bluuebunny/crossref_metadata_2025 huggingface dataset:
Highly Reactive Nonheme Iron(III) Iodosylarene Complexes in Alkane Hydroxylation and Sulfoxidation Reactions
Authors: Hong Seungwoo , Wang Bin , Seo Mi Sook , Lee Yong‐Min , Kim Myoung Jin , Kim Hyung Rok , Ogura Takashi , Garcia‐Serres Ricardo , Clémancey Martin , Latour Jean‐Marc , Nam Wonwoo
Published: May 2014

High‐spin iron(III) iodosylarene complexes bearing an N‐methylated cyclam ligand are synthesized and characterized using various spectroscopic methods. The nonheme high‐spin iron(III) iodosylarene intermediates are highly reactive oxidants capable of activating strong CH bonds of alkanes; the reactivity of the iron(III) iodosylarene intermediates is much greater than that of the corresponding iron(IV) oxo complex. The electrophilic character of the iron(III) iodosylarene complexes is demonstrated in sulfoxidation reactions.
Controlled Directional Water‐Droplet Spreading on a High‐Adhesion Surface
Authors: Feng Shile , Wang Sijie , Gao Longcheng , Li Guangjun , Hou Yongping , Zheng Yongmei
Published: May 2014

Controlled directional spreading of a droplet on a smart high‐adhesion surface was made possible by simply controlling anodic oxidation. The wettability gradient of the surface was controlled from 0.14 to 3.38° mm−1 by adjusting the anodic oxidation conditions. When a water droplet made contact with the substrate, the droplet immediately spread in the direction of the wettability gradient but did not move in other directions, such as those perpendicular to the gradient direction, even when the surface was turned upside down. The spreading behavior was mainly controlled by the wettability gradient. Surfaces with a V‐ or inverse‐V‐shaped wettability gradient were also formed by the same method, and two droplets on these surfaces spread either toward or away from one another as designed. This method could be used to oxidize many conductive substrates (e.g., copper, aluminum) to form surfaces with variously shaped wettability gradients. It has potential for application in microfluidic devices.
Formation of Mesoporous Heterostructured BiVO4/Bi2S3 Hollow Discoids with Enhanced Photoactivity
Authors: Gao Xuehui , Wu Hao Bin , Zheng Lingxia , Zhong Yijun , Hu Yong , Lou Xiong Wen (David)
Published: May 2014

Semiconductor heterostructures are of great interest in a wide range of applications. In this work, we design and synthesize a novel heteronanostructure with controlled relative composition, i.e., BiVO4/Bi2S3 hollow discoid‐like particles with mesoporous shell. The synthesis involves a facile anion exchange process by reacting pre‐synthesized BiVO4 discoid‐like particles with Na2S in an aqueous solution. Benefiting from the unique structural features and the formation of heterostructure, the as‐prepared BiVO4/Bi2S3 hollow discoids exhibit significantly enhanced photoelectrochemical current response and photocatalytic activity for reduction of CrVI under visible‐light illumination.
Mapping of the Photoinduced Electron Traps in TiO2 by Picosecond X‐ray Absorption Spectroscopy
Authors: Rittmann‐Frank M. Hannelore , Milne Chris J. , Rittmann Jochen , Reinhard Marco , Penfold Thomas J. , Chergui Majed
Published: May 2014

Titanium dioxide (TiO2) is the most popular material for applications in solar‐energy conversion and photocatalysis, both of which rely on the creation, transport, and trapping of charges (holes and electrons). The nature and lifetime of electron traps at room temperature have so far not been elucidated. Herein, we use picosecond X‐ray absorption spectroscopy at the Ti K‐edge and the Ru L3‐edge to address this issue for photoexcited bare and N719‐dye‐sensitized anatase and amorphous TiO2 nanoparticles. Our results show that 100 ps after photoexcitation, the electrons are trapped deep in the defect‐rich surface shell in the case of anatase TiO2, whereas they are inside the bulk in the case of amorphous TiO2. In the case of dye‐sensitized anatase or amorphous TiO2, the electrons are trapped at the outer surface. Only two traps were identified in all cases, with lifetimes in the range of nanoseconds to tens of nanoseconds.
Vinyl Dihydropyrans and Dihydrooxazines: Cyclizations of Catalytic Ruthenium Carbenes Derived from Alkynals and Alkynones
Authors: Cambeiro Fermín , López Susana , Varela Jesús A. , Saá Carlos
Published: May 2014

A novel synthesis of 2‐vinyldihydropyrans and dihydro‐1,4‐oxazines (morpholine derivatives) from alkynals and alkynones has been developed. The cyclizations require a mild generation of catalytic ruthenium carbenes from terminal alkynes and (trimethylsilyl)diazomethane followed by trapping with carbonyl nucleophiles. Mechanistic aspects of the new cyclizations are discussed.
Magnetic nanoparticle γ‐Fe2O3‐immobilized 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene as a highly recyclable and efficient nanocatalyst for the synthesis of α′‐oxindole‐α‐hydroxyphosphonates
Authors: Yang Xiao Juan
Published: May 2014

Magnetic nanoparticle γ‐Fe2O3‐immobilized 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene as a novel magnetic nanocatalyst was synthesized and characterized. The nanoparticle reagent catalyzed efficiently the synthesis of α′‐oxindole‐α‐hydroxyphosphonates from isatins and dimethyl phosphate under solvent‐free conditions at 60 °C. More importantly, the catalyst could be easily recovered by an external magnet and reused six times without significant loss of activity. Copyright © 2014 John Wiley & Sons, Ltd.
Numerical simulations to evaluate basic geometrical shapes as headers for equal liquid flow distribution
Authors: Darekar Mayur , Singh K. K. , Shenoy K. T. , Kundu G. , Rao H. , Ghosh S. K.
Published: May 2014

The study presents computational fluid dynamics (CFD) simulations for evaluation of basic geometrical shapes as headers for equal liquid flow distribution. The headers that have been evaluated are conical header, cylindrical header, pyramidal header, rectangular header and spherical header. The computational approach used in the study has been validated by comparing predictions of numerical simulations with experimental results for a cylindrical header. The effects of volume of header, flow rate, diameter of outlets and pressure imbalance at outlets on flow distribution have been studied. At low flow rates, there is no significant difference in the performance of the headers of different geometrical shapes. At higher flow rates, spherical header is found to be better. The possibility of ensuring equal flow distribution by having outlets of varying cross‐sectional area is discussed. The results reported in the study provide useful insights relevant for header design problems. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Investigation of biomass ash thermal decomposition by thermogravimetry using raw and artificial ashes
Authors: Li Qinghai , Meng Aihong , Li Li , Zhou Hui , Zhang Yanguo
Published: May 2014

The effects of alkali oxide (K2O), calcium oxide (CaO) and ratio of silicon oxide to aluminum oxide (SiO2/Al2O3) on the thermal decomposition of biomass ashes and artificial ashes were examined by using thermogravimetric (TG) and derivative thermogravimetric (DTG) analysis. It was observed that mass losses due to mineral evolution from the ashes mainly occur during three temperature ranges: (a) low temperature, 70–250 °C; (b) moderate temperature, 350–450 °C; and (c) high temperature, 600–1100 °C. The ratios of SiO2/Al2O3 almost have no obvious effects of on the mass loss. The CaO content mainly contributes to the peaks at moderate temperature. The alkali contents show clear effects on the TG and DTG curves. The apparent activation energy and pre‐exponential factor were obtained based on the first‐order assumption for the separate splitting consecutive reaction. The kinetic analysis of the thermal decomposition of biomass ashes to some extent confirms that the initial deformation temperature during ash fusion test is susceptible to the K2O evolution at low temperature. It also helps understand the inorganic compounds partitioning during the biomass combustions and thereof effects on the ash fusion temperature. © 2014 Curtin University of Technology and John Wiley & Sons, Ltd.
Norepinephrine Inhibition of Mesenchymal Stem Cell and Chondrogenic Progenitor Cell Chondrogenesis and Acceleration of Chondrogenic Hypertrophy
Authors: Jenei‐Lanzl Zsuzsa , Grässel Susanne , Pongratz Georg , Kees Frieder , Miosge Nicolai , Angele Peter , Straub Rainer H.
Published: May 2014

Objective

Mesenchymal progenitor cell chondrogenesis is the biologic platform for the generation or regeneration of cartilage, but the external influence of the sympathetic nervous system on this process is not yet known. Sympathetic nerve fibers are present in articular tissue, and the sympathetic nervous system influences the musculoskeletal system by, for example, increasing osteoclastogenesis. This study was initiated to explore the role of the sympathetic neurotransmitter norepinephrine (NE) in mesenchymal stem cell (MSC)–dependent and cartilage progenitor cell (CPC)–dependent chondrogenesis.

Methods

Using human MSCs or CPCs, chondrogenic differentiation was induced in the presence of NE, the specific β‐adrenergic receptor (β‐AR) agonist isoproterenol, and the specific β‐AR antagonist nadolol. We studied sympathetic nerve fibers, tyrosine hydroxylase (TH) expression, catecholamine biosynthesis, and synovial fluid levels in human joints, as well as cartilage‐specific matrix deposition during differentiation.

Results

TH+ sympathetic nerve fibers were present in the synovial tissue, meniscus, and subchondral bone marrow. In addition, synovial fluid from patients with knee trauma demonstrated high concentrations of NE. During MSC or CPC chondrogenesis, β‐AR were expressed. Chondrogenic aggregates treated with NE or isoproterenol synthesized lower amounts of type II collagen and glycosaminoglycans. NE and isoproterenol treatment dose‐dependently increased the levels of cartilage hypertrophy markers (type X collagen and matrix metalloproteinase 13). Nadolol reversed the inhibition of chondrogenesis and the up‐regulation of cartilage hypertrophy.

Conclusion

Our findings demonstrate NE‐dependent inhibition of chondrogenesis and acceleration of hypertrophic differentiation. By inhibiting cartilage repair, these sympathetic influences can be important after joint trauma. These findings may be a basis for novel neurochondrogenic therapeutic options.
The Discoidin Domain Receptor 2/Annexin A2/Matrix Metalloproteinase 13 Loop Promotes Joint Destruction in Arthritis Through Promoting Migration and Invasion of Fibroblast‐like Synoviocytes
Authors: Zhao Wei , Zhang Cun , Shi Man , Zhang Jian , Li Meng , Xue Xiaochang , Zhang Zhao , Shu Zhen , Zhu Jinyu , Mu Nan , Li Weina , Hao Qiang , Wang Zhijun , Gong Li , Zhang Wei , Zhang Yingqi
Published: May 2014

Objective

Discoidin domain receptor 2 (DDR‐2)/matrix metalloproteinase (MMP) signaling is an important pathway involved in cartilage destruction in rheumatoid arthritis (RA). However, the molecular mechanisms of this pathway have not been clearly identified. This study was undertaken to screen key molecules involved in this pathway and evaluate their biologic functions in synovium invasion of RA.

Methods

DDR‐2–interacting proteins were examined in vitro by immunoprecipitation and mass spectrometry, and annexin A2 was acquired. The effects of annexin A2 on fibroblast‐like synoviocyte (FLS) migration were evaluated using a Transwell invasion assay and an Erasion trace test. In Ddr2−/− mice with collagen‐induced arthritis (CIA), hematoxylin and eosin (H&E) staining, immunohistochemical analysis, and Western blot analysis were used to assess expression of DDR‐2, annexin A2, and MMP‐13, as well as synovial hyperplasia. Rats with CIA were treated with lentivirus annexin A2 small interfering RNA (siRNA), and annexin A2 siRNA effects on joint damage were analyzed based upon arthritis index scores and results of micro–computed tomography and H&E staining. The differences between annexin A2 expression in clinical samples from RA and osteoarthritis patients were compared using Western blotting.

Results

Annexin 2 was identified for the first time as a DDR‐2 binding protein. It may be phosphorylated by phospho–DDR‐2, leading to MMP‐13 secretion. The annexin A2 phosphorylation level and MMP‐13 expression level were decreased and collagen‐induced joint damage greatly reduced in Ddr2−/− mice. Joint damage in rats with CIA was significantly ameliorated when annexin A2 was down‐regulated. Annexin A2 expression and phosphorylation were elevated in human RA synovial tissue.

Conclusion

Annexin A2 is a key molecule in the DDR‐2/annexin A2/MMP‐13 loop, the activation of which contributes to joint destruction in RA, mainly through promoting invasion of FLS. Annexin A2 might therefore become a novel clinical target for RA treatment.
Data, censorship, and politics: Analyzing the restricted flow of information in federal scientific policy development
Authors: Oltmann Shannon M.
Published: May 2014

Citizen access to information, particularly scientific information used for public policy discussions and decision making, is important in a democracy. However, access to this information can sometimes be restricted or blocked in various ways. This research adopts Jaeger and Burnett's (2005) conceptualization of information access as “the presence of a robust system through which information is made available to citizens and others” (p. 465) with physical, intellectual, and social components. This provides the conceptual framework through which incidents of restricted access to science policy (RASP) were analyzed in a comparative case study. The research found that citizens' physical, intellectual, and social access to scientific research was restricted in these cases. Furthermore, the theoretical framework of democratic accountability held normative and symbolic power for the respondents; although democratic accountability did not accurately predict respondents' actions, it was used as a significant justification for their actions. This research suggests that the conceptual framework of information access (with physical, intellectual, and social components) and the theoretical framework of democratic accountability (although primarily normative) may be useful approaches to subsequent investigations of censorship and restricted access in other situations and research areas.
Top‐Up Fabrication of Gold Nanorings
Authors: Scheeler Sebastian P. , Lehr Dennis , Kley Ernst‐Bernhard , Pacholski Claudia
Published: May 2014

A simple method for the fabrication of gold nanorings with reliable material composition and reproducible morphology that relies on a combination of top‐down and bottom‐up techniques is presented. Here, lithographically defined hole arrays are used as templates for the deposition of gold nanoparticles. The resulting gold nanoparticle rings are joined by electroless deposition of gold, thereby leading to the formation of gold nanoring arrays that show plasmonic resonance in their optical spectra at theoretically predicted wavelengths. In addition, the gold nanorings can be released from the template by extensive rinsing with water, thereby enabling their further functionalization or assembly and the re‐use of the template for the preparation of more nanorings.
Power Control for Cellular Communications with Time‐Varying Channel Uncertainties
Authors: Subramanian Sankrith , Shea John M. , Dixon Warren E.
Published: May 2014

Power control in a code‐division multiple access (CDMA) based cellular network is a challenging problem because the communication channels change rapidly because of multipath fading. These rapid fluctuations cause detrimental effects on the control efforts required to regulate the signal‐to‐interference plus noise ratios (SINRs) to the desired level. Thus, there is a need for power‐control algorithms that can adapt to rapid changes in the channel gain caused by multipath fading. Much of the previous work has either neglected the effects of fast fading, assumed that the fading is known, or assumed that all the link gains are known. In this paper, we model the effects of fast fading and develop practical strategies for robust power control based on SINR measurements in the presence of the fading. We develop a controller for the reverse link of a CDMA cellular system, and use a Lyapunov‐based analysis to prove that the SINR error is globally uniformly ultimately bounded. We also utilize a linear prediction filter that utilizes local SINR measurements and estimates of the Doppler frequency that can be derived from local SINR measurements to improve the estimate of the channel fading used in the controller. The power‐control algorithm is simulated for a cellular network with multiple cells, and the results indicate that the controller regulates the SINRs of all the mobile terminals (MTs) with low outage probability. In addition, a pulse‐code‐modulation technique is applied to allow the control command to be quantized for feedback to the transmitter. Simulation results indicate that the outage probabilities of all the MTs are still within the acceptable range if at least 3‐bit quantization is employed. Comparisons to a standard algorithm illustrate the improved performance of the predictive controller.
2013 feedstock supply and price projections and sensitivity analysis
Authors: Langholtz Matthew , Eaton Laurence , Turhollow Anthony , Hilliard Michael
Published: May 2014

Farmgate prices (i.e. price delivered roadside ready for loading and transport) for biomass feedstocks directly influence biofuel prices. Using the latest available data, marginal (i.e. price for the last ton) farmgate prices of $51, $63, and $67 dry ton−1 ($2011) are projected as necessary to provide 21 billion gallons of biofuels from about 250 million dry tons of terrestrial feedstocks in 2022 under price‐run deterministic, demand‐run deterministic, and stochastic simulations, respectively. Sources of uncertainty in these feedstock supply and price projections include conversion efficiency, global market impacts on crop price projections, crop yields, no‐till adoption, and climate. Under a set of low, high, and reference assumptions, these variables introduce an average of +/– $11 dry ton−1 (~15%) uncertainty of feedstock prices needed to meet EISA targets of 21 billion gallons of biofuels produced with 250 million dry tons of biomass in 2022. Market uncertainty justifies the need for fairly frequent (i.e. annual or biennial) re‐assessment of feedstock price projections to inform strategies toward commercialization of biofuels. Published in 2014 by John Wiley & Sons, Ltd
Single flexible nanofiber to achieve simultaneous photoluminescence–electrical conductivity bifunctionality
Authors: Sheng Shujuan , Ma Qianli , Dong Xiangting , Lv Nan , Wang Jinxian , Yu Wensheng , Liu Guixia
Published: May 2014

In order to develop new‐type multifunctional composite nanofibers, Eu(BA)3phen/PANI/PVP bifunctional composite nanofibers with simultaneous photoluminescence and electrical conductivity have been successfully fabricated via electrospinning technology. Polyvinyl pyrrolidone (PVP) is used as a matrix to construct composite nanofibers containing different amounts of Eu(BA)3phen and polyaniline (PANI). X‐Ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), vibrating sample magnetometry (VSM), fluorescence spectroscopy and a Hall effect measurement system are used to characterize the morphology and properties of the composite nanofibers. The results indicate that the bifunctional composite nanofibers simultaneously possess excellent photoluminescence and electrical conductivity. Fluorescence emission peaks of Eu3+ ions are observed in the Eu(BA)3phen/PANI/PVP photoluminescence–electrical conductivity bifunctional composite nanofibers. The electrical conductivity reaches up to the order of 10−3 S/cm. The luminescent intensity and electrical conductivity of the composite nanofibers can be tuned by adjusting the amounts of Eu(BA)3phen and PANI. The obtained photoluminescence–electrical conductivity bifunctional composite nanofibers are expected to possess many potential applications in areas such as microwave absorption, molecular electronics, biomedicine and future nanomechanics. More importantly, the design concept and construction technique are of universal significance to fabricate other bifunctional one‐dimensional naonomaterials. Copyright © 2014 John Wiley & Sons, Ltd.
Performance of prognostic scores in predicting long-term outcome following resection of colorectal liver metastases
Authors: Roberts K J , White A , Cockbain A , Hodson J , Hidalgo E , Toogood G J , Lodge J P A
Published: May 2014

Background

Ten-year survival appears to define cure following resection of colorectal liver metastases (CRLMs). Various scores exist to predict outcome at 5 years. This study applied several scores to a patient cohort with 10 years of actual follow-up to assess their performance beyond 5 years.

Methods

The study included consecutive patients who underwent liver resection at a single institution between 1992 and 2001. The ability of eight prognostic scoring systems to predict disease-free (DFS) and disease-specific (DSS) survival was analysed using the C-statistic.

Results

Among 286 patients, the 1-, 3-, 5- and 10-year actual DSS rates were 86·6, 58·3, 39·5 and 24·5 per cent respectively. Seventy patients underwent 105 further resections for recurrent disease, of which 84·8 per cent were within 5 years of follow-up. Analysis of C-statistics showed only one score – the Rees postoperative index – to be a significant predictor of DFS and DSS at all time points. The remaining scores performed less well, and regularly showed no significant improvement in predictive accuracy over what would be expected by chance alone. No score yielded a C-statistic in excess of 0·8 at any time point.

Conclusion

Although available risk scores can predict DFS and DSS, none does so with sufficient discriminatory accuracy to identify all episodes of recurrent disease. A non-negligible proportion of patients develop recurrent disease beyond 5 years of follow-up and so surveillance beyond this point may be advantageous.
Metabolism of Nω‐methylserotonin, a serotonergic constituent of black cohosh (Cimicifuga racemosa, L. (Nutt.)), by human liver microsomes
Authors: Nikolić Dejan , Li Jinghu , van Breemen Richard B.
Published: May 2014

The roots/rhizomes of black cohosh (Cimicifuga racemosa L. (Nutt.) (syn. Actaea racemosa L.) are a popular dietary supplements among women for management of menopausal symptoms. Although not estrogenic, Nω‐methylserotonin has been identified in black cohosh as a potent agonist of serotonin 5‐HT1A and 5‐HT7 receptors. In the present study, in vitro metabolism of Nω‐methylserotonin was investigated to gain insights into aspects of the bioavailability of this compound. The major metabolic pathway was determined to be conversion into 5‐hydroxyindole acetaldehyde catalyzed by the monoamine oxidase A (MAO‐A). 5‐Hydroxyindole acetaldehyde could be further oxidized to form 5‐hydroxyindole acetic acid by the action of microsomal aldehyde dehydrogenase or reduced to 5‐hydroxy tryptophol by the action of aldehyde reductase. The cytochrome P450 enzymes had only a minor role in the metabolism of Nω‐methylserotonin and then only when MAO‐A was inhibited. In many aspects, the metabolism of Nω‐methylserotonin was similar to the metabolism of serotonin, suggesting that this compound is unlikely to elicit CNS effects due to rapid metabolism by the widely distributed MAO‐A. Copyright © 2014 John Wiley & Sons, Ltd.
An optimized HPLC/MS/MS method for quantification of excitatory amino acids in rat hippocampus and its application in brain ischemia/reperfusion research
Authors: Xu Jia , Qian Zhonglian , Zhao Libo , Fang Yi
Published: May 2014

An optimized HPLC/MS/MS method was established to quantify glutamate (Glu) and aspartic acid (Asp) in rat hippocampus with glutamate‐d5 (Glu‐d5) as internal standard. The mass spectrometry was operated under the multiple reaction monitoring mode using electrospray ionization in the positive ion mode for Glu and negative ion mode for Asp. The retention times of Glu, Asp and Glu‐d5 were 1.53, 2.07 and 1.52 min, respectively. The linearity of calibration curves was good, with r2 > 0.99 and a lower limit of quantitation of 10 ng/mL. The intra‐day precisions (relative standard deviation, RSD) of Glu and Asp were in the range of 3.61–8.17 and 4.22–10.09%, respectively; the inter‐day precisions (RSD) of Glu and Asp were in the range of 3.57–5.19 and 2.49–5.04%, respectively. The accuracies of Glu and Asp were in the range of −2.10–6.20 and −0.90–10.00%, respectively. The recovery rates of 10, 100 and 1000 ng/mL were found to be 0.89 ± 0.24, 1.01 ± 0.10 and 0.90 ± 0.12 for Glu and 0.99 ± 0.26, 0.93 ± 0.07 and 1.13 ± 0.13 for Asp, respectively. This optimized method was successfully applied to quantify the concentration of Glu and Asp in rat hippocampus in brain ischemia/reperfusion research. Copyright © 2014 John Wiley & Sons, Ltd.
Comparative pharmacokinetics of cyclophosphamide administration alone and combination with vitamin B6 in rats
Authors: Ma Bingjie , Zhang Yuanyuan , Gu Liqiang , Jiang Yu , Hou Pengyi , Zeng Yan , Zhang Lunhui , Ju Ping , Bi Kaishun , Chen Xiaohui
Published: May 2014

A fast and sensitive high performance liquid chromatography coupled with mass spectrometry (LC‐MS) method was developed and validated for the determination of cyclophosphamide in rat plasma with and without the combination of vitamin B6. After addition of digoxin used as the internal standard (IS), plasma samples were extracted by protein precipitation with acetonitrile (1:1, v/v), and the analytes were separated by a Kromasil C18 column (150 × 4.6 mm, 5 µm) with a mobile phase of acetonitrile–0.1% formic acid water (40:60, v/v). The detection of the analyte was monitored in positive electrospray ionization by selected ion monitoringmode. The linear range was 0.01–40 µg/mL for cyclophosphamide. The intra‐ and inter‐day precision and accuracy were all <15%. The extraction recoveries and matrix effects of the analyte and IS were all within acceptable range. The selectivity of the method was satisfactory with no endogenous interference. The results for stabilities of cyclophosphamide and IS under various conditions were all within the acceptance criteria. The validated method was successfully applied to evaluate the drug–drug interaction of cyclophosphamide and vitamin B6 in rat plasma. The results showed no differences of pharmacokinetic behaviors between cyclophosphamide administration with and without vitamin B6. Copyright © 2014 John Wiley & Sons, Ltd.
Evaluation of Multipoint Dosing Strategy in a Miniaturized Tubular Reactor: Nitration of Salicylic Acid
Authors: Debnath Soujoy , Kienle Achim , Kulkarni Amol A.
Published: May 2014

A 2D non‐isothermal reaction engineering model for a tubular reactor was developed for a complex reaction network of salicylic acid nitration. The influence of different operating and design parameters was studied to minimize the amount of secondary nitration products and limit the maximum temperature inside the reactor. Critical temperature effects were observed for larger reaction tubes, whereas close to isothermal conditions were perceived in smaller tubes. With single‐point dosing of both reactants, complete conversion can be achieved but formation of secondary nitration products cannot be avoided. For a given number of dosing points, a suitable combination of the operating parameters allowed to achieve complete conversion and better yield of the desired product.
Improved Metal‐Adhesive Polymers from Copper(I)‐Catalyzed Azide–Alkyne Cycloaddition
Authors: Accurso Adrian A. , Delaney Mac , O'Brien Jeff , Kim Hyonny , Iovine Peter M. , Díaz David Díaz , Finn M. G.
Published: May 2014

Electrically conductive adhesive polymers offer many potential advantages relative to SnPb solders, including reduced toxicity, low cost, low processing temperatures, and the ability to make application‐specific formulations. Polymers generated from the copper(I)‐catalyzed cycloaddition (CuAAC) reaction between multivalent azides and alkynes have previously been identified as strong metal‐binding adhesives. Herein we demonstrate that the performance of these materials can be remarkably improved by the incorporation of a flexibility‐inducing difunctionalized component and a tertiary amine additive in optimized concentrations. The best formulations were identified by means of rapid adhesion testing of a library of potential candidates by using a custom‐built instrument and validated in an American Society for Testing and Materials (ASTM)‐standard lap‐shear test. Characteristic phase transitions were identified by differential scanning calorimetry (DSC) for adhesives with and without the additives as a function of curing temperature. The incorporation of flexible components was found to more than double the strength of the adhesive. Moreover, the adhesive was made electrically conductive by the inclusion of 20 wt % silver‐coated copper flakes and further improved in this regard by the incorporation of multiwalled carbon nanotubes in the formulation.
Scale‐up Behaviour of Intensive Mixers for Lignite Granulation for Material Usage
Authors: Fehse Franz , Sperling Alexander , Herdegen Volker , Schröder Hans‐Werner , Naundorf Tom , Repke Jens‐Uwe
Published: May 2014

Die stoffliche Nutzung der Braunkohle erfordert neue Verfahren für die Rohstoffaufbereitung. Um die im Labormaßstab entwickelte Granulierung von Braunkohle in den technischen Maßstab zu überführen, wurde die Übertragbarkeit in einem Intensivmischer verschiedener Baugrößen untersucht. Dabei können sich, bei gleichen Parametersätzen, Unterschiede in der Körnung einstellen. Mit dem Abrollweg wurde jedoch eine Übertragungskenngröße identifiziert, die durch Anpassung der Parametersätze an die Mischergröße ein Granulat gleichbleibender Qualität und damit eine Maßstabsübertragung ermöglicht.
The Non‐Aqueous Processing of Canadian Oil Sand
Authors: Schmidt Elisabeth , Wacker Bernd , Peuker Urs A.
Published: May 2014

Die herkömmliche Aufbereitung des im Tagebau geförderten kanadischen Ölsands bedarf hohen energetischen Aufwands und birgt große ökologische Probleme. Daher wurde ein alternatives Aufbereitungsverfahren entwickelt, das die Folgekosten und Umweltrisiken umgeht. Das im Ölsand enthaltene Bitumen wird durch organische Lösungsmittel herausgelöst. Mithilfe einer durch einen Waschschritt erweiterten Dampf‐Druckfiltration werden die gelösten und festen Bestandteile voneinander getrennt. Damit wurde das Ziel erreicht, eine möglichst hohe Bitumenausbeute sowie einen deponierbaren Sand zu erhalten.
Optimisation of Tetrahydroisoquinoline‐Based Chimeric Microtubule Disruptors
Authors: Dohle Wolfgang , Leese Mathew P. , Jourdan Fabrice L. , Chapman Christopher J. , Hamel Ernest , Ferrandis Eric , Potter Barry V. L.
Published: May 2014

Tetrahydroisoquinoline (THIQ)‐based “chimeric” microtubule disruptors were optimised through modification of the N‐benzyl motif, in concert with changes at C3 and C7, resulting in the identification of compounds with improved in vitro antiproliferative activities (e.g. 15: GI50 20 nM in DU‐145). The broad anticancer activity of these novel structures was confirmed in the NCI 60‐cell line assay, with 12 e,f displaying MGM values in the 40 nM region. In addition, their profiles as inhibitors of tubulin polymerisation and colchicine binding to tubulin were confirmed. Compound 15, for example, inhibited tubulin polymerisation with an IC50 of 1.8 μM, close to that of the clinical drug combretastatin A‐4, and also proved effective at blocking colchicine binding. Additionally, compound 20 b was identified as the only phenol in the series to date showing both better in vitro antiproliferative properties than its corresponding sulfamate and excellent antitubulin data (IC50=1.6 μM). Compound 12 f was selected for in vivo evaluation at the NCI in the hollow fibre assay and showed very good activity and wide tissue distribution, illustrating the value of this template for further development.
Increased age and race‐specific incidence of cervical cancer after correction for hysterectomy prevalence in the United States from 2000 to 2009
Authors: Rositch Anne F. , Nowak Rebecca G. , Gravitt Patti E.
Published: May 2014

BACKGROUND

Invasive cervical cancer is thought to decline in women over 65 years old, the age at which cessation of routine cervical cancer screening is recommended. However, national cervical cancer incidence rates do not account for the high prevalence of hysterectomy in the United States.

METHODS

Using estimates of hysterectomy prevalence from the Behavioral Risk Factor Surveillance System (BRFSS), hysterectomy‐corrected age‐standardized and age‐specific incidence rates of cervical cancer were calculated from the Surveillance, Epidemiology, and End Results (SEER) 18 registry in the United States from 2000 to 2009. Trends in corrected cervical cancer incidence across age were analyzed using Joinpoint regression.

RESULTS

Unlike the relative decline in uncorrected rates, corrected rates continue to increase after age 35‐39 (APCCORRECTED = 10.43) but at a slower rate than in 20‐34 years (APCCORRECTED = 161.29). The highest corrected incidence was among 65‐ to 69‐year‐old women, with a rate of 27.4 cases per 100,000 women as opposed to the highest uncorrected rate of 15.6 cases per 100,000 aged 40 to 44 years. Correction for hysterectomy had the largest impact on older, black women given their high prevalence of hysterectomy.

CONCLUSIONS

Correction for hysterectomy resulted in higher age‐specific cervical cancer incidence rates, a shift in the peak incidence to older women, and an increase in the disparity in cervical cancer incidence between black and white women. Given the high and nondeclining rate of cervical cancer in women over the age of 60 to 65 years, when women are eligible to exit screening, risk and screening guidelines for cervical cancer in older women may need to be reconsidered. Cancer 2014;120:2032–2038. © 2014 American Cancer Society.
Advances in Modeling Sorption and Diffusion of Moisture in Porous Reactive Materials
Authors: Harley Stephen J. , Glascoe Elizabeth A. , Lewicki James P. , Maxwell Robert S.
Published: May 2014

Water‐vapor‐uptake experiments were performed on a silica‐filled poly(dimethylsiloxane) (PDMS) network and modeled by using two different approaches. The data was modeled by using established methods and the model parameters were used to predict moisture uptake in a sample. The predictions are reasonably good, but not outstanding; many of the shortcomings of the modeling are discussed. A high‐fidelity modeling approach is derived and used to improve the modeling of moisture uptake and diffusion. Our modeling approach captures the physics and kinetics of diffusion and adsorption/desorption, simultaneously. It predicts uptake better than the established method; more importantly, it is also able to predict outgassing. The material used for these studies is a filled‐PDMS network; physical interpretations concerning the sorption and diffusion of moisture in this network are discussed.
Yttrium Oxide/Gadolinium Oxide‐Modified Platinum Nanoparticles as Cathodes for the Oxygen Reduction Reaction
Authors: Luo Yun , Habrioux Aurélien , Calvillo Laura , Granozzi Gaetano , Alonso‐Vante Nicolas
Published: May 2014

Rare‐earth‐element (Y, Gd) modified Pt nanoparticles (NPs) supported on a carbon substrate (Vulcan XC‐72) are synthesized via a water‐in‐oil chemical route. In both cases, X‐ray diffraction (XRD) measurements show the non‐formation of an alloyed material. Photoemission spectroscopy (XPS) results reveal that Y and Gd are oxidized. Additionally, no evidence of an electronic modification of Pt can be brought to light. Transmission electron microscopy (TEM) studies indicate that Pt‐Y2O3 and Pt‐Gd2O3 particles are well dispersed on the substrate—and that their average particle sizes are smaller than the Pt‐NP sizes. The catalytic activity of the Pt‐Y2O3/C and Pt‐Gd2O3/C catalysts towards the oxygen reduction reaction (ORR) is studied in a 0.5 M H2SO4 electrolyte. The surface and mass specific activities of the Pt‐Y2O3/C catalyst towards the ORR at 0.9 V (vs. the reversible hydrogen electrode, RHE) are (54.3±1.2) μA cm−2Pt and MA=(23.1±0.5) mA mg−1Pt, respectively. These values are 1.3‐, and 1.6‐fold higher than the values obtained with a Pt/C catalyst. Although the as‐prepared Pt‐Gd2O3/C catalyst has a lower catalytic activity for the ORR compared to Pt/C, the heat‐treated sample shows a surface specific activity of about (53.0±0.7) μA cm−2Pt, and a mass specific activity (MA) of about (18.2±0.5) mA mg−1Pt at 0.9 V (vs. RHE). The enhancement of the ORR kinetics on the Pt‐Y2O3/C and heat‐treated Pt‐Gd2O3/C catalysts could be associated with the formation of platinum NPs presenting modified surface properties.
Smart antenna‐assisted spectrum sensing for robust detection in cognitive radio networks
Authors: Qing Haobo , Liu Yuanan , Xie Gang
Published: May 2014

In this paper, we consider the problem of multiband spectrum sensing by employing smart antenna arrays at the cognitive receiver. Although energy detection is widely used for spectrum sensing in cognitive radio networks because of its simplicity and accuracy, it is severely deteriorated by the noise uncertainty. This paper introduces robust spectrum sensing techniques to circumvent this difficulty, which operate simultaneously over the total frequency channels rather than a single channel each time. To enhance the detection performance, the proposed schemes jointly utilize the information of eigenvalues and eigenvectors, signal and noise subspace components in conjunction with the likelihood functions and Gerschgorin radii. Neither subjective decision threshold setting nor the estimation of noise power is required in our schemes, making them robust to noise uncertainty. Simulations are presented to validate the performance of the proposed schemes, and the results show that our schemes can outperform other existing spectrum sensing methods. Copyright © 2014 John Wiley & Sons, Ltd.
Diagnostic benefits and cost‐effectiveness of on‐site imprint cytology adequacy evaluation of core needle biopsies of bone lesions
Authors: Kubik Melanie J. , Mohammadi Amir , Rosa Marilin
Published: May 2014

Background

Core needle biopsy (CNB) is a well‐established, successful technique for the diagnosis of various organ system lesions. To increase diagnostic yield, on‐site cytologic evaluation of adequacy (OCA) is routinely performed at many institutions. Numerous studies evaluating the impact of OCA on CNB have been published. However, little has been said regarding accuracy of OCA for bone lesions.

Methods

To evaluate this, we reviewed our experience during a two‐year period, and compared OCA results with the final diagnosis of the corresponding CNB. For the study, diagnoses were divided into three categories: malignant, benign, and nonspecific/nondiagnostic findings.

Results

Sixty‐one cases were included. During OCA, 25 cases were diagnosed as malignant, three cases as benign, and 33 as nonspecific/nondiagnostic. On histologic evaluation, 29 cases were malignant, 16 were benign, and 16 were classified as nonspecific/nondiagnostic. Concordance with final CNB diagnosis was seen in 100% of malignant, 67% of benign, and 45% of nonspecific/nondiagnostic on‐site cytology evaluations. The overall diagnostic success rate of OCA for malignancy was 86% (25/29). The success rate of OCA for benign lesions was only 13%. Fifty‐four percent of cases were diagnosed as nonspecific/nondiagnostic on‐site. This category included four false negative cases.

Conclusions

We conclude that for lesions with a suspicion of malignancy, OCA is a valuable adjuvant diagnostic tool. However, for cases with a benign or nonspecific clinical impression, OCA has a limited diagnostic role. Careful selection of cases in which OCA is beneficial is necessary to maintain accuracy and to limit procedure costs. Diagn. Cytopathol. 2014;42:506–513. © 2013 Wiley Periodicals, Inc.
The interim regulated legal market for NPS (‘legal high’) products in New Zealand: The impact of new retail restrictions and product licensing
Authors: Wilkins Chris
Published: May 2014

New Zealand has recently established the world's first regulated legal market for new psychoactive products (NPS) (i.e. ‘legal highs’). While the new regime is currently in a transitional phase, a range of retail restrictions and an interim licensing regime for NPS products and operators has been introduced. A product safety assessment framework has been developed to determine if a product should receive an interim licence. As a result of the licensing requirements, the number of NPS retail outlets fell from 3000– 4000 largely convenience stores to 156 specialty stores, and the number of legally available NPS products fell from 200 to fewer than 46. Some of the licensed products contain potent cannabinoid compounds. The licensing system provided, for the first time, information on all the products and operators involved in the sector, and this will assist future monitoring. The effectiveness of the new product safety assessment framework will depend on the quality of the data available on adverse cases. This is a challenge as self‐reported information from users is often unreliable, and some emergency department cases do not have all the information required to make an accurate assessment. These data limitations indicate the need for retrospective studies of NPS adverse cases and additional test data. While the new legislation initially reduced the number of NPS retailers by prohibiting convenience outlets, new specialized NPS retail outlets may emerge as the new sector expands. Empirical research is required to measure the impact of the reduction in retail outlets and products on NPS availability. Copyright © 2014 John Wiley & Sons, Ltd.
Catalytic Activity of Chloro and Triflate Manganese(II) Complexes in Epoxidation Reactions: Reusable Catalytic Systems for Alkene Epoxidation
Authors: Rich Jordi , Manrique Ester , Molton Florian , Duboc Carole , Collomb Marie‐Noëlle , Rodríguez Montserrat , Romero Isabel
Published: May 2014

The catalytic oxidation of a series of alkenes by three MnII complexes, MnCl2[(–)‐L]2 (1), ({MnCl[(–)‐L]}2(μ‐Cl)2) (2), and Mn(CF3SO3)2[(–)‐L]2 (3), having the bidentate N‐ligand (–)‐pinene[5,6]bipyridine, (–)‐L, and using peracetic acid as oxidant in acetonitrile is described. The performance of catalysts 1 and 2 is enhanced by the use of additives (NaHCO3 and imidazole) and also using a [bmim]/acetonitrile mixture as reaction media. The latter conditions allow recyclability of the catalytic system, keeping good selectivity and conversion values in some cases. The nature of the species formed in acetonitrile after the addition of peracetic acid has been investigated through EPR and UV/Vis spectroscopy. The results point to the formation of high‐valent manganese species, among which a di‐μ‐oxo‐bridged Mn2(III,IV) binuclear species was unambiguously identified for complex 3 through a typical 16‐line EPR signature.
Iron‐Mediated Direct Arylation of Unactivated Arenes in Air
Authors: Huang Yuxing , Moret Marc‐Etienne , Klein Gebbink Robertus J. M.
Published: May 2014

Biaryls are a common motif in both natural and synthetic chemicals. Several methods have recently been reported for the preparation of these compounds using direct arylation catalyzed by iron, other base metals, or transition‐metal‐free systems. To date, these methods have all required inert and/or forcing conditions, which limited their application in routine organic synthesis. In this article we report a protocol for direct arylation using a convenient FeCl3/1,10‐phenanthroline system as precatalyst. The reaction proceeds under mild conditions (100 °C), under air, and with non‐distilled solvent.
Germany for the World Cup!?
Authors: Tolan Metin
Published: May 2014

“It's what happens on the pitch that matters,” said Adi Preissler and Otto Rehhagel, former German footballers and coaches, in some oft‐quoted words of football wisdom. Statistically, the German national side managed by Jogi Löw is 6.5 times more likely than an “average” team to finally bring home the title again. Here is a scientific approach to a World Cup forecast that uses a few mathematical tricks and computer simulations.
Seromucinous hamartoma in the nasal cavity medial to the middle turbinate: Report of 2 cases and review of the literature
Authors: Huang Chien‐Chia , Lee Ta‐Jen , Huang Chi‐Che , Wu Pei‐Wen
Published: May 2014

Background

Seromucinous hamartoma, a type of epithelial hamartoma, is a rare benign glandular proliferation of the sinonasal tract and nasopharynx. Herein, we present 2 rare cases of seromucinous hamartoma arising in the nasal cavity medial to the middle turbinate.

Methods and Results

This is a case report of 2 patients diagnosed with seromucinous hamartoma of the nasal cavity and a review of the literature.

Conclusion

Seromucinous hamartoma of the nasal cavity is an exceedingly rare diagnosis but should be included in the differential diagnosis of a posterior nasal tumor. Most cases arise from the posterior nasal cavity medial to the middle turbinate rather than lateral to the middle turbinate. © 2014 Wiley Periodicals, Inc. Head Neck 37: E15‐E18, 2015
Reconstructive strategies for dermatofibrosarcomas of the face: Role of regenerative dermal templates
Authors: Sartore Leonardo , Erica Dalla Venezia , Puppa Alessandro Della , Bedogni Alberto , Campana Luca , Giatsidis Giorgio
Published: May 2014

Background

Dermatofibrosarcomas protuberans is a challenging cutaneous tumor from an oncologic and reconstructive surgical point of view. Involvement of functionally and aesthetically sensitive areas, such as facial units, in young patients accounts for more demanding cases. An updated evaluation of most beneficial excisional/reconstructive strategies in these cases is still lacking.

Methods

We investigated the potential of regenerative dermal templates in staged postoncologic reconstructive management of a young woman affected by a dermatofibrosarcomas protuberans of the forehead involving the frontal bone.

Results

Final result was optimal in terms of cosmetic and functional recovery, obtaining a pliability, softness, and color similar to surrounding healthy skin.

Conclusion

In facial dermatofibrosarcomas protuberans, staged reconstruction with regenerative dermal templates provides a conservative yet safe and effective management, achieving optimal aesthetic outcomes. We suggest its adoption as first‐line treatment in facial dermatofibrosarcomas protuberans that cannot be repaired by direct suture and in equivalent benign yet challenging cases. © 2014 Wiley Periodicals, Inc. Head Neck 37: E8–E11, 2015
Early oral feeding after total laryngectomy: A systematic review
Authors: Aires Felipe Toyama , Dedivitis Rogério Aparecido , Petrarolha Sílvia Miguéis Picado , Bernardo Wanderley Marques , Cernea Claudio Roberto , Brandão Lenine Garcia
Published: May 2014

Background

Early oral feeding for patients who underwent total laryngectomy is still controversial. The purpose of this study was to evaluate the safety of initiating early oral feeding after total laryngectomy regarding pharyngocutaneous fistula. The survey included research in MEDLINE, EMBASE, and LILACS.

Methods

The intervention analyzed was early oral feeding (<5 days), whereas the control group received late oral feeding (>7 days) after total laryngectomy.

Results

From 304 studies, 4 randomized clinical trials with 180 patients were selected. In the early oral feeding group, the incidence was 6.7%, whereas in the late oral feeding group it was 10%, with no statistically significant difference (IC95% −0.11 to 0.05; p = .42; I2 = 0%). Four cohort studies with 490 patients were also selected. In the early oral feeding group, the incidence was 12.2%, whereas in the other group, it was 10.1%, with no statistically significant difference (IC95% −0.05 to 0.08; p = .67; I2 = 0%).

Conclusion

There is no increase in pharyngocutaneous fistula rates in patients who receive early oral feeding after total laryngectomy. © 2014 Wiley Periodicals, Inc. Head Neck 37: 1532–1535, 2015