bluuebunny/crossref_metadata_2025 huggingface dataset:
Age‐at‐death estimation in an Italian historical sample: A test of the Suchey‐Brooks and transition analysis methods
Authors: Godde Kanya , Hens Samantha M.
Published: August 2012

A growing body of research is demonstrating increased accuracy in aging from a relatively new method, transition analysis. Although transition analysis was developed for paleodemographic research, a majority of subsequent studies have been in the forensic arena, with very little work in bioarchaeological contexts. Using the Suchey‐Brooks pubic symphysis phases, scored on a target sample of historic Italians from the island of Sardinia, we compare accuracy of aging between transition analysis combined with a Bayesian approach and the standard Suchey‐Brooks age ranges. Because of the difficulty in identifying a reasonable informative prior for bioarchaeological samples, we also compared results of both an informative prior and a uniform prior for age estimation.

Published ages‐of‐transition for the Terry Collection and Balkan genocide victims were used in conjunction with parameters generated from Gompertz hazard models derived from the priors. The ages‐of‐transition and hazard parameters were utilized to calculate the highest posterior density regions, otherwise known as “coverages” or age ranges, for each Suchey‐Brooks phase. Each prior, along with the parameters, were input into cumulative binomial tests. The results indicate that the Bayesian approach outperformed the Suchey‐Brooks technique alone. The Terry Collection surpassed the Balkans as a reasonable sample from which to derive transition analysis parameters. This discrepancy between populations is due to different within phase age‐at‐death distributions that reflect differences in aging between the populations. These results indicate bioarchaeologists should strive to apply a Bayesian analysis when aging historic and archaeological populations by employing an informative prior. Am J Phys Anthropol 149:259–265, 2012. © 2012 Wiley Periodicals, Inc.
Effects of silica/multiwall carbon nanotube hybrid fillers on the properties of natural rubber nanocomposites
Authors: Ismail H. , Ramly A. F. , Othman N.
Published: August 2012

In this study, multiwalled carbon nanotubes (MWCNTs) and silica were used as hybrid fillers in natural rubber (NR) nanocomposites. The addition of MWCNTs and silica to NR was varied with the total filler loading fixed at 30 phr. The curing characteristics and mechanical, thermal, and morphological properties were investigated in this study. The results show that the scorch and curing time decreased as the MWCNT loading increased in the silica/MWCNT hybrid, but the maximum torque was increased by about 35%. The highest tensile strength was achieved at a loading ratio of 29 phr silica/1 phr MWCNTs. As the MWCNT loading increased in the silica/MWCNT hybrid, the tensile strength, elongation at break, and fatigue life decreased. However, the tensile modulus and rubber filler interaction increased. The scanning electron microscopy results show a good dispersion and better interaction between silica and the MWCNTs with the NR matrix at a 29/1 silica/MWCNT loading ratio. As the MWCNT loading ratio increased, the agglomeration of the MWCNTs became dominant and reduced the reinforcing effect of the MWCNTs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Preparation and properties of 4, 4′‐diphenylmethane diisocyanate blocking modified poly(propylene carbonate)
Authors: Pang Sujuan , Xu Nai , Xu Guang , Pan Lisha , Lin Qiang , Wang Xin
Published: August 2012

Poly(propylene carbonate) (PPC) is inferior in thermal stability and liable to incur thermal degradation, especially in the existence of residual bimetal catalyst. In this article, PPC containing residual catalyst was end‐capped with 4, 4′‐diphenylmethane diisocyanate (MDI) through melt compounding. The blends were characterized by infrared spectra, melt flow index (MFI), gel permeation chromatography (GPC), gel content measurement, thermogravimetric analysis, scanning electron microscopy, and tensile test. The effect of MDI on thermal stability, molecular weight, and tensile properties of PPC was studied. Thermal degradation kinetics of neat PPC and PPC+MDI blending samples was discussed with Friedman method. MFI, GPC, and gel content measurements showed that mainly end‐capping reaction was carried out on PPC chains when 0.1% of MDI was added. However, as the amount of MDI exceeded to 0.3%, end‐capping, chain‐extension, and crosslinking reactions were synchronously carried out on PPC. Results showed that the end‐capping, chain‐extension, and crosslinking reaction occurring between PPC and MDI could effectively inhibit the unzipping degradation even when the residual catalyst was not removed thoroughly. When the content of MDI reached 1.0%, the initial degradation temperatures (T‐5%) increased from 176.26°C for neat PPC to 259.56°C. As a result, the processing temperature range and processing time were largely extended, and the heat resistance of PPC was improved remarkably. Meanwhile, the tensile property of the modified PPC was enhanced obviously. It may be due to the fact that the molecular weight and gel content of PPC were increased with the increasing amount of MDI. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Cure kinetics of an acrylated epoxidized hemp oil‐based bioresin system
Authors: Francucci Gaston , Cardona Francisco , Manthey Nathan W.
Published: August 2012

In this work, the cure kinetics of a novel acrylated epoxidized hemp oil (AEHO)‐based bioresin was investigated for the first time by differential scanning calorimetry (DSC) using both isothermal and nonisothermal conditions. This new bioresin was synthesized by the acrylation of a previously epoxidized hemp oil (EHO) bioresin. The curing of the AEHO bioresin showed an autocatalytic behavior with the vitrification phenomenon preventing the conversion reaching unity for all the temperatures studied. It was found that the curing behavior can be modeled with high accuracy using a modified Kamal autocatalytic model that takes into account the vitrification phenomenon. Dynamic activation energies were determined from the Kissinger and Ozawa–Flynn–Wall methods, resulting in 58.87 and 62.02 kJmol−1, respectively. In addition, activation energies associated with the autocatalytic model constants, k1 and k2, were established to be equal to 58.94 and 45.32 kJmol−1, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Influence of temperature on mechanical properties of jute/biopolymer composites
Authors: Løvdal Alexandra , Laursen Louise Løcke , Andersen Tom Løgstrup , Madsen Bo , Mikkelsen Lars Pilgaard
Published: August 2012

Biopolymers and natural fibers are receiving wide attention for the potential to have good performance composites with low environmental impact. A current limitation of most biopolymers is however their change in mechanical properties at elevated temperatures. This study investigates the mechanical properties of two biomass‐based polymers, polylactic acid (PLA) and cellulose acetate (CA), as a function of ambient temperature in the range from 5 to 80°C. Tests were done for neat polymers and for jute fiber/biopolymer composites. Micromechanical models were applied to back‐calculate the reinforcement efficiency of the jute fibers. The elastic modulus of neat PLA is constant until a temperature of about 45°C, after which it is decreased rapidly. For neat CA, the elastic modulus is almost constant in the whole temperature range. The maximum stress of the neat biopolymers is consistently reduced. For the jute fiber composites, both the elastic modulus and maximum stress are reduced when the temperature is increased. For the elastic modulus, this is shown to be due to a reduction in the reinforcement efficiency of the jute fibers; i.e., a reduction in the back‐calculated effective elastic modulus of the fibers. Altogether, the results demonstrate that the thermal sensitivity parameters typically provided for polymers, e.g., the glass transition temperature and the heat deflection temperature, cannot be used as sole parameters for determining the gradual change in mechanical properties of polymers and composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
SILKWORM 30K PROTEIN INHIBITS ECDYSONE‐INDUCED APOPTOSIS BY BLOCKING THE BINDING OF ULTRASPIRACLE TO ECDYSONE RECEPTOR‐B1 IN CULTURED Bm5 CELLS
Authors: Kim Mi Young , Song Hwa Young , Kim Jin Hee , Kim Bo Yong , Park Sun Whan , Sung Dong Kyung , Park Hun Hee , Jeon Soung Hoo , Chung In Sik , Lee Bong Hee
Published: August 2012

This study investigates the mechanism through which increased 30K protein inhibits ecdysone‐induced apoptosis in the Bm5 silkworm ovarian cell line. Treatment of Bm5 cells with 20‐hydroxyecdysone (20E) after transfection with the pIZT/V5‐His control vector triggered apoptosis, but 20E treatment did not trigger apoptosis in Bm5 cells transfected with the pIZT/30K/V5‐His vector. To confirm its inhibitory effect on apoptosis, 30K protein was first purified from Escherichia coli transformed with a 30K expression vector and used to generate specific antibodies in mice. Anti‐30K antiserum was used to confirm synthesis of the 30K protein in pIZT/30K/V5‐His‐transfected Bm5 cells and to detect 30K protein binding to the ecdysone receptor‐B1 (EcR‐B1). Anti‐30K antiserum was used to immunoprecipitate protein complexes containing 30K from Bm5 cells transfected with pIZT/30K/V5‐His vector and treated with 20E. We observed that 30K proteins bound primarily to the EcR‐B1 and not to ultraspiracle (USP). Reciprocal immunoprecipitation of EcR‐B1‐containing complexes from Bm5 cells transfected with control pIZT/V5‐His vector and treated with 20E showed that EcR‐B1 bound to USP in the absence of 30K but did not bind to USP in pIZT/30K/V5‐His‐transfected Bm5 cells. These results demonstrate that 30K proteins block USP binding to EcR‐B1 through formation of a 30K/EcR‐B1 complex, resulting in inhibition of 20E‐induced Bm5 cell apoptosis.
Beyond growth rate 0.6: Corynebacterium glutamicum cultivated in highly diluted environments
Authors: Grünberger Alexander , van Ooyen Jan , Paczia Nicole , Rohe Peter , Schiendzielorz Georg , Eggeling Lothar , Wiechert Wolfgang , Kohlheyer Dietrich , Noack Stephan
Published: August 2012

Fast growth of industrial microorganisms, such as Corynebacterium glutamicum, is a direct amplifier for the productivity of any growth coupled or decoupled production process. Recently, it has been shown that C. glutamicum when grown in a novel picoliter bioreactor (PLBR) exhibits a 50% higher growth rate compared to a 1 L batch cultivation [Grünberger et al. (2012) Lab Chip]. We here compare growth of C. glutamicum with glucose as substrate at different scales covering batch cultivations in the liter range down to single cell cultivations in the picoliter range. The maximum growth rate of standard batch cultures as estimated from different biomass quantification methods is ${\hat {\mu }} = 0.42\pm 0.03\,{\rm h}^{- 1} $ even for microtiter scale cultivations. In contrast, growth in a microfluidic perfusion system enabling analysis of single cells reproducibly reveals a higher growth rate of ${\hat {\mu }} = 0.62\pm 0.02\,{\rm h}^{- 1} $. When in the same perfusion system cell‐free supernatant from exponentially grown shake flask cultures is used the growth rate of single cells is reduced to ${\hat {\mu }} = 0.47\pm 0.02\,{\rm h}^{- 1} $. Likewise, when fresh medium is additionally supplied with 5 mM acetate, a growth rate of ${\hat {\mu }} = 0.51\pm 0.01\,{\rm h}^{- 1} $ is determined. These results prove that higher growth rates of C. glutamicum than known from typical batch cultivations are possible, and that growth is definitely impaired by very low concentrations of byproducts such as acetate. Biotechnol. Bioeng. 2013; 110: 220–228. © 2012 Wiley Periodicals, Inc.
Refolding of detergent‐denatured lysozyme using β‐cyclodextrin‐assisted ion exchange chromatography
Authors: Zhang Li , Zhang Qinming , Wang Chaozhan
Published: August 2012

Chromatography‐based protein refolding is widely used. Detergent is increasingly used for protein solubilization from inclusion bodies. Therefore, it is necessary to develop a refolding method for detergent‐denatured/solubilized proteins based on liquid chromatography. In the present work, sarkosyl‐denatured/dithiothreitol‐reduced lysozyme was used as a model, and a refolding method based on ion exchange chromatography, assisted by β‐cyclodextrin, was developed for refolding detergent‐denatured proteins. Many factors affecting the refolding, such as concentration of urea, concentration of β‐cyclodextrin, pH and flow rate of mobile phases, were investigated to optimize the refolding conditions for sarkosyl‐denatured lysozymes. The results showed that the sarkosyl‐denatured lysozyme could be successfully refolded using β‐cyclodextrin‐assisted ion exchange chromatography. Copyright © 2012 John Wiley & Sons, Ltd.
Droplet aerodynamics, cellular uptake, and efficacy of a nebulizable corticosteroid nanosuspension are superior to a micronized dosage form
Authors: Britland Stephen , Finter Wayne , Chrystyn Henry , Eagland Donald , Abdelrahim Mohamed E.
Published: August 2012

Inhaled corticosteroids are considered to be an effective prophylactic against the morbid symptoms of several lung diseases, but scope remains for improvement in drug delivery technology to benefit bioavailability and treatment compliance. To ascertain whether dosage form might influence bioavailability, the emission characteristics and efficacy of a nanoparticulate budesonide formulation (Nanagel®) were compared with those of a proprietary micronized suspension (Pulmicort®) when delivered as a nebulized aerosol to human airway epithelial cells in a culture model. Having the visual appearance of a clear solution, Nanagel® was delivered by both jet and vibrating mesh nebulizers as an increased fine particle fraction and with a smaller mass median aerodynamic diameter (MMAD) compared to the micronized suspension. Quantitative high performance liquid chromatography (HPLC) analysis of cultured epithelia one hour after treatment with Nanagel® revealed a significantly greater cellular accumulation of budesonide when compared with Pulmicort® for an equivalent dose, a differential which persisted 24 and 48 h later. A quantitative in vitro assay measuring the activity of enzymes involved in superoxide production revealed that stressed HaCaT cells (a long‐lived, spontaneously immortalized human keratinocyte line) treated with Nanagel® continued to show significantly greater attenuation of inflammatory response compared with Pulmicort®‐treated cells 24 h after the application of an equivalent budesonide dose. The present in vitro findings suggest that formulation of inhalable drugs such as budesonide as aerosolized nanoparticulate, rather than microparticulate, suspensions can enhance bioavailability with concomitant improvements in efficacy. © 2012 American Institute of Chemical Engineers Biotechnol. Prog., 2012
An implication of novel methodology to study pancreatic acinar mitochondria under in situ conditions
Authors: Manko Bohdan O. , Klevets Myron Yu. , Manko Volodymyr V.
Published: August 2012

Mitochondria maintain numerous energy‐consuming processes in pancreatic acinar cells, yet characteristics of pancreatic mitochondrial oxidative phosphorylation in native conditions are poorly studied. Besides, it is not known which type of solution is most adequate to preserve functions of pancreatic mitochondria in situ. Here we propose a novel experimental protocol suitable for in situ analysis of pancreatic mitochondria metabolic states. Isolated rat pancreatic acini were permeabilized with low doses of digitonin. Different metabolic states of mitochondria were examined in KCl‐ and sucrose‐based solutions using Clark oxygen electrode. Respiration of digitonin‐treated, unlike of intact, acini was substantially intensified by succinate or mixture of pyruvate plus malate. Substrate‐stimulated respiration rate did not depend on solution composition. In sucrose‐based solution, oligomycin inhibited State 3 respiration at succinate oxidation by 65.4% and at pyruvate plus malate oxidation by 60.2%, whereas in KCl‐based solution, by 32.0% and 36.1%, respectively. Apparent respiratory control indices were considerably higher in sucrose‐based solution. Rotenone or thenoyltrifluoroacetone severely inhibited respiration, stimulated by pyruvate plus malate or succinate, respectively. This revealed low levels of non‐mitochondrial oxygen consumption of permeabilized acinar cells. These results suggest a stronger coupling between respiration and oxidative phosphorylation in sucrose‐based solution. Copyright © 2012 John Wiley & Sons, Ltd.
Solid Acid Catalysts for Coumarin Synthesis by the Pechmann Reaction: MOFs versus Zeolites
Authors: Opanasenko Maksym , Shamzhy Mariya , Čejka Jiří
Published: August 2012

The catalytic behavior of metal–organic frameworks Cu‐benzene‐1,3,5‐tricarboxylate (CuBTC) and Fe‐benzene‐1,3,5‐tricarboxylate (FeBTC) was investigated in the Pechmann condensation of different phenols (resorcinol, pyrogallol, and naphthol) with ethyl acetoacetate and compared with large‐pore zeolites beta (BEA) and ultrastable Y (USY). Zeolites BEA and USY exhibited high activity in transformations of the most active substrates (resorcinol and pyrogallol) but a low conversion of naphthol was observed. Almost total transformation of naphthol (94–98 % conversion) to the target product was achieved within 24 h of the reaction time over CuBTC and FeBTC. We assume that the regularity in the arrangement of active sites within the framework of CuBTC, which results in the existence of 2 active centers in close proximity, is of critical importance to the transformation of naphthol in the Pechmann reaction that leads to coumarin.
Efficient Cluster‐Based Catalysts for Asymmetric Hydrogenation of α‐Unsaturated Carboxylic Acids
Authors: Moberg Viktor , Duquesne Robin , Contaldi Simone , Röhrs Oliver , Nachtigall Jonny , Damoense Llewellyn , Hutton Alan T. , Green Michael , Monari Magda , Santelia Daniela , Haukka Matti , Nordlander Ebbe
Published: August 2012

The new clusters [H4Ru4(CO)10(μ‐1,2‐P‐P)], [H4Ru4(CO)10(1,1‐P‐P)] and [H4Ru4(CO)11(P‐P)] (P‐P=chiral diphosphine of the ferrocene‐based Josiphos or Walphos ligand families) have been synthesised and characterised. The crystal and molecular structures of eleven clusters reveal that the coordination modes of the diphosphine in the [H4Ru4(CO)10(μ‐1,2‐P‐P)] clusters are different for the Josiphos and the Walphos ligands. The Josiphos ligands bridge a metal–metal bond of the ruthenium tetrahedron in the “conventional” manner, that is, with both phosphine moieties coordinated in equatorial positions relative to a triangular face of the tetrahedron, whereas the phosphine moieties of the Walphos ligands coordinate in one axial and one equatorial position. The differences in the ligand size and the coordination mode between the two types of ligands appear to be reflected in a relative propensity for isomerisation; in solution, the [H4Ru4(CO)10(1,1‐Walphos)] clusters isomerise to the corresponding [H4Ru4(CO)10(μ‐1,2‐Walphos)] clusters, whereas the Josiphos‐containing clusters show no tendency to isomerisation in solution. The clusters have been tested as catalysts for asymmetric hydrogenation of four prochiral α‐unsaturated carboxylic acids and the prochiral methyl ester (E)‐methyl 2‐methylbut‐2‐enoate. High conversion rates (>94 %) and selectivities of product formation were observed for almost all catalysts/catalyst precursors. The observed enantioselectivities were low or nonexistent for the Josiphos‐containing clusters and catalyst (cluster) recovery was low, suggesting that cluster fragmentation takes place. On the other hand, excellent conversion rates (99–100 %), product selectivities (99–100 % in most cases) and good enantioselectivities, reaching 90 % enantiomeric excess (ee) in certain cases, were observed for the Walphos‐containing clusters, and the clusters could be recovered in good yield after completed catalysis. Results from high‐pressure NMR and IR studies, catalyst poisoning tests and comparison of catalytic properties of two [H4Ru4(CO)10(μ‐1,2‐P‐P)] clusters (P‐P=Walphos ligands) with the analogous mononuclear catalysts [Ru(P‐P)(carboxylato)2] suggest that these clusters may be the active catalytic species, or direct precursors of an active catalytic cluster species.
Computational Study of the Mechanism and Selectivity of Palladium‐Catalyzed Propargylic Substitution with Phosphorus Nucleophiles
Authors: Jiménez‐Halla J. Oscar C. , Kalek Marcin , Stawinski Jacek , Himo Fahmi
Published: August 2012

The mechanism and sources of selectivity in the palladium‐catalyzed propargylic substitution reaction that involves phosphorus nucleophiles, and which yields predominantly allenylphosphonates and related compounds, have been studied computationally by means of density functional theory. Full free‐energy profiles are computed for both H‐phosphonate and H‐phosphonothioate substrates. The calculations show that the special behavior of H‐phosphonates among other heteroatom nucleophiles is indeed reflected in higher energy barriers for the attack on the central carbon atom of the allenyl/propargyl ligand relative to the ligand‐exchange pathway, which leads to the experimentally observed products. It is argued that, to explain the preference of allenyl‐ versus propargyl‐phosphonate/phosphonothioate formation in reactions that involve H‐phosphonates and H‐phosphonothioates, analysis of the complete free‐energy surfaces is necessary, because the product ratio is determined by different transition states in the respective branches of the catalytic cycle. In addition, these transition states change in going from a H‐phosphonate to a H‐phosphonothioate nucleophile.
Isolation, Biological Activity Evaluation, Structure Elucidation, and Total Synthesis of Eliamid: A Novel Complex I Inhibitor
Authors: Höfle Gerhard , Gerth Klaus , Reichenbach Hans , Kunze Brigitte , Sasse Florenz , Forche Edgar , Prusov Evgeny V.
Published: August 2012

Eliamid is a secondary metabolite isolated from two bacterial strains. This molecule features a linear polyketide backbone terminated by a tetramic acid amide moiety. Among other biological activities, eliamid shows a high and specific cytostatic action on human lymphoma and cervix carcinoma cell lines. The 2,4‐anti relative configuration of the C‐2,C‐4‐dimethyl substituted amide fragment was assigned by means of Breit’s rule. The absolute configuration of all stereocenters was determined by a combination of degradation methods, structural similarity analysis and total synthesis. The stereogenic centers were introduced by vinylogous Mukaiyama aldol reaction and two consecutive Myers alkylations. The use of pentafluorophenyl ester as acylation agent allowed the efficient formation of tetramic acid amide. The longest linear sequence in the synthesis consist of 13 steps and proceeds with 12 % overall yield. Differential spectroscopy experiments with beef heart submitochondrial particles established that eliamid is a potent inhibitor of the NADH–ubiquinone oxidoreductase complex. Additionally, biosynthesis of eliamid was investigated by feeding experiments with 13C‐labeled precursors.
Effects of Fluorine Substitution on the Shape of Neurotransmitters: the Rotational Spectrum of 2‐(2‐Fluorophenyl)Ethanamine
Authors: Melandri Sonia , Merloni Anna , Maris Assimo
Published: August 2012

The effects of fluorination on the conformational landscape of adrenergic neurotransmitters is exemplified trough the conformation analysis of 2‐(2‐F‐phenyl)ethanamine (2FPEA) carried out by microwave spectroscopy and quantum chemical calculations. Five different conformers of the nine possible stable ones for 2FPEA are observed by molecular‐beam Fourier‐transform microwave spectroscopy. Their unambiguous identification is possible by comparing the experimental rotational constants and the quadrupole coupling constants with those obtained by quantum chemical calculations carried out at the MP2/6‐311++G(d,p) level of theory. The relative abundances of the conformers in the jet are estimated from the relative intensities in the observed spectra. A qualitative agreement between experimental and theoretical energies was found, and the remaining deviations are explained by population transfer taking place during the adiabatic expansion. The energy landscape, which also takes the interconversion barriers between the conformers into consideration, is thus characterized completely by the strong interplay of quantum chemical methods and precise experimental data. Significant changes in energy and structure of the 2FPEA conformers are found compared to those obtained for the prototype molecule 2‐phenylethanamine (PEA).
Solvothermal synthesis of mesoporous slabstone‐like TiO2 and its photodegradation preference in a methyl orange‐rhodamine B mixture solution
Authors: Liu Kun , Zhu Lianjie , Li Naixuan , Sun Youguang , Li Hongbin , Zhu Xuchen
Published: August 2012

Mesoporous slabstone‐like anatase TiO2 micro‐nanometer composite structure has been successfully synthesized by a facile solvothermal method at 180 °C using polyethylene glycol (PEG) as a structure‐directing agent, followed by calcination at 400 °C for 2 h. The crystal structure and morphology of the product were characterized by XRD, SEM, TEM and HRTEM. Its BET specific surface area was obtained from N2 adsorption‐desorption isotherm measurement. Rhodamine B (RB) aqueous solution was used to evaluate the photocatalytic activity of the as‐prepared TiO2 under simulated sunlight irradiation and compared with that of commercial TiO2 (P25). A RB and methyl orange (MO) coexisting solution was chosen to investigate the photodegradation preference of the slabstone‐like TiO2 on these two dyes. The results show that the photocatalytic activity of the as‐prepared TiO2 is much higher than that of P25, and MO is the preferential degradation species in the MO‐RB mixture solution.
Development of Heterogeneous Catalysts for the Conversion of Levulinic Acid to γ‐Valerolactone
Authors: Wright William R. H. , Palkovits Regina
Published: August 2012

γ‐Valerolactone (GVL) has been identified as a potential intermediate for the production of fuels and chemicals based on renewable feedstocks. Numerous heterogeneous catalysts have been used for GVL production, alongside a range of reaction setups. This Minireview seeks to outline the development of heterogeneous catalysts for the targeted conversion of levulinic acid (LA) to GVL. Emphasis has been placed on discussing specific systems, including heterogeneous noble and base metal catalysts, transfer hydrogenation, and application of scCO2 as reaction medium, with the aim of critically highlighting both the achievements and remaining challenges associated with this field.
Bauen im Bestand – Materialkennwerte von historischem Ziegelmauerwerk
Authors: Gierga Michael , Meyer Udo
Published: August 2012

Bei Instandsetzungsmaßnahmen besteht häufig die Notwendigkeit der statischen bzw. wärmetechnischen Beurteilung der Bausubstanz. Mauerziegel waren im 20. Jahrhundert der dominierende Baustoff im Wohnungsbau. Wenn der Erstellungszeitraum eingegrenzt werden kann, können unter Bezug auf die historischen Normen Materialkennwerte für eine Vorbemessung abgeschätzt werden. Im Beitrag werden für die wesentlichen Materialkennwerte Druckfestigkeit und Wärmeleitfähigkeit von im 20. Jahrhundert verwendeten Mauerziegeln die wichtigsten Informationen zusammengestellt.

Conservation of buildings – material properties for historic clay masonry. Restoration works often require information about the thermal and loadbearing characteristics of the applied building materials. Clay bricks are the predominant material in housing in the 20th century. An estimation of design values of these historic materials is possible if the period of construction is known. The paper summarizes information about the material properties compressive strength and thermal conductivity of clay bricks applied during the 20th century.
Design, Synthesis, and Preliminary Evaluation of Substituted Cinnamic Acid Esters as Selective Matrix Metalloproteinase Inhibitors
Authors: Shi Zhi‐Hao , Li Nian‐Guang , Shi Qian‐Ping , Hao‐Tang  , Tang Yu‐Ping
Published: August 2012

Strategy, Management and Health Policy

Preclinical Research

Substituted cinnamic acid esters with extended P1′ groups were synthesized using microwave irradiation and tested for their inhibitory activities on matrix metalloproteinase (MMP)‐1, MMP‐2, and MMP‐9. Preliminary structure–activity relationship analysis and docking studies showed that hydroxyl groups in the benzene ring and the presence of extended spatial structures in the carboxylic acid played key roles in the MMP‐2 and MMP‐9 inhibitory activity and selectivity over MMP‐1.
Consequence Management: Medical Countermeasures
Authors: Bullard William
Published: August 2012

Strategy, Management and Health Policy

Enabling Technology, Genomics, Proteomics
Preclinical Research
Preclinical Development Toxicology, Formulation Drug Delivery, Pharmacokinetics
Clinical Development Phases I‐III Regulatory, Quality, Manufacturing
Postmarketing Phase IV

Medical countermeasure drug development is a complex field that is an important component of public and private medical preparedness. Medical professionals and emergency management planners in military, government, and private settings depend on successful drug development and collaboration among project sponsors, research institution(s), and private pharmaceutical companies. When a medical countermeasure is developed, manufacturing, distribution security, logistics, training, and protocol needs are arranged within a complex economic and political reality. The medical countermeasure products that are developed sit waiting with hope that they are never used. When they are needed, rapid access and well‐developed preparedness plans are critical for the important emergency response that is expected in the aftermath of a disaster. Preparedness plans and procedures are continually changing, and medical countermeasure practices need to change and develop further to keep pace with evolving risk. Partnerships among government, research, and the private sector can help guarantee successful drug development toward improved emergency preparedness. These elements, when combined with well‐developed preparedness plans, can help ensure the rapid availability of important medications needed to treat victims following a terrorist event or other disaster.
Efficacy of a Novel Orally Administered Formulation of DTPA Tablets for Decorporating an Intravenously Injected Radionuclide: A Comparison with Intravenously Administered Licensed DTPA
Authors: Shankar Gita N. , Weber Waylon , Doyle‐Eisele Melanie , Guilmette Raymond A.
Published: August 2012

Strategy, Management and Health Policy

Enabling Tchnology, Genomics, Proteomics
Preclinical Research
Preclinical Development Toxicology, Formulation Durg Delivery, Pharmacokinetics
Clinical Development Phases I‐III Regulatory, Quality, Manufacturing
Postmarketing Phase IV

A proprietary minitablet formulation of the chelating agent diethylenetriaminepentaacetic acid (DTPAMT) was administered orally to rats injected with (241
Am) (III)‐citrate and compared with untreated controls. The positive control was intravenously administered diethylenetriaminepentaacetate (DTPA) (IVDTPA). Groups of six young adult rats (three male, three female) were injected intravenously with 241
Am, with each rat placed in an individual metabolism cage for excreta collection. The groups were then treated once with IVDTPA or DTPAMT at 1 h, or 1, 5, or 14 days postinjection, with sacrifice at 8, 8, 12, and 21 days postinjection, respectively. Sacrifice of three untreated control groups occurred 8, 12, and 21 days postinjection. At necropsy, all tissues, associated urine, feces, and cage wash samples were collected and analyzed for (241
Am) content. The average recovery for all experimental groups was 95.2 ± 3.6% administered 241
Am dose. Tissue and excreta analyses of (241
Am) were compared for the treatment groups and untreated controls and with IVDTPA using two‐way analysis of variance. DTPAMT 241
Am removal efficacy was statistically significant for all administration times compared with untreated controls. For systemically administered (241
Am), the primary deposition sites, bone and liver, incurred the highest radiation doses. DTPAMT reduced liver (241
Am) content by 60–70% and bone content by 40% at treatment times of 1 h,1 day, and 5 days when compared with untreated controls. For all times, DTPAMT compared well with IVDTPA. For DTPAMT, (241
Am) excretion elevation in urine was protracted beyond that typically observed with IVDTPA.
Evaluating new severity dimensions in the DSM‐5 for bulimic syndromes using mixture modeling
Authors: Keel Pamela K. , Crosby Ross D. , Hildebrandt Thomas B. , Haedt‐Matt Alissa A. , Gravener Julie A.
Published: August 2012

Objective:

Proposed DSM‐5 severity dimensions reveal ambiguity regarding the extent to which certain features define boundaries between similar diagnoses or represent underlying dimensions within a broader category of bulimic syndromes. The current study utilized a novel mixed modeling approach that can simultaneously model latent dimensions and latent categories to address this ambiguity.

Method:

Data from structured clinical interviews in 528 adult participants were analyzed.

Results:

A three‐class solution with one severity dimension that was invariant across groups provided the best‐fitting model. Both latent Classes 1 and 2 included bulimic syndromes but were distinguished by greater purging and weight phobia in latent Class 1. Latent Class 3 resembled a noneating disorder class. External validation analyses supported significant differences among empirically derived groups.

Discussion:

Weight phobia contributes to categorical distinctiveness among bulimic syndromes whereas other features (purging, binge eating, and weight) may do so only in specific combinations. Uniform severity criteria may be appropriate across bulimic syndromes. © 2012 by Wiley Periodicals, Inc. (Int J Eat Disord 2013)
Childbearing and mortality among women with anorexia nervosa
Authors: Papadopoulos Fotios C. , Karamanis Georgios , Brandt Lena , Ekbom Anders , Ekselius Lisa
Published: August 2012

Objective:

To assess the association between childbearing and mortality from anorexia nervosa (AN).

Method:

A total of 5,251 females, from a population‐based Swedish registry, admitted with an AN diagnosis during the period 1973–2003 were included. Standardized mortality ratios (SMR) were estimated and hazard ratios (HR) were calculated using Cox regression.

Results:

Nulliparous women had a sixfold higher mortality due to natural causes and ninefold higher mortality due to unnatural causes compared to the general population. Parous women had higher mortality compared to the general population only due to unnatural causes. Suicide was the most common cause of death. Childbearing was associated with a 65% lower mortality. One hundred forty four women out of 1,941 parous women were hospitalized perinatally for any psychiatric disorder (7.4%).

Discussion:

Childbearing is associated with lower mortality among women with AN. © 2012 by Wiley Periodicals, Inc. (Int J Eat Disord 2013)
Supramolecular Hybrid Bidentate Ligands in Asymmetric Hydrogenation
Authors: Bellini Rosalba , Reek Joost N. H.
Published: August 2012

In this study we introduce a novel class of supramolecular bidentate hybrid ligands and their application in the rhodium‐catalysed asymmetric hydrogenation of prochiral olefins. A new supramolecular strategy is reported in which the two nonequivalent phosphorus atoms are linked covalently to a chiral scaffold, and the supramolecular interactions are used to control the second coordination sphere of the transition‐metal catalyst. The supramolecular assembly is formed in situ by selective interaction between the nitrogen‐donor atoms and the zinc(II) template, which is essential for obtaining high activity and selectivity. The investigations of the different zinc(II) and ruthenium(II) templates on the reaction parameters revealed a dependence of the activity and selectivity on the association constant between the supramolecular template and the pyridyl ligands. The scope of the supramolecular assemblies was explored in the Rh‐catalysed asymmetric hydrogenation of α‐dehydroamino acid esters and Roche ester derivatives. High activities and good to excellent enantioselectivities up to 99 % ee were obtained with the supramolecular ligands. Application of the supramolecular strategy on the basis of variations of the steric and electronic properties of zinc(II) templates demonstrate that these changes can influence key reaction parameters such as activity and selectivity.
Synthesis and Characterization of Dioxopyrrolopyrrole Derivatives Having Electron‐Withdrawing Groups
Authors: Yamagata Takuya , Kuwabara Junpei , Kanbara Takaki
Published: August 2012

New dioxopyrrolopyrrole (DPP) derivatives bearing electron‐withdrawing groups have been synthesized, and their photophysical properties and redox behaviors have been examined. The electron‐accepting abilities of the derivatives were elucidated by cyclic voltammetry (CV) and redox titration analysis. The introduction of the electron‐withdrawing groups modulated the redox properties of the DPP core, and the addition of the 1,1,4,4‐tetracyanobutadiene (TCBD) moieties created a multi‐redox system. The application of TD‐DFT (time‐dependent density functional theory) revealed the HOMO and LUMO of the compounds, and the calculation results were consistent with the photophysical and electrochemical properties of the compounds. The TCBD moieties provided the dye molecule with unique physical properties such as broad charge‐transfer absorption bands and reversible multi‐redox behavior.
Corrole–Porphyrin Conjugates with Interchangeable Metal Centers
Authors: Ngo Thien H. , Nastasi Francesco , Puntoriero Fausto , Campagna Sebastiano , Dehaen Wim , Maes Wouter
Published: August 2012

Oligoporphyrinoid materials composed of two or three tetrapyrrolic macrocycles have been synthesized by either mono‐ or disubstitution (SNAr) of a phenolic Zn‐AB3‐porphyrin on a meso‐dichloropyrimidinyl‐substituted Cu‐AB2‐corrole. Selective metallation/demetallation sequences were carried out on these mixed corrole–porphyrin conjugates to afford multichromophoric systems with variable metal centers. The absorption spectra of the free‐base corrole–porphyrin systems were essentially additive, which demonstrates that only weak intercomponent interactions take place in these assemblies and therefore they can be regarded as supramolecular systems. Photophysical studies of the free‐base conjugates showed that these species are highly fluorescent, with fluorescence occurring from the lowest‐energy singlet state of the porphyrin subunit(s), which is (are) the lowest‐energy state(s) of the assemblies. Pump‐probe transient absorption spectroscopy experiments demonstrated that very efficient (>95 %) corrole‐to‐porphyrin singlet–singlet energy transfer takes place in these pyrimidinyl‐bridged multichromophoric systems by a coulombic mechanism with rate constants on the picosecond timescale.
Supra‐glacial deposition and flux of catastrophic rock–slope failure debris, south‐central Alaska
Authors: Uhlmann Manuela , Korup Oliver , Huggel Christian , Fischer Luzia , Kargel Jeffrey S.
Published: August 2012

The ongoing debate over the effects of global environmental change on Earth's cryosphere calls for detailed knowledge about process rates and their variability in cold environments. In this context, appraisals of the coupling between glacier dynamics and para‐glacial erosion rates in tectonically active mountains remain rare. We contribute to filling this knowledge gap and present an unprecedented regional‐scale inventory of supra‐glacial sediment flux and hillslope erosion rates inferred from an analysis of 123 large (> 0·1 km2) catastrophic bedrock landslides that fell onto glaciers in the Chugach Mountains, Alaska, as documented by satellite images obtained between 1972 to 2008. Assuming these supra‐glacial landslide deposits to be passive strain markers we infer minimum decadal‐scale sediment yields of 190 to 7400 t km–2 yr–1 for a given glacier‐surface cross‐section impacted by episodic rock–slope failure. These rates compare to reported fluvial sediment yields in many mountain rivers, but are an order of magnitude below the extreme sediment yields measured at the snouts of Alaskan glaciers, indicating that the bulk of debris discharged derives from en‐glacial, sub‐glacial or ice‐proximal sources. We estimate an average minimum para‐glacial erosion rate by large, episodic rock–slope failures at 0·5–0·7 mm yr–1 in the Chugach Mountains over a 50‐yr period, with earthquakes likely being responsible for up to 73% of this rate. Though ranking amongst the highest decadal landslide erosion rates for this size of study area worldwide, our inferred rates of hillslope erosion in the Chugach Mountains remain an order of magnitude below the pace of extremely rapid glacial sediment export and glacio‐isostatic surface uplift previously reported from the region. Copyright © 2012 John Wiley & Sons, Ltd.
Thermal enhancement of natural magnetism as a tool for tracing eroded soil
Authors: Armstrong Alona , Quinton John N. , Maher Barbara A.
Published: August 2012

Determining sources, quantities and travel distances of eroding soil is of increasing importance given its impact on‐ and off‐site, the sediment‐associated transport of nutrients, metals and micro‐organisms and the ongoing need to provide data for soil erosion model development and validation. Many soil tracers have been developed; however, most comprise foreign materials, such as fluorescent beads and rare earth oxides, which cast doubts on the validity of tracing results given their different physical characteristics. To avoid these problems, we have investigated the potential of soil, which has been heated under reducing conditions to enhance its ferrimagnetic content, as a soil erosion tracer; while the technique has been used successfully to trace river sediment it has not been successfully applied to soil erosion studies. For a suite of 16 magnetic concentration‐dependent properties, values were found to be significantly greater, by at least one order of magnitude, after heating, both for the bulk soil and nine individual particle size fractions. Individual size fractions could be differentiated using two different magnetic properties, thus illustrating the technique's potential to provide information on particle size‐specific erosion. Soil box experiments demonstrated the potential for both in situ measurement of magnetic susceptibility and laboratory measurement of the magnetic properties of eroded sediment, to trace and quantify soil erosion. Thus, heated soil, with artificially‐enhanced ferrimagnetic properties, is successfully demonstrated to have great potential as a size‐specific, cost‐effective and representative soil erosion tracer. Copyright © 2012 John Wiley & Sons, Ltd.
Second‐Generation Prediction Markets for Information Aggregation: A Comparison of Payoff Mechanisms
Authors: Slamka Christian , Jank Wolfgang , Skiera Bernd
Published: August 2012

Initial applications of prediction markets (PMs) indicate that they provide good forecasting instruments in many settings, such as elections, the box office, or product sales. One particular characteristic of these ‘first‐generation’ (G1) PMs is that they link the payoff value of a stock's share to the outcome of an event. Recently, ‘second‐generation’ (G2) PMs have introduced alternative mechanisms to determine payoff values which allow them to be used as preference markets for determining preferences for product concepts or as idea markets for generating and evaluating new product ideas. Three different G2 payoff mechanisms appear in the existing literature, but they have never been compared. This study conceptually and empirically compares the forecasting accuracy of the three G2 payoff mechanisms and investigates their influence on participants' trading behavior. We find that G2 payoff mechanisms perform almost as well as their G1 counterpart, and trading behavior is very similar in both markets (i.e. trading prices and trading volume), except during the very last trading hours of the market. These results indicate that G2 PMs are valid instruments and support their applicability shown in previous studies for developing new product ideas or evaluating new product concepts. Copyright © 2011 John Wiley & Sons, Ltd.
A Comparison of Bayesian and Frequentist Approaches to Incorporating External Information for the Prediction of Prostate Cancer Risk
Authors: Newcombe Paul J. , Reck Brian H. , Sun Jielin , Platek Greg T. , Verzilli Claudio , Kader A. Karim , Kim Seong‐Tae , Hsu Fang‐Chi , Zhang Zheng , Zheng S. Lilly , Mooser Vincent E. , Condreay Lynn D. , Spraggs Colin F. , Whittaker John C. , Rittmaster Roger S. , Xu Jianfeng
Published: August 2012

We present the most comprehensive comparison to date of the predictive benefit of genetics in addition to currently used clinical variables, using genotype data for 33 single‐nucleotide polymorphisms (SNPs) in 1,547 Caucasian men from the placebo arm of the REduction by DUtasteride of prostate Cancer Events (REDUCE®) trial. Moreover, we conducted a detailed comparison of three techniques for incorporating genetics into clinical risk prediction. The first method was a standard logistic regression model, which included separate terms for the clinical covariates and for each of the genetic markers. This approach ignores a substantial amount of external information concerning effect sizes for these Genome Wide Association Study (GWAS)‐replicated SNPs. The second and third methods investigated two possible approaches to incorporating meta‐analysed external SNP effect estimates – one via a weighted PCa 'risk' score based solely on the meta analysis estimates, and the other incorporating both the current and prior data via informative priors in a Bayesian logistic regression model. All methods demonstrated a slight improvement in predictive performance upon incorporation of genetics. The two methods that incorporated external information showed the greatest receiver‐operating‐characteristic AUCs increase from 0.61 to 0.64. The value of our methods comparison is likely to lie in observations of performance similarities, rather than difference, between three approaches of very different resource requirements. The two methods that included external information performed best, but only marginally despite substantial differences in complexity.