bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Introduction to the Consequences of Spin and Bond Strength in the Chemistry of Diatomic Oxygen, Peroxides, and Related Species
Authors: Greer Alexander , Balaban Alexandru T. , Liebman Joel F. 
Published: December 2014

AbstractThis review chapter discusses oxygen and peroxides in organic chemistry. Numerous types of oxygen species are described including ions, radicals, biradicals, and zwitterionic species; examples of such species are superoxide anion (O2⋅−), dioxygenyl cation (O2⋅+), ozone (O3), oxygen oligomers (Ox), and the lowest excited singlet state of oxygen (1Δ). An analysis of acyclic peroxides and cyclic peroxides (e.g., 1,2‐dioxetanes,1,2,3‐trioxolanes, and 1,4‐endoperoxides) is provided. Isoelectronic heteroatom structures and other analogs are also provided to help guide thinking for the factors that underlie the stability of peroxide and other oxygen‐containing species.
Palladium‐Catalyzed Alkoxy‐ and Aminocarbonylation of α‐Halomethyl Oxime Ethers: Synthesis of 1,3‐Alkoxyimino Esters and 1,3‐Alkoxyimino Amides
Authors: Noverges Bárbara , Medio‐Simón Mercedes , Asensio Gregorio 
Published: December 2014

Abstractα‐Halomethyl oxime ethers react in palladium‐catalyzed three‐component reactions with alcohols or amines and carbon monoxide (CO) at atmospheric pressure to afford efficiently novel β‐oxyimino esters or β‐oxyimino amides, respectively. The reactions proceed with total regiocontrol, excellent yield, and high atomic economy regarding the reagents from simple commercially available starting materials using 10 mol% palladium(II) acetate [Pd(OAc)2]/7 mol% Xantphos as catalyst. Direct nucleophilic substitution at the very reactive α‐halomethyl moiety was noticeable only in the preparation of β‐oxyimino amides derived from alkylamines. In this case, β‐oxyimino amides are obtained alternatively by a one‐pot two step alkoxycarbonylation/ester aminolysis process. Site selective alkoxy‐ and aminocarbonylation reactions of bromoaryl‐substituted α‐halomethyl oxime ethers at the Csp3Br bond are described.magnified image
Synthesis of 3‐Aryl‐1‐trifluoromethyltetrahydroisoquinolines by Brønsted Acid‐Catalyzed C(sp3)H Bond Functionalization
Authors: Mori Keiji , Umehara Nobuaki , Akiyama Takahiko 
Published: December 2014

AbstractA concise route to 3‐aryl‐1‐trifluoromethyltetrahydroisoquinolines by a benzylic [1,5]‐hydride shift‐mediated CH bond functionalization was developed. The [1,5]‐hydride shift of the benzylic C(sp3)H bond to the trifluoromethylketimine derived from para‐anisidine occurred smoothly to produce cis‐1‐trifluoromethyl‐3‐aryltetrahydroisoquinolines in good to excellent chemical yields with good diastereoselectivities. In contrast, use of the NH ketimine furnished N‐unprotected tetrahydroisoquinolines in good yields in favor of the trans‐isomer.magnified image
Copper(II)‐Catalyzed Single‐Step Synthesis of Aryl Thiols from Aryl Halides and 1,2‐Ethanedithiol
Authors: Liu Yajun , Kim Jihye , Seo Heesun , Park Sunghyouk , Chae Junghyun 
Published: December 2014

AbstractA highly efficient transition metal‐catalyzed single‐step synthesis of aryl thiols from aryl halides has been developed employing copper(II) catalyst and 1,2‐ethanedithiol. The key features are use of readily available reagents, a simple operation, and relatively mild reaction conditions. This new protocol shows a broad substrate scope with excellent functional group compatibility. A variety of aryl thiols are directly prepared from aryl halides in high yields. Furthermore, the aryl thiols are used in situ for the synthesis of more advanced molecules such as diaryl sulfides and benzothiophenes.magnified image
Effekte des Volumenausschlusses in lebenden Zellen
Authors: Gnutt David , Gao Mimi , Brylski Oliver , Heyden Matthias , Ebbinghaus Simon 
Published: December 2014

AbstractBiomoleküle entstehen und funktionieren in einer dicht gepackten und heterogenen zellulären Umgebung. Diese Bedingungen werden im Reagenzglas oft durch Zugabe künstlicher makromolekularer “Crowding”‐Reagentien imitiert. Dennoch ist es unklar, ob solche Kosolventien tatsächlich die physikalischen und chemischen Eigenschaften der zellulären Umgebung widerspiegeln, da der zelluläre “Crowding”‐Effekt bisher nicht quantifiziert wurde. Wir haben einen makromolekularen “Crowding”‐Sensor, der auf einem FRET‐markiertem Polymer basiert, entwickelt, um diese Effekte zu untersuchen. Die Ergebnisse zeigen, dass die Volumenausschlusseffekte zu keiner Kompression des Sensors in der Zelle führen. Die durchschnittliche Konformation des Sensors ist dabei ähnlich zu der im verdünnten Puffer sowie im Zell‐Lysat. Ferner ist der zelluläre “Crowding”‐Effekt heterogen verteilt und verändert sich signifikant während eines osmotischen Schocks. Mithilfe dieser Methode lässt sich der zelluläre “Crowding”‐Effekt als Regulator von biomolekularen Reaktionen systematisch untersuchen.
ZnCl2‐Promoted Asymmetric Hydrogenation of β‐Secondary‐Amino Ketones Catalyzed by a P‐Chiral Rh–Bisphosphine Complex
Authors: Hu Qiupeng , Zhang Zhenfeng , Liu Yangang , Imamoto Tsuneo , Zhang Wanbin 
Published: December 2014

AbstractA new catalytic system has been developed for the asymmetric hydrogenation of β‐secondary‐amino ketones using a highly efficient P‐chiral bisphosphine–rhodium complex in combination with ZnCl2 as the activator of the catalyst. The chiral γ‐secondary‐amino alcohols were obtained in 90–94 % yields, 90–99 % enantioselectivities, and with high turnover numbers (up to 2000 S/C; S/C=substrate/catalyst ratio). A mechanism for the promoting effect of ZnCl2 on the catalytic system has been proposed on the basis of NMR spectroscopy and HRMS studies. This method was successfully applied to the asymmetric syntheses of three important drugs, (S)‐duloxetine, (R)‐fluoxetine, and (R)‐atomoxetine, in high yields and with excellent enantioselectivities.
Synthetic Ni‐talc as filler for producing polyurethane nanocomposites
Authors: Prado Manoela Argenton , Dias Guilherme , Carone Carlos , Ligabue Rosane , Dumas Angela , Le Roux Christophe , Micoud Pierre , Martin François , Einloft Sandra 
Published: December 2014

ABSTRACTNew synthetic Ni‐talc was used as filler in the synthesis of polyurethane (PU) nanocomposites by in situ polymerization and to emphasize the contribution of the new material compared with natural talc. Good dispersion of Ni‐talc was supported by homogeneous green coloration observed in the polymer matrix. X‐ray diffraction (XRD) analyses indicate the intercalation of polymeric matrix into the filler layers by the increase in d001‐spacing value of the Ni‐talc for the nanocomposites when compared to the pristine filler. The nanocomposites obtained with synthetic talc showed an improvement in the crystallization temperature and in thermal stability when compared to pure PU and the composite obtained with natural talc. The young modulus of PU/talc materials containing both Ni‐talc and natural talc were slight higher than pure PU. As shown by scanning electron microscope (SEM), Ni‐talc fillers were well dispersed into the polymeric matrix probably due to the good compatibility of both phases filler/polymer mainly achieved by the filler OH interaction with the urethane group of the polymeric chain. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41854.
Multi‐objective optimization of reactive extrusion by genetic algorithms
Authors: Zhang Guofang , Zhang Min , Jia Yuxi 
Published: December 2014

ABSTRACTIn reactive extrusion processes for polymerization, a multi‐objective optimization model maximizing the monomer conversion whilst ensuring the low energy consumption was constructed. The selections of reactive processing conditions could be set automatically using an optimization methodology based on genetic algorithms coupled with the numerical simulation routines. Various case studies were discussed. Comparison with experimental data indicates that the design of processing conditions can be performed according to the prespecified objectives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41862.
Effect of nanofiller on the behavior of a melt‐drawn HDPE/PA6 microfibrillar composite
Authors: Kelnar Ivan , Kaprálková Ludmila , Kratochvíl Jaroslav , Kotek Jiří , Kobera Libor , Rotrekl Jakub , Hromádková Jiřina 
Published: December 2014

ABSTRACTMicrofibrillar composites (MFCs) with reinforcing fibrils formed in situ by melt drawing were modified by the addition of layered silicates using different mixing protocols, viz simultaneous addition of components, application of respective premade nanocomposites and their combinations. The objective was to combine reinforcement with changes in the final structure, especially the fibril dimensions. The presented results indicate good potential of the nanoclay to enhance the MFC based on the melt‐drawn HDPE/PA6 system. The best mechanical behavior was achieved with the simultaneous addition of all components. The majority of the nanofiller material was contained inside the PA6 fibrils. Both fibrils dimensions and mechanical behavior were significantly affected by the nanofiller migration to the PA6 phase in the course of mixing and melt drawing. Due to a complex effect of the clay, deterioration of mechanical properties was also found. As a result, numerous, in some cases contradictory, effects of nanofillers must be perfectly harmonized to improve the properties of MFCs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41868.
The Parasitic Worm Product ES‐62 Targets Myeloid Differentiation Factor 88–Dependent Effector Mechanisms to Suppress Antinuclear Antibody Production and Proteinuria in MRL/lpr Mice
Authors: Rodgers David T. , McGrath Mairi A. , Pineda Miguel A. , Al‐Riyami Lamyaa , Rzepecka Justyna , Lumb Felicity , Harnett William , Harnett Margaret M. 
Published: December 2014

ObjectiveThe hygiene hypothesis suggests that parasitic helminths (worms) protect against the development of autoimmune disease via a serendipitous side effect of worm‐derived immunomodulators that concomitantly promote parasite survival and limit host pathology. The aim of this study was to investigate whether ES‐62, a phosphorylcholine‐containing glycoprotein secreted by the filarial nematode Acanthocheilonema viteae, protects against kidney damage in an MRL/lpr mouse model of systemic lupus erythematosus (SLE).MethodsMRL/lpr mice progressively produce high levels of autoantibodies, and the resultant deposition of immune complexes drives kidney pathology. The effects of ES‐62 on disease progression were assessed by measurement of proteinuria, assessment of kidney histology, determination of antinuclear antibody (ANA) production and cytokine levels, and flow cytometric analysis of relevant cellular populations.ResultsES‐62 restored the disrupted balance between effector and regulatory B cells in MRL/lpr mice by inhibiting plasmablast differentiation, with a consequent reduction in ANA production and deposition of immune complexes and C3a in the kidneys. Moreover, by reducing interleukin‐22 production, ES‐62 may desensitize downstream effector mechanisms in the pathogenesis of kidney disease. Highlighting the therapeutic importance of resetting B cell responses, adoptive transfer of purified splenic B cells from ES‐62–treated MRL/lpr mice mimicked the protection afforded by the helminth product. Mechanistically, this reflects down‐regulation of myeloid differentiation factor 88 expression by B cells and also kidney cells, resulting in inhibition of pathogenic cross‐talk among Toll‐like receptor–, C3a‐, and immune complex–mediated effector mechanisms.ConclusionThis study provides the first demonstration of protection against kidney pathology by a parasitic worm–derived immunomodulator in a model of SLE and suggests therapeutic potential for drugs based on the mechanism of action of ES‐62.
Soluble Macrophage Biomarkers Indicate Inflammatory Phenotypes in Patients With Knee Osteoarthritis
Authors: Daghestani Hikmat N. , Pieper Carl F. , Kraus Virginia B. 
Published: December 2014

ObjectiveTo evaluate the ability of the macrophage markers CD163 and CD14 to predict different osteoarthritis (OA) phenotypes defined by severity of joint inflammation, radiographic features and progression, and joint pain.MethodsWe evaluated 2 different cohorts totaling 184 patients with radiographic knee OA. These included 25 patients from a cross‐sectional imaging study for whom there were data on activated macrophages in the knee joint, and 159 patients (134 with 3‐year longitudinal data) from the longitudinal Prediction of Osteoarthritis Progression study. Multivariable linear regression models with generalized estimating equations were used to assess the association of CD163 and CD14 in synovial fluid (SF) and blood with OA phenotypic outcomes. Models were adjusted for age, sex, and body mass index. P values less than or equal to 0.05 were considered significant.ResultsSF CD14, SF CD163, and serum CD163 were associated with the abundance of activated macrophages in the knee joint capsule and synovium. SF CD14 was positively associated with severity of joint space narrowing and osteophytes in both cohorts. SF and plasma CD14 were positively associated with self‐reported knee pain severity in the imaging study. Both SF CD14 and SF CD163 were positively associated with osteophyte progression.ConclusionSoluble macrophage biomarkers reflected the abundance of activated macrophages and appeared to mediate structural progression (CD163 and CD14) and pain (CD14) in OA knees. These data support the central role of inflammation as a determinant of OA severity, progression risk, and clinical symptoms, and they suggest a means of readily identifying a subset of patients with an active inflammatory state and worse prognosis.
Direct Infection of Primary Salivary Gland Epithelial Cells by Human T Lymphotropic Virus Type I in Patients With Sjögren's Syndrome
Authors: Nakamura Hideki , Takahashi Yoshiko , Yamamoto‐Fukuda Tomomi , Horai Yoshiro , Nakashima Yoshikazu , Arima Kazuhiko , Nakamura Tatsufumi , Koji Takehiko , Kawakami Atsushi 
Published: December 2014

ObjectiveTo investigate whether human T lymphotropic virus type I (HTLV‐I) directly infects salivary gland epithelial cells (SGECs) and induces the niche of the salivary glands in patients with Sjögren's syndrome (SS).MethodsSGECs were cultured with the HTLV‐I–producing CD4+ T cell line HCT‐5 or with Jurkat cells. Antibody arrays, immunofluorescence analysis, and enzyme‐linked immunosorbent assay (ELISA) were used to determine the profiles of inflammation‐related molecules, and the profiles of apoptosis‐related molecules were determined by antibody array and immunofluorescence analysis. The presence of HTLV‐I–related molecules was assessed by immunofluorescence analysis and in situ polymerase chain reaction. Apoptosis of SGECs was evaluated by TUNEL staining.ResultsAmong the SGECs, 7.8 ± 1.3% (mean ± SD) were positive for HTLV‐I–related proteins after 96‐hour coculture with HCT‐5 cells. Nuclear NF‐κB p65 was also detected in 10% of the SGECs. The presence of HTLV‐I proviral DNA in SGECs after coculture with HCT‐5 cells was detected by in situ polymerase chain reaction. After coculture of SGECs with HCT‐5, the expression of cytokines and chemokines, including soluble intercellular adhesion molecule 1, RANTES, and interferon γ–induced protein 10 kd (IP‐10/CXCL10) was increased in a time‐dependent manner. The expression of proapoptotic molecules (e.g., cytochrome c and Fas) and antiapoptotic molecules (e.g., Bcl‐2, Heme oxygenase 2, and Hsp27) was increased in the SGECs cocultured with HCT‐5, showing that apoptosis of SGECs was not detected after coculture with HCT‐5 or Jurkat cells.ConclusionHTLV‐I is thought to infect SGECs and alter their cellular functions. These changes may induce the niche of SS and contribute to the development of SS in anti–HTLV‐I antibody–positive individuals.
Paclitaxel/carboplatin with or without sorafenib in the first‐line treatment of patients with stage III/IV epithelial ovarian cancer: a randomized phase II study of the Sarah Cannon Research Institute
Authors: Hainsworth John D. , Thompson Dana S. , Bismayer John A. , Gian Victor G. , Merritt William M. , Whorf Robert C. , Finney Lindsey H. , Dudley B. Stephens 
Published: December 2014

AbstractThis trial compared the efficacy and toxicity of standard first‐line treatment with paclitaxel/carboplatin versus paclitaxel/carboplatin plus sorafenib in patients with advanced ovarian carcinoma. Patients with stage 3 or 4 epithelial ovarian cancer with residual measurable disease or elevated CA‐125 levels after maximal surgical cytoreduction were randomized (1:1) to receive treatment with paclitaxel (175 mg/m2, 3 h infusion, day 1) and carboplatin (AUC 6.0, IV, day 1) with or without sorafenib 400 mg orally twice daily (PO BID). Patients were reevaluated for response after completing 6 weeks of treatment (two cycles); responding or stable patients received six cycles of paclitaxel/carboplatin. Patients receiving the sorafenib‐containing regimen continued sorafenib (400 PO BID) for a total of 52 weeks. Eighty‐five patients were randomized and received treatment.Efficacy was similar for patients receiving paclitaxel/carboplatin/sorafenib versus paclitaxel/carboplatin: overall response rates 69% versus 74%; median progression‐free survival 15.4 versus 16.3 months; 2 year survival 76% versus 81%. The addition of sorafenib added substantially to the toxicity of the regimen; rash, hand–foot syndrome, mucositis, and hypertension were significantly more common in patients treated with sorafenib. The addition of sorafenib to standard paclitaxel/carboplatin did not improve efficacy and substantially increased toxicity in the first‐line treatment of advanced epithelial ovarian cancer. Based on evidence from this study and other completed trials, sorafenib is unlikely to have a role in the treatment of ovarian cancer.
Two‐factor authentication scheme using attribute and password
Authors: Wei Jianghong , Hu Xuexian , Liu Wenfen 
Published: December 2014

SummaryIn this study, based on attribute and password, we introduce a new kind of two‐factor authentication protocol that has various applications such as anonymous authentication and privacy protection. Specifically, our proposal is constructed by introducing password authentication into the generic framework of attribute‐based authentication. Consequently, it not only achieves two‐factor authentication, but also enjoys the advantages of attribute authentication and password authentication simultaneously. Furthermore, to formally evaluate the security of the proposed protocol, we present the corresponding security model, within which the detailed security proof of the proposal is given. Copyright © 2014 John Wiley & Sons, Ltd.
Structural covariance networks of striatum subdivision in patients with Parkinson's disease
Authors: Chou Kun‐Hsien , Lin Wei‐Che , Lee Pei‐Lin , Tsai Nai‐Wen , Huang Yung‐Cheng , Chen Hsiu‐Ling , Cheng Kuei‐Yueh , Chen Pei‐Chin , Wang Hung‐Chen , Lin Tsu‐Kung , Li Shau‐Hsuan , Lin Wei‐Ming , Lu Cheng‐Hsien , Lin Ching‐Po 
Published: December 2014

AbstractParkinson's disease (PD) is a neurodegenerative disorder associated with the striatum. Previous studies indicated that subdivisions of the striatum with distinct functional connectivity profiles contribute to different pathogeneses in PD. Segregated structural covariance (SC) pattern between the striatum and neocortex observed in healthy subjects, however, remain unknown in PD. The purpose of this study is to map and compare the subregional striatal SC network organization between 30 healthy controls and 48 PD patients and to investigate their association with the disease severity. The striatal SC network was statistically inferred by correlating the mean gray matter (GM) volume of six striatal subdivisions (including the bilateral dorsal caudate, superior ventral striatum, inferior ventral striatum, dorsal caudal putamen, dorsal rostral putamen, and ventral rostral putamen) with the entire neocortical GM volume in voxel‐wise manner. The PD patients revealed marked atrophy in the striatum, cerebellum, and extra‐striatum neocortices. As predicted, segregated striatal SC network patterns were observed in both groups. This suggests that in PD, pathological processes occurring in the striatum affect the same striato‐cortical networks that covary with the striatum in healthy brains. The PD patients further demonstrated atypical striatal SC patterns between the caudate, parahippocampus temporal cortices, and cerebellum, which corresponded to dopaminergic associated network. The areas with significant group differences in SC were further associated with disease severity. Our findings support previous studies indicating that PD is associated with altered striato‐cortical networks, and suggest that structural changes in the striatum may result in a cascade of alterations in multiple neocortices. Hum Brain Mapp 36:1567–1584, 2015. © 2014 Wiley Periodicals, Inc.
Crystal Clear? The Relationship Between Methamphetamine Use and Sexually Transmitted Infections
Authors: Mialon Hugo M. , Nesson Erik T. , Samuel Michael C. 
Published: December 2014

SummaryPublic health officials have cited methamphetamine control as a tool with which to decrease HIV and other sexually transmitted infections, based on previous research that finds a strong positive correlation between methamphetamine use and risky sexual behavior. However, the observed correlation may not be causal, as both methamphetamine use and risky sexual behavior could be driven by a third factor, such as a preference for risky behavior. We estimate the effect of methamphetamine use on risky sexual behavior using monthly data on syphilis diagnoses in California and quarterly data on syphilis, gonorrhea, and chlamydia diagnoses across all states. To circumvent possible endogeneity, we use a large exogenous supply shock in the US methamphetamine market that occurred in May 1995 and a later shock stemming from the Methamphetamine Control Act, which went into effect in October 1997. While the supply shocks had large negative effects on methamphetamine use, we find no evidence that they decreased syphilis, gonorrhea, or chlamydia rates. Our results have broad implications for public policies designed to decrease sexually transmitted infection rates. Copyright © 2014 John Wiley & Sons, Ltd.
Trends in human papillomavirus–related oropharyngeal cancer in Israel
Authors: Amit Moran , Ilana Kaplan , Avraham Sharon Pelles , Binenbaum Yoav , Bachar Gideon , Billan Salem , Zaarura Suliman , Czerninski Rakefet , Bar‐Tov Matan , Maly Alexander , Akrish Sharon , Gil Ziv 
Published: December 2014

AbstractBackgroundThe role of human papillomavirus (HPV) infection in oropharyngeal cancer (SCC) is well established. The annual incidence of oropharyngeal SCC in Israel is considerably lower than that in the United States. The purpose of this study was to assess the rate of HPV‐related oropharyngeal SCC in Israel.MethodsThe cohort included patients with oropharyngeal SCC who were treated during 1999 to 2011 in Israel. HPV typing was carried out using reverse hybridization and immunohistochemistry.ResultsOf the 74 patients analyzed, 25 (33.7%) had detectable HPV DNA. Patients in the HPV‐positive group tended to be younger, with a higher rate of nodal metastases, and no history of smoking (p < .02).ConclusionThis study demonstrated a rate of HPV‐related oropharyngeal SCC in Israel as approximately 3‐fold lower than in Western countries. Low exposure to HPV‐16, a lower rate of transformation, to cancer or protective genetic factors may contribute to the lower rate of oropharyngeal SCC in Israel. © 2015 Wiley Periodicals, Inc. Head Neck 38: E274–E278, 2016