic association. At the same initial surfactant concentration, all these three types of surfactant could be adsorbed onto the surface of viscoelastic microspheres and reduce its swelling ratio and storage modulus. Because of different amount of adsorption, the extent of reduction order on swelling ratio and storage modulus was CTAB>TX‐10>GXPS. In addition, the yield stress of viscoelastic microspheres which was obtained from modeling the data to Herschel‐Bulkley model decreases with the increase of surfactant adsorption. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42278.
Synthesis of polyhydric alcohol/ethanol phosphate flame retardant and its application in PU rigid foams
Authors: Xu Wei , Wang Guojian 
Published: April 2015

ABSTRACTTwo types of polyhydric alcohol/ethanol phosphates (PAEPs) were synthesized by a two‐step reaction using phosphorus oxychloride, ethanol, and polyhydric alcohol (glycerol and pentaerythritol). First, phosphorus oxychloride was reacted with ethanol to form a mixture of diethyl chlorophosphate and tri‐ethyl phosphate, and then PAEPs were prepared by the reaction between the above mixture and polyhydric alcohol. The chemical structures of PAEPs were characterized by 1H NMR, and the elemental compositions were analyzed by X‐ray photoelectron spectroscopy (XPS). The degradation behavior of the PAEPs and their solubility in polyols were studied. The results indicated the PAEPs could be well dissolved in polyols. When PAEPs were used as flame retardant for PU rigid foams at a content of 8 wt %, the char residue of polyurethane foam at 800°C increased from 17.2 to 28% in average, and the peak heat release rate (pHRR) of polyurethane foam decreased significantly from 207 to 133 kW/m2. In addition, PURF with PAEPs showed remarkable intumescent property. The results indicated that PAEPs were effective condensed phase flame retardant with char catalytic and intumescent property. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42298.
Brief Report: Leucine‐Rich α2‐Glycoprotein as a Potential Biomarker for Joint Inflammation During Anti–Interleukin‐6 Biologic Therapy in Rheumatoid Arthritis
Authors: Fujimoto Minoru , Serada Satoshi , Suzuki Katsuya , Nishikawa Ayumi , Ogata Atsushi , Nanki Toshihiro , Hattori Kunihiro , Kohsaka Hitoshi , Miyasaka Nobuyuki , Takeuchi Tsutomu , Naka Tetsuji 
Published: April 2015

ObjectiveTo investigate whether leucine‐rich α2‐glycoprotein (LRG) could be a biomarker for disease activity during interleukin‐6 (IL‐6) blockade treatment of rheumatoid arthritis (RA).MethodsIn 59 RA patients who were treated with tocilizumab for 24 weeks, serum LRG levels were determined by enzyme‐linked immunosorbent assay. RA disease activity was evaluated by the Clinical Disease Activity Index (CDAI). Receiver operating characteristic (ROC) curve analysis was used to examine the diagnostic performance of LRG and other biomarkers. In monkeys with experimental autoimmune arthritis, swollen joint counts, joint pathologic changes, and blood levels of C‐reactive protein (CRP) and LRG were evaluated after treatment with anti–IL‐6 receptor antibody.ResultsAmong tocilizumab‐treated RA patients, those with active disease (CDAI >2.8) had significantly higher serum LRG levels compared to those whose disease was in remission. ROC curve analysis suggested that the LRG level was more useful than the CRP or matrix metalloproteinase 3 level or the erythrocyte sedimentation rate in discriminating between remission and active disease during therapy with tocilizumab. In monkeys treated with IL‐6 blockade, joint scores were more closely correlated with LRG levels than with CRP levels. Histologic analysis of joints revealed that LRG levels correlated significantly with granulomatous tissue formation, cartilage degeneration, and bone destruction in IL‐6 blockade–treated monkeys with low levels of CRP.ConclusionUnder conditions of IL‐6 inhibition, LRG was more useful than other biomarkers in discriminating between active and inactive disease in human RA and in detecting joint inflammation in experimental arthritis. LRG may serve as a convenient biomarker for RA disease activity during IL‐6 blockade treatment.
Association Between Lipid Levels and Major Adverse Cardiovascular Events in Rheumatoid Arthritis Compared to Non–Rheumatoid Arthritis Patients
Authors: Liao Katherine P. , Liu Jun , Lu Bing , Solomon Daniel H. , Kim Seoyoung C. 
Published: April 2015

ObjectiveLower levels of low‐density lipoprotein (LDL) cholesterol may be associated with increased cardiovascular (CV) risk in rheumatoid arthritis (RA). This study was undertaken to determine whether the complex relationship between levels of LDL and high‐density lipoprotein (HDL) cholesterol and CV risk is different in RA patients as compared to non‐RA controls.MethodsUsing data from a US health insurance plan (2003–2012), we conducted a cohort study that included patients with RA and non‐RA control subjects matched with regard to age, sex, and index date. The nonlinearity of associations between lipid levels and incidence of major adverse CV events (MACE) was tested. We used multivariable Cox proportional hazards regression models to examine for an interaction between lipid levels and RA status in relation to the risk of MACE, after adjustment for CV risk factors.ResultsIn total, 16,085 RA patients and 48,499 non‐RA controls were studied. The mean age was 52.6 years and 78.6% were women. The relationship between LDL cholesterol levels and incidence of MACE was nonlinear and similar between RA patients and non‐RA controls (P for interaction = 0.72). No significant increase in CV risk was observed between the lowest quintile of LDL cholesterol levels (≤91.0 mg/dl) and the second, third, or fourth quintiles, whereas the highest quintile (>190.0 mg/dl) conveyed a 40% increase in risk of MACE (hazard ratio [HR] 1.40, 95% confidence interval [95% CI] 1.17–1.68). The relationship between HDL cholesterol levels and incidence of MACE was also nonlinear and similar between RA patients and non‐RA controls (P for interaction = 0.39). Compared to the lowest quintile of HDL cholesterol levels, each successive quintile was associated with a reduced risk of MACE (HR 0.45, 95% CI 0.48–0.72 for lowest quintile [≤43.0 mg/dl] versus highest quintile [>71.0 mg/dl]).ConclusionThe complex relationship between LDL cholesterol levels, HDL cholesterol levels, and risk of MACE was nonlinear in RA patients and also not statistically significantly different from that in an age‐ and sex‐matched non‐RA cohort.
Internalization of Rituximab and the Efficiency of B Cell Depletion in Rheumatoid Arthritis and Systemic Lupus Erythematosus
Authors: Reddy Venkat , Cambridge Geraldine , Isenberg David A. , Glennie Martin J. , Cragg Mark S. , Leandro Maria 
Published: April 2015

ObjectiveRituximab, a type I anti‐CD20 monoclonal antibody (mAb), induces incomplete B cell depletion in some patients with rheumatoid arthritis (RA) and systemic lupus erythematosus (SLE), thus contributing to a poor clinical response. The mechanisms of this resistance remain elusive. The purpose of this study was to determine whether type II mAb are more efficient than type I mAb at depleting B cells from RA and SLE patients, whether internalization influences the efficiency of depletion, and whether Fcγ receptor type IIb (FcγRIIb) and the B cell receptor regulate this internalization process.MethodsWe used an in vitro whole blood B cell–depletion assay to assess the efficiency of depletion, flow cytometry to study cell surface protein expression, and surface fluorescence–quenching assays to assess rituximab internalization, in samples from patients with RA and patients with SLE. Paired t‐test or Mann‐Whitney U test was used to compare groups, and Spearman's rank correlation test was used to assess correlation.ResultsWe found that type II mAb internalized significantly less rituximab than type I mAb and depleted B cells from patients with RA and SLE at least 2‐fold more efficiently than type I mAb. Internalization of rituximab was highly variable between patients, was regulated by FcγRIIb, and inversely correlated with cytotoxicity in whole blood B cell–depletion assays. The lowest levels of internalization were seen in IgD– B cells, including postswitched (IgD–CD27+) memory cells. Internalization of type I anti‐CD20 mAb was also partially inhibited by anti‐IgM stimulation.ConclusionVariability in internalization of rituximab was observed and was correlated with impaired B cell depletion. Therefore, slower‐internalizing type II mAb should be considered as alternative B cell–depleting agents for the treatment of RA and SLE.
Associations With Smoking and Shared Epitope Differ Between IgA‐ and IgG‐Class Antibodies to Cyclic Citrullinated Peptides in Early Rheumatoid Arthritis
Authors: Svärd Anna , Skogh Thomas , Alfredsson Lars , Ilar Anna , Klareskog Lars , Bengtsson Camilla , Kastbom Alf 
Published: April 2015

ObjectiveSmoking and HLA–DRB1/shared epitope (SE) alleles are risk factors for rheumatoid arthritis (RA) characterized by seropositivity for antibodies targeting citrullinated proteins (ACPAs)/cyclic citrullinated peptides (anti‐CCP). Previously, mainly IgG‐class antibodies have been studied. IgA‐class antibodies are to a great extent related to mucosal immunity. The aim of this study was to explore interrelations between cigarette smoking, presence of SE, and seropositivity for circulating IgA and/or IgG anti‐CCP antibodies among patients with early RA, to determine whether ACPAs of the IgA subclass are regulated by different mechanisms than those of the IgG subclass.MethodsTwo cohorts of patients with early RA, from the first Epidemiological Investigations of RA trial (n = 1,663) and the second Early Intervention in RA trial (n = 199), were grouped into 4 subsets based on anti‐CCP subclass status (IgG−/IgA−, IgG−/IgA+, IgG+/IgA−, and IgG+/IgA+), and each subset was compared with regard to associations with smoking (current and former) and presence of SE. Interaction between smoking and SE was calculated using the attributable proportion (AP) due to interaction (assessing deviation from additivity of effects).ResultsSmoking was overrepresented among IgA anti‐CCP–positive RA patients, regardless of whether IgG anti‐CCP were present, whereas in patients with IgG anti‐CCP alone, no association with smoking was found. SE alleles were overrepresented among IgG anti‐CCP–positive patients, regardless of IgA anti‐CCP status, and was not seen in patients with IgA anti‐CCP alone. An interaction between ever smoking and SE was found with regard to the risk of IgG+/IgA+ RA (AP 0.5, 95% confidence interval 0.4, 0.6). No significant interaction was observed with regard to the risk of IgG−/IgA+ RA or IgG+/IgA− RA.ConclusionIn patients with RA, a history of ever smoking was associated with seropositivity for IgA anti‐CCP antibodies, whereas presence of SE was associated with seropositivity for IgG anti‐CCP antibodies. An interaction between ever smoking and the SE was limited to the RA subset characterized by seropositivity for both IgG and IgA anti‐CCP. These findings provide novel evidence that anti‐CCP–positive RA can be divided into at least 3 serologically distinct subsets associated with different risk factors, indicating different modes of pathogenesis in RA.
Using finite element method based software to teach electrical machines—The linear switched reluctance actuator
Authors: Calado M. R. A. , Espírito‐Santo A. E. V. , Salvado J. A. C. , Cabrita C. M. P. , Mariano S. J. P. S. 
Published: April 2015

ABSTRACTIn this paper, the authors intend to propose a method to teach Electrical Machines in Electrical Engineering courses. The way that both in textbooks and classrooms treat this subject seems to limit students' understanding. The competences on electrical machines design and analysis are improved by a practical approach based on simulation and numerical analysis using Finite Element Method Software. As a complement to the previous teaching method, the students use an experimental test bench to verify the numerical results. A particular topic, concerning the study of the Linear Switched Reluctance Actuators, is here presented. Therefore, we propose a guideline for use in the classroom. © 2015 Wiley Periodicals, Inc. Comput Appl Eng Educ 23:824–836, 2015; View this article online at wileyonlinelibrary.com/journal/cae; DOI 10.1002/cae.21653
Clinical implications of hypoxia biomarker expression in head and neck squamous cell carcinoma: a systematic review
Authors: Swartz Justin E. , Pothen Ajit J. , Stegeman Inge , Willems Stefan M. , Grolman Wilko 
Published: April 2015

AbstractAwareness increases that the tumor biology influences treatment outcome and prognosis in cancer. Tumor hypoxia is thought to decrease sensitivity to radiotherapy and some forms of chemotherapy. Presence of hypoxia may be assessed by investigating expression of endogenous markers of hypoxia (EMH) using immunohistochemistry (IHC). In this systematic review we investigated the effect of EMH expression on local control and survival according to treatment modality in head and neck cancer (head and neck squamous cell carcinoma [HNSCC]). A search was performed in MEDLINE and EMBASE. Studies were eligible for inclusion that described EMH expression in relation to outcome in HNSCC patients. Quality was assessed using the Quality in Prognosis Studies (QUIPS) tool. Hazard ratios for locoregional control and survival were extracted. Forty studies of adequate quality were included. HIF‐1a, HIF‐2a, CA‐IX, GLUT‐1, and OPN were identified as the best described EMHs. With exception of HIF‐2a, all EMHs were significantly related to adverse outcome in multiple studies, especially in studies where patients underwent single‐modality treatment. Positive expression was often correlated with adverse clinical characteristics, including disease stage and differentiation grade. In summary, EMH expression was common in HNSCC patients and negatively influenced their prognosis. Future studies should investigate the effect of hypoxia‐modified treatment schedules in patients with high In summary, EMH expression. These may include ARCON, treatment with nimorazole, or novel targeted therapies directed at hypoxic tissue. Also, the feasibility of surgical removal of the hypoxic tumor volume prior to radiotherapy should be investigated.