bluuebunny/crossref_metadata_2025_split huggingface dataset:
Wohl‐Ziegler Bromination of Electrografted Films for Optimizing Atom Transfer Radical Polymerization
Authors: Nielsen Stefan Urth , Koefoed Line , Lund Henning , Daasbjerg Kim , Pedersen Steen U. 
Published: July 2016

AbstractElectrografting of aryldiazonium compounds to conducting surfaces is extensively used to alter the surface properties. The highly reactive aryl radical is the actual grafting reagent, which on one hand is pertinent for the efficiency of the procedure but, on the other hand, in some cases is problematic by introducing unwanted side reactions. The electrografting of e.g. 4‐(bromomethyl)benzenediazonium is often carried out with the aim of creating a film that may serve as initiator for a controlled atom transfer radical polymerization. Unfortunately, this is difficult to accomplish because of bromine abstraction reactions occurring during the grafting process, which diminish the bromine content of the grafted layer significantly. Yet, this problem may be resolved by enriching the initiator film with bromine through a Wohl‐Ziegler bromination prior to the polymerization. An alternative pathway consisting of grafting 4‐methylbenzenediazonium followed by a bromination reaction to introduce bromine atoms at the benzylic position is shown to work equally well. Additionally, bromination of grafted benzyl alcohol groups have been explored. Finally, the repaired bromine films are used as a platform for atom transfer radical polymerization.
Gender, identity, and bioethics
Authors: Dietz Elizabeth A. 
Published: July 2016

AbstractTransgender people and issues have come to the forefront of public consciousness over the last year. Caitlyn Jenner' very public transition, heightened media coverage of the murders of transgender women of color, and the panicked passage of North Carolina's “bathroom bill” (House Bill 2), mean that conversations about transgender health and well‐being are no longer happening only within small communities. The idea that transgender issues are bioethical issues is not new, but I think that increased public awareness of transgender people and the ways that their health is affected by systems that bioethics already engages with offers an opportunity for scholarship that works to improve transgender health in meaningful ways.
The Income–Health Relationship ‘Beyond the Mean’: New Evidence from Biomarkers
Authors: Carrieri Vincenzo , Jones Andrew M. 
Published: July 2016

AbstractThe relationship between income and health is one of the most explored topics in health economics but less is known about this relationship at different points of the health distribution. Analysis based solely on the mean may miss important information in other parts of the distribution. This is especially relevant when clinical concern is focused on the tail of the distribution and when evaluating the income gradient at different points of the distribution and decomposing income‐related inequalities in health is of interest. We use the unconditional quantile regression approach to analyse the income gradient across the entire distribution of objectively measured blood‐based biomarkers. We apply an Oaxaca–Blinder decomposition at various quantiles of the biomarker distributions to analyse gender differentials in biomarkers and to measure the contribution of income (and other covariates) to these differentials. Using data from the Health Survey for England, we find a non‐linear relationship between income and health and a strong gradient with respect to income at the highest quantiles of the biomarker distributions. We find that there is heterogeneity in the association of health to income across genders, which accounts for a substantial percentage of the gender differentials in observed health. Copyright © 2016 John Wiley & Sons, Ltd.
Heritability and Genetic Correlations for Bone Microarchitecture: The Framingham Study Families
Authors: Karasik David , Demissie Serkalem , Zhou Yanhua , Lu Darlene , Broe Kerry E , Bouxsein Mary L , Cupples L Adrienne , Kiel Douglas P 
Published: July 2016

ABSTRACT

High-resolution peripheral quantitative computed tomography (HR-pQCT) measures bone microarchitecture and volumetric bone mineral density (vBMD), important risk factors for osteoporotic fractures. We estimated the heritability (h2) of bone microstructure indices and vBMD, measured by HR-pQCT, and genetic correlations (ρG) among them and between them and regional aBMD measured by dual-energy X-ray absorptiometry (DXA), in adult relatives from the Framingham Heart Study. Cortical (Ct) and trabecular (Tb) traits were measured at the distal radius and tibia in up to 1047 participants, and ultradistal radius (UD) aBMD was obtained by DXA. Heritability estimates, adjusted for age, sex, and estrogenic status (in women), ranged from 19.3% (trabecular number) to 82.8% (p &lt; 0.01, Ct.vBMD) in the radius and from 51.9% (trabecular thickness) to 98.3% (cortical cross-sectional area fraction) in the tibia. Additional adjustments for height, weight, and radial aBMD had no major effect on h2 estimates. In bivariate analyses, moderate to high genetic correlations were found between radial total vBMD and microarchitecture traits (ρG from 0.227 to 0.913), except for cortical porosity. At the tibia, a similar pattern of genetic correlations was observed (ρG from 0.274 to 0.948), except for cortical porosity. Environmental correlations between the microarchitecture traits were also substantial. There were high genetic correlations between UD aBMD and multivariable-adjusted total and trabecular vBMD at the radius (ρG = 0.811 and 0.917, respectively). In summary, in related men and women from a population-based cohort, cortical and trabecular microarchitecture and vBMD at the radius and tibia were heritable and shared some h2 with regional aBMD measured by DXA. These findings of high heritability of HR-pQCT traits, with a slight attenuation when adjusting for aBMD, supports further work to identify the specific variants underlying volumetric bone density and fine structure of long bones. Knowledge that some of these traits are genetically correlated can serve to reduce the number of traits for genetic association studies. © 2016 American Society for Bone and Mineral Research.
Synthesis of raffinose by transfructosylation using recombinant levansucrase from Clostridium arbustiSL206
Authors: Li Wenjing , Yu Shuhuai , Zhang Tao , Jiang Bo , Mu Wanmeng 
Published: July 2016

AbstractBACKGROUNDRaffinose, a functional trisaccharide of α‐d‐galactopyranosyl‐(1 → 6)‐α‐d‐glucopyranosyl‐(1 → 2)‐β‐d‐fructofuranoside, is a prebiotic that shows promise for use as a food ingredient.RESULTSIn this study, the production of raffinose from melibiose and sucrose was studied using whole recombinant Escherichia coli cells harboring the levansucrase from Clostridium arbusti SL206. The reaction conditions were optimized for raffinose synthesis. The optimal pH, temperature and washed cell concentration were pH 6.5 (sodium phosphate buffer, 50 mmol L−1), 55 °C and 3% (w/v), respectively. High substrate concentrations, which led to low water activity and thus reduced levansucrase hydrolysis activity, strongly favored the production of raffinose through the fructosyl transfer reaction. Additionally, high concentrations of excess acceptor and donor glycosides favored raffinose production. When 30% (w/v) sucrose and 30% (w/v) melibiose were catalyzed using 3% (w/v) whole cells at pH 6.5 (sodium phosphate buffer, 50 mmol L−1) and 55 °C, the highest raffinose yield was 222 g L−1 after a 6 h reaction. The conversion ratio from each substrate to raffinose was 50%.CONCLUSIONRaffinose could be effectively produced with melibiose as an acceptor and with sucrose as a fructosyl donor by whole recombinant E. coli cells harboring C. arbusti levansucrase. The yield from E. coli was significantly higher than those of the previously reported Bacillus subtilis levansucrase and fungal α‐galactosidases. © 2016 Society of Chemical Industry
First Experimental and Theoretical Kinetic Study of the Reaction of 4‐Hydroxy‐4‐methyl 2‐pentanone as a Function of Temperature
Authors: Priya Angappan Mano , Lakshmipathi Senthilkumar , Chakir Abdelkhaleq , El Dib Gisèle 
Published: July 2016

ABSTRACTIn this work, experimental and theoretical rate coefficients were determined for the first time for the gas‐phase reaction of 4‐hydroxy‐4‐methyl‐2‐pentanone (4H4M2P) with OH radicals as a function of temperature. Experimental studies were carried out over the pressure range of 5–80 Torr and the temperature range of 280–365 K, by using a cryogenically cooled cell coupled to the pulsed laser photolysis‐laser induced fluorescence (PLP–LIF) technique. A detailed oxidation mechanism of 4H4M2P with OH radicals was discussed theoretically under three hydrogen abstraction pathways by using density functional theory calculations and wave function based MP2 method. Single‐point energy calculations were performed at CCSD(T) level of theory with 6–311++G(d,p) basis set. The H‐atom abstraction from the ‐CH2 group was found to be the dominant channel. The reaction force analysis predicts that the abstraction process is mainly dominated by structural rearrangement. Linear kinetic behavior for all the pathways was found in the range of 278–365 K. An atmospheric lifetime less than 3 days was evaluated for 4H4M2P with respect to its reaction with OH, indicating that the reaction with OH of 4H4M2P may be competitive with losses via photolysis.
Synthesis of Vegetable Oil‐Based Polyurethane: A Study on Curing Kinetics Behavior
Authors: Sahoo Swarnalata , Kalita Hemjyoti , Mohanty Smita , Nayak Sanjay K. 
Published: July 2016

ABSTRACTIn the present study, biobased polyurethane (BPU) samples were synthesized from three different polyols along with polymeric hexamethylene diisocyanate. The three different polyols were synthesized by reacting castor oil with ethylene glycol, triethylene glycol, and triethanolamine. The synthesized polyols were confirmed using proton nuclear magnetic resonance (1H NMR) spectra analysis. BPU samples were confirmed by the disappearance of isocyanate peak in the FTIR spectra. The cross‐linking densities of all BPU samples were determined using swelling studies. Curing kinetics behavior of all BPU samples were analyzed using differential scanning calorimetry at three different heating rates (5, 7.5, and 10°C/min). The curing kinetic parameters were studied using three nonisothermal methods such as Kissinger, Flynn–Wall–Ozawa, and Ozawa, respectively. The activation energies were found to increase with increasing degree of cure (α). Surface properties of all the synthesized BPU samples were evaluated by dynamic mechanical analysis and scanning electron microscopy.
Proliferation, migration, and expression of oral‐mucosal‐healing‐related genes by oral fibroblasts receiving low‐level laser therapy after inflammatory cytokines challenge
Authors: Basso Fernanda G. , Soares Diana G. , Pansani Taisa N. , Cardoso Lais M. , Scheffel Débora L. , de Souza Costa Carlos Alberto , Hebling Josimeri 
Published: July 2016

Background and ObjectivesIncreased expression of inflammatory cytokines in the oral cavity has been related to the etiopathogenesis of oral mucositis and to delayed oral mucosal repair. Low‐level laser therapy (LLLT) stimulates proliferation and migration of gingival fibroblasts, but the effects of specific inflammatory cytokines on oral mucosal cells and the modulation of these effects by LLLT have not been fully investigated. Therefore, this study investigated the effects of LLLT on oral fibroblasts after being challenged by oral‐mucositis‐related inflammatory cytokines.MethodsHuman gingival fibroblasts were seeded in plain culture medium (DMEM) containing 10% fetal bovine serum (FBS) for 24 hours. Then, cells were kept in contact with inflammatory cytokines (TNF‐α, IL‐1β, IL‐6, and IL‐8) in serum‐free DMEM for 24 hours. After this period, cells were subjected to LLLT with a diode laser device (LaserTABLE, InGaAsP, 780 nm, 25 mW) delivering energy doses from 0.5 to 3 J/cm2. Irradiation was repeated for 3 consecutive days. Twenty‐four hours after the last irradiation, cell migration (wound‐healing and transwell migration assays), cell proliferation (BrdU), gene expression of COL‐I and growth factors (real‐time PCR), and synthesis of COL‐I (Sirius Red assay) and VEGF (ELISA) were assessed. Data were subjected to two‐way ANOVA and Tukey's tests or Kruskall–Walis and Mann–Whitney tests (P < 0.05).ResultsThe inflammatory cytokines decreased the migration capacity of gingival fibroblasts. However, a statistically significant difference was observed only for IL‐6, detected by transwell assay, where 30% less cells migrated through the pores (P < 0.05) and IL‐8, with an increased wound area (116%; P < 0.05), detected by the wound healing method. Cell proliferation was not affected by contact with cytokines, while growth factors and COL‐I expression (approximately 80%; P < 0.05), as well as VEGF synthesis (approximately 20%; P < 0.05), were decreased after contact to all tested cytokines. The opposite was seen for total collagen synthesis. LLLT promoted an acceleration of fibroblast migration (30%; P < 0.05) and proliferation (112%; P < 0.05) when delivering 0.5 J/cm2 to the cells previously in contact with the inflammatory cytokines. Gene expression of VEGF (approximately 30%; P < 0.05), and EGF (17%; P < 0.05), was stimulated by LLLT after contact with TNF‐α and IL‐6.ConclusionLLLT can counteract the negative effects of high concentrations of inflammatory cytokines, especially IL‐6 and IL‐8 on gingival fibroblast functions directly related to the wound‐healing process. Lasers Surg. Med. 48:1006–1014, 2016. © 2016 Wiley Periodicals, Inc.
Mussel‐Inspired Coatings Directed and Accelerated by an Electric Field
Authors: He Ai , Zhang Chao , Lv Yan , Zhong Qi‐Zhi , Yang Xi , Xu Zhi‐Kang 
Published: July 2016

Polydopamine‐based coatings are fabricated via an electric field‐accelerating and ‐directing codeposition process of polydopamine with charged polymers such as polycations, polyanions, and polyzwitterions. The coatings are uniform and smooth on various substrates, especially on those adhesion‐resistant materials including poly(vinylidene fluoride) and poly(tetrafluoroethylene) membranes. Moreover, this electric field‐directed deposition method can be applied to facilely prepare Janus membranes with asymmetric chemistry and wettability.
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An adaptive Paris Metro Pricing scheme for mobile data networks
Authors: Huang Huai‐Sheng , Hu Shu‐Chiung , Lee Po‐Han , Tseng Yu‐Chee 
Published: July 2016

SummaryBecause static pricing models (such as flat‐rate or tiered‐rate models) cannot improve user utility for subscribers and ease network congestion for operators during peak time, Smart Data Pricing has become an important incentive for mobile data markets. Paris Metro Pricing (PMP), which is a static pricing mode inspired by the pricing model for the Paris metro system, uses differentiated prices to motivate users to choose different train classes. Before choosing a class, people will consider their expected quality of service versus the prices that they are willing to pay. Even though PMP cannot guarantee the actual quality of service during service time, a balance between users' utilities and operators' revenue is achieved. In this paper, we propose an adaptive PMP scheme, so‐called APMP, which determines the dynamic access prices of different classes for the next 24 h. The accessible prices should try to increase the revenue while operators can serve more subscribers. Our simulation results show that APMP can significantly improve total revenue and average revenue per user for the operator. Copyright © 2016 John Wiley & Sons, Ltd.
Elastomeric ethylene copolymers with carbon nanostructures having tailored strain sensor behavior and their interpretation based on the excluded volume theory
Authors: Palza Humberto , Garzon Cristhian , Rojas Mauricio 
Published: July 2016

AbstractTwo ethylene/1‐butene thermoplastic elastomer copolymers were melt mixed with either multiwalled carbon nanotubes (CNTs) or thermally reduced graphite oxide (TrGO) resulting in piezoresistive composite materials. The effect of the polymer matrix, carbon nanostructure and filler concentration on the electrical behavior of the sensors was analyzed. The percolation process confirmed the relevance of these parameters as different thresholds were found depending on both the matrix and the filler. For instance, composites based on TrGO presented higher percolation thresholds than those based on CNTs. Regarding the strain sensor behavior of the electrically conductive composites, by using a matrix with a low amount of 1‐butene comonomer, higher resistance sensitivities were observed compared with the other matrix. Noteworthy, composites based on TrGO filler presented strain sensitivities one order of magnitude higher than composites based on CNT filler. These results are explained by the excluded volume theory for percolated systems. Based on these findings, polyethylene piezoresistive sensors can be designed by a proper selection of polymer matrix, filler concentration and carbon nanoparticles. © 2016 Society of Chemical Industry
A fuzzy detection approach toward different speed port scan attacks based on Dempster–Shafer evidence theory
Authors: Shao Guo‐lin , Chen Xing‐shu , Yin Xue‐yuan , Ye Xiao‐ming 
Published: July 2016

AbstractPort scan detection is one of the important topics in network security and has received lots of attention by researchers; however a slow port scan attack can deceive most of the existing IDS. Besides, it is unreasonable in typical detection to decide whether it is a probe based on the precise threshold especially when the feature values are around the threshold without taking the uncertainty into consideration. To address these problems, a novel approach was proposed by collecting traffic statistics information called access port set (APS) for each IP address in time windows; several traffic features are extracted from APS which are considered as multiple evidences to indicate a probe. For each evidence, three probabilities are concerned to evaluate the likelihood of the probe occurring which include the probabilities of support, nonsupport and uncertainty. The comprehensive evidence can be obtained from the combination of multiple evidences to evaluate the probe threaten. Several experiments were performed to evaluate the approach with DARPA/MIT datasets and our own generated attack datasets; the experimental results show the feasibility of our approach in terms of detection accuracy and effectiveness. The mechanism can be applied not only in port scan detection but also other precise threshold based situations such as traffic abnormal analysis and intrusion detection. Copyright © 2016 John Wiley & Sons, Ltd.
Bi(OTf)3 Catalyzed Solvent Free Approach to Unsymmetrical Diaryl(2‐indolyl)methanes through 1,6‐Conjugate Addition of 3‐Substituted Indoles to para‐Quinone Methides
Authors: Goswami Prithwish , Anand Ramasamy Vijaya 
Published: July 2016

AbstractAn efficient 1,6‐conjugate addition of 3‐substituted indoles to para‐quinone methides (p‐QMs) using catalytic amount of Bi(OTf)3 is described. This mild and atom‐economical protocol allowed us to access unsymmetrical diaryl(2‐indolyl)methanes in moderate to excellent yields under solvent‐free grinding conditions.
Unusual 1,2‐Acyl Rearrangement Accompanying Ring Expansion Reaction of Alkaloid Cotarnine under the Action of α‐Haloketones: a New Route to 5‐Acyl‐1,2‐dihydro‐3‐benzazepine Moiety
Authors: Zubenko Alexander A. , Kartsev Viktor G. , Morkovnik Anatolii S. , Divaeva Ludmila N. , Suponitsky Kyrill Yu. 
Published: July 2016

AbstractThe ring expansion reaction of the isoquinoline alkaloid cotarnine with α‐haloketones which normally leads to the formation of 4‐acyl‐7,8‐metylenedioxy‐1,2‐dihydro‐3‐benzazepines, in some cases, occurs with an unusual, non‐acid‐catalytic 1,2‐acyl rearrangement. As a result, corresponding 5‐acyl isomers are formed. A carbocation mechanism of the rearrangement was proposed. It involves formation of 4‐acyl‐5‐hydroxy‐7,8‐metylenedioxy‐1,2,3,4‐tetrahydro‐3‐benzazepines and their dissociation (as leuko bases) into corresponding benzazepine carbocations. As it follows from DFT calculations, these carbocations are prone to almost barrierless intracationic 1,2‐acyl group migration with conversion into corresponding isomeric carbocations. At the last stage of the reaction, these cations are deprotonated into final rearranged compounds.
XHAMI – extended HDFS and MapReduce interface for Big Data image processing applications in cloud computing environments
Authors: Kune Raghavendra , Konugurthi Pramod Kumar , Agarwal Arun , Chillarige Raghavendra Rao , Buyya Rajkumar 
Published: July 2016

SummaryHadoop distributed file system (HDFS) and MapReduce model have become popular technologies for large‐scale data organization and analysis. Existing model of data organization and processing in Hadoop using HDFS and MapReduce are ideally tailored for search and data parallel applications, for which there is no need of data dependency with its neighboring/adjacent data. However, many scientific applications such as image mining, data mining, knowledge data mining, and satellite image processing are dependent on adjacent data for processing and analysis. In this paper, we identify the requirements of the overlapped data organization and propose a two‐phase extension to HDFS and MapReduce programming model, called XHAMI, to address them. The extended interfaces are presented as APIs and implemented in the context of image processing application domain. We demonstrated effectiveness of XHAMI through case studies of image processing functions along with the results. Although XHAMI has little overhead in data storage and input/output operations, it greatly enhances the system performance and simplifies the application development process. Our proposed system, XHAMI, works without any changes for the existing MapReduce models and can be utilized by many applications where there is a requirement of overlapped data. Copyright © 2016 John Wiley & Sons, Ltd.
Mass Spectrometric Back Reaction Screening of Quasi‐Enantiomeric Products as a Mechanistic Tool
Authors: Isenegger Patrick G. , Pfaltz Andreas 
Published: July 2016

AbstractIn this account, we discuss a mass spectrometric method that enables unambiguous identification of intermediates involved in the enantioselective step of a catalytic cycle. This method, which we originally developed for rapid evaluation of chiral catalysts, is based on monitoring the back reaction of mass‐labeled quasi‐enantiomeric products by ESI‐MS. In this way, the intrinsic enantioselectivity of a chiral catalyst can be determined directly by quantification of catalytically relevant intermediates. By comparing the results from the forward and back reaction, direct evidence for the involvement of a catalytic intermediate in the enantioselective step can be obtained. In addition, insights about the energy profile of the catalytic cycle may be gained. The potential of back reaction screening as a mechanistic tool is demonstrated for organocatalytic aldol reactions, 1,4‐additions of aldehydes to nitroolefins, Diels–Alder reactions, Michael additions, and Morita–Baylis–Hillman reactions.
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